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Spectroscopy Photoelectron spectroscopy X-ray absorption spectroscopy.

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Presentation on theme: "Spectroscopy Photoelectron spectroscopy X-ray absorption spectroscopy."— Presentation transcript:

1 Spectroscopy Photoelectron spectroscopy X-ray absorption spectroscopy

2 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 What is spectroscopy? ”Spectrum” is Latin and means ”appearance”, ”apparition” 17 th century: Particle in (here: photon) Particle out (here: photon) E dispersive scale sample

3 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011

4 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

5 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 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

6 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 hv = E B + E kin +  The photoelectric effect (Einstein, 1905) X-ray photoelectron spectroscopy

7 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 Core level binding energies: characteristic for the elements

8 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 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

9 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 Chemical shifts in x-ray photoelectron spectroscopy

10 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 Photoemission spectroscopy is surface sensitive X-ray Beam X-ray penetration depth ~1  m. Electrons can be excited in this entire volume. X-ray excitation area can be as large as ~1x1 cm 2. Electrons are emitted from this entire area Electrons are extracted only from a thin layer close to the surface. 1 mm 2 ~1-10 nm

11 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 The Auger effect (Pierre Auger, 1925)

12 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 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

13 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 Photon sources Synchrotron light sources: Advantages: wide range of energies, high intensity, high resolution Disadvantages: expensive, not readily available

14 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 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

15 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011 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 I 1 (h )-I 0 (h ). True absorption measurement (a)

16 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011  * and  * orbitals

17 Lunds universitet / Fysiska institutionen / Avdelningen för synkrotronljusfysik FYST20 VT 2011

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