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(301)

(310)

Intensity

(611) (321)

(600) (411) (002)

(200) (110) (400)

2 degrees

CHARACTERIZATION OF THE STRUCTURE OF SOLIDS

Single crystal

Powder

Principles of x-ray diffraction

X-rays are passed through a crystalline material and the patterns produced give

information of size and shape of the unit cell

X-rays passing through a crystal will be bent at various angles: this process is called

diffraction

X-rays interact with electrons in matter, i.e. are scattered by the electron clouds of

atoms

The angles at which x-rays are diffracted depends on the distance between adjacent

layers of atoms or ions.

Scattering of x-rays by crystallographic planes

We need to consider how x-rays are diffracted by parallel crystallographic planes

lattice planes d

atoms on

lattice planes

X-rays diffracted in phase will give a signal. “In phase” means that the peak of one

wave matches the peak of the following wave

A single monochromatic wave (of any type) is incident on aligned planes of lattice

points, with separation d, at angle θ,

between the ray that gets reflected

along AC' and the ray that gets

transmitted, then reflected, along AB

and BC respectively. This path

difference is:

The two separate waves will arrive at a point with the same phase, and hence

undergo constructive interference, if and only if this path difference is equal to any

integer value of the wavelength

According to the 2θ deviation, the phase shift causes:

n = 2dsin

between the planes in the atomic lattice, and θ is the angle between the incident

ray and the scattering planes.

A single monochromatic wave (of any type) is incident on aligned planes of lattice

points, with separation d, at angle θ,

AB = BC = d/sin

AC = 2d/tan

AC' = (2d/sin)cos2

2d/sin(1-cos2) = n

2dsin = n

Inter-Planar Spacing, dhkl, and Miller Indices

to the same family (h,k,l) is denoted (dhkl)

Distances between planes defined by the same set of Miller indices are

unique for each material

dhkl

d'h’k’l’

Inter-Planar Spacing, dhkl, and Miller Indices

to the same family (h,k,l) is denoted (dhkl)

Distances between planes defined by the same set of Miller indices are

unique for each material

dhkl

The lattice parameters a, b, c of a unit cell can then be calculated

geometrically and depends on the crystal system

parameters and

Miller indices

Cubic 1 h2 k 2 l 2

d 2

a2

Tetragonal 1 h2 k 2 l 2

2

d2 a2 c

Orthorhombic 1 h2 k 2 l 2

d 2 a 2 b2 c2

The expressions for the remaining crystal systems are more complex

ICDD

Systematic Absences

Permitted Reflections

(220), (300), (221) ………

BCC (110), (200), (211), (220), (310), (222)….

FCC (111), (200), (220), (311)…..

Structure Factor

Fhkl f n e

N

2 i ( hun kvn lwn )

Intensity of the diffracted beam |F|2

1

− h,k,l : indices of the diffraction plane under consideration

− u,v,w : co-ordinates of the atoms in the lattice

− N : number of atoms

− fn : scattering factor of a particular type of atom

odd or all even

Intensity of diffracted beam

The factors governing diffracted intensity in the powder method is similar to the one

of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a

powder pattern:

(2) structure factor

(3) multiplicity factor

(4) Lorentz factor

(5) absorption factor

(6) temperature factor

given by:

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Structure Factor

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Fhkl f n e

N

2i ( hu n kvn lwn )

n i

To calculate F is necessary to account for the scattering waves generate for each

individual atoms of the unit cell and the scattering waves resulting from the

arrangement of the same in the diffracting planes

Structure Factor (atoms scattering)

the coherent scattering, not from an isolated atom, but from all the atoms making up

the crystal, means that the scattered radiation is severely limited to certain definite

directions and is now referred to a set of diffracted beams.

2’ (h00)

2 '1' 2d h 00 sin

1’

M

A C

a

d h 00 AC

h

N

1

2

a

x

Atom A is radiated by beam 1, at an angle , in such a way there is coherent

diffraction at h00, meaning that Bragg’s law is fulfill by the interplanar distance 2’1’

Structure Factor (atoms scattering)

How is this reflection affected by x-rays scattered in the same direction by atom B,

located at a distance x from A?

and ray 1', 3’1’ will be less than ;

1’

if the path difference is , then the

M phase difference (radian) is:

R

3'1' 2hx

A B C (2 2hu

a

S Where:

N

1

x

3 2 3'1'

a a h

x

If the same analysis is done for (0h0) and (00h): 2 hu kv lw

Structure Factor (plane scattering)

Not only beam interaction with atoms may change de direction of diffraction but also

affect the amplitude (electric field) of the diffracted beam; the electric field intensity is

defined as:

same frequency v and

therefore same

wavelength , but

different in amplitude A

E2 A2 sin 2t 2

and in phase .

E1 A1 sin 2t

sine wave, but of different amplitude and phase.

E1 E2 E3

Structure Factor (plane scattering)

Being E3 a sine function it may be expressed by either identities:

Therefore

Ae i A cos Ai sin

Since the intensity of a wave is proportional to the square of its amplitude,

we now need an expression for A2

Ae i 2

Ae i Ae i A2

The term A2 is the wave amplitude due to the interaction of the incident beam with

the atom in the plane, is value is given by (atomic scattering factor)

Intensity of diffracted beam

The factors governing diffracted intensity in the powder method is similar to the one

of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a

powder pattern:

(2) structure factor

(3) multiplicity factor

(4) Lorentz factor

(5) absorption factor

(6) temperature factor

given by:

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Structure Factor and Symmetry Absences

a) Primitive cell

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Fhkl f n e

N

2i ( hu n kvn lwn )

000

n i

F fee 2i ( 0 )

f

F f

2 2

F2 is thus independent of fn and I is the same e 2i e 4i e 6i 1

for all reflections.

e i e i 2 cos x

Structure Factor and Symmetry Absences

Fhkl f n e

b) Base centered N

2i ( hu n kvn lwn )

n i

F f ee 2i ( 0 )

fee 2i ( h 2 k 2 )

000

½½0 F f 1 e i ( hk )

e 2i e 4i e 6i 1

F2 0 F 4f

2 2

e i e i 2 cos x

Structure Factor and Symmetry Absences

c) Body centered

N

n i

½½½

000

F f 1 e i ( hk l )

F 0

2

F2 4 f 2 e 2i e 4i e 6i 1

e i e i 2 cos x

Structure Factor and Symmetry Absences

d) Face centered

Fhkl f n e

0½½ N

2i ( hu n kvn lwn )

½0½

000 n i

½½0

F f ee 2i ( 0 )

fee 2i ( h 2 k 2 )

fee 2i ( k 2 l 2 )

fee 2i ( h 2 l 2 )

F f 1 e i (hk )

e i ( k l )

e i ( hl )

(h,k), (h,l), (k,l) mixed (h,k), (h,l), (k,l) unmixed ei e 3i e 5i 1

1

F 0, F 0

e e e

F 4 f , F 2 16 f

2i 4i 6i

2 2

e i e i 2 cos x

Structure Factor calculations

(NaCl)

Na Cl

000 ½½½

½½0 00½

½0½ 0½0

0½ ½ ½00

f Cl e 2i ( 0 ) f Cl e 2i ( h 2 k 2l / 2 ) f Cl e 2i (l 2 ) f Cl e 2i ( k 2 ) f Cl e 2i ( h 2 )

F f Na (1 e i ( h k ) fe i(k l )

fe i(h l )

f Cl 1 fe i(h k l )

fe il

fe ik

fe ih

Structure Factor calculations

(NaCl)

f Cl ei ( h k l ) 1 ei ( h k ) ei ( h l ) ei ( k l )

F 1 ei(hk) ei(kl) ei(hl ) fNa fClei(hkl)

F 0 F 0

F 4 f

2

mixed

unmixed Na f Cl e i ( h k l )

F 4 f Na f Cl

(h+k+l) even

F 4 f Na f Cl

(h+k+l) odd

F 16 f Na f Cl F 16 f Na f Cl

2 2 2 2

Intensity of diffracted beam

The factors governing diffracted intensity in the powder method is similar to the one

of monochromatic radiation.

Essentially there are six affecting the relative intensity of the diffraction lines on a

powder pattern:

(2) structure factor

(3) multiplicity factor

(4) Lorentz factor

(5) absorption factor

(6) temperature factor

given by:

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Multiplicity Factor

same d and F2

Intensity of diffracted beam

The factors governing diffracted intensity in the powder method is similar to the one

of monochromatic radiation.

powder pattern:

(2) structure factor

(3) multiplicity factor

(4) Lorentz factor

(5) absorption factor

(6) temperature factor

given by:

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Lorentz Polarization Factor

particular cone of reflected rays.

1 cos 2 2

LPF

sin cos

Intensity of diffracted beam

The factors governing diffracted intensity in the powder method is similar to the one

of monochromatic radiation.

powder pattern:

(2) structure factor

(3) multiplicity factor

(4) Lorentz factor

(5) absorption factor

(6) temperature factor

given by:

1 cos 2 2 2 M

I F p 2 e

2

sin cos

Temperature factor

f f 0e M

For cubic crystal structures where

x

A

x sin

x 4

x m

6h T 2

M T N

mk 6h T 11500T

mk

A

weight, N is Avogadro’s number, h and k are Plank’s and Boltzmann’s

constants

Intensity calculation for Cu (FCC)

Equipment parameter (nm)

x

T

1 cos 2 2 2 M

I F p 2 e

2

tables

Fhkl f n e

x sin

x

6 h T

2

2

N

1 cos 2 2 e mk 4

2i ( hu n kvn lwn )

LPF

From tables

sin cos

n i From tables

Tables

Intensity calculation for Cu

Smaller Crystals Produce Broader XRD Peaks

Scherrer’s Formula

K

t

B cosB

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

Scherrer’s Formula

What is B?

Peak

2θ low 2θ high

B is the difference in

angles at half max Noise

When to Use Scherrer’s Formula

• 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.

Remember, Crystallite Size is

Different than Particle Size

• A particle may be made up of several different

crystallites

• Crystallite size often matches grain size, but there are

exceptions

Lattice Strain

do

No Strain 2

Uniform Strain

d strain 2

Non-uniform Strain

2

d

Broadeing b 2 2 tan

d

Typical artifacts and

mistakes on XRD

operation and analysis

1. Irradiated area and

penetration depth

Slit Settings

Slit Settings, effect on the XRD

profile

How to avoid irradiated area problems, sample

preparation

2. Equipment geometry

3. Sample Preparation

(Common Mistakes and Their Problems)

• Z-Displacements

– Sample height matters

– Causes peaks to shift

• Sample orientation of single crystals

– Affects which peaks are observed

• Inducing texture in powder samples

– Causes peak integrated intensities to vary

Z-Displacements

Detector

011

θ

Disp 2θ

110

111

200

002

be at the correct height

Z-Displacements vs. Change in Lattice Parameter

• Lattice Parameters Strain/Composition?

– a=4.0215 Å a=4.07A

– c=4.1100 Å c=4.16A

111 002/200

Z-Displaced Fit

Disp.=1.5mm

Disp

and differentiable from changes in lattice parameter

Sample Preparation

Orientations Matter in Single Crystals

(a big piece of rock salt)

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 (111)

fulfilled for the (111) planes, °2; however, they are not properly planes.

producing a diffraction peak. aligned to produce a diffraction peak

For phase identification you want a random powder

(polycrystalline) sample

200

220

111 222

311

2 2 2

• When thousands of crystallites are sampled, for every set of planes, there will be a small

percentage of crystallites that are properly oriented to diffract

• All possible diffraction peaks should be exhibited

• Their intensities should match the powder diffraction file

Sample Preparation

Sample

Preparing a powder specimen

• An ideal powder sample should have many crystallites in random

orientations

– the distribution of orientations should be smooth and equally distributed

amongst all orientations

• If the crystallites in a sample are very large, there will not be a

smooth distribution of crystal orientations. You will not get a powder

average diffraction pattern.

– crystallites should be <10mm in size to get good powder statistics

• Large crystallite sizes and non-random crystallite orientations both

lead to peak intensity variation

– the measured diffraction pattern will not agree with that expected from

an ideal powder

– the measured diffraction pattern will not agree with reference patterns in

the Powder Diffraction File (PDF) database

Texture in Samples

• Common Occurrences • How to Prevent

– Plastically deformed metals – Grind samples into fine

(cold rolled) powders

– Powders with particle – Unfortunately you can’t or

shapes related to their don’t want to do this to

crystal structure many samples.

• Particular planes form the faces

• Elongated in particular

directions (Plates, needles,

acicular,cubes, etc.)

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