JP2004231930A - Bivalent metal silicate phosphor, its production method as well as phosphor paste composition and vacuum ultraviolet ray-excited light emitting element using the phosphor - Google Patents

Bivalent metal silicate phosphor, its production method as well as phosphor paste composition and vacuum ultraviolet ray-excited light emitting element using the phosphor Download PDF

Info

Publication number
JP2004231930A
JP2004231930A JP2003060646A JP2003060646A JP2004231930A JP 2004231930 A JP2004231930 A JP 2004231930A JP 2003060646 A JP2003060646 A JP 2003060646A JP 2003060646 A JP2003060646 A JP 2003060646A JP 2004231930 A JP2004231930 A JP 2004231930A
Authority
JP
Japan
Prior art keywords
phosphor
metal silicate
divalent metal
silicate phosphor
bromine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2003060646A
Other languages
Japanese (ja)
Inventor
Takayuki Hisamune
Kohei Matsuda
孝之 久宗
康平 松田
Original Assignee
Kasei Optonix Co Ltd
化成オプトニクス株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kasei Optonix Co Ltd, 化成オプトニクス株式会社 filed Critical Kasei Optonix Co Ltd
Priority to JP2003060646A priority Critical patent/JP2004231930A/en
Priority claimed from KR10-2003-0017366A external-priority patent/KR20030076397A/en
Publication of JP2004231930A publication Critical patent/JP2004231930A/en
Pending legal-status Critical Current

Links

Abstract

The present invention provides a blue-emitting divalent metal silicate phosphor having improved luminous efficiency, a method for producing the same, a phosphor paste composition using the improved phosphor, and a VUV-excited light-emitting device having high luminance.
In a Eu-activated divalent metal silicate phosphor represented by a composition formula CaMgSi 2 O 6 : Eu, at least one of bromine and iodine is contained in a crystal matrix in a total amount of 20,000 ppm or less, A phosphor having a weight-average particle diameter D50 measured by a Coulter counter method in the range of 1 to 7 micrometers, a phosphor paste composition using the phosphor, and a VUV-excited light emitting device.
[Selection diagram] None

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a divalent metal silicate phosphor that emits blue light when excited by vacuum ultraviolet (VUV) and ultraviolet (UV) light having a wavelength of 200 nm or less, a method for producing the same, and a phosphor paste composition containing the phosphor. And a VUV-excited light-emitting element (VUV-excited light-emitting element) and a fluorescent lamp.
[0002]
[Prior art]
In recent years, rare gases such as Ar, Xe, He, Ne, or a mixed gas of these gases are used as glass, as represented by rare gas lamps and plasma display panels (PDPs) used as light sources for reading scanners. Of a VUV-excited light-emitting element having a structure in which a fluorescent film made of a VUV phosphor inside the envelope is excited by VUV radiated by discharge of the rare gas and emits light by being enclosed in the envelope formed by the method described above. Is being actively conducted.
[0003]
A rare gas lamp, which is a typical example of a VUV-excited light-emitting element, has a rare gas such as Xe or Xe-Ne sealed in a thin glass tube, and emits light when excited by VUV on the inner wall surface of the tube. A phosphor film made of a VUV phosphor is formed. When electric energy is applied between the electrodes of the rare gas lamp, a rare gas discharge occurs in the glass tube, and the emitted VUV excites the fluorescent film formed on the inner wall surface of the tube to emit visible light. .
[0004]
In principle, a PDP, which is another typical example of a VUV-excited light-emitting device, has the above-mentioned VUV-excited rare gas lamps further reduced in size, and rare gas lamps of three different colors are arranged in stripes or in a matrix. Can be thought of. That is, narrow discharge spaces (cells) are arranged in a stripe or a matrix. Each cell is provided with an electrode, and a fluorescent film made of a VUV phosphor is formed inside each cell. Each cell is filled with a rare gas such as Xe, Xe-Ne, He-Xe, He-Ne-Xe, etc. When electric energy is applied from an electrode in the cell, a rare gas discharge occurs in the cell and VUV occurs. Is emitted, and the fluorescent film in the cell is excited by the VUV to emit visible light, and the light emission displays an image. In the case of a full-color PDP, full-color display can be performed by arranging the cells each having a phosphor film that emits red, blue, and green light by VUV excitation in a stripe shape or a matrix shape.
[0005]
As a phosphor for forming a phosphor film of these VUV excitation light emitting elements, a red light emitting phosphor such as (Y, Gd) BO 3 : Eu, LaPO 4 : Ce, Tb, (Ba, Sr) MgAl 10 O 17 : Green light-emitting phosphors such as Eu, Mn, and Zn 2 SiO 4 : Mn, and blue light-emitting phosphors such as BaMgAl 10 O 17 : Eu are used alone or in combination according to a desired emission color. (See Electronic Materials Magazine December 1997, Industrial Research Company, etc.). Among these practical phosphors for VUV, which are practically used as a fluorescent film of a VUV excitation light emitting element, the phosphor mainly used as a blue component mainly has a composition of BaMgAl 10 O 17 : Eu and is abbreviated as BAM. This BAM phosphor has a high emission luminance when excited by irradiating VUV and has a good color purity as blue. The luminance degradation (baking degradation) in the baking step at the time of forming the fluorescent film of the excitation light emitting element is large, and the emission luminance decreases over time when the VUV excitation light emitting element is driven and exposed to VUV for a long time ( VUV degradation) is large, and the development of a blue-emitting VUV excitation phosphor with less baking degradation and less VUV degradation is desired.
[0006]
As a remedy for such a problem, one of the blue light-emitting phosphors having relatively little baking deterioration or VUV deterioration is Eu as an activator, and the composition formula thereof is divalent CaMgSi 2 O 6 : Eu. A metal silicate phosphor has been reported (see Proceedings of The 8th International Display Works 2001 pp. 1115). However, this phosphor has a problem that its luminance is lower than that of BAM, which is a conventional blue phosphor, and improvement of the luminance to a practical level has been studied.
[0007]
In addition, when viewed with a large phosphor of the process for the preparation of impact on such a quality, the CaCO 3 as the raw material of Ca is in this phosphor, as the raw material of Mg MgCO 3 and 3MgCO 3 · Mg (OH) 2, as a raw material of Si and SiO 2, and as a raw material of Eu is possible to use Eu 2 O 3 is introduced as a general method. However, on the other hand, even if these raw materials are prepared and fired, a divalent metal silicate phosphor represented by the composition formula CaMgSi 2 O 6 : Eu having a satisfactory emission intensity as a blue phosphor cannot be produced. It is known.
[0008]
On the other hand, a method using EuF 3 instead of Eu 2 O 3 has been introduced as another method for producing the divalent metal silicate phosphor, and has a good color purity and a relatively strong blue light emission. It has been reported that the phosphor shown can be obtained (see Proceedings of The 8th International Display Works 2001 pp. 1115).
However, in order to form a uniform and dense fluorescent film on a VUV-excited light emitting device such as a rare gas lamp or a PDP without practical problems, it is necessary to give the phosphor particles appropriate powder characteristics. More specifically, the particle size D50 measured by the Coulter counter method is 10 μm or less, preferably about 1 to 7 μm, more preferably about 1 to 4 μm. Further, regarding the particle size distribution, σ log (L ) And σlog (S) are desirably 0.5 or less. According to the conventionally known manufacturing method using EuF3, the particle size of the phosphor particles obtained is too large, and a powder having a range of powder characteristics suitable for forming a phosphor film as described above cannot be obtained. It is the current situation.
[0009]
Further, it is known that in an AC type PDP, the discharge starting voltage is affected by the tendency of the applied phosphor to be charged and changes. For example, BAM or (Y, Gd) BO 3 : Eu which is easily positively charged has a low discharge starting voltage, and Zn 2 SiO 4 : Mn which is easily negatively charged has a high voltage. From the viewpoint of the circuit, it is desirable that the discharge starting voltage is low. CaMgSi 2 O 6 : Eu manufactured by a conventional manufacturing method is easily negatively charged and requires a high pressure to start discharge. This was also one of the reasons why CaMgSi 2 O 6 : Eu was not put to practical use in PDP. The charging tendency mentioned here can be evaluated by measuring the blow-off charge amount of the substance. Specifically, the phosphor powder and the poval resin beads were mixed and shaken to cause frictional charging of both, and the charge amount of the phosphor powder was evaluated by measuring the blow-off charge amount.
[0010]
[Problems to be solved by the invention]
The present invention has been made in view of the above situation, and has a powder characteristic (grain size characteristic) that has a higher emission luminance than conventional ones and is preferable for forming a fluorescent film of a VUV excitation light emitting element such as a rare gas lamp or a PDP. It is an object of the present invention to provide a blue-emitting divalent metal silicate phosphor having a small particle size, a method for producing the same, a phosphor paste composition using the improved phosphor, and a VUV-excited light emitting device.
[0011]
[Means for Solving the Problems]
The present inventors have conducted various studies on a silicate phosphor represented by the composition formula CaMgSi 2 O 6 : Eu using Eu as an activator, and found that the base material of a conventional Eu-activated divalent metal silicate phosphor was used. When a specific amount of at least one of bromine and iodine is contained therein, or in a step of firing the phosphor raw material at least once at 800 ° C. or more, bromine, iodine, a bromine compound and an iodine compound are contained in the phosphor raw material. It has been found that when an Eu-activated divalent metal silicate phosphor is produced by incorporating at least one of the above, the emission luminance under VUV excitation is improved. Further, the above improved specification makes it possible to produce a phosphor having a relatively small particle size suitable for forming a VUV-excited light emitting element phosphor film, which was not possible with the conventional specification, and furthermore, the weight median particle size D50 of the phosphor particles is reduced. It is surprisingly found that when the σlog (L) and the σlog (S) are controlled to 0.5 or less and the σlog (L) and σlog (S) are controlled to 0.5 or less, a fluorescent substance which tends to be positively charged due to the tendency to blow-off is obtained. I was able to do it.
[0012]
Further, by using the phosphor paste composition using the improved phosphor, it becomes possible to form a phosphor film on the VUV excitation light emitting device, and the VUV excitation light emitting device with improved blue component luminance I found that.
The present inventors have found various specifications for improvement of the phosphor represented by CaMgSi 2 O 6 : Eu as described above, and have reached the present invention.
That is, the above object of the present invention is achieved by adopting the following configuration.
[0013]
(1) basic composition is represented by the general formula (Ca 1-x-u Eu x M II u) O · a (Mg 1-v Zn v) O · bSiO 2 · wM III · tCl, and bromine and iodine A divalent metal silicate phosphor, characterized in that it contains at least one of the following. In the above formula, M II represents at least one metal element among barium (Ba) and strontium (Sr), and M III represents lanthanum (La), yttrium (Y), cerium (Ce), and indium. (In) and at least one metal element in bismuth (Bi), wherein a, b, x, t, u, v and w are respectively 0.9 ≦ a ≦ 1.1, 1.9 ≦ b ≦ 2.2, 5 × 10 −3 ≦ x ≦ 10 −1 , 0 ≦ t ≦ 2 × 10 −1 and 0 ≦ u + v + w ≦ 4 × 10 −1 . }
(2) The divalent metal silicate phosphor according to (1), wherein the total amount of bromine and iodine contained in the phosphor is 20,000 ppm or less.
[0014]
(3) The divalent metal silicate phosphor according to (1) or (2), wherein the weight median particle diameter D50 measured by the Coulter counter method is in the range of 1 to 7 μm.
(4) The divalent metal silicate phosphor according to (3), wherein the weight median particle diameter D50 measured by the Coulter counter method is in the range of 1 to 4 μm.
(5) The divalent metal silicate phosphor according to (3) or (4), wherein σlog (L) and σlog (S) measured by the Coulter counter method are 0.5 or less.
[0015]
(6) The divalent metal silicate phosphor according to any one of (1) to (5), wherein the blow-off charge amount relative to the Poval resin is positive.
(7) In the method for producing a divalent metal silicate phosphor, in the step of firing the phosphor material at least once at 800 ° C. or more, bromine, iodine, a bromine compound, and an iodine compound The method for producing a divalent metal silicate phosphor according to any one of the above (1) to (6), wherein at least one kind is contained.
(8) The method for producing a divalent metal silicate phosphor according to (7), wherein the amount of bromine and iodine contained in the phosphor raw material is 0.001 wt% or more.
(9) The method for producing a divalent metal silicate phosphor according to (7) or (8), wherein ammonium bromide is used as a bromine compound and ammonium iodide is used as an iodine compound contained in the phosphor raw material. .
[0016]
(10) In a phosphor paste composition obtained by dispersing a phosphor in a solvent in which a binder is dissolved, the phosphor is a divalent metal silicate phosphor according to any one of (1) to (6). Or a divalent metal silicate phosphor produced by the production method according to any one of (7) to (9).
(11) In an ultraviolet-excitation light-emitting element that excites and emits the fluorescent film by vacuum ultraviolet light emitted by discharge of a rare gas sealed in the envelope in which the fluorescent film is formed, the fluorescent film may be ( The divalent metal silicate phosphor according to any one of 1) to (6) or the divalent metal silicate phosphor produced by the production method according to any one of (7) to (9). A vacuum ultraviolet ray excited light emitting device, wherein the device is formed.
[0017]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
To produce the phosphor of the present invention, stoichiometrically (Ca 1-x-u Eu x M II u) O · a (Mg 1-v Zn v) O · bSiO 2 · wM III · tCl { However, in the above formula, M II represents at least one metal element among Ba and Sr, M III represents at least one metal element among La, Y, Ce, In and Bi, and a, b, x, t, u, v and w are respectively 0.9 ≦ a ≦ 1.1, 1.9 ≦ b ≦ 2.2, 5 × 10 −3 ≦ x ≦ 10 −1 , and 0 ≦ t ≦ 2. × 10 -1 and 0 ≦ u + v + w ≦ 4 × 10 -1 Hereinafter, the same applies. At a ratio of}, the oxides of the metal elements represented by Ca, Mg, Si, Eu, Zn, and M II and M III constituting the phosphor, or oxides of the above-described metals at a high temperature can be converted. A phosphor raw material mixture comprising a compound of each of the above metals such as carbonates and sulfates is filled into a heat-resistant container such as an alumina crucible, and is heated at a temperature of 800 ° C. or more, preferably 1000 to 1400 ° C., and 2 to 40 The firing is performed at least once over time. In this manufacturing step, in the step of firing the phosphor material at least once at 800 ° C. or more, the phosphor material contains at least one of bromine, iodine, a bromine compound and an iodine compound. In this firing step, chlorine and a chlorine compound may be contained.
Thereafter, the fired product may be subjected to post-treatments such as dispersion, washing, drying, and sieving according to the necessity of the performance of the finally used phosphor in forming a phosphor film.
[0018]
In the step of firing the Eu-activated divalent metal silicate phosphor containing at least one of bromine and iodine of the present invention and the phosphor raw material at least once at 800 ° C. or more, the phosphor raw material contains bromine and iodine. The Eu-activated divalent metal silicate phosphor produced by the production method of the present invention containing at least one of a bromine compound and an iodine compound is a conventional Eu-activated divalent metal silicate phosphor. It was found that the emission luminance under VUV excitation was higher than that of the phosphor, and the weight median particle diameter D50 was 1 to 6 μm, which was smaller than that of the conventional Eu-activated divalent metal silicate phosphor.
[0019]
In the production of the phosphor of the present invention, as a supply source of bromine and iodine contained in the phosphor material, for example, alkali metal compounds such as LiBr, LiI, NaBr, NaI, KBr, KI, CaBr 2 , CaI 2 , MgBr 2, there are MgI alkaline earth metal compounds such as 2, for the alkali metal compound, the particles of the rising a can after firing the phosphor tends to cause the generation of the fused agglomerated particles. On the other hand, the alkaline earth compound contains a metal constituting the phosphor matrix, and has an influence on the matrix composition. Ammonium bromide NH4Br and ammonium iodide NH4I are preferred because they do not have such disadvantages and are not affected by alkaline substances. Also, when ammonium bromide and ammonium iodide are used, it is possible to obtain a phosphor having desired relatively small particles and a small amount of coagulated particles, and a dense phosphor film of a VUV excitation light emitting element such as a rare gas lamp or a PDP can be obtained. With proper powder properties necessary for forming, specifically, small particles having a particle size measured by a Coulter counter method of 10 μm or less, preferably about 1 to 7 μm, more preferably about 1 to 4 μm, Regarding the particle size distribution, one having σlog (L) and σlog (S) of 0.5 or less can be obtained.
[0020]
In addition, the total amount of bromine and iodine contained in the phosphor raw material must be not less than 0.001 wt%, which is the minimum amount that exerts the effect of the present invention on the crystals of the fluorescent particles. The preferred specific content is also affected by the types of the bromine compound and the iodine compound used, the degree of sealing of the crucible at the time of firing, and the like.
[0021]
In the production of the phosphor of the present invention, apart from the effect of containing at least one of bromine and iodine, which is the object of the present invention, the influence on the quality of the basic phosphor composition and composition is affected. Therefore, the following technical matters need to be sufficiently considered.
[0022]
Further, in the divalent metal silicate phosphor of the present invention, as the a value and the b value representing the composition of the host crystal deviate from 1.0 and 2.0, respectively, an incompletely crystallized phosphor or heterophase is formed. Since the probability of light emission increases and the emission luminance gradually decreases, the values a and b are 0.9 ≦ a ≦ 1.1 and 1.9 ≦ b ≦ 2 in terms of the emission luminance of the obtained phosphor. It is preferable that the number satisfies the range of 2, and it is particularly preferable that the a value and the b value are a = 1.0 and b = 2.0, respectively. Regarding the above-mentioned x value representing the activation amount of Eu, when this value exceeds 0.1, a different phase different from the above-mentioned composition is formed, the luminance of the phosphor is reduced, and when it is smaller than 5 × 10 −3. Either is not preferable because the amount of luminescent centers is insufficient and the luminescent intensity of the obtained phosphor is reduced. Therefore, the activation amount (x value) of Eu is preferably a number that satisfies the range of 5 × 10 −3 ≦ x ≦ 1 × 10 −1 from the viewpoint of the emission luminance of the obtained phosphor. If the content t of the Cl element in the phosphor is larger than 2 × 10 −1, the emission luminance is lower than that of the phosphor containing no Cl element, which is not preferable. Therefore, the content of the Cl element is preferably a number satisfying the range of 0 ≦ t ≦ 2 × 10 −1 . The metal element M II, the total content of Zn and the metal element MIII (u + v + w) and is more than 4 × 10 -1 M II, the emission luminance becomes lower than a phosphor contains no Zn and M III preferably Absent.
Therefore, it is preferable that the total amount of the metal elements M II , Zn and the metal element M III is a number satisfying the range of 0 ≦ (u + v + w) ≦ 4 × 10 −1 .
[0023]
The phosphor paste composition of the present invention can be used for the purpose by adding the above-mentioned divalent metal silicate phosphor of the present invention to a solvent in which a binder resin is dissolved, kneading the mixture sufficiently, and adjusting the amount of the solvent. It can be produced by preparing a paste having an appropriate viscosity accordingly. Ethyl cellulose, nitrocellulose, polyethylene oxide, acrylic resin and the like are used as a binder resin when producing the phosphor paste composition containing the phosphor of the present invention, and also used for adjusting the viscosity of the paste. As the solvent, a solvent such as water, butyl acetate, butyl carbitol, butyl carbitol acetate, terpineol or the like is used. Further, as the phosphor in the phosphor paste composition of the present invention, a mixed phosphor of the divalent metal silicate phosphor of the present invention and a phosphor of other composition may be used depending on the purpose and application. It goes without saying that it is good.
[0024]
Further, the VUV-excited light-emitting device of the present invention is obtained by applying the phosphor paste composition of the present invention to a predetermined location in an envelope made of glass or the like, drying the applied paste, and baking to form a phosphor film. It is manufactured in the same manner as the conventional VUV-excited light emitting device except that a phosphor film made of the divalent metal silicate phosphor of the present invention is formed.
The thus obtained divalent metal silicate phosphor of the present invention has a smaller particle diameter than the conventional divalent metal silicate phosphor, and thus the particle diameter of the conventional divalent metal silicate phosphor is small. It has become possible to use as a phosphor for a VUV-excited light emitting device, which is too large to form a fluorescent film. Further, the divalent metal silicate phosphor of the present invention has a higher luminous luminance than a conventional divalent metal silicate phosphor, and the luminous luminance is obtained by forming a fluorescent film with a phosphor paste composition containing this phosphor. VUV-excited light-emitting device having a high VUV can be obtained.
[0025]
【Example】
Next, the present invention will be described with reference to examples.
[Example 1A]
CaCO 3 0.98 mol MgCO 3 1.0 mol SiO 2 2.0 mol Eu 2 O 3 0.01 mol NH 4 Br 0.2 mol
After sufficiently mixing the phosphor raw material containing 4.8 wt% of bromine in the above ratio, 15 g was charged into an alumina crucible and fired in a reducing atmosphere at a maximum temperature of 1150 ° C. for 14 hours including a temperature rise / fall time. . This calcined product is subjected to a sieving treatment to have a composition formula of (Ca 0.98 Eu 0.02 ) O.MgO.2SiO 2 containing 200 ppm of bromine, and a blow-off charge amount relative to the poval resin of 18. The Eu-activated divalent metal silicate phosphor of Example 1A which became positively charged at 2 μC / g was obtained.
[0027]
The content of bromine and iodine in the phosphor of the present invention was derived by comparing and measuring the Kα radiation of bromine and iodine by a standard addition method using a calibration curve with a fluorescent X-ray apparatus ZSX manufactured by Rigaku Corporation. .
The thus-obtained phosphor powder of Example 1A was filled in a cell having a cylindrical recess having a diameter of 12 mm and a depth of 1 mm, and the cell was pressed down with a glass plate to form a flat powder. A phosphor screen is prepared, and the phosphor screen is irradiated with vacuum ultraviolet rays of 146 nm to excite and emit light, and the emission luminance and the chromaticity point of the emission color at that time are measured to derive the stimulus sum (emission luminance / y value). As a result, the stimulus sum value of Comparative Example 1A below, which was measured in the same manner, was 100%, while the value of Example 1A was 120%.
[0028]
Note that the luminance of the blue phosphor changes greatly in proportion to its emission color (y value of chromaticity coordinates according to the CIE color system), so that the luminous efficiency between the blue emission phosphors having different y values of the emission color is reduced. As a simple method of comparison, the emission color is compared by a value (luminance / y) obtained by dividing the luminance by the y value when expressed in chromaticity coordinates (x, y) (hereinafter referred to as “stimulus sum”). Is generally performed. Hereinafter, comparison of the luminous efficiency of the phosphor is performed based on the sum of the stimuli.
[0029]
When the particle size distribution of the phosphor of Example 1A was derived by the Coulter counter method, the weight median particle diameter (D50) was 3.7 μm, σlog (L) = 0.37, σlog (S) = 0.42. Met.
Here, Dn indicates the particle size of n% cumulative on a weight basis from the smaller particle size, and σlog (L) and σlog (S) are respectively σlog (L) = log (D84.1 / D50) and σlog (S) = − log (D15.9 / D50). σlog (L) is a value indicating a particle size distribution of a larger particle size than D50, and σlog (S) is a value indicating a particle size distribution of a smaller particle size than D50. It indicates that it is big.
[0030]
[Example 1B]
30% by weight of Eu activated divalent metal silicate phosphor of Example 1A, 10% by weight of butyl carbitol, 53% by weight of butyl carbitol acetate and 7% by weight of ethylcellulose were thoroughly kneaded. The phosphor paste composition of Example 1B was prepared.
[0031]
[Example 1C]
The phosphor paste composition of Example 1B obtained as described above is applied on a glass plate having a width of 2 mm, dried at 120 ° C. for 30 minutes, and then baked at 500 ° C. for 30 minutes, whereby the fluorescent light is applied on the glass plate. A film was formed. This glass plate was held in a glass tube having an outer diameter of 4 mm, nickel electrodes were attached to both ends of the glass tube, and the inside of the tube was evacuated to a vacuum. Then, a gas of 98% -Xe2% Ne was sealed at 50 torr. VUV-excited light-emitting device (rare gas lamp) was manufactured. In the prior art phosphor CaMgSi 2 O 6 containing no bromine or iodine before the present invention, it was said that the sphere diameter was too large to form a dense phosphor film, but the phosphor paste composition of Example 1B was used. It was visually confirmed that the phosphor film formed by the method was dense and had no unevenness, and the VUV-excited light-emitting device of Example 1C could be used without any practical problem.
[0032]
[Example 2A]
CaCO 3 0.98 mol MgCO 3 1.0 mol SiO 2 2.0 mol Eu 2 O 3 0.01 mol NH 4 Br 0.5 mol
After the phosphor raw material having the above ratio containing 11 wt% of bromine was sufficiently mixed, the composition formula was (Ca 0.88 Eu 0.02 ) O in the same manner as in Example 1A, except that 15 g was filled in an alumina crucible. The Eu-activated divalent metal silicate phosphor of Example 2A was obtained, which contained 240 ppm of bromine in MgO · 2SiO 2 and had a positive charge of 30.3 μC / g relative to the poval resin. .
[0034]
When the phosphor of Example 2A was excited by 146 nm vacuum ultraviolet rays to emit light in the same manner as in Example 1A, the emission luminance and the chromaticity point of the emission color were measured. The value was 114% with respect to the stimulus sum value of 100% in Comparative Example 1A below.
When the particle size distribution of the phosphor of Example 2A was derived by the Coulter counter method, the weight median particle diameter (D50) was 3.6 μm, σlog (L) = 0.34, σlog (S) = 0.39. Met.
[0035]
[Example 2B]
A paste composition of Example 2B was produced in the same manner as the phosphor paste composition of Example 1B except that the phosphor of Example 2A was used instead of the phosphor of Example 1A.
[0036]
[Example 2C]
A VUV excitation light-emitting device of Example 2C was obtained in the same manner as in Example 1C, except that the phosphor paste composition of Example 2B was used instead of the phosphor paste composition of Example 1B. It was visually confirmed that the phosphor film formed of the phosphor paste composition of Example 2B was dense and uniform, and the VUV-excited light emitting device of Example 2C could be used without any practical problem. .
[0037]
[Example 3A]
CaCO 3 0.98 mol MgCO 3 1.0 mol SiO 2 2.0 mol Eu 2 O 3 0.01 mol NH 4 I 0.2 mol
After sufficiently mixing the phosphor material in the above ratio containing 7.4 wt% of iodine, 15 g was filled in an alumina crucible in the same manner as in Example 1A, except that the composition formula was (Ca 0.98 Eu 0.02). ) iodine containing 230ppm with O · MgO · 2SiO 2, relative blow-off charge amount becomes positively charged and 30.3μC / g for Poval resin, an Eu-activated divalent metal silicate phosphor of example 3A Obtained.
[0039]
When the phosphor of Example 3A was excited by 146 nm vacuum ultraviolet rays to emit light in the same manner as in Example 1A, the emission luminance and the chromaticity point of the emission color were measured. The value was 104% with respect to 100% of the stimulus sum value of Comparative Example 1A below.
Further, when the particle size distribution of the phosphor of Example 3A was derived by the Coulter counter method, the weight median particle diameter (D50) was 5.5 μm, σlog (L) = 0.45, σlog (S) = 0.47. Met.
[0040]
[Example 3B]
A paste composition of Example 3B was produced in the same manner as the phosphor paste composition of Example 1B, except that the phosphor of Example 3A was used instead of the phosphor of Example 1A.
[0041]
[Example 3C]
A VUV-excited light-emitting device of Example 3C was obtained in the same manner as in Example 1C, except that the phosphor paste composition of Example 3B was used instead of the phosphor paste composition of Example 1B. It was visually confirmed that the phosphor film formed from the phosphor paste composition of Example 3B was dense and uniform, and the VUV-excited light emitting device of Example 3C could be used without any practical problem. .
[0042]
[Example 4A]
CaCO 3 0.98 mol MgCO 3 1.0 mol SiO 2 2.0 mol Eu 2 O 3 0.01 mol NH 4 I 0.5 mol
After the phosphor raw material having the above ratio containing 16 wt% of iodine was sufficiently mixed, 15 g was filled in an alumina crucible in the same manner as in Example 1A, and the composition formula was (Ca 0.98 Eu 0.02 ) O. · in MgO · 2SiO 2 iodine containing 450 ppm, relative blow-off charge amount for Poval resin becomes positively charged and 30.3μC / g, to obtain a Eu-activated divalent metal silicate phosphor of example 4A .
[0044]
When the phosphor of Example 4A was excited with 146 nm vacuum ultraviolet rays to emit light in the same manner as in Example 1A, the emission luminance and the chromaticity point of the emission color were measured, and the stimulus sum was obtained. The value was 114% with respect to the stimulus sum value of 100% in Comparative Example 1A below.
When the particle size distribution of the phosphor of Example 4A was derived by the Coulter counter method, the weight median particle size (D50) was 5.8 μm, σlog (L) = 0.48, σlog (S) = 0.48. Met.
[0045]
[Example 4B]
A paste composition of Example 4B was produced in the same manner as the phosphor paste composition of Example 1B, except that the phosphor of Example 4A was used instead of the phosphor of Example 1A.
[0046]
[Example 4C]
A VUV-excited light-emitting device of Example 4C was obtained in the same manner as in Example 1C, except that the phosphor paste composition of Example 4B was used instead of the phosphor paste composition of Example 1B. It was visually confirmed that the phosphor film formed of the phosphor paste composition of Example 4B was dense and uniform, and the VUV-excited light emitting device of Example 4C could be used without any practical problem. .
[0047]
[Comparative Example 1A]
CaCO 3 0.98 mol MgCO 3 1.0 mol SiO 2 2.0 mol EuF 3 0.02 mol
After sufficiently mixing the phosphor raw materials in the above ratio not containing bromine and iodine, 15 g was filled in an alumina crucible in the same manner as in Example 1A, except that the composition formula was (Ca 0.98 Eu 0.02). ) O · in MgO · 2SiO 2 does not contain bromine and iodine, relative blow-off charge amount for Poval resin is negatively charged and -13.6μC / g, Eu-activated divalent metal of Comparative example 1A A silicate phosphor was obtained.
[0049]
In the same manner as in Example 1A, the phosphor of Comparative Example 1A was excited with vacuum ultraviolet rays of 146 nm to emit light, and the luminous luminance and the chromaticity point of the luminescent color were measured to obtain the stimulus sum. 100% was used as the standard for the sum of stimulation.
When the particle size distribution of the phosphor of Comparative Example 1A was derived by the Coulter counter method, the weight median particle diameter (D50) was 12.4 μm, σlog (L) = 0.87, σlog (S) = 0.70. Met.
[0050]
[Comparative Example 1B]
A paste composition of Comparative Example 1B was produced in the same manner as the phosphor paste composition of Example 1B, except that the phosphor of Comparative Example 1A was used instead of the phosphor of Example 1A.
[0051]
[Comparative Example 1C]
A VUV-excited light-emitting device of Comparative Example 1C was obtained in the same manner as the VUV-excited light-emitting device of Example 1C, except that the phosphor paste composition of Comparative Example 1B was used instead of the phosphor paste composition of Example 1B. Since the phosphor film formed of the phosphor paste composition of Comparative Example 1B had many pinholes, unevenness, and peeling points, the VUV-excited light emitting device of Comparative Example 1C was not practical.
[0052]
[Comparative Example 2A]
CaCO 3 0.98 mol MgCO 3 1.0 mol SiO 2 2.0 mol Eu 2 O 3 0.01 mol
After sufficiently mixing the phosphor raw materials in the above ratio not containing bromine or iodine, 15 g was filled in an alumina crucible, and the composition formula was changed to (Ca 0.98 Eu 0.02) in the same manner as in Example 1A. ) O · in MgO · 2SiO 2 contains no bromine or iodine, relative blow-off charge amount for Poval resin is negatively charged and -9.6μC / g, Eu-activated divalent metal of Comparative example 2A A silicate phosphor was obtained.
[0054]
When the phosphor of Comparative Example 2A was excited with 146 nm vacuum ultraviolet light to emit light in the same manner as in Example 1A, the emission luminance and the chromaticity point of the emission color were measured, and the sum of the stimuli was determined. The value was 9% with respect to 100% of the stimulus sum value of Comparative Example 1A.
When the particle size distribution of the phosphor of Comparative Example 2A was derived by the Coulter counter method, the weight median particle diameter (D50) was 41.4 μm, σlog (L) = 0.53, σlog (S) = 1.09. Met.
Since the phosphor of Comparative Example 2A had a very low emission intensity, it was not satisfactory for use as a phosphor.
[0055]
【The invention's effect】
According to the present invention, by adopting the above configuration, the emission luminance is improved as compared with the conventional Eu-activated divalent metal silicate phosphor, and a phosphor having a small particle size can be provided. This phosphor is used as a phosphor film. By using this, it has become possible to provide a VUV-excited light-emitting element having high emission luminance.

Claims (11)

  1. Basic composition has the general formula (Ca 1-x-u Eu x M II u) O · a (Mg 1-v Zn v) is represented by O · bSiO 2 · wM III · tCl, and in the bromine and iodine A bivalent metal silicate phosphor containing at least one kind.
    In the above formula, M II represents at least one metal element among barium (Ba) and strontium (Sr), and M III represents lanthanum (La), yttrium (Y), cerium (Ce), and indium. (In) and at least one metal element in bismuth (Bi), wherein a, b, x, t, u, v and w are respectively 0.9 ≦ a ≦ 1.1, 1.9 ≦ b ≦ 2.2, 5 × 10 −3 ≦ x ≦ 10 −1 , 0 ≦ t ≦ 2 × 10 −1 and 0 ≦ u + v + w ≦ 4 × 10 −1 . }
  2. 2. The divalent metal silicate phosphor according to claim 1, wherein the total amount of bromine and iodine contained in the phosphor is 20,000 ppm or less.
  3. 3. The divalent metal silicate phosphor according to claim 1, wherein the phosphor has a weight median particle diameter D50 measured by a Coulter counter method within a range of 1 to 7 [mu] m.
  4. The divalent metal silicate phosphor according to claim 3, wherein a weight median particle diameter D50 measured by a Coulter counter method is in a range of 1 to 4 µm.
  5. 5. The divalent metal silicate phosphor according to claim 3, wherein σlog (L) and σlog (S) are 0.5 or less in a particle size distribution measured by a Coulter counter method.
  6. The divalent metal silicate phosphor according to any one of claims 1 to 5, wherein the amount of blow-off charge relative to the Poval resin is positive.
  7. In the method for producing a divalent metal silicate phosphor, the phosphor raw material is baked at least once at 800 ° C. or more, and at least one of bromine, iodine, a bromine compound, and an iodine compound is contained in the phosphor raw material. The method for producing a divalent metal silicate phosphor according to claim 1, wherein the phosphor is contained.
  8. The method for producing a divalent metal silicate phosphor according to claim 7, wherein the amount of bromine and iodine contained in the phosphor raw material is 0.001 wt% or more.
  9. 9. The method for producing a divalent metal silicate phosphor according to claim 7, wherein ammonium bromide is used as a bromine compound and ammonium iodide is used as an iodine compound contained in the phosphor raw material.
  10. In a phosphor paste composition obtained by dispersing a phosphor in a solvent in which a binder is dissolved, the phosphor is the divalent metal silicate phosphor according to any one of claims 1 to 6, or A phosphor paste composition, which is a divalent metal silicate phosphor produced by the production method according to any one of claims 7 to 9.
  11. An ultraviolet-excited light-emitting element that excites and emits the fluorescent film by vacuum ultraviolet light emitted by discharge of a rare gas enclosed in an envelope in which the fluorescent film is formed, wherein the fluorescent film is A bivalent metal silicate phosphor according to any one of claims 6 to 9 or a bivalent metal silicate phosphor produced by the production method according to any one of claims 7 to 9. Vacuum ultraviolet light-emitting element.
JP2003060646A 2003-01-30 2003-01-30 Bivalent metal silicate phosphor, its production method as well as phosphor paste composition and vacuum ultraviolet ray-excited light emitting element using the phosphor Pending JP2004231930A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2003060646A JP2004231930A (en) 2003-01-30 2003-01-30 Bivalent metal silicate phosphor, its production method as well as phosphor paste composition and vacuum ultraviolet ray-excited light emitting element using the phosphor

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2003060646A JP2004231930A (en) 2003-01-30 2003-01-30 Bivalent metal silicate phosphor, its production method as well as phosphor paste composition and vacuum ultraviolet ray-excited light emitting element using the phosphor
KR10-2003-0017366A KR20030076397A (en) 2002-03-22 2003-03-20 Bivalent metal silicate phosphor and process for its production, and a phosphor paste composition and a vacuum ultraviolet ray excitation type light-emitting device employing such a phosphor
US10/391,627 US6899825B2 (en) 2002-03-22 2003-03-20 Bivalent metal silicate phosphor and process for its production, and a phosphor paste composition and a vacuum ultraviolet ray excitation type light-emitting device employing such a phosphor

Publications (1)

Publication Number Publication Date
JP2004231930A true JP2004231930A (en) 2004-08-19

Family

ID=32958922

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2003060646A Pending JP2004231930A (en) 2003-01-30 2003-01-30 Bivalent metal silicate phosphor, its production method as well as phosphor paste composition and vacuum ultraviolet ray-excited light emitting element using the phosphor

Country Status (1)

Country Link
JP (1) JP2004231930A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7597822B2 (en) 2006-05-19 2009-10-06 Canon Kabushiki Kaisha Blue phosphor and display panel using the same
JP2010500458A (en) * 2006-08-15 2010-01-07 ルミン サイエンス アンド テクノロジー グループ カンパニー リミテッド Silicate-based luminescent material with multiple emission peaks, method for preparing the luminescent material, and light emitting device using the luminescent material

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7597822B2 (en) 2006-05-19 2009-10-06 Canon Kabushiki Kaisha Blue phosphor and display panel using the same
JP2010500458A (en) * 2006-08-15 2010-01-07 ルミン サイエンス アンド テクノロジー グループ カンパニー リミテッド Silicate-based luminescent material with multiple emission peaks, method for preparing the luminescent material, and light emitting device using the luminescent material

Similar Documents

Publication Publication Date Title
KR101040627B1 (en) Plasma display display device, light emitting device and image display system using same
JP4092911B2 (en) Method for manufacturing plasma display device
KR100610216B1 (en) Phosphor and plasma display device
KR100910442B1 (en) Green Phosphor and Device Using the Same
EP1167489B1 (en) Method for producing aluminate fluorescent substance, a fluorescent and a device containing a fluorescent substance
KR100572432B1 (en) Plasma Display Device, Phosphor Used In It And Method Of Manufacturing The Same
KR100535430B1 (en) Plasma display apparatus, fluorescent material, and fluorescent material manufacturing method
KR100572782B1 (en) Plasma display unit, phosphor and process for producing phosphor
JP4122752B2 (en) Light emitting device
US7268492B2 (en) Plasma display device with green emitting phosphor that becomes positively charged
KR100716386B1 (en) Plasma display
US20060152135A1 (en) Phosphor and plasma display panel using the same
JP3915458B2 (en) Plasma display device
JP4228098B2 (en) Alkaline earth metal silicate phosphor and light emitting device
JP4042372B2 (en) Method for manufacturing phosphor
US6617788B2 (en) Phosphor and display device or light source using the same
JP4561194B2 (en) Alkaline earth aluminate phosphor for cold cathode fluorescent lamp and cold cathode fluorescent lamp
JP4123758B2 (en) Light emitting device
WO2004094558A1 (en) Phosphor and plasma display unit
KR100716387B1 (en) Plasma display
JP4449389B2 (en) Method for manufacturing phosphor for plasma display device
EP1892279B1 (en) Phosphor, phosphor paste and light-emitting device
KR100572431B1 (en) Plasma Display, Phosphor, and Phosphor Manufacturing Method
JP3988615B2 (en) Plasma display device
TW434307B (en) Aluminate phosphor, process for preparing the same, and vacuum ultraviolet-excited light emitting device

Legal Events

Date Code Title Description
A621 Written request for application examination

Free format text: JAPANESE INTERMEDIATE CODE: A621

Effective date: 20051206

A977 Report on retrieval

Effective date: 20071102

Free format text: JAPANESE INTERMEDIATE CODE: A971007

A131 Notification of reasons for refusal

Free format text: JAPANESE INTERMEDIATE CODE: A131

Effective date: 20071120

A02 Decision of refusal

Free format text: JAPANESE INTERMEDIATE CODE: A02

Effective date: 20080318