Structure analysis: Electron diffraction

LEED: Low Energy Electron Diffraction

SPA-LEED: Spot Profile Analysis Low Energy Electron diffraction
RHEED: Reflection High Energy Electron Diffraction
TEM: Transmission Electron Microscopy

LEED RHEED TEM

ki ki
kf
ki kf
kf

E = 10 500 eV E = 10 200 keV E = 10 200 keV

Electron mean free path

 Basic theory of diffraction
By the principles of wave-particle duality, the beam of electrons may be
equally regarded as a succession of electron waves incident normally on
the sample. These waves will be scattered by regions of high localized
electron density, i.e. the surface atoms, which can therefore be
considered to act as point scatterers.
The wavelength of the electrons is given be the de Broglie relation :
Wavelength, = h / p ( where p - electron momentum )
Now ,
p = m v = (2 m E )1/2 = (2 m e V)1/2
= h / ( 2 m e V )1/2

h Planck constant = 6.6 10-34 J s

m electron mass = 9.1 10-31 Kg
v electron velocity
E electron kinetic energy
e electron charge = 1.6 10-19 C

Example:
1) Electron energy = 20 eV -> Wavelength = 2.7
2) Electron energy = 200 eV -> Wavelength = 0.87

comparable to the atomic spacing

N.B.: Electron energy = 2 eV -> Wavelength = 8.5 i.e. the

hypothetical RLEED would have low resolution
 Plane wave scattered by a point

f(,r) eir k f

eir k i

In the case of many scatter points the scattered

wave is given by:
j fj(,rj) eirj kf

fj(,rj) is the atomic structure factor

 Two points scattering
ni

ki ki = 2ni/
nf

kf = 2nf/
d cos i = d ni d
i
f
kf
d cos f = - d nf

Elastic scattering: |ki| = |kf| or the incident and reflected

rays have the same wavelength

Constructive interference: d cos i + d cos f = d (ni - nf) = m

or
d (ki - kf) = 2m m integral

This is also equivalent to: e-id (ki kf) = 1

Bravais lattice
The condition of constructive interference has to be verified
by all the lattice points, i.e.
R (ki - kf) = 2m with R Bravais lattice vector,
or
(ki - kf) = G with G is a vector of the reciprocal lattice
 Laues diffraction condition: kf = ki G
Given an incident wave ki, the diffraction spots are
located by the kf vectors verifying:
1) |ki| = |kf|
2) kf = ki G

2D case or the case of a surface

2D lattice described by Rs implying Rs (ki - kf) = 2m
or (kf - ki)// = k// = Gs with Gs vector of the 2D reciprocal
lattice

The diffraction spots is a map of the 2D reciprocal lattice

Example a1* = 2/ a1 a1/ a1

a2 a2* = 2/ a2 a2/ a2

a1
Rs = 1 a1 + 1 a2 = (a1, a2,0)
ki =(0,0,1)
Gs = s (1 a1* + 1 a2*) = s (2/a1, 2/a2,0)

kf
kf = (2s/a1, 2s/a2,c) ki
with c2 = 1 (2s/a1)2 (2s/a2)2

G1 G2
 Bravais lattice with basis
Consider the elementary cell located at R and assume the
cell containing a basis of N atoms.
The coordinates of the j-atom in the cell are:
rj = R + dj with dj the position vector inside the cell

The amplitude of the diffracted wave is given by:

= h f(rh) ei rh G = f R j ei rj G (f identical for all
all atoms Bravais N

atoms)

In general f is atom dependent -> spot intensity reflects the

atomic structure factor

Diffraction from N = N1 x N2 lattice points

1 + e-i + .. e-i(N1-1) + e-i(N2-1)

I(Gs) |T(Gs) |2 = i=12 sin2(Ni Ri Gs /2)/ sin2(Ri Gs /2)

Peak width inversely proportional to N

 LEED may be used in one of two ways
Qualitatively : the diffraction pattern is recorded;
analysis of the spot positions yields information on the
size, symmetry and rotational alignment of the surface
unit cell with respect to the substrate unit cell.
Quantitatively : the intensities of the various diffracted
beams are recorded as a function of the incident electron
beam energy; comparison with theoretical curves, may
provide accurate information on atomic positions.

Experimental set-up

The LEED experiment uses a beam of electrons of a well-defined

low energy incident normally on the sample.

Only the elastically-scattered

electrons contribute to the
diffraction pattern ; the lower
energy (secondary) electrons are
removed by energy-filtering
grids placed in front of the
fluorescent screen that is
employed to display the pattern.
 fcc(100)

(0,0) represents the reflected beam along the surface normal

fcc(110)

Real space Diffraction pattern

a2*
a2
a1*
a1

a1* = 2/a1
a2* = 2/a2
 fcc(100) (2x2)

b2*

b1*

fcc(100) (2x2) R45 [c(2x2)]

 Fcc(111) + adsorbate

a1s = 2 a1 + 0 a2 Ideal surface

a2s = -1 a1 + 2 a2

Real surface

Three possible domains rotated by 60 depending on the

terrace
Spot diffraction due to surface defects

I0 Isteps I
atoms

Idown I
up
 LEED is sensible to surface defects

Steps behave like 1D adsorbate nets

 Spot Profile Analysis

Ideal case: the diffraction spots are described by functions

Real case: the diffraction spots are described by Gausss

functions

Reasons of the intrinsic width of the diffraction spot:

1) Electron energy non perfectly monochromatic
2) Electron beam non perfectly normal to the sample surface
3) Incident wave non perfectly plane
4) Aberrations of the optics

but also

The sample surface is not a ideal flat surface

steps, islands, adsorbates, etc.

The observed spot O(G) is the convolution of the ideal

diffraction spot I(G) with the instrumental transfer function
T(G) and the surface defect diffraction S(G):
O(G) = I(G) * T(G) * S(G)

The Fourier transform of T(G) is a gaussian function

The HWHM is defined as the transfer width and define the maximum
surface distance on which the diffraction is coherent (about 30-50 nm)
 SPA-LEED
Large transfer width 100 200 nm

STM images of Cu(100) ion

sputtered at room temperature.
Ion sputtering at normal
incidence produces square pits

200 x 200 nm2

SPA-LEED patterns

[Link]
Surface morphology for different ion sputtering direction

STM SPA-LEED

350 x 350 nm2

Rusponi et al. Appl. Phys. Lett. 75, 3318 (1999)

J. Wollschlger et al., Phys. Rev. B 57, 15541 (1998)
 RHEED

Electron penetration depth = 10-30 nm at 40 keV for

normal incidence
Surface sensibility if cos = d/ with d = 1- 2 atomic layers
or
about 89

Vertical bars in place of spots because due to the geometry the

technique is strongly sensible to surface defects (in the
impinging direction)

Due to the grazing incidence the surface is seen as a continuous

along the incidence direction (no diffraction) and consequently
only the periodicity perpendicularly to the incidence direction is
detected
 RHEED spectrum

e- beam

The spectrum is visible only if the incident beam is aligned

with a symmetry direction of the substrate
 RHEED sensibility to surface defects

Growth of GaAs(100) by
Molecular Beam Epitaxy
(MBE)

Neave et al. Appl. Phys. A 31, 1

(1983)

The intensity oscillations are a measure of the surface disorder

Oscillation period: 1 atomic layer

Intensity: decreasing with the Imperfect layer by
number of deposited layer growth
layers

Maximum disorder at 0.5 ML

during layer by layer growth
 What advantages does RHEED offer over LEED ?

Pro: 1) The geometry of the experiment allows much better access to

the sample during observation of the diffraction pattern. This is
particularly important if it is desired to make observations of the
surface structure during growth of a surface film by evaporation
from sources located normal to the sample surface or simultaneous
with other measurements (e.g. AES, XPS).
2) Experiments have shown that it is possible to monitor the atomic
layer-by-atomic layer growth of epitaxial films by monitoring
oscillations in the intensity of the diffracted beams in the RHEED
pattern.

Con: 1) quality of the diffraction pattern frequently lower

2) diffraction patterns have to be observed for at least two
sample alignments with respect to the incident beam in order
to determine the surface unit cell.
 Transmission Electron Microscope (TEM)
Conceptually is identical to an optical microscope where
electrons are used in place of photons

Diffraction plane

photons electrons

E = 75 keV -> = 0.05

Theoretical resolution about hundred thousands times

better than that of light.
 Unfortunately, this theoretical resolution has never come even
close to being attained. The basic draw back is that magnetic fields
can not be manipulated, shaped and grouped the way an optical
engineer does with glass lenses.

There are several disadvantages of electron optics.

1)Electrons are easily effected by any mater they encounter. When
they do encounter mater the interaction results in the emission of all
the lower forms of energy. Such as x-rays, secondary electrons,
ultraviolet, heat etc.
2) Complicate to describe the scattering process inside the object
3) The wave function resulting from the scattering process is falsified
by the optical system
4)The electrons can not pass through air. As a result the microscope
has to be kept in a high vacuum.
5)Our eyes are not sensitive to electrons so the operator must learn to
focus the instrument using different focal cues than he is used to.

Advantages of TEM over light microscopes:

1) about a thousand fold increase in resolution
2) a hundred fold increase in depth of field.

TEM image of DNA

TEM images of a single-crystal MTJ with the
Fe(001)/MgO(001)(1.8 nm)/Fe(001) structure. b is a magnification
of a. The vertical and horizontal directions respectively correspond to
the MgO(001) (Fe(001)) axis and MgO(100) (Fe(110)) axis. Lattice
dislocations are circled. The lattice spacing of MgO is 0.221 nm along
the [001] axis and 0.208 nm along the [100] axis. The lattice of the
top Fe electrode is slightly expanded along the [110] axis.

Nature Materials 3, 868871 (2004)