Research progress of two-dimensional transition metal dichalcogenide phase transition methods

Zhang Hao-Zhe; Xu Chun-Yan; Nan Hai-Yan; Xiao Shao-Qing; Gu Xiao-Feng

doi:10.7498/aps.69.20200965

Abstract

Following traditional semiconductors such as silicon and GaAs, in recent years the two-dimensional materials have attracted attention in the field of optoelectronic devices, thermoelectric devices and energy storage and conversion due to their many peculiar properties. However, the normal two-dimensional materials such as graphene, cannot be well used in the field of optoelectronics due to the lack of a band gap, and the black phosphorus is also greatly limited in practical applications due to its instability in the air. The two-dimensional transition metal dichalcogenides have attracted more attention due to the different atomic structures, adjustable energy band and excellent photoelectric properties. There are different crystal phases in transition metal dichalcogenides, some of which are stable in the ground state, and others are instable. Different phases exhibit different characteristics, some of which have semiconductor properties and others have like metal in property. These stable and metastable phases of transition metal dichalcogenides can be transformed into each other under some conditions. In order to obtain these metastable phases, thereby modulating their photoelectric performance and improving the mobility of the devices, it is essential to obtain a phase transition method that enables the crystal phase transition of the transition metal dichalcogenides. In this article, first of all, we summarize the different crystal structures of transition metal dichalcogenides and their electrical, mechanical, and optical properties. Next, the eight phase transition methods of transition metal dichalcogenides are listed, these being chemical vapor deposition, doping, ion intercalation, strain, high temperature thermal treatment, laser inducing, plasma treatment, and electric field inducing. After that, the research progress of these phase transition methods and their advantages and disadvantages are introduced. Finally, we sum up all the phase transition methods mentioned in this article and then list some of the problems that have not been solved so far. This review elaborates all of the presently existing different phase transition methods of transition metal dichalcogenides in detail, which provides a good reference for studying the phase transition of transition metal dichalcogenides in the future, the electrical performance regulated by different phases, and the applications of memory devices and electrode manufacturing.

Keywords:

two-dimensional transition metal dichalcogenides /
crystal structure /
phase transition method

Authors and contacts

Engineering Research Center of IOT Technology Applications (Ministry of Education), Department of Electronic Engineering, Jiangnan University, Wuxi 214122, China

Corresponding author: Nan Hai-Yan, jnanhaiyan@jiangnan.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 11704159), the Natural Science Foundation of Jiangsu Province, China (Grant No. BK20170167), the China Postdoctoral Science Foundation (Grant No. 2018M642154), and the Postdoctoral Foundation of Jiangsu Province, China (Grant No. 2018K057B)

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Cited By

图 1 TMD稳定性及半导体特性的总结^[5]

Figure 1. Summarize of the stability and semiconductor properties of TMD^[5].

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图 2 不同相TMD的基本结构图

Figure 2. Basic structure diagram of TMDs different phases.

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图 3 TMD的相变方法

Figure 3. Phase transition methods of TMDs.

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图 4 TMD的CVD法相变　(a) 通过CVD生长出1T' MoTe₂的示意图^[21]; (b), (c)大面积多层MoTe₂的CVD过程中金属-半导体-金属相演化与前驱体的碲化速度的关系^[24]; (d), (e) CVD法获得多层1T'-2H MoTe₂横向同质结^[25]; (f) 三元TMD的CVD法驱动2H到1T' 相变示意图^[29]

Figure 4. TMD phase transition induced by CVD method: (a) Schematic diagram of 1T' MoTe₂ grown by CVD^[21]; (b), (c) relationship between metal-semiconductor-metal phase evolution and telluride velocity of precursor during the CVD process of large-area multilayer MoTe₂^[24]; (d), (e) multilayer 1T' -2H MoTe₂ transverse homogeneous junction was obtained by CVD^[25]; (f) schematic diagram of ternary TMD 2H-1T' phase transition driven by the CVD method^[29].

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图 5 通过掺杂/合金化诱导TMD相变　(a), (b) MoTe₂掺杂部分非金属元素后发生的相位改变^[46]; (c), (d) MoS₂掺杂Cu引发2H-1T' 相的改变^[47]; (e) 过渡金属掺入MoSe₂, MoTe₂和WTe₂形成合金的相位稳定性^[48]

Figure 5. TMD phase transition induced by doping/alloying: (a), (b) The phase transition of MoTe₂ after doping part of nonmetallic elements^[46]; (c), (d) the 2H-1T' phase transition of MoS₂ induced by doping Cu^[47]; (e) the phase stability of the alloy was obtained by mixing the transition metal with MoSe₂, MoTe₂ and WTe₂^[48].

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图 6 分子插层和应力诱导TMD相变　(a) MoS₂相变难度与其层数的关系^[57]; (b) 电化学法诱导三元TMD相变示意图; (c) 相变前后三元TMD的STEM图像和XPS光谱; (d) 1T三元层状TMD的电学特性^[60]; (e) 机械拉伸诱导MoTe₂由2H-1T' 的转变^[65]; (f) 在空位与拉伸条件下MoX₂ TMD的相位稳定性^[69]; (g) 三元TMD通过拉伸引发不可逆相变^[71]

Figure 6. TMD phase transition induced by intercalation and strain: (a) The relationship between the phase transition difficulty of MoS₂ and the number of layers^[57]; (b) schematic diagram of ternary TMD phase transition induced by electrochemical method; (c) STEM image and XPS spectrum of ternary TMD before and after phase transition; (d) electrical properties of 1T ternary layered TMD^[60]; (e) mechanical tensile induced 2H-1T' transformation of MoTe₂^[65]; (f) phase stability of MoX₂ TMD under vacancy and stretch conditions^[69]; (g) irreversible phase transition of ternary TMD induced by stretching^[71].

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图 7 高温热处理、激光、等离子体诱导TMD相变　(a) MoTe₂相变程度与温度及Te浓度的关系^[72]; (b) 块状1T-TaS₂的1T-2H相变示意图^[73]; (c) NbSe₂上1T和2H相的选择性合成^[76]; (d) 激光灼烧诱导相变示意图^[78]; (e) 激光引导MoTe₂诱导相变的原理图^[81]; (f) Ar等离子体引发MoS₂相变的光学特性^[86]; (g) 温和等离子体诱导MoTe₂相变原理图; (h) 2H和1T' MoTe₂的转移特性曲线^[88]

Figure 7. TMDs phase transition induced by thermal, laser and plasma treatment: (a) The relationship between MoTe₂ phase transition and temperature and Te concentration^[72]; (b) schematic diagram of 1T-2H phase transition on the bulk 1T-TaS₂^[73]; (c) selective synthesis of 1T and 2H phases on NbSe₂^[76]; (d) schematic diagram of the phase transition by laser irradiation^[78]; (e) schematic diagram of laser-induced MoTe₂ phase transition^[81]; (f) optical properties of MoS₂ phase transition induced by Ar plasma^[86]; (g) schematic diagram of MoTe₂ phase transition induced by soft plasma; (h) transfer characteristic curves of 2H and 1T' MoTe₂^[88].

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图 8 电场引导TMD相变　(a) MoTe₂相变与门控电压的关系; (b) TaSe₂电场相变示意图及其相变与门控电压的关系^[92]; (c) 静电掺杂诱导MoTe₂相变原理图; (d) MoTe₂相变过程拉曼光谱及其相变程度与栅极电压的关系^[93]; (e) STM尖端电压脉冲诱导NbSe₂的相变^[94]; (f) 施加电场对Mo_1–_xW_xTe₂的2H-2H_d相变^[11]

Figure 8. TMDs phase transition induced by electric-field: (a) Relationship between MoTe₂ phase transition and gate voltage; (b) schematic diagram of TaSe₂ electric-field phase transition and its relationship with gate voltage^[92]; (c) schematic diagram of electrostatic doping induced MoTe₂ phase transition; (d) Raman spectrum of MoTe₂ phase transition and relationship between the phase transition and gate voltage^[93]; (e) phase transition of NbSe₂ induced by voltage pulses with an STM tip^[94]; (f) the 2H-2H_d phase transition of Mo_1–_xW_xTe₂ by applying electric field^[11].

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表 1 TMD的相变方法及其特点

Table 1. Phase transition methods of TMDs and their properties.

相变方法	特点
相变方法	优点	不足
化学气相沉积	可以通过改变温度、气流量以及源粉成分来实现不同相的选择性生长或相变, 操作简单	该方法受环境因素影响较大, 产物不稳定
掺杂/合金化	通过对TMD引入其他原子使其完成半导体到半金属的转变, 生成产物性质稳定, 不易变质	原有材料本身的化学性质容易发生改变, 一些原有的良好性能受到破坏
分子插层	将离解出的原子或离子嵌入对象TMD材料双层之间的空隙从而达到相变的目的, 该方法因其操作简单, 现已成为TMD的常用相变方法	相变产物中可能包含插层原子或离子
应力	通过机械拉伸可以实现薄层TMD的相变, 这种相变通常不可逆, 所以可以保持产物的稳定性	过度引入应力可能使材料开裂或变形
高温热处理	提高温度来实现TMD的相变, 是最为直接的相变方法, 操作容易	相变产物在长时间室温条件下可以恢复为原来的晶相
激光引导	使用激光照射TMD样品来实现其相变, 相变产物稳定, 不易恢复为原来的晶相, 有着广阔的应用前景	相变往往具有不可逆性, 且激光功率过大容易损坏样品
等离子体处理	通过低温等离子体处理TMD材料实现其相变, 可实现大范围简易相位调控, 研究前景广阔	相变产物不稳定, 高温下晶相容易恢复
电场引导	通过电场直接在TMD器件上实现相变, 避免了相变后的 TMD在制作器件时恢复为原来的晶相, 这种相变通常可逆, 在电子器件制造上有着广泛的应用	局限于电学器件制造, 很难在其他方面有所应用, 另外实验所需环境较为苛刻

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