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Experimental investigation of hydrogen peroxide RF plasmas

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2016 Plasma Sources Sci. Technol. 25 025003

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 Plasma Sources Science and Technology

Plasma Sources Sci. Technol. 25 (2016) 025003 (12pp) doi:10.1088/0963-0252/25/2/025003

Experimental investigation of hydrogen

peroxide RF plasmas
RBarni1, ADecina1, SZanini1, ADOrazio2 and CRiccardi1
1
Dipartimento di Fisica G.Occhialini, Universit degli Studi di Milano-Bicocca, p.za della Scienza 3,
I-20126 Milano, Italy
2
Dipartimento di Ingegneria Astronautica, Elettrica ed Energetica, Sapienza Universit di Roma,
via Eudossiana 18, I-00184 Roma, Italy

E-mail: claudia.riccardi@mib.infn.it and ruggero.barni@mib.infn.it

Received 11 May 2015, revised 30 November 2015

Accepted for publication 14 December 2015
Published 27 January 2016

Abstract
This work reports a detailed experimental study of the plasma properties in low pressure
RF discharges in hydrogen peroxide and a comparison with argon under the same operating
conditions. H2O2 plasmas have been proposed for sterilization purposes. Electrical properties
of the discharge were shown to be similar, as for the RF and DC voltages of the driving
electrode. Bulk plasma volume remains stable, concentrated in an almost cylindrical region
between the two facing electrodes. It was found that the electron temperature is almost
uniform across the plasma and independent of the power level. This is higher than in argon
discharges: Te=4.60.9eV versus Te=3.31.1eV. The plasma density increases almost
linearly with the power level and a substantial negative ion component has been ruled out in
hydrogen peroxide. Dissociation in the plasma gas phase was revealed by atomic hydrogen
and hydroxyl radical emission in the discharge spectra. Emission from hydroxyl and atomic
oxygen demonstrates that oxidizing radicals are produced by hydrogen peroxide discharges,
revealing its usefulness for plasma processing other than sterilization, for instance to increase
polymer film surface energy. On the other hand, argon could be considered as a candidate for
the sterilization purposes due to the intense production of UV radiation.
Keywords: radiofrequency plasma, hydrogen peroxide, plasma sterilization

(Some figuresmay appear in colour only in the online journal)

1.Introduction Plasma processing is considered to be a promising phys-

In modern medicine and in the pharmaceutical industry, as
well as in other sectors, the efficient sterilization of tools and
surfaces is of central importance [1]. The main challenge for
these applications is selecting a reliable sterilization agent.
Currently, sterilization methods based on the gas phase are
drawing significant interest, since a large number of critical
devices (according to the classification of Spaulding [2])
cannot be subjected to thermal treatments. In this framework
the use of hydrogen peroxide as a chemical decontaminant
and sterilant is widespread, mainly because of its simplicity
and its environmentally friendly decontamination products,
i.e. water vapor and oxygen [3]. In the past decade, decon-
tamination by hydrogen peroxide has been used frequently for
sterilization purposes in a wide range of applications [4].
ical method for sterilization [5]. It is generally performed
by producing oxidizing radicals in the plasma state, starting
with oxygen or water vapor in the gas phase mixture feeding
the electrical discharge [5]. Within this approach, the pros-
pect of plasma sterilization employing directly hydrogen per-
oxide has been proposed [6, 7] and applied as a commercial
sterilization device, referred as the STERRAD NX method,
by Advanced Sterilization Products [8].
Moreover, besides these very important decontamination
and sterilization applications, hydrogen peroxide may also be
used as a reactive agent, both in vapor and in plasma, aimed
at more general material surface processing, for instance the
deposition of oxide thin films [9].
Despite the hydrogen peroxide plasma sterilization process
and its applications being well characterized in literature, little

0963-0252/16/025003+12$33.00 1 2016 IOP Publishing Ltd Printed in the UK

Plasma Sources Sci. Technol. 25 (2016) 025003
is known concerning such plasmas [10]. Most of the modern
research focuses on the production of hydrogen peroxide,
mainly from water vapor and using atmospheric pressure
plasmas [1115]. No data exist so far in the literature con-
cerning key physical plasma parameters, such as the electron
temperature and density, not to mention the flux and energy of
ions impinging on an exposed surface. Furthermore, there is
little information regarding the gas phase chemical composi-
tion, like the dissociation degree or the density and fluxes of
(oxidizing) radicals towards such surfaces or the UV emission
involved. Even more disturbing is the lack of data showing
how the plasma state is influenced by operating parameters
like discharge power level, pressure range and so on. This is
mainly due to the lack of suitable plasma diagnostics installed
in the reactors used in the processing. In general, the poor
knowledge, control and understanding of plasma processes,
explain why, despite their promising properties and the claims
so abundant in scientific literature, they rarely find real appli-
cations. It is worth noting, for instance, that a recent paper
discusses openly the existence of a true plasma decontami-
nation process [16].
In this work a characterization of radiofrequency dis-
charges in hydrogen peroxide was undertaken, by means of
a dedicated plasma reactor, equipped with an extended set of
plasma diagnostics, including RF electrical probes, movable
Langmuir probes, optical emission spectroscopy (OES) with a
spectrometer and photomultiplier tube (PMT). This provided
an insight into the role of different agents acting in the plasma
processing.
2. Experimental set-up
A layout of the experimental set-up is displayed in figure1.
It consists of a cross-shaped vacuum chamber equipped with
a RF plasma source. The chamber, with a diameter 100mm
and two arms both 215mm long, had several ports on the
four CF-100 flanges and can be evacuated through the bottom
flange by a rotary pump (Varian SD-301, maximum pumping
speed S=4.4 L s1) up to a residual pressure of 3.3101 50 Pa in these experiments) with a fairly high concentration.
Pa. Taking into account the conductance of the flow duct and
the decrease in the pumping speed, an effective speed was esti-
mated to be Seff=2 L s1 at a 10 Pa pressure. The chamber
volume was estimated to be 3.4L. A constant flow of Ar or
He could be provided and controlled by a flowmeter (Aera
FC-7700C), whereas hydrogen peroxide in a sealed Pyrex
bottle was evaporated into the chamber through a micrometer
needle valve. When pumped away, a liquid nitrogen trap was
used, in order to prevent mixing of peroxide with pumping oil.
Total pressure in the chamber was measured by a Pirani gauge
(Thermovac TTR-90 by Leybold). The diffusion coefficient
of hydrogen peroxide (D0=0.19cm2 s1) could be used to
estimate the diffusion timescale in the chamber, D=1.3ms,
and the diffusion speed, vD=15 m s1, at a 10 Pa pressure
[17]. The corresponding values in argon are comparable
(D0=0.179cm2 s1). On the other hand, from the pumping
speed data a residence time of 1.7s and a flow velocity of
25cm s1 in the main chamber could be estimated at the same
R Barni et al
pressure. This means that the chamber could be considered as
a well-mixed reactor [18]. This also holds trivially when there
is no pumping.
The RF source consisted of a stainless steel disk (diam-
eter 30mm and thickness 2mm) shielded by a grounded alu-
minium cup (diameter 35mm and thickness 2mm) separated
from the source by an alumina hollow disk (1mm thick).
This prevented the formation of plasma in the part of the
chamber above the source electrode [19]. The source was cou-
pled through a vacuum feed-through on the top flange to a
semi-automated RF matching unit which could be fed by a
13.56 MHz RF supply (PFG-300 by Huettinger). The mainly
capacitive RF coupling of the discharge was enhanced by the
presence of a counter-electrode, a stainless steel disk, diam-
eter 80mm and thickness 2mm, facing the source at a fixed
distance, typically 43mm. In this configuration the electrode
system capacitance in vacuum was measured to be 91 pF
(Z=129 at 13.56 MHz).
On the front flange a 100mm quartz window is mounted,
whereas on the rear flange three vacuum ports accommodate
the two gas inlets and an optical fiber vacuum feed-through.
Hydrogen peroxide was prepared from a commercial water-
peroxide solution by Bresciani (130vol. corresponding to
35 wt %). Due to the lower vapor pressure of hydrogen
peroxide (180 Pa versus 2470 Pa at 20 C [20]), the solution
concentration could be raised by distillation, pumping away
the mainly water vapor gas phase in a sealed bottle. About 30g
of the solution (11g of H2O2) was reduced to 4.64g, which
was used in the whole experimental campaign.
A concentration of 855 wt % was estimated by repeat-
edly measuring the equilibrium vapor pressure at 20 C [20].
As already stated, for each experiment a fixed quantity (about
40 l) of the enriched solution was syringed into a sealed
bottle and frozen by immersion in liquid nitrogen (Dewar).
Residual air in the bottle was then pumped away before
melting occurred. Subsequently, the whole volume of the per-
oxide solution was evaporated into the main chamber. After
a brief pumping, the chamber was isolated. This allowed it
to reach a gas phase in the reactor at a fixed pressure (about
As a diagnostic tool of the plasma state Optical Emission
Spectroscopy (OES) was employed. OES of the discharge
could be used to gain insight into the excited species produced
in the source [21, 22]. Light was collected inside the vacuum
chamber with 50 m UV enhanced fiber optics (UV-50-FC
by Avantes) with a numerical aperture NA=0.22. The fiber
view-field was restricted with an alumina pipe in order to col-
lect light only from the central plasma region. The conical
view-field had a sectionof about 1cm radius at the center of
the vacuum chamber (see figure1). In this way, the contrib
ution of the bright plasma sheath near the RF electrode was
removed and the contribution of the side regions minimized.
This ensured the imaged plasma volume was approximately
constant under the different discharge conditions and the
changes in light intensity can be traced to those in the plasma
state. Light was delivered through a vacuum feed-through
and another fiber to a wide band, low resolution spectrometer
(PS-2000 by Avantes, with a holographic grating 600 lines mm1
2
Plasma Sources Sci. Technol. 25 (2016) 025003
Figure 1. Schematic view of the experimental setup and diagnostics of the plasma reactor. The optical fiber have been connected to a
UVVis spectrometer or to a phototube.
blazed at 400nm) which allowed the measurement of the
emission spectra. The spectra covered the UVVisNIR range
from 175 to 1100nm with a resolution of about 0.6nm. Line
intensity was measured and emitting atoms and molecules
identified [23, 24]. The data on the emission line intensities
of argon were also used to estimate the electron temperature
and the concentration of argon metastables, as presented in
section4 [25].
A calibrated voltage divider was used to measure the
RF and DC components of the voltage on the RF electrode
and inserted at the position of the RF feed-through [26].
A RF-compensated Langmuir probe was used to measure
plasma profiles along the horizontal axis of the device. The
probe scan covered the whole region across the electrodes (see
figure1). The probe had an exposed tungsten tip, 5mm length
and 1mm diameter. The probe tip connection was insulated
and shielded in a probe holder, 15cm in length, made of two
coaxial alumina tubes. RF compensation was achieved using
the method proposed long ago by Godyak et al [27] and Chen
[28]. A miniature RF choke (made of a ferrite core, Q200
with an impedance of about 85 k) was embedded near the
probe tip. A floating electrode (a copper foil, 10mm wide,
3mm diameter, glued on the probe alumina tube 3mm before
the tip) exposed to the plasma was coupled through a large
capacitor to the probe tip (100 pF) to ensure an almost con-
stant impedance load during the probe voltage scan to record
the Langmuir characteristics [28].
The Langmuir probe was calibrated by fine tuning the
choke capacitance and thus the frequency to match the 13.56
MHz RF supply. The probe was previously employed in other
plasma discharges and checked against traditional Langmuir
probes [21]. In most of the experimental conditions dis-
cussed here it has been observed that the probe compensation
improves, albeit marginally, the shape of the Langmuir char-
acteristics curve, increasing the reported value of the floating
3
R Barni et al
potential, and so the accuracy of the measure of the plasma
parameters.
In general a fixed voltage ramp was applied in a 100ms
time scan [29] and the probe current was measured with an
equivalent resistance of 100 by an Agilent scope with a
100kHz sampling rate. The Langmuir characteristics were
obtained by averaging 20 voltage ramps. Analysis of the curve
was performed using dedicated software, in order to extract
the plasma density and potential, as well as the electron
temperature [29]. In a number of instances, the scans were
limited to the measure of the floating potential or the ion satur
ation current profiles which were performed directly with the
scope. As for the former, the probe was directly connected to
the 1 M input, whereas, for the latter, the voltage drop on the
shunt resistance after imposing a constant bias (36V) to the
probe tip was measured.
3. Plasma state
The electrode system was tested initially with argon. A RF
discharge is easily ignited for pressure above 2.5 Pa and up
to 200 Pa and sustained previously at supply power as low as
2W. The breakdown voltage was measured to be 1438V
at P=50 Pa [30]. This is a smoothly decreasing function
(about15%) of the pressure in the 10200 Pa range. It started
to rise substantially only below 10 Pa. The discharge ignition
was marked by a sharp drop in the DC electrode voltage. By
increasing the supply power level stepwise the transition could
be caught many times measuring the actual RF breakdown
voltage. In the whole pressure range the power level measured
at the RF supply remained proportional to the square of the
2
RF voltage amplitude measured at the electrode (W = a VRF )
with a constant almost independent from the pressure, at least
for pressure below 70 Pa. This corresponds to an effective
Plasma Sources Sci. Technol. 25 (2016) 025003
Figure 2. Radiofrequency and the absolute value of the DC electrode potential as a function of the power level in hydrogen peroxide and
argon discharges at 50 Pa pressure. The dotted line shows a power-law fit with a close to 0.5 exponent.
impedance of about 5 k. As might be expected, because of
the electrode setup, a negative DC voltage appeared on the RF
electrode [31, 32]. Its absolute value was nicely proportional
to the RF voltage, in the whole pressure range, i.e. somewhat
larger the lower the pressure was.
The behavior of RF and DC voltage with applied power
also holds for discharges in peroxide in experiments at a fixed
pressure, about 50 Pa. This value was chosen mainly because
it was the one used in the most advanced plasma sterilization
method [8]. However, it is also quite favorable because break-
down happens easily at this pressure. This extends to nearby
pressures, at least within the 20100 Pa range. Moreover,
although the pressure level is not exactly reproducible in dif-
ferent experimental scans and it derives slightly, especially at
a high power level, it was checked that the discrepancies intro-
duced into the electrical characteristics of the discharge are
weak. The breakdown voltage in peroxide was measured to be
1285V. As for argon, it decreased slightly as a function of
the pressure, about 10% from 20 to 100 Pa. The value being
slightly lower than in argon could probably be related to the
lower ionization potential of hydrogen peroxide (10.63 with
respect to 15.8eV [32, 33]) which requires less energetic elec-
trons thus possibly compensating the expected larger electron
losses due to H2O2 electronegativity.
The RF voltage increased nicely as the root of the power
level. Its values were only slightly smaller (934% over the
whole power range) than the corresponding ones in argon.
The effective impedance of the discharge and electrodes was
5.80.1 k. The same reduction with respect to argon was
also observed in the absolute values of the DC potential.
A comparatively smaller DC bias with respect to argon was
observed only near the breakdown at a power level less than
10W. The ratio between the DC and the RF voltage values was
the same in both H2O2 and Ar, being 0.870.02 constant in
the whole power range WRF>10W. Since the instantaneous
electrode potential was the sum of the DC and RF voltages,
the fraction of the RF period when the electrode potential was
R Barni et al
positive with respect to the grounded walls (possibly draining
electrons from the gas phase) was independent from the power
level, about 0.160.01. The measured trends are displayed
in figure2.
At lower power levels, near the breakdown, the discharge
glow was concentrated just below the RF electrode, forming
a sheath separating it from the electrode surface. The sheath
thickness was mainly controlled by the pressure level, since the
conditions match those of a collisional sheath because of the
intermediate pressure range of these experiments [31]. Using
equation (11.2.54) of [31] and electron density and temper
ature values discussed below, a mean sheath thickness of
4.6mm for the argon discharge was estimated at WRF=50W
and P=50 Pa. The discharge became brighter as the power
level is increased. The glowing region, however, expanded
downwards filling quite uniformly the whole region between
the two facing plates, already at a power level of about 25W, in
hydrogen peroxide. Conversely, its lateral extension appeared
almost untouched, remaining comparable to the RF electrode
diameter. However, the estimate of the effective plasma exten-
sion based only on emission light intensity was not conclusive.
Two pictures of the discharge taken at a power level of 10 and
50W are displayed in figure3. In order to access the plasma
properties the characteristics curve of the Langmuir probe was
also analyzed. A typical example is shown in figure4, together
with the fit function used to extract the plasma parameters
[29]. However, a rough picture of the plasma distribution
could be reached initially by inspecting the spatial profiles of
the ion saturation current and of the floating potential, which
are displayed in figure5. The bell shaped profiles of the ion
saturation current are nicely reproduced by Gaussian curves.
The FWHM was 37mm for H2O2 and 39mm for argon, nicely
matching the RF electrode diameter of 35mm. Whereas the
amplitude increased with the power level, the profile shape
was only slightly affected; the FWHM also staying compa-
rable with the electrode diameter at higher power. The floating
potential showed a much shallower spatial dependence, with
4
Plasma Sources Sci. Technol. 25 (2016) 025003 R Barni et al

Figure 3. Pictures of the discharge glow in hydrogen peroxide at a power level of (a) 10W, near the breakdown and 50W (b). In the latter
the RF electrode and the shielding cup can be viewed on the upper side.

Figure 4. A typical Langmuir characteristics curve in gray together with the fitted dotted line, with a function containing the ion and
electron density and the electron temperature as free parameters. On the right axis, the second derivative of the probe current with a vertical
log-scale.

a FWHM of 90mm. Neglecting the effect of a possible spatial
dependence of the electron temperature, the sign of the radial
electric field agreed with that prescribed by ambipolar diffu-
sion. So, possibly electron and ions radial fluxes were almost
balanced, at least for the bulk plasma region.
At this stage the full Langmuir characteristics had been
measured. Its analysis allowed evaluation of the electron
temperature, together with the ion and electron density and
the plasma potential. However, the analysis also introduced
larger uncertainties which partly obscure, for instance, the
plasma potential spatial profile shape. Results are displayed in
figures68. In order to have an estimate of the level of vari-
ations in the values, repeated measurements were performed
under the same conditions which are reported as multiple
points on the plots. Discrepancies of up to 50% were observed
in repeated Langmuir probe measurements. Consistent
with the trend of the ion saturation current, plasma density
appeared to rise with the power level. The trend is somewhat
linear, more so in hydrogen peroxide than in argon. At low
power levels their density was similar, below 5 109 cm3,
although with a great uncertainty due to the small size of the
ion saturation current. The plasma density become larger in
argon with respect to hydrogen peroxide at a large power
level. For instance, it became about three times larger at the
center of the vacuum chamber with a power level of 100 W:
here there was an estimated a density of 3.20.7 1010 cm3
versus 1.00.2 1010 cm3. Electron density could be evalu-
ated from the probe current (subtracting the ion saturation
contribution) at the plasma potential [29]. In these experi-
ments, electron and positive ion densities were similar, equal

5
Plasma Sources Sci. Technol. 25 (2016) 025003 R Barni et al

Figure 5. Horizontal axis profile of the floating potential and of the ion saturation current in hydrogen peroxide (100W) and argon (50W)
discharges at 50 Pa pressure. The dotted line shows a Gaussian fit function with a FWHM of 37mm.

Figure 6. Electron temperature and ion density measured from the Langmuir characteristics fit as a function of the power level in hydrogen
peroxide and argon discharges at 50 Pa pressure.

within the measurement of uncertainty, which implies that
even in the somewhat electronegative hydrogen peroxide the
negative ion density was lower than the electron one. This
holds in the whole power range. It is at variance with other
observations, albeit made in a different electrode geometry,
using more electronegative gases, where negative ion den-
sity largely exceeded the electron one [29]. Langmuir char-
acteristics curves, after RF compensation, showed good
exponential behavior just above the floating potential, which
implies that the bulk electron energy distribution (EEDF)
is remarkably Maxwellian [29]. This could also be grasped
from figure 4, where the logarithm of the second derivative
of the (SavitzkyGolay smoothed) probe current, proportional
to the EEDF, is displayed [29]. This is roughly parabolic
between the floating and the plasma potential. This observa-
tion holds for both argon and peroxide plasmas investigated
here. Fitting the region of the characteristics curve above the
floating potential with an exponential function yielded meas-
urement of the electron temperature. This was fairly flat over
the power level range, both in H2O2 and in argon. It was some-
what larger only at the lowest values of the power. Averaging
values for WRF>15W obtained Te=3.31.1eV for argon
and Te=4.60.9eV for hydrogen peroxide. For argon,
also only a slight decreasing dependence from the pressure
in the 5200 Pa range was found. Finally, the value of the
DC plasma (space) potential could be obtained either from the
floating potential plus electron temperature or from the inflec-
tion in the characteristics curve. Both methods produced com-
parable results, although these show discrepancies of the order
of a few volts (larger than those in floating potential alone, see
figure7). This prevented their use to estimate, for instance, the
radial electric field from the spatial profile data or the accurate
shape of the profile. Plasma potential, however, was invariably
positive, about 1525V, in the whole power level range for

6
Plasma Sources Sci. Technol. 25 (2016) 025003 R Barni et al

Figure 7. Horizontal axis profile of the electron temperature and of the plasma potential, estimated from the inflection point in the probe
current, in hydrogen peroxide (25W) and argon (100W) discharges at 50 Pa pressure.

Figure 8. Horizontal axis profile of the ion and electron density in a hydrogen peroxide discharge (25W) at 50 Pa pressure. The dotted line
shows a Gaussian fit function with a FWHM of 37mm.

both argon and hydrogen peroxide. This happened notwith-
standing the fact the RF voltage and the DC potential at the
electrode changed by about one order of magnitude. It could
be noted, however, that space potentials were smaller than the
maximum positive voltage reached by the electrode potential
during the RF period (see figure4) in the whole power level
range. So, even for a small fraction of the time, electrons were
drained to the electrode across the sheath, balancing the pre-
vailing positive ion flux [30].
Finally, the spatial profiles of the plasma parameters were
measured (see figure 8). Plasma density profiles reproduced
remarkably well the ion saturation current ones. Their bell
shape was nicely Gaussian, with a FWHM of 33mm in argon
and 37mm in hydrogen peroxide. Their symmetry with respect
to the center of the chamber points towards a substantial radial
uniformity of the plasma region with respect to the inter-
electrode axis. On the other hand, the electron temperature
and, within a larger fluctuation band, the plasma potential
were flat; practically constant over the whole spatial profile.
Averaging over the whole profile yielded a Te=4.80.5eV
for hydrogen peroxide, compared with Te=2.80.3eV for
argon. Allying this to previous data, it can be safely stated
that the plasma region fills a constant portion of the vacuum
chamber when the power level exceeds a few tens of W.
This corresponds probably to an almost cylindrical volume
where height is the inter-electrode distance and the base area
matches the RF electrode extension. These considerations are
of importance in order to estimate the effective processing
region where materials can be directly exposed to the plasma.
Finally, data measured concerning the plasma density and the
electron temperature, together with those about the DC poten-
tial, could be used to estimate the effective power absorbed
by the plasma, by evaluating the stochastic and ohmic heating
power, as discussed in section 11.2 of [31]. For argon dis-
charges, a fraction between 8 and 15% of the input power
level was estimated in the 5100W power range.

7
Plasma Sources Sci. Technol. 25 (2016) 025003
Figure 9. A typical OES spectrum in a hydrogen peroxide discharge (200W) at 50 Pa pressure. The main emission lines are identified on
the spectrum.
Figure 10. Intensity of a few emission lines in hydrogen peroxide discharges at 50 Pa pressure as a function of the power level. The dotted
lines show linear fit functions to the data.
4. Optical emission spectroscopy of peroxide
plasma
The typical discharge spectra of a peroxide discharge is dis-
played in figure9. It refers to a power level (200W) and total
pressure (50 Pa) similar to those already considered in the
previous section. Discharge spectra were dominated by the
Balmer atomic hydrogen emission lines, with H the most
prominent, atomic oxygen [24] and hydroxyl [23] ones.
A clear signature of impurities, mainly CO band emission
was significant too [23]. It was decieded that only lines which
could be assigned unambiguously and the intensity of which
is large enough to withstand the noise level should be ana-
lyzed. The intensity of a hydrogen and a hydroxyl line as a
function of the power level is shown in figure10. Both dis-
play a remarkable linear trend up to the highest power level.
8
R Barni et al
As already stated, the OES view-field was chosen in such a
way to be almost independent from any changes in the dis-
charge volume. Since both the emitting states could be pro-
duced in electron dissociative interactions on the peroxide
molecule, it is straightforward to infer that the trend could
be understood as a linear increase in the electron density in
the plasma gas phase, if the electron temperature and the per-
oxide partial pressure were constant. This can be taken as a
confirmation of the direct findings based on Langmuir probe
analysis and could be extended to the highest power level
possible with the current RF supply. This was, fairly com-
monly, observed in RF discharges of other electronegative
gases [17]. This could be correlated to the linear increase with
the power level displayed by the total discharge current too.
Direct excitation by electron impact on ground state hydrogen
atoms or hydroxyl radicals, a concurrent process leading to
Plasma Sources Sci. Technol. 25 (2016) 025003
Figure 11. Intensity normalized to the atomic hydrogen H line of a few emission lines in hydrogen peroxide discharges at 50 Pa pressure
as a function of the power level.
light emission, would have caused much greater difficulties in
explaining the observed trend [22]. In fact, ground state rad-
ical and atom concentration were expected to be proportional
to electron density, being built up by electron impact dissocia-
tion too. This would have led to a stronger than linear func-
tional dependence on electron density for the excited radical
concentration and thus of the emitted light intensity. In order
to bring back OES data to the observed purely linear trend,
it was necessary to speculate a somewhat ad hoc relation-
ship between the power level and the electron density. This
also hinted at the point that electron temperature cannot vary
very much with the power level. Indeed the rate of dissocia-
tive interactions (and of direct excitation too) were strongly
dependent on the electron temperature (usually exponentially,
for temperatures of a few eV, as it was the case with RF dis-
charges [31]). This would translate to a strong dependence of
emitted light intensity. Again, to bring back OES data to the
observed purely linear trend, it was necessary to speculate an
ad hoc relationship between the electron temperature and the
electron density as the power increased. An almost constant
electron temperature agreed with the direct findings based
on Langmuir probe analysis and such a conclusion could be
extended to the highest power level possible with the current
RF supply, where RF compensation of the Langmuir probe
fails. This was also independently confirmed by the observa-
tion that the ratio between the H and H intensity was not
correlated, within 5%, with the power level: R=0.470.02. with the power level. This was observed for the clearly iden-
The same conclusion could be obtained by comparing different
oxygen atom lines, albeit with a greater uncertainty. A signifi-
cant role of energetic electrons in the bulk plasma region, for
instance accelerated by the RF sheath, could be disfavored too,
since again the voltage across the sheath and then the electron
energy gain would lead, on all evidence, to a stronger than
linear functional dependence on the power level. A significant
deviation from a purely Maxwellian energy distribution was
already ruled out by the analysis of the Langmuir characteris-
tics at a low power level. The ratio between OH-309nm and
9
R Barni et al
H intensity was also flat within errors in the whole dataset,
R=0.220.03. This also pointed towards a common origin
of both excitation mechanisms.
The trend shown by atomic oxygen emission lines was dif-
ferent, as can be better seen in figure11, where the intensities
were normalized to that of the most intense line, the H at
656nm. Atomic oxygen is another important agent for sterili-
zation and in general as the typical reactive oxidizing species
(ROS) in plasma gas phase [5]. It is clear that the linear trend
observed above no longer exists. This indicates that direct for-
mation of excited oxygen states from electron impact on water
peroxide cannot be the main excitation channel. Light emis-
sion could result from excitation of oxygen atoms produced
by the dissociation of OH and O2H radicals. However, since
radical formation is somewhat proportional to the dissociation
rate, and so to electron density, it could be expected that a
stronger than linear functional dependence on electron density
and hence on power level would be observed. This was ruled
out by the data gathered in this experiement. Excited oxygen
atoms, then, have to be quenched effectively at a high power
level. Only this could explain why saturation was observed. As
further evidence, it was also observed that the ratio between
the 844 and 777nm atomic oxygen emission line intensity was
independent from the power level: R=0.240.03. Further,
in figure11, it can be appreciated that the impurities relative
emission is quite flat, which implies a somewhat linear trend
tifiable CO lines, as well as for other minor lines, for instance
the one at 288nm, already visible in the figure 9 spectrum.
This points towards a constant impurity concentration level,
determined mainly by the absolute density of water peroxide.
It is fully consistent with impurities coming from the walls
or, more probably, from the electrode surfaces, as a conse-
quence of the diffusion flow and surface reaction of peroxide.
As could be expected, the good reproducibility displayed by
H, O and OH emission intensity in different power scans is
not preserved by impurities. It was somewhat comforting that
Plasma Sources Sci. Technol. 25 (2016) 025003
Figure 12. Comparison of the electron temperature measured by the Langmuir curve fit and by OES data in argon discharges at 50 Pa
pressure as a function of the power level.
impurities emission intensity declined as ageing of the device
proceeds.
Experiments involving OES using argon the gas phase were
also performed. As already discussed, argon discharges bear
many similarities with hydrogen peroxide ones. OES showed
that argon emission lines largely dominated the spectra, with
only small impurities, notably OH presumably arising from
water vapor wall outgassing. Light intensity was broadly
linear with the power level and also to the total pressure,
at least in the range around 50 Pa. Besides this, the rich emis-
sion line spectrum of atomic argon in VIS and near IR (RF
argon spectra were dominated by the system of 3p54p4s
transitions, the 2px system in the Paschen notation, in the red
and in the near IR [24]) could be used to measure plasma
parameters such as the electron temperature and metastable
density [25]. Here, the proposed method [34, 35] is recalled
only briefly. The core of the method was to exploit the dif-
ferent electron energy dependence of the cross section of
the 2px excited levels and the large differences in the prob-
ability of electron impact excitation of such levels starting
from metastable argon atoms [25]. The proposal was to use
the intensities of the whole set of emission lines of the 2px
system, provided that their intensity was not negligible and
no ambiguity could arise (especially because of the limited
wavelength resolution) to define a sort of 2 function:
2 = 2 N (N 1) [log 2(Rn /Rm )],
n < m = 1, N
Rn = (In /bn )/ k n(Te )(1 x *) + k*n(Te )x * ,
where I is the measured intensity of the selected emission
line and b is the branching ratio of that particular transition
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 nth emission lines, respectively from
the ground state and from the two metastable states, while
x* are their concentrations. Minimization with respect to the
R Barni et al
parameters allowed the extraction of the electron temperature
and the two metastable concentrations. As discussed in pre-
vious published papers [34, 35], this procedure is more sen-
sible, reducing the systematic errors which could affect the
proposed analytical solution [25]. Using the measured intensi-
ties of thirteen lines, a fair reproduction of the relative intensity
pattern was obtained, within 30%, which corresponds to a 2
~ 0.1. The overall agreement with the Langmuir probe meas-
urement was comforting, as can be grasped from figure 12.
This confirms more directly that the authors suggestion that
electron temperature is mostly independent from the power
level, based on Langmuir probe analysis, holds and could be
extended to the highest power level possible with the current
RF supply.
A photomultiplier tube (PMT) was used to collect light
emitted during different phases of the RF oscillation. A PMT
by Hamamatsu (H10721-210) was used for its fast temporal
response and high sensitivity (rise time is 0.57 ns, gain ~
2106). Its ultra bialkali photocathode is sensitive to light
with a wavelength in the range 230700nm and the radiant
sensitivity curve almost flat between 300 and 500nm, sub-
stantially matching the emission spectra range [36]. Both
the number of PMT counts and the intensity of the collected
light increased linearly with the power level, with a slope in
argon almost twice that of in H2O2. This trend correlated to
that already observed for individual emission lines. With quite
a large dataset of events it was possible to assess how the
light emission was correlated with the different phases of the
electrode potential RF cycle. In particular, the distribution in
PMT peak amplitude and duration were almost symmetrical
between the positive and negative parts of the RF cycle and
almost no modulation was observed during the RF period.
This is reported in figure 13. This is not entirely expected
since the effective collision frequency at 50 Pa is larger than
the 13.56 MHz RF one [32]. The independence from the RF
cycle phase points towards a substantial uniformity in time
of the emission light, at least from the central plasma region.
10
Plasma Sources Sci. Technol. 25 (2016) 025003
Figure 13. Histogram of the PMT peak number in hydrogen peroxide (at two power levels) and argon discharges at 50 Pa pressure as a
function of the phase during the RF cycle.
Incorporating the previous considerations, it can be postulated
that, even in hydrogen peroxide, the plasma region, away
from the electrode sheath, is substantially stable during the
RF oscillation period.
5.Conclusions
A rather detailed experimental study of the plasma properties
in low pressure RF discharges in hydrogen peroxide has been
performed and a comparison made with the much more inves-
tigated argon ones.
Discharges were easily ignited and sustained in hydrogen
peroxide, just as in argon. Due to the lower vapor pressure
of hydrogen peroxide with respect to water, it is possible to
obtain highly concentrated gas phases of almost pure H2O2
by differential pumping. Electrical properties of the discharge
appeared quite similar indeed, as did the RF and DC voltages
of the driving electrode.
In a wide region of power level, from the breakdown up to
300W, the bulk plasma volume remained stable, concentrated
in an almost cylindrical region between the two facing elec-
trodes. The electron temperature was probably uniform across
the plasma (only its uniformity along the radial distance from
the discharge axis was checked) and almost independent from
the power level. It was higher than on argon discharges since
Te=4.60.9eV versus Te=3.31.1eV. The DC comp [6] KyiMS, HoltonJ and RidgwayGL 1995 J. Hosp. Infect.
onent of the space potential was possibly quite uniform too
in the bulk plasma. Plasma density increased almost linearly
with the power level, being smaller than in argon at the same
power. A substantial negative ion component had been ruled
out in the hydrogen peroxide plasmas, notwithstanding the
more than negligible electro-negativity of the parent molecule.
Dissociation in the plasma gas phase was revealed by atomic
hydrogen and hydroxyl radical emission in the discharge
spectra. Atomic oxygen was produced too, besides other
impurities, but its relative emission was suppressed at a large
11
R Barni et al
power level. Any substantial modulation of the light emission
during the RF cycle period was also exlcuded.
All these findings point towards a common picture, where
hydrogen peroxide plasmas are easily produced by RF dis-
charges and their gas phase is composed of highly oxidizing
radicals, partly different from those prevailing in water vapor
plasmas, as well as from the composition of the initial neu-
tral gas phase. Hydrogen peroxide discharges, then, have the
capability to deliver different plasma processing and surface
treatments and are potentially interesting for many applica-
tions, not confined purely to improved sterilization.
Acknowledgments
We are pleased to thank M Piselli for his technical support.
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