Key Factors in Enhancing Pseudocapacitive Properties of PANI-InOx Hybrid Thin Films Prepared by Sequential Infiltration Synthesis.

Sequential infiltration synthesis (SIS) is an emerging vapor-phase synthetic route for the preparation of organic-inorganic composites. Previously, we investigated the potential of polyaniline (PANI)-InOx composite thin films prepared using SIS for application in electrochemical energy storage. In this study, we investigated the effects of the number of InOx SIS cycles on the chemical and electrochemical properties of PANI-InOx thin films via combined characterization using X-ray photoelectron spectroscopy, ultraviolet-visible spectroscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and cyclic voltammetry. The area-specific capacitance values of PANI-InOx samples prepared with 10, 20, 50, and 100 SIS cycles were 1.1, 0.8, 1.4, and 0.96 mF/cm², respectively. Our result shows that the formation of an enlarged PANI-InOx mixed region directly exposed to the electrolyte is key to enhancing the pseudocapacitive properties of the composite films.

Comparative Study of Thermal and Plasma-Enhanced Atomic Layer Deposition of Iron Oxide Using Bis(N,N'-di-butylacetamidinato)iron(II).

Only a few iron precursors that can be used in the atomic layer deposition (ALD) of iron oxides have been examined thus far. This study aimed to compare the various properties of FeOx thin films deposited using thermal ALD and plasma-enhanced ALD (PEALD) and to evaluate the advantages and disadvantages of using bis(N,N'-di-butylacetamidinato)iron(II) as an Fe precursor in FeOx ALD. The PEALD of FeOx films using iron bisamidinate has not yet been reported. Compared with thermal ALD films, PEALD films exhibited improved properties in terms of surface roughness, film density, and crystallinity after they were annealed in air at 500 °C. The annealed films, which had thicknesses exceeding ~ 9 nm, exhibited hematite crystal structures. Additionally, the conformality of the ALD-grown films was examined using trench-structured wafers with different aspect ratios.

Conductive Polyaniline-Indium Oxide Composite Films Prepared by Sequential Infiltration Synthesis for Electrochemical Energy Storage.

Composites of conductive polymers (CP) and metal oxides (MO) have attracted continued interest in the past decade for diverse application fields because the synergistic effects of CP and MO enable the realization of unusual electronic, electrochemical, catalytic, and mechanical properties of the composites. Herein, we present a novel method for the sequential infiltration synthesis of composite films of polyaniline (PANI) and indium oxide (InO x ) with high electrical conductivities (4-9 S/cm). The synthesized composite films were composed of two phases of graded concentration: InO x with oxygen vacancies and PANI with partially protonated molecular units. The PANI-InO x composite films displayed enhanced electrochemical activity with a pair of well-defined redox peaks. The open interfacial regions between the InO x and PANI phases may provide efficient pathways for ion diffusion and active sites for improved charge transfer.

Understanding Physicochemical Mechanisms of Sequential Infiltration Synthesis toward Rational Process Design for Uniform Incorporation of Metal Oxides.

Sequential infiltration synthesis (SIS) is a novel technique for fabricating organic-inorganic hybrid materials and porous inorganic materials by leveraging the diffusion of gas-phase precursors into a polymer matrix and chemical reactions between the precursors to synthesize inorganic materials therein. This study aims to obtain a fundamental understanding of the physicochemical mechanisms behind SIS, from which the SIS processing conditions are rationally designed to obtain precise control over the distribution of metal oxides. Herein, in situ FTIR spectroscopy was correlated with various ex situ characterization techniques to study a model system involving the growth of aluminum oxides in poly(methyl methacrylate) using trimethyl aluminum (TMA) and water as the metal precursor and co-reactant, respectively. We identified the prominent chemical states of the sorbed TMA precursors: (1) freely diffusing precursors, (2) weakly bound precursors, and (3) precursors strongly bonded to pre-existing oxide clusters and studied how their relative contributions to oxide formation vary in relation to the changes in the rate-limiting step under different growth conditions. Finally, we demonstrate that uniform incorporation of metal oxide is realized by a rational design of processing conditions, by which the major chemical species contributing to oxide formation is modulated.

Chromism-Integrated Sensors and Devices for Visual Indicators.

The bifunctionality of chromism-integrated sensors and devices has been highlighted because of their reversibility, fast response, and visual indication. For example, one of the representative chromism electrochromic materials exhibits optical modulation under ion insertion/extraction by applying a potential. This operation mechanism can be integrated with various sensors (pressure, strain, biomolecules, gas, etc.) and devices (energy conversion/storage systems) as visual indicators for user-friendly operation. In this review, recent advances in the field of chromism-integrated systems for visual indicators are categorized for various chromism-integrated sensors and devices. This review can provide insights for researchers working on chromism, sensors, or devices. The integrated chromic devices are evaluated in terms of coloration-bleach operation, cycling stability, and coloration efficiency. In addition, the existing challenges and prospects for chromism-integrated sensors and devices are summarized for further research.

Boosting Electrochemical Activity of Porous Transparent Conductive Oxides Electrodes Prepared by Sequential Infiltration Synthesis.

Sequential infiltration synthesis (SIS) is an emerging technique for producing inorganic-organic hybrid materials and templated inorganic nanomaterials. The application space for SIS is expanding rapidly in areas such as lithography, filtration, photovoltaics, antireflection, and triboelectricity, but not in the field of electrochemistry. This study performs SIS for the fabrication of porous, transparent, and electrically conductive films of indium zinc oxide (IZO) to evaluate their potential as an electrode for electrochemistry. The electrochemical activity of IZO-coated electrodes is evaluated when their surfaces are modified with ferrocenecarboxylic acid (FcCOOH), a model redox molecule. Results show a 25-fold enhancement in peak current densities mediated by an Fc/Fc+ redox couple for an IZO-coated electrode in comparison with bare electrodes; this is afforded by the porous morphology of the IZO film and the enhanced binding efficiency of FcCOOH on the IZO film. The results confirm the potential of SIS for the preparation of porous transparent conducting oxide electrodes, which will enable the application of SIS-derived materials in various electrochemical fields.

Uniformity of HfO2 Thin Films Prepared on Trench Structures via Plasma-Enhanced Atomic Layer Deposition.

In this study, we assessed the physical and chemical properties of HfO2 thin films deposited by plasma-enhanced atomic layer deposition (PEALD). We confirmed the self-limiting nature of the surface reactions involved in the HfO2 thin film's growth by tracing the changes in the growth rate and refractive index with respect to the different dose times of the Hf precursor and O2 plasma. The PEALD conditions were optimized with consideration of the lowest surface roughness of the films, which was measured by atomic force microscopy (AFM). High-resolution X-ray photoelectron spectroscopy (XPS) was utilized to characterize the chemical compositions, and the local chemical environments of the HfO2 thin films were characterized based on their surface roughness and chemical compositions. The surface roughness and chemical bonding states were significantly influenced by the flow rate and plasma power of the O2 plasma. We also examined the uniformity of the films on an 8″ Si wafer and analyzed the step coverage on a trench structure of 1:13 aspect ratio. In addition, the crystallinity and crystalline phases of the thin films prepared under different annealing conditions and underlying layers were analyzed.

Concurrent and Selective Determination of Dopamine and Serotonin with Flexible WS2 /Graphene/Polyimide Electrode Using Cold Plasma.

Makers of point-of-care devices and wearable diagnostics prefer flexible electrodes over conventional electrodes. In this study, a flexible electrode platform is introduced with a WS2 /graphene heterostructure on polyimide (WGP) for the concurrent and selective determination of dopamine and serotonin. The WGP is fabricated directly via plasma-enhanced chemical vapor deposition (PECVD) at 150 °C on a flexible polyimide substrate. Owing to the limitations of existing fabrication methods from physical transfer or hydrothermal methods, many studies are not conducted despite excellent graphene-based heterostructures. The PECVD synthesis method can provide an innovative WS2 /graphene heterostructure of uniform quality and sufficient size (4 in.). This unique heterostructure affords excellent electrical conductivity in graphene and numerous electrochemically active sites in WS2 . A large number of uniform qualities of WGP electrodes show reproducible and highly sensitive electrochemical results. The synergistic effect enabled well-separated voltammetric signals for dopamine and serotonin with a potential gap of 188 mV. Moreover, the practical application of the flexible sensor is successfully evaluated by using artificial cerebrospinal fluid.

Resolving the Atomic Structure of Sequential Infiltration Synthesis Derived Inorganic Clusters.

Sequential infiltration synthesis (SIS) is a route to the precision deposition of inorganic solids in analogy to atomic layer deposition but occurs within (vs upon) a soft material template. SIS has enabled exquisite nanoscale morphological complexity in various oxides through selective nucleation in block copolymers templates. However, the earliest stages of SIS growth remain unresolved, including the atomic structure of nuclei and the evolution of local coordination environments, before and after polymer template removal. We employed In K-edge extended X-ray absorption fine structure and atomic pair distribution function analysis of high-energy X-ray scattering to unravel (1) the structural evolution of InOxHy clusters inside a poly(methyl methacrylate) (PMMA) host matrix and (2) the formation of porous In2O3 solids (obtained after annealing) as a function of SIS cycle number. Early SIS cycles result in InOxHy cluster growth with high aspect ratio, followed by the formation of a three-dimensional network with additional SIS cycles. That the atomic structures of the InOxHy clusters can be modeled as multinuclear clusters with bonding patterns related to those in In2O3 and In(OH)3 crystal structures suggests that SIS may be an efficient route to 3D arrays of discrete-atom-number clusters. Annealing the mixed inorganic/polymer films in air removes the PMMA template and consolidates the as-grown clusters into cubic In2O3 nanocrystals with structural details that also depend on SIS cycle number.

Multiscale porous elastomer substrates for multifunctional on-skin electronics with passive-cooling capabilities.

In addition to mechanical compliance, achieving the full potential of on-skin electronics needs the introduction of other features. For example, substantial progress has been achieved in creating biodegradable, self-healing, or breathable, on-skin electronics. However, the research of making on-skin electronics with passive-cooling capabilities, which can reduce energy consumption and improve user comfort, is still rare. Herein, we report the development of multifunctional on-skin electronics, which can passively cool human bodies without needing any energy consumption. This property is inherited from multiscale porous polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene (SEBS) supporting substrates. The multiscale pores of SEBS substrates, with characteristic sizes ranging from around 0.2 to 7 µm, can effectively backscatter sunlight to minimize heat absorption but are too small to reflect human-body midinfrared radiation to retain heat dissipation, thereby delivering around 6 °C cooling effects under a solar intensity of 840 W⋅m-2 Other desired properties, rooted in multiscale porous SEBS substrates, include high breathability and outstanding waterproofing. The proof-of-concept bioelectronic devices include electrophysiological sensors, temperature sensors, hydration sensors, pressure sensors, and electrical stimulators, which are made via spray printing of silver nanowires on multiscale porous SEBS substrates. The devices show comparable electrical performances with conventional, rigid, nonporous ones. Also, their applications in cuffless blood pressure measurement, interactive virtual reality, and human-machine interface are demonstrated. Notably, the enabled on-skin devices are dissolvable in several organic solvents and can be recycled to reduce electronic waste and manufacturing cost. Such on-skin electronics can serve as the basis for future multifunctional smart textiles with passive-cooling functionalities.

High-Temperature Selective Emitter Design and Materials: Titanium Aluminum Nitride Alloys for Thermophotovoltaics.

The efficiency of a thermophotovoltaic (TPV) system depends critically upon the spectral selectivity and stability of an emitter, which may operate most effectively at temperatures in excess of 1000 °C. We computationally design and experimentally demonstrate a novel selective emitter design based on multilayer nanostructures, robust to off-normal emission angles. A computational search of the material and temperature compatibility space of simple emitter designs motivates new material classes and identifies several promising multilayer nanostructure designs for both TPV absorber and emitter applications. One such structure, comprising a thin (<100 nm) tunable TixAl1-xN (TiAlN) absorber and refractory oxide Bragg reflector is grown on W metal foil. In agreement with simulations, the emitter achieves record spectral efficiency (43.4%) and power density (3.6 W/cm2) for an emitter with at least 1 h of high temperature (>800 °C) operation.

Plasma-Enhanced Atomic Layer Deposition of TiAlN: Compositional and Optoelectronic Tunability.

Titanium nitride (TiN) is a unique refractory plasmonic material, the nanocomposites and alloys of which provide further opportunities to tailor its optical and photonic properties. We prepare TiAlN films of continuously variable compositions through the systematic variation of TiN versus AlN cycle ratio in plasma-enhanced atomic layer deposition (PEALD) and investigate the resulting thin-film composition, crystallinity, and optical properties. The resulting properties of TiAlN films are not simple linear combinations of the TiN and AlN films, which exhibit distinct metallic and dielectric properties, but instead are dramatically influenced by the local chemical environment of neighboring constituents. In situ spectroscopic ellipsometry further enables measurement of the varying optical properties of TiAlN films, which evolve over 10 s of nm of film thickness. The tunable optoelectronic properties of TiAlN films enable durable coatings of variable electrical resistance as well as high-temperature diffusion barriers and optical coatings with application to selective solar absorbers and emitters.

Charge Transfer Dynamics of Phase-Segregated Halide Perovskites: CH3NH3PbCl3 and CH3NH3PbI3 or (C4H9NH3)2(CH3NH3) n-1Pb nI3 n+1 Mixtures.

Lead halide perovskites present a versatile class of solution-processable semiconductors with highly tunable bandgaps that span ultraviolet, visible, and near-infrared portions of the spectrum. We explore phase-separated chloride and iodide lead perovskite mixtures as candidate materials for intermediate band applications in future photovoltaics. X-ray diffraction and scanning electron microscopy reveal that deposition of precursor solutions across the MAPbCl3/MAPbI3 composition space affords quasi-epitaxial cocrystallized films, in which the two perovskites do not alloy but instead remain phase-segregated. First-principle calculations further support the formation of an epitaxial interface and predict energy offsets in the valence band and conduction band edges that could result in intermediate energy absorption. The charge dynamics of variable mixtures of the relatively narrow bandgap (1.57 eV) MAPbI3 perovskite and wide bandgap (3.02 eV) MAPbCl3 are probed to map charge and energy flow direction and kinetics. Time-resolved photoluminescence and transient absorption measurements reveal charge transfer of photoexcited carriers in MAPbCl3 to MAPbI3 in tens of picoseconds. The rate of quenching can be further tuned by replacing MAPbI3 with two-dimensional Ruddlesden-Popper (BA)2(MA) n-1Pb nI3 n+1 ( n = 3, 2, and 1) perovskites, which also remain phase-separated.

Connecting Composition-Driven Faceting with Facet-Driven Composition Modulation in GaAs-AlGaAs Core-Shell Nanowires.

Ternary III-V alloys of tunable bandgap are a foundation for engineering advanced optoelectronic devices based on quantum-confined structures including quantum wells, nanowires, and dots. In this context, core-shell nanowires provide useful geometric degrees of freedom in heterostructure design, but alloy segregation is frequently observed in epitaxial shells even in the absence of interface strain. High-resolution scanning transmission electron microscopy and laser-assisted atom probe tomography were used to investigate the driving forces of segregation in nonplanar GaAs-AlGaAs core-shell nanowires. Growth-temperature-dependent studies of Al-rich regions growing on radial {112} nanofacets suggest that facet-dependent bonding preferences drive the enrichment, rather than kinetically limited diffusion. Observations of the distinct interface faceting when pure AlAs is grown on GaAs confirm the preferential bonding of Al on {112} facets over {110} facets, explaining the decomposition behavior. Furthermore, three-dimensional composition profiles generated by atom probe tomography reveal the presence of Al-rich nanorings perpendicular to the growth direction; correlated electron microscopy shows that short zincblende insertions in a nanowire segment with predominantly wurtzite structure are enriched in Al, demonstrating that crystal phase engineering can be used to modulate composition. The findings suggest strategies to limit alloy decomposition and promote new geometries of quantum confined structures.

He-Ion Microscopy as a High-Resolution Probe for Complex Quantum Heterostructures in Core-Shell Nanowires.

Core-shell semiconductor nanowires (NW) with internal quantum heterostructures are amongst the most complex nanostructured materials to be explored for assessing the ultimate capabilities of diverse ultrahigh-resolution imaging techniques. To probe the structure and composition of these materials in their native environment with minimal damage and sample preparation calls for high-resolution electron or ion microscopy methods, which have not yet been tested on such classes of ultrasmall quantum nanostructures. Here, we demonstrate that scanning helium ion microscopy (SHeIM) provides a powerful and straightforward method to map quantum heterostructures embedded in complex III-V semiconductor NWs with unique material contrast at ∼1 nm resolution. By probing the cross sections of GaAs-Al(Ga)As core-shell NWs with coaxial GaAs quantum wells as well as short-period GaAs/AlAs superlattice (SL) structures in the shell, the Al-rich and Ga-rich layers are accurately discriminated by their image contrast in excellent agreement with correlated, yet destructive, scanning transmission electron microscopy and atom probe tomography analysis. Most interestingly, quantitative He-ion dose-dependent SHeIM analysis of the ternary AlGaAs shell layers and of compositionally nonuniform GaAs/AlAs SLs reveals distinct alloy composition fluctuations in the form of Al-rich clusters with size distributions between ∼1-10 nm. In the GaAs/AlAs SLs the alloy clustering vanishes with increasing SL-period (>5 nm-GaAs/4 nm-AlAs), providing insights into critical size dimensions for atomic intermixing effects in short-period SLs within a NW geometry. The straightforward SHeIM technique therefore provides unique benefits in imaging the tiniest nanoscale features in topography, structure and composition of a multitude of diverse complex semiconductor nanostructures.

Quantum Transport and Sub-Band Structure of Modulation-Doped GaAs/AlAs Core-Superlattice Nanowires.

Modulation-doped III-V semiconductor nanowire (NW) heterostructures have recently emerged as promising candidates to host high-mobility electron channels for future high-frequency, low-energy transistor technologies. The one-dimensional geometry of NWs also makes them attractive for studying quantum confinement effects. Here, we report correlated investigations into the discrete electronic sub-band structure of confined electrons in the channel of Si δ-doped GaAs-GaAs/AlAs core-superlattice NW heterostructures and the associated signatures in low-temperature transport. On the basis of accurate structural and dopant analysis using scanning transmission electron microscopy and atom probe tomography, we calculated the sub-band structure of electrons confined in the NW core and employ a labeling system inspired by atomic orbital notation. Electron transport measurements on top-gated NW transistors at cryogenic temperatures revealed signatures consistent with the depopulation of the quasi-one-dimensional sub-bands, as well as confinement in zero-dimensional-like states due to an impurity-defined background disorder potential. These findings are instructive toward reaching the ballistic transport regime in GaAs-AlGaAs based NW systems.

Impact of Dopant Compensation on Graded p-n Junctions in Si Nanowires.

The modulation between different doping species required to produce a diode in VLS-grown nanowires (NWs) yields a complex doping profile, both axially and radially, and a gradual junction at the interface. We present a detailed analysis of the dopant distribution around the junction. By combining surface potential measurements, performed by KPFM, with finite element simulations, we show that the highly doped (5 × 10(19) cm(-3)) shell surrounding the NW can screen the junction's built in voltage at shell thickness as low as 3 nm. By comparing NWs with high and low doping contrast at the junction, we show that dopant compensation dramatically decreases the electrostatic width of the junction and results in relatively low leakage currents.

Alloy Fluctuations Act as Quantum Dot-like Emitters in GaAs-AlGaAs Core-Shell Nanowires.

GaAs-AlxGa1-xAs (AlGaAs) core-shell nanowires show great promise for nanoscale electronic and optoelectronic devices, but the application of these nonplanar heterostructures in devices requires improved understanding and control of nanoscale alloy composition and interfaces. Multiple researchers have observed sharp emission lines of unknown origin below the AlGaAs band edge in photoluminescence (PL) spectra of core-shell nanowires; point defects, alloy composition fluctuations, and self-assembled quantum dots have been put forward as candidate structures. Here we employ laser-assisted atom probe tomography to reveal structural and compositional features that give rise to the sharp PL emission spectra. Nanoscale ellipsoidal Ga-enriched clusters resulting from random composition fluctuations are identified in the AlGaAs shell, and their compositions, size distributions, and interface characteristics are analyzed. Simulations of exciton transition energies in ellipsoidal quantum dots are used to relate the Ga nanocluster distribution with the distribution of sharp PL emission lines. We conclude that the Ga rich clusters can act as discrete emitters provided that the major diameter is ≥4 nm. Smaller clusters are under-represented in the PL spectrum, and spectral lines of larger clusters are broadened, due to quantum tunneling between clusters.

Origin of polytype formation in VLS-grown Ge nanowires through defect generation and nanowire kinking.

We propose layer-by-layer growth mechanisms to account for planar defect generation leading to kinked polytype nanowires. Cs-corrected scanning transmission electron microscopy enabled identification of stacking sequences of distinct polytype bands found in kinked nanowires, and Raman spectroscopy was used to distinguish polytype nanowires from twinned nanowires containing only the 3C diamond cubic phase. The faceting and atomic-scale defect structures of twinned 3C are compared with those of polytype nanowires to develop a common model linking nucleation pinning to nanowire morphology and phase.