Epitaxial orthorhombic Hf0.5Zr0.5O2 (HZO) films on La0.67Sr0.33MnO3 (LSMO) electrodes show robust ferroelectricity, with high polarization, endurance and retention. However, no similar results have been achieved using other perovskite electrodes so far. Here, LSMO and other perovskite electrodes are compared. A small amount of orthorhombic phase and low polarization is found in HZO films grown on La-doped BaSnO3 and Nb-doped SrTiO3, while null amounts of orthorhombic phase and polarization are detected in films on LaNiO3 and SrRuO3. The critical effect of the electrode on the stabilized phases is not consequence of differences in the electrode lattice parameter. The interface is critical, and engineering the HZO bottom interface on just a few monolayers of LSMO permits the stabilization of the orthorhombic phase. Furthermore, while the specific divalent ion (Sr or Ca) in the manganite is not relevant, reducing the La content causes a severe reduction of the amount of orthorhombic phase and the ferroelectric polarization in the HZO film.
Density functional calculations are performed to study the effect of epitaxial strain on PbZrO3. We find a remarkably small energy difference between the epitaxially strained polar R3c and nonpolar Pbam structures over the full range of experimentally accessible epitaxial strains -3% < η< 4%. While ferroelectricity is favored for all compressive strains, for tensile strains the small energy difference between the nonpolar ground state and the alternative polar phase yields a robust antiferroelectric ground state. The coexistence of ferroelectricity and antiferroelectricity observed in thin fil…
We demonstrate room temperature ferroelectricity in the epitaxial thin films of magnetoelectric GaFeO3. Piezo-force measurements show a 180o phase shift of piezoresponse upon switching the electric field indicating nanoscale ferroelectricity in epitaxial thin films of gallium ferrite. Further, temperature dependent impedance analysis with and without the presence of an external magnetic field clearly reveals a pronounced magneto-dielectric effect across the magnetic transition temperature. In addition, our first principles calculations show that Fe ions are not only responsible for ferrimagnet…
Ferroelectric hafnia is being explored for next generation electronics due to its robust ferroelectricity in nanoscale samples and its compatibility with silicon. However, its ferroelectricity is not understood. Other ferroelectrics usually lose their ferroelectricity for nanoscopic samples and thin films, and the hafnia ground state is non-polar baddeleyite. Here we study hafnia with density functional theory (DFT) under epitaxial strain, and find that strain not only stabilizes the ferroelectric phases, but also leads to unstable modes and a downhill path in energy from the high temperature …
The structure and polarization of the as-yet hypothetical Ruddlesden-Popper compound Pb$_2$TiO$_4$ are investigated within density-functional theory. Zone enter phonons of the high-symmetry K$_2$NiF$_4$-type reference structure, space group $I4/mmm$, were calculated. At the theoretical ground-state lattice constants, there is one unstable infrared-active phonon. This phonon freezes in to give the $I2mm$ ferroelectric state. As a function of epitaxial strain, two additional ferroelectric phases are found, with space groups $I4mm$ and $F2mm$ at compressive and tensile strains, respectively.
Highly ordered Bi2FeMnO6 epitaxial thin films have been successfully grown on SrTiO3 substrate. Both synchrotron X-ray reciprocal space mapping and high resolution transmission electron microscopy confirmed the alternative alignment of Fe and Mn along [111] direction of Bi2FeMnO6 films. Magnetic and ferroelectric properties of Bi2FeMnO6 films are characterized and analyzed. The room-temperature ferroelectricity is well kept in Bi2FeMnO6 film as expected. However, it is very interesting that Bi2FeMnO6 film exhibits a typical spin-glass behavior and very weak magnetism rather than a ferri/ferrom…
We studied the ferroelectric and ferromagnetic properties of compressive strained and unstrained BiMnO3 thin films grown by rf-magnetron sputtering. BiMnO3 samples exhibit a 2D cube-on-cube growth mode and a pseudo-cubic struc-ture up to a thickness of 15 nm and of 25 nm when deposited on (001) SrTiO3 and (110) DyScO3, respectively. Above these thicknesses we observe a switching to a 3D island growth and a simultaneous structural change to a monoclinic structure characterized by a (00l) orientation of the monoclinic unit cell. While ferromagnetism is observed below Tc = 100 K for all samples, …
We report on the dielectric properties of epitaxial [001] and [100]-textured thin films of antiferromagnetic orthorhombic YMnO3 and their variation under compressive epitaxial strain. It is found that weakly strained YMnO3 films are ferroelectric with a polarization along c-axis switchable by 90 degrees by an external magnetic field. When reducing film thickness and increasing epitaxial strain, the ferroelectric order is progressively suppressed. Analysis of structural, dielectric and magnetic data indicates that suppression of ferroelectricity when reducing thickness is accompanied by an enla…
We report studies of ferroelectricity in ultra-thin perovskite films with realistic electrodes. The results reveal stable ferroelectric states in thin films less than 10 Åthick with polarization normal to the surface. Under short-circuit boundary conditions, the screening effect of realistic electrodes and the influence of real metal/oxide interfaces on thin film polarization are investigated. Our studies indicate that metallic screening from the electrodes is affected by the difference in work functions at oxide surfaces. We demonstrate this effect in ferroelectric PbTiO$_3$ and BaTiO$_3$ fil…
Zirconia and hafnia based thin films have attracted tremendous attention in the last decade due to their unexpected ferroelectric behavior at the nanoscale, which facilitates the downscaling of ferroelectric devices. The present work reports a novel ferroelectric rhombohedral phase of ZrO2 that can be achieved in thin films grown on (111)- Nb:SrTiO3 substrates by ion-beam sputtering. Structural and ferroelectric characterizations reveal that the (111)-oriented ZrO2 films are under epitaxial compressive strain and display a switchable ferroelectric polarization of about 20.2 μC/cm2 with a coerc…
First principles calculations are used to investigate the effects of epitaxial strain on the structure of the perovskite oxide CaTiO$_3$, with particular focus on the stabilization of a ferroelectric phase related to a polar instability hidden in the orthorhombic equilibrium bulk $Pbnm$ structure but found in previous first-principles studies of the ideal cubic perovskite high-symmetry reference structure. At 1.5% strain, we find an epitaxial orientation transition between the $ab$-$ePbnm$ phase, favored for compressive strains, and the $c$-$ePbnm$ phase. For larger tensile strains, a polar in…
Room temperature ferroelectricity is observed in lattice-matched ~18% ScAlN/GaN heterostructures grown by molecular beam epitaxy on single-crystal GaN substrates. The epitaxial films have smooth surface morphologies and high crystallinity. Pulsed current-voltage measurements confirm stable and repeatable polarization switching in such ferroelectric/semiconductor structures at several measurement conditions, and in multiple samples. The measured coercive field values are Ec~0.7 MV/cm at room temperature, with remnant polarization Pr~10 μC/cm2 for ~100 nm thick ScAlN layers. These values are sub…
Multiferroic materials open up the possibility to design novel functionality in electronic devices, with low energy consumption. However, there are very few materials that show multiferroicity at room temperature, which is essential to be practically useful. AlxFe2-xO3 (x-AFO) thin films, belonging to the k-Al2O3 family are interesting because they show room temperature ferrimagnetism and have a polar crystal structure. However, it is difficult to realise its ferroelectric properties at room temperature, due to low resistivity of the films. In this work, we have deposited x-AFO (0.5 <= x <= 1)…
The discovery of ferroelectricity in both pure and doped HfO$_2$-based thin films have revitalized the interest in using ferroelectrics for nanoscale device applications. To take advantage of this silicon-compatible ferroelectric, fundamental questions such as the origin of ferroelectricity and better approach to controlled realization of ferroelectricity at the nanoscale need to be addressed. The emergence of robust polarization in HfO$_2$-based thin films is considered as the cumulative effect of various extrinsic factors such as finite-size effects and surface/interface effects of small gra…
The unconventional Si-compatible ferroelectricity in hafnia-based systems, which becomes robust only at nanoscopic sizes, has attracted a lot of interest. While a metastable polar orthorhombic (o-) phase (Pca21) is widely regarded as the responsible phase for ferroelectricity, a higher energy polar rhombohedral (r-) phase is recently reported on epitaxial HfZrO4 (HZO) films grown on (001) SrTiO3 (R3m or R3), (0001) GaN (R3), and Si (111). Armed with results on these systems, here we report a systematic study leading towards identifying comprehensive global trends for stabilizing r-phase polymo…
Ferroelectric oxides have attracted much attention due to their wide range of applications, especially in electronic devices such as nonvolatile memories and tunnel junctions. As a result, the monolithic integration of these materials into silicon technology and its nanostructuration to develop alternative cost-effective processes are among the central points in current technology. In this work, we used a chemical route to obtain nanowire thin films of a novel Sr1+δMn8O16 (SMO) hollandite-type manganese oxide on silicon. Scanning transmission electron microscopy combined with crystallographic …
We performed first principles calculations for epitaxially strained orthorhombic CaTiO$_3$. The computational results reveal the existence of a metastable ferroelectric phase at compressive strain with unexpected in-plane polarization. Symmetry analysis indicates that two distortion modes at the X point combine to induce the polarization, leading to characterization as a hybrid improper ferroelectric. Our work demonstrates a mechanism for improper ferroelectricity in simple perovskites without the need for symmetry lowering by layering or cation ordering.
Epitaxial CaMnO3 films grown with 2.3% tensile strain on (001)-oriented LaAlO3 substrates are found to be incipiently ferroelectric below 25 K. Optical second harmonic generation (SHG) was used for the detection of the incipient polarization. The SHG analysis reveals that CaMnO3 crystallites with in-plane orientation of the orthorhombic b axis contribute to an electric polarization oriented along the orthorhombic a (resp.\ c) axis in agreement with the predictions from density functional calculations.
Recent experimental results demonstrate that in thin films ferroelectricity persists down to film thickness of a few unit cells. This finding opens an avenue for novel electronic devices based on ultathin ferroelectrics, but also raises questions about factors controlling ferroelectricity and the nature of the ferroelectric state at the nanoscale. Here we report a first-principles study of KNbO3 ferroelectric thin films placed between two metal electrodes, either SrRuO3 or Pt. We show that the bonding at the ferroelectric-metal interface imposes severe constraints on the displacement of atoms,…
Epitaxial strain plays an important role in determining physical properties of perovskite ferroelectric oxide thin films. However, it is very challenging to directly measure properties such as polarization in ultrathin strained films using traditional sandwich capacitor devices, because of high leakage current. We employed a planar electrode device with different crystallographical orientations between electrodes along different electric field orientation to directly measure the in-plane polarization-electric field (P-E) hysteresis loops in fully strained thin films. At high misfit strains suc…
After decades of searching for robust nanoscale ferroelectricity that could enable integration into the next generation memory and logic devices, hafnia-based thin films have appeared as the ultimate candidate because their ferroelectric (FE) polarization becomes more robust as the size is reduced. This exposes a new kind of ferroelectricity, whose mechanism still needs to be understood. Towards this end, thin films with increased crystal quality are needed. We report the epitaxial growth of Hf0.5Zr0.5O2 (HZO) thin films on (001)-oriented La0.7Sr0.3MnO3/SrTiO3 (STO) substrates. The films, whic…
We investigated the ferroelectric properties of strontium titanate (STO) thin films deposited on SrTiO3 (001) substrate with SrRuO3 electrodes. The STO layer was grown coherently on the SrTiO3 substrate without in-plane lattice relaxation, but its out-of-plane lattice constant increased with a decrease in the oxygen pressure during deposition. Using piezoresponse force microscopy and P-V measurements, we showed that our tetragonal STO films possess room-temperature ferroelectricity. We discuss the possible origins of the observed ferroelectricity.
We study ferroelectricity in thin films of pseudo-proper ferroelectrics such as the so-called spiral multiferroics. We find that this type of ferroelectricity stands better against depolarizing fields than conventional one. Its single-domain state can be easily preserved by metallic electrodes even in ultrathin films. In fact, single-domain ferroelectricty can be generated as a metastable state in the absence of electrodes. We also find a new regime of small thickness where unscreened films develop unusual multi-domain states with properties determined by non-electrostatic boundary conditions.
Hafnia (HfO$_2$)-based thin films have promising applications in nanoscale electronic devices due to their robust ferroelectricity and integration with silicon. However, HfO$_2$ has various stable and metastable polymorphs with quite similar structures and energies. Identifying and stabilizing the ferroelectric functional phases of HfO$_2$ have attracted intensive research interest in recent years. In this work, first-principles calculations on (111)-oriented HfO$_2$ are used to discover that imposing an in-plane shear strain on the tetragonal phase induces a nonpolar to polar phase transition…
Organic spintronic devices have been appealing because of the long spin life time of the charge carriers in the organic materials and their low cost, flexibility and chemical diversity. In previous studies, the control of resistance of organic spin valves is generally achieved by the alignment of the magnetization directions of the two ferromagnetic electrodes, generating magnetoresistance.1 Here we employ a new knob to tune the resistance of organic spin valves by adding a thin ferroelectric interfacial layer between the ferromagnetic electrode and the organic spacer. We show that the resista…
We report on theoretical and experimental investigation of A-site driven ferroelectricity in ferromagnetic La2NiMnO6 thin films grown on SrTiO3 substrates. Structural analysis and density functional theory calculations show that epitaxial strain stretches the rhombohedral La2NiMnO6 crystal lattice along the [111]cubic direction, triggering a displacement of the A-site La ions in the double perovskite lattice. The lattice distortion and the A-site displacements stabilize a ferroelectric polar state in ferromagnetic La2NiMnO6 crystals. The ferroelectric state only appears in the rhombohedral La2…
The evolution of tetragonality with thickness has been probed in epitaxial c-axis oriented PbTiO3 films with thicknesses ranging from 500 down to 24 Angstroms. High resolution x-ray pointed out a systematic decrease of the c-axis lattice parameter with decreasing film thickness below 200 Angstroms. Using a first-principles model Hamiltonian approach, the decrease in tetragonality is related to a reduction of the polarization attributed to the presence of a residual unscreened depolarizing field. It is shown that films below 50 Angstroms display a significantly reduced polarization but still re…
We discuss ferroelectric phase transitions into single- and multidomain states in very thin films using continuous theory. It is shown that in nearly cubic ferroelectrics the domain state may survive down to atomic film thicknesses, unlike the single domain state, which is almost always unstable or metastable. This conclusion is valid almost irrespective of the nature of electrodes (metallic or semiconducting) and whether or not the screening carriers may be present in the ferroelectric itself.
The critical impact of epitaxial stress on the stabilization of the ferroelectric orthorhombic phase of hafnia is proved. Epitaxial bilayers of Hf0.5Zr0.5O2 and La0.67Sr0.33MnO3 electrodes were grown on a set of single crystalline oxide 001-oriented, cubic or pseudocubic setting, substrates with lattice parameter in the 3.71 - 4.21 A range. The lattice strain of the La0.67Sr0.33MnO3 electrode, determined by the lattice mismatch with the substrate, is critical in the stabilization of the orthorhombic phase of Hf0.5Zr0.5O2. On La0.67Sr0.33MnO3 electrodes tensile strained most of the Hf0.5Zr0.5O2…
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…
The discovery of ferroelectricity in AlScN allowed the first clear observation of the effect in the wurtzite crystal structure, resulting in a material with a previously unprecedented combination of very large coercive fields (2-5 MV/cm) and remnant polarizations (70-110 $μ$C/cm$^2$). We obtained initial insight into the switching dynamics of AlScN, which suggests a domain wall motion limited process progressing from the electrode interfaces. Further, imprint was generally observed in AlScN films and can tentatively be traced to the alignment of charged defects with the internal and external p…
Graphene is attractive for spintronics due to its long spin life time and high mobility. So far only thick and polycrystalline slabs have been used as ferromagnetic electrodes. We report the growth of flat, epitaxial ultrathin Co films on graphene. These display perpendicular magnetic anisotropy in the thickness range 0.5-1nm, which is confirmed by theory. PMA, epitaxy and ultrathin thickness bring new perspectives for graphene-based spintronic devices such as the zero-field control of an arbitrary magnetization direction, band matching between electrodes and graphene, and interface effects su…
A major challenge for ferroelectric devices is the depolarization field, which competes with and often destroys long-range polar order in the limit of ultrathin films. Recent theoretical predictions suggest a new class of materials, termed hyperferroelectics, that should be robust against the depolarization field and enable ferroelectricity down to the monolayer limit. Here we demonstrate the epitaxial growth of hexagonal LiZnSb, one of the hyperferroelectric candidate materials, by molecular-beam epitaxy on GaSb (111)B substrates. Due to the high volatility of all three atomic species, we fin…
We report the structural and physical properties of epitaxial Bi2FeCrO6 thin films on epitaxial SrRuO3 grown on (100)-oriented SrTiO3 substrates by pulsed laser ablation. The 300 nm thick films exhibit both ferroelectricity and magnetism at room temperature with a maximum dielectric polarization of 2.8 microC/cm2 at Emax = 82 kV/cm and a saturated magnetization of 20 emu/cc (corresponding to ~ 0.26 Bohr magneton per rhombohedral unit cell), with coercive fields below 100 Oe. Our results confirm the predictions made using ab-initio calculations about the existence of multiferroic properties in …
We have evaluated the optical and electrical properties of a far-infrared (IR) transparent electrode for extrinsic germanium (Ge) photoconductors at 4 K, which was fabricated by molecular beam epitaxy (MBE). As a far-IR transparent electrode, an aluminum (Al)-doped Ge layer is formed at well-optimized doping concentration and layer thickness in terms of the three requirements: high far-IR transmittance, low resistivity, and excellent ohmic contact. The Al-doped Ge layer has the far-IR transmittance of >95 % within the wavelength range of 40--200 microns, while low resistivity (~5 ohm-cm) and o…
Finite size effects in ferroelectric thin films have been probed in a series of epitaxial perovskite c-axis oriented PbTiO3 films grown on thin La0.67Sr0.33MnO3 epitaxial electrodes. The film thickness ranges from 480 down to 28 A (7 unit cells). The evolution of the film tetragonality c/a, studied using high resolution x-ray diffraction measurements, shows first a decrease of c/a with decreasing film thickness followed by a recovery of c/a at small thicknesses. This recovery is accompanied by a change from a monodomain to a polydomain configuration of the polarization, as directly demonstrate…
We investigate the effect of polar Sr-O vacancy pairs on the electric polarization of SrMnO$_3$ (SMO) thin films using density functional theory (DFT) calculations. This is motivated by indications that ferroelectricity in complex oxides can be engineered by epitaxial strain but also \textit{via} the defect chemistry. Our results suggest that intrinsic doping by cation and anion divacancies can induce a local polarization in unstrained non-polar SMO thin films and that a ferroelectric state can be stabilized below the critical strain of the stoichiometric material. This polarity is promoted by…
By performing first-principles calculations on four capacitor structures based on BaTiO3 and PbTiO3, we determine the intrinsic interfacial effects that are responsible for the destabilization of the polar state in thin-film ferroelectric devices. We show that, contrary to the established interpretation, the interfacial capacitance depends crucially on the local chemical environment of the interface through the force constants of the metal-oxide bonds, and is not necessarily related to the bulk screening properties of the electrode material. In particular, in the case of interfaces between AO-…
We have investigated the crystal structure and the ferroelectric properties of BaTiO3 thin films with YBa2Cu3O7-d as the bottom and Au as the top electrode. Epitaxial heterostructures of YBa2Cu3O7-d and BaTiO3 were prepared by dc and rf sputtering, respectively. The crystal structure of the films was characterised by x-ray diffraction. The ferroelectric behaviour of the BaTiO3 films was confirmed by hysteresis loop measurements using a Sawyer Tower circuit. We obtain a coercive field of 30 kV/cm and a remanent polarisation of 1.25 \muC/cm. At sub-switching fields the capacitance of the films o…
The electronic transport and spincaloric properties of epitaxial magnetic tunnel junctions with half-metallic Co$_2$MnSi Heusler electrodes, MgO tunneling barriers, and different interface terminations are investigated by using first-principles calculations. A new approach to spincaloric properties is presented that circumvents the linear response approximation inherent in the Seebeck coefficient and compared to the method of Sivan and Imry. This approach supports two different temperatures in the two electrodes and provides the exact current and/or voltage response of the system. Moreover, it…
We present molecular dynamics simulations of a realistic model of an ultrathin film of BaTiO$_3$ sandwiched between short-circuited electrodes to determine and understand effects of film thickness, epitaxial strain and the nature of electrodes on its ferroelectric phase transitions as a function of temperature. We determine a full epitaxial strain-temperature phase diagram in the presence of perfect electrodes. Even with the vanishing depolarization field, we find that ferroelectric phase transitions to states with in-plane and out-of-plane components of polarization exhibit dependence on thic…
Interest in epitaxial ferroelectric nanoislands was growing rapidly in recent years driven by their potential for devices, especially ultradense memories. Recent advances in the "bottom- up" (self-assembly) nanometer scale techniques have opened up the opportunities of fabricating high-quality epitaxial ferroelectric nanoislands with extremely small thickness and lateral size on the order of 1 nm and 20 nm, respectively. On the other hand, recent emergence of powerful probes, such as piezoresponse force microscopy (PFM), has enabled imaging of a local domain structure with sub-10 nm resolution…
We fabricate fully epitaxial Fe/ZnO/MgO/Fe magnetic tunnel junctions (MTJs) with a bilayer tunnel barrier, in which ZnO has a metastable rock-salt crystal structure. We observe a high magnetoresistance ratio up to 96% at room temperature (RT) and find that these MTJs have asymmetric current-voltage characteristics, and their rectifying performances are largely dependent on the magnetization alignments of the Fe electrodes. Diode responsibilities at a zero-bias voltage ($β_{0}$), which is an important performance index for harvesting applications, are observed up to 1.3 A/W at RT in the antipar…
Sizes of Ferroelectricity Appearance and Disappearence in Nanosized Hafnia-Zirconia:Landau-type Theory
Institute of Physics of the National Academy of Sciences of Ukraine（乌克兰国家科学院物理研究所）；Frantsevich Institute for Problems in Materials Science of the National Academy of Sciences of Ukraine（乌克兰国家科学院弗兰采维奇材料科学问题研究所）；Department of Materials Science and Engineering, University of Tennessee（田纳西大学材料科学与工程系）；Faculty of Radiophysics, Electronics and Computer Systems, Taras Shevchenko National University of Kyiv（基辅塔拉斯舍甫琴科国立大学无线电物理、电子和计算机系统学院）；V. Lashkariov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine（乌克兰国家科学院V.拉什卡廖夫半导体物理研究所）
Fe$_3$O$_4$ is a ferrimagnetic spinel ferrite that exhibits electric conductivity at room temperature (RT). Although the material has been predicted to be a half metal according to ab-initio calculations, magnetic tunnel junctions (MTJs) with Fe$_3$O$_4$ electrodes have demonstrated a small tunnel magnetoresistance effect. Not even the sign of the TMR ratio has been experimentally established. Here, we report on the magnetic properties of epitaxial Fe$_3$O$_4$ films with various crystal orientations. The films exhibited apparent crystal orientation dependence on hysteresis curves. In particula…
We report on multiple fundamental qualitative improvements in the growth of improper ferroelectric hexagonal YMnO$_3$ (YMO) thin films and heterostructures by pulsed laser deposition (PLD). By a combination of pre-growth substrate annealing and low-energy-fluence PLD, we obtain a two-dimensional growth mode of the YMO films on yttria-stabilized zirconia (YSZ) with ultralow roughness and devoid of misoriented nanocrystalline inclusions. By inserting a sacrificial manganite layer capped with conducting indium-tin oxide between the substrate and the final film, the latter is grown in a fully latt…
