Solution-based Syntheses of Iron Pyrite Thin Films for Photovoltaic and Protein Foot-printing Applications
- Author(s): El Makkaoui, Mohammed
- Advisor(s): Law, Matt D
- et al.
Iron pyrite (cubic FeS2) is a non-toxic, earth abundant semiconductor possessing a set of excellent optical/electronic properties for serving as an absorber layer in PV devices. Additionally, pyrite is a very efficient hydroxyl radical generator via Fenton chemistry and has shown promise in oxidative protein and DNA foot-printing application. The main focus of this thesis is on fabricating phase and elementally pure iron pyrite thin films using a solution-based approach that employs hydrazine as a solvent. A precursor ink is formed at room temperature by mixing elemental iron and sulfur in anhydrous hydrazine and then deposited on Mo-coated glass substrates, via spin coating, to yield amorphous iron sulfide films that are then annealed in H2S (340 o C) and sulfur gas (≤ 500 o C) to form uniform, polycrystalline and phase pure pyrite films with densely packed grains. This approach is likely to yield the most elementally pure pyrite thin films made to date, through a very simple and scalable process. The ink has shown to be very sensitive to environmental conditions and has a very short shelf life (~1 day). Additionally, the film microstructure is greatly influenced by the S:Fe concentration ratio that when tuned to 3:1, yielded uniform, robust and optically flat iron sulfide thin films with an optimal thickness (~320 nm) for PV application. The results however were not reproducible, mainly due to failure in applying multiple layers without compromising film morphology. Thinner (< 100 nm) iron sulfide films, on the other hand, are reproducibly produced, but are too thin to be employed in PV devices. Direct annealing in sulfur gas at 475 o C for 4 hours, bypassing the > 12 hour H2S annealing step, yielded phase pure pyrite films, with good morphology, at lower processing time and annealing temperatures (< 500 o C). The latter part of this thesis regards the use of pyrite nano-crystals in conjunction with high surface area polymer laminates for protein foot-printing application in collaboration with the Brenowitz lab at the Albert Einstein College of Medicine and the Khine lab at the University of California, Irvine. A thin film of pyrite nano-crystals is spray deposited (Video in supplementary) onto a shape memory polymer that is then thermally treated with a heat gun, causing the sheet to retract and stiffen as the nanocrystalline layer crumples and integrates into the polyolefin, forming a mechanically robust and highly reactive laminate of pyrite nano-crystals. Micro-wells are thermoformed into the laminate under negative pressure. ·OH dose-oxidation response relationship were established via varying the H2O2 concentration and reaction time. The flexibility, cost effectiveness and scalability of this platform enables integration into macro-structural analysis systems. Pyrite shrink laminates and hydrazine ink films were characterized by Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), and Raman Spectroscopy. Drop deposition oxidation experiments and MALDI-TOF "Matrix Assisted Laser Desorption/Ionization-Time of Flight" Mass Spectroscopy of protein aliquots reacted on PSWL were conducted in the Brenowitz lab at the department of biochemistry at the Albert Einstein College of Medicine in New York.