Mixed Lead Halide Research Articles

Azetidinium as cation in lead mixed halide perovskite nanocrystals of optoelectronic quality

Previous theoretical calculations show that azetidinium has the right radial size to form a 3D perovskite with lead halides [G. Kieslich et al., Chem. Sci. 5, 4712 (2014)] and has been shown to impart, as the A-site cation of the ABX3 unit, beneficial properties to ferroelectric perovskites [B. Zhou et al., Angew. Chem., Int. Ed. 50, 11441 (2011)]. However, there has been very limited research into its use as the cation in lead halide perovskites to date. In this communication, we report the synthesis and characterization of azetidinium-based lead mixed halide perovskite colloidal nanocrystals. The mixed halide system is iodine and chlorine unlike other reported nanocrystals in the literature, where the halide systems are either iodine/bromine or bromine/chlorine. UV-visible absorbance data, complemented with photoluminescence spectroscopy, reveal an indirect-bandgap of about 2.018 eV for our nanocrystals. Structural characterization using transmission electron microscopy shows two distinct interatomic distances (2.98 Å ± 0.15 Å and 3.43 Å ± 0.16 Å) and non-orthogonal lattice angles (≈112°) intrinsic to the nanocrystals with a probable triclinic structure revealed by X-ray diffraction. The presence of chlorine and iodine within the nanocrystals is confirmed by energy dispersive X-ray spectroscopy. Finally, light-induced electron paramagnetic resonance spectroscopy with PCBM confirms the photoinduced charge transfer capabilities of the nanocrystals. The formation of such semiconducting lead mixed halide perovskites using azetidinium as the cation suggests a promising subclass of hybrid perovskites holding potential for optoelectronic applications such as in solar cells and photodetectors.

Mixed Lead Halide Passivation of Quantum Dots.

Infrared-absorbing colloidal quantum dots (IR CQDs) are materials of interest in tandem solar cells to augment perovskite and cSi photovoltaics (PV). Today's best IR CQD solar cells rely on the use of passivation strategies based on lead iodide; however, these fail to passivate the entire surface of IR CQDs. Lead chloride passivated CQDs show improved passivation, but worse charge transport. Lead bromide passivated CQDs have higher charge mobilities, but worse passivation. Here a mixed lead-halide (MPbX) ligand exchange is introduced that enables thorough surface passivation without compromising transport. MPbX-PbS CQDs exhibit properties that exceed the best features of single lead-halide PbS CQDs: they show improved passivation (43 ± 5 meV vs 44 ± 4 meV in Stokes shift) together with higher charge transport (4 × 10-2 ± 3 × 10-3 cm2 V-1 s-1 vs 3 × 10-2 ± 3 × 10-3 cm2 V-1 s-1 in mobility). This translates into PV devices having a record IR open-circuit voltage (IR Voc ) of 0.46 ± 0.01 V while simultaneously having an external quantum efficiency of 81 ± 1%. They provide a 1.7× improvement in the power conversion efficiency of IR photons (>1.1 µm) relative to the single lead-halide controls reported herein.

Cesium Lead Mixed-Halide Perovskites for Low-Energy Loss Solar Cells with Efficiency Beyond 17%

In spite of rapid progress in cesium lead halide (CsPbX3) perovskites solar cells (PSCs), their power conversion efficiencies (PCEs) achieved to date leave much space for further improvement, princ...

Compositional Engineering of Mixed-Cation Lead Mixed-Halide Perovskites for High-Performance Photodetectors.

The mixed-cation lead mixed-halide perovskites can combine the advantages of the constituents while avoiding their drawbacks, and they have been widely explored in solar cells. However, there are only few research studies on the mixed-cation lead mixed-halide perovskites for photodetectors. In this work, we fabricate photodetectors based on FA(1-x)CsxPb(BryI(1-y))3 perovskite and reveal the effect of the chemical composition on the crystal phase stability and device performance of mixed-cation mixed-halide perovskite photodetectors. The FA0.7Cs0.3Pb(I0.8Br0.2)3 photodetectors exhibit high specific detectivity, high responsivity, and excellent stability in ambient conditions. Especially, the flexible perovskite photodetectors fabricated on poly(ethylene terephthalate) substrates exhibit extremely high specific detectivity of 2.8 × 1013 Jones, which is the highest value to date for flexible perovskite photodetectors, as well as excellent stability and outstanding flexibility. These results indicate that mixed-cation mixed-halide perovskites are promising to be applied in high-performance photodetectors and other flexible optoelectronic devices.

Multi-cation Synergy Suppresses Phase Segregation in Mixed-Halide Perovskites

Summary Mixed lead halide perovskite solar cells have been demonstrated to benefit tremendously from the addition of Cs+ and Rb+, but its root cause is yet to be understood. This hinders further improvement, and processing approaches remain largely empirical. We address the challenge by tracking the solidification of precursors in situ and linking the evolutions of different crystalline phases to the presence of Cs+ and Rb+. In their absence, the perovskite film is inherently unstable, segregating into MA-I- and FA-Br-rich phases. Adding either Cs+ or Rb+ is shown to alter the solidification process of the perovskite films. The optimal addition of both Cs+ and Rb+ drastically suppress phase segregation and promotes the spontaneous formation of the desired α phase. We propose that the synergistic effect is due to the collective benefits of Cs+ and Rb+ on the formation kinetics of the α phase and on the halide distribution throughout the film.

Air-Stable and Oriented Mixed Lead Halide Perovskite (FA/MA) by the One-Step Deposition Method Using Zinc Iodide and an Alkylammonium Additive.

We present a one-step method to produce air-stable, large-grain mixed cationic lead perovskite films and powders under ambient conditions. The introduction of 2.5 % of Zn(II), confirmed by X-ray diffraction (XRD), results in stable thin films which show the same absorption and crystal structure after 2 weeks of storage under ambient conditions. Next to prolonged stability, the introduction of Zn(II) affects photophysical properties, reducing the bulk defect density, enhancing the photoluminescence (PL), and extending the charge carrier lifetime. Furthermore, 3-chloropropylamine hydrochloride is applied as the film-forming agent. The presence of this amine hydrochloride additive results in highly oriented and large crystal domains showing an ulterior improvement of PL intensity and lifetime. The material can also be prepared as black precursor powder by a solid–solid reaction under ambient conditions and can be pressed into a perovskite pellet. The prolonged stability and the easy fabrication in air makes this material suitable for large-scale, low-cost processing for optoelectronic applications.

Hydration of mixed halide perovskites investigated by Fourier transform infrared spectroscopy

The mixed lead halide perovskites are promising candidates for solar cells, but the intrinsic instabilities due to phase segregation, halide migration, and hydration hinder the practical applications. Currently, less attention is paid to the humidity induced degradation. This important issue of mixed halide perovskites is now investigated by Fourier transform infrared (FTIR) spectroscopy. After hydration of CH3NH3Pb(I1−xBrx)3, a broad band at around 3200 cm−1 of –OH vibration appears in the FTIR spectra and the bands in the range of 1200–1700 cm−1 become much stronger. The dominant FTIR mode at 1660 cm−1 due to the intermediate complex is sensitive on hydration, implying it could be used as a characteristic peak to evaluate the hydration degree of mixed halide perovskites. These information are of interest to optimize the crystal structure of this material to improve the stability so that to promote the photovoltaic applications.

On the origin of spatially dependent electronic excited-state dynamics in mixed hybrid perovskite thin films

The fundamental photophysics underlying the remarkable performance of organic-inorganic hybrid perovskites in optoelectronic device applications has been increasingly studied using complementary spectroscopic techniques. However, the spatially heterogeneous polycrystalline morphology of the solution-processed thin films is often overlooked in conventional ensemble measurements and therefore the reported results are averaged over hundreds or even thousands of nano- and micro-crystalline grains. Here, we apply femtosecond transient absorption microscopy to spatially and temporally probe ultrafast electronic excited-state dynamics in chloride containing mixed lead halide perovskite (CH3NH3PbI3–xClx) thin films. We found that the electronic excited-state relaxation kinetics are extremely sensitive to the spatial location probed, which was manifested by position-dependent transient absorption signal amplitude and decay behaviour, along with an obvious rise component at some positions. The analysis of transient absorption kinetics acquired at several distinct spatial positions enabled us to identify Auger recombination as the dominant mechanism underlying the initial portions of the spatially dependent dynamics with variable rate constants. The different rates observed suggest occurrence of distinct local electronic structures and variable contributions from impurities/defects and phonons in this nonlinear dynamical process.

Ultrafast Carrier Dynamics and Terahertz Photoconductivity of Mixed-Cation and Lead Mixed-Halide Hybrid Perovskites**Supported by the National Natural Science Foundation of China under Grant Nos 11604202, 11674213, 61735010 and 51603119, the Young Eastern Scholar under Grant Nos QD2015020 and QD2016027, the Shanghai Rising-Star Program under Grant No 18QA1401700, the ‘Chen Guang’ Project under Grant Nos 16CG45 and 16CG46, the Shanghai Municipal

Using time-dependent terahertz spectroscopy, we investigate the role of mixed-cation and mixed-halide on the ultrafast photoconductivity dynamics of two different methylammonium (MA) lead-iodide perovskite thin films. It is found that the dynamics of conductivity after photoexcitation reveals significant correlation on the microscopy crystalline features of the samples. Our results show that mixed-cation and lead mixed-halide affect the charge carrier dynamics of the lead-iodide perovskites. In the (5-AVA)0.05(MA)0.95PbI2.95Cl0.05/spiro thin film, we observe a much weaker saturation trend of the initial photoconductivity with high excitation fluence, which is attributed to the combined effect of sequential charge carrier generation, transfer, cooling and polaron formation.

Electronic Traps and Phase Segregation in Lead Mixed-Halide Perovskite

An understanding of the factors driving halide segregation in lead mixed-halide perovskites is required for their implementation in tandem solar cells with existing silicon technology. Here we report that the halide segregation dynamics observed in the photoluminescence from CH3NH3Pb(Br0.5I0.5)3 is strongly influenced by the atmospheric environment, and that encapsulation of films with a layer of poly(methyl methacrylate) allows for halide segregation dynamics to be fully reversible and repeatable. We further establish an empirical model directly linking the amount of halide segregation observed in the photoluminescence to the fraction of charge carriers recombining through trap-mediated channels, and the photon flux absorbed. From such quantitative analysis we show that under pulsed illumination, the frequency of the modulation alone has no influence on the segregation dynamics. Additionally, we extrapolate that working CH3NH3Pb(Br0.5I0.5)3 perovskite cells would require a reduction of the trap-related c...

The domination of ionic conductivity in tetragonal phase of the organometal halide perovskite CH3NH3PbI3-xClx

Organometal trihalide perovskites have recently gained extreme attention due to their high solar energy conversion in photovoltaic cells. Here, we investigate the contribution of iodide ions to a total conductivity of the mixed lead halide perovskite CH3NH3PbI3−xClx with a use of the modified DC Hebb–Wagner polarization method. It has been identified that an ionic conductivity dominates in tetragonal phase which is associated with room temperature. The obtained activation energy for this type of hopping mechanism is equal to (0.87 ± 0.02) eV, which is in a good agreement with previous literature reports. The high contribution of ionic conductivity at room temperature might be a reason of the observed hysteresis in halide perovskite solar cells.

Rubidium as an Alternative Cation for Efficient Perovskite Light-Emitting Diodes.

Incorporation of rubidium (Rb) into mixed lead halide perovskites has recently achieved record power conversion efficiency and excellent stability in perovskite solar cells. Inspired by these tremendous advances in photovoltaics, this study demonstrates the impact of Rb incorporation into MAPbBr3-based light emitters. Rb partially substitutes MA (methyl ammonium), resulting in a mixed cation perovskite with the formula MA(1- x)Rb xPbBr3. Pure MAPbBr3 crystallizes into a polycrystalline layer with highly defective sub-micrometer grains. However, the addition of a small amount of Rb forms MA(1- x)Rb xPbBr3 nanocrystals (10 nm) embedded in an amorphous matrix of MA/Rb Br. These nanocrystals grow into defect-free sub-micrometer-sized crystallites with further addition of Rb, resulting in a 3-fold increase in exciton lifetime when the molar ratio of MABr/RbBr is 1:1. A thin film fabricated with a 1:1 molar ratio of MABr/RbBr showed the best electroluminescent properties with a current efficiency (CE) of 9.45 cd/A and a luminance of 7694 cd/m2. These values of CE and luminance are, respectively, 19 and 10 times larger than those achieved by pure MAPbBr3 devices (0.5 cd/A and 790 cd/m2). We believe this work provides important information on the future compositional optimization of Rb+-based mixed cation perovskites for obtaining high-performance light-emitting diodes.

Extending the Compositional Space of Mixed Lead Halide Perovskites by Cs, Rb, K, and Na Doping

A trend in high performing lead halide perovskite solar cell devices has been increasing compositional complexity by successively introducing more elements, dopants, and additives into the structure; and some of the latest top efficiencies have been achieved with a quadruple cation mixed halide perovskite CsxFAyMAzRb1-x-y-zPbBrqI3-q. This paper continues this trend by exploring doping of mixed lead halide perovskites, FA0.83MA0.17PbBr0.51I2.49, with an extended set of alkali cations, i.e., Cs+, Rb+, K+, and Na+, as well as combinations of them. The doped perovskites were investigated with X-ray diffraction, energy-dispersive X-ray spectroscopy, scanning electron microscopy, hard X-ray photoelectron spectroscopy, UV–vis, steady state fluorescence, and ultrafast transient absorption spectroscopy. Solar cell devices were made as well. Cs+ can replace the organic cations in the perovskite structure, but Rb+, K+, and Na+ do not appear to do that. Despite this, samples doped with K and Na have substantially longer fluorescence lifetimes, which potentially could be beneficial for device performance.

The role of a vapor-assisted solution process on tailoring the chemical composition and morphology of mixed-halide perovskite solar cells

Herein, we report a modified two-step method to construct a uniform and pinhole-free polycrystalline perovskite film with large grains up to the microscale using lead mixed-halide (PbI2–PbCl2) precursor solutions to guarantee the device functioning.

Spatial Inhomogeneity of Methylammonium Lead-Mixed Halide Perovskite Examined by Space- and Time-Resolved Microwave Conductivity.

Reducing the spatial inhomogeneity of solution-processed, multicrystalline methylammonium lead iodide (MAPbI3) perovskite is of great importance for improving its power conversion efficiency, suppressing point-to-point deviations, and delaying degradation during operation. Various techniques, such as conducting-mode atomic force microscopy and photoluminescence mapping, have been applied for this intriguing class of materials, revealing nonuniform electronic properties on the nanometer-to-micrometer scale. Here, we designed a new space- and time-resolved microwave conductivity system that enables mapping of the transient photoconductivity with resolution greater than ∼45 μm. We examined the effects of the precursor concentration of MAPbI3 and the mixing of halides (I– and Br–) on the charge carrier dynamics, crystal size, and inhomogeneity of the films. The optoelectronic inhomogeneity of MAPbI3 and MAPb(I1–xBrx)3 on the sub-millimeter and millimeter scales shows a general correlation with their crystallite sizes, whereas the precursor concentration and halide mixing affect the inhomogeneity in a different way, providing a basis for uniform processing of a multicrystalline perovskite film.

CH3NH3Cl Assisted Solvent Engineering for Highly Crystallized and Large Grain Size Mixed-Composition (FAPbI3)0.85(MAPbBr3)0.15 Perovskites

High-quality mixed-cation lead mixed-halide (FAPbI3)0.85(MAPbBr3)0.15 perovskite films have been prepared using CH3NH3Cl additives via the solvent engineering method. The UV/Vis result shows that the addition of additives leads to enhanced absorptions. XRD and SEM characterizations suggest that compact, pinhole-free and uniform films can be obtained. This is attributable to the crystallization improvement caused by the CH3NH3Cl additives. The power conversion efficiency (PCE) of the F-doped SnO2 (FTO)/compact-TiO2/perovskite/Spiro-OMeTAD/Ag device increases from 15.3% to 16.8% with the help of CH3NH3Cl additive.

Fabrication and characterization of mixed lead halide thin films for perovskite solar cells

ABSTRACTRecently, a new class of perovskite was introduced as a light harvesting material that shows strong absorption in a broad region of the visible spectrum, good electron and hole conductivity, and delivers high open circuit voltages in photovoltaic devices. Perovskite solar cells consist of CH3NH3PbX3 loaded on a mesoporous TiO2 layer in conjunction with the hole transporting material between the two electrodes. Optimizing the efficiency of perovskite solar cells is important for light harvesting devices. One approach to improving the efficiency is to increase the charge collection; the electron diffusion length and recombination lifetime influence the performance of perovskite solar cells. In this study, the influence of PbCl2 content in a PbI2 solution of N,N-dimethylformamide (DMF) on the absorption, crystal phase, and morphology of lead halide thin films was systematically investigated and the photovoltaic performance of the corresponding planar perovskite solar cells was evaluated. The planar perovskite solar cell based on the 300-nm-thick methyl ammonium iodide (CH3NH3I):PbI2:PbCl2 (4 M:1.25 M:0.75 M) thin film exhibited the optimum photoelectric conversion efficiency of 6.3% along with an open-circuit voltage of 0.66 V, a short-circuit photocurrent density of 19.60 mA cm−2, and a fill factor of 58.3%.

The Effect of Stoichiometry on the Stability of Inorganic Cesium Lead Mixed-Halide Perovskites Solar Cells

Metal halide perovskite solar cells that use the inorganic cation Cs have been shown to have better thermal stability than the organic cation containing counterparts, and CsPbI2Br has a more suitable (lower) band gap than CsPbIBr2 as a photovoltaic energy harvesting material. However, increase in iodine content reduces structural stability due to the preference toward the non-perovskite orthorhombic phase when the film is exposed to air. In this work, the effect of varying stoichiometry of CsPbI2Br perovskite on film quality such as the grain size, presence of impurities and nature of impurity grains, photoluminescence, morphology, and elemental distribution are studied. Details on how to vary the stoichiometry during the dual source thermal evaporation process are reported. It is found that the air stability of CsPbI2Br film correlates with the CsBr-to-PbI2 deposition rate ratio, in which the CsBr-rich CsPbI2Br is the most stable upon air exposure, while the stoichiometrically balanced CsPbI2Br perovskit...

Bulk and interface recombination in planar lead halide perovskite solar cells: A Drift-Diffusion study

A theoretical approach based on Drift-Diffusion equations is presented to study planar mixed lead halide perovskite solar cells. Updated physical parameters such as permittivity, mobility, effective density of states and doping density is employed in simulations. Current-voltage curve data for two experimental sample is imported and through fitting with the model, density of bulk and interface defects is calculated. We obtain the bulk defect density around 1016cm−3 and surface recombination velocities in the range of 10cm/s. These values which are in good agreement with experimental measurements and considerably deviated from previous theoretical studies, verify the model and adopted constants. Shockley-Queisser limit is also presented as the ideal device and the effect of bulk and interface defects are presented as loss factors that cause departure from this limit. Our simulations conclude that the overall efficiency of perovskite solar cells is mainly governed by the open-circuit voltage and also identify the interface defects as the major loss factor in these devices.

Effects of Annealing Conditions on Mixed Lead Halide Perovskite Solar Cells and Their Thermal Stability Investigation.

In this work, efficient mixed organic cation and mixed halide (MA0.7FA0.3Pb(I0.9Br0.1)3) perovskite solar cells are demonstrated by optimizing annealing conditions. AFM, XRD and PL measurements show that there is a better perovskite film quality for the annealing condition at 100 °C for 30 min. The corresponding device exhibits an optimized PCE of 16.76% with VOC of 1.02 V, JSC of 21.55 mA/cm2 and FF of 76.27%. More importantly, the mixed lead halide perovskite MA0.7FA0.3Pb(I0.9Br0.1)3 can significantly increase the thermal stability of perovskite film. After being heated at 80 °C for 24 h, the PCE of the MA0.7FA0.3Pb(I0.9Br0.1)3 device still remains at 70.00% of its initial value, which is much better than the control MAPbI3 device, where only 46.50% of its initial value could be preserved. We also successfully fabricated high-performance flexible mixed lead halide perovskite solar cells based on PEN substrates.