Broadband antireflective coating composition and method

• US 4,830,879 A
• Filed: 09/25/1986
• Issued: 05/16/1989
• Est. Priority Date: 09/25/1986
• Status: Expired due to Fees

• Current Assignee: Battelle Memorial Institute 505 King Avenue Columbus
• Original Assignee: Battelle Memorial Institute
• Inventors: Debsikdar, Jagadish
• Primary Examiner(s): BELL, JANYCE A
• Application Number:
  US06/911,577
• Time in Patent Office: 964 Days
• Field of Search: 427/205, 427/190, 427/165, 427/203, 427/376.2, 427/162, 427/164, 427/126.5, 427/126.6, 428/428, 428/482
• US Class Current: 427/162
• CPC Class Codes: B05D 5/061 Special surface effect
• CPC Class Codes: C03C 17/25 by deposition from the liquid phase
• CPC Class Codes: C03C 17/27 by oxidation of a coating previously applied
• CPC Class Codes: C03C 2217/229 Non-specific enumeration
• CPC Class Codes: C03C 2218/113 by sol-gel processes
• CPC Class Codes: C03C 2218/322 Oxidation
• CPC Class Codes: C08G 79/00 Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
• CPC Class Codes: C09D 1/00 Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
• CPC Class Codes: C09D 183/02 Polysilicates
• CPC Class Codes: C09D 185/00 Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
• CPC Class Codes: G02B 1/111 using layers comprising organic materials

Abstract

The invention relates to antireflective coatings and to a process for depositing the antireflective coatings on solar collector cover plates, optical elements such as lenses and windows in high-energy visible and near-IR lenses and on other glass or metal or metal-alloy or single crystal surfaces, including the steps of hydrolyzing an alkoxysilane, titanium alkoxide, aluminum alkoxide, tantalum alkoxide, niobium alkoxide, or other alkoxy compounds, or a mixture thereof, depending upon the final coating composition desired; to prepare polymeric solutions of the alkoxy compound/or compounds in which the polymer molecules or macromolecules (i.e. the primary particles) grow with time; depositing layers of coatings from the polymeric solutions by state of the art processes (such as spraying, dipping or spinning method), and drying to form chemically bound microporous gel layers; thermally treating the gel-coating in a manner adapted to remove solvent, excess water and residual organics from the gel coating. Microporous coatings produced by the above procedure will be characterized by graded particles and hence graded porosity across the coating thickness, --larger porosity on the top surface and smaller porosity in the substructure--, and will have gradual transition of refractive index (i.e. graded refractive index) across the coating thickness. Coatings produced by the process of this invention can be used to reduce or eliminate reflection losses from surfaces of transmitting optical elements over a wide spectrum of light waves.

Claims

1. A process for producing broadband antireflective coatings comprising:

a. preparing a plurality of solutions of an alkoxide precursor material by reacting an alkoxide or alkoxide mixture with water with or without a catalyst at conditions adapted to produce a series of solutions containing particles of a different size in each solution so that the series of solutions has one solution of a smallest size and one or more solutions each having increasing sizes, wherein the alkoxide is represented by the general formula M(OR)_x where M is a metal atom, R is an alkyl group, having from one to five carbon atoms, and x is the valency of the metal atom, and whereby the plurality of solutions are aged or have increased solution pH so as to obtain solutions having different particle size ranges and the alkoxide or alkoxide mixture is selected from the group consisting of the alkoxides of silicon, aluminum, titanium, tantalum, niobium, or zirconium;

b. providing a substrate and depositing and drying one or more layers of a first coating over the substrate from the solution having the smallest particle size;

c. depositing and drying one or more additional coatings each having one or more layers over the coating obtained in step B. from solutions having increasing particle sizes; and

d. thermally treating the plurality of deposited coatings from the above steps to obtain a consolidated antireflective coating with a porous structure, wherein the thermal treatment is below the temperature at which the porous structure of the coating will collapse.

2. The process of claim 1 whereby the plurality of solutions in step a. are prepared sequentially and aged so as to obtain solutions having different particle size ranges.

3. The process of claim 1 whereby the plurality of solutions in step a. are prepared by use of catalysts adapted to obtain solutions having different particle size ranges.

4. The process of claim 1 whereby the step of thermally treating the deposited coating further comprises treating at a temperature below 900°

C.

5. The process of claim 1 whereby a dopant alkoxide is added to step a. that is selected form the group consisting of the alkoxides of boron, phosphorous, germanium and a mixture thereof.

11. The method of claim 3 or 8 whereby an acid catalyst is used.

12. The method of claim 3 or 8 whereby a basic catalyst is used.

13. The method of claim 3 or 8 whereby an acid catalyst is used in one set of solutions and a basic catalyst in another set.

6. A process for producing a broadband antireflective coating comprising:

a. preparing a plurality of coating solutions by the steps of mixing;

1. an alkoxide represented by the general formula M(OR)_x where M is a metal atom selected form the group consisting of silicon, aluminum, titanium, tantalum, niobium, zirconium and a mixture thereof, where R is an alkyl group having from one to five carbon atoms and x is the valency of the metal atom;

2. water, H₂ O;

3. an organic solvent selected form the group consisting of alcohols;

R₁ -OH, and ketones ##STR3## or mixtures thereof, where R₁ is an alkyl group having from one to five carbon atoms and R₂ and R₃ are alkyl groups having from one to two carbon atoms, whereby the plurality of solutions in step a. are aged or have increased solution pH so as to obtain solutions having different particle size ranges;

b. providing a substitute adapted for coating by the prepared solutions;

c. depositing and drying one or more layers of the solution having the smallest particle size onto the substrate to form a gel coating;

d. depositing and drying one or more gel coatings each having one or more layers over the gel coating of step c.; and

e. thermally treating the deposited coatings to obtain a consolidated antireflective coating with a porous structure, wherein the thermal treatment is below the temperature at which the porous structure of the coating will collapse.

7. The process of claim 6 whereby the plurality of solutions in step a. are prepared sequentially and aged so as to obtain solutions having different particle size ranges.

8. The process of claim 6 whereby the plurality of solutions in step a. are prepared by use of catalysts adapted to obtain solutions having different particle size ranges.

9. The process of claim 6 whereby the step of thermally treating the deposited coating further comprises treating at a temperature below 900°

C.

10. The process of claim 6 whereby a dopant alkoxide having the general formula Md(OR)_x where M_d is a dopant atom selected from the group consisting of boron, phosphorous, germanium, and a mixture thereof, wherein R is an alkyl group having from one to five carbon atoms and x is the valency of the dopant atom, is mixed with the alkoxide of step a.1.