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Ion−assisted sputter deposition

John S. Colligon
Phil. Trans. R. Soc. Lond. A 2004 362, 103-116
doi: 10.1098/rsta.2003.1303

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10.1098/rsta.2003.1303

Ion-assisted sputter deposition

By J o h n S. Colligon
Surface Coatings Laboratory, Department of Chemistry and Materials,
Manchester Metropolitan University, Manchester M1 5GD, UK

Published online 25 November 2003

A review of the development of the ion-assisted sputter-deposition process is given.

The special features of thin films produced by this technique are outlined and some
main applications and future developments are discussed.
Keywords: sputtering; ion-assisted deposition; thin films; ion–surface interactions

1. Introduction
One of the major developments in the application of the sputtering process to the
production of thin-film coatings has been the use of an energetic particle beam to
bombard the substrate and growing film. Ions are usually used to provide this added
energy because their arrival rate and energy are easy to control but other energetic
particles such as atoms or molecules would have similar effects. The process is known
as ion-assisted deposition and is usually referred to by the acronym IAD, but a more
universal title would be energy-assisted deposition (EAD).
This paper reviews the development of the IAD process, describes the main IAD
methods, the special coating features that result from the application of this energy-
assisted sputtering technique and the potential applications of such coatings.

2. Energy-assisted deposition
(a) Ion plating
A schematic of the IAD process is given in figure 1. The concept of providing added
energy to atoms forming a thin film is not new. More than 70 years ago Berghaus
(B. Berghaus 1938, UK Patent no. 510 993) patented such a coating process. The
technique was developed further by Mattox & McDonald (1963), who showed that
improved adhesion and increased film density (Mattox & Kominiak 1972) resulted
from the bombardment. In the Mattox system, known as ‘ion plating’, an electron
beam was used to vaporize material from the target which was placed facing, and a
few centimetres from, a negatively biased (−1 to −5 kV) substrate. Ejected atoms
and molecules passed through the low-pressure (0.1–1 Pa) discharge which developed
between target and substrate, some being ionized and then accelerated by the electric
field to provide the added energy. The mean free path was less than the target–
substrate distance so that a high number of ions collided with neutral species and

One contribution of 11 to a Theme ‘Sputtering: past, present and future. W. R. Grove 150th Anniversary
Issue’.

Phil. Trans. R. Soc. Lond. A (2004) 362, 103–116

c 2003 The Royal Society
103
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104 J. S. Colligon

ions atoms

Figure 1. Schematic of the ion-assisted deposition process.

ion source
1keV, 15mA

ion source substrate

0–500eV, 0–0.03mA

sputtered flux of
A and B

ion beam

material B

material A

Figure 2. Dual ion-beam system.

continued as energetic neutral atoms. The substrate thus experienced bombardment

by a variety of atomic, ionized and molecular species with energies from thermal
values up to several keV.

(b) Arc-ion plating

A more recently developed alternative plasma-based IAD process is the arc-plating
system. In arc-plating a discharge is run in the abnormal glow region of the current–
voltage characteristic of the diode system formed between target and substrate. The
very high arc current forms a spot with a diameter of a few millimetres on the
target material, causing it to vaporize. After striking, the gas flow (usually argon)
used to start the arc can be switched off as the discharge will continue to run in

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Ion-assisted sputter deposition 105

the target vapour. Thus a mixture of vaporized atoms and ions flows towards the
substrate providing ion-assisted deposition. Unfortunately, the arc spot also causes
ejection of droplets of target material which are collected at the substrate and form
inclusions of different texture. This macro-particle problem has now been eliminated
by using a deflected arc (Aksenov et al . 1978a, b) which steers the ionized particles to
a substrate which is out of the line-of-sight of the target and cannot collect droplets.
Various modes of operation of this system are possible, ranging from simple energetic
deposition of the ionized particles to a sequence comprising ion implantation followed
by deposition, the latter generated by applying a pulsed negative voltage to the
substrate. For high-rate energy-assisted deposition of a single species the filtered arc
system has many advantages. However, for better control of parameters, and for
multi-element deposition of materials, ion-beam systems and magnetrons, described
below, have certain advantages.

(c) Ion-beam methods

In the late 1970s Weissmantel and co-workers (Weissmantel 1976, 1981; Weiss-
mantel et al . 1979) developed ion-assisted coating units based on ion beams. In this
work the atoms were either evaporated or sputtered and were deposited onto a sub-
strate, which was also bombarded by ions produced in an ion source. A schematic of
a typical layout of such a system, where atoms are sputtered by one ion beam and
a second ion beam is used for energy assistance, is given in figure 2. Many similar
systems were developed over the next few years (Harper et al . 1982; Martin 1986a;
Kheyrandish et al . 1994).
Over the same period the present author was developing a surface-modification
process known as ‘dynamic recoil mixing’ (DRM) (Argyrokastritis et al . 1984). In
this process one ion beam sputtered a thin layer of material A onto a substrate of
material B while a second ion beam, of energy ca. 10–20 keV, bombarded this thin
layer and caused recoil implantation of atoms of A into the substrate B. A fine
balance between re-sputtering and deposition allowed the thin-film thickness to be
maintained constant at a value commensurate with the ion range so that a substantial
intermixing of the materials A and B occurred. The layers produced had excellent
adhesion and this DRM process allowed formation of ultra-thin surface-modified
layers with interesting electrical properties (Colligon et al . 1984). Similar results had
been reported by Perkins & Stroud (1972), who used an ion implanter to provide
Ar ions of energy 30–100 keV and studied the resistance of mixed layers formed by
recoil implantation of aluminium into silica. DRM is, in fact, a static version of IAD,
where the latter simply allows the deposition rate to exceed the re-sputtering rate
and the film increases in thickness.
Although the ion-beam approach has the advantage of providing excellent control
of deposition parameters and is an essential starting point when exploring the prop-
erties of new coatings, it has the disadvantages of slow growth rates and a restriction
to the treatment of small-area samples. This limits its application commercially,
although the ion-beam method has been found to be very useful for the produc-
tion of high-quality optical multilayer coatings (McNeil et al . 1985; Martin 1986;
Colligon 1992).

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106 J. S. Colligon

(d ) Unbalanced magnetron sputtering

An important solution to this problem was provided by the work of Window &
Savvides (1986a, b), who showed that the adoption of a special magnetic field config-
uration on magnetron sputtering systems gave the possibility for large-area samples
to be coated with simultaneous ion assistance (see figure 3). Whereas in conventional
magnetron systems the N and S poles are of equal strength, so that field lines form
tight closed loops above the target (figure 4), in the so-called unbalanced magnetron
mode (UBM), some flux lines move out and form a closed loop via the substrate.
Some of the ionizing electrons can now follow these lines and the plasma therefore
spreads out to the substrate. If the substrate is not connected electrically, it acquires
a floating potential of ca. 30 V negative with respect to the plasma and, therefore, it
attracts ions with energy of ca. 30 eV from the plasma to produce IAD conditions.
Alternatively, a voltage supply can be connected to the substrate to allow this ion
energy to be varied.
Another method for moving the plasma region towards the substrates is to use
arrays of two, four, six or eight magnetrons, where the magnetic poles of neighbour-
ing magnetrons are always of opposite polarity. Such a system is called a closed-field
unbalanced magnetron (CFUBM) and a four-magnetron array is illustrated in fig-
ure 5. This magnetic field configuration traps the plasma. Samples, rotating on a
carousel about the central axis, will be in this plasma region and will therefore
acquire a negative voltage and be ion bombarded. A further advantage of this type
of system is that a film comprising several species can be formed by choosing different
target materials A, B, C, D for the four magnetrons. By adjusting the magnetron
power levels the overall percentage content of materials A, B, C, D can be varied.
CFUBM systems have been described by Musil & Kadlec (1990), Kadlec et al . (1990)
and Teer (1990). Under typical operating conditions and with chamber pressures of
the order of 0.2–1 Pa, substrate currents of up to 100 mA at 10–100 eV provide the
ion assistance. A further improvement in coating adhesion has been found to occur
by using a magnetron-assisted arc discharge, with Ar or Cr ions, before starting the
CFUBM process (Münz et al . 1991, 1993). The Ar or Cr ion-bombardment etching
of the substrate appears to improve the bonding in the so-called arc-bond sputtering
(ABS) process (Hurkmans et al . 1997). The CFUBM method is also useful if a mul-
tilayer structure is required, A–B–A–B– · · · . In this case a switching mode is used
where only two magnetrons will operate with material A and, subsequently, only the
other two will operate with material B. Such multilayers (see, for example, Helmers-
son et al . (1987) for TiN/VN layers of 3–5 nm thickness) have been found to produce
much harder coatings than the hardness value of either of their components A or B
because the layer structure blocks the movement of dislocations.

3. Special features of IAD

(a) General comments
The advantages of using ion-assistance during deposition are

(i) removal of residual gases and other contaminants from the substrate by the ion
bombardment;

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Ion-assisted sputter deposition 107

substrate

n s n

Figure 3. Schematic of an unbalanced magnetron system.

substrate
film

target
–1kV
n s n
s n s

Figure 4. Schematic of a balanced magnetron system.

(ii) transfer of additional energy to surface and depositing atoms which give more
surface mobility and allow atoms to move to different sites producing denser
and better bonded films and allowing film stress to change, usually from tensile
to compressive;

(iii) provision of local added energy so that atoms move as if they were at a very
high temperature, but suddenly cool (at rates up to 1014 K s−1 )—this allows
the formation of compounds and phases which would not normally be possible
at the ambient temperature.
There has been extensive debate about how much added energy is required to
produce the best-quality coatings. Harper et al . (1982) surveyed many sets of IAD
results and showed that the main changes in film properties always occurred for added
energies between 1 and 100 eV per deposited atom. However, Petrov et al . (1993)

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108 J. S. Colligon

s n s
rotating
samples

n n

s s

n n

s n s

Figure 5. Closed-field unbalanced magnetron system.

showed that, for deposition of Ti–Al–N films, the composition, preferred orientation
and lattice spacing were different for the same added energy depending on whether
it was provided by one high-energetic ion per atom or by several lower-energy ions.
The problem, as discussed by Colligon (1995), is the different way in which energy is
transmitted to the arriving atoms. Higher-energy ions will produce additional defects
in deeper layers of the coating which may remain trapped. Another factor is that
the ion energy reflected back from the substrate will depend on substrate mass and
density. This means that the added energy required at the start of film growth, where
substrate effects are important, could be very different from the energy required at
later stages when the ion interaction is entirely with film atoms. The only general
guideline from all these studies is that added energies of ca. 10 eV per atom are
usually effective and lower energies (20–30 eV) should be used to minimize defect
production.

(b) Morphology and density

It has been well known since the work of Movchan & Demchishin (1969) that
the structure of a growing film depends critically on the film-deposition parameters.
Their results showed the effect of substrate temperature change, which is in fact
influencing the ability of the arriving atoms to diffuse on the surface. At low sub-
strate temperatures T , in a region of structure known as zone 1 (0.1 < T /TM < 0.3,
where TM is the melting point of the film material), inverted pyramidal structures
will grow which point towards the source of atoms and which have voids between
them. For 0.3 < T /TM < 0.45 (zone 2) the surface diffusion increases and columnar
crystalline grains begin to form and the films become denser. At even higher values of
T /TM (zone 3) bulk diffusion can occur, leading to the formation of equiaxed grains.
A further parameter was included in this model by Thornton (1974), who showed the
influence of pressure in the deposition system on morphology. This parameter influ-
ences the energy of arriving species and, to some extent, directional effects because,
at higher pressures, there are more collisions between the source and substrate. Ion

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Ion-assisted sputter deposition 109

assistance will, in general, provide additional energy to the arriving atoms for surface
diffusion and, in addition, cause some atomic displacements which tend to fill any
voids in the growing film. The resulting IAD coatings therefore become much denser
even when deposited at relatively low substrate temperatures. This densification
gives them more stability when exposed to moisture or corrosive elements. Such an
effect has been reported by Kelly & Arnell (1998), who showed that, for closed-field
unbalanced magnetron sputtered films of Al, Zr and W, the T /TM ratio for the onset
of zone 2 structures was reduced to 0.15. Martin et al . (1984) have shown that the
density of a ZrO2 thin coating increased by 14% compared with the normal value for
simple evaporation when it was bombarded by 600 eV oxygen ions during deposition
and that its refractive index then became more stable during changes in ambient
conditions. Müller (1989) has presented results of molecular dynamic simulations of
film density with and without ion assistance and his model confirms the change in
density found by Martin et al . (1984).
Barna & Adamik (1998) have shown that, for systems where two species are being
deposited concurrently (for example, a main component plus an impurity), a com-
petition develops with the impurity species being segregated on the growing crystal
surface or being dissolved into the crystal. The presence of such impurities can act as
an inhibitor which decreases the grain size or as a promoter which increases this grain
size. These effects can occur selectively on different crystal faces so the situation is
extremely complex; more so with the additional parameter of ion energy in IAD pro-
cesses. However, the prospect of being able to grow films with specified structure is
very attractive and it is expected that further work to study the additional impurity
effects will now continue.

(c) Compositional changes

The additional movement of atoms and the implantation of ions—which, for nitro-
gen and oxygen, are present as atomic rather than molecular species—encourages
chemical reactions so that, under appropriate conditions, not only can chemical com-
pounds with the desired stoichiometry be produced, but also metastable phases and
alloys not normally produced at lower temperature can be formed. Hentzell et al .
(1985) showed that, provided more than one N ion per Al atom reached their sub-
strate, stoichiometric AlN was formed. Kheyrandish et al . (1994) showed a similar
effect for the formation of TiNx , where an increasing N/Ti arrival ratio formed TiN.
However, under certain ion/atom arrival conditions the value of x increased to 1.3
indicating the formation of a possible new Ti3 N4 phase, which was blue in colour.
Rossnagel & Cuomo (1988) also discovered a new Cu2 O5 oxide when bombarding
evaporated copper films with oxygen ions. In studies of Al–Mg alloys, Arnell & Bates
(1991) and Baldwin et al . (1996) showed that the solubility limit of Mg in Al could
be raised from the normal 1.9% to 20% and of Al in Mg from 2.1% to 30%. This
ability to seed in additional components has been exploited by many researchers
including
(i) Cevro (1995), to produce reflective coatings with variable SiO2 and Ta2 O5
content, to give any refractive index between the SiO2 and Ta2 O5 level;
(ii) Fujimoto et al . (1993) and Davenport et al . (2001), to produce different Fe–Cr
alloys for corrosion studies;

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110 J. S. Colligon

(iii) Fox et al . (1999), to improve the wear performance of MoSi2 ; and

(iv) Donohue et al . (1997), to form a complex Ti–Al–Cr–Y–N alloy which forms a
stable high-temperature film.

(d ) Phase changes and microstructure control

The additional energy and rapid cooling available in an IAD coating process can
trigger the formation of certain phases of a coating material which would normally
only be found using much higher substrate temperatures. A typical example of this
effect is the formation of cubic boron nitride films, which require this additional
ion-assist energy to be transformed from the normal hexagonal to the cubic form.
Park et al . (1997) have shown that the peaks characteristic of hexagonal BN in
the FTIR spectra for the non-ion-assisted films disappear and are replaced by the
characteristic cubic BN peak as the ion-assisted current level increases to ca. 60 µA.
This work was performed using a 50:50 Ar:N2 ion beam at 400 eV and substrate
temperature of 400 ◦ C. Ye et al . (2001) have shown that a high percentage (80%
plus) of cubic BN content can be attained using only nitrogen ion bombardment
at substrate temperatures of ca. 150 ◦ C and that, once the cubic phase is formed,
further growth can occur even at 80 ◦ C. This is another example of the importance of
studying IAD conditions, not only at the start of film growth, but also at later stages
when substrate effects have been removed and phase changes have been established.
One of the most exciting developments in IAD is undoubtedly related to the for-
mation of super- and ultra-hard nanocomposite coatings. Veprek & Reiprich (1996)
and Veprek & Argon (2002) have shown that, when TiN and Si3 N4 are deposited
with simultaneous ion bombardment in a plasma-assisted chemical vapour depo-
sition system (PACVD), it is possible to produce crystals of TiN of the order of
3–6 nm in diameter surrounded by an amorphous layer (about one monolayer thick)
of Si3 N4 . Such a material has hardness values in excess of 50 GPa, in some cases
values near 100 GPa were reported, which is the hardness of diamond, but subse-
quent measurement of samples has shown that the hardness falls with time to the
50–60 GPa level. The most interesting factor is that this 50–60 GPa material appears
to remain hard even after heating up to over 1000 ◦ C. This makes it superior to dia-
mond which begins to oxidize in air at above 600 ◦ C.
Musil et al . (1999), Musil (2000) and Musil & Vlcek (2001) have shown that
these 50–60 GPa hard coatings can be formed using magnetron sputtering if the
substrate is heated sufficiently. This is an obvious area for detailed study using the
parameter control offered by ion-beam systems. Figure 6 shows the trend in hardness
as substrate temperature is varied (J. S. Colligon 2003, unpublished data). Under
these ion-assist conditions, a value of 45 GPa is attained at ca. 500 ◦ C and it appears
from the trend in the curve that higher values should be attainable.
The mechanism of formation of these nanocomposite structures is not understood.
Several guidelines for producing the c-TiN/a-Si3 N4 system (where ‘c-’ signifies a
crystalline and ‘a-’ an amorphous compound) can be gleaned from the available data
and may be summarized as follows.
(i) Ion-assistance is essential.
(ii) The film must contain about 9 atomic % Si.

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Ion-assisted sputter deposition 111

45

40

hardness (GPa)
35

30

25

20

200 300 400 500 600 700 800 900

substrate temperature (K)
Figure 6. Increase in hardness of ion-assisted Ti–Si–N coatings on silicon as a function of sub-
strate temperature. Si content in films 12 atomic %, N2 ion—assistance at 400 eV and an
ion:atom ratio of 2:1. Squares, experimental results; circles, curve-fitting data. (J. S. Colligon
2003, unpublished data.)

(iii) The substrate temperature must exceed 500 ◦ C.

There are clear correlations between nanocrystal size and Si content, the size
decreases as the Si content increases; this points to an effect occurring during film
nucleation being the determining factor. As noted in the previous section, Barna &
Adamik (1998) have noted the influence of impurities on the film growth modes.
In the Ti–Si–N system the impurity is, in effect, the Si. Barna et al . (2000) have
discussed this problem further and suggest that the additive species can segregate
to form a tissue layer encasing the nanocrystals; once this layer is complete, fur-
ther nucleation of the majority species can occur and the segregation process will
repeat. Such a process would certainly explain why the crystal size is dictated by the
concentration of Si and may be a reason why different systems produce films with
different hardness. The PACVD method must introduce additional chemical species
at the surface compared with ion-beam and magnetron deposition methods. Veprek
(2003) has shown that oxygen content even as low as 1 atomic % can prevent the
segregation into TiN crystallites in the Ti–Si–N system.
There are many other alloy systems that can be explored. AlN, ZrN, NbN and WN
can replace the TiN. Musil (2000) has also shown that systems comprising TiN plus
a soft material, such as Cu, can produce useful alloys which are not so hard but have
excellent ductility. Other nanocomposite systems include ncTiN/a-C:H (where ‘nc’
signifies nanocrystalline) (Voevodin & Zabinsky 1998), which can have hardness up
to 40 GPa and which has a low coefficient of friction making it useful for extrusion
components; Ti–Al–N (Kim et al . 1999), which may form a nanocomposite structure
during use; and Ti–Al–Si–N (Horling et al . 2002), which is stable up to 850 ◦ C.
Current opinion for suitable engineering material properties is that, rather than
selecting a coating with a high value of H, a better choice is to select on the basis of
the ratio H 3 :E 2 being large, where H is hardness and E is Young’s modulus (Tsui

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112 J. S. Colligon

700

600

compressive stress (MPa)

500

400

300

200

100

0
0 50 100 150 200 250 300 350
added energy (eV per atom)
Figure 7. Reduction in compressive stress in ion-assisted SiO2 films
using 150 eV oxygen ions (adapted from Sirotkina (2003)).

et al . 1995). This implies either a high value of H or a low value of E, which occurs
for ductile materials. In this situation the material will give under load but still be
reasonably hard and this has implications in protecting the substrate material from
the full impact of the load.

(e) Film stress

Ion-assisted deposition influences the stress in thin-film coatings in various ways.
If the film is under-dense, as is generally the case for evaporated films, the added
energy causes displacements which densify the film material and the initial, tensile,
stress is reduced. At the same time, some surface atoms are pushed into the material
and create compressive stresses. In addition the ions themselves are incorporated into
the film material and collision cascades develop which, if the substrate temperature
is low enough, leave interstitial defects, which introduce more compressive stress.
If the temperature is higher, the added energy can trigger annealing of some of
this damage and a reduction in stress. The situation is thus critically dependent on
deposition conditions, as shown by Pauleau (2001). Although it is possible to choose
conditions which create a small compressive stress (usually best for film adhesion to
the substrate), this stress can change during operation, especially if the component
is to be used at high temperatures, and lifetime tests must be undertaken to ensure
that such changes do not cause problems.
Nevertheless, some useful improvements in stress can be achieved by choosing the
optimum deposition parameters. Figure 7 shows data for stress in 150 eV oxygen
ion-assisted deposition of silicon-oxide thin films as a function of the added energy
per Si atom (Sirotkina 2003). There is clearly a significant reduction of stress from
525–270 MPa as the added energy goes from zero to 300 eV per atom.

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Ion-assisted sputter deposition 113

80

number of holes
60

40

20

0
uncoated TiN MoST TiN + MoST DLC + MoST

Figure 8. Increase in lifetime of steel drills coated with TiN plus MOST (8.5 mm ADX drills,
1050 RPM, 0.3 mm per revolution, 40 mm hole depth, coolant). (Adapted from Fox et al . (1999).)

4. Applications of IAD
IAD coatings are used in many fields and a review of some of these applications
may be found elsewhere (Colligon 1999). They can be used to produce an attractive
finish to a product and such decorative coatings take up a large area of the market.
Examples are sanitary items, such as bathroom taps and fittings, where a silver or
gold finish adds to the attraction of the product.
The next largest field of application is in coatings for engineering applications. The
aim here is to produce a product which has a longer lifetime and, where appropriate,
lower friction. An example of such a coating is the low-friction coating known by the
name MOST, which is produced by sputtering molybdenum disulphide and titanium
using two magnetrons (Fox et al . 1999). Figure 8 shows that the lifetime of drills
coated with TiN plus MOST is significantly increased. Also Cr-plated punches with
the MOST coating can punch out many more coins than the uncoated tool. Similar
improved performance of Ti–Al–Si–N coatings on drills used without coolant have
been reported by Morstein et al . (2003) and on TiB2 /TiC multilayer coatings on
WC inserts used without coolant to cut 1018 steel and 319 Al (Lee et al . 2003).

5. Conclusions
Whereas sputtering studies have taken place for more than 150 years, the ion-assisted
sputter deposition process, first mentioned in 1938, has really only developed in the
last 40 years. The IAD process provides some additional fine-tuning to the sputtered
coatings which make them more durable than conventionally sputtered coatings.
Much work needs to be done to improve the understanding of the formation of
special micro- and nano-features in these films as these have rather unique properties
which would improve coating performance. Ion-beam methods provide the controlled
parameters essential for such studies but, in application, plasma-based methods are
most likely to be the basis of industrial coating systems.

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114 J. S. Colligon

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