Producing solar cells by surface preparation for accelerated nucleation of microcrystalline silicon on heterogeneous substrates

• US 5,730,808 A
• Filed: 06/27/1996
• Issued: 03/24/1998
• Est. Priority Date: 06/27/1996
• Status: Expired due to Term

• Current Assignee: BP Solar International Incorporated (BP PLC)
• Original Assignee: Amoco/Enron Solar Co.
• Inventors: Chen, Liangfan, Yang, Liyou
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US08/672,110
• Time in Patent Office: 635 Days
• Field of Search: 437/4, 437/108-109, 437/113, 136/249 TJ, 136/258 AM, 438/74, 438/96-97, 438/485, 257/458, 257/440
• US Class Current: 136/249
• CPC Class Codes: H01L 31/03685 including microcrystalline silicon, uc-Si
• CPC Class Codes: H01L 31/076 Multiple junction or tandem solar cells
• CPC Class Codes: H01L 31/1824 Special manufacturing methods for microcrystalline Si, uc-Si
• CPC Class Codes: Y02E 10/545 Microcrystalline 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

Attractive multi-junction solar cells and single junction solar cells with excellent conversion efficiency can be produced with a microcrystalline tunnel junction, microcrystalline recombination junction or one or more microcrystalline doped layers by special plasma deposition processes which includes plasma etching with only hydrogen or other specified etchants to enhance microcrystalline growth followed by microcrystalline. nucleation with a doped hydrogen-diluted feedstock.

Claims

1. A process for fabricating a multi-junction solar cell by plasma enhanced chemical vapor deposition, comprising the steps of:

forming a first solar cell with a p-type doped layer p₁, an active instrinic layer i₁, and an n-type doped layer n₁ ;

forming a second solar cells with a p-type doped layer p₂, an active instrinic layer i₂, and an n-type doped layer n₂ ; and

forming a tunnel junction connecting the first solar cell to the second solar cell, said tunnel junction comprising the n-type doped layer from one of said solar cells, the p-type doped layer from the other solar cell, and at least one intermediate tunnel junction layer positioned between said first and second solar cells;

wherein said intermediate tunnel junction layer is fabricated by first plasma etching a surface of one of said doped layers in said tunnel junction in the absence of a feedstock, and, thereafter, nucleating and growing from said etched layer to form a microcrystalline tunnel junction layer, said nucleating and growing comprising plasma enhanced chemical vapor deposition with a dopant and a feedstock diluted with a diluent, and said nucleating and growing commencing only after said plasma etching of said surface of said one of said doped layers.

2. A process in accordance with claim 1, wherein said plasma etching comprises plasma etching with an etchant selected from the group consisting of hydrogen, deuterium, HD, helium, and argon.

3. A process in accordance with claim 1, wherein said plasma etching comprises hydrogen plasma etching in the absence of silane.

4. A process in accordance with claim 1, including:

preventing damage to said doped layers during said plasma etching.

5. A process in accordance with claim 1:

wherein said dopant is selected from the group consisting of an n-type dopant and a p-type dopant, said n-type dopant being selected from the group consisting of phosphine (PH₃) and other phosphorous-containing compounds, said p-type dopant being selected from the group consisting of diborane (B₂ H₆), BF₃, and other boron-containing compounds;

said feedstock being selected from the group consisting of silane, disilane, tetramethyl silane, SiF₄, SiHF₃, SiH₂ Cl₆, CH_N (SiH₃)_4-N wherein N is an integer in the range of 0 to 3, a carbon based feedstock, a germanium based feedstock, and compounds having the general formula Si_N H_{2N 2-M} Y_M wherein;

Si=silicon

H=hydrogen or deuterium

Y=a halogen

N=positive integer≧

1

M=positive integer; and

2N 2-M≧

0

said diluent being selected from the group consisting of hydrogen, deuterium, and combinations thereof; and

the dilution ratio of said diluent to said feedstock ranges from about 50;

1 to about 200;

1.

6. A process in accordance with claim 1, wherein said microcrystalline runnel junction layer is selected from the group consisting of a p-type microcrystalline layer and an n-type microcrystalline layer.

7. A process in accordance with claim 1, wherein said tunnel junction comprises an n-type doped layer, an n-type microcrystalline tunnel junction layer, a p-type microcrystalline tunnel junction layer, and a p-type doped layer.

8. A process in accordance with claim 1, wherein said solar cells are selected from the group consisting of p-i-n solar cells and n-i-p solar cells.

9. A process in accordance with claim 1, wherein:

at least one of the layers in one of said solar cells comprises a hydrogenated amorphous silicon selected from the group consisting of amorphous hydrogenated silicon carbon, amorphous hydrogenated silicon germanium, and amorphous hydrogenated silicon; and

said microcrystalline layer is selected from the group consisting of microcrystalline silicon carbon, microcrystalline silicon germanium, and microcrystalline silicon.

10. A process in accordance with claim 1, wherein said plasma enhanced chemical vapor deposition is selected from the group consisting of:

cathodic DC glow discharge, anodic DC glow discharge, RF glow discharge, VHF glow discharge, AC glow discharge, and microwave glow discharge.

11. A process in accordance with claim 1, including:

depositing a conducting oxide on a substrate, said conducting oxide being selected from the group consisting of tin oxide and zinc oxide, and said substrate being selected from the group consisting of a glass substrate, a stainless steel substrate, and a metal substrate;

forming one of said doped layers of said first solar cell on said conducting oxide; and

placing a surface of an electrically conductive plate on one of said doped layers of said second solar cell, said plate being fabricated of at least one material selected from the group consisting of aluminum, silver, metal, and other conductors.

12. A process for fabricating multi-junction tandem solar cells by plasma enhanced chemical vapor deposition, comprising the steps of:

depositing a conducting oxide on a surface of a light-transmissive vitreous substrate selected from the group consisting of transparent glass and translucent glass, said conducting oxide being selected from the group consisting of tin oxide and zinc oxide;

forming a first p-i-n solar cell by depositing a p-type doped layer p₁ on said conducting oxide, depositing an active instrinic layer i₁ on said layer p₁, and depositing an n-type doped layer n₁ on said layer i₁ ;

treating said layer n₁ with a hydrogen plasma etch in the absence of silane for a period of about 150 to about 750 seconds, said treating including etching said layer n₁ without damaging the optical and electrical properties of said layer n₁ ;

forming a microcrystalline tunnel junction layer by nucleating said hydrogen treated layer n₁ with an n-type doped plasma of hydrogen and a silicon-containing feedstock to form an n-type microcrystalline tunnel junction layer μ

n having a thickness of about 50 Å

to about 120 Å

, said nucleating occurring only after said hydrogen plasma etch of said layer n₁ ;

forming a second p-i-n solar cell by depositing a p-type doped layer p₂ on said microcrystalline tunnel junction layer comprising said layer μ

n, depositing an active instrinic layer i₂ on said layer p₂, and depositing an n-type doped layer n₂ on said layer i₂ ;

placing a back plate on said layer n₂, said back plate being fabricated of at least one material selected from the group consisting of aluminum, silver, metal, and other conductors; and

said first p-i-n solar cell being connected to said second p-i-n solar cell with a microcrystalline tunnel junction comprising said layer n₁, said layer μ

n, and said layer p₂.

13. A process in accordance with claim 12, wherein:

said microcrystalline tunnel junction layer comprises a composite microcrystalline tunnel junction layer, said composite microcrystalline tunnel junction layer comprising said microcrystalline tunnel junction layer μ

n and a microcrystalline tunnel junction layer μ

p, said microcrystalline tunnel junction layer μ

n being disposed between said layer n₁ and said microcrystalline tunnel junction layer μ

p; and

said microcrystalline tunnel junction layer μ

p being disposed between said layer μ

n and said layer p₂ ; and

said microcrystalline tunnel junction layer μ

p being formed by subjecting said microcrystalline tunnel junction layer μ

n to a p-type doped plasma of hydrogen and a silicon-containing feedstock to form said microcrystalline tunnel junction layer μ

p on said microcrystalline tunnel junction layer μ

n.

14. A process in accordance with claim 12, including coating a portion of said back plate with a conducting oxide selected from the group consisting of tin-oxide and zinc oxide.

15. A process in accordance with claim 12, wherein:

plasma enhanced chemical vapor deposition of said microcrystalline tunnel junction layer comprises supplying a feedstock diluted with a diluent at a dilution ratio of said diluent to said feedstock in the range from about 50;

1 to about 200;

1, said diluent being selected from the group consisting of hydrogen, deuterium, and combinations thereof;

said feedstock being selected from the group consisting of silane, disilane, tetramethyl silane, SiF₄, SiHF₂, SiH₂ Cl₄, CH_N (SiH₃)_4-N wherein N is an integer in the range of 0 to 3, a carbon based feedstock, a germanium based feedstock, and compounds having the general formula Si_N H_{2N 2-M} Y_M wherein;

Si=silicon

H=hydrogen or deuterium

Y=a halogen

N=positive integer≧

1

M=positive integer; and

2N 2-M≧

0

said layers n₁ and n₂ being formed by plasma enhanced chemical vapor deposition with an n-type dopant selected from the group consisting of phosphine (PH₄) and other phosphorous-containing compounds; and

said layers p₁ and p₂ being formed by plasma enhanced chemical vapor deposition with a p-type dopant selected from the group consisting of dibroane (B₂ II₆), BF₃, and other boron-containing compounds.

16. A process in accordance with claim 12, wherein plasma enhanced chemical vapor deposition of said microcrystalline tunnel junction layer comprises direct current or radio frequency glow discharge under the following conditions:

the temperature of said substrate ranging from about 80°

C. to about 300°

C.;

the pressure ranging from about 0.5 to about 5 Torr; and

the power density ranging from about 50 to about 230 mW/cm².

17. A process in accordance with claim 12, wherein:

said layers i₁ and i₂ comprise an active hydrogenated compound selected from the group consisting of amorphous hydrogenated silicon, amorphous hydrogenated silicon carbon, and amorphous hydrogenated silicon germanium;

said active layers p₁ and p₂ comprise a p-doped hydrogenated compound selected from the group consisting of amorphous hydrogenated silicon, amorphous hydrogenated silicon carbon, and amorphous hydrogenated silicon germanium; and

said active layers n₁ and n₂ comprise an n-doped hydrogenated compound selected from the group consisting of amorphous hydrogenated silicon, amorphous hydrogenated silicon carbon, and amorphous hydrogenated silicon germanium.

18. A process in accordance with claim 12, wherein:

said treating of said layer n₁ with a hydrogen plasma etch is provided for a period of about 300 to about 500 seconds;

said n-type doped, microcrystalline tunnel junction layer μ

n has a thickness of about 80 Å

to about 100 Å

;

said feedstock comprises silane; and

said layers i₁ and i₂ comprise amorphous hydrogenated silicon.

19. A multi-junction photovoltaic solar cell device, comprising:

a first solar cell with a p-type doped layer p₁, an active instrinic layer i₁, and an n-type doped layer n₁ ;

a second solar cell with a p-type doped layer p₂, an active instrinic layer i₂, and an n-type doped layer n₂ ;

a tunnel junction providing a recombination junction connecting the first solar cell to the second solar cell, said tunnel junction comprising an n-type doped layer from one of said solar cells, a p-type doped layer from the other solar cell, and at least one intermediate microcrystalline tunnel junction layer positioned between said first and second solar cell cells, and one of said doped layers in said tunnel junction having a plasma etched surface positioned adjacent said intermediate microcrystalline tunnel junction layer.

20. A photovoltaic device in accordance with claim 19, wherein said plasma etched surface comprises a surface etched in a hydrogen plasma in the absence of silane.

21. A photovoltaic device in accordance with claim 19, wherein said at least one microcrystalline tunnel junction layer is selected from the group consisting of a p-type microcrystalline layer and an n-type microcrystalline layer.

22. A photovoltaic device in accordance with claim 19, wherein said runnel junction comprises an n-type doped layer, an n-type microcrystalline tunnel junction layer, a p-type microcrystalline tunnel junction layer, and a p-type doped layer.

23. A photovoltaic device in accordance with claim 19, wherein at least one of said solar cells is selected from the group consisting of a p-i-n solar cell and an n-i-p solar cell.

24. A photovoltaic device in accordance with claim 19, wherein:

at least one of the layers in one of said solar cells comprises hydrogenated amorphous silicon selected from the group consisting of amorphous hydrogenated silicon carbon, amorphous hydrogenated silicon germanium, and amorphous hydrogenated silicon; and

said microcrystalline tunnel junction layer comprises a microcrystalline silicon- containing layer selected from the group consisting of microcrystalline silicon carbon, microcrystalline silicon germanium, and microcrystalline silicon.

25. A photovoltaic device in accordance with claim 19, comprising:

a substrate selected from the group consisting of a glass substrate, a stainless steel substrate, and a metal substrate; and

a conductive oxide on said substrate, said conducting oxide selected from the group consisting of tin oxide and zinc oxide.

26. A multi-junction tandem solar cell photovoltaic device, comprising:

a light-transmissive vitreous substrate selected from the group consisting of transparent glass and translucent glass, said substrate having a surface portion;

a conducting oxide on said surface portion, said conducting oxide selected from the group consisting of tin oxide and zinc oxide;

a first p-i-n solar cell comprising a p-type doped layer p₁ on said conducting oxide, an active instrinic layer i₁ on said layer p₁, and an n-type doped amorphous layer n₁ on said layer i₁ ;

said layer n₁ having a surface etched in a hydrogen plasma in the absence of silane;

said etched surface having solar cell-grade optical and electrical properties;

a microcrystalline tunnel junction layer comprising an n-type doped, microcrystalline tunnel junction layer μ

n having a thickness of about 50 Å

to about 120 Å

on said etched surface;

a second p-i-n solar cell comprising a p-type doped layer p₂ on said microcrystalline tunnel junction layer μ

n, an active instrinic layer i₂ on said layer p₂, and an n-type doped layer n₂ on said layer i₂ ;

a back plate on said layer n₂, said back plate comprising at least one material selected from the group consisting of aluminum, silver, metal, and other conductors; and

said first p-i-n solar cell being connected to said second p-i-n solar cell with a microcrystalline tunnel junction comprising said layer n₁, said layer μ

n on said plasma etched surface of said layer n₁, and said layer p₂ on said layer μ

n.

27. A photovoltaic device in accordance with claim 26, including

a conducting oxide on a portion of said back plate, selected from the group consisting of tin oxide and zinc oxide, and wherein

said negatively doped, microcrystalline tunnel junction μ

n layer has a thickness of about about 80 Å

to about 100 Å

on said etched surface.

28. A photovoltaic device in accordance with claim 26, wherein:

at least one of the layers in one of said solar cells comprises hydrogenated amorphous silicon selected from the group consisting of amorphous hydrogenated silicon carbon, amorphous hydrogenated silicon germanium, and amorphous hydrogenated silicon; and

said microcrystalline tunnel junction layer comprises a microcrystalline silicon layer selected from the group consisting of microcrystalline silicon carbon, microcrystalline silicon germanium, and microcrystalline silicon.

29. A photovoltaic device in accordance with claim 26, wherein:

said layer n₁ comprises n-doped amorphous silicon; and

said microcrystalline tunnel junction layer μ

n comprises n-doped microcrystalline silicon.

30. A photovoltaic device in accordance with claim 26, wherein:

said microcrystalline tunnel junction layer comprises a composite microcrystalline tunnel junction layer, said composite microcrystalline tunnel junction layer comprising said microcrystalline tunnel junction layer μ

n and a microcrystalline tunnel junction layer μ

p, said microcrystalline tunnel junction layer μ

n being positioned between said layer n₁ and said microcrystalline tunnel junction layer μ

p, and said microcrystalline tunnel junction layer μ

p being positioned between said layer μ

n and said layer p₂.

31. A photovoltaic device in accordance with claim 30, wherein:

said layer n₁ comprises n-doped amorphous silicon;

said microcrystalline tunnel junction layer μ

n comprises n-doped microcrystalline silicon;

said microcrystalline tunnel junction layer μ

p comprises p-doped microcrystalline silicon; and

said layer p₂ comprises p-doped amorphous silicon.

32. A process of producing a solar cell, comprising the steps of:

forming solar cell semiconductor layers by plasma enhanced chemical vapor deposition with a feedstock diluted by a diluent, said solar cells comprising a doped layer having one conductivity, an active intrinsic layer, and a doped layer having an opposite conductivity;

plasma etching a surface of one of said doped layers with said diluent in the absence of said feedstock; and

nucleating and growing a layer of microcrystalline semiconductor material on said plasma etched layer.

33. A process in according with claim 32 wherein said plasma etched layer comprises an amorphous hydrogenated material selected from the group consisting of amorphous hydrogenated silicon, amorphous hydrogenated silicon carbon, and amorphous hydrogenated silicon germanium;

and

said microcrystalline material is selected from the group consisting of microcrystalline silicon, microcrystalline silicon carbon, and microcrystalline silicon germanium.

34. A process in accordance with claim 32, wherein one of said doped layers comprises said microcrystalline material.

35. A process in accordance with claim 32, including a tunnel junction layer grown on one of said doped layers, said tunnel junction layer comprising said microcrystalline layer.

36. A process in accordance with claim 32, wherein said nucleating and growing comprise:

plasma enhanced chemical vapor deposition with a dopant and a feedstock diluted with a diluent;

said dopant being selected from the group consisting of an n-type dopand and a p-type dopant, said n-type dopant being selected from the group consisting of phosphine (PH₁) and other phosphorous-containing compounds, said p-type dopant being selected from the group consisting of diborane (B₂ H₆), BF₃, and other boron-containing compounds;

said feedstock being selected from the group consisting of silane, disilane, tetramethyl silane, SiF₄, SiHF₃, SiH₂ Cl₄, CH_N (SiH₃)_4-N wherein N is an integer in the range of 0 to 3, a carbon based feedstock, a germanium based feedstock, and compounds having the general formula Si_N H_{2N 2-M} Y_M wherein;

Si=silicon

H=hydrogen or deuterium

Y=a halogen

N=positive integer≧

1

M=positive integer; and

2N 2-M≧

0

said diluent being selected from the group consisting of hydrogen, deuterium, and combinations thereof; and

the dilution ratio of said diluent to said feedstock ranges from about 50;

1 to about 200;

1.

37. A process in accordance with claim 32, wherein said plasma enhanced chemical vapor deposition is selected from the group consisting of:

cathodic DC glow discharge, anodic DC glow discharge, RF glow discharge, VHF glow discharge, AC glow discharge, and microwave glow discharge.

38. A process for producing photovoltaic devices, comprising the steps of:

forming solar cell semiconductor layers on a substrate by plasma enhanced CVD with a feedstock diluted by a diluent, said solar cell comprising a p-type doped layer, an active intrinsic amorphous i-layer, and an n-type doped layer;

plasma etching a surface portion of said amorphous i-layer with an etchant selected from the group consisting of H₂, D₂, HD, helium, and argon, in the absence of said feedstock, for about 150 to about 750 seconds without damaging the optical and electrical properties of said i-layer, and after said plasma etching,

nucleating and growing one of said doped layers adjacent said etched surface portion of said amorphous i-layer to form a microcrystalline doped layer having a thickness of about 50 Å

to about 120 Å

.

39. A process in accordance with claim 38, including forming tandem multi-junction solar cells with at least one microcrystalline doped layer.

40. A process in accordance with claim 38, wherein plasma enhanced chemical vapor deposition of said microcrystalline layer comprises direct current or radio frequency glow discharge under the following conditions:

the temperature of said substrate ranging from about 80°

C. to about 300°

C.;

the pressure ranging from about 0.5 to about 5 Torr; and

the power density ranging from about 50 to about 230 mW/cm².

41. A process in accordance with claim 38, wherein:

said i-layer is selected from the group consisting of amorphous hydrogenated silicon, amorphous hydrogenated silicon carbon, and amorphous hydrogenated silicon germanium; and

said microcrystalline layer is selected from the group consisting of microcrystalline silicon, microcrystalline silicon carbon, and microcrystalline silicon germanium.

42. A process in accordance with claim 38, wherein said i-layer is amorphous silicon;

said surface of said amorphous silicon i-layer is plasma etched for a period of about 300 to about 500 seconds with a hydrogen etchant; and

said n-type doped layer is nucleated and grown to form an n-type microcrystalline silicon layer having a thickness of about 80 Å

to about 100 Å

.

43. A photovoltaic device, comprising:

at least one solar cell having a p-type doped layer,

an intrinsic amorphous i-layer, and

an n-type doped layer,

said i-layer having a plasma etched surface; and

one of said doped layers comprises a microcrystalline doped layer positioned adjacent and abutting said plasma etched surface of the i-layer.

44. A photovoltaic device in accordance with claim 43, wherein said microcrystalline doped layer has a thickness of about 50 Å

to about 120 Å

.

45. A photovoltaic device in accordance with claim 43, wherein said etched surface comprises a surface etched in a hydrogen plasma in the absence of silane, said etched surface having solar cell-grade optical and electrically properties.

46. A photovoltaic device in accordance with claim 43, wherein:

said i-layer is selected from the group consisting of amorphous hydrogenated silicon, amorphous hydrogenated silicon carbon, and amorphous hydrogenated silicon germanium; and

said microcrystalline layer is selected from the group consisting of microcrystalline silicon, microcrystalline carbon, and microcrystalline silicon germanium.

47. A photovoltaic device in accordance with claim 43, comprising:

a substrate selected from the group consisting of a glass substrate, a stainless steel substrate, and a metal substrate; and

a conductive oxide on said substrate, said conducting oxide selected from the group consisting of tin oxide and zinc oxide.

48. A photovoltaic device in accordance with claim 43, wherein:

said i-layer comprises amorphous silicon, and

said n-type doped layer comprises an n-type microcrystalline silicon layer having a thickness of about 80 Å

to about 100 Å

.

49. A photovoltaic device in accordance with claim 48, wherein:

said solar cell is disposed on a light transmissive vitreous substrate selected from the group consisting of transparent glass and translucent glass, said substrate having a surface portion; and

a conducting oxide is disposed on said surface portion, said conducting oxide being selected from the group consisting of tin oxide and zinc oxide.

50. A photovoltaic device in accordance with claim 43 comprising multi-junction tandem solar cells with at least one p-i-n solar cell, at least one i-layer comprising amorphous silicon with a hydrogen plasma etched surface, and at least one doped layer comprising an n-type microcrystalline silicon layer having a thickness of about 80 Å

to about 100 Å

.