High-temperature Metallic Phase Research Articles

Variation of the metal-insulator phase transition temperature in VO2: An overview of some possible implementation methods

The great interest in VO2, which has stimulated a large number of studies and publications in recent decades, is caused by the reversible metal-insulator phase transition (MIT) that occurs at T = 68 °C and is accompanied by the transformation of a low-temperature dielectric (semiconductor) monoclinic phase into a high-temperature metallic phase with a rutile structure. Despite the ongoing discussion about the physical mechanism of this transition, the concomitant rapid change in the electrical and optical characteristics of the material by several orders of magnitude already finds numerous applications in optics, optoelectronics and sensors. At the same time, it became obvious that both the number and performance of the applications of VO2 would greatly increase, if it were possible to decrease the temperature of the phase transition without deterioration of other properties. This issue has become the subject of numerous studies. Mechanical stress and oxygen vacancies in the VO2 lattice, the concentration of free charge carriers, tuned by impurity doping or implantation, have been investigated and discussed as the main factors affecting the transition temperature. In this review, we intend to summarize and analyze the literature data on these ways, primarily those which are most efficient in influencing the transition temperature while maintaining a significant change in the modulation characteristics.

Correlation of metal-to-insulator transition and strain state of VO2 thin films on TiO2 (110) substrates

We explore the possibility of tuning the metal-to-insulator transition (MIT) of crystalline VO2 thin films by strain engineering. We deposit high-quality VO2 epitaxial films of different thicknesses on TiO2 (110) substrates by pulsed laser deposition. The strain state of the deposited film varies with its thickness. This allows us to correlate the MIT characteristics with the strain state of the VO2 film by a careful characterization of the structural and electrical properties. Thin VO2 films on TiO2 (110) substrates are almost fully strained up to thicknesses of about 20 nm and exhibit tensile strain along the c axis of the (high-temperature) metallic rutile phase leading to an increase in the MIT temperature by as much as 30 °C in comparison to the almost fully relaxed 300 nm-thick VO2 film. The strain gradient within the thicker samples leads to a continuous serial switching of layered regions of the VO2 film from the insulating to the metallic state with increasing temperature.

Development of over 3000 cycles durable macro-encapsulated aluminum with cavity by a sacrificial layer method for high temperature latent heat storage

The high-temperature metallic phase change materials (PCMs) are attracting great attentions as alternatives to sensible heat storage materials in thermal energy storage (TES) systems. However, the high corrosivity, easy leakage and oxidation phenomena of metallic PCMs have limited their applications. This work reports a facile and novel sacrificial layer method with the purpose to create macro-encapsulating aluminum (Al) PCM by alumina (Al2O3) shell characterized by a ‘buffer’ inner cavity. The inner cavity could offer buffer space to accommodate the huge thermal volume expansion of Al core PCM during heating and melting, thereby preventing the breakage of the capsules and ensuring the long-term stability. A series of Al balls with diameters of 4–25 mm were firstly coated with paraffin sacrificial layer then by Al2O3 dough shell, which was finally conducted by the two-step heat treatment, in which a low-temperature stage aimed at removing the paraffin layer while the high-temperature stage aimed at the capsule sintering formation. The final macrocapsules with diameters of 6.5–31.5 mm were obtained, in which the capsules with Al core balls larger than 15 mm showed superior gravimetric and volumetric heat storage density because of their high core–shell ratio. For example, the 25 mm@0.75 mm@2.5 mm macrocapsules could present high heat storage density of 348 kJ/kg and 902 J/cm3 at the temperature range of 600–700 °C. The macrocapsules also showed a long-time thermal cycling stability, since that no damage or leakage was observed over 3000 times of melting and solidification under air atmosphere, indicating that they can be used over 8 years without any degradation of thermophysical properties. This demonstrates the potential application of the Al2O3 encapsulated Al macrocapsules with inner cavity in high-temperature TES systems.

Electronic structure reconstruction by trimer formation in CsW2O6 studied by x-ray photoelectron spectroscopy

We have studied the electronic structure of $\mathrm{Cs}{\mathrm{W}}_{2}{\mathrm{O}}_{6}$ across its metal-insulator transition by means of hard/soft x-ray photoelectron spectroscopy. In the high-temperature metallic phase, the W $5d$ band exhibits a clear Fermi edge. The W $4{f}_{7/2}$ and $4{f}_{5/2}$ core-level peaks are accompanied by shoulders on their lower binding energy side. The shoulder and main peaks, respectively, are attributed to the well- and poorly screened final states where the screening is due to the W $5d$ electronic states in the vicinity of the chemical potential. In going from 300 to 180 K (across the metal-insulator transition), a band gap of about 0.2 eV is created at the Fermi level. The origin of the band gap can be assigned to the trimerization of the W sites. The W $4f$ and $5d$ spectra exclude the possibility of charge disproportionation and suggest moderate electronic correlation effects.

An optoelectronic heterostructure for neuromorphic computing: CdS/V3O5

Nonvolatile resistive switching is one of the key phenomena for emerging applications in optoelectronics and neuromorphic computing. In most of the cases, an electric field is applied to a two terminal dielectric material device and leads to the formation of a low resistance filament due to ion migration. However, the stochastic nature of the ion migration can be an impediment for the device robustness and controllability, with uncontrolled variations of high and low resistance states or threshold voltages. Here, we report an optically induced resistive switching based on a CdS/V3O5 heterostructure which can overcome this issue. V3O5 is known to have a second order insulator to metal transition around Tc ≈ 415 K, with an electrically induced threshold switching at room temperature. Upon illumination, the direct transfer of the photoinduced carriers from the CdS into V3O5 produces a nonvolatile resistive switching at room temperature. The initial high resistance can be recovered by reaching the high temperature metallic phase, i.e., temperatures above Tc. Interestingly, this resistive switching becomes volatile around the Tc. By locally manipulating the volatile and nonvolatile resistive switching using electric field and light, this system is a promising platform for hardware based neuromorphic computing implementations.

Nanoscale self-organization and metastable non-thermal metallicity in Mott insulators

Mott transitions in real materials are first order and almost always associated with lattice distortions, both features promoting the emergence of nanotextured phases. This nanoscale self-organization creates spatially inhomogeneous regions, which can host and protect transient non-thermal electronic and lattice states triggered by light excitation. Here, we combine time-resolved X-ray microscopy with a Landau-Ginzburg functional approach for calculating the strain and electronic real-space configurations. We investigate V2O3, the archetypal Mott insulator in which nanoscale self-organization already exists in the low-temperature monoclinic phase and strongly affects the transition towards the high-temperature corundum metallic phase. Our joint experimental-theoretical approach uncovers a remarkable out-of-equilibrium phenomenon: the photo-induced stabilisation of the long sought monoclinic metal phase, which is absent at equilibrium and in homogeneous materials, but emerges as a metastable state solely when light excitation is combined with the underlying nanotexture of the monoclinic lattice.

The Origin of the Thermochromic Property Changes in Doped Vanadium Dioxide.

Vanadium dioxide is a promising material for novel smart window applications due to its reversible metal-insulator transition which is accompanied by a change in its optical properties. The transition temperature (TMIT) can be controlled via elemental doping, but the reduction of TMIT is generally coupled with a decrease of the optical contrast between the two phases. To better understand how the contrast is fundamentally connected to TMIT, the thermochromic properties of doped VO2 were theoretically investigated across the metal-insulator transition from first principles. Different dopants and their interaction with the VO2 host structure as well as different modes of doping were studied in detail. It was found that the transition temperature change is mainly related to the stabilization of the high-temperature metallic phase due to lattice deformations which are caused by the presence of the dopant ion. Inherent limitations to the thermochromic performance of VO2 substitutionally doped by the replacement of vanadium cations with other species were found, and alternative approaches were proposed. Specifically, a charge-neutral substitution of oxygen or an oxygen substitution in combination with interstitial doping without net charge transfer between the dopant atoms and VO2 were identified as promising avenues to ensure a low TMIT and no loss of optical contrast in vanadia-based smart window materials.

Microencapsulation of high temperature metallic phase change materials with SiCN shell

Metallic phase change materials (PCMs) have the advantages of large phase change latent heat, high heat storage density and broad application prospects in various high temperature industrial waste heat recovery and utilization. However, due to the strong corrosion of molten metal at high temperature, appropriate packaging technology is the prerequisite for the promotion and application of metallic PCMs. In this research, a high temperature PCM microencapsulating technology with SiCN shell and a new microencapsulation method was proposed. The high temperature microencapsulated phase change materials (MEPCMs) with the core–shell mass ratios of 5:1, 4:1 and 3:1 were prepared by “solvent evaporation-heating curing” method, using SiCN cured by organic polysilazane (OPSZ) as heat resistant shell material and Al-Si particles as core PCMs. The mechanisms of shell formation and coating of OPSZ were studied experimentally, as well as the material properties and thermal performance of MEPCMs. With the increase of temperature, OPSZ gradually formed a dense SiCN shell on the surface of Al-Si particles. The experimental results showed that MEPCMs with the core–shell mass ratio of 4:1 had a high phase change temperature (571.9 °C-573.7 °C) and good heat storage capability (281.2 J/g-282.9 J/g). SiCN shell was conducive to maintain a complete core–shell structure, and exhibited excellent thermal resistance and oxidation resistance to protect inner core materials during thermal cycles. Therefore, the prepared microcapsule was a potential heat storage material, which provided a new idea for developing microencapsulation method of high temperature PCMs.

Direct Observation of the Electrically Triggered Insulator-Metal Transition in V3O5 Far below the Transition Temperature

Resistive switching is one of the key phenomena for applications such as nonvolatile memories or neuromorphic computing. V3O5, a compound of the vanadium oxide Magn\'eli series, is one of the rare materials to exhibit an insulator-metal transition (IMT) above room temperature (Tc ~ 415 K). Here we demonstrate both static dc resistive switching (RS) and fast oscillatory spiking regimes in V3O5 devices at room temperature (120 K below the phase transition temperature) by applying an electric field. We use operando optical imaging to track a reflectivity change during the RS and find that a percolating high temperature metallic phase filament is formed. This demonstrates that the electrically induced RS triggers the phase transition. Furthermore, we optically capture the spiking oscillations that we link to the negative differential resistance regime and find the filament forms and dissolves via a periodic spatio-temporal instability that we describe by numerical simulations.

Tunable Infrared Optical Switch Based on Vanadium Dioxide.

A tunable infrared optical switch based on a plasmonic structure consisting of aluminum nanoarrays with a thin film of vanadium dioxide is proposed. This optical switch can realize arbitrary wavelength-selective optical switching in the mid-infrared region by altering the radii of the aluminum nanoarrays. Furthermore, since vanadium dioxide transforms from its low-temperature insulator phase to a high-temperature metallic phase when heated or applied voltage, the optical switch can achieve two-way switching of its “ON” and “OFF” modes. Finite-difference time-domain software is used to simulate the performance of the proposed infrared optical switch. Simulation results show that the switch offers excellent optical performances, that the modulation depth can reach up to 99.4%, and that the extinction ratio exceeds −22.16 dB. In addition, the phase transition time of vanadium dioxide is on the femtosecond scale, which means that this optical switch based on a vanadium dioxide thin film can be used for ultrafast switching.

Synthesis & characterization of nanostructure VO2 thin film

Vanadium dioxides are strongly correlated systems which undergo an insulator-metal transition (IMT) from a low-temperature semiconducting phase to a high-temperature metallic phase. Among them, Vanadium dioxide (VO2) undergoes IMT close to room temperature, accompanied by a structural transition resulting change of several orders of magnitude in the electrical and optical properties. Here, we present the synthesis of VO2 by sol-gel process which employs cost-effective precursors to synthesize pure phase of VO2 thin films. The synthesized thin films were characterized using an X-ray diffraction (XRD) to confirm phase purity and high resolution scanning electron microscope (HR-SEM) to study the crystallite and particle size for the synthesized films. The film’s surface was analyzed by X-ray photoelectron spectroscopy (XPS) to determine the valence state and chemical composition of vanadium dioxide.

Emergence of large thermal noise close to a temperature-driven metal-insulator transition

We report that close to a Mott transition there is an emergence of large thermal noise (${S}_{\mathrm{th}}$) which occurs concomitantly with large correlated flicker noise ($\frac{1}{f}$ noise) with significant non-Gaussian content. This was observed in films of ${\text{NdNiO}}_{3}$ (thickness 15 nm) grown on crystalline ${\text{SrTiO}}_{3}$ substrates with different crystallographic orientations that show a hysteretic transition from a high temperature metallic phase to a low temperature insulating phase in the temperature range 160 to 211 K depending on the substrate orientation and the heating and cooling cycle. The thermal noise, which is distinct from the flicker noise, deviates from the canonical Johnson-Nyquist value of $4{k}_{B}TR$ as measured through the ratio $\ensuremath{\zeta}(T)(\ensuremath{\equiv}\frac{{S}_{\mathrm{th}}(T)}{4{k}_{B}TR})$. The ratio $\ensuremath{\zeta}$ reaches a maximum value of ${\ensuremath{\zeta}}_{M}$ at a temperature ${T}^{*}$ that is close to but distinct from the metal-insulator transition (MIT) temperature ${T}_{\mathrm{MI}}$. In all the films near ${T}^{*}$, the scaled thermal noise maxima ${\ensuremath{\zeta}}_{M}\ensuremath{\gg}1$. The films were found to be largely strain relaxed with residual in-plane and out-of-plane strain as measured by x-ray reciprocal space mapping. It has been observed that the ratio $\frac{{T}^{*}}{{T}_{\mathrm{MI}}}$ as well as ${\ensuremath{\zeta}}_{M}$ have a close dependence on the in-plane-strain in the film. The enhanced thermal noise that occurs along with large correlated flicker noise both arise from slow kinetics of relaxation as established from temperature dependence of the correlation time ($\ensuremath{\tau}$) that gets significantly larger in the temperature range around ${T}^{*}$, reaching a maxima at $T={T}^{*}$. It has been proposed that the existence of large noise (both thermal and flicker noise) owes its origin to electronic phase separation (EPS) that exists near the MIT. A physical model has been suggested that EPS near MIT temperature can give rise to a sparse phase of nanometric small pockets of metallic phases (nanopuddles) that are surrounded by and embedded within the minority insulating phase. The nanopuddles act as a source of charge fluctuations and are coupled weakly to the majority metallic phase by tunneling through the layer of the minority insulating phase. Such isolated metallic nanopuddles can be Coulomb charged if the charging energy ${E}_{C}\ensuremath{\ge}{k}_{B}T$ and can have slow relaxation of fluctuations acting as a source of large noise. It has been argued that the size distribution of the nanopuddles, their average size $\ensuremath{\langle}d\ensuremath{\rangle}$, as well as the temperature dependence of their number density ${N}_{d}$ can determine the temperature ${T}^{*}$.

Recent Progress on Vanadium Dioxide Nanostructures and Devices: Fabrication, Properties, Applications and Perspectives.

Vanadium dioxide (VO2) is a typical metal-insulator transition (MIT) material, which changes from room-temperature monoclinic insulating phase to high-temperature rutile metallic phase. The phase transition of VO2 is accompanied by sudden changes in conductance and optical transmittance. Due to the excellent phase transition characteristics of VO2, it has been widely studied in the applications of electric and optical devices, smart windows, sensors, actuators, etc. In this review, we provide a summary about several phases of VO2 and their corresponding structural features, the typical fabrication methods of VO2 nanostructures (e.g., thin film and low-dimensional structures (LDSs)) and the properties and related applications of VO2. In addition, the challenges and opportunities for VO2 in future studies and applications are also discussed.

Resistivity saturation in an electron-doped cuprate

We report the observation of resistivity saturation in lightly doped ($x\sim 0.10)$ as-grown samples of the electron-doped cuprate La$_{2-x}$Ce$_x$CuO$_4$ (LCCO). The saturation occurs at resistivity values roughly consistent with the phenomenological Mott-Ioffe-Regel criterion once the low effective carrier density of these materials is included in the analysis. These results imply that, at least for light doping, the high-temperature metallic phase of these materials is not necessarily strange and may be understood as simply a low-density metal.

Negative thermal expansion of Ca2RuO4 with oxygen vacancies**Project supported by the National Natural Science Foundation of China (Grant Nos. 11874328 and 11574276). The SXRD experiments were performed at the BL02B2 and BL04B2 of SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (JASRI; proposal Nos. 2019A1167, 2019A1095, and 2019A1340). We also acknowledge the help of Beamline Scientists Dr.

Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxides but little is known about their effect on thermal expansion. Herein we report the effect of oxygen defects on the structure formation and thermal expansion properties of the layered perovskite Ca2RuO4 (CRO). It is shown that the CRO containing excess oxygen crystallizes in a metallic L-CRO phase without structure transition from 100 K to 500 K and displays a normal thermal expansion behavior, whereas those with oxygen vacancies adopt at room temperature an insulating S-CRO phase and exhibit an enormous negative thermal expansion (NTE) from 100 K to about 360 K, from where they undergo a structure transition to a high temperature metallic L-CRO phase. Compared to the L-CRO containing excess oxygen, the S-CRO structure has increasingly large orthorhombic strain and distinctive in-plane distortion upon cooling. The in-plane distortion of the RuO6 octahedra reaches a maximum across 260 K and then relaxes monotonically, providing a structure evidence for the appearance of an antiferromagnetic orbital ordering in the paramagnetic phase and the Ag phonon mode suppression and phase flip across the same temperature found recently. Both the L- and S-CRO display an antiferromagnetic ordering at about 150–110 K, with ferromagnetic ordering components at lower temperature. The NTE in S-CRO is a result of a complex interplay among the spin, orbital, and lattice.

Tunable Casimir equilibria with phase change materials: From quantum trapping to its release

A stable suspension of nanoscale particles due to the Casimir force is of great interest for many applications such as sensing, noncontract nanomachines. However, the suspension properties are difficult to change once the devices are fabricated. Vanadium dioxide (${\mathrm{VO}}_{2}$) is a phase change material, which undergoes a transition from a low-temperature insulating phase to a high-temperature metallic phase around a temperature of 340 K. In this work, we study Casimir forces between a nanoplate (gold or Teflon) and a layered structure containing a ${\mathrm{VO}}_{2}$ film. It is found that stable Casimir suspensions of nanoplates can be realized in a liquid environment, and the equilibrium distances are determined, not only by the layer thicknesses but also by the matter phases of ${\mathrm{VO}}_{2}$. Under proper designs, a switch from quantum trapping of the gold nanoplate (``on'' state) to its release (``off'' state) as a result of the metal-to-insulator transition of ${VO}_{2}$, is revealed. On the other hand, the quantum trapping and release of a Teflon nanoplate is found under the insulator-to-metal transition of ${\mathrm{VO}}_{2}$ . Our findings offer the possibility of designing switchable devices for applications in micro and nanoelectromechanical systems.

Design of Heteroanionic MoON Exhibiting a Peierls Metal-Insulator Transition.

Using a first-principles approach, we design the heteroanionic oxynitride MoON to exhibit a first-order isosymmetric thermally activated Peierls-type metal-insulator transition (MIT). We identify a ground state insulating phase (α-MoON) with monoclinic Pc symmetry and a metastable high temperature metallic phase (β-MoON) of equivalent symmetry. We find that ordered fac-MoO_{3}N_{3} octahedra with edge and corner connectivity stabilize the twisted Mo-Mo dimers present in the α phase, which activate the MIT through electron localization within the 4d a_{1g} manifold. By analyzing the temperature dependence of the soft zone-boundary instability driving the MIT, we estimate an ordering temperature T_{MIT}∼900 K. Our work shows that electronic transitions can be designed by exploiting multiple anions, and heteroanionic materials could offer new insights into the microscopic electron-lattice interactions governing unresolved transitions in homoanionic oxides.

Impact of biaxial and uniaxial strain on V2O3

Using first-principles calculations we determine the role of compressive and tensile uniaxial and equibiaxial strain on the structural, electronic and magnetic properties of V$_2$O$_3$. We find that compressive strain increases the energy cost to transition from the high-temperature paramagnetic metallic phase to the low-temperature antiferromagnetic insulating phase. This shift in the energy difference can be explained by changes in the V-V bond lengths that are antiferromagnetically aligned in the low temperature structure. The insights that we have obtained provide a microscopic explanation for the shifts in the metal-insulator transition temperature that have been observed in experiments of V$_2$O$_3$ films grown on different substrates.

Bias-Voltage Driven Switching of the Charge-Density-Wave and Normal Metallic Phases in 1T-TaS2 Thin-Film Devices.

We report on switching among three charge-density-wave phases, commensurate, nearly commensurate, incommensurate, and the high-temperature normal metallic phase in thin-film 1T-TaS2 devices induced by application of an in-plane bias voltage. The switching among all phases has been achieved over a wide temperature range, from 77 to 400 K. The low-frequency electronic noise spectroscopy has been used as an effective tool for monitoring the transitions, particularly the switching from the incommensurate charge-density-wave phase to the normal metal phase. The noise spectral density exhibits sharp increases at the phase transition points, which correspond to the step-like changes in resistivity. Assignment of the phases is consistent with low-field resistivity measurements over the temperature range from 77 to 600 K. Analysis of the experimental data and calculations of heat dissipation indicate that Joule heating plays a dominant role in the voltage induced transitions in the 1T-TaS2 devices on Si/SiO2 substrates, contrary to some recent claims. The possibility of the bias-voltage switching among four different phases of 1T-TaS2 is a promising step toward nanoscale device applications. The results also demonstrate the potential of noise spectroscopy for investigating and identifying phase transitions in the materials.

Temperature-dependent valence state within the metallic phase of BaV10O15 probed by hard x-ray photoelectron spectroscopy

We have studied electronic properties of ${\mathrm{BaV}}_{10}{\mathrm{O}}_{15}$ in the intermediate-temperature phase as well as in the high-temperature metallic phase by using hard x-ray photoemission spectroscopy (HAXPES). The V $2p$ HAXPES show a shift in the high-temperature phase between 300 and 245 K which is similar to the shift of spectral weight near the Fermi edge. The binding energy of the O $1\mathit{s}$ HAXPES peak does not change except a slight shift of the lower binding energy edge in the opposite direction between 300 and 180 K across the transition to the intermediate-temperature phase. This behavior is in sharp contrast to the transition to the low-temperature insulating phase where V $2p$ and O $1s$ HAXPES show dramatic shifts in the same direction. This indicates that the charge-orbital change in the intermediate-temperature phase is driven by the correlated V $3d$ electrons and is electronic. The ${\mathrm{V}}^{2.5+}\text{\ensuremath{-}}{\mathrm{V}}^{2.5+}$ bond ordering is related to the metallic contribution and gradually decreases with cooling from 300 K. The valence-band HAXPES show the metallic features of the pseudogap behavior near the Fermi edge in and above the intermediate-temperature phase due to ${\mathrm{V}}^{2.5+}\text{\ensuremath{-}}{\mathrm{V}}^{3+}$ charge fluctuation. The magnitude of the pseudogap increases from 300 to 180 K in parallel with the gradual breaking of the ${\mathrm{V}}^{2.5+}\text{\ensuremath{-}}{\mathrm{V}}^{2.5+}$ bond and formation of trimers.