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Thermal kinetic analysis of metal–insulator transition mechanism in W-doped VO2

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Abstract

Tungsten (W) doping can decrease the phase transition temperature of VO2, but underlining reasons are not clear. In this study, differential scanning calorimetry was employed to investigate the kinetics of the solid–solid transition in hydrothermal-synthesized W (X = 0.50, 1.09, 2.58 and 3.81 %)-doped VO2 nanoparticles. We firstly revealed the W-doping mechanism by combining the classical nucleation kinetics model with isoconversional kinetic analysis and applied them on the solid–solid transition taking place in doping. The experimentally observed large lag in the cooling stage and asymmetry effects of the decreasing temperature on insulator–metal transition and metal–insulator transition can be rationally explained. In the heating stage, W doping decreases free energy barrier (ΔG*) for homogenous nucleation and reduces geometrical factor (f(Θ)) and both factors promote the transition and thus lower the phase transition temperature quickly. However, in cooling stage, the free energy barrier (ΔG *het ) for heterogeneous nucleation was much larger than that of heating stage due to lacking of proper nucleation sites. The effect of decreasing geometrical factor was accompanied with the effect of increasing free energy barrier for homogenous nucleation by doping W. Such a competition mechanism slows down the trend of reducing temperature. It is important to unravel interaction mechanisms of doped W on different VO2 phases, which is helpful to further tailor kinetic properties of VO2 phase transition.

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Acknowledgements

The authors wish to express their deep appreciation to Prof. Sergey Vyazovkin for his useful suggestions. This work is supported by National Nature Science Foundation of China (Nos. 51325203, 51472263), Shanghai Materials Genome Project (14DZ2261200), Project supported by Shanghai technical platform for testing and characterization on inorganic materials (14DZ2292900), and Program of the Innovative Fund of Shanghai Institute of Ceramics, Chinese Academy of Science (Y37ZC4143G).

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Authors and Affiliations

  1. School of Materials Science and Engineering, Shanghai University, 99 Shangda Road, Shanghai, 200444, China

    Heng Zhang, Zhang Chen, Hongjie Luo & Yanfeng Gao

  2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai, 200050, China

    Heng Zhang, Huimei Yu, Hongjie Luo & Yanfeng Gao

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  1. Heng Zhang
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  2. Huimei Yu
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  5. Yanfeng Gao
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Correspondence to Huimei Yu or Yanfeng Gao.

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Zhang, H., Yu, H., Chen, Z. et al. Thermal kinetic analysis of metal–insulator transition mechanism in W-doped VO2 . J Therm Anal Calorim 126, 949–957 (2016). https://doi.org/10.1007/s10973-016-5579-3

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