SYNTHESIS OF TITANIA THIN FILMS WITH CONTROLLED MESOPORE ORIENTATION: NANOSTRUCTURE FOR ENERGY CONVERSION AND STORAGE

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

Incorporating Poly(3-hexyl thiophene) into Orthogonally Aligned Cylindrical Nanopores of Titania for Optoelectronics

The incorporation of hole conducting polymer poly(3-hexyl thiophene) (P3HT) into the 8-9 nm cylindrical nanopores of titania is investigated using films with a unique orthogonally oriented hexagonal close packed mesostructure. The films are synthesized using evaporation induced self-assembly (EISA) with Pluronic triblock copolymer F127 as the structure directing agent. The orthogonally oriented cylindrical nanopore structure was chosen over a cubic structure because confinement in uniform cylindrical channels is hypothesized to enhance hole conductivity of P3HT by inducing local polymer chain ordering. Orthogonal orientation of the cylindrical nanopores is achieved by modifying the substrate (FTO-coated glass slides) with crosslinked F127. After thermal treatment to remove organic templates from the films, P3HT is infiltrated into the nanopores by spin coating a 1 wt% P3HT solution in chlorobenzene onto the titania films followed by thermal annealing under vacuum at 200 °C. The results show that infiltration is essentially complete after 30 minutes of annealing, with little or no further infiltration thereafter. A final infiltration depth of ~14 nm is measured for P3HT into the nanopores of titania using neutron reflectometry measurements. Photoluminescence measurements demonstrate that charge transfer at the P3HT-TiO2 interface improves as the P3HT is infiltrated into the pores, suggesting that an active organic-inorganic heterojuction is formed in the materials