Synthesis and properties of Ba(Zn1/3Ta2/3)O3 for microwave and millimeter wave applications

High dielectric materials have gained an important position in microwave electronics by reducing the size and cost of components for a wide range of applications from mobile telephony to spatial communications. Ba(Zn_1/3Ta_2/3)O₃ (BZT) is an A(B′B″)O₃ type perovskite material, showing ultra high values of the quality factor Q. Ceramic-based BZT dielectric materials were prepared by solid state reaction. The samples were sintered at temperatures in the range 1400 ÷ 1600 °C for 4 h. Compositional, structural and morphological characterization were performed by using XRD, SEM and EDX analysis. The dielectric properties were measured in the microwave range (6 ÷ 7 GHz). An additional annealing at 1400 °C for 10 h has improved some dielectric parameters. For samples sintered at temperatures higher than 1500 °C, the permittivity values were obtained in the interval 30 ÷ 35 and almost do not change the value after the annealing. The Q × f product substantially increases up to about 135,000 GHz, exhibiting a low temperature coefficient of the resonant frequency (τ_f) in microwaves. The best parameters were obtained for the samples sintered at 1600 °C with additional annealing. The achieved high values of the Q × f product recommend these materials for microwave and millimeter wave applications.     

Low-temperature sintering of (Zn0.8 Mg0.2)2SiO4-TiO2 ceramics

Effect of Li₂O-B₂O₃-SiO₂ (LBS) glass on the sintering behavior and the microwave dielectric properties of (Zn_0.8 Mg_0.2)₂SiO₄-TiO₂ (ZMST) ceramics were investigated. The Li₂O-B₂O₃-SiO₂ glass lowered the sintering temperature of ZMST ceramics effectively from 1250 to 870 °C. The unknown second phase, which was formed in the ZMST ceramics increased with the addition of LBS glass. With increasing the LBS glass content, the bulk density, dielectric constant (ε_r) and the maximum Q × f value decreased, and the temperature coefficient of resonant frequency (τ_f) shifted to a negative value. (Zn_0.8 Mg_0.2)₂SiO₄-TiO₂ ceramics with 3 wt.% Li₂O-B₂O₃-SiO₂ glass sintered at 870 °C for 2 h shows excellent dielectric properties: ε_r = 8.48, Q × f = 11500 GHz, and τ_f = 0 ppm/°C.     

Chemical liquid deposition of CuInSe2 and CuIn(S,Se)2 films for solar cells

Several non-vacuum based approaches have been employed to deposit the Cu(In,Ga)Se₂ layer in photovoltaic devices, but most of them use processing temperatures in the vicinity of 500 °C. Here, we present the results on a facile solution-based deposition technique for CuInSe₂ (CISe) and CuIn(S,Se)₂ (CISSe) thin films with deposition temperatures of 300 °C. Cu_xSe (1.5 ≤ x ≤ 2) or Cu_yS (1 ≤ y ≤ 2) precursor films deposited on a substrate were reacted with InCl₃ and Se reactants in oleylamine to form CISe or CISSe thin films of the desired thickness, composition and crystal structure. Solar cells processed from these films on Mo-coated glass substrates demonstrated an efficiency of 2% under AM 1.5 illumination. We also present external quantum efficiency and capacitance-voltage measurements from these devices providing insights into the device performance.     

Influence of sintering temperature on piezoelectric properties of (K0.5Na0.5)NbO3-LiNbO3 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ have been synthesized by traditional ceramics process without cold-isostatic pressing. The effect of the content of LiNbO₃ and the sintering temperature on the phase structure, the microstructure and piezoelectric properties of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics were investigated. The result shows that the phase structure transforms from the orthorhombic phase to tetragonal phase with the increase of the content of LiNbO₃, and the orthorhombic and tetragonal phase co-exist in (K_0.5Na_0.5)NbO₃-LiNbO₃ ceramics when the content of LiNbO₃ is about 0.06 mol. The sintering temperature of (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ decreases with the increase of the content of LiNbO₃. The optimum composition for (1 − x)(K_0.5Na_0.5)NbO₃-xLiNbO₃ ceramics is 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃. The optimum sintering temperature of 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics is 1080 °C. Piezoelectric properties of 0.94 (K_0.5Na_0.5)NbO₃-0.06LiNbO₃ ceramics under the optimum sintering temperature are piezoelectric constant d₃₃ of 215 pC/N, planar electromechanical coupling factor k_p of 0.41, thickness electromechanical coupling factor k_t of 0.48, the mechanical quality factor Q_m of 80, the dielectric constant of 530 and the Curie temperature T_c = 450 °C, respectively. The results indicate that 0.94(K_0.5Na_0.5)NbO₃-0.06LiNbO₃ piezoelectric ceramics is a promising candidate for lead-free piezoelectric ceramics.     

Transparent glass ceramic containing Er:CaF2 nano-crystals prepared by sol-gel method

Er³⁺ doped SiO₂-CaF₂ transparent glass ceramic was prepared by sol-gel method. The microstructural evolution of the samples was studied with X-ray diffraction (XRD), transmission electron microscopy (TEM), and infrared spectra (IR). After heat-treatment at 900 °C, the Si-OH bonds and other organic groups were basically eliminated. The CaF₂ crystallites in the sample heat-treated at 900 °C are 10-20 nm in size, distributed homogeneously among the amorphous silica matrix. The efficient upconversion emission for Er^3+.4F_9/2 → ⁴I_15/2 transition was recorded under 980 nm excitation, which could be ascribed to the incorporation of Er³⁺ ions into the CaF₂ nano-crystals with low phonon energy.     

Structural and optical analysis of nanocrystalline thin films of mixed rare earth oxides (Y1-xErx)2O3

Nanocrystalline thin films of mixed rare earth oxides (Y_1-xEr_x)₂O₃(0.1 ≤ x ≤ 1) were deposited by electron beam evaporation technique on polished fused silica glass at different substrate temperatures (200-500 °C). The effect of the substrate temperature as well as the mixing parameter (x) on the structural and optical properties of these films has been investigated by using X-ray diffraction (XRD), energy dispersive x-ray analysis and optical spectrophotometry. XRD investigation shows that mixed rare earth oxides film (Y_1-xEr_x)₂O₃ grown at lower substrate temperature (T_s ≤ 300 °C) are poorly crystalline, whereas films grown at higher substrate temperatures (T_s ≥ 400 °C) tend to have better crystallinity. Furthermore, the mixing parameter (x) was found to stabilize the cubic phase over the entire of 0.1 ≤ x ≤ 1. The crystallite size of the films was found to vary in the range from 25 to 39 nm. Optical band gap of the films was deterimined by analysis of the absoprtion coeffifcient. For films deposited at different substrate temperatures direct and indirect transitions occur with energies varied from 5.29 to 5.94 eV and from 4.23 to 4.51 eV, respectively. However, films of different composition x, give optical band gap varied from 6.14 to 5.86 eV for direct transition and from 5.23 to 4.22 eV for indirect transitions. Consequently, one may conclude that it is possible to tune the energy band gap by relative fraction of constituent oxides. It was found that optical constants increase with increasing the substrate temperature. Nevertheless, the values of n and k decrease with increasing the mixing parameter, x.     

Synthesis and properties of GeS2-Ga2S3-PbI2 chalcohalide glasses

The glass-forming region in the GeS₂-Ga₂S₃-PbI₂ system was determined and the basic parameters of thermal and optical properties (glass transition temperature, density, microhardness and transmission window) for these glasses have been measured. Better thermal stability originated from their larger difference between T_x and T_g in the range of 107-161 °C, higher glass transition temperatures between 252 and 398 °C and wide optical transmission window from 0.5 to 12.7 μm make these glasses the promising candidate materials for rare earth doped fiber amplifiers and nonlinear optical devices.     

Optical properties of CdxZn(1−x)O films deposited by ultrasonic spray pyrolysis method

Cd_xZn_(1−x)O (x = 0, 0.59, 0.78 and 1) films have been produced by ultrasonic spray pyrolysis technique using aqueous solutions of CdCl₂ H₂O and ZnCl₂ on the microscope glass substrate between 325 and 400 °C. The Cd_xZn_(1−x)O samples have been crystallized both cubic and hexagonal structures. The optical properties of the samples were characterized by transmittance and absorption spectroscopy measurements. Transmissions of the samples have decreased with increasing x values. The optical band gap energies of the Cd_xZn_(1−x)O samples from the absorption spectra have been calculated between 2.48 and 3.23 eV by different Zn contents. The samples were annealed at 350 and 450 °C. The optical band gap energy has decreased at 350 °C whereas it increased at 450 °C.     

Hydrogen gas-sensing with bilayer structures of WO3 and Pd in SAW and electric systems

A bi-layer sensor structure of WO₃ (~ 100 nm) with a very thin film of palladium (Pd~ 18 nm) on the top, has been studied for hydrogen gas-sensing application at ~ 80 °C and ~ 120 °C and low hydrogen concentrations (0.025-1%). The structures were obtained by vacuum deposition (first the WO₃ and then the Pd film) onto a LiNbO₃ Y-cut Z-propagating substrate making use of the Surface Acoustic Wave method and additionally (in this same technological processes) onto a glass substrate with a planar microelectrode array for simultaneous monitoring of planar resistance of the structure. A very good correlation has been observed between these two methods — frequency changes in SAW method correlate very well with decreases in the bi-layer structure resistance. The SAW method is faster at the lower interaction temperature such as 80 °C, whereas at an elevated temperature of 120 °C, the electrical planar method is also fast and has a lower limit of detection.     

Study on properties of BaxSmyTi7O20 ceramics with CaO-SiO2-B2O3 glass

The effect of CaO-SiO₂-B₂O₃ (CSB) glass addition on the sintering temperature and dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics has been investigated using X-ray diffraction, scanning electron microscopy and differential thermal analysis. The CSB glass starts to melt at about 970 °C, and a small amount of CSB glass addition to Ba_xSm_yTi₇O₂₀ ceramics can greatly decrease the sintering temperature from about 1350 to about 1260 °C, which is attributed to the formation of liquid phase. It is found that the dielectric properties of Ba_xSm_yTi₇O₂₀ ceramics are dependent on the amount of CSB glass and the microstructures of sintered samples. The product with 5 wt% CSB glass sintered at 1260 °C is optimal in these samples based on the microstructure and the properties of sintering product, when the major phases of this material are BaSm₂Ti₄O₁₂ and BaTi₄O₉. The material possesses excellent dielectric properties: ?_r = 61, tan δ = 1.5 × 10⁻⁴ at 10 GHz, temperature coefficient of dielectric constant is −75 × 10⁻⁶ °C⁻¹.     

Crystal growth of Nd: NaLu(WO4)2

Nd: NaLu(WO₄)₂ single crystals have been grown by the top seeded solution growth (TSSG) method. The peaks shown in the X-ray powder diffraction pattern were assigned. The crystal belongs to the space group of I4₁/a and the unit-cell parameters were calculated as a = b = 5.168 Å, c = 11.174 Å, V = 298.46 Å³. It is a tetragonal scheelite-like single crystal. The DSC (differential scanning calorimeter) curve proved that the as-grown crystal had a glass transition at the temperature range of 733.8 °C-781.4 °C which was lower than its melting point at 1149.3 °C. The absorption and fluorescence spectra were measured at room temperature.     

Thermal stability and transport studies of (100 − 2x)TeO2-xAg2O-xWO3 (7.5 ≤ x ≤ 30) glass system

Differential scanning calorimetry (DSC), infrared (IR) and direct current (DC) conductivity studies have been carried out on (100 − 2x)TeO₂-xAg₂O-xWO₃ (7.5 ≤ x ≤ 30) glass system. The IR studies show that the structure of glass network consists of [TeO₄], [TeO₃]/[TeO₃₊₁], [WO₄] units. Thermal properties such as the glass transition (T_g), onset crystallization (T_o), thermal stability (ΔT), glass transition width (ΔT_g), heat capacities in the glassy and liquid state (C_pg and C_pl), heat capacity change (ΔC_p) and ratios C_pl/C_pg of the glass systems were calculated. The highest thermal stability (237 °C) obtained in 55TeO₂-22.5Ag₂O-22.5WO₃ glass suggests that this new glass may be a potentially useful candidate material host for rare earth doped optical fibers. The DC conductivity of glasses was measured in temperature region 27-260 °C, the activation energy (E_act) values varied from 1.393 to 0.272 eV and for the temperature interval 170-260 °C, the values of conductivity (σ) of glasses varied from 8.79 × 10⁻⁹ to 1.47 × 10⁻⁶ S cm⁻¹.     

Nickel diffusion in polycrystalline CuInSe2 thin films with a <112> fiber texture

Nickel diffusion in CuInSe₂ thin films was studied in the temperature range 430-520 °C. Thin films of copper indium diselenide (CuInSe₂) were prepared by selenization of CuInSe₂-Cu-In multilayered structure on glass substrate. A thin film of Nickel was deposited and annealed at different temperatures. Surface morphologies of the Ni diffused and undiffused CuInSe2 films were investigated using scanning electron microscope. The alteration of Nickel concentration in the CuInSe₂ thin film was measured by Energy Dispersive X-Ray Fluorescence (EDXRF) technique. These measurements were fitted to a complementary error function solution and the diffusion coefficients at four different temperatures were evaluated. The diffusion coefficients of Ni in CuInSe₂ films were estimated from concentration profiles at temperatures 430-520 °C as D = 1.86 × 10^− 7(cm²s^− 1)exp[− 0.68(eV)/kT].     

Temperature dependent Raman scattering of the epitaxial Sr1.9Ca0.1NaNb5O15 film

Epitaxial ferroelectric Sr_1.9Ca_0.1NaNb₅O₁₅ (SCNN) thin films have been fabricated successfully by pulsed laser deposition on (100)MgO substrates. Temperature dependency of the vibrational modes of these films was investigated for the first time using Raman scattering technique. For temperatures ranging between 50 °C and 450 °C, two strong and broad A₁(TO) phonons around 238 and 608 cm^− 1, and one weak B₁(TO) phonon around 142 cm^− 1 were observed. Changes in the temperature dependency of the peak position, the full-width at half maximum and integrated intensity of the Raman modes were observed in different temperature ranges. These changes are attributed to the structural phase transitions between 200 °C and 325 °C for the SCNN films as well as their relaxor properties.     

Influence of annealing temperature on domain shape of periodically poled LiNbO3 for Ti:LN waveguides

Periodically poled LiNbO₃ (PPLN) has been fabricated with a 16.6 μm domain-inverted period, a 3.0 μm thick photoresist grating, and a 3.3 μm pattern open width through the electric field poling process using the liquid electrode technique. The average duty cycle for the fabricated PPLN was measured to be 49.9 ± 3.3%. The effect of annealing temperatures on the domain shape of PPLN was investigated in the range of 300 to 800 °C. At 300 °C, residual stress was not relieved completely. As the annealing temperature increases above 800 °C, the domain shape changes. However, no domain damage was observed for annealing temperatures from 400 to 700 °C. The best annealing temperature for the suppression of domain damage and the improvement in the crystalline quality was found to be 400 °C.     

Fabrication of low-resistivity and gold-colored TiN films by halide chemical vapor deposition with a low [NH3]/[TiCl4] flow ratio

This work describes the preparation of titanium nitride (TiN) films on Si (111) substrates by atmospheric pressure halide chemical vapor deposition (AP-HCVD). Various TiN films were obtained by exploiting TiCl₄ + NH₃ gas chemistry with flow ratios [NH₃]/[TiCl₄] from 0.2 to 1.4, and deposition temperatures (T_d) from 600 to 900 °C. When T_d = 800 °C gold-colored films with electrical resistivities of under 100 μΩ cm were formed at almost all of the investigated [NH₃]/[TiCl₄] flow ratios. In particular, a lowest resistivity of about 23.7 μΩ cm, which is quite close to that of bulk TiN, was achieved using an [NH₃]/[TiCl₄] flow ratio of 0.3. Atomic force microscopy indicated that the root mean square surface roughness of that film was only about 5.1 nm. Under the same [NH₃]/[TiCl₄] flow ratio as above, X-ray diffraction analyses revealed the presence of a cubic TiN phase with a preferred orientation of (200) for T_d ≤ 800 °C, while additional (111) and (220) orientations emerged when the film was deposited at 900 °C. In conclusion, a low resistivity (< 100 μΩ cm) TiN film can be formed by AP-HCVD with very low [NH₃]/[TiCl₄] flow ratios 0.3-1.4.     

Growth of silicon carbide thin films by hot-wire chemical vapor deposition from SiH4/CH4/H2

Silicon carbide (SiC) thin films were prepared by hot-wire chemical vapor deposition from SiH₄/CH₄/H₂ and their structural properties were investigated by X-ray diffraction, Fourier transform infrared absorption and Raman scattering spectroscopies. At 2 Torr, Si-crystallite-embedded amorphous SiC (a-Si_1 − xC_x:H) grew at filament temperatures (T_f) below 1600 °C and nanocrystalline cubic SiC (nc-3C-SiC:H) grew above T_f = 1700 °C. On the other hand, At 4 Torr, a-Si_1 − xC_x:H grew at T_f = 1400 °C and nc-3C-SiC grew above T_f = 1600 °C. When the intakes of Si and C atoms into the film per unit time are almost the same and H radicals with a high density are generated, which takes place at high T_f, nc-3C-SiC grows. On the other hand, at low T_f the intake of Si atoms is larger than that of C atoms and, consequently, Si-rich a-Si_1 − xC_x:H or Si-crystallite-embedded a-Si_1 − xC_x:H grow.     

Investigations of thin film structures of WO3 and WO3 with Pd for hydrogen detection in a surface acoustic wave sensor system

A single thin film sensor structure of WO₃ (∼ 50 nm) and bilayer sensor structure of WO₃ (∼ 50 nm) with a very thin film of palladium (Pd ∼ 18 nm) on the top, have been studied for hydrogen gas-sensing application at ∼ 30 °C and ∼ 50 °C. The structures were obtained by vacuum deposition (first the WO₃ and than the Pd film) onto a LiNbO₃ Y-cut Z-propagating substrate making use of the surface acoustic wave method and additionally (in this same technological processes) onto a glass substrate with a planar microelectrode array for simultaneously monitoring of the planar resistance of the structure. In the case of a bilayer structure a very good correlation has been observed between these two methods — frequency changes in SAW method correlate very well with decreases of the bilayer structure resistance. These frequency changes are on the level of 2.4 kHz to 4% of hydrogen concentration in dry air, whereas in the case of a single WO₃ structure almost no frequency shift is observed.     

Multi-stage evaporation of Cu2ZnSnS4 thin films

Multi-stage evaporation is a well-established method for the controlled growth of chalcopyrite thin films. To apply this technique to the deposition of Cu₂ZnSnS₄ thin films we investigated two different stage sequences: (A) using Cu₂SnS₃ as precursor to react with Zn-S and (B) using ZnS as precursor to react with Cu-Sn-S. Both Cu₂SnS₃ and ZnS are structurally related to Cu₂ZnSnS₄. In case (A) the formation of copper tin sulphide in the first stage was realized by depositing Mo/SnS_x/CuS (1 < x < 2) and subsequent annealing. In the second stage ZnS was evaporated in excess at different substrate temperatures. We assign a significant drop of ZnS incorporation at elevated temperatures to a decrease of ZnS surface adhesion, which indicates a self-limited process with solely reactive adsorption of ZnS at high temperatures. In case (B) firstly ZnS was deposited at a substrate temperature of 150 °C. In the second stage Cu, Sn and S were evaporated simultaneously at varying substrate temperatures. At temperatures above 400 °C we find a strong decrease of Sn-incorporation and also a Zn-loss in the layers. The re-evaporation of elemental Zn has to be assumed. XRD measurements after KCN-etch on the layers prepared at 380 °C show for both sample types clearly kesterite, though an additional share of ZnS and Cu₂SnS₃ can not be excluded. SEM micrographs reveal that films of sample type B are denser and have larger crystallites than for sample type A, where the porous morphology of the tin sulphide precursor is still observable. Solar cells of these absorbers reached conversion efficiencies of 1.1% and open circuit voltages of up to 500 mV.     

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.