UNITED STATES PATENT AND TRADEMARK OFFICE
`
`________________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`
`________________________
`
`NANOCO TECHNOLOGIES, LTD.
`Petitioners
`
`v.
`
`MASSACHUSETTS INSTITUTE OF TECHNOLOGY
`
`Patent Owner
`
`________________________
`
`DECLARATION OF MARGARET A. HINES
`IN SUPPORT OF PETITION FOR INTER PARTES REVIEW
`OF U.S. PATENT NO. 6,322,901
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`1
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`1 of 32
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`Nanoco Technologies, Ltd
`EXHIBIT 1002
`
`
`
`________________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`
`________________________
`
`NANOCO TECHNOLOGIES, LTD.
`Petitioners
`
`v.
`
`MASSACHUSETTS INSTITUTE OF TECHNOLOGY
`
`Patent Owner
`
`________________________
`
`DECLARATION OF MARGARET A. HINES
`IN SUPPORT OF PETITION FOR INTER PARTES REVIEW
`OF U.S. PATENT NO. 6,322,901
`
`1
`
`1 of 32
`
`Nanoco Technologies, Ltd
`EXHIBIT 1002
`
`
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`I, Margaret A. Hines, declare:
`
`Background and Qualifications
`
`1.
`
`I am over 21 years of age. Counsel for Petitioner has asked me to
`
`review documents relating to the Petition for Inter partes Review of U.S. Patent
`
`No. 6,322,901 (“the ‘901 Patent”) and to provide my opinions regarding technical
`
`information in those documents.
`
`I am employed by Nanoco Technologies, Ltd.,
`
`Petitioner and Real Party in Interest in this proceeding, as a technical business
`
`development director.
`
`2.
`
`I previously provided Declarations in Inter partes Reexamination
`
`proceedings of patents related to the ‘901 Patent. Those proceedings were the Inter
`
`partes Reexaminations of U.S. Patent Nos. 6,861,155 (Reexamination No.
`
`95/001,268) and 7,125,605 (Reexamination No. 95/001,298). I was not an
`
`employee of Petitioner at the time I provided those declarations. Copies of my
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`declarations in those reexamination proceedings are contained within Exhibits
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`1003 and 1004 of the Petition.
`
`3.
`
`From October 1992 to March 1998, I was a graduate student in the
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`department of Chemistry at the University of Chicago, Chicago Illinois. I
`
`graduated with a Ph.D. in chemistry in 1998.
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`2
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`2 of 32
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`4. While in graduate school at the University of Chicago, I was the lead
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`author of the peer-reviewed research paper, “Synthesis and Characterization of
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`Strongly Luminescing ZnS-Capped CdSe Nanocrystals,” J. Phys. Chem. 1996,
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`100, 468-471, referred to as “Hines” in the reexamination materials. Since that
`
`time I have continued to work in the area of quantum dot nanocrystals and other
`
`nanomaterials. A copy of my resume and a list of my publications is attached to
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`this declaration as Appendix A.
`
`5.
`
`I have reviewed the following materials:
`
`a. U.S. Patent No. 6,322,901 (“the ‘901 Patent).
`
`b. U.S. Patent No. 6,861,155 (“the ‘155 Patent).
`
`c. U.S. Patent No. 7,125,605 (“the ‘605 Patent”).
`
`d. “Synthesis and Characterization of Strongly Luminescing ZnS-
`
`Capped CdSe Nanocrystals,” J. Phys. Chem. 1996, 100, 468-
`
`471 (“Hines”).
`
`e.
`
` Murray et al. “Synthesis and Characterization of Nearly
`
`Monodisperse CdE
`
`(E = S, Se, Te) Semiconductor
`
`Nanocrystallites,” J. Am. Chem. Soc. 1993, 115, 8706-15
`
`(“Murray”).
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`3
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`3 of 32
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`
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`f. Danek et al. “Preparation of II-VI quantum dot composites by
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`electrospray organometallic chemical vapor deposition,” J.
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`Cryst. Growth, 1994, 145, 714-720 (“Danek”).
`
`g. Tischchenko, et al., Solid State Communications, Vol. 96, 1995,
`
`795-798 (“Tischchenko”).
`
`h.
`
`Rodriguez-Viejo
`
`et
`
`al.,
`
`“Cathodoluminescence
`
`and
`
`Photoluminescence of Highly Luminescent CdSe/ZnS Quantum
`
`Dot Composites,” App. Phys. Let., 1997, 70, 2132-2134
`
`(“Rodriguez-Viejo”).
`
`i. Peng et al., “Epitaxial Growth of Highly Luminescent CdSe/CdS
`
`Core/Shell Nanocrystals with Photostability and electronic
`
`Accessibility,” J. Am. Chem. Soc. 1997 (119) 7019-29
`
`(“Peng”).
`
`j. Kortan et al. “Nucleation and Growth of CdSe on ZnS Quantum
`
`Crystallite Seeds, and Vice Versa, in Inverse Micelle Media,” J.
`
`Am. Chem. Soc. 1990, 112, 1327-32 (“Kortan”).
`
`k.
`
`Premachandran et al., “The Enzymatic Synthesis of Thiol-
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`Containing
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`Polymers
`
`to
`
`Prepare
`
`Polymer-CdS
`
`4
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`4 of 32
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`
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`Nanocomposites,”
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`Chem. Mater.,
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`1997,
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`1342-47
`
`(“Premachandran”).
`
`l.
`
`Coffer et al., “Characterization of quantum-confined CdS
`
`nanocrystallites stabilized by deoxyribonucleic acid (DNA),”
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`Nanotechnology 1992 69-76 (“Coffer”).
`
`6.
`
`I am informed that certain determinations are to be analyzed from the
`
`perspective of a “person of ordinary skill in the art” (POSITA) who would have
`
`been involved with the technology at issue at the time of the claimed invention,
`
`which I have been informed is November 13, 1997.
`
`I have been informed that a
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`POSITA is a hypothetical person who is presumed to be aware of all pertinent art,
`
`thinks along conventional wisdom in the art, and is a person of ordinary creativity.
`
`Based on my review of the documents listed above, as well as my own experience
`
`in the technical field, I believe that a person of ordinary skill in the art would have
`
`a high degree of understanding of chemistry and/or material science, particularly
`
`inorganic chemistry. Such a person would likely have an advanced degree
`
`(Masters or Ph.D.) in one of those disciplines or would have been working toward
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`such a degree. Based on my education and experience, I have an understanding of
`
`the capabilities of a POSITA in the field of the subject matter of the ‘901 Patent.
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`5
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`5 of 32
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`
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`Monodisperse
`
`7.
`
`Several claims of the ‘901 Patent recite a “monodisperse particle
`
`population.” In that context, the term “monodisperse” refers to how much (or how
`
`little) the sizes of the particles within the population vary. To say that a first
`
`particle population has a higher degree of monodispersity than a second particle
`
`population means that the sizes of the particles of the first population vary less than
`
`the sizes of the particles of the second population. There is no single objective
`
`standard that differentiates a population of particles that is monodisperse from one
`
`that is not.
`
`8.
`
`I have reviewed the ‘901 Patent’s definition of monodisperse, wherein
`
`it states:
`
`By monodisperse, as that term is used herein, it is meant
`a colloidal system in which the suspended particles have
`substantially identical size and shape.
`
`Col. 4, ll. 18-21. However, the ‘901 Patent does not define what constitutes
`
`“substantially identical size and shape.” A person of skill in the art would
`
`understand generally the statement “the first particle population is more
`
`monodisperse than the second particle population.” Likewise, a person of skill in
`
`the art would understand the degree of monodispersity is defined in terms of
`
`objective and measurable quantities, such as defined statistical deviation about a
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`6
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`6 of 32
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`mean particle size within a population or defined as a function of the bandwidth of
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`light emission from the population. The ‘901 Patent references both of those
`
`indicia of monodispersity, i.e., deviation about a mean particle size and emission
`
`bandwidth. See, e.g., col. 4, ll. 17-35. But the ‘901 Patent does not state where the
`
`line is drawn between a population of nanoparticles that is monodisperse and one
`
`that is not. For example, the ‘901 Patent states: “For the purposes of the present
`
`invention, monodisperse particles deviate less than 10% in rms diameter in the
`
`core, and preferably less than 5% in the core.” Col. 4, ll. 21-23. However, the
`
`‘901 Patent also states: “As a result of the narrow size distribution of the capped
`
`nanocrystallites of the invention, the illuminated quantum dots emit light of a
`
`narrow spectral range resulting in high purity light. Spectral emissions in a narrow
`
`range of no greater than about 60 nm, preferably 40 nm and most preferably 30 nm
`
`at full width half max (FWHM) are observed.” Col. 4, ll. 28-35. Because the ‘901
`
`Patent references multiple indicia of monodispersity and also refers to a range of
`
`values for those indicia, a POSITA would understand the broadest reasonable
`
`construction1 of “monodisperse” as not specifying a particular bright line defining
`
`1 I have been informed that the “broadest reasonable construction” is the standard
`to be applied when interpreting the claims and terms of the ‘901 Patent in this
`proceeding. I understand the “broadest reasonable construction” is understood in
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`7
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`7 of 32
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`
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`a particular particle population as monodisperse, but instead, providing a general
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`guidance as to what that term means. As discussed in more detail below, I have
`
`reviewed the references referred to as Danek, Rodriquez-Viejo, Peng, Murray, and
`
`Hines, which describe populations of nanocrystals similar to the ones described in
`
`the ‘901 Patent. Each of those references describe populations of nanocrystals that
`
`are disperse, as that term is used in the ‘901 Patent. For example, each of those
`
`references describes populations of nanocrystals that have emission FWHM values
`
`of less than 40 nm.
`
`Short-chain Polymer
`
`9.
`
`Claim 21 recites a nanocrystal having a coating comprising a short-
`
`chain polymer terminating in a moiety having affinity for a suspending medium.
`
`However, the ‘901 Patent does not describe what kind of polymers meet those
`
`requirements, what is meant by the term “short-chain,” or how such coated
`
`nanocrystals would be formed. In fact, the specification only mentions polymer
`
`coating in two sentences, one at col. 3, lines 1-6, which states, “The organic layer
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`may be comprised of moieties selected to provide compatibility with a suspension
`
`medium, such as a short-chain polymer terminating in a moiety having affinity for
`
`view of the specification from the perspective of a POSITA as of the earliest
`priority date of the patent.
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`8
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`a suspending medium, and moieties which demonstrate an affinity to the quantum
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`dot surface,” and the other at col. 7, lines 24-28, stating, “In other embodiments,
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`the capped quantum dots may be exposed to short chained polymers which exhibit
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`an affinity for the capped surface on one end which terminate in a moiety having
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`an affinity for the suspension or dispersion medium.” This is the sum total of the
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`‘901 specification’s discussion of polymer coatings.
`
`10.
`
`In the art there is no objective standard defining what constitutes a
`
`short-chain polymer. Terms like “short” and “long” are relative and context-
`
`specific. What might be considered a “short-chain” polymer in one context might
`
`be considered a “long-chain” polymer in a different context. Because a person of
`
`skill in the art would not be able to determine with certainty whether an organic
`
`coating would be considered to comprise a short-chain polymer based on the ‘901
`
`specification, the broadest reasonable construction would include any polymer-
`
`coated nanocrystal having an affinity for a suspending medium.
`
`“the first and second semiconductor materials are the same or different”
`
`11.
`
`Each of the independent claims of the ’901 Patent recites coated
`
`nanocrystals having a core comprising a first semiconductor material and an
`
`overcoating comprising a second semiconductor material wherein the first and
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`second semiconductor materials are the same or different. The simple drawing
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`below illustrates what that limitation means to a person of skill in the art:
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`The first and second semiconductor materials are represented by the numbers 1 and
`
`2, respectively. The claim limitation states that the core comprises a first
`
`semiconductor material (1) and the overcoating comprises a second semiconductor
`
`material (2). In the case that the first and second semiconductor materials are
`
`different, there is an interface between the core and the overcoating where the first
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`semiconductor ends and the second semiconductor begins. However, if the first
`
`and second semiconductor materials are the same, then there is no interface. In
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`other words, there is no place that the core ends and the overcoating begins.
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`Instead, the particle is simply a nanocrystal of one material. For example, an
`
`overcoated nanocrystal having a CdSe core and a CdSe overcoating is simply a
`
`CdSe nanocrystal.
`
`Overcoating “uniformly deposited”
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`10
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`10 of 32
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`
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`12. Claims 1, 32, and 44 recite an overcoating “uniformly deposited on
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`the core” of the nanoparticle. The term “uniformly deposited” does not have any
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`specific accepted meaning within the field of chemistry and the ‘901 Patent
`
`specification does not provide any specific definition of the term “an overcoating
`
`uniformly deposited on the core.” Adding to the confusion, claims 14 and 27 of
`
`the ‘901 Patent recite nanoparticles wherein the overcoating comprises “less than
`
`about one monolayer” of the second semiconductor material. If the overcoating is
`
`less than one monolayer, then that means the core is not completely coated by the
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`overcoating. In other words, some parts of the core are coated and other parts are
`
`not. That makes the meaning of uniform somewhat ambiguous. Therefore, in my
`
`opinion, a person of ordinary skill in the art would understand that “uniformly
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`deposited” as used in the ‘901 patent to include an overcoating that may be less
`
`than a monolayer, or in other words an overcoating that does not completely cover
`
`the core.
`
`Full Width at Half Max (FWHM).
`
`13.
`
`I have calculated the full width half max (FWHM) of the emission
`
`spectra illustrated in Figure 3 of Hines, the article for which I was lead author. I
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`calculated the FWHM in the way one of ordinary skill in the art would have done
`
`when the article was published. I first enlarged Figure 3. I derived a baseline for
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`11
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`11 of 32
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`
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`the emission peak by extrapolating a region of the spectrum with no emission.
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`Next, I determined the maximum value of the emission by measuring from the
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`peak emission to the baseline. I then determined where the half maximum value
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`would be by measuring half the distance between the baseline and the peak
`
`emission. Next, I determined the width of the emission curve (in nm) at that point,
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`i.e. half the maximum value. This width is the FWHM (full width half max).
`
`When Figure 3 is enlarged as explained in this paragraph, the lines denoting the
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`emission spectra have a thickness corresponding to about 2 nm. The finite width
`
`of the line itself leads to an error of no greater than ± 2 nm in the measurement of
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`the FWHM. I made all measurements using the center of the lines.
`
`14. Using the method described in paragraph 13, I determined that the
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`emission spectrum of the CdSe-ZnS nanocrystals (solid line) has a FWHM of 39
`
`nm ± 2 nm.
`
`15.
`
`I have calculated the FWHM of spectra illustrated in publications
`
`many times throughout my career. The method I described in paragraph 13 is the
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`method a person of skill in the art would use to calculate the FWHM of an
`
`emission spectrum illustrated in a publication.
`
`Thickness of monolayer
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`12
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`12 of 32
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`16.
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`The ‘901 Patent at col. 7 line 40 states that the thickness of a ZnS
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`monolayer is about 3.1 Å. The ZnS coatings of the nanocrystals described in
`
`Hines are 6 ± 3 Å thick. Hines, p. 469, col. 2. Assuming that the thickness of a
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`ZnS monolayer is about 3.1 Å, the 6 Å coating of ZnS described in Hines is about
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`2 monolayers thick (i.e. 6 Å divided by 3.1 Å per monolayer).
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`17. As I stated in paragraph 16, the ZnS overcoatings described in Hines
`
`are about 2 monolayers thick. A person of skill in the art would appreciate that
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`those overcoatings do not form instantaneously as complete monolayers. Instead,
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`the overcoating atoms (Zn and S, in the case of Hines and the ‘901 Patent) react on
`
`the surface of the core nanoparticle to gradually form the overcoating layer(s).
`
`During that process, as the overcoating is deposited there are regions of the core
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`nanoparticle that are covered with ZnS and other regions of the core nanoparticle
`
`that are not yet covered. In other words, the coverage during that intermediate
`
`overcoating stage comprises less than a monolayer of the overcoating (i.e., second)
`
`semiconductor material.
`
`Organic layer
`
`18.
`
`In the process described in Hines, both the formation of the CdSe core
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`and the ZnS overcoating occur in TOPO solvent. TOPO is an abbreviation for tri-
`
`n-octylphophine oxide, which is an organic solvent. That solvent was used during
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`13
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`13 of 32
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`
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`the reaction that formed the ZnS overcoating on the CdSe core QDs in Hines.
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`After the ZnS overcoating was formed, an organic layer of TOPO remained on the
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`surface of the ZnS overcoat layer. That TOPO layer is an organic layer on the QD
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`surface. When the nanocystals are suspended in TOPO, TOPO would be
`
`considered the suspending medium. The TOPO molecule has a phosphine oxide
`
`group that has an affinity for the QD surface. The surface-bound TOPO on the
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`nanocrystals has an affinity for the TOPO suspending medium. Therefore, the
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`TOPO organic layer includes both a moiety that has affinity for the QD surface and
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`a moiety that has affinity for the TOPO suspension medium.
`
`Emission spectrum colors
`
`19. QDs have the ability to absorb light at a first wavelength (color) and
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`emit
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`light at a second wavelength (color), a phenomena known as
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`photoluminescence. Larger QDs emit light at longer wavelengths than do smaller
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`QDs. The emission spectrum of the Hines CdSe-ZnS QD nanocrystals, which is
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`illustrated in Figure 3 of Hines (solid line), has an emission peak at about 525 nm.
`
`A person of skill in the art would recognize that light having a wavelength of 525
`
`nm would be perceived as green light. Visible light is simply the portion of the
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`electromagnetic spectrum that can be detected by the human eye. The perceived
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`14
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`14 of 32
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`color of light depends on the wavelength of the light. The color/wavelength
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`relationship is illustrated in the following table:
`
`Color
`
`Wavelength (nm)
`
`Violet
`
`Blue
`
`Green
`
`Yellow
`
`Orange
`
`Red
`
`380-450
`
`450-495
`
`495-570
`
`570-590
`
`590-620
`
`620-750
`
`As shown in the table, light having a wavelength of 525 nm corresponds to the
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`green region of the visible light spectrum.
`
`20.
`
`The emission spectrum of the Hines CdSe-ZnS nanocrystals, which is
`
`illustrated in Figure 3 of Hines (solid line), shows that the nanocrystals emit at
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`least some light at all wavelengths from about 500 nm to about 600 nm. Thus, the
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`light emitted by the nanocrystals contains green, yellow, and orange light. As
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`stated in paragraph 19 above, the peak emission occurs at 525 nm, which
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`corresponds to green light. But the emitted light also includes yellow and orange
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`light.
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`Crystalline structure
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`15
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`15 of 32
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`21. Hines at page 469, col. 1 states: “this last characteristic [i.e., the
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`characteristic that CdSe and ZnS do not alloy well] is in part due to large lattice
`
`mismatch between the two materials.” A person of skill in the art would
`
`understand that the discussion of lattice mismatch is directed to differences
`
`between atom spacing in the crystalline lattice of the core (i.e., CdSe) and a
`
`crystalline lattice of the shell (i.e., ZnS). Lattice structure is a characteristic of a
`
`crystalline structure. Therefore, lattice mismatch refers to the mismatch of the
`
`lattice structure (crystalline) of the core and the lattice structure (crystalline) of the
`
`shell.
`
`Danek Overcoating
`
`22.
`
`The CdSe cores of Danek are overcoated with ZnSe by reacting the
`
`CdSe cores with the ZnSe precursors TOPSe and diethylzinc in TOP. See Danek,
`
`page 715, col. 2. Danek states that transmission electron microscopy (TEM) shows
`
`a high degree of crystallinity of the composite nanocrystals with relatively few
`
`structural defects. P. 715, col. 2. That indicates the overcoating is uniform.
`
`Danek FWHM
`
`23.
`
`I calculated the full width at half max (FWHM) of the emission curves
`
`in Figs. 3 and 4 of Danek using the method I described in paragraph 13 above.
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`16
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`16 of 32
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`
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`Curve Fig. 3, curve a has a FWHM of 42 nm; Fig. 3, curve b has a FWHM of 33
`
`nm; and Fig. 4, curve b has a FWHM of 33 nm.
`
`Size-selective precipitation
`
`24.
`
`I have read the discussions of size-selective precipitation in the ‘901
`
`Patent, Murray, and Danek. I am familiar with size-selective precipitation. Size-
`
`selective precipitation was well known in the art more than a year before the ‘901
`
`Patent application was filed. For example, Murray and Danek both describe size-
`
`selective precipitation.
`
`During size-selective precipitation, the CdSe core
`
`nanocrystals are dispersed in a solvent. Another solvent (termed a counter solvent
`
`or “non-solvent”) is slowly added to the dispersion, causing the nanocrystals to
`
`precipitate or flocculate. The larger nanocrystals come out of precipitate first.
`
`Those nanocrystals can be isolated using a centrifuge, which separates the solid
`
`(termed a precipitate) from the liquid (termed a supernatant).
`
`Therefore, the
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`precipitate will have a narrower size distribution than the original nanocrystal
`
`population because it is more concentrated with the larger nanocrystals. The
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`supernatant will also contain a narrower size distribution than the original
`
`population because it has more of the smaller nanocrystals.
`
`If narrower size
`
`distributions are needed, one can add more nonsolvent to the dispersion to
`
`precipitate another fraction and isolate that precipitate by centrifugation. You then
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`17
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`17 of 32
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`have three populations; (1) the supernatant, (2) the precipitate from the first
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`precipitation, and (3) the precipitate from the second precipitation. This process
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`can be repeated to obtain narrower and narrower size distribution. Likewise, any
`
`of the precipitates can be redispersed and reprecipitated to yield even narrower size
`
`distributions. As the size distribution of a population narrows, the emitted color
`
`from the population becomes purer, i.e. red becomes more precisely red. A
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`POSITA would be motivated to perform the amount of size selective precipitation
`
`needed to obtain the purity of color needed for a particular application.
`
`Thickness of Danek overcoating.
`
`25. Danek states that CdSe nanocrystallites having diameters of about 3.3.
`
`nm were coated with ZnSe to yield composite nanocrystals having diameters of 5-6
`
`nm. Danek, p. 715, col. 2. Because the overcoating surrounds the nanocrystal, the
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`difference in diameters of the coated and uncoated nanocrystals is roughly twice
`
`the thickness of the coating layer. The thickness of the ZnSe layer on the surface of
`
`the nanocrystals is therefore about 1.1 nm (i.e., (5.5 nm - 3.3 nm)/2 = 1.1 nm). A
`
`nanometer (nm) is equal to 10 angstroms (Å). Therefore, the ZnSe coatings
`
`described in Danek are about 11 Å thick.
`
`26.
`
`Tischchenko states that one atomic monolayer of ZnSe is 2.83 Å
`
`thick. Assuming that thickness is correct and assuming that the overcoatings
`
`18
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`18 of 32
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`
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`described in Danek are 11 Å thick, then the overcoatings described in Danek are
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`about 3.9 monolayers thick (i.e., 11 Å / 2.83 Å per monolayer = 3.9 monolayers).
`
`27.
`
`The CdSe cores of Danek are overcoated with ZnSe by reacting the
`
`CdSe cores with the ZnSe precursors TOPSe and diethylzinc in TOP. See Danek,
`
`page 715, col. 2. As described in paragraph 26 above, the CdSe overcoatings in
`
`Danek are about 3.9 monolayers thick. A person of skill in the art would appreciate
`
`that the 3.9 monolayer ZnSe overcoating does not form instantaneously as
`
`complete monolayers. Instead, the overcoating atoms (Zn and Se) react on the
`
`surface of the core nanoparticle to gradually form the overcoating layer(s). During
`
`the formation of at least the first layer, there are regions of the core nanoparticle
`
`that are covered with ZnSe and other regions of the core nanoparticle that are not
`
`yet covered. In other words, the overcoating during that intermediate stage is less
`
`than a monolayer thick. Likewise, during the growth process toward a 3.9
`
`monolayer thickness, intermediate species have fewer than 3.9 monolayers. For
`
`example, at various times during the overcoating process, the nanocrystals will
`
`have overcoatings that are, on average, 1, 2, 3, and nearly 4 monolayers thick, as
`
`well as all values in between 0 and 3.9 monolayers thick. Danek states that the
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`overcoating process is a “controlled overgrowth” process, implying that if a person
`
`wanted fewer than 4 monolayers, they could simply use less ZnSe precursor to
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`form the monolayers. See Danek, page 715, col. 2. A POSITA would routinely
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`experiment with a range of coating thicknesses to optimize the impact of the
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`overcoating synthesis on the optical quality of the resulting nanocrystals within
`
`their own particular process.
`
`Danek Organic Coating
`
`28. As I stated above, Danek discloses overcoating CdSe nanocrystal
`
`cores with ZnSe
`
`in TOP as a solvent.
`
`TOP
`
`is an abbreviation for
`
`trioctylphosphine, which is an organic solvent used in Danek for the reaction
`
`whereby CdSe nanocrystal cores are overcoated with ZnSe. The TOP includes a
`
`phosphine moiety, which has affinity for the ZnSe overcoating. Following the
`
`overcoating, an organic layer of TOP exists on the surface of the ZnSe overcoating
`
`layer because the TOP molecules are attracted to the ZnSe material via the
`
`phosphine moiety. When the nanocystals are suspended in TOP, TOP would also
`
`be considered the suspending medium. The surface-bound TOP has an affinity for
`
`the TOP suspending medium. Thus, the TOP organic layer on the surface of the
`
`overcoated nanocrystals has an affinity for both the ZnSe overcoating and for the
`
`TOP suspending medium. Danek also describes exchanging the TOP organic layer
`
`for a pyridine organic layer. Danek, p. 715, col. 2. Danek states that a pyridine
`
`organic coating was selected to ensure compatibility of the nanocrystals with the
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`
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`matrix used for the OMCVD experiments described in Danek. Pyridine exhibits
`
`affinity for the outer ZnSe surface of the Danek nanocrystals. That is why pyridine
`
`is able to displace the TOP organic layer that is present on the nanocrystals.
`
`Danek Emission Color
`
`29.
`
`The emission spectra illustrated in Fig. 3 of Danek have peak
`
`emissions at 568 nm and 616 nm. The QDs exhibit some emission intensity at all
`
`wavelengths from about 540 nm to 640 nm, meaning that the nanocrystals emit at
`
`least some light at all wavelengths in that range. Thus, the light emitted by the
`
`nanocrystals contains green, yellow, orange, and red light.
`
`Rodriguez-Viejo FWHM.
`
`30. I have reviewed the publication referred to as Rodriguez-Viejo. I have
`
`calculated the FWHM of the luminescence spectra of the (CdSe)ZnS quantum dots
`
`illustrated in Fig. 1 of Rodriguez-Viejo using the technique described in paragraph
`
`9 above.
`
` Photoluminescence curve (a) has a FWHM of 35 nm and
`
`photoluminescence curve (b) has a FWHM of 49 nm. The QDs exhibit some
`
`emission intensity above 620 nm, meaning that the QDs emit some red light.
`
`Peng FWHM.
`
`31.
`
`Figure 3 of Peng illustrates photoluminescence spectra of two series
`
`of core/shell nanocrystals. I note that the x-axis (i.e., the horizontal axis) is
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`
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`represented in electron volts (eV) rather than in nanometers (nm). The relationship
`
`between energy in electron volts (eV) and wavelength in nanometers (nm) is given
`
`by E = hc/λ, where h is Planck’s constant, c is the speed of light, and λ is
`
`wavelength. This relationship reduces to E(eV) = 1240/λ(nm). Using that
`
`relationship and the method for calculating the FWHM described above, I
`
`determined that the top photoluminescence curve of Figure 3A has a FWHM of
`
`about 33 nm. The photoluminescence spectra illustrated in Figure 3 of Peng show
`
`emission range from about .9 eV to about 2.25 eV. Converting that range to
`
`wavelength in nanometers using the formula E(eV) = 1240/λ(nm) yields about 560
`
`nm to about 650 nm.
`
`Peng Organic layer
`
`32.
`
`Peng discloses nanocrystals capped with dodecylamine. Dodecylmine
`
`contains an amine moiety, which has affinity for the outer surface of
`
`semiconductor nanocrystals.
`
`Murray FWHM
`
`33.
`
`Turning to Murray, I have calculated the FWHM of the emission
`
`spectrum of the CdSe quantum dots illustrated in Figure 5 of Murray using the
`
`technique described in paragraph 9 above. The emission curve has a FWHM of 32
`
`nm. The emission maximum is at about 560 nm.
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`22 of 32
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`
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`34. Murray discloses preparing CdSe nanocrystals in TOPO/TOP. A
`
`layer of TOPO/TOP remains on the surface of the CdSe nanocrystals. As
`
`discussed above, that layer of TOPO/TOP can be exchanged with pyridine. Also
`
`as discussed above, each of the solvents, TOPO/TOP and pyridine, contain
`
`moieties that have an affinity for the surface of the CdSe nanocrystals.
`
`Murray Emission Color
`
`35. As stated above, the wavelength of light that a QD emits is a function
`
`of the size of the QD. Larger QDs emit longer wavelengths of light and smaller
`
`QDs emit shorter wavelengths of light. Thus, larger QDs emit light shifted toward
`
`the red end of the spectrum and smaller QDs emit light shifted toward the blue end
`
`of the spectrum. The dashed line of Figure 2 of the ‘901 Patent illustrates the
`
`photoluminescence spectra of bare CdSe QDs having the following sizes: (a) 23 Å,
`
`(b) 42 Å, (c) 48 Å, and (d) 55 Å. The following chart tabulates the wavelength of
`
`the emission peaks and the colors corresponding with those wavelengths:
`
`QD size (Å)
`
`Wavelength (nm)
`
`23
`
`42
`
`48
`
`~475
`
`~560
`
`~590
`
`23
`
`Color
`
`Blue
`
`Green
`
`Yellow
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`23 of 32
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`
`
`55
`
`~630
`
`Red
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`Murray, which describes the same type of CdSe QDs as the cores described in the
`
`‘901 Patent, states that nanocrystals with diameters of 12 Å to 115 Å were
`
`prepared. See Murray abstract. A POSITA would understand that since the
`
`materials and the preparation methods are the same in Murray and in the ‘901
`
`Patent, the correlation between the size of the CdSe nanocrystal and the emission
`
`color would be the same, or at least similar. A POSITA would therefore expect
`
`that the 12 Å to 115 Å range of QD sizes described in Murray would emit light
`
`covering the visible spectrum from blue to red.
`
`Murray/Kortan
`
`36. Kortan describes core/shell QDs having a CdSe core overcoated with
`
`a ZnS shell. A POSITA would be motivated to prepare CdSe cores according to
`
`the process described in Murray and then provide ZnS shells on those cores
`
`according to the process described in Kortan. A POSITA would understand that
`
`Murray provides QDs with a high degree of monodispersity, which, as I explained
`
`above, is desirable for optical quality. Kortan teaches that overcoating the QD
`
`core with a second semiconductor material increases the luminescence intensity, as
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`24
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`24 of 32
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`
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`illustrated in Figure 2 of Kortan. Increased luminescence intensity is also desirable
`
`for optical quality.
`
`Premachandran/Coffer
`
`37. Both Premachandran and Coffer are directed to binding QDs to
`
`polymers. Both Premachandran and Coffer explain that binding QDs to a polymer
`
`stabilizes the QDs in solution. A POSITA would have been motivated to bind the
`
`QDs prepared as described in any of the other references discussed above with
`
`polymers, as described in Premachandran and Coffer, to stabilize those QDs in a
`
`solvent. A POSITA would understand that, for a dispersion of QDs within a
`
`solvent to remain optically active, the QDs must remain suspended in the solvent.
`
`If the QDs precipitate from the solvent, then the dispersion loses its optical activity
`
`(i.e., the luminescence degrades). Thus, a POSITA would have been motivated,
`
`based on the teachings of Premachandran and Coffer, to use the polymers
`
`described therein to stabilize dispersions of QDs so that the QDs remain dispersed
`
`in the solvent.
`
`All statements made herein of my knowledge are true and all statements
`
`made on information and belief are believed to be true; and further these
`
`statements were made with the knowledge that willful false statements and the like
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`25
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`25 of 32
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`so made are punishable by fine or imprisonment, or both, under Section 1001 of
`
`Title 18 of the United States Code.
`
`Date: January 5, 2015
`
`~~Jt-LU--,
`Maret A. Hines, Ph.D.
`
`26
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`26 of 32
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`
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`APPENDIX A
`
`APPENDIX A
`
`27 of 32
`
`27 of 32
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`
`
`Location: San Jose, CA / Phone: 815.325.7878 / Email: mahines01@gmail.com
`MARGARET (PEGGY) A. HINES, PH.D.
`PROFILE
` Creative problem solver and enthusiastic self‐starter with supervisory, project management,
`and hands‐on technical experience.
` Technology forerunner with 20 years of experience in nanotechnology and advanced
`materials.
` Team leader managing semiconductor nanomaterials development and commercialization
`in photovoltaics, LEDs, and life sciences products.
` Innovator with hands on technical experience in materials synthesis and characterization,
`colloids, semiconductors, thin films, polymers, composites, emulsions, inks, printing, surface
`chemistry, self‐assembly, analytical chemistry, spectroscopy, and electron microscopy.
` Extensive experience with start‐up companies and technology development, strategy
`planning, and plotting roadmaps.
` Member of the judging panel for the first two Nano‐Entrepreneurship‐Academies (NEnA) in
`Germany. Organized internships for eight international students.
` Strong communicator. Author of 26 publications. Inventor on nine patents/applications.
`organizer at 2007 MRS Spring Meeting.
`Presenter of three invited talks. Chairman of
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