Citation: Zhang Dandan, Yuan Zhenzhou, Zhang Guoqing, Tian Nan, Liu Danmin, Zhang Yongzhe. Preparation and Characterization of Black Phosphorus[J]. Acta Chimica Sinica, ;2018, 76(7): 537-542. doi: 10.6023/A18040175 shu

Preparation and Characterization of Black Phosphorus

a.
Beijing Key Laboratory of Microstructure and Properties of Advanced Material, Institute of Microstructure and Property of Advanced Materials, Beijing University of Technology, Beijing 100124
b.
Key Laboratory of Advanced Functional Materials, Education Ministry of China, College of Materials Science and Engineering, Beijing University of Technology, Beijing 100124

Corresponding author: Liu Danmin, dmliu@bjut.edu.cn
Received Date: 28 April 2018
Available Online: 6 July 2018
Fund Project: the Science and Technology Commission of Beijing Municipality Z151100003315018the National Natural Science Foundation of China 61575010Project supported by the National Natural Science Foundation of China (Nos. 51671006 and 61575010), the Natural Science Foundation of Beijing (No. 4162016), and the Science and Technology Commission of Beijing Municipality (No. Z151100003315018)the Natural Science Foundation of Beijing 4162016the National Natural Science Foundation of China 51671006

Figures(7)

Black phosphorus has attracted broad interest because of their low-dimensional effect, and has become a new kind of two-dimensional (2D) materials. Phosphorus has several allotropes. Black phosphorus is the most thermodynamic stable in them. As a kind of two-dimensional materials, black phosphorus has high carrier mobility and on/off ratio. The band gap of black phosphorus can be adjusted by its number of layers from 0.3 to 2 eV. It is of great significance to the development of new infrared and near-infrared optoelectronic devices. Currently, the main methods for preparing black phosphorus are chemical vapor transfer and high energy ball milling methods. In this paper, black phosphorus was successfully synthesized from red phosphorus via chemical vapor transfer and high energy ball milling methods. Then black phosphorus was put in ethanol for 10 min to liquid exfoliation, in which the ultrasonic power was 400 W. The microstructures and stability of black phosphorus synthesized by two methods were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential scanning calorimeter (DSC). In situ electrical measurements of black phosphorus prepared by chemical vapor transfer were performed using a commercial scanning tunnelling microscope-transmission electron microscope probing system (STM-TEM, Nanofactory Instruments) inserted into a JEOL-2010F TEM. The microstructural characterization results show that there is some red phosphorus and amorphous phases in black phosphorus prepared by high energy ball milling method. On the contrary, the black phosphorus prepared by chemical vapor transfer method has no amorphous phases. The XRD results show that black phosphorus synthesized by chemical vapor transfer method did not change significantly after keeping in the air for 16 days. The DSC results show that the volatile points of the black phosphorus prepared by high energy ball milling and chemical vapor transfer methods are respectively 394.5 and 432.2℃, which means the latter has better thermal stability. The TEM results show that a layer or two layers of phosphorene via liquid exfoliation had been obtained, which is large in size and clean in surface. After being irradiated in TEM with a dose of 0.8 eV/(Å²·s) at 200 kV for 60 min, few new diffraction spots appeared in black phosphorus synthesized by chemical vapor transfer method, which indicates it is relatively stable under electron radiation in vacuum. In a word, the black phosphorus prepared by chemical vapor transfer method has large size, good crystallinity, high purity, and high stability. It can be used to prepare two-dimensional black phosphorus by mechanical exfoliation and liquid exfoliation, and then be applied to advanced microelectronic devices.
- black phosphorus,
- high energy ball mill method,
- chemical vapor transport method,
- stability,
- electrical property
1. [1]
  Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Zhang, Y.; Dubonos, S. V.; Grigorieva, I. V.; Firsov, A. A. Science 2004, 306, 666. doi: 10.1126/science.1102896
2. [2]
  Susarla, S.; Manimunda, P.; Morais Jaques, Y.; Hachtel, J.; Idrobo, J. C.; Syed Amanulla, S. A.; Galvao, D. S.; Tiwary, C. S.; Ajayan, P. M. ACS Nano 2018, DOI:10. 1021/acsnano. 8b01786. doi: 10.1021/acsnano.8b01786
3. [3]
  Lin, X.; Wang, J. Acta Chim. Sinica 2017, 75, 979. (in Chinese).
4. [4]
  Yang, L.; Fu, Q.; Wang, W.; Huang, J.; Huang, J.; Zhang, J.; Xiang, B. Nanoscale 2015, 7, 10490. doi: 10.1039/C5NR02652K
5. [5]
  Tan, C.; Yu, P.; Hu, Y.; Chen, J.; Huang, Y.; Cai, Y.; Luo, Z.; Li, B.; Lu, Q.; Wang, L.; Liu, Z.; Zhang, H. J. Am. Chem. Soc. 2015, 137, 10430. doi: 10.1021/jacs.5b06982
6. [6]
  Liang, Y.; Feng, R.; Yang, S.; Ma, H.; Liang, J.; Chen, J. Adv. Mater. 2011, 23, 640. doi: 10.1002/adma.201003560
7. [7]
  Yoo, J. J.; Balakrishnan, K.; Huang, J.; Meunier, V.; Sumpter, B. G.; Srivastava, A.; Conway, M.; Reddy, A. L.; Yu, J.; Vajtai, R.; Ajayan, P. M. Nano Lett. 2011, 11, 1423. doi: 10.1021/nl200225j
8. [8]
  Wang, X.; Zhi, L.; Müllen, K. Nano Lett. 2008, 8, 323. doi: 10.1021/nl072838r
9. [9]
  Balandin, A. A.; Ghosh, S.; Bao, W.; Calizo, I.; Teweldebrhan, D.; Miao, F.; Lau, C. N. Nano Lett. 2008, 8, 902. doi: 10.1021/nl0731872
10. [10]
  Nair, R. R.; Blake, P.; Grigorenko, A. N.; Novoselov, K. S.; Booth, T. J.; Stauber, T.; Peres, N. M. R.; Geim, A. K. Science 2008, 320, 1308. doi: 10.1126/science.1156965
11. [11]
  Novoselov, K. S.; Geim, A. K.; Morozov, S. V.; Jiang, D.; Katsnelson, M. I.; Grigorieva, I. V.; Dubonos, S. V.; Firsov, A. A. Nature 2005, 438, 197. doi: 10.1038/nature04233
12. [12]
  Lee, C.; Wei, X.; Kysar, J. W.; Hone, J. Science 2008, 321, 385. doi: 10.1126/science.1157996
13. [13]
  Zhang, Y.; Tan, Y. W.; Stormer, H. L.; Kim, P. Nature 2005, 438, 201. doi: 10.1038/nature04235
14. [14]
  Hu, P.; Wang, L.; Yoon, M.; Zhang, J.; Feng, W.; Wang, X.; Wen, Z.; Idrobo, J. C.; Miyamoto, Y.; Geohegan, D. B.; Xiao, K. Nano Lett. 2013, 13, 1649. doi: 10.1021/nl400107k
15. [15]
  He, X.; Liu, F.; Zeng, Q.; Liu, Z. Acta Chim. Sinica 2015, 73, 924(in Chinese).
16. [16]
  Radisavljevic, B.; Radenovic, A.; Brivio, J.; Giacometti, V.; Kis, A. Nat. Nanotechnol. 2011, 6, 147. doi: 10.1038/nnano.2010.279
17. [17]
  Liu, S.; Huo, N.; Gan, S.; Li, Y.; Wei, Z.; Huang, B.; Liu, J.; Li, J.; Chen, H. J. Mater. Chem. C 2015, 3, 10974. doi: 10.1039/C5TC01809A
18. [18]
  Xia, F.; Wang, H.; Jia, Y. Nat. Commun. 2014, 5, 4458. doi: 10.1038/ncomms5458
19. [19]
  Li, L.; Yu, Y.; Ye, G. J.; Ge, Q.; Ou, X.; Wu, H.; Feng, D.; Chen, X. H.; Zhang, Y. Nat. Nanotechnol. 2014, 9, 372. doi: 10.1038/nnano.2014.35
20. [20]
  Liu, H.; Neal, A. T.; Zhu, Z.; Luo, Z.; Xu, X.; Tománek, D.; Ye, P. D. ACS Nano 2014, 8, 4033. doi: 10.1021/nn501226z
21. [21]
  Koenig, S. P.; Doganov, R. A.; Schmidt, H.; Castro Neto, A. H.; Ozyilmaz, B. Appl. Phys. Lett. 2014, 104, 10451.
22. [22]
  Yuan, Z.; Liu, D.; Tian, N.; Zhang, G.; Zhang, Y. Acta Chim. Sinica 2016, 74, 488(in Chinese).
23. [23]
  Li, J.; Chen, C.; Liu, S.; Lu, J.; Goh, W. P.; Fang, H.; Qiu, Z.; Tian, B.; Chen, Z.; Yao, C.; Liu, W.; Yan, H.; Yu, Y.; Wang, D.; Wang, Y.; Lin, M.; Su, C.; Lu, J. Chem. Mater. 2018, DOI:10. 1021/acs. chemmater. 8b00521. doi: 10.1021/acs.chemmater.8b00521
24. [24]
  Zhang, Z.; Xin, X.; Yan, Q.; Li, Q.; Yang, Y.; Ren, T.-L. Sci. China Mater. 2016, 59, 122. doi: 10.1007/s40843-016-0122-1
25. [25]
  Qiao, J.; Kong, X.; Hu, Z. X.; Yang, F.; Ji, W. Nat. Commun. 2014, 5, 4475. doi: 10.1038/ncomms5475
26. [26]
  Buscema, M.; Groenendijk, D. J.; Blanter, S. I.; Steele, G. A.; Zant, H. S. J.; Castellanos-Gomez, A. Nano Lett. 2014, 14, 3347. doi: 10.1021/nl5008085
27. [27]
  Bridgeman, P. W. J. Am. Chem. Soc. 1914, 36, 1344. doi: 10.1021/ja02184a002
28. [28]
  Krebs, H.; Weitz, H.; Worms, K. H. Anorg. Allg. Chem. 1955, 280, 119. doi: 10.1002/(ISSN)1521-3749
29. [29]
  Brown, A.; Rundqvist, S. Acta Crystallogr. 1965, 19, 684. doi: 10.1107/S0365110X65004140
30. [30]
  Mamoru, B.; Fukunori, I.; Yuji, T.; Akira, M. Jpn. J. Appl. Phys. 1989, 28, 1019. doi: 10.1143/JJAP.28.1019
31. [31]
  Maruyama, Y.; Suzuki, S.; Kobayashi, K.; Tanuma, S. Physica B+C 1981, 105, 99. doi: 10.1016/0378-4363(81)90223-0
32. [32]
  Park, C. M.; Sohn, H. J. Adv. Mater. 2007, 19, 2465. doi: 10.1002/(ISSN)1521-4095
33. [33]
  Nilges, T.; Kersting, M.; Pfeifer, T. J. Solid State Chem. 2008, 181, 17071.
34. [34]
  Köpf, M.; Eckstein, N.; Pfister, D.; Grotz, C.; Krüger, I.; Greiwe, M.; Hansen, T.; Kohlmann, H.; Nilges, T. J. Cryst. Growth 2014, 405, 6. doi: 10.1016/j.jcrysgro.2014.07.029
35. [35]
  Lange, S.; Schmidt, P.; Nilges, T. Inorg. Chem. 2007, 46, 4028. doi: 10.1021/ic062192q
36. [36]
  Zhao, M.; Niu, X.; Guan, L.; Qian, H.; Wang, W.; Sha, J.; Wang, Y. CrystEngComm 2016, 18, 7737. doi: 10.1039/C6CE01608A
37. [37]
  Zhang, Z.; Xing, D.-H.; Li, J.; Yan, Q. CrystEngComm 2017, 19, 905. doi: 10.1039/C6CE02550A
38. [38]
  Hanlon, D.; Backes, C.; Doherty, E.; Cucinotta, C. S.; Berner, N. C.; Boland, C.; Lee, K.; Harvey, A.; Lynch, P.; Gholamvand, Z.; Zhang, S.; Wang, K.; Moynihan, G.; Pokle, A.; Ramasse, Q. M.; McEvoy, N.; Blau, W. J.; Wang, J.; Abellan, G.; Hauke, F.; Hirsch, A.; Sanvito, S.; O'Regan, D. D.; Duesberg, G. S.; Nicolosi, V.; Coleman, J. N. Nat. Commun. 2015, 6, 8563. doi: 10.1038/ncomms9563
39. [39]
  Yasaei, P.; Kumar, B.; Foroozan, T.; Wang, C.; Asadi, M.; Tuschel, D.; Indacochea, J. E.; Klie, R. F.; Salehi-Khojin, A. Adv. Mater. 2015, 27, 1887. doi: 10.1002/adma.v27.11
40. [40]
  Guo, Z.; Zhang, H.; Lu, S.; Wang, Z.; Tang, S.; Shao, J.; Sun, Z.; Xie, H.; Wang, H.; Yu, X.-F.; Chu, P. K. Adv. Funct. Mater. 2015, 25, 6996. doi: 10.1002/adfm.201502902
41. [41]
  Yang, Z.; Hao, J.; Yuan, S.; Lin, S.; Yau, H. M.; Dai, J.; Lau, S. P. Adv. Mater. 2015, 27, 3748. doi: 10.1002/adma.v27.25
42. [42]
  Smith, J. B.; Hagaman, D.; Ji, H. F. J. Nanotechnol. 2016, 27, 215602. doi: 10.1088/0957-4484/27/21/215602
43. [43]
  Shao, R.; Zheng, K.; Zhang, Y.; Li, Y.; Zhang, Z.; Han, X. Appl. Phys. Lett. 2012, 101, 1409.
44. [44]
  Tian, T.; Liu, D.; Zhang, B.; Zhang, D.; Shao, R.; Zheng, K.; Yan, H.; Zhang, Y. Mater. Lett. 2016, 183, 432. doi: 10.1016/j.matlet.2016.07.091
1. [1]
  Shitao Fu , Jianming Zhang , Cancan Cao , Zhihui Wang , Chaoran Qin , Jian Zhang , Hui Xiong . Study on the Stability of Purple Cabbage Pigment. University Chemistry, 2024, 39(4): 367-372. doi: 10.3866/PKU.DXHX202401059
2. [2]
  Jiaxi Xu , Yuan Ma . Influence of Hyperconjugation on the Stability and Stable Conformation of Ethane, Hydrazine, and Hydrogen Peroxide. University Chemistry, 2024, 39(11): 374-377. doi: 10.3866/PKU.DXHX202402049
3. [3]
  Jing SU , Bingrong LI , Yiyan BAI , Wenjuan JI , Haiying YANG , Zhefeng Fan . Highly sensitive electrochemical dopamine sensor based on a highly stable In-based metal-organic framework with amino-enriched pores. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1337-1346. doi: 10.11862/CJIC.20230414
4. [4]
  Xuyang Wang , Jiapei Zhang , Lirui Zhao , Xiaowen Xu , Guizheng Zou , Bin Zhang . Theoretical Study on the Structure and Stability of Copper-Ammonia Coordination Ions. University Chemistry, 2024, 39(3): 384-389. doi: 10.3866/PKU.DXHX202309065
5. [5]
  Xiaoning TANG , Junnan LIU , Xingfu YANG , Jie LEI , Qiuyang LUO , Shu XIA , An XUE . Effect of sodium alginate-sodium carboxymethylcellulose gel layer on the stability of Zn anodes. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1452-1460. doi: 10.11862/CJIC.20240191
6. [6]
  Yujia Luo , Yunpeng Qi , Huiping Xing , Yuhu Li . The Use of Viscosity Method for Predicting the Life Expectancy of Xuan Paper-based Heritage Objects. University Chemistry, 2024, 39(8): 290-294. doi: 10.3866/PKU.DXHX202401037
7. [7]
  Bingliang Li , Yuying Han , Dianyang Li , Dandan Liu , Wenbin Shang . One-Step Synthesis of Benorilate Guided by Green Chemistry Principles and in vivo Dynamic Evaluation. University Chemistry, 2024, 39(6): 342-349. doi: 10.3866/PKU.DXHX202311070
8. [8]
  Jingke LIU , Jia CHEN , Yingchao HAN . Nano hydroxyapatite stable suspension system: Preparation and cobalt adsorption performance. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1763-1774. doi: 10.11862/CJIC.20240060
9. [9]
  Xiaowu Zhang , Pai Liu , Qishen Huang , Shufeng Pang , Zhiming Gao , Yunhong Zhang . Acid-Base Dissociation Equilibrium in Multiphase System: Effect of Gas. University Chemistry, 2024, 39(4): 387-394. doi: 10.3866/PKU.DXHX202310021
10. [10]
  Xinxue Li . The Application of Reverse Thinking in Teaching of Boiling Point Elevation and Freezing Point Depression of Dilute Solutions in General Chemistry. University Chemistry, 2024, 39(11): 359-364. doi: 10.3866/PKU.DXHX202401075
11. [11]
  Guimin ZHANG , Wenjuan MA , Wenqiang DING , Zhengyi FU . Synthesis and catalytic properties of hollow AgPd bimetallic nanospheres. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 963-971. doi: 10.11862/CJIC.20230293
12. [12]
  Jiao CHEN , Yi LI , Yi XIE , Dandan DIAO , Qiang XIAO . Vapor-phase transport of MFI nanosheets for the fabrication of ultrathin b-axis oriented zeolite membranes. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 507-514. doi: 10.11862/CJIC.20230403
13. [13]
  Hui Shi , Shuangyan Huan , Yuzhi Wang . Ideological and Political Design of Potassium Permanganate Oxidation-Reduction Titration Experiment. University Chemistry, 2024, 39(2): 175-180. doi: 10.3866/PKU.DXHX202308042
14. [14]
  Zhenlin Zhou , Siyuan Chen , Yi Liu , Chengguo Hu , Faqiong Zhao . A New Program of Voltammetry Experiment Teaching Based on Laser-Scribed Graphene Electrode. University Chemistry, 2024, 39(2): 358-370. doi: 10.3866/PKU.DXHX202308049
15. [15]
  Feng Liang , Desheng Li , Yuting Jiang , Jiaxin Dong , Dongcheng Liu , Xingcan Shen . Method Exploration and Instrument Innovation for the Experiment of Colloid ζ Potential Measurement by Electrophoresis. University Chemistry, 2024, 39(5): 345-353. doi: 10.3866/PKU.DXHX202312009
16. [16]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
17. [17]
  Tiejun Su . The Construction and Application of the Calculation Formula for Endpoint Error in Precipitation Titration: A Case Study of the Mohr Method. University Chemistry, 2024, 39(11): 384-387. doi: 10.12461/PKU.DXHX202402039
18. [18]
  Zhiwen HU , Weixia DONG , Qifu BAO , Ping LI . Low-temperature synthesis of tetragonal BaTiO₃ for piezocatalysis. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 857-866. doi: 10.11862/CJIC.20230462
19. [19]
  Mengyao Shi , Kangle Su , Qingming Lu , Bin Zhang , Xiaowen Xu . Determination of Potassium Content in Tobacco Stem Ash by Flame Atomic Absorption Spectroscopy. University Chemistry, 2024, 39(10): 255-260. doi: 10.12461/PKU.DXHX202404105
20. [20]
  Zunxiang Zeng , Yuling Hu , Yufei Hu , Hua Xiao . Analysis of Plant Essential Oils by Supercritical CO₂Extraction with Gas Chromatography-Mass Spectrometry: An Instrumental Analysis Comprehensive Experiment Teaching Reform. University Chemistry, 2024, 39(3): 274-282. doi: 10.3866/PKU.DXHX202309069

Get Citation

PDF

XML

Metrics

PDF Downloads(149)
Abstract views(5928)
HTML views(2386)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142