IP Library Granted Patent US 12,252,784
Granted Patent B2
US 12,252,784 · App. 17/618,217 · Granted Mar 18, 2025

Copper halide layers

Inventors: Christina M. Chang (Cambridge, MA); Luke M. Davis (Cambridge, MA); Roy Gerald Gordon (Cambridge, MA)
Assignee: President and Fellows of Harvard College
C23C16/30C01G3/05C23C16/0272H01G9/20H10K30/40H10K2102/00
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Quick Facts
Patent No.
US 12,252,784
App. No.
17/618,217
Granted
Mar 18, 2025
Kind
B2
Abstract

Articles are described including a substrate and a copper halide layer on the substrate, where the interfacial free energy between the substrate and the copper halide layer allows the copper halide layer to form continuously, wherein the copper halide layer conforms to the shape of the substrate. The articles may further include an adhesion layer disposed in-between the substrate and the copper halide layer, where the surface free energy between the adhesion layer and the copper halide layer allows the copper halide layer to form continuously, wherein the copper halide layer or the adhesion layer conform to the shape of the substrate. Also described are methods of forming an article using chemical vapor deposition.

Claims (53)

1. An article comprising:

a substrate; and

a copper halide layer on the substrate;

wherein the interfacial free energy between the substrate and the copper halide layer is configured such that:

the copper halide layer is free of discontinuations of sizes of about 5 nm 2 or greater; and

the copper halide layer conforms to the shape of the substrate.

2. The article of claim 1 , wherein the copper halide comprises a compound of formula CuF a Cl b Br d I e , where a, b, d, and e are independently between 0 and 1, inclusive, and the sum of a, b, d, and e is 1.

3. The article of claim 2 , wherein the copper halide is CuF, CuCl, CuBr, or CuI.

4. The article of claim 1 , wherein the substrate has a thickness of between about 1 nm and about 1 mm.

5. The article of claim 1 , wherein the substrate has a thickness of between about 1 nm and about 1 cm.

6. The article of claim 1 , wherein the article is optically transparent.

7. The article of claim 6 , wherein the article has a transmittance of greater than about 80% over the wavelength range from about 400 nm to about 800 nm.

8. The article of claim 1 , wherein the article is electrically conductive.

9. The article of claim 8 , wherein the resistivity of the article is between about 0.00375 Ω·cm and about 20 Ω·cm.

10. The article of claim 8 , wherein the sheet resistance of the article is between about 2.5×10 2 Ω·sq −1 and about 2×10 6 Ω·sq −1 .

11. The article of claim 8 , wherein the hole concentration of the article is between about 1 ×10 17 cm −3 and about 1 ×10 19 cm −3 .

12. The article of claim 8 , wherein the mobility of the article is between about 0.07 cm 2 V −1 s −1 and about 10 cm 2 V −1 s −1 .

13. The article of claim 8 , wherein the electrical conductivity of the copper halide layer is p-type.

14. The article of claim 1 , wherein the copper halide layer has a thickness of between about 50 nm to about 1000 nm.

15. The article of claim 1 , wherein the copper halide layer is CuBr and the substrate is selected from the group consisting of silicon nitride, platinum, SiO 2 , Al 2 O 3 , and glassy carbon.

16. The article of claim 1 , wherein the copper halide layer is CuI and the substrate is selected from the group consisting of silicon nitride, platinum, SiO 2 , Al 2 O 3 , and glassy carbon.

17. The article of claim 1 , wherein:

the substrate further comprises an adhesion layer conformally formed on the substrate; and

the copper halide layer is on the adhesion layer;

wherein the interfacial free energy between the substrate or the adhesion layer and the copper halide layer allows the copper halide layer to be free of discontinuations of sizes of about 5 nm 2 or greater; and

wherein the copper halide layer conforms to the shape of the adhesion layer.

18. The article of claim 17 , wherein the substrate and adhesion layer are independently selected from the group consisting of a metal, a metalloid, a metal halide, a metal oxide, a metal nitride, glassy carbon, a semiconductor wafer, plastic, glass, and a combination thereof.

19. The article of claim 18 , wherein the metal is platinum, titanium, gold, or a combination thereof.

20. The article of claim 18 , wherein the metalloid is silicon.

21. The article of claim 18 , wherein the metal halide is NaCl or a perovskite.

22. The article of claim 21 , wherein the perovskite comprises methylammonium tin trishalide, methylammonium lead trishalide, cesium tin trishalide, cesium lead trishalide, formamidinium tin trishalide, formamidinium lead trishalide, or a combination thereof.

23. The article of claim 18 , wherein the metal oxide is SiO 2 , Al 2 O 3 , TiO 2 , quartz, or a combination thereof.

24. The article of claim 18 , wherein the metal nitride is silicon nitride, manganese nitride, or a combination thereof.

25. The article of claim 24 , wherein the silicon nitride includes silicon oxynitride at its surface.

26. The article of claim 18 , wherein the semiconductor wafer comprises silicon, a mixture of silicon and SiO 2 , GaAs, silicon carbide, or gallium nitride.

27. The article of claim 26 , wherein the semiconductor wafer comprises a mixture of silicon and SiO 2 .

28. The article of claim 17 , wherein the adhesion layer has a thickness of between about 1 nm and about 1000 nm.

29. The article of claim 28 , wherein the adhesion layer has a thickness of between about 40 nm and about 300 nm.

30. The article of claim 17 , wherein the surface free energy of the copper halide layer, the substrate, or the adhesion layer is between about 0 mJ/m 2 to about 50 mJ/m 2 .

31. The article of claim 17 , wherein the copper halide layer is CuBr, the adhesion layer is silicon nitride or platinum, and the substrate is selected from the group consisting of SiO 2 , quartz, silicon, and a SiO 2 /Si wafer.

32. The article of claim 17 , wherein the copper halide layer is CuI, the adhesion layer is silicon nitride or platinum, and the substrate is selected from the group consisting of SiO 2 , quartz, silicon, and a SiO 2 /Si wafer.

33. An optoelectronic device, comprising the article of claim 1 .

34. The optoelectronic device of claim 33 , wherein the optoelectronic device is selected from the group consisting of perovskite solar cells, dye-sensitized solar cells, photonic emitters, electrooptic modulators, optical fibers, four-wave mixing devices, flat-panel displays, and thin-film transistors.

35. A method of fabricating an article, comprising:

providing a substrate; and

depositing a copper halide layer on the substrate using a chemical vapor deposition process;

wherein the interfacial free energy between the substrate and the copper halide layer allows the copper halide layer to form free of discontinuations of sizes of about 5 nm 2 or greater; and

wherein the copper halide layer conforms to the shape of the substrate.

36. The method of claim 35 , wherein

the substrate further comprises an adhesion layer;

wherein the copper halide layer is deposited on the adhesion layer using a chemical vapor deposition process;

wherein the interfacial free energy between the substrate or adhesion layer and the copper halide layer allows the copper halide layer to form free of discontinuations of sizes of about 5 nm 2 or greater; and

wherein the copper halide layer conforms to the shape of the substrate or adhesion layer.

Assignments (3)
CONFIRMATORY LICENSE Recorded Jun 18, 2025
From: HARVARD UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 071654/0381 →
CONFIRMATORY LICENSE Recorded Feb 3, 2025
From: HARVARD UNIVERSITY
To: NATIONAL SCIENCE FOUNDATION
Reel/Frame 070084/0403 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 6, 2022
From: CHANG, CHRISTINA MARIE; DAVIS, LUKE M; GORDON, ROY G
To: PRESIDENT AND FELLOWS OF HARVARD COLLEGE
Reel/Frame 061989/0360 →
Continuity (2)
Provisional Application 62860579 · Jun 12, 2019
Related Publication 20220380893A1 · Dec 1, 2022
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