Electronic Supplementary Material (ESI) for Journal of Materials Chemistry C.

This journal is © The Royal Society of Chemistry 2016

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Stability and electronic properties of new inorganic

perovskites from high-throughput ab initio calcula-
tions

Supplementary Information
Sabine Körbel,a,b‡ Miguel A.L. Marques,c,d and Silvana Botti∗a,d

An illustrative binary convex hull for Sn–Cl is shown in panel (a) In Tables ESI-1 to ESI-3 we list the energy above the convex hull,
of Fig. ESI-1, while the ternary phase diagram of Sn–Cl–Rb is Ehull , in eV/atom for each compound, together with the magnetic
displayed in panel (b) of Fig. ESI-1. If a compound is stable with moment µ in units of µB , the indirect and direct band gaps from
respect to decomposition, it lies by definition on the convex hull; PBE and HSE, the effective hole mass in units of the electron mass,
otherwise it lies above the hull. In the binary phase diagram we the modulus of the electric polarization |P| in µC/cm2 , and the
can observe that SnCl lies above the hull. It is therefore unstable, formation energy Ef in eV/atom, for all perovskite compounds
in this case with respect to decomposition into SnCl2 and Sn. On which are within 25 meV/per atom from the convex hull of ther-
the other hand, RbSnCl3 (here in the ilmenite crystal structure) modynamic stability.
lies on the hull of the ternary phase diagram, hence it is stable.
To some extent it is possible to find a relation between the As a side comment, the concept of the effective mass is only valid
possible value for the band-gap and the minimal difference for semiconductors, and although we obtain vanishing effective
in electronegativity between A or B and X elements, ∆ χ = hole masses for the metallic compounds, in reality of course the
min (χ(X) − χ(B), χ(X) − χ(A)). As we can see in Fig. ESI-2, band- electric conductivity of these compounds will be finite. Similarly,
gaps usually increase with ∆ χ, although values are still quite the ferroelectric polarization can only be larger than zero for ma-
scattered. The upper limit of the band gap can approximately be terials with a band gap.
described by the straight line Eg ≤ 10/3∆ χ.
Where available, data for the same composition (not necessar-
Figure ESI-3 shows the dependency of the effective hole mass
ily in the perovskite crystal structure) from databases are also
on the band gap. One may identify a trend to larger effective
included in the tables. The Materials Project database is abbrevi-
masses with larger band gaps for the compounds with direct gaps,
ated as “MP”, the Computational Materials Repository 1 as “CMR”,
whereas for the indirect band gap materials, the scattering is large
and the Open Quantum Materials Database as “OQMD”. The for-
(we can identify the direct band gap materials in the graph as
mation energies in the CMR and most of those in the OQMD are
the cases where direct and indirect band gap fall on top of each
those of the ideal cubic perovskites (space group 221). Since here
other).
we allow for structural distortions which can lower the energy,
our formation energies are often more negative (stronger cohe-
a
sion) than those of the CMR and the OQMD, whereas they usually
Institut für Festkörpertheorie und -optik, Friedrich-Schiller-Universität Jena, Max-
Wien-Platz 1, 07743 Jena, Germany, E-mail: skoerbel@uni-muenster.de are very close to those in the MP database.
b
Institut Lumière Matière, UMR5306 Université Lyon 1-CNRS, Université de Lyon, F-
69622 Villeurbanne Cedex, France
c
Institut für Physik, Martin-Luther-Universität Halle-Wittenberg, D-06099 Halle, Ger- References
many
d
European Theoretical Spectroscopy Facility
‡E-mail: silvana.botti@uni-jena.de 1 https://cmr.fysik.dtu.dk, 2015.

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Table ESI-1 Calculated properties of ABX3 compounds: distance from the convex hull Ehull in eV/atom, magnetic moment µ per five-atom unit cell in
units of the Bohr magneton, indirect and direct band gaps from PBE and HSE06 functionals, effective hole mass m∗h in units of the electron mass,
modulus of the ferroelectric polarization |P| in the LDA, and formation energies Ef in eV/atom from this work and the MP, CMR, and OQMD databases.
New compounds are marked by a •

PBE gap HSE gap |P| Ef

composition Ehull µ/µB ind. direct ind. direct m∗h (LDA) this work MP CMR OQMD
PbTiO3 0.000 0.0 1.85 2.91 3.15 3.95 0.69 66 -2.848 -2.748 -2.187 -2.554
BaNbO3 0.000 0.0 0.00 0.00 0.09 0.31 0.00 1 -3.333 -3.188 -2.544 -3.062
TlZnF3 • 0.000 0.0 4.01 4.09 5.52 5.80 1.95 3 -2.137
CsSnCl3 0.000 0.0 1.00 1.00 1.57 1.57 0.14 1 -1.460 -1.807 -1.719
BaTiO3 0.000 -0.0 2.14 2.64 3.58 4.12 10.57 31 -3.580 -3.506 -2.948 -3.327
KTaO3 0.000 0.0 2.12 2.79 3.39 4.10 2.31 0 -3.151 -3.098 -2.409 -2.967
CsGeI3 0.000 0.0 1.17 1.17 1.48 1.48 0.29 7 -0.854 -0.849 -0.964
NaNbO3 0.000 0.0 2.20 3.15 3.50 4.55 10.97 44 -3.028 -2.85 -2.168 -2.72
KMgF3 0.000 0.0 7.01 7.32 9.28 9.58 3.97 0 -3.291 -3.289 -3.599
SrFeO3 0.000 3.4 0.03 0.08 0.04 1.20 0.00 1 -2.509 -2.333 -1.851
KCdF3 0.000 0.0 3.07 4.48 5.28 6.69 1.13 7 -2.429 -2.455 -2.719
TlMgF3 • 0.000 0.0 4.25 4.29 5.38 5.47 1.81 1 -2.856
RbZnF3 0.000 0.0 3.66 4.79 6.24 7.16 1.27 0 -2.531 -2.534 -2.756
RbCaF3 0.000 0.0 6.38 6.52 9.01 9.11 5.56 0 -3.463 -3.46 -3.772
RbCdF3 0.000 0.0 3.14 4.39 5.36 6.61 1.16 4 -2.446 -2.447 -2.743
RbCaCl3 • 0.000 0.0 4.96 5.22 7.04 7.31 2.61 3 -2.245
RbMnF3 0.000 0.0 1.61 3.57 4.34 6.49 1.34 0 -2.560 -2.758 -2.878
CsNaF3 • 0.000 1.0 -0.01 0.02 -0.01 0.26 0.00 1 -2.176
CsInBr3 • 0.000 0.0 0.03 0.03 0.49 0.49 0.00 1 -1.236
TlCdF3 • 0.000 0.0 3.83 4.22 5.76 5.91 1.17 0 -2.039
RbNiF3 0.000 0.0 0.52 0.76 5.30 5.56 5.55 0 -2.120 -2.233 -2.353
CsTlF3 • 0.000 0.0 0.06 0.06 0.35 0.35 0.00 5 -2.231
CsCaF3 0.000 0.0 6.89 6.94 9.97 9.97 6.85 0 -3.472 -3.469 -3.781
SrVO3 0.000 -0.0 0.02 0.02 0.04 0.04 0.00 1 -3.250 -2.895 -2.416 -2.864
CsPbF3 0.000 0.0 3.07 3.07 4.79 4.79 0.41 12 -2.563 -2.533 -2.828
CsSnBr3 0.000 0.0 0.64 0.64 1.11 1.11 0.11 1 -1.246 -1.249 -1.48
CsCdF3 0.000 0.0 3.26 4.17 5.49 6.37 1.19 0 -2.455 -2.455 -2.753
KZnF3 0.000 0.0 3.67 5.15 6.08 7.51 1.25 0 -2.556 -2.555 -2.852
KTcO3 0.000 0.0 0.01 0.06 0.03 0.13 0.00 2 -2.131 -2.008 -1.878
RbVF3 0.000 0.0 0.63 0.96 3.60 4.36 3.27 1 -2.613 -2.767 -2.908
TlIO3 0.000 0.0 2.63 2.63 4.26 4.26 2.00 47 -1.054 -0.983 -0.883
CsCaCl3 • 0.000 0.0 5.34 5.55 7.08 7.30 2.70 0 -2.290
CsGeBr3 0.000 0.0 1.48 1.48 1.97 1.97 0.24 4 -1.146 -1.14 -1.356
RbMgF3 0.000 0.0 7.03 7.16 9.45 9.55 4.47 0 -3.243 -3.252 -3.562
CsIO3 0.000 0.0 3.12 3.12 4.18 4.18 1.42 35 -1.456 -1.397 -1.291
BaHfO3 0.000 0.0 3.56 3.78 5.16 5.32 2.06 3 -3.852 -3.217 -3.671
CaFeO3 0.000 3.3 0.00 0.09 -0.00 1.41 0.00 2 -2.486 -2.342 -1.821 -2.227
BaZrO3 0.000 0.0 3.12 3.38 4.71 4.92 2.12 8 -3.778 -3.654 -3.133 -3.523
CsInF3 • 0.000 0.0 0.08 0.08 0.36 0.36 0.00 1 -2.438
CsGeCl3 0.000 0.0 2.17 2.17 2.84 2.84 0.32 6 -1.363 -1.708 -1.605
CsCdCl3 0.000 0.0 1.72 2.13 3.06 3.55 1.11 0 -1.478 -1.839 -1.717
CsAgCl3 0.000 0.0 0.06 0.06 0.37 0.37 0.00 1 -1.088 -1.445 -1.343
BaSnO3 0.000 0.0 0.34 0.86 1.97 2.34 1.99 0 -2.679 -2.602 -2.008 -2.49
KCuCl3 0.000 0.0 0.03 0.03 0.04 0.04 0.00 1 -1.087 -1.445 -1.298
KNbO3 0.000 0.0 2.18 3.04 3.52 4.44 2.24 28 -3.047 -2.872 -2.187 -2.741
TlAgCl3 • 0.000 0.0 0.09 0.09 0.39 0.39 0.00 3 -0.657
LaAlO3 0.000 0.0 3.49 3.62 4.84 5.02 1.63 0 -3.794 -3.74 -3.053 -3.607
TlPdF3 • 0.000 0.0 0.06 0.48 0.14 1.04 0.00 4 -1.460
TlAgF3 • 0.000 0.0 0.00 0.00 0.00 0.00 0.00 6 -1.474
CsTlBr3 • 0.000 0.0 0.06 0.06 0.37 0.37 0.00 2 -1.126
RbPdCl3 • 0.000 0.0 0.03 0.52 0.32 1.17 0.00 1 -1.085
CsAgBr3 • 0.000 0.0 0.00 0.00 0.34 0.34 0.00 1 -0.932
SrTiO3 0.000 0.0 1.96 2.47 3.42 3.97 3.78 0 -3.647 -3.569 -3.008 -3.393
TlHgF3 • 0.000 0.0 2.06 3.06 3.86 4.57 11.37 70 -1.571
RbAgBr3 • 0.000 0.0 0.00 0.00 0.38 0.38 0.00 0 -0.896
CsPbBr3 0.000 0.0 2.07 2.07 2.42 2.42 0.26 2 -1.323 -1.333 -1.531
CsCaBr3 0.000 0.0 4.40 4.63 6.09 6.35 2.07 1 -1.999 -2.001 -2.219
CsPbCl3 0.000 0.0 2.48 2.48 2.95 2.95 0.28 2 -1.538 -1.885 -1.775
KWO3 0.001 0.0 0.01 0.01 0.08 0.08 0.00 1 -2.607 -1.83
RbHgF3 0.001 0.0 0.63 2.66 2.59 4.77 0.82 7 -1.963 -1.972 -2.238

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Table ESI-2 Continuation of Table ESI-1

PBE gap HSE gap |P| Ef

composition Ehull µ/µB ind. direct ind. direct m∗h (LDA) this work MP CMR OQMD
KAgBr3 • 0.001 0.0 0.00 0.00 0.40 0.40 0.00 0 -0.866
KAgCl3 • 0.001 0.0 0.00 0.00 0.01 0.01 0.00 0 -1.037
CsHgF3 0.001 0.0 0.70 2.41 2.65 4.51 0.80 4 -1.988 -1.997 -2.271
RbTlF3 • 0.001 0.0 0.05 0.05 0.01 0.01 0.00 0 -2.199
RbIO3 0.001 0.0 2.79 2.79 3.88 3.88 1.48 40 -1.446 -1.389 -1.286
NaMoO3 0.001 0.0 0.00 0.00 0.02 0.02 0.00 0 -2.547 -1.714 -2.29
LaReN3 0.001 0.0 -0.01 -0.01 0.04 0.04 0.00 4 -0.726 -0.442
RbAgCl3 • 0.001 0.0 0.08 0.08 0.39 0.39 0.00 1 -1.063
KAgF3 0.001 0.0 0.03 0.03 0.32 0.54 0.00 2 -1.870 -2.138
KCuF3 0.001 0.0 0.03 0.26 1.76 2.28 0.00 0 -2.099 -2.381 -2.389
TlCuF3 0.002 0.0 0.00 0.15 1.82 2.25 0.00 0 -1.670 -1.911 -1.926
RbCuF3 0.002 0.0 0.04 0.27 1.79 2.20 0.00 1 -2.067 -2.076 -2.358
CsSrCl3 • 0.002 0.0 4.98 5.15 6.29 6.48 3.14 4 -2.300
BaBiO3 0.002 0.0 0.03 0.03 0.25 0.25 0.00 7 -2.284 -2.249 -1.654 -2.117
RbAgF3 0.002 0.0 0.03 0.03 0.02 0.02 0.00 0 -1.882 -2.151 -2.173
CsPdBr3 • 0.002 0.0 0.02 0.49 0.00 0.01 0.00 1 -0.934
RbOsO3 0.002 0.0 0.01 0.01 0.00 0.00 0.00 1 -1.584 -1.405
SrNbO3 0.003 0.0 0.00 0.00 0.08 0.08 0.00 2 -3.346 -3.195 -2.524 -3.061
KMnF3 0.003 0.0 1.31 3.32 4.04 6.23 1.35 3 -2.566 -2.764 -2.882
CsSnF3 • 0.003 0.0 2.67 2.67 4.10 4.10 0.60 3 -2.515
InGeCl3 • 0.004 0.0 2.41 2.41 3.03 3.03 0.53 26 -0.829
NaTcO3 0.004 0.0 0.00 0.08 0.01 0.13 0.00 1 -2.140 -2.0 -1.882
CsSrF3 0.004 0.0 6.19 6.21 8.24 8.24 5.74 6 -3.423 -3.419 -3.715
RbGeBr3 0.004 0.0 1.48 1.48 1.65 1.65 0.25 4 -1.095 -1.105 -1.318
RbInCl3 • 0.004 0.0 0.13 0.13 0.57 0.57 0.00 2 -1.390
RbCrCl3 0.004 4.0 0.01 0.35 0.16 0.83 0.00 0 -1.380 -1.726 -1.619
PbHfO3 0.004 0.0 2.97 3.10 4.50 4.61 1.08 0 -3.078 -3.011 -2.408 -2.847
RbPdBr3 • 0.005 0.0 0.00 0.51 0.01 0.03 0.00 1 -0.912
RbSnBr3 • 0.005 0.0 1.09 1.09 1.10 1.10 0.19 3 -1.197
TlMnF3 • 0.005 0.0 1.37 2.42 3.92 4.78 1.32 0 -2.164
CsScBr3 • 0.005 0.0 0.02 0.02 0.02 0.02 0.00 1 -1.613
NaWO3 0.006 0.0 0.00 0.00 0.01 0.01 0.00 0 -2.603 -2.114 -1.824 -2.419
RbPbF3 0.007 0.0 3.20 3.20 4.80 4.91 0.39 15 -2.525 -2.522 -2.785
KIO3 0.007 0.0 2.48 2.48 3.52 3.52 0.97 47 -1.439 -1.387 -1.277
BaPbO3 0.007 0.0 0.00 0.06 0.64 1.35 0.00 0 -2.166 -2.127 -1.519 -1.989
TlGeF3 • 0.007 -0.0 2.80 3.07 3.99 4.33 1.73 11 -2.014
CsMnF3 0.008 0.0 2.11 3.94 4.67 6.98 1.40 0 -2.528 -2.74 -2.786
TlFeF3 • 0.008 0.0 0.00 0.02 2.51 2.85 0.00 0 -1.891
KCaF3 0.008 0.0 6.13 6.29 8.59 8.71 5.35 8 -3.445 -3.744 -3.748
CsAgF3 0.009 0.0 0.02 0.02 0.02 0.02 0.00 1 -1.881 -2.154 -2.177
CsSnI3 0.009 0.0 0.59 0.59 0.85 0.85 0.12 4 -0.960 -0.964 -1.097
TlCuCl3 • 0.009 0.0 0.04 0.04 0.05 0.05 0.00 0 -0.707
CsCaI3 • 0.010 0.0 3.71 3.99 4.88 5.17 1.54 2 -1.607
KMnCl3 0.010 5.0 1.68 3.58 3.62 5.73 0.67 2 -1.416 -1.809
InSnBr3 0.011 0.0 1.13 1.13 1.58 1.58 0.25 0 -0.741 -0.727
InMnF3 • 0.011 0.0 1.25 2.28 3.81 4.65 1.38 33 -2.065
RbInBr3 • 0.013 0.0 0.03 0.03 0.50 0.50 0.00 2 -1.183
CsSrBr3 • 0.013 0.0 4.18 4.38 5.35 5.58 2.47 4 -2.023
SrCrO3 0.013 0.0 -0.00 0.01 0.14 0.61 0.00 2 -2.880 -2.595 -2.164 -2.565
KGeCl3 • 0.014 0.0 1.48 1.48 2.16 2.16 0.19 5 -1.276
RbCuBr3 • 0.014 0.0 0.00 0.00 0.24 0.24 0.00 1 -0.887
CsTlCl3 • 0.014 0.0 0.00 0.00 0.45 0.45 0.00 1 -1.301
KNiF3 0.016 0.0 0.54 0.78 5.35 5.59 3.46 0 -2.153 -2.256 -2.449
KHgF3 0.016 0.0 0.59 2.79 2.55 4.91 0.85 24 -1.937 -1.944
TlGeCl3 • 0.016 0.0 1.37 1.37 2.02 2.02 0.17 0 -0.893
RbCuCl3 0.016 0.0 0.00 0.00 0.02 0.02 0.00 1 -1.094 -1.45 -1.311
AgCuF3 0.017 0.0 0.00 0.00 0.12 0.12 0.00 4 -1.276 -1.532
InSnCl3 • 0.018 0.0 2.09 2.10 2.71 2.71 0.51 23 -0.937
LiSnCl3 • 0.018 0.0 3.87 3.94 4.87 4.94 5.29 20 -1.322
KMgCl3 0.018 0.0 4.33 4.71 6.05 6.44 1.84 1 -1.889 -2.255 -2.15

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Table ESI-3 Continuation of Table ESI-2

PBE gap HSE gap |P| Ef

composition Ehull µ/µB ind. direct ind. direct m∗h (LDA) this work MP CMR OQMD
PbZrO3 0.019 -0.0 3.05 3.16 4.54 4.65 1.18 0 -3.008 -2.87 -2.316 -2.724
RbMgCl3 0.019 0.0 4.20 4.54 5.76 6.11 1.97 0 -1.908 -2.278 -2.174
NaTaO3 0.019 0.0 2.24 3.00 4.13 4.78 2.06 0 -3.136 -3.088 -2.404 -2.966
InPbCl3 • 0.019 0.0 2.87 2.89 3.69 3.71 0.86 0 -1.023
RbGeI3 0.020 0.0 1.21 1.21 1.35 1.35 0.31 8 -0.799 -0.809 -0.924
RbGeCl3 0.020 0.0 1.73 1.73 2.45 2.45 0.24 5 -1.315 -1.682 -1.576
BaHfS3 • 0.020 0.0 0.71 1.13 1.45 1.93 1.01 7 -1.838
KCaCl3 • 0.020 0.0 4.75 5.04 6.28 6.57 2.55 0 -2.207
RbTlBr3 • 0.021 0.0 0.06 0.06 0.37 0.37 0.00 4 -1.069
RbMnCl3 0.021 0.0 1.67 3.52 3.58 5.56 0.67 1 -1.438 -1.815 -1.703
NaReO3 0.021 0.0 0.00 0.10 0.25 0.46 0.00 1 -2.158 -2.098 -1.606 -1.971
CsInI3 • 0.022 0.0 0.05 0.05 0.35 0.35 0.00 1 -0.944
BaLiF3 0.022 0.0 6.58 6.58 8.64 8.64 3.65 1 -3.489 -3.478 -3.78
CsSeBr3 • 0.022 0.0 0.00 0.07 0.02 0.15 0.00 4 -0.790
RbSnCl3 • 0.022 0.0 1.43 1.43 1.61 1.61 0.22 3 -1.408
KMoO3 0.023 0.0 0.00 0.00 0.07 0.07 0.00 1 -2.545 -1.723 -2.293
CsSrI3 • 0.023 0.0 3.61 3.84 4.74 4.84 1.85 4 -1.646
AgMgF3 • 0.023 0.0 2.03 2.65 4.16 4.83 6.85 3 -2.485
LaWN3 0.023 0.0 0.46 1.37 0.97 2.09 0.93 73 -0.984 -0.564
RbCaBr3 • 0.024 0.0 4.09 4.36 5.76 6.06 2.03 2 -1.947
TlCoF3 • 0.024 0.0 -0.04 -0.01 4.27 4.70 0.00 0 -1.746
KHfO3 0.024 1.0 0.00 0.06 0.05 0.05 0.00 0 -3.018 -2.402 -2.83
RbCdCl3 0.025 0.0 1.77 2.31 3.12 3.74 0.98 2 -1.443 -1.82 -1.693
BaMoO3 0.025 0.2 0.00 0.01 0.00 0.18 0.00 1 -2.864 -2.595 -2.121 -2.632
KCrCl3 • 0.026 4.0 0.01 0.37 0.15 0.87 0.00 0 -1.364
KGeBr3 • 0.026 0.0 1.37 1.38 1.47 1.47 0.22 7 -1.056
LaNiO3 0.026 0.3 0.02 0.29 0.03 0.03 0.00 1 -2.627 -2.378 -1.946
TlAgBr3 • 0.027 0.0 0.03 0.03 0.43 0.43 0.00 9 -0.500
InCaBr3 0.028 0.0 3.49 3.64 4.32 4.47 3.42 22 -1.484 -1.519 -1.737
LaCuO3 0.028 0.0 -0.00 0.42 0.14 1.18 0.00 0 -2.466 -2.44
TlCaF3 • 0.029 0.0 4.47 4.48 6.21 6.25 1.56 27 -3.054
SrSnO3 0.030 -0.0 0.95 1.77 2.78 3.60 1.99 7 -2.684 -2.655 -2.0
SrHfO3 0.030 0.0 3.75 4.07 5.26 5.67 2.01 0 -3.847 -3.831 -3.2 -3.693
LaFeO3 0.030 2.9 -0.02 0.02 0.02 0.02 0.00 1 -2.876 -2.94 -2.152
CsPbI3 0.033 0.0 1.51 1.51 2.04 2.04 0.23 3 -1.021 -1.053
BaZrS3 0.034 0.0 0.56 1.01 1.29 1.81 1.08 0 -1.822 -1.81 -2.008
SrRuO3 0.034 1.9 0.00 0.04 0.00 0.34 0.00 4 -2.270 -2.206 -1.513
LaCoO3 0.034 1.4 0.00 0.02 0.11 0.43 0.00 108 -2.698 -2.64 -1.994
NaOsO3 0.034 0.0 -0.00 -0.00 0.04 0.04 0.00 1 -1.693 -1.518
AgZnF3 0.035 0.0 1.56 2.27 3.86 4.45 1.17 9 -1.729 -1.736
RbSnI3 0.036 0.0 0.47 0.47 0.82 0.82 0.11 3 -0.899 -0.931 -1.061
RbPbBr3 • 0.036 0.0 2.06 2.06 2.40 2.40 0.26 0 -1.263
RbPbCl3 • 0.037 0.0 2.46 2.46 2.92 2.92 0.28 0 -1.480
KCdCl3 0.038 -0.0 1.81 2.39 3.31 3.82 0.92 0 -1.410 -1.813 -1.688
TlNiF3 • 0.038 0.0 0.40 0.69 4.19 4.41 3.29 1 -1.726
RbSrCl3 • 0.038 0.0 4.63 4.83 5.91 6.13 3.08 0 -2.242
AgTaO3 0.039 0.0 1.73 2.23 3.38 3.61 2.07 19 -2.461 -2.427 -1.774
BiNiO3 0.039 0.3 0.00 0.15 0.02 0.83 0.00 54 -1.410 -1.234
TlSnF3 0.040 0.0 2.33 2.70 3.45 3.96 1.25 21 -2.090 -2.363
TlGeBr3 • 0.040 0.0 1.28 1.28 1.28 1.28 0.21 0 -0.683
RbSeBr3 • 0.041 0.0 0.01 0.10 0.01 0.08 0.00 5 -0.747
TlCaCl3 • 0.042 0.0 3.93 4.30 5.12 5.46 2.46 0 -1.824
SrTcO3 0.044 0.0 0.02 0.07 1.82 2.52 0.00 1 -2.578 -2.474 -2.335
RbCaI3 • 0.046 0.0 3.44 3.73 4.40 4.71 1.48 3 -1.548
SrZrO3 0.047 0.0 3.33 3.63 4.86 5.27 2.08 0 -3.757 -3.68 -3.105 -3.535
AgNiF3 • 0.047 2.0 0.56 0.82 3.33 4.36 2.05 2 -1.332
TlCdCl3 0.050 -0.0 1.86 2.57 3.38 3.99 0.87 0 -1.029 -1.433 -1.308
RbSnF3 • 0.052 -0.0 1.95 1.95 3.57 3.58 0.32 3 -2.460
LaCrO3 0.054 3.0 0.25 0.78 2.95 3.71 0.00 8 -3.207 -3.193 -2.494
LaMnO3 0.054 3.5 0.01 0.02 0.32 2.26 0.00 6 -3.089 -3.025 -2.428

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Table ESI-4 Continuation of Table ESI-3

PBE gap HSE gap |P| Ef

composition Ehull µ/µB ind. direct ind. direct m∗h (LDA) this work MP CMR OQMD
KCaBr3 • 0.054 0.0 3.92 4.20 5.11 5.36 1.98 0 -1.906
CaTiO3 0.055 0.0 1.97 2.48 3.44 4.03 2.19 0 -3.589 -3.573 -2.976 -3.396
LaVO3 0.058 1.3 -0.04 0.07 0.26 2.29 0.00 3 -3.363 -3.286 -2.522
RbAuI3 0.059 -0.0 0.00 0.00 0.01 0.01 0.00 1 -0.630 -0.687
CsAuI3 0.059 0.0 0.00 0.00 0.01 0.01 0.00 1 -0.675 -0.73
TlInCl3 • 0.059 0.0 0.13 0.13 0.32 0.32 0.00 19 -0.966
RbPbI3 0.060 0.0 1.58 1.58 2.01 2.01 0.23 3 -0.958 -1.017
LaTiO3 0.061 -0.0 0.00 0.00 0.03 0.10 0.00 10 -3.684 -3.657 -2.973 -3.494
CsAuBr3 0.061 0.0 0.03 0.03 0.28 0.28 0.00 1 -0.856 -0.912
CsAuCl3 0.063 0.0 0.00 0.00 0.25 0.25 0.00 1 -0.986 -1.408 -1.304
BaZrSe3 • 0.072 -0.0 0.25 0.77 1.01 1.44 0.82 0 -1.586
CaTcO3 0.078 0.1 0.00 0.00 2.09 2.71 0.00 0 -2.496 -2.356
LaGaO3 0.080 0.0 3.30 3.58 4.77 5.08 1.98 9 -3.131 -3.116 -2.408
KCoF3 0.099 3.0 0.00 0.01 4.02 4.71 0.00 1 -2.166 -2.503
RbCoF3 0.119 3.0 -0.00 0.00 4.03 4.60 0.00 2 -2.137 -2.382
YNiO3 0.137 0.2 0.01 0.41 0.02 0.02 0.00 31 -2.497 -2.382 -2.392
TlNiO3 0.149 0.0 0.00 0.00 -0.00 -0.00 0.00 1 -0.975 -0.87
YReN3 0.149 0.0 0.00 0.00 0.12 0.12 0.00 0 -0.554 -0.354
SrCoO3 0.149 2.5 0.00 0.02 0.28 0.88 0.00 2 -2.202 -1.979 -1.565

Cl Sn 11
0.0 HSE indirect
HSE direct
10 10/3 ∆ χ
−0.2
Ef [eV/atom]

9
−0.4
SnCl
−0.6 Ehull 8

−0.8 7
SnCl4
SnCl2
−1.0
Eg (eV)

0.0 0.2 0.4 0.6 0.8 1.0 6

x in Snx Cl1−x
5

Cl 0.0 4

-0.3 3
SnCl4

SnCl2 -0.6 2
Ef (eV/atom)

Rb2 SnCl6
RbSnCl3 1
RbCl SnCl -0.9
0
-1.2 0.5 1.0 1.5 2.0 2.5 3.0 3.5
∆χ
-1.5
Fig. ESI-2 (Color online) band gaps of the stable perovskites vs
-1.8 electronegativity difference between cations and X anion (see text).

Rb RbSn RbSn3 Sn

Fig. ESI-1 (Color online) Panel (a): Formation energy (in units of
eV/atom) as a function of composition for the system Sn–Cl. Panel (b):
Projected formation energy (in units of eV/atom) as a function of
composition for the system Rb–Sn–Cl. The color map represents the
formation energy E f . Stable compounds (those on the convex hull) are
connected by lines. For the sake of readability, most unstable or
metastable phases are omitted.

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 20
PBE indirect
PBE direct

15
m∗h

10

0
-1.0 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0
Eg (eV)

Fig. ESI-3 (Color online) Effective hole mass m∗h vs. band gap for the
stable perovskites.

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