Microstructural investigations of Y2O3 thin films deposited by laser ablation on MgO

The epitaxial relationships and the microstructure of thin Y₂O₃ film, in situ grown by laser ablation at 700 °C under 0.5 mbar oxygen pressure on MgO substrate, are studied by X-ray and HRTEM investigations. X-ray φ-scanexperiments show that Y₂O₃ exhibits two different crystallographic growing directions <111> and <100> on (100) single-crystalline MgO substrate. The <111> growing direction appears with four different epitaxial relationships where the <110> Y₂O₃ in-plane direction is parallel to the <110> in-plane direction of MgO. The <100> growing direction appears with one epitaxial relationship, cube Y₂O₃ on cube MgO. The HRTEM experiments show the columnar aspect of the Y₂O₃ thin film. Both (111) and (100) Y₂O₃-oriented grains are observed in good agreement with the X-ray experiments. Received: 16 May 2000 / Accepted: 22 May 2000 / Published online: 13 September 2000     

Effects of deposition temperature and post-annealing on structure and electrical properties in (La<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>)CoO<Subscript>3</Subscript> films grown on silicon substrate

(La_0.5Sr_0.5)CoO₃ (LSCO) thin films have been fabricated on silicon substrate by the pulsed laser deposition method. The effects of substrate temperature and post-annealing condition on the structural and electrical properties are investigated. The samples grown above 650°C are fully crystalline with perovskite structure. The film deposited at 700°C has columnar growth with electrical resistivity of about 1.99×10⁻³ Ω cm. The amorphous films grown at 500°C were post-annealed at different conditions. The sample post-annealed at 700°C and 10⁻⁴ Pa has similar microstructure with the sample in situ grown at 700°C and 25 Pa. However, the electrical resistivity of the post-annealed sample is one magnitude higher than that of the in situ grown sample because of the effect of oxygen vacancy. The temperature dependence of resistivity exhibits semiconductor-like character. It was found that post-annealing by rapid thermal process will result in film cracks due to the thermal stress. The results are referential for the applications of LSCO in microelectronic devices.     

Formation of Heusler alloy Co2FeSi thin films on the surface of single-crystal silicon

The initial stages of Heusler alloy (Co₂FeSi) thin film growth by reactive epitaxy on the Si(100)2 × 1 surface are studied, and formation conditions for this alloy are found. At a substrate temperature of lower than, or equal to, 180°C, an island film of ternary Co-Fe-Si film grows on the surface. The silicon content in this film is lower than in the compound to be synthesized. The film becomes continuous when its thickness exceeds 1.2 nm. It is shown that post-growth annealing at 240°C can raise the silicon content in the film and be conducive to obtaining Heusler alloy of a desired composition. In situ measurements of the films show that ferromagnetic ordering in them has a threshold and shows up at the coalescence growth stage of the Co-Fe-Si island alloy.     

The film thickness dependent thermal stability of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>:Ag thin films as high-temperature solar selective absorbers

The monolayer Al₂O₃:Ag thin films were prepared by magnetron sputtering. The microstructure and optical properties of thin film after annealing at 700 °C in air were characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and spectrophotometer. It revealed that the particle shape, size, and distribution across the film were greatly changed before and after annealing. The surface plasmon resonance absorption and thermal stability of the film were found to be strongly dependent on the film thickness, which was believed to be associated with the evolution process of particle diffusion, agglomeration, and evaporation during annealing at high temperature. When the film thickness was smaller than 90 nm, the film SPR absorption can be attenuated until extinct with increasing annealing time due to the evaporation of Ag particles. While the film thickness was larger than 120 nm, the absorption can keep constant even after annealing for 64 h due to the agglomeration of Ag particles. On the base of film thickness results, the multilayer Al₂O₃:Ag solar selective thin films were prepared and the thermal stability test illustrated that the solar selectivity of multilayer films with absorbing layer thickness larger than 120 nm did not degrade after annealing at 500 °C for 70 h in air. It can be concluded that film thickness is an important factor to control the thermal stability of Al₂O₃:Ag thin films as high-temperature solar selective absorbers.     

Epitaxial growth of PbTiO3 thin film on (110) NdGaO3 substrate by metalorganic chemical vapor deposition

(001) preferentially oriented PbTiO₃ thin films have been grown on (110) NdGaO₃ substrates by metalorganic chemical vapor deposition (MOCVD) under reduced pressure at 650°C. Atomic force microscopy (AFM) surface morphology of the as-deposited film showed the evidence of layer-by-layer growth in the MOCVD process. By using a grazing-angle scattering technique, a highly resolved Raman spectrum of the epitaxial PbTiO₃thin film on perovskite substrate was first time recorded. Other microstructure of the film, such as the element composition, the c-domain percentage and the epitaxial nature, were investigated by Rutherford backscattering spectrometry (RBS), x-ray θ ? 2θ diffraction patterns and x-ray φ scans, respectively. All measurements indicate that NdGaO₃single crystal, which used to be a substrate for the growth of high-T_c superconducting thin films, is also suitable for the growth of high quality PbTiO₃ thin film. This indicates the promising use of the NdGaO₃ for the integration of ferroelectric thin films and superconducting electrodes.     

基底显微结构对薄膜生长影响的Monte Carlo模拟研究

利用Monte Carlo方法研究了基底显微结构对薄膜生长的影响. 对不同显微结构基底上薄膜生长的初始阶段岛的形貌和尺寸与薄膜覆盖度和入射粒子沉积速率之间的关系进行了模拟和分析. 模型中考虑了粒子沉积、吸附粒子扩散和蒸发等过程. 结果表明,基底显微结构对薄膜生长具有明显影响. 当沉积温度为300K、沉积速率为0.005ML/s（Monolayer/second,简称ML/s）、覆盖度为0.05ML时,四方基底上薄膜生长呈现凝聚生长. 随着覆盖度增加,岛的尺寸变大,岛的数目减少. 而对于六方基底,当覆盖度从0.05ML变化到0.25ML时,薄膜生长经历了一个从分散生长过渡到分形生长的过程. 无论是四方还是六方基底,随着沉积速率的增加,岛的形貌由少数聚集型岛核分布状态向众多各自独立的离散型岛核分布状态过渡.     

Effects of interface between SnO2 thin film and Si substrate on growth time

SnO₂ thin film was grown on Si substrate using the low pressure chemical vapor deposition (LPCVD) method. The SnO₂ thin film was grown in the direction of (110) as deposition time increased. The atomic ratio of O decreased by 62.4, 57.6, and 45.6%, and the thickness of the thin film increased to 0.2, 0.3, and 0.7 ? as the deposition time increased to 10, 20, and 30 min, respectively. The interface of the thin film was examined using high-resolution transmission electron microscope (HRTEM) and energy dispersive spectroscopy (EDS) analysis. The SiO₂ layer was observed at between the SnO₂ thin film and the Si substrate. This layer decreased in thickness as the deposition time increased, which indicates that the deposition time affected the interface of the thin film.     

The power of in situ pulsed laser deposition synchrotron characterization for the detection of domain formation during growth of Ba0.5Sr0.5TiO3 on MgO

A highly sophisticated pulsed laser deposition (PLD) chamber has recently been installed at the NANO beamline at the synchrotron facility ANKA (Karlsruhe, Germany), which allows for comprehensive studies on the PLD growth process of dielectric, ferroelectric and ferromagnetic thin films in epitaxial oxide heterostructures or even multilayer systems by combining in situ reflective high‐energy diffraction with the in situ synchrotron high‐resolution X‐ray diffraction and surface diffraction methods. The modularity of the in situ PLD chamber offers the opportunity to explore the microstructure of the grown thin films as a function of the substrate temperature, gas pressure, laser fluence and target–substrate separation distance. Ba_0.5Sr_0.5TiO₃ grown on MgO represents the first system that is grown in this in situ PLD chamber and studied by in situ X‐ray reflectivity, in situ two‐dimensional reciprocal space mapping of symmetric X‐ray diffraction and acquisition of time‐resolved diffraction profiles during the ablation process. In situ PLD synchrotron investigation has revealed the occurrence of structural distortion as well as domain formation and misfit dislocation which all depend strongly on the film thickness. The microstructure transformation has been accurately detected with a time resolution of 1 s. The acquisition of two‐dimensional reciprocal space maps during the PLD growth has the advantage of simultaneously monitoring the changes of the crystalline structure as well as the formation of defects. The stability of the morphology during the PLD growth is demonstrated to be remarkably affected by the film thickness. A critical thickness for the domain formation in Ba_0.5Sr_0.5TiO₃ grown on MgO could be determined from the acquisition of time‐resolved diffraction profiles during the PLD growth. A splitting of the diffraction peak into two distinguishable peaks has revealed a morphology change due to modification of the internal strain during growth.     

Transmission electron microscopy study of epitaxial La0.8MnO3 thin films on SrTiO3

The structure and microstructure of La_0.8MnO₃ thin films on SrTiO₃ substrates, fabricated by pulsed laser deposition at substrate temperatures of 873?K and 1073?K, have been studied by transmission electron microscopy. In both films, columnar growth morphology has been observed. The columnar grain size is found to increase with increasing substrate temperature. In the film deposited at a substrate temperature of 1073?K, there is only one rhombohedral phase. However, two phases, a rhombohedral one and an orthorhombic one, have been observed in the film deposited at 873?K.     

LaNiO3 under-electrode layers for the growth of textured (Pb0.4Zr0.6)TiO3 thin films using pulsed laser deposition

We investigated the structural properties of LaNiO₃ thin films of three different thicknesses deposited by pulsed laser deposition on Si(001) mainly by using a synchrotron X-ray scattering measurement. The LaNiO₃ thin films were grown with the (00l) preferred growth direction, showing completely random distribution in the in-plane direction. In the early stage of the growth, the film was almost unstrained. However, as the film grew further, tensile strain was markedly involved. Also its surface became rougher but its crystalline quality improved significantly with increasing film thickness. A completely (00l)-oriented (Pb_0.4Zr_0.6)TiO₃ thin film was successfully grown on such a LaNiO₃/Si(001) substrate at a substrate temperature of 350 °C by using the same pulsed laser deposition. Our results show that the LaNiO₃ film can serve effectively as a bottom electrode layer for the preparation of a well-oriented (Pb_0.4Zr_0.6)TiO₃ thin film on Si substrates.     

Electrical transport properties and laser-induced voltage effect in La0.8Ca0.2MnO3 epitaxial thin films

La_0.8Ca_0.2MnO₃ (LCMO) thin films about 200 nm thickness were grown on untilted and tilted (5°, 10° and 15°) LaAlO₃ (100) single crystal substrates by pulsed laser deposition technique. Electrical properties of the epitaxial thin films were studied by conventional four-probe technique and the anisotropic thermoelectric properties of the films grown on the tilted substrates have been investigated by laser-induced voltage (LIV) measurements. X-ray diffraction analysis and atomic force microscopy results show that the prepared LCMO thin films have a single phase and high crystalline quality. The remarkably large temperature coefficient of resistance (TCR) values (above 11 %/K) are observed in the all films. TCR value reaches 18 %/K on the film grown on 10° tilted substrate. The intensity of LIV signals monotonously increases with the tilting angles, and the largest signal is 148 mV with the fast time response 229 ns for the film grown on 15° tilted substrate.     

Amorphous film thickness dependence for epitaxy of perovskite oxide films under excimer laser irradiation

We have studied the epitaxial growth of perovskite manganite LaMnO₃ (LMO) on SrTiO₃(1 0 0) in the excimer laser assisted metal organic deposition process. The LMO was preferentially grown from the substrate surface by the KrF laser irradiation. The study of amorphous LMO film thickness dependence on epitaxial growth under the excimer laser irradiation revealed that the photo-thermal heating effect strongly depended on the amorphous film thickness due to a low thermal conductivity of amorphous LMO: the ion-migration for chemical bond-forming at the reaction interface would be strongly enhanced in the amorphous LMO film with the large film thickness about 210 nm. On the other hand, the photo-chemical effect occurred efficiently for the amorphous film thickness in the range of 35-210 nm. These results indicate that the epitaxial growing rate was dominated by the photo-thermal heating after the photo-chemical activation at the growth interface.     

Influence of the thickness on structural,magnetic and electrical properties of La0.7Ca0.3MnO3 thin film

We have studied the effect of thickness on the structural, magnetic and electrical properties of La_0.7Ca_0.3MnO₃ thin films prepared by pulsed laser deposition method using X-ray diffraction, electrical transport, magneto-transport and dc magnetization. X-ray diffraction pattern reflects that all films have c-axis epitaxial growth on LaAlO₃ substrate. The decrease in out-of-plane cell parameter specifies a progressive relaxation of in the plane compressive strain as the film thickness is increases. From the dc magnetization measurements, it is observed that ferromagnetic to paramagnetic transition temperature increases with increase in the film thickness. Magneto-resistance and temperature coefficient of resistance increases with film thickness and have maximum value near its metal to insulator transition temperature.     

A new approach to the synthesis of functional thin films: Hierarchical synthesis of CaCO3 thin films and their transformation into patterned metal thin films

A patterned metal thin film was synthesized based on a new approach that allows the formation of thin films with complex shape, hierarchical organization, and controlled size under ambient conditions in an aqueous environment. By using a general coating system, a CaCO₃ thin film was transformed into a patterned metal thin film with functional properties, such as adhesion and hydrophobicity. Atomic force microscopy (AFM) and surface-profiling experiments were carried out to measure the adhesion between the probe tip and the substrate and to determine the film thickness. Separation of the patterned ceramic thin film occurred very easily by means of sputtering and chemical treatment with an acidic solution.     

Thickness dependent magnetic and ferroelectric properties of LaNiO3 buffered BiFeO3 thin films

BiFeO₃ (BFO) thin films with thickness increasing from 40 to 480 nm were successfully grown on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si(100) substrate and the effects of thickness evolution on magnetic and ferroelectric properties are investigated. The LNO buffer layer promotes the growth and crystallization of BFO thin films. Highly (100) orientation is induced for all BFO films regardless of the film thickness together with the dense microstructure. All BFO films exhibited weak ferromagnetic response at room temperature and saturation magnetization is found to decrease with increase in film thickness. Well saturated ferroelectric hysteresis loops were obtained for thicker films; however, the leakage current dominated the ferroelectric properties in thinner films. The leakage current density decreased by three orders of magnitude for 335 nm film compared to 40 nm film, giving rise to enhanced ferroelectric properties for thicker films. The mechanisms for the evolution of ferromagnetic and ferroelectric characteristics are discussed.     

测量高温超导YBCO薄膜厚度的一种新方法

生长在倾斜SrTiO₃衬底上的YBCO薄膜具有激光感生电压效应,响应信号的衰减时间常量与薄膜的厚度有确定的关系.作出了衰减时间常量与薄膜厚度的关系曲线,根据该曲线,由衰减时间常量就可确定薄膜的厚度     

In situ RHEED analysis of epitaxial Gd2O3 thin films grown on Si (001)

Epitaxial Gd₂O₃ thin films were successfully grown on Si (001) substrates using a two-step approach by laser molecular-beam epitaxy. At the first step, a ～0.8 nm thin layer was deposited at the temperature of 200 ^°C as the buffer layer. Then the substrate temperature was increased to 650 ^°C and in situ annealing for 5 min, and a second Gd₂O₃ layer with a desired thickness was deposited. The whole growth process is monitored by in situ reflection high-energy electron diffraction (RHEED). In situ RHEED analysis of the growing film has revealed that the first Gd₂O₃ layer deposition and in situ annealing are the critical processes for the epitaxial growth of Gd₂O₃ film. The Gd₂O₃ film has a monoclinic phase characterized by X-ray diffraction. The high-resolution transmission electron microscopy image showed all the Gd₂O₃ layers have a little bending because of the stress. In addition, a 5–6 nm amorphous interfacial layer between the Gd₂O₃ film and Si substrate is due to the in situ high temperature annealing for a long time. The successful Gd₂O₃/Si epitaxial growth predicted a possibility to develop the new functional microelectronics devices.     

Epitaxial strain-induced magnetic anisotropy in Sm3Fe5O12 thin films grown by pulsed laser deposition

Sm₃Fe₅O₁₂ thin films of various thicknesses were grown on a (0 0 1)-oriented Gd₃Ga₅O₁₂ substrate by pulsed laser deposition. The crystal structure of the films was strongly dependent on film thickness. The lattice was strained for thinner films due to a lattice mismatch between the film and substrate. This lattice strain was relaxed when the film thickness exceeded a critical thickness of around 660 Å. It is suggested that the epitaxial strain induces uniaxial magnetic anisotropy with an out-of-plane magnetic easy axis.     

Large area excimer laser induced deposition of titanium from titanium tetrachloride

Large area excimer laser induced deposition of titanium on fused silica from TiCl₄ is studied with an emphasis on process modeling. We show that several TiCl₄ monolayers can be adsorbed if the surface is adequately prepared and that the Ti thin film growth occurs through the photodecomposition of this adsorbed TiCl₄ layer. We propose two growth regimes. During an initiation phase, up to 3 nm in thickness, the adsorbed layer is photochemically decomposed giving a growth rate of 0.015 nm/pulse. In a second phase, the deposition rate increases to between 2 and 7 nm/pulse due to the laser heating of the preceding photochemically deposited titanium film. Between consecutive pulses, TiCl₄ molecules primarily from the adsorbed layer diffuse to the reaction zone leading to a new adsorbed layer ready to be transformed to solid titanium.     

The characteristics of surface acoustic waves on AlN/LiNbO3 substrates

The characteristics of surface-acoustic-wave (SAW) devices on various substrates were measured by a network analyzer in the temperature range from 0 to 80 °C. Based on the structure of IDT/AlN/LiNbO₃, it was revealed that the magnitude of the temperature coefficient of frequency (TCF) of a SAW on a LiNbO₃ substrate was significantly decreased due to the thickness increase of AlN thin film deposited on the LiNbO₃ substrate. The TCF of a SAW on an AlN/LiNbO₃ device was measured to be about -51 ppm/°C at h/λ=0.1, where h is the thickness of the AlN film and λ is the wavelength of the SAW. This indicates that the deposition of an AlN film on a LiNbO₃ substrate could improve the temperature stability, as compared with that of a SAW on a LiNbO₃ substrate (-73 ppm/°C). The SAW device on the ST-X quartz is shown to have a positive TCF as the AlN thin film is deposited on the surface of the ST-X quartz. In addition, the phase velocity (V_p) of the SAW on an AlN/LiNbO₃ substrate was significantly increased by the increase of AlN thickness (h/λ). Received: 14 October 2002 / Accepted: 15 October 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. Fax: +886-7/525-4199, E-mail: ycc@ee.nsysu.edu.tw