Using cross-correlation current noise spectroscopy, we have investigated carrier dynamics in methylammonium lead triiodide solar cells. This method provides a space selectivity for devices with planar multi-layered structure, effectively amplifying current noise contributions coming from the most resistive element of the stack. In the studied solar cells, we observe near full-scale shot noise, indicating the dominance of noise generation by a single source, likely the interface between the perovskite and the spiro-OMeTAD hole-transport layer. We argue that the strong 1/f noise term has contributions both from the perovskite layer and interfaces. It displays non-ideal dependence on photocurrent, $S \propto I^{1.4}$ (instead of usual $S \propto I^2$ ), which is likely due to current-induced halide migration. Finally, we observe generation-recombination noise. The relaxation time of this process grows linearly with photocurrent, which allows to attribute this contribution to bimolecular recombination in the perovskite bulk absorption layer. Extrapolating our results, we estimate that at the standard 1 sun illumination the electron-hole recombination time is 5 microseconds.
Metal halide perovskites (MHPs) are known to undergo several structural phase transitions, from lower to higher symmetry, upon heating. While structural phase transitions have been investigated by a wide range of optical, thermal and electrical methods, most measurements are quasi-static and hence do not provide direct information regarding the fundamental timescale of phase transitions in this emerging class of semiconductors. Here we investigate the timescale of the orthorhombic-to-tetragonal phase transition in the prototypical metal halide perovskite, methylammonium lead triiodide (CH3NH3P…
We show that the addition of 1 % (v/v) nitrobenzene within the perovskite formulation can be used as a method to improve the power conversion efficiency and reliability performance of methylammonium-free (CsFA) inverted perovskite solar cells. Addition of nitrobenzene increased PCE due to defect passivation and provides smoother films resulting in PVSCs with narrower PCE distribution. Moreover, the nitrobenzene additive methylammonium-free hybrid PVSCs exhibit prolonged lifetime compare to additive free PVSCs due to enhanced air and moisture degradation resistance.
The most studied perovskite-based solar cells reported up to date contain the toxic lead in its composition. Photovoltaic research and development towards non-toxic, lead-free perovskite solar cells are critical to finding alternatives to reduce human health concerns associated with them. Bismuth-based perovskite variants, especially in the form of methylammonium bismuth iodide (MBI), is a good candidate for the non-toxic light absorber. However, the reported perovskite variant MBI thin flms prepared by the solution process so far suffers from poor morphology and surface coverage. In this work…
Hybrid organic-inorganic perovskites, MAPbX3 (X= halogen), containing methylammonium (MA: CH3-NH3+) in the large voids conformed by the PbX6 octahedral network, are the active absorption materials in the new generation of solar cells. CH3NH3PbBr3 is a promising alternative with a large band-gap that gives rise to a high open circuit voltage. A deep knowledge of the crystal structure and, in particular, the MA conformation inside the perovskite cage across the phase transitions undergone below room temperature, seems essential to establish structure-property correlations that may drive to furth…
We have observed short-lived optical birefringence in a CH$_3$NH$_3$PbBr$_3$ single crystal induced by a powerful nearly single-cycle terahertz pulse. Apart from the instantaneous contribution that follows the profile of the squared pump electric field, the recorded anisotropy signal contains an exponential component decaying in $\sim$ 350 fs, underdamped oscillations at the frequency of $\sim$ 0.16 THz and an intermediate picosecond relaxation process with a Gaussian tail. We associate these three non-trivial features with, respectively, Kerr effect in the inorganic lattice, terahertz-induced…
Hybrid lead halide perovskites with 2D stacking structures have recently emerged as promising materials for optoelectronic applications. We report a method for growing 2D nanosheets of hybrid lead halide perovskites (I, Br and Cl), with tunable lateral sizes ranging from 0.05 to 8 microns, and a structure consisting of n stacked monolayers separated by long alkylamines, tunable from bulk down to n=1. The key to obtaining such a wide range of perovskite properties hinged on utilizing the respective lead halide nanosheets as precursors in a hot-injection synthesis that afforded careful control o…
Detection and direct power conversion of high energy and high intensity ionizing radiation could be a key element in next generation nuclear reactor safety systems and space-born devices. For example, the Fukushima catastrophe in 2011 could have been largely prevented if 1\% of the reactor's remnant radiation ($γ$-rays of the nuclear fission) were directly converted within the reactor to electricity to power the water cooling circuit. It is reported here that the hybrid halide perovskite methylammonium lead triiodide could perfectly play the role of a converter. Single crystals were irradiated…
Due to their exceptional photovoltaic properties, metal halide perovskites (MHPs) are extensively studied for their potential applications in solar cells. In recent years, the power conversion efficiencies of MHPs-based solar cells rapidly increased from the initial few \% towards more than 25\,\% for single-junction devices. Therefore, also taking into account their low costs and ease of manufacturing, MHPs-based solar cells have become the fastest-advancing photovoltaic technology. In this regard, much of the recent work has been dominated by absorber materials based on methylammonium MHPs, …
Mixed-cation Cesium-Methylammonium lead halide perovskite (CsxMA1-xPbI3-xBrx) thin-films have been used to demonstrate stable and efficient perovskite devices. However, a systematic study of the Cs incorporation on the properties of the perovskite films has not been reported. In this report, Impact of Cesium incorporation on the minority carrier recombination lifetime of Cesium-Methylammonium lead halide perovskite thin-films is studied. The lifetime for the as-deposited perovskite films decreases with increasing concentration of cesium. However, mixed cation perovskite film is more stable, sh…
We show that adding ethylenediamine (EDA) to perovskite precursor solution improves the photovoltaic device performance and material stability of high-bromide-content, methylammonium-free, formamidinium cesium lead halide perovskites FA1-xCsxPb(I1-yBry)3 which are currently of interest for perovskite-on-Si tandem solar cells. Using spectroscopy and hyperspectral microscopy, we show that the additive improves film homogeneity and suppresses the phase instability that is ubiquitous in high-Br perovskite formulations, producing films that remain stable for over 100 days in ambient conditions. Wit…
Owing to their exceptional semiconducting properties, hybrid inorganic-organic perovskites show great promise as photovoltaic absorbers. In these materials, long-range diffusion of charge carriers allows for most of the photogenerated carriers to contribute to the photovoltaic efficiency. Here, time-resolved photoluminescence (PL) microscopy is used to directly probe ambipolar carrier diffusion and recombination kinetics in hybrid perovskites. This technique is applied to thin films of methylammonium lead tri-iodide MAPbI$_3$ obtained with two different fabrication routes, methylammonium lead …
Investigation of (CsMA)NaBiX$_6$ (MA= methylammonium; X=Cl,Br, I) Organic-Inorganic Hybrid Double Perovskites for Optoelectronic Applications: A First Principles Study
Organic-inorganic hybrid perovskites (OIHPs) exhibiting exceptional photovoltaic and optoelectronic properties are of fundamental and practical interest, owing to their tunability and low manufacturing cost. For practical applications, however, challenges such as material instability and the photocurrent hysteresis occurring in perovskite solar cells under light exposure need to be understood and addressed. While extensive investigations have suggested that ion migration is a plausible origin of these detrimental effects, detailed understanding of the ion migration pathways remains elusive. He…
Point defects in metal halide perovskites play a critical role in determining their properties and optoelectronic performance; however, many open questions remain unanswered. In this work, we apply impedance spectroscopy and deep-level transient spectroscopy to characterize the ionic defect landscape in methylammonium lead triiodide ($MAPbI_3$) perovskites in which defects were purposely introduced by fractionally changing the precursor stoichiometry. Our results highlight the profound influence of defects on the electronic landscape, exemplified by their impact on the device built-in potentia…
High-resolution TEM (HRTEM) is a powerful tool for structure characterization. However, methylammonium lead iodide (MAPbI3) perovskite is highly sensitive to electron beams and easily decompose into lead iodide (PbI2). Universal misidentifications that PbI2 is incorrectly labeled as perovskite are widely exist in HRTEM characterization, which would negatively affect the development of perovskite research field. Here misidentifications in MAPbI3 perovskite calibration are summarized, classified and corrected based on corresponding electron diffraction (ED) simulations. Corresponding crystallogr…
Metal halide perovskite (MHP) optoelectronics may become a viable alternative to standard Si-based technologies, but the current lack of long-term stability precludes their commercial adoption. Exposure to standard operational stressors (light, temperature, bias, oxygen, and water) often instigate optical and electronic dynamics, calling for a systematic investigation into MHP photophysical processes and the development of quantitative models for their prediction. We resolve the moisture-driven light emission dynamics for both methylammonium lead tribromide and triiodide thin films as a functi…
Organic-inorganic lead halide perovskites containing a mixture of iodide and bromide anions consistently perform better in donor-acceptor heterojunction solar cells than the standard methylammonium lead triiodide material. This observation is counterintuitive, as it is generally expected for photovoltaic materials that heterogeneities and compositional disorder cause reduced carrier diffusion length and conversion efficiency. Here, we combine ultrafast photoinduced electroabsorption and broadband fluorescence up-conversion spectroscopy measurements to scrutinize the carrier dynamics in mixed-c…
We explore the degradation behaviour under continuous illumination and direct oxygen exposure of inverted unencapsulated formamidinium(FA)0.83Cs0.17Pb(I0.8Br0.2)3, CH3NH3PbI3, and CH3NH3PbI3-xClx perovskite solar cells. We continuously test the devices in-situ and in-operando with current-voltage sweeps, transient photocurrent, and transient photovoltage measurements, and find that degradation in the CH3NH3PbI3-xClx solar cells due to oxygen exposure occurs over shorter timescales than FA0.83Cs0.17Pb(I0.8Br0.2)3 mixed-cation devices. We attribute these oxygen-induced losses in the power conver…
Organometallic halide perovskites (OMHPs) have undergone remarkable developments as highly efficient optoelectronic materials for a variety of applications. Several studies indicated the critical role of defects on the performance of OMHP devices. Yet, the parameters of defects and their interplay with free charge carriers remain unclear. In this study we explore the dynamics of free holes in methylammonium lead tribromide (MAPbBr3) single crystals using the time of flight (ToF) current spectroscopy. By combining the current waveform (CWF) ToF spectroscopy and the Monte Carlo (MC) simulation, …
Layered lead halide A'2An-1PbnI3n+1 perovskites (2D LHPs) are attracting considerable attention as a more stable alternative with respect to APbI3 parent phases - a promising material for a new generation of solar cells. However, a critical analysis on the photostability of 2D perovskites homologous row is still lacking. In this work, we perform a comparative study of BA2MAn-1PbnI3n+1 (BA - butylammonium, MA - methylammonium) 2D LHPs with different layer number n = 1-3, considered as study-case systems, and MAPbI3, as a reference. We discuss a stability testing protocol with general validity, …
The same optical and electronic properties that make perovskite thin films ideal absorber materials in photovoltaic applications are also beneficial in photon upconversion devices. In this contribution, we investigate the rubrene-triplet sensitization by perovskite thin films based on methylammonium formamidinium lead triiodide (MAFA). To elucidate the role of trap states which affect the free carrier lifetimes, we fabricate MAFA perovskite thin films with three different thicknesses. By measuring the change in the photoluminescence properties under different excitation fluences, we find that …
The high performance of hybrid perovskite based devices is attributed to its excellent bulk-transport properties. However, carrier dynamics, especially at the metal-perovskite interface, and its influence on device operation are not widely understood. This work presents the dominant transport mechanisms in methylammonium lead iodide (MAPbI3) perovskite-based asymmetric metal-electrode lateral devices. The device operation is studied with inter-electrode lengths varying from 4 μm to 120 μm. Device characteristics indicate distinct ohmic and space-charge limited current (SCLC) regimes that are c…
Hot-carrier cooling (HCC) in metal halide perovskites in the high-density regime is significantly slower compared to conventional semiconductors. This effect is commonly attributed to a hot-phonon bottleneck but the influence of the lattice properties on the HCC behaviour is poorly understood. Using pressure-dependent transient absorption spectroscopy (fs-TAS) we find that at an excitation density below Mott transition, pressure does not affect the HCC. On the contrary, above Mott transition, HCC in methylammonium lead iodide (MAPbI3) is around two times as fast at 0.3 GPa compared to ambient …
Metal halide perovskites possess many physical properties amenable to optoelectronic applications, whereas the realization of these potentials has been hampered by their environmental and electronic instabilities. The morphological and molecular low dimensional perovskites and perovskite related materials have shown much promise in enhancing the chemical stability due to their unique molecular structures. Here we report on robust and reproducible four-terminal (4T) electrical measurements in a one-dimensional (1D) organic metal halide hybrid, (R)-α-methylbenzylammonium lead triiodide ((R-α-MBA…
One of the key challenges for future development of efficient and stable metal halide perovskite solar cells is related to the migration of ions in these materials. Mobile ions have been linked to the observation of hysteresis in the current--voltage characteristics, shown to reduce device stability against degradation and act as recombination centers within the band gap of the active layer. In the literature one finds a broad spread of reported ionic defect parameters (e.g. activation energies) for seemingly similar perovskite materials, rendering the identification of the nature of these spe…
Organic-inorganic halide perovskites are intrinsically unstable when exposed to moisture and/or light. Additionally, the presence of lead in many perovskites raises toxicity concerns. Herein is reported a thin film of BaZrS3, a lead-free chalcogenide perovskite. Photoluminescence and X-ray diffraction measurements show that BaZrS3 is far more stable than methylammonium lead iodide (MAPbI3) in moist environments. Moisture- and light-induced degradations in BaZrS3 and MAPbI3 are compared by using simulations and calculations based on density functional theory. The simulations reveal drastically …
Owing to the increasing popularity of lead-based hybrid perovskites for photovoltaic (PV) applications, it is crucial to understand their defect physics and its influence on their optoelectronic properties. In this work, we simulate various point defects in pseudo-cubic structures of mixed iodide-bromide and bromide-chloride methylammonium lead perovskites with the general formula MAPbI_{3-y}Br_{y} or MAPbBr_{3-y}Cl_{y} (where y is between 0 and 3), and use first principles based density functional theory computations to study their relative formation energies and charge transition levels. We …
Although methylammonium lead iodide (CH$_3$NH$_3$PbI$_3$) perovskite has attracted enormous scientific attention over the last decade or so, important information on the charge extraction dynamics and recombination processes in perovskite devices is still missing. Herein we present a novel approach to evaluate the quality of CH$_3$NH$_3$PbI$_3$ layers, via in-situ monitoring of the perovskite layer charge carrier dynamics during the thermal annealing crystallization process, by means of time-resolved femtosecond transient absorption spectroscopy (TAS). In particular, CH$_3$NH$_3$PbI$_3$ films …
Photo- and charge-carrier induced ion migration is a major challenge when utilizing metal halide perovskite semiconductors for optoelectronic applications. For mixed iodide/bromide perovskites, the compositional instability due to light- or electrical bias induced phase- segregation restricts the exploitation of the entire bandgap range. Previous experimental and theoretical work suggests that excited states or charge-carriers trigger the process but the exact mechanism is still under debate. To identify the mechanism and cause of light-induced phase-segregation phenomena we investigate the fu…
Perovskite-based solar cells are promising due to their rapidly improving efficiencies, but suffer from instability issues. Recently it has been claimed that one of the key contributors to the instability of perovskite solar cells is ion migration induced electrode degradation, which can be avoided by incorporating inorganic hole blocking layers (HBL) in the device architecture. In this work, we investigate the operational environmental stability of methylammonium lead iodide (MAPbI3) perovskite solar cells that contain either an inorganic or organic HBL, with only the former effectively block…
One of the main challenges for perovskite solar cells (PSC) is their stability, due to environment-induced perovskite decomposition. The resulting decomposition compounds are mobile and may, therefore, react with charge carrier extraction layers or the contact metallization, in addition to enhancing the recombination rate in the absorber layer. In this contribution, the influence of different contact metallization layers, such as aluminum (Al), silver (Ag), gold (Au) and nickel (Ni) on the storage stability of inverted planar methylammonium lead iodide (MAPI)-based perovskite solar cells witho…
Organic-inorganic halide perovskites recently have emerged as a promising material for highly effective light-emitting diodes (LEDs) and solar cells (SCs). Despite efficiencies of both perovskite SCs and LEDs are already among the best, the development of a perovskite dual functional device that is capable of working in these two regimes with high efficiencies is still challenging. Here we demonstrate that the dual functional device based on mixed halide perovskite CH3NH3PbBr2I can be switched from SC to LED with low threshold voltage Vth < 2 V by exposing to Sun at open circuit Voc or at smal…
Solution-processed organic-inorganic lead halide perovskites have recently emerged as promising gain media for tunable semiconductor lasers, and have come to rival inorganic III-V group semiconductors as the material candidate for chip-scale lasers. Although electrically pumped lasing at room temperature is the ultimate goal, optically pumped continuous-wave lasing at room temperature,a prerequisite for a laser diode,has not been achieved so far. Here, we report lasing action in a surface emitting distributed feedback methylammonium lead iodide (MAPbI3) perovskite laser on silicon substrate, a…
Ionic migration in organo-halide perovskites plays an important role in operation of perovskite based solar cells and light emitting diodes. Despite the ionic migration being a reversible process, it often leads to worsening of perovskite based device performance, hysteresis in current-voltage characteristics, and phase segregation in mixed halide perovskites being as the most harmful effect. The reason is in dynamical band structure changes, which controllable engineering would solve one of the biggest challenges for development of light-emitting solar cells. Here we demonstrate controllable …
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…
Methylammonium lead iodide (MAPI) is the archetype of the intensively researched class of perovskites for photovoltaics. Nonetheless, even equilibrium aspects are far from being fully understood. Here we discuss equilibrium space charge effects at the MAPI/TiO2 and MAPI/Al2O3 interfaces, which are of paramount significance for solar cells. Different from the photovoltaic literature in which such built-in potentials are considered as being generated solely by electronic charge carriers, we will apply a generalized picture that considers the equilibrium distribution of both ionic and electronic …
Thin-film solar cells suffer from various types of recombination, of which leakage current usually dominates at lower voltages. Herein, we demonstrate first a three-order reduction of the shunt loss mechanism in planar methylammonium lead iodide perovskite solar cells by replacing the commonly used hole transport layer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with a better hole-selective polyarylamine. As a result, these cells exhibit superior operation under reduced light conditions, which we demonstrate for the extreme case of moonlight irradiance, at which open-ci…
Second-order Raman and anharmonic lattice dynamics in lead-halide perovskites
Institute of Science and Technology Austria（科学技术奥地利研究所）；King Fahd University of Petroleum and Minerals（法赫德国王石油与矿产大学）；Interdisciplinary Research Center (IRC) for Advanced Materials, King Fahd University of Petroleum and Minerals（法赫德国王石油与矿产大学先进材料跨学科研究中心）；King Abdullah University of Science and Technology（阿卜杜拉国王科技大学）；Center for Renewable Energy and Storage Technologies, Division of Physical Science and Engineering, King Abdullah University of Science and Technology（阿卜杜拉国王科技大学物理科学与工程学部可再生能源与储能技术中心）；Aarhus University（奥胡斯大学）
