PRECISE LATTICE

PARAMETER

PRESENTED BY,
JEEVANANTHAM.K
CONTENT

 XRD PRINCIPLE
 Precise lattice parameter
 Peak position of BaTio3
 Variation of sinθ vs θ
 Systematic error
 Procedure to measure the precise lattice parameter
 Application
XRD PRINCIPLE

 X ray diffraction is based on constructive interference of

monochromatic x rays and a crystalline sample.
 These x rays are generated by a cathode ray tube , collimated to
concentrate , and directed towards the sample.
 The interaction of the incident rays with the sample produces
constructive interference (and a diffracted ray) when condition
satisfy bragg’s law (nλ=2d sin θ).
 PRECISE LATTICE PARAMETER
 Lattice parameter measurements are used in many situation to characterize
material.
 For example , knowledge of the lattice parameter can provide information on the
thermal properties of a material, an indirect method to determine the composition
in a solid solution , a measure of the strain state, or an analysis of the defect
structure.
 Therefore , it is important to determine the lattice structure with the highest
precision.
 X ray diffraction can provide such information to an accuracy of several
significant figures if care is taken during the experiment and subsequent analysis .
CONT…
 If the crystal structure of a material is known , then the diffraction pattern can be
indexed rather easily.
 However ,in order to use this indexing to compute a precise value of lattice
parameter, careful analysis of the data is required.
 a 2 = d 2 /(h 2 + k 2 + l 2 )
 h,k,l are the miller indices.
 If there were no systematic errors in the positions of the diffraction peaks, then
there would be only random errors in Applications the individual calculations of
the lattice parameter.
PEAK POSITION OF IRON OXIDE
VARIATION OF SINθ WITH θ
CONT..

 The error in the calculation of lattice parameter decreases , with

increasing angle hence the high angle should be used for lattice
parameter calculation.
 Usually at low angle these peaks are merged ( seen as a single peak)
and at high angle these peaks are resolved.
 The error in the calculation of lattice parameter decreases with
increasing angle.
SYSTEMATIC ERROR
 SYSTEMATIC ERRORS FALL INTO THREE CATEGORIES:
 The first is the lattice parameter itself, which if incorrect will result in an error
pattern.
 Once the systematic errors due to the experimental setup have been removed,
then the lattice parameters will be computed to provide a least squares fit.
 The principal experimental errors are due to the zero-offset and sample
displacement.
 The zero-offset occurs when the zero angle position of the diffractometer is off
slightly. Such errors can generally be controlled during the alignment.
Nonetheless, small zero offsets will be present.
SAMPLE DISPLACEMENT

 The second type of error, sample displacement, is more important

and is due to small vertical displacements of the sample off the
rotation axis of the diffractometer.
 One way for this error to creep in is for dust particles to collect on
the sample holder, causing a displacement of tens of microns.
 This small error is sufficient to shift the entire diffraction pattern by
approximately 0.1 degrees.
OFF CENTERING OF THE SPECIMEN
 Computational models of the zero offset and sample displacement errors have
been derived.
 Typically, a least squares refinement is run in which the lattice parameters and
one of the mechanical errors are refined simultaneously.
WHY CORRECTION IS REQUIRED

 Ones the corrections for systematic error are applied , it is possible

to obtain lattice parameter routinely to an accuracy.
CORRECTION APPLIED TO DIFFRACTION PATTERN
TO COMPENSATE FOR SYSTEMATIC ERROR
PROCEDURE TO MEASURE THE PRECISE
LATTICE PARAMETER
 Take the values of 2θ from the powder x ray diffraction diagram and fine. Now
substitute in sin2θ and get the values .
 Now multiply 1,2,3 with the ratio of observed value of sin2θ to minimum value of
sin2θ obtained.
 Approximate the value of ( 3 sin2θ / sin2θ )min and obtained h 2 + k 2 + l 2 value.
 From the previous step find the corresponding h,k,l value.
 Substitute all the value to find the value of a and d.
 NOTE: Any value greater than 17 in h,k,l shall not be considered for calculating a
and d.
PRECISE LATTICE PARAMETER DETERMINATION OF
SPINEL MgAl2O4 FROM X-RAY POWDER
DIFFRACTION PATTERNS
 The subject of the present work is the precise determination of the lattice
parameter for the cubic spinel structure of MgAl2O4 using different methods:

 Extrapolation function
 Cohen method
 Rietveld method
EXTRAPOLATION METHOD
 For the extrapolation method the lattice parameter, ao, is computed for each line of the
pattern and is plotted against a so called “extrapolation function”.
 Extrapolation functions are functions of θ, like cos2 θ, sin2 θ, cos2 θ/sinθ

 LAEGE SYSTEMATIC ERROR SMALL SYSTEMATIC ERROR

Cohen method
 The Cohen method consist from two sets of equations.

 With the two sets of equations we can find the A and C values.
 Once the value of A is found, ao can be calculated.
 The constant C is related to the amount of systematic error involved.
Rietveld method
 The Rietveld method is more complicated and sometimes difficult to use but, as our
comparative study is about to show, it yields the best results.
 The method is a profile fitting technique involving the simulation of the diffraction
pattern, based on a structural model.
 The calculated intensities are fitted to the observed intensities, which is achieved by
minimization of the sum of the square.
Lattice parameter calculated for the MgAl2O4
powders, using different methods

The calculated values are quite similar to those from the

references for well crystallized spinel (ao=8.0831 Å).
APPLICATION

 Material synthesis
 Analysis of solid solution
 Thermal expansion
 Strain/stress determination
 Alloy formation
 Defect structures
REFERANCE

 https://
h-and-m-analytical.com/wp/wp-content/uploads/2015/04/precision_lattice_parameter.pdf
 LECTURE-18 Prof.R.K.Ray (NPTL VIDEO).
 https://physics.uvt.ro/anale_uvt_fizica/articles/v49/09_Barvinschi_32_35.pdf
 http://vlabs.iitkgp.ac.in/scm/exp4/index.html
 L.S.Zevin, G.Kimmel, Quantitative X-Ray Diffractometry, Springer-Verlag, New York
(1995)