Two-dimensional Heterostructures Research Articles

2D van der Waals Heterostructure with Tellurene Floating-Gate for Wide Range and Multi-Bit Optoelectronic Memory.

Intensive research on optoelectronic memory (OEM) devices based on two-dimensional (2D) van der Waals heterostructures (vdWhs) is being conducted due to their distinctive advantages for electrical-optical writing and multilevel storage. These features make OEM a promising candidate for the logic of reconfigurable operations. However, the realization of nonvolatile OEM with broadband absorption (from visible to infrared) and a high switching ratio remains challenging. Herein, we report a nonvolatile OEM based on a heterostructure consisting of rhenium disulfide (ReS2), hexagonal boron nitride (hBN) and tellurene (2D Te). The 2D Te-based floating-gate (FG) device exhibits excellent performance metrics, including a high switching on/off ratio (∼106), significant endurance (>1000 cycles) and impressive retention (>104 s). In addition, the narrow band gap of 2D Te endows the device with broadband optical programmability from the visible to near-infrared regions at room temperature. Moreover, by applying different gate voltages, light wavelengths, and laser powers, multiple bits can be successfully generated. Additionally, the device is specifically designed to enable reconfigurable inverter logic circuits (including AND and OR gates) through controlled electrical and optical inputs. These significant findings demonstrate that the 2D vdWhs with a 2D Te FG are a valuable approach in the development of high-performance OEM devices.

Effects of anisotropy on the electronic structure and nonlinear optical rectification in a quantum dot with hydrogen molecular ion

In this study, the effects of anisotropy and quantum dot size on energy levels and nonlinear optical rectification of a D_{2}^{ + } molecular complex confined to a two-dimensional quantum dot are investigated. The energy eigenvalues and corresponding eigenfunctions of the resulting eigenvalue equation are obtained using the adiabatic approach and the two-dimensional diagonalization method. We conclude that the evolution of the energy spectrum depends predominantly on the anisotropy-induced change of geometric confinement size. In addition, it has been determined that the peak position of the nonlinear optical rectification shifts to lower or higher energies as the asymmetry of the system increases, depending on whether the QD is in the oblate or prolate case. This feature can be considered an advantage in tuning the nonlinear optical properties of systems based on two-dimensional semiconductor heterostructures.

Engineering correlated insulators in bilayer graphene with a remote Coulomb superlattice.

Electron superlattices allow the engineering of correlated and topological quantum phenomena. The recent emergence of moiré superlattices in two-dimensional heterostructures has led to exciting discoveries related to quantum phenomena. However, the requirement for the moiré pattern poses stringent limitations, and its potential cannot be switched on and off. Here, we demonstrate remote engineering and on/off switching of correlated states in bilayer graphene. Employing a remote Coulomb superlattice realized by localized electrons in twisted bilayer WS2, we impose a Coulomb superlattice in the bilayer graphene with period and strength determined by the twisted bilayer WS2. When the remote superlattice is turned off, the two-dimensional electron gas in the bilayer graphene is described by a Fermi liquid. When it is turned on, correlated insulating states at both integer and fractional filling factors emerge. This approach enables in situ control of correlated quantum phenomena in two-dimensional materials hosting a two-dimensional electron gas.

Catalytic synergy of WS2-anchored PdSe2 for highly sensitive hydrogen gas sensor.

Hydrogen (H2) is widely used in industrial processes and is one of the well-known choices for storage of renewable energy. H2 detection has become crucial for safety in manufacturing, storage, and transportation due to its strong explosivity. To overcome the issue of explosion, there is a need for highly selective and sensitive H2 sensors that can function at low temperatures. In this research, we have adequately fabricated an unreported van der Waals (vdWs) PdSe2/WS2 heterostructure, which exhibits exceptional properties as a H2 sensor. The formation of these heterostructure devices involves the direct selenization process using chemical vapor deposition (CVD) of Pd films that have been deposited on the substrate of SiO2/Si by DC sputtering, followed by drop casting of WS2 nanoparticles prepared by a hydrothermal method onto device substrates including pre-patterned electrodes. The confirmation of the heterostructure has been done through the utilization of powder X-ray diffraction (XRD), depth-dependent X-ray photoelectron spectroscopy (XPS) and field-emission scanning electron microscopy (FE-SEM) techniques. Also, the average roughness of thin films is decided by Atomic Force Microscopy (AFM). The comprehensive research shows that the PdSe2/WS2 heterostructure-based sensor produces a response that is equivalent to 67.4% towards 50 ppm H2 at 100 °C. The response could be a result of the heterostructure effect and the superior selectivity for H2 gas in contrast to other gases, including NO2, CH4, CO and CO2, suggesting tremendous potential for H2 detection. Significantly, the sensor exhibits fast response and a recovery time of 31.5 s and 136.6 s, respectively. Moreover, the explanation of the improvement in gas sensitivity was suggested by exploiting the energy band positioning of the PdSe2/WS2 heterostructure, along with a detailed study of variations in the surface potential. This study has the potential to provide a road map for the advancement of gas sensors utilizing two-dimensional (2D) vdWs heterostructures, which exhibit superior performance at low temperatures.

Two-dimensional trilayer heterostructures with cascade dual Z-schemes to achieve efficient hydrogen evolution reaction

Electronic properties and diabatic molecular dynamics simulations reveal that the maximum solar-to-hydrogen efficiency of photocatalytic cascade dual Z-schemes with Bi(InAs3)/HfSeTe/ZrSe2 heterostructures can reach 41.04%.

A type-I van der Waals heterostructure formed by monolayer WS2 and trilayer PdSe2.

Two-dimensional (2D) heterostructures, formed by stacking 2D semiconductors through the van der Waals force, have been extensively studied recently. However, the majority of the heterostructures discovered so far possess type-II interfaces that facilitate interlayer charge separation. Type-I interfaces, on the other hand, confine both electrons and holes in one layer, which is beneficial for optical applications that utilize electron-hole radiative recombination. So far, only a few type-I 2D heterostructures have been achieved, which has limited the construction of multilayer heterostructures with sophisticated band landscapes. Here, we report experimental evidence of a type-I interface between monolayer WS2 and trilayer PdSe2. Two-dimensional PdSe2 has emerged as a promising material for infrared optoelectronic and other applications. We fabricated the heterostructure by stacking an exfoliated monolayer WS2 flake on top of a trilayer PdSe2 film, synthesized by chemical vapor deposition. Photoluminescence spectroscopy measurements revealed that the WS2 exciton peak is significantly quenched in the heterostructure, confirming efficient excitation transfer from WS2 to PdSe2. Femtosecond transient absorption measurements with various pump/probe configurations showed that both electrons and holes photoexcited in the WS2 layer of the heterostructure can efficiently transfer to PdSe2, while neither type of carriers excited in PdSe2 can transfer to WS2. These experimental findings establish a type-I band alignment between monolayer WS2 and trilayer PdSe2. Our results further highlight PdSe2 as an important 2D material for constructing van der Waals heterostructures with emergent electronic and optoelectronic properties.

Designing van der Waals magnetic tunnel junctions with high tunnel magnetoresistance via Brillouin zone filtering.

Magnetic tunnel junctions (MTJs) consisting of two-dimensional (2D) van der Waals heterostructures have no inter-layer chemical bonds; therefore, their spin tunneling is determined solely by the Brillouin zone (BZ) filtering effect. To obtain high tunnel magnetoresistance (TMR), they should possess transversal momentum-resolved conduction channels for the electrodes and transmission channels for the barriers. Here, we investigate 2D magnets as electrodes whose Curie temperatures approach room temperature and also hexagonal 2D insulators as the barrier. Iron-based compounds such as FexGeTe2 (x = 3 and 4) are calculated to have high transmission coefficients over the entire in-plane BZ for the majority spin channel, while this should only happen around Γ for the minority spin channel. Correspondingly, various 2H-type transition metal dichalcogenides (TMDs) are found to function effectively as spin barriers, where electrons are only allowed to tunnel through them around the K and M points. BZ spin filtering is confirmed to be the major mechanism of the TMR effect by the MTJ transport calculation using the non-equilibrium Green function method. Furthermore, the TMR is calculated to be nearly independent of the barrier layer thickness as the BZ filtering is an interfacial effect. This work sheds light on material selection procedures and designing ultra-thin and robust van der Waals MTJs.

Nonvolatile electric-field control of topological phase transition in a two-dimensional ferroelectric heterostructure

Topological phase transitions can be controlled by nonvolatile electric-fields through ferroelectric heterostructure engineering.

Defect-engineering of liquid-phase exfoliated 2D semiconductors: stepwise covalent growth of electronic lateral hetero-networks.

Two-dimensional (2D) in-plane heterostructures display exceptional optical and electrical properties well beyond those of their pristine components. However, they are usually produced by tedious and energy-intensive bottom-up growth approaches, not compatible with scalable solution-processing technologies. Here, we report a new stepwise microfluidic approach, based on defect engineering of liquid-phase exfoliated transition metal dichalcogenides (TMDs), to synthesize 2D hetero-networks. The healing of sulfur vacancies in MoS2 and WS2 is exploited to controllably bridge adjacent nanosheets of different chemical nature with dithiolated conjugated molecular linkers, yielding solution-processed nm-scale thick networks with enhanced percolation pathways for charge transport. In-plane growth and molecular-driven assembly synergistically lead to molecularly engineered heterojunctions suppressing the formation of tightly bound interlayer excitons that are typical of conventional TMD blends, promoting faster charge separation. Our strategy offers an unprecedented route to chemically assemble solution-processed heterostructures with functional complexity that can be further enhanced by exploiting stimuli-responsive molecular linkers.

Two-dimensional multiferroic RuClF/AgBiP2S6 van der Waals heterostructures with valley splitting properties and controllable magnetic anisotropy.

The investigation of new properties in two-dimensional (2D) multiferroic heterostructures is significant. In this work, the electronic properties and magnetic anisotropy energies (MAEs) of 2D multiferroic RuClF/AgBiP2S6 van der Waals (vdW) heterostructures are systematically studied by first principles calculations based on density functional theory (DFT). The Hubbard on-site Coulomb parameter (U) of Ru atoms is necessary to account for the strong correlation among the three-dimensional electrons of Ru. RuClF/AgBiP2S6 heterostructures in different polarizations (RuClF/AgBiP2S6-P↑ and RuClF/AgBiP2S6-P↓) are ferromagnetic semiconductors with stable structures. Valley polarizations are present in the band structures of RuClF/AgBiP2S6 heterostructures with spin-orbit coupling (SOC), the valley splitting energies of which are 279 meV and 263 meV, respectively. The MAEs of RuClF/AgBiP2S6 heterostructures indicate perpendicular magnetic anisotropy (PMA), which are primarily attributed to the differences in matrix elements within Ru (dyz, dz2) orbitals. In addition, valley splittings and MAEs of RuClF/AgBiP2S6 heterostructures are modified at different biaxial strains. Specifically, the highest valley splittings are 283 meV and 287 meV at ε = 2%, while they disappear at ε = -6%. The PMA of RuClF/AgBiP2S6-P↑ is gradually decreased at biaxial strains of -6% to 2%, and MAE is transformed into in-plane magnetic anisotropy (IMA) at ε = 4%. RuClF/AgBiP2S6-P↓ maintains PMA at different strains. The study of non-volatile electrical control of valley splitting phenomena in multiferroic RuClF/AgBiP2S6 heterostructures is crucial in the field of valleytronic devices, which has important theoretical significance.

Stacking engineering induced Z-scheme MoSSe/WSSe heterostructure for photocatalytic water splitting.

Stacking engineering is a popular method to tune the performance of two-dimensional materials for advanced applications. In this work, Jansu MoSSe and WSSe monolayers are constructed as a van der Waals (vdWs) heterostructure by different stacking configurations. Using first-principle calculations, all the relaxed stacking configurations of the MoSSe/WSSe heterostructure present semiconductor properties while the direct type-II band structure can be obtained. Importantly, the Z-scheme charge transfer mode also can be addressed by band alignment, which shows the MoSSe/WSSe heterostructure is an efficient potential photocatalyst for water splitting. In addition, the built-in electric field of the MoSSe/WSSe vdWs heterostructure can be enhanced by the S-Se interface due to further asymmetric structures, which also results in considerable charge transfer comparing with the MoSSe/WSSe vdWs heterostructure built by the S-S interface. Furthermore, the excellent optical performances of the MoSSe/WSSe heterostructure with different stacking configurations are obtained. Our results provide a theoretical guidance for the design and control of the two-dimensional heterostructure as photocatalysts through structural stacking.

二维异质结构的I、II、III能带特性综述

二维异质结构的I、II、III能带特性综述

Frustrated van der Waals heterostructures.

Geometrical frustration results from the packing of constituents in a lattice, where the constituents have conflicting forces. The phenomenon is known in glass materials, and this work expands the concept of geometrical frustration into the realm of van der Waals two-dimensional materials. Using density functional theory with the r2SCAN + rVV10 exchange-correlation potential, we find a number of two-dimensional heterostructures with alternating strains, where one layer is strained and the adjacent layer is compressed. We adopted three structural stability criteria to find synthesisable candidate materials: phonon dispersion of the individual layers, comparing the thermodynamic stability of this class of materials, frustrated van der Waals heterostructures, with the non-frustrated counterparts, and ab initio molecular dynamics simulations. These criteria were applied to 7 frustrated van der Waals heterostructures, identifying one material that is potentially stable. We discuss possible fabrication pathways for creating this class of materials.

Coplanar MoS2-MoTe2 Heterojunction With the Same Crystal Orientation.

Two-dimensional (2D)coplanar heterostructure enables high-performance optoelectronic devices, such as p-n heterojunctions. However, realizing site-controllable and shape-specific 2D coplanar heterojunctions composed of two semiconductors with the same crystal orientation still requires the development of new growth methods. Here, a route to fabricate MoS2-MoTe2 coplanar heterojunctions with the same crystal orientation is reported by exploiting the properties of phase transition and atomic rearrangement during the growth of 2H-MoTe2. Raman spectroscopy and electron microscopy techniques reveal the chemical composition and lattice structure of the heterostructure. Both MoS2 and MoTe2 in the heterojunction are single crystals and have the same lattice orientation, and their shapes can be arbitrarily defined by electron beam lithography. Electrical measurements show that the MoS2 and MoTe2 channels exhibit n-type and p-type transfer characteristics, respectively. The coplanar epitaxy technology can be used to prepare more coplanar heterostructures with novel device functions.

The Transition from Type-I to Type-II SiC/GaN Heterostructure with External Strain

Two-dimensional materials are widely used as a new generation of functional materials for photovoltaic, photocatalyst, and nano-power devices. Strain engineering is a popular method to tune the properties of two-dimensional materials so that performances can be improved or more applications can be obtained. In this work, a two-dimensional heterostructure is constructed from SiC and GaN monolayers. Using first-principle calculations, the SiC/GaN heterostructure is stacked by a van der Waals interaction, acting as a semiconductor with an indirect bandgap of 3.331 eV. Importantly, the SiC/GaN heterostructure possesses a type-II band structure. Thus, the photogenerated electron and hole can be separated in the heterostructure as a potential photocatalyst for water splitting. Then, the external biaxial strain can decrease the bandgap of the SiC/GaN heterostructure. From pressure to tension, the SiC/GaN heterostructure realizes a transformation from a type-II to a type-I semiconductor. The strained SiC/GaN heterostructure also shows suitable band alignment to promote the redox of water splitting at pH 0 and 7. Moreover, the enhanced light-absorption properties further explain the SiC/GaN heterostructure’s potential as a photocatalyst and for nanoelectronics.

Electronic and optical properties of MoSSe/borophene heterojunctions with the modulation of electric field and vacancy defects

We investigate the electronic and optical properties of MoSSe/borophene heterojunctions by first principles. Two different structures of borophene and several different stacking layers are considered. The heterojunctions of SeMoS/H, SMoSe/H, and SMoSe/β exhibit the p-type Schottky contacts, while SeMoS/β presents a n-type Schottky contact. When the external electric field is applied to heterojunctions, the Ohmic contact is achieved for SeMoS/H and SMoSe/H. The introduction of S and Se vacancy defects reduces the Schottky barrier height. The heterojunctions of SeMoS/H-VS and SMoSe/H-VS exhibit the Ohmic contact. Moreover, the optical absorption of heterojunctions with vacancy defects has been significantly enhanced, and SeMoS/β-VS has the maximum optical absorption coefficient of 2.35 × 104 cm−1. Our results can provide some guidance for the widespread application of two-dimensional heterostructures in tunable nanoelectronics devices.

Multifunctional Biocompatible Nanoparticles: Surface Modification and Synthesis of Layered Double Hydroxides for Biomedical Applications

Layered Double Hydroxides (LDHs) are considered versatile materials owing to their distinctive features resulting from the isomorphous substitution of metal cations, namely M(II) and M(III), inside their octahedral locations. The LDH layer structure is characterized by a balanced arrangement of exchangeable hydrated or solvated anions within the interlayer and outer regions. This arrangement gives rise to a two-dimensional heterostructure with an ABAB pattern. Various metal cations have a role in LDHs composition, leading to their classification as hydrocalumites and hydrotalcite. Pristine-LDHs that include diverse inorganic anions have shown significant potential in biological applications. These substances have been investigated for their potential use in many applications, including but not limited to antacids, vaccination adjuvants, etc. The attainment of monodispersity in the size of LDHs is of utmost importance for their efficacy in biomedicine. This research emphasizes that the potential of LDHs is contingent upon effectively resolving difficulties, including those associated with size polydispersity. This study suggests using Surface Modified and Synthesized Layered Double Hydroxides for Biomedical Applications (SMS-LDH-BMA). The present study presents a novel approach that incorporates various enhancements, such as a decreased hydrodynamic diameter of 44.6 nm, a zeta potential of -23.86 mV, a high encapsulation efficiency of 91.2%, a substantial drug loading capacity of 14.6%, a favorable cell viability of 96.44%, and a controlled release rate of GLIB at 3.73 μg/mL/min. These findings demonstrate the efficacy of SMS-LDH-BMA in tackling these obstacles and augmenting the drug delivery capabilities and biomedical applications of LDHs.

Platforms of graphene/MXene heterostructure for electrochemical monitoring of rutin in drug and Tartary buckwheat tea

The use of two-dimensional heterostructure composite as electrode modification material has become a new strategy to improve the electrocatalytic activity and electroactive sites of electrochemical sensor. Herein, a soluble heterostructure, namely rGO-PSS@MXene, was designed and synthesized by integrating poly (sodium p-styrenesulfonate)-functionalized reduced graphene oxide into MXene nanosheets via ultrasonic method. The interactive heterostructure can effectively alleviate the self-stacking of MXene and rGO, endowing them with superior electron transfer capacity and large specific surface area, thereby producing prominent synergistic electrocatalytic effect towards rutin. In addition, the excellent enrichment effect of rGO-PSS@MXene for rutin also plays an important role through the electrostatic and π-π stacking interactions. The electrochemical characteristics of rutin on the sensor were examined in detail and a sensitive sensing method was proposed. Under optimized conditions, the method showed satisfactory linear relationship for rutin in the concentration range of 0.005–10.0 μM, with limit of detection of 1.8 nM (S/N = 3). The quantitative validation results in herbal medicine and commercial Tartary buckwheat tea were highly consistent with the labeled quantity and the results of HPLC determination, respectively, suggesting the sensor possessed excellent selectivity and accuracy. This proposed strategy for rutin determination is expected to expand the application of MXene heterostructure in electrochemical sensors, and is envisioned as a promising candidate for quality monitoring of drugs and foods.

Anisotropy and effective medium approach in the optical response of two-dimensional material heterostructures

Anisotropy and effective medium approach in the optical response of two-dimensional material heterostructures

Controlled dynamic variation of interfacial electronic and optical properties of lithium intercalated ZrO2/MoS2 vdW heterostructure

Efficient strategies for modifying the characteristics of van der Waals (vdW) layered materials in a precise and reversible mode remain challenging. Our suggested method for customization entails the implementation of layer-sliding and intercalation. In this work, a norm-conserving approach within the context of density functional theory has been used to examine the electronic and optical properties of two-dimensional (2D) van der Waals heterostructure (vdWHS), which is modeled by using 2D zirconium dioxide (1T-ZrO2) and molybdenum disulfide (1T-MoS2) monolayers of similar phase. Both contributing monolayers have similar lattice structures, with a minimum lattice mismatch of 0.83 %, and have corrugation on both sides that can successfully retain foreign species at the vdW-gap. In the next step, interfacial engineering through Li-intercalation and layer-sliding was employed to modify physical properties of the vdWHS. It is the worth mentioning that a narrow bandgap of 0.102 eV (0.22 eV) has been observed in the unintercalated ZrO2/MoS2 vdWHS when employing PW-LDA (hybrid-functional). Li-intercalation and sliding process significantly influenced the electronic properties of the studied vdWHS. Furthermore, un-slided and fully-slided Li-intercalated vdWHS exhibit an increase in the vdW-gap by 3.78 % and 27.14 %, respectively, as compared to unintercalated vdWHS. To further understand the electrical behaviour at the interface of contributing monolayers, a comparative study has also been made for the variation in the planar average charge density difference, charge transfer, and interface dipole moment for unintercalated and intercalated vdWHS. In the unintercalated vdWHS, the calculated values of ΔQ and μ(z) provide evidence of significant charge transfer from 1T-ZrO2 to 1T-MoS2 before sliding, whereas in the fully-slided vdWHS, there is 80.11 % more charge transfer from 1T-MoS2 to 1T-ZrO2. Li-intercalation increases the magnitude of ΔQ (by 90.27 %) near 1T-MoS2, indicating a sufficient quantity of charge transfer from the 1T-MoS2 monolayer. The results of the anisotropic analysis show that the calculated in-plane and out-of-plane components of the real and imaginary parts of the dielectric function differ significantly. The optical absorption and energy losses of Li-intercalated vdWHS experience a substantial decrease of about 90 % and 50 %, respectively, as compared to unintercalated vdWHS. Our employed method promotes the notion that interfacial engineering through simultaneous layer-sliding and intercalation approach can be used to regulate and modify the physical properties of 2D insulator/metal based vdWHS.