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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-SiOx: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 1015 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-SiOx: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.

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 (PEA2MAn-1Pbn(BrxI1-x)3n+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 207Pb 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.

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 cm2 V−1 s−1 with a drain current on/off ratio of up to 108. Our findings offer a new strategy for enhancing the device performance of polymer electronic devices.

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-(9H-carbazol-9-yl)ethyl]phosphonic acid monolayer as a hole-selective contact. A triple-cation perovskite is used as the absorber layer. Thermally evaporated C60and atomic layer deposited SnO2layers serve to create an electron-selective contact. The cells use an ITO top electrode with an antireflective MgF2coating. 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 C60layer, the Ti bottom electrode, and reflection from the MgF2coating 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.

Poly(3-hexylthiophene) thin films containing carbon-based nanostructures, i.e. fullerenes such as buckminsterfullerene (C60) or phenyl-C61-butyric acid methyl ester (PCBM), or single-walled carbon nanotubes, were investigated as heterogeneous photosensitizers producing singlet oxygen (1O2) in aerated organic solvents. Thin films were deposited on borosilicate glass using spin coating and characterized by profilometry, UV-vis, Raman and XPS. Photogeneration of 1O2 was confirmed by photooxidation of 1,3-diphenylisobenzofuran and by reaction of 1,5-dihydroxynaphthalene to juglone. The photochemical efficiency of the blends was found to depend on the carbon-based photosensitizer and can be increased by varying its concentration in the poly(3-hexylthiophene) matrix.

The solid-state molecular orientation of conjugated polymers is of vital importance for their charge transport properties, where the edge-on orientation with π-stacking direction parallel to the surface is generally preferable to achieving high-mobility planar field-effect transistors. However, so far, little is known about the origin of packing-orientation formation in thin films. Here, it is shown that the solution-state supramolecular structure of widely studied PffBT4T-based polymers can be reversibly tuned between 1D worm-like and 2D lamellar structures for the same polymer/solvent system through solution temperature. Such dimensionality in solution determines the solid-state packing orientation of the polymer chains, where edge-on and face-on textures are generated from solutions with 1D and 2D structures, respectively. More importantly, the transition temperature of solution-state supramolecular dimensionality is in excellent agreement with that of solid-state packing orientation. These experimental observations unambiguously demonstrate the predominant roles of solution-state supramolecular assembly in solid-state molecular orientation, which is further verified using different molecular weight batches and other two representative polymers. The findings provide new insights into the growth mechanism of polymer semiconductors during transistor fabrication, and open prospective pathways for boosting device performance of solution-processable plastic electronics.

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 D1-A-D2-A and D-A1-D-A2 terpolymers are sensitive to the D1/D2 or A1/A2 monomer ratios. Side-chain hybridization is a strategy to address this problem. Here, six D1-A-D2-A-type random terpolymers (PF1, PF2, PF3, PF7, PF8, and PF9) comprising D1 and D2 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 (Y6-BO-4Cl). This strategy allows improving the device performance to over 18%, higher than that obtained with the corresponding D1-A or D2-A bipolymers (around 17%). Hence, side-chain hybridization is a promising strategy to design efficient D1-A-D2-A terpolymer donors that are insensitive to the D1/D2 monomer ratio, which is beneficial for the scaled-up synthesis of high-performance materials.

Targeted strategies to overcome defects in organic semiconductors require insight into their identity and origin. Here the formation, nature, and location of defects is studied in PM6:Y6 organic solar cells by sensitive EQE measurements. Exposure of the active layer to ambient atmosphere and H2O-saturated compressed air indicates that a trace constituent in ambient air causes the formation of defects. By exposing the active layer to O3-enriched air, O3 is identified as the species creating defects in PM6:Y6 blends. Aging of complete inverted (n–i–p) configuration solar cells in H2O-saturated compressed air also increases the defect response. This is attributed to a reduced band bending at the PM6:Y6 | MoO3 hole-collecting contact, caused by a change in work function of MoO3 interacting with the H2O, which allows more defect states to be filled and available for photoexcitation. By measuring energy resolved-electrochemical impedance spectroscopy and by fabricating semitransparent cells, regular architecture cells, and semitransparent cells with an optical spacer−mirror stack it is found that defects originate predominantly from PM6 and are located near the top electrode, independent of device polarity. Because O3 is omnipresent in ambient atmosphere, albeit in small amounts, it likely causes defects in many organic semiconductors exposed to ambient air.

Single junction crystalline silicon (c-Si) solar cells are reaching their practical efficiency limit whereas perovskite/c-Si tandem solar cells have achieved efficiencies above the theoretical limit of single junction c-Si solar cells. Next to low-thermal budget silicon heterojunction architecture, high-thermal budget carrier-selective passivating contacts (CSPCs) based on polycrystalline-SiOx (poly-SiOx) also constitute a promising architecture for high efficiency perovskite/c-Si tandem solar cells. In this work, we present the development of c-Si bottom cells based on high temperature poly-SiOx CSPCs and demonstrate novel high efficiency four-terminal (4T) and two-terminal (2T) perovskite/c-Si tandem solar cells. First, we tuned the ultra-thin, thermally grown SiOx. Then we optimized the passivation properties of p-type and n-type doped poly-SiOx CSPCs. Here, we have optimized the p-type doped poly-SiOx CSPC on textured interfaces via a two-step annealing process. Finally, we integrated such bottom solar cells in both 4T and 2T tandems, achieving 28.1% and 23.2% conversion efficiency, respectively.

Solution-processed photodetectors could be of use in large-area light-sensing applications because they can be fabricated at low cost on plastic substrates and their absorption spectra can be tuned by chemical design. However, fabricating photodetectors with low dark currents and integrating them into high-resolution backplanes remains challenging. Here we show that solution-processed metal halide perovskite photodiodes on top of an amorphous indium gallium zinc oxide transistor backplane can be used to create a flexible image sensor that is ~100 μm thick and has a resolution of 508 pixels per inch. We have developed a pixel edge cover layer for the system that reduces electrode current leakage and thus dark current density. The low noise current in combination with high external quantum efficiency results in high photodetectivity at wavelengths from 550 nm to 770 nm. We show that our imager can be used for document scanning and biometric fingerprinting and that it can be wrapped around objects with radii as small as 0.6 cm. Low-dark-current perovskite photodetectors can be integrated with an oxide transistor backplane to create a high-resolution optical scanning array capable of imaging flat and curved surfaces.

Recent developments toward high-energy-density all-organic redox flow batteries suggest the advantageous use of molecules exhibiting multielectron redox events. Following this approach, organic anolytes are developed that feature multiple consecutive one-electron reductions. These anolytes are based on N-methylphthalimide, which exhibits a single reversible reduction at a low potential with good cycling stability. Derivatives with two or three imide groups were synthesized to enable multielectron reduction events. By incorporating suitably designed side chains, a volumetric capacity of 65 Ah/L is achieved in electrolyte solutions. Bulk-electrolysis experiments and UV-vis-NIR absorption spectroscopy revealed good cycling stability for the first and second reduction of monoamides and diimides, respectively, but a loss of stability for the third reduction of triimides. We identify N-2-pentyl-N′-2-(2-(2-methoxyethoxy)ethoxy)ethylaminepyromellitic diimide as a very promising multielectron anolyte with an excellent volumetric capacity and superior cycling and shelf-life stability compared to monoimides and triimides. The outstanding performance of this anolyte was demonstrated in proof-of-principle redox flow batteries that reach an energy density of 24.1 Wh/L.

Side-chain engineering is an important strategy in designing novel polymer semiconductor materials for high-efficient organic solar cells. The use of trialkylsilyl side chains can improve the photovoltaic efficiency by decreasing the energy of the highest occupied molecular orbital (HOMO) of the polymer and improving its crystallinity and hole mobility. Compared to simple linear derivatives, α-branching in the alkyl groups of trialkylsilyl side chains causes strong aggregation and excessive phase separation in the photoactive layer, leading to poor device performance. β-branching of the alkyl groups has not yet been used in trialkylsilyl side chains. Herein, we describe a new polymer (J77) with triisobutylsilyl side chains to investigate the effect of β-branching on the molecular aggregation, optical properties, energy levels, and photovoltaic properties. We find that compared to α-branching, β-branching of alkyl groups in trialkylsilyl side chains significantly reduces aggregation. This enables J77 to form blend morphologies in films that provide high-efficient solar cells in combination with different non-fullerene acceptors. Moreover β-branching of the alkyl groups in trialkylsilyl side chains lowers the HOMO energy level of J77 and increases the open-circuit voltage of J77-based solar cells without sacrificing short-circuit current density or fill factor

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- A nd 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.

2H-Benzotriazol-2-ylethylammonium bromide and iodide and its difluorinated derivatives are synthesized and employed as interlayers for passivation of formamidinium lead triiodide (FAPbI3) solar cells. In combination with PbI2 and PbBr2, 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 FAPbI3 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 recombi-nation 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 FAPbI3 show that a nonuniform layer of 2D perovskites is enough to passivate defects, enhance charge extraction, and decrease nonradiative recombination. The research has received funding from the Ministry of Education, Culture, and Science (Gravity program 024.001.035) and the Netherlands Organization for Scientific Research via a Spinoza grant. This work of B.T.v.G. is part of the Advanced Research Center for Chemical Building Blocks, ARC CBBC, which is cofounded and cofinanced by the Netherlands Organization for Scientific Research (NWO) and the Netherlands Ministry of Economic Affairs (project 2016.03.Tue). W.T.M.v.G., K.V.H., L.L., and D.V. acknowledge the Research Foundation Flanders (FWO) for the funding of the SBO project PROCEED (S002019N) and the senior FWO research projects G043320N and G0A8723N. A.M. acknowledges the FWO for the funding of his FWO fundamental research PhD grant (1115721N). This study was supported by the Special Research Fund (BOF) of Hasselt University (BOF22PD01). J.F.O. acknowledges funding from the Engineering and Physical Sciences Research Council (EPSRC) Nano Doctoral Training Centre (EP/L015978/1).

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

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., Branching out: α‐Branched alkyl side chains avoid aggregation of polydiketopyrrolopyrroles and permit processing organic solar cells and light‐emitting diodes from benign solvents.

Sub-micrometer thin-film transistors (TFTs) are realized using multi-level imprint lithography. Amorphous indium gallium zinc oxide ( $\alpha $ -IGZO) TFTs with channel lengths as small as $0.7~\mu \text{m}$ , field-effect mobility of 10 cm2V−1s−1 and on/off ratio of circa 107 were integrated into a 1000-pixels per inch (ppi) TFT backplane array. The reduction of the number of patterning steps and the inherent self-registration of the most critical transistor layers on top of each other offer a cost-effective high-throughput fabrication route for high-resolution TFT arrays.

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.

The effect of the length of solubilizing alkyl side chains, ranging from hexyl to pentadecyl, on the formation and structure of two distinct semi-crystalline semiconductor phases, ß1and ß2, of a single conjugated polymer is investigated for a low band gap poly(diketopyrrolopyrrole-alt-quaterthiophene). Compared to ß1, the ß2phase exhibits a distinct redshifted absorption and an associated near infrared photoluminescence. The length of the alkyl side chains controls the formation of the ß1and ß2phases. Intermediate length alkyl side chains (nonyl and dodecyl) can selectively provide the ß1or ß2phase in solution and in semi-crystalline thin films, depending on the nature of the solvent used. For short side chains (hexyl) the ß2phase forms more readily while for long side chains (pentadecyl) the ß1phase is predominant. The kinetics of ß2phase formation is investigated and reveals a reduced growth rate when long alkyl side chains are present. X-ray diffraction reveals a closer p-p stacking distance for ß2than for ß1, consistent with its redshifted absorption and its higher mobility in field-effect transistors. The polymer with hexyl side chains adopts an edge-on orientation in thin films, while the longer alkyl chains induce a face-on orientation. Photovoltaic devices exhibit an additional near infrared spectral contribution to the photocurrent for the ß2phase. The study shows that the formation of the two polymorphs ß1and ß2is controlled by the alkyl side chains and the solubility that arises from them. Shorter side chains (lower solubility) favor ß2and longer side chains (higher solubility) ß1, and at intermediate lengths both phases can be formed.

Since their introduction in 2017, the efficiency of lead-free halide perovskite solar cells based on Cs2AgBiBr6 has not exceeded 3%. The limiting bottlenecks are attributed to a low electron diffusion length, self-trapping events and poor selectivity of the contacts, leading to large non-radiative VOC losses. Here, 2D/3D hybrid double perovskites are introduced for the first time, using phenethyl ammonium as the constituting cation. The resulting solar cells show an increased efficiency of up to 2.5% for the champion cells and 2.03% on average, marking an improvement by 10% compared to the 3D reference on mesoporous TiO2. The effect is mainly due to a VOC improvement by up to 70 mV on average, yielding a maximum VOC of 1.18 V using different concentrations of phenethylammonium bromide. While these are among the highest reported VOC values for Cs2AgBiBr6 solar cells, the effect is attributed to a change in recombination behavior within the full device and a better selectivity at the interface toward the hole transporting material (HTM). This explanation is supported by voltage-dependent external quantum efficiency, as well as photoelectron spectroscopy, revealing a better energy level alignment and thus a better hole-extraction and improved electron blocking at the HTM interface.

Thin-film organic and perovskite solar cells have seen tremendous advances in recent years. A common technique to characterize the low-energy states in these solar cells is electroluminescence spectroscopy. Stemming from their thin film nature, however, the outcoupled electroluminescence spectra of these devices are affected by cavity effects and self-absorption. Herein, a modeling approach is developed taking into account self-absorption, cavity effects, and a nonhomogeneous emission profile, to correct the outcoupled spectrum, thereby yielding the intrinsically emitted spectrum. The modeling approach is then employed to structurally investigate the impact of these effects for a variety of active layer thicknesses, complex refractive indices, device structures, and emission profiles. The data presented uncover trends and provide guidelines that enable gauging the impact of self-absorption and cavity effects on the electroluminescence spectra of a large set of thin-film devices.

Tetrathiafulvalene (TTF) exhibits two reversible oxidation steps and is used as a novel multi-electron catholyte for nonaqueous organic redox flow batteries. To increase solubility in polar organic solvents, TTF derivatives with polar side chains are synthesized. 4-Methoxymethyltetrathiafulvalene emerges as a promising two-electron catholyte because it is a liquid at room temperature and miscible with acetonitrile. Bulk-electrolysis experiments and UV-vis-NIR absorption spectroscopy reveal excellent cycling stability for the first and second electrochemical oxidations. In the doubly oxidized state, the TTF derivatives show a reversible about 1 % loss of the state of charge per day, due to extrinsic effects. In a symmetric redox flow battery, 4-methoxymethyltetrathiafulvalene shows a volumetric capacity loss of only 0.2 % per cycle with a Coulombic efficiency (CE) of 99.6 %. In an asymmetric redox flow battery with a pyromellitic diimide as two-electron anolyte, the capacity loss is 0.8 % per cycle, with CE>99 % in each cycle.

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%.

Fabricating efficient perovskite solar cells on steel substrates could enable easy building integration of this photovoltaic technology. Herein, an n–i–p perovskite solar cell is developed on steel substrates for top illumination. The optimized stack uses a Ti bottom electrode, covered with an indium tin oxide (ITO) interlayer and a SnO2 electron transport layer passivated by [6,6]-phenyl-C61-butyric acid. The active layer is a triple-cation perovskite. A thermally evaporated tris(4-carbazoyl-9-ylphenyl)amine)/MoO3 bilayer acts as hole transport layer. The transparent top contact consists of ITO with a MgF2 antireflective coating. Optical analysis shows small parasitic absorption and reflectance losses for this stack, which provides 15.9% power conversion efficiency when fabricated on glass. On steel, covered with a polyamide imide planarization coating to moderate the surface roughness (R p), the highest efficiency is 15.2% for high-gloss steel (R p≈ 200 nm), 14.9% for battery steel (R p≈ 500 nm), 14.2% for packaging steel (R p≈ 1500 nm), and 13.8% for construction steel (R p≈ 2500 nm). While the short-circuit current density and open-circuit voltage are invariant, the fill factor decreases with increasing R p due to increasing series resistance and decreasing shunt resistance. The yield of working devices remain high, also for the roughest substrates.

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.

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 × 1012 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.

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.

In recent years, noncovalently assembled monolayers of conjugated, semiconducting polymers with thickness less than 5 nm have attracted increasing attention because of their determining role in charge carrier transport in field-effect transistors and their multifunctionality in other electronic devices. This article reviews recent advances in various promising and cutting-edge polymer monolayers for high-performance field-effect transistors with the main focuses on: (I) solution processing techniques for long-range ordering; (II) the importance of polymer aggregation in solution; (III) the effect of polymer packing orientation; (IV) engineering of the interface between the polymer monolayer with electrodes and dielectrics; (V) investigating the mechanism of charge carrier transport. By summarizing the field-effect mobilities of the different classes of conjugated semiconducting polymer monolayers, further understanding of correlation between monolayer structure and device property will be revealed. Furthermore, we also highlight the recent progress of other electronic applications of polymer monolayers such as integrated circuits, chemical sensors, and light-emitting diodes. Finally, we propose future research opportunities and remaining challenges in this exciting research field.

Polymorphism of organic semiconducting materials exerts critical effects on their physical properties such as optical absorption, emission and electrical conductivity, and provides an excellent platform for investigating structure–property relations. It is, however, challenging to efficiently tune the polymorphism of conjugated polymers in aggregated, semi-crystalline phases due to their conformational freedom and anisotropic nature. Here, two distinctly different semi-crystalline polymorphs (β1 and β2) of a low-bandgap diketopyrrolopyrrole polymer are formed through controlling the solvent quality, as evidenced by spectroscopic, structural, thermal and charge transport studies. Compared to β1, the β2 polymorph exhibits a lower optical band gap, an enhanced photoluminescence, a reduced π-stacking distance, a higher hole mobility in field-effect transistors and improved photocurrent generation in polymer solar cells. The β1 and β2 polymorphs provide insights into the control of polymer self-organization for plastic electronics and hold potential for developing programmable ink formulations for next-generation electronic devices., Tuning polymorphism of conjugated polymers, though a promising method for studying and controlling the structure-property relations in these materials remains a challenge. Here, the authors identify two aggregated semi-crystalline polymorphs of a low-bandgap diketopyrrolopyrrole-based polymer.

[Image: see text] Singlet fission in pentacene creates two triplet excitons per absorbed photon. In a solar cell, each triplet can generate an electron–hole pair, and hence, external quantum efficiencies exceeding 100% have been reported for pentacene–fullerene solar cells. The energetics of this process are intriguing because the minimum photon energy loss, defined as the energy difference between the (triplet) exciton state and the open-circuit voltage, is less than 0.5 eV and distinctively smaller than that in most organic donor–acceptor solar cells. To investigate the energetics of this process, we analyze the effect of the energy of the lowest unoccupied molecular orbital (LUMO) for different fullerene derivatives. With the LUMO energy becoming less negative, the open-circuit voltage increases and charge generation decreases. For all but one of the fullerenes tested, the charge-transfer state energy is distinctively higher than the pentacene triplet energy, revealing that charge generation via singlet fission is actually endergonic. An elementary Marcus model for the rate of electron transfer provides a qualitative description of the experimental trends, in accordance with an endergonic charge transfer. Considering that charge generation from triplet states is endergonic, involvement of pentacene singlet states, either from direct photoexcitation or via triplet–triplet annihilation, cannot be excluded.

The effect of gradually replacing the branched alkyl side chains of a diketopyrrolopyrrole (DPP) conjugated polymer by linear side chains containing branched siloxane end groups on the photovoltaic performance of blends of these polymers with a common fullerene acceptor is investigated. With an increasing proportion of siloxane side chains, the molecular weight and solubility of the polymers decreases. While the siloxane containing polymers exhibit a higher hole mobility in field-effect transistors, their performance in solar cells is less than the polymer with only alkyl sides chains. Using grazing-incidence wide-angle X-ray scattering, transmission electron microscopy, and fluorescence spectroscopy we identify two main reasons for the reduced performance of siloxane containing polymers in solar cells. The first one is a somewhat coarser phase-separated morphology with slightly wider polymer fibers. This is unexpected as often the fiber width is inversely correlated with polymer solubility. The second one is stronger non-radiative decay of the pristine polymers containing siloxane side chains. G. H. L. Heintges acknowledges the Agency for Innovation by Science and Technology in Flanders (IWT). This project has further received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sklodowska-Curie grant agreement No. 747422, from the European Research Council under the European Union's Seventh Framework Programme (FP/2007-2013)/ERC Grant Agreement No. 339031 and from the Ministry of Education, Culture and Science (Gravity program 024.001.035).

The packing mode of small‐molecular semiconductors in thin films is an important factor that controls the performance of their optoelectronic devices. Designing and changing the packing mode by molecular engineering is challenging. Three structurally related diketopyrrolopyrrole (DPP)‐based compounds were synthesized to study the effect of replacing C−C bonds by isoelectronic dipolar B←N bonds. By replacing one of the bridging C−C bonds on the peripheral fluorene units of the DPP molecules by a coordinative B←N bond and changing the B←N bond orientation, the optical absorption, fluorescence, and excited‐state lifetime of the compounds can be tuned. The substitution alters the preferential aggregation of the molecules in the solid state from H‐type (for C−C) to J‐type (for B←N). Introducing B←N bonds thus provides a subtle way of controlling the packing mode. The photovoltaic properties of the compounds were evaluated in bulk heterojunctions with a fullerene acceptor and showed moderate performance as a consequence of suboptimal morphologies, bimolecular recombination, and triplet‐state formation.

The incorporation of additives to modulate the properties of metal halide perovskite thin films has become a successful approach in improving the power conversion efficiency of perovskite-based solar cells. Herein, the beneficial use of sodium diethyldithiocarbamate (NaDEDTC) as processing agent in improving the open-circuit voltage of methylammonium lead triiodide perovskite solar cells is reported. DEDTC reduces the rate of perovskite crystallization. Absorption and emission spectra show that the optical bandgap of the perovskite films remain essentially unchanged and X-ray diffraction reveals the formation of preferentially oriented crystallites independent of the use of DEDTC. The use of DEDTC, however, results in a decrease in nonradiative decay as inferred from a two order of magnitude increase in electroluminescence efficiency, explaining the increased open-circuit voltage. Fourier-transform infrared spectroscopy, nuclear magnetic resonance, and X-ray photoelectron spectroscopy show that the DEDTC ligand is not present after the film processing. Therefore, DEDTC modulates film formation but is not incorporated in the perovskite or present as a surface ligand. Sodium ions, on the contrary, are incorporated in the perovskite layer.

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.

Emerging photovoltaics (PVs), focuses on a variety of applications complementing large scale electricity generation. For instance, organic, dye-sensitized and some perovskite solar cells are considered in building integration, greenhouses, wearable and indoors, thereby motivating research on flexible, transparent, semitransparent, and multi-junction PVs. Nevertheless, it can be very time consuming to find or develop an up-to-date overview over the state-of-the-art performance for these systems and applications. Two important resources for record research cells efficiencies are the National Renewable Energy Laboratory chart and the efficiency tables compiled biannually by Martin Green and colleagues. Both publications provide an effective coverage over the established technologies, bridging research and industry. An alternative approach is proposed here summarizing the best reports in the diverse research subjects for emerging PVs. Best performance parameters are provided as a function of the photovoltaic bandgap energy for each technology and application, and are put into perspective using, e.g., the Shockley-Queisser limit. In all cases, the reported data correspond to published and/or properly described certified results, with enough details provided for prospective data reproduction. Additionally, the stability test energy yield (STEY) is included as an analysis parameter among state-of-the-art emerging PVs.

Lead–tin (Pb–Sn) hybrid perovskite materials possess ideal narrow bandgaps (1.2–1.4 eV) for efficient single-junction and tandem solar cells. Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is commonly used as hole transport layer (HTL) for Pb–Sn perovskite solar cells (PSCs), despite its poor stability with these perovskites. Here, two new octacyclic heteroaromatic molecules, pyrenodiindole (PDI) and pyrenodi-(7-azaindole) (PDAI), are presented as the HTL for narrow-bandgap (1.23 eV) p–i–n Pb-Sn PSCs. The self-assembled reciprocal hydrogen-bonded solid-state structure of PDAI bestows robustness compared to PDI, making it less vulnerable in processing the perovskite film on top, and improves the reproducibility of device fabrication. Transient photocurrent measurements and light-intensity-dependent device characteristics indicate that PDI and PDAI possess similar hole extraction properties to PEDOT:PSS. As a result, similar open-circuit voltages and fill factors are obtained in the PSCs. Interestingly, the use of thin PDI and PDAI as HTL in PSCs changes the optical interference and reduces parasitic absorption in the near-infrared region, resulting in an improved short-circuit current density. Consequently, a higher power conversion efficiency of 16.1% is obtained for PDI and PDAI, compared to 15.1% for PEDOT:PSS. In addition, the self-assembled structure of PDAI led to a notable enhancement of device stability.

Emerging photovoltaics (PVs) focus on a variety of applications complementing large scale electricity generation. Organic, dye-sensitized, and some perovskite solar cells are considered in building integration, greenhouses, wearable, and indoor applications, thereby motivating research on flexible, transparent, semitransparent, and multi-junction PVs. Nevertheless, it can be very time consuming to find or develop an up-to-date overview of the state-of-the-art performance for these systems and applications. Two important resources for recording research cells efficiencies are the National Renewable Energy Laboratory chart and the efficiency tables compiled biannually by Martin Green and colleagues. Both publications provide an effective coverage over the established technologies, bridging research and industry. An alternative approach is proposed here summarizing the best reports in the diverse research subjects for emerging PVs. Best performance parameters are provided as a function of the photovoltaic bandgap energy for each technology and application, and are put into perspective using, e.g., the Shockley-Queisser limit. in all cases, the reported data correspond to published and/or properly described certified results, with enough details provided for prospective data reproduction. Additionally, the stability test energy yield is included as an analysis parameter among state-of-the-art emerging PVs., VDI/VD Innovation + Technik GmbH; SAOT - German Research Foundation (DFG)German Research Foundation (DFG); DFGGerman Research Foundation (DFG)European Commission [INST 90/917-1 FUGG, 182849149, SFB 953]; Energy Conversion Systems-from Materials to Devices [IGK 2495]; grant "ELF-PV-Design and development of solution processed functional materials for the next generations of PV technologies" [44-6521a/20/4]; grant "Solar Factory of the Future" [FKZ 20.2-3410.5-4-5]; SolTech Initiative by the Bavarian State Government; FAPESPFundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) [2017/11986-5]; ShellRoyal Dutch Shell; ANP (Brazil's National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation; National Science FoundationNational Science Foundation (NSF) [CBET-1702591]; US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies OfficeUnited States Department of Energy (DOE) [34351]; European Research Council under the European Union's Horizon 2020 research and innovation program [742708]; Projekt DEAL, O.A. acknowledges the financial support from the VDI/VD Innovation + Technik GmbH (Project-title: PV-ZUM) and the SAOT funded by the German Research Foundation (DFG) in the framework of the German excellence initiative. C.J.B. acknowledges funding from DFG within INST 90/917-1 FUGG, the SFB 953 (DFG, project no. 182849149) and the IGK 2495 (Energy Conversion Systems-from Materials to Devices). C.J.B. further acknowledges the grants "ELF-PV-Design and development of solution processed functional materials for the next generations of PV technologies" (No. 44-6521a/20/4) and "Solar Factory of the Future" (FKZ 20.2-3410.5-4-5) and the SolTech Initiative by the Bavarian State Government. A.F.N. acknowledges support from FAPESP (Grant 2017/11986-5), Shell and the strategic importance of the support given by ANP (Brazil's National Oil, Natural Gas and Biofuels Agency) through the R&D levy regulation. R.R.L. gratefully acknowledges support from the National Science Foundation under grant CBET-1702591. N.K. acknowledges funding by the US Department of Energy, Office of Energy Efficiency and Renewable Energy, Solar Energy Technologies Office, Agreement Number 34351. J.N. thanks the European Research Council for support under the European Union's Horizon 2020 research and innovation program (grant agreement No 742708).; Open access funding enabled and organized by Projekt DEAL.