Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 1 of 29 PageID #: 39
`
`Exhibit 2
`
`

`

`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 2 of 29 PageID #: 40
`
`USOO78O3423B2
`
`(12) United States Patent
`O'Brien et al.
`
`(10) Patent No.:
`(45) Date of Patent:
`
`US 7.803,423 B2
`Sep. 28, 2010
`
`(54) PREPARATION OF NANOPARTICLE
`MATERLALS
`
`(75) Inventors: Paul O'Brien, High Peak (GB); Nigel
`Pickett, East Croydon (GB)
`(73) Assignee: Nanoco Technologies Limited,
`Manchester (GB)
`
`(*) Notice:
`
`Subject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 1003 days.
`
`(21)
`
`Appl. No.:
`
`11/579,050
`
`PCT Fled:
`
`(22)
`(86). PCT No.:
`S371 (c)(1),
`(2), (4) Date:
`
`Apr. 27, 2005
`
`PCT/GB2OOS/OO1611
`
`Oct. 27, 2006
`
`(87)
`
`PCT Pub. No.: WO2OOS/106082
`
`PCT Pub. Date: Nov. 10, 2005
`
`(65)
`
`Prior Publication Data
`US 2007/O2O2333 A1
`Aug. 30, 2007
`
`Foreign Application Priority Data
`(30)
`Apr. 30, 2004
`(GB) ................................. O4O9877.8
`
`(51) Int. Cl.
`(2006.01)
`B82B 3/00
`(2006.01)
`COIB 700
`(2006.01)
`C30B 700
`(2006.01)
`C30B 7/4
`U.S. Cl. ............... 427/213.34; 427/212; 427/213.3:
`427/213.31; 427/214; 427/215; 428/402;
`428/403
`Field of Classification Search .................. 427/212
`See application file for complete search history.
`
`(52)
`
`(58)
`
`(56)
`
`References Cited
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`Chemistry of Materials, (2002).*
`(Continued)
`Primary Examiner Michael Cleveland
`Assistant Examiner—Lisha Jiang
`(74) Attorney, Agent, or Firm Goodwin Procter LLP
`(57)
`ABSTRACT
`
`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.
`
`25 Claims, 14 Drawing Sheets
`
`
`
`(c)
`
`Diagram of a) core particle, b) core-shell particle, c) core-multishell organic capped particle
`
`

`

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`Sep. 28, 2010
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 9 of 29 PageID #: 47
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 13 of 29 PageID #: 51
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 14 of 29 PageID #: 52
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`U.S. Patent
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`Sep. 28, 2010
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`Sheet 10 of 14
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`US 7,803.423 B2
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 15 of 29 PageID #: 53
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`U.S. Patent
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`Sep. 28, 2010
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`Sheet 11 of 14
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`US 7.803.423 B2
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 16 of 29 PageID #: 54
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 17 of 29 PageID #: 55
`Case 2:20-cv-OOO38-JRG Document 1-3 Filed 02/14/20 Page 17 of 29 PageID #: 55
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`US. Patent
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`Sep. 28, 2010
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`Sheet 13 of 14
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`US 7,803,423 B2
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 18 of 29 PageID #: 56
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`U.S. Patent
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`Sep. 28, 2010
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`Sheet 14 of 14
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`US 7,803.423 B2
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`Case 2:20-cv-00038-JRG Document 1-3 Filed 02/14/20 Page 19 of 29 PageID #: 57
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`1.
`PREPARATION OF NANOPARTICLE
`MATERALS
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`This application is the U.S. national stage application of
`International (PCT) Patent Application Serial No. PCT/
`GB2005/001611, filed Apr. 27, 2005, which claims the ben
`efit of GB Application No. 0409877.8, filed Apr. 30, 2004.
`The entire disclosures of these two applications are hereby
`incorporated by reference as if set forth at length herein in
`their entirety.
`There has been substantial interest in the preparation and
`characterisation, 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
`studies have occurred mainly due to their size-tuneable elec
`tronic, 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 biological labelling, Solar cells, catalysis, biologi
`cal imaging, light-emitting diodes amongst many new and
`emerging applications.
`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 semiconductor
`materials have been the chalcogenides II-VI materials namely
`ZnS, ZnSe, CdS, CdSe, CdTe; most noticeably CdSe due to
`its tuneability over the visible region of the spectrum. As
`mentioned semiconductor nanoparticles are of academic and
`commercial interest due to their differing and unique proper
`ties from those of the same material, but in the macro crys
`tallinebulk form. Two fundamental factors, both related to the
`size of the individual nanoparticle, are responsible for their
`unique properties. The first is the large Surface to Volume
`ratio; as a particle becomes smaller, the ratio of the number of
`40
`Surface atoms to those in the interior increases. This leads to
`the Surface properties playing an important role in the overall
`properties of the material. The second factor is that, with
`semiconductor nanoparticles, there is a change in the elec
`tronic properties of the material with size, moreover, the band
`gap gradually becoming larger because of quantum confine
`ment 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 molecules, rather than a continuous band as in
`the corresponding bulk semiconductor material. Thus, for a
`semiconductor nanoparticle, because of the physical param
`eters, the “electron and hole', produced by the absorption of
`electromagnetic radiation, a photon, with energy greater then
`the first excitonic transition, are closer together than in the
`corresponding macrocrystalline material, so that the Coulom
`bic interaction cannot 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 corresponding macrocrystalline 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
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`non-radiative electron-hole recombinations. 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 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.
`However, the growth of more than a few monolayers 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 are 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.
`Over the past six years the important issues have concerned
`the synthesis of high quality semiconductor nanoparticles in
`terms of uniform shape, size distribution and quantum effi
`ciencies. This has lead to a number of methods that can
`routinely produce semiconductor nanoparticles, with mono
`dispersity of <5% with quantum yields >50%. Most of these
`methods are based on the original “nucleation and growth
`method described by Murray, Norris and Bawendi," but use
`other precursors that the organometallic ones used. Murray et
`al originally used organometallic Solutions of metal-alkyls
`(RM) M=Cd, Zn, Te: R=Me, Et and tri-n-octylphosphine
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`ticle growth. This is achieved by rapid injection of one or both
`precursors into a hot coordinating solvent (containing the
`other precursor if otherwise not present) which initiates par
`ticles nucleation, however, the sudden addition of the cooler
`Solution upon injection Subsequently lowers the reaction tem
`perature (the volume of solution added is about/3 of the total
`Solution) and inhibits further nucleation maintaining a narrow
`nanoparticle size distribution. Particle growth being a Surface
`catalyzes process or via Ostwald ripening, depending on the
`precursor's used, continues at the lower temperature and
`thus nucleation and growth are separated. This method works
`well for small scale synthesis where one solution can be
`added rapidly to another while keeping an homogenous tem
`perature throughout the reaction. However, on larger prepara
`tive scale whereby large Volumes of Solution are required to
`be rapidly injected into one another a temperature differential
`can occur within the reaction which can Subsequently lead to
`a large particle size distribution.
`Preparation from single-source molecular clusters,
`Cooney and co-workers used the cluster S.Cdo (SPh)
`MeNHL to produce nanoparticles of CdS via the oxidation
`of surface-capping SPh ligands by iodine. This route fol
`lowed the fragmentation of the majority of clusters into ions
`which were consumed by the remaining S.Cdo (SPh).It
`clusters which Subsequently grow into nanoparticles of
`CdS. Strouse and co-workers used a similar synthetic
`approach but employed thermolysis (lyothermal) rather than
`a chemical agent to initiate particle growth. Moreover, the
`single-source precursors IMoSea (SPh) X, X-Li' or
`(CH)NH", M-Cd or Zn were thermolysised whereby frag
`mentation of some clusters occurs followed by growth of
`other from scavenging of the free M and Se ions or simply
`from clusters aggregating to form larger clusters and then
`Small nanoparticles which Subsequently continue to grow
`into larger particles.
`According to the present invention there is provided a
`method of producing nanoparticles comprising effecting con
`version of a nanoparticle precursor composition to the mate
`rial of the nanoparticles, said precursor composition compris
`ing 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, wherein said conver
`sion is effected in the presence of a molecular cluster com
`pound under conditions permitting seeding and growth of the
`nanoparticles.
`The present invention relates to a method of producing
`nanoparticles of any desirable form and allows ready produc
`tion of a monodisperse population of such particles which are
`consequently of a high purity. It is envisaged that the inven
`tion is suitable for producing nanoparticles of any particular
`size, shape or chemical composition. A nanoparticle may
`have a size falling within the range 2-100 nm. A sub-class of
`nanoparticles of particular interest is that relating to com
`pound semiconductor particles, also known as quantum dots
`or nanocrystals.
`An important feature of the invention is that conversion of
`the precursor composition (comprising separate first and sec
`ond precursor species) to the nanoparticles is effected in the
`presence of a molecular cluster compound (which will be
`other than the first or second precursor species). Without
`wishing to be bound by any particular theory, one possible
`mechanism by which nanoparticle growth may take place is
`that each identical molecule of the cluster compound acts as
`a seed or nucleation point upon which nanoparticle growth
`can be initiated. In this way, nanoparticle nucleation is not
`necessary to initiate nanoparticle growth because Suitable
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`sulfide/selenide (TOPS/Se) dissolved in tri-n-octylphosphine
`(TOP). These precursor solutions are injected into hot tri-n-
`octylphosphine oxide (TOPO) in the temperature range 120
`400° C. depending on the material being produced. This
`produces TOPO coated/capped semiconductor nanoparticles
`of II-VI material. The size of the particles is controlled by the
`temperature, concentration of precursor used and length of
`time at which the synthesis is undertaken, with larger par
`ticles being obtained at higher temperatures, higher precursor
`concentrations and prolonged reaction times. This organome
`tallic route has advantages over other synthetic methods,
`including near monodispersity <5% and high particle crys
`tallinity. As mentioned, many variations of this method have
`now appeared in the literature which routinely give high
`quality core and core-shell nanoparticles with monodispesity
`of <5% and quantum yield >50% (for core-shell particles of
`as-prepared solutions), with many methods displaying a high
`degree of size' and shape' control.
`Recently attention has focused on the use of “greener”
`precursors which are less exotic and less expensive but not
`necessary more environmentally friendly. Some of these new
`precursors include the oxides, CdO;'
`carbonates
`MCOM-Cd, Zn; acetates M(CHCO),M-Cd, Zn and
`acetylacetanates CH-COCH=C(O)CHM-Cd, Zn;
`amongst other.'
`f(The use of the term “gree