† Corresponding author. E-mail:
Project supported by the National Natural Science Foundation of China (Grant Nos. 11974307 and 61574123), Zhejiang Provincial Natural Science Foundation, China (Grant No. D19A040001), the Fundamental Research Funds for the Central Universities of China, and the 2DMOST, Shenzhen University (Grant No. 2018028).
The group-V monolayers (MLs) have been studied intensively after the experimental fabrication of two-dimensional (2D) graphene and black phosphorus. The observation of novel quantum phenomena, such as quantum spin Hall effect and ferroelectricity in group-V elemental layers, has attracted tremendous attention because of the novel physics and promising applications for nanoelectronics in the 2D limit. In this review, we comprehensively review recent research progress in engineering of topology and ferroelectricity, and several effective methods to control the quantum phase transition are discussed. We then introduce the coupling between topological orders and ferroelectric orders. The research directions and outlooks are discussed at the end of the perspective. It is expected that the comprehensive overview of topology and ferroelectricity in 2D group-V materials can provide guidelines for researchers in the area and inspire further explorations of interplay between multiple quantum phenomena in low-dimensional systems.
Two-dimensional (2D) materials have revolutionized the new generation of devices. Decreasing the thickness of materials down to single (or several) atomic layer has attracted tremendous interest since they could display exotic phenomena which are different from their bulk counterparts, e.g., quantum spin Hall effect,[1–4] 2D ferroelectricity,[5] superconductivity,[6–8] or magnetism.[9–11] Motivated by the remarkable progress of graphene,[12,13] 2D materials other than graphene have been a pronounced research field of interest. Recent experimental successes in the elemental 2D layers have invigorated the search for more fascinating structures and properties based on elemental 2D systems, for example, Si (silicene),[14–16] Ge (germanene),[17,18] Sn (stanene),[19] B (borophene),[20] P (phosphorene),[21] As (arsenene),[22] Sb (antimonene),[23] Bi (bismuthene),[4] Te (tellurene),[24] and Se (selenene).[25]
Graphene, the first successfully isolated elemental material in 2D limit with the honeycomb lattice, holds the linear band dispersion and crossing at the K point in the 1st Brillouin zone (BZ), generating the Dirac fermions. Actually, a tiny energy gap opens up at the Dirac points due to spin–orbital coupling (SOC) and graphene is a quantum spin Hall (QSH) insulator.[26] QSH insulators, also named as 2D topological insulators (TI), hold counter-propagating and oppositely spin-polarized conducting states at their edges, which are protected by the time reversal symmetry against the weak localized perturbations. Therefore, these robust edge states endow 2D TIs with possibilities for a wide range of applications in dissipationless electronics, topological quantum computing, and so on.[27–30] However, the SOC effect in graphene is too small to achieve the experimental measurement and topological electronic devices,[31] which stimulates scientists to search for large-gap 2D TIs not only in compounds but also in elemental materials. For example, graphene-like honeycomb structures have been widely explored including group-IV and group-V materials.[32,33] For group-V materials, except for the graphene-like structures, the puckered structures in black phosphorus lattice are also able to exhibit topological properties.[34] This puckered structure is unique for group-V elements due to the one extra valence electron compared to group-IV elements and provides a feasible way to tune the crystal symmetry and distortion of the 2D system, allowing intimate coupling and control between various order parameters.
Ferroelectricity is also an exciting ferroic order, possessing reversible spontaneous electronic polarization which is important for applications in non-volatile memory devices, field effect transistors, solar cells, and sensors.[35–38] Normally, ferroelectricity would disappear when the film thickness is below a critical value, due to the depolarizing electric field and electron screening. A new class of materials, called as hyperferroelectrics, have been identified to remain in stable polar states in ultrathin atomic layers against unscreened depolarizing field.[39] However, the experimental evidence of these materials is still rare. Recently, the ferroelectric instability becomes of interest in 2D van der Waals materials[40,41] and 2D ferroelectricity is identified in 2D group-V binary compounds[42] and elemental monolayers (MLs),[43] which is impossible for their 3D bulk counterparts. Conventionally, the intrinsic ferroelectricity has been reported only for compounds in which the required positive and negative charge centers are carried by different elements. The elemental materials are always stable in centrosymmetric structures without intrinsic ferroelectricity. While, the lack of constrain in one dimension could break the inversion symmetry and drive the 2D elemental layers into a ferroelectric state.[43–45]
The coupling between different ordering parameters is important not only for fundamental research, but also meaningful for cross-control of different orderings in applications. The most striking of such controls is switching magnetic ordering and/or ferroelectric polarization ordering (referred as multiferroicity or magnetoelectric coupling) by electric and magnetic fields, which is important for the design of new electronic devices.[46,47] There are a lot of work and reviews discussing coupling between magnetic and electronic orderings. As far as we know, there is still no review touching interplay between electronic topological ordering and ferroelectric polarization/charge ordering in 2D materials. In this paper, we will systematically report the recent advances about the topology and ferroelectricity in group-V 2D materials. Starting from structure classification of group-V MLs, we will summarize the recent work on 2D group-V MLs about the topology and ferroelectricity with their possible approaches of modulation (e.g., electric field, chemical functionalization, and fabricating the binary systems). Lastly, we would like to discuss the possible coupling between these two interesting quantum properties. Here, the topology refers to the electronic structure, not the topological domain pattern in ferroelectric materials that is the topology of the geometrical structure. We certainly do not make any attempt to cover everything in this mini-review, and the topics chosen are more or less biased by the author’s own research interests. The review mainly focuses on group-V MLs and only the advances in the last several years will be discussed.
Before the discussion of 2D layers, we firstly discuss the structure character of bulk group-V elements. There are five valence electrons in group-V elements and diverse valence states (–3, +3, and +5) are possible for them, resulting in a variety of structural allotropes for bulk of group-V elements at ambient conditions. Phosphorus, the most studied element of group-V, has several allotropes, which are named as white, red, blue, violet, and black phosphorus.[48–51] In addition, amorphous phosphorus is also very popular.[51,52] The discovery of black phosphorus, the most stable allotrope of phosphorus at ambient conditions, is dated back in 1914[50,53] and it crystallizes in parallel puckered layer orthorhombic structure with space group Cmca as shown in Fig.
Although the most stable crystal structure of phosphorus is the α phase with orthorhombic space group, the other elements of group-V (As, Sb, and Bi) favor the β phase due to the weak s–p hybridization.[55,56] The delocalized p–p coupling causes more and more metallic bonding between atoms from As, Sb to Bi and the hexagonal honeycomb structure becomes more stable. For example, the most common and stable allotrope of As and Sb has the rhombohedral layered structure with space group
Generally, there are more crystal allotropes for 2D materials than the corresponding 3D ones due to the lack of periodic boundary constrain along one dimension. For 2D group-V layers, a lot of allotropes have been predicted by theoretical calculations,[58–61] as shown in Fig.
For the β phase, all group-V MLs have buckled honeycomb lattices with two atomic layers, the same as silicene, which are not in the same plane due to the special valence electrons (s2p3) and mixed sp3 hybridization. There is buckling difference for different group-V MLs, but the space group (symmetry) is the same for all of them. For the α phase, all group-V MLs take the puckered lattice with orthogonal structure and there is also buckling difference (Fig.
Topological insulators, as a new quantum state of matter, have attracted intensive research interest due to their applications in spintronics and topological quantum computation as well as academic importance as a novel quantum phenomenon.[75,76] Actually, topological properties in 3D group-V have attracted attention for more than ten years. The valence band of bulk Sb is equivalent to that of a strong topological insulator and bulk Bi is a conventional insulator due to the band inversion at L point. Both bulk Bi and Sb are semimetal with electron and hole pockets at different K points. Since they both have the rhombohedral structure, the Bi–Sb alloy is introduced to open a global bandgap in BZ and maintains the nontrival character.[77]
Two-dimensional TIs also named as QSH insulators are considered as more valuable than 3D TIs for spin transport applications, because the edge states in the former are more robust against back-scattering caused by non-magnetic defects than the surface states in the latter. QSH insulators possess edge states protected by the time reversal symmetry. As stated above, graphene was the first predicted QSH insulator. But, due to the lack of strong SOC, it is difficult to open up a bandgap for experimental observation in graphene. The 2D MLs of group-V elements (P, As, Sb, and Bi) are considered as new emerging 2D materials with much stronger SOC effect than graphene. Moreover, there are diversified ways to tune the topological character of 2D MLs of group-V elements and the cross-control of quantum states may be more easily accessed in the 2D systems. Therefore, as new members in the 2D material family, they can be potential candidates to study the QSH effect under appropriate conditions.
Firstly, we discuss the α phase without buckling (h = 0 in Fig.
As mentioned above, the atomic buckling in α phase is related to the inversion symmetry and quite important for topological properties. Except for α-P, the atomic buckling (h) of other group-V elements could be nonzero and different from each other due to different hybridization between two atomic layers or substrate effect. This buckling breaks the inversion symmetry and degeneracy of crossing points, and even causes the topological phase transition. This effect is most remarkable in α-Bi. Because of the negligible s–p hybridization and the formation of lone pair,[43] the spontaneous buckling height of α-Bi can vary in a wide range (0.0–0.5 Å). The different buckling height results in different pz interaction and thus changes the topological gap. The non-trivial QSH effect (phase transition) is determined by atomic buckling (h), as shown in Fig.
Bismuth ML in β phase has attracted attention immediately after the discovery of graphene due to the similar honeycomb structure. Bismuth is the heaviest group-V element and actually, it is also the heaviest element in periodic table without radioactivity. So, it possesses large SOC effect and is the most promising candidate to achieve 2D QSH phase. In 2006, β-Bi ML had been predicted to be topologically non-trivial with protected edge states[83] and the non-trivial gap is large enough for experimental measurement. Several experimental works provide evidences of the topological edge states in β-Bi ML as shown in Fig.
The β-Sb and β-As in ground state are trivial insulators. However, they can sustain large tensile strain (e.g., 18.4 % for As[85] and 18 % for Sb[86]) that assists the topological phase transition. It was proposed that the topological phase transition from normal insulator to 2D QSH insulator occurs under biaxial strain of 11.7 % and 14.5 % for Sb and As, respectively.[85,86] This large strain may be achieved by some substrate as buffer layer during epitaxial growth. As the second heaviest element of group-V, β-Sb could become 2D TI by other ways. It was predicted that β-Sb becomes 2D TI when the thickness increases between 4 ML and 7 ML, where the surface band splitting provides a robust QSH gap at room temperature.[87] With further increased film thickness, a crossover from the 2D TI to the 3D TI occurs.[87] On the other hand, coupling with substrate could also cause the topological phase transition in β-Sb and most recently, an experimental evidence of nontrivial topological edge states has been observed in epitaxially grown 2D β-Sb islands on copper Cu (111) substrate,[72] where the topological gap lies ∼ 1.5 eV above the Fermi level (Fig.
In general, crystal defects are really important for semiconductors, which could introduce additional defect states in bandgap affecting the transport properties. For topological materials, these defect states in bulk could introduce additional conducting states overcoming the advantage of the protected boundary states within bandgap. In comparison with compound systems, elemental systems are better with less defect problems, which is very important for the application of topological materials. This is one reason that researchers struggle to realize topological character in elemental systems. Recently, due to rising interest in QSH effect in group-V elemental MLs, 2D honeycomb structures of group-V binary compounds have also gained much attention,[90] e.g., SbAs, BiP, BiAs, BiSb, AsP, and SbP. Because all elements are group-V elements with isovalent electrons, there is no additional state appearing in the bandgap and the gap size can be tuned by applying a lattice strain. They all exhibit metal–indirect gap semiconductor–direct gap semiconductor–TI transitions under strain.[91] This broadens the potential candidates of 2D TIs in hexagonal β phase of group-V elements.
Chemical functionalization is an important tool to control electronic properties of materials and oxidation process is easy for group-V elements. This could change the topological character and help the emergence of new topological states. For example, β-P ML (blue phosphorus) is a trivial insulator with large bandgap. This gap size decreases largely after oxidation (P2O2) due to the saturation of the lone pair electrons. And, a moderate strain can easily tune the three bands around the Fermi energy, resulting in tunable quantum phase transition between pseudospin-1 fermions and 2D double Weyl fermions (Figs.
Hydrogenation or halogenation is another effective method to introduce topological phase transition in group-V MLs. Here, we firstly discuss the functionalized β phases. After functionalization, Bi2X2 or Sb2X2 (X = H, F, Cl, Br) were predicted to be topologically non-trivial insulators and stable above room temperature (Figs.
As both α and β phases of group-V MLs have one lone pair of electrons, functionalization by monovalence chemical groups is normally preferred to maintain chemical stability with tunable electronic structures. Although chemical functionalization is a good way to change the electronic structure of 2D materials including the topological properties of 2D group-V MLs, this functionalization is permanent with fixed change of electronic structure. It is hard to reversibly tune the electronic structure by chemical reaction which mostly evolves irreversible bond formation. It is more desirable for device application to change or switch the electronic character between two or more topological states reversibly.
Ferroelectricity is a quantum order characterized by spontaneous alignment of electronic dipoles with switchable macroscopic electronic polarization. Ferroelectric materials with this switchable electrical polarization have attracted much research interest due to their applications in non-volatile memory devices, field effect transistors, sensors, solar cells, and so on.[37,38,99] Normally, ferroelectricity disappears when the film thickness is below a critical value because of the depolarizing electric field and electron screening. A new class of materials, called as hyperferroelectrics, has been identified, which can endure stable polar states in ultrathin atomic layers against unscreened depolarizing field.[39] This requires instability of a longitudinal optical mode in addition to the transverse-optical-mode instability of normal ferroelectrics. However, there is still lack of solid experimental evidence of these materials. Recently, the ferroelectric instability becomes of interest in 2D van der Waals materials. A lot of atomically thin ferroelectric materials have been predicted and experimentally realized in 2D van der Waals materials[100–102] and readers may refer to two recent topic review papers.[41,46] Such depolarization field effect in a true 2D system may no longer be an issue. Moreover, ferroelectric transition driven by electric field is even observed in 2D semimetals,[103,104] expanding our understanding of ferroelectricity.[105] These results show again that dimensionality makes major impact on materials properties and underlying physics.
By scanning tunneling microscope and transport measurement, the 2D ferroelectricity has been confirmed in group-IV monochalcogenides, SnTe ML, which has puckered atomic structure.[100] The key condition of this ferroelectricity is the resonance bonding between cations and anions composing the puckered structure.[106] After that, ferroelectricity has been identified in a lot of 2D systems by replacing elements with isoconvalent state as SnTe, e.g., MX (M = Ge, Sn; X = S, Se).[45] The α phase of 2D group-V elemental MLs has similar structure and the same valence electrons with 2D group-IV monochalcogenides. Thus, they are also possible to present ferroelectricity in puckered α phase.
Ferroelectricity has been mostly observed in compounds of different elements rather than elemental materials. The appearance of FE in elemental materials does not contradict the requirement of broken inversion symmetry. The major obstacle is that most nonmetallic elemental materials are stabilized in nonpolar structures of high symmetry, which prevents the electric polarization. This obstacle could be overcome in 2D system. As mentioned above, the atomic buckling in α phase breaks the inversion symmetry and very recently, Xiao et al. predicted the existence of FE in buckled α-As, α-Sb, and α-Bi elemental MLs for the first time, as shown in Figs.
Compared with the 2D FE group-IV monochalcogenide materials, besides the fundamental distinction (compound vs. elemental), the mechanisms for the ferroelectric polarization of 2D group-V MLs are also different. The group-IV monochalcogenide materials break the centrosymmetry via in-plane distortion from the cubic structure as well as the occupation of lattice sites with different kinds of elements. In comparison, the group-V MLs break centrosymmetry by the out-of-plane atomic-layer buckling, whereas the in-plane distortion does not break the symmetry. As a result, the transformation between two degenerate FE structures of group-IV monochalcogenide materials requires the breaking and reforming bonds between atoms. This is the reason that the resonance bonding between atoms is important and required for the generation of ferroelectronic polarization in group-IV monochalcogenide compounds.[107] Whereas for the group-V monolayers, there is no significant bonding and bond-breaking character in the transformation between two degenerate FE structures. Moreover, the puckered structure of the elemental MLs permits the presence of an AFE phase (for α-Bi), which is absent in the compound materials. The coexistence of FE and AFE phases in the same materials is important. As the symmetry and geometrical structure of AFE phase are different from those of FE phase, its electronic structures could be largely changed in topological nature. This interplay between geometrical phase transition and electronic polarization allows an extraordinary control of the electronic structure (e.g., electronic topological properties) via external field. In addition, the electronic polarization is sensitive to buckling height h and interaction with the substrate, giving us more freedom to engineer the electronic structures and phase transition of the van der Waals heterostructure devices based on group-V elemental MLs.
It has also been predicted that 2D group-V binary compounds composed of both light and heavy group-V elements present ferroelectricity in α or γ phase with notable large and strain tunable spontaneous polarization, e.g., BiN,[107] SbN, BiP.[108] SbP, and SbAs.[109] Such large polarization is caused by the immense electronegativity difference of the light and heavy group-V elements and their displacement in the polarization plane. The mechanism for the ferroelectric transition is almost the same as that of 2D group-IV monochalcogenide compounds requiring the breaking and reforming bonds between atoms. In addition, ferroelectricity is also predicted in halogen-intercalated α-P bilayer without buckling, where the ferroelectric transition is determined by the shift of the halogen atoms covalently bonded to up-layer or down-layer.[110] This concept may be extended to other van der Waals bilayers, but it is really challenging in experiment to precisely functionalize the target material to control these quantum orders.
In hexagonal honeycomb β phase, the out-of-plane atomic-layer buckling does not break the inversion symmetry and the group-V elemental MLs remain centrosymmetric without ferroelectricity no matter whether they are planar or buckled 2D layers. One possible way to break centrosymmetry is to fabricate AB binary monolayer with a bipartite corrugated honeycomb lattice, where the A and B atoms are different elements. Binary group-V compounds show a spontaneous FE polarization in freestanding buckled β phase and their polarization is switched by changing the relative position of the two atoms along out-of-plane direction. The presence of a diatomic basis that breaks the inversion symmetry even in the planar geometry leads to the emergence of Zeeman-like spin-split bands with coupled spin-valley physics analogous to the MoS2 case.[111] Meanwhile, it is mainly responsible for the onset of the FE phase when the honeycomb lattice buckles, allowing for an electrically controllable Rashba-like spin-texture around the valleys, whose chirality is locked to the polarization direction and therefore fully reversible upon FE switching.[42] These spin split bands can be effectively detected by spin-resolved spectroscopic techniques and binary β phase compounds allow for the engineering of 2D spin field-effect-transistors.[112]
Chemical functionalization of polar chemical group is another direct and possible way to transform centrosymmetric β phase into polar structure. It is proposed that ferroelectricity can be introduced into β-As ML by passivation of CH2OCH3 ligand.[90] The fully relaxed structure of CH2OCH3 functionalized β-As is shown in the inset of Fig.
As both ferroelectricity and electronic topological character are closely linked to the geometrical symmetry and structural distortion, the interplay between them can be mediated by geometrical distortion and their coexistence could enable precise control of electronic topology using electric fields (determined by geometrical distortion in phase transition), enhancing the applicability of topological materials in electronics and spintronics. Unfortunately, the crystal structure of 3D group-V is the centrosymmetric one without electronic polarization. Very recently, it is found that both electronic polarization and nontrivial topology can coexist in some compounds containing group-V elements.[115–117] An extremely rich physics strongly links to the ferroelectric properties, ranging from electric control of bulk Rashba effect to the transitions among a 3D topological insulator, normal insulator, and Weyl semimetals. It is also proposed to realize topologically protected Weyl semimetal and nodal line semimetal phases in IV–VI semiconducting compounds (isovalent as group-V in average) with the low-temperature ferroelectric phase.[118,119] These pave a way to explore the coupling between topological properties and electronic polarization in low dimensional systems.
There is more freedom allowing crystal-symmetry variation and distortion in 2D group-V MLs, which is important for the emergence of multiple quantum ordering. In puckered α phase, out-of-plane atomic-layer buckling is flexible and can vary in a wide range. This buckling breaks centrosymmetry and also changes the electronic topological character. For α-Bi, it is an intrinsic 2D TI with QSH effect when the buckling is zero. This corresponds to a paraelectric state. When the buckling is strong and large ( > 0.1 Å), α-Bi becomes a normal insulator without centrosymmetry and corresponds to a ferroelectric state. Thus, the topological phase transition with and without topological protected boundary states may be controlled by the ferro–paraelectric phase transition through geometrical distortion. It is interesting that when the buckling is weak ( > 0.1 Å) under strain, the QSH effect is persisted and coexists with FE in this single phase material. As there are two ferroelectric states with opposite polarizations and they are related to each other via an inversion operation, the chirality and direction of the spin-locked current at boundary rely on the direction of the ferroelectric polarization, as shown in Figs.
One the other hand, AFE could coexist with FE in 2D group-V elemental ML. The crystal symmetry and distortion of AFE are distinctly different from those of FE, resulting in different electronic structure and topological character. For example, AFE and FE states may correspond to an antipolar normal insulator (NI) state and two polar topological insulator (TI) states, respectively, as shown in Fig.
The recent progress in QSH insulators, 2D ferroelectricity, and experimental fabrication of group-V elemental MLs has motivated the researchers to revisit group-V materials. They are potential candidates for realization of 2D TIs and their topological properties can be controlled by electric field, strain, substrate effect, or chemical functionalization. Recent experimental evidences of non-trivial topology in 2D Bi and Sb have robustly boosted the research interest. Moreover, group-V MLs are the first predicted ferroelectric elemental materials in 2D limit, which violate the traditional concept and broaden the 2D ferroelectric family.
Ferroelectricity and QSH effect are two intriguing quantum phenomena in modern condensed matter physics and both of them are related to the integration of Berry phase in BZ. The co-existing QSH effect and ferroelectricity in the same material may lead to novel physical properties, e.g., topological magneto-electric effect.[120] The effective integration of these two properties is not only important for the novel applications in devices, but also leads to the discoveries of unusual quantum phenomena, e.g., the formation of quantum Hall ferroelectric states[121,122] and nonlinear Hall effect.[123,124] In addition, as 2D materials, they can easily grow or deposit on substrates with other quantum properties. Actually, it has been confirmed in experiment that superconductivity can be introduced into 2D Bi ML by deposition on a superconducting substrate due to the superconductor proximity effect.[125] Therefore, 2D group-V MLs provide a good platform to study the interplay between multiple quantum properties.
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