The Rigaku Journal
Vol. 13/ number 1/ 1996
CONTRIBUTED PAPERS
X-RAY FLUORESCENCE ANALYSIS OF HEAVY ATOMS
BY USE OF ULTRASHORT WAVELENGTH X-RAYS
YASUHIKO TAKAHASHI
Institute of Applied Physics, University of Tsukuba, Tsukuba 305, Japan
1. Introduction
The purpose of this paper is to report on an
experiment and its result using X-ray fluorescence
(XRF) analysis. The experiment was conducted on
samples that contain heavy elements, employing an
analytical system designed for the determination of
ultrashort-wavelength-photon electron density distri-
bution. The system is currently installed at the Nation-
al Institute for Research in Inorganic Materials,
Science and Technology Agency of Japan. One of its
salient features is that it is capable of exciting X-rays
in far higher energy (i.e. ultrashort wavelength) re-
gions than the conventional X-ray wavelength regions
hitherto in use. This is enabled by applying an exceed-
ingly high excitation voltage of 200 kV. The experi-
mental techniques using short wavelength X-rays dif-
fer accordingly in some respects from the ones with
the conventional X-rays. Also, it seems important to
clarify where the effectiveness lies in using short-
wavelength X-rays.
Fig. 1 X-ray spectra due to air scattering
23
The advantage of using short-wavelength X-rays
will therefore be discussed by taking up an example of
sample analysis with XRF, one of the X-ray experi-
mental methods.
2. System for Experiment
The analytical system for the determination of
ultrashort-wavelength-photon electron density distri-
butions used for the present experiment is first
explained [1]. Its X-ray generator is of Rigaku make.
The maximum output is 2 kW and the maximum tube
voltage and tube current are 200 kV and 12 mA
respectively. Because of X-ray generation with a de-
mountable tube type fixed anode, the source stability
is substantially higher. The most remarkable charac-
teristic of X-rays emitted from this generator is that
X-radiation can excite WKα rays with high efficiency
thanks to the use of a tungsten (W) target and of a high
voltage 200 kV maximum. Figure 1 shows measure-
ment by air scattering (2θ=2°), where the tube voltage
The Rigaku Journal
was varied in 20 kV steps from 60 kV to 200 kV with
the tube current kept constant. One can see a linear
increase in the top peak intensity with the rise of the
tube voltage. Detected also were fluorescent X-rays
due to Pb (PbKα, PBKβ) generated from a beam
stopper attached to a four-circle diffractometer. This
diffractometer is the HUBER Model 512 off-center
type. As the X-ray detector, a CANBERRA semi-
conductor detector (SSD-pure Ge) was used, which
features high detection efficiency and high energy
resolution. Further, a main amplifier and a pulse
height analyzer (P.H.A.), both from CANBERRA,
were used along with a NAIG multichannel pulse
height analyzer (M.C.A.) and an NEC personal
computer PC-9801 (Photo 1).
Semiconductor Detector:
In general, X-ray crystal structure analysis is
performed mainly by the angular dispersive method
(ADX). This method is such that regarding X-rays
emitted from the ray source, the Kα radiation alone is
spectrally separated with an analyzing crystal such as
HOPC or Ge, and is applied to a sample for measure-
ment. The X-ray intensities are thereby measured. On
the other hand, in the case of using a semiconductor
detector as with the present system, the detector itself
is so good in terms of energy resolution that the sort-
ing of the diffracted X-rays can be done by the detec-
tor itself, making it unnecessary to use the dispersive
system like the analyzing crystal. Thus the system
Photo 1 Precision analysis system for ultrashort wavelength photon electron density distribution
Vol. 13 No. 1 1996
configuration can be much simplified. This method is
called the energy dispersive method (EDX) to
differentiate from the angular dispersive method.
The energy dispersive method is characteristic in
that it permits simultaneous observation of the whole
X-ray spectra with no need of moving the system
during measurement.
Figure 2 shows an example of simultaneous
observation by the energy dispersive method where
X-ray diffraction was confirmed in such a way as to
satisfy the Bragg condition for the 333 reflection of an
YB6 single crystal with respect to the WKα, radiation.
Here, the relations between the energy and incident
ray wavelength λ may be represented by E=12.39/λ
(keV) (for λ in C). It can be seen from this figure that
besides the 333 reflection, other reflections such as
111, 222, 444, 555 and 666 caused by diffraction
upon satisfying the Bragg condition with respect to
the white components of the incident X-rays were
observed as well.
3. X-ray Fluorescence Analysis
Brief explanations will be made on the principles
of X-ray fluorescence emission from the sample and
on the XRF technique. When a substance is irradiated
with X-rays, inner-shell electrons of the constituent
atoms are excited and removed. The atoms become
ionized by losing their inner electrons, so electrons
from outer shells drop into the vacancies left by the
24
 Fig. 2 Fluorescent X-rays of YB6 single crystal by the energy dispersive system.
departed electrons. There is surplus energy occurring
on this occasion, i.e. a characteristic X-ray, called a
fluorescent X-ray, and it is inherent to each type of
element. Since its wavelength is constant depending
on the element type, fluorescent X-rays can be utilized
for identification of substances and like work.
In the XRF technique, the qualitative and
quantitative analyses of elements contained in a sub-
stance are performed by conducting spectral analysis
of fluorescent X-rays produced from the substance. A
crystal spectroscope is mainly used for this spectral
analysis. In quantitative analysis, however, since a
number of factors depend on the X-ray wavelength,
such as absorption due to the air, crystal reflecting
power, fluorescence excitation efficiency and counter
efficiency, these factors entail lots of corrections to be
made. Generally, the qualitative and quantitative
analyses of heavy elements existing among light
elements can be easily carried out. Automatic mea-
surement is also easy, so their analytical techniques
are useful for handling large quantities of oxides, etc.
4. Experiment and Result
All of the XRF analyses under the present
experiment was conducted by an energy dispersive
type apparatus. It uses a multichannel pulse height
analyzer. The time constant of the main amplifier was
set at 2.0 µs. If a longer time constant were set, the
energy resolution would improve. But as the intensity
of X-rays entering the SSD becomes higher, counting
25
loss of the signals coming into the amplifier will occur
increasingly. A conclusion drawn after these consi-
derations was that a 1 to 2 µs time constant was appro-
priate.
In actual measurement, the 2θ angle of the
diffractometer was set at 90° in order to avoid
mixing-in of characteristic X-rays emitted from the
tungsten target itself. Three types of samples were
used: rare earth oxide powder, rare earth hexaboride
single crystal, and Pt and Pt13 A at%Rh. Each mea-
surement result will be described below in order.
1) Rare Earth Oxide
A powder sample was used for the measurement
of rare oxide (R2O3). It was fixed onto both-side
adhesive tape and was placed at the center of the four
circle diffractometer. Then direct X-ray irradiation
was made.
The XRF spectra detected from elements having
the atomic numbers in a lower to higher order starting
with La were superposed for comparison (Fig. 3). The
result shows that in the case of samples whose atomic
numbers are about the same as those of the rare earth,
the sample identification can be made sufficiently
with XRF peaks. Also, regarding Kα1 and Kα2, the
way they are going to separate from each other as the
atomic number increases can be clearly known. This
is because the energy difference between Kα1 and
Kα2 becomes greater with an increase in the atomic
number. On the other hand, there is no peak separa-
The Rigaku Journal
 Fig. 3 Fluorescent X-rays of rare earth oxide.

Fig. 4 Fluorescent X-rays of RB6 single crystal.

tion in the case of La, Ca, etc. for the reason that the
energy resolution of the SSD is inferior to their energy
difference. The SSD resolution can be improved to
some extent, though, by varying the preamplifier set-
ting for the SSD (e.g. by making the time constant
greater).
From the above result, it may be known that
regarding powder samples containing heavy ele-
ments, even a very simple experiment can satisfy the
requirements for identification.
2) Rare Earth Boride
The sample used was an RB6 (R=rare earth) single
crystal synthesized by the floating zone method. With
a discharge cutter, a cylindrical sample was cut out
into a similar shape, 3 mm in thickness and 5 mm in
diameter approximately. Figure 4 shows the outcome
of X-irradiation to the sample surface.
The result was such that the same thing can be
said as with the measurement result of the above rare
earth oxide. What should be noted here is that heavy-
element impurities can be detected far more easily
when conducting the crystal structure analysis, elec-
tron density distribution analysis and the like analysis
with single crystals. For the structure analysis, in
particular, it is possible to identify impurities in a very
convenient way with a sample for measurement kept
mounted on the four-circle diffractometer. We are

Vol. 13 No. 1 1996 26

 Fig. 5 Fluorescent X-rays of Pt, Pt13 A at%RH.
currently making only the qualitative XRF analysis.
But when quantitative analysis becomes practical, it
will then be possible to experimentally determine the
sample composition and to proceed on the structure
analysis and the electron density distribution analysis
while maintaining the same sample condition.
3) Pt, Ptl3 A at%Rh
Two types of samples, Pt and Pt13 A at%Rh, pre-
pared by Furuya Metal Co. were used. They were
cylindrical, 1 mm in diameter and 5 mm in height. To
effect the same measurement condition, the samples
were placed in parallel to the incident X-ray beam.
Each of them was adhered to a glass rod to facilitate
their installation in a similar way to that for single
crystal measurement. Figure 5 shows the result of
XRF analysis of them with the K series radiation.
One can see that because the excitation voltage of
the X-ray source is exceedingly high, the observation
of the Kα and Kβ rays of Pt (PtKα1 λ = 65.122 keV), a
heavy element, can be made sufficiently well.
Moreover, the way the PtKα1 and PtKα2 peaks are
distinctly separated can be seen. In the measurement
result of the Pt sample containing 13%Rh, one can
know that the fluorescent X-rays of Rh (RhKα1 =
20.074 keV) were also detected and that the Pt X-ray
fluorescence peak was diminished. Hence, ultrashort-
wavelength X-rays are considered to display high
performance in detecting heavy-element impurities
27
existing in heavy element samples. For light-element
impurities, however, the measurement method using
ultrashort wavelength X-rays cannot be regarded as
effective at the present stage.
5. Study
For XRF analysis using long wavelengths, high-
precision experiments have been going on, and the
quantitative analysis techniques are now on the ppm
order. Since, however, no higher energy fluorescent
X-rays will be emitted from the sample for measure-
ment than the given energy, heavy-element analysis is
performed by analyzing L-series XRF spectra.
Where, then, should one find the advantages of
XRF analysis using short-wavelength X-rays? The
first advantage may be the simplicity of peaks for
detection. Regarding L-series fluorescent X-rays,
there are many kinds. Moreover, because energy
differences between the respective X-rays are small,
this poses a problem in that peak separation by
calculation becomes necessary when dealing with
samples containing elements of adjoining atomic
numbers. Whereas, in the case of analysis with the K-
series radiation, there are only four kinds of
fluorescence X-rays to be observed, that is, Kα1,2 and
Kβl,2. Further, their respective energy widths are
larger compared with the L-series radiation. As a
result, experiment and analysis may be made much
simpler, especially for qualitative analysis of samples.
The Rigaku Journal
 The second advantage may be that information on
the sample's inner part can be obtained. With long
wavelength X-rays, the effect of the sample surface,
especially those of samples containing heavy ele-
ments may be said to be great. Whereas, short wave-
length X-rays can penetrate deep into the interior of
the sample. For instance, it is easy for such X-rays to
penetrate through a 2 cm aluminum plate.
Reported above is the XRF analysis conducted on
samples containing heavy elements by use of short-
wavelength X-rays. The sample shape (powder, single
crystal, alloy) was disregarded. However, the present
experiment is by only qualitative analysis, and there-
fore the author is considering to work on more and
more experiments toward quantitative analysis.
6. Concluding Remarks
Currently, the SPring-8 storage ring is being built
at Nishiharima, Hyogo Pref., and is scheduled to be
commissioned in 1997. This facility, when completed,
will offer ultrashort-wavelength X-rays featuring high
brilliancy. As one of the experiments utilizing such
short-wavelength X-rays, XRF analysis using the K-
series radiation may be cited.
The present system referred to in this paper is
originally designed for electron density distribution
analysis using single crystal samples. In fact, the
analysis of Si, Ge, etc. is being carried on [2], and the
analysis of superconductive materials, RB6 (R=rare
earth), etc. is also scheduled to be put into practice for
Vol. 13 No. 1 1996
the time ahead. Since short wavelength X-radiation is
available in a laboratory as well, the author hopes to
continue varied experiments in such a way as to serve
for the oncoming stepped-up experiments at the
SPring-8.
Acknowledgment
I would like to acknowledge the many assistances
given by the following people in preparing this report.
I am indebted to Dr. Fujio Okamura, chief
researcher, and Dr. Takeshi Yukino, at National
Institute for Research in Inorganic Materials, Science
and Technology Agency of Japan for providing
research environments and pertinent advices. I thank
Dr. Kazuki Yamamoto in Physical Engineering Dept.
of University of Tsukuba for various ideas and
suggestions. I thank Dr. Yoshihiro Kino at Rigaku
Corporation for providing Pt, Pt13 A at%Rh, and thank
Dr. Shigeru Otani and Dr. Takaho Tanaka at the
aforementioned institute for RB6 single crystals. I am
also grateful to Prof. Ken’ichi Ohshima in Institute of
Applied Physics of the above university, where I am a
graduate student, for considerations given officially
and privately.
References
[1] F. P. Okamura: The Rigaku Journal, Vol. 11, No. 2,1994.
[2] K. Yamamoto, et al.:in press.
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29 The Rigaku Journal