深圳大学学报理工版

为降低二氧化钒（VO2）材料的相变温度并提高VO2材料的光学特性，采用溶胶-凝胶辅助水热法，控制硼（B）的掺杂原子数分数为6.0%，通过后续的高温退火处理制备硼-镁（B-Mg）共掺杂的纳米VO2粉体，然后将粉体制备成薄膜．通过对B-Mg共掺纳米VO2粉体微结构进行表征，探究Mg的原子数分数对复合材料相变温度和光学特性的影响，获得满足应用标准的B-Mg共掺杂纳米VO2材料．结果表明，复合材料中掺杂的B元素和Mg元素分别以B3+和Mg2+形式存在于VO2结构中，当Mg的原子数分数为1.8%时，复合材料表现出相对优秀的热致变色特性，且具有最低的相变温度（tc=30.8℃），其太阳光调制幅度（ΔTsol=11.8%）能维持在10%以上，平均可见光透过率（Tˉlum=69.7%）比未掺杂的VO2薄膜高12.1%，满足热致变色智能窗户的要求．研究结果为制备适用于热致变色智能窗户领域的VO2材料提供了理论依据．

In order to reduce the phase transition temperature of vanadium dioxide (VO2) materials and improve the optical properties of VO2 materials, the boron-magnesium (B-Mg) co-doped vanadium dioxide (VO2) powders were prepared through a sol-gel-assisted hydrothermal method in combination with the subsequent high-temperature annealing. The obtained powder was further prepared into a thin film. X-ray diffraction (XRD), X-ray electron spectroscopy (XPS), field emission scanning electron microscope (FESEM), differential scanning calorimeter (DSC), ultraviolet-visible-near-infrared spectrophotometer (UV-vis-NIR) were used to explore the microstructure of the material and effects of the doping concentrations of Mg on the phase transition temperature tc and the optical properties of VO2 materials. The B-Mg co-doped nano-VO2 material that satisfies various application standards was obtained. The results show that the doped elements of B and Mg exist in the VO2 structure as the form of B3+ and Mg2+. When the atomic percentages of B and Mg are 6. 0% and 1. 8%, the material shows a relatively excellent thermochromic properties, with the lowest phase transition temperature tc = 30. 8 ℃. The sunlight modulation amplitude ΔTsol of the material is 11. 8%, which is maintained above 10%. The average visible light transmittance Tlum of the material is 69. 7%, which is 12. 1% higher than that of the undoped VO2 film. The properties above meet the requirements for the application in thermochromic smart windows. This work provides scientific basis for the preparation of VO2 materials suitable for thermochromic smart windows.

引言
1 实验
2 结果与讨论
结语

表1 样品S1—S4中的B-Mg共掺杂原子数分数Table 1 Atomic percentages of B-Mg in samples S1-S4 %

图1 样品S2的XPS全谱Fig. 1 XPS full spectrum of sample S2.

图2 样品S2的Mg 1s高分辨率扫描XPS图谱Fig. 2 One second high-resolution scan pattern of Mg in sample S2.

图3 样品S2的B 1s高分辨率扫描XPS图谱Fig. 3 One second high-resolution scan pattern of B in sample S2.

图4 样品S2的V 2p高分辨率扫描XPS图谱（黑色曲线为原始扫描图；红色和蓝色曲线分别为峰V 2p3/2和V 2p1/2的拟合曲线；绿色和紫色曲线分别为峰V 2p3/2中V5+和V4+的拟合曲线） Fig. 4 High-resolution scan pattern of V 2p in sample S2. Black curve is the original scan pattern, red and blue curves are the fitted curves of peaks V 2p3/2 and V 2p1/2 respectively, and green and purple curves are peak the fitted curves of V5+and V4+in V 2p3/2.

图5 样品S1—S4的XRD全谱Fig. 5 XRD spectra of samples S1-S4.

图6 样品S2的FE-SEM照片（a）和（b）为样品S2在不同放大倍率下的SEM照片；（c）B元素（蓝色）在图（b）区域中的分布；（d） Mg元素（红色）在图（b）区域中的分布Fig. 6 FE-SEM images of sample S2. (a) and (b) are SEM images of sample S2 at different magnifications, (c) is the distribution of boron (blue dots) in the area of figure (b), (d) is magnesium (red dots) distribution in the area of figure (b).

图7 样品S1—S4的冷却段DSC曲线Fig. 7 DSC curves of cooling sections of samples S1-S4.

图8 样品S1—S4的升温段DSC曲线Fig. 8 DSC curves of heating sections of samples S1-S4.

表2 样品S1—S4的MIT特性Table 2 MIT characteristics of samples S1-S4

图9 样品S1—S4在20℃和90℃下的透过率光谱Fig. 9 Transmittance spectra of samples S1-S4 at 20℃and 90℃.

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