`
`Exhibit 3
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 2 of 33 PageID #: 69
`
`US007867557B2
`
`(12) United States Patent
`Pickett et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 7,867,557 B2
`*Jan. 11, 2011
`
`(54) NANOPARTICLES
`(75) Inventors: Nigel Pickett, East Croyden (GB);
`Steven Daniels, Manchester (GB); Paul
`O’Brien, High Peak (GB)
`(73) Assignee: Nanoco Technologies Limited,
`Manchester (GB)
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 168 days.
`This patent is Subject to a terminal dis
`claimer.
`
`(*) Notice:
`
`(21) Appl. No.:
`
`11/997,973
`
`(22) PCT Filed:
`(86). PCT No.:
`
`Aug. 14, 2006
`PCT/GB2OO6/OO3O28
`
`S371 (c)(1),
`Feb. 5, 2008
`(2), (4) Date:
`(87) PCT Pub. No.: WO2007/020416
`
`PCT Pub. Date: Feb. 22, 2007
`
`(65)
`
`Prior Publication Data
`US 2008/O220593 A1
`Sep. 11, 2008
`
`Foreign Application Priority Data
`(30)
`Aug. 12, 2005 (GB) ................................. O516598.O
`
`(51) Int. Cl.
`(2006.01)
`C30B 700
`(2006.01)
`B82B3/00
`(52) U.S. Cl. ....................... 427/214; 427/212; 427/215;
`428/402; 428/403; 428/404: 428/405; 428/406
`(58) Field of Classification Search ................... 257/14;
`427/212, 214, 215; 428/403, 404, 405
`See application file for complete search history.
`
`
`
`(56)
`
`References Cited
`
`U.S. PATENT DOCUMENTS
`
`2,769,838 A 11/1956 Matter et al.
`
`(Continued)
`FOREIGN PATENT DOCUMENTS
`
`CN
`
`1394599
`
`2, 2003
`
`(Continued)
`OTHER PUBLICATIONS
`Zhong et al., “Composition-Tunable ZnxCu1-xSe Nanocrystals with
`High Luminescence and Stability”, Journal of American Chemical
`Society. (2003).*
`
`(Continued)
`Primary Examiner Michael Cleveland
`Assistant Examiner—Lisha Jiang
`(74) Attorney, Agent, or Firm Bingham McCutchen LLP
`
`(57)
`
`ABSTRACT
`
`Method for producing a nanoparticle comprised of core, first
`shell and second shell semiconductor materials. Effecting
`conversion of a core precursor composition comprising sepa
`rate first and second precursor species to the core material and
`then depositing said first and second shells. The conversion is
`effected in the presence of a molecular cluster compound
`under conditions permitting seeding and growth of the nano
`particle core. Core/multishell nanoparticles in which at least
`two of the core, first shell and second shell materials incor
`porate ions from groups 12 and 15, 14 and 16, or 11, 13 and 16
`of the periodic table. Core/multishell nanoparticles in which
`the second shell material incorporates at least two different
`group 12 ions and group 16 ions. Core/multishell nanopar
`ticles in which at least one of the core, first and second
`semiconductor materials incorporates group 11, 13 and 16
`ions and the other semiconductor material does not incorpo
`rate group 11, 13 and 16 ions.
`
`17 Claims, 12 Drawing Sheets
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 3 of 33 PageID #: 70
`
`US 7,867,557 B2
`Page 2
`
`U.S. PATENT DOCUMENTS
`
`8, 1970 Green ........................ 136,203
`3,524,771 A
`9, 1986 Schwartz et al.
`4,609.689 A
`9, 2000 Castro et al.
`6,114,038 A
`3, 2001 Bawendi et al.
`6,207,229 B1
`4/2001 Barbera-Guillem et al.
`6,221,602 B1
`7/2001 Barbera-Guillem et al.
`6,261,779 B1
`11/2001 Bawendi et al.
`6,322.901 B1
`12/2001 Bawendi et al.
`6,326,144 B1
`12/2001 Barbera-Guillem
`6,333,110 B1
`4/2002 O'Brien et al.
`6,379,635 B2
`7/2002 Weiss et al.
`6,423,551 B1
`7/2002 Bawendi et al.
`6.426,513 B1
`8, 2003 Bawendi et al.
`6,607,829 B1
`6,660,379 B1 12/2003 Lakowicz et al.
`6,699,723 B1
`3, 2004 Weiss et al.
`6,815,064 B2 * 1 1/2004 Treadway et al. ........... 428,403
`6,855,551 B2
`2/2005 Bawendi et al.
`6,914,264 B2
`7/2005 Chen et al.
`7,041,362 B2
`5, 2006 Barbera-Guillem
`7,151,047 B2 12/2006 Chan et al.
`7,235,361 B2
`6, 2007 Bawendi et al.
`7,264,527 B2
`9, 2007 Bawendi et al.
`2003, OO17264 A1
`1, 2003 Treadway et al.
`2003/0106488 A1
`6/2003 Huang et al.
`2003/0148024 A1
`8, 2003 Kodas et al.
`2004.0007169 A1
`1/2004 Ohtsu et al.
`2004/01 10002 A1
`6, 2004 Kim et al.
`2004/O110347 A1
`6, 2004 Yamashita
`2004/0178390 A1
`9, 2004 Whiteford et al.
`2004/O250745 A1 12, 2004 Ogura et al.
`2005/0129.947 A1
`6/2005 Peng et al. .................. 428,403
`2005, 0145853 A1
`7/2005 Sato et al.
`2006, OO19098 A1
`1/2006 Chan et al.
`2006, OO61017 A1
`3, 2006 Strouse et al.
`2006, OO68154 A1
`3, 2006 Parce et al.
`2006/01 18757 A1
`6, 2006 Klimov et al.
`2006/0130741 A1
`6/2006 Peng et al.
`2007/0012941 A1
`1/2007 Cheon
`2007.0034.833 A1
`2/2007 Parce et al.
`2007/0059.705 A1
`3/2007 Lu et al.
`2007, 0104865 A1
`5/2007 Pickett ....................... 427,212
`2007, 011081.6 A1
`5, 2007 Jun et al.
`2007/0114520 A1
`5, 2007 Garditz et al.
`2007/O125983 A1
`6/2007 Treadway et al.
`2007/013 1905 A1
`6, 2007 Sato et al.
`2007/0199.109 A1
`8, 2007 Yi et al.
`2007/0202333 A1
`8, 2007 O'Brien et al.
`2007/0238126 A1 10, 2007 Pickett et al.
`2008. O107911 A1
`5, 2008 Liu et al.
`2008/O112877 A1
`5, 2008 Xiao et al.
`2008/O121844 A1
`5/2008 Jang et al.
`2008.0160306 A1
`7/2008 Mushtaq et al.
`2008.O220593 A1
`9, 2008 Pickett et al.
`2008/0257.201 A1 10, 2008 Harris et al.
`2008/0264479 A1 10, 2008 Harris et al.
`2009/O139574 A1
`6, 2009 Pickett et al.
`2009, 0212258 A1
`8, 2009 McCairn et al.
`2009,0263816 A1 10, 2009 Pickett et al.
`2010.0059721 A1
`3/2010 Pickett et al.
`2010.0068522 A1
`3/2010 Pickett et al.
`2010.0113813 A1
`5, 2010 Pickett et al.
`2010, 0123155 A1
`5, 2010 Pickett et al.
`2010.0193767 A1
`8/2010 Naasani et al.
`
`FOREIGN PATENT DOCUMENTS
`
`EP
`EP
`GB
`GB
`JP
`
`1783 137 A1
`1854,792 A1
`9518910.6
`2429838 A
`2005,139389
`
`5/2007
`11, 2007
`9, 1995
`3, 2007
`6, 2005
`
`3, 1997
`WO-97/101.75
`WO
`3, 2000
`WO-OOf 17642
`WO
`1, 2002
`WO-O2,04527
`WO
`3, 2002
`WO-0224623 A2
`WO
`4/2002
`WO-O2,29140
`WO
`12/2003
`WO-03/099708
`WO
`1, 2004
`WO WO-2004OO8550 A2
`4/2004
`WO WO-2004/033366
`8, 2004
`WO WO-2004/066361
`8, 2004
`WO WO-2004O65362 A2
`3, 2005
`WO WO-2005/021150
`11, 2005
`WO WO-2005,106082
`WO WO-2005106082 A1 11, 2005
`WO WO-2005 123575 A1 12/2005
`WO WO-2006001848 A2
`1, 2006
`WO WO-2006/017125
`2, 2006
`WO WO-2006O75974 A1
`T 2006
`WO WO-2006/116337
`11, 2006
`WO WO-2006 118543 A1
`11 2006
`WO WO-2006134599 A1 12/2006
`WO WO-2007020416 A1
`2, 2007
`WO WO-2007/049052
`5/2007
`WO WO-2007/060591
`5/2007
`WO WO-2007-060591 A
`5/2007
`WO WO-2007049052 A2
`5/2007
`WO WO-2007/065039
`6, 2007
`WO WO-2007 102799 A2
`9, 2007
`WO WO-2008O13780 A2
`1, 2008
`WO WO-2008.054874 A2
`5, 2008
`WO WO-2008133660 A2 11, 2008
`WO WO-2009016354 A1
`2, 2009
`WO WO-2009010681.0 A1
`9, 2009
`
`OTHER PUBLICATIONS
`
`Cumberland et al., “Inorganic Clusters as Single-Source Precursors
`for Preparation of CdSe, ZnSe, and CdSe/ZnS Nanomaterials.”
`Chemistry of Materials (2002).*
`Sheng et al., “In-Situ Encapsulation of Quantum Dots into Polymer
`Microspheres'. Langmuir, (2006), vol. 22(8), pp. 3782-3790.*
`Agger, J.R. et al., J. Phys. Chem. B (1998) 102, p. 3345.
`Aldana, J. et al. “Photochemical Instability of CdSe Nanocrystals
`Coated by Hydrophilic Thiols”. J. Am. Chem. Soc. (2001), 123:
`8844-8850.
`Alivisatos, A.P. "Perspectives on the Physical Chemistry of Semi
`conductor Nanocrystals'. J. Phys. Chem. (1996), 100, pp. 13226
`13239.
`Arici et al. Thin Solid Films 451-452 (2004) 612-618.
`Battaglia et al., “Colloidal Two-dimensional Systems: CodSe Quan
`tum Shells and Wells.” Angew Chem. (2003) 115:5189.
`Bawendi, M.G. The Quantum Mechanics of Larger Semiconductor
`Clusters ("Quantum Dots'), Annu. Rev. Phys. Chem. (1990), 42:
`477-498.
`Berry, C.R. “Structure and Optical Absorption of Agl Microcrystals'.
`Phys. Rev. (1967) 161: 848-851.
`Bunge, S.D. et al. “Growth and morphology of cadmium
`chalcogenides: the synthesis of nanorods, tetrapods, and spheres
`from CdO and CdCOCCH), J. Mater. Chem. (2003) 13: 1705
`1709.
`Castro et al., Chem. Mater. (2003) 15:3142-3147.
`Castro et al., “Synthesis and Characterization of Colloidal CuInS
`Nanoparticles from a Molecular Single-Source Precursors.” J. Phys.
`Chem. B (2004) 108: 12429.
`Chun et al. Thin Solid Films 480-481 (2005) 46-49.
`Contreraset al., “ZnO/ZnS(O,OH)/Cu(In,Ga)Se/Mo Solar Cell with
`18:6% Efficiency.” from3d World Conf. on Photovol. Energy Conv.,
`Late News Paper, (2003) pp. 570-573.
`Cui et al., “Harvest of near infrared light in PbSe nanocrystal-poly
`mer hybrid photovoltaic cells.” Appl. Physics Lett. 88 (2006)
`183111-183111-3.
`Cumberland et al., “Inorganic Clusters as Single-Source Precursors
`for Preparation of CdSe, ZnSe, and CdSe/ZnS Nanomaterials”
`Chemistry of Materials, 14, pp. 1576-1584. (2002).
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 4 of 33 PageID #: 71
`
`US 7,867,557 B2
`Page 3
`
`Dance et al., J. Am. Chem. Soc. (1984) 106:6285.
`Daniels et al., “New Zinc and Cadmium Chalcogenide Structured
`Nanoparticles.” Mat. Res. Soc. Symp. Proc. 789 (2004).
`Eychmüller, A. etal. "A quantum dot quantum well: CdS/HgS/CdS'.
`Chem. Phys. Lett. 208, pp. 59-62 (1993).
`Fendler, J.H. et al. “The Colloid Chemical Approach to
`Nanostructured Materials”. Adv. Mater. (1995) 7:607-632.
`Gao, M. etal. “Synthesis of PbS Nanoparticles in Polymer Matrices'.
`J. Chem. Soc. Commun. (1994) pp. 2779-2780.
`Gou et al., J. Am. Chem. Soc. (2006) 128:7222-7229.
`Gur et al., “Air stable all-inorganic nanocrystal Solar cells processed
`from solution.” Lawrence Berkeley Natl. Lab., Univ. of California,
`paper LBNL-58424 (2005).
`Gurin, Colloids Surf. A (1998) 142:35-40.
`Guzelian, A. etal. "Colloidal chemical synthesis and characterization
`of InAs nanocrystal quantum dots”, Appl. Phys. Lett. (1996) 69:
`1432-1434.
`Guzelian, A. et al., J. Phys. Chem. (1996) 100: 7212.
`Hagfeldt, A. et al. “Light-induced Redox Reactions in Nanocrystal
`line Systems”, Chem. Rev. (1995) 95: 49-68.
`Henglein, A. "Small-Particle Research: Physicochemical Properties
`of Extremely Small Colloidal Metal and Semiconductor Particles'.
`Chem Rev. (1989) 89: 1861-1873.
`Hirpo et al., “Synthesis of Mixed Copper-Indium Chalcogenolates.
`Single-Source Precursors for the Photovoltaic Materials CuInO2
`(Q=S. Se).” J. Am. Chem. Soc. (1993) 115:1597.
`Hu et al., Sol. State Comm. (2002) 121:493-496.
`International Search Report for PCT/GB2005/00 1611 mailed Sep. 8,
`2005 (5 pages).
`Jegier, J.A. et al. “Poly(imidogallane): Synthesis of a Crystalline 2-D
`Network Solid and Its Pyrolysis To Form Nanocrystalline Gallium
`Nitride in Supercritical Ammonia'. Chem. Mater. (1998) 10: 2041
`2043.
`Jiang et al., Inorg. Chem. (2000) 39:2964-2965.
`Kaelin et al., “CIS and CIGS layers from selenized nanoparticle
`precursors.” Thin Solid Films 431-432 (2003) pp. 58-62.
`Kapur et al., “Non-Vacuum processing of Culin-Ga, Se Solar cells
`on rigid and flexible Substrates using nanoparticle precursor inks.”
`Thin Solid Films 431-432 (2003) pp. 53-57.
`Kher, S. et al. “A Straightforward, New Method for the Synthesis of
`Nanocrystalline GaAs and GaP”, Chem. Mater. (1994) 6: 2056-2062.
`Kim et al., J. Mech. Sci. Tech. (2005) 19:2085-2090.
`Law et al., “Nanowire dye-sensitized solar cells.” Nature Mater.
`(2005) vol. 4 pp. 455-459.
`Li et al., Adv. Mat. (1999) 11:1456-1459.
`Lieber, C. et al. “Understanding and Manipulating Inorganic Mate
`rials with Scanning Probe Microscopes'. Angew. Chem. Int. Ed.
`Engl. (1996) 35: 687-704.
`Little
`et al., “Formation of Quantum-dot quantum-well
`heteronanostructures with large lattice mismatch: Zn/CdS/ZnS,” 114
`J. Chem. Phys. 4 (2001).
`Lu et al., Inorg. Chem. (2000) 39:1606-1607.
`LOver, T. etal. "Preparation of a novel CodSnanocluster material from
`a thiophenolate-capped CdS cluster by chemical removal of SPh
`ligands”. J. Mater. Chem. (1997) 7(4): 647-651.
`Malik et al., Adv. Mat., (1999) 11:1441-1444.
`Matijevic, E., “Monodispersed Colloids: Art and Science”, Langmuir
`(1986) 2:12-20.
`Matijevic, E. "Production of Mondispersed Colloidal Particles'.
`Ann. Rev. Mater. Sci. (1985) 15:483-5 18.
`Mekis, I. et al., “One-Pot Synthesis of Highly Luminescent CdSet.
`CdS Core-Shell Nanocrystals via Organometallic and "Greener”
`Chemical Approaches”, J. Phys. Chem. B. (2003) 107: 7454-7462.
`Mews et al., J. Phys. Chem. (1994) 98:934.
`Micic et al., “Synthesis and Characterization of InP, GaP, and GainP.
`Quantum Dots”, J. Phys. Chem. (1995) pp. 7754–7759.
`Milliron et al., “Electroactive Surfactant Designed to Mediate Elec
`tron Transfer between CdSe Nanocrystals and Organic Semicondic
`tors.” Adv. Materials (2003) 15, No. 1, pp. 58-61.
`Murray, C.B. et al., “Synthesis and Characterization of Nearly
`Monodisperse CoE (E=S, Se, Te) Semiconductor Nanocrystallites”.
`J. Am. Chem. Soc. (1993) 115 (19) pp. 8706-8715.
`Nairn et al., Nano Letters (2006) 6:1218-1223.
`
`Nazeeruddin et al., “Conversion of Light to Electricity by cis
`X2Bis(2.2"bipyridyl-4,4'-dicarboxylate)ruthenium(II)
`Charge
`Transfer Sensitizers (X=C1-, Br-, I-, CN-, and SCN-) on
`Nanocrystalline TiO, Electrodes,” J. Am. Chem. Soc. (1993)
`115:6382-6390.
`Nazeeruddin et al., “Engineering of Efficient Panchromatic Sensitiz
`ers for Nanocrystalline TiO2-Based Solar Cells,” J. Am. Chem. Soc.
`(2001) 123:1613-1624.
`O'Brien et al., “The Growth of Indium Selenide Thin Films from a
`Novel Asymmetric Dialkydiselenocarbamate.” 3 Chem. Vap. Depos.
`4, pp. 227 (1979).
`Olshaysky, M.A., et al. “Organometallic Synthesis of GaAs Crystal
`lites Exhibiting Quantum Confinement”. J. Am. Chem. Soc. (1990)
`1.12: 9438-9439.
`Olson et al., J. Phys. Chem. C. (2007) 111:16640-16645.
`Patents Act 1977: Search Report under Section 17 for Application
`No. GB0409877.8 dated Oct. 7, 2004 (2 pages).
`Patent Act 1977 Search Report under Section 17 for Application No.
`GB0522027.2 dated Jan. 27, 2006 (1 page).
`Patent Act 1977 Search Report under Section 17 for Application No.
`GB0606845.6 dated Sep. 14, 2006.
`Patent Act 1977 Search Report under Section 17 for Application No.
`GBO7190739.
`Patent Act 1977 Search Report under Section 17 for Application No.
`GBO7190754.
`Patent Act 1977 Search Report under Section 17 for Application No.
`GB0723539.3 dated Mar. 27, 2008 (1 page).
`Peng et al., J. Am. Chem. Soc. (2001) 123: 1389.
`Peng et al., “Kinetics of I-VI and III-V Colloidal Semiconductor
`Nanocrystal Growth: "Focusing” os Size Distributions”. J. Am.
`Chem. Soc., (1998) 129: 5343-5344.
`Penget al., “Shape control of CdSe nanocrystals', Nature, (2000) vol.
`404, No. 6773, pp. 59-61.
`Pradhan, N. et al. “Single-Precursor, One-Pot Versatile Synthesis
`under near Ambient Conditions of Tunable. Single and Dual Band
`Flourescing Metal Sulfide Nanoparticles'. J. Am. Chem. Soc. (2003)
`12.5: 2050-2051.
`Qi et al., “Efficient polymer-nanocrystal quantum-dot photodetec
`tors.” Appl. Physics Lett. 86 (2005) 093103-093103-3.
`Qu, L. et al. “Alternative Routes toward High Quality CdSe
`Nanocrystals', Nano Lett. (2001) vol. 1, No. 6, pp. 333-337.
`Robel et al., “Quantum Dot Solar Cells. Harvesting Light Energy
`with CdSe Nanocrystals Molecularly Linked to Mesoscopic TiO2
`Films,” J. Am. Chem. Soc. (2006) 128: 2385-2393.
`Salata, O.V. et al. “Uniform GaAs quantum dots in a polymer
`matrix”, Appl. Phys. Letters (1994) 65(2): 189-191.
`Sercel, P.C. et al. “Nanometer-scale GaAs clusters from
`organometallic percursors”, Appl. Phys. Letters (1992) 61: 696-698.
`Shulz et al., J. Elect. Mat. (1998) 27:433-437.
`Steigerwald, M.L. et al. “Semiconductor Crystallites: A Class of
`Large Molecules”. Acc. Chem. Res. (1990) 23: 183-188.
`Stroscio, J.A. et al. "Atomic and Molecular Manipulation with the
`Scanning Tunneling Microscope'. Science (1991), 254: 1319-1326.
`Trinidade et al., “A Single Source Spproach to the Synthesis of CdSe
`Nanocrystallites”. Advanced Materials, (1996) vol. 8, No. 2, pp.
`161-163.
`Vayssieres et al., “Highly Ordered SnO, Nanorod Arrays from Con
`trolled Aqueous Growth.” Angew. Chem. Int. Ed. (2004) 43: 3666
`3670.
`Wang Y. et al. “PbS in polymers, From molecules to bulk solids'. J.
`Chem. Phys. (1987) 87: 73.15-7322.
`Weller, H. "Colloidal Semiconductor Q-Particles: Chemistry in the
`Transition Region Between Solid State and Molecules”. Angew.
`Chem. Int. Ed. Engl. (1993) 32: 41-53.
`Weller, H. "Quantized Semiconductor Particles: A Novel State of
`Mater for Materials Science”, Adv. Mater. (1993) 5: 88-95.
`Wells, R.L. etal. “Synthesis of Nanocrystalline Indium Arsenide and
`Indium Phosphide from Indium(III) Halides and Tris
`(trimethylsilyl)pnicogens. Synthesis, Characterization, and Decom
`position Behavior of I-In-P(SiMe),”, Chem. Mater. (1995) 7: 793
`800.
`Xiao et al., J. Mater. Chem. (2001) 11:1417-1420.
`Yang et al., Crystal Growth & Design (2007) 12:2562-2567.
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 5 of 33 PageID #: 72
`
`US 7,867,557 B2
`Page 4
`
`Yu et al., “Polymer Photovoltaic Cells: Enhanced Efficiencies via a
`Network of Internal Donor-Acceptor Heterojunctions,” 270 Science
`5243 (1995), pp. 1789-1791.
`Zhong et al., Nanotechnology 18 (2007) 025602.
`Barron, “Group III Materials: New Phases and Nono-particles with
`Applications in Electronics and Optoelectronics.” Office of Naval
`Research Final Report (1999).
`Dabousi et al., “(CdSe)ZnS Core—Shell Quantum Dots: Synthesis
`and Characterization of a Size Series of Highly Luminescent
`Nanocrystallites.” Jrl. Phys. Chem...(1997) 101, pp. 9463-9475.
`Dehnen et al., “Chalcogen-Bridged Copper Clusters.” Eur, J. Inorg.
`Chem. (2002) pp. 279-317.
`Eisenmann et al., “New Phosphido-bridged Multinuclear Complexes
`of Ag and Zn. Zeitschrift fur anorganische und allgemeine Chemi
`(1995). (1 page—abstract).
`Huang et al., "Bio-Inspired Fabrication of Antireflection
`Nanostructures by Replicating Fly Eyes' Nanotechnology (2008)
`vol. 19.
`International Search Report for PCT/GB2006/003028 mailed Jan.
`22, 2007 (5 pages).
`International Search Report for PCT/GB2009/001928 mailed Dec. 8,
`2009 (3 pages).
`International Search Report for PCT/GB2009/002605 mailed Feb.
`22, 2010 (3 pages).
`Kim et al. “Engineering InASXP1-X/InP/ZnSe III-V Alloyed Core
`Shell Quantum Dots for the Near-Infrared” JACS Articles published
`on web Jul. 8, 2005.
`Materials Research Society Symposium Proceedings Quantum Dots,
`Nanoparticles and Nanowires, 2004, ISSN: 0272-9172.
`Miller et al., “From Giant Molecular Clusters and Precursors to
`Solid-state Structures.” Current Opinion in Solid State and Materials
`Science, 4 (Apr. 1999) pp. 141-153.
`Nielsch et al., “Uniform Nickel Deposition into Ordered Alumina
`Pores by Pulsed Electrodeposition”. Advanced Materials, 2000 vol.
`12, No. 8, pp. 582-586.
`Rao et al. (2004) “The Chemistry of Nanomaterials: Synthesis, Prop
`erties and Applications' p. 443.
`
`Search Report for GB0813273.0 searched Dec. 8, 2008 (1 page).
`Search Report for GB0814458.6 searched Dec. 5, 2008 (1 page).
`Search Report for GB0820101.4 searched Mar. 3, 2009 (1 page).
`Search Report for GB0821122.9 searched Mar. 19, 2009 (2 pages).
`Trinidade et al., “Nanocrystalline Seminconductors: Synthesis, Prop
`erties, and Perspectives”. Chemistry of Materials, (2001) vol. 13, No.
`11, pp. 3843-3858.
`Vittal, “The chemistry of inorganic and organometallic compounds
`with adameantane-like structures.” Polyhedron, vol. 15, No. 10, pp.
`1585-1642 (1996).
`Xie et al. “Synthesis and Characterization of Highly Luminescent
`CdSe-Core CdS/ZnO.5CdO.5S/ZnS Multishell Nanocrystals” JACS
`Articles published on web Apr. 29, 2005.
`Zhong et al., “Composition-Tunable ZnCu-XSe Nanocrytals with
`High Luminescence and Stability”, Jrl Amer. Chem. Soc. (2003).
`Foneberov et al., (2005) “Photoluminescence of tetrahedral quan
`tum-dot quantum wells' Physica E, 26:63-66.
`Cao, (2005) “Effect of Layer Thickness on the Luminescence Prop
`erties of ZnS/CdS/ZnSquantum dot quantum well'. J. of Colloid and
`Interface Science 284:516-520.
`Harrison et al. (2000) “Wet Chemical Synthesis on Spectroscopic
`Study of CdHgTe Nanocrystals with Strong Near-Infrared Lumines
`cence” Mat. Sci and Eng.B69-70:355-360.
`Sheng et al. (2006) "In-Situ Encapsulation of Quantum Dots into
`Polymer Microsphers”. Langmuir 22(8):3782-3790.
`Timoshkin, “Group 13 imido metallanes and their heavier analogs
`RMYRIn (M=AI, Ga. In;Y=N. P. As, Sb).” Coordination Chemis
`try Reviews (2005).
`W. Peter Wuelfing et al: “Supporting Information for Nanometer
`Gold Clusters Protected by Surface Bound Monolayers of Thiolated
`Poly (ethylene glycol) Polymer Electrolyte” Journal of the American
`Chemical Society (XP002529160), (1998).
`International Search Report for PCT/GB2009/000510 mailed Jul. 6,
`2010 (16 pages).
`* cited by examiner
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 6 of 33 PageID #: 73
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 1 of 12
`
`US 7,867,557 B2
`
`Figure l
`
`
`
`(a)
`
`(b)
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 7 of 33 PageID #: 74
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 2 of 12
`
`US 7,867,557 B2
`
`Figure 2
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 8 of 33 PageID #: 75
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 3 of 12
`
`US 7,867,557 B2
`
`Figure 3
`
`
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 9 of 33 PageID #: 76
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 4 of 12
`
`US 7,867,557 B2
`
`Figure 4
`
`s
`
`(b)
`
`
`
`250
`
`300
`
`450
`400
`350
`Wavelength inm
`
`500
`
`550
`
`25
`
`30
`
`35
`
`AO
`
`45
`
`50
`
`55
`
`60
`
`2 - the ta degree)
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 10 of 33 PageID #: 77
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 5 of 12
`
`US 7,867,557 B2
`
`Figure 5
`
`s
`
`
`
`
`
`emission
`
`absorption
`
`3OO
`
`4OO
`
`500
`Wavelength/nm
`
`6OO
`
`700
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 11 of 33 PageID #: 78
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 6 of 12
`
`US 7,867,557 B2
`
`Figure 6
`
`
`
`s
`
`emission
`
`absorption
`
`300
`
`500
`400
`Wavelength/nm
`
`6OO
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 12 of 33 PageID #: 79
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 7 of 12
`
`US 7,867,557 B2
`
`Figure 7
`
`emission
`
`absorption
`
`2.
`
`1.O
`
`0.8
`
`0.6
`
`0.4
`
`0.2
`
`
`
`250
`
`300
`
`350
`400
`450
`Wavelength (nm)
`
`500
`
`550
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 13 of 33 PageID #: 80
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 8 of 12
`
`US 7,867,557 B2
`
`Figure 8
`
`
`
`o.O.
`400
`
`450
`5CO
`Wavelength (nm)
`
`550
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 14 of 33 PageID #: 81
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 9 of 12
`
`US 7,867,557 B2
`
`absorption
`
`1 +
`
`-absorption
`
`O
`3OO
`
`350
`
`O)
`
`55)
`
`OO
`
`SOC)
`
`45)
`wavelength (nm)
`Figure 9A
`
`emission
`
`f
`| f
`
`3000
`
`2000 +
`
`1000
`
`-emission
`
`I
`30
`
`30
`
`1)
`
`30
`
`51.
`
`530
`
`55
`
`490
`
`d
`50
`Wavelength (nm)
`Figure 9B
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 15 of 33 PageID #: 82
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 10 of 12
`
`US 7,867,557 B2
`
`Absorption
`
`2.5 T.
`
`2
`
`1.5 +
`
`E 1+
`
`0.5 +
`
`O
`3O
`
`350
`
`OO
`
`OO
`
`SO
`
`550
`
`500
`O
`Wavelength (m)
`Figure 10A
`
`SOOOOOO I
`
`OOOOOO +
`
`6OOOOOO +
`
`5OOOOOO +
`40000+
`30000+
`
`OOOOOO +
`
`1OOOOOO -
`
`O
`45)
`
`emission
`
`f
`|
`
`|
`f
`
`550
`
`850
`Wavelength (nm)
`Figure 10B
`
`750
`
`--Absorption
`
`--- mission
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 16 of 33 PageID #: 83
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 11 of 12
`
`US 7,867,557 B2
`
`Absorption
`
`Absorption
`
`Emission
`
`350
`
`400
`
`5OO
`450
`Wvel ength (nm)
`
`550
`
`600
`
`650
`
`Figure 11A
`
`mission
`
`50OOOO --
`
`45OOOO --
`
`400000 --
`
`
`
`3500 OO
`
`3000 00
`
`1500 OO
`
`100000 --
`
`400
`
`450
`
`500
`
`600
`550
`Wive ength (nm)
`
`650
`
`700
`
`750
`
`Figure 11B
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 17 of 33 PageID #: 84
`
`U.S. Patent
`
`Jan. 11, 2011
`
`Sheet 12 of 12
`
`US 7,867,557 B2
`
`Figure 12
`
`
`
`n
`
`350
`
`AOO
`A50
`Wavelength (nm)
`
`5OO
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 18 of 33 PageID #: 85
`
`US 7,867,557 B2
`
`1.
`NANOPARTICLES
`
`This application is the U.S. national stage application of
`International (PCT) Patent Application Serial No. PCT/
`GB2006/003028, filed Aug. 14, 2006, which claims the ben
`efit of GBApplication No. 0516598.0, filed Aug. 12, 2005.
`The entire disclosures of these two applications are hereby
`incorporated by reference as if set forth at length herein in
`their entirety.
`The present invention relates to nanoparticles and methods
`for preparing nanoparticles.
`
`BACKGROUND
`
`10
`
`15
`
`25
`
`30
`
`35
`
`45
`
`There has been substantial interest in the preparation and
`characterisation of compound semiconductors comprising of
`particles with dimensions in the order of 2-100 nm, often
`referred to as quantum dots and nanocrystals mainly because
`of their optical, electronic or chemical properties. These inter
`ests 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 labelling, Solar cells, catalysis, biological imaging,
`light-emitting diodes amongst many new and emerging appli
`cations.
`Although some earlier examples appear in the literature,
`recently methods have been developed from reproducible
`“bottom up' techniques, whereby particles are prepared
`atom-by-atom, i.e. from molecules to clusters to particles
`using “wet chemical procedures. Rather from “top down”
`techniques involving the milling of Solids to finer and finer
`powders.
`To-date the most studied and prepared of nano-Semicon
`ductor materials have been the chalcogenides II-VI materials
`namely ZnS, ZnSe, CdS, CdSe, CdTe; most noticeably CdSe
`due to its tunability over the visible region of the spectrum.
`Semiconductor nanoparticles are of academic and commer
`40
`cial interest due to their differing and unique properties from
`those of the same material, but in the macro crystalline bulk
`form. Two fundamental factors, both related to the size of the
`individual nanoparticle, are responsible for these unique
`properties.
`The first is the large Surface to Volume ratio; as a particle
`becomes Smaller, the ratio of the number of surface atoms to
`those in the interior increases. This leads to the surface prop
`erties playing an important role in the overall properties of the
`material.
`The second factor is that, with semiconductor nanopar
`ticles, there is a change in the electronic properties of the
`material with size, moreover, the band gap gradually becom
`ing larger because of quantum confinement effects as the size
`of the particles decreases. This effect is a consequence of the
`confinement of an electron in a box giving rise to discrete
`energy levels similar to those observed in atoms and mol
`ecules, rather than a continuous band as in the corresponding
`bulk semiconductor material. For a semiconductor nanopar
`ticle, because of the physical parameters, the “electron and
`hole', produced by the absorption of electromagnetic radia
`tion, a photon, with energy greater then the first excitonic
`transition, are closer together than in the corresponding mac
`rocrystalline material, so that the Coulombic interaction can
`not be neglected. This leads to a narrow bandwidth emission,
`which is dependent upon the particle size and composition.
`Thus, quantum dots have higher kinetic energy than the cor
`
`50
`
`55
`
`60
`
`65
`
`2
`responding macrocrystalline material and consequently the
`first excitonic transition (band gap) increases in energy with
`decreasing particle diameter.
`The coordination about the final inorganic Surface atoms in
`any core, core-shell or core-multi shell nanoparticles is
`incomplete, with highly reactive "dangling 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
`sis.
`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 dan
`gling bonds situated on the nanoparticle Surface which lead to
`non-radiative electron-hole recombinations.
`One method to eliminate defects and dangling 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 centres.
`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.
`Quantum Dot-Quantum Wells
`Another approach which can further enhance the efficien
`cies of semiconductor nanoparticles is to prepare a core-multi
`shell structure where the “electron-hole' pair are completely
`confined to a single shell Such as a quantum dot-quantum well
`structure. Here, the core is of a wide bandgap material, fol
`lowed 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 a few monolayer of HgS.
`The resulting structures exhibited clear confinement of pho
`toexcited carriers in the Hg.S. Other known Quantum dot
`quantum well (QDQW) structures include—ZnS/CdSe/ZnS,
`CdS/CdSe/CdS and ZnS/CdS/ZnS.
`Colloidally grown QD-QW nanoparticles are relatively
`new. The first and hence most studied systems were of CdS/
`HgS/CdS grown by the substitution of cadmium for mercury
`on the core surface to deposit one monolayer of HgS. A wet
`chemical synthetic method for the preparation of spherical
`CdS/HgS/CdS quantum wells was presented with a study of
`their unique optical properties. The CdS/HgS/CdS particles
`emitted a red band-edge emission originating from the HgS
`
`
`
`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 19 of 33 PageID #: 86
`
`US 7,867,557 B2
`
`10
`
`15
`
`4
`(to both chemical environment and photo effects) can be
`produced. It will be appreciated that while the first aspect of
`the present invention defines a method for producing nano
`particles having a core, and first and second layers, the
`method forming the first aspect of the present invention may
`be used to provide nanoparticles comprising any desirable
`number of additional layers (e.g. third, fourth and fifth layers
`provides on the second, third and fourth layers respectively)
`of pure or doped semiconductor materials, materials having a
`ternary or quaternary structure, alloyed materials, metallic
`materials or non-metallic materials. The invention addresses
`a number of problems, which include the difficulty of pro
`ducing high efficiency blue emitting dots.
`The nanoparticle core, first and second semiconductor
`materials may each possess any desirable number of ions of
`any desirable element from the periodic table. Each of the
`core, first and second semiconductor material is preferably
`separately selected from the group consisting of a semicon
`ductor material incorporating ions from groups 12 and 15 of
`the periodic table, a semiconductor material incorporating
`ions from groups 13 and 15 of the periodic table, a semicon
`ductor material incorporating ions from groups 12 and