JPH0662947B2 - Fluorescent body and its manufacturing method - Google Patents
Fluorescent body and its manufacturing methodInfo
- Publication number
- JPH0662947B2 JPH0662947B2 JP59240452A JP24045284A JPH0662947B2 JP H0662947 B2 JPH0662947 B2 JP H0662947B2 JP 59240452 A JP59240452 A JP 59240452A JP 24045284 A JP24045284 A JP 24045284A JP H0662947 B2 JPH0662947 B2 JP H0662947B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- range
- composition formula
- numerical value
- phosphor according
- 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.)
- Expired - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 75
- 239000000203 mixture Substances 0.000 claims description 34
- 229910052693 Europium Inorganic materials 0.000 claims description 23
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 18
- 238000010304 firing Methods 0.000 claims description 14
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims description 13
- 229910014307 bSiO Inorganic materials 0.000 claims description 10
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- 150000002367 halogens Chemical class 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims 4
- 229910052789 astatine Inorganic materials 0.000 claims 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 32
- 230000005855 radiation Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- -1 barium halides Chemical class 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 241001289141 Babr Species 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052788 barium Inorganic materials 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010894 electron beam technology Methods 0.000 description 3
- 150000002178 europium compounds Chemical class 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000002601 radiography Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- LEARFKLHSNWJQW-UHFFFAOYSA-L P.[Cl-].[Br-].[Ba+2] Chemical compound P.[Cl-].[Br-].[Ba+2] LEARFKLHSNWJQW-UHFFFAOYSA-L 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003745 diagnosis Methods 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- QEDFUJZRPHEBFG-UHFFFAOYSA-K europium(3+);tribromide Chemical compound Br[Eu](Br)Br QEDFUJZRPHEBFG-UHFFFAOYSA-K 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Conversion Of X-Rays Into Visible Images (AREA)
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】 ［発明の分野］ 本発明は、蛍光体およびその製造法に関するものであ
る。さらに詳しくは、本発明は、二価のユーロピウムに
より賦活されているアルカリ土類金属ハロゲン化物系蛍
光体およびその製造法に関するものである。Description: FIELD OF THE INVENTION The present invention relates to a phosphor and a method for producing the same. More specifically, the present invention relates to an alkaline earth metal halide phosphor activated by divalent europium and a method for producing the same.
［発明の背景］ 二価のユーロピウムで賦活したアルカリ土類金属ハロゲ
ン化物系蛍光体の一種として、従来より二価ユーロピウ
ム賦活アルカリ土類金属弗化ハロゲン化物蛍光体（ＭII
ＦＸ：Ｅｕ2+、ただしＭIIはＢａ、ＳｒおよびＣａから
なる群より選ばれる少なくとも一種のアルカリ土類金属
であり、Ｘは弗素以外のハロゲンである）がよく知られ
ている。この蛍光体は、Ｘ線などの放射線で励起すると
近紫外発光（瞬時発光）を示し、また、Ｘ線などの放射
線を照射したのち可視乃至赤外領域の電磁波で励起する
と近紫外発光（輝尽発光）を示すものである。BACKGROUND OF THE INVENTION As one kind of divalent europium-activated alkaline earth metal halide phosphors, a divalent europium-activated alkaline earth metal fluoride halide phosphor (M II
FX: Eu 2+ , where M II is at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca, and X is halogen other than fluorine) are well known. This phosphor exhibits near-ultraviolet emission (instantaneous emission) when excited with radiation such as X-rays, and near-ultraviolet emission (stimulated emission) when irradiated with radiation such as X-rays and then excited with electromagnetic waves in the visible or infrared region. Light emission).
また、上記の二価ユーロピウム賦活アルカリ土類金属弗
化ハロゲン化物蛍光体とは別の蛍光体として、本出願人
は、下記組成式で表わされる新規な二価ユーロピウム賦
活アルカリ土類金属ハロゲン化物系蛍光体について、既
に特許出願している（特願昭５８−１９３１６１号）。Further, as a phosphor different from the above-mentioned divalent europium-activated alkaline earth metal fluoride halide phosphor, the applicant of the present invention is a novel divalent europium-activated alkaline earth metal halide system represented by the following composition formula. A patent application has already been made for the phosphor (Japanese Patent Application No. 58-193161).
組成式：ＭIIＸ２・ａＭIIＸ′２：ｘＥｕ2+ （ただし、ＭIIはＢａ、ＳｒおよびＣａからなる群より
選ばれる少なくとも一種のアルカリ土類金属であり；Ｘ
およびＸ′はＣｌ、ＢｒおよびＩからなる群より選ばれ
る少なくとも一種のハロゲンであって、かつＸ≠Ｘ′で
あり；そしてａは０．１≦ａ≦１０．０の範囲の数値で
あり、ｘは０＜ｘ≦０．２の範囲の数値である） この二価ユーロピウム賦活アルカリ土類金属ハロゲン化
物蛍光体は、上記の出願明細書に記載されているように
そのＸ線回折パターンから、前記ＭIIＦＸ：Ｅｕ2+蛍光
体とは結晶構造を異にする別種の蛍光体であることが判
明しており、Ｘ線、紫外線、電子線などの放射線を照射
すると４０５ｎｍ付近に発光極大を有する近紫外乃至青
色発光（瞬時発光）を示すものである。また、この蛍光
体にＸ線、紫外線、電子線などの放射線を照射した後４
５０〜１０００ｎｍの波長領域の電磁波で励起すると、
近紫外乃至青色領域に発光（輝尽発光）を示す。従っ
て、Ｘ線撮影などに用いられる放射線増感スクリーン、
および蛍光体の輝尽性を利用する放射線像変換方法に用
いられる放射線像変換パネル用の蛍光体として有用なも
のである。Compositional formula: M II X 2 · a M II X ′ 2 : xEu 2+ (where M II is at least one alkaline earth metal selected from the group consisting of Ba, Sr and Ca; X
And X ′ is at least one halogen selected from the group consisting of Cl, Br and I, and X ≠ X ′; and a is a numerical value in the range of 0.1 ≦ a ≦ 10.0, x is a numerical value in the range of 0 <x ≦ 0.2.) This divalent europium-activated alkaline earth metal halide phosphor is obtained from its X-ray diffraction pattern as described in the above-mentioned application. It has been found that the M II FX: Eu 2+ phosphor is a different kind of phosphor having a different crystal structure, and when irradiated with radiation such as X-rays, ultraviolet rays, and electron beams, it has a maximum emission at around 405 nm. It exhibits near-ultraviolet to blue emission (instantaneous emission). After irradiating this phosphor with radiation such as X-rays, ultraviolet rays, and electron beams, 4
When excited by electromagnetic waves in the wavelength range of 50 to 1000 nm,
Light emission (stimulated luminescence) is shown in the near ultraviolet to blue region. Therefore, a radiographic intensifying screen used for X-ray photography,
And, it is useful as a phosphor for a radiation image conversion panel used in a radiation image conversion method utilizing the stimulability of the phosphor.
このように有用な蛍光体においても、その輝尽発光輝度
は少しでも高いものであることが望まれている。Even in such a useful phosphor, it is desired that its stimulated emission luminance be as high as possible.
［発明の要旨］ 本発明は、Ｘ線などの放射線を照射したのち４５０〜１
０００ｎｍの波長領域の電磁波で励起したときの輝尽発
光輝度の向上した上記の新規な二価ユーロピウム賦活ア
ルカリ土類金属ハロゲン化物蛍光体およびその製造法を
提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention, after irradiating radiation such as X-ray, 450-1
It is an object of the present invention to provide the above-mentioned novel divalent europium-activated alkaline earth metal halide phosphor having improved stimulated emission luminance when excited with an electromagnetic wave in the wavelength region of 000 nm and a method for producing the same.
本発明者は、上記目的を達成するために、上記の新規な
二価ユーロピウム賦活アルカリ土類金属ハロゲン化物蛍
光体について種々の研究を行なった。その結果、該蛍光
体に特定量の一酸化ケイ素を添加して得られる蛍光体
は、高輝度の輝尽発光を示すことを見出し、本発明に到
達したものである。In order to achieve the above object, the present inventor has conducted various studies on the novel divalent europium-activated alkaline earth metal halide phosphor described above. As a result, they have found that a phosphor obtained by adding a specific amount of silicon monoxide to the phosphor exhibits high-intensity stimulated luminescence, and arrived at the present invention.
すなわち本発明の蛍光体は、組成式（Ｉ）： ＭIIＸ２・ａＭIIＸ′２・ｂＳｉＯ：ｘＥｕ2+…（Ｉ） （ただし、ＭIIはＢａであり；ＸおよびＸ′はいずれも
Ｃｌ、ＢｒおよびＩからなる群より選ばれる少なくとも
一種のハロゲンであって、かつＸ≠Ｘ′であり；そし
て、ａは０．１≦ａ≦１０．０の範囲の数値であり、ｂ
は０＜ｂ≦３×１０-2の範囲の数値であり、ｘは０＜ｘ
≦０．２の範囲の数値である） で表わされる二価ユーロピウム賦活アルカリ土類金属ハ
ロゲン化物系蛍光体である。That is, the phosphor of the present invention has a composition formula (I): M II X 2 · aM II X ′ 2 · bSiO: xEu 2+ (I) (where M II is Ba; X and X ′ are both Is at least one halogen selected from the group consisting of Cl, Br and I, and X ≠ X ′; and a is a numerical value in the range of 0.1 ≦ a ≦ 10.0 and b
Is a numerical value in the range of 0 <b ≦ 3 × 10 −2 , and x is 0 <x
It is a divalent europium-activated alkaline earth metal halide-based phosphor represented by the following formula.
また本発明の蛍光体の製造法は、化学量論的に組成式
（II）： ＭIIＸ２・ａＭIIＸ′２・ｂＳｉＯ：ｘＥｕ…（II） （ただし、ＭII、Ｘ、Ｘ′、ａ、ｂおよびｘの定義は前
述と同じである） に対応する相対比となるように蛍光体原料混合物を調整
したのち、この混合物を中性雰囲気もしくは弱還元性雰
囲気中で４００乃至１３００℃の範囲の温度で焼成する
ことを特徴とする。The method for producing the phosphor of the present invention is stoichiometrically represented by the composition formula (II): M II X 2 · aM II X ′ 2 · bSiO: xEu (II) (where M II , X, X ′). , A, b, and x are the same as those defined above), and the phosphor raw material mixture was adjusted to a relative ratio corresponding to the above, and the mixture was heated to 400 to 1300 ° C. in a neutral atmosphere or a weak reducing atmosphere. It is characterized by firing at a temperature in the range.
本発明は、上記の新規な二価ユーロピウム賦活アルカリ
土類金属ハロゲン化物蛍光体に特定量の一酸化ケイ素を
添加することにより、蛍光体にＸ線などの放射線を照射
したのち４５０〜１０００ｎｍの波長領域の電磁波で励
起したときの輝尽発光輝度の向上を実現するものであ
る。The present invention is to add a specific amount of silicon monoxide to the above-mentioned novel divalent europium-activated alkaline earth metal halide phosphor to irradiate the phosphor with radiation such as X-ray, and then to a wavelength of 450 to 1000 nm. It is intended to improve the stimulated emission luminance when excited by electromagnetic waves in the region.
［発明の構成］ 本発明の二価ユーロピウム賦活アルカリ土類金属ハロゲ
ン化物系蛍光体は、たとえば、次に記載するような製造
法により製造することができる。[Structure of the Invention] The divalent europium-activated alkaline earth metal halide phosphor of the present invention can be produced, for example, by the production method described below.
まず、蛍光体原料として、 １）ＢａＣｌ２、ＢａＢｒ２、およびＢａＩ２からなる
群より選ばれる少なくとも二種のバリウムハロゲン化
物、 ２）ＳｉＯ（一酸化ケイ素）、および ３）ハロゲン化物、酸化物、硝酸塩、硫酸塩などのユー
ロピウムの化合物からなる群より選ばれる少なくとも一
種の化合物、 を用意する。First, as phosphor raw materials, 1) at least two kinds of barium halides selected from the group consisting of BaCl 2 , BaBr 2 , and BaI 2 , 2) SiO (silicon monoxide), and 3) halides, oxides, At least one compound selected from the group consisting of europium compounds such as nitrates and sulfates is prepared.
ここで、上記１）の蛍光体原料としては、少なくともハ
ロゲンが異なる二種もしくはそれ以上のバリウムハロゲ
ン化物が用いられる。場合によっては、さらにハロゲン
化アンモニウム（ＮＨ４Ｘ″；ただし、Ｘ″はＣｌ、Ｂ
ｒまたはＩである）などをフラックスとして使用しても
よい。Here, as the phosphor material of the above 1), at least two kinds of barium halides having different halogens are used. In some cases, ammonium halide (NH 4 X ″; where X ″ is Cl, B
r or I) or the like may be used as the flux.
蛍光体の製造に際しては、上記１）のバリウムハロゲン
化物、２）の一酸化ケイ素および３）のユーロピウム化
合物を用いて、化学量論的に、組成式（II）： ＭIIＸ２・ａＭIIＸ′２・ｂＳｉＯ：ｘＥｕ…（II） （ただし、ＭIIはＢａであり；ＸおよびＸ′はいずれも
Ｃｌ、ＢｒおよびＩからなる群より選ばれる少なくとも
一種のハロゲンであって、かつＸ≠Ｘ′であり；そし
て、ａは０．１≦ａ≦１０．０の範囲の数値であり、ｂ
は０＜ｂ≦３×１０-2の範囲の数値であり、ｘは０＜ｘ
≦０．２の範囲の数値である） に対応する相対比となるように秤量混合して、蛍光体原
料の混合物を調製する。In the production of the phosphor, the barium halide of 1), the silicon monoxide of 2) and the europium compound of 3) are used stoichiometrically to prepare a composition formula (II): M II X 2 · aM II. X ′ 2 · bSiO: xEu ... (II) (wherein M II is Ba; X and X ′ are at least one halogen selected from the group consisting of Cl, Br and I, and X ≠ X ′; and a is a numerical value in the range of 0.1 ≦ a ≦ 10.0 and b
Is a numerical value in the range of 0 <b ≦ 3 × 10 −2 , and x is 0 <x
A mixture of phosphor raw materials is prepared by weighing and mixing so as to obtain a relative ratio corresponding to (a value in the range of ≦ 0.2).
本発明の蛍光体の製造法において、輝尽発光輝度の点か
ら、組成式（II）において添加成分である一酸化ケイ素
（ＳｉＯ）の量を表わすｂ値は１０-4≦ｂ≦１０-2の範
囲にあるのが好ましい。同じく輝尽発光輝度の点から、
組成式（II）におけるＭIIＸ２とＭIIＸ′２との割合を
表わすａ値は０．２５≦ａ≦６．０の範囲にあるのが好
ましく、さらに好ましくは０．５≦ａ≦２．０の範囲で
あり、ユーロピウムの賦活量を表わすｘ値は１０-5≦ｘ
≦１０-1の範囲にあるのが好ましい。In the method for producing a phosphor of the present invention, the b value representing the amount of silicon monoxide (SiO) as an additive component in the composition formula (II) is 10 −4 ≦ b ≦ 10 −2 from the viewpoint of stimulated emission luminance. It is preferably within the range. Similarly, in terms of stimulated emission brightness,
The value a representing the ratio of M II X 2 and M II X ′ 2 in the composition formula (II) is preferably in the range of 0.25 ≦ a ≦ 6.0, more preferably 0.5 ≦ a ≦. It is in the range of 2.0, and the x value representing the activation amount of europium is 10 −5 ≦ x
It is preferably in the range of ≦ 10 −1 .
蛍光体原料混合物の調製は、 ｉ）上記１）〜３）の蛍光体原料を単に混合することに
よって行なってもよいし、あるいは、 ii）まず、上記１）および２）の蛍光体原料を混合し、
この混合物を１００℃以上の温度で数時間加熱したの
ち、得られた熱処理物に上記３）の蛍光体原料を混合す
ることによって行なってもよいし、あるいは、 iii）まず、上記１）および２）の蛍光体原料を溶液の
状態で混合し、この溶液を加温下（好ましくは５０〜２
００℃）で、減圧乾燥、真空乾燥、噴霧乾燥などにより
乾燥し、しかるのち得られた乾燥物に上記３）の蛍光体
原料を混合することによって行なってもよい。The phosphor material mixture may be prepared by simply mixing i) the phosphor materials of 1) to 3) above, or ii) first, mixing the phosphor materials of 1) and 2) above. Then
This mixture may be heated at a temperature of 100 ° C. or higher for several hours, and then the obtained heat-treated product may be mixed with the phosphor raw material of the above 3), or iii) first, the above 1) and 2 ) The phosphor raw materials are mixed in a solution state, and the solution is heated (preferably 50 to 2).
It may be carried out by drying at 00 ° C.) under reduced pressure, vacuum drying, spray drying or the like, and then mixing the dried material thus obtained with the phosphor raw material of 3) above.
なお、上記ii）の方法の変法として、上記１）〜３）の
蛍光体原料を混合し、得られた混合物に上記熱処理を施
す方法、あるいは上記１）および３）の蛍光体原料を混
合し、この混合物に上記熱処理を施し、得られた熱処理
物に上記２）の蛍光体原料を混合する方法を利用しても
よい。また、上記iii）の方法の変法として、上記１）
〜３）の蛍光体原料を溶液の状態で混合し、この溶液を
乾燥する方法、あるいは上記１）および３）の蛍光体原
料を溶液の状態で混合し、この溶液を乾燥したのち得ら
れた乾燥物に上記２）の蛍光体原料を混合する方法を利
用してもよい。As a modification of the above method ii), the phosphor raw materials of 1) to 3) above are mixed and the resulting mixture is subjected to the heat treatment, or the phosphor raw materials of 1) and 3) above are mixed. Alternatively, the method of subjecting the mixture to the heat treatment and mixing the obtained heat-treated product with the phosphor material of the above 2) may be used. In addition, as a modification of the above method iii), the above 1)
To 3) the phosphor raw materials are mixed in a solution state, and the solution is dried, or the phosphor raw materials 1) and 3) above are mixed in a solution state, and the solution is dried. The method of mixing the phosphor material described in 2) above with the dried product may be used.
上記ｉ）、ii）、およびiii）のいずれの方法において
も、混合には、各種ミキサー、Ｖ型ブレンダー、ボール
ミル、ロッドミルなどの通常の混合機が用いられる。In any of the above methods i), ii), and iii), an ordinary mixer such as various mixers, V-type blenders, ball mills, and rod mills is used for mixing.
次に、上記のようにして得られた蛍光体原料混合物を石
英ボート、アルミナルツボ、石英ルツボなどの耐熱性容
器に充填し、電気炉中で焼成を行なう。焼成温度は４０
０〜１３００℃の範囲が適当であり、好ましくは５００
〜１０００℃の範囲である。発光輝度などの点から、蛍
光体の融点（約８７５℃）より低い温度で焼成を行なう
のが特に好ましい。焼成時間は蛍光体原料混合物の充填
量および焼成温度などによっても異なるが、一般には
０．５〜６時間が適当である。焼成雰囲気としては、窒
素ガス雰囲気、アルゴンガス雰囲気等の中性雰囲気、ま
たは少量の水素ガスを含有する窒素ガス雰囲気、一酸化
炭素を含有する二酸化炭素雰囲気等の弱還元性雰囲気を
利用する。一般に上記３）の蛍光体原料として、ユーロ
ピウムの価数が三価のユーロピウム化合物が用いられる
が、その場合に焼成過程において三価のユーロピウムは
二価のユーロピウムに還元される。Next, the phosphor raw material mixture obtained as described above is filled in a heat-resistant container such as a quartz boat, an alumina crucible, a quartz crucible, and baked in an electric furnace. Firing temperature is 40
The range of 0 to 1300 ° C is suitable, and preferably 500
The range is up to 1000 ° C. From the viewpoint of emission brightness and the like, it is particularly preferable to perform the firing at a temperature lower than the melting point (about 875 ° C.) of the phosphor. Although the firing time varies depending on the filling amount of the phosphor raw material mixture and the firing temperature, generally 0.5 to 6 hours is appropriate. As the firing atmosphere, a neutral atmosphere such as a nitrogen gas atmosphere or an argon gas atmosphere, or a weakly reducing atmosphere such as a nitrogen gas atmosphere containing a small amount of hydrogen gas or a carbon dioxide atmosphere containing carbon monoxide is used. Generally, a europium compound having a trivalent europium valence is used as the phosphor raw material in the above 3). In that case, the trivalent europium is reduced to a divalent europium in the firing process.
なお、上記の焼成条件で蛍光体原料混合物を一度焼成し
た後にその焼成物を放冷後粉砕し、さらに再焼成（二次
焼成）を行なう方法を利用してもよい。再焼成は上記の
中性雰囲気または弱還元性雰囲気下で、４００〜８００
℃の焼成温度で０．５〜１２時間かけて行なわれる。A method may be used in which the phosphor raw material mixture is once fired under the above firing conditions, the fired product is allowed to cool, then pulverized, and then refired (secondary firing). The re-baking is carried out at 400 to 800 in the above neutral atmosphere or weak reducing atmosphere.
It is carried out at a firing temperature of ° C for 0.5 to 12 hours.
上記焼成によって粉末状の本発明の蛍光体が得られる。
なお、得られた粉末状の蛍光体については、必要に応じ
て、さらに、洗浄、乾燥、ふるい分けなどの蛍光体の製
造における各種の一般的な操作を行なってもよい。A powdery phosphor of the present invention is obtained by the above firing.
The obtained powdered phosphor may be subjected to various general operations in the manufacture of the phosphor such as washing, drying, and sieving, if necessary.
以上に説明した製造法によって、下記組成式（Ｉ）で表
わされる本発明の二価ユーロピウム賦活アルカリ土類金
属ハロゲン化物系蛍光体が製造される。The divalent europium-activated alkaline earth metal halide phosphor of the present invention represented by the following composition formula (I) is manufactured by the manufacturing method described above.
組成式（Ｉ）： ＭIIＸ２・ａＭIIＸ′２・ｂＳｉＯ：ｘＥｕ2+…（Ｉ） （ただし、ＭII、Ｘ、Ｘ′、ａ、ｂおよびｘの定義は前
述と同じである） なお、上述の製造法に従って製造される本発明の蛍光体
は、Ｘ線、紫外線、電子線などの放射線を照射した後、
４５０〜１０００ｎｍの可視乃至赤外領域の電磁波で励
起すると近紫外乃至青色領域（発光のピーク波長：４０
９ｎｍ）に蛍光（輝尽発光）を発し、前記の新規なＭII
Ｘ２・ａＭIIＸ′２：Ｅｕ2+蛍光体とほぼ同一の輝尽発
光スペクトルおよび輝尽励起スペクトルを示す。Composition formula (I): M II X 2 · aM II X ′ 2 · bSiO: xEu 2+ (I) (where M II , X, X ′, a, b and x are the same as defined above). ) In addition, the phosphor of the present invention manufactured according to the above-mentioned manufacturing method, after being irradiated with radiation such as X-rays, ultraviolet rays, and electron beams,
When excited by electromagnetic waves in the visible to infrared region of 450 to 1000 nm, the near ultraviolet to blue region (emission peak wavelength: 40
Fluorescence (stimulated luminescence) is emitted at 9 nm), and the novel M II
It shows almost the same stimulated emission spectrum and stimulated excitation spectrum as the X 2 · aM II X ′ 2 : Eu 2+ phosphor.
本発明の蛍光体は、特に医療診断を目的とするＸ線撮影
等の医療用放射線撮影および物質の非破壊検査を目的と
する工業用放射線撮影などにおいて用いられる放射線像
変換パネル用の蛍光体として非常に利用価値の高いもの
である。The phosphor of the present invention is particularly useful as a phosphor for a radiation image conversion panel used in medical radiography such as X-ray photography for the purpose of medical diagnosis and industrial radiography for the purpose of nondestructive inspection of substances. It is extremely useful.
次に本発明の実施例および比較例を記載する。ただし、
これらの各例は本発明を限定するものではない。Next, examples and comparative examples of the present invention will be described. However,
Each of these examples does not limit the invention.
［実施例１］ 臭化バリウム（ＢａＢｒ２）の水溶液（1.55×10-3mol
／ｇ）１９２．７ｇ、塩化バリウム（ＢａＣｌ２）の水
溶液（1.18×10-3mol／ｇ）２５３．５ｇ、および臭化
ユーロピウム（ＥｕＢｒ３）の水溶液（2.841×10-4mol
／ml）１．０６ｍを混合した。この水溶液を６０℃で
３時間減圧乾燥した後、さらに１５０℃で３時間の真空
乾燥を行なった。Example 1 An aqueous solution of barium bromide (BaBr 2 ) (1.55 × 10 −3 mol
/ G) 192.7 g, an aqueous solution of barium chloride (BaCl 2 ) (1.18 × 10 −3 mol / g) 253.5 g, and an aqueous solution of europium bromide (EuBr 3 ) (2.841 × 10 −4 mol
/ Ml) 1.06 m. This aqueous solution was dried under reduced pressure at 60 ° C. for 3 hours and then vacuum dried at 150 ° C. for 3 hours.
次に、得られた蛍光体原料混合物１０ｇと一酸化ケイ素
（ＳｉＯ）０．８８mgを充分に混合した後アルミナルツ
ボに充填し、これを高温電気炉に入れて焼成を行なっ
た。焼成は、一酸化炭素を含む二酸化炭素雰囲気中にて
８５０℃の温度で１．５時間かけて行なった。焼成が完
了した後、焼成物を炉外に取り出して冷却した。このよ
うにして、一酸化ケイ素が含有された二価ユーロピウム
賦活塩化臭化バリウム蛍光体（ＢａＣｌ２・ＢａＢｒ２
・0.001ＳｉＯ：0.001Ｅｕ2+）を得た。Next, 10 g of the obtained phosphor raw material mixture and 0.88 mg of silicon monoxide (SiO) were sufficiently mixed and then filled in an alumina crucible, which was placed in a high temperature electric furnace and fired. The calcination was performed in a carbon dioxide atmosphere containing carbon monoxide at a temperature of 850 ° C. for 1.5 hours. After the firing was completed, the fired product was taken out of the furnace and cooled. Thus, the divalent europium-activated barium chlorobromide phosphor (BaCl 2 · BaBr 2) containing silicon monoxide is obtained.
・ 0.001SiO: 0.001Eu 2+ ) was obtained.
［実施例２］ 実施例１において、一酸化ケイ素の添加量を０．１mgに
変えること以外は実施例１の方法と同様の操作を行なう
ことにより、一酸化ケイ素が含有された二価ユーロピウ
ム賦活塩化臭化バリウム蛍光体（ＢａＣｌ２・ＢａＢｒ
２・0.0001ＳｉＯ：0.001Ｅｕ2+）を得た。[Example 2] The same procedure as in Example 1 was carried out except that the amount of silicon monoxide added was changed to 0.1 mg, to activate divalent europium containing silicon monoxide. Barium chloride bromide phosphor (BaCl 2 · BaBr
2 · 0.0001SiO: 0.001Eu 2+ ) was obtained.
［実施例３］ 実施例１において、一酸化ケイ素の添加量を８．７５mg
に変えること以外は実施例１の方法と同様の操作を行な
うことにより、一酸化ケイ素が含有された二価ユーロピ
ウム賦活塩化臭化バリウム蛍光体（ＢａＣｌ２・ＢａＢ
ｒ２・0.01ＳｉＯ：0.001Ｅｕ2+）を得た。Example 3 In Example 1, the amount of silicon monoxide added was 8.75 mg.
A divalent europium-activated barium chlorobromide phosphor (BaCl 2 .BaB) containing silicon monoxide was obtained by performing the same operation as in Example 1 except that
r 2 .0.01SiO: 0.001Eu 2+ ) was obtained.
［比較例１］ 実施例１において、蛍光体原料混合物に一酸化ケイ素を
添加しないこと以外は実施例１の方法と同様の操作を行
なうことにより、二価ユーロピウム賦活塩化臭化バリウ
ム蛍光体（ＢａＣｌ２・ＢａＢｒ２：0.001Ｅｕ2+）を
得た。Comparative Example 1 A divalent europium-activated barium chlorobromide phosphor (BaCl) was prepared in the same manner as in Example 1 except that silicon monoxide was not added to the phosphor raw material mixture. 2 · BaBr 2 : 0.001Eu 2+ ) was obtained.
次に、実施例１〜３および比較例１で得られた各蛍光体
に管電圧８０ＫＶｐのＸ線を照射したのち、半導体レー
ザー光（７８０ｎｍ）で励起したときの輝尽発光輝度を
測定した。その結果を第１表および第１図にまとめて示
す。Next, each of the phosphors obtained in Examples 1 to 3 and Comparative Example 1 was irradiated with X-rays having a tube voltage of 80 KVp, and the stimulated emission luminance when excited with a semiconductor laser beam (780 nm) was measured. The results are summarized in Table 1 and FIG.
また第１図は、ＢａＣｌ２・ＢａＢｒ２・ｂＳｉＯ：0.
001Ｅｕ2+蛍光体における一酸化ケイ素の含有量（ｂ
値）と輝尽発光輝度との関係を示すグラフである。 In addition, FIG. 1 shows BaCl 2 .BaBr 2 .bSiO: 0.
Content of silicon monoxide in 001Eu 2+ phosphor (b
It is a graph which shows the relationship between (value) and stimulated emission luminance.
第１図から明らかなように本発明のＢａＣｌ２・ＢａＢ
ｒ２・ｂＳｉＯ：0.001Ｅｕ2+蛍光体は、ｂ値が０＜ｂ
≦３×１０-2の範囲にある場合に輝尽発光輝度が向上す
る。特に、ｂ値が１０-4≦ｂ≦１０-2の範囲にある蛍光
体は高輝度の輝尽発光を示す。As is clear from FIG. 1, BaCl 2 .BaB of the present invention
r 2 · bSiO: 0.001Eu 2+ phosphor has ab value of 0 <b
When it is in the range of ≦ 3 × 10 −2, the stimulated emission luminance is improved. In particular, a phosphor having ab value in the range of 10 −4 ≦ b ≦ 10 −2 exhibits stimulated emission with high brightness.
第１図は、本発明の二価ユーロピウム賦活アルカリ土類
金属ハロゲン化物系蛍光体の具体例であるＢａＣｌ２・
ＢａＢｒ２・ｂＳｉＯ：0.001Ｅｕ2+蛍光体におけるｂ
値と輝尽発光輝度との関係を示すグラフである。FIG. 1 is a specific example of the divalent europium-activated alkaline earth metal halide-based phosphor of the present invention, which is BaCl 2 ·.
BaBr 2 · bSiO: 0.001 Eu 2 + b in phosphor
It is a graph which shows the relationship between a value and stimulated emission luminance.
Claims (11)
Ｃ、ＢｒおよびＩからなる群より選ばれる少なくとも
一種のハロゲンであって、かつＸ≠Ｘ′であり；そし
て、ａは０．１≦ａ≦１０．０の範囲の数値であり、ｂ
は０＜ｂ≦３×１０-2の範囲の数値であり、ｘは０＜ｘ
≦０．２の範囲の数値である） で表わされる二価ユーロピウム賦活アルカリ土類金属ハ
ロゲン化物系蛍光体。1. A composition formula (I): M II X 2 · aM II X ′ 2 · bSiO: xEu 2+ (I) (wherein M II is Ba; X and X ′ are both C, At least one halogen selected from the group consisting of Br and I, and X ≠ X ′; and a is a numerical value in the range of 0.1 ≦ a ≦ 10.0, and b
Is a numerical value in the range of 0 <b ≦ 3 × 10 −2 , and x is 0 <x
A divalent europium-activated alkaline earth metal halide-based phosphor represented by the formula: ≦ 0.2.
０-2の範囲の数値である特許請求の範囲第１項記載の蛍
光体。2. b in the composition formula (I) is 10 −4 ≦ b ≦ 1.
The phosphor according to claim 1, which has a numerical value in the range of 0 -2 .
６．０の範囲の数値である特許請求の範囲第１項記載の
蛍光体。3. A in the composition formula (I) is 0.25 ≦ a ≦
The phosphor according to claim 1, which has a numerical value in the range of 6.0.
ぞれ、ＣおよびＢｒのいずれかである特許請求の範囲
第１項記載の蛍光体。4. The phosphor according to claim 1, wherein X and X'in the composition formula (I) are either C or Br, respectively.
０-1の範囲の数値である特許請求の範囲第１項記載の蛍
光体。5. In the composition formula (I), x is 10 −5 ≦ x ≦ 1.
The phosphor according to claim 1 , which has a numerical value in the range of 0 -1 .
Ｃ、ＢｒおよびＩからなる群より選ばれる少なくとも
一種のハロゲンであって、かつＸ≠Ｘ′であり；そし
て、ａは０．１≦ａ≦１０．０の範囲の数値であり、ｂ
は０＜ｂ≦３×１０-2の範囲の数値であり、ｘは０＜ｘ
≦０．２の範囲の数値である） に対応する相対比となるように蛍光体原料混合物を調整
したのち、この混合物を中性雰囲気もしくは弱還元性雰
囲気中で４００乃至１３００℃の範囲の温度で焼成する
ことを特徴とする組成式（Ｉ）： ＭIIＸ２・ａＭIIＸ′２・ｂＳｉＯ：ｘＥｕ2+…（Ｉ） （ただし、ＭII、Ｘ、Ｘ′、ａ、ｂおよびｘの定義は前
述と同じである） で表わされる二価ユーロピウム賦活アルカリ土類金属ハ
ロゲン化物系蛍光体の製造法。6. A stoichiometric composition formula (II): M II X 2 · aM II X ′ 2 · bSiO: xEu ... (II) (wherein M II is Ba; X and X ′ are both Is at least one halogen selected from the group consisting of C, Br and I, and X ≠ X ′; and a is a numerical value in the range of 0.1 ≦ a ≦ 10.0 and b
Is a numerical value in the range of 0 <b ≦ 3 × 10 −2 , and x is 0 <x
The phosphor raw material mixture is adjusted to have a relative ratio corresponding to (a value in the range of ≦ 0.2), and the mixture is heated in a neutral atmosphere or a weak reducing atmosphere at a temperature in the range of 400 to 1300 ° C. Composition formula (I) characterized by firing at: M II X 2 · aM II X ′ 2 · bSiO: xEu 2+ (I) (where M II , X, X ′, a, b and x Is the same as defined above.) A method for producing a divalent europium-activated alkaline earth metal halide-based phosphor represented by
０-2の範囲の数値である特許請求の範囲第６項記載の蛍
光体の製造法。7. b in composition formula (II) is 10 −4 ≦ b ≦ 1
The method for producing a phosphor according to claim 6, wherein the value is in the range of 0 -2 .
６．０の範囲の数値である特許請求の範囲第６項記載の
蛍光体の製造法。8. A in the composition formula (II) is 0.25 ≦ a ≦
The method for producing a phosphor according to claim 6, which has a numerical value in the range of 6.0.
ぞれ、ＣおよびＢｒのいずれかである特許請求の範囲
第６項記載の蛍光体の製造法。9. The method for producing a phosphor according to claim 6, wherein X and X'in the composition formula (II) are either C or Br, respectively.
１０-1の範囲の数値である特許請求の範囲第６項記載の
蛍光体の製造法。10. In the composition formula (II), x is 10 −5 ≦ x ≦
The method for producing a phosphor according to claim 6, wherein the value is in the range of 10 -1 .
０００℃の範囲の温度で行なう特許請求の範囲第６項記
載の蛍光体の製造法。11. The firing of the phosphor raw material mixture is performed in the range of 500 to 1.
The method for producing a phosphor according to claim 6, which is performed at a temperature in the range of 000 ° C.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59240452A JPH0662947B2 (en) | 1984-11-16 | 1984-11-16 | Fluorescent body and its manufacturing method |
| US07/492,436 US5198679A (en) | 1984-11-16 | 1989-03-06 | Phosphor and image storage panel |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59240452A JPH0662947B2 (en) | 1984-11-16 | 1984-11-16 | Fluorescent body and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61120883A JPS61120883A (en) | 1986-06-07 |
| JPH0662947B2 true JPH0662947B2 (en) | 1994-08-17 |
Family
ID=17059705
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59240452A Expired - Fee Related JPH0662947B2 (en) | 1984-11-16 | 1984-11-16 | Fluorescent body and its manufacturing method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0662947B2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6531073B1 (en) | 1999-12-24 | 2003-03-11 | Konica Corporation | Rare earth activated alkali earth metal fluorohalide stimulable phosphor, preparation method thereof and radiation image conversion panel |
| JP5750774B2 (en) * | 2010-11-08 | 2015-07-22 | 国立大学法人 新潟大学 | Method for producing silicon-containing phosphor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6452434A (en) * | 1988-03-17 | 1989-02-28 | Katsuhiko Kagawa | Apparatus for automatically monitoring and alarming sleeping state |
-
1984
- 1984-11-16 JP JP59240452A patent/JPH0662947B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61120883A (en) | 1986-06-07 |
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