Atomic layer deposition of amorphous antimony sulfide (a-Sb2S3) is demonstrated with an alternating exposure of tris(dimethylamino)antimony (TDMASb) and hydrogen sulfide (H2S) at 150 °C in a custom-built viscous flow reactor. Growth mechanism and deposition chemistry are investigated by in situ quartz crystal microbalance and in situ Fourier Transform Infrared spectroscopy. Reaction hypothesis facilitating the binary reaction is established by quantum mechanical density functional theory calculations that essentially support the experimental findings. The developed material is used as a photon harvester in solar cells under extremely thin absorber configuration, with TiO2 and Spiro-OMeTAD as electron and hole transporting layers, respectively. Investigation of charge injection properties with surface photovoltage spectroscopy reveals low but non-negligible density of interfacial (sensitizer/TiO2) electronic defects. The conventional viscous flow reactor configuration is modified to showerhead-type reactor configuration to achieve better uniformity and conformality of a-Sb2S3 on highly porous TiO2 scaffolds. a-Sb2S3 device performance is optimized to achieve the highest power conversion efficiencies of 0.5% while annealed crystalline c-Sb2S3 device reaches power conversion efficiencies of 1.9% under 1 sun illumination.
REFERENCES
1.
O.
Niitsoo
, S. K.
Sarkar
, C.
Pejoux
, S.
Rühle
, D.
Cahen
, and G.
Hodes
, J. Photochem. Photobiol. A
181
, 306
(2006
). 2.
H. J.
Lee
, D. W.
Chang
, S.-M.
Park
, S. M.
Zakeeruddin
, M.
Gratzel
, and M. K.
Nazeeruddin
, Chem. Commun.
46
, 8788
(2010
). 3.
H.
Choi
, R.
Nicolaescu
, S.
Paek
, J.
Ko
, and P. V.
Kamat
, ACS Nano
5
, 9238
(2011
). 4.
P. K.
Santra
and P. V.
Kamat
, J. Am. Chem. Soc.
134
, 2508
(2012
). 5.
X.-Y.
Yu
, B.-X.
Lei
, D.-B.
Kuang
, and C.-Y.
Su
, J. Mater. Chem.
22
, 12058
(2012
). 6.
Z.
Du
et al, J. Phys. Chem. Lett.
7
, 3103
(2016
). 7.
J.
Yang
and X.
Zhong
, J. Mater. Chem. A
4
, 16553
(2016
). 8.
Y.
Itzhaik
, O.
Niitsoo
, M.
Page
, and G.
Hodes
, J. Phys. Chem. C
113
, 4254
(2009
). 9.
H. J.
Lee
et al, Langmuir
25
, 7602
(2009
). 10.
J. A.
Chang
, J. H.
Rhee
, S. H.
Im
, Y. H.
Lee
, H.-J.
Kim
, S. I.
Seok
, M. K.
Nazeeruddin
, and M.
Gratzel
, Nano Lett.
10
, 2609
(2010
). 11.
S.-J.
Moon
, Y.
Itzhaik
, J.-H.
Yum
, S. M.
Zakeeruddin
, G.
Hodes
, and M.
Grätzel
, J. Phys. Chem. Lett.
1
, 1524
(2010
). 12.
S. K.
Sarkar
, J. Y.
Kim
, D. N.
Goldstein
, N. R.
Neale
, K.
Zhu
, C. M.
Elliott
, A. J.
Frank
, and S. M.
George
, J. Phys. Chem. C
114
, 8032
(2010
). 13.
S. H.
Im
, C.-S.
Lim
, J. A.
Chang
, Y. H.
Lee
, N.
Maiti
, H.-J.
Kim
, M. K.
Nazeeruddin
, M.
Grätzel
, and S. I.
Seok
, Nano Lett.
11
, 4789
(2011
). 14.
L.
Etgar
, T.
Moehl
, S.
Gabriel
, S. G.
Hickey
, A.
Eychmüller
, and M.
Grätzel
, ACS Nano
6
, 3092
(2012
). 15.
L.
Zhang
, C.
Wu
, W.
Liu
, S.
Yang
, M.
Wang
, T.
Chen
, and C.
Zhu
, J. Mater. Chem. A
6
, 21320
(2018
). 16.
R.
Kondrotas
, C.
Chen
, and J.
Tang
, Joule
2
, 857
(2018
). 17.
Y. C.
Choi
, D. U.
Lee
, J. H.
Noh
, E. K.
Kim
, and S. I.
Seok
, Adv. Funct. Mater.
24
, 3587
(2014
). 18.
N.
Maiti
, S. H.
Im
, C.-S.
Lim
, and S. I.
Seok
, Dalton Trans.
41
, 11569
(2012
). 19.
Y.
Osorio Mayon
, T. P.
White
, R.
Wang
, Z.
Yang
, and K. R.
Catchpole
, Phys. Status Solidi A
213
, 108
(2016
). 20.
Y.
Li
, L.
Wei
, R.
Zhang
, Y.
Chen
, L.
Mei
, and J.
Jiao
, Nanoscale Res. Lett.
8
, 89
(2013
). 21.
A. M.
Huerta-Flores
, N. A.
García-Gómez
, S. M.
de la Parra-Arciniega
, and E. M.
Sánchez
, Semicond. Sci. Technol.
31
, 085011
(2016
). 22.
S. M.
George
, Chem. Rev.
110
, 111
(2010
). 23.
N. P.
Dasgupta
, X.
Meng
, J. W.
Elam
, and A. B. F.
Martinson
, Acc. Chem. Res.
48
, 341
(2015
). 24.
H.
Wedemeyer
, J.
Michels
, R.
Chmielowski
, S.
Bourdais
, T.
Muto
, M.
Sugiura
, G.
Dennler
, and J.
Bachmann
, Energy Environ. Sci.
6
, 67
(2013
). 25.
R. B.
Yang
, J.
Bachmann
, M.
Reiche
, J. W.
Gerlach
, U.
Gösele
, and K.
Nielsch
, Chem. Mater.
21
, 2586
(2009
). 26.
R. B.
Yang
, N.
Zakharov
, O.
Moutanabbir
, K.
Scheerschmidt
, L.-M.
Wu
, U.
Gösele
, J.
Bachmann
, and K.
Nielsch
, J. Am. Chem. Soc.
132
, 7592
(2010
). 27.
N.
Mahuli
and S. K.
Sarkar
, J. Vac. Sci. Technol. A
34
, 01A142
(2016
). 28.
N.
Mahuli
, D.
Saha
, and S. K.
Sarkar
, J. Phys. Chem. C
121
, 8136
(2017
). 29.
30.
C.
Lee
, W.
Yang
, and R. G.
Parr
, Phys. Rev. B
37
, 785
(1988
). 31.
M. J.
Frisch
et al, Gaussian 09, Revision A.02, Gaussian, Inc., Pittsburgh, PA, 2009 (Wallingford
, CT
, 2009
).32.
S.
Rühle
and D.
Cahen
, J. Appl. Phys.
96
, 1556
(2004
). 33.
L. H.
Dubois
, B. R.
Zegarski
, and G. S.
Girolami
, J. Electrochem. Soc.
139
, 3603
(1992
). 34.
B. B.
Burton
, A. R.
Lavoie
, and S. M.
George
, J. Electrochem. Soc.
155
, D508
(2008
). 35.
B. B.
Burton
, S. W.
Kang
, S. W.
Rhee
, and S. M.
George
, J. Phys. Chem. C
113
, 8249
(2009
). 36.
X.
Meng
, J. A.
Libera
, T. T.
Fister
, H.
Zhou
, J. K.
Hedlund
, P.
Fenter
, and J. W.
Elam
, Chem. Mater.
26
, 1029
(2014
). 37.
D. Y. W.
Yu
, H. E.
Hoster
, and S. K.
Batabyal
, Sci. Rep.
4
, 4562
(2015
). 38.
R.
Parize
, A.
Katerski
, I.
Gromyko
, L.
Rapenne
, H.
Roussel
, E.
Kärber
, E.
Appert
, M.
Krunks
, and V.
Consonni
, J. Phys. Chem. C
121
, 9672
(2017
). 39.
B.
Krishnan
, A.
Arato
, E.
Cardenas
, T. K. D.
Roy
, and G. A.
Castillo
, Appl. Surf. Sci.
254
, 3200
(2008
). 40.
Y. C.
Choi
and S. I.
Seok
, Adv. Funct. Mater.
25
, 2892
(2015
). 41.
K. C.
Godel
, Y. C.
Choi
, B.
Roose
, A.
Sadhanala
, H. J.
Snaith
, S. I.
Seok
, U.
Steiner
, and S. K.
Pathak
, Chem. Commun.
51
, 8640
(2015
). 42.
L.
Kronik
, N.
Ashkenasy
, M.
Leibovitch
, E.
Fefer
, Y.
Shapira
, S.
Gorer
, and G.
Hodes
, J. Electrochem. Soc.
145
, 1748
(1998
). 43.
L.
Kronik
and Y.
Shapira
, Surf. Sci. Rep.
37
, 1
(1999
). 44.
F.
Lenzmann
, J.
Krueger
, S.
Burnside
, K.
Brooks
, M.
Grätzel
, D.
Gal
, S.
Rühle
, and D.
Cahen
, J. Phys. Chem. B
105
, 6347
(2001
). 45.
L.
Barnea-Nehoshtan
, S.
Kirmayer
, E.
Edri
, G.
Hodes
, and D.
Cahen
, J. Phys. Chem. Lett.
5
, 2408
(2014
). 46.
M.
Rodríguez-Pérez
, E. J.
Canto-Aguilar
, R.
García-Rodríguez
, A. T.
De Denko
, G.
Oskam
, and F. E.
Osterloh
, J. Phys. Chem. C
122
, 2582
(2018
). 47.
N.
Mahuli
, D.
Halder
, A.
Paul
, and S. K.
Sarkar
, Chem. Mater.
31
(18
), 7434
(2019
). 48.
S. K. S.
Hagai Cohen
and Gary
Hodes
, J. Phys. Chem. B
110
, 25508
(2006
). 49.
S. K.
Sarkar
, G.
Hodes
, L.
Kronik
, and H.
Cohen
, J. Phys. Chem. C
112
, 6564
(2008
). 50.
J.
Zhao
and F. E.
Osterloh
, J. Phys. Chem. Lett.
5
, 782
(2014
). 51.
C.
Detavernier
, J.
Dendooven
, S.
Pulinthanathu Sree
, K. F.
Ludwig
, and J. A.
Martens
, Chem. Soc. Rev.
40
, 5242
(2011
). 52.
J. W.
Elam
, D.
Routkevitch
, P. P.
Mardilovich
, and S. M.
George
, Chem. Mater.
15
, 3507
(2003
). 53.
W.
Szmyt
, C.
Guerra
, and I.
Utke
, Beilstein J. Nanotechnol.
8
, 64
(2017
). 54.
See supplementary material at https://doi.org/10.1116/6.0000031 for assignment of vibrational frequencies during Sb2S3 ALD, additional details about computational calculations, X-ray diffraction of as-deposited and annealed Sb2S3 thin films, X-ray photoelectron spectroscopy of as-deposited Sb2S3 thin films, SPS spectra of TiO2 on FTO, SPS spectra of CBD and ALD grown Sb2S3/TiO2/FTO, UPS analysis of as-deposited films and energy band diagram, schematic of conventional and modified reactor configuration, and photovoltaic device performance for a-Sb2S3 and annealed c-Sb2S3 sensitized ETA solar cell.
© 2020 Author(s).
2020
Author(s)
You do not currently have access to this content.