Bright triplet excitons in lead halide perovskites
Michael A. Becker, Roman Vaxenburg, Georgian Nedelcu, Peter C. Sercel, Andrew Shabaev, Michael J. Mehl, John G. Michopoulos, Samuel G. Lambrakos, Noam Bernstein… 展开作者
Michael A. Becker, Roman Vaxenburg, Georgian Nedelcu, Peter C. Sercel, Andrew Shabaev, Michael J. Mehl, John G. Michopoulos, Samuel G. Lambrakos, Noam Bernstein, John L. Lyons, Thilo Stöferle, Rainer F. Mahrt, Maksym V. Kovalenko, David J. Norris, Gabriele Rainò, Alexander L. Efros
备注：
14 pages and 3 figures in the main text, Methods and extended data 16 pages which include 11 figures, and supporting information 28 pages
Nanostructured semiconductors emit light from electronic states known as excitons[1]. According to Hund's rules[2], the lowest energy exciton in organic materials should be a poorly emitting triplet state. Analogously, the lowest exciton level in all known inorganic semiconductors is believed to be optically inactive. These 'dark' excitons (into which the system can relax) hinder light-emitting devices based on semiconductor nanostructures. While strategies to diminish their influence have been developed[3-5], no materials have been identified in which the lowest exciton is bright. Here we show that the lowest exciton in quasi-cubic lead halide perovskites is optically active. We first use the effective-mass model and group theory to explore this possibility, which can occur when the strong spin-orbit coupling in the perovskite conduction band is combined with the Rashba effect [6-10]. We then apply our model to CsPbX3 (X=Cl,Br,I) nanocrystals[11], for which we measure size- and composition-dependent fluorescence at the single-nanocrystal level. The bright character of the lowest exciton immediately explains the anomalous photon-emission rates of these materials, which emit 20 and 1,000 times faster[12] than any other semiconductor nanocrystal at room[13-16] and cryogenic[17] temperatures, respectively. The bright exciton is further confirmed by detailed analysis of the fine structure in low-temperature fluorescence spectra. For semiconductor nanocrystals[18], which are already used in lighting[19,20], lasers[21,22], and displays[23], these optically active excitons can lead to materials with brighter emission and enhanced absorption. More generally, our results provide criteria for identifying other semiconductors exhibiting bright excitons with potentially broad implications for optoelectronic devices.
Inorganic halide perovskites have emerged as a promising platform in a wide range of applications from solar energy harvesting to computing, and light emission. The recent advent of epitaxial thin film growth of halide perovskites has made it possible to investigate low-dimensional quantum electronic devices based on this class of materials. This study leverages advances in vapor-phase epitaxy of halide perovskites to perform low-temperature magnetotransport measurements on single-domain cesium tin iodide (CsSnI$_3$) epitaxial thin films. The low-field magnetoresistance carries signatures of c…
We propose Auger-like process assisted by quantum defects in metal halide perovskite quantum dots, where a charge carrier in the ground state of the quantum dot is trapped by quantum defects, resulting in another charge carrier in defect is excited and returns back to the ground state of the quantum dot. We find that the whole process is on the femtosecond scale. More importantly, the process is independent of the depth and species of the defects, which is in good agreement with the recent theoretical prediction using ab initio nonadiabatic molecular dynamics simulation. This Auger-like proces…
Despite showing great promise for optoelectronics, the commercialization of halide perovskite nanostructure-based devices is hampered by inefficient electrical excitation and strong exciton binding energies. While transport of excitons in an energy-tailored system via Förster resonance energy transfer (FRET) could be an efficient alternative, halide ion migration makes the realization of cascaded structures difficult. Here, we show how these could be obtained by exploiting the pronounced quantum confinement effect in two dimensional CsPbBr3 based nanoplatelets (NPls). In thin films of NPls of …
Chemically prepared colloidal semiconductor quantum dots have long been proposed as scalable and color-tunable single emitters in quantum optics, but they have typically suffered from prohibitively incoherent emission. We now demonstrate that individual colloidal lead halide perovskite quantum dots (PQDs) display highly efficient single photon emission with optical coherence times as long as 80 ps, an appreciable fraction of their 210 ps radiative lifetimes. These measurements suggest that PQDs should be explored as building blocks in sources of indistinguishable single photons and entangled p…
Recent observations indicated that the photoelectric conversion properties of perovskite materials are intimately related to the presence of superlattice structures and other unusual nanoscale features in them. The low dimensional or mixed dimensional halide perovskite family are found to be more efficient materials for device application compared to 3-dimensional halide perovskites. The emergence of perovskite solar cell has revolutionized the solar cell industry because of their flexible architecture and rapidly increased efficiency. Tuning the dielectric constant, charge separation are the …
Halide perovskites are promising semiconductor materials for optoelectronics. One of their unique features is the synthesis, that could be performed by the crystallization from the solution. This method is fast, but practically couldn't be optimized due to the strongly non-equilibrium conditions of crystal growth. Another quality limitation is the typical incorporation of organic solvent molecules into crystals when perovskite crystallization is performed from solution with organic solvent. Here we report an alternative method of perovskite single crystal growth based on the counterdiffusion o…
Under continuous light illumination, it is known that localized domains with segregated halide compositions form in semiconducting mixed-halide perovskites, thus severely limiting their optoelectronic applications due to the negative changes in bandgap energies and charge-carrier characteristics. Here we deposit mixed-halide perovskite CsPbBr1.2I1.8 nanocrystals onto an indium tin oxide substrate, whose temperature can be rapidly changed by ~10 degree in a few seconds by applying or removing an external voltage. Such a sudden temperature change induces a temporary transition of CsPbBr1.2I1.8 n…
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…
Since perovskite solar cells have attracted a lot of attentions over the past years, the enhancement of their optical absorption and current density are among the basic coming challenges. For this reason, first, we have studied structural and optical properties of organic-inorganic hybrid halide perovskite CH3NH3PbI3 and the compounds doped by chlorine halogen CH3NH3PbI3-xClx in the cubic phase by using density functional theory (DFT). Then, we investigate the light absorption efficiency and optical current density of the single-junction perovskite solar cell CH3NH3PbI3-xClx for the values (x=…
Two-dimensional (2D) halide perovskites are emerging as promising candidates for nano-electronics and optoelectronics. To realize their full potential, it is important to understand the role of those defects that can strongly impact material properties. In contrast to other popular 2D semiconductors (e.g. transition metal dichalcogenides MX2) for which defects typically induce harmful traps, we show that the electronic activities of defects in 2D perovskites are significantly tunable. For example, even with a fixed lattice orientation, one can change the synthesis conditions to convert a line …
Halide perovskites are a promising optical gain media with high tunability and simple solution synthesis. In this study, two gain regimes, namely amplified spontaneous emission and random lasing, are demonstrated in same MAPbBr$_3$ halide perovskite single crystal. For this, photoluminescence is measured at a temperature of 4 K with pulsed femtosecond pumping by UV light with a 80 MHz repetition rate. Random lasing is observed in areas of the sample where a random resonator was formed due to cracks and crystal imperfections. In more homogeneous regions of the sample, the dominant regime is amp…
Halide perovskites exhibit giant photostriction, that is, volume or shape changes upon illumination. However, the microscopic origin of this phenomenon remains unclear and there are experimental reports of both light-induced lattice expansion and contraction. In this paper we establish a general method, based on first-principles calculations and molecular orbital theory, which provides a microscopic picture of photostriction in insulators based on the orbital characters of their electronic bands near the Fermi level. For lead-halide perovskites, we find that different valence states have diffe…
Perovskite solar cells with record power conversion efficiency are fabricated by alloying both hybrid and fully inorganic compounds. While the basic electronic properties of the hybrid perovskites are now well understood, key electronic parameters for solar cell performance, such as the exciton binding energy of fully inorganic perovskites, are still unknown. By performing magneto transmission measurements, we determine with high accuracy the exciton binding energy and reduced mass of fully inorganic CsPbX$_3$ perovskites (X=I, Br, and an alloy of these). The well behaved (continuous) evolutio…
We theoretically study the optical absorption of an angulon in the metal halide perovskites (MHP) based on the improved Devreese-Huybrechts-Lemmens model, where the formation of quasiparticle angulon states originates from the organic cation rotating in the inorganic octahedral cage of MHP. We find that the resonance optical absorption peaks are appeared when the energy of incident photon matches the quantum levels of angulon. Moreover, the intensity of absorption depends on the quantum states of phonon angular momentum. These theoretical results provide significant insight to study the redist…
Single crystals of Cs2BiAgBr6 lead-free perovskite were grown by crystallization from supersaturated solution. According to characterization by XRD and EBSD methods the double perovskite single crystal are of the cubic Fm-3m symmetry with the lattice constant a = 11.20 Å. DFT predictions based on the single crystal X-ray diffraction analysis reveal that the material is an indirect band gap semiconductor. Low temperature (1.4 K) photoluminescence spectra demonstrate three broadened bands that correspond to two lowest computed indirect and one direct band-to-band transitions.
Cui et al. describe the fabrication and characterization of planar pn-junction solar cells based on lead-halide perovskites. The doping densities measured using Hall effect measurements vary from $N_D = 10^{12} cm^{-3}$ to $8\times 10^{12} cm^{-3}$ for the solution-processed n-type layer and $N_A = 8\times 10^9 cm^{-3}$ for the evaporated p-type layer. While these devices outperform their counterparts, that are supposedly un-doped, the results raise three important questions: (i) Are the reported doping densities high enough to change the electrostatic potential distribution in the device from…
We use general symmetry-based arguments to construct an effective model suitable for studying optical properties of lead-halide perovskites. To build the model, we identify an atomic-level interaction between electromagnetic fields and the spin degree of freedom that should be added to a minimally-coupled $\mathbf{k\cdot p}$ Hamiltonian. As a first application, we study two basic optical characteristics of the material: the Verdet constant and the refractive index. Beyond these linear characteristics of the material the model is suitable for calculating non-linear effects such as the third-ord…
