Nanoscale fabrication and characterization of chemically modified silicon surfaces using conductive atomic force microscopy in liquids

This dissertation examines the modification and characterization of hydrogen-terminated silicon surfaces in organic liquids. Conductive atomic force microscope (cAFM) lithography is used to fabricate structures with sub-100 nm line width on H:Si(111) in n-alkanes, 1-alkenes, and 1-alkanes. Nanopatterning is accomplished by applying a positive (n-alkanes and 1-alkenes) or a negative (1-alkanes) voltage pulse to the silicon substrate with the cAFM tip connected to ground. The chemical and kinetic behavior of the patterned features is characterized using AFM, lateral force microscopy, time-of-flight secondary ion mass spectroscopy (TOF SIMS), and chemical etching. Features patterned in hexadecane, 1-octadecene, and undecylenic acid methyl ester exhibited chemical and kinetic behavior consistent with AFM field induced oxidation. The oxide features are formed due to capillary condensation of a water meniscus at the AFM tip-sample junction. A space-charge limited growth model is proposed to explain the observed growth kinetics. Surface modifications produced in the presence of neat 1-dodecyne and 1-octadecyne exhibited a reduced lateral force compared to the background H:Si(111) substrate and were resistant to a hydrofluoric acid etch, characteristics which indicate that the patterned features are not due to field induced oxidation and which are consistent with the presence of the methyl-terminated 1-alkyne bound directly to the silicon surface through silicon-carbon bonds.; In addition to the cAFM patterned surfaces, full monolayers of undecylenic acid methyl ester (SAM-1) and undec-10-enoic acid 2-bromoethyl ester (SAM-2) were grown on H:Si(111) substrates using ultraviolet light. The structure and chemistry of the monolayers were characterized using AFM, TOF SIMS, X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), X-ray standing waves (XSW), and X-ray fluorescence (XRF). These combined analyses provide evidence that SAM-1 and SAM-2 form dense monolayers with areal densities corresponding to 50% and 57% of the Si(111) surface bonds. XPS and XSW analyses of SAM-2 reveal that Br abstraction by reactive silicon dangling bonds competes with olefin addition to the surface so that 0.48 monolayer (ML) of a total Br coverage of 0.58 ML is bound to the Si(111) lattice position.