Excess Bismuth-Dependent Characteristics of Chemical Solution Deposited Bi3.15La0.85Ti3O12 Thin Films

The phase formation and electrical properties of (Bi_3.15La_0.85)Ti₃O₁₂ (BLT) thin films prepared by the chemical solution deposition method on Pt/Ti/SiO₂/Si substrates have been investigated. It was observed that the microstructure and electrical properties of BLT thin films dramatically varied with the excess Bi content. The crystallographic orientation of BLT films was varied with excess Bi content and the intermediate rapid thermal annealing (RTA) process. While BLT thin films prepared without intermediate RTA process have ?117? orientation irrespective of excess Bi content, BLT thin films with RTA process at 450°C have an orientation change with excess Bi content. The leakage current of BLT thin films slightly increased with increasing excess Bi content up to 6.5% and then considerably decreased in BLT film with 10% Bi, where was revealed to be almost stoichiometric composition.     

Phase Formations and Electrical Properties of Various (Bi, La)4Ti3O12 Thin Films by Chemical Solution Deposition

The phase formation and electrical properties of (Bi, La)₄Ti₃O₁₂ (BLT) thin film and V-, Sm-doped BLT thin films prepared by the chemical solution deposition method on Pt/TiO₂/SiO₂/Si substrates have been investigated. It was observed that the microstructure and electrical properties of BLT thin films dramatically varied with V- and Sm-doping. The crystallinity and grain size of BLT thin films were definitely increased by V- and Sm-doping into BLT films, which resulted in the enhancement of remanent polarization in doped BLT films. The remanent polarization (Pr) of Sm-doped BLT films annealed for 3 min by an RTA system was about 9 C/cm². The V- and Sm-doped BLT films also exhibited good fatigue characteristics under bipolar stressing to 10¹⁰ cycles.     

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.     

Effect of vanadium doping on ferroelectric and electrical properties of Bi3.25La0.75Ti3O12 thin film

Bi_3.25La_0.75Ti₃O₁₂ (BLT) and V-doped BLT (BLTV) thin films were prepared on Pt/Ti/SiO₂/Si substrates by a pulsed laser deposition method. The effects of V doping on ferroelectric and electrical properties were investigated by polarization-electric field hysteresis loops and leakage current-voltage measurements. BLTV single phases were confirmed by X-ray diffraction. Remnant polarization was increased and the leakage current density was decreased by V doping. The leakage current density of BLT thin films suddenly increased at 100 kV/cm while that of BLTV thin films increased at the higher electric field of 160 kV/cm. The power law relationship J α Eⁿ of current density vs. applied electric field is estimated to be J αE^2.0 for BLT and J αE^1.0 for BLTV thin films. The leakage current of the BLT/Pt junction can be explained by space-charge-limited current. However, that of the BLTV/Pt junction was characterized by the Schottky emission behavior.     

Inverse Capacitance-Voltage Characteristics of Bi3.25La0.75Ti3O12 Thin Film Pulsed Laser Deposited on Thermally Oxidized n-Type Si Substrates

Comparative studies on the electrical properties of a metal-ferroelectric-insulator-semiconductor field effect transistor were conducted using pulsed laser ablated ferroelectric Bi_3.25La_0.75Ti₃O₁₂ (BLT) thin films deposited on SiO₂/Si substrates with different SiO₂ thicknesses. The SiO₂ layer was prepared on n-type Si substrates by dry oxidation at a temperature of 800°C. Small angle x-ray reflectivity studies were used to measure the SiO₂ thickness. The capacitance-voltage (C-V) measurements revealed that the films showed good interfacial properties. Shifts in flatband voltages were observable, but were effectively reduced by deposition of the ferroelectric films. Au/BLT/SiO₂/Si diodes with 8 nm SiO₂ layer showed to be stable with relatively large memory window values of about 0.3 V, 2.5 V, 5.0 V, and 7.0 V, at increasing bias voltages of ±5 V, ±7 V, ±10 V, and ±12 V, respectively.     

Fabrication and evaluation of LaCrO3 thin film heaters

Lanthanum chromium oxide (LaCrO₃) has excellent high‐temperature properties. LaCrO₃ doped with alkaline earth metals also has high electric conductivity. The purpose of this study is to fabricate thin film heaters using LaCrO₃ doped with Ca by RF magnetron sputtering method. The crystal structure of thin films was evaluated and the surface form was studied. The results show that the thin film deposited on Si(100) single crystal and quartz glass substrates in Ar gas had a strong orientation and that its surface form was comparatively smooth. The crystal structure of the thin films deposited on Si(100) and quartz glass substrate at temperatures of 700 and 800 °C by sputtering in a mixture of Ar and O₂ gases was the same as the crystal structure of LaCrO₃. The heating characteristics of a thin film heater on Si(100) substrate with Pt electrodes were evaluated by measurement of the equilibrium temperature‐current (T–I) and resistance‐equilibrium temperature (R–T) characteristics. The maximum equilibrium heating temperature was about 1100 °C. © 2002 Wiley Periodicals, Inc. Electr Eng Jpn, 139(3): 18–25, 2002; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.1156     

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.     

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.     

Micro-structure and ferroelectric properties of BiFeO3 thin films formed on Pt-coated r-plane sapphire substrates

Magnetoelectric BiFeO₃ (BFO) materials exhibit ferroelectric and ferromagnetic properties simultaneously, therefore they have a potential to be applied in magnetic as well as ferroelectric devices. BFO thin films were formed by depositing sol-gel solutions on Pt-coated r-plane sapphire dielectric substrates. We did not observe any secondary phase such as Bi₂Fe₄O₉ on the r-plane sapphire substrates, which is generally observed on Si substrates. We observed small ferroelectric grains of about 0.1 μm on Pt/sapphire structures. The leakage current density in BFO films was found to be decreased dramatically after optimizing process conditions of stoichiometric BFO chemical solution. The leakage current densities were in the range of 10^{− 7} A/cm² at room temperature and 10^{− 9} A/cm² at 80 K under 0.4 MV/cm applied electric field. The main reason for low leakage current is considered to be reduction of oxygen vacancies due to the presence of exclusive Fe^{3 +} valance state in the films. An applied electric field higher than 0.5 MV/cm was required to pole the BFO films, which made it difficult to obtain the saturated polarization at room temperature. We could measure the saturated remanent polarization in the BFO films at 80 K and the obtained remanent polarization was 100 μC/cm².     

The Effect of La-Doped Bi4Ti3O12 Buffer Layer on Crystallinity and Ferroelectric Properties of PbZr0.58Ti0.42O3/Bi3.25La0.75Ti3O12 Multilayered Thin Films

PbZr_0.58Ti_0.42O₃ (PZT) ferroelectric thin films with Bi_3.25La_0.75Ti₃O₁₂ (BLT) buffer layer of various thickness were fabricated on Pt/TiO₂/SiO₂/p-Si(100) substrates by rf-magnetron sputtering method. The pure PZT film showed (111) preferential orientation in the XRD patterns, and the PZT/BLT films showed (110) preferential orientation with increasing thickness of the BLT layer. There were no obvious diffraction peaks for the BLT buffer layer, for its thin thickness in PZT/BLT multilayered films. There were the maximum number of largest-size grains in PZT/BLT(30 nm) film among all the samples from the surface images of FESEM. The growth direction and grain size had significant effects on ferroelectric properties of the multilayered films. The fatigue characteristics suggested that 30-nm-thick BLT was just an effective buffer layer enough to alleviate the accumulation of oxygen vacancies near the PZT/BLT interface. The comparison of these results suggests that the buffer layer with an appropriate thickness can improve the ferroelectric properties of multilayered films greatly.     

Improvement of heating characteristics of molybdenum silicide thin film electric heaters

Molybdenum silicide (MoSi₂) has an electrical conductivity as high as that of a metal, and greater chemical stability than that of, for example, SiC, in various atmospheres. Therefore, many kinds of MoSi₂ bulk‐type heaters are used in practical operations up to 1800^°C, which is higher than the temperature of SiC heaters. However, MoSi₂ is fragile at room temperature and has low creep resistance at high temperature. The purpose of this study is to fabricate heaters using thin films of MoSi₂ deposited on alumina substrates and crucibles by RF magnetron sputtering and to evaluate their characteristics. MoSi₂ thin film was deposited on the outside of an alumina crucible without heating the substrate and then Pt wire was attached using a Pt paste with sintering in a vacuum. This MoSi₂ thin film heater showed almost linear resistance–temperature (R–T) characteristics and a uniform heating state. It also showed good controllability of voltage and stability in the power–T characteristics for operations up to 1000^°C. However, at a heating temperature of 1300^°C, the heating area of MoSi₂ thin film decreased because of the reaction between Pt and MoSi₂ in the case of long‐term heating. Thus, Mo thin film was deposited as a buffer layer between Pt and MoSi₂ thin film to prevent such a reaction. This thin film heater showed good linear R–T characteristics up to 1200^°C. However, the temperature coefficient of resistance changed with repeated heating operation as a result of the diffusion of Mo atoms into MoSi₂. Thus, a thin film heater was fabricated with Mo₃Si, having a higher Mo content than MoSi₂. This heater showed a low degree of diffusion of Mo or Pt atoms into the thin film and had excellent practical characteristics up to 1000^°C. © 2009 Wiley Periodicals, Inc. Electr Eng Jpn, 168(2): 11–19, 2009; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20806     

Structure and dielectric properties of Ba(Sn0.2Ti0.8)O3 thin films grown on different substrates by a sol-gel process

Ba(Sn_0.2Ti_0.8)O₃ (BTS) thin films were deposited on Pt/Ti/SiO₂/Si and LaNiO₃/Pt/Ti/SiO₂/Si substrates by a sol-gel processing technique, respectively. The influences of substrates on the phase and microstructure of the thin films were examined. Dielectric properties of the thin films were investigated as a function of frequency and direct current electric field. The results showed that the substrates strongly influenced the microstructure and the dielectric properties of the films. The properties of BTS thin films on LaNiO₃/Pt/Ti/SiO₂/Si substrates were superior to that of the films grown on Pt/Ti/SiO₂/Si substrates.     

Preparation of Bi4Ti3O12 thin films by electron cyclotron resonance sputtering

Abstract

Ferroelectric Bi₄Ti₃O₁₂ thin films were deposited on Pt-coated oxidized Si substrate by electron cyclotron resonance (ECR) sputtering using ceramic targets. Crystal structure and dielectric properties of the films were investigated as functions of sputtering conditions such as substrate temperature and sputtering gas. Using a target with excess Bi content compared to stoichiometric composition was required to compensate Bi re-evaporation from the substrate and to obtain a perovskite single phase at 600°C. (117)-oriented films exhibited ferroelectric hysteresis loops. The remanent polarization and coercive field of the films were 9.8 μC/cm² and 180 kV/cm, respectively.     

Development of ferroelectric Pb(ZrxTi1−x)O3 thin films by metallo-organic decomposition process and rapid thermal annealing

Polycrystalline Pb(Zr_0.5Ti_0.5)O₃ thin films with good ferroelectric properties have been prepared by metallo-organic decomposition (MOD) process, using acetate-based precursors, and followed by two different kinds of annealing process, independently, including oven annealing and rapid thermal annealing (RTA). The experimental procedures were described for the films deposited on Pt-coated silicon substrates. There were distinct differences between oven annealing and RTA process, in terms of structures, morphologies, and electrical properties of the films. The films with RTA process showed denser and smoother surface, finer grain sizes, and much higher dielectric constant (1200–1400), remnant polarization of 30–35 μC/cm² and lower coercive field of 65–85 kv/cm in the entire annealing temperature range of this study. At an annealing temperature of 550°C, RTA processed films showed identical XRD patterns of perovskite phase and clear ferroelectricity; however, it was not possible to realize the perovskite structure and ferroelectricity in the films oven-annealed at that temperature. These acetate-derived PZT films with RTA process were reproducible, showed high quality in uniformity and homogeneity.     

Influence of rapid thermal annealing on pyrochlore/perovskite phase formation in laser ablated Pb(Zr,Ti)O3 thin films

Abstract

Pb(Zr,Ti)O₃ thin films were prepared by ArF excimer laser deposition on silicon and Pt-coated silicon substrates, and then were treated by rapid thermal annealing. The dependence of perovskite/pyrochlore phase formation on annealing conditions was investigated. The results show that the formation of perovskite phase or pyrochlore phase in the films was not only dependent on the heat treatment temperature, but also dependent on the heat treatment time. A wide range operational window of heat treatment time and temperature for obtaining single phase perovskite Pb(Zr,Ti)O₃ thin films was given, and the films were analyzed by Rutherford backscattering spectroscopy to explain this phase transition.     

Characterization of MOCVD Pt electrode for ferroelectric thin films

Abstract

Platinum thin films were deposited by low pressure chemical vapor deposition (LPMOCVD) on SiO₂/Si and (Ba, Sr)TiO₃/Pt/SiO₂/Si substrates using Pt-hexafluoroacetylacetonate at various deposition temperatures. The shiny mirror-like Pt thin films of a high electrical conductivity were obtained, when the deposition temperature is between 325°C and 350°C, whereas above 375°C Pt thin films showed rough surface as well as poor adhesion property to oxide substrate. Pt thin films had a good step coverage of 90%. The results indicate that LPMOCVD Pt thin films can be applied for the top electrode of high dielectric thin film, which is thought to be one of the best candidate materials for a capacitor of ULSI DRAM.     

Optical Properties of LiTaO3 Thin films crystallized by RTA processes

High-performance pyroelectric infrared detectors have been fabricated using Lithium tantalite (LiTaO₃) thin films deposited on Pt(111)/Ti/SiO₂/Si(100) substrates by diol-based sol-gel method and rapid thermal annealing (RTA) technique. The dielectric and pyroelectric properties of IR detectors of LiTaO₃ thin films crystallized by conventional and RTA processes are investigated. Experimental results reveal that the heating rate will influence strongly on dielectricity and pyroelectricity of LiTaO₃ thin films. The voltage responsivities (Rv) measured at 80 Hz increase from 5496 to 8455 V/W and the specific detecivities (D^∗) measured at 300 Hz increase from 1.94 × 10⁸ to 2.38 × 10⁸ cmHz^1/2/W with an increase of heating rate from 600 to 1800^∘C/min. However, the voltage responsivity and the specific detecivity decrease with heating rate in excess of 1800^∘C/min. The results show that the LiTaO₃ thin film detector with a heating rate of 1800^∘C/min exists both the maximums of voltage responsivity and specific detecivity.     

EFFECTS OF PZT BUFFER LAYERS ON PZFNT FERROELECTRIC THIN FILMS

ABSTRACT

PZFNT thin films were fabricated on 5-inch Pt/Ti/SiO₂/Si and PZT/Pt/Ti/SiO₂/Si substrates by RF magnetron sputtering method and rapid thermal annealing process. By investigating the two thin films at various annealing temperatures, the results show that the annealing temperature of PZFNT thin films without PZT buffer layers is about 730°C, which is higher than that of PZFNT films with PZT buffer layers. By use of PZT buffer layers, the annealing temperature of PZFNT films is decreased greatly, and the dielectric and ferroelectric properties are improved. In the optimum process, the thin films with PZT buffer layers have a dielectric constant of 1199 and dielectric loss of 3.0% at 1 KHz. The remanent polarization and coercive field of the thin films are 21.1 μC/cm² and 53.5 KV/cm respectively. The films have the significant potential for FRAM and pyroelectric infrared detectors.     

Pyroelectric properties of sol-gel derived PZT thin films with various Zr/Ti ratios

Abstract

Integrated pyroelectric arrays are receiving serious attention for the next generation of room temperature uncooled IR cameras. Such pyroelectric arrays are based on monolithic ferroelectric(FE) thin films. FE films with large values of reported pyroelectric coefficients include PbTiO₃, Ca-doped PbTiO₃, La-doped PbTiO₃, PZT 53/47 and Pb(Sc_0.5Ta_0.5)O₃. The present paper reports a systematic study of the compositional dependence of PZT thin films on their pyroelectric properties. A series of sol-gel derived PZT (lead zirconate titanate) thin films with various Zr/Ti ratios, namely, PbTiO₃, PZT 20/80, PZT 35/65, PZT 53/47, PZT 65/35, PZT 92/8 and PbZrO₃, were prepared on platinized Si substrates. The films were fired to 650 – 700°C to crystallize them into single-phase perovskite. The degree of preferred orientation, grain size and firing temperature affect the pyroelectric responses. Pyroelectric coefficients as large as 2.5 × 10^?8 C/cm²-K were obtained, making such PZT thin films attractive in pyroelectric arrays.     

PREPARATION AND PROPERTIES OF LITHIUM-DOPED K0.5Na0.5NbO3 THIN FILMS BY CHEMICAL SOLUTION DEPOSITION

ABSTRACT

Lithium-doped K_0.5Na_0.5NbO₃ (KLNN) films were fabricated by chemical solution deposition on Pt/TiO₂/SiO₂/Si substrates. Homogeneous and stable precursor solutions were prepared by controlling the reaction of starting metal alkoxides. Perovskite KLNN single-phase thin films were successfully synthesized on Pt/TiO _x /SiO₂/Si substrates. The 0.75-μ m-thick KLNN film annealed at 650°C exhibited ferroelectric polarization hysteresis loops at ?250°C. The loop at room temperature was round, indicating the film contained leakage components. The dielectric constant under zero bias was 490 at room temperature. A typical upside-down butterfly DC bias-capacitance curve was obtained in the KLNN film capacitors at room temperature, indicating that polarization reversal occurred in the obtained KLNN films.