PROCESS FOR THE PRODUCTION OF A SOLID POLYMER WITH THE LUMINESCENT NANOPARTICLES INCORPORATED IN THE

专利摘要:
process for the production of a solid polymer with the luminescent nanoparticles incorporated in the polymer, luminescent polymeric article, lighting unit and luminescent material. the invention provides a process for producing a solid polymer with incorporated luminescent nanoparticles, comprising (1) mixing the luminescent nanoparticles with a surface coated with leveling molecules comprising a first functional group and a second functional group and a precursor of a solid polymer , and (2) allowing the solid polymer to be formed; wherein the first functional group is configured to bond to the outer surface of the quantum dot and the second functional group is miscible with the solid polymer precursor and / or able to react with the solid polymer precursor. the invention also provides a luminescent polymeric article comprising a solid polymer such as the polymeric article incorporated in the luminescent nanoparticles with an outer surface coated with leveling molecules comprising a first functional group and a second functional group.
公开号:BR112014018744B1
申请号:R112014018744-4
申请日:2013-01-25
公开日:2020-12-15
发明作者:Shu Xu；Rifat Ata Mustafa Hikmet
申请人:Lumileds Holding B.V；
IPC主号:

专利说明:

FIELD OF THE INVENTION
[001] The invention relates to a process for the production of a solid polymer with the luminescent nanoparticles incorporated in the polymer, to a polymeric article thus obtained, and to a lighting unit comprising such polymer or polymeric article. HISTORY OF THE INVENTION
[002] The use of nanoparticles, such as quantum dots (QD), for lighting applications is known in the art. US20110240960, for example, describes a light emitting device comprising a light emitting source, a first quantum dot wavelength converter arranged above the light emitting source, the first point wavelength converter quantum comprising a plurality of the first quantum dots to generate light converted by the wavelength by converting the wavelength of light from the light emitting source, a first dispersive medium incorporating to it the first quantum dots dispersively, and a first sealer to seal all the outer surface of the dispersive medium incorporating the first quantum dots in a package.
[003] A first encapsulant is applied to encapsulate the entire outer surface of the first quantum dot wavelength converter. In addition, a second quantum dot wavelength converter is arranged above the first quantum dot wavelength converter, the second quantum dot wavelength converter comprising a plurality of second quantum dots to generate light converted by the length converting the wavelength of light from the light emitting source, a second dispersive medium incorporating the second quantum dots dispersively to it, and a second sealer to seal the entire outer surface of the second dispersive medium incorporating the second quantum dots in a package, where the first quantum dot wavelength converter, the second quantum dot wavelength converter and the light emitting source are separated from each other. The second encapsulant is arranged over the entire outer surface of the second quantum dot wavelength converter and to encapsulate the entire outer surface of the second quantum dot wavelength converter. In addition, the light emitting source is a light emitting diode or a laser diode. SUMMARY OF THE INVENTION
[004] Nanoparticles, such as quantum dots (QDs), have shown to be highly interesting in lighting applications. They could serve, for example, as inorganic phosphorus in converting blue light into other colors and have the advantage of a relative narrow emission band and the color advantage adjustable by the size of the QDs to be able to obtain a pure white light of high quality.
[005] Until now, incorporating nanoparticles in many types of polymers seems to lead to the aggregation of nanoparticles. The reported leveling molecules have very low photochemical stability and the leveling molecules are normally sensitive in the air.
[006] Therefore, it is an aspect of the invention to provide an alternative nanoparticle - polymer system, especially a polymer quantum dot system. In particular, it is an aspect of the invention to provide an alternative process for the production of such a polymer with incorporated nanoparticles. Furthermore, it is an aspect of the invention to provide an alternative polymeric article with nanoparticles incorporated therein. In addition, it is an additional aspect to provide an alternative lighting unit comprising such a polymer with built-in QDs. Preferably, the alternative process and / or alternative polymeric article and / or alternative lighting unit at least partially prevents one or more of the disadvantages described above (and also described below) of the prior art solutions.
[007] Among other things, it is suggested here to use high Tg, such as at least 120 ° C, even more especially at least 150 ° C, even more especially at least 200 ° C, and photochemical stable polymers, for example, polymer containing silicone, as a matrix material with high stability. Polymers containing silicon such as PDMS and Silres (silicone resins) may have much higher thermal stability and / or light transparency than prior art solutions. However, QDs with conventional surface leveling molecules do not disperse in silicones and show aggregation leading to extinction. Therefore, it is still a challenge to mix nanoparticles in such polymers, especially polymers containing silicon. The phase separation between nanoparticles and polymers causes agglomeration of QDs and dramatically decreases the quantum yields and light transparency of the nanoparticle / polymer mixture.
[008] Here, in order to achieve QD layers well dispersed in silicones, it is suggested to use the leveling molecules or binders that can attach to the surface of the QDs. A group of new compatible matrix leveling molecules, such as compatible silicone, has been developed. These leveling molecules could easily level in the QDs and bring them to form uniform QDs / silicon polymer composites (through simple ligand exchange approaches). These leveling molecules are made up of two parts; one part matches the atoms exposed on the crystal surface of the QDs and the other part has compatibility with the matrix (eg, silicone). By modifying the surface of the nanoparticles, the nanoparticles could be easily mixed into polymers containing matrix (silicone), such as PDMS and Silres, without phase separation. The new matrices could form thin, highly transparent films. The films have high thermal stability and could be used as a new light conversion phosphor. By choosing the combined PDMS / Silres and surface leveling molecules for nanoparticles, it is possible to mix most common nanoparticles homogeneously in any specific PDMS / Silres matrix. The thin films of nanoparticles / silicon matrix formed have high light transparency and stability comparable to nanoparticles in pure inorganic matrices. Nanoparticle / silicon polymer composites have overwhelming advantages compared to other nanoparticle - polymer matrices that have been tried (in the laboratory).
[009] Therefore, in a first aspect, the invention provides a process for the production of a solid polymer (article) with the nanoparticles incorporated in the polymer, especially luminescent nanoparticles, the process comprising the elements of the process: b. mixing (i) nanoparticles, especially luminescent nanoparticles, with the outer surface coated with leveling molecules comprising a first functional group and a second functional group and (ii) a solid polymer precursor (here also referred to as “polymer precursor”) , and c. allowing the solid polymer to be formed, thereby producing the nanoparticles incorporated in the solid polymer;
[001] where the first functional group is configured to bond to the outer surface of the quantum dot and where the second functional group has one or more functions selected from the group consisting of (a) being miscible with the solid polymer precursor and ( b) be able to react with the solid polymer precursor, as also defined in claim 1.
[002] Especially, nanoparticles are luminescent nanoparticles, which can be specially configured to provide, by excitation by UV and / or blue light, luminescence in at least part of the visible part of the spectrum. Therefore, these particles are also indicated here as luminescent nanoparticles.
[003] Such a polymer, obtainable by such a process, can be used as or in a polymeric article and appears to show luminescence with a high quantum yield and stability. In addition, the polymer can be relatively stable in temperature and / or photochemistry, especially when silicone-based polymers (and leveling molecules) are applied. In addition, with this process, the nanoparticles can be dispersed in the polymer in an even relative form, without the substantial disadvantage of agglomeration.
[004] Therefore, in a further aspect, the invention also provides a solid polymer or polymeric article, obtainable by the process of the invention. In particular, the invention also provides a polymeric (luminescent) article comprising nanoparticles (luminescent) incorporated into the solid polymer of the polymeric article with an outer surface coated with leveling molecules comprising a first functional group and a second functional group, as also defined in the claim 8.
[005] As these luminescent materials can be well applied in lighting devices, the invention provides, in yet an additional aspect, a lighting unit comprising (i) a light source configured to generate a light from the light source and (ii ) a light converter configured to convert at least part of the light from the light source into the light converter, wherein the light converter comprises the solid polymer obtainable from the process as defined herein or the polymeric article as defined herein.
[006] Luminescent nanoparticles can comprise, for example, group II-VI compound semiconductor nanoparticles selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSeTe, Cd ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe. In another embodiment, luminescent nanoparticles can be, for example, semiconductor nanoparticles of group III-V compounds selected from the group consisting of GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs , AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, and InAlPAs. In a further embodiment, the luminescent nanoparticles can be, for example, chalcopyrite-type semiconductor nanoparticles I-III-VI2 selected from the group consisting of CuInS2, CuInSe2, CuGaS2, CuGaSe2, AgInS2, AgInSe2, AgGaS2, and AgGaSe2. Still in a further embodiment, the luminescent nanoparticles can be, for example, I-V-VI2 semiconductor nanoparticles, such as those selected from the group consisting of LiAsSe2, NaAsSe2 and KAsSe2. In a still further embodiment, the luminescent nanoparticles can be, for example, semiconductor nanocrystals of the group IV-VI compound such as SbTe. In a specific embodiment, the luminescent nanoparticles are selected from the group consisting of InP, CuInS2, CuInSe2, CdTe, CdSe, CdSeTe, AgInS2 and AgInSe2. In yet a further embodiment, the luminescent nanoparticles can be, for example, one of the semiconductor nanocrystals of the group II-VI, IIIV, I-III-V and IV-VI selected from the materials described above with contaminants inside such as ZnSe: Mn, ZnS: Mn. Contaminating elements could be selected from Mn, Ag, Zn, Eu, S, P, Cu, Ce, Tb, Au, Pb, Tb, Sb, Sn and Tl. Here, luminescent nanoparticles based on luminescent material can also comprise different types of QDs, such as CdSe and ZnSe: Mn ...
[007] To be especially advantageous to use nanoparticles II-VI. Therefore, in one embodiment, the semiconductor-based luminescent nanoparticles comprise II-VI nanoparticles, specially selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTn, CdSe, CdSe, CdSe, CdSe , ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe, more especially selected from the group consisting of CdS, CdSe, CdSe / CdS and CdSe / CdS / ZnS.
[008] Luminescent nanoparticles (without coating) can have dimensions in the range of about 2 to 50 nm, such as 2 to 20 nm, especially 2 to 10 nm, even more especially 2 to 5 nm; especially at least 90% of the nanoparticles have dimensions in the indicated ranges, respectively, (ie, for example, at least 90% of the nanoparticles have dimensions in the range of 2 to 50 nm, or especially at least 90% of the nanoparticles have dimensions in the range 2 to 5 nm). Typical points are made of binary alloys such as cadmium selenide, cadmium sulfide, indium arsenide, and indium phosphite. However, the stitches can also be made of ternary alloys such as cadmium selenide sulfide. These quantum dots can contain only 100 to 100,000 atoms within the volume of the quantum dot, with a diameter of 10 to 50 atoms. This corresponds to about 2 to 10 nanometers. For example, spherical particles such as CdSe, InP, CuInSe2 with a diameter of about 3 nm can be supplied. Luminescent (uncoated) nanoparticles can be shaped like a sphere, cube, rods, wires, discs, multipoint, etc., with a size in a dimension of less than 10 nm. For example, CdSe nanobars with a length of 20 nm and a diameter of 4 nm can be supplied. Therefore, in one embodiment, the semiconductor-based luminescent nanoparticles comprise nanoparticles of the core shell. In yet another embodiment, semiconductor-based luminescent nanoparticles comprise nanoparticles on rods. A combination of different types of particles can also be applied. For example, core shell particles and stem points can be applied and / or combinations of two or more of the nanoparticles mentioned above can be applied, such as CdS and CdSe.
[009] Therefore, the outer surface mentioned above may be the surface of an uncovered quantum dot or it may be the surface of a coated quantum dot, such as a quantum dot on the core shell, that is, the (outer) surface of the bark.
[010] Here, the term "solid polymer" is used to indicate that the polymeric end product of the process of the invention is not a liquid or solvent polymer, but a tangible product (at room temperature (and atmospheric pressure)) in the form of , for example, particles, a film, a plate, etc. Therefore, in one embodiment, the polymeric article is selected from the group consisting of a coating, a self-supporting layer and a plate (which the polymeric article is thus solid at room temperature, especially even at 100 ° C, especially even up to 150 ° C, especially even up to 200 oC).
[011] Especially, the polymeric article is transmissive to light having a wavelength selected from the range of 380 to 750 nm. For example, the polymeric article can be transmissive to blue, and / or green, and / or red light. In particular, the polymeric article is transmissive for at least the entire range of 420 to 680 nm. In particular, the polymeric article has a light transmission in the range of 50 to 100%, especially in the range of 70 to 100%, for the light generated by the light source of the lighting unit (see also below) and which has a length of selected wave from the visible wavelength range. In this way, the article is transmissive to visible light from the lighting unit. The transmission or permeability of light can be determined by providing light at a specific wavelength with a first intensity for the material and relating it to the intensity of light at that wavelength measured after transmission through the material, for the first intensity of light delivered at that length specific waveform (see also E-208 and E-406 of the CRC Handbook of Chemistry and Physics, 69th edition, 1088-1989). The polymeric article can be transparent or translucent, but it can be especially transparent.
[012] The process of the invention comprises at least two elements of the process, which will, in general, be carried out consecutively, with the first element of the process preceding the second element of the process. The fact that two elements of the process are explicitly mentioned does not exclude the presence of one or more other elements of the process, which can be included in the process before the first element of the process, and / or between the first and the second element of the process, and / or after the second element of the process. For example, the process of the invention can also include an exchange of leveling molecules existing in the quantum nanoparticle with leveling molecules as defined in the present invention.
[013] The first element of the process includes mixing the coated nanoparticles and the solid polymer precursor. In general, this could be accelerated or optimized in the presence of a solvent for the nanoparticles and the polymer precursor. Here, a solvent is considered to be a solvent when at room temperature at least 0.1 gram / l of a species to be solved can be solved in the solvent. The solvent could be any common solvents, preferably non-polar, with preferably a boiling point less than 120 ° C. For example, the solvent could be toluene, benzene, hexane, cyclohexane, etc. The solvent could be a polar solvent. For example, the solvent could be chloroform, acetone, nitrile acetone, ethyl acetate, petroleum ether etc. The mixture can be made with conventional techniques. Optionally, the mixture can be heated.
[014] The polymer precursor can in one embodiment comprise monomers for a polymer, monomers that are capable of forming a polymer through polymerization. However, in another embodiment, the polymer precursor is a polymer, which is solvent in the solvent. In the previous embodiment, due to polymerization, the nanoparticles are incorporated into the polymer thus formed. In the last embodiment, the solvent polymer is recovered from the solution, for example, by evaporation of the solvent or other techniques known in the art. The polymer is formed (again) and the nanoparticles are thus incorporated into the polymer thus (re) formed. This last realization can be similar to the polymer crystallization techniques.
[015] The polymer can be any type of polymer, as obtainable by the polymerization of growth by step, by the polymerization of chain growth, by radical polymerization, by catalyzed polymerization, etc. Therefore, the expression "allowing the solid polymer to be formed", for example, may suggest the addition of an initiator for polymerization and / or supply of light and / or heating of the mixture to initiate polymerization etc. The polymer can be a homopolymer, a copolymer, such as an alternative copolymer, a periodic copolymer, a periodic copolymer, a statistical copolymer, a blocking copolymer, a grafted copolymer, or a terpolymer etc. In particular, the polymer precursor is a precursor to a (solid) polymer selected from the group consisting of a polysiloxane, a polystyrene and a polyacrylate, especially a polysiloxane.
[016] As indicated above, the first functional group is configured to bond to the outer surface of the quantum dot and the second functional group has one or more functions selected from the group consisting of (a) being miscible with the solid polymer precursor and ( b) be able to react with the solid polymer precursor. Due to this at least double function, the leveling molecule is able to bond to the quantum dot, but the leveling molecule is also able to be at least partially integrated into the polymer (during the formation of the solid polymer). In this way, a good dispersion of the nanoparticles in the polymer is possible, without aggregation. In the prior art, aggregation inevitably occurs. In particular, the second functional group has at least the function of being miscible with the solid polymer precursor. Optionally, the binder can also react with the solid polymer precursor (and / or with the solid polymer in the formation in the second process element). By reacting, for example, graft copolymers or copolymers can be obtained.
[017] Therefore, in one embodiment, the precursor of a solid polymer comprises monomers that are capable of forming the polymer upon polymerization, and in another embodiment, the precursor of a solid polymer comprises a polymer; wherein the first process element involves (1) mixing (i) nanoparticles with the outer surface coated with leveling molecules comprising the first functional group and the second functional group, (ii) the precursor of the solid polymer, and (iii) a solvent for the solid polymer precursor ...
[018] Therefore, the first functional group can, in one embodiment, comprise a metal ion serving as a coordination center, such as Zn (especially Zn2 +), Ni (especially Ni2 +), In (like In3 +), Cd (like Cd2 +), Cu (as Cu + or preferably Cu2 +), which allows coordination / connection with anions - for example S, Se, P - on the surface of a nanoparticle. For this reason, the first functional group (of the first type of leveling molecule; see also below) may comprise a metal ion with coordination functionality.
[019] The first functional group may, in another embodiment, comprise an organic group, such as amine, acid, thiol, which allows the coordination / connection of cations - for example, Cd, Zn, In, Cu, Mg, Ag, etc. - on the surface of a nanoparticle.
[020] Therefore, the coating with the leveling molecules can be considered to be due to the fact that the leveling molecules are in coordination with the outer surface of the nanoparticle. This can be the outer surface of a discovered nanoparticle or the outer surface of the coating (here inorganic, usually also semiconductor) of the nanoparticle. The leveling molecules can thus attach to the outer surface.
[021] The second functional group preferably comprises at least one polymer monomer (precursor), although other systems that are miscible with the polymer (precursor) can also be applied. This may depend on miscibility. The term miscible is known in the art, but can optionally be defined as that at least 0.1 gram of nanoparticles with leveling molecules that is miscible in 1 kg of the precursor polymer and optional solvent, at room temperature (and atmospheric pressure), without phase separation between the precursor polymer and nanoparticles (with leveling molecules). Optionally, miscible can, in one embodiment, also be defined as that which the quantum dot leveling molecules contain a monomer unit of the precursor polymer.
[022] The expression "contains a precursor polymer monomer" and similar expressions may, in one embodiment, indicate that the linker or leveling molecule comprises a monomer also used or usable as a monomer building block for the polymer or solid polymer . The expression "contains a precursor polymer monomer" and similar expressions may, in one embodiment, also indicate that the linker or leveling molecule comprises a monomer that is similar to the monomer also used or usable as a monomer building block for the polymer or the solid polymer. The expression "contains a precursor polymer monomer" and similar expressions may, in one embodiment, further indicate that the linker or leveling molecule comprises a group that is identical or a group of the monomer also used or usable as a monomer building block for the polymer or solid polymer. For example, the monomer (s) that are (are) used (or have been used) for the formation of the polymer may contain side chains, which are similar or identical to second functional group of the ligand. Some non-limiting examples are given below:



[023] Therefore, in one embodiment (of the process of the invention), the second functional group is selected from the group consisting of a siloxane, a styrene, and an acrylate, and the solid polymer comprises a polymer selected from the group consisting of a polysiloxane, a polystyrene and a polyacrylate, respectively. The phrase "the second functional group is selected from the group consisting of a siloxane, a styrene, and an acrylate" can also include embodiments in which the second functional group includes a polysiloxane, a polystyrene or a polyacrylate, respectively (but including a limited number characterization groups, see also below). The expression "the solid polymer comprises a polymer selected from the group consisting of a polysiloxane, a polystyrene and a polyacrylate" can especially refer to embodiments in which the (solid) polymer is essentially based on such polymers, respectively.
[024] The PDMS binder or PDMS monomer, as indicated above in the table, can certainly be smaller than the polymers in the PDMS matrix. This can also apply to (other) systems mentioned above. For example, the number of repeat units (from the characterization group) in the linker or leveling molecule can be 1 to 100 monomer units, such as 2 to 50, such as 20 to 30 monomer units, especially 4 to 20 Therefore, here the binder comprises a limited number of characterization groups. Silres are a type of silicones.
[025] For example, in an embodiment where the solid polymer (here also indicated as the polymer matrix) is a silicone, the binder or leveling molecule may, for example, comprise - [- Si (CH3) 2-O- ] n, with n = 1-100 (such as at least 2), as a second functional group, for example, NH2 - [- Si (CH3) 2-O-] n-CH3 or ZnOOC - [- Si (CH3 ) 2-O-] n-CH3. One or more of the CH3 side groups, for one or more of the silicone units n, can be optionally substituted by a phenyl group (i.e., benzene). More generally, the leveling molecule may comprise - [- Si (R) 2-O-] n, with n = 1-100 (such as, at least 2), as the second functional group, where the side groups R a from silicon may be identical or may differ, and may even differ from silicon to silicon within the functional group. R can, for example, be selected from the group consisting of methyl, phenyl, etc. - [- Si (R) 2-O-] refers to the silicone unit or silicone characterization group (ie, group that characterizes a silicone).
[026] Therefore, still in a further aspect, the invention also provides a luminescent material comprising a plurality of nanoparticles, wherein the nanoparticles comprise outer surfaces coated with leveling molecules, where the leveling molecules comprise - [- Si ( R) 2-O-] n, with n = 1-100, such as at least 2, where R is selected from methyl and phenyl. As indicated above, one can also indicate the silicone groups as - [- Si (R1R2) -O-] n, since the R groups are not necessarily the same for a silicon, but can differ by silicon within the group. However, in one embodiment, all R groups are methyl or phenyl.
[027] In yet another example, in an embodiment in which the solid polymer (here also indicated as the polymer matrix) is a polymethacrylate, the linker may, for example, comprise - [- C5O2H8-] n, with n = 1- 50, such as 1 - 20, such as at least 2, as a second functional group, for example, HSCH2 - [- C5O2H8-] n-CH3 or Ni (OOC - [- C5O2H8-] n-CH3) 2.
[028] The number of recurrent characterization units n is especially at least 4.
[029] Above, some examples of different types of leveling molecules have already been given. The leveling molecules can be distinguished between those that preferentially coordinate for nanoparticle cations and those that preferentially coordinate for nanoparticle anions (on the surface of the quantum dot). Therefore, preferably, the leveling molecules comprise two types of leveling molecules, wherein the first functional group of the first type of leveling molecules can comprise a metal ion with coordination functionality (such as with a ready free electron pair to coordinate or connect with anions) and (/ or) where the first functional group of the second type of leveling molecule has a Lewis base functionality. The first functional group of the first type of leveling molecule may have a Lewis acid function in one embodiment).
[030] As indicated above, two types of leveling molecules or ligands are preferably used: the first type of leveling molecules and the second type of leveling molecules. These leveling molecules or ligands occupy the surface of the quantum dot and can thus remove or reduce erratic bonds. In this way, the quantum efficiency can be increased. The leveling molecules can thus provide a type of (organic) coating.
[031] The first type of leveling molecule comprises Mn + Rn, where M is a metal, where n is at least 2, and where R is as indicated here, for example, a polymer precursor monomer (ie (the first type of leveling molecules are organic metal molecules). Therefore, the cation has a valence of two or more. Examples of suitable cations are cations selected from the group of transition metals, especially from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh , Ir, Ni, Pd, Pt, Cu, Zn, and Cd. Especially preferred are Zn, Mg, In, and Ga. The fact that valence n, which is preferably at least 2, such as 2, 3 or 4, also implies that two or more R groups do not imply that those R groups are necessarily identical. Each group R of the first type of leveling molecule can be unique. The first type of leveling molecules coordinate for the anions on the surface of the quantum dot. Assuming, for example, CdSe, the first type will coordinate for the If anions. The first type of leveling molecules can also be indicated as Lewis acid. The value of n is preferably (but not exclusively) 2. The first type of leveling molecule or ligand can coordinate with an anion on the (outer) surface of the nanoparticle since the metal ion has coordination functionality.
[032] The second type of leveling molecule especially comprises an organic Lewis base. A Lewis base is any species that donates an electron pair to a Lewis acid to form a Lewis adduct. For example, OH- and NH3 are Lewis bases, because they can donate a pair of lone electrons. A Lewis acid is a molecular entity (and the corresponding chemical species) that is an electron pair receptor and therefore capable of reacting with a Lewis base to form a Lewis adduct, sharing the electron pair provided by the base Lewis.
[033] Here, the Lewis base (and Lewis acid) are organic molecules, that is, a hydrocarbon having a portion of Lewis base. In particular, the second leveling molecule can be selected from the group consisting of RCN (nitrile), RNH2 (primary amine), R2NH (secondary amine), RSH (thiol), and RCOOH (carboxylic acid), and amino acid, and where R as indicated herein, for example, a monomer of the polymer precursor. Again, the fact that in some embodiments there may be two or more R groups on the second leveling molecule does not imply that those R groups are necessarily identical. Each hydrocarbon group R of the second type of leveling molecule can be unique. However, in a specific embodiment (where more than one R group is present in the second leveling molecule), all R groups of the second type of leveling molecules are identical.
[034] This method of modifying double surfactants provides close to 1: 1 coverage (or coating) of the cation and anion ions exposed on the surface of the QDs, for example, Cd and Se surfaces in CdSe and prevents erratic bonds in QD surfaces. In this, the surface coating is similar to the QDs' inorganic ZnS coated surface and provides narrow improvement to QDs like the ZnS coating. With the carefully selected stable organic molecules and organometallic molecules, the modified surface QDs showed highly improved quantum yields and photochemical stability. In addition, air-stable organic molecules could be chosen as dual surfactants to offer additional increased surface protection and air stability for even ZnS coated quantum dots. Since the process of organic coating can be through a process of exchange of binders without the problem of network incompatibility, the method could be applied to any form of quantum dots, offering this method a much more general application than inorganic coating. Especially, the molar ratio between the first type of leveling molecules and the second type of leveling molecules is in the range of 0.8 to 1.2 (that is, 8: 10-12: 10), even more especially 0, 9 to 1.1, even more especially 0.95 to 1.05. For example, 1.05 mol of zinc undecylenate and 1 mol of hexadecylamine gives a molar ratio of 1.05.
[035] The second functional group of the first type of leveling molecule and the second type of leveling molecule may be different. However, in a specific embodiment, the second functional group of the first type of leveling molecule and the second functional group of the second type of leveling molecules are the same. For example, NH2 - [- Si (CH3) 2-O-] n-CH3 and Zn (OOC - [- Si (CH3) 2-O-] n-CH3) 2 can be applied as leveling molecules.
[036] The matrices, ie solid polymers, can, for example, be chosen from the group consisting of PE (polyethylene), PP (polypropylene), PEN (polyethylene naphthalate), PC (polycarbonate), polymethylacrylate (PMA), polymethylmethacrylate (PMMA) (Plexiglas or Perspex), cellulose butyrate acetate (CAB), silicone, polyvinyl chloride (PVC), polyethylene terephthalate (PET), (PETG) (glycol modified polyethylene terephthalate), PDMS (polydimethylsiloxane) and COC -olefin), but especially silicones and poly (methyl) methacrylates, even more especially silicones, are applied ...
[037] As suggested above, the process of the invention can provide a luminescent polymeric article comprising a solid polymer with the luminescent nanoparticles incorporated in the polymeric article with an outer surface coated with leveling molecules comprising a first functional group and a second functional group. indicated above, the polymeric article can, for example, be transparent or translucent. The process of the invention can lead, in one embodiment, to a product in which at least part of the second functional group of at least part of the leveling molecules is intertwined with polymer chains of the solid polymer and / or in an embodiment for a product in which the second functional group of at least part of the leveling molecules is part of a polymer chain of the solid polymer. The latter embodiment may be the case when the second functional group may be able to react with the solid polymer precursor.
[038] As indicated above, leveling molecules can, in one embodiment, comprise two types of leveling molecules, in which the first functional group of the first type of leveling molecule has a central metal functionality and in which the first group functional of the second type of leveling molecule has Lewis base functionality. In particular, the molar ratio between the first type of leveling molecules and the second type of leveling molecules is in the range of 0.8 to 1.2. In this way, a substantial part of the quantum dot can be covered with the first type of leveling molecules and the second type of leveling molecules.
[039] In addition, as mentioned above, the invention also provides a lighting unit comprising (i) a light source configured to generate the light from the light source and (ii) a light converter configured to convert at least part of the light from the light source in the converting light, wherein the light converter comprises the solid polymer obtainable according to the process as defined herein or the polymeric article as defined herein. It may be advantageous, in view of the effectiveness and / or stability, to arrange the nanoparticles at a non-zero distance from the light source. Therefore, in one embodiment, the material of the light converter can be configured at a non-zero distance from the light source. For example, the material of the light converter, or especially the luminescent material, can be applied to or can be understood by a window of the lighting unit. In case the light source is configured to provide blue light, the luminescent material can be configured to convert only part of the light from the light source. The blue light from the light source and the light from the luminescent material of the luminescent nanoparticles based on the luminescent material together can, in one embodiment, provide white light from the lighting unit.
[040] In a further embodiment, the light source comprises a solid-state light source, such as a solid-state light emitting device or solid-state laser. The term light source can also refer to a plurality of light sources.
[041] The term white light here is known to the person skilled in the art. It especially refers to light that has a correlated color temperature (CCT) between about 2000 and 20000 K, especially 2700 and 20000 K, for general lighting in the range of about 2700 K and 6500 K, and for backlighting purposes especially in the range of about 7000 K and 20000 K, and especially within about 15 SDCM (color matching standard deviation) from BBL (blackbody locus), especially within about 10 SDCM from BBL, even more especially within about 5 SDCM of BBL.
[042] The terms "violet light" or "violet emission" especially refer to light that has a wavelength in the range of about 380 to 440 nm. The terms "blue light" or "blue emission" especially refer to light that has a wavelength in the range of about 440 to 490 nm (including some violet and cyan tones). The terms "green light" or "green emission" especially refer to light that has a wavelength in the range of about 490 to 560 nm. The terms "yellow light" or "yellow emission" especially refer to light that has a wavelength in the range of about 560 to 590 nm. The terms "orange light" or "orange emission" especially refer to light that has a wavelength in the range of about 590 to 620 nm. The terms "red light" or "red emission" especially refer to light that has a wavelength in the range of about 620 to 750 nm. The terms "visible light" or "visible emission" refer to light that has a wavelength in the range of about 380 to 750 nm.
[043] The term "substantially" here, as in "substantially every issue" or "substantially consists", will be understood by the person skilled in the matter. The term "substantially" can also include achievements with "totally", "completely", "all", etc. Therefore, in the realizations the adjective can also be substantially removed. Where applicable, the term "substantially" may also refer to 90% or more, such as 95% or more, especially 99% or more, even more especially 99.5% or more, including 100%. The term "comprises" also includes accomplishments where the term "comprises" means "consists of".
[044] Furthermore, the terms first, second, third and similar in the description and in the claims are used to distinguish between similar elements and not necessarily to describe a sequential or chronological order. It is to be understood that the terms thus used are interchangeable in appropriate circumstances and that the embodiments of the invention described here are capable of operating in sequences other than those described or illustrated herein.
[045] The devices here are among others described during the operation. As will be clear to the person skilled in the art, the invention is not limited to methods of operation or devices in operation.
[046] It should be noted that the achievements mentioned above illustrate rather than limit the invention, and that those skilled in the art will be able to design many alternative embodiments without departing from the scope of the appended claims. In the claims, any reference signs placed in parentheses should not be construed as limiting the claim. The use of the verb “to understand” and its conjugations does not exclude the presence of elements or steps other than those indicated in a claim. The article “one” or “one” preceding an element does not exclude the presence of a plurality of such elements. The mere fact that certain measures are cited in mutually different dependent claims does not indicate that a combination of these measures cannot be used to advantage.
[047] The invention also applies to a device comprising one or more of the characterization aspects described in the description and / or shown in the accompanying drawings. The invention still belongs to a method or process comprising one or more of the characterization aspects described in the description and / or and / or shown in the accompanying drawings.
[048] The various aspects discussed in that patent can be combined to provide additional advantages. In addition, some of the aspects may form the basis for one or more divisional applications. BRIEF DESCRIPTION OF THE DRAWINGS
[049] The realizations of the invention will now be described, by way of example only, with reference to the attached schematic drawings in which the corresponding reference symbols indicate corresponding parts, and in which:
[050] Figures 1a-1d schematically describe some aspects of the invention; and
[051] Figures 2a-2d schematically describe some additional aspects of the invention.
[052] Drawings are not necessarily on a scale. DETAILED DESCRIPTION OF ACHIEVEMENTS
[053] Figure 1a schematically describes a particle from the quantum dot 10, in this CdS-based realization. This means that on the surface of the QD 10 particle, indicated with reference 11, cadmium and sulfur ions are present. The leveling molecules coordinate the surface 11 of the QD 10 particle. Those leveling molecules are indicated with reference 200. Here, two types of leveling molecules are applied, which are indicated with references 1 and 2, respectively. The first type of ligand, Mn + Rn, is indicated with reference 1. Here, M is zinc (Zn), and R3 and R4 are used to indicate that the two hydrocarbons R can be different. However, R3 and R4 can also be identical. The second type of organic binder comprises an organic Lewis base, and is indicated with reference 2. Here, an amine is used, with R1, R2 and H. Instead of H, additional hydrocarbons can also be chosen. The first type of binder coordinates for sulfur; the second coordinates for cadmium. In this way, a semiconductor coated binder based on the luminescent quantum dot is provided, which is indicated with reference 100. Note that reference 10 refers to the “uncovered” quantum dot (with or without a shell), and the reference 100 refers to the coated quantum dot.
[054] Figure 1b schematically describes the same realization as the semiconductor coated binder based on the luminescent quantum dot 100 as described in figure 1a, with the difference that quantum dot 10 is now a quantum dot on the core shell. The core is indicated with reference 12; the shell is indicated with reference 13. Core 12 may, for example, be CdSe and shell 13 may, for example, be CdS.
[055] Figure 1c schematically describes a plurality of semiconductor coated binder based on the luminescent quantum dot, i.e., a luminescent material 30.
[056] This luminescent material can be applied to a lighting unit 5, as described schematically in figure 1d. Here, the lighting unit 5 comprises a light source 20, configured to generate light 21 from the light source, and a converter 40, configured to convert at least part of the light 21 from the light source into the converter light 41. For this purpose , the converter can comprise (including consist of) the luminescent material 30, it can essentially consist of the semiconductor coated binder based on the luminescent nanoparticles 100. Optionally, the converter 40 can comprise another material 42. For example, the converter can be a sheet or polymeric plate, incorporating the luminescent material 30. The converter 40 can especially be arranged at a non-zero distance d from the light source 20, which can, for example, be a light emitting diode, although the distance d can also be zero , for example, when the luminescent material 30 is applied in an LED matrix or incorporated in a (silicone) cone in the LED matrix. The converter can optionally allow at least part of the light 21 from the light source to penetrate through the converter. In this way, downstream of the converter, a combination of converter light 41 and light 21 from the light source can be found. The light downstream of the light converter is indicated a light 51 of the lighting unit.
[057] In addition to the semiconductor coated binder based on the luminescent nanoparticles 100, the luminescent material 30 can optionally also comprise other types of luminescent materials, for example, to adjust the color of the light 51 of the lighting unit, to increase the restitution of the color, to adjust the color temperature, etc.
[058] The terms "upstream" and "downstream" refer to the provision of items or aspects related to the propagation of light from a light-generating medium (here especially the first light source), in which in relation to a first position within a light beam of the light generating medium, a second position in the light beam near the light generating medium is "upstream", and the third position within the light beam furthest from the light generation is “downstream”.
[059] Figure 2a schematically describes a particle coated with a quantum dot 100, in which both cation (s) and anion (s) on the surface 11 of quantum dot 10 are coordinated by the leveling molecules. As an example, the first functional groups are Zn and NH (R) 2, respectively, and the second functional group (s) are for both leveling molecules 200 PDMS. The first linker 1 can comprise, for example, two groups of PDMS, although also only one can be used. PDMS groups can, for example, be functionalized with COO- (not described), to bind to the zinc ion. Note that here, when more than one R group is present in a compound, more than one R may be identical, but in one embodiment it may also differ.
[060] Figure 2b schematically describes a polymeric article 300. This article is described here as a coating, film or plate, but may also have other geometric properties than those described. The polymeric article 300 here comprises a body 301. The polymeric article comprises polymeric chains 302, such as, for example, PDMS or PMMA. They can be aligned, but they can also have other configurations. Nanoparticles 100 with their linker (s) 200 are incorporated in polymeric article 300. Leveling molecules 200 are in this embodiment intertwined with polymeric chains 302.
[061] Figure 2c schematically describes an additional embodiment of a polymeric article 300, with another geometric shape for illustration purposes (for example, a dome for an LED). Here, the nanoparticle binder (s) 100 is (are) part of one or more polymeric chains. Here, during the production of the polymeric article, leveling molecules were applied that were able to react with the polymer precursor.
[062] Figure 2d schematically describes an embodiment of the process of the invention. However, other avenues may also be possible. In this embodiment, a particle of the core shell is displayed, but other types of particles can also be applied. In this embodiment, the particle may also have been pre-coated with other leveling molecules, as described schematically. Therefore, first the leveling molecules of the invention are applied to the quantum dot. By way of example, two types of leveling molecules are applied. The particles are then combined with the polymer precursor, here by way of example, with monomeric units of PDMS (for example, containing 2 to 50 siloxane units), which is indicated with reference 402. Now, a mixture of the components of starting is obtained, which is subsequently treated to obtain the polymer or polymeric article 300. This element of the process is indicated with reference 403, and includes in this embodiment a polymerization process in which the monomer units polymerize to a polymer / polymeric article, in that embodiment a solid PDMS polymer or polymeric article 300. EXPERIMENTAL
[063] Preparation of the leveling molecules:
[064] Surfactants containing zinc and silicone are prepared by reacting high reactive organometallic zinc such as diethylzinc polymer and silicone with functional groups such as acid, thiol, etc. that could react with diethylzinc. For example:
[065] Prepare Zn-PDMS leveling molecules: diethylzinc + PDMS finished with monocarboxidecyl
[066] ZnEt2 + PDMS-CxH2xCOOH = (PDMS-CxH2xCOO) 2Zn
[067] React in toluene for 30 min at room temperature and finish with NaHCO3 to remove traces of remaining ZnEt2 and the products. The purified Zn-PDMS are clear or a slightly cloudy solution at room temperature.
[068] Exchanging leveling molecules: example
[069] Switching to a Cd-rich CdSe / CdS QRs: CdSe / CdS stems are pre-synthesized according to the literature (L. Carbone, et al. “Synthesis and micrometerscale assembly of colloidal CdSe / CdS nanorods prepared by a seeded growth approach ”Nano Lett., 2007, 7 (10), 2942-2950). After synthesis, the QRs are purified and redissolved in toluene to form a 2.5E-08 M / ml solution.
[070] The 2.5E-09 mol CdSe / CdS rods are dissolved, 0.2 mmol above synthesized type I leveling molecules, such as Zn-PDMS, or other commercial organometallic leveling molecules and 0.5 mmol type II, such as (3-Mercaptopropyl) -trimethoxysilane or PDMS terminated in monoamino in 5 ml of ODE. The mixture is heated to 150 ° C in N2 with stirring; 0.05 mmol of dimethylsilylsulfide is injected. The mixture is kept at 150 ° C for 30 min, then cooled to room temperature. The QDs are washed with ethanol and toluene 3 times and redispersed in 3 ml of toluene.
[071] Prepare the QDs-Silicone matrices:
[072] The modified surface QDs are mixed in silicone matrices using two processes.
[073] Process one: The surface modified QDs are directly mixed into the polymeric monomers such as siles in solvents, and then the polymeric mixture of the QDs is kept at curing temperature to give polymer matrices of QDs after removal of the solvent.
[074] Process two: the modified surface nanoparticles are mixed with silicon polymer (components A + B; see below) in solvents such as toluene or chloroform to obtain a clear solution. The solution is transferred into a model vessel. After evaporation of the solvents, the nanoparticle / silicon matrices are maintained at the curing temperature in the air to obtain a solid, transparent film.
[075] Experiment 1
[076] Prepare QDs-silicone polymer matrices as an example of QDs-sylgard PDMS:
[077] Dissolve the modified ZD-PDMS and amino-PDMS QDs in solvents such as toluene or chloroform to form a QDs solution. The PDMS component, which contains PDMS monomers, such as Sylgard 184 (component B) is first added to the solution and stirred to give a clear mixture. Then, the other component, which contains crosslinker and catalyst, such as Sylgard 184 (component A) A is added to the mixture at a desired weight ratio, in the case of Sylgard 184 the ratio is 10%. The clear mixture then dried and cured at a certain temperature, in the case of Sylgard 184, 150 ° C for 30 min to give a transparent matrix of QDs-PDMS.
[078] Experiment 2
[079] Prepare the QDs-silicon polymer matrices as an example of QDs-Silres:
[080] Dissolve the above zinc undecylate and QDs modified with (3-Mercaptopropyl) -trimethoxysilane in solvents such as toluene or chloroform to form a QD solution. Silres monomer, such as Silres 610 is added to the mixture at a desired weight ratio. The clear mixture then dried and cured at a certain temperature, in the case of Silres 610, 200 ° C for 30 min to give a transparent matrix of QDs-Silres.
[081] Experiment 3
[082] Prepare the QDs-silicone polymer matrices as an example of QDs-acrylates:
[083] Dissolve the zinc methacrylate modified QDs in solvents such as toluene or chloroform to form a QD solution. Acrylate monomers, such as methyl methacrylate are then added to the solution. The mixture is then stirred until clear and 1% by weight of the photoinitiator is added and then the mixture is cured under UV irradiation to give a transparent matrix of QDs-acrylates.
[084] Characterizations:
[085] Material characterization:
[086] The components and structures of the QDs-silicone polymer composites could be easily detected. The structure could be characterized using TEM, XRD characterization methods. The components could be characterized by IR, NMR, UV-Vis, PL, ICPMS and XPS for the type, ratio of the elements of the components.
[087] Analysis of thiol, amino or PDMS finished with carboxidecyl or silane is via standard route for commercial product.
[088] Analysis of finished PDMS from Zn-carboxy or Zn-amino or Silane via standard route plus additional IR, NMR analysis for containing Zn and analysis of ICPMS and XPS for containing Zn element in a washed solution.
[089] Characterization of optical property:
[090] Quantum yields are measured on an integration sphere using a YAG phosphor powder (95% QEs) as a standard and UV absorption to use for the absorption and transmission of QDs-PDMS films. An example of the QDs-silicon film has more than 90% transparency between 450 nm and 700 nm and maximum QEs of 90% when 0.3% by weight of QDs in the matrices and 100 µM in thickness.
[091] It appears that under constant illumination, the luminescent material could achieve high photochemical stability with a decay rate from E-8 / s to E-7 / s in air and N2 at 100 ° C. The quantum efficiency of all leveled and embedded nanoparticles was high, as was at least 80%.

权利要求:
Claims (16)
[0001]
1. PROCESS FOR THE PRODUCTION OF A SOLID POLYMER WITH THE LUMINESCENT NANOPARCULES INCORPORATED IN THE POLYMER, characterized by the process comprising the elements of the process: (1) mixing of (i) luminescent nanoparticles with an external surface coated with leveling molecules comprising a first group functional and a second functional group and (ii) a precursor to the solid polymer, and (2) allowing the solid polymer to be formed, thereby producing the solid polymer with embedded nanoparticles; where the first functional group is configured to bond to the outer surface of the quantum dot and where the second functional group has one or more functions selected from the group consisting of (a) being miscible with the solid polymer precursor and (b) being capable of reacting with the solid polymer precursor, in which the leveling molecules comprise two types of leveling molecules, in which the first functional group of the first type of leveling molecules comprises a metal ion which has a coordinating functionality, and wherein the first functional group of the second type of leveling molecules has Lewis-based functionality.
[0002]
PROCESS according to claim 1, characterized by the molar ratio between the first type of leveling molecules and the second type of leveling molecules being in the range of 0.8 to 1.2.
[0003]
PROCESS according to one of claims 1 or 2, characterized in that the second functional group of the first type of leveling molecules and the second functional group of the second type of leveling molecules are the same.
[0004]
4. PROCESS according to any one of claims 1 to 3, characterized in that the solid polymer precursor comprises monomers that are capable of forming the polymer upon polymerization.
[0005]
PROCESS according to any one of claims 1 to 3, characterized in that the precursor of a solid polymer comprises a polymer, and the first element of the process involves (1) mixtures of (i) nanoparticles with the outer surface coated with molecules of leveling comprising the first functional group and the second functional group, (ii) the solid polymer precursor, and (iii) a solvent for the solid polymer precursor.
[0006]
PROCESS according to any one of the preceding claims, characterized in that the second functional group is selected from the group consisting of a siloxane, a styrene, and an acrylate, and that the solid polymer comprises a polymer selected from the group consisting of a polysiloxane, a polystyrene and a polyacrylate, respectively.
[0007]
7. PROCESS, according to any one of the preceding claims, characterized by the nanoparticles being selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSe , ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, and HgZnSeTe HgZnSTe.
[0008]
8.LUMINESCENT POLYMERIC ARTICLE, characterized by comprising a solid polymer with luminescent nanoparticles incorporated in the polymer article with an outer surface coated with leveling molecules comprising a first functional group and a second functional group, in which the leveling molecules comprise two types of leveling molecules, where the first functional group of the first type of leveling molecules comprises a metal ion having a coordinating functionality, and where the first functional group of the second type of leveling molecules has a Lewis base functionality .
[0009]
9. POLYMERIC ARTICLE according to claim 8, characterized in that at least part of the second functional group of at least part of the leveling molecules is interlaced with polymer chains of the solid polymer.
[0010]
POLYMERIC ARTICLE according to any one of claims 8 to 9, characterized in that the second functional group of at least part of the leveling molecules is part of a polymer chain of the solid polymer.
[0011]
11. POLYMERIC ARTICLE according to any one of claims 8 to 10, characterized in that the molar ratio between the first type of leveling molecules and the second type of leveling molecules is in the range of 0.8 to 1.2.
[0012]
POLYMERIC ARTICLE according to any one of claims 8 to 11, characterized in that the second functional group is selected from the group consisting of a siloxane, a styrene, and an acrylate, and wherein the solid polymer comprises a polymer selected from the group consisting of in a polysiloxane, a polystyrene and a polyacrylate, respectively.
[0013]
13. POLYMERIC ARTICLE, according to any one of claims 8 to 12, characterized in that the nanoparticles are selected from the group consisting of CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe and HgZnSTe and by the polymeric article is selected from the group consisting of a coating, a self-supporting layer, and a plate, and the polymeric article is transmissive by light having a wavelength selected from the range of 380 to 750 nm.
[0014]
14.LIGHTING UNIT (5), characterized by comprising (i) a light source (20) configured to generate the light (21) of the light source and (ii) a light converter (40) configured to convert at least part of the light from the converted light source to light (41), wherein the light converter comprises the solid polymer obtainable according to the process according to any one of claims 1 to 7 or the polymeric article, as described in any one of claims 8 to 13.
[0015]
15. LUMINESCENT MATERIAL (30), characterized by comprising a plurality of nanoparticles (100), in which the nanoparticles (100) comprise quantum dot particles (10), comprise external surfaces coated with leveling molecules, in which leveling molecules comprise - [- Si (R) 2-O-] n, with n = 1-20, where R is selected from methyl and phenyl, where leveling molecules comprise two types of leveling molecules, where the first The functional group of the first type of leveling molecules comprises a metal ion that has a coordinating functionality, and in which the first functional group of the second type of leveling molecules has a Lewis base functionality.
[0016]
16. LUMINESCENT MATERIAL (30), according to claim 15, characterized by the molar ratio between the first type of coating molecules and the second type of coating molecules being in the range of 0.8 to 1.2.

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引用文献:

---

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

---

---

US6501091B1|1998-04-01|2002-12-31|Massachusetts Institute Of Technology|Quantum dot white and colored light emitting diodes|

---

US6251303B1|1998-09-18|2001-06-26|Massachusetts Institute Of Technology|Water-soluble fluorescent nanocrystals|

---

JP2002043633A|2000-07-25|2002-02-08|Stanley Electric Co Ltd|White light emitting diode|

---

GB2381530A|2001-11-01|2003-05-07|Oxonica Ltd|Water-soluble particles of luminescent materials and their use in Biotagging|

---

JP2003147090A|2001-11-14|2003-05-21|Mitsubishi Chemicals Corp|Molded article of thermoplastic resin composition including nano particles and method of production for the same|

---

KR100697511B1|2003-10-21|2007-03-20|삼성전자주식회사|Photocurable Semiconductor Nanocrystal, Photocurable Composition for Pattern Formation of Semiconductor Nanocrystal and Method of Patterning Nanocrystal using the same|

---

DE102005061828B4|2005-06-23|2017-05-24|Osram Opto Semiconductors Gmbh|Wavelength-converting converter material, light-emitting optical component and method for its production|

---

US8491818B2|2006-11-27|2013-07-23|Drexel University|Synthesis of water soluble non-toxic nanocrystalline quantum dots and uses thereof|

---

GB0814458D0|2008-08-07|2008-09-10|Nanoco Technologies Ltd|Surface functionalised nanoparticles|

---

RU2381304C1|2008-08-21|2010-02-10|Федеральное государственное унитарное предприятие "Научно-исследовательский институт прикладной акустики"|Method for synthesis of semiconductor quantum dots|

---

KR100982991B1|2008-09-03|2010-09-17|삼성엘이디 주식회사|Quantum dot-wavelength conversion device, preparing method of the same and light-emitting device comprising the same|

---

GB2467161A|2009-01-26|2010-07-28|Sharp Kk|Nitride nanoparticles|

---

EP2424941B1|2009-05-01|2017-05-31|Nanosys, Inc.|Functionalized matrixes for dispersion of nanostructures|

---

JP5158375B2|2009-07-27|2013-03-06|シャープ株式会社|Semiconductor nanoparticle phosphor|

---

GB0916700D0|2009-09-23|2009-11-04|Nanoco Technologies Ltd|Semiconductor nanoparticle-based materials|

---

KR101711085B1|2009-10-09|2017-03-14|삼성전자 주식회사|Nano complex particle, method of manufacturing the same, and device including the nano complex particle|CN104736662B|2012-08-06|2017-07-18|皇家飞利浦有限公司|The method that highly stable QD compounds for solid-state illumination and the polymerization by no initiator make the QD compounds|

---

WO2014064620A1|2012-10-25|2014-05-01|Koninklijke Philips N.V.|Pdms-based ligands for quantum dots in silicones|

---

WO2014064555A1|2012-10-25|2014-05-01|Koninklijke Philips N.V.|Pdms-based ligands for quantum dots in silicones|

---

GB2523645B|2014-01-23|2018-10-17|Nanoco Tech Limited|Quantum dot chip on board LEDs|

---

WO2015140642A2|2014-03-18|2015-09-24|Nanoco Technologies, Ltd|Quantum dot compositions|

---

JP6326003B2|2014-05-19|2018-05-16|富士フイルム株式会社|Wavelength conversion member, backlight unit, liquid crystal display device, and quantum dot-containing polymerizable composition|

---

EP3148712B1|2014-05-29|2021-08-18|Crystalplex Corporation|Dispersion system for quantum dots|

---

WO2016012433A1|2014-07-22|2016-01-28|Koninklijke Philips N.V.|Siloxane ligands to be used for dispersing quantum dots in silicone hosts to obtain color converters for led lighting|

---

KR101993679B1|2015-05-28|2019-06-27|후지필름 가부시키가이샤|A quantum dot-containing composition, a wavelength converting member, a backlight unit, and a liquid crystal display|

---

US11142692B2|2015-07-28|2021-10-12|The Regents Of The University Of California|Capped co-doped core/shell nanocrystals for visible light emission|

---

EP3375838B1|2015-11-12|2021-04-07|FUJIFILM Corporation|Core shell particles, production method for core shell particles, and film|

---

TW201807161A|2016-04-26|2018-03-01|昭榮化學工業股份有限公司|Quantum dot material and method for manufacturing same|

---

KR20190033071A|2016-07-20|2019-03-28|쓰리엠 이노베이티브 프로퍼티즈 컴파니|Stabilized styrene polymers for quantum dots|

---

US10526534B2|2016-12-30|2020-01-07|Unique Materials Co., Ltd.|Composite material, method of manufacturing the same, and application the same|

---

KR20180081002A|2017-01-04|2018-07-13|삼성전자주식회사|Compositions, composites prepared therefrom, and electronic devices including the same|

---

WO2018135434A1|2017-01-18|2018-07-26|三菱マテリアル株式会社|Cd-free colloidal quantum dot capable of emitting visible fluorescence, and method for producing same|

---

JP2018115315A|2017-01-18|2018-07-26|三菱マテリアル株式会社|Cd-FREE COLLOIDAL QUANTUM DOT EMITTING VISIBLE FLORESCENCE AND METHOD FOR PRODUCING THE SAME|

---

US20190044034A1|2017-08-07|2019-02-07|Sabic Global Technologies B.V.|Stable quantum dot extrusion film|

---

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法律状态:
2018-03-06| B25A| Requested transfer of rights approved|Owner name: LUMILEDS HOLDING B.V. (NL) |

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2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-11-10| B09A| Decision: intention to grant|

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2020-12-15| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201261594436P| true| 2012-02-03|2012-02-03|

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US61/594,436|2012-02-03|

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PCT/IB2013/050642|WO2013114254A2|2012-02-03|2013-01-25|Novel materials and methods for dispersing nano particles in matrices with high quantum yields and stability|

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