JPH10279935A - Fluorescent substance - Google Patents
Fluorescent substanceInfo
- Publication number
- JPH10279935A JPH10279935A JP9181197A JP9181197A JPH10279935A JP H10279935 A JPH10279935 A JP H10279935A JP 9181197 A JP9181197 A JP 9181197A JP 9181197 A JP9181197 A JP 9181197A JP H10279935 A JPH10279935 A JP H10279935A
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- Prior art keywords
- phosphor
- group
- fluorescent substance
- fluorescent
- activator
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、電子線、Ｘ線及び
紫外線等、特に紫外線の励起によって紫外域から可視域
の発光を呈するチタン酸塩蛍光体に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a titanate phosphor which emits light in an ultraviolet region to a visible region by excitation of electron beams, X-rays, ultraviolet rays and the like, in particular, ultraviolet rays.
【０００２】[0002]
【従来の技術】紫外線励起により発光する蛍光体（紫外
線励起蛍光体）は、蛍光ランプ、カラープラズマディス
プレイ、高圧水銀灯、屋内外で使用される蛍光性壁材や
蛍光性のタイル等よる装飾等に幅広く実用化されてい
る。蛍光性壁材や蛍光性タイル等は紫外線の中でも特
に、長波長（３６５ｎｍ）紫外線で励起されて、種々の
色に明るく発光する必要がある。2. Description of the Related Art Phosphors which emit light when excited by ultraviolet rays (ultraviolet excited phosphors) are used for decoration such as fluorescent lamps, color plasma displays, high-pressure mercury lamps, fluorescent wall materials and fluorescent tiles used indoors and outdoors. Widely used in practice. Fluorescent wall materials, fluorescent tiles, and the like need to be excited by long-wavelength (365 nm) ultraviolet light, particularly among ultraviolet rays, to emit bright light of various colors.
【０００３】従来、長波長紫外線励起蛍光体としては、
青色発光蛍光体のＥｕ2+付活アルカリ土類ハロ燐酸塩又
はＥｕ+2付活アルカリ土類アルミン酸塩蛍光体等、緑色
発光蛍光体のＺｎ2 ＧｅＯ4 ：Ｍｎ蛍光体等、また、赤
色発光蛍光体のＹ2 Ｏ2 Ｓ：Ｅｕ又はＹＶＯ4 ：Ｅｕ蛍
光体等が実用化されている。一方、表示の多様化、高機
能化に伴い、発光色の多色化、高輝度化、耐侯性改良等
が求められているが、従来の実用蛍光体は、発光色の種
類が限定されているため、更に種々の色の発光を呈する
実用的な蛍光体の開発が要望されている。Conventionally, as a long-wavelength ultraviolet-excited phosphor,
Blue emitting phosphor such as Eu 2+ activated alkaline earth halophosphate or Eu + 2 activated alkaline earth aluminate phosphor, green emitting phosphor Zn 2 GeO 4 : Mn phosphor, etc., and red Light emitting phosphors such as Y 2 O 2 S: Eu or YVO 4 : Eu phosphor have been put to practical use. On the other hand, with the diversification of display and the enhancement of functions, there is a demand for multicolor emission, higher brightness, improved weather resistance, and the like, but conventional practical phosphors are limited in the types of emission colors. Therefore, there is a demand for development of practical phosphors that emit light of various colors.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明は、長
波長紫外線励起下で種々の発光色の発光を示す新規な蛍
光体を提供しようとするものである。SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a novel phosphor which emits light of various emission colors under long-wavelength ultraviolet excitation.
【０００５】[0005]
【課題を解決するための手段】本発明は、下記の構成を
採用したものである。 (1) 下記組成式で表わされるチタン酸塩蛍光体。 Ｍ（Ｌｎ，Ｌｎ’）2 Ｔｉ3 Ｏ10 （式中、ＭはＣａ、Ｓｒ、Ｂａ、Ｂｅ、Ｍｇ、Ｚｎ及び
Ｃｄの群から選択された一種以上の２価金属元素であ
り、ＬｎはＹ、Ｌａ、Ｇｄ及びＬｕの群からから選択さ
れた一種以上の希土類元素であり、Ｌｎ’はＣｅ、Ｐ
ｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ
及びＹｂの群からから選択された一種以上のランタニド
族元素をそれぞれ示す。）The present invention adopts the following constitution. (1) A titanate phosphor represented by the following composition formula. M (Ln, Ln ′) 2 Ti 3 O 10 (where M is one or more divalent metal elements selected from the group consisting of Ca, Sr, Ba, Be, Mg, Zn and Cd, and Ln is Y , La, Gd and Lu are at least one rare earth element selected from the group consisting of Ce, P
r, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm
And one or more lanthanide group elements selected from the group of Yb and Yb. )
【０００６】(2) 下記組成式で表わされるチタン酸塩蛍
光体。 Ｍ（Ｌｎ1-x ，Ｌｎ’x ）2 Ｔｉ3 Ｏ10 （式中、ＭはＣａ、Ｓｒ、Ｂａ、Ｂｅ、Ｍｇ、Ｚｎ及び
Ｃｄの群から選択された一種以上の２価金属元素であ
り、ＬｎはＹ、Ｌａ、Ｇｄ及びＬｕの群からから選択さ
れた一種以上の希土類元素であり、Ｌｎ’はＣｅ、Ｐ
ｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ
及びＹｂの群からから選択された一種以上のランタニド
族元素をそれぞれ示し、ｘは１×１０-5≦ｘ≦１×１０
0 の範囲の数である。）(2) A titanate phosphor represented by the following composition formula: M (Ln 1-x , Ln ′ x ) 2 Ti 3 O 10 (where M is one or more divalent metal elements selected from the group consisting of Ca, Sr, Ba, Be, Mg, Zn and Cd) , Ln is one or more rare earth elements selected from the group of Y, La, Gd and Lu, and Ln ′ is Ce, P
r, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm
And one or more lanthanide group elements selected from the group of Yb, and x is 1 × 10 −5 ≦ x ≦ 1 × 10
A number in the range 0 . )
【０００７】(3) 上記ｘが１×１０-1≦ｘ≦８×１０-1
の範囲の数である上記(1) 記載のチタン酸塩蛍光体。 (4) 上記組成式中、ＭがＣａ、Ｓｒ及びＢａの群から選
択された１種以上の２価金属元素である上記(1) 〜(3)
のいづれか１つに記載のチタン酸塩蛍光体。 (5) 上記組成式中、Ｌｎ’がＥｕ及び／又はＴｂである
上記(1) 〜(4) のいづれか１つに記載のチタン酸塩蛍光
体。(3) The above x is 1 × 10 −1 ≦ x ≦ 8 × 10 −1
(1) the titanate phosphor according to the above (1), wherein (4) In the above composition formula, M is at least one divalent metal element selected from the group consisting of Ca, Sr and Ba.
The titanate phosphor according to any one of the above. (5) The titanate phosphor according to any one of the above (1) to (4), wherein Ln ′ is Eu and / or Tb in the above composition formula.
【０００８】[0008]
【発明の実施の形態】本発明の蛍光体組成の具体例を示
すと下記のとおりである。Ｃａ（Ｙ，Ｅｕ）2 Ｔｉ3 Ｏ
10、Ｃａ（Ｙ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｓｒ（Ｙ，Ｅｕ）
2 Ｔｉ3 Ｏ10、Ｓｒ（Ｙ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｂａ
（Ｙ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｙ，Ｔｂ）2 Ｔｉ3
Ｏ10、Ｂｅ（Ｙ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｂｅ（Ｙ，Ｔ
ｂ）2 Ｔｉ3 Ｏ10、Ｍｇ（Ｙ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｍ
ｇ（Ｙ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｚｎ（Ｙ，Ｅｕ）2 Ｔｉ
3 Ｏ10、Ｚｎ（Ｙ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｃｄ（Ｙ，Ｅ
ｕ）2 Ｔｉ3 Ｏ10、Ｃｄ（Ｙ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｃ
ａ（Ｌａ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｃａ（Ｌａ，Ｔｂ）2
Ｔｉ3 Ｏ10、Ｓｒ（Ｌａ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｓｒ
（Ｌａ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌａ，Ｅｕ）2 Ｔ
ｉ3 Ｏ10、Ｂａ（Ｌａ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｃａ（Ｇ
ｄ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｃａ（Ｇｄ，Ｔｂ）2 Ｔｉ3
Ｏ10、Ｓｒ（Ｇｄ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｓｒ（Ｇｄ，
Ｔｂ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｇｄ，Ｅｕ）2 Ｔｉ
3 Ｏ10、Ｂａ（Ｇｄ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｃａ（Ｌ
ｕ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｃａ（Ｌｕ，Ｔｂ）2 Ｔｉ3
Ｏ10、Ｓｒ（Ｌｕ，Ｅｕ）2 Ｔｉ3 Ｏ10、Ｓｒ（Ｌｕ，
Ｔｂ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌｕ，Ｅｕ）2 Ｔｉ
3 Ｏ10、Ｂａ（Ｌｕ，Ｔｂ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌ
ｕ，Ｃｅ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌｕ，Ｐｒ）2 Ｔｉ3
Ｏ10、Ｂａ（Ｌｕ，Ｎｄ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌｕ，
Ｓｍ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌｕ，Ｄｙ）2 Ｔｉ
3 Ｏ10、Ｂａ（Ｌｕ，Ｈｏ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌ
ｕ，Ｅｒ）2 Ｔｉ3 Ｏ10、Ｂａ（Ｌｕ，Ｔｍ）2 Ｔｉ3
Ｏ10、Ｂａ（Ｌｕ，Ｙｂ）2 Ｔｉ3 Ｏ10。DESCRIPTION OF THE PREFERRED EMBODIMENTS Specific examples of the phosphor composition of the present invention are as follows. Ca (Y, Eu) 2 Ti 3 O
10 , Ca (Y, Tb) 2 Ti 3 O 10 , Sr (Y, Eu)
2 Ti 3 O 10 , Sr (Y, Tb) 2 Ti 3 O 10 , Ba
(Y, Eu) 2 Ti 3 O 10 , Ba (Y, Tb) 2 Ti 3
O 10 , Be (Y, Eu) 2 Ti 3 O 10 , Be (Y, T
b) 2 Ti 3 O 10 , Mg (Y, Eu) 2 Ti 3 O 10 , M
g (Y, Tb) 2 Ti 3 O 10 , Zn (Y, Eu) 2 Ti
3 O 10 , Zn (Y, Tb) 2 Ti 3 O 10 , Cd (Y, E
u) 2 Ti 3 O 10 , Cd (Y, Tb) 2 Ti 3 O 10 , C
a (La, Eu) 2 Ti 3 O 10 , Ca (La, Tb) 2
Ti 3 O 10 , Sr (La, Eu) 2 Ti 3 O 10 , Sr
(La, Tb) 2 Ti 3 O 10 , Ba (La, Eu) 2 T
i 3 O 10 , Ba (La, Tb) 2 Ti 3 O 10 , Ca (G
d, Eu) 2 Ti 3 O 10 , Ca (Gd, Tb) 2 Ti 3
O 10 , Sr (Gd, Eu) 2 Ti 3 O 10 , Sr (Gd,
Tb) 2 Ti 3 O 10 , Ba (Gd, Eu) 2 Ti
3 O 10 , Ba (Gd, Tb) 2 Ti 3 O 10 , Ca (L
u, Eu) 2 Ti 3 O 10 , Ca (Lu, Tb) 2 Ti 3
O 10 , Sr (Lu, Eu) 2 Ti 3 O 10 , Sr (Lu,
Tb) 2 Ti 3 O 10 , Ba (Lu, Eu) 2 Ti
3 O 10 , Ba (Lu, Tb) 2 Ti 3 O 10 , Ba (L
u, Ce) 2 Ti 3 O 10 , Ba (Lu, Pr) 2 Ti 3
O 10 , Ba (Lu, Nd) 2 Ti 3 O 10 , Ba (Lu,
Sm) 2 Ti 3 O 10 , Ba (Lu, Dy) 2 Ti
3 O 10 , Ba (Lu, Ho) 2 Ti 3 O 10 , Ba (L
u, Er) 2 Ti 3 O 10 , Ba (Lu, Tm) 2 Ti 3
O 10 , Ba (Lu, Yb) 2 Ti 3 O 10 .
【０００９】本発明の蛍光体は次のようにして製造され
る。母体を構成するＭ元素、Ｌｎ元素、Ｔｉ及び付活剤
となるＬｎ’元素の各酸化物、並びに焼成により容易に
これらの元素の酸化物を生成する炭酸塩、硝酸塩、ハロ
ゲン化物等の塩からなる蛍光体原料を化学量論的に、組
成式がＭ（Ｌｎ1-x，Ｌｎ’x ）2 Ｔｉ3 Ｏ10（式中、
ＭはＣａ、Ｓｒ、Ｂａ、Ｂｅ、Ｍｇ、Ｚｎ及びＣｄの群
から選択された一種以上の２価金属元素であり、Ｌｎは
Ｙ、Ｌａ、Ｇｄ及びＬｕの群からから選択された一種以
上の希土類元素であり、Ｌｎ’はＣｅ、Ｐｒ、Ｎｄ、Ｓ
ｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ及びＹｂの群
からから選択された一種以上のランタニド族元素をそれ
ぞれ示し、ｘは１×１０-5≦ｘ≦１×１０0 の範囲の数
である。）となるような割合で秤取し、湿式又は乾式で
充分に混合する。[0009] The phosphor of the present invention is manufactured as follows. From the oxides of the M element, Ln element, Ti and Ln 'element serving as the activator, and salts such as carbonates, nitrates, and halides that easily generate oxides of these elements upon firing, The phosphor raw material is stoichiometrically represented by a composition formula of M (Ln 1-x , Ln ′ x ) 2 Ti 3 O 10 (wherein
M is at least one divalent metal element selected from the group consisting of Ca, Sr, Ba, Be, Mg, Zn and Cd, and Ln is at least one kind selected from the group consisting of Y, La, Gd and Lu. Ln 'is Ce, Pr, Nd, S
m represents one or more lanthanide group elements selected from the group consisting of Eu, Tb, Dy, Ho, Er, Tm, and Yb, and x represents a number in the range of 1 × 10 −5 ≦ x ≦ 1 × 10 0. It is. ) And weigh them in such a ratio as to give a wet or dry mixture.
【００１０】なお、これらの原料混合物はペレット状に
加圧成型しても良い。また、希土類原料（Ｌｎの化合物
及びＬｎ’の化合物）は水等に溶解後、両者を共沈させ
て混合しても良い。そして、必要に応じて、これらの混
合物にアルカリのハロゲン化物、アンモニウムのハロゲ
ン化物等、従来から蛍光体製造時に用いられる低融点化
合物を融剤として蛍光体原料中に添加、混合し、アルミ
ナルツボ等の耐熱容器に充填し、空気中又は中性ガス雰
囲気に保った状態で焼成する。焼成は比較的長時間をか
けて行うのが好ましく、蛍光体原料の充填量にもよる
が、６００〜１４００℃の温度下で１〜９６時間、好ま
しくは１２５０〜１４００℃の温度下で２４〜９６時間
かけて１回以上焼成する。この焼成物は粉砕し、水洗、
乾燥、篩分等を行い、本発明の蛍光体を得る。なお、、
付活剤のＬｎ’元素がＴｂ又はＣｅの場合は、最後の焼
成を還元性雰囲気で行うと、得られる蛍光体は発光輝度
を一層高くすることができるので好ましい。The raw material mixture may be formed into a pellet by pressure. Further, the rare earth raw materials (the compound of Ln and the compound of Ln ′) may be dissolved in water or the like, and then coprecipitated and mixed. Then, if necessary, a low melting point compound conventionally used in the production of a phosphor, such as an alkali halide or an ammonium halide, is added to the mixture as a flux in the phosphor raw material, mixed, and mixed with an alumina crucible or the like. In a heat-resistant container and fired in an air or neutral gas atmosphere. The calcination is preferably performed over a relatively long period of time. Depending on the amount of the phosphor material, the calcination is performed at a temperature of 600 to 1400 ° C. for 1 to 96 hours, preferably at a temperature of 1250 to 1400 ° C. for 24 to 1 hour. Bake at least once over 96 hours. This fired product is crushed, washed with water,
Drying, sieving and the like are performed to obtain the phosphor of the present invention. In addition,
In the case where the Ln 'element of the activator is Tb or Ce, it is preferable to perform the final baking in a reducing atmosphere since the obtained phosphor can further increase the emission luminance.
【００１１】なお、付活剤Ｌｎ’の量（ｘ値）は、１×
１０-5≦ｘ≦１×１０0 なる条件を満たすことが好まし
い。ｘ値が１×１０-5を下回ると、蛍光体がほとんど発
光せず、また、ｘ値が１×１０0 を超えると濃度消光を
起こすためか、やはり蛍光体の発光強度が著しく低下す
るので好ましくない。そして、得られる蛍光体の発光強
度の観点から、ｘ値は１×１０-1≦ｘ≦８×１０-1の範
囲とすることが特に好ましい。The amount (x value) of the activator Ln 'is 1 ×
It is preferable to satisfy the condition of 10 −5 ≦ x ≦ 1 × 10 0 . If the x value is less than 1 × 10 −5 , the phosphor hardly emits light, and if the x value exceeds 1 × 10 0 , the concentration quenching may occur, or the emission intensity of the phosphor is also significantly reduced. Not preferred. From the viewpoint of the emission intensity of the obtained phosphor, it is particularly preferable that the value x is in the range of 1 × 10 −1 ≦ x ≦ 8 × 10 −1 .
【００１２】図１は、本発明の蛍光体の１つであるＢａ
（Ｌａ0.6 Ｅｕ0.4 ）2 Ｔｉ3 Ｏ10蛍光体のＸ線回折線
図である。FIG. 1 shows Ba, which is one of the phosphors of the present invention.
FIG. 3 is an X-ray diffraction diagram of a (La 0.6 Eu 0.4 ) 2 Ti 3 O 10 phosphor.
【００１３】図２は、図１のＢａ（Ｌａ0.6 Ｅｕ0.4 ）
2 Ｔｉ3 Ｏ10蛍光体を３９７ｎｍの紫外線で励起したと
きの発光スペクトルを示したもので、その発光スペクト
ルの波長ピーク波長は６１４ｎｍであった。この蛍光体
の母体構成元素である、Ｂａ及びＬａを他の２価金属元
素及びＬｎの希土類元素と置き代えてその発光スペクト
ルを測定すると、図２と類似の形状を示し、この蛍光体
と同様に紫外線励起下で赤色の発光を呈した。また、付
活剤としてＥｕに代えてＬｎ’のランタナイド族元素を
用いると、その付活剤元素に固有の発光色を呈する蛍光
体が得られた。FIG. 2 shows Ba (La 0.6 Eu 0.4 ) of FIG.
FIG. 3 shows an emission spectrum when the 2 Ti 3 O 10 phosphor was excited by ultraviolet rays of 397 nm, and the wavelength peak wavelength of the emission spectrum was 614 nm. When the emission spectrum was measured by replacing Ba and La, which are base constituent elements of this phosphor, with another divalent metal element and a rare earth element of Ln, it showed a shape similar to that of FIG. And exhibited red light emission under ultraviolet excitation. Also, when a lanthanide group element of Ln ′ was used instead of Eu as the activator, a phosphor exhibiting an emission color unique to the activator element was obtained.
【００１４】図３は、図１のＢａ（Ｌａ0.6 Ｅｕ0.4 ）
2 Ｔｉ3 Ｏ10蛍光体の励起スペクトルを例示したもので
ある。励起スペクトルの測定は、分光光度計の出力側の
分光波長をこの蛍光体の発光スペクトルピークである６
１４ｎｍに固定し、試料に照射する励起の波長を変化さ
せた時の６１４ｎｍ出力光の強度をプロットしたもので
ある。縦軸は発光波長の相対発光強度、横軸はスキャン
する励起光の波長であり、このスペクトルのピーク波長
がその蛍光体を最も効率よく発光させることができる波
長である。FIG. 3 shows Ba (La 0.6 Eu 0.4 ) of FIG.
2 illustrates an excitation spectrum of a 2 Ti 3 O 10 phosphor. The excitation spectrum is measured by setting the spectral wavelength on the output side of the spectrophotometer to the peak of the emission spectrum of this phosphor.
FIG. 9 is a graph in which the intensity of the output light at 614 nm when the wavelength of the excitation light applied to the sample is changed while being fixed at 14 nm. The vertical axis indicates the relative emission intensity of the emission wavelength, and the horizontal axis indicates the wavelength of the excitation light to be scanned. The peak wavelength of this spectrum is the wavelength at which the phosphor can emit light most efficiently.
【００１５】図４は、図１のＢａ（Ｌａ0.6 Ｅｕ0.4 ）
2 Ｔｉ3 Ｏ10蛍光体を３９７ｎｍの紫外線で励起した時
の、蛍光体の発光強度の付活剤濃度依存性を示したグラ
フである。図４の縦軸は各発光波長における発光波長の
相対発光強度であり、横軸は蛍光体の付活剤濃度であ
る。なお、蛍光体の母体組成（選択されるＭ及びＬｎの
種類）及び付活剤元素（選択されるＬｎ’の種類）を実
施例１の蛍光体とは異なる元素に代えて蛍光体組成を代
えても、その蛍光体の発光強度の付活剤濃度依存性は図
４とほぼ類似の傾向にあり、一定のレベル以上の発光輝
度を有する蛍光体を得るのに最適な付活剤（Ｌｎ’）濃
度（ｘ値）の範囲は、１×１０-5〜１×１０0 であり、
より高輝度の発光を得るためには、１×１０-1〜８×１
０-1の範囲がよいことを確認している。FIG. 4 shows Ba (La 0.6 Eu 0.4 ) of FIG.
4 is a graph showing the activator concentration dependence of the emission intensity of the 2 Ti 3 O 10 phosphor when the phosphor is excited by ultraviolet light of 397 nm. The vertical axis in FIG. 4 is the relative emission intensity of the emission wavelength at each emission wavelength, and the horizontal axis is the activator concentration of the phosphor. The phosphor composition was changed by changing the host composition (the type of M and Ln selected) and the activator element (the type of Ln ′ selected) of the phosphor to an element different from the phosphor of Example 1. However, the dependence of the emission intensity of the phosphor on the activator concentration tends to be substantially similar to that of FIG. 4, and the most suitable activator (Ln ′) for obtaining a phosphor having a light emission luminance of a certain level or more. ) The concentration (x value) ranges from 1 × 10 −5 to 1 × 10 0 ,
In order to obtain light emission of higher luminance, 1 × 10 −1 to 8 × 1
It has been confirmed that the range of 0 -1 is good.
【００１６】本発明の蛍光体は、上記のように、特に長
波長紫外線で励起するときに、用いられる付活剤元素の
種類に応じ、付活剤に固有の発光色を呈する蛍光体が得
られるので、蛍光ランプ、カラープラズマディスプレ
イ、高圧水銀灯及び屋内外の壁面装飾用の蛍光性壁材や
タイル等に適用でき、また、電子線及びＸ線で励起して
発光させる用途にも幅広く利用することができる。As described above, the phosphor of the present invention, when excited by a long-wavelength ultraviolet ray, obtains a phosphor exhibiting an emission color specific to the activator depending on the type of the activator element used. Therefore, it can be applied to fluorescent lamps, color plasma displays, high-pressure mercury lamps, fluorescent wall materials and tiles for indoor and outdoor wall decoration, and is also widely used for applications that emit light by excitation with electron beams and X-rays. be able to.
【００１７】[0017]
ＢａＣＯ3 １９．４ ｇ Ｌａ2 Ｏ3 １９．５ ｇ Ｅｕ2 Ｏ3 １４．１ ｇ ＴｉＯ2 ２４．０ ｇ ＮＨ4 Ｃｌ（融剤） １．５ ｇ 上記の原料を充分に混合し、アルミナルツボに詰めて電
気炉を用い、空気中で１２５０℃、６時間焼成した。得
られた焼成物を粉砕、水洗、乾燥、篩分を行って蛍光体
を得た。BaCO 3 19.4 g La 2 O 3 19.5 g Eu 2 O 3 14.1 g TiO 2 24.0 g NH 4 Cl (flux) 1.5 g And baked at 1250 ° C. for 6 hours in air using an electric furnace. The obtained fired product was pulverized, washed with water, dried and sieved to obtain a phosphor.
【００１８】得られた蛍光体は、Ｂａ（Ｌａ0.6 Ｅｕ
0.4 ）2 Ｔｉ3 Ｏ10の組成を有し、図１に示したＸ線回
折線図を示し、３９７ｎｍの紫外線で励起した時の発光
スペクトルは図２のとおりで、発光波長ピークが６１４
ｎｍの赤色発光を呈した。また、励起スペクトルは、図
３のように近紫外域から可視域まで広がっていた。The obtained phosphor was Ba (La 0.6 Eu).
The composition has the composition of 0.4 ) 2 Ti 3 O 10 and the X-ray diffraction diagram shown in FIG. 1 is shown. The emission spectrum when excited by ultraviolet rays of 397 nm is as shown in FIG.
nm emission of red light. In addition, the excitation spectrum spread from the near ultraviolet region to the visible region as shown in FIG.
【００１９】[0019]
【発明の効果】本発明は、上記の構成を採用することに
より、特に紫外線励起により、添加される付活剤の希土
類元素の種類に応じて付活剤に固有の主として近紫外域
から青色〜赤色の可視域に発光する新規な蛍光体の提供
を可能にした。According to the present invention, by adopting the above constitution, particularly by excitation with ultraviolet rays, depending on the type of the rare earth element of the activator to be added, the activator inherently has a blue to blue range from the near ultraviolet region. It has made it possible to provide a novel phosphor that emits light in the red visible region.
【図１】実施例で得た蛍光体の粉末Ｘ線回折線図であ
る。FIG. 1 is a powder X-ray diffraction diagram of a phosphor obtained in an example.
【図２】実施例の蛍光体の発光スペクトルのグラフであ
る。FIG. 2 is a graph of an emission spectrum of a phosphor of an example.
【図３】実施例の蛍光体の励起スペクトルのグラフであ
る。FIG. 3 is a graph of an excitation spectrum of a phosphor of an example.
【図４】実施例の蛍光体の発光強度の付活剤濃度依存性
を示したグラフである。FIG. 4 is a graph showing the dependence of the emission intensity of a phosphor of an example on the concentration of an activator.
Claims (5)
体。 Ｍ（Ｌｎ，Ｌｎ’）2 Ｔｉ3 Ｏ10 （式中、ＭはＣａ、Ｓｒ、Ｂａ、Ｂｅ、Ｍｇ、Ｚｎ及び
Ｃｄの群から選択された一種以上の２価金属元素であ
り、ＬｎはＹ、Ｌａ、Ｇｄ及びＬｕの群からから選択さ
れた一種以上の希土類元素であり、Ｌｎ’はＣｅ、Ｐ
ｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ
及びＹｂの群からから選択された一種以上のランタニド
族元素をそれぞれ示す。）1. A titanate phosphor represented by the following composition formula. M (Ln, Ln ′) 2 Ti 3 O 10 (where M is one or more divalent metal elements selected from the group consisting of Ca, Sr, Ba, Be, Mg, Zn and Cd, and Ln is Y , La, Gd and Lu are at least one rare earth element selected from the group consisting of Ce, P
r, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm
And one or more lanthanide group elements selected from the group of Yb and Yb. )
体。 Ｍ（Ｌｎ1-x ，Ｌｎ’x ）2 Ｔｉ3 Ｏ10 （式中、ＭはＣａ、Ｓｒ、Ｂａ、Ｂｅ、Ｍｇ、Ｚｎ及び
Ｃｄの群から選択された一種以上の２価金属元素であ
り、ＬｎはＹ、Ｌａ、Ｇｄ及びＬｕの群からから選択さ
れた一種以上の希土類元素であり、Ｌｎ’はＣｅ、Ｐ
ｒ、Ｎｄ、Ｓｍ、Ｅｕ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ
及びＹｂの群からから選択された一種以上のランタニド
族元素をそれぞれ示し、ｘは１×１０-5≦ｘ≦１×１０
0 の範囲の数である。）2. A titanate phosphor represented by the following composition formula. M (Ln 1-x , Ln ′ x ) 2 Ti 3 O 10 (where M is one or more divalent metal elements selected from the group consisting of Ca, Sr, Ba, Be, Mg, Zn and Cd) , Ln is one or more rare earth elements selected from the group of Y, La, Gd and Lu, and Ln ′ is Ce, P
r, Nd, Sm, Eu, Tb, Dy, Ho, Er, Tm
And one or more lanthanide group elements selected from the group of Yb, and x is 1 × 10 −5 ≦ x ≦ 1 × 10
A number in the range 0 . )
範囲の数である請求項２記載のチタン酸塩蛍光体。3. The titanate phosphor according to claim 2, wherein x is a number in the range of 1 × 10 −1 ≦ x ≦ 8 × 10 −1 .
の群から選択された１種以上の２価金属元素である請求
項１〜３のいづれか１項に記載のチタン酸塩蛍光体。4. In the above composition formula, M is Ca, Sr and Ba.
The titanate phosphor according to claim 1, wherein the titanate phosphor is at least one divalent metal element selected from the group consisting of:
Ｔｂである請求項１〜４項のいづれか１項に記載のチタ
ン酸塩蛍光体。5. The titanate phosphor according to claim 1, wherein in the composition formula, Ln ′ is Eu and / or Tb.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9181197A JPH10279935A (en) | 1997-04-10 | 1997-04-10 | Fluorescent substance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9181197A JPH10279935A (en) | 1997-04-10 | 1997-04-10 | Fluorescent substance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10279935A true JPH10279935A (en) | 1998-10-20 |
Family
ID=14037023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9181197A Pending JPH10279935A (en) | 1997-04-10 | 1997-04-10 | Fluorescent substance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10279935A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010097545A (en) * | 2000-04-24 | 2001-11-08 | 김순택 | Low-voltage white phosphor and method of preparing same |
| CN100422287C (en) * | 2004-07-14 | 2008-10-01 | 湖南师范大学 | Red long persistence luminescent materials and their synthesis process and use |
| WO2010024480A1 (en) * | 2008-08-26 | 2010-03-04 | Kangnung-Wonju National University Industry Academy Cooperation Group | Red phosphor and forming method thereof for use in solid state lighting |
-
1997
- 1997-04-10 JP JP9181197A patent/JPH10279935A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010097545A (en) * | 2000-04-24 | 2001-11-08 | 김순택 | Low-voltage white phosphor and method of preparing same |
| CN100422287C (en) * | 2004-07-14 | 2008-10-01 | 湖南师范大学 | Red long persistence luminescent materials and their synthesis process and use |
| WO2010024480A1 (en) * | 2008-08-26 | 2010-03-04 | Kangnung-Wonju National University Industry Academy Cooperation Group | Red phosphor and forming method thereof for use in solid state lighting |
| JP2012501365A (en) * | 2008-08-26 | 2012-01-19 | カンヌン‐ウォンジュ ナショナル ユニバーシティ インダストリー アカデミー コーオペレイション グループ | RED PHOSPHOR FOR SOLID LIGHTING AND METHOD FOR PRODUCING THE SAME {REDPHOSPHORANDITOSING |
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