CO[subscript 2]-Assisted Oxidative Dehydrogenation of Propane over VO[subscript x]/In[subscript 2]O[
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Jiang, Xiao↗
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Single crystal neutron and magnetic measurements of Rb 2 Mn 3 (VO 4 ) 2 CO 3 and K 2 Co 3 (VO 4 ) 2 CO 3 with mixed honeycomb and triangular magnetic lattices
Two new alkali vanadate carbonates with divalent transition metals have been synthesized as large single crystals via a high-temperature (600 °C) hydrothermal technique. Compound I, Rb 2 Mn 3 (VO 4 ) 2 CO 3 , crystallizes in the trigonal crystal system in the space group P[3 with combining macron]1c, and compound II, K 2 Co 3 (VO 4 ) 2 CO 3 , crystallizes in the hexagonal space group P6 3 /m. Both structures contain honeycomb layers and triangular lattices made from edge-sharing MO 6 octahedra and MO 5 trigonal bipyramids, respectively. The honeycomb and triangular layers are connected along the c-axis through tetrahedral [VO 4 ] groups. The MO 5 units are connected with each other by carbonate groups in the ab-plane by forming a triangular magnetic lattice. The difference in space groups between I and II was also investigated with Density Functional Theory (DFT) calculations. Single crystal magnetic characterization of I indicates three magnetic transitions at 77 K, 2.3 K, and 1.5 K. The corresponding magnetic structures for each magnetic transition of I were determined using single crystal neutron diffraction. At 77 K the compound orders in the MnO 6 -honeycomb layer in a Néel-type antiferromagnetic orientation while the MnO 5 triangular lattice ordered below 2.3 K in a colinear ‘up–up–down’ fashion, followed by a planar ‘Y’ type magnetic structure. K 2 Co 3 (VO 4 ) 2 CO 3 (II) exhibits a canted antiferromagnetic ordering below T N = 8 K. Here, the Curie–Weiss fit (200–350 K) gives a Curie–Weiss temperature of –42 K suggesting a dominant antiferromagnetic coupling in the Co 2+ magnetic sublattices.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Broadband electrically tunable VO 2 -Metamaterial terahertz switch with suppressed reflection
Not provided.
Engineering↗
Decoupling the metal insulator transition and crystal field effects of VO 2
VO 2 is a highly correlated electron system which has a metal-to-insulator transition (MIT) with a dramatic change of conductivity accompanied by a first-order structural phase transition (SPT) near room temperature. The origin of the MIT is still controversial and there is ongoing debate over whether an SPT induces the MIT and whether the T c can be engineered using artificial parameters. We examined the electrical and local structural properties of Cr- and Co-ion implanted VO 2 (Cr-VO 2 and Co-VO 2 ) films using temperature-dependent resistance and X-ray absorption fine structure (XAFS) measurements at the V K edge. The temperature-dependent electrical resistance measurements of both Cr-VO 2 and Co-VO 2 films showed sharp MIT features. The T c values of the Cr-VO 2 and Co-VO 2 films first decreased and then increased relative to that of pristine VO 2 as the ion flux was increased. The pre-edge peak of the V K edge from the Cr-VO 2 films with a Cr ion flux ≥ 10 13 ions/cm 2 showed no temperature-dependent behavior, implying no changes in the local density of states of V 3d t 2g and e g orbitals during MIT. Extended XAFS (EXAFS) revealed that implanted Cr and Co ions and their tracks caused a substantial amount of structural disorder and distortion at both vanadium and oxygen sites. The resistance and XAFS measurements revealed that VO 2 experiences a sharp MIT when the distance of V–V pairs undergoes an SPT without any transitions in either the VO 6 octahedrons or the V 3d t 2g and eg states. This indicates that the MIT of VO 2 occurs with no changes of the crystal fields.
36 MATERIALS SCIENCE↗
Tuning Spin-Orbit Torques Across the Phase Transition in VO 2 /NiFe Heterostructure
The emergence of spin-orbit torques as a promising approach to energy-efficient magnetic switching has generated large interest in material systems with easily and fully tunable spin-orbit torques. We report current-induced spin-orbit torques in VO 2 /NiFe heterostructures are investigated using spin-torque ferromagnetic resonance, where the VO 2 layer undergoes a prominent insulator-metal transition. A roughly twofold increase in the Gilbert damping parameter, α, with temperature is attributed to the change in the VO 2 /NiFe interface spin absorption across the VO 2 phase transition. More remarkably, a large modulation (±100%) and a sign change of the current-induced spin-orbit torque across the VO 2 phase transition suggest two competing spin-orbit torque generating mechanisms. The bulk spin Hall effect in metallic VO 2 , corroborated by the first-principles calculation of the spin Hall conductivity σ SH ≈ -10 4 ($\frac{\hbar}{e}$) Ω -1 m -1 , is verified as the main source of the spin-orbit torque in the metallic phase. The self-induced/anomalous torque in NiFe, with opposite sign and a similar magnitude to the bulk spin Hall effect in metallic VO 2 , can be the other competing mechanism that dominates as temperature decreases. For applications, the strong tunability of the torque strength and direction opens a new route to tailor spin-orbit torques of materials that undergo phase transitions for new device functionalities.
36 MATERIALS SCIENCE↗
Ultrathin VO 2 Films on Functional Substrates
The metal–insulator transition (MIT) in vanadium dioxide (VO 2 ) thin films is strongly affected by grain size, thickness, and interfacial properties. Typically, a minimum thickness around 50 nm is required for VO 2 to exhibit a significant MIT when functional substrates like sapphire and silicon are used. Several works have shown that thin films below 20 nm, with up to 2–3 decades of change in the resistance across the MIT, can be achieved but require complex pre- or postprocessing of the samples. We show that predeposition substrate condition control facilitates the direct growth of VO 2 ultrathin 15 nm films, exhibiting a resistance change between 3 and 4 decades across the MIT. Our findings indicate that the interface between the film and the substrate is crucial in determining the initial growth layers and the structural evolution. With appropriate substrate surface treatment, the desired VO 2 MIT can be enhanced regardless of the substrate crystallographic orientation. Moreover, we propose a novel approach to obtain large resistance changes across the MIT in ultrathin VO 2 films by incorporating a predeposited 1.5 nm vanadium oxide buffer layer, thereby eliminating the need to use different materials or complex pre- or postprocessing of the samples. Here we also demonstrate that this method improves the transition of 25–50 nm VO 2 thin films on silicon substrates. Our study reveals a simple approach for direct growth of ultrathin VO 2 films exhibiting a significant MIT, which is commonly accepted unattainable over substrates of technological importance, such as sapphire and silicon.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Controllable Phase Transition Properties in VO 2 Films via Metal-Ion Intercalation
VO 2 has shown great promise for sensors, smart windows, and energy storage devices, because of its drastic semiconductor-to-metal transition (SMT) near 340 K coupled with a structural transition. To push its application toward room-temperature, effective transition temperature (T c ) tuning in VO 2 is desired. Here, in this study, tailorable SMT characteristics in VO 2 films have been achieved by the electrochemical intercalation of foreign ions (e.g., Li ions). By controlling the relative potential with respect to Li/Li + during the intercalation process, T c of VO 2 can be effectively and systematically tuned in the window from 326.7 to 340.8 K. The effective T c tuning could be attributed to the observed strain and lattice distortion and the change of the charge carrier density in VO 2 introduced by the intercalation process. This demonstration opens up a new approach in tuning the VO 2 phase transition toward room-temperature device applications and enables future real-time phase change property tuning.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Electrical and structural properties of VO 2 in an electric field
We examined the electrical and local structural properties of a VO 2 film at different electric fields using electrical resistance and x-ray absorption fine structure (XAFS) measurements at the V K edge in the temperature range of 30–100 °C. The T c value of the metal-to-insulator transition (MIT) during both heating and cooling decreases with electric field. When the electric field exceeds a certain value, the MIT becomes sharper due to Joule heating. Furthermore, the MIT, the structural phase transition (SPT), and the pre-edge peak transition of the VO 2 do not congruently occur at a uniform temperature. A metallic VO 2 is observed in only the rutile (or M2) symmetry. An electric field induces a substantial amount of conduction electrons in insulating VO 2 . Simultaneously measured resistance and XAFS reveal that Joule heating caused by an external electric field significantly affects the MIT and SPT of VO 2 .
36 MATERIALS SCIENCE↗
Purely electronic insulator-metal transition in rutile VO 2
Volatile resistive switching in neuromorphic computing can be tuned by external stimuli such as temperature or electric-field. However, this type of switching is generally coupled to structural changes, resulting in slower reaction speed and higher energy consumption when incorporated into an electronic device. The vanadium dioxide (VO 2 ), which has near room temperature metal-insulator transition (MIT), is an archetypical volatile resistive switching system. Here, we demonstrate an isostructural MIT in an ultrathin VO 2 film capped with a photoconductive cadmium sulfide (CdS) layer. Transmission electron microscopy, resistivity experiments, and first-principles calculations show that the hole carriers induced by CdS photovoltaic effect are driving the MIT in rutile VO 2 . The insulating-rutile VO 2 phase has been proved and can remain stable for hours. Our finding provides a new approach to produce purely electronically driven MIT in VO 2 , and widens its applications in fast-response, low-energy neuromorphic devices.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Switching speed limits in electrically driven VO 2 structural Mott–Peierls transition
Mott materials are archetypal quantum systems actively explored as next-generation electronic and photonic platforms, with potential applications spanning non-Von Neumann computing, robotics, energy storage, and microwave technologies. Among these, vanadium dioxide (VO 2 ) has emerged as one of the most intensively studied compounds, owing to its sharp, near-room-temperature insulator-to-metal phase transition. VO 2 also serves as a benchmark system for testing cutting-edge theories and experimental techniques. Here, we directly visualize the electrically driven transition dynamics in VO 2 using a microwave-driven, frequency-tunable pulsed transmission electron microscope that combines nanometer spatial and picosecond temporal resolution. Under high-frequency (MHz–GHz) excitation, we capture the ultrafast nucleation, propagation, and dissolution of metallic domains within an operating device over millions of reversible cycles. We observe the ultrafast formation of consistent metallic nuclei beneath the electrodes, followed by the propagation of a structural phase front at 4.54 nm/ns. Our experiments show that phonon-mediated structural recovery ultimately limits reversible switching of VO 2 at GHz frequencies, and that a tunable regime for reversible operation spans from kHz to GHz through device engineering. Beyond VO 2 , our approach provides a powerful framework for probing non-equilibrium structural transformations in correlated and functional materials under realistic electrical stimuli.
36 MATERIALS SCIENCE↗
Modulating charge transport via 2 MeV He + irradiation in VO 2
Vanadium dioxide (VO 2 ) is of interest for adaptive electronic applications such as neuromorphic neuristor devices and variable emissivity or tunable thermal control materials, thanks to its key property—a metal–insulator transition (MIT) at 68 °C that is accompanied by a dramatic change in electrical and optical properties. To improve performance in these roles, it is critical to develop approaches to engineer transport properties and the MIT behavior. While many documented techniques exist to modulate the MIT and film resistivities via lattice strain and chemical doping, less is known about the effects of ion irradiation on the intrinsic properties of VO 2 , despite the ability to control the spatial distribution of irradiation beams and the prevalence of high energy ion implantation in the semiconductor industry. The impact of irradiation of different acceleration energies on the responses of VO 2 is of specific interest, as charged particle energy generally impacts both the resulting defect profile and corresponding transport behavior. Here, we demonstrate that 2 MeV He ions at equivalent calculated displacements per atom, in two different types of films, can create remarkable changes to the nature of charge transport in VO 2 , especially in the low-temperature insulating phase. Simulation of resulting changes in electrical conductivity reveals that He ion irradiation offers a strategy to increase both oscillation frequency and the signal transmission. These results provide insights into the intentional design of defect populations to modulate transport for neuromorphic VO 2 devices.
Gurrola, Rebeca M. [Texas A & M Univ., College Sta↗
Inherent stochasticity during insulator–metal transition in VO 2
Vanadium dioxide (VO 2 ), which exhibits a near-room-temperature insulator–metal transition, has great potential in applications of neuromorphic computing devices. Although its volatile switching property, which could emulate neuron spiking, has been studied widely, nanoscale studies of the structural stochasticity across the phase transition are still lacking. In this study, using in situ transmission electron microscopy and ex situ resistive switching measurement, we successfully characterized the structural phase transition between monoclinic and rutile VO 2 at local areas in planar VO 2 /TiO 2 device configuration under external biasing. After each resistive switching, different VO 2 monoclinic crystal orientations are observed, forming different equilibrium states. We have evaluated a statistical cycle-to-cycle variation, demonstrated a stochastic nature of the volatile resistive switching, and presented an approach to study in-plane structural anisotropy. Furthermore, our microscopic studies move a big step forward toward understanding the volatile switching mechanisms and the related applications of VO 2 as the key material of neuromorphic computing.
36 MATERIALS SCIENCE↗
Freestanding VO 2 membranes on epidermal nanomesh for ultra-sensitive correlated breathable sensors
The interest in highly sensitive sensors is rapidly increasing for detecting very tiny signals for Internet of Things devices. Here, we achieve ultra-sensitive correlated breathable sensors based on freestanding VO 2 membranes. We fabricate the membranes by growing VO 2 films onto sacrificial Sr 3 Al 2 O 6 layer grown on SrTiO 3 , selectively dissolving the Sr 3 Al 2 O 6 in water, and then rendering freestanding VO 2 membrane on nanomesh. The nanomeshes are extremely flexible, sweat permeable, and readily skin-adhesive. The resistance of the VO 2 membranes is reversibly tuned by human’s tiny mechanical stimuli and breath stimuli. The stimuli modulate the Peierls dimerization of one-dimensional V-V chains in the VO 2 lattice which concomitantly controls the electron correlation and hence resistivity. Since our breathable sensors operate based on quantum-mechanical correlation effects, their sensitivity is 1-2 orders of magnitude higher than conventional tactile and respiratory sensors based on other materials. Thus, the freestanding membranes of correlated oxides on epidermal nanomeshes are multifunctional platforms for developing ultra-sensitive correlated breathable sensors.
36 MATERIALS SCIENCE↗
Digital Tuning of the Transition Temperature of Epitaxial VO 2 Thin Films on MgF 2 Substrates by Strain Engineering
Abstract Straining the vanadium dimers along the rutile c ‐axis can be used to tune the metal‐to‐insulator transition (MIT) of VO 2 but has thus far been limited to TiO 2 substrates. In this work VO 2 /MgF 2 epitaxial films are grown via molecular beam epitaxy (MBE) to strain engineer the transition temperature ( T MIT ). First, growth parameters are optimized by varying the synthesis temperature of the MgF 2 (001) substrate ( T S ) using a combination of X‐ray diffraction techniques, temperature dependent transport, and soft X‐ray photoelectron spectroscopy. It is determined that T S values greater than 350 °C induce Mg and F interdiffusion and ultimately the relaxation of the VO 2 layer. Using the optimized growth temperature, VO 2 /MgF 2 (101) and (110) films are then synthesized. The three film orientations display MITs with transition temperatures in the range of 15–60 °C through precise strain engineering.
Howard, Sebastian A.↗
Transforming nanoscale VO 2 (B) into a scalable sodium-ion electrode
The intermittent nature of renewable energies requires highly reliable grid-level energy storage approaches. A critical consideration in developing this technology is the areal capacity which determines battery performance and influences the cost of battery technology. Of related importance is finding new ways of developing scalable electrodes. In recent years, three-dimensional (3D) printing of conductive scaffolds has emerged as an alternative to overcome the scalability limitations of commercial tape cast electrodes. The research carried out in the current study demonstrates a successful scalability pathway for nanoscale VO 2 (B), a desirable cathode for sodium-ion batteries which has a nano-flower morphology with a crystallite size < 20 nm. By electrodepositing VO 2 (B) onto a graphene aerogel scaffold, we were able to achieve mass loading of over 100 mg·cm −2 and still possess an areal capacity of 10 mAh·cm −2 at a current density of 5 mA·cm −2 . Moreover, after 1000 cycles, these electrodes retained 75% to 80% of their initial capacity. Even at high loading levels, the electrodeposited VO 2 (B) exhibits pseudocapacitive material signatures such as a box-like voltammetry response, linear galvanostatic response, and no phase change upon lithiation. The scalability of the VO 2 (B) electrode is demonstrated in a series of experiments which show the areal capacity to scale upon increase in both mass loading and electrode thickness, with only small changes in specific capacity. Furthermore, this study establishes that nanoscale materials can be scaled up to achieve thick electrodes without compromising their electrochemical properties.
additive manufacturing↗
Improved cycle stability and high-rate capability of LiNbO 3 -coated Li 3 VO 4 as anode material for lithium-ion battery
Lithium vanadate (Li 3 VO 4 ) has garnered considerable attention as an alternative negative electrode material for non-aqueous lithium-ion batteries due to its high capacity, energy efficiency, and stable discharge voltage. Nonetheless, the Li 3 VO 4 material displays a low rate capability, attributed mainly to its poor intrinsic electronic conductivity. Here, in this study, we report the synthesis of lithium niobate LiNbO 3 -coated Li 3 VO 4 (LVO@LNO) using a one-pot sol-gel method. The resulting LVO@LNO demonstrates a high reversible capacity of approximately 530 mAh/g, which is more than double that of free Li 3 VO 4 . To explore the effect of the LNO coating process on the morphological and structural properties, Raman, XRD, operando XRD, XPS, SEM and HTEM analyses were conducted. To explain the enhancement of electronic conductivity in our modified material after a LiNbO 3 coating, we conducted an Ex-Situ electrochemical impedance (EIS) and Density Functional Theory (DFT) computational study. Additionally, we designed a full cell utilizing a 1 wt% LNO-coated LVO anode and NMC-811 cathode. The cell yielded an output voltage of approximately 2.8 V with a high initial specific capacity of 350 mAh/g versus to the anode, at 1C with a capacity retention of 85 % after 100 cycles.
25 ENERGY STORAGE↗
Experimental and Theoretical Thermokinetic Analysis of the Na 3 VO 4 –CO 2 Reaction System under Different Physicochemical Conditions
Sodium vanadate (Na 3 VO 4 ) was synthesized, structural and microstructurally characterized as well as tested as possible carbon dioxide (CO 2 ) captor through thermodynamic calculations in addition to thermogravimetric dynamic and isothermal analyses. Ceramic structural characterization evidenced the formation of the Na 3 VO 4 crystal phase, while microstructural features evidenced dense agglomerates with a poor specific surface area, although synthesis temperature (600 °C) was not as high as that for other sodium ceramics. Na 3 VO 4 was investigated for the CO 2 capture process through dynamic and isothermal experiments, in the presence or absence of oxygen. All these experiments showed that Na 3 VO 4 possesses interesting CO 2 capture properties in a specific temperature range (520 and 600 °C). Isothermal products characterization allowed to elucidate the reaction pathway, implying the Na 4 V 2 O 7 formation, as possible reactive intermediate. In fact, reaction path evolution was supported with theoretical thermodynamic data. Moreover, the kinetic analysis, performed using the Avrami-Erofeev mathematical model and subsequent thermodynamic data obtention, probed the positive influence of the temperature, in both CO 2 superficial and bulk chemical sorption processes, while oxygen addition did not enhance the superficial process. Additionally, as it would be expected, kinetics were enhanced as a function of the CO 2 concentration.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗