Domain structure and properties of triglycine sulfate crystals with profile <Emphasis Type="Italic">D</Emphasis>,<Emphasis Type="Italic">L</Emphasis>-α- and <Emphasis Type="Italic">L</Emphasis>-α-alanine-doped layers

A complex investigation of the domain structure and dielectric properties of triglycine sulfate (TGS) crystals containing profile layers doped with D,L-α-alanine (DLATGS) and L-α-alanine (LATGS) impurities is carried out. The images of the DLATGS and LATGS layers and ferroelectric domains are obtained by piezoelectric force microscopy; the parameters of the domain structure and the degree of unipolarity are determined. It is established that DLATGS layers are multidomain and LATGS stripes are mainly single-domain. The experimental data on the macroscopic dielectric properties of the crystals are compared with the results of a microscopic analysis of the domain structure.     

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.     

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.     

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.     

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.     

Characterization of defects generated by di-and trivalent cations in the potassium-dihydrophosphate structure and their influence on growth kinetics and face morphology

Different types of defect sites generated by the impurities of divalent (M²⁺) and trivalent (M³⁺) metals in the structure of potassium dihydrophosphate KH₂PO₄ (KDP) were revealed by crystal-chemical analysis and computer simulation. These sites cause different deformations of the crystal matrix by generating different local strains, which enhance the inhibiting effect of impurity atoms adsorbed on the surface. This fact accounts for the different influence of di-and trivalent cations on the growth kinetics and face morphology of KDP crystals. The effect of the M³⁺ ions is associated primarily with their adsorption on the face surfaces, whereas the influence of the M²⁺ ions results from their insertion into the surface layer of the crystal.     

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.     

Crystal growth and domain structure of triglycine sulphate doped with Pt(II)

The single crystals of triglycine sulphate doped with bivalent Pt-ions (TGS-Pt) were grown in full-shaped form, i.e. with many growth sectors. The domain structure of individual growth sectors was studied by the liquid crystal method. The growth sectors are mostly in a single domain state but spontaneous polarization is reversed in growth sector boundaries, which coincide with charged domain walls. Only the growth sector 001 reveals a blockshaped domain structure, however it differs from usual lenticular domains of the undoped TGS. The concentration of Pt in various growth sectors is different. The growth sectors with the higher concentration of Pt than 3 × 10⁻²% exhibit the unipolarity stable against thermal schocks.     

Simulation of defects formed by cations of bivalent and trivalent metals in the structure of potassium dihydrogen phosphate: A computational technique

This paper reports on the results of crystal chemical analysis and computer simulation of the defect structure of potassium dihydrogen phosphate (KDP) containing impurities of bivalent and trivalent metals. It is shown that these impurities can form defect centers of different types: isolated centers formed by M ³⁺ and Ni²⁺ ions and, in part, by Co²⁺ ions at interstitial sites, chains composed of M ²⁺ impurity ions with radii from ≈0.65 to ≈1.1 Å, and centers created through the substitution of large-sized bivalent cations for potassium ions either with the formation of additional potassium vacancies or through the heterovalent isomorphism mechanism. The calculations are performed using different-type interatomic interaction potentials, and a comparative analysis of the results obtained is carried out.     

Effect of ionic impurities on the primary nucleation of potassium sulphate solutions

A technique is described for rapidly assessing the effect of impurities on primary nucleation in solutions. The influence of Ca²⁺, Sr²⁺, Ba²⁺, Ag⁺, Pb²⁺, Cr³⁺ and Ni²⁺ on the nucleation of potassium sulphate solutions is discussed. It is generally observed that a discontinuity in the behaviour of the impurity occurs at an impurity concentration corresponding to the solubility of the “impurity sulphate” in the solution under investigation.     

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 role of hydration and complexing in the mechanism of impurity influence on crystal growth

The influence of impurities of chlorides and nitrates of divalent Ca²⁺ and Ba²⁺ cations on the kinetic growth of potassium dihydrophosphate KH₂PO₄ crystals at a saturation temperature of 323 K and relative supersaturation of 0.03 has been investigated experimentally. It is established that the impurity acts differently, depending on the face index, the impurity concentration, cation hydration, and the stability of the complexes formed in the solution by impurity salt ions. A model is proposed to explain the different influence of impurity ions on the growth of crystal faces. This influence is determined by the different hydration of cations and enhanced association of cations and anions of impurity salts in the surface layer with a lower dielectric constant.     

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.     

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.     

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.     

Scanning Capacitance Microscopy of Triglycine Sulfate Crystals with the Profile Chromium Distribution

The spatial capacitance distribution, domain wall configuration, and impurity composition of triglycine sulfate TGS–TGS + Cr crystals with a growth periodic impurity structure have been investigated using scanning capacitance microscopy and X-ray fluorescence and topography. The chromium ion concentration in the strips emerging to the surface has been determined, and the periodic impurity distribution has been established. The difference between the chromium concentrations in nominally pure and impurity strips was found to be ~0.08 wt %, which is reflected in a variation in the capacitance image contrast by 0.17%. It is shown that capacitance images carry information about localization of the impurity gradient regions and domain walls and make it possible to establish a correlation between the defect and domain structures of a ferroelectric crystal.     

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.     

A study on crystallographic characteristic of Mg-vicariate fassaites

Some relationship occurring by isomorphous change of Al³⁺ for Mg²⁺, in the presence of some impurities like iron and titanium ions, were studied. This study tooks shape as a contribution for a mineralogical and geochemical study on the contact paragenesis of Predazzo-Monzoni's area in the northern of Italy. It reveals itself also useful to drawn-up informations about the different influence that some network modifier cations bring into the mutual connection of chain systems, even if these cations are randomly dispersed and in a very few amount. This is useful for chemico-physical evaluations concerning their behaviour in multicomponent silicatic compositions whether in lattice systems as crystals or in random systems as glasses and glazes, very important in the sector of glasses and ceramics where direct informations on cations influence are more and more difficult to make display. Some results are according to some observations displayed in previous studies on amphiboles (Rossi, Ungaretti), where a certain influence of Ti⁴⁺ and Fe³⁺ on some parameters were observed.     

Effect of cationic impurities on solubility and crystal growth processes of ammonium oxalate monohydrate: Role of formation of metal‐oxalate complexes

The effect of different bi‐ and trivalent cationic impurities on the solubility of ammonium oxalate and the composition and distribution of chemical complexes formed in saturated ammonium oxalate aqueous solutions as a function of impurity concentration are investigated. The knowledge of the composition and stability of complexes formed in saturated aqueous solutions is then employed to explain the appearance of dead zones of supersaturation for growth and the difference in the effective segregation coefficient of the impurities. Analysis of the experimental results revealed that: (1) at a constant temperature, the dependence of concentration of complex species formed in saturated solutions on the concentration of different impurities can be described by an equation similar to that of the concentration dependence of density of solutions, (2) the dominant metal‐containing species present in saturated solutions are negatively‐charged, most stable oxalato complexes like Cu(C₂O₄)₂²⁻, Mn(C₂O₄)₃⁴⁻, Zn(C₂O₄)₃⁴⁻, Cr(C₂O₄)₃³⁻ and Fe(C₂O₄)₃³⁻, (3) in the investigated range of impurity concentration, the solubility of ammonium oxalates increases linearly with the concentration of all impurities and the increase is associated with the stability of dominant complexes, (4) appearance of dead supersaturation zones in the presence of impurities is associated with instantaneous adsorption of all growth sites by dominant oxalato complexes in relatively short adsorption time, and (5) the segregation coefficient of an impurity cation M of charge z + increases with a decrease in the solubility product constant K_sp for the hydrolysis products of reactions of the type: M^{z +} ↔ M₁^{(z −1)+} + H⁺ (where the cation M has z + charge, and H⁺ is hydrogen ion). (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

H2O influence evaluating and mid-IR fluorescence quenching in Tm3+-doped GeGaSCsI chalcohalide glasses

This work presents a detailed study on near-infrared and mid-infrared fluorescence emissions with five sets of Tm³⁺-doped 75GeS₂–15Ga₂S₃–10CsI chalcohalide glass. They are prepared in normal or water drying process. Based on the diffusion-limited relaxation calculation, a detailed investigation is put forward to obtain efficient near-infrared or mid-infrared fluorescence emissions of Tm³⁺ on the effect of H₂O on the Tm³⁺ fluorescence. Detailed investigations are given to the interacted energy transferring processes between rare-earth, impurities and vibrating phonons with the appearance of fluorescence quenching, along with Tm³⁺, H₂O concentrations varying and energy gaps forming. The radioactive properties are analyzed using compensated diffusion-limited relaxation calculation method, and the near-IR and mid-IR fluorescence properties are evaluated in detail with experimental and theoretical analysis.