A Ferroelectric Chloride of Perowskite Type. Crystal Structure of CsGeCl3.

Christensen, A. Nørlund; Rasmussen, Svend Erik; Karvonen, Pertti; Kjær, Anders; Shapiro, Robert H.; Westerdahl, Anders

doi:10.3891/acta.chem.scand.19-0421

Cited by 78 publications

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“…It was suggested that ferroelectric effects might exist in hybrid perovskites, since there are structural similarities with caesium plumbohalide and barium titanate crystals28. Since then, similar perovskite structures, such as CsGeCl 3 , have been reported as ferroelectrics2930. More recently, remnant polarization of ≈10 mV has been reported for MAPI, which suggest a ferroelectric response31.…”

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The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells

et al. 2015

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Methylammonium lead iodide perovskite can make high-efficiency solar cells, which also show an unexplained photocurrent hysteresis dependent on the device-poling history. Here we report quasielastic neutron scattering measurements showing that dipolar CH3NH3+ ions reorientate between the faces, corners or edges of the pseudo-cubic lattice cages in CH3NH3PbI3 crystals with a room temperature residence time of ∼14 ps. Free rotation, π-flips and ionic diffusion are ruled out within a 1–200-ps time window. Monte Carlo simulations of interacting CH3NH3+ dipoles realigning within a 3D lattice suggest that the scattering measurements may be explained by the stabilization of CH3NH3+ in either antiferroelectric or ferroelectric domains. Collective realignment of CH3NH3+ to screen a device's built-in potential could reduce photovoltaic performance. However, we estimate the timescale for a domain wall to traverse a typical device to be ∼0.1–1 ms, faster than most observed hysteresis.

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The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells

et al. 2015

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“…The high tem perature perovskite type phase of CsGeCl3 changes to a rhom bohedral low tem perature phase (space group R3, Z = 1, Tc = 155°C), and this phase exhibits ferroelectricity with a dielectric con stant com parable to that of B a T i0 3 [25]. Here the stronger polarizing power of G e2® com pared to Sn2® and Pb2®, respectively, shows up.…”

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²⁰⁷Pb and ²⁰⁵Tl NMR on Perovskite Type Crystals APbX₃ (A = Cs, Tl, X = Br, I)

Sharma

Weiden

Weiß

1987

Zeitschrift Für Naturforschung A

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“…'Transition reversible, first-order in CsGeBr, and CsGe13 (106). For CsGeC1, the evidence concerning the order of the transition is contradictory (105,106). kAii-and light-sensitive.…”

Section: Active Lp E= Inactive L P Conversionmentioning

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The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

Knop¹,

Linden²,

Vincent³

et al. 1989

Can. J. Chem.

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The results of a detailed analysis of typical situations in crystals containing trigonal-pyramidal YEL3' species are used to argue that, per se, the lone electron pair (E, LP) on the Y atom determines neither the crystal structure nor the onentation of the Y EL3' units in the crystal. Considered as a space-filling entity, the LP has practically no effective volume of its own. Whatever space-filling or orienting properties may be associated with the presence of the LP, they are not autonomous; they arise from the intrinsic stereochemical involvement of the LP in the geometry of and the charge distribution in the free YEL3' ion or molecule and hence from the consequences of this geometry for crystal packing. Ab initio (6-31G*) calculations show that the electron density in the region of the LP in an ion is only slightly perturbed by the charge on the counter ion at distances observed in crystals. There is considerable similarity in the electron density distribution in the LP region of Y between free anionic (~0~~~ and free cationic (Me3S+) species. The problem of the so-called stereochemical inertness of the LP in the 14-electron octahedral Y E X~~-ions in crystals is examined in detail. It is concluded that the crystallographic Oh symmetry of the ion in cubic crystals is the result of dynamic averaging of possible orientations of the inherently noncubic YX62-octahedron (cf. the ab initio results for S e~l~~-) .Such averaging also appears to be responsible for the stereochemical "activation" or "inactivation" of the LP in thermally induced crystallographic transitions in the AYX3 halide perovskites and related crystals. To provide a firmer basis for the discussion of the LP, the crystal structures of the five title compounds have been determined. The crystal chemistry of these and related compounds is discussed.Key words: ab initio calculations, Me3S+ and SeC162-; group V trihalides; lone electron pair; trialkylsulfonium salts; VSEPR theory.OSVALD KNOP, ANTHONY LINDEN, BEVERLY R. VINCENT, S. C. CHOI, T. STANLEY CAMERON et RUSSELL J. BOYD. Can. J. Chem. 67, 1984Chem. 67, (1989.En se basant sur les rCsultats d'une analyse dCtaillte de situations typiques dans des cristaux contenant des espkces YEL3', on suggkre que la paire dYClectron libre (E, PL) sur l'atome Y ne dCtermine pas per se la structure cristalline ou I'orientation des unit& Y EL3' dans le cristal. ConsidCrte comme une entitC qui occupe du volume, la PL n'a pratiquement pas de volume effectif intrinskque. Quelles que soient les propriCtCs associCes avec la prCsence de la PL, elles ne sont pas autonomes; elles dCcoulent de l'implication stCrCochimique intrinskque de la PL dans la gComCtrie de et de la distribution de charge dans l'ion ou la molCcule YEL$ libre et ainsi des consCquences de cette gComCtrie sur I'empilement cristallin. Des calculs ab initio (6-3 lG*) dCmontrent que, aux distances observkes dans les cristaux, la densite tlectronique dans la rkgion de la PL d'un ion n'est que ICgkrement perturbCe par la charge du contre-ion. I1 existe une gr...

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A Ferroelectric Chloride of Perowskite Type. Crystal Structure of CsGeCl3.

Cited by 78 publications

References 0 publications

The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells

The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells

²⁰⁷Pb and ²⁰⁵Tl NMR on Perovskite Type Crystals APbX₃ (A = Cs, Tl, X = Br, I)

The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆

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A Ferroelectric Chloride of Perowskite Type. Crystal Structure of CsGeCl3.

Cited by 78 publications

References 0 publications

The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells

The dynamics of methylammonium ions in hybrid organic–inorganic perovskite solar cells

207Pb and 205Tl NMR on Perovskite Type Crystals APbX3 (A = Cs, Tl, X = Br, I)

The lone electron pair and crystal packing: observations on pyramidal YEL3ε species, abinitio calculations, and the crystal structures of Me3SOI, Et3SI, (Me3S)2SnCl6, (Me3SO)2SnCl6, and (Et3S)2SnCl6

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²⁰⁷Pb and ²⁰⁵Tl NMR on Perovskite Type Crystals APbX₃ (A = Cs, Tl, X = Br, I)

The lone electron pair and crystal packing: observations on pyramidal YEL₃^ε species, abinitio calculations, and the crystal structures of Me₃SOI, Et₃SI, (Me₃S)₂SnCl₆, (Me₃SO)₂SnCl₆, and (Et₃S)₂SnCl₆