Spectrochimica Acta Part B 156 (2019) 33–41

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Spectrochimica Acta Part B

journal homepage: www.elsevier.com/locate/sab

Fundamental parameter model for quantification of total reflection X-ray T

fluorescence analysis
⁎
I. Szalóki , G. Radócz, A. Gerényi
Institute of Nuclear Techniques, Budapest University of Technology and Economics, Műegyetem rkp. 9, Budapest H-1111, Hungary

A R T I C LE I N FO A B S T R A C T

Keywords: A new fundamental parameter model and calculation algorithm is presented for quantitative analysis for total
TXRF reflection X-ray fluorescence analytical technique. The model takes into consideration the geometrical para-
FP model meters of the measuring set-up, the energy distribution of the exciter X-ray beam and its incidence angle to the
Silicon wafer surface of the sample holder. The numerical solution of this new model results the concentration of the sample
Contamination
elements. The system of equations of the fundamental parameter model involves the mathematical description of
the excitation process in the sample layer and in the sample holder. The theoretical calibration for the quan-
titative determination of the sample elements is based on the numerical comparison of the measured and cal-
culated X-ray fluorescence signal of the pure silicon sample holder. For the numerical calculation computer code
was created in order to solve numerically the model equations. The whole analytical procedure is a standard-free
method. The theoretical model and the complete numerical calculation was tested experimentally with standard
solutions of K, Sc, V, Mn, Co, Ni and Cu elements, which were dripped onto high purity silicon wafer and dried
before measurement. This standard-free analytical procedure can be utilized in the semiconductor industry and
in various total reflection X-ray fluorescence analysis performed for investigations of environmental samples,
natural waters, geological substances, foods and drinks.

1. Introduction
The TXRF (Total Reflection X-Ray Fluorescence) analysis is one of
the most effective analytical method for quantitative determination of
trace elements in small quantity of sample mass that located on the
solid and smooth surface of sample carrier [1]. By this analytical
technique highly sensitive characterization can be done on elementary
composition of the contamination layer on the surface of a high purity
silicon wafers. Hence this analytical technique is advantageous for
quality checking of silicon wafers as well, that is widely applied in the
semiconductor industry [2,3,4]. For the reason that in TXRF set-up the
primary photons impinging approximately critical angle to the surface
of the sample holder, the penetration depth of primary photons into the
surface is only couple of nm. Therefore, the probability of the scattering
in this narrow layer is extremely low that effect provides a relatively
high signal/noise ratio in the analytical energy range. On the other
hand, the small entering angle of exciter X-ray photons results a low
flux of the primary X-ray beam, which requires high power X-ray tube.
For excitation of the characteristic photons both the polychromatic or
monochromatic X-rays can be applied. Disadvantage of polychromatic
excitation mode that a higher background is detected in the TXRF
spectra, because of the critical angle for the total reflection effect de-
pends on the photon energy.
In X-ray emission spectrometry the so called Fundamental
Parameter (FP) theoretical model offers a reference-free calibration
procedure in order to determine the quantitative atomic composition of
a sample [5]. The FP model is based on mathematical relationship
between concentration of chemical elements involved in the analyzed
sample and their excited characteristic intensities. The fundamental
parameters are the energy dependent ionization cross-sections of the
sample elements, fluorescence yields, relative intensities and absorption
jump ratios. The FP approach also considers the geometrical arrange-
ment of the set-up: parameters of sample-source-detector system, ex-
citation mode, properties of the X-ray source and the detector para-
meters, some chemical or physical properties of the sample material etc.
Several publications deal with development and application of FP
technique in XRF analysis especially for those case when producing
standard samples is difficult or simply not possible. Conventional FP
model generally requires good homogeneity of the sample material and
approximately flat sample surface. FP can be used with both of poly-
chromatic and monoenergetic excitation X-ray beams. Important reason
for application of monochromatic excitation mode generally is, that the

⁎
Corresponding author.
E-mail address: szaloki@reak.bme.hu (I. Szalóki).

https://doi.org/10.1016/j.sab.2019.04.010
Received 3 May 2018; Received in revised form 18 April 2019; Accepted 19 April 2019
Available online 24 April 2019
0584-8547/ © 2019 Elsevier B.V. All rights reserved.
I. Szalóki, et al.
theoretical calculation models for quantitative analysis require exact
knowledge of the energy distribution of the primary X-ray beam. De-
termination of this function is a rather complex experimental task that
requires additional measurements on the applied X-ray tube. This dis-
advantageous property of polychromatic X-rays motivates to use
monochromatic X-ray excitation mode.
Due to the unique spectroscopic properties of the TXRF analytical
technique (high sensitivity, analysability of small sample mass), it is
suitable to investigate the atomic compositions of thin deposition layers
on a smooth surface of solid sample holder [6]. Using monochromatic
synchrotron radiation with high flux, the depth profile of the impurity
concentration can be effectively determined. This specialized analytical
technique was demonstrated by Huh et al. [7] on Ni and Fe spin coated
silicon wafer. This depth profile measurement in the range of a few
hundred angstroms were carried out by angle-scan with the exciter X-
ray beam. In TXRF analysis, the widely used calibration procedure is
the internal or external standard methods, however the preparation of
standard samples with very low quantity are rather difficult task [8]. In
this field the VPT (vapor phase treatment) sample preparation method
one of the most effective technique for improvement of detection limit
for TXRF analysis [9]. In some TXRF analytical task the use of internal
or external standard method is limited, for example when direct mea-
surements are performed on environmental substances or only the ex-
ternal calibration can be used in investigation of surface contamination
on silicon wafers. If the sample layer was originally on the surface of the
holder before the analysis was carried out and the distribution of its
quantity and the thickness are unknown this makes difficult to apply
internal calibration methods [10]. For TXRF analysis the synchrotron
radiation (SR) is more advantageous than radiation of X-ray tubes due
to the higher brilliance of synchrotron beam, therefore SR -TXRF offers
a more sensitive analysis [11]. For example, droplet samples containing
boron were analyzed by Streli et al. [12] and the detection limit was
found to be 3 ng. They have shown that a 5 nm thick Carbon layer and a
C-Ni-C multilayer on silicon wafer can be characterized and it is pos-
sible to determine the thickness and density of these layers. Moreover,
the TXRF procedure can be utilized in calibration for direct TXRF
analysis in environmental applications too, such as investigation of
natural contaminated waters [13], geological substances [14], en-
vironmental objects [15], foods [16] and breweries [17]. This wide
range of analytical applications motivates to search the possible sim-
plification of the whole quantification procedure. Adaptation of an
appropriate theoretical model for determination of the sample compo-
sition that allow to leave out these additional calibration experiments.
Considering the above reasons, in a recent research project we devel-
oped a new mathematical model with adaptation of the FP technique
for the reference-free TXRF analysis of standard solutions dropped onto
Si wafers.
2. Theory
One of the theoretical solution for calculation of the quantitative
composition of a very thin contamination layer deposited on surface of
a smooth silicon wafer is the adaptation of FP technique. In order to
create the theoretical FP model had to be developed the exact mathe-
matical relationship between the X-ray fluorescence radiation emitted
by the chemical elements of the surface layer and its elementary com-
position for the TXRF analysis [18,19]. For construction of the TXRF-FP
equations the measuring conditions of the TXRF must be restricted it
assumed as follows:
1. the exciter X-ray beam is monoenergetic, consists of parallel beam
paths and the intensity distribution of the beam is approximately
cylindrically symmetrical at the plane of the wafer surface,
2. the sample is a thin layer deposited on smooth surface of a silicon
wafer,
3. enhancement effect in the sample material is neglected due to the
34
Spectrochimica Acta Part B 156 (2019) 33–41
low thickness of the sample layer
4. the horizontal shape of the sample layer can be approximated as a
cylindrically symmetrical spot,
5. sample spot is in concentric position to the vertical axis of the de-
tector,
6. the roughness of the wafer surface is between 5 and 10 nm,
7. the quantitative distribution of the chemical elements in the sample
spot is approximately homogeneous,
8. in FP calculations the detected intensity of the Kα and Kβ lines are
used
9. the surface of detector is approximately parallel to the surface of the
silicon wafer.
Assumption 5 is not necessarily true in reality, since shape of the
contamination layer on the surface of sample holder is generally non-
cylindrical and the thickness is nor constant. However, the irregular
spatial shape of the real samples can be replaced by a fictitious pattern
having a cylindrical geometrical shape with effective thickness and
diameter. The inhomogeneous distribution of the atomic composition of
the sample must be replaced by homogeneous atomic composition.
Hereinafter, the TXRF model to be presented illustrates a possible
model calculation of these limited parameters of such kind of sample
that has regular shape and homogeneous composition. This model does
not provide a precise description of the physical and chemical para-
meters of the real sample, gives only an approximation by an effective
substitution of the real samples.
Let us supposed number of detectable elements involved in the
contamination layer forming a very thin sample on the surface of the
silicon wafer is ‘n-1’. The set of concentrations of these chemical ele-
ments is C1, …,Cn-1. For the FP model, Fig. 1 introduces in detail the
TXRF set-up with definitions of the geometrical parameters for both the
detector and the sample on the Si wafer holder. The energy of the
primary (exciter) monoenergetic X-ray beam is E and j = 1,2, …,n−1 is
the index of the chemical elements of the sample. The function Ii(r,E) is
the intensity distribution (flux density) of the exciter X-ray radiation
along surface of the sample holder at energy E and at ith incidence
angle (φi i = 1, …,k), which function is approximately cylindrical
symmetrical. The detected flux of emitted characteristic radiation of the
jth element is Iij depending on the incidence angle of excitation beam
and the detection angle (ψ). The TXRF FP model contains several
variables which are discrate and not-continous variables such as φi. In
the equations instead of brackets subscripts are used in order to indicate
mathematical dependence of variables for simple overview. The vari-
able dS (g/cm2) is the effective thickness of the sample layer that is
assumed to be extremely small compared to the distance between sur-
faces of the Si(Li) crystal and the wafer (d). These geometrical condi-
tions can be written in inequality and equality relationships (1), where r
(cm) is the radius (Fig. 1). The first term approximates the relationship
between variable r and the take-off angle (ψ) of the secondary X-rays
propagates toward to the detector crystal. The third term (m) is the
mass (in g unit) of the sample layer and the last two relationships de-
termine constraints for r and rS. The parameter rW means radius of that
area of the irradiated part of the sample holder that is in the field of
view of the detector.
d
dS < < d ⇒ sin ψ ≈ m = dS rS2 π 0 ≤ rS
r 2 + d2
≤ rW 0 ≤ r ≤ rW (1)
At the case of a very thin sample layer the intensities of the char-
acteristic X-rays emitted by the sample's elements depend on the sample
thickness approximately linearly. However, Horntrich et al. [20]
pointed out that over an certain upper limit of sample mass this re-
lationship becomes non-linear, it shows energy dependence and the
characteristic intensities becomes to be saturated. The energy-depen-
dence becomes stronger when the energy of the primary X-ray beam is
I. Szalóki, et al. Spectrochimica Acta Part B 156 (2019) 33–41

Fig. 1. Sketch drawing on the cross section of the TXRF measuring set-up.

rS
nearby to the absorption edge of the excited element. In present FP −dS G1ij (r )
model this absorption effect is taken into consideration by system of Eq. Iij = pgjE Cj ∫ εj (r ) Ii (r , E ) Ω (r ) ⎛ 1 −Ge1ij (r )
⎜
0 ⎝
(2). Variable Ω(r) is the solid angle of the detector from points of circle
with radius r. 1 − e−dS G2ij (r ) ⎞
+ e−dS G1ij (r ) Ri (E ) ⎟ r dr
G2ij (r ) ⎠
rS dS μ (E ) μSj
⎛ −z1 ⎛ S + ⎞ μS (E ) μSj
∫ εj (r ) Ii (r , E ) Ω (r ) ⎜∫ e
⎜ ⎟

Iij = pgj (E ) Cj ⎝ sin ϕi sin ψ ⎠ dz1 i = 1, …k , j = 1, 2, …, n − 1 G1ij (r ) = + G2ij (r )

sin ϕi sin ψ
0 ⎝ 0
μS (E ) μSj
dS μSj
μ (E )
−dS S
μ (E )
−z2 S − (dS − z2 ) ⎞ = −
+ e sin ϕi R
iE ∫ e sin ϕi sin ψ dz
2⎟ r dr
sin ϕi sin ψ
0 ⎠ (4)
n−1 n−1 n−1
∑ Cl = 1 μS (E ) = ∑ Cl μl (E ) μSj = ∑ Cl μlj i Kregsamer and his co-workers [26] derived Eq. (5) for calculating
l=1 l=1 l=1 the reflectivity function Ri(E), of the wafer. This function equals to ratio
= 1, …k j = 1, 2, …, n − 1 (2) of intensity of the reflected (IiR(r,E)) and the exciter X-ray beams
(Ii(r,E)). Variable φT is the refracted angle and φi (i = 1, …,k) is the
The variable p called as instrumental factor that involves all the incidence angle corresponding to Fig. 1. The reflection angle φRi equals
unknown multiplicative constants and parameters are proportional to to the incidence angle φi. The φC is the critical angle of the total re-
the characteristic intensities. The Eq. (2) consider the absorption effect flection effect going on the wafer surface.
caused by the sample material for both the primary and the reflected X- 4(δϕi2 ϕiT2 − 2δ 2ϕi ϕiT3 + δ 2ϕiT4 ) + β 2ϕC4
IiR (r , E )
ray beams. The functions μS(E) and μSj are the attenuation of the sample Ri (E ) = =
Ii (r , E ) 4(δ 2ϕi2 ϕiT2 + 2δ 2ϕi ϕiT3 + δ 2ϕiT4 ) + β 2ϕC4 (5)
at energy E and the characteristic radiation of the jth sample element.
The excitation function gj(E) is given by formula (3) as the product of Take-off angle of the refracted beam (φiT) can be derived from the
following variables: fluorescence yield (ωj), the relative intensity (qj) Fresnel's theory resulting formula (6) that term gives possibility for
and the absorption jump ratio (Jj) of the Kα X-ray fluorescence line of numerical calculation. In functions (5) and (6) the parameters β and δ
the jth chemical sample element [21]. The ionization cross section are defined as element of the complex refractive index (n = 1-δ-iβ) of
(τj(E)) can be substituted by the mass absorption function of the jth the wafer material.
sample element (μj(E)) because in energy range of 1–25 keV the
dominant process is the photoelectric effect that cause the proportion- ϕiT = δ (ϕi2 − ϕC2)/ ϕC2 + (β / δ )2 + δ (ϕi2 − ϕC2)/ ϕC2 (6)
ality between these energy dependent functions.
The absolute value of the real (δ) and imaginary (β) parts of this
gj (E ) = τj (E ) Jj qj ωj ~μj (E ) Jj qj ωj (3) complex optical parameter can be calculated by mathematical expres-
sions given in Eq. (7) including a few physical parameters of the re-
Performing the integration with Eq. (2) by variable z according to flecting matter [7]. In formula (7) r0 ≈ 2.8179·10−15 m is the classical
the geometrical conditions in Fig. 1, the Eq. (4) can be derived for electron radius, L is the Avogadro's number, ZW and ρW are the atomic
calculation of the X-ray fluorescence intensities of the ‘detectable’ ele- number and the density of the wafer material.
ments. Two new functions were introduced in system of Eq. (4) G1ij(r) 1.537⋅102r0 ZW ρW L 12.3981μW (E ) ρW
and G2ij(r) on the basis of the early FP model [22,23] and its later δ= ϕC ≈ 2δ β=
2πAW E 2 4π E
mathematical interpretation [24]. One portion of the flux of the pri-
mary X-ray beam reflects on the smooth surface of the silicon sample (7)
holder. The ratio of the flux densities of the reflected and incidence The parameter A is the atomic mass and μW(E) is the mass absorp-
beams can be calculated by the reflectivity function of the silicon wafer tion coefficient of the wafer material at energy E. The comparison of
(5), which formula can be derived from the Fresnel's theory of the re- Eqs. (5), (6) and (7) shows that through the complex refractive index
flection phenomena [25]. both the reflectivity and the critical angle depends on the excitation X-
ray energy. The values of parameters δ, and β are generally very small,

35
I. Szalóki, et al. Spectrochimica Acta Part B 156 (2019) 33–41

for example at the case of silicon at energy Mo-Kα 17.4 keV these ⎧1 if rS ≤ r
parameters equal β = 8.4·10−9 and δ = 1.6·10−6 [27]. G4i (r ) = μS (E ) G5 (r )
⎨e −d S sin ϕi if r ≤ rS
The system of FP Eq. (4) includes the efficiency function of the Si(Li) ⎩
detector (εj(r)) that is given in general form by expression (8). In the
⎧1 if rS ≤ r 1 − e−dW G3i (r ) 1
first term in (8) defines this simplified notation where (Ej) is energy of = μSW lim =
⎨ e−dS sin ψ if r ≤ rS dW →∞ G3i (r ) G3i (r )
the characteristic radiation of jth element in the sample. This function ⎩
involves the attenuation coefficients of different layers of the Si(Li) (12)
detector indicating by appropriate indexes: Be windows (Be), contact
Based on the application of approximation (12) a simplified version
layer on the detector crystal (Au), active (ac) and inactive layers (in) in
of the Eq. (11) can be derived for the sum of Kα and Kβ silicon char-
the detector crystal [28,29].
acteristic intensities.
−μBe (E ) dBe + μAu (E ) dAu + μSi (E ) dinSi −μSi (E ) dacSi rW
⎛ ⎞⎟
εj (r ) =̇ ε (r , Ej ) ε (r , E ) = e ⎜1 −e
∫ εW (r ) Ii (r , E ) Ω (r ) GG35i ((rr)) r
sin ψ sin ψ
⎝ ⎠ IWi = pgW (E )(1 − Ri (E )) Ki (E ) G4i (r )
0
(8)
dr i = 1, …, k (13)
The parameters dinSi and dacSi refer as the thickness of inactive and
active layers in the detector crystal, respectively. Of course, in the case The multiplication of the instrumental factor (p), intensity dis-
of application of other type of semiconductor detectors such as SDD tribution of excitation X-ray beam (Ii(r,E)) and the solid angle of the
(Silicon Drift Detector), the formula (8) must be modified according to detection (Ω(r)) involved in Eq. (13) is unknown function. Hence, it has
the detector structure and type of its structural layers. Corresponding to to be determined experimentally i.e. measuring Kα + Kβ intensity (IWi)
characteristic X-ray energies of the sample elements the symbol (E) in of pure silicon wafer that is free of surface contamination (dS = 0). The
function (8) must be changed, for example detection efficiency for the factor (p) can be ignored by calculating the quotient of the sample-Eq.
characteristic radiation of the jth element in the sample is symbolized (4) and wafer-Eq. (13), which results in a new system of FP Eq. (14).
by εj(r). The intensity of the entering X-ray beam in the sample holder rS
1 − e−dS G1ij (r )
medium decreases and the distance where this reduction of the initial IWi gj (E ) ∫ εj (r ) Ii (r , E ) Ω (r ) ⎛ G1ij (r )
intensity reach 37% of the initial value, this is defined as penetration 0 ⎝
depth (zi(E)). This parameter can be calculated by Eq. (9), which re- 1 − e−dS G2ij (r ) ⎞
+ e−dS G1ij (r ) Ri (E ) ⎛ G 2ij (r )
⎞ r dr
lationship shows dependence of the penetration depth of the primary X- ⎝ ⎠⎠
Iij = Cj rW
ray beam as function of entering and of critical angles and on the en- gW (E )(1 − Ri (E )) Ki (E ) G4i (r ) ∫ εW (r ) Ii (r , E ) Ω (r ) G 5 (r ) r dr
G (r )

ergy of the primary X-ray radiation [23]. 3i

0
n−1
12.3981
z i (E ) = ∑ Cv = 1 i = 1, …, k j = 1, …, n − 1
4π E δ ( ((ϕi / ϕC )2 − 1)2 + (β / δ )2 − ((ϕi / ϕC )2 − 1)) (9) v=1

The refractive part of the primary beam (IiT) propagates into the
silicon wafer and the angle of the direction of the transmitted beam in
the wafer material (φiT) is less than the entering angle (φi). During the
refraction the density of the energy current of the primary radiation is
changing. The parameter of this effect is called as compression factor
Ki(E) [30], which parameter can be calculated by formula (10).
sin ϕi
Ki (E ) =
z i (E ) μW (E ) ρW
Similarly, to Eq. (2) mathematical expression of the detected char-
acteristic intensity emitted by the silicon wafer can be calculated by Eq.
(11) where IiW is the detected characteristic intensity of the sample
holder and gw(E) is the excitation function of the wafer element (Si).
IiW = p gW (E )(1
rw
−dW G3i (r )
− Ri (E )) Ki (E ) G4i (r ) ∫ εW (r ) Ii (r , E ) Ω (r ) G5 (r ) 1 − Ge3i (r )
0 absorption of the sample layer can be calculated by expression (15),
1 μ
G3i (r ) = + WW i = 1, …k
z i (E ) sin ψ
The factor G3i(r) is an absorption-geometrical parameter for the
wafer material as it defined in (11). This term involves the penetration
depth (zi(E)) of the primary X-ray beam and parameter μWW that is
absorption coefficient of the wafer element for its own Kα + Kβ char-
acteristic radiation. Factors of G4i(r) and G5(r) defined by expressions
(12) account the absorption of the sample layer for both characteristic
radiation of the wafer material (G5(r)) and the primary X-ray beam
(G4i(r)). Absorption effect is taken into consideration for those part of
the wafer, which is covered by sample layer and from bellow the Si
characteristic radiation is emitted. Corresponding to this geometrical
condition the factors of G4i(r) and G5(r) can be calculated by relations
(12).
(14)
If low-Z elements such as H, O, C, N, Na are in the sample those
elements cannot be detected by using Si(Li) or SDD equipped with Be
window, except if the window of the detector is a very thin and low-
absorbing layer [31]. Due to the lack of X-ray signal of this part of the
sample matrix is called as dark matrix [32,33]. In the FP model these
elements are not considered as detected elements, but their attenuation
must be calculated at energy of the excitation energy and of the char-
(10) acteristic radiation of detected elements. The dark matrix can be sub-
stituted with an individual fictive chemical element assigned to one
individual atomic number [34,35], so called effective atomic number,
that is can be not only integer number. It was validated [36] that in the
range of medium and high X-ray energy (1 < E) the energy dependent
attenuation function of this fictive chemical element is approximately
equal to the absorption function of the dark matrix that consist of low-Z
elements, i.e. the effective atomic number can be applied to approx-
r dr imate absorption properties of the dark matrix. For the FP approach the
where μS(E) is the absorption of the sample and μD(E) is the absorption
of the dark matrix at energy E. Variable Cn symbolize concentration of
(11) dark matrix in the sample layer. Considering this new variable Cn, the
normalization equation has to be changed corresponding to Eq. (15).
n n−1 n−1
∑ Cl = 1 ⇒ μS (E ) = ∑ Cl μl (E ) + ⎛⎜1 − ∑ Cl ⎞⎟ μD (E )
l=1 l=1 ⎝ l=1 ⎠ (15)
Finally, the complete system of FP Eq. (13) consists of n number of
equations: (i) n-1 equations related to the concentration of the mea-
sured elements, (ii) the nth equation is the normalization condition for
the concentrations. The unknown variables are set of concentrations
(C1, …, Cn-1,Cn) of the sample elements (including the dark matrix), the
thickness (ds) and the diameter (rS) of the sample spot, i.e. altogether
the number of unknown variables are n + 2. Therefore, the FPM pro-
blem described by system of Eq. (14) contain less number of equations

36
I. Szalóki, et al.
Fig. 2. TXRF spectra of dropped and dried mixed standard solution on silicon
wafer. Measuring time was 100 s, the incidence angle 0.14 degree and
U = 30 kV, I = 300 mA. The blue points are the measured intensities and the
red curve is the fitted functions: Gaussian and polynomial functions. (For in-
terpretation of the references to colour in this figure legend, the reader is re-
ferred to the web version of this article.)
than the number of unknown variables therefore, it cannot be solved
under these limited conditions. Nevertheless, performing the TXRF
experiment on the same identical sample at different entering angles
(φi) of the excitation X-ray beam some results of these new measure-
ments can be introduced in order to increase the possible number of
independent equations.
n−1 k ⎝a
1 (meas)
χ2 = ∑∑ (Iij − Iij(cal) (C1,…, Cn − 1 , dS , rS ))2 = min
j=1 i=1
σij2
The numerical values of the unknown parameters can be de-
termined by minimization of the χ2 function (15) containing the mea-
sured and theoretically calculated fluorescence intensities of the de-
tected elements. Variables σij are the standard deviations of the
measured characteristic intensities.
The main advantage of this new FP model-calculation is that no
standard sample is needed for solution the TXRF analytical task. For the
numerical solution of the minimization problem (15) an in-house
computer code was constructed for determination of quantity of the
chemical elements involved in thin sample layer dropped on the wafer
surface. Essential measuring condition of the TXRF set-up is the surface
roughness of the sample. If this parameter is rather large it can sig-
nificantly influence the reflectivity and the refractivity of the sample
holder and the fluorescence intensity emitted by the sample elements.
However, the Fresnel-theory concerns an exactly smooth interface
surface applying for calculation both the reflectivity and refractivity. In
our experiments the average roughness of wafer surface was given by
the manufacturer as σ ≈ 0.5 − 1 nm . Since the value of the roughness
parameter is so low it allows to neglect its influence on the intensity of
the emitted characteristic radiation from the sample layer and the wafer
[7].
3. Materials and methods
The measurements were carried out with TXRF System 3750 spec-
trometer produced by Rigaku Industrial Corporation. The TXRF facility
was developed for analysis of surface and near surface contamination of
high purity silicon wafers under vacuum condition [37]. For the mea-
surements the high voltage of the W rotating anode was set as 30 kV
and the anode current to 300 mA. The instrument contains 3 different
multilayers for monochromatization of the excitation X-ray beam. Since
the maximum atomic number of the sample elements were 29, the
Spectrochimica Acta Part B 156 (2019) 33–41
energy of the excitation X-ray beam was chosen the line of W-Lβ1,
E = 9.672 keV. The whole analytical procedure such as sample chan-
ging, sample moving into different x-y positions, setting the entering
angle, spectra collection was controlled by computer. The TXRF facility
was equipped with robotics transport system carrying the wafers in-
and out the evacuated measuring chamber. All the experiments were
carried out in specially designed and built clean-room-laboratory es-
tablished at RIGAKU International Corporation. The entering angle of
the X-ray beam was adjustable and it was possible to set the orientation
of the investigated wafer, i.e. the wafer was rotatable around the ver-
tical axis. As sample holder pure Si wafers were used having 480 μm of
thickness and 5″ of diameter. The Si(Li) detector was manufactures by
Oxford Instruments with parameters dBe = 12.5 μm, dco = 20 nm (Au),
dac ≈ 5 mm, din ≈ 10 nm and the active area of the detector crystal was
A = 80 mm2. In order to test the theoretical calculations, standard
mixed solutions were prepared containing K, Sc, V, Mn, Co, Ni and Cu
elements with 0.2, 0.5, 1, 2, 5, 10 and 100 mg/l concentrations. From
this solutions, 1 μl or 10 μl volumes were dropped onto the surface of a
purified Si wafer with an automatic micropipette. The fluorescence
spectra were measured at two different values of entering angle at 0.1,
0.2 degrees. More detailed angle-scan measurements were performed
between 0.03 and 0.22 degrees to compare the theoretically calculated
and the measured characteristic intensities of pure silicon at different
entering angles in order to validating this new TXRF FP procedure.
Typical TXRF spectra is plotted on Fig. 2 that was measured on mixed
standard solution for K, Sc, V, Mn, Co, Ni and Cu elements with con-
centrations 1 mg/l of each. The sizes of the geometrical dimensions are
rD = 3 mm, d = 8.5 mm, a = 3.5 mm and parameter rW can be calcu-
lated on the basis of Fig. 1 this parameter obtained by Eq. (17) as.
2d
rW = rD ⎛ − 1⎞ ≈ 11.6 mm.
⎠ (17)
(16)
4. Determination of the instrumental functions
The arithmetical product of instrumental functions Ii(r,E)Ω(r) in
Eqs. (2), (4), (11) and (14) describes the 2D intensity distribution of the
primary X-ray beam in the plain of surface of the silicon wafer and the
solid angle for the detector along the flat surface of the wafer. The value
of this combined function must be known at each of wafer's surface
point before the calculation of the quantity of the chemical elements
and the characteristic intensity of the wafer. Due to the rather com-
plicated theoretical formalism of the exact mathematical expression of
this 2D function it worst to determine experimentally. The diameter of
the cylindrical area on the wafer surface from where the characteristic
radiation emitted and this radiation reaches the detector surface was
approximately 15–20 mm. This is a relatively large area comparing to
other geometrical parameters of the current TXRF set-up; therefore, the
2D distribution of the flux density of the primary and secondary beam
must be determined for the further FP calculations. In order to char-
acterize experimentally this property of the primary beam and the ex-
perimental set-up 1 μl quantity of mixed solution of K, Sc, V, Mn, Fe, Co,
Ni and Cu elements were dropped on the surface of Si wafer. The
concentration of each element in the droplet was 1 mg/l. After the
drying procedure the diameter of the sample spot was approximately
1.0–1.5 mm. The thickness of the dropped sample was obtained not to
be larger than 10−8 g/cm2 that value corresponds < 1 nm thickness.
Transmission functions of this kind of dropped sample was calculated at
different thicknesses of 1, 10, 50, 100 nm versus energy and plotted on
Fig. 3. The numerical procedure and dataset applied for the transmis-
sion calculation was published by Henke et al. [38]. The values of
numerically calculated functions were found very near to 100% in en-
ergy range between 1 and 10 keV. However, preparing droplet with
20–100 μg/l concentrations the absorption effect of the layer cannot be
neglected especially at the lower energy range (E < 6 keV). But, in case
of a very thin sample layer the absorption effect for the primary X-ray
37
I. Szalóki, et al. Spectrochimica Acta Part B 156 (2019) 33–41

Fig. 3. Calculated transmission functions of droplet layers on the wafer surface

versus energy [38]. Fig. 4. Intensity distribution of a point-like Co droplet (1 μl, 10 mg/l) sample on
Si wafer along the x and y coordinates in horizontal plane. The calculation of
the error bars is in the text. The incidence angle of the exciter X-ray beam was
beam can be ignored since the term of the attenuation of the sample
0.1 degree.
approximates to value of the layer thickness itself (18).
2μS (E ) dS
− 1 − e−dS G1ij (r ) 1 − e−dS G2ij (r ) polynomial functions for fitting the measured characteristic intensities.
lim e sin ϕi =1 ⇒ lim = lim
dS → 0 dS → 0 G1ij (r ) dS → 0 G2ij (r ) The error bars (σP) were calculated by σP2 = σT2 + σB2 where σT and σB
are the variances of the total counts of the peak and the background
= dS (18)
under the peak. Using these empirical data for calculation Ii(r,E)Ω(r)
Application of condition (18) for measuring set-up used for Eq. (4) function applying eq. (20), the functions (14) can be calculated and
and supposing a very thin sample layer with small (≈1 mm) diameter, solved the minimization problem with χ2 expression (16).
the system of Eq. (4) can be simplified as it given in Eq. (19). In this
expression variable Δ(cm2) is the area of the thin sample and t is the 5. Results
number of chemical elements in the droplet sample.
This new theoretical standard-free FP model under TXRF conditions
Iij (r )~gjE Cj εj (r ) Ii (r , E ) Ω (r ) dS (1 + Ri (E )) Δ i is represented by system of Eq. (14). One of the possible numerical
= 1, …, k j = 1, 2, …, t (19) solution of the system of equations requires knowledge of Si-Kα and Si-
Kβ detected intensities. Performing additional TXRF experiments at
Note, in (19) the detected intensity (Iij(r)) depends on the radius (r) different entering angles of the excitation X-ray beam on a sample layer
due to the small size of the sample spot. The characteristic radiations of result additional intensity data of characteristic X-rays emitted by the
this test sample is measured in different x,y positions in the plane of the sample elements. In order to validate this new FP approach, the cal-
wafer surface. The multiplication of variables Ii(r,E) and Ω(r) can be culated and measured Si fluorescence Kα + Kβ signals obtaining from
derived in Eq. (20) that expression allows to calculate the unknown an angle-scan type TXRF measurement carried out on cleaned and
term Ii(r,E)Ω(r) as function of r, energy and the entering angle (i) of the smooth surface of silicon wafer were compared. The measured and FP
exciter X-ray beam. The sample was prepared with mass of 1 μl and the calculated Si Kα + Kβ characteristic intensities are plotted on Fig. 5
concentrations were set 1 mg/l that resulted high transmission prop- where the scan was performed in the range of incidence angles
erty. Therefore, it was suitable in experiment for determination of the
instrumental function, which consists of intensity distribution of the
primary beam and the solid angle of the detector (20). The x and y
position of the dried droplet were changed by moving the Si wafer
horizontally in directions x and y axes, and the TXRF spectra were
collected in several individual position. As an example for determina-
tion of the intensity distribution of the excitation X-ray beam, measured
distributions of Co-Kα intensity were plotted on Fig. 4 along x and y
axes with a fitted inverse third-order polynomial function at degree 0.1.
Applying this fitted functions, the Iij(r) intensity distribution can be
calculated in the plain of the surface of the sample holder at optional
(x,y) coordinates.

Iij (r )
Ii (r , E ) Ω (r )~ i = 1, …, k j = 1, 2, …, t
gjE Cj εj (r ) dS (1 + Ri (E )) Δ
(20)
These type of measurements were performed at 12 different in-
cidence angles in the range of 0.03–0.22 degrees resulting experimental
dataset that allows to determine the multiplication of variables
Ii(r,E)Ω(r) at various incidence angle. Fig. 4 shows an example for the Fig. 5. Measured and FPM calculated intensities of the sum of Si-Kαβ peaks
calculation the 2D profile of the exciter beam using empirical versus angle of incidence of the exciter X-ray beam.

38
I. Szalóki, et al. Spectrochimica Acta Part B 156 (2019) 33–41

Fig. 6. Nominal and FPM calculated mass of droplet samples on surface of si- Fig. 7. Detection limit of the TXRF analytical set-up (MDL) given in pg and
licon wafer for K, Sc, V, Mn, Co, Ni and Cu elements. atoms/cm2 units, U = 30 kV, I = 300 mA, measuring time 100 s.

0.03–0.22 degree. An acceptable agreement was found between mea- the surface contamination: effective quantities of the chemical elements
sured and FP calculated characteristic intensities of silicon that result and effective diameter of the contamination spot. The element depen-
allows the conclusion that system of Eq. (14) can be realistically applied dent detection limits (MDL) [8] of the whole TXRF analysis and FP
for the TXRF FP calculations. Dropped solution of K, Sc, V, Mn, Co, Ni model calculations were determined for the investigated chemical ele-
and Cu elements were measured and the quantities of solved elements ments. The MDL values refers to TXRF set-up, experimental conditions
were calculated by the TXRF FP model. The calculated quantities of the and applied measuring parameters, which were described above in
chemical elements in the droplet sample was compared to the nominal chapter 3, Materials and Methods. The reference time for measuring
elementary quantities and the results are plotted on Fig. 6. was 100 s. The Fig. 7 shows the dependence of MDL on the atomic
Deviances between the two type of dataset were calculated and the number of the investigated chemical elements both in unit of pg and
numerical results are summarized in Table 1. Similarly, to the case of atoms/cm2.
the scan on pure silicon wafer acceptable agreement was found between
the nominal and calculated concentrations. The average deviations
6. Conclusions
between the two types of dataset were found around 10% relative. The
greatest deviances were obtained for K, Sc and Co elements at low
New fundamental parameter (FP) model for TXRF analysis was
concentration range (0.2, 0.5 μg/l). In order to simplify the FP model
developed in order to determine the quantity of contamination on
we have supposed for the sample layer has a cylindrically symmetric
surface of high purity silicon wafers. The FP model calculates the ab-
shape on the silicon wafer and it has constant thickness. However, in
sorption effects caused by the sample layer and considers the cylin-
reality the shape of the sample spot or the contamination on the wafer's
drically symmetric intensity distribution of the monochromatic excita-
surface are perhaps generally not symmetrical and it does not have
tion X-ray beam. For a non-cylindrically symmetric case, the FP
regular form and constant thickness. But, at the case of a real sample
equations must be modified extending the one-dimension integration
layer, the irregular form and the not constant thickness can be sub-
performed with variable r in Eq. (2) to a two-dimension versions on the
stituted by such kind of effective sample that has cylindrically sym-
excited wafer surface. This type of extension of the model is not in-
metric shape and it can be charcaterize with an effective thickness and
volved in this work.
diameter. Analyzing this effective sample, the concentrations or masses
Calibration of this FP approach for determination the level of sur-
of the chemical elements in the sample layer deposited on the wafer
face contamination by TXRF analysis is based on theoretical calculation
surface can be calculated. The influence of the inhomogeneous dis-
and measurement of fluorescence intensity of the silicon wafer. The
tribution in the sample mass on the detected characteristic intensities
main advantage of this analytical procedure that it is standard-free i.e.
can be reduced with decreasing the analyzed surface area, for example
determination of quantity of the chemical elements on the surface of the
with diminishing the solid angle of the detector. Finally, the simulta-
silicon wafer does not require application both external or internal
neous application of this new TXRF FP model and the proposed mea-
standard elements. For exact solvability of the theoretical equations a
suring procedure may provide relevant information on the quantity of
few additional angle-scan measurements has to be carried out at dif-
ferent incidence angles between the wafer surface and the exciter X-ray
Table 1 beam. For this type of additional experiments well cleaned silicon wafer
Deviation between nominal (Cnom) and the FPM calculated (Ccal) concentrations is necessary for both the sample measurement and for determination of
for K, Sc, V, Mn, Co, Ni and Cu elements. the unknown instrumental factors. In order to validate the proposed FP
Cnom (μg/l) (Ccalc − Cnom)/Cnom (%) 6 based model artificial contamination was prepared on high purity si-
1 Ccalc − Cnom
∑ (%) licon wafers as dropped solutions of K, Sc, V, Mn, Co, Ni and Cu ele-
k Cnom
i=1
K Sc V Mn Co Ni Cu ments. The level of purity of the wafer surface used for the experiments
was checked by an additional TXRF measurement before the calibration
0.2 – – – – – 15 – –
0.5 26 18 2 2 20 10 12 12.9 measurements. This new standard-free TXRF FP analytical procedure
1 28 13 16 16 6 9 20 15.4 and the developed algorithm for the numerical solution of the related
2 < 1 24 3 3 < 1 8 9 6.9 theoretical equations should become a useful tool in the quality control
5 9 2 7 7 4 3 10 6.0 of semiconductor industry for determination of the impurities on Si
10 14 14 9 8 11 13 4 10.4
wafers surface. Moreover, this method can be utilized effectively in
100 < 1 15 6 5 14 – 4 6.3
Average deviance of the TXRF FPM analysis 9.6 various so called direct-type TXRF analysis performed in investigations
of environmental samples, waters, geological substances, foods and

39
I. Szalóki, et al. Spectrochimica Acta Part B 156 (2019) 33–41

drinks. This standard-free TXRF FP analytical procedure can be utilized
in the semiconductor industry and in various TXRF analysis performed
for investigations of environmental samples, waters, geological sub-
stances, foods and drinks.
Acknowledgments
of Science, the Rigaku Industrial Corporation (Takatsuki), Department
of Solid State Electronics in Osaka Electro-Communication University
Neyagawa, Japan. This work has been partly carried out in the frame of
VKSZ-14-1-2015-0021 Hungarian project supported by the National
Research, Development and Innovation Found.

This research was supported by the Japan Society for the Promotion

Appendix A. Appendix

Summary of brief definitions and short explanations of variables, parameters and functions used in FPM model and its equations.
Measuring set-up and excitation

k Number of entering angle,

φi ith entering angle of primary X-ray beam to surface of the sample (i = 1, …,k),
ψ Take of angle of secondary X-ray beam to surface of the sample holder,
φiT Refraction angle in sample holder at the ith entering angle of the excitation X-ray beam,
E Energy of the excitation X-ray beam (E = 9.672 kev),
a Distance between Be window and surface of Si(Li) detector crystal,
d Distance between surface of sample holder and surface of Si(Li) detector crystal,
dw Thickness of silicon sample holder (g/cm2),
rD Radius of round-shaped “visible” part of Si(Li) detector crystal,
rw Radius of the irradiated part of the silicon sample holder,
p Instrumental factor,
Ii(r,E) Intensity distribution of primary X-ray radiation in the plain parallel to surface of the sample holder at energy E and at ith incidence angle (i = 1, …,k),

Detection

Ω(r) Solid angle of detector surface from point determined by r,

εj(r) Efficiency function of energy dispersive detector at energy of jth element,
εw(r) Efficiency function of energy dispersive detector at energy of wafer element,
dBe Thickness of the Be window of the Si(Li) detector (g/cm3),
μBe(E) Absorption coefficient of Be window at energy E,
dacSi Thickness of the active layer of the Si(Li) detector crystal,
dinSi Thickness of the inactive layer of the Si(Li) detector crystal,
μSi(E) Absorption coefficient of silicon crystal at energy E,
dco Thickness of the contact layer of the Si(Li) detector crystal,
μco(E) Absorption coefficient of the contact layer of the Si(Li) detector at energy E,

Sample holder

gw(E) Excitation functions of the wafer element at energy E,

μw(E) Attenuation of wafer at energy E,
μww Attenuation of the wafer at energy of characteristic X-ray radiation of the wafer,
ρw Density of the wafer (g/cm3),
Aw Atomic number of the wafer,
Iwi Intensity of characteristic peak of the wafer at ith entering angle,
μsw Attenuation of sample layer at characteristic energy of the wafer element,
φc Critical angle of the sample holder (silicon wafer),
δ Real part of the complex refractive index of wafer material,
β Imaginary part of the complex refractive index of wafer material
Ri(E) Reflection of the wafer at energy E and at ith entering angle,
Ki(E) Compression factor of the wafer at energy E and at ith entering angle,
zi(E) Penetration depth in the wafer at ith entering angle (i = 1, …,k) and energy E,
Δ Area of dropped sample for determination of the intensity distribution of the primary X-ray beam,

Samples

n Number of measured chemical elements in the sample layer,

t Number of elements in the test sample,
Cj Concentration of jth element in the sample layer (j = 1, …,n),
Iij Detected intensity of characteristic peak of the jth element in the sample layer at ith entering angle,
σij Standard deviations of the measured characteristic intensities of the jth element at ith entering angle
gj(E) Excitation functions of jth element at energy E,
ωj Fluorescence yield of the jth element,
Rj Radiative rate of the jth element,
Jj Absorption jump ratio of the jth element,
τj(E) Photoelectric cross section of the jth element at energy E,

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I. Szalóki, et al. Spectrochimica Acta Part B 156 (2019) 33–41

μs(E) Attenuation of sample layer at energy E,

μij Attenuation of the ith element at energy of characteristic X-ray radiation of jth elements,
μsj Attenuation of the sample at energy of characteristic X-ray radiation of jth elements,
dS Thickness of sample layer (g/cm2),
rs Radius of the circular-shaped sample layer,
Iji(r) Detected intensity of characteristic peak of the jth element in the test sample at ith entering angle,

Calculation

z1 Integration variable in the sample volume (0 ≤ z1 ≤ ds),

z2 Integration variable in the sample volume (0 ≤ z2 ≤ ds),
z3 Integration variable in the wafer volume (0 ≤ z3 ≤ dw),
x,y Coordinates on the plain on the surface of the sample holder,
r Radius of the surface of the sample holder.

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