高温氧化协同原位掺硼提升金刚石薄膜的亲水性

摘要
图/表
参考文献
相关文章 (7)

全文: PDF (544 KB) HTML (1 KB)
输出: BibTeX | EndNote (RIS)

摘要用H₂、CH₄和B₂H₆气体作为气源,采用热丝化学气相沉积技术在单晶硅衬底上分别制备纯金刚石膜和含硼金刚石薄膜,然后在600~800 ℃高温氧化。通过扫描电镜、拉曼光谱及X射线衍射仪对金刚石膜层的形貌和成分进行表征,用常温接触角测试仪对其亲水性进行表征,研究高温氧化协同原位掺硼对金刚石薄膜亲水性的影响。结果表明,随高温氧化温度升高,膜层逐渐被刻蚀至出现微孔形貌,其中纯金刚石膜层在700 ℃下氧化后,接触角从68.1°降低至21.5°,膜层亲水性提高。随掺硼浓度提高,微孔逐渐消失,在V(H₂):V(CH₄):V(B₂H₆)=97:3:0.4条件下制备的掺硼金刚石膜,并在800 ℃氧化处理后,具有最小接触角14.1°。在原位掺硼和高温氧化的协同作用下,膜层成分发生改变,同时金刚石完美构型出现缺陷,微孔形貌使金刚石膜层的表面能增大,从而有效提高金刚石薄膜的亲水性。

	服务

	把本文推荐给朋友
	加入我的书架
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	于杨磊
	李崧博
	安俊杰
	包胜友
	康惠元
	康翱龙
	魏秋平

关键词 ：金刚石, 热丝化学气相沉积, 高温氧化, 原位掺硼, 亲水性

Abstract：Hot filament chemical vapor deposition (HFCVD) was used to prepare high-quality diamond films and boron doped diamond films on single-crystal silicon substrates by using H₂, CH₄and B₂H₆ as gas source. After 600-800 ℃ high temperature oxidation treatment, the morphology, composition and hydrophilic of the diamond film were characterized by scanning electron microscope, Raman spectroscopy, X-ray diffraction and normal temperature contact angle instrument. The effects of high temperature oxidation and in-situ boron doping on the hydrophilic of diamond films were also studied. The results show that with the increase of high temperature oxidation temperature, the film was gradually etched to micropore morphology. The contact angle of pure diamond film decreases from 68.1° to 21.5° after oxidation at 700 ℃, and the hydrophilicity of the film is improved. With the increase of boron concentration, the micropores gradually disappear. The minimum contact angle is 14.1° when the boron-doped diamond film was prepared under the conditions of V(H₂):V(CH₄):V(B₂H₆)=97.0:3.0:0.4, and after oxidation at 800 ℃. Under the synergistic effect of in-situ boron doping and high-temperature oxidation, the composition of the film changes, and the perfect diamond configuration defects appear, as well as the surface energy of diamond film increases due to micropores. This method can effectively improve the hydrophilic of diamond film.

Key words： diamond hot filament chemical vapor deposition high temperature oxidation in-situ boron doping hydrophilic

收稿日期: 2021-01-07 出版日期: 2021-05-07

ZTFLH:

TB43

基金资助:国家重点研发计划资助项目(2016YFB0301402); 国家自然科学基金资助项目(52071345,51874370,51601226); 广东省重点研发计划资助项目(2020B010185001); 湖南省自然科学基金资助项目(2019JJ40375,2019JJ50793)

引用本文:

于杨磊, 李崧博, 安俊杰, 包胜友, 康惠元, 康翱龙, 魏秋平. 高温氧化协同原位掺硼提升金刚石薄膜的亲水性[J]. 粉末冶金材料科学与工程, 2021, 26(2): 174-181.
YU Yanglei, LI Songbo, AN Junjie, BAO Shengyou, KANG Huiyuan, KANG Aolong, WEI Qiuping. Improving the hydrophilia of diamond film by high temperature oxidation and in situ boron doping. Materials Science and Engineering of Powder Metallurgy, 2021, 26(2): 174-181.

链接本文:

http://pmbjb.csu.edu.cn/CN/ 或 http://pmbjb.csu.edu.cn/CN/Y2021/V26/I2/174

[1] 戴书刚, 李金旺, 董传俊. 金刚石/铜高导热复合材料制备工艺的研究进展[J]. 精细化工, 2019, 36(10): 1995-2008.
DAI Shugang, LI Jinwang, DONG Chuanjun.Research progress on preparation methods of high thermal conductivity diamond/copper composites[J]. Fine Chemicals, 2019, 36(10): 1995-2008.
[2] 王西涛, 张洋, 车子璠, 等. 金刚石颗粒增强金属基高导热复合材料的研究进展[J]. 功能材料, 2014, 45(7): 7001-7015.
WANG Xitao, ZHANG Yang, CHE Zifan, et al.Review on the progress of diamond particles dispersed metal matrix composites with superior high thermal conductivity[J]. Journal of Functional Materials, 2014, 45(7): 7001-7015.
[3] ZHANG L, ZHOU K C, WEI Q P, et al. Thermal conductivity enhancement of phase change materials with 3D porous diamond foam for thermal energy storage[J]. Applied Energy, 2019, 233- 234: 208-219.
[4] YE W T, WEI Q P, ZHANG L, et al.Macroporous diamond foam: A novel design of 3D interconnected heat conduction network for thermal management[J]. Materials & Design, 2018, 156: 32-41.
[5] ZHANG L, WEI Q P, AN J J, et al.Construction of 3D interconnected diamond networks in Al-matrix composite for high-efficiency thermal management[J]. Chemical Engineering Journal, 2019, 380: 122551.
[6] ZHU W, HU N X, WEI Q P, et al.Carbon nanotube-Cu foam hybrid reinforcements in composite phase change materials with enhanced thermal conductivity[J]. Materials & Design, 2019, 172: 107709.
[7] OSTROVSKAYA L Y.Studies of diamond and diamond-like film surfaces using XAES, AFM and wetting[J]. Vacuum. 2002, 68(3): 219-238.
[8] OSTROVSKAYA L, PEREVERTAILO V, RALCHENKO V, et al.Wettability and surface energy of oxidized and hydrogen plasma-treated diamond films[J]. Diamond and Related Materials, 2002, 11(3): 845-850.
[9] PINZARI F, ASCARELLI P, CAPPELLI E, et al.Wettability of HF-CVD diamond films[J]. Diamond and Related Materials, 2001, 10(3): 781-785.
[10] BIGELOW L K, D’EVELYN M P. Role of surface and interface science in chemical vapor deposition diamond technology[J]. Surface Science, 2002, 500(1): 986-1004.
[11] ZHANG X F, CUI Y X, LIU X B, et al.Wettability modulation of nano-crystalline diamond films via in-situ CVD process[J]. Surface and Coatings Technology, 2019, 375: 681-687.
[12] ZHANG D W, CUI Y X.Surface chemical modification of CVD diamond films by laser irradiation[J]. International Journal of Refractory Metals and Hard Materials, 2019, 81: 36-41.
[13] MONTANO-FIGUEROA A G, ALCANTAR-PENA J J, TIRADO P, et al. Tailoring of polycrystalline diamond surfaces from hydrophilic to superhydrophobic via synergistic chemical plus micro-structuring processes[J]. Carbon, 2018, 139: 361-368.
[14] PEI X, CHENG S, MA Y, et al.Structure and wettability property of the growth and nucleation surfaces of thermally treated freestanding CVD diamond films[J]. Applied Surface Science, 2015, 346(15): 189-193.
[15] YANG J H C, TEII K. Mechanism of enhanced wettability of nanocrystalline diamond films by plasma treatment[J]. Thin Solid Films, 2012, 520(21): 6566-6570.
[16] MASTUMAE T, KURASHIMA Y, UMEZAWA H, et al.Hydrophilic low-temperature direct bonding of diamond and Si substrates under atmospheric conditions[J]. Scripta Materialia, 2020, 175: 24-28.
[17] NETO M A, PATO G, BUNDALESKI N, et al.Surface modifications on as-grown boron doped CVD diamond films induced by the B₂O₃-ethanol-Ar system[J]. Diamond and Related Materials, 2016, 64: 89-96.
[18] YAGI I, NOTSU H, KONDO T, et al.Electrochemical selectivity for redox systems at oxygen-terminated diamond electrodes[J]. Journal of Electroanalytical Chemistry. 1999, 473(1): 173-178.
[19] 张清福, 芶清泉, 刘履华, 等. 八面体硼皮金刚石的形成与耐热性能的实验研究[J]. 高压物理学报, 1991, 5(4): 291-295.
ZHANG Qingfu, GOU Qingquan, LIU Lühua, et al.The experimental research of heat resistance of octahedral boron- skinned diamond[J]. Chinese Journal of High Pressure Physics, 1991, 5(4): 291-295.
[20] MA Y B, TONG J H, ZHUANG M S, et al.Superhydrophilic surface of oxidized freestanding CVD diamond films: Preparation and application to test solution conductivity[J]. Results in Physics, 2019, 15: 102628
[21] FENG S L, LIN X, HE P P, et al.Porous structure diamond films with super-hydrophilic performance[J]. Diamond and Related Materials, 2015, 56: 36-41.
[22] SAILS S R, GARDINER D J, BOWDEN M, et al.Monitoring the quality of diamond films using Raman spectra excited at 514.5 nm and 633 nm[J]. Diamond & Related Materials, 1996, 5(6/8): 589-591.
[23] 魏秋平, 余志明, 马莉, 等. YG6硼化综合处理后基体温度对金刚石薄膜的影响[J]. 中国表面工程, 2006, 19(6): 29-34.
WEI Qiuping, YU Zhiming, MA Li, et al.Effect of substrate temperature on diamond film on boronized WC-6%Co substrate[J]. China Surface Engineering, 2006, 19(6): 29-34.
[24] TIAN S, SUN W, HU Z, et al.Morphology modulating the wettability of a diamond film[J]. Langmuir, 2014, 30(42): 12647-12653.
[25] YOUNG T. An essay on the cohesion of fluids[J]. Philosophical Transactions of the Royal Society of London, 1805, 95: 65-87.
[26] CHOI S K, JUNG D Y, CHOI H M.Intrinsic stress and its relaxation in diamond film deposited by hot filament chemical vapor deposition[J]. Journal of Vacuum Science & Technology A, 1996, 14(1): 165-169.
[27] LEVY-CLEMENT C, NDAO N A, KATTY A, et al.Boron doped diamond electrodes for nitrate elimination in concentrated wastewater[J]. Diamond and Related Materials, 2003, 12(3): 606-612.
[28] 周春. CVD金刚石涂层电极气体法掺硼工艺研究[D]. 南京: 南京航空航天大学, 2013.
ZHOU Chun.Study on boron doping process with gas for CVD diamond coated electrode[D]. Nanjing: Nanjing University of Aeronautics and Astronautics, 2013.
[29] BREUER S J, BRIDDON P R.Ab initio study of substitutional boron and the boron-hydrogen complex in diamond[J]. Physical Review B, 1994, 49(15): 10332-10336.
[30] BARNARDa A S, STERNBERG M.Substitutional boron in nanodiamond, bucky-diamond, and nanocrystalline diamond grain boundaries[J]. The Journal of Physical Chemistry B, 2006, 110(39): 19307-19314.
[31] WENZEL, ROBERT N.Resistance of solid surfaces to wetting by water[J]. Transactions of the Faraday Society, 1936, 28(8): 988-994.
[32] PLESKOV Y V, EVSTEFEEVA Y E, KROTOVA M D, et al.Synthetic semiconductor diamond electrodes: A study of electrochemical behavior of boron-doped single crystals grown at a high temperature and high pressure[J]. Electrochimica Acta, 1999, 44(19): 3361-3366.
[33] WANG M, SIMON N, BOUTTEMY M, et al.Comparison of the chemical composition of boron-doped diamond surfaces upon different oxidation processes[J]. Electrochimica Acta, 2009, 54(24): 5818-5824.