ANALISIS DGN XRD

JURUSAN KIMIA FMIPA

UNIVERSITAS NEGERI SEMARANG
 Radiasi sinar-X untuk Pengukuran Difraksi Dihasilkan oleh
Tabung Tertutup Atau Tabung Anoda Berputar
H2O In H2O Out
• Tabung Sinar-X Tertutup Bekerja pada
daya 1,8 – 3 kW
• Tabung Anoda Berputar Menghasilkan
Jauh Lebih Banyak fluks karena
bekerja pada dayaa 9 – 18 kW Be
Cu ANODE
Be
window
– Anoda yang berputar pada 6000 rpm window

membantu mendistribusikan panas e-

berlebihan pada target sehingga XRAYS XRAYS
memungkinkan penggunaan daya FILAMENT
(cathode)
yang lebih besar tanpa merusak target metal

• Kedua sumber sinar-X tersebut

menghasilkan sinar-X dengan glass

menembak anoda dengan elektron (vacuum) (vacuum)

dari filamen Tungsten.

– Target harus didinginkan dengan air
– Target dan filamen harus dalam ruang
vakum

AC CURRENT
 Panjang Gelombang Sinar-X Ditentukan oleh
Anoda Sumber Sinar-X
• 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.

K
L
M
Wavelengths for X-Radiation are Sometimes Updated
Copper Bearden Holzer et al. Cobalt Bearden Holzer et al.
Anodes (1967) (1997) Anodes (1967) (1997)
Cu K1 1.54056Å 1.540598 Å Co K1 1.788965Å 1.789010 Å
Cu K2 1.54439Å 1.544426 Å Co K2 1.792850Å 1.792900 Å
Cu K 1.39220Å 1.392250 Å Co K 1.62079Å 1.620830 Å

Molybdenum Chromium
Anodes Anodes
Mo K1 0.709300Å 0.709319 Å Cr K1 2.28970Å 2.289760 Å
Mo K2 0.713590Å 0.713609 Å Cr K2 2.293606Å 2.293663 Å
Mo K 0.632288Å 0.632305 Å Cr K 2.08487Å 2.084920 Å

• 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 Hölzer et al. Phys. Rev. A 56 (1997)
• Has your XRD analysis software been updated?
One by-product of the beam divergence is that the length of
the beam illuminating the sample becomes smaller as the
incident angle becomes larger.
• The length of the incident
beam is determined by the
divergence slit, goniometer
radius, and incident angle.
• This should be considered 185mm Radius Goniometer, XRPD
when choosing a divergence 40.00
slits size:
– if the divergence slit is too 35.00
L
large, the beam may be I
e 30.00
significantly longer than your r
n
sample at low angles r
g 25.00
a 2°DS
– if the slit is too small, you may d
t
not get enough intensity from i
h 20.00
your sample at higher angles a
15.00
– Appendix A in the SOP 1°DS
(

t
m
contains a guide to help you e
m 10.00
choose a slit size. d 0.5°DS
• The width of the beam is
)

5.00
0.15°DS
constant: 12mm for the Rigaku 0.00
RU300. 0 20 40 60 80 100
2Theta (deg)
 Material kristalin dicirikan oleh pengaturan atom-
atom yang berubah secara periodik
Bidang (200) Bidang (220)
atom-atom NaCl atom-atom NaCl

• Unit sel adalah dasar pengulangan unit yang mendefinisikan suatu

kristal
• Bidang-bidang paralel yang memotong unit sel digunakan untuk
menetapkan arah dan jarak dalam kristal.
– Bidang-bidang ini dalam kristalografi disebut indeks Miller..
 Atom-atom dalam kristal yang tersusun secara
periodik tersebar luas sehingga dapat mendifraksi
cahaya
• 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.
 X-Ray Powder Diffraction (XRPD) uses information about
the position, intensity, width, and shape of diffraction peaks
in a pattern from a polycrystalline sample.

The x-axis, 2theta, corresponds to the angular position of the detector

that rotates around the sample.
 Bragg’s law is a simplistic model to understand
what conditions are required for diffraction.

  2d hkl sin   

d hkl d hkl
• For parallel planes of atoms, with a space d hkl between the planes, constructive
interference only occurs when Bragg’s law is satisfied.
– In our diffractometers, the X-ray wavelength  is fixed.
– Consequently, a family of planes produces a diffraction peak only at a specific angle .
– Additionally, the plane normal must be parallel to the diffraction vector
• Plane normal: the direction perpendicular to a plane of atoms
• Diffraction vector: the vector that bisects the angle between the incident and diffracted beam
• The space between diffracting planes of atoms determines peak positions.
• The peak intensity is determined by what atoms are in the diffracting plane.
ANATOMI DIFRAKTOGRAM XRD
 Background

Sinyal yang diinginkan

Noise
 It’s a single crystal
200

220

111 222
311

2

At 27.42 °2, Bragg’s law The (200) planes would diffract at 31.82 The (222) planes are parallel to the
fulfilled for the (111) planes, °2; however, they are not properly (111) planes.
producing a diffraction peak. aligned to produce a diffraction peak
 A random polycrystalline sample that contains thousands of
crystallites should exhibit all possible diffraction peaks

200

220

111 222
311

2 2 2

• 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).
• Basic assumptions of powder diffraction are that for every set of planes there is an equal number
of crystallites that will diffract and that there is a statistically relevant number of crystallites, not
just one or two.
Hubungan antara tekstur tekanan pada padatan
dengan pola difraktogram XRD
 PENETAPAN PARAMETER KRISTAL
METHOD 1:
– Diffraction will occur when Bragg law is satisfied:

  2d sin 
– The interplanar spacing d for a cubic material is given by:

a
d hkl 
h2  k 2  l 2
– Combining the above equations results in:

2
a 
d2  2 2 2

h k l 4 sin 2 

1-15
– Which gives:

h2  k 2  l 2 
2
Sin 2 
4a 2
– Since 2 / 4a2 is constant, sin 2 is proportional to (h2 + k2 + l2),
– As  increases, planes with higher Miller indices will diffract.
– Writing the above equation for two different planes and diving by the minimum
plane, we get:

sin 2 1 h12  k12  l12

2

sin  2 h22  k 22  l 22

1-16
Example: indexing of Aluminium diffraction pattern by method 1

1-17
Example: indexing of Aluminium diffraction pattern by method 1

1. Identify the peaks

2. Determine sin2
3. Calculate the ratio sin2 / sin2min and multiply by the appropriate
integers (1, 2, or 3)
4. Select the result from step (3) that yields h2 + k2 + l2 as an integer
5. Compare results with the sequences of h2 + k2 + l2 values to
identify the Bravais lattice
6. Calculate lattice parameter.

1-18
1-19
1-20
1-21
• The bravais lattice can be identified by noting the systematic
presence (or absence) of reflections in the diffraction pattern.

• The Table below illustrates the selection rules for cubic

lattices.

• According to these rules, the (h2 + k2 + l2) values for the

different cubic lattices follow the sequence:

Simple cubic : 1,2,3,4,5,6,8,9,10,11,12,13,14,16,….

BCC : 2,4,6,8,10,12,14,16,18,...
FCC : 3,4,8,11,12,16,19,20,24,27,32,…

1-22
 Bravais lattice Reflections present for Reflections absent for

Primitive (simple cubic) All None

Body Centered Cubic h + k + l = even h + k + l = odd

(BCC)

Face Centered Cubic h, k, l = unmixed (all h, k, l = mixed

(FCC) even or all odd)

1-23
CALCULATION OF THE LATTICE PARAMETER
– The lattice parameter,a, can be calculated from:

Sin 2 
2
4a 2
h2  k 2  l 2 

– Rearranging gives

 2  2
2
a   2 

 h  k2  l2 
 4 sin  

1-24
METHOD 2:

– This method can be used to index the diffraction pattern from materials with a
cubic structure. From:

h2  k 2  l 2 
2
Sin 2 
4a 2
– Since 2 / 4a2 is constant for any pattern and which we will call A, we can write:

2
sin   A h  k  l  2 2 2

1-25
– In a cubic system, the possible (h2 + k2 + l2) values are: 1, 2, 3, 4, 5, 6, 8,
…. (even though all may not be present in every type of cubic lattice).

– The observed sin2 values for all peaks in the pattern are therefore
divided by the integers 1, 2, 3, 4, 5, 6, 8, to obtain a common quotient,
which is the value of A, corresponding to (h2 + k2 + l2) =1.

– We can then calculate the lattice parameter from the value of A using the
relationship:

2 
A 2
or a 
4a 2 A

1-26
Note that 0.1448 is also common in 1, 2, 3, 4, 5, 6, BUT absent in 8

It can only be FCC 1-27

Smaller Crystals Produce Broader XRD Peaks
 Scherrer’s Formula

K 
t
B  cos  B

t = thickness of crystallite
K = constant dependent on crystallite shape (0.89)
 = x-ray wavelength
B = FWHM (full width at half max) or integral breadth
B = Bragg Angle
 PREPARASI N - DOPED TiO2
Metode - I
50 ml of 15 % TiCl3 +
50 ml of 0.5 M Na2S

Ti2S3 pH was adjusted

to 8.5 by slow
addition of ~10
ml liq NH3
(NH4)XTiSX

Calcined for 4 h in air at 400, 500 and 600 ºC

, Chem. Mater., 17 (2005) 6349

 PREPARASI N - DOPED TiO2
Metode- II
N N N N
CHO i
Ethanol,RT Ti (O Pr)4,DCM Ti
2 + H2N NH2 OH HO O O
OH RT PrOi OiPr

Ti-Salen complex
Titanium−Salen Complex

Vacuum heating at 400 ºC, 6 h

N−TiO2

Calcination in N2 atmosphere for

2 h @ 400 ºC then in air for 2 h @ 400 ºC Int. J. Nanoscience, 6 (2007) 137
 PREPARASI N - DOPED TiO2
Metode- III

Melamine
( 2:1 ethanol: water mixture)

Ti(iOPr)4 in ethanol
3:1 molar ratio
Stirred for 24 h, then
kept for 4 days

Ti-Melamine
sol-
gel
Washed with hot water,
calcined at 400, 500, 600, 700 oC

Appl Catal B, 74 (2007) 308

 Scherrer’s Formula
What is B?

Peak
B = (2θ High) – (2θ Low)
2θ low 2θ high
B is the difference in angles
at half max Noise
 When to Use Scherrer’s Formula ?
• Crystallite size <1000 Å
• Peak broadening by other factors
– Causes of broadening
• Size
• Strain
• Instrument
– If breadth consistent for each peak then assured
broadening due to crystallite size
• K depends on definition of t and B
• Within 20%-30% accuracy at best
Sherrer’s Formula References
Corman, D. Scherrer’s Formula: Using XRD to Determine Average Diameter of
Nanocrystals.
 Data Analysis

• Plot the data (2θ vs. Counts)

• Determine the Bragg Angles for the peaks
• Calculate d and a for each peak
• Apply Scherrer’s Formula to the peaks
Bragg Example
 Bragg Example

d = λ / (2 Sin θB) λ = 1.54 Ǻ

= 1.54 Ǻ / ( 2 * Sin ( 38.3 / 2 ) )
= 2.35 Ǻ
 Scherrer’s Example
Au Foil

10000

9000

8000

98.25 (400)
7000

6000
Counts

5000

4000

3000

2000

1000

0
95 95.5 96 96.5 97 97.5 98 98.5 99 99.5 100 100.5 101 101.5 102
2 Theta
 Scherrer’s Example
0.89  
t
B  cos  B

t = 0.89*λ / (B Cos θB) λ = 1.54 Ǻ

= 0.89*1.54 Ǻ / ( 0.00174 * Cos (98.25/ 2 ) )
= 1200 Ǻ

B = (98.3 - 98.2)*π/180 = 0.00174