Atomic-scale imaging of CH3NH3PbI3 structure and its decomposition pathway

Chen, Shulin; Wu, Chenjun; Han, Bo; Liu, Zhetong; Zhou, Mi; Hao, Weizhong; Zhao, Jinjin; Wang, Xiao; Liu, Kaihui; Qi, Junlei; Cao, Jian; Feng, Jicai; Yu, Dapeng; Li, Jiangyu; Gao, Peng

doi:10.1038/s41467-021-25832-9

Cited by 58 publications

(46 citation statements)

References 67 publications

(88 reference statements)

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“…[11,14] Rothmann et al used transmission electron microscopy (TEM) to quantify structural changes in methylammonium lead iodide films (MAPbI 3 ) at fluences as low as 100 e -Å -2 , [11] in which loss of the organic moieties results in lattice contraction and the formation of a supercell, further described by Chen et al as MAPbI 2.5 , ultimately degrading into PbI 2 . [15,16] The appearance of an intermediate phase of degradation agrees with similar studies by scanning electron microscopy techniques. [17][18][19] Alberti et al also reported the detrimental effect of having excess Pb-related defects during fabrication, which aggregate and feed degradation at grain boundaries upon electron irradiation.…”

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confidence: 85%

Unveiling the Interaction Mechanisms of Electron and X‐ray Radiation with Halide Perovskite Semiconductors using Scanning Nanoprobe Diffraction

et al. 2022

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The interaction of high‐energy electrons and X‐ray photons with beam‐sensitive semiconductors such as halide perovskites is essential for the characterization and understanding of these optoelectronic materials. Using nanoprobe diffraction techniques, which can investigate physical properties on the nanoscale, studies of the interaction of electron and X‐ray radiation with state‐of‐the‐art (FA0.79MA0.16Cs0.05)Pb(I0.83Br0.17)3 hybrid halide perovskite films (FA, formamidinium; MA, methylammonium) are performed, tracking the changes in the local crystal structure as a function of fluence using scanning electron diffraction and synchrotron nano X‐ray diffraction techniques. Perovskite grains are identified, from which additional reflections, corresponding to PbBr2, appear as a crystalline degradation phase after fluences of 200 e− Å−2. These changes are concomitant with the formation of small PbI2 crystallites at the adjacent high‐angle grain boundaries, with the formation of pinholes, and with a phase transition from tetragonal to cubic. A similar degradation pathway is caused by photon irradiation in nano‐X‐ray diffraction, suggesting common underlying mechanisms. This approach explores the radiation limits of these materials and provides a description of the degradation pathways on the nanoscale. Addressing high‐angle grain boundaries will be critical for the further improvement of halide polycrystalline film stability, especially for applications vulnerable to high‐energy radiation such as space photovoltaics.

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confidence: 85%

Unveiling the Interaction Mechanisms of Electron and X‐ray Radiation with Halide Perovskite Semiconductors using Scanning Nanoprobe Diffraction

et al. 2022

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“…Some of the impressive ones include the aforementioned in situ PL, and the electrical biasing of thin samples in situ in TEM, which has been reported to provide insight into biasinduced degradation mechanisms of MAPbI 3 PSCs at the nanoscale. [137][138][139] However, the beam sensitivity problem should be solved. In addition, more models that can simulate the dynamic equilibrium of ion migration are needed.…”

Section: Discussionmentioning

confidence: 99%

Ion Migration in Organic–Inorganic Hybrid Perovskite Solar Cells: Current Understanding and Perspectives

Zhu

Wang

Zhang

et al. 2022

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shown that ion migration is an inherent property of perovskite. [8][9][10][11] When discussing perovskites, due to their soft lattice feature, weak chemical bonds and low defect formation energy are generally considered. For the ABX 3 perovskites, A-site ions (methylamium ions (MA + ) and formamidium ions (FA + )), B-site ions (lead ions (Pb 2+ ) and tin ions (Sn 2+ )), and X-site ions (iodide ions (I − ), bromide ions (Br − ), chloride ions (Cl − ), and other halogen ions) have low activation barrier and high diffusion coefficient. [3] These ionic defects within the lattice are easily activated to cause severe ion migration in the perovskite films under external factors. In fact, in addition to the internal ions of perovskite, ions introduced from the ambient atmosphere also have the potential to migrate. [12] To detect the effects of ion migration, abnormal phenomenon in perovskite were given attention. Snaith et al. first reported the abnormal photocurrent-voltage hysteresis phenomenon, which was that forward and reverse scan J-V curves can't overlap in PSCs. [13] Electric field-driven ion migration was considered to be the key factor to affect photocurrent hysteresis. Xiao et al. [14] reported the switchable photovoltaic effect in a plane heterojunction structure with symmetric electrodes, in which the current direction could be completely overturned. Ion migration was speculated to be the main cause. The reason for this inference is that the migration as well as the accumulation of ions can change the intrinsic electric field of the perovskite films, even causing local crystal structure changes, which in turn lead to further degradation of the PSCs and severely affect the operating stability. [15,16] Apart from these, ion migration can also cause slow photoconductivity response, halide redistribution, and segregation. [17] In order to push the commercialization step of PSCs, a clear understanding of the ion migration in OIHPs is meaningful and highly desired. Although some reports have reviewed the ion migration in OIHPs, [18][19][20] the explanation of the mechanisms behind ion migration is still incomplete and is usually introduced directly from theoretical calculations. Meanwhile, more reviews only focused on the ion migration in PSCs; ion migration in fact has profound implications for many other applications of perovskite materials, like photodetector, light emitting diodes, and random access memories. The use of low-dimensional materials to inhibit ion migration is an effective strategy, but the various species involved are not discussed in detail. What's more, the study of ion migration is quickly Organic-inorganic hybrid perovskite (OIHPs) solar cells are the most promising alternatives to traditional silicon solar cells, with a certified power conversion efficiency beyond 25%. However, the poor stability of OHIPs is one of the thorniest obstacles that hinder its commercial development. Among all the factors affecting stability, ion migration is prominent because it is unavoidable and intrinsic in OH...

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“…[ 28,29 ] Unfortunately, the applications of organic–inorganic perovskites‐based RRAM devices are limited by the poor thermal stability and moisture sensitivity, because of the instability of the organic cations and severe ion migration. [ 30,31 ] In contrast, all‐inorganic perovskite quantum dots (QDs) [ 32,33 ] or films show superior stability and reproducibility by replacing the organic cation (MA or FA) with an inorganic one (such as Cs). Thus, all‐inorganic perovskite QDs are considered to be promising candidates for use as insulating materials in RRAM devices.…”

Section: Introductionmentioning

confidence: 99%

Flexible Transparent High‐Efficiency Photoelectric Perovskite Resistive Switching Memory

Liu

Ren

et al. 2022

Adv Funct Materials

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Perovskite resistive random-access memory (RRAM) is a promising candidate for next-generation logic, adaptive and nonvolatile memory devices, because of its high ON/OFF ratio, low-cost fabrication, and good photoelectric regulation performance. In this work, a flexible transparent CsPbBr 3 quantum dots (QDs) mixed in graphene oxide (GO) RRAM device is introduced, which is controllable by both an electric field and illumination. Under illumination, the ON/OFF ratio of the Ag/CsPbBr 3 QDs:GO/ITO device is ≈1.4 × 10 7 , which is 1077 times larger than that in the dark condition (1.3 × 10 4 ). The SET/RESET voltages are +2.28/−2.04 V and +1.68/−1.08 V under the dark and illumination conditions, respectively. As a flexible memory device, the resistances are little affected by the bending curvatures and load-cycling. Before and after 10 4 bending cycles with a radius of 5 mm under illumination, the ON/OFF ratios keep in the same order, which are 2.5 × 10 7 and 2.3 × 10 7 , respectively. The ratio values are 8.8 × 10 4 and 2.9 × 10 4 under the dark condition, respectively. This innovative resistive memory based on the CsPbBr 3 QDs:GO hybrid film supports a huge space for the development of photoelectrical dual-controlled flexible RRAM devices.

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Atomic-scale imaging of CH3NH3PbI3 structure and its decomposition pathway

Cited by 58 publications

References 67 publications

Unveiling the Interaction Mechanisms of Electron and X‐ray Radiation with Halide Perovskite Semiconductors using Scanning Nanoprobe Diffraction

Unveiling the Interaction Mechanisms of Electron and X‐ray Radiation with Halide Perovskite Semiconductors using Scanning Nanoprobe Diffraction

Ion Migration in Organic–Inorganic Hybrid Perovskite Solar Cells: Current Understanding and Perspectives

Flexible Transparent High‐Efficiency Photoelectric Perovskite Resistive Switching Memory

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