Heterostructures based on two dimensional (2D) materials offer the possibility to achieve synergistic functionalities which otherwise remain secluded by their individual counterparts. Herein ferroelectric polarization switching in alpha-In2Se3 has been utilized to engineer multilevel non-volatile conduction states in partially overlapping alpha-In2Se3-MoS2 based ferroelectric semiconducting field effect device. In particular, we demonstrate how the intercoupled ferroelectric nature of alpha-In2Se3 allows to non-volatilely switch between n-i and n-i-n type junction configurations based on a novel edge state actuation mechanism, paving the way for sub-nanometric scale non-volatile device miniaturization. Furthermore the induced asymmetric polarization enables enhanced photogenerated carriers separation resulting in extremely high photoresponse of 1275 AW-1 in the visible range and strong non-volatile modulation of the bright A- and B- excitonic emission channels in the overlaying MoS2 monolayer. Our results show significant potential to harness the switchable polarization in partially overlapping alpha-In2Se3-MoS2 based FeFETs to engineer multimodal non-volatile nanoscale electronic and optoelectronic devices.
Alpha Fe2O3 powders have been prepared by the reduction reaction method with NaHB4 as reducing agent and followed a conventional sintering process. The XRD pattern with Rietveld refinement profile reveal that the prepared Fe2O3 with corundum structure (hematite). VSM loop exhibits obvious room-temperature weak ferromagnetism, a pinched hysteresis loop may introduced by the shape anisotropy effect. The simultaneous ferroelectric behavior of α-Fe2O3 with "five-fold" ferroelectric hysteresis loops approves that this structured Fe2O3 can be known as a novel multiferroic material.
Ferroelectric tunnel junction devices based on ferroelectric thin films of solid solutions of hafnium dioxide can enable CMOS integration of ultra-low power ferroelectric devices with potential for memory and emerging computing schemes such as in-memory computing and neuromorphic applications. In this work, we present ferroelectric tunnel junctions based on Hf$_{0.5}$Zr$_{0.5}$O$_{2}$ with materials and processes compatible with CMOS back-end-of-line integration. We show a device architecture based on W-Hf$_{0.5}$Zr$_{0.5}$O$_{2}$-Al$_{2}$O$_{3}$-TiN stacks featuring low temperature annealing …
A detailed investigation of the out-of-plane electrical properties of charge-ordered alpha-(BEDT-TTF)2I3 provides clear evidence for ferroelectricity. Similar to multiferroic alpha-(BEDT-TTF)2Cu[N(CN)2]Cl, the polar order in this material is ascribed to the occurrence of bond- and site-centered charge order. Dielectric response typical for relaxor ferroelectricity is found deep in the charge-ordered state. We suggest an explanation in terms of the existence of polar and nonpolar stacks of the organic molecules in this material, preventing long-range ferroelectricity. The results are discussed …
We investigate ferroelectric- and resistive switching behavior in 18-nm-thick epitaxial BaTiO$_3$ (BTO) films in a model electrolyte-ferroelectric-semiconductor (EFS) configuration. The system is explored for its potential as a ferroelectric microelectrode in bioelectronics. The BTO films are grown by pulsed laser deposition (PLD) on semiconducting Nb-doped (0.5 wt\%) SrTiO$_{3}$ (Nb:STO) single crystal substrates. The ferroelectric properties of the bare BTO films are demonstrated by piezoresponse force microscopy (PFM) measurements. Cyclic voltammetry (CV) measurements in EFS configuration, …
2D ferroelectric narrow-bandgap semiconductor Wurtzite' type alpha-In2Se3 and its silicon-compatible growth
Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences（中国科学院金属研究所沈阳材料科学国家实验室）；School of Materials Science and Engineering, University of Science and Technology of China（中国科学技术大学材料科学与工程学院）；School of Physical Science and Technology, Jiangsu Key Laboratory of Frontier Material Physics and Devices, Soochow University（苏州大学江苏省前沿材料物理与器件重点实验室物理科学与技术学院）；Collaborative Innovation Center of Extreme Optics, Shanxi University（山西大学极端光学协同创新中心）；Center for Quantum Matter, School of Physics, Zhejiang University（浙江大学物理学院量子物质研究中心）；Department of Mechanical Engineering, The University of Hong Kong（香港大学机械工程系）
Thickness scaling of ferroelectricity in AlScN is a determining factor for its potential application in neuromorphic computing and memory devices. In this letter, we report on ultrathin (10 nm) Al0.72Sc0.28N films that are ferroelectrically switchable at room temperature. All-epitaxial Al0.72Sc0.28N/Pt heterostructures are grown by magnetron sputtering onto GaN/sapphire substrates followed by an in situ Pt capping approach to avoid oxidation of the Al0.72Sc0.28N film surface. Structural characterization by X-ray diffraction and transmission electron microscopy reveals the established epitaxy. …
Breakdown and polarization contrasts in ferroelectric devices observed by operando laser-based photoemission electron microscopy with the AC/DC electrical characterization system
Multiferroic (MF) devices based on simultaneous ferroelectric and ferromagnetic phenomena are considered to be promising candidates for future bi-functional micro/nano-electronics. The multiferroic phenomena in two-dimensional materials is rarely reported in literature. We reported a simple approach to reveal frequency-dependent ferroelectricity and mutiferroicity in Ti$_3$C$_2$T$_x$ MXene film at room-temperature. To study the frequency and poling effect on ferroelectricity as well as multiferroicity, we performed electric polarization vs. electric field measurement at different external freq…
Towards Improved Polarization Uniformity in Ferroelectric Hf$_{0.5}$Zr$_{0.5}$O$_2$ Devices within Back End of Line Thermal Budget for Memory and Neuromorphic Applications
Online training of deep neural networks (DNN) can be significantly accelerated by performing in-situ vector matrix multiplication in a crossbar array of analog memories. However, training accuracies often suffer due to device non-idealities such as nonlinearity, asymmetry, limited bit precision and dynamic weight update range within constrained power budget. Here, we report a three-terminal Ferroelectric-Field-Effect-Transistor based on low thermal budget processes that can work efficiently as an analog synaptic transistor. Ferroelectric polymer P(VDF-TrFE) as the gate insulator and 2D semicon…
The discovery of ferroelectric properties of binary oxides revitalized the interest in ferroelectrics and bridged the scaling gap between the state-of-the-art semiconductor technology and ferroelectric memories. However, before hitting the markets, the origin of ferroelectricity and in-depth studies of device characteristics are needed. Establishing a correlation between the performance of the device and underlying physical mechanisms is the first step toward understanding the device and engineering guidelines for a novel, superior device. Therefore, in this paper a holistic modeling approache…
My research is dedicated to the electronic properties of functional oxides. My activity specifically focuses on ferroelectric tunnel junctions in which an ultrathin layer of ferroelectric material is intercalated between two metallic electrodes. In these devices, polarization reversal induces large modifications of the tunnel resistance, leading to a non-destructive readout of the information. After a demonstration of the concept with scanning probe microscopy techniques, I have been exploring the properties of ferroelectric tunnel junctions with various ferroelectric materials (BaTiO3, BiFeO3…
Atomic-scale understanding of HfO2 ferroelectricity is important to help address many challenges in developing reliable and high-performance ferroelectric HfO2 (fe-HfO2) based devices. Though investigated from different angles, a factor that is real device-relevant and clearly deserves more attention has largely been overlooked by previous research, namely, the fe-HfO2/dielectric interface. Here, we investigate the electronic structures of several typical interfaces formed between ultrathin fe-HfO2 and oxide dielectrics in the sub-3-nm region. We find that interface formation introduces strong…
About ten years after ferroelectricity was first reported in doped HfO2 polycrystalline films, there is tremendous interest in this material and ferroelectric oxides are once again in the spotlight of the memories industry. Great efforts are being made to understand and control ferroelectric properties. Epitaxial films, which have fewer defects and a more controlled microstructure than polycrystalline films, can be very useful for this purpose. Epitaxial films of ferroelectric HfO2 have been much less investigated, but after the first report in 2015 significant progress has been achieved. This…
2D Ferroelectric materials are promising for designing low-dimensional memory devices. Here, we explore strain tunable ferroelectric properties of group-IV monochalcogenides MX (M=Ge, Sn; X=S, Se) and their potential application in lateral field tunnel junction devices. We find that these monolayers have in-plane ferroelectricity, with their ferroelectric parameters being on par with other known 2D ferroelectric materials. Amongst SnSe, SnS, GeSe, and GeS, we find that GeS has the best ferroelectric parameters for device applications, which can be improved further by applying uniaxial tensile …
Although technologically challenging, the integration of ferroelectric thin films with graphene spintronics potentially allows the realization of highly efficient, electrically tuneable, non-volatile memories. Here, the atomic layer deposition (ALD) of ferroelectric Hf$_{0.5}$Zr$_{0.5}$O$_2$ (HZO) directly on graphene (Gr)/Co/heavy metal (HM) epitaxial stacks is investigated via the implementation of several nucleation methods. With an in-situ method employing an Al$_2$O$_3$ layer, the HZO demonstrates a remanent polarization (2Pr) of 19.2 $μC/cm^2$. An ex-situ, naturally oxidized sputtered Ta…
Synchrotron x-ray scattering studies of anti-ferroelectric nanoregions (AFR) as fluctuations, which give rise to 1/2(hk0) superlattice reflections (alpha spots), were systematically performed in Pb(Mg1/3Nb2/3)O3 (PMN) ferroelectric relaxor. Separation of the alpha spots from underlying diffuse scattering background allowed studying them as separate entities for the first time. AFR fluctuations were shown to be different from the chemical nanodomains (CND) and ferroelectric polar nano-regions (PNR). Instead, they are formed by anti-parallel short-range correlated Pb^2+ displacements that lead t…
Graphene plasmons are able to become the fundermental of novel conceptual photonic devices, resulting from their unique characteristics containing excitation at room temperature and tunable spectral selectivity in different frequencies. The pursuit of efficiently exciting and manipulating graphene plasmons is necessary and significant for high-performance devices. Here, we investigate graphene plasmon wave propagating in ferroelectric nanocavity array. We experimentally show that the the periodic ferroelectric polarizations could be used for doping graphene into desired spatial carrier density…
Copper indium thiophosphate, CuInP2S6, has attracted much attention in recent years due to its van der Waals layered structure and robust ferroelectricity at room temperature. In this review, we aim to give an overview of the various properties of CuInP2S6, covering structural, ferroelectric, dielectric, piezoelectric and transport properties, as well as its potential applications. We also highlight the remaining questions and possible research directions related to this fascinating material and other compounds of the same family.
To optimize the performance of multifunctional carbon nanotube-ferroelectric devices, it is necessary to understand both the polarization and charge dynamics effects on their transconductance. Directly comparing ferroelectric Pb(Zr0.2Ti0.8)O3 and dielectric SrTiO3 field effect transistors, we show that the two effects strongly compete, with transient charge dynamics initially masking up to 40% of the ferroelectric field effect. For applications, it is therefore crucial to maximize the quality of the ferroelectric film and the interface with the carbon nanotube to take full advantage of the swi…
We report on the fabrication and electrical characterization of few-layer graphene (FLG) devices coated with a ferroelectric polymer layer of poly(vinylidene fluoride/trifluoroethylene) [P(VDF/TrFE)]. Highly stable and reliable resistance changes were observed under floating conditions, which were dependent on the back gate voltage applied beforehand. Nonvolatile memory functionality in the hybrid FLG-P(VDF/TrFE) devices is attributed to a remanent electric field induced by the ferroelectric polarization of the P(VDF/TrFE) layer.
Ferroelectric field-effect transistors employ a ferroelectric material as a gate insulator, the polarization state of which can be detected using the channel conductance of the device. As a result, the devices are of potential to use in non-volatile memory technology, but suffer from short retention times, which limits their wider application. Here we report a ferroelectric semiconductor field-effect transistor in which a two-dimensional ferroelectric semiconductor, indium selenide (α-In2Se3), is used as the channel material in the device. α-In2Se3 was chosen due to its appropriate bandgap, ro…
The concept of a nano-actuator that uses ferroelectric switching to generate enhanced displacements is explored using a phase-field model. The actuator has a ground state in the absence of applied electric field that consists of polarized domains oriented to form a flux closure. When electric field is applied, the polarization reorients through ferroelectric switching and produces strain. The device is mechanically biased by a substrate and returns to the ground state when electric field is removed, giving a repeatable actuation cycle. The mechanical strains which accompany ferroelectric switc…
Ferroelecticity, one of the keys to realize nonvolatile memories owing to the remanent electric polarization, has been an emerging phenomenon in the two-dimensional (2D) limit. Yet the demonstrations of van der Waals (vdW) memories using 2D ferroelectric materials as an ingredient are very limited. Especially, gate-tunable ferroelectric vdW memristive device, which holds promises in future neuromorphic applications, remains challenging. Here, we show a prototype gate-programmable memory by vertically assembling graphite, CuInP2S6, and MoS2 layers into a metal-ferroelectric-semiconductor archit…
In the quest for reliable and power-efficient memristive devices, ferroelectric tunnel junctions are being investigated as potential candidates. CMOS-compatible ferroelectric hafnium oxides are at the forefront. However, in epitaxial tunnel devices with thicknesses around ${\approx}$ 4 - 6 nm, the relatively high tunnel energy barrier produces a large resistance that challenges their implementation. Here, we show that ferroelectric and electroresistive switching can be observed in ultrathin 2 nm epitaxial Hf$_{0.5}$Zr$_{0.5}$O$_2$ (HZO) tunnel junctions in large area capacitors (${\approx} 300…
The discovery and precise manipulation of atomic-size conductive ferroelectric domain defects, such as geometrically confined walls, offer new opportunities for a wide range of prospective electronic devices, and the so-called walltronics is emerging consequently. Here we demonstrate the highly stable and fatigue-resistant nonvolatile ferroelectric memory device based on deterministic creation and erasure of conductive domain wall geometrically confined inside a topological domain structure. By introducing a pair of delicately designed co-axial electrodes onto the epitaxial BiFeO3 film, one ca…
It was discovered in 2010 that Croconic Acid, in its crystal form, has the highest polarization among organic ferroelectrics. In the context of eliminating toxic substances from electronic devices, Croconic Acid has a great potential as a sublimable lead-free ferroelectric. However, studies on ferroelectric properties of its thin films are only in their early stages and its capability to be incorporated in nanoscale devices is unknown. In this work, we demonstrate, upon ferroelectric switching at the nanoscale, stable and enduring room temperature polarization with no leakage current in Crocon…
There is currently much interest in materials and structures that provide coupled ferroelectric and ferromagnetic responses, with a long-term goal of developing new memories and spintronic logic elements. Within the field there is a focus on composites coupled by magnetostrictive and piezoelectric strain transmitted across ferromagnetic-ferroelectric interfaces, but substrate clamping limits the response in the supported multilayer configuration favoured for devices. This constraint is avoided in a ferroelectric-ferromagnetic bilayer in which the magnetic response is modulated by the electric …
We revise the possibility of having an amplified surface potential in ferroelectric field-effect transistors pointed out by [S. Salahuddin and S. Datta, Nano Lett. 8, 405 (2008)]. We show that the negative-capacitance regime that allows for such an amplification is actually bounded by the appearance of multi-domain ferroelectricity. This imposes a severe limit to the maximum step-up of the surface potential obtainable in the device. We indicate new device design rules taking into account this scenario.
The epitaxial growth of multifunctional oxides on semiconductors has opened a pathway to introduce new functionalities to semiconductor device technologies. In particular, ferroelectric materials integrated on semiconductors could lead to low-power field-effect devices that can be used for logic and memory. Essential to realizing such field-effect devices is the development of ferroelectric metal-oxide-semiconductor (MOS) capacitors, in which the polarization of a ferroelectric gate is coupled to the surface potential of a semiconducting channel. Here we demonstrate that ferroelectric MOS capa…
In this study, we propose a measurement technique for evaluating ferroelectric polarization characteristics in ferroelectric field-effect transistors (FeFETs). Different from standard metal/ferroelectric/metal capacitors, the depletion and inversion phenomena in semiconductor substrates have to be carefully taken into account when evaluating the ferroelectric properties using fast voltage sweep as input. The non-equilibrium deep depletion is found to be the limiting factor for the accurate evaluation of ferroelectric properties in metal/ferroelectric/semiconductor capacitors. By connecting the…
Here, we optimized the annealing temperature of HZO/TiN thin film heterostructure via multiscale analysis of remnant polarization, crystallographic phase, minimum ferroelectric domain size, and average grain size. We found that the remnant polarization was closely related to the relative amount of the orthorhombic phase whereas the minimum domain size was to the relative amount of the monoclinic phase. The minimum domain size was obtained at the annealing temperature of 500$^\cird$C while the optimum remnant polarization and capacitance at the annealing temperature of 600$^\circ$C. We conclude…
In this work, we report a massively parallel and time domain implementation of the 3D phase field model that can reach beyond micron scale and consider for arbitrary electrical and mechanical boundary conditions. The first part of the paper describes the theory and the numerical implementation of the model. A mixed-mode approach of finite difference and finite element grid has been used for calculating the nonlocal electrostatic and elastic interactions respectively. All the local and non-local interactions are shown to scale linearly up to thousands of processors. This massive parallelization…
The discovery of stable room temperature ferroelectricity in Croconic Acid, an organic ferroelectric material, with polarization values on par with those found in inorganic ferroelectric materials and highest among organic ferroelectric materials, has opened up possibilities to realize myriads of nano-electronic and spintronic devices based on organic ferroelectrics. Such possibilities require an adequate understanding of the ferroelectric properties of Croconic Acid grown on surfaces that are commonly employed in device fabrication. While several macroscopic studies on relatively larger cryst…
Films of Hf0.5Z0.5O2 (HZO) contain a network of grain boundaries. In (111) HZO epitaxial films on (001) SrTiO3, for instance, twinned orthorhombic (o-HZO) ferroelectric crystallites coexist with grain boundaries between o-HZO and a residual paraelectric monoclinic (m-HZO) phase. These grain boundaries contribute to the resistive switching response in addition to the genuine ferroelectric polarization switching and have detrimental effects on device performance. Here, it is shown that, by using suitable nanometric capping layers deposited on HZO film, a radical improvement of the operation wind…
Device-area selection of memristive transport regimes in epitaxial $Hf_{0.5}Zr_{0.5}O_{2}$-based ferroelectric devices
INN-CONICET-CNEA（阿根廷国家原子能委员会-国家科学研究委员会研究所）；Universidad Argentina de la Empresa (UADE)（阿根廷企业大学）；Instituto de Nanociencia y Materiales de Aragón (INMA-CSIC)（阿拉贡纳米科学与材料研究所）；Universidad de Zaragoza（萨拉戈萨大学）；Catalan Institute of Nanoscience and Nanotechnology (ICN2)（加泰罗尼亚纳米科学与技术研究所）；Centre de Nanosciences et de Nanotechnologies, CNRS, Université Paris-Saclay（巴黎萨克雷大学-CNRS纳米科学中心）；University of Groningen（格罗宁根大学）
Ferroelectric domain switching in c-axis-oriented epitaxial Pb(Zr0.2Ti0.8)O3 thin films was studied using different field geometries and compared to numerical simulations and theoretical predictions. With carbon nanotubes as electrodes, continuous nanodomains as small as 9 nm in radius in a 270 nm thick film could be switched, remaining stable for over 20 months. Defect pinning of domain walls appears to play a key role in stabilizing such domains, below the predicted thermodynamic size limit.
The conductivity of the system magnetic dielectric (EuO) - graphene channel - ferroelectric substrate was considered. The magnetic dielectric locally transforms the band spectrum of graphene by inducing an energy gap in it and making it spin-asymmetric with respect to the free electrons. The range of spontaneous polarization (2- 5)mC/m2 that can be easily realized in thin films of proper and incipient ferroelectrics, was under examination. It was demonstrated, that if the Fermi level in the graphene channel belongs to energy intervals where the graphene band spectrum, modified by EuO, becomes …
Unconventional ferroelectricity, robust at reduced nanoscale sizes, exhibited by hafnia-based thin-films presents tremendous opportunities in nanoelectronics. However, the exact nature of polarization switching remains controversial. Here, we investigate epitaxial Hf0.5Zr0.5O2 (HZO) capacitors, interfaced with oxygen conducting metals (La0.67Sr0.33MnO3, LSMO) as electrodes, using atomic resolution electron microscopy while in situ electrical biasing. By direct oxygen imaging, we observe reversible oxygen vacancy migration from the bottom to the top electrode through HZO and reveal associated r…
We present measurements of conductance hysteresis on CH3NH3PbI3 perovskite thin films, performed using the double-wave method, in order to investigate the possibility of a ferroelectric response. A strong frequency dependence of the hysteresis is observed in the range of 0.1 Hz to 150 Hz, with a hysteretic charge density in excess of 1000 μC/cm2 at frequencies below 0.4 Hz - a behaviour uncharacteristic of a ferroelectric response. We show that the observed hysteretic conductance, as well as the presence of a double arc in the impedance spectroscopy, can be fully explained by the migration of …
