Year of Publication


Degree Name

Doctor of Philosophy (PhD)

Document Type

Doctoral Dissertation




Chemical and Materials Engineering

First Advisor

Dr. Stephen E. Rankin


This dissertation addresses the synthesis mechanism of mesoporous titania thin films with 2D Hexagonal Close Packed (HCP) cylindrical nanopores by an evaporation-induced self-assembly (EISA) method with Pluronic surfactants P123 and F127 as structure directing agents, and their applications in photovoltaics and lithium ion batteries. To provide orthogonal alignment of the pores, surface modification of substrates with crosslinked surfactant has been used to provide a chemically neutral surface. GISAXS studies show not only that aging at 4°C facilitates ordered mesostructure development, but also that aging at this temperature helps to provide orthogonal orientation of the cylindrical micelles which assemble into an ordered mesophase directly by a disorder-order transition. These films provide pores with 8-9 nm diameter, which is precisely the structure expected to provide short carrier diffusion length and high hole conductivity required for efficient bulk heterojunction solar cells. In addition, anatase titania is a n-type semiconductor with a band gap of +3.2 eV. Therefore, titania readily absorbs UV light with a wavelength below 387 nm. Because of this, these titania films can be used as window layers with a p-type semiconductor incorporated into the pores and at the top surface of the device to synthesize a photovoltaic cell. The pores provide opportunities to increase the surface area for contact between the two semiconductors, to align a p-type semiconductor at the junction, and to induce quantum confinement effects.

These titania films with hexagonal phase are infiltrated with a hole conducting polymer, poly(3-hexylthiophene) (P3HT), in order to create a p-n junctions for organic-inorganic hybrid solar cells, by spin coating followed by thermal annealing. This assembly is hypothesized to give better photovoltaic performance compared to disordered or bicontinuous cubic nanopore arrangements; confinement in cylindrical nanopores is expected to provide isolated, regioregular “wires” of conjugated polymers with tunable optoelectronic properties, such as improved hole conductivity over that in bicontinuous cubic structure. The kinetics of infiltration into the pores show that maximum infiltration occurs within less than one hour in these films, and give materials with improved photovoltaic performance relative to planar TiO2/P3HT assemblies. These oriented mesoporous titania films are also used to develop an inorganic solar cell by depositing CdTe at the top using the Close Spaced Sublimation (CSS) technique. A power conversion efficiency of 5.53% is measured for heterostructures built using mesoporous titania films, which is significantly enhanced relative to planar TiO2/CdTe devices and prior reports in the literature. These mesoporous titania films have a great potential in inorganic solar cell development and can potentially replace CdS window layers which are conventionally used in inorganic CdS-CdTe solar cells. The last part of the dissertation addresses layer-by-layer synthesis to increase the thickness of mesoporous titania films with vertically oriented 2D-HCP nanopores, and their use in lithium ion batteries as negative electrodes because of advantages such as good cycling stability, small volume expansion (~3%) during intercalation/extraction and high discharge voltage plateau. The high surface area and small wall thickness of these titania films provide excellent lithium ion insertion and reduced Li-ion diffusion length, resulting in stable capacities as high as 200-250 mAh/g over 200 cycles.

Digital Object Identifier (DOI)