掺杂TGS晶体的生长及热释电性能研究

选择重稀土离子Dy3 为掺杂阳离子,DL-丙氨酸与L-谷氨酸部分取代甘氨酸分子,生长了不同掺杂配比的TGS晶体。生长和测试实验表明,掺杂TGS晶体较纯TGS晶体易于生长。将掺杂晶体生长溶液的pH值控制在1~4,可改变掺杂晶体的结晶习性。用ICP发射光谱测试了掺杂晶体中稀土元素的含量,用X射线粉末衍射法测定了晶格参数,结果表明:元素已进入晶体,晶格参数稍有变化,但掺杂晶体的对称性仍为C2-2。通过测量掺杂晶体的电滞回线,得到了内偏压场,还测量了各样品的热释电系数、自发极化强度,作了温度曲线,并分析了各掺杂剂对提高热释电性能和锁定极化的作用。结果表明:是有应用前景的热释电材料。     

Dielectric behaviour of TGS crystals poled by doping on repeated temperature cycling

Data characterizing the stability of basic dielectric properties against thermal treatement are presented for crystals of TGS and deuterated TGS doped with alanine or bivalent platinum. Complex permittivity and over-all polarization have been measured during a heating-cooling cycle. In alanine doped crystals the heating and cooling curves are perfectly reproducible. In Pt-doped samples the reproducibility is worse, for pure TGS the properties on cooling are strongly influenced by domain effects. These data made it possible to estimate the change of the figures of merit for pyroelectric ir detectors due to transient heating.     

掺三氟乙酸TGS晶体生长及其性能研究

本文以三氟乙酸作为掺质,分别按4.4mol%、9.4mol%、13.4mol%、18.4mol%的配比进行了掺质TGS晶体生长,并对其作X射线粉末衍射分析及晶体热释电性能的测试。结果表明,三氟乙酸的掺入虽然使热释电性能有一定程度下降,但却使得晶体铁电-顺电相转变延迟,提高了晶体的居里点,并产生了一定的内偏压场。     

A New Modified TGS Crystal

Triglycine sulfate (TGS) crystals doped with Cr⁶⁺ have been grown from a growth solution with various Cr⁶⁺ concentrations. The structure, transmission spectrum, pyroelectric properties, and the photorefractive effect of the crystals have been measured. It has a high internal bias field and photorefractive effect.     

Study on the Growth and Properties of Guanidine Doped Triglycine Sulfate Crystal

Guanidine doped TGS crystal is grown from the aqueous solution. The pyroelectric properties of GTGS crystal are studied, the result shows that GTGS crystal has better pyroelectric properties than those of pure TGS crystal. The effects of organic dopant on pyroelectric properties of TGS crystal are discussed.     

Internal bias field in triglycine sulphate crystals with <Emphasis Type="Italic">L</Emphasis>-, α-alanine grown at negative temperatures

The dielectric and pyroelectric properties of triglycine sulphate (TGS) crystals with L, α-alanine impurities grown at negative temperatures have been investigated. It is shown that a lower impurity concentration (2 mol % in solution) in this temperature range leads to the formation of internal bias fields of the same order of magnitude (∼800 V/cm) as for TGS crystals grown at T ⩽ 50°C but with an L, α-alanine concentration of 20 mol % in solution.     

The influence of γ-irradiation on ferroelectric and polarization properties of TGS crystals

The experimental investigation of pyroelectric and polarization properties of TGS crystals was made. TGS crystals were grown under constant growth conditions (temperature and supersaturation of the solution) and γ-irradiated in a wide range of irradiation. The influence of γ-irradiation on the quality parameter M₂ of crystals, on the form of hysteresis loops, on size of spontaneous polarization and shifting field was ascertained.     

Growth of thiourea-doped TGS crystals and their characterisation

Thiourea-doped Triglycine sulphate (ThTGS) crystal with three different concentrations of thiourea was grown from aqueous solution by slow cooling technique. The cell parameters were determined from powder X-ray diffraction analysis. A qualitative analysis of the presence of thiourea in doped crystals was estimated by FTIR analysis. Microhardness studies were carried out using Leitz Weitzler hardness tester at room temperature. Dielectric properties of the crystals were studied which showed a shift in the T_c when compared to pure TGS crystal. Pyroelectric studies were carried out and the pyroelectric coefficient was found. Piezoelectric studies (d₃₃ coefficient) has also been carried out.     

Water-soluble ferroelectric crystals with inhomogeneous impurity distribution

Stabilization of the unipolar state via the formation of inhomogeneous impurity distribution in crystal bulk is considered. Possible growth of crystals with stable characteristics is demonstrated on triglycine sulfate (TGS) crystals with a regular inhomogeneous impurity distribution. The properties of TGS crystals with an inhomogeneous distribution of chromium ions grown above and below the Curie temperature T_C are studied. Inhomogeneous TGS crystals of three types are obtained: type-I crystals with a smooth variation of the concentration gradient along the growth direction, type-II crystals with a periodic layer variation of the impurity concentration, and type-III crystals with a sawtooth-like variation of the impurity concentration along the sample length. The TGS crystals with the regular inhomogeneous impurity distribution in the ferroelectric phase are characterized by higher values of the internal bias field E _b , unipolarity coefficient k, and pyroelectric coefficient γ than the inhomogeneous crystals in the paraelectric phase and the crystals with the statistic impurity distribution grown by the conventional method.     

Effect of Doping and Irradiation on Optical Parameters of Triglycine Sulphate Single Crystals

Crystals of triglycine sulphate (TGS) doped with orthonitroaniline (ONA) irradiated with different doses of gamma-radiation were used to investigate gamma-radiation effect on electrical and optical parameters. The absorption coefficient and the reflectance were measured and hence the extinction coefficient, the optical refractive index and the dielectric constants (e_r′, e_r″) of unirradiated and irradiated TGS crystals were calculated. Values of the allowed indirect optical energy gap E_g^opt. of TGS doped with ONA were calculated as a function of gamma-dose. Value of E_g^opt. decreases from 4.72 eV to 4.25 eV with increasing gamma-doses from 0 up to 3 Mrad. The values of the static dielectric constant e_r(0) and the effective electrical conductivity sigma₀ at room temperature and their dependence on gamma-dose were also calculated.     

Temperature Dependence of the Absorption Spectra and Optical Parameters in TGS and Cu2+-Doped TGS Crystals

The effect of temperature on the optical absorption spectra and optical parameters is investigated for pure TGS and TGS doped with Cu²⁺ ions. Absorption measurements cover the range from room temperature to about 355 K in the energy range 3-5.5 eV. The temperature dependence of the band gap E_g(T) reveals an anomaly at the phase transition temperature for both pure and Cu²⁺-doped TGS crystals. In the region of the absorption edge the absorption coefficient is found to display Urbach-rule behaviour. The characteristic Urbach parameters are determined and their temperature dependence is investigated.     

Triglycine sulphate single crystals growing doped with copper and cobalt ions and study of their dielectric properties

Growing conditions for TGS single crystals doped with Cu or Co ions are given in a table. ε and tg δ values in growth pyramids depend on crystal growing temperature and the incorporated impurity: Cu²⁺ ions increase the temperature hysteresis of the dielectric permeabilty. Incorporation of Cu²⁺ and Co²⁺ ions considerably decreases the difference in the values ε at 25°C in crystals grown at different temperature.     

Porous crystal structures obtained from directionally solidified eutectic precursors

Interconnecting cage-like porous structures of several halide compounds were prepared by the selective leaching of one eutectic phase method. The binary eutectic precursors were prepared by directional solidification using the Bridgman crystal growth technique. Porous NaMgF₃ (40% pore volume), CaF₂ (57% pore volume) and BaF₂ (43% pore volume) crystals were obtained after water leaching the NaF component of the directionally solidified NaF/NaMgF₃, NaF/CaF₂ and NaF/BaF₂ eutectics with the appropriate entangled microstructure. The growth conditions for eutectic-coupled growth and the morphology of the eutectics have been determined. In the coupled growth regime, the size of the eutectic phases “λ” is fairly uniform and varies with the eutectic growth rate “v” as λ²v=constant, which allows us to control the pore size within the 0.5–10 μm range. The simplicity and versatility of the eutectic growth also allows us to fabricate highly aligned porous structures at relatively high production rates.     

Piezo-optic properties of TGS crystals doped with <Emphasis Type="Italic">D</Emphasis>-serine

The effect of uniaxial mechanical pressure along the main crystallophysical axes on the principal values of birefringence Δn _i in TGS crystals doped with 5% D-serine is investigated. It is ascertained that the values of Δn _i are rather sensitive to the action of uniaxial stresses. The temperature shift coefficients ?T _c /?σ_m are determined for the phase-transition points. The temperature and spectral dependences of the combined piezo-optic constants π _im ⁰ are calculated. The contribution of the secondary electro-optic effect to the changes in the birefringence and the piezo-optic constants of doped crystals is determined. It is found that the piezooptic constants π ₂₃ ⁰ and π ₁₂ ⁰ have the same values, which indicates a decrease in the anisotropy of the optical indicatrix of doped crystals under the action of uniaxial stress. The optical and deformation contributions to the relaxation effect of piezo-optical birefringence in doped TGS crystals are found.     

A contribution to the study of the influence of impurities on the growth and some physical properties of TGS single crystals

Single crystals of TGS doped with Ni²⁺, Cu²⁺ and Fe³⁺ have been prepared under identical conditions by the method of temperature decrease (below the phase transition point). Presentation of the influence of impurities on the development of individual crystal faces is based on goniometric measurements. The influence of impurities on the domain structure of TGS is documented by microphotographs of domain structures and by investigation of the variation with time of the average domain width. It is shown that the distribution of impurities (between the liquid and solid phases) is approximately proportional to the concentrations of metal glycino chelates in the solution. From the results concerning the influence of impurities on various physical properties follows that the degree to which the properties are affected depends not only on the impurity concentration but also on the specific intensity of their action which is due to variations in the binding forces in the structure of TGS.     

Growth and characterization of TGS and DTGS single crystals doped with Pt(II), Pt(IV) and L‐alanine

The single crystals of triglycine sulfate doped with bivalent and tetravalent Pt‐ions and with L‐alanine (LADTGS/Pt(II) and LATGS/Pt(IV)) were grown in the ferroelectric phase from low temperature solutions. Using stick seeds the full‐shaped crystals with many growth pyramids have been prepared. The growth rate along the axis c of the doped crystals is much higher than in an undoped one. Morphology, domain structure and P‐E hysteresis loops have been investigated. The effect of the dopant on the growth velocity is explained on the basis of catalytic action of supposed platinum complexes. The first series of the pyroelectric detectors have been prepared from these materials and their fundamental parameters are presented. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The influence of metallic substitution on the physical properties of manganese mercury thiyocyanate crystals

Good optical grade single crystals of pure, Cd²⁺ and Mg²⁺ doped Manganese Mercury Thiyocyanate (MMTC) crystals are grown by slow solvent evaporation technique at room temperature. Single crystal XRD studies reveal that the incorporation of metallic dopants has not changed the structure of the parent crystal. The SHG efficiencies of the pure and doped samples of MMTC are measured by Kurtz Perry powder method and the results are compared with urea. It is evident from microhardness study that the presence of dopants has increased the mechanical strength of MMTC crystal. The TG/DTG studies confirm that the thermal decomposition temperatures of pure (353°C), Mg²⁺ doped (363°C) and Cd²⁺ doped (365°C) MMTC are relatively high when compared to other NLO crystals of the same family. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Refractometry of TGS crystals doped with L-threonine impurity under uniaxial pressure

The temperature and spectral dependences of the refractive indices of triglycine sulphate (TGS) crystals doped with L-threonine impurity have been investigated. It is established that the introduction of an impurity weakens the temperature dependence of refractive indices. The electronic polarizability, refractions, and parameters of UV oscillators of mechanically deformed impurity crystals are calculated. The temperature coefficients of the phase transition shift are determined.     

Dielectric properties of triglycine sulfate crystals with defects at low and infralow frequencies

Dielectric responses of several crystals in ultraweak measuring fields at low and infralow frequencies are compared, namely, of nominally pure, Cr-and Lα-alanine-doped triglycine sulfate (TGS) crystals and TGS + Cr³⁺ crystals irradiated with X-rays. It is shown that dopant-induced bias fields give rise to crystal unipolarity, suppress the domain contribution to their dielectric response, and diffuse the phase transition. It is established that X-ray irradiation of the crystals results in “radiation annealing” of TGS + Cr³⁺ crystals, which increases their permittivity and diminishes diffusion of the phase transition.