Based on first-principles calculations, we show that chemically active metal ns2 lone pairs play an important role in exciton relaxation and dissociation in low-dimensional halide perovskites. We studied excited-state properties of several recently discovered luminescent all-inorganic and hybrid organic-inorganic zero-dimensional (0D) Sn and Pb halides. The results show that, despite the similarity in ground-state electronic structure between Sn and Pb halide perovskites, the chemically more active Sn2+ lone pair leads to stronger excited-state structural distortion and larger Stokes shift in Sn halides. The enhanced Stokes shift hinders excitation energy transport, which reduces energy loss to defects and increases the photoluminescence quantum efficiency (PLQE). The presence of the ns2 metal cations in the 0D halide perovskites also promotes the exciton dissociation into electron and hole polarons especially in all-inorganic compounds, in which the coupling between metal-halide clusters is significant.
Metal halide perovskites are attracting tremendous interest for a variety of optoelectronic applications. The ability to tune the perovskite bandgap by tweaking the chemical compositions opens up new applications as coloured emitters and as components of tandem photovoltaics. Nevertheless, non-radiative losses are still limiting performance, with luminescence yields in state-of-the-art perovskite solar cells still far from 100% under solar illumination conditions. Furthermore, in mixed halide perovskite systems designed for continuous bandgap tunability (bandgaps ~1.7-1.9 eV), photo-induced io…
We report a strongly temperature dependent luminescence Stokes shift in the electronic spectra of both hybrid and inorganic lead-bromide perovskite single crystals. This behavior stands in stark contrast to that exhibited by more conventional crystalline semiconductors. We correlate the electronic spectra with the anti-Stokes and Stokes Raman vibrational spectra. Dielectric solvation theories, originally developed for excited molecules dissolved in polar liquids, reproduce our experimental observations. Our approach, which invokes a classical Debye-like relaxation process, captures the dielect…
Using first-principles calculations, we show that CsBX$_3$ halides with B=Sn or Pb undergo octahedral rotation distortions, while for B=Ge and Si, they undergo a ferro-electric rhombohedral distortion accompanied by a rhombohedral stretching of the lattice. We show that these are mutually exclusive at their equilibrium volume although different distortions may occur as function of lattice expansion. The choice between the two distortion modes is in part governed by the Goldschmidt tolerance factor. However, another factor explaining the difference between Sn and Pb compared with Ge and Si is t…
Photo-induced phase-segregation in mixed halide perovskite MAPb(BrxI1-x)3 is investigated in the full compositional range by correlative X-ray diffraction and photo-luminescence experiments.
We develop techniques to study the temperature dependent localization, thermalization, and the effects of phonon scattering on the excitons in halide perovskites from the analysis of the emission spectra. The excitonic Urbach edge, when inferred from the low energy tails of the temperature dependent luminescence spectra, is shown to be sensitive to the electron distribution and thermalization. A method to observe the Urbach focus is devised for halide perovskites where the temperature dependence of the excitonic gap is anomalous. The value of the zero-point bandgap renormalization is inferred …
Metal halide perovskites exhibit a materials physics that is distinct from traditional inorganic and organic semiconductors. While materials such as CH3NH3PbI3 are non-magnetic, the presence of heavy elements (Pb and I) in a non-centrosymmetric crystal environment result in a significant spin-splitting of the frontier electronic bands through the Rashba-Dresselhaus effect. We show, from a combination of \textit{ab initio} molecular dynamics, density-functional theory, and relativistic quasi-particle \textit{GW} theory, that the nature (magnitude and orientation) of the band splitting depends o…
Traditional classifications of crystalline phases focus on nuclear degrees of freedom. Through examination of both electronic and nuclear structure, we introduce the concept of an electronic plastic crystal. Such a material is classified by crystalline nuclear structure, while localized electronic degrees of freedom - here lone pairs - exhibit orientational motion at finite temperatures. This orientational motion is an emergent phenomenon arising from the coupling between electronic structure and polarization fluctuations generated by collective motions, such as phonons. Using ab initio molecu…
The zero-dimensional (0D) metal halides comprise periodically distributed and isolated metal-halide polyhedra, which act as the smallest inorganic quantum systems and can accommodate quasi-localized Frenkel excitons. These excitons exhibit unique photophysics including broadband photon emission, huge Stokes shift, and long decay lifetime. The polyhedra can have different symmetries due to the coordination degree of the metal ions. Little is known about how the polyhedron type affects the characteristics of the 0D metal halide crystals. We synthesize and comparatively study three novel kinds of…
The MAPbI$_3$ halide perovskite single crystals are studied at 5 K temperature using the photoluminescence excitation spectroscopy. Two non-interacting types of states are determined: bound excitons and defect-related states. Excitation of the crystal with light energy below the bound exciton resonance reveals the complex low-density defects emission, otherwise hidden by the emission of bound excitons. A way to separate these defect-related luminescence spectra is proposed, and the thorough study of this emission regime is carried out. The results of this study opens an area of low-density def…
Three-dimensional lead halide perovskites have surprised people for their defect-tolerant electronic and optical properties, two-dimensional lead halide layered structures exhibit even more puzzling phenomena: luminescent edge states in Ruddlesden-Popper perovskites and conflicting reports of highly luminescent versus non-emissive CsPb$_{\text{2}}$Br$_{\text{5}}$. In this work, we report the observation of bright luminescent surface states on the edges of CsPb$_{\text{2}}$Br$_{\text{5}}$ microplatelets. We prove that green surface emission makes wide-bandgap single crystal CsPb$_{\text{2}}$Br$…
Methylammonium lead triiodide perovskite (MAPbI3) semiconductor displays outstanding photovoltaic and light emitting properties. We address the unique behavior in which a bias voltage can be used to switch on and off the luminescence of a planar film with lateral symmetric electrodes. Instead of a homogeneous suppression of emission, as in other organic semiconductor films, in MAPbI3 films a dark region advances from the positive electrode at a slow velocity of order of 1 um s-1. Here we explain the existence of the sharp front in terms of the drift of ionic vacancies that drastically reduce t…
Organic-inorganic halide perovskites, especially methylammonium lead halide, have recently led to a remarkable breakthrough in photovoltaic devices. However, due to the environmental and stability concerns of the heavy metal, lead, in these perovskite based solar cells, research in the non-lead perovskite structures have been attracting increasing attention. In this study, a layered perovskite-like architecture, (NH4)3Bi2I9, was prepared in solution and the structure was solved by single crystal X-ray diffraction. The results from DFT calculations showed the significant lone pair effect of the…
Materials Science Institute of Seville. Consejo Superior de Investigaciones Científicas (CSIC)- Univ. Sevilla（塞维利亚材料科学研究所。西班牙国家研究委员会-塞维利亚大学）；Departamento de Física Aplicada I, Universidad de Sevilla（塞维利亚大学应用物理系）；Departamento de Química Física, Facultad de Química. Universidad de Sevilla（塞维利亚大学化学学院物理化学系）
Halide perovskites are promising semiconductors for inexpensive, high-performance optoelectronics. Despite a remarkable defect tolerance compared to conventional semiconductors, perovskite thin films still show substantial microscale heterogeneity in key properties such as luminescence efficiency and device performance. This behavior has been attributed to spatial fluctuations in the population of sub-bandgap electronic states that act as trap-mediated non-radiative recombination sites. However, the origin of the variations, trap states and extent of the defect tolerance remains a topic of deb…
Halide perovskite nanocrystals (NCs) have emerged as a promising material for applications ranging from light-emitting diodes (LEDs) to solar cells and photodetectors. Still, several issues impede the realization of the nanocrystals' full potential, most notably their susceptibility to degradation from environmental stress. This work demonstrates highly stable perovskite nanocrystals (NCs) with quantum yields as high as 95 % by exploiting a ligand-assisted copolymer nanoreactor-based synthesis. The organic ligands thereby serve a dual function by enhancing the uptake of precursors and passivat…
Lead (Pb) halide perovskites have achieved great success in recent years due to their excellent optoelectronic properties, which is largely attributed to the lone-pair s orbital-derived antibonding states at the valence band edge. Guided by the key band-edge orbital character, a series of ns2-containing (i.e., Sn2+, Sb3+, Bi3+) Pb-free perovskite alternatives have been explored as potential photovoltaic candidates. On the other hand, based on the band-edge orbital components (i.e., M2+ s and p/X- p orbitals), a series of strategies have been proposed to optimize their optoelectronic properties…
Band-like Carriers in a Soft, Anharmonic Lattice: Lead-Halide Perovskites
Pohang Accelerator Laboratory, POSTECH（浦项加速器实验室，浦项科技大学）；YUHS-KRIBB Medical Convergence Research Institute, College of Medicine, Yonsei University（延世大学医学院佑山-韩国生命科学研究院医学融合研究所）；Department of Physics, University of Seoul（首尔大学物理系）；Global Institute of Future Technology, Shanghai Jiao Tong University（上海交通大学未来技术学院）
Halide perovskites have emerged as disruptive semiconductors for applications including photovoltaics and light emitting devices, with modular optoelectronic properties realisable through composition and dimensionality tuning. Layered Ruddlesden-Popper perovskites of the form BA2MAn-1PbnI3n+1, where n is the number of lead-halide and methylammonium (MA) sheets spaced by longer butylammonium (BA) cations, are particularly interesting due to their unique two-dimensional character and charge carrier dynamics dominated by strongly bound excitons. However, long-range energy transport through excito…
Current technologies for X-ray detection rely on scintillation from expensive inorganic crystals grown at high-temperature, which so far has hindered the development of large-area scintillator arrays. Thanks to the presence of heavy atoms, solution-grown hybrid lead halide perovskite single crystals exhibit short X-ray absorption length and excellent detection efficiency. Here we compare X-ray scintillator characteristics of three-dimensional (3D) MAPbI3 and MAPbBr3 and two-dimensional (2D) (EDBE)PbCl4 hybrid perovskite crystals. X-ray excited thermoluminescence measurements indicate the absen…
Metal-halide perovskite nanocrystals have demonstrated excellent optoelectronic properties for light-emitting applications. Isovalent doping with various metals (M2+) can be used to tailor and enhance their light emission. Although crucial to maximize performance, an understanding of the universal working mechanism for such doping is still missing. Here, we directly compare the optical properties of nanocrystals containing the most commonly employed dopants, fabricated under identical synthesis conditions. We show for the first time unambiguously and supported by first principles calculations …
We report the synthesis and optical characterization of fully inorganic gradientshell CdSe/CdZnS nanocrystals (NCs) with high luminescence quantum yield (QY, 50 percent), which were obtained by replacing native oleic-acid (OA) ligands with halide ions (Br and Cl). Absorption, photoluminescence excitation (PLE) and photoluminescence (PL) spectra in solution were unaffected by the ligand-exchange procedure. The halide-capped NCs were stable in solution for several weeks without modification of their PL spectra; once deposited as unprotected thin films and exposed to air, however, they did show s…
The instability of metal halide perovskites upon exposure to moisture or heat strongly hampers their applications in optoelectronic devices. Here, we report the large-yield synthesis of highly water-resistant total-inorganic green luminescent CsPbBr3/CsPb2Br5 core/shell heteronanocrystals (HNCs) by developing an in situ phase transition approach. It is implemented via water-driven phase transition of the original monoclinic CsPbBr3 nanocrystal and the resultant tetragonal CsPb2Br5 nanoshell has small lattice mismatch with the CsPbBr3 core, which ensures formation of an epitaxial interface for …
We report a structural reconstruction-induced high photoluminescence quantum yield of 25% in colloidal two-dimensional tin iodide nanosheets that are synthesized by a hot-injection method. The as-synthesized red-colored nanosheets of octylammonium tin iodide perovskites at room temperature transform to white hexagonal nanosheets upon washing or exposure to light. This structural change increases the bandgap from 2.0 eV to 3.0 eV, inducing a large Stokes shift and a broadband emission. Further, a long photoluminescence lifetime of about 1 microsecond is measured for the nanosheets. Such long-li…
