JP2014169421A - Phosphor containing semiconductor nanoparticle - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor containing semiconductor nanoparticles, which has low toxicity and does not cause problems such that curing is inhibited and the fluorescence efficiency is reduced when it is dispersed in a sealing resin.SOLUTION: A phosphor includes; core parts 2 each having one or a plurality of semiconductor nanoparticles constituted of sulfides of a group 11 element of the periodic table and a group 13 element of the periodic table or constituted of sulfides of zinc, a group 11 element of the periodic table and a group 13 element of the periodic table; and shell parts 3 for covering the outside of the core parts 2 and/or filling gaps between the core parts 2.

Description

  The present invention relates to a phosphor containing semiconductor nanoparticles having high emission intensity as a fluorescence source. In this specification, “fluorescence” refers to light emitted when electrons and holes in semiconductor nanoparticles are excited by light, heat, electromagnetic waves, etc., and after excitation, lose energy and fall to a lower order. That is, it does not matter whether the light emission life is long or short. So-called “phosphorescence” is also included.

So far, cadmium-based and lead-based semiconductor nanoparticles such as CdS, CdSe, CdTe, PbS, and PbSe have been developed (see, for example, Patent Documents 1 and 2). These semiconductor nanoparticles contain highly toxic elements.
Then, the semiconductor nanoparticle which does not use a highly toxic element is also proposed (refer patent document 3).

  Applications of these semiconductor nanoparticles can be used as wavelength conversion phosphors for LED light sources. In this case, as a manufacturing method of the LED light source, a package in which an LED element is arranged is prepared, an LED sealing resin mixed with the semiconductor nanoparticles is injected into the package, and is molded and cured by heat. Examples of the LED sealing resin include a silicone sealing resin.

JP 2004-243507 A JP 2004-352594 A International Publication WO2007 / 026746 Pamphlet

"Synthesis of fluorescent ZnS-AgInS2 semiconductor nanoparticles" J.AM.CHEM.SOC., Vol. 129, No. 41, pp.12388-12389 (2007)

However, there is a problem that the curing time of the sealing resin is extended due to the interaction between the composition in the LED sealing resin and the semiconductor nanoparticles, or the emission intensity of the semiconductor nanoparticles is increased in the cured sealing resin. There was a problem such as reduction (see Non-Patent Document 1).
For this reason, development of a phosphor containing semiconductor nanoparticles that has low toxicity and does not cause problems such as inhibition of curing or reduction in fluorescence efficiency in the sealing resin as described above. It was desired.

In view of the above problems, the inventors of the present application are composed of a sulfide of a Group 11 element and a Group 13 element of the periodic table, or a sulfide of zinc, a Group 11 element and a Group 13 element of the Periodic table. A phosphor having a core part having one or a plurality of semiconductor nanoparticles and a shell part covering the outside of the core part and / or filling a gap between the core parts has been devised.
The number of semiconductor nanoparticles contained in the phosphor of the present invention is not limited. One semiconductor nanoparticle may be contained in one phosphor, and a plurality of semiconductor nanoparticles may be contained in one phosphor.

The phosphor having such a configuration has the shell portion, so that when the phosphor is dispersed in the sealing resin, the curing of the sealing resin is not hindered. Moreover, since the semiconductor nanoparticle does not contain a highly toxic element, it can be used safely as a member constituting the light source device.
The shell portion can be formed of (1) silica, (2) a compound of zinc and sulfur, (3) silicone, or a combination thereof. See [Mode for Carrying Out the Invention] for each feature.

The phosphor of the present invention can be used for a light source device. In particular, in a light source device using an LED element with good luminous efficiency, it can be used as a phosphor that emits fluorescence based on light emission from the LED element.
If the phosphor is used as a wavelength converting phosphor, it is possible to obtain light of a desired color in which a light emission color unique to the light source device and a fluorescence color of the phosphor are mixed.

  In particular, in a LED light source device, a silicone sealing resin is selected as a sealing resin for sealing an LED element, and the phosphor of the present invention is dispersed in the silicone sealing resin. The phosphor of the invention can be suitably used because it does not inhibit the curing of the silicone-based sealing resin and the fluorescence efficiency is less likely to decrease.

  According to the present invention, a phosphor composed of only a low-toxic element and further exhibiting a high emission intensity in a cured sealing resin without exhibiting curing inhibition with respect to the sealing resin is realized. can do.

It is a schematic diagram which shows the positional relationship of the core part and shell part which are each component of the fluorescent substance of this invention. FIG. 3 is a schematic diagram showing a state where silica as the shell part 3 surrounds the outer periphery of the semiconductor nanoparticles constituting the core part 2. When the shell part 3 consists of zinc and sulfur, it is a schematic diagram which shows the state where the shell part 3 surrounds the circumference | surroundings of the semiconductor nanoparticle which comprises the core part 2. FIG. When a shell part is silicone, it is a schematic diagram which shows the state in which the shell part 3a which consists of fibrous silicone surrounds the circumference | surroundings of the semiconductor nanoparticle which is the core part 2. FIG. It is sectional drawing which shows schematic structure of the principal part of the LED light source device which used the fluorescent substance of this invention as a structural member of an LED light source device. In the manufacturing process of sealing resin (Example 9) containing the fluorescent substance particle of this invention, it is a graph which respectively shows the fluorescence spectrum intensity after hardening of sealing resin, and after hardening. In the manufacturing process of sealing resin (Example 10) containing the fluorescent substance particle of this invention, it is a graph which shows the fluorescence spectrum intensity | strength before hardening of a sealing resin, and after hardening, respectively. In the manufacturing process of sealing resin (Example 11) containing the fluorescent substance particle of this invention, it is a graph which respectively shows the fluorescence spectrum intensity before hardening of sealing resin, and after hardening. In the manufacturing process of sealing resin (comparative example 2), it is a graph which respectively shows the fluorescence spectrum intensity before hardening of sealing resin, and after hardening. It is an image by the transmission electron microscope of the fluorescent substance particle (Example 1) of this invention. It is an image by the transmission electron microscope of the fluorescent substance particle (Example 2) of this invention.

Embodiments of the present invention will be described below with reference to the accompanying drawings. The scope of the present invention is defined by the terms of the claims, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.
The semiconductor nanoparticles contained in the phosphor of the present invention are semiconductor nanoparticles that emit light at room temperature, and are sulfides containing Group 11 elements and Group 13 elements of the periodic table, or zinc and Group 11 of the periodic table. The main component is a sulfide containing a group element and a group 13 element of the periodic table.

  In addition, if a semiconductor nanoparticle light-emits at normal temperature, it does not ask | require whether it light-emits at temperature other than normal temperature. Moreover, normal temperature in this specification means 15-25 degreeC. The particle diameter of the semiconductor nanoparticles used in the present invention is not limited, but typically refers to particles having an average particle diameter of 20 nm or less. Preferably, the average particle diameter is 1 nm to 10 nm. More preferably, the average particle diameter is 1 nm to 6 nm.

  The Group 11 element of the periodic table is not particularly limited, and examples thereof include Cu, Ag, and Au. Of these, Cu and Ag are preferable and Ag is particularly preferable from the viewpoint of high emission intensity. Although it does not specifically limit as a periodic table group 13 element, For example, Ga, In, and Tl are mention | raise | lifted, Among these, Ga and In are preferable from a viewpoint that emitted light intensity is high, In is preferable. Particularly preferred.

An assembly of one or more semiconductor nanoparticles is referred to as a “core portion”. That is, the semiconductor nanoparticles can be the core part alone, and the assembly of a plurality of semiconductor nanoparticles can also be the core part.
In addition, a portion that covers the outside of the core portion and / or a portion that fills the gap between the core portions is referred to as a “shell portion”. When the core portion is composed of a single semiconductor nanoparticle, the shell portion is configured to cover the outer surface of the semiconductor nanoparticle. When the core portion is composed of a plurality of semiconductor nanoparticles, the shell portion covers the outer surface of each semiconductor nanoparticle. It becomes a form which coat | covers and fills the gap | interval which can be formed between semiconductor nanoparticles.

  FIG. 1 is a schematic diagram showing the relationship between a core part and a shell part in phosphor 1, FIG. 1 (a) shows a core part 2 consisting of one semiconductor nanoparticle, and shell part 3 is a semiconductor nanoparticle. The outer surface is covered. In FIG. 1B, the core part 2 is composed of two semiconductor nanoparticles, and the shell part 3 covers the outer surface of these semiconductor nanoparticles. In the case of FIG. 1B, the shell portion 3 also fills the gap between the two semiconductor nanoparticles. In FIG. 1C, the core portion 2 is composed of a large number of semiconductor nanoparticles, and the shell portion 3 covers the outer surface of these semiconductor nanoparticles. In the case of FIG. 1C, the shell portion 3 also fills the gap between adjacent semiconductor nanoparticles. Note that FIG. 1 is only a schematic diagram depicting a simple image, and the phosphor 1 may actually have various shapes and dimensions.

As a constituent material of the shell portion, silica (SiO ₂ ), a compound composed of zinc (Zn) and sulfur (S), and silicone (a molecule in which silicon (Si) and oxygen (O) are alternately bonded to form a siloxane bond) Have one. However, you may combine these shell parts as needed.
FIG. 2 shows the case where the shell part surrounding a single semiconductor nanoparticle is silica. Although FIG. 2 shows a form surrounding the outer periphery of a single semiconductor nanoparticle, as already exemplified in FIGS. 1B and 1C, a form surrounding a plurality of semiconductor nanoparticles is also conceivable.

Silica is preferably obtained by a condensation reaction of alkoxysilane. The alkoxysilane is not particularly limited, and examples thereof include an amino group-containing alkoxysilane compound, a thiol group-containing alkoxysilane compound, a carboxyl group-containing alkoxysilane compound, and an orthosilicate.
More specifically, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, tetrapropylorthosilicate, tetraethylorthosilicate, tetra And methyl orthosilicate. Among these, 3-aminopropyltrimethoxysilane is preferable from the viewpoint of reactivity, and tetraethylorthosilicate is preferable from the viewpoints of reactivity and safety.

As a method for synthesizing silica, for example, the above alkoxysilane is added to an organic solvent in which the core of semiconductor nanoparticles is dispersed, and the condensation reaction is performed outside the core by the action of moisture in the presence of a condensation catalyst. The method of making it progress and forming a shell part is mention | raise | lifted. However, the method of forming silica is not limited to this.
As a method for forming a compound comprising zinc and sulfur as the shell portion, for example, a method described in Japanese Patent Application Laid-Open No. 2011-178645 “Semiconductor Nanoparticles and Method for Producing the Same” can be mentioned.

FIG. 3 shows a case where the shell portion surrounding a single semiconductor nanoparticle is a compound composed of zinc and sulfur. Although FIG. 3 shows a form surrounding the outer periphery of a single semiconductor nanoparticle, as already exemplified in FIGS. 1B and 1C, a form surrounding a plurality of semiconductor nanoparticles is also conceivable.
From the viewpoint of improving the emission intensity of the obtained semiconductor nanoparticles, the shell portion made of zinc and sulfur has either a thiol compound, a phosphorus compound, or a mixture thereof, as schematically shown in FIG. It is preferable that a molecule (hereinafter referred to as “ligand”) is coordinated. These ligands are denoted by reference numeral 4.

  In particular, when the semiconductor nanoparticles are used as the wavelength conversion phosphor for the LED of the present invention, it is arranged from the viewpoint of ensuring the emission intensity in the cured sealing resin without hindering the curing of the sealing resin. The ligand is preferably made of a thiol compound. As the thiol compound, alkanethiol is preferable from the viewpoint of safety. Examples of the alkanethiol include methanethiol, ethanethiol, 1-propanethiol, 1-dodecanethiol and the like, and 1-dodecanethiol is preferable because of easy handling.

As a method for coordinating a ligand composed of a thiol compound or a phosphorus compound to the shell part, after forming a shell part composed of zinc and sulfur by the method described above, the obtained semiconductor nanoparticles and the desired coordination are formed. Examples of the method include mixing and stirring a compound that forms a ligand.
When the shell part is silicone, as shown in FIG. 4, a shape in which the shell part 3 a made of fibrous silicone surrounds the semiconductor nanoparticles that are the core part 2 is conceivable. Although FIG. 4 shows a form surrounding the outer periphery of a single semiconductor nanoparticle, as already exemplified in FIGS. 1B and 1C, a form surrounding a plurality of semiconductor nanoparticles is also conceivable.

The silicone preferably has an amino group, a thiol group, or a carboxyl group at the side chain or terminal. Specific examples of silicone include KF-865, KF-2001, X22-3701E, X22-167B, X22-162C, and X22-3710 manufactured by Shin-Etsu Chemical, DMS-A21 and DMS-A35 manufactured by Gelest.
Examples of the method for forming the shell portion with silicone include a method in which the obtained semiconductor nanoparticles and silicone are mixed and stirred.

Silicone may be formed outside the layer of zinc and sulfur in the shell portion.
The phosphor of the present invention can be used in various light source devices. In particular, in view of the recent power situation and environmental problems, it is desirable to use the phosphor of the present invention as a constituent member of an LED light source device.
FIG. 5 is a cross-sectional view showing a schematic structure of a main part of an LED light source device using the phosphor of the present invention as a constituent member of the LED light source device. The LED light source device includes an LED element 7 and a reflector 6 (the members 7 and 6 are collectively referred to as an LED package). As a resin for sealing the LED element 7, an epoxy-based or silicone-based LED sealing resin 5 is used. The phosphor 1 of the present invention is mixed in an LED sealing resin 5.

  The phosphor of the present invention can be used as a wavelength converting phosphor. For example, in FIG. 5, the phosphor 1 converts light of wavelength λ1 emitted from the LED element 7 into light of wavelength λ2. The LED light source device emits light in which light of wavelength λ1 and light of wavelength λ2 are mixed. For example, if the light of wavelength λ1 is blue light and the light of wavelength λ2 is yellow light, white light mixed with blue and yellow can be obtained.

When the phosphor of the present invention is used as the wavelength converting phosphor, it is particularly preferable to use a silicone-based LED sealing resin as the LED sealing resin 5. The silicone-based sealing resin for LED refers to a curable composition that contains a polysiloxane having a hydrosilyl group as a main component and is cured by the action of a compound having an unsaturated group and a platinum catalyst.
Any type of polysiloxane such as methyl silicone, phenyl silicone, and cage silsesquioxane is applicable as the polysiloxane in the silicone-based sealing resin for LED. Specific examples of silicone-based LED sealing resins include Toray Dow Corning OE series, JCR series, Shin-Etsu Chemical KJR series, LPS series, and SCR series.

  The light source device using the phosphor of the present invention as a constituent member is not limited to the LED light source device. For example, a backlight such as a light emitting / receiving device or a liquid crystal display panel, a lighting fixture, a sensor light source, and a vehicle-mounted instrument A light source, a signal lamp, a display lamp, a display device, a light source of a planar phosphor, a display, a decorative lamp, various lights, and the like can be given. However, the use of the phosphor of the present invention is not limited to these light source devices.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited thereby.
(Pretreatment Example 1-Production of Semiconductor Nanoparticles)
N, N′-diethyldithiocarbamate sodium trihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was used to prepare an aqueous solution of sodium N, N′-diethyldithiocarbamate (50 mM, 50 mL). An aqueous solution in which silver nitrate (manufactured by Wako Pure Chemical Industries, Ltd.), indium nitrate (III) (manufactured by Wako Pure Chemical Industries, Ltd.), and zinc nitrate (manufactured by Wako Pure Chemical Industries, Ltd.) are adjusted to 10 mM, 10 mM and 5 mM, respectively. 50 mL was added dropwise to an aqueous solution of sodium N, N′-diethyldithiocarbamate at room temperature. Thereby, a precursor complex of semiconductor nanoparticles was obtained. The supernatant solution was removed from the obtained precursor complex solution by centrifugation, and then washed twice with water and methanol. Finally, a precursor complex powder exhibiting a pale green color was obtained by vacuum drying.

  250 mg of the obtained precursor complex was stirred at 180 ° C. for 15 minutes in a nitrogen atmosphere, and then cooled to room temperature. Next, 15 mL of oleylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred at 180 ° C. for 7 minutes in a nitrogen atmosphere to obtain a brown suspension. The suspension was centrifuged to collect a supernatant, and methanol was added to precipitate semiconductor nanoparticles, followed by vacuum drying. 10 mL of oleylamine was added to the obtained semiconductor nanoparticle powder, and the mixture was stirred at 180 ° C. for 30 minutes in a nitrogen atmosphere and allowed to cool to room temperature. The resulting solution was centrifuged to recover the supernatant, and methanol was added to precipitate semiconductor nanoparticles. The precipitate was collected by centrifugation and vacuum-dried to obtain semiconductor nanoparticles (R1) serving as the following core part.

(Example 1-Production of phosphor particles)
The obtained semiconductor nanoparticles (R1) were dispersed in 7.5 mL of cyclohexane. Next, 1.8 mL of Triton X-100, 1.8 mL of n-hexanol, 60 eL of 28% aqueous ammonium hydroxide solution and 480 eL of ultrapure water were added, and the mixture was stirred at room temperature for 30 minutes. Further, 100 μL of tetraethyl orthosilicate (manufactured by Shin-Etsu Chemical Co., Ltd.) and 20 μL of 3-aminopropyltrimethoxysilane (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at room temperature for 3 days. The supernatant of the resulting solution was removed by centrifugation and washed twice with ethanol and water. Finally, phosphor particles (A1; schematically shown in FIG. 2) having a silica layer as a shell portion were obtained by vacuum drying.

(Pretreatment Example 2-Production of Semiconductor Nanoparticles)
250 mg of the precursor complex obtained in Pretreatment Example 1 was stirred at 180 ° C. for 15 minutes in a nitrogen atmosphere, and then allowed to cool to room temperature. Next, 15 mL of oleylamine was added and stirred at 180 ° C. for 7 minutes under a nitrogen atmosphere to obtain a brown suspension. The resulting solution was centrifuged to collect the supernatant, and methanol was added to precipitate semiconductor nanoparticles, followed by vacuum drying. 10 mL of oleylamine, 105 mg of zinc acetate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 36 mg of thioacetamide (manufactured by Wako Pure Chemical Industries, Ltd.) are added to the obtained semiconductor nanoparticle powder, and the mixture is added at 30 ° C. at 180 ° C. Stir for minutes and allow to cool to room temperature. The resulting solution was centrifuged to recover the supernatant, and methanol was added to precipitate semiconductor nanoparticles. The precipitate was collected by centrifugation and vacuum dried to obtain ZnS-coated semiconductor nanoparticles (R2).

(Example 2-Production of phosphor particles)
5 mL of 1-dodecanethiol (manufactured by Wako Pure Chemical Industries, Ltd.) was added to the obtained semiconductor nanoparticles (R2), stirred at 180 ° C. for 5 hours in a nitrogen atmosphere, and then allowed to cool to room temperature. . The supernatant of the resulting solution was removed by centrifugation, washed with methanol and ethanol, and then vacuum dried to obtain semiconductor nanoparticles. Furthermore, 1 mL of 1-dodecanethiol was added to the obtained semiconductor nanoparticles, and the mixture was stirred at 180 ° C. for 1 hour in a nitrogen atmosphere, and then allowed to cool to room temperature. The supernatant of the resulting solution was removed by centrifugation, washed with methanol and ethanol, and then vacuum-dried to obtain phosphor particles in which 1-dodecanethiol was coordinated to the shell portion made of zinc and sulfur (B1; FIG. 3 schematically).

(Example 3-Production of phosphor particles)
100 mg of the semiconductor nanoparticles (R2) were dispersed in 1.0 mL of toluene. To this solution was added 10 mL of tri-n-octylphosphine (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at room temperature for 3 days in a nitrogen atmosphere. After completion of the stirring, methanol was added and the mixture was centrifuged to collect a precipitate. Further, after washing with methanol twice, vacuum drying is performed to obtain phosphor particles (B2; schematically shown in FIG. 3) in which tri-n-octylphosphine is coordinated to a shell portion made of zinc and sulfur. Obtained.

(Example 4-Production of phosphor particles)
45 mg of the semiconductor nanoparticles (R2) were dispersed in 13 mL of toluene. To this solution, 5.0 mL of mercapto-modified silicone (Shin-Etsu Chemical KF-2001) was added and stirred at room temperature for 3 days under a nitrogen atmosphere. After completion of the stirring, methanol was added and the mixture was centrifuged to collect a precipitate. Further, washing with methanol was repeated twice, followed by vacuum drying to obtain phosphor particles (C1; schematically shown in FIG. 4) having a silicone layer as a shell portion.

(Example 5-Production of sealing resin in which phosphor particles are dispersed)
10 mg of the phosphor particles (A1) obtained in Example 1 were dispersed in 1.0 mL of chloroform. 0.5 mL of the obtained solution was added to 5.0 g of OE6630, which is a sealing resin for silicone LED manufactured by Toray Dow Corning, and stirred with a spatula. Next, chloroform was removed by vacuum devolatilization, and then kneaded for 3 minutes under conditions of 1200 rpm and 0.2 kPa using Awatori Nertaro ARV-310, manufactured by Shinky Corporation, to disperse the phosphor particles (A1). A resin composition was obtained. The obtained composition was dropped on a hot plate heated to 150 ° C., and the time from dripping to curing was measured. The obtained curing time data is shown in Table 1.

(Example 6-Production of encapsulating resin in which phosphor particles are dispersed)
A resin composition was prepared in the same manner as in Example 1 except that the phosphor particles (B1) obtained in Example 2 were used, and the curing time was measured in the same manner as in Example 1. The obtained curing time data is shown in Table 1.
(Example 7-Production of sealing resin in which phosphor particles are dispersed)
A resin composition was prepared by the same method as in Example 1 except that the phosphor particles (B2) obtained in Example 3 were used, and the curing time was measured by the same method as in Example 1. The obtained curing time data is shown in Table 1.

(Example 8-Production of encapsulating resin in which phosphor particles are dispersed)
A resin composition was prepared in the same manner as in Example 1 except that the phosphor particles (C1) obtained in Example 4 were used, and the curing time was measured in the same manner as in Example 1. The obtained curing time data is shown in Table 1.
(Comparative Example 1)
A resin composition was prepared in the same manner as in Example 1 except that the semiconductor nanoparticles (R1) obtained in Pretreatment Example 1 were used, and the curing time was measured in the same manner as in Example 1. . The obtained curing time data is shown in Table 1.

As can be seen from Table 1, the curing time of the resin of Comparative Example 1 is extremely longer than that of Example 5-8.
(Example 9-Production of sealing resin in which phosphor particles are dispersed)
A resin composition of silicone-based LED sealing resin OE6630 containing phosphor particles (A1) was produced in the same manner as in Example 1. The obtained composition was added to a methacrylate resin four-sided cell (optical path length: 10 mm), and a fluorescence spectrum (excitation wavelength: 450 nm) was measured with a fluorescence spectrophotometer F-7000 manufactured by Hitachi. Next, the used four-sided cell was heated in an oven at 60 ° C. to cure the composition. After cooling, the fluorescence spectrum was measured by the same method as described above. The combined fluorescence spectrum before and after curing of the composition is shown in FIG.

(Example 10-Production of sealing resin in which phosphor particles are dispersed)
The fluorescence spectrum was measured by the same method as in Example 9 except that the phosphor particles (B1) obtained in Example 2 were used. The obtained fluorescence spectrum is shown in FIG.
(Example 11-Production of sealing resin in which phosphor particles are dispersed)
The fluorescence spectrum was measured by the same method as in Example 9 except that the phosphor particles (B2) obtained in Example 3 were used. The obtained fluorescence spectrum is shown in FIG.

(Comparative Example 2)
10 mg of the semiconductor nanoparticles (R1) obtained in Pretreatment Example 1 were dispersed in 1.0 mL of chloroform. 0.5 mL of the obtained solution was added to 5.0 g of OE6630 which is a sealing resin for silicone-based LED manufactured by Toray Dow Corning, and stirred with a spatula, and then a xylene solution having a platinum content of about 2 wt% of a platinum vinylsiloxane complex. 2 μL of (Aldrich) was added and further stirred with a spatula. Next, after removing chloroform by vacuum devolatilization, the mixture containing semiconductor nanoparticles (R1) is kneaded for 3 minutes under conditions of 1200 rpm and 0.2 kPa using Awatori Nertaro ARV-310 manufactured by Shinky Corporation. Got. Using the obtained composition, the fluorescence spectrum was measured in the same manner as in Example 9. The obtained fluorescence spectrum is shown in FIG.

In FIGS. 6 to 8 according to the example, the fluorescence spectrum intensity after curing does not significantly decrease compared to the fluorescence spectrum intensity before curing, whereas in FIG. 9 according to the comparative example, after the curing The fluorescence spectrum intensity of is significantly reduced from the fluorescence spectrum intensity before curing.
(Measurement Example 1—TEM Image of Phosphor Particle (A1))
The image of the phosphor particles (A1) obtained in Example 1 was observed with a transmission electron microscope (TEM) manufactured by Hitachi (acceleration voltage: 100 kV). The obtained image is shown in FIG. From FIG. 10, it can be seen that in the phosphor particles (A1), one or more core parts are present in the silica as the shell part as shown in FIG. 1 (c).

(Measurement Example 2—TEM Image of Phosphor Particle (B1))
The image of the phosphor particles (B1) obtained in Example 2 was observed by TEM in the same manner as in Measurement Example 1. The obtained image is shown in FIG. In FIG. 11, the contrast between the core part and the shell part is not clear, but the dark part shows an image of the core part.
As is clear from the above examples, the phosphor obtained by the present invention has a small effect on the curability of the silicone LED sealing resin, and has a high emission intensity in the cured sealing resin. It can be seen that it can be shown.

DESCRIPTION OF SYMBOLS 1 Fluorescent substance, fluorescent substance particle 2 Core part 3 Shell part 4 Ligand 5 LED sealing resin 6 Reflector 7 LED element

Claims (18)

A core part having one or a plurality of semiconductor nanoparticles composed of the substance (a) below or the substance (b) below, and a shell part covering the outside of the core part and / or filling a gap between the core parts And a phosphor.
(A) sulfides of Group 11 elements of the periodic table and Group 13 elements of the periodic table;
(B) Zinc, sulfides of Group 11 elements of the periodic table and Group 13 elements of the periodic table.   The phosphor according to claim 1, wherein the shell portion is silica.   The phosphor according to claim 2, wherein the silica is obtained by a condensation reaction of alkoxysilane.   The phosphor according to claim 3, wherein the alkoxysilane is an orthosilicate with an amino group-containing alkoxysilane compound.   The phosphor according to claim 4, wherein the amino group-containing alkoxysilane compound is 3-aminopropyltrimethoxysilane, and the orthosilicate is tetraethyl orthosilicate.   The phosphor according to claim 1, wherein the shell portion is made of zinc and sulfur.   The phosphor according to claim 6, wherein a thiol compound or a phosphorus compound is coordinated to the shell portion.   The phosphor according to claim 7, wherein the thiol compound coordinated to the shell portion is an alkanethiol.   The phosphor according to claim 8, wherein the alkanethiol coordinated to the shell portion is 1-dodecanethiol.   The phosphor according to claim 1, wherein the shell portion is silicone.   The phosphor according to claim 10, wherein the silicone is a silicone having an amino group, a thiol group, or a carboxyl group in a side chain.   The phosphor according to claim 10, wherein the silicone is a silicone having an amino group, a thiol group, or a carboxyl group at a terminal.   The phosphor according to any one of claims 1 to 12, wherein the Group 11 element of the periodic table is Ag.   The phosphor according to any one of claims 1 to 13, wherein the group 13 element of the periodic table is In.   The light source device using the fluorescent substance of any one of Claims 1-14.   The light source device according to claim 15, wherein the phosphor is used as a wavelength converting phosphor.   An LED light source device comprising: an LED element; and the phosphor according to any one of claims 1 to 14 that emits fluorescence by light emitted from the LED element.   The light source device according to claim 17, wherein a silicone-based sealing resin is included as a sealing resin for sealing the LED element, and the phosphor is dispersed in the silicone-based sealing resin.