Properties of (K,Na)NbO3-based lead-free piezoelectric films prepared by pulsed laser deposition

To investigate the properties of (K,Na)NbO₃-based lead-free piezoelectric films at the morphotropic phase boundary composition, we fabricated epitaxial [(K_0.5Na_0.5)_0.97Li_0.03] (Nb_0.8Ta_0.2)O₃ films on (001), (110) and (111)-oriented single crystal SrTiO₃ substrates by pulsed laser deposition. The structure and electrical properties of the films were studied. Dielectric constants of 540, 390 and 300 and remnant polarizations of 4.00, 1.05, and 0.35 μC/cm² were observed for the (001), (110) and (111) oriented films, respectively.     

Epitaxial-Strain Effects on Electronic Structure and Magnetic Properties of Hexagonal YMnO3 Thin Films Studied by Femtosecond Spectroscopy

In this paper, (001)-oriented hexagonal YMnO₃ (h-YMO) thin films with various nominal strain states were deposited on MgO(100), MgO(111), and YSZ(111) substrates by pulsed laser deposition. The in-plane orientation alignment and substrate-induced epitaxial strain between the h-YMO films and substrates are examined by X-ray diffraction (XRD) θ–2θ, Φ, and ω scans. The effects of epitaxial strain on the on-site Mn d–d transition energy E _dd (T), and the Néel temperature (T _N) in these thin films are investigated by wavelength-tunable ultrafast pump-probe techniques. We find that the changes of E _dd (T) and T _N depend on the type and magnitude of the epitaxial strain. The possible mechanisms for the observed strain effect on the electronic structure and associated magnetism are discussed.     

Comparison of Bi3Fe5O12 film giant Faraday rotators grown on (111) and (001) Gd3Ga5O12 single crystals

Bismuth iron garnet (Bi₃Fe₅O₁₂, BIG) epitaxial thin films were grown on single crystal (Gd₃Ga₅O₁₂, GGG) (111) and (001) substrates by rf-magnetron sputtering technique. Processing parameters have been optimized to obtain high deposition rate (2.74 μm/h) and the surface rms roughness less than 10 nm. X-ray diffraction reveals films epitaxial quality: exclusive (111) or (001) orientation with narrow rocking curves and strong in-plane texture. Films possess low optical loss and magneto-optical Faraday rotation (FR) as high as 5 deg/μm at 677 nm wavelength. Comparative analysis of films grown on (111) and (001) substrates clearly shows significant superiority of BIG/GGG(001) film. For this film, the coercive field ∼100 Oe appears to be 2.5 times lower while the optical transmission to be 10% higher than that for BIG/GGG(111) film. Enhanced magneto-optical performance of BIG/GGG(001) films relies upon better accommodation of the film-to-substrate mismatch strain through the tetragonal BIG lattice distortions compared to the rhombohedral one in BIG/GGG(111) films.     

Phase transition characteristics and dielectric properties of rare-earth (La,Pr, Nd,Gd) doped Ba(Zr0.09Ti0.91)O3 ceramics

A-site deficient rare-earth doped barium zirconate titanate (BZT) ceramics (Ba_1−yLn_2y/3)Zr_0.09Ti_0.91O₃ (Ln = La, Pr, Nd, Gd) are obtained by a modified solid-state reaction method. Perovskite-like single-phase compounds were confirmed from X-ray diffraction data. Morphological analysis on sintered samples shows that the addition of rare-earth ions inhibits the growth of the grain and remarkably changes the grain morphology. The effect of rare-earth addition to BZT on phase transition and dielectric properties is analyzed. A dramatic fall in the transition temperature occurs when BZT ceramic is doped with rare-earths. Moreover, diffusivity degree of the phase transition increases and a relaxor-type behaviour is induced due to both the increment of the lanthanide content and the increase of the ionic radius of the dopant element. High values of dielectric tunability are obtained for lanthanum doped BZT. A direct relation between transition temperature and tunability is discussed. Conclusively, low permittivity and high tunability materials can be obtained by the adequate substitution of rare-earths into BZT ceramics.     

Enhanced ferroelectric properties of Mg doped (Ba,Sr)TiO3 thick films grown on (001) SrTiO3 substrates

Highly (001)-oriented 1 mol% Mg doped (Ba_0.67,Sr_0.33)TiO₃ (BST) films with a thickness of 1.25 μm were grown on (110) SrRuO₃/(001) SrTiO₃ substrates by pulsed laser deposition. X-ray diffraction measurements reveal that the BST thick films have very high crystalline quality, and have a distorted lattice with a large tetragonality a/c = 1.012. The BST thick films have a remanent polarization (P_r) value as large as 10.1 μC/cm² and a coercive electric field (E_c) value of 65.0 kV/cm. The films possess dielectric constant and loss values of ε_r = 385.36 and tgδ = 0.038 at 1 kHz and room temperature. The leakage currents of the films are on the order of 10^− 5 A/cm² at ± 150 kV/cm. The mechanism for enhancing electric properties of the Mg doped BST films was also discussed.     

Effects of ferroelectric-poling-induced strain on the electronic transport and magnetic properties of (001)- and (111)-oriented La0.5Ba0.5MnO3 thin films

We epitaxially grew La_0.5Ba_0.5MnO₃ (LBMO) films on (001)- and (111)-oriented ferroelectric single-crystal substrates and reduced the in-plane tensile strain of LBMO films by poling the ferroelectric substrates along the 〈001〉$〈001〉$ or 〈111〉$〈111〉$ direction. Upon poling, a large decrease in the resistance and a considerable increase in the magnetization, Curie temperature, and magnetoresistance were observed for the LBMO film, which are driven by interface strain coupling. Such strain effects can be significantly enhanced by the application of a magnetic field. An overall analysis of the findings reveals that the mutual interaction between the strain and the magnetic field is mediated by the electronic phase separation which is sensitive to both strain and magnetic field. Our findings highlight that the electronic phase separation is crucial in understanding the electric-field-manipulated strain effects in manganite film/ferroelectric crystal heterostructures.     

Growth and characterization of epitaxial anatase TiO2(001) on SrTiO3-buffered Si(001) using atomic layer deposition

Epitaxial anatase titanium dioxide (TiO₂) films have been grown by atomic layer deposition (ALD) on Si(001) substrates using a strontium titanate (STO) buffer layer grown by molecular beam epitaxy (MBE) to serve as a surface template. The growth of TiO₂ was achieved using titanium isopropoxide and water as the co-reactants at a substrate temperature of 225-250 °C. To preserve the quality of the MBE-grown STO, the samples were transferred in-situ from the MBE chamber to the ALD chamber. After ALD growth, the samples were annealed in-situ at 600 °C in vacuum (10^− 7 Pa) for 1-2 h. Reflection high-energy electron diffraction was performed during the MBE growth of STO on Si(001), as well as after deposition of TiO₂ by ALD. The ALD films were shown to be highly ordered with the substrate. At least four unit cells of STO must be present to create a stable template on the Si(001) substrate for epitaxial anatase TiO₂ growth. X-ray diffraction revealed that the TiO₂ films were anatase with only the (004) reflection present at 2θ = 38.2°, indicating that the c-axis is slightly reduced from that of anatase powder (2θ = 37.9°). Anatase TiO₂ films up to 100 nm thick have been grown that remain highly ordered in the (001) direction on STO-buffered Si(001) substrates.     

Crystallography of TiSi2 (C54) epitaxy on (111)Si and (001)Si surfaces

Following the success in understanding the textures in TiSi₂ (C49) epitaxy on (001)_Si surface using the edge-to-edge matching model that was originally developed for predicting the crystallographic features of diffusion-controlled phase transformations in solids, the present work applies this model to understand the in-plane texture in TiSi₂ (C54) thin films on Si single crystal surfaces and to explain why its epitaxial growth is more favoured on (111)_Si than on (001)_Si. Based on the actual atomic spacing along the matching directions across the interface between the thin films and the substrate, the model predicts most of the experimentally observed orientation relationships (ORs) and that the preferred order among the different systems is C49/(001)_Si system > C54/(111)_Si system > C49/(111)_Si system ≅ C54/(001)_Si system. The model has strong potential to be used to develop new thin film materials.     

Effects of oxygen to argon ratio on Ba(Zr0.2Ti0.8)O3 thin films prepared by RF magnetron sputtering

Ba(Zr_0.2Ti_0.8)O₃ (BZT) thin films were deposited on Pt/Ti/LaAlO₃ (001) substrates by radio-frequency magnetron sputtering at different O₂/Ar mixing ratios. As the O₂/Ar ratio increased (1/4–4), the preferred orientation evolved from (00l) to (111). The grain size and the surface roughness increased, and the ferroelectric properties improved with increasing O₂/Ar ratio. The BZT thin films deposited under oxygen-rich atmosphere (O₂/Ar = 4) had larger dielectric constant (443) and tunability (44%), while the BZT films deposited under argon-rich atmosphere (O₂/Ar = 1/4) had a lower loss tangent (0.016).     

Optimal growth windows of multiferroic BiFeO3 films and characteristics of ferroelectric domain structures

Multiferroic BiFeO₃ films of smooth surface and fully-saturated ferroelectric hysteresis loops have been grown by RF magnetron sputtering. The (001)-oriented epitaxial films showed a large remanent polarisation of 61 µC/cm². A strategy to grow BiFeO₃ films of good ferroelectric property was demonstrated, that was using fast growth rate to achieve accurate stoichiometry for the BiFeO₃ phase and at the same time to avoid the formation of impurity phases associated with the fast growth by accurate control of thermodynamic parameters such as oxygen partial pressure and temperature, as well as proper selection of substrates. Piezoresponse force microscopy revealed fine spontaneous domains for highly resistive epitaxial films, which were switchable under DC biases. For the polycrystalline films of increased density of free carriers, single-domain grains of about 200 nm in diameter were observed due to effective compensation of depolarisation field by free carriers and therefore allowing larger domains.     

In-situ X-ray diffraction study of the initial dealloying of Cu3Au(001) and Cu0.83Pd0.17(001)

Dealloying and selective dissolution are serious corrosion processes, but also employed in technology. We studied the surface structure of Cu_0.83Pd_0.17(001) and Cu₃Au(001) during electrochemical selective Cu dissolution below the critical potential in-situ in 0.1 M H₂SO₄ (pH = 1) electrolyte. In both cases we observe the formation of an epitaxial layer of nano-scale islands of the noble component of the original alloy (Au or Pd). These islands form a metallic passivation layer suppressing massive dissolution of Cu. The Au islands developed {111} facets. By re-deposition of Cu ions from the electrolyte solution onto Pd islands, an epitaxial Cu layer is formed.     

Two-dimensional interface structures of epitaxial (Ba,Sr)TiO3 film on miscut (001) MgO

We report on the effect of substrate miscut on the 2-dimensional interfacial structure and dielectric properties of the epitaxial Ba_0.6Sr_0.4TiO₃/MgO. Epitaxial Ba_0.6Sr_0.4TiO₃ films on vicinal (001) MgO grown by pulsed-laser ablation were studied using transmission electron microscopy (TEM). Plan-view TEM showed that the films grown on the substrate with miscut angles of 1.2°, 3.5°, and 5.3° have lattice mismatches of − 5.6%, − 6.0% and − 5.7% at the interface, larger than the values (− 5.4%, − 5.7% and − 5.5%, respectively) obtained using cross-section TEM. The films grown on 1.2° and 5.3° miscut substrates consist of commensurate domains with sizes about 30 to 40 nm at the interface, significantly larger than those of 10 to 20 nm obtained for the films grown on the 3.5° miscut substrate. The films with larger commensurate domains at the interface exhibit about 30% higher dielectric constant and dielectric tunability than those with smaller commensurate domains. Initial measurements show that their interfacial differences have a tremendous effect on the dielectric properties of the films.     

Synthesis and properties of Ba(Zn1/3Ta2/3)O3 for microwave and millimeter wave applications

High dielectric materials have gained an important position in microwave electronics by reducing the size and cost of components for a wide range of applications from mobile telephony to spatial communications. Ba(Zn_1/3Ta_2/3)O₃ (BZT) is an A(B′B″)O₃ type perovskite material, showing ultra high values of the quality factor Q. Ceramic-based BZT dielectric materials were prepared by solid state reaction. The samples were sintered at temperatures in the range 1400 ÷ 1600 °C for 4 h. Compositional, structural and morphological characterization were performed by using XRD, SEM and EDX analysis. The dielectric properties were measured in the microwave range (6 ÷ 7 GHz). An additional annealing at 1400 °C for 10 h has improved some dielectric parameters. For samples sintered at temperatures higher than 1500 °C, the permittivity values were obtained in the interval 30 ÷ 35 and almost do not change the value after the annealing. The Q × f product substantially increases up to about 135,000 GHz, exhibiting a low temperature coefficient of the resonant frequency (τ_f) in microwaves. The best parameters were obtained for the samples sintered at 1600 °C with additional annealing. The achieved high values of the Q × f product recommend these materials for microwave and millimeter wave applications.     

Growth and structure of heteroepitaxial thin films of homologous compounds RAO3(MO)m by reactive solid-phase epitaxy: Applicability to a variety of materials and epitaxial template layers

A reactive solid-phase epitaxy (R-SPE) method combines deposition of a thick amorphous or polycrystalline layer with a desired chemical composition and post-deposition solid-phase epitaxial growth. The solid-phase epitaxial growth is invoked by thermal annealing with an assistance of a sacrificial layer working as an epitaxial template. Thereby it enables us to grow high-quality epitaxial films of complex oxides whose epitaxial films are not grown by conventional high-temperature growth techniques. It was reported that 2-nm-thick ZnO layers worked as template for growing InGaO₃(ZnO)_m (m = integer) epitaxial films. The present study extended the R-SPE technique to growth of various complex oxides with chemical compositions of RAO₃(MO)_m and to use of various epitaxial template layers. We found that mono oxide epitaxial layers such as In₂O₃ and Ga₂O₃ work as template layers as well. Alternatively, a ZnO epitaxial layer is also applicable to ZnO-free compounds. The films obtained were grown heteroepitaxially on YSZ(111) and single-crystalline when the fabrication conditions are optimized.     

Effects of oxygen pressure on the microstructural,ferroelectric and magnetic properties of BiFe0.95Mn0.05O3 thin films grown on Si substrates

We have investigated the effects of oxygen pressure on the microstructure, leakage current, ferroelectric and magnetic properties of BiFe_0.95Mn_0.05O₃ (BFMO) thin films epitaxially grown on SrRuO₃, SrTiO₃, and TiN-buffered (001)-oriented Si substrates. X-ray diffraction θ?2θ scans and scanning electron microscope images reveal that the epitaxy and microstructures of the BFMO films were strongly dependent on oxygen pressure during film deposition. Epitaxial BFMO films can be obtained in a low oxygen pressure of 2 Pa while polycrystalline BFMO films were obtained in a relatively high oxygen pressure of 15 Pa. Furthermore, the oxygen pressure strongly influences the ferroelectric properties of the BFMO films grown on Si. The remnant polarization (2P _r) of approximately 107 μC/cm² and coercive field (2E _c) of approximately 580 kV/cm were observed for the epitaxial BFMO films grown in a low oxygen pressure of 2 Pa. The saturation magnetization of the BFMO films decreases with increasing oxygen pressure while the magnetic coercive field remains unchanged.     

Compositionally graded Pb(Zr,Ti)O3 thin films with different crystallographic orientations

Compositionally graded ferroelectric PbZr_xTi_1−xO₃ (PZT) films were deposited using a sputtering method and crystallized in situ at 500 °C. The films showed purely (100) or (111) crystallographic orientation when grown on Si/SiO₂/TiO₂/Pt substrates, while they exhibited c-axis epitaxial microstructure when prepared on MgO/Pt substrates. Their crystallographic orientation was controlled owing to a thin TiO_x layer sputtered on substrates prior to PZT deposition. Analysis performed by Auger depth profile clearly confirmed the variation of composition in the films. Coercive fields from 80 kV/cm to 200 kV/cm and remnant polarization as large as 45 μC/cm² were obtained. However, no typical offset was observed on hysteresis loops, unlike previous works related to graded PZT films.     

Microstructure and electric properties of (104)/(014)-oriented Bi3.15Nd0.85Ti3O12 films on Pt (111)/Ti/SiO2/Si by sol-gel method

Bi_3.15Nd_0.85Ti₃O₁₂ (BNdT) thin films with predominant (104)/(014) orientation were fabricated directly on (111)Pt/Ti/SiO₂/Si substrates through a sol-gel process. The volume fraction of (104)/(014)-oriented grains in the film was estimated to be about 65% according to X-ray pole figure. The BNdT film is dense and uniform and consists of columnar grains penetrating the whole film thickness. The (104)/(014)-oriented BNdT film capacitors showed excellent ferroelectric properties with 2P_r = 46.4 μC/cm² and E_c ≈ 140 kV/cm. The films also exhibit excellent piezoelectric property, with high piezoelectric coefficient d₃₃ ≈ 17 pm/V.     

Raman spectroscopic and X-ray diffraction investigations of epitaxial BiCrO3 thin films

Epitaxial BiCrO₃ thin films were grown onto NdGaO₃ (110)- and (LaAlO₃)_0.3-(Sr₂AlTaO₆)_0.7 (100)-oriented substrates by pulsed laser deposition. High resolution X-ray diffraction and pole figure measurements were performed in order to obtain information about the crystal structure of the films, about their quality and about the mutual crystallographic orientation between the films and the substrates. The monoclinic (111) plane of BiCrO₃ was found out to be parallel to the substrate surface. The epitaxial relation between films and substrates was verified by using polarisation dependent Raman spectroscopic experiments and theoretical calculations based on symmetry.     

Onset of hard magnetic L10 FePt phase with (001) texture

The perpendicular anisotropic magnetic properties of in-situ deposited FePt/Pt/Cr trilayer films were elucidated as functions of the deposition temperature and the sputtering rate of the FePt magnetic layer. Ordered L1₀ FePt thin films with perpendicular anisotropy and a (001) texture can be developed at a temperature as low as 300 °C with the sputtering of a FePt layer at a low rate. The larger Pt(001)[100] lattice induced an expansion of the FePt a- and b-axis, leading to the contraction of the FePt c-axis, enabling the epitaxial growth of the L1₀ FePt(001) texture to occur. A low rate of sputtering of the FePt thin film promotes the formation of the magnetically hard FePt(001) texture on the surface of the Pt(001) buffer layer at low temperature, while the high sputtering rate of FePt layer suppresses the phase transformation.     

Epitaxial growth of Cu(100) and Pt(100) thin films on perovskite substrates

Pulsed laser deposition has been used to grow epitaxially oriented thin films of Cu and Pt on (100)-oriented SrTiO₃ and LaAlO₃ substrates. X-ray diffraction results illustrated that purely epitaxial Cu(100) films could be obtained at temperatures as low as 100 °C on SrTiO₃ and 300 °C on LaAlO₃. In contrast, epitaxial (100)-oriented Pt films were attained on LaAlO₃(100) only when deposited at 600 °C. Atomic force microscopy images showed that films deposited at higher temperatures consisted of 3D islands and that flat, layered films were obtained at the lowest deposition temperatures. Importantly, Cu films deposited at 100 °C on SrTiO₃(100) were both purely (100)-oriented and morphologically flat. Pt and Cu films displaying both epitaxial growth and smooth surfaces could be obtained on LaAlO₃(100) only by using a three-step deposition process. High-resolution transmission electron microscopy demonstrated an atomically sharp Cu/SrTiO₃ interface. The crystalline and morphological features of Cu and Pt films are interpreted in terms of the thermodynamic and kinetic properties of these metals.