Chapter Introduction Introduction The discovery of carbon nanostructures (fullerenes and carbon nanotubes) in the last century brought a whole perspective to the semiconductor industry, making the development applications of silicon-based nanostructures possible. Such nanostructured materials are often produced in a metastable state, and they are unique compared to individual atoms/molecules on the one hand, and macroscopic bulk materials on the other. Their detailed atomic configuration depends sensitively on the kinetic processes by which they are fabricated. Therefore, the properties of nanostructures can be widely adjustable by changing their size, shape and processing conditions. Nanostructures of metals, semiconductors, and inorganic and organic polymers have drawn a high level of attention not only because they can be widely employed in the industry, but also for their novel characteristics which could facilitate the understanding of fundamental theories and mechanisms, for instance quantum and surface/interface effects. A protocol combining size-confinement with the electrochemical polymerization technique may offer a versatile way for the fabrication of useful organometallic conducting polymer nanostructures. Interesting properties may conceivably appear in these polymer nanostructures which hold potential for applications in electrocatalysis, as electrochemical sensors, electronic and photovoltaic devices. In the following sections, the fabrication strategies, characterizations and potential applications of conducting polymers of metal tetraaminophthalocyanines (MTAPc) in the nanostructural level will be introduced in detail. 1.1 Conducting Polymers Conducting polymers (CPs) possess a unique combination of properties as organic polymer semiconductors, and they are attractive alternatives for materials currently used in microelectronics. The field of conducting polymers could be traced back to the mid 1970’s when Shirakawa et al found the first polymer, polyacetylene, which was capable of conducting electricity [1, 2]. This work eventually resulted in the award of the Nobel Prize (2000) in Chemistry. Within a few years of the discovery, progress in the study of conjugated poly-heterocycles [3] was dramatic, and it motivated the material science community to explore increase in conductivity by doping the polymers chemically or electrochemically. In these studies, efforts were made to produce novel materials which combine properties of environmental stability, mechanical flexibility, and lightness in weight, thereby capitalizing on the easily processable advantages of an organic polymer with the available electrical properties of a metal. 1.1.1 Bandgap theory and conduction mechanism With regard to conduction properties, materials can be classified into three broad categories: Conductors (or metals), Semiconductors and Insulators. The most frequently used mechanism to explain these conduction properties may be the band theory. The highest occupied band is the valence band (VB), while the lowest unoccupied band is the conduction band (CB). The energy spacing between these two bands is known as the bandgap energy (Eg). For conductors, the VB and CB overlap and the intrinsic conductivity is attributed to the zero band gap. For semiconductors, the band gap energy is small and the electrons may be excited by vibrational, thermal or photon excitation to jump to the CB to render the material conductive. For insulators, the energy separation is too large for electrons to jump to the CB at room temperature. In terms of their bandgaps, these three classes are demonstrated in Figure 1.1. Fig. 1.1 Band structure of three categories of materials based on conducting properties Conducting polymers have always been treated as semiconductors from the viewpoint of traditional solid-state physics, though conduction in CPs is different from that in conventional inorganic materials such as doped silicon or GaAs. The bandgap in CPs is usually above 1.5eV, and thus the intrinsic conductivity is rather low (Table 1.1 shows several important conducting polymers and their conductivities). Table 1.1 Conductivities of several important conducting polymers Conductivity (S cm-1) Conducting polymer n Polyacetylene 103~105 H N n 102~103 Polyaniline (Pani) H N 102~103 n Polypyrrole (Ppy) S 102 n Polythiophene n 10-3 Poly(p-phenylene vinylene) (PPV) n 103 Poly(p-phenylene) In order to achieve conductivities comparable to metals, doping process is performed (chemically or electrochemically), and consequently the polaron-bipolaron model has been widely applied to explain the band structure changes. In chemistry, a polaron is defined as a radical cation that stabilizes itself by polarizing, while bipolaron is a bound pair of two polarons. By way of an example, these properties are explained for polypyrrole in Figure 1.2. Figure 1.2 Band structure evolution and actual structure for polypyrrole upon doping At zero doping level, the polymer is neutral and its band structure is that of a standard semiconductor. Upon the oxidative doping of polypyrrole, an electron is removed from the backbone chain to produce a polaron which is a combination of a charge site and a radical. The polaron state of polypyrrole is symmetrically located about 0.5 eV from the CB and VB edges [4]. The partial delocalization of polaron across several monomer units leads to structural distortion in the polymer. On removal of an additional electron by further oxidation, the free radical of the polaron is removed, creating a bipolaron. The bipolaron levels are located symmetrically with a band gap of 0.75 eV from both band edges. During this process, the entire polymer chains would firstly be saturated with polarons before bipolaron formation. At even higher doping level, the formation of individual bipolarons would lead to a continuous bipolaron band. Their band gap also consequently increases as newly formed bipolarons are made at the expense of the band edges. The bipolaron bandwidths are about 0.4 to 0.45eV. At such high doping levels, these spinless bipolarons exhibit high mobility under electrical field and this explains the generation of high conduction property from doped conducting polymers. Meanwhile, it is expected that the two bipolaron bands would gradually merge with the CB and VB to produce near metallic conductivity through partially filled bands. 1.1.2 Fabrication of conducting polymers The polymerization of a conducting polymer, such as polypyrrole, has been studied in depth. CPs have been synthesized mainly by three methods: electrochemical polymerization, chemical polymerization, and chemical vapor deposition. The electrochemical and chemical polymerization methods will be introduced in this chapter while the chemical vapor deposition method will be presented extensively in the next chapter. Chemical polymerization is mostly done through condensation polymerization, while nearly all electrochemical methods are based on addition polymerization. 1.1.2.1 Electrochemical polymerization Polypyrroles were produced by oxidative electropolymerization and they are the first materials synthesized by electrochemical methods in the fabrication of CPs. Very shortly after that, electrochemical polymerization drew particular interest since it allows for control of the structure, thickness, conductivity, and electrochemical properties of the resulting polymer by variation of the experimental conditions. The conditions that could be varied included film-growing rates (applied potentials and current densities), supporting electrolytes, temperatures and solvents. Since then, electrochemical polymerization using a variety of aromatic compounds (as monomers), such as indole, aniline, phenylene, furan, azulene, fluorene, pyrene and thiophene [5-9] had been investigated. Figure 1.3 lists some of these monomers employed for electropolymerization. Electropolymerization is usually initiated by oxidation via an applied potential to generate the radical ion in the first step (Figure 1.4; polypyrrole is again taken as the example here). The population of radical ions far exceeds that of neutral monomer in the vicinity of the electrode surface. This is in contrast to the situation in typical chemical polymerizations where the concentration of monomer takes the majority. The electropolymerization is terminated through the exhaustion of reactive radical species or other chain termination processes. This is a useful technique for quick and rapid fabrication of CPs. However, not all monomers undergo electrochemical polymerization. Two main key factors are the potential for the generation of radical ions and the stability of these ions in the first step. R2 R2 R1 N N N N M R1 R3 N N N N N M N N N R4 R4 Substituted Porphyrins R3 Substituted Phthalocyanines H NH2 N Pyrrole Aniline H N Indole Pyrene Figure 1.3 Examples of some monomers employed for electropolymerization Initiation of electropolymerization H N H N Potential applied + e- Propagation of electropolymerization H N H N H H N N H H H N N H H N N H n + 2H+ H N + N H n+1 + 2H+ Termination of electropolymerization H N H N H2O N H O n N H n Figure 1.4 Generic electropolymerization pathway for many CPs (taking polypyrrole as example here) CPs are mostly synthesized by galvanostatic (constant current) and potentiostatic (constant potential) polymerizations. Potentiostatic polymerization generally yields polymers with more consistent morphology. Galvanostatic deposition can be used to control charge for desired thickness, although is it universally accepted that it yields polymers of poorer morphology and conductivity. 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Journal of Molecular Science, 2003. 19(1): p. 26-32. 189 [...]... carried out in the field of synthesis, catalysis and photovoltaic properties[99, 105, 114], while special interest has been placed on the electropolymerization of MTAPc monomers 27 1.3.2 Characterization and application of electropolymerized poly-MTAPc MTAPc was first electropolymerized by Li and Guarr [115] on the surface of carbon glass electrodes Extended work on Co, Fe, Ni and Zn TAPcs were also... mechanisms of the nanostructure polymerization process chemically and electrochemically Combining the size-confinement of AAO templates with the electrochemical polymerization technique should offer a versatile way for the fabrication of MTAPc polymer nanostructures These polymer nanostructures may contribute to investigations on conductivity studies in nano-sized materials and may also have applications... microelectronics, chemical sensing, and field emission materials On the other hand, the investigation of the mechanism of MTAPc polymerization process will enhance our understanding of the electropolymerization of a series of aminosubstituted organic materials and this will help us to explain their sensing abilities However, in this thesis, dramatic improvements in the sensing properties of MTAPc nanotubes towards... to contribute to our understanding of such systems 1.4 Research Objectives Bearing in mind the above, the main objectives of this thesis are to: 1) Develop versatile and non-destructive fabrication methods for organometallic polymer nanostructures 2) Synthesize poly-CuTAPc nanostructures by template-assisted electropolymerization and analyze their properties chemically and physically 33 3) Study Electrochemical... great number of unique properties Varying the substituents at the substituted ligand on benzene rings and the central metal ion is a useful way to construct new materials, and thereby allowing process to fine-tune the physical properties of such materials Phthalocyanines are capable of incorporating more than 70 different metallic and nonmetallic cations in their ring cavity A wide variety of substituents... fabrication of nanostructures by chemical methods Self-assembled monolayers (SAMs) of thiolates have been fabricated with noble metals making use of the high affinity of thiols towards these metals [58] The SAMs can act as surfactants for other nanostructures as chemical templates Hexagonal array of pores with high aspect ratio can be formed on alumina during the anodized process of aluminum [59-62], and similar... value of the acid concentration Although these two are non-destructive methods and suitable for nanostructure characterization, the sensitivity of these 30 methods was limited by the nature of the film structure because of the relatively low surface area provided by the film morphology 1.3.3 Pc and substituted Pc nanostructures Although not as popular as polypyrrole, Pc nanostructures, on the other hand,... microelectronics in the form of field emitters and high ability capacitors • The nature of drop-dry MTAPc materials is still unclear A good understanding of the chemical structure and the surface morphology is necessary for understanding the differences in sensitivity • The mechanism of the MTAPc electropolymerization and the actual molecular linkage in polymerized structures are not yet fully understood... effective controls of size, shape and positioning of individual nanostructures fabricated Such controls can 23 be achieved by the proper selection of the process condition which allows for taking advantage of some intrinsic material properties On the other hand, using selfassembled nanostructures as template to combine other fabrication strategies of nanomaterials should provide a more versatile and convenient... analysis and field emission properties of MTAPc nanowires and nanotubes for their potential application in microelectronics 4) Investigate the chemical structure and surface morphology of drop-dried MTAPc materials; study their sensibility towards a series of oxidizing gases by Raman spectroscopy 5) Study the sensing ability of poly-MTAPc nanostructures towards oxidizing gases such as NO and NO2 as . properties of nanostructures can be widely adjustable by changing their size, shape and processing conditions. Nanostructures of metals, semiconductors, and inorganic and organic polymers have. sensors, electronic and photovoltaic devices. In the following sections, the fabrication strategies, characterizations and potential applications of 3 conducting polymers of metal tetraaminophthalocyanines. capitalizing on the easily processable advantages of an organic polymer with the available electrical properties of a metal. 1.1.1 Bandgap theory and conduction mechanism With regard to conduction