Characteristics of floating potential of a probe in electronegative plasma

A. K. Pandey and S. K. Karkari

Citation: Phys. Plasmas 24, 013507 (2017); doi: 10.1063/1.4973653

View online: http://dx.doi.org/10.1063/1.4973653
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Published by the American Institute of Physics

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 PHYSICS OF PLASMAS 24, 013507 (2017)

Characteristics of floating potential of a probe in electronegative plasma

A. K. Pandey1,2,a) and S. K. Karkari1,2,b)
1
Institute for Plasma Research, Bhat, Gandhinagar, Gujarat 382428, India
2
Homi Bhabha National Institute, Training School Complex, Anushakti Nagar, Mumbai 400094, India
(Received 30 September 2016; accepted 22 December 2016; published online 9 January 2017)
The floating potential of a cylindrical probe immersed in electronegative oxygen plasma has been
experimentally investigated as a function of electronegative parameters, a ¼ n =ne and c ¼ Te =T .
In the experiment, the bulk plasma has been found to be largely Maxwellian amid a small
component of hot electrons present in the discharge. The parameter a has been deduced from a
phenomenological model for a range of operating powers and pressures. By optimizing c in the
phenomenological model, the negative ion temperature range has been estimated by comparing the
measured floating potential with the theoretical curve. In the regime a > 1, the floating potential
has been observed to fall monotonically on increasing a in close agreement with the theoretical
curve, whereas, the theoretical results predict an increasing trend for a < 1. A qualitative
discussion has been presented to explain the overall behavior of floating potential under the
influence of negative ions. Published by AIP Publishing. [http://dx.doi.org/10.1063/1.4973653]

I. INTRODUCTION important as it governs the net outflow of flux/energy of

Electronegative plasmas are the ones having a significant
fraction of negative ions whose charge to mass ratio is compa-
rable to the background positive ions. These plasmas are
hugely popular in microelectronics industries as various elec-
tronegative gases are routinely being used for anisotropic
etching of silicon substrates.1 The negative ions facilitate thin
film deposition, plasma cleaning, and activation of material
substrates.2–4 Ions of negatively charged atomic/molecular
hydrogen are also required for the generation of MeV range
neutral beams5,6 to provide auxiliary plasma heating in fusion
devices. Due to fast recombination between positive and neg-
ative ions, plasmas containing negative ions are therefore pop-
ular in high voltage switching technology;7 besides, they are a
source for ion-ion thrusters.8 In recent years, there have been
profound studies on the characteristics of electronegative plas-
mas. Many exotic phenomena including electrostatic waves
and electric double layers have been reported in laboratory
plasma devices.9,10
An important characteristic of electronegative plasma is
the sheath voltage, which is extremely small as compared to
electro-positive plasmas. Therefore, these plasmas are good
for defect free treatment of soft polymeric substrates.11–13 A
number of analytical studies had been made regarding basic
behavior of sheaths in non-equilibrium plasmas.14–22 It has
been established that the negative ions in the plasma can
hugely impact the characteristic Bohm speed at the sheath
boundary. Consequently, the pre-sheath potential, which is
responsible for accelerating the positive ions to acquire the
characteristic Bohm speed at the sheath entrance, is modi-
fied. Theoretical results had also shown the existence of
multi-valued solution of the sheath potential when the nega-
tive ion parameters a and c exceed a certain critical
value.14–21 In particular, the pre-sheath transition region is
a)
avnish.pandey@ipr.res.in
b)
skarkari@ipr.res.in
the positive ions towards the material surface. In contrast to
voluminous theoretical study regarding the behavior of
sheaths in electronegative plasmas, a relatively fewer experi-
mental studies have been performed to validate them.
The most basic case to understand the behavior of
sheaths is the floating potential of the electrode immersed
in plasma. It is the potential at which the thermal fluxes of
electrons are balanced by the positive ions at the surface.
Due to the energetic electrons impinging the wall surface, it
acquires a negative potential with respect to plasma on the
order of few kB Te , where kB is the Boltzmann constant. The
floating potential is a function of electron temperature Te as
well as it depends on both effective charge and mass of posi-
tive ions. In electronegative discharges, the floating potential
is a function of negative ion parameters namely, a ¼ n =ne
and c ¼ Te =T . These parameters also determine the proper-
ties of electronegative discharges.
To determine negative ion parameters, the techniques
that are commonly used are the Langmuir probe/ hairpin
probe assisted pulse photo-detachment technique.23 However,
there are underlying complexities, which are associated with
these techniques. For instance, the estimation of a and c by
means of Langmuir probe assisted photo-detachment is
dependent on the laser wavelength as demonstrated in the
recent papers.24,25 Amemiya26 estimated the negative ion tem-
perature in the pressure range from few Pascal to 100 Pa in
an Ar/I2 mixture using the Druyvesteyn’s second derivative
method and electron to ion saturation current ratio obtained
from the Langmuir probe. However, Druyvesteyn’s method is
less reliable when the Ampere-Volts or I(U) characteristic of
the probe is masked by broadened electron characteristics.
Hence, this method can be only applied if the temperature of
electrons and negative ions is comparable. Recently, some
innovative means to probe negative ion parameters had been
reported by means of pulse biasing a hairpin probe27 in oxy-
gen plasma over a limited parameter space.

1070-664X/2017/24(1)/013507/9/$30.00 24, 013507-1 Published by AIP Publishing.

013507-2 A. K. Pandey and S. K. Karkari Phys. Plasmas 24, 013507 (2017)

 
The behavior of floating potential in plasma can also 1 eAw ð xÞ
Ue ð xÞ ¼ ene ðxÞveth e
¼ enes vth exp ; (1)
provide valuable information about the negative ion parame- 4 KB Te
ters. Fernandez Palop et al.28 studied the variation in floating  
potential in iodine plasma by varying the concentration of  1  eAw ð xÞ
U ðxÞ ¼ en ðxÞvth ¼ ens vth exp ; (2)
iodine I2 in an Ar/I2 discharge. Sherifian and Shokri29 have 4 KB T
reported the variation in floating potential for a large range Uþs ¼ nþs uBm : (3)
of electronegativity and an analogous work has also been
reported on the estimation for floating potential.30 From the In the above equations, the subscript, s, denotes the density
diagnostic perspective to measure electric field/potential of the individual species at the sheath edge, where the super-
inside plasma, the floating potential of the cold probe is rela- scripts have their usual meanings. Here, veth & v th are the
tively robust than that of the hot emissive probes since most mean velocities of electrons and negative ions
electronegative gases are highly corrosive. However, this  1  1
comes with a limitation that in most laboratory/industrial 8KB Te 2  8KB T 2
veth ¼ & vth ¼ : (4)
plasmas, foreseeable presence of non-thermal electrons can pme pm
drastically shift the floating potential to greater negative val-
ues, than that predicted based on single Maxwellian On the other hand, the modified Bohm speed uBm for the pos-
electrons. itive ions1 is expressed as
In the light of the above facts, the floating potential " #12
when considered carefully can be potentially useful for KB Te ð1 þ aÞ
validating analytical models concerning sheaths in low pres- uBm ¼ : (5)
mþ ð1 þ caÞ
sure electronegative discharges. Besides, it is also the aim
to establish the effectiveness of floating potential measure- For calculating floating potential, we apply the quasi-
ments to infer parameters such as a and c in electronegative neutrality condition at the sheath edge and the flux conserva-
plasmas. The basic motivation is therefore focused to under- tion can be expressed as
stand the behavior of floating potential in electronegative
discharges. In this paper, the floating potential of a cylindri- Uþs ¼ Ues þ Us ; (6)
cal probe immersed in electronegative oxygen discharge has
nþs ¼ nes ð1 þ aÞ: (7)
been investigated. In conjunction, parametric studies have
been performed to study the influence of electronegative The above equation can be solved to obtain an expression of
parameters a and c on the floating potential. The analytical the form
curves are compared with the experimental results to esti-
mate the range of negative ion temperatures in the discharge. P ¼ evw þ Qecvw : (8)
In Section II, analytical behavior of floating potential
in the presence of negative ions has been presented. The In the above expression, P, Q, & vw are given by P ¼
description about the experimental set-up is provided in 3 1 1
ðl2pðð1þa Þ 2 2
a 2 eAw
Section III. The experimental results including the phenome- þ 1þacÞÞ ; Q ¼ ðcl Þ ; vw ¼  KB Te and the constants have


nological model to determine a using the Langmuir probe been defined as follows:
have been presented in Section IV, followed by comprehen-
ns Te mþ m
sive discussion in Section V. Finally, Section VI ends with a a¼ ;c¼ ; lþ ¼ & l ¼ : (9)
nes T me me
brief summary and conclusion.
For oxygen plasma, Oþ 
2 and O have been considered to be
II. FLOATING POTENTIAL IN THE PRESENCE the most dominant ionic species.33 Therefore, lþ and l can
OF NEGATIVE IONS
be calculated by considering mþ ¼ 32 amu and m ¼ 16 amu,
Consider an electrode immersed in plasma consisting of respectively. Equation (8) can be solved to obtain the absolute
electrons, positive ions, and negative ions. The electrode is value of floating potential, vw normalized to Te. The plot of vw
spontaneously charged to a negative potential by influx of as a function of a, for c ¼ 1, 10, and 100 has been shown in
thermal electrons. In the immediate vicinity of the electrode, Fig. 1. The figure shows that above a threshold value ac , the
the negative potential is shielded by a sheath of positive absolute wall potential vw tends to fall monotonically on
ions. The region outside the sheath is quasi-neutral with a increasing a. Below this range a < ac , the vw is observed to
weak electric field in the pre-sheath pointing from the bulk increase in the case of c ¼ 10 and 100.
towards the sheath edge. These positive ions prior to entering In Fig. 2, the maxima value of vw corresponding to ac
the sheath are accelerated in the electric field to reach the has been plotted for a range of c. It is found that vwc
characteristic Bohm speed uBm . In quasi-neutral equilibrium, increases monotonically as c values are increased from 1–70,
both electrons and negative ions are assumed Boltzmann whereas, ac tends to saturate at larger values of c. The overall
throughout the pre-sheath as well as inside the sheath.31,32 trend in vc and ac can be explained as follows:
Following Liebermann and Lichtenberg,1 the individual When a < ac (i.e., a is below 50%), the electron flux to
fluxes of electrons, negative ions, and positive ions at the the probe dominates over the negative ion flux by a factor
pffiffiffi
wall/probe surface can be written as follows: 170
a c. Therefore, the negative ion flux plays a weaker role
013507-3 A. K. Pandey and S. K. Karkari
FIG. 1. Plot of the absolute value of normalized floating potential vw as a
function of alpha, for c ¼ 1; 10; 100:
in determining the floating potential in the case of low
electro-negativity (a < ac ). However as shown in Fig. 3, one
can observe a sharp fall in the characteristic Bohm speed of
positive ions on increasing the value of a. When the value of
a  1, the Bohm speed uBM becomes almost independent of
a (Fig. 3).
In Fig. 1, the magnitude of vw tends to increase slightly
in the regime a < ac , whereas in Fig. 2, the value of vwc cor-
responding ac has been shown to increase with a. This
FIG. 2. Plot of ac and vwc as a function of c.
Phys. Plasmas 24, 013507 (2017)
 
M u2
FIG. 3. Variation of normalized Bohm velocity e ¼ 12 KþB TBm
e
with electro-
negativity a.
behavior can be explained as follows. Given a constant
ion density at the sheath edge, an increasing value of a will
reduce the effective ion flux due to the sharp fall in uBM
(Fig. 3). Therefore, the potential on the probe must develop a
higher repelling potential for the electrons in order to make
the electron flux commensurate with the positive ion flux at
the probe surface.
In contrast to the above, when a is significantly higher
than ac , then contribution of negative ions begins to domi-
nate over the electron flux arriving at the probe surface.
At very high electro-negativity, the value of floating poten-
tial approaches a small but finite value, which corresponds
to the mass and temperature ratios of the two oppositely
charged ionic species, as found in the case of pair-ion
plasma.34 Here, it is important to discuss the two limiting
cases; (a) a ! 0 and (b)a ! 1. For a ! 0, it is evident
from
p Equation (8) that the floating potential vw ! ln
ffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi 36
mþ =2pme reduces to pure electropositive plasma. Onffi
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
the other hand for a ! 1. vw ! ð1=cÞ ln mþ =2pm .
Even for mþ  m (ion-ion plasma), the floating potential
vw 6¼ 0. This discrepancy is due to the simplified assump-
tion that ions are cold. In fact for large a, when e/w <
KB Tþ (Tþ is positive ion temperature), i.e., the ion thermal
energy becomes comparable to the floating potential
energy, the ion motion is no longer described by the drift
equation.
As evidenced in Fig. 2, the dependence of floating
potential corresponding to ac on c is consistent with the fact
that the floating potential in the low electro-negativity
regime is primarily decided by the electrons rather than neg-
ative ions, whereas, the value of ac tends to saturate at higher
values of c. This is due to enhancement in the contribution of
013507-4 A. K. Pandey and S. K. Karkari
FIG. 4. Experimental setup for measurement of floating potential using con-
stricted anode A and two-disc cathode C.
negative ion flux to the wall potential as compared to net
electron flux arriving at the probe surface.
III. EXPERIMENTAL SET-UP AND DIAGNOSTIC
To study the behavior of floating potential, oxygen dis-
charge has been considered. The discharge is created in a
cylindrical vacuum chamber shown in Fig. 4. The experi-
mental chamber is equipped with a Pfeiffer make HiPace-
700 TMP and a Pfeiffer make hot cathode Pirani/Penning
gauge (Model-No D-35614 Asslar). The plasma has been
produced between two concentric annular disc plates
(ID ¼ 4 cm and OD ¼ 14.2 cm) made from ss 304 acting as a
cathode and a constricted anode. The plates are separated by
a gap of 25.5 cm. The anode consists of stainless steel tube
having 8.0 mm, which has been encased inside a ceramic
tube, leaving only the tip exposed to plasma (c.f. Fig. 4). The
working gas argon and oxygen are introduced through this
tube. The overall discharge assembly is similar in configura-
tion to Ref. 35, except that the array of semi-circular cathode
plates has been replaced with two floating annular plates.
When high dc potential (0.8–1.0 kV) is applied between
the discharge electrodes, a stable plasma can be seen to be
occupying the entire volume between the cathode plates. The
range of working gas pressure is typically in the range of,
P > 1.0 Pa. In this configuration, the discharge at low pres-
sures is primarily sustained due to efficient trapping of sec-
ondary electrons between the opposing cathode plates. To
enhance the discharge, a small magnetic field, B < 3:0 mT,
has been applied by means of external electro-magnetic coils
as shown in Fig. 4. The coils are placed around the cylindri-
cal vessel.
Phys. Plasmas 24, 013507 (2017)
All the measurements have been carried out in the cen-
tral region using a cylindrical Langmuir probe. The probe is
made from a tungsten tip of length ¼ 11.0 mm and 0.2 mm in
diameter and it was positioned in the center of the discharge
plasma. The plasma parameters have been obtained by ana-
lyzing the IðUÞ characteristics under different discharge/
operating conditions.
IV. EXPERIMENTAL RESULTS AND ANALYSIS
A. Langmuir probe characteristics
A typical plot of IðUÞ characteristic of the Langmuir
probe in oxygen plasma has been shown in Fig. 5(a). The
region below the floating potential has been enlarged in the
same graph to clearly visualize the positive ion saturation
region. The ion saturation current has been determined by
extrapolating the straight line up to the plasma potential
U ¼ Vp . The value of Vp has been determined by the double
tangent intersection method on the plot of lnðIe Þ vs U curve
as shown in Fig. 5(b).
The electron temperature Te has been determined by fit-
ting straight lines to the linear portions of the semi-log plot
of the Ie ðUÞ curve. As seen in the figure, the plot of ln½Ie ðUÞ
has two distinct slopes. This characteristic suggests that the
discharge plasma comprises bi-Maxwellian electrons. The
two slopes correspond to electron populations having tem-
peratures Teb  0:6 eV and Teh  5:2 eV corresponding to
bulk and hot electrons, respectively.
Considering the bulk electron temperature Teb  0:6 eV
and floating potential, Vf  1:14 V, therefore the expected
value of the plasma potential can be estimated as Vp ¼ Vf
þ 4:7 Teb  3:8 V. Here, we have considered O2þ (mass
32 amu) as the most dominant positive ions species in oxy-
gen. It can be seen in Fig. 5(b) that Vp obtained by the double
intersection method (Vp ¼ 3.3 V) is consistent with the one
estimated from the bulk electron temperature. The hot elec-
trons constitute merely 4% of the total population and there-
fore it does not significantly alter the floating potential. This
fact is also evident as the temperature slope corresponding to
the hot electrons is found to be appearing below the floating
potential. In the overall characteristics, the hot electrons are
apparently masked by the dominant contribution of positive
ion flux to the probe.
Fig. 6 shows the plot of respective electron temperatures
for a range of operating power. The hot electrons are gener-
ally present in confined dc discharges operated at high
FIG. 5. Typical plots of (a) IðUÞ char-
acteristics with ion saturation current
Iþs ¼ 43:4 lA (b) Semi-log graph of
electron current with Vf ¼ 1:14 V, Vp
¼ 3:3 V and two slopes corresponding
to electron temperature, Teb ¼ 0:6 eV
& Teh ¼ 5:2 eV in oxygen plasma for
operating power P ¼ 100 W at 4.0 Pa
pressure.
013507-5 A. K. Pandey and S. K. Karkari
FIG. 6. (Plot of bi-Maxwellian electron temperature (in eV) with power for
4 Pa pressure using Oxygen gas).
voltages. The dc discharges are primarily sustained by ion
impact secondary electrons, which emerge with energies
corresponding to cathode fall potential. These electrons are
eventually thermalized by making ionizing collisions with
the background neutrals and constitute the bulk electron pop-
ulation in the discharge. A small fraction of energetic elec-
trons are randomized by suffering multiple reflections from
the walls and remain at higher temperatures than the back-
ground bulk population. Finally, the electrons which did not
suffer collisions with the target atoms are likely to contribute
as energetic beams impinging the probe/substrate.
In the present set-up, the characteristic geometry of the
source is such that the secondary electrons emitted from the
cathode plates are mainly constrained within the annular
region (Fig. 4). However, there exists a finite probability that
a fraction of these electrons can reach the central region after
suffering collisions at the edge. Since the majority popula-
tion of electrons in the bulk are at a low temperature, there-
fore the electron impact detachment, which is considered
to be dominant loss mechanism than ion-ion recombination
losses, can be considered to be small/or negligible [see
Section V]. Therefore, the probability of negative ion forma-
tion in the central region is relatively higher than the active
region between the cathode plates.
B. Saturation current ratios
In the I (U) characteristics in Fig. 5, the saturation
region defines the maximum positive/negative fluxes
absorbed by the probe surface. In electropositive plasma
like argon, the negative flux to the probe is entirely consti-
tuted by electrons. The ratio between the electrons to posi-
tive ion flux is therefore reduced to a constant factor R,
which is solely determined by their respective mass ratio
hence independent of external discharge parameters.
However in the case of electro-negative plasma, this rela-
tive ratio will change due to contribution of negative ions.
This fact has been illustrated in the plot of R versus dis-
charge power in Fig. 7. The value of R remains almost con-
stant in the case of argon, whereas it tends to increase in the
case for oxygen.
Phys. Plasmas 24, 013507 (2017)
FIG. 7. Plot of electron to ion saturation current ratios in (a) oxygen and
(b) argon; Pressure ¼ 4.0 Pa.
C. Expression of floating potential
The floating potential is straightforward to obtain in
electropositive plasma by equating the electron and positive
ion flux, which reduce to a simple expression as given in
Ref. 36
0 sffiffiffiffiffiffiffiffiffiffiffi1
 
Ies 2me pA
Vf ¼ Vp  Te ln ¼ Vp  Te ln@0:6 : (10)
Iþs mþ
In the above equation, Ies and Iþs are the saturation currents
corresponding to electron and positive ions. The above equa-
tion holds for moderately electronegative plasmas as well,
since the negative ion contribution can be largely ignored as
compared to the electrons at the floating potential. However,
contribution of non-thermal electrons (secondary electrons,
beams) as well as hot electrons can modify the floating
potential depending on their respective magnitudes.
The probe characteristic in Fig. 5 shows a bi-Maxwellian
nature. From the analysis of I(U), the hot component of
electrons (Teh  5 eVÞ is found to be almost one order in
magnitude higher than the bulk electrons (Teb  0:6 eVÞ [c.f.
Fig. 5]. The hot electrons in the discharge mainly contribute
to vibrational excitation of oxygen molecules, whereas low
temperature electrons constitute the major bulk population of
electrons [Ref. 1-Chap. 10].
Consider the case of electronegative plasma comprising
T
of different negative species. The net saturation current Ies
T b h h
at Vp can be expressed as, Ies ¼ Ies þ Ies þ Is , where, Ies ,
b
Ies , and Is are the saturation currents for hot electrons, bulk
electrons, and the negative ions, respectively. To find
T
whether the contribution of hot electrons in Ies is significant,
we can express
 
h Vp  Vf
Ies ¼ Iþs exp : (11)
Teh
In the above equation, the contributions due to bulk electrons
and negative ions have been neglected at the floating potential.
Therefore, (11) gives an upper estimate of hot electron contri-
bution to the probe. With this approximation, the resultant
013507-6 A. K. Pandey and S. K. Karkari Phys. Plasmas 24, 013507 (2017)

h
value of Ies has been estimated in the range of 103 mA. This  Total h h
 32
Ies Ies Ies Teb
is approximately three orders in magnitude smaller than the R p ; A b
; B  b
;
T
Iþs Ies Ies Teh
total saturation current Ies  1 mA. Therefore, we have approx- qffiffiffiffiffiffi
imated the floating potential Vf  Vfb to be largely determined h
 12 2lþ
Ies Teb p
by the bulk electrons C b
; a : (15)
Ies Teh 1:2
!
b
b Ies In the above equation, all the terms have their usual mean-
Vf ¼ Vp  Teb ln : (12)
Iþs ings. The factor p has been introduced as a correction term in
the electron to ion saturation current ratio as discussed in
In the case of moderately electronegative plasma, it is rea- Section IV C. The cubic Equation (14) gives three roots of a,
sonable to use the electron saturation flux in (12), to obtain in which only the real and positive value has been consid-
Vfb . However, as reported by various authors, the electron ered. Since the contribution of the hot electrons is small,
h
saturation current is generally underestimated due to differ- Ies  0, therefore the above equation simplifies to
ent external factors,41 such as the return current area of the " # " pffiffiffiffiffiffiffi#
2 2 2
probe, presence of energetic electrons in the discharge, and a a T  2a Teb
R2  a3 þ 3R2   pffiffiffiffiffiffiffiffiffiffiffi a2
the external magnetic field. These factors can reduce the net l Teb l T l
electron saturation flux to the probe surface; thus it will " pffiffiffiffiffiffi#
impact the electron to positive ion saturation ratios. In order a2 Teb 2a2 T
þ 3R  2
 pffiffiffiffiffiffiffiffiffiffiffiffi a þ ½R2  a2  ¼ 0: (16)
to avoid relying on the exact saturation current ratio to deter- T Teb l
mine the negative ion density, it is recommended to compare
the electron to ion saturation ratio with a known electroposi- In obtaining (14), we considered the modified Bohm speed,
tive gas, i.e., argon. This procedure has been adopted by var- which comprises bulk electrons, hot electrons, and the nega-
ious authors.41,42 In the experiment, the ratio R for argon, tive ions based on Boyd and Thompson18
which is expected to be 180 has been found to be underesti- ð
eTe 1 1 d
mated by a factor 4.7 [c.f. Fig. 7]. Hence, this factor can be nþs f ðvÞdv  Te nb ðxÞ þ nhe ðxÞ þ n ð xÞ At A¼0 :
m þ 0 v2 dA e
used for rectifying the underestimated value of electron satu-
ration current in oxygen. (17)

Here, AðxÞ is potential inside the sheath. Applying the usual

D. Phenomenological model to determine flux and energy conservation, the ion density at any point
electronegativity in the presence of multiple charge inside the sheath can be obtained. The electron density and
species the negative ion density have been assumed to follow the
The electronegativity parameter a is defined as the ratio Boltzmann equation. The modified Bohm speed due to con-
of negative ion density n to the bulk electron density, nbes . In tribution of all species can be obtained as
order to estimate the absolute value of nbes , the total negative sffiffiffiffiffiffiffiffiffiffiffisffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
T
to positive current saturation ratio Ies =Iþs is determined at Vp. kB Teb 1 þ a þ nhes =nbes
Considering multiple charge species including bulk electrons, uB : (18)
mþ 1 þ ac þ nhes Teb =nbes Teh
hot electrons, negative ions, and positive ions, the ratio of
negative to positive saturation currents can be expressed as Equation (16) can be numerically solved to determine the
  ! electronegative parameter a with the constants provided
b h
In Ies þ Ies þ Is from the experiment. The correction factor p ¼ 4.7 has been
R¼ ¼ : (13)
Iþs Iþs incorporated in R.
Fig. 8 shows the plot of a and the corresponding values
In the above equation, all the terms have usual meanings. of floating potentials vw , which has been normalized to
Using (1)–(3), the above Equation (13) may be expressed in bulk temperature Teb . In the experiment, the electronegative
the form of cubic equation in a as written below parameters a have been varied by changing the discharge
" # " power and/or the pressure. While utmost care has been taken
2 a2 3 a2 T ð1 þ BÞ to control the external power/pressure during the experiment,
R  a þ 3R2 ð1 þ CÞ 
l Teb l however minor variation within less than 5% in discharge
p ffiffiffiffiffiffi
ffi   voltage/current can lead to a corresponding change in the
2a2 ð1 þ AÞ Teb 2 2
 pffiffiffiffiffiffiffiffiffiffiffi a þ 3R2 ð1 þ CÞ values of a (obtained from Eq. (16)) and vw . However, it has
T l
been found that the variation in a and vw is strongly corre-
2 pffiffiffiffiffiffi#
a2 Teb ð1 þ AÞ 2a2 ð1 þ AÞð1 þ BÞ T lated. Therefore, in Fig. 9, we have displayed all the possible
  pffiffiffiffiffiffiffiffiffiffiffiffi a values of a and vw obtained at different powers (within 5%
T Teb l
h i variation). However in Fig. 8, only a limited set of a and vw
3 2
þ R2 ð1 þ CÞ  a2 ð1 þ AÞ ð1 þ BÞ ¼ 0: (14) has been plotted to show only the experimental trend of these
quantities as a function of power and pressures. The behavior
Here the constants have been defined as follows: of a and vw shows a contrasting trend with the applied
013507-7 A. K. Pandey and S. K. Karkari
FIG. 8. plot of a and normalized value of floating potential vw ¼ Vf =Teb as
a function of discharge power for 4, 5, 6, & 7 Pa.
discharge power. This suggests that the experimental range
lies above the critical value ac (c.f. Fig. 1).
E. Comparison of the experiments with the theoretical
model
The normalized value of the floating potential vw as a
function of a has been shown in Fig. 9. The floating potential
vw obtained from the theoretical model is dependent on T
(or c). On the other hand, the experimental value of vw has
been measured directly. However to derive a, the informa-
tion about T or c is required [c.f. (14)]. Therefore in Fig. 9,
a series of theoretical curves corresponding to different val-
ues of c are plotted, whereas the experimental data are shown
Phys. Plasmas 24, 013507 (2017)
by scattered data points. The theoretical curve, which coin-
cides accurately with the experimental data corresponds to c
(¼Teb =T Þ10–11, which is consistent with the experiment
and theoretical model used to obtain vw . Since Teb is directly
found from the experiment, therefore it is possible to esti-
mate T for which the experimental values give a best fit
with the theoretical curve. Based on this method, the electro-
negative parameter a has been determined corresponding to
T  0.05 eV to 0.07 eV, whereas Teb  0.5–0.6 eV in the
bulk plasma as obtained by the Langmuir probe. This is
shown in Fig. 9 for different operating pressures.
V. DISCUSSION
The experimental results/analysis presented in Section IV
highlights the significance of negative ions on the floating
potential of a probe in electronegative plasma. The important
aspect has been centered on the effectiveness of using this
simplistic method to determine the basic parameters viz, a
and c with the help of the Langmuir probe. The estimation of
a can be influenced by several unknown factors such as effec-
tiveness of the electron to ion saturation ratio and the uncer-
tainty in determining negative ion temperature. It is also well
known that the floating potential is susceptible to the presence
of energetic electrons in the discharge.
In the present experiment, the hot electrons have been
observed in the probe characteristics; however their popula-
tion is extremely small to cause a significant variation in the
floating potential. The negative ion parameter a in the exper-
iment has been determined from the I(U) characteristics
using a phenomenological model. In this model, the electron
to positive ion saturation ratio is provided as an input param-
eter to calculate the cubic equation in a [c.f. (14)]. To solve
FIG. 9. Plot of floating potential nor-
malized with respect to Teb has been
plotted as a function of electronegativ-
ity a for different pressures; (a) 4.0 Pa,
(b) 5.0 Pa, (c) 6.0 Pa, and (d) 7.0 Pa.
The value of negative ion temperatures
is (a) T  0:05 eV for 4.0 Pa (b),
T  0:06 eV for 5.0 Pa (c), T 
0:07 eV for 6.0, and (d) T  0:06 eV
for 7.0 Pa, while the correction factor
p ¼ 4.7. Also plotted are the theoretical
curves corresponding to different c val-
ues, namely, c ¼ 1, 5, 10, and 15,
respectively.
013507-8 A. K. Pandey and S. K. Karkari Phys. Plasmas 24, 013507 (2017)

this equation, additional information about negative ion tem-
perature T is required. Here, T is an unknown parameter,
which is related to the electronegative parameter c ¼ Te =T .
However, an optimal value of T was obtained in Fig. 9 by
comparing the vw versus a plot with the theoretical curve.
The obtained negative ion temperatures and the range of a
are found to be in reasonable agreement with those reported
by other authors.40,41 Therefore, the procedure not only
allows one to estimate the negative ion temperature range,
but it is also useful as a tool to verify the analytical models,
provided the external plasma parameters are known.
Using the above method, the variation in a as a func-
tion of discharge power has been presented in Fig. 8. The
observed fall in a on increasing the discharge power is
consistent with the earlier results.33,37,38 The negative ions
are created /lost by a series of reactions. Table I based on
Ref. 40, provides the dominant reaction mechanism,
responsible for the production / loss of negative ions. The
process also includes the production of excited neutrals,
which participate in the generation and loss of negative
ions. The production of oxygen negative ions is mainly
attributed to dissociative attachment of the ground state
and excited neutrals in the discharge (rate constants K1 to
K4 ), whereas these ions are lost via: (1) electron impact
detachment having rate constant K5 , (2) recombination of
negative with positive ions having rate constants K6 and
K8 , and (3) excited neutral impact detachment having rate
constant K7 .
The observed decrease in negative ion density in Figure
8 on increasing the discharge power can be attributed to elec-
tron impact detachment as the electron density increases
with the discharge power. Another important factor responsi-
ble for the loss of negative ions is caused by ion-ion
recombination. This reaction mechanism is higher than the
detachment loss observed at low pressures.
In our experimental system, the plasma volume V ¼ 1:60
104 cm3 and the loss area A ¼ 5:80 102 cm2 . The range
of a obtained in our case is found to be consistent with
those reported by previous authors.37–40 In Reference 1 viz.,
a > K ng =K6 where K ¼ 4K5 K7 V=c v A; where ng is neu-
trals gas density, V is discharge volume, c is loss probability
for excited species on the wall, v is average velocity of
excited neutrals, and A is the loss surface. Therefore, the RHS
of inequality in our case is approximately 0:07. This indi-
cates that our operating range lies in the low pressure regime
(or high a), where the recombination loss dominates over the
detachment loss of negative ions.
An important feature observed in Fig. 1 is the increasing
magnitude of vw versus a in the weakly electronegative
regime (a < ac ). This increase has been attributed to reduc-
tion in the Bohm flux of positive ions entering the sheath
edge (c.f. Fig. 3). In order to balance the net electron flux
with the positive ions, a higher repelling/negative potential is
necessary at the probe surface. Hence, the magnitude of
floating potential will increase on introducing a small con-
centration of negative ions. In contrast to this, at higher elec-
tronegativity (a > ac ), the floating potential vw is found to
reduce monotonically as the negative flux to the probe sur-
face is mainly contributed by negative ions than electrons.
Therefore, ion flux/ion bombarding energy at the substrate
can be controlled by introduction of negative ions.
VI. SUMMARY AND CONCLUSION
In this paper, a parametric study of floating potential has
been performed as a function of electro-negativity parameter
a, while the results have been compared with the experiment

TABLE I. Dominant reaction mechanism for production and loss of negative ions as well as the production of excited neutrals, which participate in the genera-
tion and loss of negative ions.

S. No. Reaction Rate constant Values for Te  0:5 eV & Tg  300 K

n production mechanism
1. e þ O2 ! Oð3 PÞ þ O K1 ¼ 8:8 1017 expð4:4=Te Þ 1:32 1020
2. O þ O2 ! O2 þ O K2 ¼ 2:0 1016 ð300=Tg Þ0:5 2:2 1016
3. e þ O2 ða1 Dg Þ ! Oð3 PÞ þ O K3 ¼ 4:19 1015 Te 1:376 exp ð5:19=Te Þ0:5 6:05 1017
4. e þ O2 ! Oþ þ O þ e K4 ¼ 7:10 1017 Te 0:5 exp ð1:7=Te Þ0:5 9:17 1018
n loss mechanism
5. e þ O ! e þ Oð3 PÞ þ e K5 ¼ 5:47 1014 Te 0:324 exp ð2:98=Te Þ 1:12 1016
6. þ
O2 þ O ! e þ Oð3 PÞ þ O2 K6 ¼ 2:6 1014 ð300 K=Tg Þ0:44 2:07 1014
7. O þ Oð3 PÞ ! e þ O2 K7 ¼ 1:6 1016 ð300 K=Tg Þ0:5 1:27 1016
8. Oþ þ O ! 2Oð3 PÞ K8 ¼ 4:0 1014 ð300 K=Tg Þ0:43 4:0 1014
n* production mechanism
9. e þ O2 ! e þ O2 ðv ¼ 1Þ K9 ¼ 2:80 1015 expð3:72=Te Þ 1:64 1018
10. e þ O2 ! e þ O2 ðv ¼ 2Þ K10 ¼ 1:28 1015 expð3:67=Te Þ 8:30 1019
11. e þ O2 ! e þ O2 ðv ¼ 3Þ K11 ¼ 5:00 1016 expð3:6=Te Þ 3:73 1019
12. e þ O2 ! e þ O2 ðv ¼ 4Þ K12 ¼ 2:00 1016 expð3:5=Te Þ 1:82 1019
13. e þ O2 ! e þ O2 ða1 Dg Þ K13 ¼ 1:37 1015 expð2:14=Te Þ 1:89 1017
14. e þ O2 ! Oð3 PÞ þ O K14 ¼ 8:80 1017 expð4:4=Te Þ 1:32 1020
15. e þ O2 ! Oð3 PÞ þ Oð3 PÞ K15 ¼ 6:86 1015 expð6:29=Te Þ 2:35 1020
16. e þ O2 ! Oð3 PÞ þ Oð1 DÞ K16 ¼ 1:80 1013 expð18:33=Te Þ 2:15 1029
17. e þ O2 ! Oð1 DÞ þ Oð1 DÞ K17 ¼ 1:44 1016 expð17:25=Te Þ 1:49 1031
18. e þ O2 ! 2e þ Oþ þ Oð3 PÞ K18 ¼ 1:88 1016 Te1:699 expð16:81=Te Þ 1:45 1031
013507-9 A. K. Pandey and S. K. Karkari Phys. Plasmas 24, 013507 (2017)

conducted in weakly magnetized oxygen plasma. The overall
behavior of the floating potential has been characterized into
two regimes with regard to a critical value ac . In the lower
range when a < ac , the theoretical values show an increasing
trend with a. This observation has been attributed to reduc-
tion in the positive ion flux to the probe surface owing to a
fall in the Bohm speed entering the sheath edge. When the
value of a is sufficiently large, the flux balance between the
positive and negative charge species arriving at the wall sur-
face is predominantly determined by negative ions than elec-
trons. In this case, the magnitude of potential tends to fall
monotonically as a was increased.
The theoretical predictions have been experimentally
validated in the regime, a > ac over a limited range of a. A
phenomenological model has been provided to interpret the
value of a and the corresponding values of floating potential.
The result shows excellent agreement with the theoretical
curves. Based on this model, the value of T has been found
to be in range of 0.05 eV to 0.07 eV. In principle, if the
correction factor is benchmarked against another diagnostics,
for example, pulse laser photo-detachment,40 then the above
method can be highly robust for determining the negative
ion temperature accurately. This shall be considered in our
future study.
ACKNOWLEDGMENTS
The author thanks Dr. M. Bandyopadhyay and Dr. S K
Mishra for their valuable suggestions regarding the
manuscript and Mr. Dhrumil Patel for his technical support.
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