On‐Demand Nanoscale Manipulations of Correlated Oxide Phases

Controlling material properties at the nanoscale is a critical enabler of high performance electronic and photonic devices. A prototypical material example is VO₂, where a structural phase transition in correlation with dramatic changes in resistivity, optical response, and thermal properties demonstrates particular technological importance. While the phase transition in VO₂ can be controlled at macroscopic scales, reliable and reversible nanoscale control of the material phases has remained elusive. Here, reconfigurable nanoscale manipulations of VO₂ from the pristine monoclinic semiconducting phase to either a stable monoclinic metallic phase, a metastable rutile metallic phase, or a layered insulating phase using an atomic force microscope is demonstrated at room temperature. The capability to directly write and erase arbitrary 2D patterns of different material phases with distinct optical and electrical properties builds a solid foundation for future reprogrammable multifunctional device engineering.     

Broad Range Tuning of Phase Transition Property in VO2 Through Metal‐Ceramic Nanocomposite Design

Vanadium dioxide (VO₂) is a well‐studied Mott‐insulator because of the very abrupt physical property switching during its semiconductor‐to‐metal transition (SMT) around 341 K (68 °C). In this work, through novel oxide‐metal nanocomposite designs (i.e., Au:VO₂ and Pt:VO₂), a very broad range of SMT temperature tuning from ≈ 323.5 to ≈ 366.7 K has been achieved by varying the metallic secondary phase in the nanocomposites (i.e., Au:VO₂ and Pt:VO₂ thin films, respectively). More surprisingly, the SMT T_c can be further lowered to ≈ 301.8 K (near room temperature) by reducing the Au particle size from 11.7 to 1.7 nm. All the VO₂ nanocomposite thin films maintain superior phase transition performance, i.e., large transition amplitude, very sharp transition, and narrow width of thermal hysteresis. Correspondingly, a twofold variation of the complex dielectric function has been demonstrated in these metal‐VO₂ nanocomposites. The wide range physical property tuning is attributed to the band structure reconstruction at the metal‐VO₂ phase boundaries. This demonstration paved a novel approach for tuning the phase transition property of Mott‐insulating materials to near room temperature transition, which is important for sensors, electrical switches, smart windows, and actuators.     

基于VO2相变的光控太赫兹调制器

基于VO2薄膜相变特性,通过在石英基底上制备VO2薄膜和亚波长金孔阵列,并在理论和实验上研究了金属孔阵列与VO2薄膜置于基底同侧和异侧的两种太赫兹(THz)调制器。系统研究了在光泵浦条件下两种样品的THz波的传输特性。结果表明,随着泵浦光功率的改变,两种结构的器件均可以实现对THz波强度的调制。对比分析两种结构器件的THz透射谱发现,紧邻金属孔阵列的金属相VO2能够有效地抑制THz表面等离子体的局域透射增强效应,使调制器的调制深度得到显著增强,这对基于相变材料调制器的设计具有重要意义。     

Insulator-to-metal phase transformation of VO2 films upon femtosecond laser excitation

Light-induced insulator-to-metal phase transition of vanadium dioxide films was studied by ultrafast optical pump-probe spectroscopy. The transient optical reflection measurement shows that both heating and laser illumination contribute to the phase transition of VO₂. Within 10⁻¹¹–10⁻⁹ sec, these two mechanisms are competitive. Excited-state dynamics were found to be strongly dependent on the concentration of structural defects and the pump laser power as well. Comparison of the transient reflection of VO₂ films deposited on different substrates suggests that the excitonic-controlled light-induced insulator-to-metal phase transition in VO₂ proceeded through an intermediate state. The transient reflection measurement of VO₂ in metallic phase shows a three-stage relaxation process. A polaron excitation model is introduced to describe the dynamical process for metallic VO₂.     

基于双层VO2的可调谐宽带太赫兹超材料吸收器

基于VO₂的相变特性,提出一种具有宽带特性的太赫兹超材料吸收器,包括2层VO₂图案、2层聚酰亚胺介电层和1层金属反射层,共5层结构。对吸收器的吸收特性、电场分布和可调谐特性进行仿真分析,结果表明,所设计的吸收器吸收率大于90%的带宽为2.56 THz。该吸收器将2层结构相同但尺寸不同的周期单元堆叠,有效扩展了带宽;且通过控制VO₂从绝缘态到金属态的相变,可以实现吸收率的连续调谐。通过研究不同偏振角及入射角条件下所设计超材料吸收器的吸收性能发现,该吸收器具有偏振无关、在较大入射角入射时吸收不敏感特性。所设计的吸收器有望在太赫兹通信、成像和探测器等领域得到广泛应用。     

Electrochemically Triggered Metal–Insulator Transition between VO2 and V2O5

Distinct properties of multiple phases of vanadium oxide (VO_x) render this material family attractive for advanced electronic devices, catalysis, and energy storage. In this work, phase boundaries of VO_x are crossed and distinct electronic properties are obtained by electrochemically tuning the oxygen content of VO_x thin films under a wide range of temperatures. Reversible phase transitions between two adjacent VO_x phases, VO₂ and V₂O₅, are obtained. Cathodic biases trigger the phase transition from V₂O₅ to VO₂, accompanied by disappearance of the wide band gap. The transformed phase is stable upon removal of the bias while reversible upon reversal of the electrochemical bias. The kinetics of the phase transition is monitored by tracking the time‐dependent response of the X‐ray absorption peaks upon the application of a sinusoidal electrical bias. The electrochemically controllable phase transition between VO₂ and V₂O₅ demonstrates the ability to induce major changes in the electronic properties of VO_x by spanning multiple structural phases. This concept is transferable to other multiphase oxides for electronic, magnetic, or electrochemical applications.     

Electrical Conduction at the Interface between Insulating van der Waals Materials

Emergent properties of 2D materials attract considerable interest in condensed matter physics and materials science due to their distinguished features that are missing in their bulk counterparts. A mainstream in this research field is to broaden the scope of material to expand the horizons of the research area, while developing functional interfaces between different 2D materials is another indispensable research direction. Here, the emergence of electrical conduction at the interface between insulating 2D materials is demonstrated. A new class of van der Waals heterostructures consisting of two sets of insulating transition‐metal dichalcogenides, group‐VI WSe₂ and group‐IV TMSe₂ (TM = Zr, Hf), is developed via molecular‐beam epitaxy, and it is found that those heterostructures are highly conducting although all the constituent materials are highly insulating. The WSe₂/ZrSe₂ interface exhibits more conducting behavior than the WSe₂/HfSe₂ interface, which can be understood by considering the band alignments between constituent materials. Moreover, by increasing Se flux during heterostructure fabrication, the WSe₂/ZrSe₂ interface becomes more conducting, reaching nearly metallic behavior. Further improvement of the crystalline quality as well as exploring different material combinations are expected to lead to metallic conduction, providing a novel functionality emerging at van der Waals heterostructures.     

Cover Picture: An Organic Light‐Emitting Diode with Field‐Effect Electron Transport (Adv. Funct. Mater. 1/2008)

The cover shows an organic light‐emitting diode with remote metallic cathode, reported by Sarah Schols and co‐workers on p. 136. The metallic cathode is displaced from the light‐emission zone by one to several micrometers. The injected electrons accumulate at an organic heterojunction and are transported to the light‐emission zone by field‐effect. The achieved charge‐carrier mobility and in combination with reduced optical absorption losses because of the remoteness of the cathode may lead to applications as waveguide OLEDs and possibly a laser structure. (The result was obtained in the EU‐funded project “OLAS” IST‐ FP6‐015034.) We describe an organic light‐emitting diode (OLED) using field‐effect to transport electrons. The device is a hybrid between a diode and a field‐effect transistor. Compared to conventional OLEDs, the metallic cathode is displaced by one to several micrometers from the light‐emitting zone. This micrometer‐sized distance can be bridged by electrons with enhanced field‐effect mobility. The device is fabricated using poly(triarylamine) (PTAA) as the hole‐transport material, tris(8‐hydroxyquinoline) aluminum (Alq₃) doped with 4‐(dicyanomethylene)‐2‐methyl‐6‐(julolindin‐4‐yl‐vinyl)‐4H‐pyran (DCM₂) as the active light‐emitting layer, and N,N′‐ditridecylperylene‐3,4,9,10‐tetracarboxylic diimide (PTCDI‐C₁₃H₂₇), as the electron‐transport material. The obtained external quantum efficiencies are as high as for conventional OLEDs comprising the same materials. The quantum efficiencies of the new devices are remarkably independent of the current, up to current densities of more than 10 A cm^–2. In addition, the absence of a metallic cathode covering the light‐emission zone permits top‐emission and could reduce optical absorption losses in waveguide structures. These properties may be useful in the future for the fabrication of solid‐state high‐brightness organic light sources.     

Pressure Induced Unstable Electronic States upon Correlated Nickelates Metastable Perovskites as Batch Synthesized via Heterogeneous Nucleation

Establishing condensed matters at their thermodynamically metastable or unstable structures demonstrates merit in the adjustability of their electronic structures, benefiting the discovery of emerging new material functionalities and applications. Herein, a molten‐salt assisted heterogeneous nucleation approach is demonstrated to significantly improve the effectiveness in batch synthesis of metastable perovskites correlated oxides, such as rare‐earth nickelates (ReNiO₃) with various rare‐earth compositions. In contrast to their conventional synthesis via solid state reactions, herein the metastable ReNiO₃ is heterogeneously precipitated together with potassium chloride (KCl) within the liquid phase of KCl molten‐salt that effectively dissolves the Ni‐/Re‐ precursors and largely enhances their reaction homogeneity. With this solid base overcoming their synthesis metastabilities, the beyond conventional electronic transportation of ReNiO₃ under high pressure is explored. It breaks the conventional thermodynamic equilibrium and triggers the formation of new electronic structures associated with unstable insulating and metallic SmNiO₃ beyond already known manners. The unstable insulating SmNiO₃ exhibits nontemperature‐dependent transportation character similar to saturation or bad metals but preserves 2–3 orders higher electronic conductivity, while a kinetic related hysteresis is observed in the temperature‐dependent transportations of the unstable metallic SmNiO₃. These discoveries with nonequilibrium correlated materials are worthy to be explored further.     

Ultraviolet‐Light‐Induced Reversible and Stable Carrier Modulation in MoS2 Field‐Effect Transistors

The tuning of charge carrier concentrations in semiconductor is necessary in order to approach high performance of the electronic and optoelectronic devices. It is demonstrated that the charge‐carrier density of single‐layer (SL), bilayer (BL), and few‐layer (FL) MoS₂ nanosheets can be finely and reversibly tuned with N₂ and O₂ gas in the presence of deep‐ultraviolet (DUV) light. After exposure to N₂ gas in the presence of DUV light, the threshold voltages of SL, BL, and FL MoS₂ field‐effect transistors (FETs) shift towards negative gate voltages. The exposure to N₂ gas in the presence of DUV light notably improves the drain‐to‐source current, carrier density, and charge‐carrier mobility for SL, BL, and FL MoS₂ FETs. Subsequently, the same devices are exposed to O₂ gas in the presence of DUV light for different periods and the electrical characteristics are completely recovered after a certain time. The doping by using the combination of N₂ and O₂ gas with DUV light provides a stable, effective, and facile approach for improving the performance of MoS₂ electronic devices.     

Fabrication of 128×128 element optical switch array by micromachining technology

Polycrystalline VO₂ thin films were obtained on Si substrates by ion beam sputtering deposition and annealing in flowing Ar gas. SEM images indicate that VO₂ thin films were grown into compact surfaces. Four-probe measurements indicated that the VO₂ thin films own good electrical homogeneity. After the films' production, micromachining technology including lithography, reaction ion etching and metallization connection processes was used to produce the optical switch array. As a result, the 128×128 element optical switch array was achieved.     

Synthesis of Large‐Area Atomically Thin BiOI Crystals with Highly Sensitive and Controllable Photodetection

Compared to the most studied 2D elements and binary compounds, ternary layered compounds with more adjustable physical and chemical properties have exhibited potential applications in electronic and optoelectronic devices. Here, 2D ternary layered BiOI crystals are synthesized first with a domain size up to 100 µm via space‐confined chemical vapor deposition. The photodetectors based on the as‐grown BiOI nanosheets demonstrate high sensitivity to 473 nm light. The I_on/I_off ratio and detectivity of BiOI photodetectors can reach up to 1 × 10⁵ and 8.2 × 10¹¹ Jones at 473 nm, respectively. Particularly, the contact and dark current of the photodetectors can be controlled by 254 nm ultraviolet light irradiation due to the introduction of oxygen vacancies. The facile synthesis of large‐area atomically thin BiOI and its controllable performance by ultraviolet light irradiation suggest that 2D BiOI crystal is a promising material for fundamental investigations and optoelectronic applications.     

Back‐contacted back‐junction n‐type silicon solar cells featuring an insulating thin film for decoupling charge carrier collection and metallization geometry

In this study, back‐contacted back‐junction n‐type silicon solar cells featuring a large emitter coverage (point‐like base contacts), a small emitter coverage (point‐like base and emitter contacts), and interdigitated metal fingers have been fabricated and analyzed. For both solar cell designs, a significant reduction of electrical shading losses caused by an increased recombination in the non‐collecting base area on the rear side was obtained. Because the solar cell designs are characterized by an overlap of the B‐doped emitter and the P‐doped base with metal fingers of the other polarity, insulating thin films with excellent electrical insulation properties are required to prevent shunting in these overlapping regions. Thus, with insulating thin films, the geometry of the minority charge carrier collecting emitter diffusion and the geometry of the interdigitated metal fingers can be decoupled. In this regard, plasma‐enhanced chemical vapor deposited SiO₂ insulating thin films with various thicknesses and deposited at different temperatures have been investigated in more detail by metal‐insulator‐semiconductor structures. Furthermore, the influence of different metal layers on the insulation properties of the films has been analyzed. It has been found that by applying a SiO₂ insulating thin film with a thickness of more than 1000 nm and deposited at 350 °C to solar cells fabricated on 1 Ω cm and 10 Ω cm n‐type float‐zone grown silicon substrates, electrical shading losses could be reduced considerably, resulting in excellent short‐circuit current densities of more than 41 mA/cm² and conversion efficiencies of up to 23.0%. Copyright © 2012 John Wiley & Sons, Ltd.     

Ultraviolet-electrical erasing response characteristics of Ag@SiO2 core-shell functional floating gate organic memory

In the current research of organic memory devices, optimizing the functional layers or introducing appropriate auxiliary operation signals have become two high-profile solutions for device performance optimization. In this work, floating-gate organic memory (FGOM) based on Ag@SiO₂ core-shell nanospheres as the integrated floating gate-tunneling layer are studied. The device with an average thickness of 5 nm silica shell layer exhibits ideal storage characteristics under electrical pulse programming/erasing (P/E) operations. Meanwhile, appropriate incident light with different wavelengths are also applied on the device for optimizing erasing response. The best and reliable nonvolatile memory characteristics are achieved in the one erased by the ultraviolet-assisted electrical pulse, which includes nearly 24 V memory window after 10⁴ s (charge retention rate ≈66%) and nearly 10³ on/off current ratio. By assisting the electrical erasing pulse with the ultraviolet light, a large number of photogenerated carriers can be easily transferred through the thin shell-type tunneling layer and stored. Moreover, the device that only applies the ultraviolet signal to erase also exhibits obvious data discrimination and ideal data retention ability. It stores the optical data while identifying the optical signal, which provides a new realization idea for the integration of ultraviolet light sensor and memory devices.     

Hysteresis of the photonic band gap in VO<Subscript>2</Subscript> photonic crystal in the semiconductor-metal phase transition

VO₂ photonic crystals exhibiting a semiconductor-metal phase transition at 55–75°C have been synthesized by the infiltration of vanadium dioxide (VO₂) into opal crystals and the subsequent removal of SiO₂ by etching. A study of the optical reflection spectra of such crystals demonstrated that they are characterized by a wide photonic band gap (in the [111] direction of light propagation) in the visible spectral range. The energy position of this band gap changes abruptly upon a phase transition. The temperature shift and hysteresis of the position of the photonic band gap were measured. Quantitative calculations of the reflection spectra of photonic crystals of opal and VO₂ were performed in terms of the model of a layered periodic medium, and numerical values of the geometric parameters and optical constants of the studied three-dimensional periodic structures were obtained.     

The Dynamic Phase Transition Modulation of Ion‐Liquid Gating VO2 Thin Film: Formation,Diffusion, and Recovery of Oxygen Vacancies

Electrolyte gating with ionic liquids (IL) on correlated vanadium dioxide (VO₂) nanowires/beams is effective to modulate the metal‐insulator transition (MIT) behavior. While for macrosize VO₂ film, the gating treatment shows different phase modulation process and the intrinsic mechanism is still not clear, though the oxygen‐vacancy diffusion channel is always adopted for the explanation. Herein, the dynamic phase modulation of electrolyte gated VO₂ films is investigated and the oxygen vacancies formation, diffusion, and recovery at the IL/oxide interface are observed. As a relatively slow electrochemical reaction, the gating effect gradually permeates from surface to the inside of VO₂ film, along with an unsynchronized changes of integral electric, optical, and structure properties. First‐principles‐based theoretical calculation reveals that the oxygen vacancies can not only cause the structural deformations in monoclinic VO_2, but also account for the MIT transition by inducing polarization charges and thereby adjusting the d‐orbital occupancy. The findings not only clarify the oxygen vacancies statement of electrolyte gated VO₂ film, but also can be extended to other ionic liquid/oxide systems for better understanding of the surface electrochemical stability and electronic properties modulation.     

Fast and Reversible Li Ion Insertion in Carbon‐Encapsulated Li3VO4 as Anode for Lithium‐Ion Battery

Carbon‐encapsulated Li₃VO₄ is synthesized by a facile environmentally benign solid‐state method with organic metallic precursor VO(C₅H₇O₂)₂ being chosen as both V and carbon sources yielding a core–shell nanostructure with lithium introduced in the subsequent annealing process. The Li₃VO₄ encapsulated with carbon presents exceeding rate capability (a reversible capability of 450, 340, 169, and 106 mAh g^?1 at 0.1 C, 10 C, 50 C, and 80 C, respectively) and long cyclic performance (80% capacity retention after 2000 cycles at 10 C) as an anode in lithium‐ion batteries. The superior performance is derived from the structural features of the carbon‐encapsulated Li₃VO₄ composite with oxygen vacancies in Li₃VO₄, which increase surface energy and could possibly serve as a nucleation center, thus facilitating phase transitions. The in situ generated carbon shell not only facilitates electron transport, but also suppresses Li₃VO₄ particle growth during the calcination process. The encouraging results demonstrate the significant potential of carbon encapsulated Li₃VO₄ for high power batteries. In addition, the simple generic synthesis method is applicable to the fabrication of a variety of electrode materials for batteries and supercapacitors with unique core–shell structure with mesoporous carbon shell.     

Cover Picture: Formation of Metal Nano‐ and Micropatterns on Self‐Assembled Monolayers by Pulsed Laser Deposition Through Nanostencils and Electroless Deposition (Adv. Funct. Mater. 10/2006)

The cover illustrates two‐step fabrication of metal micro‐ and nanostructures on self‐assembled monolayers (SAMs) by pulsed laser deposition and electroless deposition. Metal–SAM–metal junctions are a key component of molecular electronic devices. Pt was deposited in a micropattern by pulsed laser deposition through a stencil. XPS maps show how the Pt pattern is developed into a Cu pattern using electroless deposition as reported by Ravoo, Brugger, Reinhoudt, Blank, and co‐workers on p. 1337. The Cu pattern can also be observed by optical microscopy (background). Patterns of noble‐metal structures on top of self‐assembled monolayers (SAMs) on Au and SiO₂ substrates have been prepared following two approaches. The first approach consists of pulsed laser deposition (PLD) of Pt, Pd, Au, or Cu through nano‐ and microstencils. In the second approach, noble‐metal cluster patterns deposited through nano‐ and microstencils are used as catalysts for selective electroless deposition (ELD) of Cu. Cu structures are grown on SAMs on both Au and SiO₂ substrates and are subsequently analyzed using X‐ray photoelectron spectroscopy element mapping, atomic force microscopy, and optical microscopy. The combination of PLD through stencils on SAMs followed by ELD is a new method for the creation of (sub)‐micrometer‐sized metal structures on top of SAMs. This method minimizes the gas‐phase deposition step, which is often responsible for damage to, or electrical shorts through, the SAM.     

Changes in Electrical Characteristics of ZnO Thin Films Due to Environmental Factors

The impact of light and controlled gas ambient on the electrical characteristics of ZnO:P grown by pulsed laser deposition (PLD) is investigated with temperature-dependent Hall-effect and photo-Hall-effect using above-bandgap light. Exposure to blue/ultraviolet (UV) light results in long-lived persistent photoconductivity (PPC) effects dominated by electron conduction. However, these persistent effects can be largely reversed by exposing the sample to a controlled ambient of dry O₂ gas. These O₂-induced changes in the electronic properties persist in vacuum up to at least 400 K. Exposure to dry N₂ gas following blue/UV light has no effect on the observed PPC characteristics. The implications of these effects on the preparation of p-type ZnO will be discussed.     

Electrically-driven metal–insulator transition of vanadium dioxide thin films in a metal–oxide-insulator–metal device structure

We report the successful growth of vanadium dioxide (VO₂) films on SiO₂ buffered metal electrode and the fabrication of metal–oxide-insulator–metal (MOIM) junction. The VO₂ film has an abrupt thermal-induced metal–insulator transition (MIT) with a change of resistance of 2 orders of magnitude. The electrically-driven MIT (E-MIT) switching characteristics have been investigated by applying perpendicular voltage to VO₂ based MOIM device at particular temperatures, sharp jumps in electric current were observed in the I–V characteristics under a low threshold voltage of 1.6 V. The Ohmic behavior, non-Ohmic super-linear one, and metallic regime are sequentially observed in the MOIM device with the increase of voltage. It is expected to be of significance in exploring ultrafast electronic devices incorporating correlated oxides based MOIM structure.