石墨烯/纳米减反结构复合透明导电薄膜的研究

doi:10.15541/jim20160310

摘要/Abstract

摘要：

石墨烯具有较高的透过率及良好的电导率, 作为透明导电薄膜具有潜在的应用价值。首先在石英基底上引入SiO₂纳米球阵列结构作为光学减反射层, 使石英基底可见光区光学透过率从93.2%增加到99.0%。然后利用常压化学气相沉积方法, 通过基底表面铜颗粒远程催化碳源, 直接在减反层上可控制备具有石墨烯/纳米减反结构的新型复合透明导电薄膜。通过去除SiO₂纳米球阵列结构形成反相复制的石墨烯空心球阵列结构, 且生长时间10 min时, 对应半高宽约40 cm^-1, I_2D/I_G= 2.31, I_D/I_G= 0.77, 证明在SiO₂纳米球阵列减反结构上制备了低缺陷且连续的全包覆少层石墨烯薄膜。引入SiO₂纳米球阵列减反结构后, 其在可见光区光学550 nm波长处的透过率平均提高了5.5%, 方块电阻相对无减反射层基底平均降低了20.09%。本研究方法避免了复杂的转移工序, 减少了对石墨烯的损失与破坏, 同时实现了高透光性及高导电性的功能协同, 在光伏器件、平板显示等领域展示出更大的应用前景。

关键词: 透明导电薄膜, 石墨烯, 化学气相沉积, 铜颗粒辅助远程催化, 纳米减反结构

Abstract:

The graphene film was directly deposited on SiO₂ antireflection(AR) structure by remote catalyzation of Cu nanoparticles using chemical vapor deposition method to fabricate the transparent conducting films with graphene/AR composite structure. Continuous graphene hollow sphere array was obtained after removing SiO₂ AR structure, and the peak intensity ratios of I_2D/I_G and I_D/I_G and the full-width at half-height maximum (FWHM) of the 2D peak in the Raman spectrum of the graphene grew in 10 min were 2.31, 0.77 and about 40 cm^-1, respectively, which demonstrated that the continuous and low-defect few layer graphene was grown on the surface of SiO₂ AR structure. By introducing the SiO₂ AR structure, transmittance of the film increases by 5.5% at 550 nm and the sheet resistance decreases by 20.09% on the average. Data from this study suggest that this film can avoid complex transfer process, decrease damage, and on the meantime realize high transparency and high conductivity performance , showing obvious applicable prospects in the field of photovoltaic devices, flat panel display and so on.

Key words: transparent conducting films, graphene, CVD, remote catalyzation of Cu nanoparticles, SiO2 antireflection nanostructure

中图分类号:

TQ174

韩霜霜, 刘莉月, 单永奎, 杨帆, 李德增. 石墨烯/纳米减反结构复合透明导电薄膜的研究[J]. 无机材料学报, 2017, 32(2): 197-202.

HAN Shuang-Shuang, LIU Li-Yue, SHAN Yong-Kui, YANG Fan, LI De-Zeng. Research of Graphene/Antireflection Nanostructure Composite Transparent Conducting Films[J]. Journal of Inorganic Materials, 2017, 32(2): 197-202.

图/表 10

图1 未生长石墨烯的SiO2 NSs AR /quartz的SEM照片(a), 生长石墨烯的GE/SiO2 NSs AR film/quartz的SEM照片及其高倍放大照片(b), 残留在基底上的铜纳米粒子的EDS表征(c)

Fig. 1 SEM images of monodisperse SiO2 NSs structure before (a) and after (b) growth of graphene and the magnification image of GE/SiO2 NSs (c) with EDS characterization of the Cu NPs left on the substrate in (c)

图2 (a)GE/SiO2 NSs和(b)去除SiO2 NSs后的石墨烯空心球结构的TEM照片, (c)石墨烯空心球结构的高倍TEM照片

Fig. 2 TEM images of GE/SiO2 NSs /quartz (a) and hollow graphene NSs (b) by removing SiO2 NSs, high magnification TEM image of hollow graphene NSs (c)

表1 不同生长时间下生长的石墨烯的拉曼光谱数据分析

Table 1 Raman spectra analysis of graphene grown for different time

Growth time	2D band		I_D/I_G	I_2D/I_G	L_a/nm
	Position	FWHM
	cm^-1	cm^-1
10 min	2697.60	40	0.77	2.31	24.9
15 min	2691.69	45	0.76	0.95	25.3
20 min	2695.55	56	0.64	0.84	30.0
25 min	2690.72	55	0.60	0.49	32.0

图3 1000℃生长不同时间得到的GE/SiO2 NSs /quartz样品的拉曼光谱图

Fig. 3 Raman spectra of GE/SiO2 NSs /quartz grown at 1000℃ for different time

图4 有无SiO2纳米球阵列减反结构的透光度对比图

Fig. 4 Transmission spectra of the substrate coated with and without SiO2 NSs AR nanostructure

图5 (a)不同生长时间制备的GE/ quartz的光学透过率谱图, (b)GE/SiO2 NSs AR /quartz的光学透过率谱图, (c)550 nm处透过率和方块电阻对生长时间的折线图

Fig. 5 Optical transmittance spectra of the GE/SiO2 NSs AR /quartz (a), transmittance (at 550 nm) (b) and sheet resistance as a function of growth time(c)

表2 样品的透过率和方块电阻的数据

Table 2 Transmittance and sheet resistance of samples

Growth time		10 min	15 min	20 min	25 min
Transmittance/%	GE/quartz	90.30	88.90	86.40	78.60
	GE/SiO₂ NS AR film/quartz	96.30	95.00	91.80	83.00
	Increment/%	6.640	6.86	6.25	5.60
Sheet resistance/(kΩ·□^-1)	GE/quartz	--	16.30	6.07	1.25
	GE/SiO₂ NS AR film/quartz	20.50	12.30	5.60	0.90
	Decrease/%		24.54	7.74	28.00

图S1 不同水硅比(n(H2O) : n(TEOS) )制备的SiO2纳米球阵列减反结构的透光度图谱(a), 不同水硅比制备的减反结构的SEM照片(b~d) Fig. S1 (a) Transmission spectra of the SiO2 NSs AR/quartz with different mole ratios (n(H2O) : n(TEOS)), SEM images of the SiO2 NSs AR/quartz prepared from different mole ratios( n(H2O) : n(TEOS)) (b-d)

图S2 不同浸渍时间对SiO2纳米球阵列减反结构透光度的影响 Fig. S2 Influences on SiO2 NSs AR nanostructure reflection from dipping time

图S3 镀膜提拉速度对SiO2纳米球阵列减反结构减反性能的影响表征 Fig. S3 Relationship between on SiO2 NSs AR nanostructure reflection from the withdrawal rate(a) Transmission spectra of the SiO2 NSs AR /quartz with different withdrawal rate, (b) Transmittance of SiO2 NSs AR /quartz as a function of withdrawal rate, and (c-e) SEM images of the SiO2 NSs AR /quartz prepared with different withdrawal rates

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