Glass or glass-ceramic article coated with hard material and method for production thereof

• US 8,460,804 B2
• Filed: 07/01/2008
• Issued: 06/11/2013
• Est. Priority Date: 07/16/2007
• Status: Active Grant

• Current Assignee: Schott AG (Carl-Zeiss-Stiftung)
• Original Assignee: Schott AG (Carl-Zeiss-Stiftung)
• Inventors: Henn, Christian, Gabel, Falk
• Primary Examiner(s): McNeil, Jennifer
• Assistant Examiner(s): COLGAN, LAUREN ROBINSON
• Application Number:
  US12/452,712
• Publication Number:
  US 20100304090A1
• Time in Patent Office: 1,806 Days
• Field of Search: 428/426, 428/428, 428/688, 428/689, 428/698, 428/432, 428/704, 204/192.1, 204/298.01, 204/298.09
• US Class Current: 428/698
• CPC Class Codes: C03C 17/002 for flat glass, e.g. float glass
• CPC Class Codes: C03C 17/225 Nitrides
• CPC Class Codes: C03C 17/3435 comprising a nitride, oxynitride, boronitride or carbonitride
• CPC Class Codes: C23C 14/0652 Silicon nitride
• CPC Class Codes: C23C 14/56 Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
• CPC Class Codes: C23C 14/5806 Thermal treatment
• CPC Class Codes: Y02T 50/60 Efficient propulsion technologies, e.g. for aircraft
• CPC Class Codes: Y10T 428/24612 Composite web or sheet
• CPC Class Codes: Y10T 428/265 1 mil or less

Abstract

The object of the invention is to create a hard-material coating for glass ceramics and glasses, a coating which is particularly temperature-resistant and protects the substrate from mechanically caused damage as well as chemical attack. For this purpose, a silicon nitride coating is proposed, which has a structure-free morphology in the volume.

Claims

1. A glass or glass-ceramic article coated with hard material having a glass substrate or a glass-ceramic substrate, comprising:

a silicon nitride layer is deposited on the substrate as a hard-material layer, wherein the silicon nitride layer has an x-ray amorphous morphology in the volume, and has a structure-free morphology such that it appears structure-free in an electron micrograph of the cross section with 5 kV accelerating voltage at 100,000×

magnification.

2. The glass or glass-ceramic article of claim 1, further comprising a ceramic decoration on the substrate, the hard-material layer being deposited over the ceramic decoration.

3. The glass or glass-ceramic article of claim 1, wherein the coated surface of the substrate is annealed at a temperature between 600°

C. and 750°

C. and wherein the morphology of the silicon nitride layer is after the annealing.

4. The glass or glass-ceramic article of claim 1, wherein the coated surface of the substrate is annealed at a temperature between 600°

C. and 750°

C. and wherein the silicon nitride layer has a layer stress with a value of less than 200 MPa at room temperature after the annealing.

5. The glass or glass-ceramic article of claim 1, wherein the coated surface of the substrate is annealed at a temperature between 600°

C. and 750°

C. and wherein the silicon nitride layer has a compressive stress at room temperature after the annealing.

6. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer has a compressive stress at a temperature above 450°

C.

7. The glass or glass-ceramic article of claim 6, wherein the compressive stress at 450°

C. lies in the range between 100 and 500 MPa.

8. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer has a layer thickness in the range of 500 to 2500 nanometers.

9. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer has a layer thickness in the range of 750 to 1500 nanometers.

10. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer is on a surface of the substrate having a layer thickness of at least 1 μ

m and a Vickers hardness of more than 2000 HV.

11. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer is on a surface of the substrate having a layer thickness of at least 1 μ

m and a Vickers hardness of at least 2400 HV.

12. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer is an aluminum-doped silicon nitride layer.

13. The glass or glass-ceramic article of claim 12, wherein the silicon nitride layer has a ratio of aluminum to silicon of at least 0.05.

14. The glass or glass-ceramic article of claim 12, wherein the silicon nitride layer has a ratio of aluminum to silicon of at least 0.1.

15. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer has at least two layer parts directly following one another defining an interface, the interface being visible in an electron micrograph of the cross section with 5 kV accelerating voltage at 100,000×

magnification.

16. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer is directly, at least in regions, on the substrate, without intermediate layer therebetween.

17. The glass or glass-ceramic article of claim 1, wherein the silicon nitride layer has a layer thickness that varies by at most 5% along the layer.

18. The glass or glass-ceramic article of claim 1, wherein the substrate is selected from the group consisting of a glass ceramic, a borosilicate glass, and a soda-lime glass.

19. The glass or glass-ceramic article of claim 18, wherein the substrate is the glass ceramic and the glass ceramic has a linear temperature expansion coefficient of less than 3*10⁻

6 K<sup>−

1</sup> in a temperature range between 20°

C. and 700°

C.

20. The glass or glass-ceramic article of claim 1, wherein the glass or glass-ceramic article is annealed at between 600 and 700°

C. and shows a color change Δ

E of less than 1.5 after the annealing, Δ

E denoting the color distance in the lab color space.

21. A glass or glass-ceramic article coated with hard material having a glass substrate or a glass-ceramic substrate, comprising:

a silicon nitride layer deposited by sputtering at a power of more than 10 watts per cm² of target surface on the substrate as a hard-material layer with a layer thickness of at least 1 μ

m and a Vickers hardness of more than 2000 HV, wherein the silicon nitride layer has an x-ray amorphous morphology in the volume, and has a structure-free morphology such that it appears structure-free in an electron micrograph of the cross section with 5 kV accelerating voltage at 100,000×

magnification.

22. The glass or glass-ceramic article of claim 21, wherein the Vickers hardness is at least 2400 HV.

23. The glass or glass-ceramic article of claim 21, wherein the power is at least 12 watts per cm² of target surface.