Highly Stable HfO2 Memristors through van der Waals Electrode Lamination and Delamination.

Memristors have attracted considerable attention in the past decade, holding great promise for future neuromorphic computing. However, the intrinsic poor stability and large device variability remain key limitations for practical application. Here, we report a simple method to directly visualize the origin of poor stability. By mechanically removing the top electrodes of memristors operated at different states (such as SET or RESET), the memristive layer could be exposed and directly characterized through conductive atomic force microscopy, providing two-dimensional area information within memristors. Based on this technique, we observed the existence of multiple conducting filaments during the formation process and built up a physical model between filament numbers and the cycle-to-cycle variation. Furthermore, by improving the interface quality through the van der Waals top electrode, we could reduce the filament number down to a single filament during all switching cycles, leading to much controlled switching behavior and reliable device operation.

Reversible Amorphous-Crystalline Phase Transformation in an Ultrathin van der Waals FeTe System.

Searching for new phase-change materials for memory and neuromorphic device applications and further understanding the phase transformation mechanism are attracting wide attention. Phase transformation from the amorphous phase to the crystal phase has been unraveled in iron telluride (FeTe) bulk film deposited by pulsed laser deposition, recently. However, the van der Waals-layered feature of FeTe in the crystal form was not noted, which will benefit the scaling of the memory devices and shine light on phase-change heterostructures or interfacial phase-change materials. Moreover, the demonstration of advanced memory or neuromorphic device applications is lacking. Here, we investigate the phase transformation of FeTe starting from mechanically exfoliated van der Waals layers from a bulk single crystal. Surficial amorphization is revealed at the surface layers of FeTe flakes after exfoliation under ambient conditions, which could be transformed back to the crystalline phase with laser irradiation or heating. The conductance drop of the flake devices near 400 K verifies the phase transformation electrically. Memristor behavior of the amorphous surface in FeTe has been further demonstrated, proving the reversibility of the phase transformation and shining light on the possible applications of neuromorphic devices.

Probing the Twist-Controlled Interlayer Coupling in Artificially Stacked Transition Metal Dichalcogenide Bilayers by Second-Harmonic Generation.

Interlayer coupling plays a critical role in the electronic band structures and optoelectronic properties of van der Waals (vdW) materials and heterostructures. Here, we utilize optical second-harmonic generation (SHG) measurements to probe the twist-controlled interlayer coupling in artificially stacked WSe2/WSe2 homobilayers and WSe2/WS2 and WSe2/MoS2 heterobilayers with a postannealing procedure. In the large angle twisted WSe2/WSe2 and WSe2/WS2, the angular dependence of the SHG intensity follows the interference relations up to angles above 10°. For lower angles, the SHG is significantly suppressed. Furthermore, for the twisted WSe2/MoS2 the SHG intensity largely deviates from the coherent superposition model and shows consistent quenching for all the stacking angles. The suppressed SHG in twisted transition metal dichalcogenide (TMDC) bilayers is predominantly attributed to the interlayer coupling between the two adjacent monolayers. The evolution of the interlayer Raman mode in WSe2 demonstrates that the interlayer coupling in the twisted WSe2/WSe2 and WSe2/WS2 is highly angle-dependent. Alternatively, the interlayer coupling generally exists in the twisted WSe2/MoS2, regardless of the different angles. The interlayer coupling is further confirmed by the quenching and red-shift of the photoluminescence of WSe2 in the twisted TMDC bilayers. Combined with density functional theory calculations, we reveal that the stacking-angle-modulated interlayer coupling originates from the variation of the interlayer spacing and the binding energy in the twisted TMDC bilayers.

Silicon-Based On-Chip Tunable High-Q-Factor and Low-Power Fano Resonators with Graphene Nanoheaters.

Tunable and low-power microcavities are essential for large-scale photonic integrated circuits. Thermal tuning, a convenient and stable tuning method, has been widely adopted in optical neural networks and quantum information processing. Recently, graphene thermal tuning has been demonstrated to be a power-efficient technique, as it does not require thick spacers to prevent light absorption. In this paper, a silicon-based on-chip Fano resonator with graphene nanoheaters is proposed and fabricated. This novel Fano structure is achieved by introducing a scattering block, and it can be easily fabricated in large quantities. Experimental results demonstrate that the resonator has the characteristics of a high quality factor (∼31,000) and low state-switching power (∼1 mW). The temporal responses of the microcavity exhibit qualified modulation speed with 9.8 µs rise time and 16.6 µs fall time. The thermal imaging and Raman spectroscopy of graphene at different biases were also measured to intuitively show that the tuning is derived from the joule heating effect of graphene. This work provides an alternative for future large-scale tunable and low-power-consumption optical networks, and has potential applications in optical filters and switches.

High-Temperature Quantum Hall Effect in Graphite-Gated Graphene Heterostructure Devices with High Carrier Mobility.

Since the discovery of the quantum Hall effect in 1980, it has attracted intense interest in condensed matter physics and has led to a new type of metrological standard by utilizing the resistance quantum. Graphene, a true two-dimensional electron gas material, has demonstrated the half-integer quantum Hall effect and composite-fermion fractional quantum Hall effect due to its unique massless Dirac fermions and ultra-high carrier mobility. Here, we use a monolayer graphene encapsulated with hexagonal boron nitride and few-layer graphite to fabricate micrometer-scale graphene Hall devices. The application of a graphite gate electrode significantly screens the phonon scattering from a conventional SiO2/Si substrate, and thus enhances the carrier mobility of graphene. At a low temperature, the carrier mobility of graphene devices can reach 3 × 105 cm2/V·s, and at room temperature, the carrier mobility can still exceed 1 × 105 cm2/V·s, which is very helpful for the development of high-temperature quantum Hall effects under moderate magnetic fields. At a low temperature of 1.6 K, a series of half-integer quantum Hall plateaus are well-observed in graphene with a magnetic field of 1 T. More importantly, the ν = ±2 quantum Hall plateau clearly persists up to 150 K with only a few-tesla magnetic field. These findings show that graphite-gated high-mobility graphene devices hold great potential for high-sensitivity Hall sensors and resistance metrology standards for the new Système International d'unités.

Integrated wafer-scale ultra-flat graphene by gradient surface energy modulation.

The integration of large-scale two-dimensional (2D) materials onto semiconductor wafers is highly desirable for advanced electronic devices, but challenges such as transfer-related crack, contamination, wrinkle and doping remain. Here, we developed a generic method by gradient surface energy modulation, leading to a reliable adhesion and release of graphene onto target wafers. The as-obtained wafer-scale graphene exhibited a damage-free, clean, and ultra-flat surface with negligible doping, resulting in uniform sheet resistance with only ~6% deviation. The as-transferred graphene on SiO2/Si exhibited high carrier mobility reaching up ~10,000 cm2 V-1 s-1, with quantum Hall effect (QHE) observed at room temperature. Fractional quantum Hall effect (FQHE) appeared at 1.7 K after encapsulation by h-BN, yielding ultra-high mobility of ~280,000 cm2 V-1 s-1. Integrated wafer-scale graphene thermal emitters exhibited significant broadband emission in near-infrared (NIR) spectrum. Overall, the proposed methodology is promising for future integration of wafer-scale 2D materials in advanced electronics and optoelectronics.

Highly Tunable Carrier Tunneling in Vertical Graphene-WS2-Graphene van der Waals Heterostructures.

Owing to the fascinating properties, the emergence of two-dimensional (2D) materials brings various important applications of electronic and optoelectronic devices from field-effect transistors (FETs) to photodetectors. As a zero-band-gap material, graphene has excellent electric conductivity and ultrahigh carrier mobility, while the ON/OFF ratio of the graphene FET is severely low. Semiconducting 2D transition metal chalcogenides (TMDCs) exhibit an appropriate band gap, realizing FETs with high ON/OFF ratio and compensating for the disadvantages of graphene transistors. However, a Schottky barrier often forms at the interface between the TMDC and metallic contact, which limits the on-state current of the devices. Here, we lift the two limits of the 2D-FET by demonstrating highly tunable field-effect tunneling transistors based on vertical graphene-WS2-graphene van der Waals heterostructures. Our devices show a low off-state current below 1 pA and a high ON/OFF ratio exceeding 106 at room temperature. Moreover, the carrier transport polarity of the device can be effectively tuned from n-type under small bias voltage to bipolar under large bias by controlling the crossover from a direct tunneling region to the Fowler-Nordheim tunneling region. Further, we find that the effective barrier height can be controlled by an external gate voltage. The temperature dependence of carrier transport demonstrates that both tunneling and thermionic emission contribute to the operation current at elevated temperature, which significantly enhances the on-state current of the tunneling transistors.

Electrically Controlled Wavelength-Tunable Photoluminescence from van der Waals Heterostructures.

Achieving facile control of the wavelength of light emitters is of great significance for many key applications in optoelectronics and photonics, including on-chip interconnection, super-resolution imaging, and optical communication. The Joule heating effect caused by electric current is widely applied in modulating the refractive index of silicon-based waveguides for reconfigurable nanophotonic circuits. Here, by utilizing localized Joule heating in the biased graphene device, we demonstrate electrically controlled wavelength-tunable photoluminescence (PL) from vertical van der Waals heterostructures combined by graphene and two-dimensional transition metal dichalcogenides (2D-TMDCs). By applying a moderate electric field of 6.5 kV·cm-1 to the graphene substrate, the PL wavelength of 2D-TMDCs exhibits a continuous tuning from 662 to 690 nm, corresponding to a bandgap reduction of 76 meV. The electric control is highly reversible during sweeping the bias back and forth. The temperature dependence of Raman and PL spectroscopy reveals that the current-induced local Joule heating effect plays a leading role in reducing the optical direct bandgap of TMDCs. The bias-dependent optical reflectivity and time-resolved photoluminescence measurements show a consistent reduction of the optical band gap of 2D-TMDCs and increased PL lifetimes with the electric field over the heterostructures. Moreover, we demonstrate the consistent device operation from 2D materials grown by chemical vapor deposition, showing great advantages for the scalability.

High-Performance Photodetectors Based on MoTe2-MoS2 van der Waals Heterostructures.

Two-dimensional (2D) materials have got extensive attention for multifunctional device applications in advanced nanoelectronics and optoelectronics, such as field-effect transistors, photodiodes, and solar cells. In our work, we fabricated MoTe2-MoS2 van der Waals heterostructure photodetectors with great performance using the mechanical exfoliation method and restack technique. It is demonstrated that our MoTe2-MoS2 heterostructure photodetector device can operate without bias voltage, possessing a low dark current (10 pA) and high photocurrent on/off ratio (>104). Importantly, the room temperature photoresponsivity of the MoTe2-MoS2 photodetector can reach 110.6 and 9.2 mA W-1 under λ = 532 and 1064 nm incident laser powers, respectively. Our results indicate that the van der Waals heterostructure based on 2D semiconducting materials is expected to play an important role in nanoscale optoelectronic applications.

A monolithically sculpted van der Waals nano-opto-electro-mechanical coupler.

The nano-opto-electro-mechanical systems (NOEMS) are a class of hybrid solid devices that hold promises in both classical and quantum manipulations of the interplay between one or more degrees of freedom in optical, electrical and mechanical modes. To date, studies of NOEMS using van der Waals (vdW) heterostructures are very limited, although vdW materials are known for emerging phenomena such as spin, valley, and topological physics. Here, we devise a universal method to easily and robustly fabricate vdW heterostructures into an architecture that hosts opto-electro-mechanical couplings in one single device. We demonstrated several functionalities, including nano-mechanical resonator, vacuum channel diodes, and ultrafast thermo-radiator, using monolithically sculpted graphene NOEMS as a platform. Optical readout of electric and magnetic field tuning of mechanical resonance in a CrOCl/graphene vdW NOEMS is further demonstrated. Our results suggest that the introduction of the vdW heterostructure into the NOEMS family will be of particular potential for the development of novel lab-on-a-chip systems.

A Review on Graphene-Based Nano-Electromechanical Resonators: Fabrication, Performance, and Applications.

The emergence of graphene and other two-dimensional materials overcomes the limitation in the characteristic size of silicon-based micro-resonators and paved the way in the realization of nano-mechanical resonators. In this paper, we review the progress to date of the research on the fabrication methods, resonant performance, and device applications of graphene-based nano-mechanical resonators, from theoretical simulation to experimental results, and summarize both the excitation and detection schemes of graphene resonators. In recent years, the applications of graphene resonators such as mass sensors, pressure sensors, and accelerometers gradually moved from theory to experiment, which are specially introduced in this review. To date, the resonance performance of graphene-based nano-mechanical resonators is widely studied by theoretical approaches, while the corresponding experiments are still in the preliminary stage. However, with the continuous progress of the device fabrication and detection technique, and with the improvement of the theoretical model, suspended graphene membranes will widen the potential for ultralow-loss and high-sensitivity mechanical resonators in the near future.

Correlated states in doubly-aligned hBN/graphene/hBN heterostructures.

Interfacial moiré superlattices in van der Waals vertical assemblies effectively reconstruct the crystal symmetry, leading to opportunities for investigating exotic quantum states. Notably, a two-dimensional nanosheet has top and bottom open surfaces, allowing the specific case of doubly aligned super-moiré lattice to serve as a toy model for studying the tunable lattice symmetry and the complexity of related electronic structures. Here, we show that by doubly aligning a graphene monolayer to both top and bottom encapsulating hexagonal boron nitride (h-BN), multiple conductivity minima are observed away from the main Dirac point, which are sensitively tunable with respect to the small twist angles. Moreover, our experimental evidences together with theoretical calculations suggest correlated insulating states at integer fillings of -5, -6, -7 electrons per moiré unit cell, possibly due to inter-valley coherence. Our results provide a way to construct intriguing correlations in 2D electronic systems in the weak interaction regime.

High Mobility Two-Dimensional Bismuth Oxyselenide Single Crystals with Large Grain Size Grown by Reverse-Flow Chemical Vapor Deposition.

2D semiconductors with atomically thin body thickness have attracted tremendous research interest for high-performance nanoelectronics and optoelectronics. Most of the 2D semiconductors grown by chemical vapor deposition (CVD) methods suffer from rather low carrier mobility, small single-crystal size, and instability under ambient conditions. Here, we develop an improved CVD method with controllable reverse-gas flow to realize the direct growth of quality Bi2O2Se 2D single crystals on a mica substrate. The applied reverse flow significantly suppresses the random nucleation and thus promotes the lateral size of 2D Bi2O2Se crystals up to ∼750 µm. The Bi2O2Se field-effect transistors display high-room-temperature electron mobility up to ∼1400 cm2·V-1·s-1 and a well-defined drain current saturation. The on/off ratio of the Bi2O2Se transistor is larger than 107, and the sub-threshold swing is about 90 mV·dec-1. The responsivity, response time, and detectivity of Bi2O2Se photodetectors approach up to 60 A·W-1, 5 ms, and 2.4 × 1010 Jones at room temperature, respectively. Our results demonstrate large-size and high-quality Bi2O2Se grown by reverse-flow CVD as a high-performance channel material for next-generation transistors and photodetectors.

Strain-Induced Alternating Photoluminescence Segmentation in Hexagonal Monolayer Tungsten Disulfide Grown by Physical Vapor Deposition.

Two-dimensional semiconductors exhibit strong light emission under optical or electrical pumping due to quantum confinement and large exciton binding energies. The regulation of the light emission shows great application potential in next-generation optoelectronic devices. Herein, by the physical vapor deposition strategy, we synthesize monolayer hexagonal-shaped WS2, and its photoluminescence intensity mapping show three-fold symmetric patterns with alternating bright and dark regions. Regardless of the length of the edges, all domains with S-terminated edges show lower photoluminescence intensity, while all regions with W-terminated edges exhibit higher photoluminescence intensity. The photoluminescence segmentation mechanism is studied in detail by employing Raman spectroscopy, atomic force microscopy, high-resolution transmission electron microscopy, and Kelvin probe force microscopy, and it is found to originate from different strain distributions in the S-terminated region and the W-terminated region. The optical band gap determined by the photoluminescence in the dark region is ∼2 meV lower than that in the bright region, implying that more strain is stored in the S-terminated region than in the W-terminated region. The photoluminescence segmentation vanishes in transferred hexagonal-shaped WS2 from the initial substrate to a fresh silicon substrate, further confirming the physical mechanism. Our results provide guidance for tuning the optical properties of two-dimensional semiconductors by controllable strain engineering.

Direct Visualization and Manipulation of Stacking Orders in Few-Layer Graphene by Dynamic Atomic Force Microscopy.

Stacking order plays a central role in governing a wide range of properties in layered two-dimensional materials. In the case of few-layer graphene, there are two common stacking configurations: ABA and ABC stacking, which have been proven to exhibit dramatically different electronic properties. However, the controllable characterization and manipulation between them remain a great challenge. Here, we report that ABA- and ABC-stacked domains can be directly visualized in phase imaging by tapping-mode atomic force microscopy with much higher spatial resolution than conventional optical spectroscopy. The contrasting phase is caused by the different energy dissipation by the tip-sample interaction. We further demonstrate controllable manipulation on the ABA/ABC domain walls by means of propagating stress transverse waves generated by the tapping of tip. Our results offer a reliable strategy for direct imaging and precise control of the atomic structures in few-layer graphene, which can be extended to other two-dimensional materials.

Phase-Changing in Graphite Assisted by Interface Charge Injection.

Among many phase-changing materials, graphite is probably the most studied and interesting: the rhombohedral (3R) and hexagonal (2H) phases exhibit dramatically different electronic properties. However, up to now the only way to promote 3R to 2H phase transition is through exposure to elevated temperatures (above 1000 °C); thus, it is not feasible for modern technology. In this work, we demonstrate that 3R to 2H phase transition can be promoted by changing the charged state of 3D graphite, which promotes the repulsion between the layers and significantly reduces the energy barrier between the 3R and 2H phases. In particular, we show that charge transfer from lithium nitride (α-Li3N) to graphite can lower the transition temperature down to 350 °C. The proposed interlayer slipping model potentially offers the control over topological states at the interfaces between different phases, making this system even more attractive for future electronic applications.

Functional Group-induced p-Doping of MoS2 by Titanium(IV) Bis(ammonium lactato) Dihydroxide Physisorption.

P-type doping is of critical importance for the realization of certain high-performance electrical and optoelectronic devices based on molybdenum disulfide (MoS2 ). Charge transfer doping is a feasible strategy for tuning the conductance properties via facile treatment. In this work, the electrical properties of few-layer MoS2 were modulated with titanium(IV) bis(ammonium lactato) dihydroxide molecules (denoted as TALH) via physisorption. The functional groups such as electronegative hydroxyl (-OH) and carboxylate groups (-COO) included in TALH molecules are expected to induce p-doping effect through surface charge transfer when being attached to MoS2 . The p-doping is proved by X-ray photoelectron spectroscopy (XPS) with the downshift of Mo 3d and S 2p peaks. Control experiments and density functional theory calculations validate that the p-type doping mainly originated from the -OH group in TALH, which drew electrons from MoS2 . These results suggest that functional group-mediated p-doping effect show a path to modulate the carrier transition in MoS2, and enrich the molecule series for device modification.

Light-induced irreversible structural phase transition in trilayer graphene.

A crystal structure has a profound influence on the physical properties of the corresponding material. By synthesizing crystals with particular symmetries, one can strongly tune their properties, even for the same chemical configuration (compare graphite and diamond, for instance). Even more interesting opportunities arise when the structural phases of crystals can be changed dynamically through external stimulations. Such abilities, though rare, lead to a number of exciting phenomena, such as phase-change memory effects. In the case of trilayer graphene, there are two common stacking configurations (ABA and ABC) that have distinct electronic band structures and exhibit very different behaviors. Domain walls exist in the trilayer graphene with both stacking orders, showing fascinating new physics such as the quantum valley Hall effect. Extensive efforts have been dedicated to the phase engineering of trilayer graphene. However, the manipulation of domain walls to achieve precise control of local structures and properties remains a considerable challenge. Here, we experimentally demonstrate that we can switch from one structural phase to another by laser irradiation, creating domains of different shapes in trilayer graphene. The ability to control the position and orientation of the domain walls leads to fine control of the local structural phases and properties of graphene, offering a simple but effective approach to create artificial two-dimensional materials with designed atomic structures and electronic and optical properties.

Controllable Epitaxial Growth of MoSe2 Bilayers with Different Stacking Orders by Reverse-Flow Chemical Vapor Deposition.

The stacking order plays a critical role in the electronic and optical properties of two-dimensional materials. It is however of great challenge to achieve large-size and homogeneous bilayer crystals with precisely controlled stacking orders. Here, we demonstrate an optimized chemical vapor deposition strategy to grow MoSe2 bilayers with controlled AA or AB stacking sequences. Reverse gas flow effectively suppresses the random nucleation centers, leading to uniform growth of the second layer of MoSe2 on the first monolayer. A customized temperature profile selectively activates the growth of the MoSe2 bilayer with different stacking orders: the AA stacking MoSe2 bilayer tends to form at 810 °C, and the AB stacking MoSe2 bilayer prefers to grow at a higher temperature of 860 °C. A series of characterization methods confirm that MoSe2 bilayers with different stacking orders exhibit distinct crystal structures and physical properties. Our results demonstrate a robust and effective route for the controllable synthesis of transition metal dichalcogenide bilayers, which will benefit the development of two-dimensional materials and van der Waals heterostructures.

Enhanced Superconductivity in Few-Layer TaS2 due to Healing by Oxygenation.

When approaching the atomically thin limit, defects and disorder play an increasingly important role in the properties of two-dimensional (2D) materials. While defects are generally thought to negatively affect superconductivity in 2D materials, here we demonstrate the contrary in the case of oxygenation of ultrathin tantalum disulfide (TaS2). Our first-principles calculations show that incorporation of oxygen into the TaS2 crystal lattice is energetically favorable and effectively heals sulfur vacancies typically present in these crystals, thus restoring the electronic band structure and the carrier density to the intrinsic characteristics of TaS2. Strikingly, this leads to a strong enhancement of the electron-phonon coupling, by up to 80% in the highly oxygenated limit. Using transport measurements on fresh and aged (oxygenated) few-layer TaS2, we found a marked increase of the superconducting critical temperature (Tc) upon aging, in agreement with our theory, while concurrent electron microscopy and electron-energy loss spectroscopy confirmed the presence of sulfur vacancies in freshly prepared TaS2 and incorporation of oxygen into the crystal lattice with time. Our work thus reveals the mechanism by which certain atomic-scale defects can be beneficial to superconductivity and opens a new route to engineer Tc in ultrathin materials.