JP2016023098A - Phosphor deposited glass powder and wavelength conversion member manufacturing methods, and wavelength conversion member - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphor deposited glass powder manufacturing method in which inorganic nano phosphor particles can be dispersed in good state, a wavelength conversion member manufacturing method using said manufacturing method, and a wavelength conversion member.SOLUTION: Provided is a phosphor deposited glass powder 1 manufacturing method by depositing inorganic nano phosphor particles 3 on the surface of a glass powder 2, and in which, characterized, comprising a step for contacting inorganic nano phosphor particles 3 and a glass powder 2 in a liquid in which inorganic nano phosphor particles 3 are dispersed in a dispersion medium, and a step for depositing inorganic nano phosphor particles 3 on the surface of a glass powder 2 by removing the dispersion medium in the liquid.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for producing a phosphor-attached glass powder, a method for producing a wavelength conversion member, and a wavelength conversion member.

  In recent years, a light-emitting device using an excitation light source such as a light emitting diode (LED) or a semiconductor laser (LD) and using fluorescence generated by irradiating the phosphor with excitation light generated from these excitation light sources has been studied. Has been. In addition, the use of inorganic nanophosphor particles called semiconductor nanoparticles or quantum dots has been studied as a phosphor. Inorganic nanophosphor particles can be adjusted in fluorescence wavelength by changing their diameter, and have high luminous efficiency.

  However, inorganic nanophosphor particles have the property of being easily deteriorated when they come into contact with moisture or oxygen in the air. For this reason, it is necessary to seal the inorganic nanophosphor particles so as not to contact the external environment. When a resin is used as the sealing material, there is a problem that when the wavelength of excitation light is converted by the phosphor, a part of the energy is converted into heat, so that the resin is discolored by the heat. Further, since the resin is inferior in water resistance and easily penetrates moisture, there is a problem that the phosphor is easily deteriorated.

  Under such circumstances, Patent Document 1 proposes a wavelength conversion member using glass instead of resin as a sealing material. Specifically, Patent Document 1 proposes a wavelength conversion member using glass as a sealing material by sintering a mixture containing inorganic nanophosphor particles and glass powder.

JP 2012-87162 A

  Inorganic nanophosphor particles are much smaller than glass powders, and therefore easily aggregate. For this reason, the wavelength conversion member described in Patent Document 1 has a problem that the inorganic nanophosphor particles are sealed in the glass in an aggregated state.

  An object of the present invention is to provide a method for producing a phosphor-attached glass powder capable of producing a wavelength conversion member in which inorganic nanophosphor particles are dispersed in a good state in a glass matrix, and a wavelength conversion member using the production method. It is in providing the manufacturing method of this, and a wavelength conversion member.

  The method for producing a phosphor-attached glass powder of the present invention is a method for producing a phosphor-attached glass powder in which inorganic nanophosphor particles are attached to the surface of a glass powder, wherein the inorganic nanophosphor particles are dispersed in a dispersion medium. A step of bringing the inorganic nanophosphor particles into contact with the glass powder in the liquid, and a step of attaching the inorganic nanophosphor particles to the surface of the glass powder by removing the dispersion medium in the liquid. It is said.

  In the present invention, for example, by adding glass powder into the liquid, the inorganic nanophosphor particles and the glass powder can be brought into contact with each other.

  In the present invention, for example, the inorganic nanophosphor particles and the glass powder can be brought into contact with each other by spraying the liquid on the glass powder in the form of a mist.

  In the present invention, for example, the inorganic nanophosphor particles and the glass powder can be brought into contact by mixing the liquid and a dispersion liquid in which the glass powder is dispersed.

  In the present invention, the glass powder may be in the form of a molded body obtained by aggregating the glass powder. In this case, the molded body may be a molded body aggregated by applying pressure to the glass powder. Further, the molded body may be a molded body obtained by calcination and aggregation of glass powder. Further, the molded body may be a molded body obtained by calcination of a glass green sheet containing glass powder.

  In the present invention, for example, the inorganic nanophosphor particles and the glass powder can be brought into contact with each other by immersing the molded body in a liquid.

  In the present invention, for example, the inorganic nanophosphor particles and the glass powder can be brought into contact with each other by allowing the liquid to penetrate into the molded body.

  The method for producing a wavelength conversion member of the present invention is a method for producing a wavelength conversion member containing inorganic nanophosphor particles in glass, the step of producing a phosphor-attached glass powder by the production method of the present invention, And a step of sintering the phosphor-attached glass powder.

  Sintering is preferably performed in a vacuum atmosphere.

  The sintering temperature is preferably 400 ° C. or lower.

  The wavelength conversion member according to the first aspect of the present invention is a wavelength conversion member manufactured by the method for manufacturing a wavelength conversion member of the present invention.

  The wavelength conversion member according to the second aspect of the present invention is a wavelength conversion member obtained by sintering phosphor-attached glass powder having inorganic nanophosphor particles attached to the surface of glass powder.

  The wavelength conversion member of the 3rd aspect of the present invention is a wavelength conversion member which consists of fluorescent substance adhesion glass powder manufactured with the manufacturing method of fluorescent substance adhesion glass powder of the present invention.

  According to the present invention, it is possible to produce a wavelength conversion member in which inorganic nanophosphor particles are dispersed in a glass matrix in a good state.

It is typical sectional drawing which shows the fluorescent substance adhesion glass powder of one Embodiment of this invention. It is typical sectional drawing which shows the fluorescent substance adhesion glass powder of other embodiment of this invention. It is a typical sectional view showing the wavelength conversion member of one embodiment of the present invention.

  Hereinafter, preferred embodiments will be described. However, the following embodiments are merely examples, and the present invention is not limited to the following embodiments. Moreover, in each drawing, the member which has the substantially the same function may be referred with the same code | symbol.

  FIG. 1 is a schematic cross-sectional view showing a phosphor-attached glass powder according to an embodiment of the present invention. As shown in FIG. 1, the phosphor-attached glass powder 1 of the present embodiment is configured by attaching a large number of inorganic nanophosphor particles 3 in a well dispersed state to the surface of a glass powder 2. In the phosphor-attached glass powder 1 of the present embodiment, the inorganic nanophosphor particles 3 and the glass powder 2 are brought into contact with each other in the liquid in which the inorganic nanophosphor particles 3 are dispersed in the dispersion medium, and then the dispersion medium in the liquid is used. It can manufacture by removing.

  As a specific method of bringing the inorganic nanophosphor particles 3 and the glass powder 2 into contact in a liquid in which the inorganic nanophosphor particles 3 are dispersed in a dispersion medium, for example, the following methods may be mentioned.

  (1) A method of adding glass powder 2 to a liquid in which inorganic nanophosphor particles 3 are dispersed in a dispersion medium.

  (2) A method in which a liquid in which inorganic nanophosphor particles 3 are dispersed in a dispersion medium is sprayed on glass powder 2 in a mist form.

  (3) A method of mixing a dispersion liquid in which glass powder 2 is dispersed and a liquid in which inorganic nanophosphor particles 3 are dispersed in a dispersion medium.

  FIG. 2 is a schematic cross-sectional view showing a phosphor-attached glass powder according to another embodiment of the present invention. As shown in FIG. 2, in the phosphor-attached glass powder 11 of the present embodiment, the glass powder has a form of a molded body 4 in which the glass powder 2 is aggregated. Inorganic nanophosphor particles 3 are adhered to the surface of each glass powder 2 constituting the molded body 4 in a good dispersion state. For example, the molded body 4 may be agglomerated by applying pressure to the glass powder 2 placed in a mold. Moreover, the molded object 4 may be agglomerated by, for example, heating and pre-baking the glass powder 2 put in a mold. Moreover, the molded object 4 may be obtained by calcining a glass green sheet containing glass powder and a resin binder.

  As a specific method of bringing the glass powder 2 constituting the molded body 4 and the inorganic nanophosphor particles 3 into contact with each other in a liquid in which the inorganic nanophosphor particles 3 are dispersed in a dispersion medium, for example, the following methods may be mentioned.

  (4) A method of immersing the molded body 4 in a liquid in which the inorganic nanophosphor particles 3 are dispersed in a dispersion medium.

  (5) A method in which the molded body 4 is infiltrated with a liquid in which the inorganic nanophosphor particles 3 are dispersed in a dispersion medium.

  FIG. 3 is a schematic cross-sectional view showing a wavelength conversion member according to an embodiment of the present invention. As shown in FIG. 3, the wavelength conversion member 20 of this embodiment contains the inorganic nano fluorescent substance particle 3 in the glass 5 in a favorable dispersion state. The wavelength conversion member 20 of this embodiment can be manufactured by sintering the phosphor-attached glass powder 1 shown in FIG. 1 or the phosphor-attached glass powder 11 shown in FIG. The sintering temperature is preferably 500 ° C. or lower, more preferably 400 ° C. or lower, and particularly preferably 350 ° C. or lower. When the sintering temperature is increased, the phosphor may be deteriorated. On the other hand, in order to densely sinter the glass powder 2, the sintering temperature is preferably 150 ° C. or higher.

  The atmosphere during sintering is preferably a vacuum atmosphere or an inert atmosphere using nitrogen or argon. Thereby, deterioration and coloring of the glass powder 2 can be suppressed at the time of sintering. In particular, in a vacuum atmosphere, generation of bubbles in the wavelength conversion member 20 can be suppressed.

  Hereafter, each structure in this invention is demonstrated in detail.

(Inorganic nanophosphor particles)
The inorganic nanophosphor particles in the present invention are phosphor particles made of inorganic crystals having a particle size of less than 1 μm. As such inorganic nanophosphor particles, generally called semiconductor nanoparticles or quantum dots can be used. Examples of the semiconductor of such inorganic nanophosphor particles include II-VI group compounds and III-V group compounds. Examples of the II-VI group compound include CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe and the like. Examples of III-V compounds include InP, GaN, GaAs, GaP, AlN, AlP, AlSb, InN, InAs, InSb, and the like. At least one selected from these compounds, or a composite of two or more of these can be used as the inorganic nanophosphor particles of the present invention. Examples of the composite include those having a core-shell structure, such as those having a core-shell structure in which the surface of CdSe particles is coated with ZnS.

  The particle size of the inorganic nanophosphor particles of the present invention is appropriately selected within a range of, for example, 100 nm or less, 50 nm or less, particularly 1 to 30 nm, 1 to 15 nm, or even 1.5 to 12 nm.

  As the inorganic nanophosphor particles of the present invention, it is preferable to use particles whose surfaces are coated with a dispersant made of a polymer or the like in order to enhance dispersibility in a dispersion medium.

(Glass powder)
The glass powder used in the present invention is preferably made of glass having a softening point of 500 ° C. or lower, more preferably 400 ° C. or lower, more preferably 350 ° C. or lower. When the softening point of the glass is increased, the sintering temperature is increased, so that the inorganic nanophosphor particles are easily deteriorated. Suitable glass powders include SnO—P ₂ O ₅ glass, SnO—P ₂ O ₅ —B ₂ O ₃ glass, SnO—P ₂ O ₅ —F glass, Bi ₂ O ₃ glass, and the like. Things.

The _SnO-P 2 _{O 5} based glass, as a glass composition, in mol%, SnO 40 to _85%, those containing _P 2 O 5 15 to 60%, particularly SnO _60~80%, P 2 _{O 5} What contains 20 to 40% is preferable.

The _{SnO-P 2 O 5 -B 2} O 3 based glass, as a glass composition, in mol%, containing _{SnO 35~80%, P 2 O 5} 5~40%, the 2 O 3 1 to 30% _B Those are preferred.

The _SnO-P 2 _{O 5} based glass and _{SnO-P 2 O 5 -B 2} O 3 based glass, a further optional _{component, Al 2 O 3 0~10%,} SiO 2 0~10%, Li 2 O 0 _10%, may be contained _{Na 2 O 0~10%, K 2} O 0~10%, 0~10% MgO, CaO 0~10%, the SrO 0% and BaO 0% Absent. In addition to the above components, components that improve weather resistance such as Ta ₂ O ₅ , TiO ₂ , Nb ₂ O ₅ , Gd ₂ O ₃ , La ₂ O ₃ , components that stabilize glass such as ZnO, etc. Can further be included.

The _{SnO-P 2 O} 5 -F-based glass, ^{cationic%, P 5+ 10~70%, Sn} 2+ 10~90%, by ^{anionic%, O 2- 30~100%, F} - a 0% to 70% What is contained is preferable. Furthermore, in order to improve the weather resistance, B ³⁺ , Si ⁴⁺ , Al ³⁺ , Zn ²⁺ or Ti ⁴⁺ may be contained in a total amount of 0 to 50%.

The Bi ₂ O ₃ based glass, as a glass composition, in _{mass%, Bi 2 O 3 10~90%} , those containing 2 O 3 10~30% _B is preferred. Furthermore, 0 to 30% of SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ , P ₂ O _5, etc. may be contained as glass forming components.

From the viewpoints of lowering the softening point of SnO—P ₂ O ₅ glass and SnO—P ₂ O ₅ —B ₂ O ₃ glass and stabilizing the glass, the molar ratio of SnO to P ₂ O ₅ (SnO / P ₂ O ₅ ) is preferably within the range of 0.9 to 16, more preferably within the range of 1.5 to 10, and even more preferably within the range of 2 to 5. When the molar ratio (SnO / P ₂ O ₅ ) is too small, firing at a low temperature becomes difficult, and the inorganic nanophosphor particles may be easily deteriorated during sintering. Also, the weather resistance may be too low. On the other hand, if the molar ratio (SnO / P ₂ O ₅ ) is too large, the glass tends to be devitrified, and the transmittance of the glass may be too low.

  The average particle diameter D50 of the glass powder is preferably from 0.1 to 100 μm, particularly preferably from 1 to 50 μm. If the average particle diameter D50 of the glass powder is too small, bubbles are likely to be generated during sintering. For this reason, the mechanical strength of the wavelength conversion member obtained may fall. In addition, light scattering loss may increase due to bubbles generated in the wavelength conversion member, and the light emission efficiency may decrease. On the other hand, if the average particle diameter D50 of the glass powder is too large, the inorganic nanophosphor particles are difficult to be uniformly dispersed in the glass matrix, and as a result, the luminous efficiency of the obtained wavelength conversion member may be lowered. The average particle diameter D50 of the glass powder can be measured with a laser diffraction particle size distribution measuring apparatus.

(Dispersion medium)
The dispersion medium used in the present invention is not particularly limited as long as the inorganic nanophosphor particles can be dispersed. In general, a non-polar solvent having appropriate volatility such as hexane and octane is preferably used. However, the present invention is not limited to this, and a polar solvent having appropriate volatility may be used.

  The concentration of the inorganic nanophosphor particles in the dispersion medium is preferably 0.5% by mass to 20% by mass, more preferably 1% by mass to 10% by mass. If the concentration of the inorganic nanophosphor particles in the dispersion medium is too low, it becomes difficult to obtain a wavelength conversion member having sufficient emission intensity. On the other hand, if the concentration of the inorganic nanophosphor particles in the dispersion medium is too high, it becomes difficult to uniformly adhere to the surface of the glass powder.

(Phosphor-attached glass powder)
The content ratio of the inorganic nanophosphor particles and the glass powder in the phosphor-attached glass powder of the present invention is preferably 1: 1000 to 1:10, and 1: 200 to 1:50 in terms of mass ratio. preferable. When the ratio of the inorganic nanophosphor particles in the phosphor-attached glass powder is too low, it becomes difficult to obtain a wavelength conversion member having sufficient emission intensity. On the other hand, when the ratio of the inorganic nanophosphor particles in the phosphor-attached glass powder is too high, it is difficult to uniformly adhere to the surface of the glass powder. Moreover, it becomes difficult to irradiate excitation light to the whole inorganic nano fluorescent substance particle, and there exists a tendency for the inorganic nano fluorescent substance particle which does not emit fluorescence to increase.

(Molded body)
As described above, the glass powder in the present invention may be in the form of a molded body obtained by aggregating glass powder. Such a molded body may be agglomerated by applying pressure to the glass powder as described above, or may be agglomerated by calcining the glass powder, It may be obtained by calcining a glass green sheet.

  In addition, the following method is mentioned as a method of shape | molding a molded object by calcining a green sheet. Add a resin binder containing a predetermined amount of resin, plasticizer, solvent, etc. to glass powder to make a slurry, and form the slurry on a sheet of polyethylene terephthalate (PET) etc. by doctor blade method etc. To do. A molded body is obtained by calcining the slurry formed into a sheet.

(Wavelength conversion member)
As described above, the wavelength conversion member of the present invention can be produced by sintering the phosphor-attached glass powder of the present invention. As described above, the sintering temperature is preferably 500 ° C. or lower, more preferably 400 ° C. or lower, and particularly preferably 350 ° C. or lower.

  In the phosphor-attached glass powder of the present invention, since the inorganic nanophosphor particles are attached in a good dispersion state on the surface of the glass powder, the wavelength obtained by sintering the phosphor-attached glass powder of the present invention The conversion member contains the inorganic nanophosphor particles in a good dispersion state in the glass matrix. Therefore, it can be set as the wavelength conversion member excellent in luminous efficiency, durability, and reliability.

  Moreover, the following effects are acquired when using what attached inorganic nano fluorescent substance particle to the surface of the molded object which aggregated glass powder as fluorescent substance adhesion glass powder.

  (1) It is easy to control the content of inorganic nanophosphor particles in the wavelength conversion member.

  (2) A phosphor-attached glass powder in which inorganic nanophosphor particles are uniformly attached is easily obtained.

  (3) In order to produce the phosphor-attached glass powder, the required amount of the liquid in which the inorganic nanophosphor particles are dispersed in the dispersion medium is relatively small, and the yield can be improved (especially when the liquid is immersed in the molded body) , Wasteful inorganic nanophosphor particles are less likely to occur).

  (4) The steps of removing the dispersion medium to sintering can be performed continuously, and the production efficiency is excellent.

  The wavelength conversion member is manufactured by sintering the phosphor-attached glass powder, but it can also be used as it is as the wavelength conversion member without sintering the phosphor-attached glass powder. In this case, it is preferable to use it in a sealed state by providing a coating film on the surface or by storing it in a sealing container.

  The phosphor-attached glass powder and the wavelength conversion member of the present invention are suitable as a member used for a backlight light source of a mobile phone display such as a television, a personal computer, or a smartphone.

DESCRIPTION OF SYMBOLS 1 ... Phosphor adherence glass powder 2 ... Glass powder 3 ... Inorganic nanophosphor particle 4 ... Molded object 5 ... Glass 11 ... Phosphor adherence glass powder 20 ... Wavelength conversion member

Claims (16)

A method for producing a phosphor-attached glass powder in which inorganic nanophosphor particles are attached to the surface of a glass powder,
Contacting the inorganic nanophosphor particles with the glass powder in a liquid in which the inorganic nanophosphor particles are dispersed in a dispersion medium;
A step of attaching the inorganic nanophosphor particles to the surface of the glass powder by removing the dispersion medium in the liquid.   The manufacturing method of the fluorescent substance adhesion glass powder of Claim 1 which makes the said inorganic nano fluorescent substance particle and the said glass powder contact by adding the said glass powder in the said liquid.   The method for producing a phosphor-attached glass powder according to claim 1, wherein the inorganic nanophosphor particles and the glass powder are brought into contact with each other by spraying the liquid on the glass powder in the form of a mist.   The method for producing phosphor-attached glass powder according to claim 1, wherein the inorganic nanophosphor particles and the glass powder are brought into contact by mixing the liquid and a dispersion liquid in which the glass powder is dispersed.   The manufacturing method of the fluorescent substance adhesion glass powder as described in any one of Claims 1-4 whose said glass powder is a form of the molded object which aggregated the glass powder.   The manufacturing method of the fluorescent substance adhesion glass powder of Claim 5 which is the molded object which the said molded object aggregated by applying a pressure to glass powder.   The manufacturing method of the fluorescent substance adhesion glass powder of Claim 5 whose said molded object is a molded object which calcined and aggregated glass powder.   The manufacturing method of the fluorescent substance adhesion glass powder of Claim 5 whose said molded object is a molded object obtained by calcining the glass green sheet containing glass powder.   The manufacturing method of the fluorescent substance adhesion glass powder as described in any one of Claims 5-8 which makes the said inorganic nano fluorescent substance particle and the said glass powder contact by immersing the said molded object in the said liquid.   The method for producing a phosphor-attached glass powder according to any one of claims 5 to 8, wherein the inorganic nanophosphor particles and the glass powder are brought into contact with each other by allowing the liquid to penetrate into the molded body. A method for producing a wavelength conversion member containing inorganic nanophosphor particles in glass,
Producing the phosphor-attached glass powder by the method according to any one of claims 1 to 10,
And a step of sintering the phosphor-attached glass powder.   The method for producing a wavelength conversion member according to claim 11, wherein the sintering is performed in a vacuum atmosphere.   The manufacturing method of the wavelength conversion member of Claim 11 or 12 whose sintering temperature is 400 degrees C or less.   A wavelength conversion member manufactured by the method according to any one of claims 11 to 13.   A wavelength conversion member obtained by sintering phosphor-attached glass powder having inorganic nanophosphor particles attached to the surface of glass powder.   The wavelength conversion member which consists of the said fluorescent substance adhesion glass powder manufactured by the method as described in any one of Claims 1-10.

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