JPH0629417B2 - Fluorescent body - Google Patents
Fluorescent bodyInfo
- Publication number
- JPH0629417B2 JPH0629417B2 JP25070583A JP25070583A JPH0629417B2 JP H0629417 B2 JPH0629417 B2 JP H0629417B2 JP 25070583 A JP25070583 A JP 25070583A JP 25070583 A JP25070583 A JP 25070583A JP H0629417 B2 JPH0629417 B2 JP H0629417B2
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- emission peak
- oxide
- europium
- peak height
- 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
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ストロンチウ
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 strontium 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ストロンチウム
アルミネート螢光体としては、米国特許第３，２９４，
６９９号明細書に記載されているＳｒＡｌ２Ｏ４：Ｅ▲
2+ u▼が古くから知られており、発光ピーク波長５２０
ｎｍの緑色発光を示す。一方、ＭｅＡｌ２Ｏ４：Ｅ▲2+
u▼およびＭｅＡｌ１２Ｏ１９：Ｅ▲2+ u▼に関しては、
Ｇ．ＢＬＡＳＳＥ ａｎｄ Ａ．ＢＲＩＬ，Ｐｈｉｌｉ
ｐｓ Ｒｅｓ，Ｒｅｐｔ．，２３（１９６８）２０１に
研究報告があり、ＳｒＡｌ１２Ｏ１９：Ｅ▲2+ u▼の発
光ピークは３９５ｎｍであることが知られている。Configuration of Conventional Example and its Problems Conventionally, as a strontium aluminate phosphor activated with divalent europium, US Pat.
SrAl 2 O 4 : E ▲ described in 699 specification.
2+ u ▼ has been known for a long time, and has an emission peak wavelength of 520.
It exhibits a green emission of nm. On the other hand, MeAl 2 O 4 : E ▲ 2+
Regarding u ▼ and MeAl 12 O 19 : E ▲ 2+ u ▼,
G. BASSE and A. BRIL, Phili
ps Res, Rept. , 23 (1968) 201, and it is known that the emission peak of SrAl 12 O 19 : E (2 + u) is 395 nm.
近年、高演色性螢光ランプの効率改善に関して、特開昭
５４−１０２０７３号公報および特開昭５５−１１５４
８９号公報が提案され、４８０〜５００ｎｍ付近に発光
ピークを有する螢光体が注目されてきている。最近の研
究によれば、例えばＪ．Ｔ．Ｃ．ＶＡＮ ＫＥＭＥＮＡ
ＤＥ ａｎｄ Ｇ．Ｐ．Ｆ．ＨＯＥＫＳ，Ｅｘｔｅｎｄ
ｅｄ ａｂｓｔｒａｃｔ No．６０７，Ｅ．Ｃ．Ｓ．Ｓ
ｐｒｉｎｇ Ｍｅｅｔｉｎｇ（１９８３）に報告されて
いるＳｒ４Ａｌ１４Ｏ２５：Ｅ▲2+ u▼螢光体は発光ピ
ーク波長が４９０ｎｍにある新しいタイプのアルミネー
トである。In recent years, regarding the efficiency improvement of a high color rendering fluorescent lamp, JP-A-54-102073 and JP-A-55-1154 have been proposed.
Japanese Unexamined Patent Publication No. 89 has been proposed, and a phosphor having an emission peak near 480 to 500 nm has been attracting attention. According to recent research, for example, J. T. C. VAN KEMENA
DE and G.D. P. F. HOEKS, Extend
ed abstract No. 607, E.I. C. S. S
The Sr 4 Al 14 O 25 : E 2+ u ▼ phosphor reported in pring Meeting (1983) is a new type of aluminate with an emission peak wavelength of 490 nm.
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。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,
It is an object of the present invention to provide a divalent europium-activated 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ストロン
チ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。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ストロンチウムア
ルミネート螢光体は、その組成式が４（Ｓｒ，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６≦ｘ≦８，０＜
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６＞ｘまたは
８＜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Ｓｒ４Ａｌ１４Ｏ２５：Ｅ▲2+ u
▼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発光ピ
ーク高さの向上効果が認められた。Composition of the Invention The inventors have carried out detailed experiments on divalent europium-activated strontium aluminate phosphors, and as a result of further dissolving yttrium oxide in the phosphors, their emission peaks are obtained. It was found that the height can be further improved. That is, according to the experiments by the inventors, the composition formula of the strontium aluminate phosphor activated with divalent europium is 4 (Sr, Eu) O.
· XAl are those represented by 2 O 3 · yY 2 O 3 ,
The ranges of x and y in the above composition formula are 6 ≦ x ≦ 8 and 0 <, respectively.
When y ≦ 0.1, a more preferable improvement in emission peak height was observed. Furthermore, in the case of the phosphor according to the present invention, the effect of improving the emission peak height due to the solid solution of yttrium oxide is obtained even in the region where the Al 2 O 3 amount x is 6> x or 8 <x. Although clearly recognized, even with these improved peak heights, Sr 4 Al 14 O 25 : E ▲ 2+ u which is currently in practical use.
▼ It was confirmed that a material that exceeds the emission peak height of the phosphor was not obtained, and that it did not reach a practical level. In addition, the effect of improving the emission peak height was confirmed within the range of the europium concentration in other commonly used phosphors, with the addition amount of europium as the activator.
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) 酸化ストロンチウム（ＳｒＯ）または硝酸塩，炭
酸塩，ハロゲン化物等の高温で容易にＳｒＯに変化し得
る化合物。(2) Strontium oxide (SrO) or a compound such as nitrate, carbonate, or halide which can be easily converted to SrO 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 炭酸ストロンチウム ５７．２７ 酸化アルミニウム ７１．４０ 酸化ユーロピウム ２．１１ 無水ホウ酸 １．７４ 上記原料をボールミルにて十分粉砕混合し、還元性雰囲
気中、１１００〜１６００℃の範囲内の温度で数時間焼
成し螢光体を得た。Example 1 Yttrium oxide 0.11 g Strontium carbonate 57.27 Aluminum oxide 71.40 Europium oxide 2.11 Boric anhydride 1.74 The above raw materials were thoroughly pulverized and mixed in a ball mill to obtain a mixture of 1100 to 1600 ° C. in a reducing atmosphere. The phosphor was obtained by firing at a temperature within the range for several hours.
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.
４（Ｓｒ０．９７Ｅｕ０．０３）Ｏ・７Ａｌ２Ｏ３・
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 ４（Ｓｒ０．９７Ｅｕ０．０３）Ｏ・７Ａｌ２Ｏ３ 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。4 (Sr 0.97 Eu 0.03 ) O · 7Al 2 O 3 ·
0.005Y 2 O 3 ultraviolet excited light-emitting peak height by the phosphors conventional fluorescent body 4 containing no yttrium oxide (Sr 0.97 Eu 0.03) emission peak O · 7Al 2 O 3 High It was 107%, which was a clear improvement.
実施例２ フツ化イットリウム ０．７３ｇ 炭酸ストロンチウム ５７．８６ 酸化アルミニウム ７１．４０ 酸化ユーロピウム １．４１ 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 Strontium carbonate 57.86 Aluminum oxide 71.40 Europium oxide 1.41 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.
４（Ｓｒ０．９８Ｅｕ０．０２）Ｏ・７Ａｌ２Ｏ３・
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 ４（Ｓｒ０．９８Ｅｕ０．０２）Ｏ・７Ａｌ２Ｏ３ 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。4 (Sr 0.98 Eu 0.02 ) O · 7Al 2 O 3 ·
0.0025Y 2 O 3 light-emitting peak height by ultraviolet excitation of the fluorescent substance, the emission peak of the conventional phosphor not containing yttrium oxide 4 (Sr 0.98 Eu 0.02) O · 7Al 2 O 3 It was 105% of the height, which was a clear improvement.
実施例３ フッ化イットリウム ２．９１ｇ 炭酸ストロンチウム ５７．２７ 酸化アルミニウム ８１．６０ 酸化ユーロピウム ２．１１ 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 Strontium carbonate 57.27 Aluminum oxide 81.60 Europium oxide 2.11 Boric acid 1.34 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.
４（Ｓｒ０．９７Ｅｕ０．０３）Ｏ・８Ａｌ２Ｏ３・
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 ４（Ｓｒ０．９７Ｅｕ０．０３）Ｏ・８Ａｌ２Ｏ３ の発光ピーク高さに比べて１０３％であり、明らかな向
上が認められた。4 (Sr 0.97 Eu 0.03 ) O · 8Al 2 O 3 ·
0.1Y 2 O 3 The emission peak height of this phosphor due to ultraviolet excitation is the same as that of the conventional phosphor 4 (Sr 0.97 Eu 0.03 ) O · 8Al 2 O 3 containing no yttrium oxide. It was 103%, which was a clear improvement.
実施例４ 酸化イットリウム ０．３４ｇ 炭酸ストロンチウム ５７．８５ 酸化アルミニウム ６１．２０ 酸化ユーロピウム ０．７０ 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 4 Yttrium oxide 0.34 g Strontium carbonate 57.85 Aluminum oxide 61.20 Europium oxide 0.70 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.
４（Ｓｒ０．９９Ｅｕ０．０１）Ｏ・６Ａｌ２Ｏ３・
０．０３Ｙ２Ｏ３ 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 ４（Ｓｒ０．９９Ｅｕ０．０１）Ｏ・６Ａｌ２Ｏ３ の発光ピーク高さに比べて１１０％であり、明らかに向
上が認められた。4 (Sr 0.99 Eu 0.01 ) O · 6Al 2 O 3 ·
0.03Y 2 O 3 The emission peak height of this phosphor due to ultraviolet excitation is as high as that of the conventional phosphor 4 (Sr 0.99 Eu 0.01 ) O · 6Al 2 O 3 containing no yttrium oxide. It was 110% compared with the above, and an obvious improvement was recognized.
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４（Ｓ
ｒ，Ｅｕ）Ｏ・７Ａｌ２Ｏ３に対して０．２Ｂ２Ｏ３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いことをＸ線回折データに
より確認した。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
除去することもできるものである。In each of the above-mentioned examples, the boron-containing compound used as the flux is, for example, 4 (S) in the obtained phosphor.
It was confirmed that 0.2B 2 O 3 amount remained with respect to r, Eu) O · 7Al 2 O 3 , but it did not significantly affect the crystal structure of the present phosphor. Confirmed by data. Further, there is no particular adverse effect on the light emission characteristics, and if necessary, it can be removed to some extent by post-treatment such as washing with water.
発明の効果 以上説明したように、本発明は一般式が４（Ｓｒ，Ｅ
ｕ）Ｏ・ｘＡｌ２Ｏ３・ｙＹ２Ｏ３（ただし、６≦ｘ≦
８，ｏ＜ｙ≦０．１）で表わされる構成を有するので、
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 has the general formula of 4 (Sr, E
u) O · xAl 2 O 3 · yY 2 O 3 (where 6 ≦ x ≦
8, o <y ≦ 0.1),
It is possible to provide an excellent phosphor having an improved emission peak height.
Claims (1)
れ、式中ｘ，ｙがそれぞれ ６≦ｘ≦８ ０＜ｙ≦０．１ の範囲にあることを特徴とする螢光体。1. A general formula is represented by 4 (Sr, Eu) O · xAl 2 O 3 · yY 2 O 3, wherein x, the range y is 6 ≦ x ≦ 8 0 <y ≦ 0.1 , respectively A fluorescent substance characterized by being in.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25070583A JPH0629417B2 (en) | 1983-12-27 | 1983-12-27 | Fluorescent body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25070583A JPH0629417B2 (en) | 1983-12-27 | 1983-12-27 | Fluorescent body |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60139785A JPS60139785A (en) | 1985-07-24 |
| JPH0629417B2 true JPH0629417B2 (en) | 1994-04-20 |
Family
ID=17211814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25070583A Expired - Lifetime JPH0629417B2 (en) | 1983-12-27 | 1983-12-27 | Fluorescent body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0629417B2 (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 (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL8700808A (en) * | 1987-04-07 | 1988-11-01 | Philips Nv | METHOD FOR PREPARING A LUMINESCENT EU2-ACTIVATED STRONTIUM ALUMINATE, ALUMINATED IN SUCH A WAY AND LOW-PRESSURE VAPOR DISCHARGE LAMP INCLUDING SUCH AN ALUMINATE |
| US5376303A (en) * | 1994-06-10 | 1994-12-27 | Nichia Chemical Industries, Ltd. | Long Decay phoaphors |
| CN100381618C (en) * | 2006-08-30 | 2008-04-16 | 大连理工大学 | Method for preparing aluminate long-persistence luminous plate |
| US20130020928A1 (en) * | 2011-07-18 | 2013-01-24 | General Electric Company | Phosphor precursor composition |
-
1983
- 1983-12-27 JP JP25070583A patent/JPH0629417B2/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 |
|---|---|
| JPS60139785A (en) | 1985-07-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |