Methylammonium Lead Halide Perovskite Films Research Articles

The Impact of Atmosphere on Energetics of Lead Halide Perovskites

AbstractSolar cells based on metal halide perovskites have emerged as a promising low‐cost photovoltaic technology. In contrast to inert atmospheres where most of the lab‐scale devices are made to date, large‐area low‐cost production of perovskite solar cells often involves processing of perovskites in various atmospheres including ambient air, nitrogen, and/or vacuum. Herein, the impact of atmosphere on the energy levels of methylammonium lead halide perovskite films is systematically investigated. The atmosphere is varied to simulate the typical fabrication process. Through a comprehensive analysis combining the Fermi level evolution, surface photovoltage, photoluminescence properties, photovoltaic performance, and device simulation, an overall landscape of the energy diagram of the perovskite layer is able to be determined. The findings have direct implications for real‐world devices under typical atmospheres, and provide insights into the fabrication‐process design and optimization. Furthermore, a universal Fermi level shift under vacuum for lead halide‐based perovskites revealed in this study, urges a refreshed view on the energetics studies conducted without considering the atmospheric effect.

A Study on the Effect of Ambient Air Plasma Treatment on the Properties of Methylammonium Lead Halide Perovskite Films

Organic-inorganic halide perovskite materials are considered excellent active layers in the fabrication of highly efficient and low-cost photovoltaic devices. This contribution demonstrates that rapid and low-temperature air-plasma treatment of mixed organic-inorganic halide perovskite film is a promising technique, controlling its opto-electrical surface properties by changing the ratio of organic-to-inorganic components. Plasma treatment of perovskite films was performed with high power-density (25 kW/m2 and 100 W/cm3) diffuse coplanar surface barrier discharge (DCSBD) at 70 °C in ambient air. The results show that short plasma treatment time (1 s, 2 s, and 5 s) led to a relatively enlargement of grain size, however, longer plasma treatment time (10 s and 20 s) led to an etching of the surface. The band-gap energy of the perovskite films was related to the duration of plasma treatment; short periods (≤5 s) led to a widening of the band gap from ~1.66 to 1.73 eV, while longer exposure (>5 s) led to a narrowing of the band gap to approx. 1.63 eV and fast degradation of the film due to etching. Surface analysis demonstrated that the film became homogeneous, with highly oriented crystals, after short plasma treatment; however, prolonging the plasma treatment led to morphological disorders and partial etching of the surface. The plasma treatment approach presented herein addresses important challenges in current perovskite solar cells: tuning the optoelectronic properties and manufacturing homogeneous perovskite films.

Free Carrier Emergence and Onset of Electron-Phonon Coupling in Methylammonium Lead Halide Perovskite Films.

Sub-10 fs resolution pump-probe experiments on methylammonium lead halide perovskite films are described. Initial response to photoexcitation is assigned to localized hot excitons which dissociate to free carriers. This is attested to by band integrals of the pump-probe spectra where photoinduced bleaching rises abruptly 20 fs after photoexcitation. Later stages of spectral evolution are consistent with hot carrier cooling, during which state filling induced bleaching of interband and exciton transitions curiously more than doubles. Electron coupling to optical phonons is observed as periodic spectral modulations in the pump-probe data of both films. Fourier analysis identifies active phonons at ∼100 and 300 wavenumbers pertaining to the lead-halide framework and organic cation motions, respectively. Coupling strengths estimated from the depth of these modulations are in the weak coupling limit, in agreement with values extracted from temperature dependent emission line shape analysis. These findings support free carriers in these materials existing as large polarons. Accordingly, these modes are probably not dictating the moderate carrier mobility in this material.

Halide-Substituted Electronic Properties of Organometal Halide Perovskite Films: Direct and Inverse Photoemission Studies.

Solution-processed perovskite solar cells are attracting increasing interest due to their potential in next-generation hybrid photovoltaic devices. Despite the morphological control over the perovskite films, quantitative information on electronic structures and interface energetics is of paramount importance to the optimal photovoltaic performance. Here, direct and inverse photoemission spectroscopies are used to determine the electronic structures and chemical compositions of various methylammonium lead halide perovskite films (MAPbX3, X = Cl, Br, and I), revealing the strong influence of halide substitution on the electronic properties of perovskite films. Precise control over halide compositions in MAPbX3 films causes the manipulation of the electronic properties, with a qualitatively blue shift along the I → Br → Cl series and showing the increase in ionization potentials from 5.96 to 7.04 eV and the change of transport band gaps in the range from 1.70 to 3.09 eV. The resulting light absorption of MAPbX3 films can cover the entire visible region from 420 to 800 nm. The results presented here provide a quantitative guide for the analysis of perovskite-based solar cell performance and the selection of optimal carrier-extraction materials for photogenerated electrons and holes.

Third-order nonlinear optical properties of methylammonium lead halide perovskite films

We report third-order nonlinear coefficient values and decay time kinetics vs. halide composition (CH3NH3PbBr3 and CH3NH3PbBr2I), temperature, and excitation wavelength.

I–V hysteresis of methylammonium lead halide perovskite films on microstructured electrode arrays: Dependence on preparation route and voltage scale

Methyl ammonium lead halide materials CH3NH3PbI3 and CH3NH3Pb(I0.95Br0.05)3 were prepared as thin films via different established deposition techniques onto micro structured gold electrode arrays on Si/SiO2 wafers. Scanning electron microscopy was performed to analyze the morphology of the different films. Electrical measurements of the samples showed hysteresis in the I–V characteristics for all samples in the dark and under illumination. Persistent changes in the polarization of the perovskite films were observed following positive or negative poling leading to significant changes in the observed current density and residual current at zero applied bias. At higher bias voltages additional inverted hysteresis loops were measured pointing at a decrease in barrier width and/or height at the blocking perovskite/metal contact by migrating iodide ions. Correspondingly, the net I–V characteristics in this voltage range could be modeled by two diodes operated back‐to‐back. Time‐dependent studies were performed to analyze the decay of the different observed polarization phenomena in the films during either short‐circuit or continuous sweeping of the bias. Implications of such persistent polarization and barrier formation for use of the materials for next‐generation solar cell devices are discussed.

The Importance of Moisture in Hybrid Lead Halide Perovskite Thin Film Fabrication.

Moisture, in the form of ambient humidity, has a significant impact on methylammonium lead halide perovskite films. In particular, due to the hygroscopic nature of the methylammonium component, moisture plays a significant role during film formation. This issue has so far not been well understood and neither has the impact of moisture on the physical properties of resultant films. Herein, we carry out a comprehensive and well-controlled study of the effect of moisture exposure on methylammonium lead halide perovskite film formation and properties. We find that films formed in higher humidity atmospheres have a less continuous morphology but significantly improved photoluminescence, and that film formation is faster. In photovoltaic devices, we find that exposure to moisture, either in the precursor solution or in the atmosphere during formation, results in significantly improved open-circuit voltages and hence overall device performance. We then find that by post-treating dry films with moisture exposure, we can enhance photovoltaic performance and photoluminescence in a similar way. The enhanced photoluminescence and open-circuit voltage imply that the material quality is improved in films that have been exposed to moisture. We determine that this improvement stems from a reduction in trap density in the films, which we postulate to be due to the partial solvation of the methylammonium component and "self-healing" of the perovskite lattice. This work highlights the importance of controlled moisture exposure when fabricating high-performance perovskite devices and provides guidelines for the optimum environment for fabrication. Moreover, we note that often an unintentional water exposure is likely responsible for the high performance of solar cells produced in some laboratories, whereas careful synthesis and fabrication in a dry environment will lead to lower-performing devices.

Heterogeneous Charge Carrier Dynamics in Organic-Inorganic Hybrid Materials: Nanoscale Lateral and Depth-Dependent Variation of Recombination Rates in Methylammonium Lead Halide Perovskite Thin Films.

We reveal substantial luminescence yield heterogeneity among individual subdiffraction grains of high-performing methylammonium lead halide perovskite films by using high-resolution cathodoluminescence microscopy. Using considerably lower accelerating voltages than is conventional in scanning electron microscopy, we image the electron beam-induced luminescence of the films and statistically characterize the depth-dependent role of defects that promote nonradiative recombination losses. The highest variability in the luminescence intensity is observed at the exposed grain surfaces, which we attribute to surface defects. By probing deeper into the film, it appears that bulk defects are more homogeneously distributed. By identifying the origin and variability of a surface-specific loss mechanism that deleteriously impacts device efficiency, we suggest that producing films homogeneously composed of the highest-luminescence grains found in this study could result in a dramatic improvement of overall device efficiency. We also show that although cathodoluminescence microscopy is generally used only to image inorganic materials it can be a powerful tool to investigate radiative and nonradiative charge carrier recombination on the nanoscale in organic-inorganic hybrid materials.