二维材料及其范德瓦尔斯异质结的高压响应研究进展

裴胜海; 邓晴阳; 王曾晖; 夏娟

doi:10.11858/gywlxb.20210741

二维材料及其范德瓦尔斯异质结的高压响应研究进展

doi: 10.11858/gywlxb.20210741

电子科技大学基础与前沿研究院，四川成都　610054

基金项目: 国家重点研发计划（2019YFE0120300，2018YFE0115500）；国家自然科学基金（62004026，61774029，62004032）；四川省科技厅应用基础研究计划（2021YJ0517，21CXTD0088，2019YFSY0007，2019JDTD0006）

详细信息

作者简介:
裴胜海（1989－），男，博士，博士后，主要从事二维材料的高压拉曼光谱研究. E-mail：peish0000@gmail.com

邓晴阳（1998－），男，硕士研究生，主要从事新型低维纳米材料器件研究. E-mail：deng_qingyang@std.uestc.edu.cn

通讯作者:
夏　娟（1994－），女，博士，研究员，主要从事新型二维半导体材料的电子和光电性能研究. E-mail：juanxia@uestc.edu.cn

中图分类号: O521.2
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出版历程
- 收稿日期: 2021-03-10
- 修回日期: 2021-04-11

Pressure Engineering in Two-Dimensional Materials and vdWs Heterostructures

Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China

摘要

摘要: 高压技术是一种高效、连续、可逆的调控材料结构、电学、光学等物理特性的手段，因此利用压强工程在材料中实现超导态、制备超硬材料等成为高压领域的研究热点。不同于传统的三维体相材料，二维材料及其异质结中独特的层间耦合作用使其具有许多不同于传统材料的物理特性，且这些物理特性极易受到外场影响和调控，使得高压物理成功地拓展到低维材料领域。本文以石墨烯、黑磷、六方氮化硼和过渡金属二硫族化合物等几种典型的二维材料及其异质结为例，概述了二维材料及异质结在高压调控下的结构、电学、声子动力学、光学等方面的响应，并简要讨论这些高压调控下的二维材料在未来电子、光电器件等领域应用的潜力。
- 二维材料 /
- 范德瓦尔斯异质结 /
- 高压
Abstract: Pressure engineering, as an efficient, continuous and reversible method in tuning structure, electric and optical properties, has been extensively used in study of materials. Two-dimensional materials and vdWs heterostructures exhibit intriguing physical properties, thanks to their interlayer coupling, a unique degree of freedom. These interlayer-coupling-mediated properties are extremely sensitive to external perturbations, in particular external pressure, which can effectively tune interlayer spacing and thus modulate interlayer coupling strength. In this article, we review the responses to applied pressure in several representative two-dimensional materials (graphene, black phosphorus, h-BN, transition metal dichalcogenides and vdWs heterostructures). A plethora of phenomena are observed, including pressure-induced phase transition, structural instability, phonon dynamics, metallization, superconductivity etc. Opportunities in designing next-generation functional devices based on pressure engineering in these two-dimensional materials and heterostructures are also discussed.
- two-dimensional materials /
- van der Waals heterostructures /
- high pressure

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图 1 石墨烯在高压下的结构和电学响应：(a) DAC压强工程示意图及高压诱导下石墨烯转变为h-金刚石结构的示意图^[25]；(b) 通过高压原位拉曼光谱研究少层石墨烯在常压到51.7 GPa压强范围的结构响应^[22]；(c) 3层石墨烯在室温下的电阻率-压强曲线^[11]；(d) 不同层数的石墨烯G拉曼峰随压强变化的线性频移系数（$\partial {\omega _{\rm{G}}}/\partial p$），其中红方块、蓝圆点和绿三角分别表示传压介质为醇、氩气和氮气^[28]；(e) 双层1.27°转角石墨烯在常压下是金属态，高压下转变为超导态的现象^[30]

Figure 1. Pressure engineering in Graphene: (a) illustration of DAC high-pressure setup and pressure induced phase transition process from trilayer graphene to h-diamond structure^[25]; (b) evolution of Raman spectrum in few-layer graphene, from ambient pressure to 51.7 GPa, showing reversible shift during pressurization and depressurization^[22]; (c) resistance vs. pressure of trilayer graphene measured at room temperature^[11]; (d) linear pressure coefficients ($\partial {\omega _{\rm{G}}}/\partial p$) of graphene G peak (frequency) obtained in alcohol (red squares), argon (blue circles), and nitrogen (green triangle) as a function of thickness^[28]; (e) pressure induced superconductivity in 1.27° twisted bilayer graphene^[30]

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图 2 黑磷在高压下的结构和电学响应：(a) 用高压原位拉曼光谱研究不同层数的黑磷随压强变化的$A^1_{{\rm g}} $、B_2g和$A^2_{{\rm g}} $振动模式的演化^[35]；(b) 体相黑磷中随压强变化的$A^1_{{\rm g}} $、B_2g和$A^2_{{\rm g}} $拉曼模式的半峰全宽（FWHM）演化，虚线表示半导体到拓扑绝缘体相变压强点^[34]；(c) 少层黑磷在高压下从正常绝缘体（NI）转变为二维拓扑狄拉克半金属态（TDSM），及不同层数的黑磷的拓扑相变图，p_C和p_T分别为电子相变点和热稳定点^[39]

Figure 2. Pressure engineering in black phosphorus (BP): (a) the evolution of $A^1_{{\rm g}} $, B_2g and $A^2_{{\rm g}} $ modes in monolayer, bilayer, trilayer, and bulk BP samples as a function of pressure^[35]; (b) the evolution of full width at half maximum (FWHM) of $A^1_{{\rm g}} $, B_2g and $A^2_{{\rm g}} $ modes in bulk BP as a function of pressure^[34], (c) top: evolution of band structure in few-layer BP from normal insulator (NI) to a two dimensional topological Dirac semimetal (TDSM) at high pressure, bottom: the pressure-thickness phase diagram of BP, where p_C and p_T are the critical pressures for electronic phase transition and upper limit of thermodynamic stability respectively^[39]

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图 3 h-BN在高压下的结构和光学响应：(a) h-BN在15 GPa下的XRD谱，表明其完成了从h-BN（P6₃/mmc）到w-BN（P6₃mc）的相转变，蓝线和黑线分别为入射方向平行和垂直DAC轴的数据^[51]；(b) h-BN在13 GPa、室温下转变为密堆w-BN的原子结构变化示意图^[50]；(c) 单层（上）和双层（下）h-BN的原子结构对应力的响应^[56]；（d）多层h-BN的缺陷PL峰随压强变化的响应^[56]

Figure 3. Pressure engineering in hexagonal boron nitride (h-BN): (a) the XRD spectra of bulk h-BN at 15 GPa, collected parallel (blue)/perpendicular (black) to the DAC axis^[51]; (b) atomic structure illustration showing phase transition process from h-BN (P6₃/mmc) to w-BN (P6₃mc) at around 13 GPa at room temperature^[50]; (c) schematic diagram for the strain effect on monolayer (top) and bilayer (bottom) h-BN^[56]; (d) evolution of defect-induced PL spectrum as a function of pressure in multi-layer h-BN^[56]

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图 4 MoS₂在高压下的结构、能带及电学响应：(a) MoX₂的2H_c和2H_a原子结构侧视图，X代表S、Se和Te原子^[61]；(b) 单层、双层和3层MoS₂的价带顶（VBM）的能量劈裂以及层间距随压强变化^[70]；(c) 2H-MoS₂的压强-温度相图^[71]

Figure 4. Pressure engineering in molybdenum dichalcogenides (MoX₂): (a) schematic (side view) of 2H_c and 2H_a structures of MoX₂, with X representing S, Se and Te^[61]; (b) band splitting of VBM and interlayer distance vs. pressure for monolayer, bilayer, and trilayer MoS₂^[70]; (c) pressure-temperature phase diagram of bulk 2H-MoS₂^[71]

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图 5 不同对称性的TMDs在高压下的结构、能带及光学响应：(a) 不同层数的2H-MoS₂中的拉曼振动模式A_1g随压强变化^[62]；(b) 体相T_d-WTe₂的特征拉曼峰随压强的变化，激光入射方向平行于a轴^[83]；(c) 体相1T-ReS₂和2H-MoS₂的特征拉曼峰位随压强的变化^[84]；(d) 不同压强范围下双层MoS₂的带间跃迁示意图^[85]

Figure 5. Pressure engineering in transition metal dichalcogenides (TMDs) with different symmetries: (a) evolution of A_1g Raman mode in MoS₂ with different thickness, as functions of pressure^[62]; (b) evolution of Raman spectrum in bulk T_d-WTe₂ with the incident laser illuminating along the a-axes^[83]; (c) evolution of the featured Raman peaks in bulk ReS₂ (E_g, E_g-like, A_g-like) and MoS₂ (E_1g, E_2g, A_g), as functions of applied hydrostatic pressure^[84]; (d) transition path selection rules of bilayer MoS₂ in different pressure ranges^[85]

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图 6 二维范德瓦尔斯异质结在高压下的结构、激子发光、电荷掺杂等响应：(a) WS₂/MoS₂异质结中$A_1\!\!\!\text{′} $和E′振动模式的频率随压强增加的变化，及其与单层WS₂和单层MoS₂的对比^[89]；(b) 双层WSe₂/MoSe₂异质结的PL谱在高压下的响应（左），及第一性原理计算得到的电子能带结构随压强的变化（右）^[10]；(c) Graphene/MoS₂异质结中石墨烯的狄拉克点移动及电荷转移诱导的载流子浓度变化^[91]；(d) 不同层数（1L、2L、3L）的石墨烯/h-BN异质结中的掺杂效率在STM针尖施加压强下的响应对比^[92]

Figure 6. Pressure engineering in 2D vdWs heterostructures: (a) evolution of $A_1\!\!\!\text{′}$ and E′ vibration modes as a function of pressure^[89]; (b) evolution of measured PL spectrum (left) and calculated electronic band structure (right) with pressure in WSe₂/MoSe₂ heterobilayers, from ambient pressure to 2.8 GPa^[10]; (c) the relative shift of the Dirac point with respect to the Fermi level, together with charge-transfer-induced carrier concentration of graphene, as functions of hydrostatic pressure in graphene/MoS₂ heterostructures^[91]; (d) the relative charging efficiency in graphene/h-BN heterostructures with different number of graphene layers (1L, 2L, 3L), as functions of the applied tip force^[92]

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