Solar cells and methods for manufacture thereof

• US 4,322,571 A
• Filed: 07/17/1980
• Issued: 03/30/1982
• Est. Priority Date: 07/17/1980
• Status: Expired due to Term

• Current Assignee: The Boeing Co.
• Original Assignee: The Boeing Co.
• Inventors: Stanbery, Billy J.
• Primary Examiner(s): Weisstuch, Aaron
• Application Number:
  US06/169,790
• Time in Patent Office: 621 Days
• Field of Search: 148/186, 148/187, 148/189, 148/1.5, 29/572, 156/647, 156/648, 156/649, 156/657, 156/662, 136/255, 136/256, 357/30, 357/91, 357/88, 204/15
• US Class Current: 136/255
• CPC Class Codes: H01L 31/0236 Special surface textures
• CPC Class Codes: H01L 31/02363 of the semiconductor body itself, e.g. textured active layers
• CPC Class Codes: H01L 31/068 the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
• CPC Class Codes: H01L 31/18 Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
• CPC Class Codes: Y02E 10/547 Monocrystalline silicon PV cells
• CPC Class Codes: Y10S 205/923 Solar collector or absorber
• CPC Class Codes: Y10S 438/965 Shaped junction formation

Abstract

An improved light transducer such as a solar cell and, especially, a concentrator solar cell, together with processes for forming the same which permit the formation of improved light transducers characterized by their high thermal stability and by optimized impurity atom dispersion zones at the surface of either a p-type or an n-type substrate--such, for example, as a silicon substrate--defining: (i) a thermally stable deep junction with relatively high surface concentrations of dopant dispersed in those areas where metallic electrodes are to be formed, thus providing excellent ohmic contact characteristics in such areas; and (ii), an efficient energy conversion shallow junction with relatively lower surface concentrations of dopant in the inter-electrode photoactive regions of the cell, with such inter-electrode photoactive regions preferably being texturized, thereby optimizing current generation per unit of incident radiation and minimizing reflection losses. More particularly, a deep junction (on the order of 0.5 μm or greater) is first formed throughout the substrate'"'"'s entire near-surface area which is to be exposed to incident radiation; such deep junction is then entirely removed in the inter-electrode regions of the substrate by subjecting such regions to an acid etch, preferably with a texturizing etchant but, in some instances, with a polish etchant; and, a relatively uniform shallow junction (on the order of 0.3 μm±0.1 μm) is then formed in the etched inter-electrode near-surface regions either (i) by subjection of the substrate to a gas diffusion dopant process, or (ii), by conventional ion implantation techniques.

Claims

1. The method of forming a light transducer having a plurality of contact areas and a plurality of photoactive areas from a wafer-like semiconductor substrate comprising the steps of:

(a) dispersing dopant impurities into the near-surface region of the semiconductor substrate to form a deep dispersion layer having high surface concentrations of dopant impurities and having a chemical potential different from the chemical potential of the substrate;

(b) masking selected regions of the substrate corresponding to the contact areas of the light transducer;

(c) entirely removing the deep dispersion layer in the unmasked regions of the substrate corresponding to the photoactive regions of the light transducer while leaving raised mesa-like contact areas containing a deep dispersion layer of dopant impurities in the masked regions of the substrate;

(d) dispersing dopant impurities into the near-surface regions of the substrate inter-contact regions of the light transducer to form a relatively shallow dispersion layer having relatively lower surface concentrations of dopant impurities and having a chemical potential different from the chemical potential of the substrate; and

,

(e) forming electrodes on the contact areas of the substrate.

2. The method as set forth in claim 1 wherein the semiconductor substrate is formed of p-type semiconductor material and the dopant impurities dispersed into the near-surface regions in steps (a) and (d) are n-type dopants.

3. The method as set forth in claim 1 wherein the semiconductor substrate is formed of n-type semiconductor material and the dopant impurities dispersed into the near-surface regions in steps (a) and (d) are p-type dopants.

4. The method as set forth in claim 1 wherein the deep dispersion layer is on the order of at least 0.5 μ

m in thickness.

5. The method as set forth in claims 1 or 4 wherein the shallow dispersion layer is on the order of 0.3 μ

m±

0.1 μ

m in thickness.

6. The method as set forth in claim 1 wherein the dopant impurities are diffused into the near-surface regions by gas diffusion at a temperature in the range of:

(i) about 950°

C. to about 1000°

C. for a period of from about 15 minutes to about 20 minutes in step (a); and

(ii), about 850°

C. to about 875°

C. for a period of from about 10 minutes to about 15 minutes in step (d).

7. The method as set forth in claim 1 wherein the dopants dispersed into the near-surface regions of the substrate during at least step (d) are implanted therein by ion bombardment.

8. The method as set forth in claims 1 or 7 wherein the substrate is annealed following at least one of steps (d) and (e).

9. The method as set forth in claims 1 or 7 wherein the substrate is laser annealed following at least one of steps (d) and (e).

10. The method as set forth in claim 1 wherein the electrodes formed on the raised mesa-like contact areas in step (e) are formed by vacuum deposition.

11. The method as set forth in claims 1, 6 or 7 wherein the substrate is glass encapsulated following step (e).

12. The method as set forth in claim 1 wherein the substrate is annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

13. The method as set forth in claim 1 wherein the substrate is laser annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

14. The method of forming a light transducer having a pluarlity of contact areas and a pluarlity of photoactive areas from a wafer-like semiconductor substrate comprising the steps of:

(a) dispersing dopant impurities into the nearsurface region of the semiconductor substrate to form a deep dispersion layer having high surface concentrations of dopant impurities and having a chemical potential different from the chemical potential of the substrate;

(b) masking selected regions of the substrate corresponding to the contact areas of the light transducer;

(c) etching the unmasked regions of the substrate with a texturizing etchant to;

(i) entirely remove the deep dispersion layer in the unmasked regions of the substrate corresponding to the photoactive regions of the light transducer while leaving raised mesa-like contact areas containing a deep dispersion layer in the masked regions of the substrate; and

,

(ii) form a texturized completely undoped surface in the unmasked regions intermediate the raised mesa-like contact areas;

(d) dispersing dopant impurities into the undoped near-surface regions of the substrate in the inter-contact regions of the light transducer to form a relatively shallow dispersion layer of substantially uniform depth on the irregular texturized surface and having relatively low surface concentrations of dopant impurities and a chemical potential different from the chemical potential of the substrate; and

,

(e) forming electrodes on the contact areas of the substrate.

15. The light transducer formed by the method set forth in the claim 14.

16. The method as set forth in claim 14 wherein the semiconductor substrate is formed of p-type semiconductor material and the dopant impurities dispersed into the nearsurface regions in steps (a) and (d) are n-type dopants.

17. The method as set forth in claim 14 wherein the semiconductor substrate is formed of n-type semiconductor material and the dopant impurities into the nearsurface regions in steps (a) and (d) are p-type dopants.

18. The method as set forth in claims 14, 16 or 17 wherein the texturizing etchant used in step (c) is hydrazine hydrate and the texturized undoped surface formed is characterized by a multiplicity of randomly sized and located minute pyramids.

19. The method as set forth in claim 14 wherein the deep dispersion layer is on the order of at least 0.5 μ

m in thickness.

20. The method as set forth in claims 14 or 19 wherein the shallow dispersion layer is on the order of 0.3 μ

m±

0.1 μ

m in thickness.

21. The method as set forth in claim 14 wherein the dopant impurities are diffused into the near-surface regions by gas diffusion at a temperature in the range of:

(i) about 950°

C. to about 1000°

C. for a period of from about 15 minutes to about 20 minutes in step (a); and

(ii), about 850°

C. to about 875°

C. for a period of from about 10 minutes to about 15 minutes in step (d).

22. The method as set forth in claim 14 wherein the dopants dispersed into the near-surface regions of the substrate during at least step (d) are implanted therein by ion bombardment.

23. The method as set forth in claim 14 or 22 wherein the substrate is annealed following at least one of steps (d) and (e).

24. The method as set forth in claims 14 or 22 wherein the substrate is laser annealed following at least one of steps (d) and (e).

25. The method as set forth in claim 14 wherein the electrodes formed on the mesa-like contact areas in step (e) are formed by vacuum deposition.

26. The method as set forth in claims 14, 21 or 22 wherein the substrate is glass encapsulated following step (e).

27. The method as set forth in claim 14 wherein the substrate is annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

28. The method as set forth in claim 14 wherein the substrate is laser annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

29. The method of forming a light transducer having a plurality of contact areas and a plurality of photoactive areas from a wafer-like p-type semiconductor substrate having a high percentage of undesired impurities and/or dislocations contained therein comprising the steps of:

(a) subjecting a surface of the substrate to a high temperature gas diffusion dopant process with an n-type dopant for a period sufficient to form a deep n⁺ diffusion layer in the near-surface regions of the substrate with undesired impurities and/or dislocations contained in the substrate being gettered into the relatively deep n⁺ diffusion layer and with the deep n⁺ diffusion layer having a chemical potential different from the chemical potential of the substrate;

(b) masking selected regions of the substrate corresponding to the contact areas of the light transducer;

(c) entirely removing the deep n⁺ diffusion layer, including the undesired impurities and/or dislocations contained therein, in the unmasked regions on the light transducer while leaving raised mesa-like contact areas containing a deep n⁺ diffusion layer in the masked regions of the substrate;

(d) dispersing n⁺ dopant impurities into the nearsurface regions of the substrate in the inter-contact regions of the light transducer to form a relatively shallow n⁺ dispersion layer having relatively lower surface concentrations of n⁺ dopant impurities and having a chemical potential different from the chemical potential of the substrate; and

,

(e) forming electrodes on the contact areas of the substrate.

30. The method as set forth in claim 29 wherein the deep diffusion layer is on the order of at least 0.5 μ

m in thickness.

31. The method as set forth in claims 29 or 30 wherein the shallow dispersion layer is on the order of 0.3 μ

m±

0.1 μ

m in thickness.

32. The method as set forth in claim 29 wherein the n-type dopant impurities are diffused into the near-surface regions by gas diffusion:

(i) at a temperature on the order of at least 950°

C. for a period on the order of at least 15 minutes in step (a); and

(ii), at a temperature in the range of about 850°

C. to about 875°

C. for a period of from about 10 minutes to about 15 minutes in step (d).

33. The method as set forth in claim 29 wherein the n-type dopants dispersed into the near-surface regions of the substrate during step (d) are implanted therein by ion bombardment.

34. The method as set forth in claim 29 or 33 wherein the substrate is annealed following at least one of steps (d) and (e).

35. The method as set forth in claims 29 or 33 wherein the substrate is laser annealed following at least one of steps (d) and (e).

36. The method as set forth in claim 29 wherein the electrodes formed on the raised mesa-like contact areas in step (e) are formed by vacuum deposition.

37. The method as set forth in claims 29, 32 or 33 wherein the substrate is glass encapsulated following step (e).

38. The method as set forth in claim 29 wherein the substrate is annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

39. The method as set forth in claim 29 wherein the substrate is laser annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

40. The method as set forth in claim 29 wherein the unmasked regions of the deep n⁺ diffusion layer are entirely removed in step (c) by etching.

41. The method as set forth in claim 40 wherein a polish etchant is employed in step (c) to produce polish etched surfaces in the inter-contact regions of the substrate.

42. The method as set forth in claim 40 wherein a texturizing etchant is employed in step (c) to produce texturized surfaces in the inter-contact regions of the substrate.

43. The method as set forth in claim 42 wherein the texturizing etchant is hydrazine hydrate.

44. The method of forming a light transducer having a plurality of contact areas and a plurality of photoactive areas from a wafer-like p-type semiconductor substrate having a high percentage of undesired impurities and/or dislocations contained therein comprising the steps of:

(a) subjecting a surface of the substrate to a high temperature gas diffusion dopant process with an n-type dopant for a period sufficient to form a deep n⁺ diffusion layer in the near-surface regions of the substrate with undesired impurities and/or dislocations contained in the substrate being gettered into the relatively deep n⁺ diffusion layer and with the deep n⁺ diffusion layer having a chemical potential different from the chemical potential of the substrate;

(b) masking selected regions of the substrate corresponding to the contact areas of the light transducer;

(c) etching the unmasked regions of the substrate with a texturizing etchant to;

(i) entirely remove the deep n⁺ diffusion layer, including the undesired impurities and dislocations contained therein, in the unmasked regions of the substrate corresponding to the photoactive regions of the light transducer while leaving raised mesa-like contact areas containing a deep n⁺ diffusion layer in the masked regions of the substrate; and

,

(ii) form a texturized completely undoped surface in the unmasked regions intermediate the raised mesa-like contact areas;

(d) dispersing dopant impurities into the undoped near-surface regions of the substrate in the inter-contact regions of the light transducer to form a relatively shallow n⁺ dispersion layer having relatively lower surface concentrations of n-type dopant impurities and having a chemical potential different from the chemical potential of the substrate; and

,

(e) forming electrodes on the contact areas of the substrate.

45. The light transducer formed by the method set forth in claim 44.

46. The method as set forth in claim 44 wherein the texturizing etchant used in step (c) is hydrazine hydrate and the texturized undoped surface formed is characterized by a multiplicity of randomly sized and located minute pyramids.

47. The method as set forth in claim 44 wherein the deep diffusion layer is on the order of at least 0.5 μ

m in thickness.

48. The method as set forth in claims 44 or 47 wherein the shallow dispersion layer is on the order of 0.3 μ

m±

0.1 μ

m in thickness.

49. The method as set forth in claim 44 wherein the dopant impurities are diffused into the near-surface regions by gas diffusion:

(i) at a temperature on the order of at least 950°

C. for a period on the order of at least 15 minutes in step (a); and

(ii), at a temperature in the range of about 850°

C. to about 875°

C. for a period of from about 10 minutes to about 15 minutes in step (d).

50. The method as set forth in claim 44 wherein the dopants dispersed into the near-surface regions of the substrate during step (d) are implanted therein by ion bombardment.

51. The method as set forth in claim 50 wherein the substrate is annealed following at least one of steps (d) and (e).

52. The method as set forth in claim 50 wherein the substrate is laser annealed following at least one of steps (d) and (e).

53. The method as set forth in claim 44 wherein the electrodes formed on the raised mesa-like contact areas in step (e) are formed by vacuum deposition.

54. The method as set forth in claims 44, 49 or 50 wherein the substrate is glass encapsulated following step (e).

55. The method as set forth in claim 44 wherein the substrate is annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

56. The method as set forth in claim 44 wherein the substrate is laser annealed following at least one of steps (d) and (e) and is glass encapsulated following step (e).

64. The light transducer as set forth in claims 48, 58, 59 or 60 wherein said transducer is glass encapsulated.

57. An improved light transducer suitable for use as a solar cell comprising, in combination, a wafer-like semiconductor substrate, said substrate having:

a first relatively deep dispersion layer of dopant impurities formed in the near-surface regions of said substrate with said deep dispersion layer having relatively high surface concentrations of dopant impurities and defining a relatively deep junction at the interface of said dispersion layer and said substrate defining regions of differing chemical potential in said substrate and in said dispersion layer;

a plurality of spaced texturized surface areas formed on said substrate by complete removal of spaced areas of said first dispersion layer with a texturizing etchant and defining raised, spaced, mesa-like contact areas intermediate said spaced texturized surface areas;

a second relatively shallow dispersion layer of dopant impurities formed in the near-surface regions of said texturized surface areas with said shallow dispersion layer having a substantially uniform depth and defining a relatively shallow junction at the interface of said shallow dispersion layer and said substrate defining regions of differing chemical potential in said substrate and said shallow dispersion layer; and

, electrodes formed on said raised mesa-like contact areas and on the surface of said substrate remote from said raised contact areas.

58. The light transducer as set forth in claim 57 wherein said semiconductor substrate is formed of p-type semiconductor material and said deep and shallow dispersion layers are n⁺ layers formed from n-type dopants and defining n⁺ -p junctions.

59. The light transducer as set forth in claim 57 wherein said semiconductor substrate is formed of n-type semiconductor material and said deep and shallow dispersion layers are p⁺ layers formed from p-type dopants and defining p⁺ -n junctions.

60. The light transducer as set forth in claim 57 wherein said texturized surfaces are defined by a multiplicity of randomly sized and located, minute, pyramids.

61. The light transducer as set forth in claims 57, 58, 59 or 60 wherein said deep dispersion layer is on the order of at least 0.5 μ

m in thickness.

62. The light transducer as set forth in claims 57, 58, 59 and 60 wherein said shallow dispersion layer is on the order of 0.3 μ

m±

0.1 μ

m in thickness.

63. The light transducer as set forth in claims 57, 58, 59 and 60 wherein said deep dispersion layer is on the order of at least 0.5 μ

m in thickness and said shallow dispersion layer is on the order of 0.3 μ

m±

0.1 μ

m in thickness.