Reza Mollaaghababa
`Pepper Hamilton LLP
`125 High Street
`19th Floor, High Street Tower
`Boston, MA 02110
`(617) 204-5100 (telephone)
`(617) 204-5150 (facsimile)
`
`
`
`By:
`
`
`UNITED STATES PATENT AND TRADEMARK OFFICE
`___________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`___________________
`
`MICRON TECHNOLOGY, INC.
`Petitioner
`
`v.
`
`PRESIDENT AND FELLOWS OF HARVARD COLLEGE
`Patent Owner
`
`___________________
`
`Case No. IPR2017-00663
`Patent No. 8,334,016
`___________________
`
`PATENT OWNER’S PRELIMINARY RESPONSE
`PURSUANT TO 37 C.F.R. § 42.107
`
`
`
`
`
`
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`TABLE OF CONTENTS
`
`Page(s)
`
`Table of Authorities ................................................................................................. iii
`
`Table of Exhibits ....................................................................................................... v
`
`
`I.
`
`Introduction ..................................................................................................... 1
`
` Alleged Grounds ............................................................................................. 1
`II.
`
` Overview Of The Technology And The ’016 Patent ..................................... 2
`III.
`
`A.
`
`Technology Background ...................................................................... 2
`
`1.
`
`2.
`
`Chemical Vapor Deposition ....................................................... 3
`
`Atomic Layer Deposition ........................................................... 3
`
`B.
`
`The ’016 Patent .................................................................................... 6
`
` State of the Art of the Time of the ’016 Patent .............................................. 9
`IV.
`
`A.
`
`Precursor Chemistry in ALD Processes was Known to be
`Unpredictable ..................................................................................... 10
`
`B. Deposition of Metal Alkylamides Was Understood to Lead to
`Unsuitable Levels of Contamination in Oxide Films ......................... 13
`
`
`V.
`
`Claim Construction And Ordinary Skill In The Art ..................................... 15
`
`A.
`
`Claim Construction............................................................................. 15
`
`B. A Person Having Ordinary Skill In The Art ...................................... 15
`
` The Challenged Claims Are Not Obvious Over Buchanan In View Of
`VI.
`Min ................................................................................................................ 16
`
`A.
`
`Summary of the Asserted References ................................................ 16
`
`1.
`
`2.
`
`U.S. Patent No. 6,984,591, “Precursor Source Mixtures”
`(Buchanan) ............................................................................... 16
`
`Jae-Sik Min, et al., Atomic Layer Deposition of TiN
`Films by Alternate Supply of
`Tetrakis(ethylmethylamino)-Titanium and Ammonia
`(“Min”) ..................................................................................... 18
`
`B.
`
`The Petition Fails to Meet Its Burden to Demonstrate a
`Reasonable Likelihood That Buchanan in View of Min Renders
`Obvious Claims 1-3, 5-7, and 9-10 .................................................... 19
`
`i
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`C.
`
`There is No Reasonable Likelihood That Claims 1-3, 5-7, and
`9-10 are Rendered Obvious By Buchanan In View Of Min .............. 22
`
`1.
`
`2.
`
`The Combination of Buchanan and Min Fails to Disclose
`or Render Obvious a Self-Limiting ALD Process Using a
`Metal Alkylamide Precursor to Form a Metal Oxide
`Film, as required by Claim 1.................................................... 24
`
`There is No Reasonable Likelihood That Claims 2-3, 5-7,
`9-10 Are Rendered Obvious By Buchanan In View Of
`Min ........................................................................................... 48
`
` The Challenged Claims Are Not Obvious Over Buchanan In View Of
`VII.
`Min And Shin ............................................................................................... 53
`
`A.
`
`B.
`
`Summary of Korean Patent KR0156980 “Compound for the
`Deposition of Metal Nitride Thin Film and Deposition Method
`Thereof” (“Shin”) ............................................................................... 53
`
`There Is No Reasonable Likelihood That Claim 8 Is Rendered
`Obvious Over Buchanan In View Of Min and Shin .......................... 54
`
` Conclusion .................................................................................................... 56
`VIII.
`
`
`
`ii
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`TABLE OF AUTHORITIES
`
`Page(s)
`
`
`CASES
`
`Belden Inc. v. Berk-Tek LLC,
`805 F.3d 1064 (Fed. Cir. 2015) .......................................................................... 22
`
`Boston Scientific Corp. v. Johnson & Johnson, Inc.,
`679 F. Supp.2d 539 (D. Del. 2010) ................................................................. 9, 19
`
`In re Carleton,
`599 F.2d 1021 (C.C.P.A. 1979) .......................................................................... 10
`
`In re Fritch,
`972 F.2d 1260 (Fed. Cir. 1992) .......................................................................... 22
`
`In re Translogic Tech., Inc.,
`504 F.3d 1249 (Fed. Cir. 2007) .......................................................................... 15
`
`InTouch Techs., Inc. v. VGO Commc’ns, Inc.,
`751 F.3d 1327 (Fed. Cir. 2014) .......................................................................... 20
`
`PeronalWeb Techs. LLC v. Apple Inc.,
`2017 U.S. App. LEXIS 2544 (Fed. Cir. Feb. 14, 2017) ..................................... 20
`
`Schering Corp. v. Gilbert,
`153 F.2d 428 (2d Cir. 1946) ............................................................................... 10
`
`Takeda Pharm. Co. v. Handa Pharms., LLC,
`No. C-11-00840 JCS, 2013 U.S. Dist. LEXIS 187604 (N.D. Cal. Oct. 17,
`2013) ................................................................................................................... 19
`
`TRW Automotive U.S., LLC v. Magna Electronics, Inc.,
` IPR2015-00949, Paper 7 (Sep. 17, 2015) .......................................................... 15
`
`STATUTES
`
`35 U.S.C. § 313 .......................................................................................................... 1
`
`35 U.S.C. § 314 ........................................................................................................ 22
`
`iii
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`OTHER AUTHORITIES
`
`37 C.F.R. § 42.20(c) ................................................................................................. 19
`
`37 C.F.R. § 42.24(a)(1), (b)(1) ................................................................................. 59
`
`37 C.F.R. § 42.24(d) ................................................................................................ 59
`
`37 C.F.R. § 42.100(b) .............................................................................................. 15
`
`37 C.F.R. § 42.107 ............................................................................................... 1, 58
`
`37 C.F.R. § 42.108(c) ........................................................................................... 2, 19
`
`Office Patent Trial Practice Guide, 77 Fed. Reg. 48,756, 48,766 (Aug. 14,
`2012) ................................................................................................................... 15
`
`iv
`
`

`

`PATENT OWNER’S TABLE OF EXHIBITS
`
`
`Exhibit No.
`
`Exhibit Description
`
`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`2101
`
`2102
`
`2103
`
`2104
`
`2105
`
`2106
`
`2107
`
`2108
`
`2109
`
`2110
`
`Declaration of Wayne L. Gladfelter, Ph.D. in Support of Patent
`Owner’s Preliminary Response
`
`Jones, A.C., et al., MOCVD and ALD of High-K Dielectric Oxides
`Using Alkoxide Precursors, 12 Chem. Vap. Deposition 83-98 (2006)
`(“Jones”)
`
`Fix, R. M., et. al., Synthesis of Thin Films by Atmospheric Pressure
`Chemical Vapor Deposition Using Amido and Imido Titanium (IV)
`Compounds as Precursors, 2 Chem. Mater. 235-41 (1990) (“Fix”)
`
`Ishihara, K. et. al., Characterization of CVD-TiN Films Prepared
`with Metalorganic Source, 29 No. 10 Jpn. J. Appl. Phys. 2103-05
`(1990) (“Ishihara”)
`
`Dubois, L.H. et. al., Infrared Studies of Surface and Gas Phase
`Reactions Leading to the Growth of Titanium Nitride Thin Films
`from Tetrakis(dimethylamido)titanium and Ammonia, 139 No. 12 J.
`Electrochem. Soc. 3603-09 (1992) (“Dubois ’92”)
`
`Dubois, L.H., Model Studies of Low Temperature Titanium Nitride
`Thin Film Growth, 13 No. 8 Polyhedron 1329-36 (1994) (“Dubois
`’94”)
`
`Excerpt of U.S. Patent No. 7,507,848 File History, Gordon Decl.
`Aug. 12, 2008 (“’848 FH”)
`
`Excerpt of U.S. Patent No. 7,507,848 File History, Gordon Decl.
`Aug. 12, 2008, Exhibit B, 2000 International Technology Roadmap
`for Semiconductors (“ITRS”)
`
`Herlin, N. et. al., Investigation of the Chemical Vapor Deposition of
`Silicon Carbide from Tetramethylsilane by in Situ Temperature and
`Gas Composition Measurements, 96 J Phys Chem. 7063-72
`(1992)(“Herlin”)
`
`Bechamp, K. et. al., A Combined Electron Paramagnetic Resonance
`
`v
`
`

`

`Exhibit No.
`
`Exhibit Description
`
`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`and Fourier Transform Infrared Study of the Co(C6H6)1,2 Complexes
`Isolated in Neat Benzene or in Cryogenic Matrixes, 110 J Phys
`Chem. 6023-31 (2006) (“Bechamp”)
`
`Tiers, G.V.D., Proton Nuclear Resonance Spectroscopy. I. Reliable
`Shielding Values by “Internal Referencing” with Tetramethysilane,
`62 J. Phys. Chem. 1151-52 (1958) (“Tiers”)
`
`Hämäläinen et al, Atomic Layer Deposition and Characterization of
`Aluminum Silicate Thin Films for Optical Applications, 158 J.
`Electrochem. Soc. 15-21 (2011) (“Hämäläinen”)
`
`Zaera, F., The Surface Chemistry of Thin Film Atomic Layer
`Deposition (ALD) Processes for Electronic Device Manufacturing,
`18 J. Mater. Chem. 3521-26 (2008) (“Zaera”)
`
`Sugiyama et. al., Low Temperature Deposition of Metal Nitride by
`Thermal Decomposition of Organometallic Compounds, 122 No. 11
`J. Electrochem. Soc., Solid-State Science and Technology 1545-49
`(1975) (“Sugiyama”)
`
`Provine, J; Rincon, M., Atomic Layer Deposition: Introduction to
`the Theory and Cambridge Nanotech Savannah & Fiji, Stanford
`University (2012) https://snf.stanford.edu/SNF/equipment/chemical-
`vapor-deposition/ald/ald-tutorials. (“Provine”)
`
`2111
`
`2112
`
`2113
`
`2114
`
`2115
`
`
`
`vi
`
`

`

`Case No. IPR2017-00663
`Patent 8,334,016
`
`
`Pursuant to 37 C.F.R. § 42.107, the Patent Owner, President and Fellows of
`
`Harvard College (“Harvard”) hereby submits the following Preliminary Response
`
`to the Petition seeking inter partes review of U.S. Patent No. 8,334,016 (“the ’016
`
`Patent”). This filing is timely under 35 U.S.C. § 313 and 37 C.F.R. § 42.107, as it
`
`is being filed within three months of the mailing date of the Notice of Filing Date
`
`Accorded to the Petition (Paper 3), mailed January 31, 2017.
`
`
`I.
`
`INTRODUCTION
`
`The Petition fails to show a reasonable likelihood of prevailing on any of the
`
`challenged claims of the ’016 Patent. Accordingly, Harvard respectfully requests
`
`that the Patent Trial and Appeal Board (“the Board”) deny inter partes review as to
`
`all grounds set forth in the Petition.
`
`
`
` ALLEGED GROUNDS II.
`
`The Petition challenges claims 1-3 and 5-10 of the ’016 Patent on the
`
`following alleged grounds:
`
`1.
`
`Claims 1-3, 5-7, and 9-10 as being obvious over U.S. Patent No.
`
`6,984,591 of Buchanan et al. (Ex. 1005, “Buchanan”) in view of an
`
`article by J. Min, entitled “Atomic Layer deposition of TiN Films by
`
`Alternate Supply of Tetrakis(ethylmethylamino)-Titanium and
`
`Ammonia ” (Ex. 1006, “Min”); and
`
`1
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`2.
`
`Claim 8 as being obvious over Buchanan in view of Min and Korean
`
`Patent No. KR0156980, entitled “Compound for the Metal Nitride
`
`Thin Film Vapor Deposition and Deposition Method thereof” (Ex.
`
`1007, “Shin”).
`
`Petitioner fails to demonstrate a reasonable likelihood that any of the
`
`challenged claims of the ’016 Patent are anticipated or rendered obvious by the
`
`cited art. See 37 C.F.R. § 42.108(c). Should the Board decide to institute a trial,
`
`Patent Owner reserves the right to present additional arguments as to the
`
`patentability of the claims for which trial is instituted.
`
`
`
` OVERVIEW OF THE TECHNOLOGY AND THE ’016 PATENT III.
`
`A. Technology Background
`
`The patented inventions relate to the processes and materials used in the
`
`deposition of films on surfaces, such as thin films deposited in the manufacture of
`
`microelectronics. Ex. 1001 at 2:48-52; Ex. 2101, Decl. of Wayne L. Gladfelter,
`
`PhD. in Support of PO’s Prelim. Resp. ¶25 (“Gladfelter Decl.”). Each of these
`
`deposition methods requires chemical reactions to form films on a surface.
`
`Gladfelter Decl. at ¶25, Ex. 1001 at Abstract, 1:46-2:7.
`
`The inventions of the ’016 Patent relate to methods of depositing thin films
`
`via deposition processes such as chemical vapor deposition (CVD) and atomic
`
`layer deposition (ALD). Ex. 1001 at 1:30-32; Gladfelter Decl. at ¶24. Claims 1-3
`
`2
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`and 5-10 of the ’016 Patent, currently at issue, specifically relate to the use of a
`
`self-limiting ALD process using metal amides to produce a metal oxide film.
`
`Gladfelter Decl. at ¶24; Ex. 1001 at 30:9-26 (Claim 1).
`
`ALD is a deposition process characterized by alternately exposing a heated
`
`surface to two or more reactant vapors. Gladfelter Decl. at ¶27; Ex. 1001 at 1:48-
`
`49. In ALD, the alternate exposure keeps the reactant vapors separate from one
`
`another when exposed to the heated surface (i.e., the reactant vapors are introduced
`
`one at a time). Gladfelter Decl. at ¶27. Generally, to maintain their separation, the
`
`reaction chamber containing the heated surface is purged of any excess reactant
`
`vapor before each new reactant vapor is introduced. Gladfelter Decl. at ¶27. For
`
`suitable reactants, ALD can provide improved step coverage and thickness
`
`uniformity compared to CVD. Gladfelter Decl. at ¶27, Ex. 1001 at 1:50-53.
`
`1.
`
`Chemical Vapor Deposition
`
`In a CVD process, reactant vapors are selected that will allow for the
`
`continuous growth of a thin film on a heated surface. See Gladfelter Decl. at ¶ 28,
`
`Ex. 1001 at 1:37-48. In CVD, one or more reactant vapors are introduced into a
`
`reaction chamber, also referred to as a deposition chamber, which contains a
`
`heated surface, often referred to as a substrate. See Gladfelter Decl. at ¶ 28; Ex.
`
`1001 at 1:37-2:3, 2:26-29.
`
`2.
`
`Atomic Layer Deposition
`
`3
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`In an ALD deposition process, at least two reactant vapors are selected that
`
`will allow for the controlled, stepwise growth of a thin film on a heated surface.
`
`Gladfelter Decl. at ¶ 30; see also Ex. 1013 at 13; Ex. 1001 at 20:56-21:8, 23:54-60,
`
`24:8-15, 24:28-36, 26:44-27:9, 27:45-30:7. In ALD, reactant vapors are alternately
`
`exposed to a heated surface in the deposition chamber. Id. Fundamental to ALD is
`
`the requirement that the reactant vapors react in a self-limiting manner. Gladfelter
`
`Decl. at ¶ 30; see also Ex. 1013 at 13. In ALD, when a first reactant vapor is
`
`exposed to a heated surface the first reactant vapor will react with available sites
`
`on the surface, forming deposits. Gladfelter Decl. at ¶ 30, 32-37; Ex. 1001 at
`
`20:56-40. Because the first reactant vapor does not react with its deposits, over
`
`time, the surface will become saturated and the reactions will stop. Gladfelter
`
`Decl. at ¶ 30, 32-37; Ex. 1001 at 19:34-36, 22:20-26, 27:10-23. Once the
`
`deposition chamber is cleared of first reactant vapors and reaction by-products, a
`
`second reactant vapor is introduced. Gladfelter Decl. at ¶ 30, 32-37; Ex. 1001 at
`
`20:56-21:8, Ex. 1013 at 13. The second reactant vapor reacts with the surface
`
`sites, now containing the deposited first reactant vapor, and again, over time, the
`
`surface will become saturated and the reactions will stop. Id. The reactant vapors
`
`are selected such that cycles of the alternate exposure of a heated surface to the
`
`reactant vapors will result in a film formed by controlled layering of deposits. Id.
`
`4
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`The Petition misleadingly states that ALD techniques were “well known” at
`
`the time of the inventions in the late 1990’s. See Gladfelter Decl. at ¶ 39; see also
`
`Paper 1 at 7. However, as Dr. Gladfelter indicates, it is more accurate to note that
`
`although ALD was developed in the seventies in Finland, by the late 90’s there
`
`were “a lot of challenges and development work to be done before ALD” could be
`
`accepted for microelectronics. See Gladfelter Decl. at ¶ 39 (citing Ex. 1013 at 13,
`
`21-22). Specifically, work needed to be done in precursor chemistry development.
`
`Id.
`
`Additionally, the Petition incorrectly states that “[b]efore 2000, the art had
`
`described and/or taught ALD to form metal oxides using metal dialkylamide
`
`precursors.” Paper 1 at 11; Gladfelter Decl. at ¶ 40. This statement is simply not
`
`true. Gladfelter Decl. at ¶ 40; Ex. 1002 at 50.
`
`Further, the Petitioner provides a misleading statement regarding what was
`
`known by those of skill in the art by the mid-1990s. See Gladfelter Decl. at ¶ 41.
`
`Specifically, Petitioner asserts that “metal dialkylamides possessed qualities that
`
`made them desirable precursors for ALD processes.” Paper 1 at 12-13 (identifying
`
`precursor volatility, thermal stability, and high reactivity as desirable
`
`characteristics for ALD). As discussed in Dr. Gladfelter’s declaration, although
`
`these characteristics are desirable, a person of ordinary skill in the art would know
`
`5
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`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`that they are not indicative of whether a specific precursor would be suitable for
`
`CVD or ALD. Gladfelter Decl. at ¶ 41.
`
`The Banerjee Declaration misleadingly states that a person of ordinary skill
`
`in the art at the time of the invention, when tasked with forming metal oxides with
`
`ALD, “often looked to precursors that had been successfully used in CVD
`
`processes to form metal oxides.” See Gladfelter Decl. at ¶ 45 (citing Ex. 1003 at
`
`¶72). This implies a false premise that CVD and ALD precursors were
`
`interchangeable. Id. While precursors for both CVD and ALD share practical
`
`similarities, including the need for volatility, storage stability, and safety, it was
`
`widely known that the requirements of ALD precursors are different from CVD
`
`precursors. Gladfelter Decl. at ¶ 45; see also Ex. 1013 at 13; Ex. 2102 at 83.
`
`There are many examples of CVD precursors that turn out not to be effective for
`
`ALD. Gladfelter Decl. at ¶ 45; see also Ex. 2102.
`
`B.
`
`The ’016 Patent
`
`The title of the ’016 Patent is “Vapor Deposition of Metal Oxides, Silicates
`
`and Phosphates, and Silicon Dioxide.” The inventions claimed by the ’016 Patent
`
`include novel processes and materials for deposition of thin films that contain
`
`metal oxides, silicates, metal phosphates, or silicon dioxide. Ex. 1001 at 1:22-28;
`
`Gladfelter Decl. at ¶ 46.
`
`6
`
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`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`The claimed inventions are directed to atomic layer deposition (“ALD”).
`
`Gladfelter Decl. at ¶ 47; see also Ex. 1001 at 30:9-44. ALD is a process by which
`
`certain thin films for microelectronics are produced. Gladfelter Decl. at ¶ 47; see
`
`also Ex. 1001 at 1:48-54. ALD requires a number of process steps, and includes
`
`the use of at least two chemical precursors with appropriate reactive properties.
`
`Gladfelter Decl. at ¶ 47; see also Ex. 1001 at 20:56-21:8. The chemical precursors
`
`used in an ALD process should not leave behind elements that are deleterious to
`
`the properties of the film. Gladfelter Decl. at ¶ 47; see also Ex. 1001at 1:55-2:3.
`
`These problems have been found with the use of precursors such as metal chlorides
`
`and silicon alkoxides. Id.
`
`Additional problems were encountered when forming dielectric materials in
`
`deep trench structures, such as dynamic random access memory (DRAM) devices.
`
`Gladfelter Decl. at ¶ 48; see also Ex. 1054 at 3, Ex. 1043 at 6-7, Ex. 2107, ’848 FH
`
`at 2-4; Ex. 1003, ’663 Banerjee Decl. at ¶ 69. Not only must the capacitance
`
`values remain at a certain level despite the reduction in size, the precursors must be
`
`delivered deep into the trenches without a premature reaction that would preclude
`
`uniform coverage within the entire deep trench structure. Id.
`
`No solution for coating surfaces of deep trenches with high dielectric
`
`materials was even expected until 2008. Gladfelter Decl. at ¶ 49; see also Ex.
`
`2107 at 2-4, Ex. B. In fact, near the effective filing date of the present application,
`
`7
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`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`a group of semiconductor industry experts believed that the high-dielectric material
`
`problem would not be solved for at least another eight years. Gladfelter Decl. at ¶
`
`49.
`
`The ALD processes and materials claimed by the ’016 Patent solve some of
`
`the problems associated with the production of microelectronic devices at smaller
`
`sizes, such as the formation of dielectric coatings in deep trench structures.
`
`Gladfelter Decl. at ¶ 50; see also Ex. 1001 at FIG. 3, 2: 14-52, 19:41-48, 6:33-35,
`
`27:18-35, 30:9-44.
`
`Figure 3 of the ’016 Patent, shown below, is a cross-sectional scanning
`
`electron micrograph of holes in a silicon wafer uniformly coated with hafnium
`
`dioxide using one embodiment of the invention. Ex. 1001 at 6:33-35; Gladfelter
`
`Decl. at ¶ 51.
`
`8
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`The ’016 Patent applicants noted the surprising result of the claimed use of
`
`metal alkylamide precursors in ALD to form highly uniform films of metal oxide
`
`in holes with very high aspect ratios. Gladfelter Decl. at ¶ 52 (citing Ex. 1001 at
`
`
`
`19:41-48).
`
`
`
` STATE OF THE ART OF THE TIME OF THE ’016 PATENT IV.
`
`The scope of the claimed inventions falls within the field of chemistry,
`
`which has long been acknowledged to be unpredictable. See Boston Scientific
`
`9
`
`

`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`Corp. v. Johnson & Johnson, Inc., 679 F. Supp.2d 539, 557 (D. Del. 2010).
`
`Chemistry is an experimental science, meaning that one cannot predict the
`
`outcome of an experiment without actually carrying out the experiment in the
`
`laboratory. See, e.g., In re Carleton, 599 F.2d 1021, 1026 (C.C.P.A. 1979);
`
`Schering Corp. v. Gilbert, 153 F.2d 428, 433 (2d Cir. 1946).
`
`A.
`
`Precursor Chemistry in ALD Processes was Known to be
`Unpredictable
`
`A person of ordinary skill in the art would understand that the precursor
`
`chemistry involved in the formation of a metal film via an ALD process is
`
`unpredictable. Gladfelter Decl. at ¶ 110. In the late 1990s, at the time of the
`
`invention, it was understood that it was difficult to predict without extensive
`
`experimentation whether a precursor could be used in an ALD reaction to form a
`
`desired film. Gladfelter Decl. at ¶ 111; see also, e.g., Ex. 1044, Goodman at 8.
`
`Those of ordinary skill in the art recognized that even pre-process
`
`calculations regarding theoretical ALD process reactions are not sufficient to
`
`determine whether an ALD process will be successful. See Gladfelter Decl. at ¶
`
`111; Ex. 1008 at 20. For example, those of skill in the art understood that, while
`
`useful, thermodynamic considerations of the reactions prior to experimental work
`
`cannot be used to predict with any reasonable degree of confidence whether film
`
`growth will occur. See id.
`
`10
`
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`

`Case No. IPR2017-00663
`Patent No. 8,334,016
`
`
`Additionally, in the late 1990s, those of skill in the art understood the
`
`importance of, and difficulties with precursor chemistry in ALD processes, and
`
`understood that further development and testing was necessary. Gladfelter Decl. at
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`¶ 113; see also Ex. 1014 at 21.
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`Those of skill in the art further understood that precursor chemistry for CVD
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`processes is also unpredictable, and that due to the significant differences between,
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`and unpredictable nature of ALD and CVD processes, precursors that may be
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`suitable for one process, are not necessarily suitable for the other. See Gladfelter
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`Decl. ¶¶ 115-21. In fact, in 2006, a study concluded that a large class of
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`compounds developed to be particularly effective as CVD precursors fail to
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`achieve growth that is needed for ALD. Gladfelter Decl. ¶ 118; see also Ex. 2102
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`at 83-98.
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`The diagram below visually depicts how a person of ordinary skill in the art
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`would have understood the relationship of precursors used in ALD and CVD
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`processes. See Gladfelter Decl. at ¶ 116. A person of ordinary skill would
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`understand that, while there is overlap, not all precursors are suitable for both ALD
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`and CVD.
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`For example, tetramethysilane, Si(CH3)4, is a known CVD precursor for
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`deposition of silicon carbide (SiC), at temperatures greater than 900°C. Gladfelter
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`Decl. at ¶ 117; Ex. 2109, Herlin. However, the thermal stability and lack of
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`reactivity of tetramethylsilane render it useless as an ALD precursor. Attempts to
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`use tetramethylsilane in ALD have failed. Gladfelter Decl. at ¶ 88; Ex. 2112,
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`Hämäläinen. Gladfelter Decl. at ¶ 117. The thermal stability and lack of reactivity
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`of tetramethylsilane is so great that it was chosen decades ago to be the standard
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`reference compound in Nuclear Magnetic Resonance (NMR) spectroscopy.
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`Gladfelter Decl. at ¶ 117; Ex. 2111, Tiers at 1151-52. A person of ordinary skill in
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`the art would know that these alkylsilane “preferred precursors” would not work
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`with ALD because they do not chemisorb onto surfaces, a process required for
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`ALD. Gladfelter Decl. at ¶ 117.
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`As an additional example, commercial copper precursor CupraSelect® is
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`found to be suitable for CVD processes but not for ALD processes. Gladfelter
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`Decl. at ¶ 120.
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`Further, trimethylaluminum (TMA) is well-known to function in an ALD
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`reaction when a heated surface is alternately exposed to TMA and water vapor to
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`deposit films of aluminum oxide. Gladfelter Decl. at ¶ 121. However, TMA
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`cannot be used in a CVD process together with water to deposit films of aluminum
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`oxide. Id.
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`B. Deposition of Metal Alkylamides Was Understood to Lead to
`Unsuitable Levels of Contamination in Oxide Films
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`At the time of the inventions, research into the deposition of metal
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`alkylamides was known to lead to unsuitable levels of contamination in oxide
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`films. See Gladfelter Decl. at ¶¶ 122-29. Based on this research, those of ordinary
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`skill in the art would have expected that the use of metal alkylamides in an ALD
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`process to produce a metal oxide film would have also led to unsuitable levels of
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`contamination, in the form or carbon and nitrogen impurities, in the resulting film.
`
`See id.
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`Particularly, those of ordinary skill in the art would have considered an ALD
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`process to be similar to a CVD process known as “single source CVD,” in the way
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`a precursor would interact with a heated substrate in a deposition chamber.
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`Gladfelter Decl. at ¶ 124. Single source CVD is a CVD process using only one
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`precursor compound. Id. In single source CVD, a single precursor is introduced
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`into the deposition chamber, usually with a carrier gas, to form a film on a heated
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`substrate. Id. Similarly, in an ALD process, precursors are alternately introduced
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`into the deposition chamber, such that only a single precursor is introduced into the
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`deposition chamber at a time. Id. As discussed below, research into single source
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`CVD using metal alkylamide precursors produced films with unsuitable levels of
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`contamination. See id. at ¶¶ 122-29.
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`Additionally, when depositing a metal oxide film, as opposed to metal
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`nitride film, a reactant with an oxygen source is necessary. See id. at ¶ 130.
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`Ammonia (NH3), which was employed in the Dubois ’94 to reduce carbon
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`contamination, does not provide an oxygen source and would not be a suitable
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`reactant for the formation of an oxide film. Id. Further, when depositing an oxide
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`film, not only carbon but also nitrogen are sources of contamination in the
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`resulting film. Id. Metal alkylamides are characterized as “amides” due to their
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`bonds with nitrogen and, can act as a source of nitrogen contamination. See id.
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`As such, at the time of the claimed inventions, those of ordinary skill in the
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`art would have considered the use of a metal alkylamide in an ALD process to
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`produce a metal oxide film to be particularly susceptible to unsuitable levels of
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`contamination. See Gladfelter Decl. at ¶¶ 122-31.
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` CLAIM CONSTRUCTION AND ORDINARY SKILL IN THE ART V.
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`A. Claim Construction
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`In an inter partes review, claim terms in an unexpired patent are interpreted
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`according to their broadest reasonable construction in light of the specification of
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`the patent in which they appear. 37 C.F.R. § 42.100(b); Office Patent Trial
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`Practice Guide, 77 Fed. Reg. 48,756, 48,766 (Aug. 14, 2012). Under this standard,
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`a claim term is given its ordinary and customary meaning as it would be
`
`understood by one of ordinary skill in the art. In re Translogic Tech., Inc., 504
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`F.3d 1249, 1257 (Fed. Cir. 2007); TRW Automotive U.S., LLC v. Magna
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`Electronics, Inc., IPR2015-00949, Paper 7 at 9 (Sep. 17, 2015). For purposes of
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`this paper, Harvard interprets based on their ordinary and customary meaning, but
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`reserves its rights to present evidence and arguments as to the proper construction
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`of the claim terms within the meaning of the ’016 Patent in this or any other
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`proceeding.
`
`B. A Person Having Ordinary Skill In The Art
`
`Petitioner alleges that a hypothetical person of ordinary skill in the field of
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`the ’016 Patent at the time of the invention “would be a person with at least a
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`Bachelor of Science degree in electrical engineering, chemical engineering,
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`chemistry, physics, materials science, or a closely related field, along with at least
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`5 years of experience in developing vapor deposition processes to form thin films.
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`An individual with an advanced degree in a relevant field would require less
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`experience in developing vapor deposition processes to form thin films.” Paper 1
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`at 21. For the purposes of this paper, Patent Owner applies Petitioner’s proposed
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`standard without prejudice. Should a trial be instituted, Patent Owner reserves the
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`right to present evidence and arguments as to the above definition or an alternative
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`definition as to the level of ordinary skill in the art.
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` THE CHALLENGED CLAIMS ARE NOT OBVIOUS OVER VI.
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`
`BUCHANAN IN VIEW OF MIN
`
`The Petition alleges that Claims 1-3, 5-7, and 9-10 of the ’016 Patent are
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`obvious over Buchanan in view Min. Petition at 4. However, as discussed below,
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`Petitioner has failed to demonstrate a reasonable likelihood that any of the
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`challenged claims are rendered obvious.
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`A.
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`Summary of the Asserted References
`
`1.
`
`U.S. Patent No. 6,984,591, “Precursor Source Mixtures”
`(Buchanan)
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`Buchanan discloses the use of an inert organic liquid as a solvent in which a
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`precursor compound can be dissolved, emulsified, or suspended to form a
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`precursor mixture for use in a CVD or an ALD deposition method. Ex. 1005 at
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`Abstract, 3:56-4:21, 29:14-34:30 (Claims 1-45, all requiring an inert “organic”
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`liquid); Gladfelter Decl. at ¶ 55. Buchanan indicates that “[m]ost films deposited
`
`by CVD or ALD for semiconductor applications are grown using conventional
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`bubbler technology with a carrier gas bubbled through a neat (i.e., without solvent)
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`precursor at an elevated temperature, relying on the vapor pressure of the precursor
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`to be constant in order to deliver a uniform precursor flux to the film.” Ex. 1005 at
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`1:28-33; Gladfelter Decl. at ¶ 55. Buchanan points out that the conventional
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`bubbler technology suffers from a number of shortcomings. Gladfelter Decl. at ¶
`
`55.
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`Buchanan’s contribution for solving the problems of conventional systems
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`for the delivery of precursors to an AL