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.     

Dependence of high electric-field-induced strain on the composition and orientation of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals

Electric-field-induced strain behavior of (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMNT) crystals with different orientations and compositions was investigated for use as electromechanical actuators. Crystallographically, high strains with low hysteresis were achieved for 〈001〉 oriented rhombohedral crystals (29%≤x≤31%) near a morphotropic phase boundary, rather than 〈110〉 and 〈111〉. Domain instability could explain inferior strain levels and large hysteresis for 〈110〉 and 〈111〉 oriented crystals. Ultrahigh strain levels up to 1.8% could be achieved for 〈001〉 oriented PMNT crystals, being related to an E-field induced phase transition. −2 kV/cm negative E-field can be applied to PMNT ferroelectric material with low hysteresis. High strain with low hysteresis makes PMNT crystals promising candidates for high performance solid-state actuators.     

Investigation on optical transmission spectra of (1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals

The optical transmission spectra from 0.3 to 11 μm of relaxor ferroelectric single crystals (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-xPT) were systematically studied at room temperature in this paper. The crystal is transparent between 0.45 and 5.5 μm and becomes completely absorbing around 0.4 μm in near UV region and 10 μm in infrared region. But the wavelength cutoff in near UV is much sharper than the long wavelength cutoff. As compared with other configurations, tetragonal single crystals possess the optimal transmission properties. The optical transmittance in the wavelength region from 0.45 to 5.5 μm is about 70%. The results show that tetragonal PMN-xPT single crystals are promising for a wide range of optical applications. Some discussions about the oxygen-octahedra structure that determines the basic energy level of the crystals are also presented on the optical properties of PMN-xPT single crystals.     

Bias field effects on the dielectric properties of 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3 single crystals with different orientations

The domain states and phase transitions in 0.67Pb(Mg_1/3Nb_2/3)O₃-0.33PbTiO₃ single crystals were investigated by studying their relative permittivity under various dc bias at constant heating and cooling rates. The orientation dependence of the bias field effect was revealed by examining the temperature dependence of relative permittivity as a function of crystal orientation (the 〈111〉, 〈011〉 and 〈001〉 directions) and dc bias field. The crystals basically have a macrodomain rhombohedral ferroelectric state in the ferroelectric phase under zero dc bias. External bias field could modulate the domain state and induce a stable macrodomain state in the crystals. Also, it is proposed that the dc bias applied along the 〈001〉 or 〈011〉 direction could induce a tetragonal ferroelectric phase or an orthorhombic ferroelectric phase, respectively, in an intermediate temperature range.     

Electro-optic characterization of tetragonal (1−x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals by a modified Sénarmont setup

The refractive indices of tetragonal (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃ (PMN-xPT) single crystals were measured with a prism coupler and their linear electro-optic (EO) properties were investigated from 20 to 80 °C by the automated scanning Sénarmont system with an ac field. The composition and temperature effect on the EO coefficients were also discussed. It has been found that their EO coefficients are much larger than that of widely used LiNbO₃ single crystal and the calculated half-wave voltages are also much lower, which enable the operation at lower voltages and the smaller device dimensions. Since the excellent EO properties are very stable and such high quality single crystals with large-size have been obtained, the PMN-xPT single crystals are a very promising candidate for EO modulation applications. By linking to the polarization-related quadratic EO coefficients, we find that the linear EO properties are related with the spontaneous polarization and dielectric constants.     

Field-Induced Domain Reorientation and Polarization Rotation of <110> Oriented Pb(Mg1/3Nb2/3)O3-PbTiO3 Single Crystals

Polarization hysteresis loops, x-ray diffraction and temperature dependent dielectric constant under different electric fields for <110> oriented 0.7PMN-0.3PT crystals are measured. The field-induced phase transition and the process of depolarization are discussed. The results show that with the electric field E increasing, the single-crystal form changes from the relaxor state of rhombohedral to normal rhombohedral, then to a monoclinic state via polar-axis reorientation and polarization rotation. Orthorhombic phase may present when E≥10kV, but it is an unstable form after E removal. The depolarization process is not just the reversal of the polarization process. It is noticed that only the temperature-dependent dielectric behaviour is not enough to judge the processes of the E-field induced phase transition.     

Characterization of lead free (K0.5Na0.5)NbO3-LiSbO3 piezoceramic

(K_0.5Na_0.5)NbO₃ (KNN) based lead free ceramics have been fabricated by a solid state reaction. In this work, LiSbO₃ (LS) modified KNN based ceramics were sintered at atmospheric pressure and high density (>96% theoretical) was obtained. The detailed elastic, dielectric, piezoelectric and electromechanical properties were characterized by using the resonance technique combined with the ultrasonic method. The full set of material constants for the obtained polycrystalline ceramics were determined and compared to the pure hot pressed KNN counterpart. KNN-LS polycrystalline ceramic was found to have higher elastic compliance, dielectric permittivity and piezoelectric strain coefficients, but lower mechanical quality factor, when compared to pure KNN, exhibiting a “softening” behavior. However, a high coercive field (∼17 kV/cm) was found for the LS modified KNN material. The properties as a function of temperature were determined in the range of −50-250 ^°C, showing a polymorphic phase transition near room temperature, giving rise to improved piezoelectric behavior.     

Phase diagram of the relaxor (1−x)Pb(Zn1/3Nb2/3)O3-xPbTiO3 investigated by dielectric and Raman spectroscopies

Lead zinc niobate-lead titanate[(1−x)Pb(Zn_1/3Nb_2/3)O₃-xPbTiO₃] (PZN-PT) crystals with x=4.5% and x=12% have been investigated using dielectric and Raman measurements over a range of temperatures. Above room temperature, dielectric measurements show that both compositions exhibit structural phase transitions according to the phase diagram proposed by Kuwata et al. [Ferroelectrics 387 (1981) 579]. Below room temperature, an anomaly at around 180 K for the x=12% sample is observed, suggesting another phase transition. Raman measurements are used to study all phase transitions.     

Sub-coercive field dynamic hysteresis in morphotropic phase boundary composition of Pb(Zr1/2Ti1/2)O3-Pb(Zn1/3Nb2/3)O3 ceramic and its scaling behavior

Sub-coercive field dynamic ferroelectric hysteresis of a morphotropic phase boundary composition of the PZT-PZN ceramic was investigated under influence of the compressive stress. The scaling relation of hysteresis area 〈A〉 against frequency f, field amplitude E₀, and stress σ took a form of , which is not different significantly to that of other PZT-PZN compositions with pure tetragonal or rhombohedral structure, as well as to that of soft and hard PZT bulk ceramics. This study suggested that the domain structures, not ceramic compositions, played a key role in controlling dynamic hysteresis behavior of ferroelectric materials.     

Effects of composition on phase structure and electrical properties of (K0.5Na0.5)0.90Li0.06Sr0.02Nb(1−x)SbxO3 ceramics

Lead-free (K_0.5Na_0.5)_0.90Li_0.06Sr_0.02Nb_(1−x)Sb_xO₃ (KNLSN-Sb_x) ceramics were synthesized by ordinary sintering technique. The compositional dependence of phase structure and electrical properties of the ceramics was systematically investigated. All samples possessed pure perovskite structure, showing room temperature symmetries of orthorhombic at x<0.01, coexistence of orthorhombic and tetragonal phases at x=0.01, and tetragonal at 0.02≤x≤0.05. The temperature of the polymorphic phase transition (PPT) was shifted to lower temperature and dielectric relaxor behavior was induced by increasing Sb content. The samples near the coexistence region (x=0.01) exhibited enhanced electrical properties: d₃₃∼145 pC/N, k_p∼38% and P_r∼20.4 μC/cm².     

A comparative study of dielectric and Raman spectroscopy of Pb(Y b1/2Ta1/2)O3 and Pb(Y b1/2Nb1/2)O3

A comparative study of the properties of two highly ordered lead based complex perovskites Pb(Y b_1/2Ta_1/2)O₃ and Pb(Y b_1/2Nb_1/2)O₃ has been carried out through x-ray diffraction, dielectric and Raman scattering measurements. These two compounds differ significantly in their structure, dielectric response and phonon vibration although the ionic radii and valencies are same for Ta and Nb. The room temperature x-ray diffraction pattern and Raman spectra show that the symmetry of lead ytterbium tantalate is lower than that of lead ytterbium niobate. The Raman spectra of Pb(Y b_1/2Ta_1/2)O₃ also indicates the presence of local distortion in the lattice which may be one of the factors responsible for the existence of a secondary transition.     

Electrical properties of high Curie temperature (1−x)Pb(In1/2Nb1/2)O3-xPbTiO3 single crystals grown by the solution Bridgman technique

0.65Pb(In_1/2Nb_1/2)O₃-0.35PbTiO₃ (PINT65/35) (starting composition) single crystals were grown successfully through the solution Bridgman technique using PbO flux and PMNT67/33 seed crystals. Because of the composition variation, the final composition of achievable crystals is in a range of 0.32-0.34 with the corresponding T_c range of 265-269 °C. The (001) plates of as-grown PINT66/34 single crystals show high Curie temperature (T_c=269 °C) and rhombohedral-tetragonal phase transition temperature (T_rt=134 °C). Besides, good electrical properties with high dielectric constant (ε>3000), low dielectric loss (tan δ∼1.2%), high piezoelectric constant (d₃₃∼2000 pC/N) and large electromechanical coupling factor (k_t≈59%) at room temperature have been obtained on the (001) plates. The sound velocity, acoustic impedance and other piezoelectric parameters were also measured on the (001) plates in this study, which provide us more detailed information about PINT66/34 single crystals.     

Interrelation of antiferrodistortive and ferroelectric phase transitions in Sr1−xAxTiO3 (A=Ba, Pb)

A dielectric and ultrasonic velocity study of antiferrodistortive and ferroelectric phase transitions in Sr_1−xA_xTiO₃ (A=Ba, Pb) is reported. It is shown that both phase transitions co-exist at x<0.03 but at the higher concentration the ferroelectric phase transition entirely suppresses the antiferrodistortive phase transition. The experimentally obtained phase diagrams are discussed in the framework of the Landau phenomenological theory.     

Photoluminescence investigations on the nanoscale phase transition in Pb(Mg1/3Nb2/3)O3

The temperature dependence of the photoluminescence spectra of the relaxor ferroelectric Pb(Mg_1/3Nb_2/3)O₃ has been reported. The temperature behaviours of the 1.57, 1.67 and 1.73 eV bands indicate a phase transition at 110 K. This is attributed to a structural phase transition in the charged nanoshell. Analysis of the temperature dependence of 1.67 eV band intensity with a thermal quenching model indicated the existence of a phonon mode at 1153 cm⁻¹. This mode is identified in the Raman spectra measurement. The intensity of the 1.73 eV band showing an anomalous behaviour at 210 K is attributed to a transition from a crystalline phase to an amorphous phase in the charged nanoshell.     

Influence of niobium doping on the electrical properties of 0.58Pb(Sc1/2Nb1/2)O3-0.42PbTiO3 single crystal

Piezoelectric single crystals of 0.58Pb(Sc_1/2Nb_1/2)-0.42PbTiO₃ and Nb⁵⁺-doped PSN-PT have been grown using flux technique. It is believed that the addition of Nb⁵⁺ creates lead vacancy in order to compensate charge neutrality. The structural distortion that occured in the doped crystals has been revealed through broadening of some peaks in X-ray diffraction studies. Niobium content that increased from 0.50 to 1.00 mol% might have induced more defect dipoles associated with . This plays a significant role in improving the ferroelectric, dielectric and piezoelectric properties. Our observations clearly show an increase in the spontaneous polarization (P_r), dielectric constant at room temperature, degree of diffuseness and transition temperature (T_c) and also a decrease in coercive field. The reasons behind these enhanced electrical properties are discussed in detail.     

Dielectric and piezoelectric properties of lead-free (Na0.5K0.5)NbO3-SrTiO3 ceramics

In this article, we report successful preparation of dense [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ (x=0.005-0.100) ceramics by ordinary sintering in air. The dependence of phase structure on doping content of SrO and TiO₂ has been determined by the X-ray diffraction technique. It was found that the crystal structure changed from orthorhombic to tetragonal at x≈0.040. Dielectric study revealed that the dielectric relaxor behavior was induced by doping of SrO and TiO₂ into (Na_0.5K_0.5)NbO₃. The samples in the composition range from x=0.005 to 0.020 exhibited excellent electrical properties, piezoelectric constant of electromechanical planar and thickness coupling coefficients of k_p=26.6-32.5% and k_t=39.8-43.8%. The results show that the [(Na_0.5K_0.5)_1−xSr_x](Nb_1−xTi_x)O₃ ceramics are one of the promising lead-free materials for electromechanical transducer applications.     

High electric-field-induced strain of Pb(Mg1/3Nb2/3)O3-PbTiO3 crystals in multilayer actuators

An optimum composition range (29%≤x≤31%) of 〈001〉 oriented (1−x)Pb(Mg_1/3Nb_2/3)O₃-xPbTiO₃(PMNT) crystals was ascertained for multilayer actuator applications, which exhibited high-strain and low-hysteresis behavior. A −1.5 kV/cm negative E-field can be applied to PMNT ferroelectric samples with low hysteresis. Forty layer actuators with individual element sizes of 7×7×0.7 mm³ were fabricated under identical processing conditions using two different materials: (1) single crystal PMNT and (2) commercial PZT-SF ceramics. Under free-load conditions, 48 μm displacements can been achieved in PMNT actuators at electric fields ranging from −1.5 to 10 kV/cm, which is more than twice the displacement of the PZT-SF actuators driven from −10 to 10 kV/cm. Under 4 kg loading, the displacements in PMNT stain actuators are decreased to 42.5 μm.     

Raman study of phase transitions in KNbO3

The influence of grain size on the phase transitions of ferroelectric KNbO₃ was studied by micro Raman spectroscopy. It was found that the three transitions observed are not sharp for small particles (∼50 μm), indicating that they do not behave like bulk particles. The transition temperatures depend on the size and all particles show hysteresis. From these experiments we have obtained some evidence that in small particles monodomains of the rhombohedral and orthorhombic phases coexist in a range of temperatures.     

Low-temperature phase transformations in weakly doped quantum paraelectrics: novel features and quantum reentrant dipolar glass state in KTa0.982Nb0.018O3

An unusual sequence of phase transitions (PT) and reentrant dipole glass-like phase formation at low temperatures was found recently in KTaO₃ weakly doped with Li and Nb (K_0.9986Li_0.0014Ta_0.976Nb_0.024O₃) [Phys. Rev. B 63 (2001) 172]. We report on detailed low frequency (100 Hz-1 MHz) permittivity and Raman light scattering studies of similar composition, but without Li admixture, KTa_1−xNb_xO₃ with x=0.018 (KTN1.8). The aim of the study is to answer the question if the reentrant dipole glass-like phase exists in KTN1.8 and what is the microscopic origin of this phase. A detailed study of the sharp low-temperature PT observed at T_C∼27 K revealed properties inherent to the reentrant glass-type state at lower temperatures. The substitution of Nb for Ta influences the TO₁ soft lattice mode and leads to PT with the long-range ferroelectric ordering. A crossover to an order-disorder polar microregion dynamics with a non-standard ε′(T) behaviour and dipole glass-like formation were found below T_C (at ∼15 K), which is attributed to the randomness of the Nb distribution. A crossover to the long-range order was found under a dc bias field.     

Dielectric and optical behaviors in relaxor ferroelectric Pb(In1/2Nb1/2)1−xTixO3 crystal

Dielectric permittivities (ε′,ε″) have been measured as functions of temperature (140-535 K) and frequency (500 Hz-2.0 MHz) in a (001)-cut Pb(In_1/2Nb_1/2)_0.7Ti_0.3O₃ (PINT30%) single crystal grown by the modified Bridgman method with Pb(Mg_1/3Nb_2/3)_0.71Ti_0.29O₃ (PMNT29%) seed crystal. A diffused phase transition was observed in the temperature region of ∼430-460 K with strong frequency dispersion. Above the Burns temperature T_B≅510 K, the dielectric permittivity was found to follow the Curie-Weiss behavior, ε′=C/(T−T_C), with parameters C=3.9×10⁵ and T_C=472 K. Below T_B≅510 K, polar nanoclusters are considered to appear and are responsible for the diffused dielectric anomaly. Optical transmission, refractive indices, and the Cauchy equations were obtained as a function of wavelength at room temperature. The unpoled crystal shows almost no birefringence, indicating that the average structural symmetry is optically isotropic. The crystal exhibits a broad transparency in the wavelength range of ∼0.4-6.0 μm.