Case 2:20-cv-00038-JRG Document 1-5 Filed 02/14/20 Page 1 of 34 PageID #: 101
`
`Exhibit 4
`
`

`

`Case 2:20-cv-00038-JRG Document 1-5 Filed 02/14/20 Page 2 of 34 PageID #: 102
`
`USOO8524.365B2
`
`(12) United States Patent
`O'Brien et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 8,524,365 B2
`*Sep. 3, 2013
`
`(54) PREPARATION OF NANOPARTICLE
`MATERLALS
`
`(75) Inventors: Paul O'Brien, High Peak (GB); Nigel
`Pickett, Manchester (GB)
`(73) Assignee: Nanoco Technologies Ltd. (GB)
`
`(*) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`This patent is Subject to a terminal dis
`claimer.
`
`(21) Appl. No.: 13/267,532
`
`(22) Filed:
`
`Oct. 6, 2011
`
`(65)
`
`Prior Publication Data
`US 2012/OO25155A1
`Feb. 2, 2012
`
`Related U.S. Application Data
`(63) Continuation of application No. 12/854,611, filed on
`Aug. 11, 2010, now Pat. No. 8,062,703, which is a
`continuation of application No. 1 1/579,050, filed as
`application No. PCT/GB2005/001611 on Apr. 27,
`2005, now Pat. No. 7,803,423.
`Foreign Application Priority Data
`
`(30)
`
`Apr. 30, 2004 (GB) ................................... O4O9877.8
`
`(2006.01)
`(2006.01)
`(2006.01)
`
`(51) Int. Cl.
`B82B I/O
`B82B3/00
`C3OB 29/10
`(52) U.S. Cl.
`USPC ........... 428/403; 428/402: 428/668; 428/689:
`427/212; 427/214; 427/215; 977/700; 977/773;
`977/813; 977/814;977/815;977/824; 977/827;
`977/830
`
`(58) Field of Classification Search
`None
`See application file for complete search history.
`
`(56)
`
`References Cited
`
`CN
`EP
`
`U.S. PATENT DOCUMENTS
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`FOREIGN PATENT DOCUMENTS
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`(Continued)
`Primary Examiner —Nathan Empie
`Assistant Examiner — Lisha Jiang
`(74) Attorney, Agent, or Firm — Wong, Cabello, Lutsch,
`Rutherford & Brucculeri LLP
`
`ABSTRACT
`(57)
`A method of producing nanoparticles comprises effecting
`conversion of a nanoparticle precursor composition to the
`material of the nanoparticles. The precursor composition
`comprises a first precursor species containing a first ion to be
`incorporated into the growing nanoparticles and a separate
`second precursor species containing a second ion to be incor
`porated into the growing nanoparticles. The conversion is
`effected in the presence of a molecular cluster compound
`under conditions permitting seeding and growth of the nano
`particles.
`
`23 Claims, 18 Drawing Sheets
`
`Y
`is
`NH, d-cdc. He
`\
`Se
`s
`Miss s s
`c
`e
`Se
`idgs
`NH
`NH C:Sise- sé
`O -: sis ? '-- w a Sects
`es: N?
`CS
`-St.
`
`w
`
`O
`
`V
`
`
`
`

`

`Case 2:20-cv-00038-JRG Document 1-5 Filed 02/14/20 Page 3 of 34 PageID #: 103
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`1.
`PREPARATION OF NANOPARTICLE
`MATERALS
`
`CROSS REFERENCE TO RELATED
`APPLICATIONS
`
`This application is a continuation of U.S. patent applica
`tion Ser. No. 12/854,611 filed Aug. 11, 2010, now U.S. Pat.
`No. 8,062.703, which is a continuation of U.S. patent appli
`cation Ser. No. 1 1/579,050, filed Oct. 27, 2006, now U.S. Pat.
`No. 7,803,423, issued Sep. 28, 2010, which is a U.S. national
`stage application of International (PCT) Patent Application
`Serial No. PCT/GB2005/001611, filed Apr. 27, 2005, which
`claims the benefit of GB Application No. 0409877.8, filed
`Apr. 30, 2004. The entire disclosures of each of these appli
`cations are hereby incorporated by reference as if set forth at
`length herein in their entirety.
`
`10
`
`15
`
`BACKGROUND OF THE DISCLOSURE
`
`2
`bandwidth emission, which is dependent upon the particle
`size and composition. Thus, quantum dots have higher kinetic
`energy than the corresponding nacrocrystalline material and
`consequently the first excitonic transition (band gap)
`increases in energy with decreasing particle diameter.
`Single core nanoparticles, which consist of a single semi
`conductor material along with an outer organic passivating
`layer, tend to have relatively low quantum efficiencies due to
`electron-hole recombination occurring at defects and dag
`gling bonds situated on the nanoparticle Surface which lead to
`non-radiative electron-hole recombination. One method to
`eliminate defects and daggling bonds is to grow a second
`material, having a wider band-gap and Small lattice mismatch
`with the core material, epitaxially on the surface of the core
`particle, (e.g. another II-VI material) to produce a “core-shell
`particle'. Core-shell particles separate any carriers confined
`in the core from surface states that would otherwise act as
`non-radiative recombination centers. One example is ZnS
`grown on the surface of CdSe cores. The shell is generally a
`material with a wider bandgap then the core material and with
`little lattice mismatch to that of the core material, so that the
`interface between the two materials has as little lattice strain
`as possible. Excessive strain can further result in defects and
`non-radiative electron-hole recombination resulting in low
`quantum efficiencies.
`However, the growth of more than a few mono layers of
`shell material can have the reverse effect thus; the lattice
`mismatch between CdSe and ZnS, is large enough that in a
`core-shell structure only a few monolayers of ZnS can be
`grown before a reduction of the quantum yield is observed,
`indicative of the formation of defects due to breakdown in the
`lattice as a result of high latticed strain. Another approach is
`to prepare a core-multi shell structure where the “electron
`hole' pair is completely confined to a single shell Such as the
`quantum dot-quantum well structure. Here, the core is of a
`wide bandgap material, followed by a thin shell of narrower
`bandgap material, and capped with a further wide bandgap
`layer, such as CdS/HgS/CdS grown using a substitution of Hg
`for Cd on the surface of the core nanocrystal to depositjust 1
`monolayer of HgS.''The resulting structures exhibited clear
`confinement of photoexcited carriers in the HgSlayer.
`The coordination about the final inorganic Surface atoms in
`any core, core-shell or core-multi shell nanoparticles is
`incomplete, with highly reactive “daggling bonds' on the
`Surface, which can lead to particle agglomeration. This prob
`lem is overcome by passivating (capping) the "bare' surface
`atoms with protecting organic groups. The capping or passi
`Vating of particles not only prevents particle agglomeration
`from occurring, it also protects the particle from its Surround
`ing chemical environment, along with providing electronic
`stabilization (passivation) to the particles in the case of core
`material. The capping agent usually takes the form of a Lewis
`base compound covalently bound to Surface metal atoms of
`the outer most inorganic layer of the particle, but more
`recently, so as to incorporate the particle into a composite, an
`organic system or biological system can take the form of an
`organic polymer forming a sheaf around the particle with
`chemical functional groups for further chemical synthesis, or
`an organic group bonded directly to the Surface of the particle
`with chemical functional groups for further chemical synthe
`S1S.
`Many synthetic methods for the preparation of semicon
`ductor nanoparticles have been reported, early routes applied
`conventional colloidal aqueous chemistry, with more recent
`methods involving the kinetically controlled precipitation of
`nanocrystallites, using organometallic compounds.
`
`There has been substantial interest in the preparation and
`characterization, because of their optical, electronic and
`chemical properties, of compound semiconductors consisting
`of particles with dimensions in the order of 2-100 nm, often
`referred to as quantum dots and/or nanocrystals. These stud
`ies have occurred mainly due to their size-tunable electronic,
`optical and chemical properties and the need for the further
`miniaturization of both optical and electronic devices' that
`now range from commercial applications as diverse as bio
`logical labeling, Solar cells, catalysis, biological imaging,
`light-emitting diodes amongst m