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Two-dimensional materials (2DMs) have exhibited remarkably tunable optical characteristics, which have been applied for significant applications in communications, sensing, and computing. However, the reported tunable optical properties of 2DMs are almost volatile, impeding them in the applications of multifarious emerging frameworks such as programmable operation and neuromorphic computing. In this work, nonvolatile electro-optic response is developed by the graphene-Al2O3-In2Se3 heterostructure integrating with microring resonators (MRRs). In such compact devices, the optical absorption coefficient of graphene is substantially tuned by the out-of-plane ferroelectric polarization in α-In2Se3, resulting in a nonvolatile optical transmission in MRRs. This work demonstrates that integrating graphene with ferroelectric materials paves the way to develop nonvolatile devices in photonic circuits for emerging applications such as optical neural networks.
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Two-dimensional (2D) ferroelectric semiconductors present opportunities for integrating ferroelectrics into high-density ultrathin nanoelectronics. Among the few synthesized 2D ferroelectrics, α-In2Se3, known for its electrically addressable vertical polarization, has attracted significant interest. However, the understanding of many fundamental characteristics of this material, such as the existence of spontaneous in-plane polarization and switching mechanisms, remains controversial, marked by conflicting experimental and theoretical results. Here, our combined experimental characterizations with piezoresponse force microscope and symmetry analysis conclusively dismiss previous claims of in-plane ferroelectricity in single-domain α-In2Se3. The processes of vertical polarization switching in monolayer α-In2Se3 are explored with deep-learning-assisted large-scale molecular dynamics simulations, revealing atomistic mechanisms fundamentally different from those of bulk ferroelectrics. Despite lacking in-plane effective polarization, 1D domain walls can be moved by both out-of-plane and in-plane fields, exhibiting avalanche dynamics characterized by abrupt, intermittent moving patterns. The propagating velocity at various temperatures, field orientations, and strengths can be statistically described with a universal creep equation, featuring a dynamical exponent of 2 that is distinct from all known values for elastic interfaces moving in disordered media. This work rectifies a long-held misunderstanding regarding the in-plane ferroelectricity of α-In2Se3, and the quantitative characterizations of domain wall velocity will hold broad implications for both the fundamental understanding and technological applications of 2D ferroelectrics.
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The ferroelectric photovoltaic effect (FPVE) enables alternate pathways for energy conversion that are not allowed in centrosymmetric materials. Understanding the dominant mechanism of the FPVE at the ultrathin limit is important for defining the ultimate efficiency. In contrast to the wide band gap conventional thin-film ferroelectrics, 2D α-In2Se3 has an ideal band gap of 1.3 eV and enables the fabrication of ultrathin and stable heterostructures, providing the perfect platform to explore FPVE in the nanoscale limit. Here, we study the ferroelectric layer thickness-dependent FPVE in vertical few-layer graphene/α-In2Se3/graphene heterostructures. We find that the short-circuit photocurrent is antiparallel to the ferroelectric polarization and increases exponentially with decreasing thickness. We show that the observed behavior is predicted by the depolarization field model, originating from the unscreened bound charges due to the finite density of states in semimetal few-layer graphene. As a result, the heterostructures show enhancement of the power conversion efficiency, reaching 2.56 × 10-3% under 100 W/cm2 in 18 nm thick α-In2Se3, approximately 275 times more than the 50 nm thick α-In2Se3. These results demonstrate the importance of the depolarization field at the nanoscale and define design principles for the potential of harnessing FPVE at reduced dimension.
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Integrating two-dimensional (2D) layered materials with wide bandgap ß-Ga2O3 has unveiled impressive opportunities for exploring novel physics and device concepts. This study presents the epitaxial growth of 2D ß-In2Se3/3D ß-Ga2O3 heterostructures on c-Sapphire substrates by plasma-assisted molecular beam epitaxy. Firstly, we employed a temperature-dependent two-step growth process to deposit Ga2O3 and obtained a phase-pure ( 2 ¯ 01 ) ß-Ga2O3 film on c-Sapphire. Interestingly, the in-situ reflective high-energy electron diffraction (RHEED) patterns observed from this heterostructure revealed the in-plane 'b' lattice constant of ß-Ga2O3 ~ 3.038Å. In the next stage, for the first time, 2D In2Se3 layers were epitaxially realized on 3D ß-Ga2O3 under varying substrate temperatures (Tsub) and Se/In flux ratios (RVI/III). The deposited layers exhibited (00l) oriented ß-In2Se3 on ( 2 ¯ 01 ) ß-Ga2O3/c-Sapphire with the epitaxial relationship of [ 11 2 ¯ 0 ] ß-In2Se3 || [010] ß-Ga2O3 and [ 10 1 ¯ 0 ] ß-In2Se3 || [102] ß-Ga2O3 as observed from the RHEED patterns. Also, the in-plane 'a' lattice constant of ß-In2Se3 was determined to be ~ 4.027Å. The single-phase ß-In2Se3 layers with improved structural and surface quality were achieved at a Tsub ~ 280 °C and RVI/III ~ 18. The microstructural and detailed elemental analysis further confirmed the epitaxy of 2D layered ß-In2Se3 on 3D ß-Ga2O3, a consequence of the quasi-van der Waals epitaxy. Furthermore, the ß-Ga2O3 with an optical bandgap (Eg) of ~ 5.04 eV (deep ultraviolet) when integrated with 2D ß-In2Se3, Eg ~ 1.43eV (near infra-red) can reveal potential applications in the optoelectronic field.
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α-In2Se3 semiconductor crystals realize artificial synapses by tuning in-plane and out-of-plane ferroelectricity with diverse avenues of electrical and optical pulses. While the electrically induced ferroelectricity of α-In2Se3 shows synaptic memory operation, the optically assisted synaptic plasticity in α-In2Se3 has also been preferred for polarization flipping enhancement. Here, the synaptic memory behavior of α-In2Se3 is demonstrated by applying electrical gate voltages under white light. As a result, the induced internal electric field is identified at a polarization flipped conductance channel in α-In2Se3/hexagonal boron nitride (hBN) heterostructure ferroelectric field effect transistors (FeFETs) under white light and discuss the contribution of this built-in electric field on synapse characterization. The biased dipoles in α-In2Se3 toward potentiation polarization direction by an enhanced internal built-in electric field under illumination of white light lead to improvement of linearity for long-term depression curves with proper electric spikes. Consequently, upon applying appropriate electric spikes to α-In2Se3/hBN FeFETs with illuminating white light, the recognition accuracy values significantly through the artificial learning simulation is elevated for discriminating hand-written digit number images.
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Piezo-catalysis emerges as an efficient, safe, and affordable strategy for removing hazardous substances from aquatic environments. Here, the BiFeO3@In2Se3 heterojunction demonstrates remarkable prowess as a piezo-catalyst, enabling the high-efficiency removal of uranium (U) from U(VI)-containing water. A total U(VI) removal efficiency of 94.6% can be achieved under ultrasonic vibration without any sacrificial agents. During the entire catalytic process, piezo-induced electrons, hydroxyl radicals, and superoxide radicals play important roles in U(VI) removal, while the generated H2O2 is responsive to the transformation of soluble U(VI) into insoluble (UO2)O2â¢2H2O and UO3. Furthermore, auxiliary illumination can accelerate the increase of free charges, enabling the piezo-catalyst to retain more charges. This leads to an improved U(VI) removal efficiency of 98.8% and a significantly increased reaction rate constant. This study offers a comprehensive analysis of the fabrication of high-efficiency piezo-catalysts in the removal or extraction of U(VI) from U(VI)-containing water.
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With the discovery of two-dimensional (2D) ferroelectric materials such as CuInP2S6andα-In2Se3, the ferroelectric field effect transistors (Fe-FETs) based on these materials have entered a rapid-development period. The metal/semiconductor contact is an unavoidable topic in the construction of devices. In this paper, heterostructuresα-In2Se3/metals (Pd, Pt, Cu, Ag and Au) are discussed. According to different stacking types, the structures and energy of 160 heterostructures are calculated and compared. Whenα-In2Se3contacts with the Pd, Pt and Cu, theα-In2Se3may transforms intoß-In2Se3. This phenomenon has hardly been mentioned or analyzed in previous reports. Contacting with the Au and Ag, theα-In2Se3maintains the original structure. The internal physical mechanism of phase transition is explained from the binding energy and the charge transfer. The paper provides sufficient theoretical support for research and development of the Fe-FETs based onα-In2Se3.
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van der Waals ferroic materials exhibit rich potential for implementing future generation functional devices. Among these, layered ß'-In2Se3 has fascinated researchers with its complex superlattice and domain structures. As opposed to ferroelectric α-In2Se3, the understanding of ß'-In2Se3 ferroic properties remains unclear because ferroelectric, antiferroelectric, and ferroelastic characteristics have been separately reported in this material. To develop useful applications, it is necessary to understand the microscopic structural properties and their correlation with macroscopic device characteristics. Herein, using scanning transmission electron microscopy (STEM), we observed that the arrangement of dipoles deviates from the ideal double antiparallel antiferroelectric character due to competition between antiferroelectric and ferroelectric structural ordering. By virtue of second-harmonic generation, four-dimensional STEM, and in-plane piezoresponse force microscopy, the long-range inversion-breaking symmetry, uncompensated local polarization, and net polarization domains are unambiguously verified, revealing ß'-In2Se3 as an in-plane ferrielectric layered material. Additionally, our device study reveals analogous resistive switching behaviors of different types owing to polarization switching, defect migration, and defect-induced charge trapping/detrapping processes.
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Functional diversification at the single-device level has become essential for emerging optical neural network (ONN) development. Stable ferroelectricity harnessed with strong light sensitivity in α-In2Se3 holds great potential for developing ultrathin neuromorphic devices. Herein, we demonstrated an all-2D van der Waals heterostructure-based programmable synaptic field effect transistor (FET) utilizing a ferroelectric α-In2Se3 nanosheet and monolayer graphene. The devices exhibited reconfigurable, multilevel nonvolatile memory (NVM) states, which can be successively modulated by multiple dual-mode (optical and electrical) stimuli and thereby used to realize energy-efficient, heterosynaptic functionalities in a biorealistic fashion. Furthermore, under light illumination, the prototypical device can toggle between volatile (photodetector) and nonvolatile optical random-access memory (ORAM) logic operation, depending upon the ferroelectric-dipole induced band adjustment. Finally, plasticity modulation from short-term to prominent long-term characteristics over a wide dynamic range was demonstrated. The inherent operation mechanism owing to the switchable polarization-induced electronic band alignment and bidirectional barrier height modulation at the heterointerface was revealed by conjugated electronic transport and Kelvin-probe force microscopy (KPFM) measurements. Overall, robust (opto)electronic weight controllability for integrated in-sensor and in-memory logic processors and multibit ORAM systems was readily accomplished by the synergistic ferrophotonic heterostructure properties. Our presented results facilitate the technological implementation of versatile all-2D heterosynapses for next-generation perception, optoelectronic logic systems, and Internet-of-Things (IoT) entities.
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Despite its prevalence in experiments, the influence of complex strain on material properties remains understudied due to the lack of effective simulation methods. Here, the effects of bending, rippling, and bubbling on the ferroelectric domains are investigated in an In2Se3 monolayer by density functional theory and deep learning molecular dynamics simulations. Since the ferroelectric switching barrier can be increased (decreased) by tensile (compressive) strain, automatic polarization reversal occurs in α-In2Se3 with a strain gradient when it is subjected to bending, rippling, or bubbling deformations to create localized ferroelectric domains with varying sizes. The switching dynamics depends on the magnitude of curvature and temperature, following an Arrhenius-style relationship. This study not only provides a promising solution for cross-scale studies using deep learning but also reveals the potential to manipulate local polarization in ferroelectric materials through strain engineering.
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Owing to the emerging trend of non-volatile memory and data-centric computing, the demand for more functional materials and efficient device architecture at the nanoscale is becoming stringent. To date, 2D ferroelectrics are cultivated as channel materials in field-effect transistors for their retentive and switchable dipoles and flexibility to be compacted into diverse structures and integration for intensive production. This study demonstrates the in-plane (IP) ferroelectric memory effect of a 100 nm channel-length 2D ferroelectric semiconductor α-In2 Se3 stamped onto nanogap electrodes on Si/SiO2 under a lateral electric field. As α-In2 Se3 forms the bottom contact of the nanogap electrodes, a large memory window of 13 V at drain voltage between ±6.5 V and the on/off ratio reaching 103 can be explained by controlled IP polarization. Furthermore, the memory effect is modulated by the bottom gate voltage of the Si substrate due to the intercorrelation between IP and out-of-plane (OOP) polarization. The non-volatile memory characteristics including stable retention lasting 17 h, and endurance over 1200 cycles suggest a wide range of memory applications utilizing the lateral bottom contact structure.
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Crystal transformation of metal compound cathodes during charge/discharge processes in alkali metal-ion batteries usually generates profound impact on structural stability and electrochemical performance, while the theme in anode materials, which always occurs and completes during the first redox cycle, is rarely explored probably due to the fast transformation dynamics. Herein, for the first time, a unique crystal transformation behavior with slow dynamics in anode of sodium-ion batteries (SIBs) is reported, which further promotes electrochemical performance. Specifically, irreversible γ â ß crystal transformation of In2 Se3 is observed, induced by the persistent size degradation of In2 Se3 particles during repeated sodiation/desodiation, supported by a series of ex situ characterizations, such as HRTEM, XRD, and XPS of γ-In2 Se3 /reduced graphene oxide (γ-In2 Se3 @rGO) nanocomposite. The hybrid electrode shows ultrahigh long-term cycling stability (378 mA h g-1 at 1.0 A g-1 after 1000 cycles) and excellent rate capability (272 mA h g-1 at 20.0 A g-1 ). Full battery with Na3 V2 (PO4 )3 cathode also manifests superior performance, promising ß-In2 Se3 dominated electrode materials in high-power and long-life SIBs. The first-principle calculations suggest the crystal transformation enhances electric conductivity of ß-In2 Se3 and facilitates its accessibility to sodium. In combination with the synergistic effect between rGO matrix, substantially enhanced electrochemical performance is realized.
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Two-dimensional In2Se3, an unconventional phase-change material, has drawn considerable attention for polymorphic phase transitions and electronic device applications. However, its reversible thermally driven phase transitions and potential use in photonic devices have yet to be explored. In this study, we observe the thermally driven reversible phase transitions between α and ß' phases with the assistance of local strain from surface wrinkles and ripples, as well as reversible phase changes within the ß phase family. These transitions lead to changes in the refractive index and other optoelectronic properties with minimal optical loss at telecommunication bands, which are crucial in integrated photonic applications such as postfabrication phase trimming. Additionally, multilayer ß'-In2Se3 working as a transparent microheater proves to be a viable option for efficient thermo-optic modulation. This prototype design for layered In2Se3 offers immense potential for integrated photonics and paves the way for multilevel, nonvolatile optical memory applications.
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Driven by the rapid development of autonomous vehicles, ultrasensitive photodetectors with high signal-to-noise ratio and ultraweak light detection capability are urgently needed. Due to its intriguing attributes, the emerging van der Waals material, indium selenide (In2Se3), has attracted extensive attention as an ultrasensitive photoactive material. However, the lack of an effective photoconductive gain mechanism in individual In2Se3 inhibits its further application. Herein, we propose a heterostructure photodetector consisting of an In2Se3 photoactive channel, a hexagonal boron nitride (h-BN) passivation layer, and a CsPb(Br/I)3 quantum dot gain layer. This device manifests a signal-to-noise ratio of 2 × 106 with responsivity of 2994 A/W and detectivity of 4.3 × 1014 Jones. Especially, it enables the detection of weak light as low as 0.03 µW/cm2. These performance characteristics are ascribed to the interfacial engineering. In2Se3 and CsPb(Br/I)3 with type-II band alignment promote the separation of photocarriers, while h-BN passivates the impurities on CsPb(Br/I)3 and promises a high-quality carrier transport interface. Furthermore, this device is successfully integrated into an automatic obstacle avoidance system, demonstrating promising application prospects in autonomous vehicles.
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Optoelectronic synaptic devices capable of processing multiwavelength inputs are critical for neuromorphic vision hardware, which remains an important challenge. Here, we develop a bidirectional synaptic phototransistor based on a two-dimensional ferroelectric semiconductor of α-In2Se3, which exhibits bidirectional potentiated and depressed synaptic weight update under optical pulse stimulation. Importantly, the bidirectional optoelectronic synaptic behavior can be extended to multiwavelengths (blue, green, and red light), which could be used for color recognition. The mechanism underlying the bidirectional synaptic characteristics is attributed to the gate-configurable barrier heights as revealed by the Kelvin probe force microscopy measurement. The α-In2Se3 device exhibits versatile synaptic plasticity such as paired-pulse facilitation, short- and long-term potentiation, and long-term depression. The bidirectional optoelectronic synaptic weight updates under multiwavelength inputs enable a high accuracy of 97% for mixed color pattern recognition.
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Designing heterojunction photocatalysts with strong interfacial interactions is an effective way to reduce the recombination of photogenerated charge carriers. Here, silver phosphate (Ag3PO4) nanoparticles are coupled with hollow flower-like indium selenide (In2Se3) microspheres by a facile Ostwald ripening and in-situ growth method, resulting in the construction of In2Se3/Ag3PO4 hollow microsphere step-scheme (S-scheme) heterojunction with a large contact interface. The flower-like In2Se3 with hollow and porous structure provides a large specific surface area and numerous active sites for photocatalytic reactions to take place. The photocatalytic activity was tested by measuring the hydrogen evolution from antibiotic wastewater, and the H2 evolution rate of In2Se3/Ag3PO4 reached 4206.4 µmol g-1h-1 under visible light, which is approximately 2.8 times greater than that of In2Se3. In addition, the amount of tetracycline (TC) degradation when it was used as a sacrificial agent is about 54.4% after 1 h. On the one hand, Se-P chemical bonds act as electron transfer channels in the S-scheme heterojunctions, which can facilitate the migration and separation of photogenerated charge carriers. On the other hand, the S-scheme heterojunctions can retain the useful holes and electrons with higher redox capacities, which is very favorable for the generation of more â¢OH radicals and the photocatalytic activity is greatly enhanced. This work provides an alternative design approach for photocatalysts toward hydrogen evolution in antibiotic wastewater.
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An electrical-biased or mechanical-loaded scanning probe written on the ferroelectric surface can generate programmable domain nanopatterns for ultra-scaled and reconfigurable nanoscale electronics. Fabricating ferroelectric domain patterns by direct-writing as quickly as possible is highly desirable for high response rate devices. Using monolayer α-In2 Se3 ferroelectric with ≈1.2 nm thickness and intrinsic out-of-plane polarization as an example, a writing-speed dependent effect on ferroelectric domain switching is discovered. The results indicate that the threshold voltages and threshold forces for domain switching can be increased from -4.2 to -5 V and from 365 to 1216 nN, respectively, as the writing-speed increases from 2.2 to 10.6 µm s-1 . The writing-speed dependent threshold voltages can be attributed to the nucleations of reoriented ferroelectric domains, in which sufficient time is needed for subsequent domain growth. The writing-speed dependent threshold forces can be attributed to the flexoelectric effect. Furthermore, the electrical-mechanical coupling can be employed to decrease the threshold force, achieving as low as ≈189±41 nN, a value smaller than those of perovskite ferroelectric films. Such findings reveal a critical issue of ferroelectric domain pattern engineering that should be carefully addressed for programmable direct-writing electronics applications.
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Ferroelectric materials have received great attention in the field of data storage, benefiting from their exotic transport properties. Among these materials, the two-dimensional (2D) In2Se3 has been of particular interest because of its ability to exhibit both in-plane and out-of-plane ferroelectricity. In this article, we realized the molecular beam epitaxial (MBE) growth of ß-In2Se3 films on bilayer graphene (BLG) substrates with precisely controlled thickness. Combining in situ scanning tunneling microscopy (STM) and angle-resolved photoemission spectroscopy (ARPES) measurements, we found that the four-monolayer ß-In2Se3 is a semiconductor with a (9 × 1) reconstructed superlattice. In contrast, the monolayer ß-In2Se3/BLG heterostructure does not show any surface reconstruction due to the interfacial interaction and moiré superlattice, which instead results in a folding Dirac cone at the center of the Brillouin zone. In addition, we found that the band gap of In2Se3 film decreases after potassium doping on its surface, and the valence band maximum also shifts in momentum after surface potassium doping. The successful growth of high-quality ß-In2Se3 thin films would be a new platform for studying the 2D ferroelectric heterostructures and devices. The experimental results on the surface reconstruction and band structures also provide important information on the quantum confinement and interfacial effects in the epitaxial ß-In2Se3 films.
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The two-dimensional (2D) layered semiconductor α-In2Se3 has aroused great interest in atomic-scale ferroelectric transistors, artificial synapses, and nonvolatile memory devices due to its distinguished 2D ferroelectric properties. We have synthesized α-In2Se3 nanosheets with rare in-plane ferroelectric stripe domains at room temperature on mica substrates using a reverse flow chemical vapor deposition (RFCVD) method and optimized growth parameters. This stripe domain contrast is found to be strongly correlated to the stacking of layers, and the interrelated out-of-plane (OOP) and in-plane (IP) polarization can be manipulated by mapping the artificial domain structure. The acquisition of amplitude and phase hysteresis loops confirms the OOP polarization ferroelectric property. The emergence of striped domains enriches the variety of the ferroelectric structure types and novel properties of 2D In2Se3. This work paves a new way for the controllable growth of van der Waals ferroelectrics and facilitates the development of novel ferroelectric memory device applications.
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The low bending stiffness of atomic membranes from van der Waals ferroelectrics such as α-In2Se3 allow access to a regime of strong coupling between electrical polarization and mechanical deformation at extremely high strain gradients and nanoscale curvatures. Here, we investigate the atomic structure and polarization at bends in multilayer α-In2Se3 at high curvatures down to 0.3 nm utilizing atomic-resolution scanning transmission electron microscopy, density functional theory, and piezoelectric force microscopy. We find that bent α-In2Se3 produces two classes of structures: arcs, which form at bending angles below â¼33°, and kinks, which form above â¼33°. While arcs preserve the original polarization of the material, kinks contain ferroelectric domain walls that reverse the out-of-plane polarization. We show that these kinks stabilize ferroelectric domains that can be extremely small, down to 2 atoms or â¼4 Å wide at their narrowest point. Using DFT modeling and the theory of geometrically necessary disclinations, we derive conditions for the formation of kink-induced ferroelectric domain boundaries. Finally, we demonstrate direct control over the ferroelectric polarization using templated substrates to induce patterned micro- and nanoscale ferroelectric domains with alternating polarization. Our results describe the electromechanical coupling of α-In2Se3 at the highest limits of curvature and demonstrate a strategy for nanoscale ferroelectric domain patterning.