# US 12,006,441 B2 · Imprinting ink composition, imprinting method, optical element lighting device, optical sensor and photovoltaic device

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- Number: US 12,006,441 B2
- Document ID: US12006441B2
- Status: Granted
- Kind: B2
- Application number: 15/767,456
- Filed: 2016-10-13
- Published: 2018-10-25
- Granted: 2024-06-11
- Earliest claimed: 2015-10-20
- Assignees: Koninklijke Philips N.V.
- Applicants: Koninklijke Philips N.V.
- Inventors: Marcus Antonius Verschuuren; Anne Souren
- Web page: https://patentgrep.com/patent/US12006441B2

## CPC

- C09D 11/102: containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
- C09D 11/00: Inks
- C09D 11/02: Printing inks (C09D11/30 takes precedence)
- C09D 11/037: characterised by the pigment
- C09D 17/007: {Metal oxide}
- C09D 17/008: {Titanium dioxide}
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- H10F 77/413: {directly associated or integrated with the devices, e.g. back reflectors (directly associated or integrated with photovoltaic cells H10F77/42)}
- H10F 77/484: {Refractive light-concentrating means, e.g. lenses}
- H10H 20/855: Optical field-shaping means, e.g. lenses
- G01J 1/0407: {Optical elements not provided otherwise, e.g. manifolds, windows, holograms, gratings}
- H10H 20/0363: {of optical field-shaping means}
- Y02E 10/52: PV systems with concentrators
- 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)
- 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)
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10H: INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
- G01J: MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY (light sources F21, H01J, H01K, H05B; investigating properties of materials by optical means G01N)
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

Disclosed are imprinting ink compositions for use in imprinting techniques such as SCIL. The imprinting ink compositions comprise TMO nanoparticles stabilized by selected polymerization inhibitors that allow for the formation of a stable imprinting ink composition in which polymerization of the TMO nanoparticles is effectively suppressed and from which high refractive index patterned layers can be formed. Imprinting methods using such imprinting ink compositions, optical devices including patterned layers formed from such imprinting ink compositions and lighting devices, optical sensors and photovoltaic devices including such optical elements are also disclosed.

## Claims

### Claim 1

An imprinting ink composition for nanoimprinting lithography, comprising:
a solvent;
polymerizable content dissolved and/or dispersed in the solvent, the polymerizable content comprising transition metal oxide particles in a high concentration, forming at least 80% by weight of the total weight of the polymerizable content for increasing a refractive index of pattern layers formed from the imprinting ink composition, the polymerizable content forming 2-25% by weight based on the total weight of the imprinting ink composition; and
a polymerization inhibitor of Formula 1 present in a range of 0.1-3.0% by weight based on the total weight of the imprinting ink composition sufficient for preventing premature polymerization of the polymerizable content resulting from the high concentration of the transition metal oxide particles:
wherein in Formula 1, R1 is hydrogen, C1-C4 alkyl or —(—C2H5—O—)n—R13, wherein n is 1, 2 or 3 and R13 is a C1-C3 alkyl; R2 and R3 individually are selected from hydrogen or C1-C4 alkyl and m is 0, 1, 2 or 3; and
an ammonia solution present in a range of 10-40% by weight based on the total weight of the imprinting ink composition sufficient for increasing a pH of the imprinting ink composition to a range of 1-2.5 to reduce corrosion of substrate material of a patterned elastomeric stamp used to imprint layers formed of the imprinting ink composition.

### Claim 2 (depends on 1)

The imprinting ink composition of claim 1, wherein the transition metal oxide particles have a particle size distribution from a lower value ranging from 1-10 nm to an upper value ranging from 20-40 nm, wherein the particle size distribution is 5-30 nm.

### Claim 3 (depends on 1)

The imprinting ink composition of claim 1, wherein the transition metal oxide particles are selected from TiO2, ZrO2, HfO2, Ta2O3, V2O3, Nb2O3, Y2O3, Fe2O3, BaTiO3 and SrTiO3 particles.

### Claim 4 (depends on 3)

The imprinting ink composition of claim 3, wherein the transition metal oxide particles are anatase or rutile TiO2 particles, rutile TiO2 particles.

### Claim 5 (depends on 1)

The imprinting ink composition of claim 1, further comprising up to 20%, by weight of a polymer matrix precursor based on a total weight of the polymerizable content.

### Claim 6 (depends on 5)

The imprinting ink composition of claim 5, wherein the polymer matrix precursor is a polysiloxane precursor.

### Claim 7 (depends on 6)

The imprinting ink composition of claim 6, wherein the polysiloxane precursor is a precursor comprising at least one monomeric unit according to Formula 5:
wherein R7-R9 are individually selected from C1-C3 alkyl; and R10 is selected from C1-C3 alkyl, C1-C3 alkoxy and —(CH2)nNHR11, wherein R11 is selected from hydrogen and —(CH2)mNH2, wherein m and n are individually selected from 2, 3 and 4.

### Claim 8 (depends on 7)

The imprinting ink composition of claim 7, wherein the polysiloxane precursor comprises at least one monomeric unit according to Formula 6-9:

### Claim 9 (depends on 1)

The imprinting ink composition of claim 1, wherein the solvent is selected from at least one of water and methanol and optionally further comprises propoxyethanol up to 30% by weight based on the total weight of the imprinting ink composition.

### Claim 10 (depends on 1)

The imprinting ink composition of claim 1, wherein the ammonia solution has a mass fraction of 1.0-2.0 wt %.

### Claim 11 (depends on 1)

The imprinting ink composition of claim 1, wherein the polymerization inhibitor of Formula 1 comprises 1,2-propanediol.

### Claim 12 (depends on 1)

The imprinting ink composition of claim 1, wherein the polymerization inhibitor of Formula 1 comprises 2-(2-ethoxyethoxy) ethanol (EEOL).