Enhanced dielectric tunability properties of Ba(ZrxTi1−x)O3 thin films using seed layers on Pt/Ti/SiO2/Si substrates

The compositionally graded and homogeneous Ba(Zr_xTi_1−x)O₃ (BZT) thin films were fabricated on LaNiO₃ (LNO) buffered Pt/Ti/SiO₂/Si and Pt/Ti/SiO₂/Si substrates by a sol–gel deposition method, respectively. These films crystallized into a single perovskite phase. The BZT thin films deposited on LaNiO₃/Pt/Ti/SiO₂/Si substrates had a highly (1 0 0) preferred orientation and exhibited a preferred (1 1 0) orientation when the thin films were deposited on Pt/Ti/SiO₂/Si substrates. The LNO and Ba(Zr_0.30Ti_0.70) served as seed layer on Pt/Ti/SiO₂/Si substrates and analyze the relationship of seed layer, microstructure and dielectric behavior of the thin films. The compositionally graded thin films from BaTiO₃ to BaZr_0.35Ti_0.65O₃ were fabricated on LNO/Pt/Ti/SiO₂/Si substrates. The tunability behavior of compositionally graded films was analyzed in order to produce optimum effective dielectric properties. The dielectric constant of BaZr_xTi_1−xO₃ compositionally graded thin films showed weak temperature dependence. This kind of thin films has a potential in a fabrication of a temperature stable tunable device.     

Dependence of the properties of compositionally graded Pb(Zr,Ti)O3 ferroelectric films of the bottom electrode

Compositionally graded Pb(Zr_,Ti)O₃ thin films were prepared on the Pt(1 1 1)/Ti/SiO₂/Si, LNO/Si(1 0 0) and LNO/Pt(1 1 1)/Ti/SiO₂/Si substrates by a modified sol–gel method and rapid heat-treatment. The composition depth profile of a typical up-graded film was determined using a combination of auger electron spectroscopy and Ar-ion etching. The crystallographic orientation and the microstructure of the resulting graded PZT thin films on the different substrates were characterized by XRD. The dielectric and ferroelectric properties of the graded PZT films were discussed. The graded PZT films on LNO/Pt/Ti/SiO₂/Si and LNO/Si(1 0 0) substrates have larger dielectric constant and remnant polarizations compared to that grown on Pt/Ti/SiO₂/Si substrates.     

Spectroscopic ellipsometry characterization of TiO2 thin films prepared by the sol–gel method

TiO₂ thin films were prepared on SiO₂/Si(100) substrates by the sol–gel process. XRD results indicate that the major phase of TiO₂ thin films is anatase. The surface morphology and cross-section are observed by FE-SEM. The surface of thin films is dense, free of cracks and flat. The average grain size is about 60–100 nm in diameter. The thickness of single layer TiO₂ thin films is about 60 nm, which increases with the concentration of solution. Ellipsometric angles ψ, Δ are investigated by spectroscopic ellipsometry. The optical constant and the thickness of TiO₂ thin films are fitted according to Cauchy dispersion model. The results reveal that the refractive index and the extinction coefficient of TiO₂ thin films in wavelength above 800 nm are about 2.09–2.20 and 0.026, respectively. The influences of processing conditions on the optical constants and thicknesses of TiO₂ thin films are also discussed.     

Temperature dependence of electrical and electromechanical properties of Pb(Mg1/3Nb2/3)O3–Pb(Ni1/3Nb2/3)O3–Pb(Zr,Ti)O3 thin films

The electrical and electromechanical properties of Pb(Mg_1/3Nb_2/3)O₃–Pb(Ni_1/3Nb_2/3)O₃–Pb(Zr,Ti)O₃ (PMN–PNN–PZT, PMN/PNN/PZT = 20/10/70) on Pt/Ti/SiO₂/Si substrates by chemical solution deposition was investigated. The PMN–PNN–PZT films annealed at 650 °C exhibited slim polarization hysteresis curves and a high dielectric constant of 2100 at room temperature. A broad dielectric maximum at approximately 140–170 °C was observed. The field-induced displacement was measured by scanning probe microscopy, the bipolar displacement was not hysteretic, and the effective piezoelectric coefficient (d₃₃) was 66 × 10⁻¹² m/V. The effective d₃₃ decreased with temperature, but the value at 100 °C remained 45 × 10⁻¹² m/V.     

Metal-organic chemical liquid deposited (1 1 0)-preferred LaNiO3 buffer layer for Pb0.97La0.02(Zr0.85Sn0.13Ti0.02)O3 antiferroelectric films

Conductive perovskite lanthanum nickelate LaNiO₃ (LNO) thin films were fabricated on SiO₂/Si substrates through metal-organic chemical liquid deposition method. The effect of annealing temperature on the orientation and sheet resistance of the LNO films were investigated. XRD patterns showed that the LNO films deposited on SiO₂/Si substrates exhibited preferred-(1 1 0) orientation. The lowest sheet resistance of the LNO thin films, 250 Ω/□ was obtained after being annealed at 650 °C for 1 h. Subsequently, Pb_0.97La_0.02(Zr_0.85Sn_0.13Ti_0.02)O₃ (PLZST) antiferroelectric thin films were prepared on the LaNiO₃ buffered SiO₂/Si substrates via sol–gel process. And the crystallinity, microstructure and electric properties of the PLZST thin films were studied in details.     

Ohmic contacts to polycrystalline 3C–SiC films for extreme environment microdevices

Ohmic contact characteristics were studied under the surface treatments of poly 3C–SiC films heteroepitaxially grown on SiO₂/Si wafers by APCVD. The poly 3C–SiC surface was polished to remove submicron-sized roughness and to get flat and smooth surface using chemical–mechanical polishing (CMP) process. However, some scratching marks on the poly 3C–SiC have remained surface due to the mechanical defect of CMP process. To remove a part of subsurface damage and scratching marks, the polished surface was oxidized by wet-oxidation furnace and it has been etched by diluted HF solution. Titanium tungsten (TiW) thin film was deposited on the surface treated poly 3C–SiC using circular transmission line model as a metallization process and it was annealed through the rapid temperature annealing (RTA) process to improve interfacial adhesion. The contact resistivity of the treated 3C–SiC surface was measured as the lowest 1.2 × 10⁻⁵ Ω cm³ at 900 °C for 45 s.     

Influence of annealing atmosphere on the structure, resistivity and transmittance of InZnO thin films

Dependence of the electrical and optical properties of In₂O₃–10 wt% ZnO (IZO) thin films deposited on glass substrates by RF magnetron sputtering on the annealing atmosphere was investigated. The electrical resistivities of indium zinc oxide (IZO) thin films deposited on glass substrate can be effectively decreased by annealing in an N₂ + 10% H₂ atmosphere. Higher temperature (200 °C) annealing is more effective in decreasing the electrical resistivity than lower temperature (100 °C) annealing. The lowest resistivity of 6.2 × 10⁻⁴ Ω cm was obtained by annealing at 200 °C in an N₂ + 10% H₂ atmosphere. In contrast, the resistivity was increased by annealing in an oxygen atmosphere. The transmittance of IZO films is improved by annealing regardless of the annealing temperature.     

Effects of oxygen concentration on the electrical properties of ZnO films

In this paper, electrical characteristics by various oxygen content in ZnO films were studied. To control the oxygen content of ZnO films, post-thermal annealing was performed in N₂ and air ambient, led to improve crystallinity and optical properties of ZnO films. The oxygen concentration was measured by Auger electron spectroscopy. The ZnO films having the deficiency of oxygen showed the electron concentrations between 10²¹ and mid 6 × 10¹⁷ cm⁻³ and resistivity at 10⁻³–10⁻¹ Ω cm. On the other hand, when the oxygen concentration of the ZnO films was up to the stoichiometry with Zn, the ZnO films showed low electron concentration at −10¹⁷ cm⁻³ and resistivity at 10 Ω cm.     

On the correlation between crystallinity of platinum bottom electrode and that of MOD derived PZT thin films

Growth of well(111)-oriented Pt and Pt/Ti films on SiO₂/Si(111) substrates and crystallinity of PZT films grown on the Pt(111)/SiO₂/Si(111) and Pt(111)/Ti/SiO₂Si(111) substrates have been investigated. It was found by X-ray diffraction analysis that well (111)-oriented Pt film with a best full-width at half maximum (FWHM) of 0.28° was grown by the DC sputtering method. PZT films were prepared by metallo-organic decomposition (MOD) on Pt(111)-coated SiO₂Si(111) substrates. The crystallinity of the PZT films improved as the FWHM of the Pt(111) diffraction peak decreased. The best FWHM obtained for a PZT film grown on a Pt(111)/Ti/SiO₂/Si(111) substrate was 0.33°.     

ZSM-5 zeolite films on Si substrates grown by in situ seeding and secondary crystal growth and application in an electrochemical hydrocarbon gas sensor

ZSM-5 zeolite films were grown on Si substrates by a two-step hydrothermal synthesis consisting of in situ seeding and secondary crystal growth. The films were 8–13 μm thick and partly oriented with the c-axis perpendicular to the substrate surface. After ion exchange with sodium ions, one film was applied as solid electrolyte in a potentiometric hydrocarbon gas sensor. A fast and reversible voltage response of the sensor to varying propane concentrations (100 ppm – 10%) was observed in O₂/CO₂/N₂ gas mixtures at 723 K.     

Deposition of Pb(Zr,Ti)O3 Thin Films by Metal-Organic Chemical Vapor Deposition Using β-diketonate Precursors at Low Temperatures

Lead zirconate titanate (PZT) thin films were deposited by metal-organic chemical vapor deposition (MOCVD) using β-diketonate precursors and 0₂ at temperatures below 500°C on variously passivated Si substrates. PZT thin films could not be deposited on bare Si substrates, owing to a serious diffusion of Pb into the Si substrate during deposition. Pt/SiO₂/Si substrates could partially block the diffusion of Pb, but a direct deposition of PZT thin films on the Pt/SiO₂/Si substrates resulted in a very inhomogeneous deposition. A TiO₂ buffer layer deposited on Pt/SiO₂/Si substrates could partially suppress the diffusion of Pb and produce homogeneous thin films. However, the crystallinity of PZT thin films deposited on the TiO₂-buffered Pt/SiO₂/Si substrate was not good enough, and the films showed random growth direction. PZT thin films deposited on the PbTiO₃-buffered Pt/SiO₂/Si substrates had good crystallinity and a- and c-axis oriented growth direction. However, the PZT thin film deposited at 350°C showed fine amorphous phases at the grain boundaries, owing to the low chemical reactivities of the constituent elements at that temperature, but they could be crystallized by rapid thermal anneaiing (RTA) at 700°C. PZT thin film deposited on a 1000-å PbTiO₃,-thin-film-buffered Pt/SiO₂/Si substrate at 350°C and rapid thermally annealed at 700°C for 6 min showed a single-phase perovskite structure with a composition near the morphotropic boundary composition.     

Influences of Cr Doping on the Electrical Properties in BiFeO3 Thin Films

Cr-doped BiFeO₃ (BFO) thin films were deposited on Pt(200)/TiO₂/SiO₂/Si(100) substrates by a chemical solution deposition method. The dielectric constant and dissipation factor of the BFO thin films decrease from 165 and 0.054 (undoped) to 100 and 0.02 (3 mol% Cr-doped) at a frequency of 10 kHz as the Cr content increases. The leakage current and ferroelectric properties were improved significantly by means of Cr doping. The leakage current density of 4.1×10^-6 A/cm² for the 3 mol% Cr-doped BFO thin film is about four orders of magnitude lower than that of undoped BFO thin film at an external electric field of 100 kV/cm. The 3 mol% Cr-doped BFO thin film exhibited a well-saturated hysteresis loop with a large remanent polarization (P_r) of 61 μC/cm² at room temperature. The reason for the improved leakage current and ferroelectric properties in Cr-doped BFO thin films can be attributed to the reduced oxygen vacancies in the films by Cr doping.

Communicated by Dr. George W. Taylor     

Effect of poly(vinyl acetate) on structure and property of bismuth-doped strontium titanate thin films derived by sol–gel method

Bismuth-doped strontium titanate thin films with pure perovskite phase have been successfully deposited on Pt (1 1 1)/Ti/SiO₂/Si substrate by polymer-assisted sol–gel method. Poly(vinyl acetate) (PVAc) in precursor solution promoted the formation of perovskite phase during the heat treatment. SEM results revealed an increasing thickness from 40 to 80 nm every single layer and a porous structure with the addition of PVAc. The addition of polymer made the dielectric constant decrease from 140 to 40 and the tunability slightly increase compared with films without polymer in precursor.     

New method for selective growth of diamonds by microwave plasma chemical vapour deposition

Selective nucleation and deposition of diamonds were achieved on an SiO₂-patterned Si substrate. The substrate was pre-treated with an electric field in plasma to introduce diamond nuclei. This treatment did not affect the SiO₂ area. Consequently, diamonds grew only on the area where Si was exposed under the conventional conditions of diamond growth. The maximum nucleation density on the area of SiO₂was about 5 × 10⁷ cm⁻². The ratio of the selectivity was 2 × 10² or higher. This process will be useful and very promising for manufacturing diamond electronic devices.     

Tin oxide thin films deposited by ultrasonic spray pyrolysis

This study investigated microstructure of SnO₂ thin films deposited by ultrasonic spray pyrolysis technique using 0.2 M of SnCl₄·5H₂O in absolute ethanol as a precursor. The deposition temperature (350–450 °C) and time (20–90 min) were varied. The influence of film-deposition conditions on grain size and orientation were discussed. The deposited SnO₂ films were textured polycrystalline films. The preferred orientation of SnO₂ films were quantitatively evaluated by texture coefficient (TC). The mean grain size and film thickness determined by SEM could be controlled over a range of 50–325 nm and 80–2690 nm, respectively.     

Preparation and characterization of TiO2–SiO2 nano-composite thin films

TiO₂ nanocrystalline particles dispersed in SiO₂ have been prepared by the sol-gel method using titanium- and silicon-alkoxides as precursors. Nano-composite thin films were formed on the glass substrates by dip-coating technique and heat treated at temperatures up to 500 °C for 1 h. The size of the TiO₂ nanocrystalline particles in the TiO₂–SiO₂ solution ranged from 5 to 8 nm. The crystalline structure of TiO₂ powders was identified as the anatase phase. As the content of SiO₂ increased, the anatase phase tended to be stabilized to higher temperature. TEM results revealed the presence of spherical TiO₂ particles dispersed in a disk-shaped glassy matrix. Photocatalytic activity of the TiO₂–SiO₂ (1:1) thin films showed decomposition of 95% of methylene blue solution in 2 h and a contact angle of 10°. The photocatalytic decomposition of methylene blue increased and the contact angle decreased with the content of TiO₂ phase. TiO₂–SiO₂ with the molar ratio of 1:1 showed a reasonable combination of adhesion, film strength, and the photocatalytic activity.     

In-Plane Polarized 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 Thin Films

Ferroelectric 0.7Pb(Mg_1/3Nb_2/3)O₃–0.3PbTiO₃ (PMN-PT) thin films were deposited on ZrO₂/SiO₂/silicon substrates using a chemical-solution-deposition method. Using a thin PZT film as a seed layer for the PMN-PT films, phase-pure perovskite PMN-PT could be obtained via rapid thermal annealing at 750°C for 60 s. The electrical properties of in-plane polarized thin films were characterized using interdigitated electrode arrays on the film surface. Ferroelectric hysteresis loops are observed with much larger remanent polarizations (∼24 μC/cm²) than for through-the-thickness polarized PMN-PT thin films (10–12 μC/cm²) deposited on Pt/Ti/Si substrates. For a finger spacing of 20 μm, the piezoelectric voltage sensitivity of in–plane polarized PMN-PT thin films was ∼20 times higher than that of through-the-thickness polarized PMN-PT thin films.     

Effects of Excess Bismuth Content in Precursor Solutions on Ferroelectric Properties of BiFeO3 Thin Films Prepared by a Chemical Solution Deposition

Cr-substituted BiFeO₃ (BFCr) thin films prepared from precursor solutions with stoichiometric composition and various excess Bi contents ranged from 5 to 20 mol% were fabricated on Pt/TiO₂/SiO₂/Si(100) substrates by a chemical solution deposition method, and the effects of excess Bi content in precursor solutions on the ferroelectric properties of the as-deposited BFCr thin films were studied. It was found that the BFCr thin film prepared from precursor solution with excess Bi content of 5 mol% exhibited the best dielectric constant-frequency and polarization-electric field characteristics. In detail, its dielectric constant is 158 at frequency of 100 kHz and remnant polarization (P_r) value is 49 μ C/cm² at electric field of 600 kV/cm.     

The improvement in oxidation resistance of carbon by a graded SiC/SiO2 coating

A dense functionally gradient SiC/SiO₂ coating has been developed to improve the oxidation resistance of carbon at elevated temperatures. SiC was coated on the surface of a graphite substrate by a reaction between thermally evaporated silicon and carbon at 1400 °C. The SiO₂ layer was deposited by exposing the SiC coated specimens next to a bed of Si powder in a flowing H₂–H₂O gas (P_H2O=2.6×10⁻² atm) at 1400 °C. The formed SiC/SiO₂ layers were dense and had gradient compositions with good adhesion to the carbon substrate. However, as the coating thickness increased, the coating layer became cracked and delaminated from the substrate due to thermal stress. The specimens with the continuous SiC/SiO₂ layer showed a remarkably improved oxidation resistance up to 1200 °C.     

Fabrication of La2Ti2O7 thin films by a sol-gel technique

Sol-gel thin films of La₂Ti₂O₁₇ were deposited on fused silica and Si( 100) substrates by a spin-coating process. The La₂Ti₂O₁₇ precursor solution for the spin-coating was prepared from lanthanum acetylacetonate and titanium iso-propoxide dissolved in 2-methoxyethanol. Crystalline and crack-free films of ∼ 0.3 μm thickness were deposited on the above sulastrates using a single coating and followed by annealing at a temperature of 800 "C. Microstructural studies revealed that these films contained extremely fine grains of ∼ 0.1 μm. Thin film X-ray diffraction patterns indicated the formation of grain oriented films along [100] direction on these substrates.