Neutron powder diffraction

studies of magnetic materials

D.H. Ryan
McGill University

Neutron scattering
Many features of thermal neutrons make them
ideal for crystal structure determination:
1.
2.
3.
4.
5.

Weakly interacting
Penetrating
Non-destructive
Wavelength matches lattice spacing
Light/heavy element sensitivity

Magnetic neutron scattering

The neutron also has a magnetic moment this
means that it can scatter from other magnetic
moments in the sample.
The magnetic scattering length is comparable
luck.
to the nuclear scattering length No deepJustphysics
here.
this means that the magnetic and nuclear
signals have comparable strengths.

Magnetic structure determination

Everything that you have heard about crystal
structure determination applies equally to magnetic
structure determination.
The neutron scattering pattern observed for a
magnetic material is just the Fourier transform of the
nuclear and magnetic structure.
In principle, everything that you can learn about the
crystal structure can also be learned about the
magnetic structure.
The same basic analysis principles are followed.
Even the same programs are used

Magnetic structure determination

Neutron diffraction is the best way to study magnetic ordering.
Should always be combined with complementary methods to
obtain a more complete picture
Examples include:
Bulk magnetic methods (magnetisation, susceptibility)
Mssbauer spectroscopy
NMR
SR
TDPAC

Some key differences

Magnetic scattering involves the interaction of
the neutrons magnetic moment with that of an
atomic electron
EM not strong interaction
Both the nature of the scattering and the object
that the neutron scatters from are different.
The form of the scattering is therefore quite
different.

Magnetic form factor

Nuclear scattering involves the interaction of a neutron with a
point-like (much smaller than the wavelength) object the
nucleus so the scattering is isotropic.
Magnetic scattering involves the interaction of a neutron with
the extended atomic electron distribution, so the form factor is
more like that seen for x-ray diffraction, and it falls off quite
rapidly with angle.
Unfortunately, the situation is actually worse than it is for xrays as the coherent magnetic scattering comes ONLY from
the electrons that contribute to the net moment on the atom,
and these tend to be in the outer shells (3d, 4f)

Magnetic form factors

Magnetic form factors

The loss of higher-angle magnetic scattering is not normally a problem
for magnetic structure determinations:
1.

The underlying crystal cell is normally known

2.

The magnetic cell cannot be smaller than the crystal cell, so we do

not expect to be looking for new high-angle reflections

3.

The magnetic cell is frequently much larger than the crystal cell,
so we find new peaks at low angles where the form factor is not
an issue

4.

Some quick-and-dirty fits to the nuclear structure can be obtained

by considering only the high angle data where the magnetic
scattering should be absent

New scattering rules

Magnetic scattering of a neutron by an atomic
moment involves the EM interaction between
the neutron moment P (a vector) with the
atomic moment (also a vector) and leads to a
change in the momentum of the neutron (yet
another vector)
This is clearly going to be more complex than
the simple point-on-point nuclear scattering!

It is convenient to define a magnetic

interaction vector q as:
q = ( )

with |q| = sin

where is the angle between and .

The differential magnetic neutron
scattering cross section per atom can then
be written as:
This is zero when is zero,
i.e. when the atomic moment
and the scattering vector are
parallel to each other.

Selection rules
Only the component of the atomic moment
that is perpendicular to the scattering vector
contributes to the magnetic scattering.
Components of the atomic moments that are
perpendicular to the neutron polarisation
(neutron moment) also cause the neutron
moment to flip spin-flip scattering.

Start with a simple example: MnF2

MnF2 adopts a tetragonal
crystal structure (a = b > c, all
angles 90).
Just two species (Mn and F),
only one of which (Mn)
carries a moment.
Simple magnetic structure:
corner Mn moment up,
body-centre Mn moment
down an antiferromagnet.
TN is 67K so it is easy to
study.
Mn moment is 5B, so the
magnetic scattering is strong.

Magnetic scattering from MnF2

It immediately clear that the magnetic

signal is large!

If we consider a (fictional)
ferromagnetic form with the Mn
moments along c, all of the Mn
moments point the same way, so they
are equivalent, and the magnetic
scattering comes from a bct
arrangement of moments.

Kittel tells us that the structure factor

for bcc (or bct) requires h+k+l=2n, and
that is what we see.

Magnetic scattering from MnF2

All of the new, strong
reflections fit the h+k+l=2n
rule.
What about the absences?
Most can be understood as
violations of the h+k+l=2n
rule.
But what about the (002)
reflection?

The peak intensities and

pattern tell us about both the
symmetry and the direction
of the ordering.

Antiferromagnetic order in MnF2

The clearest effect of the c-axis AF

order is the appearance of the (100)
reflection.
The down Mn moment in the body
centre position is not equivalent to the
up Mn moment in the cell corner, so
the magnetic structure is not bodycentred and the h+k+l=2n rule does not
apply.
The (001) reflection is absent because
the moments are parallel to the c-axis.

Beyond the simple picture (I)

With one magnetic species and only two
magnetic atoms in the cell, MnF2 is a
particularly simple case.
Our simplistic description cannot easily extend
to more complex situations, and cannot begin
to accommodate the realities of magnetic
ordering.

Describing magnetic structures

The most important change is that we replace point atoms with
vector moments, as we must consider both the location and the
orientation of the moments in order to fully describe a
magnetic structure.
The underlying crystal lattice is (in principle) unchanged, and
the moments simply decorate a sub-set of the lattice points.
The symmetry operations that were developed to describe the
crystal space groups are not quite sufficient to describe
magnetic ordering, as the moment vectors are axial vectors
arising from current loops, and not the more common polar
vectors that simply indicate a direction.

Axial vs. polar vectors

Simple operations like

translations (t) and 2-fold
rotations (2) act the same way on
axial and polar vectors.

However, an inversion centre (i)

does not reverse the sense of a
current loop and so although it
would flip a polar vector, an axial
vector is not affected.

Conversely, a mirror (m) would

not flip a polar vector that lies
parallel to the mirror plane, but
does reverse the sense of a current
loop, so reversing the axial vector.

Anti-operations

The time-reversal operator (R or

1) is added in order to reverse the
sense of the final current loop and
so permit a further set of
symmetry operations.

Thus the antirotation (2) inverts

an axial vector while the
antireflection (m) does not.

All magnetic structures that

remain within the underlying cell
can be described in terms of some
combination of primed and unprimed symmetry operators.

Magnetic Bravais Lattices

Adding the time-reversal operator increases the number of Bravais

lattices from the 14 crystallographic lattices to the 36 magnetic lattices

Shubnikov Groups

By associating the 1 operator with a colour change (from black to white, or in some
usages, black to red) the new magnetic symmetry theory was termed black-white
symmetry.

The number of magnetic (or colour) space groups increases. A lot!

The original 230 space groups are retained as colourless groups and keep their labels
e.g. Pmmm.

A further 230 groups are created by adding the 1 operator as an extra symmetry
operation e.g. Pmmm1 and correspond to paramagnetic states of magnetic systems.
They are often termed grey as each magnetic site is both black and white.

The most important set is created by combining the 1 operator with one or more of
the symmetry operations in each of the 230 crystallographic space groups e.g.
Pmmm, where the mirror plane perpendicular to a is now an anti-mirror, and the
other two are unchanged.

This activity leads to a further 1191 black-white (or coloured) groups, for a total of
1651.

Shubnikov Groups
The document describing all 1651
Shubnikov groups is a 63Meg pdf that
runs to 4472 pages.
It is an object of great beauty.

D.B. Litvin, J.Appl.Cryst. A64 (2008) 419

What have we gained?

We have a compact, finite description of all possible magnetic
structures that remain within the crystallographic cell.
Once we know the crystal structure, and can establish that the
magnetic cell corresponds to the crystallographic cell, then we
can enumerate the possible magnetic space groups.
The locations of the magnetic ions in the crystallographic cell
can limit the allowed moment directions, so some magnetic
groups can be eliminated by noting the presence or absence of
key reflections (like the (001) (100) pair in MnF2)

Impact of mirrors and antimirrors

If the crystal space group involves a

mirror-plane and a moment is oriented
perpendicular to it, then the generated
moment is parallel to the original.

If we now move the moment on to the

plane there is no contradiction as the
moment is consistently mapped onto itself.

However, if we use an antimirror then the

moment is reversed, and if it is moved onto
the antimirror plane the mapping is
inconsistent we cannot have a moment
with a component perpendicular to an
antimirror.

For moments parallel to mirror planes, the

conditions are reversed: an atom located
on a mirror plane cannot have a
component parallel to the plane, while one
located on an antimirror must have all of
its components in the plane.

Examples in the Immm space group

No antimirrors
The 2d atoms lie on the
c-mirror and a-mirror so
any moment would have
to be orthogonal to both
the bc- and ab-planes,
which is not possible.
Similarly the 4e atoms
lie on the b- and cmirrors, and again no
moment is permitted.

Immm c-antimirror
This 2d atom lies on the a-mirror
moment along a,
But this 2d atom lies on the bmirror moment along b. Not
possible.
This 4e atom lies on the b-mirror
(moment along b) and the cantimirror (moment in the abplane) consistent!
This moment is inverted because it
is the product of the I operation
reflected in the a-mirror which
inverts the moment.

Antiferromagnetic order, but only on the 4e site

Immm b- and c- antimirrors

2d atom on c-antimirror
moment in ab-plane.
On a-mirror moment along a.
Centering operation does not
invert FM order along a-axis

4e on b-antimirror moment in
ac-plane.
Also on c-antimirror moment
in ab-plane.
Puts the 4e moments along a-axis
Moments are perpendicular to the
a-mirror so this does not reverse
them.
Both the 2d and 4e moments order FM along the a-axis.

Example of use: Sm3Ag4Sn4

This is a highly absorbing sample due to the

samarium, so the sample had to be quite
small.
The samarium moment was expected to be
only about 0.5B (a tenth of the Mn moment
in MnF2) so the magnetic scattering was
expected to be weak.
The only magnetic peak detected was
indexed as the (100), and its temperature
dependence could be followed.
The transition temperature was consistent
with our Mssbauer data.

The (100) peak along with other observations

imposes some clear constraints:
1. At least one Sm site must order
2. The order is not FM
3. The order is not parallel to the a-axis

Enumerate the possible groups

No order

FM order
Ordering along
a-axis

Down to only 6 possible groups

Final result comes from analysis of the (100)

intensity and 119Sn Mssbauer data

Of the six possible magnetic

space groups, only two (Ipmmm
and Ipmmm) yield significant
intensity only at the (100)
position.
Analysis of our 119Sn Mssbauer
data showed that only the Ipmmm
structure was consistent with the
observed spectrum.
This group only permits ordering
on the Sm-4e sites

With the structure established, we

could complete the fit and
determine the Sm moment to be
0.470.10B in Sm3Ag4Sn4.

C.J. Voyer et al., J. Phys.: Condens. Matter 19 (2007), 436205(12)

Powder averaging can impose limits

The main difference between the Ipmmm and Ipmmm structures for Sm3Ag4Sn4 is
that the Sm-4e moments lie along b or c respectively.

As the crystallographic cell is orthorhombic (abc, all angles 90), the b and c
directions are distinct, even in a powder, and in principle, with better statistics, we
could uniquely determine the ordering direction directly from the diffraction data.

However, if we lose this distinction by raising the symmetry to tetragonal (a=bc)

or cubic (a=b=c) then the powder averaging that is inherent to powder diffraction
imposes limits on what we can determine from the diffraction pattern.

Similar problems arise in hexagonal systems where the ab-plane is distinct from
the c-axis, but the a and b directions are equivalent.

Gen Shirane, J.Appl.Cryst. 12 (1959) 282

Ambiguity

For the tetragonal examples shown, in

each case, the peak intensities observed
from an equal mixture of (a) and (b) are
the same as those observed for the
structure shown at (c).
The (c) structures are clearly very
different, but they cannot be distinguished
from the corresponding (a) structures on
the basis of neutron powder diffraction
alone.

The rules are simple, and absolute.

For a cubic system you are stuck.

For a system with a unique axis
(tetragonal, rhombohedral or hexagonal)
the angle between the moment and the
unique axis is all that can be determined.
The projection onto the plane is
indeterminate.
Gen Shirane, J.Appl.Cryst. 12 (1959) 282

Re-orientation in a hexagonal system

(001)

4K

80K
520K

YbFe6Ge6 Magnetic peak intensity

YbFe6Ge6 Magnetic peak intensity

Counts
600Counts
600
500
500
400
400
300
300
200
200
100
100
10
10

20
20

30
30

40
40T

(K)
T (K)

50
50

60
60

70
70

80
80

Re-orientation in a hexagonal system

Analysis of the neutron diffraction data gives:

Fe = 1.60 0.13 B
= 7113 degrees

Single crystal 57Fe Mssbauer data give:

= 692 degrees
Spectacularly good agreement!
Note: the azimuthal angle is indeterminate in both
cases.

Finding magnetic peaks

One irritating problem with studying

magnetic order using neutron powder
diffraction is that all of the easy samples
have been done!
You rarely (not quite never) encounter a
new system that orders at a decent
temperature and gives huge magnetic peaks.
Generally you have to go to some pretty
extreme conditions and then you are
rewarded by finding very weak magnetic
peaks.

Nd3Cu4Sn4 is a case in point.

119Sn Mssbauer spectroscopy and

susceptibility both place the ordering at 2K,
but an earlier search for magnetic ordering
at 1.5K came up blank.
Our run at 0.4K shows a lot of very weak
peaks that are most easily detected by
subtracting the high-temperature pattern
(taken at 3.2K!)
These now need to be indexed before we
can proceed to a structure refinement.

Sometimes this does not work

Tb3Ag4Sn4 does not order simply.

It undergoes an
orthorhombicmonoclinic distortion
as the magnetism develops.
The crystal structure changes at the
same time that the new magnetic
reflections appear.
Cannot use the RT crystal cell to
guide the magnetic refinement.
Need low-T xrd to isolate the
structural changes and to determine
the low-temperature crystallographic
cell.
Only then can we return to the
magnetic problem.

Checking the magnetic cell

Once we have found our magnetic peaks, we

need to index them to get some idea of the
ordering.
One simple strategy is to use a Le Bail or
profile fit to locate the peaks.
However, as we saw with MnF2, the magnetic
selection rules are often different because only a
subset of the atoms in the cell carry moments.
This can mean that the magnetic peaks are not
allowed by the crystal symmetry.
The solution is to drop the symmetry to the
lowest space group consistent with the crystal
class (in this case P222 for the orthorhombic
cell) to allow for the generation of all hkl
combinations and then run a Le Bail fit.
For the example shown here, this strategy works
very well and all of the new peaks are fully
accounted for.
The very strong (010) peak near 10 suggests acplane ordering, but a full analysis reveals a more
complex structure.

More complex ordering

Although the magnetic ions are located on a given crystallographic cell, their ordering is not
totally restricted by that cell.

In a sense, the cell only provides guidelines for the ordering and the moments can, and
frequently do, find ways to express their independence.

The simplest change is a doubling of the cell size along one axis, so that the magnetic period is
twice that of the chemical period in one direction.

However, there is no absolute requirement that the magnetic and crystallographic periodicities
be in any way linked.

The magnetic ions are located on the crystallographic cell, so the magnetic structure is
sampled with the crystal periodicity, but the magnetic period does not need to be a simple
multiple of the crystal period.

Such incommensurate structures are relatively common in metallic systems where the
exchange interactions are mediated, at least in part, by the conduction electrons and the
structure of the Fermi surface rarely exhibits the same wavevectors as the crystal.

Cell-doubled AF
There are a total of six
different ways that you can
decorate the fcc lattice.
For I, the unit cell is
preserved, but II
corresponds to a doubling of
the cell dimensions in all
three directions.
The two forms labeled III
give a doubling on one axis,
while the IV forms are
doubled in two directions.

Yb2Cu2O5 a cell-doubling example

Orthorhombic Pna21 (#33)
2 R sites, 2 Cu sites and 5 O
sites
All sites are 4a triclinic
symmetry (1) hence (x,y,z)
undefined by symmetry
a ~ 10.7 , b ~ 3.5 and c
~ 12.4

Yb [0.85 1.08 0] B 1.37 (7) B

Cu [0 0.53 0] B 0.53 (4) B

Indexing of the peaks shows that the cell is doubled

along both the b and c axes.

170Yb Mssbauer gave Bhf = 134(1) T at 2 K.

The average hyperfine field at the 170Yb site
corresponds to an atomic Yb3+ moment of
1.29 (1) B

Incommensurate ordering
The cell-doubling in Yb2Cu2O5 can be viewed as a long-period modulation of
the crystal symmetry, which since we generally prefer to describe
diffraction-derived structures in reciprocal space, translates as a short
wavevector propagation vector.
In this language, doubling along b and c is represented as a [0,,]
propagation vector, qp.
The complete structure can be viewed as the original one modulated by this
wavevector and the new reflections due to this modulation then decorate the
basic crystallographic reflections: (h,k,l) qp.
Once we move to this kind of language, we quickly see that there is no
requirement that the components of qp be simple rational fractions, allowing
us to describe any modulated magnetic structure, with any periodicity.

(0 0)

Dy3Ag4Sn4: Neutrons
Neutrons show initial ordering
to be incommensurate at 16K
Order becomes commensurate
below 10K as the order locks in
to the lattice
Magnetic cell is doubled along
b so that it does not match the
crystallographic cell

(0 0.63 0)
is first to appear

Crystallographically equivalent
tin sites are no longer
magnetically equivalent

Dy3Ag4Sn4: Confirmation
Analysis of the derived magnetic
structure[] shows that the Sn-4f sites
have a unique magnetic environment,
while the Sn-4h sites split into two
equal sub-groups.
The Sn-4h1 and Sn-4h2 sites have very
different magnetic environments
Neutron diffraction yields the same
2:1:1 area split that is seen in the
Mssbauer data
Consistency provides independent
confirmation of the magnetic structure.
FullProf Studio

[] Perry et al.., J. Phys.: CM 18 (2006), 5783

More complex structures

The ordering of the hexagonal compound
ErCuSi shows up as a very complex pattern
of satellites.
Analysis leads to a sine-modulated structure
with a propagation vector of (1/12, 0, 0)
causing a simple decoration of the
crystallographic reciprocal lattice points.

P. Schobinger-Papamantellos et al., JMMM 223 (2001) 203

On cooling below 3.7K a weak third

harmonic peak (3q) starts to develop,
signaling a squaring up of the sinemodulated structure.

P. Schobinger-Papamantellos et al., JMMM 223 (2001) 203

Partial ordering

Modulated structures require that only

partial ordering of some of the moments
occurs.
The spiral structures (SS, FS and CS)
involve a complete ordering of the
moments as every site has a full moment.
The longitudinal and transverse spin wave
(LSW and TSW) structures have only
partial moments at most of the sites.
This is easy to accommodate in transition
metals and their alloys as the delocalised
moment is a band effect, but for local
moment systems (like the rare earths) one
needs fluctuations to cause a substantial
fraction of the moment to time-average
away.
In such cases, further cooling generally
leads to a gradual squaring-up of the
modulation.

Complementarity: Er ordering in ErFe6Sn6

Despite the expected 9B moment expected

on the Er ions, the purely AF (1,5/2,0) peak
at 12 is extremely weak. This is the
strongest magnetic peak from the Er sublattice.
The temperature dependence confirms the
4.80.4K ordering temperature.
Magnetisation data suggest mixed FM / AF
ordering of the Er moments.
Analysis of the complete pattern leads to
an Er magnetic structure with FM order
along [100] and AF order along [010],
however the derived Er moments are only
2.61.0 B (FM) and 4.91.5 B (AF) for a
net moment of 5.51.8 B.

The problem is two-fold:

(1) The weak FM scattering sits on strong
nuclear peaks and rarely amounts to more
than the statistical uncertainty on those
peaks.
(2) The AF scattering only yields a single
isolated peak.
J.M. Cadogan et al., J. Appl. Phys. 95 (2004), 7076-8.

Neutron diffraction yields the magnetic structure, but

the moment values need to be obtained from other
measurements.
Magnetisation yields a more
reliable estimate for the FM
moment: 5.90.1 B.
166Er Mssbauer spectroscopy
gives us the total Er moment:
8.50.1 B.
Combining the magnetisation
value with the AF moment
from neutron diffraction
leads to a total Er moment of:
7.71.5 B, which is
consistent with our 166Er
Mssbauer value.
J.M. Cadogan et al., J. Appl. Phys. 95 (2004), 7076-8.

Some useful references

Applications of Neutron Powder Diffraction, Erich H. Kisi and Christopher J.

Howard, Oxford 2008

Introduction to the Theory of Thermal Neutron Scattering, G.L. Squires, Dover

1978

Introduction to Crystal Geometry, M.J. Buerger, McGraw-Hill 1978

Neutron Scattering with a Triple-Axis Spectrometer, Gen Shirane, Stephen M.

Shapiro and John M. Tranquada, Cambridge 2002

Neutron Diffraction of Magnetic Materials, Yu A. Izyumov, V.E. Naish and R.P.

Ozerov, Plenum 1991

Tables of Crystallographic Properties of Magnetic Space Groups, D.B. Litvin,

J.Appl.Cryst. A64 (2008) 419