Control of Microstructure and Orientation in Solution-Deposited BaTiO3 and SrTiO3 Thin Films

Columnar and highly oriented (100) BaTiO₃ and SrTiO₃ thin films were prepared by a chelate-type chemical solution deposition (CSD) process by manipulation of film deposition conditions and seeded growth techniques. Randomly oriented columnar films were prepared on platinum-coated Si substrates by a multilayering process in which nucleation of the perovskite phase was restricted to the substrate or underlying layers by control of layer thickness. The columnar films displayed improvements in dielectric constant and dielectric loss compared to the fine-grain equiaxed films that typically result from CSD methods. Highly oriented BaTiO₃ and SrTiO₃ thin films were fabricated on LaAlO₃ by a seeded growth process that appeared to follow a standard "two-step" growth mechanism that has been previously reported. The film transformation process involved the bulk nucleation of BaTiO₃ throughout the film, followed by the consumption of this matrix by an epitaxial overgrowth process originating at the seed layer. Both BaTiO₃ and PbTiO₃ seed layers were effective in promoting the growth of highly oriented (100) BaTiO₃ films. Based on the various processing factors that can influence thin film microstructure, the decomposition pathway involving the formation of BaCO₃ and TiO₂ appeared to dictate thin film microstructural evolution.     

Low-Temperature Synthesis and Characterization of Lead Zinc Niobate Thick Films

Perovskite Pb(Zn_1/3Nb_2/3)O₃ (PZN) thick films were prepared by a hydrothermal route at a low temperature (150°C) on Ti metal, where the titanium (Ti) metal served as both the substrate and bottom electrode for the PZN films. The thickness of the PZN film fabricated on the Ti substrate was about 20 μm. We have demonstrated that the concentration of KOH plays a key role in obtaining the perovskite structure in the PZN film. The dielectric relaxation was studied as a function of temperature and frequency. A dispersion of the maximum dielectric permittivity (ɛ_max) appears around the temperature of T _m, which shifts toward higher temperatures with increasing frequency. The variation of T _m with frequency follows the Vogel–Fulcher relationship. The variation of 1/ɛ with temperature above T _m deviates from the Curie–Weiss (CW) law but satisfies the modified CW law. The relaxation indication coefficient (γ) and broadening parameter (Δ) were estimated from a quadratic fit of the modified Curie–Weiss law and were found to be 2.00 and 42 K, respectively, indicating strong relaxor behavior. The samples showed excellent reproducibility in the measurements of leakage current, a remnant polarization of 14 μC/cm², and a coercive field of 300 kV/m.     

Effects of Heating Profiles on the Orientation and Dielectric Properties of 0.5Pb(Mg1/3Nb2/3)O3-0.5PbTiO3 Thin Films by Chemical Solution Deposition

0.5Pb(Mg_1/3Nb_2/3)O₃-0.5PbTiO₃ thin films were prepared on Pt(111)/Ti/SiO₂/Si(100) substrates by varying the film formation procedures and heating processes. Depending on the multilayer film formation and appropriate heating process, the films were grown with a preferential orientation. The films showed a (100)-preferred orientation and large grain-size distribution when they were directly heat-treated after deposition of amorphous layers. The films showed a (111)-preferred orientation and small grain-size distribution when formed layer-by-layer or directly heating amorphous thin films with a perovskite seed layer. These results were explained by the effect of a seed layer. Saturation polarization of the (111)-preferred films was ∼35 µC/cm², which was somewhat higher than that of the (100)-preferred film. In contrast, the dielectric constant of the (100)-preferred film was ∼1600, which was larger than that of the (111)-preferred film.     

Processing of Novel Strontium Titanate-Based Thin-Film Varistors by Chemical Solution Deposition

Strontium titanate (SrTiO₃)-based multilayered film with varistor characteristics has successfully been fabricated by a chemical solution deposition (CSD) method. Homogeneous precursor solutions of SrTiO₃ and Nb:SrTiO₃ with long-term stability could be prepared by optimizing the reaction conditions among strontium ethoxide, titanium isopropoxide, and niobium ethoxide. Films were prepared using the precursor solutions on fused silica substrates at 700°C. Triple layered films with SrTiO₃/Nb:SrTiO₃/SrTiO₃ structure were also successfully crystallized on Pt/Ti/SiO₂/Si substrates at 700°C. The current–voltage ( I - V ) curve of the multilayered film was characteristic to varistors and the nonlinear coefficient α of the synthesized film was ∼3.0. The varistor voltages ( E _0.01) of 0.6-μm-thick film were 140 kV/cm for the forward direction and −120 kV/cm for the reverse direction, respectively, at room temperature.     

Microstructure and Electrical Properties of Chemically Prepared Nb2O5-Doped SrTiO3 Ceramics

Chemically homogeneous SrTiO₃ powders of submicrometer size were obtained by alcohol dehydration and subsequent calcination of citrate/format solutions. Nb₂O₅-doped SrTiO₃ was prepared with various Sr:Ti ratios resulting in an anomalous increase in the dielectric constant ( K 'up to ∼8000) for donor-doped SrO-excess SrTiO₃. No semiconducting behavior was observed for donor-doped TiO₂-excess SrTiO₃ when fired in air. Therefore, a "brick-wall" type of microstructure was formed as a result of the excess SrO, giving rise to anomalously high dielectric constants.     

Effect of the Pb/Ti Source Ratio on the Crystallization of PbTiO3 Thin Films Grown by Metalorganic Chemical Vapor Deposition at Low Temperature of 400oC

Crystalline PbTiO₃ thin films were successfully deposited on (111)-oriented Pt/Ti/SiO₂/Si and on (200)-oriented Pt/SiO₂/Si by metalorganic chemical vapor deposition at a substrate temperature of 400°C, using a β-diketonate complex of Pb(tmhd)₂ (tmhd = 2,2,6,6-tetramethyl-3,5-heptanedionate) and titanium isopropoxide as source precursors. The dependence of the formation of crystalline PbTiO₃ phase on the Pb/Ti input precursor ratio is qualitatively described. The structure of the films deposited at 400°C changed from amorphous to polycrystalline with an increase of the Pb/Ti ratio from 1.1 to 5.0, including a partially crystallized structure at some intermediate ratio. Partial crystallization of as-grown PbTiO₃ film was analyzed by scanning electron microscopy, micro-Raman, and Auger electron spectroscopy measurements. It was found that the control of excess Pb precursor through a change in the Pb/Ti ratio is the key process parameter for the formation of crystalline PbTiO₃ phase in the low-temperature MOCVD process.     

Fatigue-Free Lead Zirconate Titanate (Pb(Zr,Ti)O3)-Based Capacitors Co-modified by Lanthanum and Lithium for Nonvolatile Memories

Pb_0.98(La_{1− x} Li _x )_0.02(Zr_0.55Ti_0.45)O₃(PLLZT with 0.1 ≤ x ≤ 0.7) thin films were sol-gel-grown on Pt(111)/Ti/SiO₂/Si substrates, employing a thin lead zirconate titanate (PZT) template layer. Films annealed at >550°C showed a highly (111)-oriented preferential growth. Typical values of the switchable remanent polarization (2 P _r) and the coercive field ( E _c) of the PLLZT/PZT/Pt film capacitor for x = 0.3 were 50 μC/cm² and 39 kV/cm, respectively, at 5 V. All the PLLZT/PZT/Pt capacitors (for 0.1 ≤ x ≤ 0.7) exhibited fatigue-free behavior up to 6.5 × 10¹⁰ switching cycles, a quite stable charge retention profile with time, and high 2 P _rvalues, all which assure their suitability for nonvolatile ferroelectric memories.     

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°.     

Electrical and Pyroelectric Properties of Highly (001)-Oriented (Pb0.76Ca0.24)TiO3 Thin Films Grown by a Sol–Gel Process

Highly (001)-oriented (Pb_0.76Ca_0.24)TiO₃ (PCT) thin films were grown on Pt/Ti/SiO₂/Si substrates using a sol–gel process. The PCT film with a highly (001) orientation showed well-saturated hysteresis loops at an applied field of 800 kV/cm, with remanent polarization ( P _r) and coercive electric field ( E _c) values of 23.6 μC/cm² and 225 kV/cm, respectively. At 100 kHz, the dielectric constant and dielectric loss values of these films were 117 and 0.010, respectively. The leakage-current density of the PCT film was 6.15 × 10⁻⁸A/cm² at 5 V. The pyroelectric coefficient ( p ) of the PCT film was measured using a dynamic technique. At room temperature, the p values and figures-of-merit ( F _D) of the PCT film were 185 μC/m²K and 1.79 × 10⁻⁵ Pa^−0.5, respectively.     

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.     

Preparation of 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 Thin Films Via a Polyvinylpyrrolidone-Assisted Aqueous Sol–Gel Process and Dielectric Properties

Pb(Mg_1/3Nb_2/3)O₃–PbTiO₃ (PMN–PT) thin films were prepared by spin coating using aqueous solutions of metal salts containing polyvinylpyrrolidone, where niobium oxide layers and lead—magnesium–titanium oxide layers were laminated on Pt(111)/TiO _x /SiO₂/Si(100) substrates and fired at 750° or 800°C. 250 ± 20 nm thick 0.7PMN–0.3PT thin films of a single-phase perovskite could be prepared, and the film fired at 750°C had dielectric constants and dielectric loss of 1900 ± 350 and 0.13 ± 0.03, respectively, exhibiting polarization-electric field hysteresis with a remanent polarization of 5.1 μC/cm² and a coercive field of 21 kV/cm.     

Partial Conductivities in SrTiO3: Bulk Polarization Experiments, Oxygen Concentration Cell Measurements, and Defect-Chemical Modeling

Knowledge of the exchange kinetics of O₂ in SrTiO₃ allows us to design appropriate strategies to separate the ionic and the electronic conductivity. In the low-temperature range, where the overall surface reaction is very slow compared to bulk diffusion and measuring time, electrochemical cells of the type Pt|SrTiO₃|Pt are self-blocking and self-sealing and a Wagner–Hebb-type polarization succeeds without the necessity of using selectively blocking electrodes. In the present study the ionic conductivity data obtained for Feand Ni-doped SrTiO₃ in this way are compared to data obtained from the analysis of the oxygen partial pressure dependence of the total conductivity as well as to defect chemical calculations. In complete contrast to the low temperature situation, at high temperatures, where the surface reaction is fast, the emf technique is conveniently applicable. Results are presented for Pt, O₂|SrTiO₃|O₂, Pt cells. The conductivity behavior of SrTi(Fe)O₃ as a function of temperature (20°–1000°C) is complex, due to partially frozen-in equilibria, but even details can be quantitatively understood in terms of a simple defect chemistry. The turnover of the diffusion-controlled regime to the surface reaction-controlled regime can be shifted to significantly lower temperatures by using YBa₂Cu₃O_7–8 electrodes.     

Crystal Phase and Orientation Control in Integrated Ferroelectric CaBi4Ti4O15 Using a Tailored Liquid of Alkoxides

We used a Ca–Bi–Ti complex alkoxide, in which metal–oxygen bonding was confirmed by spectroscopic analysis, to deposit CaBi₄Ti₄O₁₅ (CBTi144) thin films in various configurations. The phase transition of non-ferroelectric pyrochlore to ferroelectric perovskite in the complex-alkoxy-derived CBTi144 thin films was found to depend on the Pt bottom electrodes. Matching of the atomic arrangement to the Ca–Bi–Ti–O thin films was predominant rather than the strain and crystallinity of the bottom electrode. The thin films crystallized at 650°C on (111)-oriented Pt showed random orientation and ferroelectric P – V hysteresis loops. The endurance property was excellent against a number of switchings. For this reason, CBTi144 thin films would be expected to be excellent for application to ferroelectric random access memories (FeRAM). Polar-axis-oriented CBTi144 films were fabricated on Pt foils using the complex metal alkoxide solution. The 500-nm-thick film had a columnar structure comprising well-developed grains. The a / b -axis orientation of the ferroelectric films is considered to be associated with the preferred orientation of Pt foil. The film showed improved ferro- and piezoelectric properties. The P _r, E _c, and d ₃₃ values were enhanced to become twice those of CBTi144 thin films with random orientation. These polar-axis-oriented CBTi144 films are eminently useful in devices as Pb-free piezoelectric materials.     

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.     

Orientation Control in Sol–Gel-Derived BiScO3–PbTiO3 Thin Films

BiScO₃–PbTiO₃ (BSPT) thin films were fabricated via a sol–gel method on Pt(111)/Ti/SiO₂/Si(111) substrates. The effects of different factors on the orientation of the sol–gel-derived BSPT thin films were investigated. The results showed that a higher lead excess concentration, longer drying time, higher pyrolysis temperature, longer pyrolysis time, higher crystallization temperature, and longer crystallization time could enhance the (100) orientation of the BSPT thin films. Based on the experimental results, a mechanism for the orientation evolution in the sol–gel-derived BSPT thin films was proposed. The production of the (100) orientation was attributed to the (100)-oriented PbO nanocrystals forming during the pyrolysis process due to the lattice match.     

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.     

Structure-Optical Property Correlation of Epitaxial Potassium Niobate Thin Films Deposited on Magnesium Oxide (100) Substrates Using a Strontium Titanate Transition Layer

Epitaxial thin films of orthorhombic KNbO₃ (100)/(010) were deposited on MgO (100) single-crystal substrates by pulsed laser ablation using an ε120 Å SrTiO₃ (110) transition layer in between. From X-ray diffraction, the orientation relationships were determined as (010) [100] or (100) [010] KNb0₃∥ (110) [110] SrTiO₃∥ (100) [011] MgO and (010) [001] or (100) [001] KNbO₃∥ (110) [001] SrTiO₃∥ (100) [011] MgO. The measured film refractive indices at 632.8 nm were 2.213 ± 0.003, 2.278 ± 0.003, and 2.285 ± 0.003, respectively, along MgO [100], [011], and [011] directions. A model was developed to correlate the measured effective refractive indices of the film to area fractions of domain variants in the film. Using the model, the area fraction of domains with their polarization axis normal to the substrate was estimated to be 60.0 ± 2.7%.     

TEM Characterization of Single- and Multilayer Triol-Based Sol–Gel PZT (53/47) Thin Films

Integrated lead zirconate titanate thin films deposited on Pt/Ti/SiO₂/Si substrates using a novel triol-based route were characterized using X-ray diffraction and transmission electron microscopy. Crack-free single-layer PZT films of up to 200 nm thick were prepared by triol-based sol–gel processing onto Pt/Ti/SiO₂/Si substrates. Films ∼75 nm thick exhibited a microstructure free of pores and second phase. As film thickness increased, film texture changed from {100} to {111} perovskite. Essentially, single-phase multilayer films could be prepared by the deposition and pyrolysis of several 75 nm layers, followed by a single crystallization step. The influence of heat-treatment schedule on the microstructure and orientation of the multilayer films is discussed. Comparison has been made between multilayer films prepared using the triol-based sol and an inverted mixing order/acetic acid-based sol.     

Sol–Gel Synthesis of High-k HfO2 Thin Films

HfO₂ films were prepared using alkoxy-derived precursor solutions. The effects of the chemical composition of precursor solutions on the microstructure development were investigated for HfO₂ films on Si substrates. The microstructure distinguished developed in the HfO₂ films prepared using the precursor solutions with and without diethanolamine. This result is considered to be due to the difference in the progress of organic decomposition and the behavior of nucleation and grain growth. The flatness and refractive index of the HfO₂ films were improved using diethanolamine-added solution. The refractive index and the dielectric constant of the HfO₂ film prepared at 400°C using a diethanolamine-added solution were about 1.85 and 17, respectively. A similar microstructure developed in the HfO₂ films on polyimide films. Much flat and uniform HfO₂ films are expected for application to integrated optical devices.     

Processing Effects for Integrated PZT: Residual Stress, Thickness, and Dielectric Properties

Processing effects on the dielectric properties of sol–gel-derived PbZrO₃–PbTiO₃ (PZT) films integrated onto Pt/Ti/SiO₂//Si substrates are reported. Sol–gel synthesis and deposition conditions were designed to produce films of varying thickness (95–500 nm) with consistent chemical composition (Pb (Zr_0.53Ti_0.47)O₃), phase content (perovskite), grain size (∼110 nm), crystallographic orientation (nominally (111) fiber textured), and measured residual stress. The Stoney method, using laser reflectance to determine wafer curvature, derived biaxial tensile stress values of 150 and 180 MPa for PZT films after a baseline correction for electrode interactions during thermal processing was employed. The PZT films were of high dielectric quality, with low losses and negligible dispersion. Calculated values of dielectric constant ( ̄ ') were found to decrease from 960 to 600 with decreasing film thickness. A series-capacitor model successfully recovered a room-temperature K ₁' for the PZT (1,170) in good agreement with bulk reports but was unable to reproduce the expected dielectric anomaly near 380°C. This discrepancy and the resulting diffuse phase transformation were attributed to the biaxial tensile stress present in the PZT films.