Strong angular and spectral narrowing of electroluminescence in an integrated Tamm-plasmon-driven halide perovskite LED.

Next-generation light-emitting applications such as displays and optical communications require judicious control over emitted light, including intensity and angular dispersion. To date, this remains a challenge as conventional methods require cumbersome optics. Here, we report highly directional and enhanced electroluminescence from a solution-processed quasi-2-dimensional halide perovskite light-emitting diode by building a device architecture to exploit hybrid plasmonic-photonic Tamm plasmon modes. By exploiting the processing and bandgap tunability of the halide perovskite device layers, we construct the device stack to optimise both optical and charge-injection properties, leading to narrow forward electroluminescence with an angular full-width half-maximum of 36.6° compared with the conventional isotropic control device of 143.9°, and narrow electroluminescence spectral full-width half-maximum of 12.1 nm. The device design is versatile and tunable to work with emission lines covering the visible spectrum with desired directionality, thus providing a promising route to modular, inexpensive, and directional operating light-emitting devices.

Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure.

Light-emitting diodes (LEDs) based on metal halide perovskites (PeLEDs) with high colour quality and facile solution processing are promising candidates for full-colour and high-definition displays1-4. Despite the great success achieved in green PeLEDs with lead bromide perovskites5, it is still challenging to realize pure-red (620-650 nm) LEDs using iodine-based counterparts, as they are constrained by the low intrinsic bandgap6. Here we report efficient and colour-stable PeLEDs across the entire pure-red region, with a peak external quantum efficiency reaching 28.7% at 638 nm, enabled by incorporating a double-end anchored ligand molecule into pure-iodine perovskites. We demonstrate that a key function of the organic intercalating cation is to stabilize the lead iodine octahedron through coordination with exposed lead ions and enhanced hydrogen bonding with iodine. The molecule synergistically facilitates spectral modulation, promotes charge transfer between perovskite quantum wells and reduces iodine migration under electrical bias. We realize continuously tunable emission wavelengths for iodine-based perovskite films with suppressed energy loss due to the decrease in bond energy of lead iodine in ionic perovskites as the bandgap increases. Importantly, the resultant devices show outstanding spectral stability and a half-lifetime of more than 7,600 min at an initial luminance of 100 cd m-2.

Strain Heterogeneity and Extended Defects in Halide Perovskite Devices.

Strain is an important property in halide perovskite semiconductors used for optoelectronic applications because of its ability to influence device efficiency and stability. However, descriptions of strain in these materials are generally limited to bulk averages of bare films, which miss important property-determining heterogeneities that occur on the nanoscale and at interfaces in multilayer device stacks. Here, we present three-dimensional nanoscale strain mapping using Bragg coherent diffraction imaging of individual grains in Cs0.1FA0.9Pb(I0.95Br0.05)3 and Cs0.15FA0.85SnI3 (FA = formamidinium) halide perovskite absorbers buried in full solar cell devices. We discover large local strains and striking intragrain and grain-to-grain strain heterogeneity, identifying distinct islands of tensile and compressive strain inside grains. Additionally, we directly image dislocations with surprising regularity in Cs0.15FA0.85SnI3 grains and find evidence for dislocation-induced antiphase boundary formation. Our results shine a rare light on the nanoscale strains in these materials in their technologically relevant device setting.

Polaronic Mass Enhancement and Polaronic Excitons in Metal Halide Perovskites.

In metal halide perovskites, the complex dielectric screening together with low energy of phonon modes leads to non-negligible Fröhlich coupling. While this feature of perovskites has already been used to explain some of the puzzling aspects of carrier transport in these materials, the possible impact of polaronic effects on the optical response, especially excitonic properties, is much less explored. Here, with the use of magneto-optical spectroscopy, we revealed the non-hydrogenic character of the excitons in metal halide perovskites, resulting from the pronounced Fröhlich coupling. Our results can be well described by the polaronic-exciton picture where electron and hole interactions are no longer described by a Coulomb potential. Furthermore, we show experimental evidence that the carrier-phonon interaction leads to the enhancement of the carrier's effective mass. Notably, our measurements reveal a pronounced temperature dependence of the carrier's effective mass, which we attribute to a band structure renormalization induced by the population of low-energy phonon modes. This interpretation finds support in our first-principles calculations.

Mechanochemically-induced glass formation from two-dimensional hybrid organic-inorganic perovskites.

Hybrid organic-inorganic perovskites (HOIPs) occupy a prominent position in the field of materials chemistry due to their attractive optoelectronic properties. While extensive work has been done on the crystalline materials over the past decades, the newly reported glasses formed from HOIPs open up a new avenue for perovskite research with their unique structures and functionalities. Melt-quenching is the predominant route to glass formation; however, the absence of a stable liquid state prior to thermal decomposition precludes this method for most HOIPs. In this work, we describe the first mechanochemically-induced crystal-glass transformation of HOIPs as a rapid, green and efficient approach for producing glasses. The amorphous phase was formed from the crystalline phase within 10 minutes of ball-milling, and exhibited glass transition behaviour as evidenced by thermal analysis techniques. Time-resolved in situ ball-milling with synchrotron powder diffraction was employed to study the microstructural evolution of amorphisation, which showed that the crystallite size reaches a comminution limit before the amorphisation process is complete, indicating that energy may be further accumulated as crystal defects. Total scattering experiments revealed the limited short-range order of amorphous HOIPs, and their optical properties were studied by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) spectroscopy.

Quantum barriers engineering toward radiative and stable perovskite photovoltaic devices.

Efficient photovoltaic devices must be efficient light emitters to reach the thermodynamic efficiency limit. Here, we present a promising prospect of perovskite photovoltaics as bright emitters by harnessing the significant benefits of photon recycling, which can be practically achieved by suppressing interfacial quenching. We have achieved radiative and stable perovskite photovoltaic devices by the design of a multiple quantum well structure with long (∼3 nm) organic spacers with oleylammonium molecules at perovskite top interfaces. Our L-site exchange process (L: barrier molecule cation) enables the formation of stable interfacial structures with moderate conductivity despite the thick barriers. Compared to popular short (∼1 nm) Ls, our approach results in enhanced radiation efficiency through the recursive process of photon recycling. This leads to the realization of radiative perovskite photovoltaics with both high photovoltaic efficiency (in-lab 26.0%, certified to 25.2%) and electroluminescence quantum efficiency (19.7 % at peak, 17.8% at 1-sun equivalent condition). Furthermore, the stable crystallinity of oleylammonium-based quantum wells enables our devices to maintain high efficiencies for over 1000 h of operation and >2 years of storage.

Multifold Enhanced Photon Upconversion in a Composite Annihilator System Sensitized by Perovskite Nanocrystals.

Photon upconversion via triplet-triplet annihilation (TTA-UC) provides a pathway to overcoming the thermodynamic efficiency limits in single-junction solar cells by allowing the harvesting of sub-bandgap photons. Here, we use mixed halide perovskite nanocrystals (CsPbX3, X = Br/I) as triplet sensitizers, with excitation transfer to 9,10-diphenylanthracene (DPA) and/or 9,10-bis[(triisopropylsilyl)ethynyl]anthracene (TIPS-An) which act as the triplet annihilators. We observe that the upconversion efficiency is five times higher with the combination of both annihilators in a composite system compared to the sum of the individual single-acceptor systems. Our work illustrates the importance of using a composite system of annihilators to enhance TTA upconversion, demonstrated in a perovskite-sensitized system, with promise for a range of potential applications in light-harvesting, biomedical imaging, biosensing, therapeutics, and photocatalysis.

Composition Dictates Octahedral Tilt and Photostability in Halide Perovskites.

Halide perovskites are excellent candidate materials for use in solar cell, LED, and detector devices, in part because their composition can be tuned to achieve ideal optoelectronic properties. Empirical efficiency optimization has led the field toward compositions rich in FA (formamidinium) on the A-site and I on the X-site, with additional small amounts of MA (methylammonium) or Cs A-site cations and Br X-site anions. However, it is not clear how and why the specific compositions of alloyed, that is, mixed component, halide perovskites relate to photo-stability of the materials. Here, this work combines synchrotron grazing incidence wide-angle X-ray scattering, photoluminescence, high-resolution scanning electron diffraction measurements and theoretical modelling to reveal the links between material structure and photostability. Namely, this work finds that increased octahedral titling leads to improved photo-stability that is correlated with lower densities of performance-harming hexagonal polytype impurities. These results uncover the structural signatures underpinning photo-stability and can therefore be used to make targeted changes to halide perovskites, bettering the commercial prospects of technologies based on these materials.

High carrier mobility along the [111] orientation in Cu2O photoelectrodes.

Solar fuels offer a promising approach to provide sustainable fuels by harnessing sunlight1,2. Following a decade of advancement, Cu2O photocathodes are capable of delivering a performance comparable to that of photoelectrodes with established photovoltaic materials3-5. However, considerable bulk charge carrier recombination that is poorly understood still limits further advances in performance6. Here we demonstrate performance of Cu2O photocathodes beyond the state-of-the-art by exploiting a new conceptual understanding of carrier recombination and transport in single-crystal Cu2O thin films. Using ambient liquid-phase epitaxy, we present a new method to grow single-crystal Cu2O samples with three crystal orientations. Broadband femtosecond transient reflection spectroscopy measurements were used to quantify anisotropic optoelectronic properties, through which the carrier mobility along the [111] direction was found to be an order of magnitude higher than those along other orientations. Driven by these findings, we developed a polycrystalline Cu2O photocathode with an extraordinarily pure (111) orientation and (111) terminating facets using a simple and low-cost method, which delivers 7 mA cm-2 current density (more than 70% improvement compared to that of state-of-the-art electrodeposited devices) at 0.5 V versus a reversible hydrogen electrode under air mass 1.5 G illumination, and stable operation over at least 120 h.

Remanufacturing Perovskite Solar Cells and Modules-A Holistic Case Study.

While perovskite photovoltaic (PV) devices are on the verge of commercialization, promising methods to recycle or remanufacture fully encapsulated perovskite solar cells (PSCs) and modules are still missing. Through a detailed life-cycle assessment shown in this work, we identify that the majority of the greenhouse gas emissions can be reduced by re-using the glass substrate and parts of the PV cells. Based on these analytical findings, we develop a novel thermally assisted mechanochemical approach to remove the encapsulants, the electrode, and the perovskite absorber, allowing reuse of most of the device constituents for remanufacturing PSCs, which recovered nearly 90% of their initial performance. Notably, this is the first experimental demonstration of remanufacturing PSCs with an encapsulant and an edge-seal, which are necessary for commercial perovskite solar modules. This approach distinguishes itself from the "traditional" recycling methods previously demonstrated in perovskite literature by allowing direct reuse of bulk materials with high environmental impact. Thus, such a remanufacturing strategy becomes even more favorable than recycling, and it allows us to save up to 33% of the module's global warming potential. Remarkably, this process most likely can be universally applied to other PSC architectures, particularly n-i-p-based architectures that rely on inorganic metal oxide layers deposited on glass substrates. Finally, we demonstrate that the CO2-footprint of these remanufactured devices can become less than 30 g/kWh, which is the value for state-of-the-art c-Si PV modules, and can even reach 15 g/kWh assuming a similar lifetime.

High-performance bifacial perovskite solar cells enabled by single-walled carbon nanotubes.

Bifacial perovskite solar cells have shown great promise for increasing power output by capturing light from both sides. However, the suboptimal optical transmittance of back metal electrodes together with the complex fabrication process associated with front transparent conducting oxides have hindered the development of efficient bifacial PSCs. Here, we present a novel approach for bifacial perovskite devices using single-walled carbon nanotubes as both front and back electrodes. single-walled carbon nanotubes offer high transparency, conductivity, and stability, enabling bifacial PSCs with a bifaciality factor of over 98% and a power generation density of over 36%. We also fabricate flexible, all-carbon-electrode-based devices with a high power-per-weight value of 73.75 W g-1 and excellent mechanical durability. Furthermore, we show that our bifacial devices have a much lower material cost than conventional monofacial PSCs. Our work demonstrates the potential of SWCNT electrodes for efficient, stable, and low-cost bifacial perovskite photovoltaics.

Multifunctional sulfonium-based treatment for perovskite solar cells with less than 1% efficiency loss over 4,500-h operational stability tests.

The stabilization of grain boundaries and surfaces of the perovskite layer is critical to extend the durability of perovskite solar cells. Here we introduced a sulfonium-based molecule, dimethylphenethylsulfonium iodide (DMPESI), for the post-deposition treatment of formamidinium lead iodide perovskite films. The treated films show improved stability upon light soaking and remains in the black α phase after two years ageing under ambient condition without encapsulation. The DMPESI-treated perovskite solar cells show less than 1% performance loss after more than 4,500 h at maximum power point tracking, yielding a theoretical T80 of over nine years under continuous 1-sun illumination. The solar cells also display less than 5% power conversion efficiency drops under various ageing conditions, including 100 thermal cycles between 25 °C and 85 °C and an 1,050-h damp heat test.

Electrochemical Impedance Spectroscopy of All-Perovskite Tandem Solar Cells.

This work explores electrochemical impedance spectroscopy to study recombination and ionic processes in all-perovskite tandem solar cells. We exploit selective excitation of each subcell to enhance or suppress the impedance signal from each subcell, allowing study of individual tandem subcells. We use this selective excitation methodology to show that the recombination resistance and ionic time constants of the wide gap subcell are increased with passivation. Furthermore, we investigate subcell-dependent degradation during maximum power point tracking and find an increase in recombination resistance and a decrease in capacitance for both subcells. Complementary optical and external quantum efficiency measurements indicate that the main driver for performance loss is the reduced capacity of the recombination layer to facilitate recombination due to the formation of a charge extraction barrier. This methodology highlights electrochemical impedance spectroscopy as a powerful tool to provide critical feedback to unlock the full potential of perovskite tandem solar cells.

Substitution of lead with tin suppresses ionic transport in halide perovskite optoelectronics.

Despite the rapid rise in the performance of a variety of perovskite optoelectronic devices with vertical charge transport, the effects of ion migration remain a common and longstanding Achilles' heel limiting the long-term operational stability of lead halide perovskite devices. However, there is still limited understanding of the impact of tin (Sn) substitution on the ion dynamics of lead (Pb) halide perovskites. Here, we employ scan-rate-dependent current-voltage measurements on Pb and mixed Pb-Sn perovskite solar cells to show that short circuit current losses at lower scan rates, which can be traced to the presence of mobile ions, are present in both kinds of perovskites. To understand the kinetics of ion migration, we carry out scan-rate-dependent hysteresis analyses and temperature-dependent impedance spectroscopy measurements, which demonstrate suppressed ion migration in Pb-Sn devices compared to their Pb-only analogues. By linking these experimental observations to first-principles calculations on mixed Pb-Sn perovskites, we reveal the key role played by Sn vacancies in increasing the iodide ion migration barrier due to local structural distortions. These results highlight the beneficial effect of Sn substitution in mitigating undesirable ion migration in halide perovskites, with potential implications for future device development.

Dynamic Local Structure in Caesium Lead Iodide: Spatial Correlation and Transient Domains.

Metal halide perovskites are multifunctional semiconductors with tunable structures and properties. They are highly dynamic crystals with complex octahedral tilting patterns and strongly anharmonic atomic behavior. In the higher temperature, higher symmetry phases of these materials, several complex structural features are observed. The local structure can differ greatly from the average structure and there is evidence that dynamic 2D structures of correlated octahedral motion form. An understanding of the underlying complex atomistic dynamics is, however, still lacking. In this work, the local structure of the inorganic perovskite CsPbI3 is investigated using a new machine learning force field based on the atomic cluster expansion framework. Through analysis of the temporal and spatial correlation observed during large-scale simulations, it is revealed that the low frequency motion of octahedral tilts implies a double-well effective potential landscape, even well into the cubic phase. Moreover, dynamic local regions of lower symmetry are present within both higher symmetry phases. These regions are planar and the length and timescales of the motion are reported. Finally, the spatial arrangement of these features and their interactions are investigated and visualized, providing a comprehensive picture of local structure in the higher symmetry phases.

A Practical Approach Toward Highly Reproducible and High-Quality Perovskite Films Based on an Aging Treatment.

Solution processing of hybrid perovskite semiconductors is a highly promising approach for the fabrication of cost-effective electronic and optoelectronic devices. However, challenges with this approach lie in overcoming the controllability of the perovskite film morphology and the reproducibility of device efficiencies. Here, a facile and practical aging treatment (AT) strategy is reported to modulate the perovskite crystal growth to produce sufficiently high-quality perovskite thin films with improved homogeneity and full-coverage morphology. The resulting AT-films exhibit fewer defects, faster charge carrier transfer/extraction, and suppressed non-radiative recombination compared with reference. The AT-devices achieve a noticeable improvement in the reproducibility, operational stability, and photovoltaic performance of devices, with the average efficiency increased by 16%. It also demonstrates the feasibility and scalability of AT strategy in optimizing the film morphology and device performance for other perovskite components including MAPbI3 , (MAPbBr3 )15 (FAPbI3 )85 , and Cs0.05 (MAPbBr3 )0.17 (FAPbI3 )0.83 . This method opens an effective avenue to improve the quality of perovskite films and photovoltaic devices in a scalable and reproducible manner.

Fast Near-Infrared Photodetectors Based on Nontoxic and Solution-Processable AgBiS2.

Solution-processable near-infrared (NIR) photodetectors are urgently needed for a wide range of next-generation electronics, including sensors, optical communications and bioimaging. However, it is rare to find photodetectors with >300 kHz cut-off frequencies, especially in the NIR region, and many of the emerging inorganic materials explored are comprised of toxic elements, such as lead. Herein, solution-processed AgBiS2 photodetectors with high cut-off frequencies under both white light (>1 MHz) and NIR (approaching 500 kHz) illumination are developed. These high cut-off frequencies are due to the short transit distances of charge-carriers in the ultrathin photoactive layer of AgBiS2 photodetectors, which arise from the strong light absorption of this material, such that film thicknesses well below 120 nm are sufficient to absorb >65% of NIR to visible light. It is also revealed that ion migration plays a critical role in the photo-response speed of these devices, and its detrimental effects can be mitigated by finely tuning the thickness of the photoactive layer, which is important for achieving low dark current densities as well. These outstanding characteristics enable the realization of air-stable, real-time heartbeat sensors based on NIR AgBiS2 photodetectors, which strongly motivates their future integration in high-throughput systems.