US20150240110A1 - Surface Treatments for Alignment of Block Copolymers - Google Patents
Surface Treatments for Alignment of Block Copolymers Download PDFInfo
- Publication number
- US20150240110A1 US20150240110A1 US14/698,365 US201514698365A US2015240110A1 US 20150240110 A1 US20150240110 A1 US 20150240110A1 US 201514698365 A US201514698365 A US 201514698365A US 2015240110 A1 US2015240110 A1 US 2015240110A1
- Authority
- US
- United States
- Prior art keywords
- film
- composition
- monomers
- polymer
- thickness
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N C=CC1=CC=C(C)C=C1 Chemical compound C=CC1=CC=C(C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- WHFHDVDXYKOSKI-UHFFFAOYSA-N C=CC1=CC=C(CC)C=C1 Chemical compound C=CC1=CC=C(CC)C=C1 WHFHDVDXYKOSKI-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N C=CC1=CC=C(Cl)C=C1 Chemical compound C=CC1=CC=C(Cl)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N C=CC1=CC=CC=C1 Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
Images
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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00015—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems
- B81C1/00023—Manufacture or treatment of devices or systems in or on a substrate for manufacturing microsystems without movable or flexible elements
- B81C1/00031—Regular or irregular arrays of nanoscale structures, e.g. etch mask layer
-
- 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
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/265—Selective reaction with inorganic or organometallic reagents after image-wise exposure, e.g. silylation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/002—Processes for applying liquids or other fluent materials the substrate being rotated
- B05D1/005—Spin coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0147—Film patterning
- B81C2201/0149—Forming nanoscale microstructures using auto-arranging or self-assembling material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31935—Ester, halide or nitrile of addition polymer
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
- Y10T428/31938—Polymer of monoethylenically unsaturated hydrocarbon
Definitions
- the present invention relates to a method for the synthesis and utilization of cross-linked substituted polystyrene copolymers as surface treatments (PXSTs) for control of the orientation of the physical features of a block copolymer deposited over the first copolymer.
- PXSTs surface treatments
- Such methods have many uses including multiple applications in the semiconductor industry including production of templates for nanoimprint lithography.
- Block copolymers self-assemble into regular patterns with features that are less than 100 nm [1] and can be exploited in nanomanufacturing applications such as microelectronics, solar cells, and membranes. Hexagonally packed cylinders aligned perpendicular to the substrate surface are one of the more useful nanostructures for these applications. Multiple surface treatment techniques have been reported that enable this orientation including surface treatment with alkyl chlorosilanes [2, 3], chemical patterning [4-6], and polymer “brushes” [7-10]. However, control over feature size and orientation is still lacking. What is needed is a method which provides a large process latitude in the necessary control over feature orientation.
- the present invention relates to a method for the synthesis and utilization of random cross-linked substituted polystyrene copolymers as surface treatments (PXSTs) for control of the orientation of the physical features of a block copolymer deposited over the first copolymer.
- PXSTs surface treatments
- Such methods have many uses including multiple applications in the semiconductor industry including production of templates for nanoimprint lithography. A wide range of surface energies can be obtained from these materials, and the results show the PXSTs need not be constituted from the identical two monomers in the block copolymer (BC) to obtain a wide process latitude for perpendicular orientation.
- the invention relates to a method, comprising: a) providing: i) a crosslinkable polymer comprising first and second monomers, ii) a block copolymer comprising third and fourth monomers, wherein said third and fourth monomers are chemically different from said first and second monomers; b) coating a surface with said crosslinkable polymer to create a first film; c) treating said first film under conditions such that crosslinkable polymer is crosslinked; d) coating said first film with said block copolymer to create a second film, and e) treating said second film under conditions such that nanostructures form, wherein the shape (and/or orientation) of the nanostructures is controlled (at least in part) by the chemical nature of said first film (and in some embodiments, it is also controlled in part by film thickness).
- the block copolymer forms cylindrical nanostructures, said cylindrical nanostructures being substantially vertically aligned with respect to the plane of the first film.
- said coating of step b) comprises spin coating.
- the thickness of said first film is greater than 5.5 nm and less than 30 nm. In one embodiment, the thickness of said first film is between 10 and 30 nm. In one embodiment, said thickness of said first film is between 15 and 20 nm.
- said crosslinkable polymer comprises an azido group on said first or second monomer (although other crosslinkable groups are used in other embodiments).
- the PXST can contain one or several comonomers, the comonomers need not be those that are used to produce the block copolymer.
- said treating of said first film in step c) comprises heating. Alternatively said treating comprises treating with light. Furthermore, in one embodiment said treating comprises light and heat.
- said third monomer is styrene and said block copolymer comprises polystyrene. In one embodiment, said block copolymer is a polystyrene-block-poly(methyl methacrylate) copolymer.
- said coating of said first film in step d) comprises spin coating. In one embodiment, wherein the thickness of said second film is between 10 and 100 nm.
- said thickness of said second film is between 20 and 70 nm.
- the treating of step e) comprises heating (e.g. under vacuum) so that the film is annealed.
- the nanostructures are less than 100 nm in height.
- the invention relates to a composition, comprising a second polymer film coated on a first polymer film, said first polymer film comprising first and second monomers, said second polymer film comprising third and fourth monomers, wherein said third and fourth monomers are chemically different from said first and second monomers.
- said second film comprises physical structures on a nanometer scale or “nano structures”, said physical structures controlled by the chemical nature of said first film.
- said second film comprises cylindrical nanostructures, said cylindrical nanostructures being substantially vertically aligned with respect to the plane of the first film. In one embodiment, the nanostructures are less than 100 nm in height (and more typically between 20 nm and 70 nm in height).
- said second film comprises a polystyrene-block-poly(methyl methacrylate) copolymer.
- said first polymer film is coated on a surface.
- said first polymer film is crosslinked.
- the thickness of said first film is between 10 and 30 nm. In other embodiments, said thickness of said first film is between 15 and 20 nm. In one embodiment, the thickness of said second film is between 10 and 100 nm. In other embodiments, said thickness of said second film is between 20 and 70 nm.
- FIG. 1 shows the synthesis of poly(styrene-b-methyl methacrylate) (PS-b-PMMA).
- PS-b-PMMA was anionically synthesized via standard Schlenk line techniques [11, 12].
- FIG. 2 shows the Refractive Index detector response from a Gel Permeation Chromatography (RI GPC) of PS-b-PMMA.
- FIG. 3 shows the of a family of polymers with different surface energies made by polymerization of monomers having a variety of different substituents.
- the characterization of P(SR)-r-P(SBnAz) and the impact of the various substituents are shown in Table 1.
- Table 1 shows the characterization of P(SR)-r-P(SBnAz) (shown in FIG. 3 ) with different substituents at the R position.
- FIG. 6 is a schematic which shows the difference between homopolymers, random polymers and block polymers.
- the present invention also contemplates styrene “derivatives” where the basic styrene structure is modified, e.g. by adding substituents to the ring (but preferably maintaining the vinyl group for polymerization).
- Derivatives can be, for example, hydroxy-derivatives, oxo-derivatives or halo-derivatives.
- hydrogen means —H
- hydroxy means —OH
- oxo means ⁇ O
- halo means independently —F, —Cl, —Br or —I.
- atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms.
- Isotopes include those atoms having the same atomic number but different mass numbers.
- isotopes of hydrogen include tritium and deuterium
- isotopes of carbon include 13 C and 14 C.
- one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s).
- one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s).
- Styrene is represented by the following structure:
- P-methylstyrene is an example of a styrene derivative and is represented by the following structure:
- P-chlorostyrene is another example of a styrene haloderivative and is represented by the following structure:
- the second film deposited over the first film develop “physical features on a nanometer scale,” “nanofeatures” or “nanostructures” with controlled orientation.
- These physical features have shapes and thicknesses.
- various structures can be formed by components of a block copolymer, such as vertical lamellae, in-plane cylinders, and vertical cylinders, and may depend on surface energies and film thickness.
- the second film develops cylindrical nanostructures, said cylindrical structures being substantially vertically aligned with respect to the plane of the first film. Orientation of structures in regions or domains at the nanometer level (i.e. “microdomains” or “nanodomains”) may be controlled to be approximately uniform.
- the methods described herein can generate structures with the desired size, shape, orientation, and periodicity. Thereafter, in one embodiment, these nanostructures may be etched or otherwise further treated.
- FIG. 3 Films thicker than 15 nm of polymer 3 ( FIG. 3 ) were spin-coated, heated to cross-link through the azide functionality, and thoroughly rinsed to remove any non-cross-linked materials. Surface energies of these films were obtained by goniometry with water, glycerol, and diiodomethane contact angles. Several measurements were made over the entire wafer, and the error was consistently +/ ⁇ 2 dyne/cm. FIG. 4 displays these data and shows that the substituents affect the surface energy of the film. Additionally, the surface energies of non-cross-linked homopolymer films of PS and PMMA and a wafer cleaned with piranha were measured, and these values are consistent with the literature [2, 13].
- the invention relates to the PS-b-PMMA films of various thicknesses were coated on the PXSTs. These were annealed and investigated by AFM.
- the AFM images display very different process windows for perpendicular orientation of the PXSTs.
- the Cl-substituted PXST resulted in perpendicular cylinders for block film thicknesses of 30 to 35 nm, and the PXST with a Br substituent had a process window from 23 to 41 nm ( FIG. 5 ).
- These process window results are similar to other polymeric surface treatments reported by Nealey [14] and Hawker and Russell [10, 15, 16]. This leads to the conclusion that a PXST need not consist of the same monomers as the BC being coated.
- the present invention relates to the synthesis of the polystyrene-containing block copolymer “PS-b-PMMA.”
- PS-b-PMMA was anionically synthesized via standard Schlenk line techniques ( FIG. 1 ) [11, 12].
- 1 H-NMR showed the resulting polymer is 31 mol % PMMA, which corresponds to a volume fraction of 0.27 [17]. This is within the range for cylinder morphology [1].
- FIG. 2 shows GPC chromatograms of the PS aliquot and PS-b-PMMA.
- the invention relates to the synthesis of P(SR)-r-P(SBnAz).
- SR SR-r-P(SBnAz)
- several commercially available styrene derivatives were radically copolymerized with vinyl benzyl chloride to investigate the role of substituents on the surface energy of PS.
- nucleophilic substitution of the chloride with azide ion led to cross-linkable polymers 3 ( FIG. 3 ).
- the presence of the azide was confirmed by IR, and the resulting polymers are described in Table 1.
- Film thicknesses were determined with a J. A. Woollam Co, Inc. VB 400 VASE Ellipsometer using wavelengths from 382 to 984 nm with a 70° angle of incidence. Contact angles were measured with a Ramé-Hart, inc. NRL C.A. Goniometer (Model #100-00). A Heraeus Vacutherm Type VT 6060 P from Kendro was used to thermally anneal the films under reduced pressure. A Digital Instruments Dimension 3100 atomic force microscope with NCHR Pointprobe® Non-Contact Mode tips with a force constant of 42 N/m was used to collect AFM images.
- PS-b-PMMA was synthesized as previously reported by sequential anionic polymerization of styrene and methyl methacrylate in THF at ⁇ 78° C. under Ar atmosphere via standard Schlenk line techniques [11].
- the initiator was sec-BuLi; diphenyl ethylene was used to properly initiate MMA, and NO was added to suppress side reactions during MMA propagation [12].
- polymer 2 (1.0 g) and sodium azide (3 equiv/BnCl) were dissolved in DMF (20 mL) and stirred overnight at room temperature (rt). The polymer was precipitated in MeOH, filtered, redissolved in THF (10 mL), and stirred with H 2 O (1 mL) to remove any unreacted salts. Finally, the polymer was isolated by precipitation in 0° C. MeOH, filtered, and dried in vacuo to yield white powder 3. Typical yields over these two steps were 50%; IR (KBr) 2100 cm ⁇ 1. Complete characterization is shown in Table 1.
- a film of P(SR)-r-P(SBnAz) was spin coated from a 1.0 wt % solution in toluene at 3770 rpm for 30 sec onto a wafer that had been rinsed with IPA and acetone. The wafer was immediately baked at 250° C. for 5 min to cross-link the film. The wafer was then submerged in toluene for 2 min, blown dry, submerged again for 2 min, and blown dry. Typical film thicknesses as determined by ellipsometry were 15-20 nm.
- ⁇ SV is the surface energy of the solid-vapor interface
- ⁇ SL is the interfacial energy of the solid-liquid interface
- ⁇ LV is the surface tension of the fluid
- ⁇ is the angle between the solid and liquid
- ⁇ eq is the equilibrium spreading pressure, which is approximately zero for polymeric surfaces.
- Eq 2 describes the interfacial energy between two components ( ⁇ 12 ) as the sum of the dispersion ( ⁇ 12 Lw ) and acid-base components ( ⁇ 12 AB ).
- Eq 3 relates the surface energy of the film and cosine of the contact angle ( ⁇ 2 cos ⁇ ) to the dispersion ( ⁇ 2 LW ), Lewis acid ( ⁇ 2 P+ ), and Lewis base components ( ⁇ 2 P ⁇ ).
- H 2 O, diiodomethane, and glycerol a system of equations was solved to obtain the surface energy of the PXST films.
- a clean, surface-treated wafer was spin coated with a film of PS-b-PMMA from toluene at various speeds and concentrations to give 20-70 nm films as determined by ellipsometry. Once cast, the wafer shards were annealed at 170° C. under reduced pressure for 12-18 h.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Nanotechnology (AREA)
- Analytical Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Treatments Of Macromolecular Shaped Articles (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
Abstract
The present invention relates to a method the synthesis and utilization of random, cross-linked, substituted polystyrene copolymers as polymeric cross-linked surface treatments (PXSTs) to control the orientation of physical features of a block copolymer deposited over the first copolymer. Such methods have many uses including multiple applications in the semi-conductor industry including production of templates for nanoimprint lithography.
Description
- The present invention relates to a method for the synthesis and utilization of cross-linked substituted polystyrene copolymers as surface treatments (PXSTs) for control of the orientation of the physical features of a block copolymer deposited over the first copolymer. Such methods have many uses including multiple applications in the semiconductor industry including production of templates for nanoimprint lithography.
- Appropriately structured block copolymers (BCs) self-assemble into regular patterns with features that are less than 100 nm [1] and can be exploited in nanomanufacturing applications such as microelectronics, solar cells, and membranes. Hexagonally packed cylinders aligned perpendicular to the substrate surface are one of the more useful nanostructures for these applications. Multiple surface treatment techniques have been reported that enable this orientation including surface treatment with alkyl chlorosilanes [2, 3], chemical patterning [4-6], and polymer “brushes” [7-10]. However, control over feature size and orientation is still lacking. What is needed is a method which provides a large process latitude in the necessary control over feature orientation.
- The present invention relates to a method for the synthesis and utilization of random cross-linked substituted polystyrene copolymers as surface treatments (PXSTs) for control of the orientation of the physical features of a block copolymer deposited over the first copolymer. Such methods have many uses including multiple applications in the semiconductor industry including production of templates for nanoimprint lithography. A wide range of surface energies can be obtained from these materials, and the results show the PXSTs need not be constituted from the identical two monomers in the block copolymer (BC) to obtain a wide process latitude for perpendicular orientation.
- In one embodiment, the invention relates to a method, comprising: a) providing: i) a crosslinkable polymer comprising first and second monomers, ii) a block copolymer comprising third and fourth monomers, wherein said third and fourth monomers are chemically different from said first and second monomers; b) coating a surface with said crosslinkable polymer to create a first film; c) treating said first film under conditions such that crosslinkable polymer is crosslinked; d) coating said first film with said block copolymer to create a second film, and e) treating said second film under conditions such that nanostructures form, wherein the shape (and/or orientation) of the nanostructures is controlled (at least in part) by the chemical nature of said first film (and in some embodiments, it is also controlled in part by film thickness). In one embodiment, the block copolymer forms cylindrical nanostructures, said cylindrical nanostructures being substantially vertically aligned with respect to the plane of the first film. In one embodiment, said coating of step b) comprises spin coating. In one embodiment, the thickness of said first film is greater than 5.5 nm and less than 30 nm. In one embodiment, the thickness of said first film is between 10 and 30 nm. In one embodiment, said thickness of said first film is between 15 and 20 nm. In one embodiment, said crosslinkable polymer comprises an azido group on said first or second monomer (although other crosslinkable groups are used in other embodiments). In one embodiment, the PXST can contain one or several comonomers, the comonomers need not be those that are used to produce the block copolymer. In one embodiment, said treating of said first film in step c) comprises heating. Alternatively said treating comprises treating with light. Furthermore, in one embodiment said treating comprises light and heat. In one embodiment, said third monomer is styrene and said block copolymer comprises polystyrene. In one embodiment, said block copolymer is a polystyrene-block-poly(methyl methacrylate) copolymer. In one embodiment, said coating of said first film in step d) comprises spin coating. In one embodiment, wherein the thickness of said second film is between 10 and 100 nm. In one embodiment, said thickness of said second film is between 20 and 70 nm. In one embodiment, the treating of step e) comprises heating (e.g. under vacuum) so that the film is annealed. In one embodiment, the nanostructures are less than 100 nm in height.
- In further embodiments, the invention relates to a composition, comprising a second polymer film coated on a first polymer film, said first polymer film comprising first and second monomers, said second polymer film comprising third and fourth monomers, wherein said third and fourth monomers are chemically different from said first and second monomers. In one embodiment, said second film comprises physical structures on a nanometer scale or “nano structures”, said physical structures controlled by the chemical nature of said first film. In one embodiment, said second film comprises cylindrical nanostructures, said cylindrical nanostructures being substantially vertically aligned with respect to the plane of the first film. In one embodiment, the nanostructures are less than 100 nm in height (and more typically between 20 nm and 70 nm in height).
- In one embodiment, said second film comprises a polystyrene-block-poly(methyl methacrylate) copolymer. In one embodiment, said first polymer film is coated on a surface. In one embodiment, said first polymer film is crosslinked. In one embodiment of the composition, the thickness of said first film is between 10 and 30 nm. In other embodiments, said thickness of said first film is between 15 and 20 nm. In one embodiment, the thickness of said second film is between 10 and 100 nm. In other embodiments, said thickness of said second film is between 20 and 70 nm.
- For a more complete understanding of the features and advantages of the present invention, reference is now made to the detailed description of the invention along with the accompanying figures.
-
FIG. 1 shows the synthesis of poly(styrene-b-methyl methacrylate) (PS-b-PMMA). PS-b-PMMA was anionically synthesized via standard Schlenk line techniques [11, 12]. -
FIG. 2 shows the Refractive Index detector response from a Gel Permeation Chromatography (RI GPC) of PS-b-PMMA. -
FIG. 3 shows the of a family of polymers with different surface energies made by polymerization of monomers having a variety of different substituents. The characterization of P(SR)-r-P(SBnAz) and the impact of the various substituents are shown in Table 1. -
FIG. 4 shows the surface energies of PXSTs where R=tBu, Cl, Me, H, and Br (blue), homopolymers (red), and wafer (grey). -
FIG. 5 shows an atomic force microscopy (AMF) phase image of PS-b-PMMA on PXST where (R=Br). - Table 1 shows the characterization of P(SR)-r-P(SBnAz) (shown in
FIG. 3 ) with different substituents at the R position. -
FIG. 6 is a schematic which shows the difference between homopolymers, random polymers and block polymers. - To facilitate the understanding of this invention, a number of terms are defined below. Terms defined herein have meanings as commonly understood by a person of ordinary skill in the areas relevant to the present invention. Terms such as “a”, “an” and “the” are not intended to refer to only a singular entity, but include the general class of which a specific example may be used for illustration. The terminology herein is used to describe specific embodiments of the invention, but their usage does not delimit the invention, except as outlined in the claims.
- The present invention also contemplates styrene “derivatives” where the basic styrene structure is modified, e.g. by adding substituents to the ring (but preferably maintaining the vinyl group for polymerization). Derivatives can be, for example, hydroxy-derivatives, oxo-derivatives or halo-derivatives. As used herein, “hydrogen” means —H; “hydroxy” means —OH; “oxo” means ═O; “halo” means independently —F, —Cl, —Br or —I.
- In addition, atoms making up the compounds of the present invention are intended to include all isotopic forms of such atoms. Isotopes, as used herein, include those atoms having the same atomic number but different mass numbers. By way of general example and without limitation, isotopes of hydrogen include tritium and deuterium, and isotopes of carbon include 13C and 14C. Similarly, it is contemplated that one or more carbon atom(s) of a compound of the present invention may be replaced by a silicon atom(s). Furthermore, it is contemplated that one or more oxygen atom(s) of a compound of the present invention may be replaced by a sulfur or selenium atom(s).
- Styrene is represented by the following structure:
- 1-(chloromethyl)-4-vinylbenzene is represented by the following structure:
- P-methylstyrene is an example of a styrene derivative and is represented by the following structure:
- P-chlorostyrene is another example of a styrene haloderivative and is represented by the following structure:
- It is desired that the second film deposited over the first film develop “physical features on a nanometer scale,” “nanofeatures” or “nanostructures” with controlled orientation. These physical features have shapes and thicknesses. For example, various structures can be formed by components of a block copolymer, such as vertical lamellae, in-plane cylinders, and vertical cylinders, and may depend on surface energies and film thickness. In a preferred embodiment, the second film develops cylindrical nanostructures, said cylindrical structures being substantially vertically aligned with respect to the plane of the first film. Orientation of structures in regions or domains at the nanometer level (i.e. “microdomains” or “nanodomains”) may be controlled to be approximately uniform. The methods described herein can generate structures with the desired size, shape, orientation, and periodicity. Thereafter, in one embodiment, these nanostructures may be etched or otherwise further treated.
- In the course of our efforts to employ non-traditional monomers for BCs, we became interested in the effect of surface energy on BC orientation. Films thicker than 15 nm of polymer 3 (
FIG. 3 ) were spin-coated, heated to cross-link through the azide functionality, and thoroughly rinsed to remove any non-cross-linked materials. Surface energies of these films were obtained by goniometry with water, glycerol, and diiodomethane contact angles. Several measurements were made over the entire wafer, and the error was consistently +/−2 dyne/cm.FIG. 4 displays these data and shows that the substituents affect the surface energy of the film. Additionally, the surface energies of non-cross-linked homopolymer films of PS and PMMA and a wafer cleaned with piranha were measured, and these values are consistent with the literature [2, 13]. - In one embodiments, the invention relates to the PS-b-PMMA films of various thicknesses were coated on the PXSTs. These were annealed and investigated by AFM. The AFM images display very different process windows for perpendicular orientation of the PXSTs. The Cl-substituted PXST resulted in perpendicular cylinders for block film thicknesses of 30 to 35 nm, and the PXST with a Br substituent had a process window from 23 to 41 nm (
FIG. 5 ). These process window results are similar to other polymeric surface treatments reported by Nealey [14] and Hawker and Russell [10, 15, 16]. This leads to the conclusion that a PXST need not consist of the same monomers as the BC being coated. - It is not intended that the present invention be limited to specific block polymers. However, to illustrate the invention, examples of various copolymers are provided. In one embodiment, the invention relates to the synthesis of the polystyrene-containing block copolymer “PS-b-PMMA.” PS-b-PMMA was anionically synthesized via standard Schlenk line techniques (
FIG. 1 ) [11, 12]. 1H-NMR showed the resulting polymer is 31 mol % PMMA, which corresponds to a volume fraction of 0.27 [17]. This is within the range for cylinder morphology [1]. The Mn of the PS aliquot was 45.8 kDa with a PDI of 1.18; the total molecular weight was 65.6 kDa with a PDI of 1.18.FIG. 2 shows GPC chromatograms of the PS aliquot and PS-b-PMMA. - In one embodiment, the invention relates to the synthesis of P(SR)-r-P(SBnAz). In a procedure similar to Hawker et al. [9], several commercially available styrene derivatives were radically copolymerized with vinyl benzyl chloride to investigate the role of substituents on the surface energy of PS. Upon isolation of 2, nucleophilic substitution of the chloride with azide ion led to cross-linkable polymers 3 (
FIG. 3 ). The presence of the azide was confirmed by IR, and the resulting polymers are described in Table 1. - Materials.
- All reagents were purchased from Sigma-Aldrich Chemical Co. and used without further purification unless otherwise noted. THF was purchased from JT Baker. 100 mm silicon wafers were purchased from Silicon Quest International.
- Instrumentation.
- All 1H and 13C NMR spectra were recorded on a Varian Unity Plus 400 MHz instrument. All chemical shifts are reported in ppm downfield from TMS using the residual protonated solvent as an internal standard (CDCl3, 1H 7.26 ppm and 13C 77.0 ppm). Molecular weight and polydispersity data were measured using an Agilent 1100 Series Isopump and Autosampler and a Viscotek Model 302 TETRA Detector Platform with 3 I-series Mixed Bed High MW columns against polystyrene standards. Polymer solutions were filtered with 0.20 μm PTFE filters prior to spin coating. Films were spin coated and baked on a Brewer CEE 100CB Spincoater & Hotplate. Film thicknesses were determined with a J. A. Woollam Co, Inc. VB 400 VASE Ellipsometer using wavelengths from 382 to 984 nm with a 70° angle of incidence. Contact angles were measured with a Ramé-Hart, inc. NRL C.A. Goniometer (Model #100-00). A Heraeus Vacutherm Type VT 6060 P from Kendro was used to thermally anneal the films under reduced pressure. A Digital Instruments Dimension 3100 atomic force microscope with NCHR Pointprobe® Non-Contact Mode tips with a force constant of 42 N/m was used to collect AFM images.
- PS-b-PMMA was synthesized as previously reported by sequential anionic polymerization of styrene and methyl methacrylate in THF at −78° C. under Ar atmosphere via standard Schlenk line techniques [11]. The initiator was sec-BuLi; diphenyl ethylene was used to properly initiate MMA, and NO was added to suppress side reactions during MMA propagation [12].
- In a procedure adopted from Hawker et al. [9], a substituted styrene (20 mmol) and vinyl benzyl chloride (0.62 mmol) were radically copolymerized in refluxing THF (20 mL) for 48 h with enough AIBN to obtain a theoretical MW of 25 kDa. Once
polymer 2 was precipitated in 0° C. MeOH, filtered, and dried in vacuo, the mol ratio of substituted styrene to vinyl benzyl chloride was determined by 1H-NMR. Taking into account this ratio and the Mn as determined by GPC, polymer 2 (1.0 g) and sodium azide (3 equiv/BnCl) were dissolved in DMF (20 mL) and stirred overnight at room temperature (rt). The polymer was precipitated in MeOH, filtered, redissolved in THF (10 mL), and stirred with H2O (1 mL) to remove any unreacted salts. Finally, the polymer was isolated by precipitation in 0° C. MeOH, filtered, and dried in vacuo to yieldwhite powder 3. Typical yields over these two steps were 50%; IR (KBr) 2100 cm−1. Complete characterization is shown in Table 1. - A film of P(SR)-r-P(SBnAz) was spin coated from a 1.0 wt % solution in toluene at 3770 rpm for 30 sec onto a wafer that had been rinsed with IPA and acetone. The wafer was immediately baked at 250° C. for 5 min to cross-link the film. The wafer was then submerged in toluene for 2 min, blown dry, submerged again for 2 min, and blown dry. Typical film thicknesses as determined by ellipsometry were 15-20 nm.
- Contact angles were measured with H2O, diiodomethane, and glycerol, and analyzed via the Young-Dupre equation (Eq 1) and the Acid-Base Surface Energy Model (Eq 2) [18].
-
γSV=γSL+γLV cos θ−πeq Eq 1 - γSV is the surface energy of the solid-vapor interface, γSL is the interfacial energy of the solid-liquid interface, γLV is the surface tension of the fluid, θ is the angle between the solid and liquid, and πeq is the equilibrium spreading pressure, which is approximately zero for polymeric surfaces.
-
γ12=γ12 LW+γ12AB Eq 2 -
−γ2 cos θ=γ2 LW−2(γ1 LWγ2 LW)1/2+2[(γ2 P+γ2 P−)1/2−(γ1 P+γ2 P−)1/2−(γ1 P−γ2 P+)1/2]Eq 3 - Briefly,
Eq 2 describes the interfacial energy between two components (γ12) as the sum of the dispersion (γ12 Lw) and acid-base components (γ12 AB).Eq 3 relates the surface energy of the film and cosine of the contact angle (−γ2 cos θ) to the dispersion (γ2 LW), Lewis acid (γ2 P+), and Lewis base components (γ2 P−). Using literature values for H2O, diiodomethane, and glycerol, a system of equations was solved to obtain the surface energy of the PXST films. - Spin Coating and Annealing.
- A clean, surface-treated wafer was spin coated with a film of PS-b-PMMA from toluene at various speeds and concentrations to give 20-70 nm films as determined by ellipsometry. Once cast, the wafer shards were annealed at 170° C. under reduced pressure for 12-18 h.
-
- 1. Bates, F. S., and Fredrickson, G. H. (1999) Block Copolymers—Designer Soft Materials Phys. Today 52, 32-38.
- 2. Peters, R. D., Yang, X. M., Kim, T. K., Sohn, B. H., and Nealey, P. F. (2000) Using Self-Assembled Monolayers Exposed to X-Rays to Control the Wetting Behavior of Thin Films of Diblock Copolymers, Langmuir 16, 4625-4631.
- 3. Niemz, A., Bandyopadhyay, K., Tan, E., Cha, K., and Baker, S. M. (2006) Fabrication of Nanoporous Templates from Diblock Copolymer Thin Films on Alkylchlorosilane-Neutralized Surfaces, Langmuir 22, 11092-11096.
- 4. Ruiz, R., Kang, H., Detcheverry, F. A., Dobisz, E., Kercher, D. S., Albrecht, T. R., de Pablo, J. J., and Nealey, P. F. (2008) Density Multiplication and Improved Lithography by Directed Block Copolymer Assembly, Science 321, 936-939.
- 5. Stoykovich, M. P., Müller, M., Kim, S O., Solak, H. H., Edwards, E. W., Pablo, J. J. d., and Nealey, P. F. (2005) Directed Assembly of Block Copolymer Blends into Nonregular Device-Oriented Structures, Science 5727, 1442-1446.
- 6. Kim, S. 0., Kim, B. H., Kim, K., Koo, C. M., Stoykovich, M. P., Nealey, P. F., and Solak, H. H. (2006) Defect Structure in Thin Films of a Lamellar Block Copolymer Self-Assembled on Neutral Homogeneous and Chemically Nanopatterned Surfaces, Macromolecules 39, 5466-5470.
- 7. Mansky, P., Liu, Y., Huang, E., Russell, T. P., and Hawker, C. (1997) Controlling Polymer-Surface Interactions with Random Copolymer Brushes Science 275, 1454-1457.
- 8. Han, E., In, I., Park, S.-M., La, Y.-H., Wang, Y, Nealey, P. F., and Gopalan, P. (2007) Photopattemable Imaging Layers for Controlling Block Copolymer Microdomain Orientation, Adv. Mater 19, 4448-4452.
- 9. Bang, J., Bae, J., Löwenhielm, P., Spiessberger, C., Given-Beck, S. A., Russell, T. P., and Hawker, C. J. (2007) Facile Routes to Patterned Surface Neutralization Layers for Block Copolymer Lithography, Adv. Mater. 19, 4552-4557.
- 10. Ham, S., Shin, C., Kim, E., Ryu, D. Y, Jeong, U., Russell, T. P., and Hawker, C. J. (2008) Microdomain Orientation of Ps-B-Pmma by Controlled Interfacial Interactions,
Macromolecules 41, 6431-6437. - 11. Uhrig, D., and Mays, J. W. (2005) Experimental Techniques in High-Vacuum Anionic Polymerization, J. Polym. Sci. A. 43, 6179-6222.
- 12. Allen, R. D., Long, T. E., and McGrath, J. E. (1986) Preparation. of High Purity, Anionic Polymerization Grade Alkyl Methacrylate Monomers Polym. Bull. 15, 127-134.
- 13. Jung, Y. S., and Ross, C. A. (2007) Orientation-Controlled Self-Assembled Nanolithography Using a Polystyreneâ̂′Polydimethylsiloxane Block Copolymer, Nano Lett. 7, 2046-2050.
- 14. Han, E., Stuen, K. O., Leolukman, M., Liu, C.-C., Nealey, P. F., and Gopalan, P. (2009) Perpendicular Orientation of Domains in Cylinder-Forming Block Copolymer Thick Films by Controlled Interfacial Interactions, Macromolecules 42, 4896-4901.
- 15. Ryu, D. Y, Wang, J.-Y., Lavery, K. A., Drockenmuller, E., Satija, S. K., Hawker, C. J., and Russell, T. P. (2007) Surface Modification with Cross-Linked Random Copolymers:‰ Minimum Effective Thickness,
Macromolecules 40, 4296-4300. - 16. Ryu, D. Y, Ham, S., Kim, E., Jeong, U., Hawker, C. J., and Russell, T. P. (2009) Cylindrical Microdomain Orientation of Ps-B-Pmma on the Balanced Interfacial Interactions: Composition Effect of Block Copolymers, Macromolecules 42, 4902-4906.
- 17. Fetters, L. J., Lohse, D. J., Richter, D., Witten, T. A., and Zirkel, A. (1994) Connection between Polymer Molecular Weight, Density, Chain Dimensions, and Melt Viscoelastic Properties, Macromolecules 27, 4639-4647.
- 18. Van Oss, C. J., Good, R. J., and Chaudhury, M. K. (1988) Additive and Nonadditive Surface Tension Components and the Interpretation of Contact Angles, Langmuir 4, 884-891.
Claims (11)
1-13. (canceled)
14. A composition, comprising a second polymer film coated on a first polymer film, said first polymer film comprising first and second monomers, said second polymer film comprising third and fourth monomers, wherein said third and fourth monomers are chemically different from said first and second monomers.
15. The composition of claim 14 , wherein said second film comprises nanostructures, said structures controlled by the chemical nature of said first film.
16. The composition of claim 15 , wherein said nanostructures comprise cylindrical nanostructures, said cylindrical nanostructures being substantially vertically aligned with respect to the plane of the first film.
17. The composition of claim 14 , wherein said second film comprises a polystyrene-block-poly(methyl methacrylate) copolymer.
18. The composition of claim 14 , wherein said first polymer film is coated on a surface.
19. The composition of claim 14 , wherein said first polymer film is crosslinked.
20. The composition of claim 14 , wherein the thickness of said first film is between 10 and 30 nm.
21. The composition of claim 20 , wherein said thickness of said first film is between 15 and 20 nm.
22. The composition of claim 14 , wherein the thickness of said second film is between 10 and 100 nm.
23. The composition of claim 22 , wherein said thickness of said second film is between 20 and 70 nm.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US14/698,365 US20150240110A1 (en) | 2010-03-18 | 2015-04-28 | Surface Treatments for Alignment of Block Copolymers |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US31527810P | 2010-03-18 | 2010-03-18 | |
PCT/US2011/028858 WO2011116217A1 (en) | 2010-03-18 | 2011-03-17 | Surface treatments for alignment of block copolymers |
US201213583518A | 2012-10-04 | 2012-10-04 | |
US14/698,365 US20150240110A1 (en) | 2010-03-18 | 2015-04-28 | Surface Treatments for Alignment of Block Copolymers |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US2011/028858 Division WO2011116217A1 (en) | 2010-03-18 | 2011-03-17 | Surface treatments for alignment of block copolymers |
US13/583,518 Division US9120947B2 (en) | 2010-03-18 | 2011-03-17 | Surface treatments for alignment of block copolymers |
Publications (1)
Publication Number | Publication Date |
---|---|
US20150240110A1 true US20150240110A1 (en) | 2015-08-27 |
Family
ID=44649607
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/583,518 Expired - Fee Related US9120947B2 (en) | 2010-03-18 | 2011-03-17 | Surface treatments for alignment of block copolymers |
US14/698,365 Abandoned US20150240110A1 (en) | 2010-03-18 | 2015-04-28 | Surface Treatments for Alignment of Block Copolymers |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US13/583,518 Expired - Fee Related US9120947B2 (en) | 2010-03-18 | 2011-03-17 | Surface treatments for alignment of block copolymers |
Country Status (6)
Country | Link |
---|---|
US (2) | US9120947B2 (en) |
JP (1) | JP5889868B2 (en) |
KR (1) | KR101865314B1 (en) |
CN (1) | CN102858874B (en) |
SG (1) | SG10201404909UA (en) |
WO (1) | WO2011116217A1 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9772554B2 (en) | 2015-02-26 | 2017-09-26 | Dow Global Technologies Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
US9840637B2 (en) | 2015-02-26 | 2017-12-12 | Dow Global Technologies Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
US10011713B2 (en) | 2014-12-30 | 2018-07-03 | Dow Global Technologies Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
US10294359B2 (en) | 2014-12-30 | 2019-05-21 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
US10351727B2 (en) | 2015-02-26 | 2019-07-16 | Dow Global Technologies Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
US11021630B2 (en) | 2014-12-30 | 2021-06-01 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2011116217A1 (en) | 2010-03-18 | 2011-09-22 | Board Of Regents The University Of Texas System | Surface treatments for alignment of block copolymers |
JP5994788B2 (en) * | 2011-11-09 | 2016-09-21 | Jsr株式会社 | Self-assembling composition for pattern formation and pattern forming method |
KR102245179B1 (en) | 2013-04-03 | 2021-04-28 | 브레우어 사이언스, 인코포레이션 | Highly etch-resistant polymer block for use in block copolymers for directed self-assembly |
CN103304827B (en) * | 2013-05-27 | 2014-08-06 | 四川大学 | Method for preparing macromolecule ultrathin membrane nano wrinkling patterns |
JP6558894B2 (en) | 2013-12-31 | 2019-08-14 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | DESIGN OF COPOLYMER, METHOD FOR PRODUCING THE SAME AND ARTICLE CONTAINING THE SAME |
JP6702649B2 (en) | 2013-12-31 | 2020-06-03 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | Method for controlling the properties of block copolymers and articles made from block copolymers |
JP2015129261A (en) | 2013-12-31 | 2015-07-16 | ローム アンド ハース エレクトロニック マテリアルズ エルエルシーRohm and Haas Electronic Materials LLC | Method of annealing block copolymer, article produced from block copolymer |
CN106104754B (en) | 2014-01-16 | 2020-07-28 | 布鲁尔科技公司 | High CHI block copolymers for direct self-assembly |
FR3025616A1 (en) * | 2014-09-10 | 2016-03-11 | Arkema France | METHOD FOR CONTROLLING THE DEFECT RATE IN FILMS OBTAINED WITH MIXTURES OF BLOCK COPOLYMERS AND POLYMERS |
KR20160038701A (en) * | 2014-09-30 | 2016-04-07 | 주식회사 엘지화학 | Preparation method of patterened substrate |
WO2016080972A1 (en) * | 2014-11-18 | 2016-05-26 | Seagate Technology Llc | Methods and apparatuses for directed self-assembly |
US20160186001A1 (en) * | 2014-12-30 | 2016-06-30 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
US9733566B2 (en) * | 2015-03-17 | 2017-08-15 | Tokyo Electron Limited | Spin-on layer for directed self assembly with tunable neutrality |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080176767A1 (en) * | 2007-01-24 | 2008-07-24 | Micron Technology, Inc. | Two-dimensional arrays of holes with sub-lithographic diameters formed by block copolymer self-assembly |
US20080217292A1 (en) * | 2007-03-06 | 2008-09-11 | Micron Technology, Inc. | Registered structure formation via the application of directed thermal energy to diblock copolymer films |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3056512B2 (en) * | 1990-08-02 | 2000-06-26 | 鐘淵化学工業株式会社 | Material surface modification method |
KR100930966B1 (en) * | 2007-09-14 | 2009-12-10 | 한국과학기술원 | Nanostructures of block copolymers formed on surface patterns of shapes inconsistent with the nanostructures of block copolymers and methods for manufacturing the same |
US7989026B2 (en) * | 2008-01-12 | 2011-08-02 | International Business Machines Corporation | Method of use of epoxy-containing cycloaliphatic acrylic polymers as orientation control layers for block copolymer thin films |
WO2011116217A1 (en) | 2010-03-18 | 2011-09-22 | Board Of Regents The University Of Texas System | Surface treatments for alignment of block copolymers |
-
2011
- 2011-03-17 WO PCT/US2011/028858 patent/WO2011116217A1/en active Application Filing
- 2011-03-17 US US13/583,518 patent/US9120947B2/en not_active Expired - Fee Related
- 2011-03-17 JP JP2013500212A patent/JP5889868B2/en not_active Expired - Fee Related
- 2011-03-17 KR KR1020127027172A patent/KR101865314B1/en active IP Right Grant
- 2011-03-17 SG SG10201404909UA patent/SG10201404909UA/en unknown
- 2011-03-17 CN CN201180020759.0A patent/CN102858874B/en not_active Expired - Fee Related
-
2015
- 2015-04-28 US US14/698,365 patent/US20150240110A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080176767A1 (en) * | 2007-01-24 | 2008-07-24 | Micron Technology, Inc. | Two-dimensional arrays of holes with sub-lithographic diameters formed by block copolymer self-assembly |
US20080217292A1 (en) * | 2007-03-06 | 2008-09-11 | Micron Technology, Inc. | Registered structure formation via the application of directed thermal energy to diblock copolymer films |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10011713B2 (en) | 2014-12-30 | 2018-07-03 | Dow Global Technologies Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
US10294359B2 (en) | 2014-12-30 | 2019-05-21 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
US11021630B2 (en) | 2014-12-30 | 2021-06-01 | Rohm And Haas Electronic Materials Llc | Copolymer formulation for directed self assembly, methods of manufacture thereof and articles comprising the same |
US9772554B2 (en) | 2015-02-26 | 2017-09-26 | Dow Global Technologies Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
US9840637B2 (en) | 2015-02-26 | 2017-12-12 | Dow Global Technologies Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
US10351727B2 (en) | 2015-02-26 | 2019-07-16 | Dow Global Technologies Llc | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same |
Also Published As
Publication number | Publication date |
---|---|
KR20130039728A (en) | 2013-04-22 |
US9120947B2 (en) | 2015-09-01 |
KR101865314B1 (en) | 2018-06-08 |
WO2011116217A1 (en) | 2011-09-22 |
US20130045361A1 (en) | 2013-02-21 |
CN102858874B (en) | 2015-12-16 |
JP2013528476A (en) | 2013-07-11 |
CN102858874A (en) | 2013-01-02 |
SG10201404909UA (en) | 2015-06-29 |
JP5889868B2 (en) | 2016-03-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US9120947B2 (en) | Surface treatments for alignment of block copolymers | |
JP6377600B2 (en) | Copolymer formulations for induced self-assembly, methods for making the same, and articles containing the same | |
JP6247823B2 (en) | Self-assembled structure, manufacturing method thereof, and article including the same | |
JP6613339B2 (en) | Copolymer formulations for induced self-assembly, methods for making the same, and articles containing the same | |
Bates et al. | Polymeric cross-linked surface treatments for controlling block copolymer orientation in thin films | |
US10295908B2 (en) | Block copolymer | |
JP6499596B2 (en) | Copolymer blend for induced self-assembly, process for its production, and article comprising the same | |
JP6702649B2 (en) | Method for controlling the properties of block copolymers and articles made from block copolymers | |
US9765214B2 (en) | Copolymer formulation for directed self-assembly, methods of manufacture thereof and articles comprising the same | |
JP2016192540A (en) | Copolymer compound for induction self-organization, manufacturing method thereof and article including the same | |
US20150073096A1 (en) | Process for controlling the period of a nanostructured assemblage comprising a blend of block copolymers | |
US20200231731A1 (en) | Process that enables the creation of nanometric structures by self-assembly of diblock copolymers | |
TW202132483A (en) | Neutral underlayer for a block copolymer and polymeric stack comprising such an underlayer covered with a block copolymer film | |
Wylie | Synthesis and self-assembly of gradient copolymers |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AS | Assignment |
Owner name: BOARD OF REGENTS, THE UNIVERSITY OF TEXAS SYSTEM, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WILLSON, C. GRANT;BATES, CHRISTOPHER M.;STRAHAN, JEFFREY;AND OTHERS;SIGNING DATES FROM 20120926 TO 20121002;REEL/FRAME:035977/0180 |
|
STCB | Information on status: application discontinuation |
Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION |