Chloride-Based Additive Engineering for Efficient and Stable Wide-Bandgap Perovskite Solar Cells.

Metal halide perovskite based tandem solar cells are promising to achieve power conversion efficiency beyond the theoretical limit of their single-junction counterparts. However, overcoming the significant open-circuit voltage deficit present in wide-bandgap perovskite solar cells remains a major hurdle for realizing efficient and stable perovskite tandem cells. Here, a holistic approach to overcoming challenges in 1.8 eV perovskite solar cells is reported by engineering the perovskite crystallization pathway by means of chloride additives. In conjunction with employing a self-assembled monolayer as the hole-transport layer, an open-circuit voltage of 1.25 V and a power conversion efficiency of 17.0% are achieved. The key role of methylammonium chloride addition is elucidated in facilitating the growth of a chloride-rich intermediate phase that directs crystallization of the desired cubic perovskite phase and induces more effective halide homogenization. The as-formed 1.8 eV perovskite demonstrates suppressed halide segregation and improved optoelectronic properties.

Protocol for efficient and self-healing near-infrared perovskite light-emitting diodes.

Preparation of highly efficient and stable perovskite light-emitting diodes (PeLEDs) with reproducible device performance is challenging. This protocol describes steps for fabrication of high-performance and self-healing PeLEDs. These include instructions for synthesis of charge-transporting zinc oxide (ZnO) nanocrystals, step-by-step device fabrication, and control over self-healing of the degraded devices. For complete details on the use and execution of this protocol, please refer to Teng et al. (2021).

Spacer Cation Alloying in Ruddlesden-Popper Perovskites for Efficient Red Light-Emitting Diodes with Precisely Tunable Wavelengths.

Perovskite light-emitting diodes (PeLEDs) have recently shown significant progress with external quantum efficiencies (EQEs) exceeding 20%. However, PeLEDs with pure-red (620-660 nm) light emission, an essential part for full-color displays, remain a great challenge. Herein, a general approach of spacer cation alloying is employed in Ruddlesden-Popper perovskites (RPPs) for efficient red PeLEDs with precisely tunable wavelengths. By simply tuning the alloying ratio of dual spacer cations, the thickness distribution of quantum wells in the RPP films can be precisely modulated without deteriorating their charge-transport ability and energy funneling processes. Consequently, efficient PeLEDs with tunable emissions between pure red (626 nm) and deep red (671 nm) are achieved with peak EQEs up to 11.5%, representing the highest values among RPP-based pure-red PeLEDs. This work opens a new route for color tuning, which will spur future developments of pure-red or even pure-blue PeLEDs with high performance.

Phenylalkylammonium passivation enables perovskite light emitting diodes with record high-radiance operational lifetime: the chain length matters.

Perovskite light emitting diodes suffer from poor operational stability, exhibiting a rapid decay of external quantum efficiency within minutes to hours after turn-on. To address this issue, we explore surface treatment of perovskite films with phenylalkylammonium iodide molecules of varying alkyl chain lengths. Combining experimental characterization and theoretical modelling, we show that these molecules stabilize the perovskite through suppression of iodide ion migration. The stabilization effect is enhanced with increasing chain length due to the stronger binding of the molecules with the perovskite surface, as well as the increased steric hindrance to reconfiguration for accommodating ion migration. The passivation also reduces the surface defects, resulting in a high radiance and delayed roll-off of external quantum efficiency. Using the optimized passivation molecule, phenylpropylammonium iodide, we achieve devices with an efficiency of 17.5%, a radiance of 1282.8 W sr-1 m-2 and a record T50 half-lifetime of 130 h under 100 mA cm-2.

Ultrafast long-range spin-funneling in solution-processed Ruddlesden-Popper halide perovskites.

Room-temperature spin-based electronics is the vision of spintronics. Presently, there are few suitable material systems. Herein, we reveal that solution-processed mixed-phase Ruddlesden-Popper perovskite thin-films transcend the challenges of phonon momentum-scattering that limits spin-transfer in conventional semiconductors. This highly disordered system exhibits a remarkable efficient ultrafast funneling of photoexcited spin-polarized excitons from two-dimensional (2D) to three-dimensional (3D) phases at room temperature. We attribute this efficient exciton relaxation pathway towards the lower energy states to originate from the energy transfer mediated by intermediate states. This process bypasses the omnipresent phonon momentum-scattering in typical semiconductors with stringent band dispersion, which causes the loss of spin information during thermalization. Film engineering using graded 2D/3D perovskites allows unidirectional out-of-plane spin-funneling over a thickness of ~600 nm. Our findings reveal an intriguing family of solution-processed perovskites with extraordinary spin-preserving energy transport properties that could reinvigorate the concepts of spin-information transfer.

Planar perovskite solar cells with long-term stability using ionic liquid additives.

Solar cells based on metal halide perovskites are one of the most promising photovoltaic technologies1-4. Over the past few years, the long-term operational stability of such devices has been greatly improved by tuning the composition of the perovskites5-9, optimizing the interfaces within the device structures10-13, and using new encapsulation techniques14,15. However, further improvements are required in order to deliver a longer-lasting technology. Ion migration in the perovskite active layer-especially under illumination and heat-is arguably the most difficult aspect to mitigate16-18. Here we incorporate ionic liquids into the perovskite film and thence into positive-intrinsic-negative photovoltaic devices, increasing the device efficiency and markedly improving the long-term device stability. Specifically, we observe a degradation in performance of only around five per cent for the most stable encapsulated device under continuous simulated full-spectrum sunlight for more than 1,800 hours at 70 to 75 degrees Celsius, and estimate that the time required for the device to drop to eighty per cent of its peak performance is about 5,200 hours. Our demonstration of long-term operational, stable solar cells under intense conditions is a key step towards a reliable perovskite photovoltaic technology.

Unveiling the synergistic effect of precursor stoichiometry and interfacial reactions for perovskite light-emitting diodes.

Metal halide perovskites are emerging as promising semiconductors for cost-effective and high-performance light-emitting diodes (LEDs). Previous investigations have focused on the optimisation of the emissive perovskite layer, for example, through quantum confinement to enhance the radiative recombination or through defect passivation to decrease non-radiative recombination. However, an in-depth understanding of how the buried charge transport layers affect the perovskite crystallisation, though of critical importance, is currently missing for perovskite LEDs. Here, we reveal synergistic effect of precursor stoichiometry and interfacial reactions for perovskite LEDs, and establish useful guidelines for rational device optimization. We reveal that efficient deprotonation of the undesirable organic cations by a metal oxide interlayer with a high isoelectric point is critical to promote the transition of intermediate phases to highly emissive perovskite films. Combining our findings with effective defect passivation of the active layer, we achieve high-efficiency perovskite LEDs with a maximum external quantum efficiency of 19.6%.

Efficient and Tunable Electroluminescence from In Situ Synthesized Perovskite Quantum Dots.

Semiconductor quantum dots (QDs) are among the most promising next-generation optoelectronic materials. QDs are generally obtained through either epitaxial or colloidal growth and carry the promise for solution-processed high-performance optoelectronic devices such as light-emitting diodes (LEDs), solar cells, etc. Herein, a straightforward approach to synthesize perovskite QDs and demonstrate their applications in efficient LEDs is reported. The perovskite QDs with controllable crystal sizes and properties are in situ synthesized through one-step spin-coating from perovskite precursor solutions followed by thermal annealing. These perovskite QDs feature size-dependent quantum confinement effect (with readily tunable emissions) and radiative monomolecular recombination. Despite the substantial structural inhomogeneity, the in situ generated perovskite QDs films emit narrow-bandwidth emission and high color stability due to efficient energy transfer between nanostructures that sweeps away the unfavorable disorder effects. Based on these materials, efficient LEDs with external quantum efficiencies up to 11.0% are realized. This makes the technologically appealing in situ approach promising for further development of state-of-the-art LED systems and other optoelectronic devices.

Ultra-Bright Near-Infrared Perovskite Light-Emitting Diodes with Reduced Efficiency Roll-off.

Herein, an insulating biopolymer is exploited to guide the controlled formation of micro/nano-structure and physical confinement of α-δ mixed phase crystalline grains of formamidinium lead iodide (FAPbI3) perovskite, functioning as charge carrier concentrators and ensuring improved radiative recombination and photoluminescence quantum yield (PLQY). This composite material is used to build highly efficient near-infrared (NIR) FAPbI3 Perovskite light-emitting diodes (PeLEDs) that exhibit a high radiance of 206.7 W/sr*m2, among the highest reported for NIR-PeLEDs, obtained at a very high current density of 1000 mA/cm2, while importantly avoiding the efficiency roll-off effect. In depth photophysical characterization allows to identify the possible role of the biopolymer in i) enhancing the radiative recombination coefficient, improving light extraction by reducing the refractive index, or ii) enhancing the effective optical absorption because of dielectric scattering at the polymer-perovskite interfaces. Our study reveals how the use of insulating matrixes for the growth of perovskites represents a step towards high power applications of PeLEDs.

Room-temperature film formation of metal halide perovskites on n-type metal oxides: the catalysis of ZnO on perovskite crystallization.

We investigate the effect of commonly used solution-processed TiOx, SnO2 and ZnO interlayers on the perovskite film crystallization process. We find that the ZnO/perovskite interface can efficiently catalyze the perovskite crystallization even without thermal annealing.

Oxygen- and Water-Induced Energetics Degradation in Organometal Halide Perovskites.

Organometal halide perovskites are under rapid development, and significant focus has been placed on their stability that currently presents a major obstacle for practical application. Energetics plays a vital role in charge injection/extraction and transport properties in devices. Here, we in situ investigate oxygen- and water-induced energetics degradation in organometal halide perovskite films. Oxygen gas induces an upward shift of the vacuum level of the perovskite films because of the formation of an oxygen-induced surface dipole, water vapor causes a significant vacuum-level downshift, and the valence band binding energy referenced to the Fermi level simultaneously increases so as to keep the ionization potential of the perovskite films unchanged. Moreover, the chemical compositions, crystalline structures, surface morphologies, and dynamical properties also are monitored and analyzed in detail. These results are indispensable to understand the degradation mechanisms and to perform the optimizations of stable materials and devices in the future.

Efficient perovskite light-emitting diodes based on a solution-processed tin dioxide electron transport layer.

To achieve high-performance perovskite light-emitting diodes (PeLEDs), an appropriate functional layer beneath the perovskite emissive layer is significantly important to modulate the morphology of the perovskite film and to facilitate charge injection and transport in the device. Herein, for the first time, we report efficient n-i-p structured PeLEDs using solution-processed SnO2 as an electron transport layer. Three-dimensional perovskites, such as CH(NH2)2PbI3 and CH3NH3PbI3, are found to be more chemically compatible with SnO2 than with commonly used ZnO. In addition, SnO2 shows good transparency, excellent morphology and suitable energy levels. These properties make SnO2 a promising candidate in both three- and low-dimensional PeLEDs, among which a high external quantum efficiency of 7.9% has been realized. Furthermore, interfacial materials that are widely used to improve the device performances of ZnO-based PeLEDs are also applied on SnO2-based PeLEDs and their effects have been systematically studied. In contrast to ZnO, SnO2 modified by these interfacial materials shows detrimental effects due to photoluminescence quenching.

The Light-Induced Field-Effect Solar Cell Concept - Perovskite Nanoparticle Coating Introduces Polarization Enhancing Silicon Cell Efficiency.

Solar cell generates electrical energy from light one via pulling excited carrier away under built-in asymmetry. Doped semiconductor with antireflection layer is general strategy to achieve this including crystalline silicon (c-Si) solar cell. However, loss of extra energy beyond band gap and light reflection in particular wavelength range is known to hinder the efficiency of c-Si cell. Here, it is found that part of short wavelength sunlight can be converted into polarization electrical field, which strengthens asymmetry in organic-c-Si heterojunction solar cell through molecule alignment process. The light harvested by organometal trihalide perovskite nanoparticles (NPs) induces molecular alignment on a conducting polymer, which generates positive electrical surface field. Furthermore, a "field-effect solar cell" is successfully developed and implemented by combining perovskite NPs with organic/c-Si heterojunction associating with light-induced molecule alignment, which achieves an efficiency of 14.3%. In comparison, the device with the analogous structure without perovskite NPs only exhibits an efficiency of 12.7%. This finding provides a novel concept to design solar cell by sacrificing part of sunlight to provide "extra" asymmetrical field continuously as to drive photogenerated carrier toward respective contacts under direct sunlight. Moreover, it also points out a method to combine promising perovskite material with c-Si solar cell.

Approximately 800-nm-Thick Pinhole-Free Perovskite Films via Facile Solvent Retarding Process for Efficient Planar Solar Cells.

Device performance of organometal halide perovskite solar cells significantly depends on the quality and thickness of perovskite absorber films. However, conventional deposition methods often generate pinholes within ∼300 nm-thick perovskite films, which are detrimental to the large area device manufacture. Here we demonstrated a simple solvent retarding process to deposit uniform pinhole free perovskite films with thicknesses up to ∼800 nm. Solvent evaporation during the retarding process facilitated the components separation in the mixed halide perovskite precursors, and hence the final films exhibited pinhole free morphology and large grain sizes. In addition, the increased precursor concentration after solvent-retarding process led to thick perovskite films. Based on the uniform and thick perovskite films prepared by this convenient process, a champion device efficiency up to 16.8% was achieved. We believe that this simple deposition procedure for high quality perovskite films around micrometer thickness has a great potential in the application of large area perovskite solar cells and other optoelectronic devices.

Iodomethane-Mediated Organometal Halide Perovskite with Record Photoluminescence Lifetime.

Organometallic lead halide perovskites are excellent light harvesters for high-efficiency photovoltaic devices. However, as the key component in these devices, a perovskite thin film with good morphology and minimal trap states is still difficult to obtain. Herein we show that by incorporating a low boiling point alkyl halide such as iodomethane (CH3I) into the precursor solution, a perovskite (CH3NH3PbI3-xClx) film with improved grain size and orientation can be easily achieved. More importantly, these films exhibit a significantly reduced amount of trap states. Record photoluminescence lifetimes of more than 4 µs are achieved; these lifetimes are significantly longer than that of pristine CH3NH3PbI3-xClx films. Planar heterojunction solar cells incorporating these CH3I-mediated perovskites have demonstrated a dramatically increased power conversion efficiency compared to the ones using pristine CH3NH3PbI3-xClx. Photoluminescence, transient absorption, and microwave detected photoconductivity measurements all provide consistent evidence that CH3I addition increases the number of excitons generated and their diffusion length, both of which assist efficient carrier transport in the photovoltaic device. The simple incorporation of alkyl halide to enhance perovskite surface passivation introduces an important direction for future progress on high efficiency perovskite optoelectronic devices.

Highly flexible and lightweight organic solar cells on biocompatible silk fibroin.

Organic electronics have gained widespread attention due to their flexibility, lightness, and low-cost potential. It is attractive due to the possibility of large-scale roll-to-roll processing. However, organic electronics require additional development before they can be made commercially available and fully integrated into everyday life. To achieve feasibility for commercial use, these devices must be biocompatible and flexible while maintaining high performance. In this study, biocompatible silk fibroin (SF) was integrated with a mesh of silver nanowires (AgNWs) to build up flexible organic solar cells with maximum power conversion efficiency of up to 6.62%. The AgNW/SF substrate exhibits a conductivity of ∼11.0 Ω/sq and transmittance of ∼80% in the visible light range. These substrates retained their conductivity, even after being bent and unbent 200 times; this surprising ability was attributed to its embedded structure and the properties of the specific SF materials used. To contrast, indium tin oxide on synthetic plastic substrate lost its conductivity after the much less rigid bending. These lightweight and silk-based organic solar cells pave the way for future biocompatible interfaces between wearable electronics and human skin.

Efficient planar heterojunction perovskite solar cells employing graphene oxide as hole conductor.

Graphene oxide (GO) is employed as a hole conductor in inverted planar heterojunction perovskite solar cells, and the devices with CH3NH3PbI3-xClx as absorber achieve an efficiency of over 12%. The perovskite film grown on GO exhibits enhanced crystallization, high surface coverage ratio as well as preferred in-plane orientation of the (110) plane. Efficient hole extraction from the perovskite to GO is demonstrated.