Report

Research Lab I

Experiment:

Physical Vapor Deposition

Signatures of the participants:

Attestation:

1
Table of Contents
1. .... Introduction/Motivation .................................................. Error! Bookmark not defined.
2. .... Fundamental principles ................................................. Error! Bookmark not defined.
2.1. PVD techniques....................................................... Error! Bookmark not defined.
2.2. Thermal evaporation ............................................... Error! Bookmark not defined.
2.3. Evaporation rate ...................................................... Error! Bookmark not defined.
2.4. Evaporation techniques ........................................... Error! Bookmark not defined.
2.4.1. Resistance heated evaporation sources ................. Error! Bookmark not defined.
2.5. Purity of films ........................................................... Error! Bookmark not defined.
2.6. Uniformity of films .................................................... Error! Bookmark not defined.
2.7. Sputtering ................................................................ Error! Bookmark not defined.
2.8. Quartz Crystal Microbalance: .................................. Error! Bookmark not defined.
2.9. HEX deposition system ........................................... Error! Bookmark not defined.
2.10. DektakXT stylus profiler .......................................... Error! Bookmark not defined.
3. .... Experiment.................................................................................................................... 4
3.1. Sample Preparation............................................................................................... 15
3.2. Deposition of silver thin film ................................................................................... 15
3.3. Deposition of titanium thin film............................................................................... 15
3.4. Resistance Measurement ...................................................................................... 16
3.5. Thickness Measurement ....................................................................................... 16
4. .... Results and Discussions ............................................................................................. 17
4.1. Film Thickness: ..................................................................................................... 17
4.2. Tooling Factor ....................................................................................................... 19
4.3. Concentration of Oxygen Impurities ...................................................................... 20
4.4. Resistance of 2-Point Deposited Ag- Film ............................................................. 20
5. .... Conclusion .................................................................................................................. 22
6. .... References ................................................................................................................. 23

2
Figures
Figure 1 Vapor pressures of selected elements. [2] ________________________________ Error! Bookmark not defined.
Figure 2 Resistance heated evaporation sources. (Courtesy of R. D. Mathis Company) Error! Bookmark not defined.
Figure 3 (a)Knudsen evaporation source (b) Crucible evaporation (c) Thermal boat evaporation source (d) Electron
beam evaporation source [4] ____________________________________________________ Error! Bookmark not defined.
Figure 4 Film thickness uniformity for point and surface sources. Source: M. Ohring, Materials Science of Thin
Films, Academic Press, London (2002). __________________________________________ Error! Bookmark not defined.
Figure 5 the arrangement of the source and target ensures the thickness uniformity of the film. Source: M. Ohring,
Materials Science of Thin Films, Academic Press, London (2002). ___________________ Error! Bookmark not defined.
Figure 6 Illustrations of the thin film coverage of the substrate. A) uniform coverage; B) poor side wall coverage; C)
lack of coverage. Source: M. Ohring, Materials Science of Thin Films, Academic Press, London (2002). _____ Error!
Bookmark not defined.
Figure 7 a) typical arrangement of sputter deposition with a single cathode, b) fundamental processes occurring
during ion impact at a target; c) schematic illustration of the magnetron sputtering. Source: L. Alff, A. Klein, P.
Komissinskiy, and J. Kurian, Vapor phase deposition of oxides, Ceramics Science and Technology, c) extracted
from [http://www.semicore.com/what-is-sputtering] _________________________________ Error! Bookmark not defined.
Figure 8 potential distribution with: a) DC current; b) RF plasma excitation ____________ Error! Bookmark not defined.
Figure 9 Cross-section through a magnetron cathode and typical target utilization for standard geometry with fixed
target and magnet system ______________________________________________________ Error! Bookmark not defined.
Figure 10 A QCR in casing (right) and outside of it (left). Scource: D. Johannsmann, The Quartz Crystal
Microbalance in Soft Matter, Springer, Heidelberg (2015) ___________________________ Error! Bookmark not defined.
Figure 11 The HEX deposition system outside view. Source: retrieved from
[https://ncmn.unl.edu/thinfilm/Hex%2001.jpg] ______________________________________ Error! Bookmark not defined.
Figure 12 Magnetron source and the shutter window. Source: retrieved from [https://ncmn.unl.edu/thinfilm/Hex]
______________________________________________________________________________ Error! Bookmark not defined.
Figure 13 Deposition mask for a 5×5 mm2 composed of two stripes with 5 and 10 thin-film squares for four- and
two-terminal resistance measurements. _________________________________________________________________ 15
Figure 14 Graph of Silver (Ag) 2- Point by stylus profiler ___________________________________________________ 17
Figure 15 Graph of Silver (Ag) 4- Point by stylus profiler ___________________________________________________ 17
Figure 16 Graph of Titanium (Ti) 2- Point by stylus profiler _________________________________________________ 18
Figure 17 Graph of Titanium (Ti) 4- Point by stylus profiler _________________________________________________ 18

Tables
Table 1 Film Thickness measured with DektakXT Stylus Profiler for Ag 2-Point, 4-Point, and Ti 2-Point, 4-Point __ 19
Table 2 Tabular representation of thickness and tooling factor of Ag and Ti __________________________________ 19
Table 3 Representation of total resistance _______________________________________________________________ 20
Table 4 Representation of parameters for sheet resistance and resistivity calculations ________________________ 20
Table 5 resistivity and sheet resistance tabular form ______________________________________________________ 21

3
1. Introduction/Motivation

Depositing thin films of two different materials, namely; silver (Ag) and titanium (Ti) on a sapphire
substrate using two different techniques of physical vapor deposition (PVD) is the aim of this lab
session. A study of the properties of the deposited thin film such as the thickness of the thin film
using the DektakXT software system and comparing the results with the recorded values from the
quartz crystal microbalance (QCM) and the correlated error values, the atmosphere of the
deposition process such as the concentration of the oxygen impurities, so as measuring the
values of the resistance of the thin films are carried out. Deposition of thin films is of interest to
the industry especially in the field of manufacturing microelectronics and producing optical
components such as mirrors, beam splitters and antireflection coatings. The development of the
PVD techniques over the past 30 year witnessed a lot of improvement and enabled the technique
to be implemented in many applications. The applications span from coating applications in
cutting tools to aerospace applications. The first commercially PVD coated material was the
titanium nitride (TiN) in the early 1980s used for manufacturing cutting tools. Being also hard and
wear resistant, the PVD coatings allowed the manufacture of hard punches and forming tools.
Modern uses of the PVD techniques also include the enhancement of glass properties and the
development of anti-scratch glass used in mobile phones and hand watches. These techniques
also paved the road to discover new effects that occur in materials such as the 2D electron gas
that forms at the interface of the two insulating oxide materials such as SrTiO 3 and LaAlO3.[9]

2. Fundamental principles
2.1. PVD techniques
The term PVD refers to the process of vaporizing a solid source and depositing the formed vapor
on a substrate of a chosen target. The PVD technique can be carried out using various principles,
each of which comprises different techniques. The main PVD principles are thermal vaporization,
sputtering, laser ablation.

PVD processes includes the ejection of atoms at the surface of the sources by thermal activation
or by direct collisions with electron or ion beams. The atoms can traverse the space of the
chamber with the kinetic energyy they gained to deposit themselves on the target material
overcoming the energy barriers. The major steps of the process can be summarized as the
evaporation of the material to be deposited by a high-energy source such as an electron beam or
ions. This evaporates atoms from the surface, transport of the vapor to the substrate to be coated,
reaction between the metal atoms and the appropriate reactive gas (such as oxygen, nitrogen or
methane) during the transport stage, deposition of the coating at the substrate surface. [3]

In comparison to the PVD there is another similar technique called the chemical vapor deposition
(CVD). The CVD comprises the chemical reaction of a volatile compound of a material desired to
be deposited together with other gases to produce nonvolatile deposited solid. This technique

4
also found many applications such as the solid-state electronic devices and the manufacture of
ball bearings and cutting tools. [1]

PVD is different from Chemical Vapor Deposition (CVD) in some aspects those are that PVD
relies on solid or molten sources for the atoms. The excitation mechanisms that transfer the atoms
of the source to the gas phase are physical rather than the chemical techniques employed in
CVD. The pressure inside the chamber in which the PVD process is carried out is reduced to
allow the species to traverse the distance between the source and target. No chemical reactions
take place during the PVD processes. [1]

2.2. Thermal evaporation

This method involves the evaporation or sublimation of the solid source materials, metal or non-
metal, using resistive heating element. The aim is to transform some of the surface atoms or
clusters of atoms into a vapor stream allowing them to traverse the vacuum chamber and deposit
on the target substrate. The deposition rate depends on many parameters such as the
evaporation rate, the temperature and the pressure of the chamber. [1]
The techniques that depend on this method are various among which are:
1. Resistance heated evaporation sources such as (tungsten wire source, sublimation
furnaces, crucible sources).
2. Electron beam evaporation sources.
3. Refractory metal sheet sources also known as (thermal boat). [1]

The thermal boat method will be discussed in depth separately since it was employed in this lab
session. To study the kinetics of the process the evaporation rate is considered.
2.3. Evaporation rate
The earliest attempts to quantitively describe the evaporation phenomenon were carried out by
Hertz, Knudsen and later Langmuir. Hertz noticed that the evaporation rate won’t stop if
insufficient heat was supplied to the surface of the molten vaporized species so as that the rate
is proportional to the equilibrium pressure Pe (evaporation pressure) at a certain temperature and
to the hydrostatic pressure 𝑃ℎ acting on the system. [1]

This led to the basic idea of the equation that describes the rate of evaporation from liquids and
solids
𝛼𝑒 𝑁𝐴 (𝑃𝑒 − 𝑃ℎ )
Ф= (2.1)
√2𝜋𝑀𝑅𝑇

Where Ф is the evaporation flux (atoms/m2.sec), 𝛼𝑒 is the coefficient of evaporation taking values
between ([0,1]) and M is the molecular weight of the evaporating species. When 𝛼𝑒 is 1, then 𝑃ℎ
is zero and the maximum evaporation is realized. The maximum flux possible can be written as:

3.513 ∗ 1022 (𝑃𝑒 )

Ф= (2.2)
√𝑀𝑇

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And when 𝑃𝑒 is expressed in torr, the previous equation can be written as

𝛤 = 5.834 ∗ 10−2 √𝑀⁄𝑇 (𝑃𝑒 ) (gm/cm2.sec) (2.3)

where 𝛤, is the mass evaporation rate. At a pressure of torr, a typical value of 𝛤 for many elements
is approximately g/cm2-sec of evaporating species. [1]

The vapor pressure of the vaporized species can be studied using the Clausius-Clapeyron relation
in Figure 1.
𝑑𝑃 𝑃∆𝐻(𝑇)
= (2.4)
𝑑𝑇 𝑅𝑇 2

With some approximations, such as taking the change in enthalpy to be the heat of sublimation,
the following equation can be written and used to determine the pressure of the vapor phase as
a function of T depending on the heat of sublimation for each material.
∆𝐻𝑒
ln 𝑃 = + 𝑐𝑜𝑛𝑠𝑡. (2.5)
𝑅𝑇
This equation can be used for different materials to construct the following graph relating the
pressure of the vapor phase and the temperature.

Figure 1: Vapor pressures of selected elements. [2]

The dots on the lines in figure 2.1 represent the melting points. The pressure of the vapor phase
should be high enough to enable sensible rates of deposition.

6
2.4. Evaporation techniques
2.4.1. Resistance heated evaporation sources
These heaters are used to take the source to the vaporization temperature. Upon heating, the
metal and the heater should not contaminate, react, or alloy with the evaporates or release
gases such as oxygen, nitrogen, or hydrogen at the evaporation temperature. [1]

Figure 2. Resistance heated evaporation sources. (Courtesy of R. D. Mathis Company)

Resistively heated evaporation sources are available in a wide variety of forms utilizing
refractory metals independently or in combination with inert oxide or ceramic compound
crucibles. [1] The following figure illustrates the general shape and operation concept of heaters
so as the electron beam evaporation source.

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Figure 3. (a)Knudsen evaporation source (b) Crucible evaporation (c) Thermal boat evaporation source (d) Electron
beam evaporation source [4]

In Figure the thermal evaporation sources are illustrated. In figure (2.3a) and (2.3b) heating occurs
because of induction coils which operate typically at radio frequency. The difference between
both techniques is the emitted flux. The Knudsen source produces near steady-state equilibrium
between the melt and vapor when the orifice on top is small compared to the room of the
chambers. These techniques together with the thermal boat source, produce a lot of impurity
elements in the atmosphere of the chamber and, thus, it is difficult to obtain high purity thin films
using those techniques.

In figure (2.3c), the thermal boat evaporation source is illustrated. The boat is usually a refractory
metal or a ceramic cup made of oxides or pyrolytic BN that is wrapped with tungsten wire hating
elements. Other sources rely on high frequency induction rather than heating with an element. In
figure (2.3d) the electron beam technique is illustrated. This technique employs accelerating
electrons generated from an electron gun and allowing them to go through a transverse magnetic
field to move in a circular motion, hitting the atoms’ source which lies in the trajectory of the
moving electron at ground potential. The atoms at the surface of this source will sublime and
proceed with the gained kinetic energy from collision to deposit on the substrate. The source of
the electrons should not lie in the line of sight of the atoms’ source. A major advantage of this
technique is the higher purity of the thin films achieved using this technique in comparison to the
thermal evaporation techniques. This technique also allows the production of thin films from many
materials at any production rate. [1]
2.5. Purity of films
The purity of the source and the contaminants that come from the heater, the crucible or the
support materials as well as the impurity gases that are stuck in the vacuum system can affect
8
the purity of the film. Good experimental procedure can eliminate the first two types of impurities
as much as possible. The gas impurities are present most of the time and the following treatment
is employed to assess the amount of gas impurities in the thin films.

5.82 ∗ 10−2 𝑃𝑔 𝑀
𝐶𝑂2 = 𝑘 (2.6)
√𝑀𝑔 𝑇𝜌𝑑̇
Equation (2.6) describes the concentration of the oxygen impurity present in the thin film as a
function of the partial pressure of the gas 𝑃𝑔 (Torr), the molecular weights of the thin film and the
gas M, Mg (gm/mol), respectively, the density of the thin film 𝜌 (gm/cm3) and the deposition rate
of the thin film 𝑑̇ (cm/sec).
To produce very pure films, it is important to deposit at very high rates while maintaining very low
background pressures of residual gases such as H2O, CO2, CO, O2 and N2[1]

2.6. Uniformity of films

Thin film, narrow-band optical interference filters require a thickness uniformity of ≈1%. The
source-target geometry plays an important role in this. Equation (2.7) is used to describe the
thickness of the film, more precisely, the variation of the thickness for different spots on the
surface of the target substrate as a function of the distance h between the source and the film,
the surface area of the film l and the highest value of the thickness 𝑑0 occurring at l=0, for point
sources.
𝑑 1
= (2.7)
𝑑0 (1 + (𝑙 ⁄ℎ)2 )2
The following Figure shows the dependence of equation (2.7) on the geometry of the source and
the arrangement of the components inside the vacuum chamber and describes the variation of
the thickness uniformity with the change in the location of the components. [1]

Figure 4. Film thickness uniformity for point and surface sources. Source: M. Ohring, Materials Science of Thin
Films, Academic Press, London (2002).

9
A better way to achieve thickness uniformity, however, is to locate both the surface evaporate
source and the substrates on the surface of a sphere as illustrated in the following figure.

Figure 5. The arrangement of the source and target ensures thickness uniformity of the film. Source: M. Ohring,
Materials Science of Thin Films, Academic Press, London (2002).

Surfaces of the substrates are not perfectly smooth. The irregularities that appear on the surface
might manifest themselves in step-like edges arising the potential for a major defect in the thin
film. The inadequate step coverage because of the shadowing effect is illustrated in the Figure .
Shadowing means that the angle of incidence of the evaporant atoms on the substrate varies
from point to another on the surface of the substrate since both the target and the source are at
fixed positions. This might lead to the fracture of the film in case of high-pressure applications
such as forming tools because of the minute cracks that form within the film. Another
consequence of low-quality thin films is that thinned regions on the conducting stripes can exhibit
greater joule heating effect and lead to burnout. [1]

Figure 6. Illustrations of the thin film coverage of the substrate. A) uniform coverage; B) poor side wall coverage;
C) lack of coverage. Source: M. Ohring, Materials Science of Thin Films, Academic Press, London (2002).

10
2.7. Sputtering
Sputtering is a widely-used technique for the thin-film deposition of elemental and compound
materials. It is particularly suitable for large area coatings; for example, the standard architectural
glass has a size of 3*6 m2. The Figure illustrates the setup of the sputter deposition system. It
consists of a target of the source material which faces the substrate holder. The setup is in
vacuum backfilled with process gas to pressure of 0.1-10 Pa. By applying a voltage of sufficient
magnitude between the cathode (target) and the anode (vacuum chamber), a glow discharge
(plasma) is ignited and the ionized gas ions are accelerated towards the target surface. [5]

Figure 7. a) typical arrangement of sputter deposition with a single cathode, b) fundamental processes occurring
during ion impact at a target; c) schematic illustration of the magnetron sputtering. Source: L. Alff, A. Klein, P.
Komissinskiy, and J. Kurian, Vapor phase deposition of oxides, Ceramics Science and Technology, c) extracted
from [http://www.semicore.com/what-is-sputtering]

Those ions that hit the target surface are partially reflected as ions or neutrals, or are implanted
into the target. The collisions with the target atoms transfer energy and momentum, which
causes the ejection of target atoms and ions. [5]

In Figure ,the potential distribution is illustrated in both sputtering techniques. In a discharge,

excited by applying a constant voltage (DC discharge), most of the potential drop occurs in the
so-called “cathode fall region” in front of the cathode (target). The sputter deposition of insulating,
or poorly conducting, materials requires plasma excitation with no net current flow. This can be
achieved by radiofrequency (RF of around 13.56 MHz) excitation. Because of the different mass
of electrons and gas ions in the plasma, the resulting larger electron current leads to a negative
charging of the cathode and anode with respect to the average potential in the plasma. [5]

11
 Figure 8. Potential distribution with: a) DC current; b) RF plasma excitation

The typical potential drop in such a plasma sheath is 100 V, which is much smaller than in the
case of a DC discharge. To avoid substantial bombardment and re-sputtering of the growing film
on the substrate by ions accelerated in the plasma sheath region adjacent to the substrate, the
anode sheath must be reduced. This is accomplished by a larger anode area compared to the
cathode. [5]
One disadvantage of magnetron cathodes is the strongly inhomogeneous erosion of the target,
which limits the use of the materials to about 40% of the starting material and result in what is
known as the race tracks flaws. The Figure shows this flaw and the way of applying the magnetic
field to maintain the discharge at lower pressure by reducing the number of collisions between
the electrons and the gas atoms. For small distances between the target and substrate, this
results in inhomogeneous deposition rates and particle energies, and consequently also to
inhomogeneous film properties. [5]

Figure 9. Cross-section through a magnetron cathode and typical target utilization for standard geometry with fixed
target and magnet system

2.8. Quartz Crystal Microbalance:

The QCM is a piezoelectric disk of crystalline quartz connected to an external circuit. The acoustic
resonances of this plate can be excited electrically because crystalline quartz is piezoelectric. The
12
main application of quartz resonators is in time and frequency control. However, the resonance
frequency and the resonance bandwidth depend on the resonator’s environment and the plate
can therefore be used as a frequency-based sensor. [6]

The centre piece of a quartz crystal microbalance (QCM) is a quartz crystal resonator (QCR). A
QCR essentially is a disk of crystalline quartz. Figure shows the QCR crystal.

Figure 10 A QCR in casing (right) and outside of it (left). Scource: D. Johannsmann, The Quartz Crystal
Microbalance in Soft Matter, Springer, Heidelberg (2015)

The name ‘‘microbalance’’ goes back to Günter Sauerbrey. The name suggests that the QCM is
a quartz-based device for measuring small (‘‘micro’’) masses. The sensitivity is well in the range
of ng/cm2. The crystal measures the mass per unit area and not the mass itself. On a fundamental
level, the QCM measures periodic forces exerted at its surface. It is a ‘‘force balance’’.
Coincidentally, the forces turn out to be in the micro Newton range, so that the prefix ‘‘micro’’ can
stay. At resonance, the deformation pattern is a standing plane wave with antinodes at the
surface. The wavelength of sound is twice the thickness of the plate. If a thin film is deposited on
one surface and if this film has the exact same acoustic properties as the resonator, all the film
does, is to increase the acoustic thickness of the plate. The wavelength of sound, λ, increases
and the resonance frequency, fr, decreases accordingly. [6] The Sauerbrey equation (2.8) can be
used to describe the change resonance frequency of the QCM because of the change in its mass
resulting from the deposition on the quartz crystal. [6]

∆𝑓
𝑚𝑓𝑖𝑙𝑚 = −𝐶 (2.8)
𝑛

In this equation, the change in frequency ∆𝑓 is related through the sensitivity-mass constant C to
the mass of the deposited film 𝑚𝑓𝑖𝑙𝑚 . The factor C accounts for the density of the quartz and the
shear stress of the quartz crystal. This equation is valid only if the frequency of the crystal is not
exceeding 2% of the original value because this would be in accordance with the assumptions
stating that the thin film should be an extension of the crystal itself, rigid and experience no shear
stresses. [6]

13
Beyond this extent, the crystal is now viscoelastic and another coefficient should be employed to
account for the changes; eventually yielding the following equation (2.9) to calculate the deposited
mass of the film. [6]

𝑛𝑞 𝜌𝑞 𝜋(𝑓0 − 𝑓)
∆𝑚𝑓𝑖𝑙𝑚 = 𝑡𝑎𝑛−1 [𝑍 𝑡𝑎𝑛 ( )] (2.9)
𝜋𝑍𝑓 𝑓0

The thickness of the film can now be calculated simply using equation (2.10).
∆𝑚𝑓𝑖𝑙𝑚
𝑑= (2.10)
𝜌𝑓𝑖𝑙𝑚

2.9. HEX deposition system

The HEX system is a chamber containing usually three devices for heating source atoms into
vapor phase to deposit them in high vacuum. The high vacuum state is attained with the help of
a two-pump system. One pump is used as a pre-pump and is detached from the body of the
chamber and is used to take out the dust and bring down the pressure to an intermediate state of
around 10-2 mbar. Elimination of dust is crucial before the system starts the second, high vacuum
pump as it would damage the single-crystal blades. High vacuum conditions of down to 8*10-7 bar
is attained using the high vacuum pump attached to the body of the chamber. The chamber
employs DC-RF fission sputtering sources in addition to thermal boat resistance heating system.
Every vaporization source is additionally provided with a shutter to shield against the flux of atoms.
QCM unit exists parallel to the sample which is held upside down in the chamber under a
stainless-steel mould and both are also provided with shutters to control the flow of the flux
admitted to either of them. Water cooling is used to cool down the different components. [7]

Figure 11. The HEX deposition system outside view. 10

14
 Figure 12. Magnetron source and the shutter window. 11

2.10. DektakXT stylus profiler

To measure the thickness of the film precisely and compare the results to the rough estimation of
the thickness that is carried out by the QCM technique in the HEX system, the DektakXT profiler
is used for this purpose. Stylus profilometry has four main components: topography sensor, pivot,
force compensation, stylus. The pivot connects the stylus to the topography sensor, translating
the change in motion from the stylus to the sensor. The force compensation mechanism is
connected through the pivot to determine the amount of force that will be exerted on the sample
surface.
The profilometer utilizes a LVDT (Linear Variable Differential Transformer) sensor to control the
applied force in a range between 0.03 to 15mg. This system allows a vertical range scanning up
to 1mm with a vertical resolution <0.5 nm, and provides excellent resolution for roughness
measurements, wall and trench characterization, and measurements in constrained areas. [8]
2.11. Resistivity of the thin film
According to Ohm’s law, the resistance could be measured according to equation (2.11)

𝜌𝑙
𝑅= (2.11)
𝑤𝑑
𝜌
In which the value of 𝑑 is more indicative to the value of the resistance, since the squared samples
𝜌
usually prepared have equal width and length (l, w) dimensions. The factor is named the sheet
𝑑
resistance 𝑅𝑠 and as a result, equation 2.11 can be re-written as equation (2.12).

𝑙
𝑅 = 𝑅𝑠 (2.12)
𝑤

The sheet resistance is measured in units of Ω/cm2 to differentiate it from the bulk resistance.

3. Experiment
3.1. Sample Preparation
The deposition of titanium and silver films for this experiment is made employing a pre-defined
pattern, using a deposition mask which selectively covers part of the surface area of the substrate
which allows for a further resistance measurements of the film.
15
 Figure 2 Deposition mask for a 5×5 mm2 composed of two stripes with 5 and 10 thin-film squares for
four- and two-terminal resistance measurements.

3.2. Deposition of silver thin film

The deposition of the silver film is made utilizing the thermal boat configuration of the HEX system.
Pressure was set to 1x10-5 Torr. Density of silver is 10,50 g/cm3 and its acoustic impedance is
16.69 g/cm2s.

Voltage of the equipment is slowly increased until reaching 1.289 V where a deposition rate of
45.2 A/s is established.

3.3. Deposition of titanium thin film

The deposition of the silver film is made utilizing the DC Magnetron sputtering configuration of the
HEX system. The density of titanium is 4.5 g/cm3 and acoustic impedance is 14.06 g/cm2s.
3.4. Resistance Measurement
The measurement of resistance is performed using a conventional multimeter, employing the two-
terminal resistance measurement technique. It is possible to get an approximate value of the
contact resistance by taking a reading of sample resistance while keeping the test leads as close
as possible without contact. A total of five measurements are made for both the sample resistance
and contact resistance
3.5. Thickness Measurement
During the deposition process, the quartz crystal microbalance (QCM) is constantly monitoring
the thickness of the deposition. At the end of the deposition, the measurement is automatically
displayed by the software.
A DektakXT stylus profiler is employed to measure the thicknesses of the final samples.

16
4. Results
4.1. Film Thickness:
DektakXT Stylus Profilometer was used to measure the thickness of the thin films of Ag and Ti.
This user-defined program allows selecting the substrate region and sample region highlighted in
red and green respectively. The yellow region in Figure 14 shows the shadowing effect.

Figure 3 Graph of Silver (Ag) 2- Point by stylus profiler

Figure 4 Graph of Silver (Ag) 4- Point by stylus profiler

17
 Figure 5 Graph of Titanium (Ti) 2- Point by stylus profiler

Figure 6 Graph of Titanium (Ti) 4- Point by stylus profiler

Figure 14 and Figure 15 show the stylus profiler curves for Ag 2-Point and 4-Point measurements.
It can be easily seen in Figure 14 and Figure 15 and, that there are some up and down peaks
that can be assumed due to the impurities and uneven film deposition.
Figure 16 and Figure 17 indicated the undefined peaks in the curve which may be due to some
impurities on the surface of deposited film and due to the thickness variation of deposited film.
Variation of thickness film may cause by the angular orientation of the target to the substrate.

18
Table 1 Film Thickness measured with DektakXT Stylus Profiler for Ag 2-Point, 4-Point, and Ti 2-Point, 4-Point
Deposited Thickness 1 Thickness 2 Thickness 3 Mean Standard
Film Method (nm) Deviation
(nm) (nm) (nm)
2-point 34.86 - - 34.86

Silver 4-point 38.22 - - 38.22

Average 36.54 2.37

2-point 49.51 47.29 48.58 48.46

Titanium 4-point 73.80 - - 73.80

Average 61.13 17.91

Table 1, represents the thickness values measured by stylus profilometer for Ag and Ti films. The
thickness obtained for the Ag is 36.54nm and Ti is 61.13nm. In comparison to film thickness
measured from QCM, the value of Ti deposited film is comparatively high due to high deposition
film on a substrate which could not be analyzed with the QCM. As the position of QCM and
substrate are at different angles to the target which causes the variation of thickness in contrast
to the actual thickness.
4.2. Tooling Factor
The ratio of the actual thickness to the one measured with QCM.
𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠𝑜𝑣𝑒𝑟𝑎𝑙𝑙
𝑇𝑜𝑜𝑙𝑖𝑛𝑔 𝑓𝑎𝑐𝑡𝑜𝑟 =
𝑇ℎ𝑖𝑐𝑘𝑛𝑒𝑠𝑠𝑄𝐶𝑀

Table 2 Tabular representation of thickness and tooling factor of Ag and Ti

DektakXT Stylus
Tooling
Deposited Film Profiler Thickness QCM Thickness (nm)
Factor
(nm)

Silver 36.54 30 1.218

Titanium 61.13 30 2.037

The thickness measured with the QCM should be similar to the overall thickness measured by
the profilometer, but as it can be seen in table 3, the Ag thin film is near to the actual value but
there is a difference at great extent for Ti film explained by the orientation of the chamber and the
direction of sputtered particles. As the position of the thermal evaporation boat is on the same
side to the QCM, while sputtering target and QCM lies on the opposite sides of the chamber. It
was also observed that the deposition rate on QCM kept on fluctuating during sputtering, this may
be because of the plasma ions can reach the QCM and re-sputter the deposited atoms.

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4.3. Concentration of Oxygen Impurities
Oxygen impurities in the silver thin film can be calculated by equation 2.6 using the following
parameters.

(5.82×10−2 )×( 6×10−5 𝑇𝑜𝑟𝑟)×(107.8 𝑔𝑟𝑎𝑚/𝑚𝑜𝑙)

𝐶𝑜2 = (1) 1
(32×300 𝐾)2 ×(10.50 𝑔/𝑐𝑚3 )×(1×10−8 𝑐𝑚/𝑠)

𝐶𝑜2 = 36.59

The residual gas concentration in the film is achieved at 36.59. As the partial pressure of the gas
in the chamber is near to the desired value (1x10 -5 Torr). Also, the calculation is done assuming
the maximum value of the sticking coefficient.
4.4. Resistance of 2-Point Deposited Ag- Film
The resistance of the thin film was measured by the voltmeter with a 2-Point contact method on
one of each end of the deposited film. Furthermore, the contact resistance is calculated by placing
the two probes nearly at the same point. Whereas, the total resistance of the thin film is the sum
of the resistance of sample and contact resistance represented in Table 2
𝑅𝑇𝑜𝑡𝑎𝑙 = 𝑅𝑆𝑎𝑚𝑝𝑙𝑒 + 𝑅𝐶𝑜𝑛𝑡𝑎𝑐𝑡
Table 3 Representation of total resistance

Deposited Films Resistance of Sample Resistance of Contact Total Resistance

(Ω) (Ω) (Ω)
20.7 2.4
Silver 23.7 2.1 25.3
25.0 2.2
Average 23.1 2.2
1.238 59.6
Titanium 1.284 57.3 60.15
1.255 59.9
Average 1.259 58.9

The value obtained of the total resistance of Ag 25.3 Ω and Ti 60.15 Ω can be seen in Table 3.
In order to calculate the sheet resistance and resistivity of Ag and Ti following are the parameters
are used,

Table 4 Representation of parameters for sheet resistance and resistivity calculations

Length of the Film Width of the Film Thickness of Ag Film Thickness of Ti Film
[m] [m] [m] [m]

0.002 0.0002 3.654x10-8 6.113x10-8

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Table 5 resistivity and sheet resistance tabular form

Deposited Film Resistance Resistivity Bulk Resistivity Sheet Resistance

[Ω] [Ωm] [Ωm] [Ω/Sq]
Silver 25.3 9.244 x 10-8 1.59 x 10-8 0.252
Titanium 60.15 3.67 x 10-7 4.30 x 10-7 6.015

It can be observed from Table 5 that the bulk resistivity at room temperature of silver is 1.59 ×
10−8 Ωm and titanium of 4.30 × 10−7Ωm.
The difference between the bulk resistivity and the thin film resistivity of silver and titanium is
nearly the same. In addition, the method of measuring the contact resistance is not precise, as
the samples are very small and difficult to place the probes as near as possible which may cause
an error in readings consequently resistivity of the samples shows small deviation from the bulk
resistivity. Furthermore, the contact resistance of Ag is lower than the Ti film with the fact that
silver shows high electrical conductivity besides, that the contact resistance significantly depends
upon test conditions, in particular, contact pressure.

21
5. Discussion and Conclusion
The goal of the experiment is to gets familiar with the two commonly used techniques for physical
vapor deposition. Dc magnetron sputtering and thermal evaporation boat is used to coat the
samples Silver and Titanium thin-film respectively. The thickness of the deposited films is
measured and compared using the QCM and the profilometer as well as, the resistance across
the deposited films is calculated by the two-point method and compared with the bulk values of
Silver and Titanium, as per literature. Moreover, the concentration of the residual oxygen gas is
also determined in silver films.
The Quartz Crystal Microbalance (QCM) measures the approximate value of film thickness due
to the deposition of material on the quartz crystal resulting change in resonance frequency with
added mass. The thickness measured by QCM is 30nm for Ag and Ti and the actual thickness is
measured by the DektakXT Stylus profilometer by moving a stylus tip over the sample surface to
measure the variation of the deposited films of Ag and Ti, which are found to be 36.54nm and
61.13nm respectively. The deviation of deposited thin film thickness is due to the fact that the
position of QCM was not in the line of sight with the thermal evaporation boat which causes
shadowing effect. The sensitivity of QCM is based on the deposition of the film causes to change
the resonance frequency of quartz less than 2% as compared to the unloaded quartz crystal.
Furthermore, it can also be assumed that human error while shutting down the shutter manually
causes a delay in taking measurements.
The silver film stylus graphs show the hill with fewer peaks as compared to the Ti. The more
peaks in Ti is due to the poor film coverage or irregular deposited film. So, the thickness value
calculated for Ti film shows a higher standard deviation as compared to the Ag film which can be
since the QCM position in HEX system with sputtering target and evaporation boat is different.
Furthermore, for Ag film, there is a small deviation observed in actual thickness values because
of impurities gases present in the chamber which alter the actual thickness measured with stylus
profiler. The resistivity values for both films is calculated by the 2 points method. The comparison
between the bulk resistivity and the thin film resistivity of silver is almost similar. While the
calculated resistance of the Ti sample is 1.259 Ω, smaller as compared to Ag which is 23.1 Ω.
(SURPLICE, 1971, S. 247) explains that the increase in the thickness of the thin film results in
decreasing the resistance.
Concluding, Improvement in the experimental procedure includes, the air pressure inside the
chamber, a good vacuum system can lead to better results. The enhancement of these
parameters can reduce the chances of any impurities inside the chamber along with more uniform
thin films. Another source of impurities in the metal boat in the thermal evaporation technique that
can be avoided by another evaporation source like electron-beam. might be due to the metal from
the boat which was used to heat silver.

22
6. References
[1] M. Ohring, Materials Science of Thin Films, Academic Press, London (2002).
[2] C. H. P. Lupis, Chemical Thermodynamics of Materials, North-Holland, Amsterdam, 1983.
[3] A. Makhlouf, "Current and advanced coating technologies for industrial applications",
Nanocoatings and Ultra-Thin Films, pp. 3-23, 2011.
[4] S. M. Rossnagel, J. Vac. Sci. Technol. A21, S75 (2003).
[5] L. Alff, A. Klein, P. Komissinskiy, and J. Kurian, Vapor phase deposition of oxides, Ceramics
Science and Technology, volume 3, eds R. Riedel and I.-W. Chen, Wiley-VCH Verlag GmbH &
Co. KGaA, Weinheim, Germany (2011).
[6] Johannsmann D. (2015) Gravimetric Sensing. In: The Quartz Crystal Microbalance in Soft
Matter Research. Soft and Biological Matter. Springer, Cham.
[7] KORVUS TECHNOLOGY Broschüre for HEX system.
[8] Bruker; Broschüre for DektakXT stylus profiler.
[9] Ulf Helmersson, Martina Lattemann, Johan Bohlmark, Arutiun P. Ehiasarian and Jon Tomas
Gudmundsson “Ionized Physical Vapor Deposition (IPVD): A Review of Technology and Applications”
[10] Image retrieved from [https://ncmn.unl.edu/thinfilm/Hex%2001.jpg]
[11] Image retrieved from [https://ncmn.unl.edu/thinfilm/Hex]

7. Bibliography

SURPLICE, B. S. (1971). THE ELECTRICAL RESISTIVITY AND RESISTANCE-

TEMPERATURE CHARACTERISTICS OF THIN TITANIUM FILMS. Thin Solid Films.

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