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  • C09K2113/00—Quantum dots

Definitions

• the present invention relates to a quantum dot composition, a resin composition, and a wavelength conversion material.
• Quantum dots are semiconductor particles with nano-sized particle diameters. Excitons generated by light absorption are confined in nano-sized spaces, making the energy levels of the semiconductor nanoparticles discrete, and the band gap depends on the particle diameter. For this reason, quantum dots emit fluorescent light with high efficiency and have sharp emission spectra. In addition, because the band gap changes depending on the particle diameter, quantum dots have the advantage of being able to control the emission wavelength, and are expected to be used as wavelength conversion materials for solid-state lighting and displays (Patent Document 1).
• Quantum dots that exhibit excellent fluorescent emission properties include those that contain Cd or Pb. However, because Cd and Pb are highly toxic to the human body and the environment, restrictions on their use are being considered around the world, including the European Union's RoHS Directive. For this reason, quantum dots that do not contain these toxic elements are being considered.
• quantum dots are easily destabilized due to their small nanometer particle size, large specific surface area, high surface energy, and surface activity. This makes them susceptible to surface defects due to dangling bonds and oxidation reactions on the quantum dot surface, which causes deterioration of the fluorescent emission properties.
• Currently available quantum dots have such stability problems, and are known to cause deterioration of their emission properties due to heat, humidity, photoexcitation, etc.
• organic ligands called ligands are coordinated to the quantum dot surface after synthesis.
• the coordination of these ligands improves dispersibility in solvents and resins, and by passivating defects, it is possible to suppress deterioration in the fluorescence emission efficiency.
• the ligand may be detached from the quantum dot surface due to external influences such as heat or light exposure, resulting in a deterioration in the fluorescence emission efficiency.
• the stability of quantum dots is an important issue, since changes in the fluorescence efficiency of quantum dots over time can lead to defects such as uneven color and light emission and dead dots when used in displays.
• Patent Document 3 In response to these problems, methods have been considered in which quantum dots are supported on inorganic oxides (Patent Document 3) and methods have been considered in which the stability of quantum dots is improved by using a gas barrier film with low oxygen and moisture permeability (Patent Document 4).
• the method of supporting quantum dots on oxide prevents oxygen and water from coming into direct contact with the quantum dot surface, suppressing the oxidation reaction and thereby preventing deterioration of the fluorescence emission efficiency.
• Stabilization using a barrier film also poses the problem of deterioration due to the diffusion of oxygen and water vapor from the film's edges.
• barrier films are generally around 20 to 200 ⁇ m thick, and in order to protect both sides of the film, the thickness must be at least 40 ⁇ m or more, which places a limit on how thin the wavelength conversion film can be.
• Quantum dots that do not contain toxic elements are being investigated, but degradation of the fluorescence emission efficiency is an issue.
• the present invention has been made to solve the above problems, and aims to provide a quantum dot composition that suppresses the deterioration of fluorescence emission efficiency even when low-toxicity quantum dots are used, a resin composition containing the quantum dot composition, and a wavelength conversion material.
• the present invention has been made to achieve the above object, and provides a quantum dot composition containing quantum dots that emit fluorescence when excited by excitation light, the quantum dots being composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, the quantum dot surface being coated with a metal oxide, and the quantum dot surface or the metal oxide surface being modified with a phosphonic acid derivative.
• Such a quantum dot composition suppresses the deterioration of the fluorescence emission efficiency even when it is composed of quantum dots with low toxicity.
• the quantum dot is composed of the semiconductor nanoparticle core and a single or multiple semiconductor nanoparticle shells covering the semiconductor nanoparticle core.
• Such a quantum dot composition would be preferable in terms of fluorescence emission properties and stability.
• the semiconductor nanoparticle core is selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb , AgGaS2 , AgInS2 , AgGaSe2 , AgInSe2 , CuGaS2 , CuGaSe2, CuInS2 , CuInSe2 , ZnSiP2 , and ZnGeP2 as a single crystal, multiple crystals, or mixed crystals.
• Such a quantum dot composition would be preferable in terms of fluorescence emission properties and stability.
• the semiconductor nanoparticle core surface is composed of GaCl 3 , GaI 3 , GaBr 3 , ZnCl 2 , ZnBr 2 , ZnI 2 , InCl 3 , InBr 3 , InI 3 , AgCl, AgBr, AgI, KCl, KBr, KI, NaCl , NaBr, NaI, MgCl 2 , MgBr 2 , MgI 2 , CaCl 2 , CaBr 2 , CaI 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 2 , FeBr 2 , FeI 2 , CuCl 2 , CuBr 2 , CuI 2 , ZrCl 4 , ZrBr 4 , ZrI 4 , GeCl 4 , GeBr 4 , and GeI 4 .
• Such a quantum dot composition would be preferable in terms of fluorescence emission properties and stability.
• the semiconductor nanoparticle shell is selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb as a single crystal, multiple crystals, or mixed crystals.
• Such a quantum dot composition would be preferable in terms of improving the fluorescence emission efficiency and stability.
• the metal oxide is at least one compound selected from TiO2 , ZnO , Al2O3 , SiO2 , ZrO2 , Fe2O3 , MgO , Y2O3 , HfO2 , CeO2 , In2O3 , SnO2 , WO3 , CrO3 , Ta2O3 , BaTiO3 , V2O5 , NiO , NbO , Cu2O , CuO , and MoO3 .
• Such a quantum dot composition would be preferable in terms of improving the fluorescence emission efficiency and stability.
• the phosphonic acid derivative is preferably represented by the following formula (I).
• R 1 is a monovalent organic group having one or more carbon atoms.
• Such a quantum dot composition suppresses the deterioration of the fluorescence emission efficiency and improves stability.
• the phosphonic acid derivative is 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobenzoic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, heptylphosphonic acid, xylphosphonic acid, 4-phosphonobutyric acid, propylphosphonic acid, (4-aminobenzyl)phosphonic acid, (4-aminophenyl)phosphonic acid, 3-phosphonobenzoic acid, methylphosphonic acid, nonylphosphonic acid, benzhydrylphosphonic acid, octadecylphosphonic acid, (amin
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention, which suppresses deterioration of the fluorescence emission efficiency and improves stability.
• the phosphonic acid derivative is preferably represented by the following formula (II): (In formula (II), R2 is a divalent organic group having one or more carbon atoms.)
• Such a quantum dot composition suppresses the deterioration of the fluorescence emission efficiency and improves stability.
• the phosphonic acid derivative is one or more selected from m-xylylene diphosphonic acid, o-xylylene diphosphonic acid, methylene diphosphonic acid, alendronic acid, 1,4-butylene diphosphonic acid, glycine-N,N-bis(methylenephosphonic acid), p-xylylene diphosphonic acid, zoledronic acid, 1,3-propylene diphosphonic acid, 1,5-pentylene diphosphonic acid, 1,4-phenylene diphosphonic acid, 1,2-ethylene diphosphonic acid, 1,6-hexylene diphosphonic acid, minodronate, and 1-hydroxyethane-1,1-diphosphonic acid.
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• the phosphonic acid derivative is preferably represented by the following formula (III).
• R3 is a trivalent organic group having one or more carbon atoms.
• Such a quantum dot composition suppresses the deterioration of the fluorescence emission efficiency and improves stability.
• the phosphonic acid derivative is nitrilotris(methylene phosphonic acid).
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• the phosphonic acid derivative is preferably represented by the following formula (IV).
• R4 is a divalent organic group having one or more carbon atoms.
• Such a quantum dot composition suppresses the deterioration of the fluorescence emission efficiency and improves stability.
• the phosphonic acid derivative is N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid).
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• R1 contains at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• R2 contains at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• R3 contains at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• R4 contains at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• Such phosphonic acid derivatives can be used in the quantum dot composition of the present invention.
• the present invention also provides a resin composition in which the quantum dot composition described above is dispersed in a resin.
• Such a resin composition is one in which the deterioration of the fluorescent light emission efficiency is suppressed.
• the resin is at least one selected from the group consisting of epoxy resins, acrylic resins, fluorine resins, silicone resins, carbonate resins, and glass resins.
• Such resins can be used in the resin composition of the present invention.
• the present invention also provides a wavelength converting material that contains a cured product of the resin composition described above.
• Such wavelength conversion materials suppress deterioration of the fluorescence emission efficiency and improve reliability.
• the quantum dot composition of the present invention As described above, the quantum dot composition of the present invention, the resin composition containing the quantum dot composition, and the wavelength conversion material suppress deterioration of the fluorescence emission efficiency even when low-toxicity quantum dots are used.
• a quantum dot composition containing quantum dots that emit fluorescence when excited by excitation light the quantum dots being composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, the quantum dot surfaces being coated with a metal oxide, and the quantum dot surfaces or the metal oxide surfaces being modified with a phosphonic acid derivative, can suppress deterioration in fluorescence emission efficiency even when low-toxicity quantum dots are used, and have completed the present invention.
• composition, type, and manufacturing method of the quantum dots, metal oxide, and phosphonic acid derivative are not limited to the following forms.
• the present invention is a quantum dot composition containing quantum dots that emit fluorescence when exposed to excitation light, the quantum dots being composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, the quantum dot surfaces being coated with a metal oxide, and the quantum dot surfaces or the metal oxide surfaces being modified with a phosphonic acid derivative.
• the structure of the quantum dot in the present invention is not particularly limited as long as it is composed of a semiconductor nanoparticle core and a semiconductor nanoparticle shell.
• Such quantum dots have excellent fluorescence emission properties and stability.
• the excitons generated in the shell are confined inside the core particle, improving the fluorescence emission efficiency, and further improving the stability since the core surface is covered with the shell.
• the quantum dots are composed of a semiconductor nanoparticle core and a single or multiple semiconductor nanoparticle shells covering the semiconductor nanoparticle core. With such a quantum dot composition, the deterioration of the fluorescence emission efficiency is further suppressed.
• the material for the semiconductor nanoparticle core of the core/shell semiconductor nanoparticle is not particularly limited as long as it does not contain the elements Cd or Pb from the viewpoint of toxicity, but for example, a material selected from the group consisting of II-VI compounds, III-V compounds, I-III-VI compounds, II-IV-V compounds, and alloys or mixed crystals thereof can be used.
• the material of the semiconductor nanoparticle core may be selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb , AgGaS2 , AgInS2 , AgGaSe2 , AgInSe2, CuGaS2 , CuGaSe2 , CuInS2 , CuInSe2 , ZnSiP2 , and ZnGeP2 in a single, multiple, or mixed crystal form.
• ZnSe, ZnTe, and InP are particularly preferred in terms of fluorescence emission properties and stability.
• the surface of the core particle of the core/shell semiconductor nanoparticles is preferably passivated with an inorganic compound. This inactivates defects on the surface of the core particle, improving the fluorescence emission efficiency and suppressing deterioration of the fluorescence emission efficiency over time.
• the inorganic compound for passivation is not particularly limited, but examples thereof include metal halides, and from the viewpoint of improving the fluorescence emission efficiency, GaCl3 , GaI3 , GaBr3, ZnCl2 , ZnBr2 , ZnI2 , InCl3 , InBr3 , InI3 , AgCl, AgBr , AgI, KCl, KBr, KI, NaCl, NaBr, NaI, MgCl2, MgBr2 , MgI2 , CaCl2 , CaBr2 , CaI2 , MnCl2 , MnBr2 , MnI2 , FeCl2 , FeBr2 , FeI2 , CuCl2 , CuBr2 , CuI2 , ZrCl4 , ZrBr , Particularly preferred is at least one compound selected from ZrI 4 , GeCl 4 , GeBr 4 and GeI 4
• the material for the shell of the semiconductor nanoparticle is not particularly limited as long as it does not contain the elements Cd or Pb from the viewpoint of toxicity, but it is preferable that it has a large band gap and low lattice mismatch with the core material, and can be selected from the group consisting of alloys and mixed crystals of II-VI and III-V compounds.
• Specific shell materials may be selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb, either singly, in multiple, or as mixed crystals. Of these materials, ZnSe and ZnS are particularly preferred in terms of improved fluorescence emission efficiency and stability.
• semiconductor nanoparticles there are various methods for producing semiconductor nanoparticles, such as liquid phase methods and gas phase methods, but the present invention is not particularly limited to these. From the viewpoint of exhibiting high fluorescence emission efficiency, it is preferable to use semiconductor nanoparticles obtained using the hot soap method or hot injection method, in which precursor species are reacted at high temperature in a non-polar solvent with a high boiling point.
• the quantum dots have organic ligands, called ligands, coordinated to their surfaces.
• the quantum dots of the present invention have a surface coated with a metal oxide, which prevents oxygen and water in the air from coming into direct contact with the quantum dot surface and inhibits oxidation reactions, thereby preventing deterioration of the fluorescence emission efficiency.
• the "coating" of the quantum dot surface with metal oxide may be in the form of partial or complete coating, so long as the deterioration of the fluorescence emission efficiency over time is suppressed.
• it may be a uniform coating layer such as a core-shell structure, or a non-uniform coating layer, and may be a structure in which multiple semiconductor nanoparticles are coated with metal oxide.
• the film thickness of the metal oxide is not particularly limited, but is preferably 200 nm or less from the viewpoint of translucency.
• the type of the oxide coating layer is not particularly limited, but may be at least one compound selected from TiO2, ZnO, Al2O3, SiO2, ZrO2, Fe2O3, MgO, Y2O3, HfO2, CeO2, In2O3, SnO2, WO3 , CrO3 , Ta2O3 , BaTiO3 , V2O5 , NiO , NbO , Cu2O , CuO , and MoO3 . From the viewpoint of improving the stability of the quantum dots, TiO2 , Al2O3 , SiO2 , and ZrO2 are more preferable.
• the method for forming the metal oxide coating layer is not particularly limited, but from the viewpoint of selectively progressing the reaction on the quantum dot surface, a method in which a metal oxide precursor is reacted in a liquid phase is preferred.
• one example is a method for forming an oxide coating layer using microwave treatment.
• the metal oxide precursor is heated directly from the inside, allowing the reaction to proceed selectively in a shorter time, forming an oxide layer on the quantum dot surface.
• microwaves generally refer to electromagnetic waves with a frequency of 300 MHz to 3 THz.
• methods for irradiating microwaves include, but are not limited to, a method using flexiWAVE manufactured by Milestone General.
• the surface of the semiconductor nanoparticles with metal oxide by performing a microwave irradiation treatment on the coexisting metal oxide precursor and quantum dots and a metal oxide precursor in the coexistence. This allows the efficient formation of a metal oxide coating layer, and suppresses the deterioration of the fluorescence emission efficiency.
• a polar solvent a non-polar solvent, and an ionic liquid as the dispersion medium for the quantum dots and the metal oxide precursor, and form the coating layer in that solvent.
• a heating element that absorbs microwaves such as Milestone's Weflon, a type of PTFE resin containing carbon components, may be used during the coating process.
• a catalyst to promote the reaction of the metal oxide precursor during the coating process.
• a metal alkoxide it is desirable to use a catalyst to promote the sol-gel reaction.
• catalysts include acidic aqueous solutions and basic aqueous solutions, and basic aqueous solutions are particularly preferable from the viewpoint of the film thickness of the coating layer.
• a surfactant may be added.
• the surfactant is not particularly limited, but examples include quaternary ammonium salts such as cetyltrimethylammonium bromide, which are cationic surfactants; carboxylates and sulfonates, which are anionic surfactants; and polyoxyethylene alkyl ethers and cetyltrimethylammonium bromide, which are nonionic surfactants.
• Cationic surfactants are particularly preferred from the viewpoint of dispersibility of the metal oxide precursor.
• the coating process it is also preferable to carry out the coating process in the presence of alcohol. If coating is carried out in the presence of alcohol, the dispersibility of the metal oxide precursor is better. Also, if a surfactant is added, dispersibility can be further improved by dissolving it in a polar solvent such as alcohol.
• the reaction temperature during microwave irradiation treatment varies depending on the solvent, but is preferably 40 to 200°C, more preferably 50 to 110°C, from the viewpoint of preventing deterioration of the fluorescence emission efficiency.
• microwave treatment is used, but there are no particular limitations as long as the quantum dot surface is "coated" with an oxide layer.
• a metal oxide precursor is reacted in a solution to form a metal oxide coating layer on the surface of the quantum dots, thereby preventing water and oxygen in the air from directly contacting the quantum dot surface and suppressing deterioration of the fluorescence emission efficiency.
• the modifier useful in the present invention and necessary for removing hydroxyl groups on the oxide surface is a phosphonic acid derivative
• the quantum dot composition in this embodiment is composed of the quantum dots, an oxide that covers the quantum dot surface, and a phosphonic acid derivative that modifies the quantum dot surface or the oxide surface.
• Phosphonic acid derivatives are stable compounds in themselves and do not self-polymerize, so they do not precipitate in the bulk and selectively adhere to and modify oxide surfaces or quantum dot surfaces.
• heat treatment at several tens of degrees causes a dehydration condensation reaction between the hydroxyl groups of the metal oxide and the phosphonic acid derivative, which removes the hydroxyl groups on the oxide surface and modifies the oxide surface with the phosphonic acid derivative.
• modification refers to a state in which phosphonic acid is attached to a metal oxide surface or a quantum dot surface.
• the attachment of a phosphonic acid derivative to a surface by “modification” includes partial and full surface attachment, and refers to a state in which the phosphonic acid derivative is attached to at least a part of the surface.
• the term "adhesion” as used above may refer to either physical adsorption or chemical bonding, and may broadly refer to, for example, covalent bonding, ionic bonding, or hydrogen bonding, or may refer to a combination of these.
• the quantum dot composition comprising the quantum dots, the oxide coating layer, and the modification with a phosphonic acid derivative may be in a state in which the organic ligands attached to the metal oxide or quantum dot surface during synthesis coexist with the phosphonic acid derivative.
• the type of phosphonic acid derivative is not particularly limited, but for example, the structure of this compound is preferably at least one of the following formulas (I), (II), (III), and (IV).
• R 1 is a monovalent organic group having one or more carbon atoms.
• R2 is a divalent organic group having one or more carbon atoms.
• R3 is a trivalent organic group having one or more carbon atoms.
• R 1 to R 4 preferably include at least one of a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• the compound represented by formula (I) include 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobenzoic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, acid, hexylphosphonic acid, 4-phosphonobutyric acid, propylphosphonic acid, (4-aminobenzyl)phosphonic acid, (4-aminophenyl)phosphonic acid, 3-phosphonobenzoic acid, methylphosphonic acid, nonylphosphonic acid, benzhydrylphosphonic acid, octadecylphosphonic acid, (aminomethyl)phosphonic
• compounds of formula (II) include m-xylylenediphosphonic acid, o-xylylenediphosphonic acid, methylenediphosphonic acid, alendronic acid, 1,4-butylenediphosphonic acid, glycine-N,N-bis(methylenephosphonic acid), p-xylylenediphosphonic acid, zoledronic acid, 1,3-propylenediphosphonic acid, 1,5-pentylenediphosphonic acid, 1,4-phenylenediphosphonic acid, 1,2-ethylenediphosphonic acid, 1,6-hexylenediphosphonic acid, minodronate, and 1-hydroxyethane-1,1-diphosphonic acid.
• formula (III) examples include nitrilotris(methylene phosphonic acid).
• formula (IV) include N,N,N',N'-ethylenediaminetetrakis(methylenephosphonic acid).
• the heating temperature when modifying the quantum dot surface or metal oxide surface with the above phosphonic acid derivative is not particularly limited, but in order to perform the modification efficiently, the heating temperature is preferably in the range of 50 to 300°C, and more preferably in the range of 80°C to 200°C. Within such a range, the quantum dot surface can be modified more efficiently.
• the amount of the phosphonic acid derivative added as the surface modifier is not particularly limited as long as the phosphonic acid derivative modifies the quantum dot surface or metal oxide surface.
• an amount of 30 wt% or less is preferable because it can suppress aggregation of the quantum dots and precipitation of the phosphonic acid derivative.
• An amount of 0.01 wt% or more can fully exert the effect of modifying the quantum dot surface or metal oxide surface. Therefore, the weight of the surface modifier added is preferably in the range of 0.01 to 30 wt% relative to the solid weight of the quantum dots, and more preferably in the range of 0.05 to 20 wt%.
• Quantum dot composition In a quantum dot composition in which the quantum dot surface is coated with the oxide layer and the quantum dot surface or the oxide layer surface is modified with phosphonic acid, the oxidation reaction on the quantum dot surface is suppressed, thereby suppressing deterioration in the fluorescence emission efficiency and improving stability.
• the quantum dot composition can be used as a resin composition dispersed in a resin.
• the resin material is not particularly limited, but is preferably one in which the quantum dot composition does not aggregate or the fluorescence emission efficiency does not deteriorate, and examples thereof include at least one selected from epoxy resins, acrylic resins, fluorine resins, silicone resins, carbonate resins, and glass resins.
• these resin compositions have high transmittance, and it is particularly preferable that the transmittance be 80% or more.
• the concentration of quantum dots contained in the resin composition is not particularly limited, and can be appropriately adjusted according to the film thickness, the luminous efficiency of the quantum dots, and the characteristics of the desired wavelength conversion material.
• the resin composition may contain substances other than the quantum dot composition, and may contain fine particles of silica, zirconia, alumina, titania, etc. as light scatterers, and may also contain inorganic or organic phosphors.
• inorganic phosphors examples include YAG, LSN, LYSN, CASN, SCASN, KSF, CSO, ⁇ -SIALON, GIAG, LuAG, and SBCA
• organic phosphors include perylene derivatives, anthraquinone derivatives, anthracene derivatives, phthalocyanine derivatives, cyanine derivatives, dioxazine derivatives, benzoxazinone derivatives, coumarin derivatives, quinophthalone derivatives, benzoxazole derivatives, and pyrarizone derivatives.
• the present invention also provides a wavelength converting material containing the cured product of the resin composition.
• the wavelength converting material may be used as it is or may be processed.
• One form of the wavelength converting material is a wavelength conversion film in which the quantum dot composition is dispersed in the resin by processing the material into a sheet and then curing the sheet.
• a resin composition in which a quantum dot composition is dispersed in a resin can be applied to a transparent film such as PET or polyimide, cured, and laminated to obtain the wavelength conversion material.
• the transparent film can be coated using a spraying method such as spray or inkjet, or a spin coat, bar coater, or doctor blade method, and a resin layer is formed by coating.
• a spraying method such as spray or inkjet, or a spin coat, bar coater, or doctor blade method
• a resin layer is formed by coating.
• the thickness of the resin layer and transparent film can be selected appropriately depending on the application.
• Such a wavelength conversion material suppresses deterioration of the fluorescent emission efficiency and improves reliability.
• the fluorescence emission properties of the quantum dots, quantum dot compositions, and wavelength conversion materials were evaluated by measuring the fluorescence emission efficiency (internal quantum efficiency) at an excitation wavelength of 450 nm using a quantum efficiency measurement system (QE-2100) manufactured by Otsuka Electronics Co., Ltd.
• QE-2100 quantum efficiency measurement system manufactured by Otsuka Electronics Co., Ltd.
• the flask was cooled to 200°C, after which 0.10 mL (0.02 mmol) of gallium(III) chloride/octadecene solution was added and heated for 30 minutes to passivate the surface of the InP semiconductor core particles.
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate quantum dots consisting of an InP core, a ZnSe shell, and a ZnS shell, and the supernatant was removed.
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dots and remove the supernatant. Toluene was then added to disperse the quantum dots, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the precipitate was redispersed in toluene to prepare an AgInS 2 /ZnS dispersion.
• the resulting AgInS 2 /ZnS toluene dispersion had a fluorescent emission wavelength peak of 599 nm and an internal quantum efficiency of 68%.
• the AgInS 2 /ZnS dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE CORPORATION) for 12 hours in an air atmosphere, and then the fluorescent emission efficiency was measured, resulting in an internal quantum efficiency of 49%.
• a SiO2 coating layer was formed on the InP/ZnSe/ZnS surface by heating at 60°C for 5 minutes at 2450MHz using a microwave synthesis reaction device (flexi WAVE, manufactured by Milestone General Co., Ltd.). Ethanol was added to the obtained nanoparticles, which were then centrifuged to precipitate and remove the supernatant. Toluene or octadecene was added and the nanoparticles were redispersed by ultrasonic irradiation.
• the resulting InP/ZnSe/ZnS/ SiO2 toluene dispersion had an internal quantum efficiency of 81%.
• the InP/ZnSe/ZnS/ SiO2 toluene dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE CORPORATION) for 12 hours in an air atmosphere, and then the fluorescence emission efficiency was measured. As a result, the internal quantum efficiency was 71%.
• an Al2O3 coating layer was formed on the InP/ZnSe/ZnS surface by heating at 60°C for 5 minutes at 2450MHz using a microwave synthesis reaction device (flexi WAVE, manufactured by Milestone General Co., Ltd.). Ethanol was added to the obtained nanoparticles, which were then precipitated by centrifugation to remove the supernatant, and toluene or octadecene was added and the nanoparticles were redispersed by ultrasonic irradiation.
• the internal quantum efficiency of the obtained InP/ZnSe/ZnS/Al 2 O 3 toluene dispersion was 83%.
• the InP/ZnSe/ZnS/Al 2 O 3 toluene dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE CORPORATION) for 12 hours in an air atmosphere, and then the fluorescence emission efficiency was measured. As a result, the internal quantum efficiency was 72%.
• a ZrO2 coating layer was formed on the InP/ZnSe/ZnS surface by heating at 60°C for 5 minutes at 2450MHz using a microwave synthesis reaction device (flexi WAVE, manufactured by Milestone General Co., Ltd.). Ethanol was added to the obtained nanoparticles, which were then precipitated by centrifugation to remove the supernatant, and toluene or octadecene was added and the nanoparticles were redispersed by ultrasonic irradiation.
• a TiO 2 coating layer was formed on the InP/ZnSe/ZnS surface by heating at 60° C. for 5 minutes at 2450 MHz using a microwave synthesis reaction apparatus (flexi WAVE, manufactured by Milestone General Co.).
• Ethanol was added to the obtained nanoparticles, which were then precipitated by centrifugation to remove the supernatant, and the nanoparticles were redispersed by adding toluene or octadecene and subjecting them to ultrasonic irradiation.
• the internal quantum efficiency of the obtained InP/ZnSe/ZnS/ TiO2 toluene dispersion was 78%.
• the InP/ZnSe/ZnS/ TiO2 toluene dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE CORPORATION) for 12 hours in an air atmosphere, and then the fluorescence emission efficiency was measured. As a result, the internal quantum efficiency was 70%.
• an Al 2 O 3 coating layer was formed on the AgInS 2 /ZnS surface by heating at 60° C. for 5 minutes at 2450 MHz using a microwave synthesis reaction device (flexi WAVE, manufactured by Milestone General Co., Ltd.). Ethanol was added to the obtained nanoparticles, which were then precipitated by centrifugation to remove the supernatant, and toluene or octadecene was added and the nanoparticles were redispersed by ultrasonic irradiation.
• the resulting AgInS 2 /ZnS/Al 2 O 3 toluene dispersion had an internal quantum efficiency of 64%.
• the AgInS 2 /ZnS/Al 2 O 3 toluene dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE CORPORATION) for 12 hours in an air atmosphere, and then the fluorescence emission efficiency was measured.
• the internal quantum efficiency was 54%.
• a ZrO2 coating layer was formed on the AgInS2 /ZnS surface by heating at 60°C for 5 minutes at 2450 MHz using a microwave synthesis reaction device (flexi WAVE, manufactured by Milestone General Co., Ltd.). Ethanol was added to the obtained nanoparticles, which were then precipitated by centrifugation to remove the supernatant, and toluene or octadecene was added and the nanoparticles were redispersed by ultrasonic irradiation.
• the resulting AgInS 2 /ZnS/ZrO 2 toluene dispersion had an internal quantum efficiency of 63%.
• the AgInS 2 /ZnS/ZrO 2 toluene dispersion was irradiated with blue light having a wavelength of 450 nm using a blue LED light source (HL-36, manufactured by AS ONE CORPORATION) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 53%.
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture.
• the flask was then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with HDPA for InP/ZnSe/ZnS/SiO 2.
• the resulting solution was cooled to room temperature, ethanol was added, and the mixture was centrifuged to precipitate the quantum dot composition and remove the supernatant.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 81%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 76%.
• Example 2 In a nitrogen atmosphere, 31 mg of hexadecylphosphonic acid (HDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a hexadecylphosphonic acid solution.
• HDPA hexadecylphosphonic acid
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 82%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 80%.
• Example 3 In a nitrogen atmosphere, 31 mg of hexadecylphosphonic acid (HDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a hexadecylphosphonic acid solution.
• HDPA hexadecylphosphonic acid
• the flask was then purged with nitrogen, heated to 150° C., and stirred for 3 h to obtain a HDPA-modified quantum dot composition for InP/ZnSe/ZnS/ZrO 2 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 82%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 79%.
• Example 4 In a nitrogen atmosphere, 31 mg of hexadecylphosphonic acid (HDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a hexadecylphosphonic acid solution.
• HDPA hexadecylphosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with HDPA for InP/ZnSe/ZnS/TiO 2 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 78%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 77%.
• Example 5 In a nitrogen atmosphere, 31 mg of hexadecylphosphonic acid (HDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a hexadecylphosphonic acid solution.
• HDPA hexadecylphosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with HDPA for AgInS 2 /ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 63%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 61%.
• Example 6 In a nitrogen atmosphere, 31 mg of hexadecylphosphonic acid (HDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a hexadecylphosphonic acid solution.
• HDPA hexadecylphosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with HDPA for AgInS 2 /ZnS/ZrO 2 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 65%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 62%.
• Example 7 In a nitrogen atmosphere, 25 mg of dodecylphosphonic acid (DDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a dodecylphosphonic acid solution.
• DDPA dodecylphosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with DDPA for InP/ZnSe/ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 82%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 79%.
• Example 8 In a nitrogen atmosphere, 22 mg of (4-bromobutyl)phosphonic acid (BBPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a (4-bromobutyl)phosphonic acid solution.
• BBPA (4-bromobutyl)phosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with BBPA for InP/ZnSe/ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 81%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 78%.
• Example 9 In a nitrogen atmosphere, 16 mg of phenylphosphonic acid (PhPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a phenylphosphonic acid (PhPA) solution.
• PhPA phenylphosphonic acid
• the flask was then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a PhPA-modified quantum dot composition for InP/ZnSe/ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 82%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 78%.
• Example 10 In a nitrogen atmosphere, 25 mg of dodecylphosphonic acid (DDPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a dodecylphosphonic acid solution.
• DDPA dodecylphosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with DDPA for AgInS 2 /ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 63%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 60%.
• Example 11 In a nitrogen atmosphere, 22 mg of (4-bromobutyl)phosphonic acid (BBPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a (4-bromobutyl)phosphonic acid solution.
• BBPA (4-bromobutyl)phosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with BBPA for AgInS 2 /ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 61%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 59%.
• Example 12 In a nitrogen atmosphere, 22 mg of phenylphosphonic acid (PhPA) was weighed into a 20 ml vial, and 5 ml of toluene and 1 ml of ethanol were added and stirred to prepare a phenylphosphonic acid solution.
• PhPA phenylphosphonic acid
• the flask was then heated and stirred at 50° C. under reduced pressure for 10 minutes to degas the mixture, then purged with nitrogen, heated to 150° C., and stirred for 3 hours to obtain a quantum dot composition modified with PhPA for AgInS 2 /ZnS/Al 2 O 3 .
• the resulting solution was cooled to room temperature, ethanol was added, and the solution was centrifuged to precipitate the quantum dot composition and remove the supernatant. Toluene was then added to the precipitate to disperse it, ethanol was added again, the solution was centrifuged, the supernatant was removed, and the solution was redispersed in toluene to prepare a toluene dispersion of the quantum dot composition.
• the internal quantum efficiency of the obtained toluene dispersion of the quantum dot composition was 63%.
• the obtained toluene dispersion of the quantum dot composition was irradiated with blue light of 450 nm wavelength using a blue LED light source (HL-36, manufactured by AS ONE Corporation) for 12 hours in an air atmosphere, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 60%.
• Example 13 A wavelength conversion material was produced using the quantum dot composition obtained in Example 1. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength conversion material was 97 ⁇ m.
• the internal quantum efficiency of the obtained wavelength conversion material was 44%.
• the obtained wavelength conversion material was treated for 500 hours under conditions of 85°C and 85% RH (Relative Humidity), after which the fluorescence emission efficiency was measured and the internal quantum efficiency was found to be 41%.
• Example 14 A wavelength conversion material was produced using the quantum dot composition obtained in Example 2. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 47%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 46%.
• Example 15 A wavelength conversion material was produced using the quantum dot composition obtained in Example 3. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 45%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 44%.
• Example 16 A wavelength conversion material was produced using the quantum dot composition obtained in Example 4. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 43%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 41%.
• Example 17 A wavelength conversion material was produced using the quantum dot composition obtained in Example 5. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 98 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 33%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 32%.
• Example 18 A wavelength conversion material was produced using the quantum dot composition obtained in Example 6. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 100 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 32%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 31%.
• Example 19 A wavelength conversion material was produced using the quantum dot composition obtained in Example 7. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 47%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 45%.
• Example 20 A wavelength conversion material was produced using the quantum dot composition obtained in Example 8. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 45%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 43%.
• Example 21 A wavelength conversion material was produced using the quantum dot composition obtained in Example 9. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 98 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 46%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 45%.
• Example 22 A wavelength conversion material was produced using the quantum dot composition obtained in Example 10. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 96 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 33%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 31%.
• Example 23 A wavelength conversion material was produced using the quantum dot composition obtained in Example 11. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 32%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 30%.
• Example 24 A wavelength conversion material was produced using the quantum dot composition obtained in Example 12. 2.5 g of a 20 wt % toluene solution of the quantum dot composition was mixed with 5.0 g of an acrylic resin (Acrydic BL-616-BA, manufactured by DIC Corporation), and the solvent was removed under reduced pressure while being stirred and heated at 60°C.
• an acrylic resin Acrydic BL-616-BA, manufactured by DIC Corporation
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 33%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 30%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 96 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 48%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 27%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 98 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 34%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, after which the fluorescence emission efficiency was measured and the internal quantum efficiency was found to be 20%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 97 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 44%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 33%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 47%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 36%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 97 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 46%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 36%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 99 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 42%.
• the obtained wavelength converting material was treated for 500 hours under conditions of 85°C and 85% RH, and the fluorescence emission efficiency was measured, resulting in an internal quantum efficiency of 34%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 100 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 33%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 23%.
• the mixture was vacuum degassed and applied onto a 50 ⁇ m-thick polyethylene terephthalate (PET) film, and a resin composition layer was formed using a bar coater.
• PET polyethylene terephthalate
• a PET film was then attached onto this resin composition layer for lamination. This film was heated at 60°C for 2 hours and then at 150°C for 4 hours to harden the resin composition layer and produce a wavelength converting material.
• the thickness of the obtained wavelength converting material was 98 ⁇ m.
• the internal quantum efficiency of the obtained wavelength converting material was 32%.
• the fluorescence emission efficiency of the obtained wavelength converting material was measured after it was treated for 500 hours under conditions of 85°C and 85% RH, and the internal quantum efficiency was found to be 24%.
• the internal quantum efficiency values after 500 hours of treatment under conditions of 85°C and 85% RH were compared for the wavelength converting materials produced in Example 13 and Comparative Examples 1 and 3, Examples 14, 19 to 21 and Comparative Examples 1 and 4, Example 15 and Comparative Examples 1 and 5, Example 16 and Comparative Examples 1 and 6, Examples 17, 22 to 24 and Comparative Examples 2 and 7, and Example 18 and Comparative Examples 2 and 8.
• the wavelength converting materials using the quantum dot composition of the present invention which was surface-modified with a metal oxide layer and a phosphonic acid derivative in Examples 13 to 24, showed higher internal quantum efficiency values than quantum dots and quantum dots formed with only a metal oxide layer.
• the quantum dot composition and resin composition using the quantum dot composition produced in the present invention exhibit low degradation in fluorescence emission efficiency under high temperature and high humidity conditions, and are highly reliable, even when low-toxicity quantum dots are used.
• a quantum dot composition comprising quantum dots that emit fluorescence when exposed to excitation light, the quantum dots comprising a semiconductor nanoparticle core and a semiconductor nanoparticle shell that do not contain Cd or Pb, the quantum dot surfaces being coated with a metal oxide, and the quantum dot surfaces or the metal oxide surfaces being modified with a phosphonic acid derivative.
• the semiconductor nanoparticle core is selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb , InN, InP, InAs, InSb, AgGaS2 , AgInS2, AgGaSe2 , AgInSe2
• the semiconductor nanoparticle core surface is made of GaCl 3 , GaI 3 , GaBr 3 , ZnCl 2 , ZnBr 2 , ZnI 2 , InCl 3 , InBr 3 , InI 3 , AgCl, AgBr, AgI, KCl, KBr, KI, NaCl , NaBr, NaI, MgCl 2 , MgBr 2 , MgI 2 , CaCl 2 , CaBr 2 , CaI 2 , MnCl 2 , MnBr 2 , MnI 2 , FeCl 2 , FeBr 2 , FeI 2 , CuCl 2 , CuBr 2 , CuI 2 , ZrCl 4 , ZrBr 4 , ZrI 4 , GeCl 4 , GeBr 4 , and GeI 4.
• [5] The quantum dot composition according to any one of [1] to [4], characterized in that the semiconductor nanoparticle shell is selected from ZnS, ZnSe, ZnTe, AlN, AlP, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InP, InAs, and InSb as a single crystal, a plurality of crystals, or a mixed crystal.
• [6] A quantum dot composition according to any one of [ 1 ] to [ 5 ] above , characterized in that the metal oxide is at least one compound selected from TiO2 , ZnO, Al2O3 , SiO2 , ZrO2 , Fe2O3 , MgO, Y2O3 , HfO2 , CeO2 , In2O3 , SnO2, WO3 , CrO3 , Ta2O3 , BaTiO3, V2O5 , NiO, NbO, Cu2O , CuO, and MoO3 .
• the metal oxide is at least one compound selected from TiO2 , ZnO, Al2O3 , SiO2 , ZrO2 , Fe2O3 , MgO, Y2O3 , HfO2 , CeO2 , In2O3 , SnO2, WO3 , CrO3 , Ta2O3 , BaTiO3, V2O5 ,
• the quantum dot composition according to any one of [1] to [6] above, wherein the phosphonic acid derivative is represented by the following formula (I): (In formula (I), R 1 is a monovalent organic group having one or more carbon atoms.) [8]: The phosphonic acid derivative is 3-phenyl-2-propenylphosphonic acid, tenofovir, 2-phosphonobutane-1,2,4-tricarboxylic acid, 4-phosphonobenzoic acid, vinylphosphonic acid, n-octylphosphonic acid, (3-bromopropyl)phosphonic acid, (4-bromobutyl)phosphonic acid, (2-bromoethyl)phosphonic acid, (4-bromophenyl)phosphonic acid, 3-phosphonopropionic acid, (4-hydroxyphenyl)phosphonic acid, hexylphosphonic acid, acid, 4-phosphonobutyric acid, propylphosphonic acid, (4-aminobenzyl)phosphonic acid,
• [11] The quantum dot composition according to any one of [1] to [6], wherein the phosphonic acid derivative is represented by the following formula (III): (In formula (III), R3 is a trivalent organic group having one or more carbon atoms.)
• R 1 contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• R 3 contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• R 4 contains at least one of the following: a linear or branched alkyl group having one or more carbon atoms, a linear or branched alkylene group having one or more carbon atoms, an amino group, a carboxylic acid group, an ethoxy group, a bromo group, a chloro group, a phenol group, a perfluoroalkyl group, a hydroxyl group, a phenyl group, a thiol group, an acryloyl group, and an oligoethylene glycol group.
• [19] A resin composition comprising the quantum dot composition according to any one of [1] to [18] dispersed in a resin.
• [20] The resin composition according to [19] above, characterized in that the resin is at least one selected from the group consisting of epoxy resins, acrylic resins, fluorine-based resins, silicone resins, carbonate resins, and glass resins.
• the present invention is not limited to the above-described embodiments.
• the above-described embodiments are merely examples, and anything that has substantially the same configuration as the technical idea described in the claims of the present invention and exhibits similar effects is included within the technical scope of the present invention.

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