Overview of X-ray Fluorescence

Prepared by James M. Guthrie,University of Missouri Research Reactor

Revised, August 2012, Jeffrey R. Ferguson, University of Missouri Research Reactor

Introduction

X-ray fluorescence (XRF) spectrometry is an elemental analysis

technique with broad application in science and industry. XRF is based
on the principle that individual atoms, when excited by an external
energy source, emit X-ray photons of a characteristic energy or
wavelength. By counting the number of photons of each energy
emitted from a sample, the elements present may be identified and
quantitated.

Henry Moseley was perhaps the father of this technique, since he,
building on W.C. Röentgen’s discovery of the high-energy radiation
dubbed X-rays, built an X-ray tube which he used to bombard samples
with high-energy electrons. Moseley in 1912 discovered a
mathematical relationship between the element’s emitted X-ray
frequency and its atomic number. In 1925 Coster and Nishina were the
first to use primary X-rays instead of electrons to excite a sample. After
Glocker and Schreiber were the first to perform quantitative analysis of
materials using XRF in 1928, detector technology had to catch up in
order to make the technique practical, which didn’t begin to happen
until the 1940’s. The 1950’s saw the first commercially produced X-ray
spectrometers. In 1970, the lithium drifted silicon detector was
developed, and this technology is still in use today (Jenkins 1988: 51-53).

Modern XRF instruments are capable of analyzing solid, liquid, and thin-
film samples for both major and trace (ppm-level) components. The
analysis is rapid and usually sample preparation is minimal or not
required at all.

The Archaeometry Laboratory at the MU Research Reactor is the home

of two Bruker Tracer III-V handheld instruments (one equipped with an
automated sample changer) and an Elva-X benchtop instrument.
These instruments are used primarily for the provenance research on
obsidian artifacts from around the world, but they are also used in
special circumstances for the non-destructive analysis of other
materials such as metals, ceramic paints, and soils.

Fundamentals of X-Ray Spectroscopy

The identification of elements by X-ray methods is possible due to the

characteristic radiation emitted from the inner electronic shells of the
atoms under certain conditions. The emitted quanta of radiation are X-
ray photons whose specific energies permit the identification of their
source atoms. To understand this phenomenon, we must first look at
how X-rays are generated.

When an electron beam of high energy strikes a material, one of the

results of the interaction is the emission of photons which have a broad
continuum of energies. This radiation, called bremsstrahlung, or
“braking radiation”, is the result of the deceleration of the electrons
inside the material. The bremsstrahlung continuum is illustrated as a
function of electron acceleration voltages for a molybdenum target in
Figure 1.

Another result of the interaction between the electron beam and the
material is the ejection of photoelectrons from the inner shells of the
atoms making up the material. These photoelectrons leave with a
kinetic energy (E-φ) which is the difference in energy between that of
the incident particle (E) and the binding energy (φ) of the atomic
electron. This ejected electron leaves a “hole” in the electronic
structure of the atom, and after a brief period, the atomic electrons
rearrange, with an electron from a higher energy shell filling the
vacancy. By way of this relaxation the atom undergoes fluorescence,
or the emission of an X-ray photon whose energy is equal to the
difference in energies of the initial and final states. Detecting this
photon and measuring its energy allows us to determine the element
and specific electronic transition from which it originated (Jenkins 1988:
4-6, Anzelmo 1987 Part 1). Herein lies the basis for XRF spectrometry,
where elements may be quantitated based on the rate of emission of
their characteristic X-rays from a sample that is being excited.
Figure 1. Intensity output from a Mo anode X-ray tube at different voltages (after
Jenkins 1988: 5).

Any of the electrons in the inner shells of an atom can be ejected, and
there are various electrons in the outer shells that can “drop” to fill the
void. Thus there are multiple types of allowed transitions that occur
which are governed by the laws of quantum mechanics, each
transition having its own specific energy or line (Jenkins 1988: 6). The
three main types of transitions or spectral series are labeled K, L, or M,
corresponding to the shell from which the electron was initially
removed. K series lines are of the highest energy, followed by L and
then M. Within the series, the specific transitions are denoted by the
subscripts α, β, γ, etc. to denote which upper energy shell was involved
in the relaxation and finally a numerical subscript to indicate the
quantum state within that upper energy shell. For example, the Mo Kα1
transition yields a photon of wavelength 0.071 nm. (Jenkins 1988 p. 4) It
is important to note that only the very highest resolution spectrometers
could resolve Kα1 and Kα2 lines, so for practical purposes in X-ray
spectrometry only the Kα line would be mentioned (Skoog 1998: 275).
As shown in Figure 1, once the excitation energy of the incident
electron beam exceeds the Mo K transition energies these lines begin
to appear in the tube spectrum.

Fluorescence, however, is not the only process by which an excited

atom may relax. It competes with the Auger effect, which results in
emission of a second photoelectron to regain stability. The relative
numbers of excited atoms that fluoresce are described by
the fluorescence yield, which increases with increasing atomic number
for all three series (Jenkins 1988: 6).

High energy electrons are not the only particles which can cause
ejection of photoelectrons and subsequent fluorescent emission of
characteristic radiation. High-energy X-ray photons can create the
same effect, allowing us to excite a sample with the output of an X-ray
tube or any source of photons of the proper energy. In fact, in some
applications of XRF spectrometry, X-rays from a tube are used to excite
a secondary fluorescer, which emits photons that in turn are used to
excite the sample.

When X-rays impinge upon a material, besides being absorbed,

causing electron ejection and subsequent characteristic photon
emission, they may also be transmitted or scattered. When an X-ray is
scattered with no change in energy this is called Rayleighscattering,
and when a random amount of energy is lost the phenomenon
is Compton scattering. Scattered X-rays are usually problematic in XRF,
creating high levels of background radiation (Anzelmo 1987 Part 1).

Since only the inner electron shells are involved in the emission of X-rays,
the wavelengths are independent (within our ability to measure) of the
state of chemical bonding, which involves the outer-most electron
shells only. One exception to this rule involves low-Z elements with fewer
electrons. The overall lack of chemical shifts allows the analyst to
determine the elemental composition of the sample, whether the
elements are present in their pure forms or as compounds (Skoog 1998:
275).

Instrumentation
Most of the XRF instruments in use today fall into two categories:
energy-dispersive (ED) and wavelength-dispersive (WD) spectrometers.
Within these two categories is a tremendous variety of differing
configurations, X-ray sources and optics, and detector technologies.
This paper will cover the most common types of instruments, with forays
into the more advanced or specialized components where they are of
interest.

A diagram of a WD system is shown in Figure 2. The instrument operates

based on the principle of Bragg diffraction of a collimated X-ray beam,
in this case the beam emanating from the sample. A detector is
angularly scanned relative to the analyzing crystal, registering the
spectrum.

Figure 2: Diagram of a wavelength-dispersive spectrometer. (from Jenkins 1995:

88)

A typical ED spectrometer is diagrammed in Figure 3. Here the entire

polychromatic spectrum from the sample is incident upon a detector
that is capable of registering the energy of each photon that strikes it.
The detector electronics and data system then build the X-ray
spectrum as a histogram, with number of counts versus energy.

X-Ray Source

The “front end” of both types of instruments is the X-ray source. The
source consists of an evacuated chamber with a heated cathode,
which is usually a tungsten wire, and an anode, which is held at a
potential difference of several tens of kilovolts relative to the cathode.
Thermal electrons are released from the cathode and accelerated
toward the anode. When the electron beam impinges upon the
anode, bremsstrahlung radiation as well as X-ray lines characteristic of
the anode material are emitted. These photons escape through a
beryllium window built into the side of the tube.

There is no one-size-fits-all approach for source selection in XRF. X-ray

tube powers may be set up at very different levels, from a fraction of a
watt for EDXRF instruments with high detection efficiencies to several
kilowatts for WDXRF instruments. In this latter case, the tube must be
liquid-cooled since the majority of the power is dissipated as heat. The
anode materials must be carefully chosen as well, since the
wavelength of their characteristic lines is important for proper
excitation of the sample. Some example single-element anode
materials are aluminum, chromium, tungsten, palladium, or gold. For
detection of light elements, a high intensity of low energy, i.e. 1-10 keV,
radiation must be available, while heavy elements require excitation at
higher energies up to 50 keV (Jenkins 1995: 43-47, Skoog 1998: 274). It is
also important to keep in mind that the primary source of detector
background will be the intense primary radiation from the tube, above
which the secondary sample radiation must be detected. The use of
secondary targets, or filters, can greatly reduce the background and
improve sensitivity for specific portions of the spectrum.
 Figure 3: Block diagram of a typical EDXRF spectrometer. (from Jenkins 1995:
123)

For instruments that are designed to acquire the entire spectrum with
good sensitivity on light as well as heavy elements, a different
approach is taken. A tube anode material is chosen to give a high
bremsstrahlung or continuum output, which is used to excite a
secondary fluorescer, or target, which gives off its own characteristic
lines without the continuum. The sample is then excited by the emission
from the target, which is chosen to efficiently excite elements in a
certain Z range. A system may be set up to change targets
automatically during the analysis so that the low, middle, and high end
of the sample spectrum may be sequentially boosted. When an EDXRF
instrument uses such a system, tube powers must be increased
dramatically since most of the original X-ray intensity is lost.

Certainly XRF excitation is not limited only to X-ray tubes. Less common
excitation sources include gamma-emitting radioisotopes (241Am,
109Cd, 153Gd, and others), electron sources where the sample is the
tube anode, and synchrotrons, which produce highly intense,
coherent, monochromatic X-ray beams (Jenkins 1988: 56, Jenkins 2000).

Sample Chamber

Up to this point, little has been said regarding what kinds of samples
may be analyzed by XRF. The development of portable XRF (PXRF)
instruments has greatly expanded the range of samples suitable for
analysis. There is no longer a need to fit a sample into a small
chamber. In the case of PXRF, it is possible to analyze the samples with
the instrument in a stand or the instrument can be moved to the
sample, as in the case of analyzing a exposed rock outcrop or a large
painting. The majority of the samples analyzed by XRF at MURR are
small obsidian artifacts that are placed on the nose of the instrument.
We have recently acquired an automated sample changer that
allows us to load up to 20 samples at a time and operated much like
the sample changers on large lab-based instruments.

Detector Systems
The two main types of XRF spectrometers (WD and ED) differ
completely in their detection systems. EDXRF systems depend on
semiconductor-type detectors which receive the entire emitted
spectrum from the sample and decode it into a histogram of number
of counts versus photon energy. WDXRF spectrometers, however, use
an analyzing crystal to disperse the emitted photons based on their
wavelength and place the detector in the correct physical location to
receive X-rays of a given energy.

Wavelength-Dispersive Spectrometers

Please refer to Figure 2, which displays a block diagram for a WD setup.

More collimators, usually made from a series of closely spaced parallel
metal plates, are needed to direct the beam in order to closely control
the diffraction angle of all detected photons. The analyzing crystal
angularly disperses incident radiation of wavelength l according to
Bragg’s Law (nλ = 2d sinΘ, n = 1, 2, 3,… where d is equal to the crystal
lattice spacing). In the instrument shown, the analyzing crystal may be
rotated with the detector assembly simultaneously revolving around it
to scan through the possible wavelengths. To resolve wavelengths in all
regions, different crystals must be used, since crystals with large
spacings must be used for long wavelengths but they make the short
wavelengths irresolvable at low q (Jenkins 1995: 89).

The system in the diagram utilizes two detectors in series. The first, a gas-
flow proportional detector, is efficient for detecting long-wavelength
radiation (> 0.15 nm). Most high-energy X-rays pass through it, however,
and are counted by the NaI(Tl) scintillation detector. The gas-flow
proportional detector works by placing a high voltage across a volume
of gas (usually Ar with methane). An X-ray photon will ionize a number
of Ar atoms proportional to its energy. The freed electrons are
accelerated in the high voltage, ionizing other Ar atoms and creating
an electron cascade which is controlled by the quench gas methane.
The freed charges are measured in the circuitry as a voltage pulse
whose height is proportional to the energy of the photon that initiated
the cascade (Jenkins 1988: 61).

An NaI(Tl) detector contains a large single crystal of sodium iodide that

has been doped with thallium. This crystal is sealed from light by a Be
window. When an X-ray photon enters the crystal, it places primarily the
I atoms in an excited state, in numbers again proportional to its energy.
These excited states decay exponentially with time, giving off a flash of
light or scintillation when they go. The summed intensity of light strikes a
photocathode, which releases photoelectrons that are amplified in a
discrete dynode detector. The pulse height measured from this
detector is proportional to the energy of the original X-ray photon
(Jenkins 1995: 96, Knoll 2000).

One may wonder why these detectors need to have any energy
resolution at all, since the X-ray energies are supposed to be dispersed
by the Bragg crystal. In order to improve the performance of the
spectrometer, it is useful to be able to discard X-rays from higher order
(n>1) diffraction, hence the need to resolve out photons of different
energies.

With WDXRF systems, it may be possible to have several detector

assemblies placed at fixed angular locations in order to analyze for a
few selected elements over and over. WDXRF spectrometers often offer
more flexibility for the researcher as well as very good sensitivities. The
detector outputs are also simpler to use directly and do not generally
require heavy use of electronics and computer algorithms in order to
deconvolute. Disadvantages include the inability to quickly acquire the
entire X-ray spectrum for full-element analyses, higher hardware costs,
and a larger instrumental footprint when compared to EDXRF systems.

Energy-Dispersive Spectrometers

While simpler in terms of the positioning of the detector versus the

sample, EDXRF spectrometers require sophisticated electronics and
computer software in order to interpret the detector output. Nowadays
this is less complicated, though, due to important technological
advances in multichannel analyzers and faster computers, and EDXRF is
often the technique of choice for fast multielement analyses.

Dispersion in EDXRF is accomplished through the use of a

semiconductor-type detector (Knoll 2000). Although germanium
detectors are utilized, the most common type in service is the Si(Li), or
lithium-drifted silicon, detector. A semiconductor detector operates
based on the principle that an X-ray photon incident upon the diode
material will give up its energy to form electron-hole pairs, the number
of which is proportional to the energy of the photon. The high voltage
applied across the diode quickly collects the released charge on a
feedback capacitor, and the resulting proportional voltage pulse
amplified by a charge-sensitive preamplifier. The output of the preamp
is fed to a main amplifier system. The pileup rejector, part of this system,
deals with the probable event that two pulses will arrive very close
together in time. From this point, the pulse is converted to a digital
signal and processed in the multichannel analyzer (MCA) (Jenkins
1995). In the MCA, dead time, caused by high counting rates, must be
corrected. Peaks in the energy spectrum, once acquired, are subject
to a large degree of massaging by the software in the connected
computer. Sophisticated algorithms sense and quantitatively correct
for high backgrounds due to Compton scattering from low atomic
number matrices (Metz 1994). Spectrometers that use secondary
targets may acquire several energy spectra for each sample, one from
each target. Since each target yields better sensitivity in one part of
the spectrum, the information from the energy spectra is combined to
quantitate each element being analyzed. Accurate quantitative data
on the entire mass spectrum may be obtained in a matter of minutes
using EDXRF. However, in general the detection limits are higher than
those for WDXRF.

For both of the Bruker Tracer instruments we use we have incorporated

a secondary target made of thin sheets of copper, aluminum and
titanium to optimize the spectra for the analysis of obsidian and any
other analyses focusing on elements with with fluorescent energies
between about 10 and 20 kV.

We have developed a world-renowned set of obsidian calibration

standards that we have used to calibrate our own instruments and
Bruker now runs this calibration on all portable XRF instruments heading
out to museums and archaeologists. With this calibrations it is possible
to acquire quantitative concentrations for many elements that are
comparable to data acquired by mosre costly and destructive neutron
activation analysis (NAA)

Example Instrument: The Bruker Tracer III-SD

The primary source of X-rays for the Tracer-III is an X-ray tube with a Rh
exit window. The tube voltage can be varied up to 45 kV, although we
generally analyze the obsidian with a setting of 40kV. The secondary
target, or filter, primarily used includes a 6 mil thick sheet of copper
(used to block X-rays below about 20kV) a 2 mil sheet of titanium
(added to remove the secondary copper X-rays) and a 12 mil sheet of
aluminum (to absorb the titanium X-rays).

The newly developed sample changer (designed by Dewitt Systems)

has a carousel that holds 20 samples . This sample changer has greatly
increased our analytical efficiency, allowing us to analyze up to 800
samples per week. An example sample spectrum is presented in Figure
4.

Figure 4: Example spectral output from the Bruker Tracer III-SD at MURR.

Sample Preparation for XRF

Sample preparation is highly variable depending on the matrix and

goals of the analysis. Most of the materials we analyze (obsidian,
metals, and ceramic paints) do not require any sample preparation.
The choice of sample preparation depends on the nature of the X-ray
beam relative to the sample. For example, a piece of obsidian that is 1
cm thick and has a clean, flat surface will provide ideal results. As
sample sget smaller, thinner, or less homogenous it is necessary to
understand the nature of the X-ray beam and how it interacts with the
sample.

The Bruker Tracer III instruments have a beam size of only about 2 x 3
mm. This small beam is fine for homogenous materials, but
heterogenous material such as crystalline rocks and tempered pottery
may need to be analyzed multiple times in numerous areas to
generate a representative average composition. The small beam size is
ideal for isolating specific painted elements on the surface of ceramics
and also aids in the analysis of very small obsidian artifacts.

Perhaps even more important than the area of the beam is the depth
of analysis. As a general rule, the higher up the energy spectrum, the
greater the depth of X-ray penetration in the sample. For example, the
analysis of iron (6.4 kV) in obsidian is primarily a surface analysis while
zirconium (15.78 kV) is measured from up to almost a centimeter deep.
In thick homogenous samples this depth of analysis makes little
difference, but if samples are thinner, it effects to resulting spectrum in
different ways depending on the specific sample thickness and
particular element of interest. Ferguson (in press) addresses a number
of approaches to quantitative analysis of thin samples.

The ability to analyze samples without destructive sample preparation

procedures has been a great advancement for archaeologists. We
can now analyze large and valuable artifact assemblages that would
have been off-limits to destructive proceedures. However, for non-
archaeological applications of XRFthe most common method of
sample prep is pelletizing, which can be made to work for most
matrices that can be ground into an homogeneous powder, including
soil, minerals, and dried organic matrices such as tissues or leaves.
Difficult grinding is accomplished with a hard agate mortar and pestle
but many samples can be adequately homogenized by placing into a
hard plastic vial, adding a plastic mixing ball, and violently shaking in a
mixer mill. A powdery binder containing cellulose, starch, polyvinyl
alcohol or other organics is usually weighed in and blended thoroughly
with the sample, and the resulting mixture added to a deformable
aluminum cup. (Buhrke p. 39) The sample and cup are pressed in a
cylindrical die to form a supported pellet which ideally has a smooth,
homogeneous sample surface and good physical stability.
Here particle size and homogeneity play a big factor. The thin surface
layer must be representative of the bulk sample, and studies have
shown that large errors (up to 50%) in quantitation can occur for some
elements when particle sizes exceed 50 µm. This is due to the variance
in X-ray penetration depths with energy (Jenkins 1995: 281). Particles
may be inhomogeneous also, having a different surface composition
than their bulk. For example, copper sulfides may become partially
oxidized at the surface, causing the relative absorption for Cu K lines to
differ from that of the L lines. The L line photons will not penetrate as
deeply and will tend to be emitted more from the oxide layer. By
monitoring the ratio of the Cu Kα line to the Cu Lα, the analyst can use
this phenomenon to an advantage, allowing him or her to deduce
some of the chemistry of the sample (Jenkins 2000).

One way to get around sample grinding is to fuse the sample at high
temperatures with sodium or lithium tetraborate and then to pour this
glass-like mixture into a mold (Buhrke: 41). Chemical reactions occur
within the melt which dissolve particles and create a homogeneous
liquid that hardens upon cooling. The disadvantages to this technique
include the additional time to prepare the melt and the possibility of
the sample reacting with even inert crucible materials such as
platinum.

Homogeneous solid samples such as metals may be machined and

smoothed to form disks. Whatever type of preparation is done, the
surface roughness of the sample should be taken into account. A
rough surface causes the penetration layer to look heterogeneous to
the spectrometer. In general, the surface roughness (measured in µm)
should not exceed the path length for 10% absorption of the radiation
being measured (Jenkins 1995: 278).

Applications of XRF Spectrometry

Currently XRF spectrometry is very widely applied in many industries

and scientific fields. The steel and cement industries routinely utilize XRF
devices for material development tasks and quality control. (Anzelmo
1987 Part 1) NIST utilizes XRF as one technique to quantitatively analyze
and acceptance-test many of its standard reference materials (SRMs),
from spectrometric solutions to diesel fuel to coal to metal alloys (Sieber
2000). The plastics industry is looking at a modified XRF spectrometer as
an on-line wear monitor, taking advantage of its ability to detect
particles of worn-off metal in extruded plastic pieces (Metz 1994). Polish
scientists are accomplishing XRF analyses on very thin films by placing
the source and detector at very low angles with respect to the sample.
This technique is being applied to trace element determinations in
water samples that have been evaporated to a thin film of residue
(Holynska 1998).

XRF has been one of the tools of choice for geologists for many years,
so much so that graduating geologists usually receive practical training
with these devices, whereas graduating chemists probably haven't
even heard of the technique. For geologists, the ability to determine
major and trace components in one quick analysis with relatively little
sample preparation has been a boon (Anzelmo 1987 Part 1, Part 2).
Current basic research aimed at improving XRF analyses for geological
and ecological samples focuses on methods for correcting for matrix
effects, in which major components absorb some of the X-rays emitted
from trace components (Revenko 2002).

Archaeometrists have applied XRF in order to solve their ancient

mysteries. An example of this was the study of the composition of blue
soda glass from York Minster, England, which distinguished three
compositional groups, indicating this number of possible sources for the
glass. Trace metal signatures also can effectively differentiate genuine
artifacts from modern copies (Jenkins 2000).

Forensic scientists utilize XRF spectrometry to match samples associated

with suspects (i.e. dirt or sand on clothing or shoes) to samples from
crime scenes. As for other applications, here XRF can help elucidate an
elemental fingerprint, without need to analyze the evidence
destructively (Jenkins 2000).

Comparison of XRF to Other Techniques

XRF is a versatile, rapid technique which lends itself to a wide variety of
samples from powders to liquids. It is convenient and economical to
use, with the major input cost being the hardware itself, which
averages around $75,000 for a modern industrial-use spectrometer or
$125,000 for a research-quality instrument. The instruments have few
moving parts, tend to be low-maintenance, and on a regular basis
consume only liquid nitrogen and electricity. Disadvantages include
fairly high limits of detection (LODs) when compared to other methods,
as well as the possibility of matrix effects, although these can usually be
accounted for using software-based correction procedures. LODs for
graphite furnace atomic absorption spectroscopy (GFAAS) beat XRF
by several orders of magnitude, but analyses can exhibit substantial
matrix effects. GFAAS is also relatively slow, with one element
determined at a time, and is destructive (Jenkins 1988: 161). PXRF
instruments are capable of producing results comparable in many
ways to the lab-based XRF at a fraction of the cost. PXRF instruments
can be purchased for about $30,000 to $50,000 complete with vacuum
systems, sample changer, and accompanying computer.

ICP-MS is a versatile technique that can achieve LODs many orders of

magnitude lower than XRF. In general, ICP-MS is easily capable of
determining many elements as quickly or more so than XRF with very
good accuracy. However, usually samples must be in liquid form, which
often requires acid digestion and laborious sample prep. One can
sample solids with laser ablation ICP-MS but this is better suited to tiny
spot sizes on the surface. ICP techniques also require copious amounts
of expensive high-purity argon gas.

Neutron activation analysis (NAA) uses thermal neutrons to activate

isotopes of trace elements in samples. It has ppb-level LODs and is
capable of fast, multi-element determinations. Certainly, though, it is
not as innocuous and convenient a technique as XRF, and requires
expert supervision as well as a nuclear reactor. It is dangerous and
possibly illegal to irradiate samples whose major components are
unknown.

Hopefully it is clear from this discussion what niche XRF occupies in the
field of elemental analysis. No technique is the answer to every
analytical problem, and the analyst must be judicious in his or her
selection of methodology.

Conclusion and the Future of XRF

XRF certainly does hold an important position in the realm of analytical
chemistry. Will it flourish in popularity in the future, or will it slowly fade
into obsolescence? To help provide an answer, two new XRF-related
technologies will be discussed. These advances are changing the face
of XRF spectrometry.

Total-Reflection XRF (TXRF)

By directing the beam of the X-ray source at a target at very low

angles of incidence (≤0.1°), it was found that the reflectivity of the
target increased greatly. By using this setup with a thin film of sample
on a flat support, it was possible to detect secondary X-rays emitted
from the sample with neglible contribution from the support. The
detection limits found with this method were better than conventional
XRF by five orders of magnitude, and were as low as 10–12 g. Matrix
effects were eliminated and the addition of internal standards was
simplified with this thin-film analysis. The discovery of TXRF roused the
interest of the semiconductor industry, which must control the amount
of surface contamination on cleaned wafers. Due to research directed
at this industry, limits of detection as low as 8 x 10-7 atoms Ni/cm² have
been reported (Potts 2001: 1223). A new benefit is that by varying the
angle of incidence in slight increments, analysts can now quantitate
not only the composition but the thickness of surface layers from 1 to
500 nm thick (Klockenk�mper 1997: 3–4).

In general, any type of sample can be analyzed by TXRF, as long as it is

possible to deposit it in a thin layer onto a carrier. Solutions or
suspensions may be deposited and dried, powders can be allowed to
settle as dust layers, and fibers may be simply placed on an
appropriate support (Klockenk�mper: 181). Other samples can be
laser-ablated and the resulting vapor deposited on a quartz reflector
(Potts: 1223) Clearly, TXRF is still in its infancy, but the possibilities for its
application seem vast.

Microcalorimeters and Transition Edge Sensor (TES) X-Ray Detectors

Materials at cryogenic temperatures exhibit a very low heat capacity.

Theoretically, the heat deposited by one absorbed X-ray photon could
change the temperature of a small volume of material enough to be
measured. This approach to photon detection differs fundamentally
from that of semiconductor-type devices and has been made
practical by the use of materials that become superconductive below
a specific transition temperature. Very slight ohmic heating is used to
balance these materials on the razor-edge of this transition, creating a
very sensitive thermometer. When a photon deposits its energy into a
strip of this material, the temperature and resistivity of the strip goes up,
reducing the current flow and the ohmic heating rate. The temperature
then drops back to the transition-edge. The blip in the current flow is
recorded by detector electronics, which relate current drop to photon
energy (Knoll 2000).

The advantage this very interesting new microcalorimeter brings to X-

ray detection is increased energy resolution. Recall that the X-Lab
2000's Si(Li) detector has an energy resolution of 150 eV at 5.9 keV. NIST
scientists, who developed the first TES, claim to have achieved an
energy resolution of 3 eV. This increased performance allows closely
spaced spectral peaks to be resolved, increasing the sensitivity and
accuracy of some complicated analyses. Moreover, with this new
detector, XRF can now yield information on the chemical bonding
state of elements by detecting minute X-ray energy shifts on the order
of a few eV (Sieber 2000).

Continued research into the fundamentals of XRF, stimulated partially

by the new advances mentioned above, means that the technique is
alive and well. Analytical chemists would be well-advised to keep their
eyes on the development of XRF and can look forward to better, faster
elemental analyses because of it.

References

Anzelmo, John A. and Lindsay, James R. Journal of Chemical

Education, August 1987, 64(8). A181-A185.

Anzelmo, John A. and Lindsay, James R. Journal of Chemical

Education, September 1987, 64(9). A200-A204.
Buhrke, Victor E.; Jenkins, Ron; Smith, Deane K. A Practical Guide for the
Preparation of Specimens for X-Ray Fluorescence and X-Ray Diffraction
Analysis. 1998, John Wiley & Sons, Inc. QD96.X2P73 ISBN 0-471-19458-1.

Ferrero, J. L. et al. X-Ray Spectrometry, 2002, 31, 441-447.

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