PVD Talk V9
PVD Talk V9
PVD Talk V9
V9 06/2016
Contents
Module 1: An Overview of Surface Engineering: Module 6: Sputtering Processes:
Surface modification techniques; Surface coating techniques; Basic sputtering theory; RF sputtering; Reactive sputtering
Industrial exploitation.
Development of process; Industrial applications; Web coating Wear resistant coatings; Corrosion resistant coatings;
Decorative coatings; Optical coatings; Data storage media,
etc.
Module 5: Ion Plating: Summarising comments
SURFACE ENGINEERING
- an enabling technology
Definitions:
The design of surface and substrate together as a system to give cost effective
performance enhancement of which neither is capable on its own.
(Bell and Dearnley, Surface Engineering, 1994, 10, 4, 123-128)
Biological
Therefore, Surface properties dictate behaviour and
Cell
behaviour
growth
Light Optical
transmission properties
Motivation
performance
Chemical Corrosion
attack resistance
Friction/ Hardness/
abrasion C of friction
Motivation
Improved performance;
- machining rates, operating temperature, lubricant use, smart materials
Added value;
*Coating a drill adds 15% to cost, increases life by 500% +
*DT Gawne in JS Burnell-Gray and PK Datta (eds), Surface Engineering Casebook; Solutions to corrosion and wear-
related failures. Woodhead Publishing Ltd., Cambridge, 1996.
Surface Engineering in Action
* Matthews, Artley and Holiday, 2005 revisited: the UK surface engineering industry to 2010.
Coatings in Flight Turbines
Oxidation
Corrosion resistance /
resistance thermal barriers
Corrosion
resistance
Impact
resistance
Anti-fretting
Todays modern turbine designs would not operate as intended without the use of
functional coatings.
Diffusion
Laser Thermal
PVD CVD Plasma spraying
enhanced
Solid Liquid Gas Plasma variants Welding
Vacuum Ion plating Sputtering
evaporation
Magnetron
sputtering
A general classification of surface engineering techniques
Spin coating
This process involves depositing a liquid solution onto the centre of a
rotating, flat substrate. Evaporation of the solvent leaves a solid film on the
surface of the substrate.
15mm
Digital camera images of thin films
Electroplating
Metal ions are produced by a metal anode immersed in a salt solution. these
metal cations recombine with electrons at the cathode to form a metal film.
The electrolyte solutions often contain toxic material, such as metal cyanides,
and so present a hazard when disposing of effluents from this process.
Plasma spraying
Advanced nano-crystalline
Current technology
diamond coated tools
Atmospheric Plasma CVD
Nano coating
with precursor
chemistry
retained
+
Precursor polymerisation
Polymer
web
Substrate Substrate
in out
Syringe pump
system
CVD Atomic Layer Deposition
O O O O O
O O O O O
Al Al Al Al Al
O O O O O
O O O O O
Al Al Al Al Al
O O O O O
Substrate
Transparent High Barrier PECVD SiOx Coatings For
Electronic Encapsulation
U/W R/W
5 x 10-2 mbar
Exhaust Gases
Gas Purged Electrode (Ar)
GPE plasma
Atmospheric Pressure Dielectric Barrier Discharges:
Surface treatment of polymers
Lab-Scale. To ..Industrial-Scale
CVD
electroplating
carburising/
nitriding
low pressure Versatility of PVD
plasma
spraying techniques
plasma
spray/HVOF
laser cladding
hard facing
powder/HIP
corrrosion protection
electronic
optical
decorative
CERAMICS POWDERS
Testbourne Ltd
Coating materials:
METALS ALLOYS
CERAMICS MULTI-LAYERS
MULTI-COMPONENT
Angstrom Science
FUNCTIONALLY-GRADED
Substrate materials:
METALS CERAMICS
PLASTICS POWDERS
University of Salford Teer Coatings Ltd
MODULE 2: Physical Vapour Deposition
Definition:
i.e. all PVD processes incorporate a means of evaporating coating material from a
solid source under a partial vacuum.
Vacuum evaporation;
Ion plating;
Sputtering.
Substrate holder
Coating
Vacuum
chamber To vacuum pumps
Ion Plating
-1000V DC,
Substrate holder or RF bias
Coating
Glow discharge
(plasma)
Vapour flux Typical operating pressure: 1 to 0.1 Pa
+ Argon gas Deposition rates can be several microns/min
Source
Growing film subjected to ion bombardment
Vacuum Metallic, or ceramic coatings
chamber
Crucible
To vacuum pumps
Reactive Ion Plating Triode System
-1000V DC,
Substrate holder or RF bias
Glow discharge
(plasma)
Coating
Typical operating pressure: 1 to
Vacuum
chamber
0.1 Pa
Vapour flux Deposition rates can be several
+ Argon gas microns/min
Reactive gas + Reactive gas
(N 2, O 2, etc.) Growing film subjected to ion
Source Filament bombardment
Ionisation enhanced by filament
Ceramic coatings - nitrides,
oxides, etc.
Crucible
To vacuum pumps
Ion Beam Assisted Deposition (Vacuum-based ion plating*)
Coating
Vapour
Source flux Ion gun
Crucible
*DM Mattox, 'Ion Plating', in WD Sproul and KO Legg
(eds), 'Advanced Surface Engineering' Technomic
To vacuum pumps Publishing Co, Inc., Switzerland, 1995.
Cathodic Arc Evaporation
Vacuum
chamber
Anode
Substrate
Cathode Arc discharge holder
Ar/metal
ions Typical operating pressure: 1 to
0.1 Pa
Target must be conductive
Metallic of ceramic coatings
Macro- Growing film subjected to ion
Low voltage/ particles -100V DC, bombardment
high current or RF bias Source can have any orientation
supply Highly ionised coating flux
Anode Coating
Reactive
gas supply
To vacuum pumps
Sputter Ion Plating (bias sputtering)
Vacuum
chamber Glow discharge
(plasma)
Substrate
Sputter source
holder
(target)
To vacuum pumps
Ion Beam Sputtering
Coating
Ion assist
e.g. nitrogen
To vacuum pumps
Pulsed Laser Deposition
Molecular beam epitaxy
UHV technique base pressures as low as 10-12 Torr and operating
with deposition partial pressures of ~10-6 Torr
Depositing atoms/molecules produced by heating up solid source in
effusion cells (up to 1400OC)
Substrate surface is hot (several hundred OC), enabling surface
diffusion of adatoms and the formation of epitaxial layers
Deposition rates of a few per second
Common Features/Advantages of PVD Processes:
Possibility of contamination;
- Ar, O2, hydro-carbons
DC Diode Discharge
Power
supply
Ion-plating processes make use of energetic bombardment of the substrate
and growing film by ions generated in a glow discharge plasma.
Ionisation: e-
e-
Ar + e- Ar + + 2 e-
Ar+
Ar
e-
Excitation:
Ar + e- Ar * + e-
Ar * Ar + hn
Near surface
region
- Coating atom
- Substrate atom
In the sputtering process, the vapour phase species
is also generated by the impingement of positive
ions from a plasma onto a target plate.
Sputtered atom/ion
Incident Argon ion
+ with kinetic energy
e-
Target surface
(-ve)
Source: Gencoa
Formation of Coating:
Stage 1: Creation of a vapour phase species
- sputtering, or thermal evaporation
Vapour flux
Source
Substrate
The Structure of PVD Coatings
4 mm
100nm
10mm
- Density
- Hardness and modulus
- Residual stress
- Resistivity
- Optical properties
- Grain size
- Texture (crystallographic orientation)
- Corrosion rate
- Stoichiometry (compound films)
UBMS TiN Coatings on HSS
Effect of bias voltage on selected properties
2800 20
Hardness Hv (20mN)
18
1800 8
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Bias voltage, V (-ve) Bias voltage, V (-ve)
Fracture energy (Gc), J/m^2
8
-100
4 -400
3 -500
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Bias voltage, V (-ve) Bias voltage, V (-ve)
Vacuum Evaporation
Substrate holder
Description:
Coating
Coatings are formed by the evaporation of
material from a molten source, often heated
Vapour
by an electron beam, hot filament or hot
flux
boat. The process is generally restricted to
Source Crucible low melting point materials. This is a low
energy process, therefore coating adhesion
is weak.
Vacuum
chamber To vacuum pumps
Vacuum Evaporation: Applications
Source: Vergason
Source: Kolzer Technology Inc
Wire-feed mechanism
c1
Clear Barrier
c
Oxygen 11.5n
Polymer 2
Injection m
Gas Bar film
Evaporator ` AlO
Temperatur
e 1450C Wire Feed System
Wire feeds
Zinc Sulphide Coatings for Security Devices
Source: FEP
MODULE 5: Ion Plating
Ion Plating
Definition*:
Any PVD process in which the substrate surface and growing film are
subjected to continuous or periodic bombardment by massive energetic
particles.
*DM Mattox, Ion Plating, in WD Sproul and KO Legg (eds), Advanced Surface
Engineering. Technomic Publishing Co. Inc., Switzerland, 1995
Ion-Plating:
Rotating substrate
-100V DC bias
carousel
Reactive gas
Source
Low voltage
high current
e-beam gun
BALINIT A B C D
TiN TiCN WC/C CrN
70
Threads produced
60
Uncoated
Thousands
50 Balinit A
40 Balinit B
30
20
10
0
Savings resulting from the use of TiCN PVD (BALINIT B) coated
end mills in the production of components for a hammer drill
0 10 20 30 40 50
Annual savings in SFr.
Thousands
Source: Hilti AG
Injection Moulding of Twist-off Caps
40
35
30
25
20
15
10
5
0
Chrome-plated BALINIT C
Source: Balzers
Plasma IAD with the Leybold APS
high
power
plasma
e-beam source
gun
+
-
Monomer O2
Ar
Substrate
Cathode Arc discharge holder
Ar/metal
ions Typical operating pressure: 1 to
0.1 Pa
Target must be conductive
Metallic of ceramic coatings
Macro- Growing film subjected to ion
Low voltage/ particles -100V DC, bombardment
high current or RF bias Source can have any orientation
supply Highly ionised coating flux
Anode Coating
Reactive
gas supply
To vacuum pumps
High current/low voltage arc initiated at target surface.
Plasma M e + e M e - Electrons
M e
+ e e + + - Ions
e
M +
e M - Neutral atoms
e e e
Droplet M +
+ M
+ Each arc event lasts 5-40ns
e
Spot size = 10mm
200A @ 20V
Power density: 109 W/cm2.
Target plate
Process Features:
Magnets are used to control the arc and keep it on the target surface.
Steered arc sources feature varying magnetic fields helps reduce macro-particle emission
Source: Metaplas
Filtered arc sources use additional magnetic fields to deflect
charged particles and reduce macro-particles incident at substrate
Macro-particles
Charged
particles
Substrate
Source
Source: Andre Anders, Berkeley Lab
SEM micros showing defects in
ABS TiAlN coating*
Source: Metaplas
1,200
Uncoated
800 TiN
(TiAl)N
400
Source: Metaplas
MODULE 6: Sputtering Processes
Definition:
Ions striking a surface with sufficient energy may remove surface atoms in a
momentum exchange mechanism. This process is called sputtering.
Substrate
Sp utter source M holder
(target) Ar +
e- Ar
e-
Ar +
M
Co ating
Vacuum
cham ber
To vacuum pum ps
Incident particle
Sputtered particle
Atomic collisions
3
Compounds: Ag
MP
The number
Seah, Thin Solidof atoms
Films, ejected
81 (1981) 279-287from target surface per incident ion is defined as the sputter
yield of a material.
Yield determines:
-erosion rate of target
-deposition rate of coating
Yield is material characteristic which varies from < 0.1 to > 3 with:
-energy of incident ions
-ratio of masses of incident ions and target atoms
Target:
Substrate holder:
- Grounded, biased (RF, or DC), self-biased (floating)
- Heated, or cooled
Reactive Sputtering
500
Increasing oxygen flow
450 ('metallic' regime)
Target voltage, V
400
Normal
350 operating
Decreasing oxygen flow range
300 ('poisoned' regime)
250
200
0 5 10 15
Oxygen flow rate, sccm
Set-point
OEM signal
100% metal (metallic interlayer)
Working point
(compound coating)
Mono-
Substrate
chromator
holder
Sputter
source
The reactaflo monitors the light via
a fibre-optic link to the plasma, and
Power Plasma
the gas is rapidly controlled via a
supply
peizo valve
Compound
coating
gas
controller
Vacuum
Piezo valve chamber
To vacuum pumps
Argon gas
Reactive
supply
gas supply
e.g. O2, N2
Reactive Sputtering with Spectral Line Monitoring
Source: Gencoa
Limitations of Basic Sputtering Process:
Definition*:
B B
rg
(Larmor
radius) v
vll ll E
v
v v
E ExB
Cylindrical-post magnetron
Rectangular-post magnetron
Ring discharge-post magnetron
Cylindrical-hollow magnetron
S-gun magnetron
Rotatable magnetron (C-Mag)
Planar magnetron
Magnetic
Earth
field
shield
ExB 'O-ring'
drift Target
seal
path N S N
S Magnetron
eld
N N
lec
trE
fi
body
ic
Permanent
Water magnets
MS pole piece
cooling
Source: Gencoa
Process Features:
Substrate Substrate
PLASMA
PLASMA
~60mm
Target Target
N S N N S N
Mild steel
pole piece
N S N
Electrons need to
pass all these field
lines and reach the
null point before
z
being lost to the
magnetron
W/2
Source : Gencoa
Variation in substrate ion current with
Vtech magnetrons
Unbalanced, strongest
field at target
1.4
[0,0]
1.2
1
Ion Current, A
[0,12]
0.8
Most
0.6
Most unbalanced
balanced 0.4
0.2
[15,0]
0
-20 -10 0 10 20
Balanced to Unbalanced
Dual Unbalanced Magnetron Systems
S N S S N S
Target Target
Rotating Rotating
substrate substrate
holder holder
Target Target
N S N S N S
Closed-field Mirrored
configuration configuration
High substrate Low substrate
ion current ion current
Dual Unbalanced Magnetron Systems
Opposing Linked
Source: Gencoa
Plasma confinement in dual co-planar closed field unbalanced
magnetron sputtering system
Impact of closed-field configuration: Substrate ion currents
0.35
0.25
'Closed-field' magnetron
configuration 0.2
0.15
Single magnetron 0.1
configuration
0.05
0
-120 -100 -80 -60 -40 -20 0
Substrate bias voltage, V
1mm 1mm
1mm 2mm
Planar Magnetrons:
Rectangular or circular Von Ardenne
Valmet General
Magnetic Manipulation
Dielectric
Deposition rate is low
Anode Film
Target becomes poisoned with
insulating layer
Target
Poisoned layers charge up until
breakdown occurs in the form of an Electrical breakdown
arc
Arc events prevent stable operation
Arc events are detrimental to
structure, properties and
composition of coating Micro-arc (Unipolar arc)
Can also cause power supply
damage
Commercially unattractive
Asymmetric bipolar
400
200
100 Pulse-off
0
Target Voltage, V
Voltage, V
-100 -400
-200
-300 -800
-400
-1200
-500
Pulse-on
-600
0 10 20 30 -1600
Time, microseconds Timebase, s
Idealised Actual
Pulsed DC Target I-V Waveforms:
Asymmetric Bipolar Mode
1000 4
3
600
Target Current, A
Target Voltage, V
Pulse-on Pulse-off
Dielectric layers
+ + + + - - - -
Target - - - - + + + +
Charging up by Discharging by
+ Positive ion
positive ions electrons
- Electron
Voltage
Current
Cumulative hard arcs Vs duty
To 6000 arcs
400 duty = 64%
duty = 76%
duty = 82%
200 duty = 88%
0
0 20 40 60 80 100 120 140
Time, mins
200
0
0.E+00 5.E-06 1.E-05
-200
Voltage,V
-400
-600
Target 2
-800
-1000 Target 1
-1200
Timebase, s
Rotatables
(BOC)
Co-Planar (BOC)
10m
2m
PJ Kelly, OA Abu-Zeid, RD Arnell and J Tong, Surf. Coat. Technol., 86/87, (1996) 28-32.
Structural modification: Alumina films
1 mm 2mm
100
80 DC alumina film
Profile (x10,000)
60
40
20
Dual bipolar alumina film (150kHz)
0
0.0 1.0 2.0 3.0 4.0 5.0
Horizontal distance (mm)
Ra values for DC films typically two orders higher than dual bipolar films
Ra of dual bipolar films similar to glass substrate
No discernable trend with frequency
Durability/Adhesion: Titania Coatings
PJ Kelly, CF Beevers, PS Henderson, RD Arnell, JW Bradley and H Bcker Surf. Coat. Technol., 174-175 (2003) 795
Other Benefits: Enhanced Process Flexibility
No matching/tuning of generator
Extended material and composition variety
all compositions obtainable
Long term stability
greater than 300 hours claimed (Bruer 1997)
Control of plasma parameters
temperature increases with frequency (Bradley 2001)
Control of energy delivered to growing film
ion energy increases with frequency (Bradley 2002)
Energy-Resolved Mass Spectrometry:
Driving Voltage Waveform Features
0
0 1 2 3 4 5 6 7 8 9 10
-200
-400
A A pulse on period
-600 B Positive voltage overshoot
-800 C - steady-state pulse off period
*Plasma potential
-1000
Time base, microsecs
*JW Bradley, SK Karkari and A Vetushka, Plasma Sources Sci. Technol., 13 (2004) 1
Energy Resolved Mass Spectrometry:
Ar+ Ion Energy Distribution Functions
100kHz, 500W, 50% duty
1.2E+06
A
Intensity (arb units)
8.0E+05
4.0E+05
B
0.0E+00
0 20 40 60 80 100
Energy (eV)
JW Bradley, H Bcker, Y Aranda-Gonzalvo, PJ Kelly and RD Arnell, Plasma Sources Sci. Technol., 11 (2002) 165
Commercial Applications
Low-E/Solar control
Architectural, automotive
Anti-reflective/Anti-static (AR/AS)
Architectural, flat panel displays, CRTs,
opthalmics
Transparent conductive oxides (TCOs)
Displays, photovoltaics, OLEDs
Photocatalytics
Self-cleaning (Active) glass (TiO2 coatings)
Adaptive glazing
Electrochromic, gasochromic coatings (most
commonly WO3)
Pulsed Biasing
Novel Materials/Properties/Techniques
0.5
0.4
Continuous DC
Friction
of friction
0.3
Coefficient
0.2
Coeff.
Pulsed DC (20kHz)
0.1
0.1
0 500 1000 1500 2000 2500 3000 3500
Time (s)
Pulsed @20kHz Time
DC
PJ Kelly, CF Beevers, PS Henderson, RD Arnell, JW Bradley and H Bcker Surf. Coat. Technol., 174-175 (2003) 795
TiN Coatings:
Structures
500nm 500nm
DC Sputtering
metallic target, reactive process control
equipment
alloyed, or segmented targets
expensive
single composition per target Al/Mg segmented target
RF Sputtering
hot pressed or sintered targets
prone to cracking
single composition per target
low deposition rates
Benefits of process
Dummy
Substrate heater
magnetron Infinitely variable target compositions
RF Bias available
supply
Multi-dopants combinations
Substrate possible
holder
Cheap starting materials
Powder
target Avoids target cracking issues
Magnetron driven in pulsed DC mode
Highly flexible process
To vacuum
pumps Pulsed DC
No need for reactive control
supply system
No need for matching networks
Excellent means of screening
candidate materials and identifying
optimum compositions
Powder Targets
350kHz 600
Off On
400 140kHz
200
Voltage, V
0
-5.0E-06 -3.0E-06 -1.0E-06 1.0E-06 3.0E-06 5.0E-06
-200
-400
-600
-800
On Off
-1000
Timebase, s
1
0.9 Annealed at 420oC
Transmittance, % 0.8 for 1h in N2
0.7
0.6
0.5
0.4
As-deposited
0.3
0.2
0.1
0
1mm 350 370 390 410 430 450 470 490
Wavelenth, nm
1mm
1.6
Significant implications in terms of:
1.4
film growth
Substrate current, A
1.2
substrate pre-heating
1
sputter cleaning 0.8
0.6
0.4
0.2
0
-350 -300 -250 -200 -150 -100 -50
Bias voltage, V
*PJ Kelly, et al, J. Vac. Sci. Technol. A19(6) Nov/Dec DC bias 100kHz 200kHz 300kHz 350kHz
2001, 2856-2865.
Summary: Pulsed Magnetron Sputtering
Nitrides/Alloy nitrides
Carbides/Carbo-nitrides
Carbon-based
Molybdenum-disulphide based
Diamond-like Carbon
DLC, diamond bonding, deposited in hybrid
PVD/CVD process
Hard (2000VHN), low friction (0.15), also has
decorative applications
Graphit-iC
Graphitic bonding, lower friction and wear
rates than DLC
Available as Cr/C multi-layer
Performs well in aqueous environment
Dymon-iC
Improved DLC from Teer Coatings
Lower friction (0.03 to 0.1) and wear rates
Commercial Applications of DLC
80
No. of holes drilled
70
60
No coating
50 Pure carbon
40 TiN
Graphit-iC
30
20
10
MoST TM
MoS2/metal (Ti) composites
Amorphous solid solution of Ti in MoS2
Retains low friction of MoS2 but is much harder (1500VHN)
Excellent in vacuum, or low humidity
Extreme wear resistance
0.02 coefficient of friction
High load carrying capacity
Protects opposing face
Uncoated
MoST
6000rpm 7000rpm
Dry Drilling JIS S50C steel
Al-14% Si workpiece. Drills - high speed steel drills
Drills - inch jobber drills coated with TiN, TiAlN and
TiN+MoST
Source: Tecvac
Source: Deco-Systems
Corrosion Resistant Coatings
Problem:
Cadmium plating produces toxic effluent process is likely to be banned in
near future
Ivadized coatings:
- are not fully dense and require post-deposition shot peening
- do not offer sacrificial protection to substrates
- have poor tribological properties
Solution:
Magnetron sputtered Al/Mg alloys
Co-deposited Al-Mg coatings on fasteners
Rotating barrel
Magnetrons
Al Mg
Coating flux
Components
Al/Mg Alloy Coatings
900 5
800 4.5
Substrate
4mm
Sputtered Optical Coatings
Low-E/Solar control
Architectural, automotive
Anti-reflective/Anti-static (AR/AS)
Architectural, flat panel displays, CRTs, opthalmics
Transparent conductive oxides (TCOs)
Displays, photovoltaics, OLEDs
Photocatalytics
self-cleaning (Active) glass
TiO2 coating reacts with UV light to produce OH radicals that
decompose organic matter. Forms superhydrophilic layer
Adaptive glazing
Electrochromic, gasochromic coatings (most commonly WO3)
Optical and energy transfer varies with current flow, or gas flow
Low-e and solar control films on large area substrates
ZnO
TiOx
ZnO
Ag
TiOx ZnO
Ag Ag
TiOx ZnO
Glass Glass
Energy transmission
Low-e
Solar
control
5m 50m
Source: Pilkington plc
Low-e and solar control films
Source: FEP
Anti-Reflective Coatings
SiOx
TiOx
SiOx
SnOx
Glass
4-layer AR
Stack
Source: FEP
AR/AS coatings
PC, or glass
Transparent Conductive Oxide Coatings
Organic layer
Counter electrode
Ceramic ion conductor
Electrochromic electrode
Transparent conductor
ITO/NiO/Ta2O5/WO3/ITO/Glass Glass
0.1 0.5 solar gain
Source: SageGlass
4 70% transparency
Electrochromic coatings
Source: SageGlass
Source: Unaxis
Complex multi-layer
structures deposited
in cluster systems
Source: Unaxis
Microelectronics
1mm
0.4
mm
20mm
50 mm Ti/TiN multi-layer
free-standing foil
Section from ultra-thick (4mm)
OFHC free-standing component
Duplex Processes
*Combines two surface engineering treatments, often in one process
cycle; e.g.
High
strength,
toughness
Composite:
desired tribo-,
fatigue &
High corrosion
fatigue properties Good wear &
ng
Pla
strength, corrosion
ati
resistance
sm
load bearing
co
capacity
an
c
mi
itri
era
din
DC
g
PV
Wear test results for En40B steel
Ball-on-wheel test:
Alumina ball, 20N, 620m
250
Wear volume, x 0.1mm^3
200
150
lP
tra as
m
ee
treu D
dat
50
expl
id
e
ni
dat
de
0
Treatment