IP Library Granted Patent US 8,617,640
Granted Patent B2
US 8,617,640 · App. 11/762,056 · Granted Dec 31, 2013

Thin-film devices formed from solid group IIIA alloy particles

Inventors: Matthew R. Robinson (Palo Alto, CA); Chris Eberspacher (Palo Alto, CA); Jeroen K. J. Van Duren (Menlo Park, CA)
Assignee: Nanosolar, Inc.
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Quick Facts
Patent No.
US 8,617,640
App. No.
11/762,056
Granted
Dec 31, 2013
Kind
B2
Abstract

Methods and devices are provided for forming thin-films from solid group IIIA-based particles. In one embodiment, a method is provided for creating solid alloy particles. The method may include providing a first material containing at least one alloy comprising of: a) a group IIIA element, b) at least one group IB, IIIA, and/or VIA element different from the group IIIA element of a), and c) a group IA-based material. The group IA-based material may be included in an amount sufficient so that no liquid phase of the alloy is present in a temperature range between room temperature and a deposition temperature higher than room temperature, wherein the group IIIA element is otherwise liquid in that temperature range. The method may involve formulating a precursor material comprising of: a) particles of the first material and b) particles containing at least one element from one of the following: a group IB element, a group IIIA element, a group VIA element, alloys containing any of the foregoing elements, or combinations thereof.

Claims (58)

1. A method comprising:

providing a material containing at least one compound having:

a) a group IIIA element,

b) at least one group IB, IIIA, and/or VIA element different from the element of a), and

c) a group IA-based material, wherein the group IA-based material is included in an amount sufficient so that no liquid phase of the material is present in a temperature range between room temperature and a process temperature higher than room temperature, wherein the group IIIA element is otherwise liquid in that temperature range;

formulating a precursor material comprised of the material; and

reacting the precursor material in one or more reaction steps to form a photovoltaic absorber layer.

2. The method of claim 1 wherein the group IA-based material includes at least one element from the group consisting of: a group IB element, a group IIIA element, a group VIA element, an alloy containing any of the foregoing elements, and/or combinations thereof.

3. The method of claim 2 wherein the alloy comprises In—Ga—Na.

4. The method of claim 2 wherein the alloy comprises In—Ga—Se—Na.

5. The method of claim 2 wherein the alloy comprises Ga—Se—Na.

6. The method of claim 2 wherein the alloy comprises one of the following: In—Se—Na, Cu—In—Na, or Cu—Ga—Na.

7. The method of claim 2 wherein the alloy comprises sulfur.

8. The method of claim 2 wherein the alloy comprises Cu—In—Ga—Na.

9. The method of claim 1 wherein the temperature range is between about 20° C. and about 200° C.

10. The method of claim 1 wherein the temperature range is between about 20° C. and about 500° C.

11. The method of claim 1 wherein the precursor material further includes a group IB, IIIA, and/or VIA based material.

12. The method of claim 1 wherein the precursor material is in the form of particles.

13. The method of claim 12 wherein the group IA-based material is at least partially included in the particles.

14. The method of claim 12 wherein the precursor material contains particles comprising IB-based particles.

15. The method of claim 12 wherein the precursor material contains particles comprising IB-based alloy particles.

16. The method of claim 12 wherein the precursor material contains particles comprising IB-IIIA based alloy particles.

17. The method of claim 12 wherein the precursor material contains particles comprising IB-VIA based alloy particles.

18. The method of claim 12 wherein the particles include nanoparticles.

19. The method of claim 12 wherein the particles include spherical nanoparticles.

20. The method of claim 12 wherein the particles include non-spherical, planar flakes.

21. The method of claim 12 wherein the particles are formed using at least one of the following methods: grinding, milling, electroexplosive wire (EEW) processing, evaporation condensation (EC), pulsed plasma processing, or combinations thereof.

22. The method of claim 12 wherein the particles are formed using at least one of the following methods: sonification, agitation, electromagnetically mixing of a liquid metal or liquid alloy.

23. The method of claim 12 wherein the particles are formed using at least one of the following methods: spray-pyrolysis, laser pyrolysis, or a bottom-up technique like wet chemical approaches.

24. The method of claim 1 wherein a group IIIA element is In.

25. The method of claim 1 wherein the group IIIA element of the first material is Ga.

26. The method of claim 1 wherein the group IA-based material comprises elemental sodium.

27. The method of claim 1 wherein the group IA-based material comprises a sodium-based compound.

28. The method of claim 1 , wherein the group IA-based material contains an element chosen from the group consisting of sodium (Na), potassium (K), lithium (Li), compounds containing any of the foregoing, or combinations thereof.

29. The method of claim 1 further comprising using the precursor material in a solution coatable ink for forming a film on a substrate.

30. The method of claim 1 further comprising:

formulating an ink including the precursor material;

solution depositing the ink onto a substrate to form a precursor layer on the substrate; and

reacting the precursor layer in a suitable atmosphere to form a group IB-IIIA-VIA based film.

31. The method of claim 30 wherein the film includes a group IB-IIIA-VIA compound.

32. The method of claim 1 further comprising:

formulating an ink including the precursor material;

solution depositing the ink onto a substrate to form a precursor layer on the substrate; and

reacting the precursor layer in a suitable atmosphere to form a IB-IIIA film.

33. The method of claim 30 further comprising heating the film in a group VIA based atmosphere to form a group IB-IIIA-VIA compound film.

34. The method of claim 30 wherein the film comprises a semiconductor film suitable for use in a photovoltaic device.

35. The method of claim 30 wherein the film comprises an absorber layer for a solar cell.

36. The method of claim 30 wherein reacting comprises heating the layer in the suitable atmosphere.

37. The method of claim 30 further comprising adding a mixture of one or more elemental particles selected from: aluminum, tellurium, sulfur, copper, indium, gallium, alloys containing any of the foregoing, and combinations thereof.

38. The method of claim 30 wherein the suitable atmosphere contains at least one of the following: selenium, sulfur, tellurium, H2, CO, H2Se, H2S, Ar, N2 or combinations or mixtures thereof.

39. The method of claim 30 wherein one or more classes of the particles are doped with one or more inorganic materials.

40. The method of claim 30 , wherein one or more classes of the particles are doped with one or more inorganic materials containing at least one element from the group of aluminum (Al), sulfur (S), sodium (Na), potassium (K), or lithium (Li).

41. The method of claim 30 wherein the film has a Cu/(In+Ga) compositional range of about 0.01 to about 1.0 and a Ga/(In+Ga) compositional range of about 0.01 to about 1.0.

42. The method of claim 30 wherein the film has a Cu/(In+Ga) compositional range >1.0 and a Ga/(In+Ga) compositional range of about 0.01 to about 1.0.

43. The method of claim 30 wherein the film's desired Cu/(In+Ga) molar ratio is in the range of about 0.7 to about 1.0 and a desired Ga/(Ga+In) molar ratio in the range of about 0.1 to about 0.8.

44. The method of claim 30 wherein the ink includes a carrier liquid.

45. The method of claim 30 wherein depositing comprises using at least one of the following techniques: wet coating, spray coating, spin coating, doctor blade coating, contact printing, top feed reverse printing, bottom feed reverse printing, nozzle feed reverse printing, gravure printing, microgravure printing, reverse microgravure printing, comma direct printing, roller coating, slot die coating, meyerbar coating, lip direct coating, dual lip direct coating, capillary coating, ink jet printing, jet deposition, spray deposition, or combinations thereof.

46. The method of claim 32 wherein the film is a dense film that includes a group IB-IIIA alloy.

Assignments (3)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 16, 2014
From: ROBINSON, MATTHEW R.; EBERSPACHER, CHRIS; VAN DUREN, JEROEN K.J.
To: NANOSOLAR, INC.
Reel/Frame 033111/0104 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 21, 2014
From: NANOSOLAR, INC.
To: AERIS CAPITAL SUSTAINABLE IP LTD.
Reel/Frame 033005/0701 →
SECURITY AGREE,EMT Recorded Nov 15, 2012
From: NANOSOLAR, INC.
To: AERIS CAPITAL SUSTAINABLE IMPACT PRIVATE INVESTMENT FUND CAYMAN L.P.
Reel/Frame 029556/0418 →
Continuity (1)
Related Publication 20080175982A1 · Jul 24, 2008