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Summary The most important obstacle to widespread use of perovskite solar cells is their poor stability under operational stressors. Here, we systematically monitor the evolution of the photovoltaic performance of perovskite solar cells based on formamidinium-cesium lead iodide (FA0.9Cs0.1PbI3) for 600 h, under a series of controlled operational stressors. Although these devices exhibit reasonable thermal stability, their stability under illumination or stabilized power output (SPO) is far from commercial demands. Synchrotron-based nanoprobe X-ray fluorescence and X-ray-beam-induced current measurements reveal that current-blocking Cs-rich phases segregate during stress tests. The decrease in performance is in line with the increasing density of the Cs-rich clusters in area upon illumination. Theoretical calculations indicate that light-generated carriers provide the thermodynamic driving force for that phase segregation. Our findings correlate device performance to microscopic behavior and atomistic mechanisms and shed light on inhibiting the cation-dependent phase segregation during device operation.

Organic–inorganic hybrid perovskites have electronic and optoelectronic properties that make them appealing in many device applications1–4. Although many approaches focus on polycrystalline materials5–7, single-crystal hybrid perovskites show improved carrier transport and enhanced stability over their polycrystalline counterparts, due to their orientation-dependent transport behaviour8–10 and lower defect concentrations11,12. However, the fabrication of single-crystal hybrid perovskites, and controlling their morphology and composition, are challenging12. Here we report a solution-based lithography-assisted epitaxial-growth-and-transfer method for fabricating single-crystal hybrid perovskites on arbitrary substrates, with precise control of their thickness (from about 600 nanometres to about 100 micrometres), area (continuous thin films up to about 5.5 centimetres by 5.5 centimetres), and composition gradient in the thickness direction (for example, from methylammonium lead iodide, MAPbI3, to MAPb0.5Sn0.5I3). The transferred single-crystal hybrid perovskites are of comparable quality to those directly grown on epitaxial substrates, and are mechanically flexible depending on the thickness. Lead–tin gradient alloying allows the formation of a graded electronic bandgap, which increases the carrier mobility and impedes carrier recombination. Devices based on these single-crystal hybrid perovskites show not only high stability against various degradation factors but also good performance (for example, solar cells based on lead–tin-gradient structures with an average efficiency of 18.77 per cent). A solution-based lithography-assisted epitaxial-growth-and-transfer method is used to fabricate single-crystal hybrid perovskites on any surface, with precise control of the thickness, area and chemical composition gradient.

Using scanning X-ray diffraction microscopy, we investigate the relationship between residual strains from crystal growth in CsPbBr3 thin-film crystals, their stability, and local photoluminescence (PL). We find that out-of-plane compressive strain that arises from cooldown from crystallization is detrimental to material stability under X-ray irradiation. We also find that the optical PL red-shifts as a result of the out-of-plane compressive strain. The sensitivity of the PL peak position to strain suggests possible applications such as stress-sensitive sensors. Mosaicity, the formation of small misorientations in neighboring crystalline domains we observe in some CsPbBr3 single crystals, indicates the significant variations in the crystal quality that can occur even in single-crystal halide perovskites. The nanodiffraction results suggest that reducing local strains is a necessary path to enhance the stability of perovskite optoelectronic materials and devices from light-emitting diodes to high-energy de...

Improved understanding of the origins of instability during photovoltaic operation of perovskite solar cell materials must be established to overcome barriers to commercialization. In this study, we analyze the microscopic mechanisms of degradation in high-performing methylammonium free (FA0.9Cs0.1PbI3) perovskite solar cells (PSC) over 600 hours of operation under stressors inherent to PV operation, including heat, illumination, and a load while excluding atmospheric effects by testing in a water-and oxygen-free atmosphere. While the PSCs exhibit reasonable thermal stability, they show considerable performance loss under constant illumination or stable power output. Synchrotron-based nanoprobe X-ray fluorescence and X-ray beam induced current (XRF/XBIC) measurements reveal segregation of current-blocking Cs-rich phases during stress testing. The decrease in performance correlates with the resulting number density of the Cs-rich clusters, which varies by stress condition. These findings unveil cation-dependent instability in FA0.9Cs0.1PbI3 perovskites and provide a framework for understanding the energy landscape in alloy perovskites to guide the engineering of long-lived halide perovskite devices.

The electrochemical conversion of CO2 to hydrocarbons and alcohols for use as a renewable energy storage medium is a promising approach to CO2 utilization and energy sustainability. Herein, we demonstrate that the selectivity of an electrochemically reduced Cu(OH)2 nanowire catalyst toward C2–C3 compounds (ethylene, ethanol, and n-propanol) is systemically modified by surface morphology, which is governed by the electrolysis potential. The total Faradaic efficiency of CO2 reduction to C2–C3 compounds is found to be 38% at a moderate potential of −0.81 V vs RHE, and stable electrocatalytic performance is observed for 40 h of CO2 electrolysis. Electro- and physicochemical analyses indicate that the Cu(OH)2 nanowires are completely reduced to metallic Cu, forming a mesostructured catalyst after a few minutes of electrolysis. The shift in product selectivity is strongly correlated with this change in mesoscale catalyst morphology, offering additional dimensionality and multiple length scales for catalyst desi...

Compositional engineering related to the organic and inorganic cations (A-site) in halide perovskites solar cells has helped improve efficiency and long-term durability. However, this compositional complexity can lead to phase segregation that weakens the optoelectronic performance. Here, we show the halide distribution and cation distribution by means of synchrotron-based nanoprobe x-ray fluorescence. We find that the halide distribution homogenizes upon the addition of CsI and RbI precursors. The halide homogenization coincides with long-lived charge carrier decays. Additionally, we observe Rb-rich areas that phase segregate within the film and the Rb aggregates are identified to be recombination active using X-ray and E-beam induced current microscopy.

The poor stability of halide perovskites creates a barrier for common e-beam based microscopies. Thus, carefully optimized e-beam characterization conditions are needed before any meaningful measurement can be taken. In this study, we present a range of e-beam operating conditions for characterizing perovskite materials with minimal electronic damage by monitoring plan-view electron beam induced current (EBIC) of functional solar cell devices. We see a minimum of beam induced damage in plan-view operation the range of 7.5 to 9.5 kV at low currents (

Spatial heterogeneities in the chemical makeup of thin film photovoltaic devices are pivotal in determining device efficiency. We report the in-plane spatial distribution and degree of chlorine incorporation in organic–inorganic lead halide perovskite absorbers by means of nondestructive synchrotron-based nanoprobe X-ray fluorescence. The presence of chlorine is positively identified in CH3NH3PbI3 films synthesized with Cl-containing precursors and as an impurity in some films synthesized with nominally Cl-free precursors. The impurity may be introduced from precursors or as contaminants during film synthesis. The films formed from Cl-containing precursors contain roughly an order of magnitude higher amount of chlorine, with Cl:I values greater than 0.02 found whether Cl is present in either the organic or the inorganic precursor for both one- and two-step fabrication processes. A spatial variation in the Cl incorporation is observed within single particles and as well as between particles within a given ...

Grain boundaries play a key role in the performance of thin-film optoelectronic devices and yet their effect in halide perovskite materials is still not understood. The biggest factor limiting progress is the inability to identify grain boundaries. Noncrystallographic techniques can misidentify grain boundaries, leading to conflicting literature reports about their influence; however, the gold standard - electron backscatter diffraction (EBSD) - destroys halide perovskite thin films. Here, this problem is solved by using a solid-state EBSD detector with 6000 times higher sensitivity than the traditional phosphor screen and camera. Correlating true grain size with photoluminescence lifetime, carrier diffusion length, and mobility shows that grain boundaries are not benign but have a recombination velocity of 1670 cm s(-1), comparable to that of crystalline silicon. Amorphous grain boundaries are also observed that give rise to locally brighter photoluminescence intensity and longer lifetimes. This anomalous grain boundary character offers a possible explanation for the mysteriously long lifetime and record efficiency achieved in small grain halide perovskite thin films. It also suggests a new approach for passivating grain boundaries, independent of surface passivation, to lead to even better performance in optoelectronic devices.

In this study, we use nanoprobe X-ray diffraction to measure structural variations in thin halide perovskite single crystals including mosaicity, tilt and strain. Using X-ray diffraction at 100-nm spatial resolution offers high sensitivity to structural variations within thin film materials. Here, we examine the crystal structural changes under X-ray irradiation toward understanding in detail the determining factors in this process including chemistry of materials, dose, and dose rate.

Spatial heterogeneities in the chemical makeup of thin film photovoltaic devices are pivotal in determining device efficiency. In this study, the presence of chlorine is identified in perovskite films synthesized with Cl-containing precursors by means of nanoprobe X-ray fluorescence (Nano-XRF). Additionally, a spatial variation in the Cl incorporation is observed within a given film, and the standard deviation of Cl: I ratio across the film is large. Using Nano-XRF, the Cl incorporation in methylammonium lead iodide perovskite films can be manipulated by precursor stoichiometry ratio.

The personal ultraviolet (UV) dosimeter is a useful measurement tool to prevent UV induced dermal damages; however, conventional digital dosimeters are either bulky or require external power sources. Here, a wearable, colorimetric UV film dosimeter that provides color transition, from purple to transparent, is reported to indicate the UV dose. The film dosimeter is made of a purple photodegradable dye ((2Z,6Z)-2,6-bis(2-(2,6-diphenyl-4H-thiopyran-4-ylidene)ethylidene)cyclohexanone or DTEC) blended in low density polyethylene film. The DTEC film discolored 3.3 times more under the exposure of UV light (302 nm) than visible light (543 nm), and a UV bandpass filter is developed to increase this selectivity to UV light. The DTEC film completely discolors to transparency in 2 h under an AM 1.5 solar simulator, suggesting the potential as an indicator for individuals with types I-VI skin to predict interventions to avoid sunburn. Finally, the DTEC film is integrated with the UV bandpass filter on a wristband to function as a wearable dosimeter for low cost and convenient monitoring of sunlight exposure.

Author(s): Luo, Yanqi; Aharon, Sigalit; Stuckelberger, Michael; Magana, Ernesto; Lai, Barry; Bertoni, Mariana I; Etgar, Lioz; Fenning, David P

Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. To investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH3 NH3 PbBr3 ) is varied, and changes are mapped in both their elemental composition and photoluminescence. Synchrotron-based nanoprobe X-ray fluorescence (nano-XRF) with 250 nm resolution reveals quasi-reversible field-assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH3 NH3 PbBr3 . A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy-mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field-assisted ionic migration in a model hybrid-perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite.

The journal of physical chemistry / C 124(33), 17949 - 17956 (2020). doi:10.1021/acs.jpcc.0c04645, Synchrotron micro- and nanoprobe beamlines have demonstrated great potential to advance photovoltaic devices. Most importantly, their small X-ray spot size has enabled the direct correlation of electrical performance with elemental composition at subgrain resolution for a variety of polycrystalline solar cells. Whereas the bulk of most inorganic semiconductors is stable under the high X-ray flux of focused X-ray beams, semiconductors with organic components are prone to a variety of degradation mechanisms. This is particularly critical to evaluate for the emerging organometal halide perovskite solar cells. Here, we investigate the effects of hard X-rays on the nanoscale performance and elemental distribution of these solar cells. We show that their composition does not change during common operando and in situ measurements at synchrotron nanoprobes. However, we found a significant X-ray-induced electronic degradation of solar cells with methylammonium lead iodide absorbers. Time- and dose-dependent measurements unveiled two characteristic degradation time constants on the order of 12 and 200 s that are independent of the X-ray flux. On the basis of heat and dose simulations, we attribute the fast decay to the dose-driven creation of recombination centers, while the slow decay is compatible with the observation of compositional changes. Finally, we detail how degradation-induced measurement artifacts can be outrun and showcase the high correlation of the X-ray-beam-induced current with the iodine and lead distribution., Published by Soc., Washington, DC