IP Library Granted Patent US 8,425,739
Granted Patent B1
US 8,425,739 · App. 12/565,749 · Granted Apr 23, 2013

In chamber sodium doping process and system for large scale cigs based thin film photovoltaic materials

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Quick Facts
Patent No.
US 8,425,739
App. No.
12/565,749
Granted
Apr 23, 2013
Kind
B1
Abstract

A method of processing a photovoltaic materials using a sputtering process including providing at least one transparent substrate having an overlying first electrode layer. The method further including forming an overlying copper and gallium layer using a first sputtering process within a first chamber from a first target including a copper species and a gallium species. Additionally, the method includes forming an indium layer overlying the copper and the gallium layer using a second sputtering process within the first chamber from a second target including an indium species. The method further includes forming a sodium bearing layer overlying the indium layer using a third sputtering process within the first chamber, thereby forming a composite film including the copper and gallium layer, the indium layer, and the sodium bearing layer. Furthermore, the method includes subjecting the composite film to at least a thermal treatment process to form a chalcopyrite absorber layer comprising copper, indium, gallium, and sodium therein.

Claims (49)

1. A method of processing a photovoltaic materials using a sputtering process, the method comprising:

providing at least one transparent substrate having an overlying first electrode layer;

forming, using a first sputtering process within a first chamber, an overlying copper and gallium layer from a first target including a copper species and a gallium species;

forming, using a second sputtering process within the first chamber, an indium layer overlying the copper and the gallium layer from a second target including an indium species;

forming, using a third sputtering process within the first chamber, a sodium bearing layer overlying the indium layer, thereby forming a composite film including the copper and gallium layer, the indium layer, and the sodium bearing layer, wherein forming the sodium bearing layer is performed by sputtering on a target bearing Na2SeO3 with total 8 at % of sodium mixed with copper and gallium; and

subjecting the composite film to at least a thermal treatment process to form a chalcopyrite absorber layer comprising copper, indium, gallium, and sodium therein.

2. The method of claim 1 wherein the transparent substrate comprises a soda lime glass substrate.

3. The method of claim 1 wherein the first electrode layer comprises a bi-layer molybdenum material.

4. The method of claim 1 wherein the chalcopyrite absorber layer comprises a compound semiconductor of CuInSe 2 (CIS) or CuIn(Ga)Se 2 (CIGS) or CuIn(Ga)S 2 with sodium doping.

5. The method of claim 1 wherein the chalcopyrite absorber layer comprises sodium with an average atomic density of about 5×10 19 atoms/cm 3 throughout the absorber layer after thermal treatment process.

6. The method of claim 1 wherein the third sputtering process uses a sodium bearing target with a uniform composition of the sodium species distributed within a host material.

7. The method of claim 1 wherein the first sputtering process, the second sputtering process, and the third sputtering process are carried out in a same chamber but different compartment.

8. The method of claim 1 wherein the thermal treatment process is performed at a temperature ramping up from room temperature to above about 500 degree Celsius or greater.

9. The method of claim 1 wherein the thermal treatment process is performed in a fluidic selenide or fluidic sulfide environment.

10. A method of processing a photovoltaic material using a sputtering process, the method comprising:

providing at least one transparent substrate having an overlying first electrode layer;

forming, using a first sputtering process within a first chamber, an overlying copper and gallium layer from a first target including a copper species and a gallium species;

forming, using a second sputtering process within the first chamber, an indium layer overlying the copper and the gallium layer from a second target including an indium species;

transferring the transparent substrate including the indium layer overlying the copper layer to a second chamber without breaking vacuum between the first chamber and the second chamber to maintain the copper gallium layer and indium layer substantially free from moisture;

forming, using a third sputtering process within the second chamber, a sodium bearing layer overlying the indium layer, thereby forming a composite film including the copper and gallium layer, the indium layer, and the sodium bearing layer, wherein forming the sodium bearing layer is performed by sputtering on a target bearing Na2SeO3 with total 8 at % of sodium mixed with copper and gallium;

subjecting the composite film to at least a thermal treatment process to form a chalcopyrite absorber layer comprising copper, indium, gallium, and sodium therein; and

maintaining the transparent substrate including the composite film to an environment substantially free from moisture.

11. The method of claim 10 wherein the environment comprises dry air.

12. The method of claim 10 wherein the environment comprises dry nitrogen.

13. The method of claim 10 wherein the transparent substrate comprises a soda lime glass substrate.

14. The method of claim 10 wherein the first electrode layer comprises molybdenum material.

15. The method of claim 10 wherein the chalcopyrite absorber layer comprises a compound semiconductor of CuInSe 2 (CIS) or CuIn(Ga)Se 2 (CIGS) or CuIn(Ga)S 2 .

16. The method of claim 10 wherein the chalcopyrite absorber layer comprises sodium concentration of about 5×10 19 atoms/cm 3 after thermal treatment process.

17. The method of claim 10 wherein the third sputtering process uses a sodium bearing target with a uniform composition of the sodium species distributed within a host material.

18. The method of claim 10 wherein the first sputtering process, the second sputtering process, and the third sputtering process are carried out in a same chamber but different compartment.

19. The method of claim 10 wherein the thermal treatment process is performed in a fluidic selenide or fluidic sulfide environment within a diffusion furnace.

20. The method of claim 19 wherein the fluidic selenide environment comprises a hydrogen selenide gas and the fluidic sulfide environment comprises a hydrogen sulfide gas.

21. The method of claim 19 wherein the thermal treatment process is performed with nitrogen gas added to enhance temperature uniformity in the diffusion furnace.

22. A method of processing a photovoltaic material, the method comprising:

providing a substrate having an overlying a molybdenum layer;

forming a sodium bearing layer overlying the molybdenum layer, wherein forming the sodium bearing performed by sputtering on a target bearing Na 2 SeO 3 with total 8 at % of sodium mixed with copper and gallium;

forming a precursor layer comprising copper, gallium, and indium overlying the sodium bearing layer; and

subjecting the precursor layer to a thermal treatment process to form a photovoltaic absorber layer comprising a chalcopyrite structure bearing with copper, indium, gallium, and sodium therein.

23. The method of claim 22 wherein the substrate is a smooth plate.

24. The method of claim 22 wherein subjecting the precursor layer to a thermal treatment comprises ramping up process temperature to 500 Degrees Celsius within a gaseous environment containing selenium.

25. A method of processing a photovoltaic materials using a sputtering process, the method comprising:

providing at least one transparent substrate having an overlying first electrode layer;

performing a first sputtering process within a first chamber utilizing a first target to deposit a first layer;

performing a second sputtering process within the first chamber utilizing a second target to deposit a second layer;

performing a third sputtering process within the first chamber utilizing a third target bearing Na2SeO3 with total 8 at % of sodium mixed with copper and gallium to deposit a third layer; and

subjecting the composite film to at least a thermal treatment process to form a chalcopyrite absorber layer comprising copper, indium, gallium, and sodium therein.

26. The method of claim 25 wherein the first sputtering process deposits a copper and gallium layer overlying the electrode from the first target including a copper species and a gallium species, wherein the second sputtering process deposits an indium layer overlying the copper and gallium layer from the second target including an indium species, and wherein the third sputtering process deposits a sodium bearing layer overlying the indium layer from the third target including a sodium species.

27. The method of claim 25 wherein the first sputtering process deposits an indium layer overlying the electrode from the first target including an indium species, wherein the second sputtering process deposits a copper and gallium layer overlying the indium layer from the second target including a copper species and a gallium species, and wherein the third sputtering process deposits a sodium bearing layer overlying the copper and gallium layer from the third target including a sodium species.

28. The method of claim 25 wherein the first sputtering process deposits an indium layer overlying the electrode from the first target including an indium species, wherein the second sputtering process deposits a sodium bearing layer overlying the indium layer from the second target including a sodium species, and wherein the third sputtering process deposits a copper and gallium layer overlying the sodium layer from the third target including a copper species and a gallium species.

Assignments (4)
CHANGE OF NAME Recorded Feb 21, 2014
From: HETF SOLAR INC.
To: STION CORPORATION
Reel/Frame 032324/0402 →
SECURITY AGREEMENT Recorded Feb 10, 2014
From: DEVELOPMENT SPECIALIST, INC., SOLELY IN ITS CAPACITY AS THE ASSIGNEE FOR THE BENEFIT OF THE CREDITORS OF CM MANUFACTURING, INC. (F/K/A STION CORPORATION), AND CM MANUFACTURING (F/K/A STION CORPORATION)
To: HETF SOLAR INC.
Reel/Frame 032209/0879 →
CHANGE OF NAME Recorded Jan 30, 2014
From: STION CORPORATION
To: CM MANUFACTURING, INC.
Reel/Frame 032144/0774 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 2, 2009
From: WIETING, ROBERT D.
To: STION CORPORATION
Reel/Frame 023458/0793 →