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 advantage of using short-wavelength X-rays

The purpose of this paper is to report on an will therefore be discussed by taking up an example of
experiment and its result using X-ray fluorescence sample analysis with XRF, one of the X-ray experi-
(XRF) analysis. The experiment was conducted on mental methods.
samples that contain heavy elements, employing an 2. System for Experiment
analytical system designed for the determination of
ultrashort-wavelength-photon electron density distri- The analytical system for the determination of
bution. The system is currently installed at the Nation- ultrashort-wavelength-photon electron density distri-
al Institute for Research in Inorganic Materials, butions used for the present experiment is first
Science and Technology Agency of Japan. One of its explained [1]. Its X-ray generator is of Rigaku make.
salient features is that it is capable of exciting X-rays The maximum output is 2 kW and the maximum tube
in far higher energy (i.e. ultrashort wavelength) re- voltage and tube current are 200 kV and 12 mA
gions than the conventional X-ray wavelength regions respectively. Because of X-ray generation with a de-
hitherto in use. This is enabled by applying an exceed- mountable tube type fixed anode, the source stability
ingly high excitation voltage of 200 kV. The experi- is substantially higher. The most remarkable charac-
mental techniques using short wavelength X-rays dif- teristic of X-rays emitted from this generator is that
fer accordingly in some respects from the ones with X-radiation can excite WKα rays with high efficiency
the conventional X-rays. Also, it seems important to thanks to the use of a tungsten (W) target and of a high
clarify where the effectiveness lies in using short- voltage 200 kV maximum. Figure 1 shows measure-
wavelength X-rays. ment by air scattering (2θ=2°), where the tube voltage

Fig. 1 X-ray spectra due to air scattering

23 The Rigaku Journal

was varied in 20 kV steps from 60 kV to 200 kV with configuration can be much simplified. This method is
the tube current kept constant. One can see a linear called the energy dispersive method (EDX) to
increase in the top peak intensity with the rise of the differentiate from the angular dispersive method.
tube voltage. Detected also were fluorescent X-rays The energy dispersive method is characteristic in
due to Pb (PbKα, PBKβ) generated from a beam that it permits simultaneous observation of the whole
stopper attached to a four-circle diffractometer. This X-ray spectra with no need of moving the system
diffractometer is the HUBER Model 512 off-center during measurement.
type. As the X-ray detector, a CANBERRA semi-
conductor detector (SSD-pure Ge) was used, which Figure 2 shows an example of simultaneous
features high detection efficiency and high energy observation by the energy dispersive method where
resolution. Further, a main amplifier and a pulse X-ray diffraction was confirmed in such a way as to
height analyzer (P.H.A.), both from CANBERRA, satisfy the Bragg condition for the 333 reflection of an
were used along with a NAIG multichannel pulse YB6 single crystal with respect to the WKα, radiation.
height analyzer (M.C.A.) and an NEC personal Here, the relations between the energy and incident
computer PC-9801 (Photo 1). ray wavelength λ may be represented by E=12.39/λ
(keV) (for λ in C). It can be seen from this figure that
Semiconductor Detector:
besides the 333 reflection, other reflections such as
In general, X-ray crystal structure analysis is 111, 222, 444, 555 and 666 caused by diffraction
performed mainly by the angular dispersive method upon satisfying the Bragg condition with respect to
(ADX). This method is such that regarding X-rays the white components of the incident X-rays were
emitted from the ray source, the Kα radiation alone is observed as well.
spectrally separated with an analyzing crystal such as
3. X-ray Fluorescence Analysis
HOPC or Ge, and is applied to a sample for measure-
ment. The X-ray intensities are thereby measured. On Brief explanations will be made on the principles
the other hand, in the case of using a semiconductor of X-ray fluorescence emission from the sample and
detector as with the present system, the detector itself on the XRF technique. When a substance is irradiated
is so good in terms of energy resolution that the sort- with X-rays, inner-shell electrons of the constituent
ing of the diffracted X-rays can be done by the detec- atoms are excited and removed. The atoms become
tor itself, making it unnecessary to use the dispersive ionized by losing their inner electrons, so electrons
system like the analyzing crystal. Thus the system from outer shells drop into the vacancies left by the

Photo 1 Precision analysis system for ultrashort wavelength photon electron density distribution

Vol. 13 No. 1 1996 24

 Fig. 2 Fluorescent X-rays of YB6 single crystal by the energy dispersive system.

departed electrons. There is surplus energy occurring loss of the signals coming into the amplifier will occur
on this occasion, i.e. a characteristic X-ray, called a increasingly. A conclusion drawn after these consi-
fluorescent X-ray, and it is inherent to each type of derations was that a 1 to 2 µs time constant was appro-
element. Since its wavelength is constant depending priate.
on the element type, fluorescent X-rays can be utilized
In actual measurement, the 2θ angle of the
for identification of substances and like work.
diffractometer was set at 90° in order to avoid
In the XRF technique, the qualitative and mixing-in of characteristic X-rays emitted from the
quantitative analyses of elements contained in a sub- tungsten target itself. Three types of samples were
stance are performed by conducting spectral analysis used: rare earth oxide powder, rare earth hexaboride
of fluorescent X-rays produced from the substance. A single crystal, and Pt and Pt13 A at%Rh. Each mea-
crystal spectroscope is mainly used for this spectral surement result will be described below in order.
analysis. In quantitative analysis, however, since a
number of factors depend on the X-ray wavelength, 1) Rare Earth Oxide
such as absorption due to the air, crystal reflecting A powder sample was used for the measurement
power, fluorescence excitation efficiency and counter of rare oxide (R2O3). It was fixed onto both-side
efficiency, these factors entail lots of corrections to be adhesive tape and was placed at the center of the four
made. Generally, the qualitative and quantitative circle diffractometer. Then direct X-ray irradiation
analyses of heavy elements existing among light was made.
elements can be easily carried out. Automatic mea-
The XRF spectra detected from elements having
surement is also easy, so their analytical techniques
the atomic numbers in a lower to higher order starting
are useful for handling large quantities of oxides, etc.
with La were superposed for comparison (Fig. 3). The
4. Experiment and Result result shows that in the case of samples whose atomic
All of the XRF analyses under the present numbers are about the same as those of the rare earth,
experiment was conducted by an energy dispersive the sample identification can be made sufficiently
type apparatus. It uses a multichannel pulse height with XRF peaks. Also, regarding Kα1 and Kα2, the
analyzer. The time constant of the main amplifier was way they are going to separate from each other as the
set at 2.0 µs. If a longer time constant were set, the atomic number increases can be clearly known. This
energy resolution would improve. But as the intensity is because the energy difference between Kα1 and
of X-rays entering the SSD becomes higher, counting Kα2 becomes greater with an increase in the atomic
number. On the other hand, there is no peak separa-

25 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 a discharge cutter, a cylindrical sample was cut out
energy resolution of the SSD is inferior to their energy into a similar shape, 3 mm in thickness and 5 mm in
difference. The SSD resolution can be improved to diameter approximately. Figure 4 shows the outcome
some extent, though, by varying the preamplifier set- of X-irradiation to the sample surface.
ting for the SSD (e.g. by making the time constant The result was such that the same thing can be
greater). said as with the measurement result of the above rare
From the above result, it may be known that earth oxide. What should be noted here is that heavy-
regarding powder samples containing heavy ele- element impurities can be detected far more easily
ments, even a very simple experiment can satisfy the when conducting the crystal structure analysis, elec-
requirements for identification. tron density distribution analysis and the like analysis
with single crystals. For the structure analysis, in
2) Rare Earth Boride
particular, it is possible to identify impurities in a very
The sample used was an RB6 (R=rare earth) single convenient way with a sample for measurement kept
crystal synthesized by the floating zone method. With 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. existing in heavy element samples. For light-element
But when quantitative analysis becomes practical, it impurities, however, the measurement method using
will then be possible to experimentally determine the ultrashort wavelength X-rays cannot be regarded as
sample composition and to proceed on the structure effective at the present stage.
analysis and the electron density distribution analysis
5. Study
while maintaining the same sample condition.
For XRF analysis using long wavelengths, high-
3) Pt, Ptl3 A at%Rh
precision experiments have been going on, and the
Two types of samples, Pt and Pt13 A at%Rh, pre- quantitative analysis techniques are now on the ppm
pared by Furuya Metal Co. were used. They were order. Since, however, no higher energy fluorescent
cylindrical, 1 mm in diameter and 5 mm in height. To X-rays will be emitted from the sample for measure-
effect the same measurement condition, the samples ment than the given energy, heavy-element analysis is
were placed in parallel to the incident X-ray beam. performed by analyzing L-series XRF spectra.
Each of them was adhered to a glass rod to facilitate Where, then, should one find the advantages of
their installation in a similar way to that for single XRF analysis using short-wavelength X-rays? The
crystal measurement. Figure 5 shows the result of first advantage may be the simplicity of peaks for
XRF analysis of them with the K series radiation. detection. Regarding L-series fluorescent X-rays,
One can see that because the excitation voltage of there are many kinds. Moreover, because energy
the X-ray source is exceedingly high, the observation differences between the respective X-rays are small,
of the Kα and Kβ rays of Pt (PtKα1 λ = 65.122 keV), a this poses a problem in that peak separation by
heavy element, can be made sufficiently well. calculation becomes necessary when dealing with
Moreover, the way the PtKα1 and PtKα2 peaks are samples containing elements of adjoining atomic
distinctly separated can be seen. In the measurement numbers. Whereas, in the case of analysis with the K-
result of the Pt sample containing 13%Rh, one can series radiation, there are only four kinds of
know that the fluorescent X-rays of Rh (RhKα1 = fluorescence X-rays to be observed, that is, Kα1,2 and
20.074 keV) were also detected and that the Pt X-ray Kβl,2. Further, their respective energy widths are
fluorescence peak was diminished. Hence, ultrashort- larger compared with the L-series radiation. As a
wavelength X-rays are considered to display high result, experiment and analysis may be made much
performance in detecting heavy-element impurities simpler, especially for qualitative analysis of samples.

27 The Rigaku Journal

 The second advantage may be that information on the time ahead. Since short wavelength X-radiation is
the sample's inner part can be obtained. With long available in a laboratory as well, the author hopes to
wavelength X-rays, the effect of the sample surface, continue varied experiments in such a way as to serve
especially those of samples containing heavy ele- for the oncoming stepped-up experiments at the
ments may be said to be great. Whereas, short wave- SPring-8.
length X-rays can penetrate deep into the interior of
Acknowledgment
the sample. For instance, it is easy for such X-rays to
penetrate through a 2 cm aluminum plate. I would like to acknowledge the many assistances
given by the following people in preparing this report.
Reported above is the XRF analysis conducted on
samples containing heavy elements by use of short- I am indebted to Dr. Fujio Okamura, chief
wavelength X-rays. The sample shape (powder, single researcher, and Dr. Takeshi Yukino, at National
crystal, alloy) was disregarded. However, the present Institute for Research in Inorganic Materials, Science
experiment is by only qualitative analysis, and there- and Technology Agency of Japan for providing
fore the author is considering to work on more and research environments and pertinent advices. I thank
more experiments toward quantitative analysis. Dr. Kazuki Yamamoto in Physical Engineering Dept.
of University of Tsukuba for various ideas and
6. Concluding Remarks suggestions. I thank Dr. Yoshihiro Kino at Rigaku
Currently, the SPring-8 storage ring is being built Corporation for providing Pt, Pt13 A at%Rh, and thank
at Nishiharima, Hyogo Pref., and is scheduled to be Dr. Shigeru Otani and Dr. Takaho Tanaka at the
commissioned in 1997. This facility, when completed, aforementioned institute for RB6 single crystals. I am
will offer ultrashort-wavelength X-rays featuring high also grateful to Prof. Ken’ichi Ohshima in Institute of
brilliancy. As one of the experiments utilizing such Applied Physics of the above university, where I am a
short-wavelength X-rays, XRF analysis using the K- graduate student, for considerations given officially
series radiation may be cited. and privately.
The present system referred to in this paper is References
originally designed for electron density distribution [1] F. P. Okamura: The Rigaku Journal, Vol. 11, No. 2,1994.
analysis using single crystal samples. In fact, the [2] K. Yamamoto, et al.:in press.
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 28

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