Journal of Modern Physics, 2012, 3, 1626-1638
http://dx.doi.org/10.4236/jmp.2012.330200 Published Online October 2012 (http://www.SciRP.org/journal/jmp)
A Supersonic Plasma Jet Source for Controlled and
Efficient Thin Film Deposition
Ilaria Biganzoli1, Francesco Fumagalli1, Fabio Di Fonzo2, Ruggero Barni1, Claudia Riccardi1*
1Dipartimento di Fisica Occhialini, Università degli Studi di Milano-Bicocca, Milano, Italy
2Center for Nano Science and Technology, Italian Institute of Technology, Milano, Italy
Received August 29, 2012; revised September 30, 2012; accepted October 7, 2012
ABSTRACT
A novel plasma source suitable for controllable nanostructured thin film deposition processes is proposed. It exploits the
separation of the process in two distinct phases. First precursor dissociation and radical formation is performed in a
dense oxidizing plasma. Then nucleation and aggregation of molecular clusters occur during the expansion into vacuum
of a supersonic jet. This allows a superior control of cluster size and energy in the process of film growth. Characteriza-
tion of the plasma state and source performances in precursor dissociation have been investigated. The performances of
this new Plasma Assisted Supersonic Jet Deposition technique were demonstrated using organic compounds of titanium
to obtain TiO2 thin nanostructured films.
Keywords: Plasma Sources; ICP Discharges; PECVD; Plasma Diagnostics; Titanium Dioxide; Thin Film Deposition
1. Introduction
The deposition of thin films using physical vapour depo-
sition or chemical vapour deposition (CVD) techniques is
a process that has many applications in material science
[1]. In particular the production of nanostructured mate-
rials is, currently, one of the fields of more intense re-
search and technological development. Thin films made
of oxides, semiconductors or metals are especially inter-
esting in this respect. The possibility to change their mor-
phology at the nanoscale makes them suitable for appli-
cations like catalysis and photocatalysis, energy conver-
sion or storage, rather than more conventional uses as
barrier or protective coatings [2]. Despite their interest,
few innovative techniques exists for the controlled depo-
sition of nanoscale assembled materials. As an example,
titanium and zinc oxides are usually produced by sol-gel
synthesis of nanoparticles followed by sintering, gener-
ally yielding disordered films either with moderate po-
rosity or in aerogel form [3,4]. Ordered structures, with a
somewhat controlled porosity, have been obtained by
using templating agents [5], even if their removal may
cause some dimensional changes. Template-free fabrica-
tion and photocatalytic activity of hierarchically organ-
ized nanostructured TiO2 has been reported, by typical
thin film deposition techniques, such as CVD [6,7],
sputtering [8] and pulsed laser deposition (PLD) [9]. In
particular enhanced surface reactivity was related to the
3D columnar structure increasing the surface area, con-
trolled by their thickness and spacing [6]. Other notable
examples of 3D film structure were reported in the form
of fractal “forest-like” TiO2 deposit by CVD [10]. In ge-
neral, however, the active surface area of these films is
limited and hardly controllable to a large extent and there
is only a modest control over the deposited material com-
position. Even PLD, though being a versatile, one-step,
template-free process [9], still has limited chances of up-
scalability, needed in large area applications such energy.
Plasma enhanced CVD (PECVD) is a particular version
of thin film deposition. In the field of nanostructured
materials it was pioneered by applications to Si and Ge
quantum dots production, using silane injection in an
argon plasma [11]. Although promising, no examples of
nano-assembled functional films have been demonstrated
so far. Moreover, there are very few examples of plasma
processes capable of depositing nanostructured films with
controlled chemistry, morphology and porosity [12]. The
novelty of the proposed approach, which we denomi-
nated Plasma Assisted Supersonic Jet Deposition (PA-
SJD), is the segmentation of the gas phase material syn-
thesis in two separate steps: chemistry control in a reac-
tive cold plasma environment; nucleation and assembling
control by means of a supersonic inseminated jet over a
substrate. High throughput and fast deposition rates
could be achieved using high density plasmas. Vaporiz-
able and stable monomer could be employed as the
source of the oxides, the semiconductors or even the me-
*Corresponding author.
C
opyright © 2012 SciRes. JMP

I. BIGANZOLI ET AL. 1627
tals. The extraction of a supersonic plasma jet allows to
focus the precursor flow on the substrate and to control
the growth and the sizes of clusters. Over conventional
gas phase processes the proposed technique allows con-
trol of the kinetic energy of clusters, whence control on
their assembly pattern on the substrate. In particular
when molecular cluster deposition is performed under
condition of supersonic jet several advantages could be
envisaged including the better collimation and stability
and the control of crystallinity. By changing the condi-
tions during processing it is also possible to obtain
graded films. Here we present results concerning the de-
sign and performances of a novel plasma source with a
reaction chamber where plasma dissociation and clus-
terization of precursors could be achieved and from
which a sample of reactive radicals could be extracted.
Extraction is performed through a nozzle, producing a
supersonic jet which propagates in an expansion chamber
where deposition processes happen, to be used to grow
thin films with controlled morphology at high yield. We
will characterize the plasma in our source and then we
will demonstrate that ordered nanostructured films of
TiO2 could be grown and that their morphological prop-
erties, similar to dendritic structures obtained by means
of PLD, can be tuned, by varying the process parameters.
Then a fair parameter control could be achieved in order
to tailor the optoelectronic properties of synthesized ma-
terial.
2. The Experimental Setup
As stated in the introduction, our main purpose was to
spatially separate the region where dissociation of the
precursor is achieved in a dense plasma environment and
another region where deposition takes place, on a sub-
strate which is exposed to a flow of mainly neutral parti-
cles and clusters. A sketched view of the source setup is
shown in Figure 1. As for the electrical discharge our
approach was to use an inductively coupled plasma (ICP)
[13,14]. This allows to reach quite large plasma densities
and relatively small electron temperatures at moderate
pressures, 1  100 Pa. This favours dissociation of ex-
ternal, weakly bound chemical groups in organic precur-
sors, partially preserving the backbone structures, for
instances Si-O bonds in HMDSO [15] or Ti-O ones in
titanium ethoxide [16]. A radiofrequency (RF) signal was
then applied to an antenna facing the plasma chamber.
For the discharge feeding we employed a commercial RF
power supply (PFG-1600 by Huettinger, maximum pow-
er 1.6 kW). Then our experiments have been performed
all at a fixed frequency of 13.56 MHz. An L-type match-
ing box was used along the transmission line. A passive
system fits our needs, since plasma showed to be quite
stable during operation, even during the fairly long depo-
Figure 1. Lay-out of the experimental setup.
sitions exceeding 30 minutes. To reduce cable length, the
system was mounted directly on top of the vacuum
chamber and connected with the RF antenna through
copper straps (see Figure 1). The measured reflected
power was below 1% - 2% even at power level of about
500 W. We have used a two and three quarters loop pla-
nar antenna made of hollow copper wire (4-external, 3-
internal mm diameters). This allows to circulate deion-
ized water for cooling purposes. The total length was
about 80 cm with an outer and an inner radius of 54 and
40 mm respectively. The antenna was inserted in a teflon
scaffold, a perforated disk (22 cm diameter, 17 mm thick
with a 33 mm radius hole), and voids were filled with an
epoxy patch adhesive (see Figure 1). Over the internal
side of the teflon scaffold, where the antenna is embed-
ded, an alumina perforated disk (135 mm diameter, 2 mm
thick) is placed, facing the plasma. This reduces con-
tamination due to teflon sputtering. It also sustains much
better the heat load from the plasma exposure. Under the
teflon scaffold, an aluminium disk is placed, sealing the
plasma chamber. In the central part of the disk, where
there is the transition between the plasma and the deposi-
tion chambers, the nozzle region is excavated, as de-
scribed below. The supply RF signal is connected to the
external edge of the coil (and shielded), while the inter-
nal end is connected to the ground. The RF connections
run down from the top of the device along the external
walls of the plasma chamber (see Figure 1), to reduce
contamination. The total inductance of the antenna sys-
tem was measured to be 2.5 μH with an impedance of
about 213 Ω at RF. Particular care was paid to the
earthing. Large copper straps were employed to connect
the different parts of the vacuum chamber (main body,
top and bottom plates, internal plasma chamber) and the
RF network to ensure low resistance, short ways to
ground. This proved essential to prevent discharges hap-
pening at unwanted locations and RF power dispersions.
Afterwards stable working conditions, even at relatively

I. BIGANZOLI ET AL.
1628
high power levels, could be maintained for times ex-
ceeding hour-long operations. Localized temperature
measurements on the plate under the antenna confirm
that heating is moderate even after running more than 1
hour at 500 W. Our device operates under moderate vac-
uum conditions, that is roughly in a range 1  100 Pa. It
was built up out of a commercial stainless-steel cylindri-
cal vacuum chamber (31 cm diameter and 40 cm height).
Several ports allows to monitor the discharge as well the
insertion of diagnostics or sample holders. On the bottom
a large (100 mm diameter) vacuum flange constitutes the
main connection to the pumping system. On the top
flange 11 ports where placed, for gas/vapour-inlet, RF
feed throughs, view ports and diagnostics. The plasma
chamber is appended in the upper central part of the de-
vice. It is made of a thick aluminium cylinder (125 mm
diameter and 95 mm height) closed on the bottom by the
antenna scaffold and the sealing aluminium disk. Its
volume is approximately 1.15 liters. Although a vacuum
proof insulation from the main chamber is not strictly
needed, all junctions of the plasma chamber were sealed
using Viton rings in order to prevent leakage of precur-
sors and of reactive agents in other part of the device.
The rest of the device constitutes the deposition chamber.
Its volume is approximately 30 liters. However the active
region is just below the plasma chamber. On a side port a
rotable/movable vacuum feedthrough is used to move
forward/backward the sample holder and to expose dif-
ferent substrates at fixed distances from the plasma
chamber exit. The connection between the plasma cham-
ber and the deposition chamber consists of a convergent
nozzle followed by a thin aperture. In a first realization
the latter consists of a slit (22 mm length, 2 mm width)
cut in a 0.9 mm aluminium foil. The lay-out is sketched
in Figure 2. A circular hole (7.5 mm diameter) was tried
too, the better shape being determined by the deposition
needed properties [17]. Above this orifice, the aluminium
disk was excavated forming a gentle transition (conver-
gent nozzle) from the teflon aperture, at the level of the
Figure 2. Cross section of nozzle region with a schematic
view of the jet expansion in our experimental setup.
RF coil to the bottom of the disk aperture (a 22 × 30 mm
rounded rectangle), where one of the different apertures
is to be sealed. With this choice, when a differential pres-
sure exists the flow out of the plasma chamber assumes
the form of a jet. In principle, other convergent-divergent
configurations could be used (for instance De Laval noz-
zle [18]), but this one has the advantage that the aperture
foil can be easily removed and modified. As we will dis-
cuss in a short while, when the pressure difference is
high enough the jet expansion can become supersonic.
We have already said that such a capability was one of
the main goal to be achieved in the design of the source.
In this first design of the source, we choose to use a sin-
gle pumping system composed of a turbo molecular
pump (Turbovac TW250-S by Leybold) and a rotary
pump (Alcatel 2020A). As already mentioned, the
pumping system is connected at the bottom of the main
chamber, through a gate valve. The actual pressures in
the two chambers is controlled by the conductances of
the connections (see Figure 1) and by the position of the
manual leakage valves connected to the gas-mixture feed
system, as it will be discussed below. Three direct
gas-inlet on the top plate of the device were used to pre-
pare the gas phase in the plasma chamber. The central
port was employed for the precursor injection system.
Other two ports, 50 mm out of center, are used for the
gases. Two micrometer dosing valves (EVN-116 by
Pfeiffer) were chosen, in principle supporting an ex-
tended flowrate range of more than 8 order of magnitude,
Q = 10−6  102 Pa·m3·s−1. In the experiments discussed
below, an argon and oxygen mixture was chosen. Oxy-
gen was selected as the oxidizing agent to chemically
attack the organic groups in precursors. Oxygen is in fact
the most efficient oxidizing plasma, but used as a pure
gas has many drawbacks, including strong stresses of the
pumping system and of the vacuum parts. Argon dilution
was then used to provide a stable, not so stressing plasma
environment. Argon ICPs are also well known in litera-
ture and their properties have been studied at length
[13,19]. High purity argon and oxygen cylinders (5.0 by
Sapio) were employed. A dedicated and calibrated, re-
mote controlled flow-meter (EL-Flow by Bronkhorst)
has been installed during the preliminary device test
phase, with argon. Using such calibration, we could as-
sess that during experiments flow-rate was changed in a
somewhat limited range of Q = 0.01  0.1 Pa·m3·s−1. The
nominal pumping speed S and the real ones of argon
(0.21 m3·s−1) and oxygen (0.23 m3·s−1) are similar for our
pump thus providing a sensible control of the gas-phase
composition, preventing accumulation and a derive in the
gas-phase mixing. Pressure during operation is provided
by two capacitance gauges (an Alcatel ADS-1003, upper
range of 1 kPa in the plasma chamber and a Pfeiffer CMR-
264, upper range of 100 Pa in the deposition chamber).

I. BIGANZOLI ET AL. 1629
Their pressure reading is rather unsensible to the gas-
phase composition and their precision is good in the
working pressure ranges. Then the argon/oxygen mixing
ratio was simply evaluated by measuring the pressure
ratio after opening at first argon dosing valve and subse-
quently oxygen one. To control contamination and over-
all purity, the system could be evacuated using the full
capability of the pumping system. This is performed rou-
tinely before sample preparation is to be started. Vacuum
pressure is controlled in the main chamber by a Penning
gauge (PTR-90 by Leybold). Although the use of pre-
cursors in deposition processes makes unavoidable some
contamination of the chamber walls, the quite large
volume of the chamber and the flow of the gas somewhat
limited to the central part of the device helps in keeping
at acceptable levels. Periodic cleaning of the plasma
chamber walls, which can be completely removed, is
performed. Then outgassing flowrate could be controlled
and vacuum levels of a few 10−4 Pa could be achieved
after a few hours of full speed pumping, since sealing.
For the injection of the precursor we have chosen a nee-
dle. While for the discharge ignition and development in
the plasma chamber a uniform and well mixed gas mix-
ture is a nice starting point, efficient precursor dissocia-
tion does not need it. Indeed a mixing of the precursor
outside the plasma chamber could provide complications,
since heating is useful to vaporize liquid compounds or
to increase the vapour pressure of a precursor but it is not
needed for a gas. A uniform distribution of the precursor
in the whole plasma volume is not needed too, since
deposition is performed elsewhere and most of the vol-
ume is too far from the injection point. Moreover the
effective residence time in the plasma region needs to be
optimized or, at least, controlled in each deposition
process, and cannot fit a once and for all scheme as im-
plied by performing the mixing of the gas-phase outside
the plasma chamber. We used a hollow copper wire
(6-external, 4-internal mm diameters) with a 1.5 mm hole
drilled at the bottom end. The wire is mounted on a vac-
uum feedthrough at the center of the top plate and gets
down in the plasma chamber to a regulable depth, in the
experiments reported here 87 mm, thus being a few mm
above the level of the RF coil and 30 mm from the slit.
Another micrometer dosing valve of the same kind con-
trols the vapour flow. A reservoir, a sintered aluminum
flask of a few tens of ml with a brass sealing is used to
store liquid precursors. After refilling, the flask and the
micrometer valve connections were briefly pumped by a
rotary pump. This remove most of the residual air from
the flask, allowing the reservoir to be stored with the
liquid precursor in equilibrium with its saturated vapour.
This obviously select as usable precursors only those
with a sufficiently high vapour pressure at set tempera-
ture, otherwise outgassing and residual air will contami-
nate the gas-phase. To increase the flow, heating of the
precursor flask and the injection system constitutes the
most viable way. A heater was then put under the flask.
Insulation of the injection system is provided too and
tested by the use of several thermocouples. It should be
noted that the injection needle gets heated by the plasma
and by the RF itself. So the actual temperature of the
precursor vapour at the injection in the plasma is some-
what depending on the plasma conditions. However, after
the opening of the dosing valve, equilibrium is reached
quite fast and a steady operation condition could be es-
tablished and maintained allowing long, even hour-long
deposition processes. In order to avoid contaminations
and not to perform deposition under a poorly controlled
environment, sample holder was not exposed to the jet
until such steady condition is reached. In the experiments
discussed in the present paper we have employed as a
precursor the titanium ethoxide (TEOT). It is widely used
in TiO2 depositions [20]. It already bears the tetrahedral
structure of the titanium oxide, while the lateral hydro-
carbon chains are easily removed by oxygen in the
plasma chamber. The effective interaction length of pre-
cursor molecules is determined by the position of injec-
tion point and by the plasma conditions, mainly the den-
sity of oxidizing agents. This could be tuned in order to
produce an optimal flow of seed radicals at the nozzle, to
fed the plasma jet. In this respect the injection system
and the plasma source could be easily fitted for different
kind of precursors. Even concerning only TiO2 deposi-
tions, we have demonstrated that titanium isopropoxide
could be used instead of TEOT, obtaining similar satis-
factory results. The actual pressures in the two chambers
are controlled by the conductances of the connections
shown in Figure 1, their values depending on the flow-
rate Q determined by the leakage valves opening and by
the pumping speed S. The pressures in the plasma cham-
ber PP and in the deposition chamber PD are given by the
following expressions [21]:


111
PNP
PQ CCS (1)


11,
DP
PQ CS (2)
where CN and CP are the conductances separating the
plasma from the deposition chambers and the deposition
chamber from the turbo-molecular pump, respectively.
The values of S and CN are in a sense fixed by the setup
choice. On the contrary, CP could be varied by throttling
partially the gate valve at the bottom of the main cham-
ber, reducing the overall pumping speed. This also in-
creases the pressure in the deposition chamber which, as
discussed previously, is useful to enhance clusterization
and to grow porous films with a structure at the nanome-
ter scale [9]. Q can also be easily changed regulating the
opening of the micrometer valves. From the operating

I. BIGANZOLI ET AL.
1630
point of view, at first the overall pumping speed is re-
duced by throttling partially the gate valve at the bottom
of the main chamber. Then the chosen pressures of argon
are established, by opening the dosing valve and letting
the system reach equilibrium. Afterwards the oxygen
valve is opened and regulated until the desired pressures
are reached at equilibrium. Normally plasma is switched
on before precursor is injected. Power is raised gradually,
in order to let the system heat and reach an equilibrium.
Only afterwards the injection valve is opened and the
precursor is let enter the plasma chamber. Again a few
minutes are needed before a steady plasma and pressure
is established in the device. Then deposition processes
can start, moving the sample holder in the desired posi-
tion and exposing the substrate to the jet coming from the
nozzle. Although roughly, the value of the conductances
could be estimated, in the different pressure ranges and
could be used to estimate residence times as well as the
relative weight of diffusion and flowrate of the species in
the device. The pressure range we are interested in con-
cerning the deposition chamber is 0.1  10 Pa, preferably
above 1 Pa, which is a compromise among the needs of a
pressure not too high for the turbomolecular pump to
work well, sufficient to control the clusterization, without
affecting the capability of reaching supersonic expansion.
Consequently in the plasma chamber, the pressure ranges
between 1  100 Pa. This turns out to fit nicely the max-
imum coupling efficiency of radiofrequency discharges
[14]. We have evaluated the Knudsen number Kn for
argon and oxygen at room temperature as a function of
both the pressure and the characteristic length. Kn value
gives an indication of the flow type at low pressure: mo-
lecular (M) if Kn > 0.5, transitional (T) if 0.01 < Kn < 0.5,
viscous (V) if Kn < 0.01 [21]. It turns out that our flow
regime in the deposition chamber will be mainly a transi-
tional one. In the plasma chamber it is well within the
viscous flow regime both for argon and oxygen. Only
below 7 Pa, the plasma gas phase enters into the transi-
tion regime. It is also worthy to notice that the flow is
generally transitional in the nozzle region where precur-
sor is injected. In addition well mixed reactor conditions
are fulfilled in the whole pressure range in the plasma
chamber [22]. Even more so happens in the deposition
chamber, but in general deposition is performed near or
within the Mach disk, to take advantage from the super-
sonic jet expansion. The same applies, albeit marginally
in the nozzle region, where the precursor quickly mixes
up in the plasma and reacts repeatedly, before being
ejected in the plasma jet. The ratio R of the pressures in
the two parts of the device is controlled by the CN con-
ductance value, which is dominated by the rectangular
slit, respect to the effective pumping speed. This ratio is
a very important parameter since it determines whether
the flow becomes supersonic after the nozzle. An appro-
ximate formula for the conductance of a thin slit in a
transitional flow was proposed in reference [23]. To-
gether with the correction for the finite thickness of the
slit [24], this could be used to calculate a value of CN =
(5.5 ± 0.1) × 10−3 m3·s−1, strictly valid for R > 10 and Kn <
0.1. This is in fair agreement with the estimate made
from the experimental measurements taken with an argon
flow, using the calibrated flowmeter and the pressure
readings in both chambers, CN = (5.6 ± 0.3) × 10−3 m3·s−1.
Given this conductance, the ratio R can reach a maxi-
mum equal to 38 in argon, largely sufficient for a super-
sonic jet expansion. Indeed in order to have this R ~ 2 is
enough (more precisely R = 2.05 for argon), as it could
be demonstrated under the approximation of considering
a convergent nozzle whose section decreases progres-
sively and isentropic flow [18]. Here Mach number M =
1 is reached at the nozzle exit. Corrections due to the
sharp edge thin orifice like ours are small. For instance,
with a circular orifice M = 1 on the axis is reached ap-
proximately 0.25 diameters downstream respect to the
geometrical exit [25]. For R > 2 the flow dynamic in the
nozzle region is unaffected by the background pressure
in the deposition chamber (such case is thus named
chocked nozzle). So, for instance, the local pressure at the
nozzle exit is about PP/2, independently of the pressure
PD. The flow there is underexpanded and continues its
expansion, thus reaching supersonic speeds. In this proc-
ess the pressure drops below PD, until this boundary con-
dition is re-established through compression shock waves,
which consist in thin regions where strong gradients of
pressure, temperature and velocity occur. So, the expan-
sion region constitutes a sort of plume emerging from the
nozzle, laterally limited by oblique shocks and down-
stream restricted by the so called Mach disk shock. This
region is often called zone of silence, being unaffected by
the background pressure [18]. For a Mach disk with lim-
ited lateral extension we can assume that the wavefront is
perpendicular to the flow direction, that is to say that we
have a normal shock, for which the so called Rankine-
Hugoniot relations hold, connecting flow properties up-
stream and downstream the discontinuity [18]. In first
approximation the deposition chamber conditions are
completely re-established through a single shock, so the
same background pressure PD is established downstream
the Mach disk as well as in the rest of the deposition
chamber. In the zone of silence the isentropic approxi-
mation is still adequate [18]. To further simplify, one can
notice that a few diameters from the nozzle exit the flow
field gets similar to that generated by a point source
placed in the nozzle throat: streamlines are almost
straight and radiates from the throat, velocity raises, and
density decreases along the streamline as the inverse
square of distance. Evidence in literature shows that such
approximation is sensible, since the exit geometry (noz-

I. BIGANZOLI ET AL. 1631
zle versus orifice, sharp-edges, slit vs orifice) has only a
limited influence on the central streamline properties [25].
To have an order of magnitude estimate here we report
the solution for the Mach number M and the pressure P
at a downstream distance x from the source along the
centerline, in case of a circular orifice with diameter D
[26]:

1
1
11
21
xx
Mx AA
D





 

 
 

1
1
,
xx
D
 









(3)

/( 1)1/(
2/( 1)11
12
p
Px A
P
 




 




1)2
2,
xx
D





(4)
with A = {3.26;3.65}, x1 = {0.075D;0.4D}, x2 = {0.04D;
0.13D} for γ = {1.667;1.4}. In the zone of silence the
Mach number progressively increases with the distance
from the nozzle exit. This particularity allows to select
the velocity of particles and thus to grow films with dif-
ferent characteristics. The pressure ratio R controls the
Mach disk position, and thus the maximum speed achie-
vable. With our setup Mach numbers up to 8 can be ob-
tained. It could be noticed that another way for control-
ling the cluster kinetic energy consists in modifying the
orifice shape. In general we could observe that within
this supersonic expansion region, the reduced number of
collisions does not favor cluster nucleation, so the parti-
cles available for deposition are mainly monomers and
small clusters. Consequently, the zone of silence allows
to synthesize films with small nanostructures and grains.
On the contrary, since pressure rises in correspondence
of shock waves, the deposition of clusters with higher
sizes and lower kinetic energies can be performed out-
side of the silence zone. As for the Mach disk, this is
located at a distance XMO for a circular orifice with di-
ameter D and at XMS for a slit with aspect ratio w/h >1,
where w and h are the slit width and height respectively
[27], while its lateral extension DMO can be estimated
according to [28]:


,
MO
0.47
MS
X
hwhXD (5)
MO
X
0.67 ,DR (6)
0.6 0.59.R0.36
MO
DD (7)
Such formulas predict that the Mach disk location and
lateral extension increase with R. The Mach disk turns
out to be about 7 mm from the nozzle at R = 2.05, up to
31 mm at the highest R in our setup. Mach disk lateral
extension was assessed too, increasing up to 30 mm
within the whole R range. This gives us room to work
within a somewhat extended area even inside the silence
zone where deposition could be performed.
3. Diagnostics
The electrical characteristics of the discharges have been
measured by means of probes located outside the vacuum
chamber. A high voltage probe (Tektronix P6015A, gran-
ted for a bandwidth of 75 MHz) was chosen for monitor-
ing the voltage signal sent through the antenna and was
connected at the copper strap-vacuum feed-through junc-
tion on the top of the device. The probe was calibrated
and the tuning was optimized to enhance sensitivity near
the RF frequency. Calibration factor was 1550 ± 100,
with a phase delay 1.78 ± 0.13 rad. Besides this, we have
taken some measurement using a current probe. This
consists of a home-made Rogowski coil which was de-
veloped to study fast microdischarges in atmospheric
pressure plasmas [29]. It has enough sensitivity and the
wide bandwidth necessary for use at RF. The calibration
factor at such frequency was 5.67 ± 0.01 A·V−1, with a
phase delay −0.144 ± 0.013 rad. This allowed us to
measure current and voltage signals with a digital oscil-
loscope (Tektronix TDS-5104) with sampling rate equal
to 1.25 GSa/s and 1 MΩ input impedance. Optical emis-
sion spectroscopy (OES) can be employed to reveal the
light emitted by the de-excitation of electronic energy
levels of atoms, molecules, ions and radicals which have
previously been excited in the discharge. Since in the
cold plasma environment typical of ICP the excitation
process happens mainly by impacts with plasma elec-
trons, the emission spectra could be used also to extract
information about their density or energy [30]. From the
intensity of emission lines with different wavelengths
one can identify chemical species as well as gain insight
about their abundances and those of the exciting agents.
We have analyzed the discharge emission spectra by
means of a wide band, low resolution spectrometer (Ava-
Spec-2048 by Avantes) equipped with a 10 μm slit, a ho-
lographic grating (300 lines/mm, blazed at 300 nm), a
coated quartz lens to increase sensitivity in UV and a
2048 pixels CCD. The spectrometer has a resolution of
about 0.8 nm and a spectral band extending from 180 nm
to 1150 nm. Emission spectra of the discharges have
been recorded directly imaging the plasma region through
a quartz view-port on the top flange with an UV en-
hanced optical fiber. Thanks to its aperture the effective
view-field covers most of the discharge volume. The
system made up by the optical fiber, the monochromator
and the CCD has been previously calibrated with both a
deuterium and halogen lamp (Avalight-DHc by Avantes).
This allows to correct for the device sensitivity and to
obtain the real relative intensities of emission lines at
different wavelengths. The exposure time has been opti-
mised to match the CCD sensitivity, avoiding overcounts.
During all the experiments, a large number of spectra
have been acquired and averaged for noise reduction.

I. BIGANZOLI ET AL.
1632
Dark spectra with comparable statistics were acquired
before each experiment and have been subtracted after-
wards. Although somewhat outside the scope of our pa-
per, we have also investigated thin film morphology and
composition. Deposited films were analyzed with an
FE-SEM (Zeiss Supra 40), equipped with an Oxford EDS
analyzer. Their chemical composition was then measured
with a precision of about 1%.
4. Experimental Results
As it is well known ICP discharges operates in two dif-
ferent regimes, so-called E- and H-mode [31]. The names
refer to the main actor sustaining the plasma state, being
in the former case the electrostatic electric field provided
by the voltage applied to an edge of the radiofrequency
antenna, while in the latter the oscillating magnetic field
locally inducing the electric field needed to sustain the
plasma. Only in the second case the name ICP refers ac-
tually to the prevailing impedance of the antenna plasma
coupling. By rising incrementally the voltage applied to
the antenna through the matching network, the gas-phase
undergoes an electrical breakdown and usually the ig-
nited discharge operates in the E-mode. Increasing the
voltage, a sharp transition occurs and the discharge enters
the H-mode [32]. Apart from the geometry of the RF
antenna and of the plasma chamber, the minimum volt-
age needed to enter the H-mode is determined by the
ratio between the radiofrequency ω and the momentum
transfer collision frequency which is controlled by the
gas pressure [31]. As discussed above, the relevant pres-
sure range in the plasma chamber will be 10  100 Pa.
Initially plasma was produced in argon alone. Break-
down happens at a low power level (10 - 20 W in the
pressure range) after suitable RF-line adapter conditions
are chosen and fixed to optimize network matching. The
HV signal measured by the probe at the different power
levels is shown in Figure 3. The steep rise at low power
is due to the E-mode, with voltage proportional to the
square root of the power. The voltage drops, even by a
few hundreds volts, when the regime transition starts and
the coupling is changing. The transition is somewhat
smooth happening over a quite extended range of power,
30 - 60 W, which is larger the lower the pressure. This is
in agreement with similar observations published in lit-
erature [33]. After the H-mode is fully established, the
HV starts rising linearly with the power level, at least in
the limited range considered. From the simultaneous
measurement of the current and voltage signals it is pos-
sible to calculate the values of the impedance of the an-
tenna-plasma load. The same measure could be extracted
form the values fixed for the capacitances of the RF
matching box, when the best tuning conditions are
reached [14]. This is displayed in Figure 4. The two
Figure 3. Coil HV amplitude as a function of the RF power
level in argon discharges at pressures of 10, 40 and 80 Pa.
Figure 4. Real and imaginary part of the load impedance as
a function of RF power in argon discharges at 40 Pa.
procedures agree fairly well. The second being much
more easy to employ was used in the subsequent experi-
ments. Load resistance, which is dominated by the
plasma contribution, starts to increase as the transition
happens, and to stabilize in the H-mode. Load reactance,
initially dominated by the antenna inductance, decreases
as the plasma coupling becomes inductive, as expected
from the simplified ICP model as a transformer [14]. A
typical OES spectrum of argon discharges after dark sub-
traction and sensitivity correction is shown in Figure 5.
The brightest feature in the spectra of such discharges is
the system of 3p54p → 4s transitions, the 2px system in
the Paschen notation, in the red and in the near IR [34].
Under vacuum conditions, the excitation of argon radia-
tively decaying levels happens mainly through inelastic
scattering of argon atoms by high energy electron impact.
Under such an approximation the intensity of emission
lines is proportional to the product of the electron density
and the rate of impact excitation process, which is a
function of the reduced electric field or, in other terms, of
the electron temperature alone [30]. We take advantage

I. BIGANZOLI ET AL. 1633
Figure 5. Typical spectra of the plasma before and after the
TEOT precursor injection into the chamber.
of the presence of argon. The OES of argon plasmas is
favourable in Visible and near-IR range and the dynam-
ics of the excitation and radiative emission of the main
energy levels is well known [35,36]. The relative inten-
sity of some reference lines can so be used to gain insight
mainly in the electron plasma properties. This was done
for the 751 nm (emitted from the 2p5 level, mainly popu-
lated from the ground state argon [35]), which was one of
the brightest in our OES spectra. Division by pressure
factors out the effect due to the initial density of argon
atoms, highlighting the contribution from the plasma
electron alone. Results are shown in Figure 6 using a
log-scale. As already reported, the transition between E
and H-mode in the OES intensity is sharp, at least at the
highest pressures. The increase is so large that a log-scale
is needed to appreciate features in both regimes. This is
to be compared with the much more gentle transition
displayed by electrical parameters discussed previously.
In both regimes the intensity rises with the RF power
level, although the rate is different and strongly depend-
ent from pressure. This overall trend is common to the
other emission lines of the 2px system, but their relative
intensity changes slightly but significantly within the
power and pressure ranges investigated. This reflects
shifts in the electron excitation pattern influenced by
changes in the electron temperature and the metastable
argon abundances. Radiative models have been proposed
in order to extract plasma parameters from the relative
intensities of the emission line pattern in argon [37]. In
particular a simplified model, including only the part of
the 2px system was proposed [38] and modified by us [39]
to increase precision. As a results, from the relative in-
tensities of argon emitting lines, it is possible to measure
the electron temperature and the concentration of the two
kinds of metastable argon atoms. Both measures are
valuable in order to characterize the plasma dissociation
capability and could also be implemented as a monitor
control during the deposition process. Only a brief de-
Figure 6. Intensity of 751 nm argon line normalised to the
total Ar density as a function of the RF power.
scription of the model is provided here. The core of the
method is to to exploit the different electron energy de-
pendence of the cross section of some of the 2px excited
levels and the large differences in the probability of elec-
tron impact excitation of such levels starting from me-
tastable argon atoms [35]. Our proposal was to use the
intensities of the whole set of emission lines of the 2px
system, provided that their intensity is not negligible and
that no ambiguity could arise (especially because of our
limited wavelength resolution), to define a sort of χ2
function:

 
22
1,
21log
nm
nm N
NN RR 


 
 (8)




***
1,
nnnne ne
RIbkTx kTx




 (9)

where I is the measured intensity of the selected emission
line and b is the branching ratio of that particular transi-
tion from the upper excited level involved. In the latter
formula k and k* are the electron impact collision rate to
the excited level corresponding to the n-th emission lines,
respectively from the ground state and from the two me-
tastable states, while x* are their concentrations. Minimi-
zation respect to the parameters allows to extract the
electron temperature and the two metastable concentra-
tions. As discussed in our published papers [39,40], this
procedure is more sensible, reducing the systematic er-
rors which could affect the proposed analytical solution
[38]. Using the measured intensities of nine lines we got
a fair reproduction of the relative intensity pattern, within
30%, which corresponds to a χ2 ~ 0.1. Results concerning
this kind of characterization of the plasma state are dis-
played in Figure 7. Electron temperatures are almost
constant, slightly decreasing with the power level, in the
H-mode. Their values stay in the 1  1.5 eV range. They
are somewhat larger in the E-mode, however never ex-
ceeding 2 eV. Temperature decreases steadily as the
pressure increases. It is clear that, despite being signifi-

I. BIGANZOLI ET AL.
1634
Figure 7. Electron temperature as a function of the RF
power level in dischar g e s of pure argon and mixtures.
cant, these differences cannot explain the sharp transition
in the emission line intensity between the E and H modes.
This is almost entirely due to a jump in the electron den-
sity in the H mode. Argon metastable atoms density was
estimated in the range 1014  1015 m
−3, with concentra-
tions around a ppm. Being similar, only slightly larger in
the E mode, the concentration should not depend strongly
on the electron density. This indicates that metastables
are quenched mainly through electron impact or reactions
with radicals itself produced by electron dissociation.
When oxygen is added and diluted in argon, the qualita-
tive behaviour of the source was similar. We have inves-
tigated an extended range of O2 concentrations from 5%
to 80%. In general a too high concentration of oxygen
produces an increased stress on the pumping system. The
addiction of oxygen has only a slight effect on the char-
acteristics of the E-mode. However it delays the onset of
the transition to higher power levels, between 100 - 200
W, and so voltage. Fully developed H-mode discharges
often require power levels in excess of 500 W, and volt-
age levels which continue to rise the larger is oxygen
concentration. This could be guessed in data reported in
Figure 8 with different argon/oxygen ratios at the same
total pressure. The same trend could be observed also by
keeping constant the argon partial pressure and increas-
ing oxygen concentration. This behaviour is commonly
ascribed to oxygen electronegativity, which favours the
formation of negative ions, reducing the electron plasma
density [19]. OES measurements confirm the overall
picture. Oxygen molecules are poor emitting agents, dis-
charge spectra in pure O2 being dominated by atomic and
2 ion emission lines. The former are readily revealed
also in our argon-oxygen ICP. Atomic argon and oxygen
lines intensities show the same trend, with a strong in-
crease at transition. The relative intensity decreases as
oxygen concentration rises, in agreement with the de-
crease in the discharge current, at the same power level.
Figure 8. Coil HV amplitude as a function of the RF power
in argon and mixtures at pressures about 10 Pa.
Oxygen ion signal was spotted too, although being rela-
tively weak and often undetectable, especially in the low
power, low emitting E-mode. The presence of argon is
favourable to OES in another way. Since it does not enter
in any chemistry happening in the gas-phase, the inten-
sity of its emission lines is controlled only by electron
properties in the plasma state. Argon ground state con-
centration being quite precisely determined by argon
partial pressure alone, which is easily measured and con-
trolled. Ideally in a steady, uniform and Maxwellian
plasma, by plasma density and temperature only. Then
the ratio between the intensity of any emission line and
that of one of the argon lines, generally nearby in wave-
length, factors out the electron density, whose measure
requires a plasma diagnostics. If the electron temperature
variations are not large, a feature which in ICP is gener-
ally satisfied, the excitation rates are fixed and in the
intensity ratio they introduce only a multiplicative factor.
This procedure, usually applied with noble gases in trace
and called actinometry [14], provides then a measure of
the relative abundances of the emitting particles. This is
already useful to compare dissociation capabilities of
different plasma conditions. When the electron tempera-
ture and the dynamics of the excitation process is known,
it is also possible to gain insight in the absolute concen-
tration of the parent atoms or molecules, usually the
ground state. In particular we minded the oxygen atom
emission lines, which are easily detected in our spectra.
The result of such an exercise is displayed in Figure 9,
where the oxygen 777 nm emission line intensity was
normalized against a pool of three nearby argon lines (750,
751 and 763 nm). We measured also the 844 and 615 nm
lines of oxygen, obtaining similar results. Although the
former is usually preferred being the least influenced by
indirect excitation channels [14], we found a partial con-
tamination from the close 842.5 nm emission line of argon,
due to the low resolution of the spectrometer. The intensity
ratio, so the atomic oxygen density, increases steadily
O

I. BIGANZOLI ET AL. 1635
Figure 9. Intensity ratio between oxygen and argon lines as
a function of the RF power, at the same argon pressure (10
Pa) with different O2 concentrations.
with the power level. It appears to change little whereas
oxygen percentage in the gas mixture is between 10% 
40%, then it increases strongly. It could be observed that
nevertheless the degree of dissociation of oxygen mole-
cules in the 62% mixture is less than half of that in the
9% one. Molecular oxygen ion shows an opposite trend,
decreasing with power and roughly proportional to the
O2 percentage. It partially reflects the dissociation of the
parent molecules, with a change in the charged species
concentrations. This completes the characterization of the
discharges in argon-oxygen mixtures in our device. How-
ever, since the source was developed to perform thin film
deposition processes, we briefly describe the plasma state,
when a precursor like TEOT is injected near the nozzle.
We claim that by controlling plasma parameters it is pos-
sible to control the chemistry while by changing the pres-
sure ratio R and the distance of the substrate from the
nozzle it is possible to tune nanoparticle size and energy
and their deposition rate, controlling the whole film
mesostructure. Deposition have been performed in a 450
W ICP discharge in a 2:3 Ar/O2 mixture at 8 Pa pressure.
TEOT heating was tuned to change precursor flowrate in
order to find its optimal value. However in general the
overall pressures in both the plasma and the deposition
chamber do not change after precursor injection. Also the
electrical behaviour is only slightly affected, both in the
E and in H-mode. The same observation holds on even if
the distance between the nozzle and the injection point is
varied. In order to assess the precursor dissociation de-
gree in the plasma state, it was important to monitor the
relative emission line intensities of other emitting levels,
produced in different stages of the precursor chemical
kinetics evolution. In particular, due to the extended
range of wavelength of our measured spectra, it was pos-
sible to spot the emission of several molecules produced
by the chemical kinetics of TEOT in the plasma gas
phase (see Figure 5). When the precursor is injected the
emission spectrum changes substantially, showing evi-
dences of a continuum and of several new molecules.
Signals attributable to carbon oxide, CH and OH radicals
and hydrogen atoms are readily observed in the OES
spectra. In particular the carbon oxide is thought to be
directly related to the degree of oxidation of the organic
groups of TEOT. This is mirrored by the relative decline
of O atoms emission which reveals TEOT oxidation by
such plasma radicals (see Figure 9). Even more interest-
ing was the emission attributable to TiO radicals [41]
around 615 nm. We also noticed the absence of direct
emission from Ti atoms, which could be taken as a signal
that dissociation stage was let evolve too much and so
used as a monitor to discard operating conditions proba-
bly unfavourable for TiOx thin film deposition. Argon
presence could be used again as an actinometry agent, to
measure the relative abundances of radicals. A few re-
sults are shown in Figure 10, which refers to experi-
ments aimed to study the effect of the precursor heating
temperature, which controls the flow of TEOT. Increas-
ing heating results in a generalized rise of radical emis-
sion relatively to argon atoms which are produced by
dissociation and oxidation in the plasma gas-phase. How-
ever, by considering the different pace of the rise, we
could grasp a relative decrease in the ratio of CO (and
OH) over the H atom. This suggests an incomplete oxi-
dation of the organic groups of the precursor at high
fluxes. This is also correlated to a relative decrease of
TiO abundance at the highest temperatures, respect to
both H atoms and OH/CO molecules. The data could
then be used to optimize the precursor flow and the dis-
charge power level, as well as the distance between the
injection needle and the nozzle. They were also corre-
lated with an X-rays analysis (EDX) showing that at the
highest temperatures the film is composed mainly by
metal titanium. The oxygen titanium ratio increases by
reducing the TEOT heating, reaching the optimal value
around 2 when the temperature was about 120˚C  130˚C.
This demonstrates that suitable flowrate of precursor and
chemical composition of the supersonic jet could be
somewhat controlled. Here, however, spatially resolved
measurements, to be taken by optical fibers placed di-
rectly in the vacuum chamber, will be valuable. Using
SEM imaging it was possible to investigate the structure
of the thin film and to measure its depth. This goes be-
yond the scope of our paper. However a few observations
are worthy. In particular, compact thin films can be ob-
tained when deposition occurs at high R values (gener-
ally larger than 10) and in the expansion plume region, at
deposition rates of about 200 nm/min. A more extended
characterization of the deposited thin film will be pre-
sented elsewhere [17]. Film composition could be as-
sessed too, by using EDX. The kind of results obtained
through such analysis is shown in Figure 11. Here depo-

I. BIGANZOLI ET AL.
1636
Figure 10. Intensity ratio between TiO, CO, OH, H and
argon lines as a function of TEOT heating temperature.
Figure 11. SEM image of a thin film section deposited from
TEOT on a silicon substrate.
sition was started at a the precursor flowrate which was
changed afterwards. As shown in Figure 11, uniform,
compact and quite thick film could be deposited in a re-
latively short time. The relative EDX signals of oxygen
and titanium are reported as a function of the film depth.
While, at first, an almost metal titanium film was ob-
tained, then a quite stechiometric TiO2 composition is
achieved. So, in particular under the latter operating con-
ditions, high deposition rates and pure TiO2 films can be
easily obtained. We only add that, while the deposited
film is almost amorphous, positive indications of film
crystallization were obtained after annealing process. As
a matter of fact, the RAMAN spectra of the annealed
film showed an almost complete transformation in ana-
tase. The same can be assessed from Figure 12, which
displays the angle resolved X-ray diffraction pattern of
our TiO2 nanostructured thin film. The peaks at scatter-
ing angles around 25˚, 38˚ and 48˚ correspond to the re-
flections from some crystal planes of anatase. No crystal-
line phase assignable to rutile and brookite could be
found. Then, by changing the pressure ratio R and the
substrate location, our source was shown to be able to
successfully deposit titanium oxide films with thickness
from hundreds of nanometers up to a few microns.
Figure 12. XRD of TiO2 thin film after annealing showing
the characteristic peaks of anatase allotropic phase, marked
with letter A and the corresponding scattering angles.
5. Conclusion
A new plasma source for thin film deposition was pre-
sented and characterized. It embodies the idea of a spatial
separation between the precursor dissociation, to be per-
formed in a plasma environment, and the thin film
growth, to be performed on a substrate watered by a flow
of molecular clusters, which evolve and aggregate during
the transfer. Here a supersonic jet substantially free ex-
pansion was believed to be the better environment to
allow control of cluster sizes and flowrate. Plasma char-
acterization has been performed, demonstrating the ca-
pability of the source to maintain stable ICP for long
periods, with flexible and controllable parameters that
could be tuned for an optimization of the precursor dis-
sociation. Feasibility of thin film titanium oxide deposi-
tion, with suitable growth rate and hardness and con-
trolled composition, was demonstrated using a standard
precursor like TEOT. Then, by changing the pressure
ratio R and the substrate location, the flowrate, the size
and the energy of precursor clusters can be varied and so
the thin film morphology could be controlled too.
6. Acknowledgements
Part of the work was performed under a grant by Fon-
dazione Cariplo (Scientific and Technological Research
on Advanced Materials-2010, nr. 2010.0623), an Italian
private funding agency, whose support we gratefully
acknowledge. We are also pleased to thank technical and
scientific collaborators of the PlasmaPrometeo Center for
the living and stimulating atmosphere of collaboration.
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