CuInP2S6 Research Articles

Ferroelectric van der Waals heterostructures of CuInP2S6 for non-volatile memory device applications

Two-dimensional (2D) ferroelectric materials are providing promising platforms for creating future nano- and opto-electronics. Here we propose new hybrid van der Waals heterostructures, in which the 2D ferroelectric material CuInP2S6 (CIPS) is layered on a 2D semiconductor for near-infrared (NIR) memory device applications. Using density functional theory, we show that the band gap of the hybrid bilayers formed with CIPS can be tuned and that the optical and electronic properties can be successfully modulated via ferroelectric switching. Of the 3712 heterostructures considered, we identified 19 structures that have a type II band alignment and commensurate lattice matches. Of this set, both the CuInP2S6/PbSe and CuInP2S6/Ge2H2 heterostructures possess absorption peaks in the NIR region that change position and intensity with switching polarisation, making them suitable for NIR memory devices. The CuInP2S6/ISSb, CuInP2S6/ISbSe, CuInP2S6/ClSbSe and CuInP2S6/ZnI2 heterostructures had band gaps which can be switched from direct to indirect with changing the polarisation of CIPS making them suitable for optoelectronics and sensors. The heterostructures formed with CIPS are exciting candidates for stable ferroelectric devices, opening a pathway for tuning the band alignment of van der Waal heterostructures and the creation of modern memory applications that use less energy.

Ultrafast Nonlinear Absorption and Second Harmonic Generation in Cu0.33In1.30P2S6 van der Waals Layered Crystals.

The advancement of ultrafast photonics and optoelectronic devices necessitates the exploration of new materials with optical and chemical stability to implement practical applications. Layered quaternary metal-thio/selenophosphate has attracted much interest over the past few years. Ferroelectric CuInP2S6 (CIPS) is an emerging material that belongs to this family. When synthesized with Cu deficiencies, CIPS forms self-assembled in-plane heterostructures, which in turn exhibit properties that are both compositionally and thermally dependent. These characteristics can be explored for applications in nonlinear optoelectronic and photonic devices. Herein, we study the second and third order nonlinear optical behavior of Cu0.33In1.30P2S6 bulk heterostructure. We observed large two photon induced nonlinear absorptions and self-defocusing at 1032 nm pulsed laser excitation using the Z-scan technique. Furthermore, we identified a polarization-dependent second harmonic signal and determined the laser-induced optical damage threshold. Our observations allow for the designing of optoelectronic and ultrafast photonic devices based on these materials.

Ferroelectric Tuning of ZnO Ultraviolet Photodetectors.

The ferroelectric field effect transistor (Fe-FET) is considered to be one of the most important low-power and high-performance devices. It is promising to combine a ferroelectric field effect with a photodetector to improve the photodetection performance. This study proposes a strategy for ZnO ultraviolet (UV) photodetectors regulated by a ferroelectric gate. The ZnO nanowire (NW) UV photodetector was tuned by a 2D CuInP2S6 (CIPS) ferroelectric gate, which decreased the dark current and enhanced the responsivity and detectivity to 2.40 × 104 A/W and 7.17 × 1011 Jones, respectively. This strategy was also applied to a ZnO film UV photodetector that was tuned by a P(VDF-TrFE) ferroelectric gate. Lower power consumption and higher performance can be enabled by ferroelectric tuning of ZnO ultraviolet photodetectors, providing new inspiration for the fabrication of high-performance photodetectors.

Self-Enhancing Photoelectrochemical Properties in van der Waals Ferroelectric CuInP2S6 by Photoassisted Acid Hydrolysis.

Transition metal thiophosphate, CuInP2S6 (CIPS), has recently emerged as a potentially promising material for photoelectrochemical (PEC) water splitting due to its intrinsic ferroelectric polarization for spontaneous photocarrier separation. However, the poor kinetics of the hydrogen evolution reaction (HER) greatly limits its practical applications. Herein, we report self-enhancing photocatalytic behavior of a CIPS photocathode due to chemically driven oxygen incorporation by photoassisted acid oxidation. The optimal oxygen-doped CIPS demonstrates a >1 order of magnitude enhancement in the photocurrent density compared to that of pristine CIPS. Through comprehensive spectroscopic and microscopic investigations combined with theoretical calculations, we disclose that oxygen doping will lower the Fermi level position and decrease the HER barrier, which further accelerates charge separation and improves the HER activity. This work may deliver a universal and facile strategy for improving the PEC performance of other van der Waals metal thiophosphates.

Revealing Fast Cu-Ion Transport and Enhanced Conductivity at the CuInP2S6-In4/3P2S6 Heterointerface.

Van der Waals layered ferroelectrics, such as CuInP2S6 (CIPS), offer a versatile platform for miniaturization of ferroelectric device technologies. Control of the targeted composition and kinetics of CIPS synthesis enables the formation of stable self-assembled heterostructures of ferroelectric CIPS and nonferroelectric In4/3P2S6 (IPS). Here, we use quantitative scanning probe microscopy methods combined with density functional theory (DFT) to explore in detail the nanoscale variability in dynamic functional properties of the CIPS-IPS heterostructure. We report evidence of fast ionic transport which mediates an appreciable out-of-plane electromechanical response of the CIPS surface in the paraelectric phase. Further, we map the nanoscale dielectric and ionic conductivity properties as we thermally stimulate the ferroelectric-paraelectric phase transition, recovering the local dielectric behavior during this phase transition. Finally, aided by DFT, we reveal a substantial and tunable conductivity enhancement at the CIPS/IPS interface, indicating the possibility of engineering its interfacial properties for next generation device applications.

A nanomaterial targeting the spike protein captures SARS-CoV-2 variants and promotes viral elimination.

The global emergency caused by the severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) pandemic can only be solved with effective and widespread preventive and therapeutic strategies, and both are still insufficient. Here, we describe an ultrathin two-dimensional CuInP2S6 (CIPS) nanosheet as a new agent against SARS-CoV-2 infection. CIPS exhibits an extremely high and selective binding capacity (dissociation constant (KD) < 1 pM) for the receptor binding domain of the spike protein of wild-type SARS-CoV-2 and its variants of concern, including Delta and Omicron, inhibiting virus entry and infection in angiotensin converting enzyme 2 (ACE2)-bearing cells, human airway epithelial organoids and human ACE2-transgenic mice. On association with CIPS, the virus is quickly phagocytosed and eliminated by macrophages, suggesting that CIPS could be successfully used to capture and facilitate virus elimination by the host. Thus, we propose CIPS as a promising nanodrug for future safe and effective anti-SARS-CoV-2 therapy, and as a decontamination agent and surface-coating material to reduce SARS-CoV-2 infectivity.

Flexoelectric engineering of van der Waals ferroelectric CuInP2S6.

Van der Waals layered CuInP2S6 (CIPS) is an ideal candidate for developing two-dimensional microelectronic heterostructures because of its room temperature ferroelectricity, although field-driven polarization reversal of CIPS is intimately coupled with ionic migration, often causing erratic and damaging switching that is highly undesirable for device applications. In this work, we develop an alternative switching mechanism for CIPS using flexoelectric effect, abandoning external electric fields altogether, and the method is motivated by strong correlation between polarization and topography variation of CIPS. Phase-field simulation identifies a critical radius of curvature around 5 μm for strain gradient to be effective, which is realized by engineered topographic surfaces using silver nanowires and optic grating upon which CIPS is transferred to. We also demonstrate mechanical modulation of CIPS on demand via strain gradient underneath a scanning probe, making it possible to engineer multiple polarization states of CIPS for device applications.

Extraordinary Nonlinear Optical Interaction from Strained Nanostructures in van der Waals CuInP2S6.

Local strain engineering and structural modification of 2D materials furnish benevolent control over their optoelectronic properties and provide an exciting approach to tune light-matter interaction in layered materials. Application of strain at the nanoscale is typically obtained through permanently deformed nanostructures such as nanowrinkles, which yield large band gap modulation, photoluminescence enhancement, and surface potential. Ultrathin transition metal dichalcogenides (TMDs) have been greatly analyzed for such purposes. Herein, we extend strain-induced nanoengineering to an emerging 2D material, CuInP2S6 (CIPS), and visualize extraordinary control over nonlinear light-matter interaction. Wrinkle nanostructures exhibit ∼160-fold enhancement in second harmonic generation (SHG) compared to unstrained regions, which is additionally influenced by a change in the dielectric environment. The SHG enhancement was significantly modulated by the percentage of applied strain which was numerically estimated. Furthermore, polarization-dependent SHG revealed quenching and enhancement in the parallel and perpendicular directions, respectively, due to the direction of the compressive vector. Our work provides an important advancement in controlling optoelectronic properties beyond TMDs for imminent applications in flexible electronics.

Correlative piezoresponse and micro-Raman imaging of CuInP2S6–In4/3P2S6 flakes unravels phase-specific phononic fingerprint via unsupervised learning

Characterizing the novel properties of layered van der Waals materials is key for their application in functional devices. A better understanding of this type of material requires correlative imaging of diverse nanoscale material properties. Within this class of materials, CuInP2S6 (CIPS) has received a significant degree of interest due to its ionically mediated room temperature ferroelectricity. Moreover, it is possible to form stable self-assembled heterostructures of ferroelectric CuInP2S6 (CIPS) and non-ferroelectric (i.e., lacking Cu) In4/3P2S6 (IPS) phases, by controlling the targeted composition and kinetics of synthesis. In this work, we present a correlative nanometric imaging study of the phononic modes and piezoelectricity of the phase-separated thin heteroepitaxial CIPS/IPS flakes. We show that it is possible to isolate the different phononic modes of the two phases by spatially correlating them with their distinct ferroelectric behavior. The coupling of our experimental data with unsupervised learning statistical methods enables unraveling specific Raman peaks that are characteristic of each chemical phase (CIPS and IPS) present in the composite sample, discarding the less significant ones.

Tunable photochemical deposition of silver nanostructures on layered ferroelectric CuInP2S6

Two-dimensional layered ferroelectric materials, such as CuInP2S6 (CIPS), are promising candidates for novel and high-performance photocatalysts, owing to their ultrathin layer thickness, strong interlayer coupling, and intrinsic spontaneous polarization, while how to control the photocatalytic activity in layered CIPS remains unexplored. In this work, we report for the first time, the photocatalytic activity of ferroelectric CIPS for the chemical deposition of silver nanostructures (AgNSs). The results show that the shape and spatial distribution of AgNSs on CIPS are tunable by controlling layer thickness, environmental temperature, and light wavelength. The ferroelectric polarization in CIPS plays a critical role in tunable AgNS photodeposition, as evidenced by layer thickness and temperature dependence experiments. We further reveal that AgNS photodeposition process starts from active site creation, selective nanoparticle nucleation/aggregation, to continuous film formation. Moreover, AgNS/CIPS heterostructures prepared by photodeposition exhibit excellent resistance switching behavior and good surface enhancement Raman Scattering activity. Our findings provide new insight into the photocatalytic activity of layered ferroelectrics and offer a new material platform for advanced functional device applications in smart memristors and enhanced chemical sensors.

Ferroelectricity and Piezoelectricity in 2D Van der Waals CuInP2S6 Ferroelectric Tunnel Junctions.

CuInP2S6 (CIPS) is a novel two-dimensional (2D) van der Waals (vdW) ferroelectric layered material with a Curie temperature of TC~315 K, making it promising for great potential applications in electronic and photoelectric devices. Herein, the ferroelectric and electric properties of CIPS at different thicknesses are carefully evaluated by scanning probe microscopy techniques. Some defects in some local regions due to Cu deficiency lead to a CuInP2S6–In4/3P2S6 (CIPS–IPS) paraelectric phase coexisting with the CIPS ferroelectric phase. An electrochemical strain microscopy (ESM) study reveals that the relaxation times corresponding to the Cu ions and the IPS ionospheres are not the same, with a significant difference in their response to DC voltage, related to the rectification effect of the ferroelectric tunnel junction (FTJ). The electric properties of the FTJ indicate Cu+ ion migration and propose that the current flow and device performance are dynamically controlled by an interfacial Schottky barrier. The addition of the ferroelectricity of CIPS opens up applications in memories and sensors, actuators, and even spin-orbit devices based on 2D vdW heterostructures.

Gate-tunable giant tunneling electroresistance in van der Waals ferroelectric tunneling junctions

Ferroelectric tunneling junctions (FTJs) have attracted great interest due to their potential applications in non-volatile memories and neurosynaptic computing. In this work, high performance FTJs constructed with graphene and two-dimensional (2D) layered ferroelectric CuInP2S6 (CIPS) with out-of-plane polarization have been demonstrated. These van der Waals (vdW) heterostructure tunneling devices show tunneling electroresistance (TER) up to 107. Furthermore, the FTJs exhibit noticeable gate tunability, for which the on-state tunneling current can increase by 100% by applying a 50 V gate voltage through the conventional 260-nm-thick SiO2 dielectric layer. Our demonstration of gate-tunable, giant tunneling electroresistance highlights its potential in energy-efficient non-volatile memories and computing-in-memory functions.

Ferroelectric Field‐Effect‐Transistor Integrated with Ferroelectrics Heterostructure

To address the demands of emerging data‐centric computing applications, ferroelectric field‐effect transistors (Fe‐FETs) are considered the forefront of semiconductor electronics owing to their energy and area efficiency and merged logic–memory functionalities. Herein, the fabrication and application of an Fe‐FET, which is integrated with a van der Waals ferroelectrics heterostructure (CuInP2S6/α‐In2Se3), is reported. Leveraging enhanced polarization originating from the dipole coupling of CIPS and α‐In2Se3, the fabricated Fe‐FET exhibits a large memory window of 14.5 V at V GS = ±10 V, reaching a memory window to sweep range of ≈72%. Piezoelectric force microscopy measurements confirm the enhanced polarization‐induced wider hysteresis loop of the double‐stacked ferroelectrics compared to single ferroelectric layers. The Landau–Khalatnikov theory is extended to analyze the ferroelectric characteristics of a ferroelectric heterostructure, providing detailed explanations of the hysteresis behaviors and enhanced memory window formation. The fabricated Fe‐FET shows nonvolatile memory characteristics, with a high on/off current ratio of over 106, long retention time (>104 s), and stable cyclic endurance (>104 cycles). Furthermore, the applicability of the ferroelectrics heterostructure is investigated for artificial synapses and for hardware neural networks through training and inference simulation. These results provide a promising pathway for exploring low‐dimensional ferroelectronics.

Memristive effects due to charge transfer in graphene gated through ferroelectric CuInP2S6

Ferroelectricity at the nanometre scale can drive the miniaturisation and wide application of ferroelectric devices for memory and sensing applications. The two-dimensional van der Waals (2D-vdWs) ferroelectrics CuInP2S6 (CIPS) has attracted much attention due to its robust ferroelectricity found in thin layers at room temperature. Also, unlike many 2D ferroelectrics, CIPS is a wide band gap semiconductor, well suited for use as a gate in field-effect transistors (FETs). Here, we report on a hybrid FET in which the graphene conducting channel is gated through a CIPS layer. We reveal hysteresis effects in the transfer characteristics of the FET, which are sensitive to the gate voltage, temperature and light illumination. We demonstrate charge transfer at the CIPS/graphene interface in the dark and under light illumination. In particular, light induces a photodoping effect in graphene that varies from n- to p-type with increasing temperature. These hybrid FETs open up opportunities for electrically and optically controlled memristive devices.

Ferroelectric control of pseudospin texture in CuInP2S6 monolayer

Spin–orbit coupling (SOC) plays an important role in condensed matter physics and has potential applications in spintronics devices. In this paper, we study the electronic properties of ferroelectric CuInP2S6 (CIPS) monolayer through first-principles calculations. The result shows that CIPS monolayer is a potential for valleytronics material and we find that the in-plane helical and nonhelical pseudospin texture are induced by the Rashba and Dresselhaus effect, respectively. The chirality of helical pseudospin texture is coupled to the out-of-plane ferroelectric polarization. Furthermore, a large spin splitting due to the SOC effect can be found at K valley, which can be regarded as the Zeeman effect under a valley-dependent pseudomagnetic field. The CIPS monolayer with Rashba et al effects provides a good platform for electrically controlled spin polarization physics.

Two-Dimensional CIPS-InSe van der Waal Heterostructure Ferroelectric Field Effect Transistor for Nonvolatile Memory Applications.

Channel current conduction modulation with the spontaneous polarization of ferroelectric films in ferroelectric field-effect transistors (FeFETs) has been widely investigated. Low interface quality and thermodynamic instability owing to the presence of dangling bonds in the conventional ferroelectrics have limited the memory retention and endurance of FeFETs. This, in turn, prevents their commercialization. However, the atomically thin nature of 2D ferroelectric, semiconducting, and insulating films facilitate the achievement of trap-free interfaces as van der Waal heterostructures (vdWHs) to develop FeFETs with long data retention and endurance characteristics. Here, we demonstrate a 2D vdWH FeFET fabricated with ferroelectric CuInP2S6 (CIPS), hexagonal boron nitride (h-BN) as the dielectric, and InSe as the ferroelectric semiconductor channel. The device shows an excellent performance as nonvolatile memory (NVM) with its large memory window (4.6 V at a voltage sweep of 5 V), high drain current on/off ratio (>104), high endurance, and long data retention (>104 s). These results demonstrate the considerable potential of vdWHs for the development of FeFETs for logic and NVM applications.

Van der Waals Antiferroelectric Magnetic Tunnel Junction: A First-Principles Study of a CrSe2/CuInP2S6/CrSe2 Junction.

Magnetic tunnel junctions (MTJs), ferroelectric/antiferroelectric tunnel junctions (FTJs/AFTJs), and multiferroic tunnel junctions (MFTJs) have recently attracted significant interest for technological applications of nanoscale memory devices. Until now, most of them are based on perovskite oxide heterostructures with a relatively high resistance-area (RA) product and low resistance difference unfavorable for practical applications. The recent discovery of the two-dimensional (2D) van der Waals (vdW) ferroelectric (FE) and magnetic materials has opened a new route to realize tunnel junctions with high performance and atomic-scale dimensions. Here, using first-principles calculations, we propose a new type of 2D tunnel junction: an antiferroelectric magnetic tunnel junction (AFMTJ), which inherits the features of both MTJ and AFTJ. This AFMTJ is composed of monolayer CuInP2S6 (CIPS) sandwiched between 2D magnetic electrodes of CrSe2. The AFTJ with nonmagnetic electrodes of TiSe2 on both sides of CIPS and the asymmetric AFTJ with both CrSe2 and TiSe2 electrodes are also investigated. Based on quantum-mechanical modeling of the electronic transport, sizeable tunneling electroresistance effects and multiple nonvolatile resistance states are demonstrated. More importantly, a remarkably low RA product (less than 0.1 Ω·μm2) makes the proposed vdW AFMTJs superior to the conventional MFTJs in terms of their promising nonvolatile memory applications. Our calculations provide new guidance for the experiment and application of nanoscale memory devices.

Concurrence of negative in-plane piezoelectricity and photocatalytic properties in 2D ScAgP2S6 monolayers

Apart from poly(vinylidene fluoride) and its copolymers, 2D multilayered CuInP2S6 (CIPS) is experimentally known to show negative out-of-plane piezoelectric coefficient (d 33) [2019 Sci. Adv. 5 1–10], which is attributable to weak interlayer van der Waals binding. However, CIPS monolayers exhibit positive in-plane piezoelectricity (d 11) [Phys. Status Solidi RRL, 14 2000321], as per DFT calculations. We ascribe it to strong in-plane interatomic bonding. Weakening of the in-plane interatomic bonding may even induce a negative in-plane piezoelectric coefficient, which is exceptionally rare, as observed in this work based on DFT calculations. Much smaller in-plane elastic constants found in ScAgP2S6 monolayers relative to that in CIPS monolayers indicate much weaker in-plane interatomic bonding, which induces negative in-plane piezoelectric coefficient, d 22 = −2.81 pm V−1, in ScAgP2S6 monolayers. In addition to its all-around stability, ScAgP2S6 monolayer is a semiconducting showing a bandgap of 2.04 eV, thereby making it suitable for electronics and solar energy harvesting. Upon the application of 4% biaxial strain on this flexible and stretchable 2D material, d 22 has been found to be drastically increased to −591 pm V−1. The factors causing such an enhancement in d 22 have been ascertained through the maximum rise in the Born effective charges and maximum drop in the elastic constants. With the further drop in elastic constants relative to ScAgP2S6 monolayer, d 22 reaches −3.45 pm V−1 and −13.48 pm V−1 in ScAgP2Se6 and ScAgP2Te6 monolayers respectively. 2D ScAgP2S6 monolayer is found to be a promising photocatalyst as well, since its band edges straddle the water redox potential over the entire range in pH (0–14), in addition to having a high absorption coefficient (≈105 cm−1) in the visible region. It is understood that 2D ScAgP2S6 will substantially expand the scope for its applications in piezoelectricity and visible light harvesting at the nanoscale.

Nonvolatile Electric Control of Exciton Complexes in Monolayer MoSe2 with Two-Dimensional Ferroelectric CuInP2S6.

Monolayer transition-metal dichalcogenides (TMDs) have provided a platform to investigate the excitonic states at the two-dimensional (2D) limit. The inherent properties of excitons in TMDs, such as the photoluminescence quantum yield, the charge states, and even the binding energy, can be effectively controlled via electrostatic gating, selective carrier doping, or substrate dielectric engineering. Here, aiming for the nonvolatile electrical tunability of excitonic states and thereby the optical property of TMDs, we demonstrate a 2D ferroelectric heterostructure with monolayer MoSe2 and ultrathin CuInP2S6 (CIPS). In the heterostructure, the electric polarization of CIPS results in continuous, global, and large electronic modulation in monolayer MoSe2. With the saturated ferroelectric polarization of CIPS, electron-doped or hole-doped MoSe2 is realized in a single device. The carrier density tunability in the heterostructure is as high as 5 × 1012 cm-2. The nonvolatile behavior of these devices up to 3 months is also characterized. Our results provide a new and practical strategy for low-power consumption and agelong tunable optoelectronic devices.

Ion adsorption-induced reversible polarization switching of a van der Waals layered ferroelectric

Solid-liquid interface is a key concept of many research fields, enabling numerous physical phenomena and practical applications. For example, electrode-electrolyte interfaces with electric double layers have been widely used in energy storage and regulating physical properties of functional materials. Creating a specific interface allows emergent functionalities and effects. Here, we show the artificial control of ferroelectric-liquid interfacial structures to switch polarization states reversibly in a van der Waals layered ferroelectric CuInP2S6 (CIPS). We discover that upward and downward polarization states can be induced by spontaneous physical adsorption of dodecylbenzenesulphonate anions and N,N-diethyl-N-methyl-N-(2-methoxyethyl)-ammonium cations, respectively, at the ferroelectric-liquid interface. This distinctive approach circumvents the structural damage of CIPS caused by Cu-ion conductivity during electrical switching process. Moreover, the polarized state features super-long retention time (>1 year). The interplay between ferroelectric dipoles and adsorbed organic ions has been studied systematically by comparative experiments and first-principles calculations. Such ion adsorption-induced reversible polarization switching in a van der Waals ferroelectric enriches the functionalities of solid-liquid interfaces, offering opportunities for liquid-controlled two-dimensional ferroelectric-based devices.