Phase Separation of Alkoxy-derived (Ti,Sn)O2 Oriented Thin Films

Oriented (Ti,Sn)O₂ thin films with modulated microstructure were successfully synthesized on sapphire substrates by using sol–gel processing combined with spinodal decomposition. The degree of orientation of (Ti_0.5Sn_0.5)O₂ thin films increased in the following order: sapphire (0001), (11     0), and (01     2). (Ti_0.5Sn_0.5)O₂ thin films underwent spinodal decomposition at 900°C by annealing. The variation of the 2theta value of the 202 reflection of (Ti_0.5Sn_0.5)O₂ films showed the typical behavior of spinodal decomposition. The rate of spinodal decomposition of the (Ti_0.5Sn_0.5)O₂ films on sapphire (11     0) was faster than that on sapphire (01     2) substrates. The characteristic modulated microstructure was observed for the spinodally decomposed (Ti_0.5Sn_0.5)O₂ films on sapphire (01     2) substrates by transmission electron microscopy. (Ti_0.3Sn_0.7)O₂ films on sapphire (01     2) substrates were binodally decomposed during annealing at 1300°C.     

Preparation and Phase Separation Behavior of (Co,Fe)3O4 Films

(Co,Fe)₃O₄ films were synthesized by the sol–gel method through metalorganic compounds. The (Co,Fe)₃O₄ films (Co:Fe = 2:1) showed the characteristic behavior of the spinodal decomposition by heat treatments within the miscibility gap. The coercive force of the spinodally decomposed films increased from 0.9 kOe for a solid solution to 2.0 kOe for films that underwent the spinodal decomposition. The nonmagnetic phase (rich in Co) formed by the spinodal decomposition contributes to the pinning of the movement of magnetic domain walls. On the other hand, the (Co,Fe)₃O₄ films (Co:Fe = 1:1) showed the typical feature of binodal decomposition during heat treatment within the miscibility gap. The binodally decomposed films showed a slight increase in the coercive force depending upon the evolution of the magnetic region.     

Effect of Carbon Precursors on the Microstructure and Bonding State of a Boron–Carbon Compound Grown by LPCVD

Methane (CH₄) and propylene (C₃H₆) were used to fabricate a boron–carbon coating by a low-pressure chemical vapor deposition (LPCVD) technique. The effects of carbon precursors on the phase, microstructure, and bonding state of the deposits have been investigated. X-ray diffraction results show that the 2θ value of the deposit from the C₃H₆ precursor shifts to 25.78° when the coating is deposited at 1223 K, and shifts to 26.1° when deposited at 1273 K, compared with the 2θ value of the pyrocarbon (PyC) peak deposited by LPCVD, which is 25.42°, and no boron–carbon (B–C) compound peak exists. However, the phases of coating deposited from CH₄ include B₂₅C, B₁₃C₂, elemental carbon, and boron. X-ray photoelectron spectroscopy (XPS) results show that the percent contents of boron atom in the coatings from the CH₄ precursor are 61.18% and 67.78% when deposited at 1223 and 1273 K, respectively, much higher than that from the C₃H₆ precursor, 10.85% and 15.30%, respectively. Scanning electron microscopy (SEM) results show that the coatings deposited from CH₄ have a coarse crystal-like morphology; however, the coatings deposited from the C₃H₆ precursor are smooth. The formation of PyC from C₃H₆ is more facile than that from CH₄, which leads to differences in the phase, atom content, and microstructure of coatings from CH₄ and C₃H₆ precursors.     

Phase Equilibrium in the System PbO-TiO2–ZrO2

Phase equilibrium relations in the system PbO–TiO₂–ZrO₂ were studied by quenching in the range where the PbO content is 50 mole % and more. Isotherms were examined at 1100°, 1200°, and 1300°C and tie lines were determined between the liquid and solid solution in equilibrium. The incongruent melting point of PbZrO₃ was 1570°C and the equilibrium between liquid, PbO-type solid, and PbZrO₃ is peritectic. Pb(Zr,Ti)O₃ solid solutions containing more than 14 mole % PbZrO₃ decomposed to liquid, ZrO₂, and Pb(Zr,Ti)O₃ and the decomposition temperature rises from 1340° to 1570°C with increasing PbZrO₃ content. The system PbTiO₃–PbZrO₃ should not be treated as a binary, but as a section of the ternary system.     

Synthesis of Ba2NaNb5O15 Powders and Thin Films Using Metal Alkoxides

Transparent and highly oriented Ba₂NaNb₅O₁₅ (BNN) thin films have been prepared by using metal alkoxides. A homogeneous precursor solution was prepared by the controlled reaction of NaOC₂H₅, Nb(OC₂H₅)₅, and barium metal. The BNN precursor included a molecular-level mixture of NaNb(OC₂H₅)₆ and Ba[Nb(OC₂H₅)₆]₂ in ethanol. The alkoxy-derived powder crystallized to a low-temperature phase, and then transformed to orthorhombic BNN (tungsten bronze) at 600°C. BNN precursor films on substrates crystallized to orthorhombic BNN at 800°C via the low-temperature phase. Highly (002) oriented BNN films of tungsten bronze structure were successfully prepared on MgO (100) substrates at 700°C by using BNN underlayer.     

Synthesis of Highly Oriented K(Ta,Nb)O3 (Ta:Nb = 65:35) Film Using Metal Alkoxides

Highly oriented K(Ta,Nb)O₃ (Ta:Nb = 65:35) (KTN) thin films of perovskite structure were synthesized successfully on Pt(100)/MgO(100) substrates from a metal alkoxide solution through reaction control. Homogeneous KTN coating solutions prepared from KOC₂H₅, Ta(OC₂H₅)₅, and Nb(OC₂H₅)₅ in ethanol were analyzed by ¹H, ¹³C, and ⁹³Nb NMR spectroscopy. The KTN precursor included a molecular-level mixture of K[M(OC₂H₅)₆] (M = Ta, Nb) units interacting in ethanol solution. X-ray pole figure measurement showed that perovskite KTN films crystallized on Pt(100)/MgO(100) substrates had not only a (100) orientation but also a three-dimensional regularity of grains. The remanent polarization and coercive field of the KTN film (thickness, 1.0 μm) crystallized at 700°C were 1.5 μC/cm² and 8.7 kV/cm, respectively, at 225 K.     

Spark Plasma Sintering of Nano-Sized TiN Prepared from TiO2 by Controlled Hydrolysis of TiCl4 and Ti(O-i-C3H7)4 Solution

Nano-sized TiO₂ powders were prepared by controlled hydrolysis of TiCl₄ and Ti(O-i-C₃H₇)₄ solutions and nitrided in flowing NH₃ gas at 700°–1000°C to form TiN. Nano-sized TiN was densified by spark plasma sintering at 1300°–1600°C to produce TiN ceramics with a relative density of 98% at 1600°C. The microstructure of the etched ceramic surface was observed by SEM, which revealed the formation of uniformly sized 1–2 μm grains in the TiCl₄-derived product and 10–20 μm in the Ti(O-i-C₃H₇)₄-derived TiN. The electric resisitivity and Vickers micro-hardness of the TiN ceramics was also measured.     

Aluminum Nitride Prepared by Nitridation of Aluminum Oxide Precursors

Aluminum nitride (AlN) powders were prepared from the oxide precursors aluminum nitrate, aluminum hydroxide, aluminum 2-ethyl-hexanoate, and aluminum isopropoxide (i.e., Al(NO₃)₃, Al(OH)₃, Al(OH)(O₂CCH(C₂H₅)(C₄H₉))₂, and Al(OCH(CH₃)₂)₃). Pyrolyses were performed in flowing dry NH₃ and N₂ at 1000°–1500°C. For comparison, the nitride precursors aluminum dimethylamide (Al(N(CH₃)₂)₃) and aluminum trimethylamino alane (AlH₃·N(CH₃)₃) were exposed to the same nitridation conditions. Products were investigated using XRD, TEM, EDX, SEM, and elemental analysis. The results showed that nitridation was primarily controlled by the water:ammonia ratio in the atmosphere. Single-phase AlN powders were obtained from all oxide precursors. Complete nitridation was not obtained using pure N₂, even for the non-oxide precursors.     

Synthesis and Electrical Properties of Stabilized Manganese Dioxide (α-MnO2) Thin-Film Electrodes

Manganese dioxide (α-MnO₂) thin films have been explored as a cathode material for reliable glass capacitors. Conducting α-MnO₂ thin films were deposited on a borosilicate glass substrate by a chemical solution deposition technique. High carbon activities originated from manganese acetate precursor, (Mn(C₂H₃O₂)₂·4H₂O) and acetic acid solvent (C₂H₄O₂), which substantially reduced MnO₂ phase stability, and resulted in Mn₂O₃ formation at pyrolysis temperature in air. The α-MnO₂ structure was stabilized by Ba²⁺ insertion into a (2 × 2) oxygen tunnel frame to form a hollandite structure. With 15–20 mol% Ba addition, a conducting α-MnO₂ thin film was obtained after annealing at 600–650°C, exhibiting low electrical resistivity (∼1 Ω·cm), which enables application as a cathode material for capacitors. The hollandite α-MnO₂ phase was stable at 850°C, and thermally reduced to the insulating bixbyte (Mn₂O₃) phase after annealing at 900°C. The phase transition temperature of Ba containing α-MnO₂ was substantially higher than the reported transition temperature for pure MnO₂ (∼500°C).     

Growth Mechanism of Silicon Carbide Films by Chemical Vapor Deposition below 1273

SiC films were prepared from the reaction of Si₂H₆ with C₂H₄ or C₂H₂ at relatively low temperatures ranging from 873 K to 1273 K by low-pressure chemical vapor deposition. The deposition rate profiles determined by gravimetry and the alloy composition (carbon content, x, for Si_1-xC_x) profiles determined by X-ray photoemission spectroscopy in the reactor were mainly investigated. The results revealed that the carbon content, x , was a function of the temperature, ratio of partial pressures of source gases, and source gas species (C₂H₄, C₂H₂). From these results we deduced that SiC formation occurred by two major competing reaction processes: (1) the silicon deposition processes, SiH₂ Si (wall) and Si₂H₆ Si (wall), and (2) the carbon deposition process, C₂H₄+ SiH₂ vinylsilane or C₂H₂+ SiH₂ ethynylsilane.     

A New Method for Synthesizing Li2.06Nb0.18Ti0.76O3 Powder at Low Temperatures

Li_2.06Nb_0.18Ti_0.76O₃ powder has been successfully prepared at low temperatures via a facile and manageable, activated pretreatment on the inert raw Nb₂O₅. It is demonstrated that with triethanolamine, citric acid, and hydrogen peroxide, this simple pretreatment process could activate Nb₂O₅ efficiently. Pure Li₂TiO₃ solid solution phase was thus obtained by calcining the mixture of the activated Nb₂O₅, LiOH·H₂O, and Ti(C₄H₉O)₄ at temperatures as low as 650°C, which is about 200°C lower than that of the traditional solid-state method. To the best of our knowledge, this temperature is the lowest one for preparing Li₂TiO₃ solid solution. Additionally, the phase transformation and the morphology of the final powder are also discussed.     

Fabrication and Properties of Sol–Gel-Derived BiScO3–PbTiO3 Thin Films

BiScO₃–PbTiO₃ (BSPT) thin films near the morphotropic phase boundary were successfully fabricated on Pt(111)/Ti/SiO₂/Si substrates via an aqueous sol–gel method. The thin films exhibited good crystalline quality and dense, uniform microstructures with an average grain size of 50 nm. The dielectric, ferroelectric, and piezoelectric properties of the sol–gel-derived BSPT thin films were investigated. A remanent polarization of 74 μC/cm² and a coercive field of 177 kV/cm were obtained. The local effective piezoelectric coefficient d ^*₃₃ was 23 pC/N at 2 V, measured by a scanning probe microscopy system. The dielectric peak appeared at 435°C, which was 80°C higher than that of Pb(Ti, Zr)O₃ thin films.     

Synthesis of Highly Oriented Lead Zirconate–Lead Titanate Film Using Metallo-organics

Crack-free Pb(Zr,Ti)O₃ (PZT) thin films with preferred orientation were prepared successfully on MgO (100), SrTiO₃ (100), and Pt/Ti/SiO₂/Si substrates from metal alkoxide solutions. Calcination of precursor films in a H₂O─-O₂ gas mixture was found to be effective not only for low-temperature crystallization of perovskite PZT, but also for obtaining the preferred orientation of PZT films. Single-phase PZT films with high preferred orientation were synthesized on MgO (100) and Pt/Ti/SiO₂/Si substrates at 550° and 600°C for 2 h, respectively. The PZT film on the Pt/Ti/SiO₂/Si substrate showed a permittivity of 520, tan δ of 0.03, a remanent polarization of 24 μC/cm², and a coercive field of 54 kV/cm.     

Preparation of Potassium Tantalate Niobate by Sol–Gel Method

Perovskite potassium tantalate niobate (KTN) powders and thin films were synthesized from a metal alkoxide solution. Homogeneous KTN coating solutions were prepared from KOC₂H₅, Ta(OC₂H₅)₅, and Nb(OC₂H₅)₅ in absolute ethanol. The precursor crystallized to pyrochlore at ∼ 650°C, and then to perovskite at ∼ 750°C, depending upon Ta:Nb ratio. H₂O vapor during calcination was found to play a prominent role in the direct and predominant crystallization of perovskite films with preferred orientation. Highly oriented KTN films of perovskite structure were successfully prepared on MgO (100) substrates at 675°C.     

Use of Transmission Electron Microscopy for the Characterization of Rapid Thermally Annealed, Solution-Gel, Lead Zirconate Titanate Films

The microstructure and preferred orientations of rapid thermally annealed Pb(Zr_0.53,Ti_0.47)O₃ films, deposited on Pt/Ti/SiO₂/Si electrode/substrates by solution-gel spinning, have been investigated using analytical and high-resolution electron microscopy and X-ray diffraction. The temperature of pyrolysis of the PZT films was found to influence the preferred orientation of the film: lower temperatures (350°C) favored a (111) orientation, whereas higher temperatures (420°C) favored a (100) orientation. Excess Pb was used to control the A-site stoichiometry of the film particularly at the film surface where Pb-deficient crystals could often be observed. The absence of these crystals was shown to be correlated with an improvement in the dielectric response.     

Ethene/Ethane (C2H4/C2H6) Separation through an Inorganic–Organic Hybrid Membrane Containing Silver(I) Ions as Olefin Carriers, Using Poly(N-vinylpyrrolidone) as a Mediation Agent

Novel inorganic–organic membranes that contained Ag⁺ ions as olefin carriers were prepared using sol–gel and dip-coating processes. The permeance of the membranes for nitrogen, helium, ethane (C₂H₆), and ethene (C₂H₄) were evaluated using the single-gas permeation method at temperatures of 298, 373, and 423 K. The results showed that the selectivity of the membranes to C₂H₄ against C₂H₆ increased as the measurement temperature increased, because the decomplexation rate of C₂H₄ molecules from Ag⁺ sites is enhanced by increases in the temperature. Fourier transform infrared spectrophotometry of the hybrid membranes and the performance of the membranes at 373 and 423 K indicated that poly( N -vinylpyrrolidone) (PVP) had a role in increasing the flexibility of the inorganic network and also served as a mediation agent to fix Ag⁺ ions in the polymer segments, because of the coordination interaction between the Ag⁺ ions and the PVP.     

Spin Coating of a Ca(Ti,Fe)O3 Dense Film on a Porous Substrate for Electrochemical Permeation of Oxygen

A dense Ca(Ti_0.75Fe_0.25)O_3−α (Ca(Ti,Fe)O₃) film, which is a mixed conductor of oxide ions and electrons/holes, was prepared on a porous CaTiO₃ substrate by a spin-coating method. The calcined Ca(Ti,Fe)O₃ powder with 2–3 μm grain sizes was mixed with a dispersant in ethanol to form the slurry for spin coating. A uniform Ca(Ti,Fe)O₃ green film was obtained at 1000–1500 rpm on the rotating porous CaTiO₃ substrate, which had an average pore diameter of a few micrometers. The optimum sintering conditions for the spin-coated films were a soaking temperature of 1235°C and a holding time of 2 h, in air. A dense, sintered Ca(Ti,Fe)O₃ film }20–50 μm thick was prepared by repeating the coatingsintering process. The gas-tight film prepared on the porous substrate exhibited higher electrochemical permeation of oxygen at an operating temperature of 1000°C compared with that of thicker, sintered Ca(Ti,Fe)O₃ disks.     

Preparation and Process Chemistry of SnO2 Films Derived from SnC2O4 by the Aqueous Sol–Gel Method

Nanocrystalline SnO₂ films were prepared from SnC₂O₄ by a sol–gel route. A clarified and stable Sn-containing sol was obtained by dissolving and chelating SnC₂O₄ with C₆H₈O₇ and H₂C₂O₄ in a C₆H₈O₇/triethanolamine (TEA) mixing aqueous solution with a pH of 6.5–7.0. The chelation and condensation reactions were deducted based upon infrared, Raman, and X-ray photoelectron spectra analysis. Results illuminated that a number of ionized-state carboxyl groups and active tin hydrate were produced in the mixing solution by amido association of TEA with H on –COOH of H₃L and H₂C₂O₄, supplying a precondition for tin sol formation. X-ray diffraction and field emission scanning electron microscope analysis indicated that SnO₂ film had a rutile structure and consisted of nanocrystals with a mean size of about 7 nm. Film thickness could be controlled by the number of dip coating—annealing cycles according to 30–45 nm/cycle for a Sn concentration of 0.25 mol/L.     

Synthesis of 0.4Pb(Mg1/3Nb2/3)O3–0.3Pb(Mg1/2W1/2)O3–0.3PbTiO3 Ceramics by Metal Alkoxide Method, and Its Dielectric Properties

0.4Pb(Mg_1/3Nb_2/3)O₃–0.3Pb(Mg_1/2W_1/2)O₃–0.3PbTiO₃+ x MgO ( x = 0 to 0.04) were prepared by a metal alkoxide method. The percent of perovskite phase of the calcined powders increased with increased calcination temperatures. About 89% of perovskite phase was obtained at 1050°C. The dielectric constant of the pellets fired at 1100°C was increased by the addition of 10 wt% excess Mg(OC₂H₅)₂ and had a maximum value of 7532 at 1 kHz.     

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.