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Reducing nonradiative recombination is crucial for minimizing voltage losses in metal-halide perovskite solar cells and achieving high power conversion efficiencies. Photoluminescence spectroscopy on complete or partial perovskite solar cell stacks is often used to quantify and disentangle bulk and interface contributions to nonradiative losses. Accurately determining the intrinsic loss in a perovskite layer is key to analyzing the origins of nonradiative recombination and developing defect engineering strategies. Here, we study perovskite films on glass and indium-tin-oxide-covered glass substrates, functionalized with a range of different molecules, using absolute and transient photoluminescence. We find that grafting these substrates with 1,6-hexylenediphosphonic acid (HDPA) effectively reduces the nonradiative losses in perovskite films for a series of perovskite semiconductors with bandgaps ranging from 1.26 to 2.28 eV. The results suggest that perovskites processed on HDPA-functionalized substrates suffer the least from nonradiative recombination and thus approach the properties of a defect-free semiconductor.

All-perovskite tandem photovoltaics are a potentially cost-effective technology to power chemical fuel production, such as green hydrogen. However, their application is limited by deficits in open-circuit voltage and, more challengingly, poor operational stability of the photovoltaic cell. Here we report a laboratory-scale solar-assisted water-splitting system using an electrochemical flow cell and an all-perovskite tandem solar cell. We begin by treating the perovskite surface with a propane-1,3-diammonium iodide solution that reduces interface non-radiative recombination losses and achieves an open-circuit voltage above 90% of the detailed-balance limit for single-junction solar cells between the bandgap of 1.6-1.8 eV. Specifically, a high open-circuit voltage of 1.35 V and maximum power conversion efficiency of 19.9% are achieved at a 1.77 eV bandgap. This enables monolithic all-perovskite tandem solar cells with a 26.0% power conversion efficiency at 1 cm 2 area and a pioneering photovoltaic-electrochemical system with a maximum solar-to-hydrogen efficiency of 17.8%. The system retains over 60% of its peak performance after operating for more than 180 h. We find that the performance loss is mainly due to the degradation of the photovoltaic component. We observe severe charge collection losses in the narrow-bandgap sub-cell that can be attributed to the interface degradation between the narrow-bandgap perovskite and the hole-transporting layer. Our study suggests that developing chemically stable absorbers and contact layers is critical for the applications of all-perovskite tandem photovoltaics., Competing Interests: Competing interests: H.J.S. is cofounder and CSO of Oxford PV Ltd. A.W. is co-founder and CSO of Enecoat Technologies Co., Ltd. All other authors declare no competing interests., (© 2024. The Author(s).)

Multijunction photovoltaics (PVs) are gaining prominence owing to their superior capability of achieving power conversion efficiencies (PCEs) beyond the radiative limit of single-junction cells 1-8 , where improving narrow bandgap tin-lead perovskites is critical for thin-film devices 9 . With a focus on understanding the chemistry of tin-lead perovskite precursor solutions, we herein find that Sn(II) species dominate interactions with precursors and additives and uncover the exclusive role of carboxylic acid in regulating solution colloidal properties and film crystallisation, and ammonium in improving film optoelectronic properties. Materials that combine these two function groups, amino acid salts, considerably improve the semiconducting quality and homogeneity of perovskite films, surpassing the effect of the individual functional groups when introduced as part of separate molecules. Our enhanced tin-lead perovskite layer allows us to fabricate solar cells with PCEs of 23.9, 29.7 (certified 29.26%), and 28.7% for single-, double-, and triple-junction devices, respectively. Our 1-cm 2 triple-junction devices show PCEs of 28.4% (certified 27.28%). Encapsulated triple-junction cells maintain 80% of their initial efficiencies after 860 h maximum power point tracking in ambient. We further fabricate quadruple-junction devices and obtain PCEs of 27.9% with the highest open-circuit voltage of 4.94 V. This work establishes a new benchmark for multijunction PVs., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

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.)

Few semiconducting polymers are known that possess more than one semi-crystalline structure. Guidelines for rationalizing or creating polymorphism in these materials do not exist. Two different semi-crystalline polymorphs, β 1 and β 2 , and an amorphous α phase have recently been identified for alternating diketopyrrolopyrrole-quaterthiophene copolymers (PDPP4T). The polymorphs differ structurally by the π-π stacking distance, and electronically by the optical bandgap and charge carrier mobility. Here we investigate the corresponding terthiophene (PDPP3T) derivatives, to study the effect of the relative orientation of adjacent DPP units on the polymorphism. In PDPP3T, the relative orientation of DPP units alternates along the chain, while in PDPP4T it is constant. We show that the two polymorphs, β 1 and β 2 , can also be generated for a PDPP3T polymer in solution and thin film. Interestingly, compared to PDPP4T, more solvents can induce the two distinct semi-crystalline polymorphs for PDPP3T via a β 1  →  α  →  β 2 polymorphic transition., (© 2020 The Authors. Journal of Polymer Science published by Wiley Periodicals LLC.)

Parasitic optical absorption is one of the root causes of the moderate efficiency of metal halide perovskite solar cells (PSCs) with an opaque substrate configuration. Here, we investigate the reduction of these optical losses by using thin (7-10 nm), undoped, thermally evaporated 2,2',7,7'-tetrakis[ N , N -di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-OMeTAD), N , N '-di(1-naphthyl)- N , N '-diphenyl-(1,1'-biphenyl)-4,4'-diamine) (NPB), and tris(4-carbazoyl-9-ylphenyl)amine) (TCTA) hole transport layers (HTLs). Of these, NPB is found to offer the best compromise between efficiency and stability. In semitransparent n-i-p configuration PSCs with an indium tin oxide bottom and a MoO 3 /thin-Au/ZnS dielectric-metal-dielectric top electrode, NPB gives 14.9% and 10.7% efficiency for bottom and top illumination, respectively. The corresponding substrate-configuration PSC fabricated on an Au bottom electrode has 13.1% efficiency. Compared to a 14.0% efficient PSC with a thick spin-coated doped spiro-OMeTAD layer, the cell with NPB provides an improved short-circuit current density but has slightly lower open-circuit voltage and fill factor. Detailed analysis of the optical losses in the opaque devices demonstrates that evaporated NPB offers negligible parasitic absorption compared to solution-processed spiro-OMeTAD. The optical losses that remain are due to absorption and reflection of the transparent top electrode., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Electron transport layers (ETLs) placed between the electrodes and a photoactive layer can enhance the performance of organic solar cells but also impose limitations. Most ETLs are ultrathin films, and their deposition can disturb the morphology of the photoactive layers, complicate device fabrication, raise cost, and also affect device stability. To fully overcome such drawbacks, efficient organic solar cells that operate without an ETL are preferred. In this study, a new small-molecule electron donor (H31) based on a thiophene-substituted benzodithiophene core unit with trialkylsilyl side chains is designed and synthesized. Blending H31 with the electron acceptor Y6 gives solar cells with power conversion efficiencies exceeding 13% with and without 2,9-bis[3-(dimethyloxidoamino)propyl]anthra[2,1,9-def:6,5,10-d'e'f ']diisoquinoline-1,3,8,10(2H,9H)-tetrone (PDINO) as the ETL. The ETL-free cells deliver a superior shelf life compared to devices with an ETL. Small-molecule donor-acceptor blends thus provide interesting perspectives for achieving efficient, reproducible, and stable device architectures without electrode interlayers., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

The combination of narrow-bandgap diketopyrrolopyrrole (DPP) polymers and nonfullerene acceptors (NFAs) seems well-matched for solar cells that exclusively absorb in the near infrared but they rarely provide high efficiency. One reason is that processing of the active layer is complicated by the fact that DPP-based polymers are generally only sufficiently soluble in chloroform (CF), while NFAs are preferably processed from halogenated aromatic solvents. By using a ternary solvent system consisting of CF, 1,8-diiodooctane (DIO), and chlorobenzene (CB), the short-circuit current density is increased by 50% in solar cells based on a DPP polymer (PDPP5T) and a NFA (IEICO-4F) compared to the use of CF with DIO only. However, the open-circuit voltage and fill factor are reduced. As a result, the efficiency improves from 3.4 to 4.8% only. The use of CB results in stronger aggregation of IEICO-4F as inferred from two-dimensional grazing-incidence wide-angle X-ray diffraction. Photo- and electroluminescence and mobility measurements indicate that the changes in performance can be ascribed to a more aggregated blend film in which charge generation is increased but nonradiative recombination is enhanced because of reduced hole mobility. Hence, while CB is essential to obtain well-ordered domains of IEICO-4F in blends with PDPP5T, the morphology and resulting hole mobility of PDPP5T domains remain suboptimal. The results identify the challenges in processing organic solar cells based on DPP polymers and NFAs as near-infrared absorbing photoactive layers., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

The effect of the nature of the π-conjugated linker that is positioned between electron-deficient 2,5-dihydropyrrolo[3,4- c ]pyrrole-1,4-dione (DPP) and electron-rich dithieno[3,2- b :2',3'- d ]pyrrole (DTP) units in alternating DPP-DTP copolymers on the optical and electrochemical band gaps and the effective exciton binding energy is investigated for six different aromatic linkers. The optical band gap is related to the electron-donating properties of DTP and the electron-withdrawing properties of DPP but likewise strongly affected by the nature of the linker and varies between 1.13 and 1.80 eV for the six different linkers. The lowest optical band gaps are found for linkers that either raise the highest occupied molecular orbital or lower the lowest unoccupied molecular orbital most, while the highest optical band gap is found for phenyl linkers that have neither strong donating nor strong accepting properties. Along with the optical band gap, the electrochemical band gap also changes, but to a lesser extent from 1.46 to 1.89 eV. The effective exciton binding energy ( E b ), defined as the difference between the electrochemical and optical band gaps, decreases with an increasing band gap and reaches a minimum of 0.09 eV for the copolymer with the highest band gap, that is, with phenyl linkers. The reduction in E b with an increasing band gap is tentatively explained by a reduced electronic interaction between the DTP and DPP units when the HOMO localizes on DTP and the LUMO localizes on DPP. Support for this explanation is found in the molar absorption coefficient of the copolymers, which shows an overall decreasing trend with decreasing E b ., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Inflammatory bowel disease (IBD) is a complex multi-factorial disease for which physiologically relevant in vitro models are lacking. Existing models are often a compromise between biological relevance and scalability. Here, we integrated intestinal epithelial cells (IEC) derived from human intestinal organoids with monocyte-derived macrophages, in a gut-on-a-chip platform to model the human intestine and key aspects of IBD. The microfluidic culture of IEC lead to an increased polarization and differentiation state that closely resembled the expression profile of human colon in vivo. Activation of the model resulted in the polarized secretion of CXCL10, IL-8 and CCL-20 by IEC and could efficiently be prevented by TPCA-1 exposure. Importantly, upregulated gene expression by the inflammatory trigger correlated with dysregulated pathways in IBD patients. Finally, integration of activated macrophages offers a first-step towards a multi-factorial amenable IBD platform that could be scaled up to assess compound efficacy at early stages of drug development or in personalized medicine.

The optical properties of two sets of donor-acceptor-donor molecules with terminal bithiophene donor units and a central diketopyrrolopyrrole (DPP) acceptor unit are studied. The two sets differ in the alkyl chains on the DPP, which are either branched at the α-carbon (3-pentyl) ( 1 - 4 ) or linear ( n -hexyl) ( 5 - 8 ). Within each set, the molecules differ by the absence or presence of n -hexyl chains on the terminal thiophene rings in the 3', 4', or 5' positions. While in solution, the optical spectra differ only subtly; they differ dramatically in the solid state. In contrast to 5 - 8 , 1 - 4 are nonplanar as a consequence of the sterically demanding 3-pentyl groups, which inhibit π-stacking of the DPP units. Using the crystal structures of 2 (brick layer stacking) and 6 (slipped stacking), we quantitatively explain the solid state absorption spectra. By computing the molecular transition charge density and solving the dispersion relation, the optical absorption of the molecules in the crystal is predicted and in agreement with experiments. For 2 , a single resonance frequency is obtained, while for 6 two transitions are seen, with the lower-energy transition being less intense. The results demonstrate how subtle changes in substitution exert large effects in optical properties., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Introducing solubilizing α-branched alkyl chains on a poly(diketopyrrolopyrrole-alt-terthiophene) results in a dramatic change of the structural, optical, and electronic properties compared to the isomeric polymer carrying β-branched alkyl side chains. When branched at the α-position the alkyl substituent creates a steric hindrance that reduces the tendency of the polymer to π-π stack and endows the material with a much higher solubility in common organic solvents. The wider π-π stacking and reduced tendency to crystallize, evidenced from grazing-incidence wide-angle X-ray scattering, result in a wider optical band gap in the solid state. In solar cells with a fullerene acceptor, the α-branched isomer affords a higher open-circuit voltage, but an overall lower power conversion efficiency as a result of a too well-mixed nanomorphology. Due its reduced π-π stacking, the α-branched isomer fluoresces and affords near-infrared light-emitting diodes emitting at 820 nm., (© 2020 The Authors. Published by Wiley-VCH GmbH.)

Perovskite semiconductors hold a unique promise in developing multijunction solar cells with high-efficiency and low-cost. Besides design constraints to reduce optical and electrical losses, integrating several very different perovskite absorber layers in a multijunction cell imposes a great processing challenge. Here, we report a versatile two-step solution process for high-quality 1.73 eV wide-, 1.57 eV mid-, and 1.23 eV narrow-bandgap perovskite films. Based on the development of robust and low-resistivity interconnecting layers, we achieve power conversion efficiencies of above 19% for monolithic all-perovskite tandem solar cells with limited loss of potential energy and fill factor. In a combination of 1.73 eV, 1.57 eV, and 1.23 eV perovskite sub-cells, we further demonstrate a power conversion efficiency of 16.8% for monolithic all-perovskite triple-junction solar cells.

Two asymmetric thiophene (T)/pyridine (Py) flanked diketopyrrolopyrrole (DPP) polymers with a regiorandom and regioregular conjugated backbone are synthesized via a Stille polycondensation to investigate the effect of regioregularity on their optoelectronic properties and photovoltaic performance in fullerene-based polymer solar cells. Surprisingly, both polymers possess very similar optical bandgap, energy levels, and photovoltaic performance. These findings, combined with a factor of 19 reactivity difference between the two end groups of the asymmetric DPP monomer, intuitively suggest the formation of regular chain segments in the random polymer. However, by modeling the random polymerization reaction with a kinetic Monte Carlo (KMC) simulation, evidence is obtained for exclusive formation of a fully random polymer structure. UV-vis-NIR absorption spectra of three extended DPP chromophores, containing the donor segments (T-T-T, Py-T-Py, and Py-T-T) present in the regiorandom polymer, confirm that regioregularity of the backbone has a negligible influence on the optical properties., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

Photovoltaic devices that switch color depending on illumination conditions may find application in future smart window applications. Here a photochromic diarylethene molecule is used as sensitizer in a ternary bulk heterojunction blend, employing poly(4-butylphenyldiphenylamine) (poly-TPD) and [6,6]-phenyl-C 61 -butyric acid methyl ester (PC 61 BM) for the transport of holes and electrons, respectively. Sandwiched between two electrodes, the blend creates a photochromic photovoltaic device that changes color, light absorption, and photon-to-electron conversion efficiency in the visible spectral range after having been illuminated with UV light., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Hybrid organic-inorganic perovskite solar cells have recently emerged as one of the most promising low-cost photovoltaic technologies. The remarkable progress of perovskite photovoltaics is closely related to advances in interfacial engineering and development of charge selective interlayers. Herein, we present the synthesis and characterization of a fused azapolyheteroaromatic small molecule, namely anthradi-7-azaindole (ADAI), with outstanding performance as a hole-transporting layer in perovskite solar cells with inverted architecture. Its molecular arrangement, induced by hydrogen-bond-directed self-assembly, favors a suitable morphology of the perovskite layer, reducing the effects of recombination as revealed by light intensity dependence, photoluminescence, and electroluminescence studies., (© 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Organic electrochemical transistors (OECTs) show great promise for flexible, low-cost, and low-voltage sensors for aqueous solutions. The majority of OECT devices are made using the polymer blend poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS), in which PEDOT is intrinsically doped due to inclusion of PSS. Because of this intrinsic doping, PEDOT:PSS OECTs generally operate in depletion mode, which results in a higher power consumption and limits stability. Here, a straightforward method to de-dope PEDOT:PSS using commercially available amine-based molecular de-dopants to achieve stable enhancement-mode OECTs is presented. The enhancement-mode OECTs show mobilities near that of pristine PEDOT:PSS (≈2 cm 2 V -1 s -1 ) with stable operation over 1000 on/off cycles. The electron and proton exchange among PEDOT, PSS, and the molecular de-dopants are characterized to reveal the underlying chemical mechanism of the threshold voltage shift to negative voltages. Finally, the effect of the de-doping on the microstructure of the spin-cast PEDOT:PSS films is investigated., (© 2020 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

By analyzing the optical band gap and energy levels of seven different regioregular terpolymers in which two different electron-rich donor moieties are alternating with a common electron-deficient acceptor unit along the backbone, we establish a direct correlation with the properties of the corresponding binary copolymers in which one donor and one acceptor are combined. For this study, we use diketopyrrolopyrrole as the common acceptor and different π-conjugated aromatic oligomers as donors. We find that the optical band gap and frontier orbital energies of the terpolymers are the arithmetic average of those of the parent copolymers with remarkable accuracy. The same relationship is also found for the open-circuit voltage of the bulk heterojunction solar cells made with the ter- and copolymers in combination with [6,6]-phenyl-C 71 -butyric acid methyl ester. Comparison of these findings with data in the literature suggests that this is a universal rule that can be used as a tool when designing new π-conjugated polymers. The experimental results are supported by a semiempirical quantum chemical model that accurately describes the energy levels of the terpolymers after parametrization on the energy levels of the copolymers and also provides a theoretical explanation for the observed arithmetic relations., Competing Interests: The authors declare no competing financial interest., (Copyright © 2020 American Chemical Society.)

It remains a challenge to precisely tailor the morphology of polymer monolayers to control charge transport. Herein, the effect of the dissolution temperature (T dis ) is investigated as a powerful strategy for morphology control. Low T dis values cause extended polymer aggregation in solution and induce larger nanofibrils in a monolayer network with more pronounced π-π stacking. The field-effect mobility of the corresponding monolayer transistors is significantly enhanced by a factor of four compared to devices obtained from high T dis with a value approaching 1 cm 2  V -1  s -1 . Besides that, the solution kinetics reveal a higher growth rate of aggregates at low T dis , and filtration experiments further confirm that the dependence of the fibril width in monolayers on T dis is consistent with the aggregate size in solution. The generalizability of the T dis effect on polymer aggregation is demonstrated using three other conjugated polymer systems. These results open new avenues for the precise control of polymer aggregation for high-mobility monolayer transistors., (© 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

A common bottleneck in any drug development process is finding sufficiently accurate models that capture key aspects of disease development and progression. Conventional drug screening models often rely on simple 2D culture systems that fail to recapitulate the complexity of the organ situation. In this study, we show the application of a robust high throughput 3D gut-on-a-chip model for investigating hallmarks of inflammatory bowel disease (IBD). Using the OrganoPlate platform, we subjected enterocyte-like cells to an immune-relevant inflammatory trigger in order to recapitulate key events of IBD and to further investigate the suitability of this model for compound discovery and target validation activities. The induction of inflammatory conditions caused a loss of barrier function of the intestinal epithelium and its activation by increased cytokine production, two events observed in IBD physiopathology. More importantly, anti-inflammatory compound exposure prevented the loss of barrier function and the increased cytokine release. Furthermore, knockdown of key inflammatory regulators RELA and MYD88 through on-chip adenoviral shRNA transduction alleviated IBD phenotype by decreasing cytokine production. In summary, we demonstrate the routine use of a gut-on-a-chip platform for disease-specific aspects modeling. The approach can be used for larger scale disease modeling, target validation and drug discovery purposes.