Steric engineering of metal-halide perovskites with tunable optical band gaps

Abstract

Owing to their high energy-conversion efficiency and inexpensive fabrication routes, solar cells based on metal-organic halide perovskites have rapidly gained prominence as a disruptive technology. An attractive feature of perovskite absorbers is the possibility of tailoring their properties by changing the elemental composition through the chemical precursors. In this context, rational in silico design represents a powerful tool for mapping the vast materials landscape and accelerating discovery. Here we show that the optical band gap of metal-halide perovskites, a key design parameter for solar cells, strongly correlates with a simple structural feature, the largest metal-halide-metal bond angle. Using this descriptor we suggest continuous tunability of the optical gap from the mid-infrared to the visible. Precise band gap engineering is achieved by controlling the bond angles through the steric size of the molecular cation. On the basis of these design principles we predict novel low-gap perovskites for optimum photovoltaic efficiency, and we demonstrate the concept of band gap modulation by synthesising and characterising novel mixed-cation perovskites.

ARTICLE

Received 6 Mar 2014 | Accepted 5 Nov 2014 | Published 15 Dec 2014

DOI: 10.1038/ncomms6757

Steric engineering of metal-halide perovskites with tunable optical band gaps

Marina R. Filip1, Giles E. Eperon2, Henry J. Snaith2 & Feliciano Giustino1

Owing to their high energy-conversion efciency and inexpensive fabrication routes, solar cells based on metal-organic halide perovskites have rapidly gained prominence as a disruptive technology. An attractive feature of perovskite absorbers is the possibility of tailoring their properties by changing the elemental composition through the chemical precursors. In this context, rational in silico design represents a powerful tool for mapping the vast materials landscape and accelerating discovery. Here we show that the optical band gap of metal-halide perovskites, a key design parameter for solar cells, strongly correlates with a simple structural feature, the largest metalhalidemetal bond angle. Using this descriptor we suggest continuous tunability of the optical gap from the mid-infrared to the visible. Precise band gap engineering is achieved by controlling the bond angles through the steric size of the molecular cation. On the basis of these design principles we predict novel low-gap perovskites for optimum photovoltaic efciency, and we demonstrate the concept of band gap modulation by synthesising and characterising novel mixed-cation perovskites.

1 Department of Materials, University of Oxford, Parks Road, Oxford OX1 3PH, UK. 2 Department of Physics, University of Oxford, Clarendon Laboratory, Parks Road, Oxford OX1 3PU, UK. Correspondence and requests for materials should be addressed to F.G. (email: mailto:[email protected]

Web End [email protected] ).

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Hybrid organicinorganic perovskites14 recently surged to worldwide attention following the report of highly efcient solar cells based on methylammonium lead

halides58. In fact, within less than 2 years of development, the photovoltaic energy-conversion efciency of these devices increased from the initial 10.9% (ref. 5) to the current record of17.9% (NREL certied) and 19.3% (uncertied)9. This impressive trend fuelled the expectation that perovskite photovoltaics may soon revolutionize the solar energy landscape.

Given the unusually long lifetimes of the photoexcited carriers1012 and the relatively low optical gap13,14, it has been proposed that the perovskite layer may act both as the light absorber and as the electron and hole transporter15, similarly to bulk semiconductor solar cells. Within this scenario, it is expected that the energy-conversion efciency can be increased by following the standard SchockleyQueisser analysis, that is by reducing the optical band gap to values near 1.31.4 eV (ref. 16).

Substantial efforts are currently underway to optimize these solar cells by modifying the metalhalide network or the organic cation13,14,1723. A major challenge in this research area is that, on the experimental front, the structural, electronic and optical properties of metal-organic perovskites are very sensitive to processing conditions. Similarly, computational modelling studies appear sensitive to the level of theory and calculation details. This state of affairs suggests that it may be convenient to shift the focus from the investigation of a few prototypical perovskites to global searches relying on rational design approaches.

In this work we propose that, instead of modifying the metal halide network as already conducted in refs 13,14, it could be advantageous to start from MA-PbI3 (MA CH3NH3) and

modify its electronic and optical properties without altering the PbI3 network. This strategy would allow us to investigate potential improvements while retaining highly desirable features such as long carrier lifetimes10,12. In the following, using a combination of geometric arguments and rst-principles calculations, we demonstrate that it should indeed be possible to modulate the optical gap of lead-iodide perovskites over almost an electronvolt by acting on the PbIPb bond angles in the PbI3 network. These angles, in turn, can be tailored using cations of different sizes, without altering the metalhalide chemistry.

ResultsPlatonic model of metal-halide perovskites. MA-PbI3 belongs to the family of perovskites of chemical formula ABX3. The simplest possible ABX3 perovskite consists of a high-symmetry cubic structure belonging to the space group Pm 3m, as shown in Fig. 1a (ref. 24). In this structure the halogen atoms X I occupy the

vertices of regular corner-sharing BX6 octahedra, while the divalent metal atoms B Pb sit at the centres of the octahedra.

The smallest volume enclosed by neighbouring octahedra denes a cuboctahedral cavity and hosts the monovalent cation A CH3NH3. All the other possible perovskite structures can

be imagined as obtained by rotating or distorting the BX6 octahedra, displacing the B metal atoms off-centre and rotating the A cations within the cuboctahedral cavity24.

Figure 1b shows the electronic band structure of MA-PbI3,

which represents the starting point of our investigation. Here we see that the electronic states at the top of the valence bands are of halide p-character, while those at the bottom of the conduction band are mainly derived from the metal p states. At the same time the electronic states associated with the cation dene bonding and antibonding bands arranged symmetrically around the band gap and located several electronvolts away from the band edges. An analysis of the electronic charge density shows that, as expected, the cation is singly ionized, and the PbI3 network is negatively

charged2527. These observations suggest that the electronic structure of these metal-organic perovskites may be described by removing the cation from the structural model and compensating the negative charge of the PbI3 network using a positive background. Figure 1b shows that the band structure obtained within this approximation is in good agreement with that from a complete calculation. The removal of the cation is especially useful since it eliminates the complications associated with the observed orientational disorder13,17,28,29. Another important observation can be made by inspecting X-ray diffraction data, as reported for example in ref. 17. In fact, from the structural parameters reported in that work we deduce that the PbI bond lengths are extremely regular, the largest relative deviation from the average value of 3.18 being 0.1%. Furthermore, the diagonals of the PbI6 octahedra are almost perpendicular to each other, the maximum deviation from right angles being of 4. Therefore, to a good approximation the PbI6 octahedra may be considered as Platonic solids carrying the full Oh symmetry.

On the basis of these considerations we set to build a Platonic model of metal-halide perovskites, consisting of regular corner-sharing PbI6 octahedra and no cation, as shown in Fig. 1d. In order to construct our model we start from a single regular octahedron in an orthorhombic unit cell17, with one diagonal parallel to the c axis, and the four perpendicular edges parallel to the axes a and b. In the reference frame of the octahedron this diagonal and its perpendicular edges dene the apical and equatorial directions, respectively. Within this model, the most general perovskite structure is obtained by three successive rotations around c, a and c again using the standard Euler angles30, as shown in Fig. 1c: the spinning c around the apical direction, the tilt y around the a axis and the precession f around the c axis. After these rotations, the location and orientation of all the remaining octahedra in the orthorhombic unit cell are completely determined by the corner-sharing connectivity, the metal-halide bond length and the periodicity of the crystal structure. The details of this geometric construction are given in the Methods.

An immediate result of our construction is that the only way to ensure corner-sharing connectivity is by having a vanishing spinning angle c. This leaves us with only two independent angular parameters, y and f, which refer to a spherical system of coordinates clamped on the crystallographic unit cell. It is convenient to make a change of variables to intrinsic angular parameters that are independent on the choice of the unit cell. To this end we express y and f in terms of the metal-halidemetal bond angles aa and ae, as indicated in Fig. 1d. aa denotes the PbIPb bond angles along the apical direction and ae those along the equatorial direction. The relation between these intrinsic angles and the Euler angles is given in the Methods.

At this point the atomic structure of the Platonic perovskite model is uniquely determined by the choice of two metalhalide metal bond angles and the metalhalide bond length. Given that the effect of bond length variations on the electronic and optical properties of these systems has been studied in detail, both theoretically27 and experimentally13, our geometric analysis clearly directs attention to the role of the two inequivalent PbIPb angles.

Band gap and metalhalidemetal bond angle. In Fig. 2 we show the band gap of the Platonic model calculated using density functional theory (DFT) as a function of the apical and equatorial bond angles aa and ae. For deniteness we set the PbI bond length to the average value measured in ref. 17. The incomplete coverage of the parameter space in Fig. 2 reects the fact that only certain pairs of apical and equatorial angles are compatible with

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6757 ARTICLE

5

4

Total

I-p

Pb-p

Pb-s

Cation

3

2

Energy (eV)

1

0

1

2

3

c

4

b

5

a

Z Z

c

O4

[afii9835]

O3

X15

[p10]

[afii9852]

X12

O4

X13

b

O3

[afii9825]a

[afii9825]e

O1 O2

X14

C1

O2

O1

a

c

X11

X16

b a

Figure 1 | Platonic model of metalhalide perovskites. (a) Ball-and-stick representation of MAPbI3 in the high-temperature cubic phase: the dark spheres inside the octahedra represent Pb atoms, the red spheres at the octahedral corners are I atoms and the molecule inside the cuboctahedral cavity is

CH3NH3. (b) DFT scalar-relativistic electronic band structure and partial density of states of MAPbI3 in the low-temperature orthorombic phase.

In the band structure plot we compare the electronic structure of MAPbI3 with (left) or without (right) the cation. The density of states shows that the electronic states associated with the cation are located far from the band gap. The top of the valence band is derived from I-5p states and, to a smaller extent, the Pb-6s states. The bottom of the conduction band is derived primarily from Pb-6p and I-5p states. The calculated band gap is direct at G.

(c) Schematic representation of the Euler angles dening the rotation of the Platonic octahedron: tilt (y), spinning c

and precession (f). The convention

for labelling the corners of the octahedron is indicated, together with the crystallographic axes. (d) Schematic representation of the orthorhombic unit cell considered in this work consisting of four inequivalent octahedra, O1O4 (dark blue) and their periodic replicas O1 O4 (light blue). The labelling

of the corners follows the same convention indicated in c. The intrinsic metalhalidemetal bond angles are highlighted: apical angle (aa) and

equatorial angle (ae). The geometric properties of this model are derived in the Methods section.

the corner-sharing connectivity, as discussed in the Methods. The extremal parameters of this map are, on the one side, aa

ae

180 (bottom left corner), corresponding to the most symmetric cubic perovskite structure with collinear PbIPb bonds. On the other side we have aa ae 120 (top right corner),

which we have been chosen by considering a limiting structure where the shortest distance between iodine atoms belonging to different octahedra matches the I2 bond length (aa 0 and

ae

126).

The variation of the angular coordinates in Fig. 2 clearly induces a substantial modulation of the band gap, from the top of the mid-infrared (1.1 eV) to the beginning of the visible spectrum(1.9 eV). This trend is in line with earlier calculations on simpler two-dimensional (2D) Sn-I perovskites for solution-processable electronics31.

The qualitative trend shown in Fig. 2 can be interpreted using elementary tight-binding arguments. If we consider for deniteness the bottom of the conduction band at G, which is most affected by bond angles, in the case of aa ae 180 there are

three degenerate electronic states derived from the 6p orbitals of Pb (without considering spinorbit coupling for simplicity; this coupling is fully included in all our nal results presented in Fig. 3b). It is intuitive that the energy of these states results mainly from pps bonding integrals since all the Pb-I bonds are

collinear32. By moving away from the bottom left corner, the degeneracy is lifted as the bond integrals acquire ppp components weighted by the angles aa and ae. Both components tend to raise the energy levels; therefore, the conduction band bottom results from the competition between the antibonding orbitals with the lowest energy along the apical or the equatorial direction. This is consistent with the approximate symmetry of the map in Fig. 2 with respect to the line corresponding to aa ae. More

importantly, this reasoning suggests that the band gap of the Platonic perovskite model is governed by the largest PbIPb bond angle in the metalhalide network, consistent with the trend in Fig. 2. This relation between band gap and bond angles holds unchanged when considering fully relativistic calculations including spinorbit corrections. In fact, as shown in Supplementary Fig. 1, relativistic effects induce a large but slowly varying red shift of 0.81.1 eV across the family of compounds considered in this work. For the sake of completeness we also checked that excitonic effects play only a minor role, with exciton-binding energies never exceeding 80 meV as shown by Supplementary Fig. 2. Details on the calculation of exciton binding energies are given in the Methods, and the results are discussed in the Supplementary Note 1.

After taking into account the presence of the cation and the variations in the Pb-I bond lengths and PbIPb angles, the

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1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9

Na

Li

K

Rb

PH4

Cs

NH4

AsH4

CH3NH3

Band gap (eV)

Apical bond angle ()

180

170 170 150 140 130 120

120

1.3 1.4 1.5

1.6 1.7

1.8

130

Equatorial bond angle ()

140

150

160

170

180

PF4

CH3AsH3

SbH4

(CH3)2 NH2

(CH3)2 PH2

CH3PH3

CH(NH2)2

CH3SbH3

NCI4

Figure 2 | Mapping the band gap landscape of metal-halide perovskites. (a) Two-dimensional map of the DFT band gap of the Platonic model of PbI3-based perovskites as a function of the apical and equatorial metalhalidemetal bond angles. The PbI bond length is set to the experimental value for

MA-PbI3 (ref. 17). The angles aa and ae are indicated in Fig. 1d. The calculations for the Platonic model were performed within scalar-relativistic DFT (fully relativistic calculations are shown in Fig. 3b, see Methods). The dashed line at 45 is a guide to the eye and shows the approximate symmetry of the map with respect the the exchange of the apical and equatorial angles. The dark discs represent the angular coordinates (aa, ae) of realistic models of

PbI3-based perovskites including the cation (indicated by the chemical formula), with structures fully optimized within DFT. The apical and equatorial angles are the averages among all the inequivalent angles of the same type. The size of each circle represents the deviation of the PbI bond length from that of MAPbI3 (3.18 ). This quantity is displayed because the metalhalide bond length has a small but non-negligible effect on the band gap, which we quantify as a linear shift of B3 eV/ (refs 27,31). For the same angular coordinates, the band gap difference between the largest and the smallest circle in the gure is 0.2 eV. The white discs correspond to perovskites already synthesized13,17,18. This map shows that the band gap can be modulated over

a much wider range than currently possible. (b,c) Atomistic models of the hypothetical metal-halide perovskites identied in this work exhibiting the smallest (LiPbI3) and the largest (NCl4PbI3) metalhalidemetal bond angles, respectively.

calculated band gaps deviate from the idealized predictions in Fig. 2 by 0.10.3 eV (see Fig. 3 and discussion below). Nonetheless, the general trend, which spans a range of up to 1 eV, is robust. This picture is also conrmed by relativistic GW calculations on a few selected compounds, as shown in Supplementary Fig. 4. The trend identied here suggests that in order to make low-gap perovskites for optimum photovoltaic efciency we need to engineer structures with minimal octahedral tilt. On the other hand, in order to make large-gap perovskites for light-emitting diodes operating in the visible, we need to design structures with maximum tilt. The remaining question is how the tilt angle can be controlled.

Controlling metalhalidemetal bond angles via the steric size of the cation. The PbIPb bond angles dene the volume of the cuboctahedral cavity; therefore, it is intuitive that the use of larger cations may lead to values of aa and ae closer to straight angles33.

In the search for such cations we perform DFT calculations for existing structures as well as for many hypothetical structures not considered hitherto, including full structural optimizations and spinorbit interactions, in the presence of the cation (see Methods). In order to relate these structures and their properties to the predictions of the Platonic model, we consider the average values of the PbIPb bond angles and of the PbI bond length over a crystalline unit cell. These values are used as the coordinates needed for locating each structure on the map of Fig. 2.

Previously reported cations are methylammonium CH3NH3 (ref. 17), formamidinium CH2NH22 (refs 13,18), the alkali

metal Cs 18 (synthesised) and ammonium NH4 (refs 3436)

(proposed). As shown in Fig. 2 all these cations cluster around the centre of the map; therefore, they are not expected to yield a signicant modulation of the band gap. In line with this result their measured optical absorption onsets are very similar, within0.25 eV (refs 13,18).

In order to explore a wider portion of the map we consider four

different families of cations generated from those above. The rst family consists of secondary, tertiary and quaternary ammonium cations, namely di-, tri- and tetra-methylammonium. These are large molecules obtained by replacing hydrogen atoms bonded to the N atom with methyl groups. The second family is generated from ammonium by descending the pnictogen column in the periodic table, that is by substituting N for P, As or Sb. Members of this family include phosphonium PH4

, arsonium AsH4

,

stibonium SbH4

, and similarly the methylammonium analo

gues CH3PH3 , CH3AsH3 and CH3SbH3 . The third family of cations that we consider is obtained by replacing hydrogen in ammonium by halogen atoms, and possibly nitrogen by another pnictogen: in this group we have NF4 , NCl4 , PF4 , and PCl4 .

The fourth and nal family simply consists of the alkali metals Li , Na , K and Rb . In total, we consider 22 structures, including 18 hypothetical compounds not reported to date.

In order to quantify the steric size of each cation, we use the radius of the sphere that contains 95% of the DFT electron density. This choice ensures that the steric radii of the alkali metals are in agreement with their standard ionic radii37. For completeness the calculated steric sizes are reported in Supplementary Table 1. Figure 3 shows that the steric radii of the cations considered in this work span a wide range, from 0.7 (Li ) to 2:9A PCl4

.

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NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6757 ARTICLE

180

1.0

170 160

Bond angle ()

0.8

Bond gap (ev)

2.01.81.61.4

1.2 DFT DFT+SOC

Platonic model

1.0 0.0 130 140 150

Maximum bond angle ()

1.53

0.6

1501401301200.5 1.0 1.5 2.5 3.0

2.0

Steric size ()

0.4

160 170

0.2

1.44

1.48

1.49

1.52

1.56

1.26

0.99

NCI 4

1.32

1.31

1.33

1.40

AsH 4

SbH 4

PF 4

CH 3PH 3

CH 2N 2H 4

PH 4

NH 2

CH 3NH 3

C2H 6

CH 3SbH 3

CH 3AsH 3

C2H 6

NH 4

Cs

1.58

1.61

1.65

1.70

1.72

1.79

PH 2

Rb

K

Na

Li

Figure 3 | Tuning the band gap of metal-halide perovskites via the steric size of the cation. (a) Correlation between the apical and equatorial bond angles of PbI3-based perovskites and the steric radius of the cation (discs). As the size of the cation increases the metalhalidemetal bonds (see Fig. 1d)

tend to become collinear. A linear least-square t to the data (straight line) yields a slope of 18/. (b) Correlation between the DFT band gap and the largest metalhalidemetal bond angle in the structure. We show calculations for the Platonic model (circles) and fully optimized structures within scalar-relativistic (grey discs) and fully relativistic (blue discs) DFT. The arrows point to the scales corresponding to each set of data. The signicant data dispersion at large angles is due to the distortions of the octahedra. The calculations based on the Platonic model include the effect of the average PbI bond length on the band gap, as discussed in Fig. 2. (c) Calculated band gaps (in eV) of all the PbI3-based perovskites considered in this work.

The band gaps were obtained after full structural optimization within scalar relativistic DFT (see Methods).

Our structural optimizations indicate that for some of the large cations the three-dimensional (3D) perovskite network is signicantly distorted. This is in line with previous studies showing that large molecular cations determine a reorganization of the 3D perovskite network into a 2D layered structure38,39. These large molecules include tertiary and quaternary methylammonium cations, as well as the tetrauoride NF4 and the tetrachloride PCl4 . As these structures depart substantially from the 3D metalhalide network considered in this work, a separate analysis would be required. Accordingly, we do not consider them further.

Figure 3a shows that the largest PbIPb angles correlate strongly with the steric size of the cation (Spearman correlation 88%), in line with our initial expectation. The newly proposed structures span a range of angles from 130 to 170, thereby covering a much wider portion of the band gap map in Fig. 2 than presently possible. In addition, Fig. 3b shows that, in agreement with the predictions of the Platonic model, the band gap correlates strongly with the largest PbIPb angle in the unit cell (Spearman correlation 91%). For completeness in Fig. 3b we report the band gaps obtained from this model as well as those calculated using the fully optimized structures within fully relativistic DFT calculations. The scatter of the data, which is clearly visible in Fig. 3b, is mostly because of the variation of the PbI bond lengths in the metalhalide network. We calculated the correlation coefcient between band gap and bond lengths using the same data, and we obtained a very weak correlation (Spearman coefcient 9%). This test clearly indicates that the role of bond lengths represents a second-order effect, thereby providing further support to our Platonic model. Finally, Fig. 3c shows our main nding, namely that by suitably choosing the

cation it is possible, at least in principle, to ne-tune the band gap almost continuously over a very wide range of photon energies.

Our analysis highlights several new promising structures, in particular perovskites with phosphonium PH4

, arsonium

AsH4

and stibonium SbH4

, all with band gaps ranging

between 1.2 and 1.4 eV. These values fall in the middle of the range for optimum photovoltaic efciency, and suggest that our new structures hold potential as novel solar cells materials. Besides the low gap, these perovskites are expected to exhibit higher mobilities than MAPbI3. In fact, as shown in

Supplementary Fig. 2a,b, the carrier-effective masses decrease towards larger bond angles, consistent with the concomitant reduction of the band gap. In addition to lower gaps and effective masses, large cations have the advantage that the lling of the cuboctahedral cavity should counter the known tendency of perovskite solar cells to degrade by water incorporation14.

In order to evaluate the practical feasibility of the hypothetical perovskites identied in this work we searched for possible dynamical instabilities in one of the structures with the smallest band gap, AsH4PbI3 (NCl4 is less interesting because of safety concerns related to chlorides). This structure is especially interesting since the preparation could proceed through the corresponding iodide AsH4I (ref. 40), similarly to the case of methylammonium iodide CH3NH3I. As shown by Supplementary Fig. 3, the vibrational density of states calculated using density-functional perturbation theory41 does not exhibit any soft modes, thereby indicating that the 3D perovskite structure of AsH4PbI3 should be stable against distortions. More generally, in order to assess the stability of all the structures considered here, we move to a simple semi-empirical approach based on the Goldschmidt tolerance factor t (refs 33,42) (see Methods for the denition of t).

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2

1

0 500 600 700 800

Wavelength (nm)

1.21.11.00.9

Tolerance factor

0% Rb, 100% Cs

Absorbance (a.u.)

20% Rb, 80% Cs

0.80.70.60.5

11% Rb, 89% Cs

NCI 4

AsH 4

SbH 4

K

CH 3PH 3

PF 4

PH 4

CH 2N 2H 4

C 2H 6NH 2

CH 3NH 3

CH 3SbH 3

CH 3AsH 3

C 2H 6PH 2

Rb

NH 4 Cs

Na

Li

Figure 4 | Material stability and optical measurements. (a) Calculated Goldschmidt tolerance factors for all the perovskite structures considered in this work. The open circles are obtained using the steric sizes calculated from DFT (Supplementary Table 1). For comparison we also show the tolerance factors obtained by using the ionic radii reported in ref. 37 (lled circles). The grey area bound by the solid grey lines correspond to the geometric criterion for the Goldschmidt tolerance factor42,43, while the dashed lines correspond to the empirical range proposed in ref. 44.(b) Measured absorbance spectra of the dark phase of RbxCs1 xPbI3 perovskite thin lms, with x 0, x 0.1 and x 0.2. When increasing the Rb

content a continuous blue shift of the absorption onset is observed, from 720 nm (x 0) to 690 nm (x 0.2). This blue shift corresponds to an

increase in band gap, and is assigned to the more pronounced octahedral tilt in the PbI3 network, as illustrated in the inset.

It is known empirically that 3D perovskites should form when the tolerance factor falls within a narrow range t 0.71.1

(refs 33,4244). Figure 4a shows that the tolerance factors derived from our calculated steric sizes falls within this range for most of the structures considered here. In particular, according to this criterion, all the cations up to Rb and K should be stable.

In order to demonstrate the band gap tunability we attempted the synthesis of perovskites based on elemental cations, building on our experience with CsPbI3 (ref. 18) (see Methods). As deposited, we observed that CsPbI3 formed a pale phase with a wide bandgap. Upon annealing this structure turned into a dark phase with a band gap of 1.73 eV, which we identify as the 3D perovskite structure discussed in this work. The synthesis of lms with cations smaller than Cs (Rb, K, Na and Li) yielded similar pale phases. However, upon annealing, some of the lms degraded via sublimation before we could observe a dark phase as for CsPbI3, suggesting that 3D perovskites were not formed.

This nding is in agreement with our analysis of the Goldschmidt tolerance factor shown in Fig. 4a. While the proposed 3D perovskites could possibly be synthesised using higher pressures or longer annealing runs at lower temperatures, here for the sake of simplicity we did not pursue this direction. Instead we considered an alternative approach and explored mixtures of cations, as suggested in ref. 45: if mixtures of Cs and smaller cations could gradually shift the bandgap towards the larger values, this would conrm our predicted tunabiliy via steric effects.

As a proof-of-concept we prepared perovskites with Rb/Cs cation mixtures, namely RbxCs1 xPbI3 with x 0, x 0.1 and

x 0.2 (never hitherto reported). Optical characterization of

these lms, shown in Fig. 4b, indicates that the absorption edge blue shifts from 720 to 690 nm in going from Cs to Rb. This result is in excellent agreement with our calculations, which predict a corresponding blue shift of 40 nm.

Our ndings are also in line with a recent study (which appeared while the present manuscript was under review) where the authors demonstrated band gap tunability via the mixing of CH3NH3 = Cs mixtures46. Taken together, our present results and those of refs 13,18,47 conrm the tunability of the band gap via the steric size of the cation over almost half of our predicted range, thereby providing strong support to our theory.

Finally, our theory is based on very general considerations and its predictions are not linked to the underlying calculation

methods. Therefore, it is expected that this model will carry similar predictive power across other families of metalhalide perovskites. More fundamentally, the ability to control the band gap via the steric size of the cation, as proposed in this work, may become a new paradigm in the solution deposition of solar cells, light-emitting diodes and photonic structures with layer-by-layer control of their optical properties.

Note added in proof. While this work was under peer review, a related work exploring the relation between the size of cations and the electronic and optical properties of metal-halide perovskites was submitted and published63. The key difference between the present work and that of ref. 63 is that we develop a predictive universal theory of band gap tuning via steric effects, and we perform experiments that conrm a posteriori our predictions.

Methods

Computational methods. All calculations were performed within the local density approximation to density functional theory48,49 using planewaves and pseudopotentials, as implemented in the Quantum ESPRESSO software package50. Only valence electrons were described explicitly, and the corevalence interaction was taken into account by means of ultrasoft pseudopotentials51,52 with nonlinear core correction53. For Pb and I we used fully relativistic ultrasoft pseudopotentials. In the case of Pb we included the 5d semicore states, and for Sb, Rb and Cs we used norm conserving pseudopotentials54. The electron wavefunctions and the charge density were expanded in planewave basis sets with kinetic energy cutoffs 40 and 200 Ry, respectively. Structural optimization was performed by sampling the Brillouin zone using uniform and unshifted 4 4 4 meshes. Electronic structure

calculations were performed using a 6 6 6 Brillouin zone grid. All structural

optimizations were initialized using the crystallographic data for MAPbI3 reported in ref. 17. The initial coordinates of the molecular cations were chosen in such a way that the centre of mass is located in the middle of the cuboctahedral cavity, and the orientation of the four inequivalent cations in one unit cell follows the symmetry properties of the Pnma space group. Given the complexity of the total energy landscape of these systems, we checked the sensitivity of the structure with respect to the choice of the initial conguration in the case of NH4PbI3. This compound lies close to the stability limit (Fig. 4b), and can form quasi-1D structures in the presence of water55,56. In this case we performed structural optimizations using three additional initial congurations: (i) aa ae 0, (ii) aa 0

and aea0 with octahedra in phase along the apical direction, (iii) same as in (ii) but with octahedra out of phase. The optimized structures are all 3D perovskites, with total energy differences within 6 meV per atom. The largest deviation from the band gap reported in Fig. 3c is of 0.2 eV, and reects the differences in the bond angles, following the trend predicted by the Platonic model in Fig. 2.

In the case of MAPbI3 it has been established that the spinorbit interaction tends to reduce the scalar-relativistic band gap by B11.1 eV (refs 20,22). This is consistent with our results shown in Fig. 3b. On the other hand, GW quasiparticle corrections do increase the value of the band gap22. Given these compensating

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corrections, and the fact that the very small relativistic band gaps are likely to induce signicant errors in the calculation of the screened Coulomb interaction W, it is sensible to take scalar-relativistic calculations as the most consistent and unambiguous way to capture trends and identify the most promising structures.

In order to check that the band gap trend obtained with DFT/LDA holds when using a higher level theory, we performed G0W0 calculations using the Yambo code57 for a few selected structures, namely AsH4PbI3, CH3NH3PbI3, CsPbI3 and LiPbI3. For these calculations we used LDA norm conserving fully relativistic pseudopotentials for Pb and I, with semicore 5d states included for Pb. The Kohn Sham eigenfunctions and eigenvalues were calculated using a 100-Ry kinetic energy cutoff for all structures except LiPbI3, for which we used a cutoff of 130 Ry. The exchange and the correlation parts of the GW self-energy were calculated using planewaves cutoffs of 13 and 5 Ry, respectively (this is at the limit of what we can afford given the large unit cells). The screened Coulomb interaction W was described by means of the GodbyNeeds plasmon-pole model58, and 400 bands were included in the sum over virtual states. The wavevector dependence of the screened Coulomb interaction was described by sampling the Brillouin zone using a G-centred 2 2 2 grid. A detailed discussion of these calculation is given in

Supplementary Note 2.

Exciton-binding energy. In order to estimate the magnitude of excitonic effects on the band gaps we calculate the exciton-binding energies using a simple Wannier exciton model59. In the Wannier model the exciton-binding energy is given by Eb m =e20E1s, where E1s is the energy of the fundamental state of the hydrogen

atom, m* is the effective mass of electrons and holes (that is, 1/m* 1/me 1/mh)

and e0 the static (electronic) dielectric constant of the solid. This model is very approximate but should provide a fair representation of the trends in exciton-binding energies in our compounds.

We calculated the effective mass tensors by approximating the second derivatives of the relativistic KohnSham eigenvalues via nite differences, and taking the isotropic average in each case. Supplementary Fig. 2a,b shows the hole and electron effective masses thus obtained for the Platonic perovskite model, as a function of equatorial and apical metalhalidemetal bond angles. Our calculated effective masses are in line with previous calculations for CH3NH3PbI3 and CsPbI3 (refs 2022).

For the dielectric constant we performed nite-electric eld calculations using the Berry-phase technique60,61. In this case we adopted a G-centred 2 2 4

Brillouin-zone mesh, with a nite electric eld of 0.001 a.u. directed along the c axis. While in this case we did not not evaluate the isotropic average (purely in order to contain computational costs), Supplementary Figure 2d shows that this should not pose a problem since e0 does not depend strongly on the bond angles in the range of interest (e0 5.56.0).

Platonic model of metalhalide perovskites. Our ideal model of ABX3 metal organic halide perovskites consists of four inequivalent BX6 Platonic octahedra in an orthorombic unit cell17, in absence of the cation. The octahedra are labelled O1 O4, as indicated in Fig. 1d, and are connected in a corner-sharing conguration. The B atoms occupy the centres of the octahedra, the X atoms are located at the corners and the metalhalide BX distance is denoted by d. We set the origin of the reference frame at the centre of the octahedron O1, with its axes along the primitive vectors of the crystal lattice. The centres of the remaining three octahedra O2O4 are denoted by (x,y,0), (0,0,z) and (x,y,z), respectively. The coordinates x, y and z will be determined below starting from the Euler angles described in the main text. The lattice parameters are expressed in terms of the centres of the octahedra asa 2x, b 2y and c 2z. The corners of the octhedra are labelled as Xji, with the

superscript j identifying the octahedron, and the subscript i identifying a corner of the octahedron, as shown in Fig. 1c. The coordinates of each corner Xji are referred to as xji; yji; zji.

Octahedron O1. We consider an initial conguration where the octahedron O1 has its apical diagonal along the c axis, and its equatorial edges along the a and b axes. The coordinates of the corners X11, X13 and X15 are by 1; 1; 0d = 2

p ,

y14 yz11 z14y11 yd ; q

x11 xz14 z11x14 x d ;

x14 xy11 y y14 yx11 x

d :From the location of O2 we can also determine the lattice parameters: a 2d 2

p cosf, b 2d 2

p cosycosf and c 4d cosy, where the last equation follows

simply from the common tilt angle of O1 and O2 and the fact that they represent half of the unit cell along the c axis.

In the case of vanishing tilt angle, y 0, the spinning angle and the precession

angle identify the same rotation, hence their distinction is not meaningful. In this case the relevant parameter appearing in all the equations is their sum f c. For

consistency with the above rule that c 0 whenever ya0, we here adopt the

convention that c 0 always. In this case, when y 0 the only other independent

parameter is the precession angle f. Obviously, this choice does not affect our results in any way.

Octahedra O3 and O4. From Fig. 1d we see that octahedron O3 shares the corner X15 X36 with O1. As a consequence we have that octahedra O3 and O4 are centred

at the positions 2d(0,0,cosy) and d

2

p cosf; cosycosf; 2

p cosy, respectively.

The corners of these octahedra are readily obtained by taking into account their regularity and the corner-sharing connectivity between O3 and O4 and between

O2 and O4.

From the relations stated here it is clear that a cubic perovskite is obtained in the special case y f 0. Furthermore, when the tilt angle vanishes, y 0, we

obtain two inequivalent tetragonal structures with identical lattice parameters. These structures correspond to the situations where the spinning angles of neighbouring octahedra along the apical direction are in-phase (same magnitude and same sign) or out-of-phase (same magnitude but different sign).

As a general remark, the fact that the structure of the Platonic model is completely dened once we specify the values of two angles and the BX bond length is quite remarkable. This property simplies considerably the task of rationalizing the physics of metalorganic halide perovskites. Furthermore, the model illustrated here carries general validity and it can easily be adapted to describe other idealized perovskite structures.

Apical and equatorial bond angles. The Euler angles y and f can be related to the intrinsic BXB bond angles. To this end we observe in Fig. 1d that ae is the angle between O1 and O2 through the corner X11, and aa is the angle between O1 and O3 through X15. Using the coordinates of the centres of O1O3 and the corners

X11 and X15 determined as above, we nd immediately cosaa 1 2cos2y and

cosae 1 cos2f(1 cos2y). Since cos2(f)r1, the last two relations can be

combined to yield the constraint cos(p aa)Z2cos(p ae) 1. For all the angles

considered in Fig. 2, the expansion of this inequality to rst order in the angles is accurate to within 3% and reads p ae p aa = 2

r

1

A:

p . As a result, the Platonic model does not admit solutions with continuous corner-sharing connectivity in a region of the map bound by a straight line, as can be seen in Fig. 2.

Tolerance factor. The Goldschmidt tolerance factor is given by t RA RX= 2

p RB RX, with RA, RB and RX the ionic radii of the elements in

ABX3 perovskites42. It was found empirically that 3D perovskite form when t is in the range 0.71.1 (refs 33,4244). The lower bound corresponds to a situation where the cation is close enough to the halogen component to form a bond, thereby preventing the formation of a perovskite structure. The upper bound describes the case of the close-packed cubic perovskite structure. For values of t larger than 1 the perovskite structure is expected to distort or even form a layered perovskite structure62. For each structure we evaluated the Goldschmidt tolerance factor by using the steric sizes calculated via the DFT electron density and reported in Supplementary Table 1.

Material synthesis and characterization. Perovskite precursor preparation. APbI3 precursors were prepared by dissolving equimolar amounts of AI (where A Li,

Na, K, Rb and Cs) and PbI2 in N,N-dimethylformamide at 0.5 M, in a nitrogen-lled glovebox. Mixtures were made by simply mixing the prepared precursors in the desired ratio. Film formation. Glass substrates were cleaned with acetone, isopropanol and oxygen plasma treatment. Thin lms were formed by spin-coating

1; 1; 0d = 2

p and (0,0,1)d, respectively, while X12, X14 and X16 are obtained from these by changing the sign of all coordinates. In order to generate the most general structural models we perform a rotation of O1 according to the three Euler angles c, y and f. These angles dene a sequence of spin, tilt and precession around the c axis. The tilt y is performed via a rotation around a. This is illustrated in Fig. 1c. Following ref. 30 the matrix dening the rotation of the octahedron is:

cosccosf cosysinfsinc sinccosf cosysinfcosc sinysinf

coscsinf cosycosfsinc sincsinf cosycosfcosc sinycosf

sinysinc sinycosc cosy

0

@

By applying this rotation to the initial coordinates of O1 we obtain the position of the corners X1i (i 1,y,6) in their nal orientation. These new coordinates are

used to locate the centres and orientation of the remaining three octahedra.

Octahedron O2. In order to determine the centre (x, y, 0) of the octahedron O2 we use the following observations: O1 shares the corner X11 X22 with O2,

and the corner X13 X24 with O2 , the periodic replica of O2 along the a axis.

Furthermore, O2 shares the corner X23 X14 with O1 , the periodic replica of O1

along the b axis. By requesting that the distance between the centre (Ci) of each octahedron and each corner is d in all cases, and that O2 and O2 are both regular,

we obtain the following equations relating the centre of O2 with the position of the corner X11:

C1X11 C2X11 : x2 y2 2xx11 2yy11 0;

C1 X14 C2X14 : x2 y2 2xx13 2yy13 0;

C2X14 ?C2X11 : x2 y2 xx13 x11 yy11 y13 0:After expressing the coordinates of X11 in terms of the Euler angles c, y, and f, we nd that the above relations are veried simultaneously only when the spinning angle vanishes, c 0. In this case the coordinates of the centre of O2 are given by

x d 2

p cosf, y d 2

p cosycosf and the coordinates of its corners are determined using the condition that the octahedron be regular. The explicit expressions for the coordinates of O2 in terms of the corners of O1 are:

X21 : 2x x11; 2y y11; z11 X22 : x11; y11; z11 X23 : x14; y14 2y; z14

X24 : 2x x14; y14; z14 X25 : x p; y q; r X26 : x p; y q; r where the auxiliary variables p, q, r are given by:

p

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on the substrates at 2,000 r.p.m. in the glovebox, and subsequently annealed on a hotplate by increasing the temperature until the formation of the dark phase was observed. This occurred at B400 C for CsPbI3 and even higher for the Cs/Rb mixtures discussed in the main text. The 11% Rb lm changed colour at 420 C and the 20% Rb lm at 470 C. Optical measurements. Absorbance spectra were collected with a Varian Cary 300 UVvis spectrophotometer with an internally coupled integrating sphere.

References

1. Mitzi, D. B., Feild, C. A., Harrison, W. T. A. & Guloy, A. M. Conducting tin halides with a layered organic-based perovskite structure. Nature 369, 467469 (1994).

2. Kagan, C. R., Mitzi, D. B. & Dimitrakopoulos, C. D. Organic-inorganic hybrid materials as semiconducting channels in thin-lm eld-effect transistors. Science 286, 945947 (1999).

3. Kojima, A., Teshima, K., Shirai, Y. & Miyasaka, T. Organometal halide perovskites as visible-light sensitizers for photovoltaic cells. J. Am. Chem. Soc. 131, 60506051 (2009).

4. Chung, I., Lee, B., He, J., Chang, R. P. H. & Kanatzidis, M. G. All-solid-state dye-sensitized solar cells with high efciency. Nature 485, 486489 (2012).5. Lee, M. M., Teuscher, J., Miyasaka, T., Murakami, T. N. & Snaith, H. Efcient hybrid solar cells based on meso-superstructured organometal halide perovskites. Science 338, 643647 (2012).

6. Kim, H.-S. et al. Lead iodide perovskite sensitized all-solid-state submicron thin lm mesoscopic solar cell with efciency exceeding 9%. Sci. Rep. 2, 591 (2012).

7. Liu, M., Johnston, M. B. & Snaith, H. Efcient planar heterojunction perovskite solar cells by vapour deposition. Nature 501, 395398 (2013).

8. Burschka, J. et al. Sequential deposition as a route to high-performance perovskite-sensitized solar cells. Nature 499, 316319 (2013).

9. Zhou, H. et al. Interface engineering of highly efcient perovskite solar cells. Science 345, 542546 (2014).

10. Stranks, S. D. et al. Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber. Science 342, 341344 (2013).11. Wehrenfennig, C., Eperon, G. E., Johnston, M. B., Snaith, H. J. & Herz, L. M. High charge carrier mobilities and lifetimes in organo lead trihalide perovskites. Adv. Mater. 26, 15841589 (2014).

12. Xing, G. et al. Long-range balanced electron and hole transport lengths in organic-inorganic CH3NH3PbI3. Science 342, 344347 (2013).

13. Stoumpos, C. C., Malliakas, C. D. & Kanatzidis, M. G. Semiconducting tin and lead iodide perovskites with organic cations: phase transitions, high mobilities and near-infrared photoluminescent properties. Inorg. Chem. 52, 90199038 (2013).

14. Noh, J. H., Im, S. H., Heo, J. H., Mandal, T. N. & Seok, S. I. Chemical management for colorful, efcient and stable inorganic-organic hybrid nanostructured solar cells. Nano Lett. 13, 17641769 (2013).

15. Snaith, H. J. Perovskites: the emergence of a new era for low-cost, high-efciency solar cells. J. Phys. Chem. Lett. 4, 36233630 (2013).

16. Shockley, W. & Queisser, H. J. Detailed balance limit of efciency of p-n junction solar cells. J. Appl. Phys. 32, 510519 (1961).

17. Baikie, T. et al. Synthesis and crystal chemistry of the hybrid perovskite (CH3NH3)PbI3 for solid-state sensitized solar cell applications. J. Mater. Chem.

A 1, 56285641 (2013).18. Eperon, G. E. et al. Formamidinium lead trihalide: a broadly tunable perovskite for efcient planar heterojunction solar cells. Energy Environ. Sci. 7, 982988 (2014).

19. Mosconi, E., Amat, A., Nazeeruddin, M. d. K., Gratzel, M. & De Angelis, F. First-principles modeling of mixed halide organometal perovskites for photovoltaic applications. J. Phys. Chem. C 117, 1390213913 (2013).20. Even, J., Pedesseau, L., Jancu, J.-M. & Katan, C. Importance of spin-orbit coupling in hybrid organic/inorganic perovskites for photovoltaic applications.J. Phys. Chem. Lett. 4, 29993005 (2013).21. Even, J., Pedesseau, L., Jancu, J.-M. & Katan, C. DFT and kp modelling of the phase transitions of lead and tin halide perovskites for photovoltaic cells. Phys. Status Solidi 8, 3135 (2014).

22. Umari, P., Mosconi, E. & De Angelis, F. Relativistic GW calculations on CH3NH3PbI3 and CH3NH3SnI3 perovskites for solar cell applications. Sci. Rep. 4, 4467 (2014).

23. Eperon, G. E., Burlakov, V. M., Docampo, P., Goriely, A. & Snaith, H. J. Morphological control for high performance, solution-processed planar heterojunction perovskite solar cells. Adv. Func. Mater. 24, 151157 (2014).

24. Glazer, A. M. Simple ways of determining perovskite structures. Acta Cryst. A

31, 756762 (1975).

25. Chang, Y. H., Park, C. H. & Matsuishi, K. First-principles study of the structural and the electronic properties of the lead-halide based inorganic-organic perovskites (CH3NH3)PbX3 and CsPbX3 (X Cl, Br, I). J. Kor. Phys.

Soc. 44, 889893 (2004).

26. Chiarella, F., Zappettini, A. & Licci, F. Combined experimental and theoretical investigatiion of optical, structural and electronic properties of CH3NH3SnX3 thin lms (X Cl, Br, I). Phys. Rev. B 77, 045129 (2008).

27. Boriello, I., Cantele, G. & Ninno, D. Ab initio investigation of hybrid organic-inorganic perovskites based on tin halides. Phys. Rev. B 77, 235214 (2008).

28. Kawamura, Y., Mashiyama, H. & Hasebe, K. Structural study on cubic-tetragonal transition of CH3NH3PbI3. J. Phys. Soc. Jpn 71, 16941697 (2002).

29. Poglitsch, A. & Weber, D. Dynamic disorder in methylammoniumtrihalogenoplumbates (II) observed by millimeterwave spectroscopy. J. Chem. Phys. 87, 63736378 (1987).

30. Goldstein, H., Poole, C. & Safko, J. Classical Mechanics 3rd edn (Addison Wesley 152, 2002).

31. Knutson, J. L., Martin, J. D. & Mitzi, D. B. Tuning the band gap in hybrid tin iodide perovskite semiconductors using structural templating. Inorg. Chem. 44, 46994705 (2005).

32. Slater, J. C. & Koster, G. F. Simplied LCAO method for the periodic potential problem. Phys. Rev. B 94, 1498 (1954).

33. Mitzi, D. B. Progress in Inorganic Chemistry (John Wiley & Sons, Inc 48, 1999).34. Brivio, F., Walker, A. B. & Walsh, A. Structural and electronic properties of hybrid perovskites for high-efciency thin-lm photovoltaics from rst principles. Appl. Phys. Lett. Mater. 1, 042111 (2013).

35. Brivio, F., Butler, K. T., Walsh, A. & van Schilfgaarde, M. Relativistic quasiparticle self-consistent electronic structure of hybrid halide perovskite photovoltaic absorbers. Phys. Rev. B 89, 155204 (2014).

36. Frost, H. M. et al. Atomistic origins of high-performance in hybrid halide perovskite solar cells. Nano Lett. 14, 25842590 (2014).

37. Shannon, R. D. Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta. Cryst. A 32, 751767 (1976).

38. Mitzi, D. B., Wang, S., Felid, C. A., Chess, C. A. & Guloy, A. M. Conducting layered organic-inorganic halides containing h110i-oriented perovskite sheets.

Science 267, 14731476 (1995).39. Tanaka, K. et al. Electronic and excitonic structures of inorganic-organaic perovskite-type quantum-well crystal (C4H9NH3)2PbBr4. Jpn J. Appl. Phys. 44, 59235932 (2005).

40. Durig, J. R., Pate, C. B. & Li., Y. S. Far-infrared and Raman spectra of arsonium iodide. J. Chem. Phys. 54, 10331036 (1971).

41. Baroni, S., de Gironcoli, S., Dal Corso, A. & Giannozzi, P. Phonons and related crystal properties from density-functional perturbation theory. Rev. Mod. Phys. 73, 515562 (2001).

42. Goldschmidt, V. M. Die Gesetze der Krystallochemie. Naturwissenschaften 21, 477485 (1926).

43. Jones, A. P., Wall, F. & Williams, C. T. Rare Earth Minerals: Chemistry, Origin and Ore Deposits (Springer 7, 1996).

44. Green, M. A., Ho-Baillie, A. & Snaith, H. J. The emergence of perovskite solar cells. Nat. Photonics 8, 506514 (2014).

45. Trots, D. M. & Myagkota, S. V. High-temperature structural evolution of caesium and rubidium triiodoplumbates. J. Phys. Chem. Solids 69, 25202526 (2008).

46. Choi, H. et al. Cesium-doped methylammonium lead iodide perovskite light absorber for hybrid solar cells. Nano Energy 7, 8085 (2014).

47. Pellet, N. et al. Mixed-organic-cation perovskite photovoltaics for enhanced solar-light harvesting. Angew. Chem. 53, 31513157 (2014).

48. Ceperley, D. M. & Alder, B. J. Ground state of the electron gas by a stochastic method. Phys. Rev. Lett. 45, 566569 (1980).

49. Perdew, J. P. & Zunger, A. Self-interaction correction to densityfunctional approximations for many-electron systems. Phys. Rev. B 23, 5048 (1981).

50. Giannozzi, P. et al. QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Matter 21, 395502 (2009).

51. Rappe, A. M., Rabe, K. M., Kaxiras, E. & Joannopoulos, J. D. Optimized pseudopotentials. Phys. Rev. B 41, 1227 (1990).

52. Vanderbilt, D. Soft self-consistent pseudopotentials in a generalized eigenvalue formalism. Phys. Rev. B 41, 7892 (1990).

53. Louie, S. G., Froyen, S. & Cohen, M. L. Nonlinear ionic pseudopotentials in spin-density-functional calculations. Phys. Rev. B 26, 1738 (1982).54. Martins, J. L., Troullier, N. & Wei, S.-H. Pseudopotential plane-wave calculations for ZnS. Phys. Rev. B 43, 2213 (1991).

55. Bedlivy, D. & Mereiter, K. The structures of potassium lead triiodide dihydrate and ammonium lead triiodide dihydrate. Acta Cryst. B 36, 782785 (1980).

56. Fan, L.-Q. & Wu, J.-H. NH4PbI3. Acta Cryst. E 63, 189 (2007).57. Marini, A., Hogan, C., Grning, M. & Versano, D. Yambo: an ab initio tool for excited state calculations. Comput. Phys. Commun. 180, 13921403 (2002).

8 NATURE COMMUNICATIONS | 5:5757 | DOI: 10.1038/ncomms6757 | http://www.nature.com/naturecommunications

Web End =www.nature.com/naturecommunications

& 2014 Macmillan Publishers Limited. All rights reserved.

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms6757 ARTICLE

58. Godby, R. & Needs, R. Metal-insulator transitions in Kohn-Sham theory and quasiparticle theory. Phys. Rev. Lett. 62, 1169 (1989).

59. Yu, P. & Cardona, M. Fundamentals of Semiconductors 4th edn (Springer, 2010).

60. Souza, I., Iniguez, J. & Vanderbilt, D. First-principles approach to insulators in nite electric elds. Phys. Rev. Lett. 89, 117602 (2002).

61. Umari, P. & Pasquarello, A. Ab initio molecular dynamics in a nite homogeneous electric eld. Phys. Rev. Lett. 89, 157602 (2002).

62. Im, J.-H., Chung, J., Kim, S.-J. & Park, N.-G. Synthesis, structure, and photovoltaic property of a nanocrystalline 2H perovskite-type novel sensitizer (CH3CH2NH3)PbI3. Nanoscale Res. Lett. 7, 353 (2012).

63. Amat, A. et al. Cation-induced band-gap tuning in organohalide perovskites: Interplay of spin-orbit coupling and octahedra tilting. Nano Lett. 14, 36083616 (2014).

64. Momma, K. & Izumi, F. VESTA: A three-dimensional visualization system for electronic and structural analysis. J. Appl. Cryst. 41, 653658 (2008).

Acknowledgements

We wish to thank A. N. Kolmogorov for fruitful discussions. This work was supported by

the European Research Council (EU FP7/ERC grant no. 239578), the UK Engineering

and Physical Sciences Research Council (grant no. EP/J009857/1), the Leverhulme Trust

(grant RL-2012-001) and the Graphene Flagship (EU FP7 grant no. 604391). G.E.E. is

supported by the UK EPSRC and Oxford Photovoltaics Ltd. through a Nanotechnology

KTN CASE award. Calculations were performed at the Oxford Supercomputing Centre

and at the Oxford Materials Modelling Laboratory. All structural models were rendered

using VESTA64.

Author contributions

M.R.F. performed the computational research and analysed the results. G.E.E. and H.J.S.

performed the experimental synthesis and characterization. F.G. designed the research

and led the project. All authors participated in the preparation of the manuscript.

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