2021
DOI: 10.1021/acs.jpclett.1c00334
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Bismuth Doping Alters Structural Phase Transitions in Methylammonium Lead Tribromide Single Crystals

Abstract: We study the effects of bismuth doping on the crystal structure and phase transitions of single crystals of the perovskite semiconductor methylammonium lead tribromide, MAPbBr 3 . By measuring the temperature-dependent specific heat capacity (C p ) we find that, as the Bi doping level increases, the temperatures for the bismuth structural phase transitions shift, and the phase boundary assigned to the transition from the cubic to tetragonal phase decreases in temperature. Furthermore, after doping we only obse… Show more

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Cited by 19 publications
(19 citation statements)
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“…It is difficult to compare different B-site dopants directly due to limited information available for their respective miscibility and integration into the CsPbI 3 crystal. 35 Nevertheless, considering just the relative change in unit cell volume, the largest relative reduction of 2% for 20% Zn 2+ doping is comparable to the volume change induced by 10% Br incorporation, CsPbI 2.7 Br 0.3 . The latter is a highly unstable material which still exhibits a yellow to black phase transition temperature (294 °C) only marginally lower than pure CsPbI 3 (320 °C).…”
Section: What Constitutes a Suitable Stabilizingmentioning
confidence: 97%
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“…It is difficult to compare different B-site dopants directly due to limited information available for their respective miscibility and integration into the CsPbI 3 crystal. 35 Nevertheless, considering just the relative change in unit cell volume, the largest relative reduction of 2% for 20% Zn 2+ doping is comparable to the volume change induced by 10% Br incorporation, CsPbI 2.7 Br 0.3 . The latter is a highly unstable material which still exhibits a yellow to black phase transition temperature (294 °C) only marginally lower than pure CsPbI 3 (320 °C).…”
Section: What Constitutes a Suitable Stabilizingmentioning
confidence: 97%
“…Note the impurity fractions represent the nominal concentration of the reported growth conditions and not the final composition of the crystal. 35 In units of Å, the Shannon radius of each dopant is provided in parentheses. also infers improved stability.…”
Section: Deducing Stability From Structurementioning
confidence: 99%
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“…Heterovalent doping has remained relatively less studied until recently due to the complexity of the charge compensation mechanisms that must be considered. In particular, bismuth has been investigated as a donor dopant for various inorganic and hybrid 3D perovskites [9][10][11][12][13][14][15][16] .…”
Section: Introductionmentioning
confidence: 99%
“…Different point defects compensating for Bi 3+ are possible, whose nature is, however, still unclear. 13 In MAPI, most studies attribute the formation of deep traps to Bi 3+ doping, hindering electron transport 14,16 ; it was also proposed that the Bi donors shift the Fermi level instead, causing, in turn, an increased concentration of Iinterstitials. 10 A careful control of the synthetic conditions was therefore proposed to balance the opposing tendencies towards I-vacancy and I-interstitial formation.…”
Section: Introductionmentioning
confidence: 99%