US4400409A
Expired / Lapsed
US
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Method of making p-doped silicon films
Assignee: United Solar Systems Corp
•
Filing: 1980-05-19
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Granted: 1983-08-23
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Expires: 2000-05-19
Abstract
Abstract The production of improved photovoltaic solar cells and the like comprising both p and n type deposited silicon film regions is made possible by a process which provides more efficient p-doped silicon films with higher acceptor concentrations. The process utilizes previously known p-dopant metal or boron gaseous materials in unique forms and conditions in a glow discharge silicon preferably hydrogen and fluorine compensated deposition process. Thus, p-dopant metals like aluminum may be used in an elemental evaporated form, rather than in a gaseous compound form heretofore ineffectively used and deposited with the glow discharge deposited silicon on substrates kept at lower temperatures where fluorine and hydrogen compensation is most effective. Preferably boron in a gaseous compound form like diborane and other p-dopant metals in a gaseous form are used uniquely during the glow discharge deposition of silicon by heating the substrate to heretofore believed undesirably higher temperatures, like at least about 450° C. to 800° C. where at least fluorine compensation, if desired, is still effective. The improved devices, such as solar cells, can be manufactured in a continuous process on a web type substrate moved through a plurality of film deposition chambers. Each of the chambers is dedicated to depositing a particular type of film layer (p, i or n) and is isolated from the other chambers.
Inventors
- 👤 Masatsugu Izu
- 👤 Vincent D. Cannella
- 👤 Stanford R. Ovshinsky
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-24 08:49
CPC Classifications
H; H10; H10F; H10F19/00; H10F19/30; H10F19/31; C; C23; C23C; C23C16/00; C23C16/44; C23C16/54; C23C16/50; C23C16/517; H10F10/00; H10F10/10; H10F10/17; H10F30/00; H10F30/20; H10F30/21; H10F30/22; H10F30/223; H10F71/00; H10F77/00; H10F77/10; H10F77/16; H10F77/169; Y; Y02; Y02E; Y02E10/00; Y02E10/50
Claims Analysis
Total Claims: 46
Claim 1
Independent Claim
87 words
A method of making a p-type silicon semiconductor film, said method comprising the step of depositing on a substrate a semiconductor host matrix film including at least silicon by glow discharge of a compound containing at least silicon in a partial vacuum atmosphere and during glow discharge deposition of the film, introducing an evaporated metal p-dopant modifier element into the silicon depositing glow discharge region which metal modifier element is deposited with the glow discharge deposited silicon film to modify the same to produce a p-type film.
Claim 2
Independent Claim
87 words
A method of making a p-type silicon semiconductor film, said method comprising the step of depositing on a substrate a semiconductor host matrix film including at least silicon by glow discharge of a compound containing at least silicon in a partial vacuum atmosphere and during glow discharge deposition of the film, introducing an evaporated metal p-dopant modifier element into the silicon depositing glow discharge region which metal modifier element is deposited with the glow discharge deposited silicon film to modify the same to produce a p-type film.
Claim 3
Dependent Claim
28 words
The method as defined in claim 1 wherein said evaporated metal modifier element is at least one of the group consisting of aluminum, gallium, indium, zinc or thallium.
Claim 4
Independent Claim
132 words
A method of making a p-type silicon film, said method comprising the step of depositing on a substrate heated to at least above a temperature of 500° C. a semiconductor host matrix film including at least silicon by glow discharge of a compound containing at least silicon in a partial vacuum atmosphere and during glow discharge deposition of the film introducing a p-dopant gaseous compound into the silicon depositing glow discharge region, said p-dopant gaseous compound including at least a p-dopant modifier element and a non-p-dopant substituent and which gaseous compound disassociates into said p-dopant modifier element and said non-p-dopant substituent at said substrate temperature of at least about 500° C., the p-dopant modifier element then combining with the depositing silicon to modify the silicon semiconductor material to produce a p-type film.
Claim 5
Independent Claim
132 words
A method of making a p-type silicon film, said method comprising the step of depositing on a substrate heated to at least above a temperature of 500° C. a semiconductor host matrix film including at least silicon by glow discharge of a compound containing at least silicon in a partial vacuum atmosphere and during glow discharge deposition of the film introducing a p-dopant gaseous compound into the silicon depositing glow discharge region, said p-dopant gaseous compound including at least a p-dopant modifier element and a non-p-dopant substituent and which gaseous compound disassociates into said p-dopant modifier element and said non-p-dopant substituent at said substrate temperature of at least about 500° C., the p-dopant modifier element then combining with the depositing silicon to modify the silicon semiconductor material to produce a p-type film.
Claim 6
Dependent Claim
25 words
The method of claim 3 wherein said p-dopant modifier element is at least one of the group consisting of aluminum, gallium, indium, zinc or thallium.
Claim 7
Dependent Claim
12 words
The method of claim 3 wherein said p-dopant modifier element is boron.
Claim 8
Dependent Claim
11 words
The method of claim 5 wherein said gaseous compound is diborane.
Claim 9
Dependent Claim
89 words
The method as defined in claim 1 wherein said method forms one step in a multi-step process for forming successively by glow discharge deposited silicon-containing films of opposite (p and n) conductivity type, the n-type silicon-containing film being formed by introducing into the glow discharge region a compound containing at least silicon in a partial vacuum atmosphere and during the glow discharge deposition of the film introducing an n-dopant modifier element which is deposited with the glow discharge deposited film to modify the same to produce an n-type film.
Claim 10
Dependent Claim
89 words
The method as defined in claim 3 wherein said method forms one step in a multi-step process for forming successively by glow discharge deposited silicon-containing films of opposite (p and n) conductivity type, the n-type silicon-containing film being formed by introducing into the glow discharge region a compound containing at least silicon in a partial vacuum atmosphere and during the glow discharge deposition of the film introducing an n-dopant modifier element which is deposited with the glow discharge deposited film to modify the same to produce an n-type film.
Claim 11
Dependent Claim
30 words
The method as defined in claim 1 wherein said method forms one step in a multi-step process for forming successively deposited silicon-containing films of opposite (p and n) conductivity type.
Claim 12
Dependent Claim
30 words
The method as defined in claim 3 wherein said method forms one step in a multi-step process for forming successively deposited silicon-containing films of opposite (p and n) conductivity type.
Claim 13
Dependent Claim
66 words
The method as defined in claim 8 wherein said n-type silicon-containing film is formed in the presence of at least one density of states reducing element which combines with the depositing silicon-containing film most efficiently at a temperature well below 500° C., said n-type silicon-containing film being applied over said p-type silicon-containing film while the substrate is held at said temperature well below said 500° C.
Claim 14
Dependent Claim
66 words
The method as defined in claim 7 wherein said n-type silicon-containing film is formed in the presence of at least one density of states reducing element which combines with the depositing silicon-containing film most efficiently at a temperature well below 500° C., said n-type silicon-containing film being applied over said p-type silicon-containing film while the substrate is held at said temperature well below said 500° C.
Claim 15
Dependent Claim
39 words
The method as defined in claim 7 wherein there is deposited between said p and n doped silicon films an intrinsic amorphous silicon-containing film by the glow discharge thereof without a p or n dopant modifying element present therein.
Claim 16
Dependent Claim
39 words
The method as defined in claim 9 wherein there is deposited between said p and n doped silicon films an intrinsic amorphous silicon-containing film by the glow discharge thereof without a p or n dopant modifying element present therein.
Claim 17
Dependent Claim
39 words
The method as defined in claim 8 wherein there is deposited between said p and n doped silicon films an intrinsic amorphous silicon-containing film by the glow discharge thereof without a p or n dopant modifying element present therein.
Claim 18
Dependent Claim
39 words
The method as defined in claim 10 wherein there is deposited between said p and n doped silicon films an intrinsic amorphous silicon-containing film by the glow discharge thereof without a p or n dopant modifying element present therein.
Claim 19
Independent Claim
39 words
The method as defined in claims 1 or 3 wherein there is deposited adjacent to said p-type silicon film an intrinsic amorphous silicon-containing film by the glow discharge thereof without a p or n dopant modifying element present therein.
Claim 20
Independent Claim
21 words
The method as defined in claims 7 or 8 wherein each of said doped silicon-containing film is a substantially amorphous film.
Claim 21
Independent Claim
31 words
The method as defined in claims 7 or 8 wherein said p and n doped silicon-containing films are deposited one immediately on top of the other to form a p-n junction.
Claim 22
Independent Claim
33 words
The method as defined in claims 7 or 8 wherein at least part of said p and n dopant materials are deposited in amounts which form p + and n + silicon films.
Claim 23
Independent Claim
97 words
The method as defined in claims 7 or 8 wherein at least one of said silicon-containing films is a substantially amorphous film, and there is included in said silicon compound forming each such film one density of states reducing element and at least one separate density of states reducing element not derived from the compound is introduced into said glow discharge region so that these elements are incorporated in each said substantially amorphous silicon-containing film deposited on said substrate to alter the electronic configurations and produce a reduced density of localized states in the energy gap thereof.
Claim 24
Dependent Claim
44 words
The method as defined in claim 7 wherein said substrate is formed in a substantially continuous web, and each of said silicon films is deposited at a separate glow discharge region past which said web is moved to form a substantially continuous deposition process.
Claim 25
Dependent Claim
44 words
The method as defined in claim 8 wherein said substrate is formed in a substantially continuous web, and each of said silicon films is deposited at a separate glow discharge region past which said web is moved to form a substantially continuous deposition process.
Claim 26
Independent Claim
24 words
The method as defined in claims 7 or 8 wherein said p-doped containing film is deposited to a thickness of less than 1000 angstroms.
Claim 27
Independent Claim
20 words
The method as defined in claims 7 or 8 including forming each of said semiconducting layers in a continuous process.
Claim 28
Independent Claim
79 words
The method as defined in claims 7 or 8 wherein at least one of said silicon-containing films is a substantially amorphous film and there is included in the glow discharge region forming each such film at least one density of states reducing element so that the element is incorporated in each said substantially amorphous silicon film deposited on said substrate to alter the electronic configurations thereof to produce a reduced density of localized states in the energy gap thereof.
Claim 29
Independent Claim
14 words
The method as defined in claims 1 or 3 wherein said compound includes hydrogen.
Claim 30
Independent Claim
14 words
The method as defined in claims 1 or 3 wherein said compound includes fluorine.
Claim 31
Independent Claim
16 words
The method as defined in claims 1 or 3 wherein said compound includes fluorine and hydrogen.
Claim 32
Independent Claim
24 words
The method as defined in claims 1 or 3 wherein said compound is at least a mixture of SiF 4 and H 2 .
Claim 33
Independent Claim
143 words
A method of making a photovoltaic panel comprising forming a roll of a web of a flexible substrate material with one or more electrode-forming regions thereon, unrolling said substrate roll substantially continuously into a partially evacuated space including at least one silicon depositing region therein where there is deposited over at least some of said one or more electrode-forming regions at least two thin, flexible silicon films which are of opposite conductivity (p and n) type, one or more of said films forming a photovoltaic depletion region, said substrate is formed in a substantially continuous web, and each of said silicon films is deposited at a separate glow discharge region past which said web is moved to form a substantially continuous deposition process, and subsequently applying on said silicon films a thin flexible electrode-forming layer, separately as to each of said electrode-forming regions.
Claim 34
Independent Claim
143 words
A method of making a photovoltaic panel comprising forming a roll of a web of a flexible substrate material with one or more electrode-forming regions thereon, unrolling said substrate roll substantially continuously into a partially evacuated space including at least one silicon depositing region therein where there is deposited over at least some of said one or more electrode-forming regions at least two thin, flexible silicon films which are of opposite conductivity (p and n) type, one or more of said films forming a photovoltaic depletion region, said substrate is formed in a substantially continuous web, and each of said silicon films is deposited at a separate glow discharge region past which said web is moved to form a substantially continuous deposition process, and subsequently applying on said silicon films a thin flexible electrode-forming layer, separately as to each of said electrode-forming regions.
Claim 35
Dependent Claim
82 words
The method as defined in claim 31 wherein depositing said p-type film includes depositing a semiconductor host matrix film including at least silicon by glow discharge of a compound containing at least silicon in said partial vacuum atmosphere and during the glow discharge deposition of the film introducing an evaporated metal p-dopant modifier element into the silicon depositing glow discharge station which metal modifier element is deposited with the glow discharge deposited silicon film to modify same to form the p-type film.
Claim 36
Dependent Claim
28 words
The method as defined in claim 32 wherein said evaporated metal modifier element is at least one of the group consisting of aluminum, gallium, indium, zinc or thallium.
Claim 37
Dependent Claim
136 words
The method as defined in claim 31 wherein depositing said p-type film includes depositing on said substrate heated to at least above a temperature of 500° C. and below 800° C. a semiconductor host matrix film including at least silicon by glow discharge of a compound containing at least silicon in said partial vacuum atmosphere and during the glow discharge deposition of the film introducing a p-dopant gaseous compound into the silicon depositing glow discharge region, said p-dopant gaseous compound including at least a p-dopant modifier element and a non-p-dopant substituent and which gaseous compound disassociates into said p-dopant modifier element and said non-p-dopant substituent at said substrate temperature of at least above 500° C., the p-dopant modifier element then combining with the depositing silicon to modify the silicon semiconductor material to form the p-type film.
Claim 38
Dependent Claim
27 words
The method as defined in claim 34 wherein said p-dopant modifier element is at least one of the group consisting of aluminum, gallium, indium, zinc or thallium.
Claim 39
Dependent Claim
14 words
The method as defined in claim 34 wherein said p-dopant modifier element is boron.
Claim 40
Dependent Claim
13 words
The method as defined in claim 36 wherein said gaseous compound is diborane.
Claim 41
Dependent Claim
39 words
The method as defined in claim 31 wherein there is deposited between said p and n doped silicon films an intrinsic amorphous silicon-containing film by the glow discharge thereof without a p or n dopant modifying element present therein.
Claim 42
Dependent Claim
95 words
The method as defined in claim 31 wherein at least one of said silicon-containing films is a substantially amorphous film, and there is included in said silicon compound forming each such film one density of states reducing element and at least one separate density of states reducing element not derived from the compound is introduced into said glow discharge region so that these elements are incorporated in each said substantially amorphous silicon-containing film deposited on said substrate to alter the electronic configurations and produce a reduced density of localized states in the energy gap thereof.
Claim 43
Dependent Claim
22 words
The method as defined in claim 31 wherein said p-doped silicon-containing film is deposited to a thickness of less than 1000 angstroms.
Claim 44
Dependent Claim
12 words
The method as defined in claim 31 wherein said compound includes fluorine.
Claim 45
Dependent Claim
22 words
The method as defined in claim 31 wherein said compound is at least a mixture of SiF 4 and H 2 .
Claim 46
Dependent Claim
32 words
The method as defined in claim 31 wherein said compound is at least a mixture of SiF 4 and H 2 in the ratio of 4 to 1 to 10 to 1.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1986-08-22 | 1987-02-21 | 1987-08-23 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1990-08-22 | 1991-02-21 | 1991-08-23 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1994-08-22 | 1995-02-21 | 1995-08-23 | $7700.00 | Window Closed / Lapsed |