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Energy Dispersive X-ray Fluorescence (ED-XRF)

X-ray Fluorescence Spectroscopy (XRF)

X-ray Fluorescence (XRF) - Measurement System

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HORIBA > Technology > Elemental Analysis > Energy Dispersive X-ray Fluorescence (ED-XRF)
> X-ray Fluorescence (XRF) - Measurement System

X-ray Fluorescence (XRF) - Measurement System

X-ray generator — The Basics

All XRF spectrometers require a source of X-rays, and these are usually provided by an in situ X-ray generator, or,
less frequently, by a radioisotope material.
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 A typical X-ray generator passes an electric current through a !lament, which causes electrons to be emitted.
These electrons are then accelerated by high voltage (usually somewhere between 20 and 100kV) towards an
anode (target). The deceleration of the electrons when they hit the anode causes a broad X-ray continuum to be
emitted. This radiation is known as bremsstrahlung (German: braking radiation). In addition, a fraction of the
electrons will cause characteristic X-ray "uorescence from the anode material.

Thus, the X-ray emission from a generator will comprise both the broad, relatively weak bremsstrahlung, overlaid
with very intense and sharp characteristic "uorescence lines from the target material.

A thin beryllium window is used to allow the X-rays out of the generator, and onto the sample.

X-ray generator — Target, Current and Voltage

The target material, !lament current and accelerating voltage all have signi!cant effect on the !nal output of an X-
ray generator.

Target (anode)
The target material is a !xed component of the generator – generators with different target materials are available
(eg, Mo, Rh, W), but these are not switchable within a single generator unit. A key part of the generator’s output is
formed from the characteristic X-ray Fluorescence of the target material. Since the "uorescence yield increases
with atomic mass, increased output at a set voltage/current will be seen by using higher atomic mass target
materials. In addition, the energies of the "uorescence lines will vary depending on the material used, and as a
result different target materials can result in more or less ef!cient excitation of particular elements in the sample.

Current
The !lament current controls the number of electrons bombarding the target material. As a result, the current
directly impacts on the X-ray output intensity for both the bremsstrahlung and characteristic radiation.

Voltage
The bremsstrahlung radiation displays a high energy cut off, since the energy of the radiation cannot exceed the
applied voltage. By changing this voltage, the bremsstrahlung cut off (and overall continuum pro!le) can be
modi!ed. The characteristic radiation from the anode material can only be generated when the accelerating voltage
(and hence, the energy of the impinging electrons) lies above the absorption edge for that material. Thus, if the
voltage is reduced to below the absorption edge, the characteristic line(s) will no longer be present.

Experimental Control

As stated on the previous page, a user typically has no control over the target material used in the generator,
although generators with different materials are available. However, the tube current and voltage are important
variables in an XRF experiment.

The current controls the intensity of X-rays emitted from the generator, and is primarily adjusted to optimize the
signal level at the detector.

The voltage has an important effect on the spectral pro!le of the generator output. With low voltages (eg, 15kV or
lower), the bremsstrahlung will be centered at relatively low energies, and the characteristic "uorescence will be
restricted to the low energy L (and M) lines. At high voltages (eg, 40kV or above), the bremsstrahlung will be more
intense and centered at higher energies, and the characteristic "uorescence will include the high energy K lines of
the target material.

The most ef!cient XRF is stimulated when the incident X-ray beam lies close in energy to the absorption edge in
the element(s) in the sample. Thus, by adjusting the generator voltage it is possible to tune, to some degree, the
ef!ciency of "uorescence in the sample.
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 The energy of the X-ray beam also has an strong effect on the penetration of the X-rays into the sample. The lower
the energy, the less penetration. Once again, by adjusting the generator voltage some control is possible over the
incident X-ray beam penetration and hence the sampling depth.

How to Create X-ray Micro-Beams

In a micro-XRF spectrometer it is necessary to generate an intense, narrow X-ray beam. There are two main
methods to do this which are summarized below, and will be discussed in more detail in the following pages.

Collimators (aperture)

The X-rays from the generator are passed through a small aperture usually in the range of a few millimeters down
to a few hundreds of micrometers in diameter.

X-ray optics

In 1984 a Russian scientist, Muradin Kumakhov, proposed that smooth solid surfaces could be used to form,
control, and guide X-ray beams, by virtue of total external re"ection. This led to the development of a range of X-
ray optics, which can be used to form parallel and focused beams, and transfer X-ray beams with high ef!ciency.

Collimators

The use of collimators for generating narrow X-ray beams is straightforward, but can suffer from loss of intensity as
the beam diameter decreases.

Passing a relatively large X-ray beam through a small aperture results in most of the primary X-rays being blocked
by the material around the aperture. X-rays only pass through the aperture itself, yielding a beam with a diameter
approaching that of the aperture.

However, as the aperture is narrowed, the proportion of X-rays which are blocked increases dramatically. Thus,
beams generated in this manner with diameters below 500 µm become low in intensity, and diameters below 100
µm become unworkable because of this problem.

Today collimators are successfully used for high spatial resolution analysis (beam diameters <20 µm) on
synchrotron sources, where the extremely high beamline intensities mean that intensity losses are not an issue. For
benchtop instruments with less bright X-ray sources, collimators are not used for ultra-high spatial resolutions.

Mono-Capillary Optics
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 As Kumakhov discovered, X-rays are very ef!ciently re"ected off glass surfaces when the angle of incidence is low.
By producing carefully shaped glass optics it is thus possible to use this total external re"ection to focus, collimate
and steer X-ray beams.

The solid angle from the X-ray source to the capillary is relatively large, which means that coupling between the two
is ef!cient. As a result, very high intensities of X-rays can be channeled into the capillary, and since re"ection itself is
very ef!cient, capillaries can be used to generate high intensity micro-beams with diameters as small as 10 µm.
The HORIBA X-ray guide tube (XGT) is an example of the successful use of mono-capillaries, and indeed is unique
in allowing 10 µm spatial resolution on a bench top system.

In addition to their intensity, beams generated with mono-capillary glass optics display near perfect collimation,
making them ideally suited for micro-XRF analysis.

Poly-Capillary Optics

Kumakhov also showed how capillary optics could be bundled together to form what are called poly-capillary
optics. Beams produced in this manner offer bene!ts in intensity, but they are strongly focused (and hence these
optics are often denoted Kumakhov lenses). Focused spots with diameters down to 40-50 µm are possible.

For spatially resolved XRF analysis, focused beams are not ideal. X-rays penetrate into the sample (several
micrometers through to several millimeters depending on the particular sample), so that although small spot sizes
are produced at the focus point, out of focus beams give rise to "uorescent X-rays from much larger analysis
areas.

In addition, the focused nature of the beam means that micro-XRF imaging of rough samples is dif!cult - areas in
focus will bene!t from small spot sizes, but regions showing a height difference will become blurred due to much
larger out of focus spot sizes.

X-ray Detectors

There are a range of detectors available for energy dispersive X-ray spectroscopy. These can be split into three
main types:

Solid state semiconductor

These are usually based around silicon or germanium chips. The X-rays enter through a thin beryllium window, and
produce electron-hole pairs in the semiconductor region of the detector. The number of electron-hole pairs formed
depends on the energy of the incoming X-ray. The higher the X-ray energy, the larger the number of electron hole
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 pairs. A high voltage is applied to pull the electrons to the back of the detector, where they are collectively recorded
as a negative pulse. A multi-channel analyzer (MCA) then counts these pulses, and sorts them into size (which is
equivalent to X-ray energy).

To provide acceptable energy resolution, solid state detectors are typically cooled with liquid nitrogen, resulting in
typical resolution of <165eV.

In many cases this cooling is also vital in maintaining correct dopant dispersion throughout the semiconductor, and
warming can cause serious damage to the detector. However, new generations of high purity detectors (for
example, the Xerophy™ from HORIBA) remove these concerns, and allow the detectors to be repeatedly
temperature cycled as required – cooling is only required whilst detecting.

Silicon drift detectors (SDD)

As their name suggests, silicon drift detectors are also based on a silicon detecting element, but the design is
somewhat different from the typical solid state detector discussed above. Concentric electrodes are placed on the
back surface of the silicon, which are used to steadily pull the electrons (arising from X-ray absorption) towards the
center of the chip. As before, the electrons are collected as a negative pulse, and counted by an MCA.

What is different about the SDD is that very good energy resolutions (~150eV) can be obtained solely with peltier
cooling (typically down to -20 to -30 °C). In addition, multiple incident X-rays can be detected sequentially, since
electrons formed by X-ray absorption in different regions of the detector will have different drift times to the anode.
As a result, much higher count rates can be tolerated.

In contrast to the solid state detectors, SDDs show relatively poor sensitivity for high energy X-rays.

PIN diodes

As its name suggests, a pin diode detector uses a much smaller detector element - however as with the two
varieties described above, they are typically based on a silicon semiconductor material for the detection. The small
size of the semiconductor element allows peltier cooling, but the reduced thickness compromises sensitivity,
particularly for the heavier elements.

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