# US 2019/0377115 A1 · Matrix-embedded metamaterial coating, coated article having matrix-embedded metamaterial coating, and/or method of making the same

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- Number: US 2019/0377115 A1
- Document ID: US20190377115A1
- Status: Published application
- Kind: A1
- Application number: 16/006,292
- Filed: 2018-06-12
- Published: 2019-12-12
- Earliest claimed: 2018-06-12
- Assignees: Guardian Glass, LLC
- Applicants: Guardian Glass, LLC
- Inventors: Brent BOYCE; Patricia TUCKER; Shashi SHAH; Cesar CLAVERO
- Web page: https://patentgrep.com/patent/US20190377115A1

## CPC

- C03C 17/36: at least one coating being a metal
- G02B 5/282: {reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection}
- C03C 17/3613: {Coatings of type glass/inorganic compound/metal/inorganic compound/metal/other}
- C03C 17/3636: {one layer at least containing silicon, hydrogenated silicon or a silicide}
- C03C 17/3639: {Multilayers containing at least two functional metal layers}
- C03C 17/3642: {the multilayer coating containing a metal layer}
- C03C 17/3644: {the metal being silver}
- C03C 17/366: {Low-emissivity or solar control coatings}
- C03C 17/3681: {the multilayer coating being used in glazing, e.g. windows or windscreens}
- G02B 1/002: {made of materials engineered to provide properties not available in nature, e.g. metamaterials}
- C03C 2217/213: SiO2
- C03C 2217/216: ZnO
- C03C 2217/23: Mixtures
- C03C 2217/256: Ag
- C03C 2217/45: Inorganic continuous phases
- C03C 2217/479: Metals
- C03C 2217/944: Layers comprising zinc oxide
- C03C 2218/154: by sputtering
- C03C 2218/32: After-treatment
- 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
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS

## Abstract

Certain example embodiments of this invention relate to coated articles having a metamaterial-inclusive layer, coatings having a metamaterial-inclusive layer, and/or methods of making the same. Metamaterial-inclusive coatings may be used, for example, in low-emissivity applications, providing for more true color rendering, low angular color dependence, and/or high light-to-solar gain. The metamaterial material may be a noble metal or other material, and the layer may be made to self-assemble by virtue of surface tensions associated with the noble metal or other material, and the material selected for use as a matrix. An Ag-based metamaterial layer may be provided below a plurality (e.g., 2, 3, or more) continuous and uninterrupted layers comprising Ag in certain example embodiments. In certain example embodiments, barrier layers comprising TiZrOx may be provided between adjacent layers comprising Ag, as a lower-most layer in a low-E coating, and/or as an upper-most layer in a low-E coating.

## Claims

### Claim 1

A method of making a coated article comprising a low-E coating supported by a glass substrate, the method comprising:
forming a first matrix layer comprising a matrix material, directly or indirectly on the substrate;
forming a donor layer comprising Ag over and contacting the first matrix layer;
following formation of the donor layer, forming a second matrix layer comprising the matrix material over and contacting the donor layer, wherein the first and second matrix layers have thicknesses differing from one another by no more than 20%;
heat treating the coated article with at least the first and second matrix layers and the donor layer thereon to cause the Ag in the donor layer to self-assemble into a discontinuous collection of formations distributed in the matrix material in forming a metamaterial inclusive layer that emits resonances in a desired wavelength range based at least in part on the formations located therein; and
incorporating the metamaterial inclusive layer into the low-E coating.

### Claim 2 (depends on 1)

The method of claim 1, wherein the heat treating is performed for 15-30 minutes.

### Claim 3 (depends on 2)

The method of claim 2, wherein the heat treating is performed at 600-675 degrees C.

### Claim 4 (depends on 1)

The method of claim 1, wherein the heat treating is performed at 600-675 degrees C.

### Claim 5 (depends on 1)

The method of claim 1, wherein the first and second matrix layers each have an as-deposited thickness of 30-70 nm.

### Claim 6 (depends on 1)

The method of claim 1, wherein the matrix material comprises Nb and/or Si.

### Claim 7 (depends on 6)

The method of claim 6, wherein the matrix material comprises niobium oxide.

### Claim 8 (depends on 1)

The method of claim 1, wherein the donor layer has an as-deposited thickness of 5-10 nm.

### Claim 9 (depends on 1)

The method of claim 1, wherein the formations are formed to have an interparticle spacing of 5-75 nm and diameters or major distances of 20-140 nm.

### Claim 10 (depends on 9)

The method of claim 9, wherein the formations are formed to have 10-50 nm thicknesses.

### Claim 11 (depends on 1)

The method of claim 1, wherein the formations are substantially ellipsoidal.

### Claim 12 (depends on 1)

The method of claim 1, wherein the donor layer is formed by sputter deposition performed at a power level of 10-50 kW and at a line speed of 5-15 m/min.

### Claim 13 (depends on 1)

The method of claim 1, further comprising forming a plurality of continuous and uninterrupted IR reflecting layers, each IR reflecting layer comprising Ag.

### Claim 14 (depends on 13)

The method of claim 13, further comprising forming a plurality of barrier layers comprising TiZrOx.

### Claim 15 (depends on 13)

The method of claim 13, wherein the IR reflecting layers are formed over the metamaterial inclusive layer on a side of the metamaterial inclusive layer opposite the substrate.

### Claim 16 (depends on 13)

The method of claim 13, wherein the heat treating is performed following formation of the IR reflecting layers.

### Claim 17

A method of making a coated article comprising a low-E coating supported by a glass substrate, the method comprising:
forming a first matrix layer comprising a matrix material, directly or indirectly on the substrate;
forming a continuous and uninterrupted donor layer over and contacting the first matrix layer, the donor layer comprising one or more source material(s) selected from the group consisting of: Ag, Al, Au, AZO, Be, C, Cr, Cu, ITO, Ni, Pd, Pt, RuO2, Ti, and W; and
following formation of the donor layer, forming a second matrix layer comprising the matrix material over and contacting the donor layer, wherein the first and second matrix layers have thicknesses differing from one another by no more than 20%;
wherein the coated article with at least the first and second matrix layers and the donor layer thereon are heat treatable to cause the source material(s) in the donor layer to self-assemble into a synthetic layer comprising a discontinuous collection of formations distributed in the matrix material, the formations having a major distance no larger than 300 nm, the synthetic layer having resonance in a frequency range suitable for the low-E coating.

### Claim 18 (depends on 17)

The method of claim 17, wherein the first and second matrix layers each have an as-deposited thickness of 30-70 nm.

### Claim 19 (depends on 17)

The method of claim 17, wherein the matrix material comprises an oxide of Nb and/or Si.

### Claim 20 (depends on 17)

The method of claim 17, wherein the donor layer has an as-deposited thickness of 5-10 nm.

### Claim 21 (depends on 17)

The method of claim 17, wherein the heat treating is performable at a time and at a temperature sufficient to cause the formations to have an interparticle spacing of 5-75 nm and diameters or major distances of 20-140 nm.

### Claim 22 (depends on 21)

The method of claim 21, wherein the heat treating is performable at a time and at a temperature sufficient to cause the formations to have 10-50 nm thicknesses.

### Claim 23 (depends on 17)

The method of claim 17, wherein the donor layer is formed by sputter deposition performed at a power level of 10-50 kW and at a line speed of 5-15 m/min.

### Claim 24 (depends on 17)

The method of claim 17, further comprising forming a plurality of continuous and uninterrupted IR reflecting layers, each IR reflecting layer comprising Ag.

### Claim 25 (depends on 24)

The method of claim 24, further comprising forming a plurality of barrier layers comprising TiZrOx.

### Claim 26 (depends on 24)

The method of claim 24, wherein the IR reflecting layers are formed over the synthetic layer on a side of the synthetic layer opposite the substrate, following heat treatment.

### Claim 27 (depends on 24)

The method of claim 24, wherein the IR reflecting layers are formed over the second matrix layer, prior to heat treatment.

### Claim 28

A method of making a coated article comprising a low-E coating supported by a glass substrate, the method comprising:
having a plurality of layers formed on the substrate, the layers including: (a) a first matrix layer comprising a matrix material, directly or indirectly on the substrate, (b) a donor layer comprising Ag over and contacting the first matrix layer, and (c) a second matrix layer comprising the matrix material over and contacting the donor layer, wherein the first and second matrix layers have thicknesses differing from one another by no more than 20%; and
heat treating the coated article with at least the first and second matrix layers and the donor layer thereon to cause the Ag in the donor layer to self-assemble into a discontinuous collection of formations distributed in the matrix material in forming a metamaterial inclusive layer, the metamaterial inclusive layer having resonance in a selected frequency range suitable for the low-E coating.

### Claim 29 (depends on 28)

The method of claim 28, wherein the heat treating is performed for 15-30 minutes.

### Claim 30 (depends on 29)

The method of claim 29, wherein the heat treating is performed at 600-675 degrees C.

### Claim 31 (depends on 28)

The method of claim 28, wherein the heat treating is performed at 600-675 degrees C.

### Claim 32 (depends on 28)

The method of claim 28, wherein the first and second matrix layers each have an as-deposited thickness of 30-70 nm.

### Claim 33 (depends on 28)

The method of claim 28, wherein the matrix material comprises an oxide of Nb and/or Si.

### Claim 34 (depends on 28)

The method of claim 28, wherein the heat treating is performed at a time and at a temperature sufficient to cause the formations to have an interparticle spacing of 5-75 nm and diameters or major distances of 20-140 nm.

### Claim 35 (depends on 34)

The method of claim 34, wherein the heat treating is performed at a time and at a temperature sufficient to cause the formations to have 10-50 nm thicknesses.

### Claim 36 (depends on 28)

The method of claim 28, further comprising forming a plurality of continuous and uninterrupted IR reflecting layers, each IR reflecting layer comprising Ag.

### Claim 37 (depends on 36)

The method of claim 36, further comprising forming a plurality of barrier layers comprising TiZrOx.

### Claim 38 (depends on 36)

The method of claim 36, wherein the IR reflecting layers are formed over the metamaterial inclusive layer on a side of the metamaterial inclusive layer opposite the substrate, following heat treatment.

### Claim 39 (depends on 36)

The method of claim 36, wherein the IR reflecting layers are formed over the second matrix layer, prior to heat treatment.

### Claim 40

An intermediate article, comprising:
a glass substrate;
a first matrix layer comprising a matrix material, located directly or indirectly on the substrate;
a donor layer comprising Ag located over and contacting the first matrix layer; and
a second matrix layer comprising the matrix material located over and contacting the donor layer, wherein the first and second matrix layers have thicknesses differing from one another by no more than 20%;
wherein the intermediate article is heat treatable with at least the first and second matrix layers and the donor layer thereon to cause the Ag in the donor layer to self-assemble into a discontinuous collection of formations distributed in the matrix material in forming a metamaterial inclusive layer that emits resonances in a desired wavelength range based at least in part on the formations located therein.

### Claim 41 (depends on 40)

The article of claim 40, wherein the first and second matrix layers each have an as-deposited thickness of 30-70 nm.

### Claim 42 (depends on 40)

The article of claim 40, the matrix material comprises Nb and/or Si.

### Claim 43 (depends on 42)

The article of claim 42, wherein the matrix material comprises niobium oxide.

### Claim 44 (depends on 40)

The article of claim 40, wherein the donor layer has an as-deposited thickness of 5-10 nm.

### Claim 45 (depends on 40)

The article of claim 40, wherein the heat treating is performable at a time and temperature sufficient to cause the formations to have an interparticle spacing of 5-75 nm and diameters or major distances of 20-140 nm.

### Claim 46 (depends on 45)

The article of claim 45, wherein the heat treating is performable at a time and temperature sufficient to cause the formations to have 10-50 nm thicknesses.

### Claim 47 (depends on 40)

The article of claim 40, further comprising a plurality of continuous and uninterrupted IR reflecting layers, each IR reflecting layer comprising Ag.

### Claim 48 (depends on 47)

The article of claim 47, further comprising a plurality of barrier layers comprising TiZrOx.

### Claim 49 (depends on 47)

The article of claim 47, wherein the IR reflecting layers are formed over the metamaterial inclusive layer on a side of the metamaterial inclusive layer opposite the substrate.