Photopyroelectric study of thermal properties and phase transitions in selected solids

This thesis presents in detail. the theoretical developments and calculations which are used for the simultaneous determination of thermal parameters, namely thermal diffusivity (a). thermal effusivity (e), thermal conductivity (K) and heat capacity (cr ) employing photopyroelectric technique. In our calculations. we have assumed that the pyroelectric detector is supported on a copper backing. so that there will be sufficient heat exchange between the heated pyroelectric detector and the backing so that the signal fluctuations are reduced to a minimum. Since the PPE signal depends on the properties of the detector that are also temperature dependent. a careful temperature calibration of the system need to be carried out. APPE cell has been fabricated for the measurements that can be used to measure the thermal properties of solid samples from ~ 90 K to ~ 350 K. The cell has been calibrated using standard samples and the accuracy of the technique is found to be of the order of± 1%.In this thesis, we have taken up work n photopyroelectric investigation of thermal parameters of ferroelectric crystals such as Glycine phosphite (NH3CH2COOH3P03), Triglycine sulfate and Thiourea as well as mixed valence perovskites samples such as Lead doped Lanthanum Manganate (Lal_xPb~Mn03) Calcium doped (Lal_xCaxMnOJ) and Nickel doped Lanthanum Stroncium Cobaltate (Lao~Sro5Ni,Col_x03).The three ferroelectric crystals are prepared by the slow evaporation technique and the mixed valence perovskites by solid state reaction technique.Mixed valence perovskites, with the general formula RI_xA~Mn03 (R = La. Nd or Pr and A = Ba, Ca, Sr or Pb) have been materials of intense experimental and theoretical studies over the past few years. These materials show . colossal magneloresis/ance' (CMR) in samples with 0.2 < x < 0.5 in such a doping region, resistivity exhibits a peak at T = T p' the metal - insulator transition temperature. The system exhibits metallic characteristics with d %T > Oabove Tp (wherep is the resistivity) and insulating characteristics with d % T < 0 above T p. Despite intensive investigations on the CMR phenomena and associated electrical properties. not much work has been done on the variation of thermal properties of these samples. We have been quite successful in finding out the nature of anomaly associated with thermal properties when the sample undergoes M-I transition.The ferroelectric crystal showing para-ferroelectric phase transitions - Glycine phosphite. Thiourea and Triglycine sulfate - are studied in detail in order to see how well the PPE technique enables one to measure the thermal parameters during phase transitions. It is seen that the phase transition gets clearly reflected in the variation of thermal parameters. The anisotropy in thermal transport along different crystallographic directions are explained in terms of the elastic anisotropy and lattice contribution to the thermal conductivity. Interesting new results have been obtained on the above samples and are presented in three different chapters of the thesis.In summary. we have carried investigations of the variations of the thermal parameters during phase transitions employing photopyroelectric technique. The results obtained on different systems are important not only in understanding the physics behind the transitions but also in establishing the potentiality of the PPE tool. The full potential of PPE technique for the investigation of optical and thermal properties of materials still remains to be taken advantage of by workers in this field.

Low-voltage driven ZnS:Mn MIS and MISIM thin film electroluminescent devices with Eu2O3 insulator layer

AC thin film electroluminescent devices of MIS and MISIM have been fabricated with a novel dielectric layer of Eu2O3 as an insulator. The threshold voltage for light emission is found to depend strongly on the frequency of excitation source in these devices. These devices are fabricated with an active layer of ZnS:Mn and a novel dielectric layer of Eu2O3 as an insulator. The observed frequency dependence of brightness-voltage characteristics has been explained on the basis of the loss characteristic of the insulator layer. Changes in the threshold voltage and brightness with variation in emitting or insulating film thickness have been investigated in metal-insulator-semiconductor (MIS) structures. It has been found that the decrease in brightness occurring with decreasing ZnS layer thickness can be compensated by an increase in brightness obtained by reducing the insulator thickness. The optimal condition for low threshold voltage and higher stability has been shown to occur when the active layer to insulator thickness ratio lies between one and two.

A Comaparison Study of EM and Physical Equivalent Circuit Modeling for MIM CMOS Capacitors

In this Letter a new physical model for metal-insulatormetal CMOS capacitors is presented. In the model the parameters of the circuit are derived from the physical structural details. Physical behaviors due to metal skin effect and inductance have been considered. The model has been confirmed by 3D EM simulator and design rules proposed. The model presented is scalable with capacitor geometry, allowing designers to predict and optimize quality factor. The approach has been verified for MIM CMOS capacitors

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors.

Synthesis and Characterization Of Some Transition Metal Complexes Of Multidentate Ligands

Coordination chemistry of schiff bases is of considerable interest due to their various magnetic, catalytic and biological applications. Here it describes the spectral characterization of schiff bases and its Mn (II), Cu (II) and Ni (II) complexes. Then synthesis and spectral characterization of Zn (II), Cd (II) and Co (II) complexes of schiff base derived from 3-Formylsalicilic Acid and 1,3-diaminopropane. Then it discusses the synthesis and spectral studies of Copper (II) complexes of 2-Hydroxyacetophenone N-phenyl semicarbazone. Finally it discusses the synthesis and spectral characterization of Co (III) complexes of salicylaldehyde N-phenyl semicarbazone. The preparation and characterization of Cobalt (III) complexes of salicylaldehyde, N-phenylthiosemicarbazone containing hetrocyclic bases phenalthroline and bipyridine. Thiocyanate, azide and perchlorate ions act as coligands. Elemental analysis suggests +3 state for Cobalt. HNMR, IR and UV-visible spectra characterize the complexes.

Synthesis, Spectral Characterization, Structural Studies and Biological Investigations of Transition Metal Complexes of Some Acid Hydrazones

This study concentrates the chemical properties of hydrazones due to its chelating capability and their pharmacological applications. Studies cover the preparation of different acid hydrazones and their structural studies and studies on their antimicrobial activity, synthesis and spectral characterization of different complexes of copper oxovanadium, manganese, nickel etc. Effect of incorporation of heterocyclic bases to the coordination sphere, change in the biological activity of acid hydrazones upon coordination, development of X-ray quality single crystals and its X-ray diffraction studies, studies on the redox behavior of the coordinated metal ions and correlation between the stereochemistry and biological activities.

Diversity in Structural and Spectural Characteristics of Some Transition Metal Complexes Derived From Aldehyde Based Thiosemicarbazone Ligands

The study deals with the diversity in structural and spectural characteristics of some transition metal complexes derived from aldehyde based thiosemicarbazone ligands thiosemicarbazones are a family of compounds with beneficial biological activity viz., anticancer,antitumour, antifungal, antibacterial, antimalarial, antifilarial, antiviral and anti-HIV activities. Many thiosemicarbazone ligands and their complexes have been prepared and screened for their antimicrobial activity against various types of fungi and bacteria. The results prove that the compounds exhibit antimicrobial properties and it is important to note that in some cases metal chelates show more inhibitory effects than the parent ligands. The increased lipophilicity of these complexes seems to be responsible for their enhanced biological potency. Adverse biological activities of thiosemicarbazones have been widely studied in rats and in other species. The parameters measured show that copper complexes caused considerable oxidative stress and zinc zinc complexes behaved as antioxidants. It has applications on analytical field also. Some thiosemicarbazones produce highly colored complexes with metal ions. This thesis aims to synthesis some novel thiosemicarbazone ligands and their transition metal complexes together with their physico-chemical characterization.

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.

Structural, Spectral, Biological and Electrochemical Studies Of Some 3d Transition Metal Complexes of O-N-S and N-N-S Donor Ligands

The primary aim of these investigations was to probe the spectroscopic, electrochemical, biological and single crystal X-ray diffraction studies of some selected transition metal complexes of 4N-monosubstituted thiosemicarbazones. Transition metal complexes with thiosemicarbazones exhibit a wide range of stereochemistries and possess potential biological activity. Metal complexes of thiosemicarbazones are proved to have improved pharmacological and therapeutic effects. The studies are conducted to bring about a fair understanding of the structure activity relationship and to develop certain effective and economical metal-based antimicrobial agents. Study showed that the thiosemicarbazones have antibacterial, antiviral and antiproliferative properties and hence used against tuberculosis, leprosy, psoriasis, rheumatism, trypanosomiasis and coccidiosis. Certain thiosemicarbazones showed a selective inhibition of HSV and HIV infections. The insolubility of most thiosemicarbazones in water causes difficulty in the oral administration in clinical practice. Transition metal complexes are found to have more activity than uncombined thiosemicarbazones. They exhibit a variety of denticity and can be varied by proper substitution. The stereochemistry assumed by the thiosemicarbazones during the coordination with transition metal ions depends on the factors such as preparative conditions and availability of additional bonding site in the ligand moiety and charge of the ligand. The resulting complexes exhibited a wide range of stereochemistries and have biomimic activity and potential application as sensors

Studies on Some Simple and Zeolite-Y Encapsulated 3d-Transition Metal Complexes of Schiff Bases Derived From 2-Aminobenzothiazole

In this regard Schiff base complexes have attracted wide attention. Furthermore, such complexes are found to play important role in analytical chemistry, organic synthesis, metallurgy, refining of metals, electroplating and photography. Many Schiff base complexes are reported in literature. Their properties depend on the nature of the metal ion as well as on the nature of the ligand. By altering the ligands it is possible to obtain desired electronic environment around the metal ion. Thus there is a continuing interest in the synthesis of simple and zeolite encapsulated Schiff base complexes of metal ions. Zeolites have a number of striking structural similarities to the protein portion of natural enzymes. Zeolite based catalysts are known for their remarkable ability of mimicking the chemistry of biological systems. In view of the importance of catalysts in all the areas of modern chemical industries, an effort has been made to synthesize some simple Schiff base complexes, heterogenize them by encapsulating within the supercages of zeoliteY cavities and to study their applications. The thesis deals with studies on the synthesis and characterization of some simple and zeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes and on the catalytic activity of these complexes on some oxidation reactions. Simple complexes were prepared from the Schiff base ligands SBT derived from 2-aminobenzothiazole and salicylaldehyde and the ligand VBT derived from 2-aminobenzothiazole and vanillin (4-hydroxy-3- methoxybenzaldehyde). ZeoliteY encapsulated Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) complexes of Schiff base ligands SBT and VBT and also of 2-aminobenzothiazole were synthesized. All the prepared complexes were characterized using the physico-chemical techniques such as chemical analysis (employing AAS and CHN analyses), magnetic moment studies, conductance measurements and electronic and FTIR spectra. EPR spectra of the Cu(II) complexes were also carried out to know the probable structures and nature of Cu(II) complexes. Thermogravimetric analyses were carried out to obtain the information regarding the thermal stability of various complexes. The successful encapsulations of the complexes within the cavities of zeoliteY were ascertained by XRD, surface area and pore volume analysis. Assignments of geometries of simple and zeoliteY encapsulated complexes are given in all the cases. Both simple and zeoliteY encapsulated complexes were screened for catalytic activity towards oxidation reactions such as decomposition of hydrogen peroxide, oxidation of benzaldehyde, benzyl alcohol, 1-propanol, 2-propanol and cyclohexanol.

Studies on Some Transition Metal Complexes of Schiff Bases Derived from Quinoxaline-2-carboxaldehyde

Two series of transition metal complexes of Schiff bases derived from quinoxaline-2-carboxaldehyde with semicarbazide (QSC) and furfurylamine (QFA) were synthesised and characterised by elemental analyses, molar conductance and magnetic susceptibility measurements, IR, electronic and EPR spectral studies. The QSC complexes have the general formula [M(QSC)Cl2]. A tetrahedral structure has been assigned for the Mn(II), Co(II) and Ni(II) complexes and a square-planar structure for the Cu(II) complex. The QFA complexes have the formula [M(QFA)2Cl2]. An octahedral structure has been assigned for these complexes. All of the complexes exhibit catalytic activity towards the oxidation of 3,5-di-tert-butylcatechol (DTBC) to 3,5-di-tert-butylquinone (DTBQ) using atmospheric oxygen. The cobalt(II) complex of the ligand QFA was found to be the most active catalyst.

Synthesis and Characterization of Some New Transition Metal Complexes of the Schiff Base Derived from Quinoxaline-2-Carboxaldehyde and 2- Aminophenol

Some new transition metal complexes of the Schiff base quinoxaline-2-car boxalidene-2-aminophenol (HQAP) have been synthesized and characterized by elemental analyses, conductance and magnetic measurements and IR and UV-Visible spectral studies. The complexes have the following empirical formulae: [Mn(QAP121, [Fe(QAPl2C1I, [Co(QAPl21, [Ni(QAP121 and [Cu(QAP121. A tetrahedral structure has been assigned for the manganese(=), cobalt(II1, nickel(II1 and copper(II1 complexes. For the iron(IIIl complex an octahedral dimeric structure has been suggested