Preparation and properties of V1-xTbxO2(x=0,1,2,3,4)(M) thin films
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摘要: 主要研究了重稀土铽元素(Tb)掺杂对二氧化钒薄膜V1-xTbxO2(x=0,1,2,3,4)(M)相结构、微观形貌、相变温度、光学及力学性能的影响。结果表明：V1-xTbxO2(x=0,1,2,3,4)(M)样品的衍射峰尖锐，未出现其他杂质峰，具有较高的结晶度和纯度。Tb元素掺杂能明显影响二氧化钒的微观结构特征，随着Tb掺杂量的增加，相变温度呈下降趋势，在4% (原子分数，下同)的掺杂水平下，相变温度降至59.01 ℃。紫外-可见-近红外光谱分析表明，在1%～4%的Tb掺杂水平下二氧化钒薄膜的光学性能增强。在2% Tb掺杂时太阳光调制能力(ΔTsol)达到9.1%，可见光透过率(Tlum)为61.5%；在4% Tb掺杂时可见光透过率达到72.5%。力学性能表明，Tb掺杂对二氧化钒薄膜的力学性能具有增强作用。当掺杂量为2%时，VO2薄膜的力学性能显示出最大值，弹性模量及硬度分别为
83.6065 GPa和8.0026 GPa。Abstract: This article mainly investigated the effects of heavy rare earth terbium element (Tb) doping on the phase structure, microstructure, phase transition temperature, optical, and mechanical properties of vanadium dioxide thin films V1-xTbxO2(x=0,1,2,3,4)(M). The analysis results show that the diffraction peaks of V1-xTbxO2(x=0,1,2,3,4)(M) samples are sharp, with no other impurity peaks observed, indicating high crystallinity and purity. Tb element doping can significantly affect the microstructural characteristics of vanadium dioxide, with the phase transition temperature decreasing as the Tb doping level increases, reaching 59.01 ℃ at a doping level of 4%. UV-Vis-NIR analysis indicates enhanced optical properties of vanadium dioxide thin films at Tb doping levels of 1%~4%. At 2% Tb doping, solar modulating ability (ΔTsol) reaches 9.1%, and visible transmittance (Tlum) is 61.5%. At 4% Tb doping, visible transmittance reaches 72.5%. Mechanical property tests show that Tb doping enhances the mechanical properties of vanadium dioxide thin films. When the doping level is 2%, the mechanical properties of VO2 films exhibit maximum values, with elastic modulus and hardness being 83.6065 GPa and 8.0026 GPa, respectively. -
图 1 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M) XRD谱及（011）晶面局部放大
Figure 1. XRD patterns and (011) crystal plane local amplification diagram of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)
图 2 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2 $(M)薄膜XPS谱
(a) 宽谱扫描； (b) V 2p + O 1s高分辨扫描； (c) Tb 3d高分辨扫描
Figure 2. XPS spectrum of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2 $(M) films
图 3 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)的SEM形貌
Figure 3. SEM images of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)
图 4 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)样品DSC曲线及Tc随掺杂水平变化趋势
Figure 4. DSC curves of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M) samples and the trend diagram of Tc with doping level
图 5 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)薄膜UV-Vis-NIR光谱
Figure 5. UV-Vis-NIR spectra of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M) films
图 6 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)薄膜的载荷-位移曲线
Figure 6. Load-displacement curves of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M) films
表 1 ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M)薄膜的力学性能
Table 1. Mechanical properties of ${\mathrm{V}}_{1-x}{\mathrm{Tb}}_x{\mathrm{O}}_2\;(x $=0,1,2,3,4)(M) films
Tb掺
杂量/%hf/nm A/nm2 m S/(μN∙nm−1) Er/GPa E/GPa H/GPa 0 75.9248 3.6968 1.5759 86.8107 82.5867 80.9926 6.9155 1 72.1562 4.0017 1.5601 86.2096 84.0644 82.5565 7.2658 2 69.1897 6.8657 1.4552 87.1117 85.0541 83.6065 8.0026 3 71.7205 5.2672 1.5125 84.4035 84.4123 82.9256 7.5326 4 73.8157 4.9342 1.5222 85.8891 84.1183 82.7137 7.3593 
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