X RAY DIFFRACTION

1. Diffraction of X-Rays by Crystals: -------X Rays are the electromagnetic waves of least wavelength (1Ao approximately). X Rays are produced when fast moving electrons incidents on a material of high atomic number. The wave nature of X Rays can be studied by using the diffraction patterns. X- Rays cannot be diffracted using ordinary diffraction grating. Because to diffract electromagnetic rays, the essential condition is the slit width must be approximately equal to the wavelength of the rays. Laue suggested that a crystal which consists of a 3-dimensional array of regularly spaced atoms can be used as a grating. Friedrich and Knipping succeeded in diffracting X-rays by passing them through thin crystal. The experimental arrangement used to diffract X Rays is shown in the fig. (1).

X-rays obtained from X-ray tube. Narrow beam of X Rays can be obtained by passing them through slits S1 and S2. The beam now passes through a sodium chloride (Nacl) or Zinc Sulphide (Zns) crystal. The emergent rays are made to fall on photographic plate P (screen). The diffraction pattern so obtained consists of a central spot at O and a series of spots arranged in a definite pattern about O. This symmetrical pattern of spots is known as Laue pattern. This experiment proves the wave nature of X-rays. Bragg explained the diffraction pattern as the spots are produced due to the reflections of some of incident Xrays from the various sets of parallel crystal planes which contains large number of atoms. From the Laue experiment, it can be concluded that 1. X-rays are electromagnetic waves of extremely short wavelengths. 2. The atoms in a crystal are arranged in a regular three-dimensional lattice. 2. BRAGSs LAW: --------------Let us consider a set of parallel lattice planes of a crystal separated by a distanced apart. A narrow beam of X-rays of wavelength incidents on these planes at angle as shown Fig. (2). The beam will be reflected in all directions by the atoms of various atomic planes. The condition for the construction interference of reflected waves is that the path difference between two reflected waves must be an integral multiple of wavelength.

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Consider a ray PA reflected at atom A in the direction AR from plane I. Another ray QB reflected at another atom B in the direction BS. From the atom A, draw two perpendiculars AC and AD on the incident ray QB and reflected ray BS respectively. The path difference between these two rays is (CB+BD). When the path difference (CB+BD) is equal to n, then the two rays will suffer constructive interference and produce an intense spot. Thus the conditions constructive interference is CB + BD= n . (1) From the fig. (2) From equation (1) CB = BD = d sin

2 d sin= n . (2)

Where n=1, 2, 3, etc., for first order, second order, third order, etc.., maxima respectively. Equation (2) is known as Braggs law. Different directions in which intense reflections will be produced can be obtained by giving different values to, i.e. For first maxima, sin1= (/2d)

For second maxima, sin2= 2(/2d) For third maxima, sin3= 3(/2d) etc

The intensities go on decreasing as the order of the spectrum increases. When a beam of monochromatic X-rays falls on a crystal, each atom becomes a source of scattering radiations. The scattering of X-rays from these planes can be considered as reflections from the crystal planes. In general, the Bragg scattering is regarded as Bragg reflection. At certain glancing angles, reflections from these sets of parallel planes are in phase with each other and hence they suffer constructive interference to produce maximum intensity. For other angles, the reflections from different planes are out of phase and hence they interfere to produce either zero or extremely feeble intensity. 3. BRAGGS X-RAYS SPECTROMETER: Braggs spectrometer is shown in fig. (3). X-rays are emitted from X-ray tube. A narrow beam of X rays is obtained by passing them through slits S1 and S2. The beam is now allowed to fall on a crystal C mounted on a circular turn table of the spectrometer. The turn table can be rotated about a vertical axis passing through it centre. The rotation can be read on a circular graduated scale S with the help of vernier V1. The reflected beam then passes through slit S3 and enters ionization chamber. Ionization chamber contains gas with two electrodes. The ionization chamber is mounted on a movable arm about the same axis of crystal. The position of ionization chamber can be read by a second vernier V2. The turn table and ionization chamber are linked together in such a way that when the turn table rotates through an angle, the ionization chamber turns through 2. The reflected X-rays entering the ionization chamber ionize the gas which causes a current to flow between two electrodes which can be measured by galvanometer G.

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The ionization current is measured for different values of glancing angle. A graph is plotted between glancing angle and the ionization current. The graph is shown in fig. (4). For certain values of glancing angle , the intensity of ionization current increases abruptly. From the Braggs equation 2 d sin= n Whered is the distance between crystal planes, is the wavelength of incident X rays and is incident (glancing angle).

For the first order spectrum: n = 1 For the second order spectrum: n = 2 For the third order spectrum: n = 3 From the above equations

and 2d sin1= and 2d sin2= 2 and 2d sin3= 3

sin 1: sin 2: sin 3 = 1:2:3

From the figure (4), the glancing angle 1, 2, 3 for first, second and third order reflections are measured. It can be seen that sin 1: sin 2: sin 3 = 1:2:3. Here we have assumed that the X-ray beam is monochromatic. Fig. (5). Represents the case when X-ray beam consists of two wavelengths 1 and 2. In this case, peak values like A1, B1; A2, B2; and A3, B3 are obtained. The peak values A1, A2, A3 corresponds to wavelength 1, while peak values B1, B2, B3 corresponds to wavelength 2. Braggs equation can be verified for wavelength 1 and 2 using sin 1: sin 2: sin 3 =1:2:3. And sin 11: sin 21: sin 31 =1:2:3 From the observed value of and known values of d and n, the wavelength of X-ray can be calculated by using Braggs equation, i.e., 2d sin = n. In Braggs spectrometer, it is observed that 1. As the order of the spectrum increases, the intensity of the reflected X-rays decreases. 2. The ionization current does not fall to zero for any value of glancing angle . X RAY DIFFRACTION Page 3

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4. Braggs Law and Crystal Structure: -----------------In case of KCl crystal Bragg obtained the maxima of reflected X-rays at glancing angles 5.220, 7.300 and 9.050 respectively using three different reflecting planes. From Braggs equation 2d sin = n For first order spectrum n= 1, hence 2d sin = (Or)

From this

:: sin 5.220: sin 7.300: sin 9.050 :: 0.091: 0.127: 0.157 :: 1:1.4:1.73

This results shows that KCl is simple cubic crystal.

5. CRYSTALLOGRAPHY BY LAUE METHOD: The experimental arrangement of Laue method is shown in fig. (6). Fine beam of X rays incidents on crystal. After passing through the crystal, the X-rays are diffracted and recorded on a photographic plate. The X-rays which penetrate the crystal are scattered from different atomic diffraction centers. The values of incident angles will be different for each set of planes. Each set of parallel planes will have their own value of the distance. The atoms of crystal are arranged in an orderly manner in all dimensions in space. Hence the diffraction of X-rays will occur from many families of atomic planes. The diffraction patterns consists of a central spot and set of arranged in a definite pattern about central spot. The symmetrical pattern of spot is known as Laue pattern. Each spot in the Laue pattern corresponds to an interference maximum for a set of crystal plane satisfying the Bragg equation 2d sin = n, for a particular wavelength selected from the incident beam.

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Consider a grating with atoms on the line as diffracting centers. Let a be the lattice constant, i.e., the constant distance between two successive lattice points. Suppose monochromatic X-rays of wavelength incidents on the space lattice. The electrons in the atoms at the lattice points scatter X-rays in all directions coherently. Let 0 be the angle of incidence and be the angle of diffraction as shown in fig. (7). The path difference between the two diffracted rays is (AN BM), where AM and BN are perpendiculars dropped on the incident and diffracted rays respectively. The diffracted rays will have maximum intensity if AN-BM=n1 . (1) From figure, AN = AB cos = a cos and Where n1 is an integer BM = AB cos 0 = a cos 0

Now from equation (1) a (cos cos 0) = n1 . (2) Let cos = and cos 0 = 0 Then a ( - 0 ) =n1 .. (3)

Now for a three dimensional grating, let the directional cosines along X, Y and Z directions be, and respectively, then the conditions are a ( - 0 ) = n1 a ( - 0 ) = n2 and a ( - 0 ) = n3 Where n1, n2 and n3 are integers. These are called Laue equations. 6. CRYSTALLOGRAPHY BY POWDER METHOD: Powder crystal method is a standard technique to study the structure of micro crystals. This method gives information regarding the size of crystals, presence of impurities, distortion, preferred orientation of crystals, etc. The experimental arrangement of powder method is shown in fig.(8). Monochromatic X-rays can be obtained by passing X-rays through a filter F. The beam is collimated by passing it through two fine slits S1 and S2. The narrow beam of X-rays falls on the powdered specimen C. The specimen is located at the centre of drum shaped cassette with photographic film at the inner circumference. The basic principle is that in the powder, million micro-crystals have all possible random orientations. Among these very large number of micro-crystals there will always exist some crystal whose lattice planes are so oriented to satisfy the Braggs relation 2d sin = n. Reflection takes place at these planes. For a value of, the beam reflected at an angle 2. The lattice planes with a given spacing d and same value of n and, occur in all positions around the axis of the incident beam. The reflected rays X RAY DIFFRACTION Page 5

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produce a cone with semi-vertical angle 2. For various set of d and n, various cones of rays are obtained. One such a cone is shown in fig. (8).

The scattered X-rays are incident on the photographic film. The intersections of the different cones of the photographic film will be in the form of concentric circular rings. Radii of these rings (recorded on the film) can be used to find glancing angle. Now the interplanar spacing can be calculated.

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