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
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