Electrodeposited thin-film Cu-Zn-Sn samples were reacted in varying ratios of mixed Ar/H2S/H2Se to form Cu2ZnSn(S,Se)4 (CZTSSe). Reactions were carried out at atmospheric pressure, reaching a temperature of 550 °C. Sulfur/selenium ratios in reacted films were determined as a function of [H2S]/[H2Se] in the reaction atmosphere. Relative S/Se incorporation into the CZTSSe films was used to estimate the Gibbs free energy of quaternary Cu2ZnSnSe4 to be . When chalcogen species are supplied from hydride gas sources, formation of the selenide quaternary is favored over the sulfide.
References
1.
S.
Chen
, A.
Walsh
, J.-H.
Yang
, X.-G.
Gong
, L.
Sun
, P.
Yang
, J.
Chu
, and S.
Wei
, “Compositional dependence of structural and electronic properties of Cu2ZnSn(S,Se)4 alloys for thin film solar cells
,” Phys. Rev. B
83
, 125201
(2011
).2.
J.
Paier
, R.
Asahi
, A.
Nagoya
, and G.
Kresse
, “Cu2ZnSnS4 as a potential photovoltaic material: A hybrid Hartree-Fock density functional theory study
,” Phys. Rev. B
79
, 115126
(2009
).3.
S.
Schorr
, “The crystal structure of kesterite type compounds: A neutron and X-ray diffraction study
,” Sol. Energy Mater. Sol. Cells
95
, 1482
(2011
).4.
S.
Siebentritt
and S.
Schorr
, “Kesterites-a challenging material for solar cells
,” Prog. Photovoltaics
20
, 512
(2012
).5.
S.
Siebentritt
, “Why are kesterite solar cells not 20% efficient?
,” Thin Solid Films
535
, 1
(2013
).6.
J. J.
Scragg
, T.
Ericson
, T.
Kubart
, M.
Edoff
, and C.
Platzer-Björkman
, “Chemical insights into the instability of Cu2ZnSnS4 films during annealing
,” Chem. Mater.
23
, 4625
(2011
).7.
X.
Yin
, C.
Tang
, L.
Sun
, Z.
Shen
, and H.
Gong
, “Study on phase formation mechanism of non- and near-stoichiometric Cu2ZnSn(S,Se)4 film prepared by selenization of Cu-Sn-Zn-S precursors
,” Chem. Mater.
26
, 2005
(2014
).8.
I.
Olekseyuk
, I.
Dudchak
, and L.
Piskach
, “Phase equilibria in the Cu2S-ZnS-SnS2 system
,” J. Alloys Compd.
368
, 135
(2004
).9.
L.
Choubrac
, A.
Lafond
, M.
Paris
, C.
Guillot-Deudon
, and S.
Jobic
, “The stability domain of the selenide kesterite photovoltaic materials and NMR investigation of the Cu/Zn disorder in Cu2ZnSnSe4 (CZTSe)
,” Phys. Chem. Chem. Phys.
17
, 15088
(2015
).10.
S.
Bag
, O.
Gunawan
, T.
Gokmen
, Y.
Zhu
, T. K.
Todorov
, and D. B.
Mitzi
, “Low band gap liquid-processed CZTSe solar cell with 10.1% efficiency
,” Energy Environ. Sci.
5
, 7060
(2012
).11.
W.
Wang
, M. T.
Winkler
, O.
Gunawan
, T.
Gokmen
, T. K.
Todorov
, Y.
Zhu
, and D. B.
Mitzi
, “Device characteristics of CZTSSe thin-film solar cells with 12.6% efficiency
,” Adv. Energy Mater.
4
, 1301465
(2014
).12.
I. L.
Repins
, C.
Beall
, N.
Vora
, C.
DeHart
, D.
Kuciauskas
, P.
Dippo
, B.
To
, J.
Mann
, W.-C.
Hsu
, A.
Goodrich
, and R.
Noufi
, “Co-evaporated Cu2ZnSnSe4 films and devices
,” Sol. Energy Mater. Sol. Cells
101
, 154
(2012
).13.
Y. S.
Lee
, T.
Gershon
, O.
Gunawan
, T. K.
Todorov
, T.
Gokmen
, Y.
Virgus
, and S.
Guha
, “Cu2ZnSnSe4 thin-film solar cells by thermal co-evaporation with 11.6% efficiency and improved minority carrier diffusion length
,” Adv. Energy Mater.
5
, 1401372
(2015
).14.
H.
Katagiri
, K.
Saitoh
, T.
Washio
, H.
Shinohara
, T.
Kurumadani
, and S.
Miyajima
, “Development of thin film solar cell based on Cu2ZnSnS4 thin films
,” Sol. Energy Mater. Sol. Cells
65
, 141
(2001
).15.
G.
Zoppi
, I.
Forbes
, R. W.
Miles
, P. J.
Dale
, J. J.
Scragg
, and L. M.
Peter
, “Cu2ZnSnSe4 thin film solar cells produced by selenisation of magnetron sputtered precursors
,” Prog. Photovoltaics
17
, 315
(2009
).16.
C.
Platzer-Björkman
, J. J.
Scragg
, H.
Flammersberger
, T.
Kubart
, and M.
Edoff
, “Influence of precursor sulfur content on film formation and compositional changes in Cu2ZnSnS4 films and solar cells
,” Sol. Energy Mater. Sol. Cells
98
, 110
(2012
).17.
R. A.
Wibowo
, H.
Yoo
, A.
Hölzing
, R.
Lechner
, S.
Jost
, J.
Palm
, M.
Gowtham
, B.
Louis
, and R.
Hock
, “A study of kesterite Cu2ZnSn(Se,S)4 formation from sputtered Cu-Zn-Sn metal precursors by rapid thermal processing sulfo-selenization of the metal thin films
,” Thin Solid Films
535
, 57
(2013
).18.
J. J.
Scragg
, P. J.
Dale
, L. M.
Peter
, G.
Zoppi
, and I.
Forbes
, “New routes to sustainable photovoltaics: Evaluation of Cu2ZnSnS4 as an alternative absorber material
,” Phys. Status Solidi B
245
, 1772
(2008
).19.
R.
Schurr
, A.
Hölzing
, S.
Jost
, R.
Hock
, T.
Voß
, J.
Schulze
, A.
Kirbs
, A.
Ennaoui
, M. C.
Lux-Steiner
, A.
Weber
, I.
Kötschau
, and H.-W.
Schock
, “The crystallisation of Cu2ZnSnS4 thin film solar cell absorbers from co-electroplated Cu-Zn-Sn precursors
,” Thin Solid Films
517
, 2465
(2009
).20.
M.
Ganchev
, L.
Kaupmees
, J.
Iljina
, J.
Raudoja
, O.
Volobujeva
, H.
Dikov
, M.
Altosaar
, E.
Mellikov
, and T.
Varema
, “Formation of Cu2ZnSnSe4 thin films by selenization of electrodeposited stacked binary alloy layers
,” Energy Procedia
2
, 65
(2010
).21.
D. M.
Berg
, “Kesterite equilibrium reaction and the discrimination of secondary phases from Cu2ZnSnS4
,” Ph.D. thesis (University of Luxembourg
, 2012
).22.
S.
Ahmed
, K. B.
Reuter
, O.
Gunawan
, L.
Guo
, L. T.
Romankiw
, and H.
Deligianni
, “A high efficiency electrodeposited Cu2ZnSnS4 solar cell
,” Adv. Energy Mater.
2
, 253
(2012
).23.
F.
Jiang
, S.
Ikeda
, T.
Harada
, and M.
Matsumura
, “Pure sulfide Cu2ZnSnS4 thin film solar cells fabricated by preheating an electrodeposited metallic stack
,” Adv. Energy Mater.
4
, 1301381
(2014
).24.
L.
Guo
, Y.
Zhu
, O.
Gunawan
, T.
Gokmen
, V. R.
Deline
, S.
Ahmed
, L. T.
Romankiw
, and H.
Deligianni
, “Electrodeposited Cu2ZnSnSe4 thin film solar cell with 7% power conversion efficiency
,” Prog. Photovoltaics
22
, 58
(2013
).25.
D. M.
Berg
, A.
Crossay
, J.
Guillot
, V.
Izquierdo-Roca
, A.
Pérez-Rodriguez
, S.
Ahmed
, H.
Deligianni
, S.
Siebentritt
, and P. J.
Dale
, “Simplified formation process for Cu2ZnSnS4-based solar cells
,” Thin Solid Films
573
, 148
(2014
).26.
Q.
Guo
, G. M.
Ford
, W.-C.
Yang
, B. C.
Walker
, E. A.
Stach
, H. W.
Hillhouse
, and R.
Agrawal
, “Fabrication of 7.2% efficient CZTSSe solar cells using CZTS nanocrystals
,” J. Am. Chem. Soc.
132
, 17384
(2010
).27.
R.
Mainz
, B. C.
Walker
, S. S.
Schmidt
, O.
Zander
, A.
Weber
, H.
Rodriguez-Alvarez
, J.
Just
, M.
Klaus
, R.
Agrawal
, and T.
Unold
, “Real-time observation of Cu2ZnSn(S,Se)4 solar cell absorber layer formation from nanoparticle precursors
,” Phys. Chem. Chem. Phys.
15
, 18281
(2013
).28.
J. T.
Wätjen
, J. J.
Scragg
, T.
Ericson
, M.
Edoff
, and C.
Platzer-Björkman
, “Secondary compound formation revealed by transmission electron microscopy at the Cu2ZnSnS4/Mo interface
,” Thin Solid Films
535
, 31
(2013
).29.
T. K.
Todorov
, H.
Sugimoto
, O.
Gunawan
, T.
Gokmen
, and D. B.
Mitzi
, “High-efficiency devices with pure solution-processed Cu2ZnSn(S,Se)4 absorbers
,” IEEE J. Photovoltaics
4
, 483
(2014
).30.
P.
Reddy
, Solar Power Generation: Technology, New Concepts & Policy
(Taylor & Francis
, 2012
), p. 71
.31.
O.
Knacke
, O.
Kubaschewski
, and K.
Hesselmann
, Thermochemical Properties of Inorganic Substances
(Springer-Verlag
, 1991
).32.
A.
Redinger
, D. M.
Berg
, P. J.
Dale
, and S.
Siebentritt
, “The consequences of kesterite equilibria for efficient solar cells
,” J. Am. Chem. Soc.
133
, 3320
(2011
).33.
A.
Redinger
, D. M.
Berg
, P. J.
Dale
, R.
Djemour
, L.
Gütay
, T.
Eisenbarth
, N.
Valle
, and S.
Siebentritt
, “Route toward high-efficiency single-phase Cu2ZnSn(S,Se)4 thin-film solar cells: Model experiments and literature review
,” IEEE J. Photovoltaics
1
, 200
(2011
).34.
J. J.
Scragg
, P. J.
Dale
, D.
Colombara
, and L. M.
Peter
, “Thermodynamic aspects of the synthesis of thin-film materials for solar cells
,” ChemPhysChem
13
, 3035
(2012
).35.
J. J.
Scragg
, J. T.
Wätjen
, M.
Edoff
, T.
Ericson
, T.
Kubart
, and C.
Platzer-Björkman
, “A detrimental reaction at the molybdenum back contact in Cu2ZnSn(S,Se)4 thin-film solar cells
,” J. Am. Chem. Soc.
134
, 19330
(2012
).36.
H.
Katagiri
, K.
Jimbo
, M.
Tahara
, H.
Araki
, and K.
Oishi
, in The Influence of the Composition Ratio on CZTS-based Thin Film Solar Cells
, edited by A.
Yamada
, C.
Heske
, M.
Contreras
, M.
Igalson
, and S. J. C.
Irvine
(Mater. Res. Soc. Symp. Proc.
, 2009
), Vol. 1165.37.
D. B.
Mitzi
, O.
Gunawan
, T. K.
Todorov
, K.
Wang
, and S.
Guha
, “The path towards a high-performance solution-processed kesterite solar cell
,” Sol. Energy Mater. Sol. Cells
95
, 1421
(2011
).38.
R.
Birkmire
and M.
Engelmann
, “Chemical kinetics and equilibrium analysis of I-III-VI films
,” AIP Conf. Proc.
462
, 23
(1999
).© 2015 AIP Publishing LLC.
2015
AIP Publishing LLC
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