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, CH4 and 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.
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.
[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.