Optimization and analysis of NF3 in situ chamber cleaning plasmas

Bing Ji, James H. Yang, Peter R. Badowski, and Eugene J. Karwacki

Citation: J. Appl. Phys. 95, 4452 (2004); doi: 10.1063/1.1688996

View online: http://dx.doi.org/10.1063/1.1688996
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 JOURNAL OF APPLIED PHYSICS VOLUME 95, NUMBER 8 15 APRIL 2004

Optimization and analysis of NF3 in situ chamber cleaning plasmas

Bing Ji,a) James H. Yang, Peter R. Badowski, and Eugene J. Karwacki
Air Products and Chemicals, Incorporated, 7201 Hamilton Boulevard, Allentown, Pennsylvania 18195
共Received 30 July 2003; accepted 3 February 2004兲
We report on the optimization and analysis of a dilute NF3 in situ plasma-enhanced chemical vapor
deposition chamber cleaning plasma for an Applied Materials P-5000 DxL chamber. Using design
of experiments methodology, we identified and optimized operating conditions within the following
process space: 10–15 mol % NF3 diluted with helium, 200– 400 sccm NF3 flow rate, 2.5–3.5 Torr
chamber pressure, and 950 W rf power. Optical emission spectroscopy and Fourier transform
infrared spectroscopy were used to endpoint the cleaning processes and to quantify plasma effluent
emissions, respectively. The results demonstrate that dilute NF3 -based in situ chamber cleaning can
be a viable alternative to perfluorocarbon-based in situ cleans with added benefits. The relationship
between chamber clean time and fluorine atom density in the plasma is also investigated. © 2004
American Institute of Physics. 关DOI: 10.1063/1.1688996兴

I. INTRODUCTION collapsed.15,29,30 Therefore, it is desirable to systematically

In the manufacture of semiconductor integrated circuits,
multiple thin-film depositions are performed on a wafer by
plasma-enhanced chemical vapor deposition 共PECVD兲 pro-
cess. The deposition process not only facilitates the growth
of films onto a wafer, but also leaves solid residues on the
internal surfaces of the deposition reactors. These unwanted
residues can lead to deposition process drift, particle defects,
and yield loss. Therefore, periodic cleaning of the internal
surfaces is necessary to maintain production yield. Chamber
cleaning is usually carried out by employing fluorine-based
chemistries to convert solid residues into volatile gaseous
byproducts that can be pumped out of the reactor by vacuum
pumps. Historically, perfluorocarbons 共PFCs兲, such as CF4
and C2 F6 , are used as the source of reactive fluorine in
PECVD chamber cleaning. The potential impact of these
molecules on global warming has become an increasing con-
cern in recent years.1–5 Within the last decade, several agree-
ments were signed between major semiconductor manufac-
turers and U.S., Europe, and Asia governmental institutions
calling for voluntary reduction or elimination of PFC
emissions.6,7 As a result, several strategies to reduce PFC
emissions during PECVD chamber cleaning have been pur-
sued by the industry with varying degrees of success. These
approaches include: Optimizing C2 F6 -based in situ
cleaning,8 –12 replacing C2 F6 with an alternative cleaning
gas,13–22 adopting NF3 -based remote plasma downstream
cleaning technology,23–26 and utilizing PFC recycling or
abatement processes in the reactor effluent line.1,27,28 Among
the alternative cleaning gases, NF3 is an attractive candidate
because of its short atmospheric lifetime, high destruction
efficiency, absence of fluorocarbon polymeric residues, and
faster clean time. However, developing a fully optimized
NF3 in situ plasma chamber clean for industrial production
PECVD reactors has proven to be challenging. NF3 plasmas
can become highly electronegative and become unstable or
a兲
Electronic mail: jib@airproducts.com
study the effects of various process parameters on NF3 dis-
charges under production reactor chamber cleaning condi-
tions, and compare these effects to fundamental discharge
studies conducted in smaller research reactors.
Inert diluent gases, such as argon and helium, are often
used to stabilize NF3 plasmas and enhance etch rates. The
complex relation between plasma stability and rf power, NF3
partial pressure, and flow rate was studied and is presented in
a companion publication.31 In this study, we focus on the
effect of diluent on chamber clean time, which is closely
related to etch rate. The exact relationship between etch rate
and NF3 concentration is convoluted with many factors, such
as reactor design and substrate type. Wide variations are re-
ported in literature. Some studies showed a monotonic in-
creasing of substrate etch rate as NF3 concentration
increases.32,33 Others showed peak etch rates at some inter-
mediate concentrations.34,35
While these investigations unveiled insights into the NF3
discharge processes, most of the previous studies were con-
ducted in small parallel-plate-type capacitively coupled reac-
tors, and used a test wafer/coupon located on one of the
electrodes to determine etch rates. Only a few recent efforts
were made to optimize NF3 -based chamber cleaning in ac-
tual production PECVD reactors. Hines16 reported NF3 /He
chamber cleaning on an Applied Materials 共Santa Clara, CA兲
P-5000 PECVD reactor, although no quantitative process or
emissions data were provided. Pruette et al.15 experimented
with NF3 /He in situ chamber cleaning on a Novellus 共San
Jose, CA兲 Concept One 200 PECVD reactor. The authors
reported some promising results as well as challenges in sta-
bilizing NF3 plasmas.
The objectives of this study were: 共1兲 To optimize
NF3 -based in situ chamber cleaning on a production PECVD
reactor using design of experiments 共DOE兲 methodology, 共2兲
to quantify chamber clean time and effluent emissions by
optical emissions spectroscopy 共OES兲 and Fourier transform
infrared 共FTIR兲 spectroscopy, 共3兲 to systematically investi-
gate the dependence of clean time and effluent emissions on

0021-8979/2004/95(8)/4452/11/$22.00 4452 © 2004 American Institute of Physics

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 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004
FIG. 1. Experimental setup.
various process parameters, and 共4兲 to compare discharge
behaviors in a production reactor with those in smaller re-
search reactors. Knowledge obtained from this study not
only offers a set of optimized stable NF3 chamber cleaning
plasma conditions, but also provides a general methodology
and guidance for optimizing NF3 -based in situ chamber
cleaning on other production scale PECVD reactors.
II. EXPERIMENTS
All experiments were carried out in an Applied Materials
lamp heated DxL PECVD chamber on the P-5000 platform.
The DxL chamber was fitted with a 200 mm PECVD process
kit. Figure 1 shows the experimental setup. Before each
chamber cleaning experiment, a 1.0 ␮m thick SiO2 film was
first deposited onto a 200 mm silicon wafer, using the stan-
dard Applied Materials plasma-enhanced tetraethyl
orthosilicate/O2 (TEOS/O2 ) deposition recipe 共also called
the best known method or the TEOS BKM兲. The
SiO2 -coated wafer was removed from the chemical vapor
deposition 共CVD兲 chamber after the deposition. Cleaning
gases NF3 and helium were then introduced into the CVD
chamber via mass flow controllers 共Unit, Model 1661 and
1801兲. Once the process gas flows and chamber pressure
were stabilized at the desired set points, rf power 共ENI
Model OEM-12B-02兲 was turned on and matched to the re-
actor via a matching network to ignite and sustain the plasma
for chamber cleaning. An Applied Materials standard
C2 F6 /O2 clean 共also called the C2 F6 BKM兲 always followed
the experimental NF3 clean to ensure that all SiO2 residues
had been removed from the interior surfaces of the chamber.
As part of the Applied Materials C2 F6 BKM, the interior
surfaces of the chamber were precoated 共or seasoned兲 with a
thin layer of SiO2 film after the C2 F6 /O2 plasma clean. The
seasoning step completed the sequence for one NF3 clean
DOE run. The sequence was then repeated for the next NF3
clean DOE run. The PECVD reactor electrode gap spacing
was fixed at 25.4 mm in all cleaning runs. As a reference for
performance comparison, we also measured the Applied Ma-
terials standard C2 F6 cleaning process following 1 ␮m SiO2
deposition.
A nitrogen purge of about 50 standard liters per minute
was added to the pump exhaust 共Edwards pump, model
QDP80/QMB250兲. FTIR absorption spectroscopy was used
to analyze the gaseous emissions from the chamber clean
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Ji et al. 4453
process. A Midac spectrometer with 1.0 cm path length cell
and KBr windows was utilized. Part of the plasma effluent
stream was extracted by a sample pump and pulled through
the FTIR sample cell for analysis. The 1/8 in. stainless-steel
sampling line leading from the pump exhaust pipeline to the
spectrometer cell was heat traced at 100 °C to prevent con-
densation of TEOS and other residues. AutoQuant 3.0® soft-
ware was used for data collection and off-line processing.
Effluents were continuously monitored during depositions
and cleans. The FTIR spectral window was from 650 to 4500
cm⫺1, resolution was 4 cm⫺1, gain was 1, triangle apodiza-
tion was utilized with Mertz phase correction, and linear
baseline correction was applied. An optical fiber was
mounted on a viewport on one side of the chamber. Plasma-
induced optical emission signals were collected into the fiber
and transmitted to a charge coupled device array UV/visible
spectrometer 共Ocean Optics S2000 Donedin, Florida兲. The
optical emission spectra were recorded approximately every
0.5 s during chamber cleaning. Data were then analyzed off
line for endpoint determination.
III. RESULTS AND DISCUSSIONS
A. Endpoint determination and effluent
emissions quantification
Because of the relatively low bonding energy 共2.47
eV兲,36 NF3 readily dissociates when colliding with high-
energy electrons in the plasma
NF3 ⫹e ⫺ →NF2 ⫹F⫹e ⫺ . 共1兲
NF3 can also release reactive fluorine atoms via dissociative
ionization, such as
NF3 ⫹e ⫺ →NF⫹ ⫺
2 ⫹F⫹2e , 共2兲
with a threshold energy 共i.e., appearance potential兲 of about
15 eV.37,38 The large amount of atomic fluorine generated
from reactions 共1兲 and 共2兲 is one of the most active species
for chamber cleaning. For example, F atoms can react with
deposition residues such as SiO2 via
SiO2 共 s 兲 ⫹4F→SiF4 共 g 兲 ⫹O2 共 g 兲 . 共3兲
A competing process is the recombination of atomic fluorine
radicals to form molecular fluorine,
2F⫹T→F2 共 g 兲 ⫹T* , 共4兲
where T is the third-body molecule to take away the excess
energy as T*. In most cases, the production rate of atomic
fluorine through plasma dissociation of NF3 is relatively con-
stant. As SiO2 is removed from the chamber, the rate of
fluorine consumption through reaction 共3兲 decreases. This
results in an increase of atomic fluorine density in the
plasma. The increase of fluorine atom density in the plasma
leads to the increase of atomic fluorine optical emission in-
tensity at 703.75 nm. The time when the residual SiO2 is
completely removed from the internal surfaces of the CVD
chamber is called the ‘‘endpoint.’’ The endpoint is marked by
a plateau in the atomic fluorine 共F兲 number density. As a
result, the atomic fluorine optical emission intensity at
703.75 nm also reaches a plateau at the endpoint. This pro-
 4454 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004
FIG. 2. Methods to determine chamber cleaning endpoint from atomic fluo-
rine optical emission spectra. The endpoint can be determined either from
changes in the time derivative dI F(704 nm) /dt 共the dotted line兲, or by the
intersection between the slopes of the OES intensities.
vides a convenient means to determine the cleaning end-
point. Since there was no automatic optical endpoint detector
on our DxL chamber, we collected OES and effluent emis-
sions data over a fixed period of time. The endpoint was
determined from off-line analysis of the OES data.
Figure 2 shows the two methods which can be used to
determine the endpoint from the OES data. First, one can
compute the numerical derivative dI F(704 nm) /dt of the OES
intensity at 703.75 nm. The following criteria are used to
determine the endpoint:
共i兲 dI F(704 nm) /dt has passed over a peak, then
共ii兲 dI F(704 nm) /dt has decreased to baseline noise level;
and
共iii兲 early occurrence of 共i.兲 and 共ii.兲 is ignored.
Alternatively, one can draw a line to extend the slope where
the fluorine OES intensity is increasing, and a line to extend
the asymptotic slope where the fluorine OES intensity is ap-
proaching the plateau. The intersection point between these
two lines is the endpoint. As seen in Fig. 2, both methods
generally give consistent determination of the endpoint.
Clean time is defined as the time interval between
plasma ignition and the endpoint. The SiF4 effluent emis-
sions profile from FTIR measurement is overlaid in Fig. 2.
We can see that at the OES endpoint, the SiF4 effluent con-
centration is still falling. To ensure complete removal of the
deposition residue from the chamber, it is a common practice
to extend the cleaning process by 20% of the clean time as
an overetch. It can be seen from Fig. 2 that the SiF4 emission
in the effluent approaches a steady value at the end of the
20% overetch.
The SiF4 emission profile in NF3 -based cleans is differ-
ent than that in C2 F6 -based cleans. In C2 F6 -based cleans, the
SiF4 emission generally falls to zero at the end of the 20%
overetch period. On the other hand, the SiF4 emission does
not decrease to zero at the end of the overetch period for
NF3 -based cleans. Rather, as shown in Fig. 2, the SiF4 emis-
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Ji et al.
sion flattens out to a lower value at the end. In fact, the SiF4
emission does not fall to zero even after an extended period
of time 共e.g., over 30 min兲. As shown later in this section, at
the end of the overetch, SiO2 has been completely removed
from the internal surfaces of the chamber, thus the continued
SiF4 emission after overetch must come from other sources.
NF3 plasmas can generate significant amounts of reactive
species, such as F2 , NF2 , etc. Because these reactive species
have relatively long life times and can survive outside of the
plasma, these species can react with silicon-containing resi-
dues left over in reactor components downstream to the
deposition chamber. For example, it is known that residues
accumulate on the surfaces of the pressure controlling
throttle valve and along the internal surfaces of the pump-out
manifold, or even in the effluent exhaust pipeline. Long-
lived reactive species, such as F2 and/or NF2 , can pass
through the chamber and volatize downstream silicon-
containing residues to emit SiF4 . Therefore, NF3 plasmas
not only remove residues from the internal surfaces of the
CVD chamber, but also remove residues from component
surfaces downstream to the CVD chamber. This can be par-
ticularly advantageous for certain CVD processes that may
leave heavy residues downstream to the chamber. For ex-
ample, CVD processes for low dielectric constant organosili-
cate glasses 共OSG兲 can leave large amount of residues on the
throttle valve and pump-out manifold that cannot be effec-
tively cleaned by a C2 F6 -based process. After many cycles of
OSG deposition and C2 F6 -based chamber cleaning pro-
cesses, the accumulation of solid residues downstream to the
deposition chamber was confirmed by visual inspection of
the internal components of the throttle valve. Switching to an
NF3 -based chamber cleaning process eliminated this prob-
lem.
Figure 3 shows continuous emissions monitoring by
FTIR during a sequence of chamber cleaning experiments.
The first and the last set of experiments in Fig. 3 are C2 F6
BKM clean. The species emitted from the C2 F6 BKM clean
process are: C2 F6 , CF4 , CO2 , COF2 , and SiF4 . CO2 is also
emitted during TEOS/O2 PECVD deposition process. The
middle three sets of experiments are NF3 -based cleaning fol-
lowed by a C2 F6 BKM. The species monitored during
NF3 -based cleaning are NF3 and SiF4 . While F2 is also emit-
ted from NF3 -based cleaning processes, it cannot be moni-
tored by FTIR. For C2 F6 BKM clean, the mass balance of
both carbon and fluorine elements can be achieved within
⫾5% from volumetric integration of emissions measured by
the FTIR. This confirms that the FTIR analysis has captured
all carbon and fluorine-containing species in the effluent.
However, the fluorine balance for NF3 -based DOE cleaning
processes ranges from 50% to 82% based on volumetric in-
tegration of NF3 and SiF4 emissions in the FTIR measure-
ments. The ‘‘missing’’ fluorine balance is due to the emission
of F2 and possibly other fluorine-containing byproducts that
cannot be detected by FTIR.
The destruction efficiency 共DE%兲 of NF3 is determined
by
关 NF3 兴 rf off⫺ 关 NF3 兴 rf on
DE%⫽ ⫻100%, 共5兲
关 NF3 兴 rf off
 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004
FIG. 3. Continuous emissions monitoring by FTIR during a sequence of
chamber cleaning experiments. The first and the last set of experiments are
C2 F6 BKM clean. The middle three sets of experiments are NF3 -based
cleaning followed by a C2 F6 BKM.
where 关 NF3 兴 rf off is the average NF3 concentration before the
rf power is turned on, and 关 NF3 兴 rf on is the average NF3
concentration after rf power is turned on. The same definition
can also be applied to C2 F6 -based cleans, where the appro-
priate C2 F6 concentrations replace the corresponding NF3
concentrations in Eq. 共5兲. Volumetric emissions of each ef-
fluent gas are computed by integrating the FTIR emission
profile over the clean time, as determined by the OES end-
point, and plus the 20% overetch period. Total global warm-
ing emissions per clean were reported in terms of kilograms
of carbon equivalents 共kgCE兲. The following equation is
used to calculate kgCE:
12
kgCE⫽ 兺i Q i 44 GWPi,100 ,
where Q i is the amount of effluent in kilograms and
GWPi,100 is the 100-year global warming potential of the gas.
GWP100 for NF3 , CF4 , and C2 F6 are: 8000, 6500, and 9200,
respectively.
In addition to the destruction efficiency DE% of NF3 ,
we also define fluorine utilization efficiency 共FគUE%兲 as
4V SiF4 共 emitted兲
FគUE%⫽ ⫻100%,
3V NF3 共 fed兲
where V SiF4 (emitted) is the volumetric emission of SiF4 inte-
grated over the entire cleaning process 共including the 20%
overetch period兲, and V NF3 (fed) is the total volumetric input of
NF3 that was fed into the reactor over the same time period
as for SiF4 emissions integration. Similarly, we can also de-
fine FគUE% for a C2 F6 -based clean as
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Ji et al. 4455
4V SiF4 共 emitted兲
FគUE%⫽ ⫻100%, 共8兲
6V C2 F6 共 fed兲
where V C2 F6 (fed) is the total volumetric input of C2 F6 that
was fed into the reactor over the same time period as for SiF4
emissions integration. Not all fluorine released from feed gas
destruction react with the deposition residues and emit as
SiF4 . Some of the fluorine input is converted to other
fluorine-containing byproducts such as F2 , CF4 , and COF2 ,
in addition to the unreacted PFC emissions. Therefore,
FគUE% is a better metric than the feed PFC gas DE% to
quantify the efficiency of clean gas utilization. For NF3 plas-
mas, our data show a linear correlation between FគUE% and
NF3 DE% given by
FគUE%⫽⫺88.72⫹1.70DE%, 共9兲
with the correlation coefficient R⫽0.92.
In addition to effluent quantification, we have the
following observations from the FTIR emissions profiles in
Fig. 3:
共1兲 The maximum concentrations of SiF4 emitted from
NF3 -based cleans are higher than that of the C2 F6 BKM.
This indicates that NF3 -based cleans remove deposition
residues faster than C2 F6 BKM.
共2兲 No SiF4 is emitted from the C2 F6 BKM that immediately
followed an NF3 -based clean. This confirms that the
NF3 -based cleans have completely removed deposition
residues from the chamber.
B. Process optimization by design of experiments
methodology
Common process parameters in NF3 /He in situ chamber
cleaning include rf power, chamber pressure, NF3 flow rate,
NF3 molar concentration, etc. For this study, the optimization
criteria were: Short clean time, low global warming emis-
sions 共kgCE兲, low consumption and high utilization of the
cleaning gas NF3 , and low reactor hardware damage due to
共6兲 overheating and/or ion bombardment-induced hardware deg-
radation. As reported in earlier attempts, some of the objec-
tives often compete with one another. For example, condi-
tions that offer the fastest clean time may 共and often do兲 lead
to higher global warming emissions, higher NF3 consump-
tion, and lower NF3 destruction efficiency. On the other
hand, conditions that yield nearly zero-global warming emis-
sions often have longer clean times.15,16 There is also a com-
peting optimization requirement for efficient simultaneous
cleaning of the inner part of a CVD chamber 共namely, the
共7兲 showerhead and the susceptor兲 and the outer part of the CVD
chamber 共namely, the chamber walls and other remote areas
that are downstream to the chamber兲. Operating conditions
共such as higher pressure兲 that speed up the inner-chamber
cleaning may lead to slow or even incomplete cleaning of the
peripheral areas of the chamber. In addition to competing
optimization requirements, NF3 -based plasmas can become
unstable or even collapse in the presence of large amounts of
highly electronegative species such as NF3 , F2 , F atoms, etc.
 4456 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004 Ji et al.

FIG. 4. Response surface of clean time vs NF3 flow rate and NF3 mol %.
The chamber pressure is fixed at 3 Torr.
FIG. 5. Response surface of global warming emissions kgCE vs NF3 flow
rate and NF3 mol %. The chamber pressure is fixed at 3 Torr.

Unstable and/or collapsed plasmas adversely affect all as-

共1兲 A higher NF3 mol % does not necessarily lead to shorter
pects of chamber cleaning performance, and may worsen re-
clean time.
actor hardware damage.
共2兲 A higher NF3 flow rate can reduce the clean time at low
To solve such a complex optimization problem, we
NF3 concentration. However, the global warming emis-
adopted a systematic and statistically validated DOE
sions kgCE increases dramatically with higher NF3 flow
approach.39 As reported in the companion paper,31 it took us
rate.
two rounds of exploratory DOEs before we identify a pro-
共3兲 Both clean time and global warming emissions kgCE
cess parameter space that ensures stable uniform discharges
exhibit a parabolic dependence on chamber pressure,
in all of the runs. In this study, we kept the same rf power
with minimum values around 3 Torr.
共950 W, or approximately 2.9 W/cm2 power density兲 as that
in the Applied Materials C2 F6 BKM. The other three impor- We can now examine the parametric functional depen-
tant process parameters are varied within the following dence in Figs. 4 through 7 to facilitate the chamber clean
ranges: 216 –384 standard cubic centimeter per minute optimization. From the illustrations above, it is apparent that
共sccm兲 NF3 flow, 10.49–15.52 mol % NF3 concentration, 13 mol % NF3 concentration and 3.0 Torr chamber pressure
and 1.32– 4.68 Torr chamber pressure. Identifying the viable at 950 W rf power offer the most preferred conditions to
parameter space allowed us to employ a fully rotatable 共␣ achieve both fast clean 共short clean time兲 and low global
⫽1.68兲 central composite response surface design. A fully warming emissions 共low kgCE兲. To optimize a NF3 flow
rotatable central composite design provides high statistical
validity and optimization predictability. The DESIGN-
EXPERT® software was utilized to facilitate the design and
analysis of the DOE.40
The DOE methodology allowed us to visualize func-
tional dependence of chamber cleaning performance indica-
tors on process parameters via response surface analysis, as
shown in Figs. 4 –7. The statistical validity of the response
surface models is supported by the excellent linearity in the
normal plots of residues. For the clean time model, the linear
least-squares fit between the normal % of probability and the
studentized residues has a correlation coefficient R⫽0.987
and a standard deviation ␴⫽0.16. The corresponding R and
␴ values for the kgCE model are 0.996 and 0.087, respec-
tively. To further verify the models, extra runs were per-
formed. The clean time and kgCE data from the extra runs
are compared with the response surface model predictions.
As shown in Table I, all seven extra runs are in excellent
agreement with the model predictions—well within the 95%
probability intervals. FIG. 6. Response surface of clean time vs NF3 flow rate and chamber
Here are some of the notable features in Figs. 4 –7: pressure. The NF3 concentration is fixed at 13 mol %.

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 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004 Ji et al. 4457

than that of the C2 F6 BKM. DOE run No. 5 was a notable

FIG. 7. Response surface of global warming emissions kgCE vs NF3 flow
rate and chamber pressure. The NF3 concentration is fixed at 13 mol %.
rate, tradeoffs need to be made between competing depen-
dences of clean time and kgCE. We find that an overall op-
timized flow rate of 300 sccm NF3 flow offers the best bal-
ance between clean time and kgCE emissions. However,
depending on optimization priorities, we can choose either a
slightly higher NF3 flow rate for a faster clean time, or a
slightly lower NF3 flow rate for a lower kgCE. Table II lists
some of these variations of the optimized recipes and results.
For comparative reference, an Applied Materials standard
共BKM兲 C2 F6 clean was also performed on the same CVD
chamber. Table III lists the C2 F6 BKM recipe and cleaning
performance. The clean time and the kgCE values in Table
III are averages of eight repeated measurements randomly
interleaved between the NF3 optimization runs.
SiF4 volumetric emission from each cleaning experiment
is also an important performance indicator. If a DOE experi-
mental run cleans the chamber completely, the SiF4 volumet-
ric emission should be equal to or higher than that of the
C2 F6 BKM. Table II also lists the SiF4 volumetric emissions
relative to the C2 F6 BKM. All optimized NF3 runs removed
equal or slightly higher amounts of SiF4 , confirming that
these runs cleaned the chamber completely. Relative SiF4
volumetric emissions from all the DOE and extra runs are
shown in Fig. 8. Most of the NF3 DOE and all of the extra
NF3 runs emitted equal or slightly higher amounts of SiF4
exception: It had significantly less SiF4 emission than the
C2 F6 BKM, possibly suggesting an incomplete clean. In fact,
DOE run No. 5 was an outlier during the initial DOE data
modeling and statistical analysis, and was subsequently ig-
nored in the final DOE data modeling.
Figure 9 shows the relative comparison between the
standard C2 F6 BKM clean and the balanced optimal dilute
NF3 clean. All values in Fig. 9 are normalized to the corre-
sponding values of the C2 F6 BKM. The optimized dilute NF3
clean reduces global warming emissions by 96% and short-
ens the clean time by 15%. Because of the much higher
FគUE%, the optimized dilute NF3 clean consumes 77% less
cleaning gas on a weight basis.
Minimizing hardware damage is another objective of the
optimization. In general, poorly optimized in situ plasmas
can accelerate reactor hardware degradation due to several
mechanisms: 共i兲 Reactor components, particularly the rf
powered showerhead, are subject to energetic ion bombard-
ment, which can cause sputtering and ion-enhanced damage;
共ii兲 most of the internal components of the PECVD reactor
are made of aluminum alloys, which are not highly resistive
to damage or corrosion induced by the aggressive nature of
fluorine-based plasmas; and 共iii兲 most of the internal compo-
nents of the PECVD reactor are kept at high temperatures
during both the deposition and the cleaning processes. For
example, for this study, the susceptor within the Applied Ma-
terials P-5000 D⫻L PECVD reactor was lamp heated to
maintain it at 400 °C. Elevated temperatures also hasten alloy
surface reactions that lead to hardware degradation.
NF3 -based plasmas generate large amounts of highly reactive
radicals and ions, such as F, NF2 , NF⫹ 2 , etc. Furthermore,
these ions are typically more energetic within NF3 -based
plasmas. Consequently, hardware degradation in NF3 -based
in situ chamber cleaning is of a bigger concern than that in
C2 F6 -based cleans.
Li et al.41 studied aluminum alloy 6061 surface damage
when samples were subjected to in situ NF3 /Helium plas-
mas. The authors monitored plasma-induced surface damage
by real-time in situ spectroscopic ellipsometry, and by pos-
texposure x-ray photoelectron spectroscopy analysis. Under
reactive ion etch 共RIE兲 conditions, the authors find that
plasma-induced surface damage can be minimized when the
NF3 concentration is below a threshold of 40 mol %.41 While
the specific damage threshold concentration may depend on
individual reactor design and materials of construction, Li

TABLE I. DOE model validation extra runs.

Predicted Measured
NF3 Flow He Flow NF3 Pressure clean time ⫾1 ␴ clean time Predicted Measured
Recipe 共sccm兲 共sccm兲 mol % 共Torr兲 共s兲 共s兲 kgCE ⫾1 ␴ kgCE

Ex1 300 1769 14.5 3.00 79⫾10 85 0.60⫾0.12 0.54

Ex2 300 1843 14.0 3.00 76⫾10 80 0.58⫾0.12 0.59
Ex3 300 1843 14.0 2.75 74⫾10 74 0.56⫾0.12 0.47
Ex4 300 1769 14.5 2.75 77⫾10 73 0.57⫾0.12 0.47
Ex5 300 2008 13.0 2.50 70⫾10 76 0.53⫾0.11 0.53
Ex6 300 1843 14.0 2.00 74⫾11 80 0.51⫾0.13 0.55
Ex7 250 1673 13.0 3.00 75⫾11 71 0.31⫾0.12 0.29

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 4458 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004 Ji et al.

TABLE II. Optimized dilute NF3 clean recipes and results.

Clean time Clean gas usage SiF4 emission

NF3 He ⫾1 ␴ 共s兲 kgCE ⫾1␴ 共g兲 relative to
Flow Flow 关Relative change 关Relative change 关Relative change NF3 DE% FគUE% C2 F6 BKM
Recipe 共sccm兲 共sccm兲 to C2 F6 BKM兴 to C2 F6 BKM兴 to C2 F6 BKM兴 ⫾1 ␴ ⫾1 ␴ ⫾1 ␴

Balanced 300 2008 71⫾2 0.54⫾0.03 1.13 85.91 59.83 1.06

关⫺15%兴 关⫺96%兴 关⫺77%兴 ⫾1.15 ⫾2.51 ⫾0.05
Faster 384 2570 70 0.91 1.41 78.64 44.12 1.00
关⫺15%兴 关⫺93%兴 关⫺72%兴
Lower 250 1673 71 0.29 0.95 93.94 67.63 1.01
Emission 关⫺14%兴 关⫺98%兴 关⫺81%兴
Lowest 216 1445 74 0.12 0.82 99.24 76.29 1.01
Emission 关⫺11%兴 关⫺99%兴 关⫺84%兴

et al.41 observed that surface damage decreases significantly
as NF3 concentration is lowered.
Hsueh et al.38 characterized the relative abundance and
ion energy distribution functions 共IEDFs兲 of major positive
ions at the grounded electrode in 25 mol % NF3 /Ar, 25
mol % NF3 /He, 25 mol % NF3 /O2 , and 50 mol % C2 F6 /O2
plasmas. For 25 mol % NF3 /He plasmas, the authors observe
that as the pressure increases, the IEDFs change from bimo-
dal to unimodal distribution, and both maximum ion energy
and the average ion energy decrease. The authors attribute
changes in IEDFs to the dynamics of ion transportation
across the sheath. They also observed that a ‘‘soft’’ IEDF for
the most abundant ion NF⫹ 2 in 25 mol % NF3 /He plasmas is
obtained when chamber pressure is ⭓0.75 Torr. Again, the
specific threshold values may change with different reactors.
But the general trend offers a practical guideline for produc-
tion reactor process optimization: Lower NF3 concentration
and higher chamber pressure can reduce plasma-induced
hardware degradation. Since 13 mol % NF3 concentration is
less than the 40% threshold in Li et al.’s study,41 and a cham-
ber pressure of 3 Torr is significantly higher than 0.75 Torr in
Hsueh et al.’s38 study, one can infer that the optimized reci-
pes should be within the ‘‘moderate’’ ranges to alleviate
plasma-induced hardware damage. Of course, a direct exami-
nation or quantification of hardware damage should come
from a marathon test of thousands of wafers. Such a mara-
thon test was beyond the scope of this work.
Helium is one of the most efficient coolant gases for
carrying away excessive heat from hot surfaces. The high
flow rate of helium diluent and the relatively higher pres-
sures 共2.0–3.5 Torr兲 within the optimized recipes offer an-
other distinct advantage: They prevents the susceptor and
showerhead surfaces from overheating. Fluorocarbon and O2
are not effective coolant gases. As a result, the susceptor and
showerhead can become overheated, particularly at higher rf
powers 共such as 1000 W兲. On a production platform, suscep-
tor overtemperature triggers automatic process shutdown,
causing productivity and yield losses. Moreover, the over-
heating of the interior surfaces of the reactor accelerates
component degradation. Therefore, the effective cooling
from high helium flow not only improves productivity and
yield, but also alleviates hardware degradation.
C. Chamber clean time and fluorine atom density
Spectral features in optical emissions spectra of NF3 /He
plasmas have been assigned in a previous publication.38 In
addition to endpoint detection, OES data also provide a way
to estimate atomic fluorine density by actinometry.42 We use
the following equation to estimate the relative atomic fluo-
rine density in helium diluted plasmas
ñ F⬀ñ HeI F共 704兲 /I He共 688兲 , 共10兲
where I F(704) is the OES intensity of atomic fluorine transi-
ⴰ
tion 2s 2 2 p 4 ( 3 P)3p 2 P3/2 →2s 2 2 p 4 ( 3 P)3s 2 P3/2 at 703.75 nm,
and I He(668) is the OES intensity of atomic helium transition
1s3d 1 D2 →1s2p 1 Pⴰ1 at 667.82 nm. ñ He in Eq. 共10兲 is the
relative atomic helium density estimated by
f HeP
ñ He⬀ ,
f He⫹ f NF3 共 1⫺DE%/100兲 ⫹ f NF3 共 DE%/100兲 * 3.5
共11兲
where P is the reactor pressure 共Torr兲, f He and f NF3 are feed
gas flow rates of helium and NF3 , respectively, and DE% is
NF3 destruction efficiency. Equation 共11兲 assumes complete
NF3 dissociation as
NF3 →0.5N2 ⫹3F, 共12兲
which yields a ‘‘flow expansion coefficient’’ of 3.5. Although
Eq. 共11兲 is a gross simplification of actual complex reactions,
we have found changing the flow expansion coefficient from
3.5 to some other values does not change the key conclu-
sions.

TABLE III. Standard C2 F6 BKM recipe and results.

C2 F6 Flow O2 Flow Pressure Power Clean Time Clean gas C2 F6 DE% FគUE%
共sccm兲 共sccm兲 共Torr兲 共W兲 ⫾1 ␴ 共s兲 KgCE ⫾1␴ usage 共g兲 ⫾1 ␴ ⫾1␴

600 600 4 950 83⫾3 12.72⫾0.45 5.0 35.84⫾1.35 8.61⫾0.40

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 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004 Ji et al. 4459

FIG. 8. SiF4 volumetric emission relative to the C2 F6 BKM for the DOE
and extra runs. A value of 1.0 or higher, i.e., a marker above the dashed line,
indicates that the experimental run removed equal or larger amount of SiF4
than the C2 F6 BKM.
FIG. 10. Correlation between relative fluorine atom density ñ F and
* DE), where p NF is the NF3 partial pressure before plasma ignition,
(p NF3 3
and DE is the NF3 destruction efficiency 共DE%/100兲.

where the reactor volume V r ⫽4500 cm3 , and gas tempera-

It is interesting to examine the dependence of relative
ture T r ⬇473 K; P r is the reactor pressure; and P s and T s are
atomic fluorine density on various process parameters. Fig-
standard pressure and temperature, respectively. The total
ure 10 shows the correlation between relative fluorine atom
gas flow f t is estimated by
* DE), where p NF is the NF3 partial pres-
density ñ F and (p NF
3 3
sure before plasma ignition, and DE⫽DE%/100, where DE% f t ⫽ f He⫹ f NF3 共 1⫺DE%/100兲 ⫹3.5f NF3 共 DE%/100兲 ,
is NF3 destruction efficiency as defined by Eq. 共5兲. A linear 共15兲
least-squares fit of the data gives
where DE% is the NF3 destruction efficiency 共%兲 and f NF3 is
ñ F⫽ 共 6.8⫾0.1兲共 p NF
* DE兲 , 共13兲 the NF3 feed gas flow rate. Again, the effect of NF3 disso-
3
ciation in Eq. 共15兲 is simplified by reaction 共12兲. A linear
* DE is the
with a correlation coefficient R of 0.92. Since p NF
3 least-squares fit gives
portion of feed gas NF3 that undergo dissociation reactions,
it is the source of fluorine atoms in the plasma. The linear ñ F⫽ 共 10.69⫾0.17兲 t r , 共16兲
correlation of Eq. 共13兲 is consistent with the intuition, and
with a correlation coefficient R of 0.95. As discussed in Sec.
validates the actinometry Eq. 共10兲.
III A, steady-state fluorine atom density within a plasma in-
Figure 11 shows the correlation between relative fluorine
side a completely cleaned chamber is determined by two
atom density ñ F and gas residence time inside the reactor.
competing processes: F atom production via various disso-
The gas residence time inside the reactor t r 共seconds兲 is es-
ciative collisions such as reactions 共1兲 and 共2兲, and F atom
timated by
loss due to recombination 关e.g., forming F2 via third-body
60V r P r T s collision in reaction 共4兲兴. According to Fig. 11 and Eq. 共16兲,
t r⫽ , 共14兲 increasing the gas residence time t r appears to enhance the
P s f tT r
fluorine atom production mechanisms more than the loss

FIG. 9. Relative performance comparison between the optimized NF3 recipe FIG. 11. Correlation between relative fluorine atom density ñ F and gas
and the C2 F6 BKM. residence time.

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 4460 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004
FIG. 12. Correlation between clean time and relative fluorine atom density
ñ F . Open circles are data from the third round of DOE, except the three
high pressure runs that are denoted by triangles. Solid line is linear least-
squares fit of the selected 共open circle兲 data points.
pathways. This suggests that F atom production is the rate
limiting process that determines the fluorine atom density in
the plasmas.
Under most RIE conditions, etch rates of SiO2 and Si3 N4
in CF4 /O2 , NF3 /Ar, and NF3 /He plasmas often increase
linearly with increasing fluorine atom density in the
plasma.11–13,35,38 Intuitively, a higher SiO2 etch rate would
lead to a shorter chamber clean time. Hence, higher fluorine
atom density ñ F should be correlated with a shorter clean
time. Figure 12 examines the relation between relative fluo-
rine atom density ñ F and clean time. For most of the runs 共as
denoted by the open circles in Fig. 12兲, the overall trend is a
shorter clean time at higher ñ F , consistent with the intuition.
However, the correlation between clean time and ñ F is sta-
tistically rather weak. There are three notable exceptions, as
denoted by the solid triangle points in Fig. 12. We will dis-
cuss these exceptions later. These exception points, and the
weak overall correlation between ñ F and clean time reveal
the dynamical differences between RIE in small parallel-
plate reactors and chamber cleaning in production PECVD
reactors.
A nonlinear correlation between fluorine atom density n F
and SiO2 etch rate was observed by Donnelly et al.32 in
CF4 /O2 and NF3 /Ar plasma etching of SiO2 . The authors
attributed the nonlinearity to ion-enhanced etch mechanism.
In general, the SiO2 total etch rate 共ER兲 can be modeled by a
combination of spontaneous chemical etch rate ERchem and
ion-enhanced etch rate ERion13
ER⫽ERchem⫹ERion.
The chemical etch rate ERchem in the absence of ion bom-
bardment or competing reactions was determined by Flamm
et al.43,44 and Donnelly et al.32 as
ERchem 共nm/min)⫽6.14⫻10⫺14n FT s1/2
⫻exp共 ⫺E a /k B T s 兲 ,
where n F is the fluorine atom density, T s is the substrate
surface temperature, and the activation energy E a was deter-
mined to be 0.163 eV. During chamber cleaning, various
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Ji et al.
TABLE IV. Estimated SiO2 chemical etch rate ERchem by fluorine atoms.
Surface temperature T s (°C) ERchem 共nm/min)
65 50
100 89
200 293
400 1146
parts of the chamber internal surfaces are held at vastly dif-
ferent temperatures. For example, the chamber wall surface
is maintained at 65 °C by a recirculating temperature control-
ler; the susceptor is maintained at 400 °C by lamps; and the
showerhead temperature is in between these two extremes.
We can estimate the upper limit of the fluorine atom density
n F by the following simplifications and assumptions:
共1兲 Neutral gas temperature T g is 200 °C.
共2兲 Chamber pressure is 3 Torr.
共3兲 NF3 concentration in the feed gas is 13 mol %.
共4兲 All of the fluorine atoms in the plasma react with SiO2 to
form SiF4 , and this is the only pathway for SiF4 forma-
tion.
Although assumption 共4兲 is a gross simplification of the
complex plasma–surface reactions, at least it allows basic
mass balance and is supported by the fact that spontaneous
thermal etching of SiO2 by NF3 and F2 molecules is much
slower than etching by atomic fluorine. Taking a typical
FគUE% of 50%, the fluorine atom density n F is estimated to
be 1⫻1016 cm⫺3 . Table IV gives the estimated SiO2 ERchem
from Eq. 共18兲 at various surface temperatures. We can infer
from Table IV that spontaneous thermal etching only makes
a minor contribution to the total ER on chamber walls at
65 °C. On the other hand, ERchem can be a significant com-
ponent of the total etch rate at the susceptor at 400 °C. This is
consistent with the observation of other investigators that
spontaneous thermal etching of SiO2 by fluorine atoms is not
as important as ion-enhanced etching at temperatures below
100 °C.13,32,45,46
Using an apparatus with beams of fluorine atoms 共F兲 and
argon ions (Ar⫹ ), Gary et al.46 determined the ion-enhanced
SiO2 ER as
ERion⫽ ␤ I ␪ F , 共19兲
where I is the ion flux; ␪ F is the local fraction of fluorinated
surface sites, and can be approximately taken as 1 because
the neutral fluorine to ion flux ratio (F/Ar⫹ ) is always over
three orders of magnitude higher than ion flux in typical
共17兲 capacitively coupled plasmas; and ␤ is the ion-enhanced
etching yield given by
␤ ⫽b 共 E 1/2
i ⫺E th 兲 ,
1/2
共20兲
where b is an energy dependent yield parameter, E i is the ion
energy, and E th is the surface process energy threshold and is
determined to be 4 eV.46 Ion flux and average ion energy may
共18兲
be estimated if the plasma density, electron temperature, and
plasma sheath potential are known. Unfortunately, the com-
pact rf matching and delivery circuits on the commercial
Applied Materials P-5000 DxL reactor precluded convenient
 J. Appl. Phys., Vol. 95, No. 8, 15 April 2004
access for rf electrical measurement. In a small laboratory
scale parallel-plate reactor, Hsueh et al.38 measured both ion
flux and IEDFs by energy resolved electrostatic quadruple
mass spectrometer. The authors observe that both increasing
the pressure and increasing the plasma electronegativity
leads to lower incident ion energies, which in turn leads to a
lower ERion. Gray et al.46 observe that at a flux ratio F/Ar⫹
of 300 or higher, the SiO2 etch rate nearly reaches a plateau
as F/Ar⫹ further increases. This implies that a further in-
creasing of the atomic fluorine flux can no longer increase
the ER. The observations of Donnelly et al.32 and Gray
et al.46 provide some insight for us to understand the weak
linear correlation between relative atomic fluorine density ñ F
and clean time in our data.
The lack of a strong linear correlation between ñ F and
clean time in Fig. 12 may suggest that the atomic fluorine
density is not the limiting factor for clean time. In addition to
fluorine atom density, clean time is also affected by other
important factors, such as the diffusion of reactive species
from the center of the plasma to chamber walls, recombina-
tion of reactive species, reactor gas residence time, etc. In
addition, the flux and energy distribution of reactive ions,
such as NF⫹ ⫹ ⫹
2 , NF , F , etc., also play an important role.
With a lower mass, sheath accelerated He⫹ is not as effective
as Ar⫹ to activate SiO2 surfaces to enhance etching reac-
tions. Thus, high fluxes of atomic and ionic fluorine-
containing species are essential for maintaining high ERs in
helium diluted NF3 plasmas. The three exception data points
in Fig. 12 are from runs with higher chamber pressures 共4 or
4.68 Torr兲. At high chamber pressures, plasmas become more
confined within the two electrodes. Although the atomic
fluorine emissions at 703.75 nm may be intense inside the
discharge, both neutral fluorine atoms and ions suffer more
recombination collisions as they diffuse out to the chamber
walls, resulting in lower fluxes incident upon the wall sur-
faces of the chamber. In addition, ion energies become lower
at higher pressures. This further reduces the SiO2 ER. As a
result, longer clean times are observed in these runs.
The complex dependency of clean time on fluorine den-
sity, residence time, and reactive ion production rates, are
manifested by the complex response surfaces of clean time
versus various process parameters, as shown in Figs. 4 –7
earlier. For quantitative modeling of chamber clean time in a
production PECVD chamber, we need to dissect the chamber
into several characteristic zones to account for vast differ-
ences in SiO2 residue film thickness, surface temperature,
neutral and ion fluxes, and ion energies at different parts of
the chamber. Validation of the model requires detailed ex-
perimental data in each of the characteristic zones. Obvi-
ously, this is a highly challenging task. A number of investi-
gators have made some efforts toward achieving such an
aggressive goal.47,48
IV. CONCLUSIONS
The performance of NF3 -based in situ PECVD chamber
cleaning has complex dependencies on several process pa-
rameters, as revealed by the response surfaces from the DOE
reported here. In general, a shorter clean time can be ob-
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Ji et al. 4461
tained with a higher NF3 flow rate, medium pressure 共3 Torr
or less兲, and dilute NF3 mol % 共around 13 mol %兲. On the
other hand, lower global warming emissions 共kgCE兲 can be
achieved with a lower NF3 flow rate, medium pressure, and
dilute NF3 mol %. For our reactor system, optimal process
parameters include 13 mol % NF3 concentration and 3 Torr
pressure. However, the NF3 flow rate often has opposite ef-
fects on clean time and global warming emissions. Similar to
PFC-based chamber cleaning, optimization of dilute NF3 in
situ PECVD chamber cleaning is a balancing act with regard
to the NF3 flow rate. Several optimized dilute NF3 in situ
clean processes are reported here. The results demonstrate
that dilute NF3 -based in situ chamber cleaning can be a vi-
able alternative to PFC-based in situ cleans with significant
benefits.
An analysis of atomic fluorine density by actinometry
shows there are sufficient fluorine atoms in stable and intense
NF3 plasmas so that fluorine density is not the limiting factor
for clean time. In addition to fluorine atom density, chamber
clean time is also affected by other important plasma prop-
erties, such as the flux and energy distributions of reactive
ions, and diffusion and recombination of reactive species be-
fore they reach the chamber walls to react with deposition
residues. While specific process recipes may depend on in-
dividual reactor design and deposition processes, we believe
the methodology and results reported here can provide some
practical guidance for further optimization and marathon
tests on dilute NF3 -based in situ PECVD chamber cleaning
in a production environment.
ACKNOWLEDGMENTS
The authors acknowledge the technical assistance from
Mark Bitner and helpful discussions with Dr. Delwin Elder,
Dr. Andrew Johnson, Dr. Ray Virtis, Dr. Robert Ridgeway,
Dr. Peter Maroulis, Dr. Xiaoye He, Dr. Pingping Ma, Dr.
Gabriel Font, and Dr. Lowel Morgan. They also thank Air
Products and Chemicals, Inc. for permission to publish this
work.
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