# US 11,994,651 B2 · Anti-reflective transparent oleophobic surfaces and methods of manufacturing thereof

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- Number: US 11,994,651 B2
- Document ID: US11994651B2
- Status: Granted
- Kind: B2
- Application number: 17/601,505
- Filed: 2020-03-31
- Published: 2022-06-09
- Granted: 2024-05-28
- Earliest claimed: 2019-04-11
- Assignees: Fundació Institut De CièNcies FotòNiques; Institució Catalana De Recerca I Estudis AvançAts
- Applicants: Corning Incorporated; Fundació Institut De CièNcies FotòNiques; Institució Catalana De Recerca I Estudis AvançAts
- Inventors: Prantik Mazumder; Valerio Pruneri; Juan Rombaut
- Web page: https://patentgrep.com/patent/US11994651B2

## CPC

- B08B 17/065: {the surface having a microscopic surface pattern to achieve the same effect as a lotus flower}
- G02B 1/118: having sub-optical wavelength surface structures designed to provide an enhanced transmittance, e.g. moth-eye structures
- C03C 17/32: with synthetic or natural resins (C03C17/30 takes precedence)
- C03C 17/3639: {Multilayers containing at least two functional metal layers}
- C03C 17/3649: {made of metals other than silver}
- C03C 17/3657: {the multilayer coating having optical properties}
- C03C 17/38: at least one coating being a coating of an organic material
- C09D 5/006: {Anti-reflective coatings}
- C09D 179/08: Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C09K 13/04: containing an inorganic acid
- B82Y 40/00: Manufacture or treatment of nanostructures
- C03C 2217/73: Anti-reflective coatings with specific characteristics
- C03C 2218/156: by magnetron sputtering
- C03C 2218/33: by etching
- G02B 27/0006: {with means to keep optical surfaces clean, e.g. by preventing or removing dirt, stains, contamination, condensation (G02B1/18 takes precedence; cleaning in general B08B)}
- B08B: CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- C03C: CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- 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 (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

A method for fabricating a structured surface, includes: providing a transparent substrate; disposing a dewettable film over the substrate; annealing the dewettable film to form a plurality of islands; forming a coating over the plurality of islands; and etching the plurality of islands to form a structured array of surface features in the coating. A structured polymer and/or structured glass, includes: a structured array of surface features, such that the structured array of surface features has at least one dimension in a range of 0.5 nm to 5000 nm.

## Claims

### Claim 1

A method for fabricating a structured surface, comprising:
providing a transparent substrate;
disposing a dewettable film over the transparent substrate;
annealing the dewettable film to form a plurality of islands;
forming a coating over the plurality of islands, a thickness of the coating is less than a height of the plurality of islands to leave a portion of the plurality of islands exposed;
etching the plurality of islands to form a structured array of surface features in the coating;
transferring the structured array of surface features from the coating to the transparent substrate; and
removing the coating from the transparent substrate.

### Claim 2 (depends on 1)

The method of claim 1, wherein the dewettable film has a thickness in a range of 10 Å to 500 Å.

### Claim 3 (depends on 1)

The method of claim 1, wherein the dewettable film is at least one of: metals, alloys, metal oxides, polymers, organic materials, metal nitrides, or combinations thereof.

### Claim 4 (depends on 1)

The method of claim 1, wherein the dewettable film is at least one of: Cu, Al, Ni, Cr, Ti, Au, Ag, Co, W, Pt, or combinations thereof.

### Claim 5 (depends on 1)

The method of claim 1, wherein:
the plurality of islands is an ordered array of crystallographically-oriented or randomly-distributed islands, and
at least a portion of an island of the plurality of islands have a cross-sectional shape from an axis parallel to the transparent substrate of at least one of: circular, oval, elliptical, Cassini oval, Cartesian oval, egg-shaped, or combinations thereof.

### Claim 6 (depends on 1)

The method of claim 1, wherein the annealing is a rapid thermal anneal (RTA) conducted at a temperature in a range of 150° C. to 900° C. and for a time in a range of 10 sec to 1000 sec.

### Claim 7 (depends on 1)

The method of claim 1, wherein an island of the plurality of islands has at least one dimension in a range of 0.5 nm to 5000 nm.

### Claim 8 (depends on 1)

The method of claim 1, wherein the coating is a polymer coating comprising at least one of: polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyimide (PI), or a metal oxide coating, or a glass material coating, or a semiconductor material coating, or combinations thereof.

### Claim 9 (depends on 8)

The method of claim 8, wherein the forming the coating comprises:
a first curing conducted at a first temperature in a range of 50° C. to 200° C. for a first time in a range of 30 sec to 10 min; and then
a second curing conducted at a second temperature in a range of 150° C. to 300° C. for a second time in a range of 5 min to 25 min,
wherein the first temperature is less than the second temperature, and
wherein the first time is shorter than the second time.

### Claim 10 (depends on 1)

The method of claim 1, wherein the coating is a dewettable coating comprising at least one of: Cu, Al, Ni, Cr, Ti, Au, Ag, Co, W, Pt, or combinations thereof.

### Claim 11 (depends on 1)

The method of claim 1, wherein the etching is a wet etch process comprising at least one of: ammonium persulfate, FeCl3 saturated solution, KCN, H2O:HNO3, HNO3, NH4OH:H2O2, HNO3:H2O2, NH3:H2O2, H3PO4:HNO3:HAc, HNO3:H2SO4:CrO3:NH4Cl:H2O, HCl:FeCl3:H2O, or combinations thereof.

### Claim 12 (depends on 1)

The method of claim 1, wherein the structured array of surface features has a footprint at locations of the plurality of islands.

### Claim 13 (depends on 1)

The method of claim 1, wherein the structured array of surface features has at least one dimension in a range of 0.5 nm to 5000 nm.

### Claim 14 (depends on 1)

The method of claim 1, wherein the transferring is conducted by an anisotropic etch and wherein the anisotropic etch is conducted to a depth into the transparent substrate having a range of 0.5 nm to 1000 nm.

### Claim 15 (depends on 1)

The method of claim 1, wherein the removing is a wet etch process comprising at least one of: HNO3:HAc:acetone, HF:HNO3, FeCl3, HNO3:H2SO4:HAc:H2O, HNO3:H2O, HNO3:HAc, Ce(NH4)2(NO3)6:H2O, HF, H3PO4, HNO3, HF:HNO3, HCl:HNO3, 2NH4NO3·Ce(NO3)3·4(H2O):HNO3:H2O, H3PO4:HNO3:CH3COOH:H2O, or combinations thereof.

### Claim 16 (depends on 1)

The method of claim 1, wherein the dewettable film comprises a polymer.

### Claim 17 (depends on 1)

The method of claim 1, wherein the transparent substrate comprises glass, and the transparent substrate with the structured surface exhibits a reflection of less than 5%.