Voltage tunable epitaxial Pb x Sr(1− x )TiO3 films on sapphire by MOCVD: Nanostructure and microwave properties

Frequency and phase agile microwave components such as tunable filters and phase shifters will require ferroelectric thin films that exhibit a nonlinear dependence of dielectric permittivity (ɛ _r ) with dc electric bias, as well as a high material (Δɛ _r /tan δ) and device (or K-factor in phase shift/dB) figure of merits (FOM). Therefore, voltage tunable (Pb_0.3Sr_0.7)TiO₃ (PST) thin films (90–150 nm) on (0001) sapphire were deposited by metal-organic chemical vapor deposition at rates of 10–15 nm/min. The as-deposited epitaxial PST films were characterized by Rutherford backscattering spectroscopy, X-ray methods, field emission scanning electron microscope, high resolution transmission electron microscopy, Raman spectroscopy, and electrical methods (7–17 GHz) using coplanar waveguide test structures. The epitaxial relationships were as follows: out-of-plane alignment of [111] PST//[0001] sapphire, and orthogonal in-plane alignments of [ ] PST//[ ] sapphire and [ ] PST//[ ] sapphire. The material FOM and device FOM (or K-factor) at 12 GHz were determined to be 632 and ∼13 degrees/dB, respectively. The results are discussed in light of the nanostructure and stress in epi-PST films. Finally, a rational basis for the selection of PST composition, substrate, and process parameters is provided for the fabrication of optimized coplanar waveguide (CPW) phase shifters with very high material and device FOMs.     

Synthesis and characterization of (Sr1−x′K2x)Zr4(PO4)6 ceramics

Single phase (Sr_1–x K_2x )Zr₄(PO₄)₆, where x lies between 0.0 and 1.0, ceramic powder with a submicron scale particle size has been synthesized successfully at calcination temperatures as low as 650–750°C by a sol-gel technique. The formation of the powder strongly depends on calcination temperature, but is independent of solution pH in the studied range. Dilatometric measurement shows an ultra-low linear coefficient of thermal expansion of 0.1×10^–6°C^–1 when x=0.5 at temperature intervals of 25–1000°C. Thermal conductivity and flexural strength of the materials were determined at ambient temperature to be 1.0 Wm^–1K^–1 and as high as 280 MPa, respectively, indicating that this material can be an excellent candidate in many applications, especially those subjected directly to severe environments.     

Effect of Te Substitution on (Tl0.5Pb0.5)Sr2(Ca1?x Te x )Cu2O7 (x=0.0 to 0.5) Superconductor

The (Tl_0.5Pb_0.5)Sr₂(Ca_1?x Te _x )Cu₂O_7??? (Tl-1212) superconductor for x=0.0 to 0.5 has been prepared and studied by a powder X-ray diffraction method, electrical resistance and AC susceptibility measurements. Most of the samples showed Tl-1212 as the major phase and Tl-1201 as the minor phases. Small amounts of Te substitution (x??0.3) maintained the formation of the Tl-1212 phase but larger amounts led to the formation of 1201 and an unknown impurity phase. The resistance versus temperature curve showed metallic behavior for all samples. The resistance versus temperature curves showed onset transition temperature ( $T_{\mathrm{c\ onset}}$ ) between 92 and 97 K. Our results indicated the combined effects of Te substitution, heating temperature and heating time on the formation and optimization of the (Tl_0.5Pb_0.5)Sr₂(Ca_1?x Te _x )Cu₂O₇ superconductor.     

Crystalline structure and dielectric properties of (Sr1−1.5x Bi x ) TiO3 ceramics

The crystalline structure, microstructure and dielectric properties of the (Sr_1–1.5x Bi _x )TiO₃ (0 x 0.267) ceramics were studied. Cubic solid solutions were determined for x 0.2 at room temperature. However, lattice distortion was detected by Raman spectra. A dense microstructure with the grain sizes of 2–4 m was obtained for (Sr_1–1.5x Bi _x )TiO₃ (0 x 0.2) ceramics. The Bi concentration was examined and found to be in agreement with the nominal composition and overall uniformly distributed in the sample. Different from the observations in the earlier literature for other doped quantum paraelectrics, where only an induced dielectric anomaly was reported, there are three Bi induced dielectric modes A, B, and C in the Bi doped SrTiO₃ samples. The occurrence of the impurity modes and the ferroelectric relaxor mode and their evolution are demonstrated as a function of Bi concentration.     

Superconducting and Magnetic Properties of Polycrystalline [(Bi,Pb)2Sr2Ca2Cu3O x ]1−x (La0.7Sr0.3MnO3) x Thick Films Grown Using MQA Method

Polycrystalline thick films with the nominal composition [(Bi,Pb)₂Sr₂Ca₂Cu₃O _x ]_1?x (La_0.7Sr_0.3MnO₃) _x (x=0, 0.01, 0.03, 0.05) were prepared by the melting-quenching-annealing (MQA) method on (001)-oriented LaAlO₃ (LAO) substrates. The XRD patterns show that the samples are composites consisting of (Bi,Pb)₂Sr₂Ca₂Cu₃O _x and La_0.7Sr_0.3MnO₃ particles with average grain sizes of ～60 and ～30 nm, respectively. From electric transport measurements, the superconducting onset temperature, T _onset, and superconducting critical temperature, T _c, ended up being ～80 and ～60 K, respectively. The depression of T _c may be attributed to the proximity effect between ferromagnetism and superconductivity. The M–H hysteresis loops indicate the coexistence of ferromagnetism and superconductivity in the films. The magnetic field dependence of the superconducting current density and the volume pinning force F _p=J _c×B were obtained by applying Bean’s model to the isothermal M–H loops.     

Thermal Diffusivity of La1−x Sr x MnO3 (x < 0.3)

Perovskite manganites are interesting because of their colossal magnetoresistance. In this work high resolution thermal diffusivity measurements of La_1–x Sr _x MnO₃ (0 x 0.3) single crystals in the temperature range from 250 to 400 K are presented. A photopyroelectric device in the standard back configuration has been used. The thermal diffusivity through second-order magnetic phase transitions, as well as through first- and second-order structural phase transitions has been measured. The critical parameters of the sample with x = 0.3 at the ferromagnetic-to-paramagnetic transition have been obtained, and are close to the values predicted by the Ising model.     

139La-NMR study of spin-flop and spin structure in La2−x Sr x CuO4(x∼1/8)

The external field dependence of the hyperfine field at La-site has been studied on La _2–x Sr _x CuO ₄ (x=0.115) and La _2–x Ba _x CuO ₄ (x=0.125), where the magnetic ordering in Cu-3d spins exists at low temperature. In La _1.885 Sr _0.115 CuO ₄, a significant decrease in the resonance line width was observed above a field of H _c 7.5T, which is the direct evidence of the spin-flop in the canted-spin system with Dzyaloshinski-Moriya interaction. The spin-flop field H _c of 7.5T is slightly lower than that in La ₂ CuO ₄ (H _c 10T), reflecting the decrease of the tilting angle of the CuO ₆ octahedra by the substitution of Sr ²⁺ ion for La-site.     

Physical and electrical properties of MnO2-doped Pb(Zr x Ti1−x )O3 ceramics

The effects of composition on the physical property change in the phase coexistence region between the tetragonal and rhombohedral phases have been investigated as a function of zirconium concentration, x, for the MnO₂-doped Pb(Zr _x Ti_1–x )O₃ (0.40x0.60) ceramics. The relative amount of phase coexisting between the tetragonal and rhombohedral phases affects greatly both dielectric and piezoelectric properties as a function of zirconium concentration. However, there are no detectable changes between the apparent density and microstructure. Also, in the coexistence region, the relative amount of coexistence of the rhombohedral phase increases with MnO₂ addition. The inflection points of the dielectric constant shift to lower zirconium concentration in proportion to the MnO₂ addition, owing to the substitution effect on the PZT lattice site.     

Conduction in nanostructured La1?x Sr x FeO3 (0 ≤ x ≤ 1)

We investigated electrical properties of nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) from 300 K?C400 K. The nanostructured La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was synthesized by citrate gel method requiring no pH control. X-ray diffraction pattern showed that single phase LaFeO₃ with an orthorhombic structure was formed. The structure changed into rhombohedral for x = 0.5 and it became cubic for x = 1.0. For x ?? 0.5, our material showed non-linear current-voltage characteristics and for x > 0.5 it showed linear current-voltage characteristics. Poole Frenkel type conduction mechanism was found to be operative in LaFeO₃ from 300 K?C400 K. The experimental values of field-lowering coefficient were by 2.56?C6.41 times higher than the predicted value and were attributed to the presence of localized fields. The increase in conductance with Sr content was due to formation of Fe⁴⁺ ions in addition to Fe³⁺ with the increase in Sr content. Impedance spectroscopy and ac conductivity analysis of La_1?x Sr _x FeO₃ (0 ?? x ?? 1) was also carried out in the temperature range from 300 K?C400 K and frequency was varied from 20 Hz - 2 MHz. The ac conduction followed the correlated barrier hopping model in La_0.9Sr_0.1FeO₃.     

Effect of CuO on the sintering and dielectric characteristics of (Ba1−x Sr x ) (Ti0.9Zr0.1)O3 ceramics

In order to lower the temperature required to density (Ba_1–x Sr _x ) (Ti_0.9Zr_0.1) O₃ (BSTZ-series) and to avoid the formation of a low dielectric constant phase, copper oxide is added as liquidphase promotor after BSTZ-series are calcined. Thea-axis lattice constant at room temperature elongates with both increasing amount of CuO added and higher sintering temperature, while thec-axis lattice constant elongates only slightly under the same condition. The dielectric constant increases with sintering temperature. However, for different amounts of CuO added, the dielectric constant increases with increasing amount of CuO at lower sintering temperatures (below 1100°C). When a higher sintering temperature is used (above 1200°C), the dielectric constant reaches a maximum at 1 wt % CuO added, and decreases slightly on further addition of CuO.     

Structural,electrical and magnetic properties of polycrystalline La0.67(Ca1−x Sr x )0.33MnO3 manganites

Polycrystalline La_0.67(Ca_1?x Sr _x )_0.33MnO₃ with different substitution level of strontium element, were synthesized via solid state reaction. Structure of samples was characterized by X-ray diffraction (XRD). XRD patterns reveal that La_0.67Ca_0.33MnO₃ exhibits orthorhombic structure with space group Pnma. Phase transitions from orthorhombic to rhombohedral take place as Ca ions were gradually substituted by Sr ions. The XRD data were further analyzed by Rietveld refinement technique. The data show that Mn–O–Mn bond angle increases as x increases. Microstructures obtained from SEM show that substitution of Sr ions has demoted the grain growth and densification process during sintering. The substitution of Sr ions has greatly influenced the hopping integral of electron via double exchange interaction, thus affecting the electrical properties and magnetic properties as well. The resistivity decreases and the metal–insulator transition temperature (T _p ) shifts to higher temperature as x increases. The magnetoresistance (MR) effect gradually decreases and MR peak shifts to higher temperature as x increases. The magnetization measured at room temperature is found to be increasing as x increases.     

Pb1−x Bi x /Bi/Pb1−x Bi x Josephson junction

A superconductor/semimetal/superconductor (S/SM/S) Josephson junction has been developed. We have used an alloy of Pb_1–x Bi _x (0x 0.6) as the superconductor and Bi as the semimetal. By irradiating at X-band microwave of 10 GHz, Shapiro steps were observed for various bismuth barrier thicknesses inÅ and bismuth weight ratiosx. Finally, we obtained the empirical relationship for barrier thickness, below which microwaves could be detected for various bismuth weight ratiosx at the temperature of 4.2 K.     

低电阻率的(Sr,Pb)TiO_3基PTCR陶瓷

低电阻率的（Ｓｒ，Ｐｂ）ＴｉＯ３基ＰＴＣＲ陶瓷（Ｓｒ，Ｐｂ）ＴｉＯ３ＰＴＣＲＣｅｒａｍｉｃｓｗｉｔｈＬｏｗＲｅｓｉｓｔｉｖｉｔｙ王德君郭淳桂治轮李龙土（清华大学，北京，１０００８４）ＷａｎｇＤｅｊｕｎＧｕｏＹｕｃｈｕｎＧｕｉＺｈｉｌｕｎＬｉＬｏｎ...     

Synthesis of New Superconducting Pb-Based 1222 Cuprates Containing Sulfur in the (Pb0.75S0.25)Sr2(Eu2.0−x Ce x )Cu2O z System

We have synthesized new Pb-based 1222 cuprates containing sulfur in the (Pb_0.75S_0.25)Sr₂(Eu_2.0?x Ce _x )Cu₂O _z system. X-ray diffraction study shows that almost the single 1222 phase samples can be obtained for a considerable wide area of 0.3≤x≤1.2 in the composition of (Pb_0.75S_0.25)Sr₂(Eu_2.0?x Ce _x )Cu₂O _z . Next, the sample with x=0.4 after annealing under high-pressure O₂ is discovered to show an onset of the resistivity drop at about 31 K and to show an onset of diamagnetic signal at about 29 K. These phenomena clearly indicate that the sample is a new superconductor.     

The thermal conductivity and Lorenz function of the tin-lead alloy system Sn x Pb1 − x (x = 0.85, 0.7 0.5 0.3)

The thermal conductivity and electrical resistivity of the tin-lead alloy system Sn _x Pb_{1 – x} (x = 0.85, 0.7 0.5 0.3) were measured in the temperature range 7–300 K. The thermal conductivity was analyzed at temperature T 20K, assuming 1//T+Tⁿ, where , , and n are constants. The analysis shows that n < 2, and not n 2, which would be expected for a normal pure metal. The electrical resistivities could be represented by a T ⁵ relation for temperatures up to about 60 K. The characteristic temperature _R appears to decrease with increasing weight percent of lead. The total Lorenz functions were high, indicating the presence of phonon conductivity. The phonon conductivity _g appears to vary with T, and can be represented by _g=a/Tⁿ (a > 0) and n2.Work supported by the Universiti Sains Malaysia.     

Electrical resistivity and Seebeck coefficient of La1−x M x MnO3 (M = Ca,Sr) single crystals

The temperature dependence of the electrical resistivity and Seebeck coefficient was measured on single crystals of La_1–x Ca _x MnO₃(0 <x 0.3) and La_1–x Sr _x MnO 3 (0 <x 0.4) grown by the arc-image floating zone method. The electrical conduction for La_1–x crystals withx 0.2 was of the activation type aboveT _c and of the degenerate type belowT _c, while that for the crystal withx = 0.1 was of the activation type over the whole measured temperature range between –170 and 400°C. The conduction behaviour of La_{1– x} Sr _x MnO₃ was essentially the same as that of La_1–x Ca _x MnO₃ except that the conduction of the crystals withx = 0.3 and 0.4 was of the degenerate type aboveT _c. A distinct difference in Seebeck data was observed between the calcium and the strontium compounds.     

Independent Control of Low-Energy Resonant States and Polaron States by the Zn-Doping and the Structural Transition in La2−x Sr x CuO4 and La2−x Ba x CuO4 (x=0.11)

The superconductivity depression mechanisms at x≈1/8 in La_2−x Ba _x CuO₄ and Zn substitution in La_2−x Sr _x CuO₄ were investigated by Raman scattering. About 80% of low-energy electronic states are two-dimensional at x≈1/8 and form the Fermi arc around (π/2,π/2). The low-energy states are composed of the resonant peak relating to the insulator–metal transition and the polaron states of the B _3u phonons. Zn substitution depresses the resonant peak, while the LTT structure depresses the polaron states. The superconductivity is suppressed if one of them is reduced.     

Magnetization curves of (La1−x Sr x )2CuO4−δ single crystals as functions ofx and δ

The second peak effect in magnetization curves for overdoped (La_1–xSr_x)CuO_4– single crystals was examined by means of systematic variations of Sr content x and oxygen deficiency . Oxygen defect concentration was found to sensitively affect the critical temperature T_c and the macroscopic pinning force F_p, resulting in significant changes in magnetization hysteresis loops. Observations of dependence of M and F_p at the same reduced temperature T/T_c yielded an insight into the role of oxygen defects: increasing results in increasing the pinning center density N. The second peak field B_2pk seemed to be determined by the development of a percolating network of magnetically reversible regions from the observation that the temperature dependence of B_2pk showed similar behavior to the irreversibility field B_irr.     

Phase evolution and gas-phase particle size distributions during spray pyrolysis of (Bi,Pb)SrCaCuO and Ag(Bi,Pb)SrCaCuO powders

Phase evolution, gas-phase particle size distributions and lead loss were studied during formation of (Bi,Pb)SrCaCuO powders and their composites with silver by spray pyrolysis starting from nitrate solutions. The 10 wt% Ag/90 wt% Bi_1.8Pb_0.44Sr₂Ca_2.2Cu₃O_x composite powders made at 700°C consisted of 20–60 nm grains of silver and mixed-oxide phases with a fine dispersion of Ag grains within the particles. At 700°C, the primary phases present in (Bi,Pb)SrCaCuO powders were (Bi,Pb)₂Sr₂CuO_x (2201), Ca₂PbO₄ (plumbate), (Bi,Pb)₂Sr₂CaCu₂O_x(2212), and (Bi,Pb)₃Sr₂Ca₂Cu₁O_x(3221). For T≥800°C, the powders were considerably depleted in lead, and the plumbate and 3221 phases were absent. For T = 900°C, a large number of ultrafine particles (<30 nm) were formed, probably from the PbO vapor released from the reactor walls. Using spray pyrolysis, it is easy to control stoichiometry and limit the phase segregation at the nanometer-scale so that homogeneous and phase-pure materials can be obtained rapidly during subsequent processing.