Preparation of Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films by MOCVD using ultrasonic nebulization

Thin films of Pb(Mg_1/3,Nb_2/3)O₃ (PMN) and Pb(Mg_1/3,Nb_2/3)O₃-PbTiO₃ (PMN-PT) were fabricated on Si and Pt/Ti/SiO₂/Si substrates by MOCVD using ultrasonic nebulization and their characteristics were investigated. PMN-PT films deposited at 350^∘C were annealed in a RTA (Rapid Thermal Annealing) system at 650^∘C for 30 sec to improve the micostructural properties. The crystallographic properties of PMN-PT films strongly depend on the content ratio of PbTiO₃. The content of pyrochlore phase in PMN-PT films decreased with the increase of Ti content and nearly single phase perovskite films were obtained at the composition of 80PMN-20PT. The PMN-PT films with perovskite phase showed a typical butterfly type C-V curve which verifies the ferroelectricity and had the relative dielectric constant of about 60.     

Ferroelectric properties of heterolayered lead zirconate titanate thin films

Heterolayered Pb(Zr_{1 − x} Ti _x )O₃ thin films consisting of alternating PbZr_0.7Ti_0.3O₃ and PbZr_0.3Ti_0.7O₃ layers were successfully deposited via a multistep sol-gel route assisted by spin-coating. These heterolayered PZT films, when annealed at a temperature in the range of 600–700^∘C show (001)/(100) preferred orientation, demonstrate desired ferroelectric and dielectric properties. The most interesting ferroelectric and dielectric properties were obtained from the six-layered PZT thin film annealed at 650^∘C, which exhibits a remanent polarization of 47.7 μC/cm² and a dielectric permittivity of 1002 at 100 Hz. Reversible polarization constituents a considerably high contribution towards the ferroelectric hysteresis of the heterolayered PZT films, as shown by studies obtained from C-V and AC measurement.     

Dielectric properties of ZnNb2 O 6 -TiO 2 mixture thin films

ZnNb₂O₆-TiO₂ mixture thin films with multilayer structures were fabricated via a sol-gel spin coating process. TiO₂ layers were deposited on the pre-crystallized ZnNb₂O₆ layers in order to suppress the formation of the ixiolite phase which always forms in the bulk system. The phase constitution of the thin films, confirmed by X-ray diffraction (XRD), could be controlled by the annealing temperatures, which, in turn, influenced the dielectric properties of the thin films. TiO₂ layers crystallized as the anatase phase and then transformed to the rutile phase at temperatures higher than 725^∘C. Dielectric constants of the mixture thin films, measured at 1 MHz with an MIM (metal-insulator-metal) structure, increased from 27 to 41 with dielectric losses below 0.005 as the annealing temperature increased from 700^∘C to 900^∘C. The increase in the dielectric constants was understood to originate from the increasing amounts of the rutile phase. Temperature coefficients of capacitance (TCC) were also measured between 25^∘C and 125^∘C, which showed a decreasing manner from positive values to negative values with increasing annealing temperatures. When annealed at 850^∘C, the TCC of the thin films could be tuned to be approximately 0 ppm/^oC with dielectric constant and dielectric loss of 36 and 0.002, respectively.     

Ferroelectric Properties of Bi3.25Nd0.75Ti3O12 Thin Films Prepared by MOD Process

Ferroelectric Bi_{4 – x}Nd_xTi₃O₁₂(BNdT) thin films with the composition (x = 0.75) were prepared on Pt/Ti/SiO₂/Si(100) substrate by metal-organic deposition. The films were annealed by various temperatures from 550 to 650C and then the electrical and structural characteristics were investigated for the application of FRAM. Electrical properties such as dielectric constant, 2Pr and capacitance were quite dependent on the thermal heat treatment. The measured 2Pr value on the BNdT capacitor annealed at 650C was 56 C/cm² at an applied voltage of 5 V. No fatigue was observed up to 8 × 10¹⁰ read/write switching cycles at a frequency of 1 MHz regardless of annealing temperatures.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Field-induced successive phase transitions of Pb(Zn1/3Nb2/3)O3-x%PbTiO3 crystals

The field-induced structural phase transitions of Pb[(Zn_1/3Nb_2/3)_1−x Tix]O₃ (PZN-x%PT) with x = 0.09 and 0.045 were investigated by the high-resolution micro-Brillouin scattering. PZN-9%PT crystals undergo two first order phase transitions, while PZN-4.5%PT undergo a second order phase transition under the zero-field cooling. Under the field-cooling, the higher phase transition of PZN-9%PT changed into a second order phase transition and the temperature range of a tetragonal phase was widened. Whereas a lower phase transition kept the nature of a first order phase transition. On the other hand, elastic anomaly was appeared on phase transition of PZN-4.5%PT under the field cooling.     

Study of nanocrystal TiO2 thin films by thermal annealing

The amorphous films were annealed in a wide temperature range (250–1000^∘C) and film properties of TiO₂ thin films were studied. Nano-sized anatase polycrystallites had been induced by thermal annealing for the films annealed at and above 300^∘C as confirmed by X-ray diffraction. Strong LO-phonon Raman modes, especially B_1g (395 cm⁻¹) and E _g (636 cm⁻¹) in Raman spectra and the absorption peak at 436 cm⁻¹ in absorbance spectra by Fourier transform infrared spectroscopy also indicated the existence of anatase phase in crystalline thin films. In addition, with the increase of the annealing temperature, the wettability of the film surface was enhanced as shown by the decrease of water contact angle from over 90^∘ to less than 40^∘. Moreover, upon UV laser irradiation on film surface, the water contact angle saturated at 10^∘ indicative of a highly hydrophilic surface for all the films, which arose from the dissociative adsorption of water molecules on the defect sits of the surface generated by the photocatalysis reactions of TiO₂. This behavior makes the film a good potential candidate for self-clean coatings.     

Fabrication of sub 50-nm direct-patterned Pb(Zr,Ti)O<Subscript>3</Subscript> films by electron beam-induced metal-organic deposition

Direct-patterned lead zirconate titanate (PZT) films prepared from an electron beam sensitive stock solution were investigated for advanced stage applications in sub 50-nm patterned systems. The required electron beam dose for the direct-patterning of PZT precursor films was 4.5 mC/cm². The PZT precursor films with pattern size of 500 × 500 μm² were exposed to an electron beam for 2 h and annealed at 400°C for 30 min under an O₂ ambient. After exposure and annealing, values of the remnant polarization and coercive field were 7.0 μC/cm² and 97 kV/cm at 10 V, respectively. These results suggest a possible application of PZT films in micro- or nano-electromechanical systems.     

Synthesis of Pb(Ni1/3Nb2/3)0.72Ti0.28O3 perovskite ceramics by a reaction-sintering process

Pb(Ni_1/3Nb_2/3)_0.72Ti_0.28O₃ (PNNT) perovskite ceramics produced by a reaction-sintering process were investigated. Without any calcination, the mixture of PbO, Ni(NO₃)₂, Nb₂O₅ and TiO₂ was pressed and sintered directly into PNNT ceramics. PNNT ceramics of 100% perovskite phase were obtained. For PNNT sintered for 2 h in PbO compensated atmosphere, maximum density reaches a value 8.49 g/cm³ (99.8% of the theoretical value) at 1250^∘C. A maximum dielectric constant 20600 occurred around 37^∘C at 1 kHz in PNNT sintered at 1250^∘C for 2 h.     

Characteristics of Bi4Ti3O12 thin films on ITO/glass and Pt/Si substrates prepared by R.F. sputtering and rapid thermal annealing

Bi₄Ti₃O₁₂ thin films are deposited on ITO/glass and Pt/Ti/Si(100) substrates by R.F. magnetron sputtering at room temperature. The films are then heated by a rapid thermal annealing (RTA) process conducted in oxygen atmosphere at temperatures ranging from 550–700^∘C. X-ray diffraction examination reveals that the crystalinity of the films grown on Pt/Ti/Si is better than that of the films grown on ITO/glass under the same fabrication conditions. SEM observation shows that the films grown on Pt/Ti/Si are denser than those grown on ITO/glass substrates. Interactive diffusion between the Bi₄Ti₃O₁₂ film and the ITO film increases with the increase of annealing temperature. The optical transmittance of the thin film annealed at 650^∘C is found to be almost 100% when the effect of the ITO film is excluded. The relative dielectric constants, leakage currents and polarization characteristics of the two films are compared and discussed.     

Calculation of the intrinsic dead layers thicknesses from Au/Ba0.5Sr0.5TiO3/Pt thin film capacitors

Ferroelectric Ba_0.5Sr_0.5TiO₃ (BST) films were prepared on Pt/Ti/SiO₂/Si substrates by the sol-gel process. The films were spin-coated at 2000 rpm for 30 secs and then pyrolysed for 5 mins at the temperature of 350^∘C. This coating procedure was repeated for 3, 4, 5 and 6 times to obtain BST films with different thicknesses. After coating the films with the desired repetition times, the films were finally annealed in a conventional furnace at temperatures ranging from 600^∘C to 800^∘C with a 50^∘C interval in between. The films obtained with an annealing procedure of 750^∘C were polycrystalline with the presence of an impurity BaCO₃ phase. The capacitance and leakage current were measured and used to extract information on the metal-BST interface. With the series capacitance model and modified Schottky emission equation, the thickness of the dead layers for Au/BST and Pt/BST interfaces were calculated to be less than 6 nm and 5 nm, respectively.     

Dielectric properties and morphotropic phase boundaries in the xPb(Zn1/3Nb2/3)O3−(1−x)Pb(Zr0.5Ti0.5O3 pseudo-binary system

Ceramics in the xPb(Zn_1/3Nb_2/3)O₃−(1−x)Pb(Zr_0.5Ti_0.5)O₃ [xPZN–(1−x)PZT] solid solution system are expected to display excellent dielectric, piezoelectric, and ferroelectric properties in compositions close to the morphotropic phase boundary (MPB). The dielectric behavior of ceramics with x = 0.1−0.6 has been characterized in order to identify the MPB compositions in this system. Combined with X-ray diffraction results, ferroelectric hysteresis measurements, and Raman reflectivity analysis, it was consistently shown that an MPB exists between x = 0.2 and x = 0.3 in this binary system. When x ≤ 0.2, the tetragonal phase dominates at ambient temperatures. In the range of x ≥ 0.3, the rhombohedral phase dominates. For this rhombohedral phase, electrical measurements reveal a profound frequency dispersion in the dielectric response when x ≥ 0.6, suggesting a transition from normal ferroelectric to relaxor ferroelectric between 0.5 ≤ x ≤ 0.6. Excellent piezoelectric properties were found in 0.3PZN–0.7PZT, the composition closest to the MPB with a rhombohedral structure. The results are summarized in a PZN–PZT binary phase diagram.     

Piezoelectric and dielectric characteristics of low temperature sintering Pb(Ni1/3Nb2/3)O3-Pb(Mn1/3Nb2/3)O3-Pb(Zr1/2Ti1/2)O3 ceramics for multilayer piezoelectric actuator

In this study, in order to develop the composition ceramics for multilayer piezoelectric actuator, PNN substituted PMN-PZT ceramics were fabricated using Li₂CO₃ and Na₂CO₃ as sintering aids, and their piezoelectric and dielectric characteristics were investigated. With the increase of the amount of PNN substitution, dielectric constant (εr), electromechanical coupling factor (k _p), and piezoelectric constant (d ₃₃) of specimens showed the maximum value at each sintering temperature, and crystal structure changed from tetragonal to rhombohedral. At the sintering temperature of 950^∘C, the density, εr, k _p, d ₃₃, Q_m and Tc of 12 mol% PNN substituted PMN-PNN-PZT composition ceramics showed the optimal values of 7.79 g/cm³, 1160, 0.599, 419pC/N, 894 and 332^∘C, respectively, for low loss multilayer piezoelectric actuator application.     

Influence of Post-Annealing on the Characteristics of Pb(Zr,Ti)O3 Thin Films Deposited by Liquid Delivery MOCVD Using a Cocktail Solution

Ferroelectric PZT thin films were deposited by liquid delivery MOCVD using a cocktail solution. The cocktail solution consisted of Pb(METHD)₂, Zr(METHD)₄ and Ti(MPD)(METHD)₂ diluted with ethylcyclohexane. The films deposited on Pt/Ti/SiO₂/Si at a substrate temperature of 500°C consisted of PZT, PbO and PbPt_x, and showed poor properties. However, after annealing at 450°C in air for thirty minutes, the PbPt_x phase disappeared while the volume of the PbO phase increased. The hysteresis properties were also improved by annealing at 450°C. After annealing at 600°C in air for thirty minutes, the PbPt_x and the PbO phases disappeared perfectly and the PZT thin films showed good hysteresis properties with the remanent polarization of 30 μC/cm² and the coercive field of 88 kV/cm.     

Structural and electrical properties of low resistance Pt/Pd/Au contact on p-GaN

We have investigated electrical and structural properties of Pt/Pd/Au ohmic contact on p-type GaN:Mg (2.5 × 10¹⁷ cm⁻³) using Auger electron spectroscopy (AES) and glancing angle x-ray diffraction (GXRD) analysis. It was shown that the specific contact resistivity improved with increasing annealing temperature. The annealing of the contact at 600^∘C for 2 min in flowing N₂ atmosphere resulted in a specific contact resistivity of 3.1 × 10⁻⁵ Ω cm². Both GXRD and AES depth profile results show that Ga₃Pt₅, Ga₂Pd₅, and Au₇Ga₂ phases are formed at the interface region between metal and GaN when annealed at temperatures 600^∘C. Possible explanation is suggested to describe the annealing dependence of the specific contact resistivity of the Pt/Pd/Au contacts.     

Microwave dielectric properties of Ca[(Li1/3Nb2/3)1−x Tix]O3−δ ceramics with glass

The effect of the addition of glass on the densification, low temperature sintering, and microwave dielectric properties of the Ca[(Li_1/3Nb_2/3)_1−x Ti_x]O_3−δ(CLNT) was investigated. Addition of glass (B₂O₃-ZnO-SiO₂-PbO system) improved the densification and reduced the sintering temperature from 1150^∘C to 900^∘C of Ca[(Li_1/3Nb_2/3)_1−x -Ti_x]O_3−δ microwave dielectric ceramics. As increasing glass contents from 10 wt% to 15 wt%, the dielectric constants (ε_r) and bulk density were increased. The quality factor (Q⋅f₀), however, was decreased slightly. The temperature coefficients of the resonant frequency (τ_f) shifted positive value as increasing glass contents over Ti content is 0.2 mol. The dielectric properties of Ca[(Li_1/3Nb_2/3)_0.75Ti_0.25]O_3−δ with 10 wt% glass sintered at 900^∘C for 3 h were ε_r = 40 Q·f₀ = 11500 GHz, τ_f = 8, ppm/°C. The relationship between the microstructure and dielectric properties of ceramics was studied by X-ray diffraction (XRD), and scanning electron microscope (SEM).     

Synthesis and properties of ferroelectric Si-doped (Bi, Nd)4Ti3O12 thin films by chemical solution deposition

Ferroelectric Si-doped (Bi,Nd)₄Ti₃O₁₂ thin films have been prepared on Pt/TiO_x/SiO₂/Si substrates through metal-organic compounds by the chemical solution deposition. The Bi_3.25Nd_0.75Ti_2.9Si_0.1O₁₂ (BNTS) precursor films were found to crystallize into the Bi-layered perovskite Bi₄Ti₃O₁₂ single-phase above 600^∘C. The synthesized BNTS films revealed a random orientation having a strong 117 reflection. The BNTS thin films prepared between 600^∘C and 700^∘C showed well-saturated P-E hysteresis loops with P _r of 13–14 μ C/cm² and E _c of 100–110 kV/cm at an applied voltage of 5 V. The surface roughness of the BNTS thin films was improved by Si doping compared with that of undoped Bi_3.35Nd_0.75Ti₃O₁₂ films.     

Spray pyrolysis of La0.6Sr0.4Co0.2Fe0.8O3-δ thin film cathodes

Spray pyrolysis has been used to prepare La_0.6 Sr_0.4Co_0.2Fe_0.8O_3-δ thin film cathodes for solid oxide fuel cell (SOFC) applications. The films are polycrystalline with nano-meter sized grains and less than 1 μm in thickness. Deposition parameters for film deposition have been established. The ratio of deposition temperature to solvent boiling point is found to be the most important processing parameter that determines whether a crack free homogeneous and coherent film is obtained. The morphology can be tailored by the deposition parameters. Annealing at 650^∘C for four hours in air results in coherent films of the desired perovskite phase. The films are potential cathodes for thin film micro-solid oxide fuel cells.     

Application of spark plasma sintering for growing dense Pb(Mg1/3Nb2/3)O3–35 mol% PbTiO3 single crystal by solid-state crystal growth

This study examined the effect of spark plasma sintering (SPS) on the densification behavior and resulting dielectric and piezoelectric properties of Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ ceramics with a 5 mol% excess of PbO. Through normal sintering at 1200^∘C, the density of the specimen reached only 92% of the theoretical density (TD). However, with the SPS treatment, the density of the PMN-PT ceramics increased to more than 99% of the TD at 900^∘C, and maintained over 98% of the TD during subsequent heat-treatment at 1200^∘C for 10 h. The increased density of the Pb(Mg_1/3Nb_2/3)O₃–35 mol% PbTiO₃ ceramics resulted in an improvement in the dielectric and piezoelectric properties. The SPS treatment was also successfully applied to the densification of a PMN-PT single crystal grown on a BaTiO₃ seed crystal using a solid-state crystal growth (SSCG) process.     

PZT capacitors using IrO2 electrode by RF magnetron sputtering

Abstract

RF magnetron sputtered Pb(Zr_x, Ti_1-x)O₃ [PZT] films were prepared on IrO₂/SiO₂/Si and Pt/IrO₂/SiO₂/Si substrates using the ceramic PZT target with Pb_1.1(Zr_0.52Ti_0.48)O₃ composition. In order to obtain single perovskite phase, PZT film was sputtered at room temperature under Ar plasma and followed by high temperature annealing under oxygen atmosphere. In case of Pt/PZT/IrO₂ capacitor, Δ P (=P*-P∧) was decreased with oxygen annealing temperature. However, it was increased in Pt/PZT/Pt/IrO₂ capacitor. Leakage current density of Pt/PZT/Pt/IrO₂ capacitor, which was used for improving leakage characteristics, was about 10^-2A/cm^?2 order lower than that of Pt/PZT/IrO₂ capacitor. Leakage current density of Pt/PZT/Pt/IrO₂ capacitor annealed at 700°C was 6.6x10^-6A/cm². From the fatigue test, Pt/PZT/IrO₂ capacitor annealed at 650°C and Pt/PZT/Pt/IrO₂ capacitor annealed at 700°C showed 3% and 12% degradation of Δ P after 5×10¹⁰ fatigue cycles, respectively.