ExP IVb ch4
ExP IVb ch4
• basic question:
what is the effect of the periodic crystal lattice on a wave transmitted through a
solid?
• effects are strong when the wavelength λ is of the order of the lattice constant or
the distance between parallel lattice planes.
59
60 Chapter 4 Crystal lattice and waves — the reciprocal lattice
Figure 4.3: Derivation of the Bragg equation 2d · sin Θ = nλ; d is the spacing of parallel
atomic planes and 2πn is the difference in phase between reflections from successive
planes. The reflecting planes have nothing to do with the surface planes bounding the
particular specimen. [from Kittel, Introduction to solid state physics (1996); Fig.2.2].
– let’s assume the angle between the incident wave and the lattice plane is Θ.
– the retardation (’Gangunterschied’) between two waves which are scattered
on neighboring lattice planes is 2 · d · sin Θ.
– constructive interference occurs for
Notes:
• photons:
not electrically charged → mostly relatively weak interaction
Bragg reflection requires much shorter wavelength → x-rays
energy of photons from x-rays (keV) À typical energy in a solid (meV. . . eV)
each lattice plane reflects only 10−3 to 10−5 of the incident radiation.
→ 103 to 105 lattice planes may contribute to the Bragg-reflected beam.
• electrons:
electrically charged → very strong interaction,
absorption in the lattice planes close to the surface of a crystal
for wavelengths in the Å-regime: electron energy ≈ 100 eV
• neutrons:
not electrically charged, but carry a magnetic moment:
→ relatively weak interaction,
reach far into the crystal,
’see” also magnetic properties (e.g. magnetic ordering)
for wavelengths in the Å-regime: Energy ≈ 0.1 eV
corresponds to typical energies in a solid
→ neutron (almost) ideally suited for spectroscopy with energy- and
momentum-resolution.
→ Disadvantage: requires large crystals (≈mm3 ) which are often not
available
• elekcrons and lattice vibrations in a crystal:
kinetic properties (energy-momentum-relation) are strongly modified,
when the Bragg law is fulfilled:
generation of standing waves → imobile elektrons/phonons
Figure 4.4: The difference in path length of the incident wave ~k at the points O und ~r
is r sin ϕ, and the difference in phase angle is (2πr sin ϕ)/λ, which is equal to ~k · ~r. For
the diffracted wave the difference in phase angle is −~k 0 ·~r. The total difference in phase
angle is (~k − ~k 0 ) · ~r, and the wave scattered from the volume element dV at location ~r
has the phase factor exp[i(~k − ~k 0 ) · ~r] [from Kittel, Einführung in die Festkörperphysik
(1999); Fig.2.6].
• phase difference between waves scattered at ”0” and at the volume element ”dV ”:
~ ~0
ei(k−k )·~r
• task:
determine G~ (=”reciprocal lattice vector”)
in such a way that n(~r + T~ ) = n(~r) is valid.
~ = v1~b1 + v2~b2 + v3~b3 with integer v1 , v2 , v3 and:
• solution: G
The vektors ~b1 , ~b2 , ~b3 are the axis verctors of the ”reciprocal lattice”
X ~ ~
X ~ ~~
n(~r + T~ ) = nG~ eiG(~r+T ) = nG~ eiG~r eiGT
~
G ~
G
X ~ r i2πn
X ~
iG~
= nG~ e e = nG~ eiG~r · 1 = n(~r)
~
G ~
G
q.e.d.
⇒ scattered amplitude
Z X
~ ~ ~
F = dV n(~r)e−i∆k~r = nG~ ei(G−∆k)~r
crystalvol. ~
G
– for ∆~k = G:
~ F = V ol · n ~
G
– for ∆~k 6= G:
~ F ≈0
• draw in ~k-space a line from a reciprocal lattice point ”0” to another lattice point;
~ (see figure below)
this shall be a reciprocal lattice vector G
~ a line perpendicular to G
• draw halfway at G/2 ~
µ ¶2 Ã !2
G ~
G G~ G2 ~ ~
+ h2 = k 2 ; + ~h = ~k ⇒ h2 = ~k − = k2 + − kG
2 2 2 4
µ ¶2
G G2 ~ ~
⇒ + k2 + − kG = k2
2 4
G2 ~ ~
⇒ = kG q.e.d.
2
• Note: analogous construction was used in real space,
eads to the Wigner-Seitz cell
65
We know that a diffraction maximum appears when (~a · ∆~k) = 2πn, where n is
an integer. We change ∆~k slightly and define ε in (~a · ∆~k) = 2πn + ε such that
~ (~a · ∆~k). It can be shown that
ε gives the position of the first zero in sin2 21 M
ε = 2π/M ~ , so that the width of the diffraction maximum is proportional to 1/M
and can be extremely narrow for macroscopic values of M . The same holds for a
3- dimensional crystal.
~b1 = 2π (ŷ + ẑ), ~b2 = 2π (x̂ + ẑ), ~b3 = 2π (x̂ + ŷ) = fcc lattice
a a a
Surface of the 1. Brillouin zone: see figure
Figure 4.11: 1. Brillouin zone of the body-centered cubic lattice: The figure is a regular
rhombic dodecahedron [from Kittel, Introduction to solid state physics (1996); Fig.2.13].
69
Figure 4.12: Brillouin zones of the face-centered cubic lattice. The cells are in the
reciprocal space, and the reciprocal lattice is body-centered [from Kittel, Introduction
to solid state physics (1996); Fig.2.15].
Figure 4.13: Primitive basis vectors of the face-centered cubic lattice [from Kittel,
Introduction to solid state physics (1996); Fig.2.14].
70 Chapter 4 Crystal lattice and waves — the reciprocal lattice
– until now: we considered only the effect of the lattice on the scattering amplitude
F.
here, N is the number of unit cells in the crystal and SG~ is the ”structure
~
factor” of the reciprocal lattice vector G
• assume the basis consists of s atoms; with atom j at the location ~rj and described
by an electron density nj (~r P
− ~rj ).
We then get: n(~r) = sj=1 nj (~r − ~rj )
X Z ~
⇒ SG~ = dV nj (~r − ~rj )e−iG~r
j
crystal
X Z X
~ rj
−iG~ ~ ~
= e ρ)e−iG~ρ =
dV nj (~ e−iG~rj fj
j j
crystal
→ every second reflex of the cubic unit cell is suppressed; due to destructive
interference of the wave scattered on both atoms
71
Figure 4.14: Comparison of x-ray reflections from KCl and KBr powders. In KCl the
numbers of electrons of K+ and Cl− ions are equal. The scattering amplitudes f (K+ )
and f (Cl− ) are almost exactly equal, so that the crystal look to x-rays as if it were a
monatomic simple cubic lattice of lattice constant a/2. Only even integers occur in the
reflection indices when these are based on a cubic lattice of lattice constant a. In KBr
the form factor of Br− is quite different than that of K+ , and all reflections of the fcc
lattice are present (Courtesy of Robert van Nordstrand) [from Kittel, Introduction to
solid state physics (1996); Fig.2.17].
72 Chapter 4 Crystal lattice and waves — the reciprocal lattice
Figure 4.15: The points on the right-hand side are reciprocal lattice points of the
crystal. The vector ~k is drawn in the direction of the incident x-ray beam, and the
origin is chosen such that ~k terminates at any reciprocal lattice point. We draw a
sphere of radius k = 2π λ
about the origin of ~k. A diffracted beam will be formed if
this sphere intersects any other point in the reciprocal lattice. The sphere as drawn
intercepts a point connected with the end of ~k by a reciprocal lattice vector G.
~ The
diffracted x-ray beam is in the direction ~k = ~k + G.
0 ~ The angle θ is the Bragg angle
of fig.4.3. This construction is due to P.P. Ewald [adapted from Kittel, Introduction to
solid state physics (1996); Fig.2.08].
73
– powder diffraction:
∗ In a powder all crystal orientations are present
∗ does not require large single crystals
Figure 4.17: (a) Debye-Scherrer recording from Cu powder (b) Pattern obtained from
ore (’Erz’) using a powder diffractometer (top) and diffraction lines as suggested from
a computer-software (bottom) calcualted for reference compounds from the JCPDS
data base (Fa. Stoe & CIE GmbH, Darmstadt) [from Bergmann-Schaefer, Lehrbuch
der Experimentalphysik (1992); Fig.2.33].
75
– Laue method
uses single crystal + ’white’ source
Figure 4.19: (a) Laue diffraction from Kalialaun (KAl(SO4 )2 · 12H2 O)(cubic, space
group Pa3) in [100] direction. The patterns shows clearly an absence of a 4-fold sym-
metry. This allows the unambiguous discrimination between the possible cubic Laue
classes m3 und m3m in favor of m3. (b) Laue pattern obtained from a quasi crystal
Al6 CuLi3 with 5-fold symmetry [from Bergmann-Schaefer, Lehrbuch der Experimental-
physik (1992); Fig.2.35].
76 Chapter 4 Crystal lattice and waves — the reciprocal lattice
Figure 4.20: (a) Geometry of ’Euler-Wiege’; (b) realization of the Ewald diffraction
conditions in the plane of diffraction of a ’Euler-Wiege’. [from Bergmann-Schaefer,
Lehrbuch der Experimentalphysik (1992); Fig.2.45].
77
• Neutron diffraction:
Figure 4.21: Neutron diffraction patterns for MnO below and above the spin-ordering
temperature of 120 K, after C.G.Shull, W.A.Streuser and E.O.Wollan. The reflection
indices are based on an 8.85 Å cell at 80 K and on a 4.43 Å cell at 293 K. At the higher
temperature the Mn2+ ions are still magnetic, but they are no longer ordered [from
Kittel, Einführung in die Festkörperphysik (1999); Fig.15.20].
Figure 4.23: The dependence of intensity on temeperature for the (h00) x-ray reflections
of aluminium. Reflections (h00) with h odd are forbidden for an fcc structure. (After
R. M. Nicklow und R. A. Young) [from Kittel, Einführung in die Festkörperphysik
(1999); Fig.A.01].
79
• Atom j in crystal oscillates with amplitude ~u about ~rj0 : ~rj (t) = ~rj0 + ~u(t)
~ ~ ui − 1 h(G~
~ u) 2 i + . . .
Term heiG~u i ≈ 1 + ihG~ 2
~ ui = 0, for harmonic oscillation.
– hG~
~ u)2 i = G2 hu2 ihcos2 Θi = 1 hu2 G2 i
– h(G~ 3
with Θ: angle between G ~ and ~u and hcos2 Θi = 1
with geometric
3
averaging over a sphere
~ 1 1 2 2
⇒ heiG~u i ≈ 1 − hu2 iG2 ≈ e− 6 hu iG
6
1 2 2
scattering intensity =(amplitude)2 =I0 e− 3 hu iG
3
Mean thermal energy hU i of a harmonic oscillator: k T
2 B
1 1 3 C
⇒ hU i = chu2 i = M ω 2 hu2 i = kB T ; (ω 2 = )
2 2 2 M
solve for hu2 i
2 /(M ω 2 )
⇒ I = I0 e−kB T G
q.e.d.
80 Chapter 4 Crystal lattice and waves — the reciprocal lattice