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US20080012001A1 - Shaped articles comprising semiconductor nanocrystals and methods of making and using same - Google Patents

Shaped articles comprising semiconductor nanocrystals and methods of making and using same Download PDF

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Publication number
US20080012001A1
US20080012001A1 US11/484,785 US48478506A US2008012001A1 US 20080012001 A1 US20080012001 A1 US 20080012001A1 US 48478506 A US48478506 A US 48478506A US 2008012001 A1 US2008012001 A1 US 2008012001A1
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Prior art keywords
matrix material
solution
semiconductor nanocrystal
semiconductor
shaped article
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US11/484,785
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Jennifer Gillies
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Evident Technologies Inc
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Evident Technologies Inc
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Priority to US11/484,785 priority Critical patent/US20080012001A1/en
Assigned to EVIDENT TECHNOLOGIES reassignment EVIDENT TECHNOLOGIES ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GILLIES, JENNIFER
Priority to PCT/US2007/015851 priority patent/WO2008100276A2/fr
Publication of US20080012001A1 publication Critical patent/US20080012001A1/en
Priority to US12/350,615 priority patent/US8168457B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
    • C09K11/562—Chalcogenides
    • C09K11/565—Chalcogenides with zinc cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/661—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/88—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing selenium, tellurium or unspecified chalcogen elements
    • C09K11/881—Chalcogenides
    • C09K11/883—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/01—Manufacture or treatment
    • H10H20/036—Manufacture or treatment of packages
    • H10H20/0361—Manufacture or treatment of packages of wavelength conversion means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10H—INORGANIC LIGHT-EMITTING SEMICONDUCTOR DEVICES HAVING POTENTIAL BARRIERS
    • H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
    • H10H20/80—Constructional details
    • H10H20/85—Packages
    • H10H20/851—Wavelength conversion means
    • H10H20/8511—Wavelength conversion means characterised by their material, e.g. binder
    • H10H20/8512—Wavelength conversion materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/773—Nanoparticle, i.e. structure having three dimensions of 100 nm or less
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S977/00—Nanotechnology
    • Y10S977/70—Nanostructure
    • Y10S977/832—Nanostructure having specified property, e.g. lattice-constant, thermal expansion coefficient
    • Y10S977/834—Optical properties of nanomaterial, e.g. specified transparency, opacity, or index of refraction

Definitions

  • the present invention relates generally to shaped articles comprising semiconductor nanocrystals and methods of making and using the same.
  • Semiconductor nanocrystals are typically tiny crystals of II-VI, III-V, IV-VI materials that have a diameter between 1 nanometer (nm) and 20 nm. In the strong confinement limit, the physical diameter of the nanocrystal is smaller than the bulk excitation Bohr radius causing quantum confinement effects to predominate. In this regime, the nanocrystal is a 0-dimensional system that has both quantized density and energy of electronic states where the actual energy and energy differences between electronic states are a function of both the nanocrystal composition and physical size. Larger nanocrystals have more closely spaced energy states and smaller nanocrystals have the reverse. Because interaction of light and matter is determined by the density and energy of electronic states, many of the optical and electric properties of nanocrystals can be tuned or altered simply by changing the nanocrystal geometry (i.e. physical size).
  • Single nanocrystals or monodisperse populations of nanocrystals exhibit unique optical properties that are size tunable. Both the onset of absorption and the photoluminescent wavelength are a function of nanocrystal size and composition. The nanocrystals will absorb all wavelengths shorter than the absorption onset, however, photoluminescence will always occur at the absorption onset. The bandwidth of the photoluminescent spectra is due to both homogeneous and inhomogeneous broadening mechanisms. Homogeneous mechanisms include temperature dependent Doppler broadening and broadening due to the Heisenburg uncertainty principle, while inhomogeneous broadening is due to the size distribution of the nanocrystals. The narrower the size distribution of the nanocrystals, the narrower the full-width half max (FWHM) of the resultant photoluminescent spectra.
  • FWHM full-width half max
  • Quantum yield i.e. the percent of absorbed photons that are reemitted as photons
  • Photoexcited charge carriers will emit light upon direct recombination but will give up the excitation energy as heat if photon or defect mediated recombination paths are prevalent.
  • the nanocrystal may have a large surface area to volume ratio, dislocations present on the surface or adsorbed surface molecules having a significant potential difference from the nanocrystal itself will tend to trap excited state carriers and prevent radioactive recombination and thus reduce quantum yield. It has been shown that quantum yield can be increased by removing surface defects and separating adsorbed surface molecules from the nanocrystal by adding a shell of a semiconductor with a wider bulk bandgap than that of the core semiconductor.
  • the colloids demonstrated quantum confinement effects including the observation of size dependent absorption maxima (first exciton peaks) as well as size dependent fluorescent spectra.
  • the colloids were prepared by bubbling a sulphur containing gas (H 2 S) through an alkaline solution containing dissolved cadmium ions. The size and resultant color (of the fluorescence) of the resultant nanocrystals were dependent upon the pH of the solution.
  • the colloids were further modified or “activated” by the addition of cadmium hydroxide to the solution that coated the suspended nanocrystals.
  • the resultant core-shell nanocrystals demonstrated that the quantum yield of the photoluminescence was increased from under 1% to well over 50% with a FWHM of the photoluminescent spectra under 50 nm for some of the preparations.
  • Kortan and Brus developed a method for creating CdSe coated zinc sulphide (ZnS) nanocrystals and the opposite, zinc sulphide coated cadmium selenide nanocrystals.
  • ZnS zinc sulphide
  • the preparation grew ZnS on CdSe “seeds” using a organometallic precursor-based reverse micelle technique and kept them in solution via an organic capping layer (thiol phenol).
  • the CdSe core nanocrystals had diameters between 3.5 and 4 nm and demonstrated quantum confinement effects including observable exciton absorption peaks and blue shifted photoluminescence.
  • CdSe cores were coated by a 0.4 nm layer of ZnS.
  • the photoluminescence spectra of the resultant core-shell nanocrystals indicates a peak fluorescence at 530 nm with an approximate 40-45 nm FWHM.
  • the synthesis involved a homogeneous nucleation step followed by a growth step.
  • the nucleation step is initiated by the injection of an organometallic cadmium precursor (dimethyl cadmium) with a selenium precursor (TOPSe-TriOctylPhosphine Selenium) into a heated bath containing coordinating ligands (TOPO-TriOctylPhosphineOxide).
  • the precursors disassociate in the solvent, causing the cadmium and selenium to combine to form a growing nanocrystal.
  • the TOPO coordinates with the nanocrystal to moderate and control the growth.
  • the resultant nanocrystal solution showed an approximate 10% size distribution, however, by titrating the solution with methanol the larger nanocrystals could be selectively precipitated from the solution thereby reducing the overall size distribution.
  • the resultant nanocrystals in solution were monodisperse (capable of reaching a 5% size distribution) but were slightly prolate (i.e. nonspherical having an aspect ratio between 1.1 and 1.3).
  • the photoluminescence spectra show a FWHM of approximately 30-35 nm and a quantum yield of approximately 9.6%.
  • the nanocrystals were size tunable from 1.8 nm to 6.7 nm in diameter and had an exciton peak position ranging from 1.9-2.5 eV (corresponding to 635-496 nm wavelength).
  • TOPO was used as the coordinating ligand.
  • Hines and Guyot-Sionest developed a method for synthesizing a ZnS shell around a CdSe core nanocrystal.
  • Hines et al. “Synthesis and Characterization of strongly Luminescing ZnS capped CdSe Nanocrystals”; J. Phys. Chem., 100:468-471 (1996), which is incorporated by reference herein).
  • the CdSe cores having a monodisperse distribution between 2.7 nm and 3.0 nm (i.e. 5% size distribution with average nanocrystal diameter being 2.85 nm), were produced using the Katari and Alivisatos variation of the Murray synthesis.
  • the photoluminescence spectra of the core shows a FWHM of approximately 30 nm with a peak at approximately 540 nm.
  • the core CdSe nanocrystals were separated, purified, and resuspended in a TOPO solvent. The solution was heated and injected with zinc and sulphur precursors (dimethyl zinc and (TMS) 2 S) to form a ZnS shell around the CdSe cores. The resultant shells were 0.6 ⁇ 0.3 nm thick, corresponding to 1-3 monolayers.
  • the photoluminescence of the core-shell nanocrystals had a peak at 545 nm, FWHM of 40 nm, and a quantum yield of 50%.
  • the present invention provides a shaped article comprising a plurality of semiconductor nanocrystals.
  • the present invention provides a method of manufacturing a shaped article. The method includes preparing a pre-form material by adding a plurality of semiconductor nanocrystals to a first material and forming the pre-form material into a shape article.
  • FIG. 1 is a schematic illustration of a semiconductor nanocrystal according to an embodiment of the present invention.
  • FIG. 2 is an image of a shaped article according to an embodiment of the present invention.
  • FIG. 3 is a flow chart illustrating an exemplary method of making a shaped article according to an embodiment of the present invention.
  • the present invention provides a shaped article comprising a plurality of semiconductor nanocrystals.
  • semiconductor nanocrystals are spherical nanoscale materials (although oblate and oblique spheroids can be grown as well as rods and other shapes) having a diameter between 1 nm and 20 nm and typically but not exclusively comprising II-VI, III-V, and IV-VI binary semiconductors. Referring to FIG.
  • a semiconductor nanocrystal 20 in an embodiment, includes a core 21 of a first semiconductor that has a selected composition and diameter that enables light emission at a predetermined wavelength and optionally one or more shells 22 of a second semiconductor preferably having a bulk bandgap greater than that of the first semiconductor of core 21 .
  • Optional one or more shells 22 is preferably between 0.1 nm and 10 nm thick.
  • Non-limiting examples of semiconductor materials that may comprise core 21 include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe (II-VI materials), PbS, PbSe, PbTe (IV-VI materials), AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb (III-V materials) and alloys and combinations thereof.
  • Non-limiting examples of materials that may comprise the one or more shells 22 include CdSe, CdS, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, InP, InAs, InSb, InN, GaN, GaP, GaAs, GaSb, PbSe, PbS, PbTe and alloys and combinations thereof.
  • a shaped article is an article that can be prepared by a molding technique.
  • a shaped article of the present invention can be manufactured by adding a plurality of semiconductor nanocrystals to a first material to make a pre-form material.
  • the pre-form material is then formed into a shaped article.
  • the pre-formed material can be formed into a shaped article by any suitable thermal and/or mechanical process known in the art, such as molding the pre-form material into a shaped article.
  • Non-limiting examples of molding processes include injection molding, extrusion molding, blow molding, compression molding, contact molding, impression molding, press molding, and resin transfer molding.
  • the pre-form material is formed into a shaped article by injection molding.
  • FIG. 2 depicts a shaped article made according to an embodiment of the present invention.
  • the shaped article when illuminated emits light from the semiconductor nanocrystals contained in the shaped article.
  • FIG. 3 depicts a flow chart illustrating an exemplary method of making a shaped article comprising semiconductor nanocrystals according to an embodiment of the present invention.
  • a plurality of semiconductor nanocrystals is obtained, for example, by preparing a plurality of semiconductor nanocrystals using any known method or purchasing a plurality of semiconductor nanocrystals (Evident Technologies, Troy, N.Y.).
  • the plurality of semiconductor nanocrystals can be a plurality of the same semiconductor nanocrystals or two or more different semiconductor nanocrystals.
  • the two or more different semiconductor nanocrystals may include semiconductor nanocrystals comprising different cores and/or shells or semiconductor nanocrystals that luminesce at different wavelengths.
  • the plurality of semiconductor nanocrystals may be dissolved in any appropriate solvent, such as, for example, toluene to form a semiconductor nanocrystal solution or may be obtained already in solution.
  • a first material is dissolved in the same type of solvent as is the plurality of semiconductor nanocrystals to form a first material solution.
  • materials that are soluble in toluene, a common solvent used in the preparation of semiconductor nanocrystals include polystyrene, polymethylmethacrylate, polyacrylate, poly(n-butyl methacrylate and derivatives.
  • the first material may be dissolved in the solvent by heating the solvent at approximately 110° C., for example, until the first material is dissolved to form a first material solution. It is appreciated that the temperature indicated for dissolving the first material is only exemplary and the proper temperature and time to dissolve may depend on the initial size of the first material, the temperature, as well as the type of first material used.
  • the semiconductor nanocrystal solution obtained in step 210 is added to the first material solution obtained in step 220 to form a semiconductor nanocrystal/first material solution.
  • the semiconductor nanocrystal solution comprising the plurality of two or more different semiconductor nanocrystals can similarly be added to first material solution to form a semiconductor nanocrystal/first material solution.
  • each of the plurality of two or more different semiconductor nanocrystals may be separately dissolved a solvent and then each of the resultant semiconductor nanocrystal solutions can be added to the first material solution to form a semiconductor nanocrystal/first material solution.
  • This solution is then mixed by simply stirring the solution, for example. Because the plurality of semiconductor nanocrystals and the first material are both soluble in the same solvent, the addition of the semiconductor nanocrystal solution to the first material solution allows the plurality of semiconductor nanocrystals to mix homogeneously with the first material.
  • the solvent is evaporated out of the semiconductor nanocrystal/first material solution leaving a semiconductor nanocrystal composition comprising the plurality of semiconductor nanocrystals in the first material.
  • the semiconductor nanocrystal composition comprises a first matrix material comprising a plurality of semiconductor nanocrystals.
  • the solvent may be evaporated by heating the semiconductor nanocrystal/first material solution to 110° C., for example. The solution may then be poured in a tray and placed in a fume hood to evaporate all remaining solvent leaving a solid semiconductor nanocrystal composition that can constitute a pre-form material.
  • a method of the present invention further comprises step 250 , in which the semiconductor nanocrystal composition from step 240 is processed further prior to shaping.
  • the semiconductor nanocrystal composition can be micronized prior to molding.
  • the semiconductor nanocrystal composition can be blended to reduce the size of the composition.
  • the desired size of the particles may vary depending on the equipment used to mold the pre-form material. For example, if injection molding is used, typically, injection molders are able to process particles (often referred to as pellets) from anywhere between a few microns to tens of centimeters.
  • the semiconductor nanocrystal composition can be micronized by known techniques, such as, for example, blending, grinding, milling, and jet milling.
  • the pre-processing step 250 involves micronizing the semiconductor nanocrystal composition and then dispersing the micronized composition in a second material to make a pre-form material. Further, in certain embodiments, the pre-processing step involves micronizing a first semiconductor nanocrystal composition comprising a plurality of first semiconductor nanocrystals in a first material and micronizing a second semiconductor nanocrystal composition comprising a plurality of second, different semiconductor nanocrystals in a second material and then adding the first and second micronized semiconductor nanocrystal compositions to a base material to make a pre-form material.
  • the pre-form material may comprise a plurality of the same semiconductor nanocrystals in a plurality of different materials, a plurality of different semiconductor nanocrystals in the same material, or a plurality of different semiconductor nanocrystals in a plurality of different materials.
  • Other details regarding micronizing a semiconductor nanocrystal composition can be found in co-pending U.S. application Ser. No. 11/175,196, filed on Jul. 7, 2005.
  • step 250 is not performed.
  • the semiconductor nanocrystal composition from step 240 constitutes a pre-form material that is subsequently shaped.
  • the pre-form material is formed into a shaped article by any suitable molding process known in the art.
  • the pre-form material is injection molded into a shaped article.
  • the resin or raw material for injection molding is in pellet form and is melted by heat and shearing forces shortly before being injected into the mold.
  • the pre-form material resulting from processing step 250 (the micronized semiconductor nanocrystal composition) may be used as a traditional injection moldable pellet. It is appreciated that in addition to adding processed pre-form material resulting from step 250 , traditional pellets which may or may not be of the same material as that used for the manufacture of the pre-form material may be added during step 260 . This can allow for the flexibility to control the concentration of semiconductor nanocrystals contained in the final shaped article.
  • the pellets may be poured into a feed hopper, a large open bottomed container, which feeds the granules down to a screw.
  • the screw may be turned by a hydraulic or electric motor that feeds the pellets through the grooves of the screw. As the screw rotates, the pellets may be moved forward in the screw and they undergo pressure and friction which generate the heat needed to melt the pellets. Heaters may be placed on either side of the screw to assist in heating the pellets during the melting process. The total energy provided during this step should not cause the semiconductor nanocrystals to degrade. Degradation may happen if the heat generated during formation is too high.
  • a hydraulic system may be used to secure the mold parts and the heated complex may be forced under the pressure of the injection screw to take the shape of the mold. Some machines are run by electric motors instead of hydraulics or a combination of both. Water-cooling can be may assist in cooling the mold and the heated complex solidifies into a shaped article. The shaped article may then be ejected (often with the assistance of an ejector pins within the mold).
  • the shaped articles comprising semiconductor nanocrystals of the present invention have several applications.
  • the shaped articles can be used in lighting applications, such as light emitting devices.
  • shaped articles can be fashioned into a lens and/or cup for use in conjunction with a light emitting device.
  • the semiconductor nanocrystals may be excited by the underlying light source and fluoresce at a desired wavelength. In this way, a user may take advantage of the fluorescent properties of the underlying semiconductor nanocrystals without substantially altering the manufacturing process for the existing LED devices.
  • visibly emitting semiconductor nanocrystals such as, for example, CdS, CdSe, CdTe, InP, InN, ZnSe, may be added to a material that is then shaped into a lens or cup.
  • white light emitting diodes typically are excited by a 460-480 nm InGaN emitter with a cerium doped yttrium aluminum garnet (YAG) phosphor placed on top of the light emitting diodes.
  • YAG yttrium aluminum garnet
  • the shaped articles of the present invention can form a cup of an LED device or be placed into the cup of an LED device (or a lens for use with such device) can be used in addition to or instead of YAG phosphors to create a light with more red emission.
  • red emitting CdS nanocrystals injected molded into an LED cup may be used instead of a traditional LED cup.
  • the disclosed use of the articles of the present invention can work not only for light emitting diodes but also other lighting applications such as plasma displays, fluorescent lighting, or with any other blue or ultra violet source emitter.
  • red, green and blue emitting shaped articles of the present invention or other combinations of wavelengths can be placed on top of an ultraviolet emitting diode to create a white light emitting diode.
  • shaped articles of the present invention can also be used as light scatterers in lighting applications.
  • Traditional semiconductor nanocrystals when uniformly dispersed throughout a solution or matrix do not scatter light due to their extremely small size. Some lighting applications using phosphors require scattering to ensure an optimized absorbance and optimized white light emission.
  • the shaped articles of the present invention can be used to create isotropic light emission.
  • the first material may be, for example, silica sol-gel that does not degrade under blue or UV excitation. Although, some optical epoxies do not degrade under blue or UV excitation, such optical epoxies have been shown to be incompatible with semiconductor nanocrystals.
  • the shaped articles of the present invention comprising semiconductor nanocrystals can be placed into or comprise optical epoxies to scatter light and be excitable by blue or UV excitation.
  • Shaped articles of the present invention can also have many uses in security applications. For example, shaped articles comprising semiconductor nanocrystals emitting in the infra-red range can be used for authentication purposes, providing a unique optical signature for the identification of the articles. Additionally, shaped articles comprising a plurality of CdSe nanocrystals emitting at various red, green and blue can be mixed together to make a visibly emitting spectral bar code that can be detected with a spectral bar code reader. It is appreciated that more than one type of semiconductor nanocrystal may be used in the same shaped article.
  • a shaped article is manufactured using semiconductor nanocrystals comprising PbS nanocrystals in a polystyrene matrix material that is processed with traditional materials used to make the desired shaped article.
  • the shaped article contains the fluorescent signature of the underlying PbS semiconductor nanocrystals and is able to be authenticated through the use of a reader.
  • shaped articles of the present invention can be used in the preparation of luminescent concentrator solar cells.
  • Luminescent concentrator solar cells may have light absorbing materials incorporated into a polymer or silicone layer. These materials act to absorb light from the sun and transmit the energy emitted by the light absorbing materials to a photovoltaic device optically coupled to the material.
  • a shaped article of the present invention may be prepared such that the semiconductor nanocrystals absorb at least a portion of the light emitting by the sun and the material containing the semiconductor nanocrystals may be selected such that it efficiently transmits the energy emitted by these nanocrystals.
  • the material used in the preparation of the shaped article may be the polymers or silicones that are presently used to create a luminescent concentrator solar cell.
  • the nanocrystals may be incorporated into a polycarbonate matrix material which may efficiently transmit the energy generated by the semiconductor nanocrystals to a photovoltaic device.
  • the following example describes a process for preparing a shaped article comprising a plurality of CdS nanocrystals and a first matrix material that is polystyrene.
  • CdS/ZnS core/shell nanocrystals are purchased in toluene (Evident Technologies, Troy, N.Y.). After the polystyrene is dissolved, 1.0 g of CdS/ZnS semiconductor nanocrystals are added to the solution and mixed. Next, the toluene is evaporated by heating the solution to 110.6° C. until the total volume is reduced to approximately 500 mL. The solution is then poured into a 9 ⁇ 13 inch Pyrex tray, and placed in a fume hood overnight to allow for most of the solvent to evaporate. The remaining solvent is removed using a vacuum oven (50° C.) resulting in formation of a polymer/semiconductor nanocrystal solid composition.
  • This resulting semiconductor nanocrystal composition is then processed in a blender and micronized to the desired size to form a pre-form material that is micronized.
  • the pre-formed material is placed in an injection molded machine and injection molded into a shaped article.
  • the shaped article retained the luminescent and absorption properties of the underlying semiconductor nanocrystal.
  • the following example describes a process for preparing a shaped article comprising a plurality of two different semiconductor nanocrystals (PbS and CdSe/ZnS nanocrystals) in a first material that is polystyrene.
  • PbS and CdSe/ZnS nanocrystals are purchased in toluene (Evident Technologies, Troy, N.Y.). 99 g of polystyrene are dissolved in 1.0 L of toluene at 110.6° C. (boiling). After the polystyrene is dissolved, 0.5 g of PbS semiconductor nanocrystals and 0.5 g of CdSe/ZnS nanocrystals are added to the solution and mixed. Next, the toluene is evaporated by heating the solution to 110.6° C. until the total volume is reduced to approximately 500 mL.
  • the solution is then be poured into a 9 ⁇ 13 inch Pyrex tray, and placed in a fume hood overnight to allow most of the solvent to evaporate.
  • the remaining solvent is removed using a vacuum oven (50° C.) resulting in formation of a polymer/semiconductor nanocrystal solid composition.
  • This resulting solid composition is then micronized in a blender to the desired size to form a pre-form material that is micronized.
  • the pre-form material is placed in an injection molded machine and injection molded into an article. The article retained the luminescent and absorption properties of the underlying semiconductor nanocrystal complexes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Luminescent Compositions (AREA)
  • Led Device Packages (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
US11/484,785 2006-07-12 2006-07-12 Shaped articles comprising semiconductor nanocrystals and methods of making and using same Abandoned US20080012001A1 (en)

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US9677001B2 (en) 2007-03-19 2017-06-13 Nanosys, Inc. Light-emitting diode (LED) devices comprising nanocrystals
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US9909062B2 (en) 2007-03-19 2018-03-06 Nanosys, Inc. Light-emitting diode (LED) devices comprising nanocrystals
WO2010024981A1 (fr) * 2008-08-27 2010-03-04 Osram Sylvania, Inc. Convertisseur luminescent en composite céramique et son procédé de fabrication
EP2351113B1 (fr) * 2008-11-19 2019-03-13 Nanoco Technologies Ltd Dispositifs électroluminescents à base de nanoparticules semi-conductrices, et matériaux et procédés associés
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US9199842B2 (en) 2008-12-30 2015-12-01 Nanosys, Inc. Quantum dot films, lighting devices, and lighting methods
US9804319B2 (en) 2008-12-30 2017-10-31 Nanosys, Inc. Quantum dot films, lighting devices, and lighting methods
US9139767B2 (en) 2008-12-30 2015-09-22 Nanosys, Inc. Methods for encapsulating nanocrystals and resulting compositions
US11420412B2 (en) 2008-12-30 2022-08-23 Nanosys, Inc. Quantum dot films, lighting devices, and lighting methods
US10214686B2 (en) 2008-12-30 2019-02-26 Nanosys, Inc. Methods for encapsulating nanocrystals and resulting compositions
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US10544362B2 (en) 2008-12-30 2020-01-28 Nanosys, Inc. Methods for encapsulating nanocrystals and resulting compositions
US9346998B2 (en) 2009-04-23 2016-05-24 The University Of Chicago Materials and methods for the preparation of nanocomposites
US10121952B2 (en) 2009-04-23 2018-11-06 The University Of Chicago Materials and methods for the preparation of nanocomposites
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US11518934B2 (en) * 2013-10-04 2022-12-06 King Abdullah University Of Science And Technology System and method for making quantum dots
CN104022223A (zh) * 2014-05-27 2014-09-03 河南大学 一种核壳结构硒化镉/硫化铅纳米四角体及其制备方法
US11316079B2 (en) * 2016-12-14 2022-04-26 Samsung Electronics Co., Ltd. Emissive nanocrystal particle, method of preparing the same and device including emissive nanocrystal particle
US20190378959A1 (en) * 2016-12-14 2019-12-12 Samsung Electronics Co., Ltd. Emissive nanocrystal particle, method of preparing the same and device including emissive nanocrystal particle
US10424695B2 (en) * 2016-12-14 2019-09-24 Samsung Electronics Co., Ltd. Emissive nanocrystal particle, method of preparing the same and device including emissive nanocrystal particle
US20190181306A1 (en) * 2017-12-08 2019-06-13 Chi Mei Corporation Luminescent material and light emitting device and display device using the same
US11205742B2 (en) * 2017-12-08 2021-12-21 Chimei Corporation Luminescent material and light emitting device and display device using the same
US11171263B2 (en) 2018-12-21 2021-11-09 Chimei Corporation Quantum dot and manufacturing method for the same and application using the same
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