Soft x-ray spectroscopy studies of novel electronic materials using synchrotron radiation
Newby Jr., David Henry
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Soft x-ray spectroscopy can provide a wealth of information on the electronic structure of solids. In this work, a suite of soft x-ray spectroscopies is applied to organic and inorganic materials with potential applications in electronic and energy generation devices. Using the techniques of x-ray absorption (XAS), x-ray emission spectroscopy (XES), and x-ray photoemission spectroscopy (XPS), the fundamental properties of these different materials are explored. Cycloparaphenylenes (CPPs) are a recently synthesized family of cyclic hydrocarbons with very interesting properties and many potential applications. Unusual UV/Visible fluorescence trends have spurred a number of theoretical investigations into the electronic properties of the CPP family, but thus far no comprehensive electronic structure measurements have been conducted. XPS, XAS, and XES data for two varieties, - and -CPP, are presented here, and compared with the results of relevant DFT calculations. Turning towards more application-centered investigations, similar measurements are applied to two materials commonly used in solid oxide fuel cell (SOFC) cathodes: La_(1−x)Sr_(x)MnO_(3) (LSMO) and La_(1−x)Sr_(x)Co_(1−y)Fe_(y)O_(3) (LSCF). Both materials are structurally perovskites, but they exhibit strikingly different electronic properties. SOFC systems very efficiently produce electricity by catalyzing reactions between oxygen and petroleum-based hydrocarbons at high temperatures (> 800 C). Such systems are already utilized to great effect in many industries, but more widespread adoption could be had if the cells could operate at lower temperatures. Understanding the electronic structure and operational evolution of the cathode materials is essential for the development of better low-temperature fuel cells. LSCF is a mixed ion-electron conductor which holds promise for low-temperature SOFC applications. XPS spectra of LSCF thin films are collected as the films are heated and gas-dosed in a controlled environment. The surface evolution of these films is discussed, and the effects of different gas environments on oxygen vacancy concentration are elucidated. LSMO is commonly used in commercial fuel cell devices. Here the resonant soft x-ray emission (RIXS) spectrum of LSMO is examined, and it is shown that the inelastic x-ray emission structure of LSMO arises from local atomic multiplet effects.