JPH0629416B2 - Fluorescent body - Google Patents
Fluorescent bodyInfo
- Publication number
- JPH0629416B2 JPH0629416B2 JP58250704A JP25070483A JPH0629416B2 JP H0629416 B2 JPH0629416 B2 JP H0629416B2 JP 58250704 A JP58250704 A JP 58250704A JP 25070483 A JP25070483 A JP 25070483A JP H0629416 B2 JPH0629416 B2 JP H0629416B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- emission peak
- peak height
- europium
- oxide
- 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 - Lifetime
Links
Landscapes
- Luminescent Compositions (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は２価のユーロピウムで付活されたバリウムアル
ミネート螢光体の改良に関するものである。FIELD OF THE INVENTION The present invention relates to improvements in divalent europium activated barium aluminate phosphors.
従来例の構成とその問題点 従来、２価のユーロピウムで付活されたバリウムアルミ
ネート螢光体としては、Ｇ．ＢＬＡＳＳＥ ａｎｄ
Ａ．ＢＲＩＬ，Ｐｈｉｌｉｐｓ Ｒｅｓ，Ｒｅｐｔ．，
２３（１９６８）２０１に研究報告があり、ＢａＡｌ２
Ｏ４：Ｅｕ２＋およびＢａＡｌ１２Ｏ１９：Ｅｕ２＋の
発光ピーク波長はそれぞれ５０５ｎｍおよび４３５ｎｍ
であることが知られている。Configuration of Conventional Example and its Problems Conventionally, as a barium aluminate phosphor activated with divalent europium, G. BASSE and
A. BRIL, Philips Res, Rept. ，
23 (1968) 201 has a research report, BaAl 2
The emission peak wavelengths of O 4 : Eu 2+ and BaAl 12 O 19 : Eu 2+ are 505 nm and 435 nm, respectively.
Is known to be.
近年、高演色性螢光ランプの効率改善に関して、４８０
〜５００ｎｍに発光ピークを有する螢光体が注目されて
いる。最近の研究によれば、例えば、Ｊ．Ｔ．Ｃ．ＶＡ
Ｎ ＫＥＭＥＮＡＤＥ ａｎｄ Ｇ．Ｐ．Ｆ．ＨＯＥＫ
Ｓ，Ｅｘｔｅｎｄｅｄ ａｂ ｓｔｒａｃｔ No．６０
７，Ｅ．Ｃ．Ｓ．Ｓｐｒｉｎｇ Ｍｅｅｔｉｎｇ（１９
８３）に報告されているＢａＡｌ８Ｏ１３：Ｅｕ２＋螢
光体は発光ピーク波長が４８０ｎｍにある新しいタイプ
のアルミネートである。しかしながら、この２価のユー
ロピウムで付活された青緑色螢光体は発光ピーク高さが
不十分であり、その向上が望まれていた。In recent years, regarding the efficiency improvement of the high color rendering fluorescent lamp, 480
Attention has been paid to a phosphor having an emission peak at ˜500 nm. According to recent research, for example, J. T. C. VA
N KEMENADE and G.N. P. F. HOEK
S, Extended abstruct No. 60
7, E. C. S. Spring Meeting (19
BaAl 8 O 13 : Eu 2+ phosphor reported in 83) is a new type of aluminate having an emission peak wavelength of 480 nm. However, this blue-green phosphor activated with divalent europium has an insufficient emission peak height, and its improvement has been desired.
発明の目的 本発明は、このような事情にもとづいてなされたもの
で、発光ピーク高さを向上させた２価のユーロピウム付
活バリウムアルミネート螢光体を提供することを目的と
するものである。OBJECT OF THE INVENTION The present invention has been made under these circumstances, and an object thereof is to provide a divalent europium-activated barium aluminate phosphor having an improved emission peak height. .
発明の構成 発明者らは、２価のユーロピウムで付活されたバリウム
アルミネート螢光体について詳細な実験を行なった結
果、この螢光体にさらに酸化イットリウムを固溶させる
ことによって、その発光ピーク高さを一層向上させ得る
ことを見出した。Composition of the Invention The inventors have performed detailed experiments on a barium aluminate phosphor activated with divalent europium, and as a result of further dissolving yttrium oxide in the phosphor, the emission peak thereof is obtained. It was found that the height can be further improved.
すなわち、発明者らの実験によれば、２価のユーロピウ
ムで付活されたバリウムアルミネート螢光体は、その組
成式が （Ｂａ，Ｅｕ）Ｏ・ｘＡｌ２Ｏ３・ｙＹ２Ｏ３ で表わされるものであり、上記組成式のｘ，ｙの範囲が
それぞれ ３≦ｘ≦５，０＜ｙ≦０．１ の場合に、より好ましい発光ピーク高さの向上が認めら
れたものである。さらに言えば、本発明にかかる螢光体
の場合、そのＡｌ２Ｏ３量ｘが３＞ｘまたは５＜ｘの領
域においても、酸化イットリウムの固溶により発光ピー
ク高さが向上するという効果は明らかに認められたが、
これらの向上されたピーク高さをもってしても現在実用
されているＢａＡｌ８Ｏ１３：Ｅｕ２＋螢光体の発光ピ
ーク高さを越えるものは得られず、実用的なレベルには
至らないことを確認した。また、付活剤であるユーロピ
ウム添加量は、他の一般に使用されている螢光体におけ
るユーロピウム濃度の範囲で上記酸化イットリウム固溶
による発光ピーク高さの向上効果が認められた。That is, according to the experiments by the inventors, the composition formula of the barium aluminate phosphor activated with divalent europium is represented by (Ba, Eu) O.xAl 2 O 3 .yY 2 O 3 . When the ranges of x and y in the above composition formula are 3 ≦ x ≦ 5 and 0 <y ≦ 0.1, respectively, a more preferable improvement in emission peak height was observed. Moreover, in the case of the phosphor according to the present invention, the effect of improving the emission peak height by the solid solution of yttrium oxide is obtained even in the region where the Al 2 O 3 amount x is 3> x or 5 <x. Obviously,
Even with these improved peak heights, it is not possible to obtain a material having an emission peak height exceeding that of the BaAl 8 O 13 : Eu 2+ phosphor currently in practical use, and it is not possible to reach a practical level. confirmed. Further, the addition amount of europium, which is an activator, was confirmed to have the effect of improving the emission peak height by the yttrium oxide solid solution in the range of the europium concentration in other commonly used phosphors.
実施例の説明 本発明にかかる螢光体は以下に述べる製造方法によって
得られず。まず、螢光体原料としては、 (1) 酸化イットリウム（Ｙ２Ｏ３）または硝酸塩，炭
酸塩，ハロゲン化物等の高温で容易にＹ２Ｏ３に変化し
得る化合物。Description of Examples The phosphor according to the present invention cannot be obtained by the manufacturing method described below. First, as a fluorescent material, (1) a compound such as yttrium oxide (Y 2 O 3 ) or a nitrate, a carbonate, a halide or the like which can be easily converted into Y 2 O 3 at a high temperature.
(2) 酸化バリウム（ＢａＯ）または硝酸塩，炭酸塩ハ
ロゲン化物等の高温で容易にＢａＯに変化し得る化合
物。(2) Compounds such as barium oxide (BaO) or nitrates, carbonate halides, etc., which can be easily converted to BaO at high temperature.
(3) 酸化アルミニウム（Ａｌ２Ｏ３）または硝酸塩，
水酸化物，ハロゲン化物等の高温で容易にＡｌ２Ｏ３に
変化し得る化合物。(3) Aluminum oxide (Al 2 O 3 ) or nitrate,
Compounds such as hydroxides and halides that can easily be converted to Al 2 O 3 at high temperatures.
(4) 酸化ユーロピウム（Ｅｕ２Ｏ３）または硝酸塩，
炭酸塩，ハロゲン化物等の高温で容易にＥｕ２Ｏ３に変
化し得る化合物。(4) Europium oxide (Eu 2 O 3 ) or nitrate,
Compounds such as carbonates and halides that can be easily converted to Eu 2 O 3 at high temperature.
が用いられる。上記原料を秤量し、ホウ酸，無水ホウ酸
などを適量添加して、ボールミルにより十分に粉砕混合
する。これを石英ボートに充填し、還元雰囲気中におい
て１１００〜１６００℃の範囲内の温度で数時間焼成す
ることによって螢光体を得る。Is used. The above raw materials are weighed, boric acid, anhydrous boric acid and the like are added in an appropriate amount, and they are sufficiently pulverized and mixed by a ball mill. A quartz boat is filled with this and baked in a reducing atmosphere at a temperature in the range of 1100 to 1600 ° C. for several hours to obtain a phosphor.
以下、本発明の実施例について述べる。Examples of the present invention will be described below.
実施例１ 酸化イットリウム ０．１１ｇ 炭酸バリウム １８．７４ 酸化アルミニウム ４０．８０ 酸化ユーロピウム ０．８８ 無水ホウ酸 ０．７０ 上記原料をボールミルにて十分に粉砕混合し、還元性雰
囲気中、１１００〜１６００℃の温度で数時間焼成し、
螢光体を得た。Example 1 Yttrium oxide 0.11 g Barium carbonate 18.74 Aluminum oxide 40.80 Europium oxide 0.88 Boric anhydride 0.70 The above raw materials were thoroughly pulverized and mixed in a ball mill, and 1100 to 1600 ° C. in a reducing atmosphere. Bake at the temperature of several hours,
I got a phosphor.
得られた螢光体の組成式は次のとおりである。The composition formula of the obtained phosphor is as follows.
（Ｂａ０．９５Ｅｕ０．０５）Ｏ・４Ａｌ２Ｏ３・０．００５Ｙ２Ｏ３ この螢光体の紫外線励起による発光ピーク高さは酸化イ
ットリウムを含まない従来の螢光体 （Ｂａ０．９５Ｅｕ０．０５）Ｏ・４Ａｌ２Ｏ３ の発光ピーク高さに比べて１１０％であり、明らかな向
上が認められた。 (Ba 0.95 Eu 0.05) O · 4Al 2 O 3 · 0.005Y 2 O 3 ultraviolet excited light-emitting peak height by the phosphors conventional phosphor containing no yttrium oxide (Ba 0. It was 110% of the emission peak height of 95 Eu 0.05 ) O · 4Al 2 O 3 , showing a clear improvement.
実施例２ フツ化イットリウム ０．７３ｇ 炭酸バリウム １７．７６ 酸化アルミニウム ５１．００ 酸化ユーロピウム １．７６ ホウ酸 ２．６８ 上記原料を用い、実施例１と同様にして螢光体を得た。
得られた螢光体の組成式は次のとおりである。Example 2 Yttrium fluoride 0.73 g Barium carbonate 17.76 Aluminum oxide 51.00 Europium oxide 1.76 Boric acid 2.68 Using the above raw materials, a phosphor was obtained in the same manner as in Example 1.
The composition formula of the obtained phosphor is as follows.
（Ｂａ０．９Ｅｕ０．１）Ｏ・５Ａｌ２Ｏ３・０．００２５Ｙ２Ｏ３ この螢光体の紫外線励起による発光ピーク高さは、酸化
イットリウムを含まない従来の螢光体 （Ｂａ０．９Ｅｕ０．１）Ｏ・５Ａｌ２Ｏ３ の発光ピーク高さに比べて１０５％であり、明らかな向
上が認められた。(Ba 0.9 Eu 0.1 ) O.5Al 2 O 3 .0.0025Y 2 O 3 The emission peak height of this phosphor due to ultraviolet excitation is the same as that of a conventional phosphor (Ba 0 It was 105% of the emission peak height of .9 Eu 0.1 ) O.5Al 2 O 3 , showing a clear improvement.
実施例３ フッ化イットリウム ２．９１ｇ 炭酸バリウム １９．３４ 酸化アルミニウム ３５．７０ 酸化ユーロピウム ０．３５ ホウ酸 １．３４ 上記原料を用い、実施例１と同様にして螢光体を得た。
得られた螢光体の組成式は次のとおりである。Example 3 Yttrium fluoride 2.91 g Barium carbonate 19.34 Aluminum oxide 35.70 Europium oxide 0.35 Boric acid 1.34 A phosphor was obtained in the same manner as in Example 1 using the above raw materials.
The composition formula of the obtained phosphor is as follows.
（Ｂａ０．９８Ｅｕ０．０２）Ｏ・３．５Ａｌ２Ｏ３・
０．１Ｙ２Ｏ３ この螢光体の紫外線励起による発光ピーク高さは酸化イ
ットリウムを含まない従来の螢光体 （Ｂａ０．９８Ｅｕ０．０２）Ｏ・３．５Ａｌ２Ｏ３ の発光ピーク高さに比べて１０７％であり、明らかな向
上が認められた。(Ba 0.98 Eu 0.02 ) O · 3.5Al 2 O 3 ·
0.1Y 2 O 3 The emission peak height of this phosphor due to ultraviolet excitation is the emission peak of the conventional phosphor (Ba 0.98 Eu 0.02 ) O · 3.5Al 2 O 3 containing no yttrium oxide. It was 107% of the height, which was a clear improvement.
上記各実施例において、フラックスとして用いているホ
ウ素含有化合物は得られた螢光体中に、例えば（Ｂａ，
Ｅｕ）Ｏ・４Ａｌ２Ｏ３に対して０．０５Ｂ２Ｏ３量が
残っていることが認められたが、本螢光体の結晶構造に
大きく影響するものではなく、また発光特性に対して
も、とくに悪い影響はなく、必要であれば水洗等の後処
理によりある程度は除去することができるものである。In each of the above-mentioned examples, the boron-containing compound used as the flux is contained in the obtained phosphor, for example (Ba,
It has been found that there remain 0.05b 2 O 3 amount relative Eu) O · 4Al 2 O 3 , and not significantly affect the crystal structure of the phosphor, also with respect to the emission characteristics However, there is no particular adverse effect, and it can be removed to some extent by post-treatment such as washing with water if necessary.
発明の効果 以上説明したように、本発明は２価のユーロピウムで付
活されたバリウムアルミネート螢光体であって、組成式
が（Ｂａ，Ｅｕ）Ｏ・ｘＡｌ２Ｏ３・ｙＹ２Ｏ３（ただ
し、３≦ｘ≦５，０＜ｙ≦０．１）で表わされる螢光体
としたので、発光ピーク高さを向上させた優れた螢光体
を提供することができるものである。EFFECTS OF THE INVENTION As described above, the present invention is a barium aluminate phosphor activated with divalent europium, having a composition formula of (Ba, Eu) O.xAl 2 O 3 .yY 2 O 3 Since the phosphor represented by (3 ≦ x ≦ 5, 0 <y ≦ 0.1) is used, an excellent phosphor having an improved emission peak height can be provided.
Claims (1)
アルミネート螢光体であって、組成式が（Ｂａ，Ｅｕ）
Ｏ・ｘＡｌ２Ｏ３・ｙＹ２Ｏ３（ただし、３≦ｘ≦５，
０＜ｙ≦０．１）で表わされることを特徴とする螢光
体。1. A barium aluminate phosphor activated with divalent europium having a composition formula of (Ba, Eu).
O · xAl 2 O 3 · yY 2 O 3 (where 3 ≦ x ≦ 5
A phosphor characterized by the expression 0 <y ≦ 0.1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58250704A JPH0629416B2 (en) | 1983-12-27 | 1983-12-27 | Fluorescent body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58250704A JPH0629416B2 (en) | 1983-12-27 | 1983-12-27 | Fluorescent body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60139784A JPS60139784A (en) | 1985-07-24 |
| JPH0629416B2 true JPH0629416B2 (en) | 1994-04-20 |
Family
ID=17211798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58250704A Expired - Lifetime JPH0629416B2 (en) | 1983-12-27 | 1983-12-27 | Fluorescent body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629416B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267911B1 (en) | 1997-11-07 | 2001-07-31 | University Of Georgia Research Foundation, Inc. | Phosphors with long-persistent green phosphorescence |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100381618C (en) * | 2006-08-30 | 2008-04-16 | 大连理工大学 | Method for preparing aluminate long-persistence luminous plate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5876486A (en) * | 1981-10-30 | 1983-05-09 | Matsushita Electronics Corp | Fluorescent material |
-
1983
- 1983-12-27 JP JP58250704A patent/JPH0629416B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6267911B1 (en) | 1997-11-07 | 2001-07-31 | University Of Georgia Research Foundation, Inc. | Phosphors with long-persistent green phosphorescence |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60139784A (en) | 1985-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |