An extended Tolerance Factor approach for organic–inorganic perovskites

Kieslich, Gregor; Sun, Shijing; Cheetham, Anthony K.

doi:10.1039/c5sc00961h

Cited by 633 publications

(581 citation statements)

References 57 publications

(74 reference statements)

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“…In hybrid perovskites, a modified version of Goldschmidt's equation is used to calculate t, because there is a molecular cation instead of a monatomic one (18). Cheetham and coworkers (19,20) modified the tolerance factor equation to use an effective radius of the organic cation (Table S2) 3 18.38 ± 0.85(4) 34.50 ± 1.01 MAPbBr 3 25.86 ± 0.25(4) 6.69 ± 1.41 MAPbCl 3 26.13 ± 0.32(4) −9.03 ± 1.68…”

Section: Resultsmentioning

confidence: 99%

Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

Nagabhushana

Shivaramaiah

Navrotsky

2016

Proc. Natl. Acad. Sci. U.S.A.

356

268

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Hybrid perovskites, especially methylammonium lead iodide (MAPbI 3 ), exhibit excellent solar power conversion efficiencies. However, their application is plagued by poor chemical and structural stability. Using direct calorimetric measurement of heats of formation, MAPbI 3 is shown to be thermodynamically unstable with respect to decomposition to lead iodide and methylammonium iodide, even in the absence of ambient air or light or heat-induced defects, thus limiting its long-term use in devices. The formation enthalpy from binary halide components becomes less favorable in the order MAPbCl 3 , MAPbBr 3 , MAPbI 3 , with only the chloride having a negative heat of formation. Optimizing the geometric match of constituents as measured by the Goldschmidt tolerance factor provides a potentially quantifiable thermodynamic guide for seeking chemical substitutions to enhance stability.hybrid halide perovskites | thermodynamic instability | solar cells | tolerance factor | enthalpy of formation O rganic-inorganic hybrid materials which adopt the perovskite structure have gained increasing attention due to their excellent solar to electric power conversion efficiencies (PCEs). Methylammonium lead halide (MAPbX 3 ) perovskite leads the race with a PCE of 20%. Although these perovskites were discovered in 1978 by Weber, who described their structural and physical properties (1, 2), their solar cell application was explored only in 2009 by Miyasaka and coworkers. (3). Recently a very impressive PCE of 20% has been claimed for these materials (4). The extraordinary performance of hybrid perovskites has been attributed to their large absorption efficiency, favorable band gap, high charge mobility, and long-range electron hole transport (5-8). The AMX 3 perovskite structure provides great flexibility for modifications where, in principle, a range of similar compounds with different energy gaps can be synthesized by variation and/or partial substitution of the organic moiety (A = methylammonium, ethylammonium, formamidinium, or other possible organic cations), the metal (M = Pb, Sn and possible others), or the halide (X = I, Br, Cl). All these factors make organic metal halide perovskites frontrunners compared with other conventional solar cell materials (9).

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Section: Resultsmentioning

confidence: 99%

Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

Nagabhushana

Shivaramaiah

Navrotsky

2016

Proc. Natl. Acad. Sci. U.S.A.

356

268

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“…In general, PVSK materials with a t value between 0.8 and 1.0 prefer a cubic PVSK structure, and photo-inactive non-PVSK structures are formed when the value of t is larger (>1) or smaller (<0.8), as shown in Figure 2. [27,28] To date, only three A cations are known to be able to construct the 3-dimensional PVSK structure with Pb/ Sn as the central metal in a stable manner: MA, FA, and Cs + . Cs + is the only inorganic cation with a sufficient atomic radius to sustain the PVSK structure.…”

Section: Introductionmentioning

confidence: 99%

The Emergence of the Mixed Perovskites and Their Applications as Solar Cells

Xiao

Liü

Zhang

et al. 2017

Advanced Energy Materials

126

105

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The halide perovskite (PVSK) materials (with ABX3 formulation) have emerged as “dream materials” for photovoltaic (PV) applications due to their remarkable physical properties such as high optical absorption coefficient, carrier mobility, long carrier diffusion lengths, etc. These properties have enabled the PV devices to reach higher than 20% power conversion efficiencies (PCE) in record time. The further pursuit of higher PCE and improved stability brings forth increasing interests in so‐called “mixed composition” PVSK materials, consisting of partial substitution of the A, B, and/or X‐sites with alternative elements/molecules of similar size. Herein, we highlight the recent advances in developing mixed PVSK for PVs and their relevant optoelectronic properties. We mainly focus on mixed PVSK materials in the form of polycrystalline thin films, but also discuss nanostructured and two‐dimensional (2D) PVSK materials due to the increasing interest of broad readership. Efforts are exerted to elucidate the design principles of mixed PVSK and fabrication techniques for high performance optoelectronic devices, which help deepen our fundamental understanding of mixed PVSK systems. We hope this review will shed light onto the design and synthesis of mixed PVSK materials to further the progress of PVSK photovoltaics towards higher efficiencies and longer lifetimes.

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“…Figure 1(a) is an illustration of the crystal structure of 3D perovskite, with the typical chemical formula ABX 3 , where the A, B, and X parts can be substituted by various elements (A = CH 3 − , F − · · · ) as long as the Goldschmidt tolerance rule to maintain structural stability is fulfilled. [2][3][4] Figure 1(b) shows an illustration of the crystal structure tuned from layered to bulk perovskite. 5 While the first report of perovskite "dye-sensitized" solar cells showed only a 3.8% power conversion efficiency in 2009, 6 hybrid lead-halide 3D perovskites have initiated an unprecedented breakthrough in the field of photovoltaics from 2012, 7,8 delivering now excellent power conversion efficiency above 20%, comparable with silicon-based devices.…”

Section: Introductionmentioning

confidence: 99%

Research Update: Challenges for high-efficiency hybrid lead-halide perovskite LEDs and the path towards electrically pumped lasing

Price

Deschler

2016

APL Materials

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Hybrid lead-halide perovskites have emerged as promising solution-processed semiconductor materials for thin-film optoelectronics. In this review, we discuss current challenges in perovskite LED performance, using thin-film and nano-crystalline perovskite as emitter layers, and look at device performance and stability. Fabrication of electrically pumped, optical-feedback devices with hybrid lead halide perovskites as gain medium is a future challenge, initiated by the demonstration of optically pumped lasing structures with low gain thresholds. We explain the material parameters affecting optical gain in perovskites and discuss the challenges towards electrically pumped perovskite lasers.

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An extended Tolerance Factor approach for organic–inorganic perovskites

Abstract: Tolerance Factors of possible hybrid perovskites are calculated for over 2500 amine-metal-anion permutations of the periodic table.

Cited by 633 publications

References 57 publications

Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

Direct calorimetric verification of thermodynamic instability of lead halide hybrid perovskites

The Emergence of the Mixed Perovskites and Their Applications as Solar Cells

Research Update: Challenges for high-efficiency hybrid lead-halide perovskite LEDs and the path towards electrically pumped lasing

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