Ex Parte Olsen et al

Board of Patent Appeals and Interferences

May 10, 2012

10851514 (B.P.A.I. May. 10, 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.
10/851,514 05/21/2004 Christopher Olsen AMAT/9194/FEP/GCM/RKK 2721
44257 7590 05/10/2012
PATTERSON & SHERIDAN, LLP - - APPM/TX
3040 POST OAK BOULEVARD, SUITE 1500
HOUSTON, TX 77056
EXAMINER
VETERE, ROBERT A
ART UNIT PAPER NUMBER
1712
MAIL DATE DELIVERY MODE
05/10/2012 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 BOARD OF PATENT APPEALS
AND INTERFERENCES
____________

Ex parte CHRISTOPHER OLSEN, PRAVIN K. NARWANKAR,
SHREYAS S. KHER, RANDHIR THAKUR,
SHANKAR MUTHUKRISHNAN, and PHILIP A. KRAUS

____________

Appeal 2010-006568
Application 10/851,514
Technology Center 1700
____________

Before ADRIENE LEPIANE HANLON, CHUNG K. PAK, and
JEFFREY T. SMITH, Administrative Patent Judges.

PAK, Administrative Patent Judge.

DECISION ON APPEAL
Appellants appeal under 35 U.S.C. § 134(a) from the Examiner’s final
rejection of claims 1 through 5, 8 through 11, 13, 16, 18 through 20, 23, 25,
27 through 29, 31 through 33, and 35 through 54, all of the claims pending
Appeal 2010-006568
Application 10/851,514

2
in the above-identified application.1 We have jurisdiction under 35 U.S.C. §
6.
STATEMENT OF THE CASE
The subject matter on appeal “relates to methods for depositing
materials on substrates, and more specifically, to methods for depositing and
stabilizing dielectric materials” (Spec. 1, para.0001). The methods are used
to prepare “dielectric materials used in a variety of applications, especially
…high-k dielectric materials used in transistor and/or capacitor fabrication”
(Spec. 5, para. 0019). “Some of the methods use atomic layer deposition
(ALD) to have elemental control of the composition of the dielectric
compound.” Id. According to paragraph 0021 at page 6 of the
Specification:
“Atomic layer deposition” or “cyclical deposition” as
used herein refers to the sequential introduction of two or more
reactive compounds to deposit a layer of material on a substrate
surface. The two, three or more reactive compounds may
alternatively be introduced into a reaction zone of a processing
chamber.

Details of the appealed subject matter are recited in representative claims 1,
10, 18, 19, 20, 29, and 492 reproduced from the Claims Appendix to the
Appeal Brief as shown below:

1 See Appeal Brief (“App. Br.”) filed August 17, 2009, 1 and 5; Examiner’s
Answer (“Ans.”) filed November 10, 2009, 2; and Reply Brief (“Reply Br.”)
filed January 7, 2010, 1.

2 Appellants have presented the same arguments for independent claims 1,
10, 18, 19, 20, and 29 and separate arguments for dependent claims 49
through 54 (App. Br.12-18). Therefore, for purposes of this appeal, we
select claims 1, 10, 18, 19, 20, 29, and 49 and decide the propriety of the
Appeal 2010-006568
Application 10/851,514

3
1. A method for forming a dielectric stack on a substrate, comprising:
depositing a first dielectric layer of hafnium silicate on a substrate by
an atomic layer deposition process, wherein the substrate is exposed to
precursors of an alkylamino hafnium compound, water vapor, and an
alkylamino silane compound during the atomic layer deposition process;
exposing the first dielectric layer to a plasma nitridation process to
form a first nitride layer comprising a nitrogen concentration within a range
from about 5 at% to about 25 at%;
depositing a second dielectric layer on the first nitride layer, wherein
the second dielectric layer comprises a material selected from the group
consisting of hafnium silicate, zirconium silicate, aluminum silicate,
derivatives thereof, and combinations thereof;
exposing the second dielectric layer to the plasma nitridation process
to form a second nitride layer comprising a nitrogen concentration within a
range from about 5 at% to about 25 at%; and
exposing the substrate to an annealing process.

10. A method for forming a dielectric stack on a substrate,
comprising:
a) depositing a dielectric layer having a thickness within a range from
about 5 Å to about 50 Å on a substrate by an atomic layer deposition
process, wherein the dielectric layer comprises a dielectric material
consisting of hafnium silicate from precursors of an alkylamino hafnium
compound, water vapor, and an alkylamino silane compound;
b) exposing the dielectric layer to a plasma nitridation process to form
a nitride layer thereon, wherein the dielectric layer comprises a nitrogen
concentration within a range from about 5 at% to about 25 at%;
c) optionally exposing the substrate to an annealing process; and
d) repeating a process cycle of at least a)-b) to form the dielectric
stack.
18. A method for forming a dielectric stack on a substrate,
comprising:
a) depositing a dielectric layer of hafnium silicate on the substrate by
an atomic layer deposition process, wherein the substrate is exposed to an

Examiner’s §103(a) rejections set forth in the Answer based on these claims
alone in accordance with 37 C.F.R. § 41.37(c)(1)(vii) .

Appeal 2010-006568
Application 10/851,514

4
alkylamino hafnium compound, water vapor, and alkylamino silane
compound during the atomic layer deposition process;
b) exposing the dielectric layer to a plasma nitridation process;
c) exposing the substrate to an annealing process; and
d) repeating a process cycle of steps a-c to form the dielectric stack.

19. A method for forming a dielectric stack on a substrate,
comprising:
a) depositing a dielectric layer of hafnium silicate on the substrate by
an atomic layer deposition process, wherein the hafnium silicate is formed
from precursors of alkylamino hafnium, water vapor, and alkylamino silane;
b) exposing the dielectric layer to a plasma nitridation process; and
c) repeating a process cycle of steps a-b to form the dielectric stack,
wherein the dielectric stack comprises a nitrogen concentration within a
range from about 5 at% to about 25 at%.

20. A method for forming a dielectric nitride material on a substrate,
comprising:
depositing a dielectric layer of hafnium silicate on a substrate by an
atomic layer deposition process, wherein the substrate is exposed to an
alkylamino hafnium compound, water vapor, and an alkylamino silane
compound during the atomic layer deposition process;
exposing the dielectric layer to a plasma nitridation process to form a
nitride layer thereon, wherein the nitride layer comprises a nitrogen
concentration within a range from about 5 at% to about 25 at%; and
exposing the nitride layer to an annealing process.

29. A method for forming a dielectric material on a substrate,
comprising:
depositing a metal oxide layer on a substrate during an atomic layer
deposition process, wherein the metal oxide layer comprises hafnium
silicate, wherein the substrate is exposed to an alkylamino hafnium
compound, water vapor, and an alkylamino silane compound during the
atomic layer deposition process;
exposing the metal oxide layer to a plasma nitridation process to form
a nitride layer thereon; and
exposing the substrate sequentially to the deposition and nitridation
processes while periodically exposing the substrate to an annealing process
to form a dielectric stack having a predetermined thickness.
Appeal 2010-006568
Application 10/851,514

5
49. The method of claim 1, further comprising co-flowing the
alkylamino hafnium compound and the alkylamino silane compound in a
first half reaction and sequentially pulsing water vapor in a second half
reaction, with each half reaction separated by an argon purge.
As evidence of unpatentability of the claimed subject matter, the
Examiner relies on the following prior art references at page 3 of the
Answer:
Kraft US 6,136,654 Oct. 24, 2000
Wallace US 6,291,867 B1 Sep. 18, 2001
Minami US 6,334,962 B1 Jan. 1, 2002
Doh US 7, 037,863 B2 May 2, 2006
Quevedo-Lopez US 2006/0121744 A1 Jun. 8, 2006
Kamiyama US 2006/0273408 A1 Dec. 7, 2006
Lee US 7, 151,039 B2 Dec. 19, 2006

Appellants seek review of the following grounds of rejection
maintained by the Examiner in the Answer:
1) Claims 1 through 4, 8, 9, 10, 11, 16, 18 through 20, 27 through
29, 35, 36, and 41 through 54 under 35 U.S.C. § 103(a) as
unpatentable over the combined disclosure of Quevedo-Lopez, Lee,
Kamiyama, and Doh;
2) Claims 5, 13, and 25 under 35 U.S.C. § 103(a) as unpatentable
over the combined disclosure of Quevedo-Lopez, Lee, Kamiyama,
Doh, and Wallace;
3) Claims 23, 31, and 32 under 35 U.S.C. § 103(a) as unpatentable
over the combined disclosure of Quevedo-Lopez, Lee, Kamiyama,
Doh, and Kraft;
4) Claim 33 under 35 U.S.C. § 103(a) as unpatentable over the
combined disclosure of Quevedo-Lopez, Lee, Kamiyama, Doh, Kraft,
and Wallace; and
Appeal 2010-006568
Application 10/851,514

6
5) Claims 37 through 40 under 35 U.S.C. § 103(a) as unpatentable
over the combined disclosure of Quevedo-Lopez, Lee, Kamiyama,
Doh, and Minami. (See App. Br. 11 and Ans. 3-8).

RELEVANT FACTUAL FINDINGS, PRINCIPLES OF LAW, ISSUE,
ANALYSIS, AND CONCLUSION
I. REJECTION (1)
A. CLAIMS 1-4, 8, 9, 10, 11, 16, 18-20, 27-29, 35, 36, and 41-48
Appellants contend that:
combination of the references fails to teach, show, or suggest
depositing a first dielectric layer of hafnium silicate on a
substrate by an atomic layer deposition process, wherein the
substrate is exposed to precursors of an alkylamino hafnium
compound, water vapor, and an alkylamino silane compound
during the atomic layer deposition process, as recited in
independent claim[s] 1[, 10, 18, 19, 20, and 29]. [(See, e.g.,
App. Br. 15-16 and Reply br. 9-10.)]

Thus, the dispositive question is: Has the Examiner erred in
determining that the collective teachings of Quevedo-Lopez, Lee,
Kamiyama, and Doh would have suggested depositing a first dielectric layer
of hafnium silicate on a substrate by an atomic layer deposition process,
wherein the substrate is exposed to precursors of an alkylamino hafnium
compound, water vapor, and an alkylamino silane compound during the
atomic layer deposition process, as recited in independent claims 1, 10, 18,
19, 20, and 29 within the meaning of 35 U.S.C. 103(a)? On this record, we
answer this question in the negative.
As correctly found by the Examiner at page 3 of the Answer,
Quevedo-Lopez teaches a method of forming a dielectric stack (gate
Appeal 2010-006568
Application 10/851,514

7
insulation layers) on a substrate useful for a wide variety of MOS devices,
such as transistors and capacitors, or any other type of integrated circuit
comprising, inter alia, depositing a first high-k dielectric layer of hafnium
silicate on a substrate and exposing the first high-k-dielectric layer to a
plasma nitridation process to form a first nitride layer. (See also Quevedo-
Lopez, paras. 0017, 0018, and 0022.) According to paragraphs 0009, 0020,
and 0029 of Quevedo-Lopez, the deposition of the first high-k dielectric
layer can be accomplished by, inter alia, atomic layer deposition (ALD).
(See also Ans. 3.) Consistent with the teachings of Quevedo-Lopez,
Appellants also acknowledge at paragraph 004 of the Specification that it
was known at the time of the invention that “[s]ome of the common high-k
materials produced by ALD processes include hafnium oxide, hafnium
silicate, …” Although Quevedo-Lopez does not indicate the details of its
ALD method, the Examiner has correctly found at pages 3, 4, and 8 of the
Answer that Kamiyama, in reference to depositing and nitriding a high-k
dielectric layer of hafnium silicate useful as a gate insulating film for MOS
or PMOS transistor, teaches that:
The Hf silicate film is formed by the combination of a
step for forming a hafnium oxide film (HfO2) using the ALD
(atomic layer deposition method [employing, e.g., hafnium
tetramethylethylamide [Hf(N(CH3)(C2H5)2)4], and then an
oxidizing gas, such as ozone gas,] and a step for forming a
silicon oxide film (SiO2 film) using the ALD method
[employing, e.g., tris(dimethylamino)silane corresponding to
the claimed alkylamino silane compound], and by controlling
the number of each step. [(See Kamiyama, pp.3-4, paras. 0048,
0051, 0052, 0055, 0064, 0069, 0082 and 0083.)]

The Examiner has also correctly found at page 4 of the Answer that Lee, in
forming a high-k dielectric layer useful as a gate insulating layer, teaches an
Appeal 2010-006568
Application 10/851,514

8
oxide layer, such as the hafnium oxide film taught by Kamiyama, can also
be deposited using the ALD method employing tetrakis-ethyl methyl amino
hafnium (corresponding to the claimed alkylamino hafnium compound).
(See also Lee, col. 2, l. 50 to col. 3, l. 18 and col. 8, ll. 8-40.) As also
acknowledged by Appellants at page 13 of the Appeal Brief and page 5 of
the Reply Brief, Lee, like Kamiyama, teaches supplying an oxidant,
subsequent to the deposition of a hafnium precursor, to form a hafnium
oxide layer. Although Lee mentions that H2O is less preferred than ozone as
an oxidizing gas as argued by Appellants at page 5 of the Reply Brief, it still
teaches using ozone gas or H2O as an oxidizing gas in forming its oxide
layer. (See also Lee, col. 3, ll. 29-57, col. 6, ll. 24-35, and col. 12, ll. 13-16.)
Moreover, Doh teaches that H2O, like ozone, is a known oxidizing gas in the
art, which is included by Kamiyama’s broad disclosure of an oxidizing gas,
even if it is used for post-treating a high dielectric layer as asserted by
Appellants. (See Ans. 8.)
Given the above circumstances, we concur with the Examiner that one
of ordinary skill in the art would have been led to deposit the first high-k
dielectric layer of hafnium silicate using the ALD method employing the
alkylamino or alkylamido hafnium compound, oxidant, such as water vapor
or ozone, and alkylamino silane compound suggested by Kamiyama, Lee
and Doh in the manner suggested by Kamiyama in Quevedo-Lopez’s high-k
dielectric stack forming method, with a reasonable expectation of
successfully forming the high-k dielectric layer of hafnium silicate useful as
a gate insulating film within the meaning of 35 U.S.C. § 103(a).

Appeal 2010-006568
Application 10/851,514

9
B. CLAIMS 49-54
Appellants contend that Quevedo-Lopez, Lee, Kamiyama, and Doh do
not teach and would not have suggested “co-flowing the alkyamino hafnium
compound and the alkylamino silane compound in a first half reaction and
sequentially pulsing water vapor in a second half reaction with each half
reaction separated by an argon purge” as required by claims 49 through 54.
(See App. Br. 16-18.) The Examiner has not shown, much less explained,
why one of ordinary skill in the art would have been led to sequentially
pulse water vapor after co-flowing the alkyamino hafnium compound and
the alkylamino silane compound in a first half reaction, to form a dielectric
layer of hafnium silicate. (See Ans. 6 and 9.)
Thus, we are constrained to agree with Appellants that the Examiner
has not demonstrated that Quevedo-Lopez, Lee, Kamiyama, and Doh would
have rendered the subject matter of claims 49 through 54 obvious to one of
ordinary skill in the art within the meaning of 35 U.S.C. § 103(a).
II. REJECTIONS (2), (3), (4), and (5)
Appellants rely on the same arguments made in connection with the
rejection of claims 1-4, 8, 9, 10, 11, 16, 18-20, 27-29, 35, 36, and 41-48
discussed supra. (See App. Br. 19,)
Thus, based on the same fact findings and reasons set forth above and
in the Answer, we determine that the Examiner has not reversibly erred in
determining that the collective teachings of the prior art relied upon would
have rendered the subject matter of claims 5, 13, 23, 25, 31 through 33, and
37 through 40 obvious to one of ordinary skill in the art within the meaning
of 35 U.S.C. § 103(a)

Appeal 2010-006568
Application 10/851,514

10
ORDER
In view of the foregoing, it is
ORDERED that the decision of the Examiner rejecting claims 1
through 5, 8 through 11, 13, 16, 18 through 20, 23, 25, 27 through 29, 31
through 33, and 35 through 48 under 35 U.S.C. § 103(a) is AFFIRMED;
FURTHER ORDERED that the decision of the Examiner rejecting
claims 49 through 54 under 35 U.S.C. § 103(a) is REVERSED; 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)(1)(iv).
AFFIRMED-IN-PART

sld