Modification of pyroelectric crystal TGS using thermodynamic theory

Based on the Devonshire thermodynamic theory, the relationship λ/χ = Ps/C can be regarded as a method to increase the pyroelectric material figure of merit of ferroelectric crystals. Several modified TGS crystals doped with urea or co-doped with urea and other dopants have been grown. The effect of the urea dopant on crystal growth and pyroelectric properties was investigated. The pyroelectric figures of merit M (λ/ε) of the doped TGS crystals are obviously higher than those of pure TGS. Furthermore, the variations of λ/χ and Ps/C as a function of temperature for these doped TGS single crystals were measured, and analyzed according to the Devonshire thermodynamic model.     

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。     

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.     

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.     

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.     

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.     

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 a ferroelectric domain wall on the fabrication of a pyroelectric laser energymeter

A region across a ferroelectric domain wall has been scanned, using an Nd:YAG laser beam (beam size 440 μm), in a thin crystal of TGS (triglycine sulphate), cut normal to the polar axis and the pyroelectric response of the crystal has been recorded. If a laser pulse of fixed beam size falls on the domain completely, then the output pyroelectric signal is maximum. But when the laser beam (diameter of beam greater than width of domain wall) falls on the domain wall, the pyroelectric signals from two opposite domains tries to cancel each other and net signal depends on the position of laser beam across the domain wall. When the domain wall lies in the middle of the laser beam the output pyroelctric signal will be zero. In our experiment when beam of size 440 μm falls on positive domain the pyroelectric voltage of ‐2.76 mV recorded and when beam starts crossing the domain wall (i.e from positive domain to negative domain), the pyoelectric signal changes its sign from negative to positive through zero. After 220 μm the signal decreased to minimum and again increases to maximum (+2.46 mV) in opposite direction after 440 μm i.e when beam falls on the negative domain completely. This shows that the polarization in the domain wall region (separating two domains) is zero i.e the paraelectric nature of domain wall. So before detector fabrication the sample must be poled sufficiently to avoid the non uniformity of pyroelectric signal due to the domain wall. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure of the polar (010) cleavage of a ferroelectric TGS crystal from the atomic-force microscopy data

The atomically smooth polar (010) cleavage of a ferroelectric triglycine sulfate (TGS) crystal has been studied by the method of atomic-force microscopy. It is shown that the rounded 0.6-nm-high (deep) protrusions and pits with nanometer lateral dimensions revealed on the surfaces of TGS crystals are characteristic of their microrelief. These microrelief details can be formed either as a result of crystal cleavage in the ferroelectric phase or the mechanical action of a cantilever onto the crystal surface. These two-dimensional formations are relatively stable and genetically related to the layer structure of the ferroelectric phase of TGS crystals.     

Growth of TGS crystals using uniaxially solution‐crystallization method of Sankaranarayanan‐Ramasamy

The recently discovered crystal growth method called uniaxially solution‐crystallization method of Sankaranarayanan–Ramasamy (SR) is modified in some aspects and used for growth of triglycine sulphate (TGS) crystals. The modification leads to the simplicity, reduction of cost and avoided the temperature fluctuations. The 〈010〉 direction of TGS is very important and used for fabrication of infrared detectors. Using this method, the 〈001〉, 〈010〉 directional crystals of TGS were successfully grown in a glass crystallizer. The grown crystal was characterized by HRXRD, UV‐Visible and dielectric studies. The results prove the suitability of the modified SR method for oriented TGS crystal. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

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.     

A neutron diffraction study of the phase transition of fully deuterated triglycine sulphate (ND2CD2COOD)3.D2SO4

Using neutron single crystal and powder diffraction, the first thorough investigation of the structure of fully deuterated triglycine sulphate, (ND₂CD₂COOD)₃.D₂SO₄ is presented, including its evolution with T, through its structural phase transition. This includes new precise structural parameters determined at several key temperatures above and below T_C using single crystal diffraction, and for the first time a parametric study has been undertaken over a wide temperature range — from 4 to 500 K in 2 K steps. It was found that fully deuterated TGS shows a structure consistent with hydrogenous TGS and partially deuterated TGS. The evolution of several key hydrogen bond lengths suggests that weakening of the H‐bond network with T is crucial in decoupling the polarising glycine molecules from the other glycines and allowing the long‐range ferroelectric order to break down. A new parameterisation of the phase transition is demonstrated. Contrary to results of physical properties measurements, there is no evidence of a second low temperature phase transition in TGS – no low temperature anomalies were observed in the crystal structure.     

Formation of an internal bias field in chromium-and L, α-alanine-doped triglycine sulfate crystals

The unipolar state of a chromium-and L, α-alanine-doped ferroelectric triglycine sulfate (TGS) crystal has been studied. The experimental data on the distribution of internal bias fields with respect to a seed are considered. The possible mechanisms of the formation of an internal bias field during the growth of TGS crystals with a low impurity concentration are considered.     

New method for the visualization of domain and defect structure of ferroelectrics

A new method for the visualization of domain and real structure of ferroelectric triglycine sulphate (TGS) crystals on the scale of optical microscopy by means of decoration with auramine is developed. Auramine deposits on crystal surfaces as discrete particles about 2 microns in size and as a continuous layer, thus allowing both the domains as a whole and the various electrically active elements of the domain and real TGS structure to be visualized with high resolution. Due to decoration with auramine, the domain structure of TGS detected with a very high contrast; elements of the geometrical relief-cleavage steps exhibiting different electrical properties are also revealed. Furthermore, it has been observed for the first time that the positive domains have sharp electrical boundaries, while the negative domains have erased boundaries. It has also been established that between the domains of opposite signs regions exist characterized by a very low electrical activity. Decoration of annealed TGS crystals which were rapidly cooled from the temperature of 150°C, i.e. above the Curie point (49°C) down to room temperature resulted in detection of new electrically active directions on the surface of the negative domains; these directions are likely to occur in the paraelectric state. The new method cannot only be applied to the study of the TGS crystals but can also be useful in investigation of other ferroelectrics.     

On growth and morphological studies of TGS single crystals

The effect of various growth parameters; seed morphology, growth-temperature and pH of the mother solution on the growth of TGS single crystals is studied. The effect of these variables on the crystal morphology and perfection is reported. It is shown that; (i) The crystal quality is much dependent on the seed and the growth temperature and (ii) the pH-control is a simple and an effective method for obtaining TGS crystals of required morphology.     

Study on the Growth of Triglycinsulphate Single Crystals

Crystallization of TGS at 52.0°C - above the transition point - has been studied in a wide range of supersaturation of the solution (σ = 0 to 10⁻²). The rates of growth of {110} and {001} faces were measured as a function of supersaturation at constant hydrodynamical conditions (Re = 3.4 · 10⁻³). Further, the influence of hydrodynamical conditions on the growth of {110} faces at constant supersaturation (σ = 4.2 · 10⁻³) was established. The parameters of the experimentally found dependences are determined on the basis of the surface-diffusion model of BURTON . CABRERA and FRANK . From these dependences follows that the growth rate of the {110} faces is already almost limited by the volume diffusion of TGS molecules towards the crystal surface, while in the case of {001} faces the surface diffusion mechanism of crystallization is clearly manifested. Dislocation densities in the crystals have been determined by means of etching technique. The number of dislocations increases with increasing supersaturation; hence, supersaturation of the solution together with the processes taking place in the regeneration zone surrounding the seed determine the number of dislocations in the crystal volume and thus the resulting structural perfection of single crystals. Investigation of the spontaneous redistribution of domains showed that the growth rate of TGS crystals influences the dielectric properties to much smaller extent than does chemical purity.     

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.     

Nanorelief of the natural cleavage surface of triglycine sulphate crystals with substitutional and interstitial impurities

Ferroelectric triglycine sulphate crystals (TGS) with substitutional (LADTGS+ADP, DTGS) and interstitial (Cr) impurities have been studied by atomic-force microscopy, X-ray diffraction, and X-ray fluorescence. The nanorelief parameters of the mirror cleavage TGS(010) surface have been measured with a high accuracy. A correlation between the crystal defect density in the bulk and the cleavage surface nanorelief is revealed at the submicrometer level.