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Understanding the sub-band gap luminescence in Ruddlesden-Popper 2D metal halide hybrid perovskites (2D HaPs) is essential for efficient charge injection and collection in optoelectronic devices. Still, its origins are still under debate with respect to the role of self-trapped excitons or radiative recombination via defect states. In this study, we characterized charge separation, recombination, and transport in single crystals, exfoliated layers, and polycrystalline thin films of butylammonium lead iodide (BA2PbI4), one of the most prominent 2D HaPs. We combined complementary defect- and exciton-sensitive methods such as photoluminescence (PL) spectroscopy, modulated and time-resolved surface photovoltage (SPV) spectroscopy, constant final state photoelectron yield spectroscopy (CFSYS), and constant light-induced magneto transport (CLIMAT), to demonstrate striking differences between charge separation induced by dissociation of excitons and by excitation of mobile charge carriers from defect states. Our results suggest that the broad sub-band gap emission in BA2PbI4 and other 2D HaPs is caused by radiative recombination via defect states (shallow as well as midgap states) rather than self-trapped excitons. Density functional theory (DFT) results show that common defects can readily occur and produce an energetic profile that agrees well with the experimental results. The DFT results suggest that the formation of iodine interstitials is the initial process leading to degradation, responsible for the emergence of midgap states, and that defect engineering will play a key role in enhancing the optoelectronic properties of 2D HaPs in the future.
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Multi-junction photovoltaics approaches are being explored to mitigate thermalization losses that occur in the absorption of high-energy photons. However, the design of tandem cells faces challenges such as light reflection and parasitic absorption. Nanostructures have emerged as promising solutions due to their anti-reflection properties, which enhances light absorption. III-V nanowires (NWs) solar cells can achieve strong power conversion efficiencies, offering the advantage of potentially integrating tunnel diodes within the same fabrication process. Metal halide perovskites (MHPs) have gained attention for their optoelectronic attributes and cost-effectiveness. Notably, both material classes allow for tunable bandgaps. This study explores the integration of MHPs with III-V NWs solar cells in both two-terminal and three-terminal configurations. Our primary focus lies in the optical analysis of a tandem design using III-V semiconductor nanowire arrays in combination with perovskites, highlighting their potential for tandem applications. The space offered by the compact footprint of NW arrays is used in an interpenetrated tandem structure. We systematically optimize the bottom cell, addressing reflectivity and parasitic absorption, and extend to a full tandem structure, considering experimentally feasible thicknesses. Simulation of a three-terminal structure highlights a potential increase in efficiency, decoupling the operating points of the subcells. The two-terminal analysis underscores the benefits of nanowires in reducing reflection and achieving a higher matched current between the top and the bottom cells. This research provides significant insights into NW tandem solar cell optics, enhancing our understanding of their potential to improve photovoltaic performance.
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We demonstrate a bicoloured metal halide perovskite (MHP) light emitting diode (LED) fabricated in two sequential inkjet printing steps. By adjusting the printing parameters, we selectively and deliberately redissolve and recrystallize the first printed emissive layer to add a pattern emitting in a different color. The red light emitting features (on a green light emitting background) have a minimum size of 100 µm and originate from iodide-rich domains in a phase-segregated, mixed MHP. This phase forms between the first layer, a bromide-based MHP, which is partially dissolved by printing, and the second layer, an iodide-containing MHP. With an optimised printing process we can retain the active layer integrity and fabricate bicolour, large area MHP-based LEDs with up to 1600 mm2 active area. The two emission peaks at 535 nm and 710 nm are well separated and produce a strong visual contrast.
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Halide perovskites solar cells are now approaching commercialisation. In this transition from academic research towards industrialisation, standardized testing protocols and reliable dissemination of performance metrics are crucial. In this study, we analyze data from over 16,000 publications in the Perovskite Database to investigate the assumed equality between the integrated external quantum efficiency and the short circuit current from JV measurements. We find a systematic discrepancy with the JV-values being on average 4% larger. This discrepancy persists across time, perovskite composition, and device architecture, indicating the need to explore new perovskite physics and update reporting protocols and assumptions in the field.
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Improved stability and efficiency of two-terminal monolithic perovskite-silicon tandem solar cells will require reductions in recombination losses. By combining a triple-halide perovskite (1.68 electron volt bandgap) with a piperazinium iodide interfacial modification, we improved the band alignment, reduced nonradiative recombination losses, and enhanced charge extraction at the electron-selective contact. Solar cells showed open-circuit voltages of up to 1.28 volts in p-i-n single junctions and 2.00 volts in perovskite-silicon tandem solar cells. The tandem cells achieve certified power conversion efficiencies of up to 32.5%.
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Stability issues could prevent lead halide perovskite solar cells (PSCs) from commercialization despite it having a comparable power conversion efficiency (PCE) to silicon solar cells. Overcoming drawbacks affecting their long-term stability is gaining incremental importance. Excess lead iodide (PbI2 ) causes perovskite degradation, although it aids in crystal growth and defect passivation. Herein, we synthesized functionalized oxo-graphene nanosheets (Dec-oxoG NSs) to effectively manage the excess PbI2 . Dec-oxoG NSs provide anchoring sites to bind the excess PbI2 and passivate perovskite grain boundaries, thereby reducing charge recombination loss and significantly boosting the extraction of free electrons. The inclusion of Dec-oxoG NSs leads to a PCE of 23.7 % in inverted (p-i-n) PSCs. The devices retain 93.8 % of their initial efficiency after 1,000â hours of tracking at maximum power points under continuous one-sun illumination and exhibit high stability under thermal and ambient conditions.
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Metal halide perovskite based tandem solar cells are promising to achieve power conversion efficiency beyond the theoretical limit of their single-junction counterparts. However, overcoming the significant open-circuit voltage deficit present in wide-bandgap perovskite solar cells remains a major hurdle for realizing efficient and stable perovskite tandem cells. Here, a holistic approach to overcoming challenges in 1.8 eV perovskite solar cells is reported by engineering the perovskite crystallization pathway by means of chloride additives. In conjunction with employing a self-assembled monolayer as the hole-transport layer, an open-circuit voltage of 1.25 V and a power conversion efficiency of 17.0% are achieved. The key role of methylammonium chloride addition is elucidated in facilitating the growth of a chloride-rich intermediate phase that directs crystallization of the desired cubic perovskite phase and induces more effective halide homogenization. The as-formed 1.8 eV perovskite demonstrates suppressed halide segregation and improved optoelectronic properties.
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We demonstrate the upscaling of inkjet-printed metal halide perovskite light-emitting diodes. To achieve this, the drying process, critical for controlling the crystallization of the perovskite layer, was optimized with an airblade-like slit nozzle in a gas flow assisted vacuum drying step. This yields large, continuous perovskite layers in light-emitting diodes with an active area up to 1600 mm2.
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Daily temperature variations induce phase transitions and lattice strains in halide perovskites, challenging their stability in solar cells. We stabilized the perovskite black phase and improved solar cell performance using the ordered dipolar structure of ß-poly(1,1-difluoroethylene) to control perovskite film crystallization and energy alignment. We demonstrated p-i-n perovskite solar cells with a record power conversion efficiency of 24.6% over 18 square millimeters and 23.1% over 1 square centimeter, which retained 96 and 88% of the efficiency after 1000 hours of 1-sun maximum power point tracking at 25° and 75°C, respectively. Devices under rapid thermal cycling between -60° and +80°C showed no sign of fatigue, demonstrating the impact of the ordered dipolar structure on the operational stability of perovskite solar cells.
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Wide bandgap halide perovskite materials show promising potential to pair with silicon bottom cells. To date, most efficient wide bandgap perovskites layers are fabricated by spin-coating, which is difficult to scale up. Here, we report on slot-die coating for an efficient, 1.68 eV wide bandgap triple-halide (3halide) perovskite absorber, (Cs0.22FA0.78)Pb(I0.85Br0.15)3 + 5 mol % MAPbCl3. A suitable solvent system is designed specifically for the slot-die coating technique. We demonstrate that our fabrication route is suitable for tandem solar cells without phase segregation. The slot-die coated wet halide perovskite is dried by a "nitrogen (N2)-knife" with high reproducibility and avoiding antisolvents. We explore varying annealing conditions and identify parameters allowing crystallization of the perovskite film into large grains reducing charge collection losses and enabling higher current density. At 150 °C, an optimized trade-off between crystallization and the PbI2 aggregates on the film's top surface is found. Thus, we improve the cell stability and performance of both single-junction cells and tandems. Combining the 3halide top cells with a 120 µm thin saw damage etched commercial Czochralski industrial wafer, a 2-terminal monolithic tandem solar cell with a PCE of 25.2% on a 1 cm2 active area is demonstrated with fully scalable processes.
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Perovskite-silicon tandem solar cells offer the possibility of overcoming the power conversion efficiency limit of conventional silicon solar cells. Various textured tandem devices have been presented aiming at improved optical performance, but optimizing film growth on surface-textured wafers remains challenging. Here we present perovskite-silicon tandem solar cells with periodic nanotextures that offer various advantages without compromising the material quality of solution-processed perovskite layers. We show a reduction in reflection losses in comparison to planar tandems, with the new devices being less sensitive to deviations from optimum layer thicknesses. The nanotextures also enable a greatly increased fabrication yield from 50% to 95%. Moreover, the open-circuit voltage is improved by 15 mV due to the enhanced optoelectronic properties of the perovskite top cell. Our optically advanced rear reflector with a dielectric buffer layer results in reduced parasitic absorption at near-infrared wavelengths. As a result, we demonstrate a certified power conversion efficiency of 29.80%.
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Perovskite solar cells (PSCs) have shown great potential for next-generation photovoltaics. One of the main barriers to their commercial use is their poor long-term stability under ambient conditions and, in particular, their sensitivity to moisture and oxygen. Therefore, several encapsulation strategies are being developed in an attempt to improve the stability of PSCs in a humid environment. The lack of common testing procedures makes the comparison of encapsulation strategies challenging. In this paper, we optimized and investigated two common encapsulation strategies: lamination-based glass-glass encapsulation for outdoor operation and commercial use (COM) and a simple glue-based encapsulation mostly utilized for laboratory research purposes (LAB). We compare both approaches and evaluate their effectiveness to impede humidity ingress under three different testing conditions: on-shelf storage at 21 °C and 30% relative humidity (RH) (ISOS-D1), damp heat exposure at 85 °C and 85% RH (ISOS-D3), and outdoor operational stability continuously monitoring device performance for 10 months under maximum power point tracking on a roof-top test site in Berlin, Germany (ISOS-O3). LAB encapsulation of perovskite devices consists of glue and a cover glass and can be performed at ambient temperature, in an inert environment without the need for complex equipment. This glue-based encapsulation procedure allowed PSCs to retain more than 93% of their conversion efficiency after 1566 h of storage in ambient atmosphere and, therefore, is sufficient and suitable as an interim encapsulation for cell transport or short-term experiments outside an inert atmosphere. However, this simple encapsulation does not pass the IEC 61215 damp heat test and hence results in a high probability of fast degradation of the cells under outdoor conditions. The COM encapsulation procedure requires the use of a vacuum laminator and the cells to be able to withstand a short period of air exposure and at least 20 min at elevated temperatures (in our case, 150 °C). This encapsulation method enabled the cells to pass the IEC 61215 damp heat test and even to retain over 95% of their initial efficiency after 1566 h in a damp heat chamber. Above all, passing the damp heat test for COM-encapsulated devices translates to devices fully retaining their initial efficiency for the full duration of the outdoor test (>10 months). To the best of the authors' knowledge, this is one of the longest outdoor stability demonstrations for PSCs published to date. We stress that both encapsulation approaches described in this work are useful for the scientific community as they fulfill different purposes: the COM for the realization of prototypes for long-term real-condition validation and, ultimately, commercialization of perovskite solar cells and the LAB procedure to enable testing and carrying out experiments on perovskite solar cells under noninert conditions.
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In contrast to the common conception that the interfacial energy-level alignment is affixed once the interface is formed, we demonstrate that heterojunctions between organic semiconductors and metal-halide perovskites exhibit huge energy-level realignment during photoexcitation. Importantly, the photoinduced level shifts occur in the organic component, including the first molecular layer in direct contact with the perovskite. This is caused by charge-carrier accumulation within the organic semiconductor under illumination and the weak electronic coupling between the junction components.
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Long-term stability is one of the major challenges for p-i-n type perovskite solar modules (PSMs). Here, we demonstrate the fabrication of fully laser-patterned series interconnected p-i-n perovskite mini-modules, in which either single Cu or Ag layers are compared with Cu/Au metal-bilayer top electrodes. According to the scanning electron microscopy measurements, we found that Cu or Ag top electrodes often exhibit flaking of the metal upon P3 (top contact removal) laser patterning. For Cu/Au bilayer top electrodes, metal flaking may cause intermittent short-circuits between interconnected sub-cells during operation, resulting in fluctuations in the maximum power point (MPP). Here, we demonstrate Cu/Au metal-bilayer-based PSMs with an efficiency of 18.9% on an active area of 2.2 cm2 under continuous 1-sun illumination. This work highlights the importance of optimizing the top-contact composition to tackle the operational stability of mini-modules, and could help to improve the feasibility of large-area module deployment for the commercialization of perovskite photovoltaics.
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Through the optimization of the perovskite precursor composition and interfaces to selective contacts, we achieved a p-i-n-type perovskite solar cell (PSC) with a 22.3% power conversion efficiency (PCE). This is a new performance record for a PSC with an absorber bandgap of 1.63 eV. We demonstrate that the high device performance originates from a synergy between (1) an improved perovskite absorber quality when introducing formamidinium chloride (FACl) as an additive in the "triple cation" Cs0.05FA0.79MA0.16PbBr0.51I2.49 (Cs-MAFA) perovskite precursor ink, (2) an increased open-circuit voltage, VOC, due to reduced recombination losses when using a lithium fluoride (LiF) interfacial buffer layer, and (3) high-quality hole-selective contacts with a self-assembled monolayer (SAM) of [2-(9H-carbazol-9-yl)ethyl]phosphonic acid (2PACz) on ITO electrodes. While all devices exhibit a high performance after fabrication, as determined from current-density voltage, J-V, measurements, substantial differences in device performance become apparent when considering longer-term stability data. A reduced long-term stability of devices with the introduction of a LiF interlayer is compensated for by using FACl as an additive in the metal-halide perovskite thin-film deposition. Optimized devices maintained about 80% of the initial average PCE during maximum power point (MPP) tracking for >700 h. We scaled the optimized device architecture to larger areas and achieved fully laser patterned series-interconnected mini-modules with a PCE of 19.4% for a 2.2 cm2 active area. A robust device architecture and reproducible deposition methods are fundamental for high performance and stable large-area single junction and tandem modules based on PSCs.
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Metal halide perovskites show great promise for a wide range of optoelectronic applications but are plagued by instability when exposed to air and light. This work presents low-temperature solution growth of vertically aligned CsPbBr3 nanowire arrays in AAO (anodized aluminum oxide) templates with excellent stability, with samples exposed to air for 4 months still exhibiting comparable photoluminescence and UV stability to fresh samples. The single-crystal nanowire length is adjusted from â¼100 nm to 5 µm by adjusting the precursor solution amount and concentration, and we observe length-to-diameter ratios as high as 100. Structural characterization results indicate that large-diameter CsPbBr3 nanowires have an orthorhombic structure, while the 10 nm- and 20 nm-diameter nanowires adopt a cubic structure. Photoluminescence shows a gradual blue-shift in emission with decreasing nanowire diameter and marginal changes under varying illumination power intensity. The CsPbBr3-nanowires/AAO composite exhibits excellent resistance to X-ray radiation and long-term air storage, which makes it promising for future optoelectronic applications such as X-ray scintillators. These results show how physical confinement in AAO can be used to realize CsPbBr3 nanowire arrays and control their morphology and crystal structure.
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Solvent-solute interactions in precursor solutions of lead halide perovskites (LHPs) critically impact the quality of solution-processed materials, as they lead to the formation of a variety of poly-iodoplumbates that act as building blocks for LHPs. The formation of [PbI2+n]n- complexes is often expected in diluted solutions, while coordination occurring at high concentrations is not yet well understood. In a combined ab initio and experimental work, we demonstrate that the optical spectra of the quasi-one-dimensional iodoplumbate complexes PbI2(DMSO)4, Pb2I4(DMSO)6, and Pb3I6(DMSO)8 formed in dimethyl sulfoxide solutions are compatible with the spectral fingerprints measured at high lead iodide concentrations. This finding suggests that the interpretation of optical spectra of LHP precursor solutions should account for the formation of polynuclear lead halide complexes.
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We prepared triplet-triplet annihilation photon upconverters combining thin-film methylammonium lead iodide (MAPI) perovskite with a rubrene annihilator in a bilayer structure. Excitation of the perovskite film leads to delayed, upconverted photoluminescence emitted from the annihilator layer, with triplet excitation of the rubrene being driven by carriers excited in the perovskite layer. To better understand the connections between the semiconductor properties of the perovskite film and the upconversion efficiency, we deliberately varied the perovskite film properties by modifying two spin-coating conditions, namely, the choice of antisolvent and the antisolvent dripping time, and then studied the resulting photon upconversion performance with a standard annihilator layer. A stronger upconversion effect was exhibited when the perovskite films displayed brighter and more uniform photoluminescence. Both properties were sensitive to the antisolvent dripping time and were maximized for a dripping time of 20 s (measured relative to the end of the spin-coating program). Surprisingly, the choice of antisolvent had a significant effect on the upconversion performance, with anisole-treated films yielding on average a tenfold increase in upconversion intensity compared to the chlorobenzene-treated equivalent. This performance difference was correlated with the carrier lifetime in the perovskite film, which was 52 ns and 306 ns in the brightest chlorobenzene and anisole-treated films, respectively. Since the bulk properties of the anisole- and chlorobenzene-treated films were virtually identical, we concluded that differences in the defect density at the MAPI/rubrene interface, linked to the choice of antisolvent, must be responsible for the differing upconversion performance.
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The interest in metal halide perovskites has grown as impressive results have been shown in solar cells, light emitting devices, and scintillators, but this class of materials have a complex crystal structure that is only partially understood. In particular, the dynamics of the nanoscale ferroelastic domains in metal halide perovskites remains difficult to study. An ideal in situ imaging method for ferroelastic domains requires a challenging combination of high spatial resolution and long penetration depth. Here, we demonstrate in situ temperature-dependent imaging of ferroelastic domains in a single nanowire of metal halide perovskite, CsPbBr3. Scanning X-ray diffraction with a 60 nm beam was used to retrieve local structural properties for temperatures up to 140 °C. We observed a single Bragg peak at room temperature, but at 80 °C, four new Bragg peaks appeared, originating in different real-space domains. The domains were arranged in periodic stripes in the center and with a hatched pattern close to the edges. Reciprocal space mapping at 80 °C was used to quantify the local strain and lattice tilts, revealing the ferroelastic nature of the domains. The domains display a partial stability to further temperature changes. Our results show the dynamics of nanoscale ferroelastic domain formation within a single-crystal perovskite nanostructure, which is important both for the fundamental understanding of these materials and for the development of perovskite-based devices.