Photovoltaic element and fabrication process thereof

• US 5,720,826 A
• Filed: 05/29/1996
• Issued: 02/24/1998
• Est. Priority Date: 05/30/1995
• Status: Expired due to Term

• Current Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Original Assignee: Canon Kabushiki Kaisha (Canon Inc.)
• Inventors: Koda, Yuzo, Matsuyama, Jinsho, Sakai, Akira, Kanai, Masahiro, Hayashi, Ryo, Fujioka, Yasushi, Hori, Tadashi, Okabe, Shotaro, Yajima, Takahiro
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US08/657,066
• Time in Patent Office: 636 Days
• Field of Search: 136/249 TJ, 136/258 AM, 136/258 PC, 136/249, 257/53, 257/55, 257/440, 257/458, 437/4, 437/101, 437/108-109, 437/113, 427/574-575, 427/578-579, 438/96-97, 438/482, 438/484, 438/485
• US Class Current: 136/249
• CPC Class Codes: H01L 31/03921 including only elements of Group IV of the Periodic Table
• CPC Class Codes: H01L 31/076 Multiple junction or tandem solar cells
• CPC Class Codes: H01L 31/202 including only elements of Group IV of the Periodic Table
• CPC Class Codes: H01L 31/204 including AIVBIV alloys, e.g. SiGe, SiC
• CPC Class Codes: H01L 31/206 Particular processes or apparatus for continuous treatment of the devices, e.g. roll-to roll processes, multi-chamber deposition
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells
• CPC Class Codes: Y02E 10/548 Amorphous silicon PV cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Provided are a photovoltaic element suitable for practical use, low in cost, high in reliability, and high in photoelectric conversion efficiency, and a fabrication process thereof. In the photovoltaic element having stacked layers of non-single-crystal semiconductors, at least an i-type semiconductor layer and a second conductivity type semiconductor layer are stacked on a first conductivity type semiconductor layer, and the second conduction type semiconductor layer has a layer A formed by exposing the surface of the i-type semiconductor layer to a plasma containing a valence electron controlling agent and a layer B deposited on the layer A by a CVD process using at least the valence electron controlling agent and the main constituent elements of the i-type semiconductor layer.

Claims

1. A photovoltaic element having stacked films of non-single-crystal semiconductors, comprising a first conductivity type semiconductor layer, an i-type semiconductor layer on said first conductivity type semiconductor layer and a second conductivity type semiconductor layer on said i-type semiconductor layer, wherein said second conductivity type semiconductor layer has a first layer A formed by exposing the surface of the i-type semiconductor layer to a plasma containing a valence electron controlling agent and a layer B deposited on said layer A by a CVD process using at least a valence electron controlling agent and the main constituent element(s) of said i-type semiconductor layer.

2. A photovoltaic element according to claim 1, wherein said layer A further comprises at least one element for increasing the bandgap thereof.

3. A photovoltaic element according to claim 2, wherein said at least one element for increasing the bandgap is at least one element selected from the group consisting of carbon, oxygen, and nitrogen.

4. A photovoltaic element according to claim 1, wherein said layer B further comprises at least one element for increasing the bandgap thereof.

5. A photovoltaic element according to claim 4, wherein said at least one element for increasing the bandgap is at least one element selected from the group consisting of carbon, oxygen, and nitrogen.

6. A photovoltaic element according to claim 1, wherein said layer A and said layer B further comprise at least one element for increasing the bandgap thereof.

7. A photovoltaic element according to claim 6, wherein said at least one element for increasing the bandgap is at least one element selected from the group consisting of carbon, oxygen, and nitrogen.

8. A photovoltaic element according to claim 1, wherein said first conductivity type is the n-type and said second conductivity type is the p-type.

9. A photovoltaic element according to claim 1, wherein said first conductivity type is the p-type and said second conductivity type is the n-type.

10. A photovoltaic element according to claim 1, wherein the hydrogen content of said layer A, formed by converting the surface of the i-type semiconductor layer into a p-type or n-type region, is larger than the hydrogen content of said i-type semiconductor layer.

11. A photovoltaic element according to claim 1, wherein the crystal form of said layer A is amorphous and the crystal form of said layer B is microcrystalline or polycrystalline.

12. A photovoltaic element according to claim 1, wherein said at least one valence electron controlling agent is an element belonging to Group III or Group V of the Periodic Table.

13. A photovoltaic element according to claim 1, wherein layer B contains the same at least one valence electron controlling agent as contained in layer A.

14. A photovoltaic element according to claim 13, wherein said at least one valence electron controlling agent is at least one element belonging to Group III or Group V of the Periodic Table.

15. A photovoltaic element according to claim 1, wherein said layer B has a thickness of 1 nm to 10 nm.

16. A photovoltaic element according to claim 1, wherein said i-type semiconductor layer comprises silicon or germanium.

17. A photovoltaic element according to claim 16, wherein said i-type semiconductor layer further comprises at least one element selected from the group consisting of carbon, oxygen, and nitrogen.

18. A photovoltaic element according to claim 1, wherein said i-type semiconductor layer comprises at least one element selected from the group consisting of carbon, oxygen, and nitrogen.

19. A photovoltaic element according to claim 1, wherein when a set of layers has said first conductivity type semiconductor layer, i-type semiconductor layer, layer A and layer B stacked in this order, a plurality of such sets are stacked.

20. A photovoltaic element according to claim 1, wherein there are a plurality of stacked sets of layers, comprising a first set having said first conductivity type semiconductor layer, i-type semiconductor layer, layer A and layer B stacked in this order and a second set having the first conductivity type semiconductor layer, i-type semiconductor layer, and second conductivity type semiconductor layer stacked in this order.

21. A photovoltaic element according to claim 20, which comprises a plurality of such second sets.

22. A photovoltaic element according to claim 20, which has the first set closer to a light incidence side than said second set.

23. A photovoltaic element according to claim 22, which comprises a plurality of such second sets.

24. A photovoltaic element according to claim 1, which has an electrically conductive layer on said layer B.

25. A photovoltaic element according to claim 24, wherein said electrically conductive layer comprises a transparent conductive layer.

26. A photovoltaic element according to claim 25, further comprising a collector electrode on said transparent conductive layer.

27. A photovoltaic element according to claim 1, wherein a substrate on which said semiconductors are formed has a reflective film thereon.

28. A photovoltaic element according to claim 1, wherein a substrate on which said semiconductors are formed has a buffer layer thereon.

29. A photovoltaic element according to claim 1, wherein said layer A has a thickness of 1 nm to 10 nm.

30. A photovoltaic element according to claim 1, wherein said semiconductor layers contain hydrogen atoms, and the content of the hydrogen atoms is greater near an interface between the layers.

31. A photovoltaic element according to claim 30, wherein said hydrogen content near said interface is 1.1 to 2 times greater.

32. A process for fabricating a photovoltaic element, comprising:

a step of depositing a first conductivity type semiconductor;

a step of depositing an i-type semiconductor on said first conductivity type semiconductor;

a step of exposing a surface region of said i-type semiconductor layer to a plasma atmosphere containing a valence electron controlling agent, thereby forming from said surface region a layer A of a second conductivity type semiconductor; and

a step of depositing a second conductivity type semiconductor containing a valence electron controlling agent on said layer A, thereby forming a layer B.

33. A fabrication process according to claim 32, wherein said plasma atmosphere further comprises at least one element for increasing the bandgap of said layer A.

34. A fabrication process according to claim 33, wherein said at least one element for increasing the bandgap is at least one element selected from the group consisting of carbon, oxygen, and nitrogen.

35. A fabrication process according to claim 33, wherein the pressure upon generating the plasma for forming said layer A is lower than the pressure upon depositing said layer B.

36. A fabrication process according to claim 32, wherein said layer B further comprises an element for increasing the bandgap thereof.

37. A fabrication process according to claim 32, wherein each said valence electron controlling agent comprises an element belonging to Group III or Group V of the Periodic Table.

38. A fabrication process according to claim 32, wherein a DC voltage or AC power applied when forming said layer A is greater than a DC voltage or AC power applied when depositing said layer B.

39. A fabrication process according to claim 32, wherein the hydrogen dilution ratio of a feed stock gas introduced when forming said layer A is higher than the hydrogen dilution ratio of the feed stock gas introduced when depositing said layer B.

40. A fabrication process according to claim 32, wherein the frequency of discharge power when forming said layer A is lower than the frequency of discharge power when depositing said layer B.

41. A fabrication process according to claim 40, wherein the frequency of discharge power when forming said layer A is between 5 kHz and 500 kHz.

42. A fabrication process according to claim 40, wherein the frequency of discharge power when forming said layer B is between 1 MHz and 100 MHz.