Giant Rashba splitting in 2D organic-inorganic halide perovskites measured by transient spectroscopies
TL;DR: A giant Rashba splitting in this compound, with energy splitting of (40 ± 5) meV and Rashba parameter of (1.6 ± 0.1) eV·Å, is obtained, which shows that 2D hybrid perovskites have great promise for potential applications in spintronics.
Abstract: Two-dimensional (2D) layered hybrid organic-inorganic halide perovskite semiconductors form natural "multiple quantum wells" that have strong spin-orbit coupling due to the heavy elements in their building blocks. This may lead to "Rashba splitting" close to the extrema in the electron bands. We have used a plethora of ultrafast transient, nonlinear optical spectroscopies and theoretical calculations to study the primary (excitons) and long-lived (free carriers) photoexcitations in thin films of 2D perovskite, namely, (C6H5C2H4NH3)2PbI4. The density functional theory calculation shows the occurrence of Rashba splitting in the plane perpendicular to the 2D barrier. From the electroabsorption spectrum and photoinduced absorption spectra from excitons and free carriers, we obtain a giant Rashba splitting in this compound, with energy splitting of (40 ± 5) meV and Rashba parameter of (1.6 ± 0.1) eV·A, which are among the highest Rashba splitting size parameters reported so far. This finding shows that 2D hybrid perovskites have great promise for potential applications in spintronics.
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TL;DR: In this article, a review of the state of the art in 2D perovskites is provided, providing an overview of structural and materials engineering aspects and optical and photophysical properties.
Abstract: Hybrid perovskites are currently one of the most active fields of research owing to their enormous potential for photovoltaics. The performance of 3D hybrid organic–inorganic perovskite solar cells has increased at an incredible rate, reaching power conversion efficiencies comparable to those of many established technologies. However, the commercial application of 3D hybrid perovskites is inhibited by their poor stability. Relative to 3D hybrid perovskites, low-dimensional — that is, 2D — hybrid perovskites have demonstrated higher moisture stability, offering new approaches to stabilizing perovskite-based photovoltaic devices. Furthermore, 2D hybrid perovskites have versatile structures, enabling the fine-tuning of their optoelectronic properties through compositional engineering. In this Review, we discuss the state of the art in 2D perovskites, providing an overview of structural and materials engineering aspects and optical and photophysical properties. Moreover, we discuss recent developments along with the main limitations of 3D perovskites and assess the advantages of 2D perovskites over their 3D parent structures in terms of stability. Finally, we review recent achievements in combining 3D and 2D perovskites as an approach to simultaneously boost device efficiency and stability, paving the way for mixed-dimensional perovskite solar cells for commercial applications. Combining low-dimensional and 3D perovskites is a promising approach to achieve stable and efficient solar cells. In this Review, we discuss the structural, optical and photophysical properties of low-dimensional perovskites, compare the stability and efficiency of 2D and 3D perovskite devices, and consider 2D/3D composites as a strategy to increase the stability of perovskite solar cells.
572 citations
Ludwig Maximilian University of Munich1, University of Cambridge2, University of Hyderabad3, Katholieke Universiteit Leuven4, Massachusetts Institute of Technology5, University of Antwerp6, Indian Institute of Science7, Yantai University8, King Abdullah University of Science and Technology9, University of Vigo10, Nanjing University of Science and Technology11, Lawrence Berkeley National Laboratory12, University of California, Berkeley13, Nanyang Technological University14, Soochow University (Suzhou)15, Technische Universität München16, ETH Zurich17, Lund University18, Hokkaido University19, Chinese Academy of Sciences20, University of California, Santa Cruz21, Beijing Institute of Technology22, City University of Hong Kong23, University of Texas at Austin24, Indian Association for the Cultivation of Science25, San Diego State University26, University of Washington27, Texas A&M University28, Bilkent University29, James I University30, Max Planck Society31, National Renewable Energy Laboratory32, University of Valencia33, Shanghai Jiao Tong University34, Istituto Italiano di Tecnologia35, Swiss Federal Laboratories for Materials Science and Technology36, University of Notre Dame37, Monash University, Clayton campus38, Imperial College London39
TL;DR: A comprehensive review of metal-halide perovskite nanocrystals can be found in this article, where researchers having expertise in different fields (chemistry, physics, and device engineering) have joined together to provide a state-of-the-art overview and future prospects of metalhalide nanocrystal research.
Abstract: Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.
471 citations
TL;DR: The present paper is a review of the past and present literature on both colloidal nanostructures and multilayered compounds, emphasizing that availability of accurate structural information is of dramatic importance to reach a fair understanding of quantum and dielectric confinement effects.
Abstract: Hybrid halide perovskites are now superstar materials leading the field of low-cost thin film photovoltaics technologies. Following the surge for more efficient and stable 3D bulk alloys, multilayered halide perovskites and colloidal perovskite nanostructures appeared in 2016 as viable alternative solutions to this challenge, largely exceeding the original proof of concept made in 2009 and 2014, respectively. This triggered renewed interest in lower-dimensional hybrid halide perovskites and at the same time increasingly more numerous and differentiated applications. The present paper is a review of the past and present literature on both colloidal nanostructures and multilayered compounds, emphasizing that availability of accurate structural information is of dramatic importance to reach a fair understanding of quantum and dielectric confinement effects. Layered halide perovskites occupy a special place in the history of halide perovskites, with a large number of seminal papers in the 1980s and 1990s. In ...
416 citations
TL;DR: This comprehensive review explores how the unique chemistry of halide perovskites can be exploited to tailor film growth processes and highlights the connections between processing methods and the resulting film characteristics.
Abstract: Halide perovskites are an intriguing class of materials that have recently attracted considerable attention for use as the active layer in thin film optoelectronic devices, including thin-film transistors, light-emitting devices, and solar cells. The “soft” nature of these materials, as characterized by their low formation energy and Young’s modulus, and high thermal expansion coefficients, not only enables thin films to be fabricated via low-temperature deposition methods but also presents rich opportunities for manipulating film formation. This comprehensive review explores how the unique chemistry of these materials can be exploited to tailor film growth processes and highlights the connections between processing methods and the resulting film characteristics. The discussion focuses principally on methylammonium lead iodide (CH3NH3PbI3 or MAPbI3), which serves as a useful and well-studied model system for examining the unique attributes of halide perovskites, but various other important members of this...
404 citations
TL;DR: In this article, the basic structure and optoelectronic properties of 2D perovskites, including band structure, optical properties, and charge transport, are discussed, including progress on various synthesis strategies and their impact on structural and optical properties.
Abstract: Two-dimensional (2D) perovskites have attracted considerable interest for their promising applications for solar cells and other optoelectronics, such as light-emitting diodes, spintronics, and photodetectors. Here, we review the recent achievements of 2D perovskites for various optoelectronic applications. First, we discuss the basic structure and optoelectronic properties of 2D perovskites, including band structure, optical properties, and charge transport. We then highlight recent achievements using 2D perovskites in solar cells and beyond solar cells, including progress on various synthesis strategies and their impact on structural and optoelectronic properties. Finally, we discuss current challenges and future opportunities to further develop 2D perovskites for various applications.
346 citations
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TL;DR: In this article, the authors propose a quantum theory of radiative absorption and emission in dielectric dielectrics, based on the classical propagation and interband absorption, respectively.
Abstract: Preface 1. Introduction 2. Classical propagation 3. Interband absorption 4. Excitons 5. Luminescence 6. Semiconductor quantum wells 7. Free electrons 8. Molecular materials 9. Luminescence centres 10. Phonons 11. Nonlinear optics Appendix A: Electromagnetism in dielectrics Appendix B: Quantum theory of radiative absorption and emission Appendix C: Band theory Appendix D: Semiconductor p-i-n diodes
2,660 citations
"Giant Rashba splitting in 2D organi..." refers result in this paper
...We could readily fit this PA spectrum by a Drude-type FCA response, in which the PA spectrum varies as w (32); this validates our approach....
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TL;DR: Thin films of near-single-crystalline quality are produced, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport.
Abstract: Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.
2,566 citations
TL;DR: The broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and the properties that have delivered light-emitting diodes and lasers are described.
Abstract: Metal-halide perovskites are crystalline materials originally developed out of scientific curiosity. Unexpectedly, solar cells incorporating these perovskites are rapidly emerging as serious contenders to rival the leading photovoltaic technologies. Power conversion efficiencies have jumped from 3% to over 20% in just four years of academic research. Here, we review the rapid progress in perovskite solar cells, as well as their promising use in light-emitting devices. In particular, we describe the broad tunability and fabrication methods of these materials, the current understanding of the operation of state-of-the-art solar cells and we highlight the properties that have delivered light-emitting diodes and lasers. We discuss key thermal and operational stability challenges facing perovskites, and give an outlook of future research avenues that might bring perovskite technology to commercialization.
2,513 citations
"Giant Rashba splitting in 2D organi..." refers background in this paper
...The 3D hybrid organic-inorganic perovskites (thereafter, hybrid perovskites), such asmethyl ammonium lead halogen (MAPbX3, where X is a halogen), have recently attracted immense attention because of several promising optoelectronic device applications, such as photovoltaic solar cells, light-emitting diodes, and lasers (10, 11)....
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TL;DR: In this article, the spin-orbit interaction in an inverted I${\mathrm{n}}_{0.53}$G${a}}{0.48}$As quantum well can be controlled by applying a gate voltage.
Abstract: We have confirmed that a spin-orbit interaction in an inverted I${\mathrm{n}}_{0.53}$G${\mathrm{a}}_{0.47}$As/I${\mathrm{n}}_{0.52}$A${\mathrm{l}}_{0.48}$As quantum well can be controlled by applying a gate voltage. This result shows that the spin-orbit interaction of a two-dimensional electron gas depends on the surface electric field. The dominant mechanism for the change in the spin-orbit interaction parameter can be attributed to the Rashba term. This inverted I${\mathrm{n}}_{0.53}$G${\mathrm{a}}_{0.47}$As/I${\mathrm{n}}_{0.52}$A${\mathrm{l}}_{0.48}$As heterostructure is one of the promising materials for the spin-polarized field effect transistor which is proposed by Datta and Das [Appl. Phys. Lett. 56, 665 (1990)].
1,801 citations
TL;DR: The homologous 2D halide perovskites define a promising class of stable and efficient light-absorbing materials for solid-state photovoltaics and other applications.
Abstract: We report on the fabrication and properties of the semiconducting 2D (CH3(CH2)3NH3)2(CH3NH3)n–1PbnI3n+1 (n = 1, 2, 3, and 4) perovskite thin films. The band gaps of the series decrease with increasing n values, from 2.24 eV (CH3(CH2)3NH3)2PbI4 (n = 1) to 1.52 eV CH3NH3PbI3 (n = ∞). The compounds exhibit strong light absorption in the visible region, accompanied by strong photoluminescence at room temperature, rendering them promising light absorbers for photovoltaic applications. Moreover, we find that thin films of the semi-2D perovskites display an ultrahigh surface coverage as a result of the unusual film self-assembly that orients the [PbnI3n+1]− layers perpendicular to the substrates. We have successfully implemented this 2D perovskite family in solid-state solar cells, and obtained an initial power conversion efficiency of 4.02%, featuring an open-circuit voltage (Voc) of 929 mV and a short-circuit current density (Jsc) of 9.42 mA/cm2 from the n = 3 compound. This result is even more encouraging con...
1,589 citations