Synthesis of CIGS thin film by solvothermal route

Hsiang-Chen Wang; Chao-Chi Wang; Shih-Wei Feng; Li-His Chen; Yen-Sheng Lin

doi:10.1364/OME.3.000054

Synthesis of CIGS thin film by solvothermal route

Hsiang-Chen Wang, Chao-Chi Wang, Shih-Wei Feng, Li-His Chen, and Yen-Sheng Lin

Optical Materials Express
Vol. 3,
Issue 1,
pp. 54-66
(2013)
•https://doi.org/10.1364/OME.3.000054

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Hsiang-Chen Wang, Chao-Chi Wang, Shih-Wei Feng, Li-His Chen, and Yen-Sheng Lin, "Synthesis of CIGS thin film by solvothermal route," Opt. Mater. Express 3, 54-66 (2013)

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Related Topics
Table of Contents Category
- Photovoltaics
Optics & Photonics Topics
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The topics in this list come from the OSA Optics and Photonics Topics applied to this article.
Previously assigned OCIS codes
- Electro-optical materials (160.2100)
- Photosensitive materials (160.5335)
- Materials and process characterization (310.3840)

About this Article
History
- Original Manuscript: November 20, 2012
- Revised Manuscript: December 12, 2012
- Manuscript Accepted: December 12, 2012
- Published: December 13, 2012

Accessible

Open Access

Abstract

This study presents the synthesis of copper indium gallium (di)selenide (CIGS) films by a solvothermal method. Four factors in CIGS synthesis are considered: In/Ga ratios, hydrogen contents during thermal annealing, thermal annealing temperatures, and annealing times. Experimental results show that the optimal parameters for CIGS film synthesis are the following: proportion of Cu:In:Ga:Se = 1:0.7:0.3:2; hydrogen content during thermal annealing, 5%; thermal annealing temperature, 600 °C; and annealing time, 100 min. The largest crystal grain size of a CIGS film synthesized using these optimal parameters is about 100 nm. The crystal grain size is also found to be inversely proportional to sheet resistance. This relationship holds true because a smaller crystal indicates more grain boundaries and defects. Thus, an electron encounters more barriers in the transmission process, and electric conductivity decreases.

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References

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Author
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Publication

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]
M. Kemell, M. Ritala, and M. Leskela, “Thin film deposition methods for CuInSe2 solar cells,” Crit. Rev. Solid State Mater. Sci. 30(1), 1–31 (2005).
[Crossref]
P. Jackson, D. Hariskos, E. Lotter, S. Paetel, R. Wuerz, R. Menner, W. Wischmann, and M. Powalla, “New world record efficiency for Cu(In,Ga)Se2 thin-film solar cells beyond 20%,” Prog. Photovolt. Res. Appl. 19(7), 894–897 (2011).
[Crossref]
S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]
I. Repins, M. A. Contreras, B. Egaas, C. DeHart, J. Scharf, C. L. Perkins, B. To, and R. Noufi, “19.9%-efficient ZnO/CdS/CuInGaSe2 Solar Cell with 81.2% Fill Factor,” Prog. Photovolt. Res. Appl. 16(3), 235–239 (2008).
[Crossref]
S. Kurtz and J. Geisz, “Multijunction solar cells for conversion of concentrated sunlight to electricity,” Opt. Express 18(S1), A73–A78 (2010).
[Crossref]
J. F. Geisz, D. J. Friedman, J. S. Ward, A. Duda, W. J. Olavarria, T. E. Moriarty, J. T. Kiehl, M. J. Romero, A. G. Norman, and K. M. Jones, “40.8% efficient inverted triple-junction solar cell with two independently metamorphic junctions,” Appl. Phys. Lett. 93(12), 123505 (2008).
[Crossref]
N. Tansu, J.-Y. Yeh, and L. J. Mawst, “Physics and characteristics of high performance 1200 nm InGaAs and 1300–1400 nm InGaAsN quantum well lasers obtained by metal–organic chemical vapour deposition,” J. Phys. Condens. Matter 16(31), S3277–S3318 (2004).
[Crossref]
N. Tansu, J.-Y. Yeh, and L. J. Mawst, “High-Performance 1200-nm InGaAs and 1300-nm InGaAsN Quantum-Well Lasers by Metalorganic Chemical Vapor Deposition,” IEEE J. Sel. Top. Quantum Electron. 9(5), 1220–1227 (2003).
[Crossref]
S. R. Bank, L. L. Goddard, M. A. Wistey, H. B. Yuen, and J. S. Harris, “On the temperature sensitivity of 1.5 µm GaInNAsSb lasers,” IEEE J. Sel. Top. Quantum Electron. 11(5), 1089–1098 (2005).
[Crossref]
M. Wiemer, V. Sabnis, and H. Yuen, “43.5% efficient lattice matched solar cells,” Proc. SPIE 8108, 810804, 810804-5 (2011).
[Crossref]
D. Lincot, J. F. Guillemoles, S. Taunier, D. Guimard, J. Sicx-Kurdi, A. Chaumont, O. Roussel, O. Ramdani, C. Hubert, J. P. Fauvarque, N. Bodereau, L. Parissi, P. Panheleux, P. Fanouillere, N. Naghavi, P. P. Grand, M. Benfarah, P. Mogensen, and O. Kerrec, “Chalcopyritethin film solar cells by electrodeposition,” Sol. Energy 77(6), 725–737 (2004).
[Crossref]
K. H. Yoon, S. K. Kim, R. B. V. Chalapathy, J. H. Yun, J. C. Lee, and J. Song, “Characterization of a Molybdenum Electrode Deposited by Sputtering and Its Eﬀect on Cu(In,Ga)Se2 Solar Cells,” J. Korean Phys. Soc. 45(4), 1114–1118 (2004).
Y. G. Chun, K. H. Kim, and K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films 480–481, 46–49 (2005).
[Crossref]
J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]
S. Gu, H.-S. Shin, D.-H. Yeo, Y.-W. Hong, and S. Nahm, “Synthesis of the single phase CIGS particle by solvothermal method for solar cell application,” Curr. Appl. Phys. 11(1), S99–S102 (2011).
[Crossref]
M. G. Park, S. J. Ahn, J. H. Yun, J. Gwak, A. Cho, S. K. Ahn, K. Shin, D. Nam, H. Cheong, and K. Yoon, “Characteristics of Cu(In,Ga)Se2 (CIGS) thin films deposited by adirect solution coating process,” J. Alloy. Comp. 513, 68–74 (2012).
[Crossref]
J. Olejníček, C. A. Kamler, A. Mirasano, A. L. Martinez-Skinner, M. A. Ingersoll, C. L. Exstrom, S. A. Darveau, J. L. Huguenin-Love, M. Diaz, J. Ianno, and J. Soukup, “A non-vacuum process for preparing nanocrystalline CuIn1-xGaxSe2 materials involving an open-air solvothermal reaction” (University of Nebraska–Lincoln, 2010).
E. Lee, J. W. Cho, J. Kim, J. Yun, J. H. Kim, and B. K. Min, “Synthesis of CIGS powders: Transition from binary to quaternary crystalline structure,” J. Alloy. Comp. 506(2), 969–972 (2010).
[Crossref]
J. F. Guillemoles, “Stability of Cu(In,Ga)Se2 solar cells: a thermodynamic approach,” Thin Solid Films 361–362, 338–345 (2000).
[Crossref]
K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]
J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]
M. R. Robinson and M. R. Roscheisen (Inventors), Nanosolar Inc. (Assignee), U.S. Patent No. 7604843B1 (Oct. 20, 2009).
J. Olejníček, C. A. Kamler, A. Mirasano, A. L. Martinez-Skinner, M. A. Ingersoll, C. L. Exstrom, S. A. Darveau, J. L. Huguenin-Love, M. Diaz, N. J. Ianno, and R. J. Soukup, “A non-vacuum process for preparing nanocrystalline CuIn1-xGaxSe2 materials involving an open-air solvothermal reaction,” Sol. Energy Mater. Sol. Cells 94(1), 8–11 (2010).
[Crossref]
Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]
D. Y. Lee, S. J. Park, and J. H. Kim, “Structural analysis of CIGS film prepared by chemical spray deposition,” Curr. Appl. Phys. 11(1), S88–S92 (2011).
[Crossref]
F. B. Dejene, “The structural and material properties of CuInSe2 and CuInGaSe2 prepared by selenization of stacks of metal and compound precursors by Se vapor for solar cell applications,” Sol. Energy Mater. Sol. Cells 93(5), 577–582 (2009).
[Crossref]
I. H. Choi and D. H. Lee, “Preparation of CuInGaSe2 films by metalorganic chemical vapor deposition using three precursors,” Thin Solid Films 515(11), 4778–4782 (2007).
[Crossref]
S. H. Wei, S. B. Zhang, and A. Zunger, “Effects of Ga addition to CuInSe2 on its electronic structural and defect properties,” Appl. Phys. Lett. 72(24), 3199–3201 (1998).
[Crossref]
A. Yamada, H. Miyazaki, R. Mikami, and M. Konagail, “Improved performance of Cu(InGa)Se2 thin film solar cells with high Ga composition using rapid thermal annealing process,” in 3rd World Conference on Phorovoliaic Energy Conversion, 2859–2863. Osaka, Japan (2003).
M. M. Islam, S. Ishizuka, A. Yamada, K. Matsubara, S. Niki, T. Sakurai, and K. Akimoto, “Thickness study of Al:ZnO film for application as a window layer in Cu(In1−xGax)Se2 thin film solar cell,” Appl. Surf. Sci. 257(9), 4026–4030 (2011).
[Crossref]
Y. H. Jo, B. C. Mohanty, and Y. S. Cho, “Enhanced electrical properties of pulsed laser-deposited CuIn0.7Ga0.3Se2thin films via processing control,” Sol. Energy 84(12), 2213–2218 (2010).
[Crossref]
L. Zhang, Q. He, W. L. Jiang, F. F. Liu, C. J. Li, and Y. Sun, “Effects of substrate temperature on the structural and electrical properties of Cu(In,Ga)Se2 thin films,” Sol. Energy Mater. Sol. Cells 93(1), 114–118 (2009).
[Crossref]
M. M. Islam, T. Sakurai, S. Ishizuka, A. Yamada, H. Shibata, K. Sakurai, K. Matsubara, S. Niki, and K. Akimoto, “Effect of Se/(Ga + In) ratio on MBE grown Cu(In,Ga)Se2 thin film solar cell,” J. Cryst. Growth 311(7), 2212–2214 (2009).
[Crossref]
Z. Li, H. Qing, J. Wei-Long, L. Chang-Jian, and S. Yun, “Cu(In, Ga)Se2 Thin Films on Flexible Polyimide Sheet: Structural and Electrical Properties versus Composition,” Chin. Phys. Lett. 26(2), 026801 (2009).
[Crossref]

2012 (2)

M. G. Park, S. J. Ahn, J. H. Yun, J. Gwak, A. Cho, S. K. Ahn, K. Shin, D. Nam, H. Cheong, and K. Yoon, “Characteristics of Cu(In,Ga)Se2 (CIGS) thin films deposited by adirect solution coating process,” J. Alloy. Comp. 513, 68–74 (2012).
[Crossref]

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

2011 (5)

D. Y. Lee, S. J. Park, and J. H. Kim, “Structural analysis of CIGS film prepared by chemical spray deposition,” Curr. Appl. Phys. 11(1), S88–S92 (2011).
[Crossref]

M. Wiemer, V. Sabnis, and H. Yuen, “43.5% efficient lattice matched solar cells,” Proc. SPIE 8108, 810804, 810804-5 (2011).
[Crossref]

S. Gu, H.-S. Shin, D.-H. Yeo, Y.-W. Hong, and S. Nahm, “Synthesis of the single phase CIGS particle by solvothermal method for solar cell application,” Curr. Appl. Phys. 11(1), S99–S102 (2011).
[Crossref]

M. M. Islam, S. Ishizuka, A. Yamada, K. Matsubara, S. Niki, T. Sakurai, and K. Akimoto, “Thickness study of Al:ZnO film for application as a window layer in Cu(In1−xGax)Se2 thin film solar cell,” Appl. Surf. Sci. 257(9), 4026–4030 (2011).
[Crossref]

P. Jackson, D. Hariskos, E. Lotter, S. Paetel, R. Wuerz, R. Menner, W. Wischmann, and M. Powalla, “New world record efficiency for Cu(In,Ga)Se2 thin-film solar cells beyond 20%,” Prog. Photovolt. Res. Appl. 19(7), 894–897 (2011).
[Crossref]

2010 (5)

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

J. Olejníček, C. A. Kamler, A. Mirasano, A. L. Martinez-Skinner, M. A. Ingersoll, C. L. Exstrom, S. A. Darveau, J. L. Huguenin-Love, M. Diaz, N. J. Ianno, and R. J. Soukup, “A non-vacuum process for preparing nanocrystalline CuIn1-xGaxSe2 materials involving an open-air solvothermal reaction,” Sol. Energy Mater. Sol. Cells 94(1), 8–11 (2010).
[Crossref]

Y. H. Jo, B. C. Mohanty, and Y. S. Cho, “Enhanced electrical properties of pulsed laser-deposited CuIn0.7Ga0.3Se2thin films via processing control,” Sol. Energy 84(12), 2213–2218 (2010).
[Crossref]

S. Kurtz and J. Geisz, “Multijunction solar cells for conversion of concentrated sunlight to electricity,” Opt. Express 18(S1), A73–A78 (2010).
[Crossref]

E. Lee, J. W. Cho, J. Kim, J. Yun, J. H. Kim, and B. K. Min, “Synthesis of CIGS powders: Transition from binary to quaternary crystalline structure,” J. Alloy. Comp. 506(2), 969–972 (2010).
[Crossref]

2009 (5)

F. B. Dejene, “The structural and material properties of CuInSe2 and CuInGaSe2 prepared by selenization of stacks of metal and compound precursors by Se vapor for solar cell applications,” Sol. Energy Mater. Sol. Cells 93(5), 577–582 (2009).
[Crossref]

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

L. Zhang, Q. He, W. L. Jiang, F. F. Liu, C. J. Li, and Y. Sun, “Effects of substrate temperature on the structural and electrical properties of Cu(In,Ga)Se2 thin films,” Sol. Energy Mater. Sol. Cells 93(1), 114–118 (2009).
[Crossref]

M. M. Islam, T. Sakurai, S. Ishizuka, A. Yamada, H. Shibata, K. Sakurai, K. Matsubara, S. Niki, and K. Akimoto, “Effect of Se/(Ga + In) ratio on MBE grown Cu(In,Ga)Se2 thin film solar cell,” J. Cryst. Growth 311(7), 2212–2214 (2009).
[Crossref]

Z. Li, H. Qing, J. Wei-Long, L. Chang-Jian, and S. Yun, “Cu(In, Ga)Se2 Thin Films on Flexible Polyimide Sheet: Structural and Electrical Properties versus Composition,” Chin. Phys. Lett. 26(2), 026801 (2009).
[Crossref]

2008 (3)

I. Repins, M. A. Contreras, B. Egaas, C. DeHart, J. Scharf, C. L. Perkins, B. To, and R. Noufi, “19.9%-efficient ZnO/CdS/CuInGaSe2 Solar Cell with 81.2% Fill Factor,” Prog. Photovolt. Res. Appl. 16(3), 235–239 (2008).
[Crossref]

J. F. Geisz, D. J. Friedman, J. S. Ward, A. Duda, W. J. Olavarria, T. E. Moriarty, J. T. Kiehl, M. J. Romero, A. G. Norman, and K. M. Jones, “40.8% efficient inverted triple-junction solar cell with two independently metamorphic junctions,” Appl. Phys. Lett. 93(12), 123505 (2008).
[Crossref]

J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]

2007 (1)

I. H. Choi and D. H. Lee, “Preparation of CuInGaSe2 films by metalorganic chemical vapor deposition using three precursors,” Thin Solid Films 515(11), 4778–4782 (2007).
[Crossref]

2005 (3)

S. R. Bank, L. L. Goddard, M. A. Wistey, H. B. Yuen, and J. S. Harris, “On the temperature sensitivity of 1.5 µm GaInNAsSb lasers,” IEEE J. Sel. Top. Quantum Electron. 11(5), 1089–1098 (2005).
[Crossref]

Y. G. Chun, K. H. Kim, and K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films 480–481, 46–49 (2005).
[Crossref]

M. Kemell, M. Ritala, and M. Leskela, “Thin film deposition methods for CuInSe2 solar cells,” Crit. Rev. Solid State Mater. Sci. 30(1), 1–31 (2005).
[Crossref]

2004 (4)

N. Tansu, J.-Y. Yeh, and L. J. Mawst, “Physics and characteristics of high performance 1200 nm InGaAs and 1300–1400 nm InGaAsN quantum well lasers obtained by metal–organic chemical vapour deposition,” J. Phys. Condens. Matter 16(31), S3277–S3318 (2004).
[Crossref]

D. Lincot, J. F. Guillemoles, S. Taunier, D. Guimard, J. Sicx-Kurdi, A. Chaumont, O. Roussel, O. Ramdani, C. Hubert, J. P. Fauvarque, N. Bodereau, L. Parissi, P. Panheleux, P. Fanouillere, N. Naghavi, P. P. Grand, M. Benfarah, P. Mogensen, and O. Kerrec, “Chalcopyritethin film solar cells by electrodeposition,” Sol. Energy 77(6), 725–737 (2004).
[Crossref]

K. H. Yoon, S. K. Kim, R. B. V. Chalapathy, J. H. Yun, J. C. Lee, and J. Song, “Characterization of a Molybdenum Electrode Deposited by Sputtering and Its Eﬀect on Cu(In,Ga)Se2 Solar Cells,” J. Korean Phys. Soc. 45(4), 1114–1118 (2004).

K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]

2003 (1)

N. Tansu, J.-Y. Yeh, and L. J. Mawst, “High-Performance 1200-nm InGaAs and 1300-nm InGaAsN Quantum-Well Lasers by Metalorganic Chemical Vapor Deposition,” IEEE J. Sel. Top. Quantum Electron. 9(5), 1220–1227 (2003).
[Crossref]

2000 (2)

J. F. Guillemoles, “Stability of Cu(In,Ga)Se2 solar cells: a thermodynamic approach,” Thin Solid Films 361–362, 338–345 (2000).
[Crossref]

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

1998 (1)

S. H. Wei, S. B. Zhang, and A. Zunger, “Effects of Ga addition to CuInSe2 on its electronic structural and defect properties,” Appl. Phys. Lett. 72(24), 3199–3201 (1998).
[Crossref]

Ahn, S. J.

Ahn, S. K.

Akimoto, K.

Bank, S. R.

Benfarah, M.

Bodereau, N.

Brugger, J.

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

Cahen, D.

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

Chalapathy, R. B. V.

Chang-Jian, L.

Chaumont, A.

Chen, C.

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

Cheong, H.

Cho, A.

Cho, J. W.

Cho, Y. S.

Choi, I. H.

I. H. Choi and D. H. Lee, “Preparation of CuInGaSe2 films by metalorganic chemical vapor deposition using three precursors,” Thin Solid Films 515(11), 4778–4782 (2007).
[Crossref]

Choi, Y. W.

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

Chun, Y. G.

Y. G. Chun, K. H. Kim, and K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films 480–481, 46–49 (2005).
[Crossref]

K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]

Contreras, M.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Contreras, M. A.

Darveau, S. A.

DeHart, C.

Dejene, F. B.

Diaz, M.

Duda, A.

Egaas, B.

Exstrom, C. L.

Fanouillere, P.

Fauvarque, J. P.

Friedman, D. J.

Geisz, J.

S. Kurtz and J. Geisz, “Multijunction solar cells for conversion of concentrated sunlight to electricity,” Opt. Express 18(S1), A73–A78 (2010).
[Crossref]

Geisz, J. F.

Goddard, L. L.

Grand, P. P.

Gu, S.

Guillemoles, J. F.

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

J. F. Guillemoles, “Stability of Cu(In,Ga)Se2 solar cells: a thermodynamic approach,” Thin Solid Films 361–362, 338–345 (2000).
[Crossref]

Guimard, D.

Gwak, J.

Hariskos, D.

Harris, J. S.

He, Q.

Hinds, S.

J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]

Hong, Y.-W.

Hubert, C.

Huguenin-Love, J. L.

Ianno, N. J.

Ingersoll, M. A.

Ishizuka, S.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Islam, M. M.

Jackson, P.

Jasenek, A.

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

Jiang, W. L.

Jo, Y. H.

Jones, K. M.

Joo, O. S.

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

Kamler, C. A.

Kelley, S. O.

J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]

Kemell, M.

M. Kemell, M. Ritala, and M. Leskela, “Thin film deposition methods for CuInSe2 solar cells,” Crit. Rev. Solid State Mater. Sci. 30(1), 1–31 (2005).
[Crossref]

Kerrec, O.

Kiehl, J. T.

Kim, J.

Kim, J. H.

D. Y. Lee, S. J. Park, and J. H. Kim, “Structural analysis of CIGS film prepared by chemical spray deposition,” Curr. Appl. Phys. 11(1), S88–S92 (2011).
[Crossref]

Kim, K. H.

Y. G. Chun, K. H. Kim, and K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films 480–481, 46–49 (2005).
[Crossref]

K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]

Kim, S. K.

Kong, D.

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

Kronik, L.

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

Kurtz, S.

S. Kurtz and J. Geisz, “Multijunction solar cells for conversion of concentrated sunlight to electricity,” Opt. Express 18(S1), A73–A78 (2010).
[Crossref]

Kushiya, K.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Lee, D. H.

I. H. Choi and D. H. Lee, “Preparation of CuInGaSe2 films by metalorganic chemical vapor deposition using three precursors,” Thin Solid Films 515(11), 4778–4782 (2007).
[Crossref]

Lee, D. Y.

D. Y. Lee, S. J. Park, and J. H. Kim, “Structural analysis of CIGS film prepared by chemical spray deposition,” Curr. Appl. Phys. 11(1), S88–S92 (2011).
[Crossref]

Lee, E.

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

Lee, J. C.

Leskela, M.

M. Kemell, M. Ritala, and M. Leskela, “Thin film deposition methods for CuInSe2 solar cells,” Crit. Rev. Solid State Mater. Sci. 30(1), 1–31 (2005).
[Crossref]

Li, C. J.

Li, J.

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

Li, Z.

Lincot, D.

Liu, F. F.

Liu, Y.

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

Lotter, E.

Martinez-Skinner, A. L.

Matsubara, K.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Mawst, L. J.

Menner, R.

Min, B. K.

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

Mirasano, A.

Mogensen, P.

Mohanty, B. C.

Moriarty, T. E.

Naghavi, N.

Nahm, S.

Nam, D.

Niki, S.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Norman, A. G.

Noufi, R.

Olavarria, W. J.

Olejnícek, J.

Paetel, S.

Panheleux, P.

Parissi, L.

Park, B. O.

K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]

Park, J. W.

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

Park, M. G.

Park, S. J.

D. Y. Lee, S. J. Park, and J. H. Kim, “Structural analysis of CIGS film prepared by chemical spray deposition,” Curr. Appl. Phys. 11(1), S88–S92 (2011).
[Crossref]

Perkins, C. L.

Powalla, M.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Qing, H.

Ramdani, O.

Rau, U.

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

Repins, I.

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Ritala, M.

M. Kemell, M. Ritala, and M. Leskela, “Thin film deposition methods for CuInSe2 solar cells,” Crit. Rev. Solid State Mater. Sci. 30(1), 1–31 (2005).
[Crossref]

Romero, M. J.

Roussel, O.

Sabnis, V.

M. Wiemer, V. Sabnis, and H. Yuen, “43.5% efficient lattice matched solar cells,” Proc. SPIE 8108, 810804, 810804-5 (2011).
[Crossref]

Sakurai, K.

Sakurai, T.

Sargent, E. H.

J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]

Scharf, J.

Schock, H. W.

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

Shibata, H.

Shin, H.-S.

Shin, K.

Sicx-Kurdi, J.

Song, J.

Soukup, R. J.

Sun, Y.

Tang, J.

J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]

Tansu, N.

Taunier, S.

To, B.

Ward, J. S.

Wei, S. H.

S. H. Wei, S. B. Zhang, and A. Zunger, “Effects of Ga addition to CuInSe2 on its electronic structural and defect properties,” Appl. Phys. Lett. 72(24), 3199–3201 (1998).
[Crossref]

Wei-Long, J.

Wiemer, M.

M. Wiemer, V. Sabnis, and H. Yuen, “43.5% efficient lattice matched solar cells,” Proc. SPIE 8108, 810804, 810804-5 (2011).
[Crossref]

Wischmann, W.

Wistey, M. A.

Wuerz, R.

Yamada, A.

Yeh, J.-Y.

Yeo, D.-H.

Yoon, K.

Yoon, K. H.

Y. G. Chun, K. H. Kim, and K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films 480–481, 46–49 (2005).
[Crossref]

K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]

Yoon, S.

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

Yuen, H.

M. Wiemer, V. Sabnis, and H. Yuen, “43.5% efficient lattice matched solar cells,” Proc. SPIE 8108, 810804, 810804-5 (2011).
[Crossref]

Yuen, H. B.

Yun, J.

Yun, J. H.

Yun, S.

Zhang, L.

Zhang, S. B.

S. H. Wei, S. B. Zhang, and A. Zunger, “Effects of Ga addition to CuInSe2 on its electronic structural and defect properties,” Appl. Phys. Lett. 72(24), 3199–3201 (1998).
[Crossref]

Zhao, C.

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

Zunger, A.

S. H. Wei, S. B. Zhang, and A. Zunger, “Effects of Ga addition to CuInSe2 on its electronic structural and defect properties,” Appl. Phys. Lett. 72(24), 3199–3201 (1998).
[Crossref]

Appl. Phys. Lett. (2)

S. H. Wei, S. B. Zhang, and A. Zunger, “Effects of Ga addition to CuInSe2 on its electronic structural and defect properties,” Appl. Phys. Lett. 72(24), 3199–3201 (1998).
[Crossref]

Appl. Surf. Sci. (1)

Chem. Mater. (1)

J. Tang, S. Hinds, S. O. Kelley, and E. H. Sargent, “Synthesis of Colloidal CuGaSe2, CuInSe2, and Cu(InGa)Se2 Nanoparticles,” Chem. Mater. 20(22), 6906–6910 (2008).
[Crossref]

Chin. Phys. Lett. (1)

Crit. Rev. Solid State Mater. Sci. (1)

M. Kemell, M. Ritala, and M. Leskela, “Thin film deposition methods for CuInSe2 solar cells,” Crit. Rev. Solid State Mater. Sci. 30(1), 1–31 (2005).
[Crossref]

Curr. Appl. Phys. (2)

D. Y. Lee, S. J. Park, and J. H. Kim, “Structural analysis of CIGS film prepared by chemical spray deposition,” Curr. Appl. Phys. 11(1), S88–S92 (2011).
[Crossref]

Energy Procedia (1)

Y. Liu, D. Kong, J. Li, C. Zhao, C. Chen, and J. Brugger, “Preparation of Cu(In,Ga)Se2 Thin Film by Solvothermal and Spin-coating Process,” Energy Procedia 16, 217–222 (2012).
[Crossref]

IEEE J. Sel. Top. Quantum Electron. (2)

J. Alloy. Comp. (2)

J. Cryst. Growth (2)

J. W. Park, Y. W. Choi, E. Lee, O. S. Joo, S. Yoon, and B. K. Min, “Synthesis of CIGS absorber layers via a paste coating,” J. Cryst. Growth 311(9), 2621–2625 (2009).
[Crossref]

J. Korean Phys. Soc. (1)

J. Phys. Chem. B (1)

J. F. Guillemoles, L. Kronik, D. Cahen, U. Rau, A. Jasenek, and H. W. Schock, “Stability issues of Cu(In,Ga)Se2 based solar cells,” J. Phys. Chem. B 104(20), 4849–4862 (2000).
[Crossref]

J. Phys. Condens. Matter (1)

Mater. Sci. Forum (1)

K. H. Kim, Y. G. Chun, B. O. Park, and K. H. Yoon, “Synthesis of CuInSe2 and CuInGaSe2 Nanoparticles by Solvothermal Route,” Mater. Sci. Forum 449–452, 273–276 (2004).
[Crossref]

Opt. Express (1)

S. Kurtz and J. Geisz, “Multijunction solar cells for conversion of concentrated sunlight to electricity,” Opt. Express 18(S1), A73–A78 (2010).
[Crossref]

Proc. SPIE (1)

M. Wiemer, V. Sabnis, and H. Yuen, “43.5% efficient lattice matched solar cells,” Proc. SPIE 8108, 810804, 810804-5 (2011).
[Crossref]

Prog. Photovolt. Res. Appl. (3)

S. Niki, M. Contreras, I. Repins, M. Powalla, K. Kushiya, S. Ishizuka, and K. Matsubara, “CIGS absorbers and processes,” Prog. Photovolt. Res. Appl. 18(6), 453–466 (2010).
[Crossref]

Sol. Energy (2)

Sol. Energy Mater. Sol. Cells (3)

Thin Solid Films (3)

I. H. Choi and D. H. Lee, “Preparation of CuInGaSe2 films by metalorganic chemical vapor deposition using three precursors,” Thin Solid Films 515(11), 4778–4782 (2007).
[Crossref]

Y. G. Chun, K. H. Kim, and K. H. Yoon, “Synthesis of CuInGaSe2 nanoparticles by solvothermal route,” Thin Solid Films 480–481, 46–49 (2005).
[Crossref]

J. F. Guillemoles, “Stability of Cu(In,Ga)Se2 solar cells: a thermodynamic approach,” Thin Solid Films 361–362, 338–345 (2000).
[Crossref]

Other (3)

J. Olejníček, C. A. Kamler, A. Mirasano, A. L. Martinez-Skinner, M. A. Ingersoll, C. L. Exstrom, S. A. Darveau, J. L. Huguenin-Love, M. Diaz, J. Ianno, and J. Soukup, “A non-vacuum process for preparing nanocrystalline CuIn1-xGaxSe2 materials involving an open-air solvothermal reaction” (University of Nebraska–Lincoln, 2010).

M. R. Robinson and M. R. Roscheisen (Inventors), Nanosolar Inc. (Assignee), U.S. Patent No. 7604843B1 (Oct. 20, 2009).

A. Yamada, H. Miyazaki, R. Mikami, and M. Konagail, “Improved performance of Cu(InGa)Se2 thin film solar cells with high Ga composition using rapid thermal annealing process,” in 3rd World Conference on Phorovoliaic Energy Conversion, 2859–2863. Osaka, Japan (2003).

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Fig. 1 XRD map of the CIGS samples synthesized with (a) In:Ga = 0.7:0.3 (b) In:Ga = 0.5:0.5, and (c) In:Ga = 0.3:0.7 after annealing in the range of 450 °C to 600 °C.

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Fig. 2 High-magnification top view SEM images of Samples (a) H0, (b) H5, (c) H8, (d) H13, and (e) H26; (f) XRD results of Samples H0, H5, H8, H13, and H26.

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Fig. 3 SEM end views of Samples H0, H5, H8, H13, and H26.

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Fig. 4 (a) XRD patterns of Samples T200, T400, T500, T600, and T800. SEM top views of Samples (b) T200, (c) T400, (d) T500, (e) T600, and (f) T800.

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Fig. 5 SEM end views image of Samples (a) T200, (b) T400, (c) T500, (d) T600, and (e) T800.

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Fig. 6 Distribution map (a), (b), (c), (d), and (e) of the grain sizes of Samples T200, T400, T500, T600, and T800 measured using ImageJ.

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Fig. 7 (a) XRD measured results of Samples t80, t90, t100, t110, and t120. High-magnification top view SEM images of Samples (b) t80, (c) t90, (d) t100, (e) t110, and (f) t120; (g) Top view SEM image of Sample t110 magnified 150,000 × and 500 nm in size.

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Fig. 8 SEM end views of Samples (a) t80, (b) t90, (c) t100, (d) t110, and (e) t120. The upper-right map in each figure represents the cross-sectional images of the samples.

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Fig. 9 Distribution map (a), (b), (c), (d), and (e) of the grain sizes of Samples t80, t90, t100, t110, and t120 measured using ImageJ.

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Fig. 10 Relational graph of the thermal annealing time, grain size, and resistivity.

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Tables (5)

Table 1 Parameter list of CIGS samples synthesized in different In/Ga ratios, position of diffraction peak (112) obtained after annealing, and lattice constant table^a

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Table 2 Data sheet obtained by feeding different hydrogen contents and different annealing temperatures, position of diffraction peak (112) after annealing, and lattice constant table^a

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Table 3 Data sheet of the samples at different annealing temperatures, position of diffraction peak (112) after annealing, and lattice constant table

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Table 4 Parameter of CIGS synthesis with different annealing times for Samples t80, t90, t100, t110, and t120 of 80, 90, 100, 110, and 120 min

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Table 5 Measured result of Samples t80, t90, t100, t110, and t120 using a four-point prober

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Equations (4)

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\begin{array}{l} Cu {({NO}_{3})}_{2} \cdot {3H}_{2} O \to {Cu}^{2}^{+} + {HNO}_{3} + {OH}^{-} \\ In {({NO}_{3})}_{2} \cdot {3H}_{2} O \to {In}^{2}^{+} + {HNO}_{3} + {OH}^{-} \\ Ga {({NO}_{3})}_{2} \cdot {3H}_{2} O \to {Ga}^{2}^{+} + {HNO}_{3} + {OH}^{-} \\ {SeCl}_{4} \to {Se}^{4 +} + {4Cl}^{-} \\ {Se}^{4 +} + 4ROH \to Se {(OR)}_{4} + {4H}^{+} \\ {4H}^{+} + {4Cl}^{-} \to 4HCl \\ {Cu}^{2 +} + {xIn}^{3 +} + (1 - x) {Ga}^{3 +} + Se {(OR)}_{4} + ROH \to {CuIn}_{x} {Ga}_{(1 - x)} {Se}_{2} + residual organics \end{array}

d = \frac{λ}{2 s i n θ}

\frac{1}{d^{2}} = \frac{h^{2} + k^{2}}{a^{2}} + \frac{l^{2}}{c^{2}}

ρ = R_{s h e e t} \times T_{f}

In/Ga ratio	S	Hot plate	Et.	E [g]	Spin coating [rpm/s]	Ann. Tem. [°C]	Ann. Time min	Gas	(112) 2θ angle	a (Å)
A (In:Ga = 0.7:0.3)	A1	60,400,90	5	0.25	100	450	90	Ar	27.92	5.528
	A2	60,400,90	5	0.25	100	500	90	Ar	27.62	5.587
	A3	60,400,90	5	0.25	100	550	90	Ar	27.54	5.603
	A4	60,400,90	5	0.25	100	600	90	Ar	27.22	5.668
B (In:Ga = 0.5:0.5)	B1	60,400,90	5	0.25	100	450	90	Ar	27.94	5.524
	B2	60,400,90	5	0.25	100	500	90	Ar	27.84	5.544
	B3	60,400,90	5	0.25	100	550	90	Ar	27.60	5.591
	B4	60,400,90	5	0.25	100	600	90	Ar	27.50	5.611
C (In:Ga = 0.3:0.7)	C1	60,400,90	5	0.25	100	450	90	Ar	28.08	5.497
	C2	60,400,90	5	0.25	100	500	90	Ar	27.94	5.524
	C3	60,400,90	5	0.25	100	550	90	Ar	27.68	5.575
	C4	60,400,90	5	0.25	100	600	90	Ar	27.62	5.587

Sample (CuIn_0.7Ga_0.3Se₂)	H₂	Hot plat	Et.	E [g]	Al.	Spin coating [rpm/s]	Ann. Tem. [°C]	Ann. Time min	(112) 2θ angle	a (Å)
H0	0%	60,400,120	2	0.05	1	100	600	90	26.92	5.733
H5	5%	60,400,120	2	0.05	1	100	600	90	26.92	5.733
H8	8%	60,400,120	2	0.05	1	100	600	90	26.92	5.733
H13	13%	60,400,120	2	0.05	1	100	600	90	26.92	5.733
H23	23%	60,400,120	2	0.05	1	100	600	90	26.92	5.733

Sample (CuIn_0.7Ga_0.3Se₂)	Hot plate	Et.	E [g]	Al.	Spin coating [rpm/s]	Ann. Tem. [°C]	Ann. Time min	(112) 2θ angle	a (Å)
T200	60,400,120	2	0.05	1	100	200	90	27.72	5.573
T400	60,400,120	2	0.05	1	100	400	90	26.96	5.727
T500	60,400,120	2	0.05	1	100	500	90	26.94	5.731
T600	60,400,120	2	0.05	1	100	600	90	26.92	5.836
T800	60,400,120	2	0.05	1	100	800	90	27.07	5.698

Sample (CuIn_0.7Ga_0.3Se₂)	Hot plat	Et.	E [g]	Al.	Spin coating [rpm/s]	Ann. Tem. [°C]	Ann. Time min	(112) 2θ angle	a (Å)
t80	60,400,90	2	0.05	1	100	600	80	26.92	5.733
t90	60,400,90	2	0.05	1	100	600	90	26.92	5.733
t100	60,400,90	2	0.05	1	100	600	100	26.92	5.733
t110	60,400,90	2	0.05	1	100	600	110	26.92	5.733
t120	60,400,90	2	0.05	1	100	600	120	26.92	5.733

Sample	t80	t90	t100	t110	t120
Sheet resistance [kΩ/□]	125.39	46.45	42.61	77.01	86.68
Thickness [nm]	2200	2100	1900	1880	1970
Resistivity [Ω·cm]	275.86	97.55	80.96	144.78	170.75