WO2008096335A2 - Producing an array of nanoscale structures on a substrate surface via a self-assembled template - Google Patents

Producing an array of nanoscale structures on a substrate surface via a self-assembled template Download PDF

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Publication number
WO2008096335A2
WO2008096335A2 PCT/IL2007/000168 IL2007000168W WO2008096335A2 WO 2008096335 A2 WO2008096335 A2 WO 2008096335A2 IL 2007000168 W IL2007000168 W IL 2007000168W WO 2008096335 A2 WO2008096335 A2 WO 2008096335A2
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Prior art keywords
array
nanoscale
group
self
substrate
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PCT/IL2007/000168
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French (fr)
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WO2008096335A3 (en
Inventor
Ernesto Joselevich
Rachel Gabai
Ariel Ismach
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Yeda Research And Development Co. Ltd.
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Priority to PCT/IL2007/000168 priority Critical patent/WO2008096335A2/en
Publication of WO2008096335A2 publication Critical patent/WO2008096335A2/en
Publication of WO2008096335A3 publication Critical patent/WO2008096335A3/en

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00015Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
    • B81C1/00023Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
    • B81C1/00031Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C2201/00Manufacture or treatment of microstructural devices or systems
    • B81C2201/01Manufacture or treatment of microstructural devices or systems in or on a substrate
    • B81C2201/0101Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
    • B81C2201/0147Film patterning
    • B81C2201/0149Forming nanoscale microstructures using auto-arranging or self-assembling material

Definitions

  • the present invention relates to the general field of naiioscale science (nanoscience) or technology (nanotechnology), encompassing, or at least associated with, sub-fields and areas such as nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electromechanics (nanoelectromechanics), and nanoscale semiconductor technology, focusing on methods, processes, or techniques, which are used for producing or fabricating arrays of nanoscale structures on substrate surfaces. More particularly, the present invention relates to a method for producing an array of nanoscale structures on a substrate surface, via a self-assembled template.
  • the present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures on various different types or kinds of substrate surfaces.
  • the produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior.
  • the present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components.
  • nanoscience or nanotechnology e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor
  • Nanopattern generation systems include electron-beam lithography [3], scanning probe nanolithographies, such as dip-pen nanolithography [4], and constructive nanolithography [5], which can reach feature sizes down to 5 nm, 30 nm, and 9 nm, respectively.
  • These methods have the advantage that the pattern is encoded in a computer-assisted design software file, allowing the deterministic generation of arbitrary, aperiodic patterns, as well as periodic patterns with high degrees of perfection and long-range order.
  • a major disadvantage of these 'top-down' nanopattern generation methods, however, is that they are serial, and hence extremely time-consuming for large areas.
  • a recent nanofabrication method based on the replication of superlattice cross-sections yields sub- 10 nm periodic nano wires of high perfection [6 - 8], but the width of the patterned area is limited to a few hundred microns by the thickness of the templating superlattice.
  • This aspect presents a severe size limitation, which completely precludes the manufacturing of large-area nanostructured surfaces which are needed, and widely used, in industrial applications, such as aligning layers for liquid crystal displays (LCDs).
  • LCDs liquid crystal displays
  • having a practical, efficient, and cost effective, method for large-scale production of geometrically and chemically tailored alignment layers for liquid crystal displays (LCDs) would enable a finer and more rational control of the nematic phases than the mechanically rubbed films used today.
  • Prior art includes various additional teachings [9 - 14] about manufacturing (fabricating) nanoscale structures on substrate surfaces.
  • 'Bottom-up' nanopattern generation processes based on spontaneous self-assembly are of special technological and scientific interest, especially for large-area, periodic nanostructures where perfection and long-range order are less critical. This may be the case of nanoelectronics, where connectivity and short-range order are more important than long-range order, and there can be a certain degree of defect-tolerance [15], as well as many other applications in surface and materials technology, such as display technology, microarray technology, microelectromechanics, chemical/biological sensing, etc. [16].
  • Such promising approaches of bottom-up nanopattern generation include those based on the self-assembly of block-copolymers (block-copolymer lithography) [17], colloidal particles (nanosphere lithography) [18], and biomolecules (biotemplate lithography) [19], where the patterns are encoded in the polymer block lengths and their relative affinities, the colloidal nanoparticle size, and the genetically encoded molecular shape and recognition, respectively.
  • Typical crystals are usually overlooked as nanoscopically dull, since their lattice parameters are well below the nanoscale. Though true for the bulk, this is not so for the crystal surfaces, which are intrinsically unstable, and can undergo a series of spontaneous restructurations (self-assemblies, self-organizations), eventually ending with the formation of a periodically faceted surface [20, 21]. Such surface restructuration processes lead to a progressive increase in the surface periodicity from 0.1 nm to 1 ⁇ m, encompassing the whole nanoscale. Periodically faceted surfaces have been extensively used as epitaxial substrates for the production of self-assembled nano wires such substrates [20 - 23]. Periodic faceting patterns, however, have not yet been transferred or replicated onto other substrates.
  • the present invention relates to a method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template.
  • the present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures on various different types or kinds of substrate surfaces.
  • the produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior.
  • the present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components, just a few examples of such are memories, logic gates, sensors, actuators, circuits, polarizers, and liquid crystal displays (LCDs).
  • Such nanoscale devices and components are used, or are potentially useful, in essentially every field of science and technology.
  • a method for producing an array of nanoscale structures on a substrate surface comprising: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features; treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied materials) having the replica configuration and shape; contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
  • the self-assembled template is composed of a crystalline substance selected from the group consisting of crystalline inorganic matter, crystalline organic matter, and a combination thereof.
  • the crystalline inorganic matter is selected from the group consisting of: a crystalline single metal oxide, a crystalline mixed metal oxide, a crystalline inorganic salt, a periodic table group IV element, a compound of periodic table group IV elements, a compound of a periodic table group III element and a periodic table group V element, a compound of a periodic table group II element and a periodic table group VI element, a crystalline carbide, a crystalline suicide, a crystalline hydride, a crystalline elemental metal, and a crystalline alloy.
  • the crystalline single metal oxide is selected from the group consisting of: alpha-aluminum oxide (sapphire) [ ⁇ -Al 2 O 3 ], alpha-silicon oxide (quartz) [(X-SiO 2 ], zinc oxide [ZnO], magnesium oxide [MgO], and titanium oxide [TiO 2 ].
  • the periodic table group IV element is elemental silicon [Si].
  • the compound of a periodic table group III element and a periodic table group V element is gallium arsenide [GaAs].
  • the crystalline organic matter is selected from the group consisting of: an amino acid, a protein, a carbohydrate, an aliphatic compound, and an aromatic compound.
  • the combination of crystalline inorganic matter and crystalline organic matter is selected from the group consisting of: a crystalline organic salt, and a crystalline organometallic complex.
  • the self-assembled template has a three-dimensional polyhedron bulk or overall geometrical shape or form, or a three-dimensional non-polyhedron curved bulk or overall geometrical shape or form.
  • the three-dimensional polyhedron bulk or overall geometrical shape or form is selected from the group consisting of: a parallelpiped, a prism, and a pyramid.
  • the three-dimensional non-polyhedron curved bulk or overall geometrical shape or form is selected from the group consisting of: a cylinder, a disc (disk), and a cone.
  • the self-assembled template has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a range of between about 0.1 nanometer (nm) and about 1 meter (m).
  • the self-assembled template has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron ( ⁇ m) and about 1 centimeter (cm), (ii) a second range of between about 100 microns ( ⁇ m) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
  • the self-assembled template, the array of nanoscale features corresponds to a parallelogram or parallelogram-like ordered arrangement or set of features, structures, or elements.
  • the nanoscale features of the array are selected from the group consisting of nanoscale facets (nanofacets), nanoscale grooves (nanogrooves), and nanoscale steps (nanosteps).
  • the array of nanoscale features, a single or individual nanoscale feature has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the array of nanoscale features, pitch between two neighboring similar nanoscale features has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the crystal surface is obtained by cutting at least part of a crystalline substance, or by depositing a crystalline substance onto a surface of another substance.
  • the cutting is along a singular cutting plane, corresponding to a low-index plane, of a crystal.
  • the cutting is along a vicinal cutting plane at a miscut tilt angle ( ⁇ ) relative to nearest low-index plane of a crystal.
  • the treating involves annealing the crystal surface.
  • the treating involves etching the crystal surface.
  • the applying step is performed according to a material applying process selected from the group consisting of: casting (molding), and depositing.
  • the casting (molding) process is selected from the group consisting of: a polymer cross-linking type of casting (molding) process, and a liquid-to-solid phase transition type of casting (molding) process.
  • the depositing process is selected from the group consisting of: a physical deposition process, and a chemical deposition process.
  • the at least one material applied upon the at least part of the array is composed of a substance selected from the group consisting of organic matter, inorganic matter, and a combination thereof.
  • the organic matter is an organic polymer.
  • the organic polymer is selected from the group consisting of: a thermoplastic, a thermoset, an elastomer, and any combination thereof.
  • the inorganic matter is selected from the group consisting of: a metal element, a metal alloy, a semi-metal element, a non-metal element, and any combination thereof.
  • the metal element is selected from the group consisting of: a noble metal element, a transition metal element, and a main group metal element.
  • the metal alloy is selected from the group consisting of: palladium-gold [PdAu], and platinum-iridium [PtIr].
  • the semi-metal element is selected from the group consisting of: elemental silicon [Si], and elemental germanium [Ge].
  • the non-metal element is selected from the group consisting of: an allotrope of carbon, and elemental boron [B].
  • the combination of a metal element and a non-metal element, in a form of a compound is selected from the group consisting of: indium oxide [In 2 Oa], molybdenum diselinide [MoSe 2 ], and boron nitride [BN].
  • the combination of organic matter and inorganic matter is an organic- inorganic polymer.
  • the organic-inorganic polymer is selected from the group consisting of: an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, and any combination thereof.
  • the at least one material applied upon the at least part of the array has an amorphous structure, or a crystalline structure.
  • the treating step includes forming a stand-alone cast (mold) type of surface replica element having the replica configuration and shape.
  • the treating step further includes inking, by using a suitable ink, surface of the cast (mold) type of the surface replica element.
  • the ink is selected from the group consisting of a thiol compound based ink, and a silane compound based ink.
  • the thiol compound based ink is a solution or suspension of a thiol compound selected from the group consisting of: n-hexadecanethiol, n-dodecanethiol, and n-octadecanethiol.
  • the silane compound based ink is a solution or suspension of a silane compound selected from the group consisting of: octadecyltricholorosilane, 3-aminopropyl- triethoxisilane, and 3-mercaptopropyl-trimethoxysilane.
  • the processing step includes forming a nanopattern (nanoscale pattern) upon the substrate surface.
  • the nanopattern (nanoscale pattern) is formed by using the cast (mold) type of the surface replica element with a roller.
  • the processing step further includes modifying the nanopattern (nanoscale pattern), by using a chemical functionalizing (derivatizing) procedure, or by using an etching procedure.
  • the modifying is performed by using a thiol compound based chemical functionalizing (derivatizing) procedure, involving a thiol compound based chemical functionalizing (derivatizing) reagent.
  • the modifying is performed by using a silane compound based type of functionalizing (derivatizing) procedure, involving a silane compound based chemical functionalizing (derivatizing) reagent.
  • the modifying is performed by using a wet etching procedure, or a dry etching procedure.
  • the nanoscale structures are selected from the group consisting of: nanoscale wires (nanowires), nanoscale strips (nanostrips), nanoscale belts (nanobelts), nanoscale particles (nanoparticles), and nanoscale grooves (nanogrooves).
  • a single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • a single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • pitch between two neighboring similar nanoscale structures has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the present invention is implemented by performing steps or procedures, and sub-steps or sub-procedures, in a manner selected from the group consisting of manually, semi-automatically, fully automatically, and a combination thereof, involving use and operation of various devices, instruments, and, peripheral equipment, utilities, accessories, and materials, in a manner selected from the group consisting of manually, semi-automatically, fully automatically, and a combination thereof.
  • steps or procedures, sub-steps or sub-procedures, devices, instruments, and, peripheral equipment, utilities, accessories, and materials used for implementing a particular embodiment of the disclosed invention, the steps or procedures, and sub-steps or sub-procedures, are performed by using hardware, software, or/and an integrated combination thereof, and the devices, instruments, and, peripheral equipment, utilities, accessories, and materials, operate by using hardware, software, or/and an integrated combination thereof.
  • Fig. 1 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary generalized preferred embodiment of implementing the method for producing an array of nanoscale structures on a substrate surface, in accordance with the present invention
  • Figs. 2a - 2e are schematic (flow-type) diagrams illustrating main steps
  • Figs. 3a - 3d are schematic (flow-type) diagrams illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of forming a 'nanostepped' type faceted self-assembled template, including cutting a crystal along a 'vicinal' cutting plane (at a miscut tilt angle ( ⁇ ) relative to the nearest low-index plane) of the crystal, wherein the self-assembled template is used for generating an array of nanoscale structures on a substrate surface, in accordance with the present invention;
  • Fig. 4 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanowires (nanoscale structures) on the substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface, in accordance with the present invention;
  • Fig. 5 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) a grid (waffle) type array of nanowires (nanoscale structures) on the substrate surface, in accordance with the present invention;
  • a surface replica element e.g., of Fig. 4
  • a grid (waffle) type array of nanowires (nanoscale structures) on the substrate surface in accordance with the present invention
  • Fig. 6 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with an array of nanowires (nanoscale structures) on a substrate surface (e.g., of Fig. 4), for generating (via an etching technique) an array of nanoparticles (nanoscale structures) on the substrate surface, in accordance with the present invention;
  • Fig. 6 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with an array of nanowires (nanoscale structures) on a substrate surface (e.g., of Fig. 4), for generating (via an etching technique) an array of
  • FIG. 7 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanogrooves (nanoscale structures) on the substrate surface, in accordance with the present invention;
  • a surface replica element e.g., of Fig. 4
  • nanogrooves nanoscale structures
  • Fig. 8 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with a roller for forming a nanopattern on a substrate surface, which, in turn, is useable for generating (via a functionalizing technique) an array of nanostrips on the substrate surface, in accordance with the present invention;
  • a surface replica element e.g., of Fig. 4
  • a roller for forming a nanopattern on a substrate surface which, in turn, is useable for generating (via a functionalizing technique) an array of nanostrips on the substrate surface, in accordance with the present invention
  • Fig. 9 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanobelts (nanoscale structures) on a substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface, in accordance with the present invention;
  • Fig. 10 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by treating a 'singular' crystal surface, particularly highlighting application of material upon the surface of the self-assembled template, which, in turn, is directly used for generating an array of nanowires (nanoscale structures) on a substrate surface, in accordance with the present invention;
  • Fig. 1 Ia is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface (obtained by cutting along the 'M-plane' of a sapphire (alpha-alumina [01-Al 2 O 3 ]) crystal), and characterized by R-plane and S-plane nanofacets, as exemplified and described in Example 1, in accordance with the present invention;
  • Fig. 1 Ib is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface (obtained by cutting along a 'vicinal C-plane' of a sapphire (alpha-alumina [0,-Al 2 O 3 ]) crystal), and characterized by R-plane and C-plane nanofacets, as exemplified and described in Example 2, in accordance with the present invention; Fig.
  • FIG. 12a is an atomic force microscope (AFM) topographic mode image of an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface includes an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a crystal surface;
  • the self-assembled template corresponds to an annealed sapphire M-plane crystal surface (e.g., as shown in Fig. lla), characterized by R-plane and S-plane nanofacets having inclinations of 16.7 degrees and 32.6 degrees, respectively, pitch of 37 ⁇ 3 nanometers (nm), and height (depth) of about 8 nanometers (nm), as described in Example 1, in accordance with the present invention;
  • Fig. 12b is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary nanogrooved, nanofaceted surface replica element;
  • the surface replica element (formed according to the embodiment illustrated in Fig. 4) corresponds to a polydimethylsiloxane (PDMS) cast (mold) (elastomeric stamp) (whose nanogrooves have a pitch of 40 ⁇ 5 nanometers (nm)) of the surface of the nanogrooved, nanofaceted self-assembled template (annealed sapphire M-plane crystal surface) shown in Fig. 12a, as described in Example 1, in accordance with the present invention;
  • Fig. 12b is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary nanogrooved, nanofaceted surface replica element;
  • the surface replica element formed according to the embodiment illustrated in Fig. 4
  • PDMS polydimethylsiloxane
  • mold mold
  • elastomeric stamp whose nanogroo
  • FIG. 12c is an atomic force microscope (AFM) friction mode of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of 1-hexadecanethiol functionalized nanostrips (width of 10 - 20 nanometers (nm) and pitch of 50 ⁇ 5 nanometers (nm)) on a gold [Au] with chemically bound 16-mercaptohexadecanoic acid substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by reacting a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate, with 16-mercaptohexadecanoic acid, as described in Example I 5 in accordance with the present invention;
  • AFM atomic force microscope
  • Fig. 12d is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of gold [Au] nano wires on a silicon [Si] substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate, as described in Example 1, in accordance with the present invention; Fig.
  • AFM projected atomic force microscope
  • FIG. 12e is a graphical plot of nano wire height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanowires, of the array of gold [Au] nanowires on the silicon [Si] substrate surface shown in Fig. 12d; the gold [Au] nanowires have a width (half-pitch) of about 20 nanometers (nm) and a height (diameter) of about 20 nanometers (nm), as described in Example 1, in accordance with the present invention; Fig.
  • FIG. 12f is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a grid (waffle) type array of gold [Au] nanowires on a silicon [Si] substrate surface; the array was generated (according to embodiments illustrated in Figs. 4 and 5) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate; as described in Example I 5 in accordance with the present invention;
  • AFM atomic force microscope
  • Fig. 13a is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale sti*uctures on a substrate surface; the image shows an array of nanogrooves (pitch of about 50 nanometers (nm)) on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs.
  • SEM scanning electron microscope
  • a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si] (wafer) substrate surface wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig.
  • Fig. 13b is an atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig.
  • AFM atomic force microscope
  • nanogrooves have a pitch of about 50 nanometers (urn), as described in
  • Fig. 13c is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Figs. 13a and 13b, as described in Example 2, in accordance with the present invention;
  • AFM projected atomic force microscope
  • Fig. 13d is a graphical plot of nanogroove height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanogrooves, of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13 c, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a height (depth) of about 120 nanometers (nm), as described in Example 2, in accordance with the present invention;
  • Fig. 13e is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a waffle type array of nanogrooves on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs. 5 and 7) by selective anisotropic wet etching of a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si]
  • OTS octadecyltrichlorosilane
  • nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig. 1 Ia), as described in Example 2, in accordance with the present invention; and
  • Fig. 13f is an atomic force microscope (AFM) topographic mode (zoom) image of the surface of the waffle type array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13e, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a (depth) height of about 100 nanometers (nm), as described in Example 2, in accordance with the present invention.
  • AFM atomic force microscope
  • the present invention relates to a method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template.
  • the present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures on various different types or kinds of substrate surfaces.
  • the produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior.
  • the present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components, just a few examples of such are memories, logic gates, sensors, actuators, circuits, polarizers, and liquid crystal displays (LCDs).
  • Such nanoscale devices and components are used, or are potentially useful, in essentially every field of science and technology.
  • the method for producing an array of nanoscale structures on a substrate surface includes the following main steps (procedures), and structures thereof: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features; treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
  • a main aspect of novelty and inventiveness of the present invention is provision of a method for producing (fabricating) an array of nanoscale structures on a substrate surface, via (by using) a self-assembled template, wherein the surface of the self-assembled template includes an array of nanoscale features that were spontaneously formed by treating a crystal surface of a crystal.
  • the present invention is not limited in its application to the details of the order or sequence, and number, of steps or procedures, sub-steps or sub-procedures, of operation or implementation of the method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template, or to the details of the equipment, chemical reagents, and materials, used for implementing the method, set forth in the following illustrative description, accompanying drawings, and examples, unless otherwise specifically stated herein.
  • the present invention is capable of other embodiments and of being practiced or carried out in various ways.
  • steps or procedures, sub-steps or sub-procedures, equipment, chemical reagents, and materials which are equivalent or similar to those illustratively described herein can be used for practicing or testing the present invention
  • suitable steps or procedures, sub-steps or sub-procedures, equipment, chemical reagents, and materials are illustratively described and exemplified herein.
  • 'features' refers to distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements) of an object or entity.
  • an example of such an object or entity is a surface of a self-assembled template.
  • the term 'features' refers to, for example, distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements) of a surface of a self-assembled template.
  • exemplary features i.e., distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements), of a surface of a self-assembled template, are: facets, grooves, and steps.
  • these exemplary features are indicated as being of 'nanoscale', i.e., nanofacets, nanogrooves, and nanosteps, respectively, where the term 'nano', other terms prefixed by the term 'nano', and phrases including 'nano' terms, are each defined immediately following.
  • 'nano' refers to the prefix (symbol 'n') of the unit, meter (symbol 'n ⁇ ), in the SI (International System of Units) system of units denoting a factor of 10 "9 , of a size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), expressed in terms of nanometer or nanometers, each abbreviated or symbolized as 'nm'.
  • 'nano' is also used herein as a prefix of, and combined with, each of various other terms, for indicating that the 'other' term, i.e., feature(s), structure(s), element(s), or characteristic(s), has (have), or is (are) associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch) in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
  • size dimension e.g., length, width, height (thickness), depth, diameter, pitch
  • 'nano' is used as a prefix of, and combined with, each of the following terms (expressed in singular form, or in plural form, i.e., with the suffix 's' (s)): facet(s), groove(s), grooved, step(s), stepped, wire(s), strip(s), particle(s), belt(s), pattera(s), and scale.
  • each of the following 'nano' terms: nanofacet(s), nanogroove(s), nanostep(s), nanowire(s), nanostrip(s), nanoparticle(s), nanobelt(s), and nanopattern(s), is used for indicating that the feature(s), structure(s), element(s), or characteristic ⁇ ), i.e., facet(s), groove(s), step(s), wire(s), strip(s), particle(s), belt(s), or pattern(s), respectively, has (have), or is associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
  • size dimension e.g., length, width, height (thickness), depth, diameter, pitch
  • nanoscale nanoscale, nanogrooved, and nanostepped
  • nanoscale feature(s) nanoscale structure(s)
  • nanogrooved surface nanostepped surface
  • the 'nano' phrase, nanoscale feature(s), as used herein, refers to a feature (features) (typically, on a surface) which has (have), or is (are) associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
  • nanoscale structure(s) refers to a structure (structures) (typically, on a surface) which has (have), or is (are) associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
  • size dimension e.g., length, width, height (thickness), depth, diameter, pitch
  • the 'nano' phrase, nanogrooved refers to a surface that includes and is characterized by, grooves (i.e., nanogrooves), and therefore, is described as being 'grooved' (i.e., nanogrooved), wherein each groove (i.e., nanogroove) has at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
  • a size dimension e.g., length, width, height (thickness), depth, diameter, pitch
  • the 'nano' phrase, nanostepped refers to a surface that includes and is characterized by, steps, and therefore, is described as being 'stepped' (i.e., nanostepped), wherein each step (i.e., nanostep) has at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
  • a size dimension e.g., length, width, height (thickness), depth, diameter, pitch
  • 'pitch' refers to: (1) an average center-to-center distance extending between two neighboring similar nanoscale features (e.g., two nanofacets, two nanogrooves, or two nanosteps) of an array of nanoscale features, particularly wherein the array of nanoscale features is on the surface of a self-assembled template, and also refers to: (2) an average center-to-center distance extending between two neighboring similar nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves), of an array of nanoscale structures, particularly wherein the array of nanoscale structures is on the surface of a substrate.
  • 'array' refers to a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set of features, structures, or elements, in rows or/and columns, on a surface of an object or entity.
  • an object or entity is a surface of a self-assembled template, or a surface of a substrate (i.e., substrate surface).
  • the term 'array 1 refers to a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set of features, structures, or elements, in rows or/and columns, on a surface of a self-assembled template, or on a surface of a substrate (i.e., substrate surface).
  • a parallelogram or parallelogram-like e.g., rectangular (square) or rectangular-like (square-like) ordered arrangement or set of features, structures, or elements, in rows or/and columns, on a surface of a self-assembled template, or on a surface of a substrate (i.e., substrate surface).
  • exemplary arrays i.e., parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangements or sets of features, structures, or elements, in rows or/and columns, on a surface of a self-assembled template, are: (i) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale features, in rows or/and columns, on a self-assembled template, (ii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanofacets, in rows or/and columns, on a self-assembled template, (iii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square—like)) ordered arrangement or set) of
  • exemplary arrays i.e., parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangements or sets of features, structures, or elements, in rows or/and columns, on a surface of a substrate (i.e., substrate surface) are: (i) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale structures, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), (ii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanowires, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), (iii) an array (i.e., a parallelogram or parallelogram-like (e.g., a
  • the phrase 'self-assembled template 1 refers to a pre-formed, master or standard (i.e., template type) crystal structure whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface (i.e., a surface of a crystal).
  • the 'self-assembled template 1 i.e., the pre-formed, master or standard (i.e., template type) crystal structure, is generated or formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) a surface of a crystal.
  • the (spontaneously formed) array of nanoscale features included on the surface of the 'self-assembled template' i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure
  • the dynamic type of structural self-assembly (or self-organization) process resulting in generation or formation of such a 'self-assembled template', i.e., a pre-formed, master or standard (i.e., template type) crystal structure, is generally known as being a process during which there occurs a specific type of (spontaneous) assembly or organization of atoms (groups of atoms) on a surface of a crystal without guidance or management from or by an outside (external) source.
  • an important, and potentially exploitable, result of the (spontaneous) dynamic type of structural self-assembly (or self-organization) process is spontaneous formation of an array of nanoscale features included on the surface of the 'self-assembled template 1 , i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
  • an important aspect of such a (spontaneous) structural self-assembly (or self-organization) process is that the final (desired) (spontaneously formed) array of nanoscale features included on the surface of the 'self-assembled template', i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure, is 'encoded' in the geometrical configuration (arrangement), shape, form, properties, characteristics, and features, of the atoms (groups of atoms) on the crystal surface which is subjected to the structural self-assembly (or self-organization) process.
  • Subjecting a surface of a crystal to a (spontaneous) structural self-assembly (or self-organization) process in particular, by specially treating (e.g., annealing) the surface of the crystal, for generating or forming the 'self-assembled template', i.e., the pre-formed, master or standard (i.e., template type) crystal structure, results in the treated crystal surface displaying or exhibiting 'emergent structural properties, characteristics, or features', i.e., the spontaneously formed array of nanoscale features included on the surface of the 'self-assembled template', i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
  • the 'self-assembled template' i.e., the pre-formed, master or standard (i.e., template type) crystal structure
  • the 'self-assembled template' is suitable for being used in a procedure for replicating (i.e., copying or reproducing) at least part of the array of the nanoscale features included on the surface of the 'self-assembled template' (i.e., the pre-formed, master or standard (i.e., template type) crystal structure).
  • such a procedure involves applying at least one material upon at least part of the array of the nanoscale features (included on the surface of the 'self-assembled template'), for replicating the at least part of the array of the nanoscale features, such that the applied materials) includes a replica configuration and shape, for example, as part of a surface replica element, of the at least part of the array of the nanoscale features (included on the surface of the 'self-assembled template').
  • the phrase 'self-assembled template 1 is considered synonymous and equivalent to the phrase 'self-organized template', where the term 'self-assembled' is considered synonymous and equivalent to the term 'self-organized'.
  • 'substrate surface' refers to a surface of a substrate, where the term 'substrate', as used herein, refers to an underlying layer, i.e., of a surface.
  • the substrate, or underlying layer is composed of essentially any type or kind of material or substance, or combination of materials or substances. More specifically, the substrate, or underlying layer, is composed of inorganic matter, or/and organic matter.
  • the term 'replicating' refers to copying or reproducing an object or entity.
  • an example of such an object or entity is 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • the term 'replicating' refers to copying or reproducing 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • the term 'replica' refers to a copy or reproduction of an object or entity.
  • an example of such an object or entity is 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • the term 'replica' refers to a copy or reproduction of 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • 'configuration' refers to an arrangement of parts, elements, or components, of an object or entity.
  • an example of such an object or entity is 'applied material(s)' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • the term 'configuration' refers to an arrangement of parts, elements, or components, of 'applied materials' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • 'shape' refers to the characteristic surface configuration of an object or entity.
  • 'shape' is considered synonymous and equivalent to the term 'form'.
  • the shape, Le., the characteristic surface configuration, of an object or entity is also considered the outline or contour of the object or entity.
  • an example of such an object or entity is 'applied material(s)' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • 'shape', and the phrase 'shape' each refers to the characteristic surface configuration (outline or contour) of 'applied materials' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
  • an important aspect of the method of the present invention is that such applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features which is included on a surface of a self-assembled template.
  • 'surface replica element' refers to an element (in particular, of applied materials) whose configuration and shape includes a replica (i.e., copy or reproduction) configuration and shape of at least part of a surface of a self- assembled template, where the at least part of the surface of the self-assembled template includes 'at least part of an array of nanoscale features'.
  • the term 'about' refers to ⁇ 20 % of the associated value.
  • the phrase 'room temperature' refers to a temperature in a range of between about 15 °C and about 35 °C. Steps or procedures, sub-steps or sub-procedures, equipment, reagents, and materials, as well as operation and implementation, of exemplary preferred embodiments, alternative preferred embodiments, specific configurations, and, additional and optional aspects, characteristics, or features, thereof, of the method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template, according to the present invention, are better understood with reference to the following illustrative description and accompanying drawings.
  • a method for producing an array of nanoscale structures on a substrate surface including the following main steps (procedures), and structures thereof: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features; treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
  • Fig. 1 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary generalized preferred embodiment of implementing the method for producing an array of nanoscale structures on a substrate surface.
  • the method for producing an array of nanoscale structures on a substrate surface includes the following main steps (procedures), and structures thereof: providing a self-assembled template 10 whose surface includes an array 12 of nanoscale features 14 spontaneously formed by treating (indicated as 16 [crystal surface treatment]) a crystal surface 18; applying (indicated as 20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14, for replicating the at least part of array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape of the at least part of array 12 of nanoscale features 14; treating (indicated as 22 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting (indicated as 24 [contacting]) the replica configuration and shape of the treated applied material(s), with the substrate surface 26, for forming a combination structure having the replica configuration and shape in contact with the substrate surface 26
  • this main step involves providing a self-assembled template 10 whose surface includes an array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) a crystal surface 18.
  • the phrase 'self-assembled template' as used herein, is considered synonymous and equivalent to the phrase 'self-organized template', where the term 'self-assembled' is considered synonymous and equivalent to the term 'self-organized'.
  • self-assembled template 10 is considered synonymous and equivalent to a self-organized template 10, whose surface includes an array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) a crystal surface 18.
  • self-assembled template 10 is composed of essentially any type or kind of a crystalline substance, having essentially any bulk or overall geometrical shape or form, and essentially any bulk or overall size, so long as the surface of self-assembled template 10 includes an array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) a crystal surface 18.
  • self-assembled template 10 is composed of a crystalline substance selected from the group consisting of crystalline inorganic matter, crystalline organic matter, and a combination thereof.
  • An exemplary crystalline substance being crystalline inorganic matter, of which self-assembled template 10 is composed is selected from the group consisting of: a crystalline single metal oxide, a crystalline mixed metal oxide, a crystalline inorganic salt, a periodic table group IV element, a compound of periodic table group IV elements, a compound of a periodic table group III element and a periodic table group V element, a compound of a periodic table group II element and a periodic table group VI element, a crystalline carbide, a crystalline suicide, a crystalline hydride, a crystalline elemental metal, and a crystalline alloy.
  • An exemplary crystalline single metal oxide, of which self-assembled template 10 is composed is selected from the group consisting of: alpha-aluminum oxide (sapphire) [(X-Al 2 O 3 ], alpha-silicon oxide (quartz) [(X-SiO 2 ], zinc oxide [ZnO], magnesium oxide [MgO], and titanium oxide [TiO 2 ].
  • An exemplary crystalline mixed metal oxide, of which self-assembled template 10 is composed, is selected from the group consisting of: barium titanate [BaTiO 3 ], strontium titanate [SrO 3 ], and lithium niobate [LiNbO 3 ].
  • An exemplary crystalline inorganic salt, of which self-assembled template 10 is composed is selected from the group consisting of: calcium fluoride [CaF 2 ], calcium carbonate [CaC ⁇ 3 ], and sodium chloride [NaCl].
  • An exemplary periodic table group IV element, of which self-assembled template 10 is composed is selected from the group consisting of: elemental silicon [Si], elemental germanium [Ge], graphite elemental carbon [C], and diamond elemental carbon [C].
  • An exemplary compound of periodic table group IV elements, of which self-assembled template 10 is composed is silicon carbide [SiC].
  • An exemplary compound of a periodic table group III element and a periodic table group V element, of which self-assembled template 10 is composed is selected from the group consisting of: gallium arsenide [GaAs], gallium nitride [GaN], indium phosphide [InP], and boron nitride [BN].
  • An exemplary compound of a periodic table group II element and a periodic table group VI element, of which self-assembled template 10 is composed, is selected from the group consisting of: zinc sulfide [ZnS], cadmium selenide [CdSe], and zinc telluride [ZnTe].
  • An exemplary crystalline carbide, of which self-assembled template 10 is composed is selected from the group consisting of: tungsten carbide [WC], and titanium carbide [TiC].
  • An exemplary crystalline suicide, of which self-assembled template 10 is composed is: tungsten suicide [WSi 2 ].
  • An exemplary crystalline hydride, of which self-assembled template 10 is composed is selected from the group consisting of: water (ice) [H 2 O], calcium hydride [CaH 2 ], and lithium boron hydride [LiBH 4 ].
  • An exemplary crystalline elemental metal, of which self-assembled template 10 is composed, is selected from the group consisting of: elemental gold [Au], elemental platinum [Pt], elemental molybdenum [Mo], and elemental iridum [Ir].
  • An exemplary crystalline metal alloy, of which self-assembled template 10 is composed, is selected from the group consisting of: aluminum-nickel-cobalt (Alnico) [AlNiCo], and iron-nickel (Invar) [FeNi].
  • An exemplary crystalline substance being crystalline organic matter, of which self-assembled template 10 is composed is selected from the group consisting of: an amino acid, a protein, a carbohydrate, an aliphatic compound, and an aromatic compound.
  • An exemplary amino acid, of which self-assembled template 10 is composed is selected from the group consisting of: L-glycine, and L-alanine.
  • An exemplary protein, of which self-assembled template 10 is composed is selected from the group consisting of: hemoglobin, and myoglobin.
  • An exemplary carbohydrate, of which self-assembled template 10 is composed is selected from the group consisting of: glucose, sucrose, and lactose.
  • An exemplary aliphatic compound, of which self-assembled template 10 is composed is selected from the group consisting of: urea [CON 2 H 4 ], camphor [C 10 H 16 O], and ascorbic acid [C 6 H 8 O 6 ].
  • An exemplary aromatic compound, of which self-assembled template 10 is composed is selected from the group consisting of: naphthalene [C 10 Hs], anthracene [C 14 H 10 ], pentacene [C 22 H 14 ], and benzoic acid [C 7 H 6 O 2 ].
  • An exemplary crystalline substance being a combination of crystalline inorganic matter and crystalline organic matter, of which self-assembled template 10 is composed, is selected from the group consisting of: a crystalline organic salt, and a crystalline organometallic complex.
  • An exemplary crystalline organic salt, of which self-assembled template 10 is composed, is selected from the group consisting of: calcium oxalate [CaC 2 O 4 ], and iron (III) acetate [Fe (CH 3 CO 2 ) 2 ].
  • An exemplary crystalline organometallic complex, of which self-assembled template 10 is composed, is selected from the group consisting of: ferrocene [Fe (C 5 H 5 ) 2 ], and zinc tetraphenylporphyrin [ZnC 44 H 28 N 4 ].
  • Self-assembled template 10 is composed, preferably, of gallium arsenide [GaAs], being an exemplary compound of a periodic table group III element and a periodic table group V element, which, in turn, is an exemplary crystalline substance being crystalline inorganic matter.
  • Self-assembled template 10 is composed, more preferably, of elemental Q
  • Self-assembled template 10 is composed, most preferably, of alpha-aluminum oxide (sapphire) [ ⁇ -Al 2 ⁇ 3 ], being an exemplary crystalline single metal oxide, which, in turn, is an exemplary crystalline substance being crystalline inorganic matter.
  • self-assembled template 10 has a three-dimensional polyhedron bulk or overall geometrical shape or form, or a three-dimensional non-polyhedron curved bulk or overall geometrical shape or form.
  • An exemplary three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a parallelpiped, a prism, and a pyramid.
  • An exemplary parallelpiped type of three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a rectangular parallelpiped, a square prism, and a cube.
  • An exemplary prism type of three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a triangular prism, a quadrilateral prism, a pentagonal prism, and a hexagonal prism.
  • An exemplary pyramid type of three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a triangular pyramid, a quadrilateral pyramid, a pentagonal pyramid, and a hexagonal pyramid.
  • An exemplary three-dimensional non-polyhedron curved bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a cylinder, a disc (disk), and a cone.
  • Self-assembled template 10 has a bulk or overall geometrical shape or form, preferably, of a cylinder or disc, each being an exemplary three-dimensional non- polyhedron curved bulk or overall geometrical shape or form.
  • Self-assembled template 10 has a bulk or overall geometrical shape or form, more preferably, of a prism, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
  • Self- assembled template 10 has a bulk or overall geometrical shape or form, most preferably, of a parallelpiped, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
  • self-assembled template 10 has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a general range of between about 0.1 nanometer (nm) and about 1 meter (m).
  • self-assembled template 10 has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron ( ⁇ m) and about 1 centimeter (cm), (ii) a second range of between about 100 microns ( ⁇ m) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
  • the first range of between about 1 micron ( ⁇ m) and about 1 centimeter (cm) is particularly relevant to applications in sub-fields and areas of nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electromechanics (nanoelectromechanics), and nanoscale semiconductor technology, which involve manufacturing of devices, components, and elements, such as sensors, and actuators.
  • the second range of between about 100 microns ( ⁇ m) and about 1 meter (m) is particularly relevant to applications in sub-fields and areas of nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electromechanics (nanoelectromechanics), and nanoscale semiconductor technology, which involve manufacturing of devices, components, and elements, such as displays, and, optical, electro-optical, or optoelectronic, devices, components, and elements.
  • the third range of between about 1 millimeter (mm) and about 1 meter (m) is particularly relevant to applications which involve manufacturing of macroscopic sized devices, components, and elements, such as displays (e.g., television displays, computer displays, video displays, playstation displays, cellular phone displays), and, optical, electro-optical, or opto-electronic, devices, components, and elements, such as filters and polarizers.
  • displays e.g., television displays, computer displays, video displays, playstation displays, cellular phone displays
  • optical, electro-optical, or opto-electronic, devices, components, and elements such as filters and polarizers.
  • array 12 of nanoscale features 14 included on the surface of self-assembled template 10 corresponds to a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set of features, structures, or elements, herein, generally referred to as nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10.
  • Nanoscale features 14 of array 12 included on the surface of self-assembled template 10 correspond to distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements) which are included on the surface of self-assembled template 10.
  • nanoscale features 14 of array 12 included on the surface of self-assembled template 10 can be of various different types or kinds.
  • Nanoscale features 14 of array 12 included on the surface of self-assembled template 10 are of a type or kind, preferably, selected from the group consisting of nanoscale facets (i.e., nanofacets), nanoscale grooves (i.e., nanogrooves), and nanoscale steps (i.e., nanosteps).
  • an example of such as an array of nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10 is an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale facets (i.e., nanofacets), in rows or/and columns, on the surface of self-assembled template 10.
  • a parallelogram or parallelogram-like e.g., rectangular (square) or rectangular-like (square-like) ordered arrangement or set
  • nanoscale facets i.e., nanofacets
  • an array of nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10 is an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square— like)) ordered arrangement or set) of nanoscale grooves (i.e., nanogrooves), in rows or/and columns, on the surface of self-assembled template 10.
  • a parallelogram or parallelogram-like e.g., rectangular (square) or rectangular-like (square— like) ordered arrangement or set
  • nanoscale grooves i.e., nanogrooves
  • an array of nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10 is an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale steps (i.e., nanosteps), in rows or/and columns, on the surface of self-assembled template 10.
  • a parallelogram or parallelogram-like e.g., rectangular (square) or rectangular-like (square-like) ordered arrangement or set
  • nanoscale steps i.e., nanosteps
  • any single or individual nanoscale feature (e.g., nanofacet, nanogroove, nanostep) of nanoscale features 14 has size dimensions of width, and height (or thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch, P 1 being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanoscale features (e.g., two nanofacets, two nanogrooves, or two nanosteps), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • nanoscale features 14, and therefore, array 12 of nanoscale features 14, included on the surface of the provided self-assembled template 10 are spontaneously formed by treating (16 [crystal surface treatment]) crystal surface 18 of a crystalline substance (e.g., a crystal).
  • self-assembled template 10 which is provided in accordance with this main step (procedure), corresponds to a pre-formed, master or standard (i.e., template type) crystal structure whose surface 18 includes array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) crystal surface 18 of a crystalline substance.
  • Self-assembled template 10 i.e., the pre-formed, master or standard (i.e., template type) crystal structure, is generated or formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) crystal surface 18 of a crystalline substance (a crystal).
  • Spontaneously formed array 12 of nanoscale features 14 included on the surface of self-assembled template 10 is spontaneously formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) crystal surface 18 of a crystalline substance (a crystal).
  • the dynamic type of structural self-assembly (or self-organization) process resulting in generation or formation of such a 'self-assembled template 1 , i.e., a pre-formed, master or standard (i.e., template type) crystal structure, such as self-assembled template 10, is a process during which there occurs a specific type of (spontaneous) assembly or organization of atoms (groups of atoms) on crystal surface 18 of a crystalline substance (a crystal) without guidance or management from or by an outside (external) source.
  • an important, and potentially exploitable, result of the (spontaneous) dynamic type of structural self-assembly (or self-organization) process is spontaneous formation of array 12 of nanoscale features 14 included on the surface of self-assembled template 10, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
  • an important aspect of such a (spontaneous) structural self-assembly (or self-organization) process is that the final (desired) (spontaneously formed) array 12 of nanoscale features 14 included on the surface of self-assembled template 10, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure, is 'encoded' in the geometrical configuration (arrangement), shape, form, properties, characteristics, and features, of the atoms (groups of atoms) on crystal surface 18 of a crystalline substance which is subjected to the structural self-assembly (or self-organization) process.
  • crystal surface 18 of a crystalline substance (a crystal) to a (spontaneous) structural self-assembly (or self-organization) process, in particular, by specially treating (16 [crystal surface treatment]) (e.g., annealing) crystal surface 18 of the crystalline substance, for generating or forming self-assembled template 10, i.e., the pre-formed, master or standard (i.e., template type) crystal structure, results in the treated crystal surface 18 of the crystalline substance displaying or exhibiting 'emergent structural properties, characteristics, or features'.
  • (16 [crystal surface treatment]) e.g., annealing
  • Such emergent structural properties, characteristics, or features correspond to the spontaneously formed array 12 of nanoscale features 14 included on the surface of self-assembled template 10, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
  • self-assembled template 10 i.e., the pre-formed, master or standard (i.e., template type) crystal structure
  • master or standard (i.e., template type) crystal structure is suitable for being used in a procedure for replicating (i.e., copying or reproducing) at least part of array 12 of nanoscale features 14 included on the surface of self-assembled template 10.
  • such a procedure involves applying (20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14 included on the surface of self-assembled template 10, for replicating the at least part of array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape, for example, as part of a surface replica element, of the at least part of array 12 of nanoscale features 14 included on the surface of self-assembled template 10.
  • crystal surface 18 is composed of essentially any type or kind of a crystalline substance, having essentially any bulk or overall geometrical shape or form, and essentially any bulk or overall size, so long as at least part of the crystalline substance can be cut, or alternatively processed, for forming crystal surface 18.
  • crystal surface 18 of a crystalline substance (a crystal) is subjected to a (spontaneous) structural self-assembly (or self-organization) process, in particular, by specially treating (16 [crystal surface treatment]) (e.g., annealing) crystal surface 18 of the crystalline substance, for generating or forming self-assembled template 10.
  • crystal surface 18 is composed of essentially any type or kind of a crystalline substance, as described and exemplified for self-assembled template 10. Additionally, crystal surface 18 has essentially any bulk or overall geometrical shape or form, as described and exemplified for self-assembled template 10. Additionally, crystal surface 18 has essentially any bulk or overall size, as described and exemplified for self-assembled template 10. Crystal surface 18 is obtained by cutting, or, by alternatively processing, at least part of a crystalline substance, for example, a crystal. Crystal surface 18 is, alternatively obtained, by depositing (e.g., via epitaxial growth) a crystalline substance onto a surface of another substance.
  • the crystalline substance for example, a crystal
  • crystal surface 18 can be treated (16 [crystal surface treatment]), preferably, by annealing, for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10.
  • Crystal surface 18 is treated (16 [crystal surface treatment]), preferably, by annealing, for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10.
  • Crystal surface 18 is treated (16 [crystal surface treatment]), alternatively, by etching (e.g., dry or wet etching), for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self- assembled template 10.
  • crystal surface 18 is treated (16 [crystal surface treatment]) for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10, therefore, the type or kind of composition, and bulk or overall geometrical shape or form, and bulk or overall size, of crystal surface 18, correspond to the type or kind of composition, and bulk or overall geometrical shape or form, and bulk or overall size, respectively, of self-assembled template 10, as illustratively described hereinabove.
  • this main step involves applying (20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14, for replicating the at least part of array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape of the at least part of array 12 of nanoscale features 14.
  • applying (20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14 is performed according to any of a variety of different material applying processes, using appropriate techniques, equipment, instruments, materials, and chemical reagents. Applying (20 [applying material(s)]) is performed according to a material applying process selected from the group consisting of: casting (molding), and depositing.
  • 'casting' refers to pouring or placing the at least one material upon at least part of array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10, and allowing the poured or placed material(s) to set in a solid form (i.e., solidify) upon the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10.
  • 'casting' is considered synonymous and equivalent to the term 'molding'.
  • An exemplary type or kind of casting (molding) process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: a polymer cross-linking type of casting (molding) process, and a liquid-to-solid phase transition type of casting (molding) process.
  • the term 'depositing' refers to putting or setting down the at least one material upon at least part of array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10.
  • An exemplary type or kind of depositing process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: a physical deposition process, and a chemical deposition process.
  • An exemplary physical deposition process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: evaporation, sputtering, and coating.
  • An exemplary chemical deposition process for performing the main step (procedure) of applying (20 [applying material(s)]) is selected from the group consisting of: chemical vapor depostion, adsorption, growth, polymerization, electrodeposition, and electroless deposition.
  • the at least one material that is applied upon at least part of array 12 of nanoscale features 14, is composed of essentially any type or kind of a substance, having essentially type or kind of structure.
  • the at least one material that is applied upon at least part of array 12 of nanoscale features 14, is composed of a substance selected from the group consisting of organic matter, inorganic matter, and a combination thereof.
  • An exemplary substance being organic matter, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is an organic polymer.
  • An exemplary organic polymer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: a thermoplastic, a thermoset, an elastomer, and any combination thereof.
  • An exemplary thermoplastic, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed is selected from the group consisting of: polystyrene (PS), a polyurethane (PU), and a polyamide.
  • thermoset of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: an epoxy resin, phenol formaldehyde resin, and a polyester.
  • An exemplary substance being inorganic matter, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed is selected from the group consisting of: a metal element, a metal alloy, a semi-metal element, a non-metal element, and any combination thereof.
  • An exemplary metal element, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed is selected from the group consisting of: a noble metal element (e.g., gold [Au], silver [Ag], or platinum [Pt]), a transition metal element (e.g., nickel [Ni] 3 molybdenum [Mo], or copper [Cu]), and a main o o
  • a noble metal element e.g., gold [Au], silver [Ag], or platinum [Pt]
  • a transition metal element e.g., nickel [Ni] 3 molybdenum [Mo], or copper [Cu]
  • group metal element e.g., aluminum [Al], or bismuth [Bi]
  • An exemplary metal alloy of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: palladium-gold [PdAu], and platinum-indium [PtIr].
  • An exemplary semi-metal element, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: elemental silicon [Si], and elemental germanium [Ge].
  • An exemplary non-metal element of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: an allotrope of carbon (e.g., graphitic elemental carbon, amorphous elemental carbon, diamond elemental carbon, fullerene elemental carbon, or nanotube elemental carbon), and elemental boron [B].
  • an allotrope of carbon e.g., graphitic elemental carbon, amorphous elemental carbon, diamond elemental carbon, fullerene elemental carbon, or nanotube elemental carbon
  • elemental boron [B] elemental boron
  • An exemplary combination of a metal element and a non-metal element, in the form of a compound, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: indium oxide [In 2 Os], molybdenum diselinide [MoSe2], and boron nitride [BN].
  • An exemplary substance being a combination of organic matter and inorganic matter, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is an organic-inorganic polymer.
  • An exemplary organic-inorganic polymer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: an organic-inorganic form of a thermoplastic, an organic-inorganic form of a. thermoset, an organic-inorganic form of an elastomer, and any combination thereof.
  • An exemplary organic-inorganic form of a thermoplastic of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: polyvinylchloride (PVC), and polytetrafluoroethylene (Teflon®).
  • An exemplary organic-inorganic form of an elastomer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: polydimethylsiloxane (PDMS), and a fluorosilicone.
  • the at least one material that is applied upon at least part of array 12 of nanoscale features 14 has an amorphous structure, or a crystalline structure. Treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
  • this main step involves treating (22 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
  • the main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process
  • the main step (procedure) of treating (22 [treating]) includes, as a first main sub-step (sub-procedure), separating, for example, by peeling off, the applied material(s) (e.g., an organic polymer or organic-inorganic polymer cast (mold) type of surface replica element) from the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10.
  • the applied material(s) e.g., an organic polymer or organic-inorganic polymer cast (mold) type of surface replica element
  • the applied material(s) e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element
  • the treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking, by using a suitable ink, the surface of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element).
  • step (procedure) includes, as a first main sub-step (sub-procedure), wrapping the applied material(s) (e.g., the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element) onto and around a roller, for forming a wrapped form of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element).
  • the applied material(s) e.g., the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element
  • the main step (procedure) of treating (22 [treating]) step (procedure) further includes inking, by using a suitable ink, the surface of the applied material (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element). More specifically, there is inking that surface part or area of the applied material (e.g., of the organic polymer or organic- inorganic polymer cast (mold) type wrapped surface replica element), which encompasses the replica configuration and shape of the applied material (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element).
  • a suitable ink the surface of the applied material (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element). More specifically, there is inking that surface part or area of the applied material (e.g., of the organic polymer or organic- inorganic polymer cast (mold) type wrapped surface replica element), which encompass
  • the preceding treating steps are thus performed for forming a treated applied material (e.g., a treated (inked) organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element).
  • a treated applied material e.g., a treated (inked) organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element.
  • the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element has, via the treated (inked) portion thereof, the replica configuration and shape of the applied material (e.g., of the organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element).
  • a suitable ink is an ink which is composed of essentially any type or kind of a solution or suspension of a substance that binds, adheres, or/and adsorbs, onto substrate surface 26 of substrate 34.
  • An exemplary ink is selected from the group consisting of a thiol compound based ink, and a silane compound based ink.
  • An exemplary thiol compound based ink is a solution or suspension of a thiol compound selected from the group consisting of: n-hexadecanethiol, n-dodecanethiol, and n-octadecanethiol.
  • Such a thiol compound based ink binds, adheres, or/and adsorbs, onto a metal (e.g., gold) type of substrate surface 26 of substrate 34.
  • An exemplary silane compound based ink is a solution or suspension of a silane compound selected from the group consisting of: octadecyltricholorosilane, 3-aminopropyl-triethoxisilane, and 3- mercaptopropyl-trimetlioxysilane.
  • Such a silane compound based ink binds, adheres, or/and adsorbs, onto an oxide (e.g., silicon oxide [SiO 2 ], or oxidized silicon [Si]) type of substrate surface 26 of substrate 34.
  • oxide e.g., silicon oxide [SiO 2 ], or oxidized silicon [Si]
  • the treating step (procedure) includes allowing the applied material(s) (i.e., the deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), while maintaining the replica configuration and shape thereof, upon the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, to stand at a pre-determined temperature, for a pre-determined period of time.
  • the applied material(s) i.e., the deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer
  • the treated applied material(s) i.e., the treated deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer
  • the treated applied material(s) i.e., the treated deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer
  • the replica configuration and shape of the treated applied mater ial(s) with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface.
  • this main step involves contacting (24 [contacting]) the replica configuration and shape of the treated applied material(s), with the substrate surface 26, for forming a combination structure having the replica configuration and shape in contact with the substrate surface 26.
  • the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process
  • the main step (procedure) of contacting (24 [contacting]) is performed, for example, by pressing or bringing together, the replica configuration and shape of the treated applied material(s) (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element), with the substrate surface 26 of substrate 34, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26.
  • the substrate i.e., substrate 34
  • the substrate includes two main distinct layers, i.e., a first or base layer, and a second or surface layer which is situated and lies upon the first or base layer.
  • the second or surface layer is the top or upper most layer of substrate 34 which includes a substrate surface that is brought into contact with the replica configuration and shape of the treated applied material(s) (e.g., of the treated (inked) organic polymer or organic- inorganic polymer cast (mold) type surface replica element).
  • the first or base layer is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof.
  • the first or base layer is composed of a semiconductor type or kind of material or substance, such as silicon, oxidized silicon, or gallium arsenide.
  • the first or base layer is composed of an insulating type or kind of material or substance, for example, glass, quartz, or sapphire.
  • the second or surface layer is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof.
  • the second or surface layer is composed of a metallic type or kind of material or substance, such as gold, silver, platinum, gold on chromium, or gold on titanium, which is situated and lies upon the first or base layer.
  • This main step (procedure) of contacting (24 [contacting]) involves, and results in, transferring, via the ink, the replica configuration and shape of the treated applied material(s) (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element) onto the substrate surface of the second or surface layer of substrate 34.
  • the treated applied material(s) e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element
  • This main step (procedure) of contacting (24 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with the ink, those areal portions or sections (e.g., strips or belts) of the substrate surface of the second or surface layer which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material(s) (e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element).
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips or belts) of the substrate surface of the second or surface layer which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material(s) (e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element).
  • a roller type of specific preferred embodiment of the method of the present invention for example, as illustratively described hereinbelow, along with reference to Fig. 8, there is contacting (24 [contacting]), for example, by rolling and bringing together, the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element), with the substrate surface 26 of substrate 34, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26.
  • the treated applied material e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element
  • the main step (procedure) of contacting involves, and results in, transferring, via ink, the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element) onto substrate surface 26 of substrate 34.
  • the treated applied material e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element
  • this main step (procedure) of contacting (24 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with the ink, those areal portions or sections (e.g., strips) of substrate surface 26 of substrate 34 which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., which are brought into , direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element).
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 26 of substrate 34 which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element).
  • the treated applied material e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element.
  • the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a depositing type of material applying process
  • the main step (procedure) of contacting (24 [contacting]) is performed, for example, by pressing or bringing together, the treated applied material(s) (i.e., the treated deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, with substrate surface 26 of substrate 34, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26 of substrate 34.
  • the treated applied material(s) i.e., the treated deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer
  • This main step (procedure) of contacting involves, and results in, transferring a portion or layer of the treated applied material (e.g., of the treated deposited material (in particular, the treated deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer)), having the replica configuration and shape of the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, onto substrate surface 26 of substrate 34.
  • Processing the combination structure for generating the array of the nanoscale structures on the substrate surface.
  • this main step (procedure) involves processing the combination structure, for generating (indicated as 28 [array generation]) the array 30 of the nanoscale structures 32 on the substrate surface 26 of a substrate 34.
  • the main step (procedure) of processing the combination structure includes, as a first main sub-step (sub-procedure), separating the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element), from substrate surface 26 of substrate 34.
  • the treated applied material e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element
  • the treated applied material e.g., the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element
  • the treated applied material e.g., the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element
  • this processing by this processing first main sub-step (sub-procedure), there is forming a nanopattern (nanoscale pattern) upon substrate surface 26 of substrate 34.
  • the nanopattern is composed or made up of two parts or components.
  • the first part or component of the nanopattern corresponds to: (i) those areal portions or sections (e.g., strips or belts) of the substrate surface of the second or surface layer which were chemically functionalized (derivatized) by the preceding contacting (24 [contacting]) procedure, as a result of having been brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element).
  • the treated applied material e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element
  • the second part or component of the nanopattern corresponds to: (ii) the remaining areal portion or section of the substrate surface of the second or surface layer which was not chemically functionalized (derivatized) by the preceding contacting (24 [contacting]) procedure, as a result of not having been brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element).
  • the treated applied material e.g., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element.
  • the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via [chemical functionalizing (derivatizing)], or via [etching]) the nanopattern (nanoscale pattern) upon the substrate surface of the second or surface layer of substrate 34, which was obtained from the preceding separating sub-step (sub-procedure).
  • the processing step further includes modifying (via [chemical functionalizing (derivatizing)], or via [etching]) the preceding stated second part or component of the nanopattern, i.e., the remaining areal portion or section of the substrate surface of the second or surface layer of substrate 34 which was not chemically functionalized (derivatized) by the preceding contacting (24 [contacting]) procedure (as a result of not having been brought into direct contact with the ink of the replica configuration and shape).
  • the processing step (procedure) further includes modifying (via [chemical functionalizing (derivatizing)], or via [etching]) the exposed areal portion or section of the substrate surface of the second or surface layer which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips or belts) of the nanopattern, i.e., of the nanoscale pattern of the replica configuration and shape.
  • Modifying, via [chemical functionalizing (derivatizing)], the nanopattern (nanoscale pattern) upon the substrate surface of the second or surface layer of substrate 34, is performed by using a suitable chemical functionalizing (derivatizing) procedure or technique, involving a suitable chemical functionalizing (derivatizing) reagent.
  • a suitable chemical functionalizing (derivatizing) procedure or technique is, for example, selected from the group consisting of a thiol compound based functionalizing (derivatizing) procedure or technique, and a silane compound based functionalizing (derivatizing) procedure or technique.
  • a thiol compound based chemical functionalizing (derivatizing) procedure or technique involving a thiol compound based chemical functionalizing (derivatizing) reagent.
  • a suitable thiol compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 16-mercaptohexadecanoic acid, 12-thioldodecanol, and 12-aminododecanethiol.
  • a silane compound based type of functionalizing (derivatizing) procedure or technique involving a silane compound based chemical functionalizing (derivatizing) reagent.
  • a suitable silane compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 3-aminopropyl-triethoxisilane, and 3-mercaptopropyl-trimethoxysilane.
  • this modifying, via [chemical functionalizing (derivatizing)], sub-step (sub-procedure) of the processing step (procedure), results in generating (28 [array generation]) array 30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34.
  • nanoscale structures e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves
  • Modifying, via [etching], the nanopattern (nanoscale pattern) upon the substrate surface of the second or surface layer of substrate 34 is performed by using a suitable etching procedure or technique, involving a suitable etching (etchant) reagent.
  • a suitable etching procedure or technique is, for example, selected from the group consisting of a wet etching procedure or technique, and a dry etching procedure or technique.
  • a suitable oxidizing compound based wet etching (etchant) reagent is, for example, a solution composed of: (i) potassium ferricyanide [K 3 Fe(CN) 6 ], 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1 M; and (iii) potassium hydroxide [KOH], 1.0 M, which is particularly for wet etching of gold [Au].
  • Another suitable wet etching (etchant) reagent is, for example, a solution composed of potassium hydroxide [KOH], 0.1 M, which is particularly useful for wet etching of silicon [Si] .
  • a reactive ion etching type of dry etching procedure or technique involving a reactive ion etching dry etching (etchant) reagent.
  • An exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous sulfur tetra-fluoride [SF 4 ].
  • Another exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous chlorine [Cl 2 ].
  • this modifying, via [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating (28 [array generation]) array 30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34.
  • nanoscale structures e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves
  • the main step (procedure) of processing the combination structure involves separating the replica configuration and shape of the treated applied material (e.g., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), part of the combination structure, from substrate surface 26 of substrate 34.
  • the treated applied material e.g., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer
  • This processing step results in generating (28 [array generation]) array
  • nanoscale structures e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves
  • substrate surface 26 of substrate 34 e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves
  • any single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (run) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch, P 2 being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanoscale structures, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch, P 2 between two neighboring similar (i.e., not necessarily identical) nanoscale structures 32 of array 30 of nanoscale structures 32 on substrate surface 26 of substrate 34, has a value or magnitude which is comparable to the value or magnitude of the pitch, P 1 , between two neighboring similar (i.e., not necessarily identical) nanoscale features of array 12 of nanoscale features 14 on the surface of self-assembled template 10.
  • the width of any single or individual nanoscale structure of array 30 of nanoscale structures 32 on substrate surface 26 of substrate 34 has a value or magnitude which is less than the value or magnitude of the pitch, P 2 , between two neighboring similar nanoscale structures 32 on substrate surface 26 of substrate 34.
  • Figs. 2a - 2e are schematic (flow-type) diagrams illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of forming a 'nanogrooved 1 type faceted self-assembled template, including cutting a crystal along a 'singular' cutting plane (a low-index plane) of the crystal, wherein the self-assembled template is used for generating an array of nanoscale structures on a substrate surface.
  • Fig. 2a schematically illustrates cutting (36 [cutting]) of a crystal 38 along a 'singular' cutting plane 40 (corresponding to a low-index plane 42) located within a crystal surface region 44.
  • Figs. 2b to 2c schematically and sequentially illustrate (cut) crystal surface region 46 (Fig. 2c), of crystal 38, undergoing reconstruction (48 [reconstruction]), for forming a (reconstructed) crystal surface region 50.
  • Figs. 2c to 2d schematically and sequentially illustrate self-assembly (self-organization) of (reconstructed) crystal surface region 50 resulting in facet formation (52 [facet formation]) along and within (reconstructed) crystal surface region 50, for forming a (self-assembled) crystal surface region 54.
  • nanofacets for example, nanofacets 56 and 58, are formed along and within (self-assembled) crystal surface region 54.
  • the resulting structure corresponds to (self-assembled) crystal surface region 54 including an array 60 of nanofacets 56 and 58.
  • the resulting structure is classified as a 'nanogrooved' type faceted self-assembled template 62 whose surface (i.e., (self-assembled) crystal surface region 54) includes an array (i.e., array 60) of nanoscale features (i.e., nanofacets 56 and 58) spontaneously formed by treating a crystal surface (i.e., (cut) crystal surface region 46).
  • a crystal surface i.e., (cut) crystal surface region 46.
  • Fig. 2e schematically illustrates generating (64 [array generation]) an array 66 of nanoscale structures 68 on the substrate surface 70 of substrate 72.
  • Figs. 3a - 3d are schematic (flow-type) diagrams illustrating main steps
  • Fig. 3a schematically illustrates cutting (76 [cutting]) of a crystal 78 along a 'vicinal' cutting plane 80 at a miscut tilt angle ( ⁇ ) relative to the nearest low-index plane 82 located within a crystal surface region 84.
  • Figs. 3b to 3c schematically and sequentially illustrate self-assembly (self-organization) of (cut) crystal surface region 86 resulting in facet formation (88 [facet formation]) along and within (cut) crystal surface region 86, for forming a (self-assembled) crystal surface region 90.
  • nanofacets for example, nanofacets 92, 94, and 96, are formed along and within (self-assembled) crystal surface region 90.
  • the resulting structure corresponds to (self-assembled) crystal surface region 90 including an array 98 of nanofacets 92, 94, and 96.
  • the resulting structure is classified as a 'nanostepped' type faceted self-assembled template 100 whose surface (i.e., (self-assembled) crystal surface region 90) includes an array (i.e., array 98) of nanoscale features (i.e., nanofacets 92, 94, and 96) spontaneously formed by treating a crystal surface (i.e., (cut) crystal surface region 86).
  • Fig. 3d schematically illustrates generating (102 [array generation]) an array 104 of nanoscale structures 106 on the substrate surface 108 of substrate 110. 5 ⁇
  • Fig. 4 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanowires (nanoscale structures) on the substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface.
  • Array 124 of nanogrooves is spontaneously formed, via a process of facet formation (126 [facet formation]), by treating (128 [annealing]) 'singular' crystal surface 130.
  • Singular crystal surface 130 is obtained by cutting (132 [cutting]) a crystal 134 along a 'singular' cutting plane 136 (corresponding to a low-index plane) located within a crystal surface region of crystal 134.
  • a material applying process in particular, a casting (molding) type of material applying process
  • at least one material (in particular, at least one suitable casting (molding) material such as an organic polymer [e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof], or, an organic-inorganic polymer [e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof]
  • an organic polymer e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof
  • an organic-inorganic polymer e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof
  • This step is performed for replicating (138 [replicating]) the entirety of array 124 of nanogrooves of nanogrooved surface 122, such that the applied material, i.e., the casted (molded) material (in particular, the organic polymer or organic-inorganic polymer), includes a replica configuration and shape 140, for example, as part of a surface replica element 142, of the entirety of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
  • the applied material i.e., the casted (molded) material (in particular, the organic polymer or organic-inorganic polymer
  • Surface replica element 142 has a bulk or overall geometrical shape or form, preferably, of a cylinder or disc, each being an exemplary three-dimensional non-polyhedron curved bulk or overall geometrical shape or form.
  • Surface replica element 142 has a bulk or overall geometrical shape or form, more preferably, of a prism, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
  • Surface replica element 142 has a bulk or overall geometrical shape or form, most preferably, of a parallelpiped, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
  • Surface replica element 142 has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a general range of between about 0.1 nanometer (nm) and about 1 meter (m).
  • Surface replica element 142 has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron ( ⁇ m) and about 1 centimeter (cm), (ii) a second range of between about 100 microns ( ⁇ m) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
  • the treating step (procedure) includes, as a first main sub-step (sub-procedure), separating (144 [separating]), for example, by peeling off, the applied material, i.e., the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142 from nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
  • the applied material i.e., the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142 from nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
  • replica configuration and shape 140 of the applied material i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142, for forming a stand-alone organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142 having replica configuration and shape 140.
  • the treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking (146 [inking]), by using a suitable ink 148, the surface of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142. More specifically, there is inking (146 [inking]), by using ink 148, that surface part or area of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142, which encompasses replica configuration and shape 140 of the applied material, i.e., of the organic polymer or organic— inorganic polymer cast (mold) type surface replica element 142.
  • any suitable ink 148 which is composed of essentially any type or kind of a solution or suspension of a substance that binds, adheres, or/and adsorbs, onto substrate surface 154 of substrate 156.
  • An exemplary ink which is particularly suitable for performing this main sub-step (sub-procedure) is a thiol compound based ink, or a silane compound based ink.
  • the preceding treating steps are thus performed for fonning treated applied material, i.e., a stand-alone treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142, as referenced by 150 in Fig. 4.
  • Treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 has, via the treated (inked) portion thereof, replica configuration and shape 140 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142. Additional details relating to performing this main step (procedure), and sub-steps
  • replica configuration and shape 140 of the treated applied material i.e., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150
  • the substrate surface 154 of substrate 156 for forming a combination structure 158 having replica configuration and shape 140 in contact with substrate surface 154.
  • the substrate i.e., substrate 156
  • the substrate 156 includes two main distinct layers, i.e., a first or base layer 160, and a second or surface layer 162 which is situated and lies upon first or base layer 160.
  • second or surface layer 162 is the top or upper most layer of substrate 156 which includes substrate surface 154 that is brought into contact with replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic- inorganic polymer cast (mold) type surface replica element 150.
  • first or base layer 160 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof.
  • first or base layer 160 is composed of a semiconductor type or kind of material or substance, such as silicon, oxidized silicon, or gallium arsenide.
  • first or base layer 160 is composed of an insulating type or kind of material or substance, for example, glass, quartz, or sapphire.
  • second or surface layer 162 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof.
  • second or surface layer 162 is composed of a metallic type or kind of material or substance, such as gold, silver, platinum, gold on chromium, or gold on titanium, which is situated and lies upon first or base layer 160.
  • This main step (procedure) of contacting (152 [contacting]) involves, and results in, transferring, via ink 148, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 onto substrate surface 154 of second or surface layer 162 of substrate 156.
  • This main step (procedure) of contacting (152 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • a consequence of this main step (procedure) of contacting (152 [contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portion or section of substrate surface 154 of second or surface layer 162 which is not brought into contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which is not brought into contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • the processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (164 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, from substrate surface 154 of substrate 156. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from substrate surface 154 of substrate 156.
  • Nanopattern 166 is composed or made up of two parts or components.
  • the first part or component of nanopattern 166 corresponds to: (i) those areal portions or sections (e.g., strips) of substrate surface 154 of second or surface layer 162 which were chemically functionalized (derivatized) by the preceding contacting (152 [contacting]) procedure, as a result of having been brought into direct contact with ink 148 of replica configuration and shape 140.
  • the second part or component of nanopattern 166 corresponds to: (ii) the remaining areal portion or section of substrate surface 154 of second or surface layer 162 which was not chemically functionalized (derivatized) by the preceding contacting (152 [contacting]) procedure, as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140.
  • the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 168 [chemical functionalizing (derivatizing)], or via 176 [etching]) the nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of second or surface layer 162 of substrate 156, which was obtained from the preceding separating (164 [separating]) sub-step (sub-procedure).
  • the processing step further includes modifying (via 168 [chemical functionalizing (derivatizing)], or via 176 [etching]) the preceding stated second part or component of nanopattern 166, i.e., the remaining areal portion or section of substrate surface 154 of second or surface layer 162 of substrate 156 which was not chemically functionalized (derivatized) by the preceding contacting (152 [contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140).
  • the processing step (procedure) further includes modifying (via 168 [chemical functionalizing (derivatizing)], or via 176 [etching]) the exposed areal portion or section of substrate surface 154 of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166, i.e., of the nanoscale pattern of replica configuration and shape 140.
  • Modifying, via 168 [chemical functionalizing (derivatizing)], the nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of second or surface layer 162 of substrate 156, is performed by using a suitable chemical functionalizing (derivatizing) procedure or technique, involving a suitable chemical functionalizing (derivatizing) reagent.
  • a suitable chemical functionalizing (derivatizing) procedure or technique is, for example, selected from the group consisting of a thiol compound based functionalizing (derivatizing) procedure or technique, and a silane compound based functionalizing (derivatizing) procedure or technique.
  • a thiol compound based chemical functionalizing (derivatizing) procedure or technique involving a thiol compound based chemical functionalizing (derivatizing) reagent.
  • a suitable thiol compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 16-mercaptohexadecanoic acid, 12-thioldodecanol, and 12-aminododecanethiol.
  • a silane compound based type of functionalizing (derivatizing) procedure or technique involving a silane compound based chemical functionalizing (derivatizing) reagent.
  • a suitable silane compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 3-aminopropyl-triethoxisilane, and 3-mercaptopropyl-trimethoxysilane.
  • Modifying via 168 [chemical functionalizing (derivatizing)] the exposed areal portion or section of substrate surface 154 of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166, results in formation of a different substrate surface, i.e., substrate surface 174, of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166.
  • this modifying, via 168 [chemical functionalizing (derivatizing)], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 170 of nanostrips 172 on substrate surface 174 of substrate 156.
  • any single or individual nanostrip 172 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (if) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch (e.g., analogous to P 2 , shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanostrips of array 170 of nanostrips 172, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch between two neighboring similar (i.e., not necessarily identical) nanostrips of array 170 of nanostrips 172 on substrate surface 174 of substrate 156 has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to P 1 , shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanogrooves of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
  • the width of any single or individual nanostrip of array 170 of nanostrips 172 on substrate surface 174 of substrate 156 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanostrips of array 170 of nanostrips 172 on substrate surface 174 of substrate 156.
  • Modifying, via 176 [etching], the nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of second or surface layer 162 of substrate 156, is performed by using a suitable etching procedure or technique, involving a suitable etching (etchant) reagent.
  • a suitable etching procedure or technique is, for example, selected from the group consisting of a wet etching procedure or technique, and a dry etching procedure or technique.
  • a suitable oxidizing compound based wet etching (etchant) reagent is, for example, a solution composed of: (i) potassium ferricyanide [K 3 Fe(CN) 6 ], 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1M; and (iii) potassium hydroxide [KOH], 1.0 M, which is particularly for wet etching of gold [Au].
  • Another suitable wet etching (etchant) reagent is, for example, a solution composed of potassium hydroxide [KOH], 0.1 M, which is particularly useful for wet etching of silicon [Si].
  • a reactive ion etching type of dry etching procedure or technique involving a reactive ion etching dry etching (etchant) reagent.
  • An exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous sulfur tetra-fluoride [SF 4 ].
  • Another exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous chlorine [Cl 2 ].
  • this modifying, via 176 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 178 of nanowires 180 on substrate surface 182 of substrate 160.
  • any single or individual nanowire 180 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch for array 178 of nanowires 180 on substrate surface 182 of substrate 160, the pitch
  • the pitch between two neighboring similar (i.e., not necessarily identical) nanowires of array 178 of nanowires 180 on substrate surface 182 of substrate 160 has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to P 1 , shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanogrooves of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
  • the width of any single or individual nanowire of array 178 of nano wires 180 on substrate surface 182 of substrate 160 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nano wires of array 178 of nano wires 180 on substrate surface 182 of substrate 160.
  • FIG. 5 is a schematic (flow-type) diagram illustrating selected main steps
  • the exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 5, is an extension of the preceding illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4.
  • There is cross contacting (190 [cross contacting]) for example, by pressing or bringing together, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with the previously generated nanopattern 166 on substrate surface 154 of substrate 156, for forming a combination structure 193 having replica configuration and shape 140 directly in contact (in Fig. 5, indicated by 192) with nanopattern 166 on substrate surface 154 of substrate 156.
  • the phrase 'cross contacting' refers to pressing or bringing together replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with substrate surface 154 of substrate 156, in a manner or way whereby replica configuration and shape 140 of the treated applied material is disposed (i.e., positioned or placed) at an angle in a range of between 0° and 90°, relative to nanopattern 166 on substrate surface 154 of substrate 156.
  • Such relative disposition (positioning or placing) is indicated by 192 in Fig. 5.
  • This main step (procedure) of cross contacting also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., grid strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (grid strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150.
  • the processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (194 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150, from substrate surface 154 of substrate 156. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from substrate surface 154 of substrate 156.
  • Nanopattern 196 is composed or made up of two parts or components.
  • the first part or component of nanopattern 196 corresponds to: (i) those areal portions or sections (e.g., grid strips) of substrate surface 154 of second or surface layer 162 which were chemically functionalized (derivatized) by the preceding cross contacting (190 [cross contacting]) procedure, as a result of having been brought into direct contact with ink 148 of replica configuration and shape 140.
  • the second part or component of nanopattern 196 corresponds to: (ii) the remaining areal portion or section of substrate surface 154 of second or surface layer 162 which was not chemically functionalized (derivatized) by the preceding cross contacting (190 [cross contacting]) procedure, as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140.
  • the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 198 [etching]) the grid (waffle) type of nanopattern (nanoscale pattern), i.e., nanopattern 196, upon substrate surface 154 of second or surface layer 162 of substrate 156, which was obtained from the preceding separating (194 [separating]) sub-step (sub-procedure).
  • the processing step further includes modifying (via 198 [etching]) the preceding stated second part or component of nanopattern 196, i.e., the remaining areal portion or section of substrate surface 154 of second or surface layer 162 of substrate 156 which was not chemically functionalized (derivatized) by the preceding cross contacting (190 [cross contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140).
  • the processing step further includes modifying (via 198 [etching]) the exposed areal portion or section of substrate surface 154 of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., grid strips) of nanopattern 196, i.e., of the nanoscale pattern of replica configuration and shape 140.
  • this modifying, via 198 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., grid (waffle) type array 200 of nanowires on substrate surface 182 of substrate 160.
  • Fig. 6 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with an array of nanowires (nanoscale structures) on a substrate surface (e.g., of Fig. 4), for generating (via an etching technique) an array of nanoparticles (nanoscale structures) on the substrate surface.
  • a surface replica element e.g., of Fig. 4
  • nanowires nanowires
  • substrate surface e.g., of Fig. 4
  • the exemplary specific preferred embodiment of implementing the method of the present invention is another extension of the preceding illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4.
  • cross contacting for example, by pressing or bringing together, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with the previously generated array 178 of nanowires 180 on substrate surface 182 of substrate 160, for forming a combination structure 207 having replica configuration and shape 140 directly in contact (in Fig. 6, indicated by 208) with nanowires 180 on substrate surface 182 of substrate 160.
  • the treated applied material i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150
  • the phrase 'cross contacting' refers to pressing or bringing together replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with substrate surface 182 of substrate 160, in a manner or way whereby replica configuration and shape 140 of the treated applied material is disposed (i.e., positioned or placed) at an angle in a range of between 0° and 90°, relative to array 178 of nanowires 180 on substrate surface 182 of substrate 160.
  • Such relative disposition (positioning or placing) is indicated by 208 in Fig. 6.
  • This main step (procedure) of cross contacting (206 [cross contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., sub-sections) of nanowires 180 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (sub-sections) of nanowires 180 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • the processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (210 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, from nanowires 180. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from nanowires 180.
  • nanopattern 212 of nanowires 180 upon substrate surface 182 of substrate 160.
  • the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 214 [etching]) the sub-sectioned type of nanopattern 212 of nanowires 180 upon substrate surface 182 of substrate 160, which was obtained from the preceding separating (210 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 214 [etching]) the preceding stated remaining areal portions or sections of nanowires 180 which were not chemically functionalized (derivatized) by the preceding cross contacting (206 [cross contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140).
  • the processing step further includes modifying (via 214 [etching]) the exposed areal portions or sections of nanowires 180 which are not covered or masked by the previously chemically functionalized (derivatized) portions or sections of nanopattern 212 of nanowires 180, i.e., of the nanoscale pattern of replica configuration and shape 140.
  • this modifying, via 214 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 216 of nanoparticles 218 on substrate surface 182 of substrate 160.
  • Fig. 7 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanogrooves (nanoscale structures) on the substrate surface.
  • a surface replica element e.g., of Fig. 4
  • nanogrooves nanoscale structures
  • exemplary specific preferred embodiment of implementing the method of the present invention is an alternative to the previous illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4.
  • replica configuration and shape 140 of the treated applied material i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150
  • substrate surface 232 of substrate 234 for forming a combination structure 236 having replica configuration and shape 140 in contact with substrate surface 232.
  • This main step (procedure) of contacting (230 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., strips) of substrate surface 232 of substrate 234 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150.
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 232 of substrate 234 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
  • the processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (242 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, from substrate surface 232 of substrate 234. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from substrate surface 232 of substrate 234.
  • Nanopattern 244 is composed or made up of two parts or components.
  • the first part or component of nanopattern 244 corresponds to: (i) those areal portions or sections (e.g., strips) of substrate surface 232 of substrate 234 which were chemically functionalized (derivatized) by the preceding contacting (230 [contacting]) procedure, as a result of having been brought into direct contact with ink 148 of replica configuration and shape 140.
  • the second part or component of nanopattern 244 corresponds to: (ii) the remaining areal portion or section of substrate surface 232 of substrate 234 which was not chemically functionalized (derivatized) by the preceding contacting (230 [contacting]) procedure, as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140.
  • the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 246 [etching]) the nanopattern (nanoscale pattern), i.e., nanopattern 244, upon substrate surface 232 of substrate 234, which was obtained from the preceding separating (242 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 246 [etching]) the remaining areal portion or section of substrate surface 232 of substrate 234 which was not chemically functionalized (derivatized) by the preceding contacting (230 [contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140).
  • the processing step further includes modifying (via 246 [etching]) the exposed areal portion or section of substrate surface 232 of substrate 234 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 244, i.e., of the nanoscale pattern of replica configuration and shape 140.
  • this modifying, via 246 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 248 of nanogrooves 250 on substrate surface 252 of (etched) substrate 254.
  • Fig. 8 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with a roller for forming a nanopattern on a substrate surface, which, in turn, is useable for generating (via a functionalizing technique) an array of nanostrips on the substrate surface.
  • the exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 6, is an alternative to the previous illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4.
  • Fig. 8 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with a roller for forming
  • a material applying process in particular, a casting (molding) type of material applying process
  • at least one material (in particular, at least one suitable casting (molding) material such as an organic polymer [e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof], or, an organic-inorganic polymer [e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof]
  • an organic polymer e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof
  • an organic-inorganic polymer e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof
  • This step is performed for replicating (138 [replicating]) the entirety of array 124 of nanogrooves of nanogrooved surface 122, such that the applied material, i.e., the casted (molded) material (in particular, the organic polymer or organic- inorganic polymer), includes a replica configuration and shape 264 (Fig. 8), for example, as part of a surface replica element 262, of the entirety of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
  • the applied material i.e., the casted (molded) material (in particular, the organic polymer or organic- inorganic polymer
  • the treating step includes, as a first main sub-step (sub-procedure), wrapping (260 [wrapping]) surface replica element 262 onto and around a roller 266, for forming a wrapped surface replica element 268.
  • the treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking (270 [inking]), by using a suitable ink 272, the surface of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268.
  • inking 270 [inking]
  • ink 272 that surface part or area of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268, which encompasses replica configuration and shape 264 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268.
  • Treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274 has, via the treated (inked) portion thereof, replica configuration and shape 264 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268.
  • replica configuration and shape 264 of the treated applied material Le., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274, with the substrate surface 280 of substrate 282, for forming a combination structure 284 having replica configuration and shape 264 in contact with substrate surface 280.
  • This main step (procedure) of contacting (276 [contacting]) involves, and results in, transferring, via ink 272, replica configuration and shape 264 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274 onto substrate surface 280 of substrate 282.
  • This main step (procedure) of contacting (276 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 272, those areal portions or sections (e.g., strips) of substrate surface 280 of substrate 282 which are brought into direct contact with ink 272 of replica configuration and shape 264 of the treated applied material, i.e., which are brought into direct contact with ink 272 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 274.
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 280 of substrate 282 which are brought into direct contact with ink 272 of replica configuration and shape 264 of the treated applied material, i.e., which are brought into direct contact with ink 272 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274.
  • the processing step (procedure) includes, as a first main sub-step (sub-procedure), separating replica configuration and shape 264 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274, from substrate surface 280 of substrate 282. This is accomplished by separating, for example, by lifting off and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274 from substrate surface 280 of substrate 282.
  • this processing sub-step (sub-procedure) there is forming a nanopattern (nanoscale pattern), i.e., nanopattern 286, upon substrate surface 280 of substrate 282.
  • the formed nanopattern (nanoscale pattern), i.e., nanopattern 286, upon substrate surface 280 of substrate 282, can be used for implementing the method of the present invention, for generating (via an etching technique, or via a functionalizing technique) any of various different types of an array of nanoscale structures (e.g., nanowires, nanostrips, nanoparticles, or nanogrooves) on the substrate surface.
  • nanoscale structures e.g., nanowires, nanostrips, nanoparticles, or nanogrooves
  • FIG. 9 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanobelts (nanoscale structures) on a substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface.
  • Array 304 of nanosteps is spontaneously formed, via a process of facet formation (306 [facet formation]), by treating (308 [annealing]) 'vicinal' crystal surface 310.
  • Vicinal crystal surface 310 is obtained by cutting (312 [cutting]) a crystal 314 along a 'vicinal' cutting plane 316 (at a miscut tilt angle ( ⁇ ) relative to the nearest low-index plane) located within a crystal surface region of crystal 314.
  • a material applying process in particular, a casting or molding type of material applying process
  • at least one material in particular, at least one suitable casting or molding material, such as an organic polymer [e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof], or, an organic-inorganic polymer [e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof]
  • an organic polymer e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof
  • an organic-inorganic polymer e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof
  • This step is performed for replicating (318 [replicating]) the entirety of array 304 of nanosteps of nanostepped surface 302, such that the applied material, i.e., casted or molded material (in particular, the organic polymer or organic— inorganic polymer), includes a replica configuration and shape 320, for example, as part of a surface replica element 322, of the entirety of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300.
  • the applied material i.e., casted or molded material (in particular, the organic polymer or organic— inorganic polymer)
  • Surface replica element 322 has a bulk or overall geometrical shape or form, preferably, of a cylinder or disc, each being an exemplary three-dimensional non- polyhedron curved bulk or overall geometrical shape or form.
  • Surface replica element 322 has a bulk or overall geometrical shape or form, more preferably, of a prism, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
  • Surface replica element 322 has a bulk or overall geometrical shape or form, most preferably, of a parallelpiped, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
  • Surface replica element 322 has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a general range of between about 0.1 nanometer (nm) and about 1 meter (m).
  • Surface replica element 322 has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron ( ⁇ m) and about 1 centimeter (cm), (U) a second range of between about 100 microns ( ⁇ m) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
  • the treating step (procedure) includes, as a first main sub-step (sub-procedure), separating (324 [separating]), for example, by peeling off, the applied material, i.e., the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322 from nanostepped surface 302 of nanostepped type faceted self-assembled template 300.
  • replica configuration and shape 320 of the applied material i.e., of the organic polymer or organic— inorganic polymer cast (mold) type surface replica element 322, for forming a stand-alone organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322 having replica configuration and shape 320.
  • the treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking (326 [inking]), by using a suitable ink 328, the surface of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322. More specifically, there is inking (326 [inking]), by using ink 328, that surface part or area of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322, which encompasses replica configuration and shape 320 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322.
  • any suitable ink 328 which is composed of essentially any type or kind of a solution or suspension of a substance that binds, adheres, or/and adsorbs, onto substrate surface 334 of substrate 336.
  • An exemplary ink which is particularly suitable for performing this main sub-step (sub-procedure) is a thiol compound based ink, or a silane compound based ink.
  • Treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330 has, via the treated (inked) portion thereof, replica configuration and shape 320 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322.
  • replica configuration and shape 320 of the treated applied material i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330
  • the substrate surface 334 of substrate 336 for forming a combination structure 338 having replica configuration and shape 320 in contact with substrate surface 334.
  • the substrate i.e., substrate 336
  • the substrate 336 includes two main distinct layers, i.e., a first or base layer 340, and a second or surface layer 342 which is situated and lies upon first or base layer 340.
  • second or surface layer 342 is the top or upper most layer of substrate 336 which includes substrate surface 334 that is brought into contact with replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic- inorganic polymer cast (mold) type surface replica element 330.
  • first or base layer 340 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof.
  • first or base layer 340 is composed of a semiconductor type or kind of material or substance, such as silicon, oxidized silicon, or gallium arsenide.
  • first or base layer 340 is composed of an insulating type or kind of material or substance, for example, glass, quartz, or sapphire.
  • second or surface layer 342 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof.
  • second or surface layer 342 is composed of a metallic type or kind of material or substance, such as gold, silver, platinum, gold on chromium, or gold on titanium, which is situated and lies upon first or base layer 340.
  • This main step (procedure) of contacting (332 [contacting]) involves, and results in, transferring, via ink 328, replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330 onto substrate surface 334 of second or surface layer 342 of substrate 336.
  • This main step (procedure) of contacting (332 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 328, those areal portions or sections (e.g., belts) of substrate surface 334 of second or surface layer 342 which are brought into direct contact with ink 328 of replica configuration and shape 320 of the treated applied material, i.e., which are brought into direct contact with ink 328 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330.
  • Such functionalizing alters (changes, modifies), via chemical reaction, the physicochem ⁇ cal composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 334 of second or surface layer 342 which are brought into direct contact with ink 328 of replica configuration and shape 320 of the treated applied material, Le., which are brought into direct contact with ink 328 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330.
  • the processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (344 [separating]) replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 330, from substrate surface 334 of substrate 336. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 330 from substrate surface 334 of substrate 336.
  • Nanopattern 346 is composed or made up of two parts or components.
  • the first part or component of nanopattern 346 corresponds to: (i) those areal portions or sections (e.g., belts) of substrate surface 334 of second or surface layer 342 which were chemically functionalized (derivatized) by the preceding contacting (332 [contacting]) procedure, as a result of having been brought into direct contact with ink 328 of replica configuration and shape 320.
  • the second part or component of nanopattern 346 corresponds to: (ii) the remaining areal portion or section of substrate surface 334 of second or surface layer 342 which was not chemically functionalized (derivatized) by the preceding contacting (332 [contacting]) procedure, as a result of not having been brought into direct contact with ink 328 of replica configuration and shape 320.
  • the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 348 [chemical functionalizing (derivatizing)], or via 356 [etching]) the nanopattern (nanoscale pattern), i.e., nanopattern 346, upon substrate surface 334 of second or surface layer 342 of substrate 336, which was obtained from the preceding separating (344 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 348 [chemical functionalizing (derivatizing)], or via 356 [etching]) the preceding stated second part or component of /o
  • nanopattern 346 i.e., the remaining areal portion or section of substrate surface 334 of second or surface layer 342 of substrate 336 which was not chemically functionalized (derivatized) by the preceding contacting (332 [contacting]) procedure (as a result of not having been brought into direct contact with ink 328 of replica configuration and shape 320).
  • the processing step (procedure) further includes modifying (via 348 [chemical functionalizing (derivatizing)], or via 356 [etching]) the exposed areal portion or section of substrate surface 334 of second or surface layer 342 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346, i.e., of the nanoscale pattern of replica configuration and shape 320.
  • Modifying, via 348 [chemical functionalizing (derivatizing)], the nanopattern (nanoscale pattern), i.e., nanopattern 346, upon substrate surface 334 of second or surface layer 342 of substrate 336, is performed by using a suitable chemical functionalizing (derivatizing) procedure or technique, involving a suitable chemical functionalizing (derivatizing) reagent.
  • a suitable chemical functionalizing (derivatizing) procedure, or technique is, for example, selected from the group consisting of a thiol compound based functionalizing (derivatizing) procedure or technique, and a silane compound based functionalizing (derivatizing) procedure or technique.
  • a thiol compound based chemical functionalizing (derivatizing) procedure or technique involving a thiol compound based chemical functionalizing (derivatizing) reagent.
  • a suitable thiol compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 16-mercaptohexadecanoic acid, 12-thioldodecanol, and 12-aminododecanethiol.
  • a silane compound based type of functionalizing (derivatizing) procedure or technique involving a silane compound based chemical functionalizing (derivatizing) reagent.
  • a suitable silane compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 3 -aminopropyl-triethoxisilane, and 3 -mercaptopropyl-trimethoxysilane.
  • Modifying via 348 [chemical functionaiizing (derivatizing)] the exposed areal portion or section of substrate surface 334 of second or surface layer 342 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346, results in formation of a different substrate surface, i.e., substrate surface 354, of second or surface layer 342 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346.
  • this modifying, via 348 [chemical functionalizing (derivatizing)], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 350 of nanostrips 352 on substrate surface 354 of substrate 336.
  • any single or individual nanostrip 352 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (run) and about 10 nanometers (run), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch (e.g., analogous to P 2 , shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanostrips 352, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch between two neighboring similar (i.e., not necessarily identical) nanostrips of array 350 of nanostrips 352 on substrate surface 354 of substrate 336 has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to Pi, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanosteps of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300.
  • the width of any single or individual nanostrip of array 350 of nanostrips 352 on substrate surface 354 of substrate 336 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanostrips of array 350 of nanostrips 352 on substrate surface 354 of substrate 336.
  • etching procedure or technique involving a suitable etching (etchant) reagent.
  • a suitable etching procedure or technique is, for example, selected from o
  • a suitable oxidizing compound based wet etching (etchant) reagent is, for example, a solution composed of: (i) potassium ferricyanide [K 3 Fe(CN) 6 ], 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1M; and (iii) potassium hydroxide [KOH], 1.0 M, which is particularly for wet etching of gold [Au].
  • Another suitable wet etching (etchant) reagent is, for example, a solution composed of potassium hydroxide [KOH], 0.1 M, which is particularly useful for wet etching of silicon [Si] .
  • a reactive ion etching type of dry etching procedure or technique involving a reactive ion etching dry etching (etchant) reagent.
  • An exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous sulfur tetra-fiuoride [SF 4 ].
  • Another exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous chlorine [Cl 2 ].
  • this modifying, via 356 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 358 of nanobelts 360 on substrate surface 362 of substrate 340.
  • any single or individual nanobelt 360 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch e.g., analogous to P 2 , shown in Fig.
  • the pitch between two neighboring similar (i.e., not necessarily identical) nanobelts of array 358 of nanobelts 360 on substrate surface 362 of substrate 340 has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to Pj, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanosteps of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300.
  • the width of any single or individual nanobelt of array 358 of nanobelts 360 on substrate surface 362 of substrate 340 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanobelts of array 358 of nanobelts 360 on substrate surface 362 of substrate 340.
  • Fig. 10 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved 1 type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by treating a 'singular' crystal surface, particularly highlighting application of material upon the surface of the self-assembled template, which, in turn, is directly used for generating an array of nanowires (nanoscale structures) on a substrate surface.
  • a 'nanogrooved 1 type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by treating a 'singular' crystal surface, particularly highlighting application of material upon the surface of the self-assembled template, which, in turn, is directly used for generating an array of nanowires (nanoscale structures) on a substrate surface.
  • a 'nanogrooved' type faceted self-assembled template 120 whose nanogrooved surface includes an array 124 of nanoscale features, i.e., nanogrooves.
  • Array 124 of nanogrooves is spontaneously formed, for example, as illustratively described hereinabove, with reference to Fig. 4, via a process of facet formation (Fig. 4, 126 [facet formation]), by treating (Fig. 4, 128 [annealing]) a 'singular' crystal surface (Fig. 4, 130).
  • the singular crystal surface (Fig. 4, 130) is obtained by cutting (Fig. 4, 132 [cutting]) a crystal (Fig. 4, 134) along a 'singular' cutting plane (Fig. 4, 136 (corresponding to a low-index plane) located within a crystal surface region of the crystal (Fig. 4, 134).
  • a material applying process in particular, a depositing type of material applying process [e.g., a physical deposition process, or a chemical deposition process]
  • at least one material 370 in particular, at least one suitable depositing material
  • a suitable depositing material is, for example, a metal element [e.g., platinum [Pt], gold [Au], or molybdenum [Mo]]; a metal alloy [e.g., palladium-gold [PdAu]]; a semi-metal element [e.g., elemental silicon [Si]]; a non-metal element [e.g., an allotrope of carbon, such as nanotube elemental carbon]; or an organic polymer [e.g., a thermoplastic, such as polystyrene (PS)].
  • a metal element e.g., platinum [Pt], gold [Au], or molybdenum [Mo]
  • a metal alloy e.g., palladium-gold [PdAu]
  • a semi-metal element e.g., elemental silicon [Si]
  • a non-metal element e.g., an allotrope of carbon, such as nanotube elemental carbon
  • This step is performed for replicating the at least part of array 124 of nanogrooves of the nanogrooved surface, such that the applied material(s) 374, i.e., the deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), includes a replica configuration and shape of the at least part of array 124 of nanogrooves of the nanogrooved surface of nanogrooved type faceted self-assembled template 120. Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow. Treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
  • the applied material(s) 374 i.e., the deposited material (in particular, the deposited metal
  • the treating step (procedure) includes allowing the applied material(s) 374, i.e., the deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), while maintaining the replica configuration and shape thereof, upon the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, to stand at a pre-determined temperature, for a pre-determined period of time.
  • the applied material(s) 374 i.e., the deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer)
  • treated applied material(s) 374 i.e., the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120. As shown in Fig. 10, this embodiment is indicated as element 376.
  • the treated applied material(s) 374 i.e., the treated deposited material (in particular, the treated deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, via element 376, with the substrate surface 380 of substrate 382, for forming a combination structure 384 having the replica configuration and shape in contact with substrate surface 380 of substrate 382.
  • the treated applied material(s) 374 i.e., the treated deposited material (in particular, the treated deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer)
  • This main step (procedure) of contacting (378 [contacting]) involves, and results in, transferring, via element 376, a portion or layer of the treated applied material, i.e., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, onto substrate surface 380 of substrate 382. Additional details relating to performing this main step (procedure), and sub-steps
  • the processing step involves separating (390 [separating]) the replica configuration and shape of the treated applied material, i.e., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), part of combination structure 384, via element 376, from substrate surface 380 of substrate 382.
  • the treated applied material i.e., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer)
  • this processing step results in generating the array of the nanoscale structures on the substrate surface, i.e., array 392 of nanowires 394 on substrate surface 380 of substrate 382.
  • any single or individual nanowire 394 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch (e.g., analogous to P 2 , shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanowires 394, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron ( ⁇ m).
  • the pitch between two neighboring similar (i.e., not necessarily identical) nanowires of array 392 of nanowires 394 on substrate surface 380 of substrate 382 has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to P 1 , shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanogrooves of array 124 of nanogrooves of the nanogrooved surface of nanogrooved type faceted self-assembled template 120.
  • the width of any single or individual nanowire of array 392 of nanowires 394 on substrate surface 380 of substrate 382 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanowires of array 392 of nanowires 394 on substrate surface 380 of substrate 382.
  • Fig. 1 Ia is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface (obtained by cutting along the 'M-plane' of a sapphire (alpha-alumina [(X-Al 2 O 3 ]) crystal), and characterized by R-plane and S-plane nanofacets, as exemplified and described in Example 1.
  • the main step (procedure) of providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface is performed as follows.
  • nanogrooved' type faceted self-assembled template 400 whose nanogrooved surface 402 includes an array 404 of nanoscale features, i.e., nanogrooves, characterized by R-plane and S-plane nanofacets.
  • array 404 of nanogrooves is spontaneously formed, via a process of facet formation (406 [facet formation]), by treating (408 [annealing]) 'singular' crystal surface 410.
  • Singular crystal surface 410 is obtained by cutting (412 [cutting]) a sapphire (alpha-alumina [ ⁇ -Al 2 O 3 ]) crystal 414 along a 'singular' cutting plane (M-plane) 416 (corresponding to a low-index plane) located within a crystal surface region of sapphire (alpha-alumina crystal 414.
  • the cutting (412 [cutting]) of sapphire (alpha-alumina [ ⁇ - Al 2 O 3 ]) crystal 414 is performed toward the [1,0,- 1,0] direction 418.
  • the remaining main steps (procedures) of this exemplary specific preferred embodiment of implementing the method of the present invention are as follows: applying (420 [applying materials]) at least one material upon at least part of array 404 of nanogrooves, for replicating the at least part of array 404 of nanogrooves, such that the applied material(s) includes a replica configuration and shape of the at least part of array 404 of nanogrooves; treating (422 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting (424 [contacting]) the replica configuration and shape of the treated applied material(s), with a substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing (indicated as 426 [array generation]) the combination structure, for generating the array of the nanoscale structures on the substrate surface.
  • Implementation of this exemplary specific preferred embodiment of the method of the present invention results in generating an array of nanoscale structures on a substrate surface of a substrate, for example, an array of nanostrips or nanowires on a substrate surface of a substrate.
  • Ib is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface (obtained by cutting along a 'vicinal C-plane' of a sapphire (alpha-alumina [U-Al 2 O 3 ]) crystal), and characterized by R-plane and C-plane nanofacets, as exemplified and described in Example 2.
  • a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface (obtained by cutting along a 'vicinal C-plane' of a sapphi
  • the main step (procedure) of providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface is performed as follows.
  • nanostepped surface 432 includes an array 434 of nanoscale features, i.e., nanosteps, characterized by R-plane and C-plane nanofacets.
  • array 434 of nanosteps is spontaneously formed, via a process of facet formation (436 [facet formation]), by treating (438 [annealing]) 'vicinal' crystal surface 440.
  • Vicinal crystal surface 440 is obtained by cutting (442 [cutting]) a sapphire (alpha-alumina [(X-AI 2 O 3 ]) crystal 444 along a 'vicinal' cutting plane (vicinal C-plane) 446 (at a miscut tilt angle ( ⁇ ) relative to the nearest low-index plane) located within a ciystal surface region of sapphire (alpha-alumina [(X-Al 2 O 3 ]) crystal 444.
  • the cutting (442 [cutting]) of sapphire (alpha-alumina [Oc-Al 2 O 3 ]) crystal 444 is performed toward the [1,-1,0,0] direction 448.
  • the remaining main steps (procedures) of this exemplary specific preferred embodiment of implementing the method of the present invention are as follows: applying (450 [applying materials]) at least one material upon at least part of array 434 of nanosteps, for replicating the at least part of array 434 of nanosteps, such that the applied material(s) includes a replica configuration and shape of the at least part of array 434 of nanosteps; treating (452 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting (454 [contacting]) the replica configuration and shape of the treated applied material(s), with a substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing (indicated as 456 [array generation]) the combination structure, for generating the array of _ the nanoscale structures on the substrate surface.
  • Implementation of this exemplary specific preferred embodiment of the method of the present invention results in generating an array of nanoscale structures on a substrate surface of a substrate, for example, an array of nanostrips or nanobelts on a substrate surface of a substrate.
  • crystal surfaces chosen to represent these two types of faceting surfaces were, respectively: (i) a 'singular' crystal surface (obtained by cutting along the 'M-plane' of a sapphire (alpha-alumina [ ⁇ -Al 2 ⁇ 3 ]) [1,0,-1,0] crystal), and characterized by R-plane and S-plane nanofacets (e.g., as schematically illustrated in Fig. l la), and (ii) a 'vicinal' crystal surface (obtained by cutting along a
  • the different templates of the sapphire (alpha-alumina [(X-Al 2 O 3 ]) crystals were produced as wafers by cutting into 1 x 1 cm pieces, followed by mechanical polishing.
  • Lattice and miscut orientations of the vicinal crystal surfaces were determined by a standard technique of asymmetric double-exposure back-reflection X-ray diffraction.
  • the M-plane and miscut C-plane sapphire crystal surfaces were then thermally annealed in air at 1100 0 C and 1500 0 C for 20 - 48 hrs, and 5 - 10 hrs, respectively.
  • the periodic arrays of highly straight and parallel nanofacets were generated by annealing different unstable faces of the sapphire (alpha-alumina [(X-AI2O3]) crystal.
  • the nanopatterns of these self-assembled (self-organized) templates were replicated by a standard soft lithography procedure to produce patterned self-assembled monolayers (SAMs) of silanes on a silicon/silicon dioxide [Si/SiO 2 ] surface, or of thiols on a gold [Au] surface, in parallel lines or crossbar arrays, where the thinner lines were as thin as 10 nm with a pitch of 40 nm, extending over areas on the order of square centimeters.
  • SAMs self-assembled monolayers
  • Patterned SAM samples, silanes or thiols, were made on clean native Si (100) (Boron-doped, 10 - 70 ohm-cm, obtained from VirginiaSemi, USA) and on Si (100) coated with a 50 A adhesion layer of chromium [Cr] followed by a 200 A layer of gold [Au], and then cleaned with piranha reagent (3:1, sulfuric acid [H 2 SO 4 ]: hydrogen peroxide [H 2 O 2 ]) for 2 hours, respectively.
  • the patterned SAMs were prepared by nanocontact printing (nCP), similar to microcontact ( ⁇ CP) printing.
  • nCP nanocontact printing
  • ⁇ CP microcontact
  • the templates for the fabrication of the elastomeric stamps were the above mentioned faceted sapphire surfaces.
  • each elastomeric stamp the sapphire template was placed in a polystyrene dish, and a degassed 9:1 (volume/volume) mixture of polydimethylsiloxane (PDMS), [SylgardTM 184 silicone elastomer (Sylgard) and its curing agent (obtained from Dow-Corning Corp.)], as an exemplary organic-inorganic form of an elastomer type of applying material, was applied, via casting (molding), on top of the self-assembled (annealed) crystal surfaces, and were then separated (via peeling off) therefrom.
  • PDMS polydimethylsiloxane
  • SylgardTM 184 silicone elastomer silicone elastomer
  • curing agent obtained from Dow-Corning Corp.
  • PDMS polydimethylsiloxane
  • stamps self-assembled templates
  • OTS octadecyltrichlorosilane
  • 1-hexadecanetliiol in ethanol
  • the elastomeric stamps were first washed few times with n-heptane (Merck) and ethanol (Bio Lab Ltd.), and then inked with hexane (Bio Lab Ltd.) solution of octadecyltrichlorosilane (OTS) (Aldrich), or an ethanolic (Bio Lab Ltd.) solution of
  • the printed Si surfaces were then immediately etched with a dilute potassium hydroxide [KOH] etching solution, in order to generate an array of nanoscale structures.
  • the printed Au surfaces were then allowed to react with 16-mercaptohexadecanoic acid in order to functionalize (derivatize) the remaining bare regions, or were immediately selectively etched with the oxidizing type of wet etching (etchant) reagent, being a solution composed of: (i) potassium ferricyanide [K 3 Fe(CN) 6 ] (Sigma- Aldrich), 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1 M; and (iii) potassium hydroxide [KOH] (Frutarom Ltd., Israel), 1.0 M, which is particularly for wet etching of gold [Au], in order to generate an array of nanoscale structures.
  • the faceted sapphire templates, the elastomeric stamps, and the etched Si or Au nanostructures, were topographically imaged by tapping-mode AFM.
  • the etched Si nanostructures were also imaged by scanning electron microscope (SEM).
  • SEM scanning electron microscope
  • the Au patterned SAMs were imaged by contact (friction) mode AFM.
  • Topographic images of the sapphire were obtained with Veeco NanoProbeTM AFM tips, model FESP (L: 221 ⁇ m, F 0 : 70 - 95 kHz).
  • Topographic images of the PDMS stamps were obtained with NanoProbeTM tips, model: TESP (L: 128 ⁇ m, F 0 : 272 - 322 kHz).
  • Friction-mode images were obtained with ultrasharp carbon-whisker tips from
  • NanoTOOLS GmbH Germany
  • model HDC High Dense Carbon
  • R nominal radius of curvature
  • W 15 ⁇ m
  • k 0.38 N/m
  • Scanning electron microscopy (FE-SEM) images were acquired with a LEO ULTRA, in ultra-high vacuum.
  • Example 1 The results obtained for Example 1 are presented in Figs. 12a - 12f, each of which is described hereinbelow.
  • Fig. 12a is an atomic force microscope (AFM) topographic mode image of an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface includes an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a crystal surface; the self-assembled template corresponds to an annealed sapphire M-plane crystal surface (e.g., as shown in Fig. 1 Ia), characterized by R-plane and S-plane nanofacets having inclinations of 16.7 degrees and 32.6 degrees, respectively, pitch of 37 ⁇ 3 nanometers (nm), and height (depth) of about 8 nanometers (run).
  • AFM atomic force microscope
  • Fig. 12b is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary nanogrooved, nanofaceted surface replica element; the surface replica element (formed according to the embodiment illustrated in Fig. 4) corresponds to a polydimethylsiloxane (PDMS) cast or mold (elastomeric stamp) (whose nanogrooves have a pitch of 40 ⁇ 5 nanometers (nm)) of the surface of the nanogrooved, nanofaceted self-assembled template (annealed sapphire M-plane crystal surface) shown in Fig. 12a.
  • PDMS polydimethylsiloxane
  • elastomeric stamp whose nanogrooves have a pitch of 40 ⁇ 5 nanometers (nm)
  • Fig. 12c is an atomic force microscope (AFM) friction mode of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of 1-hexadecanethiol functionalized nanostrips (width of 10 - 20 nanometers (nm) and pitch of 50 ⁇ 5 nanometers (nm)) on a gold [Au] with chemically bound 16-mercaptohexadecanoic acid substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by reacting a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig.
  • AFM atomic force microscope
  • Fig. 12d is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of gold [Au] nanowires on a silicon [Si] substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate.
  • AFM projected atomic force microscope
  • Fig. 12e is a graphical plot of nanowire height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanowires, of the array of gold [Au] nanowires on the silicon [Si] substrate surface shown in Fig. 12d; the gold [Au] nanowires have a width (half-pitch) of about 20 nanometers (nm) and a height (diameter) of about 20 nanometers (nm).
  • Fig. 12f is anatomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a grid (waffle) type array of gold [Au] nanowires on a silicon [Si] substrate surface; the array was generated (according to embodiments illustrated in Figs. 4 and 5) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate.
  • AFM atomic force microscope
  • Example 2 The results obtained for Example 2 are presented in Figs. 13a - 13f, each of which is described hereinbelow.
  • Fig. 13a is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of nanogrooves (pitch of about 50 nanometers (nm)) on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs.
  • SEM scanning electron microscope
  • a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si] (wafer) substrate surface wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig. Ha).
  • OTS octadecyltrichlorosilane
  • Fig. 13b is an atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13a, wherein the nanogrooves have a pitch of about 50 nanometers (run).
  • AFM atomic force microscope
  • Fig. 13c is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Figs. 13a and 13b.
  • AFM projected atomic force microscope
  • Fig. 13d is a graphical plot of nanogroove height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanogrooves, of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13c, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a height (depth) of about 120 nanometers (nm).
  • Fig. 13e is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a waffle type array of nanogrooves on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs.
  • SEM scanning electron microscope
  • a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si] (wafer) substrate surface wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig. 1 Ia).
  • OTS octadecyltrichlorosilane
  • Fig. 13f is an atomic force microscope (AFM) topographic mode (zoom) image of the surface of the waffle type array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13e, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a (depth) height of about 100 nanometers (nm).
  • AFM atomic force microscope
  • the present invention has several beneficial and advantageous aspects, characteristics, and features, which are based on or/and a consequence of, the above illustratively described main aspects of novelty and inventiveness. Additionally, the present invention is clearly commercial applicable in the general field of nanoscale science (nanoscience) or technology (nanotechnology), encompassing, or at least associated with, sub-fields and areas such as nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electrornechanics (nanoelectromechanics), and nanoscale semiconductor technology, focusing on methods, processes, or techniques, which are used for producing or fabricating arrays of nanoscale structures on substrate surfaces.
  • the present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures (e.g., nano wires, nanostrips, nanobelts, nanoparticles, or nanogrooves) on various different types or kinds of substrate surfaces (e.g., metallic, semi-metallic, non-metallic).
  • nanoscale structures e.g., nano wires, nanostrips, nanobelts, nanoparticles, or nanogrooves
  • substrate surfaces e.g., metallic, semi-metallic, non-metallic.
  • the produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior.
  • the present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components.
  • Such nanoscale devices and components are used, or are potentially useful, in essentially every field of science and technology.
  • the present invention successfully addresses and overcomes the shortcomings and limitations, and widens the scope, of presently known techniques and methods for producing an array of nanoscale structures on a substrate surface.
  • the present invention provides a practical, efficient, and cost effective, method for transferring or replicating periodic faceting patterns onto separate substrates.

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Abstract

Method for producing an array of nanoscale structures on a substrate surface, via a self-assembled template. Providing self-assembled template 10 whose surface includes array 12 of nanoscale features 14 spontaneously formed by treating 16 crystal surface 18; applying 20 material(s) upon array 12 of nanoscale features 14, for replicating array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape of array 12 of nanoscale features 14; treating 22 the applied material(s) while maintaining replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting 24 the replica configuration and shape of treated applied material(s), with the substrate surface 26, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26; and processing the combination structure, for generating 28 array 30 of nanoscale structures 32 on substrate surface 26 of substrate 34.

Description

PRODUCING AN ARRAY OF NANOSCALE STRUCTURES ON A SUBSTRATE SURFACE VIA A SELF-AS SEMBLED TEMPLATE
FIELD AND BACKGROUND OF THE INVENTION
The present invention relates to the general field of naiioscale science (nanoscience) or technology (nanotechnology), encompassing, or at least associated with, sub-fields and areas such as nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electromechanics (nanoelectromechanics), and nanoscale semiconductor technology, focusing on methods, processes, or techniques, which are used for producing or fabricating arrays of nanoscale structures on substrate surfaces. More particularly, the present invention relates to a method for producing an array of nanoscale structures on a substrate surface, via a self-assembled template.
The present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures on various different types or kinds of substrate surfaces. The produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior. The present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components. Just a few examples of such are memories, logic gates, sensors, actuators, circuits, polarizers, and liquid crystal displays (LCDs). Such nanoscale devices and components, among many others not specifically mentioned herein, are used, or are potentially useful, in essentially every field of science and technology.
Theories, principles, and practices thereof, and, related and associated applications and subjects thereof, relating to the general field of nanoscience or nanotechnology, and relating to sub-fields and areas such as nanoelectronics, nanomechanics, nanoelectromechanics, and nanoscale semiconductor technology, focusing on methods, processes, or techniques, which are applicable for producing or fabricating arrays of nanoscale structures on substrate surfaces, are well known and taught about in the prior art, and currently practiced in a wide variety of numerous different fields and areas of science and technology. For the purpose of establishing the scope, meaning, and fϊeld(s) or area(s) of application, of the present invention, the following background briefly describes the current state-of-the-art as relating to the field of the present invention.
The large-scale patterning of materials and molecules down to nanometer feature sizes is a critical issue of nanoscience and nanotechnology. Photolithography is limited by the wavelength of light, which is 193 nm for the Deep-UV technology used today in industry, while Extreme-UV technology under development can reach 50 nm feature sizes, aiming for 32 nm in 2009 [I]. These limitations have motivated an extensive exploration of alternative lithographies based on self-assembly. Soft lithography is a versatile approach for the replication of patterns into a broad variety of media [2], but the original pattern, as in photolithography, must usually be generated by other methods. Nanopattern generation systems (NPGS) include electron-beam lithography [3], scanning probe nanolithographies, such as dip-pen nanolithography [4], and constructive nanolithography [5], which can reach feature sizes down to 5 nm, 30 nm, and 9 nm, respectively. These methods have the advantage that the pattern is encoded in a computer-assisted design software file, allowing the deterministic generation of arbitrary, aperiodic patterns, as well as periodic patterns with high degrees of perfection and long-range order. A major disadvantage of these 'top-down' nanopattern generation methods, however, is that they are serial, and hence extremely time-consuming for large areas. A recent nanofabrication method based on the replication of superlattice cross-sections yields sub- 10 nm periodic nano wires of high perfection [6 - 8], but the width of the patterned area is limited to a few hundred microns by the thickness of the templating superlattice. This aspect presents a severe size limitation, which completely precludes the manufacturing of large-area nanostructured surfaces which are needed, and widely used, in industrial applications, such as aligning layers for liquid crystal displays (LCDs). For example, having a practical, efficient, and cost effective, method for large-scale production of geometrically and chemically tailored alignment layers for liquid crystal displays (LCDs), would enable a finer and more rational control of the nematic phases than the mechanically rubbed films used today.
Prior art includes various additional teachings [9 - 14] about manufacturing (fabricating) nanoscale structures on substrate surfaces. 'Bottom-up' nanopattern generation processes based on spontaneous self-assembly, are of special technological and scientific interest, especially for large-area, periodic nanostructures where perfection and long-range order are less critical. This may be the case of nanoelectronics, where connectivity and short-range order are more important than long-range order, and there can be a certain degree of defect-tolerance [15], as well as many other applications in surface and materials technology, such as display technology, microarray technology, microelectromechanics, chemical/biological sensing, etc. [16]. Such promising approaches of bottom-up nanopattern generation include those based on the self-assembly of block-copolymers (block-copolymer lithography) [17], colloidal particles (nanosphere lithography) [18], and biomolecules (biotemplate lithography) [19], where the patterns are encoded in the polymer block lengths and their relative affinities, the colloidal nanoparticle size, and the genetically encoded molecular shape and recognition, respectively.
Typical crystals are usually overlooked as nanoscopically dull, since their lattice parameters are well below the nanoscale. Though true for the bulk, this is not so for the crystal surfaces, which are intrinsically unstable, and can undergo a series of spontaneous restructurations (self-assemblies, self-organizations), eventually ending with the formation of a periodically faceted surface [20, 21]. Such surface restructuration processes lead to a progressive increase in the surface periodicity from 0.1 nm to 1 μm, encompassing the whole nanoscale. Periodically faceted surfaces have been extensively used as epitaxial substrates for the production of self-assembled nano wires such substrates [20 - 23]. Periodic faceting patterns, however, have not yet been transferred or replicated onto other substrates.
There is thus a need for, and it would be highly advantageous and useful to have a method for producing an array of nanoscale structures on a substrate surface via a self-assembled template.
SUMMARY OF THE INVENTION ^
The present invention relates to a method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template. The present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures on various different types or kinds of substrate surfaces. The produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior.
The present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components, just a few examples of such are memories, logic gates, sensors, actuators, circuits, polarizers, and liquid crystal displays (LCDs). Such nanoscale devices and components, among many others not specifically mentioned herein, are used, or are potentially useful, in essentially every field of science and technology.
Thus, according to the present invention, there is provided a method for producing an array of nanoscale structures on a substrate surface, the method comprising: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features; treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied materials) having the replica configuration and shape; contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
According to further characteristics in preferred embodiments of the invention described below, the self-assembled template is composed of a crystalline substance selected from the group consisting of crystalline inorganic matter, crystalline organic matter, and a combination thereof.
According to further characteristics in preferred embodiments of the invention described below, the crystalline inorganic matter is selected from the group consisting of: a crystalline single metal oxide, a crystalline mixed metal oxide, a crystalline inorganic salt, a periodic table group IV element, a compound of periodic table group IV elements, a compound of a periodic table group III element and a periodic table group V element, a compound of a periodic table group II element and a periodic table group VI element, a crystalline carbide, a crystalline suicide, a crystalline hydride, a crystalline elemental metal, and a crystalline alloy.
According to further characteristics in preferred embodiments of the invention described below, the crystalline single metal oxide is selected from the group consisting of: alpha-aluminum oxide (sapphire) [α-Al2O3], alpha-silicon oxide (quartz) [(X-SiO2], zinc oxide [ZnO], magnesium oxide [MgO], and titanium oxide [TiO2]. According to further characteristics in preferred embodiments of the invention described below, the periodic table group IV element is elemental silicon [Si].
According to further characteristics in preferred embodiments of the invention described below, the compound of a periodic table group III element and a periodic table group V element is gallium arsenide [GaAs]. According to further characteristics in preferred embodiments of the invention described below, the crystalline organic matter is selected from the group consisting of: an amino acid, a protein, a carbohydrate, an aliphatic compound, and an aromatic compound.
According to further characteristics in preferred embodiments of the invention described below, the combination of crystalline inorganic matter and crystalline organic matter is selected from the group consisting of: a crystalline organic salt, and a crystalline organometallic complex.
According to further characteristics in preferred embodiments of the invention described below, the self-assembled template has a three-dimensional polyhedron bulk or overall geometrical shape or form, or a three-dimensional non-polyhedron curved bulk or overall geometrical shape or form.
According to further characteristics in preferred embodiments of the invention described below, the three-dimensional polyhedron bulk or overall geometrical shape or form is selected from the group consisting of: a parallelpiped, a prism, and a pyramid. According to further characteristics in preferred embodiments of the invention described below, the three-dimensional non-polyhedron curved bulk or overall geometrical shape or form is selected from the group consisting of: a cylinder, a disc (disk), and a cone. According to further characteristics in preferred embodiments of the invention described below, the self-assembled template has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a range of between about 0.1 nanometer (nm) and about 1 meter (m).
According to further characteristics in preferred embodiments of the invention described below, the self-assembled template has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron (μm) and about 1 centimeter (cm), (ii) a second range of between about 100 microns (μm) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
According to further characteristics in preferred embodiments of the invention described below, the self-assembled template, the array of nanoscale features corresponds to a parallelogram or parallelogram-like ordered arrangement or set of features, structures, or elements.
According to further characteristics in preferred embodiments of the invention described below, the nanoscale features of the array are selected from the group consisting of nanoscale facets (nanofacets), nanoscale grooves (nanogrooves), and nanoscale steps (nanosteps).
According to further characteristics in preferred embodiments of the invention described below, the array of nanoscale features, a single or individual nanoscale feature has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
According to further characteristics in preferred embodiments of the invention described below, the array of nanoscale features, pitch between two neighboring similar nanoscale features has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
According to further characteristics in preferred embodiments of the invention described below, the crystal surface is obtained by cutting at least part of a crystalline substance, or by depositing a crystalline substance onto a surface of another substance.
According to further characteristics in preferred embodiments of the invention described below, the cutting is along a singular cutting plane, corresponding to a low-index plane, of a crystal.
According to further characteristics in preferred embodiments of the invention described below, the cutting is along a vicinal cutting plane at a miscut tilt angle (θ) relative to nearest low-index plane of a crystal.
According to further characteristics in preferred embodiments of the invention described below, the treating involves annealing the crystal surface.
According to further characteristics in preferred embodiments of the invention described below, the treating involves etching the crystal surface.
According to further characteristics in preferred embodiments of the invention described below, the applying step is performed according to a material applying process selected from the group consisting of: casting (molding), and depositing.
According to further characteristics in preferred embodiments of the invention described below, the casting (molding) process is selected from the group consisting of: a polymer cross-linking type of casting (molding) process, and a liquid-to-solid phase transition type of casting (molding) process.
According to further characteristics in preferred embodiments of the invention described below, the depositing process is selected from the group consisting of: a physical deposition process, and a chemical deposition process.
According to further characteristics in preferred embodiments of the invention described below, in the applying step, the at least one material applied upon the at least part of the array is composed of a substance selected from the group consisting of organic matter, inorganic matter, and a combination thereof. According to further characteristics in preferred embodiments of the invention described below, the organic matter is an organic polymer. According to further characteristics in preferred embodiments of the invention described below, the organic polymer is selected from the group consisting of: a thermoplastic, a thermoset, an elastomer, and any combination thereof.
According to further characteristics in preferred embodiments of the invention described below, the inorganic matter is selected from the group consisting of: a metal element, a metal alloy, a semi-metal element, a non-metal element, and any combination thereof.
According to further characteristics in preferred embodiments of the invention described below, the metal element is selected from the group consisting of: a noble metal element, a transition metal element, and a main group metal element.
According to further characteristics in preferred embodiments of the invention described below, the metal alloy is selected from the group consisting of: palladium-gold [PdAu], and platinum-iridium [PtIr].
According to further characteristics in preferred embodiments of the invention described below, the semi-metal element is selected from the group consisting of: elemental silicon [Si], and elemental germanium [Ge].
According to further characteristics in preferred embodiments of the invention described below, the non-metal element is selected from the group consisting of: an allotrope of carbon, and elemental boron [B]. According to further characteristics in preferred embodiments of the invention described below, the combination of a metal element and a non-metal element, in a form of a compound, is selected from the group consisting of: indium oxide [In2Oa], molybdenum diselinide [MoSe2], and boron nitride [BN].
According to further characteristics in preferred embodiments of the invention described below, the combination of organic matter and inorganic matter is an organic- inorganic polymer.
According to further characteristics in preferred embodiments of the invention described below, the organic-inorganic polymer is selected from the group consisting of: an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, and any combination thereof.
According to further characteristics in preferred embodiments of the invention described below, in the applying step, the at least one material applied upon the at least part of the array has an amorphous structure, or a crystalline structure. According to further characteristics in preferred embodiments of the invention described below, wherein for the applying step performed according to a casting (molding) type of material applying process, then, the treating step includes forming a stand-alone cast (mold) type of surface replica element having the replica configuration and shape. According to further characteristics in preferred embodiments of the invention described below, the treating step further includes inking, by using a suitable ink, surface of the cast (mold) type of the surface replica element.
According to further characteristics in preferred embodiments of the invention described below, the ink is selected from the group consisting of a thiol compound based ink, and a silane compound based ink.
According to further characteristics in preferred embodiments of the invention described below, the thiol compound based ink is a solution or suspension of a thiol compound selected from the group consisting of: n-hexadecanethiol, n-dodecanethiol, and n-octadecanethiol. According to further characteristics in preferred embodiments of the invention described below, the silane compound based ink is a solution or suspension of a silane compound selected from the group consisting of: octadecyltricholorosilane, 3-aminopropyl- triethoxisilane, and 3-mercaptopropyl-trimethoxysilane.
According to further characteristics in preferred embodiments of the invention described below, the processing step includes forming a nanopattern (nanoscale pattern) upon the substrate surface.
According to further characteristics in preferred embodiments of the invention described below, the nanopattern (nanoscale pattern) is formed by using the cast (mold) type of the surface replica element with a roller. According to further characteristics in preferred embodiments of the invention described below, the processing step further includes modifying the nanopattern (nanoscale pattern), by using a chemical functionalizing (derivatizing) procedure, or by using an etching procedure.
According to further characteristics in preferred embodiments of the invention described below, the modifying is performed by using a thiol compound based chemical functionalizing (derivatizing) procedure, involving a thiol compound based chemical functionalizing (derivatizing) reagent. According to further characteristics in preferred embodiments of the invention described below, the modifying is performed by using a silane compound based type of functionalizing (derivatizing) procedure, involving a silane compound based chemical functionalizing (derivatizing) reagent. According to further characteristics in preferred embodiments of the invention described below, the modifying is performed by using a wet etching procedure, or a dry etching procedure.
According to further characteristics in preferred embodiments of the invention described below, in the array of the nanoscale structures generated on the substrate surface, the nanoscale structures are selected from the group consisting of: nanoscale wires (nanowires), nanoscale strips (nanostrips), nanoscale belts (nanobelts), nanoscale particles (nanoparticles), and nanoscale grooves (nanogrooves).
According to further characteristics in preferred embodiments of the invention described below, a single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm). According to further characteristics in preferred embodiments of the invention described below, a single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
According to further characteristics in preferred embodiments of the invention described below, in the array of the nanoscale structures generated on the substrate surface, pitch between two neighboring similar nanoscale structures has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm). The present invention is implemented by performing steps or procedures, and sub-steps or sub-procedures, in a manner selected from the group consisting of manually, semi-automatically, fully automatically, and a combination thereof, involving use and operation of various devices, instruments, and, peripheral equipment, utilities, accessories, and materials, in a manner selected from the group consisting of manually, semi-automatically, fully automatically, and a combination thereof. Moreover, according to actual steps or procedures, sub-steps or sub-procedures, devices, instruments, and, peripheral equipment, utilities, accessories, and materials, used for implementing a particular embodiment of the disclosed invention, the steps or procedures, and sub-steps or sub-procedures, are performed by using hardware, software, or/and an integrated combination thereof, and the devices, instruments, and, peripheral equipment, utilities, accessories, and materials, operate by using hardware, software, or/and an integrated combination thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention is herein described, by way of example only, with reference to the accompanying drawings. With specific reference now to the drawings in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative description of the preferred embodiments of the present invention only, and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the present invention. In this regard, no attempt is made to show structural details of the present invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the invention may be embodied in practice. In the drawings:
Fig. 1 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary generalized preferred embodiment of implementing the method for producing an array of nanoscale structures on a substrate surface, in accordance with the present invention; Figs. 2a - 2e are schematic (flow-type) diagrams illustrating main steps
(procedures), and structures, of an exemplary specific preferred embodiment of forming a 'nanogrooved' type faceted self-assembled template, including cutting a crystal along a 'singular' cutting plane (a low-index plane) of the crystal, wherein the self-assembled template is used for generating an array of nanoscale structures on a substrate surface, in accordance with the present invention;
Figs. 3a - 3d are schematic (flow-type) diagrams illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of forming a 'nanostepped' type faceted self-assembled template, including cutting a crystal along a 'vicinal' cutting plane (at a miscut tilt angle (θ) relative to the nearest low-index plane) of the crystal, wherein the self-assembled template is used for generating an array of nanoscale structures on a substrate surface, in accordance with the present invention;
Fig. 4 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanowires (nanoscale structures) on the substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface, in accordance with the present invention;
Fig. 5 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) a grid (waffle) type array of nanowires (nanoscale structures) on the substrate surface, in accordance with the present invention;
Fig. 6 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with an array of nanowires (nanoscale structures) on a substrate surface (e.g., of Fig. 4), for generating (via an etching technique) an array of nanoparticles (nanoscale structures) on the substrate surface, in accordance with the present invention; Fig. 7 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanogrooves (nanoscale structures) on the substrate surface, in accordance with the present invention;
Fig. 8 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with a roller for forming a nanopattern on a substrate surface, which, in turn, is useable for generating (via a functionalizing technique) an array of nanostrips on the substrate surface, in accordance with the present invention;
Fig. 9 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanobelts (nanoscale structures) on a substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface, in accordance with the present invention;
Fig. 10 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by treating a 'singular' crystal surface, particularly highlighting application of material upon the surface of the self-assembled template, which, in turn, is directly used for generating an array of nanowires (nanoscale structures) on a substrate surface, in accordance with the present invention;
Fig. 1 Ia is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface (obtained by cutting along the 'M-plane' of a sapphire (alpha-alumina [01-Al2O3]) crystal), and characterized by R-plane and S-plane nanofacets, as exemplified and described in Example 1, in accordance with the present invention;
Fig. 1 Ib is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface (obtained by cutting along a 'vicinal C-plane' of a sapphire (alpha-alumina [0,-Al2O3]) crystal), and characterized by R-plane and C-plane nanofacets, as exemplified and described in Example 2, in accordance with the present invention; Fig. 12a is an atomic force microscope (AFM) topographic mode image of an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface includes an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a crystal surface; the self-assembled template corresponds to an annealed sapphire M-plane crystal surface (e.g., as shown in Fig. lla), characterized by R-plane and S-plane nanofacets having inclinations of 16.7 degrees and 32.6 degrees, respectively, pitch of 37 ± 3 nanometers (nm), and height (depth) of about 8 nanometers (nm), as described in Example 1, in accordance with the present invention;
Fig. 12b is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary nanogrooved, nanofaceted surface replica element; the surface replica element (formed according to the embodiment illustrated in Fig. 4) corresponds to a polydimethylsiloxane (PDMS) cast (mold) (elastomeric stamp) (whose nanogrooves have a pitch of 40 ± 5 nanometers (nm)) of the surface of the nanogrooved, nanofaceted self-assembled template (annealed sapphire M-plane crystal surface) shown in Fig. 12a, as described in Example 1, in accordance with the present invention; Fig. 12c is an atomic force microscope (AFM) friction mode of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of 1-hexadecanethiol functionalized nanostrips (width of 10 - 20 nanometers (nm) and pitch of 50 ± 5 nanometers (nm)) on a gold [Au] with chemically bound 16-mercaptohexadecanoic acid substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by reacting a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate, with 16-mercaptohexadecanoic acid, as described in Example I5 in accordance with the present invention;
Fig. 12d is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of gold [Au] nano wires on a silicon [Si] substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate, as described in Example 1, in accordance with the present invention; Fig. 12e is a graphical plot of nano wire height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanowires, of the array of gold [Au] nanowires on the silicon [Si] substrate surface shown in Fig. 12d; the gold [Au] nanowires have a width (half-pitch) of about 20 nanometers (nm) and a height (diameter) of about 20 nanometers (nm), as described in Example 1, in accordance with the present invention; Fig. 12f is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a grid (waffle) type array of gold [Au] nanowires on a silicon [Si] substrate surface; the array was generated (according to embodiments illustrated in Figs. 4 and 5) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate; as described in Example I5 in accordance with the present invention;
Fig. 13a is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale sti*uctures on a substrate surface; the image shows an array of nanogrooves (pitch of about 50 nanometers (nm)) on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs. 4 and 7) by selective anisotropic wet etching of a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si] (wafer) substrate surface, wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig.
1 Ia), as described in Example 2, in accordance with the present invention; Fig. 13b is an atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig.
13a, wherein the nanogrooves have a pitch of about 50 nanometers (urn), as described in
Example 2, in accordance with the present invention;
Fig. 13c is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Figs. 13a and 13b, as described in Example 2, in accordance with the present invention;
Fig. 13d is a graphical plot of nanogroove height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanogrooves, of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13 c, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a height (depth) of about 120 nanometers (nm), as described in Example 2, in accordance with the present invention;
Fig. 13e is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a waffle type array of nanogrooves on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs. 5 and 7) by selective anisotropic wet etching of a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si]
(wafer) substrate surface, wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig. 1 Ia), as described in Example 2, in accordance with the present invention; and
Fig. 13f is an atomic force microscope (AFM) topographic mode (zoom) image of the surface of the waffle type array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13e, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a (depth) height of about 100 nanometers (nm), as described in Example 2, in accordance with the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention relates to a method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template. The present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures on various different types or kinds of substrate surfaces. The produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior. The present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components, just a few examples of such are memories, logic gates, sensors, actuators, circuits, polarizers, and liquid crystal displays (LCDs). Such nanoscale devices and components, among many others not specifically mentioned herein, are used, or are potentially useful, in essentially every field of science and technology. The method for producing an array of nanoscale structures on a substrate surface, of the present invention, includes the following main steps (procedures), and structures thereof: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features; treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing the combination structure, for generating the array of the nanoscale structures on the substrate surface. A main aspect of novelty and inventiveness of the present invention is provision of a method for producing (fabricating) an array of nanoscale structures on a substrate surface, via (by using) a self-assembled template, wherein the surface of the self-assembled template includes an array of nanoscale features that were spontaneously formed by treating a crystal surface of a crystal.
It is to be understood that the present invention is not limited in its application to the details of the order or sequence, and number, of steps or procedures, sub-steps or sub-procedures, of operation or implementation of the method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template, or to the details of the equipment, chemical reagents, and materials, used for implementing the method, set forth in the following illustrative description, accompanying drawings, and examples, unless otherwise specifically stated herein. The present invention is capable of other embodiments and of being practiced or carried out in various ways. Although steps or procedures, sub-steps or sub-procedures, equipment, chemical reagents, and materials, which are equivalent or similar to those illustratively described herein can be used for practicing or testing the present invention, suitable steps or procedures, sub-steps or sub-procedures, equipment, chemical reagents, and materials, are illustratively described and exemplified herein.
It is also to be understood that all technical and scientific words, terms, or/and phrases, used herein throughout the present disclosure have either the identical or similar meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise specifically defined or stated herein. Phraseology, terminology, and, notation, employed herein throughout the present disclosure are for the purpose of description and should not be regarded as limiting. Moreover, all technical and scientific words, terms, or/and phrases, introduced, defined, described, or/and exemplified, in the above Background section, are equally or similarly applicable in the illustrative description of the preferred embodiments, examples, and appended claims, of the present invention. Immediately following are definitions and exemplary usages of words, terms, or/and phrases, which are used throughout the illustrative description of the preferred embodiments, examples, and appended claims, of the present invention, and are especially relevant for understanding thereof. The term 'producing', and grammatical forms thereof, as used herein, are considered synonymous and equivalent to the following terms, and corresponding grammatical forms thereof: 'fabricating', 'making', 'creating', 'constructing', and 'manufacturing'.
The term 'features', as used herein, refers to distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements) of an object or entity. In the context of illustratively describing the method of the present invention, an example of such an object or entity is a surface of a self-assembled template. Accordingly, the term 'features', as used herein, refers to, for example, distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements) of a surface of a self-assembled template. Herein, exemplary features, i.e., distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements), of a surface of a self-assembled template, are: facets, grooves, and steps. Herein, these exemplary features are indicated as being of 'nanoscale', i.e., nanofacets, nanogrooves, and nanosteps, respectively, where the term 'nano', other terms prefixed by the term 'nano', and phrases including 'nano' terms, are each defined immediately following.
The term 'nano', as used herein, refers to the prefix (symbol 'n') of the unit, meter (symbol 'nϊ), in the SI (International System of Units) system of units denoting a factor of 10"9, of a size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), expressed in terms of nanometer or nanometers, each abbreviated or symbolized as 'nm'. The term 'nano' is also used herein as a prefix of, and combined with, each of various other terms, for indicating that the 'other' term, i.e., feature(s), structure(s), element(s), or characteristic(s), has (have), or is (are) associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch) in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
Specifically, the term 'nano' is used as a prefix of, and combined with, each of the following terms (expressed in singular form, or in plural form, i.e., with the suffix 's' (s)): facet(s), groove(s), grooved, step(s), stepped, wire(s), strip(s), particle(s), belt(s), pattera(s), and scale. Accordingly, the following 'nano' terms (expressed in singular form, or in plural form, i.e., with the suffix 's' (s)) are used herein: nanofacet(s), nanogroove(s), nanogrooved, nanostep(s), nanostepped, nanowire(s), nanostrip(s), nanoparticle(s), nanobelt(s), nanopattern(s), and nanoscale. Thus, herein, each of the following 'nano' terms: nanofacet(s), nanogroove(s), nanostep(s), nanowire(s), nanostrip(s), nanoparticle(s), nanobelt(s), and nanopattern(s), is used for indicating that the feature(s), structure(s), element(s), or characteristic^), i.e., facet(s), groove(s), step(s), wire(s), strip(s), particle(s), belt(s), or pattern(s), respectively, has (have), or is associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
Herein, each of the following 'nano1 terms: nanoscale, nanogrooved, and nanostepped, is used as part of a phrase, i.e., nanoscale feature(s), nanoscale structure(s), nanogrooved surface, and nanostepped surface.
Thus, in a similar manner of usage, the 'nano' phrase, nanoscale feature(s), as used herein, refers to a feature (features) (typically, on a surface) which has (have), or is (are) associated with, at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
Thus, in a similar manner of usage, the 'nano1 phrase, nanoscale structure(s), as used herein, refers to a structure (structures) (typically, on a surface) which has (have), or is (are) associated with, at least one size dimension ( e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
Thus, in a similar manner of usage, the 'nano' phrase, nanogrooved, as used herein, refers to a surface that includes and is characterized by, grooves (i.e., nanogrooves), and therefore, is described as being 'grooved' (i.e., nanogrooved), wherein each groove (i.e., nanogroove) has at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron].
Thus, in a similar manner of usage, the 'nano' phrase, nanostepped, as used herein, refers to a surface that includes and is characterized by, steps, and therefore, is described as being 'stepped' (i.e., nanostepped), wherein each step (i.e., nanostep) has at least one size dimension (e.g., length, width, height (thickness), depth, diameter, pitch), whose value or magnitude is in the range of between about one (1) nanometer (nm) and about one-thousand (1000) nanometers (nm) [one (1) micron]. The term 'pitch', as used herein, refers to: (1) an average center-to-center distance extending between two neighboring similar nanoscale features (e.g., two nanofacets, two nanogrooves, or two nanosteps) of an array of nanoscale features, particularly wherein the array of nanoscale features is on the surface of a self-assembled template, and also refers to: (2) an average center-to-center distance extending between two neighboring similar nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves), of an array of nanoscale structures, particularly wherein the array of nanoscale structures is on the surface of a substrate.
The term 'array', as used herein, refers to a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set of features, structures, or elements, in rows or/and columns, on a surface of an object or entity. In the context of illustratively describing the method of the present invention, such an object or entity is a surface of a self-assembled template, or a surface of a substrate (i.e., substrate surface). Accordingly, the term 'array1, as used herein, refers to a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set of features, structures, or elements, in rows or/and columns, on a surface of a self-assembled template, or on a surface of a substrate (i.e., substrate surface).
Herein, exemplary arrays, i.e., parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangements or sets of features, structures, or elements, in rows or/and columns, on a surface of a self-assembled template, are: (i) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale features, in rows or/and columns, on a self-assembled template, (ii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanofacets, in rows or/and columns, on a self-assembled template, (iii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square—like)) ordered arrangement or set) of nanogrooves, in rows or/and columns, on a self-assembled template, and (iv) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanosteps, in rows or/and columns, on a self-assembled template.
Herein, exemplary arrays, i.e., parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangements or sets of features, structures, or elements, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), are: (i) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale structures, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), (ii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanowires, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), (iii) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanobelts, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), (iv) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanostrips, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), (v) an array of nanoparticles, in rows or/and columns, on a surface of a substrate (i.e., substrate surface), and (vi) an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanogrooves, in rows or/and columns, on a surface of a substrate (i.e., substrate surface).
The phrase 'self-assembled template1, as used herein, refers to a pre-formed, master or standard (i.e., template type) crystal structure whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface (i.e., a surface of a crystal). The 'self-assembled template1, i.e., the pre-formed, master or standard (i.e., template type) crystal structure, is generated or formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) a surface of a crystal. More specifically, the (spontaneously formed) array of nanoscale features included on the surface of the 'self-assembled template', i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure, is spontaneously formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) a surface of a crystal.
As is well known in the arts of the relevant fields and subjects, the dynamic type of structural self-assembly (or self-organization) process, resulting in generation or formation of such a 'self-assembled template', i.e., a pre-formed, master or standard (i.e., template type) crystal structure, is generally known as being a process during which there occurs a specific type of (spontaneous) assembly or organization of atoms (groups of atoms) on a surface of a crystal without guidance or management from or by an outside (external) source. Accordingly, an important, and potentially exploitable, result of the (spontaneous) dynamic type of structural self-assembly (or self-organization) process, is spontaneous formation of an array of nanoscale features included on the surface of the 'self-assembled template1, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
An important aspect of such a (spontaneous) structural self-assembly (or self-organization) process, is that the final (desired) (spontaneously formed) array of nanoscale features included on the surface of the 'self-assembled template', i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure, is 'encoded' in the geometrical configuration (arrangement), shape, form, properties, characteristics, and features, of the atoms (groups of atoms) on the crystal surface which is subjected to the structural self-assembly (or self-organization) process.
Subjecting a surface of a crystal to a (spontaneous) structural self-assembly (or self-organization) process, in particular, by specially treating (e.g., annealing) the surface of the crystal, for generating or forming the 'self-assembled template', i.e., the pre-formed, master or standard (i.e., template type) crystal structure, results in the treated crystal surface displaying or exhibiting 'emergent structural properties, characteristics, or features', i.e., the spontaneously formed array of nanoscale features included on the surface of the 'self-assembled template', i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
In the context of illustratively describing the method of the present invention, the 'self-assembled template', i.e., the pre-formed, master or standard (i.e., template type) crystal structure, is suitable for being used in a procedure for replicating (i.e., copying or reproducing) at least part of the array of the nanoscale features included on the surface of the 'self-assembled template' (i.e., the pre-formed, master or standard (i.e., template type) crystal structure). In general, such a procedure involves applying at least one material upon at least part of the array of the nanoscale features (included on the surface of the 'self-assembled template'), for replicating the at least part of the array of the nanoscale features, such that the applied materials) includes a replica configuration and shape, for example, as part of a surface replica element, of the at least part of the array of the nanoscale features (included on the surface of the 'self-assembled template'). The phrase 'self-assembled template1, as used herein, is considered synonymous and equivalent to the phrase 'self-organized template', where the term 'self-assembled' is considered synonymous and equivalent to the term 'self-organized'.
The phrase 'substrate surface', as used herein, refers to a surface of a substrate, where the term 'substrate', as used herein, refers to an underlying layer, i.e., of a surface. In general, the substrate, or underlying layer, is composed of essentially any type or kind of material or substance, or combination of materials or substances. More specifically, the substrate, or underlying layer, is composed of inorganic matter, or/and organic matter.
The term 'replicating', as used herein, refers to copying or reproducing an object or entity. In the context of illustratively describing the method of the present invention, an example of such an object or entity is 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template. Accordingly, the term 'replicating', as used herein, refers to copying or reproducing 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template. Thus, in a similar manner of usage, the term 'replica', as used herein, refers to a copy or reproduction of an object or entity. In the context of illustratively describing the method of the present invention, an example of such an object or entity is 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template. Accordingly, the term 'replica', as used herein, refers to a copy or reproduction of 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
The term 'configuration', as used herein, refers to an arrangement of parts, elements, or components, of an object or entity. In the context of illustratively describing the method of the present invention, an example of such an object or entity is 'applied material(s)' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template. Accordingly, the term 'configuration', as used herein, refers to an arrangement of parts, elements, or components, of 'applied materials' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template. The term 'shape', as used herein, refers to the characteristic surface configuration of an object or entity. The term 'shape', as used herein, is considered synonymous and equivalent to the term 'form'. Moreover, the shape, Le., the characteristic surface configuration, of an object or entity is also considered the outline or contour of the object or entity. In the context of illustratively describing the method of the present invention, an example of such an object or entity is 'applied material(s)' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template. Accordingly, the term 'shape', and the phrase 'shape', as used herein, each refers to the characteristic surface configuration (outline or contour) of 'applied materials' (i.e., material(s) which is (are) applied) upon 'at least part of an array of nanoscale features' which is included on a surface of a self-assembled template.
As illustratively described in detail, hereinbelow, an important aspect of the method of the present invention, is that such applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features which is included on a surface of a self-assembled template.
The phrase 'surface replica element', as used herein, refers to an element (in particular, of applied materials) whose configuration and shape includes a replica (i.e., copy or reproduction) configuration and shape of at least part of a surface of a self- assembled template, where the at least part of the surface of the self-assembled template includes 'at least part of an array of nanoscale features'.
The term 'about', as used herein, refers to ± 20 % of the associated value. The phrase 'room temperature', as used herein, refers to a temperature in a range of between about 15 °C and about 35 °C. Steps or procedures, sub-steps or sub-procedures, equipment, reagents, and materials, as well as operation and implementation, of exemplary preferred embodiments, alternative preferred embodiments, specific configurations, and, additional and optional aspects, characteristics, or features, thereof, of the method for producing (fabricating) an array of nanoscale structures on a substrate surface, via a self-assembled template, according to the present invention, are better understood with reference to the following illustrative description and accompanying drawings. Throughout the following illustrative description and accompanying drawings, same reference notation and terminology (i.e., numbers, letters, or/and symbols), refer to same components, elements, and parameters. Additionally, throughout the following accompanying drawings (Figs. 1 through l ib), main steps (procedures) are consistently indicated by double-tailed arrows along with corresponding reference numbers.
In the following illustrative description of the method of the present invention, included are main or principal steps or procedures, sub-steps or sub-procedures, equipment, chemical reagents, and materials, needed for sufficiently understanding proper 'enabling' utilization and implementation of the disclosed method. Accordingly, description of various possible preliminary, intermediate, minor, or/and optional, steps or procedures, sub-steps or sub-procedures, equipment, chemical reagents, or/and materials, of secondary importance with respect to enabling implementation of the invention, which are readily known by one of ordinary skill in the art, or/and which are available in the prior art and technical literature relating to producing (fabricating) arrays of nanoscale structures on substrate surfaces, are at most only briefly indicated herein.
According to a main aspect of the present invention, there is provision of a method for producing an array of nanoscale structures on a substrate surface, the method including the following main steps (procedures), and structures thereof: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features; treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
Immediately following is detailed illustrative description of main steps (procedures), and structures, of an exemplary generalized preferred embodiment of implementing the method for producing an array of nanoscale structures on a substrate surface, in accordance with the present invention. Thereafter, are provided detailed illustrative descriptions of exemplary specific preferred embodiments, alternative preferred embodiments, specific configurations, and, additional and optional aspects, characteristics, or features, thereof, of the method of the present invention. Referring now to the drawings, Fig. 1 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary generalized preferred embodiment of implementing the method for producing an array of nanoscale structures on a substrate surface. Accordingly, the method for producing an array of nanoscale structures on a substrate surface, of the present invention, includes the following main steps (procedures), and structures thereof: providing a self-assembled template 10 whose surface includes an array 12 of nanoscale features 14 spontaneously formed by treating (indicated as 16 [crystal surface treatment]) a crystal surface 18; applying (indicated as 20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14, for replicating the at least part of array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape of the at least part of array 12 of nanoscale features 14; treating (indicated as 22 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting (indicated as 24 [contacting]) the replica configuration and shape of the treated applied material(s), with the substrate surface 26, for forming a combination structure having the replica configuration and shape in contact with the substrate surface 26; and processing the combination structure, for generating (indicated as 28 [array generation]) the array 30 of the nanoscale structures 32 on the substrate surface 26 of a substrate 34.
Providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface.
As shown in Fig. 1, this main step (procedure) involves providing a self-assembled template 10 whose surface includes an array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) a crystal surface 18. As stated hereinabove, the phrase 'self-assembled template', as used herein, is considered synonymous and equivalent to the phrase 'self-organized template', where the term 'self-assembled' is considered synonymous and equivalent to the term 'self-organized'. Accordingly, self-assembled template 10 is considered synonymous and equivalent to a self-organized template 10, whose surface includes an array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) a crystal surface 18. Composition, bulk or overall geometrical shape or form, bulk or overall size, of self-assembled template 10
In general, provided self-assembled template 10 is composed of essentially any type or kind of a crystalline substance, having essentially any bulk or overall geometrical shape or form, and essentially any bulk or overall size, so long as the surface of self-assembled template 10 includes an array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) a crystal surface 18. Regarding composition and type or kind of crystalline substance, self-assembled template 10 is composed of a crystalline substance selected from the group consisting of crystalline inorganic matter, crystalline organic matter, and a combination thereof.
An exemplary crystalline substance being crystalline inorganic matter, of which self-assembled template 10 is composed, is selected from the group consisting of: a crystalline single metal oxide, a crystalline mixed metal oxide, a crystalline inorganic salt, a periodic table group IV element, a compound of periodic table group IV elements, a compound of a periodic table group III element and a periodic table group V element, a compound of a periodic table group II element and a periodic table group VI element, a crystalline carbide, a crystalline suicide, a crystalline hydride, a crystalline elemental metal, and a crystalline alloy.
An exemplary crystalline single metal oxide, of which self-assembled template 10 is composed, is selected from the group consisting of: alpha-aluminum oxide (sapphire) [(X-Al2O3], alpha-silicon oxide (quartz) [(X-SiO2], zinc oxide [ZnO], magnesium oxide [MgO], and titanium oxide [TiO2]. An exemplary crystalline mixed metal oxide, of which self-assembled template 10 is composed, is selected from the group consisting of: barium titanate [BaTiO3], strontium titanate [SrO3], and lithium niobate [LiNbO3]. An exemplary crystalline inorganic salt, of which self-assembled template 10 is composed, is selected from the group consisting of: calcium fluoride [CaF2], calcium carbonate [CaCθ3], and sodium chloride [NaCl]. An exemplary periodic table group IV element, of which self-assembled template 10 is composed, is selected from the group consisting of: elemental silicon [Si], elemental germanium [Ge], graphite elemental carbon [C], and diamond elemental carbon [C]. An exemplary compound of periodic table group IV elements, of which self-assembled template 10 is composed, is silicon carbide [SiC]. An exemplary compound of a periodic table group III element and a periodic table group V element, of which self-assembled template 10 is composed, is selected from the group consisting of: gallium arsenide [GaAs], gallium nitride [GaN], indium phosphide [InP], and boron nitride [BN]. An exemplary compound of a periodic table group II element and a periodic table group VI element, of which self-assembled template 10 is composed, is selected from the group consisting of: zinc sulfide [ZnS], cadmium selenide [CdSe], and zinc telluride [ZnTe]. An exemplary crystalline carbide, of which self-assembled template 10 is composed, is selected from the group consisting of: tungsten carbide [WC], and titanium carbide [TiC]. An exemplary crystalline suicide, of which self-assembled template 10 is composed, is: tungsten suicide [WSi2]. An exemplary crystalline hydride, of which self-assembled template 10 is composed, is selected from the group consisting of: water (ice) [H2O], calcium hydride [CaH2], and lithium boron hydride [LiBH4]. An exemplary crystalline elemental metal, of which self-assembled template 10 is composed, is selected from the group consisting of: elemental gold [Au], elemental platinum [Pt], elemental molybdenum [Mo], and elemental iridum [Ir]. An exemplary crystalline metal alloy, of which self-assembled template 10 is composed, is selected from the group consisting of: aluminum-nickel-cobalt (Alnico) [AlNiCo], and iron-nickel (Invar) [FeNi].
An exemplary crystalline substance being crystalline organic matter, of which self-assembled template 10 is composed, is selected from the group consisting of: an amino acid, a protein, a carbohydrate, an aliphatic compound, and an aromatic compound.
An exemplary amino acid, of which self-assembled template 10 is composed, is selected from the group consisting of: L-glycine, and L-alanine. An exemplary protein, of which self-assembled template 10 is composed, is selected from the group consisting of: hemoglobin, and myoglobin. An exemplary carbohydrate, of which self-assembled template 10 is composed, is selected from the group consisting of: glucose, sucrose, and lactose. An exemplary aliphatic compound, of which self-assembled template 10 is composed, is selected from the group consisting of: urea [CON2H4], camphor [C10H16O], and ascorbic acid [C6H8O6]. An exemplary aromatic compound, of which self-assembled template 10 is composed, is selected from the group consisting of: naphthalene [C10Hs], anthracene [C14H10], pentacene [C22H14], and benzoic acid [C7H6O2].
An exemplary crystalline substance being a combination of crystalline inorganic matter and crystalline organic matter, of which self-assembled template 10 is composed, is selected from the group consisting of: a crystalline organic salt, and a crystalline organometallic complex. An exemplary crystalline organic salt, of which self-assembled template 10 is composed, is selected from the group consisting of: calcium oxalate [CaC2O4], and iron (III) acetate [Fe (CH3CO2)2]. An exemplary crystalline organometallic complex, of which self-assembled template 10 is composed, is selected from the group consisting of: ferrocene [Fe (C5H5)2], and zinc tetraphenylporphyrin [ZnC44H28N4]. Self-assembled template 10 is composed, preferably, of gallium arsenide [GaAs], being an exemplary compound of a periodic table group III element and a periodic table group V element, which, in turn, is an exemplary crystalline substance being crystalline inorganic matter. Self-assembled template 10 is composed, more preferably, of elemental Q
silicon [Si], being an exemplary periodic table group IV element, which, in turn, is an exemplary crystalline substance being crystalline inorganic matter. Self-assembled template 10 is composed, most preferably, of alpha-aluminum oxide (sapphire) [α-Al2θ3], being an exemplary crystalline single metal oxide, which, in turn, is an exemplary crystalline substance being crystalline inorganic matter.
Regarding bulk or overall geometrical shape or form, self-assembled template 10 has a three-dimensional polyhedron bulk or overall geometrical shape or form, or a three-dimensional non-polyhedron curved bulk or overall geometrical shape or form.
An exemplary three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a parallelpiped, a prism, and a pyramid. An exemplary parallelpiped type of three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a rectangular parallelpiped, a square prism, and a cube. An exemplary prism type of three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a triangular prism, a quadrilateral prism, a pentagonal prism, and a hexagonal prism. An exemplary pyramid type of three-dimensional polyhedron bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a triangular pyramid, a quadrilateral pyramid, a pentagonal pyramid, and a hexagonal pyramid.
An exemplary three-dimensional non-polyhedron curved bulk or overall geometrical shape or form of self-assembled template 10 is selected from the group consisting of: a cylinder, a disc (disk), and a cone.
Self-assembled template 10 has a bulk or overall geometrical shape or form, preferably, of a cylinder or disc, each being an exemplary three-dimensional non- polyhedron curved bulk or overall geometrical shape or form. Self-assembled template 10 has a bulk or overall geometrical shape or form, more preferably, of a prism, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form. Self- assembled template 10 has a bulk or overall geometrical shape or form, most preferably, of a parallelpiped, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
Regarding bulk or overall size, self-assembled template 10 has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a general range of between about 0.1 nanometer (nm) and about 1 meter (m). More specifically, self-assembled template 10 has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron (μm) and about 1 centimeter (cm), (ii) a second range of between about 100 microns (μm) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
The first range of between about 1 micron (μm) and about 1 centimeter (cm) is particularly relevant to applications in sub-fields and areas of nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electromechanics (nanoelectromechanics), and nanoscale semiconductor technology, which involve manufacturing of devices, components, and elements, such as sensors, and actuators.
The second range of between about 100 microns (μm) and about 1 meter (m) is particularly relevant to applications in sub-fields and areas of nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electromechanics (nanoelectromechanics), and nanoscale semiconductor technology, which involve manufacturing of devices, components, and elements, such as displays, and, optical, electro-optical, or optoelectronic, devices, components, and elements.
The third range of between about 1 millimeter (mm) and about 1 meter (m) is particularly relevant to applications which involve manufacturing of macroscopic sized devices, components, and elements, such as displays (e.g., television displays, computer displays, video displays, playstation displays, cellular phone displays), and, optical, electro-optical, or opto-electronic, devices, components, and elements, such as filters and polarizers. Special technical features regarding array 12 of nanoscale features 14 included on the surface of self-assembled template 10
In general, array 12 of nanoscale features 14 included on the surface of self-assembled template 10 corresponds to a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set of features, structures, or elements, herein, generally referred to as nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10. Nanoscale features 14 of array 12 included on the surface of self-assembled template 10 correspond to distinct, distinguishing, or characterizing, parts (e.g., structures, sub-structures, elements, sub-elements) which are included on the surface of self-assembled template 10. In general, nanoscale features 14 of array 12 included on the surface of self-assembled template 10 can be of various different types or kinds. Nanoscale features 14 of array 12 included on the surface of self-assembled template 10 are of a type or kind, preferably, selected from the group consisting of nanoscale facets (i.e., nanofacets), nanoscale grooves (i.e., nanogrooves), and nanoscale steps (i.e., nanosteps).
Accordingly, an example of such as an array of nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10, is an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale facets (i.e., nanofacets), in rows or/and columns, on the surface of self-assembled template 10.
Another example of such as an array of nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10, is an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square— like)) ordered arrangement or set) of nanoscale grooves (i.e., nanogrooves), in rows or/and columns, on the surface of self-assembled template 10.
Another example of such as an array of nanoscale features 14, in rows or/and columns, on the surface of self-assembled template 10, is an array (i.e., a parallelogram or parallelogram-like (e.g., rectangular (square) or rectangular-like (square-like)) ordered arrangement or set) of nanoscale steps (i.e., nanosteps), in rows or/and columns, on the surface of self-assembled template 10.
For an array 12 of nanoscale features 14 included on the surface of self-assembled template 10, any single or individual nanoscale feature (e.g., nanofacet, nanogroove, nanostep) of nanoscale features 14 has size dimensions of width, and height (or thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
For an array 12 of nanoscale features 14 included on the surface of self-assembled template 10, the pitch, P1, being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanoscale features (e.g., two nanofacets, two nanogrooves, or two nanosteps), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
An important aspect of this main step (procedure) of the method of the present invention is that nanoscale features 14, and therefore, array 12 of nanoscale features 14, included on the surface of the provided self-assembled template 10, are spontaneously formed by treating (16 [crystal surface treatment]) crystal surface 18 of a crystalline substance (e.g., a crystal). More specifically, self-assembled template 10, which is provided in accordance with this main step (procedure), corresponds to a pre-formed, master or standard (i.e., template type) crystal structure whose surface 18 includes array 12 of nanoscale features 14 spontaneously formed by treating (16 [crystal surface treatment]) crystal surface 18 of a crystalline substance. Self-assembled template 10, i.e., the pre-formed, master or standard (i.e., template type) crystal structure, is generated or formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) crystal surface 18 of a crystalline substance (a crystal). Spontaneously formed array 12 of nanoscale features 14 included on the surface of self-assembled template 10, is spontaneously formed as a result of a dynamic type of structural self-assembly (or self-organization) process which takes place, for example, by specially treating (e.g., annealing) crystal surface 18 of a crystalline substance (a crystal).
The dynamic type of structural self-assembly (or self-organization) process, resulting in generation or formation of such a 'self-assembled template1, i.e., a pre-formed, master or standard (i.e., template type) crystal structure, such as self-assembled template 10, is a process during which there occurs a specific type of (spontaneous) assembly or organization of atoms (groups of atoms) on crystal surface 18 of a crystalline substance (a crystal) without guidance or management from or by an outside (external) source. Accordingly, an important, and potentially exploitable, result of the (spontaneous) dynamic type of structural self-assembly (or self-organization) process, is spontaneous formation of array 12 of nanoscale features 14 included on the surface of self-assembled template 10, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
An important aspect of such a (spontaneous) structural self-assembly (or self-organization) process, is that the final (desired) (spontaneously formed) array 12 of nanoscale features 14 included on the surface of self-assembled template 10, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure, is 'encoded' in the geometrical configuration (arrangement), shape, form, properties, characteristics, and features, of the atoms (groups of atoms) on crystal surface 18 of a crystalline substance which is subjected to the structural self-assembly (or self-organization) process.
Subjecting crystal surface 18 of a crystalline substance (a crystal) to a (spontaneous) structural self-assembly (or self-organization) process, in particular, by specially treating (16 [crystal surface treatment]) (e.g., annealing) crystal surface 18 of the crystalline substance, for generating or forming self-assembled template 10, i.e., the pre-formed, master or standard (i.e., template type) crystal structure, results in the treated crystal surface 18 of the crystalline substance displaying or exhibiting 'emergent structural properties, characteristics, or features'. Such emergent structural properties, characteristics, or features correspond to the spontaneously formed array 12 of nanoscale features 14 included on the surface of self-assembled template 10, i.e., on the surface of the pre-formed, master or standard (i.e., template type) crystal structure.
In the context of illustratively describing the method of the present invention, self-assembled template 10, i.e., the pre-formed, master or standard (i.e., template type) crystal structure, is suitable for being used in a procedure for replicating (i.e., copying or reproducing) at least part of array 12 of nanoscale features 14 included on the surface of self-assembled template 10. In general, such a procedure involves applying (20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14 included on the surface of self-assembled template 10, for replicating the at least part of array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape, for example, as part of a surface replica element, of the at least part of array 12 of nanoscale features 14 included on the surface of self-assembled template 10. Special technical features regarding crystal surface 18 and treating thereof
In general, crystal surface 18 is composed of essentially any type or kind of a crystalline substance, having essentially any bulk or overall geometrical shape or form, and essentially any bulk or overall size, so long as at least part of the crystalline substance can be cut, or alternatively processed, for forming crystal surface 18. As previously described, crystal surface 18 of a crystalline substance (a crystal) is subjected to a (spontaneous) structural self-assembly (or self-organization) process, in particular, by specially treating (16 [crystal surface treatment]) (e.g., annealing) crystal surface 18 of the crystalline substance, for generating or forming self-assembled template 10. Accordingly, crystal surface 18 is composed of essentially any type or kind of a crystalline substance, as described and exemplified for self-assembled template 10. Additionally, crystal surface 18 has essentially any bulk or overall geometrical shape or form, as described and exemplified for self-assembled template 10. Additionally, crystal surface 18 has essentially any bulk or overall size, as described and exemplified for self-assembled template 10. Crystal surface 18 is obtained by cutting, or, by alternatively processing, at least part of a crystalline substance, for example, a crystal. Crystal surface 18 is, alternatively obtained, by depositing (e.g., via epitaxial growth) a crystalline substance onto a surface of another substance. The crystalline substance, for example, a crystal, is preferably cut (or alternatively processed) along a cutting plane (processing plane), resulting in the formation of crystal surface 18 being in a relatively unstable state. In such a relatively unstable state, crystal surface 18 can be treated (16 [crystal surface treatment]), preferably, by annealing, for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10.
Crystal surface 18 is treated (16 [crystal surface treatment]), preferably, by annealing, for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10. Crystal surface 18 is treated (16 [crystal surface treatment]), alternatively, by etching (e.g., dry or wet etching), for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self- assembled template 10. In either embodiment, since crystal surface 18 is treated (16 [crystal surface treatment]) for spontaneously forming array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10, therefore, the type or kind of composition, and bulk or overall geometrical shape or form, and bulk or overall size, of crystal surface 18, correspond to the type or kind of composition, and bulk or overall geometrical shape or form, and bulk or overall size, respectively, of self-assembled template 10, as illustratively described hereinabove.
Applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features.
With reference to Fig. 1, this main step (procedure) involves applying (20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14, for replicating the at least part of array 12 of nanoscale features 14, such that the applied material(s) includes a replica configuration and shape of the at least part of array 12 of nanoscale features 14. Material applying process
In general, applying (20 [applying material(s)]) at least one material upon at least part of array 12 of nanoscale features 14 is performed according to any of a variety of different material applying processes, using appropriate techniques, equipment, instruments, materials, and chemical reagents. Applying (20 [applying material(s)]) is performed according to a material applying process selected from the group consisting of: casting (molding), and depositing. The term 'casting', as used herein, refers to pouring or placing the at least one material upon at least part of array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10, and allowing the poured or placed material(s) to set in a solid form (i.e., solidify) upon the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10. The term 'casting', as used herein, is considered synonymous and equivalent to the term 'molding'.
An exemplary type or kind of casting (molding) process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: a polymer cross-linking type of casting (molding) process, and a liquid-to-solid phase transition type of casting (molding) process. The term 'depositing', as used herein, refers to putting or setting down the at least one material upon at least part of array 12 of nanoscale features 14 which is included on the surface of self-assembled template 10.
An exemplary type or kind of depositing process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: a physical deposition process, and a chemical deposition process. An exemplary physical deposition process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: evaporation, sputtering, and coating. An exemplary chemical deposition process for performing the main step (procedure) of applying (20 [applying material(s)]), is selected from the group consisting of: chemical vapor depostion, adsorption, growth, polymerization, electrodeposition, and electroless deposition. Composition and structure of material^ applied upon at least part of array 12 of nanoscale features 14
In general, the at least one material that is applied upon at least part of array 12 of nanoscale features 14, is composed of essentially any type or kind of a substance, having essentially type or kind of structure.
Regarding composition, the at least one material that is applied upon at least part of array 12 of nanoscale features 14, is composed of a substance selected from the group consisting of organic matter, inorganic matter, and a combination thereof.
An exemplary substance being organic matter, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is an organic polymer. An exemplary organic polymer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: a thermoplastic, a thermoset, an elastomer, and any combination thereof. An exemplary thermoplastic, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: polystyrene (PS), a polyurethane (PU), and a polyamide. An exemplary thermoset, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: an epoxy resin, phenol formaldehyde resin, and a polyester. An exemplary elastomer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: polyisoprene (isoprene rubber [IR]), a polyacrylate rubber (ABR), and ethylene-vinyl acetate (EVA).
An exemplary substance being inorganic matter, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: a metal element, a metal alloy, a semi-metal element, a non-metal element, and any combination thereof. An exemplary metal element, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: a noble metal element (e.g., gold [Au], silver [Ag], or platinum [Pt]), a transition metal element (e.g., nickel [Ni]3 molybdenum [Mo], or copper [Cu]), and a main o o
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group metal element (e.g., aluminum [Al], or bismuth [Bi]). An exemplary metal alloy, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: palladium-gold [PdAu], and platinum-indium [PtIr]. An exemplary semi-metal element, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: elemental silicon [Si], and elemental germanium [Ge]. An exemplary non-metal element, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: an allotrope of carbon (e.g., graphitic elemental carbon, amorphous elemental carbon, diamond elemental carbon, fullerene elemental carbon, or nanotube elemental carbon), and elemental boron [B]. An exemplary combination of a metal element and a non-metal element, in the form of a compound, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: indium oxide [In2Os], molybdenum diselinide [MoSe2], and boron nitride [BN].
An exemplary substance being a combination of organic matter and inorganic matter, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is an organic-inorganic polymer. An exemplary organic-inorganic polymer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: an organic-inorganic form of a thermoplastic, an organic-inorganic form of a. thermoset, an organic-inorganic form of an elastomer, and any combination thereof. An exemplary organic-inorganic form of a thermoplastic, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: polyvinylchloride (PVC), and polytetrafluoroethylene (Teflon®). An exemplary organic-inorganic form of an elastomer, of which the at least one material that is applied upon at least part of array 12 of nanoscale features 14 is composed, is selected from the group consisting of: polydimethylsiloxane (PDMS), and a fluorosilicone. Regarding structure, the at least one material that is applied upon at least part of array 12 of nanoscale features 14, has an amorphous structure, or a crystalline structure. Treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
With reference to Fig. 1, this main step (procedure) involves treating (22 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
For specific preferred embodiments (e.g., as illustratively described hereinbelow, along with reference to Figs. 4 - 9) of the method, wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process, then, the main step (procedure) of treating (22 [treating]) includes, as a first main sub-step (sub-procedure), separating, for example, by peeling off, the applied material(s) (e.g., an organic polymer or organic-inorganic polymer cast (mold) type of surface replica element) from the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10. While performing the treating step (procedure), there is maintaining the replica configuration and shape of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element), for forming a stand-alone organic polymer or organic-inorganic polymer cast (mold) type of surface replica element having a replica configuration and shape. Also, for such specific preferred embodiments of the method wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process, then, the treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking, by using a suitable ink, the surface of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element). More specifically, there is inking, by using a suitable ink, that surface part or area of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element) which encompasses the replica configuration and shape of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element). Also, for such specific preferred embodiments of the method wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process, then, as illustratively described hereinbelow, along with reference to Fig. 8, the main step (procedure) of treating (22 Q
[treating]) step (procedure) includes, as a first main sub-step (sub-procedure), wrapping the applied material(s) (e.g., the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element) onto and around a roller, for forming a wrapped form of the applied material(s) (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type of surface replica element).
In such a roller type of specific preferred embodiment, the main step (procedure) of treating (22 [treating]) step (procedure) further includes inking, by using a suitable ink, the surface of the applied material (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element). More specifically, there is inking that surface part or area of the applied material (e.g., of the organic polymer or organic- inorganic polymer cast (mold) type wrapped surface replica element), which encompasses the replica configuration and shape of the applied material (e.g., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element).
In such a roller type of specific preferred embodiment, the preceding treating steps (procedures) are thus performed for forming a treated applied material (e.g., a treated (inked) organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element). The treated (inked) organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element has, via the treated (inked) portion thereof, the replica configuration and shape of the applied material (e.g., of the organic polymer or organic— inorganic polymer cast (mold) type wrapped surface replica element).
In general, a suitable ink is an ink which is composed of essentially any type or kind of a solution or suspension of a substance that binds, adheres, or/and adsorbs, onto substrate surface 26 of substrate 34. An exemplary ink is selected from the group consisting of a thiol compound based ink, and a silane compound based ink. An exemplary thiol compound based ink is a solution or suspension of a thiol compound selected from the group consisting of: n-hexadecanethiol, n-dodecanethiol, and n-octadecanethiol. Such a thiol compound based ink binds, adheres, or/and adsorbs, onto a metal (e.g., gold) type of substrate surface 26 of substrate 34. An exemplary silane compound based ink is a solution or suspension of a silane compound selected from the group consisting of: octadecyltricholorosilane, 3-aminopropyl-triethoxisilane, and 3- mercaptopropyl-trimetlioxysilane. Such a silane compound based ink binds, adheres, or/and adsorbs, onto an oxide (e.g., silicon oxide [SiO2], or oxidized silicon [Si]) type of substrate surface 26 of substrate 34. For specific preferred embodiments (e.g., as illustratively described hereinbelow, along with reference to Fig. 10) of the method wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a depositing type of material applying process, then, the treating step (procedure) includes allowing the applied material(s) (i.e., the deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), while maintaining the replica configuration and shape thereof, upon the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, to stand at a pre-determined temperature, for a pre-determined period of time. This results in forming the treated applied material(s) (i.e., the treated deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer) having the replica configuration and shape of the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10. Contacting the replica configuration and shape of the treated applied mater ial(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface.
With reference to Fig. 1, this main step (procedure) involves contacting (24 [contacting]) the replica configuration and shape of the treated applied material(s), with the substrate surface 26, for forming a combination structure having the replica configuration and shape in contact with the substrate surface 26.
For specific preferred embodiments (e.g., as illustratively described hereinbelow, along with reference to Figs. 4 - 9) of the method, wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process, then, the main step (procedure) of contacting (24 [contacting]) is performed, for example, by pressing or bringing together, the replica configuration and shape of the treated applied material(s) (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element), with the substrate surface 26 of substrate 34, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26. Also, for such specific preferred embodiments of implementing the method of the present invention (e.g., as shown in Figs. 4 and 9), the substrate, i.e., substrate 34, includes two main distinct layers, i.e., a first or base layer, and a second or surface layer which is situated and lies upon the first or base layer. During this contacting step (procedure), the ._
second or surface layer is the top or upper most layer of substrate 34 which includes a substrate surface that is brought into contact with the replica configuration and shape of the treated applied material(s) (e.g., of the treated (inked) organic polymer or organic- inorganic polymer cast (mold) type surface replica element). In general, the first or base layer is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof. For example, the first or base layer is composed of a semiconductor type or kind of material or substance, such as silicon, oxidized silicon, or gallium arsenide. Alternatively, for example, the first or base layer is composed of an insulating type or kind of material or substance, for example, glass, quartz, or sapphire. In general, the second or surface layer is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof. For example, the second or surface layer is composed of a metallic type or kind of material or substance, such as gold, silver, platinum, gold on chromium, or gold on titanium, which is situated and lies upon the first or base layer.
This main step (procedure) of contacting (24 [contacting]) involves, and results in, transferring, via the ink, the replica configuration and shape of the treated applied material(s) (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element) onto the substrate surface of the second or surface layer of substrate 34.
This main step (procedure) of contacting (24 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with the ink, those areal portions or sections (e.g., strips or belts) of the substrate surface of the second or surface layer which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material(s) (e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element). Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips or belts) of the substrate surface of the second or surface layer which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material(s) (e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element). 3
A consequence of this main step (procedure) of contacting (24 [contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portion or section of the substrate surface of the second or surface layer which is not brought into contact with the ink of the replica configuration and shape of the treated applied material(s) (e.g., which is not brought into contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element).
In a roller type of specific preferred embodiment of the method of the present invention, for example, as illustratively described hereinbelow, along with reference to Fig. 8, there is contacting (24 [contacting]), for example, by rolling and bringing together, the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element), with the substrate surface 26 of substrate 34, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26. In such a roller type of specific preferred embodiment, the main step (procedure) of contacting (24 [contacting]) involves, and results in, transferring, via ink, the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element) onto substrate surface 26 of substrate 34. In such a roller type of specific preferred embodiment, this main step (procedure) of contacting (24 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with the ink, those areal portions or sections (e.g., strips) of substrate surface 26 of substrate 34 which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., which are brought into , direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element). Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 26 of substrate 34 which are brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., which are brought into direct contact with the ink of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element). For specific preferred embodiments (e.g., as illustratively described hereinbelow, along with reference to Fig. 10) of the method wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a depositing type of material applying process, then, the main step (procedure) of contacting (24 [contacting]) is performed, for example, by pressing or bringing together, the treated applied material(s) (i.e., the treated deposited material, such as a deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, with substrate surface 26 of substrate 34, for forming a combination structure having the replica configuration and shape in contact with substrate surface 26 of substrate 34.
This main step (procedure) of contacting (24 [contacting]) involves, and results in, transferring a portion or layer of the treated applied material (e.g., of the treated deposited material (in particular, the treated deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer)), having the replica configuration and shape of the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, onto substrate surface 26 of substrate 34. Processing the combination structure, for generating the array of the nanoscale structures on the substrate surface. With reference to Fig. 1, this main step (procedure) involves processing the combination structure, for generating (indicated as 28 [array generation]) the array 30 of the nanoscale structures 32 on the substrate surface 26 of a substrate 34.
For specific preferred embodiments (e.g., as illustratively described hereinbelow, along with reference to Figs. 4 - 9) of the method, wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a casting (molding) type of material applying process, then, the main step (procedure) of processing the combination structure, includes, as a first main sub-step (sub-procedure), separating the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element), from substrate surface 26 of substrate 34. This is accomplished by separating, for example, by lifting back and removing, the treated applied material (e.g., the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element) from substrate surface 26 of substrate 34. Also, for such specific preferred embodiments of implementing the method of the present invention (e.g., as shown in Figs. 4 and 9), by this processing first main sub-step (sub-procedure), there is forming a nanopattern (nanoscale pattern) upon substrate surface 26 of substrate 34. The nanopattern is composed or made up of two parts or components. The first part or component of the nanopattern corresponds to: (i) those areal portions or sections (e.g., strips or belts) of the substrate surface of the second or surface layer which were chemically functionalized (derivatized) by the preceding contacting (24 [contacting]) procedure, as a result of having been brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element). The second part or component of the nanopattern corresponds to: (ii) the remaining areal portion or section of the substrate surface of the second or surface layer which was not chemically functionalized (derivatized) by the preceding contacting (24 [contacting]) procedure, as a result of not having been brought into direct contact with the ink of the replica configuration and shape of the treated applied material (e.g., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element).
Also, for such specific preferred embodiments of implementing the method of the present invention (e.g., as shown in Figs. 4 and 9), the processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via [chemical functionalizing (derivatizing)], or via [etching]) the nanopattern (nanoscale pattern) upon the substrate surface of the second or surface layer of substrate 34, which was obtained from the preceding separating sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via [chemical functionalizing (derivatizing)], or via [etching]) the preceding stated second part or component of the nanopattern, i.e., the remaining areal portion or section of the substrate surface of the second or surface layer of substrate 34 which was not chemically functionalized (derivatized) by the preceding contacting (24 [contacting]) procedure (as a result of not having been brought into direct contact with the ink of the replica configuration and shape). Alternatively, and equivalently stated, the processing step (procedure) further includes modifying (via [chemical functionalizing (derivatizing)], or via [etching]) the exposed areal portion or section of the substrate surface of the second or surface layer which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips or belts) of the nanopattern, i.e., of the nanoscale pattern of the replica configuration and shape.
Modifying, via [chemical functionalizing (derivatizing)], the nanopattern (nanoscale pattern) upon the substrate surface of the second or surface layer of substrate 34, is performed by using a suitable chemical functionalizing (derivatizing) procedure or technique, involving a suitable chemical functionalizing (derivatizing) reagent. A suitable chemical functionalizing (derivatizing) procedure or technique, is, for example, selected from the group consisting of a thiol compound based functionalizing (derivatizing) procedure or technique, and a silane compound based functionalizing (derivatizing) procedure or technique.
For example, there is using a thiol compound based chemical functionalizing (derivatizing) procedure or technique, involving a thiol compound based chemical functionalizing (derivatizing) reagent. A suitable thiol compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 16-mercaptohexadecanoic acid, 12-thioldodecanol, and 12-aminododecanethiol. Alternatively, for example, there is using a silane compound based type of functionalizing (derivatizing) procedure or technique, involving a silane compound based chemical functionalizing (derivatizing) reagent. A suitable silane compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 3-aminopropyl-triethoxisilane, and 3-mercaptopropyl-trimethoxysilane.
Modifying, via [chemical functionalizing (derivatizing)] the exposed areal portion or section of the substrate surface of the second or surface layer which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips or belts) of the nanopattern, results in formation of a different substrate surface of the second or surface layer which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips or belts) of the nanopattern.
Thus, this modifying, via [chemical functionalizing (derivatizing)], sub-step (sub-procedure) of the processing step (procedure), results in generating (28 [array generation]) array 30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34.
Modifying, via [etching], the nanopattern (nanoscale pattern) upon the substrate surface of the second or surface layer of substrate 34, is performed by using a suitable etching procedure or technique, involving a suitable etching (etchant) reagent. A suitable etching procedure or technique is, for example, selected from the group consisting of a wet etching procedure or technique, and a dry etching procedure or technique.
For example, there is using an oxidizing type of wet etching procedure or technique, involving an oxidizing compound based wet etching (etchant) reagent. A suitable oxidizing compound based wet etching (etchant) reagent is, for example, a solution composed of: (i) potassium ferricyanide [K3Fe(CN)6], 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1 M; and (iii) potassium hydroxide [KOH], 1.0 M, which is particularly for wet etching of gold [Au]. Another suitable wet etching (etchant) reagent is, for example, a solution composed of potassium hydroxide [KOH], 0.1 M, which is particularly useful for wet etching of silicon [Si] .
For example, there is using a reactive ion etching type of dry etching procedure or technique, involving a reactive ion etching dry etching (etchant) reagent. An exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous sulfur tetra-fluoride [SF4]. Another exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous chlorine [Cl2].
Modifying, via [etching], the exposed areal portion or section of the substrate surface of the second or surface layer of substrate 34 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of the nanopattern, results in formation of a different substrate surface on the previously indicated first or base layer of the remaining (non-etched) part of substrate 34. Accordingly, the previously indicated first or base layer of substrate 34, now functions as substrate 34.
Thus, this modifying, via [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating (28 [array generation]) array 30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34.
Alternatively, for specific preferred embodiments (e.g., as illustratively described hereinbelow, along with reference to Fig. 10) of the method wherein the preceding main step (procedure) of applying (20 [applying material(s)]) is performed according to a depositing type of material applying process, then, the main step (procedure) of processing the combination structure, involves separating the replica configuration and shape of the treated applied material (e.g., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), part of the combination structure, from substrate surface 26 of substrate 34. This is accomplished by separating, for example, by lifting back and removing, the treated deposited material having the replica configuration and shape of the at least part of array 12 of nanoscale features 14 on the surface of self-assembled template 10, from substrate surface 26 of substrate 34. This processing step (procedure) results in generating (28 [array generation]) array
30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34.
For array 30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34, any single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (run) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm). For array 30 of nanoscale structures (e.g., nanowires, nanostrips, nanobelts, nanoparticles, or nanogrooves) 32 on substrate surface 26 of substrate 34, the pitch, P2, being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanoscale structures, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
Typically, the pitch, P2, between two neighboring similar (i.e., not necessarily identical) nanoscale structures 32 of array 30 of nanoscale structures 32 on substrate surface 26 of substrate 34, has a value or magnitude which is comparable to the value or magnitude of the pitch, P1, between two neighboring similar (i.e., not necessarily identical) nanoscale features of array 12 of nanoscale features 14 on the surface of self-assembled template 10. Typically, the width of any single or individual nanoscale structure of array 30 of nanoscale structures 32 on substrate surface 26 of substrate 34, has a value or magnitude which is less than the value or magnitude of the pitch, P2, between two neighboring similar nanoscale structures 32 on substrate surface 26 of substrate 34.
Following hereinbelow, are illustrative descriptions of the main steps (procedures) and main sub-steps (sub-procedures) thereof, and structures, of various exemplary specific preferred embodiments, alternative preferred embodiments, specific configurations, and, additional and optional aspects, characteristics, or features, thereof, of implementing the method for producing an array of nanoscale structures on a substrate surface, of the present invention. These illustrative descriptions are accompanied by schematic (flow-type) diagrams illustrated in Figs. 2a - 2e, 3a - 3d, 4, 5, 6, 7, 8, 9, 10, 11a, and l ib. For the objective of precluding unnecessary repetition, while simultaneously maintaining proper illustrative description of the disclosed invention, it is to be fully understood that all details and aspects of the hereinabove illustrative description of the main steps (procedures), and structures, of the exemplary generalized preferred embodiment of implementing the method of the present invention, along with reference to Fig. 1 thereof, are fully applicable to illustratively describing the various exemplary specific preferred embodiments, alternative preferred embodiments, specific configurations, and, additional and optional aspects, characteristics, or features, thereof, of implementing the method for producing an array of nanoscale structures on a substrate surface, of the present invention. Forming a 'nanogrooved' type faceted self-assembled template
Figs. 2a - 2e are schematic (flow-type) diagrams illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of forming a 'nanogrooved1 type faceted self-assembled template, including cutting a crystal along a 'singular' cutting plane (a low-index plane) of the crystal, wherein the self-assembled template is used for generating an array of nanoscale structures on a substrate surface.
Fig. 2a schematically illustrates cutting (36 [cutting]) of a crystal 38 along a 'singular' cutting plane 40 (corresponding to a low-index plane 42) located within a crystal surface region 44.
Figs. 2b to 2c schematically and sequentially illustrate (cut) crystal surface region 46 (Fig. 2c), of crystal 38, undergoing reconstruction (48 [reconstruction]), for forming a (reconstructed) crystal surface region 50.
Figs. 2c to 2d schematically and sequentially illustrate self-assembly (self-organization) of (reconstructed) crystal surface region 50 resulting in facet formation (52 [facet formation]) along and within (reconstructed) crystal surface region 50, for forming a (self-assembled) crystal surface region 54. As shown in Fig. 2d, nanofacets, for example, nanofacets 56 and 58, are formed along and within (self-assembled) crystal surface region 54. The resulting structure corresponds to (self-assembled) crystal surface region 54 including an array 60 of nanofacets 56 and 58. The resulting structure is classified as a 'nanogrooved' type faceted self-assembled template 62 whose surface (i.e., (self-assembled) crystal surface region 54) includes an array (i.e., array 60) of nanoscale features (i.e., nanofacets 56 and 58) spontaneously formed by treating a crystal surface (i.e., (cut) crystal surface region 46).
Fig. 2e schematically illustrates generating (64 [array generation]) an array 66 of nanoscale structures 68 on the substrate surface 70 of substrate 72. Forming a 'nanostepped' type faceted self-assembled template Figs. 3a - 3d are schematic (flow-type) diagrams illustrating main steps
(procedures), and structures, of an exemplary specific preferred embodiment of forming a 'nanostepped' type faceted self-assembled template, including cutting a crystal along a 'vicinal' cutting plane (at a miscut tilt angle (θ) relative to the nearest low-index plane) of the crystal, wherein the self-assembled template is used for generating an array of nanoscale structures on a substrate surface.
Fig. 3a schematically illustrates cutting (76 [cutting]) of a crystal 78 along a 'vicinal' cutting plane 80 at a miscut tilt angle (θ) relative to the nearest low-index plane 82 located within a crystal surface region 84.
Figs. 3b to 3c schematically and sequentially illustrate self-assembly (self-organization) of (cut) crystal surface region 86 resulting in facet formation (88 [facet formation]) along and within (cut) crystal surface region 86, for forming a (self-assembled) crystal surface region 90. As shown in Fig. 3c, nanofacets, for example, nanofacets 92, 94, and 96, are formed along and within (self-assembled) crystal surface region 90.
The resulting structure corresponds to (self-assembled) crystal surface region 90 including an array 98 of nanofacets 92, 94, and 96. The resulting structure is classified as a 'nanostepped' type faceted self-assembled template 100 whose surface (i.e., (self-assembled) crystal surface region 90) includes an array (i.e., array 98) of nanoscale features (i.e., nanofacets 92, 94, and 96) spontaneously formed by treating a crystal surface (i.e., (cut) crystal surface region 86). Fig. 3d schematically illustrates generating (102 [array generation]) an array 104 of nanoscale structures 106 on the substrate surface 108 of substrate 110. 5 χ
Producing an array of nanoscale structures (nanowires or nanostriys) on a substrate surface via a 'nanogrooved' type faceted self-assembled template formed from a 'singular' crystal surface: (forming and using a surface replica element)
Fig. 4 is a schematic (flow-type) diagram illustrating main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanowires (nanoscale structures) on the substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface. Providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface.
There is providing a 'nanogrooved' type faceted self-assembled template 120 whose nanogrooved surface 122 includes an array 124 of nanoscale features, i.e., nanogrooves. Array 124 of nanogrooves is spontaneously formed, via a process of facet formation (126 [facet formation]), by treating (128 [annealing]) 'singular' crystal surface 130. Singular crystal surface 130 is obtained by cutting (132 [cutting]) a crystal 134 along a 'singular' cutting plane 136 (corresponding to a low-index plane) located within a crystal surface region of crystal 134.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Figs. 2a - 2d, and are exemplified in the Example section, hereinbelow.
Applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features. There is applying, via a material applying process (in particular, a casting (molding) type of material applying process), at least one material (in particular, at least one suitable casting (molding) material, such as an organic polymer [e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof], or, an organic-inorganic polymer [e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof]), upon the entirety of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120. This step (procedure) is performed for replicating (138 [replicating]) the entirety of array 124 of nanogrooves of nanogrooved surface 122, such that the applied material, i.e., the casted (molded) material (in particular, the organic polymer or organic-inorganic polymer), includes a replica configuration and shape 140, for example, as part of a surface replica element 142, of the entirety of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
Surface replica element 142 has a bulk or overall geometrical shape or form, preferably, of a cylinder or disc, each being an exemplary three-dimensional non-polyhedron curved bulk or overall geometrical shape or form. Surface replica element 142 has a bulk or overall geometrical shape or form, more preferably, of a prism, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form. Surface replica element 142 has a bulk or overall geometrical shape or form, most preferably, of a parallelpiped, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
Surface replica element 142 has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a general range of between about 0.1 nanometer (nm) and about 1 meter (m). More specifically, Surface replica element 142 has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron (μm) and about 1 centimeter (cm), (ii) a second range of between about 100 microns (μm) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Example section, hereinbelow. Treating the applied materials) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
The treating step (procedure) includes, as a first main sub-step (sub-procedure), separating (144 [separating]), for example, by peeling off, the applied material, i.e., the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142 from nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120. While performing the treating step (procedure), there is maintaining replica configuration and shape 140 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142, for forming a stand-alone organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142 having replica configuration and shape 140.
The treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking (146 [inking]), by using a suitable ink 148, the surface of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142. More specifically, there is inking (146 [inking]), by using ink 148, that surface part or area of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142, which encompasses replica configuration and shape 140 of the applied material, i.e., of the organic polymer or organic— inorganic polymer cast (mold) type surface replica element 142.
For performing this second main sub-step (sub-procedure) of inking (146 [inking]), there is using any suitable ink 148 which is composed of essentially any type or kind of a solution or suspension of a substance that binds, adheres, or/and adsorbs, onto substrate surface 154 of substrate 156. An exemplary ink which is particularly suitable for performing this main sub-step (sub-procedure) is a thiol compound based ink, or a silane compound based ink.
The preceding treating steps (procedures) are thus performed for fonning treated applied material, i.e., a stand-alone treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142, as referenced by 150 in Fig. 4. Treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 has, via the treated (inked) portion thereof, replica configuration and shape 140 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 142. Additional details relating to performing this main step (procedure), and sub-steps
(sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow. Contacting the replica configuration and shape of the treated applied material^), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface.
There is contacting (152 [contacting]), for example, by pressing or bringing together, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150, with the substrate surface 154 of substrate 156, for forming a combination structure 158 having replica configuration and shape 140 in contact with substrate surface 154. hi this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 4, the substrate, i.e., substrate 156, includes two main distinct layers, i.e., a first or base layer 160, and a second or surface layer 162 which is situated and lies upon first or base layer 160. During this contacting step (procedure), second or surface layer 162 is the top or upper most layer of substrate 156 which includes substrate surface 154 that is brought into contact with replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic- inorganic polymer cast (mold) type surface replica element 150.
In general, first or base layer 160 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof. For example, first or base layer 160 is composed of a semiconductor type or kind of material or substance, such as silicon, oxidized silicon, or gallium arsenide. Alternatively, for example, first or base layer 160 is composed of an insulating type or kind of material or substance, for example, glass, quartz, or sapphire. In general, second or surface layer 162 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof. For example, second or surface layer 162 is composed of a metallic type or kind of material or substance, such as gold, silver, platinum, gold on chromium, or gold on titanium, which is situated and lies upon first or base layer 160.
This main step (procedure) of contacting (152 [contacting]) involves, and results in, transferring, via ink 148, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 onto substrate surface 154 of second or surface layer 162 of substrate 156.
This main step (procedure) of contacting (152 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150. Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
A consequence of this main step (procedure) of contacting (152 [contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portion or section of substrate surface 154 of second or surface layer 162 which is not brought into contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which is not brought into contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow.
Processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
The processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (164 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, from substrate surface 154 of substrate 156. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from substrate surface 154 of substrate 156.
In this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 4, by this processing first main sub-step (sub- procedure), there is forming a nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of substrate 156. Nanopattern 166 is composed or made up of two parts or components. The first part or component of nanopattern 166 corresponds to: (i) those areal portions or sections (e.g., strips) of substrate surface 154 of second or surface layer 162 which were chemically functionalized (derivatized) by the preceding contacting (152 [contacting]) procedure, as a result of having been brought into direct contact with ink 148 of replica configuration and shape 140. The second part or component of nanopattern 166 corresponds to: (ii) the remaining areal portion or section of substrate surface 154 of second or surface layer 162 which was not chemically functionalized (derivatized) by the preceding contacting (152 [contacting]) procedure, as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140.
The processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 168 [chemical functionalizing (derivatizing)], or via 176 [etching]) the nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of second or surface layer 162 of substrate 156, which was obtained from the preceding separating (164 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 168 [chemical functionalizing (derivatizing)], or via 176 [etching]) the preceding stated second part or component of nanopattern 166, i.e., the remaining areal portion or section of substrate surface 154 of second or surface layer 162 of substrate 156 which was not chemically functionalized (derivatized) by the preceding contacting (152 [contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140). Alternatively, and equivalently stated, the processing step (procedure) further includes modifying (via 168 [chemical functionalizing (derivatizing)], or via 176 [etching]) the exposed areal portion or section of substrate surface 154 of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166, i.e., of the nanoscale pattern of replica configuration and shape 140. Modifying, via 168 [chemical functionalizing (derivatizing)], the nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of second or surface layer 162 of substrate 156, is performed by using a suitable chemical functionalizing (derivatizing) procedure or technique, involving a suitable chemical functionalizing (derivatizing) reagent. A suitable chemical functionalizing (derivatizing) procedure or technique, is, for example, selected from the group consisting of a thiol compound based functionalizing (derivatizing) procedure or technique, and a silane compound based functionalizing (derivatizing) procedure or technique.
For example, there is using a thiol compound based chemical functionalizing (derivatizing) procedure or technique, involving a thiol compound based chemical functionalizing (derivatizing) reagent. A suitable thiol compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 16-mercaptohexadecanoic acid, 12-thioldodecanol, and 12-aminododecanethiol. Alternatively, for example, there is using a silane compound based type of functionalizing (derivatizing) procedure or technique, involving a silane compound based chemical functionalizing (derivatizing) reagent. A suitable silane compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 3-aminopropyl-triethoxisilane, and 3-mercaptopropyl-trimethoxysilane.
Modifying (via 168 [chemical functionalizing (derivatizing)] the exposed areal portion or section of substrate surface 154 of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166, results in formation of a different substrate surface, i.e., substrate surface 174, of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166.
Thus, this modifying, via 168 [chemical functionalizing (derivatizing)], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 170 of nanostrips 172 on substrate surface 174 of substrate 156. For array 170 of nanostrips 172 on substrate surface 174 of substrate 156, any single or individual nanostrip 172 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (if) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
For array 170 of nanostrips 172 on substrate surface 174 of substrate 156, the pitch (e.g., analogous to P2, shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanostrips of array 170 of nanostrips 172, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
Typically, the pitch between two neighboring similar (i.e., not necessarily identical) nanostrips of array 170 of nanostrips 172 on substrate surface 174 of substrate 156, has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to P1, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanogrooves of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120. Typically, the width of any single or individual nanostrip of array 170 of nanostrips 172 on substrate surface 174 of substrate 156 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanostrips of array 170 of nanostrips 172 on substrate surface 174 of substrate 156.
Modifying, via 176 [etching], the nanopattern (nanoscale pattern), i.e., nanopattern 166, upon substrate surface 154 of second or surface layer 162 of substrate 156, is performed by using a suitable etching procedure or technique, involving a suitable etching (etchant) reagent. A suitable etching procedure or technique is, for example, selected from the group consisting of a wet etching procedure or technique, and a dry etching procedure or technique.
For example, there is using an oxidizing type of wet etching procedure or technique, involving an oxidizing compound based wet etching (etchant) reagent. A suitable oxidizing compound based wet etching (etchant) reagent is, for example, a solution composed of: (i) potassium ferricyanide [K3Fe(CN)6], 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1M; and (iii) potassium hydroxide [KOH], 1.0 M, which is particularly for wet etching of gold [Au]. Another suitable wet etching (etchant) reagent is, for example, a solution composed of potassium hydroxide [KOH], 0.1 M, which is particularly useful for wet etching of silicon [Si].
For example, there is using a reactive ion etching type of dry etching procedure or technique, involving a reactive ion etching dry etching (etchant) reagent. An exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous sulfur tetra-fluoride [SF4]. Another exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous chlorine [Cl2].
Modifying, via 176 [etching], the exposed areal portion or section of substrate surface 154 of second or surface layer 162 of substrate 156 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 166, results in formation of a different substrate surface, i.e., substrate surface 182, on the previously indicated first or base layer 160 of the remaining (non- etched) part of previously indicated substrate 156. Accordingly, the previously indicated first or base layer 160 of previously indicated substrate 156, now functions as the substrate, referenced as substrate 160, having substrate surface 182.
Thus, this modifying, via 176 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 178 of nanowires 180 on substrate surface 182 of substrate 160.
For array 178 of nanowires 180 on substrate surface 182 of substrate 160, any single or individual nanowire 180 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm). For array 178 of nanowires 180 on substrate surface 182 of substrate 160, the pitch
(e.g., analogous to P2, shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanowires 180, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
Typically, the pitch between two neighboring similar (i.e., not necessarily identical) nanowires of array 178 of nanowires 180 on substrate surface 182 of substrate 160, has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to P1, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanogrooves of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120. Typically, the width of any single or individual nanowire of array 178 of nano wires 180 on substrate surface 182 of substrate 160 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nano wires of array 178 of nano wires 180 on substrate surface 182 of substrate 160.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Fig. 2e, and are exemplified in the Example section, hereinbelow. Producing a grid (waffle) type array of nanoscale structures (nanowires) on a substrate surface via a 'nanogrooved' type faceted self-assembled template formed from a 'singular' crystal surface: (forming and using a surface replica element) Fig. 5 is a schematic (flow-type) diagram illustrating selected main steps
(procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) a grid (waffle) type array of nanowires (nanoscale structures) on the substrate surface.
The exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 5, is an extension of the preceding illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4. There is cross contacting (190 [cross contacting]), for example, by pressing or bringing together, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with the previously generated nanopattern 166 on substrate surface 154 of substrate 156, for forming a combination structure 193 having replica configuration and shape 140 directly in contact (in Fig. 5, indicated by 192) with nanopattern 166 on substrate surface 154 of substrate 156.
The phrase 'cross contacting', as used herein, refers to pressing or bringing together replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with substrate surface 154 of substrate 156, in a manner or way whereby replica configuration and shape 140 of the treated applied material is disposed (i.e., positioned or placed) at an angle in a range of between 0° and 90°, relative to nanopattern 166 on substrate surface 154 of substrate 156. Such relative disposition (positioning or placing) is indicated by 192 in Fig. 5.
This main step (procedure) of cross contacting (190 [cross contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., grid strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150. Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (grid strips) of substrate surface 154 of second or surface layer 162 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150.
A consequence of this main step (procedure) of cross contacting (190 [cross contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portion or section of substrate surface 154 of second or surface layer 162 which is not brought into contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which is not brought into contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
The processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (194 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150, from substrate surface 154 of substrate 156. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from substrate surface 154 of substrate 156.
In this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 5, by this processing first main sub-step (sub- procedure), there is forming a grid (waffle) type of nanopattern (nanoscale pattern), i.e., nanopattern 196, upon substrate surface 154 of substrate 156. Nanopattern 196 is composed or made up of two parts or components. The first part or component of nanopattern 196 corresponds to: (i) those areal portions or sections (e.g., grid strips) of substrate surface 154 of second or surface layer 162 which were chemically functionalized (derivatized) by the preceding cross contacting (190 [cross contacting]) procedure, as a result of having been brought into direct contact with ink 148 of replica configuration and shape 140. The second part or component of nanopattern 196 corresponds to: (ii) the remaining areal portion or section of substrate surface 154 of second or surface layer 162 which was not chemically functionalized (derivatized) by the preceding cross contacting (190 [cross contacting]) procedure, as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140.
The processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 198 [etching]) the grid (waffle) type of nanopattern (nanoscale pattern), i.e., nanopattern 196, upon substrate surface 154 of second or surface layer 162 of substrate 156, which was obtained from the preceding separating (194 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 198 [etching]) the preceding stated second part or component of nanopattern 196, i.e., the remaining areal portion or section of substrate surface 154 of second or surface layer 162 of substrate 156 which was not chemically functionalized (derivatized) by the preceding cross contacting (190 [cross contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140). Alternatively, and equivalently stated, the processing step (procedure) further includes modifying (via 198 [etching]) the exposed areal portion or section of substrate surface 154 of second or surface layer 162 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., grid strips) of nanopattern 196, i.e., of the nanoscale pattern of replica configuration and shape 140. „
63
Thus, this modifying, via 198 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., grid (waffle) type array 200 of nanowires on substrate surface 182 of substrate 160. Producing an array of nanoscale structures (nanoparticles) on a substrate surface via a 'nanogrooved' type faceted self-assembled template formed from a 'singular' crystal surface: (forming and using a surface replica element)
Fig. 6 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with an array of nanowires (nanoscale structures) on a substrate surface (e.g., of Fig. 4), for generating (via an etching technique) an array of nanoparticles (nanoscale structures) on the substrate surface.
The exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 6, is another extension of the preceding illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4.
There is cross contacting (206 [cross contacting]), for example, by pressing or bringing together, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with the previously generated array 178 of nanowires 180 on substrate surface 182 of substrate 160, for forming a combination structure 207 having replica configuration and shape 140 directly in contact (in Fig. 6, indicated by 208) with nanowires 180 on substrate surface 182 of substrate 160. The phrase 'cross contacting', as used herein, refers to pressing or bringing together replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with substrate surface 182 of substrate 160, in a manner or way whereby replica configuration and shape 140 of the treated applied material is disposed (i.e., positioned or placed) at an angle in a range of between 0° and 90°, relative to array 178 of nanowires 180 on substrate surface 182 of substrate 160. Such relative disposition (positioning or placing) is indicated by 208 in Fig. 6. This main step (procedure) of cross contacting (206 [cross contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., sub-sections) of nanowires 180 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150. Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (sub-sections) of nanowires 180 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
A consequence of this main step (procedure) of cross contacting (206 [cross contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portions or sections of nanowires 180 which are not brought into contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which is not brought into contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150. The processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (210 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, from nanowires 180. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from nanowires 180.
In this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 6, by this processing first main sub-step (sub- procedure), there is forming a sub-sectioned type of nanopattern (nanoscale pattern), i.e., nanopattern 212 of nanowires 180 upon substrate surface 182 of substrate 160.
The processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 214 [etching]) the sub-sectioned type of nanopattern 212 of nanowires 180 upon substrate surface 182 of substrate 160, which was obtained from the preceding separating (210 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 214 [etching]) the preceding stated remaining areal portions or sections of nanowires 180 which were not chemically functionalized (derivatized) by the preceding cross contacting (206 [cross contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140). Alternatively, and equivalently stated, the processing step (procedure) further includes modifying (via 214 [etching]) the exposed areal portions or sections of nanowires 180 which are not covered or masked by the previously chemically functionalized (derivatized) portions or sections of nanopattern 212 of nanowires 180, i.e., of the nanoscale pattern of replica configuration and shape 140.
Thus, this modifying, via 214 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 216 of nanoparticles 218 on substrate surface 182 of substrate 160. Producing an array of nanoscale structures (nanogrooves) on a substrate surface via a 'nanogrooved' type faceted self-assembled template formed from a 'singular' crystal surface: (forming and using a surface replica element)
Fig. 7 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanogrooves (nanoscale structures) on the substrate surface.
The exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 7, is an alternative to the previous illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4.
There is contacting (230 [contacting]), for example, by pressing or bringing together, replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, with the substrate surface 232 of substrate 234, for forming a combination structure 236 having replica configuration and shape 140 in contact with substrate surface 232. 6
This main step (procedure) of contacting (230 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 148, those areal portions or sections (e.g., strips) of substrate surface 232 of substrate 234 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 150. Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 232 of substrate 234 which are brought into direct contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which are brought into direct contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150.
A consequence of this main step (procedure) of contacting (230 [contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portion or section of substrate surface 232 of substrate 234 which is not brought into contact with ink 148 of replica configuration and shape 140 of the treated applied material, i.e., which is not brought into contact with ink 148 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150. The processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (242 [separating]) replica configuration and shape 140 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150, from substrate surface 232 of substrate 234. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 150 from substrate surface 232 of substrate 234.
In this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 7, by this processing first main sub-step (sub- procedure), there is forming a nanopattern (nanoscale pattern), i.e., nanopattern 244, upon substrate surface 232 of substrate 234. Nanopattern 244 is composed or made up of two parts or components. The first part or component of nanopattern 244 corresponds to: (i) those areal portions or sections (e.g., strips) of substrate surface 232 of substrate 234 which were chemically functionalized (derivatized) by the preceding contacting (230 [contacting]) procedure, as a result of having been brought into direct contact with ink 148 of replica configuration and shape 140. The second part or component of nanopattern 244 corresponds to: (ii) the remaining areal portion or section of substrate surface 232 of substrate 234 which was not chemically functionalized (derivatized) by the preceding contacting (230 [contacting]) procedure, as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140.
The processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 246 [etching]) the nanopattern (nanoscale pattern), i.e., nanopattern 244, upon substrate surface 232 of substrate 234, which was obtained from the preceding separating (242 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 246 [etching]) the remaining areal portion or section of substrate surface 232 of substrate 234 which was not chemically functionalized (derivatized) by the preceding contacting (230 [contacting]) procedure (as a result of not having been brought into direct contact with ink 148 of replica configuration and shape 140). Alternatively, and equivalently stated, the processing step (procedure) further includes modifying (via 246 [etching]) the exposed areal portion or section of substrate surface 232 of substrate 234 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., strips) of nanopattern 244, i.e., of the nanoscale pattern of replica configuration and shape 140.
Thus, this modifying, via 246 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 248 of nanogrooves 250 on substrate surface 252 of (etched) substrate 254. Use of a surface replica element with a roller for producing a nanopattern on a substrate surface
Fig. 8 is a schematic (flow-type) diagram illustrating selected main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting production and use of a surface replica element (e.g., of Fig. 4) with a roller for forming a nanopattern on a substrate surface, which, in turn, is useable for generating (via a functionalizing technique) an array of nanostrips on the substrate surface. The exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 6, is an alternative to the previous illustratively described exemplary specific preferred embodiment of implementing the method of the present invention, illustrated in Fig. 4. With additional reference to Fig. 4, for this embodiment, there is applying, via a material applying process (in particular, a casting (molding) type of material applying process), at least one material (in particular, at least one suitable casting (molding) material, such as an organic polymer [e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof], or, an organic-inorganic polymer [e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof]), upon the entirety of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120. This step (procedure) is performed for replicating (138 [replicating]) the entirety of array 124 of nanogrooves of nanogrooved surface 122, such that the applied material, i.e., the casted (molded) material (in particular, the organic polymer or organic- inorganic polymer), includes a replica configuration and shape 264 (Fig. 8), for example, as part of a surface replica element 262, of the entirety of array 124 of nanogrooves of nanogrooved surface 122 of nanogrooved type faceted self-assembled template 120.
Then, the treating step (procedure) includes, as a first main sub-step (sub-procedure), wrapping (260 [wrapping]) surface replica element 262 onto and around a roller 266, for forming a wrapped surface replica element 268.
The treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking (270 [inking]), by using a suitable ink 272, the surface of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268. More specifically, there is inking (270 [inking]), by using ink 272, that surface part or area of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268, which encompasses replica configuration and shape 264 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268.
The preceding treating steps (procedures) are thus performed for forming treated applied material, i.e., a treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268, as referenced by 274 in Fig. 8. Treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274 has, via the treated (inked) portion thereof, replica configuration and shape 264 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 268. Then, there is contacting (276 [contacting]), for example, by rolling and bringing together, replica configuration and shape 264 of the treated applied material, Le., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274, with the substrate surface 280 of substrate 282, for forming a combination structure 284 having replica configuration and shape 264 in contact with substrate surface 280.
This main step (procedure) of contacting (276 [contacting]) involves, and results in, transferring, via ink 272, replica configuration and shape 264 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274 onto substrate surface 280 of substrate 282.
This main step (procedure) of contacting (276 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 272, those areal portions or sections (e.g., strips) of substrate surface 280 of substrate 282 which are brought into direct contact with ink 272 of replica configuration and shape 264 of the treated applied material, i.e., which are brought into direct contact with ink 272 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 274. Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemical composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 280 of substrate 282 which are brought into direct contact with ink 272 of replica configuration and shape 264 of the treated applied material, i.e., which are brought into direct contact with ink 272 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274.
The processing step (procedure) includes, as a first main sub-step (sub-procedure), separating replica configuration and shape 264 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274, from substrate surface 280 of substrate 282. This is accomplished by separating, for example, by lifting off and removing, the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type wrapped surface replica element 274 from substrate surface 280 of substrate 282. In this exemplary specific preferred embodiment of implementing the method of the present invention, similar to that shown in Fig. 4, by this processing sub-step (sub-procedure), there is forming a nanopattern (nanoscale pattern), i.e., nanopattern 286, upon substrate surface 280 of substrate 282.
The formed nanopattern (nanoscale pattern), i.e., nanopattern 286, upon substrate surface 280 of substrate 282, can be used for implementing the method of the present invention, for generating (via an etching technique, or via a functionalizing technique) any of various different types of an array of nanoscale structures (e.g., nanowires, nanostrips, nanoparticles, or nanogrooves) on the substrate surface.
Producing an array of nanoscale structures (nanobelts or nanostrips) on a substrate surface via a 'nanostepped' type faceted self-assembled template formed from a 'vicinal' crystal surface: (forming and using a surface replica element) Fig. 9 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanobelts (nanoscale structures) on a substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface. Providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface.
There is providing a 'nanostepped' type faceted self-assembled template 300 whose nanostepped surface 302 includes an array 304 of nanoscale features, i.e., nanosteps. Array 304 of nanosteps is spontaneously formed, via a process of facet formation (306 [facet formation]), by treating (308 [annealing]) 'vicinal' crystal surface 310. Vicinal crystal surface 310 is obtained by cutting (312 [cutting]) a crystal 314 along a 'vicinal' cutting plane 316 (at a miscut tilt angle (θ) relative to the nearest low-index plane) located within a crystal surface region of crystal 314. Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Figs. 3a - 3c, and are exemplified in the Examples section, hereinbelow. Applying at least one material upon at least part of the array of the nanoscale features, for replicating the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features.
There is applying, via a material applying process (in particular, a casting or molding type of material applying process), at least one material (in particular, at least one suitable casting or molding material, such as an organic polymer [e.g., a thermoplastic, a thermoset, an elastomer, or any combination thereof], or, an organic-inorganic polymer [e.g., an organic-inorganic form of a thermoplastic, an organic-inorganic form of a thermoset, an organic-inorganic form of an elastomer, or any combination thereof]), upon the entirety of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300. This step (procedure) is performed for replicating (318 [replicating]) the entirety of array 304 of nanosteps of nanostepped surface 302, such that the applied material, i.e., casted or molded material (in particular, the organic polymer or organic— inorganic polymer), includes a replica configuration and shape 320, for example, as part of a surface replica element 322, of the entirety of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300.
Surface replica element 322 has a bulk or overall geometrical shape or form, preferably, of a cylinder or disc, each being an exemplary three-dimensional non- polyhedron curved bulk or overall geometrical shape or form. Surface replica element 322 has a bulk or overall geometrical shape or form, more preferably, of a prism, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form. Surface replica element 322 has a bulk or overall geometrical shape or form, most preferably, of a parallelpiped, being an exemplary three-dimensional polyhedron bulk or overall geometrical shape or form.
Surface replica element 322 has a bulk or overall size wherein each size dimension of length (L), width (W), and height (thickness) (T), has a value or magnitude in a general range of between about 0.1 nanometer (nm) and about 1 meter (m). More specifically, Surface replica element 322 has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron (μm) and about 1 centimeter (cm), (U) a second range of between about 100 microns (μm) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow.
Treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape. The treating step (procedure) includes, as a first main sub-step (sub-procedure), separating (324 [separating]), for example, by peeling off, the applied material, i.e., the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322 from nanostepped surface 302 of nanostepped type faceted self-assembled template 300. While performing the treating step (procedure), there is maintaining replica configuration and shape 320 of the applied material, i.e., of the organic polymer or organic— inorganic polymer cast (mold) type surface replica element 322, for forming a stand-alone organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322 having replica configuration and shape 320.
The treating step (procedure) further includes, as a second main sub-step (sub-procedure), inking (326 [inking]), by using a suitable ink 328, the surface of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322. More specifically, there is inking (326 [inking]), by using ink 328, that surface part or area of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322, which encompasses replica configuration and shape 320 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322.
For performing this second main sub-step (sub-procedure) of inking (326 [inking]), there is using any suitable ink 328 which is composed of essentially any type or kind of a solution or suspension of a substance that binds, adheres, or/and adsorbs, onto substrate surface 334 of substrate 336. An exemplary ink which is particularly suitable for performing this main sub-step (sub-procedure) is a thiol compound based ink, or a silane compound based ink. The preceding treating steps (procedures) are thus performed for forming treated applied material, i.e., a stand-alone treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322, as referenced by 330 in Fig. 9. Treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330 has, via the treated (inked) portion thereof, replica configuration and shape 320 of the applied material, i.e., of the organic polymer or organic-inorganic polymer cast (mold) type surface replica element 322.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow.
Contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface.
There is contacting (332 [contacting]), for example, by pressing or bringing together, replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330, with the substrate surface 334 of substrate 336, for forming a combination structure 338 having replica configuration and shape 320 in contact with substrate surface 334. In this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 9, the substrate, i.e., substrate 336, includes two main distinct layers, i.e., a first or base layer 340, and a second or surface layer 342 which is situated and lies upon first or base layer 340. During this contacting step (procedure), second or surface layer 342 is the top or upper most layer of substrate 336 which includes substrate surface 334 that is brought into contact with replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic- inorganic polymer cast (mold) type surface replica element 330.
In general, first or base layer 340 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof. For example, first or base layer 340 is composed of a semiconductor type or kind of material or substance, such as silicon, oxidized silicon, or gallium arsenide. Alternatively, for example, first or base layer 340 is composed of an insulating type or kind of material or substance, for example, glass, quartz, or sapphire. In general, second or surface layer 342 is composed of a material or substance selected from the group consisting of inorganic matter, organic matter, and a combination thereof. For example, second or surface layer 342 is composed of a metallic type or kind of material or substance, such as gold, silver, platinum, gold on chromium, or gold on titanium, which is situated and lies upon first or base layer 340.
This main step (procedure) of contacting (332 [contacting]) involves, and results in, transferring, via ink 328, replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330 onto substrate surface 334 of second or surface layer 342 of substrate 336.
This main step (procedure) of contacting (332 [contacting]) also involves, and also results in, chemically functionalizing (derivatizing), via contacting with ink 328, those areal portions or sections (e.g., belts) of substrate surface 334 of second or surface layer 342 which are brought into direct contact with ink 328 of replica configuration and shape 320 of the treated applied material, i.e., which are brought into direct contact with ink 328 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330. Such functionalizing (derivatizing) alters (changes, modifies), via chemical reaction, the physicochemϊcal composition or make-up (as well as properties, characteristics, and behavior) of those areal portions or sections (strips) of substrate surface 334 of second or surface layer 342 which are brought into direct contact with ink 328 of replica configuration and shape 320 of the treated applied material, Le., which are brought into direct contact with ink 328 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330.
A consequence of this main step (procedure) of contacting (332 [contacting]) is that there is no chemically functionalizing (derivatizing) of the remaining (surrounding) areal portion or section of substrate surface 334 of second or surface layer 342 which is not brought into contact with ink 328 of replica configuration and shape 320 of the treated applied material, i.e., which is not brought into contact with ink 328 of the treated (inked) organic polymer or organic-inorganic polymer cast (mold) type surface replica element 330. Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow. Processing the combination structure, for generating the array of the nanoscale structures on the substrate surface.
The processing step (procedure) includes, as a first main sub-step (sub-procedure), separating (344 [separating]) replica configuration and shape 320 of the treated applied material, i.e., of the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 330, from substrate surface 334 of substrate 336. This is accomplished by separating, for example, by lifting back and removing, the treated (inked) organic polymer or organic— inorganic polymer cast (mold) type surface replica element 330 from substrate surface 334 of substrate 336.
In this exemplary specific preferred embodiment of implementing the method of the present invention, as shown in Fig. 9, by this processing first main sub-step (sub- procedure), there is forming a nanopattern (nanoscale pattern), i.e., nanopattern 346, upon substrate surface 334 of substrate 336. Nanopattern 346 is composed or made up of two parts or components. The first part or component of nanopattern 346 corresponds to: (i) those areal portions or sections (e.g., belts) of substrate surface 334 of second or surface layer 342 which were chemically functionalized (derivatized) by the preceding contacting (332 [contacting]) procedure, as a result of having been brought into direct contact with ink 328 of replica configuration and shape 320. The second part or component of nanopattern 346 corresponds to: (ii) the remaining areal portion or section of substrate surface 334 of second or surface layer 342 which was not chemically functionalized (derivatized) by the preceding contacting (332 [contacting]) procedure, as a result of not having been brought into direct contact with ink 328 of replica configuration and shape 320.
The processing step (procedure) further includes, as a second main sub-step (sub-procedure), modifying (via 348 [chemical functionalizing (derivatizing)], or via 356 [etching]) the nanopattern (nanoscale pattern), i.e., nanopattern 346, upon substrate surface 334 of second or surface layer 342 of substrate 336, which was obtained from the preceding separating (344 [separating]) sub-step (sub-procedure). More specifically, the processing step (procedure) further includes modifying (via 348 [chemical functionalizing (derivatizing)], or via 356 [etching]) the preceding stated second part or component of /o
nanopattern 346, i.e., the remaining areal portion or section of substrate surface 334 of second or surface layer 342 of substrate 336 which was not chemically functionalized (derivatized) by the preceding contacting (332 [contacting]) procedure (as a result of not having been brought into direct contact with ink 328 of replica configuration and shape 320). Alternatively, and equivalently stated, the processing step (procedure) further includes modifying (via 348 [chemical functionalizing (derivatizing)], or via 356 [etching]) the exposed areal portion or section of substrate surface 334 of second or surface layer 342 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346, i.e., of the nanoscale pattern of replica configuration and shape 320.
Modifying, via 348 [chemical functionalizing (derivatizing)], the nanopattern (nanoscale pattern), i.e., nanopattern 346, upon substrate surface 334 of second or surface layer 342 of substrate 336, is performed by using a suitable chemical functionalizing (derivatizing) procedure or technique, involving a suitable chemical functionalizing (derivatizing) reagent. A suitable chemical functionalizing (derivatizing) procedure, or technique, is, for example, selected from the group consisting of a thiol compound based functionalizing (derivatizing) procedure or technique, and a silane compound based functionalizing (derivatizing) procedure or technique.
For example, there is using a thiol compound based chemical functionalizing (derivatizing) procedure or technique, involving a thiol compound based chemical functionalizing (derivatizing) reagent. A suitable thiol compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 16-mercaptohexadecanoic acid, 12-thioldodecanol, and 12-aminododecanethiol. Alternatively, for example, there is using a silane compound based type of functionalizing (derivatizing) procedure or technique, involving a silane compound based chemical functionalizing (derivatizing) reagent. A suitable silane compound based chemical functionalizing (derivatizing) reagent is, for example, selected from the group consisting of 3 -aminopropyl-triethoxisilane, and 3 -mercaptopropyl-trimethoxysilane.
Modifying (via 348 [chemical functionaiizing (derivatizing)] the exposed areal portion or section of substrate surface 334 of second or surface layer 342 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346, results in formation of a different substrate surface, i.e., substrate surface 354, of second or surface layer 342 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346.
Thus, this modifying, via 348 [chemical functionalizing (derivatizing)], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 350 of nanostrips 352 on substrate surface 354 of substrate 336.
For array 350 of nanostrips 352 on substrate surface 354 of substrate 336, any single or individual nanostrip 352 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (run) and about 10 nanometers (run), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
For array 350 of nanostrips 352 on substrate surface 354 of substrate 336, the pitch (e.g., analogous to P2, shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanostrips 352, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm). Typically, the pitch between two neighboring similar (i.e., not necessarily identical) nanostrips of array 350 of nanostrips 352 on substrate surface 354 of substrate 336, has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to Pi, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanosteps of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300. Typically, the width of any single or individual nanostrip of array 350 of nanostrips 352 on substrate surface 354 of substrate 336 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanostrips of array 350 of nanostrips 352 on substrate surface 354 of substrate 336. Modifying, via 356 [etching], the nanopattern (nanoscale pattern), i.e., nanopattern
346, upon substrate surface 334 of second or surface layer 342 of substrate 336, is performed by using a suitable etching procedure or technique, involving a suitable etching (etchant) reagent. A suitable etching procedure or technique is, for example, selected from o
the group consisting of a wet etching procedure or technique, and a dry etching procedure or technique.
For example, there is using an oxidizing type of wet etching procedure or technique, involving an oxidizing compound based wet etching (etchant) reagent. A suitable oxidizing compound based wet etching (etchant) reagent is, for example, a solution composed of: (i) potassium ferricyanide [K3Fe(CN)6], 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1M; and (iii) potassium hydroxide [KOH], 1.0 M, which is particularly for wet etching of gold [Au]. Another suitable wet etching (etchant) reagent is, for example, a solution composed of potassium hydroxide [KOH], 0.1 M, which is particularly useful for wet etching of silicon [Si] .
For example, there is using a reactive ion etching type of dry etching procedure or technique, involving a reactive ion etching dry etching (etchant) reagent. An exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous sulfur tetra-fiuoride [SF4]. Another exemplary suitable reactive ion etching dry etching (etchant) reagent is gaseous chlorine [Cl2].
Modifying, via 356 [etching], the exposed areal portion or section of substrate surface 334 of second or surface layer 342 of substrate 336 which is not covered or masked by the previously chemically functionalized (derivatized) portions or sections (e.g., belts) of nanopattern 346, results in formation of a different substrate surface, i.e., substrate surface 362, on the previously indicated first or base layer 340 of the remaining (non- etched) part of previously indicated substrate 336. Accordingly, the previously indicated first or base layer 340 of previously indicated substrate 336, now functions as the substrate, referenced as substrate 340, having substrate surface 362.
Thus, this modifying, via 356 [etching], sub-step (sub-procedure) of the processing step (procedure), results in generating the array of the nanoscale structures on the substrate surface, i.e., array 358 of nanobelts 360 on substrate surface 362 of substrate 340.
For array 358 of nanobelts 360 on substrate surface 362 of substrate 340, any single or individual nanobelt 360 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm). For array 358 of nanobelts 360 on substrate surface 362 of substrate 340, the pitch (e.g., analogous to P2, shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanobelts 360, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μrn).
Typically, the pitch between two neighboring similar (i.e., not necessarily identical) nanobelts of array 358 of nanobelts 360 on substrate surface 362 of substrate 340, has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to Pj, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanosteps of array 304 of nanosteps of nanostepped surface 302 of nanostepped type faceted self-assembled template 300. Typically, the width of any single or individual nanobelt of array 358 of nanobelts 360 on substrate surface 362 of substrate 340 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanobelts of array 358 of nanobelts 360 on substrate surface 362 of substrate 340.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Fig. 3d, and are exemplified in the Examples section, hereinbelow.
Producing an array of nanoscale structures (nanowires) on a substrate surface via a 'nanogrooved' type faceted self-assembled template formed from a 'singular' crystal surface: (without forming and using, a surface replica element)
Fig. 10 is a schematic (flow-type) diagram illustrating the main steps (procedures), and structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved1 type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by treating a 'singular' crystal surface, particularly highlighting application of material upon the surface of the self-assembled template, which, in turn, is directly used for generating an array of nanowires (nanoscale structures) on a substrate surface.
Providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface. There is providing a 'nanogrooved' type faceted self-assembled template 120 whose nanogrooved surface includes an array 124 of nanoscale features, i.e., nanogrooves. Array 124 of nanogrooves is spontaneously formed, for example, as illustratively described hereinabove, with reference to Fig. 4, via a process of facet formation (Fig. 4, 126 [facet formation]), by treating (Fig. 4, 128 [annealing]) a 'singular' crystal surface (Fig. 4, 130). The singular crystal surface (Fig. 4, 130) is obtained by cutting (Fig. 4, 132 [cutting]) a crystal (Fig. 4, 134) along a 'singular' cutting plane (Fig. 4, 136 (corresponding to a low-index plane) located within a crystal surface region of the crystal (Fig. 4, 134).
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Figs. 2a - 2d, and are exemplified in the Examples section, hereinbelow. Applying at least one material upon at least part of the array of the nanoscale features, for replicatiiiR the at least part of the array of the nanoscale features, such that the applied material(s) includes a replica configuration and shape of the at least part of the array of the nanoscale features.
There is applying (372 [applying material(s)]), via a material applying process (in particular, a depositing type of material applying process [e.g., a physical deposition process, or a chemical deposition process]), at least one material 370 (in particular, at least one suitable depositing material), upon at least part of array 124 of nanogrooves of the nanogrooved surface of nanogrooved type faceted self-assembled template 120.
A suitable depositing material is, for example, a metal element [e.g., platinum [Pt], gold [Au], or molybdenum [Mo]]; a metal alloy [e.g., palladium-gold [PdAu]]; a semi-metal element [e.g., elemental silicon [Si]]; a non-metal element [e.g., an allotrope of carbon, such as nanotube elemental carbon]; or an organic polymer [e.g., a thermoplastic, such as polystyrene (PS)].
This step (procedure) is performed for replicating the at least part of array 124 of nanogrooves of the nanogrooved surface, such that the applied material(s) 374, i.e., the deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), includes a replica configuration and shape of the at least part of array 124 of nanogrooves of the nanogrooved surface of nanogrooved type faceted self-assembled template 120. Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow. Treating the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape.
The treating step (procedure) includes allowing the applied material(s) 374, i.e., the deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), while maintaining the replica configuration and shape thereof, upon the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, to stand at a pre-determined temperature, for a pre-determined period of time. This results in forming treated applied material(s) 374, i.e., the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120. As shown in Fig. 10, this embodiment is indicated as element 376.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow. Contacting the replica configuration and shape of the treated applied material(s), with the substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface.
There is contacting (378 [contacting]), for example, by pressing or bringing together, the treated applied material(s) 374, i.e., the treated deposited material (in particular, the treated deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, via element 376, with the substrate surface 380 of substrate 382, for forming a combination structure 384 having the replica configuration and shape in contact with substrate surface 380 of substrate 382.
This main step (procedure) of contacting (378 [contacting]) involves, and results in, transferring, via element 376, a portion or layer of the treated applied material, i.e., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, onto substrate surface 380 of substrate 382. Additional details relating to performing this main step (procedure), and sub-steps
(sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1, and are exemplified in the Examples section, hereinbelow.
Processing the combination structure, for generating the array of the nanoscale structures on the substrate surface. The processing step (procedure) involves separating (390 [separating]) the replica configuration and shape of the treated applied material, i.e., of the treated deposited material (in particular, the deposited metal element, metal alloy, semi-metal element, non-metal element, or organic polymer), part of combination structure 384, via element 376, from substrate surface 380 of substrate 382. This is accomplished by separating, for example, by lifting back and removing, the treated deposited material having the replica configuration and shape of the at least part of array 124 of nanogrooves on the nanogrooved surface of nanogrooved type faceted self-assembled template 120, via element 376, from substrate surface 380 of substrate 382.
Thus, this processing step (procedure) results in generating the array of the nanoscale structures on the substrate surface, i.e., array 392 of nanowires 394 on substrate surface 380 of substrate 382.
For array 392 of nanowires 394 on substrate surface 380 of substrate 382, any single or individual nanowire 394 has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
For array 392 of nanowires 394 on substrate surface 380 of substrate 382, the pitch (e.g., analogous to P2, shown in Fig. 1, bottom), being the average center-to-center distance extending between two neighboring similar (i.e., not necessarily identical) nanowires 394, has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
Typically, the pitch between two neighboring similar (i.e., not necessarily identical) nanowires of array 392 of nanowires 394 on substrate surface 380 of substrate 382, has a value or magnitude which is comparable to the value or magnitude of the pitch (e.g., analogous to P1, shown in Fig. 1, top) between two neighboring similar (i.e., not necessarily identical) nanogrooves of array 124 of nanogrooves of the nanogrooved surface of nanogrooved type faceted self-assembled template 120. Typically, the width of any single or individual nanowire of array 392 of nanowires 394 on substrate surface 380 of substrate 382 has a value or magnitude which is less than the value or magnitude of the pitch between two neighboring similar nanowires of array 392 of nanowires 394 on substrate surface 380 of substrate 382.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Fig. 2e, and are exemplifiedin the Examples section, hereinbelow.
Producing an array of nanoscale structures on a substrate surface via a 'nanogrooved' type faceted self-assembled template formed from a 'singular' crystal surface: 'M-plane' of a sapphire (alpha-alumina [a-Al?Oi]) crystal)
Fig. 1 Ia is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface (obtained by cutting along the 'M-plane' of a sapphire (alpha-alumina [(X-Al2O3]) crystal), and characterized by R-plane and S-plane nanofacets, as exemplified and described in Example 1.
For this exemplary specific preferred embodiment of implementing the method of the present invention, the main step (procedure) of providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface, is performed as follows.
There is providing a 'nanogrooved' type faceted self-assembled template 400 whose nanogrooved surface 402 includes an array 404 of nanoscale features, i.e., nanogrooves, characterized by R-plane and S-plane nanofacets. Array 404 of nanogrooves is spontaneously formed, via a process of facet formation (406 [facet formation]), by treating (408 [annealing]) 'singular' crystal surface 410. Singular crystal surface 410 is obtained by cutting (412 [cutting]) a sapphire (alpha-alumina [α-Al2O3]) crystal 414 along a 'singular' cutting plane (M-plane) 416 (corresponding to a low-index plane) located within a crystal surface region of sapphire (alpha-alumina
Figure imgf000086_0001
crystal 414. The cutting (412 [cutting]) of sapphire (alpha-alumina [α- Al2O3]) crystal 414 is performed toward the [1,0,- 1,0] direction 418.
Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Figs. 2a - 2d, and are exemplified in the Examples section, hereinbelow.
The remaining main steps (procedures) of this exemplary specific preferred embodiment of implementing the method of the present invention, are as follows: applying (420 [applying materials]) at least one material upon at least part of array 404 of nanogrooves, for replicating the at least part of array 404 of nanogrooves, such that the applied material(s) includes a replica configuration and shape of the at least part of array 404 of nanogrooves; treating (422 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting (424 [contacting]) the replica configuration and shape of the treated applied material(s), with a substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing (indicated as 426 [array generation]) the combination structure, for generating the array of the nanoscale structures on the substrate surface.
The preceding indicated remaining main steps (procedures) of this exemplary specific preferred embodiment of the method are performed in accordance with the main steps (procedures), and structures, of the exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanogrooved' type faceted self-assembled template whose surface includes an array of nanogrooves (nanoscale features) spontaneously formed by annealing (treating) a 'singular' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanowires (nanoscale structures) on the substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface, as illustratively described hereinabove, with reference to Fig. 4.
Implementation of this exemplary specific preferred embodiment of the method of the present invention results in generating an array of nanoscale structures on a substrate surface of a substrate, for example, an array of nanostrips or nanowires on a substrate surface of a substrate.
Producing an array of nanoscale structures on a substrate surface via a 'nanostepped' type faceted self-assembled template formed from a 'vicinal' crystal surface: 'vicinal C~plane'ofa sapphire (alpha-alumina fa-AhOi)) crystal) Fig. 1 Ib is a schematic (flow-type) diagram illustrating the main steps (procedures), and selected structures, of an exemplary specific preferred embodiment of implementing the method of the present invention, particularly highlighting provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a 'vicinal' crystal surface (obtained by cutting along a 'vicinal C-plane' of a sapphire (alpha-alumina [U-Al2O3]) crystal), and characterized by R-plane and C-plane nanofacets, as exemplified and described in Example 2.
For this exemplary specific preferred embodiment of implementing the method of the present invention, the main step (procedure) of providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface, is performed as follows.
There is providing a 'nanostepped' type faceted self-assembled template 430 whose nanostepped surface 432 includes an array 434 of nanoscale features, i.e., nanosteps, characterized by R-plane and C-plane nanofacets. Array 434 of nanosteps is spontaneously formed, via a process of facet formation (436 [facet formation]), by treating (438 [annealing]) 'vicinal' crystal surface 440. Vicinal crystal surface 440 is obtained by cutting (442 [cutting]) a sapphire (alpha-alumina [(X-AI2O3]) crystal 444 along a 'vicinal' cutting plane (vicinal C-plane) 446 (at a miscut tilt angle (θ) relative to the nearest low-index plane) located within a ciystal surface region of sapphire (alpha-alumina [(X-Al2O3]) crystal 444. The cutting (442 [cutting]) of sapphire (alpha-alumina [Oc-Al2O3]) crystal 444 is performed toward the [1,-1,0,0] direction 448. Additional details relating to performing this main step (procedure), and sub-steps (sub-procedures) thereof, are illustratively described hereinabove, with reference to Fig. 1 and Figs. 3a - 3c, and are exemplified in the Examples section, hereinbelow.
The remaining main steps (procedures) of this exemplary specific preferred embodiment of implementing the method of the present invention, are as follows: applying (450 [applying materials]) at least one material upon at least part of array 434 of nanosteps, for replicating the at least part of array 434 of nanosteps, such that the applied material(s) includes a replica configuration and shape of the at least part of array 434 of nanosteps; treating (452 [treating]) the applied material(s) while maintaining the replica configuration and shape thereof, for forming treated applied material(s) having the replica configuration and shape; contacting (454 [contacting]) the replica configuration and shape of the treated applied material(s), with a substrate surface, for forming a combination structure having the replica configuration and shape in contact with the substrate surface; and processing (indicated as 456 [array generation]) the combination structure, for generating the array of _ the nanoscale structures on the substrate surface.
The preceding indicated remaining main steps (procedures) of this exemplary specific preferred embodiment of the method are performed in accordance with the main steps (procedures), and structures, of the exemplary specific preferred embodiment of implementing the method of the present invention, including provision of a 'nanostepped' type faceted self-assembled template whose surface includes an array of nanosteps (nanoscale features) spontaneously formed by annealing (treating) a Vicinal' crystal surface, and production of a corresponding surface replica element which is used for forming a nanopattern on a substrate surface, which, in turn, is used for generating (via an etching technique) an array of nanobelts (nanoscale structures) on the substrate surface, or for generating (via a functionalizing technique) an array of nanostrips (nanoscale structures) on the substrate surface, as illustratively described hereinabove, with reference to Fig. 4.
Implementation of this exemplary specific preferred embodiment of the method of the present invention results in generating an array of nanoscale structures on a substrate surface of a substrate, for example, an array of nanostrips or nanobelts on a substrate surface of a substrate.
Above illustratively described novel and inventive aspects and characteristics, and advantages thereof, of the present invention further become apparent to one ordinarily skilled in the art upon examination of the following examples, which are not intended to be limiting. Additionally, each of the various embodiments and aspects of the present invention as delineated herein above and as claimed in the claims section below finds experimental support in the following examples.
EXAMPLES
Reference is now made to the following examples, which together with the above description, illustrate the invention in a non-limiting fashion.
In the following Examples, two types of faceting surfaces were studied: (i) an unstable singular surface (i.e. a crystal surface cut along a low-index plane), which spontaneously facets into V-shaped nanogrooves, and (ii) a vicinal surface (i.e. a crystal surface cut along a high-index plane that is slightly tilted from a low-index plane), which spontaneously facets into L-shaped nanosteps. The crystal surfaces chosen to represent these two types of faceting surfaces were, respectively: (i) a 'singular' crystal surface (obtained by cutting along the 'M-plane' of a sapphire (alpha-alumina [α-Al2θ3]) [1,0,-1,0] crystal), and characterized by R-plane and S-plane nanofacets (e.g., as schematically illustrated in Fig. l la), and (ii) a 'vicinal' crystal surface (obtained by cutting along a
Vicinal C-plane' of a sapphire (alpha-alumina [α- Al2O3]) [0001] crystal, tilted by 2 degrees toward the [1,-1,0,0] direction), and characterized by R-plane and C-plane nanofacets (e.g., as schematically illustrated in Fig. 1 Ib).
MATERIALS AND EXPERIMENTAL METHODS
Crystals and crystal surfaces M-plane sapphire (alpha-alumina [α- Al2O3]) [1,0,-1,0]) wafers were obtained from
Monocrystal PIc, Stavropol, Russia.
Vicinal C-plane sapphire (alpha-alumina [α- Al2O3]) [0001] wafers (one side polished), with a miscut inclination angle of 2 degrees towards the [1,-1,0,0] direction, were obtained from Gavish Industrial & Materials Ltd., Omer, Israel (one side polished). The different templates of the sapphire (alpha-alumina [(X-Al2O3]) crystals were produced as wafers by cutting into 1 x 1 cm pieces, followed by mechanical polishing.
Lattice and miscut orientations of the vicinal crystal surfaces were determined by a standard technique of asymmetric double-exposure back-reflection X-ray diffraction. The M-plane and miscut C-plane sapphire crystal surfaces were then thermally annealed in air at 11000C and 15000C for 20 - 48 hrs, and 5 - 10 hrs, respectively.
The periodic arrays of highly straight and parallel nanofacets were generated by annealing different unstable faces of the sapphire (alpha-alumina [(X-AI2O3]) crystal. The nanopatterns of these self-assembled (self-organized) templates were replicated by a standard soft lithography procedure to produce patterned self-assembled monolayers (SAMs) of silanes on a silicon/silicon dioxide [Si/SiO2] surface, or of thiols on a gold [Au] surface, in parallel lines or crossbar arrays, where the thinner lines were as thin as 10 nm with a pitch of 40 nm, extending over areas on the order of square centimeters. Wet etching of the SAM-masked silicon surface, and of the SAM-masked gold surface led to generating periodic arrays of nanoscale structures (e.g., wires, grids, V-grooves, and waffles) of nanoscale widths and pitches, on different substrate surfaces of substrates. Patterned SAM samples
Patterned SAM samples, silanes or thiols, were made on clean native Si (100) (Boron-doped, 10 - 70 ohm-cm, obtained from VirginiaSemi, USA) and on Si (100) coated with a 50 A adhesion layer of chromium [Cr] followed by a 200 A layer of gold [Au], and then cleaned with piranha reagent (3:1, sulfuric acid [H2SO4]: hydrogen peroxide [H2O2]) for 2 hours, respectively.
The patterned SAMs were prepared by nanocontact printing (nCP), similar to microcontact (μCP) printing. The templates for the fabrication of the elastomeric stamps were the above mentioned faceted sapphire surfaces.
For the production of each elastomeric stamp, the sapphire template was placed in a polystyrene dish, and a degassed 9:1 (volume/volume) mixture of polydimethylsiloxane (PDMS), [Sylgard™ 184 silicone elastomer (Sylgard) and its curing agent (obtained from Dow-Corning Corp.)], as an exemplary organic-inorganic form of an elastomer type of applying material, was applied, via casting (molding), on top of the self-assembled (annealed) crystal surfaces, and were then separated (via peeling off) therefrom.
The polydimethylsiloxane (PDMS) silicone elastomer, and its curing agent, was carefully poured over each template, and allowed to cure in an oven at 60 0C for 2 hours. Each elastomer stamp was then very gently peeled off from the template, and used as a stamp for nanocontact printing.
The resulting elastomeric type of stamps (self-assembled templates) were inked either with a solution of octadecyltrichlorosilane (OTS) in hexane, or with a solution of 1-hexadecanetliiol in ethanol, and manually pressed for 1 minute onto bare native-oxide Si wafers, or onto Au-coated wafers, respectively.
The elastomeric stamps were first washed few times with n-heptane (Merck) and ethanol (Bio Lab Ltd.), and then inked with hexane (Bio Lab Ltd.) solution of octadecyltrichlorosilane (OTS) (Aldrich), or an ethanolic (Bio Lab Ltd.) solution of
1-hexadecanethiol (Fluka), and pressed for 1 minute onto Si or gold-coated Si substrates, respectively, to transfer the pattern.
The printed Si surfaces were then immediately etched with a dilute potassium hydroxide [KOH] etching solution, in order to generate an array of nanoscale structures. The printed Au surfaces were then allowed to react with 16-mercaptohexadecanoic acid in order to functionalize (derivatize) the remaining bare regions, or were immediately selectively etched with the oxidizing type of wet etching (etchant) reagent, being a solution composed of: (i) potassium ferricyanide [K3Fe(CN)6] (Sigma- Aldrich), 0.001 M; (ii) potassium thiocyanate [KSCN], 0.1 M; and (iii) potassium hydroxide [KOH] (Frutarom Ltd., Israel), 1.0 M, which is particularly for wet etching of gold [Au], in order to generate an array of nanoscale structures.
Microscopy
The faceted sapphire templates, the elastomeric stamps, and the etched Si or Au nanostructures, were topographically imaged by tapping-mode AFM. The etched Si nanostructures were also imaged by scanning electron microscope (SEM). The Au patterned SAMs were imaged by contact (friction) mode AFM.
Topographic tapping-mode, and friction-mode images were taken in air using a commercial AFM (Veeco, Nanoscope IV, Multi-Mode). Friction-mode load: 40-50 nN.
Topographic images of the sapphire were obtained with Veeco NanoProbe™ AFM tips, model FESP (L: 221 μm, F0: 70 - 95 kHz). Topographic images of the PDMS stamps were obtained with NanoProbe™ tips, model: TESP (L: 128 μm, F0: 272 - 322 kHz).
Friction-mode images were obtained with ultrasharp carbon-whisker tips from
NanoTOOLS GmbH (Germany), model HDC (High Dense Carbon), with nominal radius of curvature R > 1 nm, mounted on short-thin and narrow Si3N4-cantilevers (L: 115. μm, W: 15 μm, k = 0.38 N/m). Scanning electron microscopy (FE-SEM) images were acquired with a LEO ULTRA, in ultra-high vacuum.
EXPERIMENTAL RESULTS EXAMPLE 1
[Using a self-assembled template prepared via a 'singular' (M-plane) crystal surface of a sapphire (alpha-alumina [C1-AI2O3]) [1,0,-1,0] crystal, for preparing arrays of gold [Au] nanowires on silicon [Si] substrate surfaces]
The results obtained for Example 1 are presented in Figs. 12a - 12f, each of which is described hereinbelow.
Fig. 12a is an atomic force microscope (AFM) topographic mode image of an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface includes an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a crystal surface; the self-assembled template corresponds to an annealed sapphire M-plane crystal surface (e.g., as shown in Fig. 1 Ia), characterized by R-plane and S-plane nanofacets having inclinations of 16.7 degrees and 32.6 degrees, respectively, pitch of 37 ± 3 nanometers (nm), and height (depth) of about 8 nanometers (run).
Fig. 12b is an atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary nanogrooved, nanofaceted surface replica element; the surface replica element (formed according to the embodiment illustrated in Fig. 4) corresponds to a polydimethylsiloxane (PDMS) cast or mold (elastomeric stamp) (whose nanogrooves have a pitch of 40 ± 5 nanometers (nm)) of the surface of the nanogrooved, nanofaceted self-assembled template (annealed sapphire M-plane crystal surface) shown in Fig. 12a.
Fig. 12c is an atomic force microscope (AFM) friction mode of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of 1-hexadecanethiol functionalized nanostrips (width of 10 - 20 nanometers (nm) and pitch of 50 ± 5 nanometers (nm)) on a gold [Au] with chemically bound 16-mercaptohexadecanoic acid substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by reacting a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate, with 16-mercaptohexadecanoic acid. Fig. 12d is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of gold [Au] nanowires on a silicon [Si] substrate surface; the array was generated (according to the embodiment illustrated in Fig. 4) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate.
Fig. 12e is a graphical plot of nanowire height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanowires, of the array of gold [Au] nanowires on the silicon [Si] substrate surface shown in Fig. 12d; the gold [Au] nanowires have a width (half-pitch) of about 20 nanometers (nm) and a height (diameter) of about 20 nanometers (nm).
Fig. 12f is anatomic force microscope (AFM) topographic mode image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a grid (waffle) type array of gold [Au] nanowires on a silicon [Si] substrate surface; the array was generated (according to embodiments illustrated in Figs. 4 and 5) by selective wet etching of a 1-hexadecanethiol functionalized nanopattern (formed by inking the surface replica element shown in Fig. 12b) on a gold [Au] substrate surface of a gold [Au] on silicon [Si] substrate.
EXAMPLE 2
[Using a self-assembled template prepared via a 'singular' (M-plane) crystal surface of a sapphire (alpha-alumina [(X-AI2O3]) [1,0,-1,0] crystal, for preparing arrays of nanogrooves on silicon [Si] (wafer) substrate surfaces]
The results obtained for Example 2 are presented in Figs. 13a - 13f, each of which is described hereinbelow.
Fig. 13a is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows an array of nanogrooves (pitch of about 50 nanometers (nm)) on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs. 4 and 7) by selective anisotropic wet etching of a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si] (wafer) substrate surface, wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig. Ha).
Fig. 13b is an atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13a, wherein the nanogrooves have a pitch of about 50 nanometers (run).
Fig. 13c is a three-dimensional projected atomic force microscope (AFM) topographic mode image of the surface of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Figs. 13a and 13b.
Fig. 13d is a graphical plot of nanogroove height (nanometers (nm)) as a function of lateral position (nanometers (nm)) spanning across the nanogrooves, of the array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13c, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a height (depth) of about 120 nanometers (nm).
Fig. 13e is a scanning electron microscope (SEM) image of the surface of an actual exemplary array of nanoscale structures on a substrate surface; the image shows a waffle type array of nanogrooves on a silicon [Si] (wafer) substrate surface; the array was generated (according to embodiments illustrated in Figs. 5 and 7) by selective anisotropic wet etching of a octadecyltrichlorosilane (OTS) functionalized nanopattern on a silicon [Si] (wafer) substrate surface, wherein the nanopattern was formed from an actual exemplary nanogrooved, nanofaceted self-assembled template whose surface included an array of nanoscale features (nanogrooves, nanofacets) spontaneously formed by treating (annealing) a sapphire M-plane crystal surface (e.g., as shown in Fig. 1 Ia).
Fig. 13f is an atomic force microscope (AFM) topographic mode (zoom) image of the surface of the waffle type array of nanogrooves on silicon [Si] (wafer) substrate surface shown in Fig. 13e, wherein the nanogrooves have a pitch of about 50 nanometers (nm) and a (depth) height of about 100 nanometers (nm).
The present invention, as illustratively described and exemplified hereinabove, has several beneficial and advantageous aspects, characteristics, and features, which are based on or/and a consequence of, the above illustratively described main aspects of novelty and inventiveness. Additionally, the present invention is clearly commercial applicable in the general field of nanoscale science (nanoscience) or technology (nanotechnology), encompassing, or at least associated with, sub-fields and areas such as nanoscale electronics (nanoelectronics), mechanics (nanomechanics), electrornechanics (nanoelectromechanics), and nanoscale semiconductor technology, focusing on methods, processes, or techniques, which are used for producing or fabricating arrays of nanoscale structures on substrate surfaces.
The present invention is generally applicable for producing (fabricating) various different types or kinds of arrays of various different types or kinds of nanoscale structures (e.g., nano wires, nanostrips, nanobelts, nanoparticles, or nanogrooves) on various different types or kinds of substrate surfaces (e.g., metallic, semi-metallic, non-metallic).
The produced (fabricated) arrays, in general, and the nanoscale structures and substrate surfaces thereof, can be of widely varying compositions, geometrical shapes, forms, configurations, size dimensions, and can exhibit widely varying physicochemical properties, characteristics, and behavior. The present invention is generally applicable to a wide variety of different nanoscience or nanotechnology (e.g., nanoelectronic, nanomechanical, nanoelectromechanical, and nanoscale semiconductor) based manufacturing processes which involve, or/and would benefit from, production (fabrication) of arrays of nanoscale structures on substrate surfaces, which, in turn, are used for manufacturing a wide variety of different nanoscale types of devices and components. Just a few examples of such are memories, logic gates, sensors, actuators, circuits, polarizers, and liquid crystal displays (LCDs). Such nanoscale devices and components, among many others not specifically mentioned herein, are used, or are potentially useful, in essentially every field of science and technology. Based upon the hereinabove illustratively described and exemplified aspects of novelty and inventiveness, and, beneficial and advantageous aspects, characteristics, and features, the present invention successfully addresses and overcomes the shortcomings and limitations, and widens the scope, of presently known techniques and methods for producing an array of nanoscale structures on a substrate surface. The present invention provides a practical, efficient, and cost effective, method for transferring or replicating periodic faceting patterns onto separate substrates. It is appreciated that certain aspects and characteristics of the invention, which are, for clarity, described in the context of separate embodiments, may also be provided in combination in a single embodiment. Conversely, various aspects and characteristics of the invention, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any suitable sub-combination.
While the invention has been described in conjunction with specific embodiments and examples thereof, it is evident that many alternatives, modifications, and variations, will be apparent to those skilled in the art. Accordingly, it is intended to embrace all such alternatives, modifications, and variations, that fall within the scope of the appended claims.
AU patents, patent applications, and publications, cited or referred to in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual patent, patent application, or publication, was specifically and individually indicated to be incorporated herein by reference. In addition, citation or identification of any reference in this application shall not be construed as an admission that such reference is available as prior art to the present invention.
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Claims

WHAT IS CLAIMED IS:
1. A method for producing an array of nanoscale structures on a substrate surface, the method comprising: providing a self-assembled template whose surface includes an array of nanoscale features spontaneously formed by treating a crystal surface; applying at least one material upon at least part of said array of said nanoscale features, for replicating said at least part of said array of said nanoscale features, such that said applied material(s) includes a replica configuration and shape of said at least part of said array of said nanoscale features; treating said applied material(s) while maintaining said replica configuration and shape thereof, for forming treated applied material(s) having said replica configuration and shape; contacting said replica configuration and shape of said treated applied material(s), with the substrate surface, for forming a combination structure having said replica configuration and shape in contact with the substrate surface; and processing said combination structure, for generating the array of the nanoscale structures on the substrate surface.
2. The method of claim 1, wherein said self-assembled template is composed of a crystalline substance selected from the group consisting of crystalline inorganic matter, crystalline organic matter, and a combination thereof.
3. The method of claim 2, wherein said crystalline inorganic matter is selected from the group consisting of: a crystalline single metal oxide, a crystalline mixed metal oxide, a crystalline inorganic salt, a periodic table group IV element, a compound of periodic table group IV elements, a compound of a periodic table group III element and a periodic table group V element, a compound of a periodic table group II element and a periodic table group VI element, a crystalline carbide, a crystalline suicide, a crystalline hydride, a crystalline elemental metal, and a crystalline alloy.
4. The method of claim 3, wherein said crystalline single metal oxide is selected from the group consisting of: alpha-aluminum oxide (sapphire) [Ot-Al2O3], alpha- silicon oxide (quartz) [α-SiO2], zinc oxide [ZnO], magnesium oxide [MgO], and titanium oxide [TiO2].
5. The method of claim 3, wherein said periodic table group IV element is elemental silicon [Si].
6. The method of claim 3, wherein said compound of a periodic table group III element and a periodic table group V element is gallium arsenide [GaAs].
7. The method of claim 2, wherein said crystalline organic matter is selected from the group consisting of: an amino acid, a protein, a carbohydrate, an aliphatic compound, and an aromatic compound.
8. The method of claim 2, wherein said combination of crystalline inorganic matter and crystalline organic matter is selected from the group consisting of: a crystalline organic salt, and a crystalline organometallic complex.
9. The method of claim 1, wherein said self-assembled template has a three-dimensional polyhedron bulk or overall geometrical shape or form, or a three-dimensional non-polyhedron curved bulk or overall geometrical shape or form.
10. The method of claim 9, wherein said three-dimensional polyhedron bulk or overall geometrical shape or form is selected from the group consisting of: a parallelpiped, a prism, and a pyramid.
11. The method of claim 9, wherein said three-dimensional non-polyhedron curved bulk or overall geometrical shape or form is selected from the group consisting of: a cylinder, a disc (disk), and a cone.
12. The method of claim 1, wherein said self-assembled template has a bulk or overall size wherein each size dimension of length (L)5 width (W), and height (thickness) (T), has a value or magnitude in a range of between about 0.1 nanometer (nm) and about 1 meter (m).
13. The method of claim 1, wherein said self-assembled template has a bulk or overall size wherein each size dimension of length (L), and width (W), has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 micron (μm) and about 1 centimeter (cm), (ii) a second range of between about 100 microns (μm) and about 1 meter (m), and (iii) a third range of between about 1 millimeter (mm) and about 1 meter (m).
14. The method of claim 1, wherein said self-assembled template, said array of nanoscale features corresponds to a parallelogram or parallelogram-like ordered arrangement or set of features, structures, or elements.
15. The method of claim 1, wherein said nanoscale features of said array are selected from the group consisting of nanoscale facets (nanofacets), nanoscale grooves (nanogrooves), and nanoscale steps (nanosteps).
16. The method of claim 1, wherein said array of nanoscale features, a single or individual nanoscale feature has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
17. The method of claim 1, wherein said array of nanoscale features, pitch between two neighboring similar nanoscale features has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
18. The method of claim 1, wherein said crystal surface is obtained by cutting at least part of a crystalline substance, or by depositing a crystalline substance onto a surface of another substance.
19. The method of claim 18, wherein said cutting is along a singular cutting plane, corresponding to a low-index plane, of a crystal.
20. The method of claim 18, wherein said cutting is along a vicinal cutting plane at a miscut tilt angle (θ) relative to nearest low-index plane of a crystal.
21. The method of claim 1, wherein said treating involves annealing said crystal surface.
22. The method of claim 1 , wherein said treating involves etching said crystal surface.
23. The method of claim 1, wherein said applying step is performed according to a material applying process selected from the group consisting of: casting (molding), and depositing.
24. The method of claim 23, wherein said casting (molding) process is selected from the group consisting of: a polymer cross-linking type of casting (molding) process, and a liquid-to-solid phase transition type of casting (molding) process.
25. The method of claim 23, wherein said depositing process is selected from the group consisting of: a physical deposition process, and a chemical deposition process.
26. The method of claim 1, wherein said applying step, said at least one material applied upon said at least part of said array is composed of a substance selected from the group consisting of organic matter, inorganic matter, and a combination thereof.
27. The method of claim 26, wherein said organic matter is an organic polymer.
28. The method of claim 27, wherein said organic polymer is selected from the group consisting of: a thermoplastic, a thermoset, an elastomer, and any combination thereof.
29. The method of claim 26, wherein said inorganic matter is selected from the group consisting of: a metal element, a metal alloy, a semi-metal element, a non-metal element, and any combination thereof.
30. The method of claim 29, wherein said metal element is selected from the group consisting of: a noble metal element, a transition metal element, and a main group metal element.
31. The method of claim 29, wherein said metal alloy is selected from the group consisting of: palladium-gold [PdAu], and platinum— iridium [PtIr].
32. The method of claim 29, wherein said semi-metal element is selected from the group consisting of: elemental silicon [Si], and elemental germanium [Ge].
33. The method of claim 29, wherein said non-metal element is selected from the group consisting of: an allotrope of carbon, and elemental boron [B].
34. The method of claim 29, wherein said combination of a metal element and a non-metal element, in a form of a compound, is selected from the group consisting of: indium oxide [In2O3], molybdenum diselinide [MoSe2], and boron nitride [BN].
35. The method of claim 26, wherein said combination of organic matter and inorganic matter is an organic-inorganic polymer.
36. The method of claim 35, wherein said organic-inorganic polymer is selected from the group consisting of: an organic-inorganic form of a thermoplastic, an organic- inorganic form of a thermoset, an organic-inorganic form of an elastomer, and any combination thereof.
37. The method of claim 1, wherein said applying step, said at least one material applied upon said at least part of said array has an amorphous structure, or a crystalline structure.
38. The method of claim 1, wherein for said applying step performed according to a casting (molding) type of material applying process, then, said treating step includes forming a stand-alone cast (mold) type of surface replica element having said replica configuration and shape.
39. The method of claim 38, wherein said treating step further includes inking, by using a suitable ink, surface of said cast (mold) type of said surface replica element.
40. The method of claim 39, wherein said ink is selected from the group consisting of a thiol compound based ink, and a silane compound based ink.
41. The method of claim 40, wherein said thiol compound based ink is a solution or suspension of a thiol compound selected from the group consisting of: n- hexadecanethiol, n-dodecanethiol, and n-octadecanethiol.
42. The method of claim 40, wherein said silane compound based ink is a solution or suspension of a silane compound selected from the group consisting of: octadecyltricholorosilane, 3-aminopropyl-triethoxisilane, and 3-mercaptopropyl- trimethoxysilane.
43. The method of claim 39, wherein said processing step includes forming a nanopattern (nanoscale pattern) upon the substrate surface.
44. The method of claim 43, wherein said nanopattern (nanoscale pattern) is formed by using said cast (mold) type of said surface replica element with a roller.
45. The method of claim 43, wherein said processing step further includes modifying said nanopattern (nanoscale pattern), by using a chemical functioiializing (derivatizing) procedure, or by using an etching procedure.
46. The method of claim 45, wherein said modifying is performed by using a thiol compound based chemical functionalizing (derivatizing) procedure, involving a thiol compound based chemical functionalizing (derivatizing) reagent.
47. The method of claim 45, wherein said modifying is performed by using a silane compound based type of functionalizing (derivatizing) procedure, involving a silane compound based chemical functionalizing (derivatizing) reagent.
48. The method of claim 45, wherein said modifying is performed by using a wet etching procedure, or a dry etching procedure.
49. The method of claim 1, wherein the array of the nanoscale structures generated on the substrate surface, the nanoscale structures are selected from the group consisting of: nanoscale wires (nanowires), nanoscale strips (nanostrips), nanoscale belts (nanobelts), nanoscale particles (nanoparticles), and nanoscale grooves (nanogrooves).
50. The method of claim 1, wherein a single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (run), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
51. The method of claim 1, wherein a single or individual nanoscale structure has size dimensions of width, and height (thickness), each of whose value or magnitude is in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
52. The method of claim 1, wherein the array of the nanoscale structures generated on the substrate surface, pitch between two neighboring similar nanoscale structures has a value or magnitude in a range selected from the group consisting of: (i) a first range of between about 1 nanometer (nm) and about 10 nanometers (nm), (ii) a second range of between about 10 nanometers (nm) and about 100 nanometers (nm), and (iii) a third range of between about 100 nanometers (nm) and about 1 micron (μm).
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