Ex Parte Vlassiouk et al

Patent Trial and Appeal Board

Mar 16, 2018

13734823 (P.T.A.B. Mar. 16, 2018)

UNITED STA TES p A TENT AND TRADEMARK OFFICE
APPLICATION NO. FILING DATE FIRST NAMED INVENTOR
13/734,823 01/04/2013 Ivan V. Vlassiouk
95895 7590 03/20/2018
Warner Norcross & Judd, LLP
900 Fifth Third Center
111 Lyon Street, NW
Grand Rapids, MI 49503-2487
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
ATTORNEY DOCKET NO. CONFIRMATION NO.
138974.152220-US 7558
EXAMINER
TUROCY, DAVID P
ART UNIT PAPER NUMBER
1718
NOTIFICATION DATE DELIVERY MODE
03/20/2018 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):
patents@wnj.com
gbondarenko@wnj.com
PTOL-90A (Rev. 04/07)
UNITED STATES PATENT AND TRADEMARK OFFICE
BEFORE THE PATENT TRIAL AND APPEAL BOARD
Ex parte IV AN V. VLASSIOUK, SERGEI N. SMIRNOV,
WILLIAM H. PETER, ADRIAN S. SABAU, SHENG DAI,
PASQUALE F. FULVIO, LLIA N. IVANOV, NICKOLAY V.
LA VRIK, and PANA GI OTIS G. DATSKOS
Appeal2017-006674
Application 13/734,823
Technology Center 1700
Before TERRY J. OWENS, CHRISTOPHER C. KENNEDY, and
JANEE. INGLESE, Administrative Patent Judges.
OWENS, Administrative Patent Judge.
DECISION ON APPEAL
STATEMENT OF THE CASE
The Appellants appeal under 35 U.S.C. § 134(a) from the Examiner's
rejection of claims 1-9, 11-17 and 19-23. We have jurisdiction under
35 U.S.C. § 6(b ).
The Invention
The Appellants claim a method for forming by chemical vapor
deposition at atmospheric pressure a monolayer or multilayer of graphene
including crystal hexagonal grains. Claim 1 is illustrative:
1. A method of making a monolayer or multilayer of
poly-crystalline and single crystalline graphene comprising:
Appeal2017-006674
Application 13/734,823
providing a chemical vapor deposition chamber
including a pre-deposition region and a deposition region in
fluid communication with each other at atmospheric pressure;
providing a continuous copper substrate for movement
through the chemical vapor deposition chamber;
drawing the copper substrate through the pre-deposition
region of the chemical vapor deposition chamber at
atmospheric pressure and in the presence of hydrogen gas to
anneal the copper substrate;
introducing a hydrocarbon gas and a buff er gas at a
nozzle opening coextensive with the deposition region of the
chemical vapor deposition chamber to mix with hydrogen
gas escaping from the pre-deposition region at the nozzle
opening, thereby forming a reaction gas mixture in the
deposition region, the reaction gas mixture being at
atmospheric pressure;
drawing the copper substrate through the deposition
region of the chemical vapor deposition chamber while
introducing the hydrocarbon gas at the nozzle opening so that
the copper substrate continuously reacts with the reaction gas
mixture in the deposition region, the reaction gas mixture
having a partial pressure of hydrogen gas at 10-20 Torr and a
partial pressure of hydrocarbon gas at 23-100 mTorr with a
ratio of hydrogen gas partial pressure to hydrocarbon gas
partial pressure of greater than 400 to form a monolayer or
multilayer of graphene including crystal hexagonal grains,
wherein the hydrogen gas contributes to the annealing of the
copper substrate in the pre-deposition region and contributes
to the formation of active surface-bound carbon species in the
deposition region; and
continuously extracting the copper substrate from the
chemical vapor deposition chamber, the extracted copper
substrate supporting the monolayer or multilayer of graphene
including crystal hexagonal grains.
Choi
Veerasamy
The References
US 2009/0068471 Al
US 2011/0143045 Al
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Mar. 12, 2009
June 16, 2011
Appeal2017-006674
Application 13/734,823
Hong US 2011/0195207 Al Aug. 11, 2011
Sreekar Bhaviripudi et al., Role of Kinetic Factors in Chemical Vapor
Deposition Synthesis of Uniform Large Area Graphene Using Copper
Catalyst, 10 Nano Lett. 4128-33 (2010).
Thorsten Hesjedal, Continuous roll-to-roll growth of graphene films by
chemical vapor deposition, 98 Appl. Phys. Lett. 133106-1 - 106-3.
The Rejections
The claims stand rejected under 35 U.S.C. § 103 as follows: claims 1-
5, 7-9, 11-14, 17, and 19-23 over Hesjedal in view of Hong and
Bhaviripudi, claims 6, 13, 15, and 16 over Hesjedal in view of Hong,
Bhaviripudi and Veerasamy and claims 6, 7, 13, 15, and 16 over Hesjedal in
view of Hong, Bhaviripudi and Choi.
OPINION
We reverse the rejections. We need address only the independent
claims (1, 8 and 17). Claim 1 requires a reaction gas mixture having a 10-
20 Torr partial pressure of hydrogen gas and a 23-100 mTorr partial
pressure of hydrocarbon gas with a ratio of hydrogen gas partial pressure to
hydrocarbon gas partial pressure of greater than 400. Claims 8 and 17
require a reaction gas mixture having a partial pressure of hydrogen gas
between about 10 Torr and about 20 Torr and a partial pressure of
hydrocarbon gas between about 23 mTorr and about 100 mTorr with a ratio
of hydrogen gas partial pressure to hydrocarbon gas partial pressure of
greater than 400.
Hesjedal continuously grows graphene on a copper substrate by
atmospheric pressure chemical vapor deposition from a gas mixture
comprising methane as the carbon feedstock, hydrogen for etching unwanted
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Application 13/734,823
oxides and other contaminants from the copper surface prior to growth and
for selectively etching amorphous carbon deposits, and argon as an inert
transport gas (p. 133106-1 ). Typical gas flows are approximately 50 seem
for H2, 25 seem for methane and 1,000 seem for argon (id.).
Hong coats a metallic member surface with graphene by atmospheric
pressure chemical vapor deposition from a gas mixture comprising a carbon
source (which can be methane), hydrogen to keep the metallic member
surface clean and thereby control the gas phase reaction, and optionally a
nonreactive gas such as helium or argon (iJiJ 76-78). "The amount of the
hydrogen may range from about 1 to 40 volume % of the entire volume of a
vessel, desirably, about 10 to 30 volume % and, more desirably, about 15 to
25 volume %" (iJ 77). The exemplified volumetric ratio of hydrogen to
methane is 10: 3 0 (iJ 116).
Bhaviripudi synthesizes graphene on copper by atmospheric chemical
vapor deposition from methane (p. 4132) and teaches that graphene is a
single atomic layer of carbon atoms in a hexagonal network (p. 4128). In an
example the gas flow rates are 50 seem hydrogen and 450 seem argon
containing 100 ppm methane (p. 4129, Table 1 (Cu APCVD-S5)) (which, as
indicated by the Appellants, corresponds to a hydrogen partial pressure of
about 76 Torr (which is outside the Appellants' 10-20 Torr range), a
methane partial pressure of about 68 mTorr (which is within the Appellants'
23-100 mTorr range), and a ratio of hydrogen partial pressure to methane
partial pressure of about 1111 (which is within the Appellants' range of
greater than 400) (Reply Br. 4).
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Appeal2017-006674
Application 13/734,823
The Examiner finds that Bhaviripudi's "disclosure that graphene
exists in hexagonal arrangement would indicate that the requirement of
'including crystal hexagonal grains' is met" (Ans. 16).
The Appellants challenge that finding, arguing that although graphene
has a hexagonal bonding geometry (hexagonal network) its grains may or
may not have a hexagonal shape (Reply Br. 1-2, 7-8). That argument is
supported by the Appellants' experimental evidence (Spec. iii! 45, 51;
Figs. 4, 7). Accordingly, we do not accept the Examiner's finding as fact.
See In re Kunzmann, 326 F.2d 424, 425 n.3 (CCPA 1964). The Examiner,
therefore, must support the finding with evidence, and the Examiner has not
done so.
The Examiner finds that "Hong discloses at (0077) the hydrogen gas
is a result effective variable, directly affecting the process and the amount of
carbon gas is clearly a result effective variable as its reacting to deposit a
film (i.e. too little and no film is formed and too much overloads the
chamber for deposition)" (Ans. 4) and "Bharviripudi [sic] discloses the
carbon flow is a result effective variable, directly affecting the deposition
(see entire reference e.g. Table 1, page 4132), see additionally Figure 1
which discloses the differing optimal images under APCVD 'at different
methane gas concentrations' and stating 'graphene synthesis using Cu
catalyst under APCVD conditions using a range of methane gas composition
revealed that growth varied from monolayer graphene at low methane
concentrations (ppm) to multilayer domains on a monlayer [sic] at higher
methane concentrations' (page 4132, right column first full paragraph)"
(Ans. 12).
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Appeal2017-006674
Application 13/734,823
The Examiner does not establish that Hong and/or Bhaviripudi would
have indicated to one of ordinary skill in the art that hydrogen partial
pressure, hydrocarbon partial pressure or hydrogen partial
pressure/hydrocarbon partial pressure ratio is an effective variable for
achieving either the Appellants' result of hexagonal grain shape or any other
result achievable by using the Appellants' recited values of those variables.
The Examiner's mere finding that Hong and Bhaviripudi would have
indicated to one of ordinary skill in the art that those variables affect the
process does not establish that the applied references would have led one of
ordinary skill in the art to the values of those variables used by the
Appellants to obtain a hexagonal grain shape.
Thus, the Examiner has not established a prima face case of
obviousness of the Appellants' claimed method.
DECISION/ORDER
Therejectionsunder35U.S.C. § 103ofclaims1-5, 7-9, 11-14, 17,
and 19-23 over Hesjedal in view of Hong and Bhaviripudi, claims 6, 13, 15,
and 16 over Hesjedal in view of Hong, Bhaviripudi and Veerasamy and
claims 6, 7, 13, 15, and 16 over Hesjedal in view of Hong, Bhaviripudi and
Choi are reversed.
It is ordered that the Examiner's decision is reversed.
REVERSED
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