WO2006101222A1

WO2006101222A1 - Fluorescent substance and electron beam excited light emitting element

Info

Publication number: WO2006101222A1
Application number: PCT/JP2006/306059
Authority: WO
Inventors: Yoshiko Nakamura; Toshinori Isobe; Satoru Kuze; Susumu Miyazaki
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2005-03-24
Filing date: 2006-03-20
Publication date: 2006-09-28
Also published as: TW200704753A; TWI398505B; JP2006265377A; KR20070113301A

Abstract

A fluorescent substance and an electron beam excited light emitting element. The fluorescent substance comprises a compound represented by the formula (I) below and, as an activator, at least one element selected from the group consisting of Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Mn: M1O•mM2O•nM3O2 (I) wherein M1 represents at least two elements selected from the group consisting of Ca, Sr and Ba, or Sr alone or Ba alone; M2 represents at least one element selected from the group consisting of Mg and Zn; M3 represents a least one element selected from the group consisting of Si, Ge and Zr; and m satisfies the requirement: 0.8≤m≤1.2; and n satisfies the requirement: 1.6≤n≤2.4. The electron beam excited light emitting element comprises the fluorescent substance.

Description

Phosphors and electrical springs ^ ¹ έ elements

顯 field

The present invention relates to a phosphor and an electron spring excitation element. Light

Background contract

In recent years, field emission display (FED) and surface electric field display (SED) have been attracting attention and developed as light emitting devices. These light-emitting elements consist of a phosphor and an electro-knitting source that excites it. For example, CaMgS i ₂ 0 ₆ : Ειι is known as a phosphor that emits light under illumination (Ex t ended Abs t rac t of the Fifth In te rna ti ona l Con fer ence on the Sc i enc e and Technolog of Di s Phosphor s. 1999 ”p. 317—p. 320).

However, from the viewpoint of improving the performance of light emission, high-luminance phosphors have been demanded.

Disclosure of the invention

An object of the present invention is to provide a phosphor exhibiting high luminance under electron beam irradiation and electro-excited light emission using the phosphor. Is to share with ίΜί.

As a result of intensive research on phosphors, the present invention came to be honest with the present invention.

That is, the present invention comprises a compound represented by the formula (I) and Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and ^ Mn as activators. A phosphor containing at least one selected from the group is provided.

M ^x O -mM ² 0-nM ³ 0 ₂ (I) CM ¹ is at least two selected from the group consisting of C a, S r and B a, S r ^ fi or B a alone,

M ² is at least one selected from the group consisting of Mg and Zn,

M ³ is at least one selected from the group consisting of S i, Ge and Z r,

m is 0.8 or more and 1.2 or less,

n is 1.6 or more and 2.4 or less. ]

In addition, the present invention provides an electric exciter element including a selfish phosphor and an electron emission portion. BEST MODE FOR CARRYING OUT THE INVENTION

Body

The phosphor of the present invention contains a compound represented by the selfish formula (I) and an activator.

In formula (I), M ¹ is a divalent metal element such as calcium (Ca), strontium (Sr), or no Jum (B a), and Sr, 8 &1;& And 3]: a combination ^ ¾ :, a combination of Ca and B a, a combination of S r and B a; a combination of Ca, S r and B a ^ :.

M ² is a divalent metal element such as magnesium (Mg) or (Zn), one of Mg and Zn; a combination of Mg and Zn, preferably Mg or a combination of Mg and Zn More preferably, it is Mg.

M ³ is a tetravalent metal element such as silicon (S i), germanium (Ge), zirconium (Zr), one of S i, Ge, Z r; combination of S i and Ge, 31 and ∑ 1 ", Ge and Z r ^ :; S i, Ge, Z r ^ i, preferably S i, S i

A combination of Ge, a combination of 31 and 21 ", or a combination of Si, Ge, and Zr, and more preferably Si.

In the formula (I), m is 0.8 or more and 1.2 or less, and n is 1.6 or more and 2.4 or less. Tongues include cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), tellurium Bium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), manganese (Mn), preferably Eu.

The tongue may be any of these worms or combinations.

The phosphor may further contain other metal elements such as a monovalent metal element and a trivalent metal element. Other metal elements include, for example, lithium (L i), sodium (Na), potassium (K), rubidium (Rb), iron (Fe), indium (In), lanthanum (La), lutetium

(Lu), Bismuth (B i), Antimony (Sb). These may be jobs or groups.

The phosphor is preferably a compound represented by the formula (II).

In formula (II), M ¹ M ² and are the same as MM ² and M ^{3 in} formula (I), respectively, a is greater than 0, preferably greater than or equal to 0.003 and less than 0.3 Preferably, it is 0.2 or less.

Furthermore, the phosphor is preferably a compound represented by the formula (III)

Ca --b-cS r _b Eu _c MgS i ₂ 0 ₆ (III)

b is greater than 0.7, preferably greater than or equal to 0.75, more preferably greater than or equal to 0.8, less than 1, preferably less than or equal to 0.98, and c is greater than 0, preferably greater than or equal to 0.003. Yes, less than 0.3, preferably 0.2 or less. The sum of b and c is more than 0.7 and less than 1. The phosphor preferably has the same crystal structure as that of diopside (5). Phosphors satisfy the above-mentioned conditions, and are excited when exposed to an electric field and give a rough outline. Phosphors can, for _{_{_{example, S r 0. 98 Eu 0}}} . 02 MgS i 2 〇 _{_{_{6, S r 0. 72 Eu}}} 0. 28 Mg S i 2 〇 _{_{_{6, B a 0. 98 Eu}}} 0. 02 MgS i 2 〇 _{_{_{_{6, Ba 0. 72 Eu 0}}}} . 28 MgS i 2 〇 _{_{_{6, Ca 0. 26 S r}}} 0. 72 E u 0. 02 MgS i 2 〇 _{_{_{6, Ca 0. 08 S r}}} 0. 72 Eu 0, 2 It is a compound represented by MgS i ₂ 0 ₆ . For example, low-voltage springs (acceleration voltage: about 0.0OOlkV to about 10kV), high-speed springs (acceleration voltage: about 20kV to about 30kV), preferably Is a slow spring It is. Therefore, the phosphor is used for an electron beam excitation light emitting device such as FED or SED whose excitation source is a low-speed spring, CRT or VFD which is a high-speed spring, preferably FED or SED. The phosphor of the present invention can be obtained by performing a mixture of a compound represented by the formula (I) and a metal compound to be a phosphor containing the activator according to 例えば ii. For example, a metal compound And a mixture satisfying the molar ratio of the metal elements in the phosphor is obtained, and then the mixture is added.

Metal compounds are calcium, strontium, norium, magnesium, β, kaium, germanium, zirconium, cerium, praseodymium, neodymium, promethium, samarium, succulent pium, gadolinium, te J lebium, dysprosium, holmium, elepium, It is a compound of thulium, ytterbium, and manganese. For example, it may be an oxide, or a hydroxide, carbonate, salt, halide, or oxalate that decomposes or becomes an oxide at high temperature. Instead of adding a halide as a flux, a metal halide, more preferably a metal fluoride or metal chloride, may be used as the metal compound.

_{_{_{.. S r 0 98 Eu 0}}} 02 MgS i 2 0 consisting of compounds represented by ₆ phosphor, S RC_〇 _{_3,} Eu ₂ 0 _3, Mg_〇, S and抨量the S I_〇 ₂ r: eu: Mg: S i of molar ratio of 0.98: 0. 0 2: 1:.. give 2. it mixture, the mixture Ba ₀ obtained by舰the ₉₈ Eu ₀ ₀₂ with MgS i ₂ 0 ₆ The phosphor composed of the compound represented by weighing BaC 0 ₃ , Eu ₂ 0 ₃ , MgO, S i 0 _2, and the molar ratio of Ba: Eu: Mg: S i is 0.98: 0.02: 1:... 2 to give the mixed compound is the mixture further obtained by _{_{_{_{Rukoto, Ca 0 26 S r 0 72}}}} Eu 0 02 M gS i 2 〇 phosphor consisting of compounds represented by _6, CAC0 _3, S RC_〇 _3, Eu ₂ 〇 _3, M G_〇, weighing the _{S i0 2 Ca: S r:} Eu: Mg: S molar ratio of i is 0.26: 0.7 2: 0. It is obtained by obtaining a mixture that is 02: 1: 2, and then refining the mixture.

For example, mixing may be performed using a device such as a pole mill, a V-type mixer, or a stirring device. Mixture of metal compounds ^^ or oxidized to oxides at high temperature, including metal hydroxides, carbonates, «salts, halides, oxalates« Good. Fiber Is about 400 ° C or more, about 1000. What is necessary is just to perform at the temperature below C, and you may grind | pulverize the calcined mixture.

For example, the dredging can be performed under the following conditions.

Temperature: about 1000 ° C or higher, preferably about 1 100. C or more and about 150 ° C. or less, preferably about 1200. C or less,

Retention time: 0.3 hours or more, within 100 hours,

Atmosphere: Nitrogen containing hydrogen from 0.1 to: L 0 body, Argon and other gases containing 0.1 to 10% by volume of hydrogen.

In this method, carbon may be added to the mixture of metal compounds before navigation. By adding carbon, soot is performed in a stronger atmosphere. In addition, you may add flux to the metal compound mixture. By adding the flux, a highly crystalline phosphor or a phosphor having a large average tree weight can be obtained. For example, L i F, NaF, KF, L i C l, NaC K KC 1, L i ₂ C 0 ₃ , Na ₂ C 0 ₃ , K ₂ C 0 ₃ , NaHC 0 ₃ , NH ₄ C 1, NH ₄ I. Sincerely, it can be done once, but it can be done more than once.

The phosphor may be pulverized, washed or classified. For example, the powder cake and the powder can be made with a device that adjusts the ilS of the phosphor. For example, the powder frame can be made with a pole mill or a jet mill. ^ 1 can be made with a sieve or a cyclone.

The spring excitation example of the present invention includes the above-described phosphor, and usually includes a phosphor and an electron emission portion. The electron emission part emits a spring that excites the phosphor to emit light, and is, for example, m, a planar electron emission source (emitter).

For example, the FED, SED, CRT, and VFD, preferably FED and SED are used as the electrical excitation. FED may be a method including steps (i) to (iv) as described in JP-A-2002-138279, for example.

(i) For the blue phosphor, the green phosphor, and the red phosphor, a step of preparing each solution by dispersing the phosphor in a solvent (for example, polyvinyl alcohol aqueous solution,

(ii) applying each liquid to a glass base, thigh, forming a phosphor layer to make a face spray 卜,

(i i i) a process of assembling a face plate and a rear plate on which a large number of electron emission portions are formed via a support frame;

(iv) A step of evacuating and sealing the gap between the face plate and the rear plate.

The blue phosphor is a phosphor containing the compound represented by the formula (I) and the activator, and other blue phosphors may be combined as necessary. Other blue phosphors, for example, sulfur sulfide phosphors

(ZnS: Ag, Cu, Au, A1). Green phosphor, for example, sulfide phosphors: a (ZnS Cu, Au, Al) , red phosphor, for example, yttrium oxide phosphor (Y ₂ 〇 _3: Eu), sulfides yttrium phosphor (Y ₂ 〇 ₂ S: Eu).

The SED may be ordered in the same manner as the FED. For example, the method disclosed in paragraph No. 0182-0189 of JP-A-2002-83537 (providing a plurality of surface conduction electron-emitting devices on the rear plate) The glass substrate, the phosphor layer formed on the inner surface of the glass substrate, and a face plate made of a metal back are arranged on the substrate via a ¾f frame, and frit glass is applied to these joints, After sealing in the air, the voids are evacuated and sealed. When performing monochrome display, ^ ffl the phosphor containing the compound represented by formula (I) and the activator to form a color display, a black stripe, and a selfish fluorescence in the gap. A phosphor layer is prepared by applying phosphors of various colors including the body to form a black stripe or black matrix.

CRT and VFD may be S ^ by the method using the above phosphor. Example

The present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

Luminance was measured by irradiating a phosphor with a spring accelerated by an acceleration voltage of 10 kV and having a cross-sectional area of 1 A / C m ² . Chromaticity X and chromaticity y were determined in accordance with the XYZ color system of the CIE color system defined by CIE (International Commission on Lighting: International LEDa 1 Ec lair age). Reference example 1

Calcium carbonate (CaC_〇 _3, Ube Material stock meetings, trade name: ultra-high纖炭acid force Rushiumu CS · 3N-A), oxidation Yu opening Piumu (Ειι ₂ 0 _3, manufactured by Shin-Etsu Chemical Co., Ltd.), magnesium carbonate 0 ^ ^ 〇 content: 42.0%, manufactured by Kyowa chemical Engineering Shushikikaine Product name: high-purity magnesium carbonate), silicon (S I_〇 ₂ dioxide, Japan Aerojiru stock Board machine, product name: AEROS I L200) weighed To obtain a mixture in which the molar ratio of C a: Eu: Mg: S i is 0.99 2: 0.0.008: 1: 2, and the mixture is contained in a N ₂ atmosphere containing 2 # ¾% H ₂ . 1 Heated at 220 ° C for 2 hours.舰is done a total of three times to obtain a phosphor 1 comprising formula Ca _{_0.} ₉₉₂ Eu _0. ₀₀₈ represented by MgS i ₂ 〇 ₆ compound.

Is phosphor 1 electric? ! It turned blue under fountain irradiation. Table 1 shows the measurement results of luminance, chromaticity X, and chromaticity y. In this example, the luminance of phosphor 1 was set to 100. In addition, as a result of examining the crystal position with an X-ray diffractometer, Phosphor 1 had the same crystal key as Dopside. Example 1

Strontium carbonate (S r C0 _3, Sakai Gakue Shashu formula Board machine, product name: High繊炭acid strike opening Nchiumu SW- K), oxide Yu opening Piumu (Eu ₂ 〇 _3, Shin-Etsu Chemical E Nada formula Board擺), magnesium carbonate (MgO content: 42.0%, Kyowa Chemical Industry Co., Ltd. ± $ ¾, Product name: High purity coal Acid magnesium), silicon dioxide (S I_〇 _2, Japan Aerojiru stock Kaine懷, trade name: AE ROS I L200) are weighed and mixed to S r: Eu: Mg: the molar ratio of S i is 0.98: A mixture was obtained which was 0.0.02: 1: 2. The mixture was incubated at 1150 ° C. for 2 hours under N ₂ atmosphere containing 2% H ₂ . «Is to obtain a phosphor 2 consisting of compounds represented by performing a total of 3 times with the formula _{_{_{S r 98 Eu 0. 02 MgS}}} i 2 0 6.

Phosphor 2 emitted blue light under illumination. Table 1 shows the measurement results of luminance, chromaticity X and chromaticity y. Phosphor 2 had the same crystal position as Diopside. Fluorescent yarn bandits and cocoon properties

Industrial application fields

The phosphor of the present invention emits high-luminance light when excited by an electric source. The phosphor is suitably used for electrical excitation light such as FED and SED.

Claims

The scope of the claims

1. selected from the group consisting of the compound represented by formula (I) and the activator Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and ^ Mn Provide a phosphor containing at least one of the above.

M ^x O -mM ² 0-nM ³ 0 ₂ (I)

[M ¹ is at least two selected from the group consisting of Ca, Sr and Ba, Srβί or Ba alone,

M ² is at least one selected from the group consisting of Mg and Zn,

M ³ is at least one selected from the group consisting of S i, Ge and Z r,

0.8≤m≤1.2

1. 6≤n≤2. ]

2. The phosphor according to claim 1, comprising a compound represented by the formula (II).

(M ¹ ₁ _ _a Eu _a ) M ² M ³ ₂ 0 ₆ (II)

CM ¹ , M ² and M ³ are the same as in formula (I).

0 <a <0.3

3. The phosphor according to claim 1, comprising a compound represented by the formula (III).

S r _b Eu _c MgS i ₂ 0 ₆ (III)

CO. 7 <b <l,

0 <c <0. 3

0. 7 b + c≤l.

4. The phosphor according to claim 1, wherein the phosphor has the same crystal structure as that of diopside.

5. An electric spring excitation comprising the phosphor according to claim 1.

6. The electric excitation light emitting element according to claim 5, wherein the electron II excitation light emission further includes an electron emission portion.

7. Electric ^! The spring excited light emitting device according to claim 5, wherein the spring excited light emitting element is selected from FED, SED, CRT, and VFD.

8. The electrical excitation light emitting element according to claim 7, wherein the electrical excitation light emission ^? Is selected from FED and SED.

9. ™ as a spring-excited light emitting eave of the phosphor according to any one of claims 1 to 4.