Hostname: page-component-78c5997874-j824f Total loading time: 0 Render date: 2024-11-13T01:51:14.391Z Has data issue: false hasContentIssue false
  • English
  • Français

Atmospheric pressure synthesis of In2Se3, Cu2Se, and CuInSe2 without external selenization from solution precursors

Published online by Cambridge University Press:  31 January 2011

Jennifer A. Nekuda Malik ,
Maikel F.A.M. van Hest ,
Alexander Miedaner ,
Calvin J. Curtis ,
Jennifer E. Leisch ,
Philip A. Parilla ,
Michael Kaufman ,
Matthew Taylor ,
B.J. Stanbery  and
Ryan P. O’Hayre
...Show all authors
Jennifer A. Nekuda Malik*
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401; and National Renewable Energy Laboratory, Golden, Colorado 80401
Maikel F.A.M. van Hest
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401; and National Renewable Energy Laboratory, Golden, Colorado 80401
Alexander Miedaner
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401; and National Renewable Energy Laboratory, Golden, Colorado 80401
Calvin J. Curtis
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401; and National Renewable Energy Laboratory, Golden, Colorado 80401
Jennifer E. Leisch
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401; and National Renewable Energy Laboratory, Golden, Colorado 80401
Philip A. Parilla
Affiliation:
National Renewable Energy Laboratory, Golden, Colorado 80401
Michael Kaufman
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401
Matthew Taylor
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401; and National Renewable Energy Laboratory, Golden, Colorado 80401
B.J. Stanbery
Affiliation:
HelioVolt Corporation, Austin, Texas 78744
Ryan P. O’Hayre
Affiliation:
Department of Metallurgical and Materials Engineering, Colorado School of Mines, Golden, Colorado 80401
David S. Ginley*
Affiliation:
National Renewable Energy Laboratory, Golden, Colorado 80401
*
a) e-mail: jnekuda@gmail.com
b) e-mail: david_ginley@nrel.gov
Get access

Abstract

In2Se3, Cu2Se, and CuInSe2 thin films have been successfully fabricated using novel metal organic decomposition (MOD) precursors and atmospheric pressure-based deposition and processing. The phase evolution of the binary (In-Se and Cu-Se) and ternary (Cu-In-Se) MOD precursor films was examined during processing to evaluate the nature of the phase and composition changes. The In-Se binary precursor exhibits two specific phase regimes: (i) a cubic-InxSey phase at processing temperatures between 300 and 400 °C and (ii) the γ-In2Se3 phase for films annealed above 450 °C. Both phases exhibit a composition of 40 at.% indium and 60 at.% selenium. The binary Cu-Se precursor films show more diverse phase behavior, and within a narrow temperature processing range a number of Cu-Se phases, including CuSe2, CuSe, and Cu2Se, can be produced and stabilized. The ternary Cu-In-Se precursor can be used to produce relatively dense CuInSe2 films at temperatures between 300 and 500 °C. Layering the binary precursors together has provided an approach to producing CuInSe2 thin films; however, the morphology of the layered binary structure exhibits a significant degree of porosity. An alternative method of layering was explored where the Cu-Se binary was layered on top of an existing indium-gallium-selenide layer and processed. This method produced highly dense and large-grained (>3 µm) CuInSe2 thin films. This has significant potential as a manufacturable route to CIGS-based solar cells.

Keywords

OrganometallicPhase transformationSolution deposition
Type
Articles
Information
Journal of Materials Research , Volume 24 , Issue 4 , April 2009 , pp. 1375 - 1387
Copyright
Copyright © Materials Research Society 2009

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1AbuShama, J.A.M.Johnston, S.Moriarty, T.Teeter, G.Ramanathan, K. and Noufi, R.: Properties of ZnO/CdS/CuInSe2solar cells with improved performance. Prog. Photovoltaics Res. Appl. 12,(1) 39 (2004).CrossRefGoogle Scholar
2Contreras, M.A.Egaas, B.Ramanathan, K.Hiltner, J.Swartzlander, A.Hasoon, F. and Noufi, R.: Progress toward 20% efficiency in Cu(In,Ga)Se2 polycrystalline thin-film solar cells. Prog. Photovoltaics Res. Appl. 7,(4) 311 (1999).3.0.CO;2-G>CrossRefGoogle Scholar
3Repins, I.Contreras, M.A.Egaas, B.DeHart, C.Scharf, J.Perkins, C.L.To, B. and Noufi, R.: 19.9%-efficient ZnO/CdS/ CuInGaSe2 solar cell with 81.2% fill factor. Prog. Photovoltaics Res. Appl. Early View, 1 (2008).Google Scholar
4Noufi, R.Gabor, A.Tuttle, J.Tennant, A.Contreras, M.Albin, D. and Carapella, J.: Method of fabricating high-efficiency Cu(In,Ga) (Se,S)2 thin films for solar cells. U.S. Patent No. 5441897 (1995).Google Scholar
5Eberspacher, C.Fredric, C.Pauls, K. and Serra, J.: Thin-film CIS alloy PV materials fabricated using non-vacuum, particles-based techniques. Thin Solid Films 387(1-2), 18 (2001).CrossRefGoogle Scholar
6Kapur, V.K.Fishe, M. and Roe, R.: Nanoparticle oxides precursor inks for thin film copper indium gallium selenide (CIGS) solar cells, in II-VI Compound Semiconductor Photovoltaic Materials,edited by Noufi, R.Birkmire, R.W.Lincot, D. and Schock, H.W. (Mater. Res. Soc. Symp. Proc. 668, Warrendale, PA, 2001), H2.6.1.Google Scholar
7Kaelin, M.Rudmann, D.Kurdesau, F.Meyer, T.Zogg, H. and Tiwari, A.N.: CIS and CIGS layers from selenized nanoparticle precursors. Thin Solid Films 431, 58 (2003).CrossRefGoogle Scholar
8Banger, K.K.Hepp, A.F.Harris, J.D.Jin, M.H-C. and Castro, S.L.: Single-source precursors for ternary chalcopyrite materials, and methods of making and using the same. U.S. Patent No. 6992202 (2006).Google Scholar
9Hollingsworth, J.A.Banger, K.K.Jin, M.H.C.Harris, J.D.Cowen, J.E.Bohannan, E.W.Switzer, J.A.Buhro, W. and Hepp, A.F.: Single-source precursors for fabrication of I-III-VI2 thin-film solar cells via spray CVD. Thin Solid Films 431, 63 (2003).CrossRefGoogle Scholar
10Banger, K.K.Hollingsworth, J.A.Harris, J.D.Cowen, J.Buhro, W.E. and Hepp, A.F.: Ternary single-source precursors for polycrystalline thin-film solar cells. Appl. Organomet. Chem. 16,(11) 617 (2002).CrossRefGoogle Scholar
11Banger, K.K.Harris, J.D.Cowen, J.E. and Hepp, A.F.: Facile modulation of single-source precursors: The synthesis and characterization of single-source precursors for deposition of ternary chalcopyrite materials. Thin Solid Films 403, 390 (2002).CrossRefGoogle Scholar
12Hepp, A.F.Raffaelle, R.P.Banger, K.K.Jin, M.H.Lau, J.E.Harris, J.D.Cowen, J.E. and Duraj, S.A.: Chemical vapor deposition for ultra-lightweight thin-film solar arrays for space. 37th Intersociety Energy Conversion Engineering Conference (IECEC), (2002), 198.Google Scholar
13Mitzi, D.B.Yuan, M.Liu, W.Kellock, A.Chey, S.J.Schrott, A. and Deline, V.: Solution processing of CIGS absorber layers using a hydrazine-based approach. 33rd IEEE Photovoltaic Specialists Conference (2008).CrossRefGoogle Scholar
14Mitzi, D.B.Yuan, M.Liu, W.Kellock, A.J.Chey, S.J.Deline, V. and Schrott, A.G.: A high-efficiency solution-deposited thin-film photovoltaic device. Adv. Mater. 20, 3657 (2008).CrossRefGoogle Scholar
15Probst, V.Karg, F.Rimmasch, J.Riedl, W.Stetter, W.Harms, H. and Eibl, O.: Advanced stacked elemental layer process for Cu (InGa)Se2 thin film photovoltaic devices, in Photovoltaic and Related Device Applications 165 (1996).CrossRefGoogle Scholar
16Probst, V.Stetter, W.Riedl, W.Vogt, H.Wendl, M.Calwer, H.Zweigart, S.Ufert, K.D.Freienstein, B.Cerva, H. and Karg, F.H.: Rapid CIS-process for high efficiency PV-modules: Development towards large area processing. Thin Solid Films 387(1-2), 262 (2001).CrossRefGoogle Scholar
17Probst, V.Palm, J.Visbeck, S.Niesen, T.Tolle, R.Lerchenberger, A.Wendl, M.Vogt, H.Calwer, H.Stetter, W. and Karg, F.: New developments in Cu(In,Ga)(S, Se)2 thin film modules formed by rapid thermal processing of stacked elemental layers. Sol. Energy Mater. Sol. Cells 90(18-19), 3115 (2006).CrossRefGoogle Scholar
18Curtis, C.J.Miedaner, A.Hest, M. van, Ginley, D.S. and Nekuda, J.A.: Formation of copper-indium-selenide and/or copper-indium-gallium-selenide films from indium selenide and copper selenide precursors. Patent Cooperation Treaty (PCT) Patent No. (2008).Google Scholar
19Mitzi, D.B.Copel, M. and Chey, S.J.: Low-voltage transistor employing a high-mobility spin-coated calcogenide semiconductor. Adv. Mater. 17,(10) 1285 (2005).CrossRefGoogle Scholar
20Mitzi, D.B.Kosbar, L.L.Murray, C.E.Copel, M. and Afzali, A.: High-mobility ultrathin semiconducting films prepared by spin coating. Nature 428, 299 (2004).CrossRefGoogle ScholarPubMed
21SONO-TEK Corporation: http://www.sono-tek.com/index.php.Google Scholar
22ULVAC-RIKO MILA-3000 Series Desktop Lamp Heating Unit: http://www.ulvac-riko.co.jp/English/E-5en.html.Google Scholar
23Marsillac, S.Combot-Marie, A.M., Bernede, J.C. and Conan, A.: Experimental evidence of the low-temperature formation of gamma-In2Se3 thin films obtained by a solid-state reaction. Thin Solid Films 288, 14 (1996).CrossRefGoogle Scholar
24Li, J.B.Record, M.C. and Tedenac, J.C.: A thermodynamic assessment of the In-Se system. Z. Metallkd. 94,(4) 381 (2003).CrossRefGoogle Scholar
25Okamoto, H.: In-Se (Indium-Selenium). J. Phase Equilib. Diffus. 25,(2) 201 (2004).CrossRefGoogle Scholar
26Gysling, H.J.Wernberg, A.A. and Blanton, T.N.: Molecular design of single-source precursors for 3-6 semiconductor films: Control of phase and stoichiometry in InxSey films deposited by a spray MOCVD process using single-source reagents. Chem. Mater. 4, 900 (1992).CrossRefGoogle Scholar
27Cheon, J.Arnold, J.Yu, K-M. and Bourret, E.D.: Metal-organic chemical vapor deposition of semiconducting III/VI In2Se3 thin films from the single-source precursor: In[SeC(SiMe3)3]3. Chem. Mater. 7,(12) 2273 (1995).CrossRefGoogle Scholar
28Contreras, M.A.Egaas, B.King, D.Swartzlander, A. and Dullweber, T.: Texture manipulation of CuInSe2 thin films. Thin Solid Films 361-362, 167 (2000).CrossRefGoogle Scholar
29Casteleyn, M.Burgelman, M.Depuydt, B.Niemegeers, A. and Clemminck, I.: Growth studies of CuInSe2 using Cu-Se fluxes. First World Conference on Photovoltaic Energy Conversion, Twenty Fourth IEEE Photovoltaic Specialists Conference (1994), 230.Google Scholar
30Glazov, V.M.Pashinkin, A.S. and Fedorov, V.A.: Phase equilibria in the Cu-Se system. Inorg. Mater. 36,(7) 641 (2000).CrossRefGoogle Scholar
31Heyding, R.D. and Murray, R.M.: The crystal structures of Cu1.8Se, Cu3Se2, a- and γCuSe, CuSe2, and CuSe2II. Can. J. Chem. 54,(6) 841 (1976).CrossRefGoogle Scholar
32Ohtani, T.Motoki, M.Koh, K. and Ohshima, K.: Synthesis of binary copper chalcogenides by mechanical alloying. Mater. Res. Bull. 30,(12) 1495 (1995).CrossRefGoogle Scholar
33Heyding, R.D.: The copper/selenium system. Can. J. Chem. 44 (10), 1233 (1966).CrossRefGoogle Scholar
34Kogut, A.N.Mel'nik, A.I., and Mikolaichuk, A.G.: Structure and electrical properties of thin films of copper selenide. Russ. J. Phys. 16,(8) 1113 (1973).Google Scholar
35Stanbery, B.J.: Copper indium selenides and related materials for photovoltaic devices. Crit. Rev. Solid State Mater. Sci. 27,(2) 73 (2002).CrossRefGoogle Scholar
36Stanbery, B.J.: Synthesis of layers, coatings or films using templates. U.S. Patent No. 6881647 (2005).Google Scholar
37Abou-Ras, D., Kostorz, G.Bremaud, D.Kalin, M.Kurdesau, F.V.Tiwari, A.N. and Dobeli, M.: Formation and characterisation of MoSe2 for Cu(In,Ga)Se2 based solar cells. Thin Solid Films 480-481, 433 (2005).CrossRefGoogle Scholar
38Nishiwaki, S.Kohara, N.Negami, T. and Wada, T.: MoSe2 layer formation at Cu(In,Ga)Se2/Mo interfaces in high efficiency Cu(In1-xGax)Se2 solar cells. Jpn. J. Appl. Phys. 37, L71 (1998).CrossRefGoogle Scholar
39Terasako, T.Uno, Y.Kariya, T. and Shirakata, S.: Structural and optical properties of In-rich Cu-In-Se polycrystalline thin films prepared by chemical spray pyrolysis. Sol. Energy Mater. Sol. Cells 90,(3) 262 (2006).CrossRefGoogle Scholar