A comparative study of energy transfer in dye mixtures in monomer and polymer matrices under pulsed laser excitation

This study was conducted to identify the concentration dependence of the operating wavelengths and the relative intensities in which a dye mixture doped polymer optical fibre can operate. A comparative study of the radiative and Forster type energy transfer processes in Coumarin 540:Rhodamine 6G, Coumarin 540:Rhodamine B and Rhodamine 6G:Rhodamine B in methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) was done by fabricating a series of dye mixture doped polymer rods which have two emission peaks with varying relative intensities. These rods can be used as preforms for the fabrication of polymer optical fibre amplifiers operating in the multi-wavelength regime. The 445 nm line from an Nd:YAG pumped optical parametric oscillator (OPO) was used as the excitation source for the first two dye pairs and a frequency doubled Nd:YAG laser emitting at 532 nm was used to excite the Rh 6G:Rh B pair. The fluorescence lifetimes of the donor molecule in pure form as well as in the mixtures were experimentally measured in both monomer and polymer matrices by time-correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed. It was found that radiative energy transfer mechanisms are more efficient in all the three dye pairs in liquid and solid matrices.

Excitation wavelength dependence of energy transfer in dye mixture doped polymer optical fibre preforms

Dependence of energy transfer parameters on excitation wavelength has been investigated in poly (methyl methacrylate) (PMMA) optical fibre preforms doped with C 540:Rh B dye mixture by studying the fluorescence intensity and the lifetime variations. A fluorescence spectrophotometer was used to record the excitation spectra of the samples for the emission wavelengths 495 and 580 nm. The fluorescence emission from the polymer rods was studied at four specific excitation wavelengths viz; 445, 465, 488 and 532 nm. The fluorescence lifetime of the donor molecule was experimentally measured in polymer matrix by time correlated single photon counting technique. The energy transfer rate constants and transfer efficiencies were calculated and their dependence on the acceptor concentration was analysed for three excitation wavelengths. It was found that any change in the excitation wavelength leads to significant variations in the quenching characteristics, which in turn affect the calculated energy transfer parameters.

Photothermal Characterization of Nanogold Under Conditions of Resonant Excitation and Energy Transfer

We have performed thermal diffusion measurements of nanofluid containing gold and rhodamine 6G dye in various ratios. At certain concentrations, gold is nearly four times more efficient than water in dissipating small temperature fluctuations in a medium, and therefore it will find applications as heat transfer fluids. We have employed dual-beam mode-matched thermal lens technique for the present investigation. It is a sensitive technique in measuring photothermal parameters because of the use of a lowpower, stabilized laser source as the probe. We also present the results of fluorescence measurements of the dye in the nanogold environment.

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Excitation wavelength dependent fluorescence behaviour of nano colloids of ZnO

In this paper, the fluorescence behaviour of nano colloids of ZnO has been studied as a function of the excitation wavelength. We have found that excitation at the tail of the absorption band gives rise to an emission that shifts with the change of the excitation wavelength. The excitation wavelength dependent shift of the fluorescence maximum is measured to be between 60 and 100 nm. This kind of excitation wavelength dependent fluorescence behaviour, which may appear to be in violation of Kasha’s rule of excitation wavelength independence of the emission spectrum, has been observed for nano ZnO colloids prepared by two different chemical routes and different capping agents. It is shown that the existence of a distribution of energetically different molecules in the ground state coupled with a low rate of the excited state relaxation processes, namely, solvation and energy transfer, are responsible for the excitation wavelength dependent fluorescence behaviour of the systems.

Thermal lens technique to study the effect of pH on electronic energy transfer in organic dye mixtures.

The effect of pH on the fluorescence efficiency of fluorescein is evaluated using thermal lens technique. Fluorescence efficiency increases as the sample becomes more and more alkaline. But when fluorescein is mixed with rhodamine B fluorescence quenching of fluorescein takes place with the excitation of rhodamine B. The electronic energy transfer in this mixture is investigated using Optical Parametric Oscillator as the excitation source. The effect of pH on the efficiency of energy transfer in fluorescein–rhodamine B mixture is presented.

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.

Side illumination fluorescence emission characteristics from a dye doped polymer optical fiber under two-photon excitation.

Two-photon excited (TPE) side illumination fluorescence studies in a Rh6G-RhB dye mixture doped polymer optical fiber (POF) and the effect of energy transfer on the attenuation coefficient is reported. The dye doped POF is pumped sideways using 800 nm, 70 fs laser pulses from a Ti:sapphire laser, and the TPE fluorescence emission is collected from the end of the fiber for different propagation distances. The fluorescence intensity of RhB doped POF is enhanced in the presence of Rh6G as a result of energy transfer from Rh6G to RhB. Because of the reabsorption and reemission process in dye molecules, an effective energy transfer is observed from the shorter wavelength part of the fluorescence spectrum to the longer wavelength part as the propagation distance is increased in dye doped POF. An energy transfer coefficient is found to be higher at shorter propagation distances compared to longer distances. A TPE fluorescence signal is used to characterize the optical attenuation coefficient in dye doped POF. The attenuation coefficient decreases at longer propagation distances due to the reabsorption and reemission process taking place within the dye doped fiber as the propagation distance is increased.

Selective mode excitation in dye-doped DNA polyvinyl alcohol thin film

A solid-state laser based on a dye-doped deoxyribonucleic acid (DNA) matrix is described. A thin solid film of DNA has been fabricated by treating with polyvinyl alcohol (PVA) and used as a host for the laser dye Rhodamine 6G. The edge emitted spectrum clearly indicated the existence of laser modes and amplified spontaneous emission. Lasing was obtained by pumping with a frequency-doubled Nd:YAG laser at 532 nm. For a pump energy of 10 mJ/pulse, an intense line with FWHM ≈0.2 nm was observed at 566 nm due to selective mode excitation.

Laser induced fluorescence of BaS: Sm phosphor and energy level splitting of Sm3+ ion

Fluorescence of BaS: Sm phosphor has been studied using a pulsed Nitrogen laser (337.1 nm) as the excitation source. The spectrum consists of a broad band in the region 540–660nm superposed by the characteristic Sm3+ lines. Energy level splitting pattern of Sm3+ due to crystal field effects has been calculated and relevent field parameters are evaluated. Analysis shows that Sm3+ takes up Ba2+ substitutional sites.

Energy-Efficient Cluster based Routing Schemes for Static and Mobile Sensor Networks

The theme of the thesis is centred around one important aspect of wireless sensor networks; the energy-efficiency.The limited energy source of the sensor nodes calls for design of energy-efficient routing protocols. The schemes for protocol design should try to minimize the number of communications among the nodes to save energy. Cluster based techniques were found energy-efficient. In this method clusters are formed and data from different nodes are collected under a cluster head belonging to each clusters and then forwarded it to the base station.Appropriate cluster head selection process and generation of desirable distribution of the clusters can reduce energy consumption of the network and prolong the network lifetime. In this work two such schemes were developed for static wireless sensor networks.In the first scheme, the energy wastage due to cluster rebuilding incorporating all the nodes were addressed. A tree based scheme is presented to alleviate this problem by rebuilding only sub clusters of the network. An analytical model of energy consumption of proposed scheme is developed and the scheme is compared with existing cluster based scheme. The simulation study proved the energy savings observed.The second scheme concentrated to build load-balanced energy efficient clusters to prolong the lifetime of the network. A voting based approach to utilise the neighbor node information in the cluster head selection process is proposed. The number of nodes joining a cluster is restricted to have equal sized optimum clusters. Multi-hop communication among the cluster heads is also introduced to reduce the energy consumption. The simulation study has shown that the scheme results in balanced clusters and the network achieves reduction in energy consumption.The main conclusion from the study was the routing scheme should pay attention on successful data delivery from node to base station in addition to the energy-efficiency. The cluster based protocols are extended from static scenario to mobile scenario by various authors. None of the proposals addresses cluster head election appropriately in view of mobility. An elegant scheme for electing cluster heads is presented to meet the challenge of handling cluster durability when all the nodes in the network are moving. The scheme has been simulated and compared with a similar approach.The proliferation of sensor networks enables users with large set of sensor information to utilise them in various applications. The sensor network programming is inherently difficult due to various reasons. There must be an elegant way to collect the data gathered by sensor networks with out worrying about the underlying structure of the network. The final work presented addresses a way to collect data from a sensor network and present it to the users in a flexible way.A service oriented architecture based application is built and data collection task is presented as a web service. This will enable composition of sensor data from different sensor networks to build interesting applications. The main objective of the thesis was to design energy-efficient routing schemes for both static as well as mobile sensor networks. A progressive approach was followed to achieve this goal.

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.