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Handbook of Practical X-Ray Fluorescence Analysis

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4. X-Ray Detectors and XRF Detection Channels

4.1. Introduction
F Scholze
The discovery of x-rays by Wilhelm Conrad Röntgen was based on the
observation of fluorescence in materials well away from his tube. Soon it was
recognized that photographic plates and gas-filled ionization chambers
(electrometers) are also sensitive to x-rays. With these principles the basis for x-
ray detection was laid almost 70 years ago. After the initial observation of x-ray
and γ-ray with photographic plates the development of gas filled counters 1
enabled the instantaneous detection of radiation. Proportional counters provided
the capability to measure the photon energy of x-rays.
Although proportional counters have been in use for almost 100 years now, they
are still valuable detectors that offer strong advantages. First, they are cheap and
easy to operate because the internal gas-amplification yields a high charge
output, which can be quickly and easily processed by the following electronics.
These detectors are specifically insensitive to electronic interference and thus
suited for harsh environments. Gas detectors are also a good choice if large areas
are needed for detection, and they are capable of spatial resolution if, e.g. a
resistive anode is used. More sophisticated, though still easy to produce,
structures like multiwire or multistrip anode designs allow for simultaneous
spatial and energy resolution over large areas 2. The main disadvantage of gas
detectors is their low density that results in a low efficiency for x-ray detection
unless the detectors are made rather large.
An alternative with much higher detection efficiency for high energy photons is
the scintillation detector. While early observations of ionizing radiation were
made by looking at fluorescence screens in darkened laboratories, state-of-the-
art scintillation detectors use a scintillating material coupled to photo
multipliers, photodiodes or CCDs for the detection of fluorescence light. The
benefit of these detectors is that they can be made very small and effective for
hard x-rays by using scintillating crystals of heavy elements. Depending on the
scintillator, the speed of these detectors can also be increased. When large areas
of scintillating material are coupled to a large number of light detectors, a high-
efficiency imaging detector is obtained that can be used for, e.g. medical
applications. The disadvantage of scintillation detectors is their poor energy
resolution.
Therefore, there has constantly been a search for a way to realize the principle of
the ionization chamber with a high-density material. Consequently, shortly after
high-purity germanium and silicon became available, the first Ge(Li) 3 and Si(Li)
detectors were produced in the early 1960s. These detectors offered a much
higher resolution than the gas detectors and scintillators. The reason is that the
mean energy needed to create one primary elementary charge is about 20–30 eV
for gases while for semiconductors it is only a few electron volts. Thus, a ten
times higher number of primary charge carrier is produced reducing the
statistical fluctuations by about a factor of 3. Furthermore, the higher charge
generated allows for the direct measurement by low-noise electronics. For the
proportional counters, the gas amplification process added additional noise.
The planar Si(Li) and Ge(Li) detectors are the semiconductor analogue to the
ionization chamber. In principle also a solid-state proportional counter, the
avalanche diode, exists. However, due to the high noise of the avalanche
process, it is not used for high-resolution applications. The search for a solid-
state analogue to the multiwire chambers, however, resulted in a versatile device
– the silicon drift detector (SDD). Originally introduced for spatially resolving
detectors for high-energy particle detection, the device became one of the most
promising new x-ray detectors.
One of the main disadvantages of the planar Si(Li) and Ge(Li) detectors is the
need for liquid nitrogen cooling. The vacuum-isolated cryostats make these
detection systems rather large and difficult to handle. The reason for the cooling
is the high leakage current at room temperature combined with a rather high
read-out capacitance, because these detectors form a plate condenser with the
capacitance proportional to the area. The high capacitance results in a high
contribution of the serial noise component that requires longer shaping time. For
long shaping time, however, the shot-noise contribution from the leakage current
increases. In the SDD, the charge is drifted from a large area into a small read-
out node with low capacitance. Thus, the serial noise decreases and shorter
shaping time can be used. This offers two advantages, first faster counting is
enabled and at the same time, higher leakage current can be accepted, drastically
reducing the need for cooling. Presently, SDD at room temperature achieves an
energy resolution of the order of 180 eV 4, comparable to the early liquid
nitrogen cooled systems, with shaping times of 250 ns. A detailed discussion of
these detectors is given in the first section of the chapter. In the second section,
the perspective of a combination of energy and spatial resolution using silicon
detectors is discussed.
A consequent next step on the path to higher energy resolution was the search
for “materials” with even lower “ionization” energy. The electrons of
superconductors bound in Cooper pairs are such a material. The binding energy
of the Cooper pairs is of the order of a few millielectron volts. Thus about 1,000
times more charge is generated per absorbed energy. This charge can be
detected with a super conducting tunnel junction (STJ), a Josephson contact
where the super conducting Josephson current is suppressed by a magnetic field.
Potentially, the resolution limit should be about 30 times lower as compared to
semiconductor detectors. Energy resolution in the range of 12 eV for manganese
x-rays (6 keV photon energy) has, indeed, been demonstrated 5. Even more
impressive, these detectors allow to measure energy dispersive spectra of optical
photons that look very much like the spectra of few-kiloelectron-volt x-ray
photons measured with a Si(Li) 6. The price to be paid is to go to ever-lower
temperature. Si(Li) detectors are operated at about 100 K, STJ below a few
100 mK. If detectors are cooled to about 100 mK or below, the heat capacitance
becomes low enough such that single photons create a measurable increase of
the detector temperature. The best energy resolution demonstrated so far, 4.5 eV
for Mn Kα, was done so with the so-called micro-bolometer7. A micro-
bolometer consists of an absorber at low temperature coupled to a heat sink and
a thermometer to measure the temperature change. A large variety of
possibilities 8 exist for the realization of either the absorber or the thermometer
and further subgroups of detectors can be defined by whether the signal detected
corresponds to thermal equilibrium (classical bolometer) or nonequilibrium
excitations e.g. hot electrons or phonons that are detected. Based on such
indirect detection schemes, also for low-temperature detectors, spatially
resolving devices have been demonstrated 9. Although mK-operation sounds
difficult even if liquid nitrogen is a disadvantage for many applications, these
systems are no longer exotic. First low-temperature detectors of the STJ and
bolometer type are already being operated in scanning electron microscopes and
there is an increasing number of commercial suppliers. A comprehensive
overview of the recent achievements of low-temperature detectors for x-ray
spectroscopy was presented in a paper by M. Frank et al. 10.
This is a short summary of the means to ever better energy resolution. There are,
however, other criteria that are even more important for many applications. A
main issue for all detectors is the purity of the spectra recorded. X-ray
fluorescence spectroscopy is based on the excitation with higher energy x-rays
and the detection of the lower energy fluorescence x-rays. If monochromatic x-
rays are used for excitation, low detection limits are principally possible because
there is no background radiation at the fluorescence line energies. If, for some of
the detected x-rays, energy loss processes in the detector shift the measured
energy toward lower energy, an artificial low energy background in the energy
region of the fluorescence lines is created. Especially for total reflection x-ray
fluorescence, this low-energy background from higher energy photons incident
at the detector deteriorates the detection limits of trace elements. Therefore, for
many applications the so-called peak-to-background ratio, which defines the
relative height of the full-energy peak in a spectrum relative to the low energy
background, is very important. An unavoidable effect, which causes an energy
loss, is that caused by the escape of photoelectron or Auger electron from the
active detector volume. X-rays are indirectly ionizing, i.e. after absorption of an
x-ray the energy is either fully or partially transferred to a compton electron or
photoelectron, respectively. These electrons create the charge carriers that are
subsequently detected by scattering processes during their slowdown. During
this process, the electrons travel a certain distance depending on their initial
energy. If such an electron is created close to the boundary of the active detector
volume it might escape from the detector and a corresponding part of the initial
energy would be lost. There is also the possibility for the opposite process, that
is, energy from photons absorbed close to the active detector volume is partially
transferred into the detector. It is obvious that the probability of these processes
scales with the ratio of the active detector volume to the surface. This effect
strongly compromises practical use, especially for the small low-energy
detectors. This is especially true for the pure STJ detectors, which are made of
thin layers of superconductors serving also as the absorber. For photon energies
above about 1 keV, the majority of pulses detected with such a device are
background pulses most often originating from photons absorbed in the substrate
close to the active region 11. Therefore, advanced designs use an absorber made
of a different material from where the energy is transferred to the STJ junction
where it is detected 5. If several junctions are used for reading the signal, spatial
resolution is also achieved9.
Besides these intrinsic unavoidable effects, there are several others which cause
partial detection of the charge generated. For semiconductor detectors, field
distortions might force the charge to drift to inactive regions. This was a
problem for the early Ge(Li) and Si(Li) detectors caused by charging of the side-
walls of the crystal. Improved passivation techniques solved this problem and
Si(Li) detectors with a Ni-front contact achieve the best peak-to-background
ratios. Basically, SDD also could achieve the same performance. The
background in the present SDD is not caused by processes at the front but by
charge that is partially drifted to the outer region and an inactive region around
the integrated read-out transistor. New designs with the transistor shifted to the
outer region of the detector significantly reduced the background 12. Using small
collimated photon beams in the area well away from the edge of the active
region, a background comparable to Si(Li) detectors is demonstrated for SDD.
For some applications, however, it might also be advantageous to filter the
spectrum before detection. So, high energy photons of a high rate e.g. scattered
excitation radiation or intense fluorescence of the main matrix elements that
need not be analysed, could be removed from the spectrum to reduce the total
count rate, and thus enable higher count rates for the analysed elements. Such
pre-dispersion could be done using mirrors or broadband synthetic crystals or
multilayer reflectors.
A consequent application of such pre-dispersion approaches leads back to the
so-called wavelength-dispersive analysis (WDX), covered in the last section of
the chapter. The classical set-up of WDX uses a crystal that disperses the x-rays
and a detector placed at the position where the respective energy is diffracted,
counting the photons. In most cases, proportional counters or scintillators are
used for this purpose. Two other more sophisticated solutions are available.
First, the dispersing crystal could be replaced by a broader bandpass filter like
the multilayer mirrors or mosaic crystals from e.g. highly orientated pyrolithic
graphite (HOPG). Both solutions offer also the opportunity to use focusing
optics increasing the collection angle for the fluorescence radiation at the
sample. Second, the detector could be replaced by e.g. a spatially resolving
device for the multichannel WDX or a detector with higher energy resolution
could be used to detect diffusely scattered background radiation and higher
diffraction orders.
The chapter provides an overview of the vast variety of x-ray detectors and
wavelength-dispersive arrangements that could be used as building bricks for
intelligent solutions adapted to the specific needs of an application.

References
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Rudman, D. A. Wollman, “A Mo–Cu superconducting transition-edge microcalorimeter
with 4.5 eV energy resolution at 6 keV”, Nucl. Instrum. Meth. A 444, 184–187 (2000)
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R. den Hartog, P. Verhove, D. Martin, N. Rando, A. Peacock, M. Krumrey, D.J. Goldie, “An
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S. Bechstein * , B. Beckhoff, R. Fliegauf, J. Weser, G. Ulm, “ Characterization of an
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