Ag-doped non-imperfection-enabled uniform memristive neuromorphic device based on van der Waals indium phosphorus sulfide.

Memristors are considered promising energy-efficient artificial intelligence hardware, which can eliminate the von Neumann bottleneck by parallel in-memory computing. The common imperfection-enabled memristors are plagued with critical variability issues impeding their commercialization. Reported approaches to reduce the variability usually sacrifice other performances, e.g., small on/off ratios and high operation currents. Here, we demonstrate an unconventional Ag-doped nonimperfection diffusion channel-enabled memristor in van der Waals indium phosphorus sulfide, which can combine ultralow variabilities with desirable metrics. We achieve operation voltage, resistance, and on/off ratio variations down to 3.8, 2.3, and 6.9% at their extreme values of 0.2 V, 1011 ohms, and 108, respectively. Meanwhile, the operation current can be pushed from 1 nA to 1 pA at the scalability limit of 6 nm after Ag doping. Fourteen Boolean logic functions and convolutional image processing are successfully implemented by the memristors, manifesting the potential for logic-in-memory devices and efficient non-von Neumann accelerators.

Intrinsic Defect-Driven Synergistic Synaptic Heterostructures for Gate-Free Neuromorphic Phototransistors.

The optoelectronic synaptic devices based on two-dimensional (2D) materials offer great advances for future neuromorphic visual systems with dramatically improved integration density and power efficiency. The effective charge capture and retention are considered as one vital prerequisite to realizing the synaptic memory function. However, the current 2D synaptic devices are predominantly relied on materials with artificially-engineered defects or intricate gate-controlled architectures to realize the charge trapping process. These approaches, unfortunately, suffer from the degradation of pristine materials, rapid device failure, and unnecessary complication of device structures. To address these challenges, an innovative gate-free heterostructure paradigm is introduced herein. The heterostructure presents a distinctive dome-like morphology wherein a defect-rich Fe7S8 core is enveloped snugly by a curved MoS2 dome shell (Fe7S8@MoS2), allowing the realization of effective photocarrier trapping through the intrinsic defects in the adjacent Fe7S8 core. The resultant neuromorphic devices exhibit remarkable light-tunable synaptic behaviors with memory time up to ≈800 s under single optical pulse, thus demonstrating great advances in simulating visual recognition system with significantly improved image recognition efficiency. The emergence of such heterostructures foreshadows a promising trajectory for underpinning future synaptic devices, catalyzing the realization of high-efficiency and intricate visual processing applications.

van der Waals Epitaxial Growth of One-Unit-Cell-Thick Ferroelectric CuCrS2 Nanosheets.

Ferroelectric two-dimensional (2D) materials with a high transition temperature are highly desirable for new physics and next-generation memory electronics. However, the long-range polar order of ferroelectrics will barely persist when the thickness reaches the nanoscale. In this work, we synthesized 2D CuCrS2 nanosheets with thicknesses down to one unit cell via van der Waals epitaxy in a chemical vapor deposition system. A combination of transmission electron microscopy, second-harmonic generation, and Raman spectroscopy measurements confirms the R3m space group and noncentrosymmetric structure. Switchable ferroelectric domains and obvious ferroelectric hysteresis loops were created and visualized by piezoresponse force microscopy. Theoretical calculation helps us understand the mechanism of ferroelectric switching in CuCrS2 nanosheets. Finally, we fabricated a ferroelectric memory device that achieves an on/off ratio of ∼102 and remains stable after 2000 s, indicating its applicability in novel nanoelectronics. Overall, 2D CuCrS2 nanosheets exhibit excellent ferroelectric properties at the nanoscale, showing great promise for next-generation devices.

Engineering Atomic-Scale Patterning and Resistive Switching in 2D Crystals and Application in Image Processing.

The ultrathin thickness of 2D layered materials affords the control of their properties through defects, surface modification, and electrostatic fields more efficiently compared with bulk architecture. In particular, patterning design, such as moiré superlattice patterns and spatially periodic dielectric structures, are demonstrated to possess the ability to precisely control the local atomic and electronic environment at large scale, thus providing extra degrees of freedom to realize tailored material properties and device functionality. Here, the scalable atomic-scale patterning in superionic cuprous telluride by using the bonding difference at nonequivalent copper sites is reported. Moreover, benefitting from the natural coupling of ordered and disordered sublattices, controllable piezoelectricity-like multilevel switching and bipolar switching with the designed crystal structure and electrical contact is realized, and their application in image enhancement is demonstrated. This work extends the known classes of patternable crystals and atomic switching devices, and ushers in a frontier for image processing with memristors.

2D Ferroic Materials for Nonvolatile Memory Applications.

The emerging nonvolatile memory technologies based on ferroic materials are promising for producing high-speed, low-power, and high-density memory in the field of integrated circuits. Long-range ferroic orders observed in 2D materials have triggered extensive research interest in 2D magnets, 2D ferroelectrics, 2D multiferroics, and their device applications. Devices based on 2D ferroic materials and heterostructures with an atomically smooth interface and ultrathin thickness have exhibited impressive properties and significant potential for developing advanced nonvolatile memory. In this context, a systematic review of emergent 2D ferroic materials is conducted here, emphasizing their recent research on nonvolatile memory applications, with a view to proposing brighter prospects for 2D magnetic materials, 2D ferroelectric materials, 2D multiferroic materials, and their relevant devices.

Phase Engineering of 2D Spinel-Type Manganese Oxides.

2D magnetic materials have been of interest due to their unique long-range magnetic ordering in the low-dimensional regime and potential applications in spintronics. Currently, most studies are focused on strippable van der Waals magnetic materials with layered structures, which typically suffer from a poor stability and scarce species. Spinel oxides have a good environmental stability and rich magnetic properties. However, the isotropic bonding and close-packed nonlayered crystal structure make their 2D growth challenging, let alone the phase engineering. Herein, a phase-controllable synthesis of 2D single-crystalline spinel-type oxides is reported. Using the van der Waals epitaxy strategy, the thicknesses of the obtained tetragonal and hexagonal manganese oxide (Mn3 O4 ) nanosheets can be tuned down to 7.1 nm and one unit cell (0.7 nm), respectively. The magnetic properties of these two phases are evaluated using vibrating-sample magnetometry and first-principle calculations. Both structures exhibit a Curie temperature of 48 K. Owing to its ultrathin geometry, the Mn3 O4 nanosheet exhibits a superior ultraviolet detection performance with an ultralow noise power density of 0.126 pA Hz-1/2 . This study broadens the range of 2D magnetic semiconductors and highlights their potential applications in future information devices.

Room-Temperature Intrinsic Ferromagnetic Chromium Tellurium Compounds with Thickness-Tunable Magnetic Texture.

2D ferromagnetic chromium tellurides exhibit intriguing spin configurations and high-temperature intrinsic ferromagnetism, providing unprecedented opportunities to explore the fundamental spin physics and build spintronic devices. Here, a generic van der Waals epitaxial approach is developed to synthesize the 2D ternary chromium tellurium compounds with thicknesses down to mono-, bi-, tri-, and few-unit cells (UC). The Mn0.14 Cr0.86 Te evolves from intrinsic ferromagnetic behavior in bi-UC, tri-UC, and few-UC to temperature-induced ferrimagnetic behavior as the thickness increases, resulting in a sign reversal of the anomalous Hall resistance. Temperature- and thickness-tunable labyrinthine-domain ferromagnetic behaviors are derived from the dipolar interactions in Fe0.26 Cr0.74 Te and Co0.40 Cr0.60 Te. Furthermore, the dipolar-interaction-induced stripe domain and field-induced domain wall (DW) motion velocity are studied, and multibit data storage is realized through an abundant DW state. The magnetic storage can function in neuromorphic computing tasks, and the pattern recognition accuracy can reach up to 97.93%, which is similar to the recognition accuracy of ideal software-based training (98.28%). Room-temperature ferromagnetic chromium tellurium compounds with intriguing spin configurations can significantly promote the exploration of the processing, sensing, and storage based on 2D magnetic systems.

Heteroepitaxy of 2D CuCr2 Te4 with Robust Room-temperature Ferromagnetism.

Magnetic materials in 2D have attracted widespread attention for their intriguing magnetic properties. 2D magnetic heterostructures can provide unprecedented opportunities for exploring fundamental physics and novel spintronic devices. Here, the heteroepitaxial growth of ferromagnetic CuCr2 Te4 nanosheets is reported on Cr2 Te3 and mica by chemical vapor deposition. Magneto-optical Kerr effect measurements reveal the thickness-dependent ferromagnetism of CuCr2 Te4 nanosheets on mica, where a decrease of Curie temperature (TC ) from 320 to 260 K and an enhancement of perpendicular magnetic anisotropy with reducing thickness are observed. Moreover, lattice-matched heteroepitaxial ultrathin CuCr2 Te4 on Cr2 Te3 exhibits an enhanced robust ferromagnetism with TC up to 340 K due to the interfacial charge transfer. Stripe-type magnetic domains and single magnetic domain are discovered in this heterostructure with different thicknesses. The work provides a way to construct robust room-temperature 2D magnetic heterostructures for functional spintronic devices.

Van der Waals Epitaxy Growth of 2D Single-Element Room-Temperature Ferromagnet.

2D single-element materials, which are pure and intrinsically homogeneous on the nanometer scale, can cut the time-consuming material-optimization process and circumvent the impure phase, bringing about opportunities to explore new physics and applications. Herein, for the first time, the synthesis of ultrathin cobalt single-crystalline nanosheets with a sub-millimeter scale via van der Waals epitaxy is demonstrated. The thickness can be as low as ≈6 nm. Theoretical calculations reveal their intrinsic ferromagnetic nature and epitaxial mechanism: that is, the synergistic effect between van der Waals interactions and surface energy minimization dominates the growth process. Cobalt nanosheets exhibit ultrahigh blocking temperatures above 710 K and in-plane magnetic anisotropy. Electrical transport measurements further reveal that cobalt nanosheets have significant magnetoresistance (MR) effect, and can realize a unique coexistence of positive MR and negative MR under different magnetic field configurations, which can be attributed to the competition and cooperation effect among ferromagnetic interaction, orbital scattering, and electronic correlation. These results provide a valuable case for synthesizing 2D elementary metal crystals with pure phase and room-temperature ferromagnetism and pave the way for investigating new physics and related applications in spintronics.

Van der Waals epitaxial growth of two-dimensional PbSe and its high-performance heterostructure devices.

Inspired by the great success of ultrathin two-dimensional (2D) layered crystals, more and more attention is being paid to preparing 2D nanostructures from non-layered materials. They can significantly enrich the 2D materials and 2D heterostructures family, extend their application prospects, and bring us distinct properties from their bulk counterparts due to the strong 2D confinement effect. However, the realization of 2D non-layered semiconductors with strong light-harvesting capability and the ability to construct high-performance 2D heterostructures is still a critical challenge. Herein, we successfully synthesized 2D PbSe semiconductors with a large lateral dimension and ultrathin thickness via van der Waals epitaxy. The fabricated 2D PbSe device exhibits good electrical conductivity and superior multi-wavelength photoresponse performance with high responsivity (∼103 A/W) and impressive detectivity (∼2 × 1011 Jones). Furthermore, we demonstrate that 2D PbSe nanosheets can serve as component units for constructing high-performance heterostructure devices. With our strategy, ultrahigh current on/off ratio (∼108) and rectification ratio (∼106), as well as high responsivity (∼3 × 103 A/W) and detectivity (∼7 × 1012 Jones), can be achieved in PbSe/MoS2 back-gated transistors. These results indicate that 2D PbSe nanosheets and their heterostructures have tremendous applications potential in electrical and optoelectronic devices.

Ultrathin ferrite nanosheets for room-temperature two-dimensional magnetic semiconductors.

The discovery of magnetism in ultrathin crystals opens up opportunities to explore new physics and to develop next-generation spintronic devices. Nevertheless, two-dimensional magnetic semiconductors with Curie temperatures higher than room temperature have rarely been reported. Ferrites with strongly correlated d-orbital electrons may be alternative candidates offering two-dimensional high-temperature magnetic ordering. This prospect is, however, hindered by their inherent three-dimensional bonded nature. Here, we develop a confined-van der Waals epitaxial approach to synthesizing air-stable semiconducting cobalt ferrite nanosheets with thickness down to one unit cell using a facile chemical vapor deposition process. The hard magnetic behavior and magnetic domain evolution are demonstrated by means of vibrating sample magnetometry, magnetic force microscopy and magneto-optical Kerr effect measurements, which shows high Curie temperature above 390 K and strong dimensionality effect. The addition of room-temperature magnetic semiconductors to two-dimensional material family provides possibilities for numerous novel applications in computing, sensing and information storage.

Mechanoluminescence from an Ion-Irradiated Single Crystal of Lithium Niobium Oxide.

Mechanoluminescence (ML) is a well-known phenomenon that has a wide range of applications in security monitoring, biomechanical sensing, and displays. Although several mechanisms relating to ML have been proposed, significant ambiguity persists due to the coexistence of crystal boundaries, luminescence centers, and defects within the samples, making them hard to disentangle. Here we preclude such ambiguity by using a Kr+-irradiated single crystal of lithium niobium oxide (LiNbO3) as the ML materials so that oxygen vacancies are retained to modulate the ML properties. We explore the ion concentration- and species-dependent ML properties along with the band calculations to explicitly reveal that it is the trapped electrons at the oxygen vacancies that are transferred to the conduction band under the piezopotentials of LiNbO3, which combine with holes in the valence band and emit photons. This in-depth understanding not only clarifies the long-standing obscurity of the ML mechanism but also paves a rational and scalable way for the design of advanced ML materials with superior performances.

Controllable Synthesis Quadratic-Dependent Unsaturated Magnetoresistance of Two-Dimensional Nonlayered Fe7S8 with Robust Environmental Stability.

Two-dimensional (2D) iron chalcogenides (FeX, X = S, Se, Te) are emerging as an appealing class of materials for a wide range of research topics, including electronics, spintronics, and catalysis. However, the controlled syntheses and intrinsic property explorations of such fascinating materials still remain daunting challenges, especially for 2D nonlayered Fe7S8 with mixed-valence states and high conductivity. Herein, we design a general and temperature-mediated chemical vapor deposition (CVD) approach to synthesize ultrathin and large-domain Fe7S8 nanosheets on mica substrates, with the thickness down to ∼4.4 nm (2 unit-cell). Significantly, we uncover a quadratic-dependent unsaturated magnetoresistance (MR) with out-of-plane anisotropy in 2D Fe7S8, thanks to its ultrahigh crystalline quality and high conductivity (∼2.7 × 105 S m-1 at room temperature and ∼1.7 × 106 S m-1 at 2 K). More interestingly, the CVD-synthesized 2D Fe7S8 nanosheets maintain robust environmental stability for more than 8 months. These results hereby lay solid foundations for synthesizing 2D nonlayered iron chalcogenides with mixed-valence states and exploring fascinating quantum phenomena.

High-Performance Memristors Based on Ultrathin 2D Copper Chalcogenides.

Copper chalcogenides represent a class of materials with unique crystal structures, high electrical conductivity, and earth abundance, and are recognized as promising candidates for next-generation green electronics. However, their 2D structures and the corresponding electronic properties have rarely been touched. Herein, a series of ultrathin copper chalcogenide nanosheets with thicknesses down to two unit cells are successfully synthesized, including layered Cu2 Te, as well as nonlayered CuSe and Cu9 S5 , via van der Waals epitaxy, and their nonvolatile memristive behavior is investigated for the first time. Benefiting from the highly active Cu ions with low migration barriers, the memristors based on ultrathin 2D copper chalcogenide crystals exhibit relatively small switching voltage (≈0.4 V), fast switching speed, high switching uniformity, and wide operating temperature range (from 80 to 420 K), as well as stable retention and good cyclic endurance. These results demonstrate their tangible applications in future low-power, cryogenic, and high temperature harsh electronics.

Tunable Room-Temperature Ferromagnetism in Two-Dimensional Cr2Te3.

The manipulation of magnetism provides a unique opportunity for the development of data storage and spintronic applications. Until now, electrical control, pressure tuning, stacking structure dependence, and nanoscale engineering have been realized. However, as the dimensions are decreased, the decrease of the ferromagnetism phase transition temperature (Tc) is a universal trend in ferromagnets. Here, we make a breakthrough to realize the synthesis of 1 and 2 unit cell (UC) Cr2Te3 and discover a room-temperature ferromagnetism in two-dimensional Cr2Te3. The newly observed Tc increases strongly from 160 K in the thick flake (40.3 nm) to 280 K in 6 UC Cr2Te3 (7.1 nm). The magnetization and anomalous Hall effect measurements provided unambiguous evidence for the existence of spontaneous magnetization at room temperature. The theoretical model revealed that the reconstruction of Cr2Te3 could result in anomalous thickness-dependent Tc. This dimension tuning method opens up a new avenue for manipulation of ferromagnetism.