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A bilayer perovskite photodetector that operates in broadband and narrowband modes, depending on the illumination side, is presented. It consists of two perovskite films with different bandgaps, separated by a metal oxide layer to avoid intermixing.

We report semitransparent NIR perovskite photodetectors based on tin–lead hybrid perovskites, by using very thin film perovskite layers and transparent indium tin oxide electrodes.

The syntheses and characterisations of a series of heteroleptic copper(i) compounds [Cu(POP)(Mebpy)][A], [Cu(POP)(Me2bpy)][A], [Cu(xantphos)(Mebpy)][A] and [Cu(xantphos)(Me2bpy)][A] in which [A]− is [BF4]−, [PF6]−, [BPh4]− and [BArF4]− (Mebpy = 6-methyl-2,2′-bipyridine, Me2bpy = 6,6′-dimethyl-2,2′-bipyridine, POP = oxydi(2,1-phenylene)bis(diphenylphosphane), xantphos = (9,9-dimethyl-9H-xanthene-4,5-diyl)bis(diphenylphosphane), [BArF4]− = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) are reported. Nine of the compounds have been characterised by single crystal X-ray crystallography, and the consequences of the different anions on the packing interactions in the solid state are discussed. The effects of the counterion on the photophysical properties of [Cu(POP)(N^N)][A] and [Cu(xantphos)(N^N)][A] (N^N = Mebpy and Me2bpy) have been investigated. In the solid-state emission spectra, the highest energy emission maxima are for [Cu(xantphos)(Mebpy)][BPh4] and [Cu(xantphos)(Me2bpy)][BPh4] (λemmax = 520 nm) whereas the lowest energy λemmax values occur for [Cu(POP)(Mebpy)][PF6] and [Cu(POP)(Mebpy)][BPh4] (565 nm and 563 nm, respectively). Photoluminescence quantum yields (PLQYs) are noticeably affected by the counterion; in the [Cu(xantphos)(Me2bpy)][A] series, solid-state PLQY values decrease from 62% for [PF6]−, to 44%, 35% and 27% for [BF4]−, [BPh4]− and [BArF4]−, respectively. This latter series of compounds was used as active electroluminescent materials on light-emitting electrochemical cells (LECs). The luminophores were mixed with ionic liquids (ILs) [EMIM][A] ([EMIM]+ = [1-ethyl-3-methylimidazolium]+) containing the same or different counterions than the copper(i) complex. LECs containing [Cu(xantphos)(Me2bpy)][BPh4] and [Cu(xantphos)(Me2bpy)][BArF4] failed to turn on under the LEC operating conditions, whereas those with the smaller [PF6]− or [BF4]− counterions had rapid turn-on times and exhibited maximum luminances of 173 and 137 cd m−2 and current efficiencies of 3.5 and 2.6 cd A−1, respectively, when the IL contained the same counterion as the luminophore. Mixing the counterions ([PF6]− and [BF4]−) of the active complex and the IL led to a reduction in all the figures of merit of the LECs., The choice of counterion in heteroleptic copper(i) luminophores for LECs has a critical effect on the photoluminescence quantum yields of the solid materials, and on the device figures-of-merit.

Lead-free halide double perovskites (DPs) are highly tunable materials in terms of chemical composition and optical properties. One of the most widely reported DPs is Cs2AgBiBr6, which is envisaged as a promising absorber for photovoltaics. Nevertheless, its bandgap (around 1.9−2.3 eV) remains too large for common tandem solar cells. In this work, we report the mechanochemical synthesis of Sn-, Ge-, and Zn-substituted Cs2AgBiBr6 in powder form; their bandgaps reach 1.55, 1.80, and 2.02 eV, respectively. These differences are rationalized through density functional theory calculations, demonstrating combined electronic and structural (disorder) effects introduced by the divalent metal-cation substituents. Finally, we present the first vacuum-deposited thin films of the Sn-substituted DP, which also show a notable narrowing of the bandgap, and this paves the way toward its implementation in photovoltaic solar cells.

Perovskite/perovskite tandem solar cells have recently exceeded the record power conversion efficiency (PCE) of single-junction perovskite solar cells. They are typically built in the superstrate configuration, in which the device is illuminated from the substrate side. This limits the fabrication of the solar cell to transparent substrates, typically glass coated with a transparent conductive oxide (TCO), and adds constraints because the first subcell that is deposited on the substrate must contain the wide-bandgap perovskite. However, devices in the substrate configuration could potentially be fabricated on a large variety of opaque and inexpensive substrates, such as plastic and metal foils. Importantly, in the substrate configuration the narrow-bandgap subcell is deposited first, which allows for more freedom in the device design. In this work, we report perovskite/perovskite tandem solar cells fabricated in the substrate configuration. As the substrate we use TCO-coated glass on which a solution-processed narrow-bandgap perovskite solar cell is deposited. All of the other layers are then processed using vacuum sublimation, starting with the charge recombination layers, then the wide-bandgap perovskite subcell, and finishing with the transparent top TCO electrode. Proof-of-concept tandem solar cells show a maximum PCE of 20%, which is still moderate compared to those of best-in-class devices realized in the superstrate configuration yet higher than those of the corresponding single-junction devices in the substrate configuration. As both the top and bottom electrodes are semitransparent, these devices also have the potential to be used as bifacial tandem solar cells.

Vacuum deposition methods are increasingly applied to the preparation of perovskite films and devices, in view of the possibility to prepare multilayer structures at low temperature. Vacuum-deposited, wide-bandgap solar cells based on mixed-cation and mixed-anion perovskites have been scarcely reported, due to the challenges associated with the multiple-source processing of perovskite thin films. In this work, we describe a four-source vacuum deposition process to prepare wide-bandgap perovskites of the type FA1-n Cs n Pb(I1-x Br x )3 with a tunable bandgap and controlled morphology, using FAI, CsI, PbI2, and PbBr2 as the precursors. The simultaneous sublimation of PbI2 and PbBr2 allows the relative Br/Cs content to be decoupled and controlled, resulting in homogeneous perovskite films with a bandgap in the 1.7-1.8 eV range and no detectable halide segregation. Solar cells based on 1.75 eV bandgap perovskites show efficiency up to 16.8% and promising stability, maintaining 90% of the initial efficiency after 2 weeks of operation.

Vacuum processing of multicomponent perovskites is not straightforward, because the number of precursors is in principle limited by the number of available thermal sources. Herein, we present a process which allows increasing the complexity of the formulation of vacuum-deposited lead halide perovskite films by multisource deposition and premixing both inorganic and organic components. We apply it to the preparation of wide-bandgap CsMAFA triple-cation perovskite solar cells, which are found to be efficient but not thermally stable. With the aim of stabilizing the perovskite phase, we add guanidinium (GA+) to the material formulation and obtained CsMAFAGA quadruple-cation perovskite films with enhanced thermal stability, as observed by X-ray diffraction and rationalized by microstructural analysis. The corresponding solar cells showed similar performance with improved thermal stability. This work paves the way toward the vacuum processing of complex perovskite formulations, with important implications not only for photovoltaics but also for other fields of application.

Halide perovskites have generated considerable research interest due to their excellent optoelectronic properties in the past decade. To ensure the formation of high-quality semiconductors, the deposition process for the perovskite film is a critical issue. Vacuum-based processing is considered to be a promising method, allowing, in principle, for uniform deposition on a large area. One of the benefits of vacuum processing is the control over the film composition through the use of quartz crystal microbalances (QCMs) that monitor the rates of the components in situ. In metal halide perovskites, however, one frequently employed component or precursor, CH3NH3I, exhibits nonstandard sublimation properties. Here, we study in detail the sublimation properties of CH3NH3I and demonstrate that by correcting for its complex adsorption properties and by modeling the film growth, accurate predictions of the stoichiometry of the final perovskite film can be obtained.

Migraine is a complex brain disorder, characterized by attacks of unilateral headache and global dysfunction in multisensory information processing, whose underlying cellular and circuit mechanisms remain unknown. The finding of enhanced excitatory, but unaltered inhibitory, neurotransmission at cortical synapses between pyramidal cells (PCs) and fast-spiking interneurons (FS INs) in mouse models of familial hemiplegic migraine (FHM) suggested the hypothesis that dysregulation of the excitatory-inhibitory (E/I) balance in specific circuits is a key pathogenic mechanism. Here, we investigated the cortical layer 2/3 (L2/3) feedback inhibition microcircuit involving somatostatin-expressing (SOM) INs in FHM1 mice of both sexes carrying a gain-of-function mutation in Ca

Vacuum processing is considered to be a promising method allowing the scalable fabrication of perovskite solar cells (PSCs). In vacuum processed PSCs, the n-i-p structure employing organic charge transport layers is less common than the p-i-n structure due to limited options to achieve an efficient electron extraction layer (EEL) on indium tin oxide (ITO) with vacuum thermal evaporation. There are a number of specific applications where an n-i-p structure is required and therefore, it is of interest to have alternative solutions for the n-type contact in vacuum processed PSCs. In this work, we report an efficient vacuum deposited EEL using a mixture of conventional organic small molecules, C60 and bathocuproine (BCP). Incorporation of BCP into C60 does not result in conventional n-doping; however, we observed enhanced charge extraction, which significantly increased the power conversion efficiency (PCE) from 13.1% to 18.1% in all-vacuum processed PSCs. The C60:BCP mixed (co-sublimated) film most likely results in shifted energy levels leading to better alignment with the electrodes.

Thin polymeric and small-molecular-weight organic semiconductors are widely employed as hole transport layers (HTLs) in perovskite solar cells. To ensure ohmic contact with the electrodes, the use of doping or additional high work function (WF) interlayer is common. In some cases, however, intrinsic organic semiconductors can be used without any additive or buffer layers, although their thickness must be tuned to ensure selective and ohmic hole transport. Herein, the characteristics of thin HTLs in vacuum-deposited perovskite solar cells are studied, and it is found that only very thin (= 5 nm), a dynamic behavior for consecutive electrical measurements is observed, a phenomenon which is also common to other widely used HTLs. Finally, it is found that despite their glass transition temperature, small-molecule HTLs lead to thermally unstable solar cells, asopposed to polymeric materials. The origin of the degradation is still not clear, but might be related to chemical reactions/diffusion at the HTL/perovskite interface, in detriment of the device stability

Narrowband photodetectors (PDs) are sought after for many applications requiring selective spectral response. The most common systems combine optical bandpass filters with broadband photodiodes. This work reports a method to obtain a narrowband response in a perovskite PD by the monolithic integration of a perovskite photoconductor and a perovskite photodiode. The spectral response of the tandem PD is determined by the bandgap energy difference of the two perovskites, and exhibits a full width at half maximum below 85 nm, an external quantum efficiency up to 68% and a high specific detectivity of ≈1012 Jones in reverse bias, enabling the device to detect weak light signals. The absorption profile of the narrowband PD can be tuned by changing the thickness and bandgap of the wide bandgap perovskite absorber.

We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with ΦPL of up to 35%, and in solution, with ΦPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes and light-emitting electrochemical cells (LECs), both of which showed moderate performance. Compared to the benchmark copper(I)-based LECs, [Cu(dnbp)(DPEPhos)]+ (maximum external quantum efficiency, EQEmax = 16%), complex 3 (EQEmax = 1.85%) showed a much longer device lifetime (t1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)]+ and complex 3, respectively). The electrochemiluminescence (ECL) properties of several complexes were also studied, which, to the best of our knowledge, constitutes the first ECL study for heteroleptic copper(I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in a LEC.

Lead halide perovskites (ABX3) are generally formed from a reaction of the lead halide salt (BX2) with the halide salt of the A cation (AX). The effects of varying film compositions as result of non-stoichiometric precursor ratios on electronic properties of halide perovskites are currently under debate. It is imperative, but experimentally challenging, to determine the chemical composition of thin films as a function of precursor ratio for a full understanding of the effect. Herein we report a precise quantification of the methylammonium (MA) content in differently fabricated films of MAPbI3 via infrared (IR) spectroscopy. We compare the thin film data to the first high quality dielectric function obtained from single crystals with IR ellipsometry. For spin-coated samples, we find that the MAI/PbI2 ratio in solution has an effect on the MA content in the resulting thin films which is in the range of 77-106% compared to single crystals. For co-evaporated samples, we show that a very similar range of MA co...

A rigid dinuclear Ir(III) complex showing high photoluminescence quantum yield in pure films was successfully used to fabricate light-emitting electrochemical cells with and without ionic liquid additives. The devices showed nearly instantaneous electroluminescence after biasing and maximum quantum yield approaching 1%. The lifetime of the devices was found to be limited to approximately 20 hours, which we correlated with the irreversible oxidation of the complex as seen from electrochemical measurements. This work validates the use of highly luminescent dinuclear iridium complexes in light-emitting electrochemical cells. Future studies will pursue materials with more efficient photoluminescence as well as improved electrochemical stability.

Halide perovskites have shown excellent photophysical properties for solar cell applications which led to a rapid increase of the device efficiency. Understanding the charge carrier dynamics within the active perovskite absorber and at its interfaces will be key to further progress in their development. Here we present a series of fully evaporated devices employing hole transport materials with different ionization energies. The open circuit voltage of the devices, along with their ideality factors, confirm that the former is mainly determined by the bulk and surface recombination in the perovskite, rather than by the energetic offset between the valence band of the perovskite and the highest occupied molecular orbital of the organic transport layers. These results help to further understand the origin of the open circuit potential in perovskite solar cells, which is an important parameter that needs to be improved to further boost power conversion efficiencies.

We report herein a simple ligand-assisted reprecipitation method at room temperature to synthesize mixed-cation hybrid organic–inorganic perovskite nanocrystals with low structural dimensionality., We report herein a simple ligand-assisted reprecipitation method at room temperature to synthesize mixed-cation hybrid organic–inorganic perovskite nanocrystals with low structural dimensionality. The emission wavelength of iodide-based perovskites is thus tuned from the near-infrared to the red part of the visible spectrum. While this is mostly achieved in the literature by addition of bromide, we demonstrate here a controllable blueshift of the band gap by varying the chain length of the alkylammonium ligands. Furthermore, an antisolvent washing step was found to be crucial to purify the samples and obtain single-peak photoluminescence with a narrow linewidth. The so-formed nanocrystals exhibit high and stable photoluminescence quantum yields exceeding 90% over 500 hours, making these materials ideal for light-emitting applications.

Funding: C.L. thanks the Prof. & Mrs Purdie Bequests Scholarship and AstraZeneca for a PhD Studentship. The St Andrews researchers thank the Engineering and Physical Sciences Research Council (EP/M02105X/1 and EP/R035164/1) for financial support. A.K.P. acknowledges the Leverhulme Trust and the University of St Andrews for an Early Career Fellowship (ECF-2017-326). H.J.B. and M.S. acknowledge funding from the Spanish Ministry of Science, Innovation and Universities (MAT2017‐88821‐R and RYC-2016-21316, respectively). C.F.H. acknowledges the support of the Australian Research Council (ARC) Discovery grant scheme (DP200102947). We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu(P^P)(dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid state, with ΦPL of up to 35%, and in solution, with ΦPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the % Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes and light-emitting electrochemical cells (LECs), both of which showed moderate performance. Compared to the benchmark copper(I)-based LECs, [Cu(dnbp)(DPEPhos)]+ (maximum external quantum efficiency, EQEmax = 16%), complex 3 (EQEmax = 1.85%) showed a much longer device lifetime (t1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)]+ and complex 3 , respectively). The electrochemiluminescence (ECL) properties of several complexes were also studied, which, to the best of our knowledge, constitutes the first ECL study for heteroleptic copper(I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in a LEC. Postprint

We report a series of seven cationic heteroleptic copper(I) complexes of the form [Cu (P^P) (dmphen)]BF4, where dmphen is 2,9-dimethyl-1,10-phenanthroline and P^P is a diphosphine chelate, in which the effect of the bite angle of the diphosphine ligand on the photophysical properties of the complexes was studied. Several of the complexes exhibit moderately high photoluminescence quantum yields in the solid-state, with ΦPL of up to 35%, and in solution, with ΦPL of up to 98%. We were able to correlate the powder photoluminescence quantum yields with the %Vbur of the P^P ligand. The most emissive complexes were used to fabricate both organic light-emitting diodes (OLEDs) and light-emitting electrochemical calls (LECs), both of which showed moderate performance. Compared to the benchmark Cu(I)-based LECs, [Cu(dnbp)(DPEPhos)]+ (EQEmax = 16%), complex 3 (EQEmax = 1.85%) showed much longer device lifetime (t1/2 = 1.25 h and >16.5 h for [Cu(dnbp)(DPEPhos)]+ and complex 3, respectively). The electrochemiluminescent properties of several complexes were also studied which to the best of our knowledge constitutes the first ECL study for heteroleptic copper (I) complexes. Notably, complexes exhibiting more reversible electrochemistry were associated with higher annihilation ECL as well as better performance in an LEC device.

Herein, the long-term stability of vacuum-deposited methylammonium lead iodide (MAPbI(3)) perovskite solar cells (PSCs) with power conversion efficiencies (PCEs) of around 19% is evaluated. A low-temperature atomic layer deposition (ALD) Al2O3 coating is developed and used to protect the MAPbI(3) layers and the solar cells from environmental agents. The ALD encapsulation enables the MAPbI(3) to be exposed to temperatures as high as 150 degrees C for several hours without change in color. It also improves the thermal stability of the solar cells, which maintain 80% of the initial PCEs after aging for approximate to 40 and 37days at 65 and 85 degrees C, respectively. However, room-temperature operation of the solar cells under 1sun illumination leads to a loss of 20% of their initial PCE in 230h. Due to the very thin ALD Al2O3 encapsulation, X-ray diffraction can be performed on the MAPbI(3) films and completed solar cells before and after the different stress conditions. Surprisingly, it is found that the main effect of light soaking and thermal stress is a crystal reorientation with respect to the substrate from (002) to (202) of the perovskite layer, and that this reorientation is accelerated under illumination.

The interaction between semiconductor materials and electromagnetic fields resonating in microcavities or the light-matter coupling is of both fundamental and practical significance for improving the performance of various photonic technologies. The demonstration of light-matter coupling effects in the emerging perovskite-based optoelectronic devices via optical pumping and electrical readout (e.g., photovoltaics) and vice versa (e.g., light-emitting diodes), however, is still scarce. Here, we demonstrate the microcavity formation in vacuum-deposited methylammonium lead iodide (CH3NH3PbI3, MAPI) p-i-n photovoltaic devices fabricated between two reflecting silver electrodes. We tune the position of the microcavity mode across MAPI's absorption edge and study the effect on the microcavity absorption enhancement. Tuning the microcavity mode toward lower energies enhances the absorption of the lower energy photons and steepens the absorption onset which reduces the effective optical gap (E-g) of the devices. This leads to a reduction in the open circuit voltage deficit. The research leading to these results has received funding from the Spanish Ministry of Science, Innovation and Universities (MICIU, RTI2018-095362-A-I00, PCI2019-111829-2, CEX2019-000919-M, and EQC2018-004888-P) and the Comunitat Valenciana (IDIFEDER/2018/061 and PROMETEU/2020/077). C.D. acknowledges that the project that gave rise to these results received the support of a fellowship from “la Caixa” Foundation (ID 100010434, code LCF/BQ/ DI19/11730020). M.S. acknowledges the MICIU for his RyC contract. A.P. acknowledges his Grisolia Grant from the Comunitat Valenciana GRISOLIAP/2020/134.

Herein, the preparation of fully vacuum-processed bismuth triiodide solar cells with low annealing temperature is reported. Planar n-i-p devices are prepared using a thin compact SnO2 layer as the electron extraction layer and an electron blocking/hole extraction bilayer consisting of an intrinsic and doped organic hole-transport molecule. Using this configuration, herein, higher fill-factors and overall power conversion efficiencies than with conventional solution-processed hole transport materials are achieved.

In a short period of time, the rapid development of perovskite solar cells attracted a lot of attention in the science community with the record for power conversion efficiency being broken every year. Despite the fast progress in power conversion efficiency there are still many issues that need to be solved before starting large scale commercial applications, such as, among others, the difficult and costly synthesis and usage of toxic solvents for the deposition of hole transport materials (HTMs). We herein report new enamine-based charge transport materials obtained via a simple one step synthesis procedure, from commercially available precursors and without the use of expensive organometallic catalysts. The developed materials demonstrated rapid loss of mass during thermogravimetry analysis suggesting that they could be processed not only using solution processing but also via vacuum deposition. Furthermore, all HTMs demonstrated high charge carrier mobility with H2 possessing the highest mobility of 2.5 × 10−2 cm2 V−1 s−1 under strong electric fields. The investigated materials were employed in vacuum-deposited p–i–n perovskite solar cells and champion devices with enamine H2 demonstrate a PCE of 18.4%.

Halide perovskites have generated considerable research interest due to their excellent optoelectronic properties in the past decade. To ensure the formation of high-quality semiconductors, the deposition process for the perovskite film is a critical issue. Vacuum-based processing is considered to be a promising method, allowing, in principle, for uniform deposition on a large area. One of the benefits of vacuum processing is the control over the film composition through the use of quartz crystal microbalances (QCMs) that monitor the rates of the components in situ. In metal halide perovskites, however, one frequently employed component or precursor, CH

Heteroleptic [Cu(P^P)(N^N)][PF

For the majority of biosensors or biomedical devices, immobilization of the biorecognition element is a critical step for device function. To achieve longer lifetime devices and controllable functionalization, covalent immobilisation techniques are preferred over passive adhesion and electrostatic interactions. The rapidly emerging field of organic bioelectronics uses conducting polymers (or small molecules) as the active materials for transduction of the biological signal to an electronic one. While a number of techniques have been utilized to entrap or functionalize conducting polymers deposited by electro- or vapor phase polymerization, covalent functionalization of solution processed films, essential for realizing low cost or high throughput fabrication, has not been thoroughly investigated. In this study we show a versatile biofunctionalization technique for the solution processable conducting polymer poly(3,4-ethylenedioxythiophene) doped with poly(styrenesulfonate) PEDOT:PSS, which is a commercially available material, and has a record high conductivity. Addition of poly(vinyl alcohol) (PVA) into the solution with PEDOT:PSS provides a handle for subsequent silanization with a well-characterised silane reagent, allowing for covalent linkage of biological moieties onto PEDOT:PSS films. We show homogenous and large-scale biofunctionalization with polypeptides and proteins, as well as maintenance of the biological functionalities of the proteins. In addition, no deleterious effects are noted on the electronic or ionic transport properties of the conducting polymer films due to incorporation of the PVA.

Herein, the dehydration of a hydrogen molybdenum bronze (HYMoO3), converting it to molybdenum oxide (MoOX), is explored toward the development of perovskite solar cells (PSCs) for the first time. H0.11MoO3 bronze is synthesized, characterized, and deposited on indium tin oxide (ITO) under different concentrations and annealing conditions for in situ conversion into MoOX with appropriate oxygen vacancies. Vacuum‐deposited PSCs are fabricated using the as‐produced MoOX hole injection layers, achieving a power conversion efficiency of 17.3% (average) for the optimal device. The latter has its stability and reproducibility tested, proving the robustness and affordability of the developed hole transport layer in PSCs.

Fully inorganic cesium lead halide perovskites, such as CsPbI2Br, show enhanced thermal stability compared to hybrid ones and are being widely investigated as wide bandgap absorbers for tandem applications. Despite their simple stoichiometry, the preparation of highly crystalline and stable cesium lead halide thin films is not trivial. In general, high-efficiency solar cells based on solution-processed CsPbI2Br thin films are prepared by hightemperature annealing or the use of chemical additives. In this work, we use solvent-free synthesis to investigate the formation of CsPbI2Br in bulk or in thin films via mechanochemical synthesis and multiple-source vacuum deposition, respectively. We demonstrate the importance of fostering halide alloying in the vacuum processing of inorganic lead halide perovskites, which can be attained either by using mixed halide precursors or by increasing the number of precursors (and hence deposition sources). These strategies lead to highly oriented perovskite films even at room temperature, with improved optoelectronic properties. We obtained promising power conversion efficiencies of 8.3% for solar cells employing asdeposited perovskites (without any annealing) and 10.0% for devices based on CsPbI2Br annealed at low temperatures (150 °C). This study allowed us to highlight the most promising processes and strategies to further optimize the material deposition as well as the solar cell architecture. Hetero-structures for Efficient Luminescent Devices (HELD) REFERENCIA: 834431 PCIN-2019-111829-2

In perovskite solar cells, the choice of appropriate transport layers and electrodes is of great importance to guarantee efficient charge transport and collection, minimizing recombination losses. The possibility to sequentially process multiple layers by vacuum methods offers a tool to explore the effects of different materials and their combinations on the performance of optoelectronic devices. In this work, the effect of introducing interlayers and altering the electrode work function has been evaluated in fully vacuum-deposited perovskite solar cells. We compared the performance of solar cells employing common electron buffer layers such as bathocuproine (BCP), with other injection materials used in organic light-emitting diodes, such as lithium quinolate (Liq), as well as their combination. Additionally, high voltage solar cells were obtained using low work function metal electrodes, although with compromised stability. Solar cells with enhanced photovoltage and stability under continuous operation were obtained using BCP and BCP/Liq interlayers, resulting in an efficiency of approximately 19%, which is remarkable for simple methylammonium lead iodide absorbers.

Chirality-induced spin selectivity (CISS), whereby helical molecules polarize the spin of electrical current, is an intriguing effect with potential applications in nanospintronics. In this nascent field, the study of the CISS effect using paramagnetic chiral molecules, which could introduce another degree of freedom in controlling the spin transport, remains so far unexplored. To address this challenge, herein we propose the use of self-assembled monolayers (SAMs) of helical lanthanide-binding peptides. To elucidate the effect of the paramagnetic nuclei, monolayers of the peptide coordinating paramagnetic or diamagnetic ions are prepared. By means of spin-dependent electrochemistry, the CISS effect is demonstrated by cyclic voltammetry and electrochemical impedance measurements for both samples. Additionally, an implementation of the standard liquid-metal drop electron transport setup has been carried out, and this process helped to demonstrate the peptides' suitability for solid-state devices. Remarkably, the inclusion of a paramagnetic center in the peptide increases the spin polarization as was independently proved by different techniques. These findings permit the inclusion of magnetic biomolecules in the CISS field and pave the way to their implementation in a new generation of (bio)spintronic nanodevices.

Herein we demonstrate the dry synthesis of CsBi3I10 both as a free-standing material and in the form of homogeneous thin films, deposited by thermal vacuum deposition. Chemical and optical characterization shows high thermal stability, phase purity, and photoluminescence centered at 700 nm, corresponding to a bandgap of 1.77 eV. These characteristics make CsBi3I10 a promising low-toxicity material for wide bandgap photovoltaics. Nevertheless, the performance of this material as a semiconductor in solar cells remains rather limited, which can be at least partially ascribed to a low charge carrier mobility, as determined from pulsed-radiolysis time-resolved microwave conductivity. Further developments should focus on understanding and overcoming the current limitations in charge mobility, possibly by compositional tuning through doping and/or alloying, as well as optimizing the thin film morphology which may be another limiting factor. Perovskite Thin-film Photovoltaics (PERTPV) REFERENCIA: 763977 Hetero-structures for Efficient Luminescent Devices (HELD) REFERENCIA: 834431

The dual-source vacuum deposition of 2D perovskite films of the type PEA2PbX4, (PEA = phenethylammonium and X = I−, Br−, or a combination of both) is presented. Low-temperature deposited 2D perovskite films showed high crystallinity with the expected trend of bandgap as a function of halide type and concentration. Importantly, we observed an unavoidable halide cross-contamination among different deposition runs, as well as a strong dependence of the material quality on the type of halide precursors used. These findings should be taken into account in the development of vacuum processing for low-dimensional mixed halide perovskites.

New cycloplatinated N-heterocyclic carbene (NHC) compounds with chelate diphosphines (P^P) as ancillary ligands: [Pt(R-C^C*)(P^P)]PF6 (R = H, P^P = dppm (1A), dppe (2A), dppbz (3A); R = CN, P^P = dppm (1B), dppe (2B), dppbz (3B)) have been prepared from the corresponding starting material [{Pt(R-C^C*)(μ-Cl)}2] (R = H, A, R = CN, B) and fully characterized. The new compound A has been prepared by a stepwise protocol. The photophysical properties of 1A–3A and 1B–3B have been widely studied and supported by the time-dependent-density functional theory. These compounds show an efficient blue (dppe, dppbz) or cyan (dppm) emission in PMMA films (5 wt %), with photoluminescence quantum yield (PLQY) ranging from 30% to 87% under an argon atmosphere. This emission has been assigned mainly to transitions from 3ILCT [π(NHC) → π*(NHC)] excited states with some 3LL‘CT [π(NHC) → π*(P^P)] character. The electroluminescence of these materials in proof-of-concept solution-processed organic light-emitting diodes containing 3A and 3B as dopants was investigated. The CIE coordinates for devices based on 3A (0.22, 0.41) and 3B (0.24, 0.44) fit within the sky blue region., This work was supported by the Spanish Ministerio de Economia y Competitividad (Ministerio de Ciencia Innovación y Universidades)/FEDER (Project No. PGC2018-094749-B-I00) and by the Gobierno de Aragon (Grupo E17_17R: Quimica Inorganica y de los Compuestos Organo-metalicos, led by Prof. J. M. Casas) and FEDER 2014-2020 (Construyendo Europa desde Aragon).

Conductive metal-organic frameworks are opening new perspectives for the use of these porous materials for applications traditionally limited to more classical inorganic materials, such as their integration into electronic devices. This has enabled the development of chemiresistive sensors capable of transducing the presence of specific guests into an electrical response with good selectivity and sensitivity. By combining experimental data with computational modelling, a possible origin for the underlying mechanism of this phenomenon in ultrathin films (ca. 30 nm) of Cu-CAT-1 is described. ispartof: ANGEWANDTE CHEMIE-INTERNATIONAL EDITION vol:57 issue:46 pages:15086-15090 ispartof: location:Germany status: published

Hole transport layers HTLs are of fundamental importance in perovskite solar cells PSCs , as they must ensure an efficient and selective hole extraction, and ohmic charge transfer to the corresponding electrodes. In p i n solar cells, the ITO HTL is usually not ohmic, and an additional interlayer such as MoO3 is usually placed in between the two materials by vacuum sublimation. In this work, we evaluated the properties of the MoO3 TaTm TaTm is the HTL N4,N4,N4 amp; 8243;,N4 amp; 8243; tetra [1,1 amp; 8242; biphenyl] 4 yl [1,1 amp; 8242; 4 amp; 8242;,1 amp; 8243; terphenyl] 4,4 amp; 8243; diamine hole extraction interface by selectively annealing either MoO3 prior to the deposition of TaTm or the bilayer MoO3 TaTm without pre treatment on the MoO3 , at temperature ranging from 60 to 200 C. We then used these p contacts for the fabrication of a large batch of fully vacuum deposited PSCs, using methylammonium lead iodide as the active layer. We show that annealing the MoO3 TaTm bilayers at high temperature is crucial to obtain high rectification with low non radiative recombination, due to an increase of the electrode work function and the formation of an ohmic interface with TaTm

Metal-halide perovskites have become the most studied material for efficient next-generation solar cells, in part because of the possibility of depositing high quality semiconducting perovskites by simple solution-based methods. However, the majority of solvent systems implemented in literature for deposition of lead halide perovskites are hazardous to handle. Investigation of alternatives perovskite processing methods are hence key to safely upscale the perovskite photovoltaic manufacturing. In this manuscript we use the Hansen theory to find suitable nonhazardous solvents to solubilize two lead salts, PbBr2 and PbI2, used to fabricate the corresponding methylammonium (MA) lead halide perovskite films. The method is based on the use of the Hansen solubility parameters (HSPs) of a lead salt and a solvent to provide insight into whether interactions between them are favorable or not. We first studied the solubility properties of each lead salt (PbBr2 and PbI2) by determining experimentally their Hansen solubility spheres. Using these results, computer simulations allow us to determine compatible nonhazardous solvents with these two compounds in terms of solubility. We further investigated the use of a nonhazardous diester blend polar solvent to deposit MAPbI3 and MAPbBr3 thin films.