Effect of the substrate on the insulator-metal transition of vanadium dioxide films

NASA Astrophysics Data System (ADS)

Kovács, György J.; Bürger, Danilo; Skorupa, Ilona; Reuther, Helfried; Heller, René; Schmidt, Heidemarie

2011-03-01

Single-phase vanadium dioxide films grown on (0001) sapphire and (001) silicon substrates show a very different insulator-metal electronic transition. A detailed description of the growth mechanisms and the substrate-film interaction is given, and the characteristics of the electronic transition are described by the morphology and grain boundary structure. (Tri-)epitaxy-stabilized columnar growth of VO2 takes place on the sapphire substrate, whereas on silicon the expected Zone II growth is identified. We have found that in the case of the Si substrate the reasons for the broader hysteresis and the lower switching amplitude are the formation of an amorphous insulating VOx (x > 2.6) phase coexisting with VO2 and the high vanadium vacancy concentration of the VO2. These phenomena are the result of the excess oxygen during the growth and the interaction between the silicon substrate and the growing film.

Tunable multiband polarization conversion and manipulation in vanadium dioxide-based asymmetric chiral metamaterial

NASA Astrophysics Data System (ADS)

Song, Shichao; Ma, Xiaoliang; Pu, Mingbo; Li, Xiong; Zhang, Zuojun; Gao, Ping; Luo, Xiangang

2018-04-01

Tunable multiband polarization conversion and manipulation are achieved by introducing vanadium dioxide (VO2) into a planar spiral asymmetric chiral metamaterial. Numerical simulations demonstrate that when VO2 is in the insulating state, circularly polarized electromagnetic waves are emitted at two distinct resonant frequencies. When VO2 is in the metallic state, the number of resonant frequencies changes from two to four. In addition, the initial left-handed and right-handed circularly polarized transmitted waves correspondingly transform into right and left ones. Moreover, the surface current distributions are studied in order to investigate the transformation behaviors of both the insulating and metallic states.

Rapid hydrothermal synthesis of VO2 (B) and its conversion to thermochromic VO2 (M1).

PubMed

Popuri, Srinivasa Rao; Miclau, Marinela; Artemenko, Alla; Labrugere, Christine; Villesuzanne, Antoine; Pollet, Michaël

2013-05-06

The present study provides a rapid way to obtain VO2 (B) under economical and environmentally friendly conditions. VO2 (B) is one of the well-known polymorphs of vanadium dioxide and is a promising cathode material for aqueous lithium ion batteries. VO2 (B) was successfully synthesized by rapid single-step hydrothermal process using V2O5 and citric acid as precursors. The present study shows that phase-pure VO2 (B) polytype can be easily obtained at 180 °C for 2 h and 220 °C for 1 h, that is, the lowest combination of temperature and duration reported so far. The obtained VO2 (B) is characterized by X-ray powder diffraction, high-resolution scanning electron microscopy, and Fourier transform infrared spectroscopy. In addition, we present an indirect way to obtain VO2 (M1) by annealing VO2 (B) under vacuum for 1 h.

Semiconductor-metal phase transition of vanadium dioxide nanostructures on silicon substrate: Applications for thermal control of spacecraft

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leahu, G. L., E-mail: roberto.livoti@uniroma1.it; Li Voti, R., E-mail: roberto.livoti@uniroma1.it; Larciprete, M. C., E-mail: roberto.livoti@uniroma1.it

2014-06-19

We present a detailed infrared study of the semiconductor-to-metal transition (SMT) in a vanadium dioxide (VO2) film deposited on silicon wafer. The VO2 phase transition is studied in the mid-infrared (MIR) region by analyzing the transmittance and the reflectance measurements, and the calculated emissivity. The temperature behaviour of the emissivity during the SMT put into evidence the phenomenon of the anomalous absorption in VO2 which has been explained by applying the Maxwell Garnett effective medium approximation theory, together with a strong hysteresis phenomenon, both useful to design tunable thermal devices to be applied for the thermal control of spacecraft. Wemore » have also applied the photothermal radiometry in order to study the changes in the modulated emissivity induced by laser. Experimental results show how the use of these techniques represent a good tool for a quantitative measurement of the optothermal properties of vanadium dioxide based structures.« less

Solution-processed phase-change VO(2) metamaterials from colloidal vanadium oxide (VO(x)) nanocrystals.

PubMed

Paik, Taejong; Hong, Sung-Hoon; Gaulding, E Ashley; Caglayan, Humeyra; Gordon, Thomas R; Engheta, Nader; Kagan, Cherie R; Murray, Christopher B

2014-01-28

We demonstrate thermally switchable VO2 metamaterials fabricated using solution-processable colloidal nanocrystals (NCs). Vanadium oxide (VOx) NCs are synthesized through a nonhydrolytic reaction and deposited from stable colloidal dispersions to form NC thin films. Rapid thermal annealing transforms the VOx NC thin films into monoclinic, nanocrystalline VO2 thin films that show a sharp, reversible metal-insulator phase transition. Introduction of precise concentrations of tungsten dopings into the colloidal VOx NCs enables the still sharp phase transition of the VO2 thin films to be tuned to lower temperatures as the doping level increases. We fabricate "smart", differentially doped, multilayered VO2 films to program the phase and therefore the metal-insulator behavior of constituent vertically structured layers with temperature. With increasing temperature, we tailored the optical response of multilayered films in the near-IR and IR regions from that of a strong light absorber, in a metal-insulator structure, to that of a Drude-like reflector, characteristic of a pure metallic structure. We demonstrate that nanocrystal-based nanoimprinting can be employed to pattern multilayered subwavelength nanostructures, such as three-dimensional VO2 nanopillar arrays, that exhibit plasmonic dipolar responses tunable with a temperature change.

Electric-field-driven phase transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Wu, B.; Zimmers, A.; Aubin, H.; Gosh, R.; Liu, Y.; Lopez, R.

2011-03-01

In recent years, various strongly correlated materials have shown sharp switching from insulator to metallic state in their I(V) transport curves. Determining if this is purely an out of equilibrium phenomena (due to the strong electric field applied throughout the sample) or simply a Joule heating issue is still an open question. To address this issue, we have first measured local I(V) curves in vanadium dioxide (VO2) Mott insulator at various temperatures using a conducting AFM setup and determined the voltage threshold of the insulator to metal switching. By lifting the tip above the surface (> 35 nm) , wehavethenmeasuredthepurelyelectrostaticforcebetweenthetipandsamplesurfaceasthevoltagebetweenthesetwowasincreased . Inaverynarrowtemperaturerange (below 360 K) , atipheightrange (below 60 nm) andavoltageappliedrange (above 8 V) , weobservedswitchingintheelectrostaticforce (telegraphicnoisevs . timeandvs . voltage) . ThispurelyelectricfieldeffectshowsthattheswitchingphenomenonisstillpresentevenwithoutJouleheatinginVO 2 .

On the metal-insulator-transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Godoy, Salvador; Suzuki, Akira

2012-02-01

Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity σ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop.

VO{sub 2} precipitates for self-protected optical surfaces

DOEpatents

Gea, L.A.; Boatner, L.A.

1999-03-23

A method for forming crystallographically coherent precipitates of vanadium dioxide in the near-surface region of sapphire and the resulting product is disclosed. Ions of vanadium and oxygen are stoichiometrically implanted into a sapphire substrate (Al{sub 2}O{sub 3}), and subsequently annealed to form vanadium dioxide precipitates in the substrate. The embedded VO{sub 2} precipitates, which are three-dimensionally oriented with respect to the crystal axes of the Al{sub 2}O{sub 3} host lattice, undergo a first-order monoclinic-to-tetragonal (and also semiconducting-to-metallic) phase transition at ca. 77 C. This transformation is accompanied by a significant variation in the optical transmission of the implanted region and results in the formation of an optically active, thermally ``switchable`` surface region on Al{sub 2}O{sub 3}. 5 figs.

VO.sub.2 precipitates for self-protected optical surfaces

DOEpatents

Gea, Laurence A.; Boatner, Lynn A.

1999-01-01

A method for forming crystallographically coherent precipitates of vanadium dioxide in the near-surface region of sapphire and the resulting product is disclosed. Ions of vanadium and oxygen are stoichiometrically implanted into a sapphire substrate (Al.sub.2 O.sub.3), and subsequently annealed to form vanadium dioxide precipitates in the substrate. The embedded VO.sub.2 precipitates, which are three-dimensionally oriented with respect to the crystal axes of the Al.sub.2 O.sub.3 host lattice, undergo a first-order monoclinic-to-tetragonal (and also semiconducting-to-metallic) phase transition at .about.77.degree. C. This transformation is accompanied by a significant variation in the optical transmission of the implanted region and results in the formation of an optically active, thermally "switchable" surface region on Al.sub.2 O.sub.3.

Tunable assembly of vanadium dioxide nanoparticles to create porous film for energy-saving applications.

PubMed

Ding, Shangjun; Liu, Zhanqiang; Li, Dezeng; Zhao, Wei; Wang, Yaoming; Wan, Dongyun; Huang, Fuqiang

2013-03-13

Nanoparticle-assembled vanadium dioxide (VO2) films have been easily prepared with the assistance of cetyltrimethylammonium vanadate (CTAV) precursor which exhibits self-assembly properties. The obtained VO2 film has a micro/nano hierarchical porous structure, so its visible-light transmittance is significantly improved (∼25% increased compared to continuous film). The VO2 particle density as well as the film porosity can be facilely controlled by adjusting experimental parameters such as dip-coating speed. Accordingly, film optical properties can also be tuned to a large extent, in particular the visible transmittance (Tvis) and near-infrared switching efficiency (ΔTnir). These VO2 nanoparticle-assembled films prepared by this novel method provide a useful model to research the balance between Tvis and ΔTnir.

Effects of gamma irradiations on reactive pulsed laser deposited vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Madiba, I. G.; Émond, N.; Chaker, M.; Thema, F. T.; Tadadjeu, S. I.; Muller, U.; Zolliker, P.; Braun, A.; Kotsedi, L.; Maaza, M.

2017-07-01

Vanadium oxide films are considered suitable coatings for various applications such as thermal protective coating of small spacecrafts because of their thermochromic properties. While in outer space, such coating will be exposed to cosmic radiations which include γ-rays. To study the effect of these γ-rays on the coating properties, we have deposited vanadium dioxide (VO2) films on silicon substrates and subjected them to extensive γ-irradiations with typical doses encountered in space missions. The prevalent crystallographic phase after irradiation remains the monoclinic VO2 phase but the films preferential orientation shifts to lower angles due to the presence of disordered regions caused by radiations. Raman spectroscopy measurements also evidences that the VO2 structure is slightly affected by gamma irradiation. Indeed, increasing the gamma rays dose locally alters the crystalline and electronic structures of the films by modifying the V-V inter-dimer distance, which in turns favours the presence of the VO2 metallic phase. From the XPS measurements of V2p and O1s core level spectra, an oxidation of vanadium from V4+ towards V5+ is revealed. The data also reveal a hydroxylation upon irradiation which is corroborated by the vanishing of a low oxidation state peak near the Fermi energy in the valence band. Our observations suggest that gamma radiations induce the formation of Frenkel pairs. Moreover, THz transmission measurements show that the long range structure of VO2 remains intact after irradiation whilst the electrical measurements evidence that the coating resistivity decreases with gamma irradiation and that their transition temperature is slightly reduced for high gamma ray doses. Even though gamma rays are only one of the sources of radiations that are encountered in space environment, these results are very promising with regards to the potential of integration of such VO2 films as a protective coating for spacecrafts.

Electrochemically Induced Insulator-Metal-Insulator Transformations of Vanadium Dioxide Nanocrystal Films

NASA Astrophysics Data System (ADS)

Milliron, Delia; Dahlman, Clayton; Leblanc, Gabriel; Bergerud, Amy

Vanadium dioxide (VO2) undergoes significant optical, electronic, and structural changes as it transforms between the low-temperature monoclinic and high-temperature rutile phases. The low-temperature state is insulating and transparent, while the high-temperature state is metallic and IR blocking. Alternative stimuli have been utilized to trigger insulator-to-metal transformations in VO2, including electrochemical gating. Here, VO2 nanocrystal films have been prepared by solution deposition of V2O3 nanocrystals followed by oxidative annealing. Nanocrystalline VO2 films are electrochemically reduced, inducing changes in their electronic and optical properties. We observe a reversible transition between infrared transparent insulating phases and a darkened metallic phase by in situ visible-near-infrared spectroelectrochemistry and correlate these observations with structural and electronic changes monitored by X-ray absorption spectroscopy, X-ray diffraction, Raman spectroscopy, and conductivity measurements. Reduction causes an initial transformation to a metallic, IR-colored distorted monoclinic phase. However, an unexpected reversible transition from conductive, reduced monoclinic VO2 to an infrared-transparent insulating phase is observed upon further reduction.

Photoinduced surface plasmon switching at VO2/Au interface.

PubMed

Kumar, Nardeep; Rúa, Armando; Aldama, Jennifer; Echeverría, Karla; Fernández, Félix E; Lysenko, Sergiy

2018-05-28

Angle-resolved reflection, light scattering and ultrafast pump-probe spectroscopy combined with a surface plasmon-polariton (SPP) resonance technique in attenuated total reflection geometry was used to investigate the light-induced plasmonic switching in a photorefractive VO 2 /Au hybrid structure. Measurements of SPP scattering and reflection shows that the optically-induced formation of metallic state in a vanadium dioxide layer deposited on a gold film significantly alters the electromagnetic field enhancement and SPP propagation length at the VO 2 /Au interface. The ultrafast optical manipulation of SPP resonance is shown on a picosecond timescale. Obtained results demonstrate high potential of photorefractive vanadium oxides as efficient plasmonic modulating materials for ultrafast optoelectronic devices.

Electron Microscopy Characterization of Vanadium Dioxide Thin Films and Nanoparticles

NASA Astrophysics Data System (ADS)

Rivera, Felipe

Vanadium dioxide (VO_2) is a material of particular interest due to its exhibited metal to insulator phase transition at 68°C that is accompanied by an abrupt and significant change in its electronic and optical properties. Since this material can exhibit a reversible drop in resistivity of up to five orders of magnitude and a reversible drop in infrared optical transmission of up to 80%, this material holds promise in several technological applications. Solid phase crystallization of VO_2 thin films was obtained by a post-deposition annealing process of a VO_{x,x approx 2} amorphous film sputtered on an amorphous silicon dioxide (SiO_2) layer. Scanning electron microscopy (SEM) and electron-backscattered diffraction (EBSD) were utilized to study the morphology of the solid phase crystallization that resulted from this post-deposition annealing process. The annealing parameters ranged in temperature from 300°C up to 1000°C and in time from 5 minutes up to 12 hours. Depending on the annealing parameters, EBSD showed that this process yielded polycrystalline vanadium dioxide thin films, semi-continuous thin films, and films of isolated single-crystal particles. In addition to these films on SiO_2, other VO_2 thin films were deposited onto a-, c-, and r-cuts of sapphire and on TiO_2(001) heated single-crystal substrates by pulsed-laser deposition (PLD). The temperature of the substrates was kept at ˜500°C during deposition. EBSD maps and orientation imaging microscopy were used to study the epitaxy and orientation of the VO_2 grains deposited on the single crystal substrates, as well as on the amorphous SiO_2 layer. The EBSD/OIM results showed that: 1) For all the sapphire substrates analyzed, there is a predominant family of crystallographic relationships wherein the rutile VO_2{001} planes tend to lie parallel to the sapphire's {10-10} and the rutile VO_2{100} planes lie parallel to the sapphire's {1-210} and {0001}. Furthermore, while this family of

Photo-driven nanoactuators based on carbon nanocoils and vanadium dioxide bimorphs.

PubMed

Ma, He; Zhang, Xinping; Cui, Ruixue; Liu, Feifei; Wang, Meng; Huang, Cuiying; Hou, Jiwei; Wang, Guang; Wei, Yang; Jiang, Kaili; Pan, Lujun; Liu, Kai

2018-06-06

Photo-driven actuators are highly desirable in various smart systems owing to the advantages of wireless control and possible actuation by solar energy. Miniaturization of photo-driven actuators is particularly essential in micro-robotics and micro-/nano-electro-mechanical systems. However, it remains a great challenge to build up nano-scale photo-driven actuators with competitive performance in amplitude, response speed, and lifetime. In this work, we developed photo-driven nanoactuators based on bimorph structures of vanadium dioxides (VO2) and carbon nanocoils (CNCs). Activated by the huge structural phase transition of VO2, the photo-driven VO2/CNC nanoactuators deliver a giant amplitude, a fast response up to 9400 Hz, and a long lifetime more than 10 000 000 actuation cycles. Both experimental and simulation results show that the helical structure of CNCs enables a low photo-driven threshold of VO2/CNC nanoactuators, which provides an effective method to construct photo-driven nanoactuators with low power consumption. Our photo-driven VO2/CNC nanoactuators would find potential applications in nano-scale electrical/optical switches and other smart devices.

Ultrafast electron-lattice coupling dynamics in VO2 and V2O3 thin films

NASA Astrophysics Data System (ADS)

Abreu, Elsa; Gilbert Corder, Stephanie N.; Yun, Sun Jin; Wang, Siming; Ramírez, Juan Gabriel; West, Kevin; Zhang, Jingdi; Kittiwatanakul, Salinporn; Schuller, Ivan K.; Lu, Jiwei; Wolf, Stuart A.; Kim, Hyun-Tak; Liu, Mengkun; Averitt, Richard D.

2017-09-01

Ultrafast optical pump-optical probe and optical pump-terahertz probe spectroscopy were performed on vanadium dioxide (VO2) and vanadium sesquioxide (V2O3 ) thin films over a wide temperature range. A comparison of the experimental data from these two different techniques and two different vanadium oxides, in particular a comparison of the spectral weight oscillations generated by the photoinduced longitudinal acoustic modulation, reveals the strong electron-phonon coupling that exists in both materials. The low-energy Drude response of V2O3 appears more amenable than VO2 to ultrafast strain control. Additionally, our results provide a measurement of the temperature dependence of the sound velocity in both systems, revealing a four- to fivefold increase in VO2 and a three- to fivefold increase in V2O3 across the insulator-to-metal phase transition. Our data also confirm observations of strong damping and phonon anharmonicity in the metallic phase of VO2, and suggest that a similar phenomenon might be at play in the metallic phase of V2O3 . More generally, our simple table-top approach provides relevant and detailed information about dynamical lattice properties of vanadium oxides, paving the way to similar studies in other complex materials.

Current induced polycrystalline-to-crystalline transformation in vanadium dioxide nanowires

PubMed Central

Jeong, Junho; Yong, Zheng; Joushaghani, Arash; Tsukernik, Alexander; Paradis, Suzanne; Alain, David; Poon, Joyce K. S.

2016-01-01

Vanadium dioxide (VO2) exhibits a reversible insulator-metal phase transition that is of significant interest in energy-efficient nanoelectronic and nanophotonic devices. In these applications, crystalline materials are usually preferred for their superior electrical transport characteristics as well as spatial homogeneity and low surface roughness over the device area for reduced scattering. Here, we show applied electrical currents can induce a permanent reconfiguration of polycrystalline VO2 nanowires into crystalline nanowires, resulting in a dramatically reduced hysteresis across the phase transition and reduced resistivity. Low currents below 3 mA were sufficient to cause the local temperature in the VO2 to reach about 1780 K to activate the irreversible polycrystalline-to-crystalline transformation. The crystallinity was confirmed by electron microscopy and diffraction analyses. This simple yet localized post-processing of insulator-metal phase transition materials may enable new methods of studying and fabricating nanoscale structures and devices formed from these materials. PMID:27892519

Optical switching and photoluminescence in erbium-implanted vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Lim, Herianto; Stavrias, Nikolas; Johnson, Brett C.; Marvel, Robert E.; Haglund, Richard F.; McCallum, Jeffrey C.

2014-03-01

Vanadium dioxide (VO2) is under intensive consideration for optical switching due to its reversible phase transition, which features a drastic and rapid shift in infrared reflectivity. Classified as an insulator-to-metal transition, the phase transition in VO2 can be induced thermally, electrically, and optically. When induced optically, the transition can occur on sub-picosecond time scales. It is interesting to dope VO2 with erbium ions (Er3+) and observe their combined properties. The first excited-state luminescence of Er3+ lies within the wavelength window of minimal transmission-loss in silicon and has been widely utilized for signal amplification and generation in silicon photonics. The incorporation of Er3+ into VO2 could therefore result in a novel photonic material capable of simultaneous optical switching and amplification. In this work, we investigate the optical switching and photoluminescence in Er-implanted VO2 thin films. Thermally driven optical switching is demonstrated in the Er-implanted VO2 by infrared reflectometry. Photoluminescence is observed in the thin films annealed at ˜800 °C or above. In addition, Raman spectroscopy and a statistical analysis of switching hysteresis are carried out to assess the effects of the ion implantation on the VO2 thin films. We conclude that Er-implanted VO2 can function as an optical switch and amplifier, but with reduced switching quality compared to pure VO2.

Graphene‐Nanowall‐Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2 +/VO2+ Couple for All Vanadium Redox Flow Battery

PubMed Central

Li, Wenyue; Zhang, Zhenyu; Bian, Haidong; Ng, Tsz‐Wai

2015-01-01

3D graphene‐nanowall‐decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO2 +/VO2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging–discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode. PMID:27774399

Graphene-Nanowall-Decorated Carbon Felt with Excellent Electrochemical Activity Toward VO2+/VO2+ Couple for All Vanadium Redox Flow Battery.

PubMed

Li, Wenyue; Zhang, Zhenyu; Tang, Yongbing; Bian, Haidong; Ng, Tsz-Wai; Zhang, Wenjun; Lee, Chun-Sing

2016-04-01

3D graphene-nanowall-decorated carbon felts (CF) are synthesized via an in situ microwave plasma enhanced chemical vapor deposition method and used as positive electrode for vanadium redox flow battery (VRFB). The carbon fibers in CF are successfully wrapped by vertically grown graphene nanowalls, which not only increase the electrode specific area, but also expose a high density of sharp graphene edges with good catalytic activities to the vanadium ions. As a result, the VRFB with this novel electrode shows three times higher reaction rate toward VO 2 + /VO 2+ redox couple and 11% increased energy efficiency over VRFB with an unmodified CF electrode. Moreover, this designed architecture shows excellent stability in the battery operation. After 100 charging-discharging cycles, the electrode not only shows no observable morphology change, it can also be reused in another battery and practical with the same performance. It is believed that this novel structure including the synthesis procedure will provide a new developing direction for the VRFB electrode.

Multilevel radiative thermal memory realized by the hysteretic metal-insulator transition of vanadium dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ito, Kota, E-mail: kotaito@mosk.tytlabs.co.jp; Nishikawa, Kazutaka; Iizuka, Hideo

Thermal information processing is attracting much interest as an analog of electronic computing. We experimentally demonstrated a radiative thermal memory utilizing a phase change material. The hysteretic metal-insulator transition of vanadium dioxide (VO{sub 2}) allows us to obtain a multilevel memory. We developed a Preisach model to explain the hysteretic radiative heat transfer between a VO{sub 2} film and a fused quartz substrate. The transient response of our memory predicted by the Preisach model agrees well with the measured response. Our multilevel thermal memory paves the way for thermal information processing as well as contactless thermal management.

Role of microstructures on the M1-M2 phase transition in epitaxial VO2 thin films

PubMed Central

Ji, Yanda; Zhang, Yin; Gao, Min; Yuan, Zhen; Xia, Yudong; Jin, Changqing; Tao, Bowan; Chen, Chonglin; Jia, Quanxi; Lin, Yuan

2014-01-01

Vanadium dioxide (VO2) with its unique sharp resistivity change at the metal-insulator transition (MIT) has been extensively considered for the near-future terahertz/infrared devices and energy harvesting systems. Controlling the epitaxial quality and microstructures of vanadium dioxide thin films and understanding the metal-insulator transition behaviors are therefore critical to novel device development. The metal-insulator transition behaviors of the epitaxial vanadium dioxide thin films deposited on Al2O3 (0001) substrates were systematically studied by characterizing the temperature dependency of both Raman spectrum and Fourier transform infrared spectroscopy. Our findings on the correlation between the nucleation dynamics of intermediate monoclinic (M2) phase with microstructures will open a new avenue for the design and integration of advanced heterostructures with controllable multifunctionalities for sensing and imaging system applications. PMID:24798056

Tunable VO{sub 2}/Au hyperbolic metamaterial

DOE Office of Scientific and Technical Information (OSTI.GOV)

Prayakarao, S.; Noginov, M. A., E-mail: mnoginov@nsu.edu; Mendoza, B.

2016-08-08

Vanadium dioxide (VO{sub 2}) is known to have a semiconductor-to-metal phase transition at ∼68 °C. Therefore, it can be used as a tunable component of an active metamaterial. The lamellar metamaterial studied in this work is composed of subwavelength VO{sub 2} and Au layers and is designed to undergo a temperature controlled transition from the optical hyperbolic phase to the metallic phase. VO{sub 2} films and VO{sub 2}/Au lamellar metamaterial stacks have been fabricated and studied in electrical conductivity and optical (transmission and reflection) experiments. The observed temperature-dependent changes in the reflection and transmission spectra of the metamaterials and VO{sub 2}more » thin films are in a good qualitative agreement with theoretical predictions. The demonstrated optical hyperbolic-to-metallic phase transition is a unique physical phenomenon with the potential to enable advanced control of light-matter interactions.« less

Vanadium doped tin dioxide as a novel sulfur dioxide sensor.

PubMed

Das, S; Chakraborty, S; Parkash, O; Kumar, D; Bandyopadhyay, S; Samudrala, S K; Sen, A; Maiti, H S

2008-04-15

Considering the short-term exposure limit of SO2 to be 5 ppm, we first time report that semiconductor sensors based on vanadium doped SnO2 can be used for SO2 leak detection because of their good sensitivity towards SO2 at concentrations down to 5 ppm. Such sensors are quite selective in presence of other gases like carbon monoxide, methane and butane. The high sensitivity of vanadium doped tin dioxide towards SO2 may be understood by considering the oxidation of sulfur dioxide to sulfur trioxide on SnO2 surface through redox cycles of vanadium-sulfur-oxygen adsorbed species.

Enhanced luminous transmittance of thermochromic VO2 thin film patterned by SiO2 nanospheres

NASA Astrophysics Data System (ADS)

Zhou, Liwei; Liang, Jiran; Hu, Ming; Li, Peng; Song, Xiaolong; Zhao, Yirui; Qiang, Xiaoyong

2017-05-01

In this study, an ordered SiO2 nanosphere array coated with vanadium dioxide (VO2) has been fabricated to enhance transmittance with the potential application as an energy-efficient coating in the field of smart windows. SiO2 arrays were formed using the methods of self-assembly, and VO2 thin films were prepared by rapid thermal annealing (RTA) of sputtered vanadium films. VO2@SiO2 arrays were characterized by scanning electron microscopy, X-ray diffraction, a four-point probe, and UV-vis-NIR spectrophotometry. Compared with the planar films, the films deposited on 300 nm diameter SiO2 nanospheres can offer approximately 18% enhancement of luminous transmission (Tlum) because the diameter is smaller than the given wavelength and the protuberance of the surface array behaves as a gradation of refractive index producing antireflection. The solar regulation efficiency was not much deteriorated.

Vanadium dioxide nanogrid films for high transparency smart architectural window applications.

PubMed

Liu, Chang; Balin, Igal; Magdassi, Shlomo; Abdulhalim, Ibrahim; Long, Yi

2015-02-09

This study presents a novel approach towards achieving high luminous transmittance (T(lum)) for vanadium dioxide (VO(2)) thermochromic nanogrid films whilst maintaining the solar modulation ability (ΔT(sol)). The perforated VO(2)-based films employ orderly-patterned nano-holes, which are able to favorably transmit visible light dramatically but retain large near-infrared modulation, thereby enhancing ΔT(sol). Numerical optimizations using parameter search algorithms have implemented through a series of Finite Difference Time Domain (FDTD) simulations by varying film thickness, cell periodicity, grid dimensions and variations of grid arrangement. The best performing results of T(lum) (76.5%) and ΔT(sol) (14.0%) are comparable, if not superior, to the results calculated from nanothermochromism, nanoporosity and biomimic nanostructuring. It opens up a new approach for thermochromic smart window applications.

Origin of phase transition in VO2

NASA Astrophysics Data System (ADS)

Basu, Raktima; Sardar, Manas; Dhara, Sandip

2018-04-01

Vanadium dioxide (VO2) exhibits a reversible first-order metal to insulator transition (MIT) along with a structural phase transition (SPT) from monoclinic M1 to rutile tetragonal R via another two intermediate phases of monoclinic M2 and triclinic T at a technologically important temperature of 340K. In the present work, besides synthesizing M1 phase of VO2, we also stabilized M2 and T phases at room temperature by introducing native defects in the system and observed an increase in transition temperature with increase in native defects. Raman spectroscopic measurements were carried out to confirm the pure VO2 phases. Since the MIT is accompanied by SPT in these systems, the origin of the phase transition is still under debate. The controversy between MIT and SPT, whether electron-phonon coupling or strong electron-electron correlation triggers the phase transition in VO2 is also resolved by examining the presence of intermediate phase M2 during phase transition.

Stress compensation for arbitrary curvature control in vanadium dioxide phase transition actuators

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dong, Kaichen, E-mail: dkc12@mails.tsinghua.edu.cn, E-mail: wuj@berkeley.edu; Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720; State Key Laboratory of Precision Measurement Technology and Instruments, Department of Precision Instrument, Tsinghua University, Beijing 100084

2016-07-11

Due to its thermally driven structural phase transition, vanadium dioxide (VO{sub 2}) has emerged as a promising material for micro/nano-actuators with superior volumetric work density, actuation amplitude, and repetition frequency. However, the high initial curvature of VO{sub 2} actuators severely obstructs the actuation performance and application. Here, we introduce a “seesaw” method of fabricating tri-layer cantilevers to compensate for the residual stress and realize nearly arbitrary curvature control of VO{sub 2} actuators. By simply adjusting the thicknesses of the individual layers, cantilevers with positive, zero, or negative curvatures can be engineered. The actuation amplitude can be decoupled from the curvaturemore » and controlled independently as well. Based on the experimentally measured residual stresses, we demonstrate sub-micron thick VO{sub 2} actuators with nearly zero final curvature and a high actuation amplitude simultaneously. This “seesaw” method can be further extended to the curvature engineering of other microelectromechanical system multi-layer structures where large stress-mismatch between layers are inevitable.« less

Vanadium dioxide-based materials for potential thermal switching applications

NASA Astrophysics Data System (ADS)

Jeong, Minyoung

One of the materials able to exhibit a transition from insulators to metals (IMT materials) is vanadium dioxide (VO2). Through IMT, VO2 shows a drop of resistivity of five orders of magnitude at a picosecond timescale. In this work, the feasibility of using VO2 as an efficient thermal switching device is discussed. Several synthesis methods (sol-gel, hot press and spark plasma sintering) were attempted to obtain VO2 sample in pellet form. From the X-ray diffraction results, it was found that spark plasma sintering (SPS) yielded the highest phase purity. Several sintering parameters such as temperature or sintering time were tested to determine the optimal sintering conditions. For better thermal switching behavior, high-energy ball milling was used to reduce lattice thermal conductivity (klat.) in the insulator phase. Ball-milling time was varied from 30 minutes to 2 hours. It was found that with increasing milling time, the k lat. was reduced. Thus, it was demonstrated that thermal switching behavior was most efficient with 2 hour-milling. To improve electronic thermal conductivity ( kelec.) in the metallic state, nano-sized copper particles were added to the VO2 system with a subtle amount variation ranging from 3at % to 5 at%. Results show that a composite with 5 at% Cu (copper) addition exhibited the largest increase in thermal conductivity ( k) in the metallic state. In addition to this, a basic mechanism behind IMT and some of the exemplary IMT-based applications were introduced.

Nonlinear-optical properties of thick composite media with vanadium dioxide nanoparticles. II. Self-focusing of mid-IR radiation

NASA Astrophysics Data System (ADS)

Vinogradova, O. P.; Ostrosablina, A. A.; Sidorov, A. I.

2006-02-01

This paper presents the experimental and theoretical results of a study of the interaction of pulsed laser radiation with thick composite media containing nanoparticles of vanadium dioxide (VO2). It is established that the reversible semiconductor-metal phase transition that occurs in the VO2 nanoparticles under the action of radiation can produce self-focusing of the mid-IR radiation by the formation of a photoinduced dynamic lens. An analysis is carried out of how the radiation intensity affects the dynamics of the given process.

Variable electrical properties in composites: Application to vanadium dioxide pigments in a polyethylene host

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alfred-Duplan, C.; Musso, J.; Gavarri, J.R.

1994-05-01

Composite pellets were prepared from low-density polyethylene (LDPE) and vanadium dioxide powders. The VO[sub 2] pigments are used for their insulating-to-metallic transition at 341 K in order to obtain electrically variable composite materials. The volume fractions of VO[sub 2] powders vary from [phi] = 0 to [phi] = 0.55. The composite samples are characterized by X-ray diffraction and scanning electron microscopy. Complex impedance analysis in the frequency range 10[sup [minus]1] to 10[sup 6]. Hz is carried out at room temperature and at T = 363 K, to observe the insulator-metal transition of VO[sub 2] pigments dispersed in the polymer host.more » The variation of the complex impedance modulus [vert bar]Z[vert bar] with frequency and with VO[sub 2] volume fraction ([phi]) is discussed. A specific (R, C) impedance model permits interpretation of the experimental results in terms of percolation; the observed variations can be accounted for.« less

Flexible thermochromic window based on hybridized VO2/graphene.

PubMed

Kim, Hyeongkeun; Kim, Yena; Kim, Keun Soo; Jeong, Hu Young; Jang, A-Rang; Han, Seung Ho; Yoon, Dae Ho; Suh, Kwang S; Shin, Hyeon Suk; Kim, TaeYoung; Yang, Woo Seok

2013-07-23

Large-scale integration of vanadium dioxide (VO2) on mechanically flexible substrates is critical to the realization of flexible smart window films that can respond to environmental temperatures to modulate light transmittance. Until now, the formation of highly crystalline and stoichiometric VO2 on flexible substrate has not been demonstrated due to the high-temperature condition for VO2 growth. Here, we demonstrate a VO2-based thermochromic film with unprecedented mechanical flexibility by employing graphene as a versatile platform for VO2. The graphene effectively functions as an atomically thin, flexible, yet robust support which enables the formation of stoichiometric VO2 crystals with temperature-driven phase transition characteristics. The graphene-supported VO2 was capable of being transferred to a plastic substrate, forming a new type of flexible thermochromic film. The flexible VO2 films were then integrated into the mock-up house, exhibiting its efficient operation to reduce the in-house temperature under infrared irradiation. These results provide important progress for the fabrication of flexible thermochromic films for energy-saving windows.

Infrared characteristics of VO2 thin films for smart window and laser protection applications

NASA Astrophysics Data System (ADS)

Huang, Zhangli; Chen, Sihai; Lv, Chaohong; Huang, Ying; Lai, Jianjun

2012-11-01

Vanadium dioxide (VO2) films with a low semiconductor-to-metal transition temperature of 45 °C were fabricated through direct current magnetron sputtering followed by a post-annealing. Atomic force microscopy measurements show that the VO2 grain size is about one hundred of nanometers. Infrared (IR) characteristic is well investigated by applying a He-Ne laser power intensity measurement, and the result reveals that the VO2 film exhibits excellent IR switching property. Furthermore, solar smart window and laser protection experiments demonstrate that the obtained VO2 thin film is a promising material for the application in related fields.

Microstructures and thermochromic characteristics of VO2/AZO composite films

NASA Astrophysics Data System (ADS)

Xiao, Han; Li, Yi; Yuan, Wenrui; Fang, Baoying; Wang, Xiaohua; Hao, Rulong; Wu, Zhengyi; Xu, Tingting; Jiang, Wei; Chen, Peizu

2016-05-01

A vanadium dioxide (VO2) thin film was fabricated on a ZnO doped with Al (AZO) conductive glass by magnetron sputtering at room temperature followed by annealing under air atmosphere. The microstructures and optical properties of the thin film were studied. The results showed that the VO2/AZO composite film was poly-crystalline and the AZO layer did not change the preferred growth orientation of VO2. Compared to the VO2 film fabricated on soda-lime glass substrate through the same process and condition, the phase transition temperature of the VO2/AZO composite film was decreased by about 25 °C, thermal hysteresis width narrowed to 6 °C, the visible light transmittance was over 50%, the infrared transmittances before and after phase transition were 21% and 55%, respectively at 1500 nm.

Naturally formed ultrathin V2O5 heteroepitaxial layer on VO2/sapphire(001) film

NASA Astrophysics Data System (ADS)

Littlejohn, Aaron J.; Yang, Yunbo; Lu, Zonghuan; Shin, Eunsung; Pan, KuanChang; Subramanyam, Guru; Vasilyev, Vladimir; Leedy, Kevin; Quach, Tony; Lu, Toh-Ming; Wang, Gwo-Ching

2017-10-01

Vanadium dioxide (VO2) and vanadium pentoxide (V2O5) thin films change their properties in response to external stimuli such as photons, temperature, electric field and magnetic field and have applications in electronics, optical devices, and sensors. Due to the multiple valence states of V and non-stoichiometry in thin films, it is challenging to grow epitaxial, single-phase V-oxide on a substrate, or a heterostructure of two epitaxial V-oxides. We report the formation of a heterostructure consisting of a few nm thick ultrathin V2O5 epitaxial layer on pulsed laser deposited tens of nm thick epitaxial VO2 thin films grown on single crystal Al2O3(001) substrates without post annealing of the VO2 film. The simultaneous observation of the ultrathin epitaxial V2O5 layer and VO2 epitaxial film is only possible by our unique reflection high energy electron diffraction pole figure analysis. The out-of-plane and in-plane epitaxial relationships are V2O5[100]||VO2[010]||Al2O3[001] and V2O5[03 2 bar ]||VO2[100]||Al2O3[1 1 bar 0], respectively. The existence of the V2O5 layer on the surface of the VO2 film is also supported by X-ray photoelectron spectroscopy and Raman spectroscopy.

VO2 /TiN Plasmonic Thermochromic Smart Coatings for Room-Temperature Applications.

PubMed

Hao, Qi; Li, Wan; Xu, Huiyan; Wang, Jiawei; Yin, Yin; Wang, Huaiyu; Ma, Libo; Ma, Fei; Jiang, Xuchuan; Schmidt, Oliver G; Chu, Paul K

2018-03-01

Vanadium dioxide/titanium nitride (VO 2 /TiN) smart coatings are prepared by hybridizing thermochromic VO 2 with plasmonic TiN nanoparticles. The VO 2 /TiN coatings can control infrared (IR) radiation dynamically in accordance with the ambient temperature and illumination intensity. It blocks IR light under strong illumination at 28 °C but is IR transparent under weak irradiation conditions or at a low temperature of 20 °C. The VO 2 /TiN coatings exhibit a good integral visible transmittance of up to 51% and excellent IR switching efficiency of 48% at 2000 nm. These unique advantages make VO 2 /TiN promising as smart energy-saving windows. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Effects of Vanadium Pentoxide to Oxalic Acid Ratio and Different Atmospheres on the Formation of VO2 Nanopowders Synthesized via Sol-Gel Method

NASA Astrophysics Data System (ADS)

Vostakola, Mohsen Fallah; Yekta, Bijan Eftekhari; Mirkazemi, Seyed Mohammad

2017-11-01

Thermochromic VO2 nanopowders were synthesized via the sol-gel method through mixing oxalic acid and vanadium pentoxide in ethanol. We investigated the effect of oxalic acid to vanadium pentoxide ratio on the formation of final product and found that excessive oxalic acid reduced the final product from VO2 to V2O3. Because decreasing the oxalic acid to vanadium pentoxide ratio is a time-consuming process, oxygen was introduced by using a low-porosity alumina tube. The heat treatment was performed inside an electrical tube furnace and in a variety of atmospheres, including pure nitrogen (99.999% purity) and nitrogen containing 5 vol.%, 10 vol.%, and 15 vol.% hydrogen. According to x-ray diffraction (XRD) results, the appropriate atmosphere for synthesizing VO2 nanopowder was the one which contained 10 vol.% hydrogen. In order to decrease the transition temperature in VO2 from 63.5°C to room temperature, W6+ doping was done by adding different amounts of tungstic acid sol to vanadium sol precursor. Differential scanning calorimetry (DSC) results showed that W6+ reduced the transition temperature of VO2 approximately 23°C/wt.%. Lattice straining estimated from XRD results confirmed that VO2 was doped. XRD results at 25°C and 100°C along with DSC results indicated that VO2 was transformed from a low-temperature monoclinic phase to a high-temperature rutile one along this temperature interval.

Control of the metal-insulator transition in vanadium dioxide by modifying orbital occupancy

NASA Astrophysics Data System (ADS)

Aetukuri, Nagaphani B.; Gray, Alexander X.; Drouard, Marc; Cossale, Matteo; Gao, Li; Reid, Alexander H.; Kukreja, Roopali; Ohldag, Hendrik; Jenkins, Catherine A.; Arenholz, Elke; Roche, Kevin P.; Dürr, Hermann A.; Samant, Mahesh G.; Parkin, Stuart S. P.

2013-10-01

External control of the conductivity of correlated oxides is one of the most promising schemes for realizing energy-efficient electronic devices. Vanadium dioxide (VO2), an archetypal correlated oxide compound, undergoes a temperature-driven metal-insulator transition near room temperature with a concomitant change in crystal symmetry. Here, we show that the metal-insulator transition temperature of thin VO2(001) films can be changed continuously from ~285 to ~345K by varying the thickness of the RuO2 buffer layer (resulting in different epitaxial strains). Using strain-, polarization- and temperature-dependent X-ray absorption spectroscopy, in combination with X-ray diffraction and electronic transport measurements, we demonstrate that the transition temperature and the structural distortion across the transition depend on the orbital occupancy in the metallic state. Our findings open up the possibility of controlling the conductivity in atomically thin VO2 layers by manipulating the orbital occupancy by, for example, heterostructural engineering.

Chemical composition of an aqueous oxalato-/citrato-VO(2+) solution as determinant for vanadium oxide phase formation.

PubMed

Peys, Nick; Maurelli, Sara; Reekmans, Gunter; Adriaensens, Peter; De Gendt, Stefan; Hardy, An; Van Doorslaer, Sabine; Van Bael, Marlies K

2015-01-05

Aqueous solutions of oxalato- and citrato-VO(2+) complexes are prepared, and their ligand exchange reaction is investigated as a function of the amount of citrate present in the aqueous solution via continuous-wave electron paramagnetic resonance (CW EPR) and hyperfine sublevel correlation (HYSCORE) spectroscopy. With a low amount of citrate, monomeric cis-oxalato-VO(2+) complexes occur with a distorted square-pyramidal geometry. As the amount of citrate increases, oxalate is gradually exchanged for citrate. This leads to (i) an intermediate situation of monomeric VO(2+) complexes with a mix of oxalate/citrate ligands and (ii) a final situation of both monomeric and dimeric complexes with exclusively citrato ligands. The monomeric citrato-VO(2+) complexes dominate (abundance > 80%) and are characterized by a 6-fold chelation of the vanadium(IV) ion by 4 RCO2(-) ligands at the equatorial positions and a H2O/R-OH ligand at the axial position. The different redox stabilities of these complexes, relative to that of dissolved O2 in the aqueous solution, is analyzed via (51)V NMR. It is shown that the oxidation rate is the highest for the oxalato-VO(2+) complexes. In addition, the stability of the VO(2+) complexes can be drastically improved by evacuation of the dissolved O2 from the solution and subsequent storage in a N2 ambient atmosphere. The vanadium oxide phase formation process, starting with the chemical solution deposition of the aqueous solutions and continuing with subsequent processing in an ambient 0.1% O2 atmosphere, differs for the two complexes. The oxalato-VO(2+) complexes turn into the oxygen-deficient crystalline VO2 B at 400 °C, which then turns into crystalline V6O13 at 500 °C. In contrast, the citrato-VO(2+) complexes form an amorphous film at 400 °C that crystallizes into VO2 M1 and V6O13 at 500 °C.

Electro-thermal control of aluminum-doped zinc oxide/vanadium dioxide multilayered thin films for smart-device applications

PubMed Central

Skuza, J. R.; Scott, D. W.; Mundle, R. M.; Pradhan, A. K.

2016-01-01

We demonstrate the electro-thermal control of aluminum-doped zinc oxide (Al:ZnO) /vanadium dioxide (VO2) multilayered thin films, where the application of a small electric field enables precise control of the applied heat to the VO2 thin film to induce its semiconductor-metal transition (SMT). The transparent conducting oxide nature of the top Al:ZnO film can be tuned to facilitate the fine control of the SMT of the VO2 thin film and its associated properties. In addition, the Al:ZnO film provides a capping layer to the VO2 thin film, which inhibits oxidation to a more energetically favorable and stable V2O5 phase. It also decreases the SMT of the VO2 thin film by approximately 5–10 °C because of an additional stress induced on the VO2 thin film and/or an alteration of the oxygen vacancy concentration in the VO2 thin film. These results have significant impacts on technological applications for both passive and active devices by exploiting this near-room-temperature SMT. PMID:26884225

The preparation of a plasmonically resonant VO2 thermochromic pigment.

PubMed

Bai, Huaping; Cortie, Michael B; Maaroof, Abbas I; Dowd, Annette; Kealley, Catherine; Smith, Geoffrey B

2009-02-25

Vanadium dioxide (VO(2)) undergoes a reversible metal-insulator transition, normally at approximately 68 degrees C. While the properties of continuous semi-transparent coatings of VO(2) are well known, there is far less information available concerning the potential use of discrete VO(2) nanoparticles as a thermochromic pigment in opaque coatings. Individual VO(2) nanoparticles undergo a localized plasmon resonance with near-infrared light at about 1100 nm and this resonance can be switched on and off by simply varying the temperature of the system. Therefore, incorporation of VO(2) nanoparticles into a coating system imbues the coating with the ability to self-adaptively modulate its own absorptive efficiency in the near-infrared. Here we examine the magnitude and control of this phenomenon. Prototype coatings are described, made using VO(2) powder produced by an improved process. The materials are characterized using calorimetry, x-ray diffraction, high-resolution scanning electron microscopy, transmission electron microscopy, and by measurement of optical properties.

Near-zero IR transmission of VO2 thin films deposited on Si substrate

NASA Astrophysics Data System (ADS)

Zhang, Chunzi; Koughia, Cyril; Li, Yuanshi; Cui, Xiaoyu; Ye, Fan; Shiri, Sheida; Sanayei, Mohsen; Wen, Shi-Jie; Yang, Qiaoqin; Kasap, Safa

2018-05-01

Vanadium dioxide (VO2) thin films of different thickness have been deposited on Si substrates by using DC magnetron sputtering. The effects of substrate pre-treatment by means of seeding (spin coating and ultrasonic bathing) and biasing on the structure and optical properties were investigated. Seeding results in a smaller grain size in the oxide film, whereas biasing results in square-textured crystals. VO2 thin films of 150 nm thick show a near-zero IR transmission in switched state. Especially, the 150 nm thick VO2 thin film with seeding treatment shows an enhanced switching efficiency.

Atomic Layer Deposition of Vanadium Dioxide and a Temperature-dependent Optical Model.

PubMed

Currie, Marc; Mastro, Michael A; Wheeler, Virginia D

2018-05-23

Vanadium dioxide is a material that has a reversible metal-insulator phase change near 68 °C. To grow VO2 on a wide variety of substrates, with wafer-scale uniformity and angstrom level control of thickness, the method of atomic-layer deposition was chosen. This ALD process enables high-quality, low-temperature (≤150 °C) growth of ultrathin films (100-1000 Å) of VO2. For this demonstration, the VO2 films were grown on sapphire substrates. This low temperature growth technique produces mostly amorphous VO2 films. A subsequent anneal in an ultra-high vacuum chamber with a pressure of 7x10 -4 Pa of ultra-high purity (99.999%) oxygen produced oriented, polycrystalline VO2 films. The crystallinity, phase, and strain of the VO2 were determined by Raman spectroscopy and X-ray diffraction, while the stoichiometry and impurity levels were determined by X-ray photoelectron spectroscopy, and finally the morphology was determined by atomic force microscopy. These data demonstrate the high-quality of the films grown by this technique. A model was created to fit to the data for VO2 in its metallic and insulating phases in the near infrared spectral region. The permittivity and refractive index of the ALD VO2 agreed well with the other fabrication methods in its insulating phase, but showed a difference in its metallic state. Finally, the analysis of the films' optical properties enabled the creation of a wavelength- and temperature-dependent model of the complex optical refractive index for developing VO2 as a tunable refractive index material.

Voltage switching of a VO{sub 2} memory metasurface using ionic gel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldflam, M. D.; Liu, M. K.; Chapler, B. C.

2014-07-28

We demonstrate an electrolyte-based voltage tunable vanadium dioxide (VO{sub 2}) memory metasurface. Large spatial scale, low voltage, non-volatile switching of terahertz (THz) metasurface resonances is achieved through voltage application using an ionic gel to drive the insulator-to-metal transition in an underlying VO{sub 2} layer. Positive and negative voltage application can selectively tune the metasurface resonance into the “off” or “on” state by pushing the VO{sub 2} into a more conductive or insulating regime respectively. Compared to graphene based control devices, the relatively long saturation time of resonance modification in VO{sub 2} based devices suggests that this voltage-induced switching originates primarilymore » from electrochemical effects related to oxygen migration across the electrolyte–VO{sub 2} interface.« less

Core-shell VO2@TiO2 nanorods that combine thermochromic and photocatalytic properties for application as energy-saving smart coatings.

PubMed

Li, Yamei; Ji, Shidong; Gao, Yanfeng; Luo, Hongjie; Kanehira, Minoru

2013-01-01

Vanadium dioxide (VO2) is a Mott phase transition compound that can be applied as a thermochromic smart material for energy saving and comfort, and titanium dioxide (TiO2) is a well-known photocatalyst for self-cleaning coatings. In this paper, we report a VO2@TiO2 core-shell structure, in which the VO2 nanorod core exhibits a remarkable modulation ability for solar infrared light, and the TiO2 anatase shell exhibits significant photocatalytic degradation of organic dye. In addition, the TiO2 overcoating not only increased the luminous transmittance of VO2 based on an antireflection effect, but also modified the intrinsic colour of VO2 films from yellow to light blue. The TiO2 also enhanced the chemical stability of VO2 against oxidation. This is the first report of such a single nanoparticle structure with both thermochromic and photocatalytic properties that offer significant potential for creating a multifunctional smart coating.

Core-shell VO2@TiO2 nanorods that combine thermochromic and photocatalytic properties for application as energy-saving smart coatings

PubMed Central

Li, Yamei; Ji, Shidong; Gao, Yanfeng; Luo, Hongjie; Kanehira, Minoru

2013-01-01

Vanadium dioxide (VO2) is a Mott phase transition compound that can be applied as a thermochromic smart material for energy saving and comfort, and titanium dioxide (TiO2) is a well-known photocatalyst for self-cleaning coatings. In this paper, we report a VO2@TiO2 core-shell structure, in which the VO2 nanorod core exhibits a remarkable modulation ability for solar infrared light, and the TiO2 anatase shell exhibits significant photocatalytic degradation of organic dye. In addition, the TiO2 overcoating not only increased the luminous transmittance of VO2 based on an antireflection effect, but also modified the intrinsic colour of VO2 films from yellow to light blue. The TiO2 also enhanced the chemical stability of VO2 against oxidation. This is the first report of such a single nanoparticle structure with both thermochromic and photocatalytic properties that offer significant potential for creating a multifunctional smart coating. PMID:23546301

Gate-tunable gigantic lattice deformation in VO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okuyama, D., E-mail: okuyama@riken.jp, E-mail: nakano@imr.tohoku.ac.jp, E-mail: iwasa@ap.t.u-tokyo.ac.jp; Hatano, T.; Nakano, M., E-mail: okuyama@riken.jp, E-mail: nakano@imr.tohoku.ac.jp, E-mail: iwasa@ap.t.u-tokyo.ac.jp

2014-01-13

We examined the impact of electric field on crystal lattice of vanadium dioxide (VO{sub 2}) in a field-effect transistor geometry by in-situ synchrotron x-ray diffraction measurements. Whereas the c-axis lattice parameter of VO{sub 2} decreases through the thermally induced insulator-to-metal phase transition, the gate-induced metallization was found to result in a significant increase of the c-axis length by almost 1% from that of the thermally stabilized insulating state. We also found that this gate-induced gigantic lattice deformation occurs even at the thermally stabilized metallic state, enabling dynamic control of c-axis lattice parameter by more than 1% at room temperature.

Preparation of VO2 thin film and its direct optical bit recording characteristics.

PubMed

Fukuma, M; Zembutsu, S; Miyazawa, S

1983-01-15

Vanadium dioxide (VO2) film which has nearly the same transition point as single crystal has been obtained by reactive evaporation of vanadium on glass and subsequent annealing in N2 gas. Relations between optical properties of V02 film and its preparation conditions are presented. We made optical direct bit recording on V02 film using a laser diode as the light source. The threshold recording energy and bit density are 2 mJ/cm 2 and 350 bits/mm, respectively. We also made tungsten doping to lower the V02 film transition temperature.

Elevated transition temperature in Ge doped VO2 thin films

NASA Astrophysics Data System (ADS)

Krammer, Anna; Magrez, Arnaud; Vitale, Wolfgang A.; Mocny, Piotr; Jeanneret, Patrick; Guibert, Edouard; Whitlow, Harry J.; Ionescu, Adrian M.; Schüler, Andreas

2017-07-01

Thermochromic GexV1-xO2+y thin films have been deposited on Si (100) substrates by means of reactive magnetron sputtering. The films were then characterized by Rutherford backscattering spectrometry (RBS), four-point probe electrical resistivity measurements, X-ray diffraction, and atomic force microscopy. From the temperature dependent resistivity measurements, the effect of Ge doping on the semiconductor-to-metal phase transition in vanadium oxide thin films was investigated. The transition temperature was shown to increase significantly upon Ge doping (˜95 °C), while the hysteresis width and resistivity contrast gradually decreased. The precise Ge concentration and the film thickness have been determined by RBS. The crystallinity of phase-pure VO2 monoclinic films was confirmed by XRD. These findings make the use of vanadium dioxide thin films in solar and electronic device applications—where higher critical temperatures than 68 °C of pristine VO2 are needed—a viable and promising solution.

Voltage-induced switching dynamics based on an AZO/VO2/AZO sandwiched structure

NASA Astrophysics Data System (ADS)

Xiao, Han; Li, Yi; Fang, Baoying; Wang, Xiaohua; Liu, Zhimin; Zhang, Jiao; Li, Zhengpeng; Huang, Yaqin; Pei, Jiangheng

2017-11-01

A vanadium dioxide (VO2) thin film was prepared on an Al-doped ZnO (AZO) conductive glass substrate by DC magnetron sputtering and a post-annealing process. The AZO/VO2/AZO sandwiched structure was fabricated on the VO2/AZO composite film using photolithography and a chemical etching process. The composition, microstructure and optical properties of the VO2/AZO composite film were tested. The results showed that the VO2/AZO composite film was poly-crystalline and the AZO layer did not change the preferred growth orientation of VO2. When the voltage was applied on both of the transparent conductive layers of the AZO/VO2/AZO sandwiched structure, an abrupt change in the current was observed at different temperatures. The temperature dependence of I-V characteristic curves for the AZO/VO2/AZO sandwiched structure was analyzed. The phase transition voltage value is 7.5 V at 20 °C and decreases with increasing temperature.

Hydrothermal route to VO2 (B) nanorods: controlled synthesis and characterization

NASA Astrophysics Data System (ADS)

Song, Shaokun; Huang, Qiwei; Zhu, Wanting

2017-10-01

One-dimensional vanadium dioxides have attracted intensive attention owing to their distinctive structure and novel applications in catalysis, high energy lithium-ion batteries, chemical sensors/actuators and electrochemical devices etc. In this paper, large-scale VO2 (B) nanorods have been successfully synthesized via a versatile and environment friendly hydrothermal strategy using V2O5 as vanadium source and carbohydrates/alcohols as reductant. The obtained samples are characterized by XRD, FT-IR, TEM, and XPS techniques to investigate the effects of chemical parameters such as reductants, temperature, and time of synthesis on the structure and morphology of products. Results show that pure B phase VO2 with homogeneous nanorod-like morphology can be prepared easily at 180 °C for 3 days with glycerol as reluctant. Typically, the nanorod-like products are 0.5-1 μm long and 50 nm width. Furthermore, it is also confirmed that the products are consisted of VO2, corresponding to the B phase. More importantly, this novel approach is efficient, free of any harmful solvents and surfactants. Therefore, this efficient, green, and cost-saving route will have great potential in the large-scale fabrication of 1D VO2 (B) nanorods from the economic and environmental point of view.

A metal-insulator transition study of VO 2 thin films grown on sapphire substrates

DOE PAGES

Yu, Shifeng; Wang, Shuyu; Lu, Ming; ...

2017-12-15

In this paper, vanadium thin films were deposited on sapphire substrates by DC magnetron sputtering and then oxidized in a tube furnace filled with oxygen under different temperatures and oxygen flow rates. The significant influence of the oxygen flow rate and oxidation temperature on the electrical and structural properties of the vanadium oxide thin films were investigated systematically. It shows the pure vanadium dioxide (VO 2) state can only be obtained in a very narrow temperature and oxygen flow rate range. The resistivity change during the metal-insulator transition varies from 0.2 to 4 orders of magnitude depending on the oxidationmore » condition. Large thermal hysteresis during the metal-insulator phase transition was observed during the transition compared to the results in literature. Proper oxidation conditions can significantly reduce the thermal hysteresis. Finally, the fabricated VO 2 thin films showed the potential to be applied in the development of electrical sensors and other smart devices.« less

Substrate-mediated strain effect on the role of thermal heating and electric field on metal-insulator transition in vanadium dioxide nanobeams.

PubMed

Kim, Min-Woo; Jung, Wan-Gil; Hyun-Cho; Bae, Tae-Sung; Chang, Sung-Jin; Jang, Ja-Soon; Hong, Woong-Ki; Kim, Bong-Joong

2015-06-04

Single-crystalline vanadium dioxide (VO2) nanostructures have recently attracted great attention because of their single domain metal-insulator transition (MIT) nature that differs from a bulk sample. The VO2 nanostructures can also provide new opportunities to explore, understand, and ultimately engineer MIT properties for applications of novel functional devices. Importantly, the MIT properties of the VO2 nanostructures are significantly affected by stoichiometry, doping, size effect, defects, and in particular, strain. Here, we report the effect of substrate-mediated strain on the correlative role of thermal heating and electric field on the MIT in the VO2 nanobeams by altering the strength of the substrate attachment. Our study may provide helpful information on controlling the properties of VO2 nanobeam for the device applications by changing temperature and voltage with a properly engineered strain.

Substrate-mediated strain effect on the role of thermal heating and electric field on metal-insulator transition in vanadium dioxide nanobeams

PubMed Central

Kim, Min-Woo; Jung, Wan-Gil; Hyun-Cho; Bae, Tae-Sung; Chang, Sung-Jin; Jang, Ja-Soon; Hong, Woong-Ki; Kim, Bong-Joong

2015-01-01

Single-crystalline vanadium dioxide (VO2) nanostructures have recently attracted great attention because of their single domain metal-insulator transition (MIT) nature that differs from a bulk sample. The VO2 nanostructures can also provide new opportunities to explore, understand, and ultimately engineer MIT properties for applications of novel functional devices. Importantly, the MIT properties of the VO2 nanostructures are significantly affected by stoichiometry, doping, size effect, defects, and in particular, strain. Here, we report the effect of substrate-mediated strain on the correlative role of thermal heating and electric field on the MIT in the VO2 nanobeams by altering the strength of the substrate attachment. Our study may provide helpful information on controlling the properties of VO2 nanobeam for the device applications by changing temperature and voltage with a properly engineered strain. PMID:26040637

VO 2 thin films synthesis for collaborators and various applications.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Raegan Lynn; Clem, Paul G.

2016-11-01

Vanadium dioxide (VO 2) is an attractive material for a variety of applications due to its metal-to-insulator transition (MIT) observed at modest temperatures. This transition takes VO 2 from its low temperature insulating monoclinic phase to a high temperature (above 68°C) metallic rutile phase. This transition gives rise to a change in resistivity up to 5 orders of magnitude and a change in complex refractive index (especially at IR wavelengths), which is of interest for radar circuit protection and tunable control of infrared signature. Recently, collaborations have been initiated between CINT scientists and external university programs. The Enhanced Surveillance fundsmore » help fund this work which enabled synthesis of VO 2 films for several collaborations with internal and external researchers.« less

Preparation and enhanced infrared response properties of ordered W-doped VO2 nanowire array

NASA Astrophysics Data System (ADS)

Xie, Bing He; Fu, Wen Biao; Fei, Guang Tao; Xu, Shao Hui; Gao, Xu Dong; Zhang, Li De

2018-04-01

In this article, pure and tungsten-doped (W-doped) highly ordered two-dimensional (2D) vanadium dioxide (VO2) nanowire arrays were successfully prepared by a hydrothermal treatment, followed by a self-assembly progress and the in-situ high temperature treatment. The infrared photodetector devices based on monoclinic VO2 (VO2(M)) and W-doped VO2(M) nanowires were comparatively studied . It was found that the device based on W-doped VO2(M) nanowires exhibits a rapid infrared response and an enhanced photoelectric responsivity of 21.4 mA/W under the incident infrared light intensity of 280 mW/cm2, which is nearly two orders of magnitude superior to pure VO2(M) nanowire array. Our experimental results provided a direct and convenient path for design of future high-performance photodetector devices.

Porous carbon derived from disposable shaddock peel as an excellent catalyst toward VO2+/VO2+ couple for vanadium redox battery

NASA Astrophysics Data System (ADS)

Liu, J.; Wang, Z. A.; Wu, X. W.; Yuan, X. H.; Hu, J. P.; Zhou, Q. M.; Liu, Z. H.; Wu, Y. P.

2015-12-01

Functional porous carbon (PC) derived from bio-friendly shaddock peel has been firstly explored as catalyst for vanadium redox flow battery (VRB). The prepared PC is micro-mesoporous with high BET surface area of 882.7 m2 g-1, has some surface oxygen-containing functional groups, and is doped with N and P heteroatoms. These three factors greatly favor the electrochemical reactions of VO2+/VO2+ on the PC modified glass carbon (PC-GC). Compared with the naked GC and graphite modified GC, the PC-GC presents a lower peak separation (66 mV), higher anodic current density (17.1 mA cm-2) and cathodic current density (15.0 mA cm-2). The VRB using PC modified graphite felt (GF) as positive electrode demonstrates an enhanced voltage efficiency of 82.7% at the current density of 60 mA cm-2, and a better rate performance than that from the virginal GF.

Optical diffraction in ordered VO2 nanoparticle arrays

NASA Astrophysics Data System (ADS)

Lopez, Rene; Feldman, Leonard; Haglund, Richard

2006-03-01

The potential of oxide electronic materials as multifunctional building blocks is one of the driving concepts of the field. In this presentation, we show how nanostructured particle arrays with long-range order can be used to modulate an optical response through exploiting the metal-insulator transition of vanadium dioxide. Arrays of VO2 nanoparticles with long-range order were fabricated by pulsed laser deposition in an arbitrary pattern defined by focused ion-beam lithography. The interaction of light with the nanoparticles is controlled by the nanoparticle size, spacing and geometrical arrangement and by switching between the metallic and semiconducting phases of VO2. In addition to the near-infrared surface plasmon response observed in previous VO2 studies, the VO2 nanoparticle arrays exhibit size-dependent optical resonances in the visible region that likewise show an enhanced optical contrast between the semiconducting and metallic phases. The collective optical response as a function of temperature gives rise to an enhanced scattering state during the evolving phase transition, while the incoherent coupling between the nanoparticles produces an order-disorder-order transition.

Persistent electrochemical performance in epitaxial VO 2(B)

DOE PAGES

Lee, Shinbuhm; Sun, Xiao -Guang; Lubimtsev, Andrew A.; ...

2017-03-07

Discovering high-performance energy storage materials is indispensable for renewable energy, electric vehicle performance, and mobile computing. Owing to the open atomic framework and good room temperature conductivity, bronze-phase vanadium dioxide [VO 2(B)] has been regarded as a highly promising electrode material for Li ion batteries. However, previous attempts were unsuccessful to show the desired cycling performance and capacity without chemical modification. Here, we show with epitaxial VO 2(B) films that one can accomplish the theoretical limit for capacity with persistent charging–discharging cyclability owing to the high structural stability and unique open pathways for Li ion conduction. Atomic-scale characterization by scanningmore » transmission electron microscopy and density functional theory calculations also reveal that the unique open pathways in VO 2(B) provide the most stable sites for Li adsorption and diffusion. Furthermore, this work ultimately demonstrates that VO 2(B) is a highly promising energy storage material and has no intrinsic hindrance in achieving superior cyclability with a very high power and capacity in a Li-ion conductor.« less

Defect-mediated room temperature ferromagnetism in vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Yang, Tsung-Han; Nori, Sudhakar; Zhou, Honghui; Narayan, Jagdish

2009-09-01

High quality epitaxial undoped vanadium oxide (VO2) thin films on c-plane sapphire (0001) substrate have been grown using pulsed laser deposition technique. The as-grown films exhibited excellent structural and transport properties without requiring further annealing treatments for these oxygen-deficient oxide films. The epitaxial growth has been achieved via domain matching epitaxy, where matching of integral multiples of planes occurs across the film-substrate interface. The magnetic properties of vanadium oxide (VO2) films investigated at different temperatures in the range of 10-360 K showed significant magnetic hysteresis as well as saturation of the magnetic moment. The origin of ferromagnetic properties with an estimated Curie temperature above 500 K is discussed in the absence of magnetic impurities in VO2 thin films as determined by x-ray photoelectron spectroscopy, x-ray diffraction, and transmission electron microscopy.

Preparation and investigation of sputtered vanadium dioxide films with large phase-transition hysteresis loops

NASA Astrophysics Data System (ADS)

Zhang, Huafu; Wu, Zhiming; He, Qiong; Jiang, Yadong

2013-07-01

Vanadium dioxide (VO2) films with large phase-transition hysteresis loops were fabricated on glass substrates by reactive direct current (DC) magnetron sputtering in Ar/O2 atmosphere and subsequent in situ annealing process in pure oxygen. The crystal structure, chemical composition, morphology and metal-insulator transition (MIT) properties of the deposited films were investigated. The results reveal that the films show a polycrystalline nature with a (0 1 1) preferred orientation and consist of small spheroidal nanoparticles. All the deposited VO2 films show large hysteresis loops due to the small density of nucleating defects and the large interfacial energies, which are determined by the characteristics of the particles in the films, namely the small transversal grain size and the spheroidal shape. The film comprising the smallest spheroidal nanoparticles not only shows a large hysteresis width of 36.3 °C but also shows a low transition temperature of 32.2 °C upon cooling. This experiment facilitates the civilian applications of the VO2 films on glass substrates in optical storage-type devices.

Ultrafast Dynamics in Vanadium Dioxide: Separating Spatially Segregated Mixed Phase Dynamics in the Time-domain

NASA Astrophysics Data System (ADS)

Hilton, David

2011-10-01

In correlated electronic systems, observed electronic and structural behavior results from the complex interplay between multiple, sometimes competing degrees-of- freedom. One such material used to study insulator-to-metal transitions is vanadium dioxide, which undergoes a phase transition from a monoclinic-insulating phase to a rutile-metallic phase when the sample is heated to 340 K. The major open question with this material is the relative influence of this structural phase transition (Peirels transition) and the effects of electronic correlations (Mott transition) on the observed insulator-to-metal transition. Answers to these major questions are complicated by vanadium dioxide's sensitivity to perturbations in the chemical structure in VO2. For example, related VxOy oxides with nearly a 2:1 ratio do not demonstrate the insulator-to- metal transition, while recent work has demonstrated that W:VO2 has demonstrated a tunable transition temperature controllable with tungsten doping. All of these preexisting results suggest that the observed electronic properties are exquisitely sensitive to the sample disorder. Using ultrafast spectroscopic techniques, it is now possible to impulsively excite this transition and investigate the photoinduced counterpart to this thermal phase transition in a strongly nonequilibrium regime. I will discuss our recent results studying the terahertz-frequency conductivity dynamics of this photoinduced phase transition in the poorly understood near threshold temperature range. We find a dramatic softening of the transition near the critical temperature, which results primarily from the mixed phase coexistence near the transition temperature. To directly study this mixed phase behavior, we directly study the nucleation and growth rates of the metallic phase in the parent insulator using non-degenerate optical pump-probe spectroscopy. These experiments measure, in the time- domain, the coexistent phase separation in VO2 (spatially

Investigation of electron beam lithography effects on metal-insulator transition behavior of vanadium dioxide

NASA Astrophysics Data System (ADS)

Yuce, H.; Alaboz, H.; Demirhan, Y.; Ozdemir, M.; Ozyuzer, L.; Aygun, G.

2017-11-01

Vanadium dioxide (VO2) shows metal-insulator phase transition at nearly 68 °C. This metal-insulator transition (MIT) in VO2 leads to a significant change in near-infrared transmittance and an abrupt change in the resistivity of VO2. Due to these characteristics, VO2 plays an important role on optic and electronic devices, such as thermochromic windows, meta-materials with tunable frequency, uncooled bolometers and switching devices. In this work, VO2 thin films were fabricated by reactive direct current magnetron sputtering in O2/Ar atmosphere on sapphire substrates without any further post annealing processes. The effect of sputtering parameters on optical characteristics and structural properties of grown thin films was investigated by SEM, XRD, Raman and UV/VIS spectrophotometer measurements. Patterning process of VO2 thin films was realized by e-beam lithography technique to monitor the temperature dependent electrical characterization. Electrical properties of VO2 samples were characterized using microprobe station in a vacuum system. MIT with hysteresis behavior was observed for the unpatterned square samples at around 68 °C. By four orders of magnitude of resistivity change was measured for the deposited VO2 thin films at transition temperature. After e-beam lithography process, substantial results in patterned VO2 thin films were observed. In this stage, for patterned VO2 thin films as stripes, the change in resistivity of VO2 was reduced by a factor of 10. As a consequence of electrical resistivity measurements, MIT temperature was shifted from 68 °C to 50 °C. The influence of e-beam process on the properties of VO2 thin films and the mechanism of the effects are discussed. The presented results contribute to the achievement of VO2 based thermochromic windows and bolometer applications.

Epitaxial VO2 thin-film-based radio-frequency switches with electrical activation

NASA Astrophysics Data System (ADS)

Lee, Jaeseong; Lee, Daesu; Cho, Sang June; Seo, Jung-Hun; Liu, Dong; Eom, Chang-Beom; Ma, Zhenqiang

2017-09-01

Vanadium dioxide (VO2) is a correlated material exhibiting a sharp insulator-to-metal phase transition (IMT) caused by temperature change and/or bias voltage. We report on the demonstration of electrically triggered radio-frequency (RF) switches based on epitaxial VO2 thin films. The highly epitaxial VO2 and SnO2 template layer was grown on a (001) TiO2 substrate by pulsed laser deposition (PLD). A resistance change of the VO2 thin films of four orders of magnitude was achieved with a relatively low threshold voltage, as low as 13 V, for an IMT phase transition. VO2 RF switches also showed high-frequency responses of insertion losses of -3 dB at the on-state and return losses of -4.3 dB at the off-state over 27 GHz. Furthermore, an intrinsic cutoff frequency of 17.4 THz was estimated for the RF switches. The study on electrical IMT dynamics revealed a phase transition time of 840 ns.

Microwave-assisted synthesis and electrochemical evaluation of VO 2 (B) nanostructures

DOE PAGES

Ashton, Thomas E.; Borras, David Hevia; Iadecola, Antonella; ...

2015-12-01

Understanding how intercalation materials change during electrochemical operation is paramount to optimising their behaviour and function and in situ characterisation methods allow us to observe these changes without sample destruction. Here, we first report the improved intercalation properties of bronze phase vanadium dioxide VO2 (B) prepared by a microwave assisted route which exhibits a larger electrochemical capacity (232 mAh g -1) compared to VO 2 (B) prepared by a solvothermal route (197 mAh g -1). These electrochemical differences have also been followed using in situ X-ray absorption spectroscopy allowing us to follow oxidation state changes as they occur during batterymore » operation.« less

High pressure spectroscopic studies of phase transition in VO2

NASA Astrophysics Data System (ADS)

Basu, Raktima; Mishra, K. K.; Ravindran, T. R.; Dhara, Sandip

2018-04-01

Vanadium dioxide (VO2) exhibits a reversible first-order metal to insulator transition (MIT) at a technologically important temperature of 340K. A structural phase transition (SPT) from monoclinic M1 to rutile tetragonal R is also reported via another two intermediate phases of monoclinic M2 and triclinic T. Metastable monoclinic M2 phase of VO2 was synthesized by Mg doping in the vapour transport process. Raman spectroscopic measurements were carried out at high pressure on V1-xMgxO2 microrods. Two reversible structural phase transitions from monoclinic M2 to triclinic T at 1.6 GPa and T to monoclinic M1 at 3.2 GPa are observed and are explained by structural relaxation of the strained phases.

Improving the electrocatalytic performance of carbon nanotubes for VO2+/VO2+ redox reaction by KOH activation

NASA Astrophysics Data System (ADS)

Dai, Lei; Jiang, Yingqiao; Meng, Wei; Zhou, Huizhu; Wang, Ling; He, Zhangxing

2017-04-01

In this paper, carbon nanotubes (CNTs) was activated by KOH treatment at high temperature and investigated as catalyst for VO2+/VO2+ redox reaction for vanadium redox flow battery (VRFB). X-ray photoelectron spectroscopy results suggest that the oxygen-containing groups can be introduced on CNTs by KOH activation. The mass transfer of vanadium ions can be accelerated by chemical etching by KOH activation and improved wettability due to the introduction of hydrophilic groups. The electrochemical properties of VO2+/VO2+ redox reaction can be enhanced by introduced oxygen-containing groups as active sites. The sample treated at 900 °C with KOH/CNTs mass ratio of 3:1 (CNTs-3) exhibits the highest electrocatalytic activity for VO2+/VO2+ redox reaction. The cell using CNTs-3 as positive catalyst demonstrates the smallest electrochemical polarization, the highest capacity and efficiency among the samples. Using KOH-activated CNTs-3 can increase the average energy efficiency of the cell by 4.4%. This work suggests that KOH-activated CNTs is a low-cost, efficient and promising catalyst for VO2+/VO2+ redox reaction for VRFB system.

Hydrothermal growth of VO2 nanoplate thermochromic films on glass with high visible transmittance

PubMed Central

Zhang, Jiasong; Li, Jingbo; Chen, Pengwan; Rehman, Fida; Jiang, Yijie; Cao, Maosheng; Zhao, Yongjie; Jin, Haibo

2016-01-01

The preparation of thermochromic vanadium dioxide (VO2) films in an economical way is of interest to realizing the application of smart windows. Here, we reported a successful preparation of self-assembly VO2 nanoplate films on TiO2-buffered glass by a facile hydrothermal process. The VO2 films composed of triangle-shaped plates standing on substrates exhibit a self-generated porous structure, which favors the transmission of solar light. The porosity of films is easily controlled by changing the concentration of precursor solutions. Excellent thermochromic properties are observed with visible light transmittance as high as 70.3% and solar modulating efficiency up to 9.3% in a VO2 film with porosity of ~35.9%. This work demonstrates a promising technique to promote the commercial utilization of VO2 in smart windows. PMID:27296772

Control of electromagnetically induced transparency via a hybrid semiconductor quantum dot-vanadium dioxide nanoparticle system

NASA Astrophysics Data System (ADS)

Zamani, Naser; Hatef, Ali; Nadgaran, Hamid; Keshavarz, Alireza

2017-07-01

We numerically investigate the electromagnetically induced transparency (EIT) of a hybrid system consisting of a three-level quantum dot (QD) in the vicinity of vanadium dioxide nanoparticle (VO2NP). VO2NP has semiconductor and metallic phases where the transition between the two phases occurs around a critical temperature. When the QD-VO2NP hybrid system interacts with continuous wave laser fields in an infrared regime, it supports a coherent coupling of exciton-polariton and exciton-plasmon polariton in semiconductor and metal phases of VO2NP, respectively. In our calculations a filling fraction factor controls the VO2NP phase transition. A probe and control laser field configuration is studied for the hybrid system to measure the absorption of QD through the filling fraction factor manipulations. We show that for the VO2NP semiconductor phase and proper geometrical configuration, the absorption spectrum profile of the QD represents an EIT with two peaks and a clear minimum. These two peaks merge to one through the VO2NP phase transition to metal. We also show that the absorption spectrum profile is modified by different orientations of the laser fields with the axis of the QD-VO2NP hybrid system. The innovation in comparison to other research in the field is that robust variation in the absorption profile through EIT is due to the phase transition in VO2NP without any structural change in the QD-VO2NP hybrid system. Our results can be employed to design nanothermal sensors, optical nanoswitches, and energy transfer devices.

Equivalent circuit for VO{sub 2} phase change material film in reconfigurable frequency selective surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sanphuang, Varittha; Ghalichechian, Nima; Nahar, Niru K.

We developed equivalent circuits of phase change materials based on vanadium dioxide (VO{sub 2}) thin films. These circuits are used to model VO{sub 2} thin films for reconfigurable frequency selective surfaces (FSSs). This is important as it provides a way for designing complex structures. A reconfigurable FSS filter using VO{sub 2} ON/OFF switches is designed demonstrating −60 dB isolation between the states. This filter is used to provide the transmission and reflection responses of the FSS in the frequency range of 0.1–0.6 THz. The comparison between equivalent circuit and full-wave simulation shows excellent agreement.

Plasmonic enhancement of the vanadium dioxide phase transition induced by low-power laser irradiation

NASA Astrophysics Data System (ADS)

Ferrara, Davon W.; MacQuarrie, Evan R.; Diez-Blanco, Victor; Nag, Joyeeta; Kaye, Anthony B.; Haglund, Richard F.

2012-08-01

Nanocomposites consisting of gold nanoparticle (NP) arrays and vanadium dioxide (VO2) thin films are noteworthy for the tunability of both their thermal and optical properties. The localized surface plasmon resonance (LSPR) of the Au can be tuned when its dielectric environment is modulated by the semiconducting-to-metal phase transition (SMT) of the VO2; the LSPR itself can be altered by changing the shape of the NPs and the pitch of the NP array. In principle, then it should be possible to choose a combination of VO2 film and Au LSPR properties that maximizes the overall optical response of the nanocomposite. To demonstrate this effect, transient transmission measurements were conducted on lithographically fabricated arrays of Au NPs of diameter 140 nm, array spacing 350 nm, and covered with a 60 nm thick films of VO2 via pulsed laser deposition. Both Au::VO2 nanocomposites and bare VO2 film were irradiated with a shuttered 785 nm pump laser, and their optical response was probed at 1550 nm by a fixed-frequency diode laser. The Au::VO2 nanocomposite exhibited an increased effective absorption coefficient 1.5 times that of the plain film and required 37 % less laser power to induce the SMT. The time-dependent temperature rise in the film as a function of laser intensity was calculated from these measurements and compared with both analytic and finite-element models. Our results suggest that Au::VO2 nanocomposites may be useful in applications such as thermal-management coatings for energy efficient "smart" windows.

Oxidizing annealing effects on VO2 films with different microstructures

NASA Astrophysics Data System (ADS)

Dou, Yan-Kun; Li, Jing-Bo; Cao, Mao-Sheng; Su, De-Zhi; Rehman, Fida; Zhang, Jia-Song; Jin, Hai-Bo

2015-08-01

Vanadium dioxide (VO2) films have been prepared by direct-current magnetron sputter deposition on m-, a-, and r-plane sapphire substrates. The obtained VO2 films display different microstructures depending on the orientation of sapphire substrates, i.e. mixed microstructure of striped grains and equiaxed grains on m-sapphire, big equiaxed grains on a-sapphire and fine-grained microstructure on r-sapphire. The VO2 films were treated by the processes of oxidation in air. The electric resistance and infrared transmittance of the oxidized films were characterized to examine performance characteristics of VO2 films with different microstructures in oxidation environment. The oxidized VO2 films on m-sapphire exhibit better electrical performance than the other two films. After air oxidization for 600 s at 450 °C, the VO2 films on m-sapphire show a resistance change of 4 orders of magnitude over the semiconductor-to-metal transition. The oxidized VO2 films on a-sapphire have the highest optical modulation efficiency in infrared region compared to other samples. The different performance characteristics of VO2 films are understood in terms of microstructures, i.e. grain size, grain shape, and oxygen vacancies. The findings reveal the correlation of microstructures and performances of VO2 films, and provide useful knowledge for the design of VO2 materials to different applications.

New Insights into the Diverse Electronic Phases of a Novel Vanadium Dioxide Polymorph: A Terahertz Spectroscopy Study

PubMed Central

Lourembam, James; Srivastava, Amar; La-o-vorakiat, Chan; Rotella, H.; Venkatesan, T.; Chia, Elbert E. M.

2015-01-01

A remarkable feature of vanadium dioxide is that it can be synthesized in a number of polymorphs. The conductivity mechanism in the metastable layered polymorph VO2(B) thin films has been investigated by terahertz time-domain spectroscopy (THz-TDS). In VO2(B), a critical temperature of 240 K marks the appearance of a non-zero Drude term in the observed complex conductivity, indicating the evolution from a pure insulating state towards a metallic state. In contrast, the THz conductivity of the well-known VO2(M1) is well fitted only by a modification of the Drude model to include backscattering. We also identified two different THz conductivity regimes separated by temperature in these two polymorphs. The electronic phase diagram is constructed, revealing that the width and onset of the metal-insulator transition in the B phase develop differently from the M1 phase. PMID:25777320

Non-catalytic hydrogenation of VO2 in acid solution.

PubMed

Chen, Yuliang; Wang, Zhaowu; Chen, Shi; Ren, Hui; Wang, Liangxin; Zhang, Guobin; Lu, Yalin; Jiang, Jun; Zou, Chongwen; Luo, Yi

2018-02-26

Hydrogenation is an effective way to tune the property of metal oxides. It can conventionally be performed by doping hydrogen into solid materials with noble-metal catalysis, high-temperature/pressure annealing treatment, or high-energy proton implantation in vacuum condition. Acid solution naturally provides a rich proton source, but it should cause corrosion rather than hydrogenation to metal oxides. Here we report a facile approach to hydrogenate monoclinic vanadium dioxide (VO 2 ) in acid solution at ambient condition by placing a small piece of low workfunction metal (Al, Cu, Ag, Zn, or Fe) on VO 2 surface. It is found that the attachment of a tiny metal particle (~1.0 mm) can lead to the complete hydrogenation of an entire wafer-size VO 2 (>2 inch). Moreover, with the right choice of the metal a two-step insulator-metal-insulator phase modulation can even be achieved. An electron-proton co-doping mechanism has been proposed and verified by the first-principles calculations.

Electronic structure of HxVO2 probed with in-situ spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Kim, So Yeun; Sandilands, Luke J.; Kang, Taedong; Son, Jaeseok; Sohn, C. H.; Yoon, Hyojin; Son, Junwoo; Moon, S. J.; Noh, T. W.

Vanadium dioxide (VO2) undergoes a metal-to-insulator transition (MIT) near 340K. Despite extensive studies on this material, the role of electron-electron correlation and electron-lattice interactions in driving this MIT is still under debate. Recently, it was demonstrated that hydrogen can be reversibly absorbed into VO2 thin film without destroying the lattice framework. This H-doping allows systematic control of the electron density and lattice structure which in turn leads to a insulator (VO2) - metal (HxVO2) - insulator (HVO2) phase modulation. To better understand the phase modulation of HxVO2, we used in-situ spectroscopic ellipsometry to monitor the electronic structure during the hydrogenization process, i.e. we measured the optical conductivity of HxVO2 while varying x. Starting in the high temperature rutile metallic phase of VO2, we observed a large change in the electronic structure upon annealing in H gas at 370K: the low energy conductivity is continuously suppressed, consistent with reported DC resistivity data, while the conductivity peaks at high energy show strong changes in energy and spectral weight. The implications of our results for the MIT in HxVO2 will be discussed.

Tailoring of the thermomechanical performance of VO2 nanowire bimorph actuators by ion implantation

NASA Astrophysics Data System (ADS)

Karl, H.; Peyinghaus, S. C.

2015-12-01

Vanadium dioxide VO2 nanowire bimorph actuators work on the basis of the large abrupt length change at the metal-insulator phase transition (MIT). A key parameter for the bimorph performance and efficiency is the bending curvature and the width of the temperature hysteresis of the MIT which is inherently large for single domain VO2 metal side coated nanowires. In this work we present single-clamped Ir side coated VO2 bimorphs which show unprecedented high bending curvatures of up to 105 m-1 and new type of side ion-implanted VO2 nanowire bimorph actuators with a nearly completely suppressed temperature hysteresis. It is assumed that ion-beam induced radiation defects in the VO2 crystal structure act as nucleation sites for the MIT. Moreover it will be shown that mechanical strain intentionally built-in during VO2 nanowire bimorph fabrication allows to direct phase transformation via a strain stabilized metastable phase and thus allows to control bending response on temperature change.

Investigation on onset voltage and conduction channel temperature in voltage-induced metal-insulator transition of vanadium dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoon, Joonseok; Kim, Howon; Ju, Honglyoul, E-mail: tesl@yonsei.ac.kr

2016-03-28

The characteristics of onset voltages and conduction channel temperatures in the metal-insulator transition (MIT) of vanadium dioxide (VO{sub 2}) devices are investigated as a function of dimensions and ambient temperature. The MIT onset voltage varies from 18 V to 199 V as the device length increases from 5 to 80 μm at a fixed width of 100 μm. The estimated temperature at local conduction channel increases from 110 to 370 °C, which is higher than the MIT temperature (67 °C) of VO{sub 2}. A simple Joule-heating model is employed to explain voltage-induced MIT as well as to estimate temperatures of conduction channel appearing after MIT inmore » various-sized devices. Our findings on VO{sub 2} can be applied to micro- to nano-size tunable heating devices, e.g., microscale scanning thermal cantilevers and gas sensors.« less

Electrical switching and oscillations in vanadium dioxide

NASA Astrophysics Data System (ADS)

Pergament, Alexander; Velichko, Andrey; Belyaev, Maksim; Putrolaynen, Vadim

2018-05-01

We have studied electrical switching with S-shaped I-V characteristics in two-terminal MOM devices based on vanadium dioxide thin films. The switching effect is associated with the metal-insulator phase transition. Relaxation oscillations are observed in circuits with VO2-based switches. Dependences of the oscillator critical frequency Fmax, threshold power and voltage, as well as the time of current rise, on the switching structure size are obtained by numerical simulation. The empirical dependence of the threshold voltage on the switching region dimensions and film thickness is found. It is shown that, for the VO2 channel sizes of 10 × 10 nm, Fmax can reach the value of 300 MHz at a film thickness of 20 nm. Next, it is shown that oscillatory neural networks can be implemented on the basis of coupled VO2 oscillators. For the weak capacitive coupling, we revealed the dependence of the phase difference upon synchronization on the coupling capacitance value. When the switches are scaled down, the limiting time of synchronization is reduced to Ts 13 μs, and the number of oscillation periods for the entering to the synchronization mode remains constant, Ns 17. In the case of weak thermal coupling in the synchronization mode, we observe in-phase behavior of oscillators, and there is a certain range of parameters of the supply current, in which the synchronization effect becomes possible. With a decrease in dimensions, a decrease in the thermal coupling action radius is observed, which can vary in the range from 0.5 to 50 μm for structures with characteristic dimensions of 0.1-5 μm, respectively. Thermal coupling may have a promising effect for realization of a 3D integrated oscillatory neural network.

Facile Phase Control of Multivalent Vanadium Oxide Thin Films (V2O5 and VO2) by Atomic Layer Deposition and Postdeposition Annealing.

PubMed

Song, Gwang Yeom; Oh, Chadol; Sinha, Soumyadeep; Son, Junwoo; Heo, Jaeyeong

2017-07-19

Atomic layer deposition was adopted to deposit VO x thin films using vanadyl tri-isopropoxide {VO[O(C 3 H 7 )] 3 , VTIP} and water (H 2 O) at 135 °C. The self-limiting and purge-time-dependent growth behaviors were studied by ex situ ellipsometry to determine the saturated growth conditions for atomic-layer-deposited VO x . The as-deposited films were found to be amorphous. The structural, chemical, and optical properties of the crystalline thin films with controlled phase formation were investigated after postdeposition annealing at various atmospheres and temperatures. Reducing and oxidizing atmospheres enabled the formation of pure VO 2 and V 2 O 5 phases, respectively. The possible band structures of the crystalline VO 2 and V 2 O 5 thin films were established. Furthermore, an electrochemical response and a voltage-induced insulator-to-metal transition in the vertical metal-vanadium oxide-metal device structure were observed for V 2 O 5 and VO 2 films, respectively.

Growth temperature-dependent metal–insulator transition of vanadium dioxide epitaxial films on perovskite strontium titanate (111) single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Liangxin; Zhao, Jiangtao; Hong, Bin

2016-04-14

Vanadium dioxide (VO{sub 2}) epitaxial films were grown on perovskite single-crystal strontium titanate (SrTiO{sub 3}) substrates by reactive radio-frequency magnetron sputtering. The growth temperature-dependent metal–insulator transition (MIT) behavior of the VO{sub 2} epitaxial films was then investigated. We found that the order of magnitude of resistance change across the MIT increased from 10{sup 2} to 10{sup 4} with increasing growth temperature. In contrast, the temperature of the MIT does not strongly depend on the growth temperature and is fairly stable at about 345 K. On one hand, the increasing magnitude of the MIT is attributed to the better crystallinity and thusmore » larger grain size in the (010)-VO{sub 2}/(111)-SrTiO{sub 3} epitaxial films at elevated temperature. On the other hand, the strain states do not change in the VO{sub 2} films deposited at various temperatures, resulting in stable V-V chains and V-O bonds in the VO{sub 2} epitaxial films. The accompanied orbital occupancy near the Fermi level is also constant and thus the MIT temperatures of VO{sub 2} films deposited at various temperatures are nearly the same. This work demonstrates that high-quality VO{sub 2} can be grown on perovskite substrates, showing potential for integration into oxide heterostructures and superlattices.« less

Thermal aging effect of vanadyl acetylacetonate precursor for deposition of VO{sub 2} thin films with thermochromic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yu, Jung-Hoon; Nam, Sang-Hun; Kim, Donguk

Highlights: • 7 day aged VO(acac){sub 2} sol shows enhanced adhesivity on the SiO{sub 2} compared with non-aged sol. • The aging process has significantly affected the morphologies of VO{sub 2} films. • From the FT-IR spectra, thermal aging process provides the deformation of precursor. • The metal insulator transition (MIT) efficiency (ΔT{sub at2000} {sub nm}) reached a maximum value of 51% at 7 day aging. • Thermal aging process could shorten the aging time of sol solution. - Abstract: Thermochromic properties of vanadium dioxide (VO{sub 2}) have been studied extensively due to their IR reflection applications in energy smartmore » windows. In this paper, we studied the optical switching property of VO{sub 2} thin film, depending on the thermal aging time of the vanadyl acetylacetonate (VO(acac){sub 2}) precursor. We found the alteration of the IR spectra of the precursor by tuning the aging time as well as heat treatments of the precursor. An aging effect of vanadium precursor directly affects the morphologies, optical switching property and crystallinity of VO{sub 2} films. The optimum condition was achieved at the 7 day aging time with metal insulator transition (MIT) efficiency of 50%.« less

Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

2012-04-01

We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

Broadband and high modulation-depth THz modulator using low bias controlled VO2-integrated metasurface.

PubMed

Zhou, Gaochao; Dai, Penghui; Wu, Jingbo; Jin, Biaobing; Wen, Qiye; Zhu, Guanghao; Shen, Ze; Zhang, Caihong; Kang, Lin; Xu, Weiwei; Chen, Jian; Wu, Peiheng

2017-07-24

An active vanadium dioxide integrated metasurface offering broadband transmitted terahertz wave modulation with large modulation-depth under electrical control is demonstrated. The device consists of metal bias-lines arranged with grid-structure patterned vanadium dioxide (VO 2 ) film on sapphire substrate. Amplitude transmission is continuously tuned from more than 78% to 28% or lower in the frequency range from 0.3 THz to 1.0 THz, by means of electrical bias at temperature of 68 °C. The physical mechanism underlying the device's electrical tunability is investigated and found to be attributed to the ohmic heating. The developed device possessing over 87% modulation depth with 0.7 THz frequency band is expected to have many potential applications in THz regime such as tunable THz attenuator.

Nano crystalline Bi2(VO5) phases in lithium bismuth borate glasses containing mixed vanadium-nickel oxides

NASA Astrophysics Data System (ADS)

Yadav, Arti; Khasa, S.; Dahiya, M. S.; Agarwal, A.

2016-05-01

Glass composition 7V2O5.23Li2O.20Bi2O3.50B2O3 and x(2NiO.V2O5).(30-x)Li2O.20Bi2O3.50B2O3, x=0, 2, 5, 7 and 10, were produced by conventional melt quenching technique. The quenched amorphous glass samples were annealed at temperatures 400°C and 500°C for 6 hours. The Bi2(VO5) crystallite were grown in all prepared glass matrix. Tn vanadium lithium bismuth borate glass (annealed), the some phrase of V2O5-crystal were observed along with the nano crystalline Bi2(VO5) phase. The sharp peaks in FTTR spectra of all annealed compositions were also compatible with the XRD diffraction peaks of the system under investigation. Average crystalline size (D) of the Bi2(VO5) nano-crystallite was ~30nm for samples annealed at 400°C and ~42nm for samples annealed at 500°C. Lattice parameter and the lattice strain for all the samples was also calculated corresponding to the (113) plane of Bi2(VO5) crystallite.

Ab Initio Metadynamics Study of the VO2+/VO2+ Redox Reaction Mechanism at the Graphite Edge/Water Interface.

PubMed

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2018-06-20

Redox flow batteries (RFBs) are promising electrochemical energy storage systems, for which development is impeded by a poor understanding of redox reactions occurring at electrode/electrolyte interfaces. Even for the conventional all-vanadium RFB chemistry employing V 2+ /V 3+ and VO 2 + /VO 2+ couples, there is still no consensus about the reaction mechanism, electrode active sites, and rate-determining step. Herein, we perform Car-Parrinello molecular dynamics-based metadynamics simulations to unravel the mechanism of the VO 2 + /VO 2+ redox reaction in water at the oxygen-functionalized graphite (112̅0) edge surface serving as a representative carbon-based electrode. Our results suggest that during the battery discharge aqueous VO 2 + /VO 2+ species adsorb at the surface C-O groups as inner-sphere complexes, exhibiting faster adsorption/desorption kinetics than V 2+ /V 3+ , at least at low vanadium concentrations considered in our study. We find that this is because (i) VO 2 + /VO 2+ conversion does not involve the slow transfer of an oxygen atom, (ii) protonation of VO 2 + is spontaneous and coupled to interfacial electron transfer in acidic conditions to enable VO 2+ formation, and (iii) V 3+ found to be strongly bound to oxygen groups of the graphite surface features unfavorable desorption kinetics. In contrast, the reverse process taking place upon charging is expected to be more sluggish for the VO 2 + /VO 2+ redox couple because of both unfavorable deprotonation of the VO 2+ water ligands and adsorption/desorption kinetics.

Metal-insulator transition properties of sputtered silicon-doped and un-doped vanadium dioxide films at terahertz range

NASA Astrophysics Data System (ADS)

Zhang, Huafu; Wu, Zhiming; Niu, Ruihua; Wu, Xuefei; he, Qiong; Jiang, Yadong

2015-03-01

Silicon-doped and un-doped vanadium dioxide (VO2) films were synthesized on high-purity single-crystal silicon substrates by means of reactive direct current magnetron sputtering followed by thermal annealing. The structure, morphology and metal-insulator transition properties of silicon-doped VO2 films at terahertz range were measured and compared to those of un-doped VO2 films. X-ray diffraction and scanning electron microscopy indicated that doping the films with silicon significantly affects the preferred crystallographic orientation and surface morphologies (grain size, pores and characteristics of grain boundaries). The temperature dependence of terahertz transmission shows that the transition temperature, hysteresis width and transition sharpness greatly depend on the silicon contents while the transition amplitude was relatively insensitive to the silicon contents. Interestingly, the VO2 film doped with a silicon content of 4.6 at.% shows excellent terahertz switching characteristics, namely a small hysteresis width of 4.5 °C, a giant transmission modulation ratio of about 82% and a relatively low transition temperature of 56.1 °C upon heating. This work experimentally indicates that silicon doping can effectively control not only the surface morphology but also the metal-insulator transition characteristics of VO2 films at terahertz range.

Local probing of thermal energy transfer and conversion processes in VO2 nanostructures

NASA Astrophysics Data System (ADS)

Menges, Fabian

Nanostructures of strongly correlated materials, such as metal-insulator transition (MIT) oxides, enable unusual coupling of charge and heat transport. Hence, they provide an interesting pathway to the development of non-linear thermal devices for active heat flux control. Here, we will report the characterization of local thermal non-equilibrium processes in vanadium dioxide (VO2) thin films and single-crystalline nanobeams. Using a scanning thermal microscope and calorimetric MEMS platforms, we studied the MIT triggered by electrical currents, electrical fields, near-field thermal radiation and thermal conduction. Based on out recently introduced scanning probe thermometry method, which enables direct imaging of local Joule and Peltier effects, we quantified self-heating processes in VO2 memristors using the tip of a resistively heated scanning probe both as local sensor and nanoscopic heat source. Finally, we will report on recent approaches to build radiative thermal switches and oscillators using VO2 nanostructures. We quantified variations of near-field radiative thermal transport between silicon dioxide and VO2 down to nanoscopic gap sizes, and will discuss its implications for the development of phonon polariton based radiative thermal devices. Funding of the Swiss Federal Office of Energy under Grant Agreement No. SI/501093-01 is gratefully acknowledged.

Nonlinear optical properties of thick composite media with vanadium dioxide nanoparticles. I. Self-defocusing of radiation in the visible and near-IR regions

NASA Astrophysics Data System (ADS)

Ostrosablina, A. A.; Sidorov, A. I.

2005-07-01

This paper presents the experimental and theoretical results of a study of the interaction of pulsed laser radiation with thick composite media containing nanoparticles of vanadium dioxide (VO2). It establishes that the reversible semiconductor-metal phase transition that occurs in VO2 nanoparticles under the action of radiation can produce self-defocusing of radiation in the visible and near-IR regions because of the formation of a photoinduced dynamic lens. An analysis is carried out of how the radiation intensity affects the dynamics of these processes. It is shown that photoinduced absorption and scattering play a role in forming the nonlinear optical response.

Two-Dimensional SiO2/VO2 Photonic Crystals with Statically Visible and Dynamically Infrared Modulated for Smart Window Deployment.

PubMed

Ke, Yujie; Balin, Igal; Wang, Ning; Lu, Qi; Tok, Alfred Iing Yoong; White, Timothy J; Magdassi, Shlomo; Abdulhalim, Ibrahim; Long, Yi

2016-12-07

Two-dimensional (2D) photonic structures, widely used for generating photonic band gaps (PBG) in a variety of materials, are for the first time integrated with the temperature-dependent phase change of vanadium dioxide (VO 2 ). VO 2 possesses thermochromic properties, whose potential remains unrealized due to an undesirable yellow-brown color. Here, a SiO 2 /VO 2 core/shell 2D photonic crystal is demonstrated to exhibit static visible light tunability and dynamic near-infrared (NIR) modulation. Three-dimensional (3D) finite difference time domain (FDTD) simulations predict that the transmittance can be tuned across the visible spectrum, while maintaining good solar regulation efficiency (ΔT sol = 11.0%) and high solar transmittance (T lum = 49.6%). Experiments show that the color changes of VO 2 films are accompanied by NIR modulation. This work presents a novel way to manipulate VO 2 photonic structures to modulate light transmission as a function of wavelength at different temperatures.

Highly infrared sensitive VO2 nanowires for a nano-optical device.

PubMed

Bhuyan, Prabal Dev; Gupta, Sanjeev K; Kumar, Ashok; Sonvane, Yogesh; Gajjar, P N

2018-04-25

Recent studies on the electronic, magnetic and optical properties of VO2 (vanadium dioxide) materials have motivated the exploration of one dimensional VO2 nanowires. First principles calculations were performed to investigate the structural, electronic, magnetic and optical properties of the monoclinic (M) and rutile (R) phases of VO2 nanowires. The monoclinic phase shows semiconducting behaviour with a band gap of 1.17 eV, whereas the rutile phase of VO2 nanowires behaves as a spin gapless semiconducting material, as band lines cross the Fermi level due only to up spin contribution. The monoclinic structure of VO2 nanowires is found to be paramagnetic and the rutile structure shows ferromagnetic half metal behavior. The conductivity calculation for VO2 nanowires shows the metal-insulator transition (MIT) temperature to be 250 K. The possible mechanism of VO2 nanowires to be used as smart windows has been discussed, as the nanowires are highly sensitive in the infrared (IR) region. Interestingly, at low temperature, the VO2 monoclinic structure allows infrared light to be transmitted, while VO2 with the rutile phase blocks light in the IR region. Furthermore, we adsorbed CO2, N2 and SO2 gas molecules on 1D VO2 monoclinic nanowire to investigate their interaction behaviour. It was observed that the absorption and transmission properties of VO2 dramatically change upon the adsorption of CO2 and SO2 gas molecules, which is likely to open up its application as an optical gas sensor.

Dynamic structural colour using vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Wilson, K.; Marocico, C. A.; Bradley, A. L.

2018-06-01

A thin film stack consisting of layers of indium tin oxide (ITO) with an intermediate vanadium oxide (VO2) layer on an optically thick silver film has been investigated for dynamic structural colour. The structure benefits from the phase change properties of VO2. Compared with other phase change materials, such as germanium antimony telluride (GST), VO2 can be offered as a lower power consumption alternative. It has been overlooked in the visible spectral range due to its smaller refractive index change below 700 nm. We demonstrate that the sensitivity of the visible reflectance spectrum to the change in phase of a 30 nm VO2 layer is increased after it is incorporated in a thin film stack, with performance comparable to other phase change materials. The extent to which dynamic tuning of the reflectance spectra of ITO–VO2–ITO–Ag thin film stacks can be exploited for colour switching is reported, with approximately 25% change in reflectance demonstrated at 550 nm. Inclusion of a top ITO layer is also shown to improve the chromaticity change on phase transition.

Vanadium dioxide thin films prepared on silicon by low temperature MBE growth and ex-situ annealing

NASA Astrophysics Data System (ADS)

Homm, Pia; van Bilzen, Bart; Menghini, Mariela; Locquet, Jean-Pierre; Ivanova, Todora; Sanchez, Luis; Sanchis, Pablo

Vanadium dioxide (VO2) is a material that shows an insulator to metal transition (IMT) near room temperature. This property can be exploited for applications in field effect devices, electro-optical switches and nonlinear circuit components. We have prepared VO2 thin films on silicon wafers by combining a low temperature MBE growth with an ex-situ annealing at high temperature. We investigated the structural, electrical and optical characteristics of films with thicknesses ranging from 10 to 100 nm. We have also studied the influence of the substrate cleaning. The films grown with our method are polycrystalline with a preferred orientation in the (011) direction of the monoclinic phase. For the films produced on silicon with a native oxide, an IMT at around 75 °C is observed. The magnitude of the resistance change across the IMT decreases with thickness while the refractive index at room temperature corresponds with values reported in the literature for thin films. The successful growth of VO2 films on silicon with good electrical and optical properties is an important step towards the integration of VO2 in novel devices. The authors acknowledge financial support from the FWO project G052010N10 and EU-FP7 SITOGA project. PH acknowledges support from Becas Chile - CONICYT.

Tracking the insulator-to-metal phase transition in VO2 with few-femtosecond extreme UV transient absorption spectroscopy

PubMed Central

Jager, Marieke F.; Ott, Christian; Kraus, Peter M.; Kaplan, Christopher J.; Pouse, Winston; Marvel, Robert E.; Haglund, Richard F.; Neumark, Daniel M.; Leone, Stephen R.

2017-01-01

Coulomb correlations can manifest in exotic properties in solids, but how these properties can be accessed and ultimately manipulated in real time is not well understood. The insulator-to-metal phase transition in vanadium dioxide (VO2) is a canonical example of such correlations. Here, few-femtosecond extreme UV transient absorption spectroscopy (FXTAS) at the vanadium M2,3 edge is used to track the insulator-to-metal phase transition in VO2. This technique allows observation of the bulk material in real time, follows the photoexcitation process in both the insulating and metallic phases, probes the subsequent relaxation in the metallic phase, and measures the phase-transition dynamics in the insulating phase. An understanding of the VO2 absorption spectrum in the extreme UV is developed using atomic cluster model calculations, revealing V3+/d2 character of the vanadium center. We find that the insulator-to-metal phase transition occurs on a timescale of 26 ± 6 fs and leaves the system in a long-lived excited state of the metallic phase, driven by a change in orbital occupation. Potential interpretations based on electronic screening effects and lattice dynamics are discussed. A Mott–Hubbard-type mechanism is favored, as the observed timescales and d2 nature of the vanadium metal centers are inconsistent with a Peierls driving force. The findings provide a combined experimental and theoretical roadmap for using time-resolved extreme UV spectroscopy to investigate nonequilibrium dynamics in strongly correlated materials. PMID:28827356

Correlation of plume dynamics and oxygen pressure with VO2 stoichiometry during pulsed laser deposition

NASA Astrophysics Data System (ADS)

Lafane, S.; Kerdja, T.; Abdelli-Messaci, S.; Khereddine, Y.; Kechouane, M.; Nemraoui, O.

2013-07-01

Vanadium dioxide thin films have been deposited on Corning glass substrates by a KrF laser ablation of V2O5 target at the laser fluence of 2 J cm-2. The substrate temperature and the target-substrate distance were set to 500 ∘C and 4 cm, respectively. X-ray diffraction analysis showed that pure VO2 is only obtained at an oxygen pressure range of 4×10-3-2×10-2 mbar. A higher optical switching contrast was obtained for the VO2 films deposited at 4×10-3-10-2 mbar. The films properties were correlated to the plume-oxygen gas interaction monitored by fast imaging of the plume.

Optical bistability and optical response of an infrared quantum dot hybridized to VO2 nanoparticle

NASA Astrophysics Data System (ADS)

Zamani, Naser; Hatef, Ali; Nadgaran, Hamid; Keshavarz, Alireza

2017-08-01

In this work, we theoretically investigate optical bistability and optical response of a hybrid system consisting of semiconductor quantum dot (SQD) coupled with a vanadium dioxide nanoparticle (VO2NP) in the infrared (IR) regime. The VO2 material exists in semiconductor and metallic phases below and above the critical temperature, respectively where the particle optical properties dramatically change during this phase transition. In our calculations a filling fraction factor controls the VO2NP phase transition when the hybrid system interacts with a laser field. We demonstrate that the switch-up threshold for optical bistability is strongly controlled by filling fraction without changing the structure of the hybrid system. Also, it is shown that, the threshold of optical bistability increases when the VO2NP phases changes from semiconductor to metallic phase. The presented results have the potential to be applied in designing optical switching and optical storage.

Enhanced Visible Transmittance of Thermochromic VO2 Thin Films by SiO2 Passivation Layer and Their Optical Characterization

PubMed Central

Yu, Jung-Hoon; Nam, Sang-Hun; Lee, Ji Won; Boo, Jin-Hyo

2016-01-01

This paper presents the preparation of high-quality vanadium dioxide (VO2) thermochromic thin films with enhanced visible transmittance (Tvis) via radio frequency (RF) sputtering and plasma enhanced chemical vapor deposition (PECVD). VO2 thin films with high Tvis and excellent optical switching efficiency (Eos) were successfully prepared by employing SiO2 as a passivation layer. After SiO2 deposition, the roughness of the films was decreased 2-fold and a denser structure was formed. These morphological changes corresponded to the results of optical characterization including the haze, reflectance and absorption spectra. In spite of SiO2 coating, the phase transition temperature (Tc) of the prepared films was not affected. Compared with pristine VO2, the total layer thickness after SiO2 coating was 160 nm, which is an increase of 80 nm. Despite the thickness change, the VO2 thin films showed a higher Tvis value (λ 650 nm, 58%) compared with the pristine samples (λ 650 nm, 43%). This enhancement of Tvis while maintaining high Eos is meaningful for VO2-based smart window applications. PMID:28773679

VO2 film temperature dynamics at low-frequency current self-oscillations

NASA Astrophysics Data System (ADS)

Bortnikov, S. G.; Aliev, V. Sh.; Badmaeva, I. A.; Mzhelskiy, I. V.

2018-02-01

Low-frequency (˜2 Hz) current self-oscillations were first obtained in a millimeter-sized two-terminal planar device with a vanadium dioxide (VO2) film. The film temperature distribution dynamics was investigated within one oscillation period. It was established that the formation and disappearance of a conductive channel occur in a film in less than 60 ms with oscillation period 560 ms. The experimentally observed temperature in the channel region reached 413 K, being understated due to a low infrared microscope performance (integration time 10 ms). The VO2 film temperature distribution dynamics was simulated by solving a 2D problem of the electric current flow and heat transfer in the film. The calculation showed that the thermally initiated resistance switching in the film occurs in less than 4 ms at a channel temperature reaching ˜1000 K. The experimental results and simulation are consistent with the current self-oscillation mechanism based on the current pinching and dielectric relaxation in the VO2 film at the metal-insulator phase transition.

Gate-tunable gigantic changes in lattice parameters and optical properties in VO2

NASA Astrophysics Data System (ADS)

Nakano, Masaki; Okuyama, Daisuke; Shibuya, Keisuke; Ogawa, Naoki; Hatano, Takafumi; Kawasaki, Masashi; Arima, Taka-Hisa; Iwasa, Yoshihiro; Tokura, Yoshinori

2014-03-01

The field-effect transistor provides an electrical switching function of current flowing through a channel surface by external gate voltage (VG). We recently reported that an electric-double-layer transistor (EDLT) based on vanadium dioxide (VO2) enables electrical switching of the metal-insulator phase transition, where the low-temperature insulating state can be completely switched to the metallic state by application of VG. Here we demonstrate that VO2-EDLT enables electrical switching of lattice parameters and optical properties as well as electrical current. We performed in-situ x-ray diffraction and optical transmission spectroscopy measurements, and found that the c-axis length and the infrared transmittance of VO2 can be significantly modulated by more than 1% and 40%, respectively, by application of VG. We emphasize that these distinguished features originate from the electric-field induced bulk phase transition available with VO2-EDLT. This work was supported by the Japan Society for the Promotion of Science (JSPS) through its ``Funding Program for World-Leading Innovative R&D on Science and Technology (FIRST Program).''

Tracking the insulator-to-metal phase transition in VO 2 with few-femtosecond extreme UV transient absorption spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jager, Marieke F.; Ott, Christian; Kraus, Peter M.

We present coulomb correlations can manifest in exotic properties in solids, but how these properties can be accessed and ultimately manipulated in real time is not well understood. The insulator-to-metal phase transition in vanadium dioxide (VO 2) is a canonical example of such correlations. Here, few-femtosecond extreme UV transient absorption spectroscopy (FXTAS) at the vanadium M 2,3 edge is used to track the insulator-to-metal phase transition in VO 2 . This technique allows observation of the bulk material in real time, follows the photoexcitation process in both the insulating and metallic phases, probes the subsequent relaxation in the metallic phase,more » and measures the phase-transition dynamics in the insulating phase. An understanding of the VO 2 absorption spectrum in the extreme UV is developed using atomic cluster model calculations, revealing V 3+/d 2 character of the vanadium center. We find that the insulator-to-metal phase transition occurs on a timescale of 26 ± 6 fs and leaves the system in a long-lived excited state of the metallic phase, driven by a change in orbital occupation. Potential interpretations based on electronic screening effects and lattice dynamics are discussed. A Mott–Hubbard-type mechanism is favored, as the observed timescales and d 2 nature of the vanadium metal centers are inconsistent with a Peierls driving force. In conclusion, the findings provide a combined experimental and theoretical roadmap for using time-resolved extreme UV spectroscopy to investigate nonequilibrium dynamics in strongly correlated materials.« less

Tracking the insulator-to-metal phase transition in VO 2 with few-femtosecond extreme UV transient absorption spectroscopy

DOE PAGES

Jager, Marieke F.; Ott, Christian; Kraus, Peter M.; ...

2017-08-21

We present coulomb correlations can manifest in exotic properties in solids, but how these properties can be accessed and ultimately manipulated in real time is not well understood. The insulator-to-metal phase transition in vanadium dioxide (VO 2) is a canonical example of such correlations. Here, few-femtosecond extreme UV transient absorption spectroscopy (FXTAS) at the vanadium M 2,3 edge is used to track the insulator-to-metal phase transition in VO 2 . This technique allows observation of the bulk material in real time, follows the photoexcitation process in both the insulating and metallic phases, probes the subsequent relaxation in the metallic phase,more » and measures the phase-transition dynamics in the insulating phase. An understanding of the VO 2 absorption spectrum in the extreme UV is developed using atomic cluster model calculations, revealing V 3+/d 2 character of the vanadium center. We find that the insulator-to-metal phase transition occurs on a timescale of 26 ± 6 fs and leaves the system in a long-lived excited state of the metallic phase, driven by a change in orbital occupation. Potential interpretations based on electronic screening effects and lattice dynamics are discussed. A Mott–Hubbard-type mechanism is favored, as the observed timescales and d 2 nature of the vanadium metal centers are inconsistent with a Peierls driving force. In conclusion, the findings provide a combined experimental and theoretical roadmap for using time-resolved extreme UV spectroscopy to investigate nonequilibrium dynamics in strongly correlated materials.« less

Study on Thermochromic VO2 Films Grown on ZnO-Coated Glass Substrates for “Smart Windows”

NASA Astrophysics Data System (ADS)

Kato, Kazuhiro; Song, Pung Keun; Odaka, Hidehumi; Shigesato, Yuzo

2003-10-01

Vanadium dioxide (VO2) is one of the most attractive thermochromic materials, which show large changes in optical and electrical properties at the transition temperature (Tt) close to the atmospheric temperature (approximately 340 K). We already reported for VO2 deposition by rf magnetron sputtering using V2O3 or V2O5 targets that VO2 films thicker than 400 nm showed high thermochromic performance, whereas the VO2 films thinner than 200 nm did not show such performance because of their poor crystallinity and off-stoichiometry. In this study, very thin thermochromic VO2 films with thicknesses of about 50 nm were successfully deposited using highly < 001>-preferred oriented ZnO polycrystalline films as a buffer layer between the VO2 film and glass substrate (VO2/ZnO/glass) because of the heteroepitaxial growth of VO2 polycrystalline films. W-doped VO2 films were also deposited on the ZnO-coated glass substrates (ZnO/glass) by cosputtering. It was confirmed that W doping for thin VO2 films deposited on the ZnO/glass can decrease Tt systematically. Such very thin VO2 films should have high potential for application in “smart windows”.

Tunable subwavelength hot spot of dipole nanostructure based on VO2 phase transition.

PubMed

Park, Jun-Bum; Lee, Il-Min; Lee, Seung-Yeol; Kim, Kyuho; Choi, Dawoon; Song, Eui Young; Lee, Byoungho

2013-07-01

We propose a novel approach to generate and tune a hot spot in a dipole nanostructure of vanadium dioxide (VO2) laid on a gold (Au) substrate. By inducing a phase transition of the VO2, the spatial and spectral distributions of the hot spot generated in the feed gap of the dipole can be tuned. Our numerical simulation based on a finite-element method shows a strong intensity enhancement difference and tunability near the wavelength of 678 nm, where the hot spot shows 172-fold intensity enhancement when VO2 is in the semiconductor phase. The physical mechanisms of forming the hot spots at the two-different phases are discussed. Based on our analysis, the effects of geometric parameters in our dipole structure are investigated with an aim of enhancing the intensity and the tunability. We hope that the proposed nanostructure opens up a practical approach for the tunable near-field nano-photonic devices.

Characterization of pulsed laser deposition grown V2O3 converted VO2

NASA Astrophysics Data System (ADS)

Majid, Suhail; Shukla, D. K.; Rahman, F.; Gautam, Kamini; Sathe, V. G.; Choudhary, R. J.; Phase, D. M.

2016-10-01

Controllable tuning of Metal-insulator transition in VxOy thin film has been a field of extensive research. However controlled synthesis of desired Vanadium oxide phase is a challenging task. We have successfully achieved VO2 phase on Silicon substrate after post deposition annealing treatment to the PLD grown as deposited V2O3 thin films. The annealed thin film was characterized by x-ray diffraction (XRD), resistivity, Raman spectroscopy, X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS) measurements. XRD confirms the crystalline nature and growth of VO2 phase in thin film. The characteristic MIT was observed from resistivity measurements and transition temperature appeared at lower value around 336 K, compared to bulk VO2. The structural transition accompanied with MIT from lower temperature monoclinic phase to higher temperature Rutile phase became evident from temperature dependent Raman measurements. Chemical state of vanadium was examined using XAS and XPS measurements which confirm the presence of +4 oxidation state of vanadium in thin film.

Optoelectronic and all-optical multiple memory states in vanadium dioxide

NASA Astrophysics Data System (ADS)

Coy, Horacio; Cabrera, Rafmag; Sepúlveda, Nelson; Fernández, Félix E.

2010-12-01

Vanadium dioxide exhibits a well-known insulator-to-metal transition during which several of its physical properties change significantly. A hysteresis loop develops for each of them as the material is heated and then cooled through the transition. In this work VO2/SiO2 samples were maintained—by heat sinking—at a selected temperature within the heating branch of the hysteresis loops for resistance and near-infrared transmittance, while brief thermal excursions of the VO2 film were caused by either voltage pulses applied to the film or laser light pulses irradiating the film. These pulses had durations from milliseconds to a few seconds and the resulting drops in resistance or transmittance were easily and repeatably measurable without appreciably affecting their new values. A sequence of equal-duration pulses (for either equal-voltage or equal-irradiation pulses) caused the resistance and infrared transmittance to continue to drop, each time by a smaller amount, and larger energy pulses were required in order to cause drops comparable with the initial one. The ability of the film to change the values of the measurands in this manner with additional pulses was maintained up to a limit defined by the outer hysteresis curve for the measurand in question. The results presented show that a plurality of memory "states" in VO2 can be established or "written" either by voltage pulses or by light pulses applied to the material, and queried or "read" by resistance or transmittance readings, or both. These states were found to remain stable for at least several hours, as long as temperature was kept constant, and are expected to persist indefinitely under this condition. In the all-optical case, if the same light beam is used for writing and reading the memory state, the device is an optical analog of a memristor.

Influence of Heat Treatment Conditions on the Properties of Vanadium Oxide Thin Films for Thermochromic Applications.

PubMed

Kim, Donguk; Kwon, Samyoung; Park, Young; Boo, Jin-Hyo; Nam, Sang-Hun; Joo, Yang Tae; Kim, Minha; Lee, Jaehyeong

2016-05-01

In present work, the effects of the heat treatment on the structural, optical, and thermochromic properties of vanadium oxide films were investigated. Vanadium dioxide (VO2) thin films were deposited on glass substrate by reactive pulsed DC magnetron sputtering from a vanadium metal target in mixture atmosphere of argon and oxygen gas. Various heat treatment conditions were applied in order to evaluate their influence on the crystal phases formed, surface morphology, and optical properties. The films were characterized by an X-ray diffraction (XRD) in order to investigate the crystal structure and identify the phase change as post-annealing temperature of 500-600 degrees C for 5 minutes. Surface conditions of the obtained VO2(M) films were analyzed by field emission scanning electron microscopy (FE-SEM) and the semiconductor-metal transition (SMT) characteristics of the VO2 films were evaluate by optical spectrophotometry in the UV-VIS-NIR, controlling temperature of the films.

Epitaxial growth of VO2 by periodic annealing

NASA Astrophysics Data System (ADS)

Tashman, J. W.; Lee, J. H.; Paik, H.; Moyer, J. A.; Misra, R.; Mundy, J. A.; Spila, T.; Merz, T. A.; Schubert, J.; Muller, D. A.; Schiffer, P.; Schlom, D. G.

2014-02-01

We report the growth of ultrathin VO2 films on rutile TiO2 (001) substrates via reactive molecular-beam epitaxy. The films were formed by the cyclical deposition of amorphous vanadium and its subsequent oxidation and transformation to VO2 via solid-phase epitaxy. Significant metal-insulator transitions were observed in films as thin as 2.3 nm, where a resistance change ΔR/R of 25 was measured. Low angle annular dark field scanning transmission electron microscopy was used in conjunction with electron energy loss spectroscopy to study the film/substrate interface and revealed the vanadium to be tetravalent and the titanium interdiffusion to be limited to 1.6 nm.

Dynamically Babinet-invertible metasurface: a capacitive-inductive reconfigurable filter for terahertz waves using vanadium-dioxide metal-insulator transition

NASA Astrophysics Data System (ADS)

Urade, Yoshiro; Nakata, Yosuke; Okimura, Kunio; Nakanishi, Toshihiro; Miyamaru, Fumiaki; Takeda, Mitsuo W.; Kitano, Masao

2016-03-01

This paper proposes a reconfigurable planar metamaterial that can be switched between capacitive and inductive responses using local changes in the electrical conductivity of its constituent material. The proposed device is based on Babinet's principle and exploits the singular electromagnetic responses of metallic checkerboard structures, which are dependent on the local electrical conductivity. Utilizing the heating-induced metal-insulator transition of vanadium dioxide ($\\mathrm{VO}_2$), the proposed metamaterial is designed to compensate for the effect of the substrate and is experimentally characterized in the terahertz regime. This reconfigurable metamaterial can be utilized as a switchable filter and as a switchable phase shifter for terahertz waves.

Dynamically Babinet-invertible metasurface: a capacitive-inductive reconfigurable filter for terahertz waves using vanadium-dioxide metal-insulator transition.

PubMed

Urade, Yoshiro; Nakata, Yosuke; Okimura, Kunio; Nakanishi, Toshihiro; Miyamaru, Fumiaki; Takeda, Mitsuo W; Kitano, Masao

2016-03-07

This paper proposes a reconfigurable planar metamaterial that can be switched between capacitive and inductive responses using local changes in the electrical conductivity of its constituent material. The proposed device is based on Babinet's principle and exploits the singular electromagnetic responses of metallic checkerboard structures, which are dependent on the local electrical conductivity. Utilizing the heating-induced metal-insulator transition of vanadium dioxide (VO 2 ), the proposed meta-material is designed to compensate for the effect of the substrate and is experimentally characterized in the terahertz regime. This reconfigurable metamaterial can be utilized as a switchable filter and as a switchable phase shifter for terahertz waves.

Microwave-Assisted Synthesis of Silver Vanadium Phosphorus Oxide, Ag 2VO 2PO 4 : Crystallite Size Control and Impact on Electrochemistry

DOE PAGES

Huang, Jianping; Marschilok, Amy C.; Takeuchi, Esther S.; ...

2016-03-07

We study silver vanadium phosphorus oxide, Ag 2VO 2PO 4, that is a promising cathode material for Li batteries due in part to its large capacity and high current capability. Herein, a new synthesis of Ag 2VO 2PO 4 based on microwave heating is presented, where the reaction time is reduced by approximately 100× relative to other reported methods, and the crystallite size is controlled via synthesis temperature, showing a linear correlation of crystallite size with temperature. Notably, under galvanostatic reduction, the Ag 2VO 2PO 4 sample with the smallest crystallite size delivers the highest capacity and shows the highestmore » loaded voltage. Further, pulse discharge tests show a significant resistance decrease during the initial discharge coincident with the formation of Ag metal. Thus, the magnitude of the resistance decrease observed during pulse tests depends on the Ag 2VO 2PO 4 crystallite size, with the largest resistance decrease observed for the smallest crystallite size. Additional electrochemical measurements indicate a quasi-reversible redox reaction involving Li + insertion/deinsertion, with capacity fade due to structural changes associated with the discharge/charge process. In summary, this work demonstrates a faster synthetic approach for bimetallic polyanionic materials which also provides the opportunity for tuning of electrochemical properties through control of material physical properties such as crystallite size.« less

Passive Q switching and mode-locking of Er:glass lasers using VO2 mirrors

NASA Astrophysics Data System (ADS)

Pollack, S. A.; Chang, D. B.; Chudnovky, F. A.; Khakhaev, I. A.

1995-09-01

Passive Q switching of an Er:glass laser with the pulse width varying between 14 and 80 ns has been demonstrated, using three resonator vanadium-dioxide-coated (VO2) mirror samples with temperature-dependent reflectivity and differing in the reflectivity contrast. The reflectivity changes because of a phase transition from a semiconductor to a metallic state. Broad band operating characteristics of VO2 mirrors provide Q switching over a wide range of wavelengths. In addition, mode-locked pulses with much shorter time scales have been observed, due to exciton formation and recombination. A simple criterion is derived for the allowable ambient temperatures at which the Q switching operates effectively. A simple relation has also been found relating the duration of the Q-switched pulse to the contrast in reflectivities of the two mirror phases.

Electrochemical gating-induced reversible and drastic resistance switching in VO2 nanowires

PubMed Central

Sasaki, Tsubasa; Ueda, Hiroki; Kanki, Teruo; Tanaka, Hidekazu

2015-01-01

Reversible and drastic modulation of the transport properties in vanadium dioxide (VO2) nanowires by electric field-induced hydrogenation at room temperature was demonstrated using the nanogaps separated by humid air in field-effect transistors with planer-type gates (PG-FET). These PG-FETs allowed us to investigate behavior of revealed hydrogen intercalation and diffusion aspects with time and spatial evolutions in nanowires. These results show that air nanogaps can operate as an electrochemical reaction field, even in a gaseous atmosphere, and offer new directions to explore emerging functions for electronic and energy devices in oxides. PMID:26584679

Low loss millimeter-wave switches based on the Vanadium Dioxide Metal - Insulator - Transition

NASA Astrophysics Data System (ADS)

Field, Mark; Hillman, Christopher; Stupar, Philip; Griffith, Zachary; Rodwell, Mark

2014-03-01

A new ultra-low-loss and broad band millimeter wave switch technology based on the reversible metal / insulator phase transition of vanadium dioxide has been developed. We report having fabricated series configured, single-pole single-throw (SPST) switches having measured S-parameters from DC to 110 GHz. The on-state insertion loss is 0.2 dB and off-state isolation is 21 dB at 50 GHz. The resulting impedance contrast ratio, ZOFF / ZON, is greater than 500:1 at 50 GHz (i.e. cut-off frequency fc ~ 40 THz). As a demonstration of the technology's utility, we also present the results of a 2-bit real time delay phase shifter incorporating a pair of VO2 SP4T switches. This switch technology's high impedance contrast ratio combined with its compactness, ease of integration, and low voltage operation make it an enabler of previously unachievable high-performance millimeter wave FPGAs.

Nano crystalline Bi{sub 2}(VO{sub 5}) phases in lithium bismuth borate glasses containing mixed vanadium-nickel oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yadav, Arti, E-mail: artidabhur@gmail.com; Khasa, S.; Dahiya, M. S.

2016-05-23

Glass composition 7V{sub 2}O{sub 5}·23Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3} and x(2NiO·V{sub 2}O{sub 5})·(30-x)Li{sub 2}O·20Bi{sub 2}O{sub 3}·50B{sub 2}O{sub 3}, x=0, 2, 5, 7 and 10, were produced by conventional melt quenching technique. The quenched amorphous glass samples were annealed at temperatures 400°C and 500°C for 6 hours. The Bi{sub 2}(VO{sub 5}) crystallite were grown in all prepared glass matrix. Tn vanadium lithium bismuth borate glass (annealed), the some phrase of V{sub 2}O{sub 5}-crystal were observed along with the nano crystalline Bi{sub 2}(VO{sub 5}) phase. The sharp peaks in FTTR spectra of all annealed compositions were also compatible with the XRDmore » diffraction peaks of the system under investigation. Average crystalline size (D) of the Bi{sub 2}(VO{sub 5}) nano-crystallite was ~30 nm for samples annealed at 400°C and ~42 nm for samples annealed at 500°C. Lattice parameter and the lattice strain for all the samples was also calculated corresponding to the (113) plane of Bi{sub 2}(VO{sub 5}) crystallite.« less

Nanoscale Engineering in VO2 Nanowires via Direct Electron Writing Process.

PubMed

Zhang, Zhenhua; Guo, Hua; Ding, Wenqiang; Zhang, Bin; Lu, Yue; Ke, Xiaoxing; Liu, Weiwei; Chen, Furong; Sui, Manling

2017-02-08

Controlling phase transition in functional materials at nanoscale is not only of broad scientific interest but also important for practical applications in the fields of renewable energy, information storage, transducer, sensor, and so forth. As a model functional material, vanadium dioxide (VO 2 ) has its metal-insulator transition (MIT) usually at a sharp temperature around 68 °C. Here, we report a focused electron beam can directly lower down the transition temperature of a nanoarea to room temperature without prepatterning the VO 2 . This novel process is called radiolysis-assisted MIT (R-MIT). The electron beam irradiation fabricates a unique gradual MIT zone to several times of the beam size in which the temperature-dependent phase transition is achieved in an extended temperature range. The gradual transformation zone offers to precisely control the ratio of metal/insulator phases. This direct electron writing technique can open up an opportunity to precisely engineer nanodomains of diversified electronic properties in functional material-based devices.

Non-Congruence of Thermally Induced Structural and Electronic Transitions in VO2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nag, Joyeeta; HaglundJr., Richard F; Payzant, E Andrew

2012-01-01

The multifunctional properties of vanadium dioxide (VO2) arise from coupled first-order phase transitions: an insulator-to-metal transition (IMT) and a structural phase transition (SPT) from monoclinic to tetragonal. The characteristic signatures of the IMT and SPT are the hysteresis loops that track the phase transition from nucleation to stabilization of a new phase and back. A long-standing question about the mechanism of the VO2 phase transition is whether and how the almost-simultaneous electronic and structural transitions are related. Here we report independent measurements of the IMT and SPT hystereses in epitaxial VO2 films with differing morphologies. We show that, in bothmore » cases, the hystereses are not congruent, that the structural change requires more energy to reach completion. This result is independent of nanoscale morphology, so that the non- congruence is an intrinsic property of the VO2 phase transition. Our conclusion is supported by effective-medium calculations of the dielectric function incorporating the measured volume fractions of the monoclinic and tetragonal states. The results are consistent with the existence of an monoclinic correlated metallic state in which the electron- electron correlations characteristic of the monoclinic state begin to disappear before the transition to the tetragonal structural state.« less

Evolution of Structural and Electrical Properties of Oxygen-Deficient VO2 under Low Temperature Heating Process.

PubMed

Zhang, Jiasong; Zhao, Zhengjing; Li, Jingbo; Jin, Haibo; Rehman, Fida; Chen, Pengwan; Jiang, Yijie; Chen, Chunxu; Cao, Maosheng; Zhao, Yongjie

2017-08-16

Structural stability and functional performances of vanadium dioxide (VO 2 ) are strongly influenced by oxygen vacancies. However, the mechanism of metal-insulator transition (MIT) influenced by defects is still under debate. Here, we study the evolution of structure and electrical property of oxygen-deficient VO 2 by a low temperature annealing process (LTP) based on a truss-structured VO 2 nanonet. The oxygenation process of the oxygen-deficient VO 2 is greatly prolonged, which enables us to probe the gradual change of properties of the oxygen-deficient VO 2 . A continuous lattice reduction is observed during LTP. No recrystallization and structural collapse of the VO 2 nanonet can be found after LTP. The valence-band X-ray photoelectron spectroscopy (XPS) measurements indicate that the oxygen deficiency strongly affects the energy level of the valence band edge. Correspondingly, the resistance changes of the VO 2 films from 1 to 4.5 orders of magnitude are achieved by LTP. The effect of oxygen vacancy on the electric field driven MIT is investigated. The threshold value of voltage triggering the MIT decreases with increasing the oxygen vacancy concentration. This work demonstrates a novel and effective way to control the content of oxygen vacancies in VO 2 and the obvious impact of oxygen vacancy on MIT, facilitating further research on the role of oxygen vacancy in structure and MIT of VO 2 , which is important for the deep understanding of MIT and exploiting innovative functional application of VO 2 .

Silver Vanadium Phosphorous Oxide, Ag(2)VO(2)PO(4): Chimie Douce Preparation and Resulting Lithium Cell Electrochemistry.

PubMed

Kim, Young Jin; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2011-08-15

Recently, we have shown silver vanadium phosphorous oxide (Ag(2)VO(2)PO(4), SVPO) to be a promising cathode material for lithium based batteries. Whereas the first reported preparation of SVPO employed an elevated pressure, hydrothermal approach, we report herein a novel ambient pressure synthesis method to prepare SVPO, where our chimie douce preparation is readily scalable and provides material with a smaller, more consistent particle size and higher surface area relative to SVPO prepared via the hydrothermal method. Lithium electrochemical cells utilizing SVPO cathodes made by our new process show improved power capability under constant current and pulse conditions over cells containing cathode from SVPO prepared via the hydrothermal method.

Thermal tuning of infrared resonant absorbers based on hybrid gold-VO{sub 2} nanostructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kocer, Hasan; Department of Electrical Engineering, Turkish Military Academy, 06654 Ankara; Butun, Serkan

2015-04-20

Resonant absorbers based on plasmonic materials, metamaterials, and thin films enable spectrally selective absorption filters, where absorption is maximized at the resonance wavelength. By controlling the geometrical parameters of nano/microstructures and materials' refractive indices, resonant absorbers are designed to operate at wide range of wavelengths for applications including absorption filters, thermal emitters, thermophotovoltaic devices, and sensors. However, once resonant absorbers are fabricated, it is rather challenging to control and tune the spectral absorption response. Here, we propose and demonstrate thermally tunable infrared resonant absorbers using hybrid gold-vanadium dioxide (VO{sub 2}) nanostructure arrays. Absorption intensity is tuned from 90% to 20%more » and 96% to 32% using hybrid gold-VO{sub 2} nanowire and nanodisc arrays, respectively, by heating up the absorbers above the phase transition temperature of VO{sub 2} (68 °C). Phase change materials such as VO{sub 2} deliver useful means of altering optical properties as a function of temperature. Absorbers with tunable spectral response can find applications in sensor and detector applications, in which external stimulus such as heat, electrical signal, or light results in a change in the absorption spectrum and intensity.« less

Enhancing Modulation of Thermal Conduction in Vanadium Dioxide Thin Film by Nanostructured Nanogaps

DOE PAGES

Choe, Hwan Sung; Suh, Joonki; Ko, Changhyun; ...

2017-08-02

Efficient thermal management at the nanoscale is important for reducing energy consumption and dissipation in electronic devices, lab-on-a-chip platforms and energy harvest/conversion systems. For many of these applications, it is much desired to have a solid-state structure that reversibly switches thermal conduction with high ON/OFF ratios and at high speed. We describe design and implementation of a novel, all-solid-state thermal switching device by nanostructured phase transformation, i.e., modulation of contact pressure an d area between two poly-silicon surfaces activated by microstructural change of a vanadium dioxide (VO 2 ) thin film. Our solid-state devices demonstrate large and reversible alteration ofmore » cross-plane thermal conductance as a function of temperature, achieving a conductance ratio of at least 2.5. This new approach using nanostructured phase transformation provides new opportunities for applications that require advanced temperature and heat regulations.« less

Enhancing Modulation of Thermal Conduction in Vanadium Dioxide Thin Film by Nanostructured Nanogaps

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choe, Hwan Sung; Suh, Joonki; Ko, Changhyun

Efficient thermal management at the nanoscale is important for reducing energy consumption and dissipation in electronic devices, lab-on-a-chip platforms and energy harvest/conversion systems. For many of these applications, it is much desired to have a solid-state structure that reversibly switches thermal conduction with high ON/OFF ratios and at high speed. We describe design and implementation of a novel, all-solid-state thermal switching device by nanostructured phase transformation, i.e., modulation of contact pressure an d area between two poly-silicon surfaces activated by microstructural change of a vanadium dioxide (VO 2 ) thin film. Our solid-state devices demonstrate large and reversible alteration ofmore » cross-plane thermal conductance as a function of temperature, achieving a conductance ratio of at least 2.5. This new approach using nanostructured phase transformation provides new opportunities for applications that require advanced temperature and heat regulations.« less

The metal-insulator triple point in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cobden, David

2014-03-01

The metal-insulator transition (MIT) in vanadium dioxide is a candidate for optical and electrical switching applications. However, being a first-order solid-state phase transition makes it challenging to study reproducibly in any detail. The combination of the change in unit cell shape, symmetry reduction, long range of elastic distortion, and latent heat leads to domain structure, hysteresis, and cracking of even the highest quality samples. At the MIT two stable insulating phases (M1 and M2) occur in addition to the metallic phase (R), but their phase stability diagram was poorly known. To establish it precisely we studied single-crystal nanobeams of VO2 in a purpose-built nanomechanical strain apparatus. We were able to measure the transition temperature accurately to be 65.0 +- 0.1 oC, to determine the phase boundary slopes, and to detect the intermediate metastable triclinic (T) phase where it is metastable towards M2. We were surprised to find that the transition occurs precisely at the solid-state triple point of the metallic and two insulating phases, a fact that is not explained by existing theories. See J.H. Park et al, Nature 500, 431-4 (August 2013), doi:10.1038/nature12425. Supported by US Department of Energy, Office of Basic Energy Sciences, Division of Materials Science and Engineering, award DE-SC0002197.

Controlling the Temperature and Speed of the Phase Transition of VO 2 Microcrystals

DOE PAGES

Yoon, Joonseok; Kim, Howon; Chen, Xian; ...

2015-12-29

Here, we investigated the control of two important parameters of vanadium dioxide (VO 2 ) microcrystals, the phase transition temperature and speed, by varying microcrystal width. By using the reflectivity change between insulating and metallic phases, phase transition temperature is measured by optical microscopy. As the width of square cylinder-shaped microcrystals decreases from ~70 to ~1 μm, the phase transition temperature (67 °C for bulk) varied as much as 26.1 °C (19.7 °C) during heating (cooling). In addition, the propagation speed of phase boundary in the microcrystal, i.e., phase transition speed, is monitored at the onset of phase transition bymore » using the high-speed resistance measurement. The phase transition speed increases from 4.6 × 10 2 to 1.7 × 10 4 μm/s as the width decreases from ~50 to ~2 μm. While the statistical description for a heterogeneous nucleation process explains the size dependence on phase transition temperature of VO 2 , the increase of effective thermal exchange process is responsible for the enhancement of phase transition speed of small VO 2 microcrystals. These findings not only enhance the understanding of VO 2 intrinsic properties but also contribute to the development of innovative electronic devices.« less

Controlling the Temperature and Speed of the Phase Transition of VO 2 Microcrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yoon, Joonseok; Kim, Howon; Chen, Xian

Here, we investigated the control of two important parameters of vanadium dioxide (VO 2 ) microcrystals, the phase transition temperature and speed, by varying microcrystal width. By using the reflectivity change between insulating and metallic phases, phase transition temperature is measured by optical microscopy. As the width of square cylinder-shaped microcrystals decreases from ~70 to ~1 μm, the phase transition temperature (67 °C for bulk) varied as much as 26.1 °C (19.7 °C) during heating (cooling). In addition, the propagation speed of phase boundary in the microcrystal, i.e., phase transition speed, is monitored at the onset of phase transition bymore » using the high-speed resistance measurement. The phase transition speed increases from 4.6 × 10 2 to 1.7 × 10 4 μm/s as the width decreases from ~50 to ~2 μm. While the statistical description for a heterogeneous nucleation process explains the size dependence on phase transition temperature of VO 2 , the increase of effective thermal exchange process is responsible for the enhancement of phase transition speed of small VO 2 microcrystals. These findings not only enhance the understanding of VO 2 intrinsic properties but also contribute to the development of innovative electronic devices.« less

Near-infrared localized surface plasmon resonance of self-growing W-doped VO2 nanoparticles at room temperature

NASA Astrophysics Data System (ADS)

Nishikawa, Kazutaka; Kishida, Yoshihiro; Ito, Kota; Tamura, Shin-ichi; Takeda, Yasuhiko

2017-11-01

Nanoparticles (NPs) of vanadium dioxide (VO2) in the metal state exhibit localized surface plasmon resonance (LSPR) at 1200-1600 nm, which fills the gap between the absorption ranges of silicon and the LSPR of conventional transparent conductor NPs (ZnO:Al, In2O3:Sn, etc.). However, two issues of the lithographic process for NP formation and the metal-insulator transition temperature (69 °C) higher than room temperature have made it difficult to use VO2 NPs for applications such as energy conversion devices, near infrared (NIR) light detectors, and bio-therapy. In this study, we developed a self-growing process for tungsten (W)-doped VO2 NPs that are in the metal state at room temperature, using sputter deposition and post-lamp annealing. The changes in the LSPR peak wavelengths with the NP size were well controlled by changing the deposited film thickness and oxygen pressure during the post-annealing treatment. The presented results resolve the difficulties of using the metal-insulator transition material VO2 for practical NIR utilization.

Roles of strain and domain boundaries on the phase transition stability of VO2 thin films

NASA Astrophysics Data System (ADS)

Jian, Jie; Chen, Aiping; Chen, Youxing; Zhang, Xinghang; Wang, Haiyan

2017-10-01

The fundamental phase transition mechanism and the stability of the semiconductor-to-metal phase transition properties during multiple thermal cycles have been investigated on epitaxial vanadium dioxide (VO2) thin films via both ex situ heating and in situ heating by transmission electron microscopy (TEM). VO2 thin films were deposited on c-cut sapphire substrates by pulsed laser deposition. Ex situ studies show the broadening of transition sharpness (ΔT) and the width of thermal hysteresis (ΔH) after 60 cycles. In situ TEM heating studies reveal that during thermal cycles, large strain was accumulated around the domain boundaries, which was correlated with the phase transition induced lattice constant change and the thermal expansion. It suggests that the degradation of domain boundary structures in the VO2 films not only caused the transition property reduction (e.g., the decrease in ΔT and ΔH) but also played an important role in preventing the film from fracture during thermal cycles.

Effect of ZnO buffer layer on phase transition properties of vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Zhu, Huiqun; Li, Lekang; Li, Chunbo

2016-03-01

VO2 thin films were prepared on ZnO buffer layers by DC magnetron sputtering at room temperature using vanadium target and post annealing at 400 °C. The ZnO buffer layers with different thickness deposited on glass substrates by magnetron sputtering have a high visible and near infrared optical transmittance. The electrical resistivity and the phase transition properties of the VO2/ZnO composite thin films in terms of temperature were investigated. The results showed that the resistivity variation of VO2 thin film with ZnO buffer layer deposited for 35 min was 16 KΩ-cm. The VO2/ZnO composite thin films exhibit a reversible semiconductor-metal phase transition at 48 °C.

Aqueous citrato-oxovanadate(IV) precursor solutions for VO2: synthesis, spectroscopic investigation and thermal analysis.

PubMed

Peys, Nick; Adriaensens, Peter; Van Doorslaer, Sabine; Gielis, Sven; Peeters, Ellen; De Dobbelaere, Christopher; De Gendt, Stefan; Hardy, An; Van Bael, Marlies K

2014-09-07

An aqueous precursor solution, containing citrato-VO(2+) complexes, is synthesized for the formation of monoclinic VO2. With regard to the decomposition of the VO(2+) complexes towards vanadium oxide formation, it is important to gain insights into the chemical structure and transformations of the precursor during synthesis and thermal treatment. Hence, the conversion of the cyclic [V4O12](4-) ion to the VO(2+) ion in aqueous solution, using oxalic acid as an acidifier and a reducing agent, is studied by (51)Vanadium nuclear magnetic resonance spectroscopy. The citrate complexation of this VO(2+) ion and the differentiation between a solution containing citrato-oxalato-VO(2+) and citrato-VO(2+) complexes are studied by electron paramagnetic resonance and Fourier transform infra-red spectroscopy. In both solutions, the VO(2+) containing complex is mononuclear and has a distorted octahedral geometry with a fourfold R-CO2(-) ligation at the equatorial positions and likely a fifth R-CO2(-) ligation at the axial position. Small differences in the thermal decomposition pathway between the gel containing citrato-oxalato-VO(2+) complexes and the oxalate-free gel containing citrato-VO(2+) complexes are observed between 150 and 200 °C in air and are assigned to the presence of (NH4)2C2O4 in the citrato-oxalato-VO(2+) solution. Both precursor solutions are successfully used for the formation of crystalline vanadium oxide nanostructures on SiO2, after thermal annealing at 500 °C in a 0.1% O2 atmosphere. However, the citrato-oxalato-VO(2+) and the oxalate-free citrato-VO(2+) solution result in the formation of monoclinic V6O13 and monoclinic VO2, respectively.

Inhomogeneity of the ultrafast insulator-to-metal transition dynamics of VO2.

PubMed

O'Callahan, Brian T; Jones, Andrew C; Hyung Park, Jae; Cobden, David H; Atkin, Joanna M; Raschke, Markus B

2015-04-21

The insulator-metal transition (IMT) of vanadium dioxide (VO2) has remained a long-standing challenge in correlated electron physics since its discovery five decades ago. Most interpretations of experimental observations have implicitly assumed a homogeneous material response. Here we reveal inhomogeneous behaviour of even individual VO2 microcrystals using pump-probe microscopy and nanoimaging. The timescales of the ultrafast IMT vary from 40±8 fs, that is, shorter than a suggested phonon bottleneck, to 200±20 fs, uncorrelated with crystal size, transition temperature and initial insulating structural phase, with average value similar to results from polycrystalline thin-film studies. In combination with the observed sensitive variations in the thermal nanodomain IMT behaviour, this suggests that the IMT is highly susceptible to local changes in, for example, doping, defects and strain. Our results suggest an electronic mechanism dominating the photoinduced IMT, but also highlight the difficulty to deduce microscopic mechanisms when the true intrinsic material response is yet unclear.

Electrolysis-induced protonation of VO2 thin film transistor for the metal-insulator phase modulation

NASA Astrophysics Data System (ADS)

Katase, Takayoshi; Endo, Kenji; Ohta, Hiromichi

2016-02-01

Compared to state-of-the-art modulation techniques, protonation is the most ideal to control the electrical and optical properties of transition metal oxides (TMOs) due to its intrinsic non-volatile operation. However, the protonation of TMOs is not typically utilized for solid-state devices because of imperative high-temperature annealing treatment in hydrogen source. Although one solution for room temperature (RT) protonation of TMOs is liquid-phase electrochemistry, it is unsuited for practical purposes due to liquid-leakage problem. Herein we demonstrate solid-state RT-protonation of vanadium dioxide (VO2), which is a well-known thermochromic TMO. We fabricated the three terminal thin-film-transistor structure on an insulating VO2 film using a water-infiltrated nanoporous glass, which serves as a solid electrolyte. For gate voltage application, water electrolysis and protonation/deprotonation of VO2 film surface occurred, leading to reversible metal-insulator phase conversion of ~11-nm-thick VO2 layer. The protonation was clearly accompanied by the structural change from an insulating monoclinic to a metallic tetragonal phase. Present results offer a new route for the development of electro-optically active solid-state devices with TMO materials by engineering RT protonation.

Effect of annealing on optical properties and structure of the vanadium dioxide thin films

NASA Astrophysics Data System (ADS)

Zhu, Huiqun; Li, Yi; Li, Yuming; Huang, Yize; Tong, Guoxiang; Fang, Baoying; Zheng, Qiuxin; Li, Liu; Shen, Yujian

2012-10-01

VO2 thin films were prepared on soda-lime glass substrates by DC magnetron sputtering at room temperature using vanadium target and post annealing in air. X-ray diffraction and FTIR spectroscopy analyses showed that the films obtained at the optimized parameters have high VO2 (011) orientation. Both low temperature deposition and post annealing method were beneficial to grow the nano-films with pure VO2 phase-structure and composition. Metalinsulator transition properties of the VO2 films in terms of infrared transmittance, transmittance variation and film thickness were investigated under varying annealing temperature. Results showed that infrared transmittance variation and transition temperature of the nano-films were significantly improved and reduced respectively. Therefore, this study was able to develop practical low-cost preparation methods for high-performance intelligent energy-saving thin films.

Electrode Reaction Mechanism of Ag 2VO 2PO 4 Cathode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Ruibo; Abtew, Tesfaye A.; Quackenbush, Nicholas F.

In this study, the high capacity of primary lithium-ion cathode Ag 2VO 2PO 4 is facilitated by both displacement and insertion reaction mechanisms. Whether the Ag extrusion (specifically, Ag reduction with Ag metal displaced from the host crystal) and V reduction are sequential or concurrent remains unclear. A microscopic description of the reaction mechanism is required for developing design rules for new multimechanism cathodes, combining both displacement and insertion reactions. However, the amorphization of Ag 2VO 2PO 4 during lithiation makes the investigation of the electrode reaction mechanism difficult with conventional characterization tools. For addressing this issue, a combination ofmore » local probes of pair-distribution function and X-ray spectroscopy were used to obtain a description of the discharge reaction. We determine that the initial reaction is dominated by silver extrusion with vanadium playing a supporting role. In addition, once sufficient Ag has been displaced, the residual Ag + in the host can no longer stabilize the host structure and V–O environment (i.e., onset of amorphization). After amorphization, silver extrusion continues but the vanadium reduction dominates the reaction. As a result, the crossover from primarily silver reduction displacement to vanadium reduction is facilitated by the amorphization that makes vanadium reduction increasingly more favorable.« less

Electrode Reaction Mechanism of Ag 2VO 2PO 4 Cathode

DOE PAGES

Zhang, Ruibo; Abtew, Tesfaye A.; Quackenbush, Nicholas F.; ...

2016-05-09

In this study, the high capacity of primary lithium-ion cathode Ag 2VO 2PO 4 is facilitated by both displacement and insertion reaction mechanisms. Whether the Ag extrusion (specifically, Ag reduction with Ag metal displaced from the host crystal) and V reduction are sequential or concurrent remains unclear. A microscopic description of the reaction mechanism is required for developing design rules for new multimechanism cathodes, combining both displacement and insertion reactions. However, the amorphization of Ag 2VO 2PO 4 during lithiation makes the investigation of the electrode reaction mechanism difficult with conventional characterization tools. For addressing this issue, a combination ofmore » local probes of pair-distribution function and X-ray spectroscopy were used to obtain a description of the discharge reaction. We determine that the initial reaction is dominated by silver extrusion with vanadium playing a supporting role. In addition, once sufficient Ag has been displaced, the residual Ag + in the host can no longer stabilize the host structure and V–O environment (i.e., onset of amorphization). After amorphization, silver extrusion continues but the vanadium reduction dominates the reaction. As a result, the crossover from primarily silver reduction displacement to vanadium reduction is facilitated by the amorphization that makes vanadium reduction increasingly more favorable.« less

Plasmonic Structures for CMOS Photonics and Control of Spontaneous Emission

DTIC Science & Technology

2013-04-01

structures; v) developed CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vi) also engaged in a partnership with...CMOS Si photonic switching device based on the vanadium dioxide ( VO2 ) phase transition. vii. exploring approaches to enhance spontaneous emission in...size and bandwidth, we are exploring phase-change materials and, in particular, vanadium dioxide. VO2 undergoes an insulator-to-metal phase transition

Resistance modulation in VO2 nanowires induced by an electric field via air-gap gates

NASA Astrophysics Data System (ADS)

Kanki, Teruo; Chikanari, Masashi; Wei, Tingting; Tanaka, Hidekazu; The Institute of Scientific; Industrial Research Team

Vanadium dioxide (VO2) shows huge resistance change with metal-insulator transition (MIT) at around room temperature. Controlling of the MIT by applying an electric field is a topical ongoing research toward the realization of Mott transistor. In this study, we have successfully switched channel resistance of VO2 nano-wire channels by a pure electrostatic field effect using a side-gate-type field-effect transistor (SG-FET) viaair gap and found that single crystalline VO2 nanowires and the channels with narrower width enhance transport modulation rate. The rate of change in resistance ((R0-R)/R, where R0 and R is the resistance of VO2 channel with off state and on state gate voltage (VG) , respectively) was 0.42 % at VG = 30 V in in-plane poly-crystalline VO2 channels on Al2O3(0001) substrates, while the rate in single crystalline channels on TiO2 (001) substrates was 3.84 %, which was 9 times higher than that using the poly-crystalline channels. With reducing wire width from 3000 nm to 400 nm of VO2 on TiO2 (001) substrate, furthermore, resistance modulation ratio enhanced from 0.67 % to 3.84 %. This change can not be explained by a simple free-electron model. In this presentation, we will compare the electronic properties between in-plane polycrystalline VO2 on Al2O3 (0001) and single crystalline VO2 on TiO2 (001) substrates, and show experimental data in detail..

Enhancement of electrical transport modulation in epitaxial VO2 nanowire field-effect transistor

NASA Astrophysics Data System (ADS)

Tanaka, Hidekazu; Chikanari, Masashi; Kanki, Teruo

Strongly correlated system vanadium dioxide VO2 has attracted widespread concerns from researchers as an exciting electronic material, due to the many intriguing features, especially metal-insulator transition (MIT) in vicinity of room temperature. In this work, we report a diverse geometry for high sensitivity in the transport modulation. By taking advantage of nanometer scale channel, instead of thin film channels, we demonstrated the enhancement of resistance modulation by applying gate voltage. Also we designed the insulating gate, consisting of high-k material Ta2O5/organic polymer parylene-C hybrid insulator. Such as this hybrid gate dielectric would effectively reduce interface deterioration of active channel oxide and provide sufficient carrier density. Moreover, benefited from the nanometer scale channel, the VO2 nanowire-based transistor could deliver a resistance modulation ratio over 8.5%, which are about 10 folds higher than that of the film case. Furthermore, this result is explained that in spite of the stronger field distribution in the edge parts of VO2 nanowire channel yielded little carrier density, the generated mobility modulation would biquadratic increase according to Brinkman-Rice picture as new finding.

Local coexistence of VO 2 phases revealed by deep data analysis

DOE PAGES

Strelcov, Evgheni; Ievlev, Anton; Tselev, Alexander; ...

2016-07-07

We report a synergistic approach of micro-Raman spectroscopic mapping and deep data analysis to study the distribution of crystallographic phases and ferroelastic domains in a defected Al-doped VO 2 microcrystal. Bayesian linear unmixing revealed an uneven distribution of the T phase, which is stabilized by the surface defects and uneven local doping that went undetectable by other classical analysis techniques such as PCA and SIMPLISMA. This work demonstrates the impact of information recovery via statistical analysis and full mapping in spectroscopic studies of vanadium dioxide systems, which is commonly substituted by averaging or single point-probing approaches, both of which suffermore » from information misinterpretation due to low resolving power.« less

Hydrothermal Synthesis of VO2 Polymorphs: Advantages, Challenges and Prospects for the Application of Energy Efficient Smart Windows.

PubMed

Li, Ming; Magdassi, Shlomo; Gao, Yanfeng; Long, Yi

2017-09-01

Vanadium dioxide (VO 2 ) is a widely studied inorganic phase change material, which has a reversible phase transition from semiconducting monoclinic to metallic rutile phase at a critical temperature of τ c ≈ 68 °C. The abrupt decrease of infrared transmittance in the metallic phase makes VO 2 a potential candidate for thermochromic energy efficient windows to cut down building energy consumption. However, there are three long-standing issues that hindered its application in energy efficient windows: high τ c , low luminous transmittance (T lum ), and undesirable solar modulation ability (ΔT sol ). Many approaches, including nano-thermochromism, porous films, biomimetic surface reconstruction, gridded structures, antireflective overcoatings, etc, have been proposed to tackle these issues. The first approach-nano-thermochromism-which is to integrate VO 2 nanoparticles in a transparent matrix, outperforms the rest; while the thermochromic performance is determined by particle size, stoichiometry, and crystallinity. A hydrothermal method is the most common method to fabricate high-quality VO 2 nanoparticles, and has its own advantages of large-scale synthesis and precise phase control of VO 2 . This Review focuses on hydrothermal synthesis, physical properties of VO 2 polymorphs, and their transformation to thermochromic VO 2 (M), and discusses the advantages, challenges, and prospects of VO 2 (M) in energy-efficient smart windows application. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Exploratory Phase Transition-Based Switches Using Functional Oxides

DTIC Science & Technology

2011-02-02

TECHNICAL REPORT Abstract Vanadium dioxide ( VO2 ) undergoes a sharp metal-insulator transition (MIT) in the vicinity of room temperature and there is...18 The mechanisms governing metal-insulator transition (MIT) in vanadium dioxide ( VO2 ) is an intensively explored subject in condensed matter...textured vanadium dioxide films were grown on single crystal Al2O3 (0001) substrates by RF-sputtering from a VO2 target (99.5%, AJA International Inc

Electrochemical Synthesis of Amorphous VO2 Colloids and Their Rapid Thermal Transforming to VO2 (M) Nanoparticles with Good Thermochromic Performance.

PubMed

Wu, Hao; Li, Ming; Zhong, Li; Luo, Yuan Yuan; Li, Guang Hai

2016-12-05

Amorphous VO 2 (a-VO 2 ) colloids were synthesized by electrochemical anodic oxidation of metallic vanadium. It was found that the a-VO 2 colloids have a cotton-like morphology composed of very small clusters, and that the crystallization temperature of the a-VO 2 colloids can be adjusted either by the electrolyte of the anodic oxidation or/and the dispersion agent of the colloids. VO 2 (M) nanoparticles (NPs) (and a NP film) with an average size of about 50 nm can be obtained by a rapid thermal annealing of the a-VO 2 colloids at 310 °C under air, which is beneficial for practical applications. The VO 2 (M) NP film shows an obvious metal-semiconductor transition with a resistance less than 10 Ω in the metallic state. An integral visible transmittance of 40.7 %, a solar transmittance modulation of 9.4 %, and a resistance modulation in the order of 5×10 4 were realized in the VO 2 (M) NP film. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

n-VO2/p-GaN based nitride-oxide heterostructure with various thickness of VO2 layer grown by MBE

NASA Astrophysics Data System (ADS)

Wang, Minhuan; Bian, Jiming; Sun, Hongjun; Liu, Weifeng; Zhang, Yuzhi; Luo, Yingmin

2016-12-01

High quality VO2 films with precisely controlled thickness were grown on p-GaN/sapphire substrates by oxide molecular beam epitaxy (O-MBE). Results indicated that a distinct reversible semiconductor-to-metal (SMT) phase transition was observed for all the samples in the temperature dependent electrical resistance measurement, and the influence of VO2 layer thickness on the SMT properties of the as-grown n-VO2/p-GaN based nitride-oxide heterostructure was investigated. Meanwhile, the clear rectifying transport characteristics originated from the n-VO2/p-GaN interface were demonstrated before and after SMT of the VO2 over layer, which were attributed to the p-n junction behavior and Schottky contact character, respectively. Moreover, the X-ray photoelectron spectroscopy (XPS) analyses confirmed the valence state of vanadium (V) in VO2 films was principally composed of V4+ with trace amount of V5+. The design and modulation of the n-VO2/p-GaN based heterostructure devices will benefit significantly from these achievements.

Comprehensive studies of interfacial strain and oxygen vacancy on metal-insulator transition of VO2 film

NASA Astrophysics Data System (ADS)

Fan, L. L.; Chen, S.; Liao, G. M.; Chen, Y. L.; Ren, H.; Zou, C. W.

2016-06-01

As a typical strong correlation material, vanadium dioxide (VO2) has attracted wide interest due to its particular metal-insulator transition (MIT) property. However, the relatively high critical temperature (T c) of ~68 °C seriously hinders its practical applications. Thus modulating the phase transition process and decreasing the T c close to room temperature have been hot topics for VO2 study. In the current work, we conducted a multi-approach strategy to control the phase transition of VO2 films, including the interfacial tensile/compressive strain and oxygen vacancies. A synchrotron radiation reciprocal space mapping technique was used to directly record the interfacial strain evolution and variations of lattice parameters. The effects of interfacial strain and oxygen vacancies in the MIT process were systematically investigated based on band structure and d-orbital electron occupation. It was suggested that the MIT behavior can be modulated through the combined effects of the interfacial strain and oxygen vacancies, achieving the distinct phase transition close to room temperature. The current findings not only provide better understanding for strain engineering and oxygen vacancies controlling phase transition behavior, but also supply a combined way to control the phase transition of VO2 film, which is essential for VO2 film based device applications in the future.

Comprehensive studies of interfacial strain and oxygen vacancy on metal-insulator transition of VO2 film.

PubMed

Fan, L L; Chen, S; Liao, G M; Chen, Y L; Ren, H; Zou, C W

2016-06-29

As a typical strong correlation material, vanadium dioxide (VO2) has attracted wide interest due to its particular metal-insulator transition (MIT) property. However, the relatively high critical temperature (T c) of ~68 °C seriously hinders its practical applications. Thus modulating the phase transition process and decreasing the T c close to room temperature have been hot topics for VO2 study. In the current work, we conducted a multi-approach strategy to control the phase transition of VO2 films, including the interfacial tensile/compressive strain and oxygen vacancies. A synchrotron radiation reciprocal space mapping technique was used to directly record the interfacial strain evolution and variations of lattice parameters. The effects of interfacial strain and oxygen vacancies in the MIT process were systematically investigated based on band structure and d-orbital electron occupation. It was suggested that the MIT behavior can be modulated through the combined effects of the interfacial strain and oxygen vacancies, achieving the distinct phase transition close to room temperature. The current findings not only provide better understanding for strain engineering and oxygen vacancies controlling phase transition behavior, but also supply a combined way to control the phase transition of VO2 film, which is essential for VO2 film based device applications in the future.

Invited Article: An active terahertz polarization converter employing vanadium dioxide and a metal wire grating in total internal reflection geometry

NASA Astrophysics Data System (ADS)

Liu, Xudong; Chen, Xuequan; Parrott, Edward P. J.; Han, Chunrui; Humbert, Georges; Crunteanu, Aurelian; Pickwell-MacPherson, Emma

2018-05-01

Active broadband terahertz (THz) polarization manipulation devices are challenging to realize, but also of great demand in broadband terahertz systems. Vanadium dioxide (VO2) shows a promising phase transition for active control of THz waves and provides broadband polarization characteristics when integrated within grating-type structures. We creatively combine a VO2-based grating structure with a total internal reflection (TIR) geometry providing a novel interaction mechanism between the electromagnetic waves and the device, to realize a powerful active broadband THz polarization-controlling device. The device is based on a Si-substrate coated with a VO2 layer and a metal grating structure on top, attached to a prism for generating the TIR condition on the Si-VO2-grating interface. The grating is connected to electrodes for electrically switching the VO2 between its insulating and conducting phases. By properly selecting the incident angle of the THz waves, the grating direction, and the incident polarization state, we first achieved a broadband intensity modulator under a fused silica prism with an average modulation depth of 99.75% in the 0.2-1.1 THz region. Additionally, we realized an active ultra-broadband quarter-wave converter under a Si prism that can be switched between a 45° linear rotator and a quarter wave converter in the 0.8-1.5 THz region. This is the first demonstration of an active quarter-wave converter with ultra-broad bandwidth performance. Our work shows a highly flexible and multifunctional polarization-controlling device for broadband THz applications.

Metallization of vanadium dioxide driven by large phonon entropy

DOE PAGES

Budai, John D.; Hong, Jiawang; Manley, Michael E.; ...

2014-11-10

Phase competition underlies many remarkable and technologically important phenomena in transition-metal oxides. Vanadium dioxide exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. Ongoing attempts to explain this coupled structural and electronic transition begin with two classic starting points: a Peierls MIT driven by instabilities in electron-lattice dynamics versus a Mott MIT where strong electron-electron correlations drive charge localization1-10. A key-missing piece of the VO2 puzzle is the role of lattice vibrations. Moreover, a comprehensive thermodynamic treatment must integrate both entropic and energetic aspects of themore » transition. Our measurements establish that the entropy driving the MIT is dominated by strongly anharmonic phonons rather than electronic contributions, and provide a direct determination of phonon dispersions. Our calculations identify softer bonding as the origin of the large vibrational entropy stabilizing the metallic rutile phase. They further reveal how a balance between higher entropy in the metal and orbital-driven lower energy in the insulator fully describes the thermodynamic forces controlling the MIT. This study illustrates the critical role of anharmonic lattice dynamics in metal-oxide phase competition, and provides guidance for the predictive design of new materials.« less

Intensity tunable infrared broadband absorbers based on VO2 phase transition using planar layered thin films

PubMed Central

Kocer, Hasan; Butun, Serkan; Palacios, Edgar; Liu, Zizhuo; Tongay, Sefaattin; Fu, Deyi; Wang, Kevin; Wu, Junqiao; Aydin, Koray

2015-01-01

Plasmonic and metamaterial based nano/micro-structured materials enable spectrally selective resonant absorption, where the resonant bandwidth and absorption intensity can be engineered by controlling the size and geometry of nanostructures. Here, we demonstrate a simple, lithography-free approach for obtaining a resonant and dynamically tunable broadband absorber based on vanadium dioxide (VO2) phase transition. Using planar layered thin film structures, where top layer is chosen to be an ultrathin (20 nm) VO2 film, we demonstrate broadband IR light absorption tuning (from ~90% to ~30% in measured absorption) over the entire mid-wavelength infrared spectrum. Our numerical and experimental results indicate that the bandwidth of the absorption bands can be controlled by changing the dielectric spacer layer thickness. Broadband tunable absorbers can find applications in absorption filters, thermal emitters, thermophotovoltaics and sensing. PMID:26294085

Study of the resonant frequencies of silicon microcantilevers coated with vanadium dioxide films during the insulator-to-metal transition

NASA Astrophysics Data System (ADS)

Rúa, Armando; Fernández, Félix E.; Hines, Melissa A.; Sepúlveda, Nelson

2010-03-01

Vanadium dioxide (VO2) thin films were grown on silicon microcantilevers and companion test substrates by pulsed laser deposition followed by in situ annealing in an oxidizing atmosphere, with annealing times used to control crystallite sizes. Annealing times of 18 min produced VO2 films with average crystallite sizes of ˜10 nm or less, while those annealed for 35 min had crystallites of average size ˜90 nm, comparable to sample thickness. X-ray diffraction and x-ray photoelectron spectroscopy studies of the samples showed that films with crystallite sizes ˜40 nm or greater consisted of substoichiometric VO2 in its monoclinic phase, with preferential orientation with (011) planes parallel to the sample surface, while finer structured samples had a substantially similar composition, but showed no clear evidence of preferential orientation and were probably partially amorphous. Forced vibration experiments were performed with the cantilevers as they were thermally cycled through the VO2 insulator-to-metal transition (IMT). Very large reversible changes in the resonant frequencies of up to 5% (3.6 kHz) as well as hysteretic behavior were observed, which depend strongly on film crystallite size. The average value of Young's modulus for VO2 films with crystallite sizes of ˜90 nm was estimated from the mechanical resonance data at room temperature to be ˜120 GPa, but the large tensile stresses which develop between film and substrate through the IMT impede a similar determination for the VO2 tetragonal phase, since the commonly used relationships for cantilever frequencies derived from elasticity theory are not applicable for strongly curved composite beams. The results presented show that VO2 thin films can be useful in novel microscale and nanoscale electromechanical resonators in which effective stiffness can be tuned thermally or optically. This response can provide additional functionality to VO2—based devices which take advantage of other property changes

C=C bond cleavage on neutral VO3(V2O5)n clusters.

PubMed

Dong, Feng; Heinbuch, Scott; Xie, Yan; Bernstein, Elliot R; Rocca, Jorge J; Wang, Zhe-Chen; Ding, Xun-Lei; He, Sheng-Gui

2009-01-28

The reactions of neutral vanadium oxide clusters with alkenes (ethylene, propylene, 1-butene, and 1,3-butadiene) are investigated by experiments and density function theory (DFT) calculations. Single photon ionization through extreme ultraviolet radiation (EUV, 46.9 nm, 26.5 eV) is used to detect neutral cluster distributions and reaction products. In the experiments, we observe products (V(2)O(5))(n)VO(2)CH(2), (V(2)O(5))(n)VO(2)C(2)H(4), (V(2)O(5))(n)VO(2)C(3)H(4), and (V(2)O(5))(n)VO(2)C(3)H(6), for neural V(m)O(n) clusters in reactions with C(2)H(4), C(3)H(6), C(4)H(6), and C(4)H(8), respectively. The observation of these products indicates that the C=C bonds of alkenes can be broken on neutral oxygen rich vanadium oxide clusters with the general structure VO(3)(V(2)O(5))(n=0,1,2...). DFT calculations demonstrate that the reaction VO(3) + C(3)H(6) --> VO(2)C(2)H(4) + H(2)CO is thermodynamically favorable and overall barrierless at room temperature. They also provide a mechanistic explanation for the general reaction in which the C=C double bond of alkenes is broken on VO(3)(V(2)O(5))(n=0,1,2...) clusters. A catalytic cycle for alkene oxidation on vanadium oxide is suggested based on our experimental and theoretical investigations. The reactions of V(m)O(n) with C(6)H(6) and C(2)F(4) are also investigated by experiments. The products VO(2)(V(2)O(5))(n)C(6)H(4) are observed for dehydration reactions between V(m)O(n) clusters and C(6)H(6). No product is detected for V(m)O(n) clusters reacting with C(2)F(4). The mechanisms of the reactions between VO(3) and C(2)F(4)/C(6)H(6) are also investigated by calculations at the B3LYP/TZVP level.

Van der Waals MoS2/VO2 heterostructure junction with tunable rectifier behavior and efficient photoresponse.

PubMed

Oliva, Nicoló; Casu, Emanuele Andrea; Yan, Chen; Krammer, Anna; Rosca, Teodor; Magrez, Arnaud; Stolichnov, Igor; Schueler, Andreas; Martin, Olivier J F; Ionescu, Adrian Mihai

2017-10-27

Junctions between n-type semiconductors of different electron affinity show rectification if the junction is abrupt enough. With the advent of 2D materials, we are able to realize thin van der Waals (vdW) heterostructures based on a large diversity of materials. In parallel, strongly correlated functional oxides have emerged, having the ability to show reversible insulator-to-metal (IMT) phase transition by collapsing their electronic bandgap under a certain external stimulus. Here, we report for the first time the electronic and optoelectronic characterization of ultra-thin n-n heterojunctions fabricated using deterministic assembly of multilayer molybdenum disulphide (MoS 2 ) on a phase transition material, vanadium dioxide (VO 2 ). The vdW MoS 2 /VO 2 heterojunction combines the excellent blocking capability of an n-n junction with a high conductivity in on-state, and it can be turned into a Schottky rectifier at high applied voltage or at temperatures higher than 68 °C, exploiting the metal state of VO 2 . We report tunable diode-like current rectification with a good diode ideality factor of 1.75 and excellent conductance swing of 120 mV/dec. Finally, we demonstrate unique tunable photosensitivity and excellent junction photoresponse in the 500/650 nm wavelength range.

Chromium–niobium co-doped vanadium dioxide films: Large temperature coefficient of resistance and practically no thermal hysteresis of the metal–insulator transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miyazaki, Kenichi, E-mail: kenichi-miyazaki@denso.co.jp, E-mail: k.shibuya@aist.go.jp; University of Tsukuba, Tsukuba 305-8571; Shibuya, Keisuke, E-mail: kenichi-miyazaki@denso.co.jp, E-mail: k.shibuya@aist.go.jp

We investigated the effects of chromium (Cr) and niobium (Nb) co-doping on the temperature coefficient of resistance (TCR) and the thermal hysteresis of the metal–insulator transition of vanadium dioxide (VO{sub 2}) films. We determined the TCR and thermal-hysteresis-width diagram of the V{sub 1−x−y}Cr{sub x}Nb{sub y}O{sub 2} films by electrical-transport measurements and we found that the doping conditions x ≳ y and x + y ≥ 0.1 are appropriate for simultaneously realizing a large TCR value and an absence of thermal hysteresis in the films. By using these findings, we developed a V{sub 0.90}Cr{sub 0.06}Nb{sub 0.04}O{sub 2} film grown on amore » TiO{sub 2}-buffered SiO{sub 2}/Si substrate that showed practically no thermal hysteresis while retaining a large TCR of 11.9%/K. This study has potential applications in the development of VO{sub 2}-based uncooled bolometers.« less

Anomalous spectral-weight transfers unraveling oxygen screening and electronic correlations in the insulator-metal transition of VO2

NASA Astrophysics Data System (ADS)

Yeo, L. H.; Srivastava, A.; Majidi, M. A.; Sutarto, R.; He, F.; Poh, S. M.; Diao, C.; Yu, X.; Motapothula, M.; Saha, S.; Ojha, S.; Kanjilal, D.; Trevisanutto, P. E.; Breese, M. B. H.; Venkatesan, T.; Rusydi, A.

2015-02-01

Vanadium dioxide (VO2) undergoes an unusual insulator-metal transition (IMT), and after decades of study, the origin of the IMT remains hotly debated. Here, by analyzing spectral-weight transfers (SWTs) of x-ray absorption spectroscopy at the V L3 ,2 and O K edges on specially designed VO2 films, we observe d||(dx2-y2) band splitting at the V L3 ,2 edges across the IMT, accompanied by anomalous SWTs as high as ˜12 eV at the O K edge, indicating strong electronic correlations. Surprisingly, a few oxygen vacancies induce dramatic SWTs at the O K edge, but the sample remains conducting. Supported by theoretical calculations, we find that in the metallic state, direct V (3 d∥) -V(3 d∥) and O(2 p ) -V(3 d∥) hybridized orbital correlations are screened by O(2 p ) -V(3 dπ) hybridized orbitals, while in the insulating state they are strongly correlated due to changes in the oxygen orbital occupancy. Our result shows the importance of screenings and electronic correlations for IMTs in VO2.

Coherent control of optical absorption and the energy transfer pathway of an infrared quantum dot hybridized with a VO2 nanoparticle

NASA Astrophysics Data System (ADS)

Hatef, Ali; Zamani, Naser; Johnston, William

2017-04-01

We systematically investigate the optical response of a semiconductor quantum dot (QD) hybridized with a vanadium dioxide nanoparticle (VO2NP) in the infrared (IR) region. The VO2NP features a semiconductor to metal phase change characteristic below and above a critical temperature that leads to an abrupt change in the particle’s optical properties. This feature means that the QD-VO2NP hybrid system can support the coherent coupling of exciton-polaritons and exciton-plasmon polaritons in the semiconductor and metal phases of the VO2NP, respectively. In our calculations, the VO2NP phase transition is modelled with a filling fraction (f), representing the fraction of the VO2NP in the metallic phase. The phase transition is driven by the hybrid system’s interaction with a continuous wave (CW) IR laser field. In this paper, we show how control over the filling fraction results in the enhancement or suppression of the QD’s linear absorption. These variations in the QD absorption is due to dramatic changes in the effective local field experienced by the QD and the non-radiative energy transfer from the QD to the VO2NP. The presented results have the potential to be applied to the design of thermal sensors at the nanoscale.

Preparation, Characterization and Thermo-Chromic Properties of EVA/VO2 Laminate Films for Smart Window Applications and Energy Efficiency in Building

PubMed Central

Srirodpai, Onruthai; Wootthikanokkhan, Jatuphorn; Nawalertpanya, Saiwan; Yuwawech, Kitti; Meeyoo, Vissanu

2017-01-01

Thermochromic films based on vanadium dioxide (VO2)/ethylene vinyl acetate copolymer (EVA) composite were developed. The monoclinic VO2 particles was firstly prepared via hydrothermal and calcination processes. The effects of hydrothermal time and tungsten doping agent on crystal structure and morphology of the calcined metal oxides were reported. After that, 1 wt % of the prepared VO2 powder was mixed with EVA compound, using two different mixing processes. It was found that mechanical properties of the EVA/VO2 films prepared by the melt process were superior to those of which prepared by the solution process. On the other hand, percentage visible light transmittance of the solution casted EVA/VO2 film was greater than that of the melt processed composite film. This was related to the different gel content of EVA rubber and state of dispersion and distribution of VO2 within the polymer matrix phase. Thermochromic behaviors and heat reflectance of the EVA/VO2 film were also verified. In overall, this study demonstrated that it was possible to develop a thermochromic film using the polymer composite approach. In this regard, the mixing condition was found to be one of the most important factors affecting morphology and thermo-mechanical properties of the films. PMID:28772413

Imaging metal-like monoclinic phase stabilized by surface coordination effect in vanadium dioxide nanobeam

PubMed Central

Li, Zejun; Wu, Jiajing; Hu, Zhenpeng; Lin, Yue; Chen, Qi; Guo, Yuqiao; Liu, Yuhua; Zhao, Yingcheng; Peng, Jing; Chu, Wangsheng; Wu, Changzheng; Xie, Yi

2017-01-01

In correlated systems, intermediate states usually appear transiently across phase transitions even at the femtosecond scale. It therefore remains an open question how to determine these intermediate states—a critical issue for understanding the origin of their correlated behaviour. Here we report a surface coordination route to successfully stabilize and directly image an intermediate state in the metal-insulator transition of vanadium dioxide. As a prototype metal-insulator transition material, we capture an unusual metal-like monoclinic phase at room temperature that has long been predicted. Coordinate bonding of L-ascorbic acid molecules with vanadium dioxide nanobeams induces charge-carrier density reorganization and stabilizes metallic monoclinic vanadium dioxide, unravelling orbital-selective Mott correlation for gap opening of the vanadium dioxide metal–insulator transition. Our study contributes to completing phase-evolution pathways in the metal-insulator transition process, and we anticipate that coordination chemistry may be a powerful tool for engineering properties of low-dimensional correlated solids. PMID:28613281

Atomic Origins of Monoclinic-Tetragonal (Rutile) Phase Transition in Doped VO2 Nanowires.

PubMed

Asayesh-Ardakani, Hasti; Nie, Anmin; Marley, Peter M; Zhu, Yihan; Phillips, Patrick J; Singh, Sujay; Mashayek, Farzad; Sambandamurthy, Ganapathy; Low, Ke-Bin; Klie, Robert F; Banerjee, Sarbajit; Odegard, Gregory M; Shahbazian-Yassar, Reza

2015-11-11

There has been long-standing interest in tuning the metal-insulator phase transition in vanadium dioxide (VO2) via the addition of chemical dopants. However, the underlying mechanisms by which doping elements regulate the phase transition in VO2 are poorly understood. Taking advantage of aberration-corrected scanning transmission electron microscopy, we reveal the atomistic origins by which tungsten (W) dopants influence the phase transition in single crystalline WxV1-xO2 nanowires. Our atomically resolved strain maps clearly show the localized strain normal to the (122̅) lattice planes of the low W-doped monoclinic structure (insulator). These strain maps demonstrate how anisotropic localized stress created by dopants in the monoclinic structure accelerates the phase transition and lead to relaxation of structure in tetragonal form. In contrast, the strain distribution in the high W-doped VO2 structure is relatively uniform as a result of transition to tetragonal (metallic) phase. The directional strain gradients are furthermore corroborated by density functional theory calculations that show the energetic consequences of distortions to the local structure. These findings pave the roadmap for lattice-stress engineering of the MIT behavior in strongly correlated materials for specific applications such as ultrafast electronic switches and electro-optical sensors.

Solution-Processed VO2-SiO2 Composite Films with Simultaneously Enhanced Luminous Transmittance, Solar Modulation Ability and Anti-Oxidation property

PubMed Central

Zhao, Lili; Miao, Lei; Liu, Chengyan; Li, Chao; Asaka, Toru; Kang, Yipu; Iwamoto, Yuji; Tanemura, Sakae; Gu, Hui; Su, Huirong

2014-01-01

Recently, researchers spare no efforts to fabricate desirable vanadium dioxide (VO2) film which provides simultaneously high luminous transmittance and outstanding solar modulation ability, yet progress towards the optimization of one aspect always comes at the expense of the other. Our research devotes to finding a reproducible economic solution-processed strategy for fabricating VO2-SiO2 composite films, with the aim of boosting the performance of both aspects. Compare to VO2 film, an improvement of 18.9% (from 29.6% to 48.5%) in the luminous transmittance as well as an increase of 6.0% (from 9.7% to 15.7%) in solar modulation efficiency is achieved when the molar ratio of Si/V attains 0.8. Based on the effective medium theory, we simulate the optical spectra of the composite films and the best thermochromic property is obtained when the filling factor attains 0.5, which is consistent with the experimental results. Meanwhile, the improvement of chemical stability for the composite film against oxidation has been confirmed. Tungsten is introduced to reduce the phase transition temperature to the ambient temperature, while maintain the thermochromism required for application as smart window. Our research set forth a new avenue in promoting practical applications of VO2-based thermochromic fenestration. PMID:25384345

Solution-Processed VO2-SiO2 Composite Films with Simultaneously Enhanced Luminous Transmittance, Solar Modulation Ability and Anti-Oxidation property

NASA Astrophysics Data System (ADS)

Zhao, Lili; Miao, Lei; Liu, Chengyan; Li, Chao; Asaka, Toru; Kang, Yipu; Iwamoto, Yuji; Tanemura, Sakae; Gu, Hui; Su, Huirong

2014-11-01

Recently, researchers spare no efforts to fabricate desirable vanadium dioxide (VO2) film which provides simultaneously high luminous transmittance and outstanding solar modulation ability, yet progress towards the optimization of one aspect always comes at the expense of the other. Our research devotes to finding a reproducible economic solution-processed strategy for fabricating VO2-SiO2 composite films, with the aim of boosting the performance of both aspects. Compare to VO2 film, an improvement of 18.9% (from 29.6% to 48.5%) in the luminous transmittance as well as an increase of 6.0% (from 9.7% to 15.7%) in solar modulation efficiency is achieved when the molar ratio of Si/V attains 0.8. Based on the effective medium theory, we simulate the optical spectra of the composite films and the best thermochromic property is obtained when the filling factor attains 0.5, which is consistent with the experimental results. Meanwhile, the improvement of chemical stability for the composite film against oxidation has been confirmed. Tungsten is introduced to reduce the phase transition temperature to the ambient temperature, while maintain the thermochromism required for application as smart window. Our research set forth a new avenue in promoting practical applications of VO2-based thermochromic fenestration.

Structure and Properties of VO2 and Titanium Dioxide Based Epitaxial Heterostructures Integrated with Silicon and Sapphire Substrates

NASA Astrophysics Data System (ADS)

Bayati, Mohammad Reza

application in environmental remediation was taken into account. The photochemical efficiency of the samples was evaluated under ultraviolet and visible illuminations. I was able to establish a correlation between the growth conditions and the photocatalytic activity of single crystalline TiO 2 thin films. Visible-light-responsive TiO2 films were fabricated via vacuum annealing of the samples where point defects, namely oxygen vacancies and titanium interstitial, are surmised to play a critical role. An ultrafast switching was observed in wetting characteristics of the single crystalline rutile TiO2 films from a hydrophobic state to a superhydrophilic state by single pulsed excimer laser annealing. It was observed that the laser annealing almost doubles the photocatalytic efficiency of the anatase epitaxial thin films. I was able to measure the photochemical properties of the rutile and the anatase TiO2 heterostructures in a controlled way due to the single crystalline nature of the films. Second, the rutile TiO2 epilayers with different out-of-plane orientations were deposited and used as a platform for VO2 based epitaxial heterostructures with the aim of manipulating of microstructure and electrical properties of the VO 2 films. Vanadium dioxide (VO2) is an interesting material due to the abrupt change in electrical resistivity and infrared transmittance at about 68 °C. The transition temperature can be tuned through microstructural engineering. It was the idea behind using rutile TiO2 with different crystallographic orientations as a template to tune the semiconductor to metal transition characteristics of the VO2 top layer. I successfully grew VO2(001), VO2(100), and VO2(2¯01) epitaxial thin films on TiO2(100)/c-sapphire, TiO2(101)/r-sapphire, and TiO2(001)/ m-sapphire platforms, respectively. It was observed that tetragonal phase of VO2 was stabilized at lower temperatures leading to a significant decrease in the semiconductor to metal transition temperature. In other

In-Plane Impedance Spectroscopy measurements in Vanadium Dioxide thin films

NASA Astrophysics Data System (ADS)

Ramirez, Juan; Patino, Edgar; Schmidt, Rainer; Sharoni, Amos; Gomez, Maria; Schuller, Ivan

2012-02-01

In plane Impedance Spectroscopy measurements have been done in Vanadium Dioxide thin films in the range of 100 Hz to 1 MHz. Our measurements allows distinguishing between the resistive and capacitive response of the Vanadium Dioxide films across the metal-insulator transition. A non ideal RC behavior was found in our thin films from room temperature up to 334 K. Around the MIT, an increase of the total capacitance is observed. A capacitor-network model is able to reproduce the capacitance changes across the MIT. Above the MIT, the system behaves like a metal as expected, and a modified equivalent circuit is necessary to describe the impedance data adequately.

Identifying the active site in nitrogen-doped graphene for the VO2+/VO2(+) redox reaction.

PubMed

Jin, Jutao; Fu, Xiaogang; Liu, Qiao; Liu, Yanru; Wei, Zhiyang; Niu, Kexing; Zhang, Junyan

2013-06-25

Nitrogen-doped graphene sheets (NGS), synthesized by annealing graphite oxide (GO) with urea at 700-1050 °C, were studied as positive electrodes in a vanadium redox flow battery. The NGS, in particular annealed at 900 °C, exhibited excellent catalytic performance in terms of electron transfer (ET) resistance (4.74 ± 0.51 and 7.27 ± 0.42 Ω for the anodic process and cathodic process, respectively) and reversibility (ΔE = 100 mV, Ipa/Ipc = 1.38 at a scan rate of 50 mV s(-1)). Detailed research confirms that not the nitrogen doping level but the nitrogen type in the graphene sheets determines the catalytic activity. Among four types of nitrogen species doped into the graphene lattice including pyridinic-N, pyrrolic-N, quaternary nitrogen, and oxidic-N, quaternary nitrogen is verified as a catalytic active center for the [VO](2+)/[VO2](+) couple reaction. A mechanism is proposed to explain the electrocatalytic performance of NGS for the [VO](2+)/[VO2](+) couple reaction. The possible formation of a N-V transitional bonding state, which facilitates the ET between the outer electrode and reactant ions, is a key step for its high catalytic activity.

Metal-semiconductor phase transition of order arrays of VO2 nanocrystals

NASA Astrophysics Data System (ADS)

Lopez, Rene; Suh, Jae; Feldman, Leonard; Haglund, Richard

2004-03-01

The study of solid-state phase transitions at nanometer length scales provides new insights into the effects of material size on the mechanisms of structural transformations. Such research also opens the door to new applications, either because materials properties are modified as a function of particle size, or because the nanoparticles interact with a surrounding matrix material, or with each other. In this paper, we describe the formation of vanadium dioxide nanoparticles in silicon substrates by pulsed laser deposition of ion beam lithographically selected sites and thermal processing. We observe the collective behavior of 50 nm diameter VO2 oblate nanoparticles, 10 nm high, and ordered in square arrays with arbitrary lattice constant. The metal-semiconductor-transition of the VO2 precipitates shows different features in each lattice spacing substrate. The materials are characterized by electron microscopy, x-ray diffraction, Rutherford backscattering. The features of the phase transition are studied via infrared optical spectroscopy. Of particular interest are the enhanced scattering and the surface plasmon resonance when the particles reach the metallic state. This resonance amplifies the optical contrast in the range of near-infrared optical communication wavelengths and it is altered by the particle-particle coupling as in the case of noble metals. In addition the VO2 nanoparticles exhibit sharp transitions with up to 50 K of hysteresis, one of the largest values ever reported for this transition. The optical properties of the VO2 nanoarrays are correlated with the size of the precipitates and their inter-particle distance. Nonlinear and ultra fast optical measurements have shown that the transition is the fastest known solid-solid transformation. The VO2 nanoparticles show the same bulk property, transforming in times shorter than 150 fs. This makes them remarkable candidates for ultrafast optical and electronic switching applications.

Exploring the work function variability and structural stability of VO2(1 1 0) surface upon noble metal (Ag, Au, Pt) adsorption and incorporation

NASA Astrophysics Data System (ADS)

Chen, Lanli; Cui, Yuanyuan; Shi, Siqi; Luo, Hongjie; Gao, Yanfeng

2018-08-01

Vanadium dioxide (VO2) has attracted great attention, with scientific and technological advances over the past few decades due to its reversible metal-insulator transition at 340 K. However, the high phase transition temperature (Tc) of VO2 limits its practical applications. Our first-principles calculations show that VO2(1 1 0) surfaces with adsorbed noble metals (Ag, Au, Pt) exhibit a lower work function compared with the clean surface and further induces a lower Tc due to charge transfer from the noble metals to the VO2(1 1 0) surface. However, the work functions of the VO2(1 1 0) surfaces after the incorporation of noble metals are higher than that of the clean surface. In addition, the results of formation energies of various configurations show that the VO2(1 1 0) surface with the adsorption and incorporation of Ag is energetically more favorable than those with Au and Pt. Therefore, it may be concluded that the adsorption and incorporation of noble metals can not only tailor the work function of VO2, in turn realizing the rational tuning of Tc of VO2, but also stabilize the structures of VO2 thin films. These results provide guidance for further exploration of VO2-based optical switching devices and smart windows.

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

NASA Astrophysics Data System (ADS)

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan; Heinonen, Olle; Kent, Paul R. C.; Krogel, Jaron T.

2017-11-01

Diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3 d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et al. [Science 355, 371 (2017), 10.1126/science.aag0410] in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VO2, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development. With our reference data, the accuracy of both the energy and the electron density can be monitored simultaneously, which is useful for functional development. So far, this kind of detailed high accuracy reference data for correlated materials has been absent from the literature.

Effect of annealing temperature on thermochromic properties of vanadium dioxide thin films deposited by organic sol-gel method

NASA Astrophysics Data System (ADS)

Wu, Jing; Huang, Wanxia; Shi, Qiwu; Cai, Jinghan; Zhao, Dong; Zhang, Yubo; Yan, Jiazhen

2013-03-01

This paper described the synthesis of vanadium dioxide (VO2) thin films on mica substrates with different annealing temperatures by an organic sol-gel method. We performed X-ray diffraction, scanning electron microscope and optical transmission measurements to investigate the effect of the annealing temperature on the crystalline structure, morphology, and phase transition properties of these films. The results showed that a polycrystalline structure with high crystallinity and compact surface at the annealing temperature of 500 °C. The film exhibited a V6O13 phase and a flat surface with small grain size at 440 °C. By contrast, the VnO2n-1 appeared when the annealing temperature at 540 °C, and the film surface split into segregation of spherical grain and aggregates of continuously dendritic particles. Accordingly, the optimal annealing temperature was 500 °C using the organic sol-gel method. And it turned out that the films mainly contained VO2 (M) phase at room temperature with high content of V4+ valence. Particularly, the films showed different changes in the infrared transmittance and hysteresis width during the phase transition. The largest transformation of the infrared transmittance before and after MIT was 73%, while the narrowest temperature hysteresis width was 8 °C at 500 °C.

VO2 Thermochromic Films on Quartz Glass Substrate Grown by RF-Plasma-Assisted Oxide Molecular Beam Epitaxy

PubMed Central

Zhang, Dong; Sun, Hong-Jun; Wang, Min-Huan; Miao, Li-Hua; Liu, Hong-Zhu; Zhang, Yu-Zhi; Bian, Ji-Ming

2017-01-01

Vanadium dioxide (VO2) thermochromic thin films with various thicknesses were grown on quartz glass substrates by radio frequency (RF)-plasma assisted oxide molecular beam epitaxy (O-MBE). The crystal structure, morphology and chemical stoichiometry were investigated systemically by X-ray diffraction (XRD), atomic force microscopy (AFM), Raman spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. An excellent reversible metal-to-insulator transition (MIT) characteristics accompanied by an abrupt change in both electrical resistivity and optical infrared (IR) transmittance was observed from the optimized sample. Remarkably, the transition temperature (TMIT) deduced from the resistivity-temperature curve was reasonably consistent with that obtained from the temperature-dependent IR transmittance. Based on Raman measurement and XPS analyses, the observations were interpreted in terms of residual stresses and chemical stoichiometry. This achievement will be of great benefit for practical application of VO2-based smart windows. PMID:28772673

Voltage- and current-activated metal-insulator transition in VO2-based electrical switches: a lifetime operation analysis.

PubMed

Crunteanu, Aurelian; Givernaud, Julien; Leroy, Jonathan; Mardivirin, David; Champeaux, Corinne; Orlianges, Jean-Christophe; Catherinot, Alain; Blondy, Pierre

2010-12-01

Vanadium dioxide is an intensively studied material that undergoes a temperature-induced metal-insulator phase transition accompanied by a large change in electrical resistivity. Electrical switches based on this material show promising properties in terms of speed and broadband operation. The exploration of the failure behavior and reliability of such devices is very important in view of their integration in practical electronic circuits. We performed systematic lifetime investigations of two-terminal switches based on the electrical activation of the metal-insulator transition in VO 2 thin films. The devices were integrated in coplanar microwave waveguides (CPWs) in series configuration. We detected the evolution of a 10 GHz microwave signal transmitted through the CPW, modulated by the activation of the VO 2 switches in both voltage- and current-controlled modes. We demonstrated enhanced lifetime operation of current-controlled VO 2 -based switching (more than 260 million cycles without failure) compared with the voltage-activated mode (breakdown at around 16 million activation cycles). The evolution of the electrical self-oscillations of a VO 2 -based switch induced in the current-operated mode is a subtle indicator of the material properties modification and can be used to monitor its behavior under various external stresses in sensor applications.

Ultrafast diffraction conoscopy of the structural phase transition in VO2: Evidence of two lattice distortions

NASA Astrophysics Data System (ADS)

Kumar, Nardeep; Rúa, Armando; Fernández, Félix E.; Lysenko, Sergiy

2017-06-01

Photoinduced phase transitions in complex correlated systems occur very rapidly and involve the interplay between various electronic and lattice degrees of freedom. For these materials to be considered for practical applications, it is important to discover how their phase transitions take place. Here we use a novel ultrafast diffraction conoscopy technique to study the evolution of vanadium dioxide (VO2) from biaxial to uniaxial symmetry. A key finding in this study is an additional relaxation process through which the phase transition takes place. Our results show that the biaxial monoclinic crystal initially, within the first 100-300 fs, transforms to a transient biaxial crystal, and within the next 300-400 fs converts into a uniaxial rutile crystal. The characteristic times for these transitions depend on film morphology and are presumably altered by misfit strain. We take advantage of Landau phenomenology to describe the complex dynamics of VO2 phase transition in the femtosecond regime.

Bidirectional current triggering in planar devices based on serially connected VO₂ thin films using 965 nm laser diode.

PubMed

Kim, Jihoon; Park, Kyongsoo; Kim, Bong-Jun; Lee, Yong Wook

2016-08-08

By incorporating a 965 nm laser diode, the bidirectional current triggering of up to 30 mA was demonstrated in a two-terminal planar device based on serially connected vanadium dioxide (VO₂) thin films grown by pulsed laser deposition. The bidirectional current triggering was realized by using the focused beams of laser pulses through the photo-thermally induced phase transition of VO₂. The transient responses of laser-triggered currents were also investigated when laser pulses excited the device at a variety of pulse widths and repetition rates of up to 4.0 Hz. A switching contrast between off- and on-state currents was obtained as ~8333, and rising and falling times were measured as ~39 and ~29 ms, respectively, for 50 ms laser pulses.

Self Assembly and Properties of C:WO3 Nano-Platelets and C:VO2/V2O5 Triangular Capsules Produced by Laser Solution Photolysis

PubMed Central

2010-01-01

Laser photolysis of WCl6 in ethanol and a specific mixture of V2O5 and VCl3 in ethanol lead to carbon modified vanadium and tungsten oxides with interesting properties. The presence of graphene’s aromatic rings (from the vibrational frequency of 1,600 cm−1) together with C–C bonding of carbon (from the Raman shift of 1,124 cm−1) present unique optical, vibrational, electronic and structural properties of the intended tungsten trioxide and vanadium dioxide materials. The morphology of these samples shows nano-platelets in WOx samples and, in VOx samples, encapsulated spherical quantum dots in conjunction with fullerenes of VOx. Conductivity studies revealed that the VO2/V2O5 nanostructures are more sensitive to Cl than to the presence of ethanol, whereas the C:WO3 nano-platelets are more sensitive to ethanol than atomic C. PMID:20671779

Effects of V2O3 buffer layers on sputtered VO2 smart windows: Improved thermochromic properties, tunable width of hysteresis loops and enhanced durability

NASA Astrophysics Data System (ADS)

Long, Shiwei; Cao, Xun; Sun, Guangyao; Li, Ning; Chang, Tianci; Shao, Zewei; Jin, Ping

2018-05-01

Vanadium dioxide (VO2) is one of the most well-known thermochromic materials, which exhibits a notable optical change from transparent to reflecting in the infrared region upon a metal-insulator phase transition. For practical applications, VO2 thin films should be in high crystalline quality to obtain a strong solar modulation ability (ΔTsol). Meanwhile, narrow hysteresis loops and robust ambient durability are also indispensable for sensitivity and long-lived utilization, respectively. In this work, a series of high-quality V2O3/VO2 bilayer structures were grown on quartz glass substrates by reactive magnetron sputtering. Basically, the bottom V2O3 acts as the buffer layer to improve the crystallinity of the top VO2, while the VO2 serves as the thermochromic layer to guarantee the solar modulation ability for energy-saving. We observed an obvious increase in ΔTsol of 76% (from 7.5% to 13.2%) for VO2 films after introducing V2O3 buffer layers. Simultaneously, a remarkable reduction by 79% (from 21.9 °C to 4.7 °C) in width of hysteresis loop was obtained when embedding 60 nm V2O3 buffer for 60 nm VO2. In addition, VO2 with non-stoichiometry of V2O3±x buffer demonstrates a broadening hysteresis loops width, which is derived from the lattice distortion caused by lattice imperfection. Finally, durability of VO2 has been significantly improved due to positive effects of V2O3 buffer layer. Our results lead to a comprehensive enhancement in crystallinity of VO2 and shed new light on the promotion of thermochromic property by homologous oxides for VO2.

Room-temperature subnanosecond waveguide lasers in Nd:YVO4 Q-switched by phase-change VO2: A comparison with 2D materials

NASA Astrophysics Data System (ADS)

Nie, Weijie; Li, Rang; Cheng, Chen; Chen, Yanxue; Lu, Qingming; Romero, Carolina; Vázquez de Aldana, Javier R.; Hao, Xiaotao; Chen, Feng

2017-04-01

We report on room-temperature subnanosecond waveguide laser operation at 1064 nm in a Nd:YVO4 crystal waveguide through Q-switching of phase-change nanomaterial vanadium dioxide (VO2). The unique feature of VO2 nanomaterial from the insulating to metallic phases offers low-saturation-intensity nonlinear absorptions of light for subnanosecond pulse generation. The low-loss waveguide is fabricated by using the femtosecond laser writing with depressed cladding geometry. Under optical pump at 808 nm, efficient pulsed laser has been achieved in the Nd:YVO4 waveguide, reaching minimum pulse duration of 690 ps and maximum output average power of 66.7 mW. To compare the Q-switched laser performances by VO2 saturable absorber with those based on two-dimensional materials, the 1064-nm laser pulses have been realized in the same waveguide platform with either graphene or transition metal dichalcogenide (in this work, WS2) coated mirror. The results on 2D material Q-switched waveguide lasers have shown that the shortest pulses are with 22-ns duration, whilst the maximum output average powers reach ~161.9 mW. This work shows the obvious difference on the lasing properties based on phase-change material and 2D materials, and suggests potential applications of VO2 as low-cost saturable absorber for subnanosecond laser generation.

Room-temperature subnanosecond waveguide lasers in Nd:YVO4 Q-switched by phase-change VO2: A comparison with 2D materials.

PubMed

Nie, Weijie; Li, Rang; Cheng, Chen; Chen, Yanxue; Lu, Qingming; Romero, Carolina; Vázquez de Aldana, Javier R; Hao, Xiaotao; Chen, Feng

2017-04-06

We report on room-temperature subnanosecond waveguide laser operation at 1064 nm in a Nd:YVO 4 crystal waveguide through Q-switching of phase-change nanomaterial vanadium dioxide (VO 2 ). The unique feature of VO 2 nanomaterial from the insulating to metallic phases offers low-saturation-intensity nonlinear absorptions of light for subnanosecond pulse generation. The low-loss waveguide is fabricated by using the femtosecond laser writing with depressed cladding geometry. Under optical pump at 808 nm, efficient pulsed laser has been achieved in the Nd:YVO 4 waveguide, reaching minimum pulse duration of 690 ps and maximum output average power of 66.7 mW. To compare the Q-switched laser performances by VO 2 saturable absorber with those based on two-dimensional materials, the 1064-nm laser pulses have been realized in the same waveguide platform with either graphene or transition metal dichalcogenide (in this work, WS 2 ) coated mirror. The results on 2D material Q-switched waveguide lasers have shown that the shortest pulses are with 22-ns duration, whilst the maximum output average powers reach ~161.9 mW. This work shows the obvious difference on the lasing properties based on phase-change material and 2D materials, and suggests potential applications of VO 2 as low-cost saturable absorber for subnanosecond laser generation.

Room-temperature subnanosecond waveguide lasers in Nd:YVO4 Q-switched by phase-change VO2: A comparison with 2D materials

PubMed Central

Nie, Weijie; Li, Rang; Cheng, Chen; Chen, Yanxue; Lu, Qingming; Romero, Carolina; Vázquez de Aldana, Javier R.; Hao, Xiaotao; Chen, Feng

2017-01-01

We report on room-temperature subnanosecond waveguide laser operation at 1064 nm in a Nd:YVO4 crystal waveguide through Q-switching of phase-change nanomaterial vanadium dioxide (VO2). The unique feature of VO2 nanomaterial from the insulating to metallic phases offers low-saturation-intensity nonlinear absorptions of light for subnanosecond pulse generation. The low-loss waveguide is fabricated by using the femtosecond laser writing with depressed cladding geometry. Under optical pump at 808 nm, efficient pulsed laser has been achieved in the Nd:YVO4 waveguide, reaching minimum pulse duration of 690 ps and maximum output average power of 66.7 mW. To compare the Q-switched laser performances by VO2 saturable absorber with those based on two-dimensional materials, the 1064-nm laser pulses have been realized in the same waveguide platform with either graphene or transition metal dichalcogenide (in this work, WS2) coated mirror. The results on 2D material Q-switched waveguide lasers have shown that the shortest pulses are with 22-ns duration, whilst the maximum output average powers reach ~161.9 mW. This work shows the obvious difference on the lasing properties based on phase-change material and 2D materials, and suggests potential applications of VO2 as low-cost saturable absorber for subnanosecond laser generation. PMID:28383017

Substrate bias effect on the fabrication of thermochromic VO2 films by reactive RF sputtering

NASA Astrophysics Data System (ADS)

Miyazaki, H.; Yasui, I.

2006-05-01

Vanadium oxide VOx films were deposited by reactive RF magnetron sputtering by applying a substrate bias, in which the Ar ions in plasma impacted the growing film surface. The vanadium valence of the VOx film decreased when the substrate negative bias voltage was increased. The VO2 film was successfully deposited at a substrate temperature of 400 °C and with a bias voltage of -50 to -80 V. The transition temperatures of the VO2 films with a substrate bias of -50 and -80 V were about 56 °C and 44 °C, respectively.

Electrocatalytic activity of cobalt phosphide-modified graphite felt toward VO2+/VO2+ redox reaction

NASA Astrophysics Data System (ADS)

Ge, Zhijun; Wang, Ling; He, Zhangxing; Li, Yuehua; Jiang, Yingqiao; Meng, Wei; Dai, Lei

2018-04-01

A novel strategy for improving the electro-catalytic properties of graphite felt (GF) electrode in vanadium redox flow battery (VRFB) is designed by depositing cobalt phosphide (CoP) onto GF surface. The CoP powder is synthesized by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) followed by phosphidation. Cyclic voltammetry results confirm that the CoP-modified graphite felt (GF-CoP) electrode has excellent reversibility and electro-catalytic activity to the VO2+/VO2+ cathodic reaction compared with the pristine GF electrode. The cell using GF-CoP electrode shows apparently higher discharge capacity over that based on GF electrode. The cell using GF-CoP electrode has the capacity of 67.2 mA h at 100 mA cm-2, 32.7 mA h larger than that using GF electrode. Compared with cell using GF electrode, the voltage efficiency of the cell based on GF-CoP electrode increases by 5.9% and energy efficiency by 5.4% at a current density of 100 mA cm-2. The cell using GF-CoP electrode can reach 94.31% capacity retention after 50 cycles at a current density of 30 mA cm-2. The results show that the CoP can effectively promote the VO2+/VO2+ redox reaction, implying that metal phosphides are a new kind of potential catalytic materials for VRFB.

The electro-optic mechanism and infrared switching dynamic of the hybrid multilayer VO2/Al:ZnO heterojunctions.

PubMed

Zhang, Peng; Zhang, Wu; Wang, Junyong; Jiang, Kai; Zhang, Jinzhong; Li, Wenwu; Wu, Jiada; Hu, Zhigao; Chu, Junhao

2017-06-30

Active and widely controllable phase transition optical materials have got rapid applications in energy-efficient electronic devices, field of meta-devices and so on. Here, we report the optical properties of the vanadium dioxide (VO 2 )/aluminum-doped zinc oxide (Al:ZnO) hybrid n-n type heterojunctions and the corresponding electro-optic performances of the devices. Various structures are fabricated to compare the discrepancy of the optical and electrical characteristics. It was found that the reflectance spectra presents the wheel phenomenon rather than increases monotonically with temperature at near-infrared region range. The strong interference effects was found in the hybrid multilayer heterojunction. In addition, the phase transition temperature decreases with increasing the number of the Al:ZnO layer, which can be ascribed to the electron injection to the VO 2 film from the Al:ZnO interface. Affected by the double layer Al:ZnO, the abnormal Raman vibration mode was presented in the insulator region. By adding the external voltage on the Al 2 O 3 /Al:ZnO/VO 2 /Al:ZnO, Al 2 O 3 /Al:ZnO/VO 2 and Al 2 O 3 /VO 2 /Al:ZnO thin-film devices, the infrared optical spectra of the devices can be real-time manipulated by an external voltage. The main effect of joule heating and assistant effect of electric field are illustrated in this work. It is believed that the results will add a more thorough understanding in the application of the VO 2 /transparent conductive film device.

Role of thermal heating on the voltage induced insulator-metal transition in VO2.

PubMed

Zimmers, A; Aigouy, L; Mortier, M; Sharoni, A; Wang, Siming; West, K G; Ramirez, J G; Schuller, Ivan K

2013-02-01

We show that the main mechanism for the dc voltage or dc current induced insulator-metal transition in vanadium dioxide VO(2) is due to local Joule heating and not a purely electronic effect. This "tour de force" experiment was accomplished by using the fluorescence spectra of rare-earth doped micron sized particles as local temperature sensors. As the insulator-metal transition is induced by a dc voltage or dc current, the local temperature reaches the transition temperature indicating that Joule heating plays a predominant role. This has critical implications for the understanding of the dc voltage or dc current induced insulator-metal transition and has a direct impact on applications which use dc voltage or dc current to externally drive the transition.

Broadband planar multilayered absorbers tuned by VO2 phase transition

NASA Astrophysics Data System (ADS)

Peng, Hao; Ji, Chunhui; Lu, Lulu; Li, Zhe; Li, Haoyang; Wang, Jun; Wu, Zhiming; Jiang, Yadong; Xu, Jimmy; Liu, Zhijun

2017-08-01

The metal-insulator transition makes vanadium dioxide an attractive material for developing reconfigurable optoelectronic components. Here we report on dynamically tunable broadband absorbers consisting of planar multilayered thin films. By thermally triggering the phase transition of vanadium dioxide, the effective impedance of multilayered structures is tuned in or out of the condition of impedance matching to free-space, leading to switchable broadband absorptions. Two types of absorbers are designed and demonstrated by using either the insulating or metallic state of vanadium dioxide at the impedance matched condition. The planar multilayered absorbers exhibit tunable absorption bands over the wavelength ranges of 5-9.3 μm and 3.9-8.2 μm, respectively. A large modulation depth up to 88% is measured. The demonstrated broadband absorbance tunability is of potential interest for reconfigurable bolometric sensing, camouflaging, and modulation of mid-infrared lights.

Size and composition-controlled fabrication of VO2 nanocrystals by terminated cluster growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anders, Andre; Slack, Jonathan

2013-05-14

A physical vapor deposition-based route for the fabrication of VO2 nanoparticles is demonstrated, consisting of reactive sputtering and vapor condensation at elevated pressures. The oxidation of vanadium atoms is an efficient heterogeneous nucleation method, leading to high nanoparticle throughtput. Fine control of the nanoparticle size and composition is obtained. Post growth annealing leads to crystalline VO2 nanoparticles with optimum thermocromic and plasmonic properties.

Anion-conductive membranes with ultralow vanadium permeability and excellent performance in vanadium flow batteries.

PubMed

Mai, Zhensheng; Zhang, Huamin; Zhang, Hongzhang; Xu, Wanxing; Wei, Wenping; Na, Hui; Li, Xianfeng

2013-02-01

Anion exchange membranes prepared from quaternized poly(tetramethyl diphenyl ether sulfone) (QAPES) were first investigated in the context of vanadium flow battery (VFB) applications. The membranes showed an impressive suppression effect on vanadium ions. The recorded vanadium permeability was 0.02×10(-7)-0.09×10(-7) cm(2) min(-1), which was two orders of magnitude lower than that of Nafion 115. The self-discharge duration of a VFB single cell with a QAPES membrane is four times longer than that of Nafion 115. The morphological difference in hydrophilic domains between QAPES and Nafion was confirmed by TEM. After soaking the membranes in VO(2)(+) solution, adsorbed vanadium ions can barely be found in QAPES, whereas the hydrophilic domains of Nafion were stained. In the ex situ chemical stability test, QAPES showed a high tolerance to VO(2)(+) and remained intact after immersion in VO(2)(+) solution for over 250 h. The performance of a VFB single cell assembled with QAPES membranes is equal to or even better than that of Nafion 115 and remains stable in a long-term cycle test. These results indicate that QAPES membranes can be an ideal option in the fabrication of high-performance VFBs with low electric capacity loss. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The optical gap in VO2 insulating phases is dominated by Coulomb repulsion

NASA Astrophysics Data System (ADS)

Hendriks, Christopher; Walter, Eric; Krakauer, Henry; Huffman, Tyler; Qazilbash, Mumtaz

Under doping, tensile strain or heating, vanadium dioxide (VO2) transforms from an insulating monoclinic (M1) to a metallic rutile (R) phase, progressing through intermediate insulating triclinic (T) and magnetic (M2) phases. Broadband optical spectroscopy data have been obtained on the T and M2 phases in the same sample. While only half the V atoms are dimerized in M2 compared to M1 and T, the measured optical gap is essentially unaltered by the first-order structural phase transition between them. Moreover, the optical interband features in the T and M2 phases are remarkably similar to those previously observed in the well-studied M1 phase. This shows that the electronic structure is insensitive to the lattice structure. Our ab-initio HSE optical conductivity calculations on the insulating phases of VO2 are in excellent agreement with the experimental measurements. We will discuss the choice of α, the fraction of exact exchange. As the energy gap is insensitive to the different lattice structures of the three insulating phases, we rule out Peierls effects as the dominant contributor to the opening of the gap. Rather, the energy gap arises from intra-atomic Coulomb correlations. Supported by ONR.

Reduction of V2O5 thin films deposited by aqueous sol-gel method to VO2(B) and investigation of its photocatalytic activity

NASA Astrophysics Data System (ADS)

Monfort, Olivier; Roch, Tomas; Satrapinskyy, Leonid; Gregor, Maros; Plecenik, Tomas; Plecenik, Andrej; Plesch, Gustav

2014-12-01

A way of preparation of VO2(B) thin films by reduction of V2O5 films synthesized from an aqueous sol-gel system has been developed and photocatalytic properties of the obtained films were studied. The reduction was performed by annealing of the V2O5 film in vacuum as well as in H2/Ar atmosphere, which was followed by temperature dependent XRD. It has been shown that the reduction is influenced by the layered-structure of the vanadium oxides. It is a two-step process, where the mixed-valence vanadium oxide V4O9 is first formed before reaching the VO2(B) phase. The film microstructure was characterized by SEM and AFM and the valence states of vanadium in VO2(B) films were evaluated by XPS. The VO2(B) polymorph shows an energy band-gap around 2.8 eV and it exhibits photocatalytic properties. It was measured by following the degradation of rhodamine B under UVA as well as metalhalogenide lamp irradiation, which has similar spectral distribution as natural sunlight. The VO2(B) films show distinct photoactivities under both lamps, although they were found to be more active under the UVA irradiation. The film annealed under reducing hydrogen atmosphere, which exhibits higher granularity and surface roughness, shows higher photoactivity than the vacuum-annealed film.

Relative Influence of Intrinsic and Extrinsic Factors on the Metal-Insulator Transition of VO2 Nanowires

NASA Astrophysics Data System (ADS)

Kim, In Soo

The influence of stoichiometry on the metal-insulator transition of vanadium dioxide (VO2) nanowires was investigated using Raman spectroscopy. Controlled reduction of nominally strain-free suspended VO2 nanowires was conducted by rapid thermal annealing (RTA). The deficiency in oxygen assisted in the unprecedented suppression of the metallic (R) phase to temperatures as low as 103 K through generation of free electrons. In a complementary manner, oxygen-rich conditions stabilized the metastable monoclinic (M2) and triclinic (T) phases. A pseudo-phase diagram with dimensions of temperature and stoichiometry was established, highlighting the accessibility of new phases in the nanowire geometry. Detection of the dynamic elastic response across the metal-insulator transition in suspended VO2 nanowires was enabled by fiber-coupled polarization dependent interferometry. Dual-beam Raman spectroscopy was developed to determine the local domain/phase structure of VO2 nanowires, which allowed for accurate modeling using COMSOL finite element analysis (FEA). The Young's moduli of the single crystal insulating (M1) and metallic (R) phases without artifacts were determined for the first time. The sources of dissipation were identified as clamping losses, structural losses, thermoelastic damping, and domain wall motion. While contribution of thermoelastic damping was found to be dominant in the terminal phases, extraordinary dissipation was observed upon formation and movement of domain walls. Finally, it was shown that creation of local defects could lead to new classes of tunable sensors with a discrete and programmable frequency response with temperature.

Electrical switching dynamics and broadband microwave characteristics of VO2 radio frequency devices

NASA Astrophysics Data System (ADS)

Ha, Sieu D.; Zhou, You; Fisher, Christopher J.; Ramanathan, Shriram; Treadway, Jacob P.

2013-05-01

Vanadium dioxide (VO2) is a correlated electron system that features a metal-insulator phase transition (MIT) above room temperature and is of interest in high speed switching devices. Here, we integrate VO2 into two-terminal coplanar waveguides and demonstrate a large resistance modulation of the same magnitude (>103) in both electrically (i.e., by bias voltage, referred to as E-MIT) and thermally (T-MIT) driven transitions. We examine transient switching characteristics of the E-MIT and observe two distinguishable time scales for switching. We find an abrupt jump in conductivity with a rise time of the order of 10 ns followed by an oscillatory damping to steady state on the order of several μs. We characterize the RF power response in the On state and find that high RF input power drives VO2 further into the metallic phase, indicating that electromagnetic radiation-switching of the phase transition may be possible. We measure S-parameter RF properties up to 13.5 GHz. Insertion loss is markedly flat at 2.95 dB across the frequency range in the On state, and sufficient isolation of over 25 dB is observed in the Off state. We are able to simulate the RF response accurately using both lumped element and 3D electromagnetic models. Extrapolation of our results suggests that optimizing device geometry can reduce insertion loss further and maintain broadband flatness up to 40 GHz.

Properties of the correlated metal phase induced by electrolyte gating of insulating vanadium dioxide nanobeams

NASA Astrophysics Data System (ADS)

Singh, Sujay; Horrocks, Gregory; Marley, Peter; Banerjee, Sarbajit; Sambandamurthy, G.

2014-03-01

Vanadium oxide (VO2) undergoes a first order metal to insulator transition (MIT) and a structural phase transition (monoclinic insulator to rutile metal) near 340 K. Over the past few years, several attempts are made to trigger the MIT in VO2 using ionic liquids (IL). Parkin's group has recently showed that IL gating leads to the creation of oxygen vacancies in VO2 and stabilizes the metallic phase. Our goal is to study the electronic properties, changes in the stoichiometry and structure of this metallic phase created by oxygen vacancies. Electrical transport measurements on single crystal nanobeams show that the metallic phase has a higher resistance while IL gating is applied and results from Raman spectroscopy studies on any structural change during IL gating will be presented. The role of substitutional dopants (such as W, Mo) on the creation of oxygen vacancies and subsequent stabilization of metallic phase in IL gated experiments will also be discussed. The work is supported by NSF DMR 0847324 and 0847169.

Frequency tunable near-infrared metamaterials based on VO2 phase transition.

PubMed

Dicken, Matthew J; Aydin, Koray; Pryce, Imogen M; Sweatlock, Luke A; Boyd, Elizabeth M; Walavalkar, Sameer; Ma, James; Atwater, Harry A

2009-09-28

Engineering metamaterials with tunable resonances from mid-infrared to near-infrared wavelengths could have far-reaching consequences for chip based optical devices, active filters, modulators, and sensors. Utilizing the metal-insulator phase transition in vanadium oxide (VO(2)), we demonstrate frequency-tunable metamaterials in the near-IR range, from 1.5 - 5 microns. Arrays of Ag split ring resonators (SRRs) are patterned with e-beam lithography onto planar VO(2) and etched via reactive ion etching to yield Ag/VO(2) hybrid SRRs. FTIR reflection data and FDTD simulation results show the resonant peak position red shifts upon heating above the phase transition temperature. We also show that, by including coupling elements in the design of these hybrid Ag/VO(2) bi-layer structures, we can achieve resonant peak position tuning of up to 110 nm.

Modulated scattering technique in the terahertz domain enabled by current actuated vanadium dioxide switches

PubMed Central

Vitale, W. A.; Tamagnone, M.; Émond, N.; Le Drogoff, B.; Capdevila, S.; Skrivervik, A.; Chaker, M.; Mosig, J. R.; Ionescu, A. M.

2017-01-01

The modulated scattering technique is based on the use of reconfigurable electromagnetic scatterers, structures able to scatter and modulate an impinging electromagnetic field in function of a control signal. The modulated scattering technique is used in a wide range of frequencies up to millimeter waves for various applications, such as field mapping of circuits or antennas, radio-frequency identification devices and imaging applications. However, its implementation in the terahertz domain remains challenging. Here, we describe the design and experimental demonstration of the modulated scattering technique at terahertz frequencies. We characterize a modulated scatterer consisting in a bowtie antenna loaded with a vanadium dioxide switch, actuated using a continuous current. The modulated scatterer behavior is demonstrated using a time domain terahertz spectroscopy setup and shows significant signal strength well above 0.5 THz, which makes this device a promising candidate for the development of fast and energy-efficient THz communication devices and imaging systems. Moreover, our experiments allowed us to verify the operation of a single micro-meter sized VO2 switch at terahertz frequencies, thanks to the coupling provided by the antenna. PMID:28145523

Phase Transformation of VO2 Nanoparticles Assisted by Microwave Heating

PubMed Central

Sikong, Lek.

2014-01-01

The microwave assisted synthesis nowadays attracts a great deal of attention. Monoclinic phase VO2 (M) was prepared from NH4VO3 and H2C2O4 · 2H2O by a rapid microwave assisted technique. The synthesis parameters, microwave irradiation time, microwave power, and calcinations temperature were systematically varied and their influences on the structure and morphology were evaluated. The microwave power level has been carried out in range 180–600 W. TEM analysis demonstrated nanosized samples. The structural and morphological properties were measured using XRD, TEM, and thermal analyses. The variations of vanadium phase led to thermochromic properties. PMID:24688438

Sharpness and intensity modulation of the metal-insulator transition in ultrathin VO2 films by interfacial structure manipulation

NASA Astrophysics Data System (ADS)

McGee, Ryan; Goswami, Ankur; Pal, Soupitak; Schofield, Kalvin; Bukhari, Syed Asad Manzoor; Thundat, Thomas

2018-03-01

Vanadium dioxide (VO2) undergoes a structural transformation from monoclinic (insulator) to tetragonal (metallic) upon heating above 340 K, accompanied by abrupt changes to its electronic, optical, and mechanical properties. Not only is this transition scientifically intriguing, but there are also numerous applications in sensing, memory, and optoelectronics. Here we investigate the effect different substrates and the processing conditions have on the characteristics metal-insulator transition (MIT), and how the properties can be tuned for specific applications. VO2 thin films were grown on c -plane sapphire (0001) and p-type silicon <100 > by pulsed laser deposition. High-resolution x-ray diffraction along with transmission electron microscopy reveals textured epitaxial growth on sapphire by domain-matching epitaxy, while the presence of a native oxide layer on silicon prevented any preferential growth resulting in a polycrystalline film. An orientation relationship of <001 > (010)VO2||<11 ¯00 > (0001)Al 2O3 was established for VO2 grown on sapphire, while no such relationship was found for VO2 grown on silicon. Surface-energy minimization is the driving force behind grain growth, as the lowest energy VO2 plane grew on silicon, while on sapphire the desire for epitaxial growth was dominant. Polycrystallinity of films grown on silicon caused a weaker and less prominent MIT than observed on sapphire, whose MIT was higher in magnitude and steeper in slope. The position of the MIT was shown to depend on the competing effects of misfit strain and grain growth. Higher deposition temperatures caused an increase in the MIT, while compressive strain resulted in a decreased MIT.

Reactions of sulfur dioxide with neutral vanadium oxide clusters in the gas phase. I. Density functional theory study.

PubMed

Jakubikova, Elena; Bernstein, Elliot R

2007-12-27

Thermodynamics of reactions of vanadium oxide clusters with SO2 are studied at the BPW91/LANL2DZ level of theory. BPW91/LANL2DZ is insufficient to properly describe relative V-O and S-O bond strengths of vanadium and sulfur oxides. Calibration of theoretical results with experimental data is necessary to compute reliable enthalpy changes for reactions between VxOy and SO2. Theoretical results indicate SO2 to SO conversion occurs for oxygen-deficient clusters and SO2 to SO3 conversion occurs for oxygen-rich clusters. Stable intermediate structures of VOy (y = 1 - 4) clusters with SO2 are also obtained at the BPW91/TZVP level of theory. Some possible mechanisms for SO3 formation and catalyst regeneration for condensed-phase systems are suggested. These results are in agreement with, and complement, gas-phase experimental studies of neutral vanadium oxide clusters.

Homology of vanadium oxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vasyutinskii, N.A.

1987-05-01

The authors examine the homology of vanadium oxide and note that data on the existence of phases and homogeneity limits in the V-O system are very contradictory. A graphical illustration shows the homologous series of vanadium oxides. The predominant part of the discrete formations in the system V-O is characterized by integral stoichiometry and forms six homologous series. It is found that homologous series of vanadium oxides are not only a basis for systematization of such oxides, but also may serve as a means for predicting the composition of new phases, limits of homogeneity, their structure, and properties.

Facile and Low-Temperature Fabrication of Thermochromic Cr2O3/VO2 Smart Coatings: Enhanced Solar Modulation Ability, High Luminous Transmittance and UV-Shielding Function.

PubMed

Chang, Tianci; Cao, Xun; Li, Ning; Long, Shiwei; Gao, Xiang; Dedon, Liv R; Sun, Guangyao; Luo, Hongjie; Jin, Ping

2017-08-09

In the pursuit of energy efficient materials, vanadium dioxide (VO 2 ) based smart coatings have gained much attention in recent years. For smart window applications, VO 2 thin films should be fabricated at low temperature to reduce the cost in commercial fabrication and solve compatibility problems. Meanwhile, thermochromic performance with high luminous transmittance and solar modulation ability, as well as effective UV shielding function has become the most important developing strategy for ideal smart windows. In this work, facile Cr 2 O 3 /VO 2 bilayer coatings on quartz glasses were designed and fabricated by magnetron sputtering at low temperatures ranging from 250 to 350 °C as compared with typical high growth temperatures (>450 °C). The bottom Cr 2 O 3 layer not only provides a structural template for the growth of VO 2 (R), but also serves as an antireflection layer for improving the luminous transmittance. It was found that the deposition of Cr 2 O 3 layer resulted in a dramatic enhancement of the solar modulation ability (56.4%) and improvement of luminous transmittance (26.4%) when compared to single-layer VO 2 coating. According to optical measurements, the Cr 2 O 3 /VO 2 bilayer structure exhibits excellent optical performances with an enhanced solar modulation ability (ΔT sol = 12.2%) and a high luminous transmittance (T lum,lt = 46.0%), which makes a good balance between ΔT sol and T lum for smart windows applications. As for UV-shielding properties, more than 95.8% UV radiation (250-400 nm) can be blocked out by the Cr 2 O 3 /VO 2 structure. In addition, the visualized energy-efficient effect was modeled by heating a beaker of water using infrared imaging method with/without a Cr 2 O 3 /VO 2 coating glass.

Multifunctional overcoats on vanadium dioxide thermochromic thin films with enhanced luminous transmission and solar modulation, hydrophobicity and anti-oxidation

NASA Astrophysics Data System (ADS)

Liu, Chang; Wang, Ning; Long, Yi

2013-10-01

Vanadium dioxide (VO2) has a great potential to be utilized as solar energy switching glazing, even though there exist some intrinsic problems of low luminous transmittance (Tlum) and poor oxidation resistance. Si-Al based anti-reflection (AR) sol-gel coatings processed at low temperature have been developed to tackle these issues assisted by adjusting ramping rate and annealing temperature. Si-Al based AR coating gives large relative enhancement on the transmittance (22% for Tlum, 14% for the whole solar spectrum Tsol,) and successfully maintains IR contrast at 2500 nm wavelength with 18% relative increase in solar modulation (ΔTsol). The optimized Si-Al based AR coating annealing conditions are recorded at 3 °C/min ramping rate and 100 °C annealing temperature. Fluorinated-Si based gel offers a new direction of multifunctional overcoat on thermochromic smart windows with hydrophobicity (contact angle 111°), averaged 14% relatively increased luminous transmittance and enhanced oxidation resistance.

The 1201 superconductors Hg1-y(VO4)y(Ba, Sr)2CuO4-2y+δ: evidence for VO4 tetrahedra

NASA Astrophysics Data System (ADS)

Malo, S.; Hervieu, M.; Maignan, A.; Knížek, K.; Raveau, B.; Michel, C.

1997-02-01

A series of mercury based cuprates with nominal composition Hg1-yV(y)Ba2-xSrxCuO4+2y+δ has been prepared for x = 0, 0.25, 0.5, 0.75, 1 and 1.25. The actual solid solution limit from the EDS measurement is x = 1.1, y ranges from 0.2 to 0.35. The single crystal study coupled with high resolution electron microscopy shows for the first time the presence of VO4 tetrahedra replacing partly the mercury atoms according to the formulation Hg1-y(VO4)y(Ba,Sr)2 CuO4-2y+δ. The role of vanadium for the stabilisation of the structure and as a doping agent in the superconducting properties is discussed.

Dynamically Switching the Polarization State of Light Based on the Phase Transition of Vanadium Dioxide

NASA Astrophysics Data System (ADS)

Jia, Zhi-Yong; Shu, Fang-Zhou; Gao, Ya-Jun; Cheng, Feng; Peng, Ru-Wen; Fan, Ren-Hao; Liu, Yongmin; Wang, Mu

2018-03-01

There have been great endeavors devoted to manipulating the polarization state of light by plasmonic nanostructures in recent decades. However, the topic of active polarizers has attracted much less attention. We present a composite plasmonic nanostructure consisting of vanadium dioxide that can dynamically modulate the polarization state of the reflected light through a thermally induced phase transition of vanadium dioxide. We design a system consisting of anisotropic plasmonic nanostructures with vanadium dioxide that exhibits distinct reflections subjected to different linearly polarized incidence at room temperature and in the heated state. Under a particular linearly polarized incidence, the polarization state of the reflected light changes at room temperature, and reverts to its original polarization state above the phase-transition temperature. The composite structure can also be used to realize a dynamically switchable infrared image, wherein a pattern can be visualized at room temperature while it disappears above the phase-transition temperature. The composite structure could be potentially used for versatile optical modulators, molecular detection, and polarimetric imaging.

A combined theoretical-experimental study of interactions between vanadium ions and Nafion membrane in all-vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Intan, Nadia N.; Klyukin, Konstantin; Zimudzi, Tawanda J.; Hickner, Michael A.; Alexandrov, Vitaly

2018-01-01

Vanadium redox flow batteries (VRFBs) are a promising solution for large-scale energy storage, but a number of problems still impede the deployment of long-lifetime VRFBs. One important aspect of efficient operation of VRFBs is understanding interactions between vanadium species and the membrane. Herein, we investigate the interactions between all four vanadium cations and Nafion membrane by a combination of infrared (IR) spectroscopy and density-functional-theory (DFT)-based static and molecular dynamics simulations. It is observed that vanadium species primarily lead to changes in the IR spectrum of Nafion in the SO3- spectral region which is attributed to the interaction between vanadium species and the SO3- exchange sites. DFT calculations of vanadium -Nafion complexes in the gas phase show that it is thermodynamically favorable for all vanadium cations to bind to SO3- via a contact pair mechanism. Car-Parrinello molecular dynamics-based metadynamics simulations of cation-Nafion systems in aqueous solution suggest that V2+ and V3+ species coordinate spontaneously to SO3-, which is not the case for VO2+ and VO2+ . The interaction behavior of the uncycled membrane determined in this study is used to explain the experimentally observed changes in the vibrational spectra, and is discussed in light of previous results on device-cycled membranes.

Double-use linear polarization convertor using hybrid metamaterial based on VO2 phase transition in the terahertz region

NASA Astrophysics Data System (ADS)

Zou, Huanling; Xiao, Zhongyin; Li, Wei; Li, Chuan

2018-04-01

A number of polarization convertors based on metamaterials(MMs) have been investigated recently, but no one has proposed a high-efficiency linear polarization transformer both in transmission and reflection modes. Here, a bilayered MM embedded with vanadium dioxide (VO2) composed of a pair of sloping gold patches, bottom hybrid layer and a dielectric spacer is proposed as a double-use linear polarization convertor. It has been demonstrated numerically that this device has advantages of switching between transmission polarization conversion and reflection polarization conversion based on the phase transition of the VO2 film in the terahertz (THz) regime and the polarization conversion ratios (PCR) in both cases are higher than 90% in wide bands. The simulated linear polarization transmission/reflection coefficients and the surface current distributions give insight into the mechanism of the linear polarization conversions. Moreover, the physical mechanism of polarization sensitivity of the designed structure is investigated by the distributions of electric field. The proposed double-use linear polarization convertor shows great prospects in polarization imaging, and polarized light communications.

The phase transition in VO 2 probed using x-ray, visible and infrared radiations

DOE PAGES

Kumar, Suhas; Strachan, John Paul; Kilcoyne, A. L. David; ...

2016-02-15

Vanadium dioxide (VO 2) is a model system that has been used to understand closely occurring multiband electronic (Mott) and structural (Peierls) transitions for over half a century due to continued scientific and technological interests. Among the many techniques used to study VO 2, the most frequently used involve electromagnetic radiation as a probe. Understanding of the distinct physical information provided by different probing radiations is incomplete, mostly owing to the complicated nature of the phase transitions. Here, we use transmission of spatially averaged infrared (λ = 1.5 μm) and visible (λ = 500 nm) radiations followed by spectroscopy andmore » nanoscale imaging using x-rays (λ = 2.25–2.38 nm) to probe the same VO 2 sample while controlling the ambient temperature across its hysteretic phase transitions and monitoring its electrical resistance. We directly observed nanoscale puddles of distinct electronic and structural compositions during the transition. The two main results are that, during both heating and cooling, the transition of infrared and visible transmission occurs at significantly lower temperatures than the Mott transition, and the electronic (Mott) transition occurs before the structural (Peierls) transition in temperature. We use our data to provide insights into possible microphysical origins of the different transition characteristics. We highlight that it is important to understand these effects because small changes in the nature of the probe can yield quantitatively, and even qualitatively, different results when applied to a non-trivial multiband phase transition. Our results guide more judicious use of probe type and interpretation of the resulting data.« less

Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

PubMed

Sepehr, Fatemeh; Paddison, Stephen J

2015-06-04

Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

Measurement of a solid-state triple point at the metal-insulator transition in VO2.

PubMed

Park, Jae Hyung; Coy, Jim M; Kasirga, T Serkan; Huang, Chunming; Fei, Zaiyao; Hunter, Scott; Cobden, David H

2013-08-22

First-order phase transitions in solids are notoriously challenging to study. The combination of change in unit cell shape, long range of elastic distortion and flow of latent heat leads to large energy barriers resulting in domain structure, hysteresis and cracking. The situation is worse near a triple point, where more than two phases are involved. The well-known metal-insulator transition in vanadium dioxide, a popular candidate for ultrafast optical and electrical switching applications, is a case in point. Even though VO2 is one of the simplest strongly correlated materials, experimental difficulties posed by the first-order nature of the metal-insulator transition as well as the involvement of at least two competing insulating phases have led to persistent controversy about its nature. Here we show that studying single-crystal VO2 nanobeams in a purpose-built nanomechanical strain apparatus allows investigation of this prototypical phase transition with unprecedented control and precision. Our results include the striking finding that the triple point of the metallic phase and two insulating phases is at the transition temperature, Ttr = Tc, which we determine to be 65.0 ± 0.1 °C. The findings have profound implications for the mechanism of the metal-insulator transition in VO2, but they also demonstrate the importance of this approach for mastering phase transitions in many other strongly correlated materials, such as manganites and iron-based superconductors.

Computational studies of small neutral vanadium oxide clusters and their reactions with sulfur dioxide

NASA Astrophysics Data System (ADS)

Jakubikova, Elena; He, Sheng-Gui; Xie, Yan; Matsuda, Yoshiyuki; Bernstein, Elliot

2007-03-01

Vanadium oxide is a catalytic system that plays an important role in the conversion of SO2 to SO3. Density functional theory at the BPW91/LANL2DZ level is employed to obtain structures of VOy (y=1,,5), V2Oy (y=2,,7), V3Oy (y=4,,9), V4Oy (y=7,,12) and their complexes with SO2. BPW91/LANL2DZ is insufficient to describe properly relative V-O and S-O bond strengths of vanadium and sulfur oxides. Calibration of theoretical results with experimental data is necessary to compute enthalpies of reactions between VxOy and SO2. Theoretical results indicate SO2 to SO conversion occurs for oxygen-deficient clusters and SO2 to SO3 conversion occurs for oxygen-rich clusters. Subsequent experimental studies confirm the presence of SO in the molecular beam as well as the presence of VxOy complexes with SO2. Some possible mechanisms for SO3 formation and catalyst regeneration for solids are also suggested.

Nanostructured Electrocatalysts for All-Vanadium Redox Flow Batteries.

PubMed

Park, Minjoon; Ryu, Jaechan; Cho, Jaephil

2015-10-01

Vanadium redox reactions have been considered as a key factor affecting the energy efficiency of the all-vanadium redox flow batteries (VRFBs). This redox reaction determines the reaction kinetics of whole cells. However, poor kinetic reversibility and catalytic activity towards the V(2+)/V(3+) and VO(2+)/VO2(+) redox couples on the commonly used carbon substrate limit broader applications of VRFBs. Consequently, modified carbon substrates have been extensively investigated to improve vanadium redox reactions. In this Focus Review, recent progress on metal- and carbon-based nanomaterials as an electrocatalyst for VRFBs is discussed in detail, without the intention to provide a comprehensive review on the whole components of the system. Instead, the focus is mainly placed on the redox chemistry of vanadium ions at a surface of various metals, different dimensional carbons, nitrogen-doped carbon nanostructures, and metal-carbon composites. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and theoretical study of the reactions between neutral vanadium oxide clusters and ethane, ethylene, and acetylene.

PubMed

Dong, Feng; Heinbuch, Scott; Xie, Yan; Rocca, Jorge J; Bernstein, Elliot R; Wang, Zhe-Chen; Deng, Ke; He, Sheng-Gui

2008-02-13

Reactions of neutral vanadium oxide clusters with small hydrocarbons, namely C2H6, C2H4, and C2H2, are investigated by experiment and density functional theory (DFT) calculations. Single photon ionization through extreme ultraviolet (EUV, 46.9 nm, 26.5 eV) and vacuum ultraviolet (VUV, 118 nm, 10.5 eV) lasers is used to detect neutral cluster distributions and reaction products. The most stable vanadium oxide clusters VO2, V2O5, V3O7, V4O10, etc. tend to associate with C2H4 generating products V(m)O(n)C2H4. Oxygen-rich clusters VO3(V2O5)(n=0,1,2...), (e.g., VO3, V3O8, and V5O13) react with C2H4 molecules to cause a cleavage of the C=C bond of C2H4 to produce (V2O5)(n)VO2CH2 clusters. For the reactions of vanadium oxide clusters (V(m)O(n)) with C2H2 molecules, V(m)O(n)C2H2 are assigned as the major products of the association reactions. Additionally, a dehydration reaction for VO3 + C2H2 to produce VO2C2 is also identified. C2H6 molecules are quite stable toward reaction with neutral vanadium oxide clusters. Density functional theory calculations are employed to investigate association reactions for V2O5 + C2H(x). The observed relative reactivity of C2 hydrocarbons toward neutral vanadium oxide clusters is well interpreted by using the DFT calculated binding energies. DFT calculations of the pathways for VO3+C2H4 and VO3+C2H2 reaction systems indicate that the reactions VO3+C2H4 --> VO2CH2 + H2CO and VO3+C2H2 --> VO2C2 + H2O are thermodynamically favorable and overall barrierless at room temperature, in good agreement with the experimental observations.

Structure, hydrolysis, and diffusion of aqueous vanadium ions from Car-Parrinello molecular dynamics

NASA Astrophysics Data System (ADS)

Jiang, Zhen; Klyukin, Konstantin; Alexandrov, Vitaly

2016-09-01

A molecular level understanding of the properties of electroactive vanadium species in aqueous solution is crucial for enhancing the performance of vanadium redox flow batteries. Here, we employ Car-Parrinello molecular dynamics simulations based on density functional theory to investigate the hydration structures, first hydrolysis reaction, and diffusion of aqueous V2+, V3+, VO2+, and VO 2+ ions at 300 K. The results indicate that the first hydration shell of both V2+ and V3+ contains six water molecules, while VO2+ is coordinated to five and VO 2+ to three water ligands. The first acidity constants (pKa) estimated using metadynamics simulations are 2.47, 3.06, and 5.38 for aqueous V3+, VO 2+ , and VO2+, respectively, while V2+ is predicted to be a fairly weak acid in aqueous solution with a pKa value of 6.22. We also show that the presence of chloride ions in the first coordination sphere of the aqueous VO 2+ ion has a significant impact on water hydrolysis leading to a much higher pKa value of 4.8. This should result in a lower propensity of aqueous VO 2+ for oxide precipitation reaction in agreement with experimental observations for chloride-based electrolyte solutions. The computed diffusion coefficients of vanadium species in water at room temperature are found to increase as V 3 + < VO 2 + < V O 2 + < V 2 + and thus correlate with the simulated hydrolysis constants, namely, the higher the pKa value, the greater the diffusion coefficient.

Vanadium dioxide as a material to control light polarization in the visible and near infrared

NASA Astrophysics Data System (ADS)

Cormier, Patrick; Son, Tran Vinh; Thibodeau, Jacques; Doucet, Alexandre; Truong, Vo-Van; Haché, Alain

2017-01-01

We report on the possible use of vanadium dioxide to produce ultrathin (<100 nm) adjustable phase retarders working over a wide spectral range. The refractive index of vanadium dioxide undergoes large changes when the material undergoes a phase transition from semiconductor to metal at a temperature of 68 °C. In a thin film, the resulting optical phase shift is different for s- and p-polarizations in both reflection and transmission, and under certain conditions the polarization state changes between linear or circular or between linear polarizations oriented differently when the material phase transitions. Specific ultrathin modulators are proposed based on the results.

Formation, structure and bond dissociation thresholds of gas-phase vanadium oxide cluster ions

NASA Astrophysics Data System (ADS)

Bell, R. C.; Zemski, K. A.; Justes, D. R.; Castleman, A. W.

2001-01-01

The formation and structure of gas-phase vanadium oxide cluster anions are examined using a guided ion beam mass spectrometer coupled with a laser vaporization source. The dominant peaks in the anion total mass distribution correspond to clusters having stoichiometries of the form (VO2)n(VO3)m(O2)q-. Collision-induced dissociation studies of the vanadium oxide species V2O4-6-, V3O6-9-, V4O8-10-, V5O11-13-, V6O13-15-, and V7O16-18- indicate that VO2, VO3, and V2O5 units are the main building blocks of these clusters. There are many similarities between the anion mass distribution and that of the cation distribution studied previously. The principal difference is a shift to higher oxygen content by one additional oxygen atom for the stoichiometric anions (VxOy-) as compared to the cations with the same number of vanadium atoms, which is attributed to the extra pair of electrons of the anionic species. The oxygen-rich clusters, VxOy(O2)-, are shown to more tightly adsorb molecular oxygen than those of the corresponding cationic clusters. In addition, the bond dissociation thresholds for the vanadium oxide clusters ΔE(V+-O)=6.09±0.28 eV, ΔE(OV+-O)=3.51±0.36 eV, and ΔE(O2V--O)=5.43±0.31 eV are determined from the energy-dependent collision-induced dissociation cross sections with Xe as the collision partner. To the best of our knowledge, this is the first bond dissociation energy reported for the breaking of the V-O bond of a vanadium oxide anion.

A VO-seeded Approach for the Growth of Star-shaped VO2 and V2O5 Nanocrystals: Facile Synthesis Structural Characterization and Elucidation of Electronic Structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

L Whittaker; J Velazquez; S Banerjee

2011-12-31

Obtaining shape and size control of strongly correlated materials is imperative to obtain a fundamental understanding of the influence of finite size and surface restructuring on electronic instabilities in the proximity of the Fermi level. We present here a novel synthetic approach that takes advantage of the intrinsic octahedral symmetry of rock-salt-structured VO to facilitate the growth of six-armed nanocrystallites of related, technologically important binary vanadium oxides VO2 and V2O5. The prepared nanostructures exhibit clear six-fold symmetry and most notably show remarkable retention of electronic structure. The latter has been evidenced through extensive X-ray absorption spectroscopy measurements.

Electron and hole dynamics in the electronic and structural phase transitions of VO2

NASA Astrophysics Data System (ADS)

Haglund, Richard

2015-03-01

The ultrafast, optically induced insulator-to-metal transition (IMT) and the associated structural phase transition (SPT) in vanadium dioxide (VO2) have been studied for over a decade. However, only recently have effects due to the combined presence of electron-hole pairs and injected electrons been observed. Here we compare and contrast IMT dynamics when both hot electrons and optically excited electron-hole pairs are involved, in (1) thin films of VO2 overlaid by a thin gold foil, in which hot electrons are generated by 1.5 eV photons absorbed in the foil and accelerated through the VO2 by an applied electric field; (2) VO2 nanoparticles covered with a sparse mesh of gold nanoparticles averaging 20-30 nm in diameter in which hot electrons are generated by resonant excitation and decay of the localized surface plasmon; and (3) bare VO2 thin films excited by intense near-single-cycle THz pulses. In the first case, the IMT is driven by excitation of the bulk gold plasmon, and the SPT appears on a few-picosecond time scale. In the second case, density-functional calculations indicate that above a critical carrier density, the addition of a single electron to a 27-unit supercell drives the catastrophic collapse of the coherent phonon associated with, and leading to, the SPT. In the third case, sub-bandgap-energy photons (approximately 0.1 eV) initiate the IMT, but exhibit the same sub-100 femtosecond switching time and coherent phonon dynamics as observed when the IMT is initiated by 1.5 eV photons. This suggests that the underlying mechanism must be quite different, possibly THz-field induced interband tunneling of spatially separated electron-hole pairs. The implications of these findings for ultrafast switching in opto-electronic devices - such as hybrid VO2 silicon ring resonators - are briefly considered. Support from the National Science Foundation (DMR-1207407), the Office of Science, U.S. Department of Energy (DE-FG02-01ER45916) and the Defense Threat

Axially engineered metal-insulator phase transition by graded doping VO2 nanowires.

PubMed

Lee, Sangwook; Cheng, Chun; Guo, Hua; Hippalgaonkar, Kedar; Wang, Kevin; Suh, Joonki; Liu, Kai; Wu, Junqiao

2013-03-27

The abrupt first-order metal-insulator phase transition in single-crystal vanadium dioxide nanowires (NWs) is engineered to be a gradual transition by axially grading the doping level of tungsten. We also demonstrate the potential of these NWs for thermal sensing and actuation applications. At room temperature, the graded-doped NWs show metal phase on the tips and insulator phase near the center of the NW, and the metal phase grows progressively toward the center when the temperature rises. As such, each individual NW acts as a microthermometer that can be simply read out with an optical microscope. The NW resistance decreases gradually with the temperature rise, eventually reaching 2 orders of magnitude drop, in stark contrast to the abrupt resistance change in undoped VO2 wires. This novel phase transition yields an extremely high temperature coefficient of resistivity ~10%/K, simultaneously with a very low resistivity down to 0.001 Ω·cm, making these NWs promising infrared sensing materials for uncooled microbolometers. Lastly, they form bimorph thermal actuators that bend with an unusually high curvature, ~900 m(-1)·K(-1) over a wide temperature range (35-80 °C), significantly broadening the response temperature range of previous VO2 bimorph actuators. Given that the phase transition responds to a diverse range of stimuli-heat, electric current, strain, focused light, and electric field-the graded-doped NWs may find wide applications in thermo-opto-electro-mechanical sensing and energy conversion.

Vanadium Flow Battery Electrolyte Synthesis via Chemical Reduction of V2O5 in Aqueous HCl and H2SO4.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Small, Leo J.; Pratt, Harry; Staiger, Chad

We report a simple method to synthesize V 4+ (VO 2+ ) electrolytes as feedstock for all- vanadium redox flow batteries (RFB). By dissolving V 2 O 5 in aqueous HCl and H 2 SO 4 , subsequently adding glycerol as a reducing agent, we have demonstrated an inexpensive route for electrolyte synthesis to concentrations >2.5 M V 4+ (VO 2+ ). Electrochemical analysis and testing of laboratory scale RFB demonstrate improved thermal stability across a wider temperature range (-10-65 degC) for V 4+ (VO 2+ ) electrolytes in HCl compared to in H 2 SO 4 electrolytes.

Direct observation of the M2 phase with its Mott transition in a VO2 film

NASA Astrophysics Data System (ADS)

Kim, Hoon; Slusar, Tetiana V.; Wulferding, Dirk; Yang, Ilkyu; Cho, Jin-Cheol; Lee, Minkyung; Choi, Hee Cheul; Jeong, Yoon Hee; Kim, Hyun-Tak; Kim, Jeehoon

2016-12-01

In VO2, the explicit origin of the insulator-to-metal transition is still disputable between Peierls and Mott insulators. Along with the controversy, its second monoclinic (M2) phase has received considerable attention due to the presence of electron correlation in undimerized vanadium ions. However, the origin of the M2 phase is still obscure. Here, we study a granular VO2 film using conductive atomic force microscopy and Raman scattering. Upon the structural transition from monoclinic to rutile, we observe directly an intermediate state showing the coexistence of monoclinic M1 and M2 phases. The conductivity near the grain boundary in this regime is six times larger than that of the grain core, producing a donut-like landscape. Our results reveal an intra-grain percolation process, indicating that VO2 with the M2 phase is a Mott insulator.

Evolution of Metallicity in Vanadium Dioxide by Creation of Oxygen Vacancies

NASA Astrophysics Data System (ADS)

Zhang, Zhen; Zuo, Fan; Wan, Chenghao; Dutta, Aveek; Kim, Jongbum; Rensberg, Jura; Nawrodt, Ronny; Park, Helen Hejin; Larrabee, Thomas J.; Guan, Xiaofei; Zhou, You; Prokes, S. M.; Ronning, Carsten; Shalaev, Vladimir M.; Boltasseva, Alexandra; Kats, Mikhail A.; Ramanathan, Shriram

2017-03-01

Tuning of the electronic state of correlated materials is key to their eventual use in advanced electronics and photonics. The prototypical correlated oxide (VO2 ) is insulating at room temperature and transforms to a metallic state when heated to 67 °C (340 K). We report the emergence of a metallic state that is preserved down to 1.8 K by annealing thin films of VO2 at an ultralow oxygen partial pressure (PO2˜10-24 atm ). The films can be reverted back to their original state by annealing in oxygen, and this process can be iterated multiple times. The metallic phase created by oxygen deficiency has a tetragonal rutile structure and contains a large number of oxygen vacancies far beyond the solubility at equilibrium (greater than approximately 50 times). The oxygen starvation reduces the oxidation state of vanadium from V4 + to V3 + and leads to the metallization. The extent of resistance reduction (concurrent with tuning of optical properties) can be controlled by the time-temperature envelope of the annealing conditions since the process is diffusionally driven. This experimental platform, which can extensively tune oxygen vacancies in correlated oxides, provides an approach to study emergent phases and defect-mediated adaptive electronic and structural phase boundary crossovers.

Electron-electron correlations in Raman spectra of VO2

NASA Astrophysics Data System (ADS)

Goncharuk, I. N.; Ilinskiy, A. V.; Kvashenkina, O. E.; Shadrin, E. B.

2013-01-01

It has been shown that, in single crystals and films of a strongly correlated material, namely, vanadium dioxide, upon a thermally stimulated phase transition from the low-temperature monoclinic phase to the high-temperature tetragonal phase, the narrow-line Raman spectrum of the insulating (monoclinic) phase transforms into the broad-band Raman spectrum, which contains two peaks at 500 and 5000 cm-1 with widths of 400 and 3500 cm-1, respectively. It has been found that, as the temperature of the monoclinic phase approaches the structural phase transition temperature (340 K), the line profile of soft-mode phonons at a frequency of 149 cm-1 with A g symmetry and the line profile of phonons at a frequency of 201 cm-1 with A g symmetry acquire an asymmetric shape with a Fano antiresonance that is characteristic of the interaction of a single phonon vibration with a continuum of strongly correlated electrons. It has been demonstrated that the thermal transformation of peaks in the Raman spectra of the VO2 metallic phase is in quantitative agreement with the theory of Raman scattering in strongly correlated materials.

Suspended sub-50 nm vanadium dioxide membrane transistors: fabrication and ionic liquid gating studies

NASA Astrophysics Data System (ADS)

Sim, Jai S.; Zhou, You; Ramanathan, Shriram

2012-10-01

We demonstrate a robust lithographic patterning method to fabricate self-supported sub-50 nm VO2 membranes that undergo a phase transition. Utilizing such self-supported membranes, we directly observed a shift in the metal-insulator transition temperature arising from stress relaxation and consistent opening of the hysteresis. Electric double layer transistors were then fabricated with the membranes and compared to thin film devices. The ionic liquid allowed reversible modulation of channel resistance and distinguishing bulk processes from the surface effects. From the shift in the metal-insulator transition temperature, the carrier density doped through electrolyte gating is estimated to be 1 × 1020 cm-3. Hydrogen annealing studies showed little difference in resistivity between the film and the membrane indicating rapid diffusion of hydrogen in the vanadium oxide rutile lattice consistent with previous observations. The ability to fabricate electrically-wired, suspended VO2 ultra-thin membranes creates new opportunities to study mesoscopic size effects on phase transitions and may also be of interest in sensor devices.

Induction of apoptosis in human colorectal cancer cell line, HCT-116 by a vanadium- Schiff base complex.

PubMed

Sinha, Abhinaba; Banerjee, Kaushik; Banerjee, Arpita; Sarkar, Avijit; Ahir, Manisha; Adhikary, Arghya; Chatterjee, Mitali; Choudhuri, Soumitra Kumar

2017-08-01

Vanadium compounds are well known for their therapeutic interventions against several diseases. Various biochemical attributes of vanadium complexes inspired us to evaluate the cancer cell killing efficacy of the vanadium complex, viz., vanadyl N-(2-hydroxyacetophenone) glycinate [VO(NG) 2 ]. Previously we showed that VO(NG) 2 is an effective anticancer agent in in vitro and in vivo cancer models and imposed miniscule side effects. Herein we report that VO(NG) 2 is significantly cytotoxic to various cancer cell lines. Furthermore, this redox active vanadyl complex altered the redox homeostatsis of many human cancer cell lines significantly. VO(NG) 2 actuates programmed cell death in human colorectal carcinoma cells(HCT-116) through mitochondrial outer membrane permeabilization but in caspase independent manner, possibly by altering cellular redox status and by inflicting DNA damage. Thus, the present work is an attempt to provide many evidences regarding the potent and selective chemotherapeutic efficacy of the novel VO(NG) 2 . Copyright © 2017 Elsevier Masson SAS. All rights reserved.

System Assessment of Carbon Dioxide Used as Gas Oxidant and Coolant in Vanadium-Extraction Converter

NASA Astrophysics Data System (ADS)

Du, Wei Tong; Wang, Yu; Liang, Xiao Ping

2017-10-01

With the aim of reducing carbon dioxide (CO2) emissions and of using waste resources in steel plants, the use of CO2 as a gas oxidant and coolant in the converter to increase productivity and energy efficiency was investigated in this study. Experiments were performed in combination with thermodynamic theory on vanadium-extraction with CO2 and oxygen (O2) mixed injections. The results indicate that the temperature of the hot metal bath decreased as the amount of CO2 introduced into O2 increased. At an injection of 85 vol.% O2 and 15 vol.% CO2, approximately 12% of additional carbon was retained in the hot metal. Moreover, the content of vanadium trioxide in the slag was higher. In addition, the O2 consumption per ton of hot metal was reduced by 8.5% and additional chemical energy was recovered by the controlled injection of CO2 into the converter. Therefore, using CO2 as a gas coolant was conducive to vanadium extraction, and O2 consumption was reduced.

Structure-property relationships in NOx sensor materials composed of arrays of vanadium oxide nanoclusters

NASA Astrophysics Data System (ADS)

Putrevu, Naga Ravikanth; Darling, Seth B.; Segre, Carlo U.; Ganegoda, Hasitha; Khan, M. Ishaque

2017-12-01

The mixed-valent vanadium oxide based three-dimensional framework structure species [Cd3(H2O)12V16IVV2VO36(OH)6 (AO4)]·24H2O, (A = V,S) (Cd3(VO)o) represents a rare example of an interesting sensor material which exhibits NOx {NO + NO2} semiconducting gas sensor properties under ambient conditions. The electrical resistance of the sensor material Cd3(VO)o decreases in air. Combined characterization studies revealed that the building block, {V18O42(AO4)} cluster, of 3-D framework undergoes oxidation and remains intact for at least 2 months. The decrease in resistance is attributable to the reactivity of molecular oxygen towards vanadium which results in an increase in the oxidation state as well as the coordination number of vanadium center and decrease in band gap of Cd3(VO)o. Based on these results we propose that the changes in semiconducting properties of Cd3(VO)o under ambient conditions are due to the greater overlap between the O 2p and V 3d orbitals occurring during the oxidation.

Structural and silver/vanadium ratio effects on silver vanadium phosphorous oxide solution formation kinetics: impact on battery electrochemistry.

PubMed

Bock, David C; Takeuchi, Kenneth J; Marschilok, Amy C; Takeuchi, Esther S

2015-01-21

The detailed understanding of non-faradaic parasitic reactions which diminish battery calendar life is essential to the development of effective batteries for use in long life applications. The dissolution of cathode materials including manganese, cobalt and vanadium oxides in battery systems has been identified as a battery failure mechanism, yet detailed dissolution studies including kinetic analysis are absent from the literature. The results presented here provide a framework for the quantitative and kinetic analyses of the dissolution of cathode materials which will aid the broader community in more fully understanding this battery failure mechanism. In this study, the dissolution of silver vanadium oxide, representing the primary battery powering implantable cardioverter defibrillators (ICD), is compared with the dissolution of silver vanadium phosphorous oxide (Ag(w)VxPyOz) materials which were targeted as alternatives to minimize solubility. This study contains the first kinetic analyses of silver and vanadium solution formation from Ag0.48VOPO4·1.9H2O and Ag2VP2O8, in a non-aqueous battery electrolyte. The kinetic results are compared with those of Ag2VO2PO4 and Ag2V4O11 to probe the relationships among crystal structure, stoichiometry, and solubility. For vanadium, significant dissolution was observed for Ag2V4O11 as well as for the phosphate oxide Ag0.49VOPO4·1.9H2O, which may involve structural water or the existence of multiple vanadium oxidation states. Notably, the materials from the SVPO family with the lowest vanadium solubility are Ag2VO2PO4 and Ag2VP2O8. The low concentrations and solution rates coupled with their electrochemical performance make these materials interesting alternatives to Ag2V4O11 for the ICD application.

Resistance noise spectroscopy across the thermally and electrically driven metal-insulator transitions in VO2 nanobeams

NASA Astrophysics Data System (ADS)

Alsaqqa, Ali; Kilcoyne, Colin; Singh, Sujay; Horrocks, Gregory; Marley, Peter; Banerjee, Sarbajit; Sambandamurthy, G.

Vanadium dioxide (VO2) is a strongly correlated material that exhibits a sharp thermally driven metal-insulator transition at Tc ~ 340 K. The transition can also be triggered by a DC voltage in the insulating phase with a threshold (Vth) behavior. The mechanisms behind these transitions are hotly discussed and resistance noise spectroscopy is a suitable tool to delineate different transport mechanisms in correlated systems. We present results from a systematic study of the low frequency (1 mHz < f < 10 Hz) noise behavior in VO2 nanobeams across the thermally and electrically driven transitions. In the thermal transition, the power spectral density (PSD) of the resistance noise is unchanged as we approach Tc from 300 K and an abrupt drop in the magnitude is seen above Tc and it remains unchanged till 400 K. However, the noise behavior in the electrically driven case is distinctly different: as the voltage is ramped from zero, the PSD gradually increases by an order of magnitude before reaching Vth and an abrupt increase is seen at Vth. The noise magnitude decreases above Vth, approaching the V = 0 value. The individual roles of percolation, Joule heating and signatures of correlated behavior will be discussed. This work is supported by NSF DMR 0847324.

Fabrication of VO2 thin film by rapid thermal annealing in oxygen atmosphere and its metal—insulator phase transition properties

NASA Astrophysics Data System (ADS)

Liang, Ji-Ran; Wu, Mai-Jun; Hu, Ming; Liu, Jian; Zhu, Nai-Wei; Xia, Xiao-Xu; Chen, Hong-Da

2014-07-01

Vanadium dioxide thin films have been fabricated through sputtering vanadium thin films and rapid thermal annealing in oxygen. The microstructure and the metal—insulator transition properties of the vanadium dioxide thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and a spectrometer. It is found that the preferred orientation of the vanadium dioxide changes from (1¯11) to (011) with increasing thickness of the vanadium thin film after rapid thermal annealing. The vanadium dioxide thin films exhibit an obvious metal—insulator transition with increasing temperature, and the phase transition temperature decreases as the film thickness increases. The transition shows hysteretic behaviors, and the hysteresis width decreases as the film thickness increases due to the higher concentration carriers resulted from the uncompleted lattice. The fabrication of vanadium dioxide thin films with higher concentration carriers will facilitate the nature study of the metal—insulator transition.

Imaging Nanometer Phase Coexistence at Defects During the Insulator-Metal Phase Transformation in VO2 Thin Films by Resonant Soft X-ray Holography.

PubMed

Vidas, Luciana; Günther, Christian M; Miller, Timothy A; Pfau, Bastian; Perez-Salinas, Daniel; Martínez, Elías; Schneider, Michael; Gührs, Erik; Gargiani, Pierluigi; Valvidares, Manuel; Marvel, Robert E; Hallman, Kent A; Haglund, Richard F; Eisebitt, Stefan; Wall, Simon

2018-05-18

We use resonant soft X-ray holography to image the insulator-metal phase transition in vanadium dioxide with element and polarization specificity and nanometer spatial resolution. We observe that nanoscale inhomogeneity in the film results in spatial-dependent transition pathways between the insulating and metallic states. Additional nanoscale phases form in the vicinity of defects which are not apparent in the initial or final states of the system, which would be missed in area-integrated X-ray absorption measurements. These intermediate phases are vital to understand the phase transition in VO 2 , and our results demonstrate how resonant imaging can be used to understand the electronic properties of phase-separated correlated materials obtained by X-ray absorption.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Oxidation State Discrimination in the Atomic Layer Deposition of Vanadium Oxides

DOE PAGES

Weimer, Matthew S.; Kim, In Soo; Guo, Peijun; ...

2017-06-02

We describe the use of a vanadium 3+ precursor for atomic layer deposition (ALD) of thin films that span the common oxidation states of vanadium oxides. Self-limiting surface synthesis of V 2O 3, VO 2, and V 2O 5 are realized via four distinct reaction mechanisms accessed via judicious choice of oxygen ALD partners. In situ quartz crystal microbalance and quadrupole mass spectrometry were used to study the reaction mechanism of the vanadium precursor with O 3, H 2O 2, H 2O/O 2, and H 2O 2/H 2. A clear distinction between non-oxidative protic ligand exchange and metal oxidation ismore » demonstrated through sequential surface reactions with different non-metal precursors. This synergistic effect, provides greater control of the resultant metal species in the film, as well as reactive surface species during growth. In an extension of this approach, we introduce oxidation state control through reducing equivalents of H 2 gas. When H 2 is dosed after H 2O 2 during growth, amorphous films of VO 2 are deposited that are readily crystallized with a low temperature anneal. These VO 2 films show a temperature dependent Raman spectroscopy response in the expected range and consistent with the well-known phase-change behavior of VO 2.« less

A functionalized surface modification with vanadium nanoparticles of various valences against implant-associated bloodstream infection.

PubMed

Wang, Jiaxing; Zhou, Huaijuan; Guo, Geyong; Cheng, Tao; Peng, Xiaochun; Mao, Xin; Li, Jinhua; Zhang, Xianlong

2017-01-01

Bloodstream infection, especially with implants involved, is an often life-threatening condition with high mortality rates, imposing a heavy burden on patients and medical systems. Herein, we firstly deposited homogeneous vanadium metal, V 2 O 3 , VO 2 , and V 2 O 5 nanofilms on quartz glass by magnetron sputtering. Using these platforms, we further investigated the potential antimicrobial efficiency of these nano-VO x films and the interactions of human erythrocytes and bacteria (methicillin-resistant Staphylococcus aureus and Pseudomonas aeruginosa ) with our samples in a novel cell-bacteria coculture model. It was demonstrated that these nano-VO x precipitated favorable antibacterial activity on both bacteria, especially on S. aureus , and this effect increased with higher vanadium valence. A possible mechanism accountable for these results might be elevated levels of vanadium-induced intracellular reactive oxygen species. More importantly, based on hemolysis assays, our nano-VO x films were found to be able to kill prokaryotic cells but were not toxic to mammalian cells, holding the potential for the prevention of implant-related hematogenous infections. As far as we know, this is the first report wherein such nano-VO x films have assisted human erythrocytes to combat bacteria in a valence-dependent manner. Additionally, vanadium ions were released from these nano-VO x films in a sustained manner, and low-valence films possessed better biocompatibility with human fibroblasts. This work may provide new insights for biomedical applications of inorganic vanadium compounds and attract growing attention in this field. From the perspective of surface modification and functionalization, this study holds promise to avail the prophylaxis of bloodstream infections involving implantable biomedical devices.

ZrO2-Nanoparticle-Modified Graphite Felt: Bifunctional Effects on Vanadium Flow Batteries.

PubMed

Zhou, Haipeng; Shen, Yi; Xi, Jingyu; Qiu, Xinping; Chen, Liquan

2016-06-22

To improve the electrochemical performance of graphite felt (GF) electrodes in vanadium flow batteries (VFBs), we synthesize a series of ZrO2-modified GF (ZrO2/GF) electrodes with varying ZrO2 contents via a facile immersion-precipitation approach. It is found that the uniform immobilization of ZrO2 nanoparticles on the GF not only significantly promotes the accessibility of vanadium electrolyte, but also provides more active sites for the redox reactions, thereby resulting in better electrochemical activity and reversibility toward the VO(2+)/VO2(+) and V(2+)/V(3+) redox reactions as compared with those of GF. In particular, The ZrO2/GF composite with 0.3 wt % ZrO2 displays the best electrochemical performance with voltage and energy efficiencies of 71.9% and 67.4%, respectively, which are much higher than those of 57.3% and 53.8% as obtained from the GF electrode at 200 mA cm(-2). The cycle life tests demonstrate that the ZrO2/GF electrodes exhibit outstanding stability. The ZrO2/GF-based VFB battery shows negligible activity decay after 200 cycles.

Understanding the Reduction Kinetics of Aqueous Vanadium(V) and Transformation Products Using Rotating Ring-Disk Electrodes.

PubMed

Chen, Gongde; Liu, Haizhou

2017-10-17

Vanadium(V) is an emerging contaminant in the most recent Environmental Protection Agency's candidate contaminant list (CCL4). The redox chemistry of vanadium controls its occurrence in the aquatic environment, but the impact of vanadium(V) speciation on the redox properties remains largely unknown. This study utilized the rotating ring-disk electrode technique to examine the reduction kinetics of four pH- and concentration-dependent vanadium(V) species in the presence and the absence of phosphate. Results showed that the reduction of VO 2 + , H x V 4 O 12+x (4+x)- (V 4 ), and HVO 4 2- proceeded via a one-electron transfer, while that of Na x H y V 10 O 28 (6-x-y)- (V 10 ) underwent a two-electron transfer. Koutecky-Levich and Tafel analyses showed that the intrinsic reduction rate constants followed the order of V 10 > VO 2 + > V 4 > HVO 4 2- . Ring-electrode collection efficiency indicated that the reduction product of V 10 was stable, while those of VO 2 + , HVO 4 2- , and V 4 had short half-lives that ranged from milliseconds to seconds. With molar ratios of phosphate to vanadium(V) varying from 0 to 1, phosphate accelerated the reduction kinetics of V 10 and V 4 and enhanced the stability of the reduction products of VO 2 + , V 4 , and HVO 4 2- . This study suggests that phosphate complexation could enhance the reductive removal of vanadium(V) and inhibit the reoxidation of its reduction product in water treatment.

Rate Dependency of Silver Vanadium Phosphorous Oxide Reduction

NASA Astrophysics Data System (ADS)

Cheng, Po-Jen

2011-12-01

The silver vanadium phosphorus oxide (Ag2VO2PO 4) is a high-capacity and good-compatibility material for the cathode in the battery. Due to their innovative properties, they are used as cathode in lithium batteries. Therefore, when the lithium batteries begin to discharge, the anodes of the cell perform an electrochemical oxidation and release electrons. In the mean time, the cathodes in the cells perform the electrochemical reduction and catch the electrons. For reduction of Ag2VO2PO 4, two silver ions (Ag+) catch two electrons to form silver particles, and the vanadium ions (V5+) catch two electrons to form V3+. It means that four electrons will be released by lithium anode. We call this four electrons discharge as 100% discharge. In my most of the projects, the Ag2VO2PO4 material is tested by differential scanning calorimetry (DSC) to check purity. My study is based on the discharge of batteries, and I focus on the morphology and the intensity of silver particles on the cathode after discharge. Depending on different adjustment of factors, such as discharge time, discharge rate, storage time, storage temperature, I try to investigate the silver intensity, conductivity as a function of DOD (Depth of Discharge). The silver particles could be examined by optical microscope, and scanning electron microscope (SEM). Moreover, I do some x-ray diffraction analysis to quantify the silver particles after discharge. Also, I perform magnetic susceptibility measurement to check the mechanism of the reduction of vanadium ions. Under the research on silver ions and vanadium ions, I will know a big frame of reduction process on silver vanadium phosphorous oxide and the time effect on this cathode material.

UV-vis-DR study of VO x/SiO 2 catalysts prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Moussa, N.; Ghorbel, A.

2008-12-01

Vanadia-silica catalysts with different vanadium loadings were prepared by sol-gel process. UV-vis diffuse-reflectance spectroscopy was used to elucidate the effect of drying mode (i.e., xerogel vs. aerogel), vanadium loading and calcination on the molecular structure of supported vanadium species. The results indicate that for vanadium loading ranging from 2.8 to 11.2 wt.%, the band-gap energies of all catalysts varying from 2.28 to 2.68 eV which demonstrate that vanadium oxides are predominantly in octahedral structure with the presence of tetrahedral species. The discrimination of different surface VO x species has been based on their characteristic Ligand to Metal Charge Transfer (LMCT) O → V(V) and d-d transition. It was found that the LMCT band position of V dbnd O bond is not affected by calcination either in xerogels or in aerogels but the position and the shape of bands relative to bridging V sbnd O sbnd V bonds are affected by vanadium loading, calcination and drying mode. For the same V/Si ratio, band-gap energy of xerogel is lower than that of aerogel which indicate that vanadium species are more dispersed in aerogels than in xerogels. Drying and calcination led to rearrangement, dehydration, cleavage and crystallization of vanadium species which explain the presence of some amount of crystalline V 2O 5 in calcined samples.

Temperature and electric field induced metal-insulator transition in atomic layer deposited VO2 thin films

NASA Astrophysics Data System (ADS)

Tadjer, Marko J.; Wheeler, Virginia D.; Downey, Brian P.; Robinson, Zachary R.; Meyer, David J.; Eddy, Charles R.; Kub, Fritz J.

2017-10-01

Amorphous vanadium oxide (VO2) films deposited by atomic layer deposition (ALD) were crystallized with an ex situ anneal at 660-670 °C for 1-2 h under a low oxygen pressure (10-4 to 10-5 Torr). Under these conditions the crystalline VO2 phase was maintained, while formation of the V2O5 phase was suppressed. Electrical transition from the insulator to the metallic phase was observed in the 37-60 °C range, with an ROFF/RON ratio of up to about 750 and ΔTC ≅ 7-10 °C. Lateral electric field applied across two-terminal device structures induced a reversible phase change, with a room temperature transition field of about 25 kV/cm in the VO2 sample processed with the 2 h long O2 anneal. Both the width and slope of the field induced MIT I-V hysteresis were dependent upon the VO2 crystalline quality.

Effect of W addition on the electrical switching of VO{sub 2} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rajeswaran, Bharathi, E-mail: rajeswaran.bharathi@gmail.com, E-mail: rbharathi@mrc.iisc.ernet.in; Umarji, Arun M.

2016-03-15

Vanadium Oxide has been a frontrunner in the field of oxide electronics because of its metal-insulator transition (MIT). The interplay of different structures of VO{sub 2} has played a crucial role in deciding the magnitude of the first order MIT. Substitution doping has been found to introduce different polymorphs of VO{sub 2}. Hence the role of substitution doping in stabilizing the competing phases of VO{sub 2} in the thin film form remains underexplored. Consequently there have been reports both discounting and approving such a stabilization of competing phases in VO{sub 2}. It is reported in the literature that the bandwidthmore » of the hysteresis and transition temperature of VO{sub 2} can be tuned by substitutional doping of VO{sub 2} with W. In this work, we have adopted a novel technique called, Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) to deposit VO{sub 2} and W- doped VO{sub 2} as thin films. XRD and Raman spectroscopy were used to investigate the role of tungsten on the structure of VO{sub 2} thin films. Morphology of the thin films was found to be consisting of globular and porous nanoparticles of size ∼ 20 nm. Transition temperature decreased with the addition of W. We found that for 2.0 at % W doping in VO{sub 2}, the transition temperature has reduced from 68 {sup o} C to 25 {sup o} C. It is noted that W-doping in the process of reducing the transition temperature, alters the local structure and also increases room temperature carrier concentration.« less

Photocatalytic Water Splitting for O2 Production under Visible Light Irradiation Using NdVO4-V2O5 Hybrid Powders

PubMed Central

Chiang, Tzu Hsuan; Chen, Tso-Ming

2017-01-01

The study investigated photocatalytic water splitting for O2 production under visible light irradiation using neodymium vanadium oxide (NdVO4) and vanadium oxide (V2O5) hybrid powders. The results in a sacrificial agent of 0.01 M AgNO3 solution were obtained, and the highest photocatalytic O2 evolution was 2.63 μmol/h, when the hybrid powders were prepared by mixing Nd and V at a volume ratio of 1:3 at a calcination temperature of 350 °C for 1 h. The hybrid powders were synthesized by neodymium nitrate and ammonium metavanadate using the glycothermal method in ethylene glycol at 120 °C for 1 h. The hybrid powders consisted of two shapes, NdVO4 nanoparticles and the cylindrical V2O5 particles, and they possessed the ability for photocatalytic oxygen (O2) evolution during irradiation with visible light. The band gaps and structures of the hybrid powders were analyzed using UV-visible spectroscopy and transmission electron microscopy. PMID:28772692

Catalytic properties of the VO x /Ce0.46Zr0.54O2 oxide system in the oxidative dehydrogenation of propane

NASA Astrophysics Data System (ADS)

Turakulova, A. O.; Kharlanov, A. N.; Levanov, A. V.; Isaikina, O. Ya.; Lunin, V. V.

2017-01-01

Ce0.46Zr0.54O2 solid solution prepared using a cellulose template was employed as a carrier for vanadium catalysts of the oxidative dehydrogenation of propane. The properties of VO x /Ce0.46Zr0.54O2 catalyst (5 wt % vanadium) are compared with the properties of the neat support. The carrier and catalyst are studied by means of BET, SEM, DTA, XRD, and Raman spectroscopy. It is shown that the CeVO4 phase responsible for the ODH process is formed upon interaction between vanadate ions and cerium ions on the surface of the solid solution. The catalytic properties of the catalyst and the support are studied in the propane oxidation reaction at temperatures of 450 and 500°C with pulse feeding of the reagent. It is found that the complete oxidation of propane occurs on the support with formation of CO2 and H2O. Three products (propene, CO2, and H2O) form in the presence of the vanadium catalyst. It is suggested that there are two types of catalytic centers on the catalyst's surface. It is concluded that the centers responsible for the complete oxidation of propane are concentrated mainly on the carrier, while the centers responsible for propane ODH are on the CeVO4.

In situ electrical resistivity measurements of vanadium thin films performed in vacuum during different annealing cycles

NASA Astrophysics Data System (ADS)

Pedrosa, Paulo; Cote, Jean-Marc; Martin, Nicolas; Arab Pour Yazdi, Mohammad; Billard, Alain

2017-02-01

The present study describes a sputtering and in situ vacuum electrical resistivity setup that allows a more efficient sputtering-oxidation coupling process for the fabrication of oxide compounds like vanadium dioxide, VO2. After the sputtering deposition of pure V thin films, the proposed setup enables the sample holder to be transferred from the sputtering to the in situ annealing + resistivity chamber without venting the whole system. The thermal oxidation of the V films was studied by implementing two different temperature cycles up to 550 °C, both in air (using a different resistivity setup) and vacuum conditions. Main results show that the proposed system is able to accurately follow the different temperature setpoints, presenting clean and low-noise resistivity curves. Furthermore, it is possible to identify the formation of different vanadium oxide phases in air, taking into account the distinct temperature cycles used. The metallic-like electrical properties of the annealed coatings are maintained in vacuum whereas those heated in air produce a vanadium oxide phase mixture.

In situ electrical resistivity measurements of vanadium thin films performed in vacuum during different annealing cycles.

PubMed

Pedrosa, Paulo; Cote, Jean-Marc; Martin, Nicolas; Arab Pour Yazdi, Mohammad; Billard, Alain

2017-02-01

The present study describes a sputtering and in situ vacuum electrical resistivity setup that allows a more efficient sputtering-oxidation coupling process for the fabrication of oxide compounds like vanadium dioxide, VO 2 . After the sputtering deposition of pure V thin films, the proposed setup enables the sample holder to be transferred from the sputtering to the in situ annealing + resistivity chamber without venting the whole system. The thermal oxidation of the V films was studied by implementing two different temperature cycles up to 550 °C, both in air (using a different resistivity setup) and vacuum conditions. Main results show that the proposed system is able to accurately follow the different temperature setpoints, presenting clean and low-noise resistivity curves. Furthermore, it is possible to identify the formation of different vanadium oxide phases in air, taking into account the distinct temperature cycles used. The metallic-like electrical properties of the annealed coatings are maintained in vacuum whereas those heated in air produce a vanadium oxide phase mixture.

Tuning phase transition temperature of VO2 thin films by annealing atmosphere

NASA Astrophysics Data System (ADS)

Liu, Xingxing; Wang, Shao-Wei; Chen, Feiliang; Yu, Liming; Chen, Xiaoshuang

2015-07-01

A simple new way to tune the optical phase transition temperature of VO2 films was proposed by only controlling the pressure of oxygen during the annealing process. Vanadium films were deposited on glass by a large-scale magnetron sputtering coating system and then annealed in appropriate oxygen atmosphere to form the VO2 films. The infrared transmission change (at 2400 nm) is as high as 58% for the VO2 thin film on the glass substrate, which is very good for tuning infrared radiation and energy saving as smart windows. The phase transition temperature of the films can be easily tuned from an intrinsic temperature to 44.7 °C and 40.2 °C on glass and sapphire by annealing oxygen pressure, respectively. The mechanism is: V3+ ions form in the film when under anaerobic conditions, which can interrupt the V4+ chain and reduce the phase transition temperature. The existence of V3+ ions has been observed by x-ray photoelectron spectroscopy (XPS) experiments as proof.

Phase Stability and Transformations in Vanadium Oxide Nanocrystals

NASA Astrophysics Data System (ADS)

Bergerud, Amy Jo

to the bulk stable corundum phase of V2O3 with concurrent particle coarsening. This, in combination with the enhanced stability of the nanocrystals over bulk, suggests that the bixbyite phase may be stabilized due to surface energy effects, a well-known phenomenon in nanocrystal research. In Chapter 3, the reversible incorporation of oxygen in bixbyite V 2O3 is reported, which can be controlled by varying temperature and oxygen partial pressure. Based on XRD and thermogravimetric analysis, it is found that oxygen occupies interstitial sites in the bixbyite lattice. Two oxygen atoms per unit cell can be incorporated rapidly and with minimal changes to the structure while the addition of three or more oxygen atoms destabilizes the structure, resulting in a phase change that can be reversed upon oxygen removal. Density functional theory (DFT) supports the reversible occupation of interstitial sites in bixbyite by oxygen and the 1.1 eV barrier to oxygen diffusion predicted by DFT matches the activation energy of the oxidation process derived from observations by in situ XRD. The observed rapid oxidation kinetics are thus facilitated by short diffusion paths through the bixbyite nanocrystals. Due to the exceptionally low temperatures of oxidation and reduction, this material, made from earth-abundant atoms, is proposed for use in oxygen storage applications, where oxygen is reversibly stored and released. Further oxidation of bixbyite V2O3 under controlled oxygen partial pressure can lead to the formation of nanocrystalline vanadium dioxide (VO2), a material that is studied for its MIT that occurs at 68 C in the bulk. This transformation is accompanied by a change in crystal structure, from monoclinic to rutile phase, and a change in optical properties, from infrared transparent to infrared blocking. Because of this, VO2 is promising for thermochromic smart window applications, where optical properties vary with temperature. Recently, alternative stimuli have been

Cottonseed meal, dehydrated grass and ascorbic acid as dietary factors preventing toxicity of vanadium for the chick

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berg, L.R.; Lawrence, W.W.

1971-01-01

Studies have been conducted which show that the replacement of 5% sucrose in a sucrose-fish meal diet for chicks with degossypolized cottonseed meal prevents the toxicity of 20 ppm added vanadium. The addition of 5% dehydrated grass to the same ration markedly reduced the toxicity symptoms. No such reduction in vanadium toxicity resulted when soybean meal, corn gluten meal, meat meal, fish meal, casein, isolated soybean protein, zein or wheat gluten were added to the ration. No evidence was found that the gossypol remaining in the cottonseed meal was the detoxifying agent. The addition of 0.25 to 0.50% ascorbic acidmore » to the sucrose-fish meal basal ration prevented the toxic symptoms resulting from the addition of 20 ppm vanadium derived from HN/sub 4/VO/sub 3/. The vanadium derived from VOSO/sub 4/ and VOCl/sub 2/ (vanadium valence 4) was as toxic as vanadium derived from HN/sub 4/VO/sub 3/ (V = valence 5). This leads one to question that the action of ascorbic acid in reducing vanadium toxicity is through its property of a reducing agent which might change the vanadium in VH/sub 4/VO/sub 3/ to a lower valence, presumably less toxic.« less

Reactively sputtered thermochromic tungsten-doped VO2 films

NASA Astrophysics Data System (ADS)

Sobhan, M. A.; Kivaisi, R. T.; Stjerna, B. A.; Granqvist, Claes-Goeran

1994-09-01

Tungsten-doped vanadium oxide (V1-xWxO2) films were prepared by concurrent reactive dc magnetron sputtering of vanadium and tungsten in an Ar + O2 plasma with a controlled oxygen partial pressure. Films were deposited onto glass substrates at 400 degree(s)C. The films had a metal-semiconductor transition at a temperature (tau) t that was depressed when x was increased. Rutherford Back Scattering was used to determine x. X- ray diffraction was employed to confirm the monoclinic low-temperature VO2 phase. The relation between x and (tau) t was studied and compared with results from the literature. It was shown that (tau) t could be set to a value between 17 and 65 degree(s)C by proper choice of x. The optical and electrical properties of the films were investigated around the metal-semiconductor phase transition. The luminous transmittance was rather unaffected by the temperature, whereas the near infrared transmittance showed lower values above (tau) t. The degree of thermochromic modulation decreased for increased x. Electrical measurements showed that the ratio of the resistance above and below (tau) t decreased with increasing x.

Hybrid Ag 2VO 2PO 4/CF x as a High Capacity and Energy Cathode for Primary Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Yue Ru; Bruck, Andrea M.; Brady, Alexander B.

In this report, we describe the electrochemistry of hybrid dual silver vanadium phosphorus oxide/carbon fluoride (Ag 2VO 2PO 4/CF x) cathodes with various weight ratios. Through modification of the Ag 2VO 2PO 4/CF x ratio, we can control the gravimetric and volumetric capacity, as well as mitigate the voltage drop during high current pulses. The increase in impedance caused by irreversible LiF formation in CFx was reduced by the silver reduction-displacement during electrochemical discharge of the Ag 2VO 2PO 4. Moreover, the addition of graphite was shown to reduce initial voltage delay. When Ag 2VO 2PO 4 dominates the electrodemore » mass (i.e. 75/25 Ag 2VO 2PO 4/CF x) in the hybrid cathode, pulse testing shows less voltage drop and delay, but at the expense of capacity and energy density. As the amount of CFx in the composite increases (i.e. Ag 2VO 2PO 4/CF x ratio of to 50/50 or 25/75), charge capacity and energy density increases, but at the expense of larger voltage drops and delays early in the discharge process. Thus, controlling the Ag 2VO 2PO 4/CF x ratio can be used to tune the electrochemical properties of the dual cathode, allowing for optimization of capacity and power depending on the application.« less

Hybrid Ag 2VO 2PO 4/CF x as a High Capacity and Energy Cathode for Primary Batteries

DOE PAGES

Li, Yue Ru; Bruck, Andrea M.; Brady, Alexander B.; ...

2017-08-18

In this report, we describe the electrochemistry of hybrid dual silver vanadium phosphorus oxide/carbon fluoride (Ag 2VO 2PO 4/CF x) cathodes with various weight ratios. Through modification of the Ag 2VO 2PO 4/CF x ratio, we can control the gravimetric and volumetric capacity, as well as mitigate the voltage drop during high current pulses. The increase in impedance caused by irreversible LiF formation in CFx was reduced by the silver reduction-displacement during electrochemical discharge of the Ag 2VO 2PO 4. Moreover, the addition of graphite was shown to reduce initial voltage delay. When Ag 2VO 2PO 4 dominates the electrodemore » mass (i.e. 75/25 Ag 2VO 2PO 4/CF x) in the hybrid cathode, pulse testing shows less voltage drop and delay, but at the expense of capacity and energy density. As the amount of CFx in the composite increases (i.e. Ag 2VO 2PO 4/CF x ratio of to 50/50 or 25/75), charge capacity and energy density increases, but at the expense of larger voltage drops and delays early in the discharge process. Thus, controlling the Ag 2VO 2PO 4/CF x ratio can be used to tune the electrochemical properties of the dual cathode, allowing for optimization of capacity and power depending on the application.« less

Highly repeatable nanoscale phase coexistence in vanadium dioxide films

NASA Astrophysics Data System (ADS)

Huffman, T. J.; Lahneman, D. J.; Wang, S. L.; Slusar, T.; Kim, Bong-Jun; Kim, Hyun-Tak; Qazilbash, M. M.

2018-02-01

It is generally believed that in first-order phase transitions in materials with imperfections, the formation of phase domains must be affected to some extent by stochastic (probabilistic) processes. The stochasticity would lead to unreliable performance in nanoscale devices that have the potential to exploit the transformation of physical properties in a phase transition. Here we show that stochasticity at nanometer length scales is completely suppressed in the thermally driven metal-insulator transition (MIT) in sputtered vanadium dioxide (V O2 ) films. The nucleation and growth of domain patterns of metallic and insulating phases occur in a strikingly reproducible way. The completely deterministic nature of domain formation and growth in films with imperfections is a fundamental and unexpected finding about the kinetics of this material. Moreover, it opens the door for realizing reliable nanoscale devices based on the MIT in V O2 and similar phase-change materials.

Vanadyl (IV) and vanadate (V) binding to selected endogenous phosphate, carboxyl, and amino ligands; calculations of cellular vanadium species distribution.

PubMed

Nechay, B R; Nanninga, L B; Nechay, P S

1986-11-15

Vanadium enters cells as vanadate (V) where it is reduced to vanadyl (IV), VO2+. Vanadate species at plasma pH, H2VO4-, and HVO4(2-) are referred to as VO3-. To gain an insight into the subcellular vanadium distribution we measured the binding of VO3- and VO2+ to extra- and intracellular ligands, and calculated free and bound fractions of these ions for expected in vivo conditions. The association constants (K) were determined by the pH shift caused by an addition of VOSO4 or NaVO3 to individual ligand solutions at 20 degrees C and a pH equal to the pK of the reactive groups. The pk's for binding of VO2+ were ATP, 5.9; ADP, 5.5; AMP, 5.1; Pi 4.3; creatine phosphate (CP), 3.6; glutamic acid, 3.4; aspartic acid, 3.1; human serum albumin, 3.1; glutathione, 2.7; ascorbic acid, 3.3; citric acid, 4.0. The pk of VO3- and human serum albumin was 3.3 and of that VO3- and glutathione was 4.2. VO3- did not bind to ATP, even via Mg2+ or Ca2+ bridges. We calculated that in cells approximately 1% of total VO2+ is unbound, which is 10(-10)-10(-9) M since published values for total vanadium (mainly VO2+) concentrations in tissues are on the order of 10(-8)-10(-7) M. Free VO2+ may be even less because of binding to additional ligands not considered and due to spontaneous hydrolysis to VOOH+ and VO(OH)2(2+) at intracellular pH. The binding of VO2+ to each ligand was corrected for presence of multiple ligands and competition by H+, K+, and Mg2+. In cells with no CP, up to 70% of VO2+ is bound to phosphates and up to 29% to proteins; in cells with 30 mM CP (as in muscle), approximately 95% is bound to phosphates (CP binds up to 61% of total VO2+) and approximately 4% to proteins; in cells with 2 mM ascorbic acid (as in brain), the vitamin binds approximately 3% of total VO2+. These binding values apply for the total VO2+ concentration range of 10(-8)-10(-5) M. The intracellular binding and a reducing environment protect the freshly reduced VO2+ from oxidation to VO3- that would

Surface charge sensing by altering the phase transition in VO2

NASA Astrophysics Data System (ADS)

Kumar, S.; Esfandyarpour, R.; Davis, R.; Nishi, Y.

2014-08-01

Detection of surface charges has various applications in medicine, electronics, biotechnology, etc. The source of surface charge induction may range from simple charge-polarized molecules like water to complicated proteins. It was recently discovered that surface charge accumulation can alter the temperature at which VO2 undergoes a Mott transition. Here, we deposited polar molecules onto the surface of two-terminal thin-film VO2 lateral devices and monitored the joule-heating-driven Mott transition, or conductance switching. We observed that the power required to induce the conductance switching reduced upon treatment with polar molecules and, using in-situ blackbody-emission direct measurement of local temperature, we show that this reduction in power was accompanied by reduction in the Mott transition temperature. Further evidence suggested that this effect has specificity to the nature of the species used to induce surface charges. Using x-ray absorption spectroscopy, we also show that there is no detectable change in oxidation state of vanadium or structural phase in the bulk of the 40 nm VO2 thin-film even as the phase transition temperature is reduced by up to 20 K by the polar molecules. The ability to alter the phase transition parameters by depositing polar molecules suggests a potential application in sensing surface charges of different origins and this set of results also highlights interesting aspects of the phase transition in VO2.

Vanadium dioxide based frequency tunable metasurface filters for realizing reconfigurable terahertz optical phase and polarization control.

PubMed

Nouman, M Tayyab; Hwang, Ji Hyun; Faiyaz, Mohd; Lee, Kye-Jeong; Noh, Do-Young; Jang, Jae-Hyung

2018-05-14

Metasurfaces are two dimensional arrays of artificial subwavelength resonators, which can manipulate the amplitude and phase profile of incident electromagnetic fields. To date, limited progress has been achieved in realizing reconfigurable phase control of incident waves using metasurfaces. Here, an active metasurface is presented, whose resonance frequency can be tuned by employing insulator to metal transition in vanadium dioxide. By virtue of the phase jump accompanied by the resonance frequency tuning, the proposed metasurface acts as a phase shifter at THz frequency. It is further demonstrated that by appropriately tailoring the anisotropy of the metasurface, the observed phase shift can be used to switch the transmitted polarization from circular to approximately linear. This work thus shows potential for reconfigurable phase and polarization control at THz frequencies using vanadium dioxide based frequency tunable metasurfaces.

Combined Thermochromic And Plasmonic: Optical Responses In Novel Nanocomposite Au-VO2 Films Prepared By RF Inverted Cylindrical Magnetron Sputtering

NASA Astrophysics Data System (ADS)

Kana, J. B. Kana; Ndjaka, J. M.; Manyala, N.; Nemraoui, O.; Beye, A. C.; Maaza, M.

2008-09-01

We prepared gold/Vanadium dioxide nanocomposites thin films by the rf reactive inverted cylindrical magnetron sputtering (ICMS) for the first time and report their enhanced surface plasmon resonance (SPR) tunable shift reversibility. ICMS has been attracting much attention for its ability for uniform coating of three-dimensional objects and high-rate deposition of dielectric materials. To investigate the optical properties of gold nanoparticles embedded in an active matrix (VO2) composite film was synthesized on corning glass substrates for several substrate temperatures ranging from 400 °C to 600 °C. The X-ray diffraction results demonstrated that the Au and VO2 were well crystallized. The optical transmission properties were measured from 300nm to 1100nm and the absorption peak due to the surface plasmon resonance (SPR) of Au nanoparticles were observed. Under external temperature stimuli, the tunable reversibility of the SPR shift was observed when the nanocomposites temperature varies from 20 °C to 100 °C. The enhancement of this shift of SPR was observed as the substrate temperature increases and it was found that the shift of SPR increased rapidly with increasing substrate temperature but then remained constant at ˜57 nm for substrate temperature higher than 500 °C.

Measurement of collective excitations in VO 2 by resonant inelastic x-ray scattering

DOE PAGES

He, Haowei; Gray, A. X.; Granitzka, P.; ...

2016-10-15

Vanadium dioxide is of broad interest as a spin-1/2 electron system that realizes a metal-insulator transition near room temperature, due to a combination of strongly correlated and itinerant electron physics. Here, resonant inelastic x-ray scattering is used to measure the excitation spectrum of charge and spin degrees of freedom at the vanadium L edge under different polarization and temperature conditions, revealing excitations that differ greatly from those seen in optical measurements. Furthermore, these spectra encode the evolution of short-range energetics across the metal-insulator transition, including the low-temperature appearance of a strong candidate for the singlet-triplet excitation of a vanadium dimer.

Anisotropic vanadium dioxide sculptured thin films with superior thermochromic properties.

PubMed

Sun, Yaoming; Xiao, Xiudi; Xu, Gang; Dong, Guoping; Chai, Guanqi; Zhang, Hua; Liu, Pengyi; Zhu, Hanmin; Zhan, Yongjun

2013-09-25

VO2 (M) STF through reduction of V2O5 STF was prepared. The results illustrate that V2O5 STF can be successfully obtained by oblique angle thermal evaporation technique. After annealing at 550 °C/3 min, the V2O5 STF deposited at 85° can be easily transformed into VO2 STF with slanted columnar structure and superior thermochromic properties. After deposition SiO2 antireflective layer, Tlum of VO2 STF is enhanced 26% and ΔTsol increases 60% compared with that of normal VO2 thin films. Due to the anisotropic microstructure of VO2 STF, angular selectivity transmission of VO2 STF is observed and the solar modulation ability is further improved from 7.2% to 8.7% when light is along columnar direction. Moreover, the phase transition temperature of VO2 STF can be depressed into 54.5 °C without doping. Considering the oblique incidence of sunlight on windows, VO2 STF is more beneficial for practical application as smart windows compared with normal homogenous VO2 thin films.

Synthesis, characterization, X-ray crystal structure, DFT calculation and antibacterial activities of new vanadium(IV, V) complexes containing chelidamic acid and novel thiourea derivatives.

PubMed

Farzanfar, Javad; Ghasemi, Khaled; Rezvani, Ali Reza; Delarami, Hojat Samareh; Ebrahimi, Ali; Hosseinpoor, Hona; Eskandari, Amir; Rudbari, Hadi Amiri; Bruno, Giuseppe

2015-06-01

Three new thiourea ligands derived from the condensation of aroyl- and aryl-isothiocyanate derivatives with 2,6-diaminopyridine, named 1,1'-(pyridine-2,6-diyl)bis(3-(benzoyl)thiourea) (L1), 1,1'-(pyridine-2,6-diyl)bis(3-(2-chlorobenzoyl)thiourea) (L2) and 1,1'-(pyridine-2,6-diyl)bis(3-(4-chlorophenyl)thiourea) (L3), their oxido-vanadium(IV) complexes, namely [VO(L1('))(H2O)] (C1), [VO(L2('))(H2O)] (C2) and [VO(L3('))(H2O)] (C3), and also, dioxo-vanadium(V) complex containing 4-hydroxy-2,6-pyridine dicarboxylic acid (chelidamic acid, H2dipic-OH) and metformin (N,N-dimethylbiguanide, Met), named [H2Met][VO2(dipic-OH)]2·H2O (C4), were synthesized and characterized by elemental analysis, FTIR and (1)H NMR and UV-visible spectroscopies. Proposed structures for free thiourea ligands and their vanadium complexes were corroborated by applying geometry optimization and conformational analysis. Solid state structure of complex [H2Met][VO2(dipic-OH)]2·H2O (triclinic, Pī) was fully determined by single crystal X-ray diffraction analysis. In this complex, metformin is double protonated and acted as counter ion. The antibacterial properties of these compounds were investigated in vitro against standard Gram-positive and Gram-negative bacterial strains. The experiments showed that vanadium(IV) complexes had the superior antibacterial activities than novel thiourea derivatives and vanadium(V) complex against all Gram-positive and Gram-negative bacterial strains. Copyright © 2015 Elsevier Inc. All rights reserved.

Deposition of vanadium oxide films by direct-current magnetron reactive sputtering

NASA Astrophysics Data System (ADS)

Kusano, E.; Theil, J. A.; Thornton, John A.

1988-06-01

It is demonstrated here that thin films of vanadium oxide can be deposited at modest substrate temperatures by dc reactive sputtering from a vanadium target in an O2-Ar working gas using a planar magnetron source. Resistivity ratios of about 5000 are found between a semiconductor phase with a resistivity of about 5 Ohm cm and a metallic phase with a resistivity of about 0.001 Ohm cm for films deposited onto borosilicate glass substrates at about 400 C. X-ray diffraction shows the films to be single-phase VO2 with a monoclinic structure. The VO2 films are obtained for a narrow range of O2 injection rates which correspond to conditions where cathode poisoning is just starting to occur.

Deposition of vanadium oxide films by direct-current magnetron reactive sputtering

NASA Technical Reports Server (NTRS)

Kusano, E.; Theil, J. A.; Thornton, John A.

1988-01-01

It is demonstrated here that thin films of vanadium oxide can be deposited at modest substrate temperatures by dc reactive sputtering from a vanadium target in an O2-Ar working gas using a planar magnetron source. Resistivity ratios of about 5000 are found between a semiconductor phase with a resistivity of about 5 Ohm cm and a metallic phase with a resistivity of about 0.001 Ohm cm for films deposited onto borosilicate glass substrates at about 400 C. X-ray diffraction shows the films to be single-phase VO2 with a monoclinic structure. The VO2 films are obtained for a narrow range of O2 injection rates which correspond to conditions where cathode poisoning is just starting to occur.

Effects of Vanadium-Containing Compounds on Membrane Lipids and on Microdomains Used in Receptor-Mediated Signaling

PubMed Central

Roess, Deborah A.; Smith, Steven M. L.; Winter, Peter; Zhou, Jun; Dou, Ping; Baruah, Bharat; Trujillo, Alejandro M.; Levinger, Nancy E.; Yang, Xioda; Barisas, B. George; Crans, Debbie C.

2011-01-01

There is increasing evidence for the involvement of plasma membrane microdomains in insulin receptor function. Moreover, disruption of these structures, which are typically enriched in sphingomyelin and cholesterol, results in insulin resistance. Treatment strategies for insulin resistance include the use of vanadium compounds which have been shown in animal models to enhance insulin responsiveness. One possible mechanism for insulin-enhancing effects might involve direct effects of vanadium compounds on membrane lipid organization. These changes in lipid organization promote the partitioning of insulin receptors and other receptors into membrane microdomains where receptors are optimally functional. To explore this possibility, we have used several strategies involving vanadium complexes such as [VO2dipic]− (pyridin-2,6-dicarboxylatodioxovanadium(V)), decavanadate (V10O286−, V10), BMOV (bis(maltolato)oxovanadium(IV)) and [VO(saltris)]2 (2-salicylideniminato-2-(hydroxymethyl)-1,3-dihydroxypropane-oxovanadium(V)). Our strategies include an evaluation of interactions between vanadium-containing compounds and model lipid systems, an evaluation of the effects of vanadium compounds on lipid fluidity in erythrocyte membranes, and studies of the effects of vanadium-containing compounds on signaling events initiated by receptors known to use membrane microdomains as signaling platforms. PMID:18729092

Speciation of vanadium in Chinese cabbage (Brassica rapa L.) and soils in response to different levels of vanadium in soils and cabbage growth.

PubMed

Tian, Liyan; Yang, Jinyan; Alewell, Christine; Huang, Jen-How

2014-09-01

This study highlights the accumulation and speciation of vanadium in Chinese cabbage (Brassica rapa L.) in relation to the speciation of soil vanadium with pot experiments at 122-622mgVkg(-1) by spiking NH4VO3. Cabbage planting decreased the bioavailable and residual vanadium based on sequential extraction, leading to enrichment of oxalate-extractable vanadium in soils. The biomass production increased with increasing concentrations of soil vanadium from 122 to 372mgVkg(-1), probably due to the increasing nitrogen availability and low vanadium availability in our soils with a consequent low vanadium toxicity. Although the concentrations of root vanadium (14.4-24.9mgVkg(-1)) related positively with soil vanadium, the bio-dilution alleviated the increase of leaf vanadium (2.1-2.7mgVkg(-1)). The predominance of vanadium(IV) in leaves (∼60-80% of total vanadium) indicates bio-reduction of vanadium in Chinese cabbage, since the mobile vanadium in oxic soils was usually pentavalent. Approximately 15-20% of the leaf vanadium was associated with recalcitrant leaf tissues. The majority of leaf vanadium was water and ethanol extractable, which is considered mobile and may cause more toxic effects on Chinese cabbage. Copyright © 2014 Elsevier Ltd. All rights reserved.

Three-dimensional Nitrogen-Doped Reduced Graphene Oxide/Carbon Nanotube Composite Catalysts for Vanadium Flow Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

The development of vanadium redox flow battery is limited by the sluggish kinetics of the reaction, especially the cathodic VO2+/VO2+ redox couples. Therefore, it is vital to develop new electrocatalyst with enhanced activity to improve the battery performance. Herein, we first synthesized the hydrogel precursor by a facile hydrothermal method. After the following carbonization, nitrogen-doped reduced graphene oxide/carbon nanotube composite was obtained. By virtue of the large surface area and good conductivey, which are ensured by the unique hybrid structure, as well as the proper nitrogen doping, the as-prepared composite presents enhanced catalytic performance toward the VO2+/VO2+ redox reaction. Wemore » also demonstrated the composite with carbon nanotube loading of 2 mg/mL exhibits the highest activity and remarkable stability in aqueous solution due to the strong synergy between reduced graphene oxide and carbon nanotubes, indicating that this composite might show promising applications in vanadium redox flow battery.« less

Anisotropic vanadium dioxide sculptured thin films with superior thermochromic properties

PubMed Central

Sun, Yaoming; Xiao, Xiudi; Xu, Gang; Dong, Guoping; Chai, Guanqi; Zhang, Hua; Liu, Pengyi; Zhu, Hanmin; Zhan, Yongjun

2013-01-01

VO2 (M) STF through reduction of V2O5 STF was prepared. The results illustrate that V2O5 STF can be successfully obtained by oblique angle thermal evaporation technique. After annealing at 550°C/3 min, the V2O5 STF deposited at 85° can be easily transformed into VO2 STF with slanted columnar structure and superior thermochromic properties. After deposition SiO2 antireflective layer, Tlum of VO2 STF is enhanced 26% and ΔTsol increases 60% compared with that of normal VO2 thin films. Due to the anisotropic microstructure of VO2 STF, angular selectivity transmission of VO2 STF is observed and the solar modulation ability is further improved from 7.2% to 8.7% when light is along columnar direction. Moreover, the phase transition temperature of VO2 STF can be depressed into 54.5°C without doping. Considering the oblique incidence of sunlight on windows, VO2 STF is more beneficial for practical application as smart windows compared with normal homogenous VO2 thin films. PMID:24067743

Preparation and modification of VO2 thin film on R-sapphire substrate by rapid thermal process

NASA Astrophysics Data System (ADS)

Zhu, Nai-Wei; Hu, Ming; Xia, Xiao-Xu; Wei, Xiao-Ying; Liang, Ji-Ran

2014-04-01

The VO2 thin film with high performance of metal-insulator transition (MIT) is prepared on R-sapphire substrate for the first time by magnetron sputtering with rapid thermal process (RTP). The electrical characteristic and THz transmittance of MIT in VO2 film are studied by four-point probe method and THz time domain spectrum (THz-TDS). X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and search engine marketing (SEM) are employed to analyze the crystalline structure, valence state, surface morphology of the film. Results indicate that the properties of VO2 film which is oxidized from the metal vanadium film in oxygen atmosphere are improved with a follow-up RTP modification in nitrogen atmosphere. The crystallization and components of VO2 film are improved and the film becomes compact and uniform. A better phase transition performance is shown that the resistance changes nearly 3 orders of magnitude with a 2-°C hysteresis width and the THz transmittances are reduced by 64% and 60% in thermal and optical excitation respectively.

Combined Thermochromic And Plasmonic: Optical Responses In Novel Nanocomposite Au-VO{sub 2} Films Prepared By RF Inverted Cylindrical Magnetron Sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kana, J. B. Kana; Department of physics, University of Yaounde I, P.O. Box 812 Yaounde; Ndjaka, J. M.

2008-09-23

We prepared gold/Vanadium dioxide nanocomposites thin films by the rf reactive inverted cylindrical magnetron sputtering (ICMS) for the first time and report their enhanced surface plasmon resonance (SPR) tunable shift reversibility. ICMS has been attracting much attention for its ability for uniform coating of three-dimensional objects and high-rate deposition of dielectric materials. To investigate the optical properties of gold nanoparticles embedded in an active matrix (VO{sub 2}) composite film was synthesized on corning glass substrates for several substrate temperatures ranging from 400 deg. C to 600 deg. C. The X-ray diffraction results demonstrated that the Au and VO{sub 2} weremore » well crystallized. The optical transmission properties were measured from 300nm to 1100nm and the absorption peak due to the surface plasmon resonance (SPR) of Au nanoparticles were observed. Under external temperature stimuli, the tunable reversibility of the SPR shift was observed when the nanocomposites temperature varies from 20 deg. C to 100 deg. C. The enhancement of this shift of SPR was observed as the substrate temperature increases and it was found that the shift of SPR increased rapidly with increasing substrate temperature but then remained constant at {approx}57 nm for substrate temperature higher than 500 deg. C.« less

Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Xiaoya; Huang, Yiqing; Ji, Dongsheng

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safetymore » of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.« less

Structure evolution and thermal stability of high-energy density Li-ion battery cathode Li 2VO 2F

DOE PAGES

Wang, Xiaoya; Huang, Yiqing; Ji, Dongsheng; ...

2017-05-24

Lithium-ion batteries (LIBs) provide high-energy-density electrochemical energy storage, which plays a central role in advancing technologies ranging from portable electronics to electric vehicles (EVs). However, a demand for lighter, more compact devices and for extended range EVs continues to fuel the need for higher energy density storage systems. Li 2VO 2F, which is synthesized in its lithiated state, allows two-electron transfer per formula during the electrochemical reaction providing a high theoretical capacity of 462 mAh/g. Herein, the synthesis and electrochemical performance of Li 2VO 2F are optimized. The thermal stability of Li 2VO 2F, which is related to the safetymore » of a battery is studied by thermal gravimetric analysis. The structure and vanadium oxidation state evolution along Li cycling are studied by ex-situ X-ray diffraction and absorption techniques. It is shown that the rock-salt structure of pristine Li 2VO 2F is stable up to at least 250°C, and is preserved upon Li cycling, which proceeds by the solid-solution mechanism. However, not all Li can be removed from the structure upon charge to 4.5 V, limiting the experimentally obtained capacity.« less

Heterogeneous nucleation and growth dynamics in the light-induced phase transition in vanadium dioxide

DOE PAGES

Brady, Nathaniel F.; Appavoo, Kannatassen; Seo, Minah; ...

2016-03-02

Here we report on ultrafast optical investigations of the light-induced insulator-to-metal phase transition in vanadium dioxide with controlled disorder generated by substrate mismatch. These results reveal common dynamics of this optically-induced phase transition that are independent of this disorder. Lastly, above the fluence threshold for completing the transition to the rutile crystalline phase, we find a common time scale, independent of sample morphology, of 40.5 ± 2 ps that is consistent with nucleation and growth dynamics of the R phase from the parent M1 ground state.

Porous poly(benzimidazole) membrane for all vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Luo, Tao; David, Oana; Gendel, Youri; Wessling, Matthias

2016-04-01

Porous poly(benzimidazole) (PBI) membranes of low vanadium ions permeability are described for an all vanadium redox flow battery (VRFB). The PBI membrane was prepared by a water vapour induced phase inversion process of a PBI polymer solution. The membrane has a symmetrical cross-sectional morphology. A low water permeability of 16.5 L (m2 h bar)-1 indicates the high hydraulic resistance stemming from a closed cell morphology with nanoporous characteristics. The PBI membrane doped with 2.5 M H2SO4 shows a proton conductivity of 16.6 mS cm-1 and VO2+ permeability as low as 4.5 × 10-8 cm2 min-1. The stability test of dense PBI membrane in VO2+ solution indicates good chemical stability. An all vanadium redox flow battery (VRFB) operated with the porous PBI membrane shows 98% coulombic efficiency and more than 10% higher energy efficiency compared to VRFB operated with Nafion 112 at applied current densities of 20-40 mA cm-2. High in situ stability of the porous PBI membrane was confirmed by about 50 cycles of continuous charge and discharge operation of the battery.

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.

Studies of the complexation of new promising ligands with uranyl (UO 2 2+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO 2 2+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO 2 2+, VO 2+, and VO 2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques,more » along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO 2 2+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO 2 2+, VO 2+, and VO 2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO 2 2+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Highly Preorganized Ligand 1,10-Phenanthroline-2,9-dicarboxylic Acid for the Selective Recovery of Uranium from Seawater in the Presence of Competing Vanadium Species

DOE PAGES

Lashley, Mark A.; Ivanov, Alexander S.; Bryantsev, Vyacheslav S.; ...

2016-09-30

Studies of the complexation of new promising ligands with uranyl (UO 2 2+) and other seawater cations can aid the development of more efficient, selective, and robust sorbents for the recovery of uranium from seawater. Here, we propose that the ligand design principles based on structural preorganization can be successfully applied to obtain a dramatic enhancement in UO 2 2+ ion binding affinity and selectivity. This concept is exemplified through the investigation of the com-plexes of UO 2 2+, VO 2+, and VO 2+ with the highly preorganized ligand PDA (1,10-phenanthroline-2,9-dicarboxylic acid) using a combination of fluores-cence and absorbance techniques,more » along with den-sity functional theory (DFT) calculations. Moreover, the measured stability constant value, log K1, of 16.5 for the UO 2 2+/PDA complex is very high compared to uranyl complexes with other dicarboxylic ligands. Moreover, PDA exhibits strong selectivity for uranyl over vanadium ions, since the determined sta-bility constant values of the PDA complexes of the vanadium ions are quite low (V(IV) log K1 = 7.4, V(V) = 7.3). Finally, the structures of the corresponding UO 2 2+, VO 2+, and VO 2+ complexes with PDA were identified by systematic DFT calculations, and helped to interpret the stronger binding affinity for uranium over the vanadium ions. Due to its high chemical stability, selectivity, and structural preor-ganization for UO 2 2+ complexation, PDA is a very promising candidate that can be potentially used in the development of novel adsorbent materials for the selective extraction of uranium from sea-water.« less

Structure-property relationships in NO x sensor materials composed of arrays of vanadium oxide nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Putrevu, Naga Ravikanth; Darling, Seth B.; Segre, Carlo U.

The mixed-valent vanadium oxide based three-dimensional framework structure species [Cd 3(H 2O) 12V 16 IVV 2 VO 36(OH) 6(AO 4)]∙24H 2O, (A=V,S) (Cd 3(VO) o) represents a rare example of an interesting sensor material which exhibits NO x {NO+NO 2} semiconducting gas sensor properties under ambient conditions. The electrical resistance of the sensor material Cd 3(VO) o decreases in air. Combined characterization studies revealed that the building block, {V 18O 42(AO 4)} cluster, of 3-D framework undergoes oxidation and remains intact for at least 2 months. The decrease in resistance is attributable to the reactivity of molecular oxygen towards vanadiummore » which results in an increase in the oxidation state as well as the coordination number of vanadium center and decrease in band gap of Cd 3(VO) o. Based on these results we propose that the changes in semiconducting properties of Cd 3(VO) o under ambient conditions are due to the greater overlap between the O 2p and V 3d orbitals occurring during the oxidation.« less

Growth control of the oxidation state in vanadium oxide thin films

NASA Astrophysics Data System (ADS)

Lee, Shinbuhm; Meyer, Tricia L.; Park, Sungkyun; Egami, Takeshi; Lee, Ho Nyung

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase pure epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V2 + 3 O 3 , V + 4 O 2 , and V2 + 5 O 5 . A well pronounced MIT was only observed in VO2 films grown in a very narrow range of oxygen partial pressure P(O2). The films grown either in lower (<10 mTorr) or higher P(O2) (>25 mTorr) result in V2O3 and V2O5 phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO2 thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.

Vanadium oxide thin films produced by magnetron sputtering from a V2O5 target at room temperature

NASA Astrophysics Data System (ADS)

de Castro, Marcelo S. B.; Ferreira, Carlos L.; de Avillez, Roberto R.

2013-09-01

Vanadium oxide thin films were grown by RF magnetron sputtering from a V2O5 target at room temperature, an alternative route of production of vanadium oxide thin films for infrared detector applications. The films were deposited on glass substrates, in an argon-oxygen atmosphere with an oxygen partial pressure from nominal 0% to 20% of the total pressure. X-ray diffraction (XRD) and X-ray photon spectroscopy (XPS) analyses showed that the films were a mixture of several vanadium oxides (V2O5, VO2, V5O9 and V2O3), which resulted in different colors, from yellow to black, depending on composition. The electrical resistivity varied from 1 mΩ cm to more than 500 Ω cm and the thermal coefficient of resistance (TCR), varied from -0.02 to -2.51% K-1. Computational thermodynamics was used to simulate the phase diagram of the vanadium-oxygen system. Even if plasma processes are far from equilibrium, this diagram provides the range of oxygen pressures that lead to the growth of different vanadium oxide phases. These conditions were used in the present work.

Synthesis, Magnetism, and X-ray Molecular Structure of the Mixed-Valence Vanadium(IV/V)-Oxygen Cluster [VO(4) subset(V(18)O(45))](9-).

PubMed

Suber, Lorenza; Bonamico, Mario; Fares, Vincenzo

1997-05-07

Within the transition metal oxide systems, vanadium presents a unique chemistry due to its capacity to form a great number of mixed-valence oxo clusters which often have the peculiarity to incorporate species that function, for size, shape, and charge, as templates. Prismatic, lustrous dark brown crystals of [(n-C(4)H(9))NH(3)](9)[V(19)O(49)].7H(2)O are obtained by reacting (n-C(4)H(9)NH(3))VO(3), VOSO(4), and (n-C(4)H(9))NH(2) in H(2)O. The X-ray crystal structure shows an ellipsoidal metal-oxo cluster formed by 15 VO(5) and 3 VO(4) polyhedra surrounding an almost regular VO(4) tetrahedron located on the 3-fold axis of a trigonal cell of dimensions a = 19.113(5) Å and c = 13.743(5) Å with space group P&thremacr; and Z = 2. Exponentially weighted bond valence sum calculations, manganometric titration of the V(IV) centers, and magnetic measurements are consistent with the presence of three localized and three delocalized electrons. Variable-temperature solid-state susceptibility studies indicate antiferromagnetic coupling between V(IV) centers. Cyclic voltammetry in acetonitrile shows a irreversible reduction at -1.24 V and a reversible oxidation at +0.17 V (vs Ag/AgCl). The title compound converts quantitatively to the metal oxide K(2)V(3)O(8) with an extended layered structure as soon as a potassium salt is added to a neutral aqueous solution of the polyoxoanion.

Synthesis and thermochromic property studies on W doped VO2 films fabricated by sol-gel method.

PubMed

Pan, Guoping; Yin, Jinhua; Ji, Keli; Li, Xiang; Cheng, Xingwang; Jin, Haibo; Liu, Jiping

2017-07-21

Tungsten-doped VO 2 thin films have been synthesized by a modified sol-gel process and followed by a post annealing. Vanadium pentoxide and tungstic acid as raw materials with the addition of hydrogen peroxide, concentrated hydrochloric acid (catalyst) and oxalic acid used as reducing agent were reacted in isobutanol. Finally, the uniform sol of vanadyl oxalate in isobutanol solvent was obtained as precursor. Detailed study suggested that W doped in VO 2 introduces additional electron carriers and induces the formation of V 3+ . Post annealing under vacuum promotes the releasing of chemical stress and generates oxygen vacancies in the samples. Temperature dependent transmittance study revealed that the releasing of chemical stress and deliberately introducing oxygen vacancies in W-doped VO 2 films have positive effects on enhancing its switching ability in the infrared transmittance as the metal-insulator transition (MIT) occurs. The largest switching of transmittance was obtained about 48% in the infrared range at 43 °C in 1.5%W doped VO 2 films, which is significantly larger than the reported ones. The findings in this work open a new way to synthesize the novel and thermochromic W doped VO 2 films with facility and low cost. Therefore, it has extensive application to construct smart windows and electronic devices.

Semiconductor to Metal Transition Characteristics of VO2/NiO Epitaxial Heterostructures Integrated with Si(100)

NASA Astrophysics Data System (ADS)

Molaei, Roya

The novel functionalities of Vanadium dioxide (VO2), such as, several orders of magnitude transition in resistivity and IR transmittance, provide the exciting opportunity for the development of next generation memory, sensor, and field-effect based devices. A critical issue in the development of practical devices based on metal oxides is the integration of high quality epitaxial oxide thin films with the existing silicon technology which is based on silicon (100) substrates. However, silicon is not suitable for epitaxial growth of oxides owing to its tendency to readily form an amorphous oxide layer or silicide at the film-substrate interface. The oxide films deposited directly on silicon exhibit poor crystallinity and are not suitable for device applications. To overcome this challenge, appropriate substrate templates must be developed for the growth of oxide thin films on silicon substrates. The primary objective of this dissertation was to develop an integration methodology of VO2 with Si (100) substrates so they could be used in "smart" sensor type of devices along with other multifunctional devices on the same silicon chip. This was achieved by using a NiO/c- YSZ template layer deposited in situ. It will be shown that if the deposition conditions are controlled properly. This approach was used to integrate VO 2 thin films with Si (100) substrates using pulsed laser deposition (PLD) technique. The deposition methodology of integrating VO2 thin films on silicon using various other template layers will also be discussed. Detailed epitaxial relationship of NiO/c-YSZ/Si(100) heterostructures as a template to growth of VO2 as well as were studied. We also were able to create a p-n junction within a single NiO epilayer through subsequent nanosecond laser annealing, as well as established a structure-property correlation in NiO/c-YSZ/Si(100) thin film epitaxial heterostructures with especial emphasis on the stoichiometry and crystallographic characteristics. Ni

Thermochromic VO2 thin films: solution-based processing, improved optical properties, and lowered phase transformation temperature.

PubMed

Zhang, Zongtao; Gao, Yanfeng; Chen, Zhang; Du, Jing; Cao, Chuanxiang; Kang, Litao; Luo, Hongjie

2010-07-06

This paper describes a solution-phase synthesis of high-quality vanadium dioxide thermochromic thin films. The films obtained showed excellent visible transparency and a large change in transmittance at near-infrared (NIR) wavelengths before and after the metal-insulator phase transition (MIPT). For a 59 nm thick single-layer VO(2) thin film, the integral values of visible transmittance (T(int)) for metallic (M) and semiconductive (S) states were 54.1% and 49.1%, respectively, while the NIR switching efficiencies (DeltaT) were as high as 50% at 2000 nm. Thinner films can provide much higher transmittance of visible light, but they suffer from an attenuation of the switching efficiency in the near-infrared region. By varying the film thickness, ultrahigh T(int) values of 75.2% and 75.7% for the M and S states, respectively, were obtained, while the DeltaT at 2000 nm remained high. These results represent the best data for VO(2) to date. Thicker films in an optimized range can give enhanced NIR switching efficiencies and excellent NIR blocking abilities; in a particularly impressive experiment, one film provided near-zero NIR transmittance in the switched state. The thickness-dependent performance suggests that VO(2) will be of great use in the objective-specific applications. The reflectance and emissivity at the wavelength range of 2.5-25 microm before and after the MIPT were dependent on the film thickness; large contrasts were observed for relatively thick films. This work also showed that the MIPT temperature can be reduced simply by selecting the annealing temperature that induces local nonstoichiometry; a MIPT temperature as low as 42.7 degrees C was obtained by annealing the film at 440 degrees C. These properties (the high visible transmittance, the large change in infrared transmittance, and the near room-temperature MIPT) suggest that the current method is a landmark in the development of this interesting material toward applications in energy-saving smart

The structural conversion from α-AgVO3 to β-AgVO3: Ag nanoparticle decorated nanowires with application as cathode materials for Li-ion batteries.

PubMed

McNulty, David; Ramasse, Quentin; O'Dwyer, Colm

2016-09-15

The majority of electrode materials in batteries and related electrochemical energy storage devices are fashioned into slurries via the addition of a conductive additive and a binder. However, aggregation of smaller diameter nanoparticles in current generation electrode compositions can result in non-homogeneous active materials. Inconsistent slurry formulation may lead to inconsistent electrical conductivity throughout the material, local variations in electrochemical response, and the overall cell performance. Here we demonstrate the hydrothermal preparation of Ag nanoparticle (NP) decorated α-AgVO 3 nanowires (NWs) and their conversion to tunnel structured β-AgVO 3 NWs by annealing to form a uniform blend of intercalation materials that are well connected electrically. The synthesis of nanostructures with chemically bound conductive nanoparticles is an elegant means to overcome the intrinsic issues associated with electrode slurry production, as wire-to-wire conductive pathways are formed within the overall electrode active mass of NWs. The conversion from α-AgVO 3 to β-AgVO 3 is explained in detail through a comprehensive structural characterization. Meticulous EELS analysis of β-AgVO 3 NWs offers insight into the true β-AgVO 3 structure and how the annealing process facilitates a higher surface coverage of Ag NPs directly from ionic Ag content within the α-AgVO 3 NWs. Variations in vanadium oxidation state across the surface of the nanowires indicate that the β-AgVO 3 NWs have a core-shell oxidation state structure, and that the vanadium oxidation state under the Ag NP confirms a chemically bound NP from reduction of diffused ionic silver from the α-AgVO 3 NWs core material. Electrochemical comparison of α-AgVO 3 and β-AgVO 3 NWs confirms that β-AgVO 3 offers improved electrochemical performance. An ex situ structural characterization of β-AgVO 3 NWs after the first galvanostatic discharge and charge offers new insight into the Li + reaction

HF/H2O2 treated graphite felt as the positive electrode for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

He, Zhangxing; Jiang, Yingqiao; Meng, Wei; Jiang, Fengyun; Zhou, Huizhu; Li, Yuehua; Zhu, Jing; Wang, Ling; Dai, Lei

2017-11-01

In order to improve the electrochemical performance of the positive graphite felt electrode in vanadium flow redox battery, a novel method is developed to effectively modify the graphite felt by combination of etching of HF and oxidation of H2O2. After the etching of HF for the graphite felt at ambient temperature, abundant oxygen-containing functional groups were further introduced on the surface of graphite felt by hydrothermal treatment using H2O2 as oxidant. Benefiting from the surface etching and introduction of functional groups, mass transfer and electrode process can be improved significantly on the surface of graphite felt. VO2+/VO2+ redox reaction on the graphite felt modified by HF and H2O2 jointly (denote: GF-HF/H2O2) exhibits superior electrochemical kinetics in comparison with the graphite felt modified by single HF or H2O2 treatment. The cell using GF-HF/H2O2 as the positive electrode was assembled and its electrochemical properties were evaluated. The increase of energy efficiency of 4.1% for GF-HF/H2O2 at a current density of 50 mA cm-2 was obtained compared with the pristine graphite felt. The cell using GF-HF/H2O2 also demonstrated higher discharge capacity. Our study revealed that HF/H2O2 treatment is an efficient method to enhance the electrochemical performance of graphite felt, further improving the comprehensive energy storage performance of the vanadium flow redox battery.

Growth control of the oxidation state in vanadium oxide thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Shinbuhm; Meyer, Tricia L.; Lee, Ho Nyung, E-mail: hnlee@ornl.gov

2014-12-01

Precise control of the chemical valence or oxidation state of vanadium in vanadium oxide thin films is highly desirable for not only fundamental research but also technological applications that utilize the subtle change in the physical properties originating from the metal-insulator transition (MIT) near room temperature. However, due to the multivalent nature of vanadium and the lack of a good understanding on growth control of the oxidation state, stabilization of phase pure vanadium oxides with a single oxidation state is extremely challenging. Here, we systematically varied the growth conditions to clearly map out the growth window for preparing phase puremore » epitaxial vanadium oxides by pulsed laser deposition for providing a guideline to grow high quality thin films with well-defined oxidation states of V{sub 2}{sup +3}O{sub 3}, V{sup +4}O{sub 2}, and V{sub 2}{sup +5}O{sub 5}. A well pronounced MIT was only observed in VO{sub 2} films grown in a very narrow range of oxygen partial pressure P(O{sub 2}). The films grown either in lower (<10 mTorr) or higher P(O{sub 2}) (>25 mTorr) result in V{sub 2}O{sub 3} and V{sub 2}O{sub 5} phases, respectively, thereby suppressing the MIT for both cases. We have also found that the resistivity ratio before and after the MIT of VO{sub 2} thin films can be further enhanced by one order of magnitude when the films are further oxidized by post-annealing at a well-controlled oxidizing ambient. This result indicates that stabilizing vanadium into a single valence state has to compromise with insufficient oxidation of an as grown thin film and, thereby, a subsequent oxidation is required for an improved MIT behavior.« less

Analyzing optical properties of thin vanadium oxide films through semiconductor-to-metal phase transition using spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Sun, Jianing; Pribil, Greg K.

2017-11-01

We investigated the optical behaviors of vanadium dioxide (VO2) films through the semiconductor-to-metal (STM) phase transition using spectroscopic ellipsometry. Correlations between film thickness and refractive index were observed resulting from the absorbing nature of these films. Simultaneously analyzing data at multiple temperatures using Kramers-Kronig consistent oscillator models help identify film thickness. Nontrivial variations in resulting optical constants were observed through STM transition. As temperature increases, a clear increase is observed in near infrared absorption due to Drude losses that accompany the transition from semiconducting to metallic phases. Thin films grown on silicon and sapphire substrate present different optical properties and thermal hysteresis due to lattice stress and compositional differences.

Dynamical heat transport amplification in a far-field thermal transistor of VO{sub 2} excited with a laser of modulated intensity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ordonez-Miranda, Jose, E-mail: jose.ordonez@cnrs.pprime.fr; Ezzahri, Younès; Drevillon, Jérémie

2016-05-28

Far-field radiative heat transport in a thermal transistor made up of a vanadium dioxide base excited with a laser of modulated intensity is analytically studied and optimized. This is done by solving the equation of energy conservation for the steady-state and modulated components of the temperature and heat fluxes that the base exchanges with the collector and emitter. The thermal bistability of VO{sub 2} is used to find an explicit condition on the laser intensity required to maximize these heat fluxes to values higher than the incident flux. For a 1 μm-thick base heated with a modulation frequency of 0.5 Hz, itmore » is shown that both the DC and AC components of the heat fluxes are about 4 times the laser intensity, while the AC temperature remains an order of magnitude smaller than the DC one at around 343 K. Higher AC heat fluxes are obtained for thinner bases and/or lower frequencies. Furthermore, we find that out of the bistability temperatures associated with the dielectric-to-metal and metal-to-dielectric transitions of VO{sub 2}, the amplification of the collector-to-base and base-to-emitter heat fluxes is still possible, but at modulation frequencies lower than 0.1 Hz.« less

Ultrafast electron crystallography of the cooperative reaction path in vanadium dioxide

PubMed Central

Yang, Ding-Shyue; Baum, Peter; Zewail, Ahmed H.

2016-01-01

Time-resolved electron diffraction with atomic-scale spatial and temporal resolution was used to unravel the transformation pathway in the photoinduced structural phase transition of vanadium dioxide. Results from bulk crystals and single-crystalline thin-films reveal a common, stepwise mechanism: First, there is a femtosecond V−V bond dilation within 300 fs, second, an intracell adjustment in picoseconds and, third, a nanoscale shear motion within tens of picoseconds. Experiments at different ambient temperatures and pump laser fluences reveal a temperature-dependent excitation threshold required to trigger the transitional reaction path of the atomic motions. PMID:27376103

A coordination chemistry study of hydrated and solvated cationic vanadium ions in oxidation states +III, +IV, and +V in solution and solid state

PubMed Central

Krakowiak, Joanna; Lundberg, Daniel

2012-01-01

The coordination chemistry of hydrated and solvated vanadium(III), oxovanadium(IV), and dioxovanadium(V) ions in the oxygen donor solvents water, dimethylsulfoxide (dmso) and N,N′-dimethylpropyleneurea (dmpu) has been studied in solution by EXAFS and large angle X-ray scattering (LAXS) and in solid state by single crystal X-ray diffraction and EXAFS. The hydrated vanadium(III) ion has a regular octahedral configuration with a mean V-O bond distance of 1.99 Å. In the hydrated and dimethylsulfoxide solvated oxovanadium(IV) ions vanadium binds strongly to an oxo group at ca. 1.6 Å. The solvent molecule trans to the oxo group is very weakly bound, at ca. 2.2 Å, while the remaining four solvent molecules, with a mean V-O bond distance of 2.0 Å, form a plane slightly below the vanadium atom; the mean O=V-Operp bond angle is ca. 98°. In the dmpu solvated oxovanadium(IV) ion, the space demanding properties of the dmpu molecule leaving no solvent molecule in the trans position to the oxo group which reduces the coordination number to 5. The O=V-O bond angle is consequently much larger, 106°, and the mean V=O and V-O bond distances decrease to 1.58 and 1.97 Å, respectively. The hydrated and dimethylsulfoxide solvated dioxovanadium(V) ions display a very distorted octahedral configuration with the oxo groups in cis position with mean V=O bond distances of 1.6 Å and a O=V=O bond angle of ca. 105°. The solvent molecules trans to the oxo groups are weakly bound, at ca. 2.2 Å, while the remaining two have bond distances of 2.02 Å. The experimental studies of the coordination chemistry of hydrated and solvated vanadium(III,IV,V) ions are complemented by summarizing previously reported crystal structures to yield a comprehensive description of the coordination chemistry of vanadium with oxygen donor ligands. PMID:22950803

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

DOE PAGES

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan; ...

2017-11-27

Here, diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et~al. in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VOmore » $$_2$$, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development.« less

Accuracy of ab initio electron correlation and electron densities in vanadium dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kylänpää, Ilkka; Balachandran, Janakiraman; Ganesh, Panchapakesan

Here, diffusion quantum Monte Carlo results are used as a reference to analyze properties related to phase stability and magnetism in vanadium dioxide computed with various formulations of density functional theory. We introduce metrics related to energetics, electron densities and spin densities that give us insight on both local and global variations in the antiferromagnetic M1 and R phases. Importantly, these metrics can address contributions arising from the challenging description of the 3d orbital physics in this material. We observe that the best description of energetics between the structural phases does not correspond to the best accuracy in the charge density, which is consistent with observations made recently by Medvedev et~al. in the context of isolated atoms. However, we do find evidence that an accurate spin density connects to correct energetic ordering of different magnetic states in VOmore » $$_2$$, although local, semilocal, and meta-GGA functionals tend to erroneously favor demagnetization of the vanadium sites. The recently developed SCAN functional stands out as remaining nearly balanced in terms of magnetization across the M1-R transition and correctly predicting the ground state crystal structure. In addition to ranking current density functionals, our reference energies and densities serve as important benchmarks for future functional development.« less

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties.

PubMed

Dey, Arjun; Nayak, Manish Kumar; Esther, A Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A K; Bera, Parthasarathi; Barshilia, Harish C; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D Raghavendra; Sridhara, N; Sharma, Anand Kumar

2016-11-17

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V 2 O 5 , V 2 O 3 and VO 2 along with MoO 3 . Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10 -5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

NASA Astrophysics Data System (ADS)

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-11-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21-475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45-50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10-5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films.

Nanocolumnar Crystalline Vanadium Oxide-Molybdenum Oxide Antireflective Smart Thin Films with Superior Nanomechanical Properties

PubMed Central

Dey, Arjun; Nayak, Manish Kumar; Esther, A. Carmel Mary; Pradeepkumar, Maurya Sandeep; Porwal, Deeksha; Gupta, A. K.; Bera, Parthasarathi; Barshilia, Harish C.; Mukhopadhyay, Anoop Kumar; Pandey, Ajoy Kumar; Khan, Kallol; Bhattacharya, Manjima; Kumar, D. Raghavendra; Sridhara, N.; Sharma, Anand Kumar

2016-01-01

Vanadium oxide-molybdenum oxide (VO-MO) thin (21–475 nm) films were grown on quartz and silicon substrates by pulsed RF magnetron sputtering technique by altering the RF power from 100 to 600 W. Crystalline VO-MO thin films showed the mixed phases of vanadium oxides e.g., V2O5, V2O3 and VO2 along with MoO3. Reversible or smart transition was found to occur just above the room temperature i.e., at ~45–50 °C. The VO-MO films deposited on quartz showed a gradual decrease in transmittance with increase in film thickness. But, the VO-MO films on silicon exhibited reflectance that was significantly lower than that of the substrate. Further, the effect of low temperature (i.e., 100 °C) vacuum (10−5 mbar) annealing on optical properties e.g., solar absorptance, transmittance and reflectance as well as the optical constants e.g., optical band gap, refractive index and extinction coefficient were studied. Sheet resistance, oxidation state and nanomechanical properties e.g., nanohardness and elastic modulus of the VO-MO thin films were also investigated in as-deposited condition as well as after the vacuum annealing treatment. Finally, the combination of the nanoindentation technique and the finite element modeling (FEM) was employed to investigate yield stress and von Mises stress distribution of the VO-MO thin films. PMID:27853234

Release kinetics of vanadium from vanadium (III, IV and V) oxides: Effect of pH, temperature and oxide dose.

PubMed

Hu, Xingyun; Yue, Yuyan; Peng, Xianjia

2018-05-01

Batch experiments were performed to derive the rate laws for the proton-promoted dissolution of the main vanadium (III, IV and V) oxides at pH 3.1-10.0. The release rates of vanadium are closely related to the aqueous pH, and several obvious differences were observed in the release behavior of vanadium from the dissolution of V 2 O 5 and vanadium(III, IV) oxides. In the first 2hr, the release rates of vanadium from V 2 O 3 were r=1.14·([H + ]) 0.269 at pH 3.0-6.0 and r=0.016·([H + ]) -0.048 at pH 6.0-10.0; the release rates from VO 2 were r=0.362·([H + ]) 0.129 at pH 3.0-6.0 and r=0.017·([H + ]) -0.097 at pH 6.0-10.0; and the release rates from V 2 O 5 were r=0.131·([H + ]) -0.104 at pH 3.1-10.0. The release rates of vanadium from the three oxides increased with increasing temperature, and the effect of temperature was different at pH 3.8, pH 6.0 and pH 7.7. The activation energies of vanadium (III, IV and V) oxides (33.4-87.5kJ/mol) were determined at pH 3.8, pH6.0 and pH 7.7, showing that the release of vanadium from dissolution of vanadium oxides follows a surface-controlled reaction mechanism. The release rates of vanadium increased with increasing vanadium oxides dose, albeit not proportionally. This study, as part of a broader study of the release behavior of vanadium, can help to elucidate the pollution problem of vanadium and to clarify the fate of vanadium in the environment. Copyright © 2017. Published by Elsevier B.V.

VO2 responses to intermittent swimming sets at velocity associated with VO2max.

PubMed

Libicz, Sebastien; Roels, Belle; Millet, Gregoire P

2005-10-01

While the physiological adaptations following endurance training are relatively well understood, in swimming there is a dearth of knowledge regarding the metabolic responses to interval training (IT). The hypothesis tested predicted that two different endurance swimming IT sets would induce differences in the total time the subjects swam at a high percentage of maximal oxygen consumption (VO(2)max). Ten trained triathletes underwent an incremental test to exhaustion in swimming so that the swimming velocity associated with VO(2)max (vVO(2)max) could be determined. This was followed by a maximal 400-m test and two intermittent sets at vVO(2)max: (a) 16 x 50 m with 15-s rest (IT(50)); (b) 8 x 100 m with 30-s rest (IT(100)). The times sustained above 95% VO(2)max (68.50 +/- 62.69 vs. 145.01 +/- 165.91 sec) and 95% HRmax (146.67 +/- 131.99 vs. 169.78 +/- 203.45 sec, p = 0.54) did not differ between IT(50) and IT(100)(values are mean +/- SD). In conclusion, swimming IT sets of equal time duration at vVO(2)max but of differing work-interval durations led to slightly different VO(2)and HR responses. The time spent above 95% of VO(2)max was twice as long in IT(100) as in IT (50), and a large variability between mean VO(2)and HR values was also observed.

Tuning of thermally induced first-order semiconductor-to-metal transition in pulsed laser deposited VO2 epitaxial thin films

NASA Astrophysics Data System (ADS)

Behera, Makhes K.; Pradhan, Dhiren K.; Pradhan, Sangram K.; Pradhan, Aswini K.

2017-12-01

Vanadium oxide (VO2) thin films have drawn significant research and development interest in recent years because of their intriguing physical origin and wide range of functionalities useful for many potential applications, including infrared imaging, smart windows, and energy and information technologies. However, the growth of highly epitaxial films of VO2, with a sharp and distinct controllable transition, has remained a challenge. Here, we report the structural and electronic properties of high quality and reproducible epitaxial thin films of VO2, grown on c-axis oriented sapphire substrates using pulsed laser deposition at different deposition pressures and temperatures, followed by various annealing schedules. Our results demonstrate that the annealing of epitaxial VO2 films significantly enhances the Semiconductor to Metal Transition (SMT) to that of bulk VO2 transition. The effect of oxygen partial pressure during the growth of VO2 films creates a significant modulation of the SMT from around room temperature to as high as the theoretical value of 68 °C. We obtained a bulk order transition ≥104 while reducing the transition temperature close to 60 °C, which is comparatively less than the theoretical value of 68 °C, demonstrating a clear and drastic improvement in the SMT switching characteristics. The results reported here will open the door to fundamental studies of VO2, along with tuning of the transition temperatures for potential applications for multifunctional devices.

Luminescence Properties of Self-Activated Mm(VO4)2 (M = Mg, Ca, Sr, and Ba) Phosphors Synthesized by Solid-State Reaction Method.

PubMed

Min, Xin; Huang, Zhaohui; Fang, Minghao; Liu, Yan'gai; Tang, Chao; Wu, Xiaowen

2016-04-01

In this paper, M3(VO4)2 (M = Mg, Ca, Sr, and Ba) self-activated phosphors were prepared by a solid-state reaction method at 1,000 °C for 5 h. The phase formation and micrographs were analyzed by X-ray diffraction and scanning electron microscopy. The Ca3(VO4)2 phosphor does not show any emission peaks under excitation with ultraviolet (UV) light. However, the M3(VO4)2 (M = Mg, Sr, and Ba) samples are effectively excited by UV light chips ranging from 200 nm to 400 nm and exhibit broad emission bands due to the charge transfer from the oxygen 2p orbital to the vacant 3d orbital of the vanadium in the VO4. The color of these phosphors changes from yellow to light blue via blue-green with increasing ionic radius from Mg to Sr to Ba. The luminescence lifetimes and quantum yield decrease with the increasing unit cell volume and V-V distance, in the order of Mg3(VO4)2 to Sr3(VO4)2 to Ba3(VO4)2. The emission intensity decreases with the increase of temperatures, but presents no color shift. This confirms that these self-activated M3(VO4)2 phosphors can be suggested as candidates of the single-phase phosphors for light using UV light emitting diodes (LEDs).

A Kinetics and Equilibrium Study of Vanadium Dissolution from Vanadium Oxides and Phosphates in Battery Electrolytes: Possible Impacts on ICD Battery Performance.

PubMed

Bock, David C; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2013-06-01

Silver vanadium oxide (Ag 2 V 4 O 11 , SVO) has enjoyed widespread commercial success over the past 30 years as a cathode material for implantable cardiac defibrillator (ICD) batteries. Recently, silver vanadium phosphorous oxide (Ag 2 VO 2 PO 4 , SVPO) has been studied as possibly combining the desirable thermal stability aspects of LiFePO 4 with the electrical conductivity of SVO. Further, due to the noted insoluble nature of most phosphate salts, a lower material solubility of SVPO relative to SVO is anticipated. Thus, the first vanadium dissolution studies of SVPO in battery electrolyte solutions are described herein. The equilibrium solubility of SVPO was ~5 times less than SVO, with a rate constant of dissolution ~3.5 times less than that of SVO. The vanadium dissolution in SVO and SVPO can be adequately described with a diffusion layer model, as supported by the Noyes-Whitney equation. Cells prepared with vanadium-treated anodes displayed higher AC impedance and DC resistance relative to control anodes. These data support the premise that SVPO cells are likely to exhibit reduced cathode solubility and thus less affected by increased cell resistance due to cathode solubility compared to SVO based cells.

Electron affinity of cubic boron nitride terminated with vanadium oxide

NASA Astrophysics Data System (ADS)

Yang, Yu; Sun, Tianyin; Shammas, Joseph; Kaur, Manpuneet; Hao, Mei; Nemanich, Robert J.

2015-10-01

A thermally stable negative electron affinity (NEA) for a cubic boron nitride (c-BN) surface with vanadium-oxide-termination is achieved, and its electronic structure was analyzed with in-situ photoelectron spectroscopy. The c-BN films were prepared by electron cyclotron resonance plasma-enhanced chemical vapor deposition employing BF3 and N2 as precursors. Vanadium layers of ˜0.1 and 0.5 nm thickness were deposited on the c-BN surface in an electron beam deposition system. Oxidation of the metal layer was achieved by an oxygen plasma treatment. After 650 °C thermal annealing, the vanadium oxide on the c-BN surface was determined to be VO2, and the surfaces were found to be thermally stable, exhibiting an NEA. In comparison, the oxygen-terminated c-BN surface, where B2O3 was detected, showed a positive electron affinity of ˜1.2 eV. The B2O3 evidently acts as a negatively charged layer introducing a surface dipole directed into the c-BN. Through the interaction of VO2 with the B2O3 layer, a B-O-V layer structure would contribute a dipole between the O and V layers with the positive side facing vacuum. The lower enthalpy of formation for B2O3 is favorable for the formation of the B-O-V layer structure, which provides a thermally stable surface dipole and an NEA surface.

Comparison of distribution and toxicity following repeated oral dosing of different vanadium oxide nanoparticles in mice.

PubMed

Park, Eun-Jung; Lee, Gwang-Hee; Yoon, Cheolho; Kim, Dong-Wan

2016-10-01

Vanadium is an important ultra-trace element derived from fuel product combustion. With the development of nanotechnology, vanadium oxide nanoparticles (VO NPs) have been considered for application in various fields, thus the possibility of release into the environment and human exposure is also increasing. Considering that verification of bioaccumulation and relevant biological responses are essential for safe application of products, in this study, we aimed to identify the physicochemical properties that determine their health effects by comparing the biological effects and tissue distribution of different types of VO NPs in mice. For this, we prepared five types of VO NPs, commercial (C)-VO2 and -V2O5 NPs and synthetic (S)-VO2, -V2O3, and -V2O5 NPs. While the hydrodynamic diameter of the two types of C-VO NPs was irregular and impossible to measure, those of the three types of S-VO NPs was in the range of 125-170nm. The S- and C-V2O5 NPs showed higher dissolution rates compared to other VO NPs. We orally dosed the five types of VO NPs (70 and 210μg/mouse, approximately 2 and 6mg/kg) to mice for 28 days and compared their biodistribution and toxic effects. We found that S-V2O5 and S-V2O3 NPs more accumulated in tissues compared to other three types of VO NPs, and the accumulated level was in order of heart>liver>kidney>spleen. Additionally, tissue levels of redox reaction-related elements and electrolytes (Na(+), K(+), and Ca(2+)) were most clearly altered in the heart of treated mice. Notably, all S- and C-VO NPs decreased the number of WBCs at the higher dose, while total protein and albumin levels were reduced at the higher dose of S-V2O5 and S-V2O3 NPs. Taken together, we conclude that the biodistribution and toxic effects of VO NPs depend on their dissolution rates and size (surface area). Additionally, we suggest that further studies are needed to clarify effects of VO NPs on functions of the heart and the immune system. Copyright © 2016 Elsevier Inc. All

Phase transition in bulk single crystals and thin films of V O 2 by nanoscale infrared spectroscopy and imaging

DOE PAGES

Liu, Mengkun; Sternbach, Aaron J.; Wagner, Martin; ...

2015-06-29

We have systematically studied a variety of vanadium dioxide (VO 2) crystalline forms, including bulk single crystals and oriented thin films, using infrared (IR) near-field spectroscopic imaging techniques. By measuring the IR spectroscopic responses of electrons and phonons in VO 2 with sub-grain-size spatial resolution (~20nm), we show that epitaxial strain in VO 2 thin films not only triggers spontaneous local phase separations, but leads to intermediate electronic and lattice states that are intrinsically different from those found in bulk. Generalized rules of strain- and symmetry-dependent mesoscopic phase inhomogeneity are also discussed. Furthermore, these results set the stage for amore » comprehensive understanding of complex energy landscapes that may not be readily determined by macroscopic approaches.« less

Investigation of Silica-Supported Vanadium Oxide Catalysts by High-Field 51 V Magic-Angle Spinning NMR

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaegers, Nicholas R.; Wan, Chuan; Hu, Mary Y.

Supported V2O5/SiO2 catalysts were studied using solid state 51V MAS NMR at a sample spinning rate of 36 kHz and at a magnetic field of 19.975 T for a better understanding of the coordination of the vanadium oxide as a function of environmental conditions . Structural transformations of the supported vanadium oxide species between the catalyst in the dehydrated state and hydrated state under an ambient environment were revisited to examine the degree of oligomerization and the effect of water. The experimental results indicate the existence of a single dehydrated surface vanadium oxide species that resonates at -675 ppm andmore » two vanadium oxide species under ambient conditions that resonate at -566 and -610 ppm, respectively. No detectable structural difference was found as a function of vanadium oxide loading on SiO2 (3% V2O5/SiO2 and 8% V2O5/SiO2). Quantum chemistry simulations of the 51V NMR chemical shifts on predicted surface structures were used as an aide in understanding potential surface vanadium oxide species on the silica support. The results suggest the formation of isolated surface VO4 units for the dehydrated catalysts with the possibility of dimer and cyclic trimer presence. The absence of bridging V-O-V vibrations (~200-300 cm-1) in the Raman spectra [Gao et al. J. Phys. Chem. B 1998, 102, 10842-10852], however, indicates that the isolated surface VO4 sites are the dominant dehydrated surface vanadia species on silica. Upon exposure to water, hydrolysis of the bridging V-O-Si bonds is most likely responsible for the decreased electron shielding experienced by vanadium. No indicators for the presence of hydrated decavanadate clusters or hydrated vanadia gels previously proposed in the literature were detected in this study.« less

Reductive transformation of V(iii) precursors into vanadium(ii) oxide nanowires.

PubMed

Ojelere, Olusola; Graf, David; Ludwig, Tim; Vogt, Nicholas; Klein, Axel; Mathur, Sanjay

2018-05-15

Vanadium(ii) oxide nanostructures are promising materials for supercapacitors and electrocatalysis because of their excellent electrochemical properties and high surface area. In this study, new homoleptic vanadium(iii) complexes with bi-dentate O,N-chelating heteroarylalkenol ligands (DmoxCH[double bond, length as m-dash]COCF3, PyCH[double bond, length as m-dash]COCF3 and PyN[double bond, length as m-dash]COCF3) were synthesized and successfully transformed by reductive conversion into VO nanowires. The chemical identity of V(iii) complexes and their redox behaviour were unambiguously established by single crystal X-ray diffraction studies, cyclic voltammetry, spectrometric studies and DFT calculations. Transformation into the metastable VO phase was verified by powder X-ray diffraction and thermo-gravimetry. Transmission electron microscopy and X-ray photoelectron spectroscopy data confirmed the morphology and chemical composition of VO nanostructures, respectively.

Amphiphilic block copolymer membrane for vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Wang, Fei; Sylvia, James M.; Jacob, Monsy M.; Peramunage, Dharmasena

2013-11-01

An amphiphilic block copolymer comprised of hydrophobic polyaryletherketone (PAEK) and hydrophilic sulfonated polyaryletherketone (SPAEK) blocks has been synthesized and characterized. A membrane prepared from the block copolymer is used as the separator in a single cell vanadium redox flow battery (VRB). The proton conductivity, mechanical property, VO2+ permeability and single VRB cell performance of this block copolymer membrane are investigated and compared to Nafion™ 117. The block copolymer membrane showed significantly improved vanadium ion selectivity, higher mechanical strength and lower conductivity than Nafion™ 117. The VRB containing the block copolymer membrane exhibits higher coulombic efficiency and similar energy efficiency compared to a VRB using Nafion™ 117. The better vanadium ion selectivity of the block copolymer membrane has led to a much smaller capacity loss during 50 charge-discharge cycles for the VRB.

Photocatalytic Activity of Vanadium-Substituted ETS-10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nash,M.; Rykov, S.; Lobo, R.

2007-01-01

Various amounts of vanadium have been isomorphously substituted for titanium in ETS-10, creating samples with V/(V+Ti) ratios of 0.13, 0.33, 0.43, and 1.00 and characterized experimentally using Raman, near-edge X-ray absorption fine structure (NEXAFS), X-ray powder diffraction, N{sub 2} adsorption, scanning electron microscopy (SEM), UV/vis spectroscopy, and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Raman spectra reveal a disordered chain structure that contains different V-O bonds along with the presence of a V-O-Ti peak. The UV/vis spectra of the vanadium samples have three new absorption features in the visible region at 450, 594, and 850 nm, suggesting both V{sup 4+}more » and V{sup 5+} are present in the samples. NEXAFS results confirm the presence of both V{sup 5+} and V{sup 4+} in the vanadium samples, with a fraction of V{sup 4+} within the range of 0.2-0.4. The addition of vanadium lowers the band gap energy of ETS-10 from 4.32 eV to a minimum of 3.58 eV for the 0.43ETVS-10 sample. Studies of the photocatalytic polymerization of ethylene show that the 594 nm transition has no photocatalytic activity. The visible transition around 450 nm in the vanadium-incorporated samples is photocatalytically active, and the lower-concentration vanadium samples have higher photocatalytic activity than that of ETS-10 and AM-6, the all-vanadium analogue of ETS-10.« less

Reversible phase transition in vanadium oxide films sputtered on metal substrates

NASA Astrophysics Data System (ADS)

Palai, Debajyoti; Carmel Mary Esther, A.; Porwal, Deeksha; Pradeepkumar, Maurya Sandeep; Raghavendra Kumar, D.; Bera, Parthasarathi; Sridhara, N.; Dey, Arjun

2016-11-01

Vanadium oxide films, deposited on aluminium (Al), titanium (Ti) and tantalum (Ta) metal substrates by pulsed RF magnetron sputtering at a working pressure of 1.5 x10-2 mbar at room temperature are found to display mixed crystalline vanadium oxide phases viz., VO2, V2O3, V2O5. The films have been characterized by field-emission scanning electron microscopy, X-ray diffraction, differential scanning calorimetry (DSC) and X-ray photoelectron spectroscopy, and their thermo-optical and electrical properties have been investigated. Studies of the deposited films by DSC have revealed a reversible-phase transition found in the temperature range of 45-49 °C.

Glassy carbon/multi walled carbon nanotube/cadmium sulphide photoanode for light energy storage in vanadium photoelectrochemical cell

NASA Astrophysics Data System (ADS)

Peimanifard, Zahra; Rashid-Nadimi, Sahar

2015-12-01