Abstract

Metallic multilayers are widely used in scientific research and in

industries. Many characterisation techniques are used to determine the
properties of nanostructured metallic multilayers. In this report we will
discuss the techniques that are used to determine the thickness of
nanostructured metallic multilayers i.e. destructive techniques and non
destructive techniques and will discuss the more accurate techniques i.e.
TEM and HRTEM in detail.

1
Metallic multilayers
Metallic multilayers are composed of two very thin different materials
layers alternatively. These layers can vary from a few to more than
thousands individual layers, thickness range from a few atom to a
thousand atoms and the corresponding maximum structure thickness
could be of about 10 millionth of an inch

Multilayers are the part of “nanostructured” material which is a well

known scientific field. It shows the limits of material science and there is
numerous research programmes are running on that field. Multilayers are
among the first material to be designed and fabricated at atomic level.
Atomic multilayers posses’ enhanced optical, mechanical (i.e.-strength,
hardness and heat resistance), magnetic and other unexpected new
properties [7]

History
The first application of multilayers performed more than 60 years ago. In
the semiconductor industry for making hard disks and computer chips,
macro multilayers became an essential part. Then advances in fabrication
techniques took place and with the applications in the x-ray and
ultraviolet regions of the electromagnetic spectrum, we got more
advanced multilayers for the industry and for the research work. A new
class of telescope could be possible because of high reflectivity multilayer
mirrors, which is very useful for solar physics and astronomical
research .Multilayers optics have applications in electron microprobes,
scanning electron microscopes (SEM) and X-ray layers etc[7]

Properties of multilayers

 Higher strength

 Less friction and wear

 Corrosion resistance

 Heat resistance

 Low electrical resistance

 Fracture resistance

2
  Better optical properties

Techniques to determine the thickness of

nanostructured metallic multilayers
Two types of techniques are used for film thickness determination of
metallic multilayers

1 Destructive Technique

2 Non destructive Technique

Destructive and non destructive techniques are widely used in research

industry to evaluate the properties of material i.e. thickness of material.

In destructive methods we evaluate the properties of metal layers by

damaging the element and in non destructive techniques we evaluate the
properties without causing damage.

Destructive techniques for determining the thickness of metallic

multilayers

 Scanning electron microscopy(SEM)

 Transmission electron microscopy (TEM)

 High resolution transmission electron microscopy(HRTEM)

Non destructive techniques for determining the thickness of metallic

multilayers

 Spectroscopic ellipsometry

 Interferometry

 X ray reflectometry

 Electron probe microscopy

Destructive techniques are better as compared to Non destructive

techniques.

SEM,TEM,HRTEM all are imaging techniques ,so we can actually see many
layers of different metals and measure the thickness ,but sample
preparation is a difficult and time consuming task.[1]

3
Formation of nanostructured metallic multilayers
Formation of nanostructures is based on mechanical deformation under
high strain rate and shear condition. Mechanical alloying of powder
particles has been used in preparing nanoscaled material with large range
of chemical composition and atomic structure. When a mechanical
deformation takes place there is a change in thermodynamic, mechanical
and chemical properties of these materials, which has been observed with
properties of nano phase materials. There are two methods of
nanostructure formation. [2]

The first method mechanical attrition (MA) was developed as industrial

process to produce alloys and phase mixture.[2] This method can yield
alloy of metals with different melting points, with improved strength and
corrosion resistance.

The other method is high energy milling, which is a non equilibrium solid
state process which results in material with nano microstructures. [2]

In this report we will first discuss the non destructive techniques and how
to determine the thickness from that technique and then we will discuss
the destructive techniques and will compare the results and advantages.

X- Ray diffraction (XRD)

In x ray diffraction a beam of X-rays with 0.5 – 2 Armstrong wavelength
incident on a specimen and is diffracted according to Bragg’s law. [1]

λ = 2d sin θ

Where λ is wavelength, d is distance and θ is the angle.

It can identify the specimen’s crystalline phase, structural properties,

strain, size and orientation of the crystallites. XRD can also determine film
thickness, atomic arrangements in amorphous materials and multilayers.
The diffracting power of thin film is small so XRD instruments are
designed to maximise the diffracted X-ray intensities. T his technique has
a range of element, but not element specific, low Z elements may be
difficult to detect. Probing depth is few micrometers but it is material
dependent. XRD is a non destructive technique for most of materials. Any
material greater than ~0.5 cm can be used for sample. The main use of
this technique is identification of crystalline phases, determination of
strain, accurate determination f atomic rearrangement and determination
4
of size and crystalline orientation. It can also use in different imaging and
characterization, atomic rearrangement in amorphous materials and
multilayers and in film thickness measurement. [1]

Basic principle
of XRD
In the figure
below the
diffraction angle
2θ is the angle
between incident
and diffracted x
rays. The
diffracted
intensity is
measured as a
function of 2θ and the orientation of the specimen. The x-ray wavelength
λ is 0.7 – 2 A˚ [1]

Fig 1- Basic features of typical XRD experiment from [1]

5
Electron probe microscopy (EPMA)
Electron probe X-ray microanalysis (EPMA) is an elemental analysis
technique in which a specimen is bombarded with a focused beam of
energetic electrons. Beam energy is 5 – 30 keV. The X- rays are measured
by EDS or WDS X- ray spectrometers. EDS is energy dispersive and WDS is
wave length dispersive spectrometer. In this technique we can use
beryllium to actinides range of elements. This is a non destructive
technique and in rare cases there is a chemical bonding as well in EPMA.
Depth profiling is rarely by changing incident beam energy. Accuracy is
±40% relative in 95% cases in polished, flat sample. The detection limit in
WDS is 100 ppm and in EDS it is 1000 ppm. Sampling depth is dependent
on energy and matrix and it ranges between 100 nm- 5 µm. Lateral
resolution is also depend on energy and matrix, which ranges between
100 nm- 5 µm. EPMA is suitable for compositional mapping and SEM
imaging. [1]

The sample used in EPMA should be solid conductors and insulator, <2.5
cm in diameter and <1 cm thick, rough surface, thin film and polished flat
particles. The major uses of EPMA are in non destructive quantitative
analysis of major, minor and trace constituents of materials. The size of
EPMA instrument is 3m*1.5m*2m high. [1]

Reflected electron energy loss spectroscopy (REELS)

In reflected electron energy loss spectroscopy (REELS) we place a solid
specimen in a vacuum which is irradiated with beam of energetic
electrons, which induces the electron excitation with atoms. Some of the
incident electrons lose their energy and remerge from the sample, relative
to the well defined energy E of incident electron. An electron energy
analyser is used to measure the energy of emitted electrons and
direction. Composition, chemical bonding and crystal structure
information can be obtained from the surface of the sample, from energy
loss spectra, by comparison to standards. Range of elements in REELS is
hydrogen to uranium (no isotopes). This is a non destructive technique.
Accuracy could be few percent to tens of percent. Probing depth is 0.07-3
nm. Lateral resolution is 100 nm -50µm, which is independent from
sample. Sample should be solid, liquid and vacuum compatible, typically
<2.5 cm diameter, <1.5cm thickness. Main use of REELS is in few
monolayer thin film analysis and in submicron detection of metal
hydrides. [1]

6
Reflectance spectroscopy
In the reflectance spectroscopy the reflectance spectrum of a coated
sample is used to determine the thickness of a polymeric coating. Based
on the interference fringes observed, the thickness of the film is
calculated.

The measurement of the film thickness using reflected light is a well

established technique. This is an optical technique for the determination
of thin films and depends upon the interaction of film with light. It can not
only determine thickness but the roughness and optical constants as well.
All the measurements are depending upon the interference pattern or
fringe pattern from transmission through two partially reflecting surfaces.
This process has application in glass and automotive industries. [4]

The principle of reflectance spectroscopy is a thin film on the surface of

other material reflects light from both top and bottom surfaces, with the
total amount reflected depend on the sum of two reflections. These
reflections may add together in constructive way or destructive way,
depending on phase relationship. The behaviour of light is like a wave, the
resulting interference fringe pattern can be used to determine the
thickness assuming the refractive index and angle of incident are known.
We use the formula given below for the following experiment. [4]

Where

d= film thickness

m= number of fringe

n= refractive index

θ= angle of incident

Wave number region

Reflectance spectrum is shown in the figure below.

7
Fig 2- Reflectance spectrum showing interference pattern from [4]

Interferometry
In the interferometry we use an optical interference system, which after
deposition allows us to determine the thickness of metallic films. In this
process we
compare the two
patterns
generated by the
substrate with and
without deposited
film on it. The
thickness of film is
determined by the
difference of
measure of
pattern. [6]

In the interferometer, one of the mirrors is substituted by a flat glass plate

and a thin film is grown up in one single portion of substrate. In some
cases the film has poor reflection so plate has an aluminium metallization
on it, which makes plate work as a mirror. The following sequence occurs
in this process of mirror formation. [6]

1 Film get placed on a glass plate to be measured

2 Formation of mirror by metallization with aluminium.

8
Fig 3- Michelson interferometer used to measure the thickness from [6]

At first to measure the source wavelength, the interferometer was used

without changing any mirror and then we replace the mirror to obtain a
double interference pattern. The figure above shows the setting of a
specimen inside the interferometer.

We use the following equation for the thickness in interferometry.

g = (a/b) (λ/2)

Where λ is the laser wave length

The thickness of layer grown up can be measured as function of

interference bandwidth. By interferometry we obtain thickness of metallic
film, grown up through a high vacuum evaporation system. Accuracy in
this method directly depends on the radiation source wavelength that is
being used in the system. [6]

So this method is suitable for determining the thickness of metallic layers,

based on the shift in the interference fringe between both patterns
compared.

Scanning electron microscopy (SEM)

9
Traditionally for the small scale material characterization first instrument
comes in mind is optical microscope but it gives limited results, for the
detailed result optical microscopes are replaced by scanning electron
microscopes and transmission electron microscopes .SEM gives the highly
magnified image of the surface of the material.SEM not only just provides
the information about surface region but it provides the information
concerning composition near the surface region of the material as well. [1]

In the SEM an electron source in vacuum is focused on a sample. When

the electron penetrates the surface, it emits electron or photons .the
photons are collected by the detectors and the output can be used for the
brightness of the cathode ray tube (CRT). whose x and y inputs are
synchronous with x and y voltage of the electron beam .Finally we get an
image on CRT .The SEM image is highly magnified and has a look of
traditional optical microscope but this image has greater depth of the
field .There are three types of images produced in SEM . [1]

1 Secondary electron images

2 Back scattered electron images

3 Elemental X ray maps

Fig 4 – Schematic describing an operation of SEM from [1]

The main use of SEM is high magnification imaging and elemental

mapping. SEM is a destructive technique and there is damage of some
electron beam. The magnification range is between 10x-300,000x: 5000x-
100,000x and the beam energy range is typically 20-30kev.[1]
10
Sample requirement is minimal and sample must be coated with a
conducting film and must be vacuum compatible. The size of the sample
is less than 0.1mm and up to 10 cm or more .lateral resolution is 1-50nm.
Depth sample varies from a few nanometres to few micrometers
depending upon the voltage and mode of analysis .The size of instrument
is 3ft*5ft electronics console and 3ft*3ft electron beam column. [1]

Transmission electron microscopy (TEM)

TEM has become a very powerful technique for material scientists. TEM
gives lateral spatial resolution better than 0.2 nm point to point.TEM
provides both image and diffraction information from a single sample. A
very highly energetic electron beam used in TEM meets with sample
matter to produce radiations and creates signal, the signal gives the
material characterization by using energy dispersive x ray spectroscopy
(EDS), electron energy loss spectroscopy (EELS), extended energy less
fine structure (EXELFS), backscattered and secondary electron imaging.
[1] and [3]

In TEM a focused highly energetic electron beam is incident on a sample

which is less than 200nm.The electron penetrates the sample thickness
and we can obtain signal in TEM by both deflected and un deflected
electrons. The magnetic lenses usually a film plate r video camera deliver
the signal to the detector, this provides a very high magnification range.
[1] and [3]

In TEM a highly focused beam is used as a probe which provides high

spatial resolution. In most TEM experiments, samples are usually less than
200nm thin. The lateral spatial resolution depends on the operating
voltage of a TEM instrument, higher the voltage higher would be the
lateral spatial resolution.

High voltage TEM has better electron penetration because high energy
electrons interact less strongly with matter, so we can work with thicker
samples n a high voltage TEM.

TEM offers two methods of specimen observation

1 diffraction mode

2 image mode

In diffraction mode, an electron diffraction pattern is obtained on a

fluorescent screen, which is equivalent to an x ray diffraction pattern.

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Single crystal produces spot pattern and polycrystalline produces a ring
pattern. [1] and [3]

The image mode produces an image of the illuminated sample area. There
are several mechanisms to contain contrast to image i.e. mass contrast,
thickness contrast, and diffraction contrast and phase contrast.

Mass contrast is due to spatial separation and thickness contrast is due to

non uniformity of sample thickness.

The most difficult task in TEM is the specimen preparation, which is a very
time consuming process. Earlier specimen preparation was divided in two
categories; for thin films and for bulk materials. Now a days we use
complementary specimen geometry for observations, that of the cross
section, which are made up of layered materials [1]

(a)
(b) (c)

Fig 5- (a) – diffraction pattern from a single crystal (b)- diffraction pattern
from a polycrystalline thin film (c)- diffraction pattern from the same film
with 400 keV kr ion from [1]

12
Fig 6- schematic representation of ray paths of scattered and unscattered
rays

High resolution transmission electron microscopy

(HRTEM)
This technique is developed to image the atomic structure of material in
1970. This technique is the further development of TEM. We use digital
controllers in this technique. HRTEM uses the phase contrast, which is
based on the coherent interference of many electron beams to show the
atomic structure and the lattice fringes. The difference in the phase of
electron waves scattered through a thin specimen develops the contrast.
Phase contrast images are sensitive in thickness, orientation so they are
difficult to interpret. So the computer simulation is required. [3]

Knowledge of the atomic rearrangement of surfaces and interfaces is the

key to understand the material properties. HRTEM is by far the best
technique to obtain structural information. The local 3D information is
required to understand the properties of material, so the local structure is
vital for understanding the properties. Resolution of HRTEM is about 0.1
nm. HRTEM gives 2-D information about atom positions but by combining
13
HRTEM information from different directions, we can create a 3-D model.
[3] HRTEM provides the required accuracy and creates new possibilities in
science.

Conclusion
All the above explained 'destructive' imaging techniques (SEM, TEM, and
HRTEM), by far are the best techniques for determining the thickness,
structure, and composition of the metal multilayer’s. Despite, having
higher resolution and ability of qualitative analysis, sample preparation for
these techniques is a difficult job in case of metal multilayer’s which
requires precision tools such as diamond saw, metal vapor deposition, FIB,
sophisticated grinding, milling, and polishing equipments and a series of
complex process steps. Longitudinal (surface & structure) and Cross-
sectional (thickness & composition of layers) imaging can be done after
sample preparation.

In case of SEM a small section of the sample is cut and stuck vertically on
a copper support using carbon tape held on to a sample holder which is
then analyzed in SEM using different detectors. Secondary electron
detector is most prominently used which sends all the data to the
computer program to do the computation and generate the image.
Compositional analysis is done in on the sample using the EDAX detector
on the equipment. [1]

For TEM and HRTEM sample preparation is a very critical stage as the
thickness of the sample on the copper grid is limited to a few 100nm
(<<500nm). Sample preparation for TEM involves around 9 complex
process steps and the precision equipments stated above. A very thin
slice is cut through the sample that is then positioned onto the copper
grid and a series of different milling; grinding and polishing steps then
remove all the aberrations and artifacts from the sample surface and also
make it thin enough for the TEM analysis. This a very effective and most
used way of imaging and measuring the thickness of the metal multilayer
and also qualitative analysis is done by studying the difference in contrast
of various metal layers. [1] [2] and [3]

14
Bibliography

Books:
[1] Encyclopaedia of material characterization (electronic recourse)
Surfaces, interfaces, thin films Editors: C. Richard Brundle, Charles
A.Evans, and Shaun Wilson part 1-6

1.3.5 page 15, 1.4.1 page 16, 4.1 page 198-200, 1.5.4 page 25, 1.2.4, 2.4
page 99-100, 1.2.2page 8, 2.2page 70-71

[2] Copyright (2002) William Andrew publishing/Noyes retrieved from

www.knovel.com nanostructured materials and composites prepared by
solid state processing Hans.J Fetch

[3] Nanostructured material (2009) Elsevier Ltd. S.divinski, H. Rosrer,

G.Wilde functional nanostructured material-microstructure,
thermodynamic stability and atomic mobility

Journal articles:
[4] The determination of thin film thickness using reflectance
spectroscopy
Andrew R. Hind PhD and Lisette Chometteb
Varian Limited, 28 Manor Road, Walton-on-Thames, Surrey KT12 2QF,
England
Varian France S.A., 7 Avenue des Tropiques, Z.A. Courtaboeuf 2 - B.P. 12,
91941 Les Ulis, France

[5] Nanostructured Reactive Metallic Multilayers

M A Mat Yajid1,2 and G Möbus1
1 Dept of Engineering Materials, University of Sheffield, Sheffield S1 3JD,
UK
2 Dept of Engineering Materials, Faculty of Mechanical Engineering,
Universiti
Teknologi Malaysia, 81310, Skudai, Johor, Malaysia source:
iopscience.iop.org

[6] Interferometric thickness determination of thin metallic films

15
M. Hernández, A. Juárez,* R. Hernández
Laboratorio de Ciencias Aplicadas, Facultad de Ciencias Físico
Matemáticas -UAP
Av. San Claudio Esq. Río Verde, Col. San Manuel, 72 570 Puebla, México
December 1999

Web reference
www.varianinc.com

www.iopscience.iop.org

[7] www.llnl.gov/str/Barbee

Troy W barbee Jr. Lawrence Livermore national laboratory

16