Determination of Carrier Diffusion Length Using Transient Electron Photoemission Microscopy in the GaAs/InSe Heterojunction

Carrier diffusion length and lifetime parameters for electron transport at nanoscale semiconductor slabs have been fitted using a 1D model and the decay data extracted from transient photoemission electron microscopy. Meanwhile, a conventional photoluminescence quenching measurement needs two separate samples with an active material between blocking and quenching layers to characterize the carrier transport properties. In this work, only one few-layer monocrystalline sample of gamma-InSe containing different thicknesses of active material is used to obtain a common diffusion coefficient consistent with previously reported values for vertical carrier diffusion in layered InSe

Atomic-level understanding of a formamidinium hybrid halide perovskite, FAPbBr₃

Herein, we show how electron microscopy can provide atomic-level understanding of FAPbBr3 , where electron diffraction and high-resolution imaging were combined allowing not only the characterization of the pristine material but also the identification of different intermediates upon its structural disintegration. Additionally, a minor tetragonal phase was also identified whose structure was also solved

Solar energy storage using a Cu2O-TiO photocathode in a lithium battery

A Cu2O-TiO2 photoelectrode is pr+oposed for simultaneous solar light energy harvesting and storing of electrochemical energy in an adapted lithium coin cell. The p-type Cu2O semiconductor layer is the light harvester component of the photoelectrode and the TiO2 film performs as the capacitive layer. The rationale of the energy scheme shows that the photocharges generated in the Cu2O semiconductor induce lithiation/delithiation processes in the TiO2 film as a function of the applied bias voltage and light power. A photorechargeable lithium button cell drilled on one side recharges with visible white light in ≈9 h in open circuit. It provides an energy density of ≈150 mAh g−1 at 0.1 C discharge current in dark, and the overall efficiency is 0.29%. This work draws a new approach for the photoelectrode role to advance in monolithic rechargeable batteries

Thermal degradation of formamidinium based lead halide perovskites into sym-triazine and hydrogen cyanide observed by coupled thermogravimetry-mass spectrometry analysis

The thermal stability and decomposition products of formamidinium, a widely used organic cation in perovskite solar cell formulation, were investigated. The thermal degradation experiments of formamidinium-based perovskites and their halide precursors were carried out under helium atmosphere and vacuum at a constant heating rate of 20 degrees C min(-1). In addition, pulsed heating steps were employed under illumination/dark conditions to simulate a more realistic working temperature condition for photovoltaic devices. The identification of gas decomposition products was based on the quadrupole mass spectrometry technique. The released amounts of sym-triazine, formamidine, and hydrogen cyanide (HCN) were observed to highly depend on the temperature. For the experimental conditions used in this study, sym-triazine was obtained as the thermal product of degradation at temperatures above 95 degrees C. Below this temperature, only formamidine and HCN generation routes were observed. The energy pathways of formamidinium thermal degradation under photovoltaic working temperature conditions were further assessed by density functional theory calculations. The results indicated that formamidinium was more resilient to thermal degradation and the release of irreversible decomposition products compared to methylammonium because of a larger enthalpy and activation energy obtained for the decomposition reactions. The HCN instantaneous concentration observed during the low temperature heating tests and the estimations of the maximum release of HCN achievable per meter-square of an FA based perovskite based solar cell were compared to acute exposure guideline levels of airborne HCN concentration

Progress on Perovskite Materials and Solar Cells with Mixed Cations and Halide Anions

Organic–inorganic halide perovskite materials (e.g., MAPbI3, FAPbI3, etc.; where MA = CH3NH3+, FA = CH(NH2)2+) have been studied intensively for photovoltaic applications. Major concerns for the commercialization of perovskite photovoltaic technology to take off include lead toxicity, long-term stability, hysteresis, and optimal bandgap. Therefore, there is still need for further exploration of alternative candidates. Elemental composition engineering of MAPbI3 and FAPbI3 has been proposed to address the above concerns. Among the best six certified power conversion efficiencies reported by National Renewable Energy Laboratory on perovskite-based solar cells, five are based on mixed perovskites (e.g., MAPbI1–xBrx, FA0.85MA0.15PbI2.55Br0.45, Cs0.1FA0.75MA0.15PbI2.49Br0.51). In this paper, we review the recent progress on the synthesis and fundamental aspects of mixed cation and halide perovskites correlating with device performance, long-term stability, and hysteresis. In the outlook, we outline the future research directions based on the reported results as well as related topics that warrant further investigation.(Some mathematical expressions are not properly displayed. Please see the attachment.

Degradation Mechanism and Relative Stability of Methylammonium Halide Based Perovskites Analyzed on the Basis of Acid–Base Theory

The correct identification of all gases released during hybrid perovskite degradation is of great significance to develop strategies to extend the lifespan of any device based on this semiconductor. CH3X (X = Br/I) is a released degradation gas/low boiling point liquid arising from methylammonium (MA+) based perovskites, which has been largely overlooked in the literature focusing on stability of perovskite solar cells. Herein, we present an unambiguous identification of CH3I release using microwave (rotational) spectroscopy. An experimental back-reaction test demonstrates that the well-known CH3NH2/HX degradation route may not be the ultimate degradation pathway of MAPbX3 in thermodynamic closed systems. Meanwhile, the CH3X/NH3 route cannot back-react selectively to MAX formation as occurred for the former back-reaction. Metadynamics calculations uncover the X halide effect on energy barriers for both degradation reactions showing a better stability of Br based perovskite ascribed to two aspects: (i) lower Brönsted–Lowry acidity of HBr compared to HI and (ii) higher nucleophilic character of CH3NH2 compared to NH3. The latter property makes CH3NH2 molecules stay preferentially attached on the electrophilic perovskite surface (Pb2+) during the dynamic simulation instead of being detached as observed for the NH3 molecule

Electrical field profile and doping in planar lead halide perovskite solar cells

Hybrid lead halide perovskites (PVKs) have emerged as novel materials for photovoltaics and have rapidly reached very large solar to electricity power conversion efficiencies. As occurring with other kind of solar technologies establishing the working energy-band diagram constitutes a primary goal for device physics analysis. Here, the macroscopic electrical field distribution is experimentally determined using capacitance-voltage and Kelvin probe techniques. Planar struc- tures comprising CH3NH3PbI3�����xClx PVK exhibit p-doping character and form a p-n heterojunc- tion with n-doped TiO2 compact layers. Depletion width at equilibrium within the PVK bulk has an extent about 300 nm (approximately half of the layer thickness), leaving as a consequence a significant neutral zone towards the anode contact. Charge collection properties are then accessi- ble relying on the relative weight that diffusion and drift have as carrier transport driven forces

Photodecomposition and thermal decomposition in methylammonium halide lead perovskites and inferred design principles to increase photovoltaic device stability

Hybrid lead halide perovskites have emerged as promising active materials for photovoltaic cells. Although superb efficiencies have been achieved, it is widely recognized that long-term stability is a key challenge intimately determining the future development of perovskite-based photovoltaic technology. Herein, we present reversible and irreversible photodecomposition reactions of methylammonium lead iodide (MAPbI3). Simulated sunlight irradiation and temperature (40–80 °C) corresponding to solar cell working conditions lead to three degradation pathways: (1) CH3NH2 + HI (identified as the reversible path), (2) NH3 + CH3I (the irreversible or detrimental path), and (3) a reversible Pb(0) + I2(g) photodecomposition reaction. If only the reversible reactions (1) and (3) take place and reaction (2) can be avoided, encapsulated MAPbI3 can be regenerated during the off-illumination timeframe. Therefore, to further improve operational stability in hybrid perovskite solar cells, detailed understanding of how to mitigate photodegradation and thermal degradation processes is necessary. First, encapsulation of the device is necessary not only to avoid contact of the perovskite with ambient air, but also to prevent leakage of volatile products released from the perovskite. Second, careful selection of the organic cations in the compositional formula of the perovskite is necessary to avoid irreversible reactions. Third, selective contacts must be as chemically inert as possible toward the volatile released products. Finally, hybrid halide perovskite materials are speculated to undergo a dynamic formation and decomposition process; this can gradually decrease the crystalline grain size of the perovskite with time; therefore, efforts to deposit highly crystalline perovskites with large crystal sizes may fail to increase the long-term stability of photovoltaic devices

The influence of secondary solvents on the morphology of a spiro-MeOTAD hole transport layer for lead halide perovskite solar cells

2,2 \u27,7,7 \u27-tetrakis(N,N-di-p-methoxyphenylamine)-9,9 \u27-spirobifluorene (spiro-MeOTAD) has been widely employed as a hole transport layer (HTL) in perovskite-based solar cells. Despite high efficiencies, issues have been reported regarding solution processed spiro-MeOTAD HTL such as pinholes and the strong dependence of electrical properties upon air exposure, which poses challenges for solar cell stability and reproducibility. In this work, we perform a systematic study to unravel the fundamental mechanisms for the generation of pinholes in solution-processed spiro-MeOTAD films. The formation of pinholes is closely related to the presence of small amounts of secondary solvents (e.g. H2O, 2-methyl-2-butene or amylene employed as a stabilizer, absorbed moisture from ambient, etc), which have low miscibility in the primary solvent generally used to dissolve spiro-MeOTAD (e.g. chlorobenzene). The above findings are not only applicable for spiro-MeOTAD (a small organic molecule), but also applicable to polystyrene (a polymer). The influence of secondary solvents in the primary solvents is the main cause for the generation of pinholes on film morphology. Our findings are of direct relevance for the reproducibility and stability in perovskite solar cells and can be extended to many other spin-coated or drop-casted thin films

Reduction of lead leakage from damaged lead halide perovskite solar modules using self-healing polymer-based encapsulation

In recent years, the major factors that determine commercialization of perovskite photovoltaic technology have been shifting from solar cell performance to stability, reproducibility, device upscaling and the prevention of lead (Pb) leakage from the module over the device service life. Here we simulate a realistic scenario in which perovskite modules with different encapsulation methods are mechanically damaged by a hail impact (modified FM 44787 standard) and quantitatively measure the Pb leakage rates under a variety of weather conditions. We demonstrate that the encapsulation method based on an epoxy resin reduces the Pb leakage rate by a factor of 375 compared with the encapsulation method based on a glass cover with an ultraviolet-cured resin at the module edges. The greater Pb leakage reduction of the epoxy resin encapsulation is associated with its optimal self-healing characteristics under the operating conditions and with its increased mechanical strength. These findings strongly suggest that perovskite photovoltaic products can be deployed with minimal Pb leakage if appropriate encapsulation is employed