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Letter
Structural and Optical Properties of Cs2AgBiBr6 Double Perovskite.
Laura Schade, Adam D. Wright, Roger D. Johnson, Markus Dollmann, Bernard Wenger, Pabitra Nayak,
Dharmalingam Prabhakaran, Laura M. Herz, Robin J. Nicholas, Henry J. Snaith, and Paolo Radaelli
ACS Energy Lett., Just Accepted Manuscript • DOI: 10.1021/acsenergylett.8b02090 • Publication Date (Web): 19 Dec 2018
Downloaded from http://pubs.acs.org on December 19, 2018

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Page 1 of 20 ACS Energy Letters

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8 Structural and Optical Properties of
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11 Cs2 AgBiBr6 Double Perovskite.
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Laura Schade, Adam D. Wright, Roger D. Johnson, Markus Dollmann, Bernard
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Wenger, Pabitra K. Nayak, Dharmalingam Prabhakaran, Laura M. Herz, Robin
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20 Nicholas, Henry J. Snaith, and Paolo G. Radaelli
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23 Clarendon Laboratory, Department of Physics, University of Oxford, OX1 3 PU, United
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25 Kingdom.
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28 E-mail: laura.schade@physics.ox.ac.uk.
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Abstract
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34 We present a comprehensive study of the relationship between the crystal struc-
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36 ture and optoelectronic properties of the double perovskite Cs2 AgBiBr6 , which has
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38 emerged as a promising candidate for photovoltaic. Based on single-crystal/powder
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X-ray diraction and neutron powder diraction, we have revealed the presence of a
41 structural phase transition at Ts ∼122K between the room-temperature cubic structure
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43 (space group F m3̄m) and a new low-temperature tetragonal structure (I4/m). From
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45 reectivity measurements we found that the peak exciton energy Eex ≈ 2.85 eV near
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47 the direct gap shifts proportionally to the tetragonal strain, which is consistent with the
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49 Eex being primarily controlled by a rotational degree of freedom of the crystal structure,
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51 thus by the angle Bi-Br-Ag. We observed the time-resolved photoluminescence kinetics
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and we found that, among the relaxation channels, a fast one is mainly present in the
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tetragonal phase, suggesting that its origin may lie in the formation of tetragonal twin
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56 domains.
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14 Table of contents
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17 Hybrid halide perovskites, with general formula ABX3 (A=organic/inorganic 1+ cation,
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19 B=inorganic 2+ cation and X= halide anion) have gained increasing attention in the scientic
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21 community as high-performing semiconductors in solar cell devices. The Power Conversion
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23 Eciency of devices based on these materials has increased to a remarkable 28% in the
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25 last few years,
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due to high carrier mobility, a tunable band gap, long diusion lengths,
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27 and strong optical absorption.
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For highest thermal stability, an all-inorganic perovskite
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29 would be preferable. However, to-date it has proven highly challenging to stabilise the room
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31 temperature crystalline polymorph of the inorganic lead halide CsPbI3 .
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Furthermore, the
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33 realisation of the unexpected functionality of the lead halide perovskites has directed the
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35 research community to attempt to discover new metal halide based semiconductors with
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37 improved, or complementary, functionality.
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39 Recently,
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double perovskites with general formula A2 M1+ M'3+ X6 have been proposed as
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41 all-inorganic alternatives. In particular, Cs2 AgBiBr6 is one of the few materials investigated
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43 since the discovery of ecient PV operation of lead halide perovskites which delivers sub-
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stantial performance in a PV cell. It is highly stable, it has been predicted to have relatively
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low carrier eective masses and it has shown long carrier recombination lifetimes. Greul
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49 et al. 10 and Gao et al. 11 demonstrated the fabrication of Cs2 AgBiBr6 lms and incorporated
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51 them into working devices for the rst time. However, there is very little know about the
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53 crystallography and its impact upon the optoelectronic properties. This information is im-
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55 portant in order to both improve the present family of double perovskites, and to design
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new and improved compounds. Although the maximum power conversion eciency so far
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achieved in double perovskites (2.23%) is lower than for hybrid perovskites, these materi-
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als are much less mature in terms of device technologies and have signicant potential for
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9 applications, as demonstrated for example by the discovery of highly ecient near white
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11 light emission from Cl double perovskites.
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Furthermore, they represent a very good model
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13 system to study, in order to understand deciencies and hence routes to improved properties
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15 through either design of new compounds, or the tuning of the present ones.
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17 Based on X-ray diraction measurements, McClure et al. 13 determined the ambient-
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19 temperature crystal structure of Cs2 AgBiBr6 to be cubic with a =11.2711(1) Å and space
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21 group F m3̄m, which accounts for the Bi/Ag ordering on a rock-salt superstructure. An
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23 indirect band gap has also been reported around ∼ 2 eV, but the community is yet to nd
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25 consensus on its exact value.
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Recently, the charge carrier dynamics of this compound
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27 has been explored with dierent techniques.
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In spite of these eorts, very little is known
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29 about the relationship between structural and optical properties, and in particular the direct
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31 band gap transition. Originally predicted to be at the X-point and 0.7 eV higher than the
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33 indirect gap,
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it is visible at ∼ 2.8eV as a sharp feature typical of two-particle transitions,
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35 and is the dominant feature in the absorbance and reectivity of thin lms,
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nanocrystals
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37 and bulk crystal reectivity.
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Regardless of whether Cs2 AgBiBr6 devices can be optimised,
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39 the remainder of this paper will demonstrate that Cs2 AgBiBr6 is an extraordinary interesting
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41 model system for understanding the physics of the wider family of halide perovskites. All
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43 these materials have closely related crystal structures, and understanding structure-property
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45 relations is highly relevant for materials that are already known to have higher eciency, and
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47 for guiding the design of future compounds. For instance, MAPbI3 undergoes ferroelastic
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49 phase transitions both above and below room temperature
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that are closely related to
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51 Cs2 AgBiBr6 and crystallises in a distorted phase at operating temperatures. Therefore,
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53 rational design of better halide PV materials will be greatly facilitated by understanding
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55 structure-property relations in model systems such as Cs2 AgBiBr6 .
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In this paper, we describe the structural properties of Cs2 AgBiBr6 as a function of tem-
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perature, and their correlation with its optoelectronic properties. Based on heat capacity
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measurements, X-ray powder and single-crystal diraction and neutron powder diraction,
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9 we demonstrate that this compound undergoes a low-temperature cubic to tetragonal struc-
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11 tural phase transition at TS ∼ 122 K. We rene the published cubic crystal structure above
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13 TS , and we present a complete structural solution for the low-temperature tetragonal phase.
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15 Having established the temperature dependence of the excitonic transition at the direct band
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17 gap from reectivity measurements, we found a linear relationship with the tetragonal strain.
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19 This demonstrates that the direct gap is primarily controlled by M Br6 octahedral rotations
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21 that characterize the tetragonal phase. Finally, based on photoluminescence measurements,
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23 we evidence the presence of enhanced PL near the tetragonal phase transition, and, below
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25 it, of an additional fast charge-carrier recombination mechanism, which is suppressed in the
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27 cubic phase and may be associated with strain at tetragonal twin boundaries.
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29 Polycrystalline powder samples were synthesized through precipitation: the chemicals
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31 AgBr (2mmol, 99.5% of purity), CsBr (4mmol, 99% of purity) and BiBr3 (2mmol, purity >
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33 98%) were dissolved in ∼ 4 ml of DMSO (dimethyl sulfoxide) and then precipitated with
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35 acetone, producing ∼ 2 grams of powder after drying. Using commercial chemicals, we could
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37 not grow single crystals as previously reported
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due to the lack of complete solubility of the
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39 salts in hot HBr solution. So, we rst precipitated the polycrystalline powder, and then
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41 we dissolved the compound (∼1 g) in ∼ 10 ml of 9-M HBr, heating it at 110° in an oven.
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43 Cooling down to room temperature at a rate of 0.5 degrees per hour we obtained ∼ 1 mm-
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45 size single crystals. We characterized both single crystal and powder samples with the use
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47 of X-ray diraction (see Section 7 in the Supplementary Information (SI) for experimental
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49 details). The single crystal data were t with the established cubic crystal structure
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giving
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51 outstanding goodness-of-t, which demonstrated excellent crystal quality (see Figure S1, S2
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53 and table S1 in the SI). The X-ray powder diraction data was also t using the same cubic
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55 structure model, which well reproduced the majority of peaks in the diraction pattern.
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However, a 20wt% CsAgBr2 impurity phase was also identied. In both renements, the
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B-site cations were found to be fully ordered within the sensitivity of the measurement (the
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occupancy of both the atoms was found to be 1.00±0.05). This is important to note since
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9 it has been predicted that the optical properties may change with the degree of positional
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11 disorder of the B-site cations.
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Figure 1: The temperature dependence of a) the heat capacity (error bars are smaller than
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the data points). The dashed line is a Debye t to the data below the phase transition.
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52 b) lattice parameters, c) the unit cell volume, and d) the spontaneous strain. The red line
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We performed specic heat capacity (cp ) measurements on a 5.2 mg single crystal (Exper-
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imental details in the SI). We show the data in Figure 1 , where we observe a sharp anomaly

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at Ts ' 122K , indicative of a second-order or weakly rst-order phase transition. Further-
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more, from detailed cp measurements on heating and cooling near the transition temperature
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9 Ts (see Figure S5 in the SI) we observe the absence of thermal hysteresis. From the data
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11 in Figure 1a, we t the T< Ts cp range with a Debye model, yielding a Debye temperature
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13 TD =114(4) K. This temperature is consistent with lower values of the sound velocity and
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15 bulk modulus than the most commonly known hybrid-halide perovskites
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suggesting that
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17 Cs2 AgBiBr6 is slightly softer.
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19 We conrmed the presence of a structural phase transition at TS by powder XRD. Imme-
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21 diately below TS , diraction peaks became strongly split (see Figure S4 in the SI), consistent
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23 with the lowering of the crystal symmetry to tetragonal with a unit-cell elongation along the
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25 c axis. This symmetry then persists down to the lowest measured temperature (15K). As-
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27 suming tetragonal symmetry, we tted the lattice parameters to the data, which we display
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29 in Figure 1 b).
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31 In order to determine the low-temperature tetragonal crystal structure of Cs2 AgBiBr6
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33 accurately, we collected neutron powder diraction (NPD) data at room temperature and
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35 at 30 K (see Experimental details in SI). To check for consistency, we rened the cubic
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37 structure
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against our room-temperature NPD data (Figure S3 a in the SI) and we found
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39 it in excellent agreement with our previous renement using single-crystal XRD. We list the
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41 two sets of room-temperature structural parameters in Table I.
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43 Symmetry analysis was performed using the Isotropy Suite.
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There are just two candi-
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45 date tetragonal subgroups of the F m3̄m parent structure: I4/mmm (no. 189) is reached by
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47 a tetragonal distortion of the M Br6 octahedra. Alternatively, subgroup I4/m (no. 87) also
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49 allows for a coherent rotation of MBr6 octahedra about the tetragonal c axis, where BiBr6
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51 and AgBr6 octahedra rotate in opposite senses (see Figure S2 in the SI). Since I4/m is a
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53 subgroup of I4/mmm, the atomic displacements allowed in I4/mmm are also allowed in
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55 I4/m; hence, we can rene the crystal structure using the I4/m space group, and assess a
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3 Table 1:
1 1 1 1
Rened crystal structure parameters of Cs2 AgBiBr6 . at = ac + bc ; bt =- ac + bc ,
2 2 2 2
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where subscripts c and t refer to the cubic and tetragonal unit cells, respectively. In F m3̄m
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6 the atoms are located at the following Wycko positions. Cs: 8c ( , , ) ; Bi: 4a (0, 0,
4 4 4
1 1 1 1 1
7 0); Ag: 4b ( , , ); Br1: 24e (x, 0, 0). In the I4/m space group: Cs: 4d ( , 0, ); Bi: 2a
2 2 2 2 4
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(0,0,0); Ag: 2b (0,0, ); Br1: 8h (x,y,0); Br2: 4e (0,0,z). Vf.u. stands for volume per formula
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9 unit.
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11 NPD 30K NPD RT PXRD RT
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I4/m F m3̄m F m3̄m
14 Lattice Parameters [Å]
15 at,c 7.8794(4) 11.2784(5) 11.27301(9)
16 ct,c 11.3236(7) 11.2784(5) 11.27301(9)
17 Vf.u. 3
[Å ] 351.51(3) 358.66(3) 358.145(5)
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Renable atomic fractional coordinates
20 Br1 x 0.27976(2) 0.25072(1) 0.25143(2)
21 y 0.77941(2) - -
22 Br2 z 0.24959(2) - -
23 Atomic displacement parameters 100×Uiso [Å2 ]
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Cs 0.900(9) 4.517(1) 3.56(4)
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26 Ag 0.204(5) 1.169(1) 0.55(4)
27 Bi 0.475(5) 2.229(2) 1.99(8)
28 Br1 0.966(7) 4.879(1) 4.05(4)
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Br2 0.966(7) - -
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31 Renement reliability parameters [%]
32 Rp 1.02 1.37 0.96
33 Rwp 1.04 1.41 2.59
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36 posteriori whether the additional symmetry lowering is justied. An I4/m crystal structure
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38 model was Rietveld-rened against neutron powder diraction data collected at 30 K, giving
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40 excellent agreement (see Figure S3 b) and Table I). With respect to the cubic phase, the
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42 octahedra underwent a tetragonal distortion of rz /rxy =1.009±0.008 for the AgBr6 one and
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44 1.007±0.009 for the BiBr6 one (where rxy and rz represent the bond lengths between Ag/Bi
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46 and Br in the plane and along the c axis respectively). On the other hand, the octahedra
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48 in the tetragonal phase rotate by θ=6.75°±0.15 (see Figure S2 in the SI). Based on these
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50 results, it is clear that the primary distortion below TS is the octahedral rotations and the
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52 tetragonal elongation is negligible, further conrming the choice of the I4/m space group.
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54 The F m3̄m → I4/m phase transition is allowed to be second-order, and its order pa-
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56 rameter η is proportional to the octahedral rotation angle, while the spontaneous tetragonal
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strain σ = 2(a − c)/(a + c) is proportional to η 2 . It is important to note that η is here related
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to the rotational degree of freedom, and it should not be confused with any order parameter
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associated with a transition driven by the disorder on the B-site cations as discussed previ-
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9 ously.
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In the mean-eld approximation, η2 should be linearly proportional to the reduced
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11 temperature t = 1 − T /Ts . More generally, the order parameter should follow the relation
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13 η = tβ , with the critical exponent β = 1/2 in mean eld.
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d
The tetragonal strain (shown in Figure 1 ) obeys a linear relationship reasonably well

17 near the phase transition, whilst departing from it markedly at low temperatures; it is in
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19 general very dicult to determine β with any accuracy, and even the possibility of a weakly
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21 rst-order transition (always allowed) cannot be completely excluded.
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23 From reectivity measurements (Experimental details in the SI) performed on a sin-
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25 gle crystal, we observe that the predominant feature in the spectrum is a dispersive edge,
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27 characteristic of a band-edge, free-carrier excitonic absorption, which strengthens rapidly
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29 and narrows with decreasing temperature (see Figure S7). Using an approximation of the
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31 Kramers-Kronig relations, the negative energy derivative of the reectivity (−dR/dE), pro-
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33 duces peaks at almost exactly the energies of the resonant absorption and improves the
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35 spectral resolution (see SI for a full analysis). Figure 2 a demonstrates the narrowing and
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37 shift with temperature. By 1.5K the full width at half maximum is only 30 meV (correspond-
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39 ing to a spectral broadening of 60 meV) allowing much greater accuracy in measurement of
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41 the interband excitonic transition energy Eex . In Figure 2 b we show the temperature depen-
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43 dence of the absorbance peak values (open circles). The dashed line is a model constructed
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45 based on the strain data in Figure 1 d and assuming the following functional relation:
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49 ∆V
Eex = Egap − Eb = c0 + c1 + c2 σ (1)
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52 where Eex is the exciton energy, Egap is the direct energy gap, Eb is the exciton binding
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54 energy, V is the unit cell volume, and σ is the spontaneous strain, derived from the data in
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56 Figure 1 b. The model, in excellent agreement with the data, was constructed by assuming
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Figure 2: ( ) Temperature dependence of normalized dierential reectivity (-dR/dE). The
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data are scaled for a better visualization. The lowest temperature spectrum has been tted
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ratio of 2:1 and a splitting of 25 meV. ( ) Absorbance peaks values (empty circles) plotted
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phase and the tetragonal strain.
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that Eb is independent of temperature, while Egap is controlled by and proportional to the

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electronic bandwidth W in the temperature range we probed. In this framework, there

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are two parameters controlling the bandwidth: the M-X bond length d, which increases
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monotonically with temperature, and the M-X-M' bond angle θ, which is related to the
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octahedral rotation (the order parameter η) as θ + 2η = π . By denoting ∆Eg as the change
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in gap energy from the a hypothetical undistorted perovskite (θ = π ), d0 and V0 as the
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9 zero-temperature M-X bond length and cell volume respectively, and γ as the appropriate
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11 exponent for the bond length, we obtain:
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c̃1 dγ0 + 2c̃2 η 2 (2)
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23 which is equivalent to Equation 1. It is evident from Figure 2 b that, for Cs2 AgBiBr6 ,
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25 changes in the exciton energy are largely dominated by bond angles rather than bond dis-
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27 tances. In fact, our determinated value for c1 ∼ 0.16 eV is small in comparison with c2 =
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29 1.01 ± 0.02 eV. A change in band gap of ∼ 1 eV has also been observed by Stoumpos and
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31 Kanatzidis for the family of APbI3 compounds where θ varies from π to π /2 in a sequence
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33 of dierent crystal structures, while the dominant role of the M-X-M angle on the bandgap
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35 changes has been discussed for the tin-iodide perovskites. At the lowest temperatures, the
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37 spectra in Fig. 2 a suggest that there is an unresolved splitting of ∼ 25 meV into two peaks
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39 with an intensity ratio of 2:1, consistent with a strain induced lifting of the X band gap
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41 degeneracy.
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43 We performed steady state photoluminescence (PL) measurements, collected at room and
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45 at low temperatures with an excitation wavelength of 398 nm (see the SI for details of the
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47 experimental set-up). At 25K we observe the presence of a PL peak at (EPL ) at ∼ 1.97(1) eV,
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49 i.e., ∼ 0.9 eV below the exciton energy, with a FWHM of ∼ 0.2 eV. We only observe
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51 a weak dependence of the PL peak position with increasing temperature, while the peak
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53 width increases to ∼ 0.6 eV at room temperature. The values of the peak maxima correlate
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55 well with our absorption measurements (Figure 3, panels a and b). We t the absorption
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spectrum accurately to the functional form ∝ (E − Egi )2 , which is consistent with an indirect
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bandgap whose onset correlates well with the values of the PL peak maxima. This agrees
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with the consensus that the PL can be assigned to recombination across the indirect
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9 bandgap, although a defect-assisted recombination pathway has also been proposed.
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The
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11 value of the indirect gap at room temperature (1.87(3) eV) is within the range of those
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13 previously reported in the literature (between 1.83 eV and 2.25 eV), 25 and increases to ∼
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15 1.97eV at 25K. We note that this direction of band gap change with temperature is opposite
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17 to that usually observed for lead and tin halide perovskites, but the same as that observed
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19 for most conventional semiconductors, such as Si and GaAs.
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21 Time-dependent PL measurements collected at T=4 K (Figure 3, panel c) indicate the
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23 presence of two dierent channels for PL decay: the rst component, labelled S for `short',
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25 was modelled with a mono-exponential, and has a very short time constant of τshort ∼ 1 ns,
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27 while the second, labelled L has a very long time constant, such that it cannot be reliably
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29 measured at this temperature. As shown in Figure 3 c, on warming the lifetime of the S
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31 component remains much lower than that of the L component, while its overall intensity
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33 decreases. By contrast, the decay of the L component becomes faster on warming. Above ∼
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35 50 K, the L component can be tted with a stretched exponential, yielding average lifetimes
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37 that vary between ∼ 50 µs at 50 K to a few ns at 200 K and above (panel c and d).
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39 We show the intensity ratio between the S and L components in an inset of Figure 3,
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41 panel e). When correlated with the structural and reectivity measurements, these data
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43 demonstrate that the S decay channel is only present in the tetragonal phase, and that it
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45 rapidly becomes weaker as the tetragonal distortion is reduced. One intriguing possibility is
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47 that S could be associated with defects concentrating at the twin boundaries, which spon-
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49 taneously form on cooling through the phase transition. In this scenario, the onset of the S
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51 component need not correlate precisely with TS , because a minimum value of twin boundary
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53 strain is usually required for the formation of defects. This hypothesis could be veried by
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55 repeating the PL measurements on a single crystal cooled under biaxial compressive strain
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Figure 3: Photoluminescence and absorbance measurements. Steady-state PL (solid

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blue line) and absorption coecient (solid red line) at 25 K ( ) and 275 K ( ) as a function
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44 of photon energy E. Quadratic ts (∼ (E-Eg ) ) to the absorption onsets are plotted in black,
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with the minimum energy (Eg ) indicated by dotted red lines. The dashed blue lines indicate
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the energy at the maximum PL intensity. ( ) Dots : PL transients (excitation at 398 nm,
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uence 210 nJ cm ) at temperatures between 4 and 100 K ( tetragonal phase). Solid
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49 lines : global ts of the sum of a stretched exponential (long) and a monoexponential (short)
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component, with the lifetime of the latter common between the temperatures, ( )Dots : PL
51 transients at temperatures from 125 to 295 K (cubic phase) Solid lines : stretched exponential
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ts. Black arrows indicate the overall temperature trends. ( ) Lifetimes of the long (blue)
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and short (red) components, shown on both sides of the phase transition temperature Ts .
55 Below 50 K, the tted long component lifetimes exceed the measurement capability of the
56 system, as indicated by the blue arrow. The inset shows the temperature dependence of the
57 ratio between the intensities of the short and long components.
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to promote the formation of a single tetragonal domain.
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In Figure 3 (panels c and d) we are only tting the early time decay (up to 100ns),

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for approximately the rst order of magnitude reduction in PL signal. In the SI, we show
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9 a transient PL decay for a Cs2 AgBiBr6 crystal, measured at room temperature over a
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11 longer time-period (Figure S6). Here it is indeed apparent that there exists a much slower
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13 longer component to the PL decay at room temperature (in agreement with the literature ).
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15 Therefore, it appears that there are 3 component to the PL dynamics. The very fast short
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17 decay S, at low temperature, which we interpret to be governed by charge trapping at
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19 twinning defects. The longer time decay L, at intermediate temperatures, which is sped
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21 up considerably as the temperature increases, likely to be due to charge trapping where
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23 the required emission of phonons becomes faster as the temperature is raised. The third
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25 component is the slow decay visible in the room temperature PL dynamics at long times,
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27 which may be governed by the trap depopulation time, rather than the lifetime of the free
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29 carrier.
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31 We show further evidence of the inuence of the phase transition on the electronic be-
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33 haviour from steady-state PL measurements excited with constant intensity 532nm radiation
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35 (Eph = 2.33 eV) (Figure 4). Using low intensity CW excitation at 532nm, below the direct
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37 band gap, the excitation region is considerably deeper thus sampling a much greater region of
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39 the crystal. Under these conditions the intensity of the emission around 1.9 eV is particularly
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41 sensitive to temperature, showing a very pronounced maximum just above the tetragonal to
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43 cubic transition. Considering going from room temperature down to low temperature, this
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45 observation may be due to the non-radiative trapping slowing down with reducing temper-
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47 ature, which would be expected to lead to an increased fraction of radiative emission, as
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49 usually observed in lead halide perovskites.
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The sudden drop in PL intensity upon further
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51 reducing the temperature below the cubic to tetragonal phase transition, is consistent with
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53 an large increase in strain induced electronic defects.
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55 In conclusion, our measurements and analysis demonstrate a strong link between the
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Figure 4: a ) Temperature-dependent steady-state PL excited by a 532 nm CW laser with a
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36 constant excitation intensity of 0.05 W cm . b ) Cut of panel a at an energy of ∼ 1.912 eV,
37 near the indirect band gap.
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40 structural and optical properties of the double perovskite Cs2 AgBiBr6 . Using heat capacity
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42 and diraction measurements, we determined the presence of a structural phase transition
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44 at ∼ 122K, between a room-temperature cubic phase (space group F m3̄m) and a low-
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46 temperature tetragonal phase (space group I4/m). This phase transition aects the optical
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48 properties quite dramatically: the exciton energy, and the corresponding band gap energy,
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50 extracted from our reectance measurement, increases in the tetragonal phase by as much as
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52 20 meV, and the excess energy scales linearly with the tetragonal strain, strongly suggesting
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54 that the direct gap energy is controlled by the M Br6 octahedral rotation. Moreover, our time-
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56 resolved PL measurements demonstrate that the charge carriers lifetimes are also aected
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by the structural transition, with a fast relaxation channel being present mainly in the
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tetragonal phase, possibly associated with tetragonal twin boundaries. Cs2 AgBiBr6 based
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solar cells show poorer photo-current and photo-voltage compared to the Pb(Sn)-halide based
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9 solar cells
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possibly due to the trapping of charge carriers and subsequent non-radiative
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11 recombination. Our ndings suggest that the formation of twinning boundaries can reduce
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13 the charge carrier lifetime. It is likely, therefore, that grain boundaries in polycrystalline
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15 thin lms could also aect the charge carrier behaviour. As a consequence further device
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17 improvement could be expected via better management of grain boundaries.
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Acknowledgement
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25 Experiments at the ISIS Pulsed Neutron and Muon Source were supported by a beamtime
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27 allocation from the Science and Technology Facilities Council under the Xpress programme.
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29 We acknowledge Ron Smith for support for these experiments. We acknowledge nancial
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31 support from the UK Engineering and Physical Sciences Research Council (EPSRC) and
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33 from Balliol college at Oxford University (J.T. Hamilton scholarship). The work was funded
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35 by EPSRC grant No. EP/P033229/1, entitled Unravelling halide segregation in hybrid
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37 perovskites for Si tandem photovoltaics.
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39

Supporting Information Available

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44 The following les are available free of charge.
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47 ˆ 2 2
Plot of Fcalc versus Fobs for the structural renement of a Cs2 AgBiBr6 single crystal
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49 and crystal structure (Figure S1 and Table S1);
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52 ˆ Photograph of a Cs2 AgBiBr6 single crystal and real-space representation of the tetrag-
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54 onal phase (Figure S2);
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ˆ Neutron-diraction patterns with Rietveld renement for the diraction proles mea-
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sured for Cs2 AgBiBr6 polycrystalline powder (Figure S3);
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8 ˆ X-ray diraction peak splitting (Figure S4);
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11 ˆ Specic heat capacity near the transition edge (Figure S5);
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14 ˆ Modelling of the transition energy (paragraph 3);
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17 ˆ Room temperature time-resolved photoluminescence of a Cs2 AgBiBr6 single crystal on
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19 larger time-scale (Figure S6);
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ˆ Reectivity measurements analysis (section 5);

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24 ˆ Experimental details (section 6).
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