Surface treatments

Vacuum plasmas

M.P. Delplancke – Ogletree

 Introduction

• Treatments developed over the last 45 years

• Processes that uses

– Low gas pressure
– Electrical energy to generate a plasma
– Precursor(s) : gaseous or solid

• Major classes of methods:

– Physical vapor deposition (PVD) : evaporation, sputtering, arc
– Plasma enhanced chemical vapor deposition (PECVD):
 Gas properties
Kinetic theory of gases
The distribution of particle velocities calculated by Maxwell and Boltzmann is
3/2
dN 2N ! m $ 2 −mv2 /kT
= # & ve
dv π 1/2 " kT %
Where m is the particle mass, T the temperature in Kelvin, N the total number of
particles and k the Boltzmann constant.
The average velocity v is given by
1/2
! 8kT $
v =# &
" πm %
The peak velocity vp is:
1/2
! 2kT $
vp = # &
" m %
The root of the mean square velocity vrms is:
1/2
! 3kT $
vrms = # &
" m %
 Gas properties

Energy distribution :
dN 2N E1/2 −E/(kT )
= 1/2 3/2
e
dE π ( kT )

The average energy is : Eave = 3kT/2

The most probable energy is : Ep = kT/2

 Gas properties
Mean free path l
l = mean distance between two collisions of a given molecule

1
λ=
2π d02 n
d0= molecular diameter (in m), n = gas density (in molecules per cubic meter)

− x/ λ
Distribution of free paths : N = N 'e
where N’ is the number of molecules in the volume and N the number of molecules
that cross a distance x before suffering a collision.

For two gases, a and b, the mean free path of a in b is:

1
λa =
' ! 2$
1/2 *
2 v π 2
) 2π na da #1+ b2 & nb ( da + db ) ,
)( " va % 4 ,+
 Gas properties
Particle flux

G = flux of an ideal gas striking a unit surface or crossing an imaginary lane of unit
area from one side:
1/2
nv " kT %
Γ= = n$ '
4 # 2π m &
n = the particle density, v = average velocity

Monolayer formation time

= time to saturate a surface with one layer of molecules
= function of the molecular arrival rate G, molecular size and sticking coefficient.
For a sticking coefficient = 1, we have:

1 4
tml = =
Γd02 nvd02
 Gas properties
Pressure

Absolute pressure on a surface : rate at which momentum mv is imparted to a unit

surface
1 2
P = nmvrms = nkT
3
SI unit for pressure: Pa = N/m2

Gas law
Ideal gas law: PV = nRT with R = 8.31 J/(mol. K) = NAk

Graham’s law or effusion law:

Effusion of gases through very small holes in porous membranes: at P, T constant
1/2
effusion ratea ! M b $
=# &
effusion rateb " M a %
With Ma and Mb = the molecular weight or molar mass of the two gases.
 Gas properties
Elementary gas transport phenomena

Viscosity

A viscous force is present in a gas when it is undergoing shear

The coefficient of absolute viscosity h :
Fx du
=η
Axz dy
With Fx the force in the x direction , Axz the surface area in the x-z plane and du/dy the
rate of change of the gas velocity at this position between two surfaces.
 Gas properties
h is due to transfer of momentum between the plates by successive molecular
collisions. So from the kinetic theory we have:

1
η = nmvλ
3
With h in N.s (SI units)

A more rigorous treatment gives :

1/2
0.499 ( 4mkT )
η = 0.499nmvλ =
π 3/2 d02
This relationship is only valid as long as the distance between the plates is greater
than the mean free path

For a rarefied gas in which l/y >> 1 (y= plate separation), the viscous force can be
expressed as

F ! Pmv $ U1
=# &
Axz " 4kT % β
The term in parentheses is the free-molecular viscosity, b is constant
 Gas properties

Thermal conductivity
Heat conductivity between two infinite parallel plates at temperature T1 and T2
respectively and with T1 < T2
H = heat flow, K = heat conductivity
If the mean free path is smaller than the plate spacing

dT 1
H = AK K= (9γ − 5)ηcv
dy 4

With h = viscosity, cv = specific heat at constant volume, g = cp/cv

 Gas properties
In the low pressure regime, the heat transfer between parallel plates is :

E0 = αΛP (T2 − T1 )
Where

α1α 2 1 (γ +1) ν1
α= Λ=
α1 + α 2 − α1α 2 8 (γ −1) T1

L is the free-molecular heat conductivity and a1, a2, a are the accommodation
coefficients of the cold surface, hot surface and system respectively.
Heat conductivity is determined by the energy transfer during collision
E0 in W.m2, L in W.m-2.K-1
The accommodation coefficient of a material is dependent on the material but also
on its cleanliness, surface roughness, and gas adsorption.

Diffusion

Simplification: vessel containing two gases

 Gas properties
The diffusion coefficient D of each gas is defined in terms of their particle fluxes G1,2
dn1 dn2
Γ1 = −D Γ 2 = −D
dx dx
The fluxes result from the partial pressure gradient of the two gases
1/2 1/2
! 2kT $ ! 1 1 $
8# & # + &
" π % " m1 m2 %
D12 = 2
3π ( n1 + n2 ) ( d01 + d02 )
With D12 is the interdiffusion coefficient of the two gases
For a single gas, the coefficient of self-diffusion is
1/2
4 ! kT $
D11 = # &
3π nd02 " π m %

If n, the density is replaced by P/kT, it comes that diffusion is approximately

proportional to T3/2 and P-1.

2
At low pressure (l >>>d ) D = rv
3
With r the radius of the pipe and v the thermal velocity, D = Knudsen diffusion
coefficient for a long capillary
 Gas flow
Gas flow regimes are characterized by the nature of the gas and the relative
quantity of gas flowing in a pipe.

Nature determined by examining the Knudsen’s number Kn = l / d

Relative flow described by the Reynolds’ number R = Urd / h with the mass
density, U the stream velocity, d the pipe diameter.

High pressure: l is small,

viscous flow , Kn < 0,01, (turbulent R > 2200) or viscous R <
1200
p.d > 6 10-1 mbar.cm
Medium pressure: l is medium,
Knudsen flow or transition flow ,
6 10-1 > p d > 3 10-2 mbar.cm
d/100 < l < d/2
Low pressure: l is large
molecular flow, Kn > 1.0
p.d < 3 10-2 mbar.cm
l > d/2
Gas flow
Gas flow
 Vacuum pumps
Mechanical pumps:

A special rotor rotates at a nominal speed by use of an electrical motor. The rotor-
stator geometry is such that during each cycle a certain amount of gas is
compressed and leaves the pump through a valve at the exit.
- rotary valve
- rotary piston
- roots
- turbomolecular
- scroll

Fluid entrainment pumps

A pressure depression is formed by the flow of a specific fluid (water, oil vapor…)

Other pumps: condensation pumps, absorption …

Primary pump: exit at atmospheric pressure

Secondary pump: exit at the inlet of a primary pump.
 Vacuum pumps
All pumps are characterized by a graph « pumping speed » = f (pressure)

A gas ballast is used when pumping condensable vapors (for example water). The
use of a gas ballast increases the pressure limit p0

Simple rotary valve pump

---- with gas ballast

 Vacuum pumps
Working range of vacuum pumps
Vacuum pumps
Pressure gauges

Two main classes of gauges:

– direct-reading gauges:
measure pressure by
calculating the force exerted
on the surface by incident
particle flux

– Indirect-reading gauges:
record the pressure by
measuring a gas property
that changes in a predictable
manner with gas density
Pressure gauges
Pressure gauges
 Vacuum plasma
Plasma = partially or totally ionized gas phase.
All types of plasma are characterized by :
– Plasma density Ne : number of electrons per unit volume
– Electron energy kTe in eV or Joule
– Ion density Ni : number of ions per unit volume
– Ion energy in eV or Joule
Comparison « cold » and thermal plasmas

parameters Low pressure plasma High temperature plasma

pressure 10-2 – 1000 Pa 105 Pa

Discharge current 0.01 – 1 A/cm2 10 – 105 A/cm2

density
Neutral gas temperature 77 – 1300 K 10 000 – 40 000 K
Tn
Electron temperature Te 2 104 – 105 K

Vibrational temperature 5 000 K

Tv
Rotational temperature Tn < Tr < Tv
Tr
Degree of ionization 10-8 – 0,8 ~1
 Vacuum plasmas

1018
-6 cm
= 10 Shockwave cm
lD High -4
10
1016 breakdown lD =
pressure
arcs
1014 Low pressure
arcs -2 cm Thermo nuclear
10
1012 lD = reactors (goal)
Controlled
1010 fusion
Ne (cm-3)

Glow experiments
0 m
10 c
discharges lD =
108 Flames
Electron
106 beams
2 m
Ionosphere Solar 10 c
corona lD =
104

102
4 m
Interplanetary 10 c
Interstellar
space lD =
100 space

0.1 1.0 10 100 1000 10000

kTe (eV)
1/2
! εTe $
lD = Debye length λD = # & with e0 = 8.85 10-12 F m-1
" ene %
 Vacuum plasmas
Electron and « heavy » particle temperature in a plasma

For a cold and low pressure

plasma:

F = qE
a = F/m
a = qE/m
v = qEt/m

Ee = mv2/2
Ee = (qEt)2/2m

ve >>> vh
Ece >>> Ech

E = 3kT/2
 Vacuum plasmas: glow discharges
DC glow discharge characteristic:

• if the pressure is low enough: unstable discharge (Townsend) at high voltage Vb

and low current density. Low degree of ionization and no glow
• Stable « normal » glow: increase in the current density , drop of the voltage.
Higher degree of ionization. The glow will cover progressively the whole surface
of the cathode
• Stable « abnormal » discharge: voltage and current density are both increasing
• Arc regime: high current density and low voltage.
 Vacuum plasmas: glow discharges
The glow discharge is composed of
– Free electrons
– Ions
– Atoms
– Molecules It is globally neutral
– Metastable species
– Excited particles

Degree of ionization : a = ni/n

In a DC discharge: electrons moves from the cathode (target) to the anode and
their energy is high enough to induce inelastic collisions with gas atoms or
molecules:
e- + Ar 4 2e- + Ar+
Argon ions are accelerated towards the cathode and are sputtering the target
(sputtering).

If the gas phase contains molecules that can be broken, reactive species can be
generated (Reactive sputtering)
 Vacuum plasmas: glow discharges

cathode anode

glow

potential

density

current
 Vacuum plasmas: glow discharges
Constituents and energy in a glow discharge

constituents Energy (eV)

In glow discharges
Electrons 0 - 20
Ions 0-2
Metastables/excited 0 - 20
UV / Visible 3 - 40
In bond
C-H 4.3
C-N 3.17
C-Cl 3.52
C-F 5.53
C=O 7.78
C-C 3.61
C=C 6.35
 Vacuum plasmas: glow discharges
Cross section of electron – atom collision
 Vacuum plasmas: glow discharges
Ionization potential of atoms and molecules
 Vacuum plasmas: glow discharges
Sputtering yield:

As a function of ion energy

As a function of the incident ion

atomic number
 Vacuum plasmas: magnetron sputtering
1) Without bias

permanent magnet

Target (-)
e ; Ar+; Ar ; sputtered atoms

Plasma

Substrate
Anode (+)
 Vacuum plasmas: magnetron sputtering
2) With bias potential on the anode

permanent magnet

Target (-)

Plasma

Substrate
Anode (+)
 Vacuum plasmas: magnetron sputtering
Characteristic I-V curve for an argon magnetron sputtering plasma
 Vacuum plasmas: magnetron sputtering
Deposit structure: Thornton diagram
 Vacuum plasmas: magnetron sputtering
Zone 1:
• T/Tm low
• High Ar pressure
Þ Diffusion of the atoms on the surface is low => strong shading effect
Þ Columnar structure with voids and poor mechanical link between the
columns
Þ High surface roughness
Zone T:
• Higher T/Tm
Þ Fibrous structure of small crystals with pour adherence between the fibers
but less voids
Þ Better mechanical properties
Zone 2:
• High T/Tm
Þ Growth dominated by surface diffusion of atoms
Þ Columnar structure with dense inter-crystals links
Þ The length of the columns can be equal to the film thickness
Zone3
• Growth dominated by bulk diffusion
=> Structure with fine crystals, recrystallization
 Vacuum plasmas: magnetron sputtering
Influence of a bias potential
 Vacuum plasmas: magnetron sputtering
Applications of PVD coatings
• Optical: glasses, mirrors, selective absorption, reflective coatings…

• Electrical: contacts, solid state electronics, solar energy …

• Mechanical: tribology, wear protection, solid lubricant layers

• Decorative: jewelry, taps, door handles, spectacles…

• Biomedical: valves, prosthesis…

Common coating compositions

• Nitrides, carbides and carbonitrides of transition metals (Ti,Zr, Cr…)

• Diamond like carbon

…
 Vacuum plasmas: magnetron sputtering
Industrial application: glass coating
 Cathodic arc evaporation and characteristics
• Characteristic of arc spots: strong thermo-field emission:
– High surface temperature of the spot root
– Strong electric field
e high plasma density in front of the cathode
e collective processes in the plasma e
– High current density ~ 1011 A/m2
– High power density > 1012 W/m2
• Expulsion of ions with very high kinetic energy
– Pressure gradient within the cathodic plasma
– Electron-ion friction
– Electric field (opposite direction in the plasma expansion zone)
• Plasma jets:
– Totally ionized flux
– 103 – 104 m/s
– 20 – 200 eV
 Cathodic arc evaporation and characteristics
• Explosive nature of plasma formation in a cathode spot e
source of droplets and debris particles < 1 µm or ~µm
• Continuous arc (dc)
– 30 to 300 A
– High deposition rate
– Importance of cooling
– Requirements on cables and electrical feed-throughs
– Usually magnetic steering of the cathode spots
– Density fluctuations e reproducible production of ultrathin films is difficult
• Pulsed arc
– Low average power e reduced cooling requirements
– High current : up to few kA
– Stable reproducible high plasma density
– Less macroparticles
– Flexibility
– Enhance incorporation of contaminants
– Importance of duty cycle d
d = ton / ( ton + toff )
Cathodic arc evaporation and characteristics: filtering

• Filtered arc deposition

– Macroparticles = problems for many applications e elimination or reduction of
their number e filters to:
• prevent line-of-sight trajectories between cathode and substrate
• guide the plasma to the substrate
– Guidance efficiency given by k (system coefficient): characterizes the couples
arc source and filter system

k = I i , filtered / I arc k ~1%

Transport mechanism: combination of an applied magnetic field and a self-

generated electric field
Electrons: follow and spiral around the magnetic field line
Ions: follow the electrons to maintain the plasma quasi-neutrality
Macroparticles: larger mass – to – charge ratio e move along straight
trajectories e arrive to the walls
Filtering does not guarantee a particle-free film
Cathodic arc evaporation and characteristics: filtering

Carbon Metal
Plasma Source Plasma Source

Substrate
Cathodic arc evaporation and characteristics: PIIID
• Hybrid methods combining phases (high energy) of implantation
and phases (low-energy) of deposition:
– PIIID = plasma immersion ion implantation and deposition
– MePIIID = Metal PIIID, if metal ions are involved

High-voltage phases:
– Sputter cleaning
– Formation of a mixed interface by implantation
– Stress « annealing »
Low-voltage phases:
– Ion assistance during the growth process
– With vacuum arc plasmas: no foreign species added e self-assistance

But
• Multiple ion charge states give rise to multiple ion energies
EZ = ZVb + E0
• High ion flux, ion current density and deposition rates e very thin sheath e
potential drop concentrated across a short distance e risk of sheath
breakdown: « arcing »
• Partial loss of the advantage of an isotropic 3D treatment
Cathodic arc evaporation and characteristics: PIIID

• PIIID = energetic deposition technique

– A large fraction of the incident particles penetrates the surface
– Ion delivers:
• Kinetic energy
• Potential energy
e thermal spike
Q -1
E( Q ) = Ekin,0 + AQeVsheat + Eic + Ec + Eexc + å EQ'
Q' =0

Ionization energy
Acceleration at Acceleration by
the cathode spot the image charge

Acceleration Cohesive energy Excitation energy

in the sheath
Cathodic arc evaporation and characteristics: PIIID
– Mechanisms of potential energy release:
• Photon radiation
• Auger processes
• Local electronic excitation
• Secondary electron emission…

– Ekin + Ep > binding energy

– Ekin + Ep > activation energy for surface diffusion

e effect on film formation and evolution

Cathodic arc evaporation and characteristics:impact on
film properties
• Good adhesion of films deposited by cathodic arc process due to ion
bombardment:
– Desorption of physisorbed impurities
– Increase of sticking coefficient for gases such as N2 and change of the
nature of the adsorption sites e formation of nitrides and carbides
– Formation of rough interfaces
– Implantation :
• Formation of a diffuse interface
• Breaking of bonds and formation of new bonds across the interface
• Spreading of the stress over a wider volume
– BUT :
• the substrate could be damaged
• Backscattering and self sputtering can prevent nucleation and growth
(Al/W multilayers, PhD F.A. Burgmann, RMIT university 2007)
 PIIID: example TiC-DLC

Deposition : mixing of C and Ti fluxes, pulsed biasing, « stress » hardened

nanocomposite
TiCx (x ~ 1) TiCx (x ~ 10)

TiC nanocrystals
Nanocrystalline TiC dispersed in
amorphous C matrix
Reactive Arc Evaporation

–Strong interaction between the ion

flux and the gas
–Modification of the charge state
distribution: exchange collision
processes and electron impact
ionization e - reduction of the
total ion current

From: M.M.M. Bilek et al.

J. Appl. Phys. 83 (1998) 2965
 Reactive Arc Evaporation: examples

Cr-Al-Si-N nanocomposites:
– 2 cathodes system
• Al + Si 11at.%
• Cr
– Nitrogen atmosphere
– Structure:
• Cr-Al(Si)-N nanocrystallites +
amorphous phase
for [Cr]/([Cr]+[Al]+[Si]) < 0.7

D. Rafaja et al., Surf. Coat. Technol. 201 (2006) 2835-2843