Retarding Ion Migration for Stable Blade-Coated Inverted Perovskite Solar Cells.

The fabrication of perovskite solar cells (PSCs) through blade coating is seen as one of the most viable paths toward commercialization. However, relative to the less scalable spin coating method, the blade coating process often results in more defective perovskite films with lower grain uniformity. Ion migration, facilitated by those elevated defect levels, is one of the main triggers of phase segregation and device instability. Here, a bifunctional molecule, p-aminobenzoic acid (PABA), which enhances the barrier to ion migration, induces grain growth along the (100) facet, and promotes the formation of homogeneous perovskite films with fewer defects, is reported. As a result, PSCs with PABA achieved impressive power conversion efficiencies (PCEs) of 23.32% and 22.23% for devices with active areas of 0.1 cm2 and 1 cm2 , respectively. Furthermore, these devices maintain 93.8% of their initial efficiencies after 1 000 h under 1-sun illumination, 75 °C, and 10% relative humidity conditions.

Effect of Feature Shape and Dimension of a Confinement Geometry on Selectivity of Electrocatalytic CO2 Reduction.

The local confinement effect, which can generate a high concentration of hydroxide ions and reaction intermediates near the catalyst surface, is an important strategy for converting CO2 into multi-carbon products in electrocatalytic CO2 reduction. Therefore, understanding how the shape and dimension of the confinement geometry affect the product selectivity is crucial. In this study, we report for the first time the effect of the shape (degree of confinement) and dimension of the confined space on the product selectivity without changing the intrinsic property of Cu. We demonstrate that geometry influences the outcomes of products, such as CH4 , C2 H4 , and EtOH, in different ways: the selectivity of CH4 and EtOH is affected by shape, while the selectivity of C2 H4 is influenced by dimension of geometry predominantly. These phenomena are demonstrated, both experimentally and through simulation, to be induced by the local confinement effect within the confined structure. Our geometry model could serve as basis for designing the confined structures tailored for the production of specific products.

Atomic-Scale Homogeneous RuCu Alloy Nanoparticles for Highly Efficient Electrocatalytic Nitrogen Reduction.

Ruthenium (Ru) is the most widely used metal as an electrocatalyst for nitrogen (N2 ) reduction reaction (NRR) because of the relatively high N2 adsorption strength for successive reaction. Recently, it has been well reported that the homogeneous Ru-based metal alloys such as RuRh, RuPt, and RuCo significantly enhance the selectivity and formation rate of ammonia (NH3 ). However, the metal combinations for NRR have been limited to several miscible combinations of metals with Ru, although various immiscible combinations have immense potential to show high NRR performance. In this study, an immiscible combination of Ru and copper (Cu) is first utilized, and homogeneous alloy nanoparticles (RuCu NPs) are fabricated by the carbothermal shock method. The RuCu homogeneous NP alloys on cellulose/carbon nanotube sponge exhibit the highest selectivity and NH3 formation rate of ≈31% and -73 µmol h-1 cm-2 , respectively. These are the highest values of the selectivity and NH3 formation rates among existing Ru-based alloy metal combinations.

Synergistic Effect of Cu2 O Mesh Pattern on High-Facet Cu Surface for Selective CO2 Electroreduction to Ethanol.

Although the electroconversion of carbon dioxide (CO2 ) into ethanol is considered to be one of the most promising ways of using CO2 , the ethanol selectivity is less than 50% because of difficulties in designing an optimal catalyst that arise from the complicated pathways for the electroreduction of CO2 to ethanol. Several approaches including the fabrication of oxide-derived structures, atomic surface control, and the Cu+ /Cu interfaces have been primarily used to produce ethanol from CO2 . Here, a combined structure with Cu+ and high-facets as electrocatalysts is constructed by creating high-facets of wrinkled Cu surrounded by Cu2 O mesh patterns. Using chemical vapor deposition graphene growth procedures, the insufficiently grown graphene is used as an oxidation-masking material, and the high-facet wrinkled Cu is simultaneously generated during the graphene growth synthesis. The resulting electrocatalyst shows an ethanol selectivity of 43% at -0.8 V versus reversible hydrogen electrode, which is one of the highest ethanol selectivity values reported thus far. This is attributed to the role of Cu+ in enhancing CO binding strength, and the high-facets, which favor C-C coupling and the ethanol pathway. This method for generating the combined structure can be widely applicable not only for electrochemical catalysts but also in various fields.

Generation of high-density nanoparticles in the carbothermal shock method.

The carbothermal shock (CTS) method has attracted considerable attention in recent years because it enables the generation of finely controlled polyelemental alloy nanoparticles (NPs). However, fabricating high surface coverage of NPs with minimized exposure of the carbon substrate is essential for various electrochemical applications and has been a critical limitation in CTS method. Here, we developed a methodology for creating NPs with high surface coverage on a carbon substrate by maximizing defect sites of cellulose during CTS. Cu NPs with high surface coverage of ~85%, various single NPs and polyelemental alloy NPs were densely fabricated with high uniformity and dispersity. The synthesized Cu NPs on cellulose/carbon paper substrate were used in electrocatalytic CO2 reduction reaction showing selectivity to ethylene of ~49% and high stability for over 30 hours of reaction. Our cellulose-derived CTS method enables the greater availability of polyelemental NPs for a wide range of catalytic and electrochemical applications.

Nanoscale Wrinkled Cu as a Current Collector for High-Loading Graphite Anode in Solid-State Lithium Batteries.

Solid-state lithium batteries have been intensively studied as part of research activities to develop energy storage systems with high safety and stability characteristics. Despite the advantages of solid-state lithium batteries, their application is currently limited by poor reversible capacity arising from their high resistance. In this study, we significantly improve the reversible capacity of solid-state lithium batteries by lowering the resistance through the introduction of a graphene and wrinkle structure on the surface of the copper (Cu) current collector. This is achieved through a process of chemical vapor deposition (CVD) facilitating graphene-growth synthesis. The modified graphene/wrinkled Cu current collector exhibits a periodic wrinkled pattern 420 nm in width and 22 nm in depth, and we apply it to a graphite composite electrode to obtain an improved areal loading average value of ∼2.5 mg cm-2. The surface-modified Cu current collector is associated with a significant increase in discharge capacity of 347 mAh g-1 at 0.2 C when used with a solid polymer electrolyte. Peel test results show that the observed enhancement is due to the improved strength of adhesion occurring between the graphite composite anode and the Cu current collector, which is attributed to mechanical interlocking. The surface-modified Cu current collector structure effectively reduces resistance by improving adhesion, which subsequently improves the performance of the solid-state lithium batteries. Our study can provide perspective and emphasize the importance of electrode design in achieving enhancements in battery performance.

Interface Matters: Enhanced Photoluminescence and Long-Term Stability of Zero-Dimensional Cesium Lead Bromide Nanocrystals via Gas-Phase Aluminum Oxide Encapsulation.

Cesium lead halide perovskite nanocrystals (PNCs), while possessing facile chemical synthesis routes and high photoluminescence (PL) properties, are still challenged by issues of instability and degradation. Although atomic layer deposition (ALD) of metal oxides has been one of the common encapsulation approaches for longer term stability, its application inevitably resulted in severe loss of emission efficiency and at times partial loss of structural integrity of perovskites, creating a bottleneck in its practical viability. We demonstrate a nondestructive modified gas-phase technique with codeposition of both precursors trimethylaluminum and water to dramatically enhance the PL emission in zero-dimensional (0D) Cs4PbBr6 PNCs via alumina encapsulation. X-ray photoelectron spectroscopy analysis of Cs4PbBr6 films reveals the alumina deposition to be accompanied by elemental composition changes, particularly by the reduction of the excessive cesium content. Ab initio density functional theory simulations further unfold that the presence of excess Cs on the surface of PNCs leads to decomposition of structural [PbBr6]4- octahedra in the 0D perovskite lattice, which can be prevented in the presence of added hydroxyl groups. Our study thus unveils the pivotal role of the PNC surface composition and treatment in the process of its interaction with metal oxide precursors to control the PL properties as well as the stability of PNCs, providing an unprecedented way to use the conventional ALD technique for their successful integration into optoelectronic and photonic devices with improved properties.

Dynamical Interconversion between Excitons and Geminate Charge Pairs in Two-Dimensional Perovskite Layers Described by the Onsager-Braun Model.

Time-resolved photoluminescence (PL) and femtosecond transient absorption (TA) spectroscopy are employed to study the photoexcitation dynamics in a highly emissive two-dimensional perovskite compound (en)4Pb2Br9·3Br with the ethylene diammonium (en) spacer. We find that while the PL kinetics is substantially T-dependent over the whole range of studied temperatures T ∼ 77-350 K, the PL quantum yield remains remarkably nearly T-independent up to T ∼ 280-290 K, appreciably decreasing only at higher temperatures. Considerable differences are also revealed between the TA spectra and the responses to the excitation power at low and at room temperatures. Numerical solutions of Onsager-Braun-type kinetic-diffusion equations illustrate that the salient features of the experimental observations are consistent with the picture of a T-dependent dynamic interplay between tightly bound emissive excitons and larger-size, loosely bound, nonemissive geminate charge pairs arising already at earlier relaxation times. The geminate pairs play the role of "reservoir" states providing a delayed feeding into the emitting excitons, thus giving rise to the longer-time PL decay components and accounting for a stable PL output at lower temperatures. At higher temperatures, the propensity for thermal dissociation of excitons and bound pairs increases, leading subsequently to the precipitous decrease of the PL.

Delayed Photoluminescence and Modified Blinking Statistics in Alumina-Encapsulated Zero-Dimensional Inorganic Perovskite Nanocrystals.

We demonstrate enhancement of the photoluminescence (PL) properties of individual zero-dimensional (0D) Cs4PbBr6 perovskite nanocrystals (PNCs) upon encapsulation by alumina using an appropriately modified atomic layer deposition method. In addition to the increased PL intensity and improved long-term stability of encapsulated PNCs, our single-particle studies reveal substantial changes in the PL blinking statistics and the persistent appearance of the long-lived, "delayed" PL components. The blinking patterns exhibit a modification from the fast switching between fluorescent ON and OFF states found in bare PNCs to a behavior with longer ON states and more isolated OFF states in alumina-encapsulated PNCs. Controlled exposure of 0D nanocrystals to moisture suggests that the observed PL lifetime changes may be related to water-induced "reservoir" states that allow for longer-lived charge storage with subsequent back-feeding into the emissive states. Viable encapsulation of PNCs with metal oxides that can preserve and even enhance their PL properties can be utilized in the fabrication of extended structures on their basis for optoelectronic and photonic applications.

Understanding effects of precursor solution aging in triple cation lead perovskite.

The solution process is the most widely used method to prepare perovskite absorbers for high performance solar cells due to its ease for fabrication and low capital cost. However, an insufficient level of reproducibility of the solution process is often a concern. Complex precursor solution chemistry is likely one of the main reasons for the reproducibility issue. Here we report the effects of triple cation lead mixed-halide perovskite precursor solution aging on the quality of the resulting films and the device performance. Our study revealed that precursor solution aging has a great influence on the colloidal size distribution of the solution, which then affects the phase purity of the films and device performance. We determined the optimum aging hours that led to the best device efficiency along with the highest reproducibility. Dynamic light scattering revealed the formation of micron-sized colloidal intermediates in the solution when aged longer than the optimum hours and further analysis along with X-ray diffraction measurements suggested there were two chemical origins of the large aggregates, FA-based and Cs-based complexes.

Improving Uniformity and Reproducibility of Hybrid Perovskite Solar Cells via a Low-Temperature Vacuum Deposition Process for NiOx Hole Transport Layers.

Recently, the trend in inverted hybrid perovskite solar cells (PVSCs) has been to utilize NiOx as hole transport layers. However, the majority of reported solution-processed NiOx films require a high-temperature thermal annealing process, which is unfavorable for large-scale manufacturing and suffers from lack of uniformity. We report, for the first time, e-beam evaporation as a low-temperature vacuum process for the deposition of NiOx hole transport layers for PVSCs. Device characterization shows that efficiency is on par with solution-processed methods, the highest efficiency at 15.4% with no obvious hysteresis. Differences are found to be due to the presence of more Ni3+ in e-beam evaporated NiOx, which are responsible for a lower transmittance but higher conductivity. Most importantly, e-beam-evaporated NiOx-based PVSCs show greater uniformity and reproducibility compared to spin-coated NiOx-based PVSCs. Finally, e-beam-evaporated NiOx has the additional advantage of being produced by a low-temperature deposition process and applicable over large areas. This work, therefore, represents a significant step toward large-area PVSCs, where e-beam evaporation can be used for the low-temperature uniform deposition of charge-transport layers, such as NiOx.

Ultralong Radiative States in Hybrid Perovskite Crystals: Compositions for Submillimeter Diffusion Lengths.

Organic-inorganic hybrid perovskite materials have recently evolved into the leading candidate solution-processed semiconductor for solar cells due to their combination of desirable optical and charge transport properties. Chief among these properties is the long carrier diffusion length, which is essential to optimizing the device architecture and performance. Herein, we used time-resolved photoluminescence (at low excitation fluence, 10.59 µJ·cm-2 upon two-photon excitation), which is the most accurate and direct approach to measure the radiative charge carrier lifetime and diffusion lengths. Lifetimes of about 72 and 4.3 µs for FAPbBr3 and FAPbI3 perovskite single crystals have been recorded, presenting the longest radiative carrier lifetimes reported to date for perovskite materials. Subsequently, carrier diffusion lengths of 107.2 and 19.7 µm are obtained. In addition, we demonstrate the key role of the organic cation units in modulating the carrier lifetime and its diffusion lengths, in which the defect formation energies for FA cations are much higher than those with the MA ones.

CsPb2 Br5 Single Crystals: Synthesis and Characterization.

CsPb2 Br5 is a ternary halogen-plumbate material with close characteristics to the well-reported halide perovskites. Owing to its unconventional two-dimensional structure, CsPb2 Br5 is being looked at broadly for potential applications in optoelectronics. CsPb2 Br5 investigations are currently limited to nanostructures and powder forms of the material, which present unclear and conflicting optical properties. In this study, we present the synthesis and characterization of CsPb2 Br5 bulk single crystals, which enabled us to finally clarify the material's optical features. Our CsPb2 Br5 crystal has a two-dimensional structure with Pb2 Br5- layers spaced by Cs+ cations, and exhibits approximately 3.1 eV indirect band gap with no emission in the visible spectrum.

Highly transparent and UV-resistant superhydrophobic SiO(2)-coated ZnO nanorod arrays.

Highly transparent and UV-resistant superhydrophobic arrays of SiO2-coated ZnO nanorods are prepared in a sequence of low-temperature (<150 °C) steps on both glass and thin sheets of PET (2 × 2 in.(2)), and the superhydrophobic nanocomposite is shown to have minimal impact on solar cell device performance under AM1.5G illumination. Flexible plastics can serve as front cell and backing materials in the manufacture of flexible displays and solar cells.

Demonstration of the feasibility of a complete ellipsometric characterization method based on an artificial neural network.

Ellipsometry is an optical technique that is widely used for determining optical and geometrical properties of optical thin films. These properties are in general extracted from the ellipsometric measurement by solving an inverse problem. Classical methods like the Levenberg-Marquardt algorithm are generally too long, depending on direct calculation and are very sensitive to local minima. In this way, the neural network has proved to be an efficient tool for solving these kinds of problems in a very short time. Indeed, it is rapid and less sensitive to local minima than the classical inversion method. We suggest a complete neural ellipsometric characterization method for determining the index dispersion law and the thickness of a simple SiO(2) or photoresist thin layer on Si, SiO(2), and BK7 substrates. The influence of the training couples on the artificial neural network performance is also discussed.

Recognition of diffraction-grating profile using a neural network classifier in optical scatterometry.

Optical scatterometry has been given much credit during the past few years in the semiconductor industry. The geometry of an optical diffracted structure is deduced from the scattered intensity by solving an inverse problem. This step always requires a previously defined geometrical model. We develop an artificial neural network classifier whose purpose is to identify the structural geometry of a diffraction grating from its measured ellipsometric signature. This will take place before the characterization stage. Two types of geometry will be treated: sinusoidal and symmetric trapezoidal. Experimental results are performed on two manufactured samples: a sinusoidal photoresist grating deposited on a glass substrate and a trapezoidal grating etched on a SiO2 substrate with periods of 2 microm and 0.565 microm, respectively.