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 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

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

In X-ray spectrometry: Wavelength in ngstrom units (1 = 0.1 nm = 10-10 m) Energy in kilo-electronvolt (keV) 1 J = 6.24x1015 keV

12.4 E[keV] = []
Wavelength, 8 100

Fe K Be K U K
10.

E = 6.40 keV = 1.94 E = 0.11 keV = 113 E = 98.4 keV = 0.126

1.0 0.1

UV

Ultrasoft x-rays
Be K"

Soft x-rays
Fe K"

Hard x-rays
U K"

( -rays

Analytical Range Energy, E 0.1 1.0 10. 100 keV

Interaction of X-rays with matter

The Bohr approximation of the atom
Z electrons are grouped in shells designated K, L, M, N, O, P (principal quantum number n = 1, 2, 3, 4, 5, and 6). A shell can have at maximum 2n2 electrons. In each shell the electrons are further distinguished by their azimuthal (l = 0, ... , n-1), magnetic (m = -l, ..., 0, ..., l) and spin (s = - , + ) quantum numbers. Two electrons in an atom cannot have the same set of quantum numbers (Pauli's exclusion principle).

The electrons in an atom occupy discrete energy levels.

K-shell electrons are more tightly bound than the L-shell electrons. The number of energy levels (or sub-shells) in each shell is equal to the number of allowed values of j (spin-orbit coupling), j = |l |. The K-shell has 1 energy level, the L-shell has 3 (L1, L2, L3) and the M-shell has 5

Energy levels of the K-, L- and M-shells (n - principal, l - azimuthal quantum numbers; j spin-orbit coupling)
Shell n l = 0,...,n-1 j = |l | Max. 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

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.

Energy levels in copper

Sub-shell Binding energy (keV) K 8.981 L1 1.102 L2 0.953 L3 0.933

The interaction of X-rays with atomic electrons

absorption of the photon photoelectric absorption is the dominant interaction, causes the generation of the characteristic X-rays in the sample. 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)

Photoelectric absorption
a photon is completely absorbed by the atom an (inner shell) electron is ejected.

Part of the photon energy is used to overcome the binding energy of the electron, 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 atom (actually ion) is in a highly excited state. A vacancy has been created in one of the inner shells. The atom will almost immediately return to a more stable electron configuration emission of an Auger electron or a characteristic X-ray photon. The probability of the emission of characteristic x-ray is called the fluorescent yield, .

The photoelectric cross section of copper as function of the energy of the interacting photon ph (E)
absorption edges

Cu

At high energy the probability of ejecting a electron is rather low At E slightly greater than 8.98 keV the cross section is higher !!! At 8.98 keV there is an abrupt decrease in the cross section X-rays with lower energy can only interact with the L- and M- electrons. The ratio of the cross section just above and just below the absorption edge is called the jump ratio, r.

Absorption edge energies and wavelengths for some elements

Elem. 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 0.283 1.837 4.037 5.987 7.109 8.329 16.101 23.217 37.399 69.479 88.037 115.61 0.098 0.349 0.574 0.708 0.853 1.940 3.001 5.245 10.196 13.041 17.160 0.780 1.814 2.502 3.545 L3 M5 Absorption edge wavelength () K 43.767 6.745 3.070 2.070 1.743 1.488 0.770 0.534 0.331 0.178 0.141 0.108 127 35.5 21.6 17.5 14.5 6.387 4.130 2.363 1.216 0.950 0.722 15.89 6.83 4.955 3.497 L3 M5

Elastic and Inelastic Scattering

Scattering causes the photon to change direction.
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. Inelastic or Compton scattering The photon loses some of its energy Occurs when X-ray photons interact with weakly bound electrons. A photon with energy E, inelasticly scattered over an angle will have an energy E' given by the Compton equation: ' Compton Scatter
>

E = 1+

E E (1 - cos ) 511
K L M

e-

E = 20 keV, = 90 E' = 19.25

Rayleigh Scatter

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 is reduced to an intensity I according to the well-known law of Lambert-Beer:

I = I 0 exp( d )
The number of photons (the intensity) is reduced but their energy is unchanged. is called the mass attenuation coefficient and has the dimension of [cm2/g]. The total mass attenuation coefficient is the contribution from photo-electric absorption, coherent and incoherent scattering

= Photo + Coh + Inc

Log-log plot of the mass attenuation coefficient of aluminium, iron, and lead for X-rays with energies between 0.1 and 50 keV.

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 of a complex matrix (a compound, a mixture or an alloy) can be calculated as:

M = i wi
i=1

i - the mass attenuation coefficient element i

wi - the weight fraction of element i

Radiation Line O K-L3,2 Si K-L3,2 Fe K-L3,2 Ni K-L3,2 keV 0.525 1.74 6.40 7.47 23.6 7.13 1.94 1.66

Mass attenuation coefficient in cm2/g of absorber O 1270 1050 23.5 14.6 Si 7930 360 124 78.7 Fe Pb

4000 12300 2490 75.5 389 1970 426 286

Characteristic X-rays emission

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

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 (1.9360 ) (Fe K-L3 or Fe K1) L2 K transition Fe K-L2 or K2 line doublet with very small energy difference K-L3,2 or K M- or N-shell transitions

K lines higher energy, but less intensity

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

Principal X-ray diagram lines, IUPAC, 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-N5,4 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 K1 K2 K1 K3 L1 L2 L2,15 Ll L6 L1 L1 L L6 L3 L4 L3 L2 M1 M2 M Relative intensity 100 ~50 ~17 ~8 100 ~10 ~25 ~5 ~1 100 ~20 3 3 100 ~70 ~30 ~30

fK

is the K to total K (K+K) ratio

Energy in keV of the major characteristic lines of some elements

Elem. 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 (K1) 0.525 1.740 3.692 5.415 6.404 7.478 14.165 20.216 32.194 59.318 74.969 98.439 K-L2 (K2) 3.688 5.406 6.391 7.461 14.098 20.074 31.817 57.982 72.804 94.665 K-M3 (K1) 4.013 5.947 7.058 8.265 15.836 22.724 36.378 67.244 84.936 111.300 K-M2 (K3) L3-M5 (L1) L2-M4 (L1) M5-N5,7 (M)

15.825 22.699 36.304 66.951 84.450 110.406

0.341 0.573 0.583 0.705 0.719 0.852 0.869 1.807 1.872 2.697 2.834 4.451 4.828 8.398 9.672 10.552 12.614 13.615 17.220

1.775 2.345 3.171

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- (or M-) electron The electron receives sufficient energy to leave the atom and is called an Auger electron. The probability that the vacancy will result in X-ray emission is called the fluorescence yield, e.g., for the K-shell: Number of K X rays emitted = K Number of K vacancies created K is very small (~0.01) for elements below sodium (Z = 11) For high Z elements K tends toward one XRF is less sensitive for light elements, many vacancies are created, but only few characteristic X-rays are emitted.

Calculation of Mass Attenuation Coefficients: the Wernisch Algorithm.

The total mass attenuation coefficient in cm2g-1 can be calculated using the relation:

= 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, of the absorber

Depending on the region below the M-edge (D), the L-edge C, the K-edge (B) or above the K-edge (A) different constants are used

= He

d + k ln E

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 -2.685 -2.669 -2.514 -2.451

d0 5.955 3.257 2.382 4.838

d1 3.917 10-1 3.936 10-1 2.212 10-1 4.911 10-2

d2 -1.054 10-2 -8.483 10-3 -2.028 10-3 0

d3 1.520 10-4 9.491 10-5 6.891 10-6 0

d4 -8.508 10-7 -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 0.862 0.611 1 0.935 0.842 0.638 0.443 1

To calculate the edge energies, Wernisch proposed the following equation

Ei = ri + si Z + ti Z 2 + ni Z 3
With Ei Z ri, si, ti, 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 -2.63310-3 1.56610-2 1.96410-2 -4.93110-2 3.97710-1 3.45910-1 2.83110-1 2.18410-1 1.17210-1 ti 9.71810-3 7.59910-4 5.93510-4 2.33610-3 -5.96310-3 -5.25010-3 -4.11710-3 -3.30310-3 -1.84510-3 nI Zmin Zmax 11 63 4.14410-5 28 83 1.79210-5 30 83 1.84310-5 -6 30 83 1.83610 -5 52 83 3.62410 -5 55 83 3.26310 55 83 2.50510-5 60 83 2.11510-5 61 83 1.39710-5

rI -1.30410-1 -4.50610-1 -6.01810-1 3.39010-1 -8.645 -7.499 -6.280 -4.778 -2.421

See MACWernisch.xls