`
`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 DR. SANJAY K. BANERJEE
`
`IN SUPPORT OF PETITIONER’S REPLY TO PATENT OWNER’S
`RESPONSE AND OPPOSITION TO MOTION TO AMEND
`
`FOR INTER PARTES REVIEW OF UNITED STATES
`PATENT NO. 6,538,324
`
`Page 1 of 23
`
`TSMC Exhibit 1038
`TSMC v. IP Bridge
`IPR2016-01264
`
`
`
`TABLE OF CONTENTS
`INTRODUCTION ........................................................................................... 2
`
`I.
`
`II. MATERIALS REVIEWED ............................................................................ 2
`
`III. LEVEL OF ORDINARY SKILL .................................................................... 6
`
`IV. LEGAL STANDARDS ................................................................................... 7
`
`V.
`
`CLAIM CONSTRUCTION ............................................................................ 8
`
`VI. OPINIONS ....................................................................................................... 8
`
`A.
`
`B.
`
`C.
`
`D.
`
`E.
`
`F.
`
`G.
`
`H.
`
`Patent Owner’s Substitute Claims 11-13 .............................................. 8
`
`The combinations of Zhang and Ding in view of Chiang render
`the Substitute Claims obvious ............................................................. 10
`
`Nogami teaches a multi-layer diffusion barrier structure similar
`to those in Zhang and Ding ................................................................. 11
`
`The combinations of Ding and Zhang in view of Nogami
`renders Substitute Claim 11 obvious. .................................................. 13
`
`The combinations of Ding and Zhang in view of Nogami
`renders Substitute Claim 12 obvious. .................................................. 14
`
`The combinations of Ding and Zhang in view of Nogami
`renders Substitute Claim 13 obvious. .................................................. 15
`
`The construction of “solid solution” in Substitute Claim 13 is
`“a homogeneous mixture of a substance in a single solid phase” ....... 17
`
`Lack of written description for the “first film . . . is a solid
`solution” in Substitute Claim 13 ......................................................... 18
`
`VII. CONCLUSION .............................................................................................. 21
`
`
`
`1
`
`
`
`
`
`Page 2 of 23
`
`
`
`I, Sanjay Kumar Banerjee, declare as follows:
`
`I.
`
`INTRODUCTION
`
`1. My name is Dr. Sanjay Kumar Banerjee, and I submitted an expert
`
`declaration (Exhibit 1003) in this proceeding on June 24, 2016.
`
`2.
`
`I have been asked to submit this declaration on behalf of Taiwan
`
`Semiconductor Manufacturing Company Limited (“TSMC” or “Petitioner”) in
`
`connection with its Reply to Patent Owner’s Response and Opposition to Patent
`
`Owner’s Motion to Amend Claims in the current proceeding.
`
`3.
`
`I have been asked to provide opinions in response to certain positions
`
`taken by IP Bridge (“Patent Owner”) in its Patent Owner’s Response and Motion
`
`to Amend Claims. My opinions in this declaration are presented in addition to my
`
`opinions in my previous declaration. This declaration does not replace, modify, or
`
`withdraw any of my earlier opinions and analyses offered in this proceeding.
`
`II. MATERIALS REVIEWED
`
`4.
`
`In forming my opinions, I have reviewed the materials listed in my
`
`previous declaration (Exhibit 1003) and the following materials and any other
`
`materials I identify in this declaration or in my previous declaration:
`
` 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 to Tagami et al.
`
` Exhibit 1004: U.S. Patent No. 5,893,752 to Zhang et al.
`
`
`
`
`2
`
`Page 3 of 23
`
`
`
` 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.
`
` Exhibit 1017: Duan et al., “Magnetic Property and Microstructure
`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 1025: U.K. Patent No. GB 2,298,657 to Cho.
`
` Exhibit 1026: U.S. Patent No. 5,780,908 to Sekiguchi et al.
`
`
`
`3
`
`Page 4 of 23
`
`
`
`
` Exhibit 1027: U.S. Patent No. 5,869,902 to Lee et al.
`
` Exhibit 1028: U.S. Patent No. 5,882,399 to Ngan et al.
`
` Exhibit 1029: U.S. Patent No. 6,057,237 to Ding et al.
`
` Exhibit 1030: U.S. Patent No. 6,136,682 to Hegde et al.
`
` Exhibit 1031: U.S. Patent No. 6,242,804 to Inoue et al.
`
` Exhibit 1032: Annotated FIG. 4 of Zhang (Ex. 1004).
`
` Exhibit 1033: U.S. Patent No. 6,458,255 to Chiang et al.
`
` Exhibit 1034: Excerpt of “The American Heritage College Dictionary,” 3rd
`Ed., Houghton Mifflin Company (1993).
`
` Exhibit 1035: U.S. Patent No. 5,281,485 to Colgan et al.
`
` Exhibit 1036: May 5, 2017, Deposition Transcript of Harlan (Rusty) Harris,
`Ph.D., and all exhibits thereto
`
` Institution Decision in IPR2016-01249
`
` Institution Decision in IPR2016-01264
`
` Patent Owner Response in IPR2016-01249
`
` Patent Owner Response in IPR2016-01264
`
` Patent Owner’s Contingent Motion to Amend Claims
`
` 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.
`
`
`
`4
`
`Page 5 of 23
`
`
`
`
` 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, M.J., Plane, R.A. Chemistry. 2d ed. New York,
`McGraw-Hill, 1961, pp. 193-195. Print.
`
` Exhibit 2011: Declaration of Harlan (Rusty) Harris, Ph.D. in IPR2016-01249
`
` Exhibit 2011: Declaration of Harlan (Rusty) Harris, Ph.D. in IPR2016-01264
`
` Exhibit 2012: MPEP, 2111.03 Transitional Phrases [R-08.2012].
`
` Exhibit 2013: Claim Construction Memorandum And Order, November 9,
`2016, pp. 31-32 (Godo Kaisha IP Bridge 1 v. Broadcom Limited et al.,
`USDC EDTEX 2:16-cv-00134-JRG-RSP).
`
` Exhibit 2015: English translation of JP H08-139092A
`
` Exhibit 2017: English translation of JP H08-250596A
`
` Exhibit 2019: English translation of JP H08-274098A
`
` Exhibit 2021: English translation of JP H09-64044A
`
` Exhibit 2023: English translation of JP H09-293690A
`
` Exhibit 2025: English translation of JP H10-125627A
`
` Exhibit 2027: English translation of JP H10-256256A
`
` Exhibit 2029: English translation of JP H10-330938A
`
` Exhibit 2031: English translation of JP H11-67686A
`
`
`
`
`5
`
`Page 6 of 23
`
`
`
` Exhibit 2032: D. Denning, et al., “An Inlaid CVD Cu Based Integration for
`Sub 0.25μm 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 for ULSI
`Applications in 1997, 1998, pp. 711-716.
`
` Exhibit 2035: English translation of Awaya.
`
` Exhibit 2036: Grant, J., ed. “Solid Solution.” Hackh’s Chemical Dictionary.
`4th ed. McGraw-Hill, 1969. Print.
`
` Exhibit 2037: Declaration of Harlan (Rusty) Harris, Ph.D. In Support of
`Patent Owner’s Contingent Motion to Amend
`
` Exhibit 2039: U.S. Patent No. 6,346,745 to Nogami et al.
`
` 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, and Phenomena, 14(5), pp.
`3263-3269 (1996).
`III. LEVEL OF ORDINARY SKILL
`
`5.
`
`As I explained in ¶¶ 64-65 of my previous declaration, a person of
`
`ordinary skill in the art (POSITA) when the application leading to the ’324 patent
`
`was filed, which I was told to assume is June 24, 1999, would have an equivalent
`
`of a Master of Science degree from an accredited institution in electrical
`
`engineering, materials science, or physics, or the equivalent, a working knowledge
`
`
`
`6
`
`Page 7 of 23
`
`
`
`of semiconductor processing technologies for integrated circuits, and at least two
`
`years of experience in semiconductor processing analysis, design, and
`
`development. Additional graduate education could substitute for professional
`
`experience, and significant work experience could substitute for formal education.
`
`I was at least a person of ordinary skill in the art when the application leading to
`
`the ’324 patent was filed. I have applied this understanding of the level of ordinary
`
`skill in the art at the relevant time in forming my opinions in this declaration.
`
`IV. LEGAL STANDARDS
`
`6.
`
`In this declaration, I have applied my understanding of the legal
`
`standards for anticipation and obviousness as I described in ¶¶ 21-37 of my
`
`previous declaration, Exhibit 1003.
`
`7.
`
`I have also been told that the ’324 patent must contain a written
`
`description of the claimed invention, and of the manner and process of making and
`
`using it, in such full, clear, concise, and exact terms as to enable a POSITA in the
`
`art to which it pertains, or with which it is most nearly connected, to make and use
`
`the invention. I also have been told that a claim of a patent may be unpatentable if
`
`the patent lacks written-description support for the subject matter of the claim.
`
`8.
`
`I have been told that the purpose of the written description
`
`requirement is to prevent an applicant or patent owner from later claiming that
`
`he/she possesses an invention which he/she did not. I also have been told that the
`
`
`
`7
`
`Page 8 of 23
`
`
`
`requirement does not mandate the specification recite the claimed subject matter
`
`verbatim, but that a description in the specification rendering a claimed invention
`
`obvious does not satisfy the written description requirement.
`
`9.
`
`In addition, I have been told that to establish whether the specification
`
`inherently supports the subject matter of a claimed invention requires an applicant
`
`or patent owner show the missing descriptive matter is necessarily, not merely
`
`possibly or probably, present in the specification, and a POSITA would have
`
`recognized it.
`
`V. CLAIM CONSTRUCTION
`
`10.
`
`I was informed by counsel that, for purposes of this inter partes
`
`review proceeding, the claims in the ’324 patent should have their broadest
`
`reasonable construction in light of the patent specification.
`
`11. Unless otherwise noted, my opinions in this declaration are consistent
`
`with the broadest reasonable construction of the claims to a person of ordinary skill
`
`in the art when the application leading to the ‘324 patent was filed.
`
`VI. OPINIONS
`
`A.
`12.
`
`Patent Owner’s Substitute Claims 11-13
`
`I understand Patent Owner proposes to amend claims 1, 5, and 9, and
`
`replace them with the following Substitute Claims 11-13:
`
`Substitute Claim 11 (Substitute for claim 5 if claim 5 is canceled) A
`multi-layered wiring structure comprising a barrier film which
`
`
`
`8
`
`Page 9 of 23
`
`
`
`prevents diffusion of copper from a copper wiring layer formed on a
`semiconductor substrate,
`said barrier film having a multi-layered structure of first and
`second films,
`said first film being composed of crystalline metal containing
`nitrogen therein, the nitrogen being present throughout
`the first film,
`said second film being composed of amorphous metal nitride,
`
`said barrier film being constituted of common metal
`atomic species,
`said first film being formed on said second film,
`said first film in direct contact with said second film,
`said first film containing nitrogen in a smaller content than that
`of said second film.
`
`
`
`
`
`Substitute Claim 12 (Substitute for claim 9 if claim 9 is canceled) The
`multi-layered wiring structure as set forth in claim 5, comprising a
`barrier film which prevents diffusion of copper from a copper wiring
`layer formed on a semiconductor substrate,
`said barrier film having a multi-layered structure of first and
`second films,
`said first film being composed of crystalline metal containing
`nitrogen therein,
`said second film being composed of amorphous metal nitride,
`said barrier film being constituted of common metal atomic
`species,
`
`
`
`9
`
`Page 10 of 23
`
`
`
`said first film being formed on said second film,
`said first film in direct contact with said second film,
`said first film containing nitrogen in a smaller content than that
`of said second film,
`a copper film formed on said first film, 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.
`
`
`
`Substitute Claim 13 (Substitute for claim 7 if claim 7 is canceled) The
`multi-layered wiring structure as set forth in claim 11, wherein said
`first film has a thickness in the range of 60 angstroms to 300
`angstroms both inclusive;
`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.
`It is my opinion that each of the Substitute Claims 11-13 proposed by
`
`13.
`
`Patent Owner would be invalid over the prior art in the record.
`
`14.
`
`It is also my opinion that the ’324 patent lacks written description
`
`support for the “first film . . . is a solid solution” recited in Substitute Claim 13.
`
`B.
`
`15.
`
`The combinations of Zhang and Ding in view of Chiang render the
`Substitute Claims obvious
`In my opinion, although Ding does not expressly disclose the top
`
`crystalline tantalum film contains nitrogen, a POSITA at the time of filing of the
`
`
`
`10
`
`Page 11 of 23
`
`
`
`application leading to the ’324 patent would have understood that there would be a
`
`small amount of nitrogen in Ding’s top film. For example, the inventors of the
`
`Ding patent disclose in their co-pending application, U.S. Patent No. 6,458,255
`
`(Exhibit 1033 to Chiang) that the surface of Ding’s top barrier film may contain “a
`
`small amount of nitrogen (typically less than about 15 atomic percent).” Ex. 1033
`
`at 1:44-57. A POSITA would have understood, especially in view of Chiang, that
`
`Ding’s top barrier film does not require a “pure” tantalum top layer.
`
`16. At least a combination of Ding with its related Chiang patent, clarifies
`
`that it would have been obvious to a POSITA that the upper surface of Ding’s top
`
`film would contain “a small amount of nitrogen.” Ex. 1033, 1:44-57. In my
`
`opinion, a combination of Ding and Zhang further in view of Chiang would render
`
`obvious Patent Owner’s Substitute Claims with the added limitations of requiring
`
`nitrogen throughout the “first film.” A POSITA would have understood that Ding
`
`alone, or in further combination with Chiang, discloses a crystalline Ta film
`
`containing nitrogen as required in the Substitute Claims.
`
`C. Nogami teaches a multi-layer diffusion barrier structure similar
`to those in Zhang and Ding
`17. Nogami discloses a multi-layered barrier layer for preventing copper
`
`diffusion, where the barrier layer includes a lower layer of amorphous TaN and an
`
`upper layer of Ta or TaN having a nitrogen content less than the lower layer’s. Ex.
`
`2039, Abstract. The upper layer is in contact with a copper layer. Id., 3:8-15
`
`
`
`11
`
`Page 12 of 23
`
`
`
`(disclosing a barrier layer “comprising: a first layer . . . ; a second layer . . . ; a third
`
`layer [the lower layer] comprising TaN having a nitrogen content less than that of
`
`the TaN of the second layer . . . ; and a fourth layer [the upper layer], comprising
`
`Ta or TaN having a nitrogen content less than the TaN of the third layer, on the
`
`third layer and in contact with a surface the Cu or Cu alloy feature”). Nogami
`
`teaches the upper layer has “a nitrogen content less than 15 at. % enhances the
`
`adhesion of Cu to the third layer, thereby improving electromigration resistance.”
`
`Id., 5:39-42.
`
`18.
`
`In my opinion, to the extent Nogami does not expressly disclose a
`
`crystalline upper layer, it would have been obvious to a POSITA to modify
`
`Nogami to ensure its upper layer is crystalline, for enhancing the adhesion of Cu
`
`and electromigration resistance. See, e.g., Ex. 1005, Abstract, 8:1-4.
`
`19.
`
`I believe a POSITA would have found it obvious to have combined
`
`Nogami’s disclosure of nitrogen content throughout an upper layer of Ta or TaN
`
`with Ding and Zhang to achieve the predictable benefits of such a combination, as
`
`each of Nogami, Ding, and Zhang aims to improve adhesion of the top film of a
`
`barrier layer with copper, and Ding further discloses that a crystalline upper layer
`
`improves adhesion. Ex. 1005, 8:1-4, Abstract; Ex. 1004, Abstract; Ex. 1036,
`
`78:6-83:7; Ex. 2039, 5:39-42.
`
`
`
`12
`
`Page 13 of 23
`
`
`
`20.
`
`It is my opinion the combination of Nogami with Ding and Zhang
`
`applies known techniques to yield predictable results. Nogami, similar to Ding and
`
`Zhang, sputters the barrier layer in “a single sputter deposition chamber
`
`comprising a Ta target and adjusting the amount of nitrogen in the sputter
`
`deposition chamber to form the [multi-layered barrier layer] having different
`
`nitrogen contents.” Ex. 2039, 5:11-16; Ex. 1004, 3:37-62; Ex. 1005, 7:21-29.
`
`D. The combinations of Ding and Zhang in view of Nogami renders
`Substitute Claim 11 obvious.
`It is also my opinion that Nogami alone or with Ding and Zhang
`
`21.
`
`discloses and renders obvious the added subject matter in Substitute Claim 11,
`
`which recites the limitations in claim 5 and the added limitation that “the nitrogen
`
`being present throughout the first film.”
`
`22. The combined teachings of Ding and Zhang render obvious claim 5.
`
`Nogami teaches the new limitation of Substitute Claim 11, since Nogami discloses
`
`the upper Ta or TaN layer contains nitrogen less than about 15% and the layer was
`
`formed using a certain amount of nitrogen during sputtering. Ex. 2039, 3:38-39
`
`(“fourth layer of Ta or TaN having a nitrogen content less than about 15 at %.”);
`
`5:11-16 (“a single sputter deposition chamber comprising a Ta target and adjusting
`
`the amount of nitrogen in the sputter deposition chamber to form the second, third,
`
`and fourth layers 15 having different nitrogen contents”). In my opinion, a
`
`POSITA would have understood that Nogami teaches an upper layer containing
`
`
`
`13
`
`Page 14 of 23
`
`
`
`nitrogen throughout, from the upper surface to the bottom surface of the layer,
`
`because the layer was formed using a certain amount of nitrogen during sputtering.
`
`23. Thus, in my opinion, Nogami, when combined with Ding and Zhang,
`
`renders obvious Substitute Claim 11 obvious.
`
`E.
`
`The combinations of Ding and Zhang in view of Nogami renders
`Substitute Claim 12 obvious.
`24. Nogami alone or with Ding and Zhang discloses and renders obvious
`
`the added subject matter in Substitute Claim 12, which recites the limitations in
`
`claim 9 and adds the limitation “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.” Claim 9 depends from claim 5 and adds “a copper film
`
`formed on said first film.”
`
`25. The Board found in its Institution Decision that the combined
`
`teachings of Ding and Zhang render obvious claim 9. I agree. Nogami further
`
`discloses “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
`
`Substitute Claim 12 recites, since Nogami discloses the upper Ta or TaN layer,
`
`which is in contact with copper, contains nitrogen throughout, from the upper
`
`surface to the bottom surface of the layer, as discussed above. See, e.g., Ex. 2039,
`
`3:14-15. In my opinion, Nogami, when combined with Ding and Zhang, renders
`
`Substitute Claim 12 obvious.
`
`
`
`14
`
`Page 15 of 23
`
`
`
`F.
`
`The combinations of Ding and Zhang in view of Nogami renders
`Substitute Claim 13 obvious.
`
`26.
`
`It is my opinion that Nogami alone or with the combination of Ding
`
`and Zhang discloses and renders obvious the subject matter in Substitute Claim 13,
`
`which depends from Substitute Claim 11. Claim 13 recites the limitations from
`
`claim 7, “wherein said first film has a thickness in the range of 60 angstroms to
`
`300 angstroms both inclusive;” and adds new limitations, “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.”
`
`27. Nogami discloses “said first film has a thickness in the range of 60
`
`angstroms to 300 angstroms both inclusive” as Substitute Claim 13 recites. Ex.
`
`2039, 3:38-40 (“depositing the fourth layer of Ta or TaN having a nitrogen content
`
`less than about 15 at. % at a thickness of about 50 (cid:1344) to about 150 (cid:1344).”). Nogami
`
`further discloses the added limitation “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 it discloses the upper Ta or TaN
`
`layer contains nitrogen throughout, from the upper surface to the bottom surface of
`
`the layer, as discussed above; and Nogami does not refer to the upper Ta or TaN
`
`layer as a mixture of distinct material phases. See id. A POSITA would understand
`
`that Nogami’s disclosure of the upper Ta or TaN layer containing less than about
`
`
`
`15
`
`Page 16 of 23
`
`
`
`15 at. % nitrogen would include a solid solution of TaNx in the upper layer, like the
`
`TaN0.1 solid solution taught in the ’324 patent.
`
`28. Because each of Zhang, Ding, and Nogami discloses less than 10%
`
`nitrogen content in a top tantalum film of a diffusion barrier structure, in my
`
`opinion, a POSITA would have recognized each reference discloses forming solid
`
`solutions in their top films. Each of these references discloses a crystalline metal
`
`film having a nitrogen content close to or less than 10 atomic percent nitrogen,
`
`which the ’324 patent teaches is a solid solution. See Ex. 1004 at 3:59-62 (Zhang
`
`disclosing “At the upper surface, the atomic percent tantalum may be at least 95%
`
`and the atomic percent nitrogen may be less than 5% if copper adhesion is
`
`particularly problematic”); Ex. 1033 at 1:44-47 (describing Ding’s “barrier layer
`
`having a surface which is essentially pure tantalum or tantalum including only a
`
`small amount of nitrogen (typically less than about 15 atomic percent) performs
`
`well as a barrier layer and also as a wetting layer to enhance the subsequent
`
`application of an overlying copper layer”) (emphasis added); Ex. 2039 at 3:38-39
`
`(Nogami disclosing “the fourth layer [the upper layer] of Ta or TaN having a
`
`nitrogen content less than about 15 at. %”) (emphases added).
`
`29. Accordingly, it is my opinion that a POSITA at the time of the ’324
`
`patent would have understood that Zhang and Ding in view of Nogami render
`
`obvious Substitute Claim 13.
`
`
`
`16
`
`Page 17 of 23
`
`
`
`G. The construction of “solid solution” in Substitute Claim 13 is
`“a homogeneous mixture of a substance in a single solid phase”
`
`30.
`
`I understand that Patent Owner’s Substitute Claim 13 recites the term
`
`“solid solution,” which appears only once in the brief description of a figure in the
`
`’324 patent. Ex. 1001, 8:25-29.
`
`31.
`
`I have been told that Petitioner proposes the term “solid solution,” as
`
`Substitute Claim 13 recites, means “a homogeneous mixture of a substance in a
`
`single solid phase.” I agree with this proposed construction. In my opinion, a
`
`POSITA would have understood at the time of the ’324 patent that Petitioner’s
`
`proposed construction is consistent with the plain meaning of “solid solution”
`
`under a broadest reasonable construction.
`
`32. Exhibit 2036 is an excerpt from Hackh’s Chemical Dictionary (4th ed.
`
`1972) that defines a “solid solution” as a “homogeneous, solid mixture of
`
`substance.” See Ex. 2036 at 3 (definition of s. [i.e., solid] solution). Exhibit 2010 is
`
`an excerpt from the chemistry textbook entitled Chemistry (2nd ed. 1961), by
`
`Sienko et al., that explains “a mixture is classified as heterogeneous or
`
`homogeneous,” and “a heterogeneous mixture consists of distinct phases,” whereas
`
`“a homogeneous mixture consists of a single phase.” Ex. 2010 at 193.
`
`33. A POSITA at the time that the application leading to the ’324 patent
`
`was filed would have known of the definition of a “solid solution” in Exhibit 2036,
`
`
`
`17
`
`Page 18 of 23
`
`
`
`and of the differences between homogeneous and heterogeneous mixtures as
`
`Exhibit 2010 describes.
`
`34.
`
`In my opinion, this evidence makes it clear that the plain meaning of a
`
`“solid solution” at the time of filing of the application leading to the ’324 patent is
`
`“a homogeneous mixture of a substance in a single solid phase.”
`
`H. Lack of written description for the “first film . . . is a solid
`solution” in Substitute Claim 13
`35. Substitute Claim 13 recites: “The multi-layered wiring structure as set
`
`forth in claim 11, wherein said first film has a thickness in the range of 60
`
`angstroms to 300 angstroms both inclusive; 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.”
`
`36.
`
`It is my opinion a POSITA reading the ’324 patent would have
`
`understood the specification describes a top barrier film with multiple solid phases,
`
`namely a crystalline -Ta phase and crystalline TaN0.1 phase. Ex. 1001, 13:15-24
`
`(describing a multi-layered barrier film in FIG. 21 having a top crystalline metal
`
`film “composed of crystalline -Ta and crystalline TaN0.1 in mixture”), 12:65-67,
`
`13:8-10, 13:57-61, 16:41-43, 19:10-12; see also Ex. 1036, 194:2-195:6 (testifying
`
`-Ta and TaN0.1 are different material phases). Because the top barrier film in the
`
`’324 patent has multiple distinct phases, it cannot be a solid solution, which is a
`
`homogeneous mixture of a substance in a single solid phase.
`
`
`
`18
`
`Page 19 of 23
`
`
`
`37. Although the TaN0.1 phase in the top film is a solid solution with a
`
`homogeneous mixture of tantalum and nitrogen (see, e.g., id. 194:13-195:6), the
`
`brief description of FIG. 21 at Ex. 1001, col. 8, lines 25-29, does not teach the
`
`entire top film (consisting of distinct -Ta and TaN0.1 phases) is a solid solution. A
`
`solid solution consists of a single phase, and the ’324 patent consistently describes
`
`the top crystalline film as a mixture of a crystalline β-Ta phase and a crystalline
`
`TaN0.1 phase. See, e.g., Ex. 1002 (’324 patent file history) at 75 (“crystalline metal
`
`film 16 [in FIG. 21] is composed of crystalline β-Ta and crystalline TaN0.1 in
`
`mixture”); 220 (“TaN0.1 . . . is called nitrogen-containing α-Ta.”).
`
`38. A POSITA would have understood from the prosecution history that
`
`the inventors of the ’324 patent also referred to TaN0.1 as “nitrogen-containing
`
`α-Ta,” where “α-Ta” corresponds to an alpha phase of tantalum. Ex. 1002 at 220.
`
`The POSITA at the time of the ’324 patent would have known that the beta phase
`
`of tantalum (β-Ta) consists of a lattice structure with a generally tetragonal unit
`
`cell, whereas the alpha phase of tantalum (Ta) is a different solid phase having a
`
`body centered cubic (bcc) lattice structure.
`
`39. A POSITA would have understood the ’324 patent’s disclosure of a
`
`film “containing nitrogen in solid solution” at col. 8, lines 25-29 does not mean
`
`that the entire film is a solid solution. Nitrogen only exists in the portions of the
`
`film formed of nitrogen-containing α-Ta phase tantalum (TaN0.1), while the
`
`
`
`19
`
`Page 20 of 23
`
`
`
`portions containing the β-Ta phase lack nitrogen. I believe a POSITA would
`
`understand the disclosed -Ta phase in the specification was a well-known
`
`material phase consisting of only tantalum. The specification does not support the
`
`entire “first film” is “a solid solution” as Substitute Claim 13 recites.
`
`40.
`
`It is also my opinion that a POSITA would understand that the top
`
`film disclosed by the ’324 patent is not homogenous because it contains a mixture
`
`of multiple distinct phases (a β-Ta phase and a nitrogen-containing α-Ta phase)
`
`and, therefore, is a heterogeneous mixture rather than a homogeneous mixture as
`
`required for a solid solution. The specification does not support the amendment
`
`seeking to limit the claims to “said first film . . . is a solid solution” as Substitute
`
`Claim 13 recites.
`
`41. The ’324 patent describes a top barrier film as a “mixture” of
`
`crystalline -Ta and crystalline TaN0.1 phases. Ex. 1001, 13:15-24. It further
`
`describes the TaN0.1 phase is a solid solution, where TaN0.1 contains 10% nitrogen
`
`(TaN0.1 means the Ta-to-N atomic ratio is equal to 10 to 1, or 10% nitrogen in the
`
`nitrogen-containing tantalum). Ex. 1001 at 8:25-29.
`
`42.
`
`In view of this teaching of the TaN0.1 phase in the ’324 patent, a
`
`POSITA would have understood the specification teaches that 10 at. % nitrogen is
`
`within the solid solubility limit for forming a solid solution in a tantalum film, such
`
`
`
`20
`
`Page 21 of 23
`
`
`
`that 10% nitrogen would not be a high enough concentration to form other phases
`
`such as N precipitates.
`
`43. The ’324 patent describes the top film as a heterogeneous “mixture”
`
`of TaN0.1 and -Ta phases. See, e.g., Ex. 1001 at 12:65-67, 13:15-24, 12:65-67,
`
`13:8-10, 13:57-61, 16:41-43, 19:10-12. I do not believe the specification’s
`
`disclosed “mixture” refers to a solution of a metal and nitrogen. Motion at 12 (“a
`
`film composed of crystalline metal and nitrogen ‘in mixture’”). Rather, as
`
`discussed above, the specification teaches a heterogeneous mixture of two different
`
`solid phases, one containing nitrogen (TaN0.1) and the other only tantalum (-Ta).
`
`See Ex. 2010 at 4. The first film does not contain nitrogen throughout the film
`
`since there are localized -Ta portions of the film that lack nitrogen.
`
`44. The ’324 patent uses “throughout” five times, and only uses the term
`
`in the context of physical structures, such as recesses, holes, and grain boundaries.
`
`In my opinion, those uses are unrelated to the nitrogen content in a tantalum film.
`
`Ex. 1001 at 2:67, 5:26, 7:49, 14:56, 20:15. The specification never uses
`
`“throughout” to define the concentration of an element, such as nitrogen.
`
`VII. CONCLUSION
`
`45.
`
`I declare that all statements made herein of my own knowledge are
`
`true and that all statements made on information and belief are believed to be true;
`
`and further that these statements were made with the knowledge that willful false
`
`
`
`21
`
`Page 22 of 23
`
`
`
`statements and the like so made are punishable by fine or imprisonment, or both,
`
`under Section 1001 of Title 18 o
Accessing this document will incur an additional charge of $.
After purchase, you can access this document again without charge.
Accept $ Charge
Still Working On It
This document is taking longer than usual to download. This can happen if we need to contact the court directly to obtain the document and their servers are running slowly.
Give it another minute or two to complete, and then try the refresh button.
A few More Minutes ... Still Working
It can take up to 5 minutes for us to download a document if the court servers are running slowly.
Thank you for your continued patience.
This document could not be displayed.
We could not find this document within its docket. Please go back to the docket page and check the link. If that does not work, go back to the docket and refresh it to pull the newest information.
Your account does not support viewing this document.
You need a Paid Account to view this document. Click here to change your account type.
Your account does not support viewing this document.
Set your membership
status to view this document.
With a Docket Alarm membership, you'll
get a whole lot more, including:
- Up-to-date information for this case.
- Email alerts whenever there is an update.
- Full text search for other cases.
- Get email alerts whenever a new case matches your search.
One Moment Please
The filing “” is large (MB) and is being downloaded.
Please refresh this page in a few minutes to see if the filing has been downloaded. The filing will also be emailed to you when the download completes.
Your document is on its way!
If you do not receive the document in five minutes, contact support at support@docketalarm.com.
Sealed Document
We are unable to display this document, it may be under a court ordered seal.
If you have proper credentials to access the file, you may proceed directly to the court's system using your government issued username and password.
Access Government Site
