基于石墨烯竖立片层常压相变制备纳米金刚石

朱奕衡; 朱志光; 陈成克; 蒋梅燕; 李晓; 鲁少华; 胡晓君

doi:10.7498/aps.73.20231064

摘要

采用热丝化学气相沉积法制备了含有钽原子的石墨烯竖立片层, 并将其置于含氧环境中进行退火处理, 在常压环境中发生相变得到纳米金刚石, 并研究退火环境中氧含量变化对纳米金刚石形成的影响. 结果表明, 当退火环境气压为10 Pa和50 Pa (对应氧原子百分比为1.96%和2.04%) 时, 退火后样品形貌与结构和未处理的石墨烯片层无异; 样品100 Pa和500 Pa气压下退火后(对应氧原子百分比为2.77%和3.11%), 在其中观察到了尺寸为2—4 nm的纳米金刚石, 这些金刚石晶粒多分布于非晶碳中; 继续升高退火环境气压则发现退火后样品被大面积氧化, 石墨结构遭到严重破坏. 该研究结果为纳米金刚石的制备提供了新方法.

关键词:

Abstract

A basic and important way to prepare diamond is to make graphite experience the phase transformation under the high-pressure high-temperature (HPHT) condition. However, this method needs stringent equipment and high investment cost. Recently, we proposed a method to prepare the diamond by phase transformation of graphite at atmospheric pressure with monodispersed Ta atoms. It is found that a phase transformation happens to H atoms under atmospheric pressure, but the role of O atoms has not been investigated. Here, we use tantalum wires as Ta source and heat the filaments to prepare vertical graphene containing Ta atoms in hot filament chemical vapor deposition (HFCVD) system. And then the vertical graphene layers are annealed in oxygen-containing environment, and nanodiamonds are obtained by phase transformation from the vertical graphene under atmospheric pressure. The results show that the sample morphologies are the same as the untreated vertical graphene’s, when the annealed ambient air pressure is at 10 Pa and 50 Pa with oxygen atom content of 1.96% and 2.04%, respectively; TEM tests reveal TaC and graphite but no diamond in these samples . Nanodiamond grains with the size range of 2–4 nm are observed in the amorphous carbon region of samples annealed at 100 Pa and 500 Pa air pressure with oxygen atom content increasing to 2.77% and 3.11%, respectively, indicating that oxidation facilitates the phase change from Ta-containing vertical graphene to diamond at atmospheric pressure. When the air pressure of the annealing environment rises to 1000 Pa with the oxygen atom content of 3.54%, the sample is extensively oxidized and the graphite structure is severely damaged,which means that a large number of oxygen atoms tend to disrupt the graphite structure rather than promote the phase change into diamond. These results supply a way to prepare nanodiamond and show the effect of O atoms in the graphite phase transition at atmospheric pressure.

Keywords:

graphene /
nanodiamond /
phase transition under ordinary pressure

作者及机构信息

1.
浙江工业大学材料科学与工程学院, 杭州　310014

2.
莫干山金刚石研究中心, 湖州　313200

3.
浙江工业大学-唐合科技金刚石联合研究院, 湖州　313200

通信作者: 胡晓君, huxj@zjut.edu.cn

基金项目: 国家自然科学基金联合重点项目(批准号: U1809210)、国家自然科学基金(批准号: 52102052, 11504325, 52002351, 50972129, 50602039)、国家国际科技合作项目(批准号: 2014DFR51160)、国家重点研发计划 (批准号: 2016YFE0133200)、浙江省自然科学基金(批准号: LQ15A040004, LY18E020013, LGC21E020001)和浙江省重点研发计划国际科技合作“一带一路”专项(批准号: 2018C04021)资助的课题.

Authors and contacts

1.
College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou 310014, China

2.
Moganshan Diamond Research Center, Huzhou 313200, China

3.
Diamond Joint Research Center for Zhejiang University of Technology and Tanghe Scientific & Technology Company, Huzhou 313200, China

Corresponding author: Hu Xiao-Jun, huxj@zjut.edu.cn

Funds: Project supported by the Key Project of National Natural Science Foundation of China (Grant No. U1809210), the National Natural Science Foundation of China (Grant Nos. 52102052, 11504325, 52002351, 50972129, 50602039), the International Science and Technology Cooperation Program of China (Grant No. 2014DFR51160), the National Key Research and Development Program of China (Grant No. 2016YFE0133200), the Natural Science Foundation of Zhejiang Province, China (Grant Nos. LQ15A040004, LY18E020013, LGC21E020001), and the Key Research and Development Program of Zhejiang Province, China (Grant No. 2018C04021).

文章全文 : translate this paragraph

参考文献

[1]	Sildos I, Loot A, Kiisk V, Puust L, Hizhnyakov V, Yelisseyev A, Osvet A, Vlasov I, Kiisk V 2017 Diam. Relat. Mater. 76 27 Google Scholar
[2]	Santacruz-Gomez Karla, Sarabia-Sainz Acosta-Elias M, Sarabia-Sainz M, Janetanakit Woraphong, Khosla Nathan, Melendrez R, Montero Martin Pedroza, Lal Ratnesh 2018 Nanotechnology 29 12.Google Scholar
[3]	Mochalin V N, Shenderova O, Ho D, Gogotsi Y 2012 Nat. Nanotechnol. 7 11 Google Scholar
[4]	李莲莲, 陈冠钦 2022 金刚石与磨料磨具工程 42 543 Google Scholar Li L L, Chen G Q 2022 Diam. Abras. Eng. 42 543 Google Scholar
[5]	Bulut B, Gunduz O, Baydogan M, Kayali E S 2020 Int. J. Refract. Met. H. 95 105466 Google Scholar
[6]	Chen C K, He Z, Xu A C, Hu X J 2021 Funct. Diam. 1 117 Google Scholar
[7]	Chen C K, Mei Y S, Cui J, Xiao L, Jiang M Y, Lu S H, Hu X J 2018 Carbon 139 982 Google Scholar
[8]	Li X, Chen H, Wang C C, Chen C K, Jiang M Y, Hu X J 2023 Diam. Relat. Mater. 136 109927 Google Scholar
[9]	Chen P, Huang F, Yun S 2004 Mater. Res. Bull. 39 1589 Google Scholar
[10]	Jenei Z, O'bannon E F, Weir S T, Cynn H, Lipp M J, Evans W J 2018 Nat. Commun. 9 3563 Google Scholar
[11]	Xu X Y, Yu Z M, Zhu Y W, Wang B C 2005 J. Solid State Chem. 178 688 Google Scholar
[12]	苗卫朋, 丁玉龙, 翟黎鹏, 包华 2019 金刚石与磨料磨具工程 39 18 Google Scholar Miao W P, Ding Y L, Zhai L P, Bao H 2019 Diam. Abras. Eng. 39 18 Google Scholar
[13]	Chen C, Fan D, Xu H, Jiang M, Li X, Lu S, Ke C, Hu X 2022 Carbon 196 466 Google Scholar
[14]	Jiang M Y, Chen C K, Wang P, Guo D F, Han S J, Li X, Lu S H, Hu X J 2022 P. Natl. Acad. Sci. USA 119 e2201451119 Google Scholar
[15]	Zhu Z G, Jiang C Q, Chen C K, Lu S H, Jiang M Y, Li X, Hu X J 2023 Carbon 211 118098 Google Scholar
[16]	Bo Z, Mao S, Han Z J, Cen K F, Chen J H, Ostrikov K 2015 Chem. Soc. Rev. 44 2108 Google Scholar
[17]	Cancado L G, Jorio A, Ferreira E H, Capaz R B, Moutinhc W V O, Ferrari A C 2012 Nano Lett. 11 3190 Google Scholar
[18]	Shimada T, Sugai T, Fantini C , Souza M, Cancado L G 2005 Carbon 43 1049 Google Scholar
[19]	Ferrari A C, Robertson J 2001 Phys. Rev. B 64 075414 Google Scholar
[20]	Gilkes K, Sands H S, Batchelder D N, Robertson J, Milne W I 1997 Appl. Phys. Lett. 70 1980 Google Scholar
[21]	Liu F B, Wang J D, Chen D R, Yan, D Y 2009 Chin. Phys. B 18 2041 Google Scholar
[22]	Gnien D M 1999 Annu. Rev. Mater. Res. 29 211

施引文献

图 1 样品FESEM图像　(a) 未处理样品; (b) 10 Pa样品; (c) 50 Pa样品; (d) 100 Pa样品; (e) 500 Pa样品; (f) 1000 Pa样品

Fig. 1. FESEM images of samples: (a) Untreated sample; (b) 10 Pa sample; (c) 50 Pa sample; (d) 100 Pa sample; (e) 500 Pa sample; (f) 1000 Pa sample.

下载: 全尺寸图片幻灯片

图 2 (a) 未处理样品与不同气压下退火样品的Raman光谱; (b) 样品的I_D/I_G, I_2D/I_G和I_D’/I_G值随退火气压变化图

Fig. 2. (a) Raman spectra of untreated sample and annealed samples at different air pressures; (b) I_D/I_G, I_2D/I_G and I_D’/I_G evolution with different annealed pressure of samples.

下载: 全尺寸图片幻灯片

图 3 (a) 未处理样品的低倍率HRTEM图片, 内插图为SAED图; (b) 未处理样品的高倍率HRTEM图片, 内插图为FT变换图; (c) 10 Pa样品的低倍率HRTEM图片, 内插图为SAED图; (d) 10 Pa样品的高倍率HRTEM图片, 内插图为FT变换图; (e) 50 Pa样品的HRTEM低倍率图片, 内插图为SAED图; (f) 50 Pa样品的高倍率HRTEM图片, 内插图为FT变换图

Fig. 3. (a) Low-magnification HRTEM picture of untreated sample and its inset SAED pattern; (b) high-magnification picture of untreated sample and its inset FT graph; (c) low-magnification HRTEM picture of 10 Pa sample and its inset SAED pattern; (d) high-magnification HRTEM picture of 10 Pa sample and its inset FT graph; (e) low-magnification HRTEM picture of 50 Pa sample and its inset SAED pattern; (f) high-magnification HRTEM picture of 50 Pa sample and its inset FT graph.

下载: 全尺寸图片幻灯片

图 4 (a) 100 Pa样品的低倍率HRTEM图片, 内插图为SAED图; (b) 100 Pa样品的高倍率HRTEM图片, 内插图为FT变换图; (c)—(f) 图4(b)中框选区域放大图, FT-c, FT-d, FT-e和FT-f分别为其对应的FT变换图; (g) 100 Pa样品的能谱(TEM-EDS)图; (h) 100 Pa样品的HAADF和EDS-mapping图

Fig. 4. (a) Low-magnification HRTEM picture of 10 Pa sample and its inset SAED pattern; (b) high-magnification HRTEM picture of 100 Pa sample and its inset FT graph; (c)–(f) enlarged of picture high-magnification in Fig. 4(b), FT-c, FT-d, FT-e and FT-f are all FT graphs; (g) TEM-EDS of 100 Pa sample; (h) HAADF and EDS-mapping of 100 Pa sample.

下载: 全尺寸图片幻灯片

图 5 (a) 500 Pa样品的低倍率HRTEM图片, 内插图为SAED图; (b) 500 Pa样品的高倍率HRTEM图片, 内插图为FT变换图; (c), (d) 图5(b)中框选区域放大图, FT-c和FT-d分别为对应的FT变换图; (e) 1000 Pa样品的低倍率HRTEM图片, 内插图为SAED图; (f) 1000 Pa样品的高倍率HRTEM图片, 内插图为FT变换图; (g) 1000 Pa样品的HAADF和EDS-mapping图

Fig. 5. (a) Low-magnification HRTEM picture of 500 Pa sample and its inset SAED pattern; (b) high-magnification HRTEM picture of 500 Pa sample and its inset FT graph; (c), (d) enlarged images of d and e in Fig.5(b), FT-c and FT-d are FT graphs; (e) low-magnification HRTEM picture of 1000 Pa sample and its inset SAED pattern; (f) high-magnification HRTEM picture of 1000 Pa sample and its inset FT graph; (g) HAADF and EDS-mapping of 1000 Pa sample.

下载: 全尺寸图片幻灯片

图 6 (a) 未处理样品与不同气压下退火样品的XPS全谱图; (b) 样品的C 1s核心能级谱及其拟合曲线; (c) 样品表面C和O的原子百分比随退火气压变化图; (d), (e) 样品表面sp² C, sp³ C, C—O键含量随退火气压变化图

Fig. 6. (a) Full range XPS spectra of untreated sample and annealed samples at different air pressures; (b) C 1s core energy level spectra and their deconvolution of samples; (c) variation of atomic content of C and O on the sample surface with annealing air pressure; (d), (e) variation of sp²-C, sp³-C, C—O and C=O content of sample surface with annealing air pressure.

下载: 全尺寸图片幻灯片

map

[1]	Sildos I, Loot A, Kiisk V, Puust L, Hizhnyakov V, Yelisseyev A, Osvet A, Vlasov I, Kiisk V 2017 Diam. Relat. Mater. 76 27 Google Scholar
[2]	Santacruz-Gomez Karla, Sarabia-Sainz Acosta-Elias M, Sarabia-Sainz M, Janetanakit Woraphong, Khosla Nathan, Melendrez R, Montero Martin Pedroza, Lal Ratnesh 2018 Nanotechnology 29 12.Google Scholar
[3]	Mochalin V N, Shenderova O, Ho D, Gogotsi Y 2012 Nat. Nanotechnol. 7 11 Google Scholar
[4]	李莲莲, 陈冠钦 2022 金刚石与磨料磨具工程 42 543 Google Scholar Li L L, Chen G Q 2022 Diam. Abras. Eng. 42 543 Google Scholar
[5]	Bulut B, Gunduz O, Baydogan M, Kayali E S 2020 Int. J. Refract. Met. H. 95 105466 Google Scholar
[6]	Chen C K, He Z, Xu A C, Hu X J 2021 Funct. Diam. 1 117 Google Scholar
[7]	Chen C K, Mei Y S, Cui J, Xiao L, Jiang M Y, Lu S H, Hu X J 2018 Carbon 139 982 Google Scholar
[8]	Li X, Chen H, Wang C C, Chen C K, Jiang M Y, Hu X J 2023 Diam. Relat. Mater. 136 109927 Google Scholar
[9]	Chen P, Huang F, Yun S 2004 Mater. Res. Bull. 39 1589 Google Scholar
[10]	Jenei Z, O'bannon E F, Weir S T, Cynn H, Lipp M J, Evans W J 2018 Nat. Commun. 9 3563 Google Scholar
[11]	Xu X Y, Yu Z M, Zhu Y W, Wang B C 2005 J. Solid State Chem. 178 688 Google Scholar
[12]	苗卫朋, 丁玉龙, 翟黎鹏, 包华 2019 金刚石与磨料磨具工程 39 18 Google Scholar Miao W P, Ding Y L, Zhai L P, Bao H 2019 Diam. Abras. Eng. 39 18 Google Scholar
[13]	Chen C, Fan D, Xu H, Jiang M, Li X, Lu S, Ke C, Hu X 2022 Carbon 196 466 Google Scholar
[14]	Jiang M Y, Chen C K, Wang P, Guo D F, Han S J, Li X, Lu S H, Hu X J 2022 P. Natl. Acad. Sci. USA 119 e2201451119 Google Scholar
[15]	Zhu Z G, Jiang C Q, Chen C K, Lu S H, Jiang M Y, Li X, Hu X J 2023 Carbon 211 118098 Google Scholar
[16]	Bo Z, Mao S, Han Z J, Cen K F, Chen J H, Ostrikov K 2015 Chem. Soc. Rev. 44 2108 Google Scholar
[17]	Cancado L G, Jorio A, Ferreira E H, Capaz R B, Moutinhc W V O, Ferrari A C 2012 Nano Lett. 11 3190 Google Scholar
[18]	Shimada T, Sugai T, Fantini C , Souza M, Cancado L G 2005 Carbon 43 1049 Google Scholar
[19]	Ferrari A C, Robertson J 2001 Phys. Rev. B 64 075414 Google Scholar
[20]	Gilkes K, Sands H S, Batchelder D N, Robertson J, Milne W I 1997 Appl. Phys. Lett. 70 1980 Google Scholar
[21]	Liu F B, Wang J D, Chen D R, Yan, D Y 2009 Chin. Phys. B 18 2041 Google Scholar
[22]	Gnien D M 1999 Annu. Rev. Mater. Res. 29 211

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基于石墨烯竖立片层常压相变制备纳米金刚石