Structural probes for

solid materials

2. Physical interaction
of X-rays with solid
materials
 Contents

1. Introduction to properties of X-rays

2. Generation of lab X-rays
3. Scattering (diffraction) of X-rays from electrons, atoms and crystals
4. Other interactions of X-rays with solid materials

Lecture material and further reading:

1. “The Basics of Crystallography and Diffraction” (C. Hammond), Chapter 7, 8.3, 9.8

2. “Elements of X-ray Diffraction” (B.D. Cullity and S.R. Stock, chapters 1, 3, 4.1-4.3)

3. “Fundamentals of Powder Diffraction and Structural Characterization of Materials” (V.K.

Pecharsky and P.Y. Zavalij), chapter 2

4. “Elements of Modern X-ray Physics” (J. Als-Nielsen and D. McMorrow), chapters 1, 2

5. “X-ray Structure Determination” (G.H. Stout and L.H. Jensen), chapter 2

6. “Fundamentals of Crystallography” (C. Giacovazzo), chapters 3, 5

 Diffraction of waves

•Diffraction involves the apparent bending of waves around obstacles.

•Most significant effect is when obstacle is of similar size to the wavelength.
Atomic radii in a crystal lie in the range 0.3 – 2.0 Å.
 X-rays

Wavelength (m)

1Å 1nm 1μm 1mm

•Refractive index of X-rays is close to 1, thus they cannot easily be focused by

lenses. Direct observation of objects using an “X-ray microscope” is hence
difficult. Instead, crystal structures must be probed indirectly using diffraction.
 Diffraction of waves

•Path differences of waves diffracted from different points give rise to an

interference pattern.
•When diffraction is from a crystal lattice, such interference patterns can be
used to probe crystal structures.
 X-rays

A polarised X-ray beam

can be approximated z
as a plane wave.

Electric field of a
plane-polarised wave wavelength wavenumber
as a function of Spatial variation
position z can be
expressed as a sine or E0
cosine wave, either in
its real form 0 π 2π

E = E0cos(kz)

or in its complex form

E = Eoeikz

(because eix = cosx + isinx,

Euler’s formula)
 X-rays
•A wave vector can alternatively be represented in the complex plane:

Im
•The wave can be described by
E0

φ
E  E0 cos   E0i sin   E0 ei
Re

•The intensity of a wave is given by the square of its amplitude. For a complex
quantity, multiply by the complex conjugate:

i  i i 2
I  E0 e E0 e  E0 e

or 
I  E0 cos   i sin  E0 cos   i sin    E02 cos 2   sin 2  
 X-rays

A polarised X-ray beam

can be approximated z
as a plane wave.

Electric field of a
plane-polarised wave wavelength wavenumber
as a function of time t Spatial variation
can be expressed as
E0
E = E0cos(ωt)
0 π 2π
E = Eoeiωt
period cyclic frequency
Temporal variation
Combining position
and time:
E0
E = E0cos(kz-ωt) 0 π 2π

E = E0ei(kz-ωt)
 Properties of X-rays

•From a quantum mechanical point of view, a monochromatic X-ray beam is

quantized into photons, each with energy ħω and momentum ħk.

•Intensity of X-ray beam = number of photons passing through a given area per
unit time.

•Magnitude of electric field is thus quantised.

 Properties of X-rays

Numerical relation between wavelength (in Å) and photon energy ε (in keV) is:

 Å 
hc 12.398

  keV

X-ray energies are interchangeably expressed in units Å or keV.

 First demonstrations of X-rays

Wilhelm Röntgen 1845 – 1923 Max von Laue 1879 – 1960

(First Nobel prize in physics 1901) (Nobel prize in physics 1914)

•Discovered X-rays in 1895. •Predicted in 1912 that X-rays might be

waves and be diffracted by crystals.
•X-rays were immediately used for
medical imaging, but their nature •Demonstrated X-ray diffraction from a
remained unknown for 17 years. copper sulfate crystal.
 First crystal structure solution

William Henry Bragg 1862 – 1942 William Lawrence Bragg 1890 – 1971
(Joint Nobel prize in physics 1915)

•Used X-ray diffraction in 1914 to solve the first crystal structures (NaCl) which
proved that not all crystals were composed of covalently bonded molecules.
 Sealed tube X-ray generators

High
vaccuum

(metal target)

•X-ray production efficiency is only ~0.1%: remaining energy is dissipated as heat.

•The tube cooling system determines the maximum power that can be applied.
 Rotating anode X-ray generators

•Cylindrical anode rotates. Anode is

larger, can be cooled better, input
power can be ~20 times greater.

•Expensive and less reliable

 Microfocus X-ray generators

•The electron beam is focused on a thin target by an electromagnetic lens.

•X-rays are extracted through a pinhole.
•Gives a very intense but very small (typically tens of microns) beam diameter.
 Generation of X-rays in the lab - bremsstrahlung

Needed in order to generate X-rays:

1. Source of electrons (cathode)

2. Means of accelerating the electrons (high voltage)

3. Metal target for accelerated electrons to interact with

A continuous spectrum of X-ray radiation is emitted by bremsstrahlung.

Electrons are decelerated and eventually stopped in the metal target.
 Generation of X-rays in the lab - bremsstrahlung

Maximum possible X-ray energy: Emax  max  eV

(assuming all of the electron energy is transformed to radiation)
 Generation of X-rays – emission lines
1.) Ionization
Free space
2c.)

2a.) 2b.) Relaxation

High
energy
electrons 3.) Emitted
X-rays
(fluorescence)

Inner shell
 Generation of X-rays – emission lines

Sharp lines are superimposed on the white bremsstrahlung spectrum when the
electron energy is large enough to ionise the metal.
 Generation of X-rays – emission lines

0.7107 Å

1.5418 Å

•Choose a metal target (anode) to obtain emission peaks at the desired

wavelength for the diffraction experiment. Typically Mo and Cu are used.
 Scattering of X-rays from an electron

•Oscillating electric field forces an electron to oscillate with the same frequency.
•Oscillating electron then emits X-rays in a spherical wave.
 Scattering of X-rays from an electron

•Classically, the incident and scattered wavelengths are the same (elastic).

•This is not necessarily true for quantum mechanical description; energy may be
transferred to the electron such that the scattered photon has a lower frequency
(inelastic). (This is the Compton effect- see later).
 Thomson scattering of X-rays from an electron

Joseph Thomson 1856 – 1940

[Discovered the electron (1897)]
For an unpolarised source, intensity of scattered wave at observation point X
 r2 
 
(distance R from electron) is 1
I   02  E02 1  cos2 
R  2
Thomson scattering length r0 = 2.82 × 10-5 Å
(the “ability” of an electron to scatter X-rays)

•Wave crests of elastically scattered spherical wave lie in between those of the
incident wave due to a phase shift of 180° - coherent scattering.
 Compton scattering of X-rays from an electron

collision of photon + electron

Arthur Compton 1892 – 1962

•Here we need to imagine X-rays as photons rather than waves.

hν2 < hν1 (energy is transferred from photon to electron)

λ2 – λ1 = 0.0486 sin2θ

•Scattered radiation wavelength depends on θ.

•Phase has no relation to incident beam- incoherent.
•Compton scattering gives rise to a background signal in an elastic scattering
experiment.
 Thomson scattering of X-rays from an atom

•When two or more electrons are involved, each gives rise to a spherical
scattered wave.
•The different spherical waves will interfere by addition of their amplitudes.
•Interference can be constructive or destructive.
 Thomson scattering of X-rays from an atom

•Amplitude of X-rays scattered in direction of incident wavevector k is proportional

to number of core electrons.
•For any scattering angle 2θ > 0 the core electrons introduce a path difference δ,
which leads to more destructive interference with increasing 2θ. The size of δ is
significant because the size of an atom is comparable to the X-ray wavelength.
 Scattering of X-rays from an atom

Cl Cl-
Intensity  f 2

K+

f (electrons)
•Scattered intensity
scales with square of
O atomic number.

•Light elements
scatter X-rays weakly.

(sinθ)/λ (Å-1)
•Atomic scattering factor f is defined as:
amplitude of the wave scattered by an atom
f 
amplitude of the wave scattered by one electron
•f = Z (the atomic number) when scattering is in the forward direction (θ = 0).
•As θ increases, waves scattered by individual electrons become more out of phase
and f decreases.
 Diffraction of X-rays by a crystal

k k'

Bragg’s Law: n  2d hkl sin 

•n is the order of diffraction (for fixed λ and dhkl, there may be more than one
angle at which diffraction can occur, but we usually assume that n = 1).

Note: the terms “scattering”, “diffraction” and “reflection” are often used interchangeably!
 Bragg’s Law

n  2d hkl sin 

•We can use Bragg’s Law to calculate the d-spacing of a set of lattice planes
(hkl) when a diffraction peak for that set of planes is observed at an angle θ.

1 h2 k 2 l 2
2
 2  2  2 for a unit cell with all angles 90°
d a b c

•If we determine enough d-spacings for different (hkl) planes we can obtain
the unit cell dimensions and angles (although this is often not easy to
calculate if we do not know what (hkl) planes the diffraction peaks
correspond to!)
 Positions of diffraction peaks
Example: diffraction pattern of ZrO2
The unit cell parameters a, b and c can be determined from the hkl indices
and angles of the diffraction peaks shown below, assuming that the unit cell
angles are all 90º and that λ is known.

200   2dsin 
50.08°
1 h2 k 2 l 2
2
 2 2 2
d hkl a b c
202
61.91° 220
73.53°
004
71.56°
 Bragg’s Law- limits of diffraction

n
Consequences of Bragg’s law:  sin   1
2d hkl

•nλ must be less than 2dhkl.

•Therefore, when n = 1, λ < 2dhkl.

•For most crystal planes dhkl is ~3 Å or less, thus λ must be smaller than ~6 Å.

•This shows that a crystal cannot diffract long-wavelength radiation (eg. UV and
visible light).

•To obtain a lot of data (to measure scattered intensity from many crystal
planes), choose a small wavelength.

•Bragg’s law allows us to determine unit cell lengths and angles, but does not
predict the scattered intensity, which we need to obtain atomic positions in the
crystal. We will look at this later.
 X-ray absorption and emission

incident photon

Photoelectric absorption results in the ejection of a core electron, leaving the

atom ionized and a hole in the inner shell.
X-ray absorption and emission

Fluorescent X-ray emission

Instead of emitting
fluorescent X-rays,
another electron (from
an outer shell) may be
emitted.

Auger electron emission

 X-ray absorption and emission

•In diffraction experiments, fluorescent X-rays can give a high background if the
incident X-ray energy is close to the binding energy of inner shell electrons.

•However, fluorescent X-ray emission gives a “fingerprint” of the electronic

structure of the atom involved and can be used for chemical analysis and
spectroscopy.

•The radiation that creates the inner shell hole can also be protons or electrons
(eg. electrons are used in energy dispersive X-ray spectroscopy - EDX).
 X-ray absorption and emission

Typical EDX spectrum for elemental analysis

• In energy dispersive X-ray spectroscopy (EDX) the radiation that creates

the inner shell hole is an electron beam. The energy and intensity of the
emitted X-rays are measured.
 X-ray absorption

K-edge

The absorption of an element decreases with increasing X-ray energy.

In the Kr example above, at energies below the absorption K-edge electrons
can only be expelled from the L and M-shells.
At energies above the K-edge electrons can also be expelled from the K-shell.
•In diffraction experiments, absorption can give a high background due to
fluorescence if the incident X-ray energy is close to that of an absorption edge.
 X-ray absorption - example

Mo Kα radiation Cu Kα radiation Cu Kα radiation

Cobalt Nickel

• Samples containing Co are strongly absorbing towards Cu Kα radiation

(common for lab diffractometers).
• Samples containing Co are better measured using lower wavelength X-rays
– gives more intensity at detector and less background from fluorescence.
 X-ray absorption

•Absorption cross-section varies with the atomic number of the absorber as ~Z4.

•X-ray absorption thus shows great contrast between different elements and can
be used in medical applications; eg. CAT (computer aided tomography) scanning
of bones (containing Ca), which have much lower X-ray transmission than tissue
(mostly H, C, O).
 X-ray absorption

dz

I(z)

linear absorption coefficient

Incident beam is attenuated by μdz through an infinitesimally thin sheet of

thickness dz at a depth of z from the sample surface.
 X-ray absorption

Values of 1/μ for various materials

λ = 0.56 Å λ = 1.54 Å
Vacuum ∞ ∞
Helium 600 m 300 m
Air 15 m 1m
Beryllium 23.5 mm 3.6 mm
Aluminium 1.4 mm 76 μm
NaCl 1.1 mm 61 μm
Lead 13 μm 4 μm

(1/μ is considered the “optimal” sample thickness, at which the incident intensity
is reduced to 37% of its initial value.)

• Beryllium is used for X-ray “windows”.

• Lead is used for safety, to stop X-ray beams.
Interaction of X-rays with bulk matter - summary
Typical X-ray diffraction data (diffraction pattern)

Thomson scattering
n  2d hkl sin 

Compton scattering
and fluorescence
X-ray refraction and reflection from surfaces and interfaces
•Because X-rays are electromagnetic waves, one should expect refraction at
interfaces between different media.

•For visible light in glass the refractive index n' is ~1.5 – 1.8, compared to 1.0 in
vacuum.

•This allows visible light to be focused by lenses and “white” visible light to be split.
X-ray refraction and reflection from surfaces and interfaces

Light X-rays

n n
n′ n′

Snell’s law: n cos   n cos  

For X-rays in a solid material n  1    i
of the order 10-5 much smaller than δ
X-ray refraction and reflection from surfaces and interfaces

Light X-rays

n
n
n′ n′

n  1    i
cos   n cos  

•Because for X-rays n′ < 1, this implies that α′ < α

•Below a critical incidence angle where cos α’ must apparently be greater than
unity, X-rays undergo total external reflection and Snell’s Law no longer holds.

Neglecting β, it can be shown that  c  2  0.05

X-ray refraction and reflection from surfaces and interfaces

•Total external reflection can be used to construct a focusing X-ray mirror.

•Below αc the reflectivity is almost 100%. A so-called evanescent wave

propagates parallel to the interface with a penetration of ~10 Å. This allows the
nature of surfaces and interfaces to be probed (see later).
 Magnetic interactions of X-rays

•Thus far the magnetic field component of X-ray radiation and the spin of
electrons have been neglected.

•The magnetic field component is sensitive to the spin and orbital magnetic
moments of the electron (magnetic dipoles).

•It is thus possible to probe ordered arrangements of electron spins (magnetic

structures) using X-rays.
 Magnetic interactions of X-rays

CePt3Si
•For 10 keV X-rays:

Amagnetic   
  2   0.01
Acharge  mc 

Amplitude ratio of magnetic to charge scattering

J. Phys.: Condens. Matter 16, L207 (2004)

•The scattered intensity from magnetic moments is ~104 times weaker.

•A very intense X-ray beam is needed to probe electron spins.

 Magnetic interactions of X-rays

• The above paper is the first report of magnetic X-ray scattering (using a lab sealed tube X-ray source). Each
peak was scanned for 3 days. Nowadays synchrotron X-ray radiation is used to probe magnetism (see later).