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Reciprocal Lattices and Diffraction

Suggested
gg
Reading
g
Chapter 6, M. DeGraef and M.E. McHenry, Structure of Materials, Cambridge (2007).
Appendix A from Cullity & Stock

1

Many physical properties of crystals as well
as the geometry of the three
three-dimensional
dimensional
patterns resulting from a diffraction event
are most easily represented using the
concept of the reciprocal lattice!
Diffraction occurs in inverse proportion
to the spacing between objects causing
diffraction
2

Reciprocal Lattice
• Vector representation of directions and
interplanar spacing of diffracting planes.
• Real Space:
– a,
a b,
b c,
c , , 
• Reciprocal Space: (just another type of lattice)
– a*,
* b*
b*, c*,
* *,
* *,
* *
3

Reciprocal Lattice
(FCC)
0,0,2
2,0,2

022
0,2,2

c* 2,2,2

1,1,1

b*

a*
0,0,0
2,0,0

Real Space

0,2,0
2,2,0

Reciprocal Space

Recall simple vector operations • Dot product (scalar product): x  y  x y cos  z y h2  k 2  l 2 h2  k 2  l 2 • Cross product (vector product): x  y  z  x y sin i   x z is the direction  x  y plane 5 .

Useful Properties of the reciprocal lattice c  * a  b  c  a  b  area of base  unit cell volume 1  height 1  d001 For orthogonal crystals. c* c B b O a C A z d001 in real space Plane normal to (001) y x 1 1 * c  d001 c 6 .

b  c b  c   a*   a  b  c  V c  a c  a   b*   b c  a V a  b a  b   c*   c  a  b V c** c b* b O a a* V  unit cell volume  a   b  c   b   c  a   c   a  b  a*  bc plane in real space. it is the reciprocal lattice vector for a b*  ac plane in real space. it is the reciprocal lattice vector for b c*  ab plane in real space.We can define reciprocal lattices • F For an arbitrary bit llattice tti [a  b  c and d      ( 90°)] in i real space. it is the reciprocal lattice vector for c 7 .

Useful Properties of the reciprocal lattice – cont’d 1 *  a . b cos  cos   cos  cos   sin  sin  1 1 * c   c . a cos  cos   cos  cos   sin  sin  1 *  b . d001 c cos  cos   cos  cos   sin  sin  a  * b  * 1 d100 1 d010 * * * * For orthogonal crystals 8 .

Relationship between real and reciprocal In orthogonal real lattices (a= b = c and =  =  (= 90°)) a*  a. b*  b. c*  c Not necessarily so in non-orthogonal non orthogonal lattices We can draw an analogy gy between reciprocal p and real lattices: ruvw  ua  vb  wc We use this to build a real lattice from unit cells rhkl*  ha*  kb*  lc* We can use this to build a reciprocal lattice 9 .

NJ. Hoboken.Construction of a 2D reciprocal lattice b a 01  10 (a) draw the plane lattice and mark the unit cell Adapted from R. John Wiley & Sons. Tilley. 2006 10 . Crystals and Crystal Structures.

Hoboken. 2006 00 01 * b* 10 a* (b) draw lines perpendicular to the two sides of the unit cell to give the axial directions of the reciprocal lattice basis vectors. Tilley. Crystals and Crystal Structures.Construction of a 2D reciprocal lattice Adapted from R. NJ. 11 . John Wiley & Sons.

NJ. and take the inverse of these distances.Construction of a 2D reciprocal lattice Adapted from R. as the reciprocal lattice axial lengths. John Wiley & Sons. (c) determine the perpendicular distances from the origin of the direct lattice to the end faces of the unit cell. 1/d10 and 1/d01. d10 and d01. Crystals and Crystal Structures. 2006 00 01 * b* 10 a* Sets axes and interaxial angle What you’re doing first is finding the spacing between the planes making up the unit cell sides. a* and b. Hoboken. Tilley. 12 .

Crystals and Crystal Structures. John Wiley & Sons. Tilley.Construction of a 2D reciprocal lattice Adapted from R. NJ. Hoboken. and complete the lattice. 13 . t (d) mark the lattice points at the appropriate reciprocal distances. 2006 00 1  a*  * d 01 10 b*  1 / d 01 01 Draw reciprocal lattice using axes a* = 1/d10 a b* = 1/d01 T k reciprocals Take i l tto gett reciprocal i l llattice tti parameters.

Crystals and Crystal Structures. Hoboken. 14 . John Wiley & Sons.Construction of a 2D reciprocal lattice Everyy p point on a reciprocal lattice represents a set of planes in the real space crystal! Adapted from R. 2006 00 00 01 b a 10 11 Real lattice 1  a* d 01 10 b*  1 / d 01 01 1 d11 11 Reciprocal lattice The vector joining the origin of the reciprocal lattice to a lattice point hk is perpendicular to the (hk) planes in the real lattice and of length 1/dhk. Tilley. NJ.

(d) the lattice plane is completed by extending the lattice. y Crystals y and Crystal y Structures. (e) the reciprocal lattice is completed by adding layers above and below the first plane. (b) reciprocal lattice aces lie perpendicular to the end faces of the direct cell.c* c c a* d 001  a (a) d100 a (b) c* c** 102 a* 101 c*  1 d 001  * a*  1 d100 100 10 1 (d) (c) 002 001 000 b*  1 d 010 010 020 (e) 030 100 102 101 * 302 201 001 000 100 00 1 10 1 200 301 401 401 300 20 1 30 1 400 40 1 a* Figure 2.10 The construction of a reciprocal l tti (a) lattice: ( ) the th a-c section ti off the th unit it cell ll in i a monoclinic (mP) direct lattice. Hoboken. plane 200 012 011 110 002 202 Construction of a 3D reciprocal p lattice Adapted p from R. NJ. (c) reciprocal lattice points aree spaced ed a** = 1/d100 andd c** = 1/d001. Tilley. 2006 210 Just like 2 2-D D 15 . John Wiley & Sons.

Cubic Reciprocal Lattice b* b 0.25 Å-1 040 (010) (110) 4Å (210) c 020 a [010] 4Å REAL LATTICE ruvw  ua  vb  wc c* 90° 90 020 120 220 010 110 210 [110] [210] a* 200 400 RECIPROCAL LATTICE r hkl*  ha *  kb *  lc * • Every point on a reciprocal lattice represents a set of planes in the real space crystal! • Reciprocal lattice vectors are 90° away from real space planes! 16 .

. planes in crystals).Importance of Reciprocal Space • When a diffraction event occurs. the diffracted waves/pattern will “match” match the reciprocal lattice. • We make the use of this fact in x-ray y diffraction and transmission electron microscopy. ►Radiation ‘scatters’ scatters in inverse proportion to the spacings between diffraction centers (i.e. 17 .

Why use reciprocal space • Bragg’s Law: (Defines conditions where a crystal is oriented for coherent scattering) n  2d sin  We can combine n and d as follows: d d hkl  n Thi allows This ll us to t write it B Bragg's ' Law L as:   2d hkl sin  hkl sin  hkl 1 opposite  / 2 d hkl    2 d hkl hypotenuse  (Simple geometric proof on vg #226) 18 .

cam.sin  hkl 1 opposite BC  / 2 d hkl     2 d hkl hypotenuse AC h Ewald Sphere Construction  B Reflection or Ewald sphere Limiting sphere A CRITICAL Only lattice points lying within the limiting g sphere p can diffract. θhkl 2θhkl 2 1 *  dhkl dhkl C  (0.0) 1 2 Origin g of reciprocal lattice and center of limiting sphere See this web site for an explanation and example http://www.uk/doitpoms/tlplib/xray-diffraction/ewald.php 19 .ac.msm.0. Points lying on the Ewald sphere will satisfy the Bragg condition.

20 . “ fl ti ” off “reflecting” ff off crystallographic t ll hi planes l in i a direction di ti s. Let point O represent the origin of the reciprocal lattice. s/ s Incident wave so   B so C Incident wave   A  s  so   g  d *  so /  1  REAL SPACE • • • • hkl O g is the diffraction vector RECIPROCAL SPACE Consider incident waves of radiation (i. A.. Rotation of crystal rotates the reciprocal lattice about O.e. This will bring different reciprocal lattice points into contact w/ Ewald’s sphere.Ewald’s Sphere Construction • Graphical representation of Bragg Bragg’ss Law in reciprocal space space. on CO but passing through O. X-rays) moving in a direction so. Draw a circle of radius 1/λ w/ center.

Bragg’s law is satisfied! 21 .0) 1  d 0*10 RECIPROCAL SPACE My original way to show it. it Next page is better. • When points lie on the sphere. • Rotation of the crystal will cause points to lie on the sphere. • Size of sphere p corresponds p to wavelength g of radiation used (see next page). s  so   Ewald’s sphere  2sin  To satisfy Bragg's Law: s  so 1 *  d hkl   d hkl 1 d sin  hkl  Bragg's Law 2  * d 130  Crystalline C t lli solid so  * d 030 * d130 * d 230 * d 020 * d120 * d 220 * d 010 * d110 * d 210 * d100 * d 200 (0.0.

0.0)  A 1 O  d 0*10 RECIPROCAL SPACE • Size of sphere p corresponds p to wavelength g of radiation used (see next page). • When points lie on the sphere. • Rotation of the crystal will cause points to lie on the sphere. Bragg’s law is satisfied! 22 .Ewald’s sphere OB OB sin    CO 2 /  Which can be re-written as: C 1 2 sin    OB Since B is a reciprocal lattice point: 1 * OB   d hkl g d hkl  so  Crystalline C t lli solid 1  d hkl and 2d hkl sin    OB [Bragg’s Law] B * d 130 * d 030 * d130 * d 230 * d 020 * d120 * d 220 * d 010 * d110 * d 210 * d100 * d 200 (0.

. you change the radius of the Ewald’s sphere. 3rd Ed. The Basics of Crystallography and Diffraction. Oxford. 2009. UK. This is how the Laue technique works. 201.If you change λ. works Diffractometers generally use fixed λ and variable θ. Reflecting sphere for smallest wavelength Reflecting sphere for largest wavelength C. p. Oxford University Press. Hammond. 23 .

24 . Krawitz.A. New York. 2001 0° 0 θ1° θ2° Increasing diffraction angle Diffractometers generally use fixed λ and variable θ. Wiley.D. Introduction to Diffraction in Materials Science and Engineering Engineering.

Diffraction iff i off X-rays (and ( d electrons) l ) is i described d ib d by b the h Bragg equation. which relates the radiation wavelength (λ) to g (θ) ( ) and the spacing p g between crystal y the diffraction angle planes (dhkl). The length of the reciprocal lattice vector is equal to the inverse of the spacing between the corresponding planes. The reciprocal lattice vector d*hkl with components (hkl) is perpendicular to the plane with Miller indices (hkl).Synopsis 1. 25 . The reciprocal lattice allows us to compute the spacing between successive lattice planes in a crystal lattice. 2. 4. 3.

M M. Fundamentals of Powder Diffraction and Structural Characterization of Materials. Chapter 7. 2nd Edition.Diffraction and the Recripocal Lattice Suggested Reading 1 Chapters 11-14 1. Springer (2009) 26 . Structure of Materials. 2. DeGraef and M M. Materials Cambridge (2007). Pecharsky and Zavalij.E. 11 14. E McHenry McHenry.

wikipedia.Electromagnetic (EM) Radiation Self-propagating S lf i waves with ih perpendicular electric and magnetic components http://en.org/wiki/File:Onde_electromagnetique.svg 27 .

00 3 00  108 m/s /   wavelength of radiation 28 .Properties of Electromagnetic Waves – cont’d E  photon of energy  h  hc  h  Planck's constant  6.626  10 34 Js   frequency of the wave c  speed d of f light li ht  3.

05 Å http://en.5 Å •Electrons: λ ~0.•Visible Light: g λ ~6000 Å •X-rays: λ ~0.svg 29 .org/wiki/File:EM_Spectrum_Properties_edit.5 – 2.wikipedia.

org/wiki/File:EM_Spectrum_Properties_edit.svg 30 .http://en.wikipedia.

the EMR wavelength ≤ lattice spacing.e. absorbed + re-emitted): – Elastic (little or no energy loss  diffraction peak) – Inelastic (energy loss  no diffraction peak) 31 .Scattering of EM Radiation by Crystals • For a material to yield a diffraction pattern. – Neutrons – Electrons – X-rays • X-radiation is scattered (i..

Laue’s Equations • When scattering occurs there is a change in the path of the incident radiation. k . simultaneously 32 .  x  a (cos (   cos  o )  a ( S  So )  h  y  b(cos   cos  o )  b( S  So )  k   z  c(cos (   cos  o )  c( S  So )  l  [h. Diffracted beam  n  path difference between incident and S scattered beams. l are integers] α αo So a Incident beam • Constructive interference occurs when all 3 equations are satisfied simultaneously.

Bragg’s Law   A C  d  B   path difference  AB  BC  2d sin  For constructive interference   n    2d sin   n d d hkl  n   2d hkl sin  (or n  2d sin  ) 33 .

Bragg’s Law • Bragg’s la law can be expressed e pressed in vector ector form as: * S  So  2sin    d hkl * d hkl  hkl * d hkl 1 d hkl Incident beam So • Thus: S  So  -So S-So θ *  d hkl lc * hkl  ha *  kb * lc θ S Diffracted b beam Trace of (hkl) reflecting plane • This tells us that constructive interference occurs when S–So coincides with the reciprocal lattice vector of the reflecting planes. 61 in text 34 . Ref p.

e. is generally used for convenience. point • Point’s satisfying this criteria represent planes that are oriented for diffraction d h*kl  S  So  (13) S  (01) (11) (00) (10) 2θ 1  So  (10) Reflecting sphere • Bragg’s law. 35 . • For diffraction to be observed (i (i. hi ll • Similar to Ewald’s sphere.Laue’s Equations and the Reciprocal Lattice • We W can representt the th Laue L equations ti graphically. which describes diffraction in terms of scalars. e Bragg Bragg’s s law satisfied) S must end on a reciprocal lattice point.

Diffracted beam d * hkl  S  So  (13) Limiting sphere RADIUS = 2So/λ S  INCIDENT BEAM (01) (11) (00) (10) 2θ So  Reflecting sphere (10) To satisfy Bragg’ss Bragg law So S *  d hkl    n  2d sin * d hkl  g  1 2 sin  d n 36 .

Reciprocal Lattice • The lattice constructed from all diffraction vectors (i.. However. • Changes in wavelength (λ) changes the circle radius which can lead radius. 000 Incident beam c*000 b* a* 37 . to diffraction. we generally do not change λ.e. • Points that intersect the reflecting sphere will satisfy Bragg’s law. g) for a crystal defines possible Bragg reflections.

and limiting sphere. reflecting sphere. • We mentioned this a few lectures ago.Reciprocal Lattice • A change in orientation of the incident beam relative to the crystal changes the orientation of the reciprocal lattice. 000 38 . Incident beam • Change g will eventuallyy yield a condition where diffraction is possible.

X-ray Diffractometer • X-ray source is generally fixed. Focal circle Source Detector Fixed Rotates on focal circle θ 2θ Sample Rotates or remains stationary Bragg Bretano Bragg-Bretano 39 . • Rotate sample and detector to adjust θ/2θ. θ/2θ • On instruments such as our Bruker D8. the source and detector move while th sample the l remains i stationary.

Bragg’s Law   A C  d  B   path difference  AB  BC  2d sin  For constructive interference   n    2d sin   n d d hkl  n   2d hkl sin  40 .

y • Cubic:   2d sin  sin 2    1 d2 h   2  k2  l2  2 4a 2 h 2  k2  l2  a2 • This equation predicts.Diffraction Directions • We can determine which reflections are allowed by combining Bragg’s law with the plane-spacing equations q for a crystals. for a particular incident λ and a particular cubic crystal of unit cell size a. all of the possible Bragg angles for the diffracting planes (hkl) 41 .

Diffraction Directions – cont’d • Example: What are the possible Bragg angles for {111} planes in a cubic crystal? • Solution: 3 sin 111  2 1  1  1   2 4a 4a 2 2 2 h 2 k 2 l 42 .

sin   2  2  2  4 a 4a c  • Solution: must know c and a. Will be one p peak. • What about {110}? I’ve intentionally given you a family here 43 .Diffraction Directions • What about other systems? • Tetragonal:   2d sin  sin 2    1 d2 h   2  k2  a2 l    2 c2  2  h2  k 2 4a 2  a2 l2   2 c  2  2 1  2 For 111 .

Fundamentals of Powder Diffraction and Structural Characterization 44 of Materials. reciprocal lattice vectors. • Theyy pproduce ppowder diffraction cones at different Bragg angles (see the next slide). but identical.Ewald s Ewald’s Sphere Diffraction Cone S Incident Beam • In powder diffraction you generate an infinite i fi i number b off randomly oriented. Zavalij. © Kluwer Academic Publishers (2005) . Pecharsky and Peter Y. • They form a circle with their ends placed on the surface of Ewald’s sphere. Debye Ring * d hkl 2 So S Detector * R *  g  d hkl  1 d hkl Adapted from Vitalij K.

p.Adapted from Vitalij K. Zavalij.2 45 . 2nd Edition. 154. Ewald’s Ewald s sphere * d hkl  Incident Beam 1 d hkl So Figure 8. Pecharsky and Peter Y. Fundamentals of Powder Diffraction and Structural Characterization of Materials. © Kluwer Academic Publishers (2009).

the detector scans through an arc that intersects each Debye cone at a single point. p. Figure 8. 46 . 2nd Edition. © Kluwer Academic Publishers (2009). thus giving i i th the appearance off a discrete diffraction peak.Adapted from Vitalij K. Zavalij. Fundamentals of Powder Diffraction and Structural Characterization of Materials. 156.4 In a linear diffraction pattern. Pecharsky and Peter Y.

c = 9 Å) crystal. 47 .Exercises 1. Develop equations for the angles of diffraction for a tetragonal (a = 3 Å.