Eur. Phys. J.

D 60, 653–660 (2010)

DOI: 10.1140/epjd/e2010-00245-x THE EUROPEAN
PHYSICAL JOURNAL D
Regular Article

Characterization of an atmospheric pressure plasma jet

for surface modification and thin film deposition
S. Bornholdt, M. Wolter, and H. Kerstena
Institute of Experimental and Applied Physics, Christian-Albrechts-Universität zu Kiel, 24098 Kiel, Germany

Received 12 May 2010 / Received in final form 29 July 2010

Published online 28 September 2010 – 
c EDP Sciences, Società Italiana di Fisica, Springer-Verlag 2010

Abstract. In this paper, an experimental study is presented to characterize a commercially available atmo-
spheric pressure plasma jet (APPJ) kINPen which can be used for local surface modification, e.g. changing
the wettability as well as for thin film deposition with silicon-organic and metal-organic precursors to
enhance scratch resistance or to lower the gas permeability. Characterization of the jet discharge has been
carried out by three methods: (i) measurement of the energy influx from the jet plasma to a substrate by a
calorimetric probe, (ii) spatial resolved investigation of the plasma beam by optical emission spectroscopy
(OES) and (iii) observation of the plasma jet by video imaging. The deposited SiOx and AlOx films were
analyzed by XPS measurements.

1 Introduction chemical surface reactions [8–11]. On the other hand, es-

pecially in the case of thin film deposition, the structure
Atmospheric pressure plasma jets have been established as and morphology as well as the stoichiometry of the film
suitable sources of low-temperature and non-equilibrium depend strongly on the energetic conditions at the sur-
atmospheric pressure plasmas [1–3]. The main distinctive face [8,12–14]. For example, surface diffusion of adsorbed
feature of this kind of plasma tools is that the jet is not atoms can be enhanced, which results in a rearrangement
confined by electrodes and its dimension can be adjusted of deposited atoms [15,16]. A bombardment of growing
in a wide range allowing local treatment of 3D surfaces, film with low-energy ions from the surrounding plasma
e.g. the inner walls of wells, trenches or cavities [2]. Among results in a modification of its properties, too [17].
other applications, the treatment of temperature-sensitive Since the surface temperature is essentially influenced
surfaces such as polymers or biomedical tissues is of inter- by the energy fluxes resulting from energetic particle bom-
est. For example, Kuchenbecker et al. [4] and Rajasekaran bardment, chemical surface reactions and plasma radia-
et al. [5] used a dielectric barrier discharge for medical ap- tion [18,19], the different contributions to substrate heat-
plication on human body, whereas Bibinov et al. [6] used ing are separated and studied independently by a suitable
a dc atmospheric pressure plasma jet. Mostly nitrogen, variation of the experimental conditions [20].
oxygen or a mixture of these gases are used to operate The experimental determination of the energy influx
the discharge. The authors characterized the discharge by in atmospheric pressure plasma processes, especially for
measurement and simulation of the spatial distribution of APPJ operation is only rarely done, because measuring
nitrogen and oxide gas density. The diagnostics are mainly the energy influx at atmospheric pressure is challenging.
based on UV radiation and emission spectroscopy of ni- In contrast to low pressure plasmas (LPP) atmospheric
trogen or the flux of ozone. pressure plasmas (APP) are often more inhomogeneous,
In this paper a low-temperature, rf-powered (1.7 MHz, e.g. they form tiny, filamentary discharge channels or have
2.5–3.5 kVpp ) capillary APPJ (kINPen) is studied, which a small size like micro hollow cathodes [21,22]. In the at-
is operated with argon in air at a constant argon gas flow of mospheric environment the mean free path and the kinetic
5 L/min. Related experiments and previous measurements energy of the plasma species (electrons, ions, radicals)
have been published elsewhere [7]. are different from LPP. From calorimetric probe measure-
The investigations are focused on the energy influx ments it is possible to obtain information on the energy
from the APPJ to a substrate, e.g. glass and metal. Of influx as well as on the real temperature evolution on the
special interest in respect to the energy influx is the contri- surface of the substrate. This is a crucial point for the
bution of charge carriers which interact with the surface. treatment of sensitive biomedical material and of special,
The final surface temperature TS of treated substrates temperature-sensitive synthetic materials (e.g. polyethy-
during plasma processing effects elementary surface pro- lene, polymethyl methacrylate).
cesses like adsorption, desorption, and diffusion as well as In addition to the energy influx optical emission spec-
troscopy (OES) in the spectral range between 280 and
a
e-mail: [email protected] 1100 nm is performed. Spectra of the APPJ plasma
654 The European Physical Journal D

is constant 5 L/min. The working gas inside the jet is ar-

gon. Other process gases (precursors) are supplied to the
plasma beam outside the nozzle through a small gas inlet
by forming an own precursor atmosphere. The length of
the plasma jet depends on the rf power and is between
1 and 14 mm. The diameter of the plasma jet is about
1 mm. The gas temperature has been measured to be in
the range from 30 to 95 ◦ C [24].

2.2 Calorimetric probe measurement

The integral energy flux from the plasma towards the

substrate has been measured by a compact calorimetric
probe [19,25].
The probe is mounted on a manipulator arm to allow
horizontal and vertical motions in front of the plasma jet.
Fig. 1. The operating scheme (top) and a photograph (bot- In these experiments, the energy flux measurements are
tom) of the used plasma jet “kINPen 08”. carried out by observing the rate of temperature change
dTS /dt of the probe which is brazed to a thermocouple
(type K) and placed within a solid shield. The probe is a
radiation (e.g. argon and nitrogen lines) were measured thin metal plate which serves as a kind of substrate. The
in different axial distances from the plasma jet orifice. By probe is connected only by the thermocouple and a wire
the OES it is possible to get a spatially resolved map for for additional biasing. Due to its large heat capacity the
the evolution of the gas mixtures in front of the plasma jet. shield is at a constant environmental temperature Tenv
Besides OES the plasma jet has been observed by video during the measurement. The technical reliability of this
imaging. From high speed video imaging one obtains in- calorimetric probe setup was successfully demonstrated [7,
formation on the time-resolved behavior of the plasma jet 20,26]. The measurement of the total energy flux Qin is
in front of different substrate materials, especially on the based on the determination of the difference between the
formation of filamentary discharge channels. Observation time derivatives of the substrate temperature Ts during
by video imaging is a rather new technique for the char- heating (which means the plasma-on phase) and cooling
acterization of the APPJ kINPen providing data on the (plasma-off) multiplied with the heat capacity of the probe
light intensity and inhomogeneities in the jet. has to be determined by calibration [27,28].
The surfaces of the modified substrates are studied The schematic setup for the different experiment se-
by X-ray photoelectron spectroscopy (XPS) in order to ries is shown in Figure 2. For the thin film deposition the
proof the deposition by using a silicon-organic precursor calorimetric probe was replaced by a “real” substrate.
(HMDSO) or an aluminum-organic precursor (ATI), re- In general, the power balance at the substrate is given
spectively, in the process plasma. by [28,29]:
Qin = ḢS + Qout (1)
where Qin marks the energy gain by the several energetic
2 Experimental method contributions from the plasma, ḢS = mc(dTS /dt) denotes
the temporal rate of enthalpy change of the substrate and
2.1 Plasma jet Qout summarizes the heat losses by radiation and thermal
conduction by the gas and the substrate. Due to the con-
For the experiments presented in this paper a miniaturized struction of the calorimetric probe (shielding) the losses
capillary APPJ was used. This plasma jet “kINPen 08”is by radiation are always small in comparison with the in-
a commercially available system, distributed by the INP coming fluxes due to the plasma process. ḢS is deter-
Greifswald [23]. mined by Qin − Qout . During the heating phase (Qin > 0)
The general working principle of the APPJ is shown ḢS (heat) is given by Qin − Qout and during the cooling
schematically in Figure 1, which shows a photograph of phase (Qin = 0) it is ḢS (cool) = −Qout . Inserting these
the plasma jet, too. expressions into equation (1) yields:
The rf-power supply (1.7 MHz) is connected to the
center rod electrode by a matching network. The system
Qin = ḢS (heat) − ḢS (cool) (2)
power is 65 W (250 V) and the peak to peak voltage is     
between 2.5 and 3.5 kV. The electrode is surrounded by a dTS dTS
= mc − . (3)
ceramic cap which forms the gas stream and a ring elec- dt heat dt cool Tenv
trode which is connected to ground. The ring electrode
stabilizes the operation of the jet. The gas pressure is con- Assuming no change of the environmental temperature
stant at 1.5 bar and the resulting gas flow through the jet Tenv , which is achieved by short measurement times and
 S. Bornholdt et al.: Characterization of an APPJ for surface modification and thin film deposition 655

(fps) and the exposure time was 0.5 ms. The observed area
was a field of 72 × 96 pixel, e.g. 72 pixels in vertical (ax-
ial) direction and 96 pixels in radial (horizontal) direction.
The calibration of this field of view centered around the
jet results in an observation window of 5.14 × 6.86 mm.
This area is large enough to monitor the plasma jet out-
side the nozzle and in front of an insulating (glass plate) or
conductive (copper plate) material, respectively. By this
way it is possible to study the formation and expansion
of filaments in front of the surface material. The recorded
video file was cut into single frames and analyzed with a
c
MatLab program to observe the motion of the plasma
jet and the processed surface in detail.

2.5 Sample preparation and XPS analysis

Fig. 2. Schema of the experimental setup for the calorimet- The precursors (HMDSO and ATI) were heated in a wa-
ric probe measurements (a) and the optical emission spec- ter or oil bath at 63 ◦ C and 155 ◦ C, respectively, and then
troscopy (b). The calorimetric probe as well as the optical fibre fed via an argon flow into the cap, which was mounted
for OES could be moved in axial direction. For observation by on top of the jet-system (see Fig. 2d). The chemical com-
video imaging (c) the camera was mounted side-on. For the de- position in case of thin film deposition (SiOx , AlOx ) has
position experiments the precursor was mixed into the plasma been studied by XPS [30]. For the XPS measurements the
jet by using a small gas box surrounding the jet (d). substrates were cut into square pieces with a edge length
of 1 by 1 cm. After plasma deposition the probes were
the large heat capacity of the shield, the expression within analyzed with a XPS spectrometer which used a Al-K-
the brackets of equation (3) is a quantity proportional to X-ray source (1486.6 eV). The spectrometer energy scale
the thermal power at the substrate, if the slopes dTS /dt was calibrated in respect to the C1S (C–C, C–H) compo-
are determined at the same environmental temperature nents set at 285 eV. For the analysis of the XPS spectra
Tenv . In order to obtain absolute values of Qin the specific the CASA XSP software [31] was employed.
heat capacity of the calorimetric probe has been deter-
mined by a known thermal power, e.g. diode laser radia-
tion. For the used calorimetric probe (copper) we obtained 3 Results and discussion
a value for CS = mc of 0.16 J/K.
3.1 Calorimetric probe

2.3 Optical emission spectroscopy The energy influx from the plasma jet to a substrate has
been measured by the calorimetric probe.
For the purpose of the optical diagnostic of the plasma The integral energy influx Qin obtained by the proce-
jet a commercial spectrometer (HVR 2000+) was used. dure described above has been measured at different axial
The emitted light from the plasma jet is collected by an distances from the nozzle, see Figure 3 (top).
optical fibre. This apparatus allows to study emission lines The measurements of the total energy influx started
in the range between 280 and 1100 nm. The sensitivity at a distance of 25 mm from the nozzle. In this rather far
is 75 photons/count at 400 nm and the optical resolution distance the plume of the plasma jet could not been de-
is 1 nm FWHM. The used spectrometer and the analysis tected by naked eyes and an energy influx was just able to
software is a commercial equipment by Ocean Optics. The measure. About 14 mm from the orifice the visible plasma
fiber optics is mounted side-on by a movable holder. By jet ends (see Fig. 1). Up to this position the total energy
this construction it is possible to measure the emission influx is in the order of about 20 mW/cm2 . When the
lines at different vertical and horizontal distances from calorimetric probe was moved closer to the nozzle along
the jet, see Figure 2b. Only relative intensities of related the plasma jet the total energy influx slowly increases and
lines have been measured in order to compare the axial at a distance of 11 mm the mean value of the energy influx
distribution of the several gas species. is ca. 50 mW/cm2 .
In order to asses and to measure the effect of free
charge carriers (electrons, ions) which may exist in the
2.4 Video imaging plasma jet plume and which contribute to the energy bal-
ance the calorimetric probe has been biased (70 V, 0 V,
In order to observe the behavior of the plasma jet in front −70 V). By probe biasing either the electrons (+70 V) are
of substrates (metal plate, insulating glass) a high speed accelerated and the ions are repelled or vice versa (−70 V).
camera (PixeLINK) which was mounted side-on has been We assume that in a rather long distance from the noz-
used (Fig. 2c). The frame rate was 1000 frames per seconds zle only very few free electrons and ions exist. However,
656 The European Physical Journal D

higher density of charge carriers which cause the remark-

able increase in heating the calorimetric probe.
In addition to the energy influx the current onto the
calorimetric probe was simultaneously measured, too. In
Figure 3 (bottom) the measured electrical currents are
plotted. If the probe is far away from the plasma jet (e.g.
25 mm from the nozzle) no current is detectable. By mov-
ing the probe along the direction of the jet there is almost
no current detectable up to a distance of about 13 mm.
This observation corresponds with the results for the en-
ergy influx. When the probe moves closer to the nozzle
a different behavior is observed. The grounded and neg-
atively biased probe show an increase of the current up
to 2 mA. The behavior of the probe current for a posi-
tively biased calorimetric probe is similar to the negatively
biased probe, but the maximum value now is −2 mA. Un-
fortunately, we had only the possibility to put a bias volt-
age of ±70 V. The fact that the positive deviation is as
big as the negative could be an indication that the ion
saturation current is not attained.
When the bias voltage of the calorimetric probe is
more positive than the floating potential of the surround-
ing plasma more electrons are collected and the resulting
current to the probe is negative. On the opposite, if the
bias voltage is more negative than the floating potential
the current to the probe is positive due to the collection
of ions. In general, the current to the calorimetric probe
is very low in comparison to experiments in low pressure
Fig. 3. Total energy influx (top) and probe current (bottom)
plasmas which deliver an energy influx in the same order
in dependence on the distance from the nozzle along the plasma of magnitude as for the APPJ [20]. One reason is that the
jet for three different bias voltages of the probe. plasma jet is operated at atmospheric pressure. Therefore,
we assume that the most part of the measured energy in-
flux stems from the UV-radiation of the plasma jet. Due to
if the calorimetric probe is positively or negatively biased the short mean free path the contribution of the charged
either the few electrons or ions are repelled. The trans- plasma species do not play an important role. We esti-
ferred kinetic energy is rather low since the charge carriers mated this part to be less than 10% of the total energy
are located due to the high pressure and the cannot gain influx. If the charged species would play a dominant role
much kinetic energy as in low pressure plasmas. In case for the energy influx, a dramatic increase for higher nega-
of grounded probe (0 V) both types of charge carriers can tive bias voltages should be observed due to positive ions.
reach the probe with higher probability and they can re- But this is obviously not the case. Also we have no indi-
combine at the copper surface of the calorimetric probe. cation of extraordinary high ion density from the spectral
This recombination might be the reason for the constantly observations: no ArII (Ar+ ) lines are detected.
higher energy influx for 0 V than for biased operation at The investigations are further experimental proof that
distances larger than 12 mm. obviously free charge carriers can exist in the plasma jet
Depending on the bias voltage of the probe a fast in- at a certain distance from the nozzle even at atmospheric
crease of the energy flux starts between 10 and 12 mm in pressure. In distances larger than 12 mm no electrons or
front of the nozzle. Again, three mm closer to the noz- ions, respectively, could be detected. The energy influx
zle the energy influx reaches a maximum for all bias volt- which still can be measured at this long distance and
ages. For the negative voltage (−70 V) the highest value is which increases slowly by approaching the nozzle is mainly
250 mW/cm2 , for the positive voltage (+70 V) this max- due to radiation. The influence of free charge carriers in
imum is about 210 mW/cm2 and for the grounded probe the jet can be slightly observed by the difference in the
the maximal energy influx is 230 mW/cm2 . When the strong increase of Qin at about 11 mm (Fig. 3 top). Just
calorimetric probe comes still closer to the nozzle the en- in this region an electric current is detectable. Unfortu-
ergy influx is almost constant. At a distance less than nately, it cannot be distinguished if the charge carriers are
6 mm it was not possible to perform any measurements. coming from the plasma inside the nozzle or if they are
The reason for that was the strong interaction between produced by collisions or photo-ionization in this region
the plasma and the probe. Many filaments are generated of the jet.
and reasonable measurements are not possible. Obviously, Spectroscopic measurements by Foest et al. [2] yield
in distances smaller than 12 mm from the nozzle there is a energy influxes due to VUV/UV radiation between 15 and
 S. Bornholdt et al.: Characterization of an APPJ for surface modification and thin film deposition 657

4
10 Ar (763 nm) A detailed description of the profiles and the con-
O (777 nm)
OH (308 nm)
volution procedure may be found in [33,34]. In general,
N (337 nm)
2
two tendencies can be observed. The maximum of ar-
gon, oxygen and OH lines is immediately at the nozzle
intensity [arb. units]

3
10
of the plasma jet. With increasing distance these sig-
nals decrease. The signal of O and OH lines vanishes at
ca. 11 mm. In comparison with visual observation (Fig. 1)
also a change in the light of the plasma jet is observable
at that position. The beam becomes smaller and the color
2
10 changes from white to light blue.
The nitrogen lines show a quite different behavior.
At the nozzle the nitrogen intensity is in the order of
40 counts ±20. The signal increases with increasing dis-
1 tance and reaches a maximum of ca. 1000 counts at about
10
0 2 4 6 8 10 12 14 16 9 mm from the nozzle. At this point the signal also de-
distance from nozzle [mm]
creases as well as any other intensities. The detectable
Fig. 4. Relative intensities of selected species, e.g. Ar, O, OH intensity for argon and nitrogen lines ends at a distance
and N2 in dependence on the distance between the spectrom- of about 14 mm. We assume that the excited (metastable)
eter and the nozzle of the plasma jet. argon atoms and the UV-radiation interact with the mole-
cules of the surrounding air. The excitation and dissoci-
ation of oxygen and water molecules is due to the UV-
50 mW/cm2 for a comparable plasma jet. For wave- radiation similar to the formation of the ozonosphere on
lengths between 115 and 200 nm a spectral radiance up earth [35]. In contrast, the nitrogen molecules are mainly
to 880 µW/mm2 sr was reported. With these results we excited due to collisions with the metastable argon atoms.
calculated an energy influx by the VUV/UV radiation to Hence, the nitrogen molecules have to diffuse into the
the calorimetric probe of 17 mW for the used probe area plasma jet from the surrounding air. Because of these
of 0.19 cm2 . The comparison between the values by Foest different mechanisms the different evolution of the axial
and our measurements shows a good agreement. line intensities can be explained. The analysis of the ar-
The maximum temperature which has been obtained gon line intensity confirmed the measurements by Foest
at the calorimetric probe under our experimental condi- et al. [2] where the formation of an argon channel is de-
tions was 55 ◦ C. The knowledge of the maximum tem- scribed which hardly interacts with the environment.
perature is very important for applications of the plasma The behavior of excitation and interaction of the am-
jet, e.g. modification of temperature sensitive surfaces or bient nitrogen with the Ar metastables has to be consid-
biomedical materials. ered for the injection of other molecular gases/precursors
into the plasma jet regarding technological application,
e.g. thin film deposition. Obviously, it is possible to inject
3.2 Optical emission spectroscopy (OES) such species into the jet at a certain distance from the
nozzle to prevent the electrode from erosion and keep the
capillary free from film growth, which may happen by a
A lot of effort has already been made in spectral charac- direct injection together with the working gas. This fact
terization of the discharge [2,7]. The most intensive argon can enhance the life time and reduces maintenance costs,
lines can be found in the spectral region between 670 and which is desired for industrial use.
970 nm. Few argon lines with a much lower intensity in
the spectra can be found at 415 and 420 nm. In addition
to the argon lines spectral lines from nitrogen, oxygen,
hydrogen and hydroxyl groups can be identified, e.g. the 3.3 Video imaging
Hα line at 656.28 nm or the hydroxyl group at 308 nm, re-
spectively. These lines are resulting from dissociation and During the visual observation of the plasma jet it was fig-
ionization (due to the plasma jet) of the surrounding at- ured out that the beam looks quite homogeneously when
mosphere which contains nitrogen, oxygen and water. The the free jet does not interact with any surfaces. In contrast,
reference lines (or wavenumbers) are taken from the NIST when the plasma jet interacts with a surface a broaden-
database [32]. ing of the plasma plume was observed. Figure 5 illustrates
As expected the intensity of the spectral lines varies such behavior of the plasma jet. In case of a free jet (left
along the plasma jet. In Figure 4 the most intensive lines photograph) a small plasma needle is formed. In case of
for argon, nitrogen, oxygen and the hydroxyl group in de- substrate material in front of the plasma jet (right photo-
pendence on the distance between the spectrometer and graph) it grows wider and the formation of filaments can
the plasma jet nozzle are shown. be observed. Note that the photos taken with a common
The Hα line is not plotted in Figure 4 because of its photo camera.
marginal intensity in front of the plasma jet orifice. At a For better visibility the region of the interaction be-
larger distance this line cannot be identified clearly. tween the plasma and the surface has been observed with
658 The European Physical Journal D

Fig. 5. Comparison of the behavior of the plasma jet with

and without a substrate in front of the plasma. On the left
photograph the “free” plasma jet is shown. The interaction
with a metal plate is shown on the right hand side of this
photograph.

a high speed camera. The left series in Figure 6 shows Fig. 6. Temporal evolution of the plasma jet in front of a
the time evolution of the plasma beam in front of a metal conductor (copper plate) on the left and in front of an insulator
(copper) plate. The formation of some discharge channels (glass wall) on the right. The substrate is always located at
(filaments) can be clearly observed. In the right series in the bottom of the photographs. The dashed line indicates the
Figure 6 the behavior of the plasma jet in front of an insu- position of the measured light intensities evaluated in Figure 7.
lating material (glass) is shown. Here we can find a rather
quiet discharge without visible filaments. It looks like the
undisturbed free plasma jet. in a larger horizontal plane, e.g. between 5 and 80 pixels.
For deeper understanding of the plasma discharge the The formation of filaments is a common feature in opera-
c
images from the movies were analyzed by a MatLab pro- tion of microplasmas [36].
gram and plotted in color code diagrams. To get an im-
pression of the temporal evolution the single photographs
are combined to a series of e.g. 60 frames, respectively 3.4 Thin film deposition in precursor-containing
60 ms. The intensity distribution at every millisecond has atmosphere
been recorded along the line indicated in Figure 6. By
this procedure the differences in the time-dependent be- The APPJ has been designed for surface treatment, e.g.
havior of the plasma jet in front of the surfaces can be for change of wettability etc. An interesting feature is the
identified very easily. In Figure 7a the plasma jet inter- use of the APPJ for thin film deposition of slica or alu-
acts with a glass surface. The relative light intensity of mina layers, respectively, in order to protect polymer sub-
the jet is about 40% (normalized to the maximum light strates. For this purpose, silicon-containing (HMDSO) or
intensity for the metal plate). Therefore, the photograph aluminum-containing (ATI) precursors have been added
is not so bright than for the case in front of a metal plate to the jet plasma.
(Fig. 7b). The light intensity is mainly distributed between During the plasma process the HMDSO molecules dis-
25 and 55 pixels, respectively between 1.8 and 3.9 mm in sociate into C5 H15 OSi+
2 radicals and CH3 groups [3]. The
horizontal plane. This region corresponds with the region radicals can be deposited onto the substrate surface and
where the plasma beam is located (center of the jet is at form thin films. The properties of the films (hardness,
40 pixels). In contrast, in front of the copper plate (see transparency etc.) depend on the stoichiometry, e.g. on
Fig. 7b) the maximum relative intensity is 100% (normal- the composition and the percentage of SiOx . During the
ized). The position of the maximum peaks is more ran- film deposition hydrocarbon groups and carbon atoms are
domly distributed in time. also incorporated into the films. The reason for this is that
The intensity fluctuations and position of the plasma the precursor is commonly only partly dissociated. With
jet in front of the copper plate are justified by the forma- additional oxygen the ratio between silicon and oxygen
tion of small filaments (discharge channels) which “jump” in the SiOx film can be varied from polymer-like (1:1)
 S. Bornholdt et al.: Characterization of an APPJ for surface modification and thin film deposition 659

Fig. 8. XPS overview spectra for untreated (grey line) PMMA

sample and for the sample coated by the plasma jet in
Ar/HMDSO atmosphere (black line). The inset shows a typical
“footprint” of the deposited film.

Fig. 7. Relative distribution of light intensities of the plasma

jet in horizontal plane in front of an insulator (glass) (a) and
in front of a conductor (copper) (b). The dashed line indicates
the photograph at 10 ms, as indicated in Figure 6.

to quartz-like (1:2) structures. The XPS-spectra for the

coated and uncoated PMMA substrates in Ar/HMDSO
plasma are plotted in Figure 8. The diameter of the ring Fig. 9. XPS overview spectra of an alumina layer deposited
of highest deposition rate corresponds to the capillary and by the APPJ onto a glass substrate in an ATI-containing at-
jet diameter. mosphere. The Al peaks are clearly visible.
The XPS spectra of the deposited sample show typi-
cal peaks of Si2s (154.5 eV), Si2p (103.5 eV) states and an
increase of the oxygen (533.5 eV) peaks which are clear been demonstrated for the first time the possibility of alu-
indications for SiOx deposition. The static “footprint” of mina layer deposition by the atmospheric pressure plasma
the deposited film has a crater-like shape, see inset in Fig- jet “kINPen”. A local deposition of thin AlOx films un-
ure 8. This structure is due to the operation of the jet: in der atmospheric conditions might be highly desirable for
the centre the layer thickness is smaller compared to the corrosion protection.
edge of the jet. This observation, which has also been re-
ported in literature [37], is caused by transport phenomena
at the interaction zone between jet and substrate surface. 4 Summary
Furthermore, the APPJ has been operated in ATI-
containing atmosphere to deposit AlOx thin films. Sim- The atmospheric pressure plasma jet (APPJ, kINPen) has
ilar to the HMDSO-containing plasma the ATI molecules been characterized by different types of diagnostics.
are fragmented by dissociation of methyl groups and the By using the calorimetric probe we were able to mea-
stronger Al–O bindings are preserved, resulting in the for- sure the energy influx by the plasma jet at different dis-
mation of alumina films. In order to proof the mechanism, tances between nozzle and substrate surface. With this
we deposited the films onto silicon wafers. After examina- knowledge the optimal position for surface modification of
tion by XPS not only the Si peaks of the substrate but different materials can be determined. It was found that
also the Al peaks of the deposited layers can be clearly rec- the VUV/UV radiation from the plasma jet provides the
ognized (Fig. 9). To our knowledge, this experiment has main contribution of the energy influx to the substrate
660 The European Physical Journal D

surface. In addition we can estimate the real surface 8. J. Thornton, J. Vac. Sci. Technol. 11, 666 (1974)
temperate which plays an important role for activation of 9. I. Hussla, K. Enke, H. Grunwald, G. Lorenz, H. Stoll, J.
temperature sensitive surfaces or organic/biomedical ma- Phys. D 20, 889 (1987)
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the measured electric probe currents the influence of free Plasma Phys. 28, 149 (1988)
charged carriers in the plasma jet could be demonstrated. 11. H. Deutsch, H. Kersten, A. Rutscher, Contrib. Plasma
By optical emission spectroscopy the composition of Phys. 29, 263 (1989)
the plasma jet could be identified. It was shown that in 12. S. Bernstein, T. Wong, R. Tustison, J. Vac. Sci. Technol.
the plasma not only the inert gas (argon) is included. In B 12, 605 (1994)
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László, R. Bellissent, J. Non Cryst. Solids 164, 1143 (1993)
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