AN

INTO

INVESTIGATION

ION

I11ATING

AND PARATJIETERS

MECHANISMS

by
Bogdan

Dipl.

(Bucharest

Eng.

A thesis
for

Department

degree

of zero

t;o the
of

University

Doctor

& Mechanical
1978

Romania)
-

Institute

Polytechnic

submitted
the

Delcea

Lucian

of

of

Salford

Philosophy

Engineering

Copy
Best

Available

PRE

The work
out

in

the

the

University

December

Institution

Department
of

in

this

thesis

of I,4echnical

Salford

between

are

submitted
for

declare

to

wishes

thesis

has been

described

was carried

Engineering
April

at

1975 and

1977.

The author
`this

FACE

his

own work,
to

any

any degree

that

other
or

the

no part

contents
of which

University
qualification.

or

of

ACKNOWLEDGEMENTS

for

his

to

indebted

deeply

is

The author

D. G. Teer
this

throughout

supervision

competent

dir.

project.
He is

financially

He is

wishes

to

Spectroscopy

to

constant

also

are

technical

express
moral

J. France

advice

Dr.

thank
for

and Mr.

H.

help.

constant

University

Loughborough

for

Mr.

to

their

for

The author

for

A. J. Kirkham

indebted

Pendlebury

He wishes

and thanks

discussions.

helpful

also

Auger

Mr.

for

Ltd.
work.

entire

appreciation
to

expressed
and very

this

supporting

The author's

Lucas

Joseph

to

indebted

also

from

J. M. Walls

carrying

the

out

tests.

his
support

thanks

to

and for

his

wife,

typing

thesis.

it

this

Nona,

INDEX

I*
Page

List

of

Symbols

1
3

Synopsis

CHAPTER 1 -

INTRODUCTION

CHAPTER 2 -

ION PLATING

Introduction

2.2.

Ion

2.3.

Ion

2.4.

Glow Discharge

2.5.

Collisions

2.6.

The

Plating

Rig

11

Plating

Procedure

18

Role

of

Ionization

Energetic

of
Ion

the

Ionization

2.9.

Neutrals

Spectrum

2.10.

Neutrals

Energy

2.11.

Ions

45
Involved
57

Process

67

Efficiency

Energy

Experimental

2.11.2.

Theoretical

2.11.3.

Experimental
Result

74
85

Spectrum

100

Spectrum

2.11.1.

2.11.4:

Particles

38

in

Films

Plating

2.8.

Mechanism
Neutrals

Adhesive

Energies
the

28

and

Obtaining

in

Lt CHANIS&'IS

2.1.

2.7.

100

Arrangement
Approach

103

Procedure

and
107

31

Parameters
Effect
of
-The'.
the Dark Space/Mean Free

upon
Path
117

Ratio
0

2.11.5.

2.11.6.

The

Effect

the

Ion

Parameters

upon

Current

120

Concluoions

CILi iER3-

NU CI. JTI

Nucleation

OF ION PLATED FIf;

and

3.1.1.

Theoretical

3.1.2.

Experimental

3.2.

123

ON AND Iid'1 L 3FiC'

ADHESION
3.1.

of

124

I3

Growth

124

Approach

124

Results

128

Interface

136

3.2.1.

Experimental

136

3.2.2.

Results

139

3.2.3.

Conclusions

147

3.3.

Adhesion
Factors

CHAPTER 4-

4.1.

of

Ion

Plated

Determining

Films

and
148

It

THIN FILMS CHARACTERISTICS

Surface

Morphology

and

153

Film

Microstructure

154

4.2.

Lattice

161

4.3.

Crystallite

4.4.

Film

CHAPTER 5-

Parameters
Size

and

Strain

Internal

181

Thickness

THE EFFECT

OF PROCESS PAR v1ETERS

182

UPON IO1 PLATED FII2,2S

5.1.

Theoretical

169

182

Approach
4

5.2.

Experimental

5.3.

Results

11.190
197

5.3.1.

Microstructure

197

5.3.2.

Throwing

Power

226

5.3.3.

Internal

Strain

229

5.3'. 4.

Conclusions

232

APPENDIX

233

REFERENCES

238

-ITlist

symbols

,.

Aef

= activation

efficiency

= interplanar

spacing

df

= film

DR

= deposition

`e

= electron

= lattice

= energy

Li

= ion

E
n

= neutral

Go

= gas

atom

G*

= gas

metastable

%G+

= gas

positive

thickness
rate
charge

internal

strain

a particle

of

energy

energy

ion

= current

intensity

Ic

= cathodic

current

Ie

= electronic

Ii

= ionic

Ief

= ionization

current

current
efficiency
dark

= cathode

free
mean
=

Lhke

= crystallite

I'll
l2

= mass of

s
1110

of

space

mean free

path
dark

cathode

space

size
the

particle

= metal.

atom

M+

= metal

positive

Ne

= number

of

electrons

i,I

= number

of

ions

,j/
ion

length

path

ratio

-2-

Nn

of neutrals

number

Nne

= number

of

Nno

= number

of nonenergetic

N
np

, = number

gas

in

= radio

Sc

= cathode

SpR

= sputtering

impinging
for

a second

the

1 cm2 of
'p'

pressure

frequency

T=

temperature

V=

voltage

Vc

= cathode

W=

power
rays
= molecular
x-

neutrals

pressure

R. F.

e=x-

neutrals

?f rp6.rticlbs

surface
p=

energetic

area

surface
rate

voltage

diffraction
free

angle

path;

wave

length

of

the

rays

= deposition

rate

sputtering

rate

ratio-

MISSING
PAGES

NOT.

AVAILABLE
I

.\

- *I-

Synopsis

Ion

is

for
new and modern technique
films
obtaining
very adhesive
on any kind of surface
and
The development
substrate
of electron
material.
gun evapothe possibility
to de.osit,
ration
sources
created
with
high rates,
high melting
having
like
materials
points
:
plating

'tolybdenum,

Tungsten

A part

which

energetic

neutrals

For

in

role

this

involved

energy

ion

in

have

coating

the

td

attempts

that

purpose,

and their

work

are
the

Carbon.

and even

this

of

particles

major

a fairly

been

the

establish

kind

of
the

especially

plating,
considered

to

not

play

process.

ions

from the neutrals

ate separated
determined
theoretical
using

spectrums

and experimental
methods.
ters upon the energies
of

The influence
the

iond

work

is

of

process
is
and neutrals

parame-

a parametric
study
films
as compared

of

also

studied.
Another
the

part

the

vacuum

straight
interface
of

ion

to

attempt-in
formation

ion

of

nucleatioh.

this

of

evaporated
films

plated
the

clarify
a deep

of

grossed

Finely
aim-of

a parametric
improved
producing

manner

by

pressure,
temperature

A physical
produced

the

varying
bias
is

voltage
also

model

thin

plated

for

snd reported.

is

and

analysed

also

that

processes

and

lead

to

measured

the

interface.
study
film

main

film-substrate

The

ones.

to

is

in

structures

process
ion

out

carried

parameters

current.

The

with

the

a controlled
such

as

substrate

considered.

removing

the

columnar

structure

is

-4-

k.

CHAPTERI

INTRODUCT ION

The

most

evident

by

coating

it

change
with

deposition

The
final
.

three

another

of

physical

vapour

lable:

developed
nology

1,

tioP5etc,
tioned
to

sputter

ion

The

more

above,

is

surface

achieved

material.

important
coated

deposition

in

At

surface.

moment,

the

techniques
(high

the

determining

are

avai-

low

vacuum)

techniques

have

or

deposition

plating

deposition

recently

are
but

like:

basically

one of

substrate

the

have

been

Beam Tech-

Vacuum Deposi-

Activated

some facilities

io. i. zatibn,

Cluster

Ionized

Sputterin4

Magnetron
which

a solid

deposition

alternative

control

sition

the

properties

Some other

is

method

vacuum

of

methods

been

men-

incorporated

temperature,

or

depo-

rate.
energy

of

a vacuum

evaporated

atom

is

given

by:

-5-

The

eT

for

T=2900K

energies

20-100

of

eV but

barding

our

atoms

are

are

on the

own work

tendsto

atoms

(l

eV

sputtered

species

sputtered

0.2

--

indicate

that

lower

probably

to

reported2

energy

the

of

the

)
l.
.

be
bom-

energies

than

previously

ions

has been

of

thought.
For

on Plating,

ter'4to
for

be equal

good

recent

toms

injected

low,

in
is

efficiency

the

Even

in

ions

these

particles

are

i. e. 3000 eV

energy,

and thus

the

was explained

films.
However,
plated
more
20
that
the ionization
proved
efficien-

and even

this
well

is

acceleration

repor-

ion

of

into

Experiments

the

of

voltage,

experiments

very

energy

the

adhesion

cy is

of

to

kV bias

a-3

very

the

the

lower

in

below

case

of

metal

proved

that

the

ionization

l% and

that

the

average

much lower

than

the

conditions,

more energetic

a-

discharge.

plasma

work

the

the

ion

energy

acceleration

depositing

plating

than

in

full

energy

energy.

tech-

any other

nique.
Ions

charge,

and

neutrals

though

their

previously

th%ht.

The

domains

energy

methods

take

can

place

have

average

where
are

the

energy

three

represented

is

of

lower

vapour
in

Figure

the

dis-

than

deposition
1.2.

was

-6-

k,

E (eV)

YE
II

SD
IP

Figure

1.2.

where:
VE = Vacuum

Evaporation

SD = Sputter

What

IP

= Ion

Plating

II

= Ion

Implantation

makes

ion

is

the

of

film-substrate
ion

like

carbides,

that

by

and
be

the

plating
producible

of

a very

good
and

combination,
the

plating,
or

altering

the

Therefore,

process
and

is

has

It

nitrides.
process

improved

due

also,

in

coatings.

to

been

proved

the

study
to

kind

the

films

of

re-

structure
films

they resulting

order

any

complex

also

a parametric
necessary

for

adhesion

parameters,
of

method

coating

of

production

aL properties

physi

changed

desirable

a very

plating

achievement

active

Deposition

the

produce

can
ion
re-

-7-

importance

Of a great

is

the

of

stages
face

interface

poor

The

types

of

in:

mechanical,

fusion

formed

in

growth,

leading

interface

to

have

the

very

since

film

a thin

of

early
inter-

a porous

and

concentration

stress

been

to

monolayer

by

clasified

Piattox4

compound,

monolayer,

dif-

and Pseudodiffusion.

is
the

characterize

incompatible

early

resulting

a term

kind
is

which

plating,

The

adhesion

strength3.

Fseudodiffusion
.

'even

and

weak,

therefore

the

is

which

nucleation
be

will

for

of

morphology

of

coat

out

of

ence

of

for

is

sight

a term

parts
upon

parameters

accepted8to

obtained

in

good

reust also

of

adhesion

describing

of

the

it,

is

influence

the

film.

thin

the

substrate
also

studied

,,

ion

materials.

growth
the

been

the

film-substrate

and

power

interface

responsible

nucleation

Throwing

has

which

'

to

capacity

and the
in

this

influwork.

--

CHAPTER

ION PLATING

2.1.

MECHANISMS

Introduction

As shown

in

deposition

vapour
number,

technique

sition

method.
in

presented
riority

film

are

available

Plating

and

as

as well

the
it

the

is

which

the

four
shows
the

regards

as

this

depo-

electro-chemical

of

2.1.1.5

Table

to

and

be added,

a wet

physical

methods

is

the

supe-

net

large

obtaining

area

where

improved

of

properties.
Plating

of

high

is

a diode

system

cathode
of

pressure

used,

mainly
metal

complex
The

in

Ion

ion

anode,

is

cave
react

earthed

in

discharge.

glow

of
with

plating

to

set

arrangement
the

and

be

chamber

in

Other

gases

can

gas

ion
to

high

An argon

coated.

the

reactive
the

deposition

a plasma

substrate

mTorr

the

as

basic

the

the

as

vapours
compound.

The

with

10-50
the

establish

defined

was
ions8

energy

voltage

the

is

three

chapter,

could
and

be used,

Ion

to

methods

A comparison

Ion

of

can

previous

electroplating

oldest

it

the

plating
deposit

order
be
when
as

'

Plating

process

is

composed

of

two

stages:

9
3`

E`

0
;; 0

4'

42

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of

TN

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--C

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11 q

CL
v

10
-

a.

The

cleaning

sputter

bardment

and,

neutrals

continued

during

b.

bombardment,
the

this

by

work,

a process

is

which

stage.

second

bombardment,

by the

In

substrate.

covered

total

drawn

secondary

steady

value,

resulting

moment

when

The

completed.

During
itself,

metal

second

on the

is

as ions

substrate

to

considered
3-5

W.

deposition

the

the

into

injected

current,

usually

is

to

drops

is

give

being

are

cathodic

step

which

stage
are

oxides

a steady

voltage

to

current

current

cleaning

cathode

electronic

plasma

and high

or

and
low-

neutrals.

energy

time,

this

All
to

order

in

vapours

deposit

will

the

the

surface

ion

the

electronic

sputter

when the

As these

current.

the

the

adds to

and

emitted

a high

oxides,

ion

the
are

electrons

beginning,
of

which

cathodic

removed,

the

a layer

with

is

current

secondary

is

process

During

etching"8

free

oxide
a highly

and this

produced

as "ion

to

referred

neutral

, the

is

clean,

same time,

the

and at

lattice

a very

stage,

achieved

deffective
often

first

the

is

surface

be

in

bom-

Deposition
During

is

later

ion

by

substrate

demonstrated

as

energetic

the

of

A very
formed,
affect
(adhesion,

at
the

important
the

clean

dep<osAed

very

whole
structure,

and to

surface

is

beginning

when

the

remove

interface
which

of'evaporation,

deposited
etc).

maintained-in

particles.

moment

further

is

discharge

glow

a very

maintain

non-adhesive

the

At

the

films
same

is
will

properties
time,

the

de-

10
-

a.

The

cleaning

sputter

bardment

and,

neutrals

continued

during

b.

second

in

ion

this

bomby

work,

a process

is

which

stage.

Deposition
During

as "ion

by

the

is

covered

with

is

current
total

steady

value,

resulting
-

moment

when

During
itself,

metal

energy

to

give

being

are

to

drops

current,
to

considered
3-5

usually

the

ions

and

discharge

is

kV.

deposition

the

into

as

substrate

electronic

is

is

which

injected

are

surface

cathodic

is

voltage

stage

the

and

plasma

high

or

low-

neutrals.

All

time,

this

to

order

at
the

(adhesion,

clean

very

whole

maintained-in

and to

remove

particles.

beginning

further

structure,

surface

moment is

important
the

glow

deposited

non-adhegive

formed,

the
a very

maintain

A very

affect

second

emitted-

current

step

and

are

oxides

a steady

is
ion

the

current

cleaning

cathode

on the

ion

the

As these

in

vapours

deposit

will

the

the

to

electronic

sputter
The

completed.

a high

current.

secondary

the

oxides,

adds

the

electrons
when

which

a highly
process

beginning,
of

cathodic

removed,

the

free

oxide

During

etching"$

a layer

drawn

and this

secondary
In

substrate.

clean,

same time,

produced

bombardment,

neutral

, the

is

to

the

and at

lattice

referred

a very

stage,

achieved

deffective
often

first

the

is

surface

be

later

bombardment,
the

by

substrate

demonstrated

as

energetic

the

of

of

when the

evaporation,

deposited
etc).

interface

At the

films

which

is
will

properties

same time,

the

de-

11 -

position

rate

to

the

allow

2.2.

Ion

must

film

Figure

tron

2.2.1.

both

plating

Salford

at

is

procedure

presented

University.
for

similar

systems.
The

and

is

arround

the

cathode

the

in

back

water

substrate

quired

surface

and

pump

nitrogen

cooled

For
ration

the

rig

source

is

In

merit.

that

the

the

discharge

the

system

for

an oil

diffusion

baffle

valve.

both

same time,

is

rigs

boat

in

the

a Tungsten

to

fila-

produce

thicker

films.
For
electron
gun

is

the

rig

gun

is

mounted

presented
used
in

to

a collar,

in
produce

Figure
the

separated

a 15 kV

2.2.1..,
evaporation.
from

evapo-

can be

or filaments
order

of

a liquid

2.2.1.,
or

re-

on the

composed

pump with

a Molybdenum

confined

is

effect

in'Figure

presented

is

distance

masking

hung

is

shield

and a certain

avoid

H. T.

the

represents

An earth

case,.,, foL ' boats

this`
in

mounted

so

to

order
6.

coated

cooled.

only,

The vacuum
rotary

be

to

substrate

cathode

to

order

an elec-

presents

built

unit

is

rig

plating

2.2.2.

Figure

plating
ion

an ion

of

)and

basic

The

in

rate

grow.

diagram

beam ion

sputtering

Rig

The schematic
in

to

Plating

the

exceed

the

The
main

12
-

43

2.2.9a
ie
ARRANGEMENT
PLATING
ON

14

1S

13
-

k.

2.2.1.

Figure

Index

1.

Pirane

2.

Thermocouple

3.

Earthed

4.

Substrate

5.

Positive

6.

Metal

shield

7.

Glass

chamber

8.

Protective

gauge

shield

cathode

probe

shield

Molybdenum

9. Evaporation
lo.

Baffle

valve

11.

Liquid

Nitrogen

12.

Oil

13.

Magnetic

valve

14.

Foreline

trap

15.

Rotary

16.

Magnetic

17.

Penning

18.

Magnetic

trap

diffusion

19.

Needle.

20.

Shutter

boat

pump

pump
valve
gauge
valve

valve

".I

k,

ION PLATING ARRANGEMENT

b
2.2.1
figure

_L` -

,.

"`---

Thermoca; ple unit

Vacuum 8ouget.

p%
\tocuurn Controt Unit

0
it

>Hi

2.2.1
17iure
c
The ccn+r(l panel

voltage supply

16
LIT

GAS

ELECTRON GUN ION PLATING RAG

Figure 2.2.2

17
2.2.2.

Figure

k.

Index

Deposition

II

1.

Electron

stainless

steel

gun collar

Substrate-cathode

2. Viewing

window

3.

Shutter

4.

Shield

5.

Watter

6.

Penning

7.

Liquid

8.

Magnetic

9.

Pirani

gauge

10.

Rotary

pump

11.

Foreline

12.

Oil

13.

Baffle

14.

Differential

15.

Needle

16.

Positive

17.

Earthed

cooled

electron

gun

gauge
trap

nitrogen
valve

trap

diffusion

pump

valve
pressure

valve
probe
shield

valve

chamber

18
by a variable

chamber
tain

differential

the

10-50

of

pressure
the

optimum

collar,
sure

better

avoid

discharges

parts

of

the

filament.
is

to

The

beam

can

hearth

The
,

use

2.3.

The

be

scanned

so

that

Ion

Plating

authors;

a brief

in

this

wor

sure
are

der

10

removed.

to

allow

the

obtained.

the

heating

is

achieved.

the

1/h

a7

the

material

flow.
to

possibility
and

also

to

same time,

the

with

electron

an
beam.

Procedure

is

First,

by

be

gun

of

conbined

produced

the

of

A can

with

to

of-the

surface

In

be deposited

a pres-

earthed

life

materials

rates.

here

performed

1.5

provides

point

has

procedure

6,8,20

of

gun

melting

can

the

cooled

water

the

order

the

and

voltage
of

in

in

required

extend

on the

is

Plating

Ion

to

to provide

mounted,

HT parts

a uniform

ionization,

enhanced

is

current

evaporation

films

thicker

Torr

acceleration

an electron

higher

is

chamber,

while

plating,

assembly

also

maximum

high

evaporate
have

and

crucible
of

ion

the

a maximum

be melted

The

10-4

between

gun

10 kW and

The

be maintained

filament

than

the

must
for

to main-

order

Inside

rTorr

the

in

valve

pressure.

conditions

where
of

baffle

whole

5-10-6Torr
Then,

outgasing.

described

of

presentation

the

by

many

way it

was

./
system
so-that

the

been

film

After

is

down

pumped

most
material.

this,

of

to

the/residual
is

the

premelted

baffle

a presgases
in

valve

or-

19
-

between

the

diffusion

system

in

collar

and the

is

moment,

the

density

of

stage

called

lasts

until

tant

value,

the

total

when

rent

which

higher
peat
in

an

than
with

the
new

is

value

will

value

continue

to

drop

previous

one,
in

the

when
end

to

and

a new

the

bias

voltage

V2

time
/,

Figure 2.3.1

<VZ4

\3

"

it

and
to

a cons-

to

the

be

clean

cathodic
the

of

cleanis

cathode

value,

will
as

folcur-

steady

process

2.3.1.

Figure

first

this

the

a cur-

the

considered

of

vale

the

kV and

drops

increased,

the

At this

and

thus,

the

as

2.2.2.

a needle

commenced

moment

is

voltage

increases

3-5

is

the

and allowed

current

substrate

in

via

(anode)

and

between

obtained.

mA/sq.

cm,

the,,.

Figure

established

cathodic

increase

is

of

a steady
the

in,

a voltage

the

if

system

in

let

cleaning

the

valve

parts

we consider

reaches

by

0.5-0.8
sputter

process,

lowed

earthed
at

Although

ing

the

is

(for

chamber

baffle

mTorr

discharge

glow

(cathode),

substrate

10-50

of

between

strike

the

gas is

and argon

a pressure

.current

(for

chamber

so that

rent

), or the

2.2.1.

Figure

throttled,

to

pump and the

re-

shown

20 -

This

does

voltage
but

could

that

mean

not

remove
of

is

obtained

not

However,

cleaning.
tice

the

that

proves

the

even

end

the

of

clean

sputter

obtained

in

prac-

cleaning

is

suf-

a partial

such

particles,

a perfectly

adhesion

good

a given

contaminant

therefore
at

for

sputtering

the

all

them,

a percentage

surface

the

ficient.
After
ted

evaporated

and

this

maintain

a perfectly

non-adhesive

combined
.

clean

the

with

back

mixture

of

substrate

deposit

as

a graded

in

role

surface

beginning,

very

and

film

to

on the

the

to
the

remove

sputtering,

will

good

During
order

continuous

which

mel-

substrate.

produce

materials

interface
very

in

and

scattering,

the

obtaining

begins.

maintained

deposited

particles

the

At

is

is

material

deposition

discharge

the

stage,

the

and

film

the

cleaning,

sputter

which
will
a
determinant

play

ion

of

adhesion

plated

films.

iinother
must
is

the

exeed

the

After

evaporation

is

pumped

down

ger

allow

than

the

is

the

the

cathode
important
sputter

deposition

the

stopped
is

closed

to

substrate
surface

distance
dark
stage
cleaning,

in

thick-

discharge
the

system
in

cool

is

a clean

contamination.
could

space

and

film

the

required

the

and

rate

that

so

rate

obtaining

inlet

reducing

source-substrate

A very
dure

to
thus

atmoophere
The

argon

the

removal

grow.

the

quenched,

that

sputtering

to

allowed

ness,

is

condition

and
the
a term

but

lon-

be

any,

is

usually

8. l5cm

ion

plating

proce-

used

to

define

21 -

the

of

process

layers

continuous

on the

means

the

solid

surface

ment.

The

substrate

removal

incident

is

above

which

also

solid

and

Of

course,

at

particles

must
in

is

particle.

will

this

of

tering

yield

will

On the

other

energies,

damaging

by

have

bombard-

particles

e-

a minimum

to

produce

order
of

20-30

of

eV.

50 keV

about
deeply

into

'implantation'.

called

producing

hand,

atoms

penetrate

high

be very

from

limit

is

particles

of

order

process

these

sputtering

the

of

energy

number

be

energetic

which

In fact,
group

to

a maximum
the

the

or

threshold)

energy

There

atoms

k.

contaminant

of

surface.

subjected

sputtering,

can

of

(sputtering

nergy

removal

there

be

will
but

sputtering

the

sput-

low.
high

a too

removing

rate

sputtering
too

unnecessarily

much

material.
Heavier

particles

than

yields

the

have

will

lighter

higher

ones. for

sputtering

the

same

incident

energy.
Considering
the

transfer

the
of

quation:

where

1,21 and

ticles,

E is

a1d
As

transfer
same

M2 are
the

particle

ticle.

it

of

the

energy
Ei

can

more

energy

is

energy

4n7 r!
PJI1+b12)2

ry

case

energy

given

the

by

following

the

of

e)

energy

of

a heavier

a lighter

par-

colliding
the

to

transferred

than

collision,

spheres'

(2-3.2.

masses

seen,

incidence.

'hard

E.

iithe
be

of

the

stationa-

incident

particle

one having
0

parwill

the

22
-

the

at
.

same time,

bombardment
lattice

induces

which

trate

and

face

defects

the

also

process

of

The

often

referred

shows

a scanning

tage
the

to

10 mTorr

grain

structure

nert
.

either

low

energies

film

(caused

desorption

the

in

gas

to

with

the

the

graded

the
In

the

film

be noticed,

can
different

for

ion

the

surface

due

in

rise

lose

gas

much

thermal

their

atoms

deposited
to

the

enerdue

Also,

sputtered

contributing

can

scattering

of

particles.

and

they
the

to

co-

and

temperature).
the

is

i-

plating,

and

released

the

of

to

vol-

to

scat-

are
together

formation

of

interface.

sputter.

as edges
In

the

of

edges

-ghat the

particles

and sharp

points

case

threshold

sputtering
case

be

substrate

atoms

as well

the

due

in

other

can be demonstratod

sive,
to

many

As it

deposition,

the

with

5 kV bias

boundaries.

particles

collisions

scattering,

of

process

energetic

tered-back

It

by

important

A very

gy

or

is

picture

trapped

there

defects

at

sur-

nucle-

rlicroscope

typical

during

film

2.3.3.

35 min.

atoms

subs-

Figure

grain

be

can

the
These

for

lattice

revealed

the

(of

centres

pressure.

is
and

remain

when

argon

substrate

etching'.

for

grains

by

as

'ion

as

of

gas- atoms

vered

act

the

together.

inducing

etched

and

At

couple

in

energetic

lattices

two

to

Electron

surface

etching

defects

the

film)

will

ation.

copper

help

to

subjection

surface

will

of

the

of

non adhesive

will

and sharp

have

less
are

easier

particles,

a lower.

points,

adhe-

the

value.
electric

, ..

u!
lY,
'f.
M4 " '`

;:

Figure2.3.E
Co , per
5 kV

surface
; 10 m`lorr

ion

etched

; 35 minutes

24
-

field

concentration

the

last

This

rates.

columnar

lead

to higher

sputtering

could

be useful

for

resulting

in

will
effect

structure

cuum evaporated

and most

shown in

Figure

2.3.4.7

type

of film

This
is

created

either

the

case

when

cuum evaporation),
the

valleys
better

peaks,
'result

is
If

the
peaks
back

to

exposed

by

bias

as

and valleys

of

micro-

crystallo-

scattering

are

ceramic
conductors-

Sometimes,

if

occur
the
The

grow.

beams of

and

the

valleys.

sources

2.3.5.8
available

also

for

deposition.

can vaporize

and par-

metal

sourcel0
film

are

the

sputtering

evaporation

Figure

sources

substrate,
erode

fill

will

of

the

will

forward

by

in

ions

material.

potentiralfis
or

will

to

applied

types

various

the

will
while

evaporant

redeposition

evaporation
ionize

(va-

applied

deposition,

sufficient,

and
,

can provide

is

shadowing

the

is

if

sputtering

The R. F.

for

films,

structure.

bombardment,

plasma

glass,

of va-

surface

voltage

the

preventing

a negative

ion

bias

no

and they are presented

Some special
ion

tially

the

growth

a geometrical

a columnar

There

which

case

plated

peaks

to

as a replica

removing

planes.

In

in

ion

in

growth

or by prefferential

roughness,
graphic

the

of

the

"

organic

normally
insulators,

used
but

for

coating

can be used

as well.
the

insulators

are

exposed

to

the

plas-

-25-

n.

MMM

.A /A

Hea ily shadowed

Shadowed
areas

areas

a.

Columnor 5tructure

MW
GtE)
M
2

MW
(4) Sputtering (erosion of the peok)
(2) Scattenrxj redeposik
(3) Forwond sputtering

IL

Gt

()Back

sputtered

Not ColumnarStructure

"

6.

Q. Nobias vo!{fie (vacuumevaporo(ion)

b.

Bias volta e(Ton pla+inp

Figure 2.3.4

26
-

ob

Jr

,C
C

.0

10
.y
a

I
I

(I

o
CL

LL.

E
i
0

-2

i7
i

<(1

U'?
t-0
L_

(n
c,ri

to
41
L

dc

LL.

>

So

a,

OD
C
.0

Gb
Q

C3fi
x^

.+

27 -

4.

Metal

CT

Insulator

PLASMA

Well potential

Figure2.3.6

Electrode

configuration

insulators
R. F.

potential

exposed

and surface
to

plasma

in

the

of

potential
case

of

the

R.V.

28
-

to

madue
lion

ultraviolet

scrubbing
better

give
The

of

Figure

an electrode,

the

plasma

to

higher

more
This

bias

posing

the

surface

2.4.

Glow

If
of
two

in

several

applied,

R, F.

on the
as the
the

and

than

ions

facing

accelerate
to

ion

a
as

electrode.

surface

facing
alternating

the

electrons
.

for

and

plasma
attain

will

acting

other

the

thus

and

shown
like

acts
back

But

the

surface

is

negative,

frequency.

will

mTorr,

is

at

very

high

will

at-

a negative
ions,

positive

ex-

bombardment.

andran

Increasing

the
the

by

a D. C.
a low

across
extremely

when

in

is

voltage,

the
the

the

a gas

the

space

low

current

breakdown
current

potential.

pressure
between

applied

a uniform

current

the

achieved,

a drop

containing

voltage

voltage,

moment
are

conditions

chamber

obtained

electrodes

followed

is

a vaccum

electrodes

at

will

Discharge

gradient

and

plasma

electrons

bias.

"'

the

to

surface

electrode

plate

the

mobility
the

the

arrangement

be positive
the

frequencies,
tract

metal

field

will

according
have

substrate
This

the
and

an R. F.

allen

an R. F.

with

in

change

due

also

11

2.3.6.12,13.

capacitor

and

the

effect',
adhesion.

set-up

in

radiation

potential

between

the

two

passes.

increases

slowly

voltage-pressure
increases
This

is

fast
the'nor-

29
discharge

mal'

glow

the

current

can

be observed

'cathode

depends

sputtered
ment
The

with

the

density

by
of

is

due

observed

gas

the

called

current

excited

the

upon

A spot

pressure.

release

to

the

bombard-

the

(h').

radiation
the

and

the

pressure,

nature

the

of

ion

which

2.4.1.

a function

I-V

constant

of

voltage.

discharge
Figure

place.
of

characteristics

the

at

glow

takes

normally

the

and,

'abnormal'

the

plating

presents

area

becomes

called

10 mTorr),

over

cathode

whole

current
is

region

(usually

pressure

the

coverer

This

the

constant,

material.

Increasing
spot

is

voltage

surface

is

colour

depends

colour

gas

the

which

concomitant

the

cathode

which

material

cathode

in

over

A certain

constant.

the

upon

on the

spot'

keeping

and

a glow

dischargel4.
2.4.2.

Figure
normal
and

discharge

glow

its

In

region,

is

composed

and ions,

point

of view.

occurs

ionizations
width

of

occur
the

cathode

pL =

where

p is

the

dark

cgth6de
in

the

most

negative

dark

constant

gas pressure.

space,

value
number

of

the

the

space
glow.
then:

of

luminosity

from

neutral

discharge,

ir-the

field

an equal

of

behaving

1 glow

a nori'

the

regions

its

regarding

the

plasma

the

shows

characteristicsl4..

trons

drop

as

electrical

low,, and it

For

a and

is
of

very
elec-

electrical

potential

and most
If'L'is

of

the
the

30
4

I (cofhodiccurrent)

Voltoge
breKdown voltoge

I Normalglowdischarge
IT Abnormalglowdv5ckarre

Fiure2l4.i.
r

I-V

characteristic

/
of

a glow

discharge

31
-

b.
s

Distnce

1.

Cathode

2.

Cathode

3.

Cathode

4.

Negative

5.

Faraday

6.

Positive

7.

Anode

spot
dark

space

glow

dark

space
(
plasma
column

Figure2.4.2
Normal

glow

discharge

32
The value
little

of'L'depends

In
ion

the

nature

case

plating

rent

in

the

cm and

The anode
the

brought
tight
.

the

following

experi-

is

shown

ache-

from

as the
is
the

to

back

the

earthed

a diameter

with

on the

shield

a mobile,

closer

when

disk

an aluminium

distance

:node

discharge

2.4.3.

same dimensions

thode-t

glow

The arrangement

earthed

is

and very,

gas and temperature.

place,

3 mm distance

proximately

the

of

takes

figure
is

cathode

upon pressure

an abnormal

was performed.

The

is

ap-"

cathode.
disk,

aluminium

having

The maximum ca-

cathode.

22 cm and

the

anode

by means

cathode

at

of

of

be

can

a vaccum

lead-through..

A certain

voltage

chamber,

and then

thode

and the

versus

distance

argon

pressure

the

is

'D'
in

parallel
quench.

to

Figure

variation

of

of

otheF

cathode

the

can

dark

the

ca-

and plotted

voltages

and

means that

the

to

the

must

10 mtorr

and Figure
space

be noticed

space

quite

accurately.

width

flat

to, obtain
2.4.6.
'L'
that

with

and

an instant
present

with

dark

and the

be perfectly

:)tn order

dark

cathode

instantly

nearly

be determined

anode

2.4.5.

It

pressure.

variation

each

it

equal

happens

and the

The cathode

the

2.4.4.

is

could

width

space

in

set

measured

different

quenches,

distance

are

moved towards
is

current

Figure

The quench

space.

anode

for

discharge

cathode-anode

dark

and argon

cathodic

pressure

When the

and

of

process

inatically

10

the

upon

mostly

the

voltage

there

the

is

little

voltage,

33
-

:.

.5

1. Vacuum chamber
2. Earthed

shield

3.

Cathode

disk

4.

Perspex

tube

5.

Mobile

anode

6.

Needle

valve

disk

Experimenta(

arraq

ent

Fiure2.43
0

34
-

ti

04

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36
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37
-

while

the

The

increase

in

dark

cathode
pressures

pressure

leads

effect

in

the

cathode

It

can

also

for

applies

From

dark

the

cathode,

of

30-406

in

the

it

the
for

obvious

with

the

relation

for

V=constant
discharge

12-13

the

anode at
is

which

consequently

ionization

efficiency.

a drop

as well.

that

the

cm', in

order

For

current.

there

decrease

a slight

results

is

ion

maximum

to

glow

2.4.4.

but

conditions,

less

of

width.

that

distance

anode-cathode
the

space

abnormal

Figure

it.

upon

a restrain
is

which

constant

the

to

leads

voltage

be noticed
pL

influence

25 mtorr.

exceeding

in

-from

a large

space,

The increase

obtain

has

pressure

13
in

the

current

means a similar

to

same p-V

cm and

optimum

at

22 cm
density

drop

38
2.5.

Collisions

During
plating

the

is

(G)

cleaning

stage

of

the

ion

the

substrate

which

is

the

HT

accelerated

cathode

cathode

dark

charge

transfer

the

cathode

surface

the

surface

(on. the
in

or

reflected

as high

The

for

excitation
having
the

a low

of

energy

The

of'
is

particles

This
the

poriod

ionize

into

into

the
and

or metastables(G*).

short

keeps

which

time,

of

another
loses

its

emitting

this
while

neutral

or

in

becoming

energy;,

(h')

a quantum

the

emission
of

of

the

material

sputtering
surface

bombardment

substrate

sputtering

energetic

striking

neutralized

a very

and

energy

of

radiation.

effect

and*the

ions,

atom

neutral

ultraviolet

implanted

neutrals

a collision

high

be incorporated

excited

can

the
have

neutrals

an

a collision

absence

ions

they

until

will

or
of

and

these

becoming

surface
case

gas atoms

space

energetical

energy

is

matastable

dark

can either

the

surface),

the

across

collisions15
and

bombardment.

Travelling

some of

ions

ion

collisions

cathode

surface.

space,

The

neutrals.

some of

electron-atom
the

across

the

strike

by

a positive

that

assumes

ionized

are

to

subjected

A theory8

Mechanism

sputter

procedure,

cathode,

Ionization

and

(due
neutrals)

to

small
or

with

(e)
(s).

material

may be

scattered

angle

collisions

back-sputtered.

energy

electrons

secondary

substrate

high

back
with
The

back

to

39
sputtered
of

can

particles

the

metastable
cathode

be

or

system,

(hy)

radiation

and

accelerated

is

in

the

discharge,

is

which

surfaces16,17,18

These

by

also
can

the

atoms

ion,

electron

or

back

to

exposed
affect

to

the

of

stage

itself,

without

injected

ar

an ultraviolet

organic

second

deposition

film

on some parts.

(s+).

ions

The substrate

which

ionized

collisions
as positive

deposit

either

and

insulating

the

procedure

the

cutting

into

the

discharge.

may be:

atoms

1.

Scattered

2.

Ionized

by

electron-atom

3.

Ionized

by

metastable-atom

4.

Transferred

a high
5.

6.

back

to

the

by a collision

(charge

transfer
to

collisions
a collision

with

neutral

Ionized

Scattered

collisions

by

energy

energetic

source

an ion

with

collision)
other

some

the

of

parts

system
7.

Nucleate'with
gas

phase

and

(clusters).
assume
The

metal

and

ions

atoms
when

2.5.1.

Figure

in

particles
Since
neutral

fine

These

ions

the

presents

a model

atoms

of

the

(-1008)
in

charge

cathode

in

particles

particles

behave

will

entering

like
dark

the
gas

can

plasma.

19

atoms

space.

collisions

and

discharge.

a glow

plasma

(equal

form

a negative

and

film

other

is

number;

a low
of

field

electrons

region,
and

electrically
ions),

due

to

40
-

K,-;

HT H
Field tines
410*

lp

1%

ThODE
w("

eI

GO

lp

'}

Gt

Gt

04

Cathode
dark space
Plasma
region

Uftrovtole} n3da4
on
Go% pressure
Io-5v

So

mtorr

...
Mo

Me

Evoporatbn source
ANODE
M= Coating
Substrate

Metal

Note

Material

: The same process

place

on the

back

G= Gas

cathode

dire to

Gs Metastable

and the

scattering

8
Ion pIc+in Mechanisms

Fi

2.5.1

the

will-take

surface

of

field

lines

effect.

the

:. ,,

41
-

difference

the

potential

the

anode,

and

accelerated

neutral

and

place
of

ions

the

is

nature

the

reaching

by

energy
Davis

of

for

It

was

in

ion

the

that

low

process

but

(as

If

(Figure

the

only

the

2.5.2)

of
these

cathode

energies

the

effect
dark

glow

the

to

the

transfer

billiard

are

energy

and change
lead

assumptions

figures

average

is

of metastables
involved

further

is

in

and a neutral,

collisions

(share

in

neutrals

varies

charge

an ion

between

low

and

negative

The number
the

ex-

originate

reasonably-accurate

proved
their

simpler

field

the

Of course,

due to

therefore,

ions

all

of

reported

conditions.

neutral-neutral

can be calculated.
very

obtained

of

different

on ions

that

and

collisions

an error

particles

choosing

electric

edge

can occur

to

was

plating

the

surface

direction).

the

to

order

dischrge

distribution

that

cathode

of

in

determination

arid,

that

from

type

understanding

the

a glow

assumed

linearly

and also

the

to

Teer20

the

glow,

balls

ions

the

negative

collisions

take

will

and

Ion-

space.

of

Vanderslice15

for

energies

dark

region

energy

approach

conditions,

pressions

plasma

important

very

and

cathode'.

and

boundary

the

cathode

space,

and

A theoretical
the

cathode

collisions

this

collisions

determine

the

neutral-neutral
cr"ocsing

the

from

extracted

across

while

these

are

between

in

chapters)

the
and

negligible.

space

and the. mean free

has

a width

path

'L'

between

two

-42--

VZ-o,

V=Vc

W
O
O
V

Figure2.5.2

43
(related

collisions
if

field

the

assumed

to

strength

following

expression

variation

along

the

dark

cathode
space

is

as it

boundary
found

dark

for

space

the

was
the

the

voltage

:
(2.5.3.

number
the

space,

dx, undergone

and_

conditions,

V=7X

Ni

linearly

varies

is

'Q'

gas pressure)is

by applying

above,

If

the

ions

of

number

by these

the

entering
of

in

collisions

ions,

is

the

:
(2-5-4.

Ni
and the

probability

cathode

without

these

of
further

ions

to

the

reach

is

collisions

L-X

e
The number
(Vc

energy

of
-

ions
V)

is

IF
dN =T'6
The total
cathode

energy
is

the

reaching

cathode

_L-X

(2-5.5.

dX

of the

ions

arriving

at

Substituting

and integrating

can be obtained

"22e

the

dE = (V0 - V) e dN

energy

the

with

[2e
E=

NlV

(2.5.6.
an expression

of

this

22

(2.5.7.

+2L2Le

L
If

no collisions

ported

to

the

occurred,
cathode

would

the

total

be equal

energy
to

trans-

NiVice

44
lost

thus

The energy
and their

is

to

transferred

the

neutrals.

is:

energy

En. = NIVice -E
or:
f

EnN1Vce

2e+

1-

(2.5.9.

LLLJ
2e

22e
L

The term

has been neglected

a very

has

it

since

value.

small

total

the

Assuming

of

energy

the

is

ions

9NiVc 20

10
it

Thus,
'energy

than

longer

be neglected

in

ion

the

Using

the
lowest

the

highest

around

the

ions

results

they

play

they
an

more

carry

neutrals

can

no

important

role

process.
for

expressions

neutral
about

is

energy
300

3 kV bias

voltage,
T eV and

approximately

eV.

The

average

in

the

following

energy

is

150eV.
Rxperimental

proved

the

therefore,

and
as

plating
above

the

that

appears

that
are

work

despite
extremely

all

the
accurate.

assumptions,

chapters
these

45
-

2.6.

The Role

of Energetic

Neutrals

in

Adhesive

Obtaining

Looking
adhesion

and the

stresses

expansion

coefficients
ion

the
,
lattice

phenomenon
etching
of

often

has

bombardment

The other

in

is
the

the

factor

of

being

due to

local

heating

the

of

than
But

5keV,

diffusion
the

This

ion
the

result

ions.

energetic

a good adhesion,
is

easy

to

explain
as

materials,
by the

induced

bombardment

with

energetic

21

implantation.
depth

the
22

50
the

to

substrate

centres,

substrate-film

by

the

be

at

and

process

to

interface,

enhanced

created

Fornoncompatible

was ion

high

is

surface

etching'.

leading

alloying

thermal

into

considered

with

deep graded

case

particles

been

main

bond and

nucleation

'ion

called

process

surface

that

dense

very

clean

induced

are

the

are

cleaning

sputter

the

and substrate.

the

defects

creating

film

of

different

e. g.

good

that

opinion

interface

graded

of

the

s&-me time,

very

kind

any

the

due to

plating

during

obtained

the

a good metallurgical

dispersing

In

onto

expressed

by causing

reasons,

films

plated

Ivlattox2

surface

for

an explanation

ion

of

substrate,

clean

for

Films

materials,
21

the

However,

of

implantation

explanation

even

for

cannot

given

energies
be more

.
ions

will

lose

energy

in

collisions

with

46
-

neutrals
with

therefore

and

energies

and

therefore

for

the

ion

is

the

sensibly

and

that

their
the

of

plating
ions

of

mean
order

and

ion

number

and

energy

being

100

150eV

of

experiment23

is

is

A part

mesh.
the

mesh

for

and

the

current

The

substrate,

ultrafinely

mesh
to

between

the
made

at

behind

was

shadowed

was unshadowed

the

mesh
of

optical

lOmtorr
earthed
for

maintained

polished,
immersion

H. T.
is

substrate

millimeters

potential

was

The

process.

evaporation.

gas pressure

discharge
the

part

-4kV

Argon
-

2.6.1.

(B)

potential

plating

(A)

were:

Substrate

rig

a few

prove

neutrals

ion

the

and

conditions

glow

the

substrate

other

direct

Mesh

The

the

to

aimed

energetic

Figure

mesh

of

to

subjected

in

placed

the

and

in

wire
and

the

films

shown

a fine

was

by

played

adhesive

potential

oil

responsible

chapter

appears

a small

and

The experimental

an

energy,

be

cannot

previous

neutrals

role

apparatus

earth

by

it

following

obtaining

cathode

the

of

important

The

acceleration

voltage.
The

in

the

of

similar

bias

the

in

Teer20,

number

the

cathode

interface.

deposition

large

the

reach

implantation

As calculated
by

will

than

smaller

graded

concluded

they

and

substrate

copper,

which

was

then

50 minutes,
were
was

examined

microscope

which

the

of

parts

and

measured.

previously
by

means
indicated

of

3kV

47
-

-1

arson
1.

Substrate

2.

Wire

mesh
3. Vacuum chamber

4. -'vaporation
A=
B=

source

Mesh shadowed part

of the substrate
Unshadovied part
of,. -the-substrate

Ex per Imenlal cirrcincem-en-

Figure2.61

48
that

the

the

substrate

bombardment

Durring

the

dropped

to

the

as

at

the

argon

pressure

were
During

dropped
the

to

the

and

the

A net

mesh

flow

of

was measured

-0.4mA

steel

3kV bias

the

while

boat.

the

the

mesh

detected

be

could

The

from
to

current

current

no

discharge

voltage,

away

and

placed

of

a molybdenum

behind

deposition,

then

were

50 minutes

and

from

coated

lmA,

substrate.

The scratch
tester

of

following

and

evaporated

substrates

to

6mA.

of

copper

mesh,

was

mesh.

to

current

a current

of

lOmtorr

silver

value

to

2.6.2.

Figure

the

due

etched

substrate.

New substrates
behind

in

shown

a steady

deeply

was

bombardment,

drawing

electrons
to

surface

tests

using

and a diamond
films

deposited

indentor,
on both

by means of

examined
and the

results

afnodified

are

microhardness
were

regions

a scanning
presented

performed

on

and were

then

electron
in

Figure

microscope
2.6.3.

and

2.6.4.
Figure
for

2.6.3.

a shows the
deposited

silver

Figure

2.6.3.

silver

film

copper

substrate.

Behind

the

obtained
the
of

mesh,
vacuum

mesh,
by
the

on copper

shows the

deposited

the

adhesion
ion

evaporated

is
films.

good

very

adhesion

behind

the

track

scratch

on the

conventional
adhesion

very

unshadowed

is

poor,

mesh,

of
part

to

that

while,
similar

and

the
of

similar

plating

obtained

away
to

the

from
that

'J

::1''rl (

Figure2S.Z

look,

iaj,

ai.

/'

)ehlrid

-tpie mesh

4.

b)

: sway from

the

co-I

mesh

Fi9vre2.6.3
Silver

on ro7ppe

cratch

test

(diamond)

51
-

deposited

films
is

a &: b

2.6.4.

Figure

the

for

track

scratch

and the

on steel,
good behind

very

also

show the

adhesion

silver
film

the

of

away from

mesh and poor

it.
Figures

2.6.5.

ing

same test

the

indentor

steel
that

and

the

is

while

adhesive

and

tics

of

mesh

are

these

from

As seen

the

The

parts

not

shadowed

expected

since

the

films

is

which

adhesion

But

evaporation

films

deposited

behind

the

of

to

removed

on the

was
It

copper,

are

the
to

that

ion

the

enhanced

the

good

and

sputter
the

could

have

low

current

the
clean

copper

the
was

a
been

have

bombardment.

ions

alloy.

can

represent
must

films.

adhesion

surface

of

their

plated

and

no

mesh

for

they

films.

mesh,

compatible

copper

earthed,

unable
results

for

reason

50 minutes

through

penetrated

and

as

therefore

the
was

substrate

same

copper

diffusion,

during

the

be the

and

oxides

be

silver

could

to

surface.

gas

con-

the

silver

electrons

or

be

to

under

produced

a vacuum

was

mesh,

nonadhesive

barrier

the

were

obtained

giving

case

the

adhesion

the

the

from

away

and

poor

by

characteris-

be a method

diffusion
since

behind

to

proved

the

not

known

Regarding

In

to

equivalent

the

behind

on those

ditions

is

mesh

deposited

one

micrographs,

different.

very

showing

ductile.

deposited

films

the

the

from

away

ended

comparable

are

results

brittle

perform-

a hemispherically

using

the

by

obtained

were

deposited

adhesive
mesh

but

and

film

the

2.6.6.

and

Since

of

copper
bombarded

'4

r1

ems,

jehind

a)

b)

the

from

mesh

the

mesh

Figure2.b.4
Jilver

on steel

;; cratcli

test

(diamond)

y-y''

,,,,.

_"

c;

ti

'
. .
_

F,
iitj

4
-

cl)

-s E:iliiia

-Eile

X.,..

..

r; esn

"___

th V,

41r

b)

way

from

the

mesh

Figure2.6.5
Jilver

Copper
on

Scratch

test

(ball)

44

Ar

rc_

he mesh

r
.
,

b)

frc-.

way

thy:

mesu

Figure2.6.r)'
Silver

on

steel

Scratch

test

(ball-)

55
-

by. energetic

neutrals

energetic

neutrals

Regarding

the

the

mesh,
two

cannot

deposited

adhesion

adhesion

explanation

be that

was

by

energetic

argon

was

by energetic

silver

There

is

their

number

affect

the

to

energetic

particles.

Being

proved

the

so

films,

number

the

that

further
of

the

the
the
diffusion

very

that

good

the

substrate

the

deposition

of

substrate.

was

due

to

is

work

the

low

This

neutrals

the

current

as

play
ion

determine

to
well

with

for

adhesion

required

neutrals

not

bombardment

under

in

but

secondary

energetic

role

could
by

the

the

energetic

they

explained

mesh

ions,

negative

that

small

by

important

extremely

for

and

a fact

by

emitted

therefore

existing

substrate

electrons

plated

of

drawn

the

by

atoms.

adhesion,

measured

behind

and

cleaning

atoms

be

must

current

an

the

a possibility

negative

was

good although

incompatible

The

must

deposition

on steel

was extremely

are

occur.

the

as well.

silver

materials

that

and

as

their

energies.
It
is

has

been
it

started,

is

current

indicating

(usually

a 50A

However,

the

while

most

potentials
expected

observed

that

followed

by

less

ions

a drop

in
to

going

evaporation
the

the

cathodic
cathode

drop).

ionization

for

potential

of

the

evaporated

of

4-

lOeV.

the

metal

that

the

when

atoms

have

metals
it

Therefore
to

be

argon

15.7eV

ionization

would
easily

is

be
ionized

56
-

in

the

followed

plasma

by

in

the

cathodic

the

ion

current

a rise

current.
The

explanation

lie

in

than

fact

the

the
be

due

group

to

form

difficult

to
despite

adhesion
neutrals

the

that

to

the

the

obtained

in

evaporation

capacity

fine
be

drop

the

ionization

could

But,

for

fact

of

that

the

the

plasma,

metal

(clusters)

particles

is

rate

could
higher

or

vapours
and

are

it
will
more

ionized.
low

ionization

must

be

due

efficiency,
to

the

the

energetical

good

57
2.7.

Energies
Ion

the

The

Plating

following
the

energy
by

substrate
the

number

neutrals.

the

to

determine

the

real

and neutrals

lost

in

The
in

Figure

bulk

earthed

to

the

by

cathode

the

energy

The

'c'

and

'd',
its

and

is

substrate

schematically

a vacuum

Tl

the

is

a power

can

copper

the
through

earthed

temperature

made of

measures

to

supply

substrate

bulk

The

chamber.
a heating

which

substrate

shown

the

be indepenmeasured

and

its

with

dimensions

35 x 31 x 9cm.

are:
A wire

ceramic
the

direct,

possible

incorporates

By connecting

heated

The

and

in

a thermocouple

an A-meter.

Tl.

by

in

is

which

was set

temperature.

dently

discharge

glow

determine

to

also

arrangement

and

contacts

is

inflicted

power

the

process.

is

resistor

it

separate

their

inputs

power
Thus,

and

2.7.1,

substrate

the

the

was to

of

power

cathode,

to

determine

to

total

the

idea

to

order

carried

The

inputs.

ions

the

the

in

reaching

energy

neutrals,

simulate

heat

equivalent,

atoms

the

the

to

then,

and

of

also

participation

in

was performed

and

from

ions

Involved

Process

experiment

determine
their

Particles

the

of

mesh with
holder,

a diameter
and

at

of

0.3mm is

a distance

of

fixed

2 mm in

substrate.

The mesh is

connected

to

the

H. T.

supply

and

on a
front

of

58
-

123

65

VACUUM
1.

Earthed

substrate

2.

Heating

resistor

3.

Ceramic

support

4.; Shield

"

5.

Wire

6.

Shield

Tl,

T2 -

mesh
Thermocouple

Figure2.Z1
Ep flmenft arronoement

59
the

represents

be heated

also

the

with

the

its

is

which

mesh

'a'

to

connected

so that

the

'b'.

and

In

thermocouple

the

H. T.
is

can

contact

T2 that

The

discharge

It

a power

a thermocouple

temperature.

also

screened

is

discharge.

glow

by connecting

contacts

there

mesh,

measures

the

of

separately

between

supply

The

cathode

was

wire
carefully
to

confined

the

only.
transmission

geometrical

which

means

mesh

and

that

angle

shown

earthed

the
in
1/4

approximately
electrons

the

strike

Assuming
as

92; 1) of

that

emitted
parts

of

the

earthed

Figure
the

of

by the
the

SUBSTRATE

e2

9cr

1. E9uipotentio! lines
z, Wire mesh

Figure

lines

2.7.2.

it

pass

92j
the

make a 900

rather

that

means

number

mesh will

system

will

is

substrate.

2.7.2.,
total

'A'

mesh

neutrals

equipotential

substrate.

"

the

of

of

go to
than

secondary
some other
to

the

60
-

In

first

the

the

whole

let

in

the

chamber.

Then, the

dischrge

The
the

is

to

are

recorded.

Then,

steps

(by

increasing

the

2.7.3.

Fip; ure
and

Secondary
is

after

discharge
the

making
(which

current

is

in

increased

by

followed

above.

discharge
the

to

the

of

mesh

power.

earthed

substrate
in

discharge

power

Ie

means

power

the

calculated

for

correction

the

electronic
from

be substracted

must

power

the

total

current).

cathodic
is

substrate

the
and

The
positive
riesh.

assuming

The

the

to

current

the

mesh

and by the
discharge

Y,G =5"(I

xV

the

is

then

given

the
is

(watt)

go

be:

total

5/4

by the

electrons

will

the

electrons

cathode

secondary
power

'e)

of

system,
the

leaving

current

ions

of

parts

1/4

that

to

measured

current

electronic

some other

electronic

the

temperatures

constant

voltage)

versus

and plotted

until

power

temperatures

current

electron

remote

2.7.4.
The

to

bias

in

mesh.

cathode

power

versus

plotted

measured

Figure

If

presents

substrate

the

the

the

a certain

as described

same procedure

between

reach

mesh

is

argon

established

and the

maintained

which

is

struck

system

and the

substrate

the

the

of

parts

is

pumping

10-6torr,

of

10 mtorr

of

dischrge

glow

after

experiment,

a pressure

a: pressure

and

earthed

to

system

the

of

stage

Ie.
arriving
leaving

Ul"

_O

tD

SHE

in
64

"

o
p_
ZS

_Z

-0

Lnco
ti
CV

.o

c3qD

s-

J
0

I-

0cr..

coo

ON
to

62
-

dM

h
lV

4
M
_C'.

_CV)

-0

"C

'O

-4-

0
a-

co
_ lV

cri
aV
ILL

"L

u
"
c
4

w
N

_N

0o

63
Ic

total

the

is

the

bias

The

second

V is

the

both

cathodic

by

obtained
temperatures

those

to

bombardment.

plotted

These

heating

versus

to

adjusted

correspondent

discharge

are

is

power

the

of

means

in

power

2.7.3.

Figure

heating

represent

the

real

bombardment,

the

difference

powers

neutral

and

ion

senting

the

power

The

mesh

is

the

ions

and

is

the

pairs

glow

(by

heat

to

is

experiment

substrate

and

temperature

obtain

The

the

and

the

of

stage

heating)

resistive

(V)

voltage

mesh

(A)

current

8% of
by

the

the

bombardment

neutrals,
the

92o of

repre-

process.

the

to

subjected

bombarded

in

lost

the

of

power

the

while

neutrals

by

100% of
substrate

and

the

two

corresponding

secondary

electrons.
Choosing

temperatures
curves,

are

and

possible

to

heating

which

in

Since
for

them

the

(Figure

the

the

real

the

result

of

these

two

direct

the

ion

values

value

correspondent
represents

is

it

by

power

Adding

on.

),

2.7.3.

inflicted

power

from

temperatures

the

power

process.

the

a sufficiently

powers

the

represents

power,

these

curves

determine

discharge

lost

to

TTieater

and substracting
of

on TSG1ow and TMGlow

bombardment.

neutral

power,

determined

corresponding

and

TSHeater

and

discharge

a certain

adjusted

two heaters
long

were

of

period

continuously

kept

to

on simultaneously

time-and

give

the

the
two

64
temperatures,

correspondent

due to heat
The

lost

loss

Power

the

through

radiation

plotted

versus

is

loss

power

is

not

and convection.
in

volt&ge

Figure

2.7.5.
Since
it

the

the

kV,

30%%. This

Using

the

to

easy

From figure
3 kV bias

in

is

power

over

value

later

explained

the

neutrals

the

of

in

this

ions

of

discharge

total

2.7.3.,

Figure

energies

losses,

and these

it

are

it

and neutrals
after

power,

in

presented

the

their

that

energy

to

adhesion

to

other

parts

ions

will

these

plated

figures

their

as their
films.

a
(ions

is

due
of

to

the
75-$076

transfer

coincide

any

number

role

in

neutrals

with

available,

be neglected

determine

as well
ion

which

neutrals

cannot
to

of

the

by

carried
power

loss

for

energy

in

30-

the

With

neutrals

spectrum,

the

total

the
is

cathode)

that

results20.

important

60% of

scattered

results

that

can be concluded

around

being

it

system,

energetic

in

plotted

of the

reaching

considering

Teer's

results

2.7.6.,

and

the

a steady

voltage,

neutrals

energy

reaches

loss

voltage

mtorr

2.7.6.

Figure
,

is

the

the

substracting

it

increasing

calculate

as percentages

of

that

lo

at

constant

(2.10).

chapter

is

was

power
loss

kept

pressure

be noticed

can

2.5.

argon

more

and

and

obtaining

65
-

wf

In
m

ti
N

L1.
_

"0I

f
L

66
-

.
I

-f

r%

w
_N

W
LL-

N
C

a
H
Z

,O

'1

8
Mir

r9i

67
2.8,.

Efficiency

Ionization

Initially,

ion

deposition

of

high

substrate.

The

field

which

lines

throwing

an are

found

to

front

surface,

ionized

it

a clean
electric
for

explanation

the

gas'
at

the

30% of

the

that

30- of
it

therefore,

due to

field,

due

are

coated

that

on the

to

ions

The ionization
percentage

the

those

used

ions

atmos-
in

ion
there

when

effect,

scattering

of

surface6.
throwing
gas

the

power

of

scattering

field

in

the

total

and

lines.

can be calculated

efficiency
of

case,

a thickness

due to
following

experiments
a gas

gas

caused

deposit

in

this

the

front

more

the

in

with

that

appears
is

plating

even

was

will

recent

to

was

being

and

(evaporation

indicated

this

atoms

However,

case

on the

that

lines

the

surface

thickness

field

the

pressures

around

back

been

50%.

even

metal

comparable

surfaces

the

on the

have
in

and

source

considered

evaporation.

electric

30'x,

ioniza-

the

figures

to

1 up

surface.

hidden

being

the

estimated

300 of

follow

back

plating)

less

the

as being

ionson

controversial

was

that

will
the

ion

only

thickness

be around

fact

the

no

the

was

evaporation

film

Since

is

followed

from

of using

phere

ions

and

ranging

using

metal

metal

efficiency

onto

defined

energetic

authors24'25

reported

by

been

power.

Different
tion

has

plating

number

as
of

63
-

particles

striking

cathode

Using

a square
in

surface

the

results

to

current

the

electronic

is

to

the

number

rj
sec. cm2

the

be

From the

'n'

cm2, the

is

the

centimeter

the

ion

density

current

theory

of gases,

number

of

of

Ni

for

is

a given

collisions

received

is

surface

(2.8.1)

number
'u'

and

to

nu

=4

the

lA = 1019

calculated.

centimeter
Nnp

that

mesh subjected

3.5

'p',

by a square

calculate

knowing

mesh,

kinetic

gas pressure

where

possible

of the

can

ion

the

being

( ions

the

substracting

area

bombardment

from

obtained

mesh (after

of ions striking
ions per second.
The total

the

of

a second.

previously

it

current),

centimetre

in

of molecules

the

a cubic
of the

mean velocity

molecules.
If

the

components
(argon)

molecule

dicular

to

the

of
along

and parallel

'c'

velocity

axes

rectangular

to

the

surface

a typical

of

perpen,

are

u, v, w,

then:
c2= u2 + v2
Having

no preferred

values

of u2,

molecules

will

c
It

results:

2=

2c2

(2.8.2.

.+ w2

directions

v2 and w2 taken

in
for

the

gas,

the

all

the

gas ,

)
mean

be equal.

3u2

(2.8.3.

(2.8.4. )

69
which

is

From

the

the

component

theory

of

to

perpendicular

gases

the

miloc2 = 3RT
) it

From (2.8.5.

follows

results

Introducing

0-0
(2.8.1.

u in

Where

No
-

represents

centimetre

is

) it,

results

(2.8.7.

gas at

in

of molecules

atmospheric

a cubic

pressure

constant

gas

the

number

CM2

x 10

is

se

temperature

absolute

of

the

gas

2960K

T=
Another

method

force

is

:m
u

the

given

is

Nnp

calculating

which

is

the

is

is

a molecule

a second

over

f=
where

of

With

integrated

In

19 mol
10

the

R=8.31

the

of

No = 2.68

the

(2.8.6.

Nnp =4nR

-T

u=

-R

(2-8-5.

3RT
M11
0

c2
It

wall.

following:
a wall,

striking

2m7u sf
,
the
as

molecular
calculated

pressure

(2.8.8.
mass
)

(2.8.6.

from

'p

conditions

the

force

cm
applied

on a square

centimetre

of

the

wall

is

70
t

FP-= pig

(2.8.9)
cm2

The number of molecules

of the wall-in
order to
to

equal

Fp is

is

plotted

2.8.13.

the

2m

are

NniP

ion

usual

versus

has

is
is

to

compared

particles

striking

the

Analysing

Figures

2.8.13.

that

noticed
change

in

the

Therefore,

the

efficiency

in

the

bias

substantial

value

voltage

only

of

W.

kV,

The

the

%a
in

are

number

a very

of

surface.
2.8.14.

pressure

ionizations,

it

diode

efficiency.

can

be

little

gives

efficiency.

control

however,
in

value

4.5

ions

total

anf

means to

which

0.1

the

the

of

a classical

increase

0.03. -

cathode

alteration

steady

3-5

being

kV,

low values

extremely

a nearly

that

2.5

under

exceeding

voltages

conclusion

number

to

Figure

2.8.14.

Figure

voltages

voltages

efficiency

The

small

for

in

voltage
in

efficiency

plating

ionization

(2.8.12.1

pressure

0.1% for

be :

x 100

by an increase

0.08

2.8.11.

Figure

then

will

plotted

ionization

in

pressure

can be noticed,

followed
of

and versus

As it

8. -LO)

efficiency

Ief

values

an applied

Pg

versus

The ionization

Its

obtain

1 cm2
force

strike

Fp
Nnp
-_ T _
Nnp

to

necessary

ionization

system,

is

cannot

bring

by varying
a

71
-

. rcd
NCU

LLN

a) b

a}'

O
C

z
in

72
-

u.

A
43

M
co
4\1
4u
cv
LJ..

N
X
v
al

oo

0
.

-73 . E
M1

to

i
.

dy)

g
4
L

s
a
'

..

1
L
4)

>

C
U

.7
(DID

.0

C
r.0

.a

o,.

Cam!
L

,F

74
2. g.

Energy

Neutrals

f
L

Using
it

results
Ni

the

results

that

there

= the

Nn = the

the

ions

will

pass

the

mesh.
Ni

A,

neutrals

and

the

strike

of

ions

the

neutrals

the

of

neutrals
behind

substrate

energy

is

the
=

number

of

the
is

energy

number

of

the

striking
is

the

striking

total

energy

their

with

a geometrical
A%

that

striking

Nn
the
=
-0
.

striking

number

has

mesh

Therefore
the

surface

separates

means

through

their

100-A
100

the

it

eVi

energy

energetic

arrangement
and

cathode

eVn

energy

the

transparency

mean

cathode-substrate

mean

from

of

the

striking

their

with

2.7.,

Section

ions

of

number

the

Since

are

number

surface

in

presented

Nievi

energetic
mesh

100-A
100

energetic
substrate

A
NneVn
100

mesh and

and

neutrals
their

total

Nn Vn

neutrals
and their

total

75
-

Ne = the

number

the

of

secondary

substrate

and

electrons

their

total

striking
is

energy

NJVe
From
I,

2.7.3.

Figure

to

the

the

mesh

and

Ls to

heating

resistive

heat

we
can
,

inputs

due to

the

which

ion,

determine
substrate
be

will

neutral

heat

the

inputs
by

simulated
to

equal

the

bombard-

and electron

ment.
'ti

TdieVi

LS

+ 100-A

N eVn

Nn6Vn + NeeVe

100

(2.9.1.

(2.9.2.

A=92%

i.

N;.
, 1(

is

2)
sec. cm
the

minus

The

energetic

their

neutral-collisions,
of

Ni.

Assuming
an ion

after

being

neutrals

that

has

number

every

crossed

cathodic

current

a result

of

Ie.

current

electronic

the

from

obtained

a mean

a function

Nft is

collision
free

takes

k is

cathode

for

dark

a given

a factor
space

depending
'L'

and

on the
the

mean

length
free

the

following

of

)
the
'e'

path

pressure:

(2.9.4.

has been previously

conditions

results:

(2-9-3.

k=e
'L'

place
it

path,

Nn -- kN1
where

ion-

and

'e'

plotted

can be easily

expression

for

different

calculated

)
p-V

using

76
Vii
.2=(

or

a'2 y 2-1

kT
T2

pTi
V

where

(2.9.5.

the

represents

number

of molecules

per

unit

volume
U- is

the

molecule

is

the

gas

T is

the

absolute

p is

the

gas

The mean free

average

length

without

collision

upon

gas

Using

previously
values
and

argon
.

can

there

is

ranee

15 -

energetic

and depends

in

Figure

2.4.5.

of

25 mtorr

which

for
the

),

2.4.6.

different

the

voltages

2.9.7.

Fi-,gure

no variation

space`L'

and

for

be noticed,

2.9.6.

dark

cathode

plotted
in

and room temperature

bias

a given
L

ratio

means

in

voltage,

the

a constant

pressure

yield

of

neutrals.

For

experiment
namely

the

can travel

molecule

argon

(figures

pressures

As it

for

the

were

as being

a gas molecule

pressure
of

k=e

of

gas.

temperature.

path

plotted

the

of

defined

another

and

values

is

which

with

versus

the

temperature

pressure

over

pressure

plotted

constant

path

The mean free

is

diameter

p=

the

in

conditions

particular

described

in

10 mtorr,

the

Section

2.7.

mean free

which

the

was performed
path

is

ec0.47cm

77
-

(cm)

05

04

0.3

0.2

0.4

to

i5

20

Figure2.9.6

25

30

10. p
(mtorr)

78
-

. r"

'sC
N

Az

C"
0-

CV L

3
Qv

LL-

rc
N

0
b
C
.
N

79
The

dark

cathode

intervals

as

Applying

Davis

an ion

that

shown

before

having

the
is

collision

the

the

the

having

is

transferred
is

and

and
This

le'

the

to

by

accelerated

next

transfer

charge

a neutral

with

collision.

the

across

path

transfer

ion

an

results

space. must

mean free

charge

positive

next

the

a charge

field

electric

dark

collision

becomes

which

neutral

first

k equal

it

theory15,

cathode

to

equal

into.

2.9.8.

Figure

the

entering

a length

means that

in

divided

be

and Vanderslice's

travel

this

L can

space

before

space

collision

with

charge,

becomes

neutral.

it

but

neutral

Thus

it

travels

fact,

an

another

e space

with

with

direction,

space
generate

first

the

a nonenergetic
(share

so
means

(due

to

that,

a total

. ,h ne _kn

and

field),

electric
number

2 -1)

of

change

the

It

nne

()energetic

-(k+2)

dark

will

neutrals

energetic

n=1

can be observed

of

cathode

an ion

k+l
-2

a billiard

effect').

crossing

while

before

in

neutral
energy

and

neutral
energy

'scattering

called

the

of

as an ion.

energetic
this

while

gained

Iefspace

in

collision

It

energy

becomes

colliding
balls

the

keeps

across

accelerated

its

by losing

ion,

The previous

neutrals
ion

(2.9.9. )
that

'according

to

this

theory,

an

80
-

1}

.+

`R

Z16

u
W
Z

ct

positive ion

neutral
energetic

non energeticneutral

Figure29.8

ion
11,

cannot

generate

through

neutrals
number

ions

of

after

transfer
which

undergoing

collisions,

will

ions

Ni

total
from

the

the

ions

negative

ion

in

the

the

space

by the

same

number

of

as being

current,

extracted

glow

dark

the

transfer

we can consider
the

Thus,

cathode

cathode

from

energetic

charge.

the

reach

of

the

of

enter

only

charge

calculated

number

but

subsequent

Therefore

number.

ions

more

field

electric
towards

and accelerated

the

the

cathode.
),

(2.9.9.

From
number

of

it

is

energetic

collisions

neutrals
the

across

An energetic
neutral
with

an ion

than

the

The

or with

is

of

= Nix

nne

and p=
exceeds

the

This

born

one collision
having

in

more

an ion-neutral

in

= Nir2k+1_(k+2)]

number

(2.9.10.

case

of

3 kV bias

18),

Nne thus

Nnp of particles

a second. on a square
energetic

amongst

^ Ni2k+1

cm

(K=e=

total

means that

collisions

least

neutrals

particular

10 mtorr,

cathode

as being

neutral

neutrals

sec.

the

at

another

energetic

the

defined

Nrie

For

by ion-neutral

energy.

number

collision

total

space.
is

neutral

thermal

total

dark

the

calculate

produced

has undergone

which

to

possible

neutrals

themselves,

thus

voltage
calculated
striking

centimetre.
will

have

contributing

further
to

-82-

,.
the

energetic

scattering

effect.

reducing

the

A simplifying
duced
z,

is

from

taking

place,

formed

is

the

cathode

the

number

distance

could
the

thermal

each

end of

Fron

) and

determine
levels

the

heat

at

input

energy

(I. = 9,8...
100
eVn =
ANn

that

that
to

lose

their

conditions

last

took

with

place

(2.9.10)

the

making

determine

the

at

the

charge-transfer

level..
the

(Figure

substrate
),

of neutrals

it

is

to

possible

produced

at

different

2,1,0)
(LS

to

9 ', e'

be produced

all

at

collisions

to

could

(2.9.2.

expression

the

in

possible

paths

comparable

the

energy

is

these

energies

provided

place

cathode,

entering

N,, that

space

took

collisions

2.7.3.

'C'

formed

and from

it

it

conditions,

and in

with

neglected,

of neutrals

number

thus

neutrals

of mean free

the

collisions

2,1,0,

k=9,8...

collisions
,

neutrals

receive
all

91 are

before

the

But,

will

Therefore,

ions.

which

number

cathode

energy.
they

spacings,

intro-

ofletspacings,

10 mtorr

collisions

the

reach

be

could

energetic

9e from

than

further

in

of

this

means that

longer

energy

in

enhancing

Nnp,

that

This

9.

number

3 kV and p=

the

was calculated
is

to

equal

For

the

to

and

that

restriction

determine

to

starting

differences

l
NeeVe)
-

(2.9.11)

83
-

l'

I'

These

energies

I
I!

are

447
vnI
ev

is

:k

very

vicinity

From

Table

The

due

to

sions

collision
the

2.9.1.2.

for

with

Considering
decay

function,

Figure

2.9.13.

level'k;

in

place

that
is

the

to

an ion
and
will

to
due
have

eV.
the

reach

exponentially

reach
to

a'k'level

the

further

-7fact
colli-

neutrals.
this

that
it

was

the

average
150

about

decreases

energy
of

because

surface.

collisions

other

take

a neutral

probability

at

could

kV bias

a3

a certain

a neutral

0 (zero)

results

of

previous

value

cathode
it

probability

the

the

given

of

with

without
that

also

energy

cathode

2.9.12.

transfer

a charge

neutral

2.9.12.

Table

894 178 357 715 143 286 572 1144 228

Table

Note

in

calculated

probability
plotted

is
versus

an

exponential

energy

in

-84-

4-.

Soo
400

300

200

400

'I

Figure2.9.13

-852.10.

Energy

Neutrals

A theoretical
done

be

can

free

path

than

the

an

'e'

the

without

''

the

collision

more

the

energy

that

an ion

than

a mean

have

cannot

during

gained

neutrals

assumption

therefore

and

one

to

approach

by making

travel

cannot

Spectrum

more

acceleration

energy
across

space.
Let

1S
that

consider

us

linearly

from

surface,

as

the

negative
in

shown

field

the

strength

to

glow

the

2.10.1.

Figure

varies

cathode

That

means

dV
d

integrated

which

Vc

[v];

From

gives

boundary

[ic

2X21L

conditions

(2.10.2.

(2.10.3.

kL

K=-2V2
t

The

cathode

rank

interval

space

is

then

Considering

intervals.

equal
the

dark

'm. ,

an

will

gain

ion.
an

devided
an

Eim
= e(Vm - Vm-1)
.

space

across

accelerated
energy

'e'

into

equal

having

the(m-1;

to

(2.10.4)

m)

:
Yr t

"F
#

86
-

'
Ir

x
1

i
W

US

d
U
C

OKI

Q
uff'

. c

C\i

LL

'?

87
-

,,
tr

(2.10.2)

From

calculate

(2.10.3.

and

and

It

is

possible

2Vc

Vm-1

2Vc [X2]m_1)
-T
0

(2. 10.5 )

L-me

-Vc

to

Im.

results

it

m-1

rVVm

[I

),

mL

[L-(m-1)l

-yc
v_
M-1 -

(2.10.6)

these

Introducing

"VC

Eim =

For

this

[2L
-

case

particular
Vc=3

(2.10.4.

into

expressions

e(2m-1)]

) :-

(2.10.7)

kV

10 mtorr

p=
L=9

cm

'e0.5

cm
18

k=
E

is
m

plotted

The highest
about

for
energy

m=k....
that

0
an ion

in

Figure

2.10.8.

can achieve

is

of

330 eV.
Although

an ion

can travel

longer

or

shorter

88
!OEJ
-

j'

llk
3'r

79
Q
d3

co

'x'
w
x

tI

go

No

4 aAJID&
I

-89-

. ti,

than

free

a mean

to

movement
the

a mean free

that

Supposing

place

at

the

shown

in

Figure

energy

the

figures

average

an ion-neutral
the

of

2.10.9.,

for

ion

while

mean free

takes

collision
last

the

eV gained

previous

free

can be obtained.

beginning

320

of

its

we restrict

path,

distribution

energy

,,.

if

path,

'e"space,
comes

as
an

with

accelerated

across

path.

CATHODE
6

e
Figure

It

"

a charge

undergoes
and

neutral
(3)

(1)"is

itself
previous

accelerated

it

transfer

an

neutral

becomes

neutral

(2).

neutral

striking

the

across

can have
The ion
the

collision

becomes

330 eV, but

of

an energy
cathode,

it,

the

while

2.10.9.

just

a last
(1)

'C'

before
charge

then

cathode

energetic

last

neutral

an ion

(1).

space

gaining
the

striking
transfer

becomes

with

with

with

an energetic

an energy

of

330eV.

- 90 The

that

conclusion

be

can

drawn

so far

is

that

both

ions

and neutrals

average

maximum energy

for

kV bias.

a3

Looking

now at

an

energetic
energy

level

having

the

towards

the

cathode,

it

other

neutrals

shown

in

Thus

,a

reach

their

with

eVc

approximately

neutral

produced

Em and

in

at

travelling

undergo

energy

after

equal

the

at

produced

cathode

cathode

collisions

each

with

collision

as

2.10.10.

neutral

an energy

will

shearing

Figure

the

to

equal

'm'

an

the

strike

level

subsequent

'm'

will

collisions

with

(2.10.11.

2m-1
Since
that

an

energetic

loses

its

accelerated,

keeping

charge
the

across

'm'

the
level

energy
will

with
arrive

the

energy
'V

energy

of

across

which

a neutral

the

cathode

an

gained

space,

rated

at

from

produced

previous

(the

Em = Eim+l

Thus,

is

neutral

an ion

't'

Eim+l
(2.10.12)
2m-1

Ei

has bean

plotted

in

Figure

2.10.8.

accele-

produced
is

while

then

(m+l)

the

ion

space)

at

the

91
-

f}

.'

ti
'D

6 (birf,

m-i

o non enerre{ic neutral

p ener e{ic neutral

Fiu re 2.10.10
neutral-neufrolcollisions

m-2

92
-

<.
),

(2.10.12.

Using

the

space,

could

in

Figure

2.10.13.

Assuming
it

energetic,
thermal
neutrals

result

the

At

the

neutrals

end

can

similar

than

the

that

only

those

9 mean

free

paths

that

considered
to

energy
to

be-considered

means
last

that

as

the

they

cathode,
from

obtained

the

experiment.

entire

number

energy
the

be

through

produced

it

it

2.10.14.

Figure

2 eV),

of

surface,

higher

energy

and

an ion

they
of

enters

sequence

collisions

neutral

an

the

that

the

paths,

to

energy
levels

cathode

a neutral

within

is

inputs

Considering

the

of

which

given

have

produced

most

heat

must
(c-o.

energetic

carry

for

the

plot

different

at
the

reach

that

energy

to

possible

produced

dark

shown

are

is

a neutral

which

with

it

of

the

schematically

Below

each level

energetic

subsequent

9 mean free

ion-neutral

are

of

last

and neutral-

shown in
line,.

neutrals

it
which

collisions

as well

carry.
the'k'interval,

Number of
energetic
neutrals

2k-2

there

are

Energy
of
each neutral

13
1
2k-2

2k-3

is

E2
2k-3

are

as

93
2k-4

;,

(2910-15.

E3

2k-4

2k-k

E
2

This

represents

their

energies

cathode

For

dark

the

total
by

by

one

of

neutrals

ion

and
the

crossing

space.

their

the

energies-and

(neutrals
ion

are

number

produced

3 kV and 10 ntorr,

number

k-1
k -k

given

Nn/ion

in

Table

number

of neutrals

percentages
2.10.16.

eVn
(eV)

128

1.37

64,3

50
25

32

12.5

16

14.5

6.2

31

3.1

67

1.6

143

0.8

305

0.4

Table

2.10.16.

in

the

total

94 "

't
- .

C,

g v

a'

'

'

a, 2

4'

E 1

ci
,X

5
4t

ca

'`

"r-+

O\

f/

I'7

v
W

95 -

1234.....

k.....

1E1

22; 4E2

44; 22 ; 4E3
-El

ion)
(heir
(per
of
number neufrals and
enerries

Figure 1O14

-96-

From

2.9.16.,

Table

75 of

it

the

neutrals

energies

of

Several

numbers

are

this

multiplying

that

a'

will

ion,

of neutrals

ions

number

of

ions

will

strike

the

energy

of

300

eV for

a3

kV bias

The

energy

neutral

that
it

the

total

cathode

is

spectrum

the

2)

sec. cm

to

with

since

results

equal

50 -

cathode
but

it

byy1 N

number

number

the

volts,

one

that

concluded

arrive

electron
for

given

be

can

comes

out

an

with

voltage.
drawn

in

2.10.17.

Figure

this

Following

drawn

current

coming
dary

positive

energy

sions

with

ps.rts

of

first

neutrals

by

plating
be

as

the

(plotted

process
follows

the
in

:
is

cathode

(after

for

explanation

due

to

the

the

substracting

secon-

current).

energetical

whole

ion

ions

electrons

The

At

the

) could

2.7.5.

Figure
The

in

lost

power

the

calculation,

neutrals,
from

the

other

the

ions,

neutrals

are
and

in

scattered

could

their
colli-

go to

some

total

energetic

other

system.
a percentage

sight,
equal

taking

practically

to

Sc = cathode

yx

frontal

100

of

the

% should

surface

be

area

lost,

where

97 -

.A
b"
I

ig

ti
ci

N
4.1

.34 o
it 11

LL

m
..
'

N
C'

10

i'

E! 31

"

"L

S
M

d
'^ N

98
the

S=

area
the

at

.t

of

a plane

the

crossing

same distance

the

with

chamber

cathode

surface.

Since

the

all

go to

will

through

lost

energy

ions

the

the

neutrals

the

cathode,
be

should

B.

where

is

) En,

1-

-g-

the

total

transferred

energy

to

the

neutrals.
For

the

98 j% of

experiment

previously

the

should

energy
work

experimental

is

This

neutrals

the

fact

take

place

at

energetic

neutral

a charge

transfer

field

lines

cathode

the

less
are

strong
that

system

the

from

the

along
means that

neutral
it

an

(through

an ion

it

the

Since

travelling

direct

a discreet

at

towards

energetic
other

oriented
low

than

energetic
ionization

bombardment

and

the

field

neutrals
the
is

of

the

cathode

bombardment.

neutral

electric

The conclusion

the

between

angles.

cathode,

energetic
ion

oriented

an

discreet

produced

less

the

collisions

a. nonenergetic
or

But

surface.

Therefore,
is

that

the

approximately

a 30 o loss.

only

collision)

more

will

angle

is

towards
with

colliding

be lost.

showed

due to

described,

is,
will

the
go to

The

more chances
of

parts

the

cathode.
that

deposition
efficiency,

ion

plating

process,,
this

is

a cathode

and due to

orientation

is

99 mainly

due

to

neutral

scattering

random

but

at

discreet

angles

field

lines

power

is

going

a result

which
with

to

the

cathode.

of

the

neutrals

the

is

not

electric

The throwing
scattering.

at

i,
a

yy

100 -

2.11.

Energy

Ions

Spectrum

The

experiments

presented

at

determining

the

aimed

number

energy

distribution

for

the

system.

The

of

argon

voltage

upon

2.11.1.

Experimental

In

of

this

an

the

around
unshielded

the

behind
is

shown

-intended
the

requirements
for

the

also

wire

mesh.

strike

the

built

was

At

of

The

the

2.11.1.1.

to

act

as

an

of

appying

This

ion

one

arrangement

a fixed
to

the

does
very

obtaining
reasons

in

leaving
placed

arrangement
set

up was

voltage

substrate.
not

the

and

analyser

energy

to

same time,

substrste

schmatic

cathode

on the

behind

the

ions

but

be applied

placed

area

Figure

following

studied.

2 mm distance,

at

that

for

bias

and

of

mesh.

in

this

their

plating

arrangement

can

wire

was

only

a variable

and

course,

the

substrate

possibility

mesh

voltage

shield

earthed

are

and

number

they

2.7.1.

Figure

behind

substrate

ion

also

similar

,a

a high

case,

is

the

which

dischrge

prvcsented

ions

of

pressure

energy

part

Arrangement

with

in

this

diode

determine

to

energy

a glow

one

ion

the

order

the

and

effect

in

satisfy
accurate

due

to

to

the

Of
all
results

the

lW.

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-

than

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of

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electrons

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be approxi-

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-

The

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the

are

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guration

but,,, -since

to

followed
to

their

reality

the

confi-

complex.

inaccurate
is

being

results

known

in

this

could

results

-these

giving

more

little

tigation,

in

when

much

leads

to

assumed

surface

substrate

this
L11
;

giving

information

about

to

arrangement

area

prove

the

obtained
inves-

of

by

worthwhile

shape

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ion

energy

in

Figure

spectrum.
Returning
2.11.1.1.,

the

is

mesh

A=

carefully

working

A negative
the

dischrge
voltage

is
(VS)

at
thus
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in

pumped
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argon

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zero

parts

down
let

the

of
in

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discharge

glow

front

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of

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substrate.

a vacuum
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in

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to

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the

torr

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is

potential,

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on the

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Then,

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applied

H. T.

placed

pressure

votage

substrate

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following

quired

the

is

-transparency

all

so

to

which

chamber
and

92 o and

only

whole

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geometrical

shielded

confined
The

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the

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a glow
a negative

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i

103 -

..

increased

slowly
The

to

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(IS)

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until

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the

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mesh

monitored

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and
1)

and

plotted

VS.

versus

2.11.2.

Theoretical

Approach

One explanation
at
a.

the

mesh

to

substrate

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the

A%

of

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being
and

This

neutral

At

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the

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and therefore,

that

field

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and the
simulating

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while

field,

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to

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mesh is

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secondary

arises

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method

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& energetic

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mesh surface.

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electrons

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electric

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particles

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emitted

due

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VS = 0,

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by the
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field,
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to

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and this

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One

approximate

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on a conductive

104

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-x

This

paper.
as

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gives

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presented

approximate
2.11.2.1

Figure

(Vg=O)

SUBSTRATE

42

ti go

10

due to

1.. Electrons

bombardment

neutral

of

the

substrate
2.

by the

Electrons

emitted
bombardment

tic

mesh under

energe-

to

assume

3. Wire mesh (VM)

field

4. Equipotential

Figure

According
that
,

to

this,

approximately

electrons
by the
substrate

emitted
substrate
current.

lines

2.11.2.1.

it

is

reasonable

75 of the
by the

mesh are

and contribute
IS

secondary

to

attracted
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total

-105-

,.
b.

dith

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(increasing)

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that

assuming
to

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having

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That

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e
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,
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surface

metrical
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is

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ions

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probably
by

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with

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overall

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electrical

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surface,
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one

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).

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to

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electronic

determine
for

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their

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to

According

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Figure

the

pass

mesh.
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all

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of

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difference

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The equipotential

that

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VS).
-

Vrj = VS the

C., With

approximately

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the

and sub/tracting

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only
due to

possible

and it

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SUBSTRATE

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electrons

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some other
to

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(vg vM)

1
2
3

J'

Figure 2.19.2.3

107 -

1.

Equipotential

2.

Electrons

emitted

3.

Wire

(Vri

mesh

by

the

substrate

r{,

4.

Electrons

2.11.3.

argon

to

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system
the

the

required

applied

discharge
parts

to

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in

small

steps

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it

voltage.

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this

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current

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V11 =2

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in

plotted
With

Figure

VS = 0,

was detected
no ions
due to

to

the

flow

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kV and p=

under

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electrons

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and Figure

substrate

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10 mtorr,

2.11.3.1.

the

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Experimental

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2.11.3.2.

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emitted

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2.11.3.3c.

Figure

2.11.3.2.

Figure

the

to

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shield

the

to

).

electrons

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electronic

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was assumed

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2.11-. 4.2.,

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2.11.3.2.

111

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the

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2.11.3.2.

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the

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approximate

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ion

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a smooth

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equals

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the

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.

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electrons),

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graph

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112

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Me

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Fiure2M.3.3

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113

axes,

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Figure

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2.11.3.4.
is

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2.11.3.5.

Figure

in

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versus

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represents

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energy

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Davis

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energy

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2.11.3.5.
during

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of
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of

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due

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Since

intermolecular
and

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than
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tribution
function49

N
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Davis

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=exp
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could

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Figure

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to

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the

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5 %.

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theory15,

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( 2.11.3.6.

of

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114 -

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115
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spice,

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118

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the

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than,

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of

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2. g.7.

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for

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Figure

prove

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Therefore,

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the

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2.11.5.

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to

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The

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2.11.5.1.

region.

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Figure

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to

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121

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the

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there-

The

extracted.

the

that

that

is

fact

most

that

probably

spectrum
ion

an

remains

which

fact

constant

remains

regard

the

to

leads

current

higher

at
can

fact

pressure

cathodic

stronger

fore

due

is

increase

becomes

(sharp

the

emission).

electrons

in

giving

further

are

surface

a drop

emission

electron

An

to

leading

eroded

the

on the

micropeaks

and

is

not

neutral

energy

is

higher,

number

of

particles.

t..

123

i.

2.11.6.

Conclusions
4

Although

the

did

section
information

give

was

acquired

and

ion

is

min. ed,
Davis

and
the

glow

discharge

only

are

spectrum,

The

of
had

to

to

that

collisions
are

and

charge

that

energy

parameters

deter-

take

assumption
in

place
for

responsible
transfer

by

calculated

based on the

and

difference

probably
the

process

ion

experimentally

identical

the

the

and

the
the

a
energy

elastic

collisions.

spheres

most

spectrum

Vanderslice

that

some valuable

concerning
of

this

spectrum.

energy

almost

results,

effect

theenezgy

upon
The

the

in

presented

accurate

not

distribution
(p; V)

experiments

due

electrons
be

roughly

between
to
to

the
the

fact
total

approximated.

the

two

that

graphs
the

substrate

is

contribution
current

-124i
s,

t.

CHAPTER3

t
.a

3"
AND

NUCLEATION

INTERFACE.

ADHESION OF ION PLPTED FILMS.

The

experiments

ion.

formation

and
films

3.1.

analysed

film

a thin

film

the

time,

adhesion

processes

that

the

stages

the

interface
ion

of

discussed.

in

its

take

physical
from

due to

mainly

which

early

The
and

different

are

is

and this

the

of

Approach

the

of

nucleation

and Growth

Theoretical

Most

are

chapter

as with

composition.
is

this

of

stages

as well

Nucleation

3.1.1.

early

films,

plated

plated

the

with

concerned

in

presented

the

turn,
place

properties

the

bulk

of

material

microstructure

is

of

dependant

during

film

formation

and during

of nucleation

the

upon

in
film

the

growth-.
Therefore,
films

could

possibly
the

a study

the
Due to

have

is
ion
the

much higher

for

useful

prove

the

controlling

moment,

facing

of nucleation

one of
plating
fact

the

thin

of

ion

understanding

and
which; at

microstructure
most

plated

problems

pressing

technology.
that

energies

ion

plated

than

the

film
vacuum

atoms
evaporated

125 -

difference

the

atoms,

to

expected

be noticed

nucleation
In

the

growth.

of

vacuum

is,

the

formation

of

surface

nuclei

which

Nucleation
taking

Finally,

the

the

into
case

are

metallurgically

the

the

case

film

thermal

energy,

substrate
creates

these

atoms

in
surface

lattice

two

of

the

from

As presented

atoms)

nucleation.

thermo

migrate

in

the

initial

islands.

small
two

simultaneous

the

evaporation.
to

pro-

form

two

the

and

processes

diffusion

lattice

can
(film

materials

dependirg;

of film
take

in

place

& substrate)

compatible49

arriving

different

by

substrate

when

phase

of

called

coalesce

temperature,

the

is

islands

with

on substrate

In

during

small

Parallel

are

growth

film49

continuous

into

grow

initiated

incorporated

are

place

(gas)

is

is

of

involving

(groups

process

of

process

vapour

particles

and

and

cesses

atoms

the

thus

the

is

stages

the

clusters

depositing

on the

early

very

Condensation

small

and

nuclei

two films

process

from

phase.

Other

the

a condensation

solid

callec?

the

evaporation,

transformation

phase

the

in

arid
case

nucleation

to

between

ion
have

case

Section
the

defects

when most

of

higher

than

energies

production

the

to

plating

of nucleation

of vacuum

2.12,

the

energetic
such

the
centres

evaporation

subjection
bombardment

as lattice

the

steps,

of the

126 -

s
:., '
i

defects

point

the

for

ion

density

lattice

it

on the
the

Due to

centres,

substrate

film

(stickThus, "

centres.

to

find

a high

uniformly

distri-

surface.
bombardment,

energetic

atoms

are

from

sputtered

are

centres

and new nucleation

surface

atoms

depths

small

expected

continuous

nonadhesive

in

nucleation

is

of nucleation

buted

as nucleation

of-film

penetration

additional

plating,

act

which

substrate

generates

"cing)

the

Also,
.

centres4'S2
into

and vacancies,

the

the

continuously

produced.
Thermo

bombardment

enert, etic
having

a minimum

the

Therefore,
to

expected

will

be

one

migrating

the

particles
the

are

substrate

growth

remain

small

evaporated
and size

depend

parameters

upon

a continuous
these

around
in

formation

film

of

of

The density

voltage

to

adhesion

process

and

of vacuum

the

since

by the

reduced

probably

be sputtered.

to

easiest

nuclei

is

- migration

size

compared

film

islands6

like

of

generation

nuclei

for

of nuclei,

is

which
the

with

ion

: pressure,

however,
size

plating,
bias

and ratio.:

energetic
particles
depositing
total
particles

where

the

and neutrals

energetic
with

particles
energies

are
higher

the
than

film
the

ions
thermal

le

enerr
This

and

capable
highly

is

ratio

of

producing

sputtering.

dependant

upon

the

ionization

efficiency.

and Growth

Nucleation
the
in

a small

island
film
of

becomes
large

grains

small
will
will

which

a film

will

become
have

persist

even

grow

more

continuous

at

finer

the

grain

grow

the

after

formation

large

a very
in

to

On the

structure.
of

upon

have an

will

facilitating

consisting

a much

effect

beginning

islands

a columnar

that

islands

A film

large

of

and

an essential

film.

continuous,

haiid,

size,
and

number

L;tructuxe

other
of

the

of

structure

have

number

number

than
thickness

a small
structure.

lb

in

3.1.2.

Experimental

In

films
:.

Results

'to

order

study

deposited

glass

and

500 A in

approximately

of

vacuum

nucleation
o

from

an arc

growth,

thickness

carbon

were

source

onto

quantities

of

microscope

slidess

On the

carbon

vacuum

evaporated

films

films,

and ion
the

containing

from

the

glass

then

deposit

by immersion

slide

on transmission

collected

into

were

the

carbon.

detached

were

The small

water.

copper

and then,

plated

copper

distilled

in

alcohol

small

a solution
flakes

electron

of

were

microscope

grids.
The vacuum
of

5x

case

of

pressure
In

the

evaporation
10-6
ion

the

carbon

by sputtering,

ness

of

seconds

before

0.8

1.2

then
(a,

and

As

b).

it

glow

discharge

the

evaporation

is

due

new

to

a background

the

be noticed,
on the

the

islands

parallel

the

thick-

small

can be easily

removed
on a few

was set
started.

were

TEM as

to

vacuum

shown
the

evaporated

in

Figure

nuclei

the

and

growing

larger

formation

the

were

obtained

3.1.1.
are

surface

with

and

not
growth

and

of

a few

nuclei.

The ion
0.8.

copper

can

distributed

coalescing,

owing

the

uniformly
mainly

plating,
which

in

at

torr.

film

mg of

analysed

was performed

plated

and 1.2

and argon

films
mg copper

pressures

of

at

3 and 4.5

by evaporating
kV bias

10 and 20 mtorr.

voltage

A wire

ley

tt

mesh,

attached

glass

slides

to

the

H. T.

was

5,

The

ion

3.1.3.

but,

which

in

can

variation
kept

be

seen

of

the

from
bias

With

the

nuclei

become smaller

is

explained

by the

the

in

increase

bias.

the

to

a higher

also,

the

nuclei

intense

at

are

older

in

due

not

the

voltage,

energy

of

ions

(due

to

the

follows

increase

an

pressure).
nucleation

This
and

centres

to

grow

quantity

of

allowed

which

larger

by

a larger

copper

was

is

result

that

bombarded
as

sputtering.

more nuclei

appear

and become smaller

compared

to

Figure

in

The increase

argon

pressureifrom

20 mtorr,

did

not

seem to

difference

in

the

nucleation.

the

in

number

constant

ones are
to

the

that

of

in

and denser

size

their

the

bombardment.

c,

and the

and the

but

ioni-

parameters

changes

in

current

energetic

evaporated

as

other

increase

in

density

3.1.2.

Figure

size

ion

voltage

leads

the

increase

as well

neutrals,

3.1.2.

higher

the

(a, b),

(the

important

process.

In

in

3.1.2.

voltage

induces

constant)

the

argon

times

increase

Figure

nucleation

in

10 mtorr

efficiency.

it

and

a similar

three

current

a threefold

(a, b, c, d).

of

3 kV and

the

of

2 mm.

3.1.2.

nucleation

ion

front

approximately

Figure

at

an

with

results

zation

the

film,

copper

of

in

shown

shows

plated

pressure

As

are

results

Figure

a distance

at

in

set

remanent

pattern

produce

of

10 mtorr
any marked

as shown in
island

to

type

Figure
growth

3.1.2c
is

130 -

completely
the

ion

porated

ones,

it

growing

in

for

kV,

Comparing

4.5

is

can

for

whereas
size1,

due

mainly

filling

the

nuclei

growing

larger

Figure

3.1.3.

centres

film

ion

plated

in

Figure

shown

but

using

in

is

The
not
of

This

in

dense

the

c),

the

of

conditions

with

mg Cu,

a three

times

increase

It

results

nuclei

it

those
10 mtorr)

was
higher

the

in

the

creation

The growth

centres.
uniform

a copper

current
times

nucleation

other

3 kV,

a three

to

growth

new nucleation

than

he ion

though

As the

nucleation

(0.8

of

distributed

surface.
increasing

of

effect

the

chanching
the

the

system.

much smaller

on the

size..

efficiency.

very
in

in

increased

ionization

of

rather

tendency

islands,

3.1.2.
of

eva-

nonexistent

persist.

similar

a triode

resulting

value,

small

gaps

*3.1.2.

independently

3 kV

formation

presents

vacuum

the

practically

(Figure

the

to

that

is

still

continues

the

with

concluded

islands

in

deposition

films

plated

small

smaller

much

20 mtorr.

for

removed

pressure

current
is.

denbity

a threefold

but
increase

ratio

also

the

sputtering

rate

d position

rate

leads

same quantity

to

slightly

evaporated.

thinner

films,

for

the

131

!l

The

.,

e. g.

parameters,
can
1 from

beginning
can

possibly,
films.

These

first

steps

which

is

the

better

the
the

early

stages
the
for

A large

substrate.

throughout

will
the
overall

and

affect

important

variation

lead
substrate

ion
in

changes
of

towards

distributed,

that

voltage

important

induce
the

is

conclusion

of

thin

nucleation

films

formation
the

adhesion

number
to

of

of

surface

are
the

of

and

the

also

interface
the

nuclei,

a continuous

thicker

of

nucleation

right
and

process

microstructure
of

plating

density,

current
the

ion

film

to

uniformly
interface

therefore

adhesion.

-l,

.
I

0
0

G;

a.

ma Cu

i
- vacuum

evaporated

Albb

vww

loop

40
4(
X 150,000

b.

4-2 mit Cu

Figure3M

vacuum eoporafed

-l

""""i".

;`'

, "ti

11'

;"':

": r

"

1'
1.

11-: ", io

"'

t-0,

i1"

'

a.

""..
j1`"
.

"l"', ,.

"
:!

17""'!

. w"

150,0oo
0 ,6 rnS.Cu on plofed of 3KV& 40
mtorr
,

.-"

..,

"
k,%

f.

{"

i"

:"

.
.

'..

"4

'i
r" r.

r.

0- 4
`. ;..
w
".
"

",.
' /b1.
..

b,

A,

0.8 TT Cu ion pbted

of
,

Figure
3.1.2

"

"""
,_.
",

.0 ' r,
, t

"
".

as

"d

1"
4

41.

'A450,000
4S kV be lo mforr

"

___

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--

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";

s,
,, ter

..

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. R". /.
"i"

k'.

*"""

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, ``e '`, o}~y,

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"L".

b"

i'.

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. y

_.

't.

x 450,000

"' m.Cu ion plated at 4.5 kV& 10mtorr

,

"

X 1501000

d,

30
Cu,
on plated of
o.8 m.

F19ure3.12

'

"v.

Z;:.

C,

& 20 mtorr

1. V'&^

':

;1"-..

4".
.'

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1, 450)000
0 .8 rrd. Cu ion pkrfed
a

W,
3
3I
10
${
miorr

at

I. is the ion curreni dre,vln to-t{)e

cathode in similar p-Vccnditions
bud wifh oufa pos:+ive probe
in a normal diode system
.

Figure3.1.3
3kV -pasiHve prod---acfivcated

136
y
is
"j"

)Y

*r
fk
"

3.2.

Interface

3.2.1.

Experimental

The

ion

of
its

rg

uthor,
.

a graded

interface

and

the

substrate.

The

basic

in

a.

the

formation

case

ion

of

Cu on

S'teel21),

depth

depends

are
an

giving

of

time

for

as

well

as upon

this

which
the

graded

are

materials
( e. g.

compatible
interface

temperature

upon

such

two

whose

and

temperature

nature

the
is

film

of

of

films

plated

of

the

depth.

existance

plating,

when

substrate)
Iad
--.

amount
kept,

and

subs-

materials.

Atomistic

ionization

substrate

film

atoms

mixed

material
and deposit

diffusion

sputtering,

and back
which

back

scattering

will

of

mix with

together,

producing

interface.

The induction
the

due to

mixture4

the

in

the
ion

with

its

measuring

the

the

concerning

connected

reported

(film

sputtering,

c.

and

diffusion,

Thermal

trate

b.

the

are

between

for

reasons

interfaces

films

plated

composition
21924,53

Several

so far

encountered

problems

interface
analysi.

r.
t'

of

substrate
process

a large

number

lattice

leads

possibly

even

of
to
for

defects
an enhanced
non-

"h
F{'

137

26
compatible

materials

(in

depths).

smaller

Ion ' implantat

to

the

to

fact

and

neutrals)

occurs

deep

ener., ies),

determination

of

its

the

of
10-9
order

peak

peals

3A

were

to

the

and depth

10 keV

of

beam

in

used

Scanning

Scanning

was

auger
was <
3 keV

of

energies

is

analysis

Beam diameter

as the

as well

The

a background

approximate

calculate

heights

measured28.
by

removing

succesive

ion

'beam

*The

depths22

10
and

pressure

torr.

The

of

of

against-

layers

composition

sputtering

values

time

peaks
were

by

for
the

elements,

Auger

profiles

atomic
The

the

selected

composition

sputtering.

irrere plotted

the

for

responsible

concentrations

relative
to

though

small

technique

modern

electron

primary

In

very

than

having

neutrals

com.position

ipecurometer

1x

parti-

lower

interface,

a Varian

using

currents

energetic

implantation,

Spectroscopy27.

*lectroi

Electron

of

the

u; in

performed

iL

interface.

a graded

and

:
S,
:.

interface21

energies

in

be

cannot

of

er

bulk

and

happens

it

graded

possible

the

the

The existance

eu

the

of

have

ions

the

therefore

and

that

energy,

(for

highest

'

the

acceleration

it

considered
',

(ions

cles

i roces:

formation

the

in

part

xtake
but
due

another

wns
on
.

were

obtained

means

of

profiles

and approxi-

Dr.
J.
I
by
the
SAES
was
performed
work on
.
K.
Loughboro
University
;h-U.
the
of
';falls
at

138
-

..

`.
:

.Ttb

mate
pu:b

were

obtained
The

yields29,30.

of, high

made

were

depth

sputtering

shed

the

for

values

using
substrates
Nickel

electrolitic

purity

1`
'.
4,

1 polished
The

down

to

torr

3 kV

bias

Prior

to

ion

3 kV and

15 mtorr

cleaning

the

Film
to

was

substrate
a set

give

incompatible
while

silver

e-,)proximately

of

does

not.

for

sputter
evaporation

temperature

rise

process

The

at

bulk

and

temperature

120C.

Cu/Ni

and

metallurgically

materials.

30 minutes

vacuum

depth.

interface

pairs

for

diffusion

the

the

evaporation,

of

effect

influence
the

therefore
reached

the

at

plated
pressure

reason

before

substrates

compeilsate
could

which

The

argon.

ion

argon

cleaned

sputter

vacuui,, i evaporated

and

vacuum

On these

area.

were

15 mtorr
and

plating

substrates

silver

pressure

and

voltage

grade.
1 sq. cm in

and

chamber

were

was

flat,

copper

10-5

to

magnezia

ere
,,.,

surfaces

substrates,
at

Y "

Copper

Ag/Ni

were

chosen

compatible

and

alloyswith

nickel

139
-

,.
tw

3.2.2.

a.

Result

;; Dut ter

A sputter

found

cleaned
a few

and

analysed
to

contain

atmospheric

tering

as

the

in

shown

on the
oxygen

quickly

the

was

surface
and

were
due

sulphur

the

and

ion

But

method.
element

to

the

maximum
to

to

the

sputprofile

introduced

was

sputter
employed

process

profiling

found

v'erp

Argon
due

ion

depth

concentration

both

surface

by

removed

3.2.2.1.

Figure

nickel

the

this

were

in

cleaning
by
,

layers

substrate

contamination.

presented
in

nickel

carbon,

impuritie

These

Nickel

cleaned

concentrations

of

be approximately

1 atomic

percent.

b.

Silver

on _lickel

Silver

and

thermal

and

materials

in

nonexistent

of

concentration
is

case

silver,

is

of vacuum
vacuum
of

to

expected

be

The

evaporation.

evaporated

sputtering

on nickel,

time

in

3.2.2.2.

Figure

A few

incompatible

diffusion

a function

as

plotted

the

two

are

nickel

on the

layers

carbon,
subjection

sulphur
to

surface

and oxygen
atnospheric

were

contaminated

impurities
environment.

due to

with
their

The level

-140

't

6,
a

.Tta

,"f

aT

of contwninating
we"e

found

with

of

50 nm.
be

the

it

the

is

sputter
The

were

The width
is

which
the

very

ing

of

taking

influence

depth

the

the

can

the

200'nm

of

the

of

concerned,

only

argon

to

Even if

then

purity

broadenthe

to

interface.

of

due

occur

diffusion,

as the

same pre

incompatible

will

other

with

Being

vacuum

As far

250 nm

processes

evaporation

effect

sputtering.

be

only

the

processes

the

this

for

50 nit found

of

comparison

achieved,

plating,

the

of

silver

he same

by

Since

diffusion

little

with

plated

topmost

redeposition

ion

during

place

materials,

depth
and

ion

in

were

interface
mix-Lure

atoiaistic

but

was approximately

one.

conditions
the

inducement

associated

removed

broadened

much

deposition

the

3.2.2.3.

on the

quickly

evaporated

vacuum

to

preferential

of

interface

the

of

be

could

cleaning,

the

Figure

found

surface

which

due

to

expected

depth

on effects

:shown in
ere

was

its

profile

contaminants

to

The

technique.

composition

is

be approximately

by

rirofiling

on nickel

found

sputter

caused

knock

and

percent.

of

during

interface

1 atomic

soi: 1e diffusion

defects

sputtering

in. the

interface

broadening

by

likely

was

a sharp

the

lattice

than

_iterface

both

most

less

Although

caused
of

tolbe

found,

(s, 0)

species

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interface
than
the

and oxygen

the

due to
be

must

diffusion.

interface
peaks. viere

is
present

141
14

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total

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0.8

4.

the

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Conner

iovelc

of

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did

ot

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impurity
of

were

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contrast

of

the

interfaces

were

evaporated

and

280
3.2.2.5.

explanation

for

to

raised

for

ion

was
few

the

Since

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and

evaporated
seconds,

surface

temperatures
and ion

plat

there

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of

cf .

the
was

films
shown

the

to

the

for

both

and

were

Figures

surface

to
prior

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lasted

`. down and therefore,

vacuum

material
only

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btained

width

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as

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3.2.2.4.

film

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similar
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depth
C

of

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3,2,3,

ion

Conclusions

The

results

Since

the

result

of

interface,

this

compatible
due

inducement

of

noncompatible

raixing

and

the

interface

materials

to

high

high

to

the

prove

film

plated

graded

local

is

main
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factors

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physical

temperatures
defects

lattice

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and
the

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particles

energetic
For

ion

a deep graded
for

seem

2.1.2.

Section

of

diffusion

b.

in

good adhesion

responsible
For

above

presented

drawn

conclusions

a.

films.

plated,

materials

redeposition

of

atomistic

film

and

ls.
eria.
r>.

lb

substrate

14

k'
R

+.
.
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r

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Adhesion

3.3;.

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Plated

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Determining

it

4.

D. LT.Ivlattox
technique2

plating

by

other
to

order

to

extremely

vacuum

techniques.

obtain

a good adhesion,

clean

taminating

It

substrate
(mainly

layers

weak and brittle

that

was stated
it

oxides)

of

deposited

is

to

of

which

lead

film

and

between

in

required

free

surface,

interface

ion

adhesion

films

with

the

some factors

good

compared

a very

describe

presented

films8

plated

have

the

first
he

and

determined

which
ion

the

was

conto

, substrate.
determinant

Another
was

to

considered
the

by

obtained

be the

his

by

diffusion,

due

of

compatible

materials)

production
vacancies

which

diffusion

process.

authors21
into

the

materials)
film
and

and

deep,

graded

have

ion

defects
effect

material
onto

the

to

of

substrate.

case

as

film

for

to

the

the

and other

physical'mixing
(due

caused

enhancing

of

(mainly

the

the

such

by Mattox

the

be

(in

due

also

into

atoms
can

implantation

with

combined

film

adhesion

interface

temperatures

lattice

substrate

substrate

the

a good

penetration

and

given

was the

of

surface

explanation

redeposition

high

to

dense

of

Another

for

penetration

lattice.

substrate

factor

the

atoms

noncompatible
of
sputtering)

now the

Considering
in

obtained
'ions
", '

and

this

work

adhesion

in

ion

alloying

materials,

most

for

has

been

is

in
21

reported

the

the
in

rise

good

case

the

of

surface
be the

could

the

good adhesion
or for

materials
on ceramics,

depths

of

cannot

be a. viable.

and

Colligo22

5 keV,

the

the

plastic

or

several

of

it

explanation

demonstrated
depth

as

microns

for

that

implantation

is

0
50 A. .

energies
although

there

having

With

ionization
0.1

around
"
total

number

for

of

in

neutrals

3 kV bias
to

the

have

voltage,
total

an extremely
energy.

values

of

during
number

small
the

deposited

as demonstrated

arriving

values

an extremely

be responsible

cannot

having

% and even lower

voltage

acceleration

efficiencies

such

position,

full

the

in

have

ions

3 kV bias

be some ions

could

number,

small

550 eV for

0-

bulk

the

demonstrated,

as previously
ranging

equal

in

explain

films

of metal.

of

about

for

to

non - alloying

Carter

energies

But,

for

diffusion

enhanced

implantation

bince

But

the

the

substrates.

organic
Ion

be:

could

of

energies

reasons

due to

More difficult

deposition

the

explanation.

probable

obtained

real

plating

the

temperature,

previously

regarding

the

neutrals,

results

the
of

good adhesion

de-

ions
of

the

of

the

particles.
this

the

bulk

ranging

0-

work,

energies

and a number

number

of

ions

550 eV

of neutrals.
reach

the

cathode

150 -

with

energies

small

number

arrive

with
it

to

to

In
diffusion

ions

plating

of

energetic
neutrals

ion

it

the

of

3 kV bias.
(compared

be

can

highest

of

to

energies.

the

due to

role

energetic

very

due

materials,

by the

is

in

occur

this

an important

with

implantation

might

cpmpatible

is

the

local

bombardment

with

and neutrals.
the

case

diffusion

some

by

This

the

in

the

growth,

dense

in

the

which

-the overall
these

formation

stages

of

the

the

inducement

substrate

(by

and

the

fact

the

centres
for

to

the

strongholds

The film

adhesion.

of

formation

adhesive

very
in

and

sputtering)

to

and

of new centres

deposition

nucleation

removal

represent

nucleation

to

during

centres,

film

materials,

bombardment.

particles

nucleation

substrate,

around

(vacancies)

early

film

nonadhesive

due

bombardment

to

leads

compatible

occur,

energetic

continuous

mainly

non

might

deffects

high

lattice

the

case

produced

In

for

ion

energies

and

with

plays

heating

low

although

ions

the

i) that

150 eV for

of about

(sticking),

and

neutrals

0.1

energetic

reported),

question,
depths

small

of

relatively

previously

of

that

number

number

these

those

out

of

a small

of

mean energy

Owing

of

can be concluded

and a large

overall

a very

maximum energy.

deposition

ions.
,

to

(approximately

ions

of
this

Therefore,
the

550 eV as compared

of

parallell
nucleation

grows
with
due to

151 -

a,

the
Also,

'

during

atoms
or

are

to

and

with

energetic

leads

materials

However,

when using

means that

which
patible,

are

for

that

means
lattice,
non

into

knocked

some

high

As

adhesion
-

copper

lattice

energies

and

diffusion

ion

Removal
during

for

lead

which

take

this
bom-

surface

some

in-a

a highly

atoms
again

deffective
even

place

with

materials.
the

a conclusion,

of

could

in

the

of

films

plated

for

reasons

are

oxides

and other

the

sputter

cleaning

Removal,
nonadhesive
formation

by energetic

the

impurity

bombardment,
during

particles
and throughout

good

of

the

the

layers

of

any

interface

deposition

period
Penetration
-

of

film

atoms

interpe0
of 40 A

explanation

a result

film

ae incom-

place

SIMS analysis,

the

compatible

as

the

during

bardment

take

Some other

This

composition.

materials

could

scattered

a mixed

a depth

over

the

although

be that

could

result

in

graded

and copper

lattice.

defective

are

of

ions

as

neutrals).

deposition

diffusion

some

and

SILTS, Ahmed26 detected

lead

of

netration

the

these

some of

substrate

energetic

layer,

substrate

the

neutrals
(as

to

and

to

return

substrate

phenomenon

substrate

sputtering,

ionized

the

ent.

formation,

by

removed

collide

back

interface

the

is

material
,,

bombard,

energetic

continuous

(ions-and

neutrals)

-152f

into

F
n

the

to-depths

substrate,

Enhanced
local

physical

diffusion

temperature

induced

(for

bombardment

lattice

(for

compatible

Mixing
-

during

due to

of

the

high

energetic

materials)
inducement

of

bombardment

and noncompatible

and redeposition

materials

by the

due to=the

defects

high

Angstroms.

due to

compatible

diffusion

Enhanced
_

few

o .a

film

sputtering,

materials)
and substrate

ionization

and

scattering
Formation
-

of

distributed
to
4

the

dense,
nucleation

substrate.

relatively
centres,

uniform
very

adherent

153
-

fit!

yj,

CHAPTER

.,

CHARACTERISTICS

FILMS

THIN

The internal
to

appear

determinant

be

chemical

behaviour

friction

coefficient,

A dense

film

less

protection

the

with

film
and

physical

resistance,

strength,

corrosion

cohesion,

is

preferred

high

internal

and a porous

to

a thin

affecting

adhesion,

or buckle

will

of

deposit

wear

A film

crack

the

of

microstructure

applications.

The main

for

ductility,

resistance,

"

characteristics

etc.
different

for

stresses

structure

offers

corrosion.
of

characteristics

a thin

film

are

morphology

surface

- microstructure

This

lattice

crystallite

internal

film

chapter

methods

of

parameters
size
strain

thickness

presents
determining

and uniformity

a theoretical
thin

film

approach
characteristics.

to

the

-154Ga

4.1.

Surface

Morphology

and

rr,

Film

There
the

and

two

Microstructure

characteristics

i. icrostructure

morphology

is

the

of

Average

grain

generally

surface

by means

analyzed

in

reflected
be

can

the

easily'

Electron

be measured

can

size

which

a Scanning

of

interdependant

are

Microscope.

on the

micro-

graphs.

In

the

case
is

aspect

to

burface,

the

film

one deposited

to

method

deposited

on a frontal
of

capability

sight
of

films

uniform

produce

important

one very

on an out
the

reflects

which

coating

films,

plated

compare

with

surface

ion

of

the

on complex

substrates.

Regarding
31

Demchishin

the

film

4.1.1.

formed

by condensation

The

This

is

structure

kinetic

of

sputtered
Out

worst

highly

of

one is

directly

the

a great
copper
the
the

defective

three

to
from

upon

arriving

influence

films

solid
vapour

temperature

film

stage.
and

(ions

particles

demonstrated
upon

the

and

shown in

of merrit

refers

and Thornton32

and neutrals)
has

model

dependant

of

energy

pressure

a figure

presented

Figure

Movchan

microstructure,

that

gas

microstructure

films.
presented

tapered

structure.

structures,

crystallites

which

the
is

155 -

I Tapered
crystallites

f1

j(

I1.

Columnarstructure

45

III

Equaxed grains

Movchan and Demthistiin

hin
model o4.

Figure4.1.1

-F'm sfructure5 ,

e'

156
-

r
E
-

Film

adhesion

between

rV

film

the

of

the

conical

affected,

and the

rY

be

could

concoct

is

substrate

as shown in

growth

the

since

on the

Figure

111
,

contact

peaks

4.1.1:

film

SUBSTRATE

Figure

the

Generally,
structure

towards.

of having
the

preferred

the

the

number

of

small

columns

directed

Crystallite
the

columns

crystallites

for

leads
while

of

peaks

of
to
the

the

are

which

columnar

the
the

and valleys
surface
valleys

peaks

grow

growth

size
made of
have

(due

or due to
being
faster

could

assumes

which

presented7

one previously

microroughness

shadowed

of the

showed the

orientation.

formation

process),

deposits

evaporation"source33.
that

1; A.
/,

exceeds

axis

indicated

a columnar

present

thickness

The explanation
be the

films

plated

beam evaporated

measurements
a large

ion

when their

Electron
property

4.1.1.

to
the

that

the
nucleation

heavily
since

they

are

157
directly

to

exposed

the

stream

film

of

atoms.

RIM atoms

t
A

8
Columnarstructure

A. Exposed

area

B, Shadowed area
6

Figure

the

In
deposition,
ion

For

remove
is

the

the

same

could

this

effect

high

higher
be

is

of

Since

are

which

forward

sputtering

valleys.

But

pressures

for

rates

sputtering
(for

sputter

parameters
the

could

substrate

bombardment,

particles

peaks

and

unremovable.

structure.

energetic

the

evaporation

variation

columnar

the

fill

vacuum

the

time,

obtained,
and

of

to

erode

could

case

plating,

exposed

could

4.1.2.

more
and
this
(to

a massive

this
in

exposed

and

back

scattering
to

effect
erode
back

the

be

peaks)

scattering)

required.

Another

method

of

removing

the

columnar

structure

158
-

.A

is

to

the

aneal

' presents

4.1.3.

Table

of

peratures

deposition

after

recrystallization

relief,

stress

film

and

the

grain

growth.
tem-

recrystallization

34

some more common metals

Table

in

resulting

4.1.3.

Approximative

Metal

Melting

point

recrystallization
temperatures(C)

Nickel

600

1455

Iron

450

1533

Copper

200

1083

'Aluminium

150

660

Magnezium

150

651

Zinc

Room temp.

419

Lead

Room temp.

327

Tin

Room temp.

232

This
point

it

is

since

produce

unwanted

changes

structure.

requires

a long

method

and

Carbide35,
structure

Two methods

At
time,

sometimes
even
was

are

after
still

most

it
as

low
for

acceptable

not

materials,

internal

for

applied

point

melting
could

but

films

be

could

method

the
is
in

heating

high

a high

temperature

in

substrate

the

same time,
a very
the

melting

anealing

since

uneconomical

case

of

Titanium

it,

the

for

observing

columnar

present.

suitable

thin

159
M *.

film

microstructure
a.

Cross

sectioning

gical

mounting

followed

by

metallur-

and

polished
is

then

cope
cross
in

b.

an

the

this

Fracture

cross

ion

the

substrate

which

Scanning

Electron

plated

the

an

immersion
of

finely
The

this

optical
lens.

type

section
micros-

A typical

is

presented

4.1.4.

Figure

work,

then
etched.

using

oil

section

by breaking

Ili

chemically

analysed

and

is

which

second

films

section
film
is

which
together

then

is

obtained
the

with

analysed

in

Microscope.

method

microstructure.

was used

to

analyse

1C(

"

=--"

...

4.

E'! : otro-plated

2. Ci

nickel

mically

3. i1iccel

etched

substrl.

(for

protection
edge
retention)

film

copper

Le

Figure4:x.4
-! 0 ?,
at

ot,.Lck

3 kV and

u ippper
-k) intorr

film,

ion

plated

ar 7;or1 pressure

on nickel
.

and

Jl

4.2.

Parameters

Lattice

Metals

their

solidify,

of

a lattice

such

by

surrounded

are
free

common metals

main

types

of

cubic,

body

packed

as

the

cubic

in

Figure

shown

as

shown

solid

Each

of

the

as

shown

the
same

orientation

4.2.3.

and

the

the

metal
as

of

the

grain,

the

axes
but

one grain

to

another

property

is

called

atoms.

conditions
their

a multitude

same direction

This
of

have

each

from

vary

when certain

crystallites
direction

could

orientation

crystalline

Sometimes,

in

all

Figure

in

are

structure

of

up
In

cells.
point

direction

this

grain

built

is

grains

cells

atoms

4.2.2.

crystalline

small
of

the

centred

represent

a pure

of

examination

Figure

in

shown

The

three

close

They

units.

a polygonal

reveals

surface

the

of

spheres.
ic

Microsco;

through

: face

4.2.1..

points

maintained.

hexagonal

and

crystalline

one

lattice

space

metalic

is

ions

rapidly

density
in

The

positive

moving

crystallize

centred

smallest

by

occupied

a uniform

Most

in

positions

Lattice'.

electrons

so that

metal

fixed

'space

called

pattern

and when they

substances

atoms-take

regular

the

crystalline

are

axis

phenomenon

are

achieved,

pointing

in

is

called

all

the
preferred

,.-

162

t"

tF-,

11

a.

Face

centred

b.

cubic

centred

lattice.

lattice.
Ex:

Body

Ex:

Cu, Al, Ni, Ag.

w,Cr, Mo.

Cc.

Hexagonal

close

packed

lattice

Ex : Zn, 1V2g,
Ti, Cd.

Flure4.2.1
The

types
'An
.

of

space

lattices

cubic

1G3 -

.-

Figure

4.2.2.

fJ

I""

Figure

the

If
is

orientation
the

different,

in

arranged

not

lattices

film

substrate

lattices

must

a good adhesion,
in

the

of

one lattice

case

in

at

the

grain

boundary

space

a thing

together
that

of noncompatible
into

the

when two
fit

the

other

the

are

so that
fit

to

the
each

is
it

grains,

means

different.

be

with

lattice

structure
of

will

each grain

grains

boundary

happens

and the

space

atoms

structure

properties

The same thing

the

neighbouring

grain

the

from

their

that

two

the

Since

different

atoms

of

a regular

the

of

other.

4.2.3.

interface
completely
in

is

order

different
to

obtain'

even more difficult

materials
is

between

not

when diffusion
possible.

the

'

d ,'"

.f

164 -

"_
r

4.2.4.

Figure

It

has

(more

been

than

stronger

films,

the

while

for

boundaries

grain
therefore

a large

boundary)

could

for

proved
the

boundary

grain

high.
are

boundaries

grain

for

grain
resistant

temperatures,

working

than

weaker

are

a finer

be desired

could

low

relatively

therefore

grains,

boundary)

grain

at

4that

temperatures,

working

Misfit
-

the

grains

grain

structure

(less

be useful

as

in

shown

the
and

grain
Figure

4.2.5.

percrfure
Transcrysta (line

1nTercrysiouinefoIture

pai! ure

Figure

4.2.5.

165
-

:
:'
"'

If

in

a crystal

representing

and'choosing

three

unit

on the

axes

e. g.

dimensions

three
(parametric

lengths

units)

t':

three

corresponding

to

the

called

of

al
7-v

a2P a3,

unit

lengths

the

three

points

determine

a plane

plane.

parametric

The intercept
expressed

these

ai,

any plane

as fractions

of

the

with
the

three

axes
units

parametric

are

a3
a2
,
,

h,
After

L'
removing

(h, k, G) are
cutting

the

the

common factors

the

Miller

can define

obtained

and they

crystal

as shown in

Figure

indices

any plane
4.2.6.

Figure

4.2.6.

166
I

h,

k, e

the

in

Because
times
is

in

of

a 'form'

called

respect

which

repeated.

axes,

and

All

planes
the

By

joining

4 series

of

parallel

obtained

each

obtained

give

by

completely

the

distances
alorgthe

between

the

the

unic

cell

bo,

col

and

of

a space

'unic

cells'

side

a space

dimensions
These

by

lattice,
are
unit

and

of

is
side.

lattice,

one

must

lattice

neighbouring

usually

are

space

cells

are

with

a unique

structure

"i

**

in

whole

directions.

h, C)

are:

The

three

{k,

elements

a complete

between

planes

crystal

containing

define

some-

symetry.

sided

these

packing

To

points

it

of

the

are

symetry

syrnetry

points

by

of

incorporated

pattern.

crystal

of

of

the

'family'

similar

represented

These

are

crystals

of

elements

centres

lattice.

the

some planes

some parts

symetrically

indices

crystal.

is

and

and

a whole

collection

can have

A crystal
to

the

the

and

These

represent

elements,

symetry

repeated

k, E ).

(h,

is

parantheses
planes

parallel

common divisor

without

plane

parametric

enclosed
of

integers

are
,

the

dimensions
designated

angles
determine
as

[a0,

167
the
by

crystals

of

the

is

change

the

result

by the

rays

_: in

the

beam is

when

certain

geometrical

which

are

sented

expressed

space

process

a
lattice

by

scattering
a

scattering).
this

conditions
Bragg's

of

without

(coherent

produced

by

diffrac-tion3S,

ray
of

wavelength

A diffracted

in

X-

of

phenomenon

37,3g

phenomenon
are

Law and

satisfied
are

repre-

4.2.7.

Figure

loitice
space

sin A

4.2.7.

Figure
Lift'roction.

Bragg'

is
Law
s
n

where

of

the

X-

Rays

:
2d ; in9

(4.2.8.

-166
1

is

integer

an

the

giving

order

the

of

reflection

is

the

wavelength

is

the

interplanar

atomic
e

both

the

of

unit
the

determination

tnd

the

of

interplanar

lographic

boy

and

and

plane

beams,

analysing
leads

effects,

shape

and

orientation

to

the

identification

leads

to
of

substance.

The

means

succesive

reflected

angles

size,
also

and

cell

atomic

diffraction

the
the

about

the

and the

incidence

of

positions

knowledge
the

incident

the

RaJys

x-

between
spacing
the crystal

between

angle

different

Choosing

in

planes

the

is

of the

planes
the

the

dimensions
for

spacing
is

calculation

referred

to

of

the

different
as

crystal-

'indexing',

of

the

dimensions

are

the

cubic

cell

unit

of

and
d,

ao,

co.

The easiest

to"index

a0= bo= co .-

lattices

where

169 -

;
,.
:;
F
.

C
:

4.3.

.
'- .

Cjystallite

Size

and

Crystallite

size

or

crystallite

composing

Internal

Strain

1 ,

ofa

from

determined

the

pure

by the

broadening'p'

is

its

a constant

(h, k, e)

the

Generally,

determination

line

measured

The

to

equal

crystallographic
are

and

unity

rays

diffractometer

at

broadening

of

the

half

of

and

of

the

by using
is

breadth
the

frequently

x-

in

plane

made.

obtained

line

diffraction

a chart
x-

the

diffraction

x -, ray

0
GsL(h, (A

measurements

conventional

can be

tabulated36.

indicate

the

which

L ( )

dimensions

a powder,

approximately

are

values

niain

equation

k, e )=-

the

rays

of

handy

noted

of
as

the
B1

(4.3.2. )

=B1-b1

where

Bl

is

the

half

breadth

as experimentally

breadth

of a line

calculated
bl

is

the

half

for

a diffraction

intensity

is

produced

170

ro

under
t'F

similar

geometrical

a cristallite
R
loon
and is

with

material
of

excess

instrumental

and lattice

strains
the

separate

two

Internal

film

possibility

intrinsic
The

is

because,

in

to

to

used

Integral

of

if

If
to

important

very

a tensile

stress

and there

contract

a compressive

expand

a thin

thermal

is

the

stress

and there

film

is

can be caused

coefficients

during

substrate

size

the

buckling.

stress

by different

film

a thin

tends

of

Internal

method

the

is

pattern

crystallite

is

cracking.

film

the

of

often

tends

of

occurs,

the

in

film

possibility

the

called

and a method

quality

the

exists,

usually

"

stress

the

in

well

diffraction

rays

effect

effects

Breadths39'40,41

for

x-

by a combined

produced

size

broadening.

of the

The broadening

by

conditions

the

of

film

and secondly,

cooling

firstly
and
by

causes42.

most

usual

film

a thin

methods

are

of

cantilever
internal
stress

the
-

broadening

measures

method which
film
during

interferometric

line

in

stresses

the

the

measuring

the

growth

method
of

the

x-

rays

diffraction

pattern

The first
(tens

of

method

showed that

angstroms),

the

ion

for

small

Plated

thichnesses

films

are

stress

I- /'I

free

in

this

t1s

the

ciiueo
r
OU:

tiii

becomes
the

for

slightly
In

by

indicates

x-

the

lattice

the

mnount

advan-i, u es

the

of

a nondestructive

of

stress

or

the

crystallite

in

the

respective

X-

rays

the

elastic

or

even xdecreases

in
which

(strain)

in

the

there

and

the

stress

kind
be

can

either

that

internal

of

elongated

or

plane.

procedures

can only

compressed

determine

stresses.

The elastic

stress
is

'e'

strain

strain

defined

is

relationship
as

(4.3.3.

where
body
The
single

bf
whose
strain

is

determined

crystallographic

diffraction

it

measurements
the

compressive)

The

--Li stress.

no need to
(
the unstressed

in

material

being

which

fact

is

line

em; ployed,
;pv.ttern

intern,

lie

the

is

diffraction

lattice

of

is

as

film

stress

dimensions,

crystallite
(tensile

the

internal

distorsion

Corelating

the

with

qid

method

rays

method

qonditions.

es

di scon_1

increase

the

third

method

: easurements

E;-ti?

a sharp

constant

the

the

of

is

fi]_i: is.

work,

broadening

is

of

thicker

this

caused

value

t.rratelly

appro::.

rc iains

The

there

the

of

film
increa

'i,! iiclcness

continuous,

value

make

the

is

tte
initial

is

direction

change

in

length

and

was
by

produced
:

the

length

of

a stressed

e.

a stress

yr

acting

in

(4.3.4. )

e
,i

Hooke'

is

which

to

When starting

of

an

x-

ray

line

profile

the

Rachinger

koL1

line

the

ot2

are

profiles

but

intensity

the

identical

it

29

of oCz and

is

is

the
the

speed

line

half

one

towards

with

kit,

and

and

that

of

the

o.,

larger

(4.3.5.

difference

the

in

that

reflections,

O(

also

and the
to

ray

integral

both
After

profiles.
pure

line

separate

and lattice
x-

that

assumed

Gaussian

possible
size

pur-

shape

is

the

profile
the

breadths

applying
is

method

d2

profiles

this

correc-

determined,

on the
line

wavelength

0
(A)

and

influence

distorsion

diffraction

o(,

c-1)

tion

this

(k)

tan6

=2

A\

where

are

work

by-:

angles

It

this

the

in
is

pure

chart

pure
that

assumed

from

shifted

for

a fast

and

intensity

reflection

the
in

and

obtain

is

It

broadening

all

of

was used

to

order

s modulus.
line

determined,

speed

accuracy.

maximum

first

scanning
in

the

measure

correction43

chosen

were

be

must

Young'

is

reflection,

A low

pose.

I E"

s Law.

and for

of

it

crystallite

broadening
this

can be used.

of

purpose,

is

173
A

breadth

The integral
of

devided

by the

Bl

line

the

intensity

yl`
=

of

length

The integral
(A rl))

units

GVilson44,
by

of

to

of the

line

the

line

profile.
in's'

As shown by
breadth

profile
alone

sinne
4e

same

and the

can be written

(radians).

(strain)

is

2es
=
=

generated

2e
hkE
(4-3.7.

scale

:
)Di = 4e tan6

( rr 28

on the'20'

in

height

integral

on -the' s'

having
profile

breadth

(d' v)D

or

significance

by the

the

distorsion

the

geometrical

a rectangle

ortWunits

the

(4-3.6.

enclosed

profile

background

the

)d(28)

has the

area

equal

integrated

width

the

with

area

above

profile

I(20

The integral
the

as the

peak height.

being

defined

is

a direction

scale

perpendicular

designates

integral

designates

distorsion

S=

2 sin

( '1)

to

the

(h, k, e)

plane.

breadth
effect

(4.3.8")

,;

174
-

:,
i

The

integral

breadth

profile

crystallite

be

can

size

generated

by the

from

Scherrer

obtained

equation
P'

Lk=

(4.3.9.

pcosh

where
L

is

the

is

a constant

dimension

main

usually

the

of

crystallite
to

equal

unity

=B-b
B

is

the

integral

is

the

geometrical

breadth)

breadth
(instrumental
by a reference

generated

powder with crystallite

in excess of 1000

From

Scherrer
by

generated

the

equation,
the

( s)i

integral

crystallite

size

breadth

profile
is

size

well

on the's'scale

=L

(4.3.10.
2e )S

The

designates

integral

designates

size

either

of

combination

broadening
based

k--= L
cosh

effect

on the
both

the

Cauchy

scale

breadth
effect

two

dS)o
(

assumption

on the12A'

effect
gives the overall
[g(20)]o
and it is
or

that

or both

the

two

Gaussian

effects
as'regards

are
the

175
-

shapes

of

it

Therefore

two

the

profiles.
be written

can

(ds)S + (ds)D
( Cauchy
[sS]

[(g5)D]

2+

(Gaussian

Making

-the substitutions

(Js)o=L+2

es

Experimental
broadening
function

results

equation

the

while
by

approximated
was

have

found

a2
G'

-1-(

well
the

function.

by Halder

B'
BB

of

effect

a Cauchy

that

shown

be approximated

can

2
Gaussian)

(4.3.11.

(4.3.12.

and

the
by

strain
a Gaussian

can

size

be

An approximate
Yagner45

(4.3.13")
or

:
A
B_

1-.

(B

(2 es)2

2=(L)+

[(s)0]

Cauchy

)2
I

-176:
t

C designates

where
the

Gaussian

the

Cauchy profile,

G designates

and S and D have

profile

the

usual

meaning.
The maximum error

by this

given

does not

method

10 %.

exceed

(4.3.7.

Introducin--;
equation

) and

(4.3.10.

) into

Halder's

:
k1_

2O

2es

(d' )oL

(A-1)

in's'units

(s)o
(4.3.14.

or
16 e2

J(20

)L cosh0

[d(2e)1cot28o
'2A'
in
units

two

These
Cauchy
of

the

Gaussian

and

Substitution

6o

can be written

of

triplets

two,

both

consideration

functions.

as determined

profile,

into

is

the

position

maximum.

peak

The equations

or

take

equations

(radians)

doublets

of c29

or more

using
of

Ao,
cos.
,

for

the

the

Rachinger

and's'values

cot26o

values

to

numerical

line

correction.

(J s)o

leads

reflections

k d,, pure

from
values

forLande
If

as

X29'

scale

is

[J(28
tan2O0

the

used,

2=

equation

S(29)

kX
L

can be written

tango

+ 16 e2
sin6o,

(4.3.15. )

177
t+.

if

and

we notify

2y

28
tan

5`

and

80

:
(2e)
tan.

the

eosin.

eo

becomes

equation

lc""

Y=

X+

L
which
Thus,

is

the

it

is

=x

equation

to

a line.

of

possible

(4.3.16.

16 e2

draw

a linear

plot

[S(2G)

of

tan
S(2e)

against

and

from

the

oC it

slope

60

results:

taneosineo

tan

c4 =k

From
to

the

which
L

L=

calculate

tanol
intercept

ordinate
the

calculate

the

Converting

to

enables

kX.

to

strain

into

make a linear

s=
0-1 )
(A

plot

equations

(29)

16

it

e2,

is

possible

it

is

e=-

equation

possible
2
The conversion
s.

n=

the's'scale,
C(

of
are

s)0]2

against

coseo

(4.3.17.

(rad)
0

178

jl

'.
'

2+
(h

sine
For.

lattice

a cubic

:o_

2)2

2a
J

where

is

the

perfect

is

the

incidence

the

(in

different

the

alters

(in

the

die

is

where
The line

in

different

dd
the

Ad

= ed

AA

= etan6

distance

(4.3.18.

the

'e'

is

(4-3-19.

strain

cot

e &e

from

the

to

origin

the

sphere.

PS =2 AE) = 2etan8
S is the
broadening
broadening

ways

different

crystallite)46

a=&=

powder

Thus

and

radians.

in

size

and differentiating,

e=6,

in,

2sin9

d=

where

lattice

same

X.

Logs

to

corresponding
2

as

crystallites)

directions

Taking

angle

be taken

can

strain

dimension

main

peal.

c1(2e)

The

lattice

(4.3.20.
due to

due to-the.

the

crystallite

lattice
size

strain.
is:

(4.3.21. )
L cosh
The

combined

effect

of

both

stress

and'crystallite

179
S

Slue

1S

S+

where
.

c =2

etan6

(4.3.22.

+N
Lcos6

=B-b:

or

coo9

the

is

which
If

cos6

of

minimum

two

occur

in

more

likely

occur

in

the

accuracy

with

which

P is

ray

diffraction

chart

a more precise

method.

'e'

Algebrically,
the

and

formulas

following

'L'

with

and small

size

fact

it

is

crystallites.

measured

be

can

a number

different

does not

obtained

when in

same crystallite
they

x-

is

strain

that

But

of

the

for

sin8

that

assumes

(4.3.15.

equation

a line
L

an intercept

method

of

against

reflections,

2e and

This

form

plotted

(4.3.23. )

+ L

simplified
is

a slope

2esine
=

from

an

the

use

justify

calculated

using

/(B1_b)2cos2e1_(B2_b)2co2e2
e=-

sin2e1

sin2e2

(4.3.24.
where

B1 and B` are

reflections
given

in

(hl,

integral

the
kl,

l)

by 81 and 62 incidence

breadths

(h2,
and
angles

k2,
for

reflection.
b is

the

instrumental

broadening.

of
e2)
the

the
planes
ko(1

1UU

s
. "3

The

thus

strain

given

(h2,

by

k2,

the

intersection

planes

2)

Crystallite
plane

(h,

size
k, 2)

L(h,

The error
that

fact
is

kl,

1)

in

a direction

and

for

is

k oC,

is

radiation

Xkcc1
k, Q) _

(B - b)

it

that

assumes
by strain
values

alone

cosh

is

due to

line

entire

and by size

can be quickly

modulus

alone,

but

calculated.

using

is

the

broadening

(4.3.26.

and it

the

(4-3.25.

method

the

can be calculated

Young's

to

perpendicular

Q"= eE

and

by this

approximate

a direction

along
(hl,,

of

introduced

produced

The stress

is

calculated

tabulated.

181 -

ek"

4.4.

is

Thickness

Film

The

determination

important

in

and

order

determine

to

also

parameters

films

plated

to

observe

the

effect

throwing

the

upon

ion

of

film

thickness

uniformity
deposition

of

power

of

the

x-

the

coating

method.
For

thin

both

tion

intensity

the
is

by the

is

There

are

is

mine
the

power'.

the

to

Therefore,

and the

x-ray

uncoated

to

possibility

film

measure

and several

is

)
a handy
p.

direct

the

and

less

the

of

measurement
polished

and

exact

thickness
by using

etched,

Microscope.

in

used

influence

thickness

specimens,

film.

evaporation

(>l,

Electron

method
the

due

available49.

section

on a cross

This

the

films

thicker

Scanning

absorbtion

when a monocromatic

coated

the

also

during

thickness

method

on the

radiation
the

diffrac-

ray

material

substrate

methods

differ

will

diffracted

For

through

transmission.

double

based

diffracted

the

of

attenuation

films,

be used47'48

can

method

thick

and

of

on the
usually

this
ion

front

referred

work
plating

in

to

parameters

and back
to

order

surfaces

as the

'throwing

deterupon,
of

flat

1-82 -

CHAPTER

10

THE EFFECT

OF PROCESS PARAMETERS
UPON ION PLATED

5.1..

effect

of

very

studied

process

variables

extensively

proved

that

induce

changes

Approach

Theoretical

The

FILMS

variation
in

it

although
these

of
the

has

not

has

been

parameters

structure

can

ion

of

been

plated

'films50
The

main

Wan,

discharge

Substrate

bias

Substrate

temperature

Source

Substrate

Deposition

Current

At

of

of

1-

pressure

(T)
(D)

distance

substrate
geometry
(DD)

rate

and

(Ii)

Carmichael5C

other

found

film

morphology

variables

in

influence

the

(p)

(V)

density

can

1 mtorr

growth

to

Chambers

most

range

Gazeous

pressure
of

are

parameters

the

that

the

gas

independently
pressure

50 mtorr.
and below

characteristics

it,

the
are

coating

structure

more dependant

and

on other

183
Y'

'R

)h

variables.
The

of

rates

collision

atomistic

the

and

particles

thus

pressure

The

one

effects:
the

The

on the

influencing

thus

Substrate

geometry

formity

because

smaller

thickness

concentration

the

other

work.

the

arriving

a graded

interface.

also

influence

can affect

the

and sharp

than

other

exposed

hollow

the

unihave

edges
of

parts

the

and field

cathode

associated

that

thickness

parts

effects

two

process

hidden

due to

substrate

diffusion

structure51

the

with

this

by

grain

and

size

the

and
in

early

can

substrate-temperature

crystallite

neutrals

affected

of

for

yield

the

formation

the

to

leads

and

also

the

power.,

sputtering

is

gas

process,

determinant

as proved

heating

local

is
ions

arriving

nucleation

energy

The

the

upon

ionization

throwing

bias

substrate

of

energy

the
the

and

dependant

much

affecting

spectrum

energy

on

are

effect

scattering

these

with

two

geometries.

Deposition

rate,

evaporation
to

ters

affect

between

ratio

which

rate,

the
the

is

a direct

can interact

function

of

other

parame-

with

ionization

and the

efficiency
rate

sputtering

the

and the

deposition

rate.
Source
density
Ion

substrate

distance

as proved

in

current

ionization

density
efficiency

early
is

the

can affect
this

current

work.

a direct

measure

and affects

the

for

the

nucleation

184
i

and

is

It

growth.

rate

sputtering
the

nonadhesive

for

eroding

determinant

also
is

which

peaks

r. moving
$1

(during

deposition)

lead

which

he

for

essential

particles

the

for

to

and

a columnar

structure.
In
is

this

kept

constant

(limited

by

varied

in

that

shape

of

can

temperature

Ii

T is

and

the

at

measured

Ii

chapters,

previous

'Ief'

be generalized

which
for

any

determines
is

a para-

kind

and

substrate.

the

total

centimetre

and is

a direct

ions

of

of

IefNi

and

of

+ Nn

Ni
Tef _
-NxNn

100 %

and

surface
ion

x100f

lrl

as

neutrals

substrate

function
N

defined
(argon

ions

of

number

number

Ni

is

efficiency

square

since

achieved

evaporation

V and

: p,

efficiency

ionization

between
the

are

bulk

the

ionization

meter

The

is

).

the

proved

the

13 cm and

deposition.

during
As

heating

resistive

12 -

of

1J. /min

of

distance

substrate

optimum

rate

parameters

time,

same

the

employed

method

its

at,.

to

source

deposition

a constant

The

the

work,

current

the

film)

ratio
and

striking

in

a second

density.

(5-1--l.. )

-185But

has

it

since

demonstrated

been

have'energies

neutrals

that

ions

to, the

similar

the

energetic
and
40

therefore

.-

characteristics
efficiency

having

sufficient

to

role

of an ion

plated

values

describe

Therefore,

process.
include

those

cathode

with

ions,

important

an

play

by

defined

another

term

(Nne

neutrals

the

'activation

is

not
of

the

to

the

strike

to

the

introduced

accelerated
Aef

efficiency'

and

:
Nne

where

ionization

status

) which

comparable

the

0.1101o is

energetic

the

obtaining

film,

the

energies

called

0.01

of

in

%
100
-x

Aef

_N+
N+Nn

Ni

= number

of

ions

NnI

= number

of

activated

(5.1.2.

or

energetic

neutrals
= total

Nn

number

of neutrals

N
+ Nno
ne

where

Nno = number
thermal

"

From the
to

for
Aef

instance

30 eV
3 kV
10 rntorr

arriving

with

energy

plotted,

previously

graphs

calculate

of neutrals

3.6
=

is

it

:
"

possible

"f

-186-

tS
,
Lta

fYr
J

',

is

which
.
r
4

the

activation

for

efficiency

energies

higher

than

30 eV giving

the

percentage

of

particles

dT

capable

of

producing

sputtering

The main

importance

of

reflects

the

spectrum

whole,

energetic
the

the

most

factors

it

essential

the

improved

ion

number

the

ions

of

number

films

plated
influencing
to

variation

analyse

of

is

one

the

film

the

way

lead

could

density

a sufficient

during

the

to

possible

first

stage

to

of

in

an

to

important
deposition

But

achieve
rate

of nucleation
of

a uniform

obtain

thickness.

a small

the

in

as a

plating

the

it

structure.

centres

is

is

parameters

By
creating
,

for

of

important

properties,

is

in

that

neutrals.
microstructure

which

ion

of

increase

a sensible

is

parameter

increase

a small

since

can induce

As

energy

this

an

and

deposition,

as

the

film

optimum

the

dense

and

it
film

even
it

grows,

ratio

sputtering

between
rate.

DR

(5.1.3.
SpR

where

DR is

the

SpR is

a.

If

sputtering

( < 1),

rate
b.

the

If

the

the

no film

deposition

deposition

rate
rate

sputtering

rate

exceeds

growth
rate

the

deposition

can occur.

exceeds

by far

the

sputtering

167 -

rate

1),

be

cannot

nonadhesive
in

removed

particles

time,

and

and

peak

a columnar

growths

structure
0

is

obtained

parallel

with

a worse

to

adhesion

the

substrate.
Therefore,

a good-balancing

the

to

answer

the

problem

To reduce

structure.
the

deposition

rates

and

therefore,

the

to

appears
a direct

Most
ion

be

of

the

pressure
ionization

DR is
are

density
but,

very

of

the

columnar

for

be

since
ion

to

plating

adjust

SpR

to

proved

variation

in

Analysing

SpR and DR
they
,

constant
diode

plating

in

are

the

the
this

gas

with

pressure

system.
:

+ Nne )

)=
Nn
+

K2 (Ni

K2 (Ni+Nn

"

Ni+Nne

Ni

+Nno

+ Nne

N.

+ Nn

N. + Nne

(5.1.5. )

where

K
2
Y: =K
1"

+Nno)

then
K2

the

work,

(5.1.4.
DR

is

which

control

by modifying

remains

K1 (Ni

way

tended

as previously

SPR

could

mainly

an ion

low

controlling

so far

efficiency

Spx

uneconomical

already

Ief

of

removing

efficient

by means

research

current

of

only

function

DR and

of

188
N. +Nne
but

:A

Ni

+ Nn

) becomes

(5.1.5.

Then

of

Ni

+N-

ne

(since

Nn

K
Aef

but

and

N. <'N
in

(5.1.6.

Ni

+ Nn;

= f(N1)

"n

= f(ER)

for

p and v constant

ER is

where

the

rate

evaporation

Ii
K3

Hi

K3 is

where

a time

constant

Ii

is

the

ion

current

is

the

total

area of the cathode

surface
the ion bombardment
and is

to

exposed
a constant

or

It

;:

that

results

iL

Therefore,

in

Ii

for

a diode

One method
introducing

is

where

(Ii,

=f

ER which

modifying
ling

KIi
=

Ni

EE) for
to

possible
is

of

plating

which

either

by

or by control-

economical

not

is

not

possible

system.

independently

an auxilliary

p and V constant.

control

p and V constant
ion

...

controlliixg
anode

in

this

Ii

is

case

by
called

-Log

ef

'positive

I.

can accelerate

on it

applied

to

energies
The voltage

produce

the

applied

being

Theoretically,
the

due to

take

the

and

the

below

vapour
the

creating

film

ionization

in

low

with

form

the

this

of

to

energy.

voltages

conditions,

of

produce

significant

better

for

gas

the

of

could

case

the

maximum.
are

(weak

gas pressures

several

a plasma

which

is

efficiencies

one or

dropped

be

with
in

vapours

pressures

evaporant,

work

source

low

could

efficiency

electron

auxilliary

gains

to

ionization

When higher
combined

electron

pressure

film

maintained

atoms

collisions

possibility
the

be sufficient

sould
path,

pressure

by

be :

must

current.

argon

partial

could

mean free

proved

efficiency-.,,

atoms.

of neutral

energy

required

ion

the

in

increases

sufficient
4

of VE which

plating

30 V were

least

to

+V, an electron

volts

the

ion

normal

Probe

small

before

place

Under
at

several

voltage

electrons

Ionization

>i

Ve

a positive

ionization

a maximum energy

achieve

but

having

which

probe',

required
an

plasma),

be introduced
hot

saturated

filaments.
In
of

this

work,

a semicircle

equal

distances

probe

-the positive
placed
from

within
the

the

cathode

was in

the

dark

space

and the

shape
at

negative

190 -

Voltages

glow.

0-

of

250 V were

on the

available

probe.
,

5.2.

Experimental

In
Ii,

flat,

cm2

The

sputter
and

bulk

to

a current
was

back

of

of

the

area

a bias

15 mtorr

14 mA.

cm and

was achieved.

the

at

plated

having

a total

performed

of
12

were ion

The

voltage
45
to

source

/min)

A thermocouple
to

of

for

a constant(lt

substrate

the

was
measure

temperature.

The variation
5.2.1.

pressure

rate

connected
the

an argon

p, V and

of

substrates

mm giving

was

distance

deposition

thickness

cleaning

drawing

substrate

influence

nickel

25 x 25 x3

15.5

minutes,

10/

of

polished,

dimensions

3 kV

the

study

films

copper

on

of

to

order

of

the

parameters

is

shown in

Table

191

T,,,Lble
Spec
No.

5.2.1.
Idep
(mA)

-V
p
(kV) (mtorr)

T
C)

+V
(V)
0

20

95

30

14

100

40

19

110

10

90

20

16

130

30

31

150

40

45

165

50

55

175

10

100

10

20

21

145

11

30

38

170

12

40

50

185

13

10

10

115

14

20

25

170

15

30

42

200

16

10

8(21i)

150

60

17

10

12(311)

240

100

18

20

32(2Ii)

280

200

NOTE

Ii

the

represents

p-V

conditions

21i

and

ditions

probe.

Ni
by

ion

but
are

applying

the

without

obtained

drawn

current

for

a positive

positive

the

in

the
probe;

same p-V

voltage

con-

on the

-192

Afier

ion

in

by

the

being
was

L(R)

the

two

radiation

in

For

a large

grain

test

and a load

hardness

tester.
bad

of

typical
However,

this

obtained

by

indication
Fracture

ion

plating

about

the

the

In

to

measure

were

front

etched

chemically
Electron
The

versus

The deposition
ters

in

strength

of

quantitative

the

bond.
to

these

reveal
were

Microscope.
film

surfaces,
bakelite,

and then

adhesion

no

and

in

and

5.2.2.

Electron

back

test

employed

and compare

showed

observed

thickness
the

substrates

polished,,
in

Scannirg

the

Microscope.

substrate

plotted

this

superior

gives

micro-

films

plated

but

mounted

sedtioned,

a diamond

using

the

Scanning

and the

diffracto-

ray

broadening,

Figure

structures

in

on the

in

were

X ray

copper

x-

using

when

sections

internal

the

of

was used.

ion

proves

observed
order

the

shown

test

cross

films

the

is

size

200 g. on a modified

of

adhesion

scratch

size,

crystallite

instrumental

powder

All

crystallite

purpose,

was performed

indentor

sign

of

this

the

silicon

scratch

the

. standard

removing

dimension

broadening

For

was used

meter.

no
,

line

was

Microscope.

a single

effects

pattern.

morphology

Electron

calculate

on the

diffraction

surface

crystal,

to

required

distorsion

The

film

Scanning

a cubic

separating

and

the

plating,

analysed
Copper

Figure

bulk

temperature

parameters
ion
5.2.5.

current

in
is

during
Figure
plotted

deposition
5.2.3

is

and 5.2.4.

versus

parame-

'`
.

_.

_ . -_

...

5.2.2
re
Tit , :.,I sc.rotchteste.

--3a.

--

: i='^"
.,

'

_194_

fpmpro+ure
bias
rate
Yerrus pressureand
volfaoe

5s

5kV

250

4V
Zoo

3 kV

03%
xO.

450

2W

too.

Jo

20

Figure5.2.3

4,0

50

(mtorr )

195
-

Ior I

t'

oc

4
';
R

O
,-2.

200

150

100

it

2IL

3Ii

Fiure5.2.4

"
Positiveprobe-ocf;vofed

Subsfrate femperafure vtrrus

ion current

ion current

196
r

`Y

I dep (mA)

1
C

5kV
a

kV
/4

60

/3kV

50

3kvi 20 mtorr; 2ri

40

30-

3kV; IOariorr; 2IL

2kV

kv; to mtorr; 3i;

20

10.

10

20

30

40

F1ure 5.2.5
Deposiiionion current
pos4;ve probe" activated .

(mtJ )

197
5.3.

Resu1ts

5.3.1.

Microstructure

The microstructure
on fracture

cross

The effect
bias

is

voltage

was analysed

shown in

2,3,4

for

pressure

the

Figures

SEM.

and 5 kV

5.3.1.1,5.3.1.2,

and 5.3.1.4.

5.3.1.3
For

films

by means of

sections

argon

of

the

of

2 kV,

the

and the

improvement

brings

variation

pressure

tapered

consists-of

structure

little

crystallites.
,

Of the

three

structures

40 mtorr

with

5.3.1.1

gure

of

of

40 mtorr

of

in

and sep. rated

or

less

the

tapered

sirnii.

r to

pattern

which

into

columnar

leads

consists

a porous
to

30 mtorr
crystallites

in

(Fi-

size

that

is

the

For

nearly

growth

a structure

is

uniform

voids.

obtained
a).

to

relatively

by large

5.3.1.2

doomed structure
of

a)

tapered

crystallites

3 kV and 10 mtorr,

(Figure

mtorr

and

b)

composed

_.

and 20,30

smaller

others

pressure

For

5.3.1.1.

raised

large

some

An argon

size..

is

pressure

consists

alternating

is

one

embeded

As the

structure

voltage

worst

crystallites

structure.
the

the

argon,

tapered

of

2 kV bias

to

corresponding

Figure

in

presented

structure
for

is

more

2 1c1 and 20

3 kV and 20 mtorr,
removed

observed

and a definite
(Figure

198

5.3.1.2

b)

3 kV and

For

is

structure
columns

d)

but

structure

the

it
than

in

pressure

columns

be noticed,

the

tapered
to'40

the

produces

the
crys-

mtorr

columnar

same

denser

are

the

c),

can

size

increase

5.3.1.2

5.3.1.2

as

in

smaller
The

(Figure

in

columnar-and

are

tallites.

(Figure

30 ritorr

and

smaller

size.
50 mtorr,

3 kV and

For

to

similar

maintained
features

the

columnar

but

one

taking

is

structure

previous

bonding

of

signs

the

it

among

place

the

columns.

5.3.1.2

Figure
-of

the

from

This

could

no

the

or

likelSr
film.

signs

of

interface

it

not

is

the

to

adhesion

the

adhesion

created

the

is

than

or

interface
test,

scratch

observed

be harder

fracture

interface,

the

were

to

expected

fracture.

between

during

and

since

the

film,

more likely

to

occur

at

3 kV

the

film.

copper

the

The improvement

in

can be observed

by analysing

as shown in

:?igure

in

is

pressure

a bad

tensile

deep
is

section

was pulled

the

sufficiently

However,

means that

within

due

fracture

bad

film

during

either

the

the

the

cross

3 kV and 40 mtorr

at

produced

substrate

be

a weak

and

a fracture

can be noticed,

away

more

film

copper

and as it

by

f presents

structure.

5.3.1.2

followed

the
g, h-

produced

topography

surface
i.

by a reduction

The increase
in

the

grain

199
size

and

size

of
it

As

an improvement
the

dicates

the

bonding

among

the

film

increase

of

is

the

formation

The

argon

e)

columnar

structure.

is

growth

still

to

similar

the

which

with

alternating
The
is

to

30 and

to

raised

which
of

a denser

topography

(Figure
a denser,

remanent

composed
for

a ductile

of

some

quickly

as

non-

a low

for

5.3.1.4

a)
of

nodular
.

parts

4 kV and 40
fracture

denser
the

film

(Figure

voltage
even

this

by

obtained

40 mtorr.

as

produced

although

to

in

observed

indicate

is

due

patches

improves

structure
raised

be

are

(Figure

structure

to

leads

a bonding

5 kV bias

20 mtorr

structure

could

bond,

structure

presept

the

Apparently,

mtorr

of

pressure

structure

is

pressure

given

to

a better

20 mtorr

columnar

that

surface

at

has

a), and the

probably

appears

10 mtorr

"

fracture

produced

have

5.3.1.4)

argon

also

files

The

most

the

5.3.1.3

and a weak

4 kV and 40*mtorr

for

cones)

a ductile
since

0,

in-

which

stress

to

to

start

d)

and
are

structure,

cohesion

packed

As the

5.3.1.3

microstructure

a close

completed

(cups

of

the

5.3.1.3

pressure

columns

(Figure

result

d,

4 kV and

at

b).

the

voids

5.3.1.2

columns.

of

apparently

argon

the

of

(Figure

5.3.1.3

30 mtorr,

of

internal

of

produced

columnar

(Figure

uniformity

Figure

lack

of

existance

structure

the

from

signs

presents

The

the

grains.

be noticed

can

film

in

structure.

argon

A recrystallization

pressure

200 -

is

process

to

possible

structure

for

specially

(Figure

5.3.1.4

40 mtorr

to

argon

denser

pressure

c)

when the

microstructure

resembling

a ductile

surrounded

by

features

ding
.

le

occur

is

structure
to

similar

of

(cups

fracture

a denser

are

composed

and

whose

those

small

by

given

patches

cones)
fracture
a brittle

material.
Looking

the

at

surface

recrystallization
5 kV /

with

fracture.

5.2.3.,

to

zation

film

grows
of

growth

which

"ray

diameter
alternating

structure

also

graph

for

are

the

in

that

met

large

with

does

and
,

indicated

some larger

iriprovement

case

the

takes

method

of

in
5 kV

of

10 minutes

place

is

the
in

fact

(using
fine

allow

is
the

as

place

not

not

It

recrystallization.

layer

4.1.3.

a recrystalli-

takes

crystallites

beam) which

the

such

deposition

reflection

noticed

presented

although

recrystallization
by

structure

recrystallization

2000 C (table

conditions

The activation

a definite

dense

a complete

layer

back

grain

results

place

that

possible

take

for

sufficient

x-

the

during

time

"

it

40 mtorr

and

equiaxed

temperature

for

of the

the

copper
the

analysing

Figure

The aspect

being

specially

The approximative

for

temperature
and

less

of

patches

on the

for

d, e & f)

observed

conditions.

typical

is

5.3.1.4

is

process

40 rtorr

surface

(Figure

the

confirmed

by

a 400

in

the

crystallites

ones.
positive

the

probe

microstructure.

leads

to

GU!

3 kV and

At
the

positive

of

the

(Figure

also

the

reveals

these
is

that

the

ionization

temperature
30 mtorr.

and
is

which

a typical

leads

to

in

crease

the

sputtering

with

the

that
shown

an

efficiency
value

increase

in

these

the

for

obtained

3 kV

conditions
c)

improved

which

structure
due

not

effect

and

the

of

same conditions

+100 V applied
increase

film

structure

appears

to

in

is

an

is

probe

but,

probe

to

the

of

therefore

the

increase

an

in-

(higher

coefficient

rate).

threefold
dense

positive

positive

5.3.1.2

the

Sc)

under

increased

for

that

5.3.1.

is

level

(Figure

one

temperature
ionization

the

For

the

by

structure

conclusion

with

in

rise

the

columnar

the

obtained

in

But

the

of

the

al-

200CC,

obtained

% followed
reaches

a),

(Figure

efficiency

0.06

fracture

recrystallization

structure

One effect

% to

0.03

from

bellow

aspect

denser

a combination

5.3.1.5

the

removes

on

cathodic

a ductile

well

surface

conditions.

is

(Figure

) which
The

initial

giving

temperature-was

possibility.

the

structure

fractures

5.2.4.

+60 V applied

with

double

resulting

some denser

though

to

and

approximately

patches

and

10 mtorr

probe
the

current,

Figure

of

on the
in

the
is

be due

but

to

give

positive

probe

cathodic

current,

obtained
to

a very

a fracture

giving

a brittle

as

material

b.

5.3.1.5

The corresponding

surface

5 d)

fine

shows a very

3 kV and 10 mtorr,

micrograph

structure

(Figure

probably

5.3.1.

due to

the

11

intense
large

the

x-

in

the

that

indicates

(Figure

as

in

shown

as

revealed
with

the

This

leads

ture

is

the

tal.; ered.

The xetched

larger

crys-

that

of

the

probe

ray
cross

is

the

dense
has
pure

hard
and

due

strucand

than
the

to

the

case

an

valleys.
was

columnar
obtained

0.105
that

indicated
pure

even

a balanced

to

and

this

structure
a hardness

ones.

dense

the

measurement

copper

for

structures,
using

the
equal

approximately

copper.

L: ck reflection
ection
,

larger

(due

peaks
for

less

is
grains

small

mainly

errosion
the

all

chemical

a recrystallization

is

but

crystallites

very

of

to

due

Microscope

structure

fairly

of

section

the

to

grain

conclusion

efficiency

film

the

relatively

microhardness

copper

that

a combination

cross

Owing

some

process,

the

beam

diameter

Electron

Scanning

seen,

of

through

the

positive

the

composed

the

ionization

while

etched

back

ray

x-

a few

slightly

entirely

coefficient

to

being

to

not

The

the

in. fact

is
and

be

presence

growth

The

in

5.3.1.8.

can

growth

film

a 400

crystals

in

Figure
it

as

etching

grain

and

analysed

also

and

crys-

5.3.1.7).

A polished
was

indicated

rot

structure

small

relatively

tals

(using

method

reflection

1000

of

broadening

line

The

pattern

of

excess

of

signs

a temperature

although

diffraction

ray

no

with

achieved.

was

24000

tallite,

of

formed

being

grains

approximately
of

bombardment,

energetic

and the

showed very

chemically

small

grains

and

%.

203
-

this

that

indicates

5.3.1.5

b is

fracture

work

performed

for

the

as follows

film

along

the

shape

takes

rance

of a brittle

consisting

of

the

in

sections

this

the

5.3"l.

expla

5b could

be

enough

nature

of

that

takes

following

and
thus

is

grains

the
the

giving

placegrains

appea-

fracture.

these
the

small

fracture

line

a straight

end of

the

Figure

boundaries

grain

Since

was not

temperatures

temperature',

in

therefore

and

produced

the

low

cross

room

section

dense

A very

at

Figure

Such a brittle

at very

fracture

all'the

in

presented

one.

be obtained

and since

nation

fracture

a brittle

not

could

were

the

experiments

these

further

for

some more research

this

there

work,

films

but

in

however,

be done and reported

will

towards

out

investigations

dense

very

carried

to

affected

period
time

were

later

on.
The

+200 V on the

and with
the

twice

value

(ionization

shown in

the

argon
current
reaches

2800C which

confirms

has a role

in

fact

obtaining

to

increase

%)

for

current

lesdsto

5.3.1.6.

Figure

5.3.1.5a),

the

20 mtorr

cathodic

0.06

is

3 kV and

probe

initial

and a twofold

(Figure

This

at

positive

obtained

structure
pressure

films

the

of

efficiency

structure
to

of

production

a film
is

which

similar

3 kV and 10 mtorr
increase

although

in
the

the

cathodic

temperature

a much higher

value.

that

temperature

the

although
structure,

the

ionization

204
-

r
'0

the

the

is

efficiency
deposition
in

ment

rate,

the

lead

can

balanced

which

parameter

microstructure

to

improve-

radical

ion

of

against

films.

plated

**

films

Aluminium

plated

on flat

argon.

and
the

with

steel

then

positive
in

rate

sition

in

The

structure

is

columnar,

morphology

(Figure

probe

The film
tensile
In
with

lacks
stress

contrast
the

obvious

signs

easily

The film
(Figure

cohesion

as

shown
these,

is

shown

of

by

Figure

5.3.1.11b).
*

section

positive
the

surface

b,

in

plated

with

cubic

(Figure
to

ion

a dense

presents

surface

a.

film

5.3.1.9

Figure

under

easily

aluminium

and adhesive

cohesive

the

5.3.1.11

recrystallization

noticed

the

and breaks

(311)

on the

and

).
a

the

probe
in

in

depo-

b.

a and

revealed

The

fracture

without

5.3.1.10

positive

structure

also

in

with

as

tals

obtained
as

the

5.3.1.9

Figure

a three-

give

/min

0.5p
through

obtained

presented

to
current.

cathodic

approximately

was

microstructures
are

the

but

conditions

activated

ion

were

3 kV and 10 mtorr

at

same V-p

the

probe

increase

times

substrates

in

5Ju. thick

approximately

-'

the

crys5.3.1.10b).

substrate

205
I-

'

The
that

the-main

that

parameter

can

could

ionization

isthe

structures

"f

that

conclusion

general

be

drawn

lead

to

efficiency

is

improved
is

which.

}rE

ion

function

of

perature

which

lead

could

cular,

for

low
to

followed

density

current

materials

melting

by

-tem-

in

partitaking

recrystallization

some

place.
The
variation
manner,
structures
ending-with

introduction
Ii

of
proved

of

a triode

independently
successful

beginning

with

some unusually

to

allbw".

in

a controlled

producing

controlled

and
in

system..

tapered
dense

crystallites
structures.

and

the

0-

2 kV
20 mtorr

40

b.
?_kv
ii

f1tJv

t
.

2 kV
40 mtorr

5.3.7.1
F,:
eure
kV
2

"I

Iq

a. 3kV ; 10 mtorr

S. '
r
R

_.

r4
.a

b.

3 kV ; 20 mtorr

Figure5.3.1.2
3 kV

C.

3KV ; 30 mbrr

"MW

'Or Al AILI,

cl.

:J;

40 mtorr

Fi!.-!ure 5.3.1.2
3kV

l;

IL,

`IM

3kV ; 50 mt-rr

"mmorr

the

film

hic
5.3.1.2
ore
3kV

puilc

ff'-

%.

3KV ; 10 mtorr

40 mtwr'

Fiure5.3.1.2
3kV

L.

'1
,

50 morr

Fiure 5.3.1.2
3kV

i ,
<:

212

..
t .,
..

CL.

kV ; 1omtorr

,
b"

4KV ; 20 mtorr

fl9ure5.3...
3
4kV

._
V
-i ...

'J
1

fflLf

n, iutr

5.3.1.3

Fire
.>=;

4kV

.
d,,.

C.,

30 mrr

.i
40 mforr

5.3.1.3
Fiere

e.

4kV

; 40 rntorr

Figure5.3.1.3
4-KV

-=

_J

abi .w
I-,
I-

20 mtorr

Remanent nodular growth .

Figure 5.3.i.4
5kV

"III%

Ni&

b.

AV

30 mforr

-. f-.

...
.F'.
+.

.4w
4W&

.
..
c.

V;

40 mforr

F ;pure5.3.1.4
SkV

ct.

I-7 -

5 kV ;

20 m{orr

Fi9ure;. 3.1.4
skv

e.

kV ; 30 m+orr

'

y, '

i
4

40 mtorr

",

Figu.
ure 53.1.4
(mot

Sky

NUMBERING

AS ORIGINAL

C_l

0
L

10

'""''T

2 L yr

""now

p,

.=_;
.

T
.

,.

6.3kV

40m orr

-3

IL (+400V)

5.3.1.5
hure
3kV& positive
probe

__

1.

;-

C.

3`d

10 mtorr

2Ii
-

Fijure 5.315
iN

3kV 8- posIRveprobe

(+60V)

:. . U-

:.

j,

',V

10m&rr

(+400V)
3Ii
-

5.3.9.5
Rure
3kV$cposi}iveprobe

221 -

,
.

"
I,. Y :.

M icrosfructure

surface

3KV; 20mtorr

2It
(t2oov)
-

't ure5.3.1.6

3kV Scpositive probe

2'2 -

3kV ; 10mtorr

31L
(+ioov)
-

Figure5.3.1.7
X -roy back re1lec+ion(400p beam)

F'i4

3kV ; 10mfo r-

3IL (+4OOV)

Figure5.3.1.8
3KV k pcet+ ive
probe

Z C".i

!..,

wry

a'1f "`

`
i`

'R'.

e'-

#='r,

10A.
A-e

It
1111i'llf,
,
&,,
,f

Q, .

3kV

40 mtorr

,...

`"

.,r,,;

zw
LYy,
..
31

b.

"KV; 40mtorr

Fiiure 5.3.9
Aluminium

3I;,

0..

3KV ; 40 mtorr

b. 3kV; 4omtorr - 31i

Figure5.3.1.90
Aluminium

rn

G.

,.,r

.r.

a.

3kV ; 40m+orr

to mtorr

Fi2ure

Aluminium

3I
-

226 -

;.

Power

Throwing

5.3.2.

The throwing
is

defined

to

coat,

mine

the

(out

of

sight

to

The throwing

is

power

the

process
A

substrate.
the

throwing

then

and

thicknesses

front

the

and

sight)

the

of

substrate
the

technique

plating

determining

between

ratio

of

parts

a flat

coat

ion

capability

quantitatively

of
is

power

of

out

Method

the

as being

the

of

power

deter-,.

to

on the

back

surfaces.

dfB
dfF

where

dfa

= film

thickness

on the

back

= film

thickness

on the

front

fF

ideal

In

conditionsTp
on the

thickness

for

However,

under

substrates
power

is

plotted

and the

front

films

copper

which

ion

different
versus

surface
surface

means uniform

back.
on flat

plated

the

conditions,
in

parameters

nickel
throwing

Figure

5.3.2.1

and 5.3.2.2.
It
"

argon

pressure

power

which

nation

is

field
that
lines

however

as well

place

induce

at

in

voltage

improvement

of

the

remains

as the

that

increases
take

to

leads

increase

the

that

can be noticed

voltage

0.7.

increases,

angles

orrientation

throwing

The expla-

and therefore,

discreet

e. stronger

below

and

the
the

with
of

electric

collisions

the

field

the

neutrals

;
,
,

f}
..

227

towards

the

will

go to

The

increase,

in

the

gas

area

cathode
the

out
in

of

argon

factor

responsible

The

activation

of

upon

the

thus,

and

sight

back

the

throwing

for

more

which
the

positive
power

neutrals

surface.

leads

pressure
effect

scattering

main

effect

to

an increase

however

throwing
probe

is

the

power.

had

(Figure

a negligible

5.3.2.2.

).

228 -

dfF
4
0.7

4 kV

skV

RV

O. 6

2Kv

O"S

0.4
0.3

Q`2
y

0.1

f (mtont)

10

20

30

40

50

5.3.2.1
Figure

d; s

TP=
dfF

04
0.3

3kv;
lo miorr.
io

0o

0.2

on current
o

+60V

+iO V

Figure5.32,2

positive
probevoltaae

1'

229 -

tl
5.3.3.

internal

The
was

Strain

Internal

the

to

applied
diffraction

presented

in

Figures

ion

current

value

'e',

and

produced

for

and

pressure
strain

than

higher

at

3 kV,

'2

Ii

also

One explanation
of these

value
the

internal

positive
&3

free

probe,

the

Ii

at

and

could

be that

parameters

the

produces

leading

to

1 of

the

stress

= o)

pressures

films
3 kV,

produced
20 mtorr

increase-in

&

the

an increase
a relief

of

can be'calculated

(5.3.3.3)

IT= eE

For

(e

films

the

of

in
the

stress.

The value

where

voltage,

free.

stress

temperature

local

is

reduction

4 and 5 kV and argon

10 mtorr

are

in

to

leads

The

20 mtorr.
the

Using

ray

5.3.3.2.

increase

stress

x-

parameters

and

the

method

described.

process

5.3.3.1.

films

plated

the

of

previously

with

be noticed,

can

ion

breadths

broadening
as

strain

are

integral

pattern
of

it

the

line

variation

As

of

using

measured

thin

strain

`Young's

modulus.,,

copper:.

E=

17 x 106 psi

-'

using:

2 30

0
O'1

c1rl

Cl

t'

231

-1

3
C
0

"J
'l

.J
6-4

04

Izz'

en

f4!

aq

232
_

Conc1usions

5.3.4.
e

As a general
a positive

probe

and

adhesive
`the

two

the

results

are

The

factors

deposition

ion

current

(that
,

A well.

and the
the
film

The

to

place

It
the
or

group

from

for

metal

voint
tc

for

) which

depends

T
film

rate

and

upon

the

for

rate,

p and V

results

in

growth)

being

of

the

peaks
erroded

results

all

in

nonadhesive

surface.
important

is

to

some
to

leads

the

since

a high

recrystallization
reduction

of

value.

stress

ion

sputtering

sputtering,

also

further

plating
since

of rr.etals,

the':: pelting

the

leads

and

remains

optimum

stress..

responsible

and also

temperature

internal

be

filled

on the

surface

the

to

the

through

temperature

take

thought

evaporation

being

valleys

particles

very

internal

balanced,

during

removal

structure,
no

(tJi

rate

appear

in

useful

having

between

and the

constant.

of

ratio

the

introduction

be very

a dense

with
cohosive.

main

to

proves

films

producing

the

conclusion,

conditions
the

temperature

metal.

to

research
for

sputtering
vary

determine
each metal
yield

extensively

axed

Conclusions

General

1.

Energetical
the

ion

neutrals

on an

coating

earthed

2.

The ionization
low

3.

energy

simulation
indicate

The

ion

and

found

have

the

that

voltage,
about 300 eV.

although

a small

the

upon
bias

process

density

and

upon

effects

indicated
the

of

voltages

structure.
The AUGER analysis
for

also

found

conditions

to

be arqund

of
that

deep -graded

films
using

experimentally
ions

of

number

ion

plated

parameters
the nuclei

have

of

ion

the

interface

the

physical
interface
are

were
a triode

ion

3 kV
be of

films

and

a major
that
higher

density

current

can

lead

distributed
uniform
nuclei
film
the resulting
micro-

the
and
pairs)
compatible
(for
incompatible
redeposition
Copper

extremely

plating

determined

(for

7.

is

also

nucleation

and relatively

major

films

various

energy

is

the

that

indicated

with

have

using
a heat imput
as a thoretical
method,

spectrum

on the

Experiments

dense

to

energy of 3 KeV for

acceleration
their
average
energy is found to

full

bias

to

films.

3 kV bias.

energy

pressured

plating

have

obtained

can have
their
avbrage

voltage
150 eV for

effect

; for

spectrum

a mesh,

in

that

proved

behind

found

part

neutrals
carry
approxithe depositing
particles.
up to the acceleration
energies

but

5.

is

as well
method,
that
the energetictt
60; of the energy of

mately
The neutrals

4.

ion

for

efficiency
about 0.1

of

values

Neutral

substrate

typical

characteristics

a major

play

c--id experiments

mechanism

plating

to

found

are

in
plated
arrangement

of

the

ion

plated

processes
responsable
the thermal
diffusion

atomistic

mixture

and

pairs).
a diode
aimed

system
and
at controlling

ion

the
bias

density

current

of

pressure

and

voltage.

A set

of

microstructures

lites

to

very

at

independent

low

continuous
as a high
ponsible
the relief

dense

unusually

relatively

from

ranging

substrate

structures
temperatures.

thought

very dense structures

the internal
stresci.

the
in

Recomr. ndations

for

Future

better

to

crystal-

was

obtained

The

bombardment,

and enhanced cnerjetic

temperature,
local
are
for

tapered

as well

to be resand also for

Research

the

effect
of a third
it
is
the
recommended
mechanisms,
upon
plating
electrode
for
the neutral
to determine
and ion energy spectrum
In

these
It

is

of

understand

case
also

bombardment
dense

order

necessary
and

structures
the
removing

to

substrate
in

order

Columnar

the
separate
temperature
to

effect
in

understand

structure

of

ion

the
obtaining
the mechanisms

233
APPENDIX
{

Calculation

of

the

coefficient

DR
SPR

where

DR

{1)

= deposition

rate

deposited
(

atoms)

Cm2 sec.

SpR

SpR could

sputtering

rate

from

be calculated

XE
3c4
S E) =_4`"Tf1uo

incident

where

sputtering

atoms
ion/neutral

having

particle

41,11"1)

(1121+I"2)2

E=
,E=
pJl1' III

S(E)

the

S(E)

yield29'30'49

The

atoms
(sputtered
2
cm sec.

the

Ei;

transferred

energy

of

incidence

of

the

can be written

energy

(3)

energy

= masses

(2)

incident

and static

:
4

atoms

tj4

r`
{Z

0.042
=

S(E)

tu

(E)
sn
off

(4)

is

as

the

the
heat
is

S(E)

barrier

surface
of

energy

which

sublimation

tabulated49

cm

and Nne(s)

Ni(s)

having

neutrals

higher

Ax

(s)

ne(s)

is

Aef

where

and

sputtering
)

(5.1.2.

using

np

( particles

100

the

the

ions

11

efsp

+N

of

than

(5)

sec.

number

and can be calculated

threshold

Ni

the

are

energies

atoms

(2) sputtred

+ Nne(S)

T1i(s)

SpN = S(E)
T

where

be taken

can

(6)

cm2 sec.

of

percentage

particles

sp
of

capable

An average

for

calculated

are

be

could

rate

sputtering

and s(E)

Aef

sputtering.

producing

determined

the

average

if.

ion

sp
and neutral
S(E)

energies.
for

tabulated

is

The deposition
the

depositing

different
rate

same amount

and pressure

geometrical

N.

1S

could

(E)

in

Table

be calculated

of material

conditions,

in

149.
after

similar

as follows

(7)

235
-

5f

NM
am

where

'Ma

of

F=

film

density

S=

total

surface

df

film

thickness

df
D
R

mat

p' is thepartial
atoms

(sec)

time

area

it

atom

or

results

molecule

deposited
atoms
(
cm2 sec.

pressure
) could

be

of the
calculated

film

vapours,

using

the

method

cm2 sec.

described
DR could

in

Substituting

2.8.

Section

be taken

Dx = Nnp (

(6)

as being

approximately

to

cm

sec,

and

(10)

into

100

(1),

it

results

(11)

NnP
p

or
100
sp

Nnp

(10)

x
ex

equal

atoms

ldnp

.:

film

a film

of
(7),

in

Substituting

N(
np

the

TLI = mass

ma = mass

If'

deposition

total

t=

(8

(12)

MISSING
PAGES

NOT.

AVAILABLE
i

J7

TABLE

-`
Sputtering

Yield

of

Argon

:
Ions

Incident

on Various

Materials,

T
Voltage

200

600

1,000
Sputtering

Ag

1.6

3.4

Al

0.35

1.2

AU

1.1

2.8

0.05*

0.2k

Cr

0.7

1.3

1.1

Fe

2000
Yields,

5,000
Atoms /-Ion

8.8
2.0

3.6

5.6

7.9

2.3

3.2

4.3

5.5

0.5

1.3

1.4

2.0

2.5

Ge

0.5

1.2

1.5

2.0

3.0

160

0.4

0.9

1.1

Nb

0.25

0.65

Ni

0.7

1.5

Pd

1.0

2.4

Pt

0.6

1.6

Si

0.2

0.5

Ta

0.3

0.6

Ti

0.2

0.6

vi

0.3

0.6

Zr.

0.3

0.75

-Cu

Sic(0001)
Si02
. 11203
*Kr+

ions

1.5

6.6

2.2

2.1

0.6

0.9

1.4'
1.05

1.1

1.7
1.1

Sputtering

"

10,000

Yields,

0.45
0.13

0.4

0.04

0.11

Molecules/Ion

2.1

238
-

P;
r
,,

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