International Union of Pure and Applied Chemistry

11th INTERNATIONAL SYMPOSIUM

ON PLASMA CHEMISTRY

LOUGHBOROUGH UNIVERSITY

LOUGHBOROUGH. LEICESTERSHIRE. ENGLAND.

AUGUST 22 - 27 1993

SYMPOSIUM PROCEEDINGS

VOLUME 4

Edited by J E Harry

t.. _. _ .
 THE PHENOMENA OF DIRECT ELECTRIC FIELD EFFECTS

IN PLASMA-SURFACE INTERACTIONS
Georgy K. Vinogradov
Department of Electrical Engineering and Electronics,
Nagoya University, Nagoya 464-01, Japan

MlST.RACT
Direct lnrluence of electric fields in a surface layer of dielectric
films contacting with plasma on heterogeneous processes of plasma­
surface interaction was experimentally revealed. The phenomena
described here are to be basic and might be of essential interest for
studying of plasma-surface interactions and for fine surface plasma
chemi cal processi ng as well.

INTRODUCTION
Practically all plasma processes utilizing low temperature low pressure non­
equilibrium plasma are dealing with plasma-surface interactions. Namely on these inter­
actions main electronic technolcg~e~ of dry p.tching are ~~sed, a~ well as amorphous
silicon growth, [liamond filws synthesi£, plusma-CV~. plasma polymerization etc. These
systems represent rather black boxes fror~ the mecnanistic point of view. A self­
consistency of mul ti c;);~plJnp.nt 1'1 asma chemical objects Sef!mS to be one of the main
obstacle for experimental studies.
One of the [rui tfu1 ways to disrupt the self-consistency '>f plasma chemical
objects may cons~st ot the disruption of only pia ma-(plasilla sheath) self-consistency
without any variation of a bulk plasma itself. Only operations with small enough sub­
strates give this chance. The idea was utilized in a series of works based on specially
developed methods of electric kinetic probes [1-3]. The methods have been developed to
study direct effects of particle fluxes and electric fields on surface processes.
If a substrate is really small, for example, a Langmuir probe or even larger,
variations of a probe current, temperature, surface properties and electric potential
don't change essentially surrounding plasma and hence fluxes of neutral particles on the
probe. Consequently, in this case all variations of surface processes may be assigned
directly and definitely to the variations of fluxes of electrically charged particles
and electric fields.
Until now the electric field in plasma-surface layer was known to be
responsible only for energy pumping in a plasma volume, for formation of corresponding
sheath energy distribution functions of charged particles bombarding the surface, and
various kinds of surface damages. This field itself was not considered as an influential
parameter of growth or etching kinetics.
Certainly, the outer electric f~eld strength near the surface contacting with
plasma is not so high: of the order of 10 _lO J V/cm. In principle, it can generate field
effects under some limited conditions. However fluxes of energetic particles onto the
surface usually obscure field effects.
. Here we are trying to show that that there exist not only space or plasma
sheath electric field, but another electric field inside a surface layer of solid body
and it does produce very strong influence on surface processes and must be considered
. as a new representable internal parameter of plasma-surface interactions. Qualitative
concept of the phenomena is proposed as well.

EXPERIMENTAL
Deposition of thin fluorocarbon films was studied on the surface of electric
probes contacting with a uniform bulk plasma or plasma-wall sheath. RF discharge (40.68
MHz) was initiated in a plug flow (ideal replacement) capacitively coupled "box-type"

1559

tr
rp.actor (2). It was shaped as a rectangular channel between two copper temperature sta­

bilized electrodes inser~ed in an electrically shielded teflon case and placed under a

fused si.lica bell jar. A distributor with nlL1ll?rous small orifices produced a uniform gas

flux. An opposite output end of the reactor was opened to the bell jar and crossed with

CI copper mesh to limit the plasma volume. So the RF plasma was entirely defined from all

six sides of the reactor and was not changed with variations of discharge ~rameters to

keep specific parameten; well ueternlined. The plasma volume was 2x6x12 cm).

Heated thin probes made from tungsten (5 microns in radius) or platinum (10

microns) were used for probe ioeasurements. These probes have being used as Langmuir pro­

bes, as hot wires (for measurements of the probe temperature and heat fluxes), as an em­

issive probe to analyze the validity of a probe circuitry and, at last, as kinetic probe

capable for a voltage drop control across growing or being etched dielectric films.

."
I
Flat probe-substrates made from different materials were used as well. These
probe-substrates were placed in a plane of the lower grounded electrode. Small polished
Si wafers were used as substrates routinely. It allows us to measure several parameters
of the same film: voltage drop across the film by means of kinetic probe method,
thickness (optical micro interferometer), and a weight gain. The diameter of a working
area of the probe-substrates was usually 3 mm to avoid remarkable plasma perturbations.
The degree of perturbations was controlled with a movable Langmuir probe located in the
vicinity of the probe-substrate surface. Typical discharge conditions were as follows:
power 2-30 Wt, gas composition Ar+c-Cls (1-97%). total pressure 0.1-1 Torr, gas flow
rate 5-30 ccjmin (STP).
The main i.dea of these experimE'nts was based on a natural and well controllable

assumption, - that a 'Jery slnc3ll substrate produce negligi ble vnr.i.ations of plasma

parameters even nndHI variable electrically charged par::icle fluxes and surface

potential. Actually, the density of acti,e neutral particles is determined by a volume

plasma productivity, kinetic residence time and a plasma-surface material balance. The

small substrate can perturb only very small plasma area, so neutral particle fluxes can

not be affected too much (he~e we we ale not consid~ring a special case of

electronically excited free radicals which fluxes on the surface can be strongly

dependent on excitation processes in a sheath area). And hence, all variations in the

reaction kinetics of surface processes may be assigned directly to the influence of the

variations of charged particle fluxes and electric fields. These charged particles

fluxes can be easyly controlled and interpreted. And the kinetic probe techniques allows

one to separate additionally the effects of charged particles from the effects of

electric fields by means of their independent variations.

~SULTS AND DISCUSSION

Fig.l demonstrates typical
film growth rat.e5. nrn/min;
dependencies of' the film growth rate on
Volts/rnin
its surface electric potential in respect
•
v - 100
to the floating' potential which is ac­
d
cepted to be zero. The growth rate was

4O.68MB-z
measured as an average growth of thickness
15% c-C4F1hAr
for the prescribed time interval and con­
0,5 Torr;
tinuously as a vol tage drop across the
8.5
growing films during their formation

(kinetic probing). The kinetic curves were

] inear within a 5-10% accuracy. It appears

after the quanti tati ve treatment taking

-80 -40 0 40
into accounts I-V probe characteristics,
surface electric potentiaL Volts
that the film growth rate is usually dire­

ctly proportional to both charged partic­

Fig.l. Dependencies of film growth rate on
les fluxes with corresponding coefficients
surface electric potential: vd - growth of
of their efficiency in the surface activa­
thickness; vR- growt.'l of voltage drop.
t ion. And the growth mechanism can be

cescribed in the frame of ,an activation-chemisorption model of plasma polymerization

proposed preViously for hydrocarbons [4]. This model is considering activation processes

in the living surface area of a growing film caused by neutralizing positive ions and

electrons bringing about a rupture of chemical bond and further recombination of surface

1560

-------------------- srn
and gas pr.ase free radicals, leading to the formation of new chemical bonds.
A surprising and important feature in the recent case consist of a large
activation rate produczd by electrons. It was newer observed in plasma polymerization
so definitely for our best knowledge.
Also, an area near the floa­ .-----------------------------------------~
ting potential of the surface looks .c lEi, V/cm . .K)6 15-'-( Ff)+Al'
strange. The non-monotonous behavior 9F O.:"5T( r1"
of both curves can not be explained ... 12
by corresponding variations of charg­ E
ed particle fluxes. Actually, the po­
sitive ion flux, which cause intensi­
ti .. Irl.
• ,'I
e .0 Wt
16 Wt
ve surface activation is changing mon 8 - --,""~--",,.o.
_-"""-_-a-- ~\t
:rt .:..5 Wt
ctcnously illid ~ery insufficiently in •
I
this region. An electron flux is cha­
nging al so monotonousl y, and its act­ ~ _-,-_ _ _ _----l._ _--'-­-\f

0'--_ ~

ivation rate near the floating poten­ -120 -80 -40 0 -:1-0
tial may be neglected in compare with
ion activation. So, particle fluxes surface electric potential \blts
can not originate this featu-re. The
only one reason which do can produce Fig.2. Electric field strength in growing films
some addi tional effects can be the measured during their formation in RF discharge.
electric field in the surface layer
of the growing film. It changes both direction and magnitude crossing the point of Vf •
Variations of the elec:tri.: field st~ength ml;st be in somr:. proport ion to the current
density across ti1e fi 1m. In case of dielHctr ic organic fi l,ns thl';!::>!! variations must be
extremely strong ina very narrow range at currents. And the ;lse of hnetic probes gives
a unique possibili ty to measur'e tl1f: eiectric field strength inside tile growing or being
etched films during their interaction with pl~sma, i.e. in situ. Fig.2 shows a very high
electric field strength in tht! grc~~ing films. 'J,1riations of this fie~c1 near the floating
potential are inside a limit of few volts of the surface electric potential. It reflects
natural electric properties of dielectric films which possess non-ohmic I-V characteris­
tics in strong electric fields. The I-V characteristics of depositing films were
measured in a wide r~ge of current densities. They are represented by straight lines
in coordinates lnI-VI/ I [2].
For thin cylindrical probes the dependencies of the rate of film formation on
surface electric potential look quite different and unique (Fig.3). A sharp switching
phenomena of the deposition rate is observed in a very narrow range near the floating
potential. Practically it is switched to zero. Particle fluxes are not changing here
remarkably. The outside electric field also is not changing essentially. So, there are
no other reasons except of the switching of the electric field inside the film body, and
hence in the surface layer as well.
The switching effect for 4O.68MHz I
thin probes is well reproducible and
controllable. The shape of these cur­
E 4 . 15% c-CAF6+Ar

"''Iv
;S 80 • I Torr
ves depend on experimental conditions 25 lVt
preserving main features near the <C Ci
floating potential.
;;l. ~ 40
.~
The saturation effect of the ~ Vi

growth rate under the ion bombardment e... :ll 0

is to be easy explained by saturation :;l f -20 -10 /0 10, Volts
of the activation rate. The limitati­
Q
..cl
...
surface potential" V s - v f
on for the growth rate in this case ~... ...~-.I-O /

~
Pro!>¥.:
comes from neutral part icles, that Q,
too Pl
was specially studied along wi th a I' =lOp
gas phase chemical kinetics /8,9/. -60
1=15nuD
It was interesting to
disclose the reason for such a strong Flg.3. "Swltchlng"effect of the f;.lmgrowth rate
Suppression of the film growth rate on the surface of thin probe.
in the electron branch of the I-V
characteristic. There are two main distinc-tions in operation between the thin probe and

1561
 ..
i

thp. /?r"cbQ-s;:bstrate: the thin probe operates under higher temperature (i t is almost

equal to n.~ gas temperature: 300-450 K) and 10-100 times higher charged particle fluxes

(djffu~ion does not limit charged fluxes) in compare with the probe-substrate. It was

supposed to be an essential difference in surface adsorption for two kinds of probes and

it was proved experimentally.

Fig.4 shows temperature variati­

(ms of the film growth rate on the flat

probe-substrate. It was revealed, that the

temperature effect was different in posi­

ti ve and negati ve branches of the I.-V cha­

racteristic of the surface. The growth ra­

te in the electron branch is suppressed by

el~vatea tem~erdture very easily with an

apparent activation energy from -6 to -12

kcal/mol depending on temperature range.

The experimental data strongly suggest the

electric field control of adsorption sta­

-20 -to '0 ID. Volts
i
ges in the film growth mechanism in elect­
surface electric potential. Vs - Vf
ron branches of I-V characteristics.
Fig. 4. Film growth rate on thin probe
Specially low power (2 Watt) and
surface in a low power discharge. Gas "
consequent ly low gas temperature about
temperature is about 310 K.
]10-320 K discharge was initiated. And the

electron activation was also observed on

the surface of a thin wire probe lfi;.~j.

It is we) l knmtffi that the surface rilm growth rale. p..oo.:, ';'lll·rent.
electronic struc~:ure of semiconductors nlD/min J.lA
influence their et:::hing ratE>. By \lsi:~g of 3~~K .68t.lHz
different dopants the -:..lectroIllc Etructure 15% c-«F8+Ar
of Si, for example, can N:! changed from i­ ~:J Torr
type to n- or p-type. .in this case an
5Wl
electronic structure of the surface is

changed and effects adsorption properties

of the surface interact ing wi th neutral

particles with donor or acceptor proper-

v,,-v, -40

ties to electrons. The adsorption proces­ --~-o~~:~~-;a;OL~:::~~~--------'~~~-20

ses both for the reactive species and et­
ching products in this case may be cont­ surface electric pot.entiaL \bIts
rolled by type and density of the surface
Fig. 5. Substrate temperature effect on
charge carriers and their distributions.
dependence of film growth rate. Flat probe­
It was never measured directly under the
substrate, working area 3 /1lITJ in diameter.
plasma condition. But the results of et­

ching obtained in this case suggested for

such effect [5].

Direct effect of an external electric field was observed in case of silicon

etching in SF! RF discharge [6]. And also a well reproducible local maximum of the et­
ching rate near the floating potential was observed. In these experiments utilizing the
~:inetic probe method the influence of charged particles fluxes was separated from the
influence of electric field between the surface and plasma by corresponding varia-tions
of a mask material from dielectric (SiO.) to conducting (AI). In these two cases the co­
nfiguration of the electric field near the probe-substrate surface was different. In the
last case (AI mask) the surface electric potential of the mask was kept the same as of
the probe. So, the collecting surface of the probe was corresponding to the real flat
probe. Al mask played the role of a guard ring. It was revealed, that the charged par­
ticles flux does not determine the etching rate. It depends on the surface electric
potential only, that is only on the electric field between plasma and surface. But the
nature of the local maximum of the etching rate was not disclosed. .
The nature of local variations of plasma-surface interactions near the floatlOg
potential might be the same in both cases of film deposition and etching. A strong
influence of the intrinsic electric field on the deposition rate was clearly demonstra­
ted for plasma polymerization. The effect is very distinct only under the condition of

_-......--",.

1562

---~---~~~_
.................
 strong electric field which is easy to create only in case of low conducting materials.
But it is also not a problem in the most of the real situation even metal and semicon­
ductor substrate. Their surface is usually covered with an appropriate layer of oxides
or chemical compounds. So, in the most cases we have some low conductive surface layer.
When electric current is flowing through the surface though it may be very
small the electric field strength can be very high. But this electric field may be and
must be generated in the surface layer not only by the bias current but under the action
of only plasma itself as well.
A schematic representation of the
distribution of electric potentials during - ......
the plasma-surface interaction is showm in PL AS 11 A . .
Fig.6.
The actual situation, if any
dielectric surface is in a contact with a
low temperature non-equilibrium plasma. it
is bombarded by charged particles. The
zero net current means that the surface is
at floating potential.
Let us consider now the mechanism
of electric charge neutralization on the
surface. It was extensively studied by =~
Hagst rum et all [7] for cl ean metal '"=":-_-=---::-:--:-----:-:-----:-_....L::;-==~----:---,----_..,_~
surfaces and adsorbates. Some general Fig. 6. Distributions of electric potentials
features of charge neutralization O~ di­ bet""/'Oen a cond!lctive substrate with di­
electrics may be spe:::ulate t;ecause of a el ectric film itnd p1asrr.a (not scaled).
lack of experimental information.
In10ur cqse charged parti::;le fluxes on the surface are not so large - in the
range of 10' - 10') C;:l-I. SO, ~ver,;, surface site can 'Jet about one clHrged particle per
second in average. But the film ~rowth rate or etching is usually faster than several
monolayers per second. It means that electrons sticking the surface and transformed to
negative ions can not meet directly positive ions arriving from plasma because they must
be recovered by the deposited dielectric layer. Even if nor deposition neither etching
occur the rest time is high enough for charge dissipation or redistribution to exclude
di reet interact ion of charged particles
from plasma on the surface. In other
words, eleetricly charged particles from
plasma strike the surface and live as
localized states before to recombine.
However, physical properties of tIeId 'ltrt"D!llb
electrons and ions are quit different. ----\
Electrons can penetrate dielectric compa­ 1==:=="7"'9_4"--_ _V~g
plasma shOlll1 b
ratively deep depending on their kinetic
energy represented by the EEDF (electron
energy distribution function). Bulky posi­
tive ions are neutralized usually by elec­
trons tunneling from the surface before
they arrive [7]. Gas phase ions have high
ionization potential in compare with wor­ Fig. 7. Current of ions and electrons (a);
king functions of solid bodies. Hence, electric field strength in a plasma sheath
even in case of dielectric materials the (b1), film (b2), and in a surface layer (c).
tunneling mechanism of positive ion neut­
ralization is very probable. It means,
that in a dielectric surface under the action of plasma a double electric layer must be
formed. This layer must be positive outside and negative inside the solid body. In case
of very high efficiency of secondary electron emission through the Auger processes under
the ion bombardment some more complicated situation may exist. This must be the subject
of further investigations. And for our recent consideration the existence of this
electric double layer itself is important to assume.
This double layer whether it produce some electric field must effect surface
processes, for example adsorption. And hence, the resulting field in the surface layer

1563

_7... . - _. . - -, \.J, j t't' J.'t:J-u':ll~l:lb}.

~.G.K.VInogradov, Yu.A.Ivanov, L.S.Polak. High Energy Chem., vIS, pp 120-126 (1981).

J.L.Baldl and D.Beardo, J.Appl.Phys., v.57, (6) pp 2221-2225 (1985).

6.p.I.~evzorov, .E.F.Shelykchrnanov, G.K.Vinogradov, D.I.Slovetsky. Surface.

PhYSICS, ChemIstry, Mechanics (Russ.), v12, 84 (1987),

7.H.D,Hagstrum, Phys.Rev. vISa, (2), pp 495-515 (1966).
8·fi~9~~~ogradov. D.I.S10vetsky, A.G.Timokhov, High Energy Chem., v25, PP 268-272
9.G.K.Vinogradov, A I Z· k
(1992). . . Imeno , D.I.Slovetsky, A.G.Timokhov. Ibid., v26, pp 173-177

1564