Reversible doping polarity and ultrahigh carrier density in two-dimensional van der Waals ferroelectric heterostructures

Van der Waals semiconductor heterostructures (VSHs) composed of two or more two-dimensional (2D) materials with different band gaps exhibit huge potential for exploiting high-performance multifunctional devices. The application of 2D VSHs in atomically thin devices highly depends on the control of their carrier type and density. Herein, on the basis of comprehensive first-principles calculations, we report a new strategy to manipulate the doping polarity and carrier density in a class of 2D VSHs consisting of atomically thin transition metal dichalcogenides (TMDs) and α-In₂X₃ (X = S, Se) ferroelectrics via switchable polarization field. Our calculated results indicate that the band bending of In₂X₃ layer driven by the FE polarization can be utilized for engineering the band alignment and doping polarity of TMD/In₂X₃ VSHs, which enables us to control their carrier density and type of the VSHs by the orientation and magnitude of local FE polarization field. Inspired by these findings, we demonstrate that doping-free p−n junctions achieved in MoTe₂/In₂Se₃ VSHs exhibit high carrier density (10¹³−10¹⁴ cm⁻²), and the inversion of the VHSs from n−p junctions to p−i−n junctions has been realized by the polarization switching from upward to downward states. This work provides a nonvolatile and nondestructive doping strategy for obtaining programmable p−n van der Waals (vdW) junctions and opens the possibilities for self-powered and multifunctional device applications.     

Electronic and optical properties of 3N-doped graphdiyne/MoS2 heterostructures tuned by biaxial strain and external electric field

The construction of van der Waals (vdW) heterostructures by stacking different two-dimensional layered materials have been recognised as an effective strategy to obtain the desired properties. The 3N-doped graphdiyne (N-GY) has been successfully synthesized in the laboratory. It could be assembled into a supercapacitor and can be used for tensile energy storage. However, the flat band and wide forbidden bands could hinder its application of N-GY layer in optoelectronic and nanoelectronic devices. In order to extend the application of N-GY layer in electronic devices, MoS₂ was selected to construct an N-GY/MoS₂ heterostructure due to its good electronic and optical properties. The N-GY/MoS₂ heterostructure has an optical absorption range from the visible to ultraviolet with a absorption coefficient of 10⁵ cm^-1. The N-GY/MoS₂ heterostructure exhibits a type-Ⅱ band alignment allows the electron-hole to be located on N-GY and MoS₂ respectively, which can further reduce the electron-hole complexation to increase exciton lifetime. The power conversion efficiency of N-GY/MoS₂ heterostructure is up to 17.77%, indicating it is a promising candidate material for solar cells. In addition, the external electric field and biaxial strain could effectively tune the electronic structure. Our results provide a theoretical support for the design and application of N-GY/MoS₂ vdW heterostructures in semiconductor sensors and photovoltaic devices.     

Giant Rashba-like spin-orbit splitting with distinct spin texture in two-dimensional heterostructures

Based on first-principles density functional theory calculation, we discover a novel form of spin-orbit (SO) splitting in two-dimensional (2D) heterostructures composed of a single Bi(111) bilayer stacking with a 2D semiconducting In₂Se₂ or a 2D ferroelectric α-In₂Se₃ layer. Such SO splitting has a Rashba-like but distinct spin texture in the valence band around the maximum, where the chirality of the spin texture reverses within the upper spin-split branch, in contrast to the conventional Rashba systems where the upper branch and lower branch have opposite chirality solely in the region below the band crossing point. The ferroelectric nature of α-In₂Se₃ further enables the tuning of the spin texture upon the reversal of the electric polarization with the application of an external electric field. Detailed analysis based on a tight-binding model reveals that such SO splitting texture results from the interplay of complex orbital characters and substrate interaction. This finding enriches the diversity of SO splitting systems and is also expected to promise for spintronic applications.     

Interfacial defect engineering and photocatalysis properties of hBN/MX2 (M = Mo,W, and X = S,Se heterostructures

Van der Waals (VDW) heterostructures have attracted significant research interest due to their tunable interfacial properties and potential applications in many areas such as electronics, optoelectronic, and heterocatalysis. In this work, the influences of interfacial defects on the electronic structures and photocatalytic properties of hBN/MX₂ (M = Mo, W, and X=S, Se) are studied using density functional theory calculations. The results reveal that the band alignment of hBN/MX₂ can be adjusted by introducing vacancies and atomic doping. The type-I band alignment of the host structure is maintained in the heterostructure with n-type doping in the hBN sublayer. Interestingly, the band alignment changed into the type-II heterostructrue due to V_B defect and p-type doping is introduced into the hBN sublayer. This can conduce to the separation of photo-generated electron-hole pairs at the interfaces, which is highly desired for heterostructure photocatalysis. In addition, two Z-type heterostructures including hBN(Be_B)/MoS₂, hBN(Be_B)/MoSe₂, and hBN(V_N)/MoSe₂ are achieved, showing the decreasing of band gap and ideal redox potential for water splitting. Our results reveal the possibility of engineering the interfacial and photocatalysis properties of hBN/MX₂ heterostructures via interfacial defects.     

应力调控BlueP/XTe2(X=Mo,W)范德瓦耳斯异质结电子结构及光学性质理论研究

通过第一性原理计算探讨了蓝磷烯与过渡金属硫化物MoTe₂/WTe₂形成范德瓦耳斯异质结的电子结构和光学性质,以及施加双轴应力对相关性质的影响.计算结果表明,形成BlueP/XTe₂(X=Mo,W)异质结,二者能带排列为间接带隙type-Ⅱ并有较强的红外光吸收,同时屏蔽特性增强.随压缩应力增加,BlueP/XTe₂转变为直接带隙type-Ⅱ能带排列最后转变为金属性;随拉伸应力增加,异质结转变为间接带隙type-Ⅰ能带排列.外加应力也能有效调控异质结的光吸收性质,随压缩应力增加吸收边红移,光吸收响应拓展至中红外光谱区且吸收系数增大;BlueP/MoTe₂较BlueP/WTe₂在中红外至红外光区间表现出更强的光吸收响应;静态介电常数ε1(0)大幅增加.结果表明,压缩应力对BlueP/MoTe₂和BlueP/WTe₂能带排列、光吸收特性均有显著的调控作用,其中BlueP/MoTe₂对调控更敏感,这些特性也使BlueP/XTe₂异质结在窄禁带中红外半导体材料及光电器件具有令人期待的应用价值.     

Photoemission oscillation in epitaxially grown van der Waals β-In2Se3/WS2 heterobilayer bubbles

Thin films of millimeter-scale continuous monolayer WS₂ have been grown on SiO₂/Si substrate, followed by the deposition of β-In₂Se₃ crystals on monolayer WS₂ to prepare In₂Se₃/WS₂ van de Waals heterostructures by a two-step chemical vapor deposition (CVD) method. After the growth of In₂Se₃ at elevated temperatures, high densities of In₂Se₃/WS₂ heterostructure bubbles with monolayer to multilayer β-In₂Se₃ crystals atop are observed. Fluorescence of the resultant β-In₂Se₃/WS₂ heterostructure is greatly enhanced in intensity upon the formation of bubbles, which are evidenced by the Newton's rings in optical image owing to constructive and destructive interference. In photoluminescence (PL) mapping images of monolayer β-In₂Se₃/monolayer WS₂ heterobilayer bubble, significant oscillatory behavior of emission intensity is demonstrated due to constructive and destructive interference. However, oscillatory behaviors of peak position are also observed and come from a local heating effect induced by an excitation laser beam. The oscillatory mechanism of PL is further verified by changing the exterior pressure of bubbles placed in a home-made vacuum chamber. In addition, redshifted in peak position and broadening in peak width are observed due to strain effect during decreasing the exterior pressure of bubbles.     

Thermally induced band hybridization in bilayer-bilayer MoS_2/WS_2 heterostructure

Transition metal dichalcogenides(TMDs), being valley selectively, are an ideal system hosting excitons. Stacking TMDs together to form heterostructure offers an exciting platform to engineer new optical and electronic properties in solid-state systems. However, due to the limited accuracy and repetitiveness of sample preparation, the effects of interlayer coupling on the electronic and excitonic properties have not been systematically investigated. In this report, we study the photoluminescence spectra of bilayer-bilayer MoS_2/WS_2 heterostructure with a type Ⅱ band alignment. We demonstrate that thermal annealing can increase interlayer coupling in the van der Waals heterostructures, and after thermally induced band hybridization such heterostructure behaves more like an artificial new solid, rather than just the combination of two individual TMD components. We also carry out experimental and theoretical studies of the electric controllable direct and indirect infrared interlayer excitons in such system. Our study reveals the impact of interlayer coupling on interlayer excitons and will shed light on the understanding and engineering of layer-controlled spin-valley configuration in twisted van der Waals heterostructures.     

(Cu,N)共掺杂TiO2/MoS2异质结的电子和光学性能:杂化泛函HSE06

在密度泛函理论的基础上,系统地研究了Cu/N（共）掺杂的TiO₂/MoS₂异质结体系的几何结构、电子结构和光学性质.计算发现,TiO₂/MoS₂异质结的带隙相比于纯的TiO₂（101）表面明显变小,Cu/N（共）掺杂TiO₂/MoS₂异质结体系的禁带宽度也明显地减小,这导致光子激发能量的降低和光吸收能力的提高.通过计算Cu/N（共）掺杂TiO₂/MoS₂的差分电荷密度,发现光生电子与空穴积累在掺杂后的TiO₂（101）表面和单层MoS₂之间,这表明掺杂杂质体系可以有效地抑制光生电子-空穴对的复合.此外,我们计算了在不同压力下TiO₂/MoS₂异质结的几何、电子和光学性质,发现适当增加压力可以有效提高异质结的光吸收性能.本文结果表明,Cu/N（共）掺杂TiO₂/MoS₂异质结和对TiO₂/MoS₂异质结加压都能有效地提高材料的光学性能.     

基于AsP/MoS2异质结的偏振光电探测器

线偏振光的探测能力是评价偏振光电探测器件的重要指标。黑砷磷(AsP)是一种较为稳定的平面内各向异性材料,由于其面内结构各向异性,其对线偏振光较为敏感,在偏振探测领域有着重要的应用潜力。本文介绍了一种基于AsP/MoS2的高度偏振敏感光电探测器。由于AsP各向异性的光吸收、MoS2有效的载流子收集和输运能力以及范德华异质结对暗电流的抑制作用,该光电探测器实现了大于300的电流开关比,0.27 A/W的电流光响应度以及2×10^10 Jones的比探测率。更重要的是,此类光电探测器在638 nm波段实现了高达3.06二向色性比的偏振特性。这些实验结果表明AsP/MoS2异质结构在偏振光电探测领域有着广阔的应用前景。     

石墨烯封装单层二硫化钼的热稳定性研究

将单层二硫化钼用石墨烯进行封装,构造了石墨烯和二硫化钼的范德瓦耳斯异质结构,并且分别在氩气（Ar）和氢气（H₂）氛围下,详细研究了被封装的二硫化钼的热稳定性.结果表明：在氩气氛围中,石墨烯封装的二硫化钼在400–1000℃下一直保持稳定,而石墨烯和氧化硅上裸露的二硫化钼在1000℃时几乎全部分解;在氢气氛围中,石墨烯封装的二硫化钼在400–1000℃下一直稳定存在,而石墨烯和氧化硅上裸露的二硫化钼在800℃下已经完全分解.综上可得,在氩气和氢气的氛围下,被石墨烯封装的二硫化钼的热稳定性得到了显著的提高.该研究通过用石墨烯将单层的二硫化钼进行封装以提高其热稳定性,在未来以单层二硫化钼作为基础材料的电子器件中,可以保证其在高温下能够正常工作.该研究也为提高其他二维材料的热稳定性提供了一种可行的方法和思路.     

二硫化钼/石墨烯异质结的界面结合作用及其对带边电位影响的理论研究

采用基于色散修正的平面波超软赝势方法研究了二硫化钼/石墨烯异质结的界面结合作用及其对电荷分布和带边电位的影响.研究表明二硫化钼与石墨烯之间可以形成范德瓦耳斯力结合的稳定堆叠结构.通过能带结构计算,发现二硫化钼与石墨烯的耦合导致二硫化钼成为n型半导体,石墨烯转变成小带隙的p型体系.并通过电子密度差分图证实了界面内二硫化钼附近聚集负电荷,石墨烯附近聚集正电荷,界面内形成的内建电场可以抑制光生电子-空穴对的复合.石墨烯的引入可以调制二硫化钼的能带,使其导带底上移至-0.31 eV,提高了光生电子还原能力,有利于光催化还原反应.     

Two dimensional GeO2/MoSi2N4 van der Waals heterostructures with robust type-II band alignment

Constructing two-dimensional (2D) van der Waals heterostructures (vdWHs) can expand the electronic and optoelectronic applications of 2D semiconductors. However, the work on the 2D vdWHs with robust band alignment is still scarce. Here, we employ a global structure search approach to construct the vdWHs with monolayer MoSi₂N₄ and wide-bandgap GeO₂. The studies show that the GeO₂/MoSi₂N₄ vdWHs have the characteristics of direct structures with the band gap of 0.946 eV and type-II band alignment with GeO₂ and MoSi₂N₄ layers as the conduction band minimum (CBM) and valence band maximum (VBM), respectively. Also, the direct-to-indirect band gap transition can be achieved by applying biaxial strain. In particular, the 2D GeO₂/MoSi₂N₄ vdWHs show a robust type-II band alignment under the effects of biaxial strain, interlayer distance and external electric field. The results provide a route to realize the robust type-II band alignment vdWHs, which is helpful for the implementation of optoelectronic nanodevices with stable characteristics.     

Valley-polarized quantum anomalous Hall effect in van der Waals heterostructures based on monolayer jacutingaite family materials

We numerically study the general valley polarization and anomalous Hall effect in van der Waals (vdW) heterostructures based on monolayer jacutingaite family materials Pt₂AX₃ (A = Hg, Cd, Zn; X = S, Se, Te). We perform a systematic study on the atomic, electronic, and topological properties of vdW heterostructures composed of monolayer Pt₂AX₃ and two-dimensional ferromagnetic insulators. We show that four kinds of vdW heterostructures exhibit valley-polarized quantum anomalous Hall phase, i.e., Pt₂HgS₃/NiBr₂, Pt₂HgSe₃/CoBr₂, Pt₂HgSe₃/NiBr₂, and Pt₂ZnS₃/CoBr₂, with a maximum valley splitting of 134.2 meV in Pt₂HgSe₃/NiBr₂ and sizable global band gap of 58.8 meV in Pt₂HgS₃/NiBr₂. Our findings demonstrate an ideal platform to implement applications on topological valleytronics.     

Energy band alignment of 2D/3D MoS2/4H-SiC heterostructure modulated by multiple interfacial interactions

The interfacial properties of MoS₂/4H-SiC heterostructures were studied by combining first-principles calculations and X-ray photoelectron spectroscopy. Experimental (theoretical) valence band offsets (VBOs) increase from 1.49 (1.46) to 2.19 (2.36) eV with increasing MoS₂ monolayer (1L) up to 4 layers (4L). A strong interlayer interaction was revealed at 1L MoS₂/SiC interface. Fermi level pinning and totally surface passivation were realized for 4H-SiC (0001) surface. About 0.96e per unit cell transferring forms an electric field from SiC to MoS₂. Then, 1L MoS₂/SiC interface exhibits type I band alignment with the asymmetric conduction band offset (CBO) and VBO. For 2L and 4L MoS₂/SiC, Fermi level was just pinning at the lower MoS₂ 1L. The interaction keeps weak vdW interaction between upper and lower MoS₂ layers. They exhibit the type II band alignments and the enlarged CBOs and VBOs, which is attributed to weak vdW interaction and strong interlayer orbital coupling in the multilayer MoS₂. High efficiency of charge separation will emerge due to the asymmetric band alignment and built-in electric field for all the MoS₂/SiC interfaces. The multiple interfacial interactions provide a new modulated perspective for the next-generation electronics and optoelectronics based on the 2D/3D semiconductors heterojunctions.     

Computational screening of vdWs heterostructures of BSe with MoSe2 and WSe2 as sustainable hydrogen production materials

Recently, fabricating type-II vertical van der Waals (vdWs) heterostructure is a promising material for hydrogen production. The absorption capability, charge density distributions, band alignments and electronic properties of the monolayers and heterostructures are systematically investigated using computational studies. Using ab initio molecular dynamics, binding energy and phonon calculations, the stability of the heterostructures are verified. Both heterostructures are type-II materials, which can increase the separation of charge carriers. Moreover, the charge density difference and the potential drop across the interface of MSe₂/BSe creates a high built-in electric field that can prevent the recombination of charge carriers. We found that the visible-light optical properties of both heterostructures are much enhanced with suitable bandgap energy for water splitting. The band alignment suggests that the heterostructures straddle water redox potentials in acid solutions (0 < pH < 7). Our study predicted that MSe₂/BSe vdW heterostructures have great potential for photocatalytic hydrogen production.     

First-principles investigation of the valley and electrical properties of carbon-doped α-graphyne-like BN sheet

Based on ab initio density functional theory calculations, we demonstrate that two carbon-doped boron nitride analog of α-graphyne structures, B_3C_2N_3 and BC_6 N monolayers, are two-dimensional direct wide band gap semiconductors, and there are two inequivalent valleys in the vicinities of the vertices of their hexagonal Brillouin zones. Besides, B_3C_2N_3 and BC_6 N monolayers exhibit relatively high carrier mobilities, and their direct band gap feature is robust against the biaxial strain. More importantly, the energetically most favorable B_3C_2N_3 and BC_6 N bilayers also have direct wide band gaps, and valley polarization could be achieved by optical helicity. Finally, we show that BC_6 N monolayer might have high efficiency in photo-splitting reactions of water, and a vertical van der Waals heterostructure with a type-II energy band alignment could be designed using B_3C_2N_3 and BC_6 N monolayers. All the above-mentioned characteristics make B_3C_2N_3 and BC_6 N monolayers, bilayers, and their heterostructures recommendable candidates for applications in valleytronic devices,metal-free photocatalysts, and photovoltaic cells.     

Strain drived band aligment transition of the ferromagnetic VS_2/C_3N van der Waals heterostructure

Exploring two-dimensional(2 D) magnetic heterostructures is essential for future spintronic and optoelectronic devices.Herein,using first-principle calculations,stable ferromagnetic ordering and colorful electronic properties are established by constructing the VS_2/C_3 N van der Waals(vdW) heterostructure.Unlike the semiconductive properties with indirect band gaps in both the VS_2 and C_3 N monolayers,our results indicate that a direct band gap with type-Ⅱ band alignment and p-doping characters are realized in the spin-up channel of the VS_2/C_3 N heterostructure,and a typical type-Ⅲband alignment with a broken-gap in the spin-down channel.Furthermore,the band alignments in the two spin channels can be effectively tuned by applying tensile strain.An interchangement between the type-Ⅱ and type-Ⅲ band alignments occurs in the two spin channels,as the tensile strain increases to 4%.The attractive magnetic properties and the unique band alignments could be useful for prospective applications in the next-generation tunneling devices and spintronic devices.     

Interface engineering of transition metal dichalcogenide/GaN heterostructures: Modified broadband for photoelectronic performance

The GaN-based heterostructures are widely used in optoelectronic devices, but the complex surface reconstructions and lattice mismatch greatly limit the applications. The stacking of two-dimensional transition metal dichalcogenide (TMD = MoS₂, MoSSe and MoSe₂) monolayers on reconstructed GaN surface not only effectively overcomes the larger mismatch, but also brings about novel electronic and optical properties. By adopting the reconstructed GaN (0001) surface with adatoms (N-ter GaN and Ga-ter GaN), the influences of complicated surface conditions on the electronic properties of heterostructures have been investigated. The passivated N-ter and Ga-ter GaN surfaces push the mid-gap states to the valence bands, giving rise to small bandgaps in heterostructures. The charge transfer between Ga-ter GaN surface and TMD monolayers occurs much easier than that across the TMD/N-ter GaN interfaces, which induces stronger interfacial interaction and larger valence band offset (VBO). The band alignment can be switched between type-I and type-II by assembling different TMD monolayers, that is, MoS₂/N-ter GaN and MoS₂/Ga-ter GaN are type-II, and the others are type-I. The absorption of visible light is enhanced in all considered TMD/reconstructed GaN heterostructures. Additionally, MoSe₂/Ga-ter GaN and MoSSe/N-ter GaN have larger conductor band offset (CBO) of 1.32 eV and 1.29 eV, respectively, extending the range from deep ultraviolet to infrared regime. Our results revel that the TMD/reconstructed GaN heterostructures may be used for high-performance broadband photoelectronic devices.     

Effect of deposited temperatures of the buffer layer on the band offset of CZTS/In_2S_3 heterostructure and its solar cell performance

The effect of the deposition temperature of the buffer layer In_2S_3 on the band alignment of CZTS/In_2S_3 heterostructures and the solar cell performance have been investigated.The In_2S_3 films are prepared by thermal evaporation method at temperatures of 30,100,150,and 200 ℃,respectively.By using x-ray photoelectron spectroscopy(XPS),the valence band offsets(VBO) are determined to be-0.28 ±0.1,-0.28 ±0.1,-0.34 ±0.1,and-0.42 ±0.1 eV for the CZTS/In_2S_3heterostructures deposited at 30,100,150,and 200 ℃,respectively,and the corresponding conduction band offsets(CBO)are found to be 0.3 ±0.1,0.41 ±0.1,0.22±0.1,and 0.01 ±0.1 eV,respectively.The XPS study also reveals that interdiffusion of In and Cu occurs at the interface of the heterostructures,which is especially serious at 200 ℃ leading to large amount of interface defects or the formation of CuInS_2 phase at the interface.The CZTS solar cell with the buffer layer In_2S_3 deposited at 150 ℃ shows the best performance due to the proper CBO value at the heterostructure interface and the improved crystal quality of In_2S_3 film induced by the appropriate deposition temperature.The device prepared at 100 ℃presents the poorest performance owing to too high a value of CBO.It is demonstrated that the deposition temperature is a crucial parameter to control the quality of the solar cells.     

酞菁铜与MoS_2(0001)范德瓦耳斯异质结研究

利用光电子能谱、原子力显微镜以及低能电子衍射等表面研究手段系统研究了真空沉积生长的酞菁铜薄膜与衬底MoS2(0001)之间的范德瓦耳斯异质结界面电子结构和几何结构.角分辨光电子能谱清楚地再现了MoS2(0001)衬底在Γ点附近的能带结构.低能电子衍射结果表明,CuPc薄膜在MoS2(0001)表面沿着衬底表面[11ˉ20],[1ˉ210]和[ˉ2110]三个晶向有序生长,反映了衬底对CuPc的影响.原子力显微镜结果表明,CuPc在MoS2衬底上遵循层状-岛状生长模式:在低生长厚度下(单层薄膜厚度约为0.3 nm),CuPc分子平面平行于MoS2表面上形成均匀连续的薄膜;在较高的沉积厚度下,CuPc沿衬底晶向形成棒状晶粒,表现出明显的各向异性.光电子能谱显示界面偶极层为0.07 eV,而且能谱在膜厚1.2 nm饱和,揭示了酞菁铜与MoS2(0001)范德瓦耳斯异质结的能级结构.