Organic multiferroic tunnel junctions (OMFTJs) with multi-resistance states have been proposed and drawn intensive interests due to their potential applications, for examples of memristor and spintronics based synapse devices. The ferroelectric control of spin-polarization at ferromagnet (FM)/ferroelectric organic (FE-Org) interface by electrically switching the ferroelectric polarization of the FE-Org has been recently realized. However, there is still a lack of understanding of the transport properties in OMFTJs, especially the interplay between the ferroelectric domain structure in the organic barrier and the spin-polarized electron tunneling through the barrier. Here, we report on a systematic study of the temperature dependent transport behavior in La0.6Sr0.4MnO3/PVDF/Co OMFTJs. It is found that the thermal fluctuation of the ferroelectric domains plays an important role on the transport properties. When T>120K, the opposite temperature dependence of resistance for in up and down ferroelectric polarization states results in a rapid diminishing of tunneling electroresistance (TER). These results contribute to the understanding of the transport properties for designing high performance OMFTJs for memristor and spintronics applications.
Organic-inorganic multiferroics are promising for the next generation of electronic devices. To date, dozens of organic-inorganic multiferroics have been reported; however, most of them show magnetic Curie temperature much lower than room temperature, which drastically hampers their application. Here, by performing first-principle calculations and building effective model Hamiltonians, we reveal a molecular orbital-mediated magnetic coupling mechanism in two-dimensional Cr(pyz)2 (pyz=pyrazine), and the role that the valence state of the molecule plays in determining the magnetic coupling type …
We show by means of ab-initio calculations that the organic molecular crystal TTF-CA is multiferroic: it has an instability to develop spontaneously both ferroelectric and magnetic ordering. Ferroelectricity is driven by a Peierls transition of the TTF-CA in its ionic state. Subsequent antiferromagnetic ordering strongly enhances the opposing electronic contribution to the polarization: it is so large that it switches the direction of the total ferroelectric moment. Within an extended Hubbard model we capture the essence of the electronic interactions in TTF-CA, confirm the presence of a multi…
There is great interest in hybrid organic-inorganic materials such as metal-organic frameworks (MOFs). The compounds [C(NH$_{2}$)$_{3}$]M(HCOO)$_{3}$, where M=Cu$^{2+}$ or Cr$^{2+}$ are Jahn-Teller (JT) active ions, are MOF with perovskite topology which crystallizes in polar space group Pna2$_{1}$. In inorganic compounds, octahedral tilting and Jahn-Teller structural distortions are usually non-polar distortions. However, in this MOF cooperative interactions between the antiferro-distortive distortions of the framework and the C(NH2)$_{3}$ organic cation via hydrogen bonding breaks the invers…
Spin-dependent electronic transport through multiferroic Co/PbTiO$_{3}$/Co tunnel junctions is studied theoretically. Conductances calculated within the Landauer-Büttiker formalism yield both a large tunnel magnetoresistance (TMR) and a large tunnel electroresistance (TER). On top of this, we establish a four-conductance state. The conductances depend crucially on the details of the electronic structure at the interfaces. In particular, the spin polarization of the tunneling electronic states is affected by the hybridization of orbitals and the associated charge transfer at both interfaces. Di…
We report on the fabrication of organic multiferroic tunnel junction (OMFTJ) based on an organic barrier of Poly(vinylidene fluoride) (PVDF):Fe3O4 nanocomposite. By adding Fe3O4 nanoparticles into the PVDF barrier, we found that the ferroelectric properties of the OMFTJ are considerably improved compared to that with pure PVDF barrier. It can lead to a tunneling electroresistance (TER) of about 450% at 10K and 100% at room temperature (RT), which is much higher than that of the pure PVDF based device (70% at 10K and 7% at RT). OMFTJs based on the PVDF:Fe3O4 nanocomposite could open new functio…
Manipulation of tunneling spin-polarized electrons via a ferroelectric interlayer sandwiched between two ferromagnetic electrodes, dubbed Multiferroic Tunnel Junctions (MFTJs), can be achieved not only by the magnetic alignments of two ferromagnets but also by the electric polarization of the ferroelectric interlayer, providing great opportunities for next-generation multi-state memory devices. Here we show that a La0.67Sr0.33MnO3 (LSMO)/PbZr0.2Ti0.8O3(PZT)/Co structured MFTJ device can exhibit multilevel resistance states in the presence of gradually reversed ferroelectric domains via tunneli…
We demonstrate that ethylammonium copper chloride, (C2H5NH3)2CuCl4, a member of the hybrid perovskite family is an electrically polar and magnetic compound with dielectric anomaly around the Curie point (247 K). We have found large spontaneous electric polarization below this point accompanied with a color change in the sample. The system is also ferroelectric, with large remnant polarization (37μC/cm2) that is comparable to classical ferroelectric compounds. The results are ascribed to hydrogen-bond ordering of the organic chains. The coexistence of ferroelectricity and dominant ferromagnetic…
Within the broad class of multiferroics (compounds showing a coexistence of magnetism and ferroelectricity), we focus on the subclass of "improper electronic ferroelectrics", i.e. correlated materials where electronic degrees of freedom (such as spin, charge or orbital) drive ferroelectricity. In particular, in spin-induced ferroelectrics, there is not only a {\em coexistence} of the two intriguing magnetic and dipolar orders; rather, there is such an intimate link that one drives the other, suggesting a giant magnetoelectric coupling. Via first-principles approaches based on density functiona…
Self-poled ultra-thin ferroelectric PbZr0.52Ti0.48O3 (PZT) (5 and 7 nm) films have been grown by pulsed laser deposition technique on ferromagnetic La0.67Sr0.33MnO3 (LSMO) (30 nm) to check the effect of polar capping on magnetization for ferroelectric tunnel junction (FTJ) devices. PZT/LSMO heterostructures with thick polar PZT (7 nm) capping show nearly 100% enhancement in magnetization compared with thin polar PZT (5 nm) films, probably due to excess hole transfer from the ferroelectric to the ferromagnetic layers. Core-level X-ray photoelectron spectroscopy studies revealed the presence of …
Multiferroic tunnel junctions (MFTJs) have already been proved to be promising candidates for application in spintronics devices. The coupling between tunnel magnetoresistance (TMR) and tunnel electroresistance (TER) in MFTJs can provide four distinct resistive states in a single memory cell. Here we show that in an all-oxide asymmetric MFTJ of La0.7Sr0.3MnO3 /PbZr0.2Ti0.8O3 /La0.7Te0.3MnO3 (LSMO/PZT/LTMO) with p-type and n-type electrodes, the intrinsic rectification is observed and can be modified by the ferroelectric polarization of PZT. Owing to the combined TMR, TER and diode effects, two…
We report on the functionalization of multiferroic BiFeO3 epitaxial films for spintronics. A first example is provided by the use of ultrathin layers of BiFeO3 as tunnel barriers in magnetic tunnel junctions with La2/3Sr1/3MnO3 and Co electrodes. In such structures, a positive tunnel magnetoresistance up to 30% is obtained at low temperature. A second example is the exploitation of the antiferromagnetic spin structure of a BiFeO3 film to induce a sizeable (~60 Oe) exchange bias on a ferromagnetic film of CoFeB, at room temperature. Remarkably, the exchange bias effect is robust upon magnetic f…
Multiferroics are singular materials that can display simultaneously electric and magnetic orders. Some of them can be ferroelectric and ferromagnetic and, for example, provide the unique opportunity of encoding information independently in electric polarization and magnetization to obtain four different logic states. However, schemes allowing a simple electrical readout of these different states have not been demonstrated so far. In this article, we show that this can be achieved if a multiferroic material is used as the tunnel barrier in a magnetic tunnel junction. We demonstrate that thin f…
Perovskite metal-organic frameworks (MOFs) have recently emerged as potential candidates for multiferroicity. However, the compounds synthesized so far possess only weak ferromagnetism and low polarization. Additionally, the very low magnetic transition temperatures ($T_c$) also pose a challenge to the application of the materials. We have computationally designed a mixed metal perovskite MOF -[C(NH2)3][(Cu0.5Mn0.5)(HCOO)3]- that is predicted to have magnetization two orders of magnitude larger than its parent ([C(NH2)3][Cu(HCOO)3]), a significantly larger polarization (9.9 μC/cm2), and an enh…
We deduce the intrinsic conductivity properties of the ferroelectric domain walls around the topologically protected domain vortex cores in multiferroic YMnO3. This is achieved by performing a careful equivalent-circuit analysis of dielectric spectra measured in single-crystalline samples with different vortex densities. The conductivity contrast between the bulk domains and the less conducting domain boundaries is revealed to reach up to a factor 500 at room temperature, depending on sample preparation. Tunneling of localized defect charge carriers is the dominant charge-transport process in …
First-principles density functional calculations show that the $\textrm{SrRuO}_{3}/\textrm{PbTiO}_{3}/\textrm{SrRuO}_{3}$ multiferroic junction with asymmetric (RuO$_{2}$/PbO and TiO$_{2}$/SrO) interfaces has a large ferroelectric depolarizing field, whose switching changes the interface transmission probabilities for tunneling electrons, leading to electroresistance modulation over several orders of magnitude. The switching further affects the interface spin density, naturally driving magnetoresistance as well as modulated spin-dependent in-plane resistivity, which may be exploited in field-e…
Above room temperature multiferroic tunnel junction with the altermagnetic metal CrSb
Huazhong University of Science and Technology（华中科技大学）；Florida State University（佛罗里达州立大学）；National High Magnetic Field Laboratory（国家强磁场实验室）；Charles University（查理大学）
The transport properties of domain walls in oxygen deficient multiferroic YMnO3 single crystals have been probed using conductive atomic force microscopy and piezoresponse force microscopy. Domain walls exhibit significantly enhanced conductance after being poled in electric fields, possibly induced by oxygen vacancy ordering at domain walls. The electronic conduction can be understood by the Schottky emission and Fowler-Nordheim tunnelling mechanisms. Our results show that the domain wall conductance can be modulated through band structure engineering by manipulating ordered oxygen vacancies …
Magnetic Tunnel Junctions whose basic element consists of two ferromagnetic electrodes separated by an insulating non-magnetic barrier have become intensely studied and used in non-volatile spintronic devices. Since ballistic tunnel of spin-polarized electrons sensitively depends on the chemical composition and the atomic geometry of the lead/barrier interfaces their proper design is a key issue for achieving the required functionality of the devices such as e.g. a high tunnel magneto resistance. An important leap in the development of novel spintronic devices is to replace the insulating barr…
Coexistence of ferromagnetism and ferroelectricity in the van der Waals multiferroic CuIn0.2V0.8P2S6
D crystal consortium, Materials Research Institute, Pennsylvania State University（宾夕法尼亚州立大学材料研究所）；Department of Physics, Pennsylvania State University（宾夕法尼亚州立大学物理系）；Department of Electrical and Computer Engineering and Quantum Technology Center, University of Maryland（马里兰大学电气与计算机工程系及量子技术中心）；Department of Chemistry, Michigan State University（密歇根州立大学化学系）；Department of Materials Science and Engineering, Pennsylvania State University（宾夕法尼亚州立大学材料科学与工程系）
Oxyhydroxide minerals like FeOOH have been a research focus in geology for studying the Earth interior, and also in chemistry for studying oxygen electrocatalysis activity. In this paper we provide first-principles evidence of a new class of ferroelectrics or multiferroics among them:GaOOH,InOOH,CrOOH,FeOOH, which are earth-abundant minerals and have been experimentally verified to possess distorted rutile structures, are ferroelectric with considerable polarizations(up to 24 muC/cm2) and piezoelectric coefficients. Their atomic-thick layer may possess vertical polarization robust against depo…
State Key Laboratory of Spintronics, Hangzhou International Innovation Institute, Beihang University（北京航空航天大学杭州创新研究院自旋电子学国家重点实验室）；Fert Beijing Institute, School of Integrated Circuit Science and Engineering, Beihang University（北京航空航天大学集成电路科学与工程学院法伯北京研究所）；CNRS, Institute Jean Lamour, Université de Lorraine（洛林大学让·拉缪尔研究所法国国家科学研究中心）
We present a combined experimental and theoretical study to get insight into both memory and negative differential resistance (NDR) effect in organic memory devices. The theoretical model we propose is simply a one-dimensional metallic island array embedding within two electrodes. We use scattering operator method to evaluate the tunneling current among the electrode and islands to establish the basic bistable I-V curves for several devices. The theoretical results match the experiments very well, and both memory and NDR effect could be understood comprehensively. The experimental corresponden…
We investigate the spin- and energy dependent tunneling through a single organic molecule (CoPc) adsorbed on a ferromagnetic Fe thin film, spatially resolved by low-temperature spin-polarized scanning tunneling microscopy. Interestingly, the metal ion as well as the organic ligand show a significant spin-dependence of tunneling current flow. State-of-the-art ab initio calculations including also van-der-Waals interactions reveal a strong hybridization of molecular orbitals and surface 3d states. The molecule is anionic due to a transfer of one electron, resulting in a non-magnetic (S= 0) state…
Delocalized carbon-based radical species with unpaired spin, such as phenalenyl (PLY) radical, opened avenues for developing multifunctional organic spintronic devices. Here we develop a novel technique based on a three-dimensional shadow mask and the in-situ deposition to fabricate PLY-, Cu-PLY-, and Zn-PLY-based organic magnetic tunnel junctions (OMTJs) with area 3x8 μm2 and improved morphology. The nonlinear and weakly temperature-dependent current-voltage (I-V) characteristics in combination with the low organic barrier height suggest tunneling as the dominant transport mechanism in the st…
The conductance-voltage spectrum of molecular nanostructures measured by scanning tunneling spectroscopy (STS) is generally assumed to reflect the local density of states of the molecule. This excludes the possibility of observing negative differential resistance (NDR). We report here the observation of NDR in the scanning tunneling microscope (STM) current-voltage (I-V) characteristics of self-assembled monolayer (SAM) of 4-p-Terphenylthiol molecules on gold substrate measured using a platinum probe. We argue that the NDR arises from narrow structures in the local density of states at the tip…
Metal-organic frameworks (MOFs) possess a hybrid nature, combining the inorganic properties from the metal ions and the organic properties from the molecular linkers. Stroppa, \textit{et al.}, showed that the perovskite-type MOF [C(NH$_2$)$_3$]M[(HCOO)$_3$] (M = Cr, Cu) exhibits the magneto-electric coupled multiferroicity [Angew. Chem. Int. Ed. 50, 5847 (2011) and Adv. Mater. 25, 2284 (2013)]. Moreover, their ferroelectricity arises from the hybrid improper mechanism, which also explains the magneto-electric coupling. In this work, we further examine the electric and magnetic properties of [C…
Multiferroics are materials where two or more ferroic orders coexist owing to the interplay between spin, charge, lattice and orbital degrees of freedom. The explosive expansion of multiferroics literature in recent years demon-strates the fast growing interest in this field. In these studies, the first-principles calculation has played a pioneer role in the experiment explanation, mechanism discovery and prediction of novel multiferroics or magnetoelectric materials. In this review, we discuss, by no means comprehensively, the extensive applications and successful achievements of first-princi…
We report on the structural and electronic properties of the interface between the multiferoic oxide YMnO$_3$ and wide band-gap semiconductor GaN studied with the Hubbard-corrected local spin density approximation (LSDA+U) to density-functional theory (DFT). We find that the band offsets at the interface between antiferromagnetically ordered YMnO$_3$ and GaN are different for spin-up and spin-down states. This behavior is due to the spin splitting of the valence band induced by the interface. The energy barrier depends on the relative orientation of the electric polarization with respect to th…
Hybrid conjugated polymer/fullerene filaments based on MEH-PPV/PVP/PCBM are prepared by electrospinning, and their properties assessed by scanning electron, atomic and lateral force, tunnelling, and confocal microscopy, as well as by attenuated total reflection Fourier transform-infrared spectroscopy, photoluminescence quantum yield and spatially-resolved fluorescence. Highlighted features include ribbon-shape of the realized fibers, and the persistence of a network serving as a template for heterogeneous active layers in solar cell devices. A set of favorable characteristics is evidenced in t…
Chirality-induced magnetoresistance in hybrid organic-inorganic perovskite semiconductors
National Laboratory of the Rockies（落基山国家实验室）；Renewable and Sustainable Energy Institute, University of Colorado Boulder（科罗拉多大学博尔德分校可再生能源与可持续能源研究所）；North Carolina State University（北卡罗来纳州立大学）；University of Wisconsin-Madison（威斯康星大学麦迪逊分校）；Center for Hybrid Organic Inorganic Semiconductors for Energy（能源混合有机无机半导体中心）
Multiferroic van der Waals (vdW) heterostrucutres offers an exciting route towards novel nanoelectronics and spintronics device technology. Here we investigate the electronic and transport properties of multiferroic vdW heterostructure composed of ferromagnetic FeCl$_2$ monolayer and ferroelectric Sc$_2$CO$_2$ monolayer using first-principles density functional theory and quantum transport simulations. We show that FeCl$_2$/Sc$_2$CO$_2$ heterostructure can be reversibly switched from semiconducting to half-metallic behavior by electrically modulating the ferroelectric polarization states of Sc…
This work describes an innovative concept for the development of organized molecular systems thanks to the template effect of the pre-structured semi-conductive SmSi(111) interface. This substrate was selected because Sm deposition in the submonolayer range leads to a 8x2-reconstruction, which is a well-defined one-dimensional semi-metallic structure. Adsorption of aromatic molecules (1,4-di-(9-ethynyltriptycenyl)-benzene) on SmSi(111)-8x2 and Si(111)-7x7 interfaces has been investigated by scanning tunneling microscopy (STM) at room temperature. Density functional theory (DFT) and semi-empiri…
In this paper, the photocatalytic activity of multiferroics BiFeO3 (BFO) and Bi0.8La0.2FeO3 (BLFO) nanocrystals with two different morphologies which were synthesized by two different sol-gel (SG) and hydrothermal (HT) methods have been studied. All the obtained samples were characterized using X-ray diffractometer, Fourier transform infrared spectroscopy, transmission electron microscopy, UV-vis spectroscopy and vibrating sample magnetometer. Differential thermal analysis (DTA) measurements were probed ferroelectric- paraelectric first-order phase transition (TC) for all samples. Addition of …
A ferroelectric tunnel barrier in between two ferromagnetic electrodes (multiferroic tunnel junction, MFTJ), is one of the most promising concepts for future microelectronic devices. In parallel, Hafnia based ferroelectrics are showing great potential for device miniaturization down to the nanoscale. Here we utilize ferroelectric Hf0.5Zr0.5O2 (HZO) with thickness of only 2 nm, epitaxially grown on La0.7Sr0.3MnO3 (LSMO) ferromagnetic electrodes, as a large band-gap insulating barrier integrated in MFTJs with cobalt top electrodes. As previously reported for other MFTJs with similar electrodes, …
Magnetic tunnel junctions (MTJs), composed of two ferromagnetic electrodes separated by a thin insulating barrier layer, are currently used in spintronic devices, such as magnetic sensors and magnetic random access memories. Recently, driven by demonstrations of ferroelectricity at the nanoscale, thin-film ferroelectric barriers were proposed to extend the functionality of MTJs. Due to the sensitivity of conductance to the magnetization alignment of the electrodes (tunnelling magnetoresistance) and the polarization orientation in the ferroelectric barrier (tunnelling electroresistance), these …
By means of ab initio calculations and spin-polarized scanning tunneling microscopy experiments we show how to manipulate the local spin-polarization of a ferromagnetic surface by creating a complex energy dependent magnetic structure. We demonstrate this novel effect by adsorbing organic molecules containing pi(pz)-electrons onto a ferromagnetic surface, in which the hybridization of the out-of-plane pz atomic type orbitals with the d-states of the metal leads to the inversion of the spin-polarization at the organic site due to a pz - d Zener exchange type mechanism. As a key result, we demon…
Understanding charge transport in organic semiconductors in large electric fields is relevant to many applications. We present transport measurements in organic field-effect transistors based on poly(3-hexylthiophene) and 6,13-bis(triisopropyl-silylethynyl) pentacene with short channels, from room temperature down to 4.2 K. Near 300 K transport in both systems is well described by thermally assisted hopping with Poole-Frenkel-like enhancement of the mobility. At low temperatures and large gate voltages, transport in both materials becomes nearly temperature independent, crossing over into fiel…
Magnetoelectric coupling between magnetic and electric dipoles is one of the cornerstones of modern physics towards developing the most energy-efficient magnetic data storage. Conventionally, magnetoelectric coupling is achieved in single-phase multiferroics or in magnetoelectric composite nanostructures consisting of ferromagnetic and ferroelectric/piezoelectric materials. Here, we demonstrate an electric-field-induced strain-mediated magnetoelectric effect in ultrathin CoFeB/MgO magnetic tunnel junction employing non-piezoelectric material, which is a vitally important structure for spintron…
Achieving large-area uniform two-dimensional (2D) metal-organic frameworks (MOFs) and controlling their electronic properties on inert surfaces is a big step towards future applications in electronic devices. Here we successfully fabricated a 2D monolayer Cu-dicyanoanthracene (DCA) MOF with long-range order on an epitaxial graphene surface. Its structural and electronic properties are studied by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) complemented by density-functional theory (DFT) calculations. We demonstrate access to multiple molecular charge states in the…
After evaporation of the organic solvents, benzene, toluene, and cyclohexane on gold substrates, Scanning Tunneling Microscope (STM) shows the presence of a remaining adsorbed layer. The different solvent molecules were individually observed at ambient conditions, and their electronic transport properties characterized through the STM in the Break Junction approach. The combination of both techniques reveals, on one hand, that solvents are not fully evaporated over the gold electrode and, secondly, determines the role of the electronic transport of the solvents in molecular electronics.
We report low frequency tunnel current noise characteristics of an organic monolayer tunnel junction. The measured devices, n-Si/alkyl chain (C18H37)/Al junctions, exhibit a clear 1/ f γ power spectrum noise with 1< γ <1.2. We observe a slight bias-dependent background of the normalized current noise power spectrum (SI/I^2). However, a local increase is also observed over a certain bias range, mainly if V > 0.4 V, with an amplitude varying from device to device. We attribute this effect to an energy-dependent trap-induced tunnel current. We find that the background noise, SI, scales …
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…
We show evidence that tunnel junctions (TJs) in GaN grown by metal-organic vapor phase epitaxy are dominated by trap-assisted (Poole-Frenkel) tunneling. This stems from observations of the careful optimized doping for the TJs. Especially the p$^{++}$ and the n$^{++}$ layers are far from ideal. The n$^{++}$ layer induces 3D growth, which can be seen by a rising oxygen signal in Secondary Ions Mass Spectroscopy (SIMS). Furthermore, Mg segregation observed by SIMS indicates a depletion region of more than 10 nm. Still, we could realize TJ based LEDs with a low penalty voltage of 1.1 V and a speci…
The combination of two-dimensional (2D) materials into vertical heterostructures has emerged as a promising path to designer quantum materials with exotic properties. Here, we extend this concept from inorganic 2D materials to 2D metal-organic frameworks (MOFs) that offer additional flexibility in realizing designer heterostructures. We successfully fabricate a monolayer 2D Cu-dicyanoanthracene MOF on a 2D van der Waals NbSe$_2$ superconducting substrate. The structural and electronic properties of two different phases of the 2D MOF are characterized by low-temperature scanning tunneling micro…
We present a detailed study of a monolayer film of 3,4,9,10-perylene-tetracarboxylic acid dianhydride (PTCDA) on Ag(111) (the PTCDA/Ag(111) system). The study is done within density functional theory with the use of the periodic slab model. The slab is chosen to contain a PTCDA monolayer film on a silver thin film of different thicknesses (6, 9, and 12 layers) with the (111) orientation. We show that one of two surface states of the pure Ag(111) films transforms into an unoccupied interface state due to the adsorbate-substrate interaction. The relation of the resulting state to the unoccupied …
