Plasma etching of Si and SiO2—The effect of oxygen additions to CF4 plasmas

C. J. Mogab, A. C. Adams, and D. L. Flamm

Citation: Journal of Applied Physics 49, 3796 (1978); doi: 10.1063/1.325382

View online: http://dx.doi.org/10.1063/1.325382
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Abstract: Plasma etching of Si and SiO2−The effect of oxygen additions to CF4 plasmas
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 Plasma etching of Si and Si02- The effect of oxygen
additions to CF 4 plasmas
C. J. Mogab, A. C. Adams, and D. L. Flamm
Bell Laboratories. Murray Hill. New Jersey 09794
(Received 22 September 1977; accepted for publication 26 January 1978)

The plasma etching of silicon and silicon dioxide in CF.-02 mixtures has been studied as a function of feed-
gas composition in a 13.56-MHz plasma generated in a radial-flow reactor at 200 Wand 0.35 Torr.
Conversion of CF. to stable products (CO. CO 2, COF 2• and SiF.) and the concentration of free F atoms
([F]) in the plasma were measured using a number of different diagnostics. The rate of etching, the
concentration of F atoms, and the intensity of emission from electronically excited F atoms (3 s 2p_ 3p 21'"
transition at 703.7 nm) each exhibit a maximum value as a function of feed-gas composition ([0 2]); these
respective maxima occur at distinct oxygen concentrations. For Si02, the variation in etching rate with
[021 is accounted for by a proportional variation in [F], the active etchant. The etching of silicon also
occurs by a reaction with F atoms, but, oxygen competes with F for active surface sites. A quantitative
model which takes oxygen adsorption into account is used to relate the etch rate to [Fl. The initial
increase of [F] with [0 21 is accounted for by a sequence of reactions initiating with the production of CF 3
radicals by electron impact and followed by a reaction of CF 3 with oxygen. When [0 21 exceeds -23%
(under the present discharge conditions), [Fl decreases due, probably, to a decrease in electron energy
with an increase of oxygen in the feed gas,

PACS numbers: 52.40.Hf, 8L60.-j, 82.30.Cf, 82.65.Nz

I. INTRODUCTION lack of proportionality. First, the population of excited

states is a function of gas composition as well as power
Plasma etching of a solid substance occurs when the
and pressure, and even though the emission intensity
solid and an active species formed in a low-pressure
may be proportional to the F atom concentration accord-
glow discharge react to form a volatile compound. Be-
ing to
cause many inorganic halides are volatile in the temper-
ature range compatible with silicon intergrated-circuit IF=aJF], (2)
(SIC) lithographic masking materials, halogen-bearing
a F may vary with gas composition (at constant power and
gases are widely employed in plasma etching for pattern
pressure). 2 Second, oxygen may partiCipate in reactions
generation. The halocarbons are particularly useful
on the Si surface. In that case, oxygen may affect etch-
etchants since they are relatively easy to handle, non-
ing and homogeneous plasma reactions in distinct ways.
corrosive, and have low toxicity. Tetrafluoromethane
(CF 4) is one of the most frequently used gases for plas- In order to clarify the role of oxygen, we have studied
ma etching in SIC fabrication. CF r 02 plasmas by means of emission spectroscopy,
mass spectrometry, infrared spectroscopy, gas-phase
It is known that the addition of several percent oxygen
titration, and etch-rate measurements using both single-
to a CF 4 plasma dramatically increases the etch rate of
crystal and thermally oxidized silicon. Our main objec-
Si and SiO:!. Recently, Harshbarger et al. 1 found that the
tives were to obtain quantitative data on the relationship
etch rate of Si was correlated with the intensity of opti-
between etch rate and atomic fluorine concentration and
cal emission from excited fluorine atoms (IF) when oxy-
to develop a qualitative understanding of the chemistry
gen was added to CF 4 in a rf plasma; hence, they con-
associated with enhanced F atom production.
cluded that F atoms are the principal etchant.
If atomic flourine is the active etchant, one might ex- II. EXPERIMENTAL
pect the etch rate for Si (R) to be proportional to the
The apparatus is shown in Fig. 1. The parallel-plate
concentration of F atoms in the plasma,
(1)
where (3eff is a "rate constant". However, the data of SAPPHIRE
WINDOW EMISSION
Harshbarger et al. seemingly do not support this model.
PYREX ~SPECTROMETER
As the concentration of oxygen in the feed ([02]) is vari- VACUUM
ed, R and IF each reach a maximum value and then de- ENCLOSURE
crease. However, the maximum etch rate pc curs at a
lower oxygen concentration than that which produces a
26 CFM
maximum IF' Furthermore, for oxygen concentrations
~~~---.--+----+~~M~~u~tCAL
greater than the value corresponding to the maximum IF
the rate of decrease in R is substantially greater than
the rate of decrease of IF' These trends have been con-
firmed in the present investigation (see Fig. 6). 201 /s ION PUMP
Assuming that atomic fluorine is indeed the etch-ac-
tive species, there are at least two explanations for this FIG. 1. Schematic diagram of the experimental apparatus.

3796 J. Appl. Phys. 49(7), July 1978 0021·8979/78/4907-3796$01.10 @ 1978 American Institute of Physics 3796

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 substrates, throughout this work, either as blanks with
the polished surface exposed to the plasma of alter the
growth of 1. 0 Ilm of steam oxide. Etch rates for Si were
determined gravimetrically by assuming uniform remov-
al from the exposed surface. Etch rates for SiO, were
determined from thickness measurements made with
a He-Ne iaser and garnet prisrn coupler. I;
--PLASMA O N - -
m
III. RESULTS AND DISCUSSION
-e----
A. Discharge products
Figure 2 shows mass spectra of the effluent from an
empty reactor using 8 ri{ 02 in CF 4 with and without the
discharge. The peaks are identified in Table 1. In the
absence of discharge, the major peak at mass 28 is clue
to residual CO and to small leaks in the reactor (N; at
mass 28 and N+ at mass 14) which had a base pressure
of 5 mTorr. With a discharge, the CO and CO 2 peaks at
masses 28 and 44, respectively, increase substantially
wbile the O2 (mass 32) and CF I peaks (masses 25, 31,
34.5, 50, and 69) decrease; peaks corresponding to
FIG 2. l\Iass spectra for a cr,-s"; 0" mixture at 0.35 Torr o
0
COF 2 appear at masses 47 and 66. The peaks at 85, 86,
[l\Iain pe8,k at !!?cc'60 (CFj) is ~ff scale. I Axis divisions and 87 indicate the formation of SiFj due to etching of
correslxmd to ::; amu o
the Pyrex reactor wall. Atomic oxygen and atomic fluo-
rine in the plasma are detected by emission spectrosco-

radial-flow reactor consisted of two 40-cm-diam elec-

trodes with a 4. 4-cm interelectrode gap. All data were TABLE Io Identification of mass spectra (Fig. 2).
taken at 0.35 Torr total pressure, 200 cm 3/min total
Parent
flow, and 200 W of rf power applied through a matching l\lass No. a Species molecule (s) Hemarks
network. Substrates were maintained at 100°C during
12 All C-contnining
etching. Feed-gas composition ([02V[CF 4 ]) was the only species
variable throughout these experiments.
14 K2 From smu II leaks
The quadrupole mass spectrometer and ir cell were 16 °z,CO,C0 2
situated such that only stable end products of the dis-
17 H 20 Hesidtwl
charge could be observed, The mass spectrometer uti-
lized an orifice to sample from the exhaust line at re- 18 H2 0
duced pressure (-10- 6 Torr), A perkin- Elmer model 19 CF4
621 spectrophotometer and a 10-cm-path sampling cell 20 H? HF Heaction with
with NaCI windows were used for ir analysis. Infrared residual H 20
extinction coefficients for CF,) and SiF,j were measured
22 CO"
2 CO 2
at appropriate wavelengths by using samples of the pure
gases at known pressures. These coefficients were used 25 CFr CF,j
to determine the partial pressure of products from mea- 2S CO+,Ni CO,K2
surements of optical density. 31 CF+ CF 4
Optical emission from the plasma was spectrally ana- 32 O2 Oz
lyzed with a O. 3-m Ebert polychromator and a PARC 33 COFi+ COF 2
model l200A optical multichannel analyzer. The instru-
34.5 C}T CF 4
ment viewed the plasma volume immediately above the
substrates through a sapphire window and appropriate 44 CO2 CO 2
focusing lenses. 47 COF+ COF 2 Negligible contri-
bution from SiF+
Fluorine atoms were titrated using the chemilumine- 50 CFi CF 4
scent reaction with C1 2 • 3-5 The chlorine was injected
66 COFi COF z Negligible contri-
near the reactor exhaust where the rapid reaction bution from SiFi
F + Cl 2 - FCl + Cl (Rl) 69 cq CF,j
occurred. The chemiluminescence from Cl recombina- 70 CFj CF 4 13C; isotope
tion (600- 700 nm) was observed through a glass section 85 SiF:\ SiF 4
of the exhaust line 7 cm downstream of the Cl 2 injection 86 SiFj SiF 4
point. The luminous intensity increases until all atomic
F is consumed by reaction (R1) (see Fig. 5). 8'7 Si F 1i SiF 4 29Si, :JOSi isotopes

3-in-diam silicon wafers ([111], p type) were used as a Mass-to-charge ratio.

3797 J, AppL Phys" Vol, 49, No, 7, July 1978 Mogab, Adams, and Flamm 3797

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 30 ible outside the plasma since reaction products corre-
z sponding to fluorine-oxygen reactions were not detected
Q
(/) in the mass spectrometer.
II::
UJ 20
z> Then the principal loss of F atoms in transit to the
8 titration point ("" 15 cm from the reactor exhaust port) is
f- due to a heterogeneous recombination of F atoms,
Z
F+F~F2
UJ
U
II::
UJ
a.. so that

~
[Fltltratlon pt/[Flplaama = exp( -yv t/d) ,
g where y is the recombination probability, d is the ex-
Ii! haust line diameter, v is the mean thermal velocity, and
~
UJ
t is the time of transit to the titration point. The exhaust
II:: 0.2 line was fabricated from an aluminum alloy and had
a..
-J many hours of plasma exposure prior to titration. Nor-
<t
t= - - - FEED GAS dine and LeGrange have measured the recombination
II::
if 0.1
• EFFLUENT probability for F atoms on aluminum and report a value
of L 8 ± 0, 2 x 10- 3 • 9 However, they indicate that this
IJ..v
u value depends somewhat on previous exposure to F a-
00 toms as well as the amount of copper alloyed in the alu-
10 20 30 40 50 60
PERCENT 02
minum.
Because of these factors, the atom recombination rate
FIG. 3. Lower curve shows CF 4 partial pressure. The upper
curve indicates the percentage of CF 4 converted to products. on the exhaust tube is uncertain. If, nevertheless, the
value 1. 8X 10- 3 is assumed, it is calculated that 60% of
the F atoms in the plasma survive to reach the point of
py, the most prominent lines occurring at 703. 7 nm for titration, On this basis, a plasma F atom concentration
F* and 777.5 nm for 0*. was computed as shown in Fig. 5 for an empty reactor.

The major reaction products are unchanged by vari-
ations in the O2 content of the feed gas although their
relative proportions are altered; CO2 increases with
respect to CO and COF 2 as the feed is made more O2-
rich, and as previously shown, I the F atom emission
first increases, reaches a maximum, and then de-
creases (see Fig. 6).
s
Some C2FS was detected (C 2F at mass 119) when pure
Owing mainly to the uncertainty in y, it is felt that the
absolute values in Fig. 5 may be in error by a constant
factor of 5 or more; however, the shape of the curve
and relative preCision are clearly unaffected by this fac-
tor. It may be noted that the maximum atom concentra-
8.-----.-----~------~-----r----~

CF 4 was used as the feed. Small quantities of CO and

COF 2 were produced from pure CF 4 in the usual Pyrex
vacuum enclosure; however, these gases were not de- (f)
f-
tected when an aluminum enclosure (insulated from the Z
electrodes by Viton boot gaskets) was substituted for the ::l

Pyrex. >-
II::
<t
II:: 6
The extent of conversion of CF 4 into stable products t:
aJ
was measured by comparing ir absorption of the effluent II::
<t
with that of feed (113 fundamental mode at 1238 cm-I ). >-
f-
The maximum conversion occurs at - 23% O2 'as shown in
in Fig. 3. z
UJ
f-
Z
A typical gas- phase titration of F atoms in the reactor
effluent is shown in Fig. 4. The ordinate is the relative
chemiluminescent intensity1 at 650 nm due to the recom-
bination of Cl formed according to Eq. (R1). The end
point indicated by the arrow in Fig. 4 (with an uncer-
tainty of about 8% of the indicated value) can be used to
compute the F atom concentration inside the plasma
when certain assumptions are made regarding the side
reactions which consume F atoms downstream of the
20 30 40 50
plasma:
C'2 FLOW (cm 3/ MIN, 25"C)
(1) Homogeneous three body F recombination is very
slow and can be ignored8 and (2) reactions between F FIG. 4. Typical titration curve for the reaction of Ci2 with F
atoms and other species (prinCipally oxygen) are negUg- atoms. Arrow denotes the endpoint.

3798 J. Appl. Phys., Vol. 49, No.7, July 1978 Mogab, Adams, and Flamm 3798

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 3r------r-----.------'I------.-I----, The first reaction has a higher threshold energy10 and
proceeds more slowly than at least one of the latter two
--f ..... reactions, but, nevertheless, generates sufficient posi-
K' "-, tive ions and electrons to sustain the discharge. Reac-
/ "- tion (R3) is energetically less favorable than (R4) (the
i""E / "- I electron affinity of F is - 2 eV) and may be slow by com-
u
/ ''i parison.
t..... 2 J. ' In the oxygen-free discharge, reaction (R4) together
z
)(
/ with the detachment reaction

f
0
~
0:::
e+F--F+2e (R5)
~
Z
IJ..I I is apt to be a principal source of fluorine atoms; disso-

~
U
Z ciative recombination
0
U
(R6)
~
g may also be a significant contributor. The concentration
<l
u. of negative fluorine ions is also limited by the recombin-
ation
(R7)

O~ ____ ~l _____~~____~____~~~__~
Fluorine atoms are lost by heterogeneous recombina-
o 10 20 30 40 50 tion,
PERCENT 02
CF3+F~CF4' (R8)
FIG. 5. F atom concentration in the plasma versus 02 content F+Fwall F2 (R9)
of the feed determined by gas-phase titration. These data were
taken with the reactor empty. Error bars indicate titration and homogeneous recombination
endpo int uncertainty.
CF 3 +F +M- CF 4 +M, (RIO)

F +F +M- F2 +M. (Rl1)

tion occurs at about the same oxygen content that pro-
duces maximum CF 4 conversion (Fig. 3).
B. Effect of oxygen on fluorine concentration
Several plausible explanations can be proposed for the
increase in [F) due to added oxygen:
(1) Oxygen retards the heterogeneous recombination of
fluorine atoms with other species either by reacting with
them or by blocking access to a favorable recombination
surface.
(2) Oxygen retards the rate of the homogeneous reac-
tion of F atoms with other species by depleting the re-
actants via oxidation.
(3) Oxygen retards the loss rate of fluorine precur-
sors such as F- by removing species which would other-
wise consume the precursors.
(4) Oxygen reacts with fluorine-containing species to
liberate fluorine atoms. The reaction may occur on sur-
faces or in the gas phase.
We have carefully reviewed the literature of elemen-
tary reactions involving species found in the present
system. Based on this review, a set of reactions has
been formulated which is consistent with the experiment-
al results; a brief outline is given here.
In the absence of oxygen, electrons in the proper en-
ergy range decompose CF 4 via the reaction
e+CF 4 -CF:-CF;+F+2e,
e+CF 4 -CF 3 +F+e,
e +CF 4 - CF 3 + F".
CF 3 radicals can also recombine according to
CF 3 +CF3 wall C2F e (R12)
or
(R131
which accounts for the presence of some C2F s in the ef-
fluent of the oxygen-free discharge. The observation thai
with no added oxygen there is very little C2FS formed or
CF 4 converted suggests that reactions (R8) and/or (R9)
- (Rll) are rapid under the present conditions, hence,
the low fluorine atom concentration.
One function of oxygen might be to poison the surfaces
against reaction (R8) which would be the favored recom-
bination route at low pressure. However, one would ex-
pect, if this was the sole function of oxygen, that only a
small amount would be required in the feed gas to reach
a maximum [F], and additional oxygen would not have a
marked influence. Furthermore, this explanation does
not account for the production of CO, CO 2 , and COF 2•
A second possibility, a reaction of oxygen with a de-
posited surface film which would otherwise deplete F
atoms from the gas phase, could account for the in-
crease in [F] with [~]. As an example, fluorocarbon
deposits might react with oxygen to form volatile pro-
ducts: CO, CO2 , and COF 2 ; whereas, in the absence of
oxygen, these deposits might trap or recombine F a-
toms. Thus, the function of oxygen would be to remove
(R2) trapping sites by converting the fluorocarbon film to
volatile products. These deposits need only be a few
(R3)
monolayers thick and, therefore, might not be visible.
(R4) In fact, under slightly reducing conditions (e. g., a few

3799 J. Appl. Phys., Vol. 49, No.7, July 1978 Mogab, Adams, and Flamm 3799

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 percent H2 in CF 4), we have observed visible film de- The decrease in [F] and CF 4 conversion with a large
position in the present reactor, so the possibility of excess of oxygen cannot be accounted for by dilution a-
monolayer coverages cannot be rejected. lone. However, this decrease is qualitatively consistent
In order to gain some insight into the importance of with the expected effect of composition on electron en-
this mechanism for F atom enhancement, we have look- ergy. For E/p (field-strength-to-pressure ratio) in the
ed at the production of F atoms in an SiF r02 plasma by range of the present experiments (35- 50 V/cm- Torr),
observing the optical emission from excited F atoms. the electron energy in pure CF4 is 6- 8.3 eV, 13 whereas,
it is only 4.5- 6 eV for the same E/p in pure oxy-
Pure SiF 4 discharges produce almost no discernible
gen. 14-16 The rate of CF 4 dissociation [reactions (R2)
emission from F atoms. When oxygen is added, F atom
emission is observed (most prominently at 703.7 nm), and (R3)] is a function of electron energy and will be
greater in the energy range of a pure CF 4 discharge.
and SiOF 2 appears in the effluent mass spectrum. More-
over, SiF 4-02 plasmas etch Si and Si02 • Thus, oxygen Since electron dissociation of CF 4 is a necessary pre-
cursor to the oxidation reactions which liberate fluorine
has an analogous effect in the SiF 4 and CF 4 discharges.
atoms, this implies that the conversion of CF 4 will di-
The surface film mechanism cannot easily account for minish as the addition of oxygen shifts the electron en-
enhanced fluorine atom production in the SiF 4-02 plasma ergy distribution to lower energies.
since the analogous fluorosilicon compounds would not
be expected to deposit, and the analogous silicon oxida-
tion products, SiO and Si02 , are not volatile, and, c. The role of oxygen in etching silicon and silicon dioxide
therefore, a silicon-based surface film will not be re-
Figure 6 illustrates the relationship between the etch
moved by oxygen. Accordingly, while oxygen may inde-
rate of a 3-in Si wafer, the emission intensity from ex-
ed keep surfaces free of carbon-containing deposits in
cited F atoms (703. 7 nm) and the O 2 content of the feed
CFr 0 2 discharges, it seems unlikely that this process
gas. Each set of data has been normalized to its own
alone can account for an eightfold to tenfold increase in
maximum value in order to display the relative dis-
[FJ. Therefore, we conclude that mechanisms of type 1
placement of these curves as a function of O 2 content.
(above) do not playa major role.
The lack of proportionality between the etch rate and
This leaves mechanisms of type 2- 4, wherein oxygen
IF alluded to previously can be seen in Fig. 6.
reacts with some species to free fluorine atoms or pre-
vent their recombination. Although spectroscopic mea- If Eqs. (I) and (2) are combined,
surements reveal the presence of atomic oxygen, we
may exclude its direct reaction with CF 4 to form fluo- R = ({3.tt! a F) IF' (3)
rine since neither ground-state oxygen atoms (03p) nor According to Eq. (3), when i3.lr and aF are independent of
oxygen metastables (OlD) react with CF 4. 11 .t2 O2 content, the normalized curves for R and I F will co-
incide. Since this is not the case, (3.ff and/or aF depend
Instead we propose either
on the oxygen content. The gas- phase titration data of
(R14) Fig. 5 can be used to calibrate the 703. 7-nm emission
line intensity in order to determine the relative depen-
or
dence of a F on the O2 concentration in the feed gas. This
CF 3 +02 +M- CF3~ +M (R15)
as the most probable initial step. The combination of
CF 3 with oxygen competes with reactions (R8) and (RIO) 1 1 1 1
so that it represents fluorine enhancement via type-2
1.0 9-8 ",...x
and type-3 mechanisms. However, the OF radical is QI' XX)(~
highly reactive and can be converted to F atoms by se-
veral paths
CF 3 +OF- COF 2 +2F, (R16)
~~ 0.8
<1:-
a: II)
z
::J:W
lJ\
fI
"-
\ ~
OF +OF- O2 +Ft - 02 +2F, (R17) <..>t-
t-z 0.6 ,/ \\ '\.
w-
while CF 30 2 may produce F atoms directly by a series
~~ I '0 '\
of free radical reactions involving fluoroxy compounds
(e.g., CF 3OOCF 3 , CFsOF, ... ) and radicals (CF 300, ~S
iilii1 0.4
pi
I
" "'8
CF 30, ... ). Thus, reactions (R14) and (R15) are initial
steps of a type-4 mechanism as well. a: a: If "
Oxygen atoms are produced in the discharge via 02 1
.V
1 0 ETCH RATE (Sil '<l...
)( 703.7nm LINE INTENSITY-ETCHING Si
e+02- 0 + 0 + e , (R18a)
ooL-----1LO-----2Lo----~30~---4~O-----5~O----~60
e +02-0-+0 (R18b)
PERCENT 02
and can augment F atom production indirectly through
reactions such as FIG. 6. The normalized etch rate for Si and normalized inten-
sity of the emission from electronically excited F atoms
(R19) (703. 7-nm line) versus 02 concentration in the feed.

3800 J. Appl. Phys., Vol. 49, No.7, July 1978 Mogab, Adams, and Flamm 3800

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 1.0....-----r---r-----.----,------, is present in the feed, silicon etches so rapidly that the
reaction is rate limited by the supply of etching species
(F atoms) at the surface. 11 Thus, the rate constant for
F atom removal through the formation of volatile SiFx is
0.8
much larger than the rate constant for F atom adsorp-
tion. Consequently, (J F «1 and
",
[0]. (6)
E0.6 r.=k.(l- (Jo)
The rate of oxygen removal rd is given by
t.....
rd=kd(Jo [F] (7)
'"
~0.4
since it has been assumed that etching releases oxygen.
At steady state, rd = r.. and
0.2 1- (Jo =kd[F]/(kd[F] + k.[ 0]). (8)
Substitution of Eq. (8) into Eq. (4) yields
OL-_ _ ~ _ __ J_ _ _ ~ _ _ _ _ L_ _ _ _ ~
R =f3[F]2/([F] +K[O]), (9)
o 10 20 30 40 50
where K =kjk d • Thus, for competitive adsorption, the
PERCENT 02
etch rate is not strictly first order in [F] unless K[O]
FIG. 7. O!Fversus O 2 concentration (see text). «[F]. The latter condition will be met at a low enough
oxygen concentration.
In order to test Eq. (9) in an expedient manner, we
is shown in Fig. 7. Since a F decreases with O2 addition, have utilized emission intensities to measure the rela-
the absolute intensity IF gives a relative measure of [F] tive values of [F] and [0] during etching of Si. Taking
which is too low. This correction to aF is in the wrong [F]=I F/a F with aF determined from Fig. 7 and [0]=10 1
direction to bring f3et/Fla F into coincidence with the a o , Eq. (9) can be expressed in the form
etch-rate curve (R) as per Eq. (3). Accordingly, f3 eff al-
so must decrease with the concentration of oxygen in the ~ _.! +If- lOaF (10)
feed gas. This is also apparent from Fig. 8 where [F] a~ -(3 f3a o IF '
has been determined from emission data using Eq. (2) where 10 is the intensity of emission from electronically
and Fig. 7. A given [F] can yield two different etch excited oxygen atoms (777.5 nm) and a o is a proportion-
rates depending on [02 ], ality constant. If any dependence of a o on the oxygen
Therefore, we consider a simple model of the etching concentration is ignored, according to Eq. (10), a plot
process wherein F atoms are the active etchant but I1
of 1F/aFR againstIo a F F will be linear; as shown in
where these F atoms compete with a second species, Fig. 9, the data are consistent with this prediction.
which we presume to be atomic oxygen, for the active (These data span a range 3- 40% in O2 concentration.)
sites on the Si surface. This is consistent with the fact
that a freshly exposed Si surface is readily oxidized,
5000....-------.-------~------~-------,--~
particularly by atomic oxygen. The chemisorption of 0
atoms on the Si surface (tantamount to oxidation) would
slow down the rate of etching since Si etches faster than
Si02 under the present experimental conditions. This 4000
model also accounts for the reduction in emission from
excited atomic oxygen during the etching of Si. 1 Allowing z
for the competition between oxygen and fluorine atoms, :::!!
.....
Eq. (1) can be written oe:( 3000

(4) W
l-
e:(
Q:
where f3(1- (Jo) = f3 eff • f3 is a rate constant which may de-
J: 2000
pend on temperature but is independent of [0], and (Jo is u

I
I-
the fraction of surface sites occupied by oxygen atoms. W

To develop this model further, we assume (1) F atoms III

on the surface are removed mainly by formation of vola- 1000

tile SiFx products, (2) oxygen atoms are removed by the
etching, and (3) thermal desorption of F and 0 atoms is
negligible.
Then the rate of oxygen atom adsorption r. is
[F] (ARBITRARY UNITS)
(5)
where (JF is the fraction of surface sites occupied by FIG. 8. Etch rate of Si versus [Fl. Arrows indicate the direc-
fluorine atoms and k. is a rate constant. When oxygen tion of increasing O2 concentration in the feed.

3801 J. Appl. Phys., Vol. 49, No.7, July 1978 Mogab, Adams, and Flamm 3801

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128.151.244.46 On: Tue, 04 Nov 2014 09:02:51
 12r----r----.----.----~--_.----._--~ try or ir absorption. In this work, the partial pressure
of SiF4 in the effluent (during steady- state etching of Si
was determined from ir absorption' using the SiF 4 band
at 1036 cm- t • This pressure was then corrected for a
small "background" contribution due to etching of the
Pyrex enclosure. There was good agreement between

·~ri
the quantity of SiF 4 observed and that expected from the
gravimetrically measured etch rate of Si assuming SiF 4
N to be the only silicon-containing product. These mea-
-0
surements were made at both low and high O2
concentrations.
~Ia:
.... ~
4
0 In the case of Si02, a similar mass balance could not
be carried out because the low etch rates did not pro-
2 duce enough SiF 4 relative to the background contribution
from the reaction with the Pyrex enclosure. However,
no silicon oxyfluorides were detected by mass spectro-
metry. Similar results were obtained by Clyne and co-
(ARB. UNITS) workers 4,t9 who used mass spectrometry to study a CF 4
(1 %)-argon discharge produced in a silica tube. Ac-
cordingly, we conclude that the overall stoichiometry of
FIG. 9. IF/O/pR versus IOO/F/IF' [See Eq. (11).1 The data etching by atomic F is
points span the range 3-40% 02 in the feed gas.
Si+4F-SiF 4 (R20)
and
Therefore, the model postulated can account quantita-
(R21)
tively for the observed dependence of etch rate on the 02
concentration of the feed gas. Evidently, Si02 etches much more slowly than Si be-
cause of the necessity of breaking strong Si-O bonds in
Oxygen is seen to have a dual role in the etching of Si:
reaction (R21) rather than as a result of a reaction with
(0 It enhances production of the etchant (F) in the plas-
a different active speCies.
ma, and (ii) it retards the etching reaction by adsorbing
on active surface sites. These two phenomena have op- As indicated previously, both silicon and Si02 can be
posing effects on the etch rate, and the net result is that
the etch rate reaches a maximum value at a lower O 2
etched in plasmas formed in mixtures of SiF 4 and 2,
although the rate is slower than that in comparable mix-
°
concentration in the feed gas than that which produces a tures of CF 4 and 02' Furthermore, atomic fluorine is
maximum fluorine atom concentration. also a prominent species in the SiF 4-02 discharge.
The etching of Si02 was found to be similar to that of
Si except that oxygen had no significant retarding effect
in the range investigated (0- 50% O2), Figure 10 shows
the etch rate of Si0 2 films versus relative F atom con-
centration as deduced from the emission intensity of ex- 300
• •••••
• •
• • ••
cited F atoms (703. 7-nm line, corrected for the effect
of gas composition). The F atom concentration was
varied by changing the O2 content of the feed gas over the z
~
• ••
range 3- 50% 02' Within the scatter of these data, the
etch rate scales with [F] regardless of the O2 concentra- "'
oc(
200 •
••
tion. The reason for this scatter is unknown; it is too LU

large to be explained by typical fluctuations in emission ~

II::
intensity (indicated by the error bar on the point near :I:
the center of Fig. 8), and it cannot be attributed to the ~
preCision of film-thickness measurements. The emis-
LU
N •
sion intensity was measured after the discharge had Q
(/)
100
reached a steady state; however, depending on the prior
length of exposure of the reactor to atmosphere, up to
10% of the total run time was required to reach a steady
state. 18 This transient may account for the scatter. De-
spite this, the results suggest that F atoms are a major O~ ___ ~l __ ~ ____ ~ ____ ~ __ ~ ____ ~.

etchant for Si02 in CF r 02 discharges. o 5 10 15 20 25 30

D. Etch reaction products
SiF 4 was the only silicon-containing product detected
in the effluent when etching either Si or Si02• This pro-
duct can be readily analyzed either by mass spectrome-
[F] (ARBITRARY UNITS)
FIG. 10. Dependence of the etch rate of Si0 2 on the F atom
concentration. The data points cover the range ~ 3-50% 02 in
the feed gas. (The error bar indicates the magnitude of typical
fluctuations in the emission intenSity.)

3802 J. Appl. Phys., Vol. 49, No.7, July 1978 Mogab, Adams, and Flamm 3802

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128.151.244.46 On: Tue, 04 Nov 2014 09:02:51
 These facts again suggest that atomic fluorine is the do-
minant etchant and, further, that CF 3 radicals are not
essential for etching Si or Si02 •
IV. CONCLUSIONS
The addition of O2 to a CF 4 plasma produces a marked
increase in the emission from electronically excited
states of atomic fluorine. The enhanced emission cor-
relates approximately with an increase in the concen-
tration of F atoms in the plasma as determined by gas-
phase titration. The proportionality constant between
the emission intensity from the 703. 7-nm F line and the
absolute F atom concentration decreases slowly as the
O2 content increases. At 200 W rf power and 0.35 Torr
total pressure, the maximum F atom concentration oc-
curs at an O2 content of - 23%. Based on mass and in-
frared spectrometric analyses of the discharge effluent,
it is suggested that enhanced production of F atoms is
probably initiated by a reaction of oxygen with CF 3 radi-
cals to ultimately form CO, CO2 , COF 2 , and F.
Fluorine atoms are active in etching Si, but the etch
rate is not strictly proportional to [F] because of com-
°
petition between F atoms and atoms for active Si sur-
face sites. Adsorption of oxygen retards the etch rate;
when due account of this is taken, a quantitative corre-
lation is obtained between the etch rate of Si and the F
atom concentration in the plasma.
The etching of Si02 differs from Si (apart from being
much slower) in that no significant retarding effect of
oxygen is observed. Consequently, the maximum etch
rate coincides with the O2 content which produces a
maximum F atom concentration in the plasma. Experi-
ments with SiF r02 plasmas indicate that CF 3 radicals
are not necessary for the reaction between Si02 and
F atoms.
Finally, from mass and infrared spectral analyses
of the reactor effluent, we conclude that SiF 4 is the
3803 J. Appl. Phys., Vol. 49, No.7, July 1978
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128.151.244.46 On: Tue, 04 Nov 2014 09:02:51
only stable volatile Si-containing etch product produced
by etching of Si and Si02 in CFr02 plasmas.
lW.R. Harshbarger, T.A. Miller, p. Norton, and R.A.
Porter, Appl. Spectrosc. 31, 201 (1977).
2For a system consisting of ground-state and electronically
exited atoms in thermal equilibrium, the emission intenSity
for any particular transition is proportional to the atom con-
centration, but the plasmas of interest here are not equilibri-
um systems. However, the data presented in this paper and
in Fig. 2 of Ref. 17 suggest that the proportionality is main-
tained in the present case.
3G. Schatz and M. Kaufman, J. Phys. Chem. 76, 3586 (1972).
4M.A.A. Clyne, D.J. McKenney, and R.F. Walker, Can. J.
Chem. 51, 3596 (1973).
5P.C. Nordine and D.E. Rosner, J. Chem. Soc. Faraday
Trans. 1 72, 1526 (1976).
sP.K. Tien, R. Ulrich, and R.J. Martin, Appl. Phys. Lett.
14, 291 (1969).
7M.A.A. Clyne and D.H. Stedman, Trans. Faraday Soc. 64,
1816 (1968).
8P.S. Ganguli and M. Kaufman, Chem. Phys. Lett. 26, 221
(1974).
9P.C. Nordine and J.D. LeGrange, AIAA J. 14, 644 (1976).
10J.L. Franklin, J.G. Dillard, H.M. Rosenstock, J.T.
Herron, K. Draxl, and F. H. Field, Ionization Potentials,
Appearance Potentials and Heats of Formation of Gaseous
Positive Ions (U .S. GPO, Washington, D. C., 1969), p. 26.
l1J.N. Pitts, H.J. Sandoval, and R. Atkinson, Chem. Phys.
Lett. 29, 31 (1974).
12R. Atkinson, .G.M. Breven, J.N. Pitts, Jr., and H.J.
Sandoval, J. Geophys. Res. 81, 5765 (1976).
13M.S. Naidu and A.N. Prasad, J. Phys. D 6, 983 (1972).
14G. Hake and A. V. Phelps, Phys. Rev. 168, 70 (1967).
15J.A. Rees, Aust. J. Phys. 18, 41 (1965).
16D. A. Price, J. Lucus, and J. L. Moruzzi, J. Phys. D 6,
1249 (1972).
17C.J. Mogab, J. Electrochem. Soc. 124, 1262 (1977).
18During the transient period, the F emission gradually in-
creases while that of atomic hydrogen decreases. These
events are thought to be related to plasma-activated desorp-
tion of strongly bound H20 on the interior reactor surfaces.
1~.A.A. Clyne and R. T. Watson, J. Chem. Soc. Faraday
Trans. 1 70, 1109 (1974).
Mogab, Adams, and Flamm 3803