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X-rays and XRF

Physical aspects

P. Van Espen Dept. of Chemistry University of Antwerp, Belgium piet.vanespen@ua.ac.be

The Nature of X-rays
X-ray are part of the electromagnetic spectrum between ultraviolet radiation and gamma-rays. • When dealing with diffraction we best consider X-rays as electromagnetic waves with wavelength λ • When discussing absorption and scattering X-rays are best considered as photons with a certain energy E. Relation between energy and wavelength: h c

E=

hc

λ

λ
E

Planck's constant (6.6254x10-34 J s) the velocity light the wave (3.00x108 m/s) wavelength in meters Energy in joules.

E 0.1 Å UV Ultrasoft x-rays Be K" Soft x-rays Fe K" Hard x-rays U K" ( -rays Analytical Range Energy.40 keV ⇒ λ = 1.0 10. 100 keV .In X-ray spectrometry: Wavelength in Ångstrom units (1Å = 0.1 1.94 Å E = 0.24x1015 keV 12.1 nm = 10-10 m) Energy in kilo-electronvolt (keV) 1 J = 6. E = 6.11 keV ⇒ λ = 113 Å E = 98.4 E[keV] = λ [Å] Wavelength.126 Å 1.0 0. 8 100 Fe Kα Be Kα U Kα 10.4 keV ⇒ λ = 0.

. N. . • In each shell the electrons are further distinguished by their azimuthal (l = 0. 5.½ . l) and spin (s = . • A shell can have at maximum 2n2 electrons. and 6). magnetic (m = -l.Interaction of X-rays with matter The Bohr approximation of the atom • Z electrons are grouped in shells designated K.. . . 0. 2.. 3. • K-shell electrons are more tightly bound than the L-shell electrons. L2. n-1). O. j = |l ± ½|. • The K-shell has 1 energy level. • Two electrons in an atom cannot have the same set of quantum numbers (Pauli's exclusion principle). • The number of energy levels (or sub-shells) in each shell is equal to the number of allowed values of j (spin-orbit coupling). + ½) quantum numbers... The electrons in an atom occupy discrete energy levels. L3) and the M-shell has 5 . L... the L-shell has 3 (L1. 4. .. P (principal quantum number n = 1. M.

azimuthal quantum numbers.principal... L..n-1 j = |l ± ½| Max.and M-shells (n .Energy levels of the K-. j spin-orbit coupling) Shell n l = 0.. number of electrons 2j+1 K L1 L2 L3 M1 M2 M3 M4 M5 1 2 2 2 3 3 3 3 3 0 0 1 1 0 1 1 2 2 1/2 1/2 1/2 3/2 1/2 1/2 3/2 3/2 5/2 2 2 2 4 2 2 4 4 6 . l .

102 L2 0.933 . Energy levels in copper Sub-shell Binding energy (keV) K 8.953 L3 0.981 L1 1.The binding energy of inner electrons in the atom is of the same order of magnitude as the energy of the X-ray photons. ⇒ X-rays can interact with the inner shell electrons.

causes the generation of the characteristic X-rays in the sample.The interaction of X-rays with atomic electrons absorption of the photon photoelectric absorption is the dominant interaction. scattering of the photon responsible for most of the continuum observed in XRF spectra (part of the exciting radiation is scattered by the sample and enters the detector system) .

⇒ A vacancy has been created in one of the inner shells.Photoelectric absorption a photon is completely absorbed by the atom an (inner shell) electron is ejected. . ω. the rest is transferred to the electron in the form of kinetic energy Photoelectric absorption can only occur if EPhoton > Eab !!! • After the interaction. The probability of the emission of characteristic x-ray is called the fluorescent yield. • Part of the photon energy is used to overcome the binding energy of the electron. the atom (actually ion) is in a highly excited state. • The atom will almost immediately return to a more stable electron configuration ⇒ emission of an Auger electron or a characteristic X-ray photon.

and M. .98 keV there is an abrupt decrease in the cross section • X-rays with lower energy can only interact with the L.98 keV the cross section is higher !!! • At 8. r.The photoelectric cross section of copper as function of the energy of the interacting photon τph (E) absorption edges Cu • At high energy the probability of ejecting a electron is rather low • At E slightly greater than 8.electrons. The ratio of the cross section just above and just below the absorption edge is called the jump ratio.

5 21.83 4.987 7.745 3.940 3.534 0.545 L3 M5 Absorption edge wavelength (Å) K 43.109 8.399 69.108 127 35.245 10.770 0.814 2.178 0.101 23.722 15.001 5.708 0.037 5.070 1.Absorption edge energies and wavelengths for some elements Elem.217 37.329 16.130 2.955 3.853 1.89 6.037 115.488 0.502 3.363 1.780 1.141 0.216 0.331 0.479 88.837 4.5 14.070 2.743 1.283 1.497 L3 M5 .160 0.387 4.61 0.767 6.574 0.5 6.196 13.349 0.098 0.041 17. C Si Ca Cr Fe Ni Sr Rh Ba W Pb U 6 14 20 24 26 28 38 45 56 74 82 92 Absorption edge energy (keV) K 0.6 17.950 0.

inelasticly scattered over an angle θ will have an energy E' given by the Compton equation: ' Compton Scatter > E′ = 1+ E E (1 . • A photon with energy E.Elastic and Inelastic Scattering Scattering causes the photon to change direction.cos θ ) 511 K L M e- E = 20 keV. θ = 90° ⇒ E' = 19. Elastic or Rayleigh scattering • The energy of the photon is the same before and after scattering • Occurs on bound electrons • Forms the basis of X-ray diffraction.25 Rayleigh Scatter . Inelastic or Compton scattering • The photon loses some of its energy • Occurs when X-ray photons interact with weakly bound electrons.

coherent and incoherent scattering µ = τ Photo + τ Coh + τ Inc . The total mass attenuation coefficient is the contribution from photo-electric absorption.X-ray attenuation X-rays pass through matter ⇒ some photons will be affected • by photoelectric absorption • by scattering The intensity I0 of an X-ray beam passing through a layer of thickness d and density ρ is reduced to an intensity I according to the well-known law of Lambert-Beer: I = I 0 exp( − µρ d ) The number of photons (the intensity) is reduced but their energy is unchanged. µ is called the mass attenuation coefficient and has the dimension of [cm2/g].

Log-log plot of the mass attenuation coefficient of aluminium. and lead for X-rays with energies between 0. .1 and 50 keV. iron. • • • The absorption edge discontinuities due to photoelectric absorption are clearly visible. Low Z materials (Al) attenuate X-rays less than high Z materials (Pb). High energy (hard) X-rays are attenuated less than low energy (soft) X-rays.

the mass attenuation coefficient element i wi .7 Fe Pb 4000 12300 2490 75.2 keV 0.525 1. a mixture or an alloy) can be calculated as: µ M = ∑ µ i wi i=1 n µi .2 Si K-L3.94 1.47 Å 23.5 389 1970 426 286 .6 Si 7930 360 124 78.5 14.40 7.6 7.13 1.66 Mass attenuation coefficient µ in cm2/g of absorber O 1270 1050 23.The mass attenuation coefficient of a complex matrix (a compound.2 Ni K-L3.the weight fraction of element i Radiation Line O K-L3.74 6.2 Fe K-L3.

Those give rise to the allowed or diagram lines. • These X-rays are called "characteristic" because their energy is different for each element. . • The vacancy will be filled by an electron from a higher shell. Forbidden transitions have very low intensity. ∆n > 0. • The emission governed by quantum mechanical selection rules. and ∆j = 0 or ±1. (vacancy in the Kshell and vacancy in the L3-shell) can be emitted as an X-ray photon. as every element has its own energy level.Characteristic X-rays emission • After photoelectric absorption the atom is in a highly excited state. ∆l = ±1. • The energy difference between those two states.

or N-shell transitions ⇒ Kβ lines higher energy.K-lines: X-ray lines that originate from a vacancy in the K-shell • L3 →K transition Transition diagram of iron ⇒ X-ray with an energy of 6.404 keV (1. but less intensity .2 or Kα • M.9360 Å) (Fe K-L3 or Fe Kα1) • L2 →K transition ⇒ Fe K-L2 or Kα2 line doublet with very small energy difference ⇒ K-L3.

. • L-lines are used to determine elements with an atomic number greater than 45 (Rh). In case of interference. the L2-M4 (Lβ) line can be used.and L-lines from lower Z elements (S). L2 and L3) sub-shells ⇒ the L-line spectrum is more complex than the K-line spectrum.and M-lines L-lines result from filling a vacancy in the L-shell. • There are 3 (L1. M-lines are due to a vacancy in one of the five M sub-cells • Seldom used in XRF.L. • The M-lines of the heavy elements (Pb) can interfere with K.4 (Lα) line is the most suitable analytical line. • The L3-M5.

and Siegbahn notation. and their intensity relative to the major line in each sub-shell Notation IUPAC K-lines K-L3 K-L2 K-M3 K-M2 L3-lines L3-M5 L3-M4 L3-N5.15 Ll Lβ6 Lβ1 Lγ1 Lη Lγ6 Lβ3 Lβ4 Lγ3 Lγ2 Mα1 Mα2 Mβ Relative intensity 100 ~50 ~17 ~8 100 ~10 ~25 ~5 ~1 100 ~20 3 3 100 ~70 ~30 ~30 fKα is the Kα to total K (Kα+Kβ) ratio .4 L3-M1 L3-N1 L2-lines L2-M4 L2-N4 L2-M1 L2-O1 L1-lines L1-M3 L1-M2 L1-N3 L1-N2 M-lines M5-N7 M5-N6 M4-N6 Siegbahn Kα1 Kα2 Kβ1 Kβ3 Lα1 Lα2 Lβ2. IUPAC.Principal X-ray diagram lines.

451 4.672 10.817 57.318 74.7 (Mα) 15.525 1.951 84.828 8.378 67.098 20.345 3.171 .869 1.194 59.552 12.724 36.074 31.614 13.461 14.705 0.947 7.697 2.834 4.775 2.852 0.740 3.216 32.699 36.615 17.450 110.982 72.300 K-M2 (Kβ3) L3-M5 (Lα1) L2-M4 (Lβ1) M5-N5.304 66.872 2.439 K-L2 (Kα2) 3.341 0.825 22.406 0.692 5.058 8.807 1.Energy in keV of the major characteristic lines of some elements Elem.220 1.665 K-M3 (Kβ1) 4.165 20.573 0.836 22.265 15.398 9.478 14.391 7.969 98. C Si Ca Cr Fe Ni Sr Rh Ba W Pb U 6 14 20 24 26 28 38 45 56 74 82 92 K-L3 (Kα1) 0.404 7.688 5.415 6.013 5.583 0.804 94.719 0.936 111.244 84.406 6.

.(or M-) electron The electron receives sufficient energy to leave the atom and is called an Auger electron.g. for the K-shell: Number of K X − rays emitted = ωK Number of K vacancies created ωK is very small (~0. . e. many vacancies are created.Fluorescence yield and Auger electron emission The energy released when an L-electron drops into a K-vacancy can also be transferred to another L.01) for elements below sodium (Z = 11) For high Z elements ωK tends toward one XRF is less sensitive for light elements. but only few characteristic X-rays are emitted. The probability that the vacancy will result in X-ray emission is called the fluorescence yield.

of the absorber . The total mass attenuation coefficient µ in cm2g-1 can be calculated using the relation: µ = He E k H d d + k ln E the energy of the x-ray in keV a constant for each edge a constant for each sub-edge a function of the atomic number. Z.Calculation of Mass Attenuation Coefficients: the Wernisch Algorithm.

the K-edge (B) or above the K-edge (A) different constants are used µ = He d + k ln E . the L-edge C.Depending on the region below the M-edge (D).

917 10-1 3.520 10-4 9.838 d1 3.935 0.257 2.212 10-1 4.058 10-7 0 0 H takes the sub shell jump ratio into account Energy Range E>EK EL1<E<EK EL2<E<EL1 EL3<E<EL2 EM1<E<EL3 EM1<E<EM2 EM2<E<EM3 EM3<E<EM4 EM4<E<EM5 E<EM5 H 1 1 0.508 10-7 -4.936 10-1 2.483 10-3 -2.862 0.054 10-2 -8.638 0.955 3.842 0.2 3 4 d is given by: d = d o + d1Z + d 2 Z + d 3 Z + d 4 Z Energy Range E>EK EL3<E<EK EM5<E<EL3 E<EM5 k -2.611 1 0.685 -2.669 -2.514 -2.891 10-6 0 d4 -8.451 d0 5.443 1 .382 4.028 10-3 0 d3 1.491 10-5 6.911 10-2 d2 -1.

506⋅10-1 -6.843⋅10-5 -6 30 83 1.280 -4.115⋅10-5 61 83 1. si.459⋅10-1 2.018⋅10-1 3.499 -6.718⋅10-3 7.633⋅10-3 1.303⋅10-3 -1. Wernisch proposed the following equation Ei = ri + si Z + ti Z 2 + ni Z 3 With Ei Z ri.566⋅10-2 1.421 See MACWernisch.390⋅10-1 -8. ni Edge K L1 L2 L3 M1 M2 M3 M4 M5 the energy in keV of a particular edge i the atomic number of the atom coefficients for a particular edge i. given in the table si -2.184⋅10-1 1.397⋅10-5 rI -1.To calculate the edge energies. ti.117⋅10-3 -3.935⋅10-4 2.263⋅10 55 83 2.645 -7.172⋅10-1 ti 9.144⋅10-5 28 83 1.963⋅10-3 -5.836⋅10 -5 52 83 3.792⋅10-5 30 83 1.831⋅10-1 2.931⋅10-2 3.599⋅10-4 5.505⋅10-5 60 83 2.336⋅10-3 -5.xls .778 -2.964⋅10-2 -4.624⋅10 -5 55 83 3.250⋅10-3 -4.304⋅10-1 -4.845⋅10-3 nI Zmin Zmax 11 63 4.977⋅10-1 3.