Lead Halide Perovskite CsPbBr3 Research Articles

Extreme Electron-Photon Interaction in Disordered Perovskites.

The interaction of light with solids can be dramatically enhanced owing to electron-photon momentum matching. This mechanism manifests when light scattering from nanometer-sized clusters including a specific case of self-assembled nanostructures that form a long-range translational order but local disorder (crystal-liquid duality). In this paper, a new strategy based on both cases for the light-matter-interaction enhancement in a direct bandgap semiconductor - lead halide perovskite CsPbBr3 - by using electric pulse-driven structural disorder, is addressed. The disordered state allows the generation of confined photons, and the formation of an electronic continuum of static/dynamic defect states across the forbidden gap (Urbach bridge). Both mechanisms underlie photon-momentum-enabled electronic Raman scattering (ERS) and single-photon anti-Stokes photoluminescence (PL) under sub-band pump. PL/ERS blinking is discussed to be associated with thermal fluctuations of cross-linked [PbBr6]4- octahedra. Time-delayed synchronization of PL/ERS blinking causes enhanced spontaneous emission at room temperature. These findings indicate the role of photon momentum in enhanced light-matter interactions in disordered and nanostructured solids.

A Strategy for Tuning Electron-Phonon Coupling and Carrier Cooling in Lead Halide Perovskite Nanocrystals.

Perovskites have been recognized as a class of promising materials for optoelectronic devices. We intentionally include excessive Cs+ cations in precursors in the synthesis of perovskite CsPbBr3 nanocrystals and investigate how the Cs+ cations influence the lattice strain in these perovskite nanocrystals. Upon light illumination, the lattice strain due to the addition of alkali metal Cs+ cations can be compensated by light-induced lattice expansion. When the Cs+ cation in precursors is about 10% excessive, the electron-phonon coupling strength can be reduced by about 70%, and the carrier cooling can be slowed down about 3.5 times in lead halide perovskite CsPbBr3 nanocrystals. This work reveals a new understanding of the role of Cs+ cations, which take the A-site in ABX3 perovskite and provide a new way to improve the performance of perovskites and their practical devices further.

Understanding the phase transition mechanism in the lead halide perovskite CsPbBr3 via theoretical and experimental GIWAXS and Raman spectroscopy

Metal-halide perovskites (MHPs) exhibit excellent properties for application in optoelectronic devices. The bottleneck for their incorporation is the lack of long-term stability such as degradation due to external conditions (heat, light, oxygen, moisture, and mechanical stress), but the occurrence of phase transitions also affects their performance. Structural phase transitions are often influenced by phonon modes. Hence, an insight into both the structure and lattice dynamics is vital to assess the potential of MHPs. In this study, GIWAXS and Raman spectroscopy are applied, supported by density functional theory calculations, to investigate the apparent manifestation of structural phase transitions in the MHP CsPbBr3. Macroscopically, CsPbBr3 undergoes phase transitions between a cubic (α), tetragonal (β), and orthorhombic (γ) phase with decreasing temperature. However, microscopically, it has been argued that only the γ phase exists, while the other phases exist as averages over length and time scales within distinct temperature ranges. Here, direct proof is provided for this conjecture by analyzing both theoretical diffraction patterns and the evolution of the tilting angle of the PbBr6 octahedra from molecular dynamics simulations. Moreover, sound agreement between experimental and theoretical Raman spectra allowed to identify the Raman active phonon modes and to investigate their frequency as a function of temperature. As such, this work increases the understanding of the structure and lattice dynamics of CsPbBr3 and similar MHPs.

An In Situ‐Fabricated All‐Inorganic Perovskite/MoO3 Heterojunction by Chemical Vapor Deposition and Its Photoresponse Properties

All‐inorganic lead halide perovskite CsPbBr3 has received a lot of attention in the field of optoelectronic devices due to its high absorption coefficient and photoelectric conversion efficiency. Using a heterojunction as the core of a photodetector (PD) to transform the optical signal into an electrical signal compensates for the deficiencies of using a single material. Here, a simple and efficient chemical vapor deposition (CVD) method is used to fabricate a CsPbBr3/MoO3/ITO heterojunction PD with superior photoresponse properties, including photoresponsivity of 37.209 A W−1 and detectivity of 1.64 × 1012 Jones at bias voltage of 3 V. Compared with pure CsPbBr3 perovskite, the responsivity of the PD is 3.54 times as great. As a photosensitive layer, CsPbBr3 absorbs photons and releases electrons due to its high optical absorption coefficient. The introduction of MoO3 plays a role in promoting the separation and transport of photogenerated carriers of the heterojunction structure and improves device performance. This study provides groundwork facilitating the use of CVD for in situ growth of high‐performance all‐inorganic perovskite heterostructures to realize the prospect of large‐scale production of perovskite PDs.

Studies on the optical stability of CsPbBr3 with different dimensions (0D, 1D, 2D, 3D) under thermal environments.

The thermal stability of phosphor materials had long been a bottleneck in their commercialization. Nowadays, cesium lead halide perovskite CsPbBr3 has been considered a potential replacement for the next generation of optoelectronic devices due to its excellent optical and electronic properties, however, the devices inevitably generate high temperatures on the surface under prolonged energization conditions in practical applications, which can be fatal to CsPbBr3. Despite the various strategies that have been employed to improve the thermal stability of CsPbBr3, systematic studies of the thermal stability of the basis CsPbBr3 are lacking. In this study, CsPbBr3 with different dimensions (0D quantum dots (QDs), 1D nanowires (NWs), 2D nanoplate (NPs), 3D micron crystals (MCs)) was prepared by traditional high-temperature thermal injection, and a systematic study was carried out on their optical properties and thermal stability. The results revealed that the dimensional change will directly influence the optical properties as well as the thermal stability of CsPbBr3. In particular, 3D CsPbBr3 MCs maintained relatively high thermal stability under high-temperature environments, which will bring interest for the commercialization of next-generation perovskite optoelectronic devices.

Effect of thickness on the electronic structure and optical properties of quasi two-dimensional perovskite CsPbBr3 nanoplatelets

The effect of thickness of cesium lead halide perovskite CsPbBr3 nanoplatelets (NPLs) on their electronic structure and optical properties are investigated using an effective-mass envelope function theory based on the 8-band k·p model with the consideration of exciton binding energy. We first reported the CsPbBr3 nanoplatelets’ band structure and optical gain with exciton effect. As the thickness of NPLs decreases, their bandgap increases and the band mixing is more obvious which influences the transition matrix element (TME). The optical gain of CsPbBr3 nanoplatelets is calculated by taking into account of TME, Fermi factor, injected carrier density and thickness. A blue shift of peak position in optical gain can be observed as the thickness of NPLs decreases. As the injected carrier density arises, the maximum optical gain of thicker NPLs reach saturation much faster than the thinner ones. To obtain high differential gain, NPLs with less thickness are better choices. Experimental work is carried out and the results agree with our theoretical results very well.

Preparation of surface modified CsPbBr3@CsPb2Br5 nanocrystals with high stability by a pseudo-peritectic method

Lead halide perovskite CsPbBr3 nanocrystals (NCs) have attracted great interest in recent years owing to their excellent properties such as strong light absorption, high photoluminescence quantum yield (PLQY), good wavelength tunability, and narrow FWHM. However, their instability is still a bottleneck for their potential application. In this work, a pseudo-peritectic method, which is a peritectic reaction in solutions, was proposed. The phenomenon of “Survival of the fittest” was observed. The synthesized CsPb2Br5 phase greatly reduces the surface defects, and improves the stability and PL properties. The pseudo-peritectic method using for preparing surface modified CsPbBr3@CsPb2Br5 nanocrystals is a significant pathway to achieve long-term stable lead halide perovskite for optoelectronic devices.

Characterization of Crystalline CsPbBr3 Perovksite Dosimeters for Clinical Radiotherapy

Lead halide perovskite CsPbBr3 is a wide-gap semiconductor material potentially very attractive for next generations of real-time monitors and particle detectors in high-energy physics. Here, we present the first characterization of crystalline CsPbBr3 point dosimeters with submillimeter size, under 6 MV X-photon beams used in clinical radiotherapy. Current response of the devices proved to be promising in terms of fast rise and decay times, of the same order of the X-ray beam onset and offset ones; absence of polarization effects; reproducibility to repeated irradiations; and linearity of the collected charge as a function of the absorbed dose. Comparing the measured sensitivity with the theoretical one, a charge collection distance of about 100 μm has been evaluated, of the same order of the linear dimensions of crystallites within the samples, suggesting that recombination centers are mainly placed at grain boundaries. A much higher sensitivity per unit area measured with crystalline CsPbBr3 as compared with drop-casted ones can be explained in terms of a less disordered crystalline structure. This work opens the way to CsPbBr3 point dosimeters, with linear dimensions meeting the strict spatial resolution constraints for bidimensional dose mapping required in clinical radiotherapy.

Curing the fundamental issue of impurity phases in two-step solution-processed CsPbBr3 perovskite films

Inorganic lead halide perovskite CsPbBr3 offers attractive photophysical properties and phase stability for high-performance optoelectronic devices. However, CsPbBr3 films produced by the classic solution-based two-step method are always accompanied with impurity phases of CsPb2Br5 and Cs4PbBr6, which represents a major efficiency-limiting factor for future advances of CsPbBr3-based devices. The challenge lies in the complexity of the Cs-Pb-Br phase system, requiring both spatially and temporally precise control of the precursor stoichiometry during solution-phase growth of CsPbBr3 films. By adopting 2-methoxyethanol as the solution conversion medium instead of commonly applied methanol, the reaction between CsBr and PbBr2 can be finely controlled to yield single phase CsPbBr3 films within a few minutes; extending the solution-conversion step to 24 h does not alter the phase purity of resulting CsPbBr3 films. The present work paves the way to regulate the crystal growth behaviors of two-step solution-processed CsPbBr3 films by simple solvent engineering.

Hot-Pressed CsPbBr3 Quasi-Monocrystalline Film for Sensitive Direct X-ray Detection.

An X-ray detector with high sensitivity would be able to increase the generated signal and reduce the dose rate; thus, this type of detector is beneficial for applications such as medical imaging and product inspection. The inorganic lead halide perovskite CsPbBr3 possesses relatively larger density and a higher atomic number in contrast to its hybrid counterpart. Therefore, it is expected to provide high detection sensitivity for X-rays; however, it has rarely been studied as a direct X-ray detector. Here, a hot-pressing method is employed to fabricate thick quasi-monocrystalline CsPbBr3 films, and a record sensitivity of 55 684 µC Gyair -1 cm-2 is achieved, surpassing all other X-ray detectors (direct and indirect). The hot-pressing method is simple and produces thick quasi-monocrystalline CsPbBr3 films with uniform orientations. The high crystalline quality of the CsPbBr3 films and the formation of self-formed shallow bromide vacancy defects during the high-temperature process result in a large µτ product and, therefore, a high photoconductivity gain factor and high detection sensitivity. The detectors also exhibit relatively fast response speed, negligible baseline drift, and good stability, making a CsPbBr3 X-ray detector extremely competitive for high-contrast X-ray detections.

Coherent spin dynamics of electrons and holes in CsPbBr3 perovskite crystals

The lead halide perovskites demonstrate huge potential for optoelectronic applications, high energy radiation detectors, light emitting devices and solar energy harvesting. Those materials exhibit strong spin-orbit coupling enabling efficient optical orientation of carrier spins in perovskite-based devices with performance controlled by a magnetic field. Here we show that elaborated time-resolved spectroscopy involving strong magnetic fields can be successfully used for perovskites. We perform a comprehensive study of high-quality lead halide perovskite CsPbBr3 crystals by measuring the exciton and charge carrier g-factors, spin relaxation times and hyperfine interaction of carrier and nuclear spins by means of coherent spin dynamics. Owing to their ‘inverted’ band structure, perovskites represent appealing model systems for semiconductor spintronics exploiting the valence band hole spins, while in conventional semiconductors the conduction band electrons are considered for spin functionality.

Low defects, large area and high stability of all-inorganic lead halide perovskite CsPbBr3 thin films with micron-grains via heat-spraying process for self-driven photodetector.

All-inorganic lead halide perovskite CsPbBr3 has important applications in photoelectronic devices such as photodetectors, LEDs and photovoltaic devices. However, preparing high-quality CsPbBr3 thin films has proven to be challenging. In this study, we prepared all-inorganic lead halide perovskite CsPbBr3 thin films with micron-grains (MG-CsPbBr3-TF) via a heat-spraying process (HSP) using a CsPbBr3-saturated solution (CsPbBr3-SS), and the films exhibited large area, low defects and high stability. The grain size of MG-CsPbBr3-TF was about 1–5 microns. The micron-sized grains in MG-CsPbBr3-TF enabled the absorption cutoff edge to be extended from 537 to 545 nm. In addition, the presence of fewer boundaries in MG-CsPbBr3-TF reduced the defects in MG-CsPbBr3-TF (the blue shift of luminescence). The response wavelengths of a low-cost and self-driven (zero-biased) photodetector based on MG-CsPbBr3-TF were from 330 to 600 nm. CsPbBr3 thin films having a large area (10 cm × 10 cm) and micron-sized grains were also prepared by HSP and exhibited excellent stability (1944 h) in air (T = 298 K, 40% humidity). To the best of our knowledge, this is the first study of high-quality CsPbBr3 thin films prepared by HSP. The results are of great interest for both fundamental research and practical applications of CsPbBr3 in photodetectors, LEDs and photovoltaic devices.

Full coverage all-inorganic cesium lead halide perovskite film for high-efficiency light-emitting diodes assisted by 1,3,5-tri(m-pyrid-3-yl-phenyl)benzene

Abstract A full coverage all-inorganic cesium lead halide perovskite CsPbBr3 film is achieved by introducing a small organic molecule material, 1,3,5-tri(m-pyrid-3-yl-phenyl)benzene (TmPyPB), as a solution additive. The light-emitting diode (LED) using this CsPbBr3:TmPyPB perovskite film as light emitting layer exhibit improved electroluminescent (EL) performance with the maximum brightness of 22309 cd/m2, highest current efficiency of 8.77 cd/A, and external quantum efficiency (EQE) of 2.27%, which are 8.6, 10.2 and 10.3 times to that of neat CsPbBr3 film based LED, respectively. The enhanced EL performances are ascribed to less current leakage due to full coverage, and improved electron transporting in the CsPbBr3:TmPyPB perovskite film.

Electronic structure of the CsPbBr3/polytriarylamine (PTAA) system

The inorganic lead halide perovskite CsPbBr3 promises similar solar cell efficiency to its hybrid organic-inorganic counterpart CH3NH3PbBr3 but shows greater stability. Here, we exploit this stability for the study of band alignment between perovskites and carrier selective interlayers. Using ultraviolet, X-ray, and inverse photoemission spectroscopies, we measure the ionization energy and electron affinities of CsPbBr3 and the hole transport polymer polytriarylamine (PTAA). We find that undoped PTAA introduces a barrier to hole extraction of 0.2–0.5 eV, due to band bending in the PTAA and/or a dipole at the interface. p-doping the PTAA eliminates this barrier, raising PTAA's highest occupied molecular orbital to 0.2 eV above the CsPbBr3 valence band maximum and improving hole transport. However, IPES reveals the presence of states below the PTAA lowest unoccupied molecular level. If present at the CsPbBr3/PTAA interface, these states may limit the polymer's efficacy at blocking electrons in solar cells with wide band gap materials like CsPbBr3 and CH3NH3PbBr3.

High Defect Tolerance in Lead Halide Perovskite CsPbBr3.

The formation energies and charge-transition levels of intrinsic point defects in lead halide perovskite CsPbBr3 are studied from first-principles calculations. It is shown that the formation energy of dominant defect under Br-rich growth condition is much lower than that under moderate or Br-poor conditions. Thus avoiding the Br-rich condition can help to reduce the defect concentration. Interestingly, CsPbBr3 is found to be highly defect-tolerant in terms of its electronic structure. Most of the intrinsic defects induce shallow transition levels. Only a few defects with high formation energies can create deep transition levels. Therefore, CsPbBr3 can maintain its good electronic quality despite the presence of defects. Such defect tolerance feature can be attributed to the lacking of bonding-antibonding interaction between the conduction bands and valence bands.