Filed on behalf of Godo Kaisha IP Bridge 1
`
`
`
`
`UNITED STATES PATENT AND TRADEMARK OFFICE
`
`____________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`
`____________
`
`TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY LIMITED,
`Petitioner,
`
`v.
`
`GODO KAISHA IP BRIDGE 1,
`Patent Owner.
`____________
`
`
`
`DECLARATION OF HARLAN RUSTY HARRIS, PH.D.
`IN SUPPORT OF
`PATENT OWNER’S CONTINGENT MOTION TO AMEND
`
`IP Bridge Exhibit 2037
`TSMC v. IP Bridge
`IPR2016-01264
`
`Page 1 of 64
`
`
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`
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`UNITED STATES PATENT AND TRADEMARK OFFICE
`
`____________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`
`____________
`
`TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY LIMITED,
`Petitioner,
`
`v.
`
`GODO KAISHA IP BRIDGE 1,
`Patent Owner.
`____________
`
`
`
`DECLARATION OF HARLAN RUSTY HARRIS, PH.D.
`IN SUPPORT OF
`PATENT OWNER’S CONTINGENT MOTION TO AMEND
`
`IP Bridge Exhibit 2037
`TSMC v. IP Bridge
`IPR2016-01264
`
`Page 1 of 64
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`
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`I, Harlan Rusty Harris, declare as follows:
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`INTRODUCTION
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`1.
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`I have been retained by Godo Kaisha IP Bridge 1 (“Patent Owner”) in
`
`Cases IPR2016-01249 and IPR2016-01264 as a technical expert.
`
`2.
`
`I have been asked to study and provide my opinions concerning U.S.
`
`Patent No. 6,538,324 (“the ‘324 patent”) and the arguments and exhibits in the
`
`Petitions For Inter Partes Review of United States Patent No. 6,538,324 filed in
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`Cases IPR2016-01249 and IPR2016-01264, concerning the novelty and
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`nonobviousness of Claims 1-3, 5-7, and 9 in the ’324 patent (“Challenged
`
`Claims”).
`
`3.
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`I have been also been asked to study and provide my opinions
`
`regarding the novelty and nonobviousness of substitute claims 11-13 (“Substitute
`
`Claims”) proposed in Patent Owner’s Motion to Amend.
`
`4.
`
`I have been asked to provide my opinions based upon the state of the
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`relevant art prior to June 24, 1999, and the level and knowledge of one having
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`ordinary skill in the art in the June 1999 time frame.
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`5. My opinions and views set forth in this declaration are based on my
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`education, training, and experience in the field of semiconductor materials, devices
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`and process integration, as well as the materials I reviewed in this case.
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`1
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`Page 2 of 64
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`SUMMARY OF OPINIONS
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`6.
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`Based on my education, experience, knowledge of the art at the
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`relevant time, analysis of the prior art references as understood by a person having
`
`ordinary skill in the art at the relevant time, as well as a review of Petitioner’s
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`arguments, a review of Petitioner’s Expert Dr. Sanjay K. Banerjee’s declaration,
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`and the understanding a person having ordinary skill in the art would give to the
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`claim terms in light of the specification, it is my opinion that each of the Substitute
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`Claims is supported by the original specification, and each of the Substitute Claims
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`is neither anticipated by nor obvious over any prior art or combination of prior art
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`that I have reviewed or am aware of.
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`BACKGROUND AND QUALIFICATIONS
`
`7.
`
`I earned a bachelor of science in Engineering Physics from Texas
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`Tech University in 1997, a master of science in Electrical Engineering from Texas
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`Tech University in 1999, and a Ph.D. in Electrical and Computer Engineering from
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`the Texas Tech University in 2003. I was a visiting Assistant Professor at the
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`University of Missouri from August 2003 to May 2004; a visiting scientist at
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`International Sematech from May 2004 to August 2004; and a member of technical
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`staff at Advanced Micro Devices from September 2004 to August 2008. In August
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`2008 I became an Assistant Professor at Texas A&M University. I became an
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`Associate Professor in September 2014. I am currently an Associate Professor at
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`2
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`Page 3 of 64
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`Texas A&M University in the Department of Electrical and Computer Engineering
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`as well as the Department of Physics and Astronomy.
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`8. My research specialization is in CMOS and silicon technology;
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`materials and device integration; novel electrical and physical device and material
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`characterization; and III-V and nanophotonics. I am a recognized international
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`expert in silicon device and process technology at 32nm node and below, have
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`authored over 85 publications in refereed journals and conferences. A listing of
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`my publications and research is included in my curriculum vitae, a copy of which
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`is attached.
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`9.
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`I have not previously served as an expert witness in a litigation matter,
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`although I have been retained.
`
`10.
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`I am being compensated for services provided in this matter at a rate
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`of $300/hr. plus reasonable expenses. My compensation is not contingent on my
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`opinions, on the outcome of any matter, or on any of the technical positions I
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`explain in this declaration.
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`11.
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`I have no financial interest in the Petitioner, the Patent Owner or the
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`‘324 patent.
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`DOCUMENTS REVIEWED
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`12.
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`I have reviewed the Petitions For Inter Partes Review of United
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`States Patent No. 6,538,324 filed in Cases IPR2016-01249 and IPR2016-01264,
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`3
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`Page 4 of 64
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`the Exhibits submitted in support of the Petitions, including prior art references of
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`record therein as well as prior art references of record in the ‘324 patent.
`
`13.
`
`Thus, I have reviewed the following Exhibits:
`
`• Exhibit 1001: U.S. Patent No. 6,538,324 to Tagami et al.
`
`• Exhibit 1002: File History of U.S. Patent No. 6,538,324.
`
`• Exhibit 1003: Expert Declaration of Dr. Sanjay Kumar Banerjee.
`
`• Exhibit 1004: U.S. Patent No. 5,893,752 to Zhang et al.
`
`• Exhibit 1005: U.S. Patent No. 6,887,353 to Ding et al.
`
`• Exhibit 1006: Holloway et al., “Tantalum as a diffusion barrier between
`
`copper and silicon: Failure mechanism and effect of nitrogen additions,”
`
`Journal of Applied Physics, 71(11), 5433-5444 (1992).
`
`• Exhibit 1007: Sun et al., “Properties of reactively sputter-deposited Ta-
`
`N thin films,” Thin Solid Films, 236 (1993) 347-351.
`
`• Exhibit 1008
`
` U.S. Patent No. 5,858,873 to Vitkavage et al.
`
`• Exhibit 1009
`
` U.S. Patent No. 5,668,411 to Hong et al.
`
`• Exhibit 1010: Excerpt of El-Kareh, “Fundamentals of Semiconductor
`
`Processing Technologies,” Kluwer Academic Publishers (1995).
`
`• Exhibit 1015: Stavrev et al., “Crystallographic and morphological
`
`characterization of reactively sputtered Ta, Ta-N and Ta-N-O thin films,”
`
`Thin Solid Films, 307 (1997) 79-88.
`
`4
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`Page 5 of 64
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`
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`• Exhibit 1017: Duan et al., “Magnetic Property and Microstructure
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`Dependence of CoCrTa/Cr Media on Substrate Temperature and Bias,”
`
`IEEE Transactions on Magnetics, Vol. 28, No. 5, September 1992.
`
`• Exhibit 1019: Moussavi et al., “Comparison of Barrier Materials and
`
`Deposition Processes for Copper Integration,” Proceedings of the IEEE
`
`1998 International Interconnect Technology Conference, pp. 295-97
`
`(1998).
`
`• Exhibit 1021: Wijekoon et al., “Development of a Production Worthy
`
`Copper CMP Process,” 1998 IEEE/SEMI Advanced Semiconductor
`
`Manufacturing Conference, pp. 354-63 (1998).
`
`• Exhibit 1023: Wang et al., “Barrier Properties of Very Thin Ta and
`
`TaN layers Against Copper Diffusion,” J. Electrochem. Soc., Vol. 145,
`
`No. 7, pp. 2538-45.
`
`• Exhibit 2001: Chang, C.C., Chen, J.S. and Hsu, W.S., “Failure
`
`Mechanism of Amorphous and Crystalline Ta-N Films in the Cu/Ta
`
`N/Ta/SiO2 Structure.” Journal of The Electrochemical Society, 151(11),
`
`pp.G746-G750 (2004).
`
`• Exhibit 2002: U.S. Patent Application No. 08/995,108, Amendment
`
`“A” Under 37 C.F.R. §1.111, dated February 1, 2000.
`
`• Exhibit 2003: “Amorphous.” Merriam-Webster.com. Accessed
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`5
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`Page 6 of 64
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`
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`September 30, 2016. http://www.merriam-
`
`webster.com/dictionary/amorphous.
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`• Exhibit 2004: “Nitride.” Merriam-Webster.com. Accessed September
`
`30, 2016. http://www.merriam-webster.com/dictionary/nitride.
`
`• Exhibit 2008: Guralnik, D. B., ed. “Amorphous.” Def. 4. Webster’s
`
`New World Dictionary of the American Language. Modern desk ed.
`
`Prentice Hall Press, 1979. Print.
`
`• Exhibit 2009: Grant, J., ed. “Nitride.” Hackh’s Chemical Dictionary.
`
`4th ed. McGraw-Hill, 1969. Print.
`
`• Exhibit 2010: Sienko, Michell J., and Robert A. Plane. Chemistry:
`
`principles and applications. McGraw-Hill, 1979.
`
`• Exhibit 2014: JP H08-139092A.
`
`• Exhibit 2015: English translation of JP H08-139092A.
`
`• Exhibit 2016: JP H08-250596A.
`
`• Exhibit 2017: English translation of JP H08-250596A.
`
`• Exhibit 2018: JP H08-274098A.
`
`• Exhibit 2019: English translation of JP H08-274098A.
`
`• Exhibit 2020: JP H09-64044A.
`
`• Exhibit 2021: English translation of JP H09-64044A.
`
`• Exhibit 2022: JP H09-293690A.
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`6
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`Page 7 of 64
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`
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`• Exhibit 2023: English translation of JP H09-293690A.
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`• Exhibit 2024: JP H10-125627A.
`
`• Exhibit 2025: English translation of JP H10-125627A.
`
`• Exhibit 2026: JP H10-256256A.
`
`• Exhibit 2027: English translation of JP H10-256256A.
`
`• Exhibit 2028: JP H10-330938A.
`
`• Exhibit 2029: English translation of JP H10-330938A.
`
`• Exhibit 2030: JP H11-67686A.
`
`• Exhibit 2031: English translation of JP H11-67686A.
`
`• Exhibit 2032: D. Denning, et al., “An Inlaid CVD Cu Based Integration
`
`for Sub 0.25mum Technology.” 1998 Symposium on VLSI Technology
`
`Digest of Technical Papers, 1998, pp. 22-23.
`
`• Exhibit 2033: K. Kwon et al., “Characteristics of Ta As An Underlayer
`
`for Cu Interconnects.” Advanced Metallization and Interconnect Systems
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`for ULSI Applications in 1997, 1998, pp. 711-716.
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`• Exhibit 2034: N. Awaya, “Semiconductor World.” Feb. 1998, pp. 91-96
`
`(“Awaya”).
`
`• Exhibit 2035: English translation of Awaya.
`
`• Exhibit 2036: Grant, J., ed. “Solid Solution.” Hackh’s Chemical
`
`Dictionary. 4th ed. McGraw-Hill, 1969. Print.
`
`7
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`Page 8 of 64
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`
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`• Exhibit 2039: U.S. Patent No. 6,346,745 to Nogami et al.
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`• Exhibit 2040: U.S. Patent No. 6,156,647 to Hogan.
`
`• Exhibit 2041: U.S. Patent No. 6,139,699 to Chiang et al.
`
`• Exhibit 2042: Min, K. H. et al., “Comparative study of tantalum and
`
`tantalum nitrides (Ta2N and TaN) as a diffusion barrier for Cu
`
`metallization.” Journal of Vacuum Science & Technology B:
`
`Microelectronics and Nanometer Structures Processing, Measurement,
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`and Phenomena, 14(5), pp. 3263-3269 (1996).
`
`14.
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`I have also reviewed the Patent Owner’s Preliminary Response
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`Pursuant To 37 C.F.R. §42.107, including the above-noted Exhibits 2001, 2002,
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`2003 and 2004, submitted in support thereof filed in Cases IPR2016-01249 and
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`IPR2016-01264.
`
`15.
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`I have also reviewed the Decisions on Institution of Inter Partes
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`Review 37 C.F.R. § 42.108 in Cases IPR2016-01249 and IPR2016-01264.
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`16.
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`I have also reviewed the Patent Owner’s Responses filed in Cases
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`IPR2016-01249 and IPR2016-01264.
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`17.
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`I have also reviewed the Patent Owner’s Motions to Amend filed in
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`Cases IPR2016-01249 and IPR2016-01264.
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`8
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`Page 9 of 64
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`MY UNDERSTANDING OF THE RELEVANT LEGAL STANDARDS
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`18. For purposes of this Declaration, I have been asked to analyze and
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`assess the three Substitute Claims. I have been informed of and am familiar with
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`the relevant legal standards for amending claims and the burden of proof to
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`demonstrate patentability pertaining to anticipation and obviousness under 35
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`U.S.C. §§ 102 and 103.
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`19.
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`I understand that the proposed Substitute Claims must be supported
`
`by the original patent specification at the time of filing and that no new matter is
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`allowed.
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`20.
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`I understand that in the context of amending claims in an IPR, the
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`burden is on the Patent Owner to show patentable distinction over the prior art of
`
`record and also prior art known to the patent owner.
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`21.
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`I understand that, to show patentability of a claim under 35 U.S.C. §
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`102, the Patent Owner must show that a single prior art reference fails to disclose
`
`each and every element of the claims. Otherwise, a claim is said to be
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`“anticipated by the prior art.” An anticipating prior art reference must disclose
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`each of the claim elements expressly or inherently. I understand that “inherent”
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`disclosure means that the claim element, although not expressly described by the
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`prior art reference, must necessarily be present based on the disclosure. A mere
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`9
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`probability that the element is present is not sufficient to qualify as “inherent
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`disclosure.”
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`22.
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`I understand that a claim may be rendered obvious under 35 U.S.C. §
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`103. To show nonobviousness of a claim under 35 U.S.C. § 103, the Patent Owner
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`must show that the differences between the claimed subject matter and the prior art
`
`references be such that the subject matter as a whole would have been nonobvious
`
`to one of ordinary skill in the art at the time of the invention. I understand that
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`several factual inquiries underlie a determination of nonobviousness. These
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`inquiries include (1) the scope and content of the prior art, (2) the level of ordinary
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`skill in the field of the invention, (3) the differences between the claimed invention
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`and the prior art, and (4) any objective evidence of non-obviousness. I also
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`understand that the legal standard of invalidity requires a “common sense”
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`approach of examining whether the claimed subject matter would have been
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`obvious to one of ordinary skill in the art.
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`23.
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`I have been informed that in an obviousness determination, I must
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`avoid analyzing the prior art through the prism of hindsight. Instead, I must cast
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`the mind back to the time the invention was made and occupy the mind of a person
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`having ordinary skill in the art who is presented only with the references, and who
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`is normally guided by the then-accepted wisdom in the art.
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`10
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`24.
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`I have been informed that a patent claim is not proved obvious merely
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`by demonstrating that each of its elements was, independently, known in the prior
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`art. Rather, obviousness requires the additional showing that a person of ordinary
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`skill at the time of the invention would have selected and combined those prior art
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`elements in the normal course of research and development to yield the claimed
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`invention.”
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`25.
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`I have been informed that for an obviousness analysis, it can be
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`important to identify a reason that would have prompted a person of ordinary skill
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`in the relevant field to combine the elements in the way the claimed new invention
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`does, and that an assertion of obviousness cannot be sustained by mere conclusory
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`statements; instead, there must be some articulated reasoning with some rational
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`underpinning to support the legal conclusion of obviousness.
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`26.
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`I have also been informed that the prior art must be considered in its
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`entirety, i.e., as a whole, including portions that would teach away from the
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`claimed invention in suit.
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`A PERSON HAVING ORDINARY SKILL IN THE RELEVANT FIELD IN
`THE RELEVANT TIMEFRAME
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`27.
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`I have applied the above legal standards in forming the opinions
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`presented in this Declaration.
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`11
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`28.
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`I have been informed that an obviousness determination is made
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`from the perspective of person having ordinary skill in the art to which said
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`subject matter pertains.
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`29. A person having ordinary skill in the art ("PHOSITA") at the
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`relevant would have at least a Bachelor's degree in Electrical, Materials,
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`Mechanical, or Chemical Engineering, or a related degree, and at least two years
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`of experience working in semiconductor processing and fabrication,
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`semiconductor equipment manufacturing, or semiconductor materials.
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`PROPOSED SUBSTITUTE CLAIMS
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`30.
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`I have been asked to assess the following three Substitute Claims
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`11-13:
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`11. (Substitute for claim 5 if claim 5 is canceled) A multi-layered
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`wiring structure comprising a barrier film which prevents diffusion of
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`copper from a copper wiring layer formed on a semiconductor substrate,
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`said barrier film having a multi-layered structure of first and second
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`films,
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`said first film being composed of crystalline metal containing
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`nitrogen therein, the nitrogen being present throughout the first film,
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`said second film being composed of amorphous metal nitride,
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`said barrier film being constituted of common metal atomic species,
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`12
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`Page 13 of 64
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`said first film being formed on said second film,
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`said first film in direct contact with said second film,
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`said first film containing nitrogen in a smaller content than that of
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`said second film.
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`12. (Substitute for claim 9 if claim 9 is canceled) [[A]] The multi-
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`layered wiring structure as set forth in claim 5, comprising a barrier film
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`which prevents diffusion of copper from a copper wiring layer formed on a
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`semiconductor substrate,
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`said barrier film having a multi-layered structure of first and second
`
`films,
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`said first film being composed of crystalline metal containing
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`nitrogen therein,
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`said second film being composed of amorphous metal nitride,
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`said barrier film being constituted of common metal atomic species,
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`said first film being formed on said second film,
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`said first film in direct contact with said second film,
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`said first film containing nitrogen in a smaller content than that of
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`said second film,
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`further comprising a copper film formed on said first film,
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`13
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`Page 14 of 64
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`said copper film being in direct contact with said first film, wherein
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`said first film contains nitrogen in a portion being in contact with said
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`copper film.
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`13. (Substitute for claim 7 if claim 7 is canceled) The multi-layered
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`wiring structure as set forth in claim [[5]] 11, wherein said first film has a
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`thickness in the range of 60 angstroms to 300 angstroms both inclusive;
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`wherein said first film being composed of crystalline metal containing
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`nitrogen therein is a solid solution; and a copper film is formed on and in
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`direct contact with said first film.
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`SUPPORT OF SUBSTITUTE CLAIMS IN THE APPLICATION THAT
`ISSUED AS THE ‘324 PATENT
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`31.
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`It is my opinion that the proposed Substitute Claims 11-13 are
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`supported by Application No. 09/596,415 (“the ‘415 application”), filed June 19,
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`2000 (Exhibit 1002, ‘415 application file history). Based on the ‘415
`
`application, a PHOSITA would know that there is support in the ‘415 application
`
`for “the nitrogen being present throughout the first film” as more explicitly
`
`defined in Substitute Claim 11; for “said copper film being in direct contact with
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`said first film, wherein said first film contains nitrogen in a portion being in
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`contact with said copper film” as more explicitly recited in Substitute Claim 12;
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`and, for “wherein said first film being composed of crystalline metal containing
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`14
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`Page 15 of 64
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`nitrogen therein is a solid solution; and a copper film is formed on and in direct
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`contact with said first film” as recited in Substitute Claim 13.
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`32. Support for the Substitute Claims is present in the originally filed
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`U.S. application as shown in the Tables and discussion below:
`
`Substitute Claim 11
`
`Support in ‘415 application
`
`A multi-layered wiring structure
`
`At least p. 8:21-22; and claim 5 at line
`
`comprising
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`1 (p. 33); Ex. 1002, pp. 61, 86.
`
`a barrier film which prevents diffusion of
`
`At least p. 8:22-23; and claim 5 at lines
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`copper from a copper wiring layer
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`1-3 (p.33); Ex. 1002, pp. 61, 86.
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`formed on a semiconductor substrate,
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`said barrier film having a multi-layered
`
`At least p. 8:23-24; and claim 5, at line
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`structure of first and second films,
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`4; Ex. 1002, pp. 61, 86.
`
`said first film being composed of
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`At least p. 8:24-25; and claim 5 at lines
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`crystalline metal containing nitrogen
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`5-6 (p.33); Ex. 1002, pp. 61, 86.
`
`therein,
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`the nitrogen being present throughout the
`
`See discussion below
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`first film,
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`said second film being composed of
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`At least p. 8:25-26; and claim 5 at line
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`amorphous metal nitride,
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`7 (p.33); Ex. 1002, pp. 61, 86.
`
`said barrier film being constituted of
`
`At least p. 8:26-27; and claim 5 at line
`
`common metal atomic species,
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`8 (p.33); Ex. 1002, pp. 61, 86.
`
`said first film being formed on said
`
`At least p. 8:16; and claim 6 (pp.33-
`
`second film,
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`34); Ex. 1002, pp. 61, 86 and 87.
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`said first film in direct contact with said
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`At least p. 15:27-16:2; and Fig. 4B,
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`second film,
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`amorphous metal nitride film 15 and a
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`15
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`Page 16 of 64
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`
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`crystalline metal film 16 containing
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`nitrogen therein; Ex. 1002, pp. 68, 69
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`and 95.
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`said first film containing nitrogen in a
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`At least pp. 23:8-15; 28:17-20; Ex.
`
`smaller content than that of said second
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`1002, pp. 76, 81.
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`film.
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`
`
`Substitute Claim 12
`
`Support in ‘415 application as filed
`
`A multi-layered wiring structure
`
`At least p. 8:21-22; and claim 5 at line
`
`comprising
`
`1 (p. 33); Ex. 1002, pp. 61, 86.
`
`a barrier film which prevents diffusion of
`
`At least p. 8:22-23; and claim 5 at lines
`
`copper from a copper wiring layer
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`1-3 (p.33); Ex. 1002, pp. 61, 86.
`
`formed on a semiconductor substrate,
`
`said barrier film having a multi-layered
`
`At least p. 8:23-24; and claim 5, at line
`
`structure of first and second films,
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`4; Ex. 1002, pp. 61, 86.
`
`said first film being composed of
`
`At least p. 8:24-25; and claim 5 at lines
`
`crystalline metal containing nitrogen
`
`5-6 (p.33); Ex. 1002, pp. 61, 86.
`
`therein,
`
`
`
`said second film being composed of
`
`At least p. 8:25-26; and claim 5 at line
`
`amorphous metal nitride,
`
`7 (p.33); Ex. 1002, pp. 61, 86.
`
`said barrier film being constituted of
`
`At least p. 8:26-27; and claim 5 at line
`
`common metal atomic species,
`
`8 (p.33); Ex. 1002, pp. 61, 86.
`
`said first film being formed on said
`
`At least p. 8:16; and claim 6 (pp.33-
`
`second film,
`
`34); Ex. 1002, pp. 61, 86 and 87.
`
`said first film in direct contact with said
`
`At least p. 15:27-16:2; and Fig. 4B,
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`second film,
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`amorphous metal nitride film 15 and a
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`16
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`Page 17 of 64
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`
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`crystalline metal film 16 containing
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`nitrogen therein; Ex. 1002, pp. 68, 69
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`and 95.
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`said first film containing nitrogen in a
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`At least pp. 23:8-15; 28:17-20; Ex.
`
`smaller content than that of said second
`
`1002, p. 76, 81.
`
`film,
`
`a copper film formed on said first film,
`
`At least p. 9:1-2; and claim 10 (p. 34);
`
`said copper film being in direct contact
`
`At least p. 10:29-11:3; Ex. 1002, pp.
`
`Ex. 1002, pp. 62 and 87.
`
`with said first film,
`
`63-64.
`
`wherein said first film contains nitrogen
`
`
`
`in a portion being in contact with said
`
`At least p. 30:20-24; Ex. 1002, p. 83;
`
`copper film.
`
`and see discussion below.
`
`
`
`Substitute Claim 13
`
`Support in ‘415 application as filed
`
`The multi-layered wiring structure as set
`
`At least p. 8:21-22; and claim 5 at
`
`forth in claim [[5]] 11,
`
`line 1 (p. 33); Ex. 1002, pp. 61 and
`
`86.
`
`wherein said first film has a thickness in
`
`At least p. 9:19-20; and claim 8
`
`the range of 60 angstroms to 300
`
`(p.34); Ex. 1002, pp. 62, 87.
`
`angstroms both inclusive;
`
`wherein said first film being composed
`
`At least pp. 14:8-11; 22:22-25; and
`
`of crystalline metal containing nitrogen
`
`Fig. 21, Ex. 1002, pp. 67, 75.
`
`therein is a solid solution; and
`
`a copper film is formed on and in direct
`
`At least pp. 9:1-2; 10:29-11:3; claim
`
`contact with said first film.
`
`5, at line 7, and claim10 (pp. 33-34);
`
`17
`
`Page 18 of 64
`
`
`
`
`
`Ex. 1002, pp. 62-64, 86, 87.
`
`33. With respect to “the nitrogen being present throughout the first
`
`film”, as more explicitly recited in Substitute Claim 11, the presence of nitrogen
`
`throughout the first film would be readily apparent to a PHOSITA from the ‘415
`
`application from its description of being a solid solution, and also from the
`
`manner in which the first film is formed.
`
`34. The ‘415 application specification consistently describes a
`
`“crystalline metal film containing nitrogen therein” as a film composed of
`
`crystalline metal and nitrogen, for example, which includes β-Ta and TaN0 .1, in
`
`mixture. Exhibit 1002, 74 (21:4-7); see also 75 (22:6-10); 75 (22:13-28); 76
`
`(23:25-24:1); 81 (28:17-26). As depicted in Fig. 21, the crystalline metal film
`
`containing nitrogen therein is a “solid solution.” Exhibit 1002, 67 (14:8-11); 75
`
`(22:22-25); and Fig. 21. A solution is a “homogeneous mixture of two or more
`
`components” (Exhibit 2010, p. 193), while a “solid solution” is defined as a solid
`
`material “in which one component is randomly dispersed on an atomic or
`
`molecular scale throughout another component.” Exhibit 2010, p. 194. A solid
`
`solution is crystalline, although “there is no particular order as to which lattice
`
`points are occupied by which kind of atom.” Exhibit 2010, p. 194.
`
`18
`
`Page 19 of 64
`
`
`
`35. The ‘415 application includes as an example a film composed of β-
`
`Ta and TaN0 .1, and that these components are in mixture. Furthermore, the
`
`components themselves have nitrogen in solid solution. In the case of β-Ta,
`
`nitrogen is included within the limits of solid solubility by definition of
`
`maintaining its β-Ta identity and knowing that, when nitrogen is actively added,
`
`it can be included in the β-Ta. The same applies toTaN0 .1, and supporting XRD
`
`data is shown. Therefore, both are solid solutions. Because the ‘415 application
`
`describes the first film as “crystalline metal film containing nitrogen therein” as
`
`a solid solution, which is by definition homogenous, a PHOSITA would
`
`understand that the film is homogeneous, i.e., contains crystalline metal and
`
`nitrogen throughout from the top of the upper surface to the bottom of the first
`
`film.
`
`36. The discovery upon which the ‘415 application is indicated to be
`
`based, for example, ‘415 application, at 21:13-19, is included in each generally
`
`disclosed embodiment and each example in the ‘415 application. This discovery
`
`includes the “nitrogen in plasma gas being kept constant” when forming the
`
`amorphous and crystalline layers. See ‘415 application at 9:29-10:7; 11:22-
`
`12:1; 21:20-25; 31:23-28 (Exhibit 1002; pp.62, 63, 64, 65, 74, 84. The ‘415
`
`application teaches that increasing the RF power while maintaining the N2 gas
`
`ratio will change the film’s structural characteristics from amorphous to
`
`19
`
`Page 20 of 64
`
`
`
`crystalline metal film containing nitrogen therein. Exhibit 1002, 64-65 (11:22-
`
`12:1; 31:23-28). “In accordance with this method, an upper film in the
`
`diffusion-barrier film inevitably contains nitrogen therein.” Exhibit 1002, 84
`
`(31:27-28). A PHOSITA would have understood a film that is produced with
`
`“nitrogen in plasma gas being kept constant” and increased RF power would
`
`have nitrogen present throughout the “crystalline metal film containing nitrogen
`
`therein.” The continuous supply of nitrogen gas during the deposition would
`
`ensure such.
`
`37.
`
`“Said copper film being in direct contact with said first film” is
`
`taught in the ‘415 application at least at 10:29-11:3, (p. 33), Ex, 1002, pp. 63-43.
`
`38. Therefore, with respect to “said copper film being in direct contact
`
`with said first film, wherein said first film contains nitrogen in a portion being in
`
`contact with said copper film”, as more explicitly recited in Substitute Claim 12,
`
`a PHOSITA reading the ‘415 application would readily understand that the ‘415
`
`application teaches these features.
`
`39.
`
` “Wherein said first film contains nitrogen in a portion being in
`
`contact with said copper film” is taught in the ‘415 application at least at 30:20-
`
`24; Ex. 1002, p.88. Additionally, a PHOSITA would readily recognize that, as
`
`discussed in paragraph 33-36 above, nitrogen is present throughout the first film.
`
`Accordingly, with the copper film being in direct contact with the first film, the
`
`20
`
`Page 21 of 64
`
`
`
`first film would contain nitrogen in a portion being in contact with the copper
`
`film.
`
`40. With respect to “wherein said first film being composed of
`
`crystalline metal containing nitrogen therein is a solid solution; and a copper film
`
`is formed on and in direct contact with said first film” as recited in Substitute
`
`Claim 13, a PHOSITA reading the ‘415 application would readily understand
`
`that the ‘415 application teaches these features.
`
`41.
`
`“Wherein said first film being composed of crystalline metal
`
`containing nitrogen therein is a solid solution” is taught in the ‘415 application at
`
`least at 14:8-11; 22:22-25; and Fig. 21, Ex. 1002, pp. 67 and 75. “A copper film
`
`is formed on and in direct contact with said first film” is taught in the ‘415
`
`application at least at 9:1-2; 10:29-11:3; claim 5, at line 7, and claim10 (pp. 33-
`
`34); Ex. 1002, pp. 62-64 and 87.
`
`DESCRIPTION OF THE STATE OF THE ART
`
`42.
`
`In the late 1990s, there was a desire to use copper wiring layers in the
`
`manufacture of semiconductor devices. Exhibit 1001, 1:16. Copper, however, acts
`
`as a charge conduction point in silicon (Si), drifts through Si and silicon dioxide
`
`(SiO2) due to a voltage applied across these materials, and has a high diffusion rate
`
`in both Si and SiO2. Exhibit 1001, 1:21-25. For these reasons, it was determined
`
`that copper can be used, but it must be thoroughly and completely encapsulated in
`
`21
`
`Page 22 of 64
`
`
`
`another material that was suitably high in conductivity (albeit not as high a copper)
`
`and acted as a barrier for the diffusion of copper downward into either SiO2 or Si.
`
`Furthermore, in order to provide the appropriate amount of conductivity while also
`
`being reliable as a conductor in chip product, it was found that copper must be
`
`crystalline with a particular crystal orientation. Therefore, the material on which
`
`the copper was deposited must also foster the formation of the crystalline copper.
`
`These two properties are in tension with each other as, normally, a material that
`
`prevents diffusion is the opposite of crystalline, otherwise known as amorphous.
`
`43. The ‘324 patent describes prior art attempts which formed
`
`unsatisfactory copper diffusion-barriers. E.g., see Exhibit 1001, Fig. 2, 2:62-64
`
`(depicting a single layer metal film composed of crystallized pillar structures); Fig.
`
`3, 3:21-23 (depicting single layer metal film composed of amorphous particles).
`
`Barriers composed of crystallized pillar structures did not provide sufficient barrier
`
`characteristics to prevent copper diffusion. Exhibit 1001, 3:1-4. Barriers composed
`
`of amorphous material did not allow sufficient adhesion of copper. Exhibit 1001,
`
`29-33.
`
`44. Fig. 1 of the ‘324 patent depicts “a multi-layered barrier structure 3
`
`comprised of the titanium film 1 and the thin titanium nitride film 2.” Exhibit
`
`1001, 2:49-51.
`
`22
`
`Page 23 of 64
`
`
`
`45. The ‘324 patent discloses an improved diffusion-barrier over the prior
`
`
`
`art diffusion barriers.
`
`THE ‘324 PATENT
`
`46. The ‘324 patent discloses a multi-layered barrier film that prevents
`
`copper diffusion and sufficiently adheres to copper. The barrier film has first and
`
`second films wherein the first film is composed of crystalline metal containing
`
`nitrogen therein, and the second film is composed of amorphous metal nitride. The
`
`barrier film is constituted of common metal atomic species, the first film is formed
`
`on the second film and in direct contact with the second film, and the first film
`
`contains nitrogen in a smaller content than that of the second film. Exhibit 1001,
`
`18:65-19:3.
`
`47. The ‘324 patent teaches that an improved diffusion-barrier can be
`
`created by first forming an amorphous metal nitride film, and then forming a
`
`crystalline metal film containing nitrogen therein on the amorphous metal nitride
`
`film. Exhibit 1001, 5:1-8.
`
`23
`
`Page 24 of 64
`
`
`
`48. The ‘324 patent discloses that increasing the RF power while
`
`maintaining the nitrogen/argon gas ratio will change the film’s structural
`
`characteristics from amorphous to crystalline metal film containing nitrogen
`
`therein. Exhibit 1001, 12:58-67.
`
`49. As such, the multi-layered barrier film taught by the ‘324 patent does
`
`not have a pure metal surface, but rather has a crystalline metal layer containing
`
`nitrogen throughout the film, including the surface which contacts a copper layer.
`
`This is very different from the prior art films that stop the nitrogen flow to form a
`
`layer with a pure metal surface.
`
`50. Fig. 21 of the ‘324 patent (depicted below) shows a claimed
`
`embodiment having a first film (18)1 composed of crystalline metal containing
`
`nitrogen therein, and a second film (15) composed of amorphous metal nitride.
`
`Exhibit 1001, 8:24-29; 13:15-23.
`
`
`1 In Fig. 21, the crystalline metal film containing nitrogen is labeled element
`
`
`
`18 but is referred to in the specification as element 16. Exhibit 1001, 13:15-23.
`
`24
`
`Page 25 of 64
`
`
`
`51. Fig. 21 (depicted above) is a cross-sectional view of a diffusion-
`
`barrier film “comprised of a crystalline Ta film containing nitrogen in solid
`
`solution and an amorphous metal TaN film.” Exhibit 1001, 8:24-28.
`
`52. A solution is a “homogeneous mixture of two or more components,
`
`while a “solid solution” is a solid material “in which one component is randomly
`
`dispersed on an atomic or molecular scale throughout another material.”
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