Emergence of the sub‐THz central peak at phase transitions in artificial BaTiO3/(Ba,Sr)TiO3 superlattices

A prominent central peak in the sub‐THz frequency range was observed in the Raman spectra of BaTiO₃/(Ba,Sr)TiO₃ (BT/BST) superlattice grown on (001)MgO substrate. Both soft and central mode show an anomaly around 200 K and 280 K, which can be correlated with orthorhombic to monoclinic phase transition of BST and BT, respectively. The observed temperature dependence of the central mode enabled us to explain rather broad temperature dependence of the dielectric permittivity previously observed in BT/BST superlattices. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Coupled mode behavior of the soft E(TO) phonon of Pb(Ti1-x,Zrx)O3 and (Pb1-3x2, Lax)TiO3

We report the temperature dependence of the low frequency part (ω < 100 cm^?1) of the Raman spectra of the Pb(Ti_1-x, Zr_x)O₃ and $\text{(}\text{Pb}{}_{\mathrm{<mtext>1-</mtext><mtext>3x</mtext><mtext>2</mtext>}}$, La_x)TiO₃ systems. The spectra indicate a coupled mode behavior between the soft E(TO) phonon and a mode which produces an additional band in the spectra. We discuss the possibility that the additional band might be due to zone boundary tranverse acoustical phonons which couple to the q ～ 0 soft E(TO) mode because of the disorder existing in the systems.     

氧压对Ba0.6Sr0.4TiO3薄膜晶格常数的影响及BaTiO3/Ba0.6Sr0.4TiO3超晶格的制备

采用脉冲激光沉积(PLD)技术,经一系列的优化实验成功地制备了BaTiO₃(BT)和Ba_0.6Sr_0.4TiO₃(BST)单层膜.X射线衍射分析表明,在LaAlO₃(001)单晶平衬底上生长的BT和BST薄膜都是沿[001]取向的近外延生长.且随着氧压在10^-3—25 Pa范围内逐渐增大,BST薄膜的晶格常数与氧压之间近似满足Boltzmann函数关系.其次,在此优化条件下还 关键词： 超晶格 晶格常数 激光感生热电电压 脉冲激光沉积     

Microstructures and dielectric properties of compositionally graded (Ba1-xSrx) TiO3 thin films prepared by pulsed laser deposition

Compositionally graded (Ba_1-xSr_x)TiO₃ (BST) (x:0.0∼0.25) thin films were grown on Pt (111)/TiO₂/SiO₂/Si (100) substrates using layer-by-layer pulsed laser deposition in the temperature range 550–650 °C. Both downgraded (Ba/Sr ratio varying from 100/0 at the bottom surface to 75/25 at the top surface) and upgraded (Ba/Sr ratio varying from 75/25 at the bottom surface to 100/0 at the top surface) BST films were prepared. Their microstructures were systematically studied by X-ray diffractometry and scanning electron microscopy. A grain morphology transition from large ‘rosettes’ (>0.30 μm) to small compact grains (70–110 nm) was observed in the downgraded BST films as the deposition temperature was increased from 550 to 650 °C. No such grain morphology transition was detected in the upgraded BST films. Dielectric measurements with metal electrodes revealed an enhanced dielectric behavior in the downgraded films. This enhancement is mainly attributed to the large compressive stress field built up near the interface between the downgraded film and substrate. Furthermore, the BaTiO₃ layer in the downgraded BST films not only serves as a bottom layer but also as an excellent seeding layer for enhancing the crystallization of the subsequent film layers in the downgraded films. Received: 10 December 2001 / Accepted: 12 March 2002 / Published online: 19 July 2002 RID="*" ID="*"Corresponding author. Fax: 86-25/359-5535, E-mail: xhzhu@public1.ptt.js.cn     

X-ray diffraction investigation of BaTiO3/(Ba,Sr)TiO3 superlattices

Samples of BaTiO₃/(Ba_{1 ? x} Sr _x )TiO₃ (BT/BST-x) superlattices have been studied using X-ray diffraction analysis. A complete parallel orientation of all the studied films and the substrate has been revealed, and the modulation periods ?? of the superlattices, the parameters of the unit cell averaged over the ?? period, and the parameters of individual components of the superlattices have been determined.     

Characteristics of Ba xSr 1–xTiO 3 thin films grown by pulsed laser ablation of rotating split targets of BaTiO 3 and SrTiO 3

We have grown heterostructures of Ba_xSr_1-xTiO₃(BST)/La_0.7Sr_0.3MnO₃(LSMO) on LaAlO₃(LAO) substrates by the pulsed laser deposition method. BST films with x=0.2,0.5,0.7 and 0.8 have been prepared using a novel rotating split-target arrangement. The lattice constant of the BST films is found to vary linearly with Ba/Sr ratio. An excellent cube-on-cube epitaxial relationship of (100)_BST||(100)_LSMO||(100)_LAO has also been obtained. Scanning electron microscopy studies have revealed smooth and crack-free BST films with a uniform grain size of about 100 nm. Dielectric measurements, made with patterned Au top electrodes and conducting LSMO bottom layers, have shown a maximum permittivity of approximately 280 at 5 kHz in BST films with x=0.7. P–E loop analyses of the Ba_0.7Sr_0.3TiO₃ and Ba_0.8Sr_0.2TiO₃ films have yielded remnant polarization values of 1.66 and 1.81C/cm², respectively. PACS 81.15Fg; 68.55Jk; 77.55+f     

A one-dimensional SiGe superlattice grown by UHV epitaxy

One-dimensional SiGe superlattices with periods ranging from 100 to 800 Å have been deposited on Si substrates by periodically varying the Ge content of a mixed Si_1-x Ge _x multilayer structure fromx=0 tox=0.15. The deposition was successful, employing and UHV evaporation technique at a substrate temperature of 750°C fulfilling the four conditions: Single crystal growth, no interdiffusion, two-dimensional growth, and pseudomorphic growth. It is shown that mismatch above 8 · 10^?3 favours growth by three-dimensional nucleation. The experimentally determined spacing of misfit dislocations is compared with theoretical results obtained by van der Merwe. The pseudomorphic growth behaviour of layers thinner than a critical thickness could be confirmed.     

Relationships between the structural properties and the superconductivity in Y0:4Pr0:6Ba2-xSrxCu3O7-δ (x = 0;1:0)

The Y_0:4Pr_0:6Ba_2-xSr_xCu₃O_7-δ (x = 0;1:0) samples were prepared and the structural properties were studied by X-ray Rietveld analysis. It has been found that the average Pr-O bond length increases from 2.435Å at x = 0 to 2.457Å at x = 1:0, the Cu(2)-O-Cu(2) angles within the CuO₂ planes become larger, and there is no significant mutual substitution between Pr and Sr ions. The BVS calculation suggests that Sr doping brings about the increase of the hole concentration on CuO₂ planes and the weakening of Pr-O covalent mixing. Our work supports that Pr-O covalent mixing effect is responsible for the superconductivity suppression by Pr.     

‘Soft’ optical phonons and the morphotropic phase transition of the Pb(Ti1−x, Zrx)O3 system

Room temperature Raman scattering results for the Pb(Ti_1?x, Zr_x)O₃ system in its tetragonal ferroelectric phase are analyzed. For x ≤ 0.25, the square of the frequency of the ‘soft’ E(TO) phonon is linear in the Zr concentration. In addition, we find that the morphotropic phase transition at x = 0.535 may be associated with an instability of this ‘soft’ phonon. It is shown that changes in the short-range harmonic forces play an important role in the x-dependence of the ‘soft’ E(TO) phonon frequency.     

Anomalous phonon intensities in the Raman spectrum of disordered CsMg1−xCoxCl3

The five Raman-active $\text{k}\text{= 0}$ phonons have been measured at low temperatures and for a range of x in the disordered lattice CsMg_1-xCo_xCl₃. While the E_2g^a, E_2g^b, E_2g^c and A_1g modes at 55.0, 132.0, 189.0 and 255.0 cm^?1 for x = 0 exhibit normal one-mode behaviour, the intensity of the E_1g phonon at 127.5 cm^?1 has a most unusual concentration dependence which requires a new theory.     

Ba0.5Sr0.5TiO3有序构型的第一性原理研究

采用第一性原理计算了Ba_0.5Sr_0.5TiO₃三种有序构型的晶格结构和对应的电子结构,晶格结构的详细分析结果表明BST{100}有序构型为四方相,Ti-O八面体中Ti原子和Ba-Sr平面上的O原子沿[100]方向分别偏心位移0.040 Å和0.065 Å,八面体畸变导致反平行自发极化出现,构型处于反铁电态. BST{110}构型也是四方相,并且(110)和(1 关键词： 钛酸锶钡 第一性原理 有序结构 铁电性     

Synthesis and ferroelectric properties of bismuth layer-structured (Bi7−xSrx)(Fe3−xTi3+x)O21 solid solutions

Bismuth layer-structured (Bi_7−xSr_x)(Fe_3−xTi_3+x)O₂₁ (BSFT) ceramics were synthesized and the ferroelectric properties and crystal structure were investigated. X-ray powder diffraction profiles and refinement of the lattice parameters indicated single phase BSFT was obtained in the composition range 0-1.5. The lattice parameter b of BSFT remained almost constant, while a slight decrease in the lattice parameter a was observed by the Sr and Ti substitution for Bi and Fe, respectively, which indicated an increase in the orthorhombicity. The dependence of the BSFT lattice parameter on temperature implied a phase transition from the orthorhombic to the tetragonal phase, which was in good agreement with the Curie temperature. The remnant polarization P_r, of BSFT was significantly improved by the Sr and Ti substitution for Bi and Fe, and ranged from 9 to 16 μC/cm², although no remarkable variation in the coercive field E_c was observed. As a result, a well-saturated P-E hysteresis loop of BSFT ceramic was obtained at x=0.5 with a P_r of 30 μC/cm at an applied voltage of 280 kV/cm.     

High pressure tuning of optical transitions in Mg[Pt(CN)4]·7H2O

Mg[Pt(CN)₄]·7H₂O belongs to the class of tetracyanoplatinates(II) which crystallize in columnar structures. In different M_x[Pt(CN)₄]·yH₂O (MCP) single crystals the in-chain Pt-Pt-distance R varies between 3.67 Å (NaCP) and 3.15 Å (MgCP). Two optical transitions can be observed in polarized emission with the electric field vector E either parallel or perpendicular to the columnar (c)-axis. Polarized emission spectra of MgCP are recorded under hydrostatic pressure up to p ≈ 18 kbar (at 295 K). The transition energy v?₆ can be tuned from 17,600 cm^-1 to about 12,000 cm^-1 (2.18-1.48 eV). The pressure induced red shift for the two transitions is: E 6 c: dv?₆/dp = -320±20 cm^-1/kbar, E ⊥ c: dv?_⊥/dp = -270±20 cm^-1/kbar. These values are discussed in the context of the known functional relationship (for ambient conditions) between v? and R.     

Interfacial reactions of Ba2YCu3O6+z with coated conductor buffer layer,LaMnO3

Chemical interactions between the Ba₂YCu₃O_6+x superconductor and the LaMnO₃ buffer layers employed in coated conductors have been investigated experimentally by determining the phases formed in the Ba₂YCu₃O_6+x–LaMnO₃ system. The Ba₂YCu₃O_6+x–LaMnO₃ join within the BaO–(Y₂O₃–La₂O₃)–MnO₂–CuO_x multi-component system is non-binary. At 810 °C (p_O2 = 100 Pa) and at 950 °C in purified air, four phases are consistently present along the join, namely, Ba_2?x(La_1+x?yY_y)Cu₃O_6+z, Ba(Y_2?xLa_x)CuO₅, (La_1?xY_x)MnO₃, (La,Y)Mn₂O₅. The crystal chemistry and crystallography of Ba(Y_2?xLa_x)CuO₅ and (La_1?xY_x)Mn₂O₅ were studied using the X-ray Rietveld refinement technique. The Y-rich and La-rich solid solution limits for Ba(Y_2?xLa_x)CuO₅ are Ba(Y_1.8La_0.2)CuO₅ and Ba(Y_0.1La_1.9)CuO₅, respectively. The structure of Ba(Y_1.8La_0.2)CuO₅ is Pnma (No. 62), a = 12.2161(5) Å, b = 5.6690(2) Å, c = 7.1468(3) Å, V = 494.94(4) Å³, and D_x = 6.29 g cm^?3. YMn₂O₅ and LaMn₂O₅ do not form solid solution at 810 °C (p_O2 = 100 Pa) or at 950 °C (in air). The structure of YMn₂O₅ was confirmed to be Pbam (No. 55), a = 7.27832(14) Å, b = 8.46707(14) Å, c = 5.66495(10) Å, and V = 349.108(14) Å³. A reference X-ray pattern was prepared for YMn₂O₅.     

EXAFS of the superconducting oxide BaPb1−xBixO3

The two-valence state Bi³⁺ and Bi⁵⁺ of Bi in the semiconductor BaBiO₃ and in the BaPb_1?xBi_xO₃ (x = 0, 0.25, 0.6 and 1) system has been determined from the EXAFS spectra above the L_III-edges of Ba, Pb and Bi. Peaks in the radial distribution function up to 5 Å from the absorber have been identified through a model calculation using theoretical amplitudes and phase shifts and the interatomic distances from neutron diffraction measurements. We found indication of local disorder in the Pb-Bi sublattice for the mixed compound.     

Ionic conductivity of Zr1−xIn2xO2−x

As x in Zr(In)O_2?x is increased from 0.08 to 0.16 (9–19 mole per cent In₂O₃) the activation energy E(x) for ionic conduction increases from 1.05 to 1.51 eV; the concuctivity decreases from 2 × 10^?5 to 3 × 10^?6Ω^?1cm^?1at 400°C, is composition-independent at about 580°C, and increases from 1 × 10^?2 to 4 × 10^?2Ω^?1cm^?1 at 800°C. The pre-exponential term of the Boltzmann-type conductivity equation depends exponentially on E(x), a much stronger dependence on x than theoretically expected with a model for ionic conductivity that includes nearest-neighbor defect interactions. Analysis of reported conductivity data for Zr(M)O_2?x (M = Sc, Y, Ca and rare earth metals) and other doped oxide electrolytes with fluorite-type structure reveals that the same relationship is observed with these materials when x γ0.08. It is shown that ionic conduction in these oxides is consistent with nearest neighbor vacancy-cation defect interaction forx < 0.08 but that an additional complex interaction with composition-dependent free energy ΔG(x) occurs when xγ 0.08.The lattice constant of Zr(In)O_2?x with the cubic fluorite-type structure is independent of composition, 5.114 ± 0.002 Å, in agreement with ionic size considerations.     

Engineering coercivity in YFe<Subscript>2</Subscript> dominated DyFe<Subscript>2</Subscript>/YFe<Subscript>2</Subscript> superlattice by patterning

Single crystal 400 nm thick Laves phase [20 Å?DyFe₂/80 Å?YFe₂]₄₀ superlattice have been grown by MBE with a (110) growth direction. VSM measurements performed at room temperature with an applied field range of ±1.2×10⁵ Oe, directed along the [001] direction, reveal a unique single-phase-liked ferrimagnetic behavior. A dominant exchange spring behavior is revealed by MOKE measurement along the [–110] direction. Furthermore, for striped arrays patterned along the [001] direction with height-to-width ratio of 0.05, a shape anisotropy of the order of 10⁴ erg/cm³ is induced, resulting into a pronounced change of coercivity due to the comparable magnitude with intrinsic anisotropies. The results demonstrate the feasibility of engineering both single-phase-liked and exchange-spring magnet behavior in Laves phase epitaxial hard/soft superlattices by patterning.     

Temperature dependent of thermal expansion and ferroelectric properties for BiAlO3-modified BaTiO3 lead-free ceramics

Perovskite structure (1 − x)BaTiO₃–xBiAlO₃ (BT–xBA, x = 0.05, 0.08 and 0.1, corresponding to BT–5BA, BT–8BA and BT–10BA, respectively) ceramics were prepared by a solid state reaction route. Crystal structure of BT–xBA ceramics was determined by using XRD. Dielectric properties were studied as a function of temperature at different frequencies, which indicated that the phase transition temperature (T_m) decreased with increasing x. With increasing temperature, thermal expansion dl/l increased while thermal expansion coefficient α had weak concentration dependence. The Burns temperature was much higher than the transition temperature T_m for the BT–5BA and BT–10BA ceramics. Polarization hysteresis loops (P–E), electrostrictive (S–E) and S versus P² (S–P²) at different temperatures were displayed. P_max slightly decreased due to thermally activated leakage current, meanwhile, S_max decreased at above T_m with the contribution of ferroelectric domain reorientation decreased. The electrostrictive coefficient Q value was clearly larger than that of lead-based electrostrictors at room temperature. Furthermore, it exhibited a slim loop with negligible hysteresis and a subtle linear feature at higher temperature.     

Rotational analysis of the B-X band system of the SbO molecule

Rotational analyses of the two 0-0 bands of theB ²ΣX ²Π_reg system of SbO were carried out for the first time from spectrograms taken in the second order of a 21 ft. concave grating spectrograph having a dispersion of 1·25 Å/mm. The rotational constants of the ν=0 vibrational levels of the upper and lower states, and of the coupling constant A₀ of the lower²Π_reg state were deduced. These values are summarised below. v₀₀=25 334·93 cm^?1 B′₀=0·3190 cm^?1 B″₀=0·3490 cm^?1 A ₀=2276 cm^?1 r′₀=1·933 Å r″₀=1·848 Å.     

Dielectric response of (Ba,Sr)TiO3 thin films in a terahertz and IR ranges

Dependences of the dielectric response spectra on the thickness of the films based on the (Ba,Sr)TiO₃ (BST) solid solutions, which were deposited on single-crystal MgO substrates, have been analyzed. Using the Lorentz and Lyddane-Sachs-Teller models, the mutual correspondence of longitudinal optical (LO) and transverse optical (TO) phonon frequencies has established. The giant LO-TO splitting of the lowest-frequency vibration and inversion of LO and TO frequencies of other phonons in the IR spectrum of BST films has been found for the first time.