UNIVERSITY OF DELHI

PHYSICS AT NANOSCALE-I LAB

MSc PHYSICS
SEM-III

SUBMITTED TO: SUBMITTED BY:

DR. S Murugavel Prince
DR.Debabrata Mishra
CONTENT:
1. DC Sputtering ………………………1
2. RF Sputtering………………………6
3. DC VS RF Sputtering……………..7
4. X-rays……………………………………8
5. XRD………………………………………..15
6. Observation…………………………..21
7. Discussion……………………………26
8. Precautions…………………………27

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No index entries found.

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SPUTTERING:
Sputtering is the process by which atoms and molecules
are ejected from a source material (target material) by
high energy particle bombardment.
The ejected atoms or molecules travel to the substrate
where they condense as a ‘thin film’.

Principle:
When a fast moving strikes the surface of a material then
target atoms are ejected (sputtered) from the cathode by
energy and momentum transfer.
Sputtered atoms from the target are deposited on the
substrate (anode).

DC Sputtering and its mechanism :

Introduction: Overview of the process –

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A gaseous plasma is generated by applying an electric
field inside a vacuum chamber filled with a heavy inert
gas such as Argon, at a specific pressure.

The inert gas ions accelerate under the field towards the
cathode which is made of the source material (called the
target).
Momentum transfer from the bombarding ions to the
surface atoms of the target results in their ejection.

The ejected atoms diffuse towards the substrate

(attached to the anode) and are deposited.

Plasma is formed by the ionization of Argon due to the

electric field.

This process begins when a free electron from the

cathode is accelerated towards the anode.

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On its way the electron encounters a neutral Argon gas
atom and collides with it to produce a positively charged
ion and two more free electrons.

The newly generated free electrons go on to ionize more

Argon atoms.

This continues until the gas breaks down. The break

down voltage depends on the Argon pressure and
distance between the cathode and the anode.

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Plasma generation and control:
• Plasma generation is optimized by determining the gas
pressure required for maximum efficiency
• If the pressure is too low, there aren’t enough collisions
between electrons and atoms to sustain a plasma
• If the pressure is too high there too many collisions and the
electrons do not have enough time to gain energy in order to
ionize atoms
• Mean free path for the electron should be a tenth or less
than the typical size of the chamber • Typical pressure ranges of
10-1000 m -Torr and plasma densities of 1010 to 1012 cm

Ion-Surface Interaction
• When ions bombard the cathode surface, several possible
interactions can take place:
– Reflection
– Adsorption
– Sputtering
– Ion implantation
– Electron and photon emission
– Chemical reactions

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• The type of interaction is dictated by the energy of the ion-
beam:
– Less than 5 eV => Adsorption or reflection
– 5 – 10 eV => Surface damage and migration
– 0.01 – 3 keV => Sputtering
– > 10 keV => Ion implantation

Advantages of DC Sputtering:
• Deposition rate fast, damages to the film is small.
• Well combined thin film on substrate.
• Uniform thickness, large area substrate.
• Easy to industrialize.

Limitation of DC Sputtering :
Suppose instead of a metal, we want to sputter an insulator like
quartz, Due to the high resistivity of the target running an
appreciable current through would require an impossibly large
voltage (~10^12V).
Practically this limits for DC sputtering to materials of a
resistivity 10^6Ω.m is not possible.

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RF Sputtering:
RF Sputtering is a technique that uses radio frequency (RF)
power to create a plasma and bombard a target with ions to
eject atoms that coat a substrate.

Instead of applying a DC voltage to the cathode, apply a voltage

oscillating at radio frequency (RF), typically around 13.5 M-Hz.
•The RF peak to peak voltage is around 1000V, electron
densities are around 109-1011 cm-3and the chamber pressure
is 0.5 -10 m-Torr.
•On the positive cycle, electrons are attracted to the cathode,
creating a negative bias (think of it as replenishing the negative
charge on the target surface).
• On the negative cycle ion bombardment continues.

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Difference between DC Sputtering and
RF Sputtering:
DC sputtering has a higher deposition rate than RF sputtering . While DC
sputtering is suitable for depositing large quantities onto large substrates,
RF is more effective within smaller substrates.

DC and RF sputtering can deposit different types of target materials. While

DC sputtering can deposit electrically conductive target materials, an RF
sputtering method is suitable for various sputtering targets, including
conductive and non-conductive materials.

Finally, DC and RF sputtering vary in their complexities and price points.

DC sputtering is more affordable overall, as it uses less specialized
processes. RF sputtering involves a more complex process, yet its
versatility and excellent campaign length make up for its high price point.

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 X-Rays
x-ray was the name given to highly penetrating rays which
emanated when high energy electrons stuck a material target.
Within a short period of their discovery, they were being used
in medical facilities to image broken bones.

Production of X-Rays:-
i. A current is passed through the tungsten filament and
heats it up.

ii. As it is heated up the increased energy enables electrons

to be released from the filament through thermionic
emission.
iii. The electrons are attracted towards the positively
charged anode and hit the tungsten target with a
maximum energy determined by the tube potential
(voltage).
iv. As the electrons bombard the target they interact via
Bremsstrahlung and characteristic interactions which
result in the conversion of energy into heat (99%) and x-
ray photons (1%).
v. The x-ray photons are released in a beam with a range of
energies (x-ray spectrum) out of the window of the tube
and form the basis for x-ray image formation.

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 Diagram of x ray tube

 Cathode:
We use tungsten filament as cathode in x-rays tube because:
 It has a high atomic number (A 184, Z 74).
 It is a good thermionic emitter (good at emitting electrons).
 It can be manufactured into a thin wire.
 It has a very high melting temperature (3422°c).

 Anode :
 Target made of tungsten for same reasons as for filament.
 Positively charged to attract electrons.

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  Set at angle to direct x-ray photon beam down towards
patient.

Summary:
 Filament current is applied across the tungsten cathode
filament (10 A) and affects the number of electrons released.
 Tube current is applied across the x-ray tube from cathode
to anode and affects the energy and number of electrons
released.
X-Rays can be produced by two methods:
i. Continuous X-Ray production
ii. Characteristic X-Ray production

Continuous X-Ray:
Electrons with very high initial kinetic energies can penetrate deep
into the target molecule’s atom. It comes in close proximity to the
nucleus. The electron is negatively charged, and an atom’s
nucleus is positively charged. The nucleus exerts an electrostatic
force on the incoming electron, changing its initial trajectory. The
speed of electrons decreases, and their energy also diminishes
significantly. Thus, the x-rays do not have one fixed frequency,
but they have a range (which goes up to a maximum frequency)
due to the deceleration of electrons.
It is also known as bremsstrahlung, which means breaking
radiation. It is also referred to as white light since it comprises
radiation of differing wavelengths, just like white light.

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Bremsstrahlung accounts for the majority of x-ray photon production.

Production of continuous x-rays:

To produce x-rays, we use an X-ray tube or a Coolidge tube. It is a glass tube having a
vacuum environment inside. There is a cathode (mostly tungsten filament) at one end
and an anode at another. Cathode produces high-speed electrons that hit the anode.

The maximum frequency of continuous x-rays depends on the voltage of the anode. Let
V be the accelerating potential of the X-ray tube or the potential difference between the
anode and the cathode.

Maximum energy or minimum wavelength (𝝀min) photons are released by the kind of
electrons which lose all their energy upon a single collision with the anode material.
Their entire energy (denoted by eV) is transformed into radiation energy.

Now, we know that eV = h-c /𝝀min

Rearranging the equation, we get 𝝀min = h-c/eV

We know the values of h, c and eV

h = 6.6 x 10-34 J-s

c = 3 x 108 ms-1

eV = 1.602 x 10-19 V

Substituting these values in the equation, we get, 𝝀min = 12.4 x 103 Ao/V

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Characteristic X-Ray:
i-A bombarding electron knocks a k-shell or l-shell electron out.
ii-A higher shell electron moves into the empty space.
iii-This movement to a lower energy state releases energy in the form
of an x-ray photon.
iv-The bombarding electron continues on its path but is diverted.

It is called “characteristic” as energy of emitted electrons is

dependent upon the anode material, not on the tube
voltage. Energy is released in characteristic values
corresponding to the binding energies of different shells.
For tungsten:
Ek – El (Kα) = 59.3 keV
El – Em (Kβ) = 67.6 keV

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 X-Ray Spectrum:
Spectrum of the X-rays emitted by an Xray tube with a
tungsten target. The smooth, continuous curve is due to
bremsstrahlung, and the spikes are characteristic K lines for
tungsten atoms.
Bremsstrahlung accounts for the majority of x-ray photon
production.

X-Ray Diffraction:
x-rays are used over visible light for crystal diffraction because of shorter
wavelength. It is used to address the issues related to crystal structures of solid

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 including lattice constant and geometry, identification of unknown material
orientation of single crystals, preferred orientation of polycrystals, defects,
stresses etc.

How XRD works :-

 X-ray diffraction is a common technique that determine a
sample's composition or crystalline structure.
 If the crystal size is too small, it can determine sample
composition, crystallinity, and phase purity. This technique
sends x-ray beams through it.
 X-ray beams are chosen because their wavelength is
similar to the spacing between atoms in the sample, so the
angle of diffraction will be affected by the spacing of the
atoms in the molecule, as opposed to using much larger
wavelengths, which would be unaltered by the spacing
between atoms.
 The x-rays then pass through the sample of the atoms in
the structure, and changing the direction of the beam at
some different angle ( ) from the original beam. This is the
angle of diffraction.
 This is the angle of diffraction. Some of these diffracted
beams cancel each other out, but if the beams have similar
wavelengths, then constructive interference occurs.
 Constructive interference is when the xray beams that are
whole number integers of the same wavelength add together
to create a new beam with a higher amplitude. The greater

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 amplitude of the wave translates into a greater signal for this
specific angle of diffraction.
 The angle of diffraction can then be used to determine the
difference between atomic planes using Bragg’s law.

Bragg’s Law:-
Bragg's law determines the angles of coherent and incoherent
scattering from a crystal lattice. When incident X-rays falls on lattice,
interference pattern occurs. This interference pattern is the basis of
diffraction analysis. This is called Bragg's diffraction.

*Bragg's diffraction results from interference phenomenon between

the periodic lattice.

*When incident wave having wavelength comparable with atomic

spacing falls on crystalline lattice, then scattered waves are
produced. When the scattered waves interfere constructively, then
the path difference between two scattered waves is an integral
multiple of wavelength.
nλ=2dsinθ
where:
 λ is the wavelength of the x-ray,
 d is the spacing of the crystal layers (path difference),
 θ is the incident angle (the angle between incident ray and the
scatter plane), and
 n is an integer

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Peak width:
Peak width depends upon 2 factors:
(i)Crystallite size (ii) Lattice strain

(i)Crystallite size:

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 It is the size of coherently diffracting piece of crystal. As crystallite in
powder gets smaller diffraction peaks in powder pattern gets wider.
In XRD pattern crystallite size can be calculated by Sherrer’s formula:

d=k λ /β cosθ

Derivation of Scherrer’s Equation:

Bragg's law is given by,
n λ =2 d sin θ …………. (1)
Multiply both sides by an integer m such that md=t,the thickness of the
crystal. This leads to, n=1:
m λ =2 m d sin θ
m λ =2 t sin θ ….………. (2)

Eqn. (2) can also be interpreted as the m th order reflection from a set
of planes with a interplanar distance t. Differentiate both sides of eqn.
(2) remembering m λ is a constant. This gives,

0 = 2 Δt sin θ + 2 t cos θ Δθ … (3)

Remembering that as Δ θ can be positive or negative (we are only

interested in absolute values) leads to,

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 t= Δ t ⋅ sin (θ)
cos (θ) Δθ ……… (4)

Since the smallest increment in t is d, using Δ t=d, and substituting λ /2

for dsinθ (from Bragg's law) we get,
t= λ .
2 cos (θ) Δ θ ………. (5)
Substituting B for 2 Δθ, the angular width, we get,

t= λ .
B cos (θ) ……..….…. (6)
which is essentially Scherrer’s equation.
A more sophisticated analysis of the problem only adds a prefactor of
0.9 to the right hand side of eqn. (6) and leads to the correct Scherrer’s
equation.

t= 0.9 ⋅ λ
B cos (θ)
Where :
 t is the size of crystallite
 k is Scherr’s constant
 λ is wavelength of X-rays
 B is full width of half maximum
 θ is peak position

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Observations:
. Constant time, t=8 min
Sample Voltage(v) Time(min.) 2Θ(in FWHM FWHM( Crystallite
no degree) (in in size[d](nm)
radian) degree)
1 120 V 8 min 44.59 0.009075 0.518 15.27 nm
4 140 V 8 min 36.28 0.006632 0.380 21.2 nm

Constant voltage, v=140V

Sample Voltage(v) Time(min.) 2Θ(in FWHM FWHM( Crystallite
no degree) (in in size[d](nm)
radian) degree)
4 140 V 8 min 36.28 0.006632 0.380 21.2 nm
6 140 V 12 min 44.65 0.005916 0.339 25.57 nm

Sample 1:

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 Discussion:
• standard values for the copper nanocrystal are - 43.4, 50.5, and 74.2
correspond to the (1 1 1), (2 0,0),and (2 2 0) peaks of copper (JCPDS, file
no. 04-0836).
• As we can see from the graphs, the peak values we got from the XRD
of the copper sample are – (44.6)(36.3)(44.7) (degrees) . So, our data
matched from the JCPD file.
• The peak has been obtained for the copper nano crystal due to the
highly nanocrystalline properties of the metal.
• From XRD pattern, it was found that crystallite size of copper
deposited on glass slide increases as we increase the sputtering time.
For 8 min 120V crystallite size is 15.27nm and for 8 min 140V 21.2nm.
For 140V constant voltage we got crystallite size at 8 min 21.2 nm and
for 12 min 25.57nm.

• When the geometry of the incident x-rays impinging the sample

satisfies the Bragg’s Law, Constructive interference occur and a peak in
the intensity appears.
• As we can see from the Graphs, we have peaks at angles other than
44.59,36.28,44.65(degrees) are due to the impurities and the oxides
formation of copper.

Precautions:

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• Surfaces of the sputtering unit may be very hot or very cold. Do not
touch hot or cold surfaces such as the source, substrate holder,
diffusion pump, cryopump or liquid nitrogen pump.
• Wear clean lint – free gloves when you handle components in the
chamber to prevent the contamination of the source and its
accessories.
• Do not operate the source in the area where there is equipment
subject to magnet interference.
• After depositing thin film of copper on the glass substrate leave it for
2-3 min then take out it from the chamber and cover it with the tissue.
(Do not cover it until it cools down.)
• Place all the thin films in the air tight chamber to avoid contacts with
moisture and air to prevent it from the oxides and sulphides in air.

. References:
• Lab manual copy provided by lab staff
• https://www.researchgate.net/topic/DC-Sputtering
• https://byjus.com/physics/braggs-law/
•https://www.sciencedirect.com/science/article/pii/S18785352
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