Thomas Knisley et al.

Patent Trials and Appeals Board

Jan 8, 2020

15215041 - (D) (P.T.A.B. Jan. 8, 2020)

UNITED STATES PATENT AND TRADEMARK OFFICE
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.
15/215,041 07/20/2016 Thomas Knisley 023223USA 6011
67251 7590 01/08/2020
SERVILLA WHITNEY LLC/AMT
33 WOOD AVE SOUTH
SUITE 830
ISELIN, NJ 08830
EXAMINER
TUROCY, DAVID P
ART UNIT PAPER NUMBER
1718
NOTIFICATION DATE DELIVERY MODE
01/08/2020 ELECTRONIC
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.
Notice of the Office communication was sent electronically on above-indicated "Notification Date" to the
following e-mail address(es):
docket@dsiplaw.com
hservilla@dsiplaw.com
lmurphy@dsiplaw.com
PTOL-90A (Rev. 04/07)
UNITED STATES PATENT AND TRADEMARK OFFICE
BEFORE THE PATENT TRIAL AND APPEAL BOARD
Ex parte THOMAS KNISLEY and DAVID THOMPSON
Appeal 2019-002041
Application 15/215,041
Technology Center 1700
Before LINDA M. GAUDETTE, CHRISTOPHER L. OGDEN, and
DEBRA L. DENNETT, Administrative Patent Judges.
GAUDETTE, Administrative Patent Judge.
DECISION ON APPEAL1
The Appellant2 appeals under 35 U.S.C. § 134(a) from the Examiner’s
decision finally rejecting claims 7, 9, and 12–20.3

1 This Decision includes citations to the following documents: Specification
filed July 20, 2016 (“Spec.”); Final Office Action dated May 14, 2018
(“Final”); Advisory Action dated July 23, 2018 (“Advisory”); Appeal Brief
filed Oct. 8, 2018 (“Appeal Br.”); Examiner’s Answer dated Nov. 19, 2018
(“Ans.”); and Reply Brief filed Jan. 14, 2019 (“Reply Br.”).
2 We use the word “Appellant” to refer to “applicant” as defined in 37
C.F.R. § 1.42. The Appellant identifies the real party in interest as Applied
Materials, Inc. Appeal Br. 3.
3 We have jurisdiction under 35 U.S.C. § 6(b).
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Application 15/215,041

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We AFFIRM IN PART and enter a new ground of rejection pursuant
to 37 C.F.R. § 41.50(b).
CLAIMED SUBJECT MATTER
The claims are directed to methods of using heteroleptic diazadiene
(“DAD”)-containing tungsten precursors for thin film deposition. Spec. ¶¶ 2,
13. The precursors used in the inventive method include a neutral donor
(“ND”), such as carbonyl (“CO”), and an anionic or dianionic metallorganic
ligand, such as cyclopentadienyl (“Cp”). Id. ¶ 13. The inventive methods
utilize atomic layer deposition (“ALD”) or chemical vapor deposition
(“CVD”) techniques. See id. ¶ 45. ALD “refers to the sequential exposure of
two or more reactive compounds to deposit a layer of material on a substrate
surface.” Id. ¶ 15.
Claim 7, reproduced below, is illustrative of the claimed subject
matter:
7. A processing method comprising sequentially exposing a
substrate to a first reactive gas comprising a tungsten-
containing compound comprising a compound with the
representative formula W(ND)x(DAD)yRz, where each ND is a
neutral donor, each DAD is a diazadiene, each R is an anionic
or dianionic ligand and x is in the range of 1 to 4, y is in the
range of 1 to 3, z is in the range of 1 to 4 and x+z is greater than
1 and a second reactive gas to form a tungsten-containing film.
Appeal Br. 28 (Claims Appendix). Claim 17, the only other independent
claim on appeal, differs substantively from claim 7 in that it does not require
“sequential” exposure to the first and second reactive gasses. See id. at 29.
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REFERENCES
The Examiner relies on the following prior art as evidence of
unpatentability:
Li (WO 2014/052642 A1, published April 3, 2014) discloses a
tungsten precursor for use in CVD and ALD. Li ¶ 29. Li’s precursor has the
following chemical structure (id. ¶ 7):

Above is the chemical structure of the fourth of twelve tungsten precursors
identified by Li as suitable for use in a method of forming a tungsten or a
tungsten-containing film on a substrate. Id. ¶¶ 7, 9.
Vaartstra (US 6,281,124 B1, issued August 28, 2001) discloses “a
method of forming a metal-containing film using one or more complexes of
Formula (I): [(R1)NC(R2)C(R3)N(R4)]xMLy” (Vaartstra 3:47–51), known as
diazadiene or diazabutadiene complexes (id. at 2:41–42). “The complexes
. . . are particularly suitable for use in a [CVD] system.” Id. at 1:10–12.
Vaarstra discloses that “M is a Group IVB, VB, or VIB metal” (id. at 3:53)
such as tungsten (id. at 1:65); “each R1, R2, R3, and R4 group is
independently H or an organic group . . . ; L is selected from the group of
CO, NO, CN, CS, CNR5, R6CN, or R7, wherein each R5, R6, and R7 group is
independently an organic group, ( . . . more preferably, R7 is
cyclopentadienyl); x=1 to 4 . . .; and y=1 to 4” (id. at 3:53–60). Vaartstra
discloses that the ligand [(R1)NC(R2)C(R3)N(R4)] typically bonds to central
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Application 15/215,041

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metal M through the nitrogen atoms as shown in the chemical structure
below (id. at 5:21–33):
Above is the chemical structure of Vaartstra’s precursor.
Shenai-Khatkhate (US 8,012,536 B2, issued September 6, 2011)
discloses a method of forming a metal-containing layer on a substrate using
CVD or ALD. Shenai-Khatkhate 1:8–11, 2:21–22. Shenai-Khatkhate
discloses that the organometallic compounds used in the method, known
generally as formamidinates or formidinate compounds, contain a metal, at
least one formamidate ligand, and at least one anionic ligand. Id. at 3:7–10.
The compounds have the formula (R1NC(H)NR2)nM+mLl(m-n)L2p. Id. at 3:31–
32. Shenai-Khatkhate discloses that suitable metals (M) include tungsten, a
wide variety of anionic ligands (L1) may be used including
cyclopentadienyls, and neutral ligands (L2) include CO. Id. at 3:63–67, 4:4–
11, 42–46. Shenai-Khatkhate discloses that anionic ligands provide
increased bonding interaction as compared to a corresponding neutral ligand.
Id. at 3:10–13.
Lansalot-Matras (US 2014/0235054 A1, published August 21, 2014)
discloses tungsten diazabutadiene precursors that are suitable for use in
depositing a tungsten-containing film, such as tungsten silicide, using CVD
or ALD. Lansalot-Matras ¶¶ 2–3, 43. Lansalot-Matras discloses that the
DAD ligands may be neutral, mono-anionic, or dianionic. Id. ¶ 25.
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Application 15/215,041

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REJECTIONS4
1. Claims 7 and 13–20 are rejected under 35 U.S.C. § 103 as
unpatentable over Li and Vaartstra (“Ground 1”).
2. Claims 9 and 12 are rejected under 35 U.S.C. § 103 as
unpatentable over Li and Vaarstra in view of Lansalot-Matras (“Ground 2”).
3. Claims 7 and 13–20 are rejected under 35 U.S.C. § 103 as
unpatentable over Li, Vaartstra, and Shenai-Khatkhate (“Ground 3”).
4. Claims 9 and 12 are rejected under 35 U.S.C. § 103 as
unpatentable over Li, Vaarstra, and Shenai-Khatkhate in view of Lansalot-
Matras (“Ground 4”).
5. Claims 7 and 13–20 are rejected under 35 U.S.C. § 103 as
unpatentable over Vaartstra and Shenai-Khatkhate (“Ground 5”).
6. Claims 7, 9, and 12–20 are rejected under 35 U.S.C. § 103 as
unpatentable over Vaartstra and Lansalot-Matras (“Ground 6”).
OPINION
Grounds 1, 2, and 6
In each of Grounds 1, 2, and 6, the Examiner relied on Vaartstra for a
teaching or suggestion of a tungsten precursor comprising DAD ligands and
both CO and Cp ligands. Final 7, 9–11. The Appellant directs us to
disclosure in Vaarstra to support its argument that Vaarstra discloses a DAD
ligand in combination with either a neutral donor (e.g., CO) or an
anionic/dianionic ligand (e.g., Cp), but does not disclose or suggest a

4 The Examiner withdrew the final rejection of claims 7, 9, and 12–20 under
35 U.S.C. § 112(b) or 35 U.S.C. § 112 (pre–AIA), second paragraph. See
Advisory 1; Ans. 3.
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precursor comprising both a neutral donor and an anionic/dianionic ligand.
Appeal Br. 12, 18, 23; see Vaartstra 2:20–30, 5:12–38.
In the Answer, the Examiner asserts that “all the claimed elements
were known in the prior art and one skilled in the art could have combined
the elements as claimed by known methods with no change in their
respective functions.” Ans. 9 (emphasis added). The Examiner further
responds to Appellant’s arguments as follows:
the Appellant appear[s] to continually argue that Vaarstra does
not disclose a DAD must include both a neutral donor and an
anionic or dianionic[ ]ligand. The examiner agrees and cites
Shenai-Khatkhate as to reasons why one would include in a
tungsten organometallic precursor both a neutral donor
(stabilizer) as well as an anionic[ ]ligand.
Ans. 17.
“[A] patent composed of several elements is not proved obvious
merely by demonstrating that each of its elements was, independently,
known in the prior art.” KSR Int’l Co. v. Teleflex Inc., 550 U.S. 398, 418
(2007). Given the Examiner’s failure to explain sufficiently why one of
ordinary skill in the art, absent consideration of Shenai-Khatkhate’s
disclosure, would have included both a neutral donor and an
anionic/dianionic ligand in Li’s or Vaartstra’s precursor, we agree with the
Appellant that the Examiner has not met the burden to show that (1) claims 7
and 13–20 would have been obvious over Li and Vaartstra, (2) claims 9 and
12 would have been obvious over Li, Vaarstra, and Lansalot-Matras, and (3)
claims 7, 9, and 12–20 would have been obvious over Vaartstra and
Lansalot-Matras. Accordingly, we do not sustain Grounds 1, 2, and 6.
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Ground 3
The Examiner rejected claims 7 and 13–20 under 35 U.S.C. § 103 as
unpatentable over Li, Vaartstra, and Shenai-Khatkhate. See generally Final
6–8. The Appellant relies on the same arguments in support of patentability
of independent claims 7 and 17, and dependent claims 18–20. See Appeal
Br. 11–17. The Appellant presents separate arguments in support of
patentability of claims 13–16. See id. at 16.
The Examiner found that Li discloses a processing method that
includes steps of exposing a substrate to a first reactive gas comprising a
tungsten DAD precursor with CO ligands (a neutral donor) and to a second
gas to form a tungsten-containing film. Final 6 (citing Li ¶¶ 7, 9, 29). The
Examiner found that Vaartstra discloses vapor deposition of a film using
tungsten precursors with a DAD ligand as well as an L group such as CO or
an anionic/dianionic ligand (e.g., Cp). Id. at 7. The Examiner found that
Shenai-Khatkhate discloses an organometallic precursor with a heteroleptic
structure that includes an anionic ligand of Cp and a stabilizer of CO. Id.
The Examiner determined that the collective teachings of the references
suggest modifying Li’s tungsten DAD precursor to include both Cp and CO
ligands. See id.
The Appellant argues that formamidinate ligands, such as those
described in Shenai-Khatkhate, differ vastly from DAD ligands in both
chemical structure and chemical properties. Appeal Br. 14. The Appellant
thus contends that in considering improvements to methods of producing
tungsten films using diazadienyl-containing tungsten precursors, the
ordinary artisan would not have looked to Shenai-Khatkhate. Id. at 14–15.
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The Appellant’s argument is not persuasive. To the extent the
Appellant is arguing that Shenai-Khatkhate is non-analogous art, we note
that “[t]wo separate tests define the scope of analogous prior art: (1) whether
the art is from the same field of endeavor, regardless of the problem
addressed and, (2) if the reference is not within the field of the inventor’s
endeavor, whether the reference still is reasonably pertinent to the particular
problem with which the inventor is involved.” In re Klein, 647 F.3d 1343,
1348 (Fed. Cir. 2011) (quoting In re Bigio, 381 F.3d 1320, 1325 (Fed. Cir.
2004)). The Appellant has not provided persuasive evidence to refute the
Examiner’s finding that Shenai-Khatkhate is at least reasonably pertinent to
the problem with which the inventors were concerned.
As explained by the Examiner, like the present invention, Shenai-
Khatkhate relates to CVD/ALD organometallic precursors with tungsten as
the central metal atom, and both DAD and formadinate are formed from two
nitrogens separated by carbon atoms, both nitrogen atoms being bonded to
the tungsten. Ans. 13. Like the present inventors, Shenai-Khatkhate is
concerned with thermally stable precursors that produce tungsten films
containing low levels of contaminants. Compare Spec. ¶ 6, with Shenai-
Khatkhate 9:15–30; see Ans. 11. Further, the Appellant has not provided
persuasive argument or evidence (see generally Reply Br.) to refute the
Examiner’s finding that the ordinary artisan would have included an anionic
ligand in Li’s organometallic precursor based on Shenai-Khatkhate’s
disclosure that the use of only a single ligand group offers less control over
achieving required thermal stability for the precursor, and that anionic
ligands “provide increased bonding interaction as compared to the neutral
ligand” (Ans. 11; see Shenai-Khatkhate 1:44–50, 3:11–13).
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Accordingly, we sustain the rejection of claims 7 and 17–20 as
unpatentable over the combination of Li, Vaartstra, and Shenai-Khatkhate.
As to claims 13–16, the Appellant notes that these claims depend from
claim 9, which was not rejected over the combination of Li, Vaartstra, and
Shenai-Khatkhate. See Appeal Br. 15. Claim 9 recites “wherein the second
reactive gas comprises a silicon-containing compound and the tungsten-
containing film comprises tungsten silicide (WSix).” Id. at 28 (Claims
Appendix). The Examiner did not identify a teaching or suggestion of these
features in Li, Vaartstra, Shenai-Khatkhate, or a combination of these
references, but relied on Lansalot-Matras for a teaching of forming tungsten
silicide and using a silicon precursor See Final 8; Ans. 15.
Accordingly, we do not sustain the rejection of claims 13–16 as
unpatentable over the combination of Li, Vaartstra, and Shenai-Khatkhate.
Ground 4 and New Ground
The Examiner rejected claims 9 and 12 under 35 U.S.C. § 103 as
unpatentable over Li, Vaartstra, Shenai-Khatkhate, and Lansalot-Matras. See
generally Final 8–9. As indicated above, in rejecting claim 9, the Examiner
determined that using a silicon-containing compound as the second reactive
gas in the modified method of Li to produce a film comprising tungsten
silicide (WSix) would have been obvious in view of Lansalot-Matras’s
disclosure. Final 8 (citing Lansalot-Matras ¶¶ 8, 16, 43, 46).
Claim 12 depends from claim 9 and recites a specific formula for at
least one DAD ligand of the tungsten-containing compound used in the
claimed method. Appeal Br. 28 (Claims Appendix). Specifically, claim 12
requires that the DAD ligand consist of a doubly anionic system where both
nitrogen atoms are capable of being covalently bound to the tungsten atom
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and that each of two R groups is independently selected from a limited list
that includes C1-C6 alkyl groups. Id. The Examiner found that Lansalot-
Matras discloses using a doubly anionic system with R1 and R6 being C1-
C6 linear alkyls. Ans. 8 (citing Lansalot-Matras ¶¶ 24–25, 52). The
Examiner determined that modifying Li’s tungsten DAD precursor to
include a DAD ligand as disclosed in Lansalot-Matras would have been
obvious to one of ordinary skill in the art. Id.
The Appellant’s arguments in support of patentability of claims 9 and
12 are limited to a contention that the ordinary artisan would not have
looked to Lansalot-Matras because the compounds described therein are
homoleptic—they “contain 3 DAD ligands and no other ligands complexed
to tungsten”—whereas the claimed invention relates to heteroleptic metal
compounds. Appeal Br. 18–19. The Appellant explains that “a metal species
having more than one type of ligand is heteroleptic, while a metal species
having all ligands identical is homoleptic.” Id. at 18. The Appellant argues
that “[h]eteroleptic and homoleptic metal compounds are distinct in their
chemical properties, such that one skilled in the art would not expect one to
be informative of the other.” Id.
The Appellant has not identified persuasive evidence to support this
argument and, therefore, we are not persuaded of reversible error in the
Examiner’s obviousness determination as to claims 9 and 12. See In re
Geisler, 116 F.3d 1465, 1471 (Fed. Cir. 1997) (explaining that argument by
counsel cannot take the place of evidence). Accordingly, we sustain the
rejection of claims 9 and 12 as unpatentable over the combination of Li,
Vaartstra, Shenai-Khatkhate, and Lansalot-Matras.
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Claims 13–16 depend from claim 9. See Appeal Br. 28 (Claims
Appendix). As discussed in the preceding paragraphs, the Appellant has not
shown reversible error in the Examiner’s determination that claim 9 is
unpatentable over the combination of Li, Vaartstra, Shenai-Khatkhate, and
Lansalot-Matras. The Examiner found, and the Appellant does not dispute,
that Li, Vaartstra, Shenai-Khatkhate, or a combination thereof, teach or
suggest the additional limitations recited in each of claims 13–16. See Final
7–8; Appeal Br. 16. Accordingly, we enter a new ground of rejection of
claims 13–16 under 35 U.S.C. § 103 as unpatentable over Li, Vaartstra,
Shenai-Khatkhate, and Lansalot-Matras.
Ground 5
The Examiner rejected claims 7 and 13–20 under 35 U.S.C. § 103 as
unpatentable over Vaartstra and Shenai-Khatkhate. See generally Final 9–
10. The Examiner found that Vaartstra discloses a method of forming a
tungsten-containing film comprising sequentially exposing a substrate to
first and second reactive gases. Id. at 9. The Examiner found that Vaartstra
discloses that the first reactive gas comprises a tungsten precursor with a
DAD ligand as well as an L group such as CO or Cp. Id. The Examiner
found that Shenai-Khatkhate discloses an organometallic precursor with a
heterolopetic structure that includes an anionic ligand of Cp and a stabilizer
of CO. Id. at 10. The Examiner determined that given Shenai-Khatkhate’s
disclosure, using a tungsten precursor with a DAD ligand and both Cp and
CO ligands in Vaarstra’s method would have been obvious to one of
ordinary skill in the art. Id.
The Appellant’s arguments are substantially the same as those made
in support of patentability of the claims over the combination of Li,
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Vaartstra, and Shenai-Khatkhate. Compare Appeal Br. 19–22, with id. at 11–
17. For the reasons discussed above, these arguments fail to identify error in
the Examiner’s rejection of claims 7 and 17–20, but are persuasive of
reversible error in the Examiner’s rejection of claims 13–16.
Accordingly, we sustain the rejection based on the combination of
Vaartstra and Shenai-Khatkhate as to claims 7 and 17–20, but reverse as to
claims 13–16.
CONCLUSION
Claims
Rejected
35
U.S.C.
§
Reference(s)/Basis Affirmed Reversed New
Ground
7, 13–20 103 Li, Vaartstra 7, 13–20
9, 12 103 Li, Vaartstra,
Lansalot-Matras
9, 12
7, 13–20 103 Li, Vaartstra,
Shenai-Khatkhate
7, 17–20 13–16
9, 12–16 103 Li, Vaartstra,
Shenai-Khatkhate,
Lansalot-Matras
9, 12 13–16
7, 13–20 103 Vaartstra, Shenai-
Khatkhate
7, 17–20 13–16
7, 9, 12–
20
103 Vaartstra,
Lansalot-Matras
7, 9, 12–
20

Overall
Outcome
7, 9, 12,
17–20
13–16 13–16

37 C.F.R. § 41.50(b) provides that an appellant, WITHIN TWO
MONTHS FROM THE DATE OF THE DECISION, must exercise one of
the following two options with respect to the new grounds of rejection to
avoid termination of the appeal as to the rejected claims:
(1) Reopen prosecution. Submit an appropriate
amendment of the claims so rejected or new
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Evidence relating to the claims so rejected, or both,
and have the matter reconsidered by the examiner,
in which event the prosecution will be remanded to
the examiner. . . .
(2) Request rehearing. Request that the
proceeding be reheard under § 41.52 by the Board
upon the same Record.

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)(iv). See 37
C.F.R. § 41.50(f) (2012).

AFFIRMED IN PART;
37 C.F.R. § 41.50(b)