Amorphous semiconductors equivalent to crystalline semiconductors

• US 4,217,374 A
• Filed: 03/08/1978
• Issued: 08/12/1980
• Est. Priority Date: 03/08/1978
• Status: Expired due to Term

• Current Assignee: United Solar Systems Corp.
• Original Assignee: Energy Conversion Devices
• Inventors: Ovshinsky, Stanford R., Izu, Masatsugu
• Primary Examiner(s): Smith, John D.
• Application Number:
  US05/884,664
• Time in Patent Office: 888 Days
• Field of Search: 148/1.5, 357/91, 357/2, 357/13, 357/20, 357/63, 427/53, 427/85, 427/86, 427/42, 427/39, 427/74, 427/76, 427/83, 427/84, 427/248 R, 204/192 S
• US Class Current: 438/92
• CPC Class Codes: C23C 14/00 Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
• CPC Class Codes: C23C 14/0021 Reactive sputtering or evaporation
• CPC Class Codes: C23C 14/14 Metallic material, boron or silicon
• CPC Class Codes: C23C 14/58 After-treatment
• CPC Class Codes: C23C 14/5846 Reactive treatment
• CPC Class Codes: H01L 21/02532 Silicon, silicon germanium, germanium
• CPC Class Codes: H01L 21/0262 Reduction or decomposition of gaseous compounds, e.g. CVD
• CPC Class Codes: H01L 31/20 such devices or parts thereof comprising amorphous semiconductor materials
• CPC Class Codes: H01L 31/202 including only elements of Group IV of the Periodic Table
• CPC Class Codes: Y02E 10/50 Photovoltaic [PV] energy
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

A method of making an amorphous semiconductor film or the like having desirable photoconductive and/or other properties comprises forming an amorphous semiconductor film, preferably by vaporizing silicon or the like in an evacuated space and condensing the same on a substrate in such space, and preferably at the same time, introducing at least two or three compensating or altering agents into the film, like activated hydrogen and fluorine, in amounts which substantially reduce or eliminate the localized states in the energy gap thereof so that greatly increased diffusion lengths for solar cell applications is obtained and dopants can be effectively added to produce p or n amorphous semiconductor films so that the films function like similar crystalline materials.

Claims

1. A method of producing an amorphous semiconductor fluid comprising a solid compensated or altered amorphous semiconductor host matrix with electronic configurations which have an energy gap and a low density of localized states therein, said method comprising depositing on a substrate an amorphous semiconductor host matrix film and introducing therein a plurality of different and complimentary compensating or altering materials comprising at least hydrogen and fluorine, each of which reduces localized states in the energy gap not similarly reducible by any amounts used of the other of same, so that the combination of said different and compensating or altering materials produces a greater reduction in the density of localized states in the energy gap than any one of the same could achieve.

2. The method of claim 1 wherein some of the localized states in the energy gap of said amorphous semiconductor host matrix in its uncompensated state are concentrated at or near the Fermi level thereof and others are located at points between these localized states and relatively close to the valence and conduction bands, and said different and compensating or altering materials introduced into said film are selected so that at least one reduces said localized states at or near the Fermi level and another reduces said localized states between those at or near said Fermi level and one of said bands.

3. The method of claim 2 wherein there is at least a third compensating or altering material introduced into the film which reduces said localized states between those at or near the Fermi level and the other of said bands.

4. The method of claim 1, 2, or 3 wherein said amorphous semiconductor film is modified by adding a dopant material which shifts the Fermi level thereof to a point at or near the valence or conduction band thereof.

17. The method of claim 1 or 5 wherein the amorphous semiconductor film is deposited in a first environment and the compensating or altering materials are injected into said film in a different environment.

18. The method of claim 17 wherein said first environment includes an evacuated space and the second environment is an environment where the pressure is greater than atmospheric pressure.

19. The method of claim 18 wherein the amorphous semiconductor film in said second environment is heated to a temperature below the crystallization temperature thereof.

20. The method of claim 1 or 5 wherein the amorphous semiconductor film is heated to a temperature below the crystallization temperature thereof as the compensating or altering materials are introduced into the same.

27. The method of claim 1, 5, 21, 22 or 23 used to fabricate the charge carrier supplying portion of a solar cell and wherein there is also introduced into the compensated or altered amorphous semiconductor host matrix film conduction modifying materials in relatively small but sufficient amounts so that the Fermi level of adjacent regions thereof are moved respectively at or near the valence and conduction bands but without appreciably increasing the dark conductivity thereof, to form therein a p-n junction with an effective depletion layer.

28. The method of claim 1, 5, 21, 22 or 23 used to fabricate the charge carrier supplying portion of a solar cell and wherein there is also introduced into the compensated or altered amorphous semiconductor host matrix film conduction modifying materials in relatively small but sufficient amounts so that the Fermi level of adjacent regions thereof are moved respectively at or near the valence or conduction band but without appreciably increasing the dark conductivity thereof, to form therein a p-n junction with an effective depletion layer, and there is further formed in a compensated or altered portion of the film an ohmic contact interface forming a region between said p-n junction and an electrode of the cell by introducing into the latter region of the film relatively large amounts of a conduction modifying material so that the dark conductivity thereof is increased so that this region has a low resistance.

29. The method of claim 1, 5, 21, 22 or 23 wherein during the depositing of said film, said compensating or altering material and one or more dopants and introduced into the depositing film in amounts to move the Fermi level of the film first at or near one of the valence or conduction bands and then to the other of same to form at least one p-n junction in the film.

30. The method of claim 1, 5, 21, 22 or 23 carried out in the process of making a Schottky barrier solar cell, the charge carrier supplying portion of which is supplied by at least a portion of said compensated or altered film.

31. The method of claim 1, 5, 21 22 or 23 carried out in the process of making a Schottky barrier solar cell, the charge carrier supplying portion of which is supplied by at least a portion of said compensated or altered film, and there is formed in a second portion of said compensated or altered film an ohmic contact interface between said first portion of the film and an electrode of the cell by introducing into the latter region of the film relatively large amounts of a conduction modifying material so that the dark conductivity thereof is increased so that this region has a low resistance.

32. The method of claim 1, 5, 21, 22 or 23 carried out in the process of making an electrostatic image-producing device, the charge holding portion of which is supplied by said compensated or altered film.

39. The method of claims 1, 5, 21, 22, 29 or 23 wherein the density of localized states in the energy gap of the film is reduced substantially to at least 10¹⁶ per cubic centimeter per eV.

41. The method of claim 1, 5, 21, 22 or 23 carried out in the process of making a solar cell and wherein there is introduced into said amorphous semiconductor host matrix film at least one modifying material which increases the carrier lifetime within the film.

43. The method of claim 1, 5, 21, 22, 33 or 34 wherein at least three compensating or altering materials are introduced into said film which include hydrogen, flourine and lithium or sodium.

44. The method of claim 1, 5, 21, 22, 33 or 34 wherein the compensating or altering materials include a rare earth metal, a transition metal, carbon or chlorine.

45. The method of claim 1, 5, 21, 22, 33 or 34 wherein said amorphous semiconductor host matrix includes silicon or alloys or mixtures of silicon and other elements forming therewith a semiconductor material.

46. The method of claim 1, 5, 21, 22, 33 or 34 where said amorphous semiconductor host matrix is a photoconductive material including selenium, cadmium, tellerium, gallium, or arsenic, or alloys or mixtures thereof.

47. The method of claim 1, 5, 21, 22, 33 or 34 wherein said amorphous semiconductor host matrix includes germanium, carbon arsenic, cadmium, tellurium, gallium, selenium, sulphur, or boron, or alloys or mixtures thereof.

5. A method of making an amorphous semiconductor film to comprise an amorphous host matrix having at least one element and which has electronic configurations which have an energy gap with a density of localized states which adversely affect the obtainment of a given electrical characteristic unless compensated or altered by a compensating or altering material, said method comprising:

depositing on a substrate an amorphous semiconductor host matrix film and introducing therein a plurality of different compensating or altering materials comprising at least fluorine and which, as they are introduced into said host matrix material, are in an activated form produced in a manner where the amount produced and the form thereof is independent of the process of depositing the film.

6. The method of claim 5 wherein said at least one element of said host matrix is silicon.

7. The method of claim 5 wherein at least two complimentary compensating or altering materials are introduced into said film, each of which reduces localized states in the energy gap thereof not similarly reduced by the other of same.

8. The method of claim 5 wherein said at least one element of said hot matrix material is silicon and said plurality of compensating of altering materials is hydrogen and fluorine.

9. The method of claim 5 wherein said activated compensating or altering materials are introduced into the film as the film is being deposited.

10. The method of claim 5 wherein said plurality of compensating or altering materials are gaseous or vaporized materials activated by elevating their temperatures to a high gas decomposing temperature.

11. The method of claim 5 wherein said plurality of compensating or altering materials are activated by radiant energy.

12. The method of claim 7 wherein said compensating or altering materials comprise at least hydrogen and fluorine.

13. The method of claim 5, 6, 7, or 9 where said plurality of compensating or altering materials is activated into a state which is relatively unstable and such compensating materials are activated in the immediate vicinity of the amorphous semiconductor film into which they are then introduced.

14. The method of claim 9 wherein the amorphous semiconductor film is formed in an evacuated space, and said compensating or altering materials are activated in said evacuated space in the immediate vicinity of the depositing amorphous semiconductor film into which they are then introduced.

15. The method of claim 5 wherein said activated compensating or altering materials are activated by an electric field generated between two spaced electrodes to form a plasma of such compensating or altering materials.

16. The method of claim 15 wherein the film of amorphous semiconductor material into which the compensating or altering materials are introduced is located between said electrodes.

21. A method of making a semiconductor film having good photoconductive properties, the film comprising an amorphous photoconductive semiconductor host matrix having structural configurations which would have a high density of localized states which adversely affects the obtainment of a high degree of photoconductivity unless compensated or altered by a compensating or altering material, said method comprising:

vaporizing the element or elements which are to form said semiconductor host matrix in an evacuated space, condensing the same on a substrate in said evacuated space while introducing into the depositing film a plurality of compensating or altering materials comprising at least fluorine and which substantially reduces the density of said localized states and the dark conductivity thereof from that which would be provided without introducing said plurality of compensating or altering materials.

42. The method of claim 5, 21, 22, 33 or 34 wherein at least two different compensating or altering materials are introduced into the amorphous semiconductor film which materials include hydrogen and fluorine.

22. A method of making a semiconductor film having a given desirable electrical characteristic and to comprise an amorphous semiconductor host matrix and which would have structural configurations having a high density of localized states in the energy gap thereof adversely affecting the obtainment of said electrical characteristic unless compensated or altered by a compensating or altering material, said method comprising:

vaporizing the element of elements which are to form said semiconductor host matrix in an evacuated space, and condensing the same on a substrate in said evacuated space while introducing into the depositing film a plurality of compensating or altering materials comprising at least fluorine and in an amount which substantially reduces the density of said localized states from that which would be provided without introducing said plurality of compensating or altering materials.

23. A method of making an amorphous semiconductor film to comprise an amorphous host matrix having at least one element including silicon and which has electronic configurations which have an energy gap with a density of localized states which adversely affect the obtainment of a given electrical characteristic unless compensated or altered by a compensating or altering material, said method comprising:

introducing into such amorphous semiconductor host matrix at least one compensating material including fluorine which, as it is introduced into said host matrix material, is in activated form.

24. The method of claim 23 wherein said film is modified by adding relatively small amounts of a dopant material which shifts the Fermi level thereof to a point at or near the valence or conduction band thereof.

25. The method of claim 23 wherein said activated compensating or altering material is introduced into the film as the film is being formed.

26. The method of claim 25 wherein the amorphous semiconductor film is formed in an evacuated space, and said compensating material or altering is activated in said evacuated space in the immediate vicinity of the depositing amorphous semiconductor film into which it is then introduced.

40. The method of claim 24 or 27 wherein the density of localized states in the energy gap of said amorphous semiconductor film is no greater than 10¹⁶ per cubic centimeter per eV and the conductivity of said ohmic contact interface region thereof is no less than about 10^-1 (ohm cm)^-1.

33. A method of making a p-n junction-containing amorphous semiconductor host matrix body having structural configurations which would have configurations having an energy gap with a high density or localized states therein unless compensated or altered by a compensating or altering material, said method comprising the steps of vaporizing in an evacuated space the element or elements which are to form said semiconductor body, condensing the same as a film upon a substrate, introducing into the depositing film a plurality of compensating or altering materials comprising at least fluorine and which will cause the film to have a relatively low density of localized states in the energy gap thereof, and during only part of the period said film is being deposited injecting a modifying agent which will impart thereto either a p or n-type conductivity to form a p-n junction in the film.

34. A method of making an amorphous semiconductor host matrix body having structural configurations which would have configurations having an energy gap with a high density of localized states therein unless compensated or altered by a compensating or altering material, said method comprising the steps of vaporizing in an evacuated space the element or elements which are to form said semiconductor body, condensing the same as a film upon a substrate, and introducing into the film a plurality of different compensating or altering materials which will cause the film to have a relatively low density of localized states in the energy gap thereof, while elevating the temperature of the film to a point below the crystallization temperature thereof to reduce the porosity of the film and the localized states in the energy gap.

35. The method of claim 34 wherein the environment in which said compensating or altering materials are introduced into said amorphous semiconductor host matrix film is different from that wherein said film was deposited and which is in excess of atmospheric pressure.

36. The method of claim 34 or 35 where said compensating or altering materials introduced into the film are activated by an electric field.

37. The method of claim 34 wherein said compensating or altering materials introduced into the film are activated by radiant energy.

38. The method of claim 34, 35, or 37 wherein said film and compensating or altering materials are subjected to an electric field.