Vacancy ordered halide perovskites have been extensively investigated as promising lead-free alternatives to halide perovskites for various opto-electronic applications. Among these, Cs2TiBr6 has been reported as a stable absorber with interesting electronic and optical properties, such as a bandgap in the visible, and long carrier diffusion lengths. Yet, a thorough theoretical analysis of the exhibited properties is still missing in order to further assess its application potential from a material's design point of view. In this Letter, we perform a detailed analysis for the established Ti-based compounds and investigate the less-known materials based on Zr. We discuss in detail their electronic properties and band symmetries, highlight the similarity between the materials in terms of properties, and reveal limits for tuning electronic and optical properties within this family of vacancy ordered double perovskites that share the same electron configuration. We also show the challenges to compute accurate and meaningful quasi-particle corrections at the GW level. Furthermore, we address their chemical stability against different decomposition reaction pathways, identifying stable regions for the formation of all materials, while probing their mechanical stability employing phonon calculations. We predict that Cs2ZrI6, a material practically unexplored to date, shall exhibit a quasi-direct electronic bandgap well within the visible range, the smallest charge carrier effective masses within the Cs2BX6 (B = Ti, Zr; X = Br, I) compounds, and a good chemical stability.

1.
J.
Jeong
,
M.
Kim
,
J.
Seo
,
H.
Lu
,
P.
Ahlawat
,
A.
Mishra
,
Y.
Yang
,
M. A.
Hope
,
F. T.
Eickemeyer
,
M.
Kim
,
Y. J.
Yoon
,
I. W.
Choi
,
B. P.
Darwich
,
S. J.
Choi
,
Y.
Jo
,
J. H.
Lee
,
B.
Walker
,
S. M.
Zakeeruddin
,
L.
Emsley
,
U.
Rothlisberger
,
A.
Hagfeldt
,
D. S.
Kim
,
M.
Grätzel
, and
J. Y.
Kim
,
Nature
592
,
381
(
2021
).
2.
See http://www.nrel.gov/ for “
Best Research-Cell Efficiencies
” (
2021
).
3.
J.
Cui
,
Y.
Liu
,
Y.
Deng
,
C.
Lin
,
Z.
Fang
,
C.
Xiang
,
P.
Bai
,
K.
Du
,
X.
Zuo
,
K.
Wen
,
S.
Gong
,
H.
He
,
Z.
Ye
,
Y.
Gao
,
H.
Tian
,
B.
Zhao
,
J.
Wang
, and
Y.
Jin
,
arXiv:2006.07611
(
2020
).
4.
Z.
Zhang
,
Y.
Liang
,
H.
Huang
,
X.
Liu
,
Q.
Li
,
L.
Chen
, and
D.
Xu
,
Angew. Chem., Int. Ed.
58
,
7263
(
2019
).
5.
L.
Li
,
X.
Liu
,
H.
Zhang
,
B.
Zhang
,
W.
Jie
,
P. J.
Sellin
,
C.
Hu
,
G.
Zeng
, and
Y.
Xu
,
ACS Appl. Mater. Interfaces
11
,
7522
(
2019
).
6.
F.
Giustino
and
H. J.
Snaith
,
ACS Energy Lett.
1
,
1233
(
2016
).
7.
S.
Shao
,
J.
Liu
,
G.
Portale
,
H.-H.
Fang
,
G. R.
Blake
,
G. H.
ten Brink
,
L. J. A.
Koster
, and
M. A.
Loi
,
Adv. Energy Mater.
8
,
1702019
(
2018
).
8.
L.
He
,
H.
Gu
,
X.
Liu
,
P.
Li
,
Y.
Dang
,
C.
Liang
,
L. K.
Ono
,
Y.
Qi
, and
X.
Tao
,
Matter
2
,
167
(
2020
).
9.
N. K.
Noel
,
S. D.
Stranks
,
A.
Abate
,
C.
Wehrenfennig
,
S.
Guarnera
,
A.-A.
Haghighirad
,
A.
Sadhanala
,
G. E.
Eperon
,
S. K.
Pathak
,
M. B.
Johnston
,
A.
Petrozza
,
L. M.
Herz
, and
H. J.
Snaith
,
Energy Environ. Sci.
7
,
3061
(
2014
).
10.
F.
Hao
,
C. C.
Stoumpos
,
D. H.
Cao
,
R. P. H.
Chang
, and
M. G.
Kanatzidis
,
Nat. Photonics
8
,
489
(
2014
).
11.
G.
Volonakis
,
M. R.
Filip
,
A. A.
Haghighirad
,
N.
Sakai
,
B.
Wenger
,
H. J.
Snaith
, and
F.
Giustino
,
J. Phys. Chem. Lett.
7
,
1254
(
2016
).
12.
A. H.
Slavney
,
T.
Hu
,
A. M.
Lindenberg
, and
H. I.
Karunadasa
,
J. Am. Chem. Soc.
138
,
2138
(
2016
).
13.
G.
Volonakis
,
A. A.
Haghighirad
,
R. L.
Milot
,
W. H.
Sio
,
M. R.
Filip
,
B.
Wenger
,
M. B.
Johnston
,
L. M.
Herz
,
H. J.
Snaith
, and
F.
Giustino
,
J. Phys. Chem. Lett.
8
,
772
(
2017
).
14.
B.
Chabot
and
E.
Parthé
,
Acta Crystallogr., Sect. B
34
,
645
(
1978
).
15.
F.
Bai
,
Y.
Hu
,
Y.
Hu
,
T.
Qiu
,
X.
Miao
, and
S.
Zhang
,
Sol. Energy Mater. Sol. Cells
184
,
15
(
2018
).
16.
X.
Qiu
,
B.
Cao
,
S.
Yuan
,
X.
Chen
,
Z.
Qiu
,
Y.
Jiang
,
Q.
Ye
,
H.
Wang
,
H.
Zeng
,
J.
Liu
, and
M.
Kanatzidis
,
Sol. Energy Mater. Sol. Cells
159
,
227
(
2017
).
17.
N.
Sakai
,
A. A.
Haghighirad
,
M. R.
Filip
,
P. K.
Nayak
,
S.
Nayak
,
A.
Ramadan
,
Z.
Wang
,
F.
Giustino
, and
H. J.
Snaith
,
J. Am. Chem. Soc.
139
,
6030
(
2017
).
18.
A. E.
Maughan
,
A. M.
Ganose
,
M. M.
Bordelon
,
E. M.
Miller
,
D. O.
Scanlon
, and
J. R.
Neilson
,
J. Am. Chem. Soc.
138
,
8453
(
2016
).
19.
H. A.
Evans
,
D. H.
Fabini
,
J. L.
Andrews
,
M.
Koerner
,
M. B.
Preefer
,
G.
Wu
,
F.
Wudl
,
A. K.
Cheetham
, and
R.
Seshadri
,
Inorg. Chem.
57
,
10375
(
2018
).
20.
M.
Chen
,
M.-G.
Ju
,
A. D.
Carl
,
Y.
Zong
,
R. L.
Grimm
,
J.
Gu
,
X. C.
Zeng
,
Y.
Zhou
, and
N. P.
Padture
,
Joule
2
,
558
(
2018
).
21.
G.
Engel
,
Naturwissenschaften
21
,
704
(
1933
).
22.
A.
Kaltzoglou
,
M.
Antoniadou
,
A. G.
Kontos
,
C. C.
Stoumpos
,
D.
Perganti
,
E.
Siranidi
,
V.
Raptis
,
K.
Trohidou
,
V.
Psycharis
,
M. G.
Kanatzidis
, and
P.
Falaras
,
J. Phys. Chem. C
120
,
11777
(
2016
).
23.
M.-G.
Ju
,
M.
Chen
,
Y.
Zhou
,
H. F.
Garces
,
J.
Dai
,
L.
Ma
,
N. P.
Padture
, and
X. C.
Zeng
,
ACS Energy Lett.
3
,
297
(
2018
).
24.
A. E.
Maughan
,
A. M.
Ganose
,
D. O.
Scanlon
, and
J. R.
Neilson
,
Chem. Mater.
31
,
1184
(
2019
).
25.
J.
Euvrard
,
X.
Wang
,
T.
Li
,
Y.
Yan
, and
D. B.
Mitzi
,
J. Mater. Chem. A
8
,
4049
(
2020
).
26.
A.
Abfalterer
,
J.
Shamsi
,
D. J.
Kubicki
,
C. N.
Savory
,
J.
Xiao
,
G.
Divitini
,
W.
Li
,
S.
Macpherson
,
K.
Gałkowski
,
J. L.
MacManus-Driscoll
,
D. O.
Scanlon
, and
S. D.
Stranks
,
ACS Mater. Lett.
2
,
1644
(
2020
).
27.
D. H.
Guthrie
and
J. D.
Corbett
,
Inorg. Chem.
21
,
3290
(
1982
).
28.
D.
Sinram
,
C.
Brendel
, and
B.
Krebs
,
Inorg. Chim. Acta
64
,
L131
(
1982
).
29.
D.
Kong
,
D.
Cheng
,
X.
Wang
,
K.
Zhang
,
H.
Wang
,
K.
Liu
,
H.
Li
,
X.
Sheng
, and
L.
Yin
,
J. Mater. Chem. C
8
,
1591
(
2020
).
30.
J.
Heyd
,
G. E.
Scuseria
, and
M.
Ernzerhof
,
J. Chem. Phys.
118
,
8207
(
2003
).
31.
X.
Mao
,
L.
Sun
,
T.
Wu
,
T.
Chu
,
W.
Deng
, and
K.
Han
,
J. Phys. Chem. C
122
,
7670
(
2018
).
32.
G.
Volonakis
,
A. A.
Haghighirad
,
H. J.
Snaith
, and
F.
Giustino
,
J. Phys. Chem. Lett.
8
,
3917
(
2017
).
33.
G.
Volonakis
,
N.
Sakai
,
H. J.
Snaith
, and
F.
Giustino
,
J. Phys. Chem. Lett.
10
,
1722
(
2019
).
34.
J.
Leveillee
,
G.
Volonakis
, and
F.
Giustino
,
J. Phys. Chem. Lett.
12
,
4474
(
2021
).
35.
Y.
Cai
,
W.
Xie
,
H.
Ding
,
Y.
Chen
,
K.
Thirumal
,
L. H.
Wong
,
N.
Mathews
,
S. G.
Mhaisalkar
,
M.
Sherburne
, and
M.
Asta
,
Chem. Mater.
29
,
7740
(
2017
).
37.
D.
Sangalli
,
A.
Ferretti
,
H.
Miranda
,
C.
Attaccalite
,
I.
Marri
,
E.
Cannuccia
,
P.
Melo
,
M.
Marsili
,
F.
Paleari
,
A.
Marrazzo
 et al,
J. Phys.
31
,
325902
(
2019
).
38.
C. E.
Patrick
and
F.
Giustino
,
J. Phys.
24
,
202201
(
2012
).
39.
M.
Salluzzo
,
J. C.
Cezar
,
N. B.
Brookes
,
V.
Bisogni
,
G. M.
De Luca
,
C.
Richter
,
S.
Thiel
,
J.
Mannhart
,
M.
Huijben
,
A.
Brinkman
,
G.
Rijnders
, and
G.
Ghiringhelli
,
Phys. Rev. Lett.
102
,
166804
(
2009
).
40.
C.
Persson
,
Y.-J.
Zhao
,
S.
Lany
, and
A.
Zunger
,
Phys. Rev. B
72
,
035211
(
2005
).
41.
A.
Jain
,
S. P.
Ong
,
G.
Hautier
,
W.
Chen
,
W. D.
Richards
,
S.
Dacek
,
S.
Cholia
,
D.
Gunter
,
D.
Skinner
,
G.
Ceder
, and
K. A.
Persson
,
APL Mater.
1
,
011002
(
2013
).

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