CHARACTERIZATION OF CHARGE INJECTION PROCESSES OF THIN FILMS ON INDIUM TIN OXIDE ELECTRODES USING A NOVEL SPECTROELECTROCHEMICAL TECHNIQUE: POTENTIAL-MODULATED ATTENUATED TOTAL REFLECTANCE SPECTROSCOPY

Persistent Link:
http://hdl.handle.net/10150/195848
Title:
CHARACTERIZATION OF CHARGE INJECTION PROCESSES OF THIN FILMS ON INDIUM TIN OXIDE ELECTRODES USING A NOVEL SPECTROELECTROCHEMICAL TECHNIQUE: POTENTIAL-MODULATED ATTENUATED TOTAL REFLECTANCE SPECTROSCOPY
Author:
Araci, Zeynep
Issue Date:
2010
Publisher:
The University of Arizona.
Rights:
Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
Abstract:
Understanding interfacial charge injection processes is one of the key factors needed for development of efficient organic electronic devices, such as biosensors and energy conversion systems, since these processes control the electrical characteristics of these devices. Spectroelectrochemical characterization of electron transfer processes occurring at the electrode - electroactive thin film interface has been evaluated to improve our understanding of charge transfer kinetics using a novel form of electroreflectance spectroscopy, potential-modulated attenuated total reflectance (PM-ATR), which makes it possible to sensitively monitor spectroscopic changes in thin films as a function of applied potential.PM-ATR was used to evaluate three different redox-active films deposited on indium tin oxide (ITO) electrodes to investigate: i) the orientation dependence of charge transfer rates of thin films of biomolecules, ii) surface treatment and modification effects on charge transfer kinetics of conducting polymers and, iii) estimation of rates of electron injection and conduction band edge of semiconductor nanocrystalline materials.First, Prussian blue film as a model system was used successfully to examine the PM-ATR technique for determination of the charge transfer rate constant between ITO and a molecular film.Second, an anisotropic and redox active protein film, cytochrome c, was used to probe charge transfer rates with respect to molecular orientation. The electron transfer rate measured using TM polarized light was four-fold greater than that measured using TE polarized light. These data are the first to correlate a distribution of molecular orientations with a distribution of electron transfer rates in a redox-active molecular film.Third, the effects of ITO surface treatment and modification on charge transfer kinetics on a conducting polymer, poly(3,4-ethylenedioxythiophene/)/poly(styrenesulfonate) (PEDOT/PSS), were studied. The apparent interfacial charge transfer rate constant for PEDOT/PSS on ITO has been reported for the first time which cannot be measured otherwise with conventional electrochemistry due to high non-Faradaic background of PEDOT/PSS films.Fourth, PM-ATR enabled characterization of reversible redox processes between submonolayer coverages of surface-tethered, CdSe nanocrystals and ITO for the first time. Optically determined onset potentials for electron injection were used for estimation for the conduction band and valance band energies (ECB and EVB, respectively).
Type:
text; Electronic Dissertation
Keywords:
charge injection rates; electroreflectance; indium tin oxide; potential-modulated ATR; surface spectroelectrochemistry; thin films
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Chemistry; Graduate College
Degree Grantor:
University of Arizona
Advisor:
Saavedra, S. Scott
Committee Chair:
Saavedra, S. Scott

Full metadata record

DC FieldValue Language
dc.language.isoenen_US
dc.titleCHARACTERIZATION OF CHARGE INJECTION PROCESSES OF THIN FILMS ON INDIUM TIN OXIDE ELECTRODES USING A NOVEL SPECTROELECTROCHEMICAL TECHNIQUE: POTENTIAL-MODULATED ATTENUATED TOTAL REFLECTANCE SPECTROSCOPYen_US
dc.creatorAraci, Zeynepen_US
dc.contributor.authorAraci, Zeynepen_US
dc.date.issued2010en_US
dc.publisherThe University of Arizona.en_US
dc.rightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.en_US
dc.description.abstractUnderstanding interfacial charge injection processes is one of the key factors needed for development of efficient organic electronic devices, such as biosensors and energy conversion systems, since these processes control the electrical characteristics of these devices. Spectroelectrochemical characterization of electron transfer processes occurring at the electrode - electroactive thin film interface has been evaluated to improve our understanding of charge transfer kinetics using a novel form of electroreflectance spectroscopy, potential-modulated attenuated total reflectance (PM-ATR), which makes it possible to sensitively monitor spectroscopic changes in thin films as a function of applied potential.PM-ATR was used to evaluate three different redox-active films deposited on indium tin oxide (ITO) electrodes to investigate: i) the orientation dependence of charge transfer rates of thin films of biomolecules, ii) surface treatment and modification effects on charge transfer kinetics of conducting polymers and, iii) estimation of rates of electron injection and conduction band edge of semiconductor nanocrystalline materials.First, Prussian blue film as a model system was used successfully to examine the PM-ATR technique for determination of the charge transfer rate constant between ITO and a molecular film.Second, an anisotropic and redox active protein film, cytochrome c, was used to probe charge transfer rates with respect to molecular orientation. The electron transfer rate measured using TM polarized light was four-fold greater than that measured using TE polarized light. These data are the first to correlate a distribution of molecular orientations with a distribution of electron transfer rates in a redox-active molecular film.Third, the effects of ITO surface treatment and modification on charge transfer kinetics on a conducting polymer, poly(3,4-ethylenedioxythiophene/)/poly(styrenesulfonate) (PEDOT/PSS), were studied. The apparent interfacial charge transfer rate constant for PEDOT/PSS on ITO has been reported for the first time which cannot be measured otherwise with conventional electrochemistry due to high non-Faradaic background of PEDOT/PSS films.Fourth, PM-ATR enabled characterization of reversible redox processes between submonolayer coverages of surface-tethered, CdSe nanocrystals and ITO for the first time. Optically determined onset potentials for electron injection were used for estimation for the conduction band and valance band energies (ECB and EVB, respectively).en_US
dc.typetexten_US
dc.typeElectronic Dissertationen_US
dc.subjectcharge injection ratesen_US
dc.subjectelectroreflectanceen_US
dc.subjectindium tin oxideen_US
dc.subjectpotential-modulated ATRen_US
dc.subjectsurface spectroelectrochemistryen_US
dc.subjectthin filmsen_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorSaavedra, S. Scotten_US
dc.contributor.chairSaavedra, S. Scotten_US
dc.contributor.committeememberArmstrong, Neal R.en_US
dc.contributor.committeememberPemberton, Jeanne E.en_US
dc.contributor.committeememberEnemark, John H.en_US
dc.identifier.proquest11182en_US
dc.identifier.oclc752261036en_US
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