The one-photon absorption cross section of nanocrystals (NCs) of the inorganic perovskite CsPbBr$_{3}$ is studied theoretically using a multiband $\mathbf{k}\cdot\mathbf{p}$ envelope-function model combined with a treatment of intercarrier correlation by many-body perturbation theory. A confined exciton is described first within the Hartree-Fock (HF) approximation, and correlation between the electron and hole is then included in leading order by computing the first-order vertex correction to the electron-photon interaction. The vertex correction is found to give an enhancement of the near-threshold absorption cross section by a factor of up to 4 relative to the HF (mean-field) value of the cross section, for NCs with an edge length $L=9$-12 nm (regime of intermediate confinement). The vertex-correction enhancement factors are found to decrease with increasing exciton energy; the absorption cross section for photons of energy $ω=3.1$ eV (about 0.7 eV above threshold) is enhanced by a factor of only 1.4-1.5 relative to the HF value. The $\mathbf{k}\cdot\mathbf{p}$ corrections to the absorption cross section are also significant; they are found to increase the cross section at an energy $ω=3.1$ eV by about 30% relative to the value found in the effective-mass approximation. The theoretical absorption cross section at $ω=3.1$ eV, assuming a Kane parameter $E_{P}=20$ eV, is found to be intermediate among the set of measured values (which vary among themselves by nearly an order of magnitude) and to obey a power-law dependence $σ^{(1)}(ω)\propto L^{2.9}$ on the NC edge length $L$, in good agreement with experiment. The dominant contribution to the theoretical exponent 2.9 is shown to be the density of final-state excitons. The main theoretical uncertainty in these calculations is in the value of the Kane parameter $E_{P}$.
We demonstrate the optical orientation and alignment of excitons in a two-dimensional layer of CsPbI$_3$ perovskite nanocrystals prepared by colloidal synthesis and measure the anisotropic exchange splitting of exciton levels in the nanocrystals. From the experimental data at low temperature (2K), we obtain the average value of anisotropic splitting of bright exciton states of the order of 120μeV. Our calculations demonstrate that there is a significant contribution to the splitting due to the nanocrystal shape anisotropy for all inorganic perovskite nanocrystrals.
The multi-quantum well (MQW) organic-inorganic perovskite offer an approach of tuning the exciton binding energy based on the well-barrier dielectric mismatch effect, which called the image charge effect. The exfoliation from MQW organic-inorganic perovskite forms a twodimensional (2D) nano-sheet. As with other 2D materials, like graphene or transition metal dichalcogenides (TMDs), the ultra-thin perovskites layers are highly sensitive to the dielectric environment. We investigate the ultrathin crystalline 2D van-der-Waals (vdW) layers of organic-inorganic perovskite crystals close to a surfac…
Inorganic nanocrystal gels retain distinct properties of individual nanocrystals while offering tunable, network structure-dependent characteristics. We review different mechanisms for assembling gels from colloidal nanocrystals including (1) controlled destabilization, (2) direct bridging, (3) depletion, as well as linking mediated by (4) coordination bonding or (5) dynamic covalent bonding, and we highlight how each impacts gel properties. These approaches use nanocrystal surface chemistry or the addition of small molecules to mediate inter-nanocrystal attractions. Each method offers advanta…
We calculate the shift in emission frequency of the trion and biexciton (relative to that of the single exciton) for nanocrystals (NCs) of inorganic perovskites CsPbBr3 and CsPbI3. The calculations use an envelope-function k.p model combined with self-consistent Hartree-Fock and a treatment of the intercarrier correlation energy in the lowest (second) order of many-body perturbation theory. The carriers in the trion and biexciton are assumed to have relaxed nonradiatively to the ground state at the band edge before emission occurs. The theoretical trion shifts for both CsPbBr3 and CsPbI3 are f…
A facile, low-temperature precipitation-based method is utilized to demonstrate the synthesis of ultra-thin and highly-uniform cesium lead bromide perovskite nanowires (NWs). The reactions facilitate the NWs crystalline nature over micron-size lengths, while they impart tailored nanowire widths that range from the quantum confinement regime (~ 7 nm) and down to 2.6 nm. This colloidal synthesis approach is the first of its kind that is carried out on the work-bench, without demanding chemical synthesis equipment. Importantly, the NWs photoluminescence is shown to become improved over time, with…
Two-dimensional (2D) layered hybrid perovskites provide an ideal platform for studying the properties of excitons. Here, we report on a strong triplet-exciton and longitudinal-optical (LO) phonon coupling in 2D (C6H5CH2CH2NH3, PEA)2PbBr4 perovskites. The triplet excitons exhibit strong photoluminescence (PL) in thick perovskite microflakes, and the PL is not detectable for monolayer microflakes. The coupling strength of the triplet exciton-LO phonon is approximately two to three times greater than that of the singlet exciton-LO phonon with a LO phonon energy of about 21 meV. This difference mi…
Millisecond-long electron spin lifetime in CsPbI$_3$ perovskite nanocrystals revealed by optically detected magnetic resonance
Technische Universität Dortmund（多特蒙德工业大学）；Ioffe Institute, Russian Academy of Sciences（俄罗斯科学院伊俄费研究所）；P.N. Lebedev Physical Institute of the Russian Academy of Sciences（俄罗斯科学院列别捷夫物理研究所）；Spin Optics Laboratory, St. Petersburg State University（圣彼得堡大学旋光实验室）；ITMO University（ITMO大学）；St. Petersburg State Institute of Technology（圣彼得堡国立理工学院）
Coherent manipulation of the exciton wave function in a single semiconductor colloidal nanocrystal (NC) has been actively pursued in the past decades without any success, mainly due to the bothersome existences of the spectral diffusion and the photoluminescence (PL) blinking effects. Such optical deficiencies can be naturally avoided in the newly-developed colloidal NCs of perovskite CsPbI3, leading to the PL spectrum with a stable intensity at the single-particle level. Meanwhile, from the first-order photon correlation measurement, a PL linewidth smaller than 20 μeV is estimated for the emi…
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 …
Quantum beats of exciton-polarons in CsPbI3 perovskite nanocrystals
Technische Universität Dortmund（多特蒙德工业大学）；St. Petersburg State University（圣彼得堡国立大学）；ITMO University（ITMO大学）；St. Petersburg State Institute of Technology（圣彼得堡国立技术学院）；Jackson State University（杰克逊州立大学）
Carrier spins in semiconductor nanocrystals are promising candidates for quantum information processing. Using a combination of time-resolved Faraday rotation and photoluminescence spectroscopies, we demonstrate optical spin polarization and coherent spin precession in colloidal CsPbBr3 nanocrystals that persists up to room temperature. By suppressing the influence of inhomogeneous hyperfine fields with a small applied magnetic field, we demonstrate inhomogeneous hole transverse spin-dephasing times (T2*) that approach the nanocrystal photoluminescence lifetime, such that nearly all emitted ph…
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…
The spin physics of perovskite nanocrystals with confined electrons or holes is attracting increasing attention, both for fundamental studies and spintronic applications. Here, stable CsPb(Cl$_{0.5}$Br$_{0.5}$)$_3$ lead halide perovskite nanocrystals embedded in a fluorophosphate glass matrix are studied by time-resolved optical spectroscopy to unravel the coherent spin dynamics of holes and their interaction with nuclear spins of the $^{207}$Pb isotope. We demonstrate the spin mode locking effect provided by the synchronization of the Larmor precession of single hole spins in each nanocrystal…
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…
Lead-halide perovskite nanocrystals (PNCs) exhibit unique optoelectronic properties, many of which originate from a purported bright-triplet exciton fine-structure. A major impediment to measuring this fine-structure is inhomogeneous spectral broadening, which has limited most experimental studies to single-nanocrystal spectroscopies. It is shown here that the linearly-polarized single-particle selection rules in PNCs are preserved in nonlinear spectroscopies of randomly-oriented ensembles. Simulations incorporating rotational-averaging demonstrate that techniques such as transient absorption …
The dynamical and static Rashba effects in hybrid methylammonium (MA) lead halide perovskites have recently been theoretically predicted. However, only the static effect was experimentally confirmed so far. Here we report on the dynamical Rashba effect observed using snapshot transient absorption spectral imaging with 400 nm pumping for a fully encapsulated film of 20-nm-sized 3D MAPbBr3 nanocrystals. The effect causes a 240 meV splitting of the lowest-energy absorption bleaching band, initially appearing over sub-ps timescale and progressively stabilizing to 60 meV during 500 ps. The integrat…
Outstanding optoelectronic properties and a facile synthesis render halide perovskite nanocrystals (NCs) a promising material for nanostructure-based devices. However, the commercialization is hindered mainly by the lack of NC stability under ambient conditions and inefficient charge carrier injection. Here, we investigate solutions to both problems, employing methylammonium lead bromide (MAPbBr_3) NCs encapsulated in diblock copolymer core-shell micelles of tunable size. We confirm that the shell does not prohibit energy transfer, as FRET efficiencies between these NCs and 2D CsPbBr_3 nanopla…
Polariton lasing is the coherent emission arising from a macroscopic polariton condensate first proposed in 1996. Over the past two decades, polariton lasing has been demonstrated in a few inorganic and organic semiconductors in both low and room temperatures. Polariton lasing in inorganic materials significantly relies on sophisticated epitaxial growth of crystalline gain medium layers sandwiched by two distributed Bragg reflectors in which combating the built-in strain and mismatched thermal properties is nontrivial. On the other hand, organic active media usually suffer from large threshold…
Two-dimensional halide perovskite nanoplatelets (NPLs) have exceptional light-emitting properties, including wide spectral tunability, ultrafast radiative decays, high quantum yields (QY), and oriented emission. To realize efficient devices, it is imperative to understand how exciton transport progresses in NPL thin films. Due to the high binding energies of electron-hole pairs, excitons are generally considered the dominant species responsible for carrier transfer. We employ spatially and temporally resolved optical microscopy to map exciton diffusion in perovskite nanocrystal (NC) thin films…
We have investigated nonlinear refraction in all-inorganic halide perovskites, the CsPbBr$_3$ and CsPbBr$_{1.5}$I$_{1.5}$ nanosheet and quantum dot colloids in toluene, by a novel beam deflection technique using near-resonant continuous wave lasers. The nonlinear refraction and its time-evolution measured here have originated from thermal lensing effect. Nonlinear behaviour of heat transport in terms of intensity dependent thermal diffusion rate has been observed. Effects of convective heat flow have been measured at high intensities. Quantum dots have higher nonlinear refraction as compared t…
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 …
Manipulating strong light-matter interaction in semiconductor microcavities is crucial for developing high-performance exciton polariton devices with great potentials in next-generation all-solid state quantum technologies. In this work, we report surface plasmon enhanced strong exciton-photon interaction in CH3NH3PbBr3 perovskite nanowires. Characteristic anti-crossing behaviors, indicating Rabi splitting energy up to ~ 560 meV, are observed near exciton resonance in hybrid semiconductor-insulator-metallic waveguide cavity at room temperature. An exciton-photon coupling strength enhancement f…
Although both epitaxial quantum dots (QDs) and colloidal nanocrystals (NCs) are quantum-confined semiconductor nanostructures, so far they have demonstrated dramatically-different exciton fine structure splittings (FSSs) at the cryogenic temperature. The single-QD photoluminescence (PL) is dominated by the bright-exciton FSS, while it is the energy separation between bright and dark excitons that is often referred to as the FSS in a single NC. Here we show that, in single perovskite CsPbI3 NCs synthesized from a colloidal approach, a bright-exciton FSS as large as hundreds of μeV can be resolv…
Although the structural phase transitions in single-crystal hybrid methyl-ammonium (MA) lead halide perovskites (MAPbX3, X = Cl, Br, I) are common phenomena, they have never been observed in the corresponding nanocrystals. Here we demonstrate that two-photon-excited photoluminescence (PL) spectroscopy is capable of monitoring the structural phase transitions in MAPbX3 nanocrystals because nonlinear susceptibilities govern the light absorption rates. We provide experimental evidence that the orthorhombic-to-tetragonal structural phase transition in a single layer of 20-nm-sized 3D MAPbBr3 nanoc…
Exciton-polaritons in semiconductor microcavities generate fascinating effects such as long-range spatial coherence and Bose-Einstein Condensation (BEC), which are attractive for their potential use in low threshold lasers, vortices and slowing light, etc. However, currently most of exciton-polariton effects either occur at cryogenic temperature or rely on expensive cavity fabrication procedures. Further exploring new semiconductor microcavities with stronger exciton photon interaction strength is extensively needed. Herein, we demonstrate room temperature photon exciton strong coupling in hyb…
Reduced Optical Gain Threshold by Carrier Multiplication in Semiconductor Perovskite Nanocrystals
National Laboratory of Solid State Microstructures, School of Physics, and Collaborative Innovation Center of Advanced Microstructures, Nanjing University（南京大学固体微结构物理国家重点实验室、物理学院和先进微结构协同创新中心）；College of Engineering and Applied Sciences, and MOE Key Laboratory of Intelligent Optical Sensing and Manipulation, Nanjing University（南京大学工程与应用科学学院和智能光学传感与操控教育部重点实验室）
Yb3+-doped inorganic metal-halide perovskites (Yb3+:CsPbX3, X = Cl, Br) have recently been discovered to display highly efficient quantum cutting, in which the energy from individual blue or UV photons absorbed by the material is re-emitted in the form of pairs of near-infrared photons by Yb3+ dopants. Experimental photoluminescence quantum yields approaching 200{%} have been reported. As the first quantum-cutting materials that combine such high photoluminescence quantum yields with strong, broadband absorption in the visible, these materials offer unique opportunities for enhancing the effic…
The outstanding performance of organic-inorganic metal trihalide solar cells benefits from the exceptional photo-physical properties of both electrons and holes in the material. Here, we directly probe the free-carrier dynamics in Cs-doped FAPbI3 thin films by spatiotemporal photoconductivity imaging. Using charge transport layers to selectively quench one type of carriers, we show that the two relaxation times on the order of 1 microsecond and 10 microseconds correspond to the lifetimes of electrons and holes in FACsPbI3, respectively. Strikingly, the diffusion mapping indicates that the diff…
