Characterization of buried interfaces using Ga Kα hard X-ray photoelectron spectroscopy (HAXPES).

The extension of X-ray photoelectron spectroscopy (XPS) to measure layers and interfaces below the uppermost surface requires higher X-ray energies and electron energy analysers capable of measuring higher electron kinetic energies. This has been enabled at synchrotron radiation facilities and by using lab-based instruments which are now available with sufficient sensitivity for measurements to be performed on reasonable timescales. Here, we detail measurements on buried interfaces using a Ga Kα (9.25 keV) metal jet X-ray source and an EW4000 energy analyser (ScientaOmicron GmbH) in the Henry Royce Institute at the University of Manchester. Development of the technique has required the calculation of relative sensitivity factors (RSFs) to enable quantification analogous to Al Kα XPS, and here we provide further substantiation of the Ga Kα RSF library. Examples of buried interfaces include layers of memory and energy materials below top electrode layers, semiconductor heterostructures, ions implanted in graphite, oxide layers at metallic surfaces, and core-shell nanoparticles. The use of an angle-resolved mode enables depth profiling from the surface into the bulk, and is complemented with surface-sensitive XPS. Inelastic background modelling allows the extraction of information about buried layers at depths up to 20 times the photoelectron inelastic mean free path.

Electronic properties of the interface between p-CuI and anatase-phase n-TiO2 single crystal and nanoparticulate surfaces: a photoemission study.

We present a study of the growth of the p-type inorganic semiconductor CuI on n-type TiO2 anatase single crystal (101) surfaces and on nanoparticulate anatase surfaces using synchrotron radiation photoemission spectroscopy. Core level photoemission data obtained using synchrotron radiation reveal that both the substrate (TiO2) and the overlayer (CuI) core levels shift to a lower binding energy to different degrees following the growth of CuI on TiO2. Valence band photoemission data show that the valence band maximum of the clean substrate differs from that of the dosed surface which may be interpreted qualitatively as due to the introduction of a new density of states within the band gap of TiO2 as a result of the growth of CuI. The valence band offset for the heterojunction n-TiO2p-CuI has been measured using photoemission for both nanoparticulate and single crystal TiO2 surfaces, and the band energy alignment for these heterojunction interfaces is presented. With the information obtained here, it is suggested that the interface between p-CuI and single crystal anatase-phase n-TiO2 is a type-II heterojunction interface, with significant band bending. The measured total band bending matches the work function change at the interface, i.e., there is no interface dipole. In the case of the nanoparticulate interface, an interface dipole is found, but band bending within the anatase nanoparticles remains quite significant. We show that the corresponding depletion layer may be accommodated within the dimension of the nanoparticles. The results are discussed in the context of the functional properties of dye-sensitized solid state solar cells.

Resonant photoemission from complex cuprates and nickelates.

Synchrotron-excited resonant-photoemission measurements at rare-earth 4d --> 4f and transition-metal 3p --> 3d thresholds have been carried out using a variety of complex cuprates and nickelates on stations 6.1 (grazing-incidence monochromator) and 6.2 (toroidal-grating monochromator) at the SRS CLRC Daresbury Laboratory. The systems studied are Nd(2)Ni(1 - x)Cu(x)O(4), La(2 - x)Sr(x)Ni(1- y)Fe(y)O(4 + delta) and Bi(2)Sr(2)Ca(1 - x)Y(x)Cu(2)O(8 + delta). A combination of EDC and constant-initial-state data is used to examine the 4f and 3d contributions to the valence-band density of states and their binding-energy positions relative to the Fermi energy. This allows the study of the valence states of the transition-metal ions and their modulation on doping. For La(2 - x)Sr(x)Ni(1 - y)Fe(y)O(4 + delta), this approach is used to infer a valence state of >/= 3.0 for Fe. In the case of Bi(2)Sr(2)Ca(1 - x)Y(x)Cu(2)O(8 + delta), the effect of Cu valence modulation on the 3p resonance is observed as x is varied. This is discussed in the light of controversy surrounding shifts in core-level photoemission with doping for this system.

The k-space components of a photoelectron from an arbitrarily oriented crystal face.

A standard rotational matrix method is described for determining the k-space components of photoelectrons emitted from a crystal surface, which is arbitrarily oriented with respect to the experimental frame. This simplifies the analysis of angle-resolved photoemission data from a crystal surface not aligned to the experimental chamber axes.