化学气相运输法制备正交黑磷

doi:10.15541/jim20210805

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1102-1108.DOI: 10.15541/jim20210805

所属专题：【能源环境】量子点；【信息功能】Max层状材料、MXene及其他二维材料

化学气相运输法制备正交黑磷

符明富(), 杨雯, 李佳保, 邓书康, 周启航, 冯小波, 杨培志()

云南师范大学可再生能源材料先进技术与制备教育部重点实验室, 昆明 650500

收稿日期:2021-12-29 修回日期:2022-03-22 出版日期:2022-10-20 网络出版日期:2022-07-08
通讯作者: 杨培志, 研究员. E-mail: pzhyang@hotmail.com
作者简介:符明富(1998-), 男, 硕士研究生. E-mail: mingfu159@foxmail.com
基金资助:
国家自然科学基金(U1802257);云南省基础研究重点项目(202201AS070023);“春城计划”高层次人才引进培养工程(2022SCP005)

Synthesis of Orthorhombic Black Phosphorus by Chemical Vapor Transport Method

FU Mingfu(), YANG Wen, LI Jiabao, DENG Shukang, ZHOU Qihang, FENG Xiaobo, YANG Peizhi()

Key Laboratory of Renewable Energy Advanced Materials and Manufacturing Technology (Ministry of Education), Yunnan Normal University, Kunming 650500, China

Received:2021-12-29 Revised:2022-03-22 Published:2022-10-20 Online:2022-07-08
Contact: YANG Peizhi, professor. E-mail: pzhyang@hotmail.com
About author:FU Mingfu (1998-), male, Master candidate. E-mail: mingfu159@foxmail.com
Supported by:
National Natural Science Foundation of China(U1802257);Yunnan Provincial Natural Science Foundation(202201AS070023);High-level Talent Promotion and Training Project of Kunming(2022SCP005)

摘要/Abstract

摘要：

黑磷(Black phosphorus, BP)以其优异而独特的物理化学性质在能源储存与转换、微纳器件、光/电催化和生物医药等领域展现出良好的应用前景。高质量正交BP前体制备是实现二维BP和零维BP量子点应用的关键。本工作采用无温度梯度的化学气相运输(CVT)法研究了矿化剂组分和比例对BP生长的影响。结果表明, 只有锡(或铅)和碘共存且比例合适时才能制备得到正交BP; 生长BP所需的锡碘质量比w(Sn/I₂)范围较宽, 当w(Sn/I₂)=0.47时制得的BP尺寸为1.2 cm, 且产率高、晶体质量较优。结合BP的成核生长机理可知, 锡和碘都对BP的成核生长具有重要作用; 碘的矿化效果较锡明显, 而足量的锡有利于无温度梯度条件下大尺寸块体BP晶体的合成。w(Sn/I₂)=0.47为本工作中制备BP的最佳砂化剂配比。

关键词: 化学气相运输法, 正交黑磷, 矿化剂, 成核生长

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

中图分类号:

TQ174

符明富, 杨雯, 李佳保, 邓书康, 周启航, 冯小波, 杨培志. 化学气相运输法制备正交黑磷[J]. 无机材料学报, 2022, 37(10): 1102-1108.

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.

图/表 8

表1 采用不同的矿化剂制备黑磷

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

表2 采用不同的w(Sn/I2)制备黑磷

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

图1 不同矿化剂组分制得的正交BP照片

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)

图2 不同w(Sn/I2)制得的正交BP的照片以及BP的产率与w(Sn/I2)之间的关系

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)

图3 不同w(Sn/I2)制备的BP的XRD图谱(a)及BP的晶胞原子及晶面示意图(b)

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

图4 不同w(Sn/I2)制备的BP的Raman表征和Raman面扫描区域的光学显微镜图像及相应的面扫描振动模式

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

图5 不同w(Sn/I2)制备的BP的组分分析

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

图6 不同w(Sn/I2)制备的BP的表面形貌和微结构

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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化学气相运输法制备正交黑磷

Synthesis of Orthorhombic Black Phosphorus by Chemical Vapor Transport Method

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