公开(公告)号：WO1994024696A1

公开(公告)日：1994-10-27

申请号：PCT/US1994003827

申请日：1994-04-07

Applicant: MIDWEST RESEARCH INSTITUTE

Inventor： MIDWEST RESEARCH INSTITUTE ,  TUTTLE, John, R. ,  CONTRERAS, Miguel, A. ,  NOUFI, Rommel ,  ALBIN, David, S.

IPC: H01L21/302

CPC classification number: H01L31/0322 ,  Y02E10/541 ,  Y02P70/521 ,  Y10S438/93

Abstract: Enhanced quality thin films of Cuw(In,Gay)Sez for semiconductor device applications are fabricated by initially forming a Cu-rich, phase-separated compound mixture comprising Cu(In,Ga):CuxSe on a substrate (12) to form a large-grain precursor (20) and then converting the excess CuxSe(18) to Cu(In,Ga)Se2 by exposing it to an activity of In (22) and/or Ga, either in vapor In and/or Ga form or in solid (In,Ga)ySez. Alternatively, the conversion can be made by sequential deposition of In and/or Ga and Se onto the phase-separated precursor (20). The conversion process is preferably performed in the temperature range of about 300-600 DEG C, where the Cu(InGa)Se2 (16) remains solid, while the excess CuxSe (18) is in a liquid flux. The characteristic of the resulting Cuw(In,Ga)ySez can be controlled by the temperature. Higher temperatures, such as 500-600 DEG C, results in a nearly stoichiometric Cu(In,Ga)Se2, whereas lower temperatures, such as 300-400 DEG C, results in a more Cu-poor compound, such as the Cu2(In,GA)4Se7 phase.

Abstract translation: 通过在衬底（12）上最初形成包含Cu（In，Ga）：CuxSe的富Cu相分离的化合物混合物来制造用于半导体器件应用的Cuw（In，Gay）Sez的增强质量薄膜，以形成大的 （20），然后通过将其过量的In（22）和/或Ga的活性暴露于In（22）和/或Ga的蒸气In和/或Ga形式中，或将其过量的CuxSe（18）转化为Cu（In，Ga）Se2 固体（In，Ga）ySez。 或者，可以通过将In和/或Ga和Se顺序沉积到相分离的前体（20）上进行转化。 转化过程优选在约300-600℃的温度范围内进行，其中Cu（InGa）Se2（16）保持固体，而过量的CuxSe（18）处于液体通量。 所得Cuw（In，Ga）ySez的特征可以由温度控制。 较高的温度（如500-600℃）导致几乎具有化学计量的Cu（In，Ga）Se2，而较低的温度（如300-400℃）会导致更多的Cu不良化合物，如Cu2 In，GA）4Se7相。

公开(公告)号：WO2003007386A1

公开(公告)日：2003-01-23

申请号：PCT/US2001/022192

申请日：2001-07-13

Applicant: MIDWEST RESEARCH INSTITUTE ,  TUTTLE, John, R. ,  NOUFI, Rommel ,  HASOON, Falah, S.

Inventor： TUTTLE, John, R. ,  NOUFI, Rommel ,  HASOON, Falah, S.

IPC: H01L31/0336

CPC classification number: H01L31/0749 ,  H01L31/02008 ,  H01L31/0392 ,  H01L31/03928 ,  Y02E10/541 ,  Y02P70/521

Abstract: A thin-film solar cell (10) is provided. The thin-film solar cell (10) comprises a flexible metallic substrate (12) having a first surface and a second surface. A back metal contact layer (16) is deposited on the first surface of the flexible metallic substrate (12). A semiconductor absorber layer (14) is deposited on the back metal contact. A photoactive film deposited on the semiconductor absorber layer (14) forms a heterojunction structure and a grid contact (24) deposited on the heterjunction structure. The flexible metal substrate (12) can be constructed of either aluminium or stainless steel. Furthermore, a method of constructing a solar cell is provided. The method comprises providing an aluminum substrate (12), depositing a semiconductor absorber layer (14) on the aluminum substrate (12), and insulating the aluminum substrate (12) from the semiconductor absorber layer (14) to inhibit reaction between the aluminum substrate (12) and the semiconductor absorber layer (14).

Abstract translation: 提供薄膜太阳能电池（10）。 薄膜太阳能电池（10）包括具有第一表面和第二表面的柔性金属基底（12）。 在柔性金属基板（12）的第一表面上沉积背金属接触层（16）。 半导体吸收层（14）沉积在背面金属触点上。 沉积在半导体吸收层（14）上的光活性膜形成异相结构和沉积在异质结结构上的栅极接触（24）。 柔性金属基底（12）可由铝或不锈钢构成。 此外，提供了构造太阳能电池的方法。 该方法包括提供铝基板（12），在铝基板（12）上沉积半导体吸收层（14），并将铝基板（12）与半导体吸收层（14）绝缘，以抑制铝基板 （12）和半导体吸收层（14）。

公开(公告)号：WO1996006454A1

公开(公告)日：1996-02-29

申请号：PCT/US1995009809

申请日：1995-08-03

Applicant: MIDWEST RESEARCH INSTITUTE

Inventor： MIDWEST RESEARCH INSTITUTE ,  ALBIN, David, S. ,  CARAPELLA, Jeffrey, J. ,  TUTTLE, John, R. ,  CONTRERAS, Miguel, A. ,  GABOR, Andrew, M. ,  NOUFI, Rommel ,  TENNANT, Andrew, L.

IPC: H01L21/208

CPC classification number: H01L31/0322 ,  Y02E10/541 ,  Y02P70/521

Abstract: A process for fabricating slightly Cu-poor thin-films of Cu(In,Ga)Se2 on a substrate (12) for semiconductor device applications includes the steps of forming initially a slightly Cu-rich, phase separated, mixture of Cu(In,Ga)Se2:CuxSe on the substrate (12) in solid form followed by exposure of the Cu(In,Ga)Se2:CuxSe solid mixture to an overpressure of Se vapor and (In,Ga) vapor for deposition on the Cu(In,Ga)Se2:CuxSe solid mixture while simultaneously increasing the temperature of the solid mixture toward a recrystallization temperature (about 550 DEG C) at which Cu(In,Ga)Se2 is solid and CuxSe is liquid. The (In,Ga) flux is terminated while the Se overpressure flux and the recrystallization temperature are maintained to recrystallize the CuxSe with the (In,Ga) that was deposited during the temperature transition and with the Se vapor to form the thin-film of slightly Cu-poor Cux(In,Ga)ySez. The initial Cu-rich, phase separated large grain mixture of Cu(In,Ga)Se2:CuxSe can be made by sequentially depositing or co-depositing the metal precursors, Cu and (In,Ga), on the substrate (12) at room temperature, ramping up the thin-film temperature in the presence of Se overpressure to a moderate anneal temperature (about 450 DEG C) and holding that temperature and the Se overpressure for an annealing period. A nonselenizing, low temperature anneal at about 100 DEG C can also be used to homogenize the precursors on the substrates before the selenizing, moderate temperature anneal.

Abstract translation: 在用于半导体器件应用的衬底（12）上制造Cu（In，Ga）Se2的略微Cu不良薄膜的方法包括以下步骤：初始形成稍微富Cu的相分离的Cu（In， Ga）Se2：固体形式的衬底（12）上的CuSee，然后将Cu（In，Ga）Se 2：CuxSe固体混合物暴露于Se蒸气和（In，Ga）蒸气的过压，沉积在Cu ，Ga）Se 2：CuxSe固体混合物，同时将固体混合物的温度同时升高至重结晶温度（约550℃），Cu（In，Ga）Se 2为固体，CuxSe为液体。 （In，Ga）通量终止，同时保持Se超压通量和再结晶温度，以在温度转变期间沉积的（In，Ga）和Se蒸气重结晶CuxSe，形成薄膜 轻微Cu-Cux（In，Ga）ySez。 Cu（In，Ga）Se2：CuxSe的初始富Cu相分离的大晶粒混合物可以通过在基底（12）上依次沉积或共沉积金属前体Cu和（In，Ga） 室温下，在Se过压的情况下将薄膜温度升高至适度退火温度（约450℃），并保持该温度和Se超压退火。 在硒化，中等温度退火之前，也可以在约100℃下进行非硒化低温退火，以使基板上的前体均匀化。

公开(公告)号：EP0724775A1

公开(公告)日：1996-08-07

申请号：EP95929367.0

申请日：1995-08-03

Applicant: Midwest Research Institute

Inventor： ALBIN, David, S. ,  CARAPELLA, Jeffrey, J. ,  TUTTLE, John, R. ,  CONTRERAS, Miguel, A. ,  GABOR, Andrew, M. ,  NOUFI, Rommel ,  TENNANT, Andrew, L.

IPC: C01B19 ,  C01G3 ,  C23C14 ,  C23C30 ,  H01L21 ,  H01L31

CPC classification number: H01L31/0322 ,  Y02E10/541 ,  Y02P70/521

Abstract: A process for fabricating slightly Cu-poor thin-films of Cu(In,Ga)Se2 on a substrate (12) for semiconductor device applications includes the steps of forming initially a slightly Cu-rich, phase separated, mixture of Cu(In,Ga)Se2:CuxSe on the substrate (12) in solid form followed by exposure of the Cu(In,Ga)Se2:CuxSe solid mixture to an overpressure of Se vapor and (In,Ga) vapor for deposition on the Cu(In,Ga)Se2:CuxSe solid mixture while simultaneously increasing the temperature of the solid mixture toward a recrystallization temperature (about 550 °C) at which Cu(In,Ga)Se2 is solid and CuxSe is liquid. The (In,Ga) flux is terminated while the Se overpressure flux and the recrystallization temperature are maintained to recrystallize the CuxSe with the (In,Ga) that was deposited during the temperature transition and with the Se vapor to form the thin-film of slightly Cu-poor Cux(In,Ga)ySez. The initial Cu-rich, phase separated large grain mixture of Cu(In,Ga)Se2:CuxSe can be made by sequentially depositing or co-depositing the metal precursors, Cu and (In,Ga), on the substrate (12) at room temperature, ramping up the thin-film temperature in the presence of Se overpressure to a moderate anneal temperature (about 450 °C) and holding that temperature and the Se overpressure for an annealing period. A nonselenizing, low temperature anneal at about 100 °C can also be used to homogenize the precursors on the substrates before the selenizing, moderate temperature anneal.

公开(公告)号：EP0694209B1

公开(公告)日：2000-07-12

申请号：EP94914072.7

申请日：1994-04-07

Applicant: Midwest Research Institute

Inventor： TUTTLE, John, R. ,  CONTRERAS, Miguel, A. ,  NOUFI, Rommel ,  ALBIN, David, S.

IPC: H01L21/302 ,  H01L21/463 ,  H01L31/032

CPC classification number: H01L31/0322 ,  Y02E10/541 ,  Y02P70/521 ,  Y10S438/93

公开(公告)号：EP0694209A1

公开(公告)日：1996-01-31

申请号：EP94914072.0

申请日：1994-04-07

Applicant: Midwest Research Institute

Inventor： TUTTLE, John, R. ,  CONTRERAS, Miguel, A. ,  NOUFI, Rommel ,  ALBIN, David, S.

IPC: C01B19 ,  C01G3 ,  C23C14 ,  C23C30 ,  H01L21 ,  H01L31

CPC classification number: H01L31/0322 ,  Y02E10/541 ,  Y02P70/521 ,  Y10S438/93

Abstract: Enhanced quality thin films of Cuw(In,Gay)Sez for semiconductor device applications are fabricated by initially forming a Cu-rich, phase-separated compound mixture comprising Cu(In,Ga):CuxSe on a substrate (12) to form a large-grain precursor (20) and then converting the excess CuxSe(18) to Cu(In,Ga)Se2 by exposing it to an activity of In (22) and/or Ga, either in vapor In and/or Ga form or in solid (In,Ga)ySez. Alternatively, the conversion can be made by sequential deposition of In and/or Ga and Se onto the phase-separated precursor (20). The conversion process is preferably performed in the temperature range of about 300-600°C, where the Cu(InGa)Se2 (16) remains solid, while the excess CuxSe (18) is in a liquid flux. The characteristic of the resulting Cuw(In,Ga)ySez can be controlled by the temperature. Higher temperatures, such as 500-600°C, results in a nearly stoichiometric Cu(In,Ga)Se2, whereas lower temperatures, such as 300-400°C, results in a more Cu-poor compound, such as the Cu2(In,GA)4Se7 phase.