Dye-sensitized solar cells (DSSCs) present an interesting method for the conversion of sunlight into electricity. Unlike in other photovoltaic technologies, the difficult tasks of light absorption and charge transport are handled by two different materials in DSSCs. At the heart of the DSSC, molecular light absorbers (dyes) are responsible for converting light into current. In this thesis the design, synthesis and properties of new metal-free D-π-A dyes for dye-sensitized solar cells will be explored. The thesis is divided into six parts: Part one offers a general introduction to DSSCs, dye design and device characterization. Part two is an investigation of a series of donor substituted dyes where structural benefits are compared against electronic benefits. In part three a dye assembly consisting of a chromophore tethered to two electronically decoupled donors is described. The assembly, capable of intramolecular regeneration, is found to impede recombination. Part four explores a method for rapidly synthesizing new D-π-A dyes by dividing them into donor, linker and acceptor fragments that can be assembled in two simple steps. The method is applied to synthesize a series of linker varied dyes for cobalt based redox mediators that builds upon the experience from part two. Part five describes the synthesis of a bromoacrylic acid based dye and explores the photoisomerization of a few bromo- and cyanoacrylic acid based dyes. Finally, in part six the experiences from previous chapters are combined in the design and synthesis of a D-π-A dye bearing a new pyridinedicarboxylic acid acceptor and anchoring group. / <p>QC 20140509</p>

With an increasing demand for renewable energy sources, research efforts on different solar cell technologies are increasing rapidly. The dye-sensitized solar cell (DSC) is one such technology, taking advantage of light absorption in dye molecules. The liquid based DSC contains several interesting and important interfaces, crucial for the understanding and development of the solar cell performance. Examples of such interfaces include dye-semiconductor, electrode-electrolyte and solute-solvent interfaces. Ultimately, complete interfaces with all these components included are of particular interest. One major challenge is to understand the key functions of these systems at an atomic level and one way to achieve this is to use an element specific and surface sensitive tool, such as photoelectron spectroscopy (PES). This thesis describes the use and development of PES for studying interfaces in the DSC. The materials part of the thesis focuses on interfaces in DSCs studied with PES and the methodology development parts focus on methods to use PES for investigations of solvated heterogeneous interfaces of interest for photoelectrochemical systems such as the DSC. More specifically, beginning with standard vacuum techniques, dye molecules bound to a semiconductor surface have been studied in terms of energy level alignment, surface coverage and binding configuration. To increase the understanding of solvation phenomena present in the liquid DSC, liquid jet experiments have been performed in close combination with theoretical quantum calculations. As a step towards an in-situ method to measure a complete, functioning (in operando) solar cell, methodology development and measurements performed with higher sample pressures are described using new high pressure X-ray photoelectron spectroscopy techniques (HPXPS).

The scalable syntheses of functional, porous nanostructures with tunable three-dimensional morphologies is a significant challenge with potential applications in chemical, electrical, electrochemical, optical, photochemical, and biochemical devices. As a result, several bio-enabled and synthetic approaches are explored in this work (with an emphasis on peptide-enabled deposition) for the generation of aligned nanotubes of nanostructured titania for application as electrodes in dye-sensitized solar cells and biofuel cells. As part of this work, peptide-enabled deposition was used to deposit conformal titania coatings onto porous anodic alumina templates under ambient conditions and near-neutral pH to generate aligned, porous-wall titania nanotube arrays that can be integrated into dye-sensitized solar cells where the arrays displayed improved functional dye loading compared to sol-gel-derived nanotubes. A detailed comparison between synthetic and bioorganic polyamines with respect to titania film properties deposition rate provided valuable information for future titania coating experimental design given specific applications. The development of template-based approaches to single-wall titania nanotube arrays led to the development of a new synthetic method to create aligned, multi-walled titania nanotube arrays. Lastly, peptide-enabled deposition methods were extended beyond inorganic mineral and used for enzyme immobilization by cross-linking the peptide with the multicopper oxidase laccase. Peptide-laccase hybrid enzyme coatings improved both the amount of enzyme adsorbed onto carbon nanotube “buckypaper” and allowed the enzyme to retain more activity upon immobilization onto the surface.

The photosensitive molecule adsorption on titanium dioxide (TiO2) forms the so-called “dye sensitized TiO2” system, a typical organic/oxide heterojunction, which is of great interest in catalysis and energy applications, e.g. dye-sensitized solar cell (DSSC). Traditionally, the transition metal complex dyes are the focus of the study. However, as the fast development of the organic semiconductors and invention of new pure organic dyes, it is necessary to expand the research horizon to cover these molecules and concrete the fundamental understanding of their basic properties, especially during sensitization.In this work, we focus on two different photosensitive molecules: phthalocyanines and triphenylamine-based dyes. Phthalocyanines are organic semiconductors with symmetric macro aromatic molecular structures. They possess good photoelectrical properties and good thermal and chemical stability, which make them widely used in the organic electronic industries. Triphenylamine-based dyes are new types of pure organic dyes which deliver high efficiency and reduce the cost of DSSC. They can be nominated as one of the strong candidates to substitute the ruthenium complex dyes in DSSC. The researches were carried out using classic surface science techniques on single crystal substrates and under ultrahigh vacuum condition. The photosensitive molecules were deposited by organic molecular beam deposition. The substrate reconstruction and ordering were checked by low energy electron diffraction. The molecular electronic, geometric structures and charge transfer properties were characterized by photoelectron spectroscopy, near edge X-ray absorption fine structure spectroscopy and resonant photoelectron spectroscopy (RPES). Scanning tunneling microscopy is used to directly image the molecular adsorption.For phthalocyanines, we select MgPc, ZnPc, FePc and TiOPc, which showed a general charge transfer from molecule to the substrate when adsorbed on rutile TiO2(110) surface with 1×1 and 1×2 reconstructions. This charge transfer can be prevented by modifying the TiO2 surface with pyridine derivatives (4-tert-butyl pyridine (4TBP), 2,2’-bipyridine and 4,4’-bipyridine), and furthermore the energy level alignment at the interface is modified by the surface dipole established by the pyridine molecules. Annealing also plays an important role to control the molecular structure and change the electronic structure together with the charge transfer properties, shown by TiOPc film. Special discussions were done for 4TBP for its ability to shift the substrate band bending by healing the oxygen vacancies, which makes it an important additive in the DSSC electrolyte. For the triphenylamine-based dye (TPAC), the systematic deposition enables the characterization of the coverage dependent changes of molecular electronic and geometric structures. The light polarization dependent charge transfer was revealed by RPES. Furthermore, the iodine doped TPAC on TiO2 were investigated to mimic the electrolyte/dye/TiO2 interface in the real DSSC.The whole work of this thesis aims to provide fundamental understanding of the interaction between photosensitive molecules on TiO2 surfaces at molecular level in the monolayer region, e.g. the formation of interfacial states and the coverage dependent atomic and electronic structures, etc. We explored the potential of the application of new dyes and modified of the existing system by identifying their advantage and disadvantage. The results may benefit the fields of dye syntheses, catalysis researches and designs of organic photovoltaic devices. / QC 20111114

Milk contains high concentrations of calcium. It occurs in two forms, a free ionic form, and calcium associated with milk proteins (caseins). The latter association is called colloidal calcium phosphate. New Zealand Dairy Foods of Takanini is marketing a range of commercial milks in supermarkets. The company uses ultra filtration to concentrate milk proteins and calcium in different milk products. During ultra filtration, the fraction that is retained by the membrane is rich in calcium bound to proteins and the portion that passes through the membrane is richer in the free ionic form. The company wanted to develop a quick and an economical method that can be applied in industrial settings to determine calcium in both these fractions and in other milk products. This research aimed to develop a quick, wet chemistry method to measure calcium in milk fractions and to trial it in an industrial environment. Two methods, the so-called EDTA method and the atomic absorption spectrophotometric method (AA) were trialled as potential reference methods against which to compare results obtained by the method to be developed. The AA method was chosen due to its ease, accuracy and precision. (This could not be selected as the industrial method for a number of reasons.) A colorimetric method was favoured over other contenders. Two colorimetric dyes, Arsenazo I and o-cresolphthalein-complexone (CPC) were chosen to work with. Arsenazo I forms a purple complex with calcium in a suitable buffer at a range of pHs. o-Cresolphthalein-complexone also forms purple-coloured complexes at alkaline pHs. During method development with Arsenazo I, different buffers were trialled and a NaOH/ KCl buffer was selected for further development at pH 12. The method worked well during the development phase but with some inconsistent results at times. o-Cresolphthalein-complexone formed clear purple complexes with Clark and Lubs and 2-amino-2-methylpropanol (AMP) buffers. The key advantage of the CPC dye with AMP buffer was that when 8-hydroxyquinoline was included in the reaction mixture, it successfully masked coloured complex formation due to CPC with magnesium, which is present in milk at about 1/3 the calcium concentration. This effect did not work with Arsenazo I. However, the results obtained with the CPC method were lower than claimed values of most milks trialled during development. Both methods were compared for their precision and it was found that CPC method has better precision and was chosen for further development. To improve the accuracy and precision, various denaturing reagents were used to (hypothetically) release calcium from the caseins. Trichloroacetic acid at 25 % was more effective than the several other denaturing treatments tested. The finalised CPC method, using trichloroacetic acid, AMP and 8-hydroxyquinoline, was then used to monitor calcium concentration over four months in three milk products, skim, Xtra (retentate) and permeate. For all milks, the CPC values were lower than the AA reference values, and the values reported by a commercial analytical laboratory. The reasons for this are discussed, as are other changes in calcium concentration in the three milks throughout the trial. The correlation between the CPC and AA values was poor for Xtra, better for skim, and best for permeate. A chemical model to explain this is discussed. The method developed is cheap and quick, and sample and reagent preparation is simple. The method could be applied in an industrial environment, but a proportionality factor would have to be applied to account for the difference in mean values between the CPC and AA methods.

Milk contains high concentrations of calcium. It occurs in two forms, a free ionic form, and calcium associated with milk proteins (caseins). The latter association is called colloidal calcium phosphate. New Zealand Dairy Foods of Takanini is marketing a range of commercial milks in supermarkets. The company uses ultra filtration to concentrate milk proteins and calcium in different milk products. During ultra filtration, the fraction that is retained by the membrane is rich in calcium bound to proteins and the portion that passes through the membrane is richer in the free ionic form. The company wanted to develop a quick and an economical method that can be applied in industrial settings to determine calcium in both these fractions and in other milk products. This research aimed to develop a quick, wet chemistry method to measure calcium in milk fractions and to trial it in an industrial environment. Two methods, the so-called EDTA method and the atomic absorption spectrophotometric method (AA) were trialled as potential reference methods against which to compare results obtained by the method to be developed. The AA method was chosen due to its ease, accuracy and precision. (This could not be selected as the industrial method for a number of reasons.) A colorimetric method was favoured over other contenders. Two colorimetric dyes, Arsenazo I and o-cresolphthalein-complexone (CPC) were chosen to work with. Arsenazo I forms a purple complex with calcium in a suitable buffer at a range of pHs. o-Cresolphthalein-complexone also forms purple-coloured complexes at alkaline pHs. During method development with Arsenazo I, different buffers were trialled and a NaOH/ KCl buffer was selected for further development at pH 12. The method worked well during the development phase but with some inconsistent results at times. o-Cresolphthalein-complexone formed clear purple complexes with Clark and Lubs and 2-amino-2-methylpropanol (AMP) buffers. The key advantage of the CPC dye with AMP buffer was that when 8-hydroxyquinoline was included in the reaction mixture, it successfully masked coloured complex formation due to CPC with magnesium, which is present in milk at about 1/3 the calcium concentration. This effect did not work with Arsenazo I. However, the results obtained with the CPC method were lower than claimed values of most milks trialled during development. Both methods were compared for their precision and it was found that CPC method has better precision and was chosen for further development. To improve the accuracy and precision, various denaturing reagents were used to (hypothetically) release calcium from the caseins. Trichloroacetic acid at 25 % was more effective than the several other denaturing treatments tested. The finalised CPC method, using trichloroacetic acid, AMP and 8-hydroxyquinoline, was then used to monitor calcium concentration over four months in three milk products, skim, Xtra (retentate) and permeate. For all milks, the CPC values were lower than the AA reference values, and the values reported by a commercial analytical laboratory. The reasons for this are discussed, as are other changes in calcium concentration in the three milks throughout the trial. The correlation between the CPC and AA values was poor for Xtra, better for skim, and best for permeate. A chemical model to explain this is discussed. The method developed is cheap and quick, and sample and reagent preparation is simple. The method could be applied in an industrial environment, but a proportionality factor would have to be applied to account for the difference in mean values between the CPC and AA methods.

With increasing concerns of global warming and the impending exhaustion of fossil fuels attention is being turned to renewable sources of energy. The sun supplies 3 x 1024 J per year to the earth which is around 104 times more energy than what the human race consumes. The world’s energy needs would be satisfied if a mere 0.1% of the planet’s surface was covered with solar cells(< = 10%)1, causing the conversion of solar energy (sunlight) into electricity to represent a very practical renewable source. Past research into solar energy has produced a photovoltaic device, which when coupled with highly coloured coordination compounds, enables this conversion. This device is known as a dye-sensitised solar cell (DSSC). Further research has been conducted into the properties of the dyes, and has shown that highly coloured coordination compounds are able to convert solar energy into electrical energy with the highest efficiencies. The dominant compounds in this area to date have been Grätzel’s ruthenium complexes and porphyrins. However, there exists a class of smaller compounds called dipyrrins, described most simply as “half a porphyrin”, which possess many of the attractive qualities for DSSC dyes. Although there are no examples of ruthenium-dipyrrin complexes in the literature, the combination of advantageous properties from both components represent very attractive synthetic targets with huge potential as dyes for DSSCs. The objectives of this thesis were firstly to develop a series of dipyrrin complexes which would be suitable as dyes for DSSCs; then to fully characterise the complexes and investigate the spectroscopic properties of each complex; and finally to determine the suitability of the complexes as dyes for DSSCs. These objectives were fully met, resulting in a set of generic target compounds characterised via 1H NMR, 13C NMR, mass spectrometry (ESI-MS), elemental analysis, and x-ray crystallography. From analyses of the UV-visible, fluorescence, emission, and Raman spectra; and electrochemistry results; the complexes were concluded to be suitable as dyes for DSSC’s. An additional bonus is that the syntheses for these complexes are applicable to any dipyrrin, thus aiding future studies into the use of dipyrrins as dyes for DSSC’s. This thesis summarises the findings of the above outlined research project.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (leaves 159-168).

Thesis (Ph. D.)--Rutgers University, 2008. / "Graduate Program in Electrical and Computer Engineering." Includes bibliographical references (p. 118-122).

Organic field-effect transistors (OFET) have attracted considerable interests as a promising technology for the next-generation flexible electronics. Thioacenes have recently emerged as potential semiconducting materials for OFETs. On the other hand, Photovoltaic (PV) technology is regarded as a prospective alternative for green and renewable energy source. Recently, dye sensitized solar cells (DSSCs) have drawn intensive attention and showed great potential for practical application. Herein, the research in this thesis would include the synthesis and characterization of novel thioacene-based semiconductors for OFET and DSSC applications. To begin with, a general review on the current status of organic semiconductors for OFET and DSSC applications was presented in Chapter 1. In chapter 2, a series of novel benzodithieno[3,2-b]thiophene derivatives (BDTT-n) with different lateral alkyloxy groups were designed and synthesized. In addition, alkyloxy-substituted benzo[2,1-b:3,4-b’]bis-[1]benzothiophenes derivatives (BBBT-n) were also synthesized. The performances of OFETs based on BDTT-n and BBBT-n have been fully investigated. Among them, BDTT-4 based OFET exhibited the highest hole mobility of 1.74 cm 2 /(Vs) with a current on/off ratio above 10 7 without annealing. In chapter 3, a novel series of naphthodithiophene-based oligomers with D-A- D-A- D structure motif were designed and synthesized. All these oligomers have 2 been fully characterized by NMR and mass spectrometry. The hole mobility properties of these oligomers were determined in OFETs as fabricated by drop- coating technique. These oligomers exhibited typical p-type semiconducting behavior. A mobility of 1.6x10 -2 cm 2 /(Vs) was demonstrated by ENBT based OFET with a current on/off ratio in the range of 10 5-7 after annealing at 160ºC. Besides, in chapter 4, a novel [pi]-bridge, namely naphthodithienothiophene was developed and employed to explore photosensitizers for DSSC application. In this work, four novel photosensitizers with D-A-[pi]-A or D-[pi]-A structure motif were designed and synthesized in which the carbazole or triphenylamine derivative was used as a donating group and benzothiadiazole was applied as auxiliary accepting group. The performances of DSSCs based on these photosensitizers have been fully investigated. Among them, CB-NDTT- CA based device exhibited the highest power conversion efficiency (PCE) of 7.29%. Meanwhile, the interfacial properties of these photosensitizers anchored on TiO 2 have also been studied by ab-initio simulation and Gaussian calculations. In chapter 5, another novel series of photosensitizers with benzodithienothiophene as the [pi]-bridge would be presented, in which different donors, auxiliary acceptors, and structures were incorporated into the frameworks of D-[pi]-A motif to investigate the relationship between the structure and properties. The performances of DSSCs based on these photosensitizers have been fully investigated, and BD-5 based device exhibited the best power conversion efficiency (PCE) of 4.66%. Furthermore, it was demonstrated that molecular engineering was an efficient way to modulate the performance of the DSSCs in 3 which benzothiadiazole was used as an effective auxiliary accepting group in constructing photosensitizers with D-A-[pi]-A structure motif. The di-anchoring approach was also found to be a promising method to design photosensitizers with improved performance.