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WO2019188679A1 - Procédé de production de points quantiques en phosphure d'indium - Google Patents

Procédé de production de points quantiques en phosphure d'indium Download PDF

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Publication number
WO2019188679A1
WO2019188679A1 PCT/JP2019/011759 JP2019011759W WO2019188679A1 WO 2019188679 A1 WO2019188679 A1 WO 2019188679A1 JP 2019011759 W JP2019011759 W JP 2019011759W WO 2019188679 A1 WO2019188679 A1 WO 2019188679A1
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indium
general formula
quantum dots
compound represented
compound
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Japanese (ja)
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一博 中對
洋介 田久保
田村　健
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Nippon Chemical Industrial Co Ltd
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Nippon Chemical Industrial Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/08—Other phosphides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/70—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing phosphorus

Definitions

  • the present invention relates to a method for producing InP quantum dots.
  • quantum dots have been developed as light emitting materials.
  • cadmium-based quantum dots such as CdSe, CdTe, and CdS are being developed because of excellent light emission characteristics.
  • the development of cadmium-free quantum dots is expected due to the high toxicity and environmental impact of cadmium.
  • One of the cadmium-free quantum dots is InP (indium phosphide).
  • InP indium phosphide
  • phosphine, aminophosphine compounds, silylphosphine compounds and the like are often used as raw materials for the phosphorus component (for example, Patent Documents 1 to 3).
  • the present inventors have reduced the amount of a specific component among the impurity components in the silylphosphine compound, thereby obtaining a particle size distribution of InP quantum dots obtained. It was found that an InP quantum dot having a small full width at half maximum of the emission peak can be obtained by narrowing, and the present invention has been completed.
  • the present invention is a method for producing an InP quantum dot by reacting a phosphorus source and an indium source, and the phosphorus source contains 0.3 mol of a compound represented by the following general formula (2).
  • the present invention provides a method for producing InP quantum dots using a silylphosphine compound represented by the following general formula (1) which is not more than%.
  • R is each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • R is the same as in general formula (1).
  • InP indium phosphide
  • InP quantum dots refer to semiconductor nanoparticles that contain In and P and have a quantum confinement effect.
  • the quantum confinement effect is that when the size of a substance is about the Bohr radius, the electrons in it cannot move freely, and in such a state, the energy of the electrons is not arbitrary and can take only a specific value.
  • the particle size of quantum dots is generally in the range of several nm to several tens of nm.
  • InP in an InP quantum dot means containing In and P, and it is not required until In and P are 1: 1 molar ratio.
  • InP quantum dots are expected to be applied to single-electron transistors, teleportation, lasers, solar cells, quantum computers, etc., using the quantum confinement effect.
  • InP quantum dots have been proposed for use as phosphors, and their application to biomarkers, light-emitting diodes, and the like has been proposed.
  • the InP quantum dots are quantum dots composed of In and P, the maximum absorption wavelength in UV-VIS is preferably 450 to 550 nm, and more preferably 460 to 540 nm.
  • the amount of In and P in the sample liquid at the time of UV-VIS measurement is preferably in the range of 0.01 mmol to 1 mmol in terms of phosphorus atoms and indium atoms with respect to 100 g of the sample liquid, and 0.02 mmol to 0. More preferably, it is in the range of 3 mmol.
  • the InP quantum dots manufactured by the manufacturing method of the present invention may be quantum dots (also referred to as composite quantum dots) made of a composite compound having an element M other than phosphorus and indium in addition to In and P.
  • the element M is preferably at least one selected from the group consisting of Be, Mg, Zn, B, Al, Ga, S, Se, and N from the viewpoint of improving the quantum yield.
  • Typical examples of InP quantum dots containing the element M include InGaP, InZnP, InAlP, InGaAlP, InNP, and the like.
  • the InP quantum dots may be a mixture of In and P, and InMP containing the element M in addition to other semiconductor compounds.
  • Such a semiconductor compound is preferably the same group III-V semiconductor as InP from the viewpoint of improving the quantum yield.
  • GaP, AlP, GaAs, AlN, AlAs, InN, BP, GaN examples include GaSb and InAs.
  • the InP quantum dots may have a core-shell structure in which an InP quantum dot material is a core and the core is covered with a coating compound.
  • a second inorganic material shell layer
  • Suitable coating compounds include ZnS, ZnSe, ZnTe, GaP, and GaN. In the present invention, those having such a core-shell structure are also included in the InP quantum dots.
  • a silylphosphine compound represented by the following general formula (1) is used as a phosphorus source to be reacted with an indium source.
  • the silylphosphine compound used as the phosphorus source is tertiary, that is, a compound in which three silyl groups are bonded to a phosphorus atom.
  • R is each independently an alkyl group having 1 to 5 carbon atoms or an aryl group having 6 to 10 carbon atoms.
  • Examples of the alkyl group having 1 to 5 carbon atoms represented by R include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, iso- Examples thereof include a butyl group, an n-amyl group, an iso-amyl group, and a tert-amyl group.
  • Examples of the aryl group having 6 to 10 carbon atoms represented by R include phenyl group, tolyl group, ethylphenyl group, propylphenyl group, iso-propylphenyl group, butylphenyl group, sec-butylphenyl group, and tert-butyl. Examples thereof include a phenyl group, an iso-butylphenyl group, a methylethylphenyl group, and a trimethylphenyl group.
  • These alkyl group and aryl group may have one or more substituents, and examples of the substituent of the alkyl group include a hydroxy group, a halogen atom, a cyano group, and an amino group.
  • substituents examples include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, a halogen atom, a cyano group, and an amino group.
  • the aryl group is substituted with an alkyl group or an alkoxy group, the carbon number of the aryl group includes the carbon number of the alkyl group or alkoxy group.
  • a plurality of R in the formula (1) may be the same or different (the same applies to the formulas (I) and (2) to (7) described later). Further, the three silyl groups (—SiR 3 ) present in the formula (1) may be the same or different.
  • the silylphosphine compound represented by the formula (1) a compound in which R is an alkyl group having 1 to 4 carbon atoms or a phenyl group substituted with an unsubstituted or alkyl group having 1 to 4 carbon atoms is a synthetic reaction. From the viewpoint of excellent reactivity with other molecules such as an indium source as a phosphorus source, a trimethylsilyl group is particularly preferable.
  • the silylphosphine compound of the formula (1) used as a phosphorus source has a low content of the compound of the formula (2).
  • the present inventor has intensively studied a method capable of narrowing the particle size distribution of InP quantum dots obtained using the silylphosphine compound of the formula (1) as a raw material. It has been found that there is a problem that particle formation does not proceed successfully due to the influence of. And it discovered that the full width at half maximum of the obtained InP quantum dot could be narrowed by reducing the content of this impurity.
  • the content of the compound represented by the general formula (2) is 0.3 mol% or less, and more preferably 0.25 mol% or less. , 0.2 mol% or less is particularly preferable.
  • the silylphosphine compound of the present invention preferably contains less other impurities from the viewpoint of effectively reducing the adverse effects of InP nanoparticle formation due to impurities and making the full width at half maximum of InP quantum dots narrower.
  • the content of the compound represented by the formula (3) is preferably 0.1 mol% or less, more preferably 0.08 mol% or less. And 0.05 mol% or less is particularly preferable.
  • the content of the silyl ether compound represented by the formula (4) is preferably 0.50 mol% or less, more preferably 0.30 mol% or less, More preferably, it is 0.15 mol% or less.
  • the content of the compound represented by the formula (5) is preferably 0.50 mol% or less, more preferably 0.30 mol% or less, and 0.15 mol%. % Or less is more preferable, and 0.05 mol% or less is particularly preferable.
  • the content of the compound represented by the formula (6) is preferably 0.30 mol% or less, more preferably 0.15 mol% or less, and 0.05 mol%. It is particularly preferred that
  • the content of the compound represented by the formula (7) is preferably 1.0 mol% or less, more preferably 0.5 mol% or less, and 0.2 mol%. It is particularly preferred that
  • the silylphosphine compound in which any one, two or more or all of the compounds represented by the formulas (3) to (7) are not more than the above upper limit is particularly a quantum dot.
  • the particle formation is further improved and the particle size distribution is narrow.
  • the content of the compound represented by the formulas (2) to (7) is a ratio with respect to the compound represented by the formula (1).
  • a suitable production method of the compound represented by the formula (1) described later is adopted, and in the production method, a silylating agent, phosphine, What is necessary is just to adjust the quantity ratio.
  • the content of the compound represented by the formula (3) can be measured, for example, by the method described in Examples described later by analysis by 31 P-NMR.
  • a suitable method for producing the compound represented by the formula (1) described later may be employed.
  • the content of the compound represented by the formula (4) can be measured by analysis by gas chromatography, for example, by the method described in Examples described later.
  • a suitable method for producing the compound of the formula (1) described later may be employed, and the high-boiling component may be separated at that time.
  • the content of the compound represented by the formula (7) can be measured, for example, by the method described in Examples described later by analysis by 31 P-NMR.
  • the amount of the compounds represented by the above formulas (2) to (7) is applicable both when the silylphosphine compound is present as a solid such as a powder or when it is dispersed in a solvent. . That is, in the former case, the preferred molar ratio of the compounds represented by the formulas (2) to (7) listed above is the formula (2) to (7) in a solid such as a powder composed of a silylphosphine compound.
  • the molar ratio of the represented compound to the compound of formula (1) is meant. In the latter case, the above preferred molar ratio means the molar ratio of the compound represented by the formulas (2) to (7) to the compound of the formula (1) in the dispersion in which the silylphosphine compound is dispersed.
  • the purity of the compound represented by the formula (1) used in the present invention is preferably 99.0 mol% or more, more preferably 99.3 mol% or more, and 99.5 mol% or more. Is particularly preferred.
  • the purity of the compound represented by the formula (1) can be measured, for example, by the method described in Examples described later by analysis by 31 P-NMR.
  • Preferred examples of the silylating agent include compounds represented by formula (I). (R is the same as in formula (1), and X is at least one selected from a fluorosulfonic acid group, a fluoroalkanesulfonic acid group, an alkanesulfonic acid group, and a perchloric acid group.)
  • the fluorosulfonic acid group represented by X is also represented by “—OSO 2 F”.
  • Examples of the fluoroalkanesulfonic acid group represented by X include a perfluoroalkanesulfonic acid group.
  • trifluoromethanesulfonic acid group —OSO 2 CF 3
  • pentafluoroethanesulfonic acid group —OSO 2 C 2 F 5
  • heptafluoropropanesulfonic acid group —OSO 2 C 3 F 7
  • nonafluorobutane examples thereof include a sulfonic acid group (—OSO 2 C 4 F 9 ) and an undecafluoropentane sulfonic acid group (—OSO 2 C 5 F 11 ).
  • alkanesulfonic acid group represented by X examples include a methanesulfonic acid group (—OSO 2 CH 3 ), an ethanesulfonic acid group (—OSO 2 C 2 H 5 ), and a propanesulfonic acid group (—OSO 2 C 3 H 7 ). , Butanesulfonic acid group (—OSO 2 C 4 H 9 ), pentanesulfonic acid (—OSO 2 C 5 H 11 ) and the like.
  • the perchloric acid group represented by X is also represented by “—OClO 3 ”. In these formulas, “-” represents a bond.
  • the relative dielectric constant is the ratio of the dielectric constant of the substance to the dielectric constant in vacuum. In general, the relative dielectric constant increases as the polarity of the solvent increases.
  • a value described in “Chemical Handbook Basic Revised Edition 5” (edited by the Chemical Society of Japan, published on February 20, 2004, pages II-620 to II-622) is used. be able to.
  • the solvent having a relative dielectric constant of 4 or less is an organic solvent, and preferably includes hydrocarbons. Particularly, hydrocarbons not containing chlorine atoms are preferable, and hydrocarbons not containing halogen atoms are particularly preferable.
  • Specific examples of the solvent include acyclic or cyclic aliphatic hydrocarbon compounds and aromatic hydrocarbon compounds.
  • Preferred examples of the acyclic aliphatic hydrocarbon compound include those having 5 to 10 carbon atoms, such as pentane (dielectric constant 1.8371), n-hexane (dielectric constant 1.8865), n-heptane.
  • cycloaliphatic hydrocarbon compound examples include those having 5 to 8 carbon atoms, such as cyclohexane (dielectric constant 2.0243) and cyclopentane (dielectric constant 1.9687). Can be mentioned.
  • aromatic hydrocarbon compound examples include those having 6 to 10 carbon atoms, such as benzene (relative permittivity: 2.2825), toluene (relative permittivity: 2.379) and p-xylene (relative permittivity: 2.2735). ) Is particularly preferable.
  • Basic compounds include not only narrowly defined bases that give hydroxide ions when dissolved in water, but also broadly defined bases such as substances that accept protons and substances that give electron pairs.
  • the basic compound is preferably an amine from the viewpoint that side reactions with phosphine can be suppressed.
  • the amines include primary, secondary or tertiary alkylamines; anilines; toluidine; piperidine; pyridines.
  • Primary, secondary or tertiary alkylamines include methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, diisopropylamine, butylamine, isobutylamine, dibutylamine, tributylamine, pentylamine, dipentylamine , Tripentylamine, 2-ethylhexylamine and the like.
  • anilines include aniline, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline and the like.
  • pyridines include pyridine and 2,6-di (t-butyl) pyridine.
  • the amount of the silylating agent in the mixed solution is that the specific amount of the silylating agent is combined with the use of a specific solvent described below, and impurities, particularly secondary silylphosphine compounds such as the compound of formula (2) and the formula (3) From the viewpoint of effectively suppressing the formation of primary silylphosphine which is a compound of the above.
  • the ratio of the silylating agent to the phosphine introduced into the mixed solution is preferably not less than the reaction equivalent, that is, not less than 3 times the mole of phosphine, more than 3 times the mole, further more than 3.01 times the mole, especially 3.05 times. More preferably, it is at least a mole.
  • the amount of the silylating agent in the mixed solution is more than the reaction equivalent with phosphine but not so much that it can be said to be excessive, reducing the residual amount of excess silylating agent and increasing the purity, This is preferable from the viewpoint of cost reduction.
  • the silylating agent in the mixed solution is preferably 2 times or less of the reaction equivalent to the phosphine introduced into the mixed solution, that is, 6 times or less, particularly preferably 4 times or less, Most preferably, it is 3.5 times mol or less.
  • the basic compound is preferably in a specific amount from the viewpoint of effectively suppressing the generation of impurities, particularly secondary or primary silylphosphine, together with the use of a specific solvent.
  • the ratio of the basic compound in the mixed solution to the phosphine introduced into the mixed solution is preferably equal to or greater than the reaction equivalent.
  • the basic compound is a monovalent base, it is preferably at least 3 times the mole of phosphine. It is more preferable that it is more than double mole, further 3.3 mole or more, particularly 3.5 mole or more.
  • the basic compound in the mixed solution is preferably not in excess, and preferably in such a large amount that it cannot be said that it is excessive, from the viewpoint of increasing the purity of the target product and reducing production costs.
  • the basic compound in the mixed solution is preferably 2 times or less of the reaction equivalent to the phosphine introduced into the mixed solution, for example, preferably 6 times or less, and preferably 5 times or less. It is particularly preferable that it is 4 times mol or less.
  • the relative dielectric constant in the solvent is preferably 0.5 or more as a lower limit, more preferably 1 or more from the viewpoint of easy progress of the reaction according to the above reaction formula. Moreover, as an upper limit, it is more preferable that it is 3.5 or less, and it is still more preferable that it is 3 or less.
  • the boiling point of the solvent is preferably 200 ° C. or lower, more preferably 40 ° C. or higher and 120 ° C. or lower. .
  • the method for preparing a mixed solution of a solvent, a basic compound, and a silylating agent is not limited, and three materials may be charged into the reaction vessel at the same time, either one or two is charged first, and the rest is charged later. But you can.
  • the solvent is dehydrated before use in order to prevent decomposition of the silylphosphine compound due to reaction with water and generation of impurities due thereto.
  • the amount of water in the solvent is preferably 20 ppm or less, and preferably 10 ppm or less on a mass basis.
  • the amount of moisture can be measured by the method described in the examples described later.
  • the solvent be degassed before use to remove oxygen. Degassing can be performed by any method such as replacement with an inert atmosphere in the reactor.
  • the amount of the solvent is not limited, but it is preferably 100 parts by mass or more and 300 parts by mass or less, and particularly preferably 120 parts by mass or more and 200 parts by mass or less, with respect to 100 parts by mass of the silylating agent, from the viewpoint of efficient reaction. .
  • the inert gas include nitrogen gas, rare gases such as helium gas and argon gas.
  • the liquid temperature of the mixed solution when introducing phosphine is preferably 20 ° C. or higher from the viewpoint of improving the reaction rate and yield, and 85 ° C. or lower is preferable from the viewpoint of preventing decomposition of the target product. From these points, the liquid temperature of the mixed solution is more preferably 25 ° C. or higher and 70 ° C. or lower.
  • the obtained solution is preferably aged before being subjected to solvent removal in the second step.
  • This aging is preferably performed at a temperature of 20 ° C. or higher and 60 ° C. or lower, more preferably 20 ° C. or higher and 50 ° C. or lower, from the viewpoint of improving the reaction rate or yield.
  • the aging time is preferably 1 hour to 48 hours, more preferably 2 hours to 24 hours. This aging is preferably performed in an inert atmosphere.
  • a solution containing a silylphosphine compound is obtained by the above first step.
  • a second step of removing (separating) at least a part of the solvent from the solution containing the silylphosphine compound to obtain a concentrated solution of the silylphosphine compound of the formula (1) is performed.
  • the amount of solvent distilled off in the third step described later is reduced, and the yield of the silylphosphine compound is reduced as the solvent is distilled off during distillation.
  • thermal alteration and decomposition of the target silylphosphine compound of formula (1) can be prevented.
  • the silylphosphine compound of the formula (1) is allowed to stand by allowing the solution containing the silylphosphine compound of the formula (1) obtained in the first step (preferably including the aging treatment) to stand. a layer containing, HB a + X - were separated and a layer comprising, separated by removal of the latter, HB a + X - can be removed.
  • the standing time is preferably 0.5 hours or more and 48 hours or less, and more preferably 1 hour or more and 24 hours or less. Separation is preferably performed under an inert atmosphere.
  • (Second step) As a method for removing the solvent in the second step, a method of evaporating the solvent by heating a solution containing the silylphosphine compound of the formula (1) under reduced pressure under a condition in which the target silylphosphine compound is almost left. It is done. This treatment can be carried out in any distillation apparatus for removing the solvent, such as a rotary evaporator.
  • the liquid temperature when heating the solution containing the silylphosphine compound of formula (1) under reduced pressure is the highest from the viewpoint of efficiently removing the solvent and preventing the decomposition and alteration of the silylphosphine compound.
  • the liquid temperature is preferably 20 ° C. or higher and 140 ° C.
  • the pressure during pressure reduction is preferably 2 kPa to 20 kPa, more preferably 5 kPa to 10 kPa, based on absolute pressure. Concentration is preferably performed under an inert atmosphere.
  • the amount of the silylphosphine compound in the solution containing the silylphosphine compound after the second step is preferably 5% by mass or less with respect to the amount of the silylphosphine compound in the solution at the start of the second step. This amount can be measured by 31 P-NMR.
  • the mass of the concentrate obtained in the second step is preferably 10% or more of the mass of the solution containing the silylphosphine compound obtained in the first step from the viewpoint of yield improvement, and is 50% or less. This is preferable in that the purity is increased by reducing the amount of remaining solvent in the next third step.
  • the conditions for distillation are the conditions for vaporizing the silylphosphine compound, and the distillation temperature (column top temperature) is preferably 50 ° C. or higher from the viewpoint of excellent separation of the target compound.
  • the distillation temperature is preferably 150 ° C. or lower from the viewpoint of inhibiting decomposition of the target compound and maintaining the quality. From these points, the distillation temperature is preferably 50 ° C. or higher and 150 ° C. or lower, and more preferably 70 ° C. or higher and 120 ° C. or lower.
  • the pressure at the time of distillation is preferably 0.01 kPa or more on the basis of absolute pressure from the viewpoint of efficiently recovering a target compound with high purity. Further, the pressure during distillation is preferably 5 kPa or less on the basis of absolute pressure, from the viewpoint of being able to suppress decomposition and alteration of the silylphosphine compound and easily obtaining the silylphosphine compound with high purity and high yield. From these points, the pressure during distillation is preferably 0.01 kPa to 5 kPa, and more preferably 0.1 kPa to 4 kPa.
  • the distillation is preferably performed under an inert atmosphere.
  • the purity can be improved by removing this.
  • the amount of the silylphosphine compound in the distillation residue after vaporizing the silylphosphine compound is preferably 90% of the reduction ratio with respect to the amount of the silylphosphine compound in the solution containing the silylphosphine compound at the start of the third step. It is at least mass%. This amount can be measured by 31 P-NMR.
  • the target silylphosphine compound of the formula (1) is obtained by the above third step.
  • the resulting silylphosphine compound is stored in a liquid or solid state in an environment in which contact with oxygen, moisture, etc. is eliminated as much as possible, or is stored as a dispersed liquid dispersed in an appropriate solvent.
  • the dispersion includes a solution.
  • the solvent in which the silylphosphine compound is dispersed is an organic solvent, and in particular, a nonpolar solvent is preferable from the viewpoint of preventing water contamination and decomposition of the silylphosphine compound.
  • a nonpolar solvent include saturated aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatic hydrocarbon compounds, and trialkylphosphine.
  • saturated aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-hexadecane, and n-octadecane.
  • Examples of the unsaturated aliphatic hydrocarbon include 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene and the like.
  • Aromatic hydrocarbons include benzene, toluene, xylene, styrene and the like.
  • Examples of the trialkylphosphine include triethylphosphine, tributylphosphine, tridecylphosphine, trihexylphosphine, trioctylphosphine, and tridodecylphosphine.
  • the organic solvent in which the silylphosphine compound is dispersed has a high boiling point because the silylphosphine compound having spontaneous ignition can be stably stored and transported.
  • the preferred boiling point of the organic solvent is 50 ° C. or higher, more preferably 60 ° C. or higher.
  • the upper limit of the boiling point of the organic solvent is preferably 270 ° C. or lower (absolute pressure 0.1 kPa) from the viewpoint of the influence on the properties of organic synthetic products and quantum dots produced using this as a raw material.
  • the solvent be sufficiently dehydrated before the silylphosphine compound is dispersed in order to prevent decomposition of the silylphosphine compound due to reaction with water and generation of impurities thereby.
  • the amount of water in the solvent is preferably 20 ppm or less, more preferably 10 ppm or less on a mass basis.
  • the amount of moisture can be measured by the method described in the examples described later.
  • the solvent is degassed and dehydrated while heating under reduced pressure or under vacuum conditions, and then mixed with a silylphosphine compound and filled in an airtight container in a nitrogen gas atmosphere. .
  • the proportion of the silylphosphine compound is preferably 3% by mass or more and 50% by mass or less, and more preferably 8% by mass or more and 30% by mass or less.
  • a high-purity tertiary silylphosphine compound with reduced amounts of various impurities can be obtained by using a specific solvent and passing through a specific process.
  • a phosphorus source containing a silylphosphine compound represented by the above formula (1) is reacted with an indium source.
  • the production method of the present invention may be any method using a silylphosphine compound with a small amount of impurities of formula (2), and various methods can be used.
  • the chemical synthesis method include a sol-gel method (colloid method), a hot soap method, a reverse micelle method, a solvothermal method, a molecular precursor method, a hydrothermal synthesis method, or a flux method.
  • indium source various sources can be used according to the chemical synthesis method employed.
  • indium trichloride may be used as described in Patent Document 4, and Patent Documents 5 and 6 describe.
  • indium organic carboxylate may be used. From the viewpoint of easily obtaining InP nanocrystals, availability, and particle size distribution control, indium organic carboxylates are preferably mentioned.
  • indium acetate, indium laurate, indium myristate, indium palmitate, indium formate, Indium propionate, indium butyrate, indium valerate, indium caproate, indium enanthate, indium caprylate, indium pelargonate, indium caprate, indium laurate, indium myristate, indium palmitate, indium margarate, indium stearate , Saturated aliphatic indium carboxylates such as indium oleate and indium 2-ethylhexanoate; unsaturated indium such as indium oleate and indium linoleate Ruboxylate and the like can be suitably used, and particularly from the viewpoint of easy availability and particle size distribution control, selected from the group consisting of indium acetate, indium laurate, indium myristate, indium palmitate, indium stearate, and indium oleate It is preferable to use at least one kind. Particular
  • an element M source is included in the reaction mixture in addition to a phosphorus source and an indium source.
  • an element M source is, for example, from the viewpoint of availability and reaction rate, if it is a metal element, it is an organic carboxylate, particularly a long chain fatty acid salt having 12 to 18 carbon atoms, chloride, It is preferable to add in the form of bromide or iodide.
  • the mixing molar ratio of the phosphorus source and the indium source during the reaction is preferably 1: 0.5 or more and 10 or less, preferably 1: 1 or more and 5 or less, from the viewpoint of successfully obtaining quantum dots. Is more preferable.
  • the molar ratio of P: M is preferably 1: 0.5 or more and 10 or less, and more preferably 1: 1 or more and 5 or less.
  • the reaction with the phosphorus source, the indium source, and the element M source added as necessary is preferably performed in an organic solvent from the viewpoints of particle size control, particle size distribution control, and quantum yield improvement.
  • organic solvent include non-polar solvents from the viewpoint of stability such as a phosphorus source and an indium source, and aliphatic hydrocarbons, unsaturated aliphatic hydrocarbons, aromatics in terms of particle size control and quantum yield improvement.
  • Preferred examples include non-coordinating solvents such as group hydrocarbons, trialkylphosphine, and trialkylphosphine oxide.
  • Examples of the aliphatic hydrocarbon include n-hexane, n-heptane, n-octane, n-nonane, n-decane, n-dodecane, n-hexadecane and n-octadecane.
  • Examples of the unsaturated aliphatic hydrocarbon include 1-undecene, 1-dodecene, 1-hexadecene, 1-octadecene and the like.
  • Aromatic hydrocarbons include benzene, toluene, xylene, styrene and the like.
  • trialkylphosphine examples include triethylphosphine, tributylphosphine, tridecylphosphine, trihexylphosphine, trioctylphosphine, and tridodecylphosphine.
  • trialkylphosphine oxide examples include triethylphosphine oxide, tributylphosphine oxide, tridecylphosphine oxide, trihexylphosphine oxide, trioctylphosphine oxide, and tridodecylphosphine oxide.
  • the solvent is dehydrated before use in order to prevent decomposition of the silylphosphine compound due to reaction with water and generation of impurities due thereto.
  • the amount of water in the solvent is preferably 20 ppm or less, and preferably 10 ppm or less on a mass basis.
  • the amount of moisture can be measured by the method described in the examples described later.
  • the solvent be degassed before use to remove oxygen. Degassing can be performed by any method such as replacement with an inert atmosphere in the reactor.
  • Each concentration of the phosphorus source, the indium source, and the M source in the reaction liquid in which the phosphorus source, the indium source, and the above-described element M source added as necessary is mixed, for example, with respect to 100 g of the solution, the phosphorus source, the indium source, M
  • Each source is preferably in the range of 0.1 mmol to 10 mmol from the viewpoint of particle size control and particle size distribution control.
  • the phosphorus source, the indium source and the element M source added as necessary, the phosphorus source, the indium source and the element M source were dissolved in an organic solvent, and the phosphorus source was dissolved in the organic solvent. It is preferable to mix the solution with a solution in which an indium source is dissolved in an organic solvent in terms of easy generation of nanoparticles.
  • the element M source it can be dissolved in the same solution as the indium source.
  • the solvent for dissolving the phosphorus source and the solvent for dissolving the indium source may be the same or different.
  • a solution in which a phosphorus source is dissolved in an organic solvent and a solution in which an indium source is dissolved in an organic solvent may be preliminarily heated to a preferable reaction temperature or a temperature lower than or higher than that described below before mixing. Later, it may be heated to the preferred reaction temperature described below.
  • an indium source and a phosphorus source are mixed. Before, it is set as the solution which mixed the raw material of the indium source and the other quantum dots, and this solution and the solution containing the phosphorus source are mixed, so that InP or a compound compound of In, P and element M and other III A semiconductor compound material of a group metal and phosphorus may be generated at the same time.
  • the Group III metal source includes a Group III metal chloride, bromide, iodide, long chain fatty acid salt, and the like.
  • the phosphorus source, the indium source and, if necessary, the element M source are preferably mixed and reacted at a predetermined temperature, and the reaction temperature is preferably 250 ° C. or higher and 350 ° C. or lower from the viewpoint of particle size control. 270 degreeC or more and 330 degrees C or less are more preferable. From the viewpoint of particle size control, the reaction time is preferably from 1 minute to 180 minutes, more preferably from 2 minutes to 60 minutes. Through the above steps, a reaction liquid containing InP quantum dot material is obtained.
  • the reaction liquid containing the above InP quantum dot material and a coating compound raw material are used.
  • the method of mixing and making it react at the temperature of 200 to 330 degreeC is mentioned.
  • a part of the coating compound for example, a metal source such as Zn
  • Zn a metal source such as Zn
  • the reaction solution containing the InP quantum dot material may be heated.
  • a metal such as Zn as a coating compound raw material
  • an organic carboxylate particularly a long chain fatty acid salt having 12 to 18 carbon atoms to control particle size, particle size distribution, and quantum yield.
  • the sulfur source is preferably a long chain alkanethiol having 8 to 18 carbon atoms such as dodecanethiol
  • the selenium source is a trialkylphosphine selenide having 4 to 12 carbon atoms such as trioctylphosphine selenide.
  • These coating compound raw materials may be directly mixed with the reaction solution containing the InP quantum dot material, or may be mixed with the reaction solution containing the InP quantum dot material after being previously dissolved in a solvent.
  • this solvent may be the same as those mentioned above as the solvent used for the reaction of the phosphorus source, the indium source and the element M source.
  • the solvent for dissolving the coating compound raw material and the solvent in the reaction solution containing the InP quantum dot material may be the same or different.
  • the amount of the coating compound material used is preferably 0.5 to 50 mol, more preferably 1 to 10 mol, relative to 1 mol of indium in the reaction solution containing the InP quantum dot material.
  • a sulfur source or a selenium source it is preferable to use an amount corresponding to the above metal amount.
  • the InP quantum dots obtained by the above method have a high quality with a narrow particle size distribution by using a phosphorus source in which the content of the compound represented by the general formula (2) is sufficiently reduced. And can be suitably used for single-electron transistors, security inks, quantum teleportation, lasers, solar cells, quantum computers, biomarkers, light-emitting diodes, display backlights, and color filters.
  • the upper layer was concentrated with a concentrator to remove low-boiling components under reduced pressure until the final pressure was 6.3 KPa on an absolute pressure basis and the liquid temperature was 70 ° C., to obtain a 60.1 kg concentrate. .
  • the amount of the silylphosphine compound in the solution containing the silylphosphine compound after the second step was 3.2% by mass with respect to the amount of the silylphosphine compound in the solution at the start of the second step.
  • the obtained concentrated liquid was distilled under reduced pressure of 0.5 kPa at a tower top temperature of 85 ° C. After removing the first fraction, 49.3 kg of the main fraction was recovered to obtain a recovered product.
  • the amount of the silylphosphine compound in the distillation residue after vaporizing the silylphosphine compound is 93% by mass with respect to the amount of the silylphosphine compound in the solution containing the silylphosphine compound at the start of the third step.
  • the amount of the compounds of the formulas (1), (2), (3), (5), (6) and (7) is an area percentage for calculating the ratio of the peak to the total peak area detected as 100%. Obtained by law.
  • Gas chromatography measurement conditions The measurement sample is subdivided into a container with a septum cap under an inert gas atmosphere, and 0.2 ⁇ L of the measurement sample is injected into a gas chromatograph (manufactured by Shimadzu Corporation, “GC-2010”) with a syringe and measured under the following conditions did.
  • the upper layer was concentrated with a condensing can to remove low-boiling components under reduced pressure until the final pressure was 2.2 kPa and the liquid temperature was 70 ° C. to obtain 59.1 g of concentrated liquid.
  • the obtained concentrated liquid was distilled at a tower top temperature of 85 ° C. under a reduced pressure of 0.5 kPa, and after removing the first fraction, 49.9 g of the main fraction was recovered.
  • the purity of tris (trimethylsilyl) phosphine in the recovered product was measured by analysis by 31 P-NMR under the above conditions. The results are shown in Table 1. In the same manner as in Production Example 1, the content of the compounds of formulas (2) to (7) was measured. The results are shown in Table 1.
  • Example 1 Synthesis of InP quantum dots 0.375 mmol of indium myristate was added to 17.8 g of 1-octadecene and heated to 120 ° C. with stirring under reduced pressure to deaerate for 90 minutes. After deaeration, the solution was cooled to 70 ° C.
  • TMSP tris (trimethylsilyl) phosphine
  • the obtained hexane dispersion was measured with a spectrofluorometer (F-7000, manufactured by Hitachi High-Tech Science Co., Ltd.) under measurement conditions of an excitation wavelength of 450 nm and a measurement wavelength of 400 to 800 nm.
  • F-7000 spectrofluorometer
  • Example 1 The same method as in Example 1 was performed except that TMSP obtained in Comparative Production Example 1 was used. The maximum fluorescence wavelength and FWHM value of the obtained InP / ZnSe / ZnS quantum dots were measured. The results are shown in Table 2.
  • Example 2 Synthesis of InZnP quantum dots
  • 2.4 mmol of indium myristate and 1.6 mmol of zinc myristate were added to 63.4 g of 1-octadecene, heated to 110 ° C. with stirring under reduced pressure, and deaerated for 90 minutes. After deaeration, the temperature was raised to 300 ° C. to obtain a 1-octadecene solution of indium myristate and zinc myristate.
  • TMSP tris (trimethylsilyl) phosphine
  • the recovered InZnP / ZnSe / ZnS quantum dots were suspended in hexane to obtain a hexane dispersion of purified InZnP / ZnSe / ZnS quantum dots.
  • the maximum fluorescence wavelength and FWHM value of the obtained InZnP / ZnSe / ZnS quantum dots were measured. The results are shown in Table 2.
  • Example 2 The same method as in Example 2 was performed except that TMSP obtained in Comparative Production Example 1 was used. The maximum fluorescence wavelength and FWHM value of the obtained InZnP / ZnSe / ZnS quantum dots were measured. The results are shown in Table 2.
  • Example 3 Synthesis of InZnP / GaP quantum dots
  • 1.5 mmol of indium myristate and 3.0 mmol of zinc myristate were added to 69.0 g of 1-octadecene, heated to 110 ° C. with stirring under reduced pressure, and deaerated for 90 minutes. After deaeration, 0.4 mmol of gallium chloride was added, and the temperature was raised to 300 ° C. to obtain a 1-octadecene solution of indium myristate, zinc myristate, and gallium chloride.
  • TMSP tris (trimethylsilyl) phosphine
  • the recovered InZnP / GaP / ZnS quantum dots were suspended in hexane to obtain a hexane dispersion of purified InZnP / GaP / ZnS quantum dots.
  • the maximum fluorescence wavelength and FWHM value of the obtained InZnP / GaP / ZnS quantum dots were measured. The results are shown in Table 2.
  • Example 3 The same procedure as in Example 3 was performed except that TMSP obtained in Comparative Production Example 1 was used. The maximum fluorescence wavelength and FWHM value of the obtained InZnP / GaP / ZnS quantum dots were measured. The results are shown in Table 2.
  • the present invention it is possible to provide a method for producing InP quantum dots from which InP quantum dots excellent in particle formation can be obtained, and to obtain high-quality InP quantum dots having a narrow particle size distribution.

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Abstract

L'Invention concerne un procédé de production de points quantiques en InP à partir d'une source de phosphore et d'une source d'indium, un composé silylphosphine représenté par la formule générale (1) est utilisé comme source de phosphore, ledit composé silylphosphine ayant une teneur en un composé représenté par la formule générale (2) de 0,3 % en mole ou moins. Il est préférable qu'un composé silylphosphine représenté par la formule générale (1), qui a une teneur en un composé représenté par la formule générale (3) de 0,1 % en mole ou moins, soit utilisé comme source de phosphore. (Dans La formule générale (1), chaque R représente indépendamment un groupe alkyle ayant de 1 à 5 atomes de carbone (inclus) ou un groupe aryle ayant de 6 à 10 atomes de carbone (inclus).) (Dans la formule générale (2), R est tel que défini dans la formule générale (1).) (Dans la formule générale (3), R est tel que défini dans la formule générale (1).)
PCT/JP2019/011759 2018-03-27 2019-03-20 Procédé de production de points quantiques en phosphure d'indium Ceased WO2019188679A1 (fr)

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CN113105887A (zh) * 2021-04-29 2021-07-13 合肥福纳科技有限公司 量子点及其制备方法
US20220195299A1 (en) * 2019-04-16 2022-06-23 Nippon Chemical Industrial Co., Ltd. METHOD FOR PRODUCING InP QUANTUM DOT PRECURSOR AND METHOD FOR PRODUCING InP-BASED QUANTUM DOT

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JP2012532953A (ja) * 2009-07-08 2012-12-20 サムスン エレクトロニクス カンパニー リミテッド 半導体ナノ結晶及びその調製方法
US20150166341A1 (en) * 2012-05-15 2015-06-18 Charles Hamilton Semiconductor nanocrystals and methods of preparation
US20180047928A1 (en) * 2016-08-10 2018-02-15 Samsung Display Co., Ltd. Light-emitting device
WO2018061869A1 (fr) * 2016-09-29 2018-04-05 日本化学工業株式会社 Procédé de fabrication d'un composé de phosphine silyle et composé de silyle-phosphine

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JP2012532953A (ja) * 2009-07-08 2012-12-20 サムスン エレクトロニクス カンパニー リミテッド 半導体ナノ結晶及びその調製方法
US20150166341A1 (en) * 2012-05-15 2015-06-18 Charles Hamilton Semiconductor nanocrystals and methods of preparation
US20180047928A1 (en) * 2016-08-10 2018-02-15 Samsung Display Co., Ltd. Light-emitting device
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Publication number Priority date Publication date Assignee Title
US20220195299A1 (en) * 2019-04-16 2022-06-23 Nippon Chemical Industrial Co., Ltd. METHOD FOR PRODUCING InP QUANTUM DOT PRECURSOR AND METHOD FOR PRODUCING InP-BASED QUANTUM DOT
US11692134B2 (en) * 2019-04-16 2023-07-04 Nippon Chemical Industrial Co., Ltd. Method for producing InP quantum dot precursor and method for producing InP-based quantum dot
CN113105887A (zh) * 2021-04-29 2021-07-13 合肥福纳科技有限公司 量子点及其制备方法
CN113105887B (zh) * 2021-04-29 2024-04-19 湖州鑫成新材料科技有限公司 量子点及其制备方法

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