Pulsed laser deposition of semiconducting crystalline double-doped barium titanate thin films on nickel substrates

We synthesized by pulsed laser deposition (Ba,Sr,Y)TiO₃ and (Ba,Pb,Y)TiO₃ thin films on mechanically polished nickel substrates.The synthesized thin films were analyzed for: crystalline structure by X-ray diffractometry, morphology and surface topography by atomic force microscopy, optical and scanning electron microscopy, and elemental composition by energy dispersive X-ray spectroscopy and electrical properties by electrical measurements.We have shown that film properties were determined by the dopants, target composition, and deposition parameters (oxygen pressure, substrate temperature and incident laser fluence). All films exhibited a semiconducting behavior, as proved by the decrease of electrical resistance with heating temperature.     

Dielectric and leakage current properties of Li doped (Ba,Sr)TiO3 thick film interdigital capacitors on the alumina substrates

Li doped (Ba,Sr)TiO₃ thick films were fabricated by employing the screen printing method on the alumina (Al₂O₃) substrates. Interdigital capacitor patterns with seven fingers of 200 μm gap, 250 μm length were designed and screen printed on the alumina substrates. Ba_0.5Sr_0.5TiO₃ materials, paraelectric state at the room temperature, have been chosen for the microwave devices due to high dielectric permittivity and low loss tangent, however, the sintering temperature of (Ba,Sr)TiO₃ is over 1350 °C. In order to lower the sintering temperature, Li (3 wt%) was added to the (Ba,Sr)TiO₃ materials. Li doped (Ba,Sr)TiO₃ thick films screen printed on the alumina (Al₂O₃) substrates were sintered at 900 °C for 1.5 h. The structural feature was analyzed with X-ray diffraction method. Temperature dependent dielectric properties were characterized from 303 to 403 K at 1 MHz. Within the ±100 V of bias voltage, current-voltage characteristics of Li doped (Ba,Sr)TiO₃ films were investigated from 303 to 403 K. Through the current-voltage characteristics, the resistivity of Li doped (Ba,Sr)TiO₃ films were calculated.In this paper, the significant negative temperature coefficient of resistance (NTCR) of Li doped (Ba,Sr)TiO₃ films will be presented through the activation energy fitting. Measured activation energy is approximately 0.366 eV.     

Multiferroic tunnel junctions

Magnetic tunnel junctions with ferroelectric barriers, often referred to as multiferroic tunnel junctions, have been proposed recently to display new functionalities and new device concepts. One of the notable predictions is that the combination of two charge polarizing states and the parallel and antiparallel magnetic states could make it a four resistance state device. We have recently studied the ferroelectric tunneling using a scanning probe technique and multiferroic tunnel junctions using ferromagnetic La_0.7Ca_0.3MnO₃ and La_0.7Sr_0.3MnO₃ as the electrodes and ferroelectric (Ba, Sr)TiO₃ as the barrier in trilayer planner junctions. We show that very thin (Ba, Sr)TiO₃ films can sustain ferroelectricity up till room temperature. The multiferroic tunnel junctions show four resistance states as predicted and can operate at room temperatures.     

Phase transition behavior of highly (100) textured sol-gel-derived Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> thin films

We have investigated the relations between microstructure and dielectric properties in order to fabricate sol-gel-derived highly (100) oriented Ba_0.5Sr_0.5TiO₃ (BST 50/50) thin films with properties comparable to those of the bulk material. For the first time, we were able to fabricate BST thin films which exhibited the orthorhombic-to-tetragonal transition in addition to the commonly observed tetragonal-to-cubic transition. We were successful in explaining the commonly observed degradation of the dielectric behavior of BST thin films, when compared to that of the bulk material, in terms of grain size, compositional inhomogeneity (measured in terms of Sr/Ba ratio) between the grain bulk and grain boundary, and mechanical stresses. PACS 77.55.+f; 77.22Gm; 77.80.Bh; 77.80.Dj     

In situ photoemission study of the contact formation of (Ba,Sr)TiO3 with Cu and Au

The contact formation of (Ba,Sr)TiO₃ thin films and SrTiO₃ single crystals with Cu and Au have been studied using X-ray and ultraviolet photoelectron spectroscopy with in situ sample preparation. During metal deposition a partial reduction of the substrate occurs. The Fermi level at the interface is found to be close to the conduction band minimum, indicating small Schottky barrier heights (< 0.2 eV).     

Enhanced stability of platinized silicon substrates using an unconventional adhesion layer deposited by CSD for high temperature dielectric thin film deposition

Almost all platinized substrates manufactured presently use an TiO₂ adhesion layer to improve the adhesion between the SiO₂ and the Pt. These substrates however are stable till only 800 °C. We show that simply by replacing the TiO₂ with Al₂O₃, the stability of the electrodes can be increased to 1000 °C and more. These substrates can be used for high temperature depositions which standard platinized substrates cannot withstand. Further we show that dielectric thin films of BaTiO₃ and (Ba,Sr)TiO₃ crystallized at higher temperatures show almost a threefold increase in permittivity on these high temperature stable platinized silicon substrates.The large increase in permittivity is attributed to an increase in grain size at high temperatures. PACS 61.82.Fk; 68.35.Np; 68.60.Dv; 77.55.+f; 81.20.Fw     

Preparation of porous (Ba,Sr)TiO3 by adding corn-starch

A new method of preparing porous (Ba,Sr)TiO₃ ceramics has been introduced, using an ordinary ceramics processing technique. The effect of corn-starch on the positive temperature coefficient of resistivity characteristics and microstructure of the porous (Ba,Sr)TiO₃ ceramics has been investigated. When the corn-starch addition was 1-20 wt%, the PTCR jump was over 10⁶ and 1-2 orders higher than that of samples without corn-starch. Also, it was found that the (Ba,Sr)TiO₃ ceramics had porous microstructure by the addition of corn-starch. The porosity of the ceramics with 20 wt% corn-starch was 44%. The electrical properties of the (Ba,Sr)TiO₃ ceramics have been discussed, based on the microstructure, resistivity of grain boundaries, donor concentration of grains and the electrical potential barrier of grain boundaries.     

Microstructures and dielectric properties of compositionally graded (Ba1-xSrx) TiO3 thin films prepared by pulsed laser deposition

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (x:0.0∼0.25) thin films were grown on Pt (111)/TiO₂/SiO₂/Si (100) substrates using layer-by-layer pulsed laser deposition in the temperature range 550–650 °C. Both downgraded (Ba/Sr ratio varying from 100/0 at the bottom surface to 75/25 at the top surface) and upgraded (Ba/Sr ratio varying from 75/25 at the bottom surface to 100/0 at the top surface) BST films were prepared. Their microstructures were systematically studied by X-ray diffractometry and scanning electron microscopy. A grain morphology transition from large ‘rosettes’ (>0.30 μm) to small compact grains (70–110 nm) was observed in the downgraded BST films as the deposition temperature was increased from 550 to 650 °C. No such grain morphology transition was detected in the upgraded BST films. Dielectric measurements with metal electrodes revealed an enhanced dielectric behavior in the downgraded films. This enhancement is mainly attributed to the large compressive stress field built up near the interface between the downgraded film and substrate. Furthermore, the BaTiO₃ layer in the downgraded BST films not only serves as a bottom layer but also as an excellent seeding layer for enhancing the crystallization of the subsequent film layers in the downgraded films. Received: 10 December 2001 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: 86-25/359-5535, E-mail: xhzhu@public1.ptt.js.cn     

The dependence of dielectric properties on the thickness of (Ba,Sr)TiO3 thin films

In the dielectric (Ba,Sr)TiO₃ thin films, the correlation between the film thickness and the dielectric properties was investigated. The dielectric properties such as the dielectric constant (ε) and dielectric loss (tan δ) were measured using the capacitor geometry. As the film thickness increased, the dielectric constant also increased due to the reduction of the interfacial dead-layer effect. However, the dielectric loss did not show a monotonous variation with the increasing film thickness. It was found that the dielectric loss correlated well with the non-uniform distribution of local strain, as analyzed by X-ray diffraction, according to the Curie–von Schweidler relaxation law.     

Synthesis and characterization of nanostructured (Pb1− x Sr x )TiO3 thin films by a modified chemical route

The coating solutions of nanostructured (Pb_{1– x} Sr _x )TiO₃ (PST) thin films have been prepared by the sol–gel combined metallo-organic decomposition method. The coating solutions were deposited on Pt/Ti/SiO₂/Si substrates using a spin-coating technique with spinning speed of 4300 rpm and annealed at 650°C. The effect of Sr content in reducing the grain size and tetragonal distortion of PST films has been studied. The optimum conditions for crystalline phase formation in the films have been analyzed by thermogravimetric, differential thermal analysis and Fourier transform infrared spectroscopy. The phase and microstructure of the films were studied by X-ray diffraction (XRD) and atomic force microscopy (AFM). The XRD pattern shows that the PST thin films are crystallized into tetragonal structures without any impurity phase and the distortion ratio reduces with increasing Sr concentration. The AFM results indicate an increase in grain size with increasing annealing temperature of the film and reduction in grain size with increasing Sr concentration.     

Thin ferroelectric films: Preparation and prospects of integration

The properties of (Ba,Sr)TiO₃ and BiFeO₃ thin films and related nanostructures have been considered. The films have been prepared by rf sputtering in an oxygen atmosphere at an elevated pressure, and the nanostructures have been produced using focused ion-beam etching. The electric field has been applied across a planar interdigital structure of electrodes. The structure, dielectric, electro-optical, and nonlinear optical properties of the prepared samples have been investigated over wide ranges of thicknesses and electric field frequencies. The high efficiency of the planar switching and its influence on the optical properties of the produced structures have been demonstrated. The nanostructuring makes it possible to change the dielectric and optical properties of the materials under investigation, thus increasing the range of switching of functional parameters.     

SrTiO3薄膜生长初期Sr，Ti，O原子分子反应机理的理论研究

在激光分子束外延(LMBE)生长SrTiO₃(STO)薄膜过程中,激光闪蒸出的Sr,Ti,O原子的微观反应过程及粒子形态是STO薄膜生长初期形成的关键.采用密度泛函理论中的广义梯度近似(DFT/GGA)方法,在PW91/DNP 水平上研究了Sr,Ti,O原子在真空中的优先反应过程和形态,计算研究了SrO,TiO₂和STO分子形成的反应机理,获得了相应的中间体和过渡态及反应活化能,并运用前线轨道理论分析了STO分子的形成机理.对比计算了STO分子可能的几何构型,得 关键词： 3薄膜')" href="#">SrTiO₃薄膜 反应机理 活化能     

Thermodynamic stability and disordering in LacSr1−cMnO3 solid solutions

Two different types of ab initio electronic and atomic structure calculations for ordered solid solutions are combined with solid solution thermodynamics in a study of the Sr-doped LaMnO₃. Unlike Ba in the isostructural (Sr,Ba)TiO₃, Sr aggregation in the LaMnO₃ matrix potentially leading to decomposition into heterogeneous mixture of LaMnO₃ and SrMnO₃ phases is energetically unfavorable. We demonstrate that for a particular solid solution with 12.5% Sr the order–disorder transition occurs only at very high temperatures otherwise Sr is supposed to be periodically distributed in the LaMnO₃ matrix.     

Micro-structuring of TiO2 thin films by laser-assisted diffraction processing

Thin films of TiO₂ are deposited by magnetron sputtering on glass substrate and are irradiated by UV radiation using a KrF excimer laser (248 nm). These thin films are patterned with a razor blade placed on the way of the radiation just in front of the TiO₂ thin film. Just near the edge of the razor blade on the thin film, diffraction lines are observed, resulting in the ablation of the film. These patterns are characterized by optical microscopy, mechanical profilometry. Diffraction up to the 35th order is observed. The results are shown to be compatible with a model in which electronic excitation plays the major role.     

Structural and optical properties of electrohydrodynamically atomized TiO2 nanostructured thin films

In this paper, we report an alternate technique for the deposition of nanostructured TiO₂ thin films using the electrohydrodynamic atomization (EHDA) technique using polyvinylpyrrolidone (PVP) as a stabilizer. The required parameters for achieving uniform TiO₂ films using EHDA are also discussed in detail. X-ray diffraction results confirm that the TiO₂ films were oriented in the anatase phase. Scanning electron microscope studies revealed the uniform deposition of the TiO₂. The purity of the films is characterized by using Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS), confirming the presence of Ti–O bonding in the films without any organic residue. The optical properties of the TiO₂ films were measured by UV-visible spectroscopy, which shows that the transparency of the films is nearly 85% in the visible region. The current–voltage (I–V) curve of the TiO₂ thin films shows a nearly linear behavior with 45 mΩ?cm of electrical resistivity. These results suggest that TiO₂ thin films deposited via the EHDA method possess promising applications in optoelectronic devices.     

Structural and ferroelectric properties of Pb1-xSrxTiO3 thin films

Strontium-modified lead titanate (PST) thin films with composition Pb_1-xSr_xTiO₃ (0.10<x0.60) were grown on Pt/Ti/SiO₂/Si substrates using a soft chemical process. The crystallization of the PST thin films was achieved by heat treatment at 600 °C. The structural and microstructural modifications in the films were studied using X-ray diffraction (XRD) and atomic force microscopy, respectively. The XRD study shows that the lattice parameters of polycrystalline PST thin films calculated from X-ray data indicate a decrease in lattice tetragonality with the increase in strontium content in these films. This indicates a gradual change from tetragonal to cubic structure. By atomic force microscopy analysis, the average grain size of the thin films was systematically reduced with the increase in Sr content. The dielectric property of the thin films was found to be strongly dependent on the Sr concentration. With 60 at.% Sr content, a ferroelectric to paraelectric phase transition was observed at room temperature. PACS 61.10.Nz; 68.37.Ps; 77.55.+f; 77.84.-s; 81.15.-z     

Mechanism of the rf sputtering of mixed oxides

New experimental data on the growth mechanisms of multicomponent Pb(Zr,Ti)O₃, (Ba,Sr)TiO₃, and Y-Ba-Cu-O films in an rf discharge plasma are presented. An investigation of the spatial distribution of the radiated intensity of the sputtered particles in the rf plasma during the deposition of films of these mixed oxides in the epitaxial state reveals general laws governing their transport from the target to the substrate, which are stipulated by features of the negative glow of the rf discharge. The roles of external and internal parameters are examined from the standpoint of describing the mechanisms of the heteroepitaxial growth of mixed oxides. Zh. Tekh. Fiz. 68, 99–103 (September 1998)     

The development of the physical and electrical characteristics of multi-layer TiO<Subscript>2</Subscript>–W–TiO<Subscript>2</Subscript> thin films

In this study, two different thin films, TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films (W, tungsten), are prepared by RF magnetron sputtering onto glass substrates. The crystal structure, morphology, and transmittance of TiO₂ and TiO₂–W–TiO₂ multi-layer thin films are investigated by X-ray diffraction, SEM, and UV-Vis spectrometer, respectively. The amorphous, rutile, and anatase TiO₂ phases are observed in the TiO₂ thin film and in the TiO₂–W–TiO₂ multi-layer thin films. The deposition of tungsten as the inter-layer will have large effect on the transmittance and phase ratios of rutile and anatase phases in the TiO₂–W–TiO₂ multi-layer thin films. The crystal intensities of amorous TiO₂ will decrease as the tungsten is used as the middle layer in the multi-layer structure. The band gap energy values of TiO₂ thin film and TiO₂–W–TiO₂ multi-layer thin films are evaluated from (αhν)^1/2 versus energy plots, and the calculated results show that the energy gap decreases from 3.21 eV (TiO₂ thin film) to 3.08∼3.03 EV (TiO₂–W–TiO₂ multi-layer thin films).     

Large piezoresponse of lead-free Bi0.5(Na0.85K0.15)0.5TiO3 thin film

0.85Bi_0.5Na_0.5TiO₃-0.15Bi_0.5K_0.5TiO₃ (BNKT15) lead-free thin films were prepared on Pt(111)/TiO₂/SiO₂/Si(100) substrates by the chemical solution deposition method. BNKT15 are MPB composition in the Bi_0.5Na_0.5TiO₃-Bi_0.5K_0.5TiO₃ (BNT-BKT) system. The maximum piezoelectric coefficient (d_33,f) value of BNKT15 thin film is approximately 75 pm/V, which is comparable to that of polycrystalline PZT thin films. These results suggest that BNKT15 thin film can be used as an alternative for PZT films in piezoelectric micro-electromechanical systems.