JP2007246918A - Phosphor for vacuum ultraviolet light-excited light emitting device - Google Patents
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Abstract
【課題】発光輝度が高く、プラズマ暴露による輝度低下が少ない真空紫外線励起発光素子用の蛍光体を提供する。
【解決手段】一般式ｍＭ1Ｏ・ｎＭ2Ｏ・２Ｍ3Ｏ2（式中のＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ2はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ3はＳｉおよびＧｅからなる群より選ばれる１種以上、０．５≦ｍ≦３．５、０．５≦ｎ≦２．５、ただしｍ＝ｎ＝１のときはＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａである。）で表される化合物に付活剤としてＥｕおよびＭｎからなる群より選ばれる１種以上が含有されてなる真空紫外線励起発光素子用の蛍光体。ディオプサイド、オケルマナイト、メルウィナイトのいずれかと同じ結晶構造を有する上記記載の蛍光体。
【選択図】なしThe present invention provides a phosphor for a vacuum ultraviolet ray-excited light emitting device having high emission luminance and low luminance reduction due to plasma exposure.
A general formula mM 1 O · nM 2 O · 2M 3 O 2 (M 1 in the formula is one or more members selected from the group consisting of Ca, Sr and Ba, M 2 is from the group consisting of Mg and Zn One or more selected, M 3 is one or more selected from the group consisting of Si and Ge, 0.5 ≦ m ≦ 3.5, 0.5 ≦ n ≦ 2.5, provided that m = n = 1 M 1 is two or more selected from the group consisting of Ca, Sr and Ba, or Sr or Ba.) As an activator, M 1 contains at least one selected from the group consisting of Eu and Mn. A phosphor for a vacuum ultraviolet ray-excited light emitting device. The phosphor according to the above, having the same crystal structure as any of diopside, akermanite, and merwinite.
[Selection figure] None
Description
本発明は、プラズマディスプレイパネル（以下「ＰＤＰ」という。）および希ガスランプなどの真空紫外線励起発光素子に好適な蛍光体に関するものである。 The present invention relates to a phosphor suitable for a vacuum ultraviolet ray excited light emitting device such as a plasma display panel (hereinafter referred to as “PDP”) and a rare gas lamp.
真空紫外線等によって励起して発光させる蛍光体はすでに知られている。例えば、Ｂａ、Ｍｇ、Ａｌ、Ｏと付活剤（Ｅｕ）とからなるＢａＭｇＡｌ10Ｏ17：Ｅｕが真空紫外線励起発光素子用の青色蛍光体として、また例えば、Ｚｎ、Ｓｉ、Ｏと付活剤（Ｍｎ）とからなるＺｎ2ＳｉＯ4：Ｍｎが緑色蛍光体として、また例えば、Ｙ、Ｇｄ、Ｂ、Ｏと付活剤（Ｅｕ）とからなる（Ｙ，Ｇｄ）ＢＯ3：Ｅｕ赤色蛍光体として実用化されており、ＰＤＰや希ガスランプ等の真空紫外線励起発光素子用に用いられている。 A phosphor that emits light by being excited by vacuum ultraviolet rays or the like is already known. For example, BaMgAl 10 O 17 : Eu composed of Ba, Mg, Al, O and an activator (Eu) is used as a blue phosphor for a vacuum ultraviolet ray-excited light emitting element, and for example, Zn, Si, O and an activator. Zn 2 SiO 4 : Mn composed of (Mn) as a green phosphor, for example, (Y, Gd) BO 3 : Eu red phosphor composed of Y, Gd, B, O and an activator (Eu) And is used for vacuum ultraviolet-excited light emitting devices such as PDPs and rare gas lamps.
しかしながら、これら真空紫外線励起発光素子用の蛍光体にはさらなる輝度の向上が望まれていた。また、ＰＤＰおよび希ガスランプ等の真空紫外線励起発光素子においては、希ガス中で放電を行いプラズマを生成させることにより真空紫外線を発生しているが、プラズマに暴露されることにより蛍光体の輝度が低下する問題があり、プラズマ暴露による輝度低下の少ない真空紫外線励起発光素子用の蛍光体が求められており、上記したようなアルミン酸塩、ケイ酸塩、ホウ酸塩からなる蛍光体が検討されている。
ケイ酸塩からなる蛍光体としては、例えば、非特許文献１には真空紫外線励起発光素子用の蛍光体としてＣａＭｇＳｉ2Ｏ6：Ｅｕが開示されているが、輝度が十分ではなかった。
なお、特許文献１にはＳｒ1.995ＭｇＳｉ2Ｏ7：Ｅｕ0.005，Ｄｙ0.025，Ｃｌ0.025およびＳｒ0.445Ｂａ1.55ＭｇＳｉ2Ｏ7：Ｅｕ0.005，Ｄｙ0.025，Ｃｌ0.025が開示されているが、暗所の表示用等に用いられる蓄光体用の蛍光体であり、真空紫外線励起については記載されていなかった。
However, further improvement in luminance has been desired for the phosphors for vacuum ultraviolet light-excited light emitting elements. Moreover, in vacuum ultraviolet light-excited light emitting devices such as PDPs and rare gas lamps, vacuum ultraviolet rays are generated by generating a plasma by discharging in a rare gas. There is a need for phosphors for vacuum-ultraviolet-excited light-emitting devices that have low brightness reduction due to exposure to plasma, and phosphors composed of aluminates, silicates, and borates as described above have been studied. Has been.
As a phosphor made of silicate, for example, Non-Patent Document 1 discloses CaMgSi 2 O 6 : Eu as a phosphor for a vacuum ultraviolet ray-excited light emitting device, but the luminance is not sufficient.
Patent Document 1 discloses Sr 1.995 MgSi 2 O 7 : Eu 0.005 , Dy 0.025 , Cl 0.025 and Sr 0.445 Ba 1.55 MgSi 2 O 7 : Eu 0.005 , Dy 0.025 , Cl 0.025 . It is a phosphor for a phosphorescent material used for display and the like, and vacuum ultraviolet excitation was not described.
本発明の目的は、輝度が高く、プラズマ暴露による輝度低下が少ない真空紫外線励起発光素子用の蛍光体を提供することにある。 An object of the present invention is to provide a phosphor for a vacuum ultraviolet ray-excited light emitting device having a high luminance and a low luminance reduction due to plasma exposure.
本発明者らは、かかる状況下、上記の課題を解決すべく鋭意研究を重ねた結果、真空紫外線励起発光素子用には、ケイ酸塩またはゲルマン酸塩蛍光体の中でも、一般式ｍＭ1Ｏ・ｎＭ2Ｏ・２Ｍ3Ｏ2（式中のＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ2はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ3はＳｉおよびＧｅからなる群より選ばれる１種以上、０．５≦ｍ≦３．５、０．５≦ｎ≦２．５、ただしｍ＝ｎ＝１のとき、Ｍ1はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａである。）で表される化合物に付活剤としてＥｕおよびＭｎからなる群より選ばれる１種以上が含有されてなる特定組成のケイ酸塩またはゲルマン酸塩蛍光体は輝度が高くかつプラズマ暴露による輝度低下が少ないことを見出し、本発明を完成するに至った。 Under these circumstances, the present inventors have intensively studied to solve the above-mentioned problems. As a result, among vacuum silicate-excited light-emitting devices, the general formula mM 1 O NM 2 O · 2M 3 O 2 (wherein M 1 is one or more selected from the group consisting of Ca, Sr and Ba, M 2 is one or more selected from the group consisting of Mg and Zn, M 3 is One or more selected from the group consisting of Si and Ge, 0.5 ≦ m ≦ 3.5, 0.5 ≦ n ≦ 2.5, provided that when m = n = 1, M 1 is Ca, Sr and Ba 2 or more selected from the group consisting of, or Sr or Ba.) A silicate having a specific composition comprising at least one selected from the group consisting of Eu and Mn as an activator. Alternatively, germanate phosphors have high brightness and brightness due to plasma exposure. Found that the decrease is small, it has led to the completion of the present invention.
すなわち本発明は、以下の（１）〜（１０）に関するものである。
（１）一般式ｍＭ1Ｏ・ｎＭ2Ｏ・２Ｍ3Ｏ2（式中のＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ2はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ3はＳｉおよびＧｅからなる群より選ばれる１種以上、０．５≦ｍ≦３．５、０．５≦ｎ≦２．５、ただしｍ＝ｎ＝１のときはＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａである。）で表される化合物に付活剤としてＥｕおよびＭｎからなる群より選ばれる１種以上が含有された真空紫外線励起発光素子用の蛍光体。
（２）ディオプサイド（Ｄｉｏｐｓｉｄｅ、透輝石）と同じ結晶構造を有する上記（１）記載の蛍光体。
（３）一般式（Ｍ4 1-aＥｕa）（Ｍ5 1-bＭｎb）Ｍ6 2Ｏ6（式中のＭ4はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａ、Ｍ5はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ6はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ａ≦０．５、０≦ｂ≦０．５、０＜ａ＋ｂ。）により表される組成を有する上記（２）記載の蛍光体。
（４）一般式Ｃａ1-c-dＳｒcＥｕdＭｇＳｉ2Ｏ6（０＜ｃ≦０．１、０＜ｄ≦０．１。）で表される上記（２）記載の蛍光体。
（５）上記（１）記載の真空紫外線励起発光素子用の蛍光体であって、オケルマナイト（Ａｋｅｒｍａｎｉｔｅ、オケルマン石）と同じ結晶構造を有する蛍光体。
（６）一般式（Ｍ7 1-eＥｕe）2（Ｍ8 1-fＭｎf）Ｍ9 2Ｏ7（式中のＭ7はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ8はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ9はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ｅ≦０．５、０≦ｆ≦０．５、０＜ｅ＋ｆ。）で表される組成を有する上記（５）記載の蛍光体。
（７）一般式（Ｍ10 1-gＥｕg）2Ｍ11Ｓｉ2Ｏ7（式中のＭ10はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ11はＭｇおよびＺｎからなる群から選ばれる１種以上、０．００１≦ｇ≦０．１）で表される組成を有する上記（５）記載の蛍光体。
（８）一般式（Ｍ12 1-hＥｕh）（Ｍ13 1-iＭｎi）2Ｍ14 2Ｏ7（式中のＭ12はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ13はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ14はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ｈ≦０．５、０≦ｉ≦０．５、０＜ｈ＋ｉ。）で表される組成を有する上記（５）記載の蛍光体。
（９）上記（１）記載の真空紫外線励起発光素子用の蛍光体であって、メルウィナイト（Ｍｅｒｗｉｎｉｔｅ）と同じ結晶構造を有する蛍光体。
（１０）一般式（Ｍ15 1-jＥｕj）3（Ｍ16 1-kＭｎk）Ｍ17 2Ｏ8（式中のＭ15はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ16はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ17はＳｉおよびＧｅからなる群より選ばれた１種以上、０≦ｊ≦０．５、０≦ｋ≦０．５、０＜ｊ＋ｋ。）で表される組成を有する上記（９）記載の蛍光体。
That is, the present invention relates to the following (1) to (10).
(1) General formula mM 1 O · nM 2 O · 2M 3 O 2 (wherein M 1 is one or more selected from the group consisting of Ca, Sr and Ba, and M 2 is selected from the group consisting of Mg and Zn) one or more elements, M 3 is at least one element selected from the group consisting of Si and Ge, is 0.5 ≦ m ≦ 3.5,0.5 ≦ n ≦ 2.5, provided that when m = n = 1 M 1 is two or more selected from the group consisting of Ca, Sr and Ba, or Sr or Ba.) As an activator, one or more selected from the group consisting of Eu and Mn is contained in the compound represented by Phosphor for vacuum ultraviolet excitation light emitting element.
(2) The phosphor according to the above (1), which has the same crystal structure as that of diopside.
(3) General formula (M 4 1-a Eu a ) (M 5 1-b Mn b ) M 6 2 O 6 (wherein M 4 is two or more selected from the group consisting of Ca, Sr and Ba, or Sr or Ba, M 5 is one or more selected from the group consisting of Mg and Zn, M 6 is one or more selected from the group consisting of Si and Ge, 0 ≦ a ≦ 0.5, 0 ≦ b ≦ 0. 5, 0 <a + b.) The phosphor according to (2) above, which has a composition represented by:
(4) General formula Ca 1-cd Sr c Eu d MgSi 2 O 6 (0 <c ≦ 0.1,0 <d ≦ 0.1.) Phosphor of the (2) described represented by.
(5) A phosphor for a vacuum ultraviolet ray-excited light emitting device as described in (1) above, which has the same crystal structure as that of akermanite.
(6) General formula (M 7 1-e Eu e ) 2 (M 8 1-f Mn f ) M 9 2 O 7 (wherein M 7 is one or more selected from the group consisting of Ca, Sr and Ba) , M 8 is one or more selected from the group consisting of Mg and Zn, M 9 is one or more selected from the group consisting of Si and Ge, 0 ≦ e ≦ 0.5, 0 ≦ f ≦ 0.5, 0 <E + f.) The phosphor according to (5) above, which has a composition represented by:
(7) General formula (M 10 1-g Eu g ) 2 M 11 Si 2 O 7 (wherein M 10 is one or more selected from the group consisting of Ca, Sr and Ba, and M 11 is from Mg and Zn) The phosphor according to (5) above, having a composition represented by at least one selected from the group consisting of 0.001 ≦ g ≦ 0.1.
(8) General formula (M 12 1-h Eu h ) (M 13 1-i Mn i ) 2 M 14 2 O 7 (wherein M 12 is one or more selected from the group consisting of Ca, Sr and Ba) , M 13 is one or more selected from the group consisting of Mg and Zn, M 14 is one or more selected from the group consisting of Si and Ge, 0 ≦ h ≦ 0.5, 0 ≦ i ≦ 0.5, 0 <H + i.) The phosphor according to (5) above having a composition represented by:
(9) A phosphor for a vacuum ultraviolet ray-excited light emitting device according to (1), wherein the phosphor has the same crystal structure as that of Merwinite.
(10) In formula (M 15 1-j Eu j ) 3 (M 16 1-k Mn k) M 17 2 O 8 (M 15 in the formula is one or more members selected from the group consisting of Ca, Sr and Ba M 16 is one or more selected from the group consisting of Mg and Zn, M 17 is one or more selected from the group consisting of Si and Ge, 0 ≦ j ≦ 0.5, 0 ≦ k ≦ 0.5, The phosphor according to (9) above, which has a composition represented by 0 <j + k.
本発明の蛍光体は輝度が高く、プラズマ暴露による輝度低下が少なく、特にＰＤＰや希ガスランプなどの真空紫外線励起発光素子用に好適であり、高輝度の真空紫外線励起発光素子が実現できるので、工業的に極めて有用である。 The phosphor of the present invention has a high luminance and is less susceptible to a decrease in luminance due to plasma exposure, and is particularly suitable for a vacuum ultraviolet excitation light emitting device such as a PDP or a rare gas lamp. It is extremely useful industrially.
以下に本発明について詳しく説明する。
本発明の真空紫外線励起発光素子用の蛍光体は、一般式ｍＭ1Ｏ・ｎＭ2Ｏ・２Ｍ3Ｏ2（式中のＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ2はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ3はＳｉおよびＧｅからなる群より選ばれる１種以上、０．５≦ｍ≦３．５、０．５≦ｎ≦２．５、ただしｍ＝ｎ＝１のとき、Ｍ1はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａである。）を母結晶とし、付活剤としてＥｕおよびＭｎからなる群より選ばれる１種以上が含有されてなることを特徴とし、ディオプサイド、オケルマナイト、メルウィナイトと同じ結晶構造をもつものが好ましい。
The present invention is described in detail below.
The phosphor for the vacuum ultraviolet ray excited light emitting device of the present invention has a general formula mM 1 O · nM 2 O · 2M 3 O 2 (wherein M 1 is one or more selected from the group consisting of Ca, Sr and Ba, M 2 is one or more selected from the group consisting of Mg and Zn, M 3 is one or more selected from the group consisting of Si and Ge, 0.5 ≦ m ≦ 3.5, 0.5 ≦ n ≦ 2. 5. However, when m = n = 1, M 1 is two or more selected from the group consisting of Ca, Sr and Ba, or Sr or Ba.) Is a mother crystal, and Eu and Mn are activators. One or more selected from the group is contained, and those having the same crystal structure as diopside, akermanite, and merwinite are preferable.
ディオプサイド（Ｄｉｏｐｓｉｄｅ、透輝石）と同型の結晶構造を有する場合の中でも、上記（１）の一般式においてｍ＝１およびｎ＝１の場合の一つである一般式（Ｍ4 1-aＥｕa）（Ｍ5 1-bＭｎb）Ｍ6 2Ｏ6（式中のＭ4はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａ、Ｍ5はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ6はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ａ≦０．５、０≦ｂ≦０．５、０＜ａ＋ｂ。）で表される組成を有する蛍光体が真空紫外線励起発光素子用として好ましい。
さらに、ディオプサイド（Ｄｉｏｐｓｉｄｅ、透輝石）と同型の結晶構造を有する場合の中でも、上記（１）の一般式においてｍ＝１およびｎ＝１の場合の一つでありＣａとＳｒを含む一般式Ｃａ1-c-dＳｒcＥｕdＭｇＳｉ2Ｏ6（０＜ｃ≦０．１、０＜ｄ≦０．１。）で表される組成を有する蛍光体がさらに好ましい。
Among the cases where the crystal structure has the same type as that of diopside (diopside), the general formula (M 4 1-a) is one of the cases where m = 1 and n = 1 in the general formula (1) above. Eu a ) (M 5 1-b Mn b ) M 6 2 O 6 (wherein M 4 is two or more selected from the group consisting of Ca, Sr and Ba, or Sr or Ba, and M 5 is Mg and Zn) least one selected from the group consisting of, M 6 is at least one element selected from the group consisting of Si and Ge, represented by 0 ≦ a ≦ 0.5,0 ≦ b ≦ 0.5,0 <a + b.) A phosphor having a composition is preferable for a vacuum ultraviolet ray excited light emitting device.
Further, among the cases where the crystal structure is the same type as that of diopside (diopside), it is one of the cases where m = 1 and n = 1 in the general formula of (1), and includes Ca and Sr. phosphor having a composition represented by the formula Ca 1-cd Sr c Eu d MgSi 2 O 6 (0 <c ≦ 0.1,0 <d ≦ 0.1.) is more preferred.
オケルマナイト（Ａｋｅｒｍａｎｉｔｅ、オケルマン石）と同じ結晶構造を有する場合の中でも、上記（１）の一般式においてｍ＝２およびｎ＝１の場合の一つである一般式（Ｍ7 1-eＥｕe）2（Ｍ8 1-fＭｎf）Ｍ9 2Ｏ7（式中のＭ7はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ8はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ9はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ｅ≦０．５、０≦ｆ≦０．５、０＜ｅ＋ｆ。）で表される組成を有する蛍光体が真空紫外線励起発光素子用として好ましい。さらに、前記一般式においてｆ＝０でＭ9がＳｉの場合の一般式（Ｍ10 1-gＥｕg）2Ｍ11Ｓｉ2Ｏ7（式中のＭ10はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ11はＭｇおよびＺｎからなる群から選ばれる１種以上、０．００１≦ｇ≦０．１）で表される
組成を有する蛍光体がさらに好ましい。
Among the cases where it has the same crystal structure as kermanite (Akermanite), the general formula (M 7 1-e Eu e ) which is one of the cases where m = 2 and n = 1 in the general formula ( 1 ) above 2 (M 8 1-f Mn f ) M 9 2 O 7 (wherein M 7 is one or more selected from the group consisting of Ca, Sr and Ba, and M 8 is 1 selected from the group consisting of Mg and Zn) A phosphor having a composition represented by the following formula: M 9 is one or more selected from the group consisting of Si and Ge, 0 ≦ e ≦ 0.5, 0 ≦ f ≦ 0.5, 0 <e + f. It is preferable for a vacuum ultraviolet excitation light emitting device. Further, a general formula (M 10 1-g Eu g ) 2 M 11 Si 2 O 7 (wherein M 10 is a group consisting of Ca, Sr and Ba) when f = 0 and M 9 is Si. more least one selected, M 11 is one or more members selected from the group consisting of Mg and Zn, the phosphor is more preferably a composition represented by 0.001 ≦ g ≦ 0.1).
また、オケルマナイトと同じ結晶構造を有する場合の中でも、上記（１）の一般式においてｍ＝１およびｎ＝２の場合の一つである一般式一般式（Ｍ12 1-hＥｕh）（Ｍ13 1-iＭｎi）2Ｍ14 2Ｏ7（式中のＭ12はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ13はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ14はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ｈ≦０．５、０≦ｉ≦０．５、０＜ｈ＋ｉ。）で表される組成を有する蛍光体も真空紫外線励起発光素子用として好ましい。 Further, among the cases where the crystal structure is the same as that of the akermanite, the general formula (M 12 1-h Eu h ) (M, which is one of the cases where m = 1 and n = 2 in the general formula (1) above. 13 1-i Mn i ) 2 M 14 2 O 7 (wherein M 12 is one or more selected from the group consisting of Ca, Sr and Ba, and M 13 is one or more selected from the group consisting of Mg and Zn) , M 14 is at least one selected from the group consisting of Si and Ge, and phosphors having a composition represented by 0 ≦ h ≦ 0.5, 0 ≦ i ≦ 0.5, 0 <h + i. It is preferable for an excitation light emitting device.
メルウィナイト（Ｍｅｒｗｉｎｉｔｅ）と同型の結晶構造を有する場合の中でも、上記（１）の一般式においてｍ＝３およびｎ＝１の場合の一つである、一般式（Ｍ15 1-jＥｕj）3（Ｍ16 1-kＭｎk）Ｍ17 2Ｏ8（式中のＭ15はＣａ、ＳｒおよびＢａからなる群より選ばれる１種以上、Ｍ16はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ17はＳｉおよびＧｅからなる群より選ばれた１種以上、０≦ｊ≦０．５、０≦ｋ≦０．５、０＜ｊ＋ｋ。）で表される組成を有する蛍光体が真空紫外線励起発光素子用として好ましい。
上記ディオプサイド、オケルマナイト、メルウィナイトと同じ結晶構造を持つ蛍光体のなかでも、ディオプサイド、メルウィナイトと同じ結晶構造を持つ蛍光体が好ましく、ディオプサイドと同じ結晶構造を持つ蛍光体がさらに好ましい。
Among the cases where the crystal structure has the same type as that of merwinite (Merwinite), the general formula (M 15 1-j Eu j ) 3 which is one of the cases where m = 3 and n = 1 in the general formula (1) above. (M 16 1-k Mn k ) M 17 2 O 8 (M 15 in the formula is one or more members selected from the group consisting of Ca, Sr and Ba, M 16 is one selected from the group consisting of Mg and Zn M 17 is a phosphor having a composition represented by one or more selected from the group consisting of Si and Ge, 0 ≦ j ≦ 0.5, 0 ≦ k ≦ 0.5, 0 <j + k.) It is preferable for a vacuum ultraviolet excitation light emitting device.
Among the phosphors having the same crystal structure as diopside, akermanite, and merwinite, phosphors having the same crystal structure as diopside and merwinite are preferable, and phosphors having the same crystal structure as diopside are more preferable. .
次に本発明の蛍光体の製造方法について説明する。
本発明の蛍光体を製造するための原料となるカルシウム源、ストロンチウム源、バリウム源としては、高純度（９９％以上）の水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解し酸化物になりうるものかまたは高純度（９９．９％以上）の酸化物が使用できる。
マグネシウム源、亜鉛源となる原料としては、高純度（９９％以上）の水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解し酸化物になりうるものかまたは高純度（９９％以上）の酸化物が使用できる。
ケイ素源、ゲルマニウム源となるとなる原料としては、高純度（９９％以上）の水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解し酸化物になりうるものかまたは高純度（９９％以上）の酸化物が使用できる。
Next, the method for producing the phosphor of the present invention will be described.
Calcium source, strontium source, and barium source that are raw materials for producing the phosphor of the present invention include high-purity (99% or more) hydroxide, carbonate, nitrate, halide, oxalate, etc. at high temperatures. An oxide that can be decomposed into an oxide or a high purity (99.9% or more) can be used.
The raw materials used as the magnesium source and zinc source include high-purity (99% or more) hydroxides, carbonates, nitrates, halides, oxalates, etc. that can decompose into high-temperature oxides or become high-purity ( 99% or more of the oxide can be used.
The raw material to be a silicon source or germanium source is a high-purity (99% or more) hydroxide, carbonate, nitrate, halide, oxalate, or the like that can be decomposed into an oxide at a high temperature or high purity. (99% or more) oxide can be used.
付活剤となるユーロピウム、マンガンを含む原料としては、高純度（９９％以上）の水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解し酸化物になりうるものかまたは高純度（９９％以上）の酸化物が使用できる。 As raw materials containing europium and manganese as activators, high purity (over 99%) hydroxides, carbonates, nitrates, halides, oxalates, etc. that can decompose at high temperatures to become oxides or High purity (99% or more) oxide can be used.
本発明の蛍光体の製造方法は特に限定されるものではなく、例えば、上記それぞれの原料を混合し焼成することにより製造することができる。好ましい組成の一つである一般式（Ｍ4 1-aＥｕa）（Ｍ5 1-bＭｎb）Ｍ6 2Ｏ6（式中のＭ4はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上またはＳｒまたはＢａ、Ｍ5はＭｇおよびＺｎからなる群より選ばれる１種以上、Ｍ6はＳｉおよびＧｅからなる群より選ばれる１種以上、０≦ａ≦０．５、０≦ｂ≦０．５、０＜ａ＋ｂ。）で表される組成を有する蛍光体は、上記原料を所定の組成となるように秤量し配合し、混合して焼成することにより製造することができる。これらの原料の混合には通常工業的に用いられているボールミル、Ｖ型混合機、または攪拌装置等を用いることができる。 The method for producing the phosphor of the present invention is not particularly limited. For example, the phosphor can be produced by mixing and firing the respective raw materials. One of the preferred compositions is the general formula (M 4 1-a Eu a ) (M 5 1-b Mn b ) M 6 2 O 6 (wherein M 4 is selected from the group consisting of Ca, Sr and Ba) 2 or more, or Sr or Ba, M 5 is one or more selected from the group consisting of Mg and Zn, M 6 is one or more selected from the group consisting of Si and Ge, 0 ≦ a ≦ 0.5, 0 ≦ A phosphor having a composition represented by b ≦ 0.5 and 0 <a + b.) can be manufactured by weighing, blending, mixing and firing the above raw materials so as to have a predetermined composition. For mixing these raw materials, a ball mill, a V-type mixer, a stirrer or the like which is usually used in industry can be used.
混合した後、例えば１０００℃から１５００℃の温度範囲にて１〜１００時間焼成することにより本発明の蛍光体が得られる。原料に水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解し酸化物になりうるものが使用した場合、本焼成の前に、例えば６００℃から９００℃の温度範囲にて仮焼することも可能である。
焼成雰囲気としては、特に限定されるものではないが、例えば水素を０．１〜１０体積％含む窒素やアルゴン等の還元性雰囲気で焼成することが好ましい。また仮焼の雰囲気は大気雰囲気、還元性雰囲気のいずれでもよい。また、反応を促進するために、適量のフラックスを添加してもよい。
After mixing, for example, the phosphor of the present invention is obtained by firing for 1 to 100 hours in a temperature range of 1000 ° C. to 1500 ° C., for example. When materials that can be decomposed into oxides at high temperatures such as hydroxide, carbonate, nitrate, halide, oxalate, etc. are used as raw materials, for example, in a temperature range of 600 ° C. to 900 ° C. before the main firing. It is also possible to calcine.
The firing atmosphere is not particularly limited. For example, firing is preferably performed in a reducing atmosphere such as nitrogen or argon containing 0.1 to 10% by volume of hydrogen. The calcination atmosphere may be either an air atmosphere or a reducing atmosphere. In order to accelerate the reaction, an appropriate amount of flux may be added.
さらに、上記方法にて得られる蛍光体を、例えばボールミル、ジェットミル等を用いて粉砕することができる。また、洗浄、分級することができる。得られる蛍光体の結晶性を高めるために、再焼成を行うこともできる。 Furthermore, the phosphor obtained by the above method can be pulverized using, for example, a ball mill, a jet mill or the like. It can also be washed and classified. In order to increase the crystallinity of the obtained phosphor, re-baking can be performed.
以上のようにして得られる本発明の蛍光体は真空紫外線励起によって高い輝度が得られ、プラズマ暴露による輝度低下が少ない。さらに、ＰＤＰおよび希ガスランプの製造においては、蛍光体にバインダーを加えて溶媒に分散させ、発光部に塗布して５００℃程度で熱処理してバインダーを除去することにより蛍光体を設置する工程が一般的であるが、本発明の蛍光体は、この熱処理工程における輝度低下も少ない。従って、本発明の蛍光体をＰＤＰおよび希ガスランプなどの真空紫外線励起発光素子用に用いた場合、高輝度で寿命の長いＰＤＰおよび希ガスランプが実現できるので、真空紫外線励起発光素子用として好適である。 The phosphor of the present invention obtained as described above can obtain high luminance by excitation with vacuum ultraviolet rays, and has little reduction in luminance due to plasma exposure. Furthermore, in the production of PDP and rare gas lamp, there is a step of installing the phosphor by adding a binder to the phosphor and dispersing it in a solvent, applying it to the light emitting part, and heat-treating at about 500 ° C. to remove the binder. Although generally, the phosphor of the present invention is less susceptible to luminance reduction in this heat treatment step. Therefore, when the phosphor of the present invention is used for a vacuum ultraviolet ray excited light emitting device such as a PDP and a rare gas lamp, a high-luminance and long life PDP and a rare gas lamp can be realized. It is.
本発明の蛍光体は真空紫外域以外の紫外線、Ｘ線および電子線などによっても励起可能であり、真空紫外域以外の紫外線、Ｘ線および電子線を励起源とした素子にも用いることができる。 The phosphor of the present invention can be excited by ultraviolet rays other than the vacuum ultraviolet region, X-rays, and electron beams, and can also be used for devices using ultraviolet rays other than the vacuum ultraviolet region, X-rays, and electron beams as excitation sources. .
次に、本発明を実施例によりさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
実施例１
炭酸カルシウム（和光純薬工業（株）製）ＣａＣＯ3、炭酸ストロンチウム（和光純薬工業（株）製）ＳｒＣＯ3、酸化ユーロピウム（信越化学工業（株）製）Ｅｕ2Ｏ3、塩基性炭酸マグネシウム（和光純薬工業（株）製）（ＭｇＣＯ3）4Ｍｇ（ＯＨ）2・５Ｈ2Ｏ、酸化珪素（和光純薬工業（株）製）ＳｉＯ2各原料をＣａＣＯ3：ＳｒＣＯ3：Ｅｕ2Ｏ3：（ＭｇＣＯ3）4Ｍｇ（ＯＨ）2・５Ｈ2Ｏ：ＳｉＯ2のモル比が０．９２１５：０．０４８５：０．０１５：０．２：２になるように配合し混合した後、２体積％Ｈ2含有Ａｒ雰囲気中で１２００℃の温度で２時間焼成、解砕後、再度２体積％Ｈ2含有Ａｒ雰囲気中で１２００℃の温度で２時間焼成した。このようにして、組成式がＣａ0.9215Ｓｒ0.0485Ｅｕ0.03ＭｇＳｉ2Ｏ6で表される蛍光体を得た。この蛍光体に、６．７Ｐａ（５×１０-2Ｔｏｒｒ）以下の真空槽内で、得られた蛍光体にエキシマ１４６ｎｍランプ（ウシオ電機社製、Ｈ００１２型）を用いて紫外線を照射したところ、青色の発光を示し、輝度は２４ｃｄ／ｍ2を示した。
Example 1
Calcium carbonate (Wako Pure Chemical Industries, Ltd.) CaCO 3 , Strontium carbonate (Wako Pure Chemical Industries, Ltd.) SrCO 3 , Europium oxide (Shin-Etsu Chemical Co., Ltd.) Eu 2 O 3 , basic magnesium carbonate (Made by Wako Pure Chemical Industries, Ltd.) (MgCO 3 ) 4 Mg (OH) 2 .5H 2 O, silicon oxide (manufactured by Wako Pure Chemical Industries, Ltd.) SiO 2 As raw materials, CaCO 3 : SrCO 3 : Eu 2 After mixing and mixing so that the molar ratio of O 3 : (MgCO 3 ) 4 Mg (OH) 2 .5H 2 O: SiO 2 is 0.9215: 0.0485: 0.015: 0.2: 2. After calcination for 2 hours at a temperature of 1200 ° C. in an Ar atmosphere containing 2% by volume of H 2 , pulverization was performed, and again for 2 hours at a temperature of 1200 ° C. in an Ar atmosphere containing 2% by volume of H 2 . In this manner, a phosphor having a composition formula represented by Ca 0.9215 Sr 0.0485 Eu 0.03 MgSi 2 O 6 was obtained. When this phosphor was irradiated with ultraviolet rays using an excimer 146 nm lamp (Hushio Corp., H0012 type) in a vacuum chamber of 6.7 Pa (5 × 10 −2 Torr) or less, Blue light was emitted, and the luminance was 24 cd / m 2 .
得られた蛍光体を、空気中で５００℃、３０分間熱処理を行った。蛍光体を取出して輝度を測定した結果、熱処理前に比較して輝度は全く低下しなかった。 The obtained phosphor was heat-treated in air at 500 ° C. for 30 minutes. As a result of taking out the phosphor and measuring the luminance, the luminance was not lowered at all as compared with that before the heat treatment.
得られた熱処理前の蛍光体を、圧力が１３．２Ｐａで５体積％Ｘｅ−９５体積％Ｎｅの組成の雰囲気中に設置し、１０Ｗのプラズマに３０分間、ついで５０Ｗのプラズマに１５分間曝露させた。蛍光体を取出して輝度を測定した結果、プラズマ曝露前に比較して輝度は全く低下しなかった。 The obtained phosphor before heat treatment was placed in an atmosphere having a composition of 5 volume% Xe-95 volume% Ne at a pressure of 13.2 Pa, and exposed to 10 W plasma for 30 minutes and then exposed to 50 W plasma for 15 minutes. It was. As a result of taking out the phosphor and measuring the luminance, the luminance was not lowered at all as compared with that before the plasma exposure.
得られた熱処理、プラズマ暴露前の蛍光体を、空気中で５００℃、３０分間熱処理を行った。次いで、圧力が１３．２Ｐａで５体積％Ｘｅ−９５体積％Ｎｅの組成の雰囲気中に設置し、１０Ｗのプラズマに３０分間、ついで５０Ｗのプラズマに１５分間曝露させた。蛍光体を取出して輝度を測定した結果、熱処理、プラズマ曝露前に比較して輝度の低下は４％であった。 The obtained phosphor before heat treatment and plasma exposure was heat-treated in air at 500 ° C. for 30 minutes. Next, it was placed in an atmosphere having a composition of 5 volume% Xe-95 volume% Ne at a pressure of 13.2 Pa, and exposed to 10 W plasma for 30 minutes and then exposed to 50 W plasma for 15 minutes. As a result of taking out the phosphor and measuring the luminance, the reduction in luminance was 4% as compared with that before the heat treatment and plasma exposure.
実施例２
炭酸ストロンチウム（和光純薬工業（株）製）ＳｒＣＯ3、炭酸バリウム（和光純薬工業（株）製）ＢａＣＯ3、酸化ユーロピウム（信越化学工業（株）製）Ｅｕ2Ｏ3、塩基性炭酸マグネシウム（和光純薬工業（株）製）（ＭｇＣＯ3）4Ｍｇ（ＯＨ）2・５Ｈ2Ｏ、酸化珪素（和光純薬工業（株）製）ＳｉＯ2各原料をＳｒＣＯ3：ＢａＣＯ3：Ｅｕ2Ｏ3：（ＭｇＣＯ3）4Ｍｇ（ＯＨ）2・５Ｈ2Ｏ：ＳｉＯ2のモル比が２．２８：０．５７：０．０７５：０．２：２になるように配合、混合した後、２体積％Ｈ2含有Ａｒ雰囲気中で１２００℃の温度で２時間焼成した。このようにして、組成式がＳｒ2.28Ｂａ0.57Ｅｕ0.15ＭｇＳｉ2Ｏ8で表される蛍光体を得た。この蛍光体に、６．７Ｐａ（５×１０-2Ｔｏｒｒ）以下の真空槽内で、得られた蛍光体にエキシマ１４６ｎｍランプ（ウシオ電機社製、Ｈ００１２型）を用いて紫外線を照射したところ、青色の発光を示し、輝度は３０ｃｄ／ｍ2を示した。
Example 2
Strontium carbonate (Wako Pure Chemical Industries, Ltd.) SrCO 3 , Barium carbonate (Wako Pure Chemical Industries, Ltd.) BaCO 3 , Europium oxide (Shin-Etsu Chemical Co., Ltd.) Eu 2 O 3 , basic magnesium carbonate (Made by Wako Pure Chemical Industries, Ltd.) (MgCO 3 ) 4 Mg (OH) 2 .5H 2 O, silicon oxide (produced by Wako Pure Chemical Industries, Ltd.) SiO 2 As raw materials, SrCO 3 : BaCO 3 : Eu 2 After mixing and mixing so that the molar ratio of O 3 : (MgCO 3 ) 4 Mg (OH) 2 .5H 2 O: SiO 2 is 2.28: 0.57: 0.075: 0.2: 2. Firing was performed at a temperature of 1200 ° C. for 2 hours in an Ar atmosphere containing 2% by volume of H 2 . In this way, a phosphor having a composition formula represented by Sr 2.28 Ba 0.57 Eu 0.15 MgSi 2 O 8 was obtained. When this phosphor was irradiated with ultraviolet rays using an excimer 146 nm lamp (Hushio Corp., H0012 type) in a vacuum chamber of 6.7 Pa (5 × 10 −2 Torr) or less, Blue light was emitted, and the luminance was 30 cd / m 2 .
実施例３
炭酸バリウム（関東化学（株）製）ＢａＣＯ3、酸化ユーロピウム（信越化学工業（株）製）Ｅｕ2Ｏ3、酸化マグネシウム（関東化学（株）製）ＭｇＯ、酸化珪素（（株）高純度化学研究所製）ＳｉＯ2各原料をＢａＣＯ3：Ｅｕ2Ｏ3：ＭｇＯ：ＳｉＯ2のモル比が１．９８：０．０１：１：２になるように配合し、また、生成物１モルに対してＢ2Ｏ3をフラックスとして０．１モル添加し、アセトン中、乳鉢で十分湿式混合し、乾燥した。得られた混合原料をステンレス製の金型に入れ、４０ＭＰａの圧力で加圧して直径１５ｍｍ×厚さ３ｍｍの円形ペレットに成形した。得られたペレットをアルミナ坩堝に入れ、５体積％Ｈ2−９５体積％Ａｒ雰囲気中で１２００℃で３時間焼成した。このようにして、組成式がＢａ1.98Ｅｕ0.02ＭｇＳｉ2Ｏ7で表される蛍光体を得た。この蛍光体に、６．７Ｐａ（５×１０-2Ｔｏｒｒ）以下の真空槽内で、得られた蛍光体にエキシマ１４６ｎｍランプ（ウシオ電機社製、Ｈ００１２型）を用いて紫外線を照射したところ、緑色の発光を示し、輝度は９５ｃｄ／ｍ2を示した。
Example 3
Barium carbonate (manufactured by Kanto Chemical Co., Ltd.) BaCO 3 , europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.) Eu 2 O 3 , magnesium oxide (manufactured by Kanto Chemical Co., Ltd.) MgO, silicon oxide (Co., Ltd.) (Made by Laboratories) Each SiO 2 raw material was blended so that the molar ratio of BaCO 3 : Eu 2 O 3 : MgO: SiO 2 was 1.98: 0.01: 1: 2, and 1 mol of product was added. On the other hand, 0.1 mol of B 2 O 3 was added as a flux, sufficiently wet-mixed in acetone in a mortar, and dried. The obtained mixed raw material was put into a stainless steel mold and pressed at a pressure of 40 MPa to form a circular pellet having a diameter of 15 mm and a thickness of 3 mm. The obtained pellets were put in an alumina crucible and fired at 1200 ° C. for 3 hours in an atmosphere of 5 vol% H 2 -95 vol%. In this way, a phosphor having a composition formula Ba 1.98 Eu 0.02 MgSi 2 O 7 was obtained. When this phosphor was irradiated with ultraviolet rays using an excimer 146 nm lamp (Hushio Corp., H0012 type) in a vacuum chamber of 6.7 Pa (5 × 10 −2 Torr) or less, Green light was emitted, and the luminance was 95 cd / m 2 .
実施例４
（Ｓｒ0.99Ｅｕ0.01）2ＭｇＳｉ2Ｏ7を製造するにあたり、出発原料として、炭酸ストロンチウム（関東化学（株）製）ＳｒＣＯ3、酸化ユーロピウム（信越化学工業（株）製）Ｅｕ2Ｏ3、酸化マグネシウム（関東化学（株）製）ＭｇＯ、酸化珪素（（株）高純度化学研究所製）ＳｉＯ2を用いた。これら原料をＳｒＣＯ3：Ｅｕ2Ｏ3：ＭｇＯ：ＳｉＯ2のモル比が１．９８：０．０１：１：２になるように配合し、また、生成物（Ｓｒ0.99Ｅｕ0.01）2ＭｇＳｉ2Ｏ7１モルに対してＢ2Ｏ3をフラックスとして０．１モル添加し、アセトン中、乳鉢で十分湿式混合し、乾燥した。得られた混合原料をステンレス製の金型に入れ、４０ＭＰａの圧力で加圧して直径１５ｍｍ×厚さ３ｍｍの円形ペレットに成形した。得られたペレットをアルミナ坩堝に入れ、５％Ｈ2−９５％Ａｒ雰囲気中で１２００℃で３時間焼成した。焼成後得られた試料に、波長２５４ｎｍまたは３６５ｎｍの紫外線を照射すると、いずれの場合も高輝度の水色発光を示した。６．７Ｐａ（５×１０-2Ｔｏｒｒ）以下の真空槽内でエキシマ１４６ｎｍランプ（ウシオ電機社製）を用いて真空紫外線を照射したところ、水色の発光を示し、輝度は２５ｃｄ／ｃｍ2を示した。
Example 4
In producing (Sr 0.99 Eu 0.01 ) 2 MgSi 2 O 7 , strontium carbonate (manufactured by Kanto Chemical Co.) SrCO 3 , europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.) Eu 2 O 3 , oxidation Magnesium (manufactured by Kanto Chemical Co., Inc.) MgO and silicon oxide (manufactured by Kojundo Chemical Laboratory Co., Ltd.) SiO 2 were used. These raw materials are blended so that the molar ratio of SrCO 3 : Eu 2 O 3 : MgO: SiO 2 is 1.98: 0.01: 1: 2, and the product (Sr 0.99 Eu 0.01 ) 2 MgSi 2 0.1 mol of B 2 O 3 was added as a flux to 1 mol of O 7 , sufficiently wet mixed in a mortar in acetone, and dried. The obtained mixed raw material was put into a stainless steel mold and pressed at a pressure of 40 MPa to form a circular pellet having a diameter of 15 mm and a thickness of 3 mm. The obtained pellets were put in an alumina crucible and fired at 1200 ° C. for 3 hours in a 5% H 2 -95% Ar atmosphere. When the sample obtained after firing was irradiated with ultraviolet light having a wavelength of 254 nm or 365 nm, in all cases, light emission with high luminance was exhibited. When irradiated with vacuum ultraviolet rays using an excimer 146 nm lamp (made by USHIO INC.) In a vacuum chamber of 6.7 Pa (5 × 10 −2 Torr) or less, it shows light blue light emission and luminance shows 25 cd / cm 2 . It was.
実施例５
（Ｓｒ0.99Ｅｕ0.01）2ＺｎＳｉ2Ｏ7を製造するにあたり、出発原料として、炭酸ストロンチウムＳｒＣＯ3、酸化ユーロピウムＥｕ2Ｏ3、酸化亜鉛ＺｎＯ、酸化珪素ＳｉＯ2を用いた。これら原料をＳｒＣＯ3：Ｅｕ2Ｏ3：ＺｎＯ：ＳｉＯ2のモル比が１．９８：０．０１：１：２になるように配合し、フラックスとして生成物（Ｓｒ0.99Ｅｕ0.01）2ＺｎＳｉ2Ｏ7１モルに対してＢ2Ｏ3を０．１モル添加し、アセトン中で乳鉢で十分湿式混合し、乾燥した。得られた混合原料をステンレス製の金型に入れ、４０ＭＰａの圧力で加圧して直径１５ｍｍ×厚さ３ｍｍの円形ペレットに成形した。得られたペレットをアルミナ坩堝に入れ、５％Ｈ2−９５％Ａｒ雰囲気中で１２００℃で３時間焼成した。焼成後得られた試料につき、２５４ｎｍもしくは３６５ｎｍの紫外線にて励起するといずれも高輝度の青緑色発光を示した。６．７Ｐａ（５×１０-2Ｔｏｒｒ）以下の真空槽内で得られた蛍光体にエキシマ１４６ｎｍランプ（ウシオ電機社製）を用いて真空紫外線を照射したところ、青緑色の発光を示した。
Example 5
In producing (Sr 0.99 Eu 0.01 ) 2 ZnSi 2 O 7 , strontium carbonate SrCO 3 , europium oxide Eu 2 O 3 , zinc oxide ZnO, and silicon oxide SiO 2 were used as starting materials. These raw materials are blended so that the molar ratio of SrCO 3 : Eu 2 O 3 : ZnO: SiO 2 is 1.98: 0.01: 1: 2, and the product (Sr 0.99 Eu 0.01 ) 2 ZnSi 2 is used as a flux. 0.1 mol of B 2 O 3 was added to 1 mol of O 7 , thoroughly wet mixed in a mortar in acetone, and dried. The obtained mixed raw material was put into a stainless steel mold and pressed at a pressure of 40 MPa to form a circular pellet having a diameter of 15 mm and a thickness of 3 mm. The obtained pellets were put in an alumina crucible and fired at 1200 ° C. for 3 hours in a 5% H 2 -95% Ar atmosphere. When the samples obtained after firing were excited with ultraviolet rays of 254 nm or 365 nm, both showed high brightness blue-green light emission. When a phosphor obtained in a vacuum chamber of 6.7 Pa (5 × 10 −2 Torr) or less was irradiated with a vacuum ultraviolet ray using an excimer 146 nm lamp (manufactured by USHIO INC.), Blue-green light was emitted.
比較例１
炭酸カルシウム（和光純薬工業（株）製）ＣａＣＯ3、酸化ユーロピウム（信越化学工業（株）製）Ｅｕ2Ｏ3、塩基性炭酸マグネシウム（和光純薬工業（株）製）（ＭｇＣＯ3）4Ｍｇ（ＯＨ）2・５Ｈ2Ｏ）、酸化珪素（和光純薬工業（株）製）ＳｉＯ2各原料をＣａＣＯ3：Ｅｕ2Ｏ3：（ＭｇＣＯ3）4Ｍｇ（ＯＨ）2・５Ｈ2Ｏ）：ＳｉＯ2のモル比が０．９５：０．０２５：０．２：２になるように配合、混合した後、２体積％Ｈ2含有Ａｒ雰囲気中で１２００℃の温度で２時間焼成した。このようにして、組成式がＣａ0.95Ｅｕ0.05ＭｇＳｉ2Ｏ6で表される蛍光体を得た。この蛍光体に、６．７Ｐａ（５×１０-2Ｔｏｒｒ）以下の真空槽内で、得られた蛍光体にエキシマ１４６ｎｍランプ（ウシオ電機社製、Ｈ００１２型）を用いて紫外線を照射したところ、青色の発光を示し、輝度は１２ｃｄ／ｍ2を示した。
Comparative Example 1
Calcium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) CaCO 3 , europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd.) Eu 2 O 3 , basic magnesium carbonate (manufactured by Wako Pure Chemical Industries, Ltd.) (MgCO 3 ) 4 Mg (OH) 2 .5H 2 O), silicon oxide (manufactured by Wako Pure Chemical Industries, Ltd.), SiO 2 raw materials, CaCO 3 : Eu 2 O 3 : (MgCO 3 ) 4 Mg (OH) 2 .5H 2 O ): SiO 2 was blended so that the molar ratio was 0.95: 0.025: 0.2: 2, and then baked at a temperature of 1200 ° C. for 2 hours in an Ar atmosphere containing 2% by volume of H 2 . . In this way, a phosphor having a composition formula represented by Ca 0.95 Eu 0.05 MgSi 2 O 6 was obtained. When this phosphor was irradiated with ultraviolet rays using an excimer 146 nm lamp (Hushio Corp., H0012 type) in a vacuum chamber of 6.7 Pa (5 × 10 −2 Torr) or less, Blue light was emitted, and the luminance was 12 cd / m 2 .
比較例２
市販の青色発光蛍光体ＢａＭｇＡｌ10Ｏ17：Ｅｕを、空気中で５００℃、３０分間熱処理を行った。蛍光体を取出して輝度を測定した結果、熱処理前に比較して輝度が１％低下した。
Comparative Example 2
A commercially available blue-emitting phosphor BaMgAl 10 O 17 : Eu was heat-treated in air at 500 ° C. for 30 minutes. As a result of taking out the phosphor and measuring the luminance, the luminance was reduced by 1% compared to before the heat treatment.
上記市販の青色発光蛍光体を、圧力が１３．２Ｐａで５体積％Ｘｅ−９５体積％Ｎｅの組成の雰囲気中に設置し、１０Ｗのプラズマに３０分間、ついで５０Ｗのプラズマに１５分間曝露させた。蛍光体を取出して輝度を測定した結果、プラズマ曝露前に比較して輝度が２５％低下した。 The commercially available blue light-emitting phosphor was placed in an atmosphere having a composition of 5 volume% Xe-95 volume% Ne at a pressure of 13.2 Pa, and exposed to 10 W plasma for 30 minutes and then exposed to 50 W plasma for 15 minutes. . As a result of taking out the phosphor and measuring the luminance, the luminance was reduced by 25% compared to before the plasma exposure.
上記市販の青色発光蛍光体を、空気中で５００℃、３０分間熱処理を行った。次いで、圧力が１３．２Ｐａで５体積％Ｘｅ−９５体積％Ｎｅの組成の雰囲気中に設置し、１０Ｗのプラズマに３０分間、ついで５０Ｗのプラズマに１５分間曝露させた。蛍光体を取出して輝度を測定した結果、熱処理、プラズマ曝露前に比較して輝度が２８％低下した。 The commercially available blue light-emitting phosphor was heat-treated in air at 500 ° C. for 30 minutes. Next, it was placed in an atmosphere having a composition of 5 volume% Xe-95 volume% Ne at a pressure of 13.2 Pa, and exposed to 10 W plasma for 30 minutes and then exposed to 50 W plasma for 15 minutes. As a result of taking out the phosphor and measuring the luminance, the luminance was reduced by 28% compared with that before the heat treatment and the plasma exposure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2009102502A (en) * | 2007-10-23 | 2009-05-14 | Hitachi Displays Ltd | Fluorescent lamp and liquid crystal display device using the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3544481A (en) * | 1967-12-01 | 1970-12-01 | Sylvania Electric Prod | Europium-activated alkaline earth orthosilicate phosphor |
| JPS4837715B1 (en) * | 1967-10-26 | 1973-11-13 | ||
| JPS528994A (en) * | 1975-07-11 | 1977-01-24 | Hitachi Ltd | Luminous unit |
| JPH01167394A (en) * | 1987-12-23 | 1989-07-03 | Hitachi Ltd | phosphor |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4837715B1 (en) * | 1967-10-26 | 1973-11-13 | ||
| US3544481A (en) * | 1967-12-01 | 1970-12-01 | Sylvania Electric Prod | Europium-activated alkaline earth orthosilicate phosphor |
| JPS528994A (en) * | 1975-07-11 | 1977-01-24 | Hitachi Ltd | Luminous unit |
| JPH01167394A (en) * | 1987-12-23 | 1989-07-03 | Hitachi Ltd | phosphor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009102502A (en) * | 2007-10-23 | 2009-05-14 | Hitachi Displays Ltd | Fluorescent lamp and liquid crystal display device using the same |
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