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The bismuth layer-structured Na0.5Bi4.5-xPrxTi4O15 (x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5) (NBT-xPr3+) ceramics were fabricated using the traditional solid reaction process. The effect of different Pr3+ contents on dielectric, ferroelectric and piezoelectric properties of Na0.5Bi4.5Ti4O15 ceramics were investigated. The grain size of Pr3+-doping ceramics was found to be smaller than that of pure one, the maximum dielectric constant and Curie temperature Tc gradually decreased with increasing Pr3+ contents, and the dielectric loss decreased at high temperature by Pr3+-doping. Moreover, the activation energy (Ea), resistivity (Z’), remanent polarization (2Pr) and piezoelectric constant (d33) increased by Pr3+-doping. The NBT-xPr3+ ceramics with x = 0.3 achieved the optimal properties with the maximum dielectric constant of 1109.18, minimum loss of 0.00822 (250 kHz), Ea of 1.122 eV, Z’ of 7.9 kΩ cm (725 oC), d33 of 18 pC/N, 2Pr of 12.04 μC/cm2. The enhancement was due to the addition of Pr3+ which suppressed the decreasing of resistivity at high temperature and made it possible for NBT-xPr3+ ceramics to be poled in perpendicular direction, implying that it is a great improvement for Na0.5Bi4.5Ti4O15 ceramics in electrical properties.

New lead-free dielectric ceramics, Na 1+x BiTi 6 O 14+0.5x (x = −0.02, − 0.01, 0.01, 0.02), were prepared by the conventional solid-state method. Micro-structural and electrical properties of Na 1+x BiTi 6 O 14+0.5x were studied. XRD showed all the samples exhibited a single structured phase. Grains decreased at the beginning, then grew with the increasing x content in SEM. Impedance spectra (IS) analysis evidenced the phenomena that the dielectric permittivity increased firstly, then decreased, while the loss had the opposite trend. Z* plots showed that Na 1+x BiTi 6 O 14+0.5x ceramics were a kind of dielectrics. The activation energy ( E a ) could be calculated in the range of 1.53–1.65 eV, which indicated they were dielectric ceramics. Na 1+x BiTi 6 O 14+0.5x ceramics (x = 0.01) sintered at 1040 °C showed prominent dielectric properties with a dielectric constant of 25.76, loss of 0.07%, E a of 1.65 eV, density of 3.463 g/cm 3 , impedance of 0.532 MΩ cm, -Z′′ max of 0.1958 MΩ cm, capacitance of 5.56 pF/cm (600 ℃), which were enhanced much compared with other samples. The existence of dielectric properties with high dielectric constant, low dielectric loss and wide operating temperature range makes it possible to develop the ceramics into high-temperature capacitors.

As a new member of lead-free Na 0.5 Bi 0.5 TiO 3 (NBT) ceramics based on bismuth layer-structured ferroelectrics (BLSFs), Bi x Ti 3 O 6+1.5 x ( x = 3.96, 3.98, 4.0, 4.02, 4.04) ceramics was prepared by a conventional mixed oxide route. In order to explore the ferroelectric and dielectric properties, we changed the content of Bi in the ceramics. XRD patterns of Bi x Ti 3 O 6+1.5 x demonstrated that the new material was a single phase of Bi-layered perovskite structure. Through impedance spectra analysis, we found that the Bi 4.02 Ti 3 O 12.03 ceramics sintered at 1100 °C showed excellent dielectric properties with a highest dielectric constant of 8967.49 and a lowest dielectric loss of 0.00298 measured under 10 kHz, which were enhanced much compared with Bi 4 Ti 3 O 12 prepared by the same means. Meantime, the Curie temperature of the whole samples was about 670 °C. In addition, the ferroelectric hysteresis loops of all the samples indicated that they were ferroelectric materials, and Bi 4 Ti 3 O 12 ceramics sintered at 1100 °C processed a remanent polarization (2 P r ) of 12.206 µC/cm 2 and a coercive field of 29.542 kV/cm. SEM can roughly describe the results of the dielectric spectrum and ferroelectricity with different Bi concentration through grain size mechanics. Because of the high dielectric constant, wide operating temperature and low dielectric loss, the Bi 4 Ti 3 O 12 ceramics have a broad application prospect in components, such as sensors, high-temperature capacitors and so on.

100-nm-thick epitaxial BaTiO 3 (BTO) films were prepared on the Nb-doped SrTiO 3 (NSTO) single-crystal substrates by pulsed laser deposition. Bipolar resistive switching (RS) behavior was observed in the as-prepared BTO/NSTO samples, which was attributed to the formation and rupture of conductive filaments in the BTO films. The RS effect was suppressed after the samples were annealed in air due to the decrease in oxygen vacancies during annealing, which was confirmed by X-ray photoelectron spectroscopy (XPS) measurements. The current–voltage curves of the as-prepared samples show linear ohmic conduction at the low resistive state and space-charge-limited conduction (SCLC) at the high resistive state, respectively. SCLC dominated in the annealed samples.

Amorphous GeSex (x = 2, 4, 6) films were prepared by pulsed laser deposition technique. The optical band gaps ( E g opt ) and refractive indices of the films were derived from the absorption spectra and optical transmission spectra, respectively. The short-wave absorption edges of the films were well consistent with the ‘non-direct transition’ model proposed by Tauc. The dispersion of the refractive index was analyzed in terms of the single-oscillator Wemple–Di Domenico model. The structural units of the films were characterized using Raman spectroscopy. In addition to the basic structural units of edge-sharing GeSe4/2 tetrahedra, there are Se Se homopolar bonds in Se-rich GeSe4 and GeSe6 films. And Ge Ge bonds exist in stoichiometric GeSe2 film. The results also show that the refractive index of the films changes with the Se content. E g opt decreases with the reduction of Se content in the GeSex films. The changes of E g opt were discussed in relation to the structures of the films confirmed by the Raman spectra analysis.

Tm-doped Ba 0.8 Sr 0.2 TiO 3 thick films were prepared by the screen-printing technique on the alumina substrate. The microstructure of the Tm-doped BST thick films was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy, respectively. All the samples showed a typical perovskite polycrystalline structure when sintered at 1260 °C. The substitution behavior of Tm 3+ ion in BST was found to change with increasing the Tm 3+ concentration. The observed Tm-related red emission reaches the maximum at 0.2 mol% Tm 3+ concentration. The effects of concentration quenching on the luminescence intensity were discussed.

Ho3+ doped Ba0.65Sr0.35TiO3 (BST) nanocrystals was prepared by sol–gel method. The structural and morphological properties of the nanocrystals were characterized using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The absorption spectrum, photoluminescence spectrum and fluorescence time decay curve were measured at room temperature. Based on the Judd–Ofelt (J–O) theory, the J–O intensity parameters Ωt (t=2, 4, 6) of Ho3+ doped BST nanocrystals were calculated to be 0.67×10−20 cm2, 1.11×10−20 cm2 and 1.09×10−20 cm2, respectively. The emission probabilities, radiative lifetimes and branching ratios of the different Ho3+ transitions were also determined. The emission cross sections of the important intermanifold transitions 5F4, 5S2→5I8, 5F5→5I8 and 5F4→5I7 have been calculated from the luminescence spectrum. The room temperature fluorescence lifetime of the 5S2→5I8 transition for Ho3+ in BST nanocrystals was measured and the radiative quantum efficiency was estimated to be 61.9%.

Amorphous GeS x (x = 2, 4, 6) films were prepared by the pulsed laser deposition (PLD) technique. The optical band gaps ( E g opt ) and refractive indices of the films were obtained from the optical absorption spectra and transmission spectra, respectively. The short-wave absorption edges of the films were described using the ‘non-direct transition’ model proposed by Tauc. The dispersion of the refractive index was analyzed in terms of the single-oscillator Wemple–Di Domenico model. The structural units of the films were characterized using Raman spectroscopy. In addition to the basic structural units of edge-sharing and corner-sharing [GeS 4 ] tetrahedra, there are S–S homopolar bonds in S-rich GeS 4 and GeS 6 films while Ge–Ge bonds exist in stoichiometric GeS 2 film. The results show that the index of refraction decreases while E g opt increases with the sulphur content in the GeS x films. The changes of E g opt were discussed in relation to the structure of GeS x films, which were confirmed by the Raman spectra analysis.

Amorphous (GeSe2)100−x –Bi x (x=0, 0.4, 2 and 4) films were prepared by the pulsed laser deposition technique. The optical transmission spectra, absorption spectra and Raman spectra of the films were measured. The short-wavelength absorption edges in the strong absorption region of the films were described using the ‘non-direct-transition’ model proposed by Tauc and the optical band gaps (\(E_{\mathrm{g}}^{\mathrm{opt}})\) were determined. The Urbach energy (E u) was derived in the exponential part of the absorption edge. Both \(E_{\mathrm{g}}^{\mathrm{opt}}\) and Tauc slopes (B 1/2) decreased with increasing Bi content, while E u had the opposite trend. The refractive indices of the films were calculated from the transmission spectra by using the Swanepoel method. Analysis of Raman spectra and absorption spectra shows that Bi addition decreases the mean bond energy and increases E u in the amorphous films, which caused the decrease of \(E_{\mathrm{g}}^{\mathrm{opt}}\). The changes of the refractive indices are also discussed.

Amorphous GeSe2 film was prepared by the pulsed laser deposition technique and annealed at different temperature from 473 to 623 K. Using the ‘non-direct transition’ model proposed by Tauc, the short wavelength absorption edges of the films were well fitted and the optical band gaps ( E g opt ) were determined. The Tauc slope of the as-deposited film is smaller than those of annealed films, which were proposed as an indicator of the degree of structural randomness of amorphous semiconductors. The refractive index and thickness of the films were calculated from the optical transmission spectra using the Swanepoel method. The index of refraction decreased while E g opt increased gradually with increasing the annealing temperature. The thermal-bleaching and thermal-contraction effects were observed, which were interpreted as the reduction in the density of homopolar bonds according to the Raman spectra analysis and the diminution of porous structure in the fragments of the annealed films, respectively.

Amorphous thin films of GeSe2 and GeSe4 were prepared by the pulsed laser deposition (PLD) technique. Refractive index, thickness and optical band gap (E opt g ) of the films were abtained from the optical transmission spectra and absorption spectra, respectively. Based on the ‘non-direct transition’ model proposed by Tauc, the absorption edges can be well fitted. As an indicator of the degree of structural randomness of amorphous semiconductors, the Tauc slopes of the prepared thin films were discussed. The dispersion of refractive index was analyzed in terms of the single-oscillator Wemple-Di Domenico model. For asdeposited films, after annealing below the glass transition temperature (Tg), the drop of refractive index and the increase of E opt g can be clearly observed. The thermal-bleaching effect was proposed to the reduction in the density of homopolar bonds confirmed by the Raman spectra analysis. The thermal-contraction effect was ascribed to the elinimination of porous structure of the as-deposited films. © 2009 Elsevier B.V. All rights reserved.

Amorphous thin films (1 − x )(4GeSe 2 –Ga 2 Se 3 )– x KBr ( x = 0, 0.1, 0.2, 0.3) were prepared by the pulsed laser deposition (PLD) technique. The optical parameters were calculated using the Swanepoel method from the optical transmission spectra. The optical band gap ( E g opt ) of the studied films increased while the index of refraction decreased when increased the content of KBr. The Tauc slopes were discussed as an indicator of the degree of structural randomness of amorphous semiconductors. The index of refraction decreased and E g opt increased after annealing of as-deposited films below the glass transition temperature. The thermal-bleaching and thermal- contraction effects were observed, which are discussed in relation to the reduction in the density of homopolar bonds confirmed by the Raman spectra analysis and the decreased amount of fragments of the as-deposited films, respectively.

Barium strontium titanate (Ba1−x Sr x )TiO3 (BST) thin films were deposited on Pt, Ru, RuO2, and Pt/RuO2 electrodes by radio frequency magnetron sputtering. The interfacial structure characteristic of the BST films deposited on various electrodes was investigated. X-ray photoelectron spectroscopy investigations showed that the interfacial diffusion layer in BST/Pt and BST/Ru are approximately 6 and 10 nm, respectively. The BST films are short of Ba and O elements comparing with the stoichiometry Ba0.65Sr0.35TiO3 in the interface region. Dielectric measurement of the BST films with thickness ranging from 70 to 400 nm revealed that the BST films deposited on Pt and Pt/RuO2 bottom electrodes have similar dielectric property, the BST films deposited on Ru have the highest bulk dielectric constant, and the thickness dependence of dielectric constant on the BST film deposited on RuO2 electrode can be neglected. The interfacial layer dielectric constant of BST films deposited on Pt and Ru electrodes are estimated to be about 34.5 and 157.1, respectively. The effect of interfacial dead-layer on the dielectric constant could be eliminated through selecting appropriate bottom electrodes.

Ba0.65Sr0.35TiO3 (BST) thin films were deposited on Pt/Ti/SiO2/Si substrates by radio frequency magnetron sputtering technique. X-ray photoelectron spectroscopy (XPS) depth profiling data show that each element component of the BST film possesses a uniform distribution from the outermost surface to subsurface, but obvious Ti-rich is present to BST/Pt interface because Ti4+ cations are partially reduced to form amorphous oxides such as TiOx (x

The influence of lattice strain on the strength of dipoles in the Ho3+-doped barium-strontium titanate (BST) thin films has been analyzed. Thin films were produced by using the sol–gel technique on Si substrate. The resulting stress due to fabrication process was quantified by analyzing the {200} planes of the cubic perovskite structure and comparing them with the data for bulk materials. The influence of strain and changes due to Ho3+-ion doping were characterized by Raman and visible photoluminescence spectroscopy, which clearly show the evidence for the increased tetragonality due to weaker dipole interaction at B-sites of cubic perovskite in the presence of Ho3+-ions at concentrations larger than 3 mol%. The film strain can therefore be controlled to enhance the intensity of emitted light at 650 nm.

Ba 0.65 Sr 0.35 TiO 3 (BST) thin films doped with Ho 3+ were prepared on silicon substrates by a modified sol–gel technique. The microstructure of the BST films was characterized by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and Raman spectroscopy. The results showed that 3 mol% Ho-doped BST has the largest grain size and surface root-mean square roughness. The thickness of the film was about 1.36 μm. The Ho 3+ luminescence intensity reached a maximum value in the sample with 3 mol% Ho 3+ ions concentration sintered at 700 °C. All the results showed that the BST: Ho 3+ films may have potential use for photonic devices.

Sol-gel-derived Ba"0"."6"5Sr"0"."3"5TiO"3 (BST) thin films were etched in CF"4/Ar/O"2 plasma using magnetically enhanced reactive ion etching technology. The maximum etch rate of BST film is 8.47nm/min when CF"4/Ar/O"2 gas mixing ratio is equal to 9/36/5. X-ray photoelectron spectroscopy analysis indicates the accumulation of fluorine-containing by-products on the etched surface due to their poor volatility, resulting in (Ba,Sr)-rich and (Ti,O)-deficient etched surface. Compared to the unetched counterparts, the etched Ba 3d"5"/"2, Ba 3d"3"/"2, Sr 3d"5"/"2, Sr 3d"3"/"2, Ti 2p"3"/"2, Ti 2p"1"/"2 and O 1s photoelectron peaks shift towards higher binding energy regions by amounts of 1.31, 1.30, 0.60, 0.79, 0.09, 0.46 and 0.50eV, respectively. X-ray diffraction (XRD) analysis reveals that intensities of the etched BST (100), (110), (200) and (211) peaks are lowered and broadened. Raman spectra confirm that the Raman peaks of the etched film shift towards lower wave number regions with the values of 7, 6, 4 and 4cm^-^1, and the corresponding phonon lifetimes are longer than those of the unetched film because of the plasma-induced damage. When the etched films are postannealed at 650^oC for 20min under an O"2 ambience, the chemical shifts of Ba 3d, Sr 3d, Ti 2p and O 1s peaks, the variations for atomic concentrations of Ba, Sr, Ti and O, and the Raman redshifts are reduced, while the corresponding XRD peak intensities increase. It is conceivable that the plasma-induced damage of the etched film could be partially recovered during the postannealing process.

Ba"0"."6"5Sr"0"."3"5TiO"3 (BST) thin films doped with holmium were prepared on silicon and fused quartz substrates by a modified sol-gel technique. The microstructures of BST films were characterized by atomic force microscopy (AFM) and X-ray diffraction (XRD). The results showed that 3mol% Ho-doped BST has the largest grain size and surface root-mean square roughness. The transmission spectra of Ho-doped BST films were measured by spectrophotometer. The refractive index and thickness of 1mol% Ho-doped BST film was calculated using envelope method from the transmission spectra. It showed that the refractive index increased from 1.94 to 2.09 as wavelength decreased from 700nm to 400nm, which was smaller than pure BST thin films we have reported. The average oscillator strength and wavelength were estimated using a Sellmeir-type dispersion equation. These results show the potential of using Ho-doped BST thin films as an electro-optical novel material.

La0.67Sr0.33MnO3 (LSMO) films were prepared on SrTiO3 single-crystal substrates by the pulsed laser deposition method. X-ray photoelectron spectra (XPS) were measured for the LSMO films as-prepared, annealed in oxygen and in vacuum, respectively. Multiple peaks fitting for Mn 2p3/2 XPS spectra shows that Mn2+ appears and the ratio of Mn3+/Mn4+ increases on the surface of LSMO film annealed in vacuum comparing with the as-prepared film, though the saturation magnetization (Ms) changes little. Mn6+ and Mn7+ can be detected while Mn4+ decreases much on the surface of LSMO film annealed in oxygen. The change of Mn3+/Mn4+ results in the obviously reduce of Ms. O1s spectra show the gradual changes of Mn-O, Sr-O and La-O. Analysis indicates that Mn2+ forms at the surface defects of LSMO films. Annealing in vacuum hardly affects the magnetic property of LSMO films. But annealing in oxygen greatly changes the valence states of Mn, which weakens the magnetic property of LSMO films.

Down graded barium strontium tianate(BST) thin films were prepared on Pt/Ti/SiO2/Si(100) substrate by radio frequency magnetron sputtering. The BST thin films were deposited at various substrate temperatures, then annealed at 700 °C for an hour. The influences of the deposition parameters on the crystallization behavior, microstructure and dielectric properties of BST thin films were investigated by X-ray diffraction, field emission scanning electron microscopy and dielectric frequency spectra. XRD results indicate that the BST thin films deposited at higher temperature have improved crystallization structure.The SEM observations show that the surface of the films is smooth with homogeneous grains.The dielectric properties of the films have been examined and discussed. The experiments show that BST thin films deposited at 650oc, 3.0Pa working pressure exhibits superior dielectric properties: the highest dielectric constant is 448 and lowest dielectric loss is 0.013 at 100 kHz, respectively. These results make BST thin films be a promising candidate for microelectronic device application.

Ba0.8Sr0.2TiO3(BST) thin films with different Nd-doped concentrations have been frabracated on silicon substrates by modified Sol-gel process. All the samples were annealed at 700°C for 60 min.The structural and morphological properties of the films were examined by X-ray diffraction (XRD) and Atomic Force Microscopy (AFM). The XRD studies indicated that both pure and doped BST thin films show crystallized perovskite structures, the particle size is about 20 nm. The AFM images displayed that the films have high quality and finegrained polycrystalline structure. The photoluminescence spectra(PL) were carried out using the 808 nm Ar+ laser line as the excitation source at room temperature. The Nd-doped BST thin films show three NIR luminescence peaks corresponding to 4F3/2-4I9/2 transition at 880 nm; 4F3/2-4I11/2 transition at 1066 nm and 4F3/2-4I13/2 transition at 1345 nm; respectively. The influence of Nd3+ concentration on the microstructure and the luminescence properties were discussed. All the results showed that the Nd-doped BST films have great potential uses for novel integrated optic devices.

Ba0.65Sr0.35TiO3 thin films have been prepared by RF magnetron sputtering. The crystallization and microstructure of the films were characterized by X-ray diffraction (XRD), scan electronic microstructure (SEM) and atom force microstructure (AFM). As-deposited thin films were found to be amorphous. The more intense characteristic diffraction peaks and improved crystallization can be observed in (Ba,Sr)TiO3 (BST) thin films deposited at high temperatures and annealed at higher than 650°C. Optical constants were determined from transmittance spectra by using the envelope method. The refractive index increased from 1.778 to 1.961 as the substrate temperature increased from 560 to 650°C. Both the refractive index and extinction coefficient increased with annealing temperature. The refractive index and extinction coefficient increased when the oxygen-to-argon ratio increased from 1:4 to 1:1. The dispersion of relation of the extinction coefficient vs wavelength was also investigated. The optical band gap of BST thin films was found to be about 3.56 eV, which decreased apparently with increasing annealing temperature.

Amorphous GeS6 bulk glass and film were prepared by the traditional melt–quenching method and pulsed laser deposition technique. The optical transmission spectra, absorption spectra and Raman spectra were measured. The short- wave absorption edges were described using the ‘non–direct transition’ model proposed by Tauc. And the optical band gaps of the bulk glass and film were derived from the absorption spectra. The results show that GeS6 film has bigger optical band gap than that of bulk glass. The structural units of the bulk glass and film were characterized using Raman spectroscopy. In addition to the basic structural units of edge-sharing and corner-sharing GeS4/2 tetrahedra, there are S–S homo–polar bonds in both GeS6 bulk glass and GeS6 film. While more S8 rings exist in GeS6 bulk glass. The bigger optical band gap of the GeS6 film was discussed in relation to the structure of the film confirmed by the Raman spectra analysis.