Progress and Insight of Van der Waals Heterostructures Containing Interlayer Transition for Near Infrared Photodetectors

Van der Waals (vdWs) heterostructures enable bandgap engineering of different 2D materials to realize the interlayer transition via type-II band alignment leading to broaden spectrum that is beyond the cut-off wavelength of individual 2D materials. Interlayer transition has a significant effect on the optoelectronic performance of vdWs heterostructure devices, and strong interlayer transition in 2D vdWs heterojunction is always demandable for sufficient charge transfer and rapid speed response. Herein, a state-of-the-art review is presented on recent progress on interlayer transition in vdWs heterostructures for near-infrared (NIR) photodetectors. First, the general synthesis techniques for vdWs heterostructures, band alignments in the vdWs heterostructures are provided. Then, the mechanism of interlayer transition in vdWs heterostructure and recent progress on interlayer transition in vdWs heterostructures for NIR photodetectors are summarized. Afterward, some worthy applications of NIR photodetectors are reviewed in related areas of this topic. At the last, an outlook, challenges, and future research directions of vdWs heterostructures for photodetectors at broaden response spectrum are presented.     

Liquid Phase Exfoliated Indium Selenide Based Highly Sensitive Photodetectors

Layered semiconductors of the IIIA–VIA group have attracted considerable attention in (opto)electronic applications thanks to their atomically thin structures and their thickness‐dependent optical and electronic properties, which promise ultrafast response and high sensitivity. In particular, 2D indium selenide (InSe) has emerged as a promising candidate for the realization of thin‐film field effect transistors and phototransistors due to its high intrinsic mobility (>10² cm² V^?1 s^?1) and the direct optical transitions in an energy range suitable for visible and near‐infrared light detection. A key requirement for the exploitation of large‐scale (opto)electronic applications relies on the development of low‐cost and industrially relevant 2D material production processes, such as liquid phase exfoliation, combined with the availability of high‐throughput device fabrication methods. Here, a β polymorph of indium selenide (β‐InSe) is exfoliated in isopropanol and spray‐coated InSe‐based photodetectors are demonstrated, exhibiting high responsivity to visible light (maximum value of 274 A W^?1 under blue excitation 455 nm) and fast response time (15 ms). The devices show a gate‐dependent conduction with an n‐channel transistor behavior. Overall, this study establishes that liquid phase exfoliated β‐InSe is a valid candidate for printed high‐performance photodetectors, which is critical for the development of industrial‐scale 2D material‐based optoelectronic devices.     

Fully-Depleted PdTe2/WSe2 van der Waals Field Effect Transistor with High Light On/Off Ratio and Broadband Detection

Due to its unique band structure and topological properties, the 2D topological semimetal exhibits potential applications in photoelectric detection, polarization sensitive imaging, and Schottky barrier diodes. However, its inherent large dark current hinders the further improvement of the performance of the semimetal-based photodetectors. In this study, a van der Waals (vdWs) field effect transistor (FET) composed of semimetal PdTe₂ and transition metal dichalcogenides (TMDs) WSe₂ is fabricated, which exhibits high sensitivity photoelectric detection performance in a wide band from visible light (405 nm) to mid-infrared (5 µm). The dark current and the noise level in the device are greatly suppressed by the effective control of the gate. Benefiting from the extremely low dark current (1.2 pA), the device achieves an optical on/off ratio up to 10⁶, a high detectivity of 9.79 × 10¹³ Jones and a rapid response speed (219 and 45 µs). This research demonstrates the latent capacity of the 2D topological semimetal/TMDs vdWs FET for broadband, high-performance, and miniaturized photodetection.     

Progress,Challenges, and Opportunities for 2D Material Based Photodetectors

2D material based photodetectors have attracted many research projects due to their unique structures and excellent electronic and optoelectronic properties. These 2D materials, including semimetallic graphene, semiconducting black phosphorus, transition metal dichalcogenides, insulating hexagonal boron nitride, and their various heterostructures, show a wide distribution in bandgap values. To date, hundreds of photodetectors based on 2D materials have been reported. Here, a review of photodetectors based on 2D materials covering the detection spectrum from ultraviolet to infrared is presented. First, a brief insight into the detection mechanisms of 2D material photodetectors as well as introducing the figure‐of‐merits which are key factors for a reasonable comparison between different photodetectors is provided. Then, the recent progress on 2D material based photodetectors is reviewed. Particularly, the excellent performances such as broadband spectrum detection, ultrahigh photoresponsivity and sensitivity, fast response speed and high bandwidth, polarization‐sensitive detection are pointed out on the basis of the state‐of‐the‐art 2D photodetectors. Initial applications based on 2D material photodetectors are mentioned. Finally, an outlook is delivered, the challenges and future directions are discussed, and general advice for designing and realizing novel high‐performance photodetectors is given to provide a guideline for the future development of this fast‐developing field.     

Nonvolatile Floating‐Gate Memories Based on Stacked Black Phosphorus–Boron Nitride–MoS2 Heterostructures

Research on van der Waals heterostructures based on stacked 2D atomic crystals is intense due to their prominent properties and potential applications for flexible transparent electronics and optoelectronics. Here, nonvolatile memory devices based on floating‐gate field‐effect transistors that are stacked with 2D materials are reported, where few‐layer black phosphorus acts as channel layer, hexagonal boron nitride as tunnel barrier layer, and MoS₂ as charge trapping layer. Because of the ambipolar behavior of black phosphorus, electrons and holes can be stored in the MoS₂ charge trapping layer. The heterostructures exhibit remarkable erase/program ratio and endurance performance, and can be developed for high‐performance type‐switching memories and reconfigurable inverter logic circuits, indicating that it is promising for application in memory devices completely based on 2D atomic crystals.     

2D Layered Material‐Based van der Waals Heterostructures for Optoelectronics

Van der Waals heterostructures (vdWHs) based on 2D layered materials with selectable materials properties pave the way to integration at the atomic scale, which may give rise to fresh heterostructures exhibiting absolutely novel physics and versatility. This feature article reviews the state‐of‐the‐art research activities that focus on the 2D vdWHs and their optoelectronic applications. First, the preparation methods such as mechanical transfer and chemical vapor deposition growth are comprehensively outlined. Then, unique energy band alignments generated in 2D vdWHs are introduced. Furthermore, this feature article focuses on the applications in light‐emitting diodes, photodetectors, and optical modulators based on 2D vdWHs with novel constructions and mechanisms. The recently reported novel constructions of the devices are introduced in three primary aspects: light‐emitting diodes (such as single defect light‐emitting diodes, circularly polarized light emission arising from valley polarization), photodetectors (such as photo‐thermionic, tunneling, electrolyte‐gated, and broadband photodetectors), and optical modulators (such as graphene integrated with silicon technology and graphene/hexagonal boron nitride (hBN) heterostructure), which show promising applications in the next‐generation optoelectronics. Finally, the article provides some conclusions and an outlook on the future development in the field.     

Junction Field-Effect Transistors Based on PdSe2/MoS2 Heterostructures for Photodetectors Showing High Responsivity and Detectivity

2D materials have shown great promise for next-generation high-performance photodetectors. However, the performance of photodetectors based on 2D materials is generally limited by the tradeoff between photoresponsivity and photodetectivity. Here, a novel junction field-effect transistor (JFET) photodetector consisting of a PdSe₂ gate and MoS₂ channel is constructed to realize high responsivity and high detectivity through effective modulation of top junction gate and back gate. The JFET exhibits high carrier mobility of 213 cm² V⁻¹ s⁻¹. What is more, the high responsivity of 6 × 10² A W⁻¹, as well as the high detectivity of 10¹¹ Jones, are achieved simultaneously through the dual-gate modulation. The high performance is attributed to the modulation of the depletion region by the dual-gate, which can effectively suppress the dark current and enhance the photocurrent, thereby realizing high detectivity and responsivity. The JFET photodetector provides a new approach to realize photodetectors with high responsivity and detectivity.     

New Polymorphs of 2D Indium Selenide with Enhanced Electronic Properties

The 2D semiconductor indium selenide (InSe) has attracted significant interest due its unique electronic band structure, high electron mobility, and wide tunability of its band gap energy achieved by varying the layer thickness. All these features make 2D InSe a potential candidate for advanced electronic and optoelectronic applications. Here, the discovery of new polymorphs of InSe with enhanced electronic properties is reported. Using a global structure search that combines artificial swarm intelligence with first‐principles energetic calculations, polymorphs that consist of a centrosymmetric monolayer belonging to the point group D_3d are identified, distinct from well‐known polymorphs based on the D_3h monolayers that lack inversion symmetry. The new polymorphs are thermodynamically and kinetically stable, and exhibit a wider optical spectral response and larger electron mobilities compared to the known polymorphs. Opportunities to synthesize these newly discovered polymorphs and viable routes to identify them by X‐ray diffraction, Raman spectroscopy, and second harmonic generation experiments are discussed.     

Recent Progress of Heterojunction Ultraviolet Photodetectors: Materials,Integrations, and Applications

Ultraviolet photodetectors (UV PDs) with “5S” (high sensitivity, high signal‐to‐noise ratio, excellent spectrum selectivity, fast speed, and great stability) have been proposed as promising optoelectronics in recent years. To realize high‐performance UV PDs, heterojunctions are created to form a built‐in electrical field for suppressing recombination of photogenerated carriers and promoting collection efficiency. In this progress report, the fundamental components of heterojunctions including UV response semiconductors and other materials functionalized with unique effects are discussed. Then, strategies of building PDs with lattice‐matched heterojunctions, van der Waals heterostructures, and other heterojunctions are summarized. Finally, several applications based on heterojunction/heterostructure UV PDs are discussed, compromising flexible photodetectors, logic gates, and image sensors. This work draws an outline of diverse materials as well as basic assembly methods applied in heterojunction/heterostructure UV PDs, which will help to bring about new possibilities and call for more efforts to unleash the potential of heterojunctions.     

Collective Dipole‐Dominated Doping of Monolayer MoS2: Orientation and Magnitude Control via the Supramolecular Approach

Molecular doping is a powerful, tuneable, and versatile method to modify the electronic properties of 2D transition metal dichalcogenides (TMDCs). While electron transfer is an isotropic process, dipole‐induced doping is a collective phenomenon in which the orientation of the molecular dipoles interfaced to the 2D material is key to modulate and boost this electronic effect, despite it is not yet demonstrated. A novel method toward the molecular functionalization of monolayer MoS₂ relying on the molecular self‐assembly of metal phthalocyanine and the orientation‐controlled coordination chemistry of axial ligands is reported here. It is demonstrated that the subtle variation of position and type of functional groups exposed on the pyridinic ligand, yields a molecular dipole with programed magnitude and orientation which is capable to strongly influence the opto‐electronic properties of monolayer MoS₂. In particular, experimental results revealed that both p‐ and n‐type doping can be achieved by modulating the charge carrier density up to 4.8 10¹² cm^?2. Density functional theory calculations showed that the doping mechanism is primarily resulting from the effect of dipole‐induced doping rather than charge transfer. The strategy to dope TMDCs is a highly modulable and robust, and it enables to enrich the functionality of 2D materials‐based devices for high‐performance applications in optoelectronics.     

Photoinduced Contact Evolution and Junction Rearrangement in Two-Dimensional van der Waals Heterostructure

Devices based on 2DMs van der Waals (vdW) heterostructures always compose of multiple contacts. Due to the instability of nanoscale 2DMs and interfaces, these contacts can be affected by the operation-induced photo or thermal effect. They can trigger the evolution of junctions and rearrange the junctions across a device, which are detrimental for applications. Herein, vdW heterostructure of indium selenide (InSe) and black phosphorus (BP) on Au electrodes are investigated to reveal the contact evolution and its relation to device performance. During operation, light irradiation changes the I–V characteristics from symmetry to strong rectification. Photocurrent mapping and Kelvin-probe force microscopy (KPFM) reveal triple junctions in this heterostructure, i.e., Au-InSe junction, InSe homojunction, and InSe-BP heterojunction. The variation of I–V characteristics of vdW heterostructure is ascribed to the evolution of Au-InSe junction from quasi-ohmic junction with a near-zero work function difference (Δφ) to a strong Schottky junction (Δφ = ≈0.27 eV). The stabilized device demonstrates distinguished time-domain response at individual junctions and overall device, indicating the evolution of contacts and the consequent opposite junction directions degrade the overall device performance. This research emphasizes the importance of dealing with heterogeneous contacts and junction directions in designing vdW heterostructure photodetectors.     

Mixed‐Dimensional 1D ZnO–2D WSe2 van der Waals Heterojunction Device for Photosensors

2D layered van der Waals (vdW) atomic crystals are an emerging class of new materials that are receiving increasing attention owing to their unique properties. In particular, the dangling‐bond‐free surface of 2D materials enables integration of differently dimensioned materials into mixed‐dimensional vdW heterostructures. Such mixed‐dimensional heterostructures herald new opportunities for conducting fundamental nanoscience studies and developing nanoscale electronic/optoelectronic applications. This study presents a 1D ZnO nanowire (n‐type)–2D WSe₂ nanosheet (p‐type) vdW heterojunction diode for photodetection and imaging process. After amorphous fluoropolymer passivation, the ZnO–WSe₂ diode shows superior performance with a much‐enhanced rectification (ON/OFF) ratio of over 10⁶ and an ideality factor of 3.4–3.6 due to the carbon–fluorine (C? F) dipole effect. This heterojunction device exhibits spectral photoresponses from ultraviolet (400 nm) to near infrared (950 nm). Furthermore, a prototype visible imager is demonstrated using the ZnO–WSe₂ heterojunction diode as an imaging pixel. To the best of our knowledge, this is the first demonstration of an optoelectronic device based on a 1D–2D hybrid vdW heterojunction. This approach using a 1D ZnO–2D WSe₂ heterojunction paves the way for the further development of electronic/optoelectronic applications using mixed‐dimensional vdW heterostructures.     

Manipulation of Magnetic Skyrmion in a 2D van der Waals Heterostructure via Both Electric and Magnetic Fields

As a promising candidate for the much-desired low power consumption spintronic devices, 2D magnetic van der Waals material also provides a versatile platform for the design and control of topological spin textures. In this work on WTe₂/CrCl₃ bilayer van der Waals heterostructures, a complete Néel-type skyrmion–bimeron–ferromagnet phase transition is demonstrated, accompanied by the evolution of the topological number. This cyclic transition, mediated by a perpendicular magnetic field, is largely driven by the competition between the out-of-plane magnetocrystalline anisotropy and magnetic dipole–dipole interaction. In the presence of a driving current, the Néel-type skyrmion gains a higher velocity yet larger skyrmion Hall angle, in comparison to the bimeron. By incorporating a ferroelectric CuInP₂S₆ monolayer as a substrate, writing and erasing of skyrmions may be regulated using a ferroelectric polarization. This work sheds light on a novel approach to the design and control of magnetic skyrmions on 2D van der Waals materials.     

2D van der Waals Heterojunction Nanophotonic Devices: From Fabrication to Performance

2D van der Waals heterojunctions (vdWhs) are a novel type of metamaterial that are flexible, adjustable, and easy to assemble. Using weak van der Waals forces (vdWfs), layered 2D materials can stack freely to form vdWhs with atomic level flat interfaces. By using different 2D materials and specific stacking methods, their unique properties can be organically combined, to exhibit more abundant optical properties. In fact, nanophotonic devices based on 2D vdWhs have developed rapidly and made significant progress. Therefore, the main progress of 2D vdWhs nanophotonic devices in recent years, including the preparation methods of 2D vdWhs and the performance improvements of various nanophotonic devices, is reviewed. Lastly, the prospects of 2D vdWhs nanophotonic devices are discussed.     

All-Inorganic CsPbBr3 Perovskite Nanocrystals/2D Non-Layered Cadmium Sulfide Selenide for High-Performance Photodetectors by Energy Band Alignment Engineering

Perovskites have attracted intensive attention as promising materials for the application in various optoelectronic devices due to their large light absorption coefficient, high carrier mobility, and long charge carrier diffusion length. However, the performance of the pure perovskite nanocrystals-based device is extremely restricted by the limited charge transport capability due to the existence of a large number of the grain boundary between perovskite nanocrystals. To address these issues, a high-performance photodetector based on all-inorganic CsPbBr₃ perovskite nanocrystals/2D non-layered cadmium sulfide selenide heterostructure has been demonstrated through energy band engineering with designed typed-II heterostructure. The photodetector exhibits an ultra-high light-to-dark current ratio of 1.36 × 10⁵, a high responsivity of 2.89 × 10² A W⁻¹, a large detectivity of 1.28 × 10¹⁴ Jones, and the response/recovery time of 0.53s/0.62 s. The enhancement of the optoelectronic performance of the heterostructure photodetector is mainly attributed to the efficient charge carrier transfer ability between the all-inorganic CsPbBr₃ perovskites and 2D cadmium sulfide selenide resulting from energy band alignment engineering. The charge carriers’ transfer dynamics and the mechanism of the CsPbBr₃ perovskites/2D non-layered nanosheets interfaces have also been studied by state-state PL spectra, fluorescence lifetime imaging microscopy, time-resolved photoluminescence spectroscopy, and Kelvin probe force microscopy measurements.     

Polarity‐Controlled Attachment of Cytochrome C for High‐Performance Cytochrome C/Graphene van der Waals Heterojunction Photodetectors

Biomolecule/graphene van der Waals heterojunction provides a generic platform for designing high‐performance, flexible, and scalable optoelectronics. A key challenge is, in controllable attachment, the biomolecules to form a desired interfacial electronic structure for a high‐efficiency optoelectronic process of photoabsorption, exciton dissociation into photocarriers, carrier transfer, and transport. Here, it is shown that a polarity‐controlled attachment of the Cytochrome c (Cyt c) biomolecules can be achieved on the channel of graphene field effect transistors (GFET). High‐efficiency charge transfer across the formed Cyt c/graphene interface is demonstrated when Cyt c attaches with positively charged side to GFET as predicted by molecular dynamics simulation and confirmed experimentally. This Cyt c/GFET van der Waals heterojunction nanohybrid photodetector exhibits a spectral photoresponsivity resembling the absorption spectrum of the Cyt c, confirming the role of Cty c as the photosensitizer in the device. The high visible photoresponsivity up to 7.57 × 10⁴ A W^?1 can be attributed to the high photoconductive gain in exceeding 10⁵ facilitated by the high carrier mobility in graphene. This result therefore demonstrates a viable approach in synthesis of the biomolecule/graphene van der Waals heterojunction optoelectronics using polarity‐controlled biomolecule attachment, which can be expanded for on‐chip printing of high‐performance molecular optoelectronics.     

Reconfigurable Logic‐in‐Memory and Multilingual Artificial Synapses Based on 2D Heterostructures

Nonvolatile logic devices have attracted intensive research attentions recently for energy efficiency computing, where data computing and storage can be realized in the same device structure. Various approaches have been adopted to build such devices; however, the functionality and versatility are still very limited. Here, 2D van der Waals heterostructures based on direct bandgap materials black phosphorus and rhenium disulfide for the nonvolatile ternary logic operations is demonstrated for the first time with the ultrathin oxide layer from the black phosphorus serving as the charge trapping as well as band‐to‐band tunneling layer. Furthermore, an artificial electronic synapse based on this heterostructure is demonstrated to mimic trilingual synaptic response by changing the input base voltage. Besides, artificial neural network simulation based on the electronic synaptic arrays using the handwritten digits data sets demonstrates a high recognition accuracy of 91.3%. This work provides a path toward realizing multifunctional nonvolatile logic‐in‐memory applications based on novel 2D heterostructures.     

Anomalous Dimensionality-Driven Phase Transition of MoTe2 in Van der Waals Heterostructure

Phase transition in nanomaterials is distinct from that in 3D bulk materials owing to the dominant contribution of surface energy. Among nanomaterials, 2D materials have shown unique phase transition behaviors due to their larger surface-to-volume ratio, high crystallinity, and lack of dangling bonds in atomically thin layers. Here, the anomalous dimensionality-driven phase transition of molybdenum ditelluride (MoTe₂) encapsulated by hexagonal boron nitride (hBN) is reported. After encapsulation annealing, single-crystal 2H-MoTe₂ transformed into polycrystalline T_d-MoTe₂ with tilt-angle grain boundaries of 60°-glide-reflection and 120°-twofold rotation. In contrast to conventional nanomaterials, the hBN-encapsulated MoTe₂ exhibit a deterministic dependence of the phase transition on the number of layers, in which the thinner MoTe₂ has a higher 2H-to-T_d phase transition temperature. In addition, the vertical and lateral phase transitions of the stacked MoTe₂ with different crystalline orientations can be controlled by inserted graphene layers and the thickness of the heterostructure. Finally, it is shown that seamless T_d contacts for 2H-MoTe₂ transistors can be fabricated by using the dimensionality-driven phase transition. The work provides insight into the phase transition of 2D materials and van der Waals heterostructures and illustrates a novel method for the fabrication of multi-phase 2D electronics.     

Strong Interlayer Transition in Few-Layer InSe/PdSe2 van der Waals Heterostructure for Near-Infrared Photodetection

Near infrared (NIR) photodetectors based on 2D materials are widely studied for their potential application in next generation sensing, thermal imaging, and optical communication. Construction of van der Waals (vdWs) heterostructure provides a tremendous degree of freedom to combine and extend the features of 2D materials, opening up new functionalities on photonic and optoelectronic devices. Herein, a type-II InSe/PdSe₂ vdWs heterostructure with strong interlayer transition for NIR photodetection is demonstrated. Strong interlayer transition between InSe and PdSe₂ is predicted via density functional theory calculation and confirmed by photoluminance spectroscopy and Kelvin probe force microscopy. The heterostructure exhibits highly sensitive photodetection in NIR region up to 1650 nm. The photoresponsivity, detectivity, and external quantum efficiency at this wavelength respectively reaches up to 58.8 A W⁻¹, 1 × 10¹⁰ Jones, and 4660%. The results suggest that the construction of vdWs heterostructure with strong interlayer transition is a promising strategy for infrared photodetection, and this work paves the way to developing high-performance optoelectronic devices based on 2D vdWs heterostructures.     

Graphene-Enhanced Metal Transfer Printing for Strong van der Waals Contacts between 3D Metals and 2D Semiconductors

2D semiconductors have shown great potentials for ultra-short channel field-effect transistors (FETs) in next-generation electronics. However, because of intractable surface states and interface barriers, it is challenging to realize high-quality contacts with low contact resistances for both p- and n- 2D FETs. Here, a graphene-enhanced van der Waals (vdWs) integration approach is demonstrated, which is a multi-scale (nanometer to centimeter scale) and reliable (≈100% yield) metal transfer strategy applicable to various metals and 2D semiconductors. Scanning transmission electron microscopy imaging shows that 2D/2D/3D semiconductor/graphene/metal interfaces are atomically flat, ultraclean, and defect-free. First principles calculations indicate that the sandwiched graphene monolayer can eliminate gap states induced by 3D metals in 2D semiconductors. Through this approach, Schottky barrier-free contacts are realized on both p- and n-type 2D FETs, achieving p-type MoTe₂, p-type black phosphorus and n-type MoS₂ FETs with on-state current densities of 404, 1520, and 761 µA µm⁻¹, respectively, which are among the highest values reported in literature.