PVD of Engineering Coatings

A short course by Prof Peter Kelly

Surface Engineering Group,

Manchester Metropolitan University

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.

Module 2: Physical Vapour Deposition: Module 7: Magnetron Sputtering:

Definitions and descriptions of PVD processes: vacuum Basic designs; Unbalanced magnetron sputtering; Multiple
evaporation, ion plating and sputtering. magnetron systems; Alternative designs.

Module 3: Glow Discharge Plasmas: Module 8: Pulsed Magnetron Sputtering:

Plasma phenomena; Ion bombardment during film growth; Problems associated with DC sputtering; Advantages of
The relationships between deposition parameters, coating pulsed sputtering; Plasma characteristics; Film properties.
structures and properties.

Module 4: Vacuum Evaporation: Module 9: Applications of Magnetron Sputtering:

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

Development of process; Reactive evaporation; Cathodic arc

evaporation; Industrial applications.
MODULE 1: An Overview of Surface Engineering

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)

The modification or coating of a surface in order to achieve a combination of

properties in both the surface and the underlying bulk which could not
otherwise be achieved.
(Hutchings, Tribology: Friction and Wear of Engineering Materials. Edwards Arnold,
London 1992)
 Components interact with their environment at the Surface

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

Optimum performance may require conflicting surface/bulk

properties;
e.g. High surface hardness, good bulk toughness
Ability to specify independent surface/bulk properties allows
novel materials, or materials with novel properties to be
developed;
Thermal barrier coatings, graded coatings, metastable alloys,
nanocomposites, etc
Surface engineering allows product differentiation;
Quality, performance, life-cycle costs, appearance, etc.
Functional coatings cannot exist without surface
coatings/treatments
Displays, data storage, semi-conductors, etc.
 Potential Benefits:

Improved component life;

- wear/corrosion protection (4% of UK GDP!)

Improved performance;
- machining rates, operating temperature, lubricant use, smart materials

Alternative base materials;

- cheaper/lighter

Reduced operating costs;

- low friction, reduced downtime/maintenance, reduced waste, increased plant life

Added value;
*Coating a drill adds 15% to cost, increases life by 500% +

Novel materials/products can be produced;

- processes are highly non-equilibrium

*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

Cutter for foil lids for food

containers combines tool
steel substrate for toughness
in the thin blade section
with hard, abrasion
resistant titanium nitride
coating
Savings achieved through
reduced tooling replacement
costs, reduced downtime,
longer production runs, etc.
 UK Surface Engineering Market & Value 2005*:
Industry Total (m) Share (%) % industry
affected by coatings
Automotive 1215 5.7 80%
Construction 885 4.2 30%
Electronic 2126 10.0 100% Engineering
Retail consumer 1221 5.7 40% sector
Aerospace 354 1.7 80%
Other Eng. 1166 5.5 51%
Optical & display 1892 8.9 100%
Data storage 2397 11.2 100% Functional
Semiconductor 8990 42.2 100% coatings
Decorative 299 1.4 100% sector
Other functional 771 3.6 100%
Total coating market 21316 71.1%

* 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

Clearance Wear resistance

control

Anti-fretting

Todays modern turbine designs would not operate as intended without the use of
functional coatings.

Source: Sulzer Metco

PVD coatings for friction and wear reduction in automotive applications

Me-DLC: low friction coating for Diesel

injectors
CrN: hard coating for piston rings
TiN: hard coating for various components
(tappets, cams, gears)
AlSnSi: self-lubricating coating for journal
bearings
Source: Hauzer Techno coating
 Surface Engineering Techniques
1. Surface Modification

Composition unchanged e.g. heat treatments

Composition changed e.g. implantation, diffusion processes (carburizing,
nitriding, boronizing, etc.)
2. Surface Coating
Four main groupings:
Solid state processes e.g. cladding, HIP
Molten, or semi-molten state processes e.g. welding, thermal spraying, laser
treatments
Solution state processes e.g. electroplating, anodising
Gaseous state processes e.g. CVD, PVD
For full process descriptions see: Hutchings, Tribology; Friction and Wear of Engineering Materials. Edward Arnold, London
1992, Holmberg and Matthews, Coatings Tribology; Properties, techniques and applications in surface engineering.
Elsevier 1994.
 SURFACE ENGINEERING

SURFACE MODIFICATION SURFACE COATING

Change of No change of Vapour Solid Solution Molten

composition composition phase state state state

Implantation Mechanical Thermal Chemical Electro- Sol-gel

chemical

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.

A. Application of liquid to centre of substrate

B. Acceleration of substrate spin spreads liquid outwards excess beads spun off edge
or washed away from beneath
C. High speed spinning (2000 4000 rpm) thins liquid to desired depth
D. Evaporation of solvent to leave solid deposit often requires further curing process
 Sol-Gel: Controlled evaporation produces thin film
A SOL consists of a colloidal suspension - solid particles (usually metal salts)
a few hundred nm in diameter, suspended in a liquid
The particles react and condense in a new phase (GEL) forming a solid
macromolecule immersed in solvent
Drying the GEL leaves behind a solid deposit ceramic/glass

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

The spraying of molten or softened material onto a surface

Powder or wire is injected into a very high temperature plasma, rapidly heated
and accelerated toward a substrate.
This material then rapidly cools to form a film on the substrate surface
Very high melting point materials such as ceramics (i.e. zirconia) and metals
such as tungsten can be deposited via plasma spraying.
Plasma spraying in action
 Chemical Vapour Deposition
CVD, describes a group of processes that involve the deposition
of a solid material from a gaseous phase
Vapour phase precursors react/decompose on a heated solid
surface to leave a solid deposit and gaseous by-products
Example: Titanium boride forms from chloride compounds in the
presence of hydrogen. The remaining chlorine combines with
hydrogen to form a gaseous by-product.

TiCl4 + 2BCl3 +5H2 TiB2 + 10HCl

Hot hydrogen chloride gas must be exhausted from the system,

providing a significant hazard as a result of the process!
Plasma enhanced deposition (PECVD): Precursor species may be
activated in the gas phase by energetic plasma species
 Diamond coatings on dental
burrs

Advanced nano-crystalline
Current technology
diamond coated tools
 Atmospheric Plasma CVD

Atmospheric plasma jet treating a catheter tube

 Atmospheric Plasma CVD

Nano coating
with precursor
chemistry
retained
+
Precursor polymerisation

Liquid Aerosol Surface activation/grafting

+
Substrate
Atmospheric Pressure Plasma
Liquid Deposition (APPLD)
Liquid delivery of precursors into the plasma
Applied Power 400 2000W (up
to 8.6 kV)
Nebulizer

Polymer
web

Substrate Substrate
in out
Syringe pump
system
 CVD Atomic Layer Deposition

Chemical vapour deposition method with sequential self-

limiting gas-solids reactions
First atomic layer onto substrate is formed by chemisorption
(in ideal case), second layer with chemical reaction
Materials are built up one atomic layer at a time (cycle)
 Al2O3 ALD Model ALD system
Sequential TMA (Trimethylaluminium) and H2O precursor pulses, with
intermediate N2 purges to remove excess reaction product and unreacted
precursor
Process cycle repeated to reach required thickness
2 Al(CH3)3 + 3 H20 Al2O3 + 6 CH4
H H H H H
O O O O O
Al Al Al Al Al
Growth rate for Al2O3
O O O O O 1/Cycle
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
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

40 KHz power supply

U/W R/W

Process gases (O2 + He) Chilled Process Drum

+ HMDSO monomer
(Hexamethyldisiloxane)

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

Untreated PP: Treated PP:

Hydrophobic Hydrophilic
 spin coating

friction transfer Why PVD?

PVD

CVD
electroplating

carburising/
nitriding
low pressure Versatility of PVD
plasma
spraying techniques
plasma
spray/HVOF

laser cladding

hard facing

powder/HIP

0.1nm 1nm 0.01 0.1 1 0.01mm 0.1mm 1mm 10mm

corrrosion protection

electronic

optical

decorative

mechanical properties enhancement

 University of Salford

Versatility of Advanced PVD Techniques:

Source materials:

METALS ALLOYS 1mm

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

Physical Vapour Deposition

Definition:

A generic term given to a group of surface engineering techniques used to

deposit solid coatings, or films from the vapour phase in vacuo.

i.e. all PVD processes incorporate a means of evaporating coating material from a
solid source under a partial vacuum.

Three basic processes:

Vacuum evaporation;

Ion plating;

Sputtering.

Important derivatives termed Advanced PVD Techniques

 Vacuum Evaporation (Metallisation)

Substrate holder

Coating

Vapour Typical operating pressure: 0.01 Pa

flux Deposition rates can be several microns/min
Low energy process - porous columnar structures
Source Crucible Mostly metallic coatings

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*)

Substrate holder Vacuum

chamber

Coating

Typical operating pressure: 0.001 Pa, or lower

Ion beam Deposition rates generally very low
Growing film subjected to ion bombardment
Metallic, or ceramic coatings

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)

Glow discharge Typical operating pressure: 1 Pa

vapour flux, Deposition rates only several
Ar ions, microns/hour
Ar atoms
Growing film subjected to ion
bombardment
-3000V DC, -1000V DC,
or RF bias
Metallic, or ceramic coatings
or RF bias
Sputter source can have any
Coating orientation

To vacuum pumps
 Ion Beam Sputtering

Substrate holder Vacuum

chamber

Coating

UHV operating pressures

Ion source Very low deposition rates
e.g. argon Metallic or ceramic coatings
Target
e.g. titanium Good control over ion energy
and flux
Limited commercial applications

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:

Films typically (not limited to) 0.1 to 10mm thick;

Processes relatively simple;

Processes highly versatile;

Deposition can take place at low substrate temperatures

(< 150oC);

Deposition rates can be relatively high (> 10mm/min);

Low environmental impact.

Additional Benefits of Advanced Processes:

Good coating adhesion, through sputter cleaning of substrate;

Surface finish can replicate substrate finish;

Uniform coating thickness through gas scattering and substrate

movement;

Controllable deposition rate;

Controllable coating structures;

High purity coatings;

Very wide range of coating and substrate materials can be used.

 Disadvantages of PVD Techniques:

Processes take place under vacuum;

- batch process
- component size limited by chamber size

Possibility of contamination;
- Ar, O2, hydro-carbons

Difficult to coat complex components compared to CVD, or electroplating;

- line-of-sight process

Dense coatings can be highly stressed.

- can cause spalling
MODULE 3: Glow Discharge Plasmas

Glow Discharge Plasmas

DC Diode Discharge

- Consist of charged and neutral particles; Cathode Anode

(-ve) (+ve)
- Result from the partial ionisation of a gas; -
- Ar
-
- Generated by a external electric field; - Ar
-
- Ar
-
- Degree of ionisation only ~ 0.1%
Argon gas at 1 to 100Pa

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

Source: Plasma Quest Ltd

 Ion Bombardment:

Three main functions*;

1. Sputter cleaning prior to deposition

- Removes surface oxide layer and/or contaminants

2. Improve adhesion by physical mixing at interface

- Influences nucleation and growth processes

3. Modifying the structure and properties of the growing film

- Enhances adatom mobility

*DM Mattox, J. Vac. Sci. Technol., 10, 1, 1973, 47-52.

 Coating/substrate interface region

Native oxide layer and/or Intermixing of coating and

contaminants substrate atoms at interface

Near surface
region

Without sputter cleaning Following sputter cleaning

- 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

Process Thermal Sputtering Low volt. Arc source

evaporation E-beam
Mean particle
energy, eV 0.1 1-40 < 50 50-150

Stage 2: Transport of vapour from source to substrate

- can be collisionless, or may involve gas-phase scattering

Mean free path:

at 10-2 Pa (1x10-4 mbar) is ~ 60cm
at 1 Pa (1x10-2 mbar) is ~ 0.6cm

Stage 3: Film growth on substrate

- nucleation and growth processes*

*M Ohring, The Materials Science of Thin Films, Academic Press, London, 1991.
 In the PVD processes of Vacuum Evaporation, Ion Plating
and Sputtering the coating flux approaches the substrate
from a limited set of directions

Vapour flux

This inherently promotes

the formation of columnar
structures

Source

Substrate
 The Structure of PVD Coatings

Zone 1 Zone 2 Zone 3

'Porous 'Dense 'Fully
columnar' columnar' dense'

Increasing energy of deposition

Final structure/properties determined by

energy delivered to growing film

After Movchan and Demchishin (1969), Thornton (1974), etc.

 Zone 1
'Porous
columnar'

Structure consists of individual columns separated by voids,

or pores.

Dominant mechanism: atomic shadowing

 Zone 2
'Dense
columnar'

Structure still has columnar element, but there are

no voids between columns

Dominant mechanism: surface diffusion

 Zone 3
'Fully
dense'

No columnar element, fully dense equiaxed grain

structure develops

Dominant mechanism: bulk diffusion

Zone 1
 Zone 2

4 mm
100nm

SEM micrograph of W coating Through thickness TEM

deposited by CFUBMS, showing micrograph of W coating
typical zone 2-type structure deposited by CFUBMS, showing
typical zone 2-type structure
 Zone 3

10mm

SEM micrograph of Al coating Through thickness TEM

deposited by CFUBMS, showing micrograph of Al coating
typical zone 3-type structure deposited by CFUBMS, showing
typical zone 3-type structure
 Energy Delivered to the Growing Film
Coating

Energy can be transferred by a number of e-

processes: Ar+

Heat of condensation of coating atoms

Kinetic energy of neutral particles
Me
Radiant heating
Ar
In the absence of significant ion
bombardment, T/Tm is the most important factor
In ion-plating processes simultaneous ion Substrate
bombardment can strongly influence structure.

Much attention has, therefore, been directed at

developing PVD systems capable of supplying high
and controllable ion currents to the growing film.
Ion Bombardment During Film Growth:

- Enhances mobility of surface adatoms

- Prevents formation of columnar morphologies
- Promotes formation of dense high energy structures

Physical and chemical properties of film are strongly related to microstructure.

Film properties which can be influenced include:

- 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

Critical load (Lc), N

2600
16
2400
14
2200
12
2000 10

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

Internal stress, MPa

7
-200
6
-300
5

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)

Muller and Fromm, Thin Solid Films, 270 (1995) 411-416.

MODULE 4: Vacuum Evaporation

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

Reflective coatings (30% - 95%) for lighting

Al wire-fed onto hot boat
E-beam Cr, Ni-Cr, or stainless steel
EMI/RFI shielding
Decorative coatings
Al coatings on glass beads for
Retroreflective materials for safety jackets,
traffic cones, etc.

Source: Vergason
Source: Kolzer Technology Inc
Wire-feed mechanism

Source: Valmet General

 Conversion Processes for AlOx coated Polymeric Web

c1

Clear Barrier

c
Oxygen 11.5n
Polymer 2
Injection m
Gas Bar film
Evaporator ` AlO
Temperatur
e 1450C Wire Feed System

E-Beam evaporated Al in O2 AlOx BOPP

atmosphere
 Pattern Metallising Striping

Oil boiler lays down oil lanes

onto substrate
Oil evaporates during coating to
produce transparent stripe (De-
metallisation
High line speed, >1000m/min.
High Definition, <0.1mm.

Source: Valmet General

 Pattern Metallising Striping

Patterned roll is sliced into 1mm

threads for bank notes/security
threads
Multi-layer MgF2/Al/MgF2
stacks give interference effects
Plastic film Industrial Systems
Industrial systems capable of handling:
- Coated widths from 100mm to 3200mm,
- Web lengths up to 45000m, 12mm thick
- Film thicknesses from 0.7mm to 250mm +,
- Web transport rates up to 20m/s (25-50mph)
- 1.5M ft2 per hour

Plasma pre-treatment systems incorporated to:

- improve adhesion
- reduce outgassing

Water Source: Valmet General

cooled
drum
Evaporation
source
Source: FEP

Wire feeds
 Zinc Sulphide Coatings for Security Devices

Pre-embossed substrate is plasma treated prior to deposition (essential!)

Line speeds up to 200m/min
Roll lengths 3-5km (PET)
Embossed material overlays pictures, photos, etc to produce holographic
image
Used in passports, driving licences, credit cards, bank notes, etc.
Source: Valmet General
 Optically variable pigments for paints, plastics and security inks

Multi-layer interference films consisting of reflector (Al), dielectric (MgF2) and

absorber (Cr) that show strong colour shifts with viewing angle
Deposited on polymer film, which is then dissolved

Source: ChromaFlair, from Flex Products

 Other Applications
Anti-static films/Bags
Al/Zn thin film capacitors
Transparent metal oxides for barrier
coatings for food packaging
Holographic security devices
Pyrotechnic devices for airbags
Co-Ni films on polyester for use in
Video cassettes
Electrochromic windows
Inkjet cartridges

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.

Now generally used to describe electron beam (E-beam) evaporation

systems

*DM Mattox, Ion Plating, in WD Sproul and KO Legg (eds), Advanced Surface
Engineering. Technomic Publishing Co. Inc., Switzerland, 1995
 Ion-Plating:

Terms first coined by Mattox in late 1960s

Initially assumed that coating flux was highly ionised
Actual ionisation in early e-beam plasmas was very low ~ 0.1%
Very high bias voltage (>1kV) required to produce dense films
Significant resputtering
High stresses
High evaporation rates can be achieved for certain metals
At the expense of low ion/atom ratios and poor film structures
Evaporation takes place from a point source and must take place upwards
Can lead to poor uniformity unless sophisticated jigging is used
 Current Systems:

Generally use low voltage/high current E-beam source

Gives high ionisation in plasma (10-50%)

Dense coatings with low (-100V) bias possible

Substrate rotation and crucible movement used to improve coating

uniformity

TiN and CrN routinely deposited onto large batches of tools

Balzers process is best known example

 Industrial Ion-Plating System

Rotating substrate
-100V DC bias
carousel

Tools Vapour flux

Reactive gas

Source
Low voltage
high current
e-beam gun

Water cooled, Source: Surface Engineering, 12, 4, 1996

movable
crucible
To vacuum pumps
 Balzers BALINIT range:

BALINIT A B C D
TiN TiCN WC/C CrN

Depn temp., oC <500 <500 <250 <500

Microhardness, Hv 2300 3000 1000 1750

Coeff of friction 0.4 0.4 0.2 0.5

(dry against steel)

Also: FUTURA/FUTURA NANO (TiAlN) high performance all round

X.CEED (TiAlN) Hard machining, high speed cutting
ALCRONA (AlCrN) high oxidation resistance and hot hardness
 Cutting Balinit A (TiN)

Metal die casting Balinit D (CrN)

Forming Balinit B (TiCN)

 Punching Balinit B (TiCN)

Plastics processing Balinit A (TiN)

Precision components Balinit C (WC/C)

 Case Studies

Many case studies demonstrate substantial cost savings and increased

productivity through:
Reduced wear
Reduced friction
Increased tool life and performance
Reduced downtime
Fewer rejections
Improved surface finish
Reduced cold welding/seizures
 Threads produced in blind holes with coated and uncoated
M8 taps (Renault de Espana SA)

Workpiece: AlSi engine block

80 Cutting speed = 12m/min

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

Savings due to reduced machine downtime

Savings due to lower tool costs

Savings due to fewer rejects

Total annual savings

0 10 20 30 40 50
Annual savings in SFr.
Thousands

Source: Hilti AG
 Injection Moulding of Twist-off Caps

Service life (million shots)

40
35
30
25
20
15
10
5
0
Chrome-plated BALINIT C

Pharmaceutical application no lubricants permitted

Maintenance interval extended from one week to 8 months
10% shorter cycle times
20% gain in productivity

Source: Balzers
 Plasma IAD with the Leybold APS

high
power
plasma
e-beam source
gun

+
-

Monomer O2

Ar

Source: Leybold Optics

 Temperature Behaviour of TiO2 Single Layer

Without ion assist With ion assist

Source: Leybold Optics

 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
 High current/low voltage arc initiated at target surface.

Target atoms and ions and droplets emitted from 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:

Very high ionisation of coating flux (50-80%)

multiple ionisation (Me2+, Me3+)
mean particle energy is highest of all PVD processes
good coating/substrate adhesion
Low deposition temperatures possible (200oC)
Targets must be conductive
Targets can be mounted in any orientation
 Main problem :
Inclusion of macro-particles in coatings

Magnets are used to control the arc and keep it on the target surface.

Random Arc Steered Arc

Random arc sources feature fixed permanent magnets behind target uniform target erosion

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

Filtered arc source

Macro-particles

Charged
particles

Substrate

Source
Source: Andre Anders, Berkeley Lab
 SEM micros showing defects in
ABS TiAlN coating*

The formation of a nodular

defect overgrowing an arc-
induced macroparticle
*IJ Smith, Surf Coat Technol 90 (1997) 164
 Large-Scale Arc PVD System

Source: Metaplas

75% of hard coated cutting tools produced by arc systems.

H Gabriel, PVT, 47th SVC conference, 2004.
 Vapor Tech System:
Patented Center-Arc Technology

Source: Vapor Tech

 Drilling Test
Comparing TiN and TiAlN coated tools
with uncoated tools
Number of drilled holes

1,200
Uncoated
800 TiN
(TiAl)N
400

8mm diameter drill; speed: 20m/min; feed: 0.3mm/rev

Taken from HK Pulker (ed) 'Wear and Corrosion Resistant coatings by CVD and PVD
Ellis Horwood Ltd., Chichester, 1989.
Performance of Arc Coated Tools

Source: Metaplas
MODULE 6: Sputtering Processes

Basic 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

-3000V DC, -1000V DC ,

or RF bias e- or R F bias

Co ating

Vacuum
cham ber

To vacuum pum ps
 Incident particle

Sputtered particle

Atomic collisions

Collision cascades that cause sufficient energy to be transferred to a

surface atom to overcome its binding energy (4-8 eV) result in a
sputtering event. The threshold for sputtering of solids is of the order
of 20-40 eV.

MW Thompson, Vacuum 66 (2002) 99

 The Sputtering Yields of Various Elements
in atoms per 500eV argon ion

3
Compounds: Ag

Sputter yield, atoms per ion

Al2O3 0.05
2.5 SiO2 0.23 Pb
Ta2O5 0.18
Cu
2 SiC 0.45 Mn Pd
Mo2C 0.20
Au
1.5 Rh
Ni
Ru Sn
Cr Ge Re Pt
1 Al Co
Ir
Nb Hf
V Fe Mo Os
Be
0.5 Si Y Zr Ta W
Ti
C
0
0 10 20 30 40 50 60 70 80 90
Atomic Number

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:

- Usually solid, can be powder

- Metallic, or ceramic (RF or pulsed sputtering)
- Can be mounted in any orientation (if solid!)
- Must be water-cooled (~ 95% of incident energy lost as heat)
- Operating voltage: 1-3kV (-ve)
- Operating pressure: 1 to 10 Pa

Substrate holder:
- Grounded, biased (RF, or DC), self-biased (floating)
- Heated, or cooled
 Reactive Sputtering

Control of reactive gas is essential to prevent target poisoning

Spectral line monitoring
Partial pressure control

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

Typical hysteresis behaviour during reactive sputtering of alumina

 Spectral Line Monitoring
The reactaflo works by monitoring and controlling the level of the
plasma intensity by controlling the input of reactive gas

Set-point

OEM signal
100% metal (metallic interlayer)

Working point
(compound coating)

Ti emission spectrum Time

 Reactive Sputtering with Spectral Line Monitoring
Fibre optic cable

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:

Low ionisation efficiency in plasma

High operating voltage
High losses to chamber walls
Significant substrate heating
High pressure process gas-phase scattering
Low deposition rates
Low ion currents at substrate

Many of these problems have been overcome

with the development of magnetron sputtering
MODULE 7: Magnetron Sputtering

Magnetron Sputtering Processes

Definition*:

A diode device in which magnetic fields are used in concert with

the cathode surface to form electron traps which are so configured that
the ExB electron drift currents close on themselves.

Developed largely by semiconductor industry in the 1970s to

improve efficiency of sputtering systems and allow deposition onto
thermally sensitive substrates.

* JA Thornton, Thin Solid Films, 80 (1981) 1-11

 Electron Motion

B B
rg

(Larmor
radius) v
vll ll E

v

v v
E ExB

Electron motion in Electron motion in uniform

uniform magnetic field, B,
magnetic field, B with perpendicular uniform
electric field, E
 Many types developed

Cylindrical-post magnetron
Rectangular-post magnetron
Ring discharge-post magnetron
Cylindrical-hollow magnetron
S-gun magnetron
Rotatable magnetron (C-Mag)
Planar magnetron

Only planar and rotatable magnetrons

still widely in use
 Magnetron Schematic

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

A circular planar magnetron cathode, showing the magnetic field and

resulting ExB drift path
Source: Angstrom Science
 Rectangular Planar Magnetron

Source: Gencoa
 Process Features:

Magnetic field restrains secondary electrons to vicinity of cathode surface;

Increases ionisation efficiency
Dense plasma region in front of target
Increases sputtering rate
Characteristic racetrack develops on target surface
Lower operating pressure than basic sputtering system:
0.1 to 0.01 Pa (1x10-2 to 1x10-3 mbar)
Higher deposition rates
microns per minute for metals
Plasma is confined to target region
Low substrate heating effects
 Process Limitations:
Plasma is strongly confined to target region
Low ion currents are drawn at substrates placed > 60mm from target (typically
< 1mA/cm2)
Insufficient to modify film microstructure
Difficult to coat complex components
Energy delivered to growing film can be raised by increasing substrate bias
voltage this can have detrimental effect on properties

A high flux ( > 2mA/cm2 ) flux of low

energy ( < 100 eV) ions has been found to
give optimum film properties

Unbalanced magnetrons can provide these

conditions
 Unbalanced Magnetron Sputtering (UBMS)

Unbalanced magnetrons are made by strengthening the

outer ring of magnets in a conventional balanced
magnetron*

Plasma is allowed to flow out towards the substrate

High ion currents drawn at substrate ( up to 20 mA/cm2 reported)
Dense coatings produced with low substrate bias
Ion current proportional to target current
Independent control of ion flux and energy
Multiple sources combined to surround work-piece

* Window and Savvides, J.Vac.Sci. Technol. A4(2) 1986, 196-202.

 Comparison of plasma confinement in conventional and
unbalanced magnetrons

Ion Current Density Ion Current Density

< 1 mA/cm^2 2-10 mA/cm^2

Substrate Substrate

PLASMA
PLASMA
~60mm

Target Target
N S N N S N

Conventional Magnetron Unbalanced

('balanced' magnetron) Magnetron

After Window and Savvides, 1986

Reviewed in e.g. PJ Kelly and RD Arnell, Vacuum, 56, 3 (2000) 159-172.

 Schematic Representation of Unbalanced Magnetron

Ferrite magnets in water chamber

Aluminium body

Directly cooled target

N S N

Mild steel
pole piece
N S N

Rare earth magnet

Water cooling Mild steel core piece

 Degree of unbalance?

Bz = Zero (Null Point)

Electrons need to
pass all these field
lines and reach the
null point before
z
being lost to the
magnetron

W/2

If Z is large, i.e., >W, then the chances of an electron

escaping is low and the magnetron is balanced
Source : Gencoa
 Increasing degree of unbalance

VT100300 fully VT100300 middle VT100300 fully

unbalanced balanced position balanced
position Bz=0 @ Bz=0 @ 61mm position Bz=0 @
44mm 80mm

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

Mirrored Closed Field

Source: Gencoa
Plasma confinement in dual co-planar closed field unbalanced
magnetron sputtering system
Impact of closed-field configuration: Substrate ion currents

0.35

Substrate ion current, A

0.3

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

Target current: 2A DC; Ds-t: 150mm

Impact of closed-field configuration: Coating structures
(ZnO:Al)

1mm 1mm

1mm 2mm

Closed field configuration Single magnetron configuration

 Multiple Magnetron Systems

Even numbers of magnetrons are arranged in closed-field

configuration
Magnetrons surround work-piece
Very high substrate ion currents possible
High rate and uniform deposition possible
E.g. PLASMAG systems patented by Teer Coatings Ltd

Source : Teer Coatings Ltd.

 BOC

Planar Magnetrons:
Rectangular or circular Von Ardenne

10s of mm diameter up to several m in length

Variable strength variable ICD
Multi-source systems vertically opposed, in-line,
web coating, indexed, etc.
 Alternative Magnetron Designs

Target erosion issues

Process stability issues

Two basic approaches

Rotatable magnetrons (C-Mags)
Flextrack (Bekaert Advanced Coatings)
Full Face Erosion magnetrons (Gencoa)
Clean Mag (Applied Films/FEP)
Scanning magnetron (Hitachi)
Cylindrical magnetrons for internal surfaces (Teer Coatings Ltd)
 Rotatable Magnetrons

BOC patent (C-Mags)

Self-cleaning
Very high target utilisation (90%)
Large anode return path BOC

Valmet General
 Magnetic Manipulation

Full Face Erosion (Gencoa)

Internal Cylinder (Teer

Coatings Ltd)
MODULE 8: Pulsed Magnetron Sputtering

Pulsed Magnetron Sputtering

Pulsed sputtering introduced in early 90s

Periodic target voltage reversals significantly modify the deposition
process
Target voltage modulated at frequencies in the range 5-350kHz
No need for tuning circuits
Very effective, but not well understood
 Problems with DC Reactive Sputtering
of Dielectric Materials

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

Hard arc (Bipolar arc)

 Pulsed DC power offers many advantages over
continuous DC processing

Pulsing magnetron discharge in mid-frequency range (20-350kHz)

suppresses arc events
Stabilises and allows control over deposition process
Results in:
enhanced structure/properties
enhanced deposition rate
modifies plasma
At the substrate*:
higher ion currents/heating rates
structural modification
Commercially attractive

*PJ Kelly, R Hall, J OBrien, JW Bradley, P Henderson, G Roche and RD Arnell,

J. Vac. Sci. Technol. A 19 (6) Nov/Dec 2001, 2856-2865.
 Target voltage waveforms

Asymmetric bipolar

400
200
100 Pulse-off
0
Target Voltage, V

0 0.00E+00 4.00E-06 8.00E-06

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

200 Pulse on Pulse off 1

0
-200 -1
-2
-600
-3
-1000 -4
0 1 2 3 4 5 6 7 8 9 10
Time, ms

Advanced Energy Pinnacle Plus

100kHz, 50% duty
 Charging and discharging at target surface

Pulse-on Pulse-off

Dielectric layers
+ + + + - - - -
Target - - - - + + + +

Charging up by Discharging by
+ Positive ion
positive ions electrons
- Electron

Arcs are suppressed if discharging during pulse-off

period is complete
 Arc event captured on oscilloscope

Voltage

Current
 Cumulative hard arcs Vs duty

C u m u lative h ard arcs 600

To 6000 arcs
400 duty = 64%
duty = 76%
duty = 82%
200 duty = 88%

0
0 20 40 60 80 100 120 140
Time, mins

Alumina coatings; 60kHz pulse frequency; Reverse times 2-6ms

PJ Kelly, PS Henderson, RD Arnell, GA Roche and D Carter,

J. Vac. Sci. Technol A 18 (6) Nov/Dec 2000, 2890-2896.
 Target Voltage Waveforms
- Dual bipolar magnetron systems

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

Pulsed DC (Advanced Energy) Mid-frequency AC (Httinger)

 Dual Magnetron Configurations

Rotatables
(BOC)

Co-Planar (BOC)

Co-Planar (Von Ardenne) Double-Ring (FEP)

 Potential Benefits of Pulsed Sputtering
- Structural Modification

10m
2m

Reactive DC sputtered Pulsed reactive DC

alumina film sputtered alumina film

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

DC reactively sputtered Pulsed DC reactively

alumina film sputtered alumina film
(150kHz)
J OBrien, and PJ Kelly, Surf. Coat. Technol. 142-144 (2001) 621-627.
 Surface Roughness

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

Typical scratch test tracks at failure point

(200mm Rockwell C indentor):
left = continuous DC (Lc = 7N);
right = pulsed DC (20kHz: Lc = 25N)
Original mag: x100

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

100kHz, 50% duty

400
B
200 C
Target Voltage, V

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

Low Friction TiN

Multi-component coatings (e.g. ZnO:Al) from powder targets
Pulsed biasing
 TiN Coatings:
Friction Response thrust washer tests

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

Typical results for unlubricated TiN coatings

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

Continuous DC high Pulsed DC (20kHz) low

friction friction
High resolution SEM micrographs of the surface of TiN coatings on Si
wafers

Micros supplied by Center for Microanalysis of Materials, University of Illinois

 Multi-Component Coatings by Pulsed Magnetron Sputtering of
Powder Targets

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

ZrB2 hot pressed target

 Powder Coating Rig

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

99.99% pure powders

~1mm particle size ZnO/Al2O3
blend 1mm
Blended in rotating
drum
60g charge for target
Lightly tamped into
recessed backing plate
ITO, doped-ZnO, CIS,
Cr-B studied to date Cr-B
blend
 Voltage Waveforms
800

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

Significant voltage overshoots at high (>200kHz) frequency may aid

plasma ignition in poorly conducting targets
 ZnO:Al Coatings From Powder Targets

Stable discharge no arcing or outgassing

Dense, defect free coatings
Composition: 2wt% Al (i.e. close to target composition)
After annealing films have low resitivity (~2.7x10-3 Wcm), high
transmission (~90%) and strong 002 texture

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

PJ Kelly, Y Zhou, A Postill, Thin Solid Films, 426 (2003) 111

 Results: Chromium Diboride Coatings

1mm

Cr-B coating deposited by pulsed magnetron sputtering from blended

powder target by pulsed magnetron sputtering (100kHz)
 The application of pulsed DC power at the substrate

Recent work* has shown that if the bias voltage is pulsed:

ion current is greater than DC bias case
ion current increases with bias voltage
both effects increase with pulse frequency

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

Widely used for deposition of dielectrics

Suppression of arc events, giving process stability
Production of defect free films possible
Commercially viable deposition rates possible
Plasma properties are modified with pulsing
Plasmas are hotter and denser on time-average
Electron temperature (Te) and plasma potential (VP) are modulated
by driving voltage waveform
High energy ions created during off-phase
Process offers benefits in deposition of other materials
Low friction TiN
Multi-component coatings from powder targets
MODULE 9: Applications of Magnetron Sputtering

Applications of Magnetron Sputtering

Magnetron sputtering has become the process of choice for a

wide range of applications
Why Magnetron Sputtering ?

Easily scaleable from lab R&D to industry

Relatively simple, reliable process
Extremely versatile
Excellent film properties
Metals, alloys, ceramics, multi-layers, graded coatings
Uniform deposition over large and/or complex surfaces
Control of process allows control of properties
 Applications include:
Wear resistant coatings
Corrosion resistant coatings
Decorative coatings
Optical coatings
Electro-optic devices
Reflective coatings
Data storage media
Sensors
Chemically active/reactive coatings
 Wear Resistant Coatings

Nitrides/Alloy nitrides
Carbides/Carbo-nitrides
Carbon-based
Molybdenum-disulphide based

Source: Teer Coatings Ltd

 Wear resistant coatings
- nitrides and carbides

Matl Hardness, Coeff of Uses

VHN friction
TiN 2200 0.6 General tooling and forming dies, drills,
punches, etc

CrN 1500 Punching applications, particularly good

against copper alloys

ZrN 3300 0.6 Machining applications against Al, Al alloys,

brass, Cu and Cu alloys

AlTiN 2800 0.6 High speed machining/dry machining of Al

alloys, cast iron, Ni alloys

CrC 1600-2000 High toughness, good wear resistance in

corrosive environments

TiCN 2800 0.6 High toughness, suitable for punching,

drilling, high speed machining

Source: Teer Coatings Ltd

 Carbon-Based Coatings

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

Motor racing engine parts

Other automotive components
E.g diesel fuel injector and plunger
Cutting tools for brass and copper alloys
Vacuum pick up nozzles
Forging tools
Worm gears
Linear bearings

Source: Hauzer Source: Teer Coatings Ltd

 Graphit-iC TM

0.08 coefficient of friction

Excellent running under water
Dry lubricant
1600-3000Hv
Electrically conductive with graphitic structure
Applications include
Engine components
Cutting tools
Parts operating in aqueous environment
Injection mould parts

Source: Teer Coatings Ltd

 Graphit-iC Field Test

80
No. of holes drilled

70

60
No coating
50 Pure carbon
40 TiN
Graphit-iC
30

20

10

6mm diameter drill, 1200rpm, feed rate: 0.63mm/rev,

workpiece: heat treatable steel

Source: Teer Coatings Ltd

 Molybdenum Sulphide-based coatings

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

Source: Teer Coatings Ltd

 MoST Field Tests

No. of holes drilled

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: Teer Coatings Ltd

 Applications: MoST

Cutting and forming tools

Dies
Valves
Saw blades
Mould parts
Bearings
Aerospace application
Dry machining

Source: Teer Coatings Ltd

 Decorative Coatings

Scratch and wear resistant

coatings on bathroom and door
furniture, pens, spectacle
frames and watches
ZrN commonly used for gold Source: Newform
coating
DLC for black coating
Metal and plastic substrates

Source: Tecvac
Source: Deco-Systems
 Corrosion Resistant Coatings

Fasteners in aerospace applications are commonly either cadmium electro-

plated, or Al-coated using the McDonnell Douglas Ivadizing (Ion Vapour
Deposition) process

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

Knoop Microhardness, GPa

Time to first red rust, hours
700 4
3.5
600
3
500
2.5
400
2
300
1.5
200 1
100 FCC Al Amorphous 'glassy' phase HCP Mg
0.5
0 0
0 20 40 60 80 100
Weight% Mg
Coating surface Corrosion resistance Cadmium (typical) Hardness

Excellent tribo- and

corrosion properties

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

Typical Low-E Typical Solar

Stack Control Stack
 Low-e and solar control films

U Visible IR Heat radiation (Black

V light
body) at 23.9 C

Energy transmission
Low-e
Solar
control

5m 50m
Source: Pilkington plc
 Low-e and solar control films

150 large area coaters worldwide (1999)

240 million m2capacity per year
Low-e films can save equivalent of 20litres of heating oil/m2
Solar control films increase comfort in buildings and vehicles
Drivers:
Increased use of glazing (40B ft2 glass produced in 2002)
Legislation (100% of new glass coated in Germany; 33% in US)
Increased glazed areas in vehicles
Fuel wastage on air con units

Source: FEP
 Anti-Reflective Coatings

SiOx
TiOx
SiOx
SnOx
Glass

4-layer AR
Stack

Source: FEP
 AR/AS coatings

Applied to PDP screens, CRTs, touch

panels, etc
Provide higher readability, better
contrast, electromagnetic shielding

Low index layer, SiO2

High index layer, TiO2

Low index layer, SiO2 Source: FEP

TCO layer

PC, or glass
 Transparent Conductive Oxide Coatings

TCO coatings are an integral part of:

Displays, OLEDs, photovoltaic solar cells, AR/AS coatings, etc
ITO most commonly used
ZnO:Al and SnO2:F also available

OLED is brighter, thinner, lighter, and faster substrate

than the normal liquid crystal (LCD) display in
use today. They also need less power to run,
offer higher contrast, look just as bright from
all viewing angles and are - potentially - a lot
cheaper to produce than LCD screens. TCO

Organic layer

Source: Applied Films

 Solar Cells

Source: Applied Films

 Photocatalytic Coatings

Active crystalline TiO2 layer breaks

down VOCs and NOX under the
action of UV and rain

The resulting surface

is self-cleaning
 Transparent conductor
Electrochromic coatings

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

Rear view mirrors incorporate

electrochromic glass to prevent dazzle

Source: SageGlass

The sunroof for the Ferrari

Superamerica uses
electrochromic glass. Five tint
levels are available, activation
takes less than one minute

Source: Classic Driver

 Flexible Circuits

Flexible circuit boards Cu

sputtered onto Kapton
 Data Storage Media

CDs, DVDs, miniDiscs, hard drives and readers all incorporate

sputtered layers

Source: Unaxis
 Complex multi-layer
structures deposited
in cluster systems

Source: Unaxis
 Microelectronics

Applications Utilising Pulsed Sputtering

Dielectric layers
Metal-insulator-metal (MIM) capacitor structures
Bulk acoustic wave devices (BAW)
Automated batch processing

Source: Trikon Technologies

 Highly Reflective Coatings

98% reflective 3m diameter mirrors for Gemini telescope

Ultra-high purity Al coatings
Magnetrons traverse across surface

Source: Teer Coatings Ltd

 Chemically Reactive Coatings

1mm
0.4
mm

Very high surface area Ti and Zr Ti/C nano-laminate pyrotechnic

pyrophoric coatings (1000x coatings**
bulk surface area)*

*PJ Kelly, J OBrien and RD Arnell, Vacuum 74

(2004) 1-10.
**PJ Kelly, Proc. 19th Int'l Pyrotechnics Seminar,
Christchurch, New Zealand, Feb. 1994, pp319-338.
 Ultra-Thick Coatings

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.

Plasma nitriding, followed by TiN coating

- increased hardness of substrate gives greater load support for TiN coating
increases adhesion
$Plasma Immersion Ion Implantation: PI3

- combines plasma nitriding with high energy 20keV - ion bombardment

TiN followed by vac. evaporated flash of gold
- cheap gold-plating
Electroless nickel followed by TiN
- improved corrosion resistance and load support
Layered DLC/metal carbide CVD/PVD coating
- &Dimigen process improves adhesion of DLC coatings

* A Matthews and A Leyland, Surf. Coat. Technol, 71 (1995) 88-92

$ C Blawert, et al, Surf. Coat. Technol, 98 (1998) 1181-1186
& H Dimigen and H Hubsch, US Patent 45254417, 1985.
Duplex plasma nitriding/PVD ceramic coating process

Low alloy steel

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

dtea ociNT DVP

100
trn U

lP
tra as
m
ee

treu D
dat

50

expl
id

e
ni

dat
de
0

Treatment

Bell, Dong and Sun, Tribology Intl, 31 (1998) 127

 High Power Pulsed Magnetron Sputtering
(HPPMS, or HIPIMS)

Very high power (kW) pulses

Average power ~ 20kW Output
Pulse widths ~ 150us Voltage
1000 V/div
Duty ~ 0.5 - 5%
Very high metal ion fraction
Up to 100% claimed Output
Power
Benefits of arc source, without the
500 kW/div
droplets
Output
Current
500 A/div

Vladimir Kouznetsov, Karol Macak, Jochen M. Schneider, Ulf Helmersson,

and Ivan Petrov, Surface and Coatings Technology 122 (1999) 290.
 10. Summarising Comments

Surface Engineering impacts our daily lives

PVD processes are extremely versatile and successful
Magnetron sputtering now process of choice in many cases
Continuous development over ~20 years has provided
improvements in properties/process
Unbalanced magnetrons
Closed field multiple magnetron systems
Pulsed magnetron sputtering
HIPIMS
Applications of magnetron sputtering will continue to grow
Versatility
Scaleability
Clean process
 Acknowledgements

Dr Dermot Monaghan, Gencoa Ltd

Dr Vanessa Fox, Teer Coatings Ltd
Dr Alf Smith, Valmet General
Advanced Energy Industries Inc
Leybold Optics
Mr Brian Garside, TECVAC
Dr Johannes Struempfel, Von Ardenne
Pilkington European Technology Centre
FEP Fraunhofer Institut
Unaxis