# US 11,110,683 B2 · Substrates comprising nano-patterning surfaces and methods of preparing thereof

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- Number: US 11,110,683 B2
- Document ID: US11110683B2
- Status: Granted
- Kind: B2
- Application number: 16/880,809
- Filed: 2020-05-21
- Published: 2020-09-10
- Granted: 2021-09-07
- Earliest claimed: 2013-12-19
- Assignees: Illumina, Inc.
- Applicants: Illumina, Inc.
- Inventors: M. Shane Bowen; Bala Murali Venkatesan; Steven M. Barnard
- Web page: https://patentgrep.com/patent/US11110683B2

## CPC

- B32B 3/266: {characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12}
- B01L 3/502: {with fluid transport, e.g. in multi-compartment structures}
- B32B 3/30: characterised by a layer formed with recesses or projections, e.g. {hollows, grooves, protuberances, ribs (apertured layer B32B3/266; layer with cavities or internal voids B32B3/26)}
- C08G 69/00: Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule (products obtained from isocyanates or isothiocyanates C08G18/00; polyamide-imides C08G73/14)
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- B01L 2300/0887: Laminated structure
- B01L 2300/0896: Nanoscaled
- B01L 2300/163: Biocompatibility
- B29C 59/005: {characterised by the choice of material}
- B29C 59/022: {characterised by the disposition or the configuration, e.g. dimensions, of the embossments or the shaping tools therefor}
- B29K 2077/00: Use of {PA, i.e.} polyamides, e.g. polyesteramides {or derivatives thereof}, as moulding material
- B29K 2105/0085: {Copolymers}
- B81B 2201/0214: Biosensors; Chemical sensors
- B81B 2201/05: Microfluidics
- B81B 2203/03: Static structures
- B81B 2203/0315: Cavities
- B81B 2203/0323: Grooves
- B81B 2203/0361: Tips, pillars
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B01L: CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- B29C: SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING (making preforms B29B11/00; making laminated products by combining previously unconnected layers which become one product whose layers will remain together B32B37/00 - B32B41/00)
- B29K: INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR {MOULDS, } REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B81B: MICROSTRUCTURAL DEVICES OR SYSTEMS, e.g. MICROMECHANICAL DEVICES (piezoelectric, electrostrictive or magnetostrictive elements per se H10N30/00, H10N35/00)

## Abstract

Substrates comprising a functionalizable layer, a polymer layer comprising a plurality of micro-scale or nano-scale patterns, or combinations thereof, and a backing layer and the preparation thereof by using room-temperature UV nano-embossing processes are disclosed. The substrates can be prepared by a roll-to-roll continuous process. The substrates can be used as flow cells, nanofluidic or microfluidic devices for biological molecules analysis.

## Claims

### Claim 1

A process of preparing a substrate, comprising:
contacting a template having a plurality of micro-scale or nano-scale patterns with a surface of a substrate comprising a photocurable polymer layer disposed thereon;
applying pressure to the template or substrate to transfer the plurality of micro-scale or nano-scale patterns to the photocurable polymer layer, wherein the contacting and applying are performed at room temperature;
irradiating the photocurable polymer with UV light to cure the photocurable polymer to form a UV cured polymer layer; and
separating the template from substrate;
wherein the substrate comprises a functionalizable layer in contact with the photocurable polymer layer, wherein the functionalizable layer comprises a functionalizable hydrogel or a functionalizable polymer, and wherein the functionalizable hydrogel or functionalizable polymer comprises one or more functional groups capable of attaching to biomolecules; and
wherein the one or more functional groups of the functionalizable hydrogel or the functionalizable polymer are selected from the group consisting of optionally substituted alkene, azide, optionally substituted amine, carboxylic acid, optionally substituted hydrazone, hydroxy, optionally substituted tetrazole, optionally substituted tetrazine, thiol, and combinations thereof.

### Claim 2 (depends on 1)

The process of claim 1, wherein at least a portion of the micro-scale or nano-scale patterns of the template are transferred to the functionalizable layer.

### Claim 3 (depends on 1)

The process of claim 1, further comprising applying a sealing layer to the substrate after removing the template to substantially seal the UV cured polymer layer and the functionalizable layer.

### Claim 4 (depends on 1)

The process of claim 1, wherein at least a portion of the micro-scale or nano-scale patterns are posts having an average diameter or an average height of less than about 500 nm.

### Claim 5 (depends on 1)

The process of claim 1, wherein the functionalizable polymer or the functionalizable hydrogel comprising Formula (Ia):
R1 is H or optionally substituted alkyl;
RA is azide, optionally substituted amine, optionally substituted alkene, optionally substituted hydrazone, carboxylic acid, halogen, hydroxy, optionally substituted tetrazole, optionally substituted tetrazine, or thiol;
R5 is H or optionally substituted alkyl;
each of the —(CH2)-p is optionally substituted;
p is an integer in the range of 1 to 50;
n is an integer in the range of 1 to 50,000; and
m is an integer in the range of 1 to 100,000.

### Claim 6 (depends on 1)

The process of claim 1, wherein functionalizable hydrogel or the functionalizable polymer comprises poly(N-(5-azidoacetamidylpentyl) acrylamide-co-acrylamide) (PAZAM).

### Claim 7 (depends on 1)

The process of claim 1, wherein the functionalizable layer further comprises biomolecules covalently attached thereto, and wherein the biomolecules comprise amino acids, nucleosides, nucleotides, peptides, oligonucleotides, polynucleotides, nucleic acids, or proteins, or combinations thereof.

### Claim 8 (depends on 7)

The process of claim 7, wherein the biomolecules comprise oligonucleotides, polynucleotides, or nucleic acids, or combinations thereof.

### Claim 9 (depends on 1)

The process of claim 1, wherein the photocurable polymer comprises urethane, acrylate, silicone, epoxy, polyacrylic acid, polyacrylates, epoxy silicone, epoxy resins, polydimethylsiloxane (PDMS), silsesquioxane, acyloxysilanes, maleate polyesters, vinyl ethers, monomers with vinyl or ethynyl groups, or copolymers or combinations thereof.

### Claim 10 (depends on 1)

The process of claim 1, wherein at least one of the polymer layer or functionalizable layer comprises a dopant material selected from the group consisting of nanoparticles, Q dots, binding receptors, ligands, nucleic acids, reactive moieties in the functionalizable layer, optical filter materials, lighter absorbing materials, light emitting materials, light scattering materials, electrical conductive materials and thermally conductive materials, and combinations thereof.

### Claim 11 (depends on 1)

The process of claim 1, wherein the process is a roll to roll process.

### Claim 12

A process of preparing a substrate, comprising:
depositing a functionalizable layer comprising one or more functional groups onto a surface of a template comprising a plurality of micro-scale or nano-scale patterns, such that the functionalizable layer is contained inside at least a portion of said micro-scale or nano-scale patterns;
contacting the surface of the template comprising the plurality of micro-scale or nano-scale patterns with a surface of a substrate comprising a photocurable polymer layer disposed thereon;
applying pressure to the template or substrate to transfer said micro-scale or nano-scale patterns to the photocurable polymer layer, wherein the contacting and applying are performed at room temperature;
irradiating the photocurable polymer with UV light to form a UV cured polymer layer; and; and
separating the template from the substrate;
wherein at least a portion of the functionalizable layer is transferred onto the UV cured polymer layer, wherein the functionalizable layer comprises a functionalizable hydrogel or a functionalizable polymer, and wherein the functionalizable hydrogel or functionalizable polymer comprises one or more functional groups capable of attaching to biomolecules; and
wherein the one or more functional groups of the functionalizable hydrogel or the functionalizable polymer are selected from the group consisting of optionally substituted alkene, azide, optionally substituted amine, carboxylic acid, optionally substituted hydrazone, hydroxy, optionally substituted tetrazole, optionally substituted tetrazine, thiol, and combinations thereof.

### Claim 13 (depends on 12)

The process of claim 12, wherein the functionalizable polymer or the functionalizable hydrogel comprising Formula (Ia):
R1 is H or optionally substituted alkyl;
RA is azide, optionally substituted amine, optionally substituted alkene, optionally substituted hydrazone, carboxylic acid, halogen, hydroxy, optionally substituted tetrazole, optionally substituted tetrazine, and thiol;
R5 is H or optionally substituted alkyl;
each of the —(CH2)-p is optionally substituted;
p is an integer in the range of 1 to 50;
n is an integer in the range of 1 to 50,000; and
m is an integer in the range of 1 to 100,000.

### Claim 14 (depends on 12)

The process of claim 12, wherein functionalizable hydrogel or the functionalizable polymer comprises poly(N-(5-azidoacetamidylpentyl) acrylamide-co-acrylamide) (PAZAM).

### Claim 15 (depends on 12)

The process of claim 12, wherein the functionalizable layer further comprises biomolecules covalently attached thereto, and wherein the biomolecules comprise amino acids, nucleosides, nucleotides, peptides, oligonucleotides, polynucleotides, nucleic acids, or proteins, or combinations thereof.

### Claim 16 (depends on 15)

The process of claim 15, wherein the biomolecules comprise oligonucleotides, polynucleotides, or nucleic acids, or combinations thereof.

### Claim 17 (depends on 12)

The process of claim 12, wherein the photocurable polymer comprises urethane, acrylate, silicone, epoxy, polyacrylic acid, polyacrylates, epoxy silicone, epoxy resins, polydimethylsiloxane (PDMS), silsesquioxane, acyloxysilanes, maleate polyesters, vinyl ethers, monomers with vinyl or ethynyl groups, or copolymers or combinations thereof.