Lead Halide Perovskite Thin Films Research Articles

Making and Breaking of Lead Halide Perovskites.

A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization kinetics can be tailored to yield improved thin film homogeneity. Because degradation of the as-formed perovskite film is in many ways analogous to its initial formation, the same suite of monitoring techniques reveals the moisture-induced transformation of low band gap methylammonium lead iodide (CH3NH3PbI3) to wide band gap hydrate compounds. The rate of degradation is increased upon exposure to light. Interestingly, the hydration process is reversible under certain conditions. This facile formation and subsequent chemical lability raises the question of whether CH3NH3PbI3 and its analogues are thermodynamically stable phases, thus posing a significant challenge to the development of transformative perovskite photovoltaics. Adequately addressing issues of structural and chemical stability under real-world operating conditions is paramount if perovskite solar cells are to make an impact beyond the benchtop. Expanding our fundamental knowledge of lead halide perovskite formation and degradation pathways can facilitate fabrication of stable, high-quality perovskite thin films for the next generation of photovoltaic and light emitting devices.

Effects of alloying on the optical properties of organic–inorganic lead halide perovskite thin films

Spectroscopic ellipsometry analysis of optical transitions and optical constants in hybrid organic–inorganic perovskite alloys.

Relationships between Lead Halide Perovskite Thin-Film Fabrication, Morphology, and Performance in Solar Cells.

Solution-processed lead halide perovskite thin-film solar cells have achieved power conversion efficiencies comparable to those obtained with several commercial photovoltaic technologies in a remarkably short period of time. This rapid rise in device efficiency is largely the result of the development of fabrication protocols capable of producing continuous, smooth perovskite films with micrometer-sized grains. Further developments in film fabrication and morphological control are necessary, however, in order for perovskite solar cells to reliably and reproducibly approach their thermodynamic efficiency limit. This Perspective discusses the fabrication of lead halide perovskite thin films, while highlighting the processing-property-performance relationships that have emerged from the literature, and from this knowledge, suggests future research directions.

Mapping Electric Field‐Induced Switchable Poling and Structural Degradation in Hybrid Lead Halide Perovskite Thin Films

For lead halide perovskite solar cells to be considered for large‐scale commercial applications, the active material must be proven to be fundamentally stable under relevant operating conditions, such as exposure to light, heat, ambient environment, and electrical bias. Reversible and irreversible effects upon applying an electric field under different environmental conditions are identified. The application of an electric field in inert conditions leads only to a reversible poling on a time scale of minutes, whose distribution is mapped throughout the semiconductor film. It is also found that the presence of moisture, and in general of small polar and hydrogen‐bonding molecules, results in an irreversible degradation in the presence of the electric field, which happens in a time scale of hours under conditions relevant for photovoltaic operation. The measurements here suggest that the irreversible field‐induced degradation in air occurs via a hydrated phase, in which the organic cation is loosely bound and can drift in response to an electric field, finally degrading the material to PbI2. This has direct relevance to perovskite solar cells; hysteretic behavior in current–voltage curves is aggravated by the presence of moisture while devices aged under load accelerates degradation.

Probing Molecular and Crystalline Orientation in Solution‐Processed Perovskite Solar Cells

The microstructure of solution‐processed organometallic lead halide perovskite thin films prepared by the “gas‐assisted” method is investigated with synchrotron‐based techniques. Using a combination of GIWAXS and NEXAFS spectroscopy the orientational alignment of CH3NH3PbI3 crystallites and CH3NH3+ cations are separately probed. The GIWAXS results reveal a lack of preferential orientation of CH3NH3PbI3 crystallites in 200–250 nm thick films prepared on both planar TiO2 and mesoporous TiO2. Relatively high efficiencies are observed for device based on such films, with 14.3% achieved for planar devices and 12% for mesoporous devices suggesting that highly oriented crystallites are not crucial for good cell performance. Oriented crystallites however are observed in thinner films (≈60 nm) deposited on planar TiO2 (but not on mesoporous TiO2) indicating that the formation of oriented crystallites is sensitive to the kinetics of solvent evaporation and the underlying TiO2 morphology. NEXAFS measurements on all samples found that CH3NH3+ cations exhibit a random molecular orientation with respect to the substrate. The lack of any NEXAFS dichroism for the thin CH3NH3PbI3 layer deposited on planar TiO2 in particular indicates the absence of any preferential orientation of CH3NH3+ cations within the CH3NH3PbI3 unit cell for as‐prepared layers, that is, without any electrical poling.

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.

Monitoring the Phase Formation of Coevaporated Lead Halide Perovskite Thin Films by in Situ X-ray Diffraction.

Perovskite solar cells based on (CH3NH3)Pb(I,Cl)3 have recently demonstrated rapidly increasing cell efficiencies. Here, we show progress identifying phases present during the growth of (CH3NH3)Pb(I,Cl)3 perovskite thin films with the vacuum-based coevaporation approach using two sources under varying deposition conditions. With in situ X-ray diffraction, crystalline phases can be identified and monitored in real time. For different (CH3NH3)I-to-PbCl2 flux ratios, two distinct (CH3NH3)Pb(IxCl(1-x))3 phases with high (x > 0.95) and with lower (x < 0.5) iodine content as well as a broad miscibility gap in-between were found. During post deposition annealing we observe recrystallization and preferential orientation effects and finally the decomposition of the perovskite film to PbI2 at temperatures above 200 °C.

Charge carrier recombination channels in the low-temperature phase of organic-inorganic lead halide perovskite thin films

The optoelectronic properties of the mixed hybrid lead halide perovskite CH3NH3PbI3−xClx have been subject to numerous recent studies related to its extraordinary capabilities as an absorber material in thin film solar cells. While the greatest part of the current research concentrates on the behavior of the perovskite at room temperature, the observed influence of phonon-coupling and excitonic effects on charge carrier dynamics suggests that low-temperature phenomena can give valuable additional insights into the underlying physics. Here, we present a temperature-dependent study of optical absorption and photoluminescence (PL) emission of vapor-deposited CH3NH3PbI3−xClx exploring the nature of recombination channels in the room- and the low-temperature phase of the material. On cooling, we identify an up-shift of the absorption onset by about 0.1 eV at about 100 K, which is likely to correspond to the known tetragonal-to-orthorhombic transition of the pure halide CH3NH3PbI3. With further decreasing temperature, a second PL emission peak emerges in addition to the peak from the room-temperature phase. The transition on heating is found to occur at about 140 K, i.e., revealing significant hysteresis in the system. While PL decay lifetimes are found to be independent of temperature above the transition, significantly accelerated recombination is observed in the low-temperature phase. Our data suggest that small inclusions of domains adopting the room-temperature phase are responsible for this behavior rather than a spontaneous increase in the intrinsic rate constants. These observations show that even sparse lower-energy sites can have a strong impact on material performance, acting as charge recombination centres that may detrimentally affect photovoltaic performance but that may also prove useful for optoelectronic applications such as lasing by enhancing population inversion.