JP2005344025A - Fluorophor particle and method for producing the same and plasma display panel, illumination device and led - Google Patents

Fluorophor particle and method for producing the same and plasma display panel, illumination device and led Download PDF

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JP2005344025A
JP2005344025A JP2004166058A JP2004166058A JP2005344025A JP 2005344025 A JP2005344025 A JP 2005344025A JP 2004166058 A JP2004166058 A JP 2004166058A JP 2004166058 A JP2004166058 A JP 2004166058A JP 2005344025 A JP2005344025 A JP 2005344025A
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phosphor particles
phosphor
sio
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JP4524469B2 (en
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Masahiro Goto
Akira Nagatomi
Katayuki Sakane
Shuji Yamashita
堅之 坂根
修次 山下
昌大 後藤
晶 永富
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Dowa Mining Co Ltd
同和鉱業株式会社
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Abstract

【Task】
For example, it has sufficient resistance to thermal degradation conditions at the heat treatment level during PDP panel manufacture, vacuum ultraviolet degradation conditions at the vacuum ultraviolet (VUV) irradiation level used as excitation light for PDP, and between phosphor particles Provided are a method for producing phosphor particles in which aggregation is suppressed, and phosphor particles produced by the production method.
[Solution]
Prepare predetermined phosphor particles, add them to a mixed solvent of isopropyl alcohol and pure water, add tetraethoxysilane (TEOS) while maintaining the liquid temperature at 40 ° C. and continue stirring. After that, ammonia water was continuously added over 45 min, further aging was performed to obtain a suspension, and after separating the phosphor particles by filtration, the phosphor particles were dried without washing, and the SiO 2 gel was washed. The coated phosphor particles are put into an alumina crucible, and the SiO 2 gel-coated phosphor particles are baked in an ammonia atmosphere in a gas flow state, and the surface is coated with a SiO 2 film containing nitrogen. Obtained phosphor particles.
[Selection] Figure 4

Description

  The present invention relates to fluorescent lamps used in displays such as cathode ray tubes, field emission displays (FEDs), plasma display panels (PDPs), lighting devices such as solid state lighting devices (LEDs), solid state lighting fixtures, fluorescent lamps, fluorescent display tubes, etc. The present invention relates to a body particle and a manufacturing method thereof, and a plasma display panel, a lighting device and an LED using the phosphor particle.

  Conventionally, a cathode ray tube display (CRT) using light emission of a fluorescent film under electron beam excitation has been widely used as a high-luminance and high-definition display. However, there are limits to the flattening and thinning of displays. In recent years, plasma display panels (hereinafter referred to as PDPs) that can be easily flattened and thinned have attracted attention as a new display and are actively researched. Development is underway.

PDP has a discharge cell filled with rare gas such as He-Xe, Ne-Xe, Ar, etc., and light is generated by vacuum ultraviolet rays (VUV) generated by applying voltage to the electrode in the discharge cell. Each of the three primary colors red (R), green (G), and blue (B) has a structure in which various phosphors exhibiting fluorescence are excited and emitted to obtain visible light of a predetermined color. Here, the phosphor that emits red light used includes (Y, Gd) BO 3 : Eu, or Y 2 O 3 : Eu, and the phosphor that emits green light includes BaAl 12 O 19 : Mn, Alternatively, Zn 2 SiO 4 : Mn and the like, and examples of the phosphor emitting blue light include BaMgAl 10 O 17 : Eu and BaMgAl 16 O 27 : Eu.

However, these phosphors are thermally deteriorated by heat treatment (usually heating at about 400 ° C. to 500 ° C. for about 30 minutes in the air) at the time of manufacturing the PDP panel. Furthermore, during operation after the completion of the PDP panel, the vacuum ultraviolet rays are deteriorated by the vacuum ultraviolet rays used as excitation light. In particular, aluminate-based phosphors such as BaMgAl 10 O 17 : Eu or BaMgAl 16 O 27 : Eu that emit blue light are greatly deteriorated compared to other phosphors and are required to be improved immediately. In addition, the same problem as the problem related to the PDP panel described above also occurs in a lighting device or LED that combines a light emitting portion emitting blue to ultraviolet light and a phosphor, and there is a demand for immediate improvement.

Initially, BaMgAl 14 O 23 : Eu was used as the aluminate-based blue phosphor, but in response to the request, a phosphor having a BaMgAl 10 O 17 : Eu composition (see Patent Document 1) was proposed, and the heat described above. Deterioration with time, deterioration of light emission luminance accompanying vacuum ultraviolet light deterioration, and change with time of emission color could be suppressed to some extent. However, compared with phosphors of other colors, thermal deterioration and vacuum ultraviolet light deterioration are still severe, and attempts are now being made to optimize the composition itself.

On the other hand, as a trial in a different direction, various substances such as SiO 2 (silica) are attached to the surface of the phosphor to protect the surface of the phosphor, thereby maintaining the emission characteristics of the phosphor itself. A method for suppressing deterioration and vacuum ultraviolet light deterioration has been proposed. For example, Patent Document 2 describes that the luminous efficiency and the like of a phosphor can be improved by adhering a SiO 2 powder to a particle surface of an aluminate-based blue phosphor used in a fluorescent lamp, although it is scattered. Yes. Further, in Patent Document 3, the aluminate-based blue phosphor powder is immersed in a solution in which a silicon polymer is dissolved in an organic solvent, and the dried phosphor powder is heated at 1000 ° C. or less in the presence of oxygen to form a film. It is described that a SiO 2 coating film having a thickness of 100 nm can be formed, and as a result, the change in emission intensity with time is reduced and the life of the phosphor can be extended. In addition, Patent Documents 4 to 7 have been proposed as manufacturing methods for forming a SiO 2 coating film on a phosphor.

Japanese Patent Laid-Open No. 8-115673 Japanese Patent Laid-Open No. 10-204429 JP 2001-303037 A JP-A-8-92549 Japanese Patent No.2884702 Japanese Patent No. 2514423 JP 2002-69442 A

  As described above, various proposals have been made for the purpose of suppressing the thermal deterioration / vacuum ultraviolet deterioration of the phosphor and extending the life of the phosphor, but the results have not yet reached a satisfactory level. Furthermore, in an attempt to protect various surfaces by attaching various substances to the surface of the phosphor powder, the cohesiveness between the phosphor particles constituting the phosphor powder increases, and unwanted aggregation occurs. A new problem was also found. The present invention has been made under such circumstances, for example, heat degradation conditions at the heat treatment level at the time of manufacturing the PDP panel described above, vacuum ultraviolet light deterioration of the vacuum ultraviolet (VUV) irradiation level used as the excitation light of the PDP Provided are phosphor particles having sufficient resistance to conditions and in which aggregation of phosphor particles is suppressed, a method for producing the same, and a plasma display panel, an illumination device, and an LED using the phosphor particles. It is in.

In order to solve the above-mentioned problems, the present inventors have conducted research, and as a result, by coating the phosphor surface with a SiO 2 film containing nitrogen and having a film thickness of a predetermined thickness or less, the above-described thermal deterioration condition / It was conceived that phosphor particles having sufficient resistance to vacuum ultraviolet ray deterioration conditions and aggregation of phosphor particles were suppressed were obtained, and the present invention was completed.

That is, the first configuration of the present invention is a method for producing phosphor particles whose surface is coated with a SiO 2 film containing nitrogen,
In the step of coating the surface of the phosphor particles with SiO 2 gel and then performing a heat treatment in an atmosphere containing nitrogen,
In the phosphor particle manufacturing method, the heat treatment is performed at a heat treatment temperature of 800 ° C. or more, and the thickness of the SiO 2 gel coating film before the heat treatment is 25 nm or less.

The second configuration is a method of manufacturing the phosphor particles according to the first configuration,
When coating the surface of the phosphor particles with SiO 2 gel,
A phosphor particle manufacturing method comprising adding a gelling agent after mixing phosphor particles, an organosilane compound, and water in a water-soluble organic solvent.

A third configuration is a method for producing a phosphor particle according to the first or second configuration,
In the phosphor particle manufacturing method, a nitrogen atmosphere containing a flow is used as the nitrogen-containing atmosphere.

A fourth configuration is a method of manufacturing a phosphor particle according to any one of the first to third configurations,
A method for producing phosphor particles, wherein ammonia gas is used as the nitrogen-containing atmosphere.

A fifth configuration is the method for producing a phosphor particle according to any one of the first to fourth configurations,
In the phosphor particle manufacturing method, ammonia gas having a concentration of 99.9% or more is used as the nitrogen-containing atmosphere.

A sixth configuration is a method for manufacturing a phosphor particle according to any one of the first to fifth configurations,
The phosphor particles are produced by performing the heat treatment for 0.5 hr to 48 hr.

A seventh configuration is a method for producing a phosphor particle according to any one of the first to sixth configurations,
In the phosphor particle manufacturing method, the nitrogen concentration in the phosphor particles coated with the SiO 2 film is increased by 0.1 wt% or more by the heat treatment.

  An eighth configuration is a phosphor particle manufactured by the method for manufacturing a phosphor particle according to any one of the first to seventh configurations.

The ninth structure is a phosphor particle characterized in that the surface is coated with a vitrified SiO 2 film containing nitrogen.

A tenth configuration is the phosphor particle according to the eighth or ninth configuration, wherein the thickness of the vitrified SiO 2 film containing nitrogen is 25 nm or less.

  An eleventh configuration is the phosphor particle according to any one of the eighth to tenth configurations, wherein the phosphor particle is a phosphor particle containing aluminum and oxygen.

  A twelfth configuration is the phosphor particle according to any one of the eighth to eleventh configurations, wherein the phosphor particle is a blue light emitting phosphor.

A thirteenth configuration is the phosphor particle according to any one of the eighth to twelfth configurations, wherein the composition of the phosphor particle is BaMgAl 10 O 17 : Eu.

  A fourteenth configuration is a plasma display panel using the phosphor particles according to any one of the eighth to thirteenth configurations.

  A fifteenth configuration is an illumination device using the phosphor particles according to any one of the eighth to thirteenth configurations.

  A sixteenth configuration is an LED using the phosphor particles according to any one of the eighth to thirteenth configurations.

According to the method for producing phosphor particles according to the first to seventh configurations, the phosphor particles have sufficient resistance to heat deterioration conditions and vacuum ultraviolet light deterioration conditions, and aggregation of the phosphor particles is suppressed, It was possible to obtain phosphor particles having excellent light emission characteristics.
In addition, the phosphor particles according to the eighth to thirteenth structures suppress aggregation of the phosphor particles, are resistant to heat and vacuum ultraviolet light, and emit light even when used in an environment receiving heat or ultraviolet light. It is difficult to deteriorate and has a long life.
Furthermore, the plasma display panels, lighting devices, and LEDs according to the fourteenth to sixteenth configurations are unlikely to deteriorate in light emission characteristics and have a long life.

Hereinafter, embodiments of the present invention will be described in detail, but the present invention is not limited thereto.
The composition of the phosphor particles according to the present invention is not particularly limited, and the present invention can be applied to various phosphor particles. However, the present invention is particularly effective for blue-emitting phosphor particles (for example, BaMgAl 10 O 17 : Eu particles) having problems in heat resistance, vacuum ultraviolet resistance, and the like. Therefore, in the following description, blue light emitting phosphor particles (hereinafter sometimes abbreviated as “phosphor”) will be described as an example. Here, the particle shape of the phosphor may be spherical or plate-like, and is not particularly limited.

First, an example of a method for producing blue-emitting phosphor particles will be described using BaMgAl 10 O 17 : Eu as an example.
Methods for producing BaMgAl 10 O 17 : Eu include spray pyrolysis method, thermal plasma method, sol-gel method, coprecipitation method, etc., but generally diffusion of atoms at the contact surface or contact point between reaction solid phases. Manufactured by solid phase reaction. As a manufacturing process, for example, BaCO 3 , MgCO 3 , Al 2 O 3, Eu 2 O 3 and the like are weighed in a predetermined amount as a raw material powder, and then mixed well with a ball mill or the like, and flux (reaction accelerator) is added thereto. Is added and fired at about 1600 ° C. for about 3 hours. Here, the firing atmosphere is a reducing atmosphere, for example, H 2 gas, H 2 + N 2 mixed gas, N 2 gas or the like. This is because in the BaMgAl 10 O 17 : Eu phosphor, Eu is emitted as Eu 2+ , so Eu existing in the form of Eu 3+ in the raw material must be reduced to Eu 2+. . After the completion of the firing, BaMgAl 10 which is a phosphor particle having a predetermined particle size through a crushing step for unraveling the sintered phosphor particles, a washing step for removing impurities mixed in the previous step, a particle size separation step, etc. O 17 : Get Eu.

Next, a method for coating the surface of the phosphor particles with the SiO 2 film will be described.
A so-called sol-gel method is preferred as a method of coating the surface of the phosphor particles with the SiO 2 film.
The sol-gel method is a method in which a hydrolysis product of a coating substance is first deposited on the surface of phosphor particles, and then the hydrolysis product is subjected to a condensation reaction with a catalyst or the like. Therefore, in the case of the present invention, the coating of the SiO 2 film on the phosphor starts by mixing phosphor particles, an organosilane compound and water in an organic solvent and performing a sol hydrolysis reaction.

Here, the organic solvent is preferably water-soluble in order to function as a sol medium for proceeding the hydrolysis reaction, and alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly preferable.
As the organosilane, an alkoxysilane represented by the general formula R1 4-a Si (OR2) a (where R1 is a monovalent hydrocarbon group, R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, a Is an integer of 3 to 4.) Among them, tetraethoxysilane (hereinafter referred to as TEOS) and methyltrimethoxysilane are preferable.

In order to hydrolyze the alkoxysilane on the surface of the phosphor particles, pure water to be subjected to hydrolysis and the phosphor particles are put in the organic solvent and stirred, and the phosphor particles are suspended. deep. Next, alkoxysilane is added to the suspension and stirred. Thereafter, a catalyst for promoting the hydrolysis / condensation reaction is added and stirred. As a result, a coating film containing SiO 2 gel is formed on the surface of the phosphor particles.

The catalyst for promoting the hydrolysis / condensation reaction may be an acid such as hydrochloric acid, sulfuric acid, or phosphoric acid, but from the viewpoint of obtaining a uniform and dense coating film, an alkali is preferable. Ammonia without it is preferred. In addition, by using ammonia, a good uniform and dense SiO 2 film can be obtained, and there are many merits such as easy availability, low cost, easy volatile removal and no residual impurities. .

  Here, as a reaction tank used for the hydrolysis reaction, it is preferable to use a ceramic reaction tank, a Teflon-coated reaction tank, or the like rather than a metal tank. This is because when stirring in an organic solvent, the stirring blade and the reaction vessel wall may be scraped off by collision with the phosphor particles and may be mixed into the phosphor powder as an impurity that lowers the emission intensity.

The hydrolysis reaction and the subsequent condensation reaction are preferably allowed to proceed by aging after adding aqueous ammonia. The addition rate of the aqueous ammonia is not particularly limited, but it is preferably added slowly over 10 min. By slowly adding aqueous ammonia, it is possible to avoid the pH of the phosphor suspension from rising all at once, and to prevent the SiO 2 film coated on the phosphor particles from becoming rough.

Moreover, when adding ammonia water, aggregation of the fluorescent substance particles coated can be prevented by adding continuously. This is because by adding ammonia water continuously and gradually raising the pH of the phosphor suspension, SiO 2 particles are generated in the suspension other than the phosphor particle surface, and the SiO 2 particles are fluorescent. The situation that it acts as a binder that induces aggregation of body particles, and if SiO 2 is generated unevenly on the surface of the phosphor particles, the surface becomes uneven, and the phosphor particles tend to aggregate. This is because the situation can be avoided. Moreover, the liquid temperature at the time of aging after completion of the addition of ammonia water is not particularly limited, but is preferably about 10 ° C to 70 ° C, and more preferably about 40 ° C. When the liquid temperature is about 10 ° C. to 70 ° C. or about 40 ° C., the coating film can be prevented from becoming rough. The aging time is not particularly limited, but is preferably 0.5 hr to 5 hr.

Since the film thickness and film density of the SiO 2 coating film on the phosphor particles obtained by the above operation generally depend on the amount of alkoxysilane at the beginning of addition, the amount of pure water, the temperature of the phosphor suspension, the aging time, etc. By controlling these, a coating film of SiO 2 gel having an arbitrary film thickness and film density can be deposited on the surface of the phosphor particles.

Here, the film thickness of the coating film of SiO 2 gel is 25 nm or less, preferably 20 nm or less, more preferably less than 10 nm. This is because the silica film can transmit ultraviolet light having a wavelength of 254 nm, but absorbs vacuum ultraviolet light having a wavelength of 147 nm. That is, by setting the film thickness of the SiO 2 gel coating film to 25 nm or less, the film thickness of the silica film on the phosphor particles to be produced is regulated, and vacuum ultraviolet rays that are excitation light of the phosphor particles are Since the amount of light that is absorbed by the silica film and reaches the phosphor particles is reduced, it is possible to suppress the effect that the emission intensity is reduced. In particular, the influence of vacuum ultraviolet absorption by the silica film on the phosphor particles produced by setting the thickness of the SiO 2 gel coating film to less than 10 nm is almost negligible. On the contrary, the present inventors have found that by controlling the film thickness to less than 10 nm, it is possible to obtain emission intensity equal to or higher than that of phosphor particles without a coating film. Although the detailed reason for this is unknown, it is considered that the surface defects of the phosphor particles generated during crushing are smoothed by the SiO 2 gel coating film, and light can be efficiently emitted outside the phosphor particles.

Furthermore, it has also been found that when the film thickness of the SiO 2 gel coating film is 25 nm or less, preferably 20 nm or less, more preferably less than 10 nm, the coated phosphor particles can be prevented from aggregating with each other. This is considered to be because the aggregation of the phosphor particles via the coating film can be suppressed by making the coating film on the phosphor particle surface thin.

Next, control of the film thickness of the SiO 2 gel coating film by adjusting the amount of added alkoxysilane will be described.
First, (W1) is the amount of alkoxysilane to be added, (L) is the thickness of the SiO 2 gel coating film, and the specific surface area of the phosphor particles determined by the BET method (hereinafter referred to as specific surface area BET). ) Is (S), and the charged amount of phosphor particles is (W3). Then, if the surface of all the added phosphor particles (S × W3) is coated with SiO 2 gel with a film thickness (L), assuming that the volume of SiO 2 gel coating is (V1), V1 = S × W3 × L (Expression 1)
On the other hand, assuming that the density of the SiO 2 gel coating is ρ (equivalent to the density of silica gel = 2.0 g / cm 3 ) and the weight of SiO 2 generated on the surface of all phosphor particles is (W2), W2 = V1 × ρ (Formula 2)
Accordingly, when the molecular weight of SiO 2 is (Mw2) and the molar amount of SiO 2 is (M1), the molar amount of SiO 2 generated on the surface of all phosphor particles is M1 = W2 / Mw2 (Equation 3) It becomes.
If here alkoxysilane example TEOS, during Si (OC 2 H 5) 4 1.0mol, since Si is present 1.0 mol, SiO 2 generated from Si (OC 2 H 5) 4 1.0mol also 1.0 mol. That is, since M1 mol of TEOS is required to generate M1 mol of SiO 2 , if the molecular weight of TEOS is (Mw1), the amount of alkoxysilane (W1) is W1 = M1 × Mw1 (Formula 4) .
From (Equations 1 to 4), W1 = S × W3 × L × ρ × Mw1 / Mw2 (Equation 5), where ρ, Mw1, Mw2 are constants, S is a measured value, and W3 is a predetermined set value. For this reason, the amount of alkoxysilane to be added (W1) can be obtained by substituting the target film thickness value L into Equation 5.
Further, when Formula 5 is solved for L, L = Mw2 / (S × W3 × ρ × Mw1) × W1 (Formula 6) is obtained, and the coating film thickness of SiO 2 gel is obtained from the amount of added alkoxysilane (W1). Value (L) can be calculated.

Furthermore, as an example of a method for directly obtaining the coating film thickness value (L) of the SiO 2 gel, it can be obtained from the result of high-magnification observation using a transmission electron microscope (TEM).

The obtained SiO 2 gel-coated phosphor particles are isolated from the phosphor suspension by solid / liquid separation. Filtration is common as a method for solid / liquid separation. The drying method may be a general method such as warm air drying, vacuum drying, or spray dryer.

The thus-obtained phosphor particles coated with SiO 2 gel are excellent in heat resistance, oxidation resistance, and ultraviolet ray resistance compared to phosphor particles without a coating film. However, to the phosphor particles, by heat treatment and nitriding treatment to be described further below, densify the coating film of SiO 2 gel, nitrided, the densified coated phosphor particles of SiO 2 film which is nitrided Can be obtained. The coating film can be mechanically and chemically strengthened by densifying and nitriding the coating film. In addition, it is generated on the surface of the phosphor particles in the crushing process performed before forming the coating film. Since the surface defects and distortions can be removed, the light emission characteristics as a phosphor can be further improved.

Nitrogen, argon, ammonia, etc. can be considered as the heat treatment atmosphere, and nitrogen, ammonia, etc. can be considered as the nitrogen treatment atmosphere. There is no problem if the heat treatment and the nitriding treatment are performed separately, but in particular, by using ammonia, the heat treatment and the nitriding treatment are performed efficiently and simultaneously, and the SiO 2 gel coating film is mechanically and chemically strong silicon nitride film It is preferable because it is formed in the shape of When ammonia gas is used, the gas concentration is not particularly limited, but it is more preferably 99.9% or more in order to efficiently nitride the SiO 2 gel coating film.
The furnace used for the heat treatment is not particularly limited, but it is preferable that the exhaust gas does not accumulate in the furnace. Therefore, a furnace capable of performing the heat treatment in a gas flow state is preferable. Also, because ammonia is a corrosive gas, be careful about the furnace material.

If the heat treatment temperature exceeds 800 ° C, preferably 900 ° C or higher, the SiO 2 gel coating film becomes dense, that is, vitrification proceeds sufficiently, and the nitriding reaction also proceeds sufficiently. An excellent coating film can be obtained. On the other hand, when the heat treatment temperature is 1000 ° C. or lower, aggregation of phosphor particles due to dissolution of the SiO 2 gel coating film having a nano-order level film thickness can be avoided.

Here, the avoidance of aggregation of the phosphor particles will be further described.
Aggregation of the phosphor particles may occur both in the heat treatment step and the above-described SiO 2 gel coating step. If the particles aggregate after the crushing step of the phosphor particles, the aggregation is not broken until the phosphor particles are finally installed in a predetermined product. As a result, for example, since the filling density when applied as a paste is lowered, the light emission as the phosphor layer is weakened.

Therefore, it is important to avoid aggregation of particles in the surface treatment step after the phosphor particle crushing step. Therefore, the heat treatment temperature exceeds 800 ° C., preferably 900 ° C. or more and 1000 ° C. or less. In addition, when heat treatment is performed in the temperature range, not only densification (vitrification) and nitridation of the SiO 2 gel coating film, but also surface defects and strains generated in the phosphor particles by the phosphor particle crushing process It can also be removed, and the effect is great from the viewpoint of improvement of emission intensity and improvement of mechanical and chemical durability. A heat treatment time of 0.5 h or longer is preferable because the nitriding reaction proceeds sufficiently and the coating film is sufficiently densified. Further, since the effect is saturated even if the heat treatment is performed for 48 hours or more, the heat treatment time is preferably 0.5 h to 48 hours.

Further, the nitrogen concentration of the phosphor particles coated with the SiO 2 film obtained after the heat treatment is preferably increased by 0.10 wt% or more, more preferably 0.20 wt% or more, compared with that before the heat treatment. Here, the nitrogen concentration means the weight of nitrogen in the particles when the total weight of the phosphor particles with a coating film of SiO 2 gel is 100 wt%. That is, the coating film containing SiO 2 gel is densified (vitrified) and simultaneously nitrided (changed from SiO 2 to Si 3 N 4 ) by heat treatment and nitriding in an ammonia atmosphere, and the machine However, when the increase in nitrogen concentration, which is a parameter of the progress of the treatment, is 0.10 wt% or more, the coating film is sufficiently nitrided and heat resistant. This is because the oxidation resistance is also satisfactory.

Furthermore, the present inventors have found that the phosphor-resistant phosphor particles coated with the heat-treated SiO 2 film also have improved ultraviolet resistance to vacuum ultraviolet characteristics. The detailed reason for this is unknown, but the surface of the phosphor particle itself is covered with a dense and chemically stable coating film. This is probably because the change does not proceed and the progress of the degradation reaction is suppressed.

  When the phosphor particles according to the present invention produced as described above are used as, for example, a phosphor for PDP, heat deterioration due to heat treatment during panel production (usually: 400 ° C. to 500 ° C. × 30 min in the atmosphere) From the viewpoints of durability and sufficient durability against deterioration caused by ultraviolet (UV) to vacuum ultraviolet (VUV) used as excitation light after the panel is completed, it can be said to be an optimal material. . Similarly, it is an effective material as a lighting device combining a light emitting part emitting vacuum ultraviolet to blue light and a phosphor, which is expected as a next-generation illumination, and a phosphor for LED.

Hereinafter, based on a reference example, an Example, and a comparative example, this invention is demonstrated more concretely.
(Reference Example 1)
Reference Example 1 is an example in which phosphor particles represented by the general formula BaMgAl 10 O 17 : Eu commonly called BAM are used as the phosphor particles.
Using commercially available 3N grade reagents as raw materials, BaCO 3 0.90mol, Eu 2 O 3 0.05mol, 4MgCO 3 · Mg (OH) 2 · 5H 2 O 0.20mol, γ-Al 2 O 3 5.00mol, AlF 3 0.09 mol was weighed. Each of the weighed raw material powders was dry-mixed in a ball mill and then filled in an alumina crucible and fired in a nitrogen atmosphere for 8 hours including firing at 1600 ° C. × 3 h and heating / cooling time. The fired sample was crushed by a vibration ball mill, and phosphor particles were obtained through a washing and drying process. The median diameter (D50) of the obtained phosphor particles was 4.00 μm, and the specific surface area BET (m 2 / g) was 1.13 m 2 / g.

Add 20 g of this phosphor particle to a mixed solvent of 500 g of isopropyl alcohol and 80.0 g of pure water, and maintain 0.45 g of tetraethoxysilane (TEOS 95%) while maintaining the liquid temperature at 40 ° C. Added. After the addition of TEOS, 66.9 g of ammonia water (21.5%) was continuously added over 45 min using a tube pump, and further aging was continued for 60 min in an air atmosphere to obtain a suspension.
After the phosphor particles were separated from the resulting suspension by filtration, the phosphor particles were directly washed and dried without washing the phosphor particles to obtain phosphor particles coated with SiO 2 gel. The median diameter (D50) of the phosphor particles was 4.29 μm. Here, by the above-described film thickness calculation method, the coating film thickness of the phosphor particles coated with the SiO 2 gel was calculated to be 2.6 nm from the added TEOS amount. Further, before and after the coating was performed, the phosphor particles were excited with vacuum ultraviolet light having a wavelength of 147 nm, and the change in emission intensity was measured. These results are shown in Table 1.

(Reference Example 2)
The SiO 2 gel coating is performed in the same manner as in Reference Example 1 except that the amount of tetraethoxysilane (TEOS) added to the phosphor particles is 1.68 g with respect to 10 g of the phosphor particles. Phosphor particles provided with a film were obtained.
The median diameter (D50) of the phosphor particles before coating was 4.47 μm, the specific surface area BET (m 2 / g) was 0.80 m 2 / g, and the median diameter (D50) after coating was 6.39 μm. It was. The coating film thickness calculated from the added TEOS amount was 28.8 nm. Moreover, the photographic data which observed the particle | grain surface at the magnification of (* 200,000 times) using the transmission electron microscope (TEM) for the fluorescent substance particle surface are shown in FIG. From FIG. 3, a uniform SiO 2 gel coating film covering the phosphor particle surface could be confirmed. Further, the coating film thickness obtained from FIG. 3 was about 26 nm, which was almost the same value as the coating film thickness calculated from the TEOS amount. Further, before and after the coating was performed, the phosphor particles were excited with vacuum ultraviolet light having a wavelength of 147 nm, and the change in emission intensity was measured. These results are shown in Table 1.

(Comparison of characteristics of samples according to Reference Examples 1 and 2)
From Table 1, as a result of comparing the phosphor particles according to Reference Examples 1 and 2, the following was found.
First, the change rate of the median diameter of Reference Example 1 is small before and after the coating film is applied, whereas it greatly increases in Reference Example 2. This is because, in Reference Example 1, the coating film thickness is 2.6 nm and the coated phosphor particles are prevented from aggregating with each other, whereas in Reference Example 2, the coating film thickness is 28.8 nm. This is considered to be because the aggregation of the phosphor particles through the coating film proceeds.
Next, in the change in light emission intensity when the phosphor was made to emit light with vacuum ultraviolet light having a wavelength of 147 nm, the reference example 1 had only a 3% decrease after coating, whereas the reference example 2 had a decrease of 24%. became. This is because, in Reference Example 1, since the coating film thickness is less than 10 nm, absorption of vacuum ultraviolet rays was suppressed, and most of the vacuum ultraviolet rays could pass through the coating film, whereas in Reference Example 2, This is probably because the coating film thickness is 28.8 nm, and vacuum ultraviolet rays are partially absorbed by the coating film.

On the other hand, regarding the film thickness of the SiO 2 gel coating film covering the phosphor particle surface, the film thickness obtained from observation data using a transmission electron microscope (TEM) and the film thickness calculated from the TEOS amount are almost the same. It was also found out.

(Example 1)
Using commercially available 3N grade reagents as raw materials, BaCO 3 0.85mol, Eu 2 O 3 0.075mol, 4MgCO 3 · Mg (OH) 2 · 5H 2 O 0.20mol, α-Al 2 O 3 5.0mol, MgF 2 0.06 mol was weighed. Each weighed raw material powder is dry-mixed in a ball mill and then filled into an alumina crucible. It takes 9 hours, including two-step firing at 1100 ° C x 1h in a nitrogen atmosphere and then 1600 ° C x 3h and heating and cooling time. And fired. Next, as in Reference Example 1, phosphor particles were obtained through crushing, sieving, washing, and drying processes. The median diameter (D50) of the obtained phosphor particles was 3.21 μm, and the specific surface area BET (m 2 / g) was 1.34 m 2 / g.

20 g of this phosphor particle was added to a mixed solvent of 500 g of isopropyl alcohol and 80.0 g of pure water, and 0.420 g of tetraethoxysilane (TEOS 95%) was added while maintaining the liquid temperature at 40 ° C. Added. After the addition of TEOS, 66.9 g of ammonia water (21.5%) was continuously added over 45 min using a tube pump, and further aging was continued for 60 min in an air atmosphere to obtain a suspension.
After the phosphor particles were separated from the resulting suspension by filtration, the phosphor particles were directly washed and dried without washing the phosphor particles to obtain phosphor particles coated with SiO 2 gel. The median diameter (D50) of the phosphor particles was 3.23 μm. The coating film thickness was calculated to be 2.2 nm from the amount of TEOS added.

The resulting coating film-coated phosphor particles of SiO 2 gel, as compared to those of the uncoated film of SiO 2 gel, oxidation resistance, is an excellent phosphor resistant ultraviolet degradation, in this embodiment, The phosphor particles with a coating film of the SiO 2 gel were further subjected to heat treatment to obtain phosphor particles according to Example 1.
The heat treatment was performed by placing the obtained phosphor particles with an SiO 2 gel coating film in an alumina crucible and firing it at 900 ° C. for 1 hour in an ammonia atmosphere in a gas flow state. In addition, 99.9% UP of ammonia gas was used.

(Example 2)
As a heat treatment, the phosphor according to Example 2 was subjected to the same treatment as Example 1 except that the baking was performed at 900 ° C. for 6 hours in an ammonia atmosphere in a gas flow state, and the SiO 2 gel coating film was subjected to high temperature nitriding treatment. Particles were obtained.
The film thickness of the phosphor particles according to Example 1 was measured in the same manner as in Reference Example 2 at a magnification of (× 200,000 times) using a transmission electron microscope (TEM). The photograph data is shown in FIG.
The SiO 2 gel coating thickness obtained from FIG. 4 was 1.5 nm. This value is less than the coating film thickness of 2.2 nm calculated from the added TEOS amount described in Example 1. The decrease in the film thickness is due to the heat treatment in an ammonia atmosphere of the SiO 2 gel coating film. This is thought to be due to densification (vitrification).

(Comparative Example 1)
In the same manner as in Example 1, the SiO 2 gel coating was deposited on the surface of the phosphor particles, but the phosphor particles according to Comparative Example 1 were obtained without subsequent heat treatment.

(Comparative Example 2)
Except that the heat treatment of the phosphor particles with the coating film of SiO 2 gel was a heat treatment at 700 ° C. × 1 h in an ammonia atmosphere in a gas flow state, the same treatment as in Example 1 was performed, and the SiO 2 gel coating film was The phosphor particles according to Comparative Example 2 that were nitrided were obtained.

(Characteristic comparison of samples according to Examples 1 and 2 and Comparative Examples 1 and 2)
For the phosphor particles according to Examples 1 and 2 and Comparative Examples 1 and 2, (a) Thermal degradation in which the sample is subjected to heat treatment under conditions that promote degradation, and the change in emission intensity of the sample before and after the thermal treatment is compared. Measurements are made and the results are shown in Table 2 and FIG. 1. (b) The particle size distribution of the sample is measured and the results are shown in Table 2. (c) The amount of oxygen and nitrogen contained in the sample (O / N) ), And the results are shown in Table 2. (d) Vacuum ultraviolet deterioration measurement is performed by applying vacuum ultraviolet irradiation under conditions that promote deterioration to the sample and comparing changes in the emission intensity of the sample at each irradiation time. The results are shown in Table 2 and FIG. In Table 2, the data of the phosphor particles before the SiO 2 gel coating film is also shown as a reference.

(A) Thermal degradation measurement FIG. 1 shows the relative intensity indicated by the sample before heat treatment according to Comparative Example 2 on the vertical axis, by measuring the relative intensity of the emission intensity of each sample before and after the heat treatment under conditions that promote degradation. The horizontal axis represents the heat treatment temperature, the data of Example 1 is a solid line, the data of Example 2 is a one-dot chain line, the data of Comparative Example 1 is a two-dot chain line, and the data of Comparative Example 2 is taken. Is a graph in which is indicated by a broken line. As is apparent from the results of Table 2 and FIG. 1, in the samples according to Examples 1 and 2 in which the phosphor particles with a coating film of SiO 2 gel were further heat-treated, the emission intensity decreased after the thermal deterioration treatment. However, in the sample according to Comparative Example 2 and Comparative Example 1 that was not subjected to the heat treatment, deterioration was observed. Among them, the sample according to Example 2 exhibited excellent heat resistance that no change was observed in the light emission characteristics before and after thermal degradation (500 ° C. and 700 ° C.).

The reason why the heat resistance of the sample according to Example 2 is excellent is that the SiO 2 gel coating film was nitrided and strengthened by performing the heat treatment in ammonia, and the heat treatment was performed at 900 ° C. × 6 h. It is thought that. That is, when the heat treatment temperature is 900 ° C., densification (vitrification) of the SiO 2 gel coating film occurs, and when the heat treatment time is 6 hours, the densification sufficiently proceeds. On the other hand, when heat treatment is not performed as in the sample according to Comparative Example 1, the SiO 2 gel coating film is not densified, and when the heat treatment temperature is 700 ° C. × 1 h as in the sample according to Comparative Example 2. 2 It is considered that thermal degradation occurs because the gel coating film is not sufficiently densified.

The thermal degradation measurement was performed as follows.
For example, when measuring thermal degradation at 500 ° C, weigh approximately 2.0g of the phosphor particles for measurement, place them in an alumina crucible, and bake them at 500 ° C for 30 minutes in the air using a muffle furnace to obtain a sample with thermal degradation. It was.
Next, using a spectrophotometer, fluorescence measurement is performed on the sample before and after thermal degradation, and the change in emission intensity associated with thermal degradation is measured. Here, the excitation wavelength used for the fluorescence measurement is a vacuum ultraviolet ray of 147 nm.
In the case of measurement of thermal deterioration at different temperatures, for example, in the case of 700 ° C., all the same except that the firing temperature was changed from 500 ° C. to 700 ° C.

(B) Measurement of particle size distribution From the results in Table 2, it was found that the particle size distribution shifted slightly higher as the heat treatment temperature increased and the heat treatment time increased. However, no aggregated particles showing a particle size exceeding 10 μm (unfavorable particle size as a phosphor for PDP), which was measured together, were found in each sample, and it was found that none of the samples was problematic from the viewpoint of particle size distribution. .
The particle size distribution of the phosphor particle sample was measured using a laser scattering / diffraction particle size distribution measuring device manufactured by Beckman Coulter.

(C) Oxygen amount / nitrogen amount (O / N) analysis From the results in Table 2, the oxygen amount / nitrogen amount (O / N) contained in the sample was 0.62 wt% in Example 1 and 0.67 in Example 2. It was found to be wt%, which was increased by 0.10 wt% or more compared with that before the heat treatment in an ammonia atmosphere. On the other hand, in the case of the comparative example 2, it was 0.38 wt% and it was only an increase of 0.09 wt%. From these results, it was found that heat treatment should be performed at a temperature exceeding 700 ° C. in order to contain a sufficient amount of nitrogen in the sample.
The amount of oxygen / nitrogen (O / N) contained in the phosphor particle sample was measured using a simultaneous oxygen / nitrogen analyzer (TC-436) manufactured by LECO.
It was.

(D) Measurement of vacuum ultraviolet ray degradation FIG. 2 shows the sample before the irradiation treatment according to Comparative Example 2, in which the vertical axis shows the relative intensity of the emission intensity of the sample at each vacuum ultraviolet ray irradiation time under the condition for promoting the deterioration. 2 is a graph in which the relative intensity is taken as a normalized value of 1, the irradiation time is taken on the horizontal axis, the data of Example 2 is indicated by a solid line, and the data of Comparative Example 2 is indicated by a broken line. As is apparent from the results of Table 2 and FIG. 2, the sample according to Example 2 does not show a decrease in emission intensity regardless of the irradiation time of vacuum ultraviolet rays, and has excellent resistance to vacuum ultraviolet ray deterioration. I understand that On the other hand, it was found that the emission intensity of the sample according to Comparative Example 2 gradually decreased as the vacuum ultraviolet irradiation time increased to 60 min and 120 min.

In addition, the said vacuum ultraviolet ray deterioration measurement was performed as follows.
A phosphor particle sample was filled in a spectrophotometer cell holder, and the filled phosphor particles were irradiated with vacuum ultraviolet light having a wavelength of 147 nm, and the emission intensity of the phosphor particles was measured every 10 minutes. At this time, the initial emission intensity was A, the emission intensity measured every 10 min was B 10 , B 20 ,..., And B 10 / A, B 20 / A,. Here, FIG. 1 shows data up to 120 min of irradiation, and Table 2 shows data of 60 min and 120 min.

It is a graph which shows the heat-resistant deterioration characteristic of a sample. It is a graph which shows the vacuum ultraviolet-ray resistant characteristic of a sample. 4 is a transmission electron micrograph of a sample according to Reference Example 2. 4 is a transmission electron micrograph of a sample according to Example 2.

Claims (16)

  1. A method for producing phosphor particles whose surface is coated with a SiO 2 film containing nitrogen,
    In the step of coating the surface of the phosphor particles with SiO 2 gel and then performing a heat treatment in an atmosphere containing nitrogen,
    A method for producing phosphor particles, characterized in that, when the heat treatment is performed at a temperature of 800 ° C. or higher, the thickness of the SiO 2 gel coating film before the heat treatment is 25 nm or less.
  2. It is a manufacturing method of the fluorescent substance particles according to claim 1,
    When coating the surface of the phosphor particles with SiO 2 gel,
    A method for producing phosphor particles, comprising mixing phosphor particles, an organosilane compound, and water in a water-soluble organic solvent, and then adding a gelling agent.
  3. It is a manufacturing method of the fluorescent substance particles according to claim 1 or 2,
    An atmosphere containing nitrogen in a flow state is used as the nitrogen-containing atmosphere.
  4. It is a manufacturing method of the fluorescent substance particles according to any one of claims 1 to 3,
    A method for producing phosphor particles, wherein an ammonia atmosphere is used as the nitrogen-containing atmosphere.
  5. A method for producing a phosphor particle according to any one of claims 1 to 4,
    A method for producing phosphor particles, wherein ammonia gas having a concentration of 99.9% or more is used as the nitrogen-containing atmosphere.
  6. A method for producing a phosphor particle according to any one of claims 1 to 5,
    The method for producing phosphor particles, wherein the heat treatment is performed for 0.5 hr to 48 hr.
  7. A method for producing a phosphor particle according to any one of claims 1 to 6,
    A method for producing phosphor particles, characterized by increasing the nitrogen concentration in the phosphor particles coated with the SiO 2 film by 0.1 wt% or more by the heat treatment.
  8.   A phosphor particle manufactured by the method for manufacturing a phosphor particle according to claim 1.
  9. A phosphor particle, the surface of which is coated with a vitrified SiO 2 film containing nitrogen.
  10. Phosphor particles according to claim 8 or 9, wherein the thickness of SiO 2 film vitrified including the nitrogen is 25nm or less.
  11.   The phosphor particles according to claim 8, wherein the phosphor particles are phosphor particles containing aluminum and oxygen.
  12.   The phosphor particle according to claim 8, wherein the phosphor particle is a blue-emitting phosphor.
  13. The phosphor particles according to claim 8, wherein the composition of the phosphor particles is BaMgAl 10 O 17 : Eu.
  14.   A plasma display panel using the phosphor particles according to claim 8.
  15.   An illuminating device using the phosphor particles according to claim 8.
  16.   An LED comprising the phosphor particles according to claim 8.
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US7273568B2 (en) 2004-06-25 2007-09-25 Dowa Mining Co., Ltd. Phosphor and production method of the same, method of shifting emission wavelength of phosphor, and light source and LED
US7291289B2 (en) 2004-05-14 2007-11-06 Dowa Electronics Materials Co., Ltd. Phosphor and production method of the same and light source and LED using the phosphor
US7319195B2 (en) 2003-11-28 2008-01-15 Dowa Electronics Materials Co., Ltd. Composite conductor, superconductive apparatus system, and composite conductor manufacturing method
US7345418B2 (en) 2004-08-27 2008-03-18 Dowa Mining Co., Ltd. Phosphor mixture and light emitting device using the same
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US7432647B2 (en) 2004-07-09 2008-10-07 Dowa Electronics Materials Co., Ltd. Light source having phosphor including divalent trivalent and tetravalent elements
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US7443094B2 (en) 2005-03-31 2008-10-28 Dowa Electronics Materials Co., Ltd. Phosphor and manufacturing method of the same, and light emitting device using the phosphor
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CN101469264A (en) * 2007-12-27 2009-07-01 宇部材料工业株式会社 Blue light-emitting fluophor
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US7291289B2 (en) 2004-05-14 2007-11-06 Dowa Electronics Materials Co., Ltd. Phosphor and production method of the same and light source and LED using the phosphor
US7434981B2 (en) 2004-05-28 2008-10-14 Dowa Electronics Materials Co., Ltd. Manufacturing method of metal paste
US7273568B2 (en) 2004-06-25 2007-09-25 Dowa Mining Co., Ltd. Phosphor and production method of the same, method of shifting emission wavelength of phosphor, and light source and LED
USRE44996E1 (en) * 2004-06-25 2014-07-08 Nichia Corporation Phosphor and production method of the same, method of shifting emission wavelength of phosphor, and light source and LED
US7432647B2 (en) 2004-07-09 2008-10-07 Dowa Electronics Materials Co., Ltd. Light source having phosphor including divalent trivalent and tetravalent elements
US7884539B2 (en) 2004-07-09 2011-02-08 Dowa Electronics Materials Co., Ltd. Light source having phosphor including divalent, trivalent and tetravalent elements
US8441180B2 (en) 2004-07-09 2013-05-14 Dowa Electronics Materials Co., Ltd. Light source having phosphor including divalent, trivalent and tetravalent elements
US8066910B2 (en) 2004-07-28 2011-11-29 Dowa Electronics Materials Co., Ltd. Phosphor and manufacturing method for the same, and light source
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US7477009B2 (en) 2005-03-01 2009-01-13 Dowa Electronics Materials Co., Ltd. Phosphor mixture and light emitting device
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US7443094B2 (en) 2005-03-31 2008-10-28 Dowa Electronics Materials Co., Ltd. Phosphor and manufacturing method of the same, and light emitting device using the phosphor
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JP2009155546A (en) * 2007-12-27 2009-07-16 Ube Material Industries Ltd Blue light-emitting phosphor particle
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