Perovskite Emission Research Articles

Efficient Inorganic Perovskite Light-Emitting Diodes with Polyethylene Glycol Passivated Ultrathin CsPbBr3 Films.

Efficient inorganic perovskite light-emitting diodes (PeLEDs) with an ultrathin perovskite emission layer (∼30 nm) were realized by doping Lewis base polyethylene glycol (PEG) into CsPbBr3 films. PEG in the perovskite films not only physically fills the crystal boundaries but also interacts with the perovskite crystals to passivate the crystal grains, reduce nonradiative recombination, and ensure efficient luminance and high efficiency. As a result, promoted brightness, current efficiency (CE), and external quantum efficiency (EQE) were achieved. The nonradiative decay rate of the PEG:CsPbBr3 composite film is 1 order of magnitude less than that of the neat CsPbBr3 film. After further optimization of the molar ratio between CsBr and PbBr2, a peak CE of 19 cd/A, a maximum EQE of 5.34%, and a maximum brightness of 36600 cd/m2 were achieved, demonstrating the interaction between PEG and the precursors. The results are expected to offer some helpful implications in optimizing the polymer-assisted PeLEDs with ultrathin emission layers, which might have potential application in see-through displays.

All-inorganic quantum-dot light-emitting diodes based on perovskite emitters with low turn-on voltage and high humidity stability

We present the all-inorganic QLEDs, including inorganic perovskite emitters (CsPbBr3) and inorganic charge transport layers (CTLs), with emphasis on the significantly improved device stability and low turn-on voltage.

Origin of unusual bandgap shift and dual emission in organic-inorganic lead halide perovskites.

Emission characteristics of metal halide perovskites play a key role in the current widespread investigations into their potential uses in optoelectronics and photonics. However, a fundamental understanding of the molecular origin of the unusual blueshift of the bandgap and dual emission in perovskites is still lacking. In this direction, we investigated the extraordinary photoluminescence behavior of three representatives of this important class of photonic materials, that is, CH3NH3PbI3, CH3NH3PbBr3, and CH(NH2)2PbBr3, which emerged from our thorough studies of the effects of temperature on their bandgap and emission decay dynamics using time-integrated and time-resolved photoluminescence spectroscopy. The low-temperature (<100 K) photoluminescence of CH3NH3PbI3 and CH3NH3PbBr3 reveals two distinct emission peaks, whereas that of CH(NH2)2PbBr3 shows a single emission peak. Furthermore, irrespective of perovskite composition, the bandgap exhibits an unusual blueshift by raising the temperature from 15 to 300 K. Density functional theory and classical molecular dynamics simulations allow for assigning the additional photoluminescence peak to the presence of molecularly disordered orthorhombic domains and also rationalize that the unusual blueshift of the bandgap with increasing temperature is due to the stabilization of the valence band maximum. Our findings provide new insights into the salient emission properties of perovskite materials, which define their performance in solar cells and light-emitting devices.

Metal halide perovskite light emitters

Twenty years after layer-type metal halide perovskites were successfully developed, 3D metal halide perovskites (shortly, perovskites) were recently rediscovered and are attracting multidisciplinary interest from physicists, chemists, and material engineers. Perovskites have a crystal structure composed of five atoms per unit cell (ABX3) with cation A positioned at a corner, metal cation B at the center, and halide anion X at the center of six planes and unique optoelectronic properties determined by the crystal structure. Because of very narrow spectra (full width at half-maximum ≤20 nm), which are insensitive to the crystallite/grain/particle dimension and wide wavelength range (400 nm ≤ λ ≤ 780 nm), perovskites are expected to be promising high-color purity light emitters that overcome inherent problems of conventional organic and inorganic quantum dot emitters. Within the last 2 y, perovskites have already demonstrated their great potential in light-emitting diodes by showing high electroluminescence efficiency comparable to those of organic and quantum dot light-emitting diodes. This article reviews the progress of perovskite emitters in two directions of bulk perovskite polycrystalline films and perovskite nanoparticles, describes current challenges, and suggests future research directions for researchers to encourage them to collaborate and to make a synergetic effect in this rapidly emerging multidisciplinary field.

Molecularly Engineered Organic-Inorganic Hybrid Perovskite with Multiple Quantum Well Structure for Multicolored Light-Emitting Diodes.

Organic-inorganic hybrid perovskites have the potential to be used as a new class of emitters with tunable emission, high color purity and good ease of fabrication. Recent studies have so far been focused on three-dimensional (3D) perovskites, such as CH3NH3PbBr3 and CH3NH3PbI3 for green and infrared emission. Here, we explore a new series of hybrid perovskite emitters with a general formula of (C4H9NH3)2(CH3NH3)n−1PbnI3n+1 (where n = 1, 2, 3), which possesses a multiple quantum well structure. The quantum well thickness of these materials is adjustable through simple molecular engineering which results in a continuously tunable bandgap and emission spectra. Deep saturated red emission was obtained with a peak external quantum efficiency of 2.29% and a maximum luminance of 214 cd/m2. Green and blue LEDs were also demonstrated through halogen substitutions in these hybrid perovskites. We expect these results to open up the way towards high performance perovskite LEDs through molecular-structure engineering of these perovskite emitters.

Band-gap tuning of lead halide perovskite using a single step spin-coating deposition process

In this paper, we present a study of the structural and optical properties of organic–inorganic halide-based perovskite semiconductors with band gaps varying from NIR to visible at room temperature. Thin films of nanocrystalline CH3NH3PbI3 with different concentrations of methylammonium iodide (MAI) have been successfully deposited onto glass substrates using single step spin-coating technique. The prepared films have been characterized by X-ray diffraction, optical absorption spectroscopy and photoluminescence measurements. X-ray diffraction scans revealed that even for stoichiometric atomic concentrations of MA:Pb:I of 1:1:3, the PbI2 phase was also present. The PbI2 phase showed a highly textured along the (001) direction in all the prepared films, with a crystallite size in the range of approximately 30–40nm. The optical absorbance edge of CH3NH3PbI3 thin films is described in terms of direct transition model proposed by Tauc in the strong absorption region. The band gap of the pure PbI2 film was calculated to be 2.40eV, whereas the band gap of the pervoskite film with stoichiometric ionic ratio of 1:1 PbI2 and CH3NH3I was calculated to be 1.46eV, while absorption coefficient is ~105cm−1. Photoluminescence measurements showed a red shift in the perovskite emission with increasing the MAI concentration, confirming the correct placement of the MA ions in the perovskite crystalline structure showing the PbI2 octahedra. Our results confirm the existence of PbI2 phase in the highly efficient perovskite solar cells, as demonstrated in the recent publication.

Unraveling the Effect of PbI2 Concentration on Charge Recombination Kinetics in Perovskite Solar Cells

CH3NH3PbI3 perovskite solar cells have rapidly risen to the forefront of emerging photovoltaic technologies. A solution-based, two-step method was reported to enhance the reproducibility of these solar cells. In this method, first a coating of PbI2 is applied by spin-coating onto a TiO2-coated substrate, followed by a dip in a methylammonium iodide solution, leading to conversion to CH3NH3PbI3. The concentration of PbI2 in the spin-coating solution is a very important factor that affects the infiltration of the perovskite and the amount deposited. The best solar cell performance of 13.9% was obtained by devices prepared using 1.0 M of PbI2 in dimethylformamide. These devices also had the longest electron lifetime and shortest carrier transport time, yielding lowest recombination losses. Rapid quenching of the perovskite emission is found in device-like structures, suggesting reasonably good efficient carrier extraction at the TiO2 interface and quantitative extraction at the spiro–OMeTAD interface.

Efficient light-emitting diodes based on nanocrystalline perovskite in a dielectric polymer matrix.

Electroluminescence in light-emitting devices relies on the encounter and radiative recombination of electrons and holes in the emissive layer. In organometal halide perovskite light-emitting diodes, poor film formation creates electrical shunting paths, where injected charge carriers bypass the perovskite emitter, leading to a loss in electroluminescence yield. Here, we report a solution-processing method to block electrical shunts and thereby enhance electroluminescence quantum efficiency in perovskite devices. In this method, a blend of perovskite and a polyimide precursor dielectric (PIP) is solution-deposited to form perovskite nanocrystals in a thin-film matrix of PIP. The PIP forms a pinhole-free charge-blocking layer, while still allowing the embedded perovskite crystals to form electrical contact with the electron- and hole-injection layers. This modified structure reduces nonradiative current losses and improves quantum efficiency by 2 orders of magnitude, giving an external quantum efficiency of 1.2%. This simple technique provides an alternative route to circumvent film formation problems in perovskite optoelectronics and offers the possibility of flexible and high-performance light-emitting displays.

Enhanced performance in fluorene-free organometal halide perovskite light-emitting diodes using tunable, low electron affinity oxide electron injectors.

Fluorene-free perovskite light-emitting diodes (LEDs) with low turn-on voltages, higher luminance and sharp, color-pure electroluminescence are obtained by replacing the F8 electron injector with ZnO, which is directly deposited onto the CH3NH3PbBr3 perovskite using spatial atmospheric atomic layer deposition. The electron injection barrier can also be reduced by decreasing the ZnO electron affinity through Mg incorporation, leading to lower turn-on voltages.

Bright light-emitting diodes based on organometal halide perovskite.

Solid-state light-emitting devices based on direct-bandgap semiconductors have, over the past two decades, been utilized as energy-efficient sources of lighting. However, fabrication of these devices typically relies on expensive high-temperature and high-vacuum processes, rendering them uneconomical for use in large-area displays. Here, we report high-brightness light-emitting diodes based on solution-processed organometal halide perovskites. We demonstrate electroluminescence in the near-infrared, green and red by tuning the halide compositions in the perovskite. In our infrared device, a thin 15 nm layer of CH3NH3PbI(3-x)Cl(x) perovskite emitter is sandwiched between larger-bandgap titanium dioxide (TiO2) and poly(9,9'-dioctylfluorene) (F8) layers, effectively confining electrons and holes in the perovskite layer for radiative recombination. We report an infrared radiance of 13.2 W sr(-1) m(-2) at a current density of 363 mA cm(-2), with highest external and internal quantum efficiencies of 0.76% and 3.4%, respectively. In our green light-emitting device with an ITO/PEDOT:PSS/CH3NH3PbBr3/F8/Ca/Ag structure, we achieved a luminance of 364 cd m(-2) at a current density of 123 mA cm(-2), giving external and internal quantum efficiencies of 0.1% and 0.4%, respectively. We show, using photoluminescence studies, that radiative bimolecular recombination is dominant at higher excitation densities. Hence, the quantum efficiencies of the perovskite light-emitting diodes increase at higher current densities. This demonstration of effective perovskite electroluminescence offers scope for developing this unique class of materials into efficient and colour-tunable light emitters for low-cost display, lighting and optical communication applications.

High temperature far-infrared dynamics of orthorhombic NdMnO3: emissivity and reflectivity

We report on near normal far- and mid-infrared emission and reflectivity of NdMnO3 perovskite from room temperature to sample decomposition above 1800 K. At 300 K the number of infrared active phonons is in close agreement with the 25 calculated for the orthorhombic –Pbnm (Z = 4) space group. Their number gradually decreases as we approach the temperature of orbital disorder at ∼1023 K where the orthorhombic O′ lower temperature cooperative phase coexists with the cubic orthorhombic O. At above ∼1200 K, the three infrared active phonons coincide with that expected for cubic Pm-3m (Z = 1) in the high temperature insulating regime. Heating samples in dry air triggers double exchange conductivity by Mn3+ and Mn4+ ions and a small polaron mid-infrared band. Fits to the optical conductivity single out the octahedral antisymmetric and symmetric vibrational modes as the main phonons in the electron–phonon interactions at 875 K. For 1745 K, it is enough to consider the symmetric stretching internal mode. An overdamped defect induced Drude component is clearly outlined at the highest temperatures. We conclude that rare earth manganite eg electrons are prone to spin, charge, orbital, and lattice couplings in an intrinsic orbital distorted perovskite lattice, favoring embryonic low energy collective excitations.

First principles calculations on the origin of violet-blue and green light photoluminescence emission in SrZrO3 and SrTiO3 perovskites

The photoluminescence (PL) emission from SrZrO3 (SZ) and SrTiO3 (ST) crystalline, quasi-crystalline, and quasi-amorphous samples, prepared by the polymeric precursor method, was examined by ab initio quantum mechanical calculations. It was used in the modeling the structural model consisting of one pyramidal TiO5 or ZrO5 unit piled upon the TiO6 or ZrO6, which are representative of disordered structures of quasi-crystalline structures such as ST and SZ. The structural crystallization process was monitored by X-ray diffraction. In quasi-crystalline powders, the photoluminescence (PL) in the visible region showed different peak positions and intensities in SZ and ST. The PL emission was linked to distinct distortions in perovskite lattices and the emission of two colors—violet-blue in SZ and green in ST—was also examined in the light of favorable structural and electronic conditions.