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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.

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.

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.

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.

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.

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.

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%.

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.

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.

Efficient organic light-emitting diodes (OLEDs) can be obtained using multilayered architectures where the processes of charge injection, transport and recombination are separated and optimized in each layer. Processing these structures from solution requires strategies to avoid redissolution or damage of the previously deposited layers. Several reports have demonstrated the development of cross-linkable hole transport materials, while less literature describes the synthesis and applications of such wide bandgap host materials for multilayered OLEDs. In this work we introduce a cross-linkable derivative of 9-(4-(10-phenylanthracene-9-yl)phenyl)-9H-carbazole incorporating styrene moieties (SPhPC) which can be efficiently cross-linked via radical polymerization. We present the synthesis and characterization of SPhPC, as well as its application as the host in the light-emitting layer to prove the concept of solution processed blue OLEDs.

Heteroleptic [Cu(P^P)(N^N)][PF6] complexes, where N^N is a halo-substituted 2,2'-bipyridine (bpy) and P^P is either bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9- dimethylxanthene (xantphos) have been synthesized and investigated. To stabilize the tetrahedral geometry of the copper(I) complexes, the steric demands of the bpy ligands have been increased by introducing 6- or 6,6'-halo-substituents in 6,6'-dichloro-2,2'-bipyridine (6,6'-Cl2bpy), 6-bromo-2,2'- bipyridine (6-Brbpy) and 6,6'-dibromo-2,2'-bipyridine (6,6'-Br2bpy). The solid-state structures of [Cu(POP)(6,6'-Cl2bpy)][PF6], [Cu(xantphos)(6,6'-Cl2bpy)][PF6].CH2Cl2, [Cu(POP)(6-Brbpy)][PF6] and [Cu(xantphos)(6-Brbpy)][PF6].0.7Et2O obtained from single crystal X-ray diffraction are described including the pressure dependence of the structure of [Cu(POP)(6-Brbpy)][PF6]. The copper(I) complexes with either POP or xantphos and 6,6'-Cl2bpy, 6-Brbpy and 6,6'-Br2bpy are orange-to-red emitters in solution and yellow-to-orange emitters in the solid state, and their electrochemical and photophysical properties have been evaluated with the help of density functional theory (DFT) calculations. The emission properties are strongly influenced by the substitution pattern that largely affects the geometry of the emitting triplet state. [Cu(POP)(6,6'-Cl2bpy)][PF6] and [Cu(xantphos)(6,6'-Cl2bpy)][PF6] show photoluminescence quantum yields of 15 and 17%, respectively, in the solid state, and these compounds were tested as luminophores in light-emitting electrochemical cells (LECs). The devices exhibit orange electroluminescence and very short turn-on times (

The preparation of densely-packed films from hybrid lead halide perovskite nanocrystals is not trivial, as during assembly into the solid state both the charge transport and photoluminescence can be substantially altered. The objective of the present study was to retain the pre-engineered confined morphologies of hybrid lead halide perovskite nanocrystals in densely-packed solid films by using short organic ligands. Therefore, the roles of the organic ligands would be to provide stable colloids and a good passivation of the nanoparticle surface, as well as to enable the efficient assembly of the nanoparticles in the solid state. We report here an effective and reproducible process to deposit lead halide perovskite nanoparticle films from colloidal CH3NH3PbBr3 nanoparticles short organic ligands. Remarkably, we demonstrate that nanoparticle solid films with thicknesses of hundreds of nanometres can retain high photoluminescence, with a quantum yield of 80%, and still sustain charge transport.

Methylammonium lead mixed-halide perovskites MAPb(BrxI1–x)3 are promising materials for the preparation of tandem devices. When exposed to light, MAPb(BrxI1–x)3 segregates in iodide- and bromide-rich phases, limiting the achievable photovoltage and hence the attainable device efficiency. To date only solution-processed mixed-halide perovskites have been demonstrated. We present fully vacuum-deposited mixed-halide perovskite thin films with band gap of 1.72 and 1.87 eV, prepared by controlling the deposition rates of the different halide precursors. When used in thin-film devices, these materials lead to power conversion efficiencies of 15.9 and 10.5%, respectively, which are among the highest reported to date for these types of wide band gap absorbers.

Summary High-quality semiconducting perovskites can be easily synthesized through several methods. The ease of fabrication has favored the adoption of lab-scale solution-processing techniques, which have yielded the highest performing devices. Most of these processes, however, are not directly applicable to larger scale and volume preparations, hindering the consolidation and market entry of this technology. Vapor-based methods, a mature technology widely adopted in the coating and semiconductor industry, could change this trend. Their application to perovskite solar cells includes a large amount of fabrication approaches, offering versatility in the employed materials as well as in the characteristics of the resulting perovskite films. It is thus essential to review the fundamentals of perovskite vapor-related techniques in order to put their real potential and challenges into perspective.

The mechanism responsible for the extremely long photoluminescence (PL) lifetimes observed in many lead halide perovskites is still under debate. While the presence of trap states is widely accepted, the process of electron detrapping back to the emissive state has been mostly ignored, especially from deep traps as these are typically associated with nonradiative recombination. Here, we study the photophysics of methylammonium lead bromide perovskite nanocrystals (PNCs) with a photoluminescence quantum yield close to unity. We show that the lifetime of the spontaneous radiative recombination in PNCs is as short as 2 ns, which is expected considering the direct bandgap character of perovskites. All longer (up to microseconds) PL decay components result from the rapid reversible processes of multiple trapping and detrapping of carriers with a slow release of the excitation energy through the spontaneous emission channel. As our modeling shows, the trap (dark) and excitonic states are coupled by the trapping...

Trap-assisted recombination, despite being lower as compared with traditional inorganic solar cells, is still the dominant recombination mechanism in perovskite solar cells (PSCs) and limits their efficiency. We investigate the attributes of the primary trap assisted recombination channels (grain boundaries and interfaces) and their correlation to defect ions in PSCs. We achieve this by using a validated device model to fit the simulations to the experimental data of efficient vacuum-deposited p-i-n and n-i-p CH3NH3PbI3 solar cells, including the light intensity dependence of the open circuit voltage and fill factor. We find that, despite the presence of traps at interfaces and grain boundaries (GBs), their neutral (when filled with photogenerated charges) disposition along with the long-lived nature of holes leads to the high performance of PSCs. The sign of the traps (when filled) is of little importance in efficient solar cells with compact morphologies (fused GBs, low trap density). On the other hand, solar cells with noncompact morphologies (open GBs, high trap density) are sensitive to the sign of the traps and hence to the cell preparation methods. Even in the presence of traps at GBs, trap-assisted recombination at interfaces (between the transport layers and the perovskite) is the dominant loss mechanism. We find a direct correlation between the density of traps, the density of mobile ionic defects, and the degree of hysteresis observed in the current voltage (J-V) characteristics. The presence of defect states or mobile ions not only limits the device performance but also plays a role in the J-V hysteresis.

Planar perovskite solar cells using organic charge selective contacts were fabricated. In a vacuum deposited perovskite-based solar cell, dopant and additive free triazatruxene as the hole transport layer was introduced for device fabrication. High open-circuit voltage of 1090 mV was obtained using methylammonium lead iodide (Eg=1.55 eV) as light harvesting material, thus representing a loss of only 460 mV which is in close vicinity of mature silicon technology (400 mV). The devices showed a very competitive photovoltaic performance, monochromatic incident photon-to-electron conversion efficiency of 80% and the power conversion efficiencies in excess of 15% were measured with a negligible degree of hysteresis.

In this work we study the band gap variation and properties of the perovskite compound Cs0.15FA0.85Pb(BrxI1−x)3 as a function of the halide composition, with the aim of developing an efficient complementary absorber for MAPbI3 in all-perovskite tandem devices. We have found the perovskite stoichiometry Cs0.15FA0.85Pb(Br0.7I0.3)3 to be a promising candidate, thanks to its band gap of approximately 2 eV. Single junction devices using this perovskite absorber lead to a maximum PCE of 11.5%, among the highest reported for solar cells using perovskites with a band gap wider than 1.8 eV.

Quasi-2D perovskites with the BA : MA molar ratio equal to 3 : 3 show a remarkable PLQY exceeding 80%, thanks to the use of an electron donor as the passivating agent. These films have been applied in LEDs that exhibit high brightness exceeding 1000 cd m−2 and current efficiencies >3 cd A−1.

In this work, we study the effect of voltage bias on the optoelectronic behavior of methylammonium lead iodide planar diodes. Upon biasing the diodes with a positive voltage, the turn-on voltage of the electroluminescence diminishes and its intensity substantially increases. This behavior is reminiscent of that observed in light-emitting electrochemical cells (LECs), single-layer electroluminescent devices in which the charge injection is assisted by the accumulation of ions at the electrode interface. Because of this mechanism, performances are largely independent from the work function of the electrodes. The similarities observed between planar perovskite diodes and LECs suggest that mobile ions in the perovskite do play an important rote in device operation. Besides enhanced electroluminescence, biasing these devices can also result in improved photovoltaic performance.

Thin-film solar cells suffer from various types of recombination, of which leakage current usually dominates at lower voltages. Herein, we demonstrate first a three-order reduction of the shunt loss mechanism in planar methylammonium lead iodide perovskite solar cells by replacing the commonly used hole transport layer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) with a better hole-selective polyarylamine. As a result, these cells exhibit superior operation under reduced light conditions, which we demonstrate for the extreme case of moonlight irradiance, at which open-circuit voltages of 530 mV can still be obtained. By the shunt removal we also observe the VOC to drop to zero after as long as 2 h after the light has been switched off. Second, at higher illumination intensities the dominant losses in the PEDOT:PSS-based cell are ascribed to surface recombination and are also proven to be substantially minimized by instead employing the polyarylamine. We attribute the reduced shunt and surface recombination to the far better suited semiconductor character of the polyarylamine, compared to that of PEDOT:PSS, efficiently blocking electrons from recombining at this electrode.

Non-toxic alternatives to lead halide perovskites are highly sought after for applications in optoelectronics. Blue-luminescent materials are especially demanded as they could be used to prepare white light-emitting diodes, with important potential applications in lighting systems. However, wide bandgap blue emitters with high photoluminescence quantum yields (PLQY) are typically more difficult to obtain as compared to green- or red-emitting ones. Here, we prepared two series of inorganic cesium copper halides, with the general formulas Cs3Cu2X5 and CsCu2X3 (X = Cl, Br, I, and mixtures thereof) by dry mechanochemical synthesis at room temperature. X-ray diffraction demonstrates quantitative conversion of binary precursors into the desired ternary structures and good halide mixing in single-phase compounds. We identified Cs3Cu2I5 as the most promising material as it maintains blue luminescence centered at 442 nm with high PLQY (>40%) after several days in air (Cs3Cu2Cl5 shows significantly higher PLQY over 80% but is unstable in air). Based on this, we fabricated homogeneous and pinhole-free Cs3Cu2I5 thin films by thermal single-source vacuum deposition. Crystalline phase and photoluminescence are maintained in the thin films, validating that these low-toxicity materials can be synthesized and processed by fully solvent-free routes for a widespread implementation in optoelectronic devices.

Summary Genetically Encoded Ca2+ Indicators (GECIs) are extensively used to study organelle Ca2+ homeostasis, although some available probes are still plagued by a number of problems, e.g., low fluorescence intensity, partial mistargeting, and pH sensitivity. Furthermore, in the most commonly used mitochondrial Förster Resonance Energy Transfer based-GECIs, the donor protein ECFP is characterized by a double exponential lifetime that complicates the fluorescence lifetime analysis. We have modified the cytosolic and mitochondria-targeted Cameleon GECIs by (1) substituting the donor ECFP with mCerulean3, a brighter and more stable fluorescent protein with a single exponential lifetime; (2) extensively modifying the constructs to improve targeting efficiency and fluorescence changes caused by Ca2+ binding; and (3) inserting the cDNAs into adeno-associated viral vectors for in vivo expression. The probes have been thoroughly characterized in situ by fluorescence microscopy and Fluorescence Lifetime Imaging Microscopy, and examples of their ex vivo and in vivo applications are described., Graphical Abstract, Highlights • Donor substitution in a mitochondrial Ca2+ sensor improves photo-physical properties • Mitochondria-targeting sequence amelioration enhances the sensor localization • Donor substitution allows FLIM-FRET analysis, with a compensation for pH bias • The performance of the sensor is improved in situ, ex vivo, and in vivo, Biological Sciences Tools; Cell Biology; Optical Imaging

Low-dimensional (quasi-) 2D perovskites are being extensively studied in order to enhance the stability and the open-circuit voltage of perovskite solar cells. Up to now, thin 2D perovskite layers on the surface and/or at the grain boundaries of 3D perovskites have been deposited solely by solution processing, leading to unavoidable intermixing between the two phases. In this work, we report the fabrication of 2D/3D/2D perovskite heterostructures by dual-source vacuum deposition, with the aim of studying the interaction between the 3D and 2D phases as well as the charge transport properties of 2D perovskites in neat 2D/3D interfaces. Unlike what is normally observed in solution-processed 3D/2D systems, we found a reduced charge transport with no direct evidence of surface passivation, in spite of larger open-circuit voltage. This is likely due to a nonfavorable orientation of the 2D perovskite with respect to methylammonium lead iodide and to the formation of 2D phases with very low dimensionality (pure 2D).

It is widely accepted that a long photoluminescence (PL) lifetime in metal halide perovskite films is a crucial and favorable factor, as it ensures a large charge diffusion length leading to a high power conversion efficiency (PCE) in solar cells. It has been recently found that vacuumevaporated CH3NH3PbI3 (eMAPI) films show very short PL lifetimes of several nanoseconds. The corresponding solar cells, however, have high photovoltage (>1.1 V) and PCEs (up to 20%). We rationalize this apparent contradiction and show that eMAPI films are characterized by a very high diffusion coefficient D, estimated from modeling the PL kinetics to exceed 1 cm2/s. Such high D values are favorable for long diffusion length as well as fast transport of carriers to film surfaces, where they recombine nonradiatively with surface recombination velocity S ∼ 104 cm/s. Possible physical origins leading to the high D values are also discussed It is widely accepted that a long photoluminescence (PL) lifetime in metal halide perovskite films is a crucial and favorable factor, as it ensures a large charge diffusion length leading to a high power conversion efficiency (PCE) in solar cells. It has been recently found that vacuumevaporated CH3NH3PbI3 (eMAPI) films show very short PL lifetimes of several nanoseconds. The corresponding solar cells, however, have high photovoltage (>1.1 V) and PCEs (up to 20%). We rationalize this apparent contradiction and show that eMAPI films are characterized by a very high diffusion coefficient D, estimated from modeling the PL kinetics to exceed 1 cm2/s. Such high D values are favorable for long diffusion length as well as fast transport of carriers to film surfaces, where they recombine nonradiatively with surface recombination velocity S ∼ 104 cm/s. Possible physical origins leading to the high D values are also discussed

Methylammonium lead triiodide (MAPI) has emerged as a high-performance photovoltaic material. Common understanding is that at room temperature it adopts a tetragonal phase and it only converts to the perfect cubic phase around 50-60 ºC. Most MAPI films are prepared using a solution-based coating process, yet they can also be obtained by vapor phase deposition methods. Vapor phase processed MAPI films have significantly different characteristics compared to their solvent processed analogous, such as a relatively small crystal grain sizes and short excited state lifetimes. Yet solar cells based on vapor phase processed MAPI films exhibit high power conversion efficiencies. Surprisingly, after detailed characterization we find that our vapor phase processed MAPI films adopt a cubic crystal structure at room temperature that is stable for weeks, even in ambient atmosphere. Furthermore, we demonstrate that by tuning the deposition rates of both precursors during co-deposition it is possible to vary the perovskite phase from cubic to tetragonal at room temperature. Our finding challenges the common belief that MAPI is only stable in tetragonal phase at room temperature. Additionally, these findings can be used to explain the somewhat unexpected high performance of solar cells based on vacuum processed MAPI films with sub 100 nm grain sizes and excited state lifetimes < 100 nanoseconds.

We have synthesized fifteen inorganic and hybrid organic-inorganic non-toxic A3Bi2X9 compounds (A = K+, Rb+, Cs+, CH3NH3+ and HC(NH2)2+; X = I−, Br−, Cl−) through dry mechanochemistry. We demonstrate that this synthetic method is very well suited to prepare compounds from poorly soluble precursors, allowing thus the preparation of so far unreported compounds. X-ray diffraction analysis demonstrates the high crystallinity of the so-formed ternary bismuth halides. Furthermore, we show that, through substitution of the A-cation and X-anion, the bandgap of these compounds can be tuned to absorb throughout the whole visible spectrum. As-prepared powders of Cs3Bi2Br9 and Cs3Bi2I9 without any passivating agents show room-temperature photoluminescence covering the visible spectrum from 450 nm to 800 nm, making them especially promising for white-light emission.

Vacuum-deposition of perovskite solar cells can achieve efficiencies rivalling solution-based methods and it allows for more complex device stacks. MoO3 has been used to enhance carrier extraction to the transparent bottom electrode in a p-i-n configuration, here we show that by inserting an organic charge transport molecule it can also be used on the top of a perovskite absorber in a n-i-p configuration. This strategy enables the first vacuum-deposited perovskite solar cells with metal oxides as charge transporting layers for both electrons and holes leading to power conversion efficiency > 19 %.

Phase‐pure CsSnI3, FASnI3, Cs(PbSn)I3, FA(PbSn)I3 perovskites (FA = formamidinium = HC(NH2)2+) as well as the analogous so‐called vacancy‐ordered double perovskites Cs2SnI6 and FA2SnI6 are mechanochemically synthesized. The addition of SnF2 is found to be crucial for the synthesis of Cs‐containing perovskites but unnecessary for hybrid ones. All compounds show an absorption onset in the near‐infrared (NIR) region, which makes them especially relevant for photovoltaic applications. The addition of Pb(II) and SnF2 is crucial to improve the electronic properties in 3D Sn(II)‐based perovskites, in particular their charge carriers mobility (≈0.2 cm2 Vs−1) which is enhanced upon reduction of the dark carrier conductivity. Stokes‐shifted photoluminescence is observed on dry powders of Sn(II)‐based perovskites, which makes these materials promising for light‐emitting and sensing applications. Thermal stability of all compounds is examined, revealing no significant degradation up to at least 200 °C. This meets the requirements for standard operation conditions of most optoelectronic devices and is potentially compatible with thermal vacuum deposition of polycrystalline thin films.

​This document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Applied Materials & Interfaces, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acsami.9b04991, A variety of experiments on vacuum-deposited methylammonium lead iodide perovskite solar cells are presented, including JV curves with different scan rates, light intensity-dependent open-circuit voltage, impedance spectra, intensity-modulated photocurrent spectra, transient photocurrents, and transient voltage step responses. All these experimental data sets are successfully reproduced by a charge drift-diffusion simulation model incorporating mobile ions and charge traps using a single set of parameters. While previous modeling studies focused on a single experimental technique, we combine steady-state, transient, and frequency-domain simulations and measurements. Our study is an important step toward quantitative simulation of perovskite solar cells, leading to a deeper understanding of the physical effects in these materials. The analysis of the transient current upon voltage turn-on in the dark reveals that the charge injection properties of the interfaces are triggered by the accumulation of mobile ionic defects. We show that the current rise of voltage step experiments allow for conclusions about the recombination at the interface. Whether one or two mobile ionic species are used in the model has only a minor influence on the observed effects. A delayed current rise observed upon reversing the bias from +3 to -3 V in the dark cannot be reproduced yet by our drift-diffusion model. We speculate that a reversible chemical reaction of mobile ions with the contact material may be the cause of this effect, thus requiring a future model extension. A parameter variation is performed in order to understand the performance-limiting factors of the device under investigation.

We studied the effect of the charge transport layers in p-i-n perovskite solar cells using vacuum deposited methylammonium lead iodide thin-film absorbers. While solution-processed perovskite films are frequently deposited directly on PEDOT:PSS leading to good solar cell performances, in some cases even to very good Voc values, we show that in devices employing vacuum deposited MAPbI3 perovskites, the removal of the polyTPD electron blocker substantially reduces the photovoltaic behavior. This is indicative of rather different charge transport properties in the vacuum deposited MAPbI3 perovskites compared to those prepared from solution. On the other hand, we investigated the use of ionic interlayers as a possible alternative to low work function electrodes, whose reactivity towards air and moisture compromises the device stability. Two different electron extraction materials were evaluated as interlayers between the fullerene electron transport layer and a silver electrode, in particular a perylenediimide derivative and a conjugated polyelectrolyte. By studying the photovoltaic response and the electroluminescence properties of planar diodes using the ionic films and comparing them with devices employing barium, we found that such ionic interlayers can successfully replace the use of reactive electrodes, since they facilitate the electron extraction while reducing the non-radiative recombination at the electron transport interface.

In this work, we demonstrate flexible solution processed light emitting electrochemical cells (LECs) which use single-walled carbon nanotubes (SWCNTs) films as the substrate. The SWCNTs were synthesized by an integrated aerosol method and dry-transferred on the plastic substrates at room temperature. The addition of a screen printed poly (3,4-ethylene dioxythiophene) doped with poly (styrene sulfonate) (PEDOT:PSS) film onto the nanostructured electrode further homogenizes the surface and enlarges the work function, enhancing the hole injection into the active layer. By using an efficient phosphorescent ionic transition metal complex (iTMC) as the active material, efficacies up to 9 cd/A have been obtained. These values are among the highest reported so far for light-emitting diodes employing CNTs as transparent electrode.

In this work we study the effect of the addition of lithium salts to light-emitting electrochemical cells (LECs), and in particular the effect of the lithium counterion. We found that the chosen lithium salts can substantially improve the device turn-on time as well as the overall lifetime, with respect to reference LECs using the pure emitter. A correlation between the lithium counterion and the corresponding device performance is established, and efficient LECs with lifetimes approaching 2000 hours are presented.

Methylammonium lead bromide nanoparticles are synthetized with a new ligand (11-aminoundecanoic acid hydrobromide) by a non-template method. Upon dispersion in toluene they show a remarkable photoluminescence quantum yield of 80%. In addition, the bifunctional ligand allows anchoring of the nanoparticles on a variety of conducting and semiconducting surfaces, showing bright photoluminescence with a quantum yield exceeding 50%. This opens a path for the simple and inexpensive preparation of multilayer light-emitting devices. NRF (Natl Research Foundation, S’pore) ASTAR (Agency for Sci., Tech. and Research, S’pore) Accepted version

Vacuum evaporated perovskite solar cells with a power conversion efficiency of 15% have been characterized using hyperspectral luminescence imaging. Hyperspectral luminescence imaging is a novel technique that offers spectrally resolved photoluminescence and electroluminescence maps (spatial resolution is 2 micrometer) on an absolute scale. This allows, using the generalized Planck’s law, the construction of absolute maps of the depth-averaged quasi-Fermi level splitting (Δμ), which determines the maximum achievable open circuit voltage (Voc) of the solar cells. In a similar way, using the generalized reciprocity relations the charge transfer efficiency of the cells can be obtained from the hyperspectral images. Very strong inhomogeneity, both in quasi-Fermi level splitting (Δμ) and in charge transfer efficiency, are found in these vacuum deposited perovskite solar cells. This implies that these efficient solar cells are still far from perfect as many areas in the device do not or only partially participate in the photon to electron conversion processes.

Methylammonium lead halide perovskites have emerged as high performance photovoltaic materials. Most of these solar cells are prepared via solution-processing and record efficiencies (>20%) have been obtained employing perovskites with mixed halides and organic cations on (mesoscopic) metal oxides. Here, we demonstrate fully vacuum deposited planar perovskite solar cells by depositing methylammonium lead iodide in between intrinsic and doped organic charge transport molecules. Two configurations, one inverted with respect to the other, p-i-n and n-i-p, are prepared and optimized leading to planar solar cells without hysteresis and very high efficiencies, 16.5% and 20%, respectively. It is the first time that a direct comparison between these two opposite device configurations has been reported. These fully vacuum deposited solar cells, employing doped organic charge transport layers, validate for the first time vacuum based processing as a real alternative for perovskite solar cell preparation.

Five different commercially available fullerenes are evaluated as hole blocking/electron transporting materials in p–i–n methylammonium lead iodide perovskite solar cells using a vacuum deposited perovskite absorber layer. A significant enhancement of the solar cell performance can be obtained by selecting a suitable fullerene derivative. Open-circuit voltages as high as 1.11 volts are obtained leading to a power conversion efficiency of 14.6%.

Herein the mechanochemical synthesis of inorganic as well as hybrid organic-inorganic monohalide perovskites with tunable bandgaps is reported. It is shown that the bandgap bowing known for iodide mixed Sn-Pb perovskites is also present in the pure bromide analogous. This results in technologically very interesting materials with bandgaps in the range of 1.7-1.9 eV. Similar bandgap perovskites are typically achieved by mixing two halides that are prone to segregate over time. This limits the achievable open circuit voltage. For monohalide perovskites this problem is eliminated, making these materials especially promising wide bandgap absorbers for tandem solar cells. Perovskite Thin-film Photovoltaics (PERTPV) Hetero-structures for Efficient Luminescent Devices (HELD)

A series of copper(I) complexes of the type [Cu(HN-xantphos)(N^N)][PF6] and [Cu(BnN-xantphos)(N^N)][PF6], in which N^N = bpy, Mebpy and Me2bpy, HN-xantphos = 4,6-bis(diphenylphosphanyl)-10H-phenoxazine and BnN-xantphos = 10-benzyl-4,6-bis(diphenylphosphanyl)-10H-phenoxazine is described. The single crystal structures of [Cu(HN-xantphos)(Mebpy)][PF6] and [Cu(BnN-xantphos)(Me2bpy)][PF6] confirm the presence of N^N and P^P chelating ligands with the copper(I) atoms in distorted coordination environments. Solution electrochemical and photophysical properties of the BnN-xantphos-containing compounds (for which the highest-occupied molecular orbital is located on the phenoxazine moiety) are reported. The first oxidation of [Cu(BnN-xantphos)(N^N)][PF6] occurs on the BnN-xantphos ligand. Time-dependent density functional theory (TD-DFT) calculations have been used to analyze the solution absorption spectra of the [Cu(BnN-xantphos)(N^N)][PF6] compounds. In the solid-state, the compounds show photoluminescence in the range 518-555 nm for [Cu(HN-xantphos)(N^N)][PF6] and 520-575 nm for [Cu(BnN-xantphos)(N^N)][PF6] with a blue-shift on going from bpy to Mebpy to Me2bpy. [Cu(BnN-xantphos)(Me2bpy)][PF6] exhibits a solid-state photoluminescence quantum yield of 55% with an excited state lifetime of 17.4 µs. Bright light-emitting electrochemical cells were obtained using this complex, and we show that the electroluminescence quantum yield can be enhanced by using less conducting hole injection layers

A cross-linkable triazatruxene that leads to insoluble films upon thermal annealing at temperatures compatible with flexible substrates is presented. The films were used as the hole transporting and electron blocking layer in partially solution processed phosphorescent organic light-emitting diodes, reaching power conversion efficiencies of 24 lm W−1, an almost 50% improvement compared to the same OLEDs without the cross-linkable hole transporting layer.

One of the most important properties of semiconductors is the possibility of controlling their electronic behavior via intentional doping. Despite the unprecedented progress in the understanding of hybrid metal halide perovskites, extrinsic doping of perovskite remains nearly unexplored and perovskite–perovskite homojunctions have not been reported. Here we present a perovskite–perovskite homojunction obtained by vacuum deposition of stoichiometrically tuned methylammonium lead iodide (MAPI) films. Doping is realized by adjusting the relative deposition rates of MAI and PbI2, obtaining p-type (MAI excess) and n-type (MAI defect) MAPI. The successful stoichiometry change in the thin films is confirmed by infrared spectroscopy, which allows us to determine the MA content in the films. We analyzed the resulting thin-film junction by cross-sectional scanning Kelvin probe microscopy (SKPM) and found a contact potential difference (CPD) of 250 mV between the two differently doped perovskite layers. Planar diode...

We report a series of [Cu(P^P)(N^N)][PF6] complexes with P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 6-methoxy-2,2′-bipyridine (MeObpy), 6-ethoxy-2,2′-bipyridine (EtObpy), 6-phenyloxy-2,2′-bipyridine (PhObpy), 6-methylthio-2,2′-bipyridine (MeSbpy), 6-ethylthio-2,2′-bipyridine (EtSbpy) and 6-phenylthio-2,2′-bipyridine (PhSbpy). The single crystal structures of all twelve compounds have been determined and confirm chelating modes for each N^N and P^P ligand, and a distorted tetrahedral geometry for copper(I). For the xantphos-containing complexes, the asymmetrical bpy ligand is arranged with the 6-substituent lying over the xanthene ‘bowl’. The compounds have been characterized in solution by 1H, 13C and 31P NMR spectroscopies, and their photophysical and electrochemical properties are described. They are yellow emitters and solid samples show photoluminescence quantum yields in the range up to 38%, with emission lifetimes ≤10.2 μs. On going from powder to frozen Me-THF, the excited state lifetimes increase which might suggest the presence of thermally activated delayed fluorescence (TADF). All the compounds have been tested in light-emitting electrochemical cells (LECs). Bright and stable LECs are obtained with complexes containing alkoxy- or phenyloxy-substituted ligands, making this family of compounds very relevant for the future development of copper-based electroluminescent devices.