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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Synthesis and Characterization of Thin films of Novel Functionalised 2,5-Dithienylpyrrole Derivatives on Oxide Substrates

Oberoi, Sonia 14 May 2005 (has links) (PDF)
Conducting polymers find variety of application in many areas in microelectronics. PPY and PT are among the most extensively studied intrinsically conducting polymers. The problem of poor adhesion of the electrochemically deposited conducting polymers was the main focus of this work. This easy peeling of the PPY layer from the oxide substrate was circumvented by design of novel adhesion promoters, which compatibilise the two incompatible surfaces- the polymer film and the oxide substrate. The first part of the research was focused on the synthesis of different classes of adhesion promoters. These monomers were based on monoheterocyclic derivative of 3-substituted pyrrole and a tricyclic derivative of 2,5-dithienylpyrrole. The synthesized monomers were bifunctional with a specified and defined task for each group. Pyrrole based monomers, 3-phenyl N-alkyl pyrrolyl phosphonic acids referred as C10PhP and C12PhP and the monomers based on 2,5-dithienylpyrrole were synthesized with different anchoring groups namely, -Si(OMe)3 and-PO3H2 and spacer groups (n= 4, 6, 10, 12, benzyl). SNSnP for [(2,5-dithiophen-2-yl-pyrrol-1-yl)-dodecyl]-phosphonic acid, SNSnTMS for [(2,5-dithiophen-2-yl-pyrrol-1-yl)-alkyl]-trimethoxysilane and ArP for 4-(2,5-di-thiophen-2-yl-pyrrol-1-yl)-1-yl)-benzyl]-phosphonic acid was used as acronym for further references. The adsorption and self-organisation process as well as the surface reactions of these adhesion promoters on different oxide surfaces have been investigated. The aim was to graft conducting polymer layers covalently on modified metal oxide surfaces. This novel molecule has the self-assembling property and can bind to the surface via acid-base interactions with the oxide surface. The pre-treated oxide substrates were modified by self-assembling technique from solution. Static contact angle gave the first indication of a successful adsorption. The kinetics of adsorption was monitored by Surface Plasmon Resonance Spectroscopy (SPR), Angle-Resolved X-Ray Photoelectron Spectroscopy (AR-XPS) confirms that the molecules are standing with the phosphonic acid group present in the inner part of the self-assembled monolayer (SAM), and the 2,5-dithienylpyrrole group is free on the top for further surface reactions. Such self-assembling molecules can find applications in grafting conducting polymer layers on metal oxide surfaces. The grafting process of conducting polymer was done either chemically or electrochemically with additional monomer. Thickness and morphology of the polymer films were studied by AFM and SEM. The film thickness could be adjusted between several hundreds of nanometer by varying the polymerization conditions. The tape-test confirms the strong adhesive bonding of the polymer to the modified substrate. Besides PPY, Poly(SNS) and Poly(SNSnP) were studied for their properties. The optical properties of Poly(SNS) were studied by UV-Vis spectroscopy. Electrochemically deposited polymer films of (Poly(SNS), Poly(SNSnTMS), Poly(ArP) and Poly(SNSnP)) was investigated by UV-Vis spectroscopy, XPS, grazing-angle FTIR spectroscopy, four-point conductivity and I-V and luminance - voltage characteristics. Grazing-angle FT-IR of the homopolymer, poly(SNSnP) showed interesting results. We observed the peaks due to P-OH at 1111 cm-1 indicating that the phosphonic acid is free on the top. This can find application as ion sensor because phosphonates are known to be good chelating agents. Comparison of the EIS and four-point conductivity measurements for the homopolymers of SNSnP and Poly(SNS) indicated a drop in the conductivity in case of substituted hompolymers. Poly(SNSnP) based LED device give white emission. EL spectra show broad bands, which cover the entire spectrum. They can be studied further for the development of light emitting diodes of different colours.

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