Effects of oxygen vacancies and interfacial strain on the metal-insulator transition of VO2 nanobeams.

The role of oxygen vacancies and interfacial strain on the metal-insulator transition (MIT) behavior of high-quality VO2 nanobeams (NBs) synthesized on SiO2/Si substrates employing V2O5 as a precursor has been investigated in this research. Selective oxygen vacancies have been generated by argon plasma irradiation. The MIT is progressively suppressed as the duration of plasma processing increases; in addition, the temperature of MIT (TMIT) drops by up to 95 K relative to the pristine VO2 NBs. Incorporating oxygen vacancies into VO2 may increase its electron concentration, which might shift the Fermi levels upward, strengthen the electronic orbital overlap of the V-V chains, and further stabilize the metallic phase at lower temperatures, based on first-principles calculations. Furthermore, in order to evaluate the influence of substrate-induced strain in our situation, the MIT in two distinct types of VO2 NB samples is examined without metal contacts by using the distinctive light scattering characteristics of the metal (M) and insulator (I) phases (i.e., M/I domains) by optical microscopy. It is found that the domain structures in the "clamped" NBs persisted up to ∼453 K, while the "released" NBs (transferred to a new substrate) did not exhibit any domain structures and turned into an entirely M phase with a dark contrast above ∼348 K. When combined with first-principles calculations, the electronic orbital occupancy in the rutile phase contributes to explaining the interfacial strain-induced modulation of MIT. The current findings shed light on how interfacial strain and oxygen vacancies impact MIT behavior. It also suggests several types of control strategies for MIT in VO2 NBs, which are essential for a broader spectrum of VO2 NB applications.

Investigating the effect of curing temperature on the corrosion resistance of epoxy-based composite coatings for aluminium alloy 7075 in artificial seawater.

Araldite LY5052 epoxy resin and Aradur HY5052 hardener were used in a ratio of 100 : 38 to produce composite coatings containing 0.05 proportion of functionalized SiO2. Coating samples were cured at curing temperatures of 60, 80, 100, 120, and 140 °C. The results of Fourier Transform Infrared Spectroscopy (FTIR) verified that silica particles were successfully functionalized with methyltrimethoxysilane (MTMS)/3-aminopropyl-triethoxysilane (APTES). The epoxide and Si-O bond peaks in the EHS100 coating were present due to the effective incorporation of functionalized silica (FSiO2) particles in the polymeric matrix (epoxy resin). The surface morphology of the bare aluminium alloy AA7075 and EHS100 coating was investigated by Field Emission Scanning Electron Microscopy (FE-SEM). Additionally, corrosion analysis was conducted at room temperature using an electrolytic solution of artificial seawater, prepared according to ASTM standard D1141-98. Charge transfer resistance (Rct) was shown to increase by 86.43, 92.15, 94.76, 90.65, and 83.96% for EHS60, EHS80, EHS100, EHS120, and EHS140 in comparison to bare AA7075 substrate using electrochemical impedance spectroscopy (EIS) examination. Furthermore, potentiodynamic polarization (PDP) measurements were carried out to determine the corrosion rates, which demonstrated a drop of 55.98, 98.96, 99.37, 98.33, and 50.39% for EHS60, EHS80, EHS100, EHS120, and EHS140, as compared to the bare AA7075 sample. The highest charge transfer resistance (29.77 kΩ) and lowest corrosion rate (0.00078 mm per year) were recorded for EHS100, which reveals that the EHS100 coating has the best anti-corrosion performance and provides the maximum corrosion protection for the aluminium alloy AA7075 substrate.

High quality VO2 thin films synthesized from V2O5 powder for sensitive near-infrared detection.

Vapor transport method has been successfully used to synthesize high quality VO2 thin films on SiO2/Si substrate using V2O5 as a precursor in an inert-gas environment. The morphological and structural evolutions of the intermediate phases during the nucleation and growth processes were investigated by SEM and Raman spectroscopy, respectively. The results showed that the conversion of V2O5 powder to VO2 thin films was dominated by a melting-evaporation-nucleation-growth mechanism. Further characterization results demonstrated that the high quality crystals of monoclinic VO2 thin films exhibit a sharp resistance change up to 4 orders of magnitude. In addition, the VO2 thin films exhibited good near-infrared response, high stability, and reproducibility under ambient conditions, which should be promising for sensitive near-infrared detection. Our work not only provided a simple and direct approach to synthesize high quality VO2 thin films with distinct phase transition properties but also demonstrated the possible infrared sensing application in the future.

Fast Photoelectric Conversion in the Near-Infrared Enabled by Plasmon-Induced Hot-Electron Transfer.

Interfacial charge transfer is a fundamental and crucial process in photoelectric conversion. If charge transfer is not fast enough, carrier harvesting can compromise with competitive relaxation pathways, e.g., cooling, trapping, and recombination. Some of these processes can strongly affect the speed and efficiency of photoelectric conversion. In this work, it is elaborated that plasmon-induced hot-electron transfer (HET) from tungsten suboxide to graphene is a sufficiently fast process to prevent carrier cooling and trapping processes. A fast near-infrared detector empowered by HET is demonstrated, and the response time is three orders of magnitude faster than that based on common band-edge electron transfer. Moreover, HET can overcome the spectral limit of the bandgap of tungsten suboxide (≈2.8 eV) to extent the photoresponse to the communication band of 1550 nm (≈0.8 eV). These results indicate that plasmon-induced HET is a new strategy for implementation of efficient and high-speed photoelectric devices.

Nonvolatile Memory Based on Molecular Ferroelectric/Graphene Field Effect Transistor.

Ferroelectric thin films are extensively attractive as next-generation nonvolatile memories. Recently, molecular ferroelectrics (MFe), as an emerging new class, have been a new research focus because of their desirable characteristics such as good solution processability, tunable chemical properties, and bio-friendly compositions. However, traditional uniaxial MFe only possess one polar axis which greatly limits their application, as it requires restricted orientational control in single crystal. To achieve macroscopic ferroelectricity and thus fully realize technological advantages of MFe, development of multiaxes is imperative to maximize effective polarization in specific crystallographic orientations. Herein, we present an early exploration on polycrystalline multiaxial MFe thin films of [Hdabco][ReO4] with a two-dimensional graphene hybrid nonvolatile memory device. The polarization switching of MFe is experimentally realized by the nonvolatile modulation of two current states in graphene. Such a hybrid device can exhibit large memory window ∼35 V implying its great potential in memory applications. Hence, by taking the advantages of multiple polarization axes of MFe, the low cost and large area MFe/graphene hybrid memory manifests new possibilities for the integration of these materials as flexible next generation memory devices.

Sequential dielectric phase transitions induced by the vibrations of water molecules in an organic-inorganic hybrid halide (N-(2-ammoniumethyl)piperazinium) CuCl5·2H2O.

Organic-inorganic hybrids represent a new type of material showing promising properties. In this report, sequential dielectric transitions have been studied in an organic-inorganic hybrid halide, (N-2-AP)CuCl5·2H2O (N-2-AP = N-(2-ammoniumethyl)piperazinium) (1). The packing structure of 1 displays discrete [CuCl5]3- rectangular pyramids and N-2-AP cations, which are linked by two water molecules, forming infinite hydrogen bond networks with inorganic and organic components along the b-axis. Characterization studies containing differential scanning calorimetry (DSC) measurements, variable-temperature X-ray diffraction and dielectric measurements were performed to investigate the phase transitions in 1. The deuterated sample of 1 (named 2) also exhibits a similar behavior to that in 1, but shows different phase transition temperatures in dielectric transitions. The arresting deuterated effect strongly confirms that the phase transitions in 1 are attributable to the local vibrations of water molecules resulting from the variation of hydrogen-bonding interactions.

Switchable Nonlinear Optical and Tunable Luminescent Properties Triggered by Multiple Phase Transitions in a Perovskite-Like Compound.

A new perovskite-like inorganic-organic hybrid compound [Et3(n-Pr)P][Cd(dca)3] (1) (where [Et3(n-Pr)P]+ is the propyltriethylphosphonium cation and dca is a dicyanamide ligand) was discovered to undergo three reversible phase transitions at 270 K (T1), 386 K (T2), and 415 K (T3), respectively. The variable-temperature single-crystal X-ray structural analyses reveal that these sequential phase transitions originate from the deformations of the [Cd(dca)3]- frameworks and the concomitant reorientations of the [Et3(n-Pr)P]+ guest cations. It is found that 1 possesses a sensitive nonlinear optical (NLO) switching at T2 with a large contrast of ∼40 within a narrow temperature range of ∼7 K. Furthermore, 1 shows intriguing photoluminescence (PL) property, and the PL intensity suffers a plunge near T3. The multiple phase transitions, switchable NLO and tunable luminescent properties simultaneously exist in this inorganic-organic perovskite-like hybrid compound, suggesting its great potential application in molecular switches and photoelectric field.

Temperature-Triggered Dielectric-Optical Duple Switch Based on an Organic-Inorganic Hybrid Phase Transition Crystal: [C5N2H16]2SbBr5.

Molecular optical-electrical duple switches (switch "ON" and "OFF" bistable states) represent a class of highly desirable intelligent materials because of their sensitive switchable physical and/or chemical responses, simple and environmentally friendly processing, light weights, and mechanical flexibility. In the current work, the phase transition of 1 (general formula R2MX5, [C5N2H16]2[SbBr5]) can be triggered by the order-disorder transition of the organic cations at 278.3 K. The temperature-induced phase transition causes novel bistable optical-electrical duple characteristics, which indicates that 1 might be an excellent candidate for a potential switchable optical-electrical (fluorescence/dielectric) material. In the dielectric measurements, remarkable bistable dielectric responses were detected, accompanied by striking anisotropy along various crystallographic axes. For the intriguing fluorescence emission spectra, the intensity and position changed significantly with the occurrence of the structural phase transition. We believe that these findings might further promote the application of halogenoantimonates(III) and halogenobismuthates(III) in the field of optoelectronic multifunctional devices.