# US 2019/0378773 A1 · Glass article having a metallic nanofilm and method of increasing adhesion between metal and glass

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- Number: US 2019/0378773 A1
- Document ID: US20190378773A1
- Status: Published application
- Kind: A1
- Application number: 16/432,472
- Filed: 2019-06-05
- Published: 2019-12-12
- Earliest claimed: 2018-06-11
- Assignees: Corning Incorporated
- Applicants: Corning Incorporated
- Inventors: Philip Simon Brown; Shrisudersan Jayaraman; Prantik Mazumder; Rajesh Vaddi
- Web page: https://patentgrep.com/patent/US20190378773A1

## CPC

- H10W 70/692: Ceramics or glasses
- C03C 17/3602: {the metal being present as a layer}
- 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 17/3649: {made of metals other than silver}
- C03C 17/3655: {the multilayer coating containing at least one conducting layer}
- C03C 17/3668: {the multilayer coating having electrical properties}
- C03C 17/38: at least one coating being a coating of an organic material
- C23C 18/1653: {Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating}
- C23C 18/18: Pretreatment of the material to be coated
- C23C 18/32: Coating with nickel, cobalt or mixtures thereof with phosphorus or boron (C23C18/50 takes precedence)
- C23C 18/38: Coating with copper
- C23C 28/02: only coatings {only including layers} of metallic material
- H10W 70/095: {of vias therein}
- H10W 70/635: {Through-vias}
- H10W 99/00: Subject matter not provided for in other groups of this subclass
- C03C 2217/256: Ag
- C03C 2217/263: Metals other than noble metals, Cu or Hg
- C03C 2218/115: electro-enhanced deposition
- C03C 2218/116: by spin-coating, centrifugation
- H10W: GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
- 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
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)

## Abstract

An article including a glass or glass ceramic substrate, a noble metal layer, an adhesion promoting layer positioned between and bonded to the substrate and the noble metal layer, and a conductive metal layer positioned on and bonded to the noble metal layer. The adhesion promoting layer includes a siloxy group bonded with the substrate and a thiol group bonded to the noble metal layer. A method for manufacturing an article including applying an adhesion promoting layer comprising mercaptosilane to at least a portion of a glass or glass ceramic substrate, wherein siloxane bonds are formed between the mercaptosilane and the substrate, applying a noble metal layer to the adhesion promoting layer, the noble metal layer bonds with a thiol present in the mercaptosilane, thermally treating the noble metal layer, and applying a conductive metal layer to the noble metal layer.

## Claims

### Claim 1

An article comprising:
a glass or glass ceramic substrate;
a noble metal layer;
an adhesion promoting layer positioned between and bonded to the glass or glass ceramic substrate and the noble metal layer; and
an electroplated conductive metal layer positioned directly on and bonded to the noble metal layer,
wherein the adhesion promoting layer comprises a siloxy group bonded with the glass or glass ceramic substrate and a thiol group bonded to the noble metal layer.

### Claim 2 (depends on 1)

The article of claim 1, wherein the noble metal layer comprises a noble metal selected from the group consisting of copper, silver, and gold.

### Claim 3 (depends on 1)

The article of claim 1, wherein the noble metal layer consists essentially of silver.

### Claim 4 (depends on 1)

The article of claim 1, wherein the electroplated conductive metal layer is a conductive metal selected from the group consisting of copper, nickel, cobalt, gold, silver, cadmium, chromium, lead, platinum, and combinations and alloys thereof.

### Claim 5 (depends on 1)

The article of claim 1, wherein the electroplated conductive metal layer consists essentially of copper.

### Claim 6 (depends on 1)

The article of claim 1, wherein the adhesion promoting layer is a monolayer.

### Claim 7 (depends on 1)

The article of claim 1, wherein the adhesion promoting layer has a thickness of less than 100 nm.

### Claim 8 (depends on 1)

The article of claim 1, wherein the noble metal layer has a thickness of less than one micron.

### Claim 9 (depends on 1)

The article of claim 1, wherein the noble metal layer is made from noble metal particles having an average particle size of less than or equal to 100 nm.

### Claim 10 (depends on 1)

The article of claim 1, wherein the noble metal layer has a sheet resistance of less than 500 ohm/square.

### Claim 11 (depends on 1)

The article of claim 1, wherein the glass or glass ceramic substrate comprises vias and/or trenches and the adhesion promoting layer, the noble metal layer, and the electroplated conductive metal layer are present in the vias and/or trenches.

### Claim 12

A method for manufacturing an article comprising:
applying an adhesion promoting layer comprising mercaptosilane to at least a portion of a glass or glass ceramic substrate, wherein siloxane bonds are formed between the mercaptosilane and the glass or glass ceramic substrate;
applying a noble metal layer to the adhesion promoting layer, wherein the noble metal layer bonds with a thiol present in the mercaptosilane;
thermally treating the noble metal layer by heating and cooling the noble metal layer; and
electroplating a conductive metal layer to the noble metal layer.

### Claim 13 (depends on 12)

The method of claim 12, wherein the noble metal layer comprises a noble metal selected from the group consisting of copper, silver, and gold.

### Claim 14 (depends on 12)

The method of claim 12, wherein the conductive metal layer is a conductive metal selected from the group consisting of copper, nickel, cobalt, gold, silver, cadmium, chromium, lead, platinum, and combinations and alloys thereof.

### Claim 15 (depends on 12)

The method of claim 12, wherein thermally treating the noble metal layer comprises heating the noble metal to a temperature from greater than or equal to 150° C. to less than or equal to 700° C. and cooling to room temperature.

### Claim 16 (depends on 12)

The method of claim 12, wherein thermally treating the noble metal layer comprises heating the noble metal to a temperature from greater than or equal to 150° C. to less than or equal to 350° C. and cooling to room temperature.

### Claim 17 (depends on 12)

The method claim 12, wherein the conductive metal layer is applied to the noble metal layer by electroplating.

### Claim 18 (depends on 17)

The method of claim 17, wherein the noble metal layer is used as an electrode for electroplating the conductive metal layer to the noble metal layer.

### Claim 19 (depends on 12)

The method of claim 12, wherein an additional metal layer is applied to the noble metal layer by electroless plating, and the conductive metal layer is applied to the additional metal layer by electroplating.

### Claim 20 (depends on 19)

The method of claim 19, wherein the additional metal layer comprises a member selected from the group consisting of copper, nickel, and cobalt.