Scalable integration of hybrid high-κ dielectric materials on two-dimensional semiconductors.

Two-dimensional (2D) semiconductors are promising channel materials for next-generation field-effect transistors (FETs). However, it remains challenging to integrate ultrathin and uniform high-κ dielectrics on 2D semiconductors to fabricate FETs with large gate capacitance. We report a versatile two-step approach to integrating high-quality dielectric film with sub-1 nm equivalent oxide thickness (EOT) on 2D semiconductors. Inorganic molecular crystal Sb2O3 is homogeneously deposited on 2D semiconductors as a buffer layer, which forms a high-quality oxide-to-semiconductor interface and offers a highly hydrophilic surface, enabling the integration of high-κ dielectrics via atomic layer deposition. Using this approach, we can fabricate monolayer molybdenum disulfide-based FETs with the thinnest EOT (0.67 nm). The transistors exhibit an on/off ratio of over 106 using an ultra-low operating voltage of 0.4 V, achieving unprecedently high gating efficiency. Our results may pave the way for the application of 2D materials in low-power ultrascaling electronics.

Nanochannel-Based Transport in an Interfacial Memristor Can Emulate the Analog Weight Modulation of Synapses.

By exploiting novel transport phenomena such as ion selectivity at the nanoscale, it has been shown that nanochannel systems can exhibit electrically controllable conductance, suggesting their potential use in neuromorphic devices. However, several critical features of biological synapses, particularly their conductance modulation, which is both memorable and gradual, have rarely been reported in these types of systems due to the fast flow property of typical inorganic electrolytes. In this work, we demonstrate that electrically manipulating the nanochannel conductance can result in nonvolatile conductance tuning capable of mimicking the analog behavior of synapses by introducing a room-temperature ionic liquid (IL) and a KCl solution into the two ends of a nanochannel system. The gradual conductance-tuning mechanism is identified through fluorescence measurements as the voltage-induced movement of the interface between the immiscible IL and KCl solution, while the successful memorization of the conductance tuning is ascribed to the large viscosity of the IL. We applied a nanochannel-based synapse to a handwritten digit-recognition task, reaching an accuracy of 94%. These promising results provide important guidance for the future design of nanochannel-based neuromorphic devices and the manipulation of nanochannel transport for computing.

Rational Concept for Reducing Growth Temperature in Vapor-Liquid-Solid Process of Metal Oxide Nanowires.

Vapor-liquid-solid (VLS) growth process of single crystalline metal oxide nanowires has proven the excellent ability to tailor the nanostructures. However, the VLS process of metal oxides in general requires relatively high growth temperatures, which essentially limits the application range. Here we propose a rational concept to reduce the growth temperature in VLS growth process of various metal oxide nanowires. Molecular dynamics (MD) simulation theoretically predicts that it is possible to reduce the growth temperature in VLS process of metal oxide nanowires by precisely controlling the vapor flux. This concept is based on the temperature dependent "material flux window" that the appropriate vapor flux for VLS process of nanowire growth decreases with decreasing the growth temperature. Experimentally, we found the applicability of this concept for reducing the growth temperature of VLS processes for various metal oxides including MgO, SnO2, and ZnO. In addition, we show the successful applications of this concept to VLS nanowire growths of metal oxides onto tin-doped indium oxide (ITO) glass and polyimide (PI) substrates, which require relatively low growth temperatures.

A Ternary Solvent Method for Large-Sized Two-Dimensional Perovskites.

Recent reports demonstrate that a two-dimensional (2D) structural characteristic can endow perovskites with both remarkable photoelectric conversion efficiency and high stability, but the synthesis of ultrathin 2D perovskites with large sizes by facile solution methods is still a challenge. Reported herein is the controlled growth of 2D (C4 H9 NH3 )2 PbBr4 perovskites by a chlorobenzene-dimethylformide-acetonitrile ternary solvent method. The critical factors, including solvent volume ratio, crystallization temperature, and solvent polarity on the growth dynamics were systematically studied. Under optimum reaction condition, 2D (C4 H9 NH3 )2 PbBr4 perovskites, with the largest lateral dimension of up to 40 µm and smallest thickness down to a few nanometers, were fabricated. Furthermore, various iodine doped 2D (C4 H9 NH3 )2 PbBrx I4-x perovskites were accessed to tune the optical properties rationally.

Rational Concept for Designing Vapor-Liquid-Solid Growth of Single Crystalline Metal Oxide Nanowires.

Metal oxide nanowires hold great promise for various device applications due to their unique and robust physical properties in air and/or water and also due to their abundance on Earth. Vapor-liquid-solid (VLS) growth of metal oxide nanowires offers the high controllability of their diameters and spatial positions. In addition, VLS growth has applicability to axial and/or radial heterostructures, which are not attainable by other nanowire growth methods. However, material species available for the VLS growth of metal oxide nanowires are substantially limited even though the variety of material species, which has fascinating physical properties, is the most interesting feature of metal oxides. Here we demonstrate a rational design for the VLS growth of various metal oxide nanowires, based on the "material flux window". This material flux window describes the concept of VLS nanowire growth within a limited material flux range, where nucleation preferentially occurs only at a liquid-solid interface. Although the material flux was previously thought to affect primarily the growth rate, we experimentally and theoretically demonstrate that the material flux is the important experimental variable for the VLS growth of metal oxide nanowires. On the basis of the material flux window concept, we discover novel metal oxide nanowires, composed of MnO, CaO, Sm2O3, NiO, and Eu2O3, which were previously impossible to form via the VLS route. The newly grown NiO nanowires exhibited stable memristive properties superior to conventional polycrystalline devices due to the single crystallinity. Thus, this VLS design route offers a useful guideline for the discovery of single crystalline nanowires that are composed of functional metal oxide materials.

Modulation of thermoelectric power factor via radial dopant inhomogeneity in B-doped Si nanowires.

We demonstrate a modulation of thermoelectric power factor via a radial dopant inhomogeneity in B-doped Si nanowires. These nanowires grown via vapor-liquid-solid (VLS) method were naturally composed of a heavily doped outer shell layer and a lightly doped inner core. The thermopower measurements for a single nanowire demonstrated that the power factor values were higher than those of homogeneously B-doped Si nanowires. The field effect measurements revealed the enhancement of hole mobility for these VLS grown B-doped Si nanowires due to the modulation doping effect. This mobility enhancement increases overall electrical conductivity of nanowires without decreasing the Seebeck coefficient value, resulting in the increase of thermoelectric power factor. In addition, we found that tailoring the surface dopant distribution by introducing surface δ-doping can further increase the power factor value. Thus, intentionally tailoring radial dopant inhomogeneity promises a way to modulate the thermoelectric power factor of semiconductor nanowires.

Revealing Strong Flexoelectricity and Optoelectronic Coupling in 2D Ferroelectric CuInP2S6 Via Large Strain Gradient.

The interplay between flexoelectric and optoelectronic characteristics provides a paradigm for studying emerging phenomena in various 2D materials. However, an effective way to induce a large and tunable strain gradient in 2D devices remains to be exploited. Herein, we propose a strategy to induce large flexoelectric effect in 2D ferroelectric CuInP2S6 by constructing a 1D-2D mixed-dimensional heterostructure. The strong flexoelectric effect is induced by enormous strain gradient up to 4.2 × 106 m-1 resulting from the underlying ZnO nanowires, which is further confirmed by the asymmetric coercive field and the red-shift in the absorption edge. The induced flexoelectric polarization efficiently boosts the self-powered photodetection performance. In addition, the improved photoresponse has a good correlation with the induced strain gradient, showing a consistent size-dependent flexoelectric effect. The mechanism of flexoelectric and optoelectronic coupling is proposed based on the Landau-Ginzburg-Devonshire double-well model, supported by density functional theory (DFT) calculations. This work provides a brand-new method to induce a strong flexoelectric effect in 2D materials, which is not restricted to crystal symmetry and thus offers unprecedented opportunities for state-of-the-art 2D devices.

Impact of preferential indium nucleation on electrical conductivity of vapor-liquid-solid grown indium-tin oxide nanowires.

Highly conductive and transparent indium-tin oxide (ITO) single-crystalline nanowires, formed by the vapor-liquid-solid (VLS) method, hold great promise for various nanoscale device applications. However, increasing an electrical conductivity of VLS grown ITO nanowires is still a challenging issue due to the intrinsic difficulty in controlling complex material transports of the VLS process. Here, we demonstrate a crucial role of preferential indium nucleation on the electrical conductivity of VLS grown ITO nanowires using gold catalysts. In spite of the fact that the vapor pressure of tin is lower than that of indium, we found that the indium concentration within the nanowires was always higher than the nominal composition. The VLS growth of ITO through gold catalysts significantly differs from ITO film formations due to the emergence of preferential indium nucleation only at a liquid-solid interface. Furthermore, we demonstrate that the averaged resistivity of ITO nanowires can be decreased down to 2.1 × 10(-4) Ω cm, which is the lowest compared with values previously reported, via intentionally increasing the tin concentration within the nanowires.

Prominent thermodynamical interaction with surroundings on nanoscale memristive switching of metal oxides.

This study demonstrates the effect of surroundings on a memristive switching at nanoscale by utilizing an open top planar-type device. NiO(x) and CoO(x) planar-type devices have exhibited a memristive behavior under atmospheric pressure, whereas TiO(2-x) planar-type devices did not show a memristive switching even under the same surroundings. A memristive behavior of TiO(2-x) planar-type devices has emerged when reducing an ambient pressure and/or employing a SiO(2) passivation layer. These results reveal that a thermodynamical interaction with surroundings critically determines the occurrence of memristive switching via varying a stability of nonstoichiometry. Since this effect tends to be more significant for smaller devices with larger specific surface area, tailoring the surrounding effect by an appropriate passivation will be essential for high density devices.

Simultaneously ultrafast and robust two-dimensional flash memory devices based on phase-engineered edge contacts.

As the prevailing non-volatile memory (NVM), flash memory offers mass data storage at high integration density and low cost. However, due to the 'speed-retention-endurance' dilemma, their typical speed is limited to ~microseconds to milliseconds for program and erase operations, restricting their application in scenarios with high-speed data throughput. Here, by adopting metallic 1T-LixMoS2 as edge contact, we show that ultrafast (10-100 ns) and robust (endurance>106 cycles, retention>10 years) memory operation can be simultaneously achieved in a two-dimensional van der Waals heterostructure flash memory with 2H-MoS2 as semiconductor channel. We attribute the superior performance to the gate tunable Schottky barrier at the edge contact, which can facilitate hot carrier injection to the semiconductor channel and subsequent tunneling when compared to a conventional top contact with high density of defects at the metal interface. Our results suggest that contact engineering can become a strategy to further improve the performance of 2D flash memory devices and meet the increasing demands of high speed and reliable data storage.

Adaptive Neural Activation and Neuromorphic Processing via Drain-Injection Threshold-Switching Float Gate Transistor Memory.

Hetero-modulated neural activation is vital for adaptive information processing and learning that occurs in brain. To implement brain-inspired adaptive processing, previously various neurotransistors oriented for synaptic functions are extensively explored, however, the emulation of nonlinear neural activation and hetero-modulated behaviors are not possible due to the lack of threshold switching behavior in a conventional transistor structure. Here, a 2D van der Waals float gate transistor (FGT) that exhibits steep threshold switching behavior, and the emulation of hetero-modulated neuron functions (integrate-and-fire, sigmoid type activation) for adaptive sensory processing, are reported. Unlike conventional FGTs, the threshold switching behavior stems from impact ionization in channel and the coupled charge injection to float gate. When a threshold is met, a sub-30 mV dec-1 increase of transistor conductance by more than four orders is triggered with a typical switch time of approximately milliseconds. Essentially, by feeding light sensing signal as the modulation input, it is demonstrated that two typical tasks that rely on adaptive neural activation, including collision avoidance and adaptive visual perception, can be realized. These results may shed light on the emulation of rich hetero-modulating behaviors in biological neurons and the realization of biomimetic neuromorphic processing at low hardware cost.

Advantages of using Ti-mesh type electrodes for flexible dye-sensitized solar cells.

We used Ti meshes for both the photoanodes and counter electrodes of dye-sensitized solar cells (DSSCs) to improve the flexibility and conductivity of the electrodes. These mesh type electrodes showed good transparency and high bendability when subjected to an external force. We demonstrated the advantages of cells using such electrodes compared to traditional transparent conducting oxide based electrodes and back side illuminated DSSCs, such as low sheet resistance, elevated photo-induced current and enhanced sunlight utilization. Nanotube layers of different thicknesses were investigated to determine their effect on the photovoltaic parameters of the cell. The overall efficiency of the best cells was approximately 5.3% under standard air mass 1.5 global (AM 1.5 G) solar conditions. Furthermore, the DSSCs showed an efficiency of approximately 3.15% due to the all Ti-mesh type electrodes even after illumination from the back side.

A non-linear two-dimensional float gate transistor as a lateral inhibitory synapse for retinal early visual processing.

Synaptic transistors that accommodate concurrent signal transmission and learning in a neural network are attracting enormous interest for neuromorphic sensory processing. To remove redundant sensory information while keeping important features, artificial synaptic transistors with non-linear conductance are desired to apply filter processing to sensory inputs. Here, we report the realization of non-linear synapses using a two-dimensional van der Waals (vdW) heterostructure (MoS2/h-BN/graphene) based float gate memory device, in which the semiconductor channel is tailored via a surface acceptor (ZnPc) for subthreshold operation. In addition to usual synaptic plasticity, the memory device exhibits highly non-linear conductance (rectification ratio >106), allowing bidirectional yet only negative/inhibitory current to pass through. We demonstrate that in a lateral coupling network, such a float gate memory device resembles the key lateral inhibition function of horizontal cells for the formation of an ON-center/OFF-surround receptive field. When combined with synaptic plasticity, the lateral inhibition weights are further tunable to enable adjustable edge enhancement for early visual processing. Our results here hopefully open a new scheme toward early sensory perception via lateral inhibitory synaptic transistors.

High-Performance Planar-Type Photodetector Based on Hot-Pressed CsPbBr3 Wafer.

Considering the disadvantages of the common methods for CsPbBr3 single crystal growth including the high cost of the melt method and the low shape controllability of the solution method, a facile hot-pressed (HP) approach has been introduced to prepare CsPbBr3 wafers. The effects of HP temperature on the phase purity of HP-CsPbBr3 wafers and the performance of the corresponding photodetectors have been investigated. The HP temperature for preparing phase-pure, shape-regular, and dense CsPbBr3 wafers has been optimized to be 150 °C, and the HP-CsPbBr3 wafer based planar-type photodetectors exhibit an ultrasensitive weak light photoresponse. Under the illumination of a 530 nm LED with a light power density of 1.1 µW cm-2, the responsivity, external quantum efficiency, and detectivity of the devices reach 19.79 A W-1, 4634%, and 2.14 × 1013 Jones, respectively, and a fast response speed with a rise time of 40.5 µs and a fall time of 10.0 µs has been achieved.

Complementary Memtransistor-Based Multilayer Neural Networks for Online Supervised Learning Through (Anti-)Spike-Timing-Dependent Plasticity.

We propose a complete hardware-based architecture of multilayer neural networks (MNNs), including electronic synapses, neurons, and periphery circuitry to implement supervised learning (SL) algorithm of extended remote supervised method (ReSuMe). In this system, complementary (a pair of n- and p-type) memtransistors (C-MTs) are used as an electrical synapse. By applying the learning rule of spike-timing-dependent plasticity (STDP) to the memtransistor connecting presynaptic neuron to the output one whereas the contrary anti-STDP rule to the other memtransistor connecting presynaptic neuron to the teacher one, extended ReSuMe with multiple layers is realized without the usage of those complicated supervising modules in previous approaches. In this way, both the C-MT-based chip area and power consumption of the learning circuit for weight updating operation are drastically decreased comparing with the conventional single memtransistor (S-MT)-based designs. Two typical benchmarks, the linearly nonseparable benchmark XOR problem and Mixed National Institute of Standards and Technology database (MNIST) recognition have been successfully tackled using the proposed MNN system while impact of the nonideal factors of realistic devices has been evaluated.

A Reconfigurable Two-WSe2 -Transistor Synaptic Cell for Reinforcement Learning.

Reward-modulated spike-timing-dependent plasticity (R-STDP) is a brain-inspired reinforcement learning (RL) rule, exhibiting potential for decision-making tasks and artificial general intelligence. However, the hardware implementation of the reward-modulation process in R-STDP usually requires complicated Si complementary metal-oxide-semiconductor (CMOS) circuit design that causes high power consumption and large footprint. Here, a design with two synaptic transistors (2T) connected in a parallel structure is experimentally demonstrated. The 2T unit based on WSe2 ferroelectric transistors exhibits reconfigurable polarity behavior, where one channel can be tuned as n-type and the other as p-type due to nonvolatile ferroelectric polarization. In this way, opposite synaptic weight update behaviors with multilevel (>6 bit) conductance states, ultralow nonlinearity (0.56/-1.23), and large Gmax /Gmin ratio of 30 are realized. By applying positive/negative reward to (anti-)STDP component of 2T cell, R-STDP learning rules are realized for training the spiking neural network and demonstrated to solve the classical cart-pole problem, exhibiting a way for realizing low-power (32 pJ per forward process) and highly area-efficient (100 µm2 ) hardware chip for reinforcement learning.

Ultrafast and stable phase transition realized in MoTe2-based memristive devices.

Phase engineering of two-dimensional transition metal dichalcogenides has received increasing attention in recent years due to its atomically thin nature and polymorphism. Here, we first realize an electric-field-induced controllable phase transition between semiconducting 2H and metallic 1T' phases in MoTe2 memristive devices. The device performs stable bipolar resistive switching with a cycling endurance of over 105, an excellent retention characteristic of over 105 s at an elevated temperature of 85 °C and an ultrafast switching of ∼5 ns for SET and ∼10 ns for RESET. More importantly, the device works in different atmospheres including air, vacuum and oxygen, and even works with no degradation after being placed in air for one year, indicating excellent surrounding and time stability. In situ Raman analysis reveals that the stable resistive switching originates from a controllable phase transition between 2H and 1T' phases. Density functional theory calculations reveal that the Te vacancy facilitates the phase transition in MoTe2 through decreasing the barrier between 2H and 1T' phases, and serving as nucleation sites due to the elimination of repulsive forces. This electric-field-induced controllable phase transition in MoTe2 devices offers new opportunities for developing reliable and ultrafast phase transition devices based on atomically thin membranes.

Approaching strain limit of two-dimensional MoS2 via chalcogenide substitution.

Strain engineering is a promising method for tuning the electronic properties of two-dimensional (2D) materials, which are capable of sustaining enormous strain thanks to their atomic thinness. However, applying a large and homogeneous strain on these 2D materials, including the typical semiconductor MoS2, remains cumbersome. Here we report a facile strategy for the fabrication of highly strained MoS2 via chalcogenide substitution reaction (CSR) of MoTe2 with lattice inheritance. The MoS2 resulting from the sulfurized MoTe2 sustains ultra large in-plane strain (approaching its strength limit ~10%) with great homogeneity. Furthermore, the strain can be deterministically and continuously tuned to ~1.5% by simply varying the processing temperature. Thanks to the fine control of our CSR process, we demonstrate a heterostructure of strained MoS2/MoTe2 with abrupt interface. Finally, we verify that such a large strain potentially allows the modulation of MoS2 bandgap over an ultra-broad range (~1 eV). Our controllable CSR strategy paves the way for the fabrication of highly strained 2D materials for applications in devices.

TiO2 nanorod arrays functionalized with In2S3 shell layer by a low-cost route for solar energy conversion.

We report the fabrication and characterization of a TiO(2)-In(2)S(3) core-shell nanorod array structure for application of semiconductor-sensitized solar cells. Hydrothermally synthesized TiO(2) nanorod arrays on FTO glass substrates are functionalized with a uniform In(2)S(3) shell layer by using the successive ion layer adsorption and reaction (SILAR) method. This low-cost technique promotes a uniform deposition of In(2)S(3) nanoshells on the surface of TiO(2) nanorods, thus forming an intact interface between the In(2)S(3) shell and TiO(2) core. Results show that the thickness of In(2)S(3) shell layers as well as the visible light absorption threshold can be effectively controlled by varying the coating cycles during the SILAR process. The best reproducible performance of the sandwich solar cell using the TiO(2)-In(2)S(3) core-shell nanorod arrays as photoelectrodes was obtained after 30 SILAR cycles, exhibiting a short-circuit current (I(sc)) of 2.40 mA cm(-2), an open-circuit voltage (V(oc)) of 0.56 V, a fill factor (ff) of 0.40 and a conversion efficiency (η) of 0.54%, respectively. These results demonstrate a feasible and controllable route towards In(2)S(3) coating on a highly structured substrate and a proof of concept that such TiO(2)-In(2)S(3) core-shell architectures are novel and promising photoelectrodes in nanostructured solar cells.

Design and tailoring of two-dimensional Schottky, PN and tunnelling junctions for electronics and optoelectronics.

Owing to their superior carrier mobility, strong light-matter interactions, and flexibility at the atomically thin thickness, two-dimensional (2D) materials are attracting wide interest for application in electronic and optoelectronic devices, including rectifying diodes, transistors, memory, photodetectors, and light-emitting diodes. At the heart of these devices, Schottky, PN, and tunneling junctions are playing an essential role in defining device function. Intriguingly, the ultrathin thickness and unique van der Waals (vdW) interlayer coupling in 2D materials has rendered enormous opportunities for the design and tailoring of various 2D junctions, e.g. using Lego-like hetero-stacking, surface decoration, and field-effect modulation methods. Such flexibility has led to marvelous breakthroughs during the exploration of 2D electronics and optoelectronic devices. To advance further, it is imperative to provide an overview of existing strategies for the engineering of various 2D junctions for their integration in the future. Thus, in this review, we provide a comprehensive survey of previous efforts toward 2D Schottky, PN, and tunneling junctions, and the functional devices built from them. Though these junctions exhibit similar configurations, distinct strategies have been developed for their optimal figures of merit based on their working principles and functional purposes.