JP2006265396A - Red phosphor - Google Patents
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- JP2006265396A JP2006265396A JP2005086281A JP2005086281A JP2006265396A JP 2006265396 A JP2006265396 A JP 2006265396A JP 2005086281 A JP2005086281 A JP 2005086281A JP 2005086281 A JP2005086281 A JP 2005086281A JP 2006265396 A JP2006265396 A JP 2006265396A
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- electron beam
- red phosphor
- zinc
- zirconium
- europium
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 18
- 238000010894 electron beam technology Methods 0.000 claims abstract description 14
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 12
- 229910052726 zirconium Chemical group 0.000 claims abstract description 12
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical group [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 8
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 6
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims 1
- 230000005284 excitation Effects 0.000 abstract description 5
- 230000003081 coactivator Effects 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract 2
- 230000001133 acceleration Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 239000012190 activator Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910001940 europium oxide Inorganic materials 0.000 description 3
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000006690 co-activation Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000002178 europium compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 yttrium compound Chemical class 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
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Abstract
Description
本発明は、電界放出型ディスプレイ（ＦＥＤ）等の電子線励起発光素子に用いる赤色蛍光体に関する。 The present invention relates to a red phosphor used for an electron beam-excited light emitting device such as a field emission display (FED).
電子線励起発光素子に用いられる赤色蛍光体としては、ユーロピウムで賦活した酸化イットリウム（Ｙ、Ｅｕ）２Ｏ３が知られている。このものはイットリウムの一部をユーロピウムで置換することにより電子線を照射した際に赤色発光するのであるが、その発光輝度は十分ではなく、発光輝度向上に向けた検討がなされている。例えば、イットリウムの一部をさらに亜鉛で置換し、共賦活することで発光輝度を向上させた（Ｙ、Ｅｕ、Ｚｎ）２Ｏ３が知られている（特許文献１及び２参照）。 As a red phosphor used in an electron beam-excited light emitting device, yttrium oxide (Y, Eu) 2 O 3 activated with europium is known. Although this emits red light when it is irradiated with an electron beam by substituting a part of yttrium with europium, the light emission luminance is not sufficient, and studies for improving the light emission luminance have been made. For example, (Y, Eu, Zn) 2 O 3 is known in which emission luminance is improved by further substituting part of yttrium with zinc and performing co-activation (see Patent Documents 1 and 2).
特許文献１及び２に記載の（Ｙ、Ｅｕ、Ｚｎ）２Ｏ３は（Ｙ、Ｅｕ）２Ｏ３に較べれば赤色発光輝度の向上は認められるものの、電界放出型ディスプレイ（ＦＥＤ）の赤色発光素子として用いるには、更なる発光輝度の向上が求められている。
Although (Y, Eu, Zn) 2 O 3 described in
本発明者らは、より一層発光輝度の向上した赤色蛍光体を見出すべく種々の研究を重ねたところ、上記の（Ｙ、Ｅｕ、Ｚｎ）２Ｏ３において、共賦活剤としてさらにジルコニウムを併用すると電子線照射による発光輝度がより一層向上し、亜鉛単独共賦活系では得られない発光輝度が得られることを見出し、本発明を完成した。 The inventors of the present invention have made various studies in order to find a red phosphor having a further improved luminance. When the above (Y, Eu, Zn) 2 O 3 is used together with zirconium as a coactivator. The present inventors have found that the light emission luminance by electron beam irradiation is further improved and that the light emission luminance that cannot be obtained by the zinc co-activation system can be obtained.
すなわち、本発明は、酸化イットリウムを母体とし、イットリウムの一部をユーロピウム、亜鉛及びジルコニウムで置換したことを特徴とする電子線励起赤色蛍光体である。 That is, the present invention is an electron beam-excited red phosphor characterized in that yttrium oxide is used as a base and a part of yttrium is substituted with europium, zinc, and zirconium.
本発明の赤色蛍光体は、共賦活剤として亜鉛にさらにジルコニウムを併用することにより、電子線照射による発光輝度が上昇し、亜鉛単独系では得られない発光輝度が得られる。 In the red phosphor of the present invention, by further using zirconium together with zinc as a coactivator, the light emission luminance by electron beam irradiation increases, and light emission luminance that cannot be obtained with a zinc single system is obtained.
本発明は、電子線励起赤色蛍光体であって、酸化イットリウムを母体とし、イットリウムの一部をユーロピウム、亜鉛及びジルコニウムで置換したことを特徴とする。 The present invention is an electron beam-excited red phosphor, characterized in that yttrium oxide is used as a base material and a part of yttrium is substituted with europium, zinc, and zirconium.
賦活剤として用いるユーロピウム、共賦活剤として用いる亜鉛及びジルコニウムの置換量は、蛍光体の組成を一般式（Ｙ１-ｘ-ｙ-ｚＥｕｘＺｎｙＺｒｚ）２Ｏ３で表すと、０．０１≦ｘ≦０．３、０．０００１≦ｙ≦０．０１、０．０００１≦ｚ≦０．０３の範囲が好ましく、より好ましくは０．０２≦ｘ≦０．２ 、０．０００５≦ｙ≦０．００５、０．０００５≦ｚ≦０．０１である。 The substitution amount of europium used as an activator and zinc and zirconium used as a co-activator is 0 when the composition of the phosphor is represented by the general formula (Y1 -xyz Eu x Zn y Zr z ) 2 O 3. .01 ≦ x ≦ 0.3, 0.0001 ≦ y ≦ 0.01, 0.0001 ≦ z ≦ 0.03 are preferable, and 0.02 ≦ x ≦ 0.2 and 0.0005 ≦ are more preferable. It is y <= 0.005 and 0.0005 <= z <= 0.01.
賦活剤として用いるユーロピウムの置換量ｘが上記範囲より少ないと発光色の色純度が劣る傾向にあり、一方、上記範囲より多く添加しても、添加量に見合った発光強度が得られ難い。 If the substitution amount x of europium used as the activator is less than the above range, the color purity of the luminescent color tends to be inferior.
また、共賦活剤として用いる亜鉛及びジルコニウムの各々の置換量ｙ及びｚが上記範囲より少ないと優位な改善効果の確認が困難であり、一方、上記範囲より多く添加しても、逆に輝度が低下する。 In addition, if the substitution amounts y and z of zinc and zirconium used as a co-activator are less than the above range, it is difficult to confirm the superior improvement effect. descend.
さらに、本発明においては、Ｚｒの置換量ｚとＺｎの置換量ｙとの比（ｚ／ｙ）は、１．０〜６．０とすると輝度向上の効果が著しく好ましい。 Furthermore, in the present invention, the effect of improving the luminance is remarkably preferable when the ratio (z / y) of the substitution amount z of Zr and the substitution amount y of Zn is 1.0 to 6.0.
電界放出型ディスプレイ（ＦＥＤ）は、１００〜５０００Ｖの電圧で加速された電子線を励起源とする低電圧型と、５０００Ｖ以上の電圧で加速された電子線を励起源とする高電圧型の２種類が検討されている。本発明の赤色蛍光体は少なくとも３０００Ｖ程度の加速電圧で励起された電子線を照射すれば十分な発光が得られるので、上記何れの型でも使用することができる。
A field emission display (FED) is a low voltage type using an electron beam accelerated by a voltage of 100 to 5000 V as an excitation source and a
本発明の赤色蛍光体は、例えば、原料としてイットリウム化合物、ユーロピウム化合物、亜鉛化合物及びジルコニウム化合物の原料粉末の混合物を、必要に応じてホウ素等のフラックスの存在下で乾式で８００〜１４００℃の温度範囲で焼成することで得られる。焼成雰囲気としては、酸化、還元、等特に制約はないが、酸化雰囲気が好ましい。 The red phosphor of the present invention is, for example, a mixture of raw material powders of yttrium compound, europium compound, zinc compound and zirconium compound as a raw material, optionally in the presence of a flux such as boron, at a temperature of 800 to 1400 ° C. It is obtained by firing in the range. The firing atmosphere is not particularly limited, such as oxidation and reduction, but an oxidation atmosphere is preferable.
以下、本発明を実施例により説明するが、本発明はそれら実施例に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples.
実施例１
酸化イットリウム（Ｙ２Ｏ３）、酸化ユーロピウム（Ｅｕ２Ｏ３）、酸化亜鉛（ＺｎＯ）、酸化ジルコニウム（ＺｒＯ２）をモル比でＹ：Ｅｕ：Ｚｎ：Ｚｒ＝０．９４６：０．０５：０．００２：０．００２になるように配合、自動瑪瑙乳鉢にて混合を行った後、得られた混合物をアルミナ製ルツボに適量入れ、大気中で１０００℃の温度で４時間保持して焼成した。これを冷却し再び混合を行った後、大気中１２００℃の温度で２０時間保持して焼成した。これを自動瑪瑙乳鉢で粉砕して本発明の蛍光体粉末（試料Ａ）を得た。
１．０×１０−５Ｐａ以下の真空槽内で、得られた試料Ａに電子銃（Ｋｉｍｂａｌｌ Ｐｈｙｓｉｃｓ Ｉｎｃ製ＥＦＧ−７）により電子線を照射したところ赤色に発光して、そのときの相対輝度は１００（加速電圧５ｋＶ）であった。
Example 1
Yttrium oxide (Y 2 O 3 ), europium oxide (Eu 2 O 3 ), zinc oxide (ZnO), and zirconium oxide (ZrO 2 ) in a molar ratio of Y: Eu: Zn: Zr = 0.946: 0.05: 0.002: After blending to 0.002 and mixing in an automatic agate mortar, an appropriate amount of the resulting mixture is put into an alumina crucible and held in the atmosphere at a temperature of 1000 ° C. for 4 hours for baking. did. This was cooled and mixed again, and then calcined by maintaining at a temperature of 1200 ° C. in the atmosphere for 20 hours. This was pulverized in an automatic agate mortar to obtain the phosphor powder of the present invention (Sample A).
When the obtained sample A was irradiated with an electron beam with an electron gun (EFG-7 manufactured by Kimball Physics Inc) in a vacuum chamber of 1.0 × 10 −5 Pa or less, it emitted red light, and the relative luminance at that time Was 100 (
比較例１（Ｚｎ単独系）
酸化イットリウム（Ｙ２Ｏ３）、酸化ユーロピウム（Ｅｕ２Ｏ３）、酸化亜鉛（ＺｎＯ）をモル比でＹ：Ｅｕ：Ｚｎ＝０．９４８：０．０５：０．００２になるように配合し、実施例１と同様の処理を行い、比較試料の蛍光体粉末（試料Ｂ）を得た。
得られた試料Ｂの電子線照射による発光を、実施例１と同様の方法で測定したところ、その相対輝度は８０．０（加速電圧５ｋＶ）であった。
Comparative Example 1 (Zn single system)
Yttrium oxide (Y 2 O 3 ), europium oxide (Eu 2 O 3 ), and zinc oxide (ZnO) are blended in a molar ratio of Y: Eu: Zn = 0.948: 0.05: 0.002. The same treatment as in Example 1 was performed to obtain a phosphor powder (sample B) as a comparative sample.
The light emission of the obtained sample B by electron beam irradiation was measured by the same method as in Example 1. As a result, the relative luminance was 80.0 (
比較例２（Ｚｒ単独系）
酸化イットリウム（Ｙ２Ｏ３）、酸化ユーロピウム（Ｅｕ２Ｏ３）、酸化ジルコニウム（ＺｒＯ２）をモル比でＹ：Ｅｕ：Ｚｒ＝０．９４８：０．０５：０．００２になるように配合し、実施例１と同様の処理を行い、比較試料の蛍光体粉末（試料Ｃ）を得た。
得られた試料Ｃの電子線照射による発光を、実施例１と同様の方法で測定したところ、その相対輝度は７０．１（加速電圧５ｋＶ）であった。
Comparative Example 2 (Zr single system)
Yttrium oxide (Y 2 O 3 ), europium oxide (Eu 2 O 3 ), zirconium oxide (ZrO 2 ) are blended so that the molar ratio is Y: Eu: Zr = 0.948: 0.05: 0.002. And the process similar to Example 1 was performed and the fluorescent substance powder (sample C) of a comparative sample was obtained.
When light emission of the obtained sample C by electron beam irradiation was measured by the same method as in Example 1, the relative luminance was 70.1 (
以上の結果からＺｒとＺｎを共に添加することによって、それぞれの元素を単独で添加したときには得られないほどの輝度が得られた。一般に単独で添加効果のある元素を組み合わせて添加しても、その効果までもが足しあわされるとは限らないので、このＺｒとＺｎとを併用することによる輝度向上の効果は有用である。 From the above results, by adding both Zr and Zn, a brightness that could not be obtained when each element was added alone was obtained. In general, even when elements having an additive effect alone are added in combination, the effects are not necessarily added. Therefore, the effect of improving luminance by using Zr and Zn in combination is useful.
また、得られた試料Ａ、Ｂ及びＣの電子線励起による発光輝度と加速電圧の関係を図１に示した。図１より、加速電圧が上昇するにしたがって本発明の試料Ａと比較試料Ｂ及びＣとの発光輝度の差が広がる傾向がみられることから、低電圧型ＦＥＤ用および高電圧型ＦＥＤ用赤色蛍光体としてのみならず、陰極線管等の高加速電圧での発光を利用する赤色蛍光体としても有用であることがわかった。 Further, FIG. 1 shows the relationship between the emission luminance of the obtained samples A, B, and C by electron beam excitation and the acceleration voltage. As shown in FIG. 1, the difference in emission luminance between the sample A of the present invention and the comparative samples B and C tends to widen as the acceleration voltage increases. Therefore, the red fluorescence for the low voltage type FED and the high voltage type FED is used. It was found that the phosphor is useful not only as a phosphor but also as a red phosphor utilizing light emission at a high acceleration voltage such as a cathode ray tube.
本発明の赤色蛍光体は、電界放出型ディスプレイ（ＦＥＤ）等の電子線励起発光素子に用いる赤色蛍光材料として有用なものである。また、加速電圧の高い陰極線管用発光素子に用いる赤色蛍光材料としても有用なものである。 The red phosphor of the present invention is useful as a red fluorescent material used for an electron beam-excited light emitting device such as a field emission display (FED). It is also useful as a red fluorescent material used in a cathode ray tube light emitting device having a high acceleration voltage.
Claims (3)
3. The electron beam excited red phosphor according to claim 2, wherein the compounding ratio (z / y) of Zn and Zr is 1.0 to 6.0.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005086281A JP2006265396A (en) | 2005-03-24 | 2005-03-24 | Red phosphor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005086281A JP2006265396A (en) | 2005-03-24 | 2005-03-24 | Red phosphor |
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| JP2006265396A true JP2006265396A (en) | 2006-10-05 |
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