WS_2与WSe_2单层膜中的A激子及其自旋动力学特性研究

单层过渡金属硫化物由于其特有的激子效应以及强自旋-谷耦合性质,在光电子学及谷电子学等方面有着很广阔的应用前景.利用超快时间分辨光谱,本文系统地比较了两类钨基单层硫化物(WS_2和WSe_2)的A-激子动力学和谷自旋弛豫特性.实验结果表明, WS_2单层膜的A-激子弛豫表现为双指数过程,而对于WSe_2,其A-激子衰减表现为三指数过程,且激子的寿命远长于前者. WS_2谷自旋极化弛豫表现为单指数衰减,其寿命约0.35 ps,主要由电子-空穴交换作用所主导.而对于WSe_2,谷自旋弛豫表现出双指数弛豫特性:一个寿命为0.5 ps的快过程和一个寿命为28 ps的慢过程.快过程的弛豫来源于电子-空穴交换作用,而慢过程则由于自旋晶格散射形成暗激子的过程.通过调谐抽运光波长,进一步证实WSe_2较WS_2更容易形成暗激子.     

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.     

Interfacial properties of 2D WS2 on SiO2 substrate from X-ray photoelectron spectroscopy and first-principles calculations

Two-dimensional (2D) WS₂ films were deposited on SiO₂ wafers, and the related interfacial properties were investigated by high-resolution X-ray photoelectron spectroscopy (XPS) and first-principles calculations. Using the direct (indirect) method, the valence band offset (VBO) at monolayer WS₂/SiO₂ interface was found to be 3.97 eV (3.86 eV), and the conduction band offset (CBO) was 2.70 eV (2.81 eV). Furthermore, the VBO (CBO) at bulk WS₂/SiO₂ interface is found to be about 0.48 eV (0.33 eV) larger due to the interlayer orbital coupling and splitting of valence and conduction band edges. Therefore, the WS₂/SiO₂ heterostructure has a Type I energy-band alignment. The band offsets obtained experimentally and theoretically are consistent except the narrower theoretical bandgap of SiO₂. The theoretical calculations further reveal a binding energy of 75 meV per S atom and the totally separated partial density of states, indicating a weak interaction and negligible Fermi level pinning effect between WS₂ monolayer and SiO₂ surface. Our combined experimental and theoretical results provide proof of the sufficient VBOs and CBOs and weak interaction in 2D WS₂/SiO₂ heterostructures.     

单层WSe2、MoSe2激子发光的压力诱导K-Λ交互转变

采用机械剥离法在金刚石对顶砧中制备了单层WSe₂和MoSe₂样品,利用高压微区荧光光谱测量技术,在氩传压介质环境下对其激子发光行为进行了高压调控研究。其中单层WSe₂的中性和负电激子演化趋势在2.43 GPa处出现拐点,单层MoSe₂中性激子发光在3.7 GPa处发生了劈裂。结合第一性原理计算分析,确认该不连续现象的产生机制为压力诱导的导带底K-Λ交互转变。该结果可以扩大至整个二维层状材料体系,为发展激子器件垫定基础。     

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.     

Mechanical properties of lateral transition metal dichalcogenide heterostructures

Transition metal dichalcogenide(TMD)monolayers attract great attention due to their specific structural,electronic and mechanical properties.The formation of their lateral heterostructures allows a new degree of flexibility in engineering electronic and optoelectronic dervices.However,the mechanical properties of the lateral heterostructures are rarely investigated.In this study,a comparative investigation on the mechanical characteristics of 1H,IT'and 1H/1T'heterostructure phases of different TMD monolayers including molybdenum disulfide(M0S₂)molybdenum diselenide(MoSe₂),Tungsten disulfide(WS₂),and Tungsten diselenide(WSe₂)was conducted by means of density functional theory(DFT)calculations.Our results indicate that the impact of the lateral heterostructures has a relatively weak mechanical strength for all the TMD monolayers.The significant correlation bet ween the mechanical properties of the TMD monolayers and their structural phases can be used to tune their stiffness of the materials.Our findings,therefore,suggest a novel strategy to manipulate the mechanical characteristics of TMDs by engineering their structural phases for their practical applications.     

单层与双层WSe2纳米片层的光致发光

采用气相沉积法制备了WSe₂二维纳米材料,对其低温光致发光谱进行了研究。结果表明：随着WSe₂层数的增加,其光致发光强度单调下降;当WSe₂层数从单层增加为双层时,其发光强度急剧下降,表明其能带结构已从直接带隙转变为间接带隙。进一步研究了双层WSe₂的变温光致发光谱,发现随着温度的升高,双层WSe₂发光峰中A峰峰位的变化基本符合半导体带隙的温度变化规律,而I峰峰位红移与温度基本成线性关系,表明双层WSe₂同时存在间接和直接跃迁,且直接跃迁和间接跃迁特性不同。     

Giant enhancement of photoluminescence emission in monolayer WS2by femtosecond laser irradiation

Monolayer transition metal dichalcogenides have emerged as promising mat erials for opt oelectTonic and nanophotonic devices.However,the low photoluminescence(PL)quantum yield(QY)hinders their various potential applications.Here we engineer and enhance the PL intensity of monolayer WS₂by femtosecond laser irradiation.More than two orders of magnitude enhancement of PL intensity as compared to the as-prepared sample is determined.Furthermore,the engineering time is shortened by three orders of magnitude as compared to the improvement of PL intensity by continuous-wave laser irradiation.Based on the evolution of PL spectra,we attribute the giant PL enhancement to the conversion from trion emission to exciton,as well as the improvement of the QY when exciton and trion are localized to the new-formed defects.We have created microstructures on the monolayer WS₂based on the enhancement of PL intensity,where the engineered structures can be stably stored for more than three years.This flexible approach with the feature of excellent long-term storage stability is promising for applications in information storage,display technology,and opto electronic devices.     

基于磁圆二向色谱的单层MoS_2激子能量和线宽温度依赖特性

以二硫化钼(MoS_2)为代表的过渡金属硫属化物属于二维层状材料,样品可以薄至单层.单层MoS_2是一种直接带隙半导体,在纳米逻辑器件、高速光电探测、纳米激光等领域具有广阔的应用前景.在实际应用中,温度是影响半导体材料能带结构和性质的主要因素之一.因此研究单层二维材料能带的温度依赖特性对理解其物理机理以及开展器件应用具有重要的意义.目前,在广泛采用的测量单层MoS_2反射谱的研究中,激子峰往往叠加在一个很强的光谱背底上,难以准确分辨激子的峰位和线宽.基于自行搭建的显微磁圆二向色谱系统,研究了单层MoS_2在65—300 K温度范围内的反射谱和磁圆二向色谱,结果表明磁圆二向色谱在研究单层材料激子能量和线宽方面具有明显的优势.通过分析变温的磁圆二向色谱,得到了不同温度下的A,B激子的跃迁能量和线宽.通过对激子能量和线宽的温度依赖关系进行拟合,进一步讨论了声子散射对激子线宽的影响.     

二硫化钨/石墨烯异质结的界面相互作用及其肖特基调控的理论研究

采用第一性原理方法研究了二硫化钨/石墨烯异质结的界面结合作用以及电子性质,结果表明在二硫化钨/石墨烯异质结中,其界面相互作用是微弱的范德瓦耳斯力.能带计算结果显示异质结中二硫化钨和石墨烯各自的电子性质得到了保留,同时,由于石墨烯的结合作用,二硫化钨呈现出n型半导体.通过改变界面的层间距可以调控二硫化钼/石墨烯异质结的肖特基势垒类型,层间距增大,肖特基将从p型转变为n型接触.三维电荷密度差分图表明,负电荷聚集在二硫化钨附近,正电荷聚集在石墨烯附近,从而在界面处形成内建电场.肖特基势垒变化与界面电荷流动密切相关,平面平均电荷密度差分图显示,随着层间距逐渐增大,界面电荷转移越来越弱,且空间电荷聚集区位置向石墨烯层方向靠近,导致费米能级向上平移,证实了肖特基势垒随着层间距的增加由p型接触向n型转变.本文的研究结果将为二维范德瓦耳斯场效应管的设计与制作提供指导.     

A self-driven photodetector based on a SnS2/WS2 van der Waals heterojunction with an Al2O3 capping layer

Photodetectors based on two-dimensional (2D) materials have attracted considerable attention because of their unique properties. To further improve the performance of self-driven photodetectors based on van der Waals heterojunctions, a conductive band minimum (CBM) matched self-driven SnS₂/WS₂ van der Waals heterojunction photodetector based on a SiO₂/Si substrate has been designed. The device exhibits a positive current at zero voltage under 365 nm laser illumination. This is attributed to the built-in electric field at the interface of the SnS₂ and WS₂ layer, which will separate and transport the photogenerated carriers, even at zero bias voltage. In addition, the Al₂O₃ layer is covered by the surface of the SnS₂/WS₂ photodetector to further improve the performance, because the Al₂O₃ layer will introduce tensile stress on the surface of the 2D materials leading to a higher electron concentration and smaller effective mass of electrons in the films. This work provides an idea for the research of self-driven photodetectors based on a van der Waals heterogeneous junction.     

(TiO2)12量子环及过渡金属化合物掺杂对其电子性质影响的密度泛函理论研究

本文采用第一性原理中基于密度泛函理论(DFT)的广义梯度近似(GGA)方法, 设计了一种新的(TiO₂)₁₂ 量子环结构, 研究了它的几何结构、平均结合能及电子云分布等属性. 在此新型结构的基础上, 分别采用过渡金属化合物MoS₂, MoSe₂, MoTe₂, WS₂, WSe₂和WTe₂进行掺杂, 并分析了掺杂后体系的几何结构及电子属性(如平均结合能、能级结构、HOMO-LUMO轨道电子云密度分布和电子态密度等). 计算结果表明: (TiO₂)₁₂量子环直径为1.059 nm, 呈中心对称分布, 且所有原子组成一个二维平面结构, 使其几何结构比较稳定, 另外该量子环HOMO-LUMO轨道电子云分布均匀, 且能隙为3.17 eV, 与半导体材料TiO₂晶体的能隙的实验值(3.2 eV)非常接近. 掺杂后量子环的能隙均大幅减小, 其中WTe₂的掺杂结果能隙最小, 仅为0.61 eV, MoTe₂的掺杂结果能隙最大, 为1.16 eV, 也比掺杂前减小约2.0 eV. 其他掺杂结果的能隙都在1 eV左右, 变化不大. 这个能隙的TiO₂可以利用大部分的太阳光能, 使TiO₂具有更为广泛的应用.     

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。     

Optical anisotropy and the direction of polarization of exciton emissions in a semiconductor quantum dot:Effect of heavy-and light-hole mixing

The dependence of the directions of polarization of exciton emissions, fine structure splittings(FSS), and polarization anisotropy on the light-and heavy-hole(LH–HH) mixing in semiconductor quantum dots(QDs) is investigated using a mesoscopic model. In general, all QDs have a four-fold exciton ground state. Two exciton states have directions of polarization in the growth-plane, while the other two are along the growth direction of the QD. The LH–HH mixing does affect the FSS and polarization anisotropy of bright exciton states in the growth-plane in the low symmetry QDs(e.g., C_(2V),C_S, C_1), while it has no effect on the FSS and polarization anisotropy in high symmetry QDs(e.g., C_(3V), D_(2d)). When the hole ground state is pure HH or LH, the bright exciton states in the growth-plane are normal to each other. The LH–HH mixing affects the relative intensities and directions of bright exciton states in the growth-plane of the QD. The polarization anisotropy of exciton emissions in the growth-plane of the QD is independent of the phase angle of LH–HH mixing but strongly depends on the magnitude of LH–HH mixing in low symmetry QDs.     

First-principles calculation of the structural,electronic, elastic,and optical properties of sulfur-doping ε-GaSe crystal

The structural,electronic,mechanical properties,and frequency-dependent refractive indexes of GaSe_(1-x)S_x(x=0,0.25,and 1) are studied by using the first-principles pseudopotential method within density functional theory.The calculated results demonstrate the relationships between intralayer structure and elastic modulus in GaSe_(1-x)S_x(x=0,0.25,and 1).Doping of ε-GaSe with S strengthens the Ga-X bonds and increases its elastic moduli of C_(11) and C_(66).Born effective charge analysis provides an explanation for the modification of cleavage properties about the doping of e-GaSe with S.The calculated results of band gaps suggest that the distance between intralayer atom and substitution of S_(Se),rather than interlayer force,is a key factor influencing the electronic exciton energy of the layer semiconductor.The calculated refractive indexes indicate that the doping of ε-GaSe with S reduces its refractive index and increases its birefringence.     

Passively Q-switched dual-wavelength Yb:LSO laser based on tungsten disulphide saturable absorber

We demonstrate a passively Q-switched Yb:LSO laser based on tungsten disulphide(WS_2) saturable absorber operating at 1034 nm and 1056 nm simultaneously. The saturable absorbers were fabricated by spin coating method. With low speed, the WS_2 nanoplatelets embedded in polyvinyl alcohol could be coated on a BK7 glass substrate coated with high-refractive-index thin polymer. The shortest pulse width of 1.6 μs with a repetition rate of 76.9 k Hz is obtained. As the pump power increases to 9 W, the maximum output power is measured to be 250 m W, corresponding to a single pulse energy of 3.25 μJ. To the best of our knowledge, this is the first time to obtain dual-wavelength Q-switched solid-state laser using few-layer WS_2 nanoplatelets.     

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.     

A field-effect WSe2/Si heterojunction diode

It is significant to develop a heterogeneous integration technology to promote the application of two-dimensional (2D) materials in silicon roadmap. In this paper, we reported a field-effect WSe₂/Si heterojunction diode based on ambipolar 2D WSe₂ and silicon on insulator (SOI). Our results indicate that the device exhibits a p-n diode behavior with a rectifying ratio of ～ 300 and an ideality factor of 1.37. As a photodetector, it has optoelectronic properties with a response time of 0.13 ms, responsivity of 0.045 A/W, detectivity of 4.5×10¹⁰ Jones and external quantum efficiency (EQE) of 8.9 %. Due to the ambipolar behavior of the WSe₂, the rectifying and optoelectronic properties of the heterojunction diode can be modulated by the gate electrical field, enabling various potential applications such as logic optoelectronic devices and neuromorphic optoelectronic devices for in-sensor computing circuits. Thanks to the process based on the mature SOI technique, our field-effect heterojunction diode should have obvious advantages in device isolation and integration.     

Excited state biexcitons in monolayer WSe2 driven by vertically grown graphene nanosheets with high-density electron trapping edges

Interface engineering in atomically thin transition metal dichalcogenides (TMDs) is becoming an important and powerful technique to alter their properties, enabling new optoelectronic applications and quantum devices. Interface engineering in a monolayer WSe₂ sample via introduction of high-density edges of standing structured graphene nanosheets (GNs) is realized. A strong photoluminescence (PL) emission peak from intravalley and intervalley trions at about 750 nm is observed at the room temperature, which indicated the heavily p-type doping of the monolayer WSe₂/thin graphene nanosheet-embedded carbon (TGNEC) film heterostructure. We also successfully triggered the emission of biexcitons (excited state biexciton) in a monolayer WSe₂, via the electron trapping centers of edge quantum wells of a TGNEC film. The PL emission of a monolayer WSe₂/GNEC film is quenched by capturing the photoexcited electrons to reduce the electron-hole recombination rate. This study can be an important benchmark for the extensive understanding of light–matter interaction in TMDs, and their dynamics.     

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.