Nanocluster evolution in Ge ion implanted Ta2O5 layers

Ion implantation-induced nanoclusters were synthesized in reactive sputtered Ta₂O₅ films by Ge⁺ implantation and subsequent annealing. The effects of ion fluence and post-implantation thermal treatment on the kinetics of the nanoclustering were investigated. Ge⁺ ions with energy of 40 keV and fluences of 5 × 10¹⁵, 1 × 10¹⁶ and 5 × 10¹⁶ cm^− 2 were implanted in the Ta₂O₅ layers at room temperature. The samples were thermally treated by rapid thermal annealing in vacuum at 700 °C and 1000 °C for 30, 60 and 180 s. Structural studies of all samples were done by Cross-sectional Transmission Electron Microscopy in diffraction and phase contrast mode. Under optimized conditions (high implantation fluence, subsequent annealing) nanoclusters are formed around the projected ion range of the implanted Ge⁺ ions. The structure of the implanted Ta₂O₅ matrix changes from amorphous to orthorhombic when the annealing was performed at 1000 °C. Although the Ta₂O₅ matrix crystallizes, no evidence is obtained for crystallization of the embedded nanoclusters even after annealing at 1000 °C.     

(5 − x)BaO-xMgO-2Nb2O5 ceramics prepared using a reaction-sintering process

(5 − x)BaO-xMgO-2Nb₂O₅ (x = 0.5 and 1; 5MBN and 10MBN) microwave ceramics prepared using a reaction-sintering process were investigated. Without any calcinations involved, the mixture of BaCO₃, MgO, and Nb₂O₅ was pressed and sintered directly. MBN ceramics were produced after 2-6 h of sintering at 1350-1500 °C. The formation of (BaMg)₅Nb₄O₁₅ was a major phase in producing 5MBN ceramics, and the formation of Ba(Mg_1/3Nb_2/3)O₃ was a major phase in producing 10MBN ceramics. As CuO (1 wt%) was added, the sintering temperature dropped by more than 150 °C. We produced 5MBN ceramics with these dielectric properties: ?_r = 36.69, Qf = 20,097 GHz, and τ_f = 61.1 ppm/°C, and 10MBN ceramics with these dielectric properties: ?_r = 39.2, Qf = 43,878 GHz, and τ_f = 37.6 ppm/°C. The reaction-sintering process is a simple and effective method for producing (5 − x)BaO-xMgO-2Nb₂O₅ ceramics for applications in microwave dielectric resonators.     

VO2 thin films deposited on silicon substrates from V2O5 target: Limits in optical switching properties and modeling

Thermochromic VO₂ thin films presenting a phase change at T_c = 68 °C and having variable thickness were deposited on silicon substrates (Si-001) by radio-frequency sputtering. These thin films were obtained from optimized reduction of low cost V₂O₅ targets. Depending on deposition conditions, a non-thermochromic metastable VO₂ phase might also be obtained. The thermochromic thin films were characterized by X-ray diffraction, atomic force microscopy, ellipsometry techniques, Fourier transform infrared spectrometry and optical emissivity analyses. In the wavelength range 0.3 to 25 μm, the optical transmittance of the thermochromic films exhibited a large variation between 25 and 100 °C due to the phase transition at T_c: the contrast in transmittance (difference between the transmittance values to 25 °C and 100 °C) first increased with film thickness, then reached a maximum value. A model taking into account the optical properties of both types of VO₂ film fully justified such a maximum value. The n and k optical indexes were calculated from transmittance and reflectance spectra. A significant contrast in emissivity due to the phase transition was also observed between 25 and 100 °C.     

Synthesis and Li ion conductivity of Li2O-Nb2O5-P2O5 glasses and glass-ceramics

Glasses with the compositions of xLi₂O-(70 − x)Nb₂O₅-30P₂O₅, x = 30-60, and their glass-ceramics are synthesized using a conventional melt-quenching method and heat treatments in an electric furnace, and Li⁺ ion conductivities of glasses and glass-ceramics are examined to clarify whether the glasses and glass-ceramics prepared have a potential as Li⁺ conductive electrolytes or not. The electrical conductivity (σ) of the glasses increases monotonously with increasing Li₂O content, and the glass of 60Li₂O-10Nb₂O₅-30P₂O₅ shows the value of σ = 2.35 × 10⁻⁶ S/cm at room temperature and the activation energy (E_a) of 0.48 eV for Li⁺ ion mobility in the temperature range of 25-200 °C. It is found that two kinds of the crystalline phases of Li₃PO₄ and NbPO₅ are formed in the crystallization of the glasses and the crystallization results in the decrease in Li⁺ ion conductivity in all samples, indicating that any high Li⁺ ion conducting crystalline phases have not been formed in the present glasses. 60Li₂O-10Nb₂O₅-30P₂O₅ glass shows a bulk nanocrystallization (Li₃PO₄ nanocrystals with a diameter of ∼70 nm) and the glass-ceramic obtained by a heat treatment at 544 °C for 3 h in air exhibits the values of σ = 1.23 × 10⁻⁷ S/cm at room temperature and E_a = 0.49 eV.     

Crystal structures of KBa2Nb5O15 and LaK2Nb5O15 with the TTB-type structure

Single crystals of two niobates, KBa₂Nb₅O₁₅ and LaK₂Nb₅O₁₅, were synthesized by high-temperature reaction and the crystal structures were determined by single crystal X-ray diffraction data. Although the space groups for these compounds were different (the non-centrosymmetrical space group P4bm (#100) for KBa₂Nb₅O₁₅ and the centrosymmetrical one P4/mbm (#127) for LaK₂Nb₅O₁₅), both compounds had the same tetragonal tungsten bronze-type (hereafter TTB-type) structure. The lattice parameters and R-factors of KBa₂Nb₅O₁₅ (LaK₂Nb₅O₁₅) were a = 12.533(2) (12.563(2)) and c = 4.0074(9) (3.9179(9)) Å, and R₁ = 0.040 (0.047) and wR₂=0.131 (0.120), respectively. From the crystal structural analysis, it was clarified that distribution of two large cations was different from each other in the way that K and Ba atoms in KBa₂Nb₅O₁₅ were distributed statistically at two crystallographic sites and K and La atoms in LaK₂Nb₅O₁₅ were ordered.     

Preparation and characterization of Nb2O5-Al2O3 composite oxide formed by cathodic electroplating and anodizing

Al foil was coated with niobium oxide by cathodic electroplating and anodized in a neutral boric acid solution to achieve high capacitance in a thin film capacitor. X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD) revealed the niobium oxide layer on Al to be a hydroxide-rich amorphous phase. The film was crystalline and had stoichiometric stability after annealing at temperatures up to 600 °C followed by anodizing at 500 V, and the specific capacitance of the Nb₂O₅-Al₂O₃ composite oxide was approximately 27% higher than that of Al₂O₃ without a Nb₂O₅ layer. The capacitance was quite stable to the resonance frequency. Overall, the Nb₂O₅-Al₂O₃ composite oxide film is a suitable material for thin film capacitors.     

Phase relations and microwave dielectric properties of vanadium modified Ba5Nb4O15 ceramics

Microwave dielectric ceramics of Ba₅Nb_4−xV_xO₁₅ (x = 0-1) were prepared by a solid-state reaction method. Vanadium substitution can markedly lower the sintering temperature of Ba₅Nb₄O₁₅ from 1450 to 1100 °C. The X-ray powder diffraction analysis reveals the multiphase nature of this system. A hexagonal-to-orthorhombic phase transition was also observed for the BaNb₂O₆ secondary phase. The microwave dielectric properties, such as τ_f, ε_r and Q × f value, decreased with increasing vanadium content for samples sintered at 1100 °C. There was an apparent increase in τ_f and Q × f value for samples (x ≥ 0.5) sintered at 1200 °C due to the hexagonal-to-orthorhombic phase transition of the BaNb₂O₆ phase. These results suggested that the microwave dielectric properties of multiphase ceramics strongly depended on the phase compositions and the phase transitions.     

Structure analysis on the Ba3Mg(Ta1−xNbx)2O9 ceramics: Coexistence of order and disorder

The Ba₃ZnTa₂O₉ (BZT) and Ba₃MgTa₂O₉ (BMT) ceramics, a family of A₃B²⁺B⁵⁺₂O₉ complex perovskites, are extensively utilized in mobile based technologies due to their intrinsic high unloaded quality factor, high dielectric constant and a low (near-zero) resonant frequency temperature coefficient at microwave frequencies. The preparation conditions as well as size and nature of B cations have a profound effect on the final dielectric properties. In this article, we report the effect of Nb⁵⁺ at the Ta⁵⁺ site on the BMT structure prepared at four synthesis temperatures (1300, 1400, 1500 and 1600 °C). The analysis has been carried out using the Rietveld technique on the X-ray powder diffraction data. Results suggest that both the preparation temperatures and Nb⁵⁺ content have significant effect on the ordering of B cations in the Ba₃Mg(Ta_1−xNb_x)₂O₉ solid solution. A disordered (cubic) structure is preferred by the 1300 °C compounds. The weight percentage of the ordered (trigonal) phase escalates, for a given composition, with increasing calcination temperature. A fully ordered trigonal arrangement exists only for x = 0.0 and 0.2 compounds calcined at 1600 °C, and the rest are biphasic (cubic and trigonal). The increase in the cubic fraction upon Nb⁵⁺ augmentation suggests that the solid solution leans more toward the disordered structural arrangement of B²⁺ and B⁵⁺ cations.     

Ion conducting properties of hydrogen-containing Ta2O5 thin films prepared by reactive sputtering

Hydrogen-containing Ta₂O₅ (Ta₂O₅:H) thin films are considered to be a candidate for a proton-conducting solid-oxide electrolyte. In this study, Ta₂O₅:H thin films were prepared by reactively sputtering a Ta metal target in an O₂ + H₂O mixed gas. The effects of sputtering power and post-deposition heat treatment on the ion conducting properties of the Ta₂O₅:H thin films were studied. The ionic conductivity of the films was improved by decreasing the RF power and a maximum conductivity of 2 × 10⁻⁹ S/cm was obtained at an RF power of 20 W. The ionic conductivity decreased by heat-treatment in air, and no ion-conduction was observed after treatment at 300 °C due to the decrease in hydrogen content in the films.     

Microwave dielectric properties and microstructures of the 11Li2O-3Nb2O5-12TiO2 ceramics with B2O3 addition

The effects of B₂O₃ addition, as a sintering agent, on the sintering behavior, microstructure and microwave dielectric properties of the 11Li₂O-3Nb₂O₅-12TiO₂ (LNT) ceramics have been investigated. With the low-level doping of B₂O₃ (≤2 wt.%), the sintering temperature of the LNT ceramic could be effectively reduced to 900 °C. The B₂O₃-doped LNT ceramics are also composed of Li₂TiO₃ss and “M-phase” phases. No other phase could be observed in the 0.5-2 wt.% B₂O₃-doped ceramics sintered at 840-920 °C. The addition of B₂O₃ induced no obvious degradation in the microwave dielectric properties but increased the τ_f values. Typically, the 0.5 wt.% B₂O₃-doped ceramics sintered at 900 °C have better microwave dielectric properties of ?_r = 49.2, Q × f = 8839 GHz, τ_f = 57.6 ppm/°C, which suggest that the ceramics could be applied in multilayer microwave devices requiring low sintering temperatures.     

Sol-gel preparation of near-infrared broadband emitting Er-doped SiO2-Ta2O5 nanocomposite films

This article reports a study on the preparation, densification process, and structural and optical properties of SiO₂-Ta₂O₅ nanocomposite films obtained by the sol-gel process. The films were doped with Er³⁺, and the Si:Ta molar ratio was 90:10. Values of refractive index, thickness and vibrational modes in terms of the number of layers and thermal annealing time are described for the films. The densification process is accompanied by OH group elimination, increase in the refractive index, and changes in film thickness. Full densification of the film is acquired after 90 min of annealing at 900 °C. The onset of crystallization and devitrification, with the growth of Ta₂O₅ nanocrystals occurs with film densification, evidenced by high-resolution transmission electron microscopy. The Er³⁺-doped nanocomposite annealed at 900 °C consists of Ta₂O₅ nanoparticles, with sizes around 2 nm, dispersed in the SiO₂ amorphous phase. The main emission peak of the film is detected at around 1532 nm, which can be assigned to the ⁴I_13/2 → ⁴I_15/2 transition of the Er³⁺ ions present in the nanocomposites. This band has a full width at half medium of 64 nm, and the lifetime measured for the ⁴I_13/2 levels is 5.4 ms, which is broader compared to those of other silicate systems. In conclusion, the films obtained in this work are excellent candidates for use as active planar waveguide.     

Low temperature sintering and microwave dielectric properties of ZnTiNb2O8 ceramics with BaCu(B2O5) additions

The phases, microstructure and microwave dielectric properties of ZnTiNb₂O₈ ceramics with BaCu(B₂O₅) additions prepared by solid-state reaction method have been investigated using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The pure ZnTiNb₂O₈ ceramic shows a high sintering temperature of about 1250 °C. However, it was found that the addition of BaCu(B₂O₅) lowered the sintering temperature of ZnTiNb₂O₈ ceramics from above 1250 °C to 950 °C due to the BCB liquid-phase. The results showed that the microwave dielectric properties were strongly dependent on densification, crystalline phases and grain size. Addition of 3 wt% BCB in ZnTiNb₂O₈ ceramics sintered at 950 °C afforded excellent dielectric properties of ?_r = 32.56, Q × f = 20,100 GHz (f = 5.128 GHz) and τ_f = −64.87 ppm/°C. These represent very promising candidates for LTCC dielectric materials.     

Fabrication of TiO2-based transparent conducting oxide on glass and polyimide substrates

We report on preparation and properties of anatase Nb-doped TiO₂ transparent conducting oxide films on glass and polyimide substrates. Amorphous Ti_0.96Nb_0.04O₂ films were deposited at room temperature by using sputtering, and were then crystallized through annealing under reducing atmosphere. Use of a seed layer substantially improved the crystallinity and resistivity (ρ) of the films. We attained ρ = 9.2 × 10^− 4 Ω cm and transmittance of ~ 70% in the visible region on glass by annealing at 300 °C in vacuum. The minimum ρ of 7.0 × 10^− 4 Ω cm was obtained by 400 °C annealing in pure H₂.     

Preparation and studies of Eu and Tb co-doped Gd2O3 and Y2O3 sol-gel scintillating films

Eu³⁺ (2.5 at.%) and Tb³⁺ (0.005-0.01 at.%) co-doped gadolinium and yttrium oxide (Gd₂O₃ and Y₂O₃) powders and films have been prepared using the sol-gel process. High density and optical quality thin films were prepared with the dip-coating technique. Gadolinium (III) 2,4-pentadionate and yttrium (III) 2,4-pentadionate were used as precursors, and europium and terbium in their nitrate forms were used as doping agents. Chemical and structural analyses (infrared spectroscopy, X-ray diffraction and high-resolution transmission electron microscopy) were conducted on both sol-gel precursor powders and dip-coated films. The morphology of thin films heat-treated at 700 °C was studied by means of atomic force microscopy. It was shown that the highly dense and very smooth films had a root mean roughness (RMS) of 2 nm ± 0.2 (A = 0.0075 Tb³⁺) and 24 nm ± 3.0 (B = 0.01 Tb³⁺). After treatment at 700 °C, the crystallized films were in the cubic phase and presented a polycrystalline structure made up of randomly oriented crystallites with grain sizes varying from 20 to 60 nm. The X-ray induced emission spectra of Eu³⁺- and Tb³⁺-doped Gd₂O₃ and Y₂O₃ powders showed that Tb³⁺ contents of 0.005, 0.0075 and 0.01 at.% affected their optical properties. Lower Tb³⁺ concentrations (down to 0.005 at.%) in both systems enhanced the light yield.     

Subsolidus phase equilibria and the Li5Nd4FeO10 phase in the Li2O-Nd2O3-Fe2O3 system

A survey of the subsolidus phase equilibria in the system Li₂O-Nd₂O₃-Fe₂O₃ was made at subsolidus temperatures in the range 1000-1050 °C. A ternary phase was identified. The phase is centered on Li₅Nd₄FeO₁₀, with a cubic lattice a = 11.9494 Å. The compound melts incongruently at 1105 °C. The magnetic susceptibility was measured in the temperature range 4-300 K. The compound is paramagnetic in the temperature range 150-300 K and follows the Curie-Weiss law. At about T_N = 10 K, a long-range magnetic ordering is observed.     

Tantalum influence on physical properties of (K0.5Na0.5)(Nb1−xTax)O3 ceramics

Lead-free (K_0.5Na_0.5)(Nb_1−xTa_x)O₃ ceramics with x = 0.00-0.30 were prepared by the solid-state reaction technique. The effects of Ta on microstructure, crystallographic structure, phase transition and piezoelectric properties have been investigated. It has been shown that the substitution of Ta decreases Curie temperature T_C and orthorhombic-tetragonal phase transition temperature T_O-T, while increasing the rhombohedral-orthorhombic phase transition temperature T_R-O. In addition, piezoelectric activity is enhanced with the increase of Ta content. The ceramics with x = 0.30 have the high value of piezoelectric coefficient d₃₃ = 205 pC/N. Moreover, k_p shows little temperature dependence between −75° C and 75 °C, and d₃₃ exhibits very good thermal stability over the range from −196 °C to 75 °C in the aging test.     

Nd-substituted SrBi2Ta2O9 ferroelectric thin films prepared by radio frequency magnetron sputtering

Nd-substituted SrBi₂Ta₂O₉ (SNBT) thin films are sputtered on Pt/Ta/SiO₂/Si substrates. X-ray diffraction and x-ray photoelectron spectroscopy studies indicate that Nd³⁺ is substituted into the bismuth layered perovskite structure, preferentially at the Sr²⁺ site. The annealed thin film is polycrystalline with plate/needle-like grain microstructure. Secondary ion mass spectrometry results show that elements in SNBT thin film homogeneously distribute along film depth and interfacial diffusion takes place during post annealing. The Nd substitution leads to enhanced remnant polarization (2P_r = 18 μC/cm²) and reduced coercivity (2E_c = 64 kV/cm) at 180 kV/cm measured at 25 °C. After 10¹⁰ switching cycles, around 9% remnant polarization is decreased.     

Phase relations of the Li2O-Ta2O5-B2O3 and Li2O-WO3-B2O3 systems and promising nonlinear optical compounds in K2O-Ta2O5-B2O3 system

The subsolidus phase equilibria of the Li₂O-Ta₂O₅-B₂O₃, K₂O-Ta₂O₅-B₂O₃ and Li₂O-WO₃-B₂O₃ systems have been investigated mainly by means of the powder X-ray diffraction method. Two ternary compounds, KTaB₂O₆ and K₃Ta₃B₂O₁₂ were confirmed in the system K₂O-Ta₂O₅-B₂O₃. Crystal structure of compound KTaB₂O₆ has been refined from X-ray powder diffraction data using the Rietveld method. The compound crystallizes in the orthorhombic, space group Pmn2₁ (No. 31), with lattice parameters a = 7.3253(4) Å, b = 3.8402(2) Å, c = 9.3040(5) Å, z = 2 and D_calc = 4.283 g/cm³. The powder second harmonic generation (SHG) coefficients of KTaB₂O₆ and K₃Ta₃B₂O₁₂ were five times and two times as large as that of KH₂PO₄ (KDP), respectively.     

Low-temperature firing and microwave dielectric properties of ZnO-Nb2O5-TiO2-SnO2 ceramics with CuO-V2O5

The effects of CuO-V₂O₅ addition on the sintering temperature and microwave dielectric properties of ZnO-Nb₂O₅-TiO₂-SnO₂ were investigated. The CuO-V₂O₅ addition lowered the sintering temperature of ZnO-Nb₂O₅-TiO₂-SnO₂ ceramics effectively from 1150 to 860 °C due to the liquid-phase effect of Cu₂V₂O₇ and Cu₃(VO₄)₂, as observed by XRD. The microwave dielectric properties were found to strongly correlate with the sintering temperature and the amount of CuO-V₂O₅ addition. The maximum Qf values decreased with increasing CuO-V₂O₅ content, due to the formation of the second phase, Cu₃(VO₄)₂ and CuNbO₃. Zero τ_f value can be obtained by properly adjusting the sintering temperature. At 860 °C, ZnO-Nb₂O₅-TiO₂-SnO₂ ceramics with 1.5 wt.% CuO-V₂O₅ gave excellent microwave dielectric properties: ?_r = 42.3, Qf = 9000 GHz and τ_f = 8 ppm/°C.     

Bi4LnNb3O15 (Ln = La, Pr, Nd) and Bi4LaTa3O15: New intergrowth Aurivillius related phases

We describe the synthesis and characterization of new intergrowth Aurivillius related phases, Bi₄LnNb₃O₁₅ (Ln = La, Pr, Nd) and Bi₄LaTa₃O₁₅. Both powder X-ray diffraction and electron microscopy investigations show that the compounds adopt orthorhombic structures with the cell parameters a ∼ 5.5 Å, b ∼ 5.5 Å and c ∼ 20.9 Å, suggesting an ordered intergrowth structure that consists of n = 1 [Bi₂NbO₆]⁻ and n = 2 [Bi₂LnNb₂O₉]⁺ Aurivillius fragments which are stacked alternately along the c-axis. The oxides do not show a second harmonic generation (SHG) response toward 1064 nm laser radiation; they do not show a ferroelectric-paraelectric transition either between 30 and 900 °C in dielectric measurements, indicating a centrosymmetric structure. Optical absorption studies show that the intergrowth phases possess considerably smaller band gaps than the parent Nb₂O₅ and Ta₂O₅.