WO2020241874A1 - 半導体ナノ粒子複合体組成物、希釈組成物、半導体ナノ粒子複合体硬化膜、半導体ナノ粒子複合体パターニング膜、表示素子、および半導体ナノ粒子複合体分散液 - Google Patents

半導体ナノ粒子複合体組成物、希釈組成物、半導体ナノ粒子複合体硬化膜、半導体ナノ粒子複合体パターニング膜、表示素子、および半導体ナノ粒子複合体分散液 Download PDF

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WO2020241874A1
WO2020241874A1 PCT/JP2020/021466 JP2020021466W WO2020241874A1 WO 2020241874 A1 WO2020241874 A1 WO 2020241874A1 JP 2020021466 W JP2020021466 W JP 2020021466W WO 2020241874 A1 WO2020241874 A1 WO 2020241874A1
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Prior art keywords
semiconductor nanoparticle
nanoparticle composite
semiconductor
cured film
ligand
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PCT/JP2020/021466
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English (en)
French (fr)
Japanese (ja)
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信人 城戸
喬史 森山
洋和 佐々木
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Shoei Chemical Inc
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Shoei Chemical Inc
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Priority to CN202410439423.7A priority Critical patent/CN118496840A/zh
Priority to CN202080040146.2A priority patent/CN113939576A/zh
Priority to US17/595,920 priority patent/US20220315833A1/en
Priority to JP2021521905A priority patent/JP7602208B2/ja
Priority to KR1020217039054A priority patent/KR20220016465A/ko
Publication of WO2020241874A1 publication Critical patent/WO2020241874A1/ja
Anticipated expiration legal-status Critical
Priority to US18/923,567 priority patent/US20250051637A1/en
Priority to JP2024205293A priority patent/JP7807729B2/ja
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Definitions

  • the present invention relates to a semiconductor nanoparticle composite composition, a diluted composition, a semiconductor nanoparticle composite cured film, a semiconductor nanoparticle composite patterning film, a display device, and a semiconductor nanoparticle composite dispersion liquid.
  • This application is Japanese Patent Application No. 2019-103243 filed on May 31, 2019, Japanese Patent Application No. 2019-103244 filed on the same day, Japanese Patent Application No. 2019-103245 filed on the same day, and Japanese Patent Application 2019 filed on the same day. -The priority based on No. 103246 is claimed, and all the contents described in the Japanese patent application are incorporated.
  • Semiconductor nanoparticles that are so small that the quantum confinement effect is exhibited have a bandgap that depends on the particle size.
  • Excitons formed in semiconductor nanoparticles by means such as photoexcitation and charge injection emit photons with energy corresponding to the bandgap by recombination, so the composition and particle size of the semiconductor nanoparticles are appropriately selected. This makes it possible to obtain light emission at a desired wavelength.
  • semiconductor nanoparticles were mainly studied for elements including Cd and Pb, but in recent years, since Cd and Pb are regulated substances such as restrictions on the use of specific harmful substances, they are non-Cd and non-Cd. Research on Pb-based semiconductor nanoparticles has been carried out.
  • semiconductor nanoparticles have begun to be formed into films and used as wavelength conversion layers. There is.
  • FIG. 2 shows an outline of a device configuration for converting a wavelength from a light source in a conventional display.
  • a blue LED 101 is used as a light source, and first, the blue light is converted into white light.
  • a QD film 102 formed by dispersing semiconductor nanoparticles in a resin to form a film having a thickness of about 100 ⁇ m is preferably used.
  • the white light obtained by a wavelength conversion layer such as the QD film 102 is further subjected to red light, green light, and green light by the color filter (R) 104, the color filter (G) 105, and the color filter (B) 106, respectively. Converted to blue light.
  • the polarizing plate is omitted.
  • FIG. 1 a display of a type that uses QD patterning as a wavelength conversion layer without using a QD film (deflection plate is not shown) has been developed.
  • QD patterning (7, 8) is used to directly convert blue light to red light or blue light to green light without converting the blue light from the blue LED 1 as a light source into white light. Convert.
  • the QD patterning (7, 8) is formed by patterning the semiconductor nanoparticles dispersed in the resin, and the thickness is about 5 ⁇ m to 10 ⁇ m due to the structural limitation of the display.
  • blue blue light from the blue LED 1 which is a light source is transmitted through a diffusion layer 9 containing a diffusing agent.
  • the QD patterning (7, 8) does not sufficiently absorb the blue light and transmits it, color mixing will occur.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 2002-162501 discloses a thin-film molded body containing semiconductor nanoparticles in a high mass fraction. Since the thin-film molded product described in Patent Document 1 does not necessarily require a polymer matrix component, it is possible to form a thin-film molded product containing semiconductor nanoparticles in a high mass fraction. However, when the thin film-shaped molded product described in Patent Document 1 is used as a wavelength conversion layer for a display or the like, it has become clear that the strength, stability, and solvent resistance of the molded product are insufficient.
  • the semiconductor nanoparticle composite When the semiconductor nanoparticle composite is used for the wavelength conversion layer, a step of forming a film of semiconductor nanoparticles, a step of baking a photoresist containing semiconductor nanoparticles, a step of removing a solvent and a step of curing a resin after inkjet patterning of semiconductor nanoparticles, etc.
  • the semiconductor nanoparticles and the semiconductor nanoparticle composite may be exposed to a high temperature of about 200 ° C. in the presence of oxygen. At that time, the ligand having a weak binding force to the semiconductor nanoparticles is easily detached from the surface of the semiconductor nanoparticles, which causes a decrease in the fluorescence quantum efficiency of the semiconductor nanoparticles composite and the wavelength conversion layer itself.
  • an object of the present invention is to provide a semiconductor nanoparticle composite composition or the like in which the semiconductor nanoparticle composite is dispersed at a high concentration and has high fluorescence quantum efficiency.
  • the semiconductor nanoparticle composite composition according to the present invention is A semiconductor nanoparticle composite composition in which a semiconductor nanoparticle composite is dispersed in a dispersion medium.
  • the semiconductor nanoparticle composite has semiconductor nanoparticles and a ligand coordinated to the surface of the semiconductor nanoparticles.
  • the ligand contains an organic group
  • the dispersion medium is a monomer or prepolymer and is
  • the semiconductor nanoparticle composite composition further contains a cross-linking agent.
  • the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition is 30% by mass or more.
  • a semiconductor nanoparticle composite composition In the present application, the range indicated by "-" is a range including the numbers indicated at both ends thereof.
  • the present invention it is possible to provide a semiconductor nanoparticle composite composition or the like in which the semiconductor nanoparticle composite is dispersed at a high concentration and has high fluorescence quantum efficiency.
  • the semiconductor nanoparticle composite composition and the semiconductor nanoparticle composite dispersion liquid of the present invention are obtained by dispersing the semiconductor nanoparticle composite in a dispersion medium.
  • the semiconductor nanoparticle composite composition has a dispersion medium of a monomer or a prepolymer, further contains a cross-linking agent, and has a mass fraction of semiconductor nanoparticles of 30% by mass or more.
  • the diluted composition of the present invention is obtained by diluting the semiconductor nanoparticle composite composition of the present invention with an organic solvent.
  • the semiconductor nanoparticle composite cured film and the semiconductor nanoparticle composite patterning film of the present invention are obtained by curing or patterning the semiconductor nanoparticle composite composition or the diluted composition of the present invention.
  • the display element of the present invention includes the semiconductor nanoparticle composite patterning film of the present invention.
  • the present invention relates to a semiconductor nanoparticle composite composed of semiconductor nanoparticles and a ligand coordinated to the semiconductor nanoparticles, a semiconductor nanoparticle composite composition in which the semiconductor nanoparticles composite is dispersed, and the like.
  • the semiconductor nanoparticle composite dispersed in the semiconductor nanoparticle composite composition of the present invention has high luminescence characteristics, and the semiconductor nanoparticle composite is a semiconductor nanoparticle composite dispersion liquid, a semiconductor nanoparticle composite composition.
  • Diluted composition, semiconductor nanoparticle composite cured film and semiconductor nanoparticle composite patterning film can be contained in a high mass fraction. Further, the obtained semiconductor nanoparticle composite cured film and the semiconductor nanoparticle composite patterning film have high fluorescence quantum efficiency.
  • the semiconductor nanoparticle composite is a semiconductor nanoparticle composite having light emitting characteristics.
  • the semiconductor nanoparticle composite contained in the semiconductor nanoparticle composite composition and the semiconductor nanoparticle composite dispersion liquid of the present invention is a particle that absorbs light of 340 nm to 480 nm and emits light having an emission peak wavelength of 400 nm to 750 nm. is there.
  • the full width at half maximum (FWHM) of the emission spectrum of the semiconductor nanoparticle composite is preferably 38 nm or less, and more preferably 35 nm or less. When the half width of the emission spectrum is within the above range, it is possible to reduce the color mixing when the semiconductor nanoparticle composite is applied to a display or the like.
  • the fluorescence quantum efficiency (QY) of the semiconductor nanoparticle composite is preferably 80% or more, and more preferably 85% or more. When the fluorescence quantum efficiency of the semiconductor nanoparticle composite is 80% or more, color conversion can be performed more efficiently. In the present invention, the fluorescence quantum efficiency of the semiconductor nanoparticle composite can be measured using a quantum efficiency measuring system.
  • the semiconductor nanoparticles constituting the semiconductor nanoparticles composite are not particularly limited as long as they satisfy the above-mentioned fluorescence quantum efficiency and light emission characteristics such as half-price width, and may be particles made of one type of semiconductor. It may be a particle composed of two or more different semiconductors. In the case of particles composed of two or more different semiconductors, the core-shell structure may be composed of those semiconductors. For example, it may be a core-shell type particle having a core containing a group III element and a group V element and a shell containing a group II and a group VI element covering at least a part of the core.
  • the shell may have a plurality of shells having different compositions, or may have one or more gradient-type shells in which the ratio of the elements constituting the shell changes in the shell.
  • Group III element examples include In, Al and Ga.
  • Group V element examples include P, N and As.
  • the composition for forming the core is not particularly limited, but InP is preferable from the viewpoint of light emission characteristics.
  • the group II element is not particularly limited, and examples thereof include Zn and Mg.
  • Group VI elements include, for example, S, Se, Te and O.
  • the composition for forming the shell is not particularly limited, but from the viewpoint of the quantum confinement effect, ZnS, ZnSe, ZnSeS, ZnTeS, ZnTeSe and the like are preferable. In particular, when the Zn element is present on the surface of the semiconductor nanoparticles, the effect of the present invention can be more exerted.
  • At least one shell having the above-mentioned composition may be included.
  • the shell has a gradient type shell in which the ratio of the elements constituting the shell changes, the shell does not necessarily have to have the composition according to the composition notation.
  • whether or not the shell covers at least a part of the core and the element distribution inside the shell use, for example, energy dispersive X-ray spectroscopy (TEM-EDX) using a transmission electron microscope. It can be confirmed by composition analysis and analysis.
  • TEM-EDX energy dispersive X-ray spectroscopy
  • the average particle size of the semiconductor nanoparticle composite is preferably 10 nm or less. Further, it is more preferably 7 nm or less.
  • the average particle size of the semiconductor nanoparticle composite is calculated by calculating the particle size of 10 or more particles by the area equivalent diameter (Heywood diameter) in the particle image observed using a transmission electron microscope (TEM). It can be measured by doing. From the viewpoint of light emission characteristics, the particle size distribution is preferably narrow, and the coefficient of variation of the particle size is preferably 15% or less.
  • a core of semiconductor nanoparticles can be formed by heating a precursor mixture obtained by mixing a group III precursor, a group V precursor, and, if necessary, an additive in a solvent.
  • Solvents include, but are not limited to, 1-octadecene, hexadecane, squalene, oleylamine, trioctylphosphine oxide, and trioctylphosphine oxide.
  • Examples of the group III precursor include, but are not limited to, acetates, carboxylates, halides and the like containing the group III.
  • Examples of the group V precursor include, but are not limited to, the organic compounds and gases containing the group V element.
  • the precursor is a gas
  • a core can be formed by reacting while injecting a gas into a precursor mixture containing a mixture other than the gas.
  • the semiconductor nanoparticles may contain one or more elements other than group III and group V as long as the effects of the present invention are not impaired.
  • a precursor of the elements may be added at the time of core formation.
  • the additive include, but are not limited to, carboxylic acids, amines, thiols, phosphines, phosphine oxides, phosphinic acids, and phosphonic acids as dispersants.
  • the dispersant can also serve as a solvent.
  • a halide is added to improve the light emitting characteristics of the semiconductor nanoparticles.
  • the In precursor and, if necessary, a metal precursor solution with a dispersant added to the solvent are mixed under vacuum, once heated at 100 ° C. to 300 ° C. for 6 to 24 hours, and then further.
  • the P precursor is added and heated at 200 ° C. to 400 ° C. for 3 to 60 minutes and then cooled.
  • a halogen precursor and heat-treating at 25 ° C. to 300 ° C., preferably 100 ° C. to 300 ° C., more preferably 150 ° C. to 280 ° C., a core particle dispersion containing core particles can be obtained. ..
  • the semiconductor nanoparticles By adding the shell-forming precursor to the core particle dispersion synthesized as described above, the semiconductor nanoparticles have a core-shell structure, and the fluorescence quantum efficiency (QY) and stability can be enhanced.
  • the elements that make up the shell are thought to have a structure such as an alloy, heterostructure, or amorphous structure on the surface of the core particles, but it is also possible that some of them have moved to the inside of the core particles due to diffusion.
  • the added shell-forming element mainly exists near the surface of the core particles and has a role of protecting the semiconductor nanoparticles from external factors.
  • the shell covers at least a part of the core, and more preferably the entire surface of the core particles is uniformly covered.
  • the Zn precursor and the Se precursor are added to the above-mentioned core particle dispersion and then heated at 150 ° C. to 300 ° C., preferably 180 ° C. to 250 ° C., and then the Zn precursor and the S precursor are added. , 200 ° C. to 400 ° C., preferably 250 ° C. to 350 ° C.
  • the Zn precursor includes carboxylates such as zinc acetate, zinc propionate and zinc myristate, halides such as zinc chloride and zinc bromide, and organic substances such as diethylzinc. Salt or the like can be used.
  • phosphine serenides such as tributylphosphine serenide, trioctylphosphine serenide and tris (trimethylsilyl) phosphine serenide, selenols such as benzenelenol and selenocysteine, and a selenium / octadecene solution are used. can do.
  • phosphine sulfides such as tributylphosphine sulfide, trioctylphosphine sulfide and tris (trimethylsilyl) phosphine sulfide, thiols such as octanethiol, dodecanethiol and octadecanethiol, and sulfur / octadecene solutions should be used.
  • the shell precursors may be premixed and added once or in multiple doses, or separately, once or in multiple doses. When the shell precursor is added in a plurality of times, the temperature may be changed and heated after each shell precursor is added.
  • the method for producing semiconductor nanoparticles is not particularly limited, and in addition to the methods shown above, conventional methods such as a hot injection method, a uniform solvent method, a reverse micelle method, and a CVD method can be used. , Any method may be adopted.
  • the semiconductor nanoparticle composite is one in which a ligand is coordinated on the surface of the semiconductor nanoparticles.
  • the coordination described here means that the ligand chemically affects the surface of the semiconductor nanoparticles. It may be coordinated to the surface of the semiconductor nanoparticles or in any other bonding mode (eg, covalent bond, ionic bond, hydrogen bond, etc.) or coordinated to at least a portion of the surface of the semiconductor nanoparticles. If it has children, it does not necessarily have to form a bond.
  • the semiconductor nanoparticle composite composition, the semiconductor nanoparticle composite cured film, and the semiconductor nanoparticle composite that can be contained in a high mass fraction during patterning preferably satisfy the following.
  • the mass ratio of the ligand to the semiconductor nanoparticles is preferably 0.05 to 0.50, more preferably 0.10 to 0.40, assuming that the semiconductor nanoparticles are 1.
  • the mass ratio of the ligand to the semiconductor nanoparticles (ligand / semiconductor nanoparticles) is 0.50 or less, it is possible to suppress an increase in the size and volume of the semiconductor nanoparticles composite, and the semiconductor nanoparticles composite composition and It can be contained in the cured film of the semiconductor nanoparticle composite in a high mass fraction.
  • the mass ratio (ligand / semiconductor nanoparticles) is 0.05 or more, the ligand can sufficiently cover the semiconductor nanoparticles, the emission characteristics of the semiconductor nanoparticles are deteriorated, and the cured film or dispersion medium. It is possible to suppress a decrease in dispersibility to.
  • the fluorescence quantum efficiency of the semiconductor nanoparticle composite composition and the semiconductor nanoparticle composite cured film is preferably 60% or more, more preferably 70% or more.
  • the ligand is an organic ligand containing an organic group. Further, the ligand preferably comprises a coordinating group that coordinates with the semiconductor nanoparticles and an organic group.
  • the organic group is preferably a monovalent hydrocarbon group which may have a substituent or a heteroatom, and more preferably an organic group in which a substituent containing a heteroatom is bonded to a vinyl group.
  • the organic group is not particularly limited, but includes an alkyl group, an alkenyl group, an alkynyl group, a vinylene group, a vinylidene group, an ether group, an ester group, a carbonyl group, an amide group, a sulfide group, and an organic group formed by combining these. Can be mentioned. Further, the organic group can include a phenyl group, a hydroxyl group, an alkoxy group, an amino group, a carboxyl group, a mercapto group, a chloro group, a bromo group, a vinyl group, an acrylic group, a methacryl group and the like as substituents.
  • the organic group preferably has one or more groups selected from an ether group, an ester group and an amide group.
  • an organic dispersion medium having an SP value (solubility parameter) of 8.5 to 15.0.
  • the organic group has a vinyl group and / or a vinylene group.
  • the semiconductor nanoparticle composite and the curable composition can be chemically bonded, and the strength of the film and the stability of the semiconductor nanoparticles in the film are improved.
  • the substituent containing a vinyl group is not particularly limited, and examples thereof include an acrylic group and a methacrylic group.
  • the coordinating group is preferably a mercapto group or a carboxyl group, and particularly preferably a mercapto group, from the viewpoint of the strength of coordination to the semiconductor nanoparticles.
  • the number of mercapto groups is preferably one or more.
  • the molecular weight of the ligand is preferably 50 or more and 600 or less, and more preferably 50 or more and 450 or less.
  • the molecular weight of each ligand is preferably 50 or more and 600 or less, and more preferably 50 or more and 450 or less.
  • the surface of the semiconductor nanoparticles can be sufficiently covered with the ligand, so that deterioration of the light emitting property of the semiconductor nanoparticles complex can be suppressed, and curing is possible. Dispersibility in a film or a dispersion medium can be improved.
  • the ligand has two or more coordinating groups per molecule.
  • the number of coordinating groups of the ligand is two or more per molecule of the ligand, one molecule of the ligand can coordinate to a plurality of locations on the surface of the semiconductor nanoparticles, so that the size and volume of the semiconductor nanoparticles complex can be arranged. Can be suppressed, and dispersibility in a dispersion medium or a cured film can be improved.
  • a mercapto group is preferable as the coordinating group of the ligand.
  • the mercapto group of the ligand strongly coordinates with the shell of the semiconductor nanoparticles, fills the defective portion of the semiconductor nanoparticles, and contributes to prevent deterioration of the light emitting property of the semiconductor nanoparticles complex.
  • Zn is present on the surface of the semiconductor nanoparticles, the above-mentioned effect can be further obtained due to the strength of the bonding force between the mercapto group and Zn.
  • the method of coordinating the ligand to the semiconductor nanoparticles is not limited, but a ligand exchange method utilizing the coordinating force of the ligand can be used.
  • the semiconductor nanoparticles in which the organic compound used in the process of producing the semiconductor nanoparticles described above is coordinated with the surface of the semiconductor nanoparticles are brought into contact with the target ligand in a liquid phase.
  • a semiconductor nanoparticle complex in which the target ligand is coordinated on the surface of the semiconductor nanoparticles can be obtained.
  • a liquid phase reaction using a solvent as described later is usually carried out, but when the ligand to be used is a liquid under the reaction conditions, the ligand itself is used as a solvent and another solvent is not added. Is also possible.
  • the purification step and the redispersion step as described later are performed before the ligand exchange, the ligand exchange can be easily performed.
  • the semiconductor nanoparticle-containing dispersion after the semiconductor nanoparticles are produced is purified, redispersed, and then a solvent containing the target ligand is added, and the temperature is 50 ° C. to 200 ° C. for 1 minute in a nitrogen atmosphere.
  • the desired semiconductor nanoparticle composite can be obtained by stirring for about 120 minutes.
  • the semiconductor nanoparticles and the semiconductor nanoparticle composite can be purified as follows.
  • the semiconductor nanoparticle composite can be precipitated from the dispersion by adding a polarity conversion solvent such as acetone.
  • the precipitated semiconductor nanoparticle composite can be recovered by filtration or centrifugation, while the supernatant containing unreacted starting material and other impurities can be discarded or reused.
  • the precipitated semiconductor nanoparticle composite can then be washed with a further dispersion medium and dispersed again. This purification process can be repeated, for example, 2-4 times, or until the desired purity is reached.
  • the method for purifying the semiconductor nanoparticle composite is not particularly limited, and in addition to the methods shown above, for example, aggregation, liquid-liquid extraction, distillation, electrodeposition, size exclusion chromatography and / or ultrafiltration, etc. Any method can be used alone or in combination.
  • the optical properties of semiconductor nanoparticles can be measured using a quantum efficiency measurement system (for example, Otsuka Electronics Co., Ltd., QE-2100).
  • the obtained semiconductor nanoparticles are dispersed in a dispersion medium, excited light is applied to obtain an emission spectrum, and the re-excitation fluorescence emission spectrum excluding the re-excitation fluorescence emission spectrum obtained by re-excitation and fluorescence emission is obtained from the emission spectrum obtained here.
  • the fluorescence quantum efficiency (QY) and half-price range (FWHM) are calculated from the later emission spectrum.
  • the dispersion medium used for the measurement include normal hexane, toluene, acetone, PGMEA and octadecene.
  • the state in which the semiconductor nanoparticle composite is dispersed in the dispersion medium means that the semiconductor nanoparticle composite does not precipitate when the semiconductor nanoparticle composite and the dispersion medium are mixed, or is visually recognizable. Indicates that the state does not remain as turbidity (cloudiness).
  • a dispersion in which the semiconductor nanoparticle composite is dispersed in a dispersion medium is referred to as a dispersion liquid.
  • the semiconductor nanoparticle composite composition of the present invention and the semiconductor nanoparticle composite contained in the semiconductor nanoparticle composite dispersion liquid have the above-mentioned constitution, and have an SP value (solubility parameter) of 8.5 to 15 as a dispersion medium.
  • the dispersion medium are not particularly limited, but are limited to alcohols such as methanol, ethanol, isopropyl alcohol and normal propyl alcohol, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, and acetic acid.
  • Esters such as methyl, ethyl acetate, isopropyl acetate, normal propyl acetate, normal butyl acetate and ethyl lactate, ethers such as diethyl ether, dipropyl ether, dibutyl ether and tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Diethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether And glycol ethers such as dipropylene glycol diethyl ether, and ethylene glycol acetate, ethylene glycol monoethy
  • glycol ether esters such as ether acetate.
  • the semiconductor nanoparticle composite can be dispersed in any one or more dispersion media selected from the above dispersion media. Further, as described in the above examples, it is also possible to select a dispersion medium having polarity such as alcohols, ketones, esters, glycol ethers and glycol ether esters. By dispersing the semiconductor nanoparticle composite in these dispersion media, it can be used while maintaining the dispersibility of the semiconductor nanoparticle composite when applied to dispersion in a cured film or resin described later.
  • glycol ethers or glycol ether esters are preferable from the viewpoint of solubility in a wide range of resins and film uniformity at the time of coating film.
  • PGMEA and PGME are generally used as diluting solvents, and if the semiconductor nanoparticles can be dispersed in PGMEA and PGME, the semiconductor nanoparticles can be widely applied to the photoresist field.
  • the SP value here is a Hildebrand solubility parameter, which is a value calculated from the Hansen solubility parameter.
  • the Hansen solubility parameter is described in the handbook, eg, "Hansen Solubility Parameters: A User's Handbook", 2nd Edition, C.I. M. The values in Hanson (2007), Hanson and Abbot et al. It can be determined using the Practice (HSPiP) program (2nd edition) provided by.
  • the concentration of the inorganic component of the semiconductor nanoparticle composite in the semiconductor nanoparticle composite dispersion is 1 mg / mL, that is, the inorganic of the semiconductor nanoparticle composite per 1 mL of the dispersion medium of the semiconductor nanoparticle composite dispersion.
  • the absorbance of the semiconductor nanoparticle composite dispersion may be 0.6 or more with an optical path length of 1 cm and 0.7 or more with respect to light having a wavelength of 450 nm. preferable.
  • the absorbance of the dispersion liquid is 0.6 or more with an optical path length of 1 cm, it is possible to absorb more light with a small amount of liquid when applied to a device or the like.
  • the semiconductor nanoparticle composite described above includes the semiconductor nanoparticle composite composition, the diluted composition, the semiconductor nanoparticle composite cured film, the semiconductor nanoparticle composite patterning film, the display element, and the semiconductor nanoparticle composite of the present invention. It is suitable as a semiconductor nanoparticle composite contained in a body dispersion.
  • a monomer or a prepolymer can be selected as the dispersion medium of the semiconductor nanoparticle composite dispersion liquid. Further, by adding a cross-linking agent, the semiconductor nanoparticle composite contained in the semiconductor nanoparticle composite composition of the present invention forms a semiconductor nanoparticle composite composition with a monomer or a prepolymer and a cross-linking agent. be able to.
  • the monomer is not particularly limited, but a (meth) acrylic monomer that can be widely selected for application of semiconductor nanoparticles is preferable.
  • the (meth) acrylic monomer is isobornyl acrylate (IBOA), methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, depending on the application of the semiconductor nanoparticle composite dispersion.
  • the prepolymer is not particularly limited, but (meth) acrylic resin prepolymer, silicone resin prepolymer, epoxy resin prepolymer, maleic acid resin prepolymer, butyral resin prepolymer, polyester resin prepolymer, melamine resin prepolymer, phenol resin prepolymer. Examples thereof include polymers and polyurethane resin prepolymers.
  • the cross-linking agent depends on the type of monomer in the semiconductor nanoparticle composite composition: polyfunctional (meth) acrylate, polyfunctional silane compound, polyfunctional amine, polyfunctional carboxylic acid, polyfunctional thiol, polyfunctional alcohol, and polyfunctional isocyanate. It is selected from.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane, isohexane, heptane, octane and petroleum ether, alcohols, ketones, esters, glycol ethers and glycol ethers are added. It can further contain various organic solvents that do not affect curing, such as esters, aromatic hydrocarbons such as benzene, toluene, xylene and mineral spirits, and alkyl halides such as dichloromethane and chloroform.
  • the semiconductor nanoparticle composite composition contains an organic solvent, the content of the organic solvent is such that the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition is 30% or more. It should be.
  • the semiconductor nanoparticle composite composition may be an appropriate initiator, scatterer, catalyst, binder, surfactant, adhesion accelerator, antioxidant, ultraviolet ray, depending on the type of monomer in the semiconductor nanoparticle composite composition. It may contain an absorbent, an anti-aggregation agent, a dispersant and the like. Further, in order to improve the optical properties of the semiconductor nanoparticle composite composition or the semiconductor nanoparticle composite cured film described later, the semiconductor nanoparticle composite composition may contain a scattering agent.
  • the scattering agent is a metal oxide such as titanium oxide or zinc oxide, and the particle size of these is preferably 100 nm to 500 nm. From the viewpoint of the effect of scattering, the particle size of the scattering agent is more preferably 200 nm to 400 nm.
  • the content of the scattering agent is preferably 2% by mass to 30% by mass with respect to the composition, and more preferably 5% by mass to 20% by mass from the viewpoint of maintaining the pattern property of the composition.
  • the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition can be set to 30% by mass or more.
  • the semiconductor nanoparticles composite and the semiconductor nanoparticles also have a high mass fraction in the cured film described later. Can be dispersed.
  • the absorbance of the film with respect to light having a wavelength of 450 nm from the normal direction is preferably 1.0 or more, preferably 1.3 or more. More preferably, it is more preferably 1.5 or more. As a result, the light from the backlight can be efficiently absorbed, so that the thickness of the cured film described later can be reduced, and the device to be applied can be miniaturized.
  • the diluted composition of the present invention is obtained by diluting the above-mentioned semiconductor nanoparticle composite composition of the present invention with an organic solvent.
  • the organic solvent for diluting the semiconductor nanoparticle composite composition is not particularly limited, and for example, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, isohexane, heptane, octane and petroleum ether, alcohols and ketones. Classes, esters, glycol ethers, glycol ether esters, aromatic hydrocarbons such as benzene, toluene, xylene and mineral spirits, alkyl halides such as dichloromethane and chloroform and the like.
  • glycol ethers and glycol ether esters are preferable from the viewpoint of solubility in a wide range of resins and film uniformity at the time of coating film.
  • a semiconductor nanoparticle composite composition having a mass fraction of semiconductor nanoparticles of 30% or more can be obtained.
  • the semiconductor nanoparticle composite cured film is a film containing a semiconductor nanoparticle composite and represents a cured film.
  • the semiconductor nanoparticle composite cured film can be obtained by curing the above-mentioned semiconductor nanoparticle composite composition or diluted composition into a film.
  • the semiconductor nanoparticle composite cured film contains a semiconductor nanoparticle, a ligand coordinated on the surface of the semiconductor nanoparticle, a polymer matrix, and a cross-linking agent.
  • the polymer matrix is not particularly limited, and examples thereof include (meth) acrylic resin, silicone resin, epoxy resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, and polyurethane resin.
  • a semiconductor nanoparticle composite cured film may be obtained by curing the semiconductor nanoparticle composite composition described above.
  • the method for curing the film is not particularly limited, but the film can be cured by a curing method suitable for the composition constituting the film, such as heat treatment and ultraviolet treatment.
  • Semiconductor nanoparticle composite The ligand contained in the cured film and coordinated to the surface of the semiconductor nanoparticles and the semiconductor nanoparticles preferably constitutes the semiconductor nanoparticle composite described above.
  • the semiconductor nanoparticle composite can be dispersed in the cured film at a higher mass fraction. It is possible.
  • the mass fraction of the semiconductor nanoparticles in the cured film of the semiconductor nanoparticle composite may be 30% by mass or more, and more preferably 40% by mass or more.
  • the semiconductor nanoparticle composite cured film of the present invention has a very high absorbance of light having a wavelength of 450 nm. Become. Therefore, the semiconductor nanoparticle composite cured film of the present invention will be described later even if the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite cured film is less than 70% by mass and further less than 60% by mass. It can have a sufficient value of absorbance.
  • the absorbance of the semiconductor nanoparticle composite cured film of the present invention can be increased.
  • the absorbance is preferably 1.0 or more, preferably 1.3 or more, with respect to light having a wavelength of 450 nm from the normal direction of the semiconductor nanoparticle composite cured film. More preferably, it is more preferably 1.5 or more.
  • the semiconductor nanoparticle composite cured film of the present invention contains a semiconductor nanoparticle composite having high light emitting characteristics, it is possible to provide a semiconductor nanoparticle composite cured film having high light emitting characteristics.
  • the fluorescence quantum efficiency of the cured film of the semiconductor nanoparticle composite is preferably 70% or more, and more preferably 80% or more.
  • the thickness of the semiconductor nanoparticle composite cured film is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and more preferably 10 ⁇ m or less in order to miniaturize the device to which the semiconductor nanoparticle composite cured film is applied. Is even more preferable.
  • the semiconductor nanoparticle composite patterning film of the present invention can be obtained by forming a film-like pattern of the above-mentioned semiconductor nanoparticle composite composition or dilution composition.
  • the method for patterning the semiconductor nanoparticle composite composition and the diluted composition is not particularly limited, and examples thereof include spin coating, bar coating, inkjet, screen printing, and photolithography.
  • the display element of the present invention uses the above-mentioned semiconductor nanoparticle composite patterning film of the present invention. For example, by using a semiconductor nanoparticle composite patterning film as a wavelength conversion layer, it is possible to provide a display element having excellent fluorescence quantum efficiency.
  • the semiconductor nanoparticle composite composition of the present invention adopts the following constitution.
  • a semiconductor nanoparticle composite composition in which a semiconductor nanoparticle composite is dispersed in a dispersion medium.
  • the semiconductor nanoparticle composite has semiconductor nanoparticles and a ligand coordinated to the surface of the semiconductor nanoparticles.
  • the ligand contains an organic group
  • the dispersion medium is a monomer or prepolymer and is
  • the semiconductor nanoparticle composite composition further contains a cross-linking agent.
  • the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition is 30% by mass or more.
  • Semiconductor nanoparticle composite composition The mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition is 40% by mass or more.
  • the absorbance of the film with respect to light having a wavelength of 450 nm from the normal direction of the film is 1.0 or more.
  • the mass ratio of the ligand to the semiconductor nanoparticles (ligand / semiconductor nanoparticles) is 0.05 to 0.50.
  • the mass ratio of the ligand to the semiconductor nanoparticles (ligand / semiconductor nanoparticles) is 0.10 to 0.40.
  • the ligand contains a hydrocarbon group which may have a substituent or a hetero atom, and a coordinating group.
  • the ligand has one or more groups selected from an ether group, an ester group and an amide group.
  • the ligand further contains a coordinating group.
  • the organic group has a vinyl group and / or a vinylidene group.
  • the average particle size of the semiconductor nanoparticles is 10 nm or less.
  • the average particle size of the semiconductor nanoparticles is 7 nm or less.
  • the fluorescence quantum efficiency of the semiconductor nanoparticle composite composition is 60% or more.
  • the fluorescence quantum efficiency of the semiconductor nanoparticle composite composition is 70% or more.
  • the molecular weight of the ligand is 50 or more and 600 or less.
  • the molecular weight of the ligand is 50 or more and 450 or less.
  • the ligand has one or more mercapto groups.
  • the ligand has two or more mercapto groups.
  • the semiconductor nanoparticles contain In and P.
  • the semiconductor nanoparticle composite composition according to any one of (1) to (17) above. (19) Zn is contained on the surface of the semiconductor nanoparticles.
  • the fluorescence quantum efficiency of the semiconductor nanoparticle composite is 80% or more.
  • the half width of the emission spectrum of the semiconductor nanoparticle composite is 38 nm or less.
  • the diluted composition of the present invention adopts the following constitution.
  • (22) A diluted composition obtained by diluting the semiconductor nanoparticle composite composition according to any one of (1) to (21) above with an organic solvent.
  • (23) The diluted composition according to (22) above, wherein the organic solvent is glycol ethers and / or glycol ether esters.
  • the semiconductor nanoparticle composite cured film of the present invention adopts the following constitution.
  • (24) A semiconductor nanoparticle composite obtained by curing the semiconductor nanoparticle composite composition according to any one of (1) to (21) above, or the diluted composition according to (22) or (23) above. Body hardening film.
  • the semiconductor nanoparticle composite patterning film of the present invention adopts the following structure. (25) Semiconductor nanoparticles obtained by patterning the semiconductor nanoparticle composite composition according to any one of (1) to (21) above or the diluted composition according to (22) or (23) above. Composite patterning film.
  • the display element of the present invention adopts the following configuration.
  • (26) A display device including the semiconductor nanoparticle composite patterning film according to (25) above.
  • the semiconductor nanoparticle composite dispersion liquid of the present invention adopts the following constitution.
  • a dispersion in which a semiconductor nanoparticle composite in which a ligand is coordinated on the surface of semiconductor nanoparticles is dispersed in a dispersion medium.
  • concentration of the inorganic component of the semiconductor nanoparticle composite in the dispersion is 1 mg / mL
  • the absorbance at an optical path length of 1 cm is 0.6 or more with respect to light having a wavelength of 450 nm.
  • the ligand contains an organic group, Semiconductor nanoparticle composite dispersion.
  • the SP value of the dispersion medium is 8.5 or more.
  • the SP value of the dispersion medium is 9.0 or more.
  • the dispersion medium is one or a mixed dispersion medium selected from glycol ethers and glycol ether esters.
  • the dispersion medium is PGMEA or PGME.
  • the mass ratio of the ligand to the semiconductor nanoparticles (ligand / semiconductor nanoparticles) is 0.05 to 0.50.
  • the ligand contains a hydrocarbon group which may have a substituent or a hetero atom, and a coordinating group.
  • the molecular weight of the ligand is 50 or more and 600 or less.
  • ⁇ 12> The molecular weight of the ligand is 50 or more and 450 or less.
  • the ligand has at least one or more mercapto groups.
  • the ligand further contains a coordinating group.
  • the organic group has one or more groups selected from ether groups, ester groups and amide groups.
  • the ligand further contains a coordinating group and contains.
  • the organic group has a vinyl group and / or a vinylidene group.
  • the ligand has two or more mercapto groups.
  • the ligand is two or more kinds, The nanoparticle complex dispersion liquid according to any one of ⁇ 1> to ⁇ 16> above.
  • ⁇ 18> Zn is contained in the surface of the semiconductor nanoparticles.
  • the semiconductor nanoparticles contain In and P.
  • ⁇ 20> The fluorescence quantum efficiency of the semiconductor nanoparticle composite is 80% or more.
  • the semiconductor nanoparticle composite cured film of the present invention adopts the following constitution.
  • the semiconductor nanoparticle composite has semiconductor nanoparticles and a ligand coordinated to the surface of the semiconductor nanoparticles.
  • the ligand contains an organic group
  • the polymer matrix is crosslinked by a crosslinking agent and is crosslinked.
  • the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite cured film is 30% by mass or more.
  • Semiconductor nanoparticle composite cured film [2]
  • the semiconductor nanoparticle composite cured film further contains a scattering agent.
  • the mass fraction of the semiconductor nanoparticles in the cured film of the semiconductor nanoparticles composite is 40% by mass or more.
  • the absorbance of the semiconductor nanoparticle composite cured film with respect to light having a wavelength of 450 nm from the normal direction is 1.0 or more.
  • the absorbance of the semiconductor nanoparticle composite cured film with respect to light having a wavelength of 450 nm from the normal direction is 1.5 or more.
  • the scattering agent is a metal oxide.
  • the mass ratio of the ligand to the semiconductor nanoparticles (ligand / semiconductor nanoparticles) is 0.05 to 0.50.
  • the mass ratio of the ligand to the semiconductor nanoparticles is 0.10 to 0.40.
  • the ligand contains an organic group which is a hydrocarbon group which may have a substituent or a heteroatom, and a coordinating group.
  • the ligand has one or more groups selected from ether groups, ester groups and amide groups.
  • the ligand further comprises a coordinating group.
  • the organic group has a vinyl group and / or a vinylidene group.
  • the average particle size of the semiconductor nanoparticles is 10 nm or less.
  • the average particle size of the semiconductor nanoparticles is 7 nm or less.
  • the fluorescence quantum efficiency of the semiconductor nanoparticle composite cured film is 70% or more.
  • the molecular weight of the ligand is 50 or more and 600 or less.
  • the molecular weight of the ligand is 50 or more and 450 or less.
  • the ligand has one or more mercapto groups.
  • the ligand has two or more mercapto groups.
  • the semiconductor nanoparticles contain In and P.
  • Zn is contained on the surface of the semiconductor nanoparticles.
  • the fluorescence quantum efficiency of the semiconductor nanoparticle composite is 80% or more.
  • the half width of the emission spectrum of the semiconductor nanoparticle composite is 38 nm or less.
  • the semiconductor nanoparticle composite of the present invention adopts the following constitution.
  • ⁇ 1 A semiconductor nanoparticle composite in which a ligand is coordinated on the surface of semiconductor nanoparticles.
  • the ligand contains an organic group
  • the mass ratio of the ligand to the semiconductor nanoparticles (ligand / semiconductor nanoparticles) is 0.05 to 0.50.
  • ⁇ 2 The mass ratio of the ligand to the semiconductor nanoparticles is 0.10 to 0.40.
  • the semiconductor nanoparticle composite according to ⁇ 1 >> above.
  • ⁇ 3 Zn is contained on the surface of the semiconductor nanoparticles.
  • ⁇ 4 The semiconductor nanoparticles contain In and P.
  • ⁇ 6 The average particle size of the semiconductor nanoparticles is 7 nm or less.
  • ⁇ 8 The half width of the emission spectrum of the semiconductor nanoparticle composite is 38 nm or less.
  • ⁇ 10 The molecular weight of the ligand is 50 or more and 600 or less.
  • ⁇ 11 The molecular weight of the ligand is 50 or more and 450 or less.
  • the organic group has one or more groups selected from ether groups, ester groups and amide groups.
  • the organic group has a vinyl group and / or a vinylidene group.
  • ⁇ 15 >> The ligand has two or more mercapto groups.
  • Example 1 Semiconductor nanoparticles synthesis
  • the reaction mixture was cooled to 25 ° C., octanoic acid chloride (0.45 mmol) was injected, heated at about 250 ° C. for 30 minutes, and then cooled to 25 ° C. -Shell formation- Then, the mixture was heated to 200 ° C., 0.75 mL of a Zn precursor solution and 0.3 mmol of selenate trioctylphosphine were simultaneously added, and the mixture was reacted for 30 minutes to form a ZnSe shell on the surface of InP-based semiconductor nanoparticles.
  • a semiconductor nanoparticle 1-octadecene dispersion was prepared by dispersing the purified semiconductor nanoparticles in a flask with 1-octadecene so as to have a mass ratio of 10% by mass. 10.0 g of the prepared semiconductor nanoparticles 1-octadecene dispersion was placed in a flask, 3.5 g of triethylene glycol monomethylthiol (TEG-SH) and 0.5 g of dodecanethiol were added, and the temperature was 110 ° C., 60 in a nitrogen atmosphere. The mixture was stirred for 1 minute and cooled to 25 ° C. to obtain a semiconductor nanoparticle composite.
  • TAG-SH triethylene glycol monomethylthiol
  • the reaction solution was transferred to a centrifuge tube and centrifuged at 4000 G for 20 minutes to separate into a transparent 1-octadecene phase and a semiconductor nanoparticle composite phase.
  • the 1-octadecene phase was removed and the remaining semiconductor nanoparticle composite phase was recovered.
  • -Purification of semiconductor nanoparticle composite 5.0 mL of acetone was added to the obtained semiconductor nanoparticle composite phase to prepare a dispersion.
  • 50 mL of normal hexane was added to the obtained dispersion, and the mixture was centrifuged at 4000 G for 20 minutes. After centrifugation, the clear supernatant was removed and the precipitate was collected. This operation was repeated several times to obtain a purified semiconductor nanoparticle composite.
  • the optical properties of the obtained semiconductor nanoparticle composite were measured. As described above, the optical characteristics were measured using a quantum efficiency measurement system (QE-2100 manufactured by Otsuka Electronics Co., Ltd.).
  • the obtained semiconductor nanoparticle composite was dispersed in PGMEA (propylene glycol monomethyl ether acetate), and a single light of 450 nm was applied as excitation light to obtain an emission spectrum, which was re-excited from the obtained emission spectrum to emit fluorescence.
  • the fluorescence quantum efficiency (QY) and the half-value width (FWHM) were calculated from the emission spectrum after re-excitation correction excluding the re-excitation fluorescence emission spectrum of the amount obtained.
  • the purified semiconductor nanoparticle composite was heated to 550 ° C. by differential thermogravimetric analysis (DTA-TG), held for 10 minutes, and cooled. The residual mass after the analysis was taken as the mass of the semiconductor nanoparticles, and the mass ratio of the semiconductor nanoparticles to the semiconductor nanoparticles composite was confirmed from this value. With reference to the mass ratio, PGMEA (SP value 9.41) was added to the semiconductor nanoparticle composite so that the mass ratio of the semiconductor nanoparticles in the semiconductor nanoparticle composite dispersion was 1 mg / mL. A nanoparticle complex dispersion was obtained.
  • DTA-TG differential thermogravimetric analysis
  • This semiconductor nanoparticle composite dispersion was placed in an optical cell having an optical path length of 1 cm, and the absorbance at 450 nm was measured using a visible ultraviolet spectrophotometer (V670 manufactured by JASCO Corporation), which was designated as OD 450 .
  • V670 visible ultraviolet spectrophotometer
  • semiconductor nanoparticle composite composition 89 parts by mass of isobornyl acrylate, 10 parts by mass of trimethylolpropane triacrylate, and 1 part by mass of 2,2-dimethoxy-2-phenylacetophenone were mixed to obtain an ultraviolet curable resin.
  • the ultraviolet curable resin and the semiconductor nanoparticle composite were mixed to obtain a semiconductor nanoparticle composite composition.
  • the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition was 40% by mass.
  • semiconductor nanoparticle composite cured film The above-mentioned semiconductor nanoparticle composite composition was formed on glass by spin coating and heated at 90 ° C. for 3 minutes to volatilize the solvent. After irradiating with ultraviolet rays in the air and photocuring, the film was baked at 200 ° C. for 20 minutes to obtain a cured semiconductor nanoparticle composite film.
  • the wavelength of the obtained semiconductor nanoparticle composite cured film is wavelengthd from the normal direction of the semiconductor nanoparticle composite cured film using a visible ultraviolet spectrophotometer (V670 manufactured by JASCO Corporation) in the same manner as the semiconductor nanoparticle composite dispersion.
  • Example 2 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 4.0 g of methyl 3-mercaptopropionate (MPA-Me) was added instead of TEG-SH to obtain a semiconductor nanoparticle composite.
  • MPA-Me methyl 3-mercaptopropionate
  • a semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 3 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 4.0 g of 2-mercaptoethanol was added instead of TEG-SH to obtain a semiconductor nanoparticle composite.
  • a semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 4 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 3.5 g of methyl dihydrolipoate prepared by the method described later was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. .. -Preparation of methyl dihydrolipoate- 2.1 g (10 mmol) of dihydrolipoic acid was dissolved in 20 mL (49 mmol) of methanol and 0.2 mL of concentrated sulfuric acid was added.
  • the solution was refluxed under a nitrogen atmosphere for 1 hour.
  • the reaction solution was diluted with chloroform, and the solution was extracted in order with a 10% HCl aqueous solution, a 10% Na 2 CO 3 aqueous solution, and a saturated NaCl aqueous solution to recover the organic phase.
  • the organic phase was concentrated by evaporation and purified by column chromatography using a hexane-ethyl acetate mixed solvent as a developing solvent to obtain methyl dihydrolipoate.
  • Example 5 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 3.5 g of 6-mercaptohexyl acrylate prepared by the method described later was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • the filtrate was extracted in the order of 10% HCl aqueous solution, 10% Na 2 CO 3 aqueous solution, and saturated NaCl aqueous solution, and the organic phase was recovered.
  • the obtained organic phase was dried over magnesium sulfate and then filtered, and concentrated by evaporation to obtain the desired 6-mercaptohexyl acrylate.
  • it was used for the preparation of the semiconductor nanoparticle composite immediately after purification.
  • Example 6 In the method for producing the semiconductor nanoparticle composite described in Example 1 above, 3.5 g of N-acetyl-N- (2-mercaptoethyl) propanamide prepared by the method described later was added instead of TEG-SH. A semiconductor nanoparticle composite was obtained. Further, in the production of the semiconductor nanoparticle composite composition according to Example 1, the monomer is a mixture of methacrylic acid, glycidyl methacrylate, and 2,2-azobis (2,4-dimethylvaleronitrile), and the cross-linking agent is PETA-SA. (Pentaerythritol triacrylate succinic acid modified product) was changed to obtain a semiconductor nanoparticle composite composition.
  • a semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. .. -Preparation of N-acetyl-N- (2-mercaptoethyl) propanamide- 1.2 g (10 mmol) of N- (2-sulfanylethyl) acetamide and 1.7 mL (12 mmol) of triethylamine were placed in a 100 mL round bottom flask and dissolved in 30 mL of dehydrated dichloromethane. The solution was cooled to 0 ° C.
  • the organic phase was concentrated by evaporation and then purified by column chromatography using a mixed solvent of hexane-ethyl acetate as a developing solvent to obtain N-acetyl-N- (2-mercaptoethyl) propanamide.
  • Example 7 In the method for producing a semiconductor nanoparticle composite according to Example 1 above, 3.5 g of N-acetyl-N- (2-mercaptoethyl) propanamide was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. Obtained. Furthermore, in the production of semiconductor nanoparticle composite compositions, a transparent sealing resin for photodevices (model "SCR-1011 (A / B)", Shinetsu, which is a thermosetting addition-reaction silicone resin in which a monomer and a cross-linking agent are used Solution A and solution B (manufactured by Silicone Co., Ltd.) were changed to a mixture of 50:50 (mass ratio) to obtain a semiconductor nanoparticle composite composition.
  • SCR-1011 (A / B) Shinetsu, which is a thermosetting addition-reaction silicone resin in which a monomer and a cross-linking agent are used
  • Solution A and solution B manufactured by Silicone Co., Ltd.
  • the semiconductor nanoparticle composite composition is coated on glass by spin coating and heated by heating at 150 ° C. for 5 hours to heat the semiconductor nanoparticle composite cured film.
  • Got A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 8 In the method for producing semiconductor nanoparticles described in Example 1 above, the amount of the Zn precursor solution used for forming the ZnS shell was changed to 1.0 mL, and the amount of trioctylphosphine sulfide was changed to 0.4 mm réellel. The average particle size (the above-mentioned Heywood diameter) of the semiconductor nanoparticles thus obtained was measured by TEM and found to be 3 nm. Further, in the method for producing a semiconductor nanoparticle composite described in Example 1, 3.5 g of methyl dihydroate was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 9 In the method for producing semiconductor nanoparticles described in Example 1 above, the amount of the Zn precursor solution used for forming the ZnS shell was changed to 1.75 mL, and the amount of trioctylphosphine sulfide was changed to 0.7 mm réellel. The average particle size of the semiconductor nanoparticles thus obtained (the above-mentioned Heywood diameter) was measured by TEM and found to be 6 nm. Further, in the method for producing a semiconductor nanoparticle composite described in Example 1, 3.5 g of PEG-SH (polyethylene glycol monomethyl ether thiol) prepared by the method described later was added instead of TEG-SH to form a semiconductor nanoparticle composite. I got a body.
  • PEG-SH polyethylene glycol monomethyl ether thiol
  • a semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. .. -Preparation of PEG-SH-
  • the flask contained 210 g of methoxyPEG-OH (molecular weight 400) and 93 g of triethylamine and was dissolved in 420 mL of THF (tetrahydrofuran). The solution was cooled to 0 ° C., and 51 g of methanesulfonic acid chloride was gradually added dropwise under a nitrogen atmosphere, taking care that the temperature of the reaction solution did not exceed 5 ° C.
  • reaction solution was heated to room temperature and stirred for 2 hours.
  • This solution was extracted with a chloroform-aqueous system to recover the organic phase.
  • the obtained solution was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the filtrate was concentrated by evaporation to obtain an oily intermediate.
  • This was transferred to another flask and 400 mL of 1.3 M aqueous thiourea solution was added under a nitrogen atmosphere. After refluxing the solution for 2 hours, 21 g of NaOH was added and the mixture was refluxed for another 1.5 hours.
  • the obtained solution was extracted with a chloroform-aqueous system to obtain the desired ligand (PEG-SH, molecular weight 400).
  • Example 10 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 3.5 g of PEG-SH was added instead of TEG-SH to obtain a semiconductor nanoparticle composite.
  • a semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 11 In the method for producing semiconductor nanoparticles described in Example 1 above, the amount of the Zn precursor solution used for forming the ZnS shell was changed to 2.0 mL, and the amount of trioctylphosphine sulfide was changed to 0.9 mm réellel. The average particle size (the above-mentioned Heywood diameter) of the semiconductor nanoparticles thus obtained was measured by TEM and found to be 7 nm. Further, in the method for producing a semiconductor nanoparticle composite according to Example 1, 3.5 g of N-acetyl-N- (2-mercaptoethyl) propanamide was added instead of TEG-SH to prepare the semiconductor nanoparticle composite. Obtained. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 12 In the method for producing semiconductor nanoparticles described in Example 1 above, the amount of the Zn precursor solution used for forming the ZnS shell was changed to 3.75 mL, and the amount of trioctylphosphine sulfide was changed to 1.5 mm réellel. The average particle size of the semiconductor nanoparticles thus obtained (the above-mentioned Heywood diameter) was measured by TEM and found to be 10 nm. Further, in the method for producing a semiconductor nanoparticle composite according to Example 1, 3.5 g of N-acetyl-N- (2-mercaptoethyl) propanamide was added instead of TEG-SH to prepare the semiconductor nanoparticle composite. Obtained. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 13 In the method for producing semiconductor nanoparticles described in Example 1 above, the amount of the Zn precursor solution used for forming the ZnS shell was changed to 3.75 mL, and the amount of trioctylphosphine sulfide was changed to 1.5 mm réellel. The average particle size of the semiconductor nanoparticles obtained thereby (the above-mentioned Heywood diameter) was measured by TEM and found to be 13 nm. Further, in the method for producing a semiconductor nanoparticle composite described in Example 1, 3.5 g of PEG-SH was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 14 In the method for producing semiconductor nanoparticles described in Example 1 above, the amount of the Zn precursor solution used for forming the ZnSe shell was changed to 1.5 mL, and the amount of selenate trioctylphosphine was changed to 0.6 mm réellel. .. Further, the amount of the Zn precursor solution used for forming the ZnS shell was changed to 4.5 mL, and the amount of trioctylphosphine sulfide was changed to 1.8 mmsteadl. The average particle size of the semiconductor nanoparticles obtained thereby (the above-mentioned Heywood diameter) was measured by TEM and found to be 13 nm.
  • Example 2 In the method for producing a semiconductor nanoparticle composite described in Example 1, 3.5 g of PEG-SH was added instead of TEG-SH to obtain a semiconductor nanoparticle composite.
  • a semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. ..
  • Example 15 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 6.5 g of PEG-COOH (molecular weight 750) prepared by the method described later is added instead of TEG-SH to obtain a semiconductor nanoparticle composite. It was. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. .. When a semiconductor nanoparticle composite cured film was produced in the same manner as in Example 1, the film was not cured.
  • the precipitate was dissolved in 1M NaOH solution (40 mL), NaCl (10 g) was added, and the mixture was stirred at room temperature for 1 hour to remove the ethyl group at the end of PEG. This solution was adjusted to pH 3.0 by adding 6M HCl. The obtained solution was extracted with a chloroform-aqueous system to obtain PEG-COOH having a molecular weight of 750.
  • Example 16 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 8.5 g of PEG-COOH (molecular weight 1000) prepared by the method described later is added instead of TEG-SH to obtain a semiconductor nanoparticle composite. It was. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. .. When a semiconductor nanoparticle composite cured film was produced in the same manner as in Example 1, the film was not cured.
  • Example 17 In the method for producing a semiconductor nanoparticle composite described in Example 1 above, 6.5 g of PEG-COOH (750) was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, a semiconductor nanoparticle composite composition, and a semiconductor nanoparticle composite cured film were prepared by the same method as in Example 1 except for the above, and their physical properties were evaluated. .. The upper limit of the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition and the semiconductor nanoparticle composite cured film was 25%.
  • Example 18 In the method for producing a semiconductor nanoparticle composite according to Example 1 above, 3.5 g of N-acetyl-N- (2-mercaptoethyl) propanamide was added instead of TEG-SH to obtain a semiconductor nanoparticle composite. Obtained. A semiconductor nanoparticle composite, a semiconductor nanoparticle composite dispersion, and a semiconductor nanoparticle composite composition were prepared in the same manner as in Example 1 except for the above, and their physical properties were evaluated. A cross-linking agent was not added to the cured semiconductor nanoparticle composite film, and an attempt was made to prepare the cured film in the same manner as in Example 1, but the film was not cured.
  • Example 19 In the method for producing the semiconductor nanoparticle composite described in Example 1 above, the operation was changed as follows. 10.0 g of a semiconductor nanoparticle hexane dispersion liquid in which purified semiconductor nanoparticles are dispersed in hexane so as to have a mass ratio of 10 mass% in a flask is placed in a flask, and 10 mL of formamide and a 0.5 mass% ammonium sulfide aqueous solution are added. 10 mL was added, and the mixture was stirred at room temperature for 10 minutes under a nitrogen atmosphere to obtain a reaction solution containing a semiconductor nanoparticle composite.
  • the reaction solution was transferred to a centrifuge tube, 40 mL of acetone was added, and the mixture was centrifuged at 4000 G for 20 minutes to separate into a transparent solution layer and a semiconductor nanoparticle composite phase.
  • the transparent solution phase was removed and the remaining semiconductor nanoparticle composite phase was recovered.
  • acetone was changed to chloroform and normal hexane was changed to acetone.
  • the fluorescence quantum efficiency of the obtained semiconductor nanoparticle composite was 15%, and the half width was 45 nm.
  • the obtained semiconductor nanoparticle composite was not dispersed in PGMEA. Furthermore, the semiconductor nanoparticle composite did not disperse in isobornyl acrylate.
  • Titanium oxide (diameter 300 nm) was mixed in an amount of 10% by mass with respect to the semiconductor nanoparticle composites of the above examples when the monomer and the semiconductor nanoparticle composite were mixed in the method for producing the semiconductor nanoparticle composite composition.
  • a semiconductor nanoparticle composite composition was obtained, and the semiconductor nanoparticle composite composition was further cured to obtain a scatterer-containing semiconductor nanoparticle composite cured film.
  • the absorbance of the cured film of the scattering agent-containing semiconductor nanoparticle composite was measured by the method described above. The results are shown in Tables 1 to 3.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113741098A (zh) * 2021-11-04 2021-12-03 拓米(成都)应用技术研究院有限公司 一种utg-qd型mini-led板及其应用、制备方法和光学架构
KR20230139954A (ko) * 2022-03-28 2023-10-06 삼성에스디아이 주식회사 경화성 조성물, 상기 조성물을 이용하여 제조된 경화막, 상기 경화막을 포함하는 컬러필터 및 상기 컬러필터를 포함하는 디스플레이 장치

Families Citing this family (1)

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Publication number Priority date Publication date Assignee Title
GB2594482B (en) * 2020-04-28 2022-04-27 Plessey Semiconductors Ltd Tuneable sub-pixel

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002162501A (ja) * 2000-11-28 2002-06-07 Mitsubishi Chemicals Corp 半導体結晶粒子を含有する薄膜状成形体、及びその用途
JP2015509125A (ja) * 2012-01-19 2015-03-26 ナノコ テクノロジーズ リミテッド 発光用途用成形ナノ粒子蛍光体
WO2017150297A1 (ja) * 2016-02-29 2017-09-08 富士フイルム株式会社 半導体ナノ粒子、分散液およびフィルム
WO2017188300A1 (ja) * 2016-04-26 2017-11-02 昭栄化学工業株式会社 量子ドット材料及び量子ドット材料の製造方法
JP2017533875A (ja) * 2014-08-11 2017-11-16 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ 反応性コロイド状ナノ結晶及びナノ結晶複合体
WO2018226654A1 (en) * 2017-06-05 2018-12-13 Austin Smith Acid stabilization of quantum dot-resin concentrates and premixes
WO2019064589A1 (ja) * 2017-09-29 2019-04-04 日立化成株式会社 波長変換部材、バックライトユニット、画像表示装置、波長変換用樹脂組成物及び波長変換用樹脂硬化物

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002121549A (ja) 2000-06-26 2002-04-26 Mitsubishi Chemicals Corp 半導体超微粒子
US8920675B2 (en) * 2010-10-27 2014-12-30 Pixelligent Technologies, Llc Synthesis, capping and dispersion of nanocrystals
KR20180084040A (ko) 2015-11-20 2018-07-24 제이에스알 가부시끼가이샤 나노 입자 집합체 및 그의 제조 방법, 나노 입자 집합체 조성물, 파장 변환층, 그리고 리간드
KR102618409B1 (ko) * 2015-12-23 2023-12-27 삼성전자주식회사 양자점-폴리머 복합체 및 이를 포함하는 소자
CN108110144B (zh) * 2016-11-25 2021-11-26 三星电子株式会社 包括量子点的发光器件和显示器件

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002162501A (ja) * 2000-11-28 2002-06-07 Mitsubishi Chemicals Corp 半導体結晶粒子を含有する薄膜状成形体、及びその用途
JP2015509125A (ja) * 2012-01-19 2015-03-26 ナノコ テクノロジーズ リミテッド 発光用途用成形ナノ粒子蛍光体
JP2017533875A (ja) * 2014-08-11 2017-11-16 ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンＨｅｎｋｅｌ ＡＧ ＆ Ｃｏ． ＫＧａＡ 反応性コロイド状ナノ結晶及びナノ結晶複合体
WO2017150297A1 (ja) * 2016-02-29 2017-09-08 富士フイルム株式会社 半導体ナノ粒子、分散液およびフィルム
WO2017188300A1 (ja) * 2016-04-26 2017-11-02 昭栄化学工業株式会社 量子ドット材料及び量子ドット材料の製造方法
WO2018226654A1 (en) * 2017-06-05 2018-12-13 Austin Smith Acid stabilization of quantum dot-resin concentrates and premixes
WO2019064589A1 (ja) * 2017-09-29 2019-04-04 日立化成株式会社 波長変換部材、バックライトユニット、画像表示装置、波長変換用樹脂組成物及び波長変換用樹脂硬化物

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113741098A (zh) * 2021-11-04 2021-12-03 拓米(成都)应用技术研究院有限公司 一种utg-qd型mini-led板及其应用、制备方法和光学架构
KR20230139954A (ko) * 2022-03-28 2023-10-06 삼성에스디아이 주식회사 경화성 조성물, 상기 조성물을 이용하여 제조된 경화막, 상기 경화막을 포함하는 컬러필터 및 상기 컬러필터를 포함하는 디스플레이 장치
JP2023145318A (ja) * 2022-03-28 2023-10-11 三星エスディアイ株式会社 硬化性組成物、該硬化性組成物の硬化物を含む硬化膜、該硬化膜を含むカラーフィルタ、および該カラーフィルタを含むディスプレイ装置
JP7518884B2 (ja) 2022-03-28 2024-07-18 三星エスディアイ株式会社 硬化性組成物、該硬化性組成物の硬化物を含む硬化膜、該硬化膜を含むカラーフィルタ、および該カラーフィルタを含むディスプレイ装置
KR102878347B1 (ko) 2022-03-28 2025-10-29 삼성에스디아이 주식회사 경화성 조성물, 상기 조성물을 이용하여 제조된 경화막, 상기 경화막을 포함하는 컬러필터 및 상기 컬러필터를 포함하는 디스플레이 장치

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