throbber
Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 1 of 33 PageID #: 68
`
`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
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`
`(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
`
`

`

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`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
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`Figure l
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`(a)
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`(b)
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`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 7 of 33 PageID #: 74
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`Figure 2
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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 8 of 33 PageID #: 75
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`Figure 3
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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 9 of 33 PageID #: 76
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`Figure 4
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`s
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`(b)
`
`
`
`250
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`300
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`450
`400
`350
`Wavelength inm
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`500
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`550
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`25
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`30
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`35
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`AO
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`45
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`50
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`55
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`2 - the ta degree)
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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 10 of 33 PageID #: 77
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`Figure 5
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`s
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`
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`
`
`emission
`
`absorption
`
`3OO
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`4OO
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`500
`Wavelength/nm
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`6OO
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`700
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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 11 of 33 PageID #: 78
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`Figure 6
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`
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`s
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`emission
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`absorption
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`300
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`500
`400
`Wavelength/nm
`
`6OO
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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 12 of 33 PageID #: 79
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`US 7,867,557 B2
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`Figure 7
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`emission
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`absorption
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`2.
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`1.O
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`0.8
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`0.6
`
`0.4
`
`0.2
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`
`
`250
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`300
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`350
`400
`450
`Wavelength (nm)
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`500
`
`550
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`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 13 of 33 PageID #: 80
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`US 7,867,557 B2
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`Figure 8
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`
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`o.O.
`400
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`450
`5CO
`Wavelength (nm)
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`550
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`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 14 of 33 PageID #: 81
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`US 7,867,557 B2
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`absorption
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`1 +
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`-absorption
`
`O
`3OO
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`350
`
`O)
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`55)
`
`OO
`
`SOC)
`
`45)
`wavelength (nm)
`Figure 9A
`
`emission
`
`f
`| f
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`3000
`
`2000 +
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`1000
`
`-emission
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`I
`30
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`30
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`1)
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`30
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`51.
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`530
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`55
`
`490
`
`d
`50
`Wavelength (nm)
`Figure 9B
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`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 15 of 33 PageID #: 82
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`Absorption
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`2.5 T.
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`2
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`1.5 +
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`E 1+
`
`0.5 +
`
`O
`3O
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`350
`
`OO
`
`OO
`
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`
`550
`
`500
`O
`Wavelength (m)
`Figure 10A
`
`SOOOOOO I
`
`OOOOOO +
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`
`5OOOOOO +
`40000+
`30000+
`
`OOOOOO +
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`
`O
`45)
`
`emission
`
`f
`|
`
`|
`f
`
`550
`
`850
`Wavelength (nm)
`Figure 10B
`
`750
`
`--Absorption
`
`--- mission
`
`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 16 of 33 PageID #: 83
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`Sheet 11 of 12
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`US 7,867,557 B2
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`Absorption
`
`Absorption
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`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
`
`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 17 of 33 PageID #: 84
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`Sheet 12 of 12
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`US 7,867,557 B2
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`Figure 12
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`
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`n
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`350
`
`AOO
`A50
`Wavelength (nm)
`
`5OO
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`

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`Case 2:20-cv-00038-JRG Document 1-4 Filed 02/14/20 Page 18 of 33 PageID #: 85
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`US 7,867,557 B2
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`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
`
`

`

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`10
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`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

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