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Despite the great progress of flexible perovskite solar cells (f-PSCs), it still faces several challenges during the homogeneous fabrication of high-quality perovskite thin films, and overcoming the insufficient exciton dissociation. To the ends, we rationally design the two-dimensional (2D) perovskite based on pyridine heterocyclic ring as the organic interlayer. Through regulating its dipole moment by attaching the ammounium cation on different positions of the pyridine ring, we succeed to realize the ferroelectricity of the 2D perovskite. We uncover that incorporation of the ferroelectric 2D material into 3D perovskite induces an increased built-in electric field (BEF), which enhances the exciton dissociation efficiency and suppresses the nonradiative recombination in the device. Moreover, the 2D seeds could assist the 3D crystallization process by forming more homogeneous and highly-oriented perovskite crystals, and releasing the tensile stress in the film. As a result, an impressive power conversion efficiency (PCE) over 23% has been achieved by the 2D/3D based f-PSCs with outstanding ambient stability. Moreover, the ferroelectric 2D perovskite shows piezoelectricity as well, which intrigues an upshifted band-bending at the ITO/perovskite interface and decreased hole transport barriers. The device thus presents higher PCE under tensile-stresses, which opens new possibilities for developing highly-efficient f-PSCs.

The rapidly increasing solar conversion efficiency (PCE) of hybrid organic-inorganic perovskite (HOIP) thin-film semiconductors has triggered interest in their use for direct solar-driven water splitting to produce hydrogen. However, application of these low-cost, electronic-structure-tunable HOIP tandem photoabsorbers has been hindered by the instability of the photovoltaic-catalyst-electrolyte (PV+E) interfaces. Here, photolytic water splitting is demonstrated using an integrated configuration consisting of an HOIP/n+silicon single junction photoabsorber and a platinum (Pt) thin film catalyst. An extended electrochemical (EC) lifetime in alkaline media is achieved using titanium nitride (TiN) on both sides of the Si support to eliminate formation of insulating silicon oxide, and as an effective diffusion barrier to allow high-temperature annealing of the catalyst/TiO2-protected-n+silicon interface necessary to retard electrolytic corrosion. Halide composition was examined in the (Cs1-xFAx)PbI3 system with a bandgap suitable for tandem operation. A fill factor (FF) of 72.5% was achieved using a Spiro-OMeTAD-hole-transport-layer (HTL)-based HOIP/n+Si solar cell, and a high photocurrent density of -15.9 mA/cm2 (at 0V vs reversible hydrogen electrode) was attained for the HOIP/n+Si/Pt photocathode in 1M NaOH under simulated one-sun illumination. While this thin-film design creates stable interfaces, the intrinsic photo- and electro-degradation of the HOIP photoabsorber remains the main obstacle for future HOIP/Si tandem PEC devices.

Summary The development of mixed tin-lead (Sn-Pb)-based perovskite solar cells (PSCs) with low band gap (1.2–1.4 eV) has become critical not only for pushing single-junction devices toward the maximum efficiency given by the Shockley-Queisser limit, but also for enabling all-perovskite tandem devices beyond this limit. However, achieving high power-conversion efficiency (PCE) and long-term device operation stability simultaneously remains a significant challenge for Sn-Pb-based PSCs. Here, we demonstrate near ideal-band-gap (∼1.34 eV) methylammonium-free Sn-Pb-based PSCs with high efficiency (∼20%) and promising operational stability of maintaining >80% of initial PCE over 750 h under maximum-power-point tracking. The key to this success is the use of a SnCl2⋅3FACl complex additive that improves the microstructure and reduces the development of residual stress in the Sn-Pb perovskite thin films, which in turn enhances the efficiency and stability of the Sn-Pb-based ideal-band-gap PSCs.

Summary Surface modification of organic-inorganic halide perovskite thin films represents a promising approach to enhance the efficiency and stability of perovskite solar cells. Here, we synthesized N-methyl-1,3-propane diammonium diiodide (Me-PDAI2) and found that Me-PDA2+ can template a three-dimensional “perovskitoid” structure (Me-PDA)Pb2I6. Simple surface treatment with Me-PDAI2 on top of a standard (FAPbI3)0.85(MAPbI2Br)0.10(CsPbI3)0.05 perovskite induces the formation of a thin (Me-PDA)Pb2I6 perovskitoid surface layer, leading to smoother surface texture, longer charge-carrier lifetime, higher charge-carrier mobility, and a reduced surface-defect density. With the perovskitoid surface modification, the device efficiency is significantly improved from 20.3% to 22.0% along with enhanced stability in both shelf life (ISOS-D-1 stability) and operation (ISOS-L-1 stability). We further demonstrated that the perovskitoid surface engineering approach is applicable to various perovskite compositions, including CsFAMA-, FAMA-, and MA-based lead halide perovskites, making perovskitoid an important design motif for perovskite surface engineering for enhanced device performance and stability.

Cost-effective, high-throughput industrial applications of metal-halide perovskites require a highly tolerant method (i.e., wide process window) that produces high-quality materials with a short an...

Towards scalable manufacturing of perovskite solar panels, high-performance planar p-i-n perovskite solar cells (PVSCs) and modules have been demonstrated with blade-coating and rapid thermal proce...

Microcellular plastics not only have excellent performance, but also can form thin-walled parts. In the paper, the thin-walled microcellular parts (notebook computershell) made of polycarbonate/acr...

Perovskite thin films are currently fabricated via solution-processible methods that rapidly deposit perovskite inks; however, annealing perovskite thin films remains a bottleneck in the manufacturing process. A combination of different methods to reduce requisite time for perovskite film formation while simultaneously protecting temperature sensitive plastic substrates are needed to make flexible PSCs at scale. Here, we introduce a blade coated perovskite thin film annealed via a two-step staggered rapid thermal annealing (RTA) for 7 seconds yielding PSCs with a PCE of 14.6% on flexible ITO/PET. This study demonstrates the advantages of RTA over conventional conductive annealing when manufacturing temperature-sensitive, flexible PSCs.

With the rapid improvements in performance of perovskite photovoltaics, scale represents one of the few remaining hurdles to commercial viability. The active perovskite layer has previously been deposited via a scalable solution-based method, blade coating. Associated transport layers, however, are often deposited using energy- and capital-intensive methods. Here, we present processes by which the electron transport layer, a mixed fullerene solution, and cathode buffer layer, bathocuproine, are blade-coated in an ambient environment to fabricate large-area solar devices that match or outperform the equivalent film deposited via thermal evaporation. With this work, a high-performing, scalable perovskite solar cell can be manufactured in ambient conditions from top to bottom contact.

For optoelectronic devices based on polycrystalline semiconducting thin films, carrier transport across grain boundaries is an important process in defining efficiency. Here we employ transient absorption microscopy (TAM) to directly measure carrier transport within and across the boundaries in hybrid organic–inorganic perovskite thin films for solar cell applications with 50 nm spatial precision and 300 fs temporal resolution. By selectively imaging sub-bandgap states, our results show that lateral carrier transport is slowed down by these states at the grain boundaries. However, the long carrier lifetimes allow for efficient transport across the grain boundaries. The carrier diffusion constant is reduced by about a factor of 2 for micron-sized grain samples by the grain boundaries. For grain sizes on the order of ∼200 nm, carrier transport over multiple grains has been observed within a time window of 5 ns. These observations explain both the shortened photoluminescence lifetimes at the boundaries as we...

A high-efficiency wide-bandgap (WBG) perovskite solar cell is critical for developing perovskite-related (e.g., all-perovskite, perovskite/Si, or perovskite/Cu(In,Ga)Se 2 ) tandem devices. Here, we demonstrate the use of non-stoichiometric precursor chemistry with excess methylammonium halides (MAX; X = I, Br, or Cl) for preparing high-quality ∼1.75-eV FA 0.83Cs0.17Pb(I0.6Br0.4)3 perovskite solar cells. Among various methylammonium halides, using excess MABr in the non-stoichiometric precursor exhibits the strongest effect on improving perovskite crystallographic properties and device characteristics without affecting the perovskite composition. In contrast, using excess MAI significantly reduces the bandgap of perovskite due to the replacement of Br with I. Using 40% excess MABr, we demonstrate a single-junction WBG perovskite solar cell with stabilized efficiency of 16.4%. We further demonstrate a 20.3%-efficient 4-terminal tandem device by using a 14.7%-efficient semi-transparent WBG perovskite top cell and an 18.6%-efficient unfiltered (5.6%-efficient filtered) Si bottom cell.

To push perovskite solar cell (PSC) technology toward practical applications, large-area perovskite solar modules with multiple subcells need to be developed by fully scalable deposition approaches. Here, we demonstrate a deposition scheme for perovskite module fabrication with spray coating of a TiO2 electron transport layer (ETL) and blade coating of both a perovskite absorber layer and a spiro-OMeTAD-based hole transport layer (HTL). The TiO2 ETL remaining in the interconnection between subcells significantly affects the module performance. Reducing the TiO2 thickness changes the interconnection contact from a Schottky diode to ohmic behavior. Owing to interconnection resistance reduction, the perovskite modules with a 10 nm TiO2 layer show enhanced performance mainly associated with an improved fill factor. Finally, we demonstrate a four-cell MA0.7FA0.3PbI3 perovskite module with a stabilized power conversion efficiency (PCE) of 15.6% measured from an aperture area of ∼10.36 cm2, corresponding to an a...

The δ → α phase transformation is a crucial step in the solution-growth process of formamidinium-based lead triiodide (FAPbI3) hybrid organic–inorganic perovskite (HOIP) thin films for perovskite solar cells (PSCs). Because the addition of cesium (Cs) stabilizes the α phase of FAPbI3-based HOIPs, here our research focuses on FAPbI3(Cs) thin films. We show that having a large grain size in the δ-FAPbI3(Cs) non-perovskite intermediate films is essential for the growth of high-quality α-FAPbI3(Cs) HOIP thin films. Here grain coarsening and phase transformation occur simultaneously during the thermal annealing step. A large starting grain size in the δ-FAPbI3(Cs) thin films suppresses grain coarsening, precluding the formation of voids at the final α-FAPbI3(Cs)–substrate interfaces. PSCs based on the interface void-free α-FAPbI3(Cs) HOIP thin films are much more efficient and stable in the ambient atmosphere. This interesting finding inspired us to develop a simple room-temperature aging method for preparing ...

The flat band potentials and carrier densities of spin coated and sprayed MAPbI3, FA0.85Cs0.15PbI3, and MAPbBr3 perovskite films were determined using the Mott-Schottky relation. The films developed a space charge layer and exhibited p-type conduction with a carrier concentration of ∼1016 cm-3 for spin coated films. Electrochemical impedance spectra showed typical space charge impedance at frequencies >1 kHz, and an exceptional high capacitance at frequency

The migration of intrinsic ions (e.g., MA+, Pb2+, I−) in organic–inorganic hybrid perovskites has received significant attention with respect to the critical roles of these ions in the hysteresis and degradation in perovskite solar cells (PSCs). Here, we demonstrate that extrinsic ions (e.g., Li+, H+, Na+), when used in the contact layers in PSCs, can migrate across the perovskite layer and strongly impact PSC operation. In a TiO2/perovskite/spiro-OMeTAD-based PSC, Li+-ion migration from spiro-OMeTAD to the perovskite and TiO2 layer is illustrated by time-of-flight secondary-ion mass spectrometry. The movement of Li+ ions in PSCs plays an important role in modulating the solar cell performance, tuning TiO2 carrier-extraction properties, and affecting hysteresis in PSCs. The influence of Li+-ion migration was investigated using time-resolved photoluminescence, Kelvin probe force microscopy, and external quantum efficiency spectra. Other extrinsic ions such as H+ and Na+ also show a clear impact on the performance and hysteresis in PSCs. Understanding the impacts of extrinsic ions in perovskite-based devices could lead to new material and device designs to further advance perovskite technology for various applications.

Here, we examine grain boundaries (GBs) with respect to non-GB regions (grain surfaces (GSs) and grain interiors (GIs)) in high-quality micrometer-sized perovskite CH3NH3PbI3 (or MAPbI3) thin films using high-resolution confocal fluorescence-lifetime imaging microscopy in conjunction with kinetic modeling of charge-transport and recombination processes. We show that, contrary to previous studies, GBs in our perovskite MAPbI3 thin films do not lead to increased recombination but that recombination in these films happens primarily in the non-GB regions (i.e., GSs or GIs). We also find that GBs in these films are not transparent to photogenerated carriers, which is likely associated with a potential barrier at GBs. Even though GBs generally display lower luminescence intensities than GSs/GIs, the lifetimes at GBs are no worse than those at GSs/GIs, further suggesting that GBs do not dominate non-radiative recombination in MAPbI3 thin films.

We report a systematic study of the gigahertz-frequency charge carrier mobility found in methylammonium lead iodide perovskite films as a function of average grain size using time-resolved microwave conductivity and a single processing chemistry. Our measurements are in good agreement with the Kubo formula for the AC mobility of charges confined within finite grains, suggesting (1) that the surface grains imaged via scanning electron microscopy are representative of the true electronic domain size and not substantially subdivided by twinning or other defects not visible by microscopy and (2) that the time scale of diffusive transport across grain boundaries is much slower than the period of the microwave field in this measurement (∼100 ps). The intrinsic (infinite grain size) minimum mobility extracted form the model is 29 ± 6 cm2 V–1 s–1 at the probe frequency (8.9 GHz).

A strong interaction of a semiconductor with a below-bandgap laser pulse causes a blue-shift of the bandgap transition energy, known as the optical Stark effect. The energy shift persists only during the pulse duration with an instantaneous response time. The optical Stark effect has practical relevance for applications, including quantum information processing and communication, and passively mode-locked femtosecond lasers. Here we demonstrate that solution-processable lead-halide perovskites exhibit a large optical Stark effect that is easily resolved at room temperature resulting from the sharp excitonic feature near the bandedge. We also demonstrate that a polarized pump pulse selectively shifts one spin state producing a spin splitting of the degenerate excitonic states. Such selective spin manipulation is an important prerequisite for spintronic applications. Our result implies that such hybrid semiconductors may have great potential for optoelectronic applications beyond photovoltaics., The band gap of bulk semiconductors widens when excited by sub-bandgap wavelengths at low temperature—it's the optical Stark effect. Here, the authors measure a room temperature optical Stark effect in lead halide perovskite films, due to their well-resolved excitonic transitions.

We investigated moisture and thermal stability of MAPbBr3 perovskite material. Cubic MAPbBr3 was found to be moisture-insensitive and can avoid the thermal stability issues introduced by low-temperature phase transition in MAPbI3. MAPbBr3 and MAPbI3 hybrid solar cells with efficiencies of ∼7.1% and ∼15.5%, respectively, were fabricated, and we identified the correlation between the working temperature, light intensity, and the photovoltaic performance. No charge-carrier transport barriers were found in the MAPbBr3 and MAPbI3 solar cells. The MAPbBr3 solar cell displays a better stability under high working temperature because of its close-packed crystal structure. Temperature-dependent photocurrent–voltage characteristics indicate that, unlike the MAPbI3 solar cell with an activation energy (EA) nearly equal to its band gap (Eg), the EA for the MAPbBr3 solar cell is much lower than its Eg. This indicates that a high interface recombination process limits the photovoltage and consequently the device perfor...

We report on the carrier-rotor coupling effect in perovskite organic-inorganic hybrid lead iodide (CH3NH3PbI3) compounds discovered by isotope effects. Deuterated organic-inorganic perovskite compounds including CH3ND3PbI3, CD3NH3PbI3, and CD3ND3PbI3 were synthesized. Devices made from regular CH3NH3PbI3 and deuterated CH3ND3PbI3 exhibit comparable performance in band gap, current-voltage, carrier mobility, and power conversion efficiency. However, a time-resolved photoluminescence (TRPL) study reveals that CH3NH3PbI3 exhibits notably longer carrier lifetime than that of CH3ND3PbI3, in both thin-film and single-crystal formats. Furthermore, the comparison in carrier lifetime between CD3NH3PbI3 and CH3ND3PbI3 single crystals suggests that vibrational modes in methylammonium (MA(+)) have little impact on carrier lifetime. In contrast, the fully deuterated compound CD3ND3PbI3 reconfirmed the trend of decreasing carrier lifetime upon the increasing moment of inertia of cationic MA(+). Polaron model elucidates the electron-rotor interaction.

Photovoltaic applications of perovskite semiconductor material systems have generated considerable interest in part because of predictions that primary defect energy levels reside outside the bandgap. We present experimental evidence that this enabling material property is present in the halide-lead perovskite, CH3NH3PbI3 (MAPbI3), consistent with theoretical predictions. By performing X-ray photoemission spectroscopy, we induce and track dynamic chemical and electronic transformations in the perovskite. These data show compositional changes that begin immediately with exposure to X-ray irradiation, whereas the predominant electronic structure of the thin film on compact TiO2 appears tolerant to the formation of compensating defect pairs of VI and VMA and for a large range of I/Pb ratios. Changing film composition is correlated with a shift of the valence-band maximum only as the halide–lead ratio drops below 2.5. This delay is attributed to the invariance of MAPbI3 electronic structure to distributed def...

Researchers have debated whether methylammonium lead iodide (MAPbI3), with a perovskite crystal structure, is ferroelectric and therefore contributes to the current–voltage hysteresis commonly observed in hybrid perovskite solar cells (PSCs). We thoroughly investigated temperature-dependent polarization, dielectric, and impedance spectroscopies, and we found no evidence of ferroelectric effect in a MAPbI3 thin film at normal operating conditions. Therefore, the effect does not contribute to the hysteresis in PSCs, whereas the large component of ionic migration observed may play a critical role. Our temperature-based polarization and dielectric studies find that MAPbI3 exhibits different electrical behaviors below and above ca. 45 °C, suggesting a phase transition around this temperature. In particular, we report the activation energies of ionic migration for the two phases and temperature-dependent permittivity of MAPbI3. This study contributes to the understanding of the material properties and device pe...

Perovskite solar cells (PSCs) employing planar and mesoscopic architectures have both resulted in high efficiency devices. However, there is presently a limited understanding of the inherent advantages of both systems, particularly in terms of the charge transport and recombination dynamics. In the present study we characterize the relative benefits of the two most prominent CH3NH3PbI3 morphologies, primarily through time-resolved microwave conductivity (TRMC) and time-resolved photoluminescence (TRPL) measurements. The comparatively large perovskite grains, typical of planar assemblies, exhibited higher charge mobilities and slower trap-mediated recombination compared to the mesoscopic architectures. These findings reveal the injurious influence of grain boundaries on both charge transport and recombination kinetics, and suggest an innate advantage of planar morphologies. However, through impedance spectroscopy (IS) measurements, mesoscopic architectures were found to limit the interfacial recombination at the transparent conductive oxide (TCO) substrate. The lessons learnt through the characterization measurements were subsequently utilized to produce an optimized cell morphology, resulting in a maximum conversion efficiency of 16%.

Both tin oxide (SnO2) and fullerenes have been reported as electron selective layers (ESLs) for producing efficient lead halide perovskite solar cells. Here, we report that SnO2 and fullerenes can work cooperatively to further boost the performance of perovskite solar cells. We find that fullerenes can be redissolved during perovskite deposition, allowing ultra-thin fullerenes to be retained at the interface and some dissolved fullerenes infiltrate into perovskite grain boundaries. The SnO2 layer blocks holes effectively; whereas, the fullerenes promote electron transfer and passivate both the SnO2/perovskite interface and perovskite grain boundaries. With careful device optimization, the best-performing planar perovskite solar cell using a fullerene passivated SnO2 ESL has achieved a steady-state efficiency of 17.75% and a power conversion efficiency of 19.12% with an open circuit voltage of 1.12 V, a short-circuit current density of 22.61 mA cm−2, and a fill factor of 75.8% when measured under reverse voltage scanning. We find that the partial dissolving of fullerenes during perovskite deposition is the key for fabricating high-performance perovskite solar cells based on metal oxide/fullerene ESLs.

In this communication, the nanoscale through-film and lateral photo-response and conductivity of large-grained methylammonium lead iodide (MAPbI3) thin films are studied. In perovskite solar cells (PSC), these films result in efficiencies >17%. The grain boundaries (GBs) show high resistance at the top surface of the film, and act as an impediment to photocurrent collection. However, lower resistance pathways between grains exist below the top surface of the film, indicating that there exists a depth-dependent resistance of GBs (RGB(z)). Furthermore, lateral conductivity measurements indicate that RGB(z) exhibits GB-to-GB heterogeneity. These results indicate that increased photocurrent collection along GBs is not a prerequisite for high-efficiency PSCs. Rather, better control of depth-dependent GB electrical properties, and an improvement in the homogeneity of the GB-to-GB electrical properties, must be managed to enable further improvements in PSC efficiency. Finally, these results refute the implicit assumption seen in the literature that the electrical properties of GBs, as measured at the top surface of the perovskite film, necessarily reflect the electrical properties of GBs within the thickness of the film.

We present efficient metal oxide-free and annealing-free planar perovskite solar cells with the regular cell structure using vacuum-deposited fullerenes C 60 and C 70 as the electron-selective layers and vacuum-processed perovskites as the light absorbers. The devices with an ultrathin C 60 layer (5.5 nm) yielded an average power conversion efficiency of 14.3% and a maximum efficiency of 15.7%. The best-performing cell produced a steady-state efficiency of 14.6%. The high performance is attributed to the efficient blocking of holes and extraction of electrons by C 60 due to a favorable energy level alignment between the C 60 and the fluorine-doped tin oxide electrodes. With the realization of efficient cells, the annealing-free vacuum deposition of perovskite absorbers and C 60 or C 70 electron-selective layers and intermediate layers demonstrates its power for fabricating all-perovskite tandem solar cells.

Metal-halide based perovskite solar cells have rapidly emerged as a promising alternative to traditional inorganic and thin-film photovoltaics. Although charge transport layers are used on either side of perovskite absorber layers to extract photogenerated electrons and holes, the time scales for charge extraction and recombination are poorly understood. Ideal charge transport layers should facilitate large discrepancies between charge extraction and recombination rates. Here, we demonstrate that highly enriched semiconducting single-walled carbon nanotube (SWCNT) films enable rapid (sub-picosecond) hole extraction from a prototypical perovskite absorber layer and extremely slow back-transfer and recombination (hundreds of microseconds). The energetically narrow and distinct spectroscopic signatures for charges within these SWCNT thin films enables the unambiguous temporal tracking of each charge carrier with time-resolved spectroscopies covering many decades of time. The efficient hole extraction by the SWCNT layer also improves electron extraction by the compact titanium dioxide electron transport layer, which should reduce charge accumulation at each critical interface. Finally, we demonstrate that the use of thin interface layers of semiconducting single-walled carbon nanotubes between the perovskite absorber layer and a prototypical hole transport layer improves device efficiency and stability, and reduces hysteresis.

Organic–inorganic perovskites have emerged as an important class of next generation solar cells due to their remarkably low cost, band gap, and sub-900 nm absorption onset. Here, we show a series of in situ observations inside electron microscopes and X-ray diffractometers under device-relevant synthesis conditions focused on revealing the crystallization process of the formamidinium lead-triiodide perovskite at the optimum temperature of 175 °C. Direct in situ observations of the structure and chemistry over relevant spatial, temporal, and temperature scales enabled identification of key perovskite formation and degradation mechanisms related to grain evolution and interface chemistry. The lead composition was observed to fluctuate at grain boundaries, indicating a mobile lead-containing species, a process found to be partially reversible at a key temperature of 175 °C. Using low energy electron microscopy and valence electron energy loss spectroscopy, lead is found to be bonded in the grain interior with iodine in a tetrahedral configuration. At the grain boundaries, the binding energy associated with lead is consequently shifted by nearly 2 eV and a doublet peak is resolved due presumably to a greater degree of hybridization and the potential for several different bonding configurations. At the grain boundaries there is adsorption of hydrogen and OH− ions as a result of residual water vapor trapped as a non-crystalline material during formation. Insights into the relevant formation and decomposition reactions of formamidinium lead iodide at low to high temperatures, observed metastabilities, and relationship with the photovoltaic performance were obtained and used to optimize device processing resulting in conversion efficiencies of up to 17.09% within the stability period of the devices.

The microstructure of the solid-PbI2 precursor thin film plays an important role in the intercalation crystallization of the formamidinium lead triiodide perovskite (α-HC(NH2)2PbI3). It is shown that microstructurally engineered PbI2 thin films with porosity and low crystallinity are the most favorable for conversion into uniform-coverage, phase-pure α-HC(NH2)2PbI3 perovskite thin films. Planar perovskite solar cells fabricated using these thin films deliver power conversion efficiency (PCE) up to 13.8%.

Goldschmidt tolerance factor (t) is an empirical index for predicting stable crystal structures of perovskite materials. A t value between 0.8 and 1.0 is favorable for cubic perovskite structure, and larger (>1) or smaller (

In the past five years, perovskite solar cells (PSCs) based on organometal halide perovskite have exhibited extraordinary photovoltaic (PV) performance. However, the PV measurements of PSCs have been widely recognized to depend on voltage scanning condition (hysteretic current density–voltage [J–V] behavior), as well as on voltage treatment history. In this study, we find that varied PSC responses are attributable to two causes. First, capacitive effect associated with electrode polarization provides a slow transient non-steady-state photocurrent that modifies the J–V response. Second, modification of interfacial barriers induced by ion migration can modulate charge-collection efficiency so that it causes a pseudo-steady-state photocurrent, which changes according to previous voltage conditioning. Both phenomena are strongly influenced by ions accumulating at outer interfaces, but their electrical and PV effects are different. The time scale for decay of capacitive current is on the order of seconds, whereas the slow redistribution of mobile ions requires several minutes. The authors gratefully acknowledge the financial support through the U.S. Army under Contract No. W15P7T-13-C-A910. The work at the National Renewable Energy Laboratory was supported by the U.S. Department of Energy SunShot Initiative under the Next Generation Photovoltaics 3 program (DE-FOA-0000990) under Contract No. DE-AC36-08-GO28308. S.P. and C.W. also appreciate support from the NSF I/UCRC: Center for Energy Harvesting Materials and Systems through Fundamental Research Program. The work at INAM-UJI was supported by Generalitat Valenciana project PROMETEO/2014/020.

Understanding carrier recombination in semiconductors is a critical component when developing practical applications. Here we measure and compare the monomolecular, bimolecular, and trimolecular (Auger) recombination rate constants of CH3NH3PbBr3 and CH3NH3PbI3. The monomolecular and bimolecular recombination rate constants for both samples are limited by trap-assisted recombination. The bimolecular recombination rate constant for CH3NH3PbBr3 is ∼3.3 times larger than that for CH3NH3PbI3 and both are in line with that found for radiative recombination in other direct-gap semiconductors. The Auger recombination rate constant is 4 times larger in lead-bromide-based perovskite compared with lead-iodide-based perovskite and does not follow the reduced Auger rate when the bandgap increases. The increased Auger recombination rate, which is enhanced by Coulomb interactions, can be ascribed to the larger exciton binding energy, ∼40 meV, in CH3NH3PbBr3 compared with ∼13 meV in CH3NH3PbI3.

Adaptability, lightweight, and low cost of materials make flexible perovskite solar cells essential for the perovskite technology to breach commercial photovoltaic markets. Roll-to-roll manufacturing has great potential for high-throughput perovskite manufacturing; however, conventional annealing methods are not capable of producing flexible perovskite solar cells at scale. Conventional methods are time consuming and may compromise functionality of flexible substrates under tension. Here, we introduce a blade-coated perovskite thin film on flexible ITO-coated PET annealed via rapid thermal annealing (RTA) that reduces post-deposition processing time from ~150 s to ~14 s. Performance was not sacrificed for scalability as a perovskite solar cell was produced with a power conversion efficiency (PCE) of 14.58%.