Chirality-Induced Spin Selectivity Enables New Breakthrough in Electrochemical and Photoelectrochemical Reactions.

To facilitate the transition from a carbon-energy-dependent society to a sustainable society, conventional engineering strategies, which encounter limitations associated with intrinsic material properties, should undergo the paradigm shift. From a theoretical viewpoint, the spin-dependent feature of oxygen evolution reaction (OER) reveals the potential of a spin-polarization strategy in enhancing the performance of electrochemical (EC) reactions. The chirality-induced spin selectivity (CISS) phenomenon attracts unprecedented attention owing to its potential utility in achieving novel breakthroughs. This paper starts with the experimental results aimed at enhancing the efficiency of the spin-dependent OER focusing on the EC system based on the CISS phenomenon. The applicability of spin-polarization to EC system is verified through various analytical methodologies to clarify the theoretical groundwork and mechanisms underlying the spin-dependent reaction pathway. The discussion is then extended to effective spin-control strategies in photoelectrochemical system based on the CISS effect. Exploring the influence of spin-state control on the kinetic and thermodynamic aspects, this perspective also discusses the effect of spin polarization induced by the CISS phenomenon on spin-dependent OER. Lastly, future directions for enhancing the performance of spin-dependent redox systems are discussed, including expansion to various chemical reactions and the development of materials with spin-control capabilities.

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.

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.

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.

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.

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.

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.

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.

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.

Chiral Perovskites for Next-Generation Photonics: From Chirality Transfer to Chiroptical Activity.

Organic-inorganic hybrid halide perovskites (OIHPs) are commonly used as prototypical materials for various applications, including photovoltaics, photodetectors, and light-emitting devices. Since the chiroptical properties of OIHPs are deciphered in 2017, chiral OIHPs have been rediscovered as new hybrid systems comprising chiral organic molecules and achiral inorganic octahedral layers. Owing to their exceptional optoelectrical properties and structural flexibility, chiral OIHPs have received a considerable amount of attention in chiral photonics, chiroptoelectronics, spintronics, and ferroelectrics. Despite their intriguing chiral properties, the transfer mechanism from chiral molecules to achiral semiconductors has not been extensively investigated. Furthermore, an in-depth understanding of the origin of chiroptical activity is still elusive. In this review article, recent advances in the chiroptical activities of chiral OIHPs and polarization-based devices adopting chiral OIHPs are comprehensively discussed, and insight into the underlying chirality transfer mechanism based on theoretical considerations is provided. This comprehensive survey, with an emphasis on the chirality transfer mechanism, will help readers understand the chiroptical properties of OIHPs, which are crucial for the development of spin-based photonic and optoelectronic devices. Additionally, promising strategies to exploit the potential of chiral OIHPs are also discussed.

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.

Chiral 2D Organic Inorganic Hybrid Perovskite with Circular Dichroism Tunable Over Wide Wavelength Range.

The effect of chemical-composition modification on the chiroptical property of chiral organic ammonium cation-containing organic inorganic hybrid perovskite (chiral OIHP) is investigated. Varying the mixing ratio of bromide and iodide anions in S- or R-C6H5CH2(CH3)NH3)2PbI4(1-x)Br4x modifies the band gap of chiral OIHP, leading to a shift of the circular dichroism (CD) signal from 495 to 474 nm. However, it is also found that an abrupt crystalline structure transition occurs, and the CD signal is turned off when iodide-determinant phases are transformed into the bromide-determinant phase. To obtain CD in the wavelength range where the bromide-determinant phase is supposed to exhibit chiroptical activity, that is, <474 nm, S- or R-C12H7CH2(CH3)NH3 with a larger spacer group can be adopted; thus, the CD signal can be further blue-shifted to ∼375 nm. Here, we show that chemical-composition modification of chiral OIHP affects the chiroptical properties of chiral OIHP in two ways: (1) tuning the wavelength of CD by modulating the excitonic band structure and (2) switching the CD on and off by inducing a crystalline-structure change. These properties can be utilized for structural engineering of high-performance chiroptical materials for spin-polarized light-emitting devices and polarization-based optoelectronics.

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.

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.

Investigating Recombination and Charge Carrier Dynamics in a One-Dimensional Nanopillared Perovskite Absorber.

Organometal halide perovskite materials have become an exciting research topic as manifested by intense development of thin film solar cells. Although high-performance solar-cell-based planar and mesoscopic configurations have been reported, one-dimensional (1-D) nanostructured perovskite solar cells are rarely investigated despite their expected promising optoelectrical properties, such as enhanced charge transport/extraction. Herein, we have analyzed the 1-D nanostructure effects of organometal halide perovskite (CH3NH3PbI3- xCl x) on recombination and charge carrier dynamics by utilizing a nanoporous anodized alumina oxide scaffold to fabricate a vertically aligned 1-D nanopillared array with controllable diameters. It was observed that the 1-D perovskite exhibits faster charge transport/extraction characteristics, lower defect density, and lower bulk resistance than the planar counterpart. As the aspect ratio increases in the 1-D structures, in addition, the charge transport/extraction rate is enhanced and the resistance further decreases. However, when the aspect ratio reaches 6.67 (diameter ∼30 nm), the recombination rate is aggravated due to high interface-to-volume ratio-induced defect generation. To obtain the full benefits of 1-D perovskite nanostructuring, our study provides a design rule to choose the appropriate aspect ratio of 1-D perovskite structures for improved photovoltaic and other optoelectrical applications.

Facile Sol-Gel-Derived Craterlike Dual-Functioning TiO2 Electron Transport Layer for High-Efficiency Perovskite Solar Cells.

Organic-inorganic hybrid perovskite solar cells (PSCs) are considered promising materials for low-cost solar energy harvesting technology. An electron transport layer (ETL), which facilitates the extraction of photogenerated electrons and their transport to the electrodes, is a key component in planar PSCs. In this study, a new strategy to concurrently manipulate the electrical and optical properties of ETLs to improve the performance of PSCs is demonstrated. A careful control over the Ti alkoxide-based sol-gel chemistry leads to a craterlike porous/blocking bilayer TiO2 ETL with relatively uniform surface pores of 220 nm diameter. Additionally, the phase separation promoter added to the precursor solution enables nitrogen doping in the TiO2 lattice, thus generating oxygen vacancies. The craterlike surface morphology allows for better light transmission because of reduced reflection, and the electrically conductive craterlike bilayer ETL enhances charge extraction and transport. Through these synergetic improvements in both optical and electrical properties, the power conversion efficiency of craterlike bilayer TiO2 ETL-based PSCs could be increased from 13.7 to 16.0% as compared to conventional dense TiO2-based PSCs.