Chemical solution processing and properties of tungsten bronze (ba,la)nb2o6 thin films

Abstract

Highly oriented (Ba,La)Nb₂O₆ thin films have been synthesized by a chemical solution deposition method. A homogeneous and stable (Ba_0.75La_0.167)Nb₂O₆ (BLN) precursor solution was prepared by controlling the reaction of metal alkoxides. BLN precursor films crystallized in the tetragonal tungsten bronze phase at 700°C. BLN thin films on MgO(100) and Pt(100)/MgO(100) substrates showed the prominent c-axis preferred orientation. BLN thin films on Pt(100)/MgO(100) exhibited the diffuse phase transition depending upon the frequency.     

Pyroelectric infrared sensors made of La-modified PbTiO3 thin films and their applications

Abstract

High sensitive pyroelectric infrared (IR) sensors have been fabricated by using c-axis oriented La-modified PbTiO₃ (Pb_1–xLa_xTi_1?x/4O₃, PLT) thin films. The PLT thin films were deposited on (100)-cleaved MgO single crystal substrates by intermittent rf-magnetron sputtering method. The PLT thin films have high figures of merit for IR sensor without a poling treatment. High performance pyroelectric IR sensors (single element type and linear array type) were fabricated by using PLT (x=0·1, γ=5·5x10^?8 C/cm²K, ?_r=200) thin films. The sensors have remarkably high D* of 3–6x10⁸ cmHz^1/2/W and very fast response. A new compact IR sensing system using the linear array sensor (8 elements) has been developed for a new type of room air-conditioner. This system can measure thermal distribution (8x64) by horizontal scanning of the vertical linear array. Image processing with neural network concept makes possible high-accuracy using a few data from the sensor elements. This sensing system provides ‘‘smart airconditioning'’to improve the comfortable control.     

Microstructural Properties of Ba0.6Sr0.4TiO3/RuO2 Multi-Layers Grown on MgO and YSZ by Pulsed-Laser Deposition

The microstructure of Ba_0.6Sr_0.4TiO₃ (BST)/RuO₂ multi-layers grown on (100) MgO and (100) YSZ substrates, respectively, by pulsed-laser deposition (PLD) has been studied by transmission electron microscopy (TEM) and high-resolution electron microscopy (HREM). The RuO₂ films deposited at 700°C adopt epitaxial relationships with both substrates. The epitaxial films on (100) MgO consist of two variants with an orientation relationship given by (110) RuO₂//(100) MgO and [001] RuO₂//[011] MgO. The epitaxial films on (100) YSZ contain four variants with an orientation relationship given by (200) RuO₂//(100) YSZ and [011] RuO₂//[001] YSZ. The BST films deposited on the RuO₂ electrode are epitaxial on the (200) RuO₂ films deposited on YSZ, and non-epitaxial on the (110) RuO₂ films deposited on MgO. The epitaxial relationship between the BST and (200) RuO₂ films can be described as (111) BST//(200) RuO₂ and [1&1macr;0] BST//[011] RuO₂. The BST films contain at least four variants. The growth and microstructural properties of the multi-layer structures can be understood based on geometrical consideration of the crystal structures.     

Improved ferroelectricity of strained SrTiO3 thin films on sapphire

Magnetron sputtered and laser deposited SrTiO₃ thin films are deposited on CeO₂ buffered sapphire substrates. Their structural properties are investigated and correlated to the dielectric properties of the SrTiO₃ films. It is shown, that the biaxial compressive strain imposed by the substrate on the ferroelectric films leads to a considerable increase of the permittivity and tunability of SrTiO₃ thin films in technically relevant temperature regimes. Generally, the permittivity and tunability decreases with increasing strain. However, the ferroelectric phase transition of the SrTiO₃ films is shifted to higher temperatures compared to that of single crystalline SrTiO₃. As a consequence, the permittivity of the films is larger than that of undistorted SrTiO₃ single crystals for small strain (Δa/a < 0.005) and temperatures above the Curie temperature. Furthermore, a linear dependence of the loss tangent and the tunability on the permittivity is observed, which indicates, that all three properties are affected by the same mechanism that itself is affected by the lattice strain.     

Preparation of BaPbO3 Electrode Thin Films by RF Magnetron Sputtering

For electrode materials of Pb(Zr,Ti)O₃ (PZT) thin films in ferroelectric random access memory (FeRAM), various materials have been studied. As new electrode material with which the polarization and fatigue properties are improved, we take notice of barium metaplumbate BaPbO₃ (BPO). Because the BPO contained lead (Pb) and oxygen is conductor that adopted same perovskite structure as PZT. BPO thin films were prepared by rf magnetron sputtering on various substrates. (SiO₂/Si, MgO, Al₂O₃ and Pt-coated substrates), and influence of growth conditions (sputtering gas, rf power, the substrate-heating temperature and post anneals) on crystallization and conductivity were investigated. In case of post anneal after sputtering at room temperature, perovskite single phase was obtained above 400°C. In case of substrate heating while sputtering, without post anneal, perovskite single phase was obtained at 350–500°C on SiO₂/Si substrates (110) preferred orientation BPO films obtained at low temperature, and resistivity of the films decreased at decreasing sputtering temperature. Resistivity of the film at substrate temperature 350°C was 3 × 10^?3 Ω cm. In the case of single crystal substrate, the BPO films were epitaxially grown. Orientation of the films was varied with the sputtering condition. The epitaxial PZT thin films were also grown on the BPO, revealing that PZT(111)[011] //BPO(111)[011] //Pt(100)[011] //MgO(100)[011] and PZT(111)[011] //BPO(111)[011] //Pt(111)[011] //Al₂O₃(001)[100] structures were obtained, and their ferroelectric properties were also evaluated.     

Microstructures and pyroelectric properties of (Pb,La)TiO3 thin films grown on MgO and ON Pt/MgO

Abstract

Comparison has been made between the microstructures and electrical properties of Pb_0·95La_0·05TiO₃ (PLT) thin films deposited on bare (100)MgO and on Pt/(100)MgO. Nearly perfect epitaxial PLT was grown on (100)MgO. (100)-oriented Pt film was obtained via coalescence of Pt islands formed on MgO. Highly c-axis oriented PLT thin film was successfully grown on the Pt bottom electrode with an electrically conductive network structure. High detectivity of 3·5 × 10⁸ and 2·6 × 10⁸ cm√Hz/W was obtained at 30 Hz without any poling treatments from the PLT/MgO- and PLT/Pt/MgO-based infrared detectors, respectively.     

Chemical solution processing of sr2(nb,ta)2o7 thin films

Abstract

Sr₂(Nb,Ta)₂O₇ thin films have been synthesized by chemical solution deposition. Homogeneous and stable Sr₂(Nb,Ta)₂O₇ precursor solutions with various Nb/Ta ratios were prepared by controlling the reaction of metal alkoxides in ethanol with a key additive of 2-ethoxyethanol. The crystallization temperature of the perovskite-type Sr₂(Nb,Ta)₂O₇ slabs structure decreased with increasing Nb substitution in amount. The crystallization temperature of Sr₂(Nb_0.2Ta_0.8)₂O₇ films on Pt/Ti/SiO₂/Si and Pt/Ir/Ti/SiO₂/Si substrates was above 800°C. On the other hand, by using Pt(100)/MgO(100) as a substrate, Sr₂(Nb,Ta)₂O₇ thin films crystallized into the Sr₂(Nb,Ta)₂O₇ phase at 700°C.     

Growth of MgTiO3 thin films by pulsed laser deposition and their electrical properties

Abstract

MgTiO₃ thin films have been grown on various substrates by pulsed laser deposition (PLD) to investigate the application for microwave dielectrics and optical devices. Highly oriented MgTiO₃ thin films were obtained on sapphire (c-plane Al₂O₃). MgTiO₃ thin films deposited on SiO₂/Si and platinized silicon (Pt/Ti/SiO₂/Si) substrates were polycrystalline nature. MgTiO₃thin films grown on sapphire were transparent in the visible and had a sharp absorption edge at 280 nm. These MgTiO₃ thin films had extremely fine feature of surface morphology, i.e., rms roughness of 0.87 nm. Dielectric constant and loss of MgTiO₃ thin films deposited by PLD were about 24 and 1.5% at 1MHz, respectively. These MgTiO₃ thin films also exhibited little dielectric dispersion.     

Textured LaNiO3 Electrode Grown by Spin-Coating Technique

LaNiO₃ thin films were deposited by spin-coating technique on various substrates using metal naphthenates as starting materials. The highly oriented LaNiO₃ films with smooth and crack-free surfaces grown on SrTiO₃(100) and LaNiO₃(012) substrates were observed by X-ray diffraction –2 scans, while the film on sapphire(0001) substrate showed polycrystalline structure. Resistivity vs. temperature curves of the textured LaNiO₃ films showed that the film possessed a good metallic character.     

Epitaxially grown ferroelectric thin film capacitors for sensing applications

Abstract

Pyroelectric infrared detectors based on La-modified PbTiO₃ (PLT) thin films have been fabricated by RF magnetron sputtering and micromachining technology. The detectors form PB_1?xLa_xTi_1?x/4O₃ (x = 0.05) thin film ferroelectric capacitors epitaxially grown in-situ by RF magnetron sputtering on Pt/ MgO(100) substrate. The sputtered PLT thin film exhibits highly c-axis oriented crystal structure (90%) that poling treatment for sensing applications is not required. The c-axis orientation ratio a of deposited PLT thin film strongly depends on the morphology of Pt layer, which in turn varies with the thickness of Pt layer on MgO substrate. We have successfully grown highly c-axis oriented PLT film on Pt electrode with a conductive percolating network structure. Micromachining technology is used to lower the thermal mass of the detector by coating Polyimide on top of the sensing elements to support the fragile structure and by selectively etching the backside of the MgO substrate to reduce the heat loss. The sensing element exhibited a low noise equivalent power (NEP) of 1.7 × 10^?10 W and a very high detectivity D? value of 8.5 × 10⁸ cmVHz/W at room temperature. The high performance for pyroelectric infrared sensing is primarily due to the highly c-axis oriented PLT thin film and its minimized thermal mass.     

Temperature dependence of mechanical deformations in strontium titanate thin film on the sapphire substrate

Abstract

The temperature dependence of the dielectric constant (ε) of SrTiO₃ films on the various dielectric substrates differs radically from ε(T) dependence for bulk single crystal. This difference may be connected with temperature dependence of mechanical stress in the film. XRD measurements suggest the high mechanical deformation (u) of STO film unit cells at room temperature. But there is no experimental data about dependence u(T) nowadays. Present work is devoted to investigation of temperature and electric field dependencies of capacitance (C(U,T), C(Q,T)) of capacitor on the structure STO film/sapphire substrate. It is shown that derivative of inverse capacitance on the temperature is not constant and has a maximum at temperature about 200 K. Position of maximum is not influenced by charge (Q_i) on the capacitor. The mechanical deformations play the dominant role in the formation of maximum. The temperature behavior of macroscopic mechanical deformations in STO thin film on sapphire substrate is discussed.     

Preparation of SrBi2Ta2O9 ferroelectric thin film by rf magnetron sputtering

Abstract

SrBi₂Ta₂O₉ (SBT) thin films were deposited on 6-inch Pt/Ti/SiO₂/Si substrates by rf magnetron sputtering using a 12-inch ceramic SBT single target. It is found that several sputtering parameters such as argon (Ar) pressure and rf power were very effective to control the Bi content of SBT thin films which is essential for obtaining good ferroelectric properties.     

Preparation of ferroelectric thin films for Si-based devices

Abstract

Lead titanate (PbTiO₃) thin films have been prepared on titanium dioxide coated silicon wafers by chemical vapor deposition (CVD). The pure PbTiO₃ thin films were deposited by controlling the experimental conditions. The gas phase reaction of TiO₂ occurred by exceeding the critical value of titanium input fraction at constant oxygen partial pressure. Strontium titanate (SrTiO₃) thin films have been prepared on p-type silicon wafers by radio frequency (RF) magnetron sputtering. The SrTiO₃ thin film was polycrystalline and the Sr/Ti ratio of this film was 0.91. The SrTiO₃ thin films contain three regions, an external surface layer, a main layer and an interfacial layer. The stoichiometric SrTiO₃ thin film was obtained by using the SrO excess target. The SrTiO₃ film annealed at 600[ddot]C has an ideal capacitance-voltage (C-V) curve and maximum effective dielectric constant.     

Growth and characterization of non-c-axis-oriented SrBi2Ta2O9 epitaxial thin films on Si(100) substrates with SrRuO3 bottom electrodes

Abstract

We have successfully grown non-c-axis-oriented epitaxial ferroelectric SrBi₂Ta₂O₉ (SBT) films with (116) and (103) orientations on Si(100) substrates using epitaxial (110)- and (111)-oriented SrRuO₃ (SRO) bottom electrodes, respectively. The SRO orientations have been induced by coating the Si(100) substrates with epitaxial YSZ(100) and MgO(111)/ YSZ(100) buffer layers, respectively. All films were sequentially grown by pulsed laser deposition. Specific in-plane orientations of the epitaxial SBT films were found, which are in turn determined by specific in-plane orientations of the epitaxial SRO bottom electrodes. These include a diagonal rectangle-on-cube epitaxy of SRO(110) on YSZ(100) and a triangle-on-triangle epitaxy of SRO(111) on MgO(111).     

Influence of deposition parameters on physico-chemical and optical properties of sputtered PbTiO3 thin films

Abstract

Stoichiometric thin films of lead titanate (PbTiO₃) have been grown “in situ” without postannealing on (0001) sapphire substrates by rf magnetron sputtering technique. X-ray diffraction scans have revealed that as-grown films consist of the perovskite phase and are polycrystalline with a high (111) orientation. The structure, the microstructure and the optical properties have been studied as a function of the process parameters i.e., substrate temperature, gas pressure and the target composition, in particular the lead content. We report the dependence of the deposition conditions on the optical constants. The optimum experimental conditions (100m Torr and 600°C) to produce thin films with high transparency and refractive indices (n = 2.61 at 633 nm), similar to values for bulk materials, are given in this paper.     

Epitaxial growth of multilayered (Bi,La)4Ti3O12/Pb(Zr,Ti)O3 ferroelectric thin films with different orientations

Epitaxial (Bi,La)₄Ti₃O₁₂ (BLT) thin films, epitaxial Pb(Zr,Ti)O₃ (PZT) thin films, and epitaxial multilayered BLT/PZT ferroelectric thin films with different orientations were prepared on SrTiO₃ (STO) single crystal substrates by pulsed laser deposition. From X-ray pole-figures and electron diffraction patterns, the epitaxial orientation relationships between BLT layers, PZT layers, and STO substrates were identified to be (1) BLT(001)//PZT(001)//STO(001), and BLT[110]//PZT[100]//STO[100] for the multilayered thin films on (001)-oriented STO substrates, and (2) BLT(118)//PZT(011)//STO(011), and $ {\text{BLT}}{\left[ {\overline{1} \overline{1} 0} \right]}//{\text{PZT}}{\left[ {100} \right]}//{\text{SrTiO}}_{3} {\left[ {100} \right]} $ for the multilayered films on (011)-oriented STO substrates. Tri-layered films of the same compositions showed well-defined hysteresis loops as well as a high fatigue resistance up to 1?×?10¹⁰ switching cycles.     

Selective orientation of SrBi4Ti4O15 thin films grown on buffered Si(100) substrates

Many efforts have been paid to uncouple the spontaneous polarizations of layer-structured bismuth-based ferroelectrics along different crystal orientations, obtaining these layered-structure films with non-c-axis orientations. In the paper, SrBi₄Ti₄O₁₅ (m?=?4) thin films have been deposited on Pt/MgO bilayer-buffered Si(100) substrates by pulsed-laser deposition. Selective orientation of SrBi₄Ti₄O₁₅ thin films mediated by different epitaxy relationships between electrode layers and MgO/Si substrates has been demonstrated. Furthermore, different hysteresis loops and remnant polarization of SrBi₄Ti₄O₁₅ thin films with varied orientations have been obtained.     

Strain tensor effects on SrTiO3 incipient ferroelectric phase transition

Structural distortion of ferroelectric thin films caused by film strain has a strong impact on the microwave dielectric properties. SrTiO₃ thin films epitaxially grown on (110) DyScO₃ substrates using molecular beam epitaxy (MBE) are extremely strained (i.e., ～1% in-plane tensional strain) from 3.905 Å of bulk SrTiO₃. The room temperature dielectric constant and its tuning of the films are observed to be 6000 and 75% with an electric field of 1 V/μm, respectively. The control of strain in SrTiO₃ provides a basis for room temperature tunable microwave applications by elevating its phase transition peak to room temperature. Also, a significant in-plane anisotropy in dielectric constant and tuning was observed in these SrTiO₃ films. The observed in-plane anisotropic dielectric properties have been interpreted based on the phenomenological thermodynamics of film strain.     

Preparation and properties of sputtered lead titanate thin films on MgO single crystals and mgo buffer layers

Abstract

By means of planar multitarget sputtering (001) oriented PbTiO₃ films were deposited onto highly preferred (100) oriented platinum electrodes on (100) MgO single crystal substrates. Single phase perovskite type films with a degree of (001) orientation between 60% and 70% have been sputtered at substrate temperatures as low as about 470°C. The as grown films exhibit a dielectric constant in the range of 120 to 140 and a pyroelectric coefficient of about 20 nCcm^?2K^?1 at room temperature. The dielectric loss is about 0.01 at frequencies from 1 to 10 kHz. (100) GaAs substrates with an evaporated, highly oriented (100) MgO buffer layer were also used as substrates. However, on these substrates the platinum bottom electrode did not grow highly oriented though the same deposition parameters for Pt deposition as in the case of the single crystalline MgO substrate were used. That's why PbTiO₃ was produced with a lower (001) preferred orientation. Therefore, the dielectric constant is higher (170–190) and the pyroelectric coefficient is lower (12 nCcm^?2K^?1).     

Substrate Surface Engineering for Functional Ceramic Thin Film Growth

A concept is introduced, using oxide substrates for functional ceramic thin film deposition beyond their usual application as chemical inert, lattice-matched support for the films. The substrates are applied as a functional element in order to controllably modify the atom arrangement and the growth mode of cuprate superconductors and colossal magnetoresistance materials. These materials have been chosen as prototypes of the general class of perovskite functional ceramics. One example studied is the use of epitaxial strain to adjust the relative positions of cations and anions in the film and thus modify their physical properties. The other makes use of vicinal cut SrTiO₃ which enables the fabrication of regular nanoscale step and terrace structures. In YBa₂Cu₃O_{7 – x} thin films grown on vicinal cut SrTiO₃ single crystals a regular array of antiphase boundaries is generated causing an anisotropic enhancement of flux-line pinning. In the case of La-Ca-Mn-O thin films grown on vicinal cut substrates it could be demonstrated that magnetic in-plane anisotropy is achieved.