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Soft x-ray fluorescence spectroscopy provides an element and angular momentum selective measure of the valence band density of states in complex materials. Results are presented demonstrating the use of SXF both as a means of solving materials problems and as a means of increasing our fundamental understanding of low energy excitation processes in various types of materials. As examples of materials applications, we discuss the L2,3 spectra of Si in various environments, and describe radiation damage studies in Beryl. Fundamental new insights are provided by the study of SXF spectra excited near an x-ray threshold. For such excitation, recent work demonstrates that an electronic Raman scattering process can greatly modify the normal fluorescence spectrum. We discuss near threshold studies of graphite, h-BN and NiS to demonstrate that the nature of the electronic excitation processes differs dramatically in various classes of materials and provides important new insights into their properties.

The full spectrum of occupied and unoccupied σ and Π orbitals is presented for solid C60, C70, and graphite, using C1s emission and absorption spectroscopy. There are significant differences between C60 and C70, and even larger changes relative to their infinite analog graphite C∞. A comparison is made with photoemission and inverse photoemission results, along with first principles quasiparticle calculations.

We are using resonant soft x-ray fluorescence at the Advanced Light Source to probe the electronic and geometric structure of novel materials. In the resonant process, a core electron is excited by a photon whose energy is near the core binding energy. In this energy regime the absorption and emission processes are coupled, and this coupling manifests itself in several ways. In boron nitride (BN), the resonant emission spectra reflect the influence of a “spectator” electron in an unoccupied excitonic state. The resonant emission can be used to distinguish between the various bulk phases of BN, and can also be used to probe the electronic structure of a monolayer of BN buried in a bulk environment, where it is inaccessible to electron spectroscopies. For highly-oriented pyrolytic graphite (HOPG) a coherent absorption-emission process takes place in the resonant regime, whereby crystalline momentum is conserved between the core excited electron and the valence hole which remains after emission

Monochromatized synchrotron radiation has been employed as the excitation source for soft x-ray emission spectroscopy. In the present paper changes in the emission spectra that occur as the excitation energy is varied near the core-absorption threshold are discussed. In the case of crystalline silicon, strong variations are seen in the L2,3 emission for excitation energies up to 30 eV above threshold. These variations are shown to be dependent on the crystalline order of the material and can be interpreted in terms of restrictions on the crystal momentum that arise in an inelastic scattering description of the combined absorption and emission. On the other hand this description is less relevant to the excitation-energy dependence of ionic insulators, in which strong phonon coupling removes these restrictions on crystal momentum. In the insulators B2O3 and BN strong variations in the emission are observed at threshold, upon creation of a core exciton: the exciton affects the emission through its influence on the phonon coupling as well as on the initial and final-state screening.