Graduation Year

2011

Document Type

Dissertation

Degree

Ph.D.

Degree Granting Department

Chemistry

Major Professor

Rudy Schlaf

Keywords

cadmium selenide, dye-sensitized solar cell, electrospray, titanium dioxide, work function, zinc oxide

Abstract

In this study, photoemission spectroscopy (PES) was used to investigate the electronic properties of nanocrystalline titanium dioxide (TiO2), zinc oxide (ZnO), and cadmium selenide (CdSe). Electrospray deposition technique enabled the preparation of thin films in vacuum from a dispersion prepared outside the vacuum chamber. This method also allowed the step-wise formation of interfaces and the monitoring of the evolution of the electronic structure with intermittent PES characterization. The work function of nanocrystalline TiO2 and ZnO was measured with ultraviolet photoemission spectroscopy (UPS) and low-intensity x-ray photoemission spectroscopy (LIXPS). Measurements on environmentally contaminated surfaces revealed an instantaneous and permanent work function decrease of 0.3-0.5 eV upon exposure to ultraviolet radiation during a UPS measurement. The work function reduction is likely to be related to the formation of a surface dipole caused by the photo-chemical hydroxylation of surface defects. This phenomenon was further investigated with regard to its influence on the electronic structure of the indium tin oxide (ITO)/TiO2 interface found in dye-sensitized solar cells. The experiments suggest that UV radiation can cause a small but significant change of the charge injection barriers at the interface. The determined band line-ups revealed electron injection barriers of ~0.3-0.5 eV, while UV radiation caused an increase of about 0.15 eV. This might have the potential to further impede electron transfer to the ITO electrode and affect the performance of solar cell device. Another type of photovoltaic cell using nanocrystalline material is a heterojunction bulk solar cell. Conversion efficiencies of such devices are currently only about 3% due to the inefficient charge separation at interfaces formed by blending organic and inorganic material. An approach to improve efficiencies in such devices is the use of covalently bonded conductive polymer/inorganic hybrid nanocrystals. In this study a prototypical model system was investigated with PES with the aim to develop a measurement protocol that allows the determination of electronic properties for such hybrid materials. The comparison of the relative core-level binding energies of the organics-functionalized CdSe nanocrystal compared to the ligand-free CdSe nanocrystal and the arylselenophosphate ligand material enabled the determination of the electronic structure at the interface. Core-level measurements support the hypothesis that the Se functionality of the organic ligand coordinates to the Cd sites on the nanopthesis surface.

Share

COinS