X-RAY EMISSION SPECTROSCOPY, METHODS 2463

X-Ray Emission Spectroscopy, Methods

George N Dolenko, Lermontova 325A/16, 664033
HIGH ENERGY
Irkutsk, Russia
Oleg Kh Poleshchuk, Tomsk Pedagogical University, SPECTROSCOPY
Tomsk, Russia Methods & Instrumentation
Jolanta N Lato i ska, Adam Mickiewicz University,
Pozna , Poland
Copyright © 1999 Academic Press

General characteristics (primary excitation) or with X-ray photons

(secondary excitation, fluorescence radiation) and
Recently, intensive development of the theory of the produces a line spectrum. These collisions may also
electronic structure of chemical compounds has re- remove an electron of any inner shell of a target
vealed a great need for physical experimental atom. The resulting vacancy is filled by an electron
methods to which modern methods of quantum transition from another inner or outer electron shell.
chemistry can be applied. Primary information pro- As a consequence of this electron transition, energy
vided by quantum chemical methods of electronic is released which may be in the form of an X-ray
structure studies concerns the energy spectrum of quantum (Figure 1).
molecules as well as the structures of wavefunctions
of molecular orbitals (MOs). There is a need for
physical methods which would allow direct measure- Characteristic X-ray emission spectra
ment of MO energies as well as the determination of
Characteristic X-ray emission spectra consist of
the degree of participation of different atomic elec-
spectral series (K, L, M, N…), whose lines have a
trons in chemical bonding. X-ray emission spectro-
common initial state with the vacancy in the inner
scopy (XES), which provides both integral informa-
level. Labels of basic X-ray transitions are shown in
tion about electronic structure (effective charges on
Figure 2. All electron levels with the principal quan-
atoms, atomic nl populations) and differential infor-
tum number n equal to 1, 2, 3, 4, etc. are named as
mation (relative energies of occupied MOs and char-
K, L, M, N etc. levels and denoted with
acteristics of their AO components), can be referred
corresponding Greek letters and digit indexes. The
to these methods.
electron transitions which satisfy the dipole selection
X-rays, discovered by Röentgen in 1895, are a
rules
form of electromagnetic radiation that occupy the
spectral area between UV and γ radiation in the range
of wavelength λ = 10–3–10 2 nm, corresponding to
energies hν = 10–10 6 eV (ν = c/λ). X-ray spectro-
scopy is divided into X-ray emission and X-ray
are most intense. The dependence of X-ray emission
absorption spectroscopy and is subclassified into
line energy on atomic number Z is defined by
short wavelength (λ ≤ 0.2 nm), long wavelength
Moseley’s law:
(0.2 ≤ λ ≤ 2 nm) and ultralong wavelength ( λ > 2 nm)
regions.
X-ray emission spectroscopy is used for the study
of electronic structure and for the qualitative and
quantitative analysis of substances. With the help of
X-ray emission spectroscopy one may investigate all
elements of the periodic table (with Z > 2) in com-
pounds of any phase.
X-rays are divided into continuous and character-
istic. Continuous X-rays occur as a result of the stop-
ping of very fast charged particles (e.g. electrons) in
the target substance and have a ‘white’ spectrum.
Characteristic X-ray emission radiation is emitted by
target atoms after their collisions with hot electrons Figure 1 Scheme of radiation interaction with a substance.
2464 X-RAY EMISSION SPECTROSCOPY, METHODS

probability pr of a radiation transition in the atom

having the vacancy in the ith level. The value of pr is
determined by the total probability of photon emis-
sion when this vacancy is filled by outer electrons.
However, with a probability pA the vacancy may be
filled by outer electrons without radiation as the
result of the Auger-effect (see Figure 1). For the K
series of medium and heavy elements pr > pA, for the
light elements pr < pA. For all others series of any ele-
ments pr << pA. The ratio f = pr /(pr+pA) is called the
yield of characteristic radiation.
However, X-ray characteristic lines appear because
of single atom ionization; in X-ray emission spectra
weaker lines are found to occur as a result of binary
(or multiple) atom ionization when two (or more)
Figure 2 Scheme of the most important X-ray emission transi- vacancies are formed simultaneously in different elec-
tions; n, I and j are correspondingly the principal, orbital and total tron shells. If, for example, one vacancy is formed in
quantum numbers of K, L1, L2, L3 levels, etc. the K shell of atoms and filled by electrons belonging
to the L2,3 shell, atoms emit an Êα1,2 doublet. If
another vacancy is formed simultaneously which too
where Z is the atomic number and V is the shielding
is filled by electrons from the L2,3 shell, then the final
constant, which varies from series to series. There-
state will have a binary ionization L2,3L2,3, and would
fore, any X-ray emission spectral line is the finger-
correspond to the emission of radiation with energy
print of an element.
exceeding that of the Êα1,2 doublet. As a result, in an
With X-ray emission excitation by electron bom-
X-ray emission spectrum a short wavelength Êα3,4
bardment (primary emission) all emission lines of the
doublet, called a satellite of the main Êα1,2 doublet,
ith series appear when the X-ray tube voltage U
would appear. Because of such processes of multiple
exceeds the ionization potential of ith level (Vi). At
ionization X-ray emission spectra may have a large
higher U the intensity of all lines of the ith series, Ii,
number of satellites of the main lines. Usually, the
increases because the electrons penetrate deeper into
satellite intensity is some orders of magnitude less
the target substance and, therefore, the number of
than that of the main lines. However, if target atoms
excited atoms in the target increases. In the
are bombarded by heavy ions with great energy, the
Vi < U < 3Vi region, the intensity obeys the rule
probability of multiple atom ionization becomes
Ii ~ (U − Vi)2. With a further increase in U X-ray
higher than that of single ionization. Therefore, in
emission begins to be absorbed by the target atoms,
this case the intensity of the main emission lines is
therefore the increase in Ii is reduced. At U ≥ 11Vi, Ii
essentially less than that of the satellites.
decreases because now most of the excited atoms are
so deep in the target that their emitted radiation is
absorbed by the target substance. The continuous X-ray spectrum
X-ray emission spectra are usually excited by X-
ray photons because most chemical compounds are The continuous X-ray radiation occurs because of
decomposed by electron bombardment. With X-ray electron deceleration in the target substance. Elec-
emission spectra excitation by photons [secondary tron energy losses by radiation have quantum char-
emission or fluorescence (XFS)] the fluorescent line acter, the emitted photon having an energy hQ, which
intensity depends on the exciting photon energy hQ can not exceed the electron kinetic energy H, i.e.
Ii = 0 if hν < åVi. All lines of the ith series appear if hQ ≤ H. The energy hQi = H is called the quantum
hν = åVi; however, Ii decreases little with further boundary of a continuous spectrum. The corre-
increase in hQ. Therefore, to excite X-ray fluoresence sponding wavelength Oi depends on the X-ray tube
one must use a target that contains a substance with voltage charge U as follows:
intense characteristic X-ray lines whose energy just
exceeds eVi. Using the continous radiation of an X-
ray tube with a target consisting mostly of heavy
elements it is possible to excite X-ray fluorescence.
The intensity of a characteristic X-ray spectrum At O < Oi the intensity of continuous radiation is
(both primary and fluorescent) depends on the absent. With an increase in O from Oi to 3 Oi /2 the
 X-RAY EMISSION SPECTROSCOPY, METHODS 2465

continuous radiation intensity increases and with where n is the order of the spectrum, O is the wave-
further increases in O it decreases. length, d is the grating constant of the crystal
analyser and I is the angle of incidence of the colli-
mated X-ray fluorescent beam on the specific set of
X-ray sources parallel planes in the crystal from which the beam is
diffracted (see Table 1).
The most widespread source of X-rays is the X-ray The X-ray fluorescence spectrum is then registered
tube. In an X-ray tube, electrons emitted from the on a photographic film or by Geiger, proportional or
cathode are accelerated by an electrical field and scintillation counters, semiconductor detectors, etc.
bombard the metal target (anode). Target atoms, ex-
cited by electron impact, and electrons losing their
kinetic energy when decelerating in the anode sub-
stance, emit X-rays. The primary radiation of the X-
ray tube consists of two parts – characteristic (line)
and continuous radiation. As a result of the primary
radiation impinging on a substance its atoms emit
characteristic fluorescence (secondary) radiation.
Other sources of X-rays are radioactive isotopes
which can directly emit X-rays or electrons or α par-
ticles. In the last two cases charged particles can
bombard the target substance which then emits X-
rays. The intensity of X-ray isotope sources is some
orders of magnitude less than that of X-ray tubes;
however the dimensions, weight and cost of X-ray
isotope sources are less than that of X-ray tubes.
X-rays are also generated as synchrotron radia- Figure 3 An X-ray fluorescence spectrometer. 1, X-ray tube;
1a, electron source; 1b, target; 2, substance investigated (sec-
tion. It can be selected by a crystal analyser and may ondary anode); 3, crystal analyser; 4, registration device; h Q1, pri-
be used as an X-ray source. The intensity of X-rays mary radiation; h Q2, secondary radiation; and h Q3, registered
selected from synchrotron radiation is some orders radiation.
higher than that from an X-ray tube.
The characteristic radiation of the X-ray tube is Table 1 Parameters of typical crystal analysers
spread in space isotropically, whereas its continuous Maximal
radiation has maximal intensity in directions in a solving
plane perpendicular to the trajectory of electrons Reflecting ability Relative
bombarding the target. The X-ray component of Crystal plane 2d (nm) (λ/∆ λ) coefficient
synchrotron radiation is polarized and spread only KAP 001 2.7714 1400 8−18
in the plane of the synchrotron ring. Mica 002 1.9884 2 000 2−3
ADP 101 1.0659 10 000 1−10
EDDT 020 0.8808 − −
Obtaining X-ray emission spectra PET 002 0.8726 8 000 10−20
Quartz 1010 0.8512 20 000 1−10
A schematic of an X-ray fluorescence instrument is
Quartz 101 1 0.671 53 10 000 2−14
presented in Figure 3. The X-ray tube is used as the
Plumbago 002 0.6696 100 50−200
source of primary radiation hν1. The vacancies in in-
Ge 111 0.653 27 6 000 −
ner shells of atoms of the substance investigated are
Si 111 0.6271 10 000 2−10
formed as a result of primary radiation action. These
Calcite 211 0.6069 15 000 2−30
vacancies are filled by other inner or outer electrons.
Quartz 1020 0.4912 30 000 0.4−3.3
This is accompanied by X-ray fluorescent photons
LiF 200 0.4028 2 000 10
hν2 being emitted. This fluorescence radiation is
Ge 220 0.400 13 000 17−23
spread out into the spectrum by means of a crystal
Si 220 0.383 99 29 000 1–6
analyser (or, for the ultrasoft X-ray region, by means
Calcite 422 0.3034 64 000 0.4−0.9
of diffraction gratings) in accordance with Bragg’s
LiF 220 0.2848 1 300 10−20
law
Quartz 2023 0.2806 90 000 0.3−0.9
Quartz 2243 0.2024 144 000 0.2−0.45
Calcite 633 0.202 122 000 0.3−0.6
2466 X-RAY EMISSION SPECTROSCOPY, METHODS

The wavelengths and energies of the characteristic complex samples but needs the special requirements
emission lines have been accurately measured and of sample preparation.
tabulated in handbooks, monographs and reference The use of the background of scattered primary
works for all chemical elements with Z > 2. radiation is based on the fact that the ratio IA:Ib (Ib is
the background intensity) mainly depends on CA and
only weakly depends on the concentration of other
X-ray fluorescence analysis
elements, Ci.
X-ray fluorescence analysis (XFA) is based on the In the method of dilution a great amount of a
X-ray emission line’s intensity dependence on the weak absorber or a small amount of strong absorber
concentration of the appropriate element. XFA is is added to the sample investigated. These additions
widely used for the quantitative analysis of various should reduce the matrix effect. This method is effec-
materials, especially in black and colour metallurgy tive for water solution analysis and for the analysis
and geology. XFA is distinguished by rapidity and a of complex samples when the internal standard
high degree of automation. The detection limits de- method is inapplicable.
pend on the element, matrix composition and spec- There are also models in which the measured
trometer used and lie in the region 10–3 –10 –10%. intensity IA is corrected on the basis of the intensities
Defining any element (with Z > 4) is possible by Ii and concentrations Ci of other elements. For exam-
means of XFA in both a solid and a liquid phase. ple, CA may be represented as:
However, the fluorescence line intensity IA of an
investigated element A depends not only on its con-
centration CA in the sample, but also on the concen-
tration of other elements, Ci, because other elements
promote both absorption and excitation of fluores-
cence of the element A (matrix effect). Moreover, the
measured value IA essentially depends on the sample
surface, phase distribution, grain sizes, etc. Numer- a and b are values determined by the least-squares
ous methods have been developed to account for method with the help of IA and Ii values measured in
such effects. Most notable are the empirical methods several standards with known concentrations CA of
of external and internal standards, using the back- element A. Such models are widely used for the serial
ground of scattered primary radiation and the analysis of many samples via computers.
method of dilution.
In the external standard method the unknown
concentration CA of the element A is determined by X-ray microanalysis
comparing the intensity IA in the sample investigated
X-ray microanalysis is a local analysis, fulfilled by
with analogous Ist values of standards for which
means of microanalyser electron probe, for sample
defined element concentrations Cst are known:
sites of ~ 1–3 µm2. The electron probe is formed by
electrostatic and magnetic fields to obtain a parallel
electron beam with a diameter of ~ 1 µm. The analy-
sis is via primary X-ray sample emission which is
spread out into a spectrum by means of X-ray spec-
This method allows one to take into account
trometer. In this method corrections for the atomic
corrections connected with the equipment used;
number of the element, the absorption of its radia-
however, the composition of the standard should be
tion in the sample, its fluorescence, and the charac-
close to that of the investigated sample to precisely
teristic spectra of other elements contained in the
match the matrix effect.
sample must be accounted for. Microanalysis is used
In the internal standard method some amount ∆ A
for the investigation of two- and three-component
of a defined element A is added to the sample investi-
systems such as mutual diffusion, crystallization
gated. This leads to an increase in the fluorescence
processes, local variations of alloy structure, etc.
intensity of ∆IA. In this case:

List of symbols
d = grating constant; IA = fluorescence line intensity
of an investigated element A; Ist = fluorescence
This method is especially effective for the analysis of intensity of a standard; n = order of spectrum;
 X-RAY FLUORESCENCE SPECTROMETERS 2467

pA = probability of a vacancy being filled without Mazalov LN, Yumatov VD, Murakhtanov VV, Gel-
emission; pr = probability of photon emission when mukhanov FK, Dolenko GN, Gluskin ES and Kon-
vacancy is filled; U = X-ray tube voltage; dratenko AV (1977) Rentgenovskie Spectry Molekul.
Vi = ionization potential of the ith level; Z = atomic Novosobirsk: Nauka, 331p.
Meisel A, Leonhardt G and Szargan R (1977) Rönt-
number; ε = electron kinetic energy; λ = wavelength;
genspektren und Chemische Bindung . Leipzig: Geest &
δ = shielding constant; I = angle of incidence. Portig, 320p.
See also: X-Ray Absorption Spectrometers; X-Ray Nemoshkalenko VV and Aleshin VG (1979) Teoreti-
Fluorescence Spectrometers; X-Ray Fluorescence cheskie osnovy rentrenovskoj emissionnoj spektrosko-
Spectroscopy, Applications. pii. Kiev: Naukova Dumka, 384p.
Siegbahn K, Nordling C, Fahlman A, Nordberg R, Hamrin
K, Yedman J, Johansson G, Bergmark T, Karlsson SE,
Further reading Lindgren I and Lindberg B (1967) ESCA. Atomic, Mo-
lecular and Solid State Structure by Means of Electron
Bearden JA (1967) X-ray wavelengths. Review of Modern Spectroscopy. Uppsala: Nova acta Regiae Societatus
Physics 39: 78–124. Scientiarum Upsaliensis, 493p.
Ehrhardt H (1981) Röntgenfluoreszenzanalyse. Leipzig:
VEB Deutscher Verlag für Grundstoffindustrie, 250p.

X-Ray Fluorescence Spectrometers

Utz Kramar, University of Karlsruhe, Germany
HIGH ENERGY
Copyright © 1999 Academic Press SPECTROSCOPY
Methods & Instrumentation

X-ray fluorescence (XRF) spectrometers are widely principles of XRF spectroscopy and descriptions of
used for the determination of elements with atomic the different kinds of instrumentation are given in an
numbers from 4 (beryllium) to 92 (uranium) at con- increasing number of monographs, books and re-
centrations from 0.1 µg g–1 to high percentage levels. views, with extensive data compilations.
These elements can be analysed using characteristic
Kα-lines (KLIII) from 11.4 nm/0.1885 keV (Be Kα) to Principles
0.0126 nm/98.4 keV (U Kα). Nevertheless, elements
of higher atomic number (e.g. Cd LIIIMV 0.3956 nm/ If a target is irradiated with photons, or charged par-
3.133 keV; U LIIIMV 0.09106 nm/13.61 keV) are of- ticles (electrons or ions) with energies exceeding the
ten determined using their L-lines. The characteristic binding energy of the bound inner electrons, an elec-
X-ray lines of these elements can be determined either tron from inner orbitals of the target atoms can be
with sequential or with simultaneous wavelength-dis- ejected.
persive spectrometers by Bragg diffraction, using the
wave phenomena of X-rays or in energy-dispersive
systems using their energy characteristic. Coherent
and incoherent scattering of primary X-rays in the
sample may cause increased background effects, and
matrix-dependent absorption of the characteristic where Zeff = effective atomic number and
secondary X-rays may also cause severe matrix ef- n = principal quantum number. If the total energy of
fects. Since XRF methods are routinely used, methods the photon is transferred to the electron this interac-
for correcting the matrix effects such as fundamental tion is called the photoeffect.
parameters have been developed and instruments The resulting atom is unstable and regains its
with drastically improved peak to background ratios ground state by transferring an electron from a high-
such as polarized X-ray fluorescence (PXRF) and energy outer orbital to the vacancy in the inner elec-
total reflection X-ray fluorescence (TXRF) spectro- tron shell. The energy difference between the initial
meters have been designed during the 1990s. The and final energy state of the transferred electron is