Photoelectrochemical properties of lead-free ferroelectric ceramic Ba(Ti<Subscript>0.96</Subscript>Mg<Subscript>0.013</Subscript>Nb<Subscript>0.026</Subscript>)O<Subscript>3</Subscript>: application to solar conversion of eosin

The lead-free Ba(Ti_0.96Mg_0.013Nb_0.026)O₃ composition has been prepared by solid state reaction. The room temperature X-ray diffraction revealed a perovskite phase with a tetragonal symmetry. The complex dielectric permittivity measured on cooling from 470 to 150 K in the frequency range (10²–10⁶ Hz) indicated a ferroelectric behavior and exhibited a large electromechanical response. This ferroelectric perovskite showed photoelectrochemical properties with an optical gap of 2.90 eV, n-type conduction and a flat band potential of ?0.57 V _SCE . As application, the oxide is successfully tested for the eosin oxidation under solar light. At pH ~ 6.3, 90 % of eosin (15 mg L^?1) disappeared after 6 h of illumination for a catalyst dose of 2.5 g L^?1.     

Structural and electric properties of (Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>)<Subscript>0.88</Subscript>Ba<Subscript>0.12</Subscript>TiO<Subscript>3</Subscript>

Lead-free (Na_0.5Bi_0.5)_0.88Ba_0.12TiO₃ ceramics have been prepared and studied by X-ray diffraction and by the complex dielectric response as a function of temperature, frequency and a.c. field intensity. Relaxor-like dielectric behaviour were induced by barium Ba dopping to Na_0.5Bi_0.5TiO₃. It was shown, that relaxor-like characteristics can be enhanced by the increase of the a.c. field intensity. A sharp increase in the electric permittivity and dielectric loss on heating near 230 °C has been observed. This sharp increase in dielectric responses indicates a transformation between classical and relaxor ferroelectric phases. The X-ray diffraction study shows that this transformation corresponds to the first order phase transition from tetragonal to cubic. The use of (Na_0.5Bi_0.5)_0.88Ba_0.12TiO₃ ceramics for device applications has been indicated.     

Temperature-stable and low loss Fe-containing dielectrics in BaO-Ln<Subscript>2</Subscript>O<Subscript>3</Subscript>-Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Ta<Subscript>2</Subscript>O<Subscript>5</Subscript> system

Polycrystalline samples of Ba₄Ln₂Fe₂Ta₈O₃₀ (Ln = La and Nd) were prepared by a high temperature solid-state reaction technique. The formation, structure, dielectric and ferroelectric properties of the compounds were studied. Both compounds are found to be paraelectrics with filled tetragonal tungsten bronze (TB) structure at room temperature. Dielectric measurements revealed that the present ceramics have exceptional temperature stability, a relatively small temperature coefficient of dielectric constant (τ _ε ) of −25 and −58 ppm/°C, with a high dielectric constant of 118 and 96 together with a low dielectric loss of 1.2 × 10⁻³ and 2.8 × 10⁻³ (at 1 MHz) for Ba₄La₂Fe₂Ta₈O₃₀ and Ba₄Nd₂Fe₂Ta₈O₃₀, respectively. The measured dielectric properties indicate that both materials are possible candidates for the fabrication of discrete multilayer capacitors in microelectronic technology.     

Electric properties of Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript>(BIT)–CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> (CCTO) composite substrates for high dielectric constant devices

A study of the effect of the presence of BIT (Bi₄Ti₃O₁₂) in the dielectric and optical properties of the CaCu₃Ti₄O₁₂ (CCTO) is presented. The samples were prepared by the solid state procedure. Mechanical alloying followed by the solid state procedure has been used successfully to produce powders of CaCu₃Ti₄O₁₂ (CCTO) and BIT (Bi₄Ti₃O₁₂) to be used in the composites. We also look at the effect of the grain size of the BIT and CCTO in the final properties of the composite. The samples were studied using X-Ray diffraction, scanning electron microscopy (SEM), Raman and infrared spectroscopy. We also did a study of the dielectric function K and dielectric loss of the samples. The role played by the grain size of CCTO and BIT in the dielectric constant and structural properties of the substrates are discussed. For frequencies below 10 MHz the K value presented by the CCTO100 sample is always higher than the K value presented by the BIT100 sample. At 100 Hz the value of K 1900 for the CCTO100 sample and 288 for the BIT100 sample. However for the composite sample one has an unexpected result. The dielectric constant is higher for all the frequencies under study. At 100 Hz the value of the K is around 10.000 for the BIT10 sample. Which is more than one order bigger compared to the CCTO100 value for the same frequency. Therefore, these measurements confirm the potential use of such materials for small high dielectric planar devices. These composites are also attractive for capacitor applications and certainly for microelectronics, microwave devices (cell mobile phones for example), where the miniaturization of the devices is crucial.     

Relaxor behavior and ferroelectric properties of Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-K<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript>-KNbO<Subscript>3</Subscript> lead-free ceramics

Lead-free ferroelectric ceramics of (1−x) [0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃]-x KNbO₃(x = 0, 0.02, 0.04, and 0.06) were prepared by the conventional ceramic fabrication technique. The crystal structure, dielectric properties and P-E hysteresis loops were investigated. XRD data showed that all compositions could form pure perovskite structure. Temperature dependence of dielectric constant ε _r and dissipation factor tanδ measurement between room temperature and 500^∘C revealed that the compounds experience phase transitions that from ferroelectric to anti-ferroelectric and anti-ferroelectric to paraelectric in the range of x = 0–0.04. The frequency dependent dielectric constant showed these compounds were relaxor ferroelectric. At low frequency and high temperature, dielectric constant and dissipation factor increased sharply attributed to the superparaelectric clusters after the KNbO₃ doped.     

Properties of Na<Subscript>0.875</Subscript>Li<Subscript>0.125</Subscript>NbO<Subscript>3</Subscript> ceramics

The structural, dielectric, and thermal properties of the Na_0.875Li_0.125NbO₃ solid solution doped with strontium and other elements have been studied in wide temperature and frequency ranges. The material has been shown to undergo a sequence of phase transitions accompanied by anomalies in its structural, dielectric, and thermal properties. The observed low-frequency dispersion of its dielectric permittivity is attributed to the effect of electrical conductivity.     

Dielectric and ferromagnetic properties of BaTiO<Subscript>3</Subscript>/Ni<Subscript>0.93</Subscript>Co<Subscript>0.02</Subscript>Cu<Subscript>0.05</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> composites

xBaTiO₃ + (1 − x)Ni_0.93Co_0.02Cu_0.05Fe₂O₄ (x = 0.5, 0.6, 0.7, 0.8) composites with ferroelectric–ferromagnetic characteristics were synthesized by the ceramic sintering technique. The presence of constituent phases in the composites was confirmed by X-ray diffraction studies. The average grain size was calculated by using a scanning electron micrograph. The dielectric characteristics were studied in the 100 kHz to 15 MHz. The dielectric constant changed higher with ferroelectric content increasing; and it was constant in this frequency range. The relation of dielectric constant with temperature was researched at 1, 10, 100 kHz. The Curie temperature would be higher with frequency increasing. The hysteresis behavior was studied to understand the magnetic properties such as saturation magnetization (M _s). The composites were a typical soft magnetic character with low coercive force. Both the ferroelectric and ferromagnetic phases preserve their basic properties in the bulk composite, thus these composites are good candidates as magnetoelectric materials.     

Effects of dc bias on dielectric relaxations in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> ceramics

Effects of dc bias on dielectric relaxations in CaCu₃Ti₄O₁₂ ceramics were investigated via an improved dielectric spectroscopy. A new low-frequency dielectric relaxation, which was assigned to space charge polarization, was found shifting towards higher frequency with increasing bias voltage in the improved spectra. It was suggested that the Schottky barrier at grain boundary was lowered under dc bias resulting in higher possibility for carriers to migrate. Therefore, the relaxation time was decreased, which was in accordance with rightward shift of this relaxation under increased dc bias. In addition, dependence of the widely reported high-frequency relaxation (>?10⁵ Hz) and middle-frequency relaxation (10³–10⁵ Hz) on bias voltage was also discussed. Permittivity contributed by either high-frequency or middle-frequency relaxation presented inverse dependence on dc bias. Discrepancy on barrier parameters was obtained assuming both of them physically correlated with the barrier at grain boundary.     

Visible photocatalytic degradation of methylene blue on magnetic semiconducting La<Subscript>0.2</Subscript>Sr<Subscript>0.7</Subscript>Fe<Subscript>12</Subscript>O<Subscript>19</Subscript>

Methylene blue (MB) is a representative of a class of dyestuffs resistant to biodegradation. This paper presents a novel photocatalytic degradation of MB by La_0.2Sr_0.7Fe₁₂O₁₉ compound, which is a traditional permanent magnet and displays a large magnetic hysteresis (M–H) loop. The remnant magnetic moment and coercive field are determined to be 52 emu/g and 5876 Oe, respectively. UV–Visible optical spectroscopy reveals that La_0.2Sr_0.7Fe₁₂O₁₉ is simultaneously a semiconductor, whose direct and indirect band gap energies are determined to be 1.47 and 0.88 eV, respectively. The near infrared band gap makes it a good candidate to harvest sunlight for photocatalytic reaction or solar cell devices. This magnetic compound demonstrates excellent photocatalytic activity on degradation of MB under visible illumination. The colour of MB dispersion solution changes from deep blue to pale white and the absorbance decreases rapidly from 1.8 down to zero when the illumination duration extends to 6 h. Five absorption bands did not make any blue shifts along with the reaction time, suggesting a one-stepwise degradation process of MB, which makes La_0.2Sr_0.7Fe₁₂O₁₉ a unique magnetic catalyst and differs from TiO₂ and other conventional catalysts.     

Properties of neodymium-doped Ca<Subscript>0.15</Subscript>Sr<Subscript>1.85</Subscript>Bi<Subscript>4</Subscript>Ti<Subscript>5</Subscript>O<Subscript>18</Subscript> ferroelectric ceramics

Bismuth-layered compound Ca_0.15Sr_1.85Bi_4−xNd_xTi₅O₁₈ (CSBNT, x = 0–0.25) ferroelectric ceramics samples were prepared by solid-state reaction method. The effects of Nd³⁺ doping on their ferroelectric and dielectric properties were investigated. The remnant polarization Pr of CSBNT ceramics increases at beginning then decreases with increasing of Nd³⁺ doping level, and a maximum Pr value of 9.6 μC/cm² at x = 0.05 was detected with a coercive field Ec = 80.2 kV/cm. Nd³⁺ dopant not only decreases the Curie temperature linearly, but also the dielectric constant (ε_r) and dielectric loss tangent (tan δ). The magnitudes of ε_r and tan δ at the frequency of 100 kHz are estimated to be 164 and 0.0083 at room temperature, respectively.     

Structures and dielectric properties of La/Sn co-substituted Ba<Subscript>4</Subscript>Nd<Subscript>2</Subscript>{T}i<Subscript>4</Subscript>Ta<Subscript>6</Subscript>O<Subscript>30</Subscript> ceramics

The effects of La/Sn co-substitution at A and B sites of Ba₄Nd₂Ti₄Ta₆O₃₀ ceramics were investigated. With La/Sn co-substitution, the temperature coefficient was significantly improved to near zero, at the same time, dielectric constant reduced and dielectric loss increased. In particular, remarkable annealing effects on dielectric properties were observed for these modified ceramics. After annealing, dielectric constant considerably increased, and temperature coefficient shifted to more negative.     

Electrical properties of some Y<Subscript>2</Subscript>O<Subscript>3</Subscript> and/or Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-containing lithium silicate glasses and glass-ceramics

The ac electrical properties of some lithium silicate glasses and glass-ceramics containing varying proportions of Y₂O₃ and/or Fe₂O₃ were measured to investigate their electronic hopping mechanism. There is a clear variation of these properties with composition. The obtained results were related to the concentration and role of Y₂O₃ and/or Fe₂O₃ in the lithium silicate glass structure. In crystalline solids the electrical properties data obtained were correlated to the type and content of the mineral phases formed as indicated by X-ray diffraction analysis (XRD). The conductivity, dielectric constant and dielectric loss of the studied glasses were studied using the frequency response in the interval 30 Hz–100 KHz and the effect of compositional changes on the measured properties was investigated. The measurements revealed that the electrical responses of the samples were different and complex. The addition of Y₂O₃ generally, decreased the ac conductivity, dielectric constant and dielectric losses of the lithium silicate glasses. The addition of Fe₂O₃ in Y₂O₃-containing glasses increases the conductivity, while, the dielectric constant and dielectric losses were found to be decreased. However, the addition of Fe₂O₃ instead of Y₂O₃ led to decrease the ac conductivity and increased their dielectric constant and dielectric losses. The obtained data were argued to the internal structure of the lithium silicate glass and the nature or role-played by weakness or rigidity of the structure of the sample. Lithium disilicate-Li₂Si₂O₅, lithium metasilicate-Li₂SiO₃, two forms of yttrium silicate Y₂Si₂O₇ & Y₂SiO₅, iron yttrium oxide-YFeO₃, lithium iron silicate-LiFeSi₂O₆ and α-quartz phases were mostly developed in the crystallized glasses. The conductivity of the crystalline materials was found to be relatively lower than those of the glass. At low frequency, as the Y₂O₃ content increased the ac conductivity, dielectric constant and dielectric loss data of the glass-ceramics decreased. However, the addition of Fe₂O₃ to the Y₂O₃ containing glass-ceramic led to increase the conductivity. The addition of high content of Fe₂O₃ instead of Y₂O₃ in the glass ceramic led to increase the ac conductivity.     

Dielectric properties of a K<Subscript>3</Subscript>Li<Subscript>1.88</Subscript>Nb<Subscript>5.12</Subscript>O<Subscript>15.24</Subscript> crystal from 90 to 300 K

The electrical conductivity, dielectric permittivity, and loss tangent of a K₃Li_1.88Nb_5.12O_15.24 crystal have been measured at temperatures from 90 to 300 K and frequencies of 0.1, 1, 10, and 10³ kHz. The results demonstrate that the dielectric permittivity of the crystal increases with increasing temperature and drops with increasing frequency. The plots of tanδ versus temperature show maxima characteristic of semiconductors. The conductivity of the crystal increases by several orders of magnitude with increasing frequency. The conductivity and dielectric properties of the K₃Li_1.88Nb_5.12O_15.24 crystal are shown to be anisotropic.     

Low-firing Li<Subscript>2</Subscript>ZnTi<Subscript>3</Subscript>O<Subscript>8</Subscript> microwave dielectric ceramics with BaCu(B<Subscript>2</Subscript>O<Subscript>5</Subscript>) additive

Phase purity, microstructure, sinterability and microwave dielectric properties of BaCu(B₂O₅)-added Li₂ZnTi₃O₈ ceramics and their cofireability with Ag electrode were investigated. A small amount of BaCu (B₂O₅) can effectively reduce the sintering temperature from 1075°C to 925°C, and it does not induce much degradation of the microwave dielectric properties. Microwave dielectric properties of ε _r = 23·1, Q × f = 22,732 GHz and τ _f = − 17·6 ppm/°C were obtained for Li₂ZnTi₃O₈ ceramic with 1·5 wt% BaCu(B₂O₅) sintered at 925°C for 4 h. The Li₂ZnTi₃O₈ +BCB ceramics can be compatible with Ag electrode, which makes it a promising microwave dielectric material for low-temperature co-fired ceramic technology application.     

Dielectric relaxation and polaronic hopping in the single-layered perovskite La<Subscript>1.5</Subscript>Sr<Subscript>0.5</Subscript>CoO<Subscript>4</Subscript> ceramics

Single tetragonal La_1.5Sr_0.5CoO₄ ceramics with the space group of I 4/mmm (139) were prepared by a solid-state reaction process, and dielectric characteristics were investigated on a broad frequency and temperature range. There was one obvious dielectric relaxation around room temperature plus a low temperature upturn on the curve of temperature dependence of dielectric properties for La_1.5Sr_0.5CoO₄ ceramics. This dielectric relaxation was a thermal-activated process. It should be attributed to the mixed-valence structure (Co²⁺/Co³⁺) since its activation energy was similar to that of small polaronic hopping process. After annealing the sample in O₂ atmosphere, dielectric constants and ac conductivities of La_1.5Sr_0.5CoO₄ ceramics increased and decreased after annealing the sample in N₂ atmosphere. This abnormal phenomenon should be attributed to the variation of concentration for holes (Co³⁺).     

Strain-induced artificial multiferroicity in Pb(Zr<Subscript>0.53</Subscript>Ti<Subscript>0.47</Subscript>)O<Subscript>3</Subscript>/Pb(Fe<Subscript>0.66</Subscript>W<Subscript>0.33</Subscript>)O<Subscript>3</Subscript> layered nanostructure at ambient temperature

Layered nanostructures (LNs) of the commercial ferroelectric Pb(Zr_0.53Ti_0.47)O₃ (PZT) and the natural ferroic relaxor Pb(Fe_0.66W_0.33)O₃ (PFW) were fabricated with a periodicity of PZT/PFW/PZT (~5/1/5 nm, thickness ~250 nm) on MgO substrates by pulsed laser deposition. The dielectric behavior of these LNs were investigated over a wide range of temperatures and frequencies, observing Debye-type relaxation with marked deviation at elevated temperatures (>400 K). High dielectric constant and very low dielectric loss were observed below 100 kHz and 400 K, whereas the dielectric constant decreases and loss increases with increase in frequency, similar to relaxor ferroelectrics. Asymmetric ferroelectric hysteresis loops across UP and DOWN electric field were observed with high remanent polarization (P_r) of about 33 μC/cm². High imprint (~5–7 V across 250 nm thin films) were seen in ferroelectric hysteresis that may be due to charge accumulation at the interface of layers or significant amount of strain (~3.21) across the layers. Room temperature ferromagnetic hysteresis was observed with remanent magnetization 5.32 emu/cc and a coercive field of ~550 Oe. Temperature and field dependent leakage current densities showed very low leakage ~10⁻⁷–10⁻⁵ A/cm² over 500 kV/cm. We observed imprint in hysteresis that may be due to charge accumulation at the interface of layers or active role of polar nano regions (PNRs) situated in the PFW regions.     

Anisotropy of dielectric losses in Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and SiO<Subscript>2</Subscript> single crystals

The procedure and results of measurements of the dielectric loss tangent using the dielectric resonator technique on azimuthal modes of the HE (quasi-E) and EH (quasi-H) types are considered. The measurements were performed for uniaxial anisotropic single crystals of Al₂O₃ (at a frequency of 11 GHz) and SiO₂ (at 39 GHz) in a temperature range of 80–373 K and for an isotropic single crystal of Y₃Al₅O₂ (YAG) at room temperature in a frequency range of 9–15 GHz. The proposed method revealed the anisotropy of dielectric losses in Al₂O₃ and SiO₂ single crystals in the temperature range studied. According to this, losses along the optical axis of these crystals are lower than in the transverse plane. In the YAG crystal, the Q values for modes of the two types with the same frequency are close, which corresponds to isotropic losses. The dielectric losses in YAG increase in proportion to the frequency.     

Compound-LiCo<Subscript>3/5</Subscript>Fe<Subscript>1/5</Subscript>Mn<Subscript>1/5</Subscript>VO<Subscript>4</Subscript> and dielectric characteristics

The LiCo_3/5Fe_1/5Mn_1/5VO₄ compound was successfully synthesized by solution-based chemical method. The variation of dielectric constant (ε_r) with frequency at different temperatures shows a dispersive behavior at low frequencies. Temperature dependence of ε_r at different frequencies indicates dielectric anomalies in ε_r at temperature (T_max) = 220, 235, 245, 260 and 275 °C with (ε_r)_max ~ 6,830, 2,312, 1,224, 649 and 305 for 10, 50, 100, 200 and 500 kHz, respectively. The variation of tangent loss with frequency at different temperatures shows the presence of dielectric relaxation in the material. The variation of relaxation time as a function of temperature follows the Vogel-Fulcher relation.     

Fabrication of conductive SrRuO<Subscript>3</Subscript> thin film and Ba<Subscript>0.60</Subscript>Sr<Subscript>0.40</Subscript>TiO<Subscript>3</Subscript>/SrRuO<Subscript>3</Subscript> bilayer films on MgO substrate

Conductive SrRuO₃ (SRO) thin films have been grown on (100) MgO substrates by pulsed laser deposition (PLD) technique. Effects of oxygen pressure and deposition temperature on the orientation of SRO thin film were investigated. X-ray diffraction (XRD) θ/2θ patterns and the temperature dependent resistivity measurements indicated that oxygen pressure of 30 Pa and deposition temperature of 700 °C were the optimized deposition parameters. A parallel-plate capacitor structure was prepared with the SRO films deposited under optimized condition as an electrode layer and Ba_0.60Sr_0.40TiO₃ (BST) thin film as the dielectric layer. XRD Φ scans indicated a epitaxial relationship between BST and SRO on MgO substrate. The dielectric constant and loss tangent measured at 10 kHz and 300 K was 427 and 0.099 under 0 V bias, and 215 and 0.062 under 8 V bias, respectively. A tunability of 49.6% has been achieved with DC bias as low as 8 V. The C–V hysteresis curve and the P–E hysteresis loop suggested that the BST films epitaxially grown on SRO/MgO have ferroelectricity at room temperature. The induced ferroelectricity was believed to originate from the compressive strain between the epitaxial BST and SRO thin films. These results show the potential application of the BST/SRO heterostructures in microelectronic devices.     

Study on dielectric and tunable properties of Cr-doped Ba<Subscript>0</Subscript><Subscript>.6</Subscript>Sr<Subscript>0.4</Subscript>TiO<Subscript>3</Subscript> thin films by rf sputtering

Ba_0.6Sr_0.4TiO₃ dielectric thin films doped by Cr(0, 1, 2.5, 5, 10 mol%) (BSTC) were prepared by radio frequency magnetron sputtering on Pt/Ti/SiO₂/Si substrates. The structure and morphology of the BSTC thin films were studied by atomic force microscopy and X-ray diffraction. The effect of Cr doping on the dielectric properties of BST thin films were analyzed. The results show that the dielectric loss of Cr doping BST thin films is lower than that undoped, and the tunability increased with Cr doping. The thin film doped with 5 mol% Cr has the best dielectric properties. The tunability, loss and figure of merit (FOM) at 1 MHz were 38.9%, 0.0183, and 21.3, respectively.