is incident on a
medium from vacuum for grazing angles less than the critical angle
, where
is
classical electron radius and
is the electron density. Below the critical angle, the wave vector
inside the medium is purely imaginary and hence the wave cannot propagate. Thus only an
evanescent wave which decays exponentially inside the medium exists within the penetration
depth shown in figure-1
Fig-1 Evanescent wave (exponentially decaying with increasing distance from the interface)
2
The typical value of penetration depth is ~50 . For incidence angles
and
respectively, make equal angles u with the boundary. Since both
and
propagate
in the same medium (vacuum), their magnitudes are equal i.e.
.
Fig-2 (a) Reflection and transmission of plane electromagnetic wave, represented by wave vector from
the surface of a medium optically characterized by refractive index . (b) Vector scattering diagram
3
However the change in momentum transfer vector perpendicular to the surface is
2
The parallel component of momentum transfer vector lying in xy plane is zero. The
perpendicular component (along z-direction) given by above equation is changed either by
varying incident angle at the fixed wavelength or by varying wavelength at the constant angle u.
A general case of scattering is depicted in figure-3.
It is shown that if the incident and reflected angles
and
and
and
4
These x and z components can be varied experimentally in four different ways by coupled and
independent motion of the sample and detector as listed below:
(a) Specular scan-
If both sample and detector are rotated such that the incident and reflected angles
are equal i.e.
then it results in
while
fixed and
. For
, where
6
Therefore the x-ray reflectivity technique becomes highly surface sensitive at extreme
grazing angles. A typical penetration depth curve for two different wavelengths, (hard
x-rays) and (soft x-ray), in molybdenum material is shown in figure-4.
6
Below critical angle the penetration depth is few tens of angstrom whereas for
it
increases drastically. As soft x-rays are highly absorbing in all materials
the
penetration depth is only few hundreds of angstrom even in
.
Reflection from a single smooth boundary can be calculated using the well-known Fresnel
formulas written below. For a single vacuum/medium interface, the Fresnel reflection and
transmission coefficients for s polarized light can be written as:
8
where
and
[Ref-2]
7
an experiment, the measured parameter is the Fresnel reflectivity R
F
that is given as the modulus
square of the amplitude reflection coefficient r.
The equation for Fresnel reflectivity can be simplified in the small angle approximation
for
as
9
An example of s-polarized reflectivity from a single smooth surface as a function of
normalized incidence angle
. The total external reflection region below the critical angle is very
sensitive to the ratio |/o. As absorption increases or ratio increases the shape of the curve
changes.
Fig-5-X-ray reflectivity from a single surface as a function of normalized angle of incidence
Below
critical angle, the total external reflection yields the 100% reflectivity if |=0. As ratio increases the
reflectivity profile gets modified.[Ref-2]
8
The Fresnel reflectivity is plotted as open circles in figure-6 against
and
respectively and
be the normal component of the wave vector transfer in
vacuum, film and substrate respectively. The reflected amplitude of the thin film structure is
given as,
10
with
11
Where is the phase difference between the scattered amplitude from the two interfaces
which give rise to the oscillatory behaviour in the reflectivity pattern measured as a function of
angle or the wave vector transfer. The oscillation frequency determines the thickness of the film;
if q is the difference in wave vector transfer (in the film taking refraction into account) between
10
any two successive maxima/minima, then gives the thickness d of the film. The
amplitude of the oscillations is proportional to the contrast in electron density between the film
and the substrate.
If only the single scattering events from the two interfaces are considered, the resultant
reflectivity can be described by the numerator of eq
n
-(10) alone and the denominator term can be
neglected. The multiple scattering effects give rise to higher order terms and the denominator
term in eq
n
-(10) becomes significant. Another important aspect is the relation between the film
thickness and the oscillation frequency. As the thickness of the film increases, the angular
separation between two successive peaks decreases. This can be understood by the fact that the
reflectivity is the Fourier transform of the electron density variation in the real space. This is
illustrated in figure-7 which shows the simulated curve of a 200 and 800 thick Pt film on a
silicon substrate.
Fig-7- X-ray reflectivity spectra of Pt film of thickness200 and 800 on Si substrate . Figure shows the
dependence of the oscillation frequency on the film thickness.
0.0 0.5 1.0 1.5 2.0 2.5 3.0
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
R
e
f
l
e
c
t
i
v
i
t
y
Incidence Angle degree
B
11
4.2-Bilayer film on a substrate:-
The formula for single layer film on the substrate can be extended to that of a two
layer film, A and B, on the substrate. The reflectivity would be due to the interference of
radiation scattered from three interfaces viz. vacuum/A, A/B and B/substrate. Due to the
presence of two layers, the oscillation frequency of the thicker layer is modulated by that of the
thinner layer. Using the analogy given in the above section for single layer films, the difference
in wave vector transfer (in the medium) between the successive maxima of the high (low)
frequency modulation gives the thickness of the thicker (thinner) layer. Figure-8 shows x-ray
reflectivity spectra corresponding to different thicknesses of Mo/C bilayer structures. Curve
corresponding to Mo and C layer thickness of 50 is marked as a where two frequency
modulation viz. 50 and 100 are shown. Similarly curve marked as b is corresponding to C-
Mo bilayer of 100 and 800 thicknesses respectively. This clearly shows the high frequency
oscillations due to the thick Mo layer modulated by the thinner C layer.
Fig-8- X-ray reflectivity spectra of Mo/C bilayer film at =1.54, (a) and (b)
on Si substrate showing the frequency of the total film thickness modulated by the individual layer
thicknesses. The curves are vertically displaced for clarity
0.0 0.5 1.0 1.5 2.0 2.5 3.0
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
10
1
R
e
f
l
e
c
t
i
v
i
t
y
Incidence Angle (in degree)
(a)
(b)
12
4.3-Multilayer structure:-
A multilayer structure consists of alternate layers of two materials A and B
repeated over N periods. Reflection and transmission of the incident wave field inside a layered
media is illustrated in figure-9. Interfaces formed at the boundaries between two materials are
assumed to be sharp. The material and its structure both are homogeneous along the surface that
is parallel to xy plane. The change in material occurs only in the z-direction. N layers of two
materials between vacuum and substrate having the thicknesses
are optically
recognized by the refractive indices
12
where
is the envelope function which depends on the composition profile within the
period. The relative thicknesses of the constituent layers in the period modulate the reflected
intensity distributed into different orders of Bragg peaks. The simulated reflectivity pattern of
Mo/Si multilayer having a period of 50 for 10 layer pairs (i.e.20 layers) is plotted in figure-10
for three different values of .
Fig-10- Simulated reflectivity spectra of Mo/Si multilayer with a period of 50 at using
different Ivalues(a) I =0.40,(b) I =0.50, and(c) I =0.33.
10
-5
10
-3
10
-1
10
-5
10
-3
10
-1
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
10
-5
10
-3
10
-1
(a)
R
e
f
l
e
c
t
i
v
i
t
y
gamma 0.4
(a)
(b)
R
e
f
l
e
c
t
i
v
i
t
y
gamma 0.5
(c)
R
e
f
l
e
c
t
i
v
i
t
y
Incidence Angle (in degree)
gamma 0.33
14
- For I=0.40, since 1/I is not an integer, there is no preferential attenuation in the intensity
of the Bragg peaks and the higher orders decrease monotonically in intensity.
- For I=0.50, the intensity at the even orders are suppressed.
- For I=0.33, the third order and its multiples are suppressed.
5- Effect of interfacial width on reflectivity:-
The amplitude reflectance can be written within the Born approximation as:
13
Equation-13 implies that the amplitude reflectance is the Fourier transformation of the
gradient of electron density variation as a function of depth. When the electron density variation
(z) in a medium is known, the calculation of reflectance of the medium is defined as the direct
problem of reflection. On the contrary, in practice, of the medium has to be evaluated from
the reflectivity data measured as a function of the wave vector transfer
which is thereby
defined as the inverse problem of reflection. The above equation is analogous to the definition
of structure factor in conventional x-ray diffraction. The reflectivity is given as:
14
where
15
which causes damping of the reflected intensity by the factor
.
16
(a) Uncorrelated type: In this case, no replication occurs towards the free surface. The
roughness profiles of different interfaces are independent.
(b) Cumulative type: The roughness increases towards the free surface, indicating
roughening during growth.
(c) Partially correlated type: The roughness of a layer is partially transmitted towards free
surfaces.
(d) Correlated type: All the interfaces have identical roughness
The damping factor is multiplied with the reflectivity of a smooth surface (Fresnel reflectivity) is
valid when the widths of all the interfaces are identical and corresponds to all the interfaces
being conformal. For a general case, the attenuation factor is multiplied with the Fresnel
reflectance and is given as:
16
The assumption made in the derivation of equation-16 is that the momentum transfer q is
constant within the transition into the material, but the change in refractive index changes the
propagation angle and the value of q within the transition layer from a value q in medium-1 to a
value
by
17
7-Effect of roughness on reflectivity of a surface:-
7.1- From a single surface:
Figure-13 shows the effect of interfacial roughness on the reflectivity of a single
surface. As an example, the simulated reflectivity (for a wavelength of 1.54 ) of a silicon wafer
is shown using the Gaussian interface model, for;
(a)-zero roughness and
(b)-7 roughness;
It can be observed that the detrimental effect of roughness on the reflectivity is higher at larger
angles (larger q-values).
Fig-13 Simulated Fresnel reflectivity from a surface with
and
for different values of root mean square roughness . (a) and (b)
0.0 0.5 1.0 1.5 2.0
10
-7
10
-6
10
-5
10
-4
10
-3
10
-2
10
-1
10
0
R
e
f
l
e
c
t
i
v
i
t
y
Incidence Angle degree
o = 0.0 A
o = 7.0 A
18
7.2 From a thin film (A single layer on a substrate):
As explained above, the amplitude of the interference oscillations from a single
layer film depends on the electron density contrast between the film and the substrate. The
presence of finite roughness
and
.[Ref-3]
19
(i)-
and
and
and
multiplies the
oscillatory terms in the numerator as well as in the denominator whereas the term
containing
and
means that a large dynamic range, typically five to six orders of magnitude, is required
to measure a reasonable range of scattering vectors. The scattering geometry is usually chosen to
have the scattering plane vertical to take advantage of the small opening angle of the synchrotron
radiation perpendicular to the plane of the ring. Resolution is determined usually by the rocking
curve width of the monochromator or analyzer crystals.
Furhter energy dispersive x-ray raflectivity has been devloped as an alternative to the
conventional angle-scanning approach described above. In this type of reflectometer,a broad-
band source of radiation is employed in a fixed angle-scattering geometry, using an
energydispersive detector to measure the reflectivity as a function of x-ray energy. A typical in
situ experimental arrangement is shown in Figure-16.
Fig-16 Schematic diagram of an energy dispersive reflectometer.
21
In this type of reflectometer x-ray energies up to 40 keV are typically used to obtain a useful
range of scattering vectors. The characteristic lines of the source provide a convenient energy
calibration for the detector, The detector is an energy-dispersive intrinsic Ge detector. The entire
energy spectrum is collected simultaneously and transferred to computer for analysis. The
resolution of the detector is typically about 1%, which limits the resolution of the
reflectivity spectrum. The optics required are extremely simple. Only slits are used to define the
incident and exit angles.
22
9- Books referred:-
1- Jens Als- Nielsen Des McMorrow, Elements of modern x-ray physics, (John Wiley &
Sons, 2001)
2- Mohammad Hussein Modi, Surfaces and interfaces studies in multilayers. (PhD Thesis
2005).
3- N Suresh, PhD Thesis 1998.
4- E. Spiller, Soft X-ray Optics (SPIE, Bellingham, USA, 1994).
5- Ullrich Pietsch, Vaclav Holy and Tilo Baumbach, High- Resolution X-Ray scattering
From Thin Films to Lateral Nanostructures, (Springer,2004)
6- M. Tolan, X-Ray scattering from soft-matter thin films, Springer Tracts in Modern
Physics, (Springer1999)
7- D. Attwood, Soft x-rays and extreme ultraviolet radiation: Principles and applications
(Cambridge University Press, 1999).
8- Ron Jenkins, X-ray Diffraction, (John Wiley & Sons, 1996)
9- E.chason and T.M.Mayer, Thin film and surface characterization by specular x-ray
reflectivity,(Critical Review in Solid State and Material sciences,22(1):1-67 (1997)