氮气流量对非晶SiN_x到含有Si_3N_4晶粒的富硅-SiN_x薄膜转变的影响
|
摘要
基于等离子体增强化学气相沉积(PECVD)技术,应用高纯硅烷和氮气为反应气体,通过设置氮气流量分别为100 sccm、200 sccm、300 sccm和400 sccm四个梯度,研究非晶SiN_x到含有Si_3N_4晶粒的富硅SiN_x薄膜材料转变的影响,并利用傅里叶红外变换谱、紫外-可见光谱和X射线衍射谱对薄膜样品结构进行表征.结果表明,随着N_2流量的增加,SiN_x薄膜中氮原子浓度减小,Si-N键密度减小,Si-H键密度增加,薄膜中出现Si-Si键并且密度逐渐增加,非晶SiN_x逐渐向富硅SiN_x薄膜转变.同时薄膜光学带隙逐渐变大,缺陷态密度增加,微观结构的有序度减小,也说明N_2的增加对富硅SiN_x薄膜产生有促进作用.此外,薄膜内出现了Si_3N_4结晶颗粒,且晶粒尺度随着N_2流量增加而减小,进一步说明薄膜从非晶SiN_x逐渐向含Si_3N_4结晶颗粒的富硅SiN_x转变.该实验证明了采用PECVD技术制备SiN_x薄膜时,通过控制N_2流量,有助于薄膜从非晶SiN_x逐渐向含有结晶的Si_3N_4的富硅SiN_x薄膜转变.
The effect of the N_2 flow rate on the transition from amorphous SiN_x to Si-rich SiN_x films containing Si_3N_4 crystal grains was studied based on the plasma enhanced chemical vapor deposition(PECVD) system,in which high purity silane and nitrogen were used as reaction gases,and other deposition parameters were optimized.Four different N_2 flow rates,including 100,200,300 and 400 sccm,were set up to investigate the effect of nitrogen on preparation of SiN_x films.The Fourier transform infrared absorption(FTIR) spectroscopy,ultraviolet-visible(UV-VIS) spectroscopy light transmittance spectroscopy and X-ray diffraction(XRD) spectroscopy were used to characterize the structure of the films. The results showed that the concentration of nitrogen atom decreased in the SiN_x films with the increase of N_2 flow rates,which led to decreasing the density of Si-N bond but increasing the concentration of Si-H bond.At the same time,the Si-Si bonds appeared in the films and its concentration increased gradually.We also found that the optical band gap and the density of defect states increased gradually,and the degree of order of microstructure decreased with the increase of N_2 flow rates,indicating that the increase of N_2 was able to promote the formation of Si-rich SiN_x films.In addition,with the increase of N_2 flow rates,Si_3N_4 crystal grains appeared in the films,and the grain size decreased,which further suggested that the films gradually changed from amorphous SiN_x to Si-rich SiN_x containing Si_3N_4 crystal grains.This experiment proved that controlling the flow rates of N_2 was able to facilitate the transition from amorphous SiN_x to Si-rich SiN_x films containing Si_3N_4 crystal grains in preparation of SiN_x films by PECVD.
The effect of the N_2 flow rate on the transition from amorphous SiN_x to Si-rich SiN_x films containing Si_3N_4 crystal grains was studied based on the plasma enhanced chemical vapor deposition(PECVD) system,in which high purity silane and nitrogen were used as reaction gases,and other deposition parameters were optimized.Four different N_2 flow rates,including 100,200,300 and 400 sccm,were set up to investigate the effect of nitrogen on preparation of SiN_x films.The Fourier transform infrared absorption(FTIR) spectroscopy,ultraviolet-visible(UV-VIS) spectroscopy light transmittance spectroscopy and X-ray diffraction(XRD) spectroscopy were used to characterize the structure of the films. The results showed that the concentration of nitrogen atom decreased in the SiN_x films with the increase of N_2 flow rates,which led to decreasing the density of Si-N bond but increasing the concentration of Si-H bond.At the same time,the Si-Si bonds appeared in the films and its concentration increased gradually.We also found that the optical band gap and the density of defect states increased gradually,and the degree of order of microstructure decreased with the increase of N_2 flow rates,indicating that the increase of N_2 was able to promote the formation of Si-rich SiN_x films.In addition,with the increase of N_2 flow rates,Si_3N_4 crystal grains appeared in the films,and the grain size decreased,which further suggested that the films gradually changed from amorphous SiN_x to Si-rich SiN_x containing Si_3N_4 crystal grains.This experiment proved that controlling the flow rates of N_2 was able to facilitate the transition from amorphous SiN_x to Si-rich SiN_x films containing Si_3N_4 crystal grains in preparation of SiN_x films by PECVD.
引文
[1] Mercaldo L V,Veneri P D,Esposito E,et al.PECVD in-situ growth of silicon quantum dots in silicon nitride from silane and nitrogen [J].Materials Science & Engineering B,2009,159(11):77-79.
[2] 部芯芯,周炳卿,丁德松.氮气对PECVD制备氮化硅薄膜结构与性质的影响 [J].内蒙古师大学报:自然科学汉文版,2017,46(3):350-353.
[3] 张龙龙,周炳卿,张林睿,等.PECVD制备富硅氮化硅薄膜的工艺条件及其性质的研究 [J].2014,33(4):757-763.
[4] 乌仁图雅,周炳卿,张林睿,等.氢流量对富硅-氮化硅薄膜键结构及光学性质的影响 [J].人工晶体学报,2015,44(12):3449-3454.
[5] 汪广进,余意,程凤,等.过渡金属氮氧化物制备方法的研究进展 [J].材料导报,2012,26(9):27-31.
[6] 高爱明,周炳卿,张林睿,等.氮流量对热丝制备富硅-氮化硅薄膜的结构及性质影响 [J].信息记录材料,2016,17(1):53-58.
[7] 刘东山.铁基软磁复合材料制备及其包覆层热稳定性的研究 [D].哈尔滨:哈尔滨工业大学材料科学与工程学院,2013.
[8] Lanford W A,Rand M J.The hydrogen content of plasma-deposited silicon nitride [J].Journal of Applied Physics,1978,49(4):2473-2477.
[9] MoliNari M,Rinnert H,Vergnat M.Improvemnt of the photoluminescence properties in a-SiNx films by introduction of hydrogen [J].ApplPhysLett,2001,79(14):2172-2174.
[10] 陈全海.氮化硅薄膜的光吸收及光致发光性质研究 [D].兰州:西北师范大学物理与电子工程学院,2007.
[11] 周东.PECVD氮化硅薄膜制备与微结构研究 [D].成都:电子科技大学光电科学与工程学院,2011.
[12] 栗蕾蕾.氧化铅薄膜的制备及其X射线光电导特性的研究 [D].杭州:杭州电子科技大学电子信息学院,2011.
[13] 冯兴联.SiO2薄膜的PECVD生长研究 [D].西安:西安电子科技大学电子工程学院,2013.
[14] Li T,Jerzy K,Kong W,et al.Interference fringe-free transmission spectroscopy of amorphous thin films [J].Journal of Applied Physics,2000,88(10):5764-5771.
[15] 丁德松,周炳卿,部芯芯,等.氮化硅薄膜的热丝化学气相沉积法制备及微结构研究 [J].硅酸盐通报,2017,2,706-711.
[16] 丁建云.硅基薄膜量子阱及其材料的研究 [D].汕头:汕头大学理学院,2012.
[17] 晁军峰.半导体Sn、Sb基硫属化合物的制备及其性能研究 [D].武汉:华中科技大学物理学院,2013.
[18] 蒋平.沉积气压对ZnO薄膜的结构与光学性能影响 [D].苏州:苏州大学物理科学与技术学院,2009.
[19] Panchal A K,Solanki C S.Post deposition annealing temperature effect on silicon quantum dots embedded in silicon nitride dielec-tric multilayer prepared by hot-wire chemical vapor deposition [J].Thin Solid Films,2009,517(2):3488-3491.
[2] 部芯芯,周炳卿,丁德松.氮气对PECVD制备氮化硅薄膜结构与性质的影响 [J].内蒙古师大学报:自然科学汉文版,2017,46(3):350-353.
[3] 张龙龙,周炳卿,张林睿,等.PECVD制备富硅氮化硅薄膜的工艺条件及其性质的研究 [J].2014,33(4):757-763.
[4] 乌仁图雅,周炳卿,张林睿,等.氢流量对富硅-氮化硅薄膜键结构及光学性质的影响 [J].人工晶体学报,2015,44(12):3449-3454.
[5] 汪广进,余意,程凤,等.过渡金属氮氧化物制备方法的研究进展 [J].材料导报,2012,26(9):27-31.
[6] 高爱明,周炳卿,张林睿,等.氮流量对热丝制备富硅-氮化硅薄膜的结构及性质影响 [J].信息记录材料,2016,17(1):53-58.
[7] 刘东山.铁基软磁复合材料制备及其包覆层热稳定性的研究 [D].哈尔滨:哈尔滨工业大学材料科学与工程学院,2013.
[8] Lanford W A,Rand M J.The hydrogen content of plasma-deposited silicon nitride [J].Journal of Applied Physics,1978,49(4):2473-2477.
[9] MoliNari M,Rinnert H,Vergnat M.Improvemnt of the photoluminescence properties in a-SiNx films by introduction of hydrogen [J].ApplPhysLett,2001,79(14):2172-2174.
[10] 陈全海.氮化硅薄膜的光吸收及光致发光性质研究 [D].兰州:西北师范大学物理与电子工程学院,2007.
[11] 周东.PECVD氮化硅薄膜制备与微结构研究 [D].成都:电子科技大学光电科学与工程学院,2011.
[12] 栗蕾蕾.氧化铅薄膜的制备及其X射线光电导特性的研究 [D].杭州:杭州电子科技大学电子信息学院,2011.
[13] 冯兴联.SiO2薄膜的PECVD生长研究 [D].西安:西安电子科技大学电子工程学院,2013.
[14] Li T,Jerzy K,Kong W,et al.Interference fringe-free transmission spectroscopy of amorphous thin films [J].Journal of Applied Physics,2000,88(10):5764-5771.
[15] 丁德松,周炳卿,部芯芯,等.氮化硅薄膜的热丝化学气相沉积法制备及微结构研究 [J].硅酸盐通报,2017,2,706-711.
[16] 丁建云.硅基薄膜量子阱及其材料的研究 [D].汕头:汕头大学理学院,2012.
[17] 晁军峰.半导体Sn、Sb基硫属化合物的制备及其性能研究 [D].武汉:华中科技大学物理学院,2013.
[18] 蒋平.沉积气压对ZnO薄膜的结构与光学性能影响 [D].苏州:苏州大学物理科学与技术学院,2009.
[19] Panchal A K,Solanki C S.Post deposition annealing temperature effect on silicon quantum dots embedded in silicon nitride dielec-tric multilayer prepared by hot-wire chemical vapor deposition [J].Thin Solid Films,2009,517(2):3488-3491.