H_2对Al-Si-GNP共掺杂ZnO透明导电薄膜性能的影响
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摘要
以玻璃为基底,采用射频磁控溅射法制备了Al_2O_3、SiO_2、氧化石墨烯(GNP)共掺杂氧化锌(GASZO)透明导电薄膜.考察了在Ar(流量不变)中H_2流量对薄膜制备的影响.采用X射线衍射仪(XRD)及扫描电子显微镜(SEM)等对薄膜形貌、结构进行了表征.结果表明薄膜晶相为纤锌矿结构、呈c轴择优取向; Scherrer公式计算发现增加H_2量,可以减小薄膜的平均晶粒尺寸; H_2流量对薄膜内应力影响较大.此外,还采用四探针测试仪、紫外—可见分光光度计(UV-Vis)等对薄膜的光电性能进行了表征.当Ar流量为70 sccm、H_2占溅射气氛1. 00%时,薄膜具有最低电阻率7. 746×10~(-4)Ω·cm;适量的H_2流量可以提高玻璃在近紫外区的透过率;镀膜后样品在可见光区的平均透过率为90%左右.
In the report,Al_2O_3,SiO_2 and grapheme oxide( GNP) co-doped ZnO( GASZO) transparent conductive films were grown on glass by radio frequency( RF) magnetron sputtering. Under certain argon flow rate,the effects of H_2 flow rate on preparation of the films were investigated. X-ray diffraction( XRD) and scanning electron microscopy( SEM) were used to analyze the structure and morphology of co-doped ZnO thin films. The results indicated that all the deposited films present a crystalline wurtzite structure with a strong preferred orientation along the c-axis. With the increase of hydrogen gas content,the average grain size of the film decreased.The internal stress of the film was affected greatly by hydrogen flow rate. Also,four-point probes technique and UV-visible spectroscopy( UV-Vis) were used to characterize the photoelectric property of thin films. The film had the lowest resistivity of 7. 746 × 10~(-4)Ω·cm with Ar-flux of 70 sccm,accounting 1% H_2. The transmittance of near ultraviolet region improved with proper H_2-flux,and the average transmittance of all the samples in the visible range was about 90%.
In the report,Al_2O_3,SiO_2 and grapheme oxide( GNP) co-doped ZnO( GASZO) transparent conductive films were grown on glass by radio frequency( RF) magnetron sputtering. Under certain argon flow rate,the effects of H_2 flow rate on preparation of the films were investigated. X-ray diffraction( XRD) and scanning electron microscopy( SEM) were used to analyze the structure and morphology of co-doped ZnO thin films. The results indicated that all the deposited films present a crystalline wurtzite structure with a strong preferred orientation along the c-axis. With the increase of hydrogen gas content,the average grain size of the film decreased.The internal stress of the film was affected greatly by hydrogen flow rate. Also,four-point probes technique and UV-visible spectroscopy( UV-Vis) were used to characterize the photoelectric property of thin films. The film had the lowest resistivity of 7. 746 × 10~(-4)Ω·cm with Ar-flux of 70 sccm,accounting 1% H_2. The transmittance of near ultraviolet region improved with proper H_2-flux,and the average transmittance of all the samples in the visible range was about 90%.
引文
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[2]Nisha M,Anusha S,Antony A,et al.Effect of Substrate Temperature on the growth of ITO thin films[J].Applied Surface Science,2005,252(5):1 430-1 435.
[3]Sharma V,Kumar P,Kumar A,et al.High-performance radiation stable Zn O/Ag/Zn O multilayer transparent conductive electrode[J].Solar energy materials and Solar cells,2017,169:122-131.
[4]Shin S W,Agawane G L,Kim I Y,et al.Development of transparent conductive Mg ang Ga co-doped Zn O thin films:Effect of Mg concentration[J].Surface and Coating Technology,2013,231:364-369.
[5]钟志有,龙路,陆轴,等.Ga-Ti共掺杂Zn O透明导电薄膜的微观结构和光电性能研究[J].材料导报B(研究篇),2015,29(8):8-12.
[6]马洪芳,马芳,刘志宝,等.Al/Ga共掺杂Zn O透明导电薄膜的正交优化[J].太阳能学报,2015,36(7):1 550-1 555.
[7]袁玉珍,王辉,张化福,等.膜厚对Zr,Al共掺杂Zn O透明导电薄膜结构和光电性能的影响[J].人工晶体学报,2010,39(1):169-173.
[8]Wang Y,Song J,Zheng W,et al.Experimental and theoretical analysis of H and Ti co-doped Zn O transparent conductive films[J].Ceramics International,2017,43(7):5 396-5 402.
[9]田淙升,陈新亮,刘杰铭,等.氢气引入对宽光谱Mg和Ga共掺杂Zn O透明导电薄膜的特性影响[J].物理学报,2014,63(3):351-356.
[10]Macco B,Knoops H C M,Verheijen M A,et al.Atomic layer deposition of high-mobility hydrogen-doped zinc oxide[J].Solar energy materials and Solar cells,2017,173:111-119.
[11]Van D W CG.Hydrogen as a cause of doping in zinc oxide[J].Phys.Rev.Lett.2000,85(5):1 012-1 015.
[12]段光申,丁春华,姜宏,等.氩气流量对多元掺杂Zn O薄膜性能的影响[J].材料导报,2016,30(28):425-428.
[13]刘汉法,张化福,袁玉珍,等.掺钛氧化锌透明导电薄膜的制备及特性研究[J].半导体技术,2009,34(11):1 092-1 095.
[14]Chen L Y,Chen W H,Wang J J,et al.Hydrogen doped high conductivity Zn O films deposited by radio-frequency magnetron sputtering[J].Applied Physics Letters,2004,85(23):5 628-5 630.
[15]Wang F H,Chao J C,Liu H W,et al.Physical properties of Zn O thin films codoped with titanium and hydrogen prepared by RF magnetron sputtering with different substrate temperatures[J].Journal of Nanomaterials.2015,2015:1-11.