X-ray photoemission spectroscopy of nonmetallic materials: Electronic structures of boron and BxOy

Although an increasing volume of x-ray photoemission spectroscopic (XPS) data has been accumulated on boron and boron-rich compounds because of their unusual properties, including a unique three-center, two-electron bonding configuration, their common nonmetallic nature has been overlooked. Typically, the measured energy-state data are not clarified by surface Fermi level positions of these nonmetallic samples, which compromises the scientific contents of the data. In the present study, we revisited the XPS studies of sputter-cleaned β-rhombohedral boron (βr-B), the oxidized surface of βr-B, B6O pellet, and polished B2O3, to illustrate the impact and resolution of this scientific issue. These samples were chosen because βr-B is the most thermodynamically stable polytype of pure boron, B2O3 is its fully oxidized form, and B6O is the best known superhard family member of boron-rich compounds. From our XPS measurements, including those from a sputter-cleaned gold as a metal reference, we deduced that our βr-B had a surface Fermi level located at 0.7±0.1 eV from its valence-band maximum (VBM) (referred as EFL) and a binding energy for its B 1s core level at 187.2 eV from VBM (Eb,VBM). The latter attribute, unlike typical XPS binding energy data that are referenced to a sample-dependent Fermi level (Eb,FL), is immune from any uncertainties and variations arising from sample doping and surface charging. For bulk B2O3, we found an Eb,VBM for its B 1s core level at 190.5 eV and an Eb,FL at 193.6 eV. For our βr-B subjected to a surface oxidation treatment, an overlayer structure of ∼1.2 nm B2O3/∼2 nm B2O/B was found. By comparing the data from this sample and those from βr-B and bulk B2O3, we infer that the oxide overlayer carried some negative fixed charge and this induced on the semiconducting βr-B sample an upward surface band bending of ∼0.6 eV. As for our B6O sample, we found an EFL of ∼1.7 eV and two different chemical states having Eb,VBM of 185.4 and 187.2 eV, with the former belonging to boron with no oxygen neighbor and the latter to boron with an oxygen neighbor. The methodology in this work is universally applicable to all nonmetallic samples.