Reliable ferroelectricity down to cryogenic temperature in wakeup free Hf_(0.5)Zr_(0.5)O_(2)thin films by thermal atomic layer deposition

The performance and reliability of ferroelectric thin films at temperatures around a few Kelvin are critical for their application in cryo-electronics.In this work,TiN/Hf_(0.5)Zr_(0.5)O_(2)/TiN capacitors that are free from the wake-up effect are investigated systematically from room temperature(300 K)to cryogenic temperature(30 K).We observe a consistent decrease in permittivity(εr)and a progressive increase in coercive electric field(Ec)as temperatures decrease.Our investigation reveals exceptional stability in the double remnant polarization(2P_(r))of our ferroelectric thin films across a wide temperature range.Specifically,at 30 K,a 2P_(r)of 36μC/cm^(2)under an applied electric field of 3.0 MV/cm is achieved.Moreover,we observed a reduced fatigue effect at 30 K in comparison to 300 K.The stable ferroelectric properties and endurance characteristics demonstrate the feasibility of utilizing HfO_(2)based ferroelectric thin films for cryo-electronics applications.

Robust and Tunable Ferroelectricity in Ba/Co Codoped (K_(0.5)Na_(0.5))NbO_(3) Ceramics

The 0.98(K_(0.5)Na_(0.5))NbO_(3)-0.02Ba(Nb_(0.5)Co_(0.5))O_(3-δ) ceramics with doped Ba^(2+) and Co^(2+) ions are fabricated,and the impacts of the thermal process are studied.Compared with the rapidly cooled (RC) sample,the slowly cooled (SC) sample possesses superior dielectric and ferroelectric properties,and an 11 K higher ferroelectricparaelectric phase transition temperature,which can be attributed to the structural characteristics such as the grain size and the degree of anisotropy.Heat treatment can reversibly modulate the content of the oxygen vacancies,and in turn the ferroelectric hysteresis loops of the samples.Finally,robust and tunable ferroelectric property is achieved in SC samples with good structural integrity.

Ferroelectricity Induced by Oxygen Vacancies in Rhombohedral ZrO_(2) Thin Films

Rhombohedral phase Hf_(x)Zr_(1.x)O_(2)(HZO,x from 0 to 1)films are promising for achieving robust ferroelectric polarization without the need for an initial wake-up pre-cycling,as is normally the case for the more commonly studied orthorhombic phase.However,a large spontaneous polarization observed in rhombohedral films is not fully understood,and there are also large discrepancies between experimental and theoretical predictions.In this work,in rhombohedral ZrO_(2)thin films,we show that oxygen vacancies are not only a key factor for stabilizing the phase,but they are also a source of ferroelectric polarization in the films.This is shown experimentally through the investigation of the structural properties,chemical composition and the ferroelectric properties of the films before and after an annealing at moderate temperature(400℃)in an oxygen environment to reduce the V_(o)concentration compared.The experimental work is supported by density functional theory(DFT)calculations which show that the rhombohedral phase is the most stable one in highly oxygen defective ZrO_(2)films.The DFT calculations also show that V_(o)contribute to the ferroelectric polarization.Our findings reveal the importance of V_(o)for stabilizing rhombohedral ZrO_(2)thin films with superior ferroelectric properties.

Ferroelectricity of hafnium oxide-based materials:Current status and future prospects from physical mechanisms to device applications

The finding of the robust ferroelectricity in HfO_(2)-based thin films is fantastic from the view point of both the fundamentals and the applications.In this review article,the current research status of the future prospects for the ferroelectric HfO_(2)-based thin films and devices are presented from fundamentals to applications.The related issues are discussed,which include:1)The ferroelectric characteristics observed in HfO_(2)-based films and devices associated with the factors of dopant,strain,interface,thickness,defect,fabrication condition,and more;2)physical understanding on the observed ferroelectric behaviors by the density functional theory(DFT)-based theory calculations;3)the characterizations of microscopic and macroscopic features by transmission electron microscopes-based and electrical properties-based techniques;4)modeling and simulations,5)the performance optimizations,and 6)the applications of some ferroelectric-based devices such as ferroelectric random access memory,ferroelectric-based field effect transistors,and the ferroelectric tunnel junction for the novel information processing systems.

Ferroelectricity induced by the absorption of water molecules on double helix SnIP

We study the ferroelectricity in a one-dimensional(1D)system composed of a double helix SnIP with absorbing water molecules.Our ab initio calculations reveal two factors that are critical to the electrical polarization.The first one is the orientation of polarized water molecules staying in the R2 region of SnIP.The second one is the displacement of I atom which roots from subtle interaction with absorbed water molecules.A reasonable scenario of polarization flipping is proposed in this study.In the scenario,the water molecule is rolling-up with keeping the magnitude of its electrical dipole and changing its direction,meanwhile,the displacement of I atoms is also reversed.Highly tunable polarization can be achieved by applying strain,with 26.5%of polarization enhancement by applying tensile strain,with only 4%degradation is observed with 4%compressive strain.Finally,the direct band gap is also found to be correlated with strain.

Ferroelectricity of pristine Hf_(0.5)Zr_(0.5)O_(2) films fabricated by atomic layer deposition

Hafnium-based ferroelectric films,remaining their ferroelectricity down to nanoscale thickness,present a promising application for low-power logic devices and nonvolatile memories.It has been appealing for researchers to reduce the required temperature to obtain the ferroelectric phase in hafnium-based ferroelectric films for applications such as flexible and wearable electronics.This work demonstrates that a remanent polarization(P_(r))value of>5μC/cm^(2)can be obtained in asdeposited Hf_(0.5)Zr_(0.5)O_(2)(HZO)films that are fabricated by thermal atomic layer deposition(TALD)under low temperature of 250℃.The ferroelectric orthorhombic phase(o-phase)in the as-deposited HZO films is detected by scanning transmission electron microscopy(STEM).This low fabrication temperature further extends the compatibility of ferroelectric HZO films to flexible electronics and avoids the cost imposed by following high-temperature annealing treatments.

Ferroelectricity and Large Rashba Splitting in Two-Dimensional Tellurium

Two-dimensional(2D)ferroelectric(FE)systems are promising candidates for non-volatile nanodevices.Previous studies mainly focused on 2D compounds.Though counter-intuitive,here we propose several new phases of tellurium with(anti)ferroelectricity.Two-dimensional films can be viewed as a collection of one-dimensional chains,and lone-pair instability is responsible for the(anti)ferroelectricity.The total polarization is determined to be 0.34×10^(-10)C/m for the FE ground state.Due to the local polarization field in the FE film,we show a large Rashba splitting(α_(R)~2 eV·?)with nonzero spin Hall conductivity for experimental detection.Furthermore,a dipole-like distribution of Berry curvature is verified,which may facilitate a nonlinear Hall effect.Because Rashba-splitting/Berry-curvature distributions are fully coupled with a polarization field,they can be reversed through FE phase transition.Our results not only broaden the elemental FE materials,but also shed light on their intriguing transport phenomena.

Coupled Ferroelectricity and Correlated States in a Twisted Quadrilayer MoS_(2) Moiré Superlattice

Moiré superlattices have emerged as a highly controllable quantum platform for exploration of various fascinating phenomena,such as Mott insulator states,ferroelectric order,unconventional superconductivity and orbital ferromagnetism.Although remarkable progress has been achieved,current research in moiré physics has mainly focused on the single species properties,while the coupling between distinct moiré quantum phenomena remains elusive.Here we demonstrate,for the first time,the strong coupling between ferroelectricity and correlated states in a twisted quadrilayer MoS2moiré superlattice,where the twist angles are controlled in sequence to be ~57°,~0°,and ~-57°.Correlated insulator states are unambiguously established at moiré band filling factors v = 1,2,3 of twisted quadrilayer MoS_(2).Remarkably,ferroelectric order can occur at correlated insulator states and disappears quickly as the moiré band filling deviates from the integer fillings,providing smoking gun evidences of the coupling between ferroelectricity and correlated states.Our results demonstrate the coupling between different moiré quantum properties and will hold great promise for new moiré physics and applications.

Strain engineering and hydrogen effect for two-dimensional ferroelectricity in monolayer group-Ⅳmonochalcogenides MX(M=Sn,Ge;X=Se,Te,S)

Two-dimensional(2D)ferroelectric compounds are a special class of materials that meet the need for devices miniaturization,which can lead to a wide range of applications.Here,we investigate ferroelectric properties of monolayer group-IV monochalcogenides MX(M=Sn,Ge;X=Se,Te,S)via strain engineering,and their effects with contaminated hydrogen are also discussed.GeSe,GeTe,and GeS do not go through transition up to the compressive strain of-5%,and consequently have good ferroelectric parameters for device applications that can be further improved by applying strain.According to the calculated ferroelectric properties and the band gaps of these materials,we find that their band gap can be adjusted by strain for excellent photovoltaic applications.In addition,we have determined the most stable hydrogen occupancy location in the monolayer SnS and SnTe.It reveals that H prefers to absorb on SnS and SnTe monolayers as molecules rather than atomic H.As a result,hydrogen molecules have little effect on the polarization and electronic structure of monolayer SnTe and SnS.

Topology and ferroelectricity in group-V monolayers

The group-V monolayers(MLs)have been studied intensively after the experimental fabrication of two-dimensional(2D)graphene and black phosphorus.The observation of novel quantum phenomena,such as quantum spin Hall effect and ferroelectricity in group-V elemental layers,has attracted tremendous attention because of the novel physics and promising applications for nanoelectronics in the 2D limit.In this review,we comprehensively review recent research progress in engineering of topology and ferroelectricity,and several effective methods to control the quantum phase transition are discussed.We then introduce the coupling between topological orders and ferroelectric orders.The research directions and outlooks are discussed at the end of the perspective.It is expected that the comprehensive overview of topology and ferroelectricity in 2D group-V materials can provide guidelines for researchers in the area and inspire further explorations of interplay between multiple quantum phenomena in low-dimensional systems.

Ferroelectricity in hexagonal YFeO_3 film at room temperature

In this paper we report the leakage current, ferroelectric and piezoelectric properties of the YFe O3 film with hexagonal structure, which was fabricated on Si（111） substrate by a simple sol-gel method. The leakage current test shows good characteristics as the leakage current density is 5.4 × 10^-6A/cm^2 under 5 V. The dominant leakage mechanism is found to be an Ohmic behavior at low electric field and space-charge-limited conduction at high electric field region. The P–E measurements show ferroelectric hysteresis loops with small remnant polarization and coercive field at room temperature.The distinct and switchable domain structures on the nanometer scale are observed by piezoresponse force microscopy,which testifies to the ferroelectricity of the YFe O3 film further.

The coexistence of ferroelectricity and ferromagnetism in Mn-doped BaTiO_3 thin films

5-at% Mn-doped and undoped BaTiO3 thin films have been grown under different oxygen partial pressures by Pulsed Laser Deposition （PLD） on platinum-coated sapphire substrates. X-ray diffraction （XRD） measurements for all the thin films reveal a similar polycrystalline single-phase perovskite structure. Ferroelectricity is observed in the Mn-doped and undoped BaTiO3 thin films grown under relatively high oxygen partial pressure. Ferromagnetic coupling of the Mn dopant ions, on the other hand, is only seen in Mn-doped BaTiO3 thin films prepared under low oxygen partial pressure in a wide temperature range from 5 K to 300 K, and is attributed to the enhanced exchange coupling between Mn dopants and electrons at oxygen vacancies. Our results show that the leakage current is decreased with the doped Mn, but increases the dielectric loss and decreases the dielectric constant, and the ferroelectricity is impaired. To produce ferromagnetism, oxygen vacancies are necessary, which unfortunately increase the leakage current. This confirms that the mutual interplay between the ferroelectricity and ferromagnetism can be tuned by exchange coupling of the doped-Mn and oxygen vacancies in the BaTiO3 thin films.

Emergent ferroelectricity in disordered tri-color multilayer structure comprised of ferromagnetic manganites

Multiferroic materials,showing the coexistence and coupling of ferroelectric and magnetic orders,are of great technological and fundamental importance.However,the limitation of single phase multiferroics with robust magnetization and polarization hinders the magnetoelectric effect from being applied practically.Magnetic frustration,which can induce ferroelectricity,gives rise to multiferroic behavior.In this paper,we attempt to construct an artificial magnetically frustrated structure comprised of manganites to induce ferroelectricity.A disordered stacking of manganites is expected to result in frustration at interfaces.We report here that a tri-color multilayer structure comprised of non-ferroelectric La;Ca;MnO;（A）/Pr;Ca;MnO;（B）/Pr;Sr;MnO;（C） layers with the disordered arrangement of ABC-ACBCAB-CBA-BAC-BCA is prepared to form magnetoelectric multiferroics.The multilayer film exhibits evidence of ferroelectricity at room temperature,thus presenting a candidate for multiferroics.

Ferroelectricity in the Ferrimagnetic Phase of Fe1-xMnxV2O4

Ferroelectric and magnetic properties of Fe1-xMnxV2O4 （0 ≤ x ≤ 0.5） spinels are investigated on the basis of dielectric, polarization, and susceptibility measurements. Ferroeleetric polarization is discovered in collinear ferrimagnetic and Yafet-Kittel magnetic phases for 0.1 ≤ x ≤ 0.4, which can be tuned by a magnetic field. As orbital-active FJ＋ is substituted with Mn2＋, ferroeleetric polarization decreases for 0 ≤ x ≤ 0.4 and disappears for x=0.5. We propose that the two polar components in ferroelectric polarization originate from the exchange striction mechanism and the spin-current model, respectively.

Highly reliable bipolar resistive switching in sol-gel derived lanthanum-doped PbTiO_3 thin film: Coupling with ferroelectricity?

Nanoscale PbxLa1-,Ti1-x/4O3 （PLT） thin film has been fabricated on Pt／Ti／SiO2／Si substrates by chemical solution deposition （CSD） method. Ferroelectricity of the fresh-made PLT thin film has been clearly detected through piezoelectric force microscopy （PFM） by writing reversible ferroelectric domains. However, PLT thin film also shows off-standard ferroelectric hysteresis loops highly dependent on frequency, indicating large amount of mobile space charges in the film. Subsequent current-voltage （C-V） studies show that sandwich-like Pt／PLT／Pt structure exhibits notable bipolar resistive switching （BRS） characteristics with high stability （〉 103 switching cycles）. It is found that the C-V curves of both high- and low-resistance states have the feature of space-charge-limited current （SCLC） conduction, indicating important roles of defects in the conduction. X-ray photoelectron spectroscopy measurement further verifies that oxygen vacancies based conductive filament mechanism is likely responsible for the observed RS effect. Our demonstration of stable RS effect in the PLT thin film and its possible coupling with ferroelectricity is promising in device development and applications, such as development of ferroelectric-tunable RS memories.

Ferroelectricity in Layered Perovskites as a Model of Ultra-Thin Films

The instability of thin ferroelectric films is discussed based on the close similarity of dielectric properties between bulk Bi-layered perovskites and thin BaTiO3 films. The dielectric properties of pseudo-two-dimensional layered perovskites suggest that the bulk layered ferroelectric is a good model of ultra-thin ferroelectric film with a few perovskite units, free from any misfit lattice strain. It seems plausible that the ferroelectric interaction is still prominent but shows a crossover from ferroelectric to antiferroelectric along the unique c-axis (perpendicular to the film plane);with decreasing thickness, the ferroelectricity appears within the plane, which results in so-called “canted ferroelectricity”. An extra relaxation mode induced by surface effect of thin films correlates with soft mode, which results in a new intermediate phase between the paraelectric and ferroelectric phases. These evidences may indicate no critical thickness even for ferroelectric ultra- thin films.

First-principles study of the relaxor ferroelectricity of Ba(Zr, Ti)O_3

Ba（Zr, Ti）O3is a lead-free relaxor ferroelectric. Using the first-principles method, the ferroelectric dipole moments for pure BaTiO3 and Ba（Zr, Ti）O3supercells are studied. All possible ion configurations of Ba Zr0.5Ti0.5O3 and Ba Zr0.25Ti0.75O3 are constructed in a 2 × 2 × 2 supercell. For the half-substituted case, divergence of ferroelectric properties is found from these structures, which greatly depends on the arrangements of Ti and Zr ions. Thus our results provide a reasonable explanation to the relaxor behavior of Ba（Zr, Ti）O3. In addition, a model based on the thermal statistics gives the averaged polarization for Ba（Zr, Ti）O3, which depends on the temperature of synthesis. Our result is helpful to understand and tune the relaxor ferroelectricity of lead-free Ba（Zr, Ti）O3.

Sr-doping effects on conductivity,charge transport,and ferroelectricity of Ba_(0.7)La_(0.3)TiO_(3) epitaxial thin films

Sr-doped Ba_(0.7)La_(0.3)TiO_(3)(BSLTO)thin films are deposited by pulsed laser deposition,and their microstructure,conductivity,carrier transport mechanism,and ferroelectricity are systematically investigated.The x-ray diffraction measurements demonstrate that Sr-doping reduces the lattice constant of BSLTO thin films,resulting in the enhanced phonon energy in the films as evidenced by the Raman measurements.Resistivity-temperature and Hall effect measurements demonstrate that Sr can gradually reduce electrical resistivity while the electron concentration remains almost unchanged at high temperatures.For the films with semiconducting behavior,the charge transport model transforms from variable range hopping to small polaron hopping as the measurement temperature increases.The metalic conductive behaviors in the films with Sr=0.30,0.40 conform to thermal phonon scattering mode.The difference in charge transport behavior dependent on the A-site cation doping,is clarified.It is revealed that the increasing of phonon energy by Sr doping is responsible for lower activation energy of small polaron hopping,higher carrier mobility,and lower electrical resistivity.Interestingly,the piezoelectric force microscopy(PFM)results demonstrate that all the BSLTO films can exhibit ferroelectricity,especially for the room temperature metallic conduction film with Sr=0.40.These results imply that Sr-doping could be a potential way to explore ferroelectric metal materials for other perovskite oxides.

Temperature dependences of ferroelectricity and resistive switching behavior of epitaxial BiFeO_3 thin films

We investigate the resistive switching and ferroelectric polarization properties of high-quality epitaxial BiFeO3 thin films in various temperature ranges. The room temperature current-voltage（I-V） curve exhibits a well-established polarization-modulated memristor behavior. At low temperatures（〈 253 K）, the I-V curve shows an open circuit voltage（OCV）, which possibly originates from the dielectric relaxation effects, accompanied with a current hump due to the polarization reversal displacement current. While at relative higher temperatures（〉 253 K）, the I-V behaviors are governed by both space-charge-limited conduction（SCLC） and Ohmic behavior. The polarization reversal is able to trigger the conduction switching from Ohmic to SCLC behavior, leading to the observed ferroelectric resistive switching. At a temperature of〉 298 K, there occurs a new resistive switching hysteresis at high bias voltages, which may be related to defect-mediated effects.

Computational studies on magnetism and ferroelectricity

Magnetics,ferroelectrics,and multiferroics have attracted great attentions because they are not only extremely im-portant for investigating fundamental physics,but also have important applications in information technology.Here,recent computational studies on magnetism and ferroelectricity are reviewed.We first give a brief introduction to magnets,fer-roelectrics,and multiferroics.Then,theoretical models and corresponding computational methods for investigating these materials are presented.In particular,a new method for computing the linear magnetoelectric coupling tensor without applying an external field in the first principle calculations is proposed for the first time.The functionalities of our home-made Property Analysis and Simulation Package for materials(PASP)and its applications in the field of magnetism and ferroelectricity are discussed.Finally,we summarize this review and give a perspective on possible directions of future computational studies on magnetism and ferroelectricity.