Iron Resonant Photoemission Spectroscopy on Anodized Hematite Points to Electron Hole Doping during Anodization

Anodization of a-Fe2O3 (hematite) electrodes in alkaline electrolyte under constant potential conditions the electrode surface in a way that an additional current wave occurs in the cyclic voltammogram. The energy position of this current wave is closely below the potential of the anodization treatment. Continued cycling or exchanging of the electrolyte causes depletion of this new feature. The O 1s and Fe 2p core-level X-ray photoelectron spectra (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectra of such conditioned hematite exhibit a chemical shift towards higher binding energies, in line with the general perception that anodization generates oxide species with dielectric properties. The valence band XPS and particularly the iron resonant valence band photoemission spectra, however, are shifted towards the opposite direction, that is, towards the Fermi energy, suggesting that hole doping on hematite has taken place during anodization. Quantitative analysis of the Fe 2p resonant valence band photoemission spectra shows that the spectra obtained at the Fe 2p absorption threshold are shifted by virtually the same energy as the anodization potential towards the Fermi energy. The tentative interpretation of this observation is that anodization forms a surface film on the hematite that is specific to the anodization potential.

Kinks in the angle resolved photoemission and inelastic x-ray spectra of high temperature superconductors

Jeff Graf

Though the high superconducting transition temperature (Tc) is the most interesting technological aspect of high temperature superconductors, the complex way in which the spin, lattice and electronic degrees of freedom interplay, makes them of the highest scientific interest. This is illustrated by their rich phase diagram characterized by a variety of exotic groundstate including; Mott insulating, pseudogap and high temperature superconductivity. One of the most serious barriers that has prevented our understanding of the mechanism of high temperature superconductors thus far is the lack of information on how low energy Landau quasiparticles result from an organization of real particles. This organization, often colloquially referred to as "dressing", is a fundamental general concept in physics that explains a variety of physical phenomena, such as exotic particle formations and phase transitions. The role of the lattice in this dressing is particularly controversial. Phonons are quanta of lattice vibration energy, and play a crucial role in conventional superconductivity. They provide an attractive interaction allowing the electrons to condensate in superconducting Cooper pairs. However, high temperature superconductivity in the cuprates in achieved through hole doping in an antiferromagnetic Mott insulator. In this case, the antiferromagnetic background, the strong coulomb repulsion and the anisotropic superconducting gap all suggest a marginal role of the phonons. In order to assess experimentally the exact role of the phonon, angle resolved photoemission spectroscopy (ARPES) is the weapon of choice given its unique ability to probe the electronic structure of solids in an energy- and momentum-resolved manner. In this thesis, I will use ARPES to characterize the various form of dressing of the quasiparticles in the high temperature superconductor from the Fermi level all the way to the valence band complex. I'll show that when combined with isotope substitution and inelastic x-rays scattering, the strong electron-phonon interaction can be probed in vivid details. This thesis presents three fundamental results. 1) Using the isotope effect, the important and unusual role of the phonon is demonstrated, as well as the strong interplay between the magnetic and phonic degrees of freedom. 2) Using inelastic scattering, the intriguing interplay between the Fermi surface and the bond stretching phonon is exposed. And 3) By exploring the ARPES data up to high energy, two new energy scales at high binding energy as well as the spectral waterfalls phenomenon are revealed. When all these new elements are considered together, they clearly show the need to consider simultaneously the spin, lattice, Fermi surface topology and electronic degrees of freedom. The spectacular progress in ARPES techniques over the past two decades was critical for these results, and I will present in this thesis our current effort in pushing the techniques even further. In particular I'll present my efforts in building a laser based ARPES setup with a hemispherical analyzer and a spin resolved time of flight analyzer.

EPFL2008

Role of the Triiodide/Iodide Redox Couple in Dye Regeneration in p-Type Dye-Sensitized Solar Cells

Ulf Anders Hagfeldt, Yann Pellegrin

A series of perylene dyes with different optical and electronic properties have been used as photosensitizers in NiO-based p-type dye-sensitized solar cells. A key target is to develop dyes that absorb light in the red to near-IR region of the solar spectrum in order to match photoanodes optically in tandem devices; however, the photocurrent produced was found to decrease dramatically as the absorption maxima of the dye used was varied from 517 to 565 nm and varied strongly with the electrolyte solvent (acetonitrile, propionitrile, or propylene carbonate). To det. the limitations of the energy properties of the dye mols. and to provide guidelines for future sensitizer design, we have detd. the redox potentials of the diiodide radical intermediate involved in the charge-transfer reactions in different solvents using photomodulated voltammetry E°(I3-/I2·-)(V vs. Fe(Cp)2+/0) = -0.64 for propylene carbonate, -0.82 for acetonitrile, and -0.87 for propionitrile. Inefficient regeneration of the sensitizer appears to be the efficiency-limiting step in the device, and the values presented here will be used to design more efficient dyes, with more cathodic redn. potentials, for photocathodes in tandem dye-sensitized solar cells.

2012

Ultrafast Optical Control of the Electronic Properties of ZrTe5

Helmuth Berger, Philippe Bugnon, Alberto Crepaldi, Marco Grioni, Arnaud Magrez

We report on the temperature dependence of the ZrTe5 electronic properties, studied at equilibrium and out of equilibrium, by means of time and angle resolved photoelectron spectroscopy. Our results unveil the dependence of the electronic band structure across the Fermi energy on the sample temperature. This finding is regarded as the dominant mechanism responsible for the anomalous resistivity observed at T* similar to 160 K along with the change of the charge carrier character from holelike to electronlike. Having addressed these long-lasting questions, we prove the possibility to control, at the ultrashort time scale, both the binding energy and the quasiparticle lifetime of the valence band. These experimental evidences pave the way for optically controlling the thermoelectric and magnetoelectric transport properties of ZrTe5.

Amer Physical Soc2015

Kinks in the angle resolved photoemission and inelastic x-ray spectra of high temperature superconductors

Jeff Graf

EPFL2008