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1. 发明授权

US5918111A Method and apparatus for manufacturing chalcopyrite semiconductor thin films 失效
公开(公告)号：US5918111A
公开(公告)日：1999-06-29
申请号：US613497
申请日：1996-03-11
申请人： Naoki Kohara , Takayuki Negami , Mikihiko Nishitani , Takahiro Wada
发明人： Naoki Kohara , Takayuki Negami , Mikihiko Nishitani , Takahiro Wada
IPC分类号： C23C14/06 , C23C14/54 , C30B23/02 , H01L31/032 , H01L31/18
CPC分类号： H01L31/0322 , C23C14/0623 , C23C14/541 , C30B23/002 , C30B23/02 , C30B29/46 , Y02E10/541
摘要： The method and the apparatus of manufacturing the I-III-VI.sub.2 type chalcopyrite semiconductor thin films of the present invention control the film composition easily and improve the reproducibility of films by monitoring the composition of the films during forming the films. The apparatus comprise the substrate holder and heater which are in the vacuum chamber and Mo-coated glass substrate on which Cu(In,Ga)Se.sub.2 films are deposited. The change of the substrate temperature is monitored by the use of a heating element to heat the substrate by releasing a certain quantity of heat, a mechanism of measuring a temperature of the heated substrate. The change of power supplied is monitored by the use of a power source for the heating element to keep the substrate at a certain temperature and a mechanism of monitoring the change of the power supplied to the heating element. The changes in substrate temperature or power supplied can be correlated to the film composition.

2. 发明授权

US5389572A Process of making chalcopyrite structure semiconductor film 失效
标题翻译：制造黄铜矿结构半导体膜的工艺
公开(公告)号：US5389572A
公开(公告)日：1995-02-14
申请号：US195948
申请日：1994-02-14
申请人： Takayuki Negami , Mikihiko Nishitani , Shigemi Kohiki , Takahiro Wada
发明人： Takayuki Negami , Mikihiko Nishitani , Shigemi Kohiki , Takahiro Wada
IPC分类号： H01L21/363 , H01L31/032 , H01L31/04 , H01L33/28 , H01L33/30 , H01L33/40 , H01S5/00 , H01L21/22
CPC分类号： H01L31/0322 , Y02E10/541 , Y02P70/521 , Y10S148/153 , Y10S438/93
摘要： A I-III-VI.sub.2 chalcopyrite semiconductor film containing a Group VII element as a dopant, and methods to produce such a chalcopyrite film are provided. The chalcopyrite film of the present invention has stoichiometric composition, and electrical characteristics such as p-n conduction type, carrier concentration and the like are controlled.
摘要翻译：提供了含有VII族元素作为掺杂剂的I-III-VI2黄铜矿半导体膜，以及制造这种黄铜矿膜的方法。本发明的黄铜矿膜具有化学计量组成，并且控制诸如p-n导电型，载流子浓度等的电特性。

3. 发明授权

US6162296A Method and apparatus for manufacturing chalcopyrite semiconductor thin films 有权
标题翻译：制造黄铜矿半导体薄膜的方法和装置
公开(公告)号：US6162296A
公开(公告)日：2000-12-19
申请号：US252388
申请日：1999-02-18
申请人： Naoki Kohara , Takayuki Negami , Mikihiko Nishitani , Takahiro Wada
发明人： Naoki Kohara , Takayuki Negami , Mikihiko Nishitani , Takahiro Wada
IPC分类号： C23C14/06 , C23C14/54 , C30B23/02 , H01L31/032 , C23C14/26
CPC分类号： H01L31/0322 , C23C14/0623 , C23C14/541 , C30B23/002 , C30B23/02 , C30B29/46 , Y02E10/541
摘要： The method and the apparatus of manufacturing the I-III-VI.sub.2 type chalcopyrite semiconductor thin films of the present invention control the film composition easily and improve the reproducibility of films by monitoring the composition of the films during forming the films. The apparatus comprise the substrate holder and heater which are in the vacuum chamber and Mo-coated glass substrate on which Cu(In,Ga)Se.sub.2 films are deposited. The change of the substrate temperature is monitored by the use of a heating element to heat the substrate by releasing a certain quantity of heat, a mechanism of measuring a temperature of the heated substrate. The change of power supplied is monitored by the use of a power source for the heating element to keep the substrate at a certain temperature and a mechanism of monitoring the change of the power supplied to the heating element. The changes in substrate temperature or power supplied can be correlated to the film composition.
摘要翻译：本发明的I-III-VI2型黄铜矿半导体薄膜的制造方法和装置通过在形成薄膜期间监测薄膜的成分，容易地控制薄膜组合并提高薄膜的再现性。该装置包括位于其中沉积有Cu（In，Ga）Se2膜的真空室和Mo涂覆的玻璃基板中的基板保持器和加热器。通过使用加热元件通过释放一定量的热来加热衬底来监测衬底温度的变化，测量加热衬底的温度的机理。通过使用用于加热元件的电源将基板保持在一定温度并监视供应到加热元件的功率的变化的机构来监测供电的变化。衬底温度或功率的变化可以与膜组成相关。

4. 发明授权

US5725671A Apparatus for manufacturing chalcopyrite film 失效
标题翻译：用于制造黄铜矿膜的装置
公开(公告)号：US5725671A
公开(公告)日：1998-03-10
申请号：US795289
申请日：1997-02-04
申请人： Mikihiko Nishitani , Takayuki Negami , Takahiro Wada
发明人： Mikihiko Nishitani , Takayuki Negami , Takahiro Wada
IPC分类号： H01L31/032 , C23C16/00
CPC分类号： H01L31/0322 , Y02E10/541
摘要： An apparatus for manufacturing an ABC.sub.2 chalcopyrite film (wherein A represents Cu or Ag, B represents In, Ga or Al, C represents S, Se or Te) includes a substrate holder, a substrate heater, a supply source for supplying elements A, B or C onto the substrate and for controlling the supply process, and a monitor for monitoring an electrical or optical property of the thin film layer deposited on the substrate. The electrical or optical property of the thin film layer abruptly changes at a first time point when the A/B ratio in the thin film layer changes from an element A-excessive state to the stoichiometric composition ratio of the ABC.sub.2. The electrical or optical property of the thin film layer demonstrates a stable value at a second time point when the A/B ratio becomes an element-B excessive state. Deposition is terminated at the second time point.
摘要翻译：一种用于制造ABC2黄铜矿膜的设备（其中A表示Cu或Ag，B表示In，Ga或Al，C表示S，Se或Te）包括基板保持器，基板加热器，用于供应元件A，B的供应源或C并且用于控制供应过程，以及用于监测沉积在基板上的薄膜层的电学或光学特性的监视器。当薄膜层中的A / B比从元素A过量状态变化到ABC2的化学计量组成比时，薄膜层的电学或光学特性在第一时间点突然变化。当A / B比变为元件B过量状态时，薄膜层的电学或光学特性在第二时间点表现出稳定的值。沉积在第二个时间点终止。

5. 发明授权

US5506426A Compound semiconductor, a method for producing a thin film thereof, and a semiconductor device having the thin film 失效
标题翻译：化合物半导体，其薄膜的制造方法以及具有该薄膜的半导体装置
公开(公告)号：US5506426A
公开(公告)日：1996-04-09
申请号：US61491
申请日：1993-05-12
申请人： Shigemi Kohiki , Takayuki Negami , Mikihiko Nishitani , Takahiro Wada
发明人： Shigemi Kohiki , Takayuki Negami , Mikihiko Nishitani , Takahiro Wada
IPC分类号： C01B19/04 , C01G1/00 , H01L21/203 , H01L31/032 , H01L31/04 , H01L31/068 , H01L31/10 , H01L29/18 , H01L31/0328 , H01L31/0336 , H01L31/103
CPC分类号： H01L31/032 , H01L31/0322 , H01L31/0323 , H01L31/068 , Y02E10/541 , Y02E10/547 , Y10S438/93
摘要： Chalcopyrite compound semiconductor thin films represented by I-III-VI.sub.2-x V.sub.x or I-III-VI.sub.2-x VII.sub.x, and semiconductor devices having a I-III-VI.sub.2 /I-III-VI.sub.2-x V.sub.x or I-III-VI.sub.2 /I-III-VI.sub.2-x VII.sub.x chalcopyrite homojunction are provided. Such chalcopyrite compound semiconductor thin films are produced by radiating molecular beams or ion beams of the I, III, VI, and V or VII group elements simultaneously, or by doping I-III-VI.sub.2 chalcopyrite thin films with VII-group atoms after the formation thereof. Pollution-free solar cells are also provided, which are formed by the steps of forming a structure of a lower electrode, a chalcopyrite semiconductor thin film, and an upper electrode and radiating accelerated ion beams of a V, VII, or VIII group element thereto.
摘要翻译：由I-III-VI2-xVx或I-III-VI2-xVIIx表示的黄铜矿化合物半导体薄膜和具有I-III-VI2 / I-III-VI2-xVx或I-III-VI2 / 提供了III-VI2-xVIIx型黄铜矿同质结。这种黄铜矿化合物半导体薄膜通过同时辐射I，III，VI和V或VII族元素的分子束或离子束，或者通过在形成之后掺杂具有VII-基团原子的I-III-VI2黄铜矿薄膜其中。还提供了无污染的太阳能电池，其通过形成下电极，黄铜矿半导体薄膜和上电极的结构的步骤形成，并且将V，VII或VIII族元素的加速离子束辐射到其上。

6. 发明授权

US5500056A Solar cell containing low melting point glass layer 失效
标题翻译：含有低熔点玻璃层的太阳能电池
公开(公告)号：US5500056A
公开(公告)日：1996-03-19
申请号：US274722
申请日：1994-07-18
申请人： Takahiro Wada , Mitsusuke Ikeda , Mikihiko Nishitani , Masaharu Terauchi , Takayuki Negami , Naoki Kohara
发明人： Takahiro Wada , Mitsusuke Ikeda , Mikihiko Nishitani , Masaharu Terauchi , Takayuki Negami , Naoki Kohara
IPC分类号： H01L31/0216 , H01L31/0336 , H01L31/0392 , H01L31/0725 , H01L31/0749 , H01L31/04 , H01L31/0203
CPC分类号： H01L31/0749 , H01L31/02167 , H01L31/0392 , H01L31/03925 , H01L31/0725 , Y02E10/541
摘要： A solar cell includes a compound semiconductor, which is a laminated film having compound semiconductor layers, and low melting point glass. When the solar cell is heated by fire, the low melting point glass melts to seal the compound semiconductor so that toxic substances contained in the compound semiconductor are not released into the air.
摘要翻译：太阳能电池包括具有化合物半导体层的层叠膜和低熔点玻璃的化合物半导体。当太阳能电池被火加热时，低熔点玻璃熔化以密封化合物半导体，使得包含在化合物半导体中的有毒物质不会释放到空气中。

7. 发明授权

US5633033A Method for manufacturing chalcopyrite film 失效
标题翻译：制造黄铜矿膜的方法
公开(公告)号：US5633033A
公开(公告)日：1997-05-27
申请号：US420183
申请日：1995-04-11
申请人： Mikihiko Nishitani , Takayuki Negami , Takahiro Wada
发明人： Mikihiko Nishitani , Takayuki Negami , Takahiro Wada
IPC分类号： H01L31/032 , C23C16/52 , C23C16/06
CPC分类号： H01L31/0322 , Y02E10/541
摘要： A method for manufacturing an ABC.sub.2 chalcopyrite film (wherein A represents Cu or Ag, B represents In, Ga or Al, C represents S, Se or Te) comprises; a first step of forming a film of a composition of ABC.sub.2 containing element A in excess; a second step of exposing the film formed in the first step to a flux or gas containing element B and C, or to a gas or flux containing element A, B and C but containing element B in excess; and monitoring an electrical or optical property of the film in order to determine an end point of the second step where the electrical or optical property of the film demonstrates a specific change.
摘要翻译：一种制备ABC2黄铜矿膜的方法（其中A表示Cu或Ag，B表示In，Ga或Al，C表示S，Se或Te）包括：形成含有过量的元素A的ABC2的组合物的膜的第一工序; 将在第一步骤中形成的膜暴露于含有助熔剂或气体的元素B和C的第二步骤，或者将含有元素A，B和C但含有元素B的气体或助熔剂过量的第二步骤; 以及监测胶片的电气或光学性能，以便确定第二步骤的终点，其中胶片的电或光学特性表现出特定的变化。

8. 发明授权

US5567469A Process for producing chalcopyrite type compound thin film 失效
标题翻译：生产黄铜矿型复合薄膜的方法
公开(公告)号：US5567469A
公开(公告)日：1996-10-22
申请号：US458015
申请日：1995-06-01
申请人： Takahiro Wada , Mikihiko Nishitani , Takayuki Negami
发明人： Takahiro Wada , Mikihiko Nishitani , Takayuki Negami
IPC分类号： H01L31/04 , H01L21/36 , H01L31/032 , B05D1/36
CPC分类号： H01L21/02422 , H01L21/02491 , H01L21/02568 , H01L21/02614 , H01L21/02631 , H01L31/0322 , Y02E10/541 , Y02P70/521
摘要： A chalcopyrite compound, for instance, CuInS.sub.2 or CuInSe.sub.2, is prepared by subjecting a thin film containing copper metal, indium metal, and an indium compound or a compound which contains both indium and copper, selected from the group consisting of oxides, sulfides and selenides, with heat under a reducing atmosphere containing at least one of the Group VIb element or under an atmosphere containing a reducing compound of at least one of the Group VIb element, thereby converting said thin film into a chalcopyrite compound.
摘要翻译：黄铜矿化合物，例如CuInS 2或CuInSe 2，通过使含有铜金属，铟金属和铟化合物的薄膜或含有铟和铜的化合物，选自氧化物，硫化物和硒化物在含有VIb族元素中的至少一种的还原气氛下或在含有VIb族元素中至少一种的还原性化合物的气氛下进行加热，从而将所述薄膜转化为黄铜矿化合物。

9. 发明授权

US6023020A Solar cell and method for manufacturing the same 失效
标题翻译：太阳能电池及其制造方法
公开(公告)号：US6023020A
公开(公告)日：2000-02-08
申请号：US950204
申请日：1997-10-14
申请人： Mikihiko Nishitani , Takayuki Negami , Naoki Kohara , Takahiro Wada , Yasuhiro Hashimoto
发明人： Mikihiko Nishitani , Takayuki Negami , Naoki Kohara , Takahiro Wada , Yasuhiro Hashimoto
IPC分类号： H01L31/032 , H01L31/0336
CPC分类号： H01L31/0749 , H01L31/0322 , Y02E10/541
摘要： A solar cell utilizing a chalcopyrite semiconductor and reducing the density of defects on the junction interface of pn junctions is provided. This solar cell includes a substrate, a back electrode formed on the substrate, a p-type chalcopyrite semiconductor thin film formed on the back electrode, an n-type semiconductor thin film formed so as to constitute a pn junction with the p-type chalcopyrite semiconductor thin film, and a transparent electrode formed on the n-type semiconductor thin film. A material having a higher resistivity than the p-type chalcopyrite semiconductor is formed between the p-type chalcopyrite semiconductor thin film and the n-type semiconductor thin film. A thin film made of this material may be formed by deposition from a solution. For example, CuInS.sub.2 is formed on the surface of a p-type chalcopyrite based semiconductor such as CuInSe.sub.2 by contacting the surface of the semiconductor with a solution in which a salt containing group IIIb elements, an organic substance containing group VIb elements and acid are mixed.
摘要翻译：提供了利用黄铜矿半导体并降低pn结的结界面上的缺陷密度的太阳能电池。该太阳能电池包括基板，形成在基板上的背面电极，形成在背面电极上的p型黄铜矿半导体薄膜，形成为与p型黄铜矿形成pn结的n型半导体薄膜半导体薄膜和形成在n型半导体薄膜上的透明电极。在p型黄铜矿半导体薄膜和n型半导体薄膜之间形成具有比p型黄铜矿半导体更高的电阻率的材料。由该材料制成的薄膜可以通过从溶液中沉积而形成。例如，通过使半导体的表面与含有IIIb族元素的盐，含有VIb族元素的有机物质和酸混合的溶液与CuInSe 2的p型黄铜矿类半导体的表面形成CuInS 2，。

10. 发明授权

US5728231A Precursor for semiconductor thin films and method for producing semiconductor thin films 失效
标题翻译：用于半导体薄膜的前体及半导体薄膜的制造方法
公开(公告)号：US5728231A
公开(公告)日：1998-03-17
申请号：US648497
申请日：1996-05-15
申请人： Takayuki Negami , Masaharu Terauchi , Mikihiko Nishitani , Takahiro Wada
发明人： Takayuki Negami , Masaharu Terauchi , Mikihiko Nishitani , Takahiro Wada
IPC分类号： C23C14/06 , C23C14/08 , C23C14/58 , H01L31/032 , H01L31/0336 , H01L31/18
CPC分类号： C23C14/5866 , C23C14/0623 , C23C14/08 , H01L31/0322 , H01L31/0323 , H01L31/0749 , Y02E10/541 , Y02P70/521 , Y10S438/93 , Y10T428/12528 , Y10T428/12611 , Y10T428/12681 , Y10T428/12903
摘要： A precursor for manufacturing a semiconductor thin film in which an oxide thin film comprising at least one element as a dopant, selected from a group which consists of Groups IA, IIA, IIB, VA, and VB elements, and Groups IB and IIIA elements which are main components of the semiconductor thin film are deposited on a substrate, or a precursor for manufacturing a semiconductor thin film which is formed by depositing a thin film of oxide comprising the Groups IB and IIIA elements on the substrate wherein the content of at least one of the Groups IB and IIIA elements is varied in the direction of film thickness, and a method for manufacturing a semiconductor thin film comprising the step of heat treating the precursor for manufacturing the semiconductor thin film in an atmosphere containing a Group VIA element. The present invention provides a precursor for manufacturing a semiconductor thin film and a method for manufacturing the semiconductor thin film using the precursor which are suitable for manufacturing a semiconductor thin film having a chalcopyrite structure that has a high and uniform energy conversion efficiency when the semiconductor thin film is used as a photoabsorptive layer of a solar cell.
摘要翻译：用于制造半导体薄膜的前体，其中包含至少一种元素作为掺杂剂的氧化物薄膜，其选自由IA，IIA，IIB，VA和VB族元素组成的组以及IB和IIIA族元素，半导体薄膜的主要成分沉积在基板上，或用于制造半导体薄膜的前体，该半导体薄膜是通过在衬底上沉积包含IB和IIIA族元素的氧化物的薄膜而形成的，其中至少一个 IB和IIIA族元素在膜厚方向上是不同的，以及一种制造半导体薄膜的方法，包括在含有VIA元素的气氛中对用于制造半导体薄膜的前体进行热处理的步骤。本发明提供一种用于制造半导体薄膜的前体和使用该前体制造半导体薄膜的方法，该半导体薄膜适用于制造具有高半导体薄片的具有高且均匀的能量转换效率的黄铜矿结构的半导体薄膜膜被用作太阳能电池的光吸收层。

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