(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.     

Tunable electronic properties of GaS-SnS2 heterostructure by strain and electric field

Vertically stacked heterostructures have received extensive attention because of their tunable electronic structures and outstanding optical properties. In this work, we study the structural, electronic, and optical properties of vertically stacked GaS-SnS₂ heterostructure under the frame of density functional theory. We find that the stacked GaS-SnS₂ heterostructure is a semiconductor with a suitable indirect band gap of 1.82 eV, exhibiting a type-II band alignment for easily separating the photo-generated carriers. The electronic properties of GaS-SnS₂ heterostructure can be effectively tuned by an external strain and electric field. The optical absorption of GaS-SnS₂ heterostructure is more enhanced than those of the GaS monolayer and SnS₂ monolayer in the visible light region. Our results suggest that the GaS-SnS₂ heterostructure is a promising candidate for the photocatalyst and photoelectronic devices in the visible light region.     

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.     

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.     

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.     

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.     

钙钛矿CsPbX3(X=Cl,Br,I)与五环石墨烯范德瓦耳斯异质结的界面相互作用和光电性能的第一性原理研究

异质结工程是一种提高半导体材料光电性能的有效方法.本文构建了全无机钙钛矿CsPbX₃(X=Cl,Br,I)和二维五环石墨烯penta-graphene(PG)的新型范德瓦耳斯(vdW)异质结,利用第一性原理研究了CsPbX₃-PG异质结不同界面接触的稳定性,进而计算了稳定性较好的Pb-X接触界面异质结的电子结构和光电性能.研究结果表明,CsPbX₃-PG(X=Cl,Br,I)异质结具有II型能带排列特征,能级差距由Cl向I逐渐缩小,具有良好的光生载流子分离能力和电荷输运性质.此外,研究发现CsPbX₃-PG异质结能有效拓宽材料的光吸收谱范围,并能显著提高其光吸收能力,尤其是CsPbI₃具有最优的光吸收性能.经理论估算,CsPbX₃-PG的光电功率转换效率(PCE)可高达21%.这些结果表明,全无机金属卤化物钙钛矿CsPbX₃-PG异质结可以有效地提高半导体材料的光电性能,预期在光电转换器件中具有重要的应用潜力.     

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.     

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.     

Tuning band alignment and optical properties of 2D van der Waals heterostructure via ferroelectric polarization switching

Favourable band alignment and excellent visible light response are vital for photochemical water splitting. In this work, we have theoretically investigated how ferroelectric polarization and its reversibility in direction can be utilized to modulate the band alignment and optical absorption properties. For this objective, 2D van der Waals heterostructures (HTSs) are constructed by interfacing monolayer MoS₂ with ferroelectric In2Se3. We find the switch of polarization direction has dramatically changed the band alignment, thus facilitating different type of reactions. In In₂Se₃/MoS₂/In₂Se₃ heterostructures, one polarization direction supports hydrogen evolution reaction and another polarization direction can favour oxygen evolution reaction. These can be used to create tuneable photocatalyst materials where water reduction reactions can be selectively controlled by polarization switching. The modulation of band alignment is attributed to the shift of reaction potential caused by spontaneous polarization. Additionally, the formed type-II van der Waals HTSs also significantly improve charge separation and enhance the optical absorption in the visible and infrared regions. Our results pave a way in the design of van der Waals HTSs for water splitting using ferroelectric materials.     

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.     

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。     

High-sensitive phototransistor based on vertical HfSe2/MoS2 heterostructure with broad-spectral response

Van der Waals heterostructures based on the two-dimensional (2D) semiconductor materials have attracted increasing attention due to their attractive properties. In this work, we demonstrate a high-sensitive back-gated phototransistor based on the vertical HfSe₂/MoS₂ heterostructure with a broad-spectral response from near-ultraviolet to near-infrared and an efficient gate tunability for photoresponse. Under bias, the phototransistor exhibits high responsivity of up to 1.42×10³ A/W, and ultrahigh specific detectivity of up to 1.39×10¹⁵ cm·Hz^1/2·W^-1. Moreover, it can also operate under zero bias with remarkable responsivity of 10.2 A/W, relatively high specific detectivity of 1.43×10¹⁴ cm·Hz^1/2·W^-1, ultralow dark current of 1.22 fA, and high on/off ratio of above 10⁵. These results should be attributed to the fact that the vertical HfSe₂/MoS₂ heterostructure not only improves the broadband photoresponse of the phototransistor but also greatly enhances its sensitivity. Therefore, the heterostructure provides a promising candidate for next generation high performance phototransistors.     

Electronic and optical properties of van der Waals vertical heterostructures based on two-dimensional transition metal dichalcogenides: First-principles calculations

Four vertical heterostructures based on two-dimensional transition-metal dichalcogenides (TMDs) – MoS₂/GeC, MoSe₂/GeC, WS₂/GeC, and WSe₂/GeC, were studied by density functional theory calculations to investigate their structure, electronic characteristics, principle of photogenerated electron–hole separation, and optical-absorption capability. The optimized heterostructures were formed by van der Waals (vdW) forces and without covalent bonding. Their most stable geometric configurations and band structures display type-II band alignment, which allows them to spontaneously separate photogenerated electrons and holes. The charge difference and built-in electric field across the interface of these vdW heterostructures also contribute to preventing the photogenerated electron–hole recombination. Finally, the high optical absorption of the four TMD-based vdW heterostructures in the visible and near-infrared regions indicates their suitability for photocatalytic, photovoltaic, and optical devices.     

Ultrafast interlayer photocarrier transfer in graphene–MoSe_2 van der Waals heterostructure

We report the fabrication and photocarrier dynamics in graphene–MoSe_2 heterostructures. The samples were fabricated by mechanical exfoliation and manual stacking techniques. Ultrafast laser measurements were performed on the heterostructure and MoSe_2 monolayer samples. By comparing the results, we conclude that photocarriers injected in MoSe_2 of the heterostructure transfer to graphene on an ultrafast time scale. The carriers in graphene alter the optical absorption coefficient of MoSe_2. These results illustrate the potential applications of this material in optoelectronic devices.     

Te掺杂单层MoS2的电子结构与光电性质

采用基于密度泛函理论的第一性原理计算,研究了Te掺杂对单层MoS₂能带结构、电子态密度和光电性质的影响。结果表明,本征单层MoS₂属于直接带隙半导体材料,其禁带宽度为1.64 eV。本征单层MoS₂的价带顶主要由S-3p态电子和Mo-4d态电子构成,而其导带底则主要由Mo-4d态电子和S-3p态电子共同决定;Te掺杂单层MoS₂为间接带隙半导体材料,其禁带宽度为1.47 eV。同时通过Te掺杂,使单层MoS₂的静态介电常数增大,禁带宽度变窄,吸收光谱产生红移,研究结果为单层MoS₂在光电器件方面的应用提供了理论基础。     

Tunable electronic and optical properties of SnC/BAs heterostructure by external electric field and vertical strain

Based on the first-principles method, we investigate the electronic structure of SnC/BAs van der Waals (vdW) heterostructure and find that it has an intrinsic type-II band alignment with a direct band gap of 0.22 eV, which favors the separation of photogenerated electron–hole pairs. The band gap can be effectively modulated by applying vertical strain and external electric field, displaying a large alteration of band gap via the strain and experiencing an indirect-to-direct band gap transition. Moreover, the band gap of the heterostructure varies almost linearly with external electric field, and the semiconductor-to-metal transition can be realized in the presence of a strong electric field. The calculated band alignment and the optical absorption reveal that the SnC/BAs heterostructure could present an excellent light-harvesting performance. Our designed heterostructure is expected to have great potential applications in nanoelectronic devices and photovoltaics and optical properties.     

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.     

Observation of magnetoresistance in CrI3/graphene van der Waals heterostructures

Two-dimensional ferromagnetic van der Waals (2D vdW) heterostructures have opened new avenues for creating artificial materials with unprecedented electrical and optical functions beyond the reach of isolated 2D atomic layered materials, and for manipulating spin degree of freedom at the limit of few atomic layers, which empower next-generation spintronic and memory devices. However, to date, the electronic properties of 2D ferromagnetic heterostructures still remain elusive. Here, we report an unambiguous magnetoresistance behavior in CrI₃/graphene heterostructures, with a maximum magnetoresistance ratio of 2.8%. The magnetoresistance increases with increasing magnetic field, which leads to decreasing carrier densities through Lorentz force, and decreases with the increase of the bias voltage. This work highlights the feasibilities of applying two-dimensional ferromagnetic vdW heterostructures in spintronic and memory devices.     

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.