In situ probing of doping- and stress-mediated phase transitions in a single-crystalline VO₂ nanobeam by spatially resolved Raman spectroscopy.

We demonstrate an experimental in situ observation of the temperature-dependent evolution of doping- and stress-mediated structural phase transitions in an individual single-crystalline VO₂ nanobeam on a Au-coated substrate under exposure to hydrogen gas using spatially resolved Raman spectroscopy. The nucleation temperature of the rutile R structural phase in the VO₂ nanobeam upon heating under hydrogen gas was lower than that under air. The spatial structural phase evolution behavior along the length of the VO₂ nanobeam under hydrogen gas upon heating was much more inhomogeneous than that along the length of the same nanobeam under air. The triclinic T phase of the VO₂ nanobeam upon heating under hydrogen gas transformed to the R phase and this R phase was stabilized even at room temperature in air after sample cooling. In particular, after the VO₂ nanobeam with the R phase was annealed at approximately 250 °C in air, it exhibited the monoclinic M1 phase (not the T phase) at room temperature during heating and cooling cycles. These results were attributed to the interplay between hydrogen doping and stress associated with nanobeam-substrate interactions. Our study has important implications for engineering metal-insulator transition properties and developing functional devices based on VO₂ nanostructures through doping and stress.

[1]  Martin Moskovits,et al.  Pd-sensitized single vanadium oxide nanowires: highly responsive hydrogen sensing based on the metal-insulator transition. , 2009, Nano letters.

[2]  Hongkun Park,et al.  Strain-induced self organization of metal-insulator domains in single-crystalline VO2 nanobeams. , 2006, Nano letters.

[3]  Emmanuelle Merced,et al.  A micro-electro-mechanical memory based on the structural phase transition of VO2 , 2013 .

[4]  In Soo Kim,et al.  Stoichiometry engineering of monoclinic to rutile phase transition in suspended single crystalline vanadium dioxide nanobeams. , 2011, Nano letters.

[5]  Yanfeng Gao,et al.  Enhanced chemical stability of VO2 nanoparticles by the formation of SiO2/VO2 core/shell structures and the application to transparent and flexible VO2-based composite foils with excellent thermochromic properties for solar heat control , 2012 .

[6]  Byung-Gyu Chae,et al.  Mott Transition in VO2 Revealed by Infrared Spectroscopy and Nano-Imaging , 2007, Science.

[7]  Docheon Ahn,et al.  Stress-induced domain dynamics and phase transitions in epitaxially grown VO2 nanowires , 2012, Nanotechnology.

[8]  Yi Xie,et al.  Design of vanadium oxide structures with controllable electrical properties for energy applications. , 2013, Chemical Society reviews.

[9]  Junqiao Wu,et al.  Strain and temperature dependence of the insulating phases of VO2 near the metal-insulator transition , 2012 .

[10]  Emile Haddad,et al.  Highly tunable-emittance radiator based on semiconductor-metal transition of VO2 thin films , 2013 .

[11]  Hidekazu Tanaka,et al.  Multistate Memory Devices Based on Free‐standing VO2/TiO2 Microstructures Driven by Joule Self‐Heating , 2012, Advanced materials.

[12]  Wei Chen,et al.  New aspects of the metal-insulator transition in single-domain vanadium dioxide nanobeams. , 2009, Nature nanotechnology.

[13]  Yong Ding,et al.  Phase and shape controlled VO2 nanostructures by antimony doping , 2012 .

[14]  Massimiliano Di Ventra,et al.  Phase-transition driven memristive system , 2009, 0901.0899.

[15]  J. M. Baik,et al.  Electrothermally Induced Highly Responsive and Highly Selective Vanadium Oxide Hydrogen Sensor Based on Metal–Insulator Transition , 2012 .

[16]  Zongtao Zhang,et al.  Nanoceramic VO2 thermochromic smart glass: A review on progress in solution processing , 2012 .

[17]  Junqiao Wu,et al.  Dynamically tracking the strain across the metal-insulator transition in VO2 measured using electromechanical resonators. , 2013, Nano letters.

[18]  M. Raschke,et al.  Nano-optical investigations of the metal-insulator phase behavior of individual VO(2) microcrystals. , 2010, Nano letters.

[19]  Guofeng Ren,et al.  Highly conductive VO2 treated with hydrogen for supercapacitors. , 2013, Chemical communications.

[20]  Yong Ding,et al.  External‐Strain Induced Insulating Phase Transition in VO2 Nanobeam and Its Application as Flexible Strain Sensor , 2010, Advanced materials.

[21]  Gokul Gopalakrishnan,et al.  Electrical triggering of metal-insulator transition in nanoscale vanadium oxide junctions , 2009 .

[22]  Byung-Gyu Chae,et al.  Temperature dependence of the first-order metal-insulator transition in VO2 and programmable critical temperature sensor , 2007 .

[23]  Heng Ji,et al.  Hydrogen stabilization of metallic vanadium dioxide in single-crystal nanobeams , 2012 .

[24]  Yanfeng Gao,et al.  VO2–Sb:SnO2 composite thermochromic smart glass foil , 2012 .

[25]  Heung Cho Ko,et al.  Probing the photothermally induced phase transitions in single-crystalline vanadium dioxide nanobeams , 2013, Nanotechnology.

[26]  F. J. Morin,et al.  Oxides Which Show a Metal-to-Insulator Transition at the Neel Temperature , 1959 .

[27]  Byung-Gyu Chae,et al.  Memory Metamaterials , 2009, Science.

[28]  Kai Liu,et al.  Giant-amplitude, high-work density microactuators with phase transition activated nanolayer bimorphs. , 2012, Nano letters.

[29]  Nicholas D M Hine,et al.  Vanadium dioxide: a Peierls-Mott insulator stable against disorder. , 2012, Physical review letters.

[30]  Harry A Atwater,et al.  Compact silicon photonic waveguide modulator based on the vanadium dioxide metal-insulator phase transition. , 2010, Optics express.

[31]  Gokul Gopalakrishnan,et al.  Three-terminal field effect devices utilizing thin film vanadium oxide as the channel layer , 2010, 1006.4373.

[32]  Emmanuelle Merced,et al.  A micro‐electro‐mechanical memory based on the structural phase transition of VO2 (Phys. Status Solidi A 9∕2013) , 2013 .

[33]  Evgheni Strelcov,et al.  Gas sensor based on metal-insulator transition in VO2 nanowire thermistor. , 2009, Nano letters.

[34]  Strongly Correlated Materials , 2012, Advanced materials.

[35]  Sarbajit Banerjee,et al.  Microscopic and Nanoscale Perspective of the Metal−Insulator Phase Transitions of VO2: Some New Twists to an Old Tale , 2011 .

[36]  S. Ramanathan,et al.  Oxide Electronics Utilizing Ultrafast Metal-Insulator Transitions , 2011 .

[37]  Chel-Jong Choi,et al.  Direct observation of the structural component of the metal-insulator phase transition and growth habits of epitaxially grown VO2 nanowires. , 2007, Nano letters.

[38]  Tae-Sung Bae,et al.  Hydrogen-induced morphotropic phase transformation of single-crystalline vanadium dioxide nanobeams. , 2013, Nano letters.

[39]  Shixiong Zhang,et al.  Direct correlation of structural domain formation with the metal insulator transition in a VO2 nanobeam. , 2009, Nano letters.

[40]  L. Boeri,et al.  Optical properties of V 1 − x Cr x O 2 compounds under high pressure , 2008 .

[41]  Masatoshi Imada,et al.  Metal-insulator transitions , 1998 .

[42]  David H. Cobden,et al.  Measurement of a solid-state triple point at the metal–insulator transition in VO2 , 2013, Nature.

[43]  Ziyu Wu,et al.  Hydrogen-incorporation stabilization of metallic VO2(R) phase to room temperature, displaying promising low-temperature thermoelectric effect. , 2011, Journal of the American Chemical Society.

[44]  Jie Zhang,et al.  Doping-based stabilization of the M2 phase in free-standing VO₂ nanostructures at room temperature. , 2012, Nano letters.