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

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

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

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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

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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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2 (deg.)

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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

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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.

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

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

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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-

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

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IMT @2009, All rights reserved

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

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

G
eSionG
e
004

O
m
ega32.93860
2Theta66.17160

Phi0.00
Psi0.19

X9.00
Y-10.00

counts/s
10M

www.imt.ro

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)

IMT @2009, All rights reserved

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IMT @2009, All rights reserved

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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IMT @2009, All rights reserved

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

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

www.imt.ro

7600

7650

mihai.danila@imt.ro

7700

7750

7800

7850
Q
x*10000(rlu)

IMT @2009, All rights reserved

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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

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

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

IMT @2009, All rights reserved

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

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

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IMT @2009, All rights reserved

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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