Curs Raze X 1

Ministry of Education, Research and Innovation
NATIONAL INSTITUTE FOR RESEARCH AND DEVELOPMENT

IN MICROTECHNOLOGIES IMT - Bucharest
Laboratorul de Nanotehnologii L1
Tehnici moderne de masura si control

nedistructiv cu radiaii X
Mihai Dnil
126A, Erou Iancu Nicolae Street, R-077190 , Bucharest, ROMANIA
PO-BOX 38-160, 023573, Bucharest, ROMANIA
mihai.danila@imt.ro
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IMT @2009, All rights reserved
1. Teoria difractiei radiatiilor X si notiuni de Fizica Starii Condensate

(background minimal)
2. Aplicatii ale metodelor XRD cu exemple
1. Difracie pe pulberi (Materiale policristaline)

X-Ray Powder Diffraction
Compoziie de faze (phase composition analysis)

in situ XRD
% cristalinitate (analiza cantitativ&calitativ)
Dimensiune de cristalit
Inciden razant GIXRD- glancing incident small angle X-ray diffraction of
mesostructures
Rafinarea parametrului de retea cristalina - lattice parameter refinement
Deformari si tensiuni reziduale - residual stress and strain
Microdifracie
Textur
2. Analiza filmelor subiri
GIXRD glancing incident angle diffraction

Msurtori de reflectivitate de raze X X - ray reflectivity
Filme epitaxiale (grosimi, tensiuni, compozi ie, deformari)
Rocking curves analiza perfec iunii de monocristal
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Definitie
Spectroscopia RX presupune analiza efectului interactiei radiatiei
electromagnetice (foton RX energie de ordinul keV, lungime de unda de
ordinul 1 Angstrom) cu proba
Geometry
Structure
- Analytic
FotonulRX
pstreaz proprietatile
radiatiei
electromagnetice
energia;
viteza;
Lungine de unda
Amplitudin
e
amplitudinea;
Modificarea a cel putin una din
frecventa;
proprietati are loc la interactia
unghiul de faza;
radiatiei electromagnetice X cu
proba
polarizarea;
directia de
propagare.
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Istoric
(http://en.wikipedia.org/wiki/X-ray#History; http://en.wikipedia.org/wiki/X-ray#
Crystallography;)
Descoperirea
Wilhelm Conrad Rntgen - 1895 este creditat pentru descoperire, fiind
primul care le-a studiat sistematic desi nu este primul care le-a
observat efectele. Tubul cu raze X a fost inventat in 1875 - tubul Crookes, de
catre fizicienii care studiau razele catodice electronii de energii mari,
accelerati la potentiale de ordinul 1-100 kV.
Ivan Pulyui, William Crookes, Johann Wilhelm Hittorf, Eugen Goldstein, Heinrich Hertz,
Philipp Lenard, Hermann von Helmholtz, Nikola Tesla, Thomas Edison,
Charles Glover Barkla, Max von Laue.
In April 1887-1892 Nikola Tesla began to investigate X-rays using high voltages and tubes
of his own design. He invented and developed a special single-electrode X-ray tube which
differed from other X-ray tubes in having no target electrode. The principle behind Tesla's
device is called the Bremsstrahlung process in which a high-energy secondary X-ray
emission is produced when concerning various experiments in his 1897 X-ray lecture
before the New York Academy of Sciences. In this lecture Tesla stated the method of
construction and safe operation of X-ray equipment. His X-ray experimentation by
Hand mit Ringen (Hand with Rings): print of

vacuum high field emissions Wilhelm
also led
him to alert the scientific community to the
Rntgen's first "medical" X-ray, of his
biological hazards associatedwife's
withhand,
X-ray
exposure.
taken
on 22 December 1895 and
presented to Professor Ludwig Zehnder of the
Physik Institut, University of Freiburg, on 1
January 1896[1][2]
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A Brief History of X-Ray Diffraction

1895: Rntgen discovers X rays
received the first Nobel prize in physics in 1901
1912: Laue diffracts X rays from single crystal
1914 Nobel prize in Physics
1912: Braggs analyze crystal structures
1915 Nobel prize in physics
1917: Ewald develops dynamical theory of X-ray diffraction
1918: Scherrer uses X rays to determine crystallite size of nanocrystalline gold
1935: X-Ray powder diffractometer developed by Le Galley
1947: first commercial powder diffractometer
Subsequently, Nobel prize winners used XRD
1962: Crick, Watson, and Wilkins: structure of DNA
1962: Perutz and Kendrew: structure of moglobin and hemoglobin
1964: Hodgkin: structure of insulin
1976: Lipscomb: structure of boron hydrides
1985: Karle and Hauptman: development of direct methods in XRD
analysis
1988: Deisenhofer, Huber, and Michel: X-ray structure of proteins for
photosynthetic center
1994: Shull and Brockhouse: Neutron diffraction
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X-rays can diffract from a periodic array of

coherent scatterers, such as atoms in a crystal
Diffraction occurs when objects
in a periodic array scatter
radiation coherently, producing
concerted constructive
interference at specific angles.
Crystalline materials are
characterized by orderly
periodic arrangements of
atoms.
The electrons in an atom
coherently scatter light.
The distance between atoms is
such that they diffract light in
the X-ray spectrum.
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Halite
Na
Cl
Fm3m (225): 5.64/5.64/5.64 <90.0/90.0/90.0> NaCl
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The atoms in a crystal are a periodic array of coherent scatterers

and thus can diffract light.
Diffraction occurs when each object in a periodic array scatters
radiation coherently, producing concerted constructive interference
at specific angles.
The electrons in an atom coherently scatter light.
The electrons interact with the oscillating electric field of the light
wave.
Atoms in a crystal form a periodic array of coherent scatterers.
The wavelength of X rays are similar to the distance between
atoms.
Diffraction from different planes of atoms produces a diffraction
pattern, which contains information about the atomic
arrangement within the crystal
X Rays are also reflected, scattered incoherently, absorbed,
refracted, and transmitted when they interact with matter.
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The X-rays can be:

attenuated
absorbed
fluoresced
incoherently scattered
coherently scattered
refracted
reflected
diffracted
The electromagnetic moment of X-ray photons interacts

with the electrons in matter
The change in X-ray photons due to interaction with
electrons can be used to discern information about the
matter
Phase information is ussually lost
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Braggs law is a simplistic model to describe the

conditions that are required for diffraction.
2d hkl sin
For parallel planes of atoms, with a space dhkl
between them, constructive interference only occurs
when Braggs law is satisfied.
In our diffractometers, the X-ray wavelength is fixed.
Each plane of atoms produces a diffraction peak at
a specific angle .
The direction perpendicular to the planes must bisect
the incident and diffracted beams.
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Powder diffractometers typically use the

Bragg-Brentano parafocusing geometry.
Detector
X-ray
tube
The incident angle between the X-ray source and the sample is .
The diffraction angle, between the incident beam and the detector angle, is 2.
The Bragg-Brentano geometry constrains to be always of the detector
angle 2
This constraint results in the incident angle the detector angle being equal
to
Do not get confused: this is an artificial constraint. Diffraction does not
rely on the incident and detector angles being equal.
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A single crystal in a Bragg-Brentano

diffractometer produces one family of
peaks in the diffraction pattern.
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The diffraction pattern consists of a record of photon

intensity versus detector angle 2.
The position, intensity, width, and shape of the observed diffraction
peaks tells us about the crystal structure and, in some cases,
microstructure of the sample.
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A polycrystalline sample should contain thousands of

crystallites. All diffraction peaks should be observed.
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).
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What can we do with XRD?
Identify phase composition

Measure unit cell lattice parameters
Estimate crystallite size, microstrain, and defect concentration
Measure residual stress
Measure texture and/or epitaxy
Evaluate thin film quality
Measure multilayer thin film thickness, roughness, and density
Determine orientation of single crystals
Solve or refine crystal structures
Analyze ordered meso- and nanostructures
Etc.
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X-Ray Analysis Methods

Significant Experimental Facts
(affecting measurements)
Detector Dynamic range & Speed

X-Ray Source (tube) High Power Beam Intensity (emited, on the sample and at the
detector)
X-ray Optics (high resolution incident and receiving optics) Resolution, Intensity, Speed
Any attempt to filter/monochromatize the incident X-Ray beam reduces intensity on the
sample
by several orders of magnitude (typically with a factor of 10 -2 - 10-6)
We need:
The plane monochromatic wave approximation to be fulfilled (for high resolution

measurements,
multiple reflections: 2- 4 for monochromator, 2 reflections for the analyzer)
Measurements to be performed as fast as possible, maintaining high resolution options
FWHM of minimum 10 -2 - 10-3
An almost perfect (and sometimes impossible) combination of Detector, X-ray tube,

goniometer,
incident X-ray optics, etc. must be chosen to minimize measurement time and increase
resolution
and
d sensitivity
7
9 (in order to detect changes in lattice parameter of
for high resolution measurements;
10 10
and beyond)
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Most XRD Analyses are Focus on Identifying the

Phases Present in a Sample
We collect the XRD pattern over a range that is suitable for the
material we are studying
typically 20 to 70 2 for inorganic specimens
typically 5 to 40 2 for organic specimens

data collection time ranges from 5 min to 1 hour for our
instruments
in the real world, these times are typically 30 min to 2 hours
We compare the experimental data to a reference database of powder
diffraction patterns
The diffraction pattern of every phase is a unique fingerprint
A crystalline phase is identified by the set of interplanar d spacings
Each lattice plane gives a diffraction peak at a specific angular value
(related to atomic plane spacing by BRAGG law) and the relative
intensities of those peaks are also a fingerprint of the crystalline
phase
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Application of X-ray Diffraction

From Sciences to Engineering
X-ray Powder diffraction (XRPD)
High resolution X-ray diffraction (HRXRD)
(including multiple refflection HR-MRXRD)
X-ray reflectometry (XRR, including HRMR XRR )

Grazing incidence diffraction (GIXRD)
In-plane grazing incidence diffraction (IPGID)
Small angle X-ray scattering (SAXS)
Single crystal diffraction (SCD)
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X-Ray Diffraction and Scattering

Principle
Debye cone
Incident beam
Sample
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Powder diffraction data consists of a record of

photon intensity versus detector angle 2.
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
Position
Intensity
Raw Data
[2]
[cts]
Reduced dI list
hkl
dhkl ()
Relative
Intensity
(%)
25.2000
372.0000
25.2400
460.0000
25.2800
576.0000
25.3200
752.0000
{012} 3.4935
49.8
25.3600
1088.0000
25.4000
1488.0000
{104} 2.5583
85.8
25.4400
1892.0000
{110} 2.3852
36.1
25.4800
2104.0000
{006} 2.1701
1.9
25.5200
1720.0000
25.5600
1216.0000
{113} 2.0903
100.0
25.6000
732.0000
{202} 1.9680
1.4
25.6400
456.0000
25.6800
380.0000
126A,
Erou Iancu
Nicolae Street, R-077190 , Bucharest, ROMANIA
25.7200
328.0000
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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
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Databases such as the Powder Diffraction File (PDF) contain dI

lists for thousands of crystalline phases.
The PDF contains over 200,000 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.
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Quantitative Phase Analysis

With high quality data, you can
determine how much of each phase is
present
must meet the constant volume
assumption (see later slides)
The ratio of peak intensities varies
linearly as a function of weight fractions
for any two phases in a mixture
need to know the constant of
proportionality
RIR method is fast and gives semiquantitative results
Whole pattern fitting/Rietveld
refinement is a more accurate but more
complicated analysis
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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
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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-Hall plot can let you separate microstrain and
crystallite size
00-043-1002> Cerianite- - CeO
Intensity (a.u.)
K
B 2
L cos
23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41
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ROMANIA
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2 (deg.)
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
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Commonly Used X-Ray Detectors

Point detectors (0-D)
Linear detectors (1-D) Area detectors (2-D)
Scintillation counter
Silicon strip detector
Proportional counter
Single wire proportional
Multi wire proportional

counter (MWPC)
Image plate detector (IP)
Si(Li) solid state

detector
Counter
CCD camera
Image plate detector (IP)
Ge solid state detectors
Photographic film
Linear CCD
Silicon pin diodes
Pixel detectors
Photographic film
Silicon drift detectors

Ionization chambers
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X- Ray Methods for structural Analysis
Amorphous
Materials
Crystalline
Materials
Crystalline Materials
new applications
X-ray investigations:
XRR: layer thickness, density, roughness, interface layers
XRD: thermal
stability
XRD: phase analysis, crystal orientation and

perfection, thermal stability
IPXRD: phase analysis, crystal
GIXRD: perfection of epitaxial
orientation/perfection, thermal
Stability, etc.
cap-layers, ultra thin layers, etc
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Not only can we identify what phases are present, we

can also determine how much of each phase is present
Red Paint Pigment Mixture
21 wt%
Anatase, TiO2
Intensity(Counts)
28 wt% Hematite,
Fe2O3
51 wt% Rutile, TiO2
24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42
2 (deg.)
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From the ratio of peak intensities, we can

determine how much of each phase there is
I
X
K
I
X
X(b)*I(Al2O3)/I(b)
The ratio of peak intensities

varies linearly with the ratio of
weight fractions
K is not easily determined if we
do not know the mass absorption
coefficients of all phases in our
sample
We can determine K:
empirically, by building
calibration curves
by using published values
(I/Ic)
by simulating the diffraction
pattern: whole pattern
refinement
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Amorphous content is difficult to quantify with XRD

We cannot directly model the scattering from the
amorphous content in a sample
at best, we can emperically fit the amorphous hump
We do not know as much about the amorphous content
as we know about the crystalline content
what is the mass absorption factor of the amorphous
material?
what is the composition of the amorphous material?
what is the density of the amorphous material?
is the amorphous composition homogeneous?
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Determining % Crystallinity without adding a

standard
If we know/assume that the mass absorption coefficient of an
amorphous phase is the same as the crystalline content, we can
sometimes use the ratio of intensities to determine % crystallinity
% Crystalline: 46.5%
% Amorphous: 53.5%
Intensity(Counts)
Area Crystalline Peaks: 108322 cts

Area Amorphous Hump: 124621 cts
10
15
20
25
30
35
2 (deg.)
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Bragg-Brentano vs PB measurements
Classical sealed X-Ray tube compared to
Rotating Anode
Sealed 2.3 kW
X-ray tube
Rotating anode 9kW

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9kW rotating anode, 200mm wafer

Triple axis, vertical goniometer
Independent Theta - Theta rotation
Capababities of the XRD system

installed at IMT Bucharest
5-10 January 2009
Horizontal sample position

X-Y Micro Area Mapping
Chi, Phi, Omega Eulerian Cradle
Bragg-Brentano (+focussing option)
Parallel beam (FWHM 0.1 to 0.003o)
XRR variable resolution (depth profiling)
HRMR-XRD [PB, Ge(220)x2, x4]
Texture Analysis and Pole Figures
GIXRD, In-plane, (GI)SAXS, RSM
D-texUltra high speed detector
CBO-f : 0.4 mm2 colimated parallel beam for increased intensity on sample
and /or X-Y mapping
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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
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Most of 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.
This arrangement provides the best
combination of intensity, peak shape,
and angular resolution for the widest
number of samples.
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F: the X-ray source

DS: the incident-beam divergence-limiting slit
SS: the Soller slit assembly
S: the sample
RS: the diffracted-beam receiving slit
C: the monochromator crystal
AS: the anti-scatter slit
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X-radiation for diffraction measurements is

produced by a sealed tube or rotating anode.
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.
A rotating anode spins the anode
at 6000 rpm, helping to distribute
heat over a larger area and
therefore allowing the tube to be
run at higher power without
melting the target.
Both sources generate X rays by
striking the anode target wth an
electron beam from a tungsten
filament.
The target must be water cooled.
The target and filament must be
contained in a vacuum.
H2O In
H2O Out
Cu
Be
window
ANODE
Be
window
eXRAYS
XRAYS
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FILAMENT
(cathode)
metal
glass
(vacuum)
(vacuum)
AC CURRENT
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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.
L
M
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Spectral Contamination in Diffraction Patterns

K1
K1
K2
K2
K1
K2
W L1
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 lines can be removed with optics
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The X-ray beam produced by the X-ray tube is divergent.

Incident-beam optics are used to limit this divergence
2d hkl sin
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
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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.
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Other optics:
limit divergence of the X-ray beam
Divergence limiting slits
Parallel plate collimators
Soller slits
refocus X rays into parallel paths
parallel-beam optics
parabolic mirrors and capillary
lenses
focusing mirrors and lenses
remove unwanted wavelengths
monochromators
Kb filters
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Parallel Plate Collimator & Soller

Slits block divergent X-rays, but
do not restrict beam size like a
divergent slit
Gbel Mirrors and capillary lenses collect

a large portion of the divergent beam and
refocus it into a nearly parallel beam
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Monochromators remove unwanted

wavelengths of radiation from the incident or
diffracted X-ray beam.
Diffraction from a crystal monochromator can be used to
select one wavelength of radiation and provide energy
discrimination.
An incident-beam monochromator might be used to
select only Ka1 radiation for the tube source.
A diffracted-beam monochromator may be used to
remove fluoresced photons, , or W-contamination
photons from reaching the detector.
Without the RSM slit, the monochromator removes ~75% of
unwanted wavelengths of radiation.
When the RSM slit is used, over 99% of the unwanted
wavelengths of radiation can be removed from the beam.
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Wavelengths for X-Radiation are Sometimes

Updated
Copper
Anodes
Bearden
(1967)
Holzer et al.
(1997)
Cobalt
Anodes
Bearden
(1967)
Cu K1
1.54056
1.540598
Co K1
1.788965 1.789010
Cu K2
1.54439
1.544426
Co K2
1.792850 1.792900
Cu K
1.39220
1.392250
Co K
1.62079
1.620830
Cr K1
2.28970
2.289760
Molybdenum
Anodes
Holzer et al.
(1997)
Chromium
Anodes
Mo K1
0.709300
0.709319
Mo K2
0.713590 0.713609
Cr K2
2.293606 2.293663
Mo K
0.632288 0.632305
Cr K
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)
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High Resolution Measurement Types available

Hardware
- In-plane difraction
- (GI)SAXS, RSM, RC
- Ge (220) 2 bounce monochromator
- Ge (220) 4 bounce monochromator
- Ge (220) 2 bounce analyzer
- CBO-f unit*
-DTexUltra high speed detector*
(* by the end of 2009, September)
Options
(future financing from other projects)
- Ge (440)x2/ x4 monocromator
- 2D Detector
- High/Low temperature chamber
- Simultaneous DSC/XRD chamber
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Crystallite Size Broadening

0.94
B 2
L cos
Peak Width B(2q) varies inversely with crystallite size
The constant of proportionality, K (the Scherrer constant) depends
on the how the width is determined, the shape of the crystal, and the
size distribution
the most common values for K are 0.94 (for FWHM of spherical
crystals with cubic symmetry), 0.89 (for integral breadth of
spherical crystals with cubic symmetry, and 1 (because 0.94 and
0.89 both round up to 1).
K actually varies from 0.62 to 2.08
For an excellent discussion of K, refer to JI Langford and AJC
Wilson, Scherrer after sixty years: A survey and some new
results in the determination of crystallite size, J. Appl. Cryst. 11
(1978) p102-113.
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Factors that contribute to peak broadening
Instrumental Broadening
Crystallite Size
Microstrain (lattice distortions)
Faulting
Dislocations
Antiphase Domain Boundaries
Grain Surface Relaxation
Solid Solution Inhomogeneity
Temperature Factors
The peak profile is a convolution of the profiles from

all of these contributions
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Lattice Parameters
The position of the diffraction peaks are a
product of the space between planes of
atoms.
Consequently, we can use XRD to probe
anything that affects that interplanar spacing.
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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 rought surfaces
Densely packed
Randomly oriented grains/crystallites
Grain size less than 10 microns
Infinitely thick
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Texture analysis is the study of orientation of

crystallites within a sample
Random Orientation
All crystallites are randomly
oriented
there is an even distribution of
all possible orientations
Textured
the orientation of crystallites
are distributed in a nonrandom manner
preferred orientation: texture
that is not wanted
Epitaxial
all crystallites are perfectly
oriented in exactly the same
way
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Intro to X-ray Pole Figures

X-ray diffraction; pole figures; measures average
texture at a surface (m penetration); projection (2
angles).
Neutron diffraction; type of data depends on neutron
source; measures average texture in bulk (cms
penetration in most materials) ; projection (2 angles).
Electron [back scatter] diffraction; easiest [to
automate] in scanning electron microscopy (SEM);
local surface texture (nms penetration in most
materials); complete orientation (3 angles).
Optical microscopy: optical activity (plane of
polarization); limited information (one angle).
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Preferred Orientation (texture)

Preferred orientation of crystallites can create a systematic variation
in diffraction peak intensities
can qualitatively analyze using a 1D diffraction pattern
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
Intensity(Counts)
8.0
(311)
(200)
6.0
(220)
4.0
(222)
2.0
(400)
3
x10
40
50
60
70
80
90
100
Two-Theta (deg)
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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
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Pole figure measurements

2 defines the Bragg angle
planes of diffraction
sample rotation
sample inclination
2
= 90-
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Si 111 pole figure / projection

Perfect Si
layer structure
111 spots 180 rotated

+ additional spots !
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By controlling the incident angle, we can control

the depth of penetration of X-rays
GIXRD can be used to optimize
the diffractometer for the
analysis of surface layers of a
sample
Varying incident angles can be
used to probe different depths,
providing depth profiling
Penetration depth is a
function of the mass
absorption coefficient,
composition, density, and
packing density of the
sample
This technique can be combined
with all of the analyses that have
been previously discussed
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High Resolution Diffraction is used to evaluate

epitaxial multilayer thin films
In a single layer epitaxial thin film, high resolution XRD (HRXRD) can
be used to evaluate the quality of the thin film
Rocking curves compare the distribution of intensity of a diffraction
peak as a function of the tilt of the sample
Poor Epitaxial Thin Film

Intensity (a.u.)
Good Epitaxial Thin Film

Horrible Quality, Not
Epitaxial At All, Thin Film
Perfect Single Crystal Substrate

30.6
30.7
30.8
30.9
31.0
31.1
2 (deg.)
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31.2
31.3
31.4
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Characterization of epitaxial layers

The general problem:
Epitaxial layer with d,L d,S
Diffusion or implantation layers with modified lattice spacing
d,Layer
d,Layer
d/ d = f(z) - depth profile

d,Substrate
substrate crystal lattice, e.g. Si
d,Substrate
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Multilayer thin films create dynamic interference

fringes produced by the multilayer
superstructure
Form and perfection of the
multilayer superstructure
layer thickness, superlattice
period, compositional profile,
miscut angle and direction
Quality of surfaces and interfaces
heterointerface transition,
interdiffusion, interface
roughness
Crytalline properties
elastic lattice distortion, strain
relaxation, porosity, structure
defects such as misfit
dislocations
G
eSionG
e
004
O
m
ega32.93860
2Theta66.17160
Phi0.00
Psi0.19
X9.00
Y-10.00
counts/s
10M
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1M
L
100K
10K
1K
100
10
1
0.1
-1000
-500
mihai.danila@imt.ro
500
1000
1500
O
m
ega/2T
heta(s)
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Direct information from a Rocking

Curve Spectra
0
10
-1
10
Reflectivity
-2
10
exp.
sim.
Ge concentration
(more general: d/d )
Cap:
(53.2 1.0) nm
SiGe: (118.0 0.5) nm
x:
(19.80 0.08) %
Ge:
-3
d/d = 0.005x2+0.03675x
10
Simulation with IHP

program RCRefSimW,
-4
10
-5
Prof. P. Zaumseil
10
Layer thickness
-6
10
-3000
-2000
-1000
1000
Delta Theta [arcsec]

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SiGe HBT structure

0
-1
10
Reflectivity
-2
10
-3
10
Ge content [ % ]
10
20
exp.
sim.
19.48 %
15
10
5
0
55.42
31.68
20 40 60 80 100 120
Depth [nm]
-4
10
-5
10
-6
10
-3000
-2000
-1000
1000
Delta Theta [arcsec]

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Reciprocal space map

82 94 4. 0
48 12 5. 8
27 92 3. 6
16 20 1. 9
940 0. 6
545 4. 5
316 4. 8
183 6. 3
106 5. 4
61 8. 2
35 8. 7
20 8. 1
12 0. 8
7 0. 1
4 0. 7
2 3. 6
1 3. 7
8 29 4. 0
7. 9
4 81 25. 8
4. 6
2 79 23. 6
2. 7
1 62 01. 9
1. 6
94 0. 6
54 54. 5
M ap 4 4b .a 0
31 64. 8
18 36. 3
G
aInAsonGaAs
444
Om
ega15.15600
2Theta140.55000
10 65. 4
618. 2
358. 7
208. 1
120. 8
70. 1
40. 7
23. 6
13. 7
7. 9
4. 6
2. 7
1. 6
Ma p4 4b .a 0
G
aInAsonG
aAs
444
O
m
ega15.15600
2Theta140.55000
Phi90.00
Psi0.27
X0.00
Y0.00
Phi90.00
Psi0.27
X0.00
Y0.00
Q
y*10000(rlu)
O
m
ega
0.8
5500
0.6
5450
0.4
0.2
5400
-0.0
-0.2
5350
-0.4
5300
-0.6
-0.8
-1.0
5250
-0.8
-0.6
-0.4
-0.2
-0.0
0.2
0.4
0.6
0.8
1.0
O
m
ega/2T
h
eta
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7600
7650
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7700
7750
7800
7850
Q
x*10000(rlu)
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Metallization / formation of cobalt

silicide on Si
10 nm Co deposited on Si,
annealed at different temperatures
different phases (CoSi and CoSi2) are

formed as a function of temperature.
optimization of thermal process

budget
TwoTheta converted to netplane

spacing D
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REFLECTIVITY PROFILE
10
10
10
10
10
10
Meas. data
Simulation
-1
-2
-3
-4
-5
-6
0.0000
1.0000
Au
Glass
2.0000
3.0000
2theta angle (deg.)
t = 41.968(3)nm = 19.3g/cm3
-
= 2.213g/cm3
4.0000
Density distr.
30.00000
= 1.028(2)nm
= 0.6nm
Density Distr.
40.00000
Density (g/cm3)
Reflectivity (a.u.)
10
20.00000
10.00000
0.00000
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0.000
mihai.danila@imt.ro
10.000
20.000
30.000
Depth (nm)
40.000
50.000
Metallization /thickness control

Ta2O3/Ta/TaN/SiO2/Si
Simulation with
IHP simulation
program
RCRefSimW
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XRR of very thin Si3N4 layer on Si

SmartLab measurement + RCRefSimW fitting
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XRR of 120 nm Ge layer on Si

SmartLab measurement + RCRefSimW fitting
dGe = (121.2 0.2) nm, = 0.4 nm
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XRR determination of layer thickness

Ultra-high resolution XRR at SmartLab and simulation with RCRefSimW 1.08
dSi
= 287.5 nm
dY2O3 = 26.0 nm
dPr2O3 =
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6.6 nm
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Ministry of Education, Research and Innovation

NATIONAL INSTITUTE FOR RESEARCH AND DEVELOPMENT

Tehnici moderne de masura si control

126A, Erou Iancu Nicolae Street, R-077190 , Bucharest, ROMANIA

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1. Teoria difractiei radiatiilor X si notiuni de Fizica Starii Condensate

1. Difracie pe pulberi (Materiale policristaline)

Compoziie de faze (phase composition analysis)

2. Analiza filmelor subiri

GIXRD glancing incident angle diffraction

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Modificarea a cel putin una din

proprietati are loc la interactia

IMT @2009, All rights reserved

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IMT @2009, All rights reserved

126A, Erou Iancu Nicolae Street, R-077190 , Bucharest, ROMANIA

IMT @2009, All rights reserved

126A, Erou Iancu Nicolae Street, R-077190 , Bucharest, ROMANIA

IMT @2009, All rights reserved

Hand mit Ringen (Hand with Rings): print of

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IMT @2009, All rights reserved

A Brief History of X-Ray Diffraction

IMT @2009, All rights reserved

X-rays can diffract from a periodic array of

Fm3m (225): 5.64/5.64/5.64 <90.0/90.0/90.0> NaCl

IMT @2009, All rights reserved

The atoms in a crystal are a periodic array of coherent scatterers

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The X-rays can be:

The electromagnetic moment of X-ray photons interacts

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126A, Erou Iancu Nicolae Street, R-077190 , Bucharest, ROMANIA

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Braggs law is a simplistic model to describe the

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Powder diffractometers typically use the

IMT @2009, All rights reserved

A single crystal in a Bragg-Brentano

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The diffraction pattern consists of a record of photon

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A polycrystalline sample should contain thousands of

For every set of planes, there will be a small percentage of

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What can we do with XRD?

Identify phase composition

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X-Ray Analysis Methods

Detector Dynamic range & Speed

The plane monochromatic wave approximation to be fulfilled (for high resolution

Measurements to be performed as fast as possible, maintaining high resolution options

FWHM of minimum 10 -2 - 10-3

An almost perfect (and sometimes impossible) combination of Detector, X-ray tube,

for high resolution measurements;

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Most XRD Analyses are Focus on Identifying the