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.     

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.     

Dielectric properties of ferroelectric/DMS heterointerface using YMnO3 and Ce doped Si

Bottom gate type Al/Si:8.2 at%Ce/YMnO₃/Pt capacitor was fabricated. Although it was polycrystalline, we successfully obtained Si:8.2 at%Ce film on ferroelectric YMnO₃. The dielectric properties of the capacitor were carefully investigated. Although the capacitance shows frequency dispersion, the capacitor exhibits a ferroelectric type C-V hysteresis loop. From the PUND and P-V measurements, ferroelectric polarization was distinguished from the another polarization, Based on these dielectric measurements, effect of polarization induced by the ferroelectric YMnO₃ on the carrier modulation in the diluted magnetic semiconductor, Ce doped Si film was discussed.     

Crystalline and photoluminescence characteristics of YVO4:Sm thin films grown by pulsed laser deposition under oxygen pressure

YVO₄:Sm³⁺ films were deposited on Al₂O₃ (0 0 0 1) substrates at various oxygen pressures changing from 13.3 to 46.6 Pa by using the pulsed laser deposition method. The crystallinity and surface morphology of these films were investigated by means of X-ray diffraction (XRD) and atomic force microscopy (AFM), respectively. The XRD pattern confirmed that YVO₄:Sm³⁺ film has zircon structure and the AFM study revealed that the films consist of homogeneous grains ranging from 100 to 400 nm. The room temperature photoluminescence (PL) spectra showed that the emitted radiation was dominated by a reddish-orange emission peak at 602 nm radiating from the transition of (⁴G_5/2→⁶H_7/2). The crystallinity, surface morphology, and photoluminescence spectra of thin-film phosphors were highly dependent on the deposition conditions, in particular, the substrate temperature. The surface roughness and photoluminescence intensity of these films showed similar behavior as a function of oxygen pressure.     

Dependence of excess bismuth content in precursor sols on ferroelectric and dielectric properties of Bi3.25La0.75Ti3O12 thin films fabricated by chemical solution deposition

Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films were fabricated on Pt/Ti/SiO₂/Si(1 0 0) substrates by chemical solution deposition (CSD), and the dependence of ferroelectric and dielectric properties of the as-deposited BLT thin films on excess Bi content in precursor sols was studied. It is found that the prepared BLT thin film shows the best polarization-electric field, capacitance-voltage and dielectric constant (?_r)-frequency characteristics, when the value of excess Bi content in precursor sols is 10%. In detail, its remnant polarization (2P_r) value is 40 μC/cm², the capacitance tunability is 21% measured at room temperature under conditions of an applied voltage of 8 V and measurement frequency of 10 kHz, and the ?_r is 696 at 100 kHz frequency.     

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.     

Structural and optical properties of nano-structured tungsten-doped ZnO thin films grown by pulsed laser deposition

Novel highly c-oriented tungsten-doped zinc oxide (WZO) thin films with 1 wt% were grown by pulsed laser deposition (PLD) technique on corning 1737F glass substrate. The effects of laser energy on the structural, morphological as well as optical transmission properties of the films were studied. The films were highly transparent with average transmittance exceeding 87% in the wavelength region lying between 400 and 2500 nm. X-ray diffraction analysis (XRD) results indicated that the WZO films had c-axis preferred orientation with wurtzite structure. Film thickness and the full width at half maximum (FWHM) of the (0 0 2) peaks of the films were found to be dependent on laser fluence. The composition determined through Rutherford backscattering spectroscopy (RBS) appeared to be independent of the laser fluence. By assuming a direct band gap transition, the band gap values of 3.36, 3.34 and 3.31 eV were obtained for corresponding laser fluence of 1, 1.7 and 2.7 J cm⁻², respectively. Compared with the reported undoped ZnO band gap value of 3.37 eV, it is conjectured that the observed low band gap values obtained in this study may be attributable to tungsten incorporation in the films as well as the increase in laser fluence. The high transparency makes the films useful as optical windows while the high band gap values support the idea that the films could be good candidates for optoelectronic applications.     

Electrical properties of highly (111)-oriented lead zirconate thin films

Antiferroelectric PbZrO₃ thin films were grown on Pt/Ti/SiO₂/Si substrates with predominant (111) orientation using a sol-gel process. The Pt/PbZrO₃/Pt film capacitor showed well-saturated hysteresis loops at an applied voltage of 5 V with remanent polarisation (P_r) and coercive electric field (E_c) values of 8.97 μC/cm² and 162 kV/cm, respectively. The leakage current density of the highly (111)-oriented PbZrO₃ film was less than 1.0×10⁻⁷ A/cm² over electric field ranges from 0 to 105 kV/cm. The conduction current depended on the voltage polarity. The PbZrO₃/Pt interface forms a Schottky barrier at electric fields from 20 to 160 kV/cm. The dielectric relaxation current behaviour of Pt/PbZrO₃/Pt capacitor obeys the well-known Curie-Von Schweidler law at electric field of 20-80 kV/cm, the currents have contributions of both dielectric relaxation current and leakage current.     

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.     

Fast photovoltaic characteristic of silver nano-cluster doped ZnO thin films induced by 1.064 μm pulsed laser

Fast photovoltaic characteristic was found from silver nano-cluster doped ZnO thin films when it was irradiated by 1.064 μm infrared laser. Its arising time is about 1 ns with an open-circuit photovoltage of ∼2 ns full width at half-maximum. A transient photovoltaic signal of ∼80 mV occurred with a full width at half-maximum of about 2 ns was observed under the illumination of a 4 mJ pulsed laser in duration of 25 ps. This fast photovoltaic response perhaps relate to the non-uniform distribution of the silver clusters along direction perpendicular to ZnO surface.     

Relaxor behavior of (Ba,Sr)(Zr,Ti)O3 ferroelectric ceramics

We examine the ferroelectric-relaxor behavior of (Ba_0.65Sr_0.35)(Zr_0.35Ti_0.65)O₃ (BSZT) ceramics in the temperature range from 80 to 380 K. A broad dielectric maximum, which shifts to higher temperature with increasing frequency, signifies the relaxor-type behavior of these ceramics. The value of the relaxation parameter γ∼2 estimated from the linear fit of the modified Curie-Weiss law, indicates the relaxor nature of the BSZT ceramics. The dielectric relaxation rate follows the Vogel-Fulcher relation with T_VF=107 K, E_a=0.121 eV, and ν₀=6.83×10¹⁴ Hz, further supports such relaxor nature. The slim P-E hysteresis loop and ‘butterfly’ shape dc bias field dependence of permittivity at T>T_m (T_m, the temperature of permittivity maximum) clearly signifies the occurrence of nanopolar clusters, which is the typical characteristic of ferroelectric relaxor. At 300 K and 10 kHz, the dielectric constant and loss tan δ are ∼1100 and 0.0015, respectively. The high tunability (∼25%) and figure of merit (∼130) at room temperature show that the BSZT ceramics could be a promising candidate for tunable capacitor applications.     

Effect of the mechanical stretching on the ferroelectric properties of a (VDF/TrFE) (75/25) copolymer film

The transition phase behaviour of a vinylidene fluoride-trifluoroethylene (VDF-TrFE) copolymer film was studied after being subjected to different mechanical stretching levels in both longitudinal (L) and transversal (T) directions relatively to the initial extrusion direction. Both ferroelectric-paraelectric (FE-PE) and melting transitions were detected in the films by differential scanning calorimetry, that were not affected by L stretching. This suggests that sliding mechanism along the c-axis of such films during plastic deformation influences slightly the all-trans chain conformations and the CF₂ dipole orientation. On the other hand, the FE-PE peak decreases in area and temperature upon T stretching, indicating a damage of the ferroelectric phase. However, the melting peak maintains unchanged. This fact provides evidence that the mechanical stretching do not change the total degree of crystallinity. The results suggest that the stretching induces a FE-PE phase transformation, without affecting the degree of crystallinity.     

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.     

Giant nonlinear optical properties of bismuth thin films grown by pulsed laser deposition

Thin films of Bi were grown by pulsed laser deposition on glass substrates at room temperature. The thickness and roughness of the films were characterized by grazing-incidence x-ray reflectivity, and the complex refractive indices were measured in the range from 1.5 to 4 eV by spectroscopic ellipsometry. We performed Z-scan measurements to study the third-order optical nonlinearity of the films. It was found that the Bi films exhibited an unusually large nonlinear refractive coefficient, n(I)~1.24x10(-1) cm(2)/kW and nonlinear absorption coefficient, alpha(I)~-3.97 cm/W , at low laser intensity, ~60 kW/cm(2) . This anomaly is believed to have an origin related to melting of the Bi films at the focus spot by the laser beam.     

The influence of Co doping on the dielectric, ferroelectric and ferromagnetic properties of Ba0.70Sr0.30TiO3 thin films

Ba_0.70Sr_0.30TiO₃ (BST) thin films doped by Co (BSTC) are fabricated by sol-gel method on a Pt/Ti/SiO₂/Si substrate. A strong correlation is observed among the microstructure, dielectric, ferroelectric, ferromagnetic properties and Co concentration. The dielectric constant of BST thin films can be tailored from 343 to 119 by manipulating the Co concentration. The dielectric loss of BSTC thin films are still kept below 0.020 and the tunability is above 30% at a dc-applied electric field of 500 kV/cm. With increasing Co doping up to 10 mol%, the coexistence of ferromagnetism and ferroelectrics is found. Suitable dielectric constant, low-dielectric loss, and high tunability of this kind of thin films can be useful for potential tunable applications.     

Crystal-chemical aspects of phase transitions in barium titanate

Structural aspects of phase transitions in barium titanate are analysed from a crystal-chemical point of view. The respective discussion is focused on two possible sources of ferroelectric deformation of TiO₆⁸⁻ octahedron. First, gradual changes of π-electron localisation are considered. Under an assumption of a mean field related to actual crystal symmetry, an adequate model is proposed. The values of bond orders are evaluated from resonance structures. They are compared with respective bond lengths. Another source of the ferroelectric deformation, which is taken into consideration, relates to the Ti-ion movements between eight potential minima on the cube diagonals. The analysis of the problem is grounded within adiabatic (local field) approximation and follows ideas of an eight-site model. The crystal structure is treated as a result of averaging of atomic positions according to the postulated disorder. Comparison of the X-ray interatomic distances with the values calculated from the disorder model is made. The collected data generally prove that the ferroelectric deformation of the TiO₆⁸⁻ octahedron, which is observed in barium titanate, contains two components. One is related to the changes of structural disorder degree and should be considered as a main factor. The other includes the effects attributed to the changes of π-electron localisation.     

Ferroelectric properties of Bi3.25−x/3La0.75Ti3−xNbxO12 films prepared by pulsed laser deposition

Bi₄Ti₃O₁₂ (BiT), Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_4−x/3Ti_3−xNb_xO₁₂ (BTN) and Bi_3.25−x/3La_0.75Ti_3−xNb_xO₁₂ (BLTN) thin films have been prepared by pulsed laser deposition. BTN and BLTN films exhibit a maximum in the remanent polarization P_r at a Nb content x=0.018. At this Nb content, the BLTN film has a P_r value (25 μC/cm²) that is much higher than that of BiT and a coercive field similar to that of BiT. The polarization of this BLTN film is fatigue-free up to 10⁹ switching cycles. The high fatigue resistance is mainly due to the substitution of Bi³⁺ ions by La³⁺ ions at the A site and the enhanced P_r arises largely from the replacement of Ti⁴⁺ ions by Nb⁵⁺ ions at the B site. The mechanisms behind the effects of the substitution at the two sites are discussed.     

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.     

Write-once blue laser recording using silicon doped SbOx thin films prepared by reactive dc-magnetron sputtering

Si:SbO_x films have been deposited by reactive dc-magnetron sputtering from a Sb target with Si chips attached in Ar + O₂ with the relative O₂ content 7%. The as-deposited films contained Sb metal, Sb₂O₃, SiO, Si₂O₃ and SiO₂. The crystallization of Sb was responsible for the changes of optical properties of the films. The results of the blue laser recording test showed that the films had good writing sensitivity for blue laser beam (406.7 nm), and the recording marks were still clear even if the films were deposited in air 60 days, which demonstrated that doping silicon in SbO_x films can improve the stability of SbO_x films. High reflectivity contrast of about 36% was obtained at a writing power 6 mW and writing pulse width 300 ns.