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研究论文

低电压电沉积类金刚石碳膜的研究

  • 王历 ,
  • 吴敏娴 ,
  • 李珺 ,
  • 陈艳丽 ,
  • 王文昌 ,
  • 陈智栋
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  • 常州大学石油化工学院,江苏 常州 213164
*Tel: (86)15961236202, E-mail: minxian.wu@cczu.edu.cn;
Tel: (86-519) 86330239, E-mail: zdchen@cczu.edu.cn

收稿日期: 2021-10-21

  修回日期: 2021-11-30

  网络出版日期: 2021-12-18

基金资助

国家自然基金项目(51874050);常州市科技项目(CJ20210139);常州市科技项目(CZ20200038)

Study on Low Voltage Electrodeposition of Diamond-like Carbon Film

  • Li Wang ,
  • Min-Xian Wu ,
  • Jun Li ,
  • Yan-Li Chen ,
  • Wen-Chang Wang ,
  • Zhi-Dong Chen
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  • School of petrochemical engineering, Changzhou University, Changzhou 213164, Jiangsu, China

Received date: 2021-10-21

  Revised date: 2021-11-30

  Online published: 2021-12-18

摘要

采用电化学沉积法,在较低电压下(4.0 ~ 8.0 V)以甲酸作为主要碳源,甲酸钠作为辅助碳源,二甲基亚砜与去离子水作为溶剂,在不锈钢表面制备了类金刚石碳薄膜,研究了沉积电压对碳膜形貌和成分的影响。电化学沉积含氢类金刚石碳薄膜致密、均匀, 膜的电导率与沉积电压呈负相关关系,电导率介于金属与半导体之间。拉曼光谱在1332 cm-1处出现金刚石的特征峰,sp3碳成分随沉积电压的增加而增加。傅里叶红外变换光谱显示沉积的类金刚石碳膜为含氢碳膜。X射线 光电子能谱分析显示这些薄膜中存在sp2和sp3键碳原子。

本文引用格式

王历 , 吴敏娴 , 李珺 , 陈艳丽 , 王文昌 , 陈智栋 . 低电压电沉积类金刚石碳膜的研究[J]. 电化学, 2022 , 28(6) : 2104441 . DOI: 10.13208/j.electrochem.210444

Abstract

Diamond-like carbon (DLC) films are receiving a lot of attention from the scientific community, thanks to the promise of DLC films for applications in microelectronics and optoelectronics. Usually, electrodeposition is the preferred common technique because of low cost, large deposition area and simplicity of the setup. However, when carbon films are electrodeposited on a stainless steel, high cell voltages (≥1000 V) are required owing to the low electric conductivity of the organic solvents. This work has developed a new electrolyte system that could achieve carbon deposition on a stainless steel under a low applied cell voltage. The DLC films were electrodeposited from 230 g·L-1 formic acid and 17 g·L-1 sodium formate in 1:1 (v/v) water-dimethyl sulfoxide mixture with the applied voltages ranged from 4.0 V to 8.0 V on the stainless steel substrate. The effects of the applied voltage on film morphology have been investigated. Dimethyl sulfoxide (DMSO) can broaden the electrochemical window of the solvents, inhibit hydrogen evolution and improve current efficiency. Nevertheless, the current efficiency was still low. X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), Raman spectroscopy, Fourier transform infrared (FTIR) spectroscopy, probe surface profiler, and four-point probe resistivity tester were employed to analyze the structure, morphology, surface chemical composition, film thickness, and electric conductivity of the DLC films. It was found that the dense and uniform hydrogenated DLC films were successfully prepared on the stainless steel substrate. The film thickness was sensitive to the cell voltage and decreased with the increase in cell voltage. The Raman spectra of these films indicated the three broad peaks. Presences of D and G peaks near 1330 cm-1 and 1570 cm-1, respectively, revealed that the as-deposited films were typical DLC films. The average grain size and sp3 carbon content of the film increased with the increase in deposition voltages. The FTIR results showed that the peaks observed at 2850 cm-1, 2920 cm-1 and 2960 cm-1 were related to the C-H symmetric and asymmetric stretching of CH2 and CH3 groups. Because of deionized water added in the solution, the infrared spectroscopic measurements supported that the DLC films were hydrogenated carbon films. The XPS results demonstrated that the two peaks for C1s at 284.5 eV and 285.2 eV with the comparatively lower intensity corresponded to C=C and C-C, respectively. The third peak at 288.5 eV may be associated with ester or carboxyl groups. The electric conductivity of the DLC film decreased with the increase in deposition voltage, falling between those of metal and semiconductor.

参考文献

[1] Robertson J R. Diamond-like amorphous carbon[J]. Mater. Sci. Eng. R-Rep., 2002, 37(4-6): 129-281.
[2] Novikov N V, Gontar A G, Khandozhko S I, Kutsay A M, Tkach V N, Gorokhov V Y, Belitsky G M, Vasin A V. Protective diamond-like coatings for optical materials and electronic devices[J]. Diam. Relat. Mater., 2000, 9(3-6): 792-795.
[3] Grill A. From tribological coatings to low-k dielectrics for ULSI interconnects[J]. Thin Solid Films, 2001, 398: 527-532.
[4] Li J J, Gu C Z, Peng H Y, Wu H H, Zheng W T, Jin Z S. Field emission properties of diamond-like carbon films annealed at different temperatures[C]// The 5th International Vacuum Electron Sources Conference Proceedings (IEEE Cat. No.04EX839), Netherlands, Elsevier, 2005: 253-255.
[5] Li R S(李瑞山), Feng Y C(冯有才), Wang X(王璇), Zhang P Z(张培增), Xie E Q(谢二庆), Yang H(杨华). The simultaneous deposition and growth mechanism of diamond-like carbon films on both surfaces of stainless steel substrate by electrodeposition[J]. Int. Mater. Rev.(材料导报), 2016, 30(2): 56-60.
[6] Namba Y. Attempt to grow diamond phase carbon films from an organic solution[J]. J. Vac. Sci. Technol. A-Vac. Surf. Films, 1992, 10(5): 3368-3370.
[7] Jiang H Q, Huang L N, Wang S J, Zhang Z J, Xu T, Liu W M. Synthesis of DLC films by electrolysis of dimethyl sulfoxide[J]. Electrochem. Solid State Lett., 2004, 7(11): D19-D21.
[8] Gupta S, Roy R K, Deb B, Kundu S, Pal A K. Low voltage electrodeposition of diamond-like carbon films[J]. Mater. Lett., 2003, 57(22-23) :3479-3485.
[9] Gupta S, Chowdhury M P, Pal A K. Synthesis of DLC films by electrodeposition technique using formic acid as electrolyte[J]. Diam. Relat. Mat., 2004, 13(9): 1680-1689.
[10] Zhang Q, Wang, Y R, Wang W C, Mitsuzak N, Chen Z D. Low voltage and ambient temperature electrodeposition of uniform carbon films[J]. Electrochem. Commun., 2016, 63: 22-25.
[11] Wu M X(吴敏娴), Tang R J(汤荣军), Xia H(夏寒), Wang W C(王文昌), Chen Z D(陈智栋). Low voltage electrodeposition of carbon films from aqueous solutions[J]. J. Changzhou Univ. -Nat. Sci. Ed.(常州大学学报:自然科学版), 2019, 31(5): 31-35.
[12] Xia H(夏寒), Wang S Y(王世颖), Guang Q S L(光崎尚利), Chen Z D(陈智栋) Study on electrodeposition of carbon films on 304 stainless steel in aqueous solutions[J]. Plat. Finish.(电镀与精饰), 2018, 40(7): 5-9.
[13] Pourbaix M. Atlas of electrochemical equilibria in aqueous solutions[M]. Houston: NACE International, 1974.
[14] Dresselhaus M S, Dresselhaus G, Saito R, Jorio A. Raman spectroscopy of carbon nanotubes[J]. Phys. Rep., 2005, 409(2): 47-99.
[15] Zhang Y G, Sun W C, Dong Y R, Ma M, Liu Y W, Tian S S, Xiao Y, Jia Y P. Electrodeposition and microstructure of Ni and B co-doped diamond-like carbon (Ni/B-DLC) films[J]. Surf. Coat. Technol., 2021, 405: 126713.
[16] Varga M, Izak T, Vretenar V, Kozak H, Holovsky J, Artemenko A, Hulman M, Skakalova V, Lee D S, Kromka A. Diamond/carbon nanotube composites: Raman, FTIR and XPS spectroscopic studies[J]. Carbon, 2017, 111: 54-61.
[17] Lin-Vien D. The handbook of infrared and Raman characteristic frequencies of organic molecules[M]. New York: Academic Press, 1991. 117-154.
[18] Ferrari A C, Robertson J. Raman spectroscopy in carbons: from nanotubes to diamond-Preface[J]. Philos. Trans. R. Soc. Lond. Ser. A-Math. Phys. Eng. Sci., 2004, 362(1824): 2269-2270.
[19] Tucureanu V, Matei A, Avram A M. FTIR spectroscopy for carbon family study[J]. Crit. Rev. Anal. Chem., 2016, 46(6): 502-520.
[20] Lascovich J C, Giorgi R, Scaglione S. Evaluation of the sp2/sp3 ratio in amorphous carbon structure by XPS and XAES[J]. Appl. Surf. Sci., 1991, 47(1): 17-21.
[21] Kulak A I, Kokorin A I, Meissner D, Ralchenko V G, Vlasov I I, Kondratyuk A V, Kulak T I. Electrodeposition of nanostructured diamond-like films by oxidation of lithium acetylide[J]. Electrochem. Commun., 2003, 5(4): 301-305.
[22] Ismail R A, Mousa A M, Hassan M A. Synthesis and characterization of diamond-like carbon film on silicon by electrodeposition from solution of ethanol and methanol[J]. Mater. Sci. Semicond. Process, 2014, 27: 461-467.
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