Antimony telluroiodide (SbTeI) is predicted to be a promising material in many technological applications based on theoretical simulations; however, the bulk structure solution remains elusive. We consolidate SbTeI belonging to the base-centered monoclinic lattice with a space group C 2/m by combining single crystal x-ray diffraction and x-ray photoemission spectroscopy techniques. The atomic arrangement of the reported crystal structure is remarkable with one-dimensional double-chains forming two-dimensional blocks. In this structure, the Sb3+ ion is surrounded by Te2− and I−, which is distinguishable by an incomplete polyhedron resulting in 5s2 (Sb) lone pair electrons in the valence band. Manipulation of this material with pressure to induce novel structures and properties is highly anticipated.
REFERENCES
1.
H.
Kunioku
, M.
Higashi
, and R.
Abe
, “Low-temperature synthesis of bismuth chalcohalides: Candidate photovoltaic materials with easily, continuously controllable band gap
,” Sci. Rep.
6
, 32664
(2016
). 2.
R.
Nie
, J.
Im
, and S. I.
Seok
, “Efficient solar cells employing light-harvesting Sb0.67Bi0.33SI
,” Adv. Mater.
31
, 1808344
(2019
). 3.
A. M.
Ganose
, S.
Matsumoto
, J.
Buckeridge
, and D. O.
Scanlon
, “Defect engineering of earth-abundant solar absorbers BiSI and BiSeI
,” Chem. Mater.
30
, 3827
–3835
(2018
). 4.
K.
Mistewicz
, M.
Nowak
, and D.
Stróż
, “A ferroelectric-photovoltaic effect in SbSI nanowires
,” Nanomaterials
9
, 580
(2019
). 5.
S.
Inagaki
, M.
Nakamura
, H.
Hatada
, R.
Nishino
, F.
Kagawa
, Y.
Tokura
, and M.
Kawasaki
, “Growth of visible-light-responsive ferroelectric SbSI thin films by molecular beam epitaxy
,” Appl. Phys. Lett.
116
, 072902
(2020
). 6.
Y.
Purusothaman
, N. R.
Alluri
, A.
Chandrasekhar
, and S.-J.
Kim
, “Photoactive piezoelectric energy harvester driven by antimony sulfoiodide (SbSI): A AVBVICVII class ferroelectric-semiconductor compound
,” Nano Energy
50
, 256
–265
(2018
). 7.
D.
Tiwari
, F.
Cardoso-Delgado
, D.
Alibhai
, M.
Mombrú
, and D. J.
Fermín
, “Photovoltaic performance of phase-pure orthorhombic BiSI thin-films
,” ACS Appl. Energy Mater.
2
, 3878
–3885
(2019
). 8.
S.-D.
Guo
, X.-S.
Guo
, Z.-Y.
Liu
, and Y.-N.
Quan
, “Large piezoelectric coefficients combined with high electron mobilities in janus monolayer XTeI (X = Sb and Bi): A first-principles study
,” J. Appl. Phys.
127
, 064302
(2020
). 9.
R.
Nishikubo
, H.
Kanda
, I.
García-Benito
, A.
Molina-Ontoria
, G.
Pozzi
, A. M.
Asiri
, M. K.
Nazeeruddin
, and A.
Saeki
, “Optoelectronic and energy level exploration of bismuth and antimony-based materials for lead-free solar cells
,” Chem. Mater.
32
, 6416
–6424
(2020
). 10.
C.
Tablero
, “Optical properties of Sb(Se,Te)I and photovoltaic applications
,” J. Alloys Compd.
678
, 18
–22
(2016
). 11.
S.-D.
Guo
, A.-X.
Zhang
, and H.-C.
Li
, “Potential 2D thermoelectric material ATeI (A = Sb and Bi) monolayers from a first principles study
,” Nanotechnology
28
, 445702
(2017
). 12.
H. L.
Zhuang
, V. R.
Cooper
, H.
Xu
, P.
Ganesh
, R. G.
Hennig
, and P. R. C.
Kent
, “Rashba effect in single-layer antimony telluroiodide SbTeI
,” Phys. Rev. B
92
, 115302
(2015
). 13.
Y.
Qi
, W.
Shi
, P. G.
Naumov
, N.
Kumar
, R.
Sankar
, W.
Schnelle
, C.
Shekhar
, F.-C.
Chou
, C.
Felser
, B.
Yan
, and S. A.
Medvedev
, “Topological quantum phase transition and superconductivity induced by pressure in the bismuth tellurohalide BiTeI
,” Adv. Mater.
29
, 1605965
(2017
). 14.
X.
Li
, Y.
Sheng
, L.
Wu
, S.
Hu
, J.
Yang
, D. J.
Singh
, J.
Yang
, and W.
Zhang
, “Defect-mediated Rashba engineering for optimizing electrical transport in thermoelectric BiTeI
,” npj Comp. Mater.
6
, 107
(2020
).15.
A.
Shevelkov
, E.
Dikarev
, R.
Shpanchenko
, and B.
Popovkin
, “Crystal structures of bismuth tellurohalides BiTeX (X = Cl, Br, I) from x-ray powder diffraction data
,” J. Solid State Chem.
114
, 379
–384
(1995
). 16.
T.
Ozer
and S.
Cabuk
, “Ab initio study of the lattice dynamical and thermodynamic properties of SbXI (X = S, Se, Te) compounds
,” Comput. Condens. Matter
16
, e00320
(2018
).17.
T.
Ozer
and S.
Cabuk
, “First-principles study of the structural, elastic and electronic properties of SbXI (X = S, Se, Te) crystals
,” J. Mol. Model
24
, 66
(2018
). 18.
H.
Koc
, S.
Palaz
, A. M.
Mamedov
, and E.
Ozbay
, “Optical, electronic, and elastic properties of some A5B6C7 ferroelectrics (A = Sb, Bi; B = S, Se; C = I, Br, Cl): First principle calculation
,” Ferroelectrics
511
, 22
–34
(2017
). 19.
V. E.
Dönges
, “Über chalkogenohalogenide des dreiwertigen antimons und wismuts.: III. Über tellurohalogenide des dreiwertigen antimons und wismuts und über antimon-und wismut(III)-tellurid und wismut(III)-selenid
,” Z. Anorg. Allg. Chem.
265
, 56
–61
(1951
). 20.
A.
Ibanez
, J.-C.
Jumas
, J.
Olivier-Fourcade
, E.
Philippot
, and M.
Maurin
, “Sur les chalcogeno-iodures d'antimoine SbXI(X = S, Se, Te) structures et spectroscopie mössbauer de 121Sb
,” J. Solid State Chem.
48
, 272
–283
(1983
). 21.
O.
Madelung
, Semiconductors Data Handbook
(Springer-Verlag
, Berlin
, 2004
), pp. 664
–673
.22.
A. G.
Papazoglou
and P. J.
Rentzeperis
, “The crystal structure of antimony telluroiodide, SbTel
,” Z. Kristallogr.
165
, 159
–167
(1983
). 23.
A. O.
Lyakhov
, A. R.
Oganov
, H. T.
Stokes
, and Q.
Zhu
, “New developments in evolutionary structure prediction algorithm USPEX
,” Comp. Phys. Comm.
184
, 1172
–1182
(2013
). 24.
A. R.
Oganov
, A. O.
Lyakhov
, and M.
Valle
, “How evolutionary crystal structure prediction works–and Why
,” Acc. Chem. Res.
44
, 227
–237
(2011
). 25.
G.
Kresse
and J.
Furthmller
, “Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
,” Comput. Mater. Sci.
6
, 15
–50
(1996
). 26.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, “Generalized gradient approximation made simple
,” Phys. Rev. Lett.
77
, 3865
(1996
). 27.
P.
Blaha
, K.
Schwarz
, G.
Madsen
, D.
Kvasnicka
, and J.
Luitz
, in WIEN2k. An Augmented Plane Wave Plus Local Orbitals Program for Calculating Crystal Properties (Techn. Universitat Wien, Austria, 2001).28.
A.
Ibanez
, J.
Olivier-Fourcade
, J. C.
Jumas
, E.
Philippot
, and M.
Maurin
, “Relations structures-propriétés physiques dans quelques semiconducteurs à paire Électronique non liée
,” Z. Anorg. Allg. Chem.
540
, 106
–116
(1986
). 29.
I.
Lefebvre
, M.
Lannoo
, G.
Allan
, and L.
Martinage
, “Theoretical Mössbauer isomer shift of antimony chalcogenides
,” Phys. Rev. B
38
, 8593
(1988
. 30.
I.
Lefebvre
, G.
Allan
, M.
Lannoo
, J.
Olivier-Fourcade
, J. C.
Jumas
, and M.
Maurin
, “Electronic structure of unconventional antimony chalcogenides: Theoretical calculations and 121Sb mössbauer spectroscopy
,” Hyperfine Interact.
53
, 351
–354
(1990
). 31.
J.
Olivier-Fourcade
, A.
Ibanez
, J. C.
Jumas
, M.
Maurin
, I.
Lefebvre
, P.
Lippens
, M.
Lannoo
, and G.
Allan
, “Chemical bonding and electronic properties in antimony chalcogenides
,” J. Solid State Chem.
87
, 366
–377
(1990
). 32.
D.
Amoroso
and S.
Picozzi
, “Ab initio approach to structural, electronic, and ferroelectric properties of antimony sulphoiodide
,” Phys. Rev. B
93
, 214106
(2016
). 33.
K.
Bu
, H.
Luo
, S.
Guo
, M.
Li
, D.
Wang
, H.
Dong
, Y.
Ding
, W.
Yang
, and X.
Lü
, “Pressure-regulated dynamic stereochemical role of lone-pair electrons in layered Bi2O2S
,” J. Phys. Chem. Lett.
11
, 9702
–9707
(2020
). 34.
M.
Nowak
, E.
Talik
, P.
Szperlich
, and D.
Stróż
, “XPS analysis of sonochemically prepared SbSI ethanogel
,” Appl. Surf. Sci.
255
, 7689
–7694
(2009
). 35.
J.
Grigas
, E.
Talik
, M.
Adamiec
, and V.
Lazauskas
, “X-ray photoelectron spectra and electronic structure of quasi-one-dimensional SbSeI crystals
,” Condens. Matter. Phys.
10
, 101
–110
(2007
). 36.
L.
Santinacci
, G. I.
Sproule
, S.
Moisa
, D.
Landheer
, X.
Wu
, A.
Banu
, T.
Djenizian
, P.
Schmuki
, and M. J.
Graham
, “Growth and characterization of thin anodic oxide films on n-InSb(1 0 0) formed in aqueous solutions
,” Corros. Sci.
46
, 2067
–2079
(2004
). 37.
H.
Bryngelsson
, J.
Eskhult
, L.
Nyholm
, M.
Herranen
, O.
Alm
, and K.
Edström
, “Electrodeposited Sb and Sb/Sb2O3 nanoparticle coatings as anode materials for Li-ion batteries
,” Chem. Mater.
19
, 1170
–1180
(2007
). 38.
R.
Izquierdo
, E.
Sacher
, and A.
Yelon
, “X-ray photoelectron spectra of antimony oxides
,” Appl. Surf. Sci.
40
, 175
–177
(1989
). 39.
C. D.
Wagner
, J. F.
Moulder
, L. E.
Davis
, and W. M.
Riggs
, Handbook of X-Ray Photoelectron Spectroscopy
(Perkin–Elmer Corporation, Physical Electronics Division
, 1995
).40.
A.
Politano
, G.
Chiarello
, C.-N.
Kuo
, C. S.
Lue
, R.
Edla
, P.
Torelli
, V.
Pellegrini
, and D. W.
Boukhvalov
, “Tailoring the surface chemical reactivity of transition-metal dichalcogenide PtTe2 crystals
,” Adv. Funct. Mater.
28
, 1706504
(2018
). 41.
H.
Bando
, K.
Koizumi
, Y.
Oikawa
, K.
Daikohara
, V. A.
Kulbachinskii
, and H.
Ozaki
, “The time-dependent process of oxidation of the surface of Bi2Te3 studied by x-ray photoelectron spectroscopy
,” J. Phys. Condens. Matter
12
, 5607
–5616
(2000
). 42.
A. A.
Volykhov
, J.
Sánchez-Barriga
, A. P.
Sirotina
, V. S.
Neudachina
, A.
Frolov
, E. A.
Gerber
, E. Y.
Kataev
, B.
Senkovsky
, N. O.
Khmelevsky
, A. A.
Aksenenko
, N. V.
Korobova
, A.
Knop-Gericke
, O.
Rader
, and L. V.
Yashina
, “Rapid surface oxidation of Sb2Te3 as indication for a universal trend in the chemical reactivity of tetradymite topological insulators
,” Chem. Mater.
28
(24
), 8916
–8923
(2016
). 43.
A.
Audzijonis
, L.
Žigas
, G.
Gaigalas
, R.
Sereika
, and B.
Žygaitienė
, “Density functional calculation of the photoelectron emission spectra of BiSCl crystal and molecular clusters
,” J. Clust. Sci.
21
, 577
–589
(2010
). 44.
Z. S.
Aliev
, M. B.
Babanly
, A. V.
Shevelkov
, D. M.
Babanly
, and J.-C.
Tedenac
, “Phase diagram of the Sb–Te–I system and thermodynamic properties of SbTeI
,” Int. J. Mat. Res.
103
, 290
–295
(2012
). 45.
F. D.
Murnaghan
, “The compressibility of media under extreme pressures
,” Proc. Natl. Acad. Sci. U.S.A.
30
, 244
(1944
). 46.
F.
Birch
, “Finite strain isotherm and velocities for single-crystal and polycrystalline NaCl at high pressures and 300° K
,” J. Geophys. Res.
83
, 1257
, https://doi.org/10.1029/JB083iB03p01257 (1978
). 47.
S.
Zhou
, J.
Long
, and W.
Huang
, “Theoretical prediction of the fundamental properties of ternary bismuth tellurohalides
,” Mat. Sci. Semicon. Proc.
27
, 605
–610
(2014
). © 2022 Author(s). Published under an exclusive license by AIP Publishing.
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