X-Ray Diffraction : Content = What, Why and How of X-rays = X-Ray Diffractometer V Peak -— Position, Intensity, and WidthWhat is X-ray? =X-ray is electromagnetic radiation. =X-rays are produced by bombarding high energy electrons on any heavy metal. TT seocinen y@ According to Mosley’s law every element has its unique signature in the form of K, emission. = X-Rays diffract treating inter Scotered Direct _ inelastically atomic distances as slits. Electrons Beam Scattered Electrons> Why X-ray? An Electromagnetic radiation can be diffracted by atomic planes only when the half of its wavelength is less than the inter atomic distance (D). ae _ = X-Rays are used over visible light for crystal diffraction because of its shorter wavelength.How X-ray? ® Diffraction is the main technique used to identify crystal structure. = When a parallel beam diffracted from a single slit causes a path difference of d.Sin@ and when incident beam is also at an angle 9 then the path difference is 2.d.Sin6 ae ss | Total Path difference Path difference = 2d.sino =d.sinoHow XRD? ® When atomic planes act as diffraction slits, then the constructive interference is defined by Bragg’s Law-= X-Ray DiffractometerX-Ray Diffractometer > Beam of electrons falls on a rotating target and throws out the X-rays generated. Target like Cu is rotating at a speed of 6000 rpm to prevent heating. A supply of cold water is also provided for keeping target cool.X-Ray Diffractometer >This emits a continuum of X- Rays. But we want a particular Ka wavelength. » Earlier some filters were used (thin Ni foil in case of Cu) » Now a days monochromators are used. Like quartz crystal. » Finally these X-Rays fall on the sample and detector containing photomultiplier tube detects it.“| oe = ! =~ }=0.139 nm | I Ni absorption edg Wavelength= XRD Peak — Position, Intensity, and Width(syun Aueniquy) Aysuayuy 40 50 60 20 (degree) 30 20Peak position All planes diffract coherently at an angle where Bragg’s Law holds good.Peak position ad = Therefore, the position of a peak determines the { inter-planar so"g for a am of planes. d= tnter-glenal — ed dor Gio Gist ciation a a Intent (Arbitrary Units)Peak Intensity Peak intensities are determined by position of atoms with in a unit cell. = Let's take an example- yp a {2.|Peak Intensity Let in 1 case, the path difference between ray 1 and 2is A. Then in 24 case, ray 3 with respect to ray 1 will have a path difference of A/2. This will show a destructive interference. similarly the other planes also cancel each other. The peak visible in 1+ case has now vanished in 2"¢ Case. ] Path Difference is ‘A/2' so Path Difference is ‘N’ so Destructive Interference Constructive InterferencePeak Intensity ®See Figure, where cubic shows all peaks and limited peaks are visible in body-centered or _ face-centered structure. > Conclusively, it can be stated that the overall intensity of a peak is because of the superposition of all the constructive and destructive contributions which is obviously guided by the position of atoms.Peak Width » Width of a peak basically depends on two factors- ® 1. Crystallite size /@ 2. Lattice Strainty4y »Crystallte size- itis the size of coherently diffracting piece of a crystal. In.on XRD pattern it can be calculated by Sherer'sformula,Peak Width : Crystallite Size »Crystallite size- it is the size of coherently diffracting piece of a crystal. In an XRD pattern it can be calculated by Sherrer's formula. “ Ka d= B cos@ » Here K is a constant generally taken as 0.9 .. Ais the wavelength used. B is the FWHM of a peak and @ is the half of corresponding peak angle.Peak Width : Crystallite Size L Big Crystallite XRD Small Crystallites yy Very Small CrystallitesPeak Width : Strain => *Case 1 > No Strain > Peak at its natural position. => *Case 2 » Compressive Strain > Lattice size decreases 20 increases. J *Case 3 % Tensile Strain > Lattice size increases 20 decreases. = *Case 4 > Non-uniform Strain > Peak gets broader. No Strain TT ‘Compressive Strain Tensile Strain oo Non-uniform StrainThe peak width could be because of both the crystallite size and the lattice strain. One could perform Williamson Hall fitting on RD data to get the distinct contribution because of crystallite size and lattice strain.Int(a.u) 10 20 30 40 «50 20(deg) 60 70 90 20 (deg)