We investigate band bending, electron affinity and work function of differently terminated, doped and oriented diamond surfaces by X-ray and ultraviolet photoelectron spectroscopy ( XPS and UPS ). The diamond surfaces were polished by a hydrogen plasma treatment and present a mean roughness below 10 Å . The hydrogen-terminated diamond surfaces have negative electron affinity (NEA), whereas the hydrogen-free surfaces present positive electron affinity (PEA). The NEA peak is only observed for the borondoped diamond (100)-(2×1):H surface, whereas it is not visible for the nitrogen-doped diamond (100)-(2×1):H surface due to strong upward band bending. For the boron-doped diamond (111)-(1×1):H surface, the NEA peak is also absent due to the conservation of the parallel wavevector component (k d ) in photoemission. Electron emission from energy levels below the conduction band minimum (CBM ) up to the vacuum level E vac allowed the electron affinity to be measured quantitatively for PEA as well as for NEA. The emission from populated surface states forms a shoulder or a peak at lower kinetic energies, depending on the NEA behavior and additionally shows a dispersion behavior. The low boron-doped diamond (100)-(2×1):H surface presents a highintensity NEA peak with a FWHM of 250 meV. Its cut-off is situated at a kinetic energy of 4.9 eV, whereas the upper limit of the vacuum level is situated at 3.9 eV, resulting in a NEA of at least −1.0 eV and a maximum work function of 3.9 eV. The high-borondoped diamond (100) surface behaves similarly, showing that the NEA peak is present due to the downward band bending independent of the boron concentration. The nitrogen-doped (100)-(2×1):H surface shows a low NEA of −0.2 eV but no NEA peak due to the strong upward band bending. The (111)-(1×1):H surface does not show a NEA peak due to the k d conservation in photoemission; E vac is situated at 4.2 eV or below, resulting in a NEA of at least −0.9 eV and a maximum work function of 4.2 eV. The high-intensity NEA peak of boron-doped diamond seems to be due to the downward band bending together with the reduced work function because of hydrogen termination. Upon hydrogen desorption at higher annealing temperatures, the work function increases, and NEA disappears. For the nitrogen-doped diamond (100) surface, the work function behaves similarly, but the observation of a NEA peak is absent because of the surface barrier formed by the high upward band bending.

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We have investigated the field emission properties of nanotube thin films deposited by a plasma enhanced chemical vapor deposition process from 2% CH4 in H2 atmosphere. Depending on the deposition of the metallic catalyst [Fe(NO3)3 in an ethanol solution or sputtered Ni] the nanotube films showed a nested or continuous dense distribution of tubes. The films consisted of multiwalled nanotubes (MWNTs) with diameters ranging from 40 down to 5 nm, with a large fraction of the tubes having open ends. The nanotube thin film emitters showed a turn-on field of less than 2 V μm−1 for an emission current of 1 nA. An emission site density of 10 000 emitters per cm−2 is achieved at fields around 4 V μm−1. The emission spots, observed on a phosphorous screen, show various irregular structures, which we attribute to open ended tubes. A combined measurement of the field emitted electron energy distribution (FEED) and the current-voltage characteristic allowed us to determine the work function at the field emission site. In the case of the MWNT thin films and arc discharge grown MWNTs we found work function values around 5 eV, which agree well with the global work function of 4.85 eV we determined by photoelectron spectroscopy. From the shape of the FEED peaks we can conclude that the field emission originates from continuum states at the Fermi energy, indicating the metallic character of the emission site. In the case of single-walled nanotubes we found significantly lower work function values of around 3.7 eV compared to those of MWNTs. We attribute this to a size dependent electrostatic effect of the image potential, which lowers the work function for small (<5 nm) structures.

Phase pure nanotube films were grown on silicon substrates by a microwave plasma under conditions which normally are used for the growth of chemical vapor deposited diamond films. However, instead of using any pretreatment leading to diamond nucleation we deposited metal clusters on the silicon substrate. The resulting films contain only nanotubes and also onion-like structures. However, no other carbon allotropes like graphite or amorphous clustered material could be found. The nanotubes adhere very well to the substrates and do not need any further purification step. Electron field emission was observed at fields above 1.5 V/μm and we observed an emission site density up to 104/cm2 at 3 V/μm. Alternatively, we have grown nanotube films by the hot filament technique, which allows to uniformly cover a two inch wafer.

The nitrogen-doped (N-doped ), type Ib, synthetic diamond (100) surface was investigated by means of X-ray photoelectron spectroscopy ( XPS) and ultraviolet photoelectron spectroscopy ( UPS ). Photoelectron emission data from the boron-doped (B-doped ) and the N-doped diamond (100) surfaces were compared and permitted the energy band diagrams for these differently terminated surfaces to be drawn. We observed emission from energy levels below the conduction band minimum up to the vacuum level and therefore succeed in evaluating the negative electron affinity (NEA) of the hydrogen-terminated diamond surfaces. Both the hydrogen-terminated N-and B-doped diamond (100) surfaces show NEA values of at least −0.2 and −1.0 eV, respectively, while the hydrogen-free surfaces show positive electron affinity. In contrast to the hydrogen-terminated B-doped (100) surface, UPS measurements on the hydrogen-terminated N-doped (100) surface do not reveal a high intensity NEA peak owing to the strong upward band bending. The high intensity NEA peak of B-doped diamond seems to be due to the downward band bending together with the reduced work function because of hydrogen termination. The work function increases for subsequent hydrogen desorption at higher annealing temperatures with associated loss of NEA. For the N-doped diamond (100) surface the work function behaves similarly but the observation of a NEA peak is absent because of the surface barrier formed by the upward band bending.