CHAPTER - DIFFRACTION AND X-RAY OCAL LATTICE RECIPRO RODUCTION i 241 oa ss, being electromagnetic radiations, also undergo the phenom, rays, i visible light. However, unlike visi enon of diffraction as peel a cadnary ical grating because ore light, x-rays cannot Pa dif i912: ‘a German physicist Max Von Laue sug. ra ce ng one iS te atoms in a single crystal are regularly arranged with interatomic spacing of the order of a few angstroms, a crystal can act as a three-dimensiong| natural grating for x-rays. Friedrich and Knipping later successfully dem. onstrated the diffraction of x-rays from a thin single crystal of zinc blende (ZnS). The diffraction pattern obtained on a photographic film consisted of a series of dark spots arranged in *. definite order. Such a pattern is calleg the Laue's pattern and reflects the sya:metry of the crystal. Apart from this, the phenomenon of x-ray diffraction has become an invaluable tool to determine the structures of sisigle crystals and polycrystalline materials, It is also extensively used to ucwsaine "re wavelength of x-rays. 2.2 X-RAY DIFFRACTION When an atomic electron is irradiated by a beam of monochromatic x-rays, it starts vibrating with a frequency equal to that of the incident beam, Since an accelerating charge emits radiations, the vibrating electrons present inside a crystal become sources of secondary radiations having the same frequency as the incident x-rays. These secondary x-rays spread out in all possible directions. The phenomenon may also be regarded as scattering of x-rays by atomic electrons. If the wavelength of incident radiations is guile large compared with the atomic dimensions, all the radiations emitted by electrons shalll be in phase another, The incident x-rays, howevet have the same order of wavelength as that of the atomic dimensions hence the radiations emitted by electrons are, in general, out of phase another. These radiations may, therefore, undergo constructive or destruc- tive interference producing maxima or minima in certain directions. peepeeRay Diffraction & Reciprocal Lattice 35 Consider a one-dimensional row of similar atoms having interatomic spacing equal to a. Let a wave front of x-rays of wavelength A be incident on the row of atoms such that the wave crests are parallel to the row. The atoms emit secondary wavelets which travel in all possible directions. As shown in Fig. 2.1, the reinforcement of secondary wavelets takes place not only in a direction perpendicular to the row of atoms but also in. other directions. These directions correspond to different orders of x-ray diffrac- tion. The zeroth, first and second order diffraction directions are shown in Fig. 2.1. It may be noted that reinforcement takes place in some particular directions only, whereas in other directions the wave fronts interfere destruc- tively and the intensity is minimum. Such reinforcements produce Laue's pattern. Second Zeroth First order order order Fig. 2.1. Reinforcement of scattered waves resulting in diffracted beams of different orders. In actual crystals, the’ problem is more complicated because of the presence of three-dimensional arrangement of atoms. The conditions for a crystal to diffract x-rays can be determined by using either Bragg's treatment or Von Laue's treatment. « 2.2.1 The Bragg's Treatment : Bragg's Law In 1912, W.H. Bragg and W.L. Bragg put forward a-model which generates the conditions for diffraction in a very simple way. They pointed that a. crystal may be divided into various ‘sets of parallel planes. Th directions of eae then be accounted for if x-rays are od ee ied by such a set of parallel atomic planes followed ive ateecace oT HANG Tete AD The the problem of diffraction of x-rays by the atoms was converted into the problem of reflection of x-rays by the parallel atomic planes. Hence the words ‘diffraction’ and ‘reflection’ are mutually interchangeable in Bragg's treat- ment, Based on these considerations, Braggs derived a simple mathematical= | relationship which serves 2s a condition for the Bragg reflection to occur, This condition is kriown as the Bragg’s law. Fig. 2.2. Bragg’s reflection of x-rays from the atomic planes. To obtain the Bragg's law, consider a set of parallel atomic planes wit interplanar spacing d and having Miller indices (hkl). Let a parallel beam of x-rays of wavelength 2 be incident on these parallel planes at a glancing angle 6 such that the rays lie in the plane of the paper. Consider ‘wo such rays 1 and 2 which strike the first two planes and get partially reflected at the same angle @ in accordance with the Bragg's treatment as shown in Fig. 2.2. The diffraction is the consequence of constructive interference of these reflected rays. Let PL and PM be the perpendiculars drawn from the point P on the incident and reflected portions of ray 2 respectively. The path difference between rays 1 and 2 is, therefore, given by (LQ + QM). Since LQ = QM =d sin®, we get Path difference = 2d sin® For constructive interference of rays 1 and 2, the path difference must be an integral multiple of wavelength A, i-e., t 2d sing = nd (2.1) where n is an integer. This equation is called the Bragg’s law. The diffraction takes place for those values of d, @, 4: and n which satisfy the Bragg’s condition. In Eq. (2.1), m represents the order of reflection. For n= 0, we | get the zeroth order reflection which occurs for 6 equal to zero, i.e., in the direction of the incident beam and hence it canaot be observed experimen- tally. For the given values of d and 4, the higher order reflections appear for larger values of 8. The diffraction lines appearing for n = 1, 2 and 3 are called first, second and third order diffraction lines respectively and so40 2.3 X-RAY DIFFRACTI ‘The phenomenon of x-ray structure of solids as well as for the stud) underlying principle in both the ae the aps sideri t order rel jection’ Considering only the first ray be writen 2S planes, real or fictitious, the Bragg’s |: 2d sin 8 =% (2.6) those values of d, ® and A which satisfy serays of known wavelength are take place are determined jections are then (ON METHODS , diffraction is employed to determine the ly of x-ray spectroscopy. The “law as given by Eq. (2.1). ‘m all the possible atomic The reflections take place for the above equation. For structural analysis, employed and the angles for which reflections experimentally. The d values corresponding t these refl obtained from Eq. (2.6). Using this information, one can proceed to deter- mine the size of the unit cell and the distribution of atoms within the unit tell. In the xray spectroscopy, x-rays are incident on a particular cleavage surface of a single crystal so that the interplanar spacing d is known. The angle for which reflections take place are determined experimentally. e wavelength A of the incident x-rays is thea obtained from Eq. (2.6). It may be noted that the x-rays used for diffraction purposes shoul have wavelength which is the most appropriate for producing diffractio effects, Since sin0 should be less than unity, Eq. (2.6) yields N<2d Normally, d~3A a<6A Longer wavelength x-rays are unable to resolve the details of the struct on the atomic scale whereas shorter wavelen; i ; igth x-rays are diffracted through __ angles which are too small to be measured experimentally. 4 In x-ray diffraction studies, the probability that the atomic planes with _ right orientations are exposed to x-rays is it i 4 een ores ‘ays is increased by adopting one of the o fe stal is held stationary and a beam of white radiations isi i a vatiee Dif ned alancing angle 8, ie. 0s fixed while select the appro * Havelengths present in the white radiations present in the er Prite reflecting planes out of the numerous This technique te eau thatthe Braga's condition is satisfied. is called the Laue's technique (ii) A single crystal is held in the path 0 monochromatic radiati S matic radiationsSe X-Ray Diffraction & Reciprocal Lattice ma and is rotated about an axis, i, A is fixed while @ varies. Different sets of parallel atomic planes are exposed to incident radiations for different values of @ and reflections take place from those atomic planes for which d and @ satisfy the Bragg’s law. This method is known as the rotating crystal method. (ii) ‘The sample in the powdered form is placed in the path of monochromatic x-rays, i.c., 0 is fixed while both @ and d vary. Thus a number of small crystallites with different orientations are exposed to x-rays. The reflections take place for those values of d, @ and A which savisfy the Brage's law. This method is called the powder method. 2.3.1 The Laue's Method An experimental arrangement used to produce Laue's patterns is shown in Fig. 2.5. Itconsists of a flat plate camera which contains 4 collimator with a fine hole to obtain a very fine beam of x-rays. The sample is placed on a goniometer which can be rotated to change the orientatien of the single crystal. Two flat photographic films are used, one for réceiving the transmit- ted diffracted beam and the other for receiving the reflected diffracted beam for back reflection experiments. Such experiments are performed particularly when there is excessive absorption of x-rays in the crystal. Film for back Film for forward reflection reflection = ee X-ray SS beam Collimator with @ pinhole Single crystal Goniometer speciman Fig. 2.5. A flat plate camera used in Laue’s diffraction method. Initially, a single crystal specimen having dimensions of the order of Imm x Imm x Imm is held stationary in the path of white x-rays having wavelengths ranging from 0.2 to 2 A. Since the crystal contains a number of sets of parallel atomic planes with different interplanar spacings, diffrac- tion is possible for certain values of 2 and d which satisfy the Brage's condition. Thus diffraction spots are produced on the photographic films as shown in Fig, 2.5. The crystal can be rotated with the help of goniometer to change its orientation with respect to the incident beam. By doing so, the42 Solid State Phy, diffraction condition may be satisfied for anew set of atomic planes and he a different type of pattern may be obtained on the photographic film, The symmetry of the crystal is, however, reflected in each pattern. ‘The Laue's method is mostly used to determine the crystal symmetry, For example, if a crystal having four-fold axial symmetry is oriented 50 tha, its axis is parallel to the beam, the resulting Laue's pattern also exhibits the four-fold symmetry. The symmetry of the pattern helps to determine the shape of the unit cell. It is, however. not practicable to determine the structure of the crystal by this method. It is because a number of wavelengths may be reflected from a single plane in different orders and may superpose ata single Point resulting in the loss of a number of reflections. The symmetry of the Laue's pattern also helps to orient the crystals for various solid state ‘experimeats, Another application of the Laue's method is the determination of imperfec- tions or strains in the crystal. An imperfect or strained crystal has atomic planes which are not exactly plane but are slightly curved. Thus instead of sharp diffraction spots one gets streaks in the Laue's pattern. This type of streaking on Laue's photographs is called asterism. 2.3.2. Rotating Crystal Method Cotimajor Photographic He rs es = 120 X-rays> >—> he Undeviated x-rays (b) I=4 Single 120 crystal SAU» Rotator (a) (c) Fig. 2.6. (a) Apparatus for rotating crystal method (b) Cones of scattered x-rays corresponding to reflections from (hkl) planes. (c) Layer lines produced after flattening the photographic film. In this method, a monochromatic beam of x-rays is incident on a single crystal mounted on a rotating spindle such that one of its; crystallographic’ Ca coincides with the axis of rotation which is kept perpendicular to the aie of the incident beam, The single crystal having dimensions of the order © Imm is positioned at the centre of a cylindrical holder concentric with o rotating spindle as shown in Fig. 2.6. A photographic film is attached at inner circular surface of the cylinder.X-Ray Diffraction & Reciprocal Lattice a The diffraction takes place from those planes which satisfy the Bragg's Jaw for a particular angle of rotation. The planes parallel to the axis of rotation diffract the incident rays in a horizontal plane. However, reflections cannot be observed for those’planes which always contain the incident beam. The planes inclined to the rotation axis produce reflections above or below the horizontal plane depending upon the angle of inclination. The horizontal lines produced by diffraction spots on the photographic film are called layer lines. If the crystal is positioned such that its c-axis coincides with the axis of rotation, all the planes with Miller indices of the type (hkO) will produce the central layer line. Likewise, the planes having Miller indices of the type (k1) and (hkl) will produce the layer lines above and below the central line respectively, and so on. These layer lines are shown in Fig. 2.6c. The vertical spacing between the layer lines depends on the distance between the lattice points along the c-axis. Hence the distance ¢ can be measured from the photographic film. Similarly, one can determine the translation vectors a and b on mounting the crystal along a and b axes respectively. Thus the dimen- sions of the unit cell can be easily determined. 2.3.3 Powder Method This is the most widely used diffraction method to determine the structure of crystalline solids. The sample used is in the form of a fine powder containing a large number of tiny crystallites with random orientations. It is prepared by crushing thc commonly available polycrystalline matcrial, thus eliminating the tedious process of growing the single crystals. The experimental arrangement used to produce diffraction is shown in Fig. 2.7. It consists of a cylindrical camera, called the Debye-Scherrer camera, whose length is small as compared to the diameter. The finely powdered sample is filled in a thin capillary tube or is simply pasted on a wire by means of a binder and mounted at the centre of the camera. The capillary tube or wire and the binder should be of a non-diffracting material. A collimated beam of monochromatic x-rays is produced by passing the x-rays through a filter and a collimator. The x-rays enter the camera through the collimator and strike the powdered sample. Since the specimen contains a large number of small crystallites (~10"? in 1mm? of powder sample) with rancom orientations, almost all the possible @ and d values are available. The diffraction takes place for those values of d and © which satisfy the Bragg's condition, i.e., 2d sinO = nd, 2 being a constant in this case. Also, since for @ particular value of the angle of incidence 8, numerous orientations of a particular set of planes are possible, the diffracted rays corresponding to fixed values of @ and d lie on the surface of a cone with its apex at the sample and the semivertical angle equal to 20. Different cones are observed for different sets of d and 0 for a particular value of n, and also for different combinationsSolid State Phys, 44 Transmitted 28 beam X-ray Fitter Photographic source Collimator Specimen ri (a) Reflected Incident x-ray Similar reflecting planes oriented differently: (b) Entrance hole Exit hole ds d,\d, dy dp dg 90° 45° 83 8, 0, 0° 0; 6) 63 $s mm — vw — > (c) Fig. 2.7. (a) Front view of the Debye-Scherrer Camera, (8) A cone produced by reflection of x-rays from identical Planes having different orientations. (6) latened photographic film after developing and indexing of diffraction line.45 X-Ray Diffraction & Reciprocal Lattice of @ and n for a particular value of d. The transmitted x-rays move out of the camera through an exit hole located diametrically opposite to the entrance hole. A photographic film is attached to the inner side of the curved surface of the camera. Each cone of the reflected beam leaves two impressions on the film which are in the form of arcs on either side of the exit hole with their centres coinciding with the hole. Similarly, cones produced by back-reflected x-rays produce arcs on either side of the entrance hole. If the sample consists of coarse grains rather than fine particles, a spotty diffraction pattern may be obtained. This is because a sufficient number of crystallites with all possible orientations may not be available in a coarse-grained sample. In such a case, the sample has to be rotated to obtain almost continuous diffraction arcs. The film is exposed for a long time (~ a few hours) in order to obtain reflected lines of sufficiently high intensity. It'is then removed from the camera and developed. The arcs produced by reflected rays appear dark on the developed film. The angle @ corresponding to a particular pair of arcs is related to the distance S between the arcs as 40 (radians) = S/R Qn where R is the radius of the camera. If 6 is measured in degrees, the above equation is modified as 40 (degrees) = 57.2965 FoR, (ei The calculations can be made simpler by taking the radius of the camera in multiples of 57.296, For example, taking R = 57.296 mm, we get © (degrees) = $ (mm)/4 29) ‘Thus one-fourth of the distance between the corresponding arcs of a particular pair in mm is a measure of the angle @ in degrees. Knowing all the possible @'sand considering only the first order reflections from all the possible planes, Bq. (2.6) is used to calculate the interplanar spacing for various sets of parallel planes which contribute to these reflections. Thus, we have d=h/ (2 sind) ‘These d values are used to determine the space lattice of the crystal structure. In modem x-ray diffractometers, the photographic film is replaced by a radiation detector, such as ionization chamber or scintillation detector, which records the positions and relative intensities of the various reflected lines as a function of the angle 20. The detector is mounted on a goniometer and is capable of rotation about the sample at different speeds. The whole system is computerised. The availability of alot of software makes the system versatile.% YAMA Wie Fay, 2A WYLAVROCAL LATION. As Oesutiteds entiien, the: diffraction fh r18ys eran tenn WN ty of parables planes having different erbentaticns (slegnay au Wen Yitcoe yp hen A 24h sev ings, Sn verti situations inch ving te preanncnsth by BP. Rewald hy deuebipiny » neom tye | “Meta lattice, The idea underlying the develeannend wes that each vA fh yer planes crnld be: regresentess by a neni! te thee planer Waving lenge Yosh, to the reciprocal of the interplanar spacing, Ths the Giteesicn of each rN represents the orientation of the umnesgymbing vA A prtslled gheewa side te Jength i proportional to the rexignezal of the interplanar wymcing ‘The normals are drawn with relerenen to an abitreey origin 200 yay sae sontkes at their ends, Theve points form 2 regular serengennecte Withee called a reciprocal lattice, Obriiemtly, each print in a recipe lation i escntative ppl ofa pelican paral vt planes and becomes cat deal with such points than with sts A planes. A reciproval lation to a direc lation is constructed sing the folowing procedure : (2) Take origin at one abiteary point and drew normals to cvey 4. Of parallel planes A the direct \asticn. (b) Take length of cach meormal equal w the reigeaal of Ge interplanar spacing for the omrenponding va f planes. The terminal points of these normals form the recigatral lection. Consider, for example, 2 unit cell of monoclinic crywal in which o# b¢c,a=7=HP and B > WF as shown in Fig. 24. For simplicity, we neat the unit cell in such 2 way that the b-axis is perpendicular wo the plane of tie paper; hence a and e-axes lie in the plane of the paper as shown in Fig 29 Consider planes of the type Wil) which ae parallel wo baste ie., perpendicular wo the plane of the paper. Hence normal 0 Sem planes lie in the plane of the papee ‘The planes (Hi1}), being perpen ular to the plane of the paper, a represented by lines. Thos the Sint (101) in fact means the plane (100% and 40 on. Taking the pois of lersection of the three anes 25 Fig. 28, Unit cell of @ monoclinic crsial. origin ono (109)‘XeRoy Diffraction & Reciprocal Lattice a planes (hand their Jengths are taken tobe I/dygp Where dy isthe interplanar spacing for the planes (hol). For example, since the planes (200) have half rnsnterplanar spacing as compared to the plane (100), the reciprocal lattice point (200) is twice as far away as point (100) from the origin. If normals to all the (hkl) planes are drawn, a three-dimensional reciprocal lattice is obtained. ! 1 | 1 Te ates | : 7; 301 ae a a fin ee 1 eel be oat al 1900: = + saan Le 1 Patel 4. bag, ' Pai] oe lege ! ? “eal i ct I 271 101 © G02 Fig. 2.9. Two-dimensional reciprocal lattice to a monoclinic lattice, “The b-axis is perpendicular 10 the plane of the paper. 24.1 Reciprocal Lattice Vectors ‘A reciprocal lattice vector, Oyyy is Uefined as a vector having mag- nitude equal to the reciprocal of the interplanar spacing 4, and direction coinciding with normal to the (hkl) planes. Thus, we have Mae =>-a (2.10) 9, Tak hia where itis the unit vector normal to the (hkl) planes. In fact, a vector drawn from the origin to any point in the reciprocal lattice is a reciprocal lattice vector. Like a direct lattice, a reciprocal lattice also has a unit cell which is of the form of a parallelopiped. The unit cell is formed by the shortest48, Solid State Physicg Formals along the three directions, ic., along the normals to the Planes (100) (010) and (001). These normals produce reciprocal lattice vectors designated & Cro Soyo aNd Gog, Which represent the fundamental reciprocal lattice vectors. Leta, band e be the primitive translation vectors ofthe direct lattice as shown in Fig. 2.8. The base of the uni is unit cell is formed by the vectors b and © and its height is equal to dog. The volume of the cell is V = (area) diog | _ area _ bx of or — ° = digi 7 Vv In vector form, it is written as (11) where fi is the unit vector normal to (100) planes. From Eq. (2.10), we get Syo= (2.12) 10 dio " Denoting the fundamental reciprocal vectors 044, dyy9 and Ooo by at, b® and e* respectively, Eqs. (2.11) and (2.12) yield Similarly, cxa So = a.bxe eo and _axb Soot = a bxe where a.bxe = b.cxa = c.axb is the volume of the direct cell, ‘Thus the réciprocal translation vectors bear a simple relationship to the crystal irans- lation vectors as a* is normal to b and c b* is normal to ¢ and a (2.14) c* is normal to a and b.X-Ray Diffraction & Reciprocal Lattice 49 In vector notation, it means a*.b=0 bre =0 (2.15) caso chb=0 Taking scalar product of a, b* and c* with a, b and c respectively and using Eqs. (2.13), we find ata=1, btb=1, che=1 (2.16) It appears from Eqs. (2.16) that a, b* and ¢* are parallel to a, b and crespectively. However, this is not always true. In non-cubic crystal systems, such as monoclinic crystal system, as shown in Fig. 2.8, a* and a point in along OA’, and OA respectively. Thus all that is. s. (2.16) is that the length of a* is the reciy il of a cos8, where 2 Ge agi Neto an _ In some texts on Solid State Physics, the primitive translation vectors a,b and ¢ of a direct lattice are related to the primitive translation vectors a*, b* and c* of the reciprocal lattice as ats btb = che = 2n (2.17) with Eqs. (2.15) still being valid. These equations can be satisfied by choosing the reciprocal lattice vectors as bxe += a sie, be = 2n (2.18) a.bxe axb = oa axe It is now obvious that every crystal structure is associated with two important lattices — the direct lattice and the reciprocal lattice. The two lattices are related to each other by Eqs. (2.13). The fundamental translation vectors of the crysial lattice and the reciprocal Tattice nave dimensions of {length} and [lengtht-! respectively. This is why the later is called the reciprocal lattice. Also, the volume of the unit cell of a reciprocal lattice is inversely proportidnal to the volume of the unit cell of its direct lattice. A crystal lattice is a lattice in real or ordinary space, i.e., the space defined by the coordinates, whereas a reciprocal lattice is a lattice in the ic ie ‘A wave vector k is reciprocal space, associated k-space ot Fourier space. A w alvaje aie in the k-space. The points of the crystal lattice are given by50 Solid Stte Phy, T = ma + nb + pe ay where m, n and p are integers. Similarly, the reciprocal lattice poins reciprocal lattice vectors may be defined as G = ha* + kb* + Ic* 2.29) where h, k and J are integers. Every point in the Fourier space has a meanin, but the reciprocal lattice points defined by Eq. (2.20) carry a special impor tance. In order to find the significance of G's, we take the dot product ot ¢ and T: GT = (ha* + bh* + le*) . (matnb+pe) = 2n (hm+kn+lp) = 2n (an integer) or exp (iG.T) = 1 where we have iised Eq. (2.17). Thus it is clear from Eq. (2.20) that h, k and ! define the coordinates of the points of reciprocal lattice space. In other words, it means that a point (/,k,!) in the reciprocal space corresponds to the set of parallel planes having the Miller indices (hkl). Hoe concentatis lattice is useful for redefining the Bragg's condition and intro sca ncept of Brillouin zones. 2.4.2 Reciprocal Lattice to SC Lattice The primitive translation vectors of a simple cubic lattice may be written as =ai,b=aj,c=ak Volume of the simple cubic unit cell = a.bxe as Similarly, (2.21) and . oe ag Akb E abxe a The Eqs. (2.21) indicate that all the three reciprocal lattice vectors are equél in magnitude which means that the reciprocal lattice to sc lattice is also simp!¢X-Ray Diffraction & Reciprocal Lattice st cubic but with lattice constant equal to 2n/a. 24.3. Reciprocal Lattice to BCC Lattice ‘The primitive translation vectors ofabody-centred cubic lattice, as shown in Fig. 2.10, are (2.22) § (idk) Fig. 2.10. Primitive translation where a is the length of the cube edge vectors of a bec lattice. Maat and 7, j and i are the orthogonal unit vectors along the cube edges. The volume of the primitive cell is given by =a Using Eqs. (2.18), the reciprocal lattice vectors are obtained’as A; wrx (72) ey 2m 3 at oon Pa (ie (isi) Similarly, op (2.23) a’. b’xe and eee (kell > ‘As will be seen later, these are the primitive translation vectors of an fcc lattice, Thus the reciprocal lattice to a bec lattice is foc lattice.} 52 Solid State Physics 2.4.4 Reciprocal Lattice to FCC Lattice The primitve translation vectors of an fec lattice, as shown in Fig. 2.11, are ras) Lge | ~“ y Zz i+}) 5 j+k) (2.24) o= 4 (isi) Fig. 2.11. Primitive translation Volume of the primitive cell is ‘vectors of an fcc lattice, given by V=a'b'xc (isi). # [isk (Gi] = 3 (Hi). © Gx =a4 vis Using Eqs. (2.18), the primitive translation vectors of the reciprocal lattice are obtained as oe at aan Pee Ly (14) (is5- Similarly, c'xa’ Qn brnon Tobe 7 a (2.25) and a'xb’ 2m fr sw = 2n ———__ = (j_}. S298 ye a (det) Comparing Eqs. (2.25) with Eqs. (2.22), we find that these are the primitive translation vectors of a bcc lattice having length of the cube edge as 2n/a. Thus the reciprocal lattice to an fec lattice is a bcc lattice,X-Ray Diffraction & Reciprocal Lattice 3 PROPERTIES OF RECIPROCAL LATTICE 28 ach point in a reciprocal latie corresponds to particular St Ke of parallel planes of the direct Tattice, 2. The distance of a reciprocal Iatice point from an arbitrarily fixed origin is inversely proportional to the interplanar spacing of the corresponding parallel planes of the direct lattice. 3. The volume of a unit cell of the reciprocal lattice is inversely proportional tothe volume of the corresponding unit cell of the direct lattice. 4, Theunitcel ofthe reciprocal lattice need not be aparallelopiped. Itis.ou ith Wigner-Seitz cell of the reciprocal lattice which constitutes Brillouin zone. 5. ‘The direct lattice is the reciprocal lattice to its own reciprocal lattice. Simple cubic lattice is self-reciprocal whereas bec and {foc lattices are reciprocal to each other. 26, BRAGG'S LAW IN RECIPROCAL LATTICE ‘The Brage’ diffraction condition obtained easier by considering re- ection from parallel lattice planes can be used to express geometrical rMationship betwen the vectors in the reciprocal lattice. Consider recip- rocal lattice as shown in Fig. 2.12. Starting from the point A (not necessarily > ‘a reciprocal lattice point), draw a vector AO.of length 1/A in the direction of the incident x-ray beam which terminates at the origin O'of the reciprocal lative, Taking A as the centre, draw a sphere of radius AO which may intersect some point B of the reciprocal lattice, Let the coordinates of point B be (ti, X, I) which may have a highest common faciorn, ie. the Coordinates are of the type (nh, mks nt) where F i > and Ido not have a common factor, other than unity. Apparently, vector OB js the reciprocal vector. It ‘must, therefore, be normal to the plane (h'kT) or (hdd) and should have length equal t0 Udyyr OF nld,y, Thus, [OB = nid, (2.26) It follows from the geometry of Fig. 2.12, that onc such plane is the plane AE. If ZEAO = 0 is the angle between the incident ray and the normal, then from AAOB, we have OB = 2 OB = 2 OA sinO = (2 sin6)/A 227) From Eqs. (2.26) and (2.27), we get (2 sinO\/A = nldyy,54 Solid State Physics or 2d,,sind = nd which is the Brage's aw, n being the order of reflection. Thus we notice that if the coordinates of a reciprocal point, (nh, nk, nl), contain a common factor rn, then it represents nth order reflection from the planes (Ak/). It is also evident from the above geometrical construction that the Bragg's condition will be satisfied for a given wavelength 2 provided the surface of radius 1/A drawn about the point A intersects a point of the reciprocal lattice. Such a construc. tion is called Ewald construction. << Retlecting Soap, Fig. 2.12. Ewald construction ; Fig. 2.13. Magnified Ewald construction in the reciprocal lattice, relating reciprocal lattice vector to the ‘Wave vectors of the incident and ‘reflected radiation. The Brage’s law itself takes a different form in the reciprocal lattice. ‘To obtain the modified form ofthe Brags law, we redraw the vectors AO, > > : OB and AB such that each is magnified by a constant factor of 2m. Let the >a > D z new vectors be A'O'", O'B' and A'B' Tespectively as shown in Fi; A’O' = 2n (AO) = 2m, Wwe can represent the wave vector k by the vector AG’. The vector O is the reciprocal vector and is written as G. Thus accordin, '8 to vector algebra, A‘B' must be equal to (k + G). For diffraction ig. 2.13. Since ‘0 occur, the point B’ must be on the sphere, i.e., ; BY =| fe k+G6P=e " P4+2kG+G=k io 2k.G + G?=0 (2.28)X-Ray Diffraction & Reciprocal Lattice 55 ‘This is the vector form of Bragg's law and is used in the construction:of the Brillouin zones. The vector A'B' represents the direction of reflected or scattered beam. Denoting it by k’, we get k+G which gives k= (2.29) and Wk =Ak=G (2.30) ‘This indicates that the scattering does not change the magnitude of wave vector k; only its direction is changed. Also, the scattered wave differs from the incident wave by a reciprocal lattice vector G. 2.7. BRILLOUIN ZONES It has been indicated in the Ewald construction that all the k-values for which the reciprocal lattice points intersect the Ewald sphere are Bragg reflected. A-Brillouin zone is the locus of all those k-values in the reciprocal lattice which are Bragg reflected. We construct the Brillouin zones for a simple square lattice of s.de a. The primitive translation vectors of this lattice are azai; b=aj ‘The corresponding translation vectors of the reciprocal lattice are : i #* a* = (nla) i; b* = (2n/a)j * . loth + be) ‘Therefore, the reciprocal lattice vector is written as (5,— G = (n/a) (hi + ki) where h and k are integers. The wave vector k can be expressed as k=ki+ki From the Bragg's condition (2.28), we have 2k.G + G=0 r 2 ; ' Gener Wat) rat? Be ras | or =p Ue,i + i) (hi +i + (+B) =0 + or hk, + kk, = (w/a) (P+) I) ‘The K-values which are Bragg reflected are obtained by considering- all possible combinations of h and k. For h= #1 and k= 0, k, = 4n/a and k, is arbitrary; Also, for h = 0 and k = #1, k, =-tn/a and k, is arbitrary,56 Solid State Physics ‘These four lines, ic., k,=n/a and k, = +n/a, are plotted in Fig. 2.14, ‘Taking origin as shown, all the k-vectors originating from it and terminating on these lines will produce Bragg reflection. The square bounded by these four lines is called the first Brillouin zone. Thus the first zone of @ square lattice of side a is a square of side 2n/a. In addition to this set of lines, some other sets of lines are also possible which satisfy (2.31). For example, for 4=21 and k= +1, the condition (2.31) gives the following set of four lines, thet k, = 2nla Ce ka ft” &, i > k # = First zone Sy & Second zone Fig. 2.14. Brillouin zones of a square lattice in its rec Ky ky and k, are Bragg reflecied whereas i, is not the same reciprocal latice vector Gy, while G, is th These lines are also plotted in Fig. 2.14. The additional area bounded by these four lines is the second Brillouin zone. Similarly the othe, zones can be constructed. The caries ofthe Brillouin zone repnesent the loci of ke Values that are Bragg reflected and hence may be consid y Values that afe Bragg reflected and hence may | ered as the reflecting lanes, aries of the first 20 nesent-the reflecting planes fo 4 lection, those of the second zone Tepresent the reflectin; 1g planes for the second order reflection, and so on. A k-vector that does net terminate at a zone boundary cannot produce Bragg reflection. Thus the Brillouin zone pattern can be employed to determine the x-ray diffraction pattern of a crystal and vice versa. iprocal lattice. The vectors The vectors i and k, have fe reciprocal vectors of ky.—— X-Ray Diffraction & Reciprocal Lattice 37 ‘The Brillouin zones for a three-dimensional cubical lattice are con- structed using the generalized equation hk, + kk, + Ik, = -(nla) (HP + + P) (2.32) where a is the length of the cube edge. It is clear from Eq. (2.32) that the first zone is a cube having side equal to 2n/a, The second zone is formed by adding pyramids to each face of the cube (first zone) as triangles are added to the square in two dimensions, and so on. There is another simple method to determine Brillouin zones. We note from Fig. 2.14 that the reciprocal lattice vector G which satisfies Eq. (2.28) is a perpendicular bisector of the zone boundary and all the k-vectors lying on this boundary have the same G for reflection. Thus it is sufficient to consider only the allowed G-values and their normal bisectors to construct the Brillouin zones. The first Brillouin zone is the region bounded by the normal bisectors of the shortest possible G-vectors, the second zone is the region bounded by the normal bisectors of the next larger G-vectors, and so on. This method will be used to determine the Brillouin zones of the bec and {ec lattices as given below. 2.7.1 Brillouin Zone of BCC Lattice The primitive translation vectors of a bcc lattice are a= (a2) = (a2) (i-j+k) The primitive translation vectors of its reciprocal lattice are (Sec. 2.4.3) a* = (2n/a) (i+]) bt = (2n/a) (j+k) c* = (2nla) (+i) ae SX K 2 YS Fig. 2.15. First Brillouin Fig. 2.16. First Brilloui zone of a bec lattice. bie ? vai Briton °c lattice.58 ‘Solid State Physics The G-type reciprocal lattice vector is G = hat + kb* + [et = (Qnla) [(h+Di+h+ Wi +k+D ky) (2.33) ‘The shortest non-zero G's are the following twelve vectors (nla) (+i j); (nla) (2] + k); (n/ayek + 7) The first Brillouin zone is the region enclosed by the normal bisector Planes to these twelve vectors. This zone has the shape of a regular twelve- faced solid as shown in Fig. 2.15 and is called rhombic dodecahedron. 2.7.2 Brillouin Zone of FCC Lattice ‘The primitive translation vectors of an fec lattice are as (a2) (i +)) b= (a2) (j +k) = (a2) (& +7) ‘The primitive translation vectors of its reciprocal lattice are (Sec. 2.4.4) a* = (2n/a) (i+j-k) b* = n/a) -i+j+ky cf = (2nla) (i-j+k) The G-type vector is G = hat + kb* + Ie* = Qnla) ((h-k+Di+hak—-yj +Ch+k+ &} (234) ‘The shortest non-zero G's are the following eight vectors Qnla) (#i sj +k) The boundaries of the first Brillouin zone are determined mostly by the ormal bisector planes to the above eight vectors. However, the come the octahedron obtained in this manner are truncated by the planes which are normal bisectors to the following six reciprocal lattice veciore (2nla) (#21); (2n/a) (22); (2nla) (2%) The first Brillouin zone has the shape of the truncated octahedron as shown in Fig. 2.16. This is also one ofthe primitive unit cells of a bee lattice 2.8 ATOMIC SCATTERING FACTOR The diffraction conditions given by Bragg and Laue are concemed with scattering of x-rays from point scattering centres arranged on a space lattice. Since an electron is the smallest scattering centre, the diffraction conditions would ideally be applicable toa lattice in which every lattice point is occupied by an electron. This is, however, not a realistic situation. Lattice