Pattern-Matched Polymer Ligands Toward Near-Perfect Synergistic Passivation for High-Performance and Stable Br/Cl Mixed Perovskite Light-Emitting Diodes.

Mixed Br/Cl perovskite nanocrystals (PeNCs) exhibit bright pure-blue emission benefiting for fulfilling the Rec. 2100 standard. However, phase segregation remains a significant challenge that severely affects the stability and emission spectrum of perovskite light-emitting diodes (PeLEDs). Here, we demonstrate the optimization of the spacing between polydentate functional groups of polymer ligands to match the surface pattern of CsPbBr1.8Cl1.2 PeNCs, resulting in effective synergistic passivation effect and significant improvements in PeLED performances. The block and alternating copolymers with different inter-functional group spacing are facilely synthesized as ligands for PeNCs. Surprisingly, block copolymers with a higher functional group density do not match PeNCs, while alternating copolymers enable efficient PeNCs with the high photoluminescence intensity, low non-radiative recombination rate and high exciton binding energy. Density functional theory calculations clearly confirm the almost perfect match between alternating copolymers and PeNCs. Finally, pure-blue PeLEDs are achieved with the emission at 467 nm and Commission Internationale de l'Eclairage (CIE) coordinates of (0.131, 0.071), high external quantum efficiency (9.1 %) and record spectral and operational stabilities (~80 mins) in mixed-halide PeLEDs. Overall, this study contributes to designing the polymer ligands and promoting the development of high-performance and stable pure-color PeLEDs towards display applications.

Dopant-free NiOx Nanocrystals: A Low-cost and Stable Hole Transport Material for Commercializing Perovskite Optoelectronics.

Advancing inverted (p-i-n) perovskite solar cells (PSCs) is critical for commercial applications given their compatibility with different bottom cells for tandem photovoltaics, low-temperature processability (≤100 °C), and promising operational stability. Although inverted PSCs have achieved an efficiency of over 25 % using doped or expensive organic hole transport materials (HTMs), their synthesis cost and stability still cannot meet the requirements for their commercialization. Recently, dopant-free and low-cost non-stoichiometric nickel oxide nanocrystals (NiOx NCs) have been extensively studied as a low-cost and effective HTM in perovskite optoelectronics. In this minireview, we summarize the synthesis and surface-functionalization methods of NiOx NCs. Then, the applications of NiOx NCs in other perovskite optoelectronics beyond photovoltaics are discussed. Finally, we provide a perspective for the future development of NiOx NCs for the commercialization of perovskite optoelectronics.

Establishing Multifunctional Interface Layer of Perovskite Ligand Modified Lead Sulfide Quantum Dots for Improving the Performance and Stability of Perovskite Solar Cells.

While organic-inorganic halide perovskite solar cells (PSCs) show great potential for realizing low-cost and easily fabricated photovoltaics, the unexpected defects and long-term stability against moisture are the main issues hindering their practical applications. Herein, a strategy is demonstrated to address the main issues by introducing lead sulfide quantum dots (QDs) on the perovskite surface as the multifunctional interface layer on perovskite film through establishing perovskite as the ligand on PbS QDs. Meanwhile, the multifunctions are featured in three aspects including the strong interactions of PbS QDs with perovskites particularly at the grain boundaries favoring good QDs coverage on perovskites for ultimate smooth morphology; an inhibition of iodide ions mobilization by the strong interaction between iodide and the incorporated QDs; and the reduction of the dangling bonds of Pb2+ by the sulfur atoms of PbS QDs. Finally, the device performances are highly improved due to the reduced defects and non-radiative recombination. The results show that both open-circuit voltage and fill factor are significantly improved to the high values of 1.13 V and 80%, respectively in CH3 NH3 PbI3 -based PSCs, offering a high efficiency of 20.64%. The QDs incorporation also enhances PSCs' stability benefitting from the induced hydrophobic surface and suppressed iodide mobilization.

Emerging Novel Metal Electrodes for Photovoltaic Applications.

Emerging novel metal electrodes not only serve as the collector of free charge carriers, but also function as light trapping designs in photovoltaics. As a potential alternative to commercial indium tin oxide, transparent electrodes composed of metal nanowire, metal mesh, and ultrathin metal film are intensively investigated and developed for achieving high optical transmittance and electrical conductivity. Moreover, light trapping designs via patterning of the back thick metal electrode into different nanostructures, which can deliver a considerable efficiency improvement of photovoltaic devices, contribute by the plasmon-enhanced light-mattering interactions. Therefore, here the recent works of metal-based transparent electrodes and patterned back electrodes in photovoltaics are reviewed, which may push the future development of this exciting field.

Enhancing the Brightness of Cesium Lead Halide Perovskite Nanocrystal Based Green Light-Emitting Devices through the Interface Engineering with Perfluorinated Ionomer.

High photoluminescence quantum yield, easily tuned emission colors, and high color purity of perovskite nanocrystals make this class of material attractive for light source or display applications. Here, green light-emitting devices (LEDs) were fabricated using inorganic cesium lead halide perovskite nanocrystals as emitters. By introducing a thin film of perfluorinated ionomer (PFI) sandwiched between the hole transporting layer and perovskite emissive layer, the device hole injection efficiency has been significantly enhanced. At the same time, PFI layer suppressed charging of the perovskite nanocrystal emitters thus preserving their superior emissive properties, which led to the three-fold increase in peak brightness reaching 1377 cd m(-2). The full width at half-maximum of the symmetric emission peak with color coordinates of (0.09, 0.76) was 18 nm, the narrowest value among perovskite based green LEDs.

Solution-Processed Metal Oxides as Efficient Carrier Transport Layers for Organic Photovoltaics.

Carrier (electron and hole) transport layers (CTLs) are essential components for boosting the performance of various organic optoelectronic devices such as organic solar cells and organic light-emitting diodes. Considering the drawbacks of conventional CTLs (easily oxidized/unstable, demanding/costly fabrication, etc.), transition metal oxides with good carrier transport/extraction and superior stability have drawn extensive research interest as CTLs for next-generation devices. In recent years, many research efforts have been made toward the development of solution-based metal oxide CTLs with the focus on low- or even room-temperature processes, which can potentially be compatible with the deposition processes of organic materials and can significantly contribute to the low-cost and scale-up of organic devices. Here, the recent progress of different types of solution-processed metal oxide CTLs are systematically reviewed in the context of organic photovoltaics, from synthesis approaches to device performance. Different approaches for further enhancing the performance of solution-based metal oxide CTLs are also discussed, which may push the future development of this exciting field.

Recent Advances in Organic Photovoltaics: Device Structure and Optical Engineering Optimization on the Nanoscale.

Organic photovoltaic (OPV) devices, which can directly convert absorbed sunlight to electricity, are stacked thin films of tens to hundreds of nanometers. They have emerged as a promising candidate for affordable, clean, and renewable energy. In the past few years, a rapid increase has been seen in the power conversion efficiency of OPV devices toward 10% and above, through comprehensive optimizations via novel photoactive donor and acceptor materials, control of thin-film morphology on the nanoscale, device structure developments, and interfacial and optical engineering. The intrinsic problems of short exciton diffusion length and low carrier mobility in organic semiconductors creates a challenge for OPV designs for achieving optically thick and electrically thin device structures to achieve sufficient light absorption and efficient electron/hole extraction. Recent advances in the field of OPV devices are reviewed, with a focus on the progress in device architecture and optical engineering approaches that lead to improved electrical and optical characteristics in OPV devices. Successful strategies are highlighted for light wave distribution, modulation, and absorption promotion inside the active layer of OPV devices by incorporating periodic nanopatterns/nanostructures or incorporating metallic nanomaterials and nanostructures.

High Efficiency Organic Solar Cells Achieved by the Simultaneous Plasmon-Optical and Plasmon-Electrical Effects from Plasmonic Asymmetric Modes of Gold Nanostars.

The plasmon-optical effects have been utilized to optically enhance active layer absorption in organic solar cells (OSCs). The exploited plasmonic resonances of metal nanomaterials are typically from the fundamental dipole/high-order modes with narrow spectral widths for regional OSC absorption improvement. The conventional broadband absorption enhancement (using plasmonic effects) needs linear-superposition of plasmonic resonances. In this work, through strategic incorporation of gold nanostars (Au NSs) in between hole transport layer (HTL) and active layer, the excited plasmonic asymmetric modes offer a new approach toward broadband enhancement. Remarkably, the improvement is explained by energy transfer of plasmonic asymmetric modes of Au NS. In more detail, after incorporation of Au NSs, the optical power in electron transport layer transfers to active layer for improving OSC absorption, which otherwise will become dissipation or leakage as the role of carrier transport layer is not for photon-absorption induced carrier generation. Moreover, Au NSs simultaneously deliver plasmon-electrical effects which shorten transport path length of the typically low-mobility holes and lengthen that of high-mobility electrons for better balanced carrier collection. Meanwhile, the resistance of HTL is reduced by Au NSs. Consequently, power conversion efficiency of 10.5% has been achieved through cooperatively plasmon-optical and plasmon-electrical effects of Au NSs.

Observing abnormally large group velocity at the plasmonic band edge via a universal eigenvalue analysis.

We developed a novel universal eigenvalue analysis for 2D arbitrary nanostructures comprising dispersive and lossy materials. The complex dispersion relation (or complex Bloch band structure) of a metallic grating is rigorously calculated by the proposed algorithm with the finite-difference implementation. The abnormally large group velocity is observed at a plasmonic band edge with a large attenuation constant. Interestingly, we found the abnormal group velocity is caused by the leaky (radiation) loss, not by metallic absorption (ohmic) loss. The periodically modulated surface of the grating significantly modifies the original dispersion relation of the semi-infinite dielectric-metal structure and induces the extraordinarily large group velocity, which is different from the near-zero group velocity at photonic band edge. The work is fundamentally important to the design of plasmonic nanostructures.

Quenching Detrimental Reactions and Boosting Hole Extraction via Multifunctional NiOx /Perovskite Interface Passivation for Efficient and Stable Inverted Solar Cells.

Nickel oxide (NiOx ) is one of the most promising hole transport materials for inverted perovskite solar cells (PSCs). However, its application is severely restrained due to unfavorable interfacial reactions and insufficient charge carrier extraction. Herein, a multifunctional modification at the NiOx /perovskite interface is developed via introducing fluorinated ammonium salt ligand to synthetically solve the obstacles. Specifically, the interface modification can chemically convert detrimental Ni≥3+ to lower oxidation state, resulting in the elimination of interfacial redox reactions. Meanwhile, interfacial dipole is incorporated simultaneously to tune the work function of NiOx and optimize energy level alignment, which effectively promotes the charge carrier extraction. Therefore, the modified NiOx -based inverted PSCs achieve a remarkable power conversion efficiency (PCE) of 22.93%. Moreover, the unencapsulated devices obtain a significantly enhanced long-term stability, maintaining over 85% and 80% of the initial PCEs after storage in ambient air with a high relative humidity of 50-60% for 1000 h and continuous operation at maximum power point under one-sun illumination for 700 h, respectively.

Selenium substitution for dielectric constant improvement and hole-transfer acceleration in non-fullerene organic solar cells.

Dielectric constant of non-fullerene acceptors plays a critical role in organic solar cells in terms of exciton dissociation and charge recombination. Current acceptors feature a dielectric constant of 3-4, correlating to relatively high recombination loss. We demonstrate that selenium substitution on acceptor central core can effectively modify molecule dielectric constant. The corresponding blend film presents faster hole-transfer of ~5 ps compared to the sulfur-based derivative (~10 ps). However, the blends with Se-acceptor also show faster charge recombination after 100 ps upon optical pumping, which is explained by the relatively disordered stacking of the Se-acceptor. Encouragingly, dispersing the Se-acceptor in an optimized organic solar cell system can interrupt the disordered aggregation while still retain high dielectric constant. With the improved dielectric constant and optimized fibril morphology, the ternary device exhibits an obvious reduction of non-radiative recombination to 0.221 eV and high efficiency of 19.0%. This work unveils heteroatom-substitution induced dielectric constant improvement, and the associated exciton dynamics and morphology manipulation, which finally contributes to better material/device design and improved device performance.

Tri-system integration in metal-oxide nanocomposites via in-situ solution-processed method for ultrathin flexible transparent electrodes.

For stable operation of ultrathin flexible transparent electrodes (uFTEs), it is critical to implement effective risk management during concurrent multi-loading operation of electrical bias and mechanical folding cycles in high-humidity environments. Despite extensive efforts in preparing solution-processed uFTEs with cost-effective and high-throughput means, achieving in-situ nano-adhesion in heterogeneous metal-oxide nanocomposites remains challenging. In this work, we observed by serendipity liquid-like behaviour of transparent metal-oxide-semiconductor zinc oxide nanoparticles (ZnONPs) onto silver nanowires (AgNWs) developed by in-situ solution processed method (iSPM). This enabled us to address the long-standing issue of vulnerability in the nanocomposite caused by the interface of dissimilar materials between AgNWs and ZnONPs, resulting in a remarkably improved multi-loading operation. Importantly, substrate-integrated uFTEs constituted of the metal-oxide nanocomposite electrode semi-embedded in the polymer matrix of greatly thin <0.5 µm thickness is successfully demonstrated with the smooth surface topography, promoted by the tri-system integration including (i) AgNW-AgNW, (ii) ZnONP-ZnONP, and (iii) AgNW-ZnONP systems. Our finding unveils the complex interfacial dynamics associated with the heterogeneous interface system between AgNWs and ZnONPs and holds great promise in understanding the in-situ nano-adhesion process and increasing the design flexibility of next generation solution-processed uFTEs.

Spin Quantum Dot Light-Emitting Diodes Enabled by 2D Chiral Perovskite with Spin-Dependent Carrier Transport.

Chiral-induced spin selectivity (CISS) effect provides innovative approach to spintronics and quantum-based devices for chiral materials. Different from the conventional ferromagnetic devices, the application of CISS effect is potential to operate under room temperature and zero applied magnetic field. Low dimensional chiral perovskites by introducing chiral amines are beginning to show significant CISS effect for spin injection, but research on chiral perovskites is still in its infancy, especially on spin-light emitting diode (spin-LED) construction. Here, the spin-QLEDs enabled by 2D chiral perovskites as CISS layer for spin-dependent carrier injection and CdSe/ZnS quantum dots (QDs) as light emitting layer are reported. The regulation pattern of the chirality and thickness of chiral perovskites, which affects the circularly polarized electroluminescence (CP-EL) emission of spin-QLED, is discovered. Notably, the spin injection polarization of 2D chiral perovskites is higher than 80% and the CP-EL asymmetric factor (gCP-EL ) achieves up to 1.6 × 10-2 . Consequently, this work opens up a new and effective approach for high-performance spin-LEDs.

Efficient and stable hybrid perovskite-organic light-emitting diodes with external quantum efficiency exceeding 40 per cent.

Light-emitting diodes (LEDs) based on perovskite semiconductor materials with tunable emission wavelength in visible light range as well as narrow linewidth are potential competitors among current light-emitting display technologies, but still suffer from severe instability driven by electric field. Here, we develop a stable, efficient and high-color purity hybrid LED with a tandem structure by combining the perovskite LED and the commercial organic LED technologies to accelerate the practical application of perovskites. Perovskite LED and organic LED with close photoluminescence peak are selected to maximize photon emission without photon reabsorption and to achieve the narrowed emission spectra. By designing an efficient interconnecting layer with p-type interface doping that provides good opto-electric coupling and reduces Joule heating, the resulting green emitting hybrid LED shows a narrow linewidth of around 30 nm, a peak luminance of over 176,000 cd m-2, a maximum external quantum efficiency of over 40%, and an operational half-lifetime of over 42,000 h.

Tuning optical responses of metallic dipole nanoantenna using graphene.

Nanoantennas play a fundamental role in the nanotechnology due to their capabilities to confine and enhance the light through converting the localized fields to propagating ones, and vice versa. Here, we theoretically propose a novel nanoantenna with the metal-insulator-graphene configuration where a graphene sheet dynamically controls the characteristics of a metallic dipole antenna in terms of near-field distribution, resonance frequency, bandwidth, radiation pattern, etc. Our results show that by modifying dispersion relation of the graphene sheet attached to the insulator through tuning chemical potentials, we can achieve strong mode couplings between the graphene sheet and the metallic nanoantenna on the top of the insulator. Interestingly, the in-phase and out-of-phase couplings between metallic plasmonics and graphene plasmonics not only split the single resonance frequency of the conventional metallic dipole antenna but also modify the near-field and far-field responses of the metal-graphene nanoantenna. This work is of a great help to design high-performance electrically-tunable nanoantennas applicable both in nano-optics and nano-electronics fields.

Highly Efficient Flexible Perovskite Solar Cells through Pentylammonium Acetate Modification with Certified Efficiency of 23.35.

Among the emerging photovoltaic technologies, rigid perovskite solar cells (PSCs) have made tremendous development owing to their exceptional power conversion efficiency (PCE) of up to 25.7%. However, the record PCE of flexible PSCs (≈22.4%) still lags far behind their rigid counterparts and their mechanical stabilities are also not satisfactory. Herein, through modifying the interface between perovskite and hole transport layer via pentylammonium acetate (PenAAc) molecule a highly efficient and stable flexible inverted PSC is reported. Through synthetic manipulation of anion and cation, it is shown that the PenA+ and Ac- have strong chemical binding with both acceptor and donor defects of surface-terminating ends on perovskite films. The PenAAc-modified flexible PSCs achieve a record PCE of 23.68% (0.08 cm2 , certified: 23.35%) with a high open-circuit voltage (VOC ) of 1.17 V. Large-area devices (1.0 cm2 ) also realized an exceptional PCE of 21.52%. Moreover, the fabricated devices show excellent stability under mechanical bending, with PCE remaining above 91% of the original PCE even after 5000 bends.

Solvent Modulation of Chiral Perovskite Films Enables High Circularly Polarized Luminescence Performance from Chiral Perovskite/Quantum Dot Composites.

Materials with circularly polarized luminescence (CPL) activity are promising in many chiroptoelectronics fields, such as for biological probes, asymmetric photosynthesis, information storage, spintronic devices, and so on. Promoting the value of the dissymmetry factor (glum) for the CPL-active materials based on chiral perovskite draws increasing attention since a higher glum value indicates better CPL. In this work, we find that, after being treated with a facile solvent modulation strategy, the chirality of 2D chiral perovskite films has been enhanced a lot, which we attribute to an increased lattice distortion degree. By forming chiral perovskite/quantum dot (QD) composites, the CPL-active material is successfully obtained. The calculated maximum |glum| of these composites increased over 4 times after solvent modulation treatment (1.53 × 10-3 for the pristine sample of R-DMF and 6.91 × 10-3 for R-NMP) at room temperature. Moreover, the enhancement of the CPL intensity is ascribed to two aspects: one is the generation and transportation of spin-polarized charge carriers from chiral perovskite films to combine in the QD layer, and the other is the solvent modulation strategy to enlarge the lattice distortion of chiral perovskite films. This facile route provides an effective way to construct CPL-active materials. More importantly, this kind of composite material (chiral perovskite film/QD layer) can be easily applied for fabricating circularly polarized light-emitting diode devices for electroluminescence.

Light harvesting improvement of organic solar cells with self-enhanced active layer designs.

We present designs of organic solar cells (OSCs) incorporating periodically arranged gradient type active layer. The designs can enhance light harvesting with patterned organic materials themselves (i.e. self-enhanced active layer design) to avoid degrading electrical performances of OSCs in contrast to introducing inorganic concentrators into OSC active layers such as silicon and metallic nanostructures. Geometry of the OSC is fully optimized by rigorously solving Maxwell's equations with fast and efficient scattering matrix method. Optical absorption is accessed by a volume integral of the active layer excluding the metallic absorption. Our numerical results show that the OSC with a self-enhanced active layer, compared with the conventional planar active layer configuration, has broadband and wide-angle range absorption enhancement due to better geometric impedance matching and prolonged optical path. This work provides a theoretical foundation and engineering reference for high performance OSC designs.

Optical and electrical study of organic solar cells with a 2D grating anode.

We investigate both optical and electrical properties of organic solar cells (OSCs) incorporating 2D periodic metallic back grating as an anode. Using a unified finite-difference approach, the multiphysics modeling framework for plasmonic OSCs is established to seamlessly connect the photon absorption with carrier transport and collection by solving the Maxwell's equations and semiconductor equations (Poisson, continuity, and drift-diffusion equations). Due to the excited surface plasmon resonance, the significantly nonuniform and extremely high exciton generation rate near the metallic grating are strongly confirmed by our theoretical model. Remarkably, the nonuniform exciton generation indeed does not induce more recombination loss or smaller open-circuit voltage compared to 1D multilayer standard OSC device. The increased open-circuit voltage and reduced recombination loss by the plasmonic OSC are attributed to direct hole collections at the metallic grating anode with a short transport path. The work provides an important multiphysics understanding for plasmonic organic photovoltaics.