Materials Science Forum Vols. 636-637

Abstract: New push-pull thiobarbituric (oligo)thiophene derivatives 1 were synthesized, in good to excellent yields (60-98%), through Knoevenagel condensation of the corresponding formyl-(oligo)thiophenes 2 with 1,3-diethylthiobarbituric acid in dichloromethane, under basic conditions. Evaluation of the thermal and solvatochromic properties of these compounds was carried out and their NLO response was estimated. The values obtained suggest that these (oligo)thiophenes have good potential to be used as novel NLO materials.

Abstract: Compounds 1 were synthesized, in good to excellent yields (72-87%), through condensation of formyl-arylthiophene precursors 2 with 1,2-diaminoanthraquinone in ethanol at reflux, followed by cyclisation of the imine intermediate with Pb(OAc)4 in acetic acid at room temperature. Evaluation of the thermal, linear and NLO properties of these compounds was carried out. The  values of chromophores 1, measured by hyper-Rayleigh scattering (HRS) technique, are several times larger (49-67) than that of the standard reference molecule p-nitroaniline (pNA). Due to their excellent thermal stability, (Td = 341-446 oC), and good NLO properties, arylthienyl-imidazo-anthraquinones 1 could be used as new efficient and thermally stable NLO materials.

Abstract: This work analyzes the processing of Pb(Zr,Ti)O3 (PZT) thin films directly on copper-coated polymer films. PZT thin film deposition was performed onto the metallized Kapton® films using a single RF plasma jet. In order to reduce the interaction of PZT and Cu during the initial growth stage, an ultrathin amorphous TiO2-x seeding layer was sputter-deposited prior to PZT deposition. The film texture was a mixture of (111)-oriented perovskite nanocrystals, rutile and pyrochlore. Topography and piezoelectric in-plane and out-of-plane response of the films were evaluated using a commercial AFM adapted for piezoforce measurements. The as-deposited films were self-polarized with polarization pointing at the surface of the sample. Polarization was switchable and a piezoelectric hysteresis was obtained.

Abstract: The paper reviews recent results of ultrasonic and piezoelectric investigation in CuInP2S6 family ferroelectric layered crystals and their solid solutions in the temperature range 100-360 K. It was shown that, Cu substitution by Ag lowers the phase transition temperature. In investigated AgxCu1-xInP2(S,Se)6 crystals above the phase transition (PT) temperature the piezoelectric response was absent and appeared only below the transition. At low temperatures T < 220 K the layered AgxCu1-xInP2Se6 crystals are ferroelectric. Piezoelectric sensitivity in the ferroelectric phase increases with DC field applied along the c-axis, then saturates, and after reversion of voltage the piezoelectric signal decreases, at field near coercive changes sign, and saturates again at high voltage of opposite polarity In the paraelectric phase under external DC electric field, applied along c-axis normal to layers, thin AgxCu1-xInP2Se6 plates can effectively excite and detect ultrasonic waves, due to electrostriction. The same behaviour was observed and in AgxCu1-xInP2S6 crystals. The critical ultrasonic velocity anomalies were observed in the vicinity of PT. In CuInP2S6 crystals with addition of In i.e. indium rich materials the phase transition temperature could be raised to T > 330 K what is important for applications in medical diagnostics ultrasonic transducers. In all these materials the poling conditions were investigated and it was shown that after long time exposing in DC field the piezoelectric sensitivity sufficiently increases and electromechanical coupling constants as high as > 50 % could be obtained.

Abstract: We have investigated the structural and magnetic properties of Sm(Co0.70Fe0.1Ni0.12Zr0.04B0.04)7.5 melt spun ribbons. The arc-melted bulk samples have been used to obtain ribbons at 37 up to 55 m/sec while annealing has been performed in argon atmosphere for 30-75 min at 600-870 oC. In as-spun ribbons the hexagonal SmCo7 (TbCu7-type of structure) of crystal structure has been determined from x-ray diffraction patterns, while fcc-Co has been identified as a secondary phase. After annealing, the 1:7 phase of the as-spun ribbons transforms into 2:17 and 1:5 phases. TEM analysis shows a homogeneous nanocrystalline microstructure with average grain size of 30-80 nm. Coercivity values of 15-27 kOe are obtained from hysteresis loops traced at non-saturating fields. The coercivity decreases as temperature increases, but it is high enough to maintain values higher than 5 kOe at 380 oC. The maximum energy product at room temperature increases, as high as 7.2 MGOe, for melt-spun ribbons produced at higher wheel speed.

Abstract: Zinc oxide (ZnO) is a direct, wide band gap semiconductor material having many promising properties for UV/blue optoelectronics, transparent electronics, spintronic devices and sensor applications. The ZnO is synthesized by the technique of Chemical Bath Deposition by microwaves heating (MW-CBD). The urea concentration in the solution is varied, maintaining constant the zinc nitrate in ratio 1:1 … 1:10. The physical properties of ZnO thin films were examined by X-ray diffraction (XRD), SEM-EDS, and Raman scattering, which are convenient tools that can provide us with plenty of information about crystal structure and elementary excitons. By X-rays one obtains that it has hexagonal polycrystalline wurtzite type structure. The IR absorption line at 3577 cm-1 detected at 300 K in bath chemical ZnO is assigned an O–H bond primarily aligned with the c-axis of the crystal and bonding between Zn-O (473cm-1, 532 cm-1). The Raman spectra show the first order experimental Raman spectra of ZnO excited by 514.5 nm laser line. The first order Raman modes A1T, E1T, E2(H), A1Land E1L are identified as the peaks sited at 385, 426, 437, 572 and 584 cm-1

Abstract: ZnO with a good crystallinity and visible photoluminescence at room temperature around 518 nm and 605 nm obtained by an electrolytic method using urea and zinc nitrate is presented. An electrolytic Teflon cell was used for the process using tungsten wire and aluminum foil as electrodes, the tungsten wire was introduced in a solution of water, zinc nitrate and urea. The electrical potential was modified, keeping constant the growth time. As substrate and cathode a 1-3 -cm, (100), n type, silicon wafer was used. The crystalline structure and photoluminescence showed interesting changes when the electrical potential was modified. XRD (X Ray Diffraction) performed on the films showed characteristic diffraction peaks of ZnO obtained in other works. The amplitude of these peaks changed with the electrical potential applied, with a predominance of the (100), (002) and (101) planes. The photoluminescence (PL) bands changed with the electrical conditions too. At low electrical currents a predominance of the green band (520 nm) was observed, and another band around 600 nm appeared from high current conditions, this behavior can be associated with different defects generated during the grow process. From these results we conclude that the change in the electrical current produces changes in the structural and optical characteristics of the material.

Abstract: Optical and electrical properties amorphous carbon nitride (a-CN) has been investigated on films deposited by reactive R.F. sputtering source with a graphite target. The amorphous carbon nitride samples were prepared under a gas mixture of nitrogen (N2) and /or Argon (Ar).The optical transitions are governed by the  and * electronic state distributions, related to sp2- and sp1-hybridized C and N atoms. Specific lonepair electronic states arise from groups (CN) with sp1-hybridized C atoms, which may form C≡N triple bonds or —N=C=N— longer chains. Photoluminescence spectra show a maximum around 650 nm. Two conduction regimes at high and low temperature are found in a-CN samples. The corresponding activation energies decrease with the increase of target voltage.

Abstract: For the characterization of the new materials and for a better understanding of the connection between structure and properties it is necessary to use more and more sensible methods to study molecular movement at nanometric scale. This paper presents the experimental basis for a new electrical method to study the fine molecular movements at nanometric scale in dielectric materials. The method will be applied for polar and non-polar materials characterization. Traditionally, the electrical methods used to study the molecular movements are based on the movements of the dipoles that are parts of the molecules. We have proposed recently a combined protocol to analyze charge injection/extraction, transport, trapping and detrapping in low mobility materials. The experimental results demonstrate that the method can be used to obtain a complex thermogram which contains information about all molecular movements, even at nanoscopic level. Actually during the charging process we are decorating the structure with space charge and during the subsequent heating we are observing an apparent peak and the genuine peaks that are related to charge de-trapping determined by the molecular movement. The method is very sensitive, very selective and allows to determinate the parameters for local and collective molecular movements, including the temperature dependence of the activation energy and the relaxation time.

Abstract: The isothermal charging current and the isothermal discharging current in low mobility materials are analyzed either in terms of polarization mechanisms or in terms of charge injection/extraction at the metal-dielectric interface and the conduction current through the dielectric material. We propose to measure the open-circuit isothermal charging and discharging currents just to overpass the difficulties related to the analysis of the conduction mechanisms in dielectric materials. We demonstrate that besides a polarization current there is a current related to charge injection or extraction at the metal-dielectric interface and a reverse current related to the charge trapped into the shallow superficial or near superficial states of the dielectric and which can move at the interface in the opposite way that occurring during injection. Two important parameters can be determined (i) the highest value of the relaxation time for the polarization mechanisms which are involved into the transient current and (ii) the height of the potential barrier W0 at the metal-dielectric interface. The experimental data demonstrate that there is no threshold field for electron injection/extraction at a metal-dielectric interface.