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Title: Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films

Abstract

Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films are provided. In one embodiment, a method comprises: during a first stage (220), performing a mass transport through vapor transport of an indium chloride (InCl.sub.x) vapor (143, 223) and Se vapor (121, 225) to deposit a semiconductor film (212, 232, 252) upon a substrate (114, 210, 230, 250); heating the substrate (114, 210, 230, 250) and the semiconductor film to a desired temperature (112); during a second stage (240) following the first stage (220), performing a mass transport through vapor transport of a copper chloride (CuCl.sub.x) vapor (143, 243) and Se vapor (121, 245) to the semiconductor film (212, 232, 252); and during a third stage (260) following the second stage (240), performing a mass transport through vapor transport of an indium chloride (InCl.sub.x) vapor (143, 263) and Se vapor (121, 265) to the semiconductor film (212, 232, 252).

Inventors:
; ; ; ; ;
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1345209
Patent Number(s):
9,583,667
Application Number:
14/382,106
Assignee:
Alliance for Sustainable Energy, LLC NREL
DOE Contract Number:
AC36-08GO28308
Resource Type:
Patent
Resource Relation:
Patent File Date: 2013 Feb 27
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 14 SOLAR ENERGY

Citation Formats

Albin, David S., Vora, Nirav, Jimenez, Sebastian Caparros, Gutierrez, Joaquin Murillo, Cortezon, Emilio Sanchez, and Romero, Manuel. Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films. United States: N. p., 2017. Web.
Albin, David S., Vora, Nirav, Jimenez, Sebastian Caparros, Gutierrez, Joaquin Murillo, Cortezon, Emilio Sanchez, & Romero, Manuel. Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films. United States.
Albin, David S., Vora, Nirav, Jimenez, Sebastian Caparros, Gutierrez, Joaquin Murillo, Cortezon, Emilio Sanchez, and Romero, Manuel. Tue . "Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films". United States. doi:. https://www.osti.gov/servlets/purl/1345209.
@article{osti_1345209,
title = {Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films},
author = {Albin, David S. and Vora, Nirav and Jimenez, Sebastian Caparros and Gutierrez, Joaquin Murillo and Cortezon, Emilio Sanchez and Romero, Manuel},
abstractNote = {Systems and methods for forming solar cells with CuInSe.sub.2 and Cu(In,Ga)Se.sub.2 films are provided. In one embodiment, a method comprises: during a first stage (220), performing a mass transport through vapor transport of an indium chloride (InCl.sub.x) vapor (143, 223) and Se vapor (121, 225) to deposit a semiconductor film (212, 232, 252) upon a substrate (114, 210, 230, 250); heating the substrate (114, 210, 230, 250) and the semiconductor film to a desired temperature (112); during a second stage (240) following the first stage (220), performing a mass transport through vapor transport of a copper chloride (CuCl.sub.x) vapor (143, 243) and Se vapor (121, 245) to the semiconductor film (212, 232, 252); and during a third stage (260) following the second stage (240), performing a mass transport through vapor transport of an indium chloride (InCl.sub.x) vapor (143, 263) and Se vapor (121, 265) to the semiconductor film (212, 232, 252).},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Tue Feb 28 00:00:00 EST 2017},
month = {Tue Feb 28 00:00:00 EST 2017}
}

Patent:

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  • A process for making a thin film ZnO/Cu(InGa)Se.sub.2 solar cell without depositing a buffer layer and by Zn doping from a vapor phase, comprising: depositing Cu(InGa)Se.sub.2 layer on a metal back contact deposited on a glass substrate; heating the Cu(InGa)Se.sub.2 layer on the metal back contact on the glass substrate to a temperature range between about 100.degree. C. to about 250.degree. C.; subjecting the heated layer of Cu(InGa)Se.sub.2 to an evaporant species from a Zn compound; and sputter depositing ZnO on the Zn compound evaporant species treated layer of Cu(InGa)Se.sub.2.
  • A process for producing a slightly Cu-poor thin film of Cu(In,Ga)(Se,S){sub 2} comprises depositing a first layer of (In,Ga){sub x} (Se,S){sub y} followed by depositing just enough Cu+(Se,S) or Cu{sub x} (Se,S) to produce the desired slightly Cu-poor material. In a variation, most, but not all, (about 90 to 99%) of the (In,Ga){sub x} (Se,S){sub y} is deposited first, followed by deposition of all the Cu+(Se,S) or Cu{sub x} (Se,S) to go near stoichiometric, possibly or even preferably slightly Cu-rich, and then in turn followed by deposition of the remainder (about 1 to 10%) of the (In,Ga){sub x} (Se,S){sub y}more » to end with a slightly Cu-poor composition. In yet another variation, a small portion (about 1 to 10%) of the (In,Ga){sub x} (Se,S){sub y} is first deposited as a seed layer, followed by deposition of all of the Cu+(Se,S) or Cu{sub x} (Se,S) to make a very Cu-rich mixture, and then followed deposition of the remainder of the (In,Ga){sub x} (Se,S){sub y} to go slightly Cu-poor in the final Cu(In,Ga)(Se,S){sub 2} thin film. 5 figs.« less
  • A process for producing a slightly Cu-poor thin film of Cu(In,Ga)(Se,S).sub.2 comprises depositing a first layer of (In,Ga).sub.x (Se,S).sub.y followed by depositing just enough Cu+(Se,S) or Cu.sub.x (Se,S) to produce the desired slightly Cu-poor material. In a variation, most, but not all, (about 90 to 99%) of the (In,Ga).sub.x (Se,S).sub.y is deposited first, followed by deposition of all the Cu+(Se,S) or Cu.sub.x (Se,S) to go near stoichiometric, possibly or even preferably slightly Cu-rich, and then in turn followed by deposition of the remainder (about 1 to 10%) of the (In,Ga).sub.x (Se,S).sub.y to end with a slightly Cu-poor composition. In yetmore » another variation, a small portion (about 1 to 10%) of the (In,Ga).sub.x (Se,S).sub.y is first deposited as a seed layer, followed by deposition of all of the Cu+(Se,S) or Cu.sub.x (Se,S) to make a very Cu-rich mixture, and then followed deposition of the remainder of the (In,Ga).sub.x (Se,S).sub.y to go slightly Cu-poor in the final Cu(In,Ga)(Se,S).sub.2 thin film.« less
  • Enhanced quality thin films of Cu.sub.w (In,Ga.sub.y)Se.sub.z for semiconductor device applications are fabricated by initially forming a Cu-rich, phase-separated compound mixture comprising Cu(In,Ga):Cu.sub.x Se on a substrate to form a large-grain precursor and then converting the excess Cu.sub.x Se to Cu(In,Ga)Se.sub.2 by exposing it to an activity of In and/or Ga, either in vapor In and/or Ga form or in solid (In,Ga).sub.y Se.sub.z. Alternatively, the conversion can be made by sequential deposition of In and/or Ga and Se onto the phase-separated precursor. The conversion process is preferably performed in the temperature range of about 300.degree.-600.degree. C., where the Cu(In,Ga)Se.sub.2 remainsmore » solid, while the excess Cu.sub.x Se is in a liquid flux. The characteristic of the resulting Cu.sub.w (In,Ga).sub.y Se.sub.z can be controlled by the temperature. Higher temperatures, such as 500.degree.-600.degree. C., result in a nearly stoichiometric Cu(In,Ga)Se.sub.2, whereas lower temperatures, such as 300.degree.-400.degree. C., result in a more Cu-poor compound, such as the Cu.sub.z (In,Ga).sub.4 Se.sub.7 phase.« less
  • A process for fabricating slightly Cu-poor thin-films of Cu(In,Ga)Se.sub.2 on a substrate for semiconductor device applications includes the steps of forming initially a slightly Cu-rich, phase separated, mixture of Cu(In,Ga)Se.sub.2 :Cu.sub.x Se on the substrate in solid form followed by exposure of the Cu(In,Ga)Se.sub.2 :Cu.sub.x Se solid mixture to an overpressure of Se vapor and (In,Ga) vapor for deposition on the Cu(In,Ga)Se.sub.2 :Cu.sub.x Se solid mixture while simultaneously increasing the temperature of the solid mixture toward a recrystallization temperature (about 550.degree. C.) at which Cu(In,Ga)Se.sub.2 is solid and Cu.sub.x Se is liquid. The (In,Ga) flux is terminated while the Semore » overpressure flux and the recrystallization temperature are maintained to recrystallize the Cu.sub.x Se 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 Cu.sub.x (In,Ga).sub.y Se.sub.z. The initial Cu-rich, phase separated large grain mixture of Cu(In,Ga)Se.sub.2 :Cu.sub.x Se can be made by sequentially depositing or co-depositing the metal precursors, Cu and (In, Ga), on the substrate at room temperature, ramping up the thin-film temperature in the presence of Se overpressure to a moderate anneal temperature (about 450.degree. C.) and holding that temperature and the Se overpressure for an annealing period. A nonselenizing, low temperature anneal at about 100.degree. C. can also be used to homogenize the precursors on the substrates before the selenizing, moderate temperature anneal.« less