Unraveling A-Site Heterogeneity-Induced Phase Behavior in Mixed-Cation Lead Halide Perovskites

The making of a reconfigurable semiconductor with a soft ionic lattice

Revealing phase evolution mechanism for stabilizing formamidinium-based lead halide perovskites by a key intermediate phase

Single-crystal halide perovskites: Opportunities and challenges

Despite the exciting progress on power conversion efficiencies, the commercialization of the emerging lead (Pb) halide perovskite solar cell technology still faces significant challenges, one of which is the inclusion of toxic Pb. Searching for Pb-free perovskite solar cell absorbers is currently an attractive research direction. The approaches used for and the consequences of Pb replacement are reviewed herein. Reviews on the theoretical understanding of the electronic, optical, and defect properties of Pb and Pb-free halide perovskites and perovskite derivatives are provided, as well as the experimental results available in the literature. The theoretical understanding explains well why Pb halide perovskites exhibit superior photovoltaic properties, but Pb-free perovskites and perovskite derivatives do not.

The halogen chemistry of halide perovskites

With the rapid development of the information age, the demand for information storage capacity and miniaturization of memory units has been being increased. However, the commonly used silicon-based flash memory has nearly approached to its physical limit. The resistive switching random access memory (ReRAM) has become one of the promising candidates for the next-generation non-volatile memory due to its simple structure, fast operation speed, excellent flexibility, and long endurance. Recently, we witnessed that the lead halide perovskites, as hot star materials, have been widely used in optoelectronic fields owning to their advantages of low cost, excellent photoelectric properties, and solution process ability. Moreover, the lead halide perovskite has been successfully used as the active layer in ReRAM device because of its tunable bandgap, long charge carrier diffusion length, fast ion migration, and high charge carrier mobility. Whereas the toxicity of lead in halide perovskite is a very horrible problem in lead halide perovskite-based ReRAM devices. The lead-free halide perovskite is considered to be the most promising material for perovskite-based ReRAM devices because it does not contain lead element. Most recently, a large number of scientists from different groups have begun to study lead-free perovskite-based ReRAM devices. For example, tin, bismuth, antimony, and copper-based halide perovskite materials have been utilized in ReRAM devices and exhibited excellent resistance switching (RS) performances. Here in this paper, the recent development of lead-free perovskite and its RS performance are reviewed, including lead-free halide perovskite materials, RS performances, and RS mechanisms of lead-free perovskite-based ReRAM. Finally, the key problems and development prospects of lead-free perovskite-based ReRAM are also presented, which provides a fundamental step towards developing the RS performance based on lead-free halide perovskites.

ABX3 Perovskites for Tandem Solar Cells

ConspectusThe rediscovery of the halide perovskite class of compounds and, in particular, the organic and inorganic lead halide perovskite (LHP) materials and lead-free derivatives has reached remarkable landmarks in numerous applications. First among these is the field of photovoltaics, which is at the core of today’s environmental sustainability efforts. Indeed, these efforts have born fruit, reaching to date a remarkable power conversion efficiency of 25.2% for a double-cation Cs, FA lead halide thin film device. Other applications include light and particle detectors as well as lighting. However, chemical and thermal degradation issues prevent perovskite-based devices and particularly photovoltaic modules from reaching the market. The soft ionic nature of LHPs makes these materials susceptible to delicate changes in the chemical environment. Therefore, control over their interface properties plays a critical role in maintaining their stability. Here we focus on LHP nanocrystals, where surface termination by ligands determines not only the stability of the material but also the crystallographic phase and crystal habit. A surface analysis of nanocrystal interfaces revealed the involvement of Brønsted type acid–base equilibrium in the modification of the ligand moieties present, which in turn can invoke dissolution and recrystallization into the more favorable phase in terms of minimization of the surface energy. A large library of surface ligands has already been developed showing both good chemical stability and good electronic surface passivation, resulting in near-unity emission quantum yields for some materials, particularly CsPbBr3. However, most of those ligands have a large organic tail hampering charge carrier transport and extraction in nanocrystal-based solid films.The unique perovskite structure that allows ligand substitution in the surface A (cation) sites and the soft ionic nature is expected to allow the accommodation of large dipoles across the perovskite crystal. This was shown to facilitate electron transfer across a molecular linked single-particle junction, creating a large built-in field across the junction nanodomains. This strategy could be useful for implementing LHP NCs in a p–n junction photovoltaic configuration as well as for a variety of electronic devices. A better understanding of the surface propeties of LHP nanocrystals will also enable better control of their growth on surfaces and in confined volumes, such as those afforded by metal–organic frameworks, zeolites, or chemically patterened surfaces such as anodic alumina, which have already been shown to significantly alter the properties of in-situ-grown LHP materials.

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.

Perovskite materials have been widely considered as emerging photocatalysts for CO2 reduction due to their extraordinary physicochemical and optical properties. Perovskites offer a wide range of benefits compared to conventional semiconductors, including tunable bandgap, high surface energy, high charge carrier lifetime, and flexible crystal structure, making them ideal for high-performance photocatalytic CO2 reduction. Notably, defect-induced perovskites, for example, crystallographic defects in perovskites, have given excellent opportunities to tune perovskites’ catalytic properties. Recently, lead (Pb) halide perovskite and their composites or heterojunction with other semiconductors, metal nanoparticles (NPs), metal complexes, graphene, and metal-organic frameworks (MOFs) have been well established for CO2 conversion. Besides, various halide perovskites have come under focus to avoid the toxicity of lead-based materials. Therefore, we reviewed the recent progress made by Pb and Pb-free halide perovskites in photo-assisted CO2 reduction into useful chemicals. We also discussed the importance of various factors like change in solvent, structure defects, and compositions in the fabrication of halide perovskites to efficiently convert CO2 into value-added products.

Metal halide perovskites have recently attracted enormous attention for photovoltaic applications due to their superior optical and electrical properties. Lead (Pb) halide perovskites stand out among this material series, with a power conversion efficiency (PCE) over 25%. According to the Shockley-Queisser (SQ) limit, lead halide perovskites typically exhibit bandgaps that are not within the optimal range for single-junction solar cells. Partial or complete replacement of lead with tin (Sn) is gaining increasing research interest, due to the promise of further narrowing the bandgaps. This enables ideal solar utilization for single-junction solar cells as well as the construction of all-perovskite tandem solar cells. In addition, the usage of Sn provides a path to the fabrication of lead-free or Pb-reduced perovskite solar cells (PSCs). Recent progress in addressing the challenges of fabricating efficient Sn halide and mixed lead-tin (Pb-Sn) halide PSCs is summarized herein. Mixed Pb-Sn halide perovskites hold promise not only for higher efficiency and more stable single-junction solar cells but also for efficient all-perovskite monolithic tandem solar cells.

Influence of Charge Transport Layers on Capacitance Measured in Halide Perovskite Solar Cells

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development.

Understanding the origin of electron–phonon coupling in lead halide perovskites is key to interpreting and leveraging their optical and electronic properties. Here we show that photoexcitation drives a reduction of the lead–halide–lead bond angles, a result of deformation potential coupling to low-energy optical phonons. We accomplish this by performing femtosecond-resolved, optical-pump–electron-diffraction-probe measurements to quantify the lattice reorganization occurring as a result of photoexcitation in nanocrystals of FAPbBr3. Our results indicate a stronger coupling in FAPbBr3 than CsPbBr3. We attribute the enhanced coupling in FAPbBr3 to its disordered crystal structure, which persists down to cryogenic temperatures. We find the reorganizations induced by each exciton in a multi-excitonic state constructively interfere, giving rise to a coupling strength that scales quadratically with the exciton number. This superlinear scaling induces phonon-mediated attractive interactions between excitations in lead halide perovskites.

The remarkable performance of lead halide perovskites in solar cells can be attributed to the long carrier lifetimes and low non-radiative recombination rates, the same physical properties that are ideal for semiconductor lasers. Here we first report new insights on the crystal growth of the perovskite materials and the solution growth of single crystal nanowires, nanorods, and nanoplates of methylammonium lead halide and other perovskites via a dissolution-recrystallization pathway from lead iodide or lead acetate films coated on substrates. We further show room temperature and wavelength tunable lasing from single crystal lead halide perovskite nanowires with the lowest lasing thresholds (220 nJ/cm2) and highest quality factors (Q ~ 3600) reported to date for semiconductor nanowire lasers. The lasing threshold corresponds to a charge carrier density as low as 1.5×1016/cm3. Kinetic analysis based on time-resolved fluorescence reveals little charge carrier trapping in these single crystal nanowires and gives estimated lasing quantum yields approaching 100%. Such lasing performance, coupled with facile solution phase growth of single crystal NWs and broad tunability of emission color from stoichiometry, makes lead halide perovskites ideal materials for the development of nano-photonics, in parallel with the rapid development in photovoltaic technology from the same materials.