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Hardware neural networks could perform certain computational tasks orders of magnitude more energy-efficiently than conventional computers. Artificial neurons are a key component of these networks and are currently implemented with electronic circuits based on capacitors and transistors. However, artificial neurons based on memristive devices are a promising alternative, owing to their potentially smaller size and inherent stochasticity. But despite their promise, demonstrations of memristive artificial neurons have so far been limited. Here we demonstrate a fully on-chip artificial neuron based on microscale electrodes and halide perovskite semiconductors as the active layer. By connecting a halide perovskite memristive device in series with a capacitor, the device demonstrates stochastic leaky integrate-and-fire behavior, with an energy consumption of 20 to 60 pJ per spike, lower than that of a biological neuron. We simulate populations of our neuron and show that the stochastic firing allows the detection of sub-threshold inputs. The neuron can easily be integrated with previously-demonstrated halide perovskite artificial synapses in energy-efficient neural networks.

The migration of mobile ions through the metal halide perovskite layer is still one of the main reasons for the poor stability of perovskite solar cells, LEDs, and photodetectors. To characterize mobile ions in the perovskite layer, time- and frequency-based electrical measurements are promising techniques. However, the presence of transport layers complicates their interpretation, limiting the information about mobile ions that can be extracted, and it is not clear how different features in frequency- and time-domain measurements relate to mobile ions. Here, we characterize a transport-layer-free device with capacitance frequency, capacitance transient, and current transient measurements in the dark, under illumination, and at different temperatures. We extract characteristic ionic signatures from the measurements, which we reproduce with drift-diffusion simulations for each technique. This allows us to explain the origins of the different ionic signatures, advancing our understanding of how electronic characterization techniques can be used to study the properties of mobile ions., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

The efficient conduction of mobile ions in halide perovskites is highly promising for artificial synapses (or memristive devices), devices with a conductivity that can be varied by applying a bias voltage. Here we address the challenge of downscaling halide perovskite-based artificial synapses to achieve low energy consumption and allow high-density integration. We fabricate halide perovskite artificial synapses in a back-contacted architecture to achieve microscale devices despite the high solubility of halide perovskites in polar solvents that are commonly used in lithography. The energy consumption of a conductance change of the device is as low as 640 fJ, among the lowest reported for two-terminal halide perovskite artificial synapses so far. Moreover, the high resistance of the device up to hundreds of megaohms, low operating voltage of 100 mV and simple two-terminal architecture enable implementation in highly dense crossbar arrays. These arrays could potentially show orders of magnitude lower energy consumption for computation compared to conventional digital computers., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Quasi-2D perovskites have been pivotal in recent efforts to stabilize perovskite solar cells. Despite the stability boost provided when these materials are introduced in perovskite solar cells, little is known about the intrinsic light and environmental stability of quasi-2D perovskites. In this study, we characterize the photostability of exfoliated quasi-2D perovskite single crystals in air using photoluminescence, infrared, X-ray fluorescence, and energy-dispersive X-ray spectroscopy. Photoexcitation leads to severe material loss with oxygen as a prerequisite for material breakdown. The effect can be traced to the formation of reactive oxygen species, as demonstrated by increases in the photostability under oxygen-free conditions. We show the effect of combined passivation steps, showcasing the stability enhancement offered by 2D-capping layers in combination with an oxygen-free atmosphere. Our results reveal that the stability of illuminated quasi-2D perovskites depends critically on oxygen exposure, highlighting the importance of oxygen-blocking passivation strategies for stable 2D perovskite-based devices., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Hybrid metal halide perovskites have demonstrated remarkable performances in modern photovoltaics, although their stabilities remain limited. We assess the capacity to advance their properties by relying on interfacial modulators featuring helical chirality based on P , M -(1-methylene-3-methyl-imidazolium)[6]helicene iodides. We investigate their characteristics, demonstrating comparable charge injection for enantiomers and the racemic mixture. Overall, they maintain the resulting photovoltaic performance while improving operational stability, challenging the role of helical chirality in the interfacial modulation of perovskite solar cells., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Temporal dynamics of confined optical fields can provide valuable insights into light-matter interactions in complex optical systems, going beyond their frequency-domain description. Here, we present a new experimental approach based on interferometric autocorrelation (IAC) that reveals the dynamics of optical near-fields enhanced by collective resonances in periodic metasurfaces. We focus on probing the resonances known as waveguide-plasmon polaritons, which are supported by plasmonic nanoparticle arrays coupled to a slab waveguide. To probe the resonant near-field enhancement, our IAC measurements make use of enhanced two-photon excited luminescence (TPEL) from semiconductor quantum dots deposited on the nanoparticle arrays. Thanks to the incoherent character of TPEL, the measurements are only sensitive to the fundamental optical fields and therefore can reveal clear signatures of their coherent temporal dynamics. In particular, we show that the excitation of a high- Q collective resonance gives rise to interference fringes at time delays as large as 500 fs, much greater than the incident pulse duration (150 fs). Based on these signatures, the basic characteristics of the resonances can be determined, including their Q factors, which are found to exceed 200. Furthermore, the measurements also reveal temporal beating between two different resonances, providing information on their frequencies and their relative contribution to the field enhancement. Finally, we present an approach to enhance the visibility of the resonances hidden in the IAC curves by converting them into spectrograms, which greatly facilitates the analysis and interpretation of the results. Our findings open up new perspectives on time-resolved studies of collective resonances in metasurfaces and other multiresonant systems., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Ion migration has been reported to be one of the main reasons for hysteresis in the current-voltage ( J - V ) characteristics of perovskite solar cells. We investigate the interplay between ionic conduction and hysteresis types by studying Cs 0.05 (FA 0.83 MA 0.17 ) 0.95 Pb(I 0.9 Br 0.1 ) 3 triple-cation perovskite solar cells through a combination of impedance spectroscopy (IS) and sweep-rate-dependent J - V curves. By comparing polycrystalline devices to single-crystal MAPbI 3 devices, we separate two defects, β and γ, both originating from long-range ionic conduction in the bulk. Defect β is associated with a dielectric relaxation, while the migration of γ is influenced by the perovskite/hole transport layer interface. These conduction types are the causes of different types of hysteresis in J - V curves. The accumulation of ionic defects at the transport layer is the dominant cause for observing tunnel-diode-like characteristics in the J - V curves. By comparing devices with interface modifications at the electron and hole transport layers, we discuss the species and polarity of involved defects.

High-harmonic generation is the frequency upconversion of an intense femtosecond infrared laser in a material. In condensed-phase high-harmonic generation, laser-driven currents of coherently excited charge carriers map the electronic structure onto the emitted light. This promises a thus far scarcely explored potential of condensed-phase time-resolved high-harmonic spectroscopy for probing carrier dynamics. Here, we realize this potential and use time-resolved solid-state high-harmonic spectroscopy from a laser-excited methylammonium lead bromide (MAPbBr 3 ) thin film, a key material in perovskite solar cells, for measuring carrier cooling and relaxation on femto- and picosecond time scales. Through comparison with transient absorption, we show the links between carrier dynamics and experimental observables of generated harmonics. By highlighting and understanding the interplay of these dynamics, we demonstrate transient optical control over the emission of solid-state high-harmonic generation in MAPbBr 3 .

Competing Interests: The authors declare no competing financial interest.

Silicon solar cells are operating close to the theoretical maximum efficiency limit. To increase their efficiency beyond this limit, it is necessary to decrease energy losses occurring for high-energy photons. A sensitizing layer of singlet-fission material can in principle double the current generated by high-energy photons, and significantly reduce energy losses from high-energy photons within the solar cell. Here, we construct a model of such a solar cell, using Si(111) surfaces and tetracene. To increase the energy transfer between the two layers, a series of tetracene derivatives was synthesized, and the molecules were covalently attached onto the silicon surface as a seed layer. Using X-ray diffraction, a shift in crystal structure and ordering of the tetracene close to the seed layer can be observed. Unfortunately, the effect on the energy transfer was limited, showing a need for further investigations into the effect of the seed layer.

Two-dimensional (2D) lead halide perovskites are an exciting class of materials currently being extensively explored for photovoltaics and other optoelectronic applications. Their ionic nature makes them ideal candidates for solution processing into both thin films and nanostructured crystals. Understanding how 2D lead halide perovskite crystals form is key towards full control over their physical properties, which may enable new physical phenomena and devices. Here, we investigate the effects of the Pb oxidation state of the initial inorganic precursor on the growth of pure-phase ( n = 1) - Popper 2D perovskite BA 2 PbI 4 in single-step synthesis. We examine the different crystallisation routes in exposing PbO 2 and PbI 2 powders to a BAI : IPA organo-halide solution, by combining in situ optical microscopy, UV-VIS spectroscopy and time-resolved high performance liquid chromatography. So far, works using PbO 2 to synthesise 3D LHPs introduce a preceding step to reduce PbO 2 into either PbO or PbI 2 . In this work, we find that BA 2 PbI 4 is directly formed when exposing PbO 2 to BAI : IPA without the need for an external reducing agent. We explain this phenomenon by the spontaneous reduction/oxidation of PbO 2 /BAI that occurs under iodine-rich conditions. We observe differences in the final morphology (rectangles vs. octagons) and nanocrystal growth rate, which we explain through the different chemistry and iodoplumbate complexes involved in each case. As such, this work spans the horizon of usable lead precursors and offers a new turning knob to control crystal growth in single-step LHP synthesis.

Lead-halide perovskites offer excellent properties for lighting and display applications. Nanopatterning perovskite films could enable perovskite-based devices with designer properties, increasing their performance and adding novel functionalities. We demonstrate the potential of nanopatterning for achieving light emission of a perovskite film into a specific angular range by introducing periodic sol-gel structures between the injection and emissive layer by using substrate conformal imprint lithography (SCIL). Structural and optical characterization reveals that the emission is funnelled into a well-defined angular range by optical resonances, while the emission wavelength and the structural properties of the perovskite film are preserved. The results demonstrate a flexible and scalable approach to the patterning of perovskite layers, paving the way toward perovskite LEDs with designer angular emission patterns.

Inorganic-Organic lead halide materials have been recognized as potential high-energy X-ray detectors because of their high quantum efficiencies and radiation hardness. Surprisingly little is known about whether the same is true for extreme-ultraviolet (XUV) radiation, despite applications in nuclear fusion research and astrophysics. We used a table-top high-harmonic generation setup in the XUV range between 20 and 45 eV to photoexcite methylammonium lead bromide (MAPbBr 3 ) and measure its scintillation properties. The strong absorbance combined with multiple carriers being excited per photon yield a very high carrier density at the surface, triggering photobleaching reactions that rapidly reduce the emission intensity. Concurrent to and in spite of this photobleaching, a recovery of the emission intensity as a function of dose was observed. X-ray photoelectron spectroscopy and X-ray diffraction measurements of XUV-exposed and unexposed areas show that this recovery is caused by XUV-induced oxidation of MAPbBr 3 , which removes trap states that normally quench emission, thus counteracting the rapid photobleaching caused by the extremely high carrier densities. Furthermore, it was found that preoxidizing the sample with ozone was able to prolong and improve this intensity recovery, highlighting the impact of surface passivation on the scintillation properties of perovskite materials in the XUV range., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Layered Dion-Jacobson (DJ) and Ruddlesden-Popper (RP) hybrid perovskites are promising materials for optoelectronic applications due to their modular structure. To fully exploit their functionality, mechanical stimuli can be used to control their properties without changing the composition. However, the responsiveness of these systems to pressure compatible with practical applications (<1 GPa) remains unexploited. Hydrostatic pressure is used to investigate the structure-property relationships in representative iodide and bromide DJ and RP 2D perovskites based on 1,4-phenylenedimethylammonium (PDMA) and benzylammonium (BzA) spacers in the 0-0.35 GPa pressure range. Pressure-dependent X-ray scattering measurements reveal that lattices of these compositions monotonically shrink and density functional theory calculations provide insights into the structural changes within the organic spacer layer. These structural changes affect the optical properties; the most significant shift in the optical absorption is observed in (BzA) 2 PbBr 4 under 0.35 GPa pressure, which is attributed to an isostructural phase transition. Surprisingly, the RP and DJ perovskites behave similarly under pressure, despite the different binding modes of the spacer molecules. This study provides important insights into how the manipulation of the crystal structure affects the optoelectronic properties of such materials, whereas the reversibility of their response expands the perspectives for future applications., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Lead-halide perovskite (LHP) nanocrystals have proven themselves as an interesting material platform due to their easy synthesis and compositional versatility, allowing for a tunable band gap, strong absorption, and high photoluminescence quantum yield (PLQY). This tunability and performance make LHP nanocrystals interesting for optoelectronic applications. Patterning active materials like these is a useful way to expand their tunability and applicability as it may allow more intricate designs that can improve efficiencies or increase functionality. Based on a technique for II-VI quantum dots, here we pattern colloidal LHP nanocrystals using electron-beam lithography (EBL). We create patterns of LHP nanocrystals on the order of 100s of nanometers to several microns and use these patterns to form intricate designs. The patterning mechanism is induced by ligand cross-linking, which binds adjacent nanocrystals together. We find that the luminescent properties are somewhat diminished after exposure, but that the structures are nonetheless still emissive. We believe that this is an interesting step toward patterning LHP nanocrystals at the nanoscale for device fabrication., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

In the research ecosystem's quest towards having deployable organic light-emitting diodes with higher-energy emission ( e.g. , blue light), we advocate focusing on fluorescent emitters, due to their relative stability and colour purity, and developing design strategies to significantly improve their efficiencies. We propose that all triplet-triplet annihilation upconversion (TTA-UC) emitters would make good candidates for triplet fusion-enhanced OLEDs ("FuLEDs"), due to the energetically uphill nature of the photophysical process, and their common requirements. We demonstrate this with the low-cost sky-blue 1,3-diphenylisobenzofuran (DPBF). Having satisfied the criteria for TTA-UC, we show DPBF as a photon upconverter ( I th 92 mW cm -2 ), and henceforth demonstrate it as a bright emitter for FuLEDs. Notably, the devices achieved 6.5% external quantum efficiency (above the ∼5% threshold without triplet contribution), and triplet-exciton-fusion-generated fluorescence contributes up to 44% of the electroluminescence, as shown by transient measurements. Here, triplet fusion translates to a quantum yield ( Φ TTA-UC ) of 19%, at an electrical excitation of ∼0.01 mW cm -2 . The enhancement is meaningful for commercial blue OLED displays. We also found DPBF to have decent hole mobilities of ∼0.08 cm 2 V -1 s -1 . This additional finding can lead to DPBF being used in other capacities in various printable electronics., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

We present a soft-stamping method to selectively print a homogenous layer of CdSeTe/ZnS core-shell quantum dots (QDs) on top of an array of Si nanocylinders with Mie-type resonant modes. Using this new method, we gain accurate control of the quantum dot's angular emission through engineered coupling of the QDs to these resonant modes. Using numerical simulations we show that the emission into or away from the Si substrate can be precisely controlled by the QD position on the nanocylinder. QDs centered on a 400 nm diameter nanocylinder surface show 98% emission directionality into the Si substrate. Alternatively, for homogenous ensembles placed over the nanocylinder top-surface, the upward emission is enhanced 10-fold for 150 nm diameter cylinders. Experimental PL intensity measurements corroborate the simulated trends with cylinder diameter. PL lifetime measurements reflect well the variations of the local density of states at the QD position due to coupling to the resonant cylinders. These results demonstrate that the soft imprint technique provides a unique manner to directly integrate optical emitters with a wide range of nanophotonic geometries, with potential applications in LEDs, luminescent solar concentrators, and up- and down-conversion schemes for improved photovoltaics., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Halide alloying in metal halide perovskites is a useful tool for optoelectronic applications requiring a specific bandgap. However, mixed-halide perovskites show ion migration in the perovskite layer, leading to phase segregation and reducing the long-term stability of the devices. Here, we study the ion migration process in methylammonium-based mixed-halide perovskites with varying ratios of bromide to iodide. We find that the mixed-halide perovskites show two separate halide migration processes, in contrast to pure-phase perovskites, which show only a unique halide migration component. Compared to pure-halide perovskites, these processes have lower activation energies, facilitating ion migration in mixed versus pure-phase perovskites, and have a higher density of mobile ions. Under illumination, we find that the concentration of mobile halide ions is further increased and notice the emergence of a migration process involving methylammonium cations. Quantifying the ion migration processes in mixed-halide perovskites shines light on the key parameters allowing the design of bandgap-tunable perovskite solar cells with long-term stability., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Highly efficient solar cells containing lead halide perovskites are expected to revolutionize sustainable energy production in the coming years. Perovskites are generally assumed to be toxic because of the lead (Pb), but experimental evidence to support this prediction is scarce. We tested the toxicity of the perovskite MAPbI 3 (MA = CH 3 NH 3 ) and several precursors in Arabidopsis thaliana plants. Both MAPbI 3 and the precursor MAI hamper plant growth at concentrations above 5 μM. Lead-based precursors without iodide are only toxic above 500 μM. Iodine accumulation in Arabidopsis correlates with growth inhibition at much lower concentrations than lead. This reveals that perovskite toxicity at low concentrations is caused by iodide ions specifically, instead of lead. We calculate that toxicity thresholds for iodide, but not lead, are likely to be reached in soils upon perovskite leakage. This work stresses the importance to further understand and predict harmful effects of iodide-containing perovskites in the environment., Competing Interests: The authors declare no competing interests., (© 2021 The Author(s).)

Singlet fission is a carrier multiplication mechanism that could make silicon solar cells much more efficient. The singlet-fission process splits one high-energy spin-singlet exciton into two lower-energy spin-triplet excitons. We calculated the efficiency potential of three technologically relevant singlet-fission silicon solar cell implementations. We assume realistic but optimistic parameters for the singlet-fission material and investigate the effect of singlet energy and entropic gain. If the transfer of triplet excitons occurs via charge transfer, the maximum efficiency is 34.6% at a surprisingly small singlet energy of 1.85 eV. For the Dexter-type triplet energy transfer, the maximum efficiency is 32.9% at a singlet energy of 2.15 eV. For Förster resonance energy transfer (FRET), the triplet excitons are first transferred into a quantum dot, from which they then undergo FRET into silicon. For this transfer mechanism, the maximum efficiency is 28.% at a singlet energy of 2.33 eV. We show that the efficiency gain from singlet fission is larger the more efficient the silicon base cell is, which stands in contrast to tandem perovskite-silicon solar cells., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

It is challenging for conventional top-down lithography to fabricate reproducible devices very close to atomic dimensions, whereas identical molecules and very similar nanoparticles can be made bottom-up in large quantities, and can be self-assembled on surfaces. The challenge is to fabricate electrical contacts to many such small objects at the same time, so that nanocrystals and molecules can be incorporated into conventional integrated circuits. Here, we report a scalable method for contacting a self-assembled monolayer of nanoparticles with a single layer of graphene. This produces single-electron effects, in the form of a Coulomb staircase, with a yield of 87 ± 13% in device areas ranging from < 800 nm 2 to 16 μm 2 , containing up to 650,000 nanoparticles. Our technique offers scalable assembly of ultra-high densities of functional particles or molecules that could be used in electronic integrated circuits, as memories, switches, sensors or thermoelectric generators., (© 2021. The Author(s).)

Hot-carrier cooling (HCC) in metal halide perovskites above the Mott transition is significantly slower than in conventional semiconductors. This effect is commonly attributed to a hot-phonon bottleneck, but the influence of the lattice properties on the HCC behavior is poorly understood. Using pressure-dependent transient absorption spectroscopy, we find that at an excitation density below the Mott transition, pressure does not affect the HCC. On the contrary, above the Mott transition, HCC in methylammonium lead iodide is around 2-3 times faster at 0.3 GPa than at ambient pressure. Our electron-phonon coupling calculations reveal ∼2-fold stronger electron-phonon coupling for the inorganic cage mode at 0.3 GPa. However, our experiments reveal that pressure promotes faster HCC only above the Mott transition. Altogether, these findings suggest a change in the nature of excited carriers above the Mott transition threshold, providing insights into the electronic behavior of devices operating at such high charge-carrier densities.

Patterning materials with different properties in a single film is a fundamental challenge and essential for the development of next-generation (opto)electronic functional components. This work introduces the concept of ion exchange lithography and demonstrates spatially controlled patterning of electrically insulating films and semiconductors with tunable optoelectronic properties. In ion exchange lithography, a reactive nanoparticle "canvas" is locally converted by printing ion exchange "inks." To demonstrate the proof of principle, a canvas of insulating nanoporous lead carbonate is spatioselectively converted into semiconducting lead halide perovskites by contact printing an ion exchange precursor ink of methylammonium and formamidinium halides. By selecting the composition of the ink, the photoluminescence wavelength of the perovskite semiconductors is tunable over the entire visible spectrum. A broad palette of conversion inks can be applied on the reactive film by printing with customizable stamp designs, spray-painting with stencils, and painting with a brush to inscribe well-defined patterns with tunable optoelectronic properties in the same canvas. Moreover, the optoelectronic properties of the converted canvas are exploited to fabricate a green light-emitting diode (LED), demonstrating the functionality potential of ion exchange lithography., (© 2021 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

Accurately controlling light emission using nano- and microstructured lenses and antennas is an active field of research. Dielectrics are especially attractive lens materials due to their low optical losses over a broad bandwidth. In this work we measure highly directional light emission from patterned quantum dots (QDs) aligned underneath all-dielectric nanostructured microlenses. The lenses are designed with an evolutionary algorithm and have a theoretical directivity of 160. The fabricated structures demonstrate an experimental full directivity of 61 ± 3, three times higher than what has been estimated before, with a beaming half-angle of 2.6°. This high value compared to previous works is achieved via three mechanisms. First, direct electron beam patterning of QD emitters and alignment markers allowed for more localized emission and better emitter-lens alignment. Second, the lens fabrication was refined to minimize distortions between the designed shape and the final structure. Finally, a new measurement technique was developed that combines integrating sphere microscopy with Fourier microscopy. This enables complete directivity measurements, contrary to other reported values, which are typically only partial directivities or estimates of the full directivity that rely partly on simulations. The experimentally measured values of the complete directivity were higher than predicted by combining simulations with partial directivity measurements. High directivity was obtained from three different materials (cadmium-selenide-based QDs and two lead halide perovskite materials), emitting at 520, 620, and 700 nm, by scaling the lens size according to the emission wavelength., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Ytterbium-doped lead halide perovskite (Yb 3+ :CsPbX 3 with x = Cl or Cl/Br) nanocrystals and thin films have shown surprisingly efficient downconversion by quantum cutting with PLQYs up to 193%. After excitation of the perovskite host with high-energy photons, the excited states of two Yb ions are rapidly populated, subsequently emitting lower-energy photons. Several synthesis routes lead to highly efficient materials, and we review the progress on both the synthesis, material quality and applicability of these downconversion layers. For solar cells they could be used to increase the power converted from high-energy photons, and first applications have already shown an increase in the power conversion efficiency of silicon and CIGS solar cells. Applications such as luminescent solar concentrators an LEDs are also explored. With further research to overcome challenges regarding power saturation and stability, this material has great potential for a simple route to enhance solar cells.

Ion migration in perovskite layers can significantly reduce the long-term stability of the devices. While perovskite composition engineering has proven an interesting tool to mitigate ion migration, many optoelectronic devices require a specific bandgap and thus require a specific perovskite composition. Here, we look at the effect of grain size to mitigate ion migration. We find that in MAPbBr 3 solar cells prepared with grain sizes varying from 2 to 11 μm the activation energy for bromide ion migration increases from 0.17 to 0.28 eV. Moreover, we observe the appearance of a second bromide ion migration pathway for the devices with largest grain size, which we attribute to ion migration mediated by the bulk of the perovskite, as opposed to ion migration mediated by the grain boundaries. Together, these results suggest the beneficial nature of grain engineering for reduction of ion migration in perovskite solar cells.

Understanding and controlling the crystallization of organic-inorganic perovskite materials is important for their function in optoelectronic applications. This control is particularly delicate in scalable single-step thermal annealing methods. In this work, the crystallization mechanisms of flash infrared-annealed perovskite films, grown on substrates with lithographically patterned Au nucleation seeds, are investigated. The patterning enables the in situ observation to study the crystallization kinetics and the precise control of the perovskite nucleation and domain growth, while retaining the characteristic polycrystalline micromorphology with larger crystallites at the boundaries of the crystal domains, as shown by electron backscattering diffraction. Time-resolved photoluminescence measurements reveal longer charge carrier lifetimes in regions with large crystallites on the domain boundaries, relative to the domain interior. By increasing the nucleation site density, the proportion of larger crystallites is increased. This study shows that the combination of rapid thermal annealing with nucleation control is a promising approach to improve perovskite crystallinity and thereby ultimately the performance of optoelectronic devices.

Photovoltaic systems have reached impressive efficiencies, with records in the range of 20-30% for single-junction cells based on many different materials, yet the fundamental Shockley-Queisser efficiency limit of 34% is still out of reach. Improved photonic design can help approach the efficiency limit by eliminating losses from incomplete absorption or nonradiative recombination. This Perspective reviews nanopatterning methods and metasurfaces for increased light incoupling and light trapping in light absorbers and describes nanophotonics opportunities to reduce carrier recombination and utilize spectral conversion. Beyond the state-of-the-art single junction cells, photonic design plays a crucial role in the next generation of photovoltaics, including tandem and self-adaptive solar cells, and to extend the applicability of solar cells in many different ways. We address the exciting research opportunities and challenges in photonic design principles and fabrication that will accelerate the massive upscaling and (invisible) integration of photovoltaics into every available surface., Competing Interests: The authors declare no competing financial interest.

Singlet fission in tetracene generates two triplet excitons per absorbed photon. If these triplet excitons can be effectively transferred into silicon (Si), then additional photocurrent can be generated from photons above the bandgap of Si. This could alleviate the thermalization loss and increase the efficiency of conventional Si solar cells. Here, we show that a change in the polymorphism of tetracene deposited on Si due to air exposure facilitates triplet transfer from tetracene into Si. Magnetic field-dependent photocurrent measurements confirm that triplet excitons contribute to the photocurrent. The decay of tetracene delayed photoluminescence was used to determine a transfer efficiency of ∼36% into Si. Our study suggests that control over the morphology of tetracene during the deposition will be of great importance to boost the triplet transfer yield further.

The bandgap tunability of mixed-halide perovskites makes them promising candidates for light-emitting diodes and tandem solar cells. However, illuminating mixed-halide perovskites results in the formation of segregated phases enriched in a single halide. This segregation occurs through ion migration, which is also observed in single-halide compositions, and whose control is thus essential to enhance the lifetime and stability. Using pressure-dependent transient absorption spectroscopy, we find that the formation rates of both iodide- and bromide-rich phases in MAPb(Br x I 1- x ) 3 reduce by 2 orders of magnitude on increasing the pressure to 0.3 GPa. We explain this reduction from a compression-induced increase of the activation energy for halide migration, which is supported by first-principle calculations. A similar mechanism occurs when the unit cell volume is reduced by incorporating a smaller cation. These findings reveal that stability with respect to halide segregation can be achieved either physically through compressive stress or chemically through compositional engineering., Competing Interests: The authors declare no competing financial interest.

Localizing light to nanoscale volumes through nanoscale resonators that are low loss and precisely tailored in spectrum to properties of matter is crucial for classical and quantum light sources, cavity QED, molecular spectroscopy, and many other applications. To date, two opposite strategies have been identified: to use either plasmonics with deep subwavelength confinement yet high loss and very poor spectral control or instead microcavities with exquisite quality factors yet poor confinement. In this work we realize hybrid plasmonic-photonic resonators that enhance the emission of single quantum dots, profiting from both plasmonic confinement and microcavity quality factors. Our experiments directly demonstrate how cavity and antenna jointly realize large cooperative Purcell enhancements through interferences. These can be controlled to engineer arbitrary Fano lineshapes in the local density of optical states.

Solar cells based on metal halide perovskites often show excellent efficiency but poor stability. This degradation of perovskite devices has been associated with the migration of mobile ions. MAPbBr 3 perovskite materials are significantly more stable under ambient conditions than MAPbI 3 perovskite materials. In this work, we use transient ion drift to quantify the key characteristics of ion migration in MAPbBr 3 perovskite solar cells. We then proceed to compare them with those of MAPbI 3 perovskite solar cells. We find that in MAPbBr 3 , bromide migration is the main process at play and that contrary to the case of MAPbI 3 , there is no evidence for methylammonium migration. Quantitatively, we find a reduced activation energy, a reduced diffusion coefficient, and a reduced concentration for halide ions in MAPbBr 3 compared to MAPbI 3 . Understanding this difference in mobile ion migration is a crucial step in understanding the enhanced stability of MAPbBr 3 versus MAPbI 3 .

Carrier multiplication (CM) generates multiple electron-hole pairs in a semiconductor from a single absorbed photon with energy exceeding twice the band gap. Thus, CM provides a promising way to circumvent the Shockley-Queisser limit of solar cells. The ideal material for CM should have significant overlap with the solar spectrum and should be able to fully utilize the excess energy above the band gap for additional charge carrier generation. We report efficient CM in mixed Sn/Pb halide perovskites (band gap of 1.28 eV) with onset just above twice the band gap. The CM rate outcompetes the carrier cooling process leading to efficient CM with a quantum yield of 2 for photoexcitation at 2.8 times the band gap. Such efficient CM characteristics add to the many advantageous properties of mixed Sn/Pb metal halide perovskites for photovoltaic applications.

Colloidal quantum dots have found many applications and patterning them on micro- and nanoscale would open a new dimension of tunability for the creation of smaller scale (flexible) electronics or nanophotonic structures. Here we present a simple, general, one-step top-down patterning technique for colloidal quantum dots by means of direct optical or electron beam lithography. We find that both photons and electrons can induce a solubility switch of both PbS and CdSe quantum dot films. The solubility switch can be ascribed to cross-linking of the organic ligands, which we observe from exposure with deep-UV photons (5.5 eV) to extreme-UV photons (91.9 eV), and low-energy (3-70 eV) as well as highly energetic electrons (50 keV). The required doses for patterning are relatively low and feature sizes can be as small as tens of nanometers. The luminescence properties as well as carrier lifetimes remain similar after patterning.