Sol-gel based antireflective coatings using alkyltrialkoxysilane binders having low refractive index and high durability

Patent metadata

Field	Value
Publication number	US-9109121-B2
Application number	US-201113273007-A
Country	US
Kind code	B2
Filing date	Oct 13, 2011
Priority date	Oct 13, 2011
Publication date	Aug 18, 2015
Grant date	Aug 18, 2015

Abstract

Methods and compositions for forming porous low refractive index coatings on substrates are provided. The method comprises coating a substrate with a sol-formulation comprising silica based nanoparticles and an alkyltrialkoxysilane based binder. Use of the alkyltrialkoxysilane based binder results in a porous low refractive index coating having bimodal pore distribution including mesopores formed from particle packing and micropores formed from the burning off of organics including the alkyl chain covalently bonded to the silicon. The mass ratio of binder to particles may vary from 0.1 to 20. Porous coatings formed according to the embodiments described herein demonstrate good optical properties (e.g. a low refractive index) while maintaining good mechanical durability due to the presence of a high amount of binder and a close pore structure.

First claim

What is claimed is:

1. A method of forming a porous coating on a substrate, comprising:
coating a substrate with a sol-formulation comprising:
an alkyltrialkoxysilane-based binder having the formula:

wherein at least one of R1, R2, and R3 represents an alkyl group containing 1 to 20 carbon atoms selected from the group consisting of n-pentyl, isopentyl, n-hexyl, isohexyl, cyclohexyl, n-heptyl, methoylcyclohexyl, octyl, and ethylcyclohexyl or an aryl group containing 6 to 20 carbon atoms selected from the group consisting of benzyl and xylyl;
wherein R4 represents a fluoro-modified alkyl group containing 1 to 20 carbon atoms; and

silica based nanoparticles, wherein a mass ratio of the alkyltrialkoxysilane-based binder to the silica based nanoparticles is between 0.1:1 to 20:1;
wherein the sol-formulation further comprises an alcohol containing solvent and an acid or base containing catalyst;
wherein the sol-formulation further comprises rare-earth-based oxide nanoparticles, the rare-earth-based oxide nanoparticles comprising at least one of Y 2 TeO 11 , Y 2 Te 5 O 13 , YInGe 2 O 2 :Eu 3+ , yttrium aluminum garnet (YAG) doped with Eu 3+ ions, La (1−x) Eu x Mn 0-9 Zn 0-1 O 3+d (LEMZ), Y 2 O 3 :Eu 3+ , or a combination thereof; and

annealing the coated substrate.

2. The method of claim 1 , wherein the total ash content of the sol-formulation is from about 0.5 wt. % to 20 wt. % of the total weight of the sol-formulation.

3. The method of claim 2 , wherein the alkyltrialkoxysilane-based binder comprises from about 10 wt. % to about 80 wt. % ash contribution in the total ash content of the sol-formulation.

4. The method of claim 1 , wherein the fluoro-modified alkyl group containing 1 to 20 carbon atoms is fluorohexyl.

5. The method of claim 1 , further comprising:
forming a gel on the substrate by drying the sol-formulation coated on the substrate prior to annealing the coated substrate.

6. The method of claim 1 , wherein the silica based nanoparticles have a shape selected from the group consisting of spherical, elongated, disc-shaped, and combinations thereof.

7. The method of claim 6 , wherein the silica based nanoparticles are selected from the group consisting of spherical particles having a particle size from about 40 to 50 nm, spherical particles having a particle size from about 70 to 100 nm, spherical particles having a particle size from about 10 to 15 nm, spherical particles having a particle size from about 17 to 23 nm, elongated particles having a diameter from 9 to 15 nm and length of 40 to 100 nm, and combinations thereof.

8. The method of claim 1 , wherein the alcohol containing solvent is n-propyl alcohol, and the acid or base containing catalyst is acetic acid.

9. The method of claim 1 , wherein the alcohol containing solvent is n-propyl alcohol, and the acid or base containing catalyst is nitric acid.

10. The method of claim 1 , wherein the sol-formulation further comprises an orthosilicate-based binder selected from the group consisting of tetraethylorthosilicate (TEOS), tetramethylorthosilicate (TMOS), tetrapropylorthosilicate, tetrabutylorthosilicate, tetrakis(trimethylsilyloxy)silane, tetrapropylorthosilicate (TPOS), propyltriethylorthosilicate (PTES), and combinations thereof.

11. The method of claim 1 , wherein the sol-formulation comprises:
from about 0.1 wt. % to about 50 wt. % of alkyltrialkoxysilane-based binder;
from about 0.1 wt. % to about 15 wt. % of silica-based nanoparticles;
from about 50 wt. % to about 95 wt. % of an alcohol containing solvent; and
from about 0.001 wt. % to about 0.1 wt. % of an acid or base containing catalyst.

12. A method of forming a porous coating on a substrate, comprising:
coating a substrate with a sol-formulation comprising:
an alkyltrialkoxysilane-based binder selected from the group consisting of n-pentyltriethoxysilane, n-hexyltriethoxysilane, and combinations thereof; and
silica based nanoparticles, wherein a mass ratio of the alkyltrialkoxysilane-based binder to the silica based nanoparticles is between 0.1:1 to 20:1; and

wherein the sol-formulation further comprises:
an alcohol containing solvent;
an acid or base containing catalyst; and
rare-earth-based oxide nanoparticles, the rare-earth-based oxide nanoparticles comprising at least one of Y 2 TeO 11 , Y 2 TeO 13 , YInGe 2 O 7 :Eu 3+ , yttrium aluminum garnet (YAG) doped with Eu 3+ ions, La (1−x) Eu x Mn 0-9 Zn 0-1 O 3+d (LEMZ), Y 2 O 3 :Eu3+, or a combination thereof;

annealing the coated substrate.

13. The method of claim 12 , further comprising:
forming a gel on the substrate by drying the sol-formulation coated on the substrate prior to annealing the coated substrate.

14. The method of claim 12 , wherein the silica based nanoparticles have a shape selected from the group consisting of spherical, elongated, disc-shaped, and combinations thereof.

15. The method of claim 14 , wherein the silica based nanoparticles are selected from the group consisting of spherical particles having a particle size from about 40 to 50 nm, spherical particles having a particle size from about 70 to 100 nm, spherical particles having a particle size from about 10 to 15 nm, spherical particles having a particle size from about 17 to 23 nm, elongated particles having a diameter from 9 to 15 nm and length of 40 to 100 nm, and combinations thereof.

Assignees

• Kalyankar Nikhil D
• Sun Zhi-Wen
• Van Duren Jeroen
• Lewis Mark
• Liang Liang
• Intermolecular Inc
• Guardian Industries

Inventors

• Kalyankar Nikhil D
• Sun Zhi-Wen
• Van Duren Jeroen
• Lewis Mark
• Liang Liang

Classifications

• G02B1/115

  Multilayers · CPC title

• C09D7/1266

  Chemistry & Metallurgy · mapped topic

• C08K3/36

  Silica · CPC title

• C09D1/00 Primary

  Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances · CPC title

• C09D5/006

  Anti-reflective coatings · CPC title