ZnS基光谱转换材料及其薄膜的研究
发布时间：2018-10-11 18:49
【摘要】：ZnS是一种重要的半导体基材,禁带宽度是3.59~3.79e V,拥有优越的特性,广泛应用于各种半导体元器件,如发光二极管、薄膜电致发光显示器件、场致发光器件、紫外光探测器件等,还可作为铜铟硒基薄膜太阳能电池的n型窗口层,以其独特的光谱转换效果和无毒、环保价值替代CdS薄膜。ZnS经适量的掺杂(如Sm、Mn等杂质原子)可拓宽其光谱响应范围、调节其的发光效率,因此也可以作为荧光基材进行研究。本文采用溶剂热法,将硝酸盐和硫粉分别作为锌源和硫源、氧化钐为掺杂剂,在填充度为75%的条件下,制备了形状规则、分散性好的微球状ZnS及ZnS:Sm发光材料。探讨了反应温度、反应时间、反应介质、掺杂摩尔浓度等对微球表面形貌、物相结构、荧光光谱的影响。实验结果表明:反应温度越高,微球粒径越大、晶体生长越完整,其发光强度随温度的上升先增后降;Sm3+的掺入量越多,其内部生成的发光中心越多、发光强度越高,然而当Sm3+掺杂量达到5%时,发光减弱;反应介质为乙醇时,生成的ZnS纳米球团聚严重,激发发射峰位置均蓝移。综合考虑,最佳的反应条件为:反应温度170℃,反应时间14h,Sm3+掺杂摩尔浓度为3%,反应介质为水。本文还通过真空蒸镀法在钠钙硅玻璃基底上制备了ZnS及ZnS:Sm荧光薄膜,并较系统的研究了衬底温度、掺杂离子、退火对其表面形貌、物相、荧光特性、表面成分、透过率、禁带宽度的影响。实验结果说明:真空蒸镀制备的薄膜表面呈“稻谷”状,且随反应基底的温度的上升其表面越发平整致密,其禁带宽度呈增大趋势,然而基底温度过高又会导致薄膜表面开裂;薄膜呈H(111)面优先生长,且随着衬底温度的升高衍射峰强度先升后降,200℃时衍射峰最强,薄膜透过率也最高;掺杂Sm3+后,(111)晶面的衍射峰有所下降,而透过率有所上升,其荧光发射峰变的尖锐且发射峰强度大幅度提高;随着退火温度逐渐上升,薄膜表面越发粗糙,出现层状生长的“凸起”,且晶粒尺寸逐渐增大;退火后ZnS:Sm薄膜的衍射峰增强,且向右略有偏移,其透过率显著下降,禁带宽度增大。
[Abstract]:ZnS is an important semiconductor substrate with a band gap of 3.59 ~ 3.79e V. it has excellent characteristics and is widely used in various semiconductor components, such as light-emitting diodes, thin film electroluminescent display devices, field luminescent devices, ultraviolet detectors and so on. It can also be used as the n-type window layer of Cu-indium selen-based thin film solar cells. With its unique spectral conversion effect and non-toxicity, the CdS film can be replaced by environmental protection value. The range of spectral response of ZnS can be widened by proper doping (such as Sm,Mn and other impurity atoms). It can also be used as a fluorescent substrate to study its luminescence efficiency. In this paper, microspherical ZnS and ZnS:Sm luminescent materials with regular shape and good dispersion were prepared by solvothermal method using nitrate and sulfur powder as zinc source and sulfur source, samarium oxide as dopant, and filling degree of 75%. The effects of reaction temperature, reaction time, reaction medium and doping molar concentration on the surface morphology, phase structure and fluorescence spectra of the microspheres were discussed. The experimental results show that the higher the reaction temperature, the larger the particle size, the more complete the crystal growth, and the higher the luminescence intensity increases and then decreases with the increase of temperature, and the more the amount of Sm3 is added, the more luminescence centers are generated and the higher the luminescence intensity is. However, when the doping amount of Sm3 reaches 5, the luminescence weakens, and when the reaction medium is ethanol, the agglomeration of the ZnS nanospheres is serious, and the position of the excitation emission peaks are all blue shifted. The optimum reaction conditions are as follows: reaction temperature 170 鈩，
本文编号：2264874
[Abstract]:ZnS is an important semiconductor substrate with a band gap of 3.59 ~ 3.79e V. it has excellent characteristics and is widely used in various semiconductor components, such as light-emitting diodes, thin film electroluminescent display devices, field luminescent devices, ultraviolet detectors and so on. It can also be used as the n-type window layer of Cu-indium selen-based thin film solar cells. With its unique spectral conversion effect and non-toxicity, the CdS film can be replaced by environmental protection value. The range of spectral response of ZnS can be widened by proper doping (such as Sm,Mn and other impurity atoms). It can also be used as a fluorescent substrate to study its luminescence efficiency. In this paper, microspherical ZnS and ZnS:Sm luminescent materials with regular shape and good dispersion were prepared by solvothermal method using nitrate and sulfur powder as zinc source and sulfur source, samarium oxide as dopant, and filling degree of 75%. The effects of reaction temperature, reaction time, reaction medium and doping molar concentration on the surface morphology, phase structure and fluorescence spectra of the microspheres were discussed. The experimental results show that the higher the reaction temperature, the larger the particle size, the more complete the crystal growth, and the higher the luminescence intensity increases and then decreases with the increase of temperature, and the more the amount of Sm3 is added, the more luminescence centers are generated and the higher the luminescence intensity is. However, when the doping amount of Sm3 reaches 5, the luminescence weakens, and when the reaction medium is ethanol, the agglomeration of the ZnS nanospheres is serious, and the position of the excitation emission peaks are all blue shifted. The optimum reaction conditions are as follows: reaction temperature 170 鈩，
本文编号：2264874
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