Nontypical Wulff-Shape Silicon Nanosheets with High Catalytic Activity.

Nanostructured silicon with an equilibrium shape has exhibited hydrogen evolution reaction activity mainly owing to its high surface area, which is distinct from that of bulk silicon. Such a Wulff shape of silicon favors low-surface-energy planes, resulting in silicon being an anisotropic and predictably faceted solid in which certain planes are favored, but this limits further improvement of the catalytic activity. Here, we introduce nanoporous silicon nanosheets that possess high-surface-energy crystal planes, leading to an unconventional Wulff shape that bolsters the catalytic activity. The high-index plane, uncommonly seen in the Wulff shape of bulk Si, has a band structure optimally aligned with the redox potential necessary for hydrogen generation, resulting in an apparent quantum yield (AQY) of 12.1% at a 400 nm wavelength. The enhanced light absorption in nanoporous silicon nanosheets also contributes to the high photocatalytic activity. Collectively, the strategy of making crystals with nontypical Wulff shapes can provide a route toward various classes of photocatalysts for hydrogen production.

Chirality-Induced Spin Selectivity of Chiral 2D Perovskite Enabling Efficient Spin-Dependent Oxygen Evolution Reaction.

The sluggish and complex multi-step oxygen evolution reaction remains an obstacle to bias-free photoelectrochemical water-splitting systems. Several theoretical studies have suggested that spin-aligned intermediate radicals can significantly enhance the kinetic rates for oxygen generation. Herein, it is reported that the chirality-induced spin selectivity phenomena can become an impressive approach by adopting chiral 2D organic-inorganic hybrid perovskites as a spin-filtering layer on the photoanode. This chiral 2D perovskite-based water-splitting device achieves enhanced oxygen evolution performance with a reduced overpotential of 0.14 V, high fill factor, and 230% increased photocurrent compared to a device without a spin-filtering layer. Moreover, combined with a superhydrophobic patterning strategy, this device realizes excellent operational stability by sustaining ≈90% of the initial photocurrent, even after 10 h.

Tailoring the Time-Averaged Structure for Polarization-Sensitive Chiral Perovskites.

Chiral perovskites have emerged as promising candidates for polarization-sensing materials. Despite their excellent chiroptical properties, the nature of their multiple-quantum-well structures is a critical hurdle for polarization-based and spintronic applications. Furthermore, as the origin of chiroptical activity in chiral perovskites is still illusive, the strategy for simultaneously enhancing the chiroptical activity and charge transport has not yet been reported. Here, we demonstrated that incorporating a Lewis base into the lattice can effectively tune the chiroptical response and electrical properties of chiral perovskites. Through solid-state nuclear magnetic resonance spectroscopic measurements and theoretical calculations, it was demonstrated that the material property manipulation resulted from the change in the time-averaged structure induced by the Lewis base. Finally, as a preliminary proof of concept, a vertical-type circularly polarized light photodetector based on chiral perovskites was developed, exhibiting an outstanding performance with a distinguishability of 0.27 and a responsivity of 0.43 A W-1.

Universal Bifacial Stamping Approach Enabling Reverse-Graded Ruddlesden-Popper 2D Perovskite Solar Cells.

Quasi 2D perovskite solar cells (PSCs) are promising light absorbers that overcome the inherent instabilities of 3D perovskites. High-performance and stable 2D PSCs require careful control over the crystallographic orientation and phase distribution. This study introduces a simple and universal bifacial stamping method to obtain highly oriented perovskite crystals with a reverse-graded structure, where the low-n-value 2D perovskite phases are located mainly at the film surfaces. Bifacial stamping of 3D perovskite films atop the 2D films enables incorporation of 2D spacer cations into the 3D film surfaces, forming reverse-graded quasi-2D perovskite films. During stamping, suppressed evaporation of the precursor solvent induces heterogeneous nucleation from the contact interface between the 2D and 3D films, resulting in well-crystallized perovskite films having out-of-plane alignments with respect to the substrate. Thus, a highly oriented and reverse-graded quasi-2D perovskite with an average n value of 18 is obtained with power conversion efficiency exceeding 17% and high open-circuit voltage of 1.11 V for iso-butylammonium (iso-BA)-based (iso-BA2 MAn -1 Pbn I3 n +1 ) PSCs. The unencapsulated device retains 92% of its initial efficiency after aging at 40 ± 5% relative humidity for 1200 h. This work provides a new strategy for fabricating highly oriented and phase-controlled quasi-2D PSCs.

Strain-Mediated Phase Stabilization: A New Strategy for Ultrastable α-CsPbI3 Perovskite by Nanoconfined Growth.

All-inorganic cesium lead triiodide (CsPbI3 ) perovskite is considered a promising solution-processable semiconductor for highly stable optoelectronic and photovoltaic applications. However, despite its excellent optoelectronic properties, the phase instability of CsPbI3 poses a critical hurdle for practical application. In this study, a novel stain-mediated phase stabilization strategy is demonstrated to significantly enhance the phase stability of cubic α-phase CsPbI3 . Careful control of the degree of spatial confinement induced by anodized aluminum oxide (AAO) templates with varying pore sizes leads to effective manipulation of the phase stability of α-CsPbI3 . The Williamson-Hall method in conjunction with density functional theory calculations clearly confirms that the strain imposed on the perovskite lattice when confined in vertically aligned nanopores can alter the formation energy of the system, stabilizing α-CsPbI3 at room temperature. Finally, the CsPbI3 grown inside nanoporous AAO templates exhibits exceptional phase stability over three months under ambient conditions, in which the resulting light-emitting diode reveals a natural red color emission with very narrow bandwidth (full width at half maximum of 33 nm) at 702 nm. The universally applicable template-based stabilization strategy can give in-depth insights on the strain-mediated phase transition mechanism in all-inorganic perovskites.

Core-Shell Perovskite Quantum Dots for Highly Selective Room-Temperature Spin Light-Emitting Diodes.

Circularly polarized light (CPL) is a crucial light source with a wide variety of potential applications such as magnetic recording, and 3D display. Here, core-shell heterostructured perovskite quantum dots (QDs) for room-temperature spin-polarized light-emitting diodes (spin-LEDs) are developed. Specifically, a 2D chiral perovskite shell is deposited onto the achiral 3D inorganic perovskite (CsPbBr3 ) core. Owing to the chiral-induced spin selectivity effect, the spin state of the injected charge carriers is biased when they are transmitted through the 2D chiral shell. The spin-controlled carriers then radiatively recombine inside the CsPbBr3 emissive core, resulting in CPL emission. It is demonstrated that the (R)- and (S)-1-(2-(naphthyl)ethylamine) (R-/S-NEA) 2D chiral cations enhance the spin polarization degree due to their strong chiroptical properties. Systematical defect analyses confirm that 2D chiral cations (i.e., R-/S-NEA) successfully passivate halide vacancies at the surface of the CsPbBr3 QDs, thereby attaining a high photoluminescence quantum yield of 78%. Moreover, the spin-LEDs prepared with core-shell QDs achieve a maximum external quantum efficiency of 5.47% and circularly polarized electroluminescence with a polarization degree (PCP-EL ) of 12% at room temperature. Finally, various patterns fabricated by inkjet printing the core-shell QDs emit strong CPL, highlighting their potential as an emitter for next-generation displays.

Stable water splitting using photoelectrodes with a cryogelated overlayer.

Hydrogen production techniques based on solar-water splitting have emerged as carbon-free energy systems. Many researchers have developed highly efficient thin-film photoelectrochemical (PEC) devices made of low-cost and earth-abundant materials. However, solar water splitting systems suffer from short lifetimes due to catalyst instability that is attributed to both chemical dissolution and mechanical stress produced by hydrogen bubbles. A recent study found that the nanoporous hydrogel could prevent the structural degradation of the PEC devices. In this study, we investigate the protection mechanism of the hydrogel-based overlayer by engineering its porous structure using the cryogelation technique. Tests for cryogel overlayers with varied pore structures, such as disconnected micropores, interconnected micropores, and surface macropores, reveal that the hydrogen gas trapped in the cryogel protector reduce shear stress at the catalyst surface by providing bubble nucleation sites. The cryogelated overlayer effectively preserves the uniformly distributed platinum catalyst particles on the device surface for over 200 h. Our finding can help establish semi-permanent photoelectrochemical devices to realize a carbon-free society.

Fluorinated Organic Cations Derived Chiral 2D Perovskite Enabling Enhanced Spin-Dependent Oxygen Evolution Reaction.

Chirality-induced spin selectivity observed in chiral 2D organic-inorganic hybrid perovskite holds promise to achieve spin-dependent electrochemistry. However, conventional chiral 2D perovskites suffer from low conductivity and hygroscopicity, limiting electrochemical performance and operational stability. Here, a cutting-edge material design is introduced to develop a stable and efficient chiral perovskite-based spin polarizer by employing fluorinated chiral cation. The fluorination approach effectively promotes the charge carrier transport along the out-of-plane direction by mitigating the dielectric confinement effect within the multi-quantum well-structured 2D perovskite. Integrating the fluorinated cation incorporated spin polarizer with BiVO4 photoanode considerably boosts the photocurrent density while reducing overpotential through a spin-dependent oxygen evolution reaction. Furthermore, the hydrophobic nature of fluorine in spin polarizer endows operational stability to the photoanode, extending the durability by 280% as compared to the device with non-fluorinated spin polarizer.

Unraveling chirality transfer mechanism by structural isomer-derived hydrogen bonding interaction in 2D chiral perovskite.

In principle, the induced chirality of hybrid perovskites results from symmetry-breaking within inorganic frameworks. However, the detailed mechanism behind the chirality transfer remains unknown due to the lack of systematic studies. Here, using the structural isomer with different functional group location, we deduce the effect of hydrogen-bonding interaction between two building blocks on the degree of chirality transfer in inorganic frameworks. The effect of asymmetric hydrogen-bonding interaction on chirality transfer was clearly demonstrated by thorough experimental analysis. Systematic studies of crystallography parameters confirm that the different asymmetric hydrogen-bonding interactions derived from different functional group location play a key role in chirality transfer phenomena and the resulting spin-related properties of chiral perovskites. The methodology to control the asymmetry of hydrogen-bonding interaction through the small structural difference of structure isomer cation can provide rational design paradigm for unprecedented spin-related properties of chiral perovskite.

Elucidating the origin of chiroptical activity in chiral 2D perovskites through nano-confined growth.

Chiral perovskites are being extensively studied as a promising candidate for spintronic- and polarization-based optoelectronic devices due to their interesting spin-polarization properties. However, the origin of chiroptical activity in chiral perovskites is still unknown, as the chirality transfer mechanism has been rarely explored. Here, through the nano-confined growth of chiral perovskites (MBA2PbI4(1-x)Br4x), we verified that the asymmetric hydrogen-bonding interaction between chiral molecular spacers and the inorganic framework plays a key role in promoting the chiroptical activity of chiral perovskites. Based on this understanding, we observed remarkable asymmetry behavior (absorption dissymmetry of 2.0 × 10-3 and anisotropy factor of photoluminescence of 6.4 × 10-2 for left- and right-handed circularly polarized light) in nanoconfined chiral perovskites even at room temperature. Our findings suggest that electronic interactions between building blocks should be considered when interpreting the chirality transfer phenomena and designing hybrid materials for future spintronic and polarization-based devices.

Multifunctional Self-Combustion Additives Strategy to Fabricate Highly Responsive Hybrid Perovskite Photodetectors.

To resolve the inherent trade-off issue between responsivity and detectivity in FA0.9Cs0.1PbI3 perovskite photodetectors, this paper proposes a novel strategy using multifunctional self-combustion additives (urea and ammonium nitrate). During the early stages of crystallization, urea allows for the formation of a strong Lewis complex-derived low-dimensional intermediate phase; this suppresses the formation of perovskite nuclei, while ammonium ions assist the preferred grain growth along the [110] direction. During the high-temperature annealing steps, a self-combusting exothermic reaction occurs between urea as a fuel and NH4NO3 as an oxidizer, through which a locally supplied heat facilitates the removal of residual urea and byproducts. These multifunctional roles of self-combustible additives facilitate the production of high-quality, enlarged grain-structured perovskite films with improved optoelectronic properties, as confirmed by various analyses, including impedance spectroscopy and intensity-modulated photocurrent spectroscopy. The resulting FA0.9Cs0.1PbI3-based photodiode-type photodetectors exhibit outstanding performance, such as a high responsivity (0.762 A W-1) and specific detectivity (over 5.08 × 1013 Jones) at a very low external reverse bias (-0.5 V). Our findings clearly suggest that the multifunctional self-combustion additives strategy could help realize the full potential of FA1-xCsxPbI3 as a photodiode-type photodetector.

Energy Level-Graded Al-Doped ZnO Protection Layers for Copper Nanowire-Based Window Electrodes for Efficient Flexible Perovskite Solar Cells.

Flexible perovskite solar cells (PSCs) have attracted significant interest as promising candidates for portable and wearable devices. Copper nanowires (CuNWs) are promising candidates for transparent conductive electrodes for flexible PSCs because of their excellent conductivity, flexibility, and cost-effectiveness. However, because of the thermal/chemical instability of CuNWs, they require a protective layer for application in PSCs. Previous PSCs with CuNW-based electrodes generally exhibited poor performances compared with their indium tin oxide-based counterparts because of the neglect of the interfacial energetics between the electron transport layer (ETL) and CuNWs. Herein, an Al-doped ZnO (AZO) protective layer fabricated using atomic layer deposition is introduced. The AZO/CuNW-based composite electrode exhibits improved thermal/chemical stability and favorable band alignment between the ETL and CuNWs, based on the Al dopant concentration tuning. As a result, the Al content gradient AZO (g-AZO), composed of three successively deposited AZO layers, leads to highly efficient flexible PSCs with a power conversion efficiency (PCE) of 14.18%, whereas the PCE of PSCs with a non-g-AZO layer is 12.34%. This improvement can be attributed to the efficient electron extraction and reduced charge recombination. Furthermore, flexible PSCs based on g-AZO-based composite electrodes retain their initial PCE, even after 600 bending cycles, demonstrating excellent mechanical stability.

All-Solution-Processed Thermally and Chemically Stable Copper-Nickel Core-Shell Nanowire-Based Composite Window Electrodes for Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (PSCs) have recently attracted tremendous attention because of their excellent efficiency and the advantage of a low-cost fabrication process. As a transparent electrode for PSCs, the application of copper nanowire (CuNW)-network was limited because of its thermal/chemical instability, despite its advantages in terms of high optical/electrical properties and low-cost production. Here, the copper-nickel core-shell nanowire (Cu@Ni NW)-based composite electrode is proposed as a bottom window electrode for PSCs, without the involvement of a high-cost precious metal and vacuum process. The dense and uniform Ni protective shell for CuNWs is attainable by simple electroless plating, and the resulting Cu@Ni NWs exhibit outstanding chemical stability as well as thermal stability compared with bare CuNWs. When the Ni layer with the optimal thickness is introduced, the Cu@Ni NW electrode shows a high transmittance of 80.5% AVT at 400-800 nm, and a sheet resistance of 49.3 ± 5 Ω sq-1. Using the highly stable Cu@Ni NWs, the composite electrode structure is fabricated with sol-gel-derived Al-doped zinc oxide (AZO) over-layer for better charge collection and additional protection against iodine ions from the perovskite. The PSCs fabricated with AZO/Cu@Ni NW-based composite electrode demonstrate a power conversion efficiency (PCE) of 12.2% and excellent long-term stability maintaining 91% of initial PCE after being stored for 500 h at room temperature. Experimental results demonstrate the potential of highly stable Cu@Ni NW-based electrodes as the cost-effective alternative transparent electrode, which can facilitate the commercialization of PSCs.