Role of the TiO6 octahedra on the ferroelectric and piezoelectric behaviour of the poled PbMg1/3Nb2/3O3-xPbTiO3 (PMN-PT) single crystal and textured ceramic

Field cooling (FC) poled/unpoled PMN-29%PT single crystal and room temperature (RT) poled/unpoled PMN-34.5%PT textured ceramic were investigated between ∼0 and 300 °C by thermal expansion, dielectric and Raman spectroscopy. New phase transitions are evidenced at 40, 91 and 180 °C in the case of FC PMN-29%PT as well as at 70 and 200 °C for RT PMN-34.5%PT and their order is discussed. The physical properties of the textured ceramics are rather similar to the ones observed for the single crystals that make them low-cost alternative for a wide range of applications. However, the temperatures and character of the phase transitions strongly depend on the kind of the poling conditions. Temperature dependences of the Raman line parameters show that the NbO₆ octahedra remain stable during temperature increase, while TiO₆ ones evolve quasi-continuously. The step transitions of the Pb²⁺ ion sublattice are evidenced. This suggests that the TiO₆ and Pb²⁺ sublattices are especially coupled. The role of the TiO₆ clusters on the structural phase transitions and dielectric properties of the PbMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-PT) system is discussed. The presence of the Raman modes above the maximum dielectric permittivity reveals that the local symmetry is lower than the cubic one (Pm3m). The decrease of the Raman line intensities vs. temperature indicates precisely the continuous evolution of the local symmetry towards the cubic one. The temperature evolution of the Rayleigh wing parameters appears sensitive to the phase transitions’ presence.     

Optical Dispersion Behavior and Band Gap Energy of Relaxor Ferroelectric 0.92Pb(Mg1/3Nb2/3)O3-0.08PbTiO3 Single Crystal

Refractive indices and extinction coefficients of 0.92Pb(Mg_1/3Nb_2/3)O₃-0.08PbTiO₃(PMN-0.08PT) single crystal are investigated by variable angle spectroscopic ellipsometry (VASE) at different wavelengths. The parameters relative to the energy band structure are obtained by fitting to the single-oscillator dispersion equation, and the band gap energy is also deduced from the Tauc equation. Similar to most oxygen-octahedra ferroelectrics, PMN-0.08PT has the same dispersion behavior described by the refractive-index dispersion parameters.     

Piezoresponse imaging and local characterization of ferroelectric domains in Pb(Zn1/3Nb2/3)O3–7%PbTiO3 single crystals

Ferroelectric domain structures of (001)‐oriented Pb(Zn_1/3Nb_2/3)O₃–7%PbTiO₃ (PZN‐7%PT) single crystals were visualized and characterized by piezoresponse force microscopy (PFM). Locally regular domain configurations are found to be possibly related to the stable macroscopic properties in the PZN‐7%PT single crystals. Nanoscale piezoresponse hysteresis loops measured by PFM tip revealed no evidence of local domain switching behavior in the PZN‐7%PT single crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Polarized Raman mapping study of the microheterogeneity in 0.67PbMg1/3 Nb2/3O3‐0.33PbTiO3 single crystal

Polarized micro‐Raman spectroscopy was carried out on the (001) face of a 0.67PbMg_1/3Nb_2/3O₃‐33%PbTiO₃ (PMN‐33%PT) single crystal. The Raman images revealed the spatial variations of the intensity of the Raman bands, suggesting that the structure in the PMN‐33%PT single crystal varied from one micro‐area to another. When changing the polarization direction of the incident light with respect to the selected crystalline axes, the intensities of the Raman modes varied periodically. According to the Raman selection rules (RSRs), the angular dependences of the Raman modes indicated that the PMN‐33%PT single crystal is in the monoclinic phase. Furthermore, the color patterns in the Raman images were associated with the coexistence of the M_A‐ and M_C‐type monoclinic phases in the PMN‐33%PT single crystal. Our results provide useful information for understanding the microheterogeneity of the relaxor PMN‐xPT single crystals with compositions near the morphotropic phase boundary region. Copyright © 2010 John Wiley & Sons, Ltd.     

Polarized Micro-Raman Study of the Temperature-Induced Phase Transition In 0.67 Pb（Mg1/3Nb2/3）O3-0.33PbTiO3

Polarized Raman spectra of ferroelectric relaxor 0.67Pb（Mg1/3Nb2/3）O3-0.33PbTiO3 （0.67PMN-0.33PT） single crystal are systematically investigated in a wide temperature range from -196 to 600℃ by micro-Raman scattering technique. The results clearly reveal that there are two structural phase transitions in such composite ferroelectric relaxor： the rhombohedral-tetragonal （R- T） phase transition and the tetragonal-cubic （T- C） phase transition. The former occurs at about TR-T =34℃, corresponding to the vanishing of the soft A1 mode at 106cm^-1 recorded in the parallel polarization. The latter appears at about TT-C = 144℃, which can be verified with the vanishing of mode at 780cm^-1 measured in the crossed polarization.     

Orthorhombic and monoclinic ferroelectric phases investigated by Raman spectroscopy in PZN-4.5%PT and PZN-9%PT crystals

Polarized Raman spectra measurements have been performed on orientated single crystals of Pb[(Zn_1/3Nb_2/3)_0.955Ti_0.045]O₃ (PZN-4.5%PT) and Pb[(Zn_1/3Nb_2/3)_0.91Ti_0.09]O₃ (PZN-9%PT) poled by an electric field along the pseudo-cubic direction in order to determine the nature of the induced ferroelectric phases. Under field-cooled (FC) conditions the ferrolectric phase transition sequence, tetragonal-orthorhombic-rhombohedral, was observed in PZN-4.5%PT. Comparison between the phase transitions induced in PZN-9%PT and PZN-4.5%PT crystals in FC shows that the low- temperature ferroelectric phase in PZN-9%PT cannot be orthorhombic and it can be attributed to the monoclinic phase. The characteristic temperatures found by Raman spectroscopy correspond to those obtained by dielectric measurements and by X-ray diffraction reported previously.     

Properties of a New Nonlinear Optical Crystal CdZn2B2O6

Cadmium dizinc diborate （CdZn2B2O6） single crystals have been grown for the first time. The crystal structure of CdZn2B2O6 is the same as that of the Cd3Zn3B4O12. The x-ray diffraction, infrared and Raman spectra, differential scanning calorimetry analysis and density indicate that the physical and chemical properties of both crystals are very similar. Especially, the nonlinear optical coefficients of CdZn2B2O6 and Cd3Zn3B4O12 crystals are 2.6 and 2.4 times as large as that of KH2PO4 crystal respectively. Chemical etching experiments indicated that these crystals are very stable in neutral solution and not hygroscopic in air at room temperature.     

Hetero-Epitaxial Diamond Single Crystal Growth on Surface of cBN Single Crystals at High Pressure and High Temperature

We report a new diamond synthesis process in which cubic boron nitride single crystals are used as seeds, FesoNi20 alloy powder is used as catalyst/solvent and natural flake-like graphite is used as the carbon source. The samples are investigated using laser Raman spectra and x-ray diffraction （XRD）. Morphology of the sample is observed by a scanning electron microscope （SEM）. Based on the measurement results, we conclude that diamond single crystals have grown on the cBN crystal seeds under the conditions of high temperature 1230℃ and high pressure 4.8 GPa. This work provides an original method for synthesis of high quality hereto-semiconductor with cBN and diamond single crystals, and paves the way for future development.     

Laser irradiation of SrTiO3 single crystals

Excimer laser irradiation (248 nm, 34 ns) of SrTiO₃(100)single crystals was studied in order to resolve the feasibility of obtaining well-defined patterned structures. Spots irradiated with a single pulse in the 0.4-1 J/cm² fluence range presented a pattern of cracks along crystallographic directions, which do not propagate beyond the borders, and no ejected material was observed on the non- irradiated areas. Arrays were patterned by translating the single crystal, and different morphologies were found depending on the width of the tracks. Tracks 10 7m wide or more developed a pattern of cracks, whereas 3 7m wide tracks did not. Artificial arrays in magnetoresistive La_2/3Sr_1/3MnO₃ thin films were prepared by using SrTiO₃(100) single-crystal substrates in which arrays had been previously patterned. The interfaces originated a substantial low-field tunnel magnetoresistance.     

Influence of Gamma-Ray Irradiation on Absorption and Fluorescent Spectra of Nd：YAG and Yb：YAG Laser Crystals

We investigate the influence of gamma-ray irradiation on the absorption and fluorescent spectra of Nd^3＋：Y3A15 O12 （Nd： YAG） and Yb^3＋ ： Y3A15 O12 （Yb： YAG） crystals grown by the Czochralski method. Two additional absorption （AA） bands induced by gamma-ray irradiation appear at 255nm and 340nm. The former is contributed due to Fe^3＋ impurity, the latter is due to Fe^2＋ ions and F-type colour centres. The intensity of the excitation and emission spectra as well as the fluorescent lifetime of Nd：YAG crystal decrease after the irradiation of 100 Mrad gamma-ray. In contrast, the same dose irradiation does not impair the fluorescent properties of Yb：YAG crystal. These results indicate that Yb： YA G crystal possesses the advantage over Nd： YA G crystal that has better reliability for applications in harsh radiant environment.     

利用压电力显微镜研究PMN-30%PT单晶体中铁电畴的结构及其演变

本文总结了我们近年米利用压电力显微镜(PFM)研究PMN-30%PT单晶体中铁电畴的结构及其演变的结果.选择PMN-30%PT品体是因为该组分在超声传感器等应用方面具有最大的潜力.铁电畴的观察是基于反压电现象;具体来讲就是当交变电场通过原子力显微镜探针加到晶体表面时,会引起品体表面的起伏振荡,而锁相放大器可以解出该振荡信号的振幅和相位角;其中振幅衬度反映了压电系数d33的大小,而相位衬度则反映了铁电畴的极化方向.文中介绍了平面内以及垂直平面的PFM成像技术,并演示了影响畴的图像的一些因素,其中包括静电倚效应,表层效应和机械抛光的影响.本文还利用有限无模型对PFM成像原理进行了模拟分析.着重研究了晶体中铁电畴的尺寸分布,畴与晶体取向,时间和温度的相关性,以及畴的演变过程.     

Effects of Interfacial Polarization on Voltage Tunability of Pb(Fe1/2Nb1/2)1-xTixO3 Single Crystals

The voltage tunability of Pb(Fe_1/2Nb_1/2)_1-xTi_xO₃ single crystals is investigated at a low electric field (<130 V/cm) in a low frequency range (<1 MHz). The results show that the capacitance is strongly suppressed by the applied dc biases for both the rhombohedral sample and the tetragonal sample. A negative voltage tunability is only detected in the tetragonal sample. The origin of the giant tunability and the negative tunability is discussed based on the multipolarization-mechanism model and the equivalent circuit model, respectively. It is ascribed to the interfacial polarization at the interface of electrode/sample.     

Dielectric, piezoelectric and elastic properties of tetragonal BiScO3-PbTiO3 single crystal with single domain

Modified BiScO₃-PbTiO₃ (BSPT) tetragonal single crystals were grown using high temperature solution method. The dielectric, piezoelectric and elastic properties of single domain BSPT crystals, after poling along [001] crystallographic direction, have been determined experimentally using the resonance method. The results showed that the BSPT tetragonal crystals possess good piezoelectric properties, with electromechanical coupling factor about 88% and piezoelectric coefficient over 400 pC/N at room temperature. BSPT tetragonal crystals have high Curie temperature around 436 °C and high coercive field ∼28 kV/cm, also, the crystal exhibited a very good temperature stability of the properties till 380 °C. For comparison, the material constants of tetragonal Pb(Zn_1/3Nb_2/3)O₃-PbTiO₃ (PZNT) single crystals were measured and listed in this paper.     

利用压电力显微镜研究PMN-30%PT单晶体中铁电畴的结构及其演变(英文)

本文总结了我们近年来利用压电力显微镜(PFM)研究PMN 30%PT单晶体中铁电畴的结构及其演变的结果。选择PMN-30%PT晶体是因为该组分在超声传感器等应用方面具有最大的潜力。铁电畴的观察是基于反压电现象;具体来讲就是当交变电场通过原子力显微镜探针加到晶体表面时,会引起晶体表面的起伏振荡,而锁相放大器可以解出该振荡信号的振幅和相位角;其中振幅衬度反映了压电系数d_(33)的大小,而相位衬度则反映了铁电畴的极化方向。文中介绍了平面内以及垂直平面的PFM成像技术,并演示了影响畴的图像的一些因素,其中包括静电荷效应,表层效应和机械抛光的影响。本文还利用有限元模型对PFM成像原理进行了模拟分析。着重研究了晶体中铁电畴的尺寸分布,畴与晶体取向,时间和温度的相关性,以及畴的演变过程。     

Mg:Fe:LiNbO3晶体的生长及光学性能研究

在Fe:LiNbO₃中掺进MgO和Fe₂O₃以提拉技术生长Mg:Fe:LiNbO₃晶体.对晶体进行极化和还原处理.测试晶体的吸收光谱,Mg:Fe:LiNbO₃晶体吸收边相对Fe:LiNbO₃晶体发生紫移.测试晶体的红外光谱,Mg:(5 mol%)Fe:LiNbO₃晶体OH^-吸收峰由Fe:LiNbO₃晶体的3482 cm^-1移到3534 cm^-1.采用锂空位模型阐述Mg:Fe:LiNbO₃晶体,吸收边和OH-吸收峰移动的机理.测试晶体的抗光致散射能力.Mg:(5 mol%)Fe:LiNbO₃晶体抗光致散射能力比Fe:LiNbO₃晶体提高一个数量级以上.测试晶体的衍射效率和响应时间.Mg:Fe:LiNbO₃晶体响应速度比Fe:LiNbO₃晶体提高四倍.     

Orientation effects on the bandgap and dispersion behavior of 0.91Pb（Zn_（1/3）Nb_（2/3））O_3-0.09PbTiO_3 single crystals

0.91Pb(Zn_1/3Nb_2/3)O₃--0.09PbTiO₃ (PZN--9%PT) single crystals with different orientations are investigated by using a spectroscopic ellipsometer, and the refractive indices and the extinction coefficients are obtained. The Sellmeier dispersion equations for the refractive indices are obtained by the least square fitting, which can be used to calculate the refractive indices in a low absorption wavelength range. Average Sellmeier oscillator parameters E_o, $\lambda$_o, S_o, and E_d are calculated by fitting with the single-term oscillator equation, which are related directly to the electronic energy band structure. The optical energy bandgaps are obtained from the absorption coefficient spectra. Our results show that the optical properties of [001] and [111] poled crystals are very similar, but quite different from those of the [011] poled crystal.     

Surface Emitting THz Wave Parametrical Oscillator Using MgO：LiNbO3

Room-temperature operation terahertz （THz） wave source is demonstrated using three MgO：LiNbO3 crystals which have a noncollinear arrangement. The experimental results show that the THz wave can be tunable from 0.8 THz to 3.0 THz, and the peak energy output is 103 pJ/pulse at 1.5 THz. The noncoilinear cavity configuration makes the THz beam have Gaussian-like spatial distribution, small divergence angle, perpendicularly eradiated from the crystal surface. The beam quality factor M2 is measured to be Mx^2 = 1.15, Mx^2 = 1.25 for characterizing the THz wave beam. Experiments also show that the THz beam can be focused by using a polyethylene lens, and the focal spot size is close to the diffraction limit.     

Giant Birefringence of Lithium Niobate Crystals in the Terahertz Region

Terahertz time-domaln spectroscopy （THz-TDS） is used to study the spectral response of lithium niobate crystals （LiNbO3） in the far infrared region. The optical constants are derived from the measured complex refractive index. A giant birefringence is observed in this material, and the average refractive-index difference between the ordinary wave and the extraordinary wave, no - ne, can reach up to about 1.6. Such a large birefrlngence is attributed to the different p honon modes orAl（z） and E （ x , y ）. This unusual property makes LiNbO3 a promising material to be used as a functional material in the terahertz region, e.g. employed as wave-plates and polarization separators.     

Influence of the electric field on structural transformations and phase boundary for PMg1/3Nb2/3O3-xPbTiO3 single crystals

The influence of different regimes of application of a dc electric field (0 < E < 4 kV/cm) on structural phase transformations and behavior of the phase boundary in [001]-oriented single crystals PMg_1/3Nb_2/3O₃-xPbTiO₃ (PMN-xPT) with compositions near the morphotropic phase boundary (x = 28 and 32%) and far from it (x = 13%) has been investigated. The studies have been performed using optical methods, namely, optical transmittance and small-angle light scattering. It has been revealed that the number, symmetry, and stability of field-induced phases depend on the regime of electric field application. During cooling of the PMN-28PT crystals from the cubic phase in the field (FC regime), the tetragonal phase is induced already in weak fields of ∼0.5 kV/cm, whereas even a field of 3 kV/cm is insufficient for inducing this phase by applying the field in the ferroelectric phase. In the PMN-32PT crystal (which has a composition closer to the morphotropic phase boundary as compared to that of the PMN-28PT crystal) in the FC regime and when the field is applied in the ferroelectric phase, the tetragonal phase is induced already in weak electric fields, even though this phase in the latter case appears to be unstable. The E-T phase diagrams have been constructed for different regimes of field application. The possible factors responsible for the observed differences have been discussed.     

Hypersound waves at the surface of CdZnTe crystals: The role of surface orientation and scattering at twin boundaries

The patterns of propagation of gigahertz surface acoustic waves (SAWs) are obtained for cuts of CdZnTe single crystals with different crystallographic orientations. By comparing the experimental patterns with the calculated ones, the existence of at least two SAW modes, one of which is a Rayleigh mode, is demonstrated. It is shown that the anisotropy of propagation of different SAW modes makes it possible to determine the local crystallographic orientation of the CdZnTe surface and detect local imperfections of the crystal structure. Strong anisotropic scattering of the Rayleigh wave by coherent twin boundaries is found.