Date Awarded

Spring 2011

Document Type


Degree Name

Doctor of Philosophy (Ph.D.)


Applied Science


Ron A Outlaw


Recent progress and a coordinated national research program have brought considerable effort to bear on the synthesis and application of carbon nanostructures for field emission. at the College of William and Mary, we have developed field emission arrays of vertically oriented graphene (carbon nanosheets, CNS) that have demonstrated promising cathode performance, delivering emission current densities up to 2 mA/mm2 and cathode lifetime > 800 hours. The work function ( & phis;) of CNS and other carbonaceous cathode materials has been reported to be &phis;∼4.5-5.1 eV. The application of low work function thin films can achieve several orders of magnitude enhancement of field emission.;Initially, the intrinsic CNS field emission was studied. The mean height of the CNS was observed to decrease as a function of operating time at a rate of ∼0.05 nm/h (I 1 ∼ 40 muA/mm2). The erosion mechanism was studied using a unique UHV diode design which allowed line-of-site assessment from the field emission region in the diode to the ion source of a mass spectrometer. The erosion of CNS was found to occur by impingement of hyperthermal H and O neutrals and ions generated at the surface oxide complex of the Cu anode by electron stimulated desorption. Techniques for minimizing this erosion are presented. ; The Mo2C (&phis;∼3.7 eV) beading on CNS at previously reported carbide formation temperatures of ∼800 ?? C was circumvented by physical vapor deposition of Mo and vacuum annealing at ∼300??C which resulted in a conformal Mo2C coating and stable field emission of 1 ∼ 50 muA/mm2. For a given applied field, the emission current was > 102 greater than uncoated CNS.;ThO2 thin film coatings were presumed to be even more promising because of a reported work function of &phis; ∼2.6 eV. The fundamental behavior of the initial oxidation of polycrystalline Th was studied in UHV (p < 1x10-11 Torr), followed by studies of thin film coatings on Ir and thermionic emission characteristics. Although a work function of 3.3 eV was determined by a RichardDushman plot, activation of the thin film was not achieved at T < 1700??C. Rather, the deposited ThO2 film decomposed, surface diffused and aggregated into stable ThO2(111) crystallites.;Thin film ThO2 coatings deposited on CNS initially demonstrated excellent field emission (up to ∼2 muA/mm2) and apparently activated spontaneously without significant thermal energy. Fowler-Nordheim plots suggested a work function of &phis; ∼2.6 eV. Undesired beading and ThO2 surface diffusion away from active emission sites resulted in rapidly deteriorating performance at higher field emission currents. Techniques that should provide a more stable ThO2/CNS conformal coating are presented.;The impact of thin films of Mo2C and ThO2on the magnitude of field emission from carbon nanosheets (CNS) was substantial. For a given field emission current density, J ∼2 muA/mm 2, the necessary applied field for uncoated CNS was ∼12 V/mum, but only ∼8 V/mum when coated with Mo2C (&phis;∼3.7 eV) and ∼5 V/mum when coated with ThO2 (&phis;∼2,6 eV). The mechanism for enhanced emission and the stability of the coatings are discussed, with special focus on the activation of ThO2 thin films. The major limitation observed in these studies has been the difference in surface energy of the graphene and the coatings which resulted in a tendency for the films to bead and separate from active emission sites at elevated currents. Suggested techniques to prevent this unwanted surface diffusion are presented.



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