IX X-Ray Diffraction
9-1 production of X-ray
X-ray is usually generated by a high energy electron beam impinging
onto the Cu target. This would generate characteristic peaks and a
continuous while radiation.
A sketch of a typical X-ray spectrum is shown below.
(i) λswl ≡short wavelength limit
E=hv
ℎ∙𝑐
eV =
𝜆𝑠𝑤𝑙
where V is the voltage applied to X-ray tube.
(ii) characteristic radiation
(iii) Cu Kα
kα1 = 1.54050 Å
for high angle line
kα2 = 1.54434 Å
kα = 1.5418 Å for low angle line
Why we can resolve kα1 and kα2 double lines at high angle?
λ = 2𝑑ℎ𝑘𝑙 sin 𝜃
𝑑𝜆 𝜆
= 2𝑑ℎ𝑘𝑙 cos 𝜃 = 2 𝑐𝑜𝑠𝜃
𝑑𝜃 2𝑠𝑖𝑛𝜃
𝑑𝜆
= 𝜆 cot 𝜃
𝑑𝜃
𝑑𝜆
dθ = 𝑡𝑎𝑛𝜃
𝜆
So, we can see kα1 and kα2 double lines at high angle
9-2. X-ray diffraction
(i) Laue method λ variable, while radition, θ fixed
(ii) Diffractometer method λ fixed, characteristic radiation,θ varible
(iii) Powder method λ fixed, characteristic radiation,θ varible
(iv) Rotating crystal method λ fixed, characteristic
radiation, θ variable (in part)
9-2-1. Laue method
(1) Laue condition
Von Laue derived the “Laue conditions” in 1912 to express the necessary
conditions for diffraction.
Assume that a, b, c are three crystal lattice vectors in a crystal
a∙ (S’-S)=a∙Ghkl=a∙ (ha*+kb*+lc*)
a∙ (S’-S)= h
Similarly,
b∙ (S’-S)= k
c∙ (S’-S)= l
Very often, the Laue conditions are expressed as
^ ^
a∙ (S’-S)= hλ
^ ^
b∙ (S’-S)= kλ
^ ^ lλ
c∙ (S’-S)=
where
The three Laue conditions must be satisfied simultaneously for diffraction to
occur. The physical meaning of the 3 Laue conditions are illustrated below.
1st Laue conditions
The path difference between the waves equals to
^ ^
AC-BD=a·(S’-S)
where a=AB. The criterion for diffraction to occur is
^ ^
a·(S’-S)=hλ
or
a·(S’-S)=h
；h is an integer ( 1st Laue conditions)
• For 1-dimensional crystal
• Cones of diffracted beams for different h
Stereographic projection representation for 1-D crystals
The projection of diffracted beams for h=0 is a great circle if the incident
beam direction is perpendicular, i.e.
S⊥a.
The projection of diffracted beams for h=0 is a small circle if the incident
beam direction is not perpendicular
2nd Laue condition
b·(S’-S)=k; k is an integer
• For a two-dimensional crystal
The 1st and 2nd conditions are simultaneously satisfied only along lines of
intersection of cones.
Stereographic projection for 2-D crystals
The lines of intersection of cones are labeled as (h, k)
3rd Laue condition
c·(S’-S)=l
For a 3-D crystal
Two Ewald spheres of radius OA and OB form, where
(2-2) zone axis
The planes belong to a zone
We define several planes belong to a zone [uvw], their plane normal
[hi,ki,li] are perpendicular to the zone axis, In other words,
[uvw]·[hikili]=0
hiu+kiv+liw=0
In the Laue experiments, all the planes meet the diffraction criterion. For a
particular plane (hi ki li) meets the 3 Laue conditions.
So
for all the plane (hi ki li) belonged to the zone [u v w]
Then, we may plot
The path difference between the waves equals to
^ ^
OA·(S’-S)=0
A’. for the condition Φ<45°
B’. for the condition Φ>45°
9-2-2 Diffractometer method
9-2-2-1 θ-2θ scan
If a new material is deposited on Si (100) and put on the substrate holder
in the diffractometer set-up, κ’-κ is always parallel to the Si (100) surface
normal.
(a) Ewald sphere construction
Rotate the incident beam at until Gh1k1l1 meets the diffraction condition at
2θ=2θ1
This is equivalent to at least one crystal with (h1k1l1) plane normal in parallel
with the Si (100) surface normal.
When the incident beam is rotated (rotating the Ewald sphere), different G h2k2l2
will meet the diffraction condition at 2θ=2θ2
This is equivalent to at least one crystal with (h2 k2 l2) plane normal also in
parallel with the Si (100) surface normal
If only one crystal of the film is observed in the diffractometer measurement the
film is epitaxial or textured on Si (100)
(b) XRD spectrum of AIN deposited on Si (100) measurement, the film epitaxial
or textured on Si (100)
A large number of grains with AIN (002) surface normal in parallel to Si (100)
surface normal, but small amount of grains of AlN (100) and AlN (101) are also
parallel to Si (100) surface normal
9-2-2-2 X-ray rocking curve
X-ray rocking is usually used to characterize the crystal quality of an epitaxial
or texture film.
At a certain diffraction condition
κ’-κ= 2πGhkl
the incident and outgoing directions of X-ray are fixed and the sample is rotated
by θ scan.
When the crystal is rotated by dθ, this is equivalent to the detector being
moved by the same dθ. The FWHM of the diffracted peak truly reflects the width
of each reciprocal lattice point i.e. the shape effect of a crystal.
Find the diffracted peak at θ and then scan the sample
rocking rotating 看晶体长得好不好
9-2-2-3 Φ scan
The Φ scan is used to characterize the quality of the epitaxial film around its
plane normal by rotating Φ (0-2π)
Example: the crystal quality of highly oriented grains each of which is columnar
structure shown below.
Each lattice point in the reciprocal lattice will be expanded into an orthorhombic
volume according to the shape effect. The Φ scan can be used to confirm the
orientation of the columnar structure relative to the substrate.
9-2-4 Powder method (Debye-Scherrer Camera)
(a) Ewald sphere construction
S’ forms a cone resulting from the intersection between Ewald sphere and the
spherical reciprocal lattice.
Powder can be treated as a very larger number of grains with grain orientation
in a random distribution.
→Reciprocal lattice become a series of concentric
spherical shells of |Ghkl*| as their radius
the intersection between the concentric spherical shells of |G hkl*| in radius and
𝜅
the Ewald sphere of radius are a series of circles.
2𝜋
→The circle are recorded as lines in the film.
9-3. The intensities of diffracted beams
For powder pattern lines Debye-scherrer method
1+𝑐𝑜𝑠2 2𝜃
I=|F|2P𝑠𝑖𝑛2 𝜃𝑐𝑜𝑠𝜃A(θ)e-2M
where I=relative integrated intensity (arbitrary unit)
P=multiplicity factor
F=structure factor
θ=Bragg angle
1+𝑐𝑜𝑠2 2𝜃
=Lorentz-polarization factor
𝑠𝑖𝑛2 𝜃𝑐𝑜𝑠𝜃
A(θ)=absorption
e-2M = temperature factor
Example
Debye-Scherrer powder pattern of Cu made with Cu kα radiation
|F|2=FF*=N2·16f2 for unmixed indices
(b)
Then,
Small θ is associated with small (h2+k2+l2).
Total 8 lines can be derived through the reflection (selection) rule for FCC in the
Debye-Scherrer powder pattern.
(b) Multiplicity P is the one counted in the point group stereogram.
In cubic,
{hkl} P=48;
{hkl} P=24;
{hkl} P=24;
{hkl} P=12;
1+𝑐𝑜𝑠2 2𝜃
(c) Lorentz-polarization factor 𝑠𝑖𝑛2 𝜃𝑐𝑜𝑠𝜃
(i) polarization factor
The scattered beam depends on the angle of scattering
Thomson equation
k=constant
α = angle between the scattering direction and the direction of
acceleration of the electron
Assuming the incident beam is traveling in 𝑥̂ direction
An unpolarized beam from X-ray tube has its electric field 𝐸⃗ in a
random direction. The y and z components of the incident beam accelerate
electrons in 𝑦̂ and 𝑧̂ directions, respectively.
E2=Ey2+Ez2
Since
2 2
𝐸2
Ey =Ez =
2
𝐼0
Ioy=Ioz=
2
According to Thomson equation
𝑘
𝐼𝑝𝑦 = 𝐼𝑜𝑦
𝑟2
𝑘
𝐼𝑝𝑧 = 𝐼𝑜𝑧 cos 2 2𝜃
𝑟2
𝑘 𝑘
𝐼𝑝 = 𝐼𝑝𝑦 + 𝐼𝑝𝑧 = 𝐼𝑜𝑦 2
+ 𝐼𝑜𝑧 2
cos 2 2𝜃
𝑟 𝑟
𝑘
𝐼𝑝 = 𝐼𝑜𝑧 (1 + 𝑐𝑜𝑠 2 2𝜃)
𝑟2
𝑘 (1 + cos 2 2θ)
𝐼𝑝 = 𝐼𝑜 2
𝑟 2
(1+cos2 2θ)
where Ip is the total scattered intensity at p and the is the
2
polarization factor
1 1
(ii) Lorentz factor ∙ 𝑐𝑜𝑠θ ∙ 𝑠𝑖𝑛2𝜃
𝑠𝑖𝑛2𝜃
1
(ii-1) factor due to grain orientation or crystal rotation
𝑠𝑖𝑛2𝜃
The factor is counted in powder method and in rotating crystal method
First the integrated intensity = ∫ 𝐼𝑑(2𝜃)
Imax
Integrated intensity = Imax∙B, where B is the width at 2
1
Imax ∝
sinθ
1
B∝
cosθ
1 1
Imax ∙ B ∝ ∝
sinθcosθ sin2θ
1
(a) Imax ∝
sinθ
When the reflecting planes make an angle θB with the incident beam, the
Bragg law is satisfied and the intensity diffracted in the direction 2θB is
maximum.
But, some are still diffracted in this direction when the angle of incident differs
slightly from θB due to the other crystals in the powder (or due to crystal
rotation)
→ such that θ1 = θB + ∆θ; θ2 = θB − ∆θ in the figure
The difference in path length for rays 1’ and 2’ is
𝛿1′ 2′ = 𝐴𝐷 − 𝐶𝐵 = 𝑎𝑐𝑜𝑠θ2 − 𝑎𝑐𝑜𝑠θ1
𝛿1′ 2′ = 𝑎[cos(θB − ∆θ) − cos(θB + ∆θ)]
𝛿1′ 2′ = 2 asin(∆θ) sinθB
𝛿1′ 2′ = 2a∆θsinθB
where we have used sin(∆θ)= ∆θ
The path difference at either end of the plane is N𝛿1′ 2′ since the distance
between two ends is Na as shown in the figure
Therefore, the maximum value of ∆θ, which allows the rays 1’ and 2’ detected
at the angle of 2θB , occurs at
N𝛿1′ 2′ = 𝜆
2N∆θsinθB = 𝜆
λ
∆θ =
2NasinθB
1
within the range of Δθ, we still obtain Imax at θB , hence Imax ∝
sinθ
Note that Δθ = 0 when N is infinite
1
(b) why B∝
cosθ
the width B increases at the thickness of the crystal decreases, as shown in the
figure in the next page
2𝜃2 −2𝜃1
B= = 𝜃2 − 𝜃1
2
write the path difference related to the total crystal thickness t
t=md, where d is the planar spacing and m+1 is the number of atomic layers.
At 𝜃 = 𝜃𝐵
2𝑑𝑠𝑖𝑛𝜃𝐵 = 𝜆
2𝑡𝑠𝑖𝑛𝜃𝐵 = 2𝑚𝑑𝑠𝑖𝑛𝜃𝐵 = 𝑚𝜆
At 𝜃 = 𝜃1
When the path difference in the atomic layers at top and bottom is 𝜆, the path
𝜆
difference at top and at the center is 2
The total phase difference in the crystal will be cancelled
In other words,
2𝑡𝑠𝑖𝑛𝜃1 = 𝑚𝜆 − 𝜆 = (𝑚 − 1)𝜆
similarly, at 𝜃 = 𝜃2
2𝑡𝑠𝑖𝑛𝜃2 = 𝑚𝜆 + 𝜆 = (𝑚 + 1)𝜆
Then
t(sinθ2 − sinθ1 ) = λ
θ1 +θ2 θ2 −θ1
2tcos( )sin( )= λ
2 2
θ2 −θ1
2tcosθB sin( )= λ
2
θ2 −θ1
Since is very small
2
θ2 −θ1
2tcosθB ( )= λ
2
λ
B=tcosθ
B
λ
B=mdcosθ
B
Therefore
1
B∝
cosθ
Note that B=0 when m is infinite.
(iii-1) cosθ factor dure to the number of crystal counted in the powder method
The number of crystal is not constant for a particular𝜃𝐵 even through the crystal
are oriented completely at random.
For the hkl reflection, the range of angle near the Braggle angle, over which
reflection is appreciable, is ∆θ
Assuming that ∆N is the number of crystals located in the circular band of width
r∆θ
π
∆N r∆θ ∙ 2πrsin(2 − θB )
=
N 4πr 2
∆N ∆θ ∙ cos(θB )
=
N 2
where N is the total number of crystal.
The number of grains satisfying the diffraction condition is proportional to cosθB .
In other words, more grains satisfying the diffraction condition at higher θB as
shown in the figure below.
1
(iii-2) factor due to the segment factor in the Debye-scherrer film
sin2𝜃𝐵
The film receives a great proportion of a diffraction cone when the reflection is
𝜋
in the forward or backward direction than it does near 2𝜃 =
2
The relative intensity per unit length is proportional to
1
2πRsin2𝜃𝐵
i.e. proportional to
1
sin2𝜃
Therefore, the Lorentz factor for the powder method is
1 1 cosθ 1
cosθ = 2
= 2
sin2θ sin2θ sin 2θ 4sin θcosθ
and for the rotating crystal method and diffractometer method is
1
sin2θ
(iv) Plot of polarization and Lorentz factors
α ≔ 0π, 0.001π. .0.5π
(1+cos(2α) cos(2α))
f(α) ≔
sin(α) sin(α)cos(α)
