X-ray Diffraction

The Basics

Judit Lisoni
 Goals
This introduction should provide a first introduction to x-ray diffraction based techniques

It should provide the necessary background to interpret most experimental results.

Practical examples will be discussed in Part 2 (2nd day).

Questions to be answered: What is x-ray diffraction and how it is used in crystallography,

what are the physical principles determining x-ray diffraction patterns, what can I learn from
x-ray diffraction pattern (peak position, intensity, width). Grazing incidence will not be
discussed.

The tutorial cannot not provide a full mathematical overview of all analysis and modeling
techniques. References to textbooks are given at the end.

The presentation focuses on general aspects of techniques commonly used in most

laboratories. It is not meant to give a complete overview of all possible x-ray based
measurement techniques.

We will mainly discussed the interpretation of the X-ray patterns based on Bragg´s law and
not from the reciprocal lattice viewpoint. This is motivated by the equipment available in
Chile.
 Crystallography

X-ray crystallography is
the science of
determining the
arrangement of atoms
within a crystal from the
manner in which a beam
of X-rays is scattered
from the electrons within
the crystal
tetrahedral arrangement of http://www.makehumans.com/htmx/X-
ray_crystallography.php
hydrogen bonds about each
water molecule
 Bravais lattice and crystals
 Set of points generated by a
set of discrete translation
operation
 Basis: one or more atoms

crystal = Bravais lattice + basis

Crystal looks the same when viewed from any

of the lattice points
Auguste Bravais (1811-1863) was the first to count the categories correctly.

CaF2, fluorite
Smithsonian Museum of Natural
History
 Bravais lattices

http://encyclopedia2.thefreedictionary.com/Bravais+lattices
Miller indices
planes in 3D: x/a+y/b+z/c=1

Reciprocal of the fractional

intercepts which the plane
makes with the
crystallographic axis
 axis: a,b,c

 Miller indices: h,k,l

 plane actually intercepts at

Elements of X-ray Diffraction
B.D. Cullity, pp 38-39 a/h b/k c/l
Axial length, Å 4 8 3
Intercept length, Å 2 6 3
Fractional intercept ½ ¾ 1
Take the reciprocals 2 4/3 1
Miller indices by reducing lo lowest term 6 4 3
 Miller indices
Some examples

 Miller index 0: plane parallel

to the axis
 No infinite intercepts
 Formulas involving Miller
indices are very similar to
related formulas from
analytical geometry

Notation conventions
Overbar represents negative
number (hexagonal systems)
(hkl) : plane
{hkl} : set of equivalent planes or
family
Cu(111), STM image [hkl] : direction (perp. to plane)
IBM web page <hkl> : set of equiv. directions
 Lattice geometry
d↔(h,k,l)
 Cubic 1 = h2+k2+k2
d2 a2

 Tetragonal 1 = h2+k2 + l2
d2 a2 c2

 Hexagonal 1 = 4(h2+hk +k2) + l2

d2 3a2 c2

 Rombohedral… and so forth

1 = (h2+k2+l2)sin2a +2(hk+kl hl)(cos2a-cosa)
d2 a2(1-3cos2a+2cos3a)

This was well known much before that X-rays were

discovered!!!!
 Hexagonal systems: Bravais indices

Hexagonal systems are often described using Bravais

indices: (hklm)
Advantage: sets of planes can be obtained by permutation,
as for e.g. cubic systems using Miller indices

ghklm = ha1 + ka2 + la3 + mc

since a1, a2, and a3 not linearly

independent:

Convention: h + k + l = 0

Miller indices can also be used

 X-ray: the discovery
Dr. A. Von Kolliker's hand
X-rays are discovered in 1895 by
W.C. Röntgen, a German physicist

If one holds the hand between

the discharge and the screen
one sees the darker shadows of
the bones within the much
fainter shadow picture of the
hand itself
Röntgen observations
 What are x-rays
X-rays are light = photons

Wavelength range:
0.1 Å ― 10 nm

Energy range:
100 eV ― 100 keV

Soft x-rays : 100 eV – a few keV

Hard x-rays: a few keV – 100
keV

Cu Kα: 1.54 Å — 8.03 keV

 X-ray generation: laboratory systems

X-ray generation by electron beam excitation

(similar to EDX)

X-ray emission characteristic of energy levels in

tube material

log Iα1/Iα2 = 2
from selection rules

• Almost all x-ray tubes today use a Cu anode

• X-ray lab in Physics dept FCFM use sealed Cu tubes without rotation (1.54 Å -
8.03 keV)
• Higher intensity possible by rotating Cu anode to avoid anode melting
 Source
X-rays source
Spectrum Ni filter

Cu Ka Cu K

• All difractometers in FCFM use sealed Cu tubes

without rotation (1.54 Å — 8.05 keV)
40 kV •The presence of Cu Ka and  (1.39 Å-8.9 keV)
(4x104 eV) filament lines complicates the diffraction patterns.
•Ni filter are used to select the Cu Ka lines
 X-ray generation: synchrotron radiation
Accelerated electrons (e.g. on a curved path) emit x-rays

Bending magnet

• Synchrotrons are very intense sources of “white light” with a very large energy range
(IR to hard x-rays)
• Monochromators can provide wavelength-tunable monochromatic light
 Interaction of x-rays with matter
Possible Interactions:

• Elastic scattering: no energy change of x-ray photon during

interaction with matter
• x-ray diffraction and x-ray reflectivity
• Inelastic scattering: energy loss of x-ray photon during
interaction
• With ionization: Compton scattering
• Without ionization: Raman scattering

• Absorption
• Subsequent x-ray emission: x-ray fluorescence
• Subsequent electron emission: XPS, Auger spectroscopy
• Absorption measurements: XAS, XAFS (EXAFS, XANES)

In this tutorial, only elastic scattering will be discussed

However, absorption can not always be neglected
 x-ray absorption
• For x-ray diffraction, the information depth is limited by x-
ray absorption
• Typical length scales vary widely with x-ray energy
(wavelength) and material properties (composition, density)
• For Cu Kα radiation (8030 eV, 1.54 Å) > 1 mm
• Air ~ 1 m
• Graphite = 1 mm
• SiO2 (Silica) = 126 µm
• Si = 67 µm
• Cu = 22 µm
Higher atomic numbers
• Al = 73 µm absorb more efficiently
• Pb = 3.9 µm
• Ta = 3.7 µm Lower energy (softer) x-rays
• Pt = 2.4 µm are more efficiently absorbed

X-rays probe mostly “bulk” properties

 Diffraction from a crystal
Laue’s conditions

1912 X-ray diffractions by crystal

phenomenon discovered, M.Von
Laue, initial problem: X-ray, wave
or particle?

Physics Nobel prize 1914

Von Laue was studying diffraction of light through narrow slits: could be X-rays
diffracted if the slit is small enough? If the X-rays were a wave then the atoms in a
crystals should cause them to diffract
 Diffraction from a crystal
Laue’s conditions: reciprocal lattice
reflected
1D 2D

incident

α(cosμ-cosν)=nλ 3D
n: interger
Δk=k-k0
Elastic
scattering:
IkI=Ik0I
 Laue Conditions
cones in 3D

a∙∆k = 2πh b∙∆k = 2πk c∙∆k = 2πl

∆k=Ghkl → giaj=2πδij
 Each of the above describes a cone in reciprocal
space about the lattice vectors a, b, and c.
– h,k,l are integers
 Reciprocal lattice condition
 Ghkl=2π/dhkl
 When a reciprocal lattice point intersects this cone
the diffraction condition is met: Ewald sphere.
 Bragg’s Law
William Lawrence Bragg 1913

nl = 2 d sin q

Bragg's interpretation of Laue's condition: the constructive interference of X-

rays are equivalent to that of a simple plane reflecting the X-ray radiation with
the condition that the plane could be described by a triplet of Miller indices

The distance travelled depends on the separation of the layers and the angle
at which the X-ray entered the material. For this wave to be in phase with the
wave which reflected from the surface it needs to have travelled a whole
number of wavelengths while inside the material.
Intensity: atomic form and structure factors
Intensity: scattering from the constituents of the
lattice – structure factor
 I a I0*re, re in the plane
– Ne per atom ~Z
– I might be calculated
 Atomic Form Factors: scattering by individual
atoms tabulated in international tables
 Interference effects within a unit cell, i.e.
selection rules (atoms positions)
 Number of equivalent planes: large spacing→low
(hkl)→higher ρe

“Extrinsic effects”
 Footprint effects: the diffraction volume of thin
films depends on the incidence angle.
 Bulk samples: absorption can also play a role
 Thermal vibrations (Debye-Waller factor)
reduce peak intensities
 Sometimes dynamic effects beyond the
kinematical approximation
 Atomic form factors and selection rules
The Bragg equation describes periodic arrangements of building blocks
The Bragg peak intensity is modified by the diffraction from a single
building block

Scattered intensity depends on atomic form factors:

(heavier atoms scatter more than light ones)
F(Q) decreases with scattering angle; same is true for XRD pattern

These scattering amplitudes have to be summed up coherently within a

unit cell. For example for face-centered cubic (fcc) with identical atoms:

Finite intensity, “allowed”

Zero intensity, “forbidden”

Peaks can be “allowed” or “forbidden”, depending on symmetry

 Selection rules I
Example Allowed/strong Forbidden/weak
Bravais lattice
compounds reflections reflections
Simple cubic Po, KCl Any h, k, l None

Body-centered
Fe, W, Ta, Cr h + k + l even h + k + l odd
cubic

Face-centered Cu, Al, Ni, NaCl, h, k, l all odd or h, k, l mixed odd

cubic LiH, PbS all even and even

ZnSe, CuCl, all: odd, or even above, or even

Diamond F.C.C.
AgI, CuF, Si, Ge & h+k+l = 4n & h+k+l ≠ 4n

l even, h + 2k ≠ h + 2k = 3n for
Triangular lattice Ti, Zr, Cd, Be
3n odd l
 Selection rules II
Including atomic factors f, f1, f2…
Reflection fcc Al Diamond Si Sphalerite GaAs
cubic
001 0 0 0 0 0 0
002 4f 0.41 0 0 4 (f1 - f2) 0.05
004 4f 0.28 8f 0.39 4 (f1 + f2) 1.02
111 4f 0.43 5.66 f 0.38 4 f12 + f 22 0.99
222 4f 0.31 0 0 4 (f1 - f2) 0.04
333 4f 0.21 5.66 f 0.24 4 f12 + f 22 0.61
011 0 0 0 0 0 0
022 4f 0.35 8f 0.45 4 (f1 + f2) 1.20
044 4f n.a. 8f 0.31 4 (f1 + f2) 0.80
112 0 0 0 0 0 0
224 4f 0.23 8f 0.35 4 (f1 + f2) 0.90
113 4f 0.32 5.66 f 0.30 4 f12 + f 22 0.79
115 4f 0.21 5.66 f 0.24 4 f12 + f 22 0.61

Atomic factors are tabulated, listed as a http://depts.washington.edu/chemcrs/bulkdisk/chem484A_spr06/

function of sinq/l (to be independent of handout_Diffraction.pdf
the wavelength)
Summary: Bragg peak position and intensity
• Positions of the Bragg peaks are characteristic of the Bravais lattice (the
“3D periodicity” of the lattice). Their measurements can be used to
determine
• lattice parameters (sometimes only up to an integer factor)
• lattice angles
It is generally not sufficient to fully determine the crystal structure
without further knowledge.

• The intensity of the Bragg peaks is characteristic of the scattering within

a unit cell. It can in principle be used to fully determine the crystal
structure (Rietveld refinement).

• For XRD on thin films, it is not obvious to obtain theoretical peak

intensity ratios. First, the diffracting volume is not independent of the
incidence angle, which reduces the peak intensity at higher angles.
Second, at room temperature, thermal vibrations reduce the peak
intensity (Debye-Waller factor). The Debye-Waller factor has a (small)
but generally unknown angle (peak) dependence. Finally, texture may
alter the peak intensity significantly.
 Data base
JCPDS or PDF files
46-1045 JCPDS-ICDD Copyright 1997 QM= *

SiO2

Silicon Oxide Quartz, syn

-----------------------------------------------------------------------------
Strong lines: 3.34/X 4.26/2 1.82/1 2.46/1 1.54/1 2.28/1 1.38/1 2.13/1
Rad: CuKa1 Lambda: 1.540598 Filter: Ge Mono.
----------------------------------------------------------------------------------------------
d-sp: Diff.
58 reflections in pattern. Page 1 of 2. Radiation= 1.78898
Cutoff: Int: Diffractometer I/Icor: 3.41
-------------------------------------------------------------------------
Ref: Kern, A., Eysel, W., Mineralogisch-Petrograph. Inst.,
| 2-theta | Int. | hkl | 2-theta | Int. | hkl |
Univ. Heidelberg, Germany, ICDD Grant-in-Aid, (1993)
|---------+-----+----------------------+---------+-----+------------- |
-----------------------------------------------------------------------------
| 24.271 | 16 | 1 0 0 | 80.661 | 6 | 2 1 2 |
Sys: Hexagonal S.G.: P3221 (154)
| 31.035 | 100 | 1 0 1 | 81.164 | 7 | 2 0 3 |
a: 4.91344(4) b: c: 5.40524(8) A: C:
| 42.701 | 9 | 1 1 0 | 81.386 | 5 | 3 0 1 |
1.1001
| 46.166 | 8 | 1 0 2 | 87.980 | 2 | 1 0 4 |
A: B: C: Z: 3 mp:
| 47.159 | 4 | 1 1 1 | 90.833 | 3 | 3 0 2 |
Ref: Ibid.
| | | | | | |
Dx: 2.65 Dm: 2.66 SS/FOM: F(30)=538.7(.0018,31)
| 49.720 | 6 | 2 0 0 | 93.477 | 1 | 2 2 0 |
-----------------------------------------------------------------------------
| 53.717 | 4 | 2 0 1 | 96.410 | 2 | 2 1 3 |
ea: nwB: 1.544 ey: 1.553 Sign: + 2V:
| 58.947 | 13 | 1 1 2 | 96.624 | <1 | 2 2 1 |
Ref: Swanson, Fuyat, Natl. Bur. Stand. (U.S.), Circ. 539, 3
| 59.533 | <1 | 0 0 3 | 98.135 | 2 | 1 1 4 |
24 (1954)
| 64.698 | 4 | 2 0 2 | 98.561 | 2 | 3 1 0 |
-----------------------------------------------------------------------------
| | | | | | |
Color: White
| 65.246 | 2 | 1 0 3 | 101.754 | 1 | 3 1 1 |
Integrated intensities. Pattern taken at 23(1) C. Low
| 67.583 | <1 | 2 1 0 | 103.286 | <1 | 2 0 4 |
temperature quartz. 2theta determination based on profile
| 70.939 | 9 | 2 1 1 | 106.757 | <1 | 3 0 3 |
fit method. O2Si type. Sincosite group. Silicon used as
| 76.000 | 2 | 1 1 3 | 111.585 | 2 | 3 1 2 |
internal standard. PSC: hP9. To replace 33-1161.
| 78.194 | <1 | 3 0 0 | 114.459 | <1 | 4 0 0 |
Structure reference: Z. Kristallogr., 198 177 (1992). Mwt:
----------------------------------------------------------------------------
60.08. Volume[CD]: 113.01.3.01.
 Summary of Bragg & Laue

 When a diffraction
condition is met there can nλ
d=
be a reflected X-ray 2sin θ
– Extra atoms in the basis can
suppress reflections
 Three variables λ, θ, and d
– λ is known
– θ is measured in the experiment
(2θ)
– d is calculated
a=d√(h2+k2+l2)
 From the planes (hkl)
– a is calculated
 θ - 2θ Scan
Powder diffraction

The θ - 2θ scan maintains these angles with the

sample, detector and X-ray source
Normal to surface
Ghk
l

2q

XPertMPD1

Only planes of atoms that share this normal will be seen in the θ - 2θ Scan
 More general: the goniometer and its angles

In many x-ray diffractometers, the x-ray source is fixed

and the detector and the sample rotate…
but in FCFM the sample is fixed and source and detector
move
ψ/χ
φ

ω
2Θ

Typically, goniometers also provide sample

translation along x,y, and z
 X-ray scans
ψ/χ
φ

ω
2Θ Surface of the sample

• 2q angle determines the lattice parameter/periodicity examined (the Bragg

equation depends on q (=2q/2) only)
• 2q= angle between detector and the projection of the source
• Standard scans to look for lattice periodicity
• 2q-ω (or q-2q) without offset or coupled scan: simultaneously scan 2q
and ω with 2q = 2ω
• 2q-ω with offset or ω-scan: as above but with 2q = 2ω + ω0
• GIXRD: Scan 2q with constant ω (generally small, ~1º)
• “Orientation scans”: check for orientation of reciprocal lattice (for a fixed
reflection). Constant 2q, vary ω, f, or ψ. (FCFM only available ω and f)
 Data Analysis

 Plot the data (2θ vs. Counts)

 Determine the Bragg Angles for the peaks
 Calculate d and a for each peak
 Apply Scherrer’s Formula to the peaks
θ - 2θ Scan
 Scherrer's formula
Size effects

x=k*l/B*cosq
x = crystallite size (not grain size!)
k = constant dependent on crystallite
shape (0.89-1)
l = x-ray wavelength
B = FWHM (full width at half max)
q = Bragg Angle
500 nm
Crystallites Grains observed
by SEM
 When to Use Scherrer’s Formula
To be discussed in more detail tomorrow
 Crystallite size <100 nm
 Peak broadening by other factors
– Causes of broadening
• Size
• Strain
• Instrument
– If breadth consistent for each peak then assured broadening
due to crystallite size
 K depends on definition of t and B, normally is ~0.98
 Within 20%-30% accuracy at best
 Strain effect

Sherrer’s Formula References

Corman, D. Scherrer’s Formula: Using XRD to Determine Average Diameter of
Nanocrystals.
 Crystal structures
How do the atoms pack together?

hillocks

 FCC: metals with low Young's modulus Cu,

Pt, Al
 hexagonal: the best packaging Ti, Ru, Zn
 Crystal structures
BCC and diamond
 BCC: harder and less malleable
metals as in the case of FCC
– high temperature form of metals that
are closed packaged at low
temperatures
– Fe, V, Ta
 Diamond:
– two interpenetrating FCC structures
– 3D covalent bonding, tetrahedral
configuration
– hardest substance known
– C, Si, Ge
 Zinc blende
– ~diamond, but two different atoms
from top
– III-V compounds GaAs, InSb
 Some crystal structures
Graphite
 Alternative to diamond
 layered structures, 2D covalent bonds
 planes pill up on top of each other with very
weak forces

Courtesy C. Whelan, IMEC

 Crystal structures
DNA
In 1962 shared the Nobel Prize
Photograph 51

Watson and Crick Wilkins

Franklin
 Some crystal structures
Perovskite:A4+B2+O3

 A-cations: cubic lattice

many of these crystalline
 B-cations: body centered structures are ferroelectric or
superconductors
 O-anions: FCC BaTiO3, Pb(Ti,Zr)O3

O
 Lattice Constants

The distance between planes of atoms is

d(hkl) = 2π / |G|
Since G can be written as
G = 2π/a (h*b1+ k*b2 +l*b3)
Substitute in G
d(hkl) = a / (h2 + k2 + l2)(1/2)
Or
a = d * (h2 + k2 + l2)(1/2)
a is the spacing between nearest neighbors
 Surfing a little bit
• Basics
http://phycomp.technion.ac.il/~sshaharr/intro.html
http://www.matter.org.uk/diffraction/x-ray/experimental_powder_diffraction.htm
http://www-outreach.phy.cam.ac.uk/camphy/xraydiffraction/xraydiffraction_exp.htm
http://serc.carleton.edu/research_education/geochemsheets/techniques/XRD.html
• X-ray data booklet:
http://xdb.lbl.gov/xdb.pdf
• Web-based calculations of interaction of x-rays with matter:
http://henke.lbl.gov/optical_constants/
• Web-based x-ray pattern simulations:
http://sergey.gmca.aps.anl.gov/
• IMD, free reflectivity simulation software:
http://www.rxollc.com/idl/
• ESRF scientific software: http://www.esrf.eu/UsersAndScience/Experiments/TBS/SciSoft
• Miscellanious x-ray based software:
http://www.ccp14.ac.uk/ccp/web-mirrors/krumm/html/software/winsoft.html
There are numerous similar other pages and software tools freely available. Not all is easy to
use and has been updated recently.You often have to understand a little what the tool is doing
(but this is where this tutorial may help).
 Literature
• M. Birkholz, Thin film analysis by x-ray scattering, Wiley, 2006
• J. Als-Nielsen, Elements of modern x-ray physics, Wiley, 2001
• U. Pietsch,V. Holý, T. Baumbach, High-resolution x-ray scattering, Springer 1999
• D.K. Bowen, B.K. Tanner, X-ray metrology in semiconductor manufacturing, CRC Press, 2006
• P.F. Fewster, X-ray scattering from semiconductors, Imperial College Press, 2003
• D.K. Bowen, B.K. Tanner, High resolution x-ray diffractometry and topography, CRC Press, 1998
• K. Ramakanth Hebbar, Basics of x-ray diffraction and its applications, IK Publishing, 2007
• C. Suryanarayana, M.G. Norton, X-ray diffraction: a practical approach, Springer, 1998
• V. Pecharsky, P. Zavalij, Fundamentals of powder diffraction and structural characterization of
materials, Springer 2008
• R. Jenkins, R.L. Snyder, Introduction to x-ray powder diffractometry, Wiley, 1996
• J. Dalliant, A. Gibaud (eds.), X-ray and neutron reflectivity, Springer, 2009

• Classic: B.E Warren, X-ray diffraction, Dover, originally 1969.

• Classic: A. Guinier, X-ray diffraction in crystals, imperfect crystals, and amorphous bodies, Dover,
originally 1963 (French 1956)
• Classic: B.D. Cullity, Elements of x-ray diffraction, Addison-Wesley 1956, free at
http://www.archive.org/details/elementsofxraydi030864mbp