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View PDF Version Nanoscale Advances View Article Online REVIEW View Journal | View Issue In-plane anisotropic electronics based on low- symmetry 2D materials: progress and prospects Cite this: Nanoscale Adv., 2020, 2,109 Siwen Zhao, a Baojuan Dong,bc Huide Wang,a Hanwen Wang,bc Yupeng Zhang, a Zheng Vitto Han*bc and Han Zhang *a Low-symmetry layered materials such as black phosphorus (BP) have been revived recently due to their high intrinsic mobility and in-plane anisotropic properties, which can be used in anisotropic electronic and optoelectronic devices. Since the anisotropic properties have a close relationship with their anisotropic structural characters, especially for materials with low-symmetry, exploring new low- symmetry layered materials and investigating their anisotropic properties have inspired numerous research efforts. In this paper, we review the recent experimental progresses on low-symmetry layered Received 4th October 2019 materials and their corresponding anisotropic electrical transport, magneto-transport, optoelectronic, Accepted 30th October 2019 thermoelectric, ferroelectric, and piezoelectric properties. The boom of new low-symmetry layered DOI: 10.1039/c9na00623k materials with high anisotropy could open up considerable possibilities for next-generation anisotropic Creative Commons Attribution 3.0 Unported Licence. rsc.li/nanoscale-advances multifunctional electronic devices. 1. Introduction energy band structure and can be regarded as a process of lowering the dimensionality of the carrier transport. Therefore, Two dimensional (2D) layered materials with strong in-plane the electrical, optical, thermal, and phonon properties of these covalent bonds and weak out-of-plane van der Waals interac- anisotropic materials are diverse along the different in-plane tions span a very broad range of solids and exhibit extraordinary crystal directions. Since these unique intrinsic angle-dependent and unique layer-dependent physical properties aer the properties of low-symmetry 2D materials cannot be easily real- This article is licensed under a discovery of graphene.1–6 Even though graphene has extremely ized in highly symmetric 2D materials, the emergence of in-plane large mobility and outstanding electron-transport properties, anisotropic properties can provide another new degree of the absence of a band gap restricts its applications in (opto) freedom to tune the previous unexplored properties and supply Open Access Article. Published on 06 December 2019. Downloaded 9/27/2021 6:50:03 AM. electronic devices. Beyond graphene, 2D layered materials have a tremendous opportunity to the design of new devices, such as become more and more popular among researchers due to their polarization sensitive photodetectors,31,32 polarization sensors,33 unique structural,7,8 mechanical,9 electrical,10,11 thermoelec- articial synaptic devices,34 digital inverters,35 and anisotropic tric,12–15 optical,16–22 catalytic,23,24 and sensing properties,.25–30 memorizers36 that are highly desired in integrated logic circuits. Transition metal dichalcogenides (TMDCs) with tunable band Thus, BP and other low-symmetry layered materials (Table 1) gap fully exert the advantages in low-cost, exible, and high- have attracted enormous research interest towards potential performance logic and optoelectronic devices, such as eld- applications and become a hot topic in the community of effect transistors (FETs), photodetectors, photonic devices and nanoscience and nanotechnology. solar cells. However, people mainly focus on the in-plane Moreover, strong in-plane anisotropic transport properties isotropic behaviors in graphene and TMDCs because of their of low-symmetry 2D materials are typically a result of the symmetric crystal structures until the rediscovery of low- different energy band structure along the different in-plane symmetry black phosphorus (BP). directions of the layered crystal lattice, leading to drastically It is known that reducing the symmetry of materials is different carrier effective mass along the different crystal generally associated with exceptional anisotropy in electronic directions. Therefore, the study on anisotropic magneto- transport properties of low-symmetry layered 2D materials could offer a powerful and useful tool to investigate energy band a International Collaborative Laboratory of 2D Materials for Optoelectronics Science structures and new physical phenomena of low-symmetry Technology of Ministry of Education, Key Laboratory of Optoelectronic Devices and Systems of Ministry of Education and Guangdong Province, Shenzhen University, layered 2D materials, such as anisotropic weak localization, Shenzhen 518060, China. E-mail: [email protected] anisotropic superconducting, and anisotropic non-linear bShenyang National Laboratory for Materials Science, Institute of Metal Research, magneto-resistance, which provide more a comprehensive Chinese Academy of Sciences, Shenyang 110000, China. E-mail: [email protected] understanding of their physical properties and insights into cSchool of Material Science and Engineering, University of Science and Technology of potential applications. China, Anhui 230026, China This journal is © The Royal Society of Chemistry 2020 Nanoscale Adv., 2020, 2,109–139 | 109 View Article Online Nanoscale Advances 110 Table 1 Low-symmetry 2D layered materials classified by the crystal structure and space group and their basic parameters | Nanoscale Adv. Space Effective mass Crystal group Absorption along different Mobility ratio Anisotropic system (bulk) Materials Band gap coefficient Band structure directions (mmax/mmin) conductance Ref. À Orthorhombic Cmca BP 0.35 eV 104 to 105 cm 1 (visible Direct Hole: 6.35/0.15 1.5 1.5 22 , 2020, region) Electron: 1.12/0.17 À Pnma SnS 1.3 eV 105 cm 1 (visible region) Indirect Hole: 0.21/0.36 z1.7 2.0 23 5 À1 Creative Commons Attribution 3.0 Unported Licence. 2 SnSe 0.86 eV >10 cm (visible region) Indirect Electron: 0.14/0.08 is 5.8 3.9 24 ,109 À GeS 1.55–1.65 eV 1.2 Â 105 cm 1 (2.0 eV) Indirect (1,2 L) to direct 41 – (3 L) 139 À GeSe 1.1–1.2 eV 105 cm 1 (visible region) Indirect Hole: 0.33/0.16 1.85 z342 5 À1 Sb2Se3 1.03 eV >10 cm (visible region) Direct 43 Cmc21 SiP 1.69 to 2.59 eV Direct (monolayer) to 44 indirect (multilayer) Pbam GeAs2 0.98 eV Indirect Hole: 0.65 : 0.41 Hole z 1.9 1.8 45 Electron: 0.57 : 0.14 0 Pmn21 1T MoS2 1.8 46 Td-MoTe2 Type II Weyl semimetal 47 This article is licensed under a Td-WTe2 Type II Weyl semimetal 1.64 48 TaIrTe4 Type II Weyl semimetal 1.8–2.2 (10–100 K) 1.7 (300 K) 49 Cmcm Ta2NiS5 0.2 eV Direct Electron: 3.64/0.34 1.41 50 Hole: 0.79/0.39 Open Access Article. Published on 06 December 2019. Downloaded 9/27/2021 6:50:03 AM. ZrTe5 Dirac semimetal 1.5 51 Monoclinic C2/m GeP 1.68 eV for monolayer to Indirect Hole: 0.98/0.57 1.52 52 0.51 eV for bulk Electron: 0.72/0.4 GeAs 0.57 (bulk) to 1.66 eV Indirect 4.6 53 (monolayer) 4 À1 GaTe 1.7 eV >10 cm (visible region) Direct 10 1000 at Vg ¼40V 36 P21/m TiS3 0.8–1 eV Direct 2.3 4.4 54 ZrS3 2.56 eV Direct 55 4 À1 P21/c GeS2 3.71 eV z1.37 Â 10 cm (4 eV) Indirect À b-GeSe 2.74 eV 104 cm 1 Direct Hole: 1.562/0.755 2.1 1.58 56 This journal is © The Royal Society of Chemistry 2020 2 MoO2 Metallic 10.1 57 Triclinic P11 ReS2 1.35 eV Direct 3.1 7.5 35 ReSe2 1.2–1.3 eV Indirect 58 MP15 (M ¼ Li, 1.16–1.52 eV Indirect Hole: 1.39–2.7 10–100 59 Na, K) Electron: 4.44–24.75 6 À1 Trigonal P3121 a-Te 0.35 eV in bulk and <1.6 mm is 4.5 Â 10 cm Indirect along Te chains 0.32/0.3 z1.43 1.35 60 1 eV in monolayer and direct perpendicular to Te chain Tetragonal I4/ TlSe 0.73 eV Indirect Hole: 0.64 : 0.35 61 mcm Review View Article Online Review Nanoscale Advances In addition, due to the anisotropy of transport properties is crucial to study the low-symmetry 2D layered crystal struc- offered by low-symmetry layered 2D materials, their optoelec- tures rst. Aer early investigations on the characterization of tronic, thermoelectric, piezoelectric, and ferroelectric proper- structures and properties of bulk samples, the family of low- ties should also be dependent on the crystalline directions. symmetry 2D layered materials have recently attracted tremen- There is no doubt that the corresponding performance along dous attentions due to the novel anisotropic properties. Here, a certain crystalline direction is better than the others. There- we will categorize the low-symmetry 2D layered materials fore, investigating the anisotropic electronic properties along through the conductivity and periodic table of elements as different crystalline orientations in low-symmetry 2D materials shown in Fig. 2. can optimize the performance of eld effect transistors,35 photodetectors,36 thermoelectric devices,15 piezoelectric 2.1 Elementary 2D material devices,37 ferroelectric devices,38 and so on. Some anisotropic Among the 2D layered anisotropic materials, black phos- semimetals exhibit large non-saturating magnetoresistance phorus (BP) has a wide thickness-tunable direct bandgap (MR) along a specular orientation and can be used in magnetic (0.3 eV of monolayer to 2 eV of bulk) and high intrinsic devices, e.g., magnetic sensors and magnetic memories.37–40 mobility, with a puckered orthorhombic structure of a Cmca Therefore, the study on anisotropic electronic properties in low- space group symmetry (see Fig. 3), which makes it a prom- symmetry 2D materials is of considerable interest and ising core material for next-generation (opto)electronic importance. devices.31,62–68 In the atomic layer, each phosphorus atom in Herein, we summarize the recent advances in low-symmetry BP is connected to three adjacent phosphorus atoms, leading layered materials and their anisotropic electrical properties.
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