WO2020250663A1 - 半導体ナノ粒子複合体、半導体ナノ粒子複合体分散液、半導体ナノ粒子複合体組成物および半導体ナノ粒子複合体硬化膜 - Google Patents

半導体ナノ粒子複合体、半導体ナノ粒子複合体分散液、半導体ナノ粒子複合体組成物および半導体ナノ粒子複合体硬化膜 Download PDF

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WO2020250663A1
WO2020250663A1 PCT/JP2020/020686 JP2020020686W WO2020250663A1 WO 2020250663 A1 WO2020250663 A1 WO 2020250663A1 JP 2020020686 W JP2020020686 W JP 2020020686W WO 2020250663 A1 WO2020250663 A1 WO 2020250663A1
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semiconductor nanoparticle
nanoparticle composite
semiconductor
ligand
fatty acid
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French (fr)
Japanese (ja)
Inventor
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 KR1020217042662A priority Critical patent/KR102809556B1/ko
Priority to CN202080043418.4A priority patent/CN114127225A/zh
Priority to US17/618,768 priority patent/US12054657B2/en
Priority to CN202311018670.1A priority patent/CN117229769A/zh
Priority to KR1020247034030A priority patent/KR20240152968A/ko
Publication of WO2020250663A1 publication Critical patent/WO2020250663A1/ja
Anticipated expiration legal-status Critical
Priority to US18/763,347 priority patent/US12365836B2/en
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Definitions

  • the present invention relates to a semiconductor nanoparticle composite.
  • Semiconductor nanoparticles (quantum dots, QDs) that are so small that the quantum confinement effect is exhibited have a band gap 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 band gap 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 since Cd and Pb are regulated substances such as restrictions on the use of specific harmful substances, in recent years non-Cd type. Research on non-Pb-based semiconductor nanoparticles has been carried out.
  • Semiconductor nanoparticles are being attempted to be applied to various applications such as display applications, biomarking applications, and solar cell applications.
  • As a display application it is expected to be applied to QD film, QD patterning, self-luminous device (QLED) and the like.
  • 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.
  • Semiconductor nanoparticles and semiconductor nanoparticles composites are generally dispersed in a dispersion medium and prepared as a dispersion liquid, and are applied to various fields.
  • a dispersion liquid dispersed in a polar organic dispersion medium such as glycol ethers and glycol ether esters is used, and the dispersion liquid is cured to cure a QD film and QD patterning. Form a film.
  • a polar organic dispersion medium such as glycol ethers and glycol ether esters
  • the semiconductor nanoparticles and the semiconductor nanoparticle composite synthesized in the non-polar dispersion medium have high hydrophobicity, they can be easily dispersed in the non-polar dispersion medium, but difficult to disperse in the polar dispersion medium. there were.
  • the semiconductor nanoparticles and the semiconductor nanoparticles composite synthesized in the non-polar dispersion medium have a small dipole-to-dipole force and hydrogen bonding force. Therefore, among the polar dispersion media, the semiconductor nanoparticles can be dispersed in toluene and chloroform, which have small dipole-to-dipole force and hydrogen bond force, as in the case of semiconductor nanoparticles synthesized in an organic solvent.
  • these polar dispersion media are highly toxic and therefore impractical.
  • the ligand exchange method is known as a method for making semiconductor nanoparticles dispersible in a polar dispersion medium.
  • the ligand exchange method is a method of replacing a ligand contained in a semiconductor nanoparticles complex obtained by binding a ligand to the surface of semiconductor nanoparticles with a ligand having a hydrophilic group.
  • the semiconductor nanoparticle composite thus obtained can be dispersed in a polar dispersion medium.
  • the semiconductor nanoparticle composites disclosed in Non-Patent Documents 1 to 5 and Patent Document 1 enable dispersion of semiconductor nanoparticles in a polar dispersion medium, but the luminous efficiency is lowered. There was a problem.
  • An encapsulation method is also known as a method for making semiconductor nanoparticles dispersible in a polar dispersion medium.
  • the encapsulation method is a semiconductor obtained by binding a ligand to the surface of semiconductor nanoparticles. Since it is a method of further coating the nanoparticle composite with an amphoteric polymer, the amount of the dispersant for the semiconductor nanoparticles increases, and it becomes difficult to increase the mass fraction of the semiconductor nanoparticles. Is difficult.
  • semiconductor nanoparticles are required to be capable of being dispersed in a polar dispersion medium at a high mass fraction while maintaining the high fluorescence quantum efficiency (QY) of the semiconductor nanoparticles. ..
  • any curing method is used as a curing method for curing the dispersion, but when the curing method is thermosetting, a semiconductor nanoparticle composite is used. Since heat is applied to the dispersion liquid of the above, heat resistance is required for the semiconductor nanoparticles and the semiconductor nanoparticle composite.
  • any curing method is used as a method for curing the dispersion, but depending on the curing method (for example, for an inkjet), the dispersion may be used. Low viscosity may be required.
  • an object of the present invention is to provide a semiconductor nanoparticle composite that can be dispersed in a polar dispersion medium with a high mass fraction while maintaining the high fluorescence quantum efficiency (QY) of the semiconductor nanoparticles.
  • Another object of the present invention is that the semiconductor nanoparticles can be dispersed in a polar dispersion medium at a high mass fraction while maintaining the high fluorescence quantum efficiency (QY), and also have high heat resistance and heat resistance. Is to provide a semiconductor nanoparticle composite useful in the required applications.
  • Another object of the present invention is that while maintaining the high fluorescence quantum efficiency (QY) of semiconductor nanoparticles, it can be dispersed in a polar dispersion medium at a high mass fraction, and when dispersed in a dispersion medium. It is an object of the present invention to provide a semiconductor nanoparticle composite useful for applications in which the viscosity of the dispersion liquid is low and the viscosity of the dispersion liquid is low.
  • QY fluorescence quantum efficiency
  • the semiconductor nanoparticle composite (1) of the present invention is a semiconductor nanoparticle composite in which a ligand is coordinated on the surface of the semiconductor nanoparticles.
  • the semiconductor nanoparticles are core / shell type semiconductor nanoparticles having a core containing In and P and a shell having one or more layers.
  • the semiconductor nanoparticles further contain halogen, and in the semiconductor nanoparticles, the molar ratio of halogen to In in terms of atoms is 0.80 to 15.00.
  • the ligand has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is 700 or less. And the average SP value of the whole ligand is 9.10 to 11.00.
  • a semiconductor nanoparticle composite characterized by the above.
  • the present invention (2) provides the semiconductor nanoparticle composite of (1), which is characterized in that the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is 300 or more and 700 or less. is there.
  • the present invention (3) provides the semiconductor nanoparticle composite of (1), which is characterized in that the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is 300 or more and 600 or less. is there.
  • the present invention (4) is characterized in that the mass ratio (ligand / semiconductor nanoparticles) of the ligand to the semiconductor nanoparticles is 1.00 or less, and the semiconductor nanoparticles composite of (2) or (3). Is to provide.
  • the present invention (5) is characterized in that the mass ratio (ligand / semiconductor nanoparticles) of the ligand to the semiconductor nanoparticles is 0.70 or less, and the semiconductor nanoparticles composite of (2) or (3). Is to provide.
  • the present invention (6) is characterized in that the mass ratio (ligand / semiconductor nanoparticles) of the ligand to the semiconductor nanoparticles is 0.40 or more, which is any of the semiconductor nanoparticles (2) to (5). It provides a complex.
  • the present invention (7) provides the semiconductor nanoparticle composite of (1), which is characterized in that the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is less than 300.
  • the present invention (8) also provides the semiconductor nanoparticles composite of (7), wherein the mass ratio (ligand / semiconductor nanoparticles) of the ligand to the semiconductor nanoparticles is 0.40 or less. Is.
  • the present invention (9) is characterized in that the content of the mercapto fatty acid ester represented by the general formula (1) in the entire ligand is 40 mol% or more, any of (1) to (8).
  • the present invention provides a semiconductor nanoparticle composite of the above.
  • the present invention (10) is characterized in that the content of the mercapto fatty acid ester represented by the general formula (1) in the entire ligand is 50 mol% or more, any of (1) to (8).
  • the present invention provides a semiconductor nanoparticle composite of the above.
  • the present invention (11) is characterized in that the content of the mercapto fatty acid ester represented by the general formula (1) in the entire ligand is 60 mol% or more, any of (1) to (8).
  • the present invention provides a semiconductor nanoparticle composite of the above.
  • the present invention (12) provides a semiconductor nanoparticle composite according to any one of (1) to (11), wherein at least one of the shells is formed of ZnSe.
  • the present invention (13) is characterized in that the shell has two or more layers and the outermost layer of the shell is formed of ZnS.
  • the shell includes at least a first shell formed of ZnSe and covering the outer surface of the core and a second shell formed of ZnS and covering the outer surface of the first shell.
  • R 2 in the general formula (1) is any one selected from the group consisting of an oligoethylene glycol group, a polyethylene glycol group and an alkoxy group (1) to.
  • R 2 in the general formula (1) is any one selected from the group consisting of an oligoethylene glycol group, a polyethylene glycol group and an alkoxy group (1) to.
  • the present invention (16) is characterized in that the terminal group that does not bind to the carboxyl group of R 2 in the general formula (1) is selected from the group consisting of an alkyl group, an alkenyl group and an alkynyl group.
  • the semiconductor nanoparticle composite according to any one of (1) to (15) is provided.
  • the present invention (17) provides the semiconductor nanoparticle composite according to any one of (1) to (16), wherein the ligand further contains an aliphatic ligand.
  • the present invention (18) is characterized in that the aliphatic ligand is at least one selected from the group consisting of an aliphatic thiol, an aliphatic carboxylic acid and an aliphatic phosphine (17). It provides a complex.
  • the present invention (19) provides the semiconductor nanoparticle composite according to any one of (1) to (18), wherein the quantum efficiency of the semiconductor nanoparticle composite after purification is 80% or more. It is a thing.
  • the present invention (20) provides the semiconductor nanoparticle composite according to any one of (1) to (19), wherein the half width of the emission spectrum of the semiconductor nanoparticle composite is 38 nm or less. Is.
  • the present invention (21) provides a semiconductor nanoparticle composite dispersion liquid in which any of the semiconductor nanoparticle composites (1) to (20) is dispersed in an organic dispersion medium.
  • the present invention (22) provides a semiconductor nanoparticle composite composition in which any of the semiconductor nanoparticle composites (1) to (20) is dispersed in a monomer or a prepolymer.
  • the present invention (23) provides a semiconductor nanoparticle composite cured film in which any of the semiconductor nanoparticle composites (1) to (20) is dispersed in a polymer matrix.
  • the present invention (24) is a core / shell type semiconductor nanoparticles having a core containing In and P and one or more layers of shells, further containing halogen, and a molar amount of halogen with respect to In in terms of atoms.
  • a semiconductor nanoparticle composite obtained by contacting semiconductor nanoparticles having a ratio of 0.80 to 15.00 with a surface-modifying compound having a binding group that binds to the semiconductor nanoparticles on one end side.
  • the surface modification compound has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is 700 or less. Moreover, the average SP value of the entire surface modification compound is 9.10 to 11.00.
  • a semiconductor nanoparticle composite characterized by the above.
  • the surface modification compound further contains an aliphatic group-containing surface modification compound having a binding group bonded to semiconductor nanoparticles on one end side and an aliphatic group on the other end side.
  • the present invention provides the semiconductor nanoparticle composite of (24).
  • 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 capable of dispersing semiconductor nanoparticles in a dispersion medium having a polarity with a high mass fraction while maintaining the high fluorescence quantum efficiency (QY) of the semiconductor nanoparticles. Further, according to the present invention, in addition to being able to disperse in a polar dispersion medium with a high mass fraction while maintaining the high fluorescence quantum efficiency (QY) of the semiconductor nanoparticles, the heat resistance is high and the heat resistance is high. It is possible to provide a semiconductor nanoparticle composite useful in the required applications.
  • the present invention while maintaining the high fluorescence quantum efficiency (QY) of the semiconductor nanoparticles, in addition to being able to disperse in a polar dispersion medium with a high mass fraction, when dispersed in the dispersion medium. It is possible to provide a semiconductor nanoparticle composite useful for applications in which the viscosity of the dispersion liquid is low and the viscosity of the dispersion liquid is low.
  • the semiconductor nanoparticle composite (A) of the present invention is a semiconductor nanoparticle composite in which a ligand is coordinated on the surface of the semiconductor nanoparticles.
  • the semiconductor nanoparticles are core / shell type semiconductor nanoparticles having a core containing In and P and a shell having one or more layers.
  • the semiconductor nanoparticles further contain halogen, and the molar ratio of halogen to In in the semiconductor nanoparticles is 0.80 to 15.00 in terms of atoms.
  • the ligand has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is 700 or less. And the average SP value of the whole ligand is 9.10 to 11.00. It is a semiconductor nanoparticle composite characterized by.
  • the semiconductor nanoparticles composite of the present invention is a composite of semiconductor nanoparticles in which a ligand is coordinated on the surface of the semiconductor nanoparticles and a ligand.
  • the semiconductor nanoparticle composite of the present invention is obtained by contacting semiconductor nanoparticles with a ligand.
  • the semiconductor nanoparticle composite is a semiconductor nanoparticle composite having light emitting characteristics.
  • the semiconductor nanoparticle composite 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.
  • the full width at half maximum (FWHM) of the emission spectrum of the semiconductor nanoparticle composite of the present invention is preferably 38 nm or less, and more preferably 35 nm or less.
  • FWHM full width at half maximum
  • the fluorescence quantum efficiency (QY) of the semiconductor nanoparticle composite of the present invention is preferably 80% or more, more preferably 85% or more.
  • QY fluorescence quantum efficiency
  • the optical properties of the semiconductor nanoparticle composite can be measured using a quantum efficiency measurement system.
  • the semiconductor nanoparticle composite is dispersed in a dispersion liquid, and excitation light is applied to obtain an emission spectrum.
  • the fluorescence quantum efficiency (QY) and the half-value width (FWHM) are calculated from the emission spectrum after re-excitation correction excluding the re-excitation fluorescence emission spectrum of the portion re-excited and fluorescently emitted from the emission spectrum obtained here.
  • the dispersion liquid include normal hexane, PGMEA, and chloroform.
  • the semiconductor nanoparticles constituting the semiconductor nanoparticles composite of the present invention are core / shell type semiconductor nanoparticles having a core containing In and P and a shell having one or more layers.
  • the shell may have at least one layer, and the semiconductor nanoparticles include, for example, a core / shell type semiconductor nanoparticles composed of a core and a one-layer shell, and a core / shell composed of a core and a two-layer shell. Examples include type semiconductor nanoparticles and core / shell type semiconductor nanoparticles composed of a core and a shell having three or more layers.
  • the fluorescence quantum efficiency of the semiconductor nanoparticles can be maintained, and the semiconductor nanoparticles composite can also have high fluorescence quantum efficiency.
  • the structure of the semiconductor nanoparticles it is sufficient that the shell covers at least a part of the surface of the core, but a structure in which the shell covers the entire surface of the core is preferable, and the shell uniformly covers the entire surface of the core. A covering structure is particularly preferred.
  • the shell preferably contains a shell having a composition containing Zn and Se, and it is preferable that at least one of the shells is formed of ZnSe.
  • the outermost layer is preferably a shell having a composition containing Zn and S, and more preferably ZnS.
  • the shell when the shell is formed of at least ZnSe and comprises a first shell that covers the outer surface of the core particles and a second shell that is formed of ZnS and covers the outer surface of the first shell, it is fluorescent. Quantum efficiency can be increased.
  • composition in the shell does not necessarily have to be a stoichiometric composition as long as the effects of the present invention are not impaired, and elements other than Zn, Se, and S may be contained in each shell, and the shell is formed in the shell. It may have one or more gradient-type shells in which the ratio of elements to be produced changes.
  • the shell covers at least a part of the core and the element distribution inside the shell are, for example, energy dispersive X-ray spectroscopy (TEM-EDX) using a transmission electron microscope. It can be confirmed by analyzing the composition using.
  • TEM-EDX energy dispersive X-ray spectroscopy
  • the semiconductor nanoparticles according to the semiconductor nanoparticle composite of the present invention contain halogen.
  • the molar ratio of halogen to In in semiconductor nanoparticles is 0.80 to 15.00, preferably 1.00 to 15.00 in terms of atoms.
  • the halogen contained in the semiconductor nanoparticles is preferably F, Cl, Br.
  • the halogen is present at the interface between the core and the shell of the semiconductor nanoparticles and / or in the shell of the semiconductor nanoparticles, so that the above-mentioned effects can be further obtained.
  • the molar ratio of P to In in the semiconductor nanoparticles according to the semiconductor nanoparticles composite of the present invention is preferably 0.20 to 0.95 in terms of atoms. Further, the molar ratio of Zn to In is preferably 10.00 to 60.00 in terms of atoms.
  • the analysis of the elements constituting the semiconductor nanoparticles can be performed using a high frequency inductively coupled plasma emission spectrometer (ICP) or a fluorescent X-ray analyzer (XRF).
  • ICP inductively coupled plasma emission spectrometer
  • XRF fluorescent X-ray analyzer
  • a core of semiconductor nanoparticles can be formed by heating a precursor mixture obtained by mixing a precursor of In, a precursor of P, and, if necessary, an additive in a solvent.
  • a solvent a coordinating solvent or a non-coordinating solvent is used.
  • solvents include 1-octadecene, hexadecane, squalene, oleylamine, trioctylphosphine, trioctylphosphine oxide and the like.
  • the precursor of In include, but are not limited to, the acetate, carboxylate, and halide containing In.
  • the precursor of P include, but are not limited to, the organic compounds and gases containing P.
  • 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 In and P 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.
  • the emission characteristics of the semiconductor nanoparticles can be improved by adding a halide as needed.
  • the In precursor and, if necessary, a precursor solution in which a dispersant is added to a solvent are mixed under vacuum, once heated at 100 ° C. to 300 ° C. for 6 to 24 hours, and then further P.
  • the precursor is added and heated at 200 ° C. to 400 ° C. for 3 to 60 minutes, and then cooled.
  • a core particle dispersion containing core particles can be obtained by further adding 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. ..
  • the semiconductor nanoparticles By adding a shell-forming precursor to the synthesized core particle dispersion, the semiconductor nanoparticles have a core / shell structure, and the fluorescence quantum efficiency (QY) and stability can be improved.
  • QY fluorescence quantum efficiency
  • 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 core particle dispersion described above, 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. Then, it is heated at 200 ° C. to 400 ° C., preferably 250 ° C. to 350 ° C. As a result, core / shell type semiconductor nanoparticles can be obtained.
  • 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. Can be done.
  • the shell precursor may be mixed in advance and added once or in multiple times, or each may be added separately in one time or in multiple 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.
  • 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 ligand that coordinates the semiconductor nanoparticles includes a mercapto fatty acid ester represented by the following general formula (1).
  • HS-R 1- COO-R 2 (1)
  • R 1 represents an alkylene group having 1 to 3 carbon atoms
  • R 2 represents a hydrophilic group. That is, the mercapto fatty acid ester represented by the general formula (1) is a compound in which -SH is bound to one of R 1 and -COO-R 2 is bound to the other.
  • the ligand that coordinates the semiconductor nanoparticles may contain one kind of mercapto fatty acid ester represented by the general formula (1), or is represented by the general formula (1). It may contain two or more kinds of mercapto fatty acid esters.
  • R 1 includes a methylene group (-CH 2- ), an ethylene group (-CH 2 CH 2- ), a propylene group (-CH 2 CH 2 CH 2- ), and a methyl ethylene group (-CH 2 CH 2- ). Examples thereof include CH (CH 3 )-) and a dimethylmethylene group (-C (CH 3 ) 2- ).
  • R 2 is not particularly limited as long as it is a hydrophilic group, and for example, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aldehyde group, a carboxyl group, an amino group, an imino group and a nitro group.
  • examples thereof include a hydrophilic group containing a group such as a group, a cyano group, a vinyl group, an aryl group, a halogeno group, a ketone group, an ether bond, an ester bond and a siloxane bond.
  • R 2 is, oligoethylene glycol group is preferably a hydrophilic group having a polyethylene glycol group or an alkoxy group, and particularly preferably oligoethylene glycol group or polyethylene glycol group. Since R 2 is a hydrophilic group having an oligoethylene glycol group, a polyethylene glycol group or an alkoxy group, semiconductor nanoparticles can be dispersed in a polar solvent at a high concentration. Further, in the general formula (1), it is preferable that the terminal group on the side that does not bond to the carboxyl group of R 2 is selected from the group consisting of an alkyl group, an alkenyl group and an alkynyl group.
  • Terminal groups on the side not bonded to the carboxyl group of R 2 is an alkyl group, that is any one selected from the group consisting of alkenyl and alkynyl groups, inhibit the interaction between the semiconductor nanoparticle composites, semiconductor
  • the nanoparticles can be dispersed in a polar solvent at a high concentration.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is 700 or less.
  • the semiconductor nanoparticles can be dispersed in a polar solvent at a high concentration.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) refers to the average molecular weight of the mercapto fatty acid ester represented by the general formula (1).
  • the average molecular weight of the mercapto fatty acid ester represented by the general formula (1) is measured by the GPC method (gel permeation chromatography), and the number average of the obtained values is defined as the average molecular weight (number average molecular weight Mn). ..
  • the SP value of the mercapto fatty acid ester represented by the general formula (1) is 9.20 or more, preferably 9.20 to 12.00.
  • the semiconductor nanoparticles can be dispersed in the polar solvent.
  • the SP value is calculated and determined by the Y-MB method.
  • the SP value of each mercapto fatty acid ester is multiplied by the body integration rate of each mercapto fatty acid ester. After that, the added SP value is taken as the SP value of the mercapto fatty acid ester.
  • the ligand may include a ligand other than the mercapto fatty acid ester represented by the general formula (1).
  • the ligand other than the mercapto fatty acid ester represented by the general formula (1) is not particularly limited as long as it is a compound having a binding group coordinating to semiconductor nanoparticles on one end side. It can be used as a compound coordinated to semiconductor nanoparticles, and when used in combination with the mercapto fatty acid ester represented by the general formula (1), the average SP value of the entire ligand is 9.20 to 11.00. It is preferable that the compound can be adjusted to 9.20 to 10.00.
  • the SP value of the ligand other than the mercapto fatty acid ester represented by the general formula (1) is not particularly limited, but is preferably 7.50 to 15.00, and particularly preferably 7.50 to 15.00.
  • the average SP value of the entire ligand coordinated to the semiconductor nanoparticles is 9.20 to 11.00, preferably 9.20 to 10.00.
  • the semiconductor nanoparticles can be dispersed in the polar solvent.
  • the SP value of the ligand can be calculated from the structural formula using the Y-MB method.
  • the SP value of each ligand is multiplied by the volume fraction of the ligand, and then the average SP value of all the ligands added is taken as the SP value of the ligand.
  • an aliphatic ligand is preferable.
  • the semiconductor nanoparticles can be dispersed in a polar solvent at a high concentration. Furthermore, it can be dispersed in an organic solvent having a wider range of SP values.
  • the choice of dispersion medium can be expanded.
  • aliphatic ligand examples include aliphatic thiol, aliphatic carboxylic acid, aliphatic phosphine, aliphatic phosphine oxide, and aliphatic amine, and due to the strength of coordinating power with semiconductor nanoparticles, aliphatic thiol and fat
  • One or more selected from the group consisting of group carboxylic acids and aliphatic phosphines is preferable.
  • the aliphatic group of the aliphatic ligand may contain a substituent or a hetero atom.
  • the content of the mercapto fatty acid ester represented by the general formula (1) in the entire ligand is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more.
  • the semiconductor nanoparticle composite (A) of the present invention includes the following first form.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) in the semiconductor nanoparticle composite (A) of the present invention is 300 or more and 700.
  • it is a semiconductor nanoparticle composite preferably 300 or more and 600 or less.
  • the first form of the semiconductor nanoparticle composite (A) of the present invention is a semiconductor nanoparticle composite in which a ligand is coordinated on the surface of the semiconductor nanoparticles.
  • the semiconductor nanoparticles are core / shell type semiconductor nanoparticles having a core containing In and P and a shell having one or more layers.
  • the semiconductor nanoparticles further contain halogen, and in the semiconductor nanoparticles, the molar ratio of halogen to In in terms of atoms is 0.80 to 15.00.
  • the ligand has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is 300 or more and 700 or less, preferably 300 or more and 600 or less.
  • the average SP value of the whole ligand is 9.10 to 11.00. It is a semiconductor nanoparticle composite characterized by.
  • the heat resistance of the semiconductor nanoparticle composite means that when the semiconductor nanoparticle composite is heat-treated at a certain temperature, it can be redispersed in the solvent dispersed before the heat treatment even after the heat treatment.
  • the semiconductor nanoparticle composite is treated in an air atmosphere at 180 ° C. for 1 hour and then redispersed in a good solvent of the semiconductor nanoparticle composite.
  • the dispersibility in a good solvent after heating is significantly reduced due to the denaturation or desorption of the ligand.
  • the mass ratio of the ligand to the semiconductor nanoparticles is preferably 1.00 or less, preferably 0.70 or less. Is even more preferable.
  • the semiconductor nanoparticles are dispersed in a polar solvent at a high concentration while maintaining the heat resistance of the semiconductor nanoparticles composite. Is possible.
  • the mass ratio of the ligand to the semiconductor nanoparticles is preferably 0.40 or more.
  • the semiconductor nanoparticles are dispersed in a polar solvent at a high concentration while maintaining the heat resistance of the semiconductor nanoparticles composite. Is possible.
  • the semiconductor nanoparticle composite (A) of the present invention includes the following second form.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) in the semiconductor nanoparticle composite (A) of the present invention is less than 300.
  • the second form of the semiconductor nanoparticle composite (A) of the present invention is a semiconductor nanoparticle composite in which a ligand is coordinated on the surface of the semiconductor nanoparticles.
  • the semiconductor nanoparticles are core / shell type semiconductor nanoparticles having a core containing In and P and a shell having one or more layers.
  • the semiconductor nanoparticles further contain halogen, and in the semiconductor nanoparticles, the molar ratio of halogen to In in terms of atoms is 0.80 to 15.00.
  • the ligand has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is less than 300, preferably 100 or more and less than 300. And the average SP value of the whole ligand is 9.10 to 11.00. It is a semiconductor nanoparticle composite characterized by.
  • the viscosity of the dispersion can be lowered even if the semiconductor nanoparticle composite is dispersed at a high mass fraction.
  • the low viscosity of the dispersion liquid when the semiconductor nanoparticles composite is dispersed at a high mass fraction means that the semiconductor nanoparticles composite is 30.0% by mass in terms of the mass ratio of the semiconductor nanoparticles. This means that the mass at 25 ° C. is 30 cp or less when dispersed in isovonyl acrylate.
  • the mass ratio of the ligand to the semiconductor nanoparticles is preferably 0.40 or less.
  • the semiconductor nanoparticles are used as a polar solvent while suppressing an increase in the viscosity of the dispersion in which the semiconductor nanoparticles are dispersed. It is possible to disperse at a high concentration.
  • the semiconductor nanoparticle composite (B) of the present invention is a core / shell type semiconductor nanoparticle having a core containing In and P and a shell having one or more layers, and further contains halogen, and is In in atomic conversion.
  • a semiconductor nanoparticle composite obtained by contacting semiconductor nanoparticles having a molar ratio of halogen to 0.80 to 15.00 with a surface-modifying compound having a binding group that binds to the semiconductor nanoparticles on one end side.
  • the surface modification compound has the following general formula (1): HS-R 1- COO-R 2 (1)
  • R 1 represents an alkylene group having 1 to 3 carbon atoms
  • R 2 represents a hydrophilic group.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is 700 or less.
  • the average SP value of the entire surface modification compound is 9.10 to 11.00. It is a semiconductor nanoparticle composite characterized by.
  • the semiconductor nanoparticle composite (B) of the present invention is a semiconductor nanoparticle composite obtained by contacting semiconductor nanoparticles with a surface-modifying compound having a binding group that binds to the semiconductor nanoparticles on one end side. ..
  • the method of bringing the surface modification compound into contact with the semiconductor nanoparticles is not particularly limited, and examples thereof include a method of adding the surface modification compound to the dispersion liquid of the semiconductor nanoparticles. Depending on the binding force of the surface modification compound to the semiconductor nanoparticles, heating or stirring may be involved when adding the surface modification compound.
  • the semiconductor nanoparticles according to the semiconductor nanoparticle composite (B) of the present invention are the same as the semiconductor nanoparticles according to the semiconductor nanoparticle composite (A) of the present invention.
  • binding group related to the surface modification compound having a binding group that binds to semiconductor nanoparticles on one end side examples include a thiol group, a carboxylic acid group, a phosphine group, a phosphine oxide group, an amine group and the like.
  • the surface modification compound having a binding group to the semiconductor nanoparticles on one end side include the ligand according to the semiconductor nanoparticles composite (A) of the present invention.
  • the semiconductor nanoparticle composite (B) of the present invention contains a mercapto fatty acid ester represented by the following general formula (1) as a surface modification compound having a binding group that binds to semiconductor nanoparticles on one end side.
  • a mercapto fatty acid ester represented by the following general formula (1) as a surface modification compound having a binding group that binds to semiconductor nanoparticles on one end side.
  • the mercapto fatty acid ester represented by the general formula (1) which is a compound for surface modification, is the general formula (1) in the semiconductor nanoparticle composite (A) of the present invention. It is the same as the mercapto fatty acid ester represented by.
  • the semiconductor nanoparticle composite (B) of the present invention by using the mercapto fatty acid ester represented by the general formula (1) as a surface modification compound, the semiconductor nanoparticle composite having high fluorescence quantum efficiency and a narrow half width is used. You can get a body.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is 700 or less.
  • the semiconductor nanoparticles can be dispersed in a polar solvent at a high concentration.
  • the SP value of the mercapto fatty acid ester represented by the general formula (1) is 9.20 or more, preferably 9.20 to 12.00.
  • the semiconductor nanoparticles can be dispersed in the polar solvent.
  • the semiconductor nanoparticle composite (B) of the present invention as a surface modification compound having a binding group that binds to semiconductor nanoparticles on one end side, for surface modification other than the mercapto fatty acid ester represented by the general formula (1). It can contain compounds.
  • the surface-modifying compound other than the mercapto fatty acid ester represented by the general formula (1) is particularly limited as long as it is a compound having a binding group that binds to semiconductor nanoparticles on one end side. However, it can be used as a compound for surface modification of semiconductor nanoparticles, and when used in combination with a mercapto fatty acid ester represented by the general formula (1), the average SP value of the entire surface modification compound can be adjusted to 9. Any compound can be used as long as it can be adjusted to 20 to 11.00, preferably 9.20 to 10.00.
  • the SP value of the surface modification compound other than the mercapto fatty acid ester represented by the general formula (1) is not particularly limited, but is preferably 7.00 to 15.00, and particularly preferably 7.50 to 15.00. ..
  • the average SP value of the entire surface-modifying compound having a binding group that binds to semiconductor nanoparticles on one end side is 9.20 to 11.00, preferably 9.20 to 10.00.
  • the semiconductor nanoparticles can be dispersed in the polar solvent.
  • the surface-modifying compound other than the mercapto fatty acid ester represented by the general formula (1) contains an aliphatic group having a binding group bonded to semiconductor nanoparticles on one end side and an aliphatic group on the other end side.
  • Surface modification compounds are preferred.
  • the semiconductor nanoparticles can be dispersed in a polar solvent at a high concentration.
  • it can be dispersed in an organic solvent having a wider range of SP values.
  • the choice of dispersion medium can be expanded.
  • Examples of the aliphatic group-containing surface modification compound include aliphatic thiol, aliphatic carboxylic acid, aliphatic phosphine, aliphatic phosphine oxide, and aliphatic amine, and are based on the strength of coordinating power with semiconductor nanoparticles.
  • One or more selected from the group consisting of aliphatic thiols, aliphatic carboxylic acids and aliphatic phosphines is preferable.
  • the aliphatic group of the aliphatic group-containing surface modification compound may contain a substituent or a hetero atom.
  • the content of the mercapto fatty acid ester represented by the general formula (1) in the entire surface-modifying compound having a binding group that binds to semiconductor nanoparticles on one end side is preferably 40 mol% or more, more preferably 40 mol% or more. It is 50 mol% or more, more preferably 60 mol% or more.
  • the semiconductor nanoparticles can be used as a polar solvent. It can be dispersed in a high concentration and the quantum efficiency can be increased.
  • the semiconductor nanoparticle composite (B) of the present invention includes the following first form.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) in the semiconductor nanoparticle composite (B) of the present invention is 300 or more and 700.
  • it is a semiconductor nanoparticle composite preferably 300 or more and 600 or less.
  • the first form of the semiconductor nanoparticle composite (B) of the present invention is a core / shell type semiconductor nanoparticle having a core containing In and P and a shell having one or more layers, and further contains halogen. , Obtained by contacting semiconductor nanoparticles having a molar ratio of halogen to In in atomic terms of 0.80 to 15.00 with a surface modifying compound having a binding group that binds to the semiconductor nanoparticles on one end side.
  • the surface modification compound has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is 300 or more and 700 or less, preferably 300 or more and 600 or less.
  • the average SP value of the entire surface modification compound is 9.10 to 11.00. It is a semiconductor nanoparticle composite characterized by.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is in the above range, sufficient steric hindrance is secured for the semiconductor nanoparticles to be dispersed in the organic solvent, and the semiconductor nanoparticles are dispersed at a higher concentration. Further, the heat resistance of the semiconductor nanoparticle composite is improved.
  • the mass ratio of the surface modification compound to the semiconductor nanoparticles is preferably 1.00 or less. It is more preferably 0.70 or less.
  • the semiconductor nanoparticles can be used as a polar solvent while maintaining the heat resistance of the conductor nanoparticles composite. It is possible to disperse at a high concentration.
  • the mass ratio of the surface modification compound and the semiconductor nanoparticles is 0.40 or more. preferable.
  • the semiconductor nanoparticles can be used as a polar solvent while maintaining the heat resistance of the semiconductor nanoparticles composite. It is possible to disperse at a high concentration.
  • the semiconductor nanoparticle composite (B) of the present invention includes the following second form.
  • the molecular weight of the mercapto fatty acid ester represented by the general formula (1) in the semiconductor nanoparticle composite (B) of the present invention is less than 300.
  • the second form of the semiconductor nanoparticle composite (B) of the present invention is a core / shell type semiconductor nanoparticle having a core containing In and P and a shell having one or more layers, and further contains halogen. , Obtained by contacting semiconductor nanoparticles having a molar ratio of halogen to In in atomic terms of 0.80 to 15.00 with a surface modifying compound having a binding group that binds to the semiconductor nanoparticles on one end side.
  • the surface modification compound has the following general formula (1): HS-R 1- COO-R 2 (1) (In the general formula (1), R 1 represents an alkylene group having 1 to 3 carbon atoms, and R 2 represents a hydrophilic group.) Contains one or more mercapto fatty acid esters represented by.
  • the SP value of the mercapto fatty acid ester is 9.20 or more, and the molecular weight of the mercapto fatty acid ester is less than 300, preferably 100 or more and less than 300. Moreover, the average SP value of the entire surface modification compound is 9.10 to 11.00.
  • the mass ratio of the surface modification compound to the semiconductor nanoparticles is preferably 0.40 or less.
  • the mass ratio of the surface modification compound and the semiconductor nanoparticles is within the above range, the semiconductor while suppressing an increase in the viscosity of the dispersion liquid in which the semiconductor nanoparticles composite is dispersed. It is possible to disperse nanoparticles in a polar solvent at a high concentration.
  • the semiconductor nanoparticle composite of the present invention can be separated and purified from the reaction solution, if necessary.
  • a purification method a method is used in which the semiconductor nanoparticle composite is aggregated with a poor solvent and then the semiconductor nanoparticle composite is separated.
  • 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.
  • a method for purifying the semiconductor nanoparticle composite in addition to the methods shown above, for example, aggregation, liquid-liquid extraction, distillation, electrodeposition, size exclusion chromatography and / or ultrafiltration or any method may be used. It may be used alone or in combination.
  • the semiconductor nanoparticle composite of the present invention can be dispersed in a polar dispersion medium to form a semiconductor nanoparticle composite dispersion liquid.
  • 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 semiconductor nanoparticle composite dispersed in a dispersion medium is referred to as a semiconductor nanoparticle composite dispersion liquid.
  • the semiconductor nanoparticle composite of the present invention is also dispersed in an organic dispersion medium having an SP value of 8.50 or more, an organic dispersion medium having an SP value of 9.00 or more, and an organic dispersion medium having an SP value of 10.00 or more. Then, a semiconductor nanoparticle composite dispersion liquid is formed.
  • the SP value here is a value calculated from the Hansen solubility parameter in the same manner as in the method for determining the SP value of the polar ligand.
  • the Hansen solubility parameter is described in the handbook, for example, "Hansen Solubility Parameters: A User's Handbook", 2nd Edition, C.I. M. Hanson (2007), values in, Hanson and Abbot et al. It can be determined using the Practice (HSPiP) program (2nd edition) provided by. Organic dispersion media not described in the handbook can be calculated and determined by the Y-MB method.
  • alcohols such as methanol, ethanol, isopropyl alcohol and normal propyl alcohol, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and the like are used.
  • Esters such as ketones, methyl acetate, ethyl acetate, isopropyl acetate, normal propyl acetate, normal butyl acetate, ethyl lactate, ethers such as diethyl ether, dipropyl ether, dibutyl ether, 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, Glycol ethers such as propylene glycol diethyl ether and dipropylene glycol diethyl ether, ethylene glycol acetate, ethylene
  • the semiconductor nanoparticle composite of the present invention it is possible to select a polar organic dispersion medium such as alcohols, glycol ethers and glycol ether esters as the organic dispersion medium.
  • a polar organic dispersion medium such as alcohols, glycol ethers and glycol ether esters
  • PGMEA and PGME are generally used as diluting solvents, and if the semiconductor nanoparticle composite can be dispersed in PGMEA and PGME, the semiconductor nanoparticle composite is widely applied to the photoresist field. can do.
  • the semiconductor nanoparticle composite of the present invention can disperse the semiconductor nanoparticle composite in an organic dispersion medium at a high mass fraction, and as a result, in the semiconductor nanoparticle composite dispersion liquid.
  • the mass fraction of the semiconductor nanoparticles in the above can be 20% by mass or more, further 30% by mass or more, and further 35% by mass or more.
  • a monomer can be selected as the dispersion medium of the semiconductor nanoparticle composite dispersion liquid of the present invention.
  • the monomer is not particularly limited, but is preferably a (meth) acrylic monomer capable of widely selecting the application destination of the semiconductor nanoparticles.
  • the (meth) acrylic monomer is methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, isoamyl, depending on the application of the semiconductor nanoparticle composite dispersion.
  • the acrylic monomer may be one or a mixture of two or more selected from lauryl (meth) acrylate and 1,6-hexadioldi (meth) acrylate depending on the application of the semiconductor nanoparticle composite dispersion. preferable.
  • a prepolymer can be selected as the dispersion medium of the semiconductor nanoparticle composite dispersion liquid of the present invention.
  • the prepolymer is not particularly limited, and examples thereof include an acrylic resin prepolymer, a silicone resin prepolymer, and an epoxy resin prepolymer.
  • the semiconductor nanoparticle composite composition of the present invention is a semiconductor nanoparticle composite composition in which the semiconductor nanoparticle composite of the present invention is dispersed in a monomer or a prepolymer.
  • the monomer or prepolymer is not particularly limited, and examples thereof include a radically polymerizable compound containing an ethylenically unsaturated bond, a siloxane compound, an epoxy compound, an isocyanate compound, and a phenol derivative.
  • the monomer include the monomers used as the above-mentioned dispersion medium.
  • examples of the prepolymer include the prepolymer used as the dispersion medium described above.
  • the semiconductor nanoparticle composite composition of the present invention can contain a cross-linking agent.
  • the cross-linking agent may be a polyfunctional (meth) acrylate, a polyfunctional silane compound, a polyfunctional amine, a polyfunctional carboxylic acid, a polyfunctional thiol, a polyfunctional alcohol, depending on the type of monomer in the semiconductor nanoparticle composite composition of the present invention.
  • polyfunctional isocyanates and the like may be a polyfunctional (meth) acrylate, a polyfunctional silane compound, a polyfunctional amine, a polyfunctional carboxylic acid, a polyfunctional thiol, a polyfunctional alcohol, depending on the type of monomer in the semiconductor nanoparticle composite composition of the present invention.
  • polyfunctional isocyanates and the like are examples of the like.
  • the semiconductor nanoparticle composite composition of the present invention comprises aliphatic hydrocarbons such as pentane, hexane, cyclohexane, isohexane, heptane, octane and petroleum ether, alcohols, ketones, esters, glycol ethers, etc. It can further contain various organic solvents that do not affect curing, such as glycol ether esters, aromatic hydrocarbons such as benzene, toluene, xylene and mineral spirits, and alkyl halides such as dichloromethane and chloroform.
  • the above-mentioned organic solvent can be used not only for diluting the semiconductor nanoparticle composite composition but also as an organic dispersion medium. That is, it is also possible to disperse the semiconductor nanoparticle composite of the present invention in the above-mentioned organic solvent to obtain a semiconductor nanoparticle composite dispersion liquid.
  • the semiconductor nanoparticle composite composition of the present invention has an appropriate initiator, scattering agent, catalyst, binder, surfactant, adhesion accelerator, and antioxidant depending on the type of monomer in the semiconductor nanoparticle composite composition.
  • Agents, UV absorbers, anti-aggregation agents, dispersants and the like may be included.
  • 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. By including the scattering agent, the absorbance is improved by about twice.
  • the content of the scattering agent in the semiconductor nanoparticle composite composition of the present invention is preferably 2% by mass to 30% by mass with respect to the composition, and from the viewpoint of maintaining the patternability of the composition, 5% by mass to More preferably, it is 20% by mass.
  • the mass fraction of the semiconductor nanoparticles in the semiconductor nanoparticle composite composition of the present invention can be 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.
  • 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 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.
  • 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 spirit, and alkyl halides such as dichloromethane and chloroform are preferable from the viewpoint of solubility in a wide range of resins and film uniformity at the time of coating film.
  • the semiconductor nanoparticle composite cured film of the present invention is a film containing the semiconductor nanoparticle composite of the present invention and represents a cured film.
  • the semiconductor nanoparticle composite cured film of the present invention can be obtained by curing the above-mentioned semiconductor nanoparticle composite composition or diluted composition into a film.
  • the semiconductor nanoparticle composite cured film of the present invention contains the semiconductor nanoparticles according to the semiconductor nanoparticle composite of the present invention, a ligand coordinated on the surface of the semiconductor nanoparticles, and a polymer matrix.
  • the semiconductor nanoparticle composite cured film of the present invention is a cured film in which the semiconductor nanoparticle composite of the present invention is dispersed in a polymer matrix.
  • the polymer matrix is not particularly limited, and examples thereof include (meth) acrylic resin, silicone resin, epoxy resin, silicone resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, and polyurethane resin.
  • the semiconductor nanoparticle composite cured film of the present invention may be obtained by curing the semiconductor nanoparticle composite composition of the present invention described above.
  • the semiconductor nanoparticle composite cured film of the present invention may further contain a cross-linking agent.
  • 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.
  • the semiconductor nanoparticles and the ligand coordinated on the surface of the semiconductor nanoparticles contained in the cured film of the semiconductor nanoparticles composite of the present invention preferably constitute the semiconductor nanoparticles composite of the present invention 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 is preferably 30% by mass or more, and more preferably 40% by mass or more. However, when it is 70% by mass or more, the amount of the composition constituting the film is reduced, and it becomes difficult to cure and form the film.
  • the absorbance of the semiconductor nanoparticle composite cured film of the present invention can be increased.
  • the absorbance is preferably 1.0 or more with respect to light having a wavelength of 450 nm from the normal direction of the semiconductor nanoparticle composite cured film. It is more preferably 3 or more, and further 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 of the present invention is preferably 70% or more, and more preferably 80% or more.
  • the thickness of the semiconductor nanoparticle composite cured film of the present invention is preferably 50 ⁇ m or less, more preferably 20 ⁇ m or less, and more preferably 10 ⁇ m in order to reduce the size of the device to which the semiconductor nanoparticle composite cured film is applied. The following is more preferable.
  • the semiconductor nanoparticle composite patterning film 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 uses the above-mentioned semiconductor nanoparticle composite patterning film.
  • a semiconductor nanoparticle composite patterning film as a wavelength conversion layer, it is possible to provide a display element having excellent fluorescence quantum efficiency.
  • PEG refers to a polyethylene glycol chain and has a structure represented by “ ⁇ (CH 2 CH 2 O) n ⁇ CH 3 ”.
  • ⁇ Making a single ligand> Metal for adjusting 1,1-dimethyl-3-oxobutyl mercaptopropionic acid
  • 5.4 g 1-hydroxybenzotriazole (40 mmol) 100 mL methylene chloride and 7.7 g hydrochloric acid 1 in a flask.
  • reaction solution was transferred to a liquid separation funnel and washed in order with saturated aqueous sodium hydrogen carbonate, water and saturated brine.
  • the obtained organic phase was dried over magnesium sulfate, filtered, and concentrated by evaporation.
  • This concentrate was purified by column chromatography using hexane and ethyl acetate as a developing solvent to obtain the desired ligand (3-mercaptopropionic acid 2- [2- (2-levulinoxycyethoxy) ethoxy] ethyl). ..
  • Example 1 An InP-based semiconductor nanoparticle composite was produced according to the following method. (Preparation of core particles) Indium acetate (0.3 mmol) and zinc oleate (0.6 mmol) are added to a mixture of oleic acid (0.9 mmol), 1-dodecanethiol (0.1 mmol) and octadecene (10 mL) under vacuum ( ⁇ 20 Pa). ) Was heated to about 120 ° C. and reacted for 1 hour. The mixture reacted under vacuum was placed in a nitrogen atmosphere at 25 ° C., tris (trimethylsilyl) phosphine (0.2 mmol) was added, and then the mixture was heated to about 300 ° C.
  • reaction solution was cooled to 25 ° C.
  • octanoic acid chloride (1.1 mmol) was injected, and the mixture was heated at about 250 ° C. for 30 minutes and then cooled to 25 ° C. to obtain a dispersion of InP-based semiconductor nanoparticles.
  • a shell was formed on the surface of the InP-based semiconductor nanoparticles (core) as follows.
  • the core dispersion was heated to 200 ° C. It was added to 6.0 mL of a Zn precursor solution and 2.0 mL of trioctylphosphine selenide at 250 ° C. and reacted for 30 minutes to form a ZnSe shell on the surface of InP-based semiconductor nanoparticles. Further, 4.0 mL of a Zn precursor solution and 1.8 mL of trioctylphosphine sulfide were added, and the temperature was raised to 280 ° C. and reacted for 1 hour to form a ZnS shell.
  • the obtained semiconductor nanoparticles were observed by STEM-EDS, it was confirmed that they had a core / shell structure.
  • Dehydrated acetone was added to the solution in which the semiconductor nanoparticles having the core / shell structure obtained by the synthesis were dispersed, and the semiconductor nanoparticles were aggregated. Then, after centrifugation (4000 rpm, 10 minutes), the supernatant was removed and the semiconductor nanoparticles were redispersed in hexane. This was repeated to obtain purified semiconductor nanoparticles.
  • Elemental analysis of semiconductor nanoparticles was performed using a radio frequency inductively coupled plasma emission spectrometer (ICP) and a fluorescent X-ray analyzer (XRF).
  • ICP radio frequency inductively coupled plasma emission spectrometer
  • XRF fluorescent X-ray analyzer
  • the purified semiconductor nanoparticles were dissolved in nitric acid, heated, diluted with water, and measured by a calibration curve method using an ICP emission spectrometer (ICPS-8100, manufactured by Shimadzu Corporation).
  • ICPS-8100 ICP emission spectrometer
  • XRF measurement a filter paper impregnated with a dispersion was placed in a sample holder and quantitative analysis was performed using a fluorescent X-ray analyzer (ZSX100e manufactured by Rigaku). The molar ratio of halogen to In of the semiconductor nanoparticles is shown in Table 1.
  • a semiconductor nanoparticle 1-octadecene dispersion was prepared by dispersing the purified semiconductor nanoparticles in 1-octadecene so as to have a mass ratio of 10% by mass in a flask. 10.0 g of the prepared semiconductor nanoparticles 1-octadecene dispersion was placed in a flask, 3.6 g of thioglycolic acid PEG ester (molecular weight 470) was added as a mercapto fatty acid ester, 0.4 g of dodecanethiol was added as a non-polar ligand, and nitrogen was added. The mixture was stirred at 110 ° C.
  • the reaction solution containing the semiconductor nanoparticle composite 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.
  • 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 semiconductor nanoparticle composite were measured using a fluorescence quantum efficiency measurement system (QE-2100, manufactured by Otsuka Electronics Co., Ltd.).
  • the semiconductor nanoparticle composite obtained by the synthesis was dispersed in a dispersion medium, and a single light of 450 nm was applied as excitation light to obtain an emission spectrum.
  • 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 portion that was re-excited and fluorescently emitted from the emission spectrum obtained here.
  • PGMEA Propylene glycol monomethyl ether acetate
  • Thermogravimetric analysis 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 (ligand / semiconductor nanoparticles) of the ligand and the semiconductor nanoparticles in the semiconductor nanoparticles complex was confirmed from this value. The results obtained are shown in Tables 1 and 3.
  • the semiconductor nanoparticle composite was dispersed in isovonyl acrylate so that the concentration of the semiconductor nanoparticles was 30.0% by mass to prepare a dispersion. Then, the viscosity of the obtained dispersion was measured at 25 ° C. with an AR-2000 rheometer manufactured by TA Instruments. The measurement was carried out by performing preliminary shearing at 0.1 s -1 for 1 minute and then changing the shear rate from 0.1 s -1 to 1000 s -1 .
  • Example 2 Same as Example 1 except that 3.2 g of 3-mercaptopropionic acid PEG ester (molecular weight 550) was used as the mercapto fatty acid ester and 0.8 g of oleic acid was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle complex.
  • a semiconductor nanoparticle composite was obtained by the above method.
  • Example 3 In the process of preparing the semiconductor nanoparticle complex, it was carried out except that 3.2 g of thioglycolic acid PEG ester (molecular weight 470) was used as the mercapto fatty acid ester and 0.8 g of ethylhexyl 3-mercaptopropionate was used instead of the aliphatic ligand.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1.
  • Example 4 Same as Example 1 except that 6.4 g of 3-mercaptopropionic acid PEG ester (molecular weight 640) was used as the mercapto fatty acid ester and 0.8 g of dodecanthiol was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle complex.
  • a semiconductor nanoparticle composite was obtained by the above method.
  • Example 5 The same method as in Example 1 except that 2.8 g of thioglycolic acid PEG ester (molecular weight 470) was used as the mercapto fatty acid ester and 1.2 g of dodecanethiol was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle composite. Obtained a semiconductor nanoparticle composite.
  • Example 6 The same method as in Example 1 except that 2.4 g of thioglycolic acid PEG ester (molecular weight 470) was used as the mercapto fatty acid ester and 1.6 g of dodecanethiol was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle composite. Obtained a semiconductor nanoparticle composite.
  • Example 7 0.45 mmol of octanoic acid chloride was used when preparing the dispersion of core particles, 3.6 g of 3-mercaptopropionic acid PEG ester (molecular weight 550) was used as the mercapto fatty acid ester when preparing the semiconductor nanoparticle complex, and dodecane was used as the aliphatic ligand.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 0.4 g of thiol was used.
  • Example 8 At the time of preparation of the dispersion of core particles, 2.5 mmol of octanoic acid chloride was used, and at the time of preparation of the semiconductor nanoparticle complex, 3.8 g of 3-mercaptopropionic acid PEG ester as a mercapto fatty acid ester and dodecanethiol as an aliphatic ligand were used.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 2 g was used.
  • Example 9 In the process of preparing the semiconductor nanoparticle complex, 3.6 g of 3-mercaptopropionic acid 2- [2- [2- (2-hexyloxyethoxy) ethoxy] ethoxy] ethyl as a mercapto fatty acid ester and dodecane as an aliphatic ligand A semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 0.4 g of thiol was used.
  • Example 10 In the process of preparing the semiconductor nanoparticle complex, 3.8 g of 2- [2- (2-levulinoxyethoxy) ethoxy] ethyl 3-mercaptopropionic acid as a mercapto fatty acid ester and 0. dodecanethiol as an aliphatic ligand.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 2 g was used.
  • Example 11 In the process of preparing the semiconductor nanoparticle complex, it was carried out except that 3.6 g of 3-mercaptopropionic acid 1,1-dimethyl-3-oxobutyl was used as the mercapto fatty acid ester and 0.4 g of trioctylphosphine as the aliphatic ligand. A semiconductor nanoparticle composite was obtained in the same manner as in Example 1.
  • Example 12 0.45 mmol of octanoic acid chloride was used as a dispersion of core particles, 3.2 g of 3-methoxybutyl 3-mercaptopropionate as a mercapto fatty acid ester, and dodecanethiol as an aliphatic ligand when preparing a semiconductor nanoparticle complex.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 0.8 g was used.
  • Example 13 When preparing the dispersion of core particles, 2.5 mmol of octanoic acid chloride was used, and when the semiconductor nanoparticle composite was prepared, 3.2 g of 3-mercaptopropionic acid 1,1-dimethyl-3-oxobutyl as a mercapto fatty acid ester was used as an aliphatic. A semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 0.8 g of dodecanethiol was used as a ligand.
  • Example 14 In the step of preparing the semiconductor nanoparticle complex, the same method as in Example 1 was used except that 2.8 g of 3-methoxybutyl 3-mercaptopropionate was used as the mercapto fatty acid ester and 1.2 g of dodecanethiol was used as the aliphatic ligand. A semiconductor nanoparticle composite was obtained.
  • Example 15 In the process of preparing the semiconductor nanoparticle complex, 3.8 g of 2- [2- (2-acetoxyethoxy) ethoxy] ethyl 3-mercaptopropionic acid as a mercapto fatty acid ester and 0.05 g of dodecanethiol as an aliphatic ligand were used. A semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except for the above.
  • Example 16 Same as in Example 1 except that 2.8 g of 3-methoxybutyl 3-mercaptopropionate was used as the mercapto fatty acid ester and 1.2 g of benzenethiol was used instead of the aliphatic ligand in the step of preparing the semiconductor nanoparticle complex.
  • a semiconductor nanoparticle composite was obtained by the above method.
  • Example 17 In the shell formation reaction, after forming a ZnSe shell, the mixture was cooled to room temperature without adding a Zn precursor solution and trioctylphosphine sulfide. Furthermore, except that 3.2 g of 3-mercaptopropionic acid 1,1-dimethyl-3-oxobutyl was used as the mercapto fatty acid ester and 0.8 g of dodecanethiol was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle complex. A semiconductor nanoparticle composite was obtained in the same manner as in Example 1.
  • Example 1 The same method as in Example 1 except that 9.6 g of thioglycolic acid PEG ester (molecular weight 760) was used as the mercapto fatty acid ester and 0.8 g of dodecanethiol was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle composite. Obtained a semiconductor nanoparticle composite.
  • Example 3 In the step of preparing the semiconductor nanoparticle composite, a semiconductor was used in the same manner as in Example 1 except that 3.2 g of 6-mercaptohexanoic acid PEG ester was used as the mercapto fatty acid ester and 0.8 g of dodecanethiol was used as the aliphatic ligand. A nanoparticle composite was obtained.
  • Example 4 The same method as in Example 1 except that 2.0 g of thioglycolic acid PEG ester (molecular weight 470) was used as the mercapto fatty acid ester and 2.0 g of dodecanethiol was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle composite. Obtained a semiconductor nanoparticle composite. Chloroform was used as a solvent for the fluorescence quantum yield measurement.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except for the above. Normal hexane was used as a solvent for the fluorescence quantum yield measurement.
  • a semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except for the above. Chloroform was used as a solvent for the fluorescence quantum yield measurement.
  • Example 8 Same as in Example 1 except that 3.2 g of 2-hydroxyethyl 3-mercaptopropionate was used as the mercapto fatty acid ester and 0.8 g of trioctylphosphine was used as the aliphatic ligand in the step of preparing the semiconductor nanoparticle complex.
  • a semiconductor nanoparticle composite was obtained by the method. This semiconductor nanoparticle composite did not disperse in chloroform and PGMEA, and fluorescence quantum yield measurement could not be performed.
  • Example 10 A semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that octanoic acid chloride was not added when the dispersion of core particles was prepared.
  • Example 11 A semiconductor nanoparticle composite was obtained in the same manner as in Example 1 except that 0.3 mm réellel of indium chloride was added instead of indium acetate and octanoic acid chloride was not added when preparing the dispersion of core particles. .. Indium chloride added during the preparation of the dispersion of core particles generates hydrogen chloride as a by-product during synthesis. Therefore, it was found that in the finally obtained semiconductor nanoparticles, the halogen content in the semiconductor nanoparticles is smaller than that in which the halogen precursor is added at the time of preparing the core particle dispersion. did.
  • the semiconductor nanoparticle composite has a high fluorescence quantum efficiency (QY), is excellent in dispersibility in a polar dispersion medium, and has a high mass. It is possible to disperse in fractions.
  • QY fluorescence quantum efficiency
  • Comparative Example 5 in which the mercapto fatty acid ester is not used, Comparative Example 1 in which the molecular weight of the mercapto fatty acid ester is too large, Comparative Example 3 and Comparative Example 7 in which the SP value of the mercapto fatty acid ester is too low, and the average SP of the entire ligand is too low.
  • Comparative Example 4 and Comparative Example 8 in which the average SP of the entire ligand is too high, the dispersibility in a polar dispersion medium is poor, and it is difficult to disperse at a high mass fraction. Further, in Comparative Example 2, Comparative Example 6, Comparative Example 9, Comparative Example 10 and Comparative Example 11, since the halogen / In of the semiconductor nanoparticles is out of the range specified in the present invention, the fluorescence quantum efficiency is low. Furthermore, the filterability was also low.
  • Examples 1 to 10 in which the molecular weight of the mercapto fatty acid ester represented by the general formula (1) is in the range of 300 or more and 700 or less are excellent in heat resistance, and the general formula (1) of the present invention is used. It has been found that the semiconductor nanoparticle composite using a mercapto fatty acid ester represented by a molecular weight of 300 or more and 700 or less is particularly suitable for applications in which heat resistance is important.
  • the viscosity of the dispersion liquid when dispersed in the dispersion medium is compared with Examples 11 to 17 using the mercapto fatty acid ester represented by the general formula (1) having a molecular weight of less than 300. Although it is expensive, it can be used except for applications that require a low viscosity of the dispersion medium.

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