MSE 110

Introduction to Materials
Characterization:
Crystal Structure and X-ray
Diffraction of Materials
Lecture 1
Fall 2015

Today:

Syllabus
Office Hours / Recitation Sections
Textbook(s): Pecharsky, Wasada, Cullity&
Origin of phemomenonBackground

Syllabus
On-line:
CCLE

Textbooks

On-line

On-line

Paperback or
hardcover

Lecture Topics and Reading List :

(Cullity chapters)

Introduction, Electromagnetic radiation - Ch. 1

Properties of x-rays: x-ray spectrum - Ch. 1
Properties of x-rays: Absorption and Filters - Ch. 1
Crystallography: Unit Cell, Cell Geometry - Ch. 2
Crystallography: Crystal Systems - Ch. 2
Crystallography: Crystal Structures, Defects - Ch. 2
Reciprocal space - Ch. 2 and Appendix 1/ Review for Quiz
QUIZ / Stereographic Projection - Ch. 2
Stereographic Projection cont. - Ch. 2
Elements of diffraction physics: Geometry - Ch. 3, 4 and 5
Elements of diffraction physics: Scattering - Ch. 4
Structure Factor Calculations - Ch. 4
Determination of Crystal Structure: Powder Method - Ch. 7, 10 and 13/ Review for Midterm
MIDTERM
Determination of Crystal Structure: Order-Disorder Transformations - Ch. 10
Analysis of Epitaxial Layers - Ch. 17, 19, handout
Orientation of Single Crystals: Laue Method - Ch. 8 and 16
Qualitative Chemical Analysis by XRD: Phase Identifications Ch. 9
Quantitative Chemical Analysis by XRD: Determination of Phase Diagrams and Phase Analysis Ch. 11 and 12
Special Topics: Internal Stresses, Crystallographic Texture - Ch.14, 15 / Review for the Final

Syllabus
Grade Distribution:
Final Exam:
Mid-term Exam:
Quiz:
Homework

35%
30% (2 hr)
15% (1 hr)
20%

Background
MSE 104
Length scales: nm, , lattice, polycrystal, amorphous, single crystal
e-m waves, constructive / destructive interference
MSG
Why 110?
Understand basic properties of crystals

Points, directions, PLANES

XRD is used among all MSE specialties

Responsible for advances in may scientific fields

Non-destructive
Evolving field
Properties of new classes of materials

?
?

Examples
Metals:
Strain hardening
Defects
Alloys vs compounds
Order-disorder transitions

Polymers
Structure
Degree of crystallinity

Examples
Semiconductors
Structural perfection
Alloy Composition (Bandgap Engineering)

Ceramics
Quantitative multi-phase analysis
Glasses: non-crystalline, s.r.o.

Bio-materials
W&C
Double Helix deduced from XRD measurement
Name of crystallographer?

Quasicrystals

Historical background:
X -ray diffraction
Mid 1850s
Cathode rays (electrons) were a hot topic
Electrons could be extracted (freed) from a
cathode placed in an evacuated container (~ 1854)
By 1895, properties of electrons fairly well
understood
Charged (negative)
could be extracted from a window in the tube
Decayed exponentially in air
Experiments worked best in a vacuum

Historical Background

William Crookes and the "Crookes Tube.

In a "Crookes" tube, a negatively biased electrode, called the cathode, emits cathode rays
(electrons) which accelerate toward the anode. Many cathode rays miss the anode and instead
strike the glass end of tube, causing it to fluoresce.
(2008 Copyright James H. Wittke, Northern Arizona University)

Discovery of x-rays
Wilhelm Conrad Rntgen (Roentgen)
November 8, 1895:

Studied e- interactions with matter

Observed a fluorescent screen illuminate when
electrons were generated in a Crookes tube

Roentgen
Observation:
Screen was too far away for these to be electrons
Some unknown ray:
X-ray

Other observations
Exposed photographic film
Could see brass key in wooden box
Mrs. Roentgens contribution

Nobel Prize in Physics (1901)

Radiography medical applications

A different era would it be any different today?

Lack of understanding: pathological science - (N-rays)
Uncritical analysis: OPERA experiment reports anomaly in
flight time of neutrinos from CERN to Gran Sasso (Italy)

First applications were not so scientific

History lesson continues

Wien showed that ~ and confirmed e-m nature
Not everyone agreed

Visible light could be diffracted

Scattering sites interspaced ~ wavelength
Could x-rays be diffracted?

Roentgen couldnt do it on his own

History Lesson
1912 Roentgen visits Munich
Labs of Debye, Laue, Summerfeld
P.P. Ewald was Summerfeld Ph.D. student
Modeled crystal as small oscillators (to
represent atoms) with ~ 1 spacing
Laue: since x-rays have 1 , atoms may be a 3dimensional diffraction grating for x-rays
Summerfeld (senior guy) thought atomic movement
was too great (> 0.3 )
Rubber balls and springs

And more history

Laue has some help
Knipping and Friendrich
Knipping: just finished Ph.D. thesis fun to help
Friedrich: good with setting up apparatus, did
experiments on the sly
X-rays CuSO4 || (film)
X-rays (film) || CuSO4
(Worked both ways)

Nobel Prize 1914

Rest of world notices

W.H. Bragg (Leeds U.) (Father)
W.L. Bragg (Cambridge) (Son)
Nobel Prize 1915
Extended ideas about phenomenon
Constructive interference
Braggs Law

n 2d sin B

= radiation wavelength
d = distance between planes
B = angle between source and plane

Properties of X-rays
X-rays are electromagnetic radiation
Much shorter wavelength than visible light

1 = 10-10m, 1 nm = 10 = 10-9m
X-ray wavelengths are in the range 0.5 2.5 .
Wavelength of visible light ~ 3900-7500

Properties of Electromagnetic Waves

x

E A sin 2 t

A = wave amplitude
c

= wavelength

= frequency
c = velocity of light = 3x108 m/s
Photon energy:
h= 6.636x10-34 Js

E h

X-ray Spectrum How x-rays are produced

[Roentgen] X-rays are produced when electrically charged particles (electrons)

decelerate
The kinetic energy of the electrons is equal to the product of the accelerating
voltage (V) and charge on the electron (e)
Most of the kinetic energy of the electrons striking the target is converted into
heat, less than 1% transformed into x-rays.

EK

1
eV mv 2
2

e = electron charge (1.610-19C)

EK = kinetic energy
V = applied voltage
m = mass of the electron (9.1110-31kg)
v = electron velocity (m/sec)

Continuous X-ray Spectrum

Results from the deceleration of electrons at the target
Each electron loses energy differently (all at once or in
differing increments)
White radiation
Continuous radiation
Bremsstrahlung

1.2 10
SWL ( )
V (volts )
4

Continuous radiation spectrum

The total x-ray energy emitted per second depends
on the atomic number Z of the target material and
on the x-ray tube current. This total x-ray intensity is
given by

I AiZV m
Aproportionality constant
itube current (measure of the number of electrons
per second striking the target)
mconstant 2

Characteristic Radiation
In addition to the continuous
radiation spectrum, there are
sharp intensity peaks that
occur. The wavelength (or
energy) of these peaks
corresponds to the target
material
Referred to as characteristic
(of the target) radiation

Physics of characteristic radiation

Kedge

The shell model of the atom,

is useful for understanding the
origin of the characteristic lines

Incident electron with sufficient energy knocks K (or L or) electron out of shell
Cascade of other electrons to fill shell releases energy
CANNOT gain energy: Energy (Kedge) > Energy (K,, etc)

Atomic Energy Transitions

Atomic Energy Transitions

Atomic Energy Transitions

Transitions

Characteristic Radiation
K lines are usually
most useful for x-ray
applications of
materials
I(k1) 2I(k2)

Twice as many states

I(k) 5I(k)

Intensity of Characteristic Spectrum

I BiV Vk

I = Intensity
i = Electron current applied to target
V = Voltage between electron source and target
Vk = Voltage that corresponds to Kedge energy
n 1.5, B is target-dependent constant

Importance of characteristic radiation

K lines provide monochromatic source to
make diffraction measurements feasible and
relatively easy to interpret
Line widths are on the order of 0.001
width usually means
FWHM: Full width at half maximum (intensity)

Other aspects of characteristic radiation

Moseleys Law
L

Shorter wavelength
(higher frequency [])
for higher Z target

C Z
K

= 1 for K
= 7.4 for L

http://chimie.scola.ac-paris.fr/sitedechimie/hist_chi/text_origin/moseley/Moseley-article.htm

Source of characteristic radiation

Roentgen experiment
Electrons decelerate and produce photons (-x-rays)
His discovery: serendipitous
Components to make a commercial x-ray tube are
based on the principles established with Roentgens
experiment

X-ray source (tube)

Basics:
Source of electrons: Filament
Acceleration of electrons to target: High Voltage
Produce characteristic radiation: Target

X-ray Tube Details

X-Ray Tube Components

Filament
Low work function, high melting point metal
Tungsten (W)

Target
Elemental metal
High thermal conductivity
More than one element more than one characteristic spectrum

High Voltage
Electrical isolation is important
Body of x-ray tube is an insulator
Glass or ceramic

Other tube details

Vacuum
Electrons absorb in air, vacuum maximizes electron
current to the target

Water cooling
X-ray production is very inefficient (99% heat)
Target melts w/o cooling

Windows
X-rays need to exit tube without excessive
absorption (next section on absorption)
Lightest solid, non-porous, relatively stable element
Beryllium