Neutron Diffraction and Comparison with X-ray

and Electron Diffraction

Graham King
Brockhouse Instrument Scientist
Canadian Light Source
October 30th, 2020
The Big Picture

• Radiation which scatters off atoms leads to interference patterns (diffraction)

which can be used to probe how the atoms are arranged in a material.
• There are three types of radiation which are used for this purpose: Photons
(X-rays), neutrons, and electrons.
• These methods have different sensitivities, advantages/disadvantages, and
much different instrumentation.
• The best method depends on the specific problem. The methods are
complementary and often two or all three methods are needed to gain a
complete structural understanding.
 X-ray Diffraction
X-ray wavelength ~ spacing between atoms. The X-ray interaction with matter is Moderate.

X-ray diffraction is by far the most common method used as X-rays can be produced relatively cheaply
with high flux.

X-ray tubes consist of an anode material which is bombarded Synchrotrons and free electron lasers can
by electrons to give off X-rays at a characteristic wavelength. produce extremely bright X-ray beams.
Cu and Mo are the most common andoes.
Mechanism and (Dis)Advantages of X-ray Diffraction

• X-rays scatter off the electrons, hence they tell you about the electron density.
• As electrons density is diffuse X-ray scattering has a form factor (the intensity
falls off at large Q from destructive interference within an atom).
• They interact strongly enough that small samples can be used, but weakly
enough that multiple diffraction usually isn’t a problem.
• X-rays can be easily produced by laboratory machines.
• Extremely bright X-ray sources at user facilities allow sub-second data
acquisition, enabling time resolved studies.
• Light elements can be difficult to locate in the presence of heavy elements.
Basics of Electron Diffraction
The interaction of electrons with matter is Strong. Electrons interact through the Coulomb force and are affected by
both the electrons and protons in the nucleus. The strong scattering is both the advantage and disadvantage of
electron diffraction.

Usually performed on individual crystals. Single crystal diffraction

patterns from powder sized crystals! Can be very useful for indexing.

Very weak peaks can be clearly seen in electron diffraction.

However, multiple diffraction is common so the structure usually cannot

be solved from the intensities like with single crystal X-ray diffraction.
Information Obtained from Electron Diffraction

• Done in conjunction with Transmission Electron Microscopy as

they use the same instrument.
• Very useful for space group determination.
• EELS (Electron Energy Loss Spectroscopy) for elemental
mapping.
• Very subtle superstructures can be clearly observed that are
undetected by other types of diffraction (figure left).
• It is not a bulk technique, only a few crystallites will be studied,
need to be representative.
• Often the first step in the solution of a complex structure.
 Mechanism of Neutron Diffraction

Basic Neutron Facts: Neutrons interact with the nuclei

• No electric charge of atoms through the strong
• Have significant mass but also nuclear force, instead of the
wave properties . electron could.* As this force is
very short range and nuclei are
• Have a magnetic moment
tiny compared to the atoms
• Unstable outside of the nucleus, neutron scattering is Weak.
lifetime of ~15 minutes

*Except in the case of magnetic scattering form

unpaired electrons. This is covered later.
Types of Neutron Interactions with Matter
Scattering Absorption
Neutron is absorbed into the
Coherent Elastic Incoherent Elastic nucleus, changing the isotope.
The kind that gives Does not contain
rise to diffraction. structural information.

Coherent means the phase of the

Coherent Inelastic Incoherent Inelastic wave is preserved after scattering.
Gives information on Measures self-correlation. Elastic means that no energy is
atom dynamics. transferred, the scattered wave has
the same energy as the incident one.
Neutron Scattering of Elements
Measured as a cross section (σ) with units of barns
(1 barn = 10-24 cm2). The scattering length, b, is more
commonly used and is related as σ=4πb2.

Scattering length does not have any periodic trend,

it varies randomly across the periodic table.

As the neutron interacts with the nucleus, each

isotope has different scattering and absorption
characteristics. Values given are for the weighted
average of all naturally occurring isotopes unless
otherwise specified.
Negative Scattering Length
When X-rays scatter there is always a phase shift. When neutrons scatter there is usually a phase
shift, but for some elements there is not. This makes these waves have opposite phase (negative
scattering length).

Ti = -3.44
O = 5.80
Negative
Mn Fe
Ti-O peak.
-3.73 9.45

This can lead to very strong

Pair distribution function and
contrast between some elements. crystal structure of SrTiO3.

Can lead to negative peaks in a PDF.

Main Advantages of Neutron Scattering Contrast

O W Co Ni
5.80 4.86 2.49 10.3

Locating light atoms in the Differentiating atoms with

presence of heavy atoms. similar X-ray scattering.

Neutrons were used to determine

the tilting of the oxygen octahedra
in NaLaMnWO6 (left). Neutron PDF
is able to separate out the local
Mn-O and Ru-O bond lengths in
AMn0.5Ru0.5O3 (right).
No Form Factor
X-rays have a form factor due to destructive interference between electrons of the same atom. As the
nucleus of an atom is very small compared to the distance between atoms neutrons have no form factor.

NaLaMnWO6 NaLaMnWO6
XRD, λ = 1.5406 NPD, λ = 1.5403

X-ray diffraction patterns fall off at high angle Neutron patterns have stronger intensity at high Q.
due to thermal motion and the form factor. Better for determining thermal parameters.
Incoherent Scattering

• Occurs as a result of having different isotopes

of an atom randomly distributed on a nucleus
having multiple nuclear spin states.
• Contains no structural information.
• Adds background to diffraction patterns.
• Needs to be removed for PDF, no analytical
way to do this but some ways to estimate
and subtract.
Absorption
Varies by many orders of magnitude between elements as well as among isotopes.
No trends based on periodic table, as with other neutron properties there is no pattern.

Some Elements with Large Neutron Absorptions (cross sections in barn):

• Gd (49,700), largest of all elements by far. 7 naturally occurring isotopes, absorption is huge for 2, large
for 1, moderate for 1 and small for 3. Isotropic substitution is therefore possible but expensive.
• Sm (5,922)
• Eu (4,530)
• Cd (2,520), sometimes used in shielding
• Dy (994)
• B (767), boron compounds often used as shielding, absorption is due to 10B (σ = 3,835; abundance
20%), pure 11B can be used (σ = 0.006).
• Ir (425)
• Hg (372), can be used a liquid shutter
• In (194); Rh (145); Er (159)
 Some Notes about Hydrogen
Both good and bad for neutrons:
• Negative b of -3.74 fm means it can be easily detected in the presence of heavy elements.
• Large incoherent σ (82 barn) gives rise to large backgrounds.
• Deuterium (2H) has a b of 6.67 fm and incoherent σ of only 2.1 barn, samples are often
deuterated to reduce incoherent noise.

Bond lengths involving H are longer when determined

by neutrons than X-rays, as the center of electron
density cannot be approximated as being at the nucleus.

Side note: In small angle scattering and reflectometery of soft matter

involving two component with similar scattering density, one
component can be deuterated while the other isn’t to increase contrast.
Scattering from a sample containing hydrogen.
Some Notes about Lithium
• Li positions are difficult to detect using X-ray diffraction, especially when heavier elements
are present.
• The neutron b of Li (-1.90) has a small magnitude but the scattering is still closer in magnitude
to most heavier metals than with X-rays. The negative sign also helps provide contrast.
• Li has a moderate absorption cross section of 70.5 barn.
• So neither X-rays nor neutrons are great for finding Li, although neutrons are usually better.
Many neutron proposals are for studying Li ion conductors.
• The absorption of Li is mainly due to the 6Li isotope, which has a an absorption of 940 barn
and a natural abundance of 7.5%. Pure 7Li can be used to reduce absorption.
Some Notes about Oxygen
Neutrons are great for studying oxygen. It has a medium sized b of 5.803 and negligible
incoherent σ and absorption. Many proposals are for accurately locating O positions in
compounds with heavy metals.

N O F
9.45 5.80 5.65

Neutrons are also great for finding N and F positions. In oxynitrides neutrons can easily
differentiate between the O and N. For oxyfluorides neither X-rays nor neutrons can tell O and
F apart with much accuracy, indirect assignments based on bond lengths are the only way.
Magnetic Scattering
• Neutrons are spin ½ particles with a magnetic moment.
• While neutrons do not interact with the electrons through the Coulomb force, they do
interact with unpaired electrons through the magnetic force.
• Magnetic scattering happens to be of a similar magnitude to nuclear scattering.
• As the unpaired electrons are in the outer shells, the are very diffuse. Therefore,
magnetic scattering does have a form factor and peaks from magnetism fall off very
rapidly with Q.
• Magnetic structure determination is a major use of neutron diffraction.
What is a Magnetic Structure
The magnetic moments of the unpaired electrons can crystallographically order.

Paramagnetic Ferromagnetic Antiferromagnetic Ferrimagnetic

Above a certain Spins all aligned in the Spins all aligned in the Unequal spins aligned
temperature the spins same direction, strong opposite direction, no oppositely, net moment.
randomly fluctuate, no net net moment. net moment.
moment without a field.
Magnetic Structure Determination
NaLaMnWO6 • Index relative to the nuclear unit cell using a
propagation vector.
• This pattern is indexed with k = ½ 0 ½
• In other words, the magnetic unit cell is 2 × 1 × 2 the
size of the nuclear unit cell.
• Propagation vectors can be incommensurate.
• Rietveld refinements used to solve magnetic
structure.

Collect diffraction patterns above and below

the magnetic ordering temperature.
Types of Magnetic Structures
Many types of magnetic structures are possible:
• Commensurate and incommensurate
• Colinear, non-collinear, spiral, conical

The AFM k = ½ 0 ½ The AFM structure of

commensurate and NaTbMnWO6, showing an
collinear structure of incommensurate spiral.
NaLaMnWO6. Red Red arrows are Mn2+
arrows are the moments and green
moments on Mn2+. arrows are Tb3+ moments.
Short Range Magnetic Order

Magnetic pair distribution function is an emerging technique

to study short range correlations in spin glasses, spin liquids,
and other exotic phases.

Magnetic PDF is obtained by subtracting the nuclear PDF

from a sample to get the contribution from diffuse magnetic
scattering.

It’s important to keep in mind that even if you are not

interested in magnetism but you have unpaired electrons,
magnetic scattering will be present and a source of error.
Overview of Neutron Sources
Two Main Types

Reactor: Spallation:
• Based on fission of radioactive elements (U), • Uses proton beams to blast apart
similar to a nuclear power plant. heavy elements.
• Usually used for monochromatic beams. • Usually used for pulsed beams
(time-of-flight).
Reactor Sources
• Neutrons are produced by controlled fission of enriched
uranium fuel.
• When a U atoms decays several neutrons are released.
Some of these trigger new nuclear decays while other
escape down flight tubes to be used for experiments.
• Similar to a nuclear power plant but the goal is neutron
production instead of heat production.
• Beryllium reflectors used inside.
235U • Reactors produce a steady supply of neutrons.
n
Reactor Powder Diffractometers

• Generally similar to synchrotron beamlines.

• A large single crystal monochromator is used to select a
single wavelength.
• The diffraction pattern is then collected as a function of
angle.
• Often many detectors are used in an array to speed data
collection as the flux is much smaller than for X-rays.

The BT-1 diffractometer at the NIST

NCNR. It has 32 detectors that only
need to rotate 5 degrees.
 Spallation Sources
• Spallation is a process by which a heavy nucleus is blasted into
pieces after being hit by another particle.
• Spallation neutron sources use pulsed proton beams.
• The protons are created by stripping the electrons off hydrogen,
accelerating them to near the speed of light in a liner
accelerator, then smashing them into a target.
• The target is often W but could be other heavy metals. Hg is
used in some newer facilities for easier cooling.
• The heavy nucleus breaks into two smaller nuclei and also
releases many free neutrons.
• This creates pulses of neutrons, usually at rates of 10’s of hertz.*
The linear accelerator at LANSCE,
• All new facilities being built are spallation. Los Alamos National Lab.

*It is possible to produce a steady source of neutrons by spallation by using a constant stream of
protons. The SINQ facility at the Paul Scherrer institute works this way.
Moderators
Neutrons produced by fission or spallation are very high energy (MeV). To be useful for diffraction they need
to be slowed down (meV).

• This is done by having the neutrons collide with nuclei to

give up their energy.
• The temperature of the moderator determines the
spectrum of neutron energies exiting.
Hot neutron Thermal neutron
• For diffraction room temperature neutrons have the right
wavelength range.
• Materials with lots of H are usually used. Often just water,
sometime liquid methane or liquid H2.
• Some neutrons don’t fully thermally equilibrate. These
epithermal neutrons are important for the high Q-range of
spallation source.
Time-of-Flight (TOF) Diffraction
In TOF the angle is fixed and Normally the wavelength is fixed
the wavelength is varied.
λ = 2dsin(θ) and the angle is varied to get d.

• As neutrons are particles with mass, their speed varies with their energy/wavelength.
• At a spallation source, pulses of neutrons with a spectrum of wavelengths are produced. The time it
takes them to reach the detector is recorded. Diffraction occurs when they have the right wavelength
to satisfy Braggs law.
• A plot of diffraction intensity vs. time is recorded, which can be converted into d-spacing.
• Detectors are placed at fixed angles. Several different angles can be used. These different detector
banks each record their own diffraction pattern. Depending on the angle the patterns have different
d-spacing coverage and resolution.
• While TOF is normally done at spallation sources, it can be done at a reactor sources by placing a
chopper in the beam to create pulses.
 Time-of-Flight Instruments
Intensity vs. Resolution
Proton beam
• Is determined by the flight path length.
Detector banks
• The longer the path the more time the
Moderator neutrons have to sort themselves by energy, so
High energy Long flight path the better the resolution.
neutrons (thermal neutrons) • The intensity falls off as 1/r2, so the closer the
sample
better the flux.
Target (heavy metal) • It is important to keep in mind that as neutrons
have no charge, they cannot be steered by
magnetic fields. They also cannot be easily
A few other notes:
focused by lenses.
• Beamlines sometimes have chopper that is closed at t0 to
• Neutron guide materials based on refraction do
protect detectors from gamma rays and fast neutrons.
exist to help keep flux on long beamlines, but
• A trigger measures the t0 when the proton pulse arrives. these are mostly used for longer wavelength
• A “get lost tube” at the end absorbs the un-scattered neutrons.
beam.
 Time-of-Flight Data
5000
Raw Normalized
2.5
4500

4000
2
3500

3000
Intensity

1.5

Intensity
2500

2000
1
1500

1000 0.5
500

0 0
2 4 6 8 10 12 14 2 4 6 8 10 12 14
Time (ms) Time (ms)

The distribution of energies in a neutron pulse is not uniform. Patterns usually divided by incident flux. Keep in
mind that the high d-spacing region of each bank has lower counting statistics than the small d-spacing region.
Incident flux is determined by measuring vanadium, which has a small coherent b of -0.38 fm but a moderate
incoherent σ of 5.08 barn.
 Low angle banks cover a
Detector Banks in TOF large range of high d-spacing
with low resolution.
31 deg 120.4 deg High angle banks cover small
range of low d-spacing with
high resolution.

65 deg 150.1 deg

TOF peaks have an odd

and complex shape.
Practical Aspects of Conducting a Neutron Experiment
Neutrons are very penetrating: Everything is bigger with neutrons.
• Neutron beams cannot be focused and must be large (mm scale). Sample sizes of a few grams are
often preferred, a few hundred mg can be used. Much more sample is needed than for X-rays.
• Samples are often contained in a V can, as V has very weak coherent scattering.
• Collection times are usually several minutes to several hours, much longer than for X-rays.
• Many samples will become radioactive. You can’t get them back right away. If some elements,
such as Co, are present you will never get them back.
Inelastic Neutron Scattering
Neutrons are great as the can probe the structure AND dynamics of matter. They can tell you where the
atoms are and what they are doing.

Thermal neutron energies are comparable to lattice vibrations. Phonons are typical a few tenths of a
percent to a few percent of the neutron energy. X-rays are much higher energy and require much greater
energy resolution for inelastic experiments. Phonons, magnons, and other excitations can be measured.

S(Q,ω) Triple Axis Spectrometer

The dynamic structure factor can Uses monochromatic radiation,
be measured and contains all the then a second analyzer crystal
information about the system. to determine energy transfer.
This is a sort of master function Slow measurement but gives
of condensed matter physics. much information.
Neutron User Facilities
USA Europe

NIST NCNR: reactor source ISIS spallation source in England

Oak Ridge has 2 neutrons sources: ILL reactor source in France

HFIR is a high flux reactor
European Spallation Source (ESS): under construction, will
SNS is a high power spallation
be the most powerful source, user program begins in 2023.

Japan

J-PARC spallation source

Note: This list is not comprehensive. These were selected as

they are probably the most relevant to Canadian researchers.
SNS at Oak Ridge
Take Home Messages
• Neutrons interact weakly with matter and are very penetrating. Neutron flux is also much
lower than at X-ray sources.
• Neutrons scattering varies randomly with Z.
• Neutrons can often locate light atoms in the presence of heavy ones.
• Neutrons can often distinguish neighboring elements.
• Neutrons can be used to solve magnetic structures.