Mixed-cation Halide Perovskites Research Articles

Crystal Growth and Structural and Optical Characterizations of Mixed-Cation MA1-xCsxPbBr3 Halide Perovskite Solid Solutions

Photovoltaic devices fabricated using mixed-cation halide perovskites have demonstrated a superior combination of high efficiency and long operating life. In this study, we synthesize a series of mixed-cation halide perovskites with the composition of MA1-xCsxPbBr3 (MA= CH3NH3), where x varies from 0 to 1. We carefully examine various polar solvents and develop a relatively facile, room temperature solution-based growth method for growing these single crystals under optimal conditions. We conduct a comprehensive investigation of the influence of the Cs+ cation on the structure and optical properties of the perovskite solid solutions. The structural characterization using X-ray diffraction confirms the successful substitution of cesium for the methylammonium (MA) cation in the MA1-xCsxPbBr3 perovskite structure, with a continuous solubility. As the Cs+ content increases, the crystal structure undergoes a gradual transformation from a cubic phase (for MAPbBr3) to an orthorhombic phase (for CsPbBr3). To study the impact of Cs substitution on their optical properties, we perform UV-Vis absorption analysis, and find no significant change in the bandgap value, which remains approximately 2.12 - 2.14 eV for the compositions with x up to 0.7, and for x > 0.7, however, the bandgap value gradually increases to reach 2.21 eV for pure CsPbBr3. This work demonstrates a valid technique for the growth of halide perovskite solid solution crystals, which can be a versatile tool for tailoring the structure, long-term stability, and optoelectronic properties for advanced photovoltaic applications.

Disorder on Mixed Cation Halide Perovskite for Photovoltaic Applications.

With reduced toxicity and tunable optoelectronic properties, mixed cation halide perovskites (MCHPs) featuring partially substituted Pb with Sn and Ge have emerged as promising candidates for photovoltaic applications. However, the introduction of the disorder through large-scale preparation and alloying strategies leads to a significant challenge in comprehending the disorder's microscopic-level impact. Here, we found that, in addition to compositional variation, a synergy of disorder and cation radii ratio significantly affects optoelectronic properties. For Pb-Ge/Ge-Sn MCHPs, severe octahedral distortion with increasing degree of disorder adjusted their bandgaps in a wide range, giving rise to large effective masses, exciton binding energies, and weak visible absorption coefficients. The synergy of disorder and distortion transforms the Wannier excitons into localized characteristics, whereas the optoelectronic properties of Pb-Sn MCHPs are modulated by the disorder. Our work highlights the role of disorder in the tunability of optoelectronic properties, providing a novel strategy for designing photovoltaic materials.

Mixed-Cation Halide Perovskite Doped with Rb+ for Highly Efficient Photodetector.

Photodetectors are widely employed as fundamental devices in optical communication, automatic control, image sensors, night vision, missile guidance, and many other industrial or military fields. Mixed-cation perovskites have emerged as promising optoelectronic materials for application in photodetectors due to their superior compositional flexibility and photovoltaic performance. However, their application involves obstacles such as phase segregation and poor-quality crystallization, which introduce defects in perovskite films and adversely affect devices' optoelectronic performance. The application prospects of mixed-cation perovskite technology are significantly constrained by these challenges. Therefore, it is necessary to investigate strategies that combine crystallinity control and defect passivation to obtain high-quality thin films. In this study, we incorporated different Rb+ ratios in triple-cation (CsMAFA) perovskite precursor solutions and studied their effects on crystal growth. Our results show that a small amount of Rb+ was enough to induce the crystallization of the α-FAPbI3 phase and suppress the formation of the yellow non-photoactive phase; the grain size increased, and the product of the carrier mobility and the lifetime (μτ) improved. As a result, the fabricated photodetector exhibited a broad photo-response region, from ultraviolet to near-infrared, with maximum responsivity (R) up to 11.8 mA W-1 and excellent detectivity (D*) values up to 5.33 × 1011 Jones. This work provides a feasible strategy to improve photodetectors' performance via additive engineering.

Facile method for synthesis of mixed-cation halide perovskites by mild equilibrium conversion via iodine-mediated transport reaction in inert liquid media

A new facile method for the synthesis of mixed-cation halide R2 = 0.9935 perovskites based on the chemical conversion of solid precursors (organic halides and lead halides) via an iodine-mediated transport reaction in inert liquid media under mild conditions is described. The equilibrium nature of the conversion provides an exact match between the stoichiometry of the resulting perovskite powder and the molar ratio of the precursors. This method can serve as a useful tool for the synthesis of complex perovskite precursors and the investigation of phase equilibria

Thermal stability and decomposition kinetics of mixed-cation halide perovskites.

Organic-inorganic halide perovskites (OIHPs) have emerged as one of the most efficient photovoltaic materials due to their superior properties. However, improving their stability remains a key challenge. Herein, we investigate the thermal decomposition properties of OIHP FAxMA1-xPbI3 with mixed cations of formamidinium (FA) and methylammonium (MA). Using thermogravimetric analysis together with Fourier transform infrared spectroscopy, we identify and monitor the gaseous decomposition products as a function of temperature and cation composition. Thermal decomposition products of both MA and FA cations were observed at all stages of the thermal decomposition process, contrary to previous expectations. The yield, release sequence and kinetics of the organic gaseous products were found to depend strongly on the ratio between FA and MA cations. Furthermore, cesium ion doping was investigated as a potential strategy to improve the thermal stability of mixed cation perovskites. These results provide new insights into the effect of cation mixing on perovskite stability, suggesting that optimizing the cation ratios and decomposition pathways can guide approaches to boost the stability and performance of mixed cation perovskites.

A Study to Improve the Performance of Mixed Cation-Halide Perovskite-Based UVC Photodetectors.

Photodetectors convert optical signals into electrical signals and demonstrate application potential in various fields, such as optical communication, image detection, environmental monitoring, and optoelectronics. In this study, a mixed cation–halide perovskite-based ultraviolet C photodetector was fabricated using a solution process. The higher the mobility of the perovskite carrier, which is one of the factors affecting the performance of electronic power devices, the better the carrier diffusion. The on/off ratio and responsivity indicate the sensitivity of the response, and together with the detectivity and external quantum efficiency, these parameters demonstrate the performance of the detector. The detector fabricated in this study exhibited a mobility of 202.2 cm2/Vs and a high on/off ratio of 105% at a −2 V bias, under 254 nm light irradiation with an intensity of 0.6 mW/cm2. The responsivity, detectivity, and external quantum efficiency of the as-fabricated detector were 5.07 mA/W, 5.49 × 1011 Jones, and 24.8%, respectively. These findings demonstrate that the solution process employed in this study is suitable for the fabrication of mixed cation–halide perovskites which show immense potential for use as photodetectors.

Excited-state charge polarization and electronic structure of mixed-cation halide perovskites: the role of mixed inorganic-organic cations in CsFAPbI3.

Mixed-cation perovskite materials have shown great potential for sunlight harvesting and have surpassed unmixed perovskite materials in solar cell efficiency and stability. The role of mixed monovalent cations in the enhanced optoelectronic properties and excited state response, however, are still elusive from a theoretical perspective. Herein, through time dependent density functional theory calculations of mixed cation perovskites, we report the electronic structure of Cs formamidinium (FA) mixed cationic lead iodide (Cs0.17FA0.87PbI3) in comparison to the corresponding single monovalent cation hybrid perovskite. The results show that the Cs0.17FA0.87PbI3 and FAPbI3 had negligible differences in the optical band gap, and partial and total density of states in comparison to a single cation perovskite, while the effective mass of carriers, the local atomic density of states, the directional transport, and the structural distortions were significantly different. A lattice-distortion-induced asymmetry in the ground-state charge density is found, and originates from the co-location of caesium atoms in the lattice and signifies the effect on the charge density upon cation mixing and corresponding symmetry breaking. The excited-state charge response and induced polarizabilities are quantified, and discussed in terms of their importance for effective light absorption, charge separation, and final solar cell performance. We also quantify the impact of such polarizabilities on the dynamics of the structure of the perovskites and the implications this has for hot carrier cooling. The results shed light on the mechanism and origin of the enhanced performance in mixed-cation perovskite-based devices and their merits in comparison to single cation perovskites.

Achieving stable and high-efficiency (>21%) lead halide perovskite solar cells with δ-CsPbI2Br seed–assisted growth strategy

Recently, mixed cation-halide perovskites have become particularly interesting for high-performance perovskite solar cells (PSCs) owing to their near-ideal bandgap. Nevertheless, mixed cation-halide perovskites prepared via the existing methods are often subject to high defect density and poor stability, especially the sequential deposition methods in view of the difficulty of incorporating cesium cations (stabilizer). Herein, a simple and effective approach of δ-CsPbI2Br seed–assisting sequential deposition is developed. It is revealed that introducing δ-CsPbI2Br seeds into PbI2 film could not only effectively incorporate Cs+ into the mixed cation-halide perovskite film but also afford δ phase crystal lattices to promote the growth of α phase perovskites during annealing. Such a process can prepare high-quality perovskite film with larger grain size, lower defect density, and longer photoluminescence carrier lifetime (1658 ns). In addition, the thermal stability and humidity stability of the perovskite film are significantly boosted. Consequently, the optimized device delivers a champion efficiency of 21.62%, with an average efficiency of 1.5% higher than that of the control device. In addition, the unencapsulated device exhibits remarkable operational stability, retaining ~92% of the initial efficiency after aging for 1000 h in ambient air. This work provides insight for further preparing the high-quality perovskite film and improving the performance of PSCs.

Reversible oxygen-induced p-doping of mixed-cation halide perovskites

To fully unlock the potential of metal halide perovskites (MHPs) for use in optoelectronic devices, a comprehensive understanding of their electronic properties is in strong demand but presently lacking. This photoelectron spectroscopy study reveals that the thin films of three important mixed-cation/mixed-halide MHPs behave like intrinsic semiconductors with a very low defect concentration. The Fermi level position in the bandgap can be varied by almost 1 eV by choosing substrates of appropriate work function for samples that were handled under inert conditions. Upon oxygen exposure, two organic/inorganic-cation MHPs become strongly p-doped due to oxygen diffusion into the bulk, a process that is fully reversible when storing the samples in ultrahigh vacuum. In contrast, all-inorganic CsPbI1.8Br1.2 exhibits no electronic property changes upon oxygen exposure. Nonetheless, oxygen is found to effectively remove (light-induced) lead-related surface states of CsPbI1.8Br1.2.

Mixed Cation Halide Perovskite under Environmental and Physical Stress.

Despite the ideal performance demonstrated by mixed perovskite materials when used as active layers in photovoltaic devices, the factor which still hampers their use in real life remains the poor stability of their physico-chemical and functional properties when submitted to prolonged permanence in atmosphere, exposure to light and/or to moderately high temperature. We used high resolution photoelectron spectroscopy to compare the chemical state of triple cation, double halide Cs(FAMA)Pb(IBr) perovskite thin films being freshly deposited or kept for one month in the dark or in the light in environmental conditions. Important deviations from the nominal composition were found in the samples aged in the dark, which, however, did not show evident signs of oxidation and basically preserved their own electronic structures. Ageing in the light determined a dramatic material deterioration with heavily perturbed chemical composition also due to reactions of the perovskite components with surface contaminants, promoted by the exposure to visible radiation. We also investigated the implications that 2D MXene flakes, recently identified as effective perovskite additive to improve solar cell efficiency, might have on the labile resilience of the material to external agents. Our results exclude any deleterious MXene influence on the perovskite stability and, actually, might evidence a mild stabilizing effect for the fresh samples, which, if doped, exhibited a lower deviation from the expected stoichiometry with respect to the undoped sample. The evolution of the undoped perovskites under thermal stress was studied by heating the samples in UHV while monitoring in real time, simultaneously, the behaviour of four representative material elements. Moreover, we could reveal the occurrence of fast changes induced in the fresh material by the photon beam as well as the enhanced decomposition triggered by the concurrent X-ray irradiation and thermal heating.

Inclusion of 2D Transition Metal Dichalcogenides in Perovskite Inks and Their Influence on Solar Cell Performance.

Organic–inorganic hybrid perovskite materials have raised great interest in recent years due to their excellent optoelectronic properties, which promise stunning improvements in photovoltaic technologies. Moreover, two-dimensional layered materials such as graphene, its derivatives, and transition metal dichalcogenides have been extensively investigated for a wide range of electronic and optoelectronic applications and have recently shown a synergistic effect in combination with hybrid perovskite materials. Here, we report on the inclusion of liquid-phase exfoliated molybdenum disulfide nanosheets into different perovskite precursor solutions, exploring their influence on final device performance. We compared the effect of such additives upon the growth of diverse perovskites, namely CH3NH3PbI3 (MAPbI3) and triple-cation with mixed halides Csx (MA0.17FA0.83)(1−x)Pb (I0.83Br0.17)3 perovskite. We show how for the referential MAPbI3 materials the addition of the MoS2 additive leads to the formation of larger, highly crystalline grains, which result in a remarkable 15% relative improvement in power conversion efficiency. On the other hand, for the mixed cation–halide perovskite no improvements were observed, confirming that the nucleation process for the two materials is differently influenced by the presence of MoS2.

Effect of reaction time on the morphology and efficiency of ambient-air-processed CsFAMAPbIBr triple cation-mixed perovskite solar cells

The mixed-cation halide perovskites containing formamidinium (FA) are vulnerable to moisture due to easy bonding of FA moieties with H2O. Thus, a strict humidity controlled environment is indispensable for the highest efficiency CsFAMAPbIBr perovskites synthesis, which hinders the development of perovskite manufacturing in ambient atmosphere. In addition, the morphological evolution of CsFAMAPbIBr perovskites in a humid environment and consequent photovoltaic performance is important for understanding ambient air processed mixed perovskite solar cells, but few have been reported. Here, CsFAMAPbIBr perovskites were synthesized in an ambient air atmosphere by a sequential two-step deposition method. The effect of the reaction time is focused to corelate morphological variation and the resultant photovoltaic properties. Using the optimal reaction time of 5 s, CsFAMAPbIBr based planar solar cells with a power conversion efficiency (PCE) of 16.01% were achieved.

Suppression of phase transitions and glass phase signatures in mixed cation halide perovskites

Cation engineering provides a route to control the structure and properties of hybrid halide perovskites, which has resulted in the highest performance solar cells based on mixtures of Cs, methylammonium, and formamidinium. Here, we present a multi-technique experimental and theoretical study of structural phase transitions, structural phases and dipolar dynamics in the mixed methylammonium/dimethylammonium MA1-xDMAxPbBr3 hybrid perovskites (0 ≤ x ≤ 1). Our results demonstrate a significant suppression of the structural phase transitions, enhanced disorder and stabilization of the cubic phase even for a small amount of dimethylammonium cations. As the dimethylammonium concentration approaches the solubility limit in MAPbBr3, we observe the disappearance of the structural phase transitions and indications of a glassy dipolar phase. We also reveal a significant tunability of the dielectric permittivity upon mixing of the molecular cations that arises from frustrated electric dipoles.

A cation-regulation strategy for achieving high-performance perovskite solar cells via a fully-evaporation process

Mixed-cation halide perovskite solar cells (PSCs) have received extensive attention due to their excellent optoelectronic properties and long-term stability. How to further promote its facile and large-scale film-formation procedure is of great significance for commercialization. In this work, a CsMA-based perovskite film was prepared via a two-step evaporation process. By regulating the cation ratio systematically, uniform and large-scale perovskite films can be obtained with excellent stability and high crystallization. Based on the perovskite active layer, typical PSCs were developed with a fully-evaporation technology, and the power conversion efficiency (PCE) of the champion device is 17.15% (J SC = 22.59 mA cm −2 , V OC = 1.03 V, FF = 73.71%). In addition, the PSC module was also explored (active area ≈10 cm 2 ), achieving a PCE of 10.24%. It prospects that our efforts could draw inspiration for pushing ahead the industrialization of the perovskite photovoltaic. • A simplified but powerful sequential vapor deposition method for perovskite films was proposed and developed. • Doping with the optimal concentration of Cs + can improve the PCE of PSC by more than 20%. • The PSC device maintains 85% PCE after stored in ambient condition (40% RH) for half a month. • The PSC module with an effective area of 10.8 cm 2 achieved a PCE of 10.24%.

Effect of rubidium incorporation on the structural, electronic and properties of MAPbI3

The structural stability, electronic and optical properties of Rb-incorporated methylammonium lead halide perovskite (MAPbI3) were investigated by first-principles calculations. A high fraction of Rb+ incorporation can degrade the phase stability of MAPbI3. Moreover, the band gap of Rb-doped MAPbI3 exhibits slightly blueshifted. The optical absorption of Rb-doped MAPbI3 is almost the same with that of the undoped MAPbI3, which can be attributed to the close band gaps of them. Our work can agree well with existing experimental results. Our calculated results can provide a basic insight into the mixed-cation halide perovskites for optoelectronic applications.

Excitonic gain and laser emission from mixed-cation halide perovskite thin films

Organic–inorganic halide perovskites have recently developed into a potential semiconductor coherent light emitter candidate beyond their promise in solar cell applications. However, despite the ample demonstrations of perovskite lasers, experimental results on the origin of optical gain in perovskites are still elusive. Here, we analyze the excitonic gain in the green from mixed-cation halide perovskites Cs0.17[CH(NH2)2]0.83PbBr3 (Cs0.17FA0.83PbBr3) by both low temperature absorption/emission spectroscopies and ultrafast pump–probe transient absorption experiments. The perovskite thin films show a robust excitonic feature up to room temperature, with estimated exciton binding energy E b =43.8 meV, which can be maintained under high electronic excitations that are required for lasers. By using a high-quality (Q=1350) vertical cavity consisting of sputtered dielectric HfO2/SiO2 distributed Bragg reflectors with perovskite optical gain medium embedded inside, we have demonstrated excitonic-gain-enabled optically pumped lasing, with improved threshold of 13.5±1.4 μJ/cm2 and device longevity lifetime >35 h (108 laser shots) at ambient environment under sustained pulsed optical excitations (3.493 eV, τpulse=0.34 ns, 1 kHz). Understanding and exploiting excitonic gain from perovskite thin film materials may help to further boost the performance of perovskite-based lasers.

Dipolar cations confer defect tolerance in wide-bandgap metal halide perovskites

Efficient wide-bandgap perovskite solar cells (PSCs) enable high-efficiency tandem photovoltaics when combined with crystalline silicon and other low-bandgap absorbers. However, wide-bandgap PSCs today exhibit performance far inferior to that of sub-1.6-eV bandgap PSCs due to their tendency to form a high density of deep traps. Here, we show that healing the deep traps in wide-bandgap perovskites—in effect, increasing the defect tolerance via cation engineering—enables further performance improvements in PSCs. We achieve a stabilized power conversion efficiency of 20.7% for 1.65-eV bandgap PSCs by incorporating dipolar cations, with a high open-circuit voltage of 1.22 V and a fill factor exceeding 80%. We also obtain a stabilized efficiency of 19.1% for 1.74-eV bandgap PSCs with a high open-circuit voltage of 1.25 V. From density functional theory calculations, we find that the presence and reorientation of the dipolar cation in mixed cation–halide perovskites heals the defects that introduce deep trap states.

Control over Self‐Doping in High Band Gap Perovskite Films

AbstractIt is reported how differences in the composition of high bandgap Pb bromide‐based perovskites affect their carrier diffusion length and junction type. Pb‐based, APbX3, halide perovskite (HaP) films and devices are studied, where A can be a mixture of formamidinium, methylammonium (MA), and Cs, and X a mixture of Br and Cl, using a combination of dark‐ and photoconductivity and steady‐state photocarrier grating. The results show the cation and anion compositions affect both majority and minority carrier diffusion lengths. In particular, using electron beam‐induced current measurements, FTO\dTiO2mp‐TiO2HaP\PTAA (poly‐triarylamine)\Au devices are studied. The results enable identifying junction and built‐in voltage formation and track position and size of the space charge region width with changes in the HaP composition. As far as it is known, it is found for the first time that a mixed‐cation HaP forms a junction that has characteristics of a p‐i‐n one, with relatively long and comparable carrier diffusion lengths, while the single cation‐based bromide HaPs form clear p‐n junctions at the interface with the TiO2 [pure CsPbBr3 and MAPbBr3(Cl)] or a buried one (MAPbBr3) and shorter diffusion lengths. These differences are attributed to lower carrier density in MAPbBr3, and especially in the mixed cation HaP, which is comparable to iodide‐based HaP films.

Mixed cation perovskite solar cells by stack-sequence chemical vapor deposition with self-passivation and gradient absorption layer

Mixed cation halide perovskite solar cells (PSCs), in a formula of ABX3 where A is a mixture of formamidinium (FA) or cesium (Cs) cations, represent a promising new architecture to achieve largely improved stability and higher power conversion efficiency (PCE). While all these mixed-cation PSCs were synthesized via a solution method, we here propose and demonstrate a precisely tunable stack sequence physical-chemical vapor deposition (SS-PCVD) approach to prepare a mixed-cation absorber in CsBr-doped hybrid organic perovskite, which features a beneficial gradient bandgap profile to enable an improvement of PCE from 11.69% in pure FAPbI3 to 18.22% in mixed-cation PSCs. Remarkably, an excellent stability in ambient exposure for 60 days has been achieved by a proper control of the CsBr cation incorporation and interface passivation. This new approach indicates a simple, precisely tunable and low cost fabrication strategy to implement high performance and scalable mixed-cation halide perovskite solar cells.

Controlled Crystal Grain Growth in Mixed Cation-Halide Perovskite by Evaporated Solvent Vapor Recycling Method for High Efficiency Solar Cells.

We developed a new and simple solvent vapor-assisted thermal annealing (VA) procedure which can reduce grain boundaries in a perovskite film for fabricating highly efficient perovskite solar cells (PSCs). By recycling of solvent molecules evaporated from an as-prepared perovskite film as a VA vapor source, named the pot-roast VA (PR-VA) method, finely controlled and reproducible device fabrication was achieved for formamidinium (FA) and methylammonium (MA) mixed cation-halide perovskite (FAPbI3)0.85(MAPbBr3)0.15. The mixed perovskite was crystallized on a low-temperature prepared brookite TiO2 mesoporous scaffold. When exposed to very dilute solvent vapor, small grains in the perovskite film gradually unified into large grains, resulting in grain boundaries which were highly reduced and improvement of photovoltaic performance in PSC. PR-VA-treated large grain perovskite absorbers exhibited stable photocurrent-voltage performance with high fill factor and suppressed hysteresis, achieving the best conversion efficiency of 18.5% for a 5 × 5 mm2 device and 15.2% for a 1.0 × 1.0 cm2 device.