Studies on Fluorescence Efficiency and Photodegradation of Rhodamine 6G Doped PMMA Using a Dual Beam Thermal Lens Technique

In this paper we report the use of the dual beam thermal lens technique as a quantitative method to determine absolute fluorescence quantum efficiency and concentration quenching of fluorescence emission from rhodamine 6G doped Poly(methyl methacrylate) (PMMA), prepared with different concentrations of the dye. A comparison of the present data with that reported in the literature indicates that the observed variation of fluorescence quantum yield with respect to the dye concentration follows a similar profile as in the earlier reported observations on rhodamine 6G in solution. The photodegradation of the dye molecules under cw laser excitation is also studied using the present method.

Effect of silver nano particles on the fluorescence quantum yield of Rhodamine 6G determined using dual beam thermal lens method

Nano structured noble metals have very important applications in diverse fields as photovoltaics, catalysis, electronic and magnetic devices, etc. Here, we report the application of dual beam thermal lens technique for the determination of the effect of silver sol on the absolute fluorescence quantum yield (FQY) of the laser dye rhodamine 6G. A 532 nm radiation from a diode pumped solid state laser was used as the excitation source. It has been observed that the presence of silver sol decreases the fluorescence quantum efficiency. This is expected to have a very important consequence in enhancing Raman scattering which is an important spectrochemical tool that provides information on molecular structures. We have also observed that the presence of silver sol can enhance the thermal lens signal which makes the detection of the signal easier at any concentration.

Investigations on polyaniline based systems for technologically important applications and some novel polymers as prospective candidates for fabricating polymer light emitting diodes

Light emitting polymers (LEP) have drawn considerable attention because of their numerous potential applications in the field of optoelectronic devices. Till date, a large number of organic molecules and polymers have been designed and devices fabricated based on these materials. Optoelectronic devices like polymer light emitting diodes (PLED) have attracted wide-spread research attention owing to their superior properties like flexibility, lower operational power, colour tunability and possibility of obtaining large area coatings. PLEDs can be utilized for the fabrication of flat panel displays and as replacements for incandescent lamps. The internal efficiency of the LEDs mainly depends on the electroluminescent efficiency of the emissive polymer such as quantum efficiency, luminance-voltage profile of LED and the balanced injection of electrons and holes. Poly (p-phenylenevinylene) (PPV) and regio-regular polythiophenes are interesting electro-active polymers which exhibit good electrical conductivity, electroluminescent activity and high film-forming properties. A combination of Red, Green and Blue emitting polymers is necessary for the generation of white light which can replace the high energy consuming incandescent lamps. Most of these polymers show very low solubility, stability and poor mechanical properties. Many of these light emitting polymers are based on conjugated extended chains of alternating phenyl and vinyl units. The intra-chain or inter-chain interactions within these polymer chains can change the emitted colour. Therefore an effective way of synthesizing polymers with reduced π-stacking, high solubility, high thermal stability and high light-emitting efficiency is still a challenge for chemists. New copolymers have to be effectively designed so as to solve these issues. Hence, in the present work, the suitability of a few novel copolymers with very high thermal stability, excellent solubility, intense light emission (blue, cyan and green) and high glass transition temperatures have been investigated to be used as emissive layers for polymer light emitting diodes.

Investigations on Photoconductivity and Electrical Switiching in Selected Chalcogenide Glasses

In this thesis, we present the results of our investigations on the photoconducting and electrical switching properties of selected chalcogenide glass systems. We have used XRD and X-ray photoelectron spectroscopy (XPS) analysis for confinuing the amorphous nature of these materials and for confirming their constituents respectively.Photoconductivity is the enhancement in electrical conductivity of materials brought about by the motion of charge carriers excited by absorbed radiation. The phenomenon involves absorption, photogeneration, recombination and transport processes and it gives good insight into the density of states in the energy gap of solids due to the presence of impurities and lattice defects. Photoconductivity measurements lead to the determination of such important parameters as quantum efficiency, photosensiti\'ity, spectral sensitivity and carrier lifetime. Extensive research work on photoconducting properties of amorphous semiconductors has resulted in the development of a variety of very sensitive photodetectors. Photoconductors are finding newer and newer uses eyery day. CdS, CdSe. Sb2S3, Se, ZnO etc, are typical photoconducting materials which are used in devices like vidicons, light amplifiers, xerography equipment etc.Electrical switching is another interesting and important property possessed by several Te based chalcogenides. Switching is the rapid and reversible transition between a highly resistive OFF state, driven by an external electric field and characterized by a threshold voltage, and a low resistivity ON state, Switching can be either threshold type or memory type. The phenomenon of switching could find applications in areas like infonnation storage, electrical power control etc. Investigations on electrical switching in chalcogenide glasses help in understanding the mechanism of switching which is necessary to select and modify materials for specific switching applications.Analysis of XRD pattern gives no further infonuation about amorphous materials than revealing their disordered structure whereas x-ray photoelectron spectroscopy,XPS) provides information about the different constituents present in the material. Also it gives binding energies (b.e.) of an element in different compounds and hence b.e. shift from the elemental form.Our investigations have been concentrated on the bulk glasses, Ge-In-Se, Ge-Bi-Se and As-Sb-Se for photoconductivity measurements and In-Te for electrical switching. The photoconducting properties of Ge-Sb-Se thin films prepared by sputtering technique have also been studied. The bulk glasses for the present investigations are prepared by the melt quenching technique and are annealed for half an hour at temperatures just below their respective glass transition temperatures. The dependence of photoconducting propenies on composition and temperature are investigated in each system. The electrical switching characteristics of In-Te system are also studied with different compositions and by varying the temperature.

Photoemission optogalvanic effect studies in N2, NO2 and Ar discharges under pulsed laser excitation

A two-photon induced photoemission optogalvanic effect which brings about a change in the discharge voltage when a pulsed dye laser beam is focused on a tungsten electrode has been described. The experiment is performed with N2, NO2 and Ar discharges. The magnitude of the signal voltage is studied as a function of laser energy and discharge current. The effective quantum efficiency in the discharge is found to be larger than that in the vacuum condition.

Photoemission optogalvanic effect studies in N2, NO2 and Ar discharges under pulsed laser excitation

A two-photon induced photoemission optogalvanic effect which brings about a change in the discharge voltage when a pulsed dye laser beam is focused on a tungsten electrode has been described. The experiment is performed with N2, NO2 and Ar discharges. The magnitude of the signal voltage is studied as a function of laser energy and discharge current. The effective quantum efficiency in the discharge is found to be larger than that in the vacuum condition.

The photoemission optogalvanic effect in a Ne-Nd hollow cathode

Laser-induced photoelectric and photoemission optogalvanic effects in a Ne-Nd hollow cathode discharge have been studied using a continuous wave laser source. The potential barrier for photoinduced electron emission from the cathode decreases as the applied voltage is increased. Owing to secondary electron emission in the plasma, the photocurrent is greater than that without discharge. The multiplication of secondary electrons and the quantum efficiency are also investigated.

Synthesis and Photoluminescence Properties of Novel Red Phosphors for White Light Emitting Diode Applications

Several series of Eu3+ based red emitting phosphor materials were synthesized using solid state reaction route and their properties were characterized. The present studies primarily investigated the photoluminescence properties of Eu3+ in a family of closely related host structure with a general formula Ln3MO7. The results presented in the previous chapters throws light to a basic understanding of the structure, phase formation and the photoluminescence properties of these compounds and their co-relations. The variation in the Eu3+ luminescence properties with different M cations was studied in Gd3-xMO7 (M = Nb, Sb, Ta) system.More ordering in the host lattice and more uniform distribution of Eu3+ ions resulting in the increased emission properties were observed in tantalate system.Influence of various lanthanide ion (Lu, Y, Gd, La) substitutions on the Eu3+ photoluminescence properties in Ln3MO7 host structures was also studied. The difference in emission profiles with different Ln ions demonstrated the influence of long range ordering, coordination of cations and ligand polarizability in the emission probabilities, intensity and quantum efficiency of these phosphor materials. Better luminescence of almost equally competing intensities from all the 4f transitions of Eu3+ was noticed for La3TaO7 system. Photoluminescence properties were further improved in La3TaO7 : Eu3+ phosphors by the incorporation of Ba2+ ions in La3+ site. New red phosphor materials Gd2-xGaTaO7 : xEu3+ exhibiting intense red emissions under UV excitation were prepared. Optimum doping level of Eu3+ in these different host lattices were experimentally determined. Some of the prepared samples exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. In the present studies, Eu3+ acts as a structural probe determining the coordination and symmetry of the atoms in the host lattice. Results from the photoluminescence studies combined with the powder XRD and Raman spectroscopy investigations helped in the determination of the correct crystal structures and phase formation of the prepared compounds. Thus the controversy regarding the space groups of these compounds could be solved to a great extent. The variation in the space groups with different cation substitutions were discussed. There was only limited understanding regarding the various influential parameters of the photoluminescence properties of phosphor materials. From the given studies, the dependence of photoluminescence properties on the crystal structure and ordering of the host lattice, site symmetries, polarizability of the ions, distortions around the activator ion, uniformity in the activator distribution, concentration of the activator ion etc. were explained. Although the presented work does not directly evidence any application, the materials developed in the studies can be used for lighting applications together with other components for LED lighting. All the prepared samples were well excitable under near UV radiation. La3TaO7 : 0.15Eu3+ phosphor with high efficiency and intense orange red emissions can be used as a potential red component for the realization of white light with better color rendering properties. Gd2GaTaO7 : Eu3+, Bi2+ red phosphors give good color purity matching to NTSC standards of red. Some of these compounds exhibited higher emission intensities than the standard Y2O3 : Eu3+ red phosphors. However thermal stability and electrical output using these compounds should be studied further before applications. Based on the studies in the closely related Ln3MO7 structures, some ideas on selecting better host lattice for improved luminescence properties could be drawn. Analyzing the CTB position and the number of emission splits, a general understanding on the doping sites can be obtained. These results could be helpful for phosphor designs in other host systems also, for enhanced emission intensity and efficiency.

Singlet Oxygen in Microporous Silica Xerogel:Quantum Yield and Oxidation at the Gas–Solid Interface

The quantum yields of singlet oxygen production and lifetimes at the gas–solid interface in silica gel material are determined. Different photosensitizers (PS) are encapsulated in parallelepipedic xerogel monoliths (PS-SG). PS were chosen according to their known photooxidation properties: 9,10-dicyanoanthracene (DCA), 9,10-anthraquinone (ANT), and a benzophenone derivative, 4-benzoyl benzoic acid (4BB). These experiments are mainly based on time-resolved 1O2 phosphorescence detection, and the obtained FD and tD values are compared with those of a reference sensitizer for production, 1H-phenalen-1- one (PN), included in the same xerogel. The trend between their ability to oxidize organic pollutants in the gas phase and their efficiency for production is investigated through photooxidation experiments of a test pollutant dimethylsulfide (DMS). The FD value is high for DCA-SG relative to the PN reference, whereas it is slightly lower for 4BB-SG and for ANT-SG. FD is related to the production of sulfoxide and sulfone as the main oxidation products for DMS photosensitized oxidation. Additional mechanisms, leading to C!S bond cleaveage, appear to mainly occur for the less efficient singlet oxygen sensitizers 4BB-SG and ANTSG.