Morphotropic phase boundary tailoring of PZST–PMN system by compositional variation for shape memory effect

Samples with representative formula (1 − y)[Pb(Zr_0.7Sn_0.3)_0.938Ti_0.062O₃] (PZST)–y(PbMg_1/3Nb_2/3O₃) (PMN), with y = 0.01, 0.02, 0.05 and 0.07, were synthesized using conventional solid state ceramic route. Detailed studies on structural, dielectric, ferroelectric and shape memory related properties of the series are presented. Best results of remnant strain (shape memory) ∼0.2% at 45 °C is observed for y = 0.01 composition. Morphotropic phase boundary (MPB) for the present series, where maximum strain is obtained, is found to shift towards higher temperatures with increasing PMN content; making it possible to design temperature specific devices. Temperature dependent polarization versus electric field (P–E) measurements show that the phase transition in this series follows the thermodynamic model proposed by Yang and Payne. On the basis of these studies, a phase diagram for PZST–PMN system is worked out and reported here.     

Effect of working pressure on the properties of BaTiO3-CoFe2O4 composite films deposited on STO (100) by PLD

The BaTiO₃-CoFe₂O₄ (BTO-CFO) composite films were grown on SrTiO₃ (STO) (100) substrates at 750 °C under various working pressures by pulsed laser deposition. The composite film grew into a supersaturated single phase at the working pressure of 10 mTorr, BTO and CFO (00 l) oriented hetero-epitaxial films on STO (100) at 100 mTorr, and a polycrystalline composite film at 500 mTorr. The slow growth rate at high working pressure led to the phase separation in the composite film. The CFO was compressively strained along out-of-plane due to the lattice mismatch with the BTO matrix phase. The BTO-CFO composite film grown at 100 mTorr showed reversible switching of ferroelectric polarization and magnetic hysteresis with strong magnetic anisotropy.     

Analysis of dichroic dye-doped polymer-dispersed liquid crystal materials for display devices

Dichroic polymer-dispersed liquid crystals (DPDLCs) based on nematic liquid crystal materials with azo dye were investigated in detail for the application of display devices. Polarizing optical microscopy, differential scanning calorimeter and electro-optic experiments all have shown that the DPDLC containing low concentration of dyes modifies the basic properties of these materials like optical transmission, threshold voltage, contrast ratio and absorbance factor. A minimum amount of dye needs to be added to the liquid crystal with the polymer matrix for its effective phase separation and to minimize the transmittance in the OFF state and therefore gives rise to an overall improvement in contrast ratio of the devices. Molecular orientation and dynamics in droplet sizes are readily controlled in these DPDLC materials. These findings imply that the value of the threshold electric field E_th is approximately 8 V/μm for pure polymer-dispersed liquid crystal (without dye) where the threshold electric field E_th values are approximately 4.0 V/μm, 2.0 V/μm, 1.7 V/μm 1.0 V/μm, for 0.0625%, 0.125%, 0.25% and 0.5% with azo dye in DPDLCs, respectively. From the results we can also infer that the maximum contrast is approximately 2.55 times the minimum contrast observed in the experiment for DPDLCs. The results show that the DPDLC with proscribed dye concentration will be possibly suitable and promising functional electronic materials for green technology flexible liquid crystal display.     

Textured strontium titanate layers on platinum by atomic layer deposition

Formation of textured strontium titanate (STO) layers with large lateral grain size (0.2-1 μm) and low X-ray reflectivity roughness (~ 1.36 nm) on Pt electrodes by industry proven atomic layer deposition (ALD) method is demonstrated. Sr(t-Bu₃Cp)₂, Ti(OMe)₄ and O₃ precursors at 250 °C were used to deposit Sr rich STO on Pt/Ti/SiO₂/Si ∅200 mm substrates. After crystallization post deposition annealing at 600 °C in air, most of the STO grains showed a preferential orientation of the {001} plane parallel to the substrate surface, although other orientations were also present. Cross sectional and plan view transmission electron microscopy and electron diffraction analysis revealed more than an order of magnitude larger lateral grain sizes for the STO compared to the underlying multicrystalline {111} oriented platinum electrode. The combination of platinum bottom electrodes with ALD STO(O₃) shows a promising path towards the formation of single oriented STO film.     

Study of SrTiO3 thin films grown by sputtering technique for tunnel barriers in quasiparticle injection contacts

High-quality, c-axis oriented YBa₂Cu₃O_7 − x/SrTiO₃/Au (YBCO/STO/Au) planar structures were fabricated in situ by direct current/radiofrequency inverted-cylinder magnetron sputtering on (001) STO oriented substrates. The sandwich-type structures were patterned to transistor dimensions by standard ultraviolet-photolithography and Ar etching. The current transport mechanism in the very thin STO barriers (2-30 nm) was examined by measuring the tunneling G as function of temperature (T), and bias voltage (V). It was found that resonant tunneling and hopping via a small number of localized states (LS) are responsible for electronic conduction in the insulating material. Elastic tunneling was observed for the case of a nominal 2 nm thick STO-barrier with an energy gap Δ ≈ 20 meV in the (001) direction of YBCO. On the other hand, inelastic hopping transport via n-LS dominated for STO barrier thickness d > 2 nm. G of the lowest-order hopping channel (hopping via two LS) exhibits the characteristic T and V dependences: G₂^hop(T) ∝ T^4/3, G₂^hop(V) ∝ V^4/3, respectively. Increasing the thickness of the STO barriers, hopping channels of higher order contribute more and more to the current transport as proven by measuring the T and V dependences. A crossover to variable range hopping behavior has been observed for junctions with thicker barriers (d ≥ 20 nm) in the high-V or high-T regime. By fitting the experimental data to theoretical models, physical parameters of the LS could be determined. For instance, the value of the localization length or radius of the localized state was determined to be ~ 4.6 × 10^− 8 cm which corresponds to the lattice constant of the STO unit cell. A value of ~ 6 × 10¹⁹ (eV)^− 1 cm^− 3 was calculated for the density of LS and the average barrier height was estimated as ~ 0.4 eV.     

Epitaxial multi-component rare earth oxide for high-K application

We studied the growth and electrical properties of single crystalline mixed (Nd_1 − xGd_x)₂O₃ (NGO) thin films and compared the results with those of the binary Gd₂O₃ and Nd₂O₃ thin films, respectively. Epitaxial ternary NGO thin films were grown on Si(100) substrates using modified solid state molecular beam epitaxy. The films were characterized physically using various techniques. The capacitance equivalent oxide thickness of a 4.5 nm NGO thin film extracted from capacitance-voltage (C-V) characteristics was 0.9 nm, which is lower than all values reported earlier for other crystalline oxides. The leakage current density and the density of interface traps were 0.3 mA/cm² at |Vg − V_FB| =  1 V and 1.4 × 10¹²/cm², respectively. These excellent electrical properties of NGO thin films demonstrate that such ternary oxides could be one of the promising candidates for gate dielectrics in the upcoming generations of complementary metal oxide semiconductor (CMOS) devices.     

Fabrication of KTa0.65Nb0.35O3 film by pulsed laser deposition on glass substrate with various buffer layers

KTa_0.65Nb_0.35O₃ (KTN) thin films were deposited on amorphous glass substrates using a range of single buffer layers such as indium tin oxide (ITO), zinc oxide (ZnO), 3 at% Al-doped ZnO (AZO), and 3 at% Ga-doped ZnO (GZO), as well as a variety of multi-buffer layers such as SrTiO₃ (STO)/ITO, STO/ZnO, STO/AZO, and STO/GZO using a pulsed laser deposition system. All films showed a polycrystalline perovskite phase with the exception of all single buffer layers and STO/ITO multi-buffer layers. The STO buffer layer is important for crystallizing KTN films due to the similar lattice constant and same crystal structure. The optical transmittance of all films exhibited a transmittance ?90% in the wavelength range.     

Polaronic Trions at the MoS2/SrTiO3 Interface

The reduced electrical screening in 2D materials provides an ideal platform for realization of exotic quasiparticles, that are robust and whose functionalities can be exploited for future electronic, optoelectronic, and valleytronic applications. Recent examples include an interlayer exciton, where an electron from one layer binds with a hole from another, and a Holstein polaron, formed by an electron dressed by a sea of phonons. Here, a new quasiparticle is reported, “polaronic trion” in a heterostructure of MoS₂/SrTiO₃ (STO). This emerges as the Fröhlich bound state of the trion in the atomically thin monolayer of MoS₂ and the very unique low energy soft phonon mode (≤7 meV, which is temperature and field tunable) in the quantum paraelectric substrate STO, arising below its structural antiferrodistortive (AFD) phase transition temperature. This dressing of the trion with soft phonons manifests in an anomalous temperature dependence of photoluminescence emission leading to a huge enhancement of the trion binding energy (≈70 meV). The soft phonons in STO are sensitive to electric field, which enables field control of the interfacial trion–phonon coupling and resultant polaronic trion binding energy. Polaronic trions could provide a platform to realize quasiparticle‐based tunable optoelectronic applications driven by many body effects.     

Giant strain in Nb-doped Bi0.5(Na0.82K0.18)0.5TiO3 lead-free electromechanical ceramics

The effect of Nb substitution on the crystal structure, ferroelectric, and electric field induced strain properties of Bi_0.5(Na₈₂K_0.18)_0.5TiO₃ (BNKT) ceramics has been investigated. The coexistence of rhombohedral and tetragonal phases was found in undoped BNKT ceramics, however, Nb doping induced a phase transition to a pseudocubic phase with high electrostriction coefficients. When 3 mol% Nb was substituted on Ti ions, the electric field induced strain was markedly enhanced up to S_max/E_max = 641 pm/V, which is higher than those previously reported on non-textured lead-free electromechanical ceramics.     

Magnetic and semi-conducting nano-composite films of spinel ferrite and cubic zinc oxide

Magnetic and semi-conducting nano-composite films have been prepared under bias polarization, by radio-frequency sputtering of a pure zinc ferrite target. These composite thin films are made of cubic Zn_1 − yFe_yO monoxide islands inside a spinel ferrite matrix. The relative proportion of each phase depends on the substrate polarization (i.e. bias power). When no bias is applied the films solely display the diffraction pattern of a spinel phase even if some islands inside the film can be observed by electron microscopy. When the bias power is increased, the spinel phase disappears progressively as enhanced formation of islands takes place in such a manner that the cubic Zn_1 − yFe_yO monoxide is solely revealed by X-ray diffraction for a bias power higher than 5 W. From bibliographical data and calculated phase diagrams, it can be inferred that these phases would require very low oxygen partial pressure, high temperature and mechanical pressure, to be obtained simultaneously by a conventional ceramic process. This underlines the strong potential of radio-frequency sputtering of oxide targets to prepare original oxides or composite materials.     

Epitaxial growth and electrical measurement of single crystalline Pb(Zr0.52Ti0.48)O3 thin film on Si(001) for micro-electromechanical systems

We report in this work the epitaxial growth and the electrical characteristics of single crystalline Pb(Zr_0.52Ti_0.48)O₃ (PZT) thin film on SrTiO₃(STO)-buffered Si(001) substrate. The STO buffer layer deposited by molecular beam epitaxy allows a coherent oxide/Si interface leading enhanced PZT crystalline quality. 70 nm-thick PZT (52:48) layer was then grown on STO/Si(001) by sol-gel method. X-ray diffraction demonstrates the single crystalline PZT film on Si substrate in the following epitaxial relationship: [110] PZT (001)//[110] STO (001)//[100] Si (001). The macroscopic electrical measurements show a hysteresis loop with memory window of 2.5 V at ± 7 V sweeping range and current density less than 1 μA/cm² at 750 kV/cm. The artificial domains created by piezoresponse force microscopy with high contrast and non-volatile properties provide further evidence for the excellent piezoelectric properties of the single crystalline PZT thin film.     

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.     

Electric and magnetic properties of Pb(Zr0.52Ti0.48)O3-CoFe2O4 particle composite thin film on the SrTiO3 substrate

We deposited a thin epitaxial Pb(Zr_0.52Ti_0.48)O₃ (PZT) layer on the (0 0 1) SrTiO₃ (STO) substrate doped with Nb (0.5 wt.%), then grew composite thin film of CoFe₂O₄ (CFO) and PZT phases on it. X-ray diffraction and high resolution transmission electron microscopy showed that the PZT and CFO phases in the film had perfect epitaxial structures. CFO nanoparticles were embedded in PZT matrix randomly, which was useful to enhance the insulativity of the composite film. The composite thin film exhibited good ferromagnetic and ferroelectric properties. The dielectric constants of the composite thin film kept unchangeable in a wide bias electric field, but increased in a magnetic field, namely, magnetodielectric effect. The possible reasons for the magnetodielectric effect were discussed.     

Effects of periodicity and oxygen partial pressure on the crystallinity and dielectric property of artificial SrTiO3/BaTiO3 superlattices integrated on Si substrates by pulsed laser deposition method

Epitaxial SrTiO₃(STO)/BaTiO₃(BTO) artificial superlattices have been grown on TiN buffered Si (001) substrates by pulsed laser deposition method and the effects of stacking periodicity and processing oxygen partial pressure on their crystallinity and dielectric properties were studied. The crystal orientation, epitaxy nature, and microstructure of STO/BTO superlattices were investigated using X-ray diffraction and transmission electron microscopy. The TiN buffer layer and superlattice thin films were grown with cube-on-cube epitaxial orientation relationship of [110](001)_films∣∣[110](001)_TiN∣∣[110](001)_Si. The c-axis lattice parameter of the STO/BTO superlattice decreased from 0.412 nm to 0.406 nm with increasing oxygen partial pressure and the dielectric constants, measured at the frequency of 100 kHz at room temperature, of the superlattices with 2 nm/2 nm periodicity increased from 312 at 1 × 10^− 5 Torr to 596 at 1 × 10^− 3 Torr. The dielectric constants of superlattices grown at oxygen partial pressure of 1 × 10^− 3 Torr increased from 264 to 678 with decreasing periodicity of the superlattices from 10 nm/10 nm to 1 nm/1 nm.     

Magneto-electric coupling in multiferroic La0.8Bi0.2Fe0.7Mn0.3O3 ceramic

We present here the structural, electrical, magnetic and magneto-electric properties of La_0.8Bi_0.2Fe_0.7Mn_0.3O₃ multiferroic sample synthesized by conventional solid state reaction route. X-ray diffraction (XRD) data show single phase character of the sample. Temperature (150-475 K) variation of dielectric constant exhibits step like escalation which consists of two transitions corresponding to the respective peaks in temperature vs. loss tangent curve. Slight shift in peak positions to higher temperatures with the increase of frequency indicates the presence of relaxor behavior. Magnetic field dependent magnetization (M-H) curve at 300 K demonstrates weak ferromagnetic conduct. Coupling between the electric and magnetic orders has been explored by means of magneto-capacitance measurement. Presence of magneto-electric (ME) coupling ascertains the candidature of this material for device application.     

Dielectric properties,thermal expansion and heat capacity of (1 − x)Na0.5Bi0.5TiO3–xBaTiO3 single crystals (x = 0, 0.02, 0.025, 0.0325 and 0.05)

High-quality and large-size lead-free (1 − x)Na_0.5Bi_0.5TiO₃–xBaTiO₃ single crystals (x = 0, 0.025, 0.0325 and 0.05) were grown using Czochralski method. The obtained samples were of pure perovskite structure with rhombohedral symmetry at room temperature. Thermal expansion, heat capacity, ferroelectric and dielectric properties were measured in a wide temperature range. The broad anomalies observed in thermal expansion and heat capacity were corresponded to structural, ferroelectric and dielectric anomalies, related to temperature features of polar regions and formation of a long-range order ferroelectric phase. The Burns temperature was found to increase with increasing BaTiO₃ content. At low-frequency (100 Hz–100 kHz) the samples showed diffuse phase transitions. The obtained results were discussed in terms of local electric and strain fields caused by a difference in ionic radii between (Na,Bi) and Ba ions.     

Fabrication of LSS bottom electrode by PLD

Polycrystalline LaNiO₃/SrTiO₃/Si(100) (LSS) conducting substrates were fabricated by pulsed laser deposition (PLD) technique. LSS substrate is a potential candidate for the multiferroic materials for use as bottom electrode. X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM) equipped with EDX system, atomic force microscopy (AFM) and electrical resistivity were employed to characterize the films. Buffer layer SrTiO₃ (STO) deposited at 700 °C resulted in dense, smooth and with crack free features. XRD studies confirmed bi-crystalline [(100), (110)] growth of STO on Si(100) substrate. Deposition of bottom electrode LaNiO₃ (LNO) epitaxially followed the buffer layer. EDX analyses determined the chemical composition of the films. The role of oxygen partial pressure during deposition affecting the crystallinity and resistivity of the films was explored in detail. Atomic force microscopy revealed the atomic scale features of the films desirable for functional devices. Resistivity of the conducting film (LNO) was ∼10⁻⁴ Ω cm at room temperature. Thus it is demonstrated that LNO/STO/Si(100) is a suitable conducting substrate for growth of the multiferroic functional materials.     

Epitaxial growth and exchange coupling of spinel ferrimagnet Ni0.3Zn0.7Fe2O4 on multiferroic BiFeO3

Thin films of the zinc nickel ferrite, Zn_0.7Ni_0.3Fe₂O₄ (ZNFO), were deposited by the RF magnetron sputtering on a number of substrates, including (001) oriented single crystals of LaAlO₃ (LAO) and SrTiO₃ (STO), polycrystalline Pt/Si, and epitaxial films of BiFeO₃ (BFO) and LaNiO₃ (LNO). Except for the films on Pt/Si, the ZNFO films grown on other substrates were epitaxial and their magnetic properties were affected by the heteroepitaxy induced strains. Typically, the coercivity (H_c) was increased with the strain, i.e. H_c varied from 31 Oe for the 150 nm thick polycrystalline films grown on Pt/Si, to 55 Oe and 155 Oe for the 20 nm thick epitaxial films grown on BFO and LAO, respectively. The saturation magnetization of the epitaxial films was reduced accordingly to about 470 emu/cm³ from 986 emu/cm³ in the polycrystalline films. The all-oxide architecture allowed field-annealing to perform at the temperature above the Neel temperature of BFO (~ 370 °C), after which clear exchange bias was observed.     

Shape controlled synthesis of iron-cobalt alloy magnetic nanoparticles using soft template method

Fe_xCo_1 − x alloy nanoparticles of spherical (x = 0.25, 0.68, 0.85), hollow spherical (x = 0.60) and sheet like (x = 0.60) shapes were prepared at room temperature by reduction of iron chloride tetrahydrate and cobalt chloride hexahydrate with sodium borohydride, using N-Cetyl-N,N,N-trimethyl ammonium bromide (CTAB)/water/hexanol system as soft template. The size and shapes of nanostructures were found to depend on the concentrations of CTAB and hexanol in water. Composition and shape dependence of magnetic properties of spherical, hollow spherical and sheet like Fe_xCo_1 − x alloy nanostructures were discussed. The highest saturation magnetization of 235 emu/g with a coercivity of 160 Oe was obtained for spherical Fe_0.68Co_0.32 nanoparticles.     

Initial stages of WO3 growth on silicon substrates

Ultrathin films (5 nm, 10 nm and 20 nm effective thickness) of WO₃ have been deposited in high vacuum (10^− 6 Torr) onto single crystal Si(100) substrates and studied with X-ray diffraction, atomic force microscopy, scanning tunneling microscopy and spectroscopy. The experiments have been carried out on “as-deposited” thin films or after 1 h post-deposition annealing at various temperatures (ranging from 300 °C to 500 °C). A size induced increase of the amorphous to crystalline (monoclinic) phase transition has been observed for the 5 nm and 10 nm films, with a critical crystallite size of 25 ± 5 nm and a critical temperature of 345 ± 5 °C. All the experimental evidences show that, upon annealing, there is a diffusion limited aggregation growth of WO₃ that forms large flat two-dimensional islands composed by aggregates of individual crystallites approximately uniform in size and shape. These islands are isolated in the 5 nm thin films, are connected in the 10 nm case and form a uniform patchwork in the 20 nm thin films. Scanning tunneling spectroscopy shows the opening of a large surface band gap (2.7 eV) in the 500 °C annealed films and the significant presence of in gap states for thin films prepared with a lower (below 400 °C) annealing temperature. These findings are discussed in view of the optimization of the best morphological, structural and electronic parameters to fabricate WO₃ gas sensing devices at the sub-micrometer length scale.