X-Ray Techniques

Francis, 2013

Electron Beam
X-rays Discovered by Roentgen, 1895
= 0.1 10 nm
For light, the minimum resolvable distance between 2 points:
= / NA Limiting case for light 200m or nm

The smaller wavelengths of X-Rays (0.1 10 nm) are similar to the size of atoms (0.1 0.2 nm), and
have energies that correspond to the energy differences between the inner atomic orbitals.

Fundamental Equivalency

Energy versus Wavelength of Photons

E = h. ergs per single photon

E = h.c/ ergs per single photon

h = Planck's constant = 1.38 10-16 erg sec

Black Body Radiation:

All matter emits continuous background

electromagnetic radiation whose energy
is a function of its temperature.

Our eyes are tuned to the Sun

whose Photosphere is 5780 K

Total emitted radiant energy:

Etotal = . T4 = ergs/sec/m2
= Stefan-Boltzmann constant = 5.672 10-16 erg/K

E = 2hc2/51/(e(hc/ (T-1))

Energy of most abundant photon:

E = hm = hc/m 3 . . T
= Boltzmann factor = 1.38 10-16 erg/K

T = hc/3m
T = (2897.8 / m) K = Wiens Law, where m is the wavelength of the most abundant photons
Characteristic Spectral Lines
Characteristic Spectral Lines
X-Ray Tubes
 60 kV Rhodium K lines and continuous spectrum

Rh K

Rh K
Braggs Law (1912)
X-Ray diffraction by atomic
lattice planes of crystals

n = 2 d sin()
 n = 2 d sin()

Antigorite

Counts

2 degrees X-ray Diffractogram

n = 2 d sin()

X-ray Diffractogram
 I = illite
S = smectite
Chl = chlorite
Clay Minerals Q = quartz
K = kaolinite

Scanning electron X-ray Diffractogram

microscope image of a
clay mineral

n = 2 d sin()
n = 2 d sin()
Illite Crystallinity

n = 2 d sin()
Mapping Alteration
Halos
Chemical Analysis

Characteristic Spectral Lines

 emission
excitation

emission

emission

excitation emission
 X-Ray Fluorescence Analysis
The excitation is produced by X-rays. The advantage of XRF
analysis is that it can analyze many elements down to levels of
ppm. The disadvantage of XRF analysis is that X-rays are
difficult to focus, and thus it is difficult to analyze small volumes.
XRF is the method of choice for obtaining the chemical
compositions of powdered or fused bulk rock samples.
 Electron Microprobe

Electrons can be focused with

magnetic fields to spot sizes on the
order of 1 micron or less. By using
an electron beam as the excitation
source, one can analyze very small
spots on mineral grains, and thus
investigate phenomena such as
compositional zoning in crystals,
partitioning of elements between
coexisting phases, etc.

The disadvantage of electron beam

excitation is that a relatively high
background radiation is created by the
electrons, which makes the detection
limits for most elements ~0.01 wt.%.
 Interaction between the Electron Beam and Sample Surface

Back-scattered electrons are those which interact with

atomic nucleii electrostatically and are flung back out
of the sample, in much the same way that a comet
interacts gravitationally with the sun.
Secondary electrons are produced by inelastic
collisions of electrons from beam with valence
electrons. These secondary electrons typically have
lower energies than backscattered electrons.

Auger electrons are produced by the interaction

between the characteristic X-rays produced by an
element with electrons in higher energy orbitals.
Auger electrons typically have energies that are the
difference between the energy of the initial electronic
transition that produced the characteristic radiation
and the ionization energy of the element.

Bremsstrahlung X-rays are the radiation that is emitted when electrons

are decelerated by a target. Accelerated charges give off electromagnetic
radiation, and when the energy of the bombarding electrons is high
enough, that radiation is in the X-ray region and is characterized by a
continuous distribution of radiation which becomes more intense and
shifts toward higher frequencies as the energy of the bombarding electrons
is increased. This background radiation is the principle limitation in
analyzing elements at very low concentrations with the electron
microprobe.
Interaction between the Electron Beam and Sample Surface

~ 1 micron
spot
WDS: Wavelength Dispersive Analysis

Electron Microprobe Analysis X-Ray Fluorescence Analysis

 Gas-Flow Proportional Counter

The counter is a chamber containing a gas

that is ionized by x-ray photons. A central
electrode is charged at ~ +1700 V with
respect to the conducting chamber walls,
and each photon triggers a pulse-like
cascade of electrons across this field. The
signal is amplified and transformed into
an accumulating digital count.
 Energy Dispersive Analysis (EDS)

In energy dispersive analysis, the

dispersion and detection of X-rays is a
single operation. The fluorescent X-
rays emitted by the sample are directed
into a solid-state detector which
produces a continuous distribution of
pulses, the voltages of which are
proportional to the incoming photon
energies. These detectors consist of a 3-
5 mm thick silicon junction type p-i-n
diode with a bias of ~ -1000 Volts
across it. The lithium-drifted centre part P-type Si is doped with 3+cation such as Al to provide
forms the non-conducting i-layer. When electron holes.
an x-ray photon passes through, it N-type Si is doped with 5+ cation such as P to provide
causes a swarm of electron-hole pairs to excess electrons.
form, and this causes a voltage pulse. I-type intrinsic semiconductor
The detector must be maintained at low
The electrical pulses generated by the detector are
temperature with liquid-nitrogen for the
processed by amplifiers and significant computer
best energy resolution. power is required to correct for pulse-pile up and for
extraction of peaks from poorly-resolved spectra.
 EDS Olivine
(Mg,Fe)2SiO4
Energy Dispersive Analysis

Diopside
Ca(MgFe)Si2O6

Hornblende
Wavelength dispersive analysis (WDS) is inherently more precise because of the better resolution of the spectral
peaks. The disadvantage of WDS is that peaks must be occupied sequentially by the spectrometer, which slows
the analytical process. With 4 spectrometers, a 10 element major analysis takes approximately ~ 4 minutes of data
acquisition. WDS is the method of choice for high-quality quantitative analysis.
Energy dispersive analysis (EDS) has less energy resolution, but has the advantage that all spectral lines are
accumulated simultaneous, giving a complete analysis in ~ 20 seconds. EDS is the method of choice for
qualitative identification analyses.
Quantitative Analysis

Conc(I)unkn ~ (Count(IPeak)unkn -(Bkgd)) / (Count(IPeak)Std (Bkgd))

 Matrix Corrections
Matrix effects can affect the X-ray spectrum produced in an electron microprobe
analysis and have to be corrected for an accurate analysis. These matrix corrections
are called ZAF corrections, in reference to their three components: atomic number
(Z), absorption (A), and fluorescence (F).

Atomic Number Correction

X-ray emission is dependent on atomic number because of the stopping power of the target and
backscattering from the target. Stopping power is the ability of a material to reduce the energy
of an electron by inelastic scattering. This property is a function of A/Z, in which A is the atomic
mass and Z is the atomic number. A/Z increases with increasing Z, as a result, the X-ray
intensity per unit concentration increases with Z.

Some of the electrons hitting the sample will be ejected back

Fe-rich
out. This process is known as backscattering and it is strongly
affected by atomic number. The effect of backscattering is to
decrease the X-ray intensity with increasing Z, which is
Mg-rich
opposite to the effect of stopping power. However, the
backscattering effect is greater and, therefore, the overall atomic
number correction follows the same trend. Minerals with high
mean atomic number appear brighter in back-scattered electron
images because they backscatter more electrons. Back-scattered electron image of
olivine phenocryst
Back Scattered Electron Image Showing Compositional Zoning in Tourmaline
Back-scattered electron image
of zoned clinopyroxene
phenocryst with superimposed
chemical analysis of Al content
and Mg# (Mg/(Mg+Fe))
Absorption Correction
X-rays are generated throughout the analytical
volume during a probe analysis. Those X-rays
produced at depth must pass through a certain
distance within the sample and risk being
absorbed, reducing the X-ray signal of the
element of interest.

Fluorescence Correction
The critical excitation energy (Ec) of an element is the energy threshold needed to dislodge inner
electrons and generate characteristic X-rays. In addition to the incident electrons, however, X-
rays from the ionization of elements with higher Ec will also ionize atoms of elements with
lower Ec, whose own characteristic X-ray emission lines will then be enhanced. There is also
fluorescence caused by the X-ray continuum or continuous X-ray background emission produced
by electron deflections. As an electron passes near an atomic nucleus, it may be slowed by the
electric field of the nucleus, causing a quantum jump to a lower energy state and the emission of
more X-rays.