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Achieving the long-term stability of perovskite solar cells is arguably the most important challenge required to enable widespread commercialization. Understanding the perovskite crystallization process and its direct impact on device stability is critical to achieving this goal. The commonly employed dimethyl-formamide/dimethyl-sulfoxide solvent preparation method results in a poor crystal quality and microstructure of the polycrystalline perovskite films. In this work, we introduce a high-temperature dimethyl-sulfoxide-free processing method that utilizes dimethylammonium chloride as an additive to control the perovskite intermediate precursor phases. By controlling the crystallization sequence, we tune the grain size, texturing, orientation (corner-up versus face-up) and crystallinity of the formamidinium (FA)/caesium (FA)yCs1–yPb(IxBr1–x)3 perovskite system. A population of encapsulated devices showed improved operational stability, with a median T80 lifetime (the time over which the device power conversion efficiency decreases to 80% of its initial value) for the steady-state power conversion efficiency of 1,190 hours, and a champion device showed a T80 of 1,410 hours, under simulated sunlight at 65 °C in air, under open-circuit conditions. This work highlights the importance of material quality in achieving the long-term operational stability of perovskite optoelectronic devices.

As perovskite-based photovoltaics near commercialization, it is imperative to develop industrial-scale defect-passivation techniques. Vapor deposition is a solvent-free fabrication technique that is widely implemented in industry and can be used to fabricate metal-halide perovskite thin films. We demonstrate markably improved growth and optoelectronic properties for vapor-deposited [CH(NH2)2]0.83Cs0.17PbI3 perovskite solar cells by partially substituting PbI2 for PbCl2 as the inorganic precursor. We find the partial substitution of PbI2 for PbCl2 enhances photoluminescence lifetimes from 5.6 ns to over 100 ns, photoluminescence quantum yields by more than an order of magnitude, and charge-carrier mobility from 46 cm2/(V s) to 56 cm2/(V s). This results in improved solar-cell power conversion efficiency, from 16.4% to 19.3% for the devices employing perovskite films deposited with 20% substitution of PbI2 for PbCl2. Our method presents a scalable, dry, and solvent-free route to reducing nonradiative recombination centers and hence improving the performance of vapor-deposited metal-halide perovskite solar cells.

Charge transport in three-dimensional metal-halide perovskite semiconductors is due to a complex combination of ionic and electronic contributions, and its study is particularly relevant in light of their successful applications in photovoltaics as well as other opto- and microelectronic applications. Interestingly, the observation of field effect at room temperature in transistors based on solution-processed, polycrystalline, three-dimensional perovskite thin films has been elusive. In this work, we study the time-dependent electrical characteristics of field-effect transistors based on the model methylammonium lead iodide semiconductor and observe the drastic variations in output current, and therefore of apparent charge carrier mobility, as a function of the applied gate pulse duration. We infer this behavior to the accumulation of ions at the grain boundaries, which hamper the transport of carriers across the FET channel. This study reveals the dynamic nature of the field effect in solution-processed metal-halide perovskites and offers an investigation methodology useful to characterize charge carrier transport in such emerging semiconductors.

Vacuumdepositionis a solvent-free method suitable for growing thin films of metal halideperovskite(MHP) semiconductors. However, most reports of high-efficiencysolarcellsbased on suchvacuum-deposited MHP films incorporate solution-processed hole transport layers (HTLs), thereby complicating prospects of industrial upscaling and potentially affecting the overall devicestability. In this work, we investigate organometallic copper phthalocyanine (CuPc) and zinc phthalocyanine (ZnPc) as alternative, low-cost, and durable HTLs in all-vacuum-deposited solvent-free formamidinium-cesium lead triodide [CH(NH2)2]0.83Cs0.17PbI3(FACsPbI3)perovskitesolarcells. We elucidate that the CuPc HTL, when employed in an “inverted” p–i–nsolarcell configuration, attains asolar-to-electrical power conversion efficiency of up to 13.9%. Importantly, unencapsulated devices as large as 1 cm2exhibited excellent long-termstability, demonstrating no observable degradation in efficiency after more than 5000 h in storage and 3700 h under 85 °C thermal stressing in N2atmosphere.

Despite the incredible progress made, the highest efficiency perovskite solar cells are still restricted to small areas (

We introduce laser-assisted Time-Resolved SEM (TR-SEM), joining Scanning Electron Microscopy and laser light excitation, to probe the long-term temporal evolution of optically excited charge distributions at the surface of Metal Ammonium Lead Triiodide (MAPbI3) hybrid perovskite thin films. Laser-assisted TR-SEM relies on the optically induced local modification of Secondary Electron (SE) detection yield to provide mapping of photoexcited potentials and charge dynamics at surfaces, and qualifies as a complementary approach to near-field probe microscopies and nonlinear photoemission spectroscopies for photovoltage measurements. Real-time imaging of evolving field patterns are provided on timescales compatible with SEM scanning rates, so that temporal resolution in the millisecond range can be ultimately envisaged. MAPbI3 is an outstanding light-sensitive material candidate for applications in solar light harvesting and photovoltaics, also appealing as an active system for light generation. In this work, the real time temporal evolution of optically induced SE contrast patterns in MAPbI3 is experimentally recorded, both under illumination by a 405 nm blue laser and after light removal, showing the occurrence of modifications related to photoinduced positive charge fields at surface. The long term evolution of these surface fields are tentatively attributed to ion migration within the film, under the action of the illumination gradient and the hole collecting substrate. This optical excitation is fully reversible in MAPbI3 over timescales of hours and a complete recovery of the system occurs within days. Permanent irradiation damage of the material is avoided by operating the SEM at 5 keV of energy and 1–10 pA of primary current. Optical excitation is provided by intense above-bandgap illumination (up to 50 W/cm2). TR-SEM patterns show a strong dependence on the geometry of SE collection. Measurements are taken at different axial orientations of the sample with respect to the entrance of the in-column detection system of the SEM and compared with numerical modeling of the SE detection process. This enables to single out the information regarding the local potential distribution. Results are interpreted by combining data about the spectral distribution of emitted SEs with the configuration of the electric and magnetic fields in the specimen chamber. The present modeling sets a robust basis for the understanding of photoinduced SE electron contrast.

Space-charge-limited current (SCLC) measurements have been widely used to study the charge carrier mobility and trap density in semiconductors. However, their applicability to metal halide perovskites is not straightforward, due to the mixed ionic and electronic nature of these materials. Here, we discuss the pitfalls of SCLC for perovskite semiconductors, and especially the effect of mobile ions. We show, using drift-diffusion (DD) simulations, that the ions strongly affect the measurement and that the usual analysis and interpretation of SCLC need to be refined. We highlight that the trap density and mobility cannot be directly quantified using classical methods. We discuss the advantages of pulsed SCLC for obtaining reliable data with minimal influence of the ionic motion. We then show that fitting the pulsed SCLC with DD modeling is a reliable method for extracting mobility, trap, and ion densities simultaneously. As a proof of concept, we obtain a trap density of 1.3 × 1013 cm-3, an ion density of 1.1 × 1013 cm-3, and a mobility of 13 cm2 V-1 s-1 for a MAPbBr3 single crystal.

Perovskite solar cells deliver high efficiencies, but are often made from high-cost bespoke chemicals, such as the archetypical hole-conductor, 2,2′,7,7′-tetrakis(N,N-di-p-methoxy-phenylamine)-9-9′-spirobifluorene (spiro-OMeTAD). Herein, new charge-transporting carbazole-based enamine molecules are reported. The new hole conductors do not require chemical oxidation to reach high power conversion efficiencies (PCEs) when employed in n-type-intrinsic-p-type perovskite solar cells; thus, reducing the risk of moisture degrading the perovskite layer through the hydrophilicity of oxidizing additives that are typically used with conventional hole conductors. Devices made with these new undoped carbazole-based enamines achieve comparable PCEs to those employing doped spiro-OMeTAD, and greatly enhanced stability under 85 °C thermal aging; maintaining 83% of their peak efficiency after 1000 h, compared with spiro-OMeTAD-based devices that degrade to 26% of the peak PCE within 24 h. Furthermore, the carbazole-based enamines can be synthesized without the use of organometallic catalysts and complicated purification techniques, lowering the material cost by one order of magnitude compared with spiro-OMeTAD. As a result, we calculate that the overall manufacturing costs of future photovoltaic (PV) modules are reduced, making the levelized cost of electricity competitive with silicon PV modules.

Metal halide perovskite semiconductors have sprung to the forefront of research into optoelectronic devices and materials, largely because of their remarkable photovoltaic efficiency records above 25% in single-junction devices and 28% in tandem solar cells, achieved within a decade of research. Despite this rapid progress, ionic conduction within the semiconductor still puzzles the community and can have a significant impact on all metal halide perovskite-based optoelectronic devices because of its influence upon electronic and optoelectronic processes. This phenomenon thus also makes the interpretation of electrical characterization techniques, which probe the fundamental properties of these materials, delicate and complex. For example, space-charge limited current measurements are widely used to probe defect densities and carrier mobilities in perovskites. However, the influence of mobile ions upon these measurements is significant but has yet to be considered. Here we report the effect of mobile ions upon electronic conductivity during space-charge limited current measurements of MAPbBr3 single crystals and show that conventional interpretations deliver erroneous results. We introduce a pulsed-voltage space-charge limited current procedure to achieve reproducible current-voltage characteristics without hysteresis. From this revised pulsed current-voltage sweep, we elucidate a lower bound trap-density value of 2.8 ± 1.8 × 1012 cm-3 in MAPbBr3 single crystals. This work will lead to more accurate characterization of halide perovskite semiconductors and ultimately more effective device optimization.

To leverage the outstanding photonic qualities of lead halide hybrid perovskites under high optical irradiance, their reliability and temporal stability must be assessed. Time-resolved scanning electron microscopy unveils that when illuminating the free surface of methylammonium lead iodide (MAPbI3) films at 500 Sun in vacuum, a giant photopotential locally develops in tens of seconds, differently evolving depending on charge-selective substrates. It is reversible on timescales of minutes in the case of hole-transporting poly(3,4-ethylenedi- oxythiophene) polystyrene sulfonate, while more persistent effects occurs, on the timescale of hours, in the case of electron-transporting TiO2. In addition, films grown on TiO2 show irreversible decay of photoluminescence measured in situ and photoinduced alteration of the work function at some grain bounda- ries. Different responses at high irradiance are ascribable to contact-dependent and light-induced spatial redistribution of charged defects, either ions or local- ized dipoles. It is also clear that photoexcited charges play different roles in the photochemistry of systems, depending on selective contacts and they are likely to mediate diverse photoassisted redox reaction paths. The TiO2 layer may act as a photocatalyst, leading to MAPbI3 degradation.

The tunable bandgap of metal-halide perovskites has opened up the possibility of tandem solar cells with over 30% efficiency. Iodide-Bromide (I-Br) mixed-halide perovskites are crucial to achieve the optimum bandgap for such tandems. However, when the Br content is increased to widen the bandgap, cells fail to deliver the expected increase in open-circuit voltage (VOC). This loss in VOC has been attributed to photo-induced halide segregation. Here, we combine Fourier Transform Photocurrent Spectroscopy (FTPS) with detailed balance calculations to quantify the voltage loss expected from the halide segregation, providing a means to quantify the VOC losses arising from the formation of low bandgap iodide-rich phases during halide segregation. Our results indicate that, contrary to popular belief, halide segregation is not the dominant VOC loss mechanism in Br-rich wide bandgap cells. Rather, the loss is dominated by the relatively low initial radiative efficiency of the cells, which arises from both imperfections within the absorber layer, and at the perovskite/charge extraction layer heterojunctions. We thus identify that focussing on maximising the initial radiative efficiency of the mixed-halide films and devices is more important than attempting to suppress halide segeregation. Our results suggest that a VOC of up to 1.33 V is within reach for a 1.77 eV bandgap perovskite, even if halide segregation cannot be supressed

Stable perovskites with ionic salts Ionic liquids have been shown to stabilize organic-inorganic perovskite solar cells with metal oxide carrier-transport layers, but they are incompatible with more readily processible organic analogs. Lin et al. found that an ionic solid, a piperidinium salt, enhanced the efficiency of positive-intrinsic-negative layered perovskite solar cells with organic electron and hole extraction layers. Aggressive aging testing showed that this additive retarded segregation into impurity phases and pinhole formation in the perovskite layer. Science , this issue p. 96

The production of highly efficient single‐ and multijunction metal halide perovskite (MHP) solar cells requires careful optimization of the optical and electrical properties of these devices. Here, precise control of CH3NH3PbI3 perovskite layers is demonstrated in solar cell devices through the use of dual source coevaporation. Light absorption and device performance are tracked for incorporated MHP films ranging from ≈67 nm to ≈1.4 µm thickness and transfer‐matrix optical modeling is utilized to quantify optical losses that arise from interference effects. Based on these results, a device with 19.2% steady‐state power conversion efficiency is achieved through incorporation of a perovskite film with near‐optimum predicted thickness (≈709 nm). Significantly, a clear signature of photon reabsorption is observed in perovskite films that have the same thickness (≈709 nm) as in the optimized device. Despite the positive effect of photon recycling associated with photon reabsorption, devices with thicker (>750 nm) MHP layers exhibit poor performance owing to competing nonradiative charge recombination in a “dead‐volume” of MHP. Overall, these findings demonstrate the need for fine control over MHP thickness to achieve the highest efficiency cells, and accurate consideration of photon reabsorption, optical interference, and charge transport properties.

Metal-halide perovskites are outstanding materials for photovoltaics. Their long carrier lifetimes and diffusion lengths favor efficient charge collection, leading to efficiencies competing with established photovoltaics. These observations suggest an apparently low density of traps in the prototype methylammonium lead iodide (MAPbI3) contrary to the expected high defect density of a low-temperature, solution-processed material. Combining first-principles calculations and spectroscopic measurements we identify less abundant iodine defects as the source of photochemically active deep electron and hole traps in MAPbI3. The peculiar iodine redox chemistry leads, however, to kinetic deactivation of filled electron traps, leaving only short-living hole traps as potentially harmful defects. Under mild oxidizing conditions the amphoteric hole traps can be converted into kinetically inactive electron traps, providing a rationale for the defect tolerance of metal-halide perovskites. Bromine and chlorine doping of MAPbI3 also inactivate hole traps, possibly explaining the superior optoelectronic properties of mixed-halide perovskites.

Summary Multi-junction device architectures can increase the power conversion efficiency (PCE) of photovoltaic (PV) cells beyond the single-junction thermodynamic limit. However, these devices are challenging to produce by solution-based methods, where dissolution of underlying layers is problematic. By employing a highly volatile acetonitrile(CH3CN)/methylamine(CH3NH2) (ACN/MA) solvent-based perovskite solution, we demonstrate fully solution-processed absorber, transport, and recombination layers for monolithic all-perovskite tandem and triple-junction solar cells. By combining FA0.83Cs0.17Pb(Br0.7I0.3)3 (1.94 eV) and MAPbI3 (1.57 eV) junctions, we reach two-terminal tandem PCEs of more than 15% (steady state). We show that a MAPb0.75Sn0.25I3 (1.34 eV) narrow band-gap perovskite can be processed via the ACN/MA solvent-based system, demonstrating the first proof-of-concept, monolithic all-perovskite triple-junction solar cell with an open-circuit voltage reaching 2.83 V. Through optical and electronic modeling, we estimate the achievable PCE of a state-of-the-art triple-junction device architecture to be 26.7%. Our work opens new possibilities for large-scale, low-cost, printable perovskite multi-junction solar cells.

Many optoelectronic properties have been reported for lead halide perovskite polycrystalline films. However, ambiguities in the evaluation of these properties remain, especially for long-range lateral charge transport, where ionic conduction can complicate interpretation of data. Here we demonstrate a new technique to measure the long-range charge carrier mobility in such materials. We combine quasi-steady-state photo-conductivity measurements (electrical probe) with photo-induced transmission and reflection measurements (optical probe) to simultaneously evaluate the conductivity and charge carrier density. With this knowledge we determine the lateral mobility to be ∼2 cm2 V−1 s−1 for CH3NH3PbI3 (MAPbI3) polycrystalline perovskite films prepared from the acetonitrile/methylamine solvent system. Furthermore, we present significant differences in long-range charge carrier mobilities, from 2.2 to 0.2 cm2 V−1 s−1, between films of contemporary perovskite compositions prepared via different fabrication processes, including solution and vapour phase deposition techniques. Arguably, our work provides the first accurate evaluation of the long-range lateral charge carrier mobility in lead halide perovskite films, with charge carrier density in the range typically achieved under photovoltaic operation.

Metal halide perovskites have become a popular material system for fabricating photovoltaics and various optoelectronic devices. However, long-term reliability must be assured. Instabilities are manifested as light-induced ion migration and segregation, which can lead to material degradation. Discordant reports have shown a beneficial role of ion migration under illumination, leading to defect healing. By combining ab initio simulations with photoluminescence measurements under controlled conditions, we demonstrate that photo-instabilities are related to light-induced formation and annihilation of defects acting as carrier trap states. We show that these phenomena coexist and compete. In particular, long-living carrier traps related to halide defects trigger photoinduced material transformations, driving both processes. Defect formation can be controlled by blocking under-coordinated surface sites, which act as a defect reservoir. By use of a passivation strategy we are thus able to stabilize the perovskite layer, leading to improved optoelectronic material quality and enhanced photostability in solar cells. The photo-instability of perovskite solar cells is investigated and controlled by the use of a passivation strategy.

The recent success of lead halide perovskites is given by their optimal primary optoelectronic properties relevant for photovoltaic and, more in general, for optoelectronic applications. However, a lack of knowledge about the nature of instabilities currently represents a major challenge for the development of such materials. Here we investigate the luminescence properties of polycrystalline thin films of lead halide perovskites as a function of the excitation density and the environment. First we demonstrate that in an inert environment photoinduced formation of emissive sub-band gap defect states happens, independently of the chemical composition of the lead halide semiconductor, which quenches the band-to-band radiative emission. Carrier trapping occurs in the subnanosecond time regime, while trapped carriers recombine in a few microseconds. Then, we show that the presence of oxygen, even in a very small amount, is able to compensate such an effect.

Despite rapid developments in both photovoltaic and light-emitting device performance, the understanding of the optoelectronic properties of hybrid lead halide perovskites is still incomplete. In particular, the polarizability of the material, the presence of molecular dipoles, and their influence on the dynamics of the photoexcitations remain an open issue to be clarified. Here, we investigate the effect of an applied external electric field on the photoexcited species of CH3NH3PbI3 thin films, both at room temperature and at low temperature, by monitoring the photoluminescence (PL) yield and PL decays. At room temperature we find evidence for electric-field-induced reduction of radiative bimolecular carrier recombination together with motion of charged defects that affects the nonradiative decay rate of the photoexcited species. At low temperature (190 K), we observe a field-induced enhancement of radiative free carrier recombination rates that lasts even after the removal of the field. We assign this to field-induced alignment of the molecular dipoles, which reduces the vibrational freedom of the lattice and the associated local screening and hence results in a stronger electron-hole interaction.

State‐of‐the‐art perovskite‐based solar cells employ expensive, organic hole transporting materials (HTMs) such as Spiro‐OMeTAD that, in turn, limits the commercialization of this promising technology. Herein an HTM (EDOT‐Amide‐TPA) is reported in which a functional amide‐based backbone is introduced, which allows this material to be synthesized in a simple condensation reaction with an estimated cost of

Lead halide perovskite semiconductors have recently gained wide interest following their successful embodiment in solid-state photovoltaic devices with impressive power-conversion efficiencies, while offering a relatively simple and low-cost processability. Although the primary optoelectronic properties of these materials have already met the requirement for high-efficiency optoelectronic technologies, industrial scale-up requires more robust processing methods, as well as solvents that are less toxic than the ones that have been commonly used so successfully on the lab-scale. Here we report a fast, room-temperature synthesis of inks based on CsPbBr3 perovskite nanocrystals using short, low-boiling-point ligands and environmentally friendly solvents. Requiring no lengthy post-synthesis treatments, the inks are directly used to fabricate films of high optoelectronic quality, exhibiting photoluminescence quantum yields higher than 30% and an amplified spontaneous emission threshold as low as 1.5 μJ cm−2. Finally, we demonstrate the fabrication of perovskite nanocrystal-based solar cells, with open-circuit voltages as high as 1.5 V. Despite their impressive performance, more efforts are required to develop industrially scalable perovskite solar cells from less toxic solvents. Towards that aim, this study presents the use of colloidal nanoparticle inks for room-temperature fabrication of CsPbBr3 solar cells.

Many of the best performing solar cells based on perovskite-halide light absorbers use TiO2 as an electron selective contact layer. However, TiO2 usually requires high temperature sintering, is related to electrical instabilities in perovskite solar cells, and causes cell performance degradation under full solar spectrum illumination. Here we demonstrate an alternative approach based on the modification of transparent conductive oxide electrodes with self-assembled siloxane-functionalized fullerene molecules, eliminating TiO2 or any other additional electron transporting layer. We demonstrate that these molecules spontaneously form a homogenous monolayer acting as an electron selective layer on top of the fluorine doped tin oxide (FTO) electrode, minimizing material consumption. We find that the fullerene-modified FTO is a robust, chemically inert charge selective contact for perovskite based solar cells, which can reach 15% of stabilised power conversion efficiency in a flat junction device architecture using a scalable, low temperature, and reliable process. In contrast to TiO2, devices employing a molecularly thin functionalized fullerene layer show unaffected performance after 67 h of UV light exposure.

Perovskites have been demonstrated in solar cells with a power conversion efficiency of well above 20%, which makes them one of the strongest contenders for next generation photovoltaics. While there are no concerns about their efficiency, very little is known about their stability under illumination and load. Ionic defects and their migration in the perovskite crystal lattice are some of the most alarming sources of degradation, which can potentially prevent the commercialization of perovskite solar cells (PSCs). In this work, we provide direct evidence of electric field-induced ionic defect migration and we isolate their effect on the long-term performance of state-of-the-art devices. Supported by modelling, we demonstrate that ionic defects, migrating on timescales significantly longer (above 10(3) s) than what has so far been explored (from 10(-1) to 10(2) s), abate the initial efficiency by 10-15% after several hours of operation at the maximum power point. Though these losses are not negligible, we prove that the initial efficiency is fully recovered when leaving the device in the dark for a comparable amount of time. We verified this behaviour over several cycles resembling day/night phases, thus probing the stability of PSCs under native working conditions. This unusual behaviour reveals that research and industrial standards currently in use to assess the performance and the stability of solar cells need to be adjusted for PSCs. Our work paves the way for much needed new testing protocols and figures of merit specifically designed for PSCs.

Solution-processed organometal trihalide perovskite solar cells are attracting increasing interest, leading to high performances over 15% in thin film architectures. Here, we probe the presence of sub gap states in both solid and mesosuperstructured perovskite films and determine that they strongly influence the photoconductivity response and splitting of the quasi-Fermi levels in films and solar cells. We find that while the planar perovskite films are superior to the mesosuperstructured films in terms of charge carrier mobility (in excess of 20 cm(2) V(-1) s(-1)) and emissivity, the planar heterojunction solar cells are limited in photovoltage by the presence of sub gap states and low intrinsic doping densities.

One of the greatest attributes of metal halide perovskite solar cells is their surprisingly low loss in potential between bandgap and open-circuit voltage, despite the fact that they suffer from a non-negligible density of sub gap defect states. Here, we use a combination of transient and steady state photocurrent and absorption spectroscopy to show that CH3NH3PbI3 films exhibit a broad distribution of electron traps. We show that the trapped electrons recombine with free holes unexpectedly slowly, on microsecond time scales, relaxing the limit on obtainable open-circuit voltage (VOC) under trap-mediated recombination conditions. We find that the observed VOCs in such perovskite solar cells can only be rationalized by considering the slow trap mediated recombination mechanism identified in this work. Our results suggest that existing processing routes may be good enough to enable open circuit voltages approaching 1.3 V in ideal devices with perfect contacts.

Solar cells based on perovskite-halide light absorbers have a unique set of characteristics that could help alleviate the global dependence on fossil fuels for energy generation. They efficiently convert sunlight into electricity using Earth-abundant raw materials processed from solution at low temperature. Thus, they offer potential for cost reductions compared with or in combination with other photovoltaic technologies. Nevertheless, to fully exploit the potential of perovskite-halides, several important challenges must be overcome. Given the nature of the materials — relatively soft ionic solids — one of these challenges is the understanding and control of their defect structures. Currently, such understanding is limited, restricting the power conversion efficiencies of these solar cells from reaching their thermodynamic limit. This Review describes the state of the art in the understanding of the origin and nature of defects in perovskite-halides and their impact on carrier recombination, charge-transport, band alignment, and electrical instability, and provides a perspective on how to make further progress. Understanding of defect physics in perovskite-halide semiconductors is essential to control the effects of structural and chemical defects on the performance of perovskite solar cells. Petrozza and Ball review the current knowledge of defects in these materials.

Reduction in the operating voltage of organic field-effect transistors (OFETs) is sought for their successful implementation into future portable and low-power electronic applications. Here we demonstrate OFETs with operation below 2 V enabled by the use of self-assembled monolayer (SAM) gate dielectrics with high geometrical capacitances. A high surface energy monolayer is chosen to allow processing of small molecule semiconductors from solution. Impedance spectroscopy measurements of metal-insulator-semiconductor devices suggest the geometrical capacitance of the alumina-SAM dielectric can reach ~1 P F/cm 2 when accumulating charge at the semiconductor-insulator interface. Atomic force microscopy images reveal that the glass substrates and the SAM-functionalized aluminum gate electrode display significant roughness. Despite this, mobilities of 0.02 cm 2 /Vs are demonstrated. These results represent an important step towards low-power solution processable electronics. Keywords: organic semiconductor, organic field-effect transistor, organic thin-film transistor, self-assembled monolayer, low-voltage, metal-insulator-semiconductor, atomic force microscopy

The family of soluble fullerene derivatives comprises a widely studied group of electron transporting molecules for use in organic electronic and optoelectronic devices. For electronic applications, electron transporting (n-channel) materials are required for implementation into organic complementary logic circuit architectures. To date, few soluble candidate materials have been studied that fulfill the stringent requirements of high carrier mobility and air stability. Here we present a study of three soluble fullerenes with varying electron affinity to assess the impact of electronic structure on device performance and air stability. Through theoretical and experimental analysis of the electronic structure, characterization of thin-film structure, and characterization of transistor device properties we find that the air stability of the present series of fullerenes not only depends on the absolute electron affinity of the semiconductor but also on the disorder within the thin-film. © 2011 American Institute of Physics.

The development of ruthenium-free sensitizers which absorb light over a broad range of the solar spectrum is important for improving the power conversion efficiency of dye-sensitized solar cells. Here we study three chemically tailored porphyrin-based dyes. We show that by fusing the porphyrin core to an anthracene unit, we can extend the conjugation length and lower the optical gap, shifting the absorption spectrum into the near-infrared (NIR). All three dyes were tested in dye-sensitized solar cells, using both titanium dioxide and tin dioxide as the electron-transport material. Solar cells incorporating the anthracene-fused porphyrin dye exhibit photocurrent collection at wavelengths up to about 1100 nm, which is the longest reported for a porphyrin-based system. Despite extending the photon absorption bandwidth, device efficiency is found to be low, which is a common property of cells based on porphyrin dyes with NIR absorption. We show that in the present case the efficiency is reduced by inefficient electron injection into the oxide, as opposed to dye regeneration, and highlight some important design considerations for panchromatic sensitizers. © 2012 The Royal Society of Chemistry.

We demonstrate electron and hole-transporting low-voltage transistors based on self-assembling monolayer (SAM) gate dielectrics and solution processed organic small-molecule semiconductors. The studied SAMs include methyl and carboxylic acid terminated molecules. Compared to methyl terminated alkylphosphonic acids, carboxylic acid terminated SAMs are found to exhibit increased surface energy. This enables solution processing of a wide range of small molecules onto the dielectric for the fabrication of low-voltage transistors. Using these transistors we demonstrate complementary inverters operating at voltages

A series of materials for field effect transistors (FETs), with pyrene at the core and four substituted thiophene arms of different lengths (1-3 thiophene units) have been synthesized using Suzuki cross-coupling reactions and characterized by 1H NMR, 13C NMR, UV-vis absorption, emission spectroscopy, and in one case by X-ray crystallography. © 2010 Elsevier B.V.

The electrical stability of low-voltage organic transistors based on phosphonic acid self-assembled monolayer (SAM) dielectrics is investigated using four different semiconductors. The threshold voltage shift in these devices shows a stretched-exponential time dependence under continuous gate bias with a relaxation time in the range of 10(3)-10(5) s, at room temperature. Differences in the bias instability of transistors based on different self-assembled monolayers and organic semiconductors suggest that charge trapping into localized states in the semiconductor is not the only mechanism responsible for the observed instability. By applying 1-5 s long programming voltage pulses of 2-3 V in amplitude, a large reversible threshold voltage shift can be produced. The retention time of the programmed state was measured to be on the order of 30 h. The combination of low voltage operation and relatively long retention times makes these devices interesting for ultra-low power memory applications.

We report temperature resolved UV-vis absorption and spectral photocurrent response measurements of MAPbI3 thin films and solar cells, together with ab initio simulations, to investigate the changes in material properties occurring across the tetragonal to cubic phase transition. We find that the MAPbI3 band-gap does not abruptly change when exceeding the tetragonal to cubic transition temperature, but it rather monotonically blue-shifts following the same temperature evolution observed within the tetragonal phase. Car–Parrinello molecular dynamics simulations demonstrate that the high temperature phase corresponds on average to the expected symmetric cubic structure assigned from XRD measurements, but that the system strongly deviates from such a structure in the sub-picosecond time scale. Thus, on the time scale of electronic transitions, the material seldom experiences a cubic environment, rather an increasingly distorted tetragonal one. This result explains the absence of dramatic changes in the optical of MAPbI3 across the explored temperature range of 270–420 K, which could have important consequences for the practical uptake of perovskite solar cells.

A study was conducted to demonstrate the fabrication of high-performance zinc oxide (ZnO) transistors and circuits using spray pyrolysis (SP) deposition technique in ambient atmosphere. The method was found to be compatible with large-area deposition and potentially addressed the issues of manufacturing cost and high operating voltages. High mobility n-channel thin-film transistors (TFTs) based on ZnO deposited at substrate temperatures in the range of 200-500 °C were realized to demonstrate the method. Semiconductor deposition was performed entirely in ambient atmosphere without the need for special precautions. It was demonstrated that the as-deposited ZnO films were of high quality and uniformity, while the SP was compatible with a number of solution-processible self-assembled monolayer (SAM) dielectrics. ZnO transistors operating at significantly low voltages were demonstrated by combining SP with soluble SAM dielectrics.

Charge extracting layers play a key role in the elimination of hysteresisfromJ–Vcharacteristics of inverted hybrid perovskite solar cells. Methanofullerene electron extracting layers stabilize short‐circuit photocurrents from the very firstJ–Vscan, while preconditioning cycles are needed to stabilize the open‐circuit voltage owing to interaction between migrating iodide ions and the charge extraction layer.

Organic–inorganic metal halide perovskite solar cells have emerged in the past few years to promise highly effi cient photovoltaic devices at low costs. Here, temperature-sensitive core–shell Ag@TiO 2 nanoparticles are successfully incorporated into perovskite solar cells through a low-temperature processing route, boosting the measured device efficiencies up to 16.3%. Experimental evidence is shown and a theoretical model is developed which predicts that the presence of highly polarizable nanoparticles enhances the radiative decay of excitons and increases the reabsorption of emitted radiation, representing a novel photon recycling scheme. The work elucidates the complicated subtle interactions between light and matter in plasmonic photovoltaic composites. Photonic and plasmonic schemes such as this may help to move highly efficient perovskite solar cells closer to the theoretical limiting efficiencies.

Metal-halide perovskite light-absorbers have risen to the forefront of photovoltaics research offering the potential to combine low-cost fabrication with high power-conversion efficiency. Much of the development has been driven by empirical optimisation strategies to fully exploit the favourable electronic properties of the absorber layer. To build on this progress, a full understanding of the device operation requires a thorough optical analysis of the device stack, providing a platform for maximising the power conversion efficiency through a precise determination of parasitic losses caused by coherence and absorption in the non-photoactive layers. Here we use an optical model based on the transfer-matrix formalism for analysis of perovskite-based planar heterojunction solar cells using experimentally determined complex refractive index data. We compare the modelled properties to experimentally determined data, and obtain good agreement, revealing that the internal quantum efficiency in the solar cells approaches 100%. The modelled and experimental dependence of the photocurrent on incidence angle exhibits only a weak variation, with very low reflectivity losses at all angles, highlighting the potential for useful power generation over a full daylight cycle.

It has been proposed that organic-inorganic perovskites may provide the ``disruptive'' technology needed to deliver widespread and affordable solar power. To reach this goal, a detailed understanding of their material properties and behavior in working devices is needed. The authors present a robust model that explains charge recombination in the presence of subgap trap states in these materials. This study provides concrete predictions regarding the most important material parameters for improved solar-cell performance of these perovskites.

Polystyrene spheres are used to template TiO2 with a single layer of 300 nm wells which are infilled with PbS quantum dots to form a heterojunction solar cell. The porous well device has an efficiency of 5.7% while the simple planar junction is limited to 3.2%. Using a combination of optical absorption and photocurrent transient decay measurement we determined that the performance enhancement comes from a combination of enhanced optical absorption and increased carrier lifetime.

Perovskite solar cells have rapidly risen to the forefront of emerging photovoltaic technologies, exhibiting rapidly rising efficiencies. This is likely to continue to rise, but in the development of these solar cells there are unusual characteristics that have arisen, specifically an anomalous hysteresis in the current-voltage curves. We identify this phenomenon and show some examples of factors that make the hysteresis more or less extreme. We also demonstrate stabilized power output under working conditions and suggest that this is a useful parameter to present, alongside the current-voltage scan derived power conversion efficiency. We hypothesize three possible origins of the effect and discuss its implications on device efficiency and future research directions. Understanding and resolving the hysteresis is essential for further progress and is likely to lead to a further step improvement in performance.

We report the low-frequency resonant Raman spectrum of methylammonium lead-iodide, a prototypical perovskite for solar cells applications, on mesoporous Al2O3. The measured spectrum assignment is assisted by DFT simulations of the Raman spectra of suitable periodic and model systems. The bands at 62 and 94 cm-1 are assigned respectively to the bending and to the stretching of the Pb-I bonds, and are thus diagnostic modes of the inorganic cage. We also assign the librations of the organic cations at 119 and 154 cm-1. The broad, unstructured 200-400 cm-1 features are assigned to the torsional mode of the methylammonium cations, which we propose as a marker of the orientational disorder of the material. Our study provides the basis to interpret the Raman spectra of organohalide perovskites, which may allow one to further understand the properties of this important class of materials in relation to their full exploitation in solar cells. © 2013 American Chemical Society.

The highest efficiencies in solution-processable perovskite-based solar cells have been achieved using an electron collection layer that requires sintering at 500 °C. This is unfavorable for low-cost production, applications on plastic substrates, and multijunction device architectures. Here we report a low-cost, solution-based deposition procedure utilizing nanocomposites of graphene and TiO2 nanoparticles as the electron collection layers in meso-superstructured perovskite solar cells. The graphene nanoflakes provide superior charge-collection in the nanocomposites, enabling the entire device to be fabricated at temperatures no higher than 150 °C. These solar cells show remarkable photovoltaic performance with a power conversion efficiency up to 15.6%. This work demonstrates that graphene/metal oxide nanocomposites have the potential to contribute significantly toward the development of low-cost solar cells. This work was funded by EPSRC, UK. The authors thank Jin Zhang for experimental assistance. J.T.-W.W. would like to acknowledge Swire Educational Trust for supporting his DPhil study at Oxford. J.M.B. and H.J.S. acknowledge the European Union Seventh Framework Programme under the SANS project (grant 246124), and DESTINY project (grant 316494). A.A. thanks the EPSRC APEX project for financial support. E.M.B, I.M.-S., and J.B. acknowledge support by a project from Generalitat Valenciana (PROMETEO/2009/058).

Organometal trihalide perovskite solar cells offer the promise of a low-cost easily manufacturable solar technology, compatible with large-scale low-temperature solution processing. Within 1 year of development, solar-to-electric power-conversion efficiencies have risen to over 15%, and further imminent improvements are expected. Here we show that this technology can be successfully made compatible with electron acceptor and donor materials generally used in organic photovoltaics. We demonstrate that a single thin film of the low-temperature solution-processed organometal trihalide perovskite absorber CH3NH3PbI3-xClx, sandwiched between organic contacts can exhibit devices with power-conversion efficiency of up to 10% on glass substrates and over 6% on flexible polymer substrates. This work represents an important step forward, as it removes most barriers to adoption of the perovskite technology by the organic photovoltaic community, and can thus utilize the extensive existing knowledge of hybrid interfaces for further device improvements and flexible processing platforms.