† Corresponding author. E-mail:
Project supported by the National Natural Science Foundation of China (Grant Nos. U1632272, 11574201, and 11521404). D. Q. acknowledges support from the Changjiang Scholars Program, China and the Program for Professor of Special Appointment (Eastern Scholar), China.
Two-dimensional (2D) topological insulators (TIs, or quantum spin Hall insulators) are special insulators that possess bulk 2D electronic energy gap and time-reversal symmetry protected one-dimensional (1D) edge state. Carriers in the edge state have the property of spin-momentum locking, enabling dissipation-free conduction along the 1D edge. The existence of 2D TIs was confirmed by experiments in semiconductor quantum wells. However, the 2D bulk gaps in those quantum wells are extremely small, greatly limiting potential application in future electronics and spintronics. Despite this limitation, 2D TIs with a large bulk gap attracted plenty of interest. In this paper, recent progress in searching for TIs with a large bulk gap is reviewed briefly. We start by introducing some theoretical predictions of these new materials and then discuss some recent important achievements in crystal growth and characterization.
Since the invaluable concept of Fermi liquid was introduced and Bloch waves were proposed by Landau and Bloch, great progress has been made in understanding the electronic properties of crystals by band theory based on the single-particle scenario. According to the band theory, band insulators are crystals that cannot conduct current because the energy bands (valence band) below the Fermi level are fully occupied, while the bands (conduction band) above the Fermi level are completely empty. There is an energy gap between the valence band and the conduction band. When the gap is relatively small (∼1 eV for silicon), we have well-known semiconductors that are the foundational materials of today’s information technology. With the rapid development of the semiconductor industry, we will eventually confront some fundamental problems. One of those is the heat problem. With increasing density of integrated circuits, chips generate more and more heat, resulting in a huge waste of energy that will strongly affect chips’ function sooner or later. Many physicists are trying to find new mechanisms that could resolve or mitigate the heat problem. In 2005 and 2006, the quantum spin Hall effect (2D TI) was proposed by Kane and Mele,[1] and Zhang et al.[2] Topological insulators are classified by the topological invariant Z2. The key phenomenon in realizing TIs is band inversion. We will not discuss the theoretical description and definition of the topological invariant of TIs here, as details can be found in the previous review papers by Kane,[3] Zhang[4] and their coauthors. The first material that was proposed to be a 2D TI was grapheme.[1] Kane and Mele showed that in the edge of a piece of graphene there is a 1D topological edge state. The bulk energy gap in graphene is caused by spin–orbital coupling (SOC). It is well known that SOC is proportional to the atomic number (weight). Carbon atoms are very light, so the bulk gap in graphene is extremely tiny. In fact, the gap of graphene is much smaller than 1 meV. In practice, no one has been able to detect the predicted 1D topological edge state in graphene. Bernevig et al. proposed a previously unknown 2D TI system based on HgTe/CdTe quantum wells,[2] and their predictions were confirmed by low temperature transport measurements in 2007 by Molenkamp’s group.[5] Later, Liu et al. predicted another quantum well (InAs/GaSb) to be a 2D TI.[6] In 2011, Du group succeeded in realizing InAs/GaSb bilayers and observed the 1D edge state.[7,8] The transport results of HgTe/CdTe and InAs/GaSb are shown in Fig.
![]() | Fig. 1. (a) The longitudinal four-terminal resistance of HgTd/CdTe quantum wells as a function of gate voltage measured at T = 30 mK, from Ref. [5]. Device I is a topologically trivial quantum well. Devices II, III, and IV are topologically nontrivial quantum wells. In device IV (1.0 μm × 0.5 μm), at suitable gate voltage, quantum resistance was observed. (b) Transport properties of the 1D edge states in InAs/GaSb bilayers, from Ref. [8]. Conductance plateaus quantized to 2e2/h and 4e2/h, respectively, for the two device configurations shown in the inset, which both have length 2 μm and width 1 μm. |
In this paper, we briefly review recent theoretical and experimental progresses in the study of 2D TIs with a large bulk energy gap. The paper is organized as follows. In Section 2, we introduce some theoretical predications of the new 2D materials that are 2D TIs with a very large gap. In Section 3, we discuss some recent experimental efforts in fabricating 2D TI materials and detecting the 1D edge states in 2D TI films as well as on the surface of particular bulk materials by angle-resolved photoemission spectroscopy (ARPES), scanning tunneling spectroscopy (STM), and transport measurements. In conclusion (Section 4), we discuss some issues and present our outlook.
Unlike quantum wells, 2D films consisting of a single element can be used to realize 2D TIs with a large energy gap. We introduce two samples below.
Bismuth (Bi) is a heavy element with a very large SOC. Bulk Bi crystal has a rhombohedral structure and is well known for its novel spin-split surface states arising from the large SOC.[9] Along the (111) direction, the stable and smallest unit of Bi is the bilayer (BL) structure shown in Fig.
![]() | Fig. 2. (a) Top and side views of single-bilayer Bi(111). (b) Calculated energy gap of ultra-thin Bi(111) film as a function of thickness, from Ref. [11]. For single-bilayer Bi(111), the energy gap is larger than 0.5 eV. |
Beyond buckled-honeycomb Bi, 2D Bi allotropes composed of eight-atom rings were recently reported by Li et al.[12] These allotropes contain unique atomic octagonal tiling (OT), as shown in Fig.
![]() | Fig. 3. Crystal and electronic structures of OT-Bi, from Ref. [12]. (a) Bird’s-eye and side views of OT-Bi single-layer. (b) Bulk electronic bands and the Dirac-cone-like 1D edge state in the OT-Bi nanoribbon. |
As we discussed in the introduction, graphene is the first 2D TI to be investigated, but its bulk energy gap is too small for electronic/spintronic application. Following the success with graphene, various 2D group IV materials with honeycomb lattices were fabricated, including a silicon counterpart of graphene (silicene),[13] a germanium graphene analogue (germanene),[14] and a tin graphene analogue (stanene).[15] Theoretically, silicene, germanene, and stanene are all 2D TIs.[16,17] The bulk energy gaps of silicene and germanene are relatively small, ∼0.0016 eV and 0.024 eV, respectively. But the bulk energy gap of stanene is much larger, ∼ 0.1 eV. The crystal structure of stanene is shown in Fig.
![]() | Fig. 4. Crystal structure and energy gap of stanene, from Ref. [17]. (a) Top and side views of stanene. (b) Top and side views of decorated stanene. (c) Energy gaps and topological properties of stanene and decorated stanene. Stanene has a bulk gap of ∼0.1 eV. After decoration, the bulk gap increases to ∼0.3 eV. |
Besides single-element 2D semiconductors, binary 2D crystals can also be used to create 2D TIs. Just as we did for the single-element case, below, we introduce two typical examples of binary compounds that have been used.
Bulk Bi4Br4is a layered material. It is a trivial insulator. Its interlayer bonding energy is comparable to those of other layered materials that have been successfully exfoliated, such as graphite and MoS2. The topological properties of single-layer Bi4Br4 are completely different from those of its bulk parent material. Figure
![]() | Fig. 5. Crystal and electronic structures of single-layer Bi4Br4, from Ref. [18]. (a) Unit cell of single-layer Bi4Br4. (b) Bulk electronic bands and the 1D edge state in Bi4Br4 nanoribbon. (c) Energy gap of single-layer Bi4Br4 as a function of external strain. |
Bulk ZrTe5 is known as a layered thermoelectric material. The interlayer bonding in ZrTe5 is only slightly stronger than that in graphite. Figure
![]() | Fig. 6. Crystal and electronic structures of single-layer ZrTe5, from Ref. [19]. (a) Bulk unit cell of ZrTe5. ZrTe5 layer is in the a–c plane. (b) Bulk electronic bands and the 1D edge states in single-layer ZrTe5 nanoribbon. Red and blue curves are from two different edge morphologies. (c) Energy gap of single-layer ZrTe5 as a function of external strain. |
In Section 2, we briefly discussed some large-gap 2D TIs recently predicted by first-principles calculations. In the last several years, some of those have been successfully fabricated and their non-trivial topological properties were confirmed. Below, we discuss the recent progress.
Single-BL Bi(111) film is the first system that was carefully explored experimentally. Between 2011 and 2012, high quality ultrathin (< 5 BL) Bi(111) films were successfully grown for the first time, on Bi2Te3 substrates, using MBE, by two groups working independently.[20,21] Figure
![]() | Fig. 7. Surface morphology and electronic structure of single-bilayer Bi(111) films grown on Bi2Te3, from Ref. [21]. (a) STM morphology of single-bilayer Bi(111)/Bi2Te3. (b) ARPES spectra overlaid with DFT calculations. (c) 1D edge state and bulk energy gap of single-bilayer Bi(111)/Bi2Te3. |
Besides the epitaxial films, the topological properties of the nearly free-standing Bi(111) have also been explored on the surface of bulk Bi. Drozdov et al. studied the edge states of 1-BL islands on the surface of bulk Bi.[22] Figure
![]() | Fig. 8. 1D edge state in single-bilayer Bi islands on the surface of bulk Bi, from Ref. [22]. (a) Schematics of Bi-bilayer’s atomic structure. Two types of edges are marked by red and blue lines, respectively. (b) STS of type-A and type-B edges, as well as of the terrace. (c) Quasi-particle interference within the edge channel. Two branches were observed: q1 and q2 come from the 1D edge state and 2D surface state, respectively. (d) Schematic of the band dispersion for the Bi bilayer on bulk Bi(111). The grey region represents the projected Bi(111) surface state continuum in the direction parallel to the 1D edge state. E1 and E2 indicate the peak positions in panel (b). |
Although spectral measurements of both thin films and bulk crystals confirmed the non-trivial TI property of 1-BL Bi(111), transport measurement cannot been done on the films or on the surface of bulk Bi because they are not in the insulating state. In 2013, Sabater et al. tried to measure the transport properties of a free-standing 1-BL Bi layer on a Bi nanocontact.[23] Figure
![]() | Fig. 9. Conductance of Bi nanocontact, from Ref. [23]. (a) The proposed process of exfoliating a Bi(111) bilayer (red) after contact with the STM tip. (b) Conductance plateaus of Bi(111) bilayers between tip and substrate. |
Stanene has a crystal structure similar to 1-BL Bi(111) films. However, the interaction between two stanene layers is very strong. In fact, a stack of stanene forms bulk grey tin with a diamond structure; hence it is impossible to isolate stanene by mechanical exfoliation. Bulk grey tin is not stable at room temperature. In 2015, Zhu et al. succeeded in growing 2D stanene films by MBE. The crystal structure of stanene and its electronic structures were determined for the first time. Figure
![]() | Fig. 10. Crystal and electronic structures of stanene, from Ref. [15]. (a) Hexagonal lattice of the stanene surface. (b) Lattice model of stanene on Bi2Te3 substrate. Orange and green balls represent stanene atoms. Grey balls represent Te atoms. (c) ARPES spectra of stanene/Bi2Te3. Blue dotted lines mark stanene bands. |
Although no single-layer ZrTe5 film or free-standing layer has been obtained yet, the topological properties of single-layer ZrTe5 were confirmed by observation of a 1D edge on the surface of bulk ZrTe5 with the help of DFT calculations. Two groups independently carried out the experiments.[24,25] Figure
![]() | Fig. 11. 1D edge state in the step edge of a single-layer ZrTe5 island on the surface of bulk ZrTe5, from Ref. [24]. (a) Morphology of single-layer ZrTe5 step. STS curves obtained from the terrace and the edge. (b) Calculated bulk bands and 1D edge state of a single-layer ZrTe5 nanoribbon. (c) Full energy gap observed on the terrace. Contributions from 1D edge state were observed near the edge (red curves). |
Two-dimensional TIs can also be realized in a very complicated material that is a weak 3D TI in the bulk. Figure
![]() | Fig. 12. Crystal structure and 1D edge state of 2D layer of Bi14Rh3I9, from Ref. [26]. (a) Bi14Rh3I9 consists of 2D (Bi4Rh)3I layers alternating with Bi2I8 space layers. (b) On the cleaved surface, 2D layers and space layers are both observed. (c) STS of different positions. Sharp feature from 1D edge state was observed on the edge of 2D (Bi4Rh)3I layer. |
We have briefly reviewed recent progress with the large gap 2D TIs, including single-BL Bi(111) films, stanene films, single-layer Bi4Br4, single-layer ZrTe5, and single-layer (Bi4Rh)3I. Those systems all include heavy elements. Energy gaps in all these materials except ZrTe5 are caused by the SOC, that is, a large SOC, which is inherent in the heavy elements, results in the large bulk gap. However, an energy gap induced by SOC cannot be very large. It would be extremely difficult to realize 2D TIs with a 1 eV gap purely due to SOC, even in theory. On the other hand, the gap in ZrTe5 is due to its very special space group, which implies that it could be possible to obtain a larger bulk gap in nonsymmorphic crystals, regardless of the SOC.
Although nontrivial TI properties and 1D edge states have been confirmed in Bi, ZrTe5, and (Bi4Rh)3I, it is still a big challenge to explore the electric transport properties along the 1D edge states at high temperature. In my view, Bi(111) film is currently the best possible candidate for transport measurements because Bi films are much more stable than stanene or ZrTe5. So far, single-BL Bi can be realized only on the surface of Bi2Te3 (or similar compounds). The surface of Bi2Te3 consists of Te atoms with a hexagonal lattice. The lattice mismatch between the Te layer and Bi is moderate, which helps us obtain smooth single-BL Bi. On the other hand, Te layers are also inert, so there are no chemical bonds between Te and Bi. The topological properties of Bi are preserved despite some hybridization between the surface state of Bi2Te3 and the Bi. However, transport measurement of Bi/Bi2Te3 films is impossible because the substrate has metallic surface states. Several methods could be explored to overcome this problem. For example, we can use a single-layer Bi2Te3 film as the substrate. Due to quantum confinement, single-layer Bi2Te3 is a trivial insulator (gap ∼0.2 eV). In addition, other semiconductors such as In2Te3 abd In2Se3 (gap ∼1 eV) that have an inert surface layer similar to that of Bi2Te3 could be very good choices if we can obtain high quality films. In the next several years, one of the most important issues in the field of 2D TI is finding stable systems that can be fabricated to explore the electric transport properties along the 1D edge states at high temperature.
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