Ag掺杂非晶碳膜结构、力学与电学行为研究

doi:10.15541/jim20180263

无机材料学报 ›› 2019, Vol. 34 ›› Issue (4): 387-393.DOI: 10.15541/jim20180263

Ag掺杂非晶碳膜结构、力学与电学行为研究

陈仁德¹,郭鹏¹,左潇¹,许世鹏²,柯培玲^1,³,汪爱英^1,³()

^1. 中国科学院宁波材料技术与工程研究所中国科学院海洋新材料与应用技术重点实验室浙江省海洋材料与防护技术重点实验室, 宁波 315201
^2. 酒泉职业技术学院甘肃省太阳能发电系统工程重点实验室, 酒泉 735000
^3. 中国科学院大学材料与光电研究中心, 北京 100049

收稿日期:2018-06-19 修回日期:2018-09-25 出版日期:2019-04-20 网络出版日期:2019-04-15
作者简介:陈仁德(1988-), 男, 硕士, 工程师. E-mail:chenrd@nimte.ac.cn
基金资助:
国家自然科学基金项目(51602319);宁波市自然科学基金(2018A610080);甘肃省高等学校科研项目(2017A-273);兰州理工大学新能源学院重点科研项目(LUT-XNY-2017009)

Ag Doped Amorphous Carbon Films: Structure, Mechanical and Electrical Behaviors

Ren-De CHEN¹,Peng GUO¹,Xiao ZUO¹,Shi-Peng XU²,Pei-Ling KE^1,³,Ai-Ying WANG^1,³()

^1. Zhejiang Key Laboratory of Marine Materials of Protective Technologies, Key Laboratory of Marine Materials and Related Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
^2. Gansu Key Laboratory of Solar Power Generation System Project, Jiuquan Vocational and Technical College, Jiuquan 735000, China
^3. Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2018-06-19 Revised:2018-09-25 Published:2019-04-20 Online:2019-04-15
Supported by:
National Natural Science Foundation of China(51602319);Ningbo Municipal Natural Science Foundation(2018A610080);Research Projects of Gansu Province(2017A-273);Key Research Projects of the New Energy Institute, Lanzhou University of Technology(LUT-XNY-2017009)

摘要/Abstract

摘要：

采用反应磁控溅射技术, 通过改变溅射靶电流实现了不同Ag掺杂含量0.7at%~41.4at%非晶碳膜(a-C:Ag)的可控制备, 并系统研究了Ag含量对薄膜组分、结构、机械特性的影响规律, 以及薄膜的电学特性。结果表明: 当Ag含量在0.7at%~1.2at%时, Ag原子固溶于非晶碳基质; 当Ag含量在13.0at%~41.4at%范围, 薄膜中出现尺寸约为6 nm的Ag纳米晶。随着Ag含量增加, 碳网络结构的sp ²团簇尺寸增大, 结构无序度降低。应力测试表明, 在低Ag含量范围, Ag原子固溶于碳膜网络结构中, 起到枢纽作用, 促进碳网络结构键长、键角畸变弛豫, 从而降低薄膜应力。随着Ag含量增加, 部分Ag原子将形成Ag纳米晶粒, 薄膜通过Ag纳米晶与非晶碳界面处的滑移以及扩散作用释放过高的畸变能降低应力。Ag含量为37.8at%时, 在11.6 K附近, 薄膜出现金属-半导体特性转变。而Ag含量为41.4at%的薄膜, 在2~400 K测试温度范围内, 均表现为半导体特性, 其中在164~400 K范围内, 薄膜表现出典型的热激活导电机制。

关键词: 非晶碳, 银掺杂, 结构表征, 机械特性, 电学特性

Abstract:

By adjusting sputter current from 1.3 A to 2.0 A in reactive magnetron sputtering deposition processes, Ag doped amorphous carbon films (a-C:Ag) with doping content from 0.7at% to 41.4at% were prepared. The influence of Ag content on structure, component, mechanical and electrical properties of a-C:Ag films were systematically studied. The results showed that Ag atoms were dissolved in amorphous carbon matrix at low Ag content (0.7at% to 1.2at%) conditions. However, Ag nanocrystal with a size around 6 nm formed when Ag content increased to 13.0at%. With the increase of Ag content, the size of sp ² clusters in the amorphous carbon matrix increased while the structural disorder degree decreased. Stress test indicated that in the low Ag content range, Ag atoms were dissolved in carbon matrix which played a pivotal role in promoting relaxation of bond length and angle distortion, thereby the film stress was reduced. Ag atoms started to form Ag nanocrystals as the Ag content increased. As a result, film stress would be reduced due to release of excessive distortion by sliding and diffusion at the grain boundaries. When Ag content reached 37.8at%, a-C:Ag exhibited transition from metal to semiconductor characteristic near 11.6 K. However, as the Ag content increased to 41.4at%, the films displayed semiconducting characteristics in the whole test temperature range (2-400 K) and exhibited typical thermal activation mechanism within temperature range of 164-400 K.

Key words: amorphous carbon, Ag doping, structure characterization, mechanical property, electrical behavior

中图分类号:

TQ127

陈仁德, 郭鹏, 左潇, 许世鹏, 柯培玲, 汪爱英. Ag掺杂非晶碳膜结构、力学与电学行为研究[J]. 无机材料学报, 2019, 34(4): 387-393.

Ren-De CHEN, Peng GUO, Xiao ZUO, Shi-Peng XU, Pei-Ling KE, Ai-Ying WANG. Ag Doped Amorphous Carbon Films: Structure, Mechanical and Electrical Behaviors[J]. Journal of Inorganic Materials, 2019, 34(4): 387-393.

图/表 11

表1 Ag掺杂含量、O含量、薄膜厚度和沉积速率随溅射电流和功率的变化关系

Table 1 Ag concentration, O concentration, film thickness and average deposition rate varied with sputtering current and power

Sputtering current /A	Sputtering power /W	Ag concentration /at%	O concentration /at%	Thickness /nm	Deposition rate /(nm?min^-1)
1.3	582	0.7	30.2	364.5	18.2
1.4	602	0.8	26.5	358.3	17.9
1.5	647	1.2	27.2	508.5	25.4
1.6	859	13.0	45.2	725.4	36.3
1.8	788	37.8	32.9	1409.1	70.5
2.0	856	41.4	32.2	1720.4	86.0

图1 不同Ag掺杂含量a-C:Ag薄膜的C1s精细XPS图谱(a)和Ag含量为41.4at%薄膜的Ag3d精细XPS图谱(b)

Fig. 1 Typical XPS spectra for the a-C:Ag films (a), and representative Ag 3d spectra of the films with 41.4at% Ag (b)

图2 不同Ag掺杂量的a-C:Ag薄膜的XRD图谱

Fig. 2 XRD patterns of a-C:Ag films with various Ag concentrations

图3 掺杂含量1.2at%的a-C:Ag薄膜FIB样品形貌(a), 界面处的透射电子显微高分辨照片以及a-C:Ag薄膜选区电子衍射花样(b)

Fig. 3 (a) Sample for TEM prepared by FIB, (b) HRTEM and SAED of sample with 1.2at% a-C:Ag

图4 不同Ag掺杂含量a-C:Ag的Raman光谱图(a), 掺杂含量0.7at%的a-C:Ag的Raman拟合结果(b)

Fig. 4 Typical Raman spectra a-C:Ag films with different Ag concentrations (a) and the fitting result of a-C:Ag film with 0.7at% Ag atoms (b)

表2 不同Ag掺杂含量a-C:Ag的Raman拟合结果

Table 2 The fitted G-peak position, ID/IG and FWHM of G-peak varied with different Ag concentrations

Ag concentration /at%	G-peak position/cm^-1	I_D/I_G	FWHM of G-peak/cm^-1
0.7	1533.0	0.75	159.4
0.8	1535.9	0.79	151.6
1.2	1539.8	0.85	151.4
13.0	1582.5	1.94	122.5
37.8	1566.4	2.15	123.6
41.4	1580.7	2.68	110.0

图5 不同Ag含量a-C:Ag表面SEM形貌

Fig. 5 Surface topographies of a-C:Ag films with different Ag concentrations (a) 0.7at%; (b) 0.8at%; (c) 1.2at%; (d) 13.0at%; (e) 37.8at%; (f) 41.4at%

图6 不同Ag掺杂含量a-C:Ag的硬度(a)与模量(b)

Fig. 6 Hardness (a) and elastic modulus (b) as a function of Ag concentration

图7 不同Ag掺杂含量a-C:Ag的残余应力

Fig.7 Residual compressive stress of a-C:Ag films as a function of Ag concentration

图8 (a)在8~400 K测试温度范围内, 掺杂含量为37.8at%的a-C:Ag电阻率随温度的变化曲线, 插图是2~24 K区域的放大图;(b)在2~400 K测试温度范围内, 金属含量为41.4at%的a-C:Ag电阻率随温度的变化曲线

Fig. 8 Temperature dependence of resistivity in a-C:Ag film with 37.8at% Ag in the range of 8~400 K (a) and the a-C:Ag with 41.4at% Ag in the range of 2~400 K (b)

图9 Ag含量为41.4at%的a-C:Ag的lnρ 随1000/T变化关系曲线, 温度区间164~400 K

Fig. 9 Plot of lnρ vs reciprocal temperature in the range of 164-400 K for a-C:Ag film with 41.4at% Ag

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Ag掺杂非晶碳膜结构、力学与电学行为研究

Ag Doped Amorphous Carbon Films: Structure, Mechanical and Electrical Behaviors

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