Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance

Yin, Wan‐Jian; Shi, Tingting; Yan, Yanfa

doi:10.1002/adma.201306281

Cited by 1,985 publications

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“…It has been established that in AM IV X VII 3 perovskites the valence band maximum (VBM) is formed by anti-bonding states between M IV -s and X VII -p orbitals, and the conduction band minimum (CBM) mainly originates from M IV -p orbitals. 24,25,55 For the A 2 M + M 3+ X VII 6 cases, the VBM is composed of anti-bonding states between M + /M 3+ -s/d orbitals and X VII -p orbitals, and the CBM is mainly dominated by M + /M 3+ -p characters (Figure 3c, see also below). Walking from fluorides, chlorides, bromides, to iodides, the X VII -p orbitals become higher in energy, resulting in raised VBM and thus reduced band gaps.…”

Section: Methodsmentioning

confidence: 99%

“…Figure 3b) is quite similar to those of APbX VII 3 . 24,25,55 The VBM is located at the zonecenter Γ point because of absence of the electronic symmetry reduction in the above type-I and II cases. The band gap is thus direct.…”

Section: Chemical Trends Of Electronic Properties and Classificationmentioning

confidence: 99%

“…that achieved similar PCEs after decades of efforts. The high PCE of halide perovskites originates from their correlative intrinsic material properties, including suitable band gaps and high threshold light absorption, 23,24 defect-tolerant feature, [25][26][27][28][29] ultra-long carrier diffusion length, 9 low exciton binding energy, 30,31 balanced electron and hole mobility, 32,33 etc. These unique properties, accompanying with the low-cost solutionbased fabrication routes, make them ideal candidates as newgeneration photovoltaic absorbers.…”

Section: Introductionmentioning

confidence: 99%

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Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

et al. 2017

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Hybrid organic-inorganic halide perovskites with the prototype material of CH 3 NH 3 PbI 3 have recently attracted intense interest as low-cost and high-performance photovoltaic absorbers. Despite the high power conversion efficiency exceeding 20% achieved by their solar cells, two key issues -the poor device stabilities associated with their intrinsic material instability and the toxicity due to water soluble Pb 2+ -need to be resolved before large-scale commercialization. Here, we address these issues by exploiting the strategy of cation-transmutation to design stable inorganic Pb-free halide perovskites for solar cells. The idea is to convert two divalent Pb 2+ ions into one monovalent M + and one trivalent M 3+ ions, forming a rich class of quaternary halides in double-perovskite structure. We find through first-principles calculations this class of materials have good phase stability against decomposition and wide-range tunable optoelectronic properties. With photovoltaic-functionality-directed materials screening, we identify eleven optimal materials with intrinsic thermodynamic stability, suitable band gaps, small carrier effective masses, and low excitons binding energies as promising candidates to replace Pb-based photovoltaic absorbers in perovskite solar cells. The chemical trends of phase stabilities and electronic properties are also established for this class of materials, offering useful guidance for the development of perovskite solar cells fabricated with them.

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Section: Methodsmentioning

confidence: 99%

Section: Chemical Trends Of Electronic Properties and Classificationmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

et al. 2017

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“…[ 17,18 ] MAPbI 3 also appears to exhibit only shallow trap-levels and although the grain boundaries have recently been shown to induce nonradiative decay, [ 19 ] regions only a few tens of nm away from the grain boundaries appear to be unaffected. [ 20,21 ] Furthermore, low Urbach energies, which are extracted from near band edge optical absorption measurements and serve as a benchmark for crystalline phase disorder, indicate low disorder and sharp band edges for lead tri-halide perovskites (15-23 meV). [ 22,23 ] All of these properties contribute to high open-circuit voltages, long charge-carrier lifetimes, and micrometer diffusion lengths, which are crucial for planar-hetero junction photovoltaics.…”

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confidence: 99%

Charge‐Carrier Dynamics and Mobilities in Formamidinium Lead Mixed‐Halide Perovskites

et al. 2015

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by at least four orders of magnitude. [ 17,18 ] MAPbI 3 also appears to exhibit only shallow trap-levels and although the grain boundaries have recently been shown to induce nonradiative decay, [ 19 ] regions only a few tens of nm away from the grain boundaries appear to be unaffected. [ 20,21 ] Furthermore, low Urbach energies, which are extracted from near band edge optical absorption measurements and serve as a benchmark for crystalline phase disorder, indicate low disorder and sharp band edges for lead tri-halide perovskites (15-23 meV). [ 22,23 ] All of these properties contribute to high open-circuit voltages, long charge-carrier lifetimes, and micrometer diffusion lengths, which are crucial for planar-hetero junction photovoltaics. [ 1,24 ] Nonetheless, these parameters are also expected to depend on the infl uence of crystallization condition on perovskite morphology in fabricated fi lms. [ 25 ] A distinct benefi t of organic-inorganic perovskite materials (e.g., over silicon) is that their bandgap can be tuned relatively easily with chemical composition, allowing attractive coloration and multijunction or tandem cell designs. For example, changing the metal cation at the M site from Pb 2+ to the less toxic Sn 2+ to form CH 3 NH 3 SnI 3 shifts the optical bandgap from 1.55 to 1.3 eV into the range of the "ideal" single-junction solar cell bandgap between 1.1 and 1.4 eV. [ 26,27 ] However, stability issues arising from the oxidation of tin have so far prevented widespread use. Alternatively, tuning the size of the A site cation has been proven to change optical and electronic properties of the perovskite and to signifi cantly infl uence solar cell performance. [ 28 ] Replacing MA in MAPbI 3 by the larger cation formamidinium HC(NH 2 ) 2 + (FA) was found to decrease the bandgap from 1.57 to 1.48 eV, [29][30][31] yield long photoluminescence (PL) lifetimes, high PCEs, [ 28 ] and lower recombination and device hysteresis. [ 32 ] Highest PCEs of 20.1% have been reported [12][13][14] to date for solar cells based on FAPbI 3 making this an attractive system to explore. In addition, the gradual replacement of the MA cation by FA through the fi lm was shown to create a mixed cation-lead-iodide PSC allowing for energetic gradients. [ 33 ] However, mixing of the halide component in the perovskite offers the fi nest tuning of the optical properties of the perovskite fi lm. Here, the mixed organic lead iodide/bromide system has recently gained strong interest for application in PSCs. [ 11,28 ] By changing the ratio between bromide and iodide (at the X site anion), the bandgap can be tailored between 1.55 eV (MAPbI 3 ) and 2.3 eV (MAPbBr 3 ), which results in the coverage of much of the visible spectrum and paves the way for the development of tandem solar cells. [ 11 ] In addition to MAPb(Br y I 1-y ) 3 , its formamidinium relative FAPb(Br y I 1-y ) 3 has been explored. [ 28 ] Most fractional mixtures of FAPb(Br y I 1-y ) 3 were found to be crystalline, with the exception of the region between y = 0.3 and Recent year...

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“…36 Many other recent works have been written on understanding the properties of hybrid lead-halide perovskites that make them excellent solar absorbers, e.g., energetic carrier screening via polarons, which may lead to new design rules. [37][38][39][40][41][42][43] In many cases, these materials are being investigated as solar absorbers for the first time. Among the multitude of physical properties to be assessed, the most critical for rigorously evaluating the promise of each material for photovoltaics at an early stage are:…”

Section: Introductionmentioning

confidence: 99%

Perovskite-Inspired Photovoltaic Materials: Toward Best Practices in Materials Characterization and Calculations

et al. 2017

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ABSTRACT:Recently, there has been an explosive growth in research based on hybrid lead-halide perovskites for photovoltaics owing to rapid improvements in efficiency. The advent of these materials for solar applications has led to widespread interest in understanding the key enabling properties of these materials. This has resulted in renewed interest in related compounds and a search for materials that may replicate the defect-tolerant properties and long lifetimes of the hybrid lead-halide perovskites. Given the rapid pace of development of the field, the rises in efficiencies of these systems have outpaced the more basic understanding of these materials. Measuring or calculating the basic properties, such as crystal/electronic structure and composition, can be challenging because some of these materials have anisotropic structures, and/or are composed of both heavy metal cations and volatile, mobile, light elements. Some consequences are beam damage during characterization, composition change under vacuum, or compound effects, such as the alteration of the electronic structure through the influence of the substrate. These effects make it challenging to understand the basic properties integral to optoelectronic operation. Compounding these difficulties is the rapid pace with which the field progresses. This has created an ongoing need to continually evaluate best practices with respect to characterization and calculations, as well as to identify inconsistencies in reported values to determine if those inconsistencies are rooted in characterization methodology or materials synthesis. This article describes the difficulties in characterizing hybrid lead-halide perovskites and new materials, and how these challenges may be overcome. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 2 challenges discussed. The focus in this article is on crystallography, composition measurements, photoemission spectroscopy and calculations on perovskites and new, related absorbers. We suggest how some of the important artifacts could be avoided and how the reporting for each technique could be streamlined between groups to ensure reproducibility as the field progresses.

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Unique Properties of Halide Perovskites as Possible Origins of the Superior Solar Cell Performance

Cited by 1,985 publications

References 47 publications

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

Design of Lead-Free Inorganic Halide Perovskites for Solar Cells via Cation-Transmutation

Charge‐Carrier Dynamics and Mobilities in Formamidinium Lead Mixed‐Halide Perovskites

Perovskite-Inspired Photovoltaic Materials: Toward Best Practices in Materials Characterization and Calculations

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