Crystallography and Diffraction Techniques

Characterization of Solids
How to characterize solid:
Diffraction, Microscopy, Spectroscopic techniques X-ray diffraction, neutron diffraction and electron diffraction

Structure:
1. Single vs. Polycrystalline structure 2. Crystal structure (unit cell, dimensions) 3. Crystal defect (vs. molecular structure) 4. Impurities (concentration and distribution) 5. Surface structure (compositional inhomogeneities)

Outline
Generation of X-ray X-ray wavelength Diffraction of X-ray Diffraction methods Qualitative identification of compounds Scatterings of X-ray Determination of X-ray Structure Electron and neutron diffraction

Generation of X-ray

X-ray are produced when high energy charged particles (e.g. 30 kV) collide with matter. Only ~1% electron can produce x-ray, the others lost as heat (anode need efficient cooling)

Incident electron has sufficient energy to remove 1s electron The place will be refilled by outer shell electron, and give X-ray radiation Fixed transition energy

X-ray Wavelength

White radiation

Fixed transition energy (Copper metal as target): 2p 3p 1s 1s Cu K Cu K 1.5418 1.3922

Moseleys Law
Cut off

Peak intensity rate of transition

= K/(Z-)2

Monochromatic X-ray Radiation

Absorption of X-rays on passing through materials depends on the atomic weight of the elements Be is the best window, while Pb is a good shielding materials White radiation and unwanted Kb lines can be filtered How to choose X-ray filter?

Diffraction of Light
Diffraction of light by an optical grating

AB = asin Separation of lines should be slightly larger than the wavelength of light In phase: AB = , 2, 3,. n n = asin

Diffraction of X-ray
Crystal with repeating structure Optical grating

Interatomic distance ~2-3, which is slightly larger than the wavelength of X-ray e.g. Cu K 1D optical grating: n = a sin 3D crystal structure: n = a1 sin1 n = a2 sin2 n = a3 sin3 Laue equations

Braggs Law
Regard crystals as built up in layers or planes such that each acts as a semi-transparent mirror

The angle of reflection is equal to the angle of incidence

X-ray Diffraction Method

1. Radiation: monochromatic or of variable 2. Sample: single crystal, powder or a solid piece 3. Detector: radiation counter or photographic film

X-ray Diffractometers
Single crystal X-ray diffractometer Powder XRD

Debye-Scherrer Method
Sample: Powder Detector: Film

S/2R = 4/360

Each set of planes (unique d-spacing) gives its own cone of radiation. d-spacing can be obtained.

Focusing of X-rays
Intense X-ray beam exposure time
Theorem of a circle:

improvement in resolution and reduced

Crystal monochromator:

Large single crystal, curved Highly monochromatic radiation Intense convergent X-ray beam

Guinier Focusing Camera

The film is place in a cassette which is in the form of a short cylinder and lies on the circle ABC

primary beam

sample

crystal monochromator

Film (in the scale of 2):

Intensity : degree of blackness are seen

Accurate d-spacing can be obtained!

Undiffracted beam A

Powder Diffractometer
1. Geiger counter scans a range of 2 value (10-80 degree) at constant angular velocity 2. Intensities taken either peak heights or peak area 3. Most intense peak gives a intensity of 100 (rest are scaled according) 4. Internal standard with known d-spacing e.g. KCl

Qualitative Identification of Compounds

1. The existence of crystalline compounds or phases (not chemical composition) 2. Peak position (d-spacing) and intensity (pattern) 3. Each crystalline phase has a characteristic powder pattern which can be used as a fingerprint for identification process

Powder Diffraction File (International Centre for Diffraction Data, USA)

Fingerprint Powder Pattern

What factors determine the powder pattern: The size and shape of the unit cell The atomic number and position of the atom in the cell

High symmetry (cubic) structure may have similar pattern

Scattering of X-ray by Electrons

1. Elastic collision between the electromagnetic wave and the electron

Coherent, without change of wavelength Thomson equation: Ip (1 + cos22) 2. Inelastic collision in that X-ray lose some of their energy on impact (Compton scattering) Incoherent, longer wavelength

X-ray scattered by an atom are the resultant of the waves scattered by each electron in the atom

Scattering of X-ray by a Crystal

Systematic absences Arises if the lattice type is non-primitive or if elements of space symmetry are present

Plane (100) Plane (200)

no intensity (diffracted beam cancel completely) strong intensity (all atom lie on the plane)

The diffracted beams must be out of phase and of the same amplitude

Rules for Systematic Absences

Phase Difference
Plane (100) Phase difference between A and B = A and C = 2x Plane (200) Phase difference between A and B = 2 A and C = 2*2x Plane (h00) = 2hx Indices of reflection and fractional coordinates

Phase Difference in 3D Crystal Structure

= 2 (hx + ky + lz) For example: -Fe fcc structure Fractional coordinates: 0,0,0 ,,0 ,0, 0,, 0, (h+k), (h+l), (k+l) Reflection to be observed when h,k,l all even or all odd For example: a-Fe bcc structure 0,0,0 , ,

0, (h+k+l) Reflection to be observed when h+k+l = 2n

Structure Factor (Fhkl)

Diffracted wave of each atom (j): Complex notation: Fj = fj sin(wt j) Fj = fj(cosj + isinj)

Summation over the j atoms in the unit cell: Structure factor: Fhkl = fj(cosj + isinj)

Intensity is obtained from the summation of the individual sine wave I f j2 Intensity of diffracted beam Ihkl Fhkl 2 = [fj(cosj + isinj)] [fj(cosj + isinj)] = (fjcosj)2 + (fjsinj)2 The structure factor and intensity of any (hkl) reflection may be calculated from a knowledge of the atomic coordinates in the unit cell

Calculation of Structure Factor

For example: CaF2 (fluorite structure) Ca F 0,0,0 ,, ,, , ,0 ,, ,, ,0, ,, ,, 0, , ,, ,,

Fhkl = fj(cosj + isinj) F202 = 4fCa + 8fF d-spacing = 1.929 (a = 5.464 ) = 23.6, sin / =0.259, = 1.5418 Scattering factor fCa = 12.65, and fF = 5.8 F202 = 97

Calculated structure factor Fcalhkl

R-factors
Residual factor is used to measure the agreement between the individual, scaled Fhklcalc and Fhklobs Fhklobs is obtained from the experimental intensities (Fhklobs = Icorr)

R=

Fobs - Fcalc Fobs

R should be less than 0.1 and 0.2 if the calculated structure is correct

Structure Determination
Intensities of x-ray diffracted beam Electron density map

Coordination variables

Structure refinement (position and thermal vibration factors)

Peak height is proportional to the number of electrons possessed by the atom Difficult to locate light atom e.g. hydrogen

Common structure determination methods: 1. The Patterson method 2. Fourier methods 3. Direct methods

Electron Diffraction
Wavelength is related to velocity, around 0.04 in conventional Electron Microscopy Interact strongly with matter, intense diffraction pattern can be obtain from small samples Secondary diffraction occurs (extra reflections and unreliable intensity) Unit cell and space group Surface polarity Small amount of impurity phases

Neutron Diffraction
Continuous spectrum of radiation (need crystal monochromator) Neutrons that are used for diffraction have wavelength of the order 0.5 to 3 (depends on velocity) Low intensity, large sample size Atomic nuclei (vs. extranuclear electron) are responsible for scattering Crystal structure determination
Locate light atoms Distinguish atoms that have similar Xray scattering

Neutron Diffraction
Neutron (spin = ) posses magnetic dipole moment Interact with unpaired electrons and diffracted by both atomic nuclei and unpaired electrons Magnetic structure analysis

NiO superstructure MnO structure