Synthesis of Orthorhombic Black Phosphorus by Chemical Vapor Transport Method

doi:10.15541/jim20210805

Abstract

Abstract:

Black phosphorus (BP) with excellent and unique physical and chemical properties has emerged as the most promising semiconductor for energy storage and conversion, micro-nano devices, photo- and electro-catalysis, biomedicine, and so on. It is crucial to synthesize high-quality precursors of orthorhombic BP for realizing the applications of two-dimensional BP and zero-dimensional BP quantum dots. Herein, the effects of mineralizer components and ratios on BP growth were studied by the chemical vapor transport (CVT) method without temperature gradient. The results indicate that orthorhombic BP can be synthesized under some experimental combinations that can be considered viable only when tin (or lead) and iodine coexist together with the appropriate ratio. And the mass ratio ranges of tin and iodine w(Sn/I₂) for BP preparation is wide, and the size of BP crystal obtained at w(Sn/I₂)=0.47 is up to 1.2 cm, of which yield and crystal quality are superior. Combined with the nucleation and growth mechanism of BP, tin and iodine are severely significant for the nucleation and growth of BP, which has been widely accepted. Mineralization effect of iodine is more obvious than that of tin, and sufficient tin contributes to the synthesis of large-size bulk BP crystals without temperature gradient. As a result, w(Sn/I₂)=0.47 is the optimal minera lizer ratia for fabricating orthorhombic BP in this work.

Key words: chemical vapor transport method, orthorhombic black phosphorus, mineralizer, nucleation growth

CLC Number:

TQ174

FU Mingfu, YANG Wen, LI Jiabao, DENG Shukang, ZHOU Qihang, FENG Xiaobo, YANG Peizhi. Synthesis of Orthorhombic Black Phosphorus by Chemical Vapor Transport Method[J]. Journal of Inorganic Materials, 2022, 37(10): 1102-1108.

Figures/Tables 8

Table 1 Preparation of BP by different mineralizers

Experiment number	Experimental materials	Mass ratio of mineralizer
1	RP@Sn@I₂	w(Sn/I₂)=2.51
2	RP@Pb@I₂	w(Pb/I₂)=3.96
3	RP@Sn@SnI₄	w(Sn/I)=2.61
4	RP@I₂	-
5	RP@Sn@SnCl₂	w(Sn/Cl)=9.29
6	RP@SnI₄	w(Sn/I)=0.23

Table 2 Synthesis of BP via diverse mass ratios of w(Sn/I2)

Experiment number	Red phosphorus/mg	w(Sn/I₂)
7	400	56.77
8	400	31.39
9	400	20.84
10	400	9.20
11	400	3.18
12	400	1.17
13	400	0.47
14	400	0.41

Fig. 1 Photos of orthorhombic BP synthesized with different mineralizer components (a-f) BP was synthesized under experiment conditions from No.1 to No.6, respectively; (g-i) Corresponding local enlarged images (A small grid of graph paper represents 1 mm)

Fig. 2 Pictures of orthorhombic BP synthesized under different w(Sn/I2) ratios and relationship between the yields of BP and w(Sn/I2) (a-h) BP synthesized under experiment conditions from No.7 to No.14, respectively; (i-n) Corresponding to (b-g) the cleaned BP, respectively (A small grid of graph paper represents 1 mm); (o) Relationship between the yield of BP and w(Sn/I2)

Fig. 3 XRD patterns (a) of BP with different w(Sn/I2) and schematic diagram (b) of cell atoms and crystal planes of BP

Fig. 4 Raman characterizations of BP with different w(Sn/I2), and optical microscope image of Raman using the surface scan and its vibration mode (a) Raman spectra; (b) Raman vibration modes; (c) Optical microscope image of Raman in the surface scan and its (d) Ag1, (e) B 2g, (f) Ag2 vibration mode with w(Sn/I2) of=0.47

Fig. 5 Component analysis of BP with different w(Sn/I2) (a) XPS full spectra; (b) P2p spectra; (c-d) EDS spectra of BP with w(Sn/I2)=31.39 and w(Sn/I2)=0.4

Fig. 6 Surface morphologies and microstructures of BP with different ratios (a-b) Element mappings of BP in the corresponding SEM images, and (c-d) TEM and SAED images of BP

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