Preparation and properties of AZO/Ag/AZO thin films on PMMA substrates
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摘要: 采用低温磁控溅射技术在有机玻璃（聚甲基丙烯酸甲酯PMMA）表面制备铝掺杂氧化锌（AZO）叠层AZO/Ag/AZO透明导电薄膜，研究AZO溅射功率对AZO/Ag/AZO薄膜结构和性能的影响，探讨PMMA层合结构的耐湿热性和加温性能。通过扫描电子显微镜（SEM）、原子力显微镜（AFM）、X射线衍射仪（XRD）表征薄膜的形貌和结构。结果表明：AZO的溅射功率影响了AZO层表面能以及薄膜的结晶度，在100 W和150 W溅射功率下制备出的AZO/Ag/AZO薄膜室温下具有3.7 Ω/sq的低薄膜电阻和86.1%的高透光率，采用PMMA和聚氨酯胶片对薄膜进行层合封装，湿热30天后仍保持光学、电学性能稳定。PMMA层合结构在加温过程中的时间-温度曲线表明在5 V直流电压下层合玻璃具有较快的温度响应时间和良好的温度均匀性。−10~−40 ℃空气对流中PMMA层合结构表现出良好的温度稳定性。
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关键词:
- PMMA /
- AZO/Ag/AZO /
- 层合 /
- 耐湿热性 /
- 电加温
Abstract: AZO/Ag/AZO transparent conductive films were prepared on PMMA substrate by DC magnetron sputtering at low temperature (70 ℃). The effect of AZO sputtering power on the structure and properties of AZO/Ag/AZO thin films were investigated. In order to encapsulate AZO/Ag/AZO films, the films were laminated with another uncoated PMMA substrate and polyurethane film. Damp and heat resistance and heating performance of this laminated structure were discussed. The morphology and structure of the films were characterized by SEM, XRD and AFM. The results show that the sputtering power of AZO affects the surface energy of AZO layer and the crystallization of AZO/Ag/AZO films. The AZO/Ag/AZO films which prepared with AZO sputtering power of 100W and 150W exhibit the best performance with a low sheet resistance of 3.7 Ω/sq and a high transmittance of 86.1% at room temperature. The optical and electrical properties of PMMA laminated structure remain stable after 30 days of damp-heat experiment. The temperature-time curve during the heating process of the PMMA laminated structure at room temperature shows fast temperature response time and good temperature uniformity under 5 V DC voltage. The PMMA laminated structure exhibits saturation temperature stability in cold convection air (−10-−40 ℃).-
Key words:
- PMMA substrate /
- AZO/Ag/AZO /
- lamination /
- damp-heat /
- transparent heaters
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图 1 PMMA基底AZO/Ag/AZO薄膜层合电加温玻璃制备流程
Figure 1. Preparation process of PMMA-based AZO/Ag/AZO thin film laminated heaters
图 2 不同AZO溅射功率沉积的AZO/Ag/AZO薄膜XRD图
Figure 2. XRD patterns of AZO/Ag/AZO thin films prepared by sputtering AZO with different powers
图 3 Ag在PMMA基体以及不同溅射功率下的AZO表面生长的AFM图 （a）PMMA/Ag；（b）PMMA/ 50 W AZO/Ag；（c）PMMA/ 100 W AZO/Ag；（d）PMMA/150 W AZO/Ag；（e）PMMA/200 W AZO/Ag；
Figure 3. AFM images of Ag growth on PMMA substrate surface and AZO surface deposited with different sputtering powers (a) PMMA/Ag; (b) PMMA/ 50 W AZO/Ag; (c) PMMA/ 100 W AZO/Ag: (d) PMMA/150 W AZO/Ag; (e) PMMA/200 W AZO/Ag
图 4 不同AZO溅射功率沉积的AZO/Ag/AZO薄膜方阻
Figure 4. Resistance of AZO/Ag/AZO thin films prepared by sputtering AZO with different powers
图 5 不同AZO溅射功率沉积的AZO/Ag/AZO薄膜可见光透光率曲线
Figure 5. Visible light transmittance curves of AZO/Ag/AZO thin films prepared by sputtering of AZO with different powers
图 6 不同时长湿热实验后AZO/Ag/AZO薄膜SEM图像 （a）10 d后；（b），（c）15 d后；（d），（e）20 d后；（f）30 d后
Figure 6. SEM images of AZO/Ag/AZO films after different time of damp-heat experiments (a) after 10 days; (b)， (c) after 15 days; (d) ，(e) after 20 days; (f) after 30 days
图 7 不同时长湿热实验后AZO/Ag/AZO薄膜微观形貌和EDS微区成分 （a）10 d后；（b）15 d后；（c）20 d后；（1）形貌；（2）、（3）微区成分
Figure 7. Micromorphology of AZO/Ag/AZO thin films and EDS microdomain composition after different time of damp-heat experiments (a) after 10 days; (b) after 15 days; (c) after 20 days; (1) micromorphology; (2), (3) microdomain composition
图 8 未层合AZO/Ag/AZO薄膜 （a）和PMMA层合AZO/Ag/AZO薄膜（b）
Figure 8. Unlaminated AZO/Ag/AZO film (a) and PMMA-laminated AZO/Ag/AZO film (b)
图 9 湿热实验对未层合与层合封装后的AZO/Ag/AZO薄膜性能的影响 （a）透光率变化；（b）雾度变化；（c）电阻变化
Figure 9. Influence of damp-heat time on performance of AZO/Ag/AZO with and without lamination (a) change in transmittance；(b) haze variation ；(c) resistance variation
图 10 不同电压加载下PMMA层合玻璃的温度-时间曲线
Figure 10. Temperature-time curves of PMMA laminated structures with different voltages
图 11 使用5 V直流电压进行除霜过程 （a）未升温；（b）升温47 s；（c）升温54 s；（d）升温224 s
Figure 11. Defrost process with 5 V DC (a) without heating; (b) after 47 s; (c) after 54 s; (d) after 224 s
图 12 低温下PMMA层合结构升温曲线 （a）稳态温度随升-降温循环变化曲线；（b）稳态温度随升温时间变化曲线
Figure 12. Temperature curves of PMMA laminated structure at low temperature (a) curves of stable temperature versus heating and cooling cycle; (b) curves of stable temperature versus heating time
表 1 不同AZO溅射功率下AZO和Ag膜的XRD特征值
Table 1. XRD data assessment for AZO and Ag films with different sputtering powers of AZO layers
Sputtering power of AZO/W Diffraction angle/（°） FWHM/rad Grain size/nm AZO Ag AZO Ag AZO Ag 50 16.94 19.08 0.01107 0.01042 12.9 13.9 100 16.98 19.09 0.01051 0.01077 13.6 13.5 150 16.90 19.05 0.01049 0.01079 13.7 13.4 200 16.92 19.06 0.01169 0.01073 12.3 13.5 
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表 2 不同溅射功率沉积的AZO和PMMA基体表面能参数
Table 2. Surface energy parameters of PMMA substrates and AZO deposited with different sputtering powers
Material $ {\gamma }_{\rm S}^{\rm LW} $/（mJ·m−2） $ {\gamma }_{\rm S}^{+} $/ （mJ·m−2） $ {\gamma }_{\rm S}^{-} $/ （mJ·m−2） $ {\gamma }_{\rm S} $/（ mJ·m−2） 50 W AZO 46.02 0.18 25.97 50.38 100 W AZO 47.57 0.21 26.95 52.36 150 W AZO 45.79 0.24 26.39 50.88 200 W AZO 44.90 0.04 20.65 46.89 PMMA 38.06 0.05 4.46 39.09 Note：$ {\gamma }_{\rm S}^{\rm LW} $ is Lifshitz-van der Waals; $ {\gamma }_{\rm S}^{+} $ is Lewis acid; $ {\gamma }_{\rm S}^{-} $ is Lewis base; $ {\gamma }_{\rm S} $ is solid surface energy.
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