Dielectric and Piezoelectric 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>-NaNbO<Subscript>3</Subscript>Lead-Free Ceramics

The ternary lead-free piezoelectric ceramics system of (1 – x) [0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃] – xNaNbO₃(x = 0, 0.02, 0.04, 0.06, 0.08, 0.10) were synthesized by conventional solid state reaction method. The crystal structure, dielectric, piezoelectric properties and P-E hysteresis loops were investigated. The crystalline structure of all compositions is mono-perovskite phase ascertained by XRD, and the lattice constant was calculated from the XRD data. Temperature dependence of dielectric constant _r and dissipation factor tan measurement revealed that all compositions experienced two phase transitions: from ferroelectric to anti-ferroelectric and from anti-ferroelectric to paraelectric, and these two phase transitions have relaxor characteristics. Both transition temperatures T_d and T_m are lowered due to introduction of NaNbO₃. P-E hysteresis loops show that 0.88Na_0.5Bi_0.5TiO₃-0.12K_0.5Bi_0.5TiO₃ ceramics has the maximum P_r and E_c corresponding to the maximum values of electromechanical coupling factor K_p and piezoelectric constant d_33. The piezoelectric constant d₃₃ and electromechanical coupling factor K_p decrease a little, while the dielectric constant ₃₃^T/₀ improves much more when the concentration of NaNbO₃ is 8 mol%.     

Bi0.5(Na0.82-xK0.18Lix)0.5TiO3无铅压电陶瓷的微结构与电性能

采用传统陶瓷制备工艺制备了[Bi0.5(Na0.82-xK0.18Lix)0.5]TiO3(x=0.01~0.07)无铅压电陶瓷.研究了该体系陶瓷的微结构以及应力对平面机电耦合系数kp和压电常数d33的影响.结果表明,[Bi0.5(Na0.82-xK0.18Lix)0.5]TiO3无铅压电陶瓷具有单一钙钛矿结构,Li+有抑制晶粒长大的作用.当x=0.03时,压电陶瓷样品表现出优良的压电性能:压电常数d33和平面机电耦合系数kp分别为154 pC/N和0.296.同时发现,退火可消除内应力,有利于提高d33,但会使kp减小;极化会引起介电常数εr减小,电畴转向过程中产生的应力对d33影响较为明显     

Microwave Tunable Properties of Ni-Doped (Ba0.5Sr0.5)TiO3 Thin Films Grown by Pulsed Laser Deposition

(Ba_0.5Sr_0.5)TiO₃ (BST) thin films were deposited by pulsed laser deposition (PLD) and investigated as a function of Ni dopant concentration in low and high frequency regions. In low frequency region (<10 MHz), the Ni-dopant concentration in BST films has a strong influence on the material properties including dielectric and tunable properties. Ni-doped (≤3 mol%) BST films showed denser, smoother morphologies and smaller grain sizes than those with 6 and 12 mol% Ni. Dielectric constant and loss of 3 mol% Ni-doped BST films were about 980 and 0.3%, respectively. In addition, tunability and figure of merit of 3 mol% doped BST films showed maximum values of approximately 39% and 108, respectively. In high frequency region (>1 GHz), the frequency tunability range at center frequency of undoped BST and 3 mol% Ni-doped BST coplanar waveguide (CPW) resonators showed 102 and 152 MHz, respectively at 30 V dc bias. The Ni-doped BST thin films are possible in applications of microwave tunable capacitors.     

The Rutile Phase of TiO2/Graphene Films: Sol–Gel Method,Phase Transition,Photocatalytic Properties

Abstract

TiO₂ materials are of great interest in different applications because of the controllable preparation of different structures. In this paper, the TiO₂ and TiO₂/graphene films with different phase structure and inserted graphene layer between Cu substrate and TiO₂ film were prepared by sol–gel method at different annealing temperatures, and then used as catalysts for photo-degradation of methylene blue (MB) dye solution under ultraviolet irradiation using 15?W of ultraviolet lamp. The effects of annealing temperature and graphene layer on the phase structure, morphology, chemical composition, binding energy level, and photocatalytic performance of TiO₂ films were studied in details. XRD results reveal that the anatase phase of TiO₂ films transfers to rutile phase with the increase in annealing temperature, and the introducing of graphene film layer can accelerate the phase transformation of anatase to rutile and improve the crystallization quality of TiO₂ films. It is found that the MB degradation efficiency of TiO₂ and TiO₂/graphene films is enhanced with the increasing annealed temperature, which shows that the existence of rutile phase, well crystalline quality and the better dispersion of the TiO₂ particles are helpful in photocatalytic behavior. In addition, compared to the rutile phase TiO₂ film, the rutile phase TiO₂/graphene films at annealed temperatures of 900?°C exhibit much higher photocatalytic activity due to the introduction of graphene films.     

PREPARATION AND PROPERTIES OF LITHIUM-DOPED K0.5Na0.5NbO3 THIN FILMS BY CHEMICAL SOLUTION DEPOSITION

ABSTRACT

Lithium-doped K_0.5Na_0.5NbO₃ (KLNN) films were fabricated by chemical solution deposition on Pt/TiO₂/SiO₂/Si substrates. Homogeneous and stable precursor solutions were prepared by controlling the reaction of starting metal alkoxides. Perovskite KLNN single-phase thin films were successfully synthesized on Pt/TiO _x /SiO₂/Si substrates. The 0.75-μ m-thick KLNN film annealed at 650°C exhibited ferroelectric polarization hysteresis loops at ?250°C. The loop at room temperature was round, indicating the film contained leakage components. The dielectric constant under zero bias was 490 at room temperature. A typical upside-down butterfly DC bias-capacitance curve was obtained in the KLNN film capacitors at room temperature, indicating that polarization reversal occurred in the obtained KLNN films.     

Structural, Thermal and Electrical Properties of Ce-Doped SrMnO3

The Sr_1-xCe_xMnO_1- system (0 x 0.5) was investigated with respect to its structural, thermal and electrical properties. Although un-doped SrMnO₃ has the perovskite structure above 1400°C, the structure is unstable at room temperature. However, partial substitution of Ce for Sr in SrMnO₃ stabilizes the perovskite structure down to room temperature. Single phase perovskite is obtained for 0.1 x 0.3 in Sr_1-xCe_xMnO_1-, and it remains stable even following heat treatment at 800°C for 100 h. The dependence of the electrical conductivity on temperature was measured from room temperature to 1000°C in air. Ce doping dramatically enhanced the electrical conductivity of SrMnO₃. Sr_0.7Ce_0.3MnO_1- exhibits a higher conductivity (290 S · cm^-1 at 1000°C) than that of La_0.8Sr_0.2MnO₃ (LSM, about 175 S · cm^-1) and remains n-type over the whole range of temperature examined. The thermal expansion coefficients in the system were nearly constant with values ranging between 1.24 × 10^-6 and 1.01 × 10^-6 cm/cm · K for temperatures of 50°C to 1000°C.     

Study of the Electrical Properties of Pb(Mg,Ni)1/3Nb2/3O3-PbTiO3 System Across the Morphotropic Phase Boundary

Phase transitional behavior and electrical properties of (1 – x)Pb(Mg,Ni)_1/3Nb_2/3O₃-xPbTiO₃ ceramics (PMNN-PT with Mg/Ni = 1:1, x = 0.20–0.40) across the morphotropic phase boundary (MPB) were examined. X-ray diffraction and dielectric measurement reveal that two phases, pseudocubic and tetragonal phases, coexist in the composition range x = 0.30–0.36. The maximum d ₃₃ (about 570 pC/N) was observed at the composition x = 0.32–0.34. Dielectric and ferroelectric properties exhibit abnormal high near the MPB. An unusual peak shoulder occurred in the dielectric measurement upon thermal cycling for poled samples. This phenomenon was considered to be associated with the macro to micro domain transition and depolarization.     

Comparative Characteristics of Na0.5K0.5NbO3 Films on Pt by Pulsed Laser Deposition and Magnetron Sputtering

Ferroelectric Na_0.5K_0.5NbO₃ (NKN) thin films were grown on the Pt₈₀Ir₂₀ polycrystalline substrates by pulsed laser deposition (PLD) and radio frequency-magnetron sputtering (RF) technique using the same stoichiometric Na_0.5K_0.5NbO₃ ceramic target. X-ray diffraction proved both PLD- and RF-made Na_0.5K_0.5NbO₃/Pt₈₀Ir₂₀ films are single phase and have preferential c-axis orientation. Temperature dependence of dielectric permittivity reveals the presence of two phase transitions around 210 and 410°C. Capacitance vs. applied voltage C-V @ 100 kHz, I-V, and P-E hysteresis characteristics recorded for the vertical capacitive structures yielded loss tanδ = 0.026 and 0.016, tunability about 44.5 and 30% @ 100 kV/cm, Ohmic resistivity 6.7 × 10¹² Ω·cm and 0.2 × 10¹² Ω·cm, remnant polarization 11.7 and 9.7 μC/cm², coercive field 28.0 and 94.6 kV/cm for PLD- and RF-films, respectively. Piezoelectric test carried out in hydrostatic conditions showed piezoelectric coefficient d _H = 21 for PLD-NKN and 15 pC/N for RF-NKN film.     

Co-Modification of Ba5NdTi3Ta7O30 Dielectric Ceramics by Substitution and Introducing Secondary Phase

Co-modification of Ba₅NdTi₃Ta₇O₃₀ dielectrics ceramics was investigated through Pb substitution for Ba and introducing Bi₄Ti₃O₁₂ secondary phase. The dielectric constant increased from 150 to 283, the temperature coefficient of the dielectric constant decreased from –2500 ppm/°C to –1279 ppm/°C, and the dielectric loss decreased to 0.0007 at 1 MHz. Meanwhile, the bi-phase ceramics were investigated to achieve temperature stable ceramics with high dielectric constant and low dielectric loss. As the composition x varied from 0.4 to 0.7 for (1 – x)(Ba_0.8Pb_0.2)₅NdTi₃Ta₇O₃₀/xBi₄Ti₃O₁₂, the temperature coefficient of the dielectric constant changed from negative to zero to positive.     

Dielectric Properties and Sintering Characteristics of CaTiO<Subscript>3</Subscript>-(Li<Subscript>1/2</Subscript>Nd<Subscript>1/2</Subscript>)TiO<Subscript>3</Subscript> Ceramics

The dielectric properties and the sintering effect upon microstructure of (1–x) CaTiO₃-x(Li_1/2Nd_1/2)-TiO₃ Ceramics are investigated in this paper. Nd³⁺ and Mg^{2 +} ions co-substitution for Ca^{2 +} on A site improves the sintering characteristic of CaTiO₃ ceramics with forming orthorhombic perovskite structure. The structure of (1 – x) CaTiO₃-x(Li_1/2Nd_1/2)TiO₃ changes from orthorhombic to tetragonal as (Li_1/2Nd_1/2)TiO₃ addition increasing. Limited solubility of (Li_1/2Nd_1/2)TiO₃ in CaTiO₃ forming a part solid solution compound achieves the adjustment of for CaTiO₃ at low sintering temperature. The proper dielectric properties with = 78, tan = 0.0006, = +7 ppm/C are obtained for 0.8Ca_0.67(Nd,Mg)_0.22TiO₃-0.2(Li_1/2Nd_1/2)TiO₃ ceramics.     

Processing and Electrical Properties of 0.5Pb(Yb1/2Nb1/2)O3-0.5PbTiO3 Ceramics

Pb(Yb_1/2Nb_1/2)O₃-PbTiO₃ ceramics at the morphotropic phase boundary (50:50) were sintered by conventional and reactive methods to 95% theoretical density and grain sizes <10 m. Excess PbO, added to enhance the densification, resulted in PbO-based non-ferroelectric phases that degraded the electrical properties. Volatilization of excess PbO by annealing the samples after sintering resulted in dense, perovskite samples and excellent electrical properties. The best electrical properties, obtained via reactive sintering, were a remanent polarization, P _r, of 0.36 C/m², a maximum dielectric constant of 31,000 (at the T _c = 371°C and 1 kHz), a piezoelectric charge coefficient, d ₃₃, of 508 pC/N, and an electromechanical coupling coefficient, k ₃₃, of 0.61.     

Calculation of the intrinsic dead layers thicknesses from Au/Ba0.5Sr0.5TiO3/Pt thin film capacitors

Ferroelectric Ba_0.5Sr_0.5TiO₃ (BST) films were prepared on Pt/Ti/SiO₂/Si substrates by the sol-gel process. The films were spin-coated at 2000 rpm for 30 secs and then pyrolysed for 5 mins at the temperature of 350^∘C. This coating procedure was repeated for 3, 4, 5 and 6 times to obtain BST films with different thicknesses. After coating the films with the desired repetition times, the films were finally annealed in a conventional furnace at temperatures ranging from 600^∘C to 800^∘C with a 50^∘C interval in between. The films obtained with an annealing procedure of 750^∘C were polycrystalline with the presence of an impurity BaCO₃ phase. The capacitance and leakage current were measured and used to extract information on the metal-BST interface. With the series capacitance model and modified Schottky emission equation, the thickness of the dead layers for Au/BST and Pt/BST interfaces were calculated to be less than 6 nm and 5 nm, respectively.     

Ferroelectric Property and Crystal Structure of KNbO3 Based Ceramics

Rietveld refinement analysis was carried out to obtain the knowledge on the solid solution structure of the La and Fe co-doped KNbO₃ ceramics. The diffraction data was well fitted with tetragonal space group P4mm, and showed that La and Fe located at K and Nb sites in KNbO₃ perovskite, respectively. The sum of both occupancy ratios agreed almost well with the doping content. Furthermore, the effects of MnO₂ addition on the ferroelectric properties and crystal structure of the La and Fe co-doped KNbO₃ ceramics were investigated. MnO₂ addition strongly affected the ferroelectric and piezoelectric properties, because the valence of Mn ions changed from Mn^{4 +} to some extents of Mn^{3 +} and Mn²⁺, which were suggested by XAFS analysis.     

Control of the Grain Boundary Electrical Features of the Semiconducting SrTiO3 Ceramics Synthesized from Surface-Coated Powders

Polycrystalline SrTi_0.99Nb_0.01O₃ (STNO) ceramics were synthesized by hot-press sintering Na-coated semiconducting STNO powders. The chemical and electrical characteristics of the grain boundary of the ceramics were investigated, and their relations were discussed in terms of process parameters. The diffusion coefficients as well as the activation energy of the Na ions near the grain boundary were obtained at particular heat-treatment conditions; it was demonstrated that these values can be used to design specific electrical features of the grain boundary. A systematic variation in the electrical characteristics of the grain boundary with process parameters was observed; it indicates that this synthesis method can be used for fine control over the chemical and electrical properties of the semiconducting ceramics.     

Structure and Properties of Hot-Pressed Pb(Lu1/2Nb1/2)O3-PbTiO3 Binary System Ceramics*

Solid solution series of the (1 - x)Pb(Lu_1/2Nb_1/2)O₃ - x PbTiO₃ binary system ceramics (PLuNT) were synthesized and hot-pressed (temperature 950°C to 1130°C, pressure 25 MPa); its structure, dielectric and piezoelectric properties were studied. Pure lutecium niobate PLuN (x = 0) has a pronounced long-range order in the B-sublattice and an antiferroelectric to paraelectric phase transition at 258°C. The phase structure of the PLuNT system, at room temperature, changes from a pseudomonoclinic (psd-M, space group Bmm2) to tetragonal (T, space group P4mm). The pseudomonoclinic phase extends over the 0 x 0.38 interval within which the monoclinic angle proceeds a minimum near to 90° at x 0.2. The morphotropic region covers the interval x = 0.38 - 0.49, the concentration ratio psd-M:T 1 (the morphotropic phase boundary—MPB) corresponds to x = 0.41. Within the morphotropic region, a rather strong distortion of the unit cell—(c/a - 1) 0.02, 90.37º, characteristic of hard piezoelectrics is maintained. Dielectric dispersion and broadening of the phase transition, features typical to relaxors, are observed within the concentration interval of 0.1 x 0.3. The highest electromechanical coupling coefficients: k_p = 0.66, k_t = 0.48, k₃₁ = 0.34 of (1 - x) PLuN–xPT ceramics are attained in compositions near the MPB at x 0.41. Non-isovalent doping of PLuNT with La³⁺ in Pb sublattice shifts the MPB to lower values of x.     

Low-temperature sintering and electrical properties of (1−x)Pb(Zr0.5Ti0.5)O3-xPb(Cu0.33Nb0.67)O3 ceramics

Electrical properties and sintering behaviors of (1 − x)Pb(Zr_0.5Ti_0.5)O₃-xPb(Cu_0.33Nb_0.67)O₃ ((1 − x)PZT-xPCN, 0.04 ≤ x ≤ 0.32) ceramics were investigated as a function of PCN content and sintering temperature. For the specimens sintered at 1050^∘C for 2 h, a single phase of perovskite structure was obtained up to x = 0.16, and the pyrochlore phase, Pb₂Nb₂O₇ was detected for further substitution. The dielectric constant (ε _r), electromechanical coupling factor (K_p) and the piezoelectric coefficient (d ₃₃) increased up to x = 0.08 and then decreased. These results were due to the coexistence of tetragonal and rhombohedral phases in the composition of x = 0.08. With an increasing of PCN content, Curie temperature (T_c) decreased and the dielectric loss (tanδ) increased. Typically, ε_r of 1636, K_p of 64% and d₃₃ of 473pC/N were obtained for the 0.92PZT-0.08PCN ceramics sintered at 950^∘C for 2 h.     

Properties of Chemical Solution Deposited Polycrystalline Neodymium-Modified Bi4Ti3O12

Thin films of neodymium-modified bismuth titanate Bi_3.44Nd_0.56Ti₃O₁₂ (BNT) were grown on Pt/TiO₂/SiO₂/Si substrates using chemical solution deposition method. The capacitors made by applying top Au electrodes on BNT films showed significantly improved values of the remanent polarization as compared to that using bismuth titanate Bi₄Ti₃O₁₂ (BT) films. The 2P _r value for the BNT capacitors was determined to be equal to 38 C/cm² at an applied voltage of 24 V, whereas, for Bi₄Ti₃O₁₂ (BT) capacitors a value of 20 C/cm² was measured at the same applied voltage. The maximum piezoelectric and pyroelectric coefficients of 22 pm/V and 112 C/m² K respectively, were measured for the BNT thin films.     

Microwave Dielectric Characteristics of MgTiO<Subscript>3</Subscript>/CaTiO<Subscript>3</Subscript> Layered Ceramics

MgTiO₃/CaTiO₃ layered ceramics with differently stacking were fabricated and the microwave dielectric properties were evaluated with TE₀₁₁ mode. With increasing CaTiO₃ thickness fraction, the resonant frequency decreased and the dielectric constant increased with a near-linear relation for the bi-layer ceramics, while the values of the tri-layer MgTiO₃/CaTiO₃/MgTiO₃ ceramics with thickness ratio of 1:1:1 derived much from the curves of the bi-layer ceramics. The finite element method was used to give an explanation for the differences between the bi-layer and tri-layer ceramics.     

Piezoelectric ceramics of (Bi1/2Na1/2)TiO3-PbTiO3-BaTiO3 system

Piezoelectric and ferroelectric properties of bismuth sodium titanate, (Bi_1/2Na_1/2)TiO₃(BNT)-based solid solution, that is, (Bi_1/2Na_1/2)(_1-x)(Pb_a Ba_b)_xTiO₃(a + b = 1) [BNPB(100x-100a/100b)], are studied from the viewpoint of a new group of lead-free or low-lead content piezo-electric ceramics with a rhombohedral(F_a-tetragonal (F_β) morphotropic phase boundary (MPB). It is evident that the MPB seems to be remarkably efficacious in promoting piezoelectric and pyroelectric activities by electrical poling. X-ray diffraction data, dielectric properties and D-E hysteresis loops show that the MPB exist near (Bi_1/2Na_1/2)TiO₃[BNT] at x = 0.13–0.14, 0.08–0.09 and 0.06–0.07 in the case of b = 0, b = 0.5 and b = 1, respectively. BNPB ceramics are superior for piezoelectric ceramics in high-frequency ultrasonic uses, or special piezoelectric actuator materials with a lower free permittivity ε₃₃Tε₀, and a high electromechanical coupling factor k₃₃, along with a high mechanical strength.     

Ferroelectric Properties of (Bi, Sm)4Ti3O12 (BST) Thin Films Fabricated by a Metalorganic Solution Deposition Method

Ferroelectric properties of samarium substituted Bi₄Ti₃O₁₂ films, Bi_3.15Sm_0.85Ti₃O₁₂ (BST), were evaluated for use as lead-free thin film ferroelectrics for FeRAM applications. The BST films were fabricated on the Pt/Ti/SiO₂/Si(100) substrates by a metalorganic solution deposition method. The measured XRD patterns revealed that the BST films showed only a Bi₄Ti₃O₁₂-type phase with a random orientation. The BST film capacitors showed excellent ferroelectric properties. For the film capacitor annealed at 700C, 2P_r of 64.2 C/cm² and 2E_c of 101.7 kV/cm at applied electric field of 150 kV/cm were observed. The capacitor did not show any significant fatigue up to 1.5 × 10⁸ read/write switching cycles at a frequency of 1 MHz, which suggests that the samarium should be considered for a promising lanthanide elements to make a good thin ferroelectric film for memory applications.