Van Der Waals Heterostructures Research Articles

Infrared optoelectronics in twisted black phosphorus

Electrons and holes, fundamental charge carriers in semiconductors, dominate optical transitions and detection processes. Twisted van der Waals (vdW) heterostructures offer an effective approach to manipulate radiation, separation, and collection processes of electron-hole pairs by creating an atomically sharp interface. Here, we demonstrate that twisted interfaces in vdW layered black phosphorus (BP), an infrared semiconductor with highly anisotropic crystalline structure and properties, can significantly alter both recombination and separation processes of electron-hole pairs. On the one hand, the twisted interface breaks the symmetry of optical transition states resulting in infrared light emission of originally symmetry-forbidden optical states along the zigzag direction. On the other hand, spontaneous electronic polarization/bulk photovoltaic effect is generated at the twisted interface enabling effective separation of electron-hole pairs without external voltage bias. This is supported by first-principles calculations and repeated experiments at various twisted angles from 0 to 90°. Importantly, these phenomena can be observed in twisted heterostructures with thickness beyond two-dimensional. Our results suggest that the engineering of vdW twisted interfaces is an effective strategy for manipulating the optoelectronic properties of materials and constructing functional devices.

Wafer-scale integration of two-dimensional perovskite oxides towards motion recognition

Two-dimensional semiconductors have shown great potential for the development of advanced intelligent optoelectronic systems. Among them, two-dimensional perovskite oxides with compelling optoelectronic performance have been thriving in high-performance photodetection. However, harsh synthesis and defect chemistry severely limit their overall performance and further large-scale heterogeneous integration. Here, we report the wafer-scale integration of highly oriented nanosheets by introducing a charge-assisted oriented assembly film-formation process and confirm its universality and scalability. The shallow-trap dominance induced by structural optimization endows the device with a distinguished performance balance, including high photosensitivity close to that of single nanosheet units and fast response speed. An integrated ultra-flexible 256-pixel device demonstrates the versatility of material-to-substrate integration and conformal imaging functionality. Moreover, the device achieves efficient recognition of multidirectional motion trajectories with an accuracy of over 99.8%. Our work provides prescient insights into the large-area fabrication and utilization of 2D perovskite oxides in advanced optoelectronics.

Novel Quantum States of Exciton-Floquet Composites: Electron-Hole Entanglement and Information.

Coulomb exchange between distinct electron-hole modes, i.e., exciton and Floquet states, in two-dimensional semiconductors is explored. Coherent ultrafast mixing of the exciton and Floquet states under weak optical pumping is investigated through a theoretical description of time-resolved and angle-resolved photoemission spectroscopy (tr-ARPES) in an extended Haldane model that includes the electron-hole Coulomb interaction. Two branches of novel quantum states are found in the form of bosonic exciton-Floquet composites, which result from exchange coupling due to the Coulomb interaction. Furthermore, tr-ARPES could be directly employed for the density matrix element of the biparticle subsystem of photoelectron and hole, and electron-hole entanglement and information could be further explored. This finding suggests a unique platform to study the buildup and dephasing of novel exciton-Floquet composites and to resolve the information carried by them, which would enable the pursuit of new reconfigurable devices based on two-dimensional semiconductors.

Quantum tunneling high-speed nano-excitonic modulator

High-speed electrical control of nano-optoelectronic properties in two-dimensional semiconductors is a building block for the development of excitonic devices, allowing the seamless integration of nano-electronics and -photonics. Here, we demonstrate a high-speed electrical modulation of nanoscale exciton behaviors in a MoS2 monolayer at room temperature through a quantum tunneling nanoplasmonic cavity. Electrical control of tunneling electrons between Au tip and MoS2 monolayer facilitates the dynamic switching of neutral exciton- and trion-dominant states at the nanoscale. Through tip-induced spectroscopic analysis, we locally characterize the modified recombination dynamics, resulting in a significant change in the photoluminescence quantum yield. Furthermore, by obtaining a time-resolved second-order correlation function, we demonstrate that this electrically-driven nanoscale exciton-trion interconversion achieves a modulation frequency of up to 8 MHz. Our approach provides a versatile platform for dynamically manipulating nano-optoelectronic properties in the form of transformable excitonic quasiparticles, including valley polarization, recombination, and transport dynamics.

High performance self-driven broadband photodetector for polarized imaging based on novel ZrS3/ReSe2 van der Waals heterojunction

The distinctive characteristics of anisotropic two-dimensional (2D) materials, including in-plane anisotropy of optical absorption and carrier mobility, render them exceptionally suitable for application in the field of polarization detection and as a novel platform for the polarization imaging. Meanwhile, the consolidation of diverse functionalities within a single photodetector is highly anticipated to meet the demands of some special scenarios. Herein, a novel ZrS3/ReSe2 van der Waals (vdWs) heterostructure device was successfully constructed to realize polarization-sensitive, self-powered, and broadband photodetection and imaging. Owing to the built-in electric field of the type-II band alignment within the heterojunction, the device achieves a self-powered photoresponse ranging from 300 to 980 nm, an ultralow dark currentt ∼1 pA, and a commendable rise/decay time of 0.35/0.28 ms. Additionally, it has been demonstrated that the self-driven photodetector possesses a polarization-sensitivity with a notable anisotropic ratio about 2.02 (1.98) under 490 nm (980 nm) light illumination with zero bias, coupled with an excellent repeatability and stability. Furthermore, we also demonstrate the polarization imaging capabilities of the device in visible and near-infrared spectrum, realizing a contrast-enhanced degree of linear polarization imaging. This work paves a new platform to develop heterojunction photodetectors for high performance polarization-sensitive photodetection and next-generation polarized imaging.

Moiré-engineered light-matter interactions in MoS2/WSe2 heterobilayers at room temperature

Moiré superlattices in van der Waals heterostructures represent a highly tunable quantum system, attracting substantial interest in both many-body physics and device applications. However, the influence of the moiré potential on light-matter interactions at room temperature has remained largely unexplored. In our study, we demonstrate that the moiré potential in MoS2/WSe2 heterobilayers facilitates the localization of interlayer exciton (IX) at room temperature. By performing reflection contrast spectroscopy, we demonstrate the importance of atomic reconstruction in modifying intralayer excitons, supported by the atomic force microscopy experiment. When decreasing the twist angle, we observe that the IX lifetime becomes longer and light emission gets enhanced, indicating that non-radiative decay channels such as defects are suppressed by the moiré potential. Moreover, through the integration of moiré superlattices with silicon single-mode cavities, we find that the devices employing moiré-trapped IXs exhibit a significantly lower threshold, one order of magnitude smaller compared to the device utilizing delocalized IXs. These findings not only encourage the exploration of many-body physics in moiré superlattices at elevated temperatures but also pave the way for leveraging these artificial quantum materials in photonic and optoelectronic applications.

Atomic and electronic properties of 2D Chevrel phases: A case study of the superatomic two-dimensional semiconductor Re6Se8Cl2

The design of two-dimensional superatomic materials, which form their atomic structures through covalently bonded clusters with variable chemical compositions, will enable the development of new materials with promised electronic properties that are beneficial for modern nanoelectronics. This paper presents ab initio calculations of the atomic and electronic structures of both bulk and 2D Re6Se8Cl2. The calculations were carried out using density functional theory, incorporating noncollinear spin density and the pseudopotential method. The results include data on the atomic structure, band gap value, formation energy of the Re6Se8Cl2 2D layer, and the redistribution of atomic charges within the structures. The differences in effective masses for electrons and holes in the two-dimensional and bulk Re6Se8Cl2 materials are demonstrated, along with an explanation of how these differences impact their transport properties. The findings are expected to be of great significance for the design, synthesis, and implementation of new two-dimensional superatomic materials with controlled properties in modern nanoelectronics.

Recent Developments on Novel 2D Materials for Emerging Neuromorphic Computing Devices

The rapid advancement of artificial intelligent and information technology has led to a critical need for extremely low power consumption and excellent efficiency. The capacity of neuromorphic computing to handle large amounts of data with low power consumption has garnered a lot of interest during the last few decades. For neuromorphic applications, 2D layered semiconductor materials have shown a pivotal role due to their distinctive properties. This comprehensive review provides an extensive study of the recent advancements in 2D materials‐based neuromorphic devices especially in multiterminal synaptic devices, two‐terminal synaptic devices, neuronal devices, and the integration of synaptic and neuronal devices. Herein, a wide range of potential applications of memory, computation, adaptation, and artificial intelligence is incorporated. Finally, the limitations and challenges of neuromorphic devices based on novel 2D materials are discussed. Thus, this review aims to illuminate the design and fabrication of neuromorphic devices based on van der Waals (vdW) heterostructure materials, leveraging promising engineering techniques to excel the applications and potential of neuromorphic computing for hardware implementations.

Building Asymmetric Zn-N3 Bridge between 2D Photocatalyst and Co-catalyst for Directed Charge Transfer toward Efficient H2O2 Synthesis.

Two-dimensional (2D) polymeric semiconductors are a class of promising photocatalysts; however, it remains challenging to facilitate their interlayer charge transfer for suppressed in-plane charge recombination and thus improved quantum efficiency. Although some strategies, such as π-π stacking and van der Waals interaction, have been developed so far, directed interlayer charge transfer still cannot be achieved. Herein, we report a strategy of forming asymmetric Zn-N3 units that can bridge nitrogen (N)-doped carbon layers with polymeric carbon nitride nanosheets (C3N4-Zn-N(C)) to address this challenge. The symmetry-breaking Zn-N3 moiety, which has an asymmetric local charge distribution, enables directed interfacial charge transfer between the C3N4 photocatalyst and the N-doped carbon co-catalyst. As evidenced by femtosecond transient absorption spectroscopy, charge separation can be significantly enhanced by the interfacial asymmetric Zn-N3 bonding bridges. As a result, the designed C3N4-Zn-N(C) catalyst exhibits dramatically enhanced H2O2 photosynthesis activity, outperforming most of the reported C3N4-based catalysts. This work highlights the importance of tailoring interfacial chemical bonding channels in polymeric photocatalysts at the molecular level to achieve effective spatial charge separation.

Tunable Schottky barriers and magnetoelectric coupling driven by ferroelectric polarization reversal of MnI3/In2Se3 multiferroic heterostructures

Two-dimensional (2D) multiferroic materials are recognized as promising candidates for next-generation nanodevices due to their tunable magnetoelectric coupling and distinctive physical phenomena. In this study, we proposed a novel 2D multiferroic van der Waals heterostructure (vdWH) by stacking atomic layers of ferroelectric In2Se3 and ferromagnetic MnI3. Using first-principles calculations, we found that the MnI3/In2Se3 vdWH exhibit robust metallic conductivity across various spin and polarization states, preserving the distinctive band characteristics of isolated In2Se3 and MnI3. However, the alignment of Fermi levels causes the conduction band minimum (CBM) and valence band maximum (VBM) of In2Se3 and MnI3 to shift relative to their original band structures. Remarkably, the MnI3/In2Se3 with the upward polarization state of In2Se3 exhibits an Ohmic contact. Switching the polarization direction of In2Se3 from upward to downward can transform the MnI3/In2Se3 vdWH from an Ohmic contact to a p-type Schottky contact, while also modifying its dipole moment, magnetic strength and direction. Based on these properties of MnI3/In2Se3 vdWH, we designed the field-effect transistors (FETs) with high on/off rates and nonvolatile data storage device. Furthermore, the Schottky barrier heights (SBHs), magnetic moment, and dipole moment of MnI3/In2Se3 vdWH can also be effectively regulated by reducing the interlayer distance. With the continuous reduction of the interlayer distance of MnI3/In2Se3 vdWH, its easy magnetization axis is expected to shift from in-plane to out-of-plane. These findings offer new insights for the design and development of the next-generation spintronic and nonvolatile memory nanodevices.

Unprecedented Hole Concentration of NiSe2 Electrodes Leading to Hole Degeneration of Entire WSe2 Channels.

Semimetal electrodes for 2D semiconductors have been extensively studied; however, research on p-type semimetals has been limited due to the scarcity of materials that satisfy both high work functions and low resistances. In response, we investigated the behavior of NiSe2 as an electrode. Utilizing a novel co-evaporation method that suppresses oxidation and contamination, we synthesized NiSe2 demonstrating a high work function of 5.53 eV, a low resistance of 5.81 × 10-5 Ω cm, and a record hole concentration exceeding 1023 cm-3. We confirmed that when WSe2 comes into contact with NiSe2, the Fermi level of WSe2 falls below the work function of NiSe2, leading to complete hole degeneration of the channel. This unusual Fermi level alignment correlates with the high hole concentration in NiSe2 and the maximum energy level of its hole pockets. Our research provides new insights into how an electrode's hole concentration affects channel behavior.

Designing High-Performance Nanoscale Spin-MOSFET Devices by Using Two-Dimensional Half-Metallic Cr2Se3.

Constructing nanoscale spin devices has been a crucial pursuit in the field of nano spintronics. Here, by using the density functional theory (DFT) and nonequilibrium Green's function (NEGF) method, high-performance nanoscale spin-MOSFET devices using half-metallic 2D Cr2Se3 as electrodes are theoretically designed. Specifically, seven typical two-dimensional (2D) semiconductors, Sb, Bi, BP, BAs, MoTe2, WTe2, and WSeTe (with two different contacting surfaces), are considered here as the channel materials. The properties of contact interfaces between these 2D semiconductors and half-metallic 2D Cr2Se3 are first investigated. It is found that except BP and BAs (having Schottky contacts with Cr2Se3), the other 2D semiconductors have vertical Ohmic contacts with Cr2Se3 among which Cr2Se3/Sb, Cr2Se3/MoTe2, Cr2Se3/WTe2, Cr2Se3/WSeTe-Se, and Cr2Se3/WSeTe-Te retain the half-metallic characteristic. Then, these 2D semiconductors with Ohmic vertical contacts are further used to construct spin-MOSFET devices. The results show that devices constructed by half-metallic vertical contacting systems have nearly 100% SIE and therefore giant MR (>107%) when the gate voltage varies. Furthermore, four designed spin-MOSFET devices, namely, Cr2Se3/MoTe2, Cr2Se3/WTe2, Cr2Se3/WSeTe-Se, and Cr2Se3/WSeTe-Te spin-MOSFET have high efficient gate modulations on the magnitude of completely spin-polarized source-drain current with Cr2Se3/WTe2 having the smallest SS value of 134.1 mV/dec. The calculations suggest that Cr2Se3 is a good candidate for constructing spin-MOSFET devices. Our study sheds light on the design of high-performance nanoscale spin-MOSFET devices by using two-dimensional half-metallic electrodes.

Light‐State Rectification Behaviors Induced by Interlayer Excitons in Mixed‐Dimensional Single‐Crystalline Perovskite Heterostructures

AbstractStacking different layers into van der Waals heterostructures (vdWHs) provides an attractive approach to integrating intrinsic prominent properties of the constituents. Mixed‐dimensional vdWHs that can interact with external fields are particularly intriguing because they host interlayer excitons (IXs) and thereby exhibiting rich physical phenomena and novel device behaviors. However, previous studies of IXs have primarily focused on TMDs systems, leaving the excitonic phenomena and correlated physics in perovskite heterostructures poorly understood. Here, the 2D‐3D ((BA)2PbBr4‐CsPbBr3) single‐crystalline perovskite vdWHs are designed to discover the modulation effects of IX states on the optical and optoelectronic properties. Interestingly, the vdWHs exhibit a newly emerging IXs emission at 546 nm and an obvious broadening phenomenon in FWHM. The vdWHs‐based photodetectors display novel light‐state rectification behaviors that can change the output photocurrents from fully off states to rectified states after illumination, resulting in a high rectification ratio up to 24342 and an obvious enhanced on/off ratio of 7000. The attractive results are attributed to the presence of IX states, which facilitate carrier hopping at the interfaces. This work establishes mixed‐dimensional single‐crystalline perovskite heterolayers as a highly adaptable platform for exciton research and applications.

3D/2D lead-free halide perovskite CsSnBr3/MoX (X = Se2, SSe, S2) heterostructures for high-efficiency solar cell: Interface engineering strategies and transition of band alignments

The rapid progress in the fabrication of van der Waals (vdW) heterostructures based on perovskite has significantly advanced the fields of optoelectronics and solar cells by integrating the exceptional properties of different materials. Overall, perovskite-based vdW heterostructures display unique functional characteristics due to their varied type-I, type-II, and type-III energy band configurations. However, it is a challenge to achieve flexible regulation of band edge alignment in heterostructures for different applications. Using first-principles density functional theory, we systematically study the electronic and optical properties of vdW heterostructures system consisting of three-dimensional lead-free all-inorganic halide perovskite materials CsSnBr3 and MoX (X = Se2, SSe, S2). The research results show that in the CsSnBr3/MoX vdW heterostructures, type I, II, and III transitions of band arrangements are achieved through interface engineering strategy to adapt to different applications. Meanwhile, by calculating the light absorption efficiency of the constructed 3D/2D vdW heterostructures, it was found that the interface effect enhances the optical absorption range and intensity of the perovskite-based heterostructures. The theoretically estimated power conversion efficiency (PCE) of the heterostructure thin-film solar cell reaches 21.4 %. The results of our research indicate that the controllable band alignment of CsSnBr3/MoX heterostructures has significant potential for future applications in optoelectronics.

Ferroelectric Semimetals with α-Bi/SnSe van der Waals Heterostructures and Their Topological Currents.

We show that proximity effects can be utilized to engineer van der Waals heterostructures (vdWHs) displaying semimetallic spin-ferroelectricity locking, where ferroelectricity and semimetallic spin states are confined to different layers, but are correlated by means of proximity effects. Our findings are supported by first principles calculations involving α-Bi/SnSe bilayers. We show that such systems support ferroelectrically switchable nonlinear anomalous Hall effect originating from large Berry curvature dipoles as well as direct and inverse spin Hall effects with giant bulk spin-charge interconversion efficiencies. The giant efficiencies are consequences of the proximity-induced semimetallic nature of low energy electron states, which are shown to behave as two-dimensional pseudo-Weyl fermions by means of symmetry analysis and first principles calculations as well as direct angle-resolved photoemission spectroscopy measurements.

Understanding the Impact of Contact-Induced Strain on the Electrical Performance of Monolayer WS2 Transistors.

Two-dimensional (2D) electronics require low contact resistance (RC) to approach their fundamental limits. WS2 is a promising 2D semiconductor that is often paired with Ni contacts, but their operation is not well understood considering the nonideal alignment between the Ni work function and the WS2 conduction band. Here, we investigate the effects of contact size on nanoscale monolayer WS2 transistors and uncover that Ni contacts impart stress, which affects the WS2 device performance. The strain applied to the WS2 depends on contact size, where long (1 μm) contacts (RC ≈ 1.7 kΩ·μm) show a 78% reduction in RC compared to shorter (0.1 μm) contacts (RC ≈ 7.8 kΩ·μm). We also find that thermal annealing can relax the WS2 strain in long-contact devices, increasing RC to 8.5 kΩ·μm. These results reveal that thermo-mechanical phenomena can significantly influence 2D semiconductor-metal contacts, presenting opportunities to optimize device performance through nanofabrication and thermal budget.

Theoretical study of the strong piezo-phototronic effect in 2D monochalcogenides for multi-junction solar cells

The piezophototronic effect is a new scientific area that investigates the synergistic interactions of piezoelectric, semiconductor, and photoexcitation features. This effect is seen in crystals lacking inversion symmetry, where applied strain alters electronic transport and provides a way to modify material properties. Monolayer 2D semiconductors, such as transition metal dichalcogenides (TMDCs) and group IV monochalcogenides, have higher piezoelectric coefficients than conventional piezoelectric materials. This study proposes the development of a stable, high-performance multijunction solar cell (MJSC) leveraging the piezo-phototronic effect. The emphasis is on single-type 5-layer 2D monochalcogenides (SnS, SnSe, GeS, and GeSe) with the assistance of strain engineering. Surprisingly, the ultrathin parallel-connected solar cell achieves an electric power conversion efficiency of over 31% when tested under blackbody radiation, surpassing the recognized Shockley–Queisser (S-Q) limit. The piezophototronic effect improves solar cell performance while also addressing voltage mismatch issues. This work introduces a novel approach to developing and manufacturing high-efficiency and robust monolayer multijunction photovoltaic solar cells (MJPSC) based on 2D monochalcogenides.

Constructing the Fulde-Ferrell-Larkin-Ovchinnikov State in a CrOCl/NbSe2 van der Waals Heterostructure.

Time reversal symmetry breaking in superconductors, resulting from external magnetic fields or spontaneous magnetization, often leads to unconventional superconducting properties. In this way, an intrinsic phenomenon called the Fulde-Ferrell-Larkin-Ovchinnikov (FFLO) state may be realized by the Zeeman effect. Here, we construct the FFLO state in an artificial CrOCl/NbSe2 van der Waals (vdW) heterostructure by utilizing the superconducting proximity effect of NbSe2 flakes. The proximity-induced superconductivity demonstrates a considerably weak gap of about 0.12 meV, and the in-plane upper critical field reveals the behavior of the FFLO state. First-principles calculations uncover the origin of the proximitized superconductivity, which indicates the importance of Cr vacancies or line defects in CrOCl. Moreover, the FFLO state could be induced by the inherent large spin splitting in CrOCl. Our findings not only provide a practical scheme for constructing the FFLO state but also inspire the discovery of an exotic FFLO state in other two-dimensional vdW heterostructures.

Unraveling the Spin-to-Charge Current Conversion Mechanism and Charge Transfer Dynamics at the Interface of Graphene/WS2 Heterostructures at Room Temperature.

We report experimental investigations of spin-to-charge current conversion and charge transfer (CT) dynamics at the interface of the graphene/WS2 van der Waals heterostructure. Pure spin current was produced by the spin precession in the microwave-driven ferromagnetic resonance of a permalloy film (Py=Ni81Fe19) and injected into the graphene/WS2 heterostructure through a spin pumping process. The observed spin-to-charge current conversion in the heterostructure is attributed to the inverse Rashba-Edelstein effect (IREE) at the graphene/WS2 interface. Interfacial CT dynamics in this heterostructure was investigated based on the framework of the core-hole clock (CHC) approach. The results obtained from spin pumping and CHC studies show that the spin-to-charge current conversion and charge transfer processes are more efficient in the graphene/WS2 heterostructure compared to isolated WS2 and graphene films. The results show that the presence of WS2 flakes improves the current conversion efficiency. These experimental results are corroborated by density functional theory (DFT) calculations, which reveal (i) Rashba spin-orbit splitting of graphene orbitals and (ii) electronic coupling between graphene and WS2 orbitals. This study provides valuable insights for optimizing the design and performance of spintronic devices.

Electrostatically Designing Materials and Interfaces.

Collective electrostatic effects arise from the superposition of electrostatic potentials of periodically arranged (di)polar entities and are known to crucially impact the electronic structures of hybrid interfaces. Here, it is discussed, how they can be used outside the beaten paths of materials design for realizing systems with advanced and sometimes unprecedented properties. The versatility of the approach is demonstrated by applying electrostatic design not only to metal-organic interfaces and adsorbed (complex) monolayers, but also to inter-layer interfaces in van der Waals heterostructures, to polar metal-organic frameworks (MOFs), and to the cylindrical pores of covalent organic frameworks (COFs). The presented design ideas are straightforward to simulate and especially for metal-organic interfaces also their experimental implementation has been amply demonstrated. For van der Waals heterostructures, the needed building blocks are available, while the required assembly approaches are just being developed. Conversely, for MOFs the necessary growth techniques exist, but more work on advanced linker molecules is required. Finally, COF structures exist that contain pores decorated with polar groups, but the electrostatic impact of these groups has been largely ignored so far. All this suggest that the dawn of the age of electrostatic design is currently experienced with potential breakthroughs lying ahead.