Basics of X-Ray Powder Diffraction

Scott A Speakman, Ph.D.

[email protected]
(617) 253-6887

http://prism.mit.edu/xray

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 Training Required to become an Independent User
in the
X-Ray Shared Experimental Facility
at the
Center for Materials Science and Engineering at MIT

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 Required Safety Training

1. The X-Ray and Lab Specific Safety Training Class taught in the X-
Ray SEF will fulfill two mandatory requirements:
All users must complete the EHS X-ray Safety training, course #EHS0361c
All users must complete the X-ray SEF Lab Specific Safety Training
2. All users must complete the MIT online chemical hygiene training,
course #EHS0100w
3. All users must be up to date on their MIT managing hazardous
waste training, course #EHS0501w
4. All users must be registered in CMSE user management system,
MUMMS
https://cmse-coral.mit.edu/mumms/home.html
5. All users must read the CMSE chemical hygiene plan and sign-off
on the chemical hygiene plan in MUMMS
 Instrument Specific Training

These courses cover how to safely operate instruments to collect data.

Users much complete the instrument specific training for each instrument
that they wish to use, even if they have used a similar instrument
elsewhere.

Powder Diffractometers:
PANalytical XPert Pro Multipurpose Powder Diffractometer
Rigaku SmartLab Multipurpose Diffractometer
Rigaku Cr-Source Powder Diffractometer
Bruker D8 with GADDS 2-dimensional detector

Other instruments
Bruker D8 HRXRD
Bruker Handheld XRF
Multiwire Back-Reflection Laue Diffractometer
 Data Analysis Workshops

These workshops are optional, but highly recommended, so that users can
perform effective and accurate analysis of their diffraction data

Basic XRPD Data Analysis using HighScore Plus

Primary focus is on phase identification and qualitative analysis, with some
discussion on topics such as lattice parameter and crystallite size calculations

Quantitative Analysis using Profile Fitting and Line Profile Analysis

Profile fitting is the most precise way to determine diffraction peak position,
intensity, and width for calculating lattice parameters and crystallite size

Rietveld Refinement
The Rietveld method is used to refine the crystal structure model of a material. It
can be used for quantitative phase analysis, lattice parameter and crystallite size
calculations, and to refine crystal structure parameters such as atomic positions
and occupancies
 High Resolution X-Ray Diffraction (HRXRD) Training

HRXRD is used to analyze epitaxial thin films

Can determine composition, strain/relaxation, lattice parameters (in-
plane and out-of-plane), thickness, and defect concentration
X-Ray Reflectivity (XRR) is used to analyze thin films, including
amorphous and non-textured films
Can determine thickness, roughness, and density

Introduction Lecture
Instrument training on the Bruker HRXRD and/or Rigaku
SmartLab
HRXRD Data Analysis Workshop
 Introduction to Crystallography and
X-Ray Diffraction Theory

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 2012 was the 100th Anniversary of X-Ray Diffraction
X-rays were discovered by WC Rontgen in 1895
In 1912, PP Ewald developed a formula to describe the
passage of light waves through an ordered array of scattering
atoms, based on the hypothesis that crystals were composed
of a space-lattice-like construction of particles.
Maxwell von Laue realized that X-rays might be the correct
wavelength to diffract from the proposed space lattice.
In June 1912, von Laue published the first diffraction pattern
in Proceedings of the Royal Bavarian Academy of Science.

The diffraction pattern of copper sulfate, published in 1912

 The Laue diffraction pattern

Von Laues diffraction pattern supported

two important hypotheses
X-rays were wavelike in nature and therefore
were electromagnetic radiation
The space lattice of crystals

Bragg consequently used X-ray diffraction

to solve the first crystal structure, which
was the structure of NaCl published in The second diffraction
June 1913. pattern published was of
ZnS. Because this is a
Single crystals produce spot patterns higher symmetry
material, the pattern was
similar to that shown to the right.
less complicated and
However, powder diffraction patterns look easier to analyze
quite different.
 An X-ray powder diffraction pattern is a plot of the intensity of
X-rays scattered at different angles by a sample

The detector moves in a circle around the

X-ray sample
tube The detector position is recorded as
w the angle 2theta (2)
2q The detector records the number of X-
sample
rays observed at each angle 2
The X-ray intensity is usually recorded
as counts or as counts per second

Many powder diffractometers use the

Intensity (Counts)

Bragg-Brentano parafocusing geometry

10000
To keep the X-ray beam properly
focused, the incident angle omega
5000 changes in conjunction with 2theta
This can be accomplished by rotating
0 the sample or by rotating the X-ray
35 40 45 50 55
Position [2Theta] (Cu K-alpha) tube.
 X-rays scatter from atoms in a material and therefore contain
information about the atomic arrangement
Counts
SiO2 Glass
4000

2000

0
4000 Quartz
3000
2000
1000
0
Cristobalite
4000

2000

0
20 30 40 50
Position [2Theta] (Copper (Cu))
The three X-ray scattering patterns above were produced by three chemically identical
forms SiO2
Crystalline materials like quartz and cristobalite produce X-ray diffraction patterns
Quartz and cristobalite have two different crystal structures
The Si and O atoms are arranged differently, but both have long-range atomic order
The difference in their crystal structure is reflected in their different diffraction patterns
The amorphous glass does not have long-range atomic order and therefore produces
only broad scattering features
Diffraction occurs when light is scattered by a periodic array with
long-range order, producing constructive interference at
specific angles.

The electrons in each atom coherently scatter light.

We can regard each atom as a coherent point scatterer
The strength with which an atom scatters light is proportional to the number of
electrons around the atom.
The atoms in a crystal are arranged in a periodic array with long-range
order and thus can produce diffraction.
The wavelength of X rays are similar to the distance between atoms in a
crystal. Therefore, we use X-ray scattering to study atomic structure.
The scattering of X-rays from atoms produces a diffraction pattern, which
contains information about the atomic arrangement within the crystal

Amorphous materials like glass do not have a periodic array with long-range order, so
they do not produce a diffraction pattern. Their X-ray scattering pattern features broad,
poorly defined amorphous humps.
 Crystalline materials are characterized by the long-
range orderly periodic arrangements of atoms.
The unit cell is the basic repeating unit that defines the crystal structure.
The unit cell contains the symmetry elements required to uniquely define the
crystal structure.
The unit cell might contain more than one molecule:
for example, the quartz unit cell contains 3 complete molecules of SiO2.
The crystal system describes the shape of the unit cell Crystal System: hexagonal
The lattice parameters describe the size of the unit cell Lattice Parameters:
4.9134 x 4.9134 x 5.4052
(90 x 90 x 120)

The unit cell repeats in all dimensions to fill space and produce the
macroscopic grains or crystals of the material
 The diffraction pattern is a product of the unique
crystal structure of a material
Quartz
8000

6000
Quartz
4000

2000

0
Cristobalite
8000

6000

4000

2000 Cristobalite
0
20 30 40 50 60
Position [2Theta] (Copper (Cu))

The crystal structure describes the atomic arrangement of a material.

The crystal structure determines the position and intensity of the
diffraction peaks in an X-ray scattering pattern.
Interatomic distances determine the positions of the diffraction peaks.
The atom types and positions determine the diffraction peak intensities.
Diffraction peak widths and shapes are mostly a function of instrument
and microstructural parameters.
 Diffraction pattern calculations treat a crystal as a
Counts
collection of planes of atoms

112
Calculated_Profile_00-005-0490

20

110

102

200
111

201
10

003
0
35 40 45 50
Position [2Theta] (Copper (Cu))

Each diffraction peak is attributed to the scattering from a specific set of

Peak List

parallel planes of atoms.

Miller indices (hkl) are used to identify the different planes of atoms

Observed diffraction peaks can be related to planes of atoms to assist in

analyzing the atomic structure and microstructure of a sample
 A Brief Introduction to Miller Indices
The Miller indices (hkl) define the reciprocal
axial intercepts of a plane of atoms with the
unit cell
The (hkl) plane of atoms intercepts the unit cell

at , , and

The (220) plane drawn to the right intercepts the
unit cell at *a, *b, and does not intercept the
c-axis.
When a plane is parallel to an axis, it is assumed to
intercept at ; therefore its reciprocal is 0

The vector dhkl is drawn from the origin of the

unit cell to intersect the crystallographic plane
(hkl) at a 90 angle.
The direction of dhkl is the crystallographic
direction.
The crystallographic direction is expressed using
[] brackets, such as [220]
The diffraction peak position is a product of interplanar
spacing, as calculated by Braggs law

Braggs Law
2d hkl sin q

Braggs law relates the diffraction angle, 2, to dhkl

In most diffractometers, the X-ray wavelength l is fixed.
Consequently, a family of planes produces a diffraction peak only at a
specific angle 2.
dhkl is a geometric function of the size and shape of the unit cell
dhkl is the vector drawn from the origin to the plane (hkl) at a 90 angle.
dhkl, the vector magnitude, is the distance between parallel planes of
atoms in the family (hkl)
Therefore, we often consider that the position of the diffraction peaks are
determined by the distance between parallel planes of atoms.
The diffraction peak intensity is determined by the arrangement
of atoms in the entire crystal
2

Fhkl N j f j exp 2ihx j ky j lz j
m

j 1

The structure factor Fhkl sums the result of scattering from all of the
atoms in the unit cell to form a diffraction peak from the (hkl) planes
of atoms
The amplitude of scattered light is determined by:
where the atoms are on the atomic planes
this is expressed by the fractional coordinates xj yj zj
what atoms are on the atomic planes
the scattering factor fj quantifies the efficiency of X-ray scattering at any
angle by the group of electrons in each atom
The scattering factor is equal to the number of electrons around the atom at 0 ,
the drops off as increases
Nj is the fraction of every equivalent position that is occupied by atom j
 Braggs law provides a simplistic model to understand
what conditions are required for diffraction.
s
[hkl]

2d hkl sin q q q

dhkl dhkl
For parallel planes of atoms, with a space dhkl between the planes, constructive
interference only occurs when Braggs law is satisfied.
In our diffractometers, the X-ray wavelength is fixed.
A family of planes produces a diffraction peak only at a specific angle 2q.

Additionally, the plane normal [hkl] must be parallel to the diffraction vector s
Plane normal [hkl]: the direction perpendicular to a plane of atoms
Diffraction vector s: the vector that bisects the angle between the incident and
diffracted beam
 Many powder diffractometers use the Bragg-Brentano
parafocusing geometry.
Detector

s
X-ray
tube

w
2q

The incident angle, w, is defined between the X-ray source and the sample.
The diffraction angle, 2q, is defined between the incident beam and the detector.
The incident angle w is always of the detector angle 2q .
In a q:2q instrument (e.g. Rigaku H3R), the tube is fixed, the sample rotates at q /min and the
detector rotates at 2q /min.
In a q:q instrument (e.g. PANalytical XPert Pro), the sample is fixed and the tube rotates at a rate -q
/min and the detector rotates at a rate of q /min.
In the Bragg-Brentano geometry, the diffraction vector (s) is always normal to the
surface of the sample.
The diffraction vector is the vector that bisects the angle between the incident and scattered beam
A single crystal specimen in a Bragg-Brentano diffractometer would
produce only one family of peaks in the diffraction pattern.

[100] [110] [200]

s s s

2q

At 20.6 2q, Braggs law The (110) planes would diffract at 29.3 The (200) planes are parallel to the (100)
fulfilled for the (100) planes, 2q; however, they are not properly planes. Therefore, they also diffract for this
producing a diffraction peak. aligned to produce a diffraction peak crystal. Since d200 is d100, they appear at
(the perpendicular to those planes does 42 2q.
not bisect the incident and diffracted
beams). Only background is observed.
 A polycrystalline sample should contain thousands of crystallites.
Therefore, all possible diffraction peaks should be observed.

[110] [200]
[100]
s s
s
2q 2q 2q

For every set of planes, there will be a small percentage of crystallites that are properly
oriented to diffract (the plane perpendicular bisects the incident and diffracted beams).
Basic assumptions of powder diffraction are that for every set of planes there is an equal
number of crystallites that will diffract and that there is a statistically relevant number of
crystallites, not just one or two.
 Powder diffraction is more aptly named polycrystalline
diffraction
Samples can be powder, sintered pellets, coatings on substrates, engine blocks...
The ideal powder sample contains tens of thousands of randomly oriented
crystallites
Every diffraction peak is the product of X-rays scattering from an equal
number of crystallites
Only a small fraction of the crystallites in the specimen actually contribute to
the measured diffraction pattern
XRPD is a somewhat inefficient measurement technique
Irradiating a larger volume of material can help ensure that a statistically relevant
number of grains contribute to the diffraction pattern
Small sample quantities pose a problem because the sample size limits the
number of crystallites that can contribute to the measurement
 X-rays are scattered in a sphere around the sample
Each diffraction peak is actually a Debye diffraction cone produced by the tens of
thousands of randomly oriented crystallites in an ideal sample.
A cone along the sphere corresponds to a single Bragg angle 2theta
The linear diffraction pattern is formed as the detector scans along an arc that
intersects each Debye cone at a single point
Only a small fraction of scattered X-rays are observed by the detector.
 X-Ray Powder Diffraction (XRPD) is a somewhat
inefficient measurement technique

Only a small fraction of crystallites in the sample actually

contribute to the observed diffraction pattern
Other crystallites are not oriented properly to produce diffraction from
any planes of atoms
You can increase the number of crystallites that contribute to the
measured pattern by spinning the sample
Only a small fraction of the scattered X-rays are observed by
the detector
A point detector scanning in an arc around the sample only observes
one point on each Debye diffraction cone
You can increase the amount of scattered X-rays observed by using a
large area (2D) detector
 Diffraction patterns are collected as absolute intensity vs 2q vs,
but are best reported as relative intensity vs dhkl.

The peak position as 2q depends on instrumental characteristics such as

wavelength.
The peak position as dhkl is an intrinsic, instrument-independent, material
property.
Braggs Law is used to convert observed 2q positions to dhkl.

The absolute intensity, i.e. the number of X rays observed in a given peak,
can vary due to instrumental and experimental parameters.
The relative intensities of the diffraction peaks should be instrument
independent.
To calculate relative intensity, divide the absolute intensity of every peak by the
absolute intensity of the most intense peak, and then convert to a percentage. The
most intense peak of a phase is therefore always called the 100% peak.
Peak areas are much more reliable than peak heights as a measure of
intensity.
 Powder diffraction data consists of a record of photon
intensity versus detector angle 2q.
Diffraction data can be reduced to a list of peak positions and intensities
Each dhkl corresponds to a family of atomic planes {hkl}
individual planes cannot be resolved- this is a limitation of powder diffraction versus
single crystal diffraction
Raw Data Reduced dI list
Counts
Position Intensity DEMO08
hkl dhkl () Relative
3600
[2q] [cts] Intensity
25.2000 372.0000 (%)
25.2400 460.0000
25.2800 576.0000 1600
{012} 3.4935 49.8
25.3200 752.0000 {104} 2.5583 85.8
25.3600 1088.0000
25.4000 1488.0000
{110} 2.3852 36.1
400
25.4400 1892.0000
{006} 2.1701 1.9
25.4800 2104.0000
25.5200 1720.0000 {113} 2.0903 100.0
25.5600 1216.0000 0
25 30 35 40 45 {202} 1.9680 1.4
25.6000 732.0000 Position [2Theta] (Copper (Cu))

25.6400 456.0000
25.6800 380.0000
25.7200 328.0000
 Applications of XRPD

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 You can use XRD to determine
Phase Composition of a Sample
Quantitative Phase Analysis: determine the relative amounts of phases in a
mixture by referencing the relative peak intensities
Unit cell lattice parameters and Bravais lattice symmetry
Index peak positions
Lattice parameters can vary as a function of, and therefore give you
information about, alloying, doping, solid solutions, strains, etc.
Residual Strain (macrostrain)
Crystal Structure
By Rietveld refinement of the entire diffraction pattern
Epitaxy/Texture/Orientation
Crystallite Size and Microstrain
Indicated by peak broadening
Other defects (stacking faults, etc.) can be measured by analysis of peak
shapes and peak width
We have in-situ capabilities, too (evaluate all properties above as a
function of time, temperature, and gas environment)
 Phase Identification
The diffraction pattern for every phase is as unique as your fingerprint
Phases with the same chemical composition can have drastically different
diffraction patterns.
Use the position and relative intensity of a series of peaks to match
experimental data to the reference patterns in the database
The diffraction pattern of a mixture is a simple sum of
the scattering from each component phase
 Databases such as the Powder Diffraction File (PDF) contain dI
lists for thousands of crystalline phases.
The PDF contains over 300,000 diffraction patterns.
Modern computer programs can help you determine what phases are
present in your sample by quickly comparing your diffraction data to all of
the patterns in the database.
The PDF card for an entry contains a lot of useful information, including
literature references.
 Quantitative Phase Analysis

With high quality data, you can determine how

much of each phase is present 60

..
must meet the constant volume assumption (see

I(phase a)/I(phase b)
later slides)
50
The ratio of peak intensities varies linearly as a 40
function of weight fractions for any two phases
in a mixture 30

=K* 20

need to know the constant of proportionality 10

RIR method is fast and gives semi-quantitative
results 0
=
0 0.2 0.4 0.6 0.8 1

Whole pattern fitting/Rietveld refinement is a X(phase a)/X(phase b)

more accurate but more complicated analysis
 You cannot guess the relative amounts of phases based
only on the relative intensities of the diffraction peaks

The pattern shown above contains equal amounts of TiO2 and Al2O3
The TiO2 pattern is more intense because TiO2 diffracts X-rays more efficiently

With proper calibration, you can calculate the amount of each phase present in the sample
 Unit Cell Lattice Parameter Refinement

By accurately measuring peak positions over a long range of

2theta, you can determine the unit cell lattice parameters of
the phases in your sample
alloying, substitutional doping, temperature and pressure, etc can
create changes in lattice parameters that you may want to quantify
use many peaks over a long range of 2theta so that you can identify
and correct for systematic errors such as specimen displacement and
zero shift
measure peak positions with a peak search algorithm or profile fitting
profile fitting is more accurate but more time consuming
then numerically refine the lattice parameters
 Crystallite Size and Microstrain
Crystallites smaller than ~120nm create broadening of diffraction peaks
this peak broadening can be used to quantify the average crystallite size of nanoparticles
using the Scherrer equation
must know the contribution of peak width from the instrument by using a calibration curve
microstrain may also create peak broadening
analyzing the peak widths over a long range of 2theta using a Williamson-Hull plot can let
you separate microstrain and crystallite size
Careful calibration is required to calculate accurate crystallite sizes!
00-043-1002> Cerianite- - CeO2

K
B2q
Intensity (a.u.)

L cos q

23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
2q (deg.)
 Preferred Orientation (texture)

Preferred orientation of crystallites can create a systematic

variation in diffraction peak intensities
can qualitatively analyze using a 1D diffraction pattern by looking at
how observed peak intensities deviate systematically from the ideal
a pole figure maps the intensity of a single peak as a function of tilt
and rotation of the sample
this can be used to quantify the texture
10.0 (111) 00-004-0784> Gold - Au

8.0

(311)
Intensity(Counts)

6.0 (200)
(220)
4.0

2.0
(222)
(400)
3
x10
40 50 60 70 80 90 100
Two-Theta (deg)
 Non-ideal samples: Texture (i.e. preferred
crystallographic orientation)

The samples consists of tens of thousands of grains, but the

grains are not randomly oriented
Some phenomenon during crystallization and growth, processing, or
sample preparation have caused the grains to have preferred
crystallographic direction normal to the surface of the sample
350

300

250

Intensity(Counts)
200

150

100

50

0 (111)
(221) JCS#98> CaCO3 - Aragonite
(021) (012)
(102) (112) (220) (041) (132) (113)
(002) (121) (211) (040) (212) (222) (042)
25 30 35 40 45 50 55
Two-Theta (deg)

The preferred orientation creates a

systematic error in the observed
diffraction peak intensities.
 Overview of the Diffractometer

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 Essential Parts of the Diffractometer

X-ray Tube: the source of X Rays

Incident-beam optics: condition the X-ray beam before it hits
the sample
The goniometer: the platform that holds and moves the
sample, optics, detector, and/or tube
The sample & sample holder
Receiving-side optics: condition the X-ray beam after it has
encountered the sample
Detector: count the number of X Rays scattered by the sample
 X-radiation for diffraction measurements is produced
by a sealed tube or rotating anode.
H2O In

H2O Out
Sealed X-ray tubes tend to operate at 1.8
to 3 kW.
Rotating anode X-ray tubes produce
much more flux because they operate at
9 to 18 kW. Be
Cu ANODE
Be
window
A rotating anode spins the anode at 6000 window

rpm, helping to distribute heat over a e-

larger area and therefore allowing the XRAYS XRAYS
FILAMENT
tube to be run at higher power without (cathode)

melting the target. metal

Both sources generate X rays by striking

the anode target with an electron beam (vacuum) (vacuum)
glass

from a tungsten filament.

The target must be water cooled.
The target and filament must be
contained in a vacuum.

AC CURRENT
The wavelength of X rays is determined by the anode of
the X-ray source.
Electrons from the filament strike the target anode, producing characteristic
radiation via the photoelectric effect.
The anode material determines the wavelengths of characteristic radiation.
While we would prefer a monochromatic source, the X-ray beam actually
consists of several characteristic wavelengths of X rays.

K
L
M
 Spectral Contamination in Diffraction Patterns
Ka1 Ka1

Ka2

Ka2 Ka1

Ka2

W La1
Kb
The Ka1 & Ka2 doublet will almost always be present
Very expensive optics can remove the Ka2 line
Ka1 & Ka2 overlap heavily at low angles and are more separated
at high angles
W lines form as the tube ages: the W filament contaminates
the target anode and becomes a new X-ray source
W and Kb lines can be removed with optics
 Monochromators remove unwanted wavelengths of radiation
from the incident or diffracted X-ray beam.

Diffraction from a monochromator crystal can be used to select one

wavelength of radiation and provide energy discrimination.
Most powder diffractometer monochromators only remove K-beta,
W-contamination, and Brehmstralung radiation
Only HRXRD monochromators or specialized powder monochromators
remove K-alpha2 radiation as well.
A monochromator can be mounted between the tube and sample
(incident-beam) or between the sample and detector (diffracted-
beam)
An incident-beam monochromator only filters out unwanted wavelengths
of radiation from the X-ray source
A diffracted-beam monochromator will also remove fluoresced photons.
A monochromator may eliminate 99% of K-beta and similar unwanted
wavelengths of radiation.
A diffracted-beam monochromator will provide the best signal-to-noise
ratio, but data collection will take a longer time
 Beta filters can also be used to reduce the intensity of
K-beta and W wavelength radiation
A material with an absorption
edge between the K-alpha and
K-beta wavelengths can be
used as a beta filter Ni filter
This is often the element just

Suppression
below the target material on
the periodic table
For example, when using Cu
radiation
Cu K-alpha = 1.541
Cu K-beta= 1.387
The Ni absorption edge= 1.488
The Ni absorption of Cu radiation
is:

Cu Kb

Cu Ka
W La
50% of Cu K-alpha
99% of Cu K-beta Wavelength
 H He
Li Be
Fluorescence B C N O F Ne
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba L Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra A
Some atoms absorb incident X-rays and fluoresce them as X-rays of a different
wavelength
The absorption of X-rays decreases the diffracted signal
The fluoresced X-rays increase the background noise
The increased background noise from fluoresced X-rays can be removed by using:
a diffracted-beam monochromator
an energy sensitive detector
The diffracted beam signal can only be increased by using a different wavelength of
radiation
The most problematic materials are those two and three below the target material:
For Cu, the elements that fluoresce the most are Fe and Co
 The X-ray Shutter is the most important safety device
on a diffractometer
H2O In H2O Out

X-rays exit the tube through X-ray

transparent Be windows. XRAYS
Be
window

Cu ANODE
Be
window

X-Ray safety shutters contain the Primary

Shutter
e-

beam so that you may work in the Secondary

Shutter FILAMENT
(cathode)
XRAYS

diffractometer without being exposed Solenoid metal

to the X-rays. glass

(vacuum) (vacuum)

Being aware of the status of the

shutters is the most important factor
in working safely with X rays. AC CURRENT

SAFETY SHUTTERS
 The X-ray beam produced by the X-ray tube is divergent.
Incident-beam optics are used to limit this divergence

2d hkl sin q
X Rays from an X-ray tube are:
divergent
contain multiple characteristic wavelengths as well as Bremmsstrahlung radiation
neither of these conditions suit our ability to use X rays for analysis
the divergence means that instead of a single incident angle q, the sample is actually
illuminated by photons with a range of incident angles.
the spectral contamination means that the smaple does not diffract a single wavelength
of radiation, but rather several wavelengths of radiation.
Consequently, a single set of crystallographic planes will produce several diffraction peaks
instead of one diffraction peak.
Optics are used to:
limit divergence of the X-ray beam
refocus X rays into parallel paths
remove unwanted wavelengths
 Most of our powder diffractometers use the Bragg-
Brentano parafocusing geometry.
A point detector and sample are
moved so that the detector is always
at 2q and the sample surface is
always at q to the incident X-ray
beam.
In the parafocusing arrangement, the
incident- and diffracted-beam slits
move on a circle that is centered on
the sample. Divergent X rays from the
source hit the sample at different
points on its surface. During the
diffraction process the X rays are
refocused at the detector slit. F: the X-ray source
This arrangement provides the best DS: the incident-beam divergence-limiting slit
SS: the Soller slit assembly
combination of intensity, peak shape, S: the sample
and angular resolution for the widest RS: the diffracted-beam receiving slit
number of samples. C: the monochromator crystal
AS: the anti-scatter slit
 Divergence slits are used to limit the divergence of the
incident X-ray beam.
The slits block X-rays that have too great a
divergence.
The size of the divergence slit influences
peak intensity and peak shapes.
Narrow divergence slits:
reduce the intensity of the X-ray beam
reduce the length of the X-ray beam hitting
the sample
produce sharper peaks
the instrumental resolution is improved so
that closely spaced peaks can be resolved.
One by-product of the beam divergence is that the length of the beam
illuminating the sample becomes smaller as the incident angle
becomes larger.

The length of the incident beam

is determined by the divergence
slit, goniometer radius, and
incident angle.
This should be considered when 185mm Radius Goniometer, XRPD
choosing a divergence slits size: 40.00
if the divergence slit is too large,
the beam may be significantly 35.00
L
longer than your sample at low I
e 30.00
angles r
n
if the slit is too small, you may r
g 25.00
not get enough intensity from a 2DS
t
your sample at higher angles d
h 20.00
i
Appendix A in the SOP contains a a
guide to help you choose a slit 15.00
1DS
(

t
size. e
m
m 10.00
The width of the beam is d 0.5DS
)

constant: 12mm for the Rigaku 5.00

0.15DS
RU300.
0.00
0 20 40 60 80 100
2Theta (deg)
 Some systems use parallel-beam optics for a parallel
beam geometry

s Detector
X-ray
tube

w 2q

Parallel beam optics do NOT require that the incident angle w is always
of the detector angle 2q .
A coupled scan with parallel-beam optics will maintain the diffraction
vector in a constant relationship to the sample.
If w is always of 2q then the diffraction vector (s) is always normal to the surface of
the sample.
If w = 2q + , then s will be always tilted by away from the vertical position.
That direction will not change as long as both omega and 2theta change in a coupled
relationship so that w is always equal to 2q +
 Parallel beam optics allow for the possibility of grazing
incidence X-ray diffraction (GIXD)
Detector

s
X-ray
tube

w 2q

The incident angle, w, is set to a very shallow angle (between 0.2 and 5 deg).
This causes the X-rays to be focused in the surface of the sample, limiting the penetration depth of the X-
rays
Only the detector moves during data collection
The value is changing during the scan (where = *2q - w)
As a consequence, the diffraction vector (s) is changing its direction during the scan
Remember the diffraction only comes from crystallites in which dhkl is parallel to s
Therefore, the direction being probed in the sample changes
This is perfectly ok for ideal samples with randomly oriented grains; however, for samples with preferred
orientation this will cause a problem.
Regular GIXD will constrain the X-ray beam in the top few microns of the surface
IP-GIXD can be configued to constrain diffraction to the top 10-20 nm of the surface.
 Other optics:
limit divergence of the X-ray beam
Divergence limiting slits Parallel Plate Collimator & Soller
Parallel plate collimators Slits block divergent X-rays, but
do not restrict beam size like a
Soller slits divergent slit
refocus X rays into parallel paths
parallel-beam optics
parabolic mirrors and capillary lenses
focusing mirrors and lenses
remove unwanted wavelengths
monochromators
Kb filters

Gbel Mirrors and capillary lenses collect

a large portion of the divergent beam and
refocus it into a nearly parallel beam
 Detectors

point detectors
observe one point of space at a time
slow, but compatible with most/all optics
scintillation and gas proportional detectors count all photons, within an
energy window, that hit them
Si(Li) detectors can electronically analyze or filter wavelengths
position sensitive detectors
linear PSDs observe all photons scattered along a line from 2 to 10 long
2D area detectors observe all photons scattered along a conic section
gas proportional (gas on wire; microgap anodes)
limited resolution, issues with deadtime and saturation
CCD
limited in size, expensive
solid state real-time multiple semiconductor strips
high speed with high resolution, robust
 Area (2D) Diffraction allows us to image complete or
incomplete (spotty) Debye diffraction rings

the area observed by a linear detector the area observed by a linear detector

Polycrystalline thin film on a Mixture of fine and coarse grains

single crystal substrate in a metallic alloy
Conventional linear diffraction patterns would miss
information about single crystal or coarse grained materials
 Instruments in the X-Ray SEF
at the Center for Material Science and
Engineering at MIT

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 PANalytical XPert Pro Multipurpose Diffractometer
Prefix optics allow the configuration to be quickly changed to accommodate a
wide variety of data collection strategies.
This diffractometer can be used to collect XRPD, GIXD, XRR, residual stress, and
texture data.
A vertical-circle theta-theta goniometer is used so that the sample always lies flat
and does not move.
Sample sizes may be as large as 60mm diameter by 3-12mm thick, though a more typical
sample size is 10-20mm diameter.
Data collection modes can be changed between:
high-speed high-resolution divergent beam diffraction
Programmable divergence slits can maintain a constant irradiated area on sample surface
parallel beam diffraction using incident Gobel mirror and receiving-side parallel plate
collimator
eliminates errors due to irregular sample surfaces, sample displacement, and defocusing during
glancing angle measurements
A variety of sample stages include:
15 specimen automatic sample changer
open Eulerian cradle with automated z-translation as well as phi and psi rotation for
texture, reflectivity, and residual stress measurements
furnace for heating a sample to 1200C in air, vacuum, or controlled atmosphere
a cryostat for cooling a sample to 11 K in vacuum
 In-situ XRD can yield quantitative analysis to study reaction
pathways, rate constants, activation energy, and phase equilibria
2 1 k
1- e-k1t -
1 k1
N Al N 0 2
1- e-k 2t N 0
1- e-k 2t N 0Al
NaAlH 4 3 3 k - k 3 k 2 - k1 Na3 AlH 6
2 1
1 0 k1 -k1t
N Na3 AlH 6 N e - e-k 2t N 0 e-k 2t
3 NaAlH 4 k 2 - k1 Na3 AlH 6

N NaAlH 4 N 0 e-k1t
NaAlH 4 Na3AlH6 Al
NaCl

NaAlH4
 Rigaku SmartLab Multipurpose Diffractometer

High power 9kw source

Available diffracted-beam monochromator for improved signal-to-noise ratio
Easy to change between Bragg-Brentano (BB) and Parellel-Beam (PB)
geometry
Capable of GIXD and IP-GIXD measurements that are very useful for the analysis of thin
films
While capable of collecting data from powder samples, we mostly use this instrument
for thin film analysis and use the PANalytical XPert Pro for powder analysis
Able to measure pole figure of highly oriented thin films using in-plane pole
figures
Specialized optics for samples sealed in capillary tubes
Incident-beam monochromator for analysis of epitaxial and nearly-epitaxial
thin films
A furnace that can heat up to 1400 C configured for very fast data collection
In-situ battery cell to collect data while battery materials are discharged and
recharged.
 Rigaku Cr-Source Powder Diffractometer
Fast, precision XRPD using theta/2theta motion
High-power (10kW) rotating anode source supplies high X ray flux
Diffracted-beam monochromators provide very good signal-to-noise ratio
Horizontal-circle powder diffractometers
Horizontal circle facilitates precision movement of goniometer
Disadvantage: sample sits vertical, can easily fall out of sample holder

Sample size is generally 20mm x 10mm x 0.3mm, though we have a variety of

sample holders and mounting procedures to accommodate varied sample
geometries.
Special accessories include:
Inert atmosphere sample chamber for air/moisture sensitive samples
Zero background sample holders for high accuracy measurements from small quantities
of powder

Requires special considerations if your sample is a single crystal or a thin film on a

single crystal substrate
 Bruker D8 Diffractometer with GADDS

Ideal for texture (pole figure) and stress measurements, as well as traditional XRPD
and limited SCD and GIXD.
Two-dimensional area detector (GADDS) permits simultaneous collection of
diffraction data over a 2theta and chi (tilt) range as large as 30
Eularian cradle facilitates large range of tilts and rotations of the sample
A selectable collimator, which conditions the X-ray beam to a spot 0.5mm to
0.05mm diameter, combined with a motorized xy stage stage, permits
microdiffraction for multiple select areas of a sample or mapping across a samples
surface.
Samples can include thin films on wafers or dense pieces up to 6 in diameter
(maximum thickness of 3 mm), powders in top-loaded sample holders or in
capillaries, dense pieces up to 60mm x 50mm x 15mm (and maybe even larger).
Has an attachment for SAXS measurements.
 Bruker D8 Triple Axis Diffractometer

For GIXD and for analysis of rocking curves, lattice mismatch, and
reciprocal space maps of thin films and semiconductors
This instrument is typically used to measure the perfection or imperfection of
the crystal lattice in thin films (i.e. rocking curves), the misalignment between
film and substrate in epitaxial films, and reciprocal space mapping.
High precision Bruker D8 triple axis goniometer
Beam-conditioning analyzer crystals remove Ka2 radiation and provide
extremely high resolution.
Accessories include a furnace for heating a sample up to 900C in air,
vacuum, or inert gas (maximum sample size of 20mm x 20mm x 1mm)
 Bruker Small Angle Diffractometer

Used for SAXS

high-power rotating anode X-ray source
two-dimensional detector for real-time data collection
A long X-ray beam path allows this instrument to measure X-rays that are
only slightly scattered away from the incident beam. The two-dimensional
detector allows entire Debye rings to be collected and observed in real
time. The current beam path length of 60.4 cm allows the resolution of
crystallographic and structural features on a length scale from 1.8nm to
40nm (1.8nm is near the maximum resolvable length scale for XRPD in our
other systems).
A heater is available to heat the sample up to 200C.
 Back Reflection Laue Diffractometer

The sample is irradiated with white radiation for Laue

diffraction
Use either Polaroid film or a two-dimensional multiwire
detector to collect back-reflection Laue patterns
The 2D multiwire detector is not currently working
Determine the orientation of large single crystals and thin film
single crystal substrates
 Bruker Single Crystal Diffractometer

Designed primarily to determine the crystal structure of single

crystals
can also be used for determining crystal orientation
This diffractometer uses a two-dimensional CCD detector for
fast, high precision transmission diffraction through small
single crystals.
A variety of goniometer heads fit on the fix chi stage
A cryostat is available to cool samples down to 100 K in air,
which permits more precise determination of atom positions
in large organic crystals.
This system is currently located in Peter Mllers lab in the
Dept. of Chemistry, Bldg 2-325
 Sample Preparation

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 Important characteristics of samples for XRPD

a flat plate sample for XRPD should have a smooth flat surface
if the surface is not smooth and flat, X-ray absorption may reduce the
intensity of low angle peaks
parallel-beam optics can be used to analyze samples with odd shapes
or rough surfaces
Densely packed
Randomly oriented grains/crystallites
Grain size less than 10 microns
So that there are tens of thousands of grains irradiated by the X-ray
beam
Infinitely thick
homogeneous
 Preparing a powder specimen

An ideal powder sample should have many crystallites in random

orientations
the distribution of orientations should be smooth and equally distributed
amongst all orientations
Large crystallite sizes and non-random crystallite orientations both lead to
peak intensity variation
the measured diffraction pattern will not agree with that expected from an
ideal powder
the measured diffraction pattern will not agree with reference patterns in the
Powder Diffraction File (PDF) database
If the crystallites in a sample are very large, there will not be a smooth
distribution of crystal orientations. You will not get a powder average
diffraction pattern.
crystallites should be <10mm in size to get good powder statistics
 Preferred orientation

If the crystallites in a powder sample have plate or needle like

shapes it can be very difficult to get them to adopt random
orientations
top-loading, where you press the powder into a holder, can cause
problems with preferred orientation
in samples such as metal sheets or wires there is almost
always preferred orientation due to the manufacturing
process
for samples with systematic orientation, XRD can be used to
quantify the texture in the specimen
 Non-Ideal Samples: a spotty diffraction pattern

The sample does not contain tens of thousands of grains

The Debye diffraction cone is incomplete because there are not a
statistically relevant number of grains being irradiated
Counts
Mount3_07

3600

1600

400

0
20 30 40 50
Position [2Theta] (Copper (Cu))

The poor particle statistics cause random

error in the observed diffraction peak
intensities.
 Non-ideal samples: Texture (i.e. preferred
crystallographic orientation)

The samples consists of tens of thousands of grains, but the

grains are not randomly oriented
Some phenomenon during crystallization and growth, processing, or
sample preparation have caused the grains to have preferred
crystallographic direction normal to the surface of the sample
350

300

250

Intensity(Counts)
200

150

100

50

0 (111)
(221) JCS#98> CaCO3 - Aragonite
(021) (012)
(102) (112) (220) (041) (132) (113)
(002) (121) (211) (040) (212) (222) (042)
25 30 35 40 45 50 55
Two-Theta (deg)

The preferred orientation creates a

systematic error in the observed
diffraction peak intensities.
 Ways to prepare a powder sample

Top-loading a bulk powder into a well

deposit powder in a shallow well of a sample holder. Use a slightly
rough flat surface to press down on the powder, packing it into the
well.
using a slightly rough surface to pack the powder can help minimize
preferred orientation
mixing the sample with a filler such as flour or glass powder may also help
minimize preferred orientation
powder may need to be mixed with a binder to prevent it from falling out
of the sample holder
alternatively, the well of the sample holder can be coated with a thin layer of
vaseline
 Dispersing a thin powder layer on a smooth surface
a smooth surface such as a glass slide or a zero background holder (ZBH) may
be used to hold a thin layer of powder
glass will contribute an amorphous hump to the diffraction pattern
the ZBH avoids this problem by using an off-axis cut single crystal
dispersing the powder with alcohol onto the sample holder and then allowing
the alcohol to evaporate, often provides a nice, even coating of powder that
will adhere to the sample holder
powder may be gently sprinkled onto a piece of double-sided tape or a thin
layer of vaseline to adhere it to the sample holder
the double-sided tape will contribute to the diffraction pattern
these methods are necessary for mounting small amounts of powder
these methods help alleviate problems with preferred orientation
the constant volume assumption is not valid for this type of sample, and so
quantitative and Rietveld analysis will require extra work and may not be
possible
 Experimental Considerations

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 Varying Irradiated area of the sample

the area of your sample that is illuminated by the X-ray beam varies
as a function of:
incident angle of X rays
divergence angle of the X rays
at low angles, the beam might be wider than your sample
beam spill-off
This will cause problems if you sample is not homogeneous
185mm Radius Goniometer, XRPD
40.00

35.00
L
I
e 30.00
r
n
r
g 25.00
a 2DS
t
d
h 20.00
i
a
15.00
1DS
(

t
m
e
m 10.00
d 0.5DS
)

5.00
0.15DS
0.00
0 20 40 60 80 100
2Theta (deg)
 Penetration Depth of X-Rays

The depth of penetration of x-rays into a material depends on:

The mass absorption coefficient, /, for the composition
The density and packing factor of the sample
The incident angle omega
The wavelength of radiation used
3.45 sin
Depth of penetration, t, is =

Depth of penetration at 20 degrees omega
W
With 100% packing: 2.4 microns
With 60% packing (typical for powder): 4 microns
SiO2 (quartz)
With 100% packing: 85 microns
With 60% packing (typical for powder): 142 microns
 The constant volume assumption

In a polycrystalline sample of infinite thickness, the change in the

irradiated area as the incident angle varies is compensated for by
the change in the penetration depth
These two factors result in a constant irradiated volume
(as area decreases, depth increases; and vice versa)
This assumption is important for any XRPD analysis which relies on
quantifying peak intensities:
Matching intensities to those in the PDF reference database
Crystal structure refinements
Quantitative phase analysis
This assumption is not necessarily valid for thin films or small
quantities of sample on a zero background holder (ZBH)
 40
X-Ray Beam Length
There are ways to control the irradiated 30 Fixed
area of the sample to accommodate thin 20
Variable
GIXD
films and/or non-homogeneous samples 10

Fixed divergence slit 0

5 15 25 35 45 55 65
The divergence aperture is fixed during the scan 1.5
Beam length and penetration depth both change X-Ray Penetration Depth
Provides a constant irradiated volume for 1.0
infinitely thick, homogeneous samples
Variable divergence slit 0.5

The divergence aperture changes during the scan

This preserves a constant irradiated length 0.0
5 15 25 35 45 55 65
Beam length is constant but the penetration 8
depth changes Irradiated Volume
(assuming infinitely thick sample)
The irradiated volume increases for thick 6

specimens but is constant for thin specimens 4

Grazing incidence XRD (GIXD)
2
The incident angle is fixed during the scan
Only the detector moves during the measurement 0
Beam length and penetration depth are fixed 8
5 15 25 35 45 55 65

Often the best option for inhomogeneous Irradiated Volume

samples 6 (assuming thin sample)
By fixing omega at a shallow angle, X-rays are 4
focused in the surface of the sample
Requires parallel beam optics 2

0
5 15 25 35 45 55 65
 Many sources of error are associated with the focusing
circle of the Bragg-Brentano parafocusing geometry

The Bragg-Brentano parafocusing

geometry is used so that the
detector divergent X-ray beam reconverges
tube
Receiving at the focal point of the detector.
Slits This produces a sharp, well-
defined diffraction peak in the
data.
If the source, detector, and sample
are not all on the focusing circle,
sample errors will appear in the data.
The use of parallel-beam optics
eliminates all sources of error
associated with the focusing circle.
 Sample Displacement Error
When the sample is not on the focusing
circle, the X-ray beam does not converge
detector at the correct position for the detector.
tube The observed peak position is incorrect.
Receiving
Slits This is the greatest source of error in
most data
This is a systematic error:
2s cos q
2q - (in radians )
R
s is the amount of displacement, R is the
goniometer radius.
at 28.4 2theta, s=0.006 will result in a
sample peak shift of 0.08
Ways to compensate for sample displacement:
This is most commonly analyzed and compensated for using data analysis algorithms
For sample ID, simply remember that your peak positions may be shifted a little bit
Historically, the internal calibration standard was required for publication quality data
The computer algorithms for calculating the displacement error are now much better
Can be minimized by using a zero background sample holder
Can be eliminated by using parallel-beam optics
 Sample Transparency Error
X Rays penetrate into your sample
detector depth of penetration depends on:
tube
Receiving the mass absorption coefficient of
your sample
Slits
the incident angle of the X-ray beam
This produces errors because not all
X rays are diffracting from the same
location in your sample
Produces peak position errors and
peak asymmetry
sample Greatest for organic and low
absorbing (low atomic number)
samples
Can be eliminated by using parallel-
beam optics
Can be reduced by using a thin
sample
 Other sources of error
Flat specimen error
The entire surface of a flat specimen
detector cannot lie on the focusing circle
tube
Receiving Creates asymmetric broadening toward
Slits low 2theta angles
Reduced by using small divergence slits,
which produce a shorter beam
For this reason, if you need to increase
intensity it is better to make the beam
wider rather than longer.
eliminated by parallel-beam optics

sample
Poor counting statistics
The sample is not made up of thousands
of randomly oriented crystallites, as
assumed by most analysis techniques
The sample might have large grain sizes
Produces random peak intensities and/or
spotty diffraction peaks

A good reference for sources of error in diffraction data is available at http://www.gly.uga.edu/schroeder/geol6550/XRD.html

 Axial divergence

Axial divergence
Due to divergence of the X-ray beam in plane with the sample
creates asymmetric broadening of the peak toward low 2theta angles
Creates peak shift: negative below 90 2theta and positive above 90
Reduced by Soller slits and/or capillary lenses

Counts
0.04rad Soller Slits
0.04rad incident Soller slit and 0.02rad detector Soller Slit
0.02rad Soller Slits
60000

40000

20000

3 4 5 6
Position [2Theta] (Copper (Cu))
 End of presentation: other slides are old or extra

Scott A. Speakman, Ph.D. http://prism.mit.edu/xray

 Techniques in the XRD SEF

X-ray Powder Diffraction (XRPD)

Single Crystal Diffraction (SCD)
Back-reflection Laue Diffraction (no acronym)
Grazing Incidence Angle Diffraction (GIXD)
X-ray Reflectivity (XRR)
Small Angle X-ray Scattering (SAXS)
 X-Ray Powder Diffraction (XRPD)

More appropriately called polycrystalline X-ray diffraction, because it can

also be used for sintered samples, metal foils, coatings and films, finished
parts, etc.
Used to determine:
phase composition (commonly called phase ID)- what phases are present?
quantitative phase analysis- how much of each phase is present?
unit cell lattice parameters
crystal structure
average crystallite size of nanocrystalline samples
crystallite microstrain
texture
residual stress (really residual strain)
in-situ diffraction (from 11 K to 1200C in air, vacuum, or inert gas)
 Grazing Incident Angle Diffraction (GIXD)

also called Glancing Angle X-Ray Diffaction

The incident angle is fixed at a very small angle (<5) so that X-rays are
focused in only the top-most surface of the sample.
GIXD can perform many of analyses possible with XRPD with the added
ability to resolve information as a function of depth (depth-profiling) by
collecting successive diffraction patterns with varying incident angles
orientation of thin film with respect to substrate
lattice mismatch between film and substrate
epitaxy/texture
macro- and microstrains
reciprocal space map
 X-Ray Reflectivity (XRR)

A glancing, but varying, incident

angle, combined with a matching
detector angle collects the X rays
reflected from the samples
surface
Interference fringes in the
reflected signal can be used to
determine:
thickness of thin film layers
density and composition of thin
film layers
roughness of films and interfaces
 Back Reflection Laue

Used to determine crystal orientation

The beam is illuminated with white radiation
Use filters to remove the characteristic radiation wavelengths from the
X-ray source
The Bremmsstrahlung radiation is left
Weak radiation spread over a range of wavelengths
The single crystal sample diffracts according to Braggs Law
Instead of scanning the angle theta to make multiple crystallographic
planes diffract, we are effectively scanning the wavelength
Different planes diffract different wavelengths in the X-ray beam,
producing a series of diffraction spots
 Small Angle X-ray Scattering (SAXS)

Highly collimated beam, combined with a long distance between the

sample and the detector, allow sensitive measurements of the X-rays that
are just barely scattered by the sample (scattering angle <6)
The length scale of d () is inversely proportional to the scattering angle:
therefore, small angles represented larger features in the samples
Can resolve features of a size as large as 200 nm
Resolve microstructural features, as well as crystallographic
Used to determine:
crystallinity of polymers, organic molecules (proteins, etc.) in solution,
structural information on the nanometer to submicrometer length scale
ordering on the meso- and nano- length scales of self-assembled molecules
and/or pores
dispersion of crystallites in a matrix
 Single Crystal Diffraction (SCD)

Used to determine:
crystal structure
orientation
degree of crystalline perfection/imperfections (twinning, mosaicity,
etc.)
Sample is illuminated with monochromatic radiation
The sample axis, phi, and the goniometer axes omega and 2theta are
rotated to capture diffraction spots from at least one hemisphere
Easier to index and solve the crystal structure because it diffraction
peak is uniquely resolved
 Instruments in the XRD SEF

Rigaku RU300 Powder Diffractometers

Bruker D8 with GADDS
Bede D3
PANalytical XPert Pro
Back-reflection Laue (polaroid)
SAXS
Bruker Smart APEX*
 Available Software

PANalytical HighScore Plus

Phase identification
Profile fitting or whole pattern fitting for
unit cell refinement
nanocrystallite size and strain
quantitative phase analysis
indexing
Rietveld refinement of crystal structures
cluster analysis
 Software
MDI Jade
phase ID
indexing and unit cell refinement
RIR quantitative phase analysis
residual stress
nanocrystallite size and strain
calculated diffraction patterns
 Available Software

PANalytical Stress- residual stress analysis

PANalytical Texture- pole figure mapping of texture
PANalytical Reflectivity- reflectivity from multilayer thin films

Bruker Multex Area- pole figure mapping of texture

Bruker Leptos for epitaxial thin film and XRR analysis.
 Available Free Software

GSAS- Rietveld refinement of crystal structures

FullProf- Rietveld refinement of crystal structures
Rietan- Rietveld refinement of crystal structures

PowderCell- crystal visualization and simulated diffraction

patterns
JCryst- stereograms
 Website

http://prism.mit.edu/xray
reserving instrument time
instrument status
training schedules
links to resources
SOPs
tutorials
 Single Crystal Diffractometers

The design challenge for single crystal diffractometers: how to

determine the position and intensity of these diffraction spots
Reflection vs transmission
Transmission: small samples & organic crystals
Reflection: large samples, epitaxial thin films
Laue vs. SCD
Laue: stationary sample bathed with white radiation (i.e. many
wavelengths)
SCD: monochromatic radiation hits a sample as it is rotated and
manipulated to bring different planes into diffracting condition
 Diffraction from a Single Crystal
X Rays striking a single crystal will produce diffraction spots in
a sphere around the crystal.
Each diffraction spot corresponds to a single (hkl)
The distribution of diffraction spots is dependent on the crystal
structure and the orientation of the crystal in the diffractometer
The diffracting condition is best illustrated with the Ewald sphere in
reciprocal space

*Diffraction spots are sometimes called reflections. Three cheers for sloppy terminology!
 Equivalent positions are points in the unit cell that are
identical to other points in the unit cell

The symmetry elements in the unit cell produce equivalent

positions
Even though there are 3 Si atoms in the unit cell of quartz, we
only have to define the position of one Si atom
The other Si atoms are on equivalent positions that are defined by the
symmetry elements of the space group

Quartz
Crystal System: hexagonal
Bravais Lattice: primitive
Space Group: P3221

Atom Positions:
x y z
Si 0.47 0 0.667
O 0.414 0.268 0.786
 Wavelengths for X-Radiation are Sometimes Updated
Copper Bearden Holzer et al. Cobalt Bearden Holzer et al.
Anodes (1967) (1997) Anodes (1967) (1997)
Cu Ka1 1.54056 1.540598 Co Ka1 1.788965 1.789010
Cu Ka2 1.54439 1.544426 Co Ka2 1.792850 1.792900
Cu Kb 1.39220 1.392250 Co Kb 1.62079 1.620830

Molybdenum Chromium
Anodes Anodes
Mo Ka1 0.709300 0.709319 Cr Ka1 2.28970 2.289760
Mo Ka2 0.713590 0.713609 Cr Ka2 2.293606 2.293663
Mo Kb 0.632288 0.632305 Cr Kb 2.08487 2.084920

Often quoted values from Cullity (1956) and Bearden, Rev. Mod. Phys. 39 (1967) are
incorrect.
Values from Bearden (1967) are reprinted in international Tables for X-Ray Crystallography and
most XRD textbooks.
Most recent values are from Hlzer et al. Phys. Rev. A 56 (1997)
Has your XRD analysis software been updated?
 Crystal structures focus on symmetry elements to
define the atomic arrangement

Symmetry in crystal structures is a product of energy

minimization in the atomic arrangement
Symmetry in the crystal structure often produces symmetry in
material properties and behavior
Quartz Primitive Bravais Lattice
Crystal System: hexagonal 32 screw axis
Bravais Lattice: primitive 2-fold rotational axis
Space Group: P3221
Lattice Parameters: 4.9134 x 4.9134 x 5.4052
(90 x 90 x 120)
Atom Positions:
x y z
Si 0.47 0 0.667
O 0.414 0.268 0.786
Symmetry elements are used to define seven different
crystal systems
Crystal System Bravais Symmetry Axis System
Lattices
Cubic P, I, F m3m a=b=c, ===90
Tetragonal P, I 4/mmm a=bc, ===90
Hexagonal P, R 6/mmm a=bc, ==90 =120
Rhombohedral* R 3m a=b=c, ==90
Orthorhombic P, C, I, F mmm abc, ===90
Monoclinic P, C 2/m abc, ==90 90
Triclinic P 1 abc, 90

Quartz
Crystal System: hexagonal
Bravais Lattice: primitive
Space Group: P3221
Lattice Parameters: 4.9134 x 4.9134 x 5.4052
(90 x 90 x 120)
 Useful things to remember about Miller indices

(hkl) is parallel to (n*h n*k n*l)

For example, (110) // (220) // (330) // (440)
Planes are orthogonal if (hkl) (hkl) = 0
Some planes may be equivalent because of
symmetry

101
In a cubic crystal, (100) (010) and (001) are

100
002

110

103
equivalent

112
102

004
202
They are the family of planes {100}
[h00] is parallel to the a-axis, [0k0] // b-axis, 0

[00l] // c-axis 30 40 50

Position [2Theta] (Copper (Cu))

60 70

In this figure, the (002) and (004) peaks

When analyzing XRD data, we look for (which are parallel to each other) are
much more intense than expected this
trends corresponding to directionality in provides information about the
the crystal structure by analyzing the Miller microstructure of the sample
indices of diffraction peaks.
 Parallel planes of atoms intersecting the unit cell define
directions and distances in the crystal.
The (200) planes The (220) planes
of atoms in NaCl of atoms in NaCl

The Miller indices (hkl) define the reciprocal of the axial intercepts
The crystallographic direction, [hkl], is the vector normal to (hkl)
dhkl is the vector extending from the origin to the plane (hkl) and is normal to
(hkl)
The vector dhkl is used in Braggs law to determine where diffraction peaks will
be observed
 A given (hkl) refers to a family of atomic planes, not a
single atomic plane
The (100) plane includes two
The Miller indices are determined faces of the cubic unit cell.
by using the plane of atoms that is These are produced by drawing
closest to the origin without the first plane (shaded orange)
at the (1,0,0) intercept, and
passing through it. then translating it by [-100].
The other members of the family
of atoms are determined by The (200) plane also includes
translating the (hkl) plane of two faces of the cubic unit cell.
These are produced by drawing
atoms by [hkl] the first plane (shaded orange)
A family of planes will always have at the (, 0, 0) intercept, and
then translating it by [, 0, 0].
one member that passes through
the origin The (400) plane includes
members of the (100) and (200)
Some planes of atoms may belong families, as well as the planes at
to more than one family (as the (, 0, 0) and (, 0, 0)
intercepts. These are produced
illustrated to the right) by drawing the first plane
(shaded orange) at the (, 0, 0)
intercept, and then translating
it by [n*, 0, 0].