Enhanced ferroelectric properties of (Pb0.90La0.10)Ti0.975O3 multilayered thin films prepared by RF magnetron sputtering

The (Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PLT/PT), PbTiO₃/(Pb_0.90La_0.10)Ti_0.975O₃/PbTiO₃ (PT/PLT/PT) multilayered thin films with a PbO_x buffer layer were in situ deposited by RF magnetron sputtering at the substrate temperature of 600 °C. With this method, highly (1 0 0)-oriented PLT/PT and PT/PLT/PT multilayered thin films were obtained. The PbO_x buffer layer leads to the (1 0 0) orientation of the films. The dielectric, ferroelectric and pyroelectric properties of the PLT multilayered thin films were investigated. It is found that highly (1 0 0)-oriented PT/PLT/PT multilayered thin films possess higher remnant polarization 2P_r (44.1 μC/cm²) and better pyroelectric coefficient at room temperature p (p = 2.425 × 10⁻⁸ C/cm² K) than these of PLT and PLT/PT thin films. These results indicate that the design of the PT/PLT/PT multilayered thin films with a PbO_x buffer layer should be an effective way to enhance the dielectric, ferroelectric and pyroelectric properties. The mechanism of the enhanced ferroelectric properties was also discussed.     

Substrate orientation-induced distinct ferromagnetic moment in Co:ZnO films

Dilute (3.8 at.%) cobalt-doped ZnO thin films are deposited on LiTaO₃ (LT) substrates with three different orientations [LT(1 1 0), LT(0 1 2) and LT(0 1 8)] by direct current reactive magnetron co-sputtering. The experimental results indicate that Co atoms with 2+ chemical valence are successfully incorporated into the ZnO host matrix on various oriented substrates, and the substrate orientations have a profound influence on the crystal growth and magnetization of Co:ZnO films. A large magnetic moment of 2.42μ_B/Co at room temperature is obtained in the film deposited on LT(0 1 2), while the corresponding values of the other films deposited on LT(1 1 0) and LT(0 1 8) are 1.21μ_B/Co and 0.65μ_B/Co, respectively. Furthermore, the crystal growth mode of Co:ZnO films on various oriented LT, the relationship between the microstructures and corresponding ferromagnetic properties are also discussed.     

Enhanced ferroelectric property of (Pb0.95Ca0.05)(Nb0.02Zr0.80Ti0.20)O3 thin films prepared by RF magnetron sputtering

(Pb_0.95Ca_0.05)(Nb_0.02Zr_0.80Ti_0.20)O₃ [PCNZT] thin films were deposited on the Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrates by RF magnetron sputtering with and without a LaNiO₃ [LNO] buffer layer. Ca and Nb elements in PZT films enhance the ferroelectric property, LaNiO₃ buffer layer improves the crystal quality of the PCNZT thin films. PCNZT thin films possess better ferroelectric property than that of PZT films for Ca and Nb ion substitution, moreover, PCNZT thin films with a LNO buffer layer possess (1 0 0) orientation and good ferroelectric properties with high remnant polarization (P_r = 38.1 μC/cm²), and low coercive field (E_c = 65 kV/cm), which is also better than that of PCNZT thin films without a LNO buffer layer (P_r = 27.9 μC/cm², E_c = 74 kV/cm). The result shows that enhanced ferroelectric property of PZT films can be obtained by ion substitution and buffer layer.     

Exchange bias and negative magnetoresistance in [Co/Bi/Co]/IrMn thin films]

The artificial control of grain-boundary resistance and its contribution to magnetic and magneto-transport properties in [Co(3 nm)/Bi(2.5 nm)/Co(3 nm)]Ir₂₀Mn₈₀(12 nm) thin films that exhibit exchange bias is studied. Transverse magnetoresistance (MR) loops exhibit a negative MR in thin films grown by magnetron sputtering on Si/SiN_x(100 nm) substrates. This negative MR effect is of the giant-MR (GMR) type, although its magnitude is less than 1%. A considerable exchange bias (EB) effect is observed only at lower temperatures, where both, GMR and isothermal magnetization loops exhibit a shift of −600 Oe at 5 K.     

Surface chemical states of barium zirconate titanate thin films prepared by chemical solution deposition

Ba(Zr_0.05Ti_0.95)O₃ (BZT) thin films grown on Pt/Ti/SiO₂/Si(1 0 0) substrates were prepared by chemical solution deposition. The structural and surface morphology of BZT thin films has been studied by X-ray diffraction (XRD) and scanning electron microscope (SEM). The results showed that the random oriented BZT thin film grown on Pt/Ti/SiO₂/Si(1 0 0) substrate with a perovskite phase. The SEM surface image showed that the BZT thin film was crack-free. And the average grain size and thickness of the BZT film are 35 and 400 nm, respectively. Furthermore, the chemical states and chemical composition of the films were determined by X-ray photoelectron spectroscopy (XPS) near the surface. The XPS results show that Ba, Ti, and Zr exist mainly in the forms of BZT perovskite structure.     

Infrared optical properties of Ba(Zr0.20Ti0.80)O3 and Ba(Zr0.30Ti0.70)O3 thin films prepared by sol-gel method

Ba(Zr_xTi_1−x)O₃ (BZT) (x = 0.20 and 0.30) thin films are deposited on Pt(1 1 1)/Ti/SiO₂/Si(1 0 0) substrate by sol-gel method. X-ray diffraction patterns show that the thin films have a good crystallinity. Optical properties of the films in the wavelength range of 2.5-12 μm are studied by infrared spectroscopic ellipsometry (IRSE). The optical constants of the BZT thin films are determined by fitting the IRSE data using a classical dispersion formula. As the wavelength increases, the refractive index decreases, while the extinction coefficients increase. The effective static ionic charges are derived, which are smaller than that in a purely ionic material for the BZT thin films.     

Pulsed-laser crystallization and epitaxial growth of metal-organic films of Ca-doped LaMnO3 on STO and LSAT substrates

Ca-doped LaMnO₃ (LCMO) thin films have been successfully prepared on SrTiO₃ (STO) and [(LaAlO₃)_0.3-(SrAlTaO₆)_0.7] (LSAT) substrates using the excimer laser assisted metal-organic deposition (ELAMOD) process. The crystallization and the epitaxial growth of the amorphous metal-organic LCMO thin films have been achieved using a KrF excimer laser irradiation while the substrates were kept at constant temperature of 500 °C. Epitaxial films were obtained using laser fluence in the interval of 50-120 mJ/cm². The microstructure of the LCMO films was studied using cross-section transmission electron microscopy. High quality of LCMO films having smooth surfaces and sharp interfaces were obtained on both the STO and the LSAT substrates. The effect of the laser fluence on the temperature coefficient of resistance (TCR) was investigated. The largest values of TCR of the LCMO grown on the LSAT and the STO substrates of 8.3% K⁻¹ and 7.46% K⁻¹ were obtained at different laser fluence of 80 mJ/cm² and 70 mJ/cm², respectively.     

Effects of substrates on the structure and dielectric properties of Ba(Sn0.15Ti0.85)O3 thin films

Ba(Sn_0.15Ti_0.85)O₃ (BTS) thin films were grown on Pt(1 1 1)/Ti/SiO₂/Si and LaNiO₃(LNO)/Pt(1 1 1)/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The BTS thin films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si and annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates exhibited strong (1 1 1) and perfect (1 0 0) orientations, respectively. The BTS thin films grown on un-annealed Pt(1 1 1)/Ti/SiO₂/Si substrates showed random orientation with intense (1 1 0) peak, while the films deposited on un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate exhibited random orientation with intense (1 0 0) peak, respectively. The dielectric constant of the BTS films deposited on annealed Pt(1 1 1)/Ti/SiO₂/Si, annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si, un-annealed Pt(1 1 1)/Ti/SiO₂/Si and un-annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates was 512, 565, 386 and 437, respectively, measured at a frequency of 100 kHz. A high tunability of 49.7% was obtained for the films deposited on annealed LNO/Pt(1 1 1)/Ti/SiO₂/Si substrate, measured at the frequency of 100 kHz with an applied electric field of 200 kV/cm. The high tunability has been attributed to the (1 0 0) texture of the films and larger grain sizes.     

Luminescent characteristics of CaTiO3:Pr thin films prepared by pulsed laser deposition method with various substrates

CaTiO₃:Pr³⁺ films were deposited on different substrates such as Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica using pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by XRD and SEM measurements. The films grown on the different substrates have different crystallinity and morphology. The FWHM of (2 0 0) peak are 0.18, 0.25, 0.28, and 0.30 for Al₂O₃ (0 0 0 1), Si (1 0 0), MgO (1 0 0), and fused silica, respectively. The grain sizes of phosphors grown on different substrates were estimated by using Scherrer's formula and the maximum crystallite size observed for the thin film grown on Al₂O₃ (0 0 0 1). The room temperature PL spectra exhibit only the red emission peak at 613 nm radiated from the transition of (¹D₂ → ³H₄) and the maximum PL intensity for the films grown on the Al₂O₃ (0 0 0 1) is 1.1, 1.4, and 3.7 times higher than that of the CaTiO₃:Pr³⁺ films grown on MgO (1 0 0), Si (1 0 0), and fused Sillica substrates, respectively. The crystallinity, surface morphology and luminescence spectra of thin-film phosphors were highly dependent on substrates.     

Synthesis and characterization of (h 0 h)-oriented silicalite-1 films on α-Al2O3 substrates

A simple and well-designed synthesis procedure is proposed to fabricate silicalite-1 films on porous α-Al₂O₃ substrates on purpose of preventing the aluminum leaching. The continuous and 2 μm thick seed layer of silicalite-1 crystals is fabricated by using a spin coater. The first-time seeded growth is performed to synthesize a thin layer of intergrown ZSM-5 crystals on the silicalite-1 seed layer, where the use of low alkalinity and short synthesis time is to reduce the aluminum leaching. The intergrown layer of ZSM-5 crystals serves as a barrier to block the aluminum leaching from porous α-Al₂O₃ substrates in the second-time seeded growth, leading to the formation of ca. 11 μm thick intergrown and oriented silicalite-1 films with an extremely high Si/Al ratio. According to SEM images and XRD measurements, the as-synthesized silicalite-1 film is dense, continuous, and (1 0 1)-oriented. The electron probe microanalysis (EPMA) of the resulting film demonstrates that there is no aluminum leaching in the second-time seeded growth. The leaking tests confirm that non-zeolitic pores in the silicalite-1 film are negligible.     

Structural and magnetic properties of evaporated Fe thin films on Si(1 1 1), Si(1 0 0) and glass substrates

We present experimental results on the structural and magnetic properties of series of Fe thin films evaporated onto Si(1 1 1), Si(1 0 0) and glass substrates. The Fe thickness, t, ranges from 6 to110 nm. X-ray diffraction (XRD) and atomic force microscopy (AFM) have been used to study the structure and surface morphology of these films. The magnetic properties were investigated by means of the Brillouin light scattering (BLS) and magnetic force microscopy (MFM) techniques. The Fe films grow with (1 1 0) texture; as t increases, this (1 1 0) texture becomes weaker for Fe/Si, while for Fe/glass, the texture changes from (1 1 0) to (2 1 1). Grains are larger in Fe/Si than in Fe/glass. The effective magnetization, 4πM_eff, inferred from BLS was found to be lower than the 4πM_S bulk value. Stress induced anisotropy might be in part responsible for this difference. MFM images reveal stripe domain structure for the 110 nm thick Fe/Si(1 0 0) only.     

Effect of substrate temperature on structure and electrical resistivity of laser-ablated IrO2 thin films

IrO₂ thin films were prepared on Si(1 0 0) substrates by laser ablation. The effect of substrate temperature (T_sub) on the structure (crystal orientation and surface morphology) and property (electrical resistivity) of the laser-ablated IrO₂ thin films was investigated. Well crystallized and single-phase IrO₂ thin films were obtained at T_sub = 573-773 K in an oxygen partial pressure of 20 Pa. The preferred orientation of the laser-ablated IrO₂ thin films changed from (2 0 0) to (1 1 0) and (1 0 1) depending on T_sub. With the increasing of T_sub, both the surface roughness and crystallite size increased. The room-temperature electrical resistivity of IrO₂ thin films decreased with increasing T_sub, showing a low value of (42 ± 6) × 10⁻⁸ Ω m at T_sub = 773 K.     

Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

We have grown lead iron niobate thin films with composition Pb(Fe_1/2Nb_1/2)O₃ (PFN) on (0 0 1) SrTiO₃ substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM?0.09°). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.     

High-frequency characteristics of CoFeVAlONb thin films

High-frequency characteristics of CoFeVAlONb thin films were studied. A thin film of Co_43.47Fe_35.30V_1.54Al_5.55O_9.93Nb_4.21 is observed to exhibit excellent magnetic properties; magnetic coercivity of 1.24 Oe, uniaxial in-plane anisotropy field of 66.99 Oe, and saturation magnetization of 19.8 kG. The effective permeability of the film is as high as 1089 and is stable up to 1.8 GHz, and with ferromagnetic resonance over 3 GHz. This film also has very high electrical resistivity of about 628 μΩ cm. These superior properties make it ideal for high-frequency magnetic applications.     

Characteristic properties of Y2SiO5:Ce thin films grown with PLD

Three different gases (nitrogen (N₂), oxygen (O₂) and argon (Ar)) were used as background gases during the growth of pulsed laser deposition (PLD) Y₂SiO₅:Ce thin films. A Krypton fluoride laser (KrF), 248 nm was used for the PLD of the films on silicon (Si) (1 0 0) substrates. The effect of the background gases on the surface morphology, crystal growth and luminescent properties were investigated. All the experimental parameters, the gas pressure (455 mT), the substrate temperature (600 °C), the pulse frequency (8 Hz), the number of pulses (4000) and the laser fluence (1.6±0.2) J/cm² were kept constant. The only parameter that was changed during the deposition was the ambient gas species. The surface morphology and average particle sizes were monitored with scanning electron microscopy (SEM) and atomic force microscopy (AFM). X-ray diffraction (XRD) and Auger electron spectroscopy (AES) were used to determine the crystal structure and composition, respectively. Cathodo- (CL) and photoluminescence (PL) were used to measure the luminescent intensities for the different phosphor thin films. The nature of the particles, ablated on the substrate, is related to the collisions between the ejected particles and the ambient gas particles. The CL and PL intensities also depend on the particle sizes. A 144 h (coulomb dose of 1.4×10⁴ C cm⁻²) electron degradation study on the thin films ablated in the Ar gas environment resulted in a decrease in the main CL intensity peak at 440 nm and to the development of a new very broad luminescent peak spectra ranging from 400 to 850 nm due to the growth of a SiO₂ layer on the surface.     

Magnetic properties of disordered ferrite and ilmenite-hematite thin films

We have synthesized thin films of disordered zinc ferrite (ZnFe₂O₄) and ilmenite-hematite (FeTiO₃-Fe₂O₃) solid solution, the former and the latter of which are interesting from the viewpoints of magnetooptics and spintronics, respectively, by utilizing sputtering and pulsed laser deposition methods, and have explored their magnetic, magnetooptical, and electrical properties. Although ZnFe₂O₄ possesses a normal spinel structure as its stable phase, some of the Fe³⁺ ions occupy the tetrahedral as well as the octahedral sites in ZnFe₂O₄ of which the sputtered thin film is composed. Consequently, the as-deposited thin film manifests large magnetization even at room temperature although the magnetic phase transition temperature of the stable phase of ZnFe₂O₄ is as low as 10 K. Also, the thin film exhibits a cluster spin glass transition at a temperature as high as 325 K. Furthermore, the ZnFe₂O₄ thin films exhibit large Faraday effects at a wavelength of 400 nm or so. The ilmenite-hematite solid solution is one of the ferrimagnetic semiconductors. Most of the compositions possess Curie temperatures higher than room temperature, and the type of carrier can be tuned only by changing the composition. We have succeeded in synthesizing solid-solution thin films of various compositions grown epitaxially on sapphire substrates with a (0 0 0 1) plane, and have shown that the thin films are ferrimagnetic semiconductors.     

Enhanced ferroelectric properties of vanadium doped bismuth titanate (BTV) thin films grown by pulsed laser ablation technique

Bi_3.99Ti_2.97V_0.03O₁₂ (BTV) thin films were grown by pulsed laser deposition at substrate temperatures ranging between 650 and 750 °C. The structural phase, and orientation of the deposited films were investigated in order to understand the effect of the deposition parameters on the properties of the BTV films. As the substrate temperature was increased to 700 °C, the films started showing a tendency of assuming a c-axis preferred orientation, while at lower temperatures polycrystalline films were formed. The Au/BTV/Pt capacitor showed an interesting dependence of the remnant polarization (P_r) as well as dc leakage current values on the growth temperature. The film deposited at 675 °C showed a very large 2P_r of 42 μC cm⁻², which is the largest for BTV thin films among the values reported so far.     

Optical and structural studies on Ba(Mg1/3Ta2/3)O3 thin films obtained by radiofrequency assisted pulsed plasma deposition

Single-phase Ba(Mg_1/3Ta_2/3)O₃ thin films were prepared by radiofrequency plasma beam assisted pulsed laser deposition (RF-PLD) starting from a bulk ceramic target synthesized by solid state reaction. Atomic force microscopy, X-ray diffraction and spectroscopic ellipsometry were used for morphological, structural and optical characterization of the BMT thin films. The X-ray diffraction spectra show that the films exhibit a polycrystalline cubic structure. From spectroscopic ellipsometry analysis, the refractive index varies with the thin films deposition parameters. By using the transmission spectra and assuming a direct band to band transition a band gap value of ≈4.72 eV has been obtained.     

Effect of growth time on the structure, Raman shift and photoluminescence of Al and Sb codoped ZnO nanorod ordered array thin films

Al and Sb codoped ZnO nanorod ordered array thin films have been deposited on glass substrate with a ZnO seed layer by hydrothermal method at different growth time. The effect of growth time on structure, Raman shift, and photoluminescence (PL) was studied. The thin films at growth time of 5 h consist of nanorods growth vertically oriented with ZnO seed layer, and the nanorods with an average diameter of 27.8 nm and a length of 1.02 μm consist of single crystalline wurtzite ZnO crystal and grow along [0 0 1] direction. Raman scattering analysis demonstrates that the thin films at the growth time of 5 h have great Raman shift of 15 cm⁻¹ to lower wavenumber and have low asymmetrical factor Г_a/Г_b of 1.17. Room temperature photoluminescence reveals that there is more donor-related PL in films with growth time of 5 h.     

Influence of crystallization on the spectral features of nano-sized ferroelectric barium strontium titanate (Ba0.7Sr0.3Tio3) thin films

Ferroelectric barium strontium titanate (Ba_0.7Sr_0.3TiO₃)(BST) thin films have been prepared from barium 2-ethylhexanoate [Ba[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂]_, strontium 2-ethylhexanoate [Sr[CH₃(CH₂)₃CH(C₂H₅)CO₂]₂] and titanium(IV) isopropoxide [TiOCH(CH₃)₂]₄ precursors using a modified sol-gel technique. The precursor except [TiOCH(CH₃)₂]₄ were synthesized in the laboratory. Transparent and crack-free films were fabricated on pre-cleaned quartz substrates by spin coating. The structural and optical properties of films annealed at different temperatures have been investigated. The as-fired films were found to be amorphous that crystallized to the tetragonal phase after annealing at 550 °C for 1 h in air. The lattice constants “a” and “c” were found to be 3.974 A and 3.990 A, respectively. The grain sizes of the films annealed at 450, 500 and 550 °C were found to be 30.8, 36.0 and 39.8 nm respectively. The amorphous film showed very high transparency (∼95%), which decreases slightly after crystallization (∼90%). The band gap and refractive index of the amorphous and crystalline films were estimated. The optical dispersion data are also analyzed in the light of the single oscillator model and are discussed.