Ex Parte Pavel et al

Board of Patent Appeals and Interferences

Sep 29, 2008

10776672 (B.P.A.I. Sep. 29, 2008)

UNITED STATES PATENT AND TRADEMARK OFFICE
____________

BEFORE THE BOARD OF PATENT APPEALS
AND INTERFERENCES
____________

Ex parte ELIZABETH G. PAVEL,
MARK N. KAWAGUCHI, and JAMES S. PAPANU,
Appellants
____________

Appeal 2008-4297
Application 10/776,6721
Technology Center 1700
____________

Decided: September 29, 2008
____________

Before EDWARD C. KIMLIN, THOMAS A. WALTZ, and
MARK NAGUMO, Administrative Patent Judges.

NAGUMO, Administrative Patent Judge.
DECISION ON APPEAL

1 Application 10/776,672, Method and Apparatus for Performing Hydrogen
Optical Emission Endpoint Detection for Photoresist Strip and Residue
Removal, filed 11 February 2004. The specification is referred to as the
“672 Specification,” and is cited as “Spec.” The real party in interest is
listed as Applied Materials, Inc. (Supplemental Appeal Brief filed 2
November 2007) Br. 2.)

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A. Introduction
Elizabeth G. Pavel, Mark N. Kawaguchi, and James S. Papanu
(“Pavel”) timely appeal under 35 U.S.C. § 134(a) from the final rejection of
claims 1, 2, 6, 7, 9, 14, 16, 17, 21, 22, 28, and 30-45, which are all of the
pending claims. We AFFIRM.
The subject matter on appeal relates to processes of removing or
etching photoresist from a substrate by a plasma.
Claims 1 and 35 are representative:
Claim 1
A method of removing a photoresist layer comprising:
positioning a substrate comprising a photoresist layer into a
processing chamber;
removing the photoresist layer using a plasma;
monitoring the plasma for both a byproduct optical emission
and a reagent optical emission during the process; and
stopping the etching upon the byproduct optical emission
obtaining a first level and the reagent optical emission obtaining
a second level.
(Claims App., Br. 10, indentation added.)
Claim 35
A method of etching a photoresist layer comprising:
providing a substrate comprising a photoresist layer to a process
chamber;
etching the photoresist layer using a plasma;
determining an early endpoint indicator by monitoring the
plasma for a reagent optical emission while etching; and
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determining a final endpoint indicator by monitoring the plasma
for a byproduct optical emission while etching.
(Claims App., Br. 12, indentation added.)
Independent claim 16 is similar to claim 35, but in place of the two
“determining” steps, recites only “monitoring the plasma for both a
byproduct optical emission and a reagent optical emission while etching.”
(Claims App. , Br. 11.)
Grounds of Rejection:
The Examiner has maintained the following grounds of rejection:2
A. Claims 1, 7, 9, 16, 21, 22, and 31-45 stand rejected under
35 U.S.C. § 103(a) in view of the combined teachings of
Ishihara3 and Powell. 4
B. Claims 2, 6, 14, and 17 stand rejected under 35 U.S.C. § 103(a)
in view of the combined teachings of Ishihara, Powell, and
Hallock5
C. Claims 28 and 30 stand rejected under 35 U.S.C. § 103(a) in
view of the combined teachings of Ishihara, Powell, and Smith6

2 Examiner’s Answer mailed 22 January 2008 (“Ans.”).
3 Shigenori Ishihara, Organic Substance Removing Methods, Methods of
Producing Semiconductor Device, and Organic Substance Removing
Apparatuses, U.S. Patent Application Publication US 2001/0027023 A1
(2001).
4 Gary Powell and Richard L. Hazard, Method and Deice Utilizing Plasma
Source for Real-Time Gas Sampling, U.S. Patent Application Publication
US 2002/0135761 A1 (26 September 2002), based on application
10/038,090, filed 29 October 2001.
5 John Scott Hallock et al., Process for Removal of Photoresist after Post Ion
Implantation, U.S. Patent Application Publication US 2002/0151156 A1
(17 October 2002), based on application 09/742,721, filed 22 December
2000.
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B. Findings of Fact
Findings of fact ("FF") throughout this Decision are supported by a
preponderance of the evidence of record.
672 Specification
1. According to the 672 Specification, semiconductor device fabrication
comprises depositing various layers of dielectric, semiconducting, and
conducting layers on a silicon substrate, in which features are defined on the
substrate by lithography and etching. (Spec. 1:[0003].)
2. In the lithographic and etching steps, a layered substrate is coated with
photoresist, the photoresist is patterned, and then the pattern is transferred to
the underlying layers during etching using the patterned photoresist as an
etch mask. (Spec. 1:[0003].)
3. From this statement, we understand the term “etch” to refer to the
transfer of a pattern to the substrate.
4. In the words of the 672 Specification, “[m]any of these etch processes
leave photoresist and post-etch residues on the substrate and must be
removed before performing the next process step.” (Spec. 1:[0003].)
5. From this statement, we infer that an etch process typically removes at
least some of the photoresist from the substrate.
6. According to the 672 Specification, the patterned photoresist also
serves as an ion implant mask for preferentially doping semiconductor

6 Michael Lane Smith, Jr., et al., Method and Apparatus for Monitoring
Plasma Processing Operations, U.S. Patent 6,419,801 B1 16 July 2002,
based on application 90/065,358, filed 23 April 1998.
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substrates in selected areas by exposing those areas to ions or electron beams
of implant species such as arsenic, boron, phosphorus, or other species.
(Spec. 1:[0004].)
7. The ion implantation process is said to dehydrogenate the photoresist
material, resulting in a hydrogen deficient, carbonized crust layer.
(Spec. 1:[0004].)
8. As a result, the characteristics of the photoresist material are said to
vary vertically, and uniform removal (“stripping”) of the photoresist from
the structure can be difficult. (Spec. 2:[0004].)
9. The 672 Specification identifies a need for a technique for monitoring
removal of the photoresist such that the removal process can be controlled as
the characteristics of the material change. (Spec. 2:[0004].)
10. Optical emission spectroscopy is said to be commonly used to detect
the endpoint of plasma etch processes. (Spec. 2:[0005].)
11. The endpoint is said usually to be based on increasing signal for
reactants or decreasing signal for products. (Spec. 2:[0005].)
12. Somewhat more particularly, the 672 specification states that “[t]he
endpoint is identified when either the reactants or products attain a specific
concentration (i.e., the respective signals cross a threshold level.)”
(Spec. 2:[0005].)
13. According to the 672 Specification, however, “such an endpoint
detection technique does not account for the variations in the characteristics
of a photoresist layer that has been exposed to an ion beam.”
(Spec. 2:[0005].
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14. The 672 describes its invention as comprising the use of the hydrogen
optical emission peak to identify the endpoint of a photoresist stripping
process. (Spec. 2:[0007].)
15. This is said to be especially useful for crust removal during post-
implant photoresist stripping because the hydrogen content of the crust layer
is significantly lower than that of the bulk photoresist. (Spec. 2:[0007].)
16. As a result, the entire photoresist removal is said to be monitored in a
simpler and more direct manner using the hydrogen signal than using, for
example, only an oxygen signal from the reactants. (Spec. 2:[0007]
and 3:[0008].)
17. In the embodiments involved in this appeal, at least one additional
emission peak, e.g., an oxygen or other reactant signal, or signal from a by-
product volatile gas formed from the components of the bulk photoresist is
also said to be monitored to provide more robust or flexible endpoint
control. (Spec. 3:[0008].)
18. According to the 672 Specification, identification of an early endpoint
indicator is provided by monitoring the reagent oxygen peak, and
identification of a late/final endpoint indicator is provided by monitoring the
by-product hydrogen peak. (Spec. 6:[0026].)
19. Because hydrogen is a by-product peak and oxygen is a reactant peak,
the hydrogen and oxygen signals are said to mirror each other, and
monitoring both is said to provide a backup, so that if one is missed, the
endpoint still can be detected by the other. (Spec. 7:[0026].)
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20. In the words of the 672 Specification, “[d]ual wavelength endpoint
triggering occurs when either wavelength meets the endpoint conditions.”
(Spec. 7:[0026].)
21. According to the 652 Specification, “[t]he oxygen emission peak(s)
of 777nm and/or 845nm can also be utilized, either singly or jointly in
combination with the hydrogen emission peak. The relative intensities of
the peaks so measured and monitored could be indicative of the conditions
of the plasma sources and chamber surfaces and be used to provide a proper
‘fingerprint’ of a clean or ‘golden’ chamber.” (Spec. 10:[0039].)
Ishihara
22. Ishihara relates to processes of removing a photoresist having an ion-
implanted region from a semiconductor wafer in a chip manufacturing
process. (Ishihara 1:[0002].)
23. Ishihara teaches that “when a photoresist used as a mask material
during local ion implantation is to be removed, since the photoresist has
become difficult to be ashed because the implanted ions deteriorate (or
affect) or harden the vicinity of the surface of the photoresist, the removal of
the photoresist takes a long time.” (Ishihara 1:[0008]; emphasis added.)
24. We understand Ishihara to be teaching that ion implantation in the
photoresist results in the formation of a crust on the photoresist that is hard
to remove by conventional techniques.
25. According to Ishihara, such a photoresist is normally removed
(“ashed”) by reaction with a plasma of oxygen containing a carbon-fluoride
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based gas that converts the ion species into volatile compounds with active
species of fluorine. (Ishihara 1:[0012].)
26. Areas of the substrate that are not coated with photoresist, however,
may be corroded by exposure to the active species of fluorine.
(Ishihara 1:[0012].)
27. Ishihara provides a two-step process to remove the photoresist while
suppressing the corrosion of areas of the substrate not covered with the
photoresist. (Ishihara 2:[0019].)
28. In an embodiment, a photoresist is coated on the surface of a
semiconductor substrate, exposed with a pattern, and developed
(Ishihara 5:[0116]); such a structure is shown in Ishihara Figure 3A (see
Ishihara 7:[0155]).
29. The substrate is then ion-implanted with arsenic, phosphorus, boron,
or similar materials (Ishihara 5:[0116]); such a structure is shown in Ishihara
Figure 3B (see Ishihara 7:[0157]).
30. The substrate, which contains exposed semiconductor areas, areas
covered by photoresist, and areas covered by ion-implanted (i.e., crusted)
photoresist, is then exposed in a “first mode” to a plasma generated in an
atmosphere comprising an oxygen-containing gas, a hydrogen-containing
gas, and a fluorine-containing gas (Ishihara 6:[0119].)
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31. Ishihara Figure 3C (described at Ishihara 7:[0160]), reproduced
below, shows the structure:

{Ishihara Figure 3C is said to show a step in the process}7
32. According to Ishihara, the ion-implanted regions 27 of the photoresist
are modified by a plasma treatment process in a “first mode” to make it
feasible to remove the resist by treatment in a “second mode” using a less
corrosive plasma generated from, e.g., only an oxygen-containing gas. (See
Ishihara 6:[0130].)
33. In the first mode, Ishihara teaches that because “the implanted ion
species of phosphorus, arsenic, or the like turn into fluoride or hydrides to
disappear in the first step, there appears no residue of the implanted ion
species.” (Ishihara 7-8:[0162].)
34. Ishihara also indicates that during the first mode, “[t]he region [of the
photoresist] deteriorated by the ion implantation may be removed at the
same time as this processing or may be only modified without being
removed.” (Ishihara 7:[0160]).)

7 The text in curly braces following the Figures is provided to ensure
compliance with section 508 of the U.S. Rehabilitation Act for publication
of this Decision on the USPTO website pursuant to the Freedom of
Information Act. It is not part of the Decision.
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35. Ishihara teaches that the switch from mode 1 to mode 2 can be based
on a signal from an in-situ monitor, such as monitoring “the light emission
caused by CO [309 nm] and H [656 nm] as products from the resist or by
O [777 nm] from the added gases . . . .” (Ishihara 6:[0135]; emission
wavelengths reported at 6:[0136].)
36. In the second mode, the residual photoresist is removed by a plasma
that does not disturb areas of the semiconductor device not covered by a
layer of photoresist. (Ishihara 6[0137].)
Powell
37. Powell teaches methods of monitoring the conditions in a reaction
chamber 101 by removing samples of the gases and analyzing their contents
by emission spectroscopy of a plasma generated from the gases in a side
excitation chamber 105. (Powell 1:[0018] and Powell Figure 1.)
38. Powell indicates that multiple peaks from multiple spectral regions
can be monitored at the same time, leading to enhanced effective signal to
noise ratio and better reaction endpoint detection. (Powell 4:[0030].)
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39. In Figure 11, Powell reports an example of monitoring the condition
of a chamber during treatment with an oxygen plasma, in which emission
from several species, e.g., oxygen at 777 nm, hydrogen at 656 nm, and CO
at 483 nm and at 520 nm, as well as fluorine and nitrogen, are monitored.
(Powell 7:[0051]): Figure 11 is shown below:

{Powell Figure 11 is said to show the emission of plasma components with
time}
40. In Powell’s words, Figure 11 shows that “[a]t approximately
5[minutes]:29[seconds], the carbon monoxide production begins to drop
steeply, as indicated by the peak centered at about 520 nm. At about the
same time, oxygen concentration increases, as indicated by the peak
centered at about 777 nm.” (Powell 7:[0051].)
41. Powell continues, “[t]he combination of decreased carbon monoxide
production and increased oxygen concentration indicates a depletion of
carbon from the chamber by the oxygen plasma.” (Powell 7:[0051].)
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42. Powell remarks further that “[m]onitoring depletion of materials from
a chamber during cleaning enables timing, control, and validation of the
cleaning process.” (Powell 7:[0051].)
43. Powell teaches further that:
[t]he monitoring may look for transitions in wall chemistry or a
predetermined chamber condition, based on a profile of a prior
chamber condition. The profile can include selected peaks,
selected bands, or a fall [sic: full?] spectrum in a predetermined
range. Analysis can be based, for instance, on peaks, spectral
differences or asymptotic changes in peaks or spectral
differences.”
(Powell 7:[0051].)
C. Discussion
The burden is on Pavel, as the Appellant, to demonstrate reversible
error in the Examiner’s rejections. See, e.g., In re Kahn, 441 F.3d 977,
985-86 (Fed. Cir. 2006) (“On appeal to the Board, an applicant can
overcome a rejection [under § 103] by showing insufficient evidence of
prima facie obviousness or by rebutting the prima facie case with evidence
of secondary indicia of nonobviousness.”) (quoting In re Rouffet, 149 F.3d
1350, 1355 (Fed. Cir. 1998)).
The Examiner finds that Ishihara describes a process of etching or
removing a photoresist layer that meets all the limitations of claims 1, 16,
and 35 but for the explicit monitoring of both a reagent and a by-product
optical emission; and (for claim 1) stopping the etching at certain signal
levels of each (Ans. 3); and (for claim 35) determining an early endpoint by
monitoring a reagent optical emission and determining a late endpoint by
monitoring a by-product optical emission. The Examiner finds, however,
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that Ishihara “clearly disclose[s that] it is possible to monitor [a] plurality of
emission[s] at the same time in order to control the endpoint (i.e. switching
time).” (Id. at 4.) Moreover, the Examiner finds that Ishihara teaches that
reagent (oxygen) emission and by-product (carbon monoxide, CO, and
hydrogen) emissions may be monitored. (Id.) The Examiner finds that
Powell teaches monitoring optical emissions from multiple species in a
plasma. (Id.) The Examiner concludes that it would have been obvious to a
person having ordinary skill in the art to monitor both reagent and by-
product emissions in order to obtain more accurate evaluation of the
progression of the plasma recipe and the endpoint. (Id.)
Pavel emphasizes that Ishihara does not teach monitoring both a by-
product emission and a reagent emission. (Br. 4.) Pavel argues that
combining the teachings of Ishihara and Powell would result in a process in
which a plasma would be formed and monitored external to the process
chamber. Accordingly, Pavel denies that a prima facie case of obviousness
has been established for any of the claims. (Br. 5.)
This argument misapprehends the rejection. We do not understand
the Examiner to have suggested that a person having ordinary skill in the art
would have adapted the entire apparatus described by Powell to perform the
process described by Ishihara with simultaneous observation of optical
emissions from multiple species. See, e.g., In re Keller, 642 F.2d 413, 425
(CCPA 1981) ("The test for obviousness is not whether the features of a
secondary reference may be bodily incorporated into the structure of the
primary reference; . . . Rather, the test is what the combined teachings of the
references would have suggested to those of ordinary skill in the art."). In
the present case, the ordinary worker would have learned from Powell, if it
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was not already appreciated from Ishihara, that the emission spectra of plural
species, including reagents and by-products, could have been
advantageously monitored simultaneously to indicate when to stop a given
plasma reaction. Powell’s teaching in paragraph 51 that “[t]he combination
of decreased carbon monoxide production and increased oxygen
concentration indicates a depletion of carbon from the chamber by the
oxygen plasma” (FF 40) would have been particularly relevant, as Ishihara
teaches an oxygen reagent and carbon monoxide as a product of reaction of
the photoresist with the oxygen plasma. Pavel has failed to show reversible
error in the Examiner’s rejection of claims 1 and 16.
Pavel objects further to the Examiner’s conclusion that monitoring the
reagent (oxygen) and by-product (CO) emissions suggested by Ishihara, and
the simultaneous monitoring suggested by Powell, would have suggested the
early endpoint indicator and the final endpoint indicator required by
claim 35, as well as by claims 42 and 43, which depend from claims 1
and 16, respectively. (Br. 5.) We are not persuaded, as we are confident
that the teachings of Powell would have suggested to the ordinary worker
that the reactant emission signal and by-product emission signal would have
provided indications, in the Ishihara process, that the first mode was nearing
the end. Moreover, as shown in Figure 11, it appears that the reactant signal
approaches its asymptotic value sooner than the by-product emission signal.
Thus, the reactant signal would have provided an “early endpoint indicator”
as recited in claim 35. Similarly, the ordinary worker would have
understood that the by-product signal would have provided a later indication
that the first mode was complete. This corresponds to the “final endpoint
indicator” required by claim 35. The level of skill in the art is quite high, as
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indicated by the sophistication of the prior art references. There is nothing
to suggest that applying a correlation derived from an example of cleaning a
chamber (Powell paragraph [0051]) to another example of etching or
removing photoresist from a semiconductor (Ishihara Figure 3C, reproduced
supra) would have been beyond the ordinary worker. Thus, Pavel has not
shown reversible error with regard to the rejection of claims 35, 42, or 43.
Claims 31, 33, and 39 (determining a condition of the plasma source)
The Examiner finds that Powell teaches determining the condition of
the plasma source (Ans. 5, citing Powell Figures 5, 6, 9, and 10, and
paragraphs [0028]-[0032]) and concludes that claims 31, 33, and 39 would
have been obvious. Pavel denies that there is any such teaching in these
passages and urges that the rejection of these claims be reversed. (Br. 6-7.)
In rebuttal, the Examiner maintains that “the condition of the plasma source
comprises any condition that [is] related to the plasma source including
emission spectrum, wavelength, and gas flow rate of the plasma.” (Ans. 9.)
Such conditions, the Examiner maintains, are determined by Powell. (Id.)
Pavel, in the Reply Brief,8 cites the disclosure in the 672 Specification that
relative intensities of oxygen and hydrogen peaks can be monitored and
could be indicative of conditions of the plasma source. (Reply Br. 6;
cf. FF 19.) Pavel asserts that this passage from the 672 Specification
indicates, without reading limitations into the claims, that the “condition”
means “a state of health of the plasma source.” (Reply Br. 6.)
It is fundamental that “during examination proceedings, claims are
given their broadest reasonable interpretation consistent with the

8 Reply Brief filed 22 April 2008, (“Reply Br.”).
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specification.” In re Hyatt, 211 F.3d 1367, 1372 (Fed. Cir. 2000). As Pavel
recognizes, it is improper to read limitations from preferred embodiments in
the specification into the claims. In re Am. Acad. of Sci. Tech. Ctr., 367 F.3d
1359, 1369 (Fed. Cir. 2004). The Examiner’s conclusion that determining
any condition related to the plasma source is within the scope of
“determining a condition of a plasma source” is not inconsistent with the
description in the 672 Specification that the relative intensities of various
peaks “could be indicative of the conditions of plasma sources.”
(Spec. 10:[0039]; FF 21.) Nor is the Examiner’s conclusion inconsistent
with Pavel’s assertion (Reply Br. 6) that “condition” here means “health,” as
both terms are so broad in the context of plasma sources that ascertaining
that a plasma exists falls within the ambit of the term. Powell’s teachings go
far beyond that level of determining characteristics—i.e., “conditions”—of
the plasma, and hence of the plasma source. Accordingly, we are not
persuaded that the Pavel has demonstrated reversible error in the Examiner’s
rejection of claims 31, 33, and 39.
Claims 41, 44, and 45 (cleaning cycle or components degrading)
Claims 41, 44, and 45 depend from upon claims 1, 16, and 35,
respectively, and add the further limitation that a determination be made
from a monitored optical emission whether a cleaning cycle is necessary or
whether components within the chamber are degrading. The Examiner finds
that Powell teaches determining the condition of the processing chamber in
paragraphs [0051]-[0053] (Ans. 5) and concludes that it would have been
obvious to the ordinary worker to adapt the processes taught by Ishihara to
include determining whether the chamber needs cleaning (id. at 6).
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Appellant objects that Powell teaches monitoring optical emissions
from an external process effluent. (Br. 7.) Pavel argues further that the
portion of Powell relied on by the Examiner provides “a chamber clean [sic]
process that may be monitored to determine when the chamber clean [sic] is
complete—not whether a chamber clean is necessary to begin with.” (Id.)
Pavel urges that no prima facie case of obviousness has been established.
(Id.)
These arguments are without merit. Powell teaches that “[p]lasma
etch reactors experience a build up of polymers and other etch byproducts,
which periodically must be cleaned or removed.” (Powell 7:[0052].) The
cleaning process described in paragraph [0051] involves monitoring oxygen
and carbon monoxide signals–signals that Ishihara recommends monitoring.
The knowledge that plasma etch reactors need periodic cleaning coupled
with the observation of the same signals during processing substrates that are
monitored during cleaning would have suggested to the person having
ordinary skill in the art that those same signals could have been used to
signal the need for cleaning.
Moreover, the process taught by Ishihara involves degrading a
component within the chamber, namely, the ion-implanted photoresist, and
monitoring the degradation. (FF 31-35.) Thus, Ishihara teaches determining
from optical emissions whether a component in the chamber is degrading.
We have already determined that monitoring both a reactant emission signal
and a by-product emission signal during the process would have been
obvious. Hence, any error in the Examiner’s reliance on Powell would have
been harmless regarding the obviousness of claims 41, 44, and 45.
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Rejections B (Hallock) and C (Smith)
Pavel does not contest the findings of the Examiner regarding Hallock
(Ans. 6) and Smith (Ans. 7). (Br. 8-9.) Rather, Pavel argues that neither
reference cures the alleged defects of Ishihara and Powell, and that a prima
facie case of obviousness has not been established. (Id.)
As we have held that Pavel has not shown reversible error in the
Examiner’s rejection of the independent claims, we find these later
arguments unpersuasive of reversible error.
D. Summary
In view of the record and the foregoing considerations, it is:
ORDERED that the rejection of claims 1, 7, 9, 16, 21, 22,
and 31-45 under 35 U.S.C. § 103(a) in view of the combined teachings of
Ishihara and Powell is AFFIRMED;
FURTHER ORDERED that the rejection of claims 2, 6, 14,
and 17 under 35 U.S.C. § 103(a) in view of the combined teachings of
Ishihara, Powell, and Hallock is AFFIRMED;
FURTHER ORDERED that the rejection of claims 28 and 30
under 35 U.S.C. § 103(a) in view of the combined teachings of Ishihara,
Powell, and Smith is AFFIRMED; and
FURTHER ORDERED that no time period for taking any
subsequent action in connection with this appeal may be extended under
37 C.F.R. § 1.136(a).
AFFIRMED
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