Spectroscopy Photoelectron spectroscopy X-ray absorption spectroscopy

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Presentation transcript:

Spectroscopy Photoelectron spectroscopy X-ray absorption spectroscopy

What is spectroscopy? ”Spectrum” is Latin and means ”appearance”, ”apparition” 17th century: Particle out (here: photon) Particle in (here: photon) E dispersive scale sample

Spectroscopy ”methods” that you have mentioned XPS XAS VMIS FTIR Absorption spectroscopy Gamma spectroscopy Alpha spectroscopy Emission spectroscopy NMR spectroscopy Atomic spectroscopy / Molecular spectroscopy IR spectroscopy

X-ray photoelectron spectroscopy Photoelectron spectroscopy = Photoemission spectroscopy XPS = X-ray photoelectron spectroscopy UPS = Ultraviolet photoelectron spectroscopy Hard x-ray: approx. 1200 – 250,000 eV Soft x-rays: approx. 20 – 1200 eV Vacuum ultraviolet: approx. 6 – 20 eV Ultraviolet: approx. 3 – 6 eV

X-ray photoelectron spectroscopy The photoelectric effect (Einstein, 1905) hv = EB + Ekin + f

Core level binding energies: characteristic for the elements

A photoelectron spectrum over the entire available energy range Secondary electrons: electrons which have lost energy due to scattering on their way out of the solid into the vacuum

Chemical shifts in x-ray photoelectron spectroscopy

Photoemission spectroscopy is surface sensitive Electrons are extracted only from a thin layer close to the surface. X-ray Beam X-ray penetration depth ~1mm. Electrons can be excited in this entire volume. ~1-10 nm 1 mm2 X-ray excitation area can be as large as ~1x1 cm2. Electrons are emitted from this entire area

The Auger effect (Pierre Auger, 1925)

Photon sources Lab sources: photons emitted from an electronically excited material (lasers, x-ray anodes, helium lamps) Advantage: cheap, can be used in home Lab, easy to use Disadvantage: only certain energies are available, the intensities and energy resolution of x-ray tubes are limited

Photon sources Synchrotron light sources: Advantages: wide range of energies, high intensity, high resolution Disadvantages: expensive, not readily available

X-ray absorption spectroscopy XANES = X-ray Absorption Near Edge Structure NEXAFS = Near Edge X-ray Absorption Fine Structure XAS = X-ray Absorption Spectroscopy Unoccupied electronic levels of atom/molecule/solid

How to measure x-ray absorption spectra The number of decays (as a function of photon energy) is (exactly) proportional to the number of excitations (as a function of photon energy)! Electron yield or fluorescence yield measurement (b) Measure I1(hn)-I0(hn). True absorption measurement (a)

s* and p* orbitals