Ex Parte Meiere

Patent Trial and Appeal Board

Nov 16, 2012

11063638 (P.T.A.B. Nov. 16, 2012)

UNITED STATES PATENT AND TRADEMARKOFFICE
UNITED STATES DEPARTMENT OF COMMERCE
United States Patent and Trademark Office
Address: COMMISSIONER FOR PATENTS
P.O. Box 1450
Alexandria, Virginia 22313-1450
www.uspto.gov
APPLICATION NO. FILING DATE FIRST NAMED INVENTOR ATTORNEY DOCKET NO. CONFIRMATION NO.
11/063,638 02/24/2005 Scott Houston Meiere 21394 7279
27182 7590 11/16/2012
PRAXAIR, INC.
LAW DEPARTMENT - M1 557
39 OLD RIDGEBURY ROAD
DANBURY, CT 06810-5113
EXAMINER
HORNING, JOEL G
ART UNIT PAPER NUMBER
1712
MAIL DATE DELIVERY MODE
11/16/2012 PAPER
Please find below and/or attached an Office communication concerning this application or proceeding.
The time period for reply, if any, is set in the attached communication.
PTOL-90A (Rev. 04/07)

UNITED STATES PATENT AND TRADEMARK OFFICE
____________

BEFORE THE PATENT TRIAL AND APPEAL BOARD
____________

Ex parte SCOTT HOUSTON MEIERE
____________

Appeal 2011-011421
Application 11/063,638
Technology Center 1700
____________

Before TERRY J. OWENS, ROMULO H. DELMENDO, and
LINDA M. GAUDETTE, Administrative Patent Judges.

GAUDETTE, Administrative Patent Judge.

DECISION ON APPEAL

Appellant appeals under 35 U.S.C. § 134(a) from the Examiner’s decision1
finally rejecting claims 1, 3-6, 8, 21, 23, and 27-32.2 We have jurisdiction under
35 U.S.C. § 6(b).
We AFFIRM.
The Examiner maintains the following grounds of rejection:
1. claims 1, 3-6, 8, 21, 23, and 27-32 are rejected under 35 U.S.C.
§103(a) as unpatentable over McCord (US 3,293,005, issued Dec. 20, 1966) in
view of Snyder (US 5,102,637, issued Apr. 7, 1992), further in view of Gutowski

1 Final Office Action mailed Aug. 10, 2010
2 Appeal Brief filed Jan. 10, 2011 (“Br.”)
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Application 11/063,638

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(Materials Research Society Symp. Proc., Vol. 716, B6.5.1- B6.5.6 (2002)) in view
of Baum (US 6,869,638 B2, issued Mar. 22, 2005) in view of Zhuang (US
6,472,337 B1, issued Oct. 29, 2002) in view of Greenberg (US 3,069,232, issued
Dec. 18, 1962) (Ans.3 8-11), or, in the alternative, under 35 U.S.C. §103(a) as
unpatentable over McCord and Snyder alone (id. at 3-8); and
2. claims 8, 28, 29, and 32 are provisionally rejected on the ground of
nonstatutory obviousness-type double patenting as unpatentable over claims 1 and
3-6 of copending US Application 11/245,104 (id. at 12-13).
Of the appealed claims, claims 1, 8, 21, 27, and 28 are independent.
Independent claims 1, 21, and 27 are method claims which recite “[a] process for
producing a low zirconium hafnium halide composition useful for synthesis of a
hafnium-containing precursor for chemical vapor or atomic layer film depositions
in semiconductor applications.” Claims 8 and 28 are product-by-process claims
which recite “[a] low zirconium hafnium halide composition useful for synthesis of
a hafnium-containing precursor for chemical vapor or atomic layer film
depositions in semiconductor applications.”
With respect to the above-identified first ground of rejection, Appellants
indicate the following two groups of claims are separately argued: (1) claims 1, 3-
6, 21, 23, 27, 30, and 31 (Br. 8-13 and 17-21), and (2) claims 8, 28, 29, and 32 (Br.
14-17 and 21-23). We decide the patentability of the separately argued groups of
claims on the basis of independent claims 27 and 28, respectively. Claim 28
recites a composition produced by the same process recited in claim 27, which is
reproduced below from the Claims Appendix to the Appeal Brief:

3 Examiner’s Answer mailed Apr. 15, 2011
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Application 11/063,638

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27. A process for producing a low zirconium hafnium halide composition
useful for synthesis of a hafnium-containing precursor for chemical vapor or
atomic layer film depositions in semiconductor applications, said hafnium-
containing precursor selected from the group consisting of an amide, alkoxide,
diketonate, cyclopentadienide, and imide, said composition comprising a hafnium
halide compound represented by the formula Hf(X)4 wherein X is the same or
different and is a halide and wherein said composition has a zirconium
concentration of less than about 500 parts per million, which process consists
essentially of reacting a hafnium oxide compound, wherein said hafnium oxide
compound has a zirconium concentration of less than about 500 parts per million,
with a halogen or halogen-containing compound in the absence of air and moisture
and under reaction conditions sufficient to produce said composition.

According to Appellant, he has discovered that by “[s]tarting with high
purity hafnium oxide, . . . hafnium halide compounds with low zirconium levels
can be synthesized utilizing a single reaction. In contrast to methods existing prior
to Appellants’ claimed invention, the hafnium halide compounds useful in this
invention do not require fractional or multiple sublimation steps to obtain low
zirconium levels.” (Br. 8.)
The issue we consider with respect to the rejection of claims 1, 3-6, 8, 21,
23, and 27-32 under 35 U.S.C. §103(a) as unpatentable over McCord in view of
Snyder, further in view of Gutowski in view of Baum in view of Zhuang in view of
Greenberg is: did the Examiner reversibly err in finding one of ordinary skill in
the art would have been motivated to use a high purity, i.e., low zirconium, HfO2
compound, in McCord’s method to produce a hafnium halide compound having a
zirconium concentration of less than about 500 parts per million?4

4 We note that while Appellants present separate arguments in support of
patentability of the above-noted claim groupings, the arguments raise the same
issue.
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Application 11/063,638

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We answer this question in the negative for the reasons expressed in the
Answer and below.
A preponderance of the evidence of record supports the following findings
of fact:
McCord discloses a method of making HfCl4 by chlorinating hafnium oxide.
(McCord, col. 1, ll. 11-13.) Zhuang, in turn, teaches a method of using HfCl4 to
form a precursor for a thin film formed by CVD processes (Zhuang Abstract, col.
1, ll. 53-55), while Baum teaches a method of using a hafnium precursor to form a
HfO2 film on a silicon substrate (Baum, col. 18, l. 44-col. 20, l. 10).
In McCord’s method, reaction pellets are fed though a gas tight feeder with
nitrogen to a gas tight reactor where chlorine gas is used as the reaction gas.
(McCord, col. 5, ll. 63-75.) McCord discloses that the recovered product is
anhydrous hafnium tetrachloride. (Id. at col. 1, ll. 15-16.) McCord discloses
recovering a product which is a “high purity powder” (id. at col. 6, ll. 38-39), but
does not teach that the HfCl4 product has a zirconium concentration of less than
about 500 ppm.
McCord teaches that
[t]he use of substantially pure reactants together with stoichiometric
amounts of reactants provides complete consumption of reactants and
thereby eliminates the problems of residue removal from the
chlorinator and impurities in the effluent gas. While the reactants
need not be 100 percent pure, they must be relatively free of
undesirable impurities. Therefore various impure oxidic ores
containing substantial amounts of impurities may not be used in this
invention, for the objects and advantages of this invention cannot be
attained when such impure ores are used.
(McCord col. 4, ll. 52-62.)
McCord does not disclose that zirconium is an undesirable impurity in the
hafnium tetrachloride product. (See Br. 9; cf. Ans. 9.) However, at the time of the
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invention, one of ordinary skill in the art would have been aware that “the presence
of zirconia is undesirable in a hafnia film on silicon because it will make the
interface less stable, which means that the presence of zirconium impurities in the
hafnium precursor would also be undesirable, since it would be incorporated into
the deposited hafnia film and decrease its stability.” (Ans. 9; see Gutowski B6.5.1.
(“The zirconia/Si interface has been found to be unstable with respect to formation
of silicides whereas the hafnia/Si interface is stable.”); cf. Br. 21 (“Gutowski . . .
concerns a qualitative study which confirms the problem of zirconium in these
compounds.” (citing the Declaration of Dr. Ronald Spohn, ¶ 11)).) At the time of
the invention, one of ordinary skill in the art would have known that Hf and Zr
metals “are normally associated together in nature” (Greenberg col. 1, ll. 15-17) ,
and that commercial methods were available by which HfO2 could be purified to
levels of less than a few hundred ppm Zr. (Spec. [0008]; Br. 10.)
Appellant acknowledges that “[a]t the time of [the] invention, chlorination of
hafnium oxide and zirconium oxide on an industrial scale was known,” but
maintains these processes resulted in a hafnium chloride product containing about
1-3% zirconium. (Br. 7.) Appellant argues that while highly pure material, i.e.,
having a zirconium content between 0.1-0.3%, could be obtained through tedious
sublimation processes (id.), one of ordinary skill in the art would have had no
motivation to produce such a product since “there was no recognition or
appreciation in the semiconductor field of any problems resulting from zirconium
impurities in hafnium halides and products made therefrom” (id.at 6).
Appellant’s argument is unpersuasive given what we find to be a clear
suggestion in Gutowski that the presence of zirconium would create instability in
hafnium compositions used in semiconductor applications. (See Ans. 13-14.)
Appellant has not refuted the Examiner’s finding that because the zirconium
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impurities in a dielectric material would come from the precursor material, it
would have been obvious to make a precursor having a very low zirconium
content. (See id. at 16.)
Appellant argues McCord is not concerned with the manufacture of
compounds for use in semiconductor processes and that use of an ultra-high purity
hafnium oxide as recited in the appealed claims “would have been wasted on a set
up like McCord that would produce material of much lower purity than that of the
starting compound.” (Br. 9.)
The facts and reasons relied on by the Examiner support findings that one of
ordinary skill in the art would have recognized from McCord’s disclosure that the
use of high purity reactants would provide a high purity product (see McCord col.
4, ll. 52-62 supra p. 4), and would have recognized from Gutowski that zirconium
is an undesirable impurity in hafnium chloride compounds intended for use in
semiconductor applications. (See Gutowski B6.5.1 supra p. 5; Spohn Declaration
¶ 11.) While McCord does not expressly disclose the use of HfCl4 for
semiconductor applications, one of ordinary skill in the art would have understood
that HfCl4 could be used to form a precursor for a dielectric film based on the
disclosures of Zhuang and Baum. (See supra p. 4.) As such, one of ordinary skill
in the art would have been motivated to use a low zirconium hafnium oxide as a
reactant in McCord’s method where the resultant hafnium chloride product was
intended for use in semiconductor applications, e.g., the synthesis of a hafnium-
containing precursor for CVD depositions. As noted by the Examiner (see
generally, Ans. 17-19), Appellant has not provided evidence which refutes a
finding that McCord’s process, if modified to use a hafnium oxide compound
having a zirconium concentration of less than 500 ppm, would result in a low
zirconium hafnium halide composition as claimed. See In re Geisler, 116 F.3d
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1465, 1471 (Fed. Cir. 1997) (argument by counsel cannot take the place of
evidence); In re Lindner, 457 F.2d 506, 508 (CCPA 1972) (mere conclusory
statements of superiority in the Specification and/or the Brief, unsupported by
factual evidence, are of little probative value).
The Examiner has fully addressed any remaining arguments made by
Appellant and not expressly discussed herein, convincingly explaining why such
arguments are unpersuasive of error in the Examiner’s obviousness determination.
(See generally, Ans. 13-22.)5 Accordingly, we affirm the rejection of claims 1, 3-
6, 8, 21, 23, and 27-32 under 35 U.S.C. §103(a) as unpatentable over McCord in
view of Snyder, further in view of Gutowski in view of Baum in view of Zhuang in
view of Greenberg. We do not reach the alternative rejection of these claims under
35 U.S.C. §103(a) as unpatentable over McCord in view of Snyder.
Turning to the provisional rejection of claims 8, 28, 29, and 32 on the
ground of nonstatutory obviousness-type double patenting, we note that Appellant
does not raise substantive arguments traversing this rejection, but indicate they will
take action to overcome the rejection upon allowance of the claims. (Br. 24.)
Accordingly, we summarily affirm this ground of rejection.
The Examiner’s decision to reject claims 1, 3-6, 8, 21, 23, and 27-32 is
affirmed.
No time period for taking any subsequent action in connection with this
appeal may be extended under 37 C.F.R. § 1.136(a)(1).
AFFIRMED
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5 We note the Examiner has expressly considered the Spohn Declaration and
explained why it fails to support a conclusion of nonobviousness. (See e.g., Ans.
21-22.)