Octasubstituted phthalocyanine assemblies: Characterization, polymerization, and patterning

Persistent Link:
http://hdl.handle.net/10150/279830
Title:
Octasubstituted phthalocyanine assemblies: Characterization, polymerization, and patterning
Author:
Zangmiester, Rebecca Anne
Issue Date:
2001
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:
This dissertation explores the characterization of new phthalocyanine materials, and the processability of these materials with regard to thin film structures envisioned for use in organic based electronic devices. Highly ordered, coherent molecular assemblies are formed by Cu centered benzyloxyethoxy-substituted phthalocyanines. The influence of molecular aggregate interactions with solid supports, based on phenyl-phenyl interactions, manifests itself in large changes in wettability, and also in molecular orientations within those molecular aggregates. Selective deposition of these Pc assemblies was achieved based on chemical interactions with a heterogeneous surface. A facile process of creating alternating hydrophobic/hydrophilic regions on a Au substrate surface through a combination of microcontact printing and electropolymerization techniques (μCP/EP) was demonstrated. Optimization of the hydrophobic channel bottom regions with a phenyl terminated dopant results in patterned phthalocyanine stripes up to 500 μm in length. The substitution of a Co metal center does not appreciably influence the properties of the benzyloxyethoxy-substituted phthalocyanine material, although the lone pair electron, in the d(z)² orbital perpendicular to the Pc macrocycle, appears to be responsible for differences in molecular orientation. The ability of the Co metal to coordinate ligands (i.e. O₂) is particularly evident in electrochemical data taken of this material. Two new photoreactive phthalocyanines, with styryl- and cinnamyl-terminations, result in the formation of new materials, whose preliminary characterization is presented. The photoexcited polymerization of the styryl-substituted material resulted in formation of a 1-dimensional rod-like polymer material, with a mean rod length of 72 nm. The conversion percentages for this material routinely reached 30%, and are expected to improve with purer monomeric materials. The photolysis of the cinnamyl-terminated material routinely reach 70% conversion, and resulted in an insoluble material, that allows for photopatterning. Conventional interdigitated microelectrode (IME) measurements made on these materials show conductivities as high as ca. 10⁻⁸Ω⁻¹·cm⁻¹, and mobility values as high as 10⁻³ cm²·V⁻¹s⁻¹. These charge carrier properties, combined with the selective deposition possibilities (i.e. using patterned substrates and/or photolysis techniques) make this class of materials desirable for further investigation and applications in organic based electronic devices.
Type:
text; Dissertation-Reproduction (electronic)
Keywords:
Chemistry, Analytical.; Chemistry, Inorganic.; Engineering, Materials Science.
Degree Name:
Ph.D.
Degree Level:
doctoral
Degree Program:
Graduate College; Chemistry
Degree Grantor:
University of Arizona
Advisor:
Armstrong, Neal R.

Full metadata record

DC FieldValue Language
dc.language.isoen_USen_US
dc.titleOctasubstituted phthalocyanine assemblies: Characterization, polymerization, and patterningen_US
dc.creatorZangmiester, Rebecca Anneen_US
dc.contributor.authorZangmiester, Rebecca Anneen_US
dc.date.issued2001en_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.abstractThis dissertation explores the characterization of new phthalocyanine materials, and the processability of these materials with regard to thin film structures envisioned for use in organic based electronic devices. Highly ordered, coherent molecular assemblies are formed by Cu centered benzyloxyethoxy-substituted phthalocyanines. The influence of molecular aggregate interactions with solid supports, based on phenyl-phenyl interactions, manifests itself in large changes in wettability, and also in molecular orientations within those molecular aggregates. Selective deposition of these Pc assemblies was achieved based on chemical interactions with a heterogeneous surface. A facile process of creating alternating hydrophobic/hydrophilic regions on a Au substrate surface through a combination of microcontact printing and electropolymerization techniques (μCP/EP) was demonstrated. Optimization of the hydrophobic channel bottom regions with a phenyl terminated dopant results in patterned phthalocyanine stripes up to 500 μm in length. The substitution of a Co metal center does not appreciably influence the properties of the benzyloxyethoxy-substituted phthalocyanine material, although the lone pair electron, in the d(z)² orbital perpendicular to the Pc macrocycle, appears to be responsible for differences in molecular orientation. The ability of the Co metal to coordinate ligands (i.e. O₂) is particularly evident in electrochemical data taken of this material. Two new photoreactive phthalocyanines, with styryl- and cinnamyl-terminations, result in the formation of new materials, whose preliminary characterization is presented. The photoexcited polymerization of the styryl-substituted material resulted in formation of a 1-dimensional rod-like polymer material, with a mean rod length of 72 nm. The conversion percentages for this material routinely reached 30%, and are expected to improve with purer monomeric materials. The photolysis of the cinnamyl-terminated material routinely reach 70% conversion, and resulted in an insoluble material, that allows for photopatterning. Conventional interdigitated microelectrode (IME) measurements made on these materials show conductivities as high as ca. 10⁻⁸Ω⁻¹·cm⁻¹, and mobility values as high as 10⁻³ cm²·V⁻¹s⁻¹. These charge carrier properties, combined with the selective deposition possibilities (i.e. using patterned substrates and/or photolysis techniques) make this class of materials desirable for further investigation and applications in organic based electronic devices.en_US
dc.typetexten_US
dc.typeDissertation-Reproduction (electronic)en_US
dc.subjectChemistry, Analytical.en_US
dc.subjectChemistry, Inorganic.en_US
dc.subjectEngineering, Materials Science.en_US
thesis.degree.namePh.D.en_US
thesis.degree.leveldoctoralen_US
thesis.degree.disciplineGraduate Collegeen_US
thesis.degree.disciplineChemistryen_US
thesis.degree.grantorUniversity of Arizonaen_US
dc.contributor.advisorArmstrong, Neal R.en_US
dc.identifier.proquest3026560en_US
dc.identifier.bibrecord.b42177479en_US
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