The effect of solvent water content on the dielectric properties of Al2O3 films grown by atmospheric pressure mist-CVD

Aluminum oxide (Al₂O₃) dielectric layers were grown by a mist-chemical vapor deposition (mist-CVD) process at 300 °C, using solvent mixtures containing acetone and water. As the acetone to water ratio was varied from 9:1 to 7:3, the leakage current of Al₂O₃ at an electric field of 7 MV/cm² decreased from 9.0 × 10^?7 to 4.4 × 10^?10 A/cm², and the dielectric constant increased from 6.03 to 6.85 with improved hysteresis during capacitance-voltage measurements. Consequently, the most robust Al₂O₃ films were obtained at an acetone to water ratio of 7:3, with a dielectric constant (κ) close to the ideal value 7.0, and a breakdown field of approximately 9 MV/cm. Thin film transistors (TFTs) incorporating In-Sn-Zn-O (ITZO) as the semiconductor were fabricated with the Al₂O₃ (7:3) dielectric onto p⁺⁺-Si substrates. The devices exhibit high electrical performance, with a high field effect mobility of 42.7 cm²V^?1s^?1, and a small subthreshold swing (S.S.) value of 0.44 V/decade.     

Effects of Tb doping on structural and electrical properties of 47(Ba0.7Ca0.3)TiO3–0.53Ba(Zr0.2Ti0.8)O3 thin films at various annealing temperature by pulsed laser deposition

The ceramic thin films of 47(Ba_0.7Ca_0.3)TiO₃–0.53Ba(Zr_0.2Ti_0.8)O₃ (BCZT) + x (x = 0.2, 0.3, 0.4 and 0.5) mol% Tb were grown on Pt(111)/Si substrates with various annealing temperature by pulsed laser deposition. The XRD spectra confirm that Tb element can enhance the (l10) and (111) orientations in ceramic films. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) images show that Tb-doping can increase particle size effectively. The surface of Tb-doped film annealed at 800 ℃ is uniform and crack-free, and the average particle size and mean square roughness (RMS) are about 280 nm and 4.4 nm, respectively. Comparing with pure BCZT, the residual polarization (P_r) of 0.4 mol% Tb-doped film annealed at 800 ℃ increase from 3.6 to 9.8 μC/cm². Moreover, the leakage current density value of Tb doped films are one order of magnitude (5.33 × 10^?9?1.97 × 10^?8 A/cm² under 100 kV/cm) smaller than those of pure BCZT films (1.02 × 10^?7 A/cm²).     

Robust SiO2 gate dielectric thin films prepared through plasma-enhanced atomic layer deposition involving di-sopropylamino silane (DIPAS) and oxygen plasma: Application to amorphous oxide thin film transistors

DIPAS (di-isopropylamino silane, H₃Si[N(C₃H₇)₂]) and O₂ plasma were employed, using plasma-enhanced atomic layer deposition (PEALD), to deposit silicon oxide to function as the gate dielectric at low temperature, i.e., below 200 °C. The superior amorphous SiO₂ thin films were deposited through the self-limiting reactions of atomic layer deposition with a deposition rate of 0.135 nm/cycle between 125 and 200 °C. PEALD-based SiO₂ thin layer films were applied to amorphous oxide thin film transistors constructed from amorphous In-Ga-Zn-O (IGZO) oxide layers, which functioned as channel layers in the bottom-gated thin film transistor (TFT) structure, with the aim of fabricating transparent electronics. The SiO₂ gate dielectric exhibited the highest TFT performance through the fabrication of heavily doped n-type Si substrates, with a saturation mobility of 16.42 cm²/V·s, threshold voltage of 2.95 V and large on/off current ratio of 3.69 × 10⁸. Ultimately, the highly doped Si was combined with the ALD-based SiO₂ gate dielectric layers, leading to a saturation mobility of 16.42 cm²/V·s, threshold voltage of 2.95 V, S-slope of 0.1944, and on/off current ratio of 3.69 × 10⁸. Semi-transparent and transparent TFTs were fabricated and provided saturation mobilities of 22.18 and 24.29 cm²/V·s, threshold voltages of 4.18 and 2.17 V, S-slopes of 0.1944 and 0.1945, and on/off current ratios of 9.63 × 10⁸ and 1.03 × 10⁷, respectively.     

Investigation on the anti-reduction mechanism of Ti4+ in high dielectric constant system Ca0.9La0.067TiO3 by doping with Al2O3

Ca_0.9La_0.067TiO₃ (abbreviated as CLT) ceramics doped with different amount of Al₂O₃ were prepared via the solid state reaction method. The anti-reduction mechanism of Ti⁴⁺ in CLT ceramics was carefully investigated. X-ray diffraction (XRD) was used to analyze the phase composition and lattice structure. Meanwhile, the Rietveld method was taken to calculate the lattice parameters. X-ray photoelectron spectroscopy (XPS) was employed to study the valence variation of Ti ions in CLT ceramics without and with Al₂O₃. The results showed that Al³⁺ substituted for Ti⁴⁺ to form solid solution and the solid solubility limit of Al³⁺ is near 1.11 mol%. Furthermore, the reduction of Ti⁴⁺ in CLT ceramics was restrained by acceptor doping process and the Q × f values of CLT ceramics were improved significantly. The CLT ceramic doped with 1.11 mol% Al₂O₃ exhibited good microwave dielectric properties: ε_r = 141, Q × f = 6848 GHz, τ_f = 576 ppm/°C.     

Controlling microstructure and film growth of relaxor-ferroelectric thin films for high break-down strength and energy-storage performance

The relaxor ferroelectric Pb_0.9La_0.1(Zr_0.52Ti_0.48)O₃ (PLZT) thin films were deposited using pulsed laser deposition, and their microstructures, break-down field strengths and energy storage performances were investigated as a function of the buffer layer and electrode. A large recoverable energy-storage density (U_reco) of 23.2 J/cm³ and high energy-storage efficiency (η) of 91.6% obtained in the epitaxial PLZT film grown on SrRuO₃/SrTiO₃/Si are much higher than those in the textured PLZT film (U_reco = 21.9 J/cm³, η = 87.8%) on SrRuO₃/Ca₂Nb₃O₁₀-nanosheet/Si and the polycrystalline PLZT film (U_reco = 17.6 J/cm³, η = 82.6%) on Pt/Ti/SiO₂/Si, under the same condition of 1500 kV/cm and 1 kHz, due to the slim polarization loop and significant antiferroelectric-like behavior. Owing to the high break-down strength (BDS) of 2500 kV/cm, a giant U_reco value of 40.2 J/cm³ was obtained for the epitaxial PLZT film, in which U_reco values of 28.4 J/cm³ (at BDS of 2000 kV/cm) and 20.2 J/cm³ (at BDS of 1700 kV/cm), respectively, were obtained in the textured and polycrystalline PLZT films. The excellent fatigue-free properties and high thermal stability were also observed in these films.     

Doping behaviors of NiO and Nb2O5 in BaTiO3 and dielectric properties of BaTiO3-based X7R ceramics

Doping behaviors of NiO and Nb₂O₅ in BaTiO₃ in two doping ways and dielectric properties of BaTiO₃-based X7R ceramics were investigated. When doped in composite form, the additions rendered higher solubility than that doped separately due to the identical valence between the complex (Ni_1/3²⁺Nb_2/3⁵⁺)⁴⁺ and Ti⁴⁺. NiO–Nb₂O₅ composite oxide was more effective in broadening dielectric constant peaks which was responsible for the temperature-stability of BaTiO₃ ceramics. A reduction in grain size was observed in the specimens with 0.5–0.8 mol% NiO–Nb₂O₅ composite oxide, whereas the abnormal growth of individual grains took place in the 1.0 mol% NiO–Nb₂O₅ composite oxide-doped specimen. When the specimen of BaTiO₃ doped with 0.8 mol% NiO–Nb₂O₅ composite oxide was sintered at 1300 °C for 1.5 h in air, good dielectric properties were obtained and the requirement of (EIA) X7R specification with a dielectric constant of 4706 and dielectric loss lower than 1.5% were satisfied.     

Low dielectric loss of Bi-doped BaZr0.15Ti0.85O3 ceramics for high-voltage capacitor applications

BaZr_0.15Ti_0.85O₃ ceramics are prepared via the conventional solid state reaction method. The effects of Bi₂O₃·3TiO₂ doped on dielectric properties and breakdown strength of BaZr_0.15Ti_0.85O₃ ceramics are systematically discussed. Doping of Bi₂O₃·3TiO₂ can obviously improve the breakdown strength and reduce the dielectric loss of the material. It is attributed to the Bi³⁺ substituted Ba²⁺ is an unequal ion substitution, and two Bi³⁺ substitute three Ba²⁺ to produce an A vacancy, thereby increasing the lattice energy and promoting the diffusion and migration of the particles during the sintering process, promoting the sintering and reducing the sintering temperature. However, the dielectric constant of the material is decreased. When the amount of Bi₂O₃·3TiO₂ is 12 mol%, the minimum dielectric loss tanδ = 0.0009, the maximum breakdown strength is E_b = 15.09 kV/mm, the insulation resistivity is 3.52 × 10¹¹ Ω cm. The energy storage density of the BaZr_0.15Ti_0.85O₃ ceramic samples doped with Bi₂O₃·3TiO₂ varies from 0.008 J/cm³ to 0.012 J/cm³.     

High tunability in (1 1 0)-oriented BaZr0.2Ti0.8O3 (BTZ) lead-free thin films fabricated by pulsed laser deposition

Using a pulsed laser deposition method the BaZr_0.2Ti_0.8 O₃ (BTZ) lead–free thin films with a thickness of ~250 nm were grown on FTO, ITO and Pt–Si substrates, respectively. The analysis results of microstructural, dielectric properties and leakage current reveal that the thin films deposited on Pt–Si substrates are oriented growth along the (1 1 0) direction and exhibit the optimal performance characteristics. Calculations of figure of merit (FoM) and dielectric tunability display a maximum value of ~42.8 and ~68.5% at E = 400 kV/cm at room temperature, respectively. The excellent tunable properties, high dielectric constant (~635@ 100 kHz) and low leakage current density of (9.3 × 10^–8 A/cm² at 400 kV/cm) make the (1 1 0)–oriented BaZr_0.2Ti_0.8 O₃ thin film to be an attractive material for applications of tunable devices.     

Enhancement of breakdown strength of SrTiO3/nano-SiO2 composite film prepared by sol-gel technology

Dielectric (1-x)SrTiO₃/xSiO₂ (x=0, 0.01, 0.05 and 0.1) composite thin films were deposited onto Pt (100)/Ti/SiO₂/Si substrates via sol-gel and spin coating technology and their surface morphology was examined by field emission scanning electron microscopy, indicating that surface morphology was apparently influenced by the nano-SiO₂ addition. A broad adsorption band at 3200–3500 cm⁻¹ attributed to stretching vibrations of O-H bonds in the absorbed water was observed in fourier transform infrared spectroscopy (FTIR). The X-ray photoelectron spectroscopy (XPS) results show that nano-SiO₂ particles facilitate water absorption of STO thin films. The breakdown strength of SrTiO₃/nano-SiO₂ composite films is increased to about 332 MV/m. At the same time, the leakage current of 0.9SrTiO₃/0.1SiO₂ composite thin films decreases by two orders of magnitude under high electric field. Above results show that nano-SiO₂ particles facilitate water absorption of the thin films, making SrTiO₃ act as an effective solid state electrolyte for the anodic oxidation to achieve higher breakdown strength.     

Preparation and characterization of transparent indium- doped TiO2 films deposited by MOCVD

Titanium dioxide (TiO₂) films doped with different indium (In) concentrations have been prepared on SrTiO₃ (STO) substrates by high vacuum metalorganic chemical vapor deposition (MOCVD). X-ray diffraction (XRD) analyses revealed the TiO₂ films doped with low In concentrations to be [001] oriented anatase phase and the films with high In concentrations to present polycrystalline structures. The 1.8% In-doped TiO₂ film exhibited the best electrical conductivity properties with the lowest resistivity of 8.68×10⁻² Ω cm, a Hall mobility of 10.9 cm² V⁻¹ s⁻¹ and a carrier concentration of 6.5×10¹⁸ cm⁻³. The films showed excellent transparency with average transmittances of over 85% in the visible range.     

Microstructure and dielectric properties of SrTiO3 ceramics by controlled growth of silica shells on SrTiO3 nanoparticles

SrTiO₃@SiO₂ nanopowder was synthesized via a core-shell nano-scale technique that is known as the Stöber process. The effect of the SiO₂ concentration on microstructure, dielectric response and energy storage properties of SrTiO₃@SiO₂ ceramics was investigated. Transmission electron microscopy (TEM) results confirmed the formation of core–shell nanostructures with controlled shell thicknesses between 2 nm and 13 nm. After increasing SiO₂, a secondary phase with Sr₂TiSi₂O₈ appeared due to inter-diffusion reactions between the SrTiO₃ core and SiO₂ shells during the sintering process. The results show that both breakdown strength and energy density improved apparently. The homogeneous coating of silica on ST cores is considered to dominate the contribution to improved breakdown strength. The composition for SrTiO₃ coated with 2.5 wt% SiO₂ shows the maximum energy storage density (1.2 J/cm³) and a breakdown strength of 310 kV/cm. The former is higher than for pure SrTiO₃ (0.19 J/cm³). Measurements of the dielectric performance indicate that the SrTiO₃@SiO₂ ceramics possess good bias stabilities compared to pure ST ceramics.     

Effects of TiO2 addition on dielectric and energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics

In this work, 25.6BaO-6.4K₂O-32Nb₂O₅-36SiO₂-xTiO₂ (0 ≤ x ≤10 mol%) (BKNST) glass ceramics were synthesized by conventional melts and controllable crystallization method. The effects of different TiO₂ addition on the phase composition, dielectric and energy storage properties of BKNS glass ceramics were systematically evaluated. With the TiO₂ concentration increasing, a growing content of Ba₂TiO₄ phase was observed in the glass ceramics. The microstructures appeared to be homogenous and uniform with very low porosity through the addition of TiO₂, for which the maximal breakdown strength of 2112 kV/cm and the corresponding energy storage density of 9.48 J/cm³ were obtained with x = 7.5. The extremely low dielectric loss of less than 1‰ (25 °C, 100 kHz) and the obviously improved microstructure contributed to the increased breakdown strength. In addition, the discharge power density of the glass-ceramic capacitor (x = 7.5) was investigated using the RLC charge-discharge circuit and a relatively high value of 16 MW/cm³ at 300 kV/cm was obtained.     

Giant permittivity and low dielectric loss of Fe doped BaTiO3 ceramics: Experimental and first-principles calculations

Fe doped BaTiO₃ ceramics with giant permittivity and low dielectric loss were synthesized in N₂/H₂ atmosphere started with BaTiO₃ powders and iron powders. XRD analysis exhibited the tetragonal-pseudocubic phase transition when the Fe content is 3 mol%. XPS spectra confirmed the iron oxides with mixed-valence structure of Fe²⁺/Fe³⁺, while Ti-ions maintain Ti⁴⁺3d⁰ states without any oxidization-reduction. For the case of ceramics with 5 mol% Fe, the dielectric constant was 66,650 at 1000 Hz at room temperature, 19 times higher than that of pure BaTiO₃ ceramics, while the dielectric loss tangent was 0.13. Comparison with other giant-permittivity materials demonstrated the superior potential of present ceramics. First-principles calculations investigated the interfacial interaction of Fe-[TiO₂] interface and Fe-[BaO] interface. Giant dielectric constant was induced by the interfacial polarization between insulating ferroelectrics and semiconducting iron oxides with mixed-valence states, as well as the contribution from the generated electron hopping conduction.     

Hot corrosion behavior of TiO2 doped,Yb2O3 stabilized zirconia exposed to V2O5 + Na2SO4 molten salt at 700–1000 °C

3.5 mol% Yb₂O₃ stabilized zirconia (YbSZ) doped with 10 mol% TiO₂ (Ti-YbSZ) was produced, and its hot corrosion behavior exposed to Na₂SO₄ + V₂O₅ molten salt was investigated. The as-fabricated ceramic mainly consists of metastable tetragonal (t′) phase. When exposed to the molten salt at 700 °C, 800 °C, 900 °C and 1000 °C for 2 h and 10 h, YbVO₄ and m-ZrO₂ formed as corrosion products due to chemical reactions between the ceramics and the salt. Ti⁴⁺ in Ti-YbSZ solid solution keeps stable during the hot corrosion tests, which acts as a stabilizer for ZrO₂, preventing total decomposition of the t′ phase. After the hot corrosion tests, Ti-YbSZ has an apparently lower m phase content than Y₂O₃ doped Zirconia and YbSZ, indicative of better corrosion resistance. The hot corrosion mechanism of Ti-YbSZ is proposed based on Lewis acid-base rule, phase diagrams and thermodynamics.     

Temperature–stable dielectrics based on Cu–doped Bi2Mg2/3Nb4/3O7 pyrochlore ceramics for LTCC

Temperature–stable dielectrics based on Cu–doped Bi₂Mg_2/3Nb_4/3O₇ pyrochlore ceramics were prepared by conventional solid–state reaction. Microstructure analysis indicates that all of the specimen maintain the cubic pyrochlore phase, a fluorite–like phase of Bi₃NbO₇ and a Bi₅Nb₃O₁₅ formed for Cu doping. The dielectric constant is dominated by densification of samples and secondary phases, while the dielectric loss is related by the secondary phases, grain boundaries, and leakage current characteristics. The (1-x)BMN - xCuO(x = 0.1 mol%) ceramic sintered at 925 °C shows excellent dielectric properties with dielectric constant of ~184.06, dielectric loss of ~0.0017 and near zero τ_ε (?20 ppm/°C) is obtained at sintering temperature of 925 °C, which could be a promising candidate for LTCC.     

Development of PLZT dielectrics on base metal foils for embedded capacitors

We have deposited Pb_0.92La_0.08Zr_0.52Ti_0.48O₃ (PLZT) films on nickel and copper substrates to create film-on-foil capacitors that exhibit excellent dielectric properties and superior breakdown strength. Measurements with PLZT films on LaNiO₃-buffered Ni foils yielded the following: relative permittivity of 1300 (at 25 °C) and 1800 (at 150 °C), leakage current density of 6.6 × 10^?9 A/cm² (at 25 °C) and 1.4 × 10^?8 A/cm² (at 150 °C), and mean breakdown field strength ≈2.5 MV/cm. With PLZT deposited directly on Cu foils, we observed dielectric constant ≈1100, dielectric loss (tan δ) ≈0.06, and leakage current density of 7.3 × 10^?9 A/cm² when measured at room temperature.     

(Al3+, Nb5+) co–doped CaCu3Ti4O12: An extended approach for acceptor–donor heteroatomic substitutions to achieve high–performance giant–dielectric permittivity

Substitution of (Al³⁺, Nb⁵⁺) co–dopants into TiO₆ octahedral sites of CaCu₃Ti₄O₁₂ ceramics, which were prepared by a solid state reaction method and sintered at 1090 °C for 18 h, can cause a great reduction in a low–frequency loss tangent (tanδ≈0.045–0.058) compared to those of Al³⁺ or Nb⁵⁺ single–doped CaCu₃Ti₄O₁₂. Notably, very high dielectric permittivities of 2.9 ? 4.1 × 10⁴ with good dielectric–temperature stability are achieved. The room–temperature grain boundary resistance (R_gb≈0.37–1.17 × 10⁹ Ω.cm) and related conduction activation energy (E_gb≈0.781–0.817 eV), as well as the non–Ohmic properties of the co–doped ceramics are greatly enhanced compared to single–doped ceramics (R_gb≈10⁴–10⁶ Ω cm and E_gb≈0.353–0.619 eV). The results show the importance of grain boundary properties for controlling the nonlinear–electrical and giant–dielectric properties of CaCu₃Ti₄O₁₂ ceramics, supporting the internal barrier layer capacitor model of Schottky barriers at grain boundaries.     

Influence of MnO2 and Co3O4 dopants on dielectric properties of Pb(Fe2/3W1/3)O3 ceramics

Dielectric properties of Pb(Fe_2/3W_1/3)O₃ ceramic doped with 0.05–1 mol% of MnO₂ or Co₃O₄ were investigated in a wide temperature range from −160 to 450 °C at frequencies 10 Hz–1 MHz. Besides the maxima corresponding to the ferroelectric–paraelectric transition, at higher temperatures other peaks in temperature dependencies of relative electrical permittivity and dissipation factor were observed, attributed to dielectric relaxation. The location and height of these peaks are strongly related to frequency and the dopant level. Both MnO₂ and Co₃O₄ addition caused a significant increase in the resistivity of PFW ceramic—from 10⁶ Ω cm for undoped samples to 10¹¹ Ω cm for those with 1 mol% of a dopant. The activation energies of relaxation calculated on the basis of dielectric measurements are very close to the conduction activation energies determined in similar temperature range.     

Structural and electrical properties of Sr2NaNb4O13 thin film grown by electrophoretic method using nanosheets synthesized from K(Sr2Na)Nb4O13 compound

Sr₂NaNb₄O₁₃⁻ (SNNO⁻) nanosheets were exfoliated from the K(Sr₂Na)Nb₄O₁₃ compound that was synthesized at 1200 °C. The SNNO⁻ nanosheets were deposited on a Pt/Ti/SiO₂/Si substrate at room temperature by the electrophoretic method. Annealing was conducted at various temperatures to remove organic defects in the SNNO film. A crystalline SNNO phase without organic defects was formed in the film annealed at 500 °C. However, a SrNb₂O₆ secondary phase was formed in the films annealed above 600 °C, probably due to the evaporation of Na₂O. The SNNO thin film annealed at 500 °C showed a dielectric constant of 74 at 1.0 MHz with a dielectric loss of 2.2%. This film also exhibited a low leakage current density of 9.0 × 10⁻⁸ A/cm² at 0.6 MV/cm with a high breakdown electric field of 0.72 MV/cm.     

Dielectric and thermal properties of AlN ceramics

The effects of slow-cooling and annealing conditions on dielectric loss, thermal conductivity and microstructure of AlN ceramics were investigated. Y₂O₃ from 0.5 to 1.25 mol% at 0.25% increments was added as a sintering additive to AlN powder and pressureless sintering was carried out at 1900 °C for 2 h in a nitrogen flowing atmosphere. To improve the properties, AlN samples were slow-cooled at a rate of 1 °C min⁻¹ from 1900 to 1750 °C, subsequently cooled to 970 °C at a rate of 10 °C min⁻¹ and then annealed at the same temperature for 4 h. AlN and YAG (5Al₂O₃/3Y₂O₃) were the only identified phases from XRD. AlN doped with 0.5 and 0.75 mol% Y₂O₃ had a low loss of <2.0 × 10⁻³ and a high thermal conductivity of >160 W m⁻¹ °C⁻¹.