Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B82—NANOTECHNOLOGY
  • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
  • B82Y40/00—Manufacture or treatment of nanostructures
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping

Definitions

• the field of invention relates generally to micro- fabrication of structures. More particularly, the present invention is directed to methods and the imprinting materials to form layers having uniform etch characteristics.
• Micro-fabrication involves the fabrication of very small structures, e.g., having features on the order of micro-meters or smaller.
• One area in which micro-fabrication has had a sizeable impact is in the processing of integrated circuits.
• micro-fabrication becomes increasingly important.
• Micro-fabrication provides greater process control while allowing increased reduction of the minimum feature dimension of the structures formed.
• Other areas of development in which micro-fabrication has been employed include biotechnology, optical technology, mechanical systems and the like.
• An exemplary micro-fabrication technique is shown in United States patent number 6,334,960 to Willson et al. Willson et al.
• the method includes providing a substrate having a transfer layer.
• the transfer layer is covered with a polymerizable fluid composition.
• An imprint device makes mechanical contact with the polymerizable fluid.
• the imprint device includes a relief structure formed from lands and grooves.
• the polymerizable fluid composition fills the relief structure with the thickness of the polymerizable fluid in superimposition with the lands defining a residual thickness.
• the polymerizable fluid composition is then subjected to conditions to solidify and polymerize the same, forming a solidified polymeric layer on the transfer layer that contains a relief structure complimentary to that of the imprint device.
• the imprint device is then separated from the solidified polymeric layer such that a replica of the relief structure in the imprint device is formed in the solidified polymeric layer.
• the transfer layer and the solidified polymeric layer are subjected to an environment to selectively etch the transfer layer relative to the solidified polymeric layer such that a relief image is formed in the transfer layer.
• conventional etching processes may be employed to transfer the pattern of the relief structure into the substrate.
• Conventional etching processes form desired patterns in a layer employing an appropriate mask, e.g. a photoresist mask.
• the mask is typically deposited on the layer and patterned, forming a patterned mask.
• the patterned mask is then exposed to an etchant, such as ions in a dry etch process or a liquid acid in a wet etch technique, to remove portions of the layer exposed through the patterned mask.
• a desired characteristic of any etch process is to obtain a uniform etch rate over the surface being etched.
• the prior art is replete with attempts to control the etch rate during an etching process.
• United States patent number 6,132,632 to Haney, et al. discloses a method and apparatus for achieving etch rate uniformity in a reactive ion etcher.
• the reactive ion etcher generates a plasma within a vacuum chamber for etching a substrate disposed at a cathode of a reactor can within the chamber wherein the plasma emanates from a top plate of the reactor can, and is influenced by localized magnetic fields for locally controlling etch rates across the cathode to produce a uniform etch rate distribution across the cathode as a result of the localized magnetic field.
• the magnet array may be disposed between the top plate and the vacuum chamber for providing the localized magnetic fields.
• the magnet array includes a plurality of individual magnets and a grid plate for holding the individual magnets in position.
• United States patent number 6,344,105 to Daugherty et al. discloses a method and apparatus for ion-assisted etch processing in a plasma processing system.
• an elevated edge ring, a grooved edge ring, and a RF coupled edge ring are disclosed.
• the invention operates to improve etch rate uniformity across a substrate (wafer) .
• Etch rate uniformity improvement provided by the invention not only improves fabrication yields but also is cost efficient and does not risk particulate and/or heavy metal contamination.
• United States patent number 6,576,408 to Meador et al. discloses anti-reflective coating compositions having improved etch rates.
• the compositions are prepared from certain acrylic polymers and copolymers, such as glycidyl methacrylate reacted with non-polycyclic carboxylic acid dyes and non-polycyclic phenolic dyes, all light absorbing at a wavelength of 193 nm.
• the present invention includes a method and a composition to form a layer on a substrate having uniform etch characteristics.
• the method includes depositing a polymerizable liquid on the substrate as a composition of a plurality of components. Each of the components has a rate of evaporation associated therewith.
• the polymerizable composition is then solidified.
• a relative rate of evaporation associated with a subset of the plurality of components is established to be within a predetermined range.
• the present invention is based upon the discovery that etch non-uniformity in a layer that is formed by solidification of a deposited liquid is a function of the relative rates of evaporation of the components that form the layer.
• the composition is formed of a plurality of components, a subset of which has a substantially identical rate of evaporation for an interval of time.
• FIG. 1 is a perspective view of a lithographic system in accordance with the present invention.
• FIG. 2 is a simplified elevation view of a lithographic system, shown in Fig. 1, employed to create a patterned imprinting layer in accordance with one embodiment of the present invention
• FIG. 3 is a simplified elevation view of an imprint device spaced-apart from the patterned imprinting layer, shown in Fig. 1, after patterning in accordance with the present invention
• Fig. 4 is a top-down view of a region of the substrate, shown in Fig. 2, upon which patterning occurs employing a pattern of droplets of polymerizable fluid disposed thereon;
• Fig. 5 is a cross-sectional view of a layer, formed from a prior art polymerizable of the imprinting material, deposited on a substrate;
• Fig. 6 is a cross-sectional view of the layer shown in Fig. 5 after being subjected to an RIE etch process, in accordance with the prior art;
• Fig. 7 is a graph showing the rate of evaporation of the differing components of a silicon-containing polymerizable of the imprinting material in accordance with the present invention,- [0014]
• Fig. 8 is a cross-section view showing a release layer and a primer layer that may be employed in accordance with the present invention;
• Fig. 9 is a cross-section view showing a release layer applied to a planarization mold shown in Fig. 8.
• Fig. 10 is a cross-section view showing formation of layer upon a substrate in accordance with an alternate embodiment of the present invention.
• Fig. 1 depicts a lithographic system 10 in accordance with one embodiment of the present invention that includes a pair of spaced- apart bridge supports 12 having a bridge 14 and a stage support 16 extending therebetween. Bridge 14 and stage support 16 are spaced- apart. Coupled to bridge 14 is an imprint head 18, which extends from bridge 14 toward stage support 16. Disposed upon stage support 16 to face imprint head 18 is a motion stage 20. Motion stage 20 is configured to move with respect to stage support 16 along X and Y axes and may provide movement along the Z axis as well.
• a radiation source 22 is coupled to system 10 to impinge actinic radiation upon motion stage 20. As shown, radiation source 22 is coupled to bridge 14 and includes a power generator 23 connected to radiation source 22.
• Patterned mold 26 includes a plurality of features defined by a plurality of spaced- apart recesses 28 and projections 30. Projections 30 have a width W 1 , and recesses 28 have a width W 2 , both of which are measured in a direction that extends transversely to the Z axis.
• the plurality of features defines an original pattern that forms the basis of a pattern to be transferred into a substrate 32 positioned on motion stage 20.
• imprint head 18 is adapted to move along the Z axis and vary a distance "d" between patterned mold 26 and substrate 32.
• motion stage 20 may move template 24 along the Z-axis.
• the features on patterned mold 26 may be imprinted into a flowable region of substrate 32, discussed more fully below.
• Radiation source 22 is located so that patterned mold 26 is positioned between radiation source 22 and substrate 32, with actinic radiation generated by radiation source 22 propagating through patterned mold 26.
• patterned mold 26 be fabricated from material that is substantially transparent to the actinic radiation.
• Exemplary materials from which patterned mold 26 may be fabricated include fused-silica, quartz, silicon, organic polymers, siloxane polymers, borosilicate glass, fluorocarbon polymers, metal, and combinations of the above dependent upon the actinic radiation employed.
• IMPRIO 100TM An exemplary system is available under the trade name IMPRIO 100TM from Molecular Imprints, Inc. having a place of business at 1807-C Braker Lane, Suite 100, Austin, Texas 78758. The system description for the IMPRIO 100TM is available at www.molecularimprints.com.
• a flowable region such as an imprinting layer 34, is formed on a portion of surface 36 that presents a substantially smooth, if not planar, profile of a surface facing template 24.
• the flowable region is deposited as a plurality of spaced-apart discrete droplets 38 of imprinting material on substrate 32, discussed more fully below.
• the imprinting material may be selectively polymerized and cross-linked to record an inverse of the original pattern therein, defining a recorded pattern.
• the plurality of features on patterned mold 26 are shown as recesses 28 extending along a direction parallel to projections 30 that provide a cross-section of patterned mold 26 with a shape of a battlement.
• recesses 28 and projections 30 may correspond to virtually any feature required to create an integrated circuit and may be as small as a few tenths of nanometer.
• the pattern recorded in imprinting layer 34 is produced, in part, by mechanical contact with patterned mold 26.
• the distance “d” is reduced to allow imprinting layer 34 to come into mechanical contact with patterned mold 26, spreading droplets 38 so as to form imprinting layer 34 with a contiguous formation of the imprinting material over surface 36.
• distance "d” is reduced to allow sub-portions 46 of imprinting layer 34 to ingress into and fill recesses 28.
• sub-portions 48 of imprinting layer 34 in superimposition with projections 30 remain after the desired, usually minimum distance "d", has been reached, leaving sub- portions 46 with a thickness t lf and sub-portions 48 with a thickness, t 2 .
• Thickness t 2 is referred to as a residual thickness. Thicknesses "ti" and “t 2 " may be any thickness desired, dependent upon the application.
• the total volume contained in droplets 38 may be such so as to minimize, or avoid, a quantity of the imprinting material from extending beyond the region of surface 36 in superimposition with patterned mold 26, while obtaining desired thicknesses t x and t 2 , i.e., through capillary attraction of the imprinting material with patterned mold 26 and surface 36 and surface adhesion of the imprinting material.
• radiation source 22 produces actinic radiation that polymerizes and cross-links the imprinting material, forming solidified imprinting layer 134.
• the composition of imprinting layer 34 transforms from a fluidic imprinting material to a solidified material. This provides solidified imprinting layer 134 with a side having a shape that conforms to a shape of a surface 50 of patterned mold 26, shown more clearly in Fig. 5. As a result, solidified imprinting layer 134 is formed having recessions 52 and protrusions 54.
• step and repeat process is disclosed in published United States patent application number 2004/0008334, filed July 11, 2002 as application number 10/194,414, entitled “Step and Repeat Imprint Lithography, " which is assigned to the assignee of the present invention.
• the thickness differential between protrusions 54 and recessions 52 facilitates formation, in substrate 32, of a pattern corresponding to the pattern in solidified imprinting layer 134.
• the thickness differential between t ! and t 2 of protrusions 54 and recessions 52, respectively results in a greater amount of etch time being required before exposing regions of substrate 32 in superimposition with protrusions 54 compared with the time required for regions of substrate 32 in superimposition with recessions 52 being exposed. For a given etching process, therefore, etching will commence sooner in regions of substrate 32 in superimposition with recessions 52 than regions in superimposition with protrusions 54.
• the relational dimensions between the differing features of the pattern eventually transferred into substrate 32 may be controlled as desired.
• the etch characteristics of solidified imprinting layer 134, for a given etch chemistry be substantially uniform.
• the characteristics of the imprinting material are important to efficiently pattern substrate 32 in light of the unique patterning process employed.
• the imprinting material is deposited on substrate 32 as a plurality of discrete and spaced-apart droplets 38.
• the combined volume of droplets 38 is such that the imprinting material is distributed appropriately over an area of surface 36 where imprinting layer 34 is to be formed.
• the total volume of the imprinting material in droplets 38 defines the distance "d” , to be obtained so that the total volume occupied by the imprinting material in the gap defined between patterned mold 26 and the portion of substrate 32 in superimposition therewith once the desired distance "d” is reached is substantially equal to the total volume of the imprinting material in droplets 38.
• imprinting layer 34 is spread and patterned concurrently, with the pattern being subsequently set by exposure to the actinic radiation.
• the imprinting material provide rapid and even spreading of the imprinting material in droplets 38 over surface 36 so that all thicknesses t x are substantially uniform and all residual thicknesses t 2 are substantially uniform.
• An exemplary composition for the imprinting material consists of the following:
• COMPOSITION 1 isobornyl acrylate acryloxymethylbis (trimethylsiloxy)methylsilane ethylene glycol diacrylate 2-hydroxy-2-methyl-1-phenyl-propan-1-one
• COMPOSITION 2 isobornyl acrylate acryloxymethyltris (trimethylsiloxy) silane ethylene glycol diacrylate 2-hydroxy-2-methyl-1-phenyl-propan-1-one
• COMPOSITION 5 isobornyl acrylate acryloxymethylbis (trimethylsiloxy)methylsilane ethylene glycol diacrylate 2-hydroxy-2-methyl-1-phenyl-propan-1-one
• COMPOSITION 6 isobornyl acrylate acryloxymethyltris (trimethylsiloxy) silane ethylene glycol diacrylate 2-hydroxy-2-methyl-1-phenyl-propan-1-one
• the first silicon-free acrylate, isobornyl acrylate comprises approximately 42% of the composition, but the quantity present therein may range from 20-60%.
• the silicon-containing acrylate comprises approximately 37% of either of COMPOSITIONS 1, 2, 3 and 4, but the quantity present therein may range from 30-50%.
• the second silicon-free acrylate, cross-linker ethylene glycol diacrylate comprises approximately 18% of either of COMPOSITIONS 1, 2, 3 and 4, but the quantity present may range from 10% to 40%.
• the initiator, 2-hydroxy-2-methyl-l-phenyl-propan-l-one comprises approximately 0.5% to 5% and is responsive to UV radiation to facilitate cross-linkable and polymerization of COMPOSITIONS 1-4.
• COMPOSITIONS 5, 6, 7 and 8 in addition to the components of COMPOSITIONS 1-4, each includes the surfactant RiR 2 to comprise approximately 0.5% of the composition. The remaining components of COMPOSITIONS 5, 6, 7, and 8 are reduced proportionally to compensate for the addition of the surfactant.
• a surfactant is defined as any molecule, one tail of which is hydrophobic.
• Surfactants may be either fluorine-containing, e.g., include a fluorine chain, or may not include any fluorine in the surfactant molecule structure.
• Additional surfactants may include fluorinated polymeric surfactants available from 3M Company under the designations FLUORAD* FC4432 and/or FLUORAD* FC4430.
• other UV photo-initiators may be employed in conjunction with or in lieu of 2- hydroxy-2-methyl-l-phenyl-propan-l-one. It should be understood that non-photo-initiators may be employed such as thermal initiators. As a result, the actinic radiation employed to facilitate cross-linkable and polymerization would be thermal in nature, e.g., infrared radiation.
• an exemplary method of forming solidified imprinting layer 134 includes depositing a plurality of droplets in a pattern 100 to minimize trapping of gases when spreading the imprinting material over surface 36.
• pattern 100 is formed from a plurality of droplets 101-149 that are deposited sequentially, in the order number with droplet 101 being dispensed first and droplet 149 being dispensed last. It was found, however, that etch characteristics of the solidified imprinting layer 134 differed as a function of the position of the droplet in the drop dispense sequence, referred to as sequential etch differential (SED) .
• SED sequential etch differential
• the present invention overcomes SED by ensuring that specified polymerizable components are present in solidified imprinting layer 134 in a desired quantity.
• the desirable polymerizable components are the silicon-containing acrylate component and the non-silicon containing/silicon-free acrylate component that includes IBOA and the cross-linker component, EDGA, all of which are acrylates.
• the non-uniformity of the etch characteristics of solidified imprinting layer 134 is due to variations of the silicon content over the area thereof.
• the present invention attenuates, if not avoids, etch non- uniformity in a silicon-containing layer by configuring compositions for imprinting material in which the desirable components have desired rates of evaporation during a desired interval of time. Although it is possible to provide compositions in which the rate of evaporation of the desired components is substantially the same for an infinite period, this was determined to be unnecessary.
• the polymerizable components of COMPOSITIONS 1-8 are selected so as to have a desired relative rate of evaporation in the interval of time between deposition and exposure to actinic radiation.
• the remaining component, i.e., the photo-initiator, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, of COMPOSITIONS 1-4 is not considered a polymerizable component, although it becomes part of the polymerized structure. Therefore, the photo- initiator, 2-hydroxy-2-methyl-l-phenyl-propan-l-one does not contribute substantially to the structural characteristics of the resulting imprinting layer, which minimizes the need to match the rate of evaporation with the rate of evaporation of the acrylate components.
• the remaining components i.e., the photo-initiator, 2- hydroxy-2-methyl-1-phenyl-propan-1-one, and the surfactant, R 1 CH 2 CH 2 O(CH 2 CH 2 O) x H of COMPOSITIONS 5-8 are not considered polymerizable components. Further, it is desired that the non-polymerizable components of COMPOSITIONS 1-8 evaporate at a rate that is slower than the rate of evaporation of the acrylate components.
• Fig. 7 shown are various curves demonstrating the relative rate of evaporation for specified components in a 400 pL droplet of COMPOSITION 1, with the specified components being as follows : ethylene glycol diacrylate (EDGA) , acryloxymethylbis
• the 400 pL droplet was formed by deposition of multiple droplets, each having a volume of 80 pL, onto a common area to provide the 400 pL droplet with a radius of approximately 82 microns.
• the relative rate of evaporation between the components of COMPOSITION 1 is shown being less than 0.1%/second that translates to less than 2% for an interval of 20 seconds and approximately 5% over an interval of 60 seconds. Similar rates of evaporation for the polymerizable components of COMPOSITIONS 2- 8 are also found.
• COMPOSITIONS 1-8 each possess desirable characteristics in that the polymerizable components thereof have substantially uniform rates of evaporation that provide a substantially uniform density of silicon over the volume of solidified imprinting layer 134, shown in Fig. 3.
• solidified imprinting layer 134 was provided with a desired silicon content of no less than 8% by- weight over the given area of solidified imprinting layer 134.
• a maximum variation of the weight of the silicon content between any two regions of solidified imprinting layer 134 should be no greater than 5%.
• COMPOSITIONS 1-8 provide a desirable viscosity that may be in a range of 1 to 20 centipoise, with less than 5 centipoise being preferable. This facilitates deposition employing droplet dispense techniques.
• COMPOSITIONS 1-8 provide solidified imprinting layer 134 with a desired mechanical strength so that the break stress is greater than or equal to 15 MPa.
• substrate 32 may include a primer layer 96.
• Primer layer 96 has proved beneficial when surface 36 of substrate 32 appears rough when compared to the features dimensions to be formed in imprinting layer 34.
• Primer layer 96 may also function, inter alia, to provide a standard interface with imprinting layer 34, thereby reducing the need to customize each process to the imprinting material from which substrate 32 is formed.
• primer layer 96 may be formed from an organic imprinting material with the same or different etch characteristics as imprinting layer 34.
• primer layer 96 is fabricated in such a manner so as to possess a continuous, smooth, relatively defect-free surface that may exhibit excellent adhesion to imprinting layer 34.
• An exemplary material to use to form primer layer 96 is available from Brewer Science, Inc. of Rolla Missouri under the trade name DUV30J-6.
• the primer layer 96 is typically provided with a thickness to facilitate providing the desired surface profile and without being opaque to optical sensing equipment employed to detect patterns, such as alignment marks, on substrate 32 surface.
• primer layer 196 when an imprinting layer 34 is present upon a surface 136 of substrate 32 that has been previously patterned.
• primer layer 196 may be deposited employing any known deposition method, including droplet dispense techniques, spin-on techniques and the like.
• planarization mold 80 having a substantially smooth, if not planar, contact surface.
• the same may be treated with a low surface energy coating 98.
• Low surface energy coating 98 may be applied using any known process.
• processing techniques may include chemical vapor deposition method, physical vapor deposition, atomic layer deposition or various other techniques, brazing and the like.
• a low surface energy coating (not shown) may be applied to mold 26, shown in Fig. 2.
• fluorinated additives may be employed to improve release properties of the imprinting material.
• Fluorinated additives like surfactants, have a surface energy associated therewith that is lower than a surface energy of the imprinting material.
• An exemplary process by which to employ the aforementioned fluorinated additive is discussed by Bender et al. in MULTIPLE IMPRINTING IN UV- BASED NANOIMPRINT LITHOGRAPHY:RELATED MATERIAL ISSUES, Microelectronic Engineering pp. 61-62 (2002) .
• the low surface energy of the additive provides the desired release properties to reduce adherence of cross- linked and polymerized imprinting material molds 26 and 80.
• the surfactant may be used in conjunction with, or in lieu of, COMPOSITIONS 5-8 that include a surfactant.
• exemplary deposition techniques that may be employed to form solidified layer 134 include spin-on techniques, laser assisted direct imprinting (LADI) techniques and the like.
• LADI laser assisted direct imprinting
• An exemplary LADI technique is disclosed by Chou et al. in "Ultrafast and Direct Imprint of Nanostructures in Silicon," Nature, Col. 417, pp. 835-837, June 2002.
• any one of COMPOSITIONS 1-8 may be deposited on substrate 32 as layer 234.
• layer 234 may be patterned by employing mold 26.
• the benefits of the present invention become salient were layer 234 to be patterned employing step and repeat techniques, during which differing regions of layer 234 would be patterned and subsequently solidified, sequentially.

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• 2005
  • 2005-08-05 JP JP2007527859A patent/JP5020079B2/ja active Active
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