氮化硅薄膜生长随时间演化过程及其特性研究

硅酸盐通报 ›› 2021, Vol. 40 ›› Issue (7): 2396-2400.

氮化硅薄膜生长随时间演化过程及其特性研究

孙佳欣, 周炳卿

内蒙古师范大学物理与电子信息学院,内蒙古材料物理与化学自治区重点实验室,呼和浩特 010022

收稿日期:2021-01-28 修回日期:2021-03-01 出版日期:2021-07-15 发布日期:2021-08-04
通讯作者: 周炳卿,博士,教授。E-mail:zhoubq@imnu.edu.cn
作者简介:孙佳欣(1994—),女,硕士研究生。主要从事光电薄膜材料与太阳能电池的研究。E-mail:2637255253@qq.com
基金资助:
国家自然科学基金(51262022);内蒙古师范大学研究生科研创新基金(CXJJS19108)

Growth Evolution of Silicon Nitride Film over Time and Its Characteristics

SUN Jiaxin, ZHOU Bingqing

Key Laboratory of Inner Mongolia Materials Science and Chemistry, College of Physics and Electron Information, Inner Mongolia Normal University, Huhhot 010022, China

Received:2021-01-28 Revised:2021-03-01 Online:2021-07-15 Published:2021-08-04

摘要/Abstract

摘要： 氮化硅SiN_x薄膜凭借介电常数高和稳定性好的特点而被广泛应用于光电器件中,但薄膜的厚度对器件的性能有重要影响。针对此问题采用等离子体化学气相沉积技术,以高纯NH₃、N₂和SiH₄为反应气体,优化其他沉积参数,通过改变沉积时间来生长SiN_x薄膜。用X射线衍射谱(XRD),紫外-可见光光谱(UV-VIS)、傅里叶变换红外光谱(FTIR)和扫描电镜(SEM)对薄膜结构进行表征,详细研究了沉积时间与薄膜厚度的关系以及沉积时间对薄膜性能的影响。试验结果表明:所制备的样品为非晶SiN_x薄膜结构,薄膜厚度随沉积时间均匀增加;薄膜折射率随沉积时间的增加而增大,光学带隙基本不随时间变化。SEM测试结果表明,随着沉积时间增加,薄膜致密性与均匀性越来越好,氧含量也越来越少,说明薄膜致密性提高可以有效阻挡O原子进入薄膜,阻止后氧化现象的发生。

关键词: 等离子增强化学气相沉积, 氮化硅薄膜, 沉积时间, 光学带隙, 折射率, 致密度

Abstract: Silicon nitride (SiN_x) films have been widely used in optoelectronic devices due to their high dielectric constant and good stability, but the thickness of silicon nitride films has an important effect on the performance of devices. In order to solve this problem,silicon nitride films have been grown by plasma enhanced chemical vapor deposition (PECVD) at 13.56 MHz on glass and N-type monocrystalline silicon substrate using high purity NH₃, N₂and SiH₄ as reactant gas sources by optimizing other deposition parameters and changing deposition time. The samples were characterized by X-ray diffraction (XRD), ultraviolet-visible(UV-VIS) light transmittance spectra, fourier transform infrared absorption spectroscopy (FTIR) and scanning electron microscope (SEM). The relationship between deposition time and film thickness and the effect of deposition time on film properties were studied in detail. The results show that the prepared samples are amorphous SiN_x thin film structure and the crystallization is independent of deposition time. The thickness of the thin film increases uniformly with deposition time, the refractive index of the thin film increases with deposition time, and the optical band gap does not change with deposition time. SEM test results show that with the increase of deposition time, the film density and uniformity become better and better. Fourier transform infrared spectra show that the silicon/nitrogen ratio of the thin film does not change with deposition time, but the oxygen content decreases, indicating that the increased film density effectively prevents O atoms from entering the film and prevents the occurrence of oxidation after the thin film is deposited. The experimental results show that good optical properties and dense structure of silicon nitride films can be obtained by changing deposition time.

Key words: plasma enhanced chemical vapor deposition, silicon nitride film, deposition time, optical band gap, refractive index, density

中图分类号:

O484

孙佳欣, 周炳卿. 氮化硅薄膜生长随时间演化过程及其特性研究[J]. 硅酸盐通报, 2021, 40(7): 2396-2400.

SUN Jiaxin, ZHOU Bingqing. Growth Evolution of Silicon Nitride Film over Time and Its Characteristics[J]. BULLETIN OF THE CHINESE CERAMIC SOCIETY, 2021, 40(7): 2396-2400.

参考文献

[1] 李攀,张倩,夏金松,等.PECVD氮化硅薄膜性质及工艺研究[J].光学仪器,2019,41(3):81.
LI P, ZHANG Q, XIA J S, et al. Properties and preparation of low stress SiN_x film by PECVD[J]. Optical Instruments, 2019, 41(3): 81 (in Chinese).
[2] XU P, ZHANG Y, ZHANG S, et al. SiN_x-Si interlayer coupler using a gradient index metamaterial[J]. Optics Letters, 2019, 44(5): 1230-1233.
[3] AHN D, KIM C, LEE J G, et al. The effect of nitrogen on the cycling performance in thin-film Si_1-xN_x anode[J]. Journal of Solid State Chemistry, 2008, 181(9): 2139-2142.
[4] LEE H, KIM K B, CHOI J W. Transparent SiN_x thin-film anode for thin-film batteries by reactive sputtering at room temperature[J]. Chemical Engineering Journal, 2020, 401: 126086.
[5] 李婷婷,周炳卿,闫泽飞.射频功率和沉积压强对富硅-SiN_x薄膜微结构的影响[J].内蒙古科技大学学报,2019,38(1):1-4+28.
LI T T, ZHOU B Q, YAN Z F. Effect of radio-frequency power and deposition pressure on the microstructure of Si-rich SiN_x films[J]. Journal of Inner Mongolia University of Science and Technology, 2019, 38(1): 1-4+28 (in Chinese).
[6] 谷鑫,周炳卿,翁秀章,等.氨气流量对富硅SiN_x薄膜结构及其光学特性的影响[J].人工晶体学报,2017,46(12):2369-2373.
GU X, ZHOU B Q, WENG X Z, et al. Effect of NH₃ flow rate on the structures and optical properties of silicon rich SiN_x thin films[J]. Journal of Synthetic Crystals, 2017, 46(12): 2369-2373 (in Chinese).
[7] 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].硅酸盐通报,2014,33(4):757-763.
ZHANG L L, ZHOU B Q, ZHANG L R, et al. Study on technological conditions and properties of Si-rich silicon nitride thin films prepared with PECVD[J]. Bulletin of the Chinese Ceramic Society, 2014, 33(4): 757-763 (in Chinese).
[8] YANG J, DE GUZMAN R C, SALLEY S O, et al. Plasma enhanced chemical vapor deposition silicon nitride for a high-performance lithium ion battery anode[J]. Journal of Power Sources, 2014, 269: 520-525.
[9] KIM S Y, KIM D S, AHN B T, et al. Electrical and optical properties of vacuum-evaporated CdS films[J]. Journal of Materials Science: Materials in Electronics, 1993, 4(2): 178-182.
[10] SUZUKI N, CERVERA R B, OHNISHI T, et al. Silicon nitride thin film electrode for lithium-ion batteries[J]. Journal of Power Sources, 2013, 231: 186-189.
[11] 陈沛丞.PECVD氮化硅薄膜性能研究及热学测试结构设计[D].成都:电子科技大学,2016.
CHEN P C. Performance analysis and design of the thermal properties testing structure of PECVD silicon nitride film[D]. Chengdu: University of Electronic Science and Technology of China, 2016 (in Chinese).
[12] 汪建强.PECVD-SiN_x钝化减反射特性研究[D].上海:上海交通大学,2008.
WANG J Q. The passivation & antireflection property investigation of PECVD-SiN_x[D]. Shanghai: Shanghai Jiaotong University, 2008 (in Chinese).
[13] ULVESTAD A, ANDERSEN H F, JENSEN I J T, et al. Substoichiometric silicon nitride-an anode material for Li-ion batteries promising high stability and high capacity[J]. Scientific Reports, 2018, 8: 8634.
[14] 邬洋,衣立新,王申伟,等.磁控溅射法沉积SiN_x非晶薄膜的生长机制及结构分析[J].光谱学与光谱分析,2009,29(5):1260-1263.
WU Y, YI L X, WANG S W, et al. Deposition and structures analysis of amorphous SiN_x films prepared by magnetron sputtering[J]. Spectroscopy and Spectral Analysis, 2009, 29(5): 1260-1263 (in Chinese).
[15] XIONG W J, JIANG H J, LI T T, et al. SiN_x films and membranes for photonic and MEMS applications[J]. Journal of Materials Science: Materials in Electronics, 2020, 31(1): 90-97.
[16] KESSELS W M M, VAN ASSCHE F J H, VAN DEN OEVER P J, et al. The growth kinetics of silicon nitride deposited from the SiH₄-N₂ reactant mixture in a remote plasma[J]. Journal of Non-Crystalline Solids, 2004, 338/339/340: 37-41.
[17] MÄCKEL H, LÜDEMANN R. Detailed study of the composition of hydrogenated SiN_x layers for high-quality silicon surface passivation[J]. Journal of Applied Physics, 2002, 92(5): 2602-2609.