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# 3.1 Basic principles:X-rays are electromagnetic waves like.s visible light.

Hence, x-rays exhibit the phenomenon like interference and diffraction. Wavelength of x-rays is of the order of 1 Ao. So, that x-ray does not produce observable diffraction effects with ordinary ruled diffraction grating. In 1912 von Laue suggested that crystals are more suitable to observe diffractio n effects with xrays. The important condition for observable diffraction effects is that the wav elength of the rays and inter planar separation should be of the same order. Here for x-rays, =1A.wh ere as inter planar separation is about 2 A.. After Fredrich and knipping who demonstra ted that x-ray beam passing through single crystal was broken up into a collection of diffracte d beams. The measurements of diffracted beam intensities and their directions would provide t he desired information about the crystals. . 3.2 Bragg s law: Bragg.s law explains the conditions under which diffracted x-ray beams from a cr ystal are possible the diffraction pattern so produced can tell us much about the internal arrangement of atoms in crystals. Now to derive the Bragg.s condition, let us consider a crysta l made up of equidistant parallel planes of atoms with inter planar spacing d further, consid er a monochromatic x-ray beam of wavelength, having a common wave front, falls at an angle on these planes. Each atom scatters the x-ray uniformly in all directions, becau se of the periodic arrangement of atoms, the scattered radiation from all the atoms in a s et of planes is in phase, where they interfere constructively and in out of phase they interfere de structively .

Consider two rays ABC and DEF, which are reflected from different planes in a gi ven set of lattice planes separated by a distance d which is called inter planar separation.

Letbe the angle made by the rays with different set of planes. The two rays reflected from different planes. Thus, the rays BC and EF are reflected from the two points nd E. the path length of ABC and DEF are not same. Extend the rays AB to cut EF at H and CB cut DE at G .the path length of the ray DEF is greater than the path length of ABC by an unt (GE+EH). The path difference between two rays reflected * From adjacent planes = GE+EH------------ (1) From BGE sin= .. GEBE = > GE =BE sin = d sin From BEH sin= . EHBE . EH = BE sin

are B a to amo

=d sin

Substituting the values of GE and EH in (1), then the total path difference is * . = GE+EH = d sin+ d sin = 2dsin ---------- (2) . = 2dsin if this path difference is an integral multiple of the wavelength ,the reflected beam will interfere constructively ,giving maximum intensity i.e., constructive diffractio n. 2sinnd...

Thus,

This is known as BRAGG.S LAW . Bragg.s law states that the x-rays reflected from different parallel Planes of a crystal interfere constructively when the path difference is integra l multiple of the wavelength of x- rays. We know that then we obtain ..maxsin1.. 12nd . .

This indicates that must not be greater than twice the inter planar spacing, oth erwise no diffraction will occur. . 3.3 Laue method: In the Laue method a single crystal is stationary in a beam of x-rays of continu ous wavelength. A crystal selects and diffracts the discrete values of for which planes exist of s pacing d. and incidence angle . satisfying Bragg.s. . .

The experimental arrangement is shown in fig. A source producing a beam of x-ray s over a wide range of wavelengths preferably 0.2 to 2A0is used. A pinhole arrangement produce s a wellcollimated beam, The dimensions of the single specimen need not be greater than 1 mm. A photograp hic plate placed at certain distance from the crystal to record the diffracted rays from s ingle crystal. The diameter of the pin holes is important for the quality of Laue spot, which a re traced on the plate. The diffraction pattern consists of a series of spots. This pattern will show the symmetry of the crystal

The most important point in this pattern is that the x-ray beam contains many wa velengths. If we take monochromatic x-ray beam and allow it to pass through single crystal, the d iffraction is not to be expected. This is because very few sets of planes will satisfy the Bragg.s diffraction condition. But if the source has whole range of wavelengths in the continuous x- ray spectr um, there will be different values of, which satisfy Bragg.s condition. .

We know that atoms of a crystal have an orderly arrangement in all three dimensi ons in space. Hence the diffraction of x- rays will occur from many families of atomic planes. Each family picks out the wavelength which it can diffract by satisfying Bragg.s law The diffraction pattern consists of a series of spots. Each dot is called as Lau e spot and the entire spots are called as Laue diffraction pattern . Each Laue spot represents a set mil ler indices of planes in the crystal. The shape of the unit cell can be established from the sy mmetry of the Laue pattern. 3.4 Powder method: The power method was developed by Debye, Scherrer and by Hill. This method is us ed to study the structure of the crystals, which cannot be obtained easily in the form of pe rfect crystals of appreciable size. There fore the sample used is in the form of a fine power cont aining a large no. of tiny crystallites with random orientations. A diagram of a powder camera is shown in fig. There is a specimen holder at the center of the cylindrical camera. The finely powdered sample is filled in a thin capillary tub e (or) is simply passed on wire by means of binder and mounted at the center of the camera.

Then the camera along with the specimen is taken to the dark room where a thin s trip of x-ray film is loaded in the cylindrical cassette. Before the camera is loaded the film is punched to make two holes one for entrance of x-rays and the other for exit of x-rays. A monochromatic x-ray beam is allowed to fall on the power sample. Since the sam ple contains a large number of tiny crystallites arranged randomly in all possible orientatio ns. For each set of planes there exist some crystallites, which are oriented in a direction to satis fy the Bragg.s condition and give raise the diffraction effect. The diffracted beam forms a con e with half-apex angle 2. In a similar way, other sets of lattice planes give their diffraction c ones on the x-ray film. These cones are recorded in the form of a pair of arcs on the x-ray film. When they diffract through an angle 900, they appear as straight lines and afterwards the curvature is reversed and when the angle approaches to 1800 the traces are nearly circular. . We know the linear distances between the pair of arcs various diffraction angles . can be calculated for a known camera radius R.. They are related as

## 4SR .. 1 radins4sR . .. .... .. 1801 degrees4sR . . .. .... ..

57.3= 4sR . .. .. .. Since the wavelength is known for a given characteristic x-ray beam. Substitutin g value of . in Bragg.s condition, the value of d. can be calculated. . 2sindn... By using the relation 222adhkl . .. The relation between crystallographic axes and Miller indices (h k l) can be obt ained. This powder method also gives the information of the structure of the unit cell.

Applications of X-ray diffraction (XRD):XRD is a nondestructive technique . To identify crystalline phases and orientation . To determine structural properties: Lattice parameters (10-4), strain, grain si ze, expitaxy, phase composition, preferred orientation (Laue) order-disorder transfo rmation, and thermal expansion. . To measure thickness of thin films and multi-layers. . To determine atomic arrangement. . X-ray diffraction is used to determine the structure of biological molecules. The discovery of the double-helical structure of the DNA molecule is one example. . it is used to study lattice imperfections such as foreign impurities, dislocat ions, regions of strain, etc. in the presence of such imperfections, the diffraction pattern no l onger corresponds to that of a perfect crystals and by studying the devation one can o btain information concerning the type of imperfections and their distributions in the crystal.

Strengths . Powerful and rapid (< 20 min) technique for identification of an unknown miner al . In most cases, it provides an unambiguous mineral determination . Minimal sample preparation is required . XRD units are widely available . Data interpretation is relatively straight forward Limitations . Homogeneous and single phase material is best for identification of an unknown . Must have access to a standard reference file of inorganic compounds (d-spacin gs, hkls) . Requires tenths of a gram of material which must be ground into a powder . For mixed materials, detection limit is ~ 2% of sample . For unit cell determinations, indexing of patterns for non-isometric crystal s ystems is complicated . Peak overlay may occur and worsens for high angle 'reflections'

Summary:1. Bragg.s Law states that the X-rays reflected from different parallel planes o f a Crystal Parallel planes of a crystal interfere constructively when the path difference i s an integral multiple of wavelength of x-rays.

2sinnd... Where n = Order of diffraction = Glancing angle . d = Inter planet distance = wavelength of incident X-ray . 2. There are three main X be analyzed. Ray diffraction methods by which crystal structure can

a) The Laue method: - For single crystal b) The powder method: - For finely divided crystalline or polycrystalline method c) The rotating crystal Method: - For single crystals.

Questions and Problems:1. (a) State and explain Bragg.s law. (b) Describe with suitable diagram, the powder method for determination of crys tal structure. (c) A beam of X-rays of wavelength 0.071 nm is diffracted by (110) plane of roc k salt with lattice constant of 0.28 nm. Find the glancing angle for the second order diffr action.

2. (a) Explain Bragg.s law of X-ray diffraction. (b) Describe Laue.s method for determination of crystal structure. (c) A beam of X-rays (= 1A.U.) is made to incident on a set of crystal planes w hose . separation is 5 A.U. Calculate the angle for the fourth Bragg reflection. (d) A beam of X-rays is incident on a NaCl crystal with lattice spacing 0.282 n m. Calculate the wavelength of X-rays if the first order Bragg reflection takes place at a gl ancing angle of 8o 35.. Also calculate the maximum order of diffraction possible

3. (a) Derive the Bragg.s law of X-ray diffraction and obtain the relation that connects the interplanar distance d in orthogonal systems with lattice parameters a, b and c. (b) Ge crystallizes in diamond (form) structures with 8 atoms per unit cell. If the lattice constant is 5.62 AU, calculate its density.