X-Ray Optics 151

Designing HOPG optics consists in optimizing both the crystal form and
local thickness for a given application involving specific constraints such as
the source size, angular emission characteristics, desirable distance to the
optics as well as the conflicting requirements (size, effective intensity gain,
and energetic resolving power) with respect to the image focal spot. This
optimization procedure can be performed best by a ray-tracing computer sim-
ulation [109, 126–128] involving all constraints and focal spot requirements.

Applications in XRF: Excitation Mode

The use of HOPG monochromators for the primary beam in XRF, i.e., in
the excitation channel, allows solving several problems at once. First, the
background in the most interesting parts of a fluorescence spectrum can be
significantly reduced due to the monochromatization, mostly due to eliminat-
ing bremsstrahlung contributions originating from the source and preserving
only a strong characteristic line of the primary beam. Besides, employing
a focusing device in the excitation channel can considerably increase the
intensity of the excitation line due to a larger angular acceptance. In addition,
focusing primary radiation onto a small spot enables performing local analysis
with a high spatial resolution or to improve absolute detection limits, which
is of particular interest in case of inhomogeneous contaminants.
Thus the use of focusing HOPG optics can also contribute to an improved
analysability of small-sized specimens by EDXRF. Of decisive importance is
a very high angular acceptance of focusing HOPG crystals for the incident
radiation in order to ensure the highest possible intensity of the reflected
beam. This requirement is due to the fact that as long as the absolute count
rate capacity of the detection system is not saturated, i.e., mainly in the case
of thin specimens, an intensity as high as possible in the fluorescence lines is
of first priority for the minimum detection limits according to [129] and [130].
Only in the second place one can profit by a reduced background count rate.
Both requirements can be met by applying monochromatic exciting radia-
tion with a high intensity. Reducing the spatial size of a specimen spot on any
kind of backing, combined with a corresponding reduction of beam diameter,
will also contribute to decrease the background, because the scattering at the
backing is decreased.
A systematic selection among 55 single crystals undertaken in [131]
revealed HOPG crystals to be superior candidates for the characteristic Kα
line of a Mo tube yielding the highest intensities. Another important result of
this work consists in experimental proof that even singly curved HOPG crys-
tals (either sagitally or meridionally bent) give a remarkable intensity gain
of the reflected beam in comparison with flat crystals. The intensity gains of
2–10 times for HOPG cylinders compared with flat HOPG was obtained also
in [120]. Using doubly bent toroidally shaped HOPG crystals [109, 121], it was
possible to concentrate the characteristic radiation of a Mo tube onto a small
focal spot of about 1 mm, achieving an intensity gain of 6.2 relative to the
corresponding intensity of the Mo Kα line of the radiation passing directly.
152 A. Antonov et al.

Table 3.4. EDXRF analysis of an aerosol loaded filter and detection limits (DL)
for different excitation modes
DL for Sn DL for DL for HOPG
Line Relative secondary direct tube focused tube
Fluorescence energy concentration target excit. excitation radiation
line (keV) (µg cm−2 ) (ng cm−2 ) (ng cm−2 ) (ng cm−2 )
Ti Kα 4.51 3.38 ± 0.20 301.0 ± 19.3 36.4 ± 2.2 26.9 ± 1.6
Mn Kα 5.89 36.73 ± 1.36 163.6 ± 6.4 39.7 ± 1.6 22.6 ± 1.0
Fe Kα 6.40 78.93 ± 2.68 134.7 ± 4.9 39.6 ± 1.5 20.1 ± 0.8
Cu Kα 8.04 1.06 ± 0.06 63.1 ± 4.2 27.5 ± 1.7 15.9 ± 1.0
Zn Kα 8.63 22.03 ± 0.79 52.8 ± 2.2 39.3 ± 1.4 12.7 ± 0.7
Pb Kα 10.55 2.65 ± 0.12 58.9 ± 3.0 72.5 ± 3.4 19.1 ± 1.1
Br Kα 11.91 3.30 ± 0.14 25.3 ± 1.2 35.2 ± 1.8 13.8 ± 1.0
Rb Kα 13.38 0.58 ± 0.03 18.7 ± 1.1 30.9 ± 1.7 8.0 ± 0.6
Zr Kα 15.75 0.33 ± 0.02 13.7 ± 0.9
Nb Kα 15.75 0.07 ± 0.01 13.1 ± 1.2
Mo Kα 17.44 0.04 ± 0.01 12.7 ± 1.3

A comparison of various excitation methods for aerosol-loaded filter spec-

imens [109] revealed an enhancement of the detection sensitivity by a factor
of 2 to 11 when implying a focusing HOPG toroid in comparison with the
direct beam excitation or with the secondary fluorescence (Sn Kα) target
excitation (see Table 3.4.) For the Bragg reflected Mo Kα radiation focused
by the HOPG toroid the X-ray tube could be operated at a current being 25
times lower (i.e., 2 mA instead of 50 mA) than in a routine set-up with the Sn
target, still using the full count-rate capacity of the detection system.
Optimization of the crystal thickness together with the crystal geometry
can lead to the reduction of a focal spot size. A spot size of 150 µm × 250 µm
was reported for thin HOPG toroids with fine focus tubes at Cr Kα and Rh Lα
lines [132].
The results obtained demonstrate the possibility to simultaneously mono-
chromatize and focus primary radiation onto small spots by means of doubly
bent HOPG crystals, thus enabling local XRF analysis with a sub-mm reso-
lution and improving absolute detection limits.

Applications in XRF: Detection Mode

In the detection mode the HOPG optics can be used as a broadband filter or
as a radiation collector between a specimen and a detector. The cylindrical
geometry is the most commonly used geometry for dispersion filters. Varying
the detector-to-sample distance and the size of the beam-stop, one can tune
the position and the width of the energy window. The advantages of the use
of a cylindrically bent HOPG in the detection channel of an EDXRF set-
up consist mainly in the possibility of modifying the spectral distribution to