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In developing organic semiconductor polymers for photovoltaic applications, chlorine substitution has become an effective strategy in replacing fluorine substitution to overcome the drawbacks of low yield and high cost, commonly associated with fluorination. In general, several molecular positions are available for chlorination. To obtain a clear understanding of the impact of chlorine substitution on the intrinsic polymer properties, an investigation of structure-property relationships is necessary. Herein, four donor-acceptor type polymers with the same conjugated backbone and flexible alkyl chains, but with chlorine atoms in different positions, are employed to systematically investigate the effect of the site of chlorination on the optoelectronic properties and photovoltaic performance. Substitution of fluorine by chlorine in the backbone slightly increases open circuit voltage (Voc) and fill factor (FF) of the solar cells but causes a loss of short-circuit current density (Jsc). The introduction of chlorine in the conjugated side chains, however, significantly improves Voc, FF, and power conversion efficiency, benefiting from a lower HOMO energy level, efficient and well-balanced transport properties, and superior nanoscale morphology. This journal is

In p-i-n perovskite solar cells optical excitation of defect states at the interface between the perovskite and fullerene electron transport layer (ETL) creates a photocurrent responsible for a distinct sub-bandgap external quantum efficiency (EQE). The precise nature of these signals and their impact on cell performance are largely unknown. Here, the effect of n-doping the fullerene on the EQE spectra is studied. The n-doped fullerene is either deposited from solution or by coevaporation. The latter method is used to create undoped-doped fullerene bilayers and investigate the effect of the proximity of the doped region on the EQE spectra. The intensity of the sub-bandgap EQE increases when the ETL is n-doped and also when the device is biased with green light. Using these results, the sub-bandgap EQE signal is attributed to originate from electron trap states in the perovskite with an energy below the conduction band that are filled by excitation with low-energy photons. The trapped electrons give rise to photocurrent when they are collected at a nearby electrode. The enhanced sub-bandgap EQE observed when the ETL is n-doped or bias light is applied, is related to a higher probability to extract trapped electrons under these conditions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Bandgap-tuneable mixed-halide 3D perovskites are of interest for multi-junction solar cells, but suffer from photoinduced spatial halide segregation. Mixed-halide 2D perovskites are more resistant to halide segregation and are promising coatings for 3D perovskite solar cells. The properties of mixed-halide compositions depend on the local halide distribution, which is challenging to study at the level of single octahedra. In particular, it has been suggested that there is a preference for occupation of the distinct axial and equatorial halide sites in mixed-halide 2D perovskites. 207 Pb NMR can be used to probe the atomic-scale structure of lead-halide materials, but although the isotropic 207 Pb shift is sensitive to halide stoichiometry, it cannot distinguish configurational isomers. Here, we use 2D isotropic-anisotropic correlation 207 Pb NMR and relativistic DFT calculations to distinguish the [PbX 6 ] configurations in mixed iodide-bromide 3D FAPb(Br 1-x I x ) 3 perovskites and 2D BA 2 Pb(Br 1-x I x ) 4 perovskites based on formamidinium (FA + ) and butylammonium (BA + ), respectively. We find that iodide preferentially occupies the axial site in BA-based 2D perovskites, which may explain the suppressed halide mobility., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The efficiency of perovskite solar cells is affected by open-circuit voltage losses due to radiative and non-radiative charge recombination. When estimated using sensitive photocurrent measurements that cover the above- and sub-bandgap regions, the radiative open-circuit voltage is often unphysically low. Here we report sensitive photocurrent and electroluminescence spectroscopy to probe radiative recombination at sub-bandgap defects in wide-bandgap mixed-halide lead perovskite solar cells. The radiative ideality factor associated with the optical transitions increases from 1, above and near the bandgap edge, to ~2 at mid-bandgap. Such photon energy-dependent ideality factor corresponds to a many-diode model. The radiative open-circuit voltage limit derived from this many-diode model enables differentiating between radiative and non-radiative voltage losses. The latter are deconvoluted into contributions from the bulk and interfaces via determining the quasi-Fermi level splitting. The experiments show that while sub-bandgap defects do not contribute to radiative voltage loss, they do affect non-radiative voltage losses., (© 2024. The Author(s).)

The short exciton diffusion length in organic semiconductors results in a strong dependence of the conversion efficiency of organic photovoltaic (OPV) cells on the morphology of the donor-acceptor bulk-heterojunction blend. Strong light-matter coupling provides a way to circumvent this dependence by combining the favorable properties of light and matter via the formation of hybrid exciton-polaritons. By strongly coupling excitons in P3HT-C 60 OPV cells to Fabry-Perot optical cavity modes, exciton-polaritons are formed with increased propagation lengths. We exploit these exciton-polaritons to enhance the internal quantum efficiency of the cells, determined from the external quantum efficiency and the absorptance. Additionally, we find a consistent decrease in the Urbach energy for the strongly coupled cells, which indicates the reduction of energetic disorder due to the delocalization of exciton-polaritons in the optical cavity., Competing Interests: Conflict of interest: Authors state no conflicts of interest., (© 2023 the author(s), published by De Gruyter, Berlin/Boston.)

Bandgap tunability of lead mixed halide perovskites (LMHPs) is a crucial characteristic for versatile optoelectronic applications. Nevertheless, LMHPs show the formation of iodide-rich (I-rich) phase under illumination, which destabilizes the semiconductor bandgap and impedes their exploitation. Here, it is shown that how I 2 , photogenerated upon charge carrier trapping at iodine interstitials in LMHPs, can promote the formation of I-rich phase. I 2 can react with bromide (Br - ) in the perovskite to form a trihalide ion I 2 Br - (I δ- -I δ+ -Br δ- ), whose negatively charged iodide (I δ- ) can further exchange with another lattice Br - to form the I-rich phase. Importantly, it is observed that the effectiveness of the process is dependent on the overall stability of the crystalline perovskite structure. Therefore, the bandgap instability in LMHPs is governed by two factors, i.e., the density of native defects leading to I 2 production and the Br - binding strength within the crystalline unit. Eventually, this study provides rules for the design of chemical composition in LMHPs to reach their full potential for optoelectronic devices., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Crystallization of low-dimensional perovskites is a complex process that leads to multidimensional films comprising two-dimensional (2D), quasi-2D, and three-dimensional (3D) phases. Most quasi-2D perovskite films possess a regular gradient with 2D phases located at the bottom of the film and 3D phases at the top. Recently, multiple studies have reported reverse-graded perovskite films, where the location of the 2D and 3D structures is inverted. The underlying reasons for such a peculiar phase distribution are unclear. While crystallization of regular-graded quasi-2D perovskites has been described as starting with 3D phases from the liquid-air interface, the film formation of reverse-graded films has not been investigated yet. Here, we examine the impact of the alkyl chain length on the formation of regular- and reverse-graded perovskites using n- alkylammonium ions. We find that long alkyl chains reverse the phase distribution gradient. By combining photoluminescence spectroscopy with in situ optical absorption measurements, we demonstrate that crystallization starts at the liquid-N 2 interface, though as 3D phases for short-chain n- alkylammonium ions and as quasi-2D phases for long chains. We link this behavior to enhanced van der Waals interactions between long-chain n- alkylammonium ions in polar solvents and their tendency to accumulate at the liquid-N 2 interface, creating a concentration gradient along the film thickness., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Organic cathode materials are attractive candidates for the development of high-performance Li-ion batteries (LIBs). The chemical space of candidate molecules is too vast to be explored solely by experiments; however, it can be systematically explored by a high-throughput computational search that incorporates a spectrum of screening techniques. Here, we present a time- and resource-efficient computational scheme that incorporates machine learning and semi-empirical quantum mechanical methods to study the chemical space of approximately 200 000 quinone-based molecules for use as cathode materials in LIBs. By performing an automated search on a commercial vendor database, computing battery-relevant properties such as redox potential, gravimetric charge capacity, gravimetric energy density, and synthetic complexity score, and evaluating the structural integrity upon the lithiation process, a total of 349 molecules were identified as potentially high-performing cathode materials for LIBs. The chemical space of the screened candidates was visualized using dimensionality reduction methods with the aim of further downselecting the best candidates for experimental validation. One such directly purchasable candidate, 1,4,9,10-anthracenetetraone, was analyzed through cyclic voltammetry experiments. The measured redox potentials of the two lithiation steps, , of 3.3 and 2.4 V, were in good agreement with the predicted redox potentials, , of 3.2 and 2.3 V vs. Li/Li + , respectively. Lastly, to lay out the principles for rational design of quinone-based cathode materials beyond the current work, we constructed and discussed the quantitative structure property relationships of quinones based on the data generated from the calculations., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Monolithic perovskite/c-Si tandem solar cells have attracted enormous research attention and have achieved efficiencies above 30%. This work describes the development of monolithic tandem solar cells based on silicon heterojunction (SHJ) bottom- and perovskite top-cells and highlights light management techniques assisted by optical simulation. We first engineered ( i )a-Si:H passivating layers for (100)-oriented flat c-Si surfaces and combined them with various ( n )a-Si:H, ( n )nc-Si:H, and ( n )nc-SiO x :H interfacial layers for SHJ bottom-cells. In a symmetrical configuration, a long minority carrier lifetime of 16.9 ms was achieved when combining ( i )a-Si:H bilayers with ( n )nc-Si:H (extracted at the minority carrier density of 10 15 cm -3 ). The perovskite sub-cell uses a photostable mixed-halide composition and surface passivation strategies to minimize energetic losses at charge-transport interfaces. This allows tandem efficiencies above 23% (a maximum of 24.6%) to be achieved using all three types of ( n )-layers. Observations from experimentally prepared devices and optical simulations indicate that both ( n )nc-SiO x :H and ( n )nc-Si:H are promising for use in high-efficiency tandem solar cells. This is possible due to minimized reflection at the interfaces between the perovskite and SHJ sub-cells by optimized interference effects, demonstrating the applicability of such light management techniques to various tandem structures., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

High-throughput virtual screening (HTVS) has been increasingly applied as an effective approach to find candidate materials for energy applications. We performed a HTVS study, which is powered by: (i) automated virtual screening library generation, (ii) automated search on a readily purchasable chemical space of quinone-based compounds, and (iii) computed physicochemical descriptors for the prediction of key battery-related features of compounds, including the reduction potential, gravimetric energy density, gravimetric charge capacity, and molecular stability. From the initial virtual library of approximately 450k molecules, a total of 326 compounds have been identified as commercially available. Among them, 289 of the molecules are predicted to be stable for the sodiation reactions that take place at the sodium-ion battery cathodes. To study the behaviour of molecules over time at room temperature, we performed molecular dynamics simulations on a group of sodiated product molecules, which was narrowed down to 21 quinones after scrutinizing the key battery performance indicators. As a result, 17 compounds are suggested for validation as candidate cathode materials in sodium-ion batteries., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

2H-Benzotriazol-2-ylethylammonium bromide and iodide and its difluorinated derivatives are synthesized and employed as interlayers for passivation of formamidinium lead triiodide (FAPbI 3 ) solar cells. In combination with PbI 2 and PbBr 2 , these benzotriazole derivatives form two-dimensional (2D) Ruddlesden-Popper perovskites (RPPs) as evidenced by their crystal structures and thin film characteristics. When used to passivate n-i-p FAPbI 3 solar cells, the power conversion efficiency improves from 20% to close to 22% by enhancing the open-circuit voltage. Quasi-Fermi level splitting experiments and scanning electron microscopy cathodoluminescence hyperspectral imaging reveal that passivation provides a reduced nonradiative recombination at the interface between the perovskite and hole transport layer. Photoluminescence spectroscopy, angle-resolved grazing-incidence wide-angle X-ray scattering, and depth profiling X-ray photoelectron spectroscopy studies of the 2D/three-dimensional (3D) interface between the benzotriazole RPP and FAPbI 3 show that a nonuniform layer of 2D perovskites is enough to passivate defects, enhance charge extraction, and decrease nonradiative recombination., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Creating new donor materials is crucial for further advancing organic solar cells. Random terpolymers have been adopted to overcome shortcomings of regular alternating donor-acceptor (D-A) polymers of which the performance is often susceptible to batch-to-batch variations. In general, the properties and performance of efficient D 1 -A-D 2 -A and D-A 1 -D-A 2 terpolymers are sensitive to the D 1 /D 2 or A 1 /A 2 monomer ratios. Side-chain hybridization is a strategy to address this problem. Here, six D 1 -A-D 2 -A-type random terpolymers comprising D 1 and D 2 monomers with the same π-conjugated D unit but with different side chains were synthesized. The side chains, containing either fluorine or trialkylsilyl substituents were chosen to provide near-identical optoelectronic properties but provide a tool to create a better-optimized film morphology when blended with a non-fullerene acceptor. This strategy allows improving the device performance to over 18 %, higher than that obtained with the corresponding D 1 -A or D 2 -A bipolymers (around 17 %). Hence, side-chain hybridization is a promising strategy to design efficient D 1 -A-D 2 -A terpolymer donors that are insensitive to the D 1 /D 2 monomer ratio, which is beneficial for the scaled-up synthesis of high-performance materials., (© 2023 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

Photoinduced halide segregation hinders widespread application of three-dimensional (3D) mixed-halide perovskites. Much less is known about this phenomenon in lower-dimensional systems. Here, we study photoinduced halide segregation in lower-dimensional mixed iodide-bromide perovskites (PEA 2 MA n -1 Pb n (Br x I 1- x ) 3 n +1 , with PEA + : phenethylammonium and MA + : methylammonium) through time-dependent photoluminescence (PL) spectroscopy. We show that layered two-dimensional (2D) structures render additional stability against the demixing of halide phases under illumination. We ascribe this behavior to reduced halide mobility due to the intrinsic heterogeneity of 2D mixed-halide perovskites, which we demonstrate via 207 Pb solid-state NMR. However, the dimensionality of the 2D phase is critical in regulating photostability. By tracking the PL of multidimensional perovskite films under illumination, we find that while halide segregation is largely inhibited in 2D perovskites ( n = 1), it is not suppressed in quasi-2D phases ( n = 2), which display a behavior intermediate between 2D and 3D and a peculiar absence of halide redistribution in the dark that is only induced at higher temperature for the quasi-2D phase., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Remote measurement of vital sign parameters like heartbeat and respiration rate represents a compelling challenge in monitoring an individual's health in a noninvasive way. This could be achieved by large field-of-view, easy-to-integrate unobtrusive sensors, such as large-area thin-film photodiodes. At long distances, however, discriminating weak light signals from background disturbance demands superior near-infrared (NIR) sensitivity and optical noise tolerance. Here, we report an inherently narrowband solution-processed, thin-film photodiode with ultrahigh and controllable NIR responsivity based on a tandem-like perovskite-organic architecture. The device has low dark currents (<10 -6 mA cm -2 ), linear dynamic range >150 dB, and operational stability over time (>8 hours). With a narrowband quantum efficiency that can exceed 200% at 850 nm and intrinsic filtering of other wavelengths to limit optical noise, the device exhibits higher tolerance to background light than optically filtered silicon-based sensors. We demonstrate its potential in remote monitoring by measuring the heart rate and respiration rate from distances up to 130 cm in reflection.

Organic bulk heterojunction photodiodes (OPDs) attract attention for sensing and imaging. Their detectivity is typically limited by a substantial reverse bias dark current density (J d ). Recently, using thermal admittance or spectral photocurrent measurements, J d has been attributed to thermal charge generation mediated by mid-gap states. Here, the temperature dependence of J d in state-of-the-art OPDs is reported with J d down to 10 -9  mA cm -2 at -0.5 V bias. For a variety of donor-acceptor bulk-heterojunction blends it is found that the thermal activation energy of J d is lower than the effective bandgap of the blends, by ca. 0.3 to 0.5 eV, but higher than expected for mid-gap states. Ultra-sensitive sub-bandgap photocurrent spectroscopy reveals that the minimum photon energy for optical charge generation in OPDs correlates with the dark current thermal activation energy. The dark current in OPDs is attributed to thermal charge generation at the donor-acceptor interface mediated by intra-gap states near the band edges., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

As a versatile class of semiconductors, diketopyrrolopyrrole (DPP)-based conjugated polymers are well suited for applications of next-generation plastic electronics because of their excellent and tunable optoelectronic properties via a rational design of chemical structures. However, it remains a challenge to unravel and eventually influence the correlation between their solution-state aggregation and solid-state microstructure. In this contribution, the solution-state aggregation of high molecular weight PDPP3T is effectively enhanced by solvent selectivity, and a fibril-like nanostructure with short-range and long-range order is generated and tuned in thin films. The predominant role of solvent quality on polymer packing orientation is revealed, with an orientational transition from a face-on to an edge-on texture for the same PDPP3T. The resultant edge-on arranged films lead to a significant improvement in charge transport in transistors, and the field-effect hole mobility reaches 2.12 cm 2 V -1 s -1 with a drain current on/off ratio of up to 10 8 . Our findings offer a new strategy for enhancing the device performance of polymer electronic devices.

In early systemic sclerosis (Scleroderma, SSc), the vasculature is impaired. Although the exact etiology of endothelial cell damage in SSc remains unclear, it is hypothesized that endothelial to mesenchymal transition (EndoMT) plays a key role. To perform physiologically relevant angiogenic studies, we set out to develop an angiogenesis-on-a-chip platform that is suitable for assessing disease parameters that are relevant to SSc and other vasculopathies. In the model, we substituted Fetal Bovine Serum (FBS) with Human Serum without impairing the stability of the culture. We showed that 3D microvessels and angiogenic factor-induced sprouts exposed to key pro-inflammatory and pro-fibrotic cytokines (TNFα and TGFβ) undergo structural alterations consisting of destructive vasculopathy (loss of small vessels). We also showed that these detrimental effects can be prevented by compound-mediated inhibition of TGFβ-ALK5 signaling or addition of a TNFα neutralizing antibody to the 3D cultures. This demonstrates that our in vitro model is suitable for compound testing and identification of new drugs that can protect from microvascular destabilization or regression in disease-mimicking conditions. To support this, we demonstrated that sera obtained from SSc patients can exert an anti-angiogenic effect on the 3D vessel model, opening the doors to screening for potential SSc drugs, enabling direct patient translatability and personalization of drug treatment., (© 2022. The Author(s).)

Low-dimensional perovskites attract increasing interest due to tunable optoelectronic properties and high stability. Here, it is shown that perovskite thin films with a vertical gradient in dimensionality result in graded electronic bandgap structures that are ideal for photodiode applications. Positioning low-dimensional, vertically-oriented perovskite phases at the interface with the electron blocking layer increases the activation energy for thermal charge generation and thereby effectively lowers the dark current density to a record-low value of 5 × 10 -9  mA cm -2 without compromising responsivity, resulting in a noise-current-based specific detectivity exceeding 7 × 10 12 Jones at 600 nm. These multidimensional perovskite photodiodes show promising air stability and a dynamic range over ten orders of magnitude, and thus represent a new generation of high-performance low-cost photodiodes., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

An efficient substrate-configuration p-i-n metal-halide perovskite solar cell (PSC) is fabricated on a polymer-coated steel substrate. The optimized cell employs a Ti bottom electrode coated with a thin indium tin oxide (ITO) interlayer covered with a self-assembled [2-(9 H -carbazol-9-yl)ethyl]phosphonic acid monolayer as a hole-selective contact. A triple-cation perovskite is used as the absorber layer. Thermally evaporated C 60 and atomic layer deposited SnO 2 layers serve to create an electron-selective contact. The cells use an ITO top electrode with an antireflective MgF 2 coating. The optimized cell fabricated on a polymer-coated steel substrate reaches a power conversion efficiency of 16.5%, which approaches the 18.4% efficiency of a p-i-n reference superstrate-configuration cell that uses a similar stack design. Optical simulations suggest that the remaining optical losses are due to the absorption of light by the ITO top electrode, the C 60 layer, the Ti bottom electrode, and reflection from the MgF 2 coating in almost equal amounts. The major loss is, however, in the fill factor as a result of an increased sheet resistance of the top ITO electrode., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Interface layers used for electron transport (ETL) and hole transport (HTL) often significantly enhance the performance of organic solar cells (OSCs). Surprisingly, interface engineering for hole extraction has received little attention thus far. By finetuning the chemical structure of carbazole-based self-assembled monolayers with phosphonic acid anchoring groups, varying the length of the alkane linker (2PACz, 3PACz, and 4PACz), these HTLs were found to perform favorably in OSCs. Compared to archetypal PEDOT:PSS, the PACz monolayers exhibit higher optical transmittance and lower resistance and deliver a higher short-circuit current density and fill factor. Power conversion efficiencies of 17.4% have been obtained with PM6:BTP-eC9 as the active layer, which was distinctively higher than the 16.2% obtained with PEDOT:PSS. Of the three PACz derivatives, the new 3PACz consistently outperforms the other two monolayer HTLs in OSCs with different state-of-the-art nonfullerene acceptors. Considering its facile synthesis, convenient processing, and improved performance, we consider that 3PACz is a promising interface layer for widespread use in OSCs.

Perovskite-based multijunction solar cells are a potentially cost-effective technology that can help surpass the efficiency limits of single-junction devices. However, both mixed-halide wide-bandgap perovskites and lead-tin narrow-bandgap perovskites suffer from non-radiative recombination due to the formation of bulk traps and interfacial recombination centers which limit the open-circuit voltage of sub-cells and consequently of the integrated tandem. Additionally, the complex optical stack in a multijunction solar cell can lead to losses stemming from parasitic absorption and reflection of incident light which aggravates the current mismatch between sub-cells, thereby limiting the short-circuit current density of the tandem. Here, an integrated all-perovskite tandem solar cell is presented that uses surface passivation strategies to reduce non-radiative recombination at the perovskite-fullerene interfaces, yielding a high open-circuit voltage. By using optically benign transparent electrode and charge-transport layers, absorption in the narrow-bandgap sub-cell is improved, leading to an improvement in current-matching between sub-cells. Collectively, these strategies allow the development of a monolithic tandem solar cell exhibiting a power-conversion efficiency of over 23%., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Defects in perovskite solar cells are known to affect the performance, but their precise nature, location, and role remain to be firmly established. Here, we present highly sensitive measurements of the sub-bandgap photocurrent to investigate defect states in perovskite solar cells. At least two defect states can be identified in p-i-n perovskite solar cells that employ a polytriarylamine hole transport layer and a fullerene electron transport layer. By comparing devices with opaque and semi-transparent back contacts, we demonstrate the large effect of optical interference on the magnitude and peak position in the sub-bandgap external quantum efficiency (EQE) in perovskite solar cells. Optical simulations reveal that defects localized near the interfaces are responsible for the measured photocurrents. Using optical spacers of different lengths and a mirror on top of a semi-transparent device, allows for the precise manipulation of the optical interference. By comparing experimental and simulated EQE spectra, we show that sub-bandgap defects in p-i-n devices are located near the perovskite-fullerene interface., (© 2022. The Author(s).)

Metal halide perovskite photodiodes (PPDs) offer high responsivity and broad spectral sensitivity, making them attractive for low-cost visible and near-infrared sensing. A significant challenge in achieving high detectivity in PPDs is lowering the dark current density (J D ) and noise current (i n ). This is commonly accomplished using charge-blocking layers to reduce charge injection. By analyzing the temperature dependence of J D for lead-tin based PPDs with different bandgaps and electron-blocking layers (EBL), we demonstrate that while EBLs eliminate electron injection, they facilitate undesired thermal charge generation at the EBL-perovskite interface. The interfacial energy offset between the EBL and the perovskite determines the magnitude and activation energy of J D . By increasing this offset we realized a PPD with ultralow J D and i n of 5 × 10 -8  mA cm -2 and 2 × 10 -14  A Hz -1/2 , respectively, and wavelength sensitivity up to 1050 nm, establishing a new design principle to maximize detectivity in perovskite photodiodes., (© 2021. The Author(s).)

Light-induced halide segregation hampers obtaining stable wide-band-gap solar cells based on mixed iodide-bromide perovskites. So far, the effect of prolonged illumination on the performance of mixed-halide perovskite solar cells has not been studied in detail. It is often assumed that halide segregation leads to a loss of open-circuit voltage. By simultaneously recording changes in photoluminescence and solar cell performance under prolonged illumination, we demonstrate that cells instead deteriorate by a loss of short-circuit current density and that the open-circuit voltage is less affected. The concurrent red shift, increased lifetime, and higher quantum yield of photoluminescence point to the formation of relatively emissive iodide-rich domains under illumination. Kinetic Monte Carlo simulations provide an atomistic insight into their formation via exchange of bromide and iodide, mediated by halide vacancies. Localization of photogenerated charge carriers in low-energy iodide-rich domains and subsequent recombination cause reduced photocurrent and red-shifted photoluminescence. The loss in photovoltaic performance is diminished by partially replacing organic cations by cesium ions. Ultrasensitive photocurrent spectroscopy shows that cesium ions result in a lower density of sub-band-gap defects and suppress defect growth under illumination. These defects are expected to play a role in the development and recovery of light-induced compositional changes., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Inflammatory bowel disease (IBD) is thought to be caused by an aberrant host response to the commensal enteric flora in genetically susceptible individuals. Dendritic cells (DCs) play a key role in the regulation of this response as they sample gut commensals. In healthy individuals DCs actively contribute to tolerance upon recognition of these resident bacteria, whereas in individuals with IBD, DCs will initiate an inflammatory response. To mimic the disease response in vitro, human monocyte-derived DCs were matured with E. coli causing the cells to produce high levels of the pro-inflammatory cytokine IL-12/IL-23p40 (p40) and low levels of the anti-inflammatory cytokine IL-10. A siRNA-based screening assay was developed and screened to identify potential therapeutic targets that shift this balance towards an immunosuppressive state with lower levels of p40 and higher levels of IL-10. The screening assay was optimized and quality controlled using non-targeting controls and positive control siRNAs targeting IL12B and TLR4 transcripts. In the primary screen, smartpool siRNAs were screened for reduction in p40 expression, induction of IL-10 levels, or increase in IL-10:p40 ratios without affecting cell viability. All potential targets were taken forward into a confirmation screen in a different DC donor in which four individual siRNAs per target were screened. At least two siRNAs per target should have an effect to be considered a valid target. This screen resulted in a concise list of ten genes, of which their role in DC maturation is currently being investigated., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)