Metastable Copper‐Phthalocyanine Single‐Crystal Nanowires and Their Use in Fabricating High‐Performance Field‐Effect Transistors

This paper describes a simple, vapor‐phase route for the synthesis of metastable α‐phase copper‐phthalocyanine (CuPc) single‐crystal nanowires through control of the growth temperature. The influence of the growth temperature on the crystal structures, morphology, and size of the CuPc nanostructures is explored using X‐ray diffraction (XRD), optical absorption, and transmission electron microscopy (TEM). α‐CuPc nanowires are successfully incorporated as active semiconductors in field‐effect transistors (FETs). Single nanowire devices exhibit carrier mobilities and current on/off ratios as high as 0.4 cm² V^?1 s^?1 and >10⁴, respectively.     

High‐Quality Cuboid CH3NH3PbI3 Single Crystals for High Performance X‐Ray and Photon Detectors

Organic–inorganic halide hybrid perovskite materials are promising materials for X‐ray and photon detection due to their superior optoelectronic properties. Single‐crystal (SGC) perovskites have increasingly attracted attention due to their substantially low crystal defects, which contribute to improving the figures of merit of the devices. Cuboid CH₃NH₃PbI₃ SGC with the naturally favorable geometry for device fabrication is rarely reported in X‐ray and photon detection application. The concept of seed dissolution‐regrowth to improve crystal quality of cuboid CH₃NH₃PbI₃ SGC is proposed and a fundamental understanding of the nucleation and growth is provided thermodynamically. The X‐ray detector fabricated from cuboid CH₃NH₃PbI₃ SGC demonstrates the firstly reported high sensitivity of 968.9 µC^?1 Gy^?1 cm^?2 under ?1 V bias. The results also show that the favorable crystal orientation and high quality of cuboid CH₃NH₃PbI₃ leads to better responsivity and faster response speed than the more common dodecahedral CH₃NH₃PbI₃ in photodetection. Consequently, the work paves a way to synthesize high‐quality perovskite SGCs and benefits the application of MAPbI₃ SGCs with preferred crystal orientation and favorable crystal geometry for emerging device applications.     

Uniform π‐System Alignment in Thin Films of Template‐Grown Dicarbonitrile‐Oligophenyls

The ordering and conformational properties of dicarbonitrile‐para‐oligophenyls are studied with complementary methods, namely X‐ray structure analysis, low‐temperature scanning tunneling microscopy, and near‐edge X‐ray absorption fine‐structure spectroscopy. The packing of the functionalized variants differs from their technologically interesting para‐oligophenyl counterparts, both in the bulk crystal phase and in thin films grown by organic molecular beam epitaxy (OMBE) under ultra‐high vacuum conditions on the Ag(111) surface. In the crystal phase, the conformation depends on the number n of phenyl rings, exhibiting an intriguing screw‐like structure in the case of n = 4 at room temperature as well as at 180 K. For OMBE‐grown thin films, the whole series acquires the same type of conformation, characterized by alternately twisted phenyl rings, similar to the pure oligophenyl species. However, for all tested molecules, the orientation of the molecular reference plane is uniform within the entire film and coincides with the surface plane. This contrasts with the herringbone ordering adopted by the phenyl backbones without the carbonitrile groups. Our results demonstrate how the functionalization of moieties with extended conjugated electron systems can help to improve the structural homogeneity in technologically relevant organic thin films.     

Reversible Amorphous‐to‐Amorphous Transitions in Chalcogenide Films: Correlating Changes in Structure and Optical Properties

Structural transitions in materials are accompanied by appreciable and exploitable changes in physical‐chemical properties. Whereas reversible optically‐driven atomistic changes in crystal‐to‐amorphous transitions are generally known and exploited in applications, the nature of the corresponding polyamorphic transitions between two structurally distinct meta‐stable amorphous phases is an unexplored theme. Direct experimental evidence is reported for the nature of the atomistic changes during fully reversible amorphous‐to‐amorphous switching between two individual states in the non‐crystalline As₅₀Se₅₀ films prepared by pulsed‐laser deposition and consequent changes in optical properties. Combination of surface sensitive X‐ray photoelectron spectroscopy and spectroscopic ellipsometry show that the near‐bandgap energy illumination and annealing induce reversible switching in the material's structure by local bonding rearrangements. This is accompanied by switching in refractive index between two well‐defined states. Exploiting the pluralism of distinct structural states in a disordered solid can provide new insights into the data storage in emerging optical memory and photonic applications.     

Long‐Term Structural Evolution of an Intercalated Layered Semiconductor

Intercalated molecules can dramatically modify the electronic band structure of layered semiconductors, significantly altering the optical properties of the material. In the layered monochalcogenide Gallium Telluride (GaTe), exposure to air induces a nearly 1 eV reduction of its band gap due to the interlayer diffusion and chemisorption of oxygen. The effect of oxygen chemisorption at the Te‐terminated surfaces on the structure of GaTe, however, is much less known. To better understand the structure–property relationship of intercalated GaTe, a systematic, long‐term, X‐ray diffraction study has been performed on GaTe exfoliated crystals exposed to ambient conditions. It is observed that the structural changes are not limited to a previously observed short‐term increase in lattice expansion. Over the course of months and even years after exfoliation, the oxygen adsorbates continue to modify the structure of GaTe, inducing significant disorder and grain reorientation. It is estimated that approximately one out of every two grains is slightly displaced by the intercalating oxygen, demonstrating a significant increase in grain mosaicity, while still maintaining the original {?2 0 1} out‐of‐plane texture. Correlating these structural transformations to observed changes in electrical and optical properties will enable capitalization of the use of adsorbates to engineer novel properties in these layered materials.     

X‐Ray Writing of Metallic Conductivity and Oxygen Vacancies at Silicon/SrTiO3 Interfaces

Tunable electronic properties of transition metal oxides and their interfaces offer remarkable functionalities for future devices. The interest in these materials has been boosted with the discovery of a 2D electron gas (2DEG) at SrTiO₃ (STO)‐based interfaces. For the majority of these systems, oxygen vacancies play a crucial role in the emergence of interface conductivity, ferromagnetism, and high electron mobility. Despite its great importance, controlling the density and spatial distribution of oxygen vacancies in a dynamic way remains extremely challenging. Here, lithography‐like writing of a metallic state at the interface between SrTiO₃ and amorphous Si using X‐ray irradiation is reported. Using a combination of transport techniques and in operando photoemission spectroscopy, it is revealed in real time that the X‐ray radiation induces transfer of oxygen across the interface leading to the on‐demand formation of oxygen vacancies and a 2DEG in STO. The formed 2DEG stays stable in ambient conditions as the interface oxygen vacancies are stabilized by the capping of Si. The study provides a fundamental understanding of X‐ray‐induced redox reactions at the SrTiO₃‐based interfaces and in addition shows the potential of X‐ray radiation for patterning stabile conductive pathways for future oxide‐based electronic devices.     

Catalyst‐Free Synthesis and Characterization of Metastable Boron Carbide Nanowires

Catalyst‐free growth of boron carbide nanowires is achieved by pyrolysis of diborane and methane at 650–750 °C and around 500 mTorr in a quartz tube furnace. Electron‐diffraction analysis using a novel diffraction‐scanning transmission electron microscopy (D‐STEM) technique indicates that the crystalline nanowires are single‐crystal orthorhombic boron carbide. TEM images show that the nanowires are covered by a 1–3 nm thick amorphous layer of carbon. Elemental analysis by electron energy loss spectroscopy (EELS) shows only boron and carbon while energy‐dispersive X‐ray spectroscopy (EDX) and X‐ray photoelectron spectroscopy (XPS) show the presence of oxygen as well as boron and carbon.     

A Solid‐State Fluorescent Material Based on Carbazole‐Containing Difluoroboron β‐Diketonate: Multiple Chromisms,the Self‐Assembly Behavior,and Optical Waveguides

A carbazole‐containing difluoroboron β‐diketonate complex ( BCZ ), which shows strong fluorescence in both the solid state and in organic solutions, is reported. The crystalline materials of BCZ obtained from different solvents display different emission colors. Single‐crystal analysis reveals that the enhanced overlap between adjacent molecules induces increased excited‐state delocalization and is responsible for the variation of the emission colors from yellow to red. The emission colors of the materials are effectively tuned by external stimuli such as grinding, heating, and solvent vapor. The powder X‐ray diffraction, differential scanning calorimetry, thermogravimetric analysis, and ¹H NMR studies on materials of BCZ reveal that the thermochromic properties of BCZ are closely related to the removal of solvent molecules from the crystalline powders upon heating. Moreover, uniform 1D microstructures of BCZ obtained by solvent exchange in solution exhibit optical waveguide property with low optical loss.     

Solvent‐Induced Morphology in Polymer‐Based Systems for Organic Photovoltaics

Studies on the influence of four different solvents on the morphology and photovoltaic performance of bulk‐heterojunction films made of poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁ butyric acid methyl ester (PCBM) via spin‐coating for photovoltaic applications are reported. Solvent‐dependent PCBM cluster formation and P3HT crystallization during thermal annealing are investigated with optical microscopy and grazing‐incidence wide‐angle X‐ray scattering (GIWAXS) and are found to be insufficient to explain the differences in device performance. A combination of atomic force microscopy (AFM), X‐ray reflectivity (XRR), and grazing‐incidence small‐angle X‐ray scattering (GISAXS) investigations results in detailed knowledge of the inner film morphology of P3HT:PCBM films. Vertical and lateral phase separation occurs during spin‐coating and annealing, depending on the solvent used. The findings are summarized in schematics and compared with the IV characteristics. The main influence on the photovoltaic performance arises from the vertical material composition and the existence of lateral phase separation fitting to the exciton diffusion length. Absorption and photoluminescence measurements complement the structural analysis.     

Large Area Self‐Assembly of Nematic Liquid‐Crystal‐Functionalized Gold Nanorods

Fascinating nematic‐ and smectic‐like self‐assembled arrays are observed for gold nanorods partially capped with either laterally or terminally attached nematic liquid crystals upon slow evaporation of an organic solvent on TEM grids. These arrays can be manipulated and reoriented by applying an external magnetic field from quasi‐planar to vertical similar to a Fréedericksz transition of common organic nematic liquid crystals. Birefringence and thin film textures of these self‐assembled gold nanorod arrays observed by polarized optical microscopy are strongly reminiscent of common organic nematic liquid crystal textures between crossed polarizers and, additionally, support the formation of ordered liquid crystal‐like anisotropic superstructures. The ordering within these arrays is also confirmed in bulk samples using small angle X‐ray scattering (SAXS).     

Hydrothermal Synthesis of Structure‐ and Shape‐Controlled Manganese Oxide Octahedral Molecular Sieve Nanomaterials

Highly uniform single‐crystal Na‐OMS‐2 (OMS: octahedral molecular sieve), pyrolusite, and γ‐MnO₂ nanostructures with an interesting 3D urchinlike morphology have been successfully prepared using a hydrothermal method based on a mild and direct reaction between sodium dichromate and manganese sulfate. The crystal phases, shapes, and tunnel sizes of the manganese dioxide nanostructures can be tailored. Reaction temperature, concentrations of the reactants, and acidity of the solution play important roles in controlling the synthesis of these manganese dioxides. Field‐emission scanning electron microscopy and transmission electron microscopy (TEM) studies show that the nanomaterials obtained are constructed of self‐assembled nanorods. X‐ray diffraction and TEM results indicate that the constituent manganese dioxide particles are single‐crystalline materials. Energy dispersive X‐ray analysis and magnetic studies imply that chromium cations may be incorporated into the framework and/or tunnels of the manganese dioxides. A mechanism for the growth of manganese dioxides with urchinlike architectures is proposed.     

Fabrication and Optical Characteristics of Position‐Controlled ZnO Nanotubes and ZnO/Zn0.8Mg0.2O Coaxial Nanotube Quantum Structure Arrays

The position‐controlled growth and structural and optical characteristics of ZnO nanotubes and their coaxial heterostructures are reported. To control both the shape and position of ZnO nanotubes, hole‐patterned SiO₂ growth‐mask layers on Si(111) substrates with GaN/AlN intermediate layers using conventional lithography are prepared. ZnO nanotubes are grown only on the hole patterns at 600 °C by catalyst‐free metal–organic vapor‐phase epitaxy. Furthermore, the position‐controlled nanotube growth method allows the fabrication of artificial arrays of ZnO‐based coaxial nanotube single‐quantum‐well structures (SQWs) on Si substrates. In situ heteroepitaxial growth of ZnO and Zn_0.8Mg_0.2O layers along the circumference of the ZnO nanotube enable an artificial formation of quantum‐well arrays in a designed fashion. The structural and optical characteristics of the ZnO nanotubes and SQW arrays are also investigated using synchrotron radiation X‐ray diffractometry and photoluminescence and cathodoluminescence spectroscopy.     

Meso‐SiO2–C12EO10OH–CF3SO3H—A Novel Proton‐Conducting Solid Electrolyte

This paper describes the synthesis and characterization of a novel mesostructured solid electrolyte composite material, denoted meso‐SiO₂–C₁₂EO₁₀OH–CF₃SO₃H. A lyotropic non‐ionic surfactant–triflic acid–silicate liquid crystal is used as a supramolecular template for a “one‐pot” synthesis of the material. Within this structure, the oligoethyleneoxide head groups of the non‐ionic surfactant that is imbibed within the channels of hexagonal mesoporous silica act in a crown‐ether‐like fashion towards the protons. The structure and dynamics of the silicate–oligo(ethylene oxide)surfactant–triflic acid co‐assembly has been studied via several analytical techniques. These methods include polarized optical microscopy (POM), powder X‐ray diffraction (PXRD), transmission electron microscopy (TEM), multinuclear nuclear magnetic resonance (NMR) spectroscopy, thermogravimetric analysis (TGA), and Fourier transform (FT) Raman spectroscopy. Together these results imply that the protons coordinate to the oxygen atoms of the ethylene oxide units on the non‐ionic surfactant and the compound has the structural integrity of the silicified liquid crystal. AC impedance spectroscopy was used to determine the proton conductivity of the meso‐SiO₂–C₁₂EO₁₀OH–CF₃SO₃H composite material at different relative humidity values giving some insight into its potential utility as a proton conducting solid electrolyte in a proton‐exchange membrane fuel cell.     

Structural and Electrical Characterization of ZnO Films Grown by Spray Pyrolysis and Their Application in Thin‐Film Transistors

The role of the substrate temperature on the structural, optical, and electronic properties of ZnO thin films deposited by spray pyrolysis using a zinc acetate precursor solution is reported. Analysis of the precursor compound using thermogravimentry and differential scanning calorimetry indicates complete decomposition of the precursor at around 350 °C. Film characterization using Fourier Transform Infrared Spectroscopy (FTIR), photoluminescence spectroscopy (PL), and ultraviolet–visible (UV–Vis) optical transmission spectroscopy suggests the onset of ZnO growth at temperatures as low as 100 °C as well as the transformation to a polycrystalline phase at deposition temperatures >200 °C. Atomic force microscopy (AFM) and X‐ray diffraction (XRD) reveal that as‐deposited films exhibit low surface roughness (rms ≈ 2.9 nm at 500 °C) and a crystal size that is monotonously increasing from 8 to 32 nm for deposition temperatures in the range of 200–500 °C. The latter appears to have a direct impact on the field‐effect electron mobility, which is found to increase with increasing ZnO crystal size. The maximum mobility and current on/off ratio is obtained from thin‐film transistors fabricated using ZnO films deposited at >400 °C yielding values on the order of 25 cm² V^?1s^?1 and 10⁶, respectively.     

X‐Ray‐Induced Persistent Luminescence Promotes Ultrasensitive Imaging and Effective Inhibition of Orthotopic Hepatic Tumors

Persistent luminescence imaging is accompanied by continuous illumination after the removal of excitation light, which can successfully prevent the generation of autofluorescence. In this study, a mesoporous silica template method is used to prepare uniform and monodisperse porous nanophosphors that can generate X‐ray‐excited persistent luminescence (XEPL). By loading photosensitizers, XEPL effectively excites the photosensitizers to produce reactive oxygen species for killing cancer cells. Imaging of orthotopic hepatic tumors in vivo shows that nanophosphors accumulate in the liver tumors through a passive targeting mechanism, as confirmed by the co‐imaging of bioluminescence and X‐ray‐excited luminescence. Under image‐guidance, X‐ray‐induced photodynamic therapy effectively inhibits the growth of orthotopic hepatic tumors with negligible side effects. Overall, X‐ray‐induced persistent luminescence promotes ultrasensitive imaging and effective inhibition of orthotopic hepatic tumors.     

Role and Optimization of the Active Oxide Layer in TiO2‐Based RRAM

TiO₂ is commonly used as the active switching layer in resistive random access memory. The electrical characteristics of these devices are directly related to the fundamental conditions inside the TiO₂ layer and at the interfaces between it and the surrounding electrodes. However, it is complex to disentangle the effects of film “bulk” properties and interface phenomena. The present work uses hard X‐ray photoemission spectroscopy (HAXPES) at different excitation energies to distinguish between these regimes. Changes are found to affect the entire thin film, but the most dramatic effects are confined to an interface. These changes are connected to oxygen ions moving and redistributing within the film. Based on the HAXPES results, post‐deposition annealing of the TiO₂ thin film was investigated as an optimisation pathway in order to reach an ideal compromise between device resistivity and lifetime. The structural and chemical changes upon annealing are investigated using X‐ray absorption spectroscopy and are further supported by a range of bulk and surface sensitive characterisation methods. In summary, it is shown that the management of oxygen content and interface quality is intrinsically important to device behavior and that careful annealing procedures are a powerful device optimisation technique.     

Helical 3D‐Printed Metal Electrodes as Custom‐Shaped 3D Platform for Electrochemical Devices

3D‐printing represents an emerging technology that can revolutionize the way object and functional devices are fabricated. Here the use of metal 3D printing is demonstrated to fabricate bespoke electrochemical stainless steel electrodes that can be used as platform for different electrochemical applications ranging from electrochemical capacitors, oxygen evolution catalyst, and pH sensor by means of an effective and controlled deposition of IrO₂ films. The electrodes have been characterized by scanning electrode microscopy and energy dispersive X‐ray spectroscopy before the electrochemical testing. Excellent pseudocapacitive as well as catalytic properties have been achieved with these 3D printed steel‐IrO₂ electrodes in alkaline solutions. These electrodes also demonstrate Nernstian behavior as pH sensor. This work represents a breakthrough in on‐site prototyping and fabrication of highly tailored electrochemical devices with complex 3D shapes which facilitate specific functions and properties.     

Controlled Synthesis of CdSe Nanowires by Solution–Liquid–Solid Method

Semiconductor nanowires prepared by wet chemical methods are a relatively new field of 1D electronic systems, where the dimensions can be controlled by changing the reaction parameters using solution chemistry. Here, the solution–liquid–solid approach where the nanowire growth is governed by low‐melting‐point catalyst particles, such as Bi nanocrystals, is presented. In particular, the focus is on the preparation and characterization of CdSe nanowires, a material which serves a prototype structure for many kinds of low dimensional semiconductor systems. To investigate the influence of different reaction parameters on the structural and optical properties of the nanowires, a comprehensive synthetic study is presented, and the results are compared with those reported in literature. How the interplay between different reaction parameters affects the diameter, length, crystal structure, and the optical properties of the resultant nanowires are demonstrated. The structural properties are mainly determined by competing reaction pathways, such as the growth of Bi nanocatalysts, the formation and catalytic growth of nanowires, and the formation and uncatalytic growth of quantum dots. Systematic variation of the reaction parameters (e.g., molecular precursors, concentration and concentration ratios, organic ligands, or reaction time, and temperature) enables control of the nanowire diameter from 6 to 33 nm, while their length can be adjusted between several tens of nanometers and tens of micrometers. The obtained CdSe nanowires exhibit an admixture of wurtzite (W) and zinc blende (ZB) structure, which is investigated by X‐ray diffraction. The diameter‐dependent band gaps of these nanowires can be varied between 650 and 700 nm while their fluorescence intensities are mainly governed by the Cd/Se precursor ratio and the ligands used.     

Laser‐Ablation Growth and Optical Properties of Wide and Long Single‐Crystal SnO2 Ribbons

Wide and long ribbons of single‐crystalline SnO₂ have been achieved via laser ablation of a SnO₂ target. Transmission electron microscopy (TEM) shows the as‐grown SnO₂ ribbons are structurally perfect and uniform, with widths of 300–500 nm, thicknesses of 30–50 nm (width‐to‐thickness ratio of ～ 10), and lengths ranging from several hundreds of micrometers to the order of millimeters. X‐ray diffraction (XRD) pattern and energy‐dispersive X‐ray spectroscopy (EDS) spectral analysis indicate that the ribbons have the phase structure and chemical composition of the rutile form of SnO₂. Selected‐area electron diffraction (SAED) patterns and high‐resolution TEM images reveal that the ribbons are single crystals and grow along the [100] crystal direction. Photoluminescence measurements show that the synthesized SnO₂ ribbons have one strong emission band at ～ 605 nm and a red‐shift of ～ 30 nm, as compared to standard SnO₂ powder, which may be attributed to crystal defects and residual strains accommodated during the growth of the ribbons.     

Single‐Crystalline Gallium Nitride Microspindles: Synthesis,Characterization, and Thermal Stability

This paper describes a facile procedure for synthesizing high‐quality gallium nitride microspindles on a large scale using a solid‐state reaction of GaI₃, NaNH₂, and NH₄Cl in a sealed system at 500 °C for 6 h. The structures, compositions, and morphologies of the as‐synthesized products are derived from X‐ray powder diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and field‐emission scanning electron microscopy (FE‐SEM). The selected‐area electron diffraction (SAED) patterns and high‐resolution transmission electron microscopy (HRTEM) images show that the as‐synthesized GaN spindles are composed of many single‐crystalline platelets. The GaN microspindles show different optical properties depending on their shape (e.g., nanowires or nanoparticles) in photoluminescence (PL) emission spectroscopy and Raman spectroscopy. The possible growth mechanism of GaN microspindles is controlled by linear kinetics with a driving force proportional to the difference between a local supersaturation and an equilibrium chemical potential. Furthermore, the thermal stability of the GaN microspindles is investigated under various annealing conditions and discussed on the basis of additional TEM and XRD analyses.