Synthesis and Characterization of Mesoporous Semiconductors
- Author(s): Kang, Chris Byung-hwa
- Advisor(s): Tolbert, Sarah H
- et al.
Widely studied mesoporous oxide materials have a range of potential applications, such as catalysis, absorption and separation. However, they are not generally considered for their optical and electronic properties. Elemental semiconductors with nano-sized pores running through them represent a different form of framework material with physical characteristics contrasting with those of the more conventional bulk, thin film and nanocrystalline forms. This thesis describes two different routes to synthesize thin film mesoporous silicon and powder mesoporous germanium.
Thin film of mesoporous silicon was produced from thin film of mesoporous silica at low temperature (<700C) using magnesium as reducing agent. Excess magnesium risks the generation of volatile products and destruction of the bulk objects. In thin films, excess magnesium was convenient resulting in some structural loss. However, our X-ray diffraction data show that conversion to silicon and retention of order is possible even after exposure to HCl to remove magnesia and HF to remove remnant silica. Top-view SEM and low angle X-ray diffraction also proves retain in order and cross-section SEM shows retention of the surface features and pores in the bulk of the film.
Nanoscale ordered germanium composite materials were produced from solution phase using surfactant as structural directing agents. Non-classic anionic germanium Zintl clusters, discrete Ge94- or polymeric (Ge92-)n, co-assemble with cationic surfactant molecules via electrostatic interactions. Depending upon size and overall charge of polymerized Zintl clusters, shape of the inorganic/organic hybrid micelle can be varied, and the periodical nano-structures of composites can be hexagonal, lamellar, or worm-like, as determined by low angle X-ray diffraction (XRD). The anionic germanium framework of the 2-D hexagonally ordered germanium cluster/surfactant composite is condensed via oxidative coupling between the germanium Zintl clusters. EXAFS (Extended X-ray Absorption Fine Structure) study indicates that the germanium clusters were destroyed upon oxidation and tetrahedrally coordinated germanium was produced afterwards. IR absorption shows that the surface of this material is mostly hydrogen terminated. Majority of the cationic surfactant molecules inside the pores can be removed. The resulting dark brown mesoporous germanium exhibits surface area up to 500 m2/g.