X-ray reflectivity technique and its application for

characterizing thin film/ multilayer structures

Reading course -2
Report submitted to the faculty of
Homi Bhabha National Institute
In partial fulfillment of the requirement for the degree of
Doctor of philosophy

Submitted By

Guided by

Indus Synchrotron Utilization Division
INDORE, M.P- 452013
August 2011

1- Introduction
2- Scattering geometry
3- Basic principle
4- Layered system
4.1- Single layer film on substrate
4.2- Bilayer film on substrate
4.3- Multilayer structure
5- Effect of interfacial width on reflectivity
6- Types of roughness
7- Effect of roughness on reflectivity of a surface
7.1-From a single surface
7.2- From a thin film (A single layer on a substrate)
8- Experimental techniques
9- Books referred


Precise characterization of thin film/multilayer structures in terms of their structural
properties is of utmost importance for their performance evaluation. These artificial structures
are deposited under non-equilibrium conditions; there exists considerable deviation of the
parameters from the designed values. The structural parameters of importance are layer
thicknesses, density, roughness, interdiffusion, crystal structure, and crystallite size. The
techniques used to extract information about these parameters are grazing incidence x-ray
reflectivity, wide angle x-ray diffraction, atomic force microscopy, and transmission electron
microscopy etc. The present reading course covers the details of x-ray reflectivity technique and
its application for characterizing thin film/ multilayer structures.
Structural characterisation with x-rays is a non-destructive way of studying the surfaces
and interfaces at atomic scale. Moreover, the x-ray techniques can be made surface sensitive by
working at grazing angles of incidence since the penetration depth is restricted to the surface
layers. In the x-ray region, the refractive index of all materials being less than unity, total
external reflection occurs when the radiation with wave vector

is incident on a
medium from vacuum for grazing angles less than the critical angle

, where

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)

The typical value of penetration depth is ~50 Å. For incidence angles

, the refracted ray
bends away from the normal as given by the Snell‟s law. A schematic of reflection and refraction
taking place at the boundary between vacuum and medium of refractive index n is shown in
2-Scattering geometry:-
In a coplanar geometry of x-ray scattering the incident wave, reflected wave and surface
normal vector lie in the same plane (figure-2) and wave vector defines the direction of
perfectly monochromatic wave. Distribution of scattered intensity in a reciprocal space gives the
information about structural parameters of a sample.

In the following section the mapping of Cartesian component of wave vector transfer in a
sample is discussed along with the formalism of a multilayer reflectivity for smooth and rough
interfaces. Geometry of x-ray scattering from a medium of refractive index is shown in figure-
2. In specular reflection condition, both incident and reflected waves, defined by wave vector


respectively, make equal angles u with the boundary. Since both


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

However the change in momentum transfer vector perpendicular to the surface is


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


are not equal, then the momentum
transfer takes place in x direction also. Such scans where the two angles are kept unequal are
subject of diffuse scattering experiments. These experiments yield the information about the
lateral surface structure.

Fig-3 If incident and reflected wave vector


make the angle


from the scattering surface,
respectively then momentum transfer along the x and z directions is given by


Sample surface lies in the xy
plane while xz is a scattering plane.

The general form of wave vector transfer can be written as



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


. This scan is known as
„ scan‟.
(b) Offset scan-
If both sample and detector are rotated such that a constant offset angle between
them is maintained i.e.

This scan is called „offset scan‟.
(c) Sample rock scan-
If detector is kept fixed at a constant angle

and only sample is
rocked around a central value , then this scan is called „sample rock scan‟.
(d) Detector scan-
When sample is kept fixed at a constant incidence angle and only detector is
scanned i.e.

fixed and

varied. (detector scan).

These scans are useful to probe the sample structure along the x and z direction both.
In scan, wave vector transfer restricts in the z-direction. Thus, this scan yields the structural
information of a sample in the perpendicular direction, where it is assumed that the sample is
laterally homogeneous and scattering process will not change the degree of coherence of the x-
rays. Nevertheless, the laterally inhomogeneous or rough structure destroys the degree of
coherence of the waves. Because of the non-homogeneity arising from, surface roughness, the
surface normal is not uniquely defined, and it increases the diffuse scattered background. The

scan modes described above are used to record the diffuse scattering components, which yield
the information of roughness correlation.

3-Basic Principle-

Reflection and refraction of electromagnetic radiation at the interfaces between two
materials depend on the optical index contrast of the materials. Since the frequency of x-ray
radiation is greater than the resonance frequency of the medium (in medium, electron undergoes
harmonic oscillations in presence of the electric field of radiation), the refractive index is found
close to unity for all the materials and is given as where o and | are real and
imaginary parts of refractive index, If

is exit angle of refracted radiation for vacuum/medium
interface, the law of refraction gives

. For

, the wave cannot propagate in
the medium. The corresponding incidence angle is called the critical angle, which is defined

, where

is electron density of the medium. Below the critical angle, the
wave vector inside the medium

is purely imaginary. Thus, wave
cannot propagate inside the medium for all incident angle

. Except for small losses due
to absorption; all other incoming radiation will be reflected. Penetration depth in the critical
angle region is restricted to few tens of angstrom and defined as:


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.


Below critical angle the penetration depth is few tens of angstrom whereas for

increases drastically. As soft x-rays are highly absorbing in all materials

penetration depth is only few hundreds of angstrom even in

region, while the same goes
in micrometer range for harder x-rays where absorption term is very small

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:




are glancing angles of incidence and refraction respectively. For p
polarized radiation (electric field vector in the scattering plane), reflection and transmission
coefficients gets modified; but for grazing incidence, either state of polarization yields identical
results for . The above coefficients are complex since the refractive indices are complex. In

Fig-4 X-ray penetration depth inside molybdenum film at two different wavelengths (hard x-rays)
and (soft x-ray)as a function of normalized angle of incidence



an experiment, the measured parameter is the Fresnel reflectivity R
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


An example of s-polarized reflectivity from a single smooth surface as a function of
normalized incidence angle

is given in figure-5. Below the critical angle the reflectivity is
almost 100%, if | is negligible. At the critical angle

, the reflectivity drops drastically
and the reflectivity fall is inversely proportional to the fourth power of momentum transfer
vector for all

. 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

Fig-5-X-ray reflectivity from a single surface as a function of normalized angle of incidence

critical angle, the total external reflection yields the 100% reflectivity if |=0. As ratio increases the
reflectivity profile gets modified.[Ref-2]

The Fresnel reflectivity is plotted as open circles in figure-6 against

in the small angle
approximation for a silicon surface. The solid line corresponds to the Porod law

Porod law is applicable to small angle x-ray scattering which has a similar functional
dependence. The deviation of the Porod law at small q-values is due to the approximations
involved viz. neglect of refraction and multiple scattering effects. This regime is also known as
the Born approximation (BA) or the kinematical approximation. In the Born approximation, the
scatterer is assumed to be illuminated by a plane wave and the scattering is calculated as if the
scatterer is absent. Each element of the sample scatters the incident wave and the resulting
scattered field by all the elements at a distant point are summed up to calculate the total
scattering. This neglects the multiple scattering effects and is thus valid for weak scattering,
where reflectivity is approximately less than 10%. It can be observed that the reflectivity drops
by five orders of magnitude over a range of 10 times the critical wave vector transfer. Hence a
very intense x-ray source is required for reflectivity measurements to collect the data over a
sufficient q-range so as to enable the determination of the electron density variation with good
accuracy. The Fresnel transmitted reflectivity is shown in the inset. For

, the incident and

Fig-6- Fresnel reflectivity of silicon surface at with


is shown as open circles. The solid line is the

decay corresponding to the Porod law applicable
to small angle x-ray scattering. The inset shows the Fresnel transmitted intensity for the same set of parameters.


specular wave fields are in counter-phase at the surface which leads to zero intensity in the
transmitted (evanescent) wave field. For

, the phases of the two waves match at the
surface which gives rise to a two-fold enhancement in the transmitted (evanescent) wave field in
the medium. This leads to a four-fold enhancement in the transmitted intensity in the absence of
4- Layered System:-

Fresnel‟s reflectivity formalism for a single smooth surface can be extended to explain
the x-ray reflectivity from a layered media of different materials. Adding the wave field reflected
from different boundaries in a recursive manner and applying the proper boundary conditions
yield the reflected intensity from a multilayer structure.

4.1-Single layer film on a substrate:-
In case of a thin film of a material deposited on the substrate, there are two
interfaces viz. vacuum/film and film/substrate that are separated by the film thickness„d‟. The
interference between the radiation scattered from the two interfaces results in the net reflectivity
of the structure. Let the Fresnel reflected amplitude of the top and bottom interfaces


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,



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 Δq is the difference in wave vector transfer (in the film taking refraction into account) between

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
-(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
-(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 Å and 800 Å thick Pt film on a
silicon substrate.

Fig-7- X-ray reflectivity spectra of Pt film of thickness200 Å and 800 Å 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

Incidence Angle degree

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 50Å is marked as „a‟ where two frequency
modulation viz. 50Å and 100Å are shown. Similarly curve marked as „b‟ is corresponding to C-
Mo bilayer of 100 and 800Å 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 ì=1.54Å, (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

Incidence Angle (in degree)

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

. Incident wave field hits the multilayer
sample at an angle and undergoes the reflections and transmissions at different boundaries
inside the sample. Final reflection amplitude from a multilayer structure is calculated with the
boundary condition that the tangential component of electric and magnetic field vectors.

Fig-9- Representation of incident reflected and transmitted waves inside a periodic multilayer system.
Corresponding vector diagram for incident and reflected wave is also shown.


The multilayer structure is characterised by its period (distance between two layers of the same
composition) and its ratio I between the thickness of the high electron density layer to the
period. A multilayer with a value equal to an integer j, suppresses the j
harmonic and its multiples. The periodicity„d‟ in the real space gives rise to Bragg diffraction
peaks in the reflectivity pattern at wave vector values of . In addition to the Bragg peaks,
N-2 subsidiary peaks are observed between the Bragg peaks due to the finite total thickness of
the film. As N is increased, the intensity of the Bragg peaks increases and that of the subsidiary
oscillations decreases.
The reflected intensity distribution from a periodic multilayer stack can be represented by
the following equation


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 Å 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 Å at using
different Ivalues(a) I =0.40,(b) I =0.50, and(c) I =0.33.

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0

gamma 0.4

gamma 0.5

Incidence Angle (in degree)
gamma 0.33

- 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:

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
ρ(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:



is the Fresnel reflectivity. For an abrupt interface, is defined as a step

is thereby given by a delta function whose Fourier transform is unity which
results in

. Thus an abrupt interface gives rise to a reflectivity that is given by the
Fresnel formulae.
In practice, the electron density variation across the interface between two media will not
be abrupt and will have a gradual transition over a finite width. Figure-11 shows a typical
variation of having the functional form of an error function and the corresponding gradient
of is also shown which has a Gaussian distribution of width σ.


Equation-(12) will thus become:

which causes damping of the reflected intensity by the factor

, termed as the „static‟
Debye-Waller factor. This term is analogous to the Debye-Waller factor used to model the
thermal disorder in conventional x-ray diffraction, the basic difference being that the interfacial
width is a “frozen” disorder. The interfacial width and the profile are the vital parameters to be
determined from the measured reflectivity data.
6-Types of roughness:-
For a single layer film, the interfacial width scales with the film thickness. The same may
not be valid for a multilayer structure due to the different growth behaviour of the two materials
forming the multilayer structure. Roughness in multilayer structures can be divided into four
limiting cases that are schematically shown in figure-12.

Fig-11- Schematics of density variation at the interfaces (a) For ideal case where density varies as step
function at interface, (b) For the real system where density varies gradually at the interfaces. (c) Variation


(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
(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:

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

in medium-2, where the refraction can be ignored (Born Approximation). So


(geometric average), where q and

are q values in the two media forming
the boundary, gives a very good approximation to a regourous theory (Novot Croce Model) and
yields for the reflectivity reduction in the amplitude and in intensity.

Fig-12- Schematic model of four different types of interface roughness in multilayer structures: (a)
uncorrelated, (b) cumulative, (c) partially correlated, and (d) correlated.

Thus equation-16 becomes:


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 Å) of a silicon wafer
is shown using the Gaussian interface model, for;
(a)-zero roughness and
(b)-7 Å 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


for different values of root mean square roughness σ. (a) and (b)

0.0 0.5 1.0 1.5 2.0

Incidence Angle degree
o = 0.0 A
o = 7.0 A

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

at the vacuum/film interface and

at the film/substrate interface
causes further reduction in the overall reflectivity and amplitude of the oscillations. The two
roughnesses affect the reflectivity pattern differently thereby allowing their independent
determination. The roughness of the top surface

affects the overall rate of fall in the
reflectivity with angle whereas the roughness of the bottom interface

reduces the amplitude of
the oscillations with increase in angle. The amplitudes


which were defined earlier for
a smooth interface are modified for a rough interface. Thus by fitting the measured reflectivity
data of a thin film to equation-10, the following parameters can be precisely determined.
(a)- Film thickness
(b)-Electron density of the film
(c)-Width of the bottom and top interfaces.
The above aspects are explained with the help of simulated curves in figure-14 where the
following four cases are presented.

Fig-14 Calculated x-ray reflectivity at wavelength for a 200 Å Mo film on Si substrate,
for different combinations of substrate roughness

and film roughness





: This situation corresponds to an ideal smooth film.


: The top interfacial roughness reduces the overall fall in reflectivity

with increase in angle.



: The bottom interfacial roughness reduces the amplitude of the
oscillations with increase in angle without affecting the envelope. This can be understood by
examining equations (10) and (17) where the roughness term containing

multiplies the
oscillatory terms in the numerator as well as in the denominator whereas the term

multiplies only the less significant term in the denominator.


: The reduction in reflectivity is more severe than the above cases. It
can be observed that the amplitude of the oscillations is still preserved even at higher angles and
is because the two waves are reduced approximately by the same amount and hence their
coherence is preserved.

8-Experimental Techniques:-
The experimental requirements for x-ray reflectivity technique are similar to those found
in a standard goniometer, in which a monochromatic x-ray beam is used and the scattering
vector is scanned by scanning the scattering angle. Other experimental considerations are source,
detector, data collection, resolution, etc. which are similar to those for grazing incidence x-ray
scattering measurements. A schematic of the typical angle scanning configuration is shown in

Fig-15 Schematic diagram of a angle scanning spectrometer

The incident and reflected angle are equal so that the scattering vector is aligned normal to the
sample surface (i.e., in the specular reflection orientation). The critical wavevector for total
external reflection is very small, typically on the order of

. This means that the incident
angle on the sample must be about

. Therefore, the incident beam must be collimated to an
angular divergence significantly less than this value, with either slits or a monochromator crystal.
The strict limitation on angular divergence typically precludes the use of focusing optics to
increase the beam intensity. In addition, at this grazing angle, a small error in the position of the
sample will make the beam miss the sample. This problem of the beam “footprint” aligning the
beam to be completely contained on the sample is one of the most significant challenges of x-ray
reflectivity. Further, the strong dependence of the Fresnel reflectivity on the scattering vector

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.

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.


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
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)