Abstract
Enhancing the semiconductor–metal phase transition temperature (TSMT) of VO2 is of great consequence for further exploring the potential applications of VO2 at elevated temperatures. In this study, Ge4+-doped VO2 (GexV1−xO2) samples were prepared by the hydrothermal and annealing approach. X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), differential scanning calorimetry (DSC) and resistivity–temperature (R-T) analyses were used to investigate the influence of Ge doping on the lattice structures and phase transition properties of GexV1–xO2 samples. We found that the lattice parameter of GexV1−xO2 decreased with the Ge concentration increasing from 2 at% to 18 at%, which was further supported by density functional theory (DFT)-based first-principle simulations. TSMT firstly increased from 64.5 to 73.0 °C at 8 at% Ge and then decreased to 71.5 °C at higher Ge concentration. Furthermore, DFT analysis revealed that the impact of lattice distortion induced by Ge doping rather than the changes in electronic structure is more pronounced on modulating TSMT of GexV1−xO2. The present work has pointed out the direction that the TSMT could be enhanced and illustrated the physical reason behind the regulation of TSMT in ions-doped VO2 systems.
Graphic Abstract
The d (logρ)/dT vs T curves are plotted for GexV1−xO2 (0≤x≤0.18) samples (a) un-doped VO2 ; (b) 2%; (c) 8%; (d) 18%, the transition temperatures upon heating, Th, and cooling, Tc. The difference between Th and Tc gives the hysteresis width, ΔTt, while the FWHM determines the sharpness of the semiconductor-to-metal transition
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References
Morin FJ. Oxides which show a metal-to-insulator transition at the neel temperature. Phys Rev Lett. 1959;3(1):34.
Goodenough JB. The two components of the crystallographic transition in VO2. J Solid State Chem. 1971;3(4):490.
Aetukuri NB, Gray AX, Drouard M, Cossale M, Gao L, Reid AH, Roopali K, Hendrik O, Catherine AJ, Elke A, Kevin PR, Hermann AD, Mahesh GS, Stuart SPP. Control of the metal–insulator transition in vanadium dioxide by modifying orbital occupancy. Nature Phys. 2013;9(10):661.
Guinneton F, Sauquesb L, Valmalettea JC, Crosb F, Gavarria JR. Comparative study between nanocrystalline powder and thin film of vanadium dioxide VO2: electrical and infrared properties. J Phys Chem Solids. 2000;62(7):1229.
Kim BJ, Lee YW, Chae BG, Yun SJ, Oh SY, Kim HT, Lim YS. Temperature dependence of the first-order metal-insulator transition in VO2 and programmable critical temperature sensor. Appl Phys Lett. 2007;90(2):3515.
Haras A, Witko M, Salahub DR, Hermann KT, okarz R. Electronic properties of the VO2 (011) surface: density functional cluster calculations. Surface Sci. 2001;491(2):77.
Zhou J, Gao Y, Zhang Z, Luo H, Cao C, Chen Z, Dai L, Liu XL. VO2 thermochromic smart window for energy savings and generation. Sci Rep. 2013;3:3029.
Cui Y, Ke Y, Liu C, Chen Z, Wang N, Zhang L, Zhou Y, Wang S, Gao Y, Long Y. Thermochromic VO2 for energy-efficient smart windows. Joule. 2018;2(9):1707.
Ryckman JD, Diez-Blanco V, Nag J, Marvel RE, Choi BK, Haglund RF, Weiss SM. Photothermal optical modulation of ultracompact hybrid Si-VO2 ring resonators. Opt Express. 2012;20:12.
Zhu Y, Vegesna S, Zhao Y, Kuryatkov V, Holtz M, Fan Z, Saed M, Bernussi AA. Tunable dual-band terahertz metamaterial bandpass filters. Opt Lett. 2013;38(14):2382.
Wu YF, Zou CW, Fan LL, Liu QH, Chen S, Huang WF, Wu ZY, Chen FH, Liao GM. Decoupling the lattice distortion and charge doping effects on the phase transition behavior of VO2 by titanium (Ti4+) doping. Sci Rep. 2015;5:9328.
Zhang Y, Zheng J, Hu T, Tian F, Meng C. Synthesis and supercapacitor electrode of VO2(B)/C core–shell composites with a pseudocapacitance in aqueous solution. Appl Surface Sci. 2016;371:189.
Li CI, Lin JC, Liu HJ, Chu MW, Chen HW, Ma CH, Tsai CY, Huang HW, Lin HJ, Liu HL, Chiu PW, Chu YH. van der Waal epitaxy of flexible and transparent VO2 film on Muscovite. Chem Mater. 2016;28(11):3914.
Guo D, Ling C, Wang C, Wang D, Li J, Zhao Z, Wang Z, Zhao Y, Zhang J, Jin H. Hydrothermal one-step synthesis of highly dispersed M-phase VO2 nanocrystals and application to flexible thermochromic film. ACS Appl Mater Interfaces. 2018;10(34):28627.
Jo YR, Myeong SH, Kim BJ. Role of annealing temperature on the sol–gel synthesis of VO2 nanowires with in situ characterization of their metal–insulator transition. RSC Adv. 2018;8(10):5158.
Chain EE. Optical properties of vanadium dioxide and vanadium pentoxide thin films. Appl Optics. 1991;30(19):2782.
Nag J, Haglund RF Jr. Synthesis of vanadium dioxide thin films and nanoparticles. J Phys: Condens Matter. 2008;20(26):264016.
Briggs Ryan M, Pryce Imogen M, Atwater HA. Compact silicon photonic waveguide modulator based on the vanadium dioxide metal-insulator phase transition. Opt Express. 2010;18(11):11192.
Benkahoul M, Chaker M, Margot J, Haddad E, Kruzelecky R, Wong B, Jamroz W, Poinas P. Thermochromic VO2 film deposited on Al with tunable thermal emissivity for space applications. Solar Energy Mater Solar Cells. 2011;95(12):3504.
Liu M, Hwang HY, Tao H, Strikwerda AC, Fan K, Keiser GR, Sternbach AJ, West KG, Kittiwatanakul S, Lu J, Wolf SA, Omenetto FG, Zhang X, Nelson KA, Averitt RD. Terahertz-field-induced insulator-to-metal transition in vanadium dioxide metamaterial. Nature. 2012;487(7407):345.
Wang S, Owusu KA, Mai L, Ke Y, Zhou Y, Hu P, Magdassi S, Long Y. Vanadium dioxide for energy conservation and energy storage applications: synthesis and performance improvement. Appl Energy. 2018;211:200.
Yang S, Gong Y, Liu Z, Zhan L, Hashim DP, Ma L, Vajtai R, Ajayan PM. Bottom-up approach toward single-crystalline VO2-graphene ribbons as cathodes for ultrafast lithium storage. Nano Lett. 2013;13(4):1596.
Mai L, Wei Q, An Q, Tian X, Zhao Y, Xu X, Xu L, Chang L, Zhang Q. Nanoscroll buffered hybrid nanostructural VO2 (B) cathodes for high-rate and long-life lithium storage. Adv Mater. 2013;25(21):2969.
Yanase I, Mori Y, Kobayashi H. Hydrothermal synthesis and thermal change in IR reflectance of Al/W co-doped VO2 powder. Mater Res Bull. 2018;100:243.
Kim BJ, Lee YW, Choi S, Lim JW, Yun SJ, Kim HT, Shin TJ, Yun HS. Micrometer X-ray diffraction study of VO2 films: separation between metal-insulator transition and structural phase transition. Phys Rev B. 2008;77(23):5401.
Zhang CX, Cheng J, Zhang J, Yang X. Simple and facile synthesis W-doped VO2 (M) powder based on hydrothermal pathway. Int J Electrochemi Sci. 2015;10(7):6014.
Hanlon TJ, Coath JA, Richardson MA. Molybdenum-doped vanadium dioxide coatings on glass produced by the aqueous sol–gel method. Thin Solid Films. 2003;436(2):269.
Manning TD, Parkin IP, Blackman C, Qureshi U. APCVD of thermochromic vanadium dioxide thin films—solid solutions V2–xMxO2 (M = Mo, Nb) or composites VO2: SnO2. J Mater Chem. 2005;15(42):4560.
Brown BL, Lee M, Clem PG, Nordquist CD, Jordan TS, Wolfley SL, Leonhardt D, Edney C, Custer JA. Electrical and optical characterization of the metal-insulator transition temperature in Cr-doped VO2 thin films. J Appl Phys. 2013;113(17):173704.
Zhou J, Gao Y, Liu X, Chen Z, Dai L, Cao C, Luo H, Kanahira M, Sun C, Yan L. Mg-doped VO2 nanoparticles: hydrothermal synthesis, enhanced visible transmittance and decreased metal-insulator transition temperature. Phys Chem Chem Phys. 2013;15(20):7505.
Pan M, Zhong H, Wang S, Liu J, Li Z, Chen X, Liu W. Properties of VO2 thin film prepared with precursor VO(acac)2. J Cryst Growth. 2004;265(1–2):121.
Krammer A, Magrez A, Vitale WA, Mocny P, Jeanneret P, Guibert E, Whitlow HJ, Ionescu AM, Schüler A. Elevated transition temperature in Ge doped VO2 thin films. J Appl Phys. 2017;122(4):5304.
Kresse G, Furthmuller J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B. 1996;54(16):11169.
Blochl PE. Projector augmented-wave method. Phys Rev B: Condens Matter. 1994;50(24):17953.
Perdew John P, Burke Kieron, Ernzerhof Matthias. Generalized gradient approximation made simple. Phys Rev Lett. 1996;77(18):3865.
Wentzcovitch RM, Schulz WW, Allen PB. VO2: Peierls or Mott–Hubbard? A view from band theory. Phys Rev Lett. 1994;72(21):3389.
Rice TM, Launois H, Pouget JP. Comment on “VO2: Peierls or Mott-Hubbard? A view from band theory”. Phys Rev Lett. 1994;73(22):3042.
Wang L, Maxisch T, Ceder G. Oxidation energies of transition metal oxides within the GGA+U framework. Phys Rev B. 2006;73(19):5107.
Liebsch A, Ishida H, Bihlmayer G. Coulomb correlations and orbital polarization in the metal-insulator transition of VO2. Phys Rev B. 2005;71(8):5109.
Cui Y, Cao C, Chen Z, Luo H, Gao Y. Atomic and electronic structures of thermochromic VO2 with Sb-doping. Comput Mater Sci. 2017;130:103.
Rogers KD. An X-ray diffraction study of semiconductor and metallic vanadium dioxide. Powder diffract. 1993;8(04):240.
Sun C, Yan L, Yue B, Liu H, Gao Y. The modulation of metal-insulator transition temperature of vanadium dioxide: a density functional theory study. J Mater Chem C. 2014;2(43):9283.
Dai L, Chen S, Liu J, Gao Y, Zhou J, Chen Z, Cao C, Luo H, Kanehira M. F-doped VO2 nanoparticles for thermochromic energy-saving foils with modified color and enhanced solar-heat shielding ability. Phys Chem Chem Phys. 2013;15(28):11723.
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This work was financially supported by the Natural Science Foundation of Ningxia (No. 2020AAC03005) and the Western Light Foundation of the Chinese Academy of Sciences.
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Wang, L., Hao, YQ., Ma, W. et al. Improving phase transition temperature of VO2 via Ge doping: a combined experimental and theoretical study. Rare Met. 40, 1337–1346 (2021). https://doi.org/10.1007/s12598-020-01655-3
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DOI: https://doi.org/10.1007/s12598-020-01655-3