XRD 1
XRD 1
XRD 1
Why XRD
1
Characterization Techniques
1. XRD
English physicists Sir W.H. Bragg and his son Sir W.L. Bragg developed a relationship in 1913 to explain why the
cleavage faces of crystals appear to reflect X-ray beams at certain angles of incidence (theta, q). The variable d is the
distance between atomic layers in a crystal, and the variable lambda λ is the wavelength of the incident X-ray beam;
n is an integer. This observation is an example of X-ray wave interference commonly known as X-ray diffraction
(XRD), and was direct evidence for the periodic atomic structure of crystals postulated for several centuries.
A.W. Hull 1919 “every crystalline substance gives a pattern; the same substance always gives the same
pattern; and in a mixture of substances, each produces its pattern independently of the others. “
2
Characterization Techniques
Production of X-rays
Cross section of sealed-off filament X-ray tube
6
Characterization Techniques
7
Characterization Techniques
8
Characterization Techniques
9
Characterization Techniques
10
Characterization Techniques
11
Characterization Techniques
11
Characterization Techniques
17
Characterization Techniques
18
Characterization Techniques
21
Characterization Techniques
22
Characterization Techniques
23
Characterization Techniques
Scherrer formula
Scherrer (1918) first observed that small crystallite size could give rise to
peak broadening. He derived a well-known equation for relating the
crystallite size to the peak width, which is called the Scherrer formula:
t = Kλ/(β cosθ)
where K is the shape factor, λ is the x-ray wavelength, β is the line
broadening at half the maximum intensity (FWHM) radians, and θ is the
bragg angle. τ is the mean size of the ordered (crystalline) domains,
which may be smaller or equal to the grain size
XRD Crystallite Size Calculator using Scherer Formula
λ =1.542 A0
24
Characterization Techniques
25
JCDPS Card Characterization Techniques
26
Characterization Techniques
27
Characterization Techniques
(i) c
6- 8
2- 4
4 12
-
-
1
Reciprocals Reciprocals =0
28
Characterization Techniques
29
Characterization Techniques
30
Characterization Techniques
31
Characterization Techniques
(ii) (iii)
. .
32
Characterization Techniques
33
Characterization Techniques
Nanoparticles
Materials letters 61 2007, 4094-4096
30
Characterization Techniques
Fig. 2 XRD results of (a) bare GaN and (b) single-crystalline rutileTiO2 nanorods array on GaN.
Fig. 5 XRD patterns of the SnO2 samples prepared using precursor solutions with
different pH values (fixed at T = 190 °C, t = 48 h): (a) standard data file of a
SnO2 crystal, (b) pH = 5, (c) pH = 7–8 and (d) pH = 12.
38
Characterization Techniques
Detector
X-ray
tube
ω θ 2
θ
• The incident angle, ω , is defined between the X-ray source and the sample.
• The diffracted angle, 2θ , is defined between the incident beam and the detector angle.
• The incident angle ω is always ½ of the detector angle 2θ .
• In a θ :2θ instrument (e.g. Rigaku RU300), the tube is fixed, the sample rotates at θ °/min and the detector
rotates at 2θ °/min.
• In a θ :θ instrument (e.g. PANalytical X’Pert Pro), the sample is fixed and the tube rotates at a rate -θ °/min and
the detector rotates at a rate of θ °/min. 12
Characterization Techniques
A single crystal specimen in a Bragg-Brentano diffractometer
would produce only one family of peaks in the diffraction
pattern.
2
θ
2θ 2θ 2θ
• 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
14
crystallites, not just one or two.
https://www.mdpi.com/2076-3417/11/2/526
X-ray diffraction (XRD) spectra of the platinum-based powder (A), sintered material (B) and mixture (1:1 by weight) of
the platinum-based powder with ZnO powder, used as a crystalline internal standard (C). The spectra were acquired by
using Cu Kα radiation. The lines corresponding to Al2O3 observed in the spectrum of the sintered material are due to
the contribution of alumina substrate, used for the deposition of the formulated ink.
https://www.sciencedirect.com/science/article/pii/S223878542031454X?via%3Dihub
* * * * * * * * *
*
NiCo-LDH/BiVO4
* * * * * * * * *
* BiVO4
* * * * * * * * *
Bi2O3
+ + + +
10 20 30 40 50 60 70
2θ / degree