Nanoscale Coating-PVD

Nanoscience & Nanoengineering
NANOSCALE COATING
METHODS
PVD
1
Physical Vapor Deposition (PVD)

The characteristic feature of PVD techniques is that the transport of vapors
from the source to the substrate takes place by physical means.
Here, in this way, the vapor species of a solid material is created by thermal
evaporation, or by mechanically knocking out the atoms or molecules, and
then deposited directly on substrate without any chemical reactions.
The mean free path (mfp) of the ambient gas molecules is greater than the
dimensions of the deposition chamber and the source-to-substrate distance.
Under low-pressure ambient conditions, the transport of the material from the
source to the substrate occurs by molecular beams.
Low Pressure High Pressure
2
Mono-source evaporation/sputtering
Multi-source co-evaporation/co-sputtering
3
Physical Vapor Deposition – Thermal PVD

• Thermal PVD – also called Vacuum Deposition
– Coating material (typically metal) is evaporated by
melting in a vacuum
– Substrate is usually heated for better bonding
– Deposition rate is increased though the use of a DC
current (substrate is the anode so it attracts the
coating material)
– Thin ~0.5 mm to as thick as 1 mm.
4
Thermal Evaporation
http://www.lesker.com/newweb/
Deposition_Sources/ThermalEv
aporationSources_Resistive.cfm
5

- Vacuum Evaporation
As the name implies, the techniques consists of vaporization of

the solid material by heating it to sufficiently high temperatures
and condensing it onto a cooler substrate to form a film.
The simplest and the most common method is to support the

material in a filament-basket or boat, which is heated
electrically, or is indirectly heated in crucibles of insulating
materials such as quartz, graphite, alumina, and zirconia, which
are supported in a metal cradle.
6
Evaporation
• Evaporating alloys is difficult Because of the differing
vapor pressures.
– Composition of the deposited material may very different
from that of the target material
• The problem can be overcome by
– Using multiple e-beams on multiple sources
• This technique causes difficulties in sample uniformity because of the
spacing of the sources
– Evaporating source to completion (until no material is left)
• Dangerous to do in e-beam system
7
Evaporation
• Compounds are also hard to evaporate
because the molecular species may be
different from the compound composition
– Energy provided may be used to dissociate
compound.
– When evaporating SiO2, SiO is deposited.
Evaporation in a reactive environment (flowing O2
gas near crucible during deposition) helps
reconstitute oxide.
8
PVD
Vapor pressure as a function of temperature of

commonly evaporated metals
9
Evaporation
• Advantages • Disadvantages
– Little damage to the – Materials with low vapor
wafer pressures are very
– Deposited films are difficult to evaporated
usually very pure • Refractory metals
– Selected step coverage • High temperature
dielectrics
– No in situ precleaning
– Limited step coverage
– Film adhesion can be
problematic
10
Kinetics of Evaporation & Condensation

The rate of free evaporation of atoms or molecules from a clean surface
of unit area in vacuum is given by Langmuir-Dushman equation,
N e  3.5131022 pe (1 / MT )1/ 2 molecules  cm 2 s 1

pe - the equilibrium vapor pressure (in Torr) of the evaporant under
saturated vapor conditions at a temperature T.
M - the molecular weight of the vapor species.
The rate of condensation of the vapors depends not only on the

evaporation rate but also on the source geometry, its position
relative to the substrate, the degree of vacuum, and the
condensation coefficient.
11
Necessary of Vacuum on PVD

Because of collisions with the ambient gas molecules, a fraction of the vapors,
proportional to exp(-d/) (, mean free path for air), is scattered and hence
randomized in direction within a distance d during their transfer through the gas.
Pressure Mean free path Time for monolayer deposition at
(Torr) (cm) 1Å/s (sec)
10-2 0.5 4400

10-4 51 44
10-5 510 4.4
10-7 51000 0.044
10-9 5100000 0.00044
Thus, pressures lower than 10-5 Torr species and for substrate-to-source
distance of ~10 to 50 cm in a vacuum chamber. Good vacuum is also
necessary for producing contamination-free deposits (also useful and required
for oxidizable species).
12
Steps & General Factors of Thin Film Growth & Nucleation

Target Medium Substrate
Production of the Transport to the substrate Condensation on substrate

appropriate atomic, through a medium The nucleation density and the
molecular, or ionic e.g.: vacuum, electric field, average nucleus size depend
species distance, stability of on a number of parameters
species, concentration of such as,
supporting electrolyte, etc.
1.the energy of the aim species
2.the rate of attachment
3.The activation energy of adsorption & desorption
4.Thermal diffusion
5.Temperature
6.Topography
7.Chemical nature of the substrate.
13
Initial Nucleation & Growth
Island
Layer-by-Layer
Stranski-Krastanov
(Mixed Type)
14
Physical Vapor Deposition – Sputter

Deposition
• Vacuum chamber is usually backfilled with Ar gas
• Chamber has high DC voltage (2,000-6,000 V)
• The Ar becomes a plasma and is used to target the
deposition material. The impact dislodges atoms from the
surface (sputtering), which are then deposited on the
substrate anode
• If the chamber is full of oxygen instead of Ar, then the
sputtered atoms will oxidize immediately and an oxide will
deposit (called reactive sputtering)
15
With sputtering, an Argon plasma is formed, causing argon ions to

strike a metal target and knock loose material. Because an electric
field is created, material is deposited on the substrate
Material Argon plasma –

target ionized argon in
an electric field
Substrate to
be coated
16
Physical Vapor Deposition (PVD) - Sputtering
The vapor species are created by mechanically knocking out the atoms
or molecules from the surface of a solid material by bombarding it with
energetic, non-reactive ions. The ejection process, known as
sputtering, occurs as a result of momentum transfer between the
impinging ions and the atoms of the target being bombarded.
Target Medium Substrate
17
Characteristics of the Sputtering Process

The sputtered species, in general, are predominantly neutral.
For higher energies, the yield approaches saturation, which occurs at higher
energies for heavier bombarding particles.
e.g.: Xe+ ~ 100KeV and Ar+ ~ 20KeV for saturation.
The yield is rather insensitive to the target temperature except at very

high temperatures where it show an apparent rapid increase due to the
accompanying thermal evaporation.
The energy of the ejected atoms shows a Maxwellian distribution with a long
tail toward higher energies.
The sputtering process is very inefficient from the energy point of view,
because most of the energy is converted to heat which becomes a serious
limitation at high deposition rates.
The sputtering process ensures layer-by-layer ejection from a multicomponent
target and results into a homogeneous film on the substrate.
18
Sputtering – Glow-Discharge Sputtering

Glow-Discharge Sputtering by different electrode configurations
Diode Sputtering
Cathode
Cathode
Target
Target
Bias Sputtering ----------------------------------
Ion Platting ++
+ ++
Getter Sputtering + +
++
Magnetron Sputtering Substrate
-----------------
Insulator
Substrate
Assisted or Triode Sputtering ++++++++++++++++++++++++++++++++++++
Anode
Anode
RF Sputtering
19
Sputtering
 Sputter deposition is done in a
vacuum chamber (~10mTorr) as
follows:
– Plasma is generated by applying
an RF signal producing energetic
ions.
– Target is bombarded by these ions
(usually Ar+).
– Ions knock the atoms from the
target.
– Sputtered atoms are transported
to the substrate where deposition
occurs.
20
Sputtering
 Wide variety of materials can be
deposited because material is put into
the vapor phase by a mechanical rather
than a chemical or thermal process
(including alloys and insulators).
 Excellent step coverage of the sharp
topologies because of a higher chamber
pressure, causing large number of
scattering events as target material
travels towards wafers.
 Film stress can be controlled to some
degree by the chamber pressure and RF
power.
21
Sputtering
Sputtering yield
atoms removed
Y ( E , ) 
incident particle
Differential sputtering yields

Y Y
, ,Yq ,Y   Yq
E1 1 q
105  Y  103
22
Sputtering
The removal of
surface atoms due to
energetic particle
bombardment
23
Sputtering
First observations
of cathode erosion in
gas discharges
W.R. Grove 1853
24
Sputter deposition
DC- and RF sputter deposition is a convenient and inexpensive coating

Technique.
25
Sputter deposition
Magnetron sputter deposition is very widely used and allows low pressure
discharge, high coating quality and fast deposition
26
Sputter sources
• Magnetron
– Magnetic field traps freed electron near target
– Move in helical pattern, causing large number of scattering
events with Ar gas – creating high density of ionized Ar
• Ion beam
– Plasma of ions generated away from target and then accelerated
toward start by electric field
• Reactive sputtering
– Gas used in plasma reacts with target material to form
compound that is deposited on wafer
• Ion-assisted deposition
– Wafer is biased so that some Ar ion impact its surface, density
the deposited film. May sputter material off of wafer prior to
deposition for in-situ cleaning.
27
Sputtering
• Advantages • Disadvantages
– Large-size targets, simplifying the – High capital expenses are
deposition of thins with uniform required
thickness over large wafers – Rates of deposition of
– Film thickness is easily controlled some materials (such as
by fixing the operating parameters SiO2) are relatively low
and simply adjusting the deposition – Some materials such as
time organic solids are easily
– Control of the alloy composition, degraded by ionic
step coverage, grain structure is bombardment
easier obtained through – Greater probability to
evaporation introduce impurities in the
– Sputter-cleaning of the substrate in substrate because the
vacuum prior to film deposition former operates under a
– Device damage from X-rays higher pressure
generated by electron beam
evaporation is avoided.
28
Crystal structure effect in Sputtering
Single crystal effects in sputtering, G. K. Wehner, Phys. Rev. 102(1956)690-704
29
A cheap and simple means of producing ions for sputtering is provided by the
well-known phenomenon of glow discharge, which occurs when an electric
field is applied between two electrodes in a gas at low pressure (~ 10-2 Torr).
The gas breaks down to conduct electricity, above a certain voltage applied
between the electrodes, The cathode dark space, across which most of the
applied voltage drops, is the most important region for sputtering. Ion and
electrons created at breakdown are accelerated across this region. The
energetic positive gas ions strike the cathode to produce sputtering and cause
emission of secondary electrons which are essential for sustaining the glow
discharge. The accelerated electrons produce more ions by collision with gas
atoms in the negative-glow region lying adjacent to the cathode dark space.
30

The energy of the bombarding ions depends on the accelerating cathode fall
(i.e., the voltage across the cathode dark space) and the thickness d of the
cathode dark space, which inversely proportional to the gas pressure p, that is
pd=const (Paschen’s law)
The number of ions striking the cathode current depends on the gas pressure
and the applied voltage. Initially, as the gas pressure is increased, the cathode
current increases due to increases of the number of the ions, also, at higher
gas pressures, the sputtered atoms are prevented from reaching the substrate
at the anode because of randomization due to the large number of collisions
with the gas molecules.
Since the sputtered species are diffusely scattered by ambient gas molecules
during their transit, they reach the substrate in randomized directions and
energies. As a result of the diffuse nature of material transport, the atoms
deposit at places not necessarily in the line of sight of the cathode. Because of
the collisions the energetic ions hit the cathode at high oblique angles, which is
actually helpful in increasing the yield.
31
Physical Vapor Deposition – Ion Plating
• Combination of thermal PVD and sputtering

• Higher rate of evaporation and deposition
• TiN coating is made this way (Ar-N2
atmosphere)
– The gold looking coating on many cutting tools to
decrease the friction, increase the hardness and
wear resistance
32
Sputter Deposition Systems
E Voltage ratio in RF sputtering: VC/VA = (AA/AC)n

RF Sputter System
DC Sputter Deposition
Magnetron Sputter Deposition
33
Physical vapor deposition (PVD): sputtering
W= kV i
PTd
Momentum transfer
-V working voltage
- i discharge current
- d, anode-cathode distance
- PT, gas pressure
- k proportionality constant
34
Bias Magnetron Sputtering for Niobium thin films
• Advantages and disadvanteges of the

bias tecnique
• Preliminary results of a mixed bias-
magnetron sputtering configuration for
coating Niobium on copper 1.5 GHz
cavities
• First applications of a large area
cavity shaped cathode in the bias
diode sputtering configuration.
35
Bias Sputtering
The positive bias applyed to the grid between
target and substrates promotes IONIC
BOMBARDMENT OF THE GROWING FILM
-
Target
Biased Grid
+
Substrate
36
Diode Bias Sputtering

IONIC BOMBARDMENT OF THE
GROWING FILM
37

Impurities re-sputtering
during the film growth
38

Impurities are preferentially removed
relative to the atoms of the main film.
fraction of
impurities fi 
 N i i   
trapped into N i i     R
the film
i = impurities sticking coefficient
Ni = atoms impurities arriving on the film
β = function of the bias current due to
impurities ions
R = sputtering rate
L.I.Maissel, P.M.Schaible; J.Appl.Phys. 36, 237 (1965)

39
Advantages
Densification of the crystal structure
Higher sputtering rate
Lattice rearrangement
Films quality improvement
40
Advantages
Increasing of the coating hardness
Similar defect annealing as does an

elevated substrate temperature
(E.Kay,G.Heim;J.Appl.Phys 49 (9) 4862 (1978))
Electrons bombardment reduction
Adhesion improvement
41
Disadvantages
Noble gas atoms embedding
Lattice defects
Thickness reduction
Biased grid shadowing
Still hydrogen removal is low

42
Bias Sputtering
500Å
Ta Resistivity (microhom-cm)
Ta Resistivity (microhom-cm)
1000Å
5000Å
High Resistivity
Cathode
Low Resistivity
Cathode
Substrate Bias (Volts) Substrate Bias (Volts)

High bias voltage reduce differences between films sputtered from different
cathodes and of different thickness. (Tantalum films studies)
43
Evaporation Rate
Evaporation
Thousand atomic layers per second
S puttering
One atomic layer per second
and Choice of materials

(e.g. 0.5 µm/min for Al)
Limited Almost unlimited
sputtering: Purity Better (no gas inclusions, very high Possibility of incorporating
vacuum) impurities (low-medium vacuum
range)
comparison S ubs trate heating Very low Unless magnetron is used substrate
heating can be substantial
S urface damage Very low, with e-beam x-ray Ionic bombardment damage
damage is possible
In-s itu cleaning Not an option Easily done with a sputter etch
Alloy compos itions , Little or no control Alloy composition can be tightly
s tochiometry controlled
X -ray damage Only with e-beam evaporation Radiation and particle damage is
possible
Changes in s ource Easy Expensive
material
Decompos ition of High Low
material
S caling-up Difficult Good
U niformity Difficult Easy over large areas
Capital Equipment Low cost More expensive
N umber of Only one deposition per charge Many depositions can be carried
depos itions out per target
Thicknes s control Not easy to control Several controls possible
Adhes ion Often poor Excellent
S hadow ing effect Large Small
Film properties (e. g. Difficult to control Control by bias, pressure,
grain s ize and s tep substrate heat
coverage)
44
Physical vapor deposition (PVD): MBE, Laser Ablation
• MBE
– Epitaxy: homo-epitaxy
hetero-epitaxy
– Very slow: 1µm/hr
– Very low pressure: 10-11
Torr
• Laser sputter deposition
– Complex compounds (e.g.
HTSC, biocompatible
- ceramics)
45
Physical vapor deposition (PVD): Ion cluster plating
• Ionized cluster: it is possible to

ionize atom clusters that are
being evaporated leading to a
higher energy and a film with
better properties (adherence,
density, etc.).
– From 100 mbar (heater
cell) to 10-5 to 10-7 mbar
(vacuum)--sudden cooling
– Deposits nanoparticles
• Combines evaporation with a
plasma
• faster than sputtering
• complex compositions
• good adhesion
46
Physical vapor deposition (PVD):Ion cluster plating

and ion plating
• Gas cluster ions consist of many atoms or
molecules weakly bound to each other and
sharing a common electrical charge. As in
the case of monomer ions, beams of cluster
ions can propagate under vacuum and the
energies of the ions can be controlled using
acceleration voltages. A cluster ion has
much larger mass and momentum with lower
energy per atom than a monomer ion
carrying the same total energy. Upon impact
on solid surfaces, cluster ions depart all their
energy to an extremely shallow region of the
surface. Cluster plating material is forced
sideways and produces highly smooth
surfaces.
• Also individual atoms can be ionized and
lead to ion plating (see figure on the right,
example coating : very hard TiN)
47
Film Deposition in IC Fabrication
Metal Contacts/Connections Low stress

Electrodes Adherent
Masks Uniformity, no pin holes
Wire insulation Conformal step coverage
Device encapsulation Thermal & electrical stability
48
Sputtering Chemistries
• Target • Deposited Layer
– Al – Al
– Cu – Cu
– TiW – TiW
– TiN – TiN
• Gas • Poly Crystalline

– Argon Columnar Structure
49
Deposition Rate
• Sputtering Yield, S
– S=α(E1/2-Eth1/2) 2/3
5.2 Zt  Zx 
  
U ( Z t2 / 3  Z x2 / 3 ) 3 / 4
 t
Z  Z x
U  surface binding energy

Z i  atomic numbers of (t) target and (x) gas
• Deposition Rate 
– Ion current into Target *Sputtering Yield
– Fundamental Charge
50
RF Plasma
• Electrons dominate in the Plasma Sheath
– Plasma Potential, Vp=0.5(Va+Vdc) Plasma rf
– Va = applied voltage amplitude (rf) Sheath
• Ions Dominate in the Sheath

– Sheath Potential, Vsp=Vp-Vdc
• Reference Voltage is ground such that Vdc is

negative
51
E-beam Evaporation
52
Brief technology description

• Key element of electron beam (EB-PVD) technology for
deposition of functionally graded coatings is the
composite ceramic ingot;
• Evaporation of a single composite ingot allows deposition
of advanced graded coating (bond coat, transition zones
and top coat) per one process run in one EB-PVD coater;
• The corresponding EB-PVD equipment is available for
sale and commercialization.
8YSZ
Transition zone
NiAl
Transition zone
Substrate
Rene 142
Composite ingot for evaporation Microstructure of graded
53 TBC
53
Advantages
This technology allows:
• producing graded coatings with a higher level of
reliability and durability and lower cost, which is at least
2 times lower than that of the traditional coatings
produced by the multistage technology, using various
kinds of equipment;
• replacing the flat interface between layers by a graded
transition zone and achieving a good adhesion of the
coating to the substrate;
• achievement of a high degree of reproducibility of the
composition and structure of the functionally graded
coating as compared with traditional multi-stage
technologies of protective coating deposition.
54
54
Experimental results
Graded thermal-barrier coatings (TBC) can allow:
• increasing gas temperature more than 1000C, keeping the cooling
blade surface temperature at the same level;
• decrease of ceramic layer thermal conductivity to 0.8-1.0 W/mK;
• improving adhesion strength with bond coat (more than 100 MPa);
• increasing thermal-cyclic life-time 1.8-2 times compared with
traditional TBC;
Graded hard erosion-resistant coatings (TiN-based, TiC-based) of
15-25 m thickness deposited at high deposition rate (up to 1
m/min) can increase the erosion resistance up to 15-30 times as
compared with steel substrate;
Graded hard damping coatings (Sn-Cr-MgO) of thickness of about
25-50 m provide several times higher damping capability and
erosion resistance of Ti-based parts at 25% improvement of fatigue
resistance.
55
55
Manufacturing of EB-PVD units in accordance with

Customer requirements
The UE-204 pilot-production unit The UE-207P production unit

(2006) (2005)
EB-PVD units of the last generation developed and manufactured at ICEBT are
used in the USA, Canada, China, India.
Typical cost of the EB-PVD unit is about 1.5-1.6 million USD.

All main vacuum and electronic components made in the USA and Western
European countries
56
Overall view of the Varian 3125 vacuum chamber. This

tool deposits thin films using e-beam evaporation
57
Varian 3125 4-pocket e-beam crucible
58
With an e-beam (electron beam) evaporator the

material is heated to a vapor (gas) and then condenses
on cooler surfaces
Substrates
(wafers) sit at the
top of the
chamber
Electron
Molten material hot beam is
enough to vaporize formed and
(become a gas) strikes the
metal crucible
59
E-beam evaporation
Crucible being heated by an

electron beam
60

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Nanoscience & Nanoengineering

Physical Vapor Deposition (PVD)

Low Pressure High Pressure

Physical Vapor Deposition (PVD)

Physical Vapor Deposition – Thermal PVD

Physical Vapor Deposition (PVD)

As the name implies, the techniques consists of vaporization of

The simplest and the most common method is to support the

Vapor pressure as a function of temperature of

Kinetics of Evaporation & Condensation

N e  3.5131022 pe (1 / MT )1/ 2 molecules  cm 2 s 1

The rate of condensation of the vapors depends not only on the

Necessary of Vacuum on PVD

10-2 0.5 4400

Steps & General Factors of Thin Film Growth & Nucleation

Production of the Transport to the substrate Condensation on substrate

Initial Nucleation & Growth

Physical Vapor Deposition – Sputter

With sputtering, an Argon plasma is formed, causing argon ions to

Material Argon plasma –

Physical Vapor Deposition (PVD) - Sputtering

Target Medium Substrate

Characteristics of the Sputtering Process

The yield is rather insensitive to the target temperature except at very

Sputtering – Glow-Discharge Sputtering

Differential sputtering yields

W.R. Grove 1853

DC- and RF sputter deposition is a convenient and inexpensive coating

Crystal structure effect in Sputtering

Single crystal effects in sputtering, G. K. Wehner, Phys. Rev. 102(1956)690-704

Sputtering – Glow-Discharge Sputtering

Sputtering – Glow-Discharge Sputtering

Physical Vapor Deposition – Ion Plating

• Combination of thermal PVD and sputtering

E Voltage ratio in RF sputtering: VC/VA = (AA/AC)n

Physical vapor deposition (PVD): sputtering

Bias Magnetron Sputtering for Niobium thin films

• Advantages and disadvanteges of the

Diode Bias Sputtering

Diode Bias Sputtering

Diode Bias Sputtering

L.I.Maissel, P.M.Schaible; J.Appl.Phys. 36, 237 (1965)

Densification of the crystal structure

Higher sputtering rate

Films quality improvement

Similar defect annealing as does an

Electrons bombardment reduction

Biased grid shadowing

Still hydrogen removal is low

Substrate Bias (Volts) Substrate Bias (Volts)

and Choice of materials

Physical vapor deposition (PVD): MBE, Laser Ablation

Physical vapor deposition (PVD): Ion cluster plating

• Ionized cluster: it is possible to

Physical vapor deposition (PVD):Ion cluster plating

Film Deposition in IC Fabrication

Metal Contacts/Connections Low stress

• Gas • Poly Crystalline

U  surface binding energy