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JP2006265377A - Fluorophor for electron beam excitation light emitting devices - Google Patents

Fluorophor for electron beam excitation light emitting devices Download PDF

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Publication number
JP2006265377A
JP2006265377A JP2005085668A JP2005085668A JP2006265377A JP 2006265377 A JP2006265377 A JP 2006265377A JP 2005085668 A JP2005085668 A JP 2005085668A JP 2005085668 A JP2005085668 A JP 2005085668A JP 2006265377 A JP2006265377 A JP 2006265377A
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phosphor
electron beam
manufactured
light emitting
formula
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Yoshiko Nakamura
善子 中村
Toshinori Isobe
敏典 磯部
Satoshi Kuze
智 久世
Susumu Miyazaki
進 宮崎
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Priority to JP2005085668A priority Critical patent/JP2006265377A/en
Priority to TW095109463A priority patent/TWI398505B/en
Priority to US11/909,090 priority patent/US20100127612A1/en
Priority to KR1020077024040A priority patent/KR20070113301A/en
Priority to PCT/JP2006/306059 priority patent/WO2006101222A1/en
Publication of JP2006265377A publication Critical patent/JP2006265377A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/77342—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
    • C09K11/7702—Chalogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7701—Chalogenides
    • C09K11/7703—Chalogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/77062—Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7707—Germanates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7729—Chalcogenides
    • C09K11/7731—Chalcogenides with alkaline earth metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J11/00—Gas-filled discharge tubes with alternating current induction of the discharge, e.g. alternating current plasma display panels [AC-PDP]; Gas-filled discharge tubes without any main electrode inside the vessel; Gas-filled discharge tubes with at least one main electrode outside the vessel
    • H01J11/20—Constructional details
    • H01J11/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J11/42—Fluorescent layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J61/00—Gas-discharge or vapour-discharge lamps
    • H01J61/02—Details
    • H01J61/38—Devices for influencing the colour or wavelength of the light
    • H01J61/42—Devices for influencing the colour or wavelength of the light by transforming the wavelength of the light by luminescence
    • H01J61/44—Devices characterised by the luminescent material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
    • H01J2211/20—Constructional details
    • H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
    • H01J2211/42—Fluorescent layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2329/00—Electron emission display panels, e.g. field emission display panels
    • H01J2329/18—Luminescent screens
    • H01J2329/20—Luminescent screens characterised by the luminescent material

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Luminescent Compositions (AREA)
  • Cathode-Ray Tubes And Fluorescent Screens For Display (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fluorophor for an electron beam excitation light emitting device showing higher luminance. <P>SOLUTION: This electron beam excitation light emitting device contains at least Ln as an activator (Ln is at least an element selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Mn) in a compound represented by the formula: M<SP>1</SP>O-mM<SP>2</SP>O-nM<SP>3</SP>O<SB>2</SB>(wherein M<SP>1</SP>is not less than two elements selected from the group consisting of Ca, Sr, and Ba, or Sr or Ba, M<SP>2</SP>is Mg and/or Zn, and M<SP>3</SP>is at least an element selected from the group consisting of Si, Ge and Zr; m is a value in the range of not smaller than 0.8 but not greater than 1.2, n is a value in the range of not smaller than 1.6 but not greater than 2.4). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明は、蛍光体に関する。さらに詳しくは電子線励起発光素子用蛍光体に関する。   The present invention relates to a phosphor. More specifically, the present invention relates to a phosphor for an electron beam excited light emitting device.

蛍光体は、ブラウン管（以下「ＣＲＴ」という。）、フィールドエミッションディスプレイ（以下「ＦＥＤ」という。）、表面電界ディスプレイ（以下「ＳＥＤ」という。）、蛍光表示管（以下「ＶＦＤ」という。）等の電子線励起発光素子に用いられている。電子線励起発光素子には、蛍光体の励起源として、電子線が用いられている。電子線励起発光素子用蛍光体としては、例えば、ＣａＭｇＳｉ2Ｏ6：Ｅｕが提案されている（例えば、非特許文献１参照。）。 The phosphor is a cathode ray tube (hereinafter referred to as “CRT”), a field emission display (hereinafter referred to as “FED”), a surface electric field display (hereinafter referred to as “SED”), a fluorescent display tube (hereinafter referred to as “VFD”), or the like. It is used for the electron beam excitation light emitting element. In the electron beam excitation light emitting element, an electron beam is used as an excitation source of a phosphor. For example, CaMgSi 2 O 6 : Eu has been proposed as a phosphor for an electron beam-excited light emitting device (see, for example, Non-Patent Document 1).

「Ｅｘｔｅｎｄｅｄ Ａｂｓｔｒａｃｔ ｏｆ ｔｈｅ Ｆｉｆｔｈ Ｉｎｔｅｒｎａｔｉｏｎａｌ Ｃｏｎｆｅｒｅｎｃｅ ｏｎ ｔｈｅ Ｓｃｉｅｎｃｅ ａｎｄ Ｔｅｃｈｎｏｌｏｇｙ ｏｆ Ｄｉｓｐｌａｙ Ｐｈｏｓｐｈｏｒｓ．（１９９９）」ｐ．３１７−ｐ．３２０“Extended Abstract of the First International Conference on the Science and Technology of Display Phosphors. (1999)” p. 317-p. 320

しかしながら、従来の電子線励起発光素子用蛍光体は輝度が十分ではなかった。本発明の目的は、より高い輝度を示す電子線励起発光素子用蛍光体を提供することにある。   However, conventional phosphors for electron beam excited light emitting devices have not been sufficiently bright. The objective of this invention is providing the fluorescent substance for electron beam excitation light emitting elements which shows higher brightness | luminance.

本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、本発明を完成するに到った。   As a result of intensive studies to solve the above problems, the present inventors have completed the present invention.

すなわち本発明は、下記の蛍光体および発光素子を提供するものである。
＜１＞式Ｍ1Ｏ・ｍＭ2Ｏ・ｎＭ3Ｏ2（式中のＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上の元素またはＳｒまたはＢａであり、Ｍ2はＭｇおよび／またはＺｎであり、Ｍ3はＳｉ、ＧｅおよびＺｒからなる群より選ばれる１種以上の元素であり、ｍは０．８以上１．２以下の範囲の値であり、ｎは１．６以上２．４以下の範囲の値である。）で表される化合物に、少なくとも付活剤としてＬｎ（ただしＬｎはＣｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＭｎからなる群より選ばれる１種以上の元素である。）が含有されてなることを特徴とする電子線励起発光素子用蛍光体。
＜２＞ディオプサイド（Ｄｉｏｐｓｉｄｅ、透輝石）と同型の結晶構造を有する前記の蛍光体。
＜３＞式（Ｍ1 1-aＥｕa）Ｍ2Ｍ3 2Ｏ6（式中のＭ1、Ｍ2およびＭ3は前記と同じ意味を有し、ａは０を超え０．２以下の範囲の値である。）で表される化合物から実質的になる前記いずれかに記載の蛍光体。
＜４＞式Ｃａ1-b-cＳｒbＥｕcＭｇＳｉ2Ｏ6（ただし、式中ｂは０．０５以上１未満の範囲の値であり、ｃは０を超え０．２以下の範囲の値である。）で表される化合物から実質的になる前記いずれかに記載の蛍光体。
＜５＞前記いずれかに記載の蛍光体を用いてなることを特徴とする電子線励起発光素子。
＜６＞蛍光体の励起源が低速電子線である前記の電子線励起発光素子。
＜７＞電子線励起発光素子がフィールドエミッションディスプレイであることを特徴とする前記＜１＞〜＜４＞のいずれかに記載の蛍光体。
＜８＞電子線励起発光素子が表面電界ディスプレイであることを特徴とする前記＜１＞〜＜４＞のいずれかに記載の蛍光体。
＜９＞前記＜７＞記載の蛍光体を含有してなるフィールドエミッションディスプレイ。
＜１０＞前記＜８＞記載の蛍光体を含有してなる表面電界ディスプレイ。 That is, the present invention provides the following phosphor and light emitting element.
<1> Formula M 1 O · mM 2 O · nM 3 O 2 (wherein M 1 is two or more elements selected from the group consisting of Ca, Sr and Ba, or Sr or Ba, and M 2 is Mg And / or Zn, M 3 is one or more elements selected from the group consisting of Si, Ge and Zr, m is a value in the range of 0.8 to 1.2, and n is 1. 6 to 2.4), at least Ln as an activator (where Ln is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho) And at least one element selected from the group consisting of Er, Tm, Yb, and Mn.).
<2> The phosphor having the same crystal structure as that of diopside.
<3> Formula (M 1 1 -a Eu a ) M 2 M 3 2 O 6 (wherein M 1 , M 2 and M 3 have the same meaning as described above, and a exceeds 0 and is 0.2 or less. The phosphor according to any one of the above, substantially consisting of a compound represented by:
<4> Formula Ca 1-bc Sr b Eu c MgSi 2 O 6 (where b is a value in the range of 0.05 or more and less than 1, and c is a value in the range of more than 0 and 0.2 or less. The phosphor according to any one of the above, substantially consisting of a compound represented by:
<5> An electron beam-excited light emitting device comprising the phosphor according to any one of the above.
<6> The electron beam excitation light-emitting device as described above, wherein a phosphor excitation source is a low-energy electron beam.
<7> The phosphor according to any one of <1> to <4>, wherein the electron beam excitation light-emitting element is a field emission display.
<8> The phosphor according to any one of <1> to <4>, wherein the electron beam excitation light-emitting element is a surface electric field display.
<9> A field emission display comprising the phosphor according to <7>.
<10> A surface electric field display comprising the phosphor according to <8>.

本発明の電子線励起発光素子用蛍光体は、電子線励起により高い輝度を示すため、本発明の蛍光体をＣＲＴ、ＦＥＤ、ＳＥＤ、ＶＦＤ等の電子線励起発光素子に用いると、高い輝度を示す電子線励起発光素子が実現できる。さらに、本発明の電子線励起発光素子用蛍光体は、発光の色純度に優れるため、電子線励起発光素子に用いると色再現性に優れた電子線励起発光素子が実現できるので、本発明は工業的に極めて有用である。   Since the phosphor for an electron beam-excited light emitting device of the present invention exhibits high luminance by electron beam excitation, high luminance is obtained when the phosphor of the present invention is used for an electron beam excited light emitting device such as CRT, FED, SED, VFD. The electron beam excitation light emitting element shown can be realized. Furthermore, since the phosphor for an electron beam excited light emitting device of the present invention is excellent in color purity of light emission, an electron beam excited light emitting device excellent in color reproducibility can be realized when used in an electron beam excited light emitting device. It is extremely useful industrially.

本発明の蛍光体は、式（Ｉ）
Ｍ1Ｏ・ｍＭ2Ｏ・ｎＭ3Ｏ2 ・・・（Ｉ）
で表される化合物に少なくとも付活剤が含有されてなる蛍光体である。式（Ｉ）のＭ1は２価の金属元素であり、Ｃａ、ＳｒおよびＢａからなる群より選ばれる２種以上の元素またはＳｒまたはＢａであり、Ｍ1がＣａのみの場合は電子線励起によって高い輝度を示す蛍光体とはならない。式（Ｉ）のＭ2は２価の金属元素であり、Ｍｇおよび／またはＺｎである。式（Ｉ）のＭ3は４価の金属元素であり、Ｓｉ、ＧｅおよびＺｒからなる群より選ばれる１種以上の元素である。また、ｍは０．８以上１．２以下の範囲の値であり、ｎは１．６以上２．４以下の範囲の値である。また前記付活剤は、Ｃｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＭｎからなる群より選ばれる１種以上の元素である。
また、本発明の蛍光体は、さらに１価または３価の金属元素を１種以上含有されてなってもよい。１価または３価の金属元素としては、例えば、Ｌｉ、Ｎａ、Ｋ、Ｒｂ、Ｆｅ、Ｉｎ、Ｌａ、Ｌｕ、Ｂｉ、Ｓｂなどが挙げられる。 The phosphor of the present invention has the formula (I)
M 1 O · mM 2 O · nM 3 O 2 (I)
A phosphor in which at least an activator is contained in a compound represented by M 1 in the formula (I) is a divalent metal element, two or more elements selected from the group consisting of Ca, Sr and Ba, or Sr or Ba. When M 1 is only Ca, electron beam excitation is performed. Therefore, it does not become a phosphor exhibiting high luminance. M 2 in the formula (I) is a divalent metal element and is Mg and / or Zn. M 3 in the formula (I) is a tetravalent metal element, and is one or more elements selected from the group consisting of Si, Ge, and Zr. M is a value in the range of 0.8 to 1.2, and n is a value in the range of 1.6 to 2.4. The activator is one or more elements selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Mn.
The phosphor of the present invention may further contain one or more monovalent or trivalent metal elements. Examples of the monovalent or trivalent metal element include Li, Na, K, Rb, Fe, In, La, Lu, Bi, and Sb.

式（Ｉ）で表される化合物としては、ディオプサイド（Ｄｉｏｐｓｉｄｅ、透輝石）と同型の結晶構造を有する化合物が、それ以外の結晶構造を有する化合物より高い輝度を示す傾向があり、好ましい。   As the compound represented by the formula (I), a compound having a crystal structure of the same type as that of diopside (diopside) has a tendency to exhibit higher luminance than a compound having a crystal structure other than that, which is preferable.

さらに付活剤としてはＥｕが好ましいので、式（ＩＩ）
（Ｍ1 1-aＥｕa）Ｍ2Ｍ3 2Ｏ6 ・・・（ＩＩ）
（式中のＭ1、Ｍ2およびＭ3は前記と同じ意味を有する。）で表される化合物から実質的になる蛍光体がより好ましい。ここで、式（ＩＩ）において、ａは０を超え０．２以下の範囲の値である方がより高い輝度を示す傾向があり好ましい。ただし、ａが０の場合は付活剤のＥｕが含有されないので蛍光体とはならない。 Further, Eu is preferred as the activator, so that the formula (II)
(M 1 1-a Eu a ) M 2 M 3 2 O 6 (II)
A phosphor substantially consisting of the compound represented by (wherein M 1 , M 2 and M 3 have the same meaning as described above) is more preferred. Here, in the formula (II), it is preferable that a is a value in the range of more than 0 and not more than 0.2 because higher brightness tends to be exhibited. However, when a is 0, Eu as an activator is not contained, so that it does not become a phosphor.

さらに、前記式（ＩＩ）のＭ1としてはＳｒが単独で含有される場合またはＣａとＳｒの両方が含有される場合、Ｍ2としてはＭｇ、Ｍ3としてはＳｉが好ましいので、式（ＩＩＩ）
Ｃａ1-b-cＳｒbＥｕcＭｇＳｉ2Ｏ6 ・・・（ＩＩＩ）
で表される化合物から実質的になる蛍光体がさらに好ましい。ここで、式（ＩＩＩ）において、ｂは０．０５以上１未満の範囲の値である方が高い輝度を示す傾向があるので好ましい。またｂは０．２以上０．９以下の範囲の値である方がより高い輝度を示す傾向があるのでより好ましい。またｂは０．４５以上０．７以下の範囲の値である方が特に高い輝度を示す傾向があるので特に好ましい。また、ｃは０を超え０．２以下の範囲である方が高い輝度を示す傾向があり好ましい。またｃは０．００３以上０．０９以下の範囲である方がより高い輝度を示す傾向があるのでより好ましい。 Furthermore, when Sr is contained alone as M 1 in the formula (II) or when both Ca and Sr are contained, Mg is preferred as M 2 , and Si is preferred as M 3. )
Ca 1-bc Sr b Eu c MgSi 2 O 6 (III)
A phosphor substantially consisting of the compound represented by Here, in the formula (III), it is preferable that b is a value in the range of 0.05 or more and less than 1, since high brightness tends to be exhibited. Further, b is more preferably in the range of 0.2 or more and 0.9 or less because it tends to show higher luminance. Further, b is particularly preferably a value in the range of 0.45 or more and 0.7 or less because it tends to exhibit a particularly high luminance. Further, it is preferable that c is in the range of more than 0 and not more than 0.2 because it tends to show higher luminance. Further, c is more preferably in the range of 0.003 or more and 0.09 or less because it tends to exhibit higher luminance.

本発明の蛍光体は、電子線によって励起され発光するため、ＣＲＴ、ＦＥＤ、ＳＥＤ、ＶＦＤ等の電子線励起発光素子に好ましく用いられる。電子線励起発光素子に用いる蛍光体の励起源である電子線としては、電子の加速電圧が２０ｋＶ〜３０ｋＶである場合の高速電子線、電子の加速電圧が１０ｋＶ以下である場合の低速電子線があるが、本発明の蛍光体は、蛍光体の励起源が低速電子線である電子線励起発光素子により好ましく用いられる。蛍光体の励起源が低速電子線である電子線励起発光素子としては、ＦＥＤ、ＳＥＤが挙げられ、本発明の蛍光体は、ＦＥＤ、ＳＥＤに特に好ましく用いられる。   Since the phosphor of the present invention is excited by an electron beam and emits light, it is preferably used for an electron beam-excited light emitting device such as a CRT, FED, SED, VFD. The electron beam that is the excitation source of the phosphor used in the electron beam excitation light-emitting device includes a high-speed electron beam when the electron acceleration voltage is 20 kV to 30 kV, and a low-speed electron beam when the electron acceleration voltage is 10 kV or less. However, the phosphor of the present invention is preferably used for an electron beam excited light emitting device in which the excitation source of the phosphor is a slow electron beam. Examples of the electron beam excited light emitting device in which the excitation source of the phosphor is a low-energy electron beam include FED and SED, and the phosphor of the present invention is particularly preferably used for FED and SED.

次に、本発明の蛍光体を製造する方法について説明する。
本発明の蛍光体は、例えば、次のようにして製造することができる。本発明の蛍光体は、焼成により、式（Ｉ）で表される化合物に少なくとも付活剤としてＬｎ（ただしＬｎはＣｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＭｎからなる群より選ばれる１種以上の元素である。）が含有されてなる蛍光体となる金属化合物混合物を焼成することにより製造することができる。すなわち、対応する金属元素を含有する化合物を所定の組成となるように秤量し、混合した後に得られた金属化合物混合物を焼成することにより製造することができる。例えば、好ましい組成の一つである式Ｃａ0.49Ｓｒ0.49Ｅｕ0.02ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体は、ＣａＣＯ3、ＳｒＣＯ3、Ｅｕ2Ｏ3、ＭｇＯ、ＳｉＯ2をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．４９：０．４９：０．０２：１：２となるように秤量し、混合した後に焼成することにより製造することができる。 Next, a method for producing the phosphor of the present invention will be described.
The phosphor of the present invention can be manufactured, for example, as follows. The phosphor of the present invention is obtained by firing with a compound represented by the formula (I) at least Ln as an activator (where Ln is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, 1 or more elements selected from the group consisting of Er, Tm, Yb, and Mn.) Can be produced by firing a metal compound mixture that becomes a phosphor. That is, it can be produced by weighing the compound containing the corresponding metal element so as to have a predetermined composition and firing the resulting metal compound mixture. For example, a phosphor composed of a compound represented by the formula Ca 0.49 Sr 0.49 Eu 0.02 MgSi 2 O 6 , which is one of preferred compositions, includes CaCO 3 , SrCO 3 , Eu 2 O 3 , MgO, and SiO 2 as Ca: Sr. : Eu: Mg: Si can be manufactured by weighing the mixture so that the molar ratio is 0.49: 0.49: 0.02: 1: 2, mixing, and firing.

前記の金属元素を含有する化合物としては、カルシウム、ストロンチウム、バリウム、マグネシウム、亜鉛、ケイ素、ゲルマニウム、ジルコニウム、セリウム、プラセオジム、ネオジム、プロメチウム、サマリウム、ユウロピウム、ガドリニウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、マンガンの化合物で、例えば、酸化物を用いるか、または水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解および／または酸化して酸化物になりうるものを用いることができる。   Examples of the compound containing the metal element include calcium, strontium, barium, magnesium, zinc, silicon, germanium, zirconium, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium. , Ytterbium, manganese compounds, for example, using oxides, or hydroxides, carbonates, nitrates, halides, oxalates, etc. that can be decomposed and / or oxidized to form oxides at high temperatures be able to.

前記金属元素を含有する化合物の混合には、例えばボールミル、Ｖ型混合機、攪拌機等の通常工業的に用いられている装置を用いることができる。   For the mixing of the compound containing the metal element, for example, a generally industrially used apparatus such as a ball mill, a V-type mixer or a stirrer can be used.

前記金属化合物混合物を、例えば１０００〜１５００℃の温度範囲にて０．３〜１００時間保持して焼成することにより本発明の蛍光体が得られる。金属化合物混合物に水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解および／または酸化して酸化物になりうるものが含有されている場合、焼成の前に、金属化合物混合物を、例えば４００℃以上１０００℃未満の温度範囲で保持して仮焼することにより、酸化物としたり、結晶水を除去することも可能である。また、仮焼後に粉砕を行うこともできる。   For example, the phosphor of the present invention is obtained by firing the metal compound mixture while maintaining it in a temperature range of 1000 to 1500 ° C. for 0.3 to 100 hours, for example. If the metal compound mixture contains hydroxides, carbonates, nitrates, halides, oxalates, etc. that can decompose and / or oxidize at high temperatures to form oxides, before firing, the metal compound mixture For example, it is possible to obtain an oxide or remove water of crystallization by holding and calcining in a temperature range of 400 ° C. or higher and lower than 1000 ° C. Moreover, it can also grind | pulverize after calcination.

焼成時の雰囲気としては、例えば水素を０．１〜１０体積％含有する窒素、水素を０．１〜１０体積％含有するアルゴン等の還元性雰囲気が挙げられる。またさらに強い還元雰囲気で焼成するために、適量の炭素を添加して焼成してもよい。また仮焼時の雰囲気は、大気等の酸化性雰囲気、還元性雰囲気のいずれでもよい。   Examples of the atmosphere during firing include reducing atmospheres such as nitrogen containing 0.1 to 10% by volume of hydrogen and argon containing 0.1 to 10% by volume of hydrogen. Further, in order to fire in a stronger reducing atmosphere, an appropriate amount of carbon may be added and fired. The atmosphere during calcination may be either an oxidizing atmosphere such as air or a reducing atmosphere.

また、上記の金属元素を含有する化合物として、フッ化物、塩化物を用いることにより、生成する蛍光体の結晶性を高めることおよび／または平均粒径を大きくすることができる。生成する蛍光体の結晶性を高めるためおよび／または平均粒径を大きくするために、適量のフラックスを添加してもよい。フラックスとしては、例えば、ＬｉＦ、ＮａＦ、ＫＦ、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ、Ｌｉ2ＣＯ3、Ｎａ2ＣＯ3、Ｋ2ＣＯ3、ＮａＨＣＯ3、ＮＨ4Ｃｌ、ＮＨ4Ｉなどを挙げることができる。 In addition, by using fluoride or chloride as the compound containing the above metal element, the crystallinity of the phosphor to be produced can be increased and / or the average particle size can be increased. In order to increase the crystallinity of the phosphor to be produced and / or to increase the average particle size, an appropriate amount of flux may be added. Examples of the flux include LiF, NaF, KF, LiCl, NaCl, KCl, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , NH 4 Cl, and NH 4 I.

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。また、得られる蛍光体の輝度をさらに向上させるために、焼成を２回以上行うこともできる。   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. Moreover, in order to further improve the brightness | luminance of the fluorescent substance obtained, baking can also be performed twice or more.

また、本発明の蛍光体を用いてなる電子線励起発光素子の例として、ＦＥＤを挙げてその製造方法について説明する。ＦＥＤの製造方法としては例えば、特開２００２−１３８２７９号公報に開示されているような公知の方法が使用できる。すなわち、青色発光蛍光体、緑色発光蛍光体および赤色発光蛍光体を、それぞれ、例えば、ポリビニルアルコール水溶液などに分散して各蛍光体塗布液を調製する。その塗布液をガラス基板上に塗布し蛍光体層を形成してフェイスプレートとする。そのフェイスプレートと多数の電子放出素子を有するリアプレートとを支持枠を介して組立てると共に、これらの間隙を真空排気しつつ気密封止するなどの工程を経て、ＦＥＤを製造することができる。前記赤色発光蛍光体としては、酸化イットリウム蛍光体（Ｙ2Ｏ3：Ｅｕ）、硫化イットリウム蛍光体（Ｙ2Ｏ2Ｓ：Ｅｕ）などが挙げられ、前記緑色発光蛍光体としては、硫化亜鉛蛍光体（ＺｎＳ：Ｃｕ、Ａｕ、Ａｌ）などが挙げられる。また、前記青色発光蛍光体として、本発明の蛍光体を単独で使用するか、本発明の蛍光体と他の青色発光蛍光体とを混合して使用してもよい。この場合、他の青色発光蛍光体としては、硫化亜鉛蛍光体（ＺｎＳ：Ａｇ、Ｃｕ、Ａｕ、Ａｌ）などが挙げられる。 In addition, as an example of an electron beam excitation light-emitting device using the phosphor of the present invention, a method for manufacturing the FED will be described. As a method for producing the FED, for example, a known method as disclosed in JP-A-2002-138279 can be used. That is, each phosphor coating liquid is prepared by dispersing a blue light-emitting phosphor, a green light-emitting phosphor, and a red light-emitting phosphor in, for example, an aqueous polyvinyl alcohol solution. The coating solution is applied on a glass substrate to form a phosphor layer to form a face plate. The FED can be manufactured through processes such as assembling the face plate and a rear plate having a large number of electron-emitting devices through a support frame and hermetically sealing the gaps while evacuating them. Examples of the red light-emitting phosphor include yttrium oxide phosphor (Y 2 O 3 : Eu), yttrium sulfide phosphor (Y 2 O 2 S: Eu), and the green light-emitting phosphor includes zinc sulfide fluorescence. Body (ZnS: Cu, Au, Al) and the like. Further, as the blue light-emitting phosphor, the phosphor of the present invention may be used alone or a mixture of the phosphor of the present invention and another blue light-emitting phosphor may be used. In this case, examples of other blue-emitting phosphors include zinc sulfide phosphors (ZnS: Ag, Cu, Au, Al).

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.

また、発光輝度の測定は蛍光体を１０ｋＶの加速電圧により加速され、１μＡ／ｃｍ2の断面積を有する電子線を照射することで行った。なお、本実施例における色度ｘおよび色度ｙとは、ＣＩＥ（国際照明委員会：Ｃｏｍｍｉｓｓｉｏｎ Ｉｎｔｅｒｎａｔｉｏｎａｌｅ ｄｅ ｌ’Ｅｃｌａｉｒａｇｅ）の定めたＣＩＥ表色系のＸＹＺ表色系における色度ｘおよび色度ｙを意味する。 The measurement of light emission luminance was performed by irradiating the phosphor with an electron beam having a cross-sectional area of 1 μA / cm 2 accelerated by an acceleration voltage of 10 kV. Note that the chromaticity x and chromaticity y in the present embodiment are the chromaticity x and chromaticity y in the XYZ color system of the CIE color system defined by the CIE (International Commission on Illumination). Means.

比較例１
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．９９２：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１２２０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.992Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体１を得た。 Comparative Example 1
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS · 3NA), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content) 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide (SiO 2 , manufactured by Nippon Aerosil Co., Ltd., product name is AEROSIL 200 ), each raw material is Ca: Eu: Mg: Si The raw materials weighed so as to have a molar ratio of 0.992: 0.008: 1: 2 were mixed and then held for 2 hours at a temperature of 1220 ° C. in a N 2 atmosphere containing 2 % by volume of H 2. did. Firing was performed three times. Thus, the phosphor 1 composed of a compound represented by the composition formula Ca 0.992 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体１に、電子線を照射したところ青色の発光を示し、このときの輝度を１００とし、以下の実施例における蛍光体の輝度は相対輝度により示した。またこのときの色度ｘは０．１５５であり、色度ｙは０．０４５であった。   When this phosphor 1 was irradiated with an electron beam, blue light was emitted. The luminance at this time was assumed to be 100, and the luminance of the phosphor in the following examples was represented by relative luminance. The chromaticity x at this time was 0.155, and the chromaticity y was 0.045.

実施例１
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．９３２：０．０６：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１２２０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして、組成式がＣａ0.932Ｓｒ0.06Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体２を得た。 Example 1
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS 3NA), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL 200 ), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.932: 0.06: 0.008: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1220 ° C. for 2 hours. Firing was performed three times. In this way, phosphor 2 made of a compound represented by the composition formula Ca 0.932 Sr 0.06 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体２に、電子線を照射したところ青色の発光を示し、輝度は１０５であり、蛍光体１より高い輝度を示した。   When this phosphor 2 was irradiated with an electron beam, it emitted blue light and had a luminance of 105, which was higher than that of phosphor 1.

実施例２
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．８９２：０．１：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１２２０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.892Ｓｒ0.1Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体３を得た。 Example 2
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS · 3N-A), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL 200 ), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.892: 0.1: 0.008: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1220 ° C. for 2 hours. Firing was performed three times. In this way, phosphor 3 made of a compound represented by the composition formula Ca 0.892 Sr 0.1 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体３に、電子線を照射したところ青色の発光を示し、輝度は１０９であり、蛍光体１より高い輝度を示した。またこのときの色度ｘは０．１５５であり、色度ｙは０．０４０であった。   When this phosphor 3 was irradiated with an electron beam, it emitted blue light and had a luminance of 109, which was higher than that of phosphor 1. At this time, the chromaticity x was 0.155, and the chromaticity y was 0.040.

実施例３
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．７９２：０．２：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１２００℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.792Ｓｒ0.2Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体４を得た。 Example 3
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS · 3N-A), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL 200 ), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.792: 0.2: 0.008: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1200 ° C. for 2 hours. Firing was performed three times. In this way, phosphor 4 made of a compound represented by the composition formula Ca 0.792 Sr 0.2 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体４に、電子線を照射したところ青色の発光を示し、輝度は１１５であり、蛍光体１より高い輝度を示した。   When this phosphor 4 was irradiated with an electron beam, it emitted blue light and had a luminance of 115, which was higher than that of phosphor 1.

実施例４
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．６９２：０．３：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１２００℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.692Ｓｒ0.3Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体５を得た。 Example 4
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS · 3N-A), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL 200 ), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.692: 0.3: 0.008: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1200 ° C. for 2 hours. Firing was performed three times. In this way, phosphor 5 made of a compound represented by the composition formula Ca 0.692 Sr 0.3 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体５に、電子線を照射したところ青色の発光を示し、輝度は１１７であり、蛍光体１より高い輝度を示した。   When this phosphor 5 was irradiated with an electron beam, it emitted blue light and had a luminance of 117, which was higher than that of the phosphor 1.

実施例５
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．６９２：０．２９６：０．０１２：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１２００℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.692Ｓｒ0.296Ｅｕ0.012ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体６を得た。 Example 5
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS 3NA), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL 200 ), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.692: 0.296: 0.012: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1200 ° C. for 2 hours. Firing was performed three times. In this way, the composition formula to obtain a phosphor 6 consisting of compounds represented by Ca 0.692 Sr 0.296 Eu 0.012 MgSi 2 O 6.

この蛍光体６に、電子線を照射したところ青色の発光を示し、輝度は１１８であり、蛍光体１より高い輝度を示した。   When this phosphor 6 was irradiated with an electron beam, it emitted blue light and had a luminance of 118, which was higher than that of phosphor 1.

実施例６
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．６６２：０．３３：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１１８０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.662Ｓｒ0.33Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体７を得た。 Example 6
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS 3NA), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL200), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.662: 0.33: 0.008: 1: 2. The weighed raw materials were mixed and then calcined by holding at a temperature of 1180 ° C. for 2 hours in an N 2 atmosphere containing 2 % by volume of H 2 . Firing was performed three times. In this way, a phosphor 7 composed of a compound represented by the composition formula Ca 0.662 Sr 0.33 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体７に、電子線を照射したところ青色の発光を示し、輝度は１１７であり、蛍光体１より高い輝度を示した。またこのときの色度ｘは０．１５５であり、色度ｙは０．０３８であった。 When this phosphor 7 was irradiated with an electron beam, it emitted blue light and had a luminance of 117, which was higher than that of phosphor 1. The chromaticity x at this time was 0.155, and the chromaticity y was 0.038.

実施例７
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．４９：０．４９：０．０２：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１１５０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.49Ｓｒ0.49Ｅｕ0.02ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体８を得た。 Example 7
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS 3NA), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL 200 ) is adjusted so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.49: 0.49: 0.02: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1150 ° C. for 2 hours. Firing was performed three times. In this way, phosphor 8 made of a compound represented by the composition formula Ca 0.49 Sr 0.49 Eu 0.02 MgSi 2 O 6 was obtained.

この蛍光体８に、電子線を照射したところ青色の発光を示し、輝度は１１９であり、蛍光体１より高い輝度を示した。またこのときの色度ｘは０．１５６であり、色度ｙは０．０３５であった。   When this phosphor 8 was irradiated with an electron beam, it emitted blue light and had a luminance of 119, which was higher than that of the phosphor 1. The chromaticity x at this time was 0.156, and the chromaticity y was 0.035.

実施例８
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．３９２：０．６：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１１５０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.392Ｓｒ0.6Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体９を得た。 Example 8
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS 3NA), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL200), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.392: 0.6: 0.008: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1150 ° C. for 2 hours. Firing was performed three times. In this way, a phosphor 9 made of a compound represented by the composition formula Ca 0.392 Sr 0.6 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体９に、電子線を照射したところ青色の発光を示し、輝度は１２１であり、蛍光体１より高い輝度を示した。またこのときの色度ｘは０．１５６であり、色度ｙは０．０３４であった。   When this phosphor 9 was irradiated with an electron beam, it emitted blue light and had a luminance of 121, which was higher than that of phosphor 1. The chromaticity x at this time was 0.156, and the chromaticity y was 0.034.

実施例９
炭酸カルシウム（ＣａＣＯ3、宇部マテリアルズ株式会社製、商品名は超高純度炭酸カルシウムＣＳ・３Ｎ−Ａ）、炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＣａ：Ｓｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．３４２：０．６５：０．００８：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１１５０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＣａ0.342Ｓｒ0.65Ｅｕ0.008ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体１０を得た。 Example 9
Calcium carbonate (CaCO 3 , manufactured by Ube Materials Co., Ltd., trade name is ultra-high purity calcium carbonate CS 3NA), strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high purity strontium carbonate SW- K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42.0%, manufactured by Kyowa Chemical Industry Co., Ltd., product name is high-purity magnesium carbonate), silicon dioxide ( Each raw material of SiO 2 , manufactured by Nippon Aerosil Co., Ltd. (trade name is AEROSIL200), so that the molar ratio of Ca: Sr: Eu: Mg: Si is 0.342: 0.65: 0.008: 1: 2. The weighed raw materials were mixed and then fired in a 2 volume% H 2 containing N 2 atmosphere at a temperature of 1150 ° C. for 2 hours. Firing was performed three times. Thus, the phosphor 10 composed of a compound represented by the composition formula Ca 0.342 Sr 0.65 Eu 0.008 MgSi 2 O 6 was obtained.

この蛍光体１０に、電子線を照射したところ青色の発光を示し、輝度は１２１であり、蛍光体１より高い輝度を示した。またこのときの色度ｘは０．１５６であり、色度ｙは０．０３４であった。   When this phosphor 10 was irradiated with an electron beam, it emitted blue light and had a luminance of 121, which was higher than that of phosphor 1. The chromaticity x at this time was 0.156, and the chromaticity y was 0.034.

実施例１０
炭酸ストロンチウム（ＳｒＣＯ3、堺化学工業株式会社製、商品名は高純度炭酸ストロンチウムＳＷ−Ｋ）、酸化ユウロピウム（Ｅｕ2Ｏ3、信越化学工業株式会社製）、炭酸マグネシウム（ＭｇＯ含有量は４２．０％、協和化学工業株式会社製、製品名は高純度炭酸マグネシウム）、二酸化ケイ素（ＳｉＯ2、日本アエロジル株式会社製、商品名はＡＥＲＯＳＩＬ２００）の各原料をＳｒ：Ｅｕ：Ｍｇ：Ｓｉのモル比が０．９８：０．０２：１：２となるように秤量した原料を、混合した後、２体積％Ｈ2含有Ｎ2雰囲気中で１１５０℃の温度で２時間保持して焼成した。焼成は３回行った。このようにして組成式がＳｒ0.98Ｅｕ0.02ＭｇＳｉ2Ｏ6で表される化合物からなる蛍光体１１を得た。 Example 10
Strontium carbonate (SrCO 3 , manufactured by Sakai Chemical Industry Co., Ltd., trade name is high-purity strontium carbonate SW-K), europium oxide (Eu 2 O 3 , manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate (MgO content is 42. 0%, manufactured by Kyowa chemical industry Co., Ltd., product names are high-purity magnesium carbonate), silicon dioxide (SiO 2, Nippon Aerosil Co., Ltd., trade name of the respective raw materials of AEROSIL200) Sr: Eu: Mg: Si molar ratio of The raw materials weighed so as to be 0.98: 0.02: 1: 2 were mixed and then calcined by holding at a temperature of 1150 ° C. for 2 hours in an N 2 atmosphere containing 2 % by volume of H 2 . Firing was performed three times. In this way, a phosphor 11 made of a compound having a composition formula represented by Sr 0.98 Eu 0.02 MgSi 2 O 6 was obtained.

この蛍光体１１に、電子線を照射したところ青色の発光を示し、輝度は１１２であり、蛍光体１より高い輝度を示した。またこのときの色度ｘは０．１５８であり、色度ｙは０．０３５であった。   When this phosphor 11 was irradiated with an electron beam, it emitted blue light and had a luminance of 112, which was higher than that of phosphor 1. The chromaticity x at this time was 0.158, and the chromaticity y was 0.035.

Claims (10)

式Ｍ1Ｏ・ｍＭ2Ｏ・ｎＭ3Ｏ2（式中のＭ1はＣａ、ＳｒおよびＢａからなる群より選ばれる２種以上の元素またはＳｒまたはＢａであり、Ｍ2はＭｇおよび／またはＺｎであり、Ｍ3はＳｉ、ＧｅおよびＺｒからなる群より選ばれる１種以上の元素であり、ｍは０．８以上１．２以下の範囲の値であり、ｎは１．６以上２．４以下の範囲の値である。）で表される化合物に、少なくとも付活剤としてＬｎ（ただしＬｎはＣｅ、Ｐｒ、Ｎｄ、Ｐｍ、Ｓｍ、Ｅｕ、Ｇｄ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、ＹｂおよびＭｎからなる群より選ばれる１種以上の元素である。）が含有されてなることを特徴とする電子線励起発光素子用蛍光体。 Formula M 1 O · mM 2 O · nM 3 O 2 (wherein M 1 is two or more elements selected from the group consisting of Ca, Sr and Ba, or Sr or Ba, and M 2 is Mg and / or Zn, M 3 is one or more elements selected from the group consisting of Si, Ge and Zr, m is a value in the range of 0.8 to 1.2, and n is 1.6 to 2 4 is a value in the range of 4 or less) at least as an activator Ln (where Ln is Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, A phosphor for an electron beam-excited light-emitting device, which contains at least one element selected from the group consisting of Tm, Yb, and Mn. ディオプサイド（Ｄｉｏｐｓｉｄｅ、透輝石）と同型の結晶構造を有する請求項１記載の蛍光体。   The phosphor according to claim 1, wherein the phosphor has the same type of crystal structure as that of diopside. 式（Ｍ1 1-aＥｕa）Ｍ2Ｍ3 2Ｏ6（式中のＭ1、Ｍ2およびＭ3は前記と同じ意味を有し、ａは０を超え０．２以下の範囲の値である。）で表される化合物から実質的になる請求項１または２に記載の蛍光体。 Formula (M 1 -a Eu a ) M 2 M 3 2 O 6 (wherein M 1 , M 2 and M 3 have the same meaning as above, a is in the range of more than 0 and not more than 0.2) 3. The phosphor according to claim 1, substantially comprising a compound represented by the formula: 式Ｃａ1-b-cＳｒbＥｕcＭｇＳｉ2Ｏ6（ただし、式中ｂは０．０５以上１未満の範囲の値であり、ｃは０を超え０．２以下の範囲の値である。）で表される化合物から実質的になる請求項１〜３のいずれかに記載の蛍光体。 Formula Ca 1-bc Sr b Eu c MgSi 2 O 6 ( where a value in the range of b is less than one least 0.05 wherein, c is a value in the range of 0.2 or less than 0.) The phosphor according to any one of claims 1 to 3, substantially consisting of a compound represented by the formula: 請求項１〜４のいずれかに記載の蛍光体を用いてなることを特徴とする電子線励起発光素子。   An electron beam-excited light emitting device comprising the phosphor according to claim 1. 蛍光体の励起源が低速電子線である請求項５記載の電子線励起発光素子。   The electron beam excited light-emitting device according to claim 5, wherein the excitation source of the phosphor is a low-energy electron beam. 電子線励起発光素子がフィールドエミッションディスプレイであることを特徴とする請求項１〜４のいずれかに記載の蛍光体。   The phosphor according to any one of claims 1 to 4, wherein the electron beam-excited light emitting element is a field emission display. 電子線励起発光素子が表面電界ディスプレイであることを特徴とする請求項１〜４のいずれかに記載の蛍光体。   The phosphor according to any one of claims 1 to 4, wherein the electron beam-excited light emitting element is a surface electric field display. 請求項７記載の蛍光体を含有してなるフィールドエミッションディスプレイ。   A field emission display comprising the phosphor according to claim 7. 請求項８記載の蛍光体を含有してなる表面電界ディスプレイ。   A surface electric field display comprising the phosphor according to claim 8.
JP2005085668A 2005-03-24 2005-03-24 Fluorophor for electron beam excitation light emitting devices Pending JP2006265377A (en)

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US11/909,090 US20100127612A1 (en) 2005-03-24 2006-03-20 Phosphor and electron beam excited light-emitting device
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