Our group has previously shown that small changes to molecular structure result in large changes to device properties and stability in organic electronic applications. By functionalizing aromatic heteroacenes with group 14 and group 16 elements, it is possible to control morphology and improve stability for a variety of applications such as thin film transistors and solar cells. Functionalization within the heteroacene core led to changes in electronic structure as observed by electrochemistry and light absorption. By substituting down the periodic table, the carbon heteroatom bond length increased, leading to subtle changes in crystal packing. Absorption maxima were red-­‐shifted and stability to light decreased. Substitution of group 14 elements to the solubilizing ethynyl groups attached to the heteroacene also had an effect on crystallization and stability. Substitution of silicon with carbon decreased solubility as well as stability to light. Substitution with germanium also decreased stability to light, but close contacts within the crystal structure and solubility in nonpolar organic solvents increased.

The rapid development in perovskite solar cells (PSC) has generated a tremendous interest in the photovoltaic community. The power conversion efficiency (PCE) of these devices has increased from 3.8% in 2009 to a recent certified efficiency of over 20% which is mainly the product of the remarkable properties of the perovskite absorber material. One of the most important advances occurred with the replacement of the liquid electrolyte with a solid state hole conductor which enhanced PCE values and improved the device stability. Spiro-OMeTAD (2,2',7,7'-tetrakis(N,N'-di-p-methoxyphenylamine)- 9,9'-spirobifluorene) is the most common hole transport material in perovskite solar cells. Nevertheless, the poor conductivity, low charge transport and expensive synthetic procedure and purification have limited its commercialisation. Triphenylamines (TPA) like Spiro-OMeTAD are commonly employed due to the easy oxidation of the nitrogen centre and good charge transport. Other triarylamines have similar properties to Spiro-OMeTAD but are easier to synthesise. The aim of this doctoral thesis is to investigate different types of hole transport materials in perovskite solar cells. Three different series of triphenylamine-based HTM were designed, synthesised, characterised and studied their function in perovskite solar cells. A series of five diacetylide-triphenylamine (DATPA) derivatives (Chapter 3) with different alkyl chain length in the para position was successfully synthesised through a five step synthesis procedure. A range of characterisation techniques was carried out on the molecules including; optical, electrochemical, thermal and computational methods. The results show that the new HTMs have desirable optical and electrochemical properties, with absorption in the UV, a reversible redox property and a suitable highest occupied molecular orbital (HOMO) energy level for hole transport. Perovskite solar cell device performances were studied and discussed in detail. This project studied the effect of varying the alkyl chain length on structurally similar triarylamine-based hole transport materials on their thermal, optical, electrochemical and charge transport properties as well as their molecular packing and solar cell parameters, thus providing insightful information on the design of hole transport materials in the future. The methoxy derivative showed the best semiconductive properties with the highest charge mobility, better interfacial charge transfer properties and highest PCE value (5.63%). The use of p-type semiconducting polymers are advantageous over small molecules because of their simple deposition, low cost and reproducibility. Styrenic triarylamines (Chapter 4) were prepared by the Hartwig-Buchwald coupling followed by their radical polymerization. All monomers and polymers were fully characterised through electrochemical, spectroscopic and computational techniques showing suitable HOMO energy levels and desirable optoelectrochemical properties. The properties and performance of these monomers and polymers as HTMs in perovskite solar cells were compared in terms of their structure. Despite the lower efficiencies, the polymers showed superior reproducibility on each of the device parameters in comparison with the monomers and spiro-OMeTAD. Finally, star-shaped structures combine the advantages of both small molecules, like well-defined structures and physical properties, and polymers such as good thermal stability. Two star-shaped triarylamine-based molecules (Chapter 5) were synthesised, fully characterised and their function as hole-transport materials in perovskite solar cells studied. These materials afford a PCE of 13.63% and high reproducibility and device stability. In total this work provided three series of triarylamine-based hole transport materials for perovskite solar cells application and enabled a comparison of the pros and cons of different design structures: small-molecule, polymeric and star-shaped.