10/1/2022
X-
X-Ray Diffraction
DIAH SUSANTI, Ph.D Philip MPD System
The Electromagnetic Spectrum
X-Rays are part of the spectrum of electromagnetic radiation
occupying the region between the ultraviolet and gamma rays.
The full spectrum is shown graphically and in tabular format
below:
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Video
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Bohr atomic model
The binding energy of an electron in an atom is
established mainly by determining the incident. It
is for this reason that the term absorption edge is
very often found in literature:
Energy level = binding energy = absorption edge
The individual shells are labeled with the letters K,
L, M, N,..., the innermost shell being the K-shell,
the second innermost the L-shell etc. The K-shell
is occupied by 2 electrons. The L-shell has three 3
levels and can contain up to 8 electrons. The M-
shell has five sub-levels and can contain up to 18
electrons.
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X-
X-Ray Production eV hX max
Potential
Source c hc
OSWL Omin
X max eV
Electron
12.40 x10 3
OSWL
V
Tube I [Link] AiZV m
X-Ray
Tube is in vacuum, target material (cathode) used
is usually Cu, W, Fe
1 Joule = 6.24 × 10 18 eV
h = Planck’s constant = 6.6261 x 10-34 J.s
c = light speed = 3x108 m/s
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X-
X-Ray Production
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Continuous Radiation
X-rays are produced whenever matter is irradiated with
a beam of high-energy charged particles or photons.
Interactions that occur between the beam (i.e.,
electrons) and target will result in a loss of energy.
Since energy must be conserved, the energy loss results
in the release of x-ray photons of energy (wavelength)
equal to the energy loss.
This process generates a broad band of continuous
radiation (a.k.a. bremsstrahlung or white radiation).
This (along with the higher-intensity characteristic lines)
is shown in the figure below (for a Cu target at a variety
of kV) as the low-intensity spectrum
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Generation of Characteristic X-rays
The simplified discussion below uses Cu as an example. The
same process applies to all of the anodes listed in Table above.
The quantum physics related to the generation of x-rays is, in
reality, much more complicated, but this simplified discussion
works for our purposes.
If a high-energy electron or photon interacts with electrons in the
target anode atoms such that an inner orbital electron is
displaced, an electron from a lower energy shell will “jump” to
replace the displaced higher-energy electron.
This results in the generation of an x-ray photon of quantum
energy equal to that of the transition. The relationship between
the energy of this x-ray and its wavelength is described by
equation above. This is shown schematically in the diagram at
left. An incoming electron displaces a K-shell electron. If an L
shell electron moves to replace it, a Kα x-ray is produced. If an
M-shell electron moves to replace it, a Kβ x-ray is produced.
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Making Monochromatic X-rays
There are a number of ways that x-rays “out of the tube”
can be modified such that the radiation detected after
diffraction is only Kα. Some of these methods include:
Use of E filter
Use of proportional detector and pulse height selection
Use of a Si(Li) solid-state detector
Use of a diffracted- or primary-beam monochromator
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X-
X-Ray Diffraction
Relative Intensity
Wave Length
Intensity Intensity
filter profile
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Diffraction Theory Summary
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Diffraction from crystals
X-ray Detector
Tube
Incident radiation “Reflected” radiation 1
T T
X Z
Y
d
? Transmitted radiation
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Incident radiation “Reflected” radiation 1
T T
X Z
Y
d
Transmitted radiation
Beam 2 lags beam 1 by XYZ = 2d sin T
so 2d sin T = nO Bragg’s Law
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How could diffraction occur?
Atoms that regularly arranged in a certain crystallographic plane cause
radiation scattering (see the picture). The lower radiation wave travels in the
longer distance than the higher one. In order to form a wave maximum,
both waves should meet Bragg’s law:
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e.g. X-rays with wavelength 1.54Å are reflected from
planes with d=1.2 Å. Calculate the Bragg angle, T, for
constructive interference.
O = 1.54 x 10-10 m, d = 1.2 x 10-10 m, T=?
2d sin T nO
n=1 : T = 39.9°
§ nO ·
1
T sin ¨ ¸ n=2 : X (nO/2d)>1
© 2d ¹
2d sin T = nO
We normally set n=1 and adjust Miller indices, to give
2dhkl sin T = O
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Example of equivalence of the two forms of Bragg’s law:
Calculate T for O=1.54 Å, cubic crystal, a=5Å
2d sin T = nO
(1 0 0) reflection, d=5 Å (2 0 0) reflection, d=2.5 Å
n=1, T=8.86o
n=2, T=17.93o n=1, T=17.93o
n=3, T=27.52o
n=4, T=38.02o n=2, T=38.02o
n=5, T=50.35o
n=6, T=67.52o n=3, T=67.52o
no reflection for nt7 no reflection for nt4
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Use Bragg’s law and the d-spacing equation
to solve a wide variety of problems
2d sin T = nO
or
2dhkl sin T = O
1 h2 k 2 l2
d2 a 2 b2 c2
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Combining Bragg and d-spacing equation
X-rays with wavelength 1.54 Å are “reflected” from the
(1 1 0) planes of a cubic crystal with unit cell a = 6 Å.
Calculate the Bragg angle, T, for all orders of reflection, n.
1 h2 k 2 l 2 11 0
0.056
d2 a2 62
d 2 18 d = 4.24 Å
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§ nO ·
d = 4.24 Å T sin 1 ¨ ¸
© 2d ¹
n=1: T = 10.46° = (1 1 0)
n=2: T = 21.30° = (2 2 0)
n=3: T = 33.01° = (3 3 0)
n=4: T = 46.59° = (4 4 0)
n=5: T = 65.23° = (5 5 0)
2dhkl sin T = O
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Summary
¾ We can imagine planes within a crystal
¾ Each set of planes is uniquely identified by its
Miller index (h k l)
¾ We can calculate the separation, d, for each set
of planes (h k l)
¾ Crystals diffract radiation of a similar order of
wavelength to the interatomic spacings
¾ We model this diffraction by considering the
“reflection” of radiation from planes - Bragg’s Law
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Exercise
1. An
1. n X X-ray
-rray
ay bea
ay beam
b am
m of of unknown
u own wnn wav
wavelength
w veeleng
enggthh hit
hitss
h
ccopper
co
copp peer wiwith
w i h a la
ith lattice
attiicee cons
attic cconstant
co
constan
stannt a = 00..333615
nt 61155 n
nm,
nmm andd
m,
makee a ddiffradiffraction
difffrra
ract
actiion n ang
aangle
an nglee ooff 43
443.
3.44 °. A sep sseparate
para
par
rate
determinations
deter
de terrm
rmi miinaatio
min a on
ons provprove
p
pro
roovvee th tthat
haat tthe
hat th
he diffr
diffraction
d
dif
ifff
ffra
ffrracti
actiion
act io
on lline
ne is
i
the
th
hee liline
inee n = 1 forr d111
ine
in 11. Determine
11 e thee wavelength
of thee x-rays
-
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2. T
2. Th
The
hee alu
h aaluminum
luum
miinum
inum m unit
u itt ce
ccell
eelll latti
llattice
attiicee const
cconstant
onst
nsttan
t t (FCC)) is
0.4049
. 9 A. ((a) a). Specify
a) p fyy d2220 200 ((b)
b). d1111 ((c)
b) c).
c)
). d200
000
3. Face
3. F e ccentered ente
nte
teereedd cubi
ccubic
ubiicc (F
((FCC)
FCC) C)) nickel
n l with
with h anan atomic
a
radius
raddiuss off 0.
dius 0.12446
.12446
24466 n nm m. (a) a)). Determinee thee distance
d2200
000, ((b)
b)) d2220
200, ((c)
c). d1111
c)
4. The
T e di ddistance
stancee between
b en n plplanes
p lanneess 1110
100 of
of a b body
bod dy-
d y-centered
cceente
ntered
cubic
bicc me metal
m ettal (BC (BCC)
BCCC)) iiss 0.20.203
.203 nm m. (a((a)
a)). F
a). Find d thee unit
cell,l,l (b)
b).
b)). Atomicc radius, s (c)
s, c). Metal
c) al type
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55.. The
T e dis ddistance
issta
taancce be
between
b etwe
twe
weeeen n tthe
hee d1111111 plan
plane
p nee ooff the
hee FC
FCC
F CC
metal
meta
etaaall is is 0.2.235
.235
35 nm m. (a
m. ((a)
aa)) wha
what
whaaatt is
is tthe
he ssi
he size
izee o
off ththe
hee unit
h u
cell,l,l ((b)
b)) thee atomicc radius, s ((c)
s, c)) thee type
y e of metal
yp
6. X-rays
-rraays
a s wit w th
with h a wawavelength
w aveelen
elengt ngtth
ho off 0..058
058
58 nm nm ar aree uused
are sed
to
o mea measure
m aasure
asur
sur
urree tthe
hee d2000 in n nick
nickel
n kel
kel
el. Dif
Diffraction
D ffract
racttion
on n ang
aangle
an gle
2T = 19
2T 19q.q. WWhat at iss thee sizee off thee unit
at it cellll forr the
it
first
st order
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