JP4972957B2 - Phosphor, light-emitting device using the same, image display device, and lighting device - Google Patents

Phosphor, light-emitting device using the same, image display device, and lighting device Download PDF

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JP4972957B2
JP4972957B2 JP2006053557A JP2006053557A JP4972957B2 JP 4972957 B2 JP4972957 B2 JP 4972957B2 JP 2006053557 A JP2006053557 A JP 2006053557A JP 2006053557 A JP2006053557 A JP 2006053557A JP 4972957 B2 JP4972957 B2 JP 4972957B2
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phosphor
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JP2006321974A (en
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康夫 下村
直人 木島
友幸 来島
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三菱化学株式会社
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/4805Shape
    • H01L2224/4809Loop shape
    • H01L2224/48091Arched
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48247Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a bond pad of the item
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L2224/42Wire connectors; Manufacturing methods related thereto
    • H01L2224/47Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/481Disposition
    • H01L2224/48151Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive
    • H01L2224/48221Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked
    • H01L2224/48245Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic
    • H01L2224/48257Connecting between a semiconductor or solid-state body and an item not being a semiconductor or solid-state body, e.g. chip-to-substrate, chip-to-passive the body and the item being stacked the item being metallic connecting the wire to a die pad of the item
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES; ELECTRIC SOLID STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H01L2224/00Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/73Means for bonding being of different types provided for in two or more of groups H01L2224/10, H01L2224/18, H01L2224/26, H01L2224/34, H01L2224/42, H01L2224/50, H01L2224/63, H01L2224/71
    • H01L2224/732Location after the connecting process
    • H01L2224/73251Location after the connecting process on different surfaces
    • H01L2224/73265Layer and wire connectors

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a phosphor that has high color rendering properties, provides a high-luminance light emitting device and emits lights from green to yellow, to provide a light emitting device using the phosphor, an image display and a lighting apparatus including the light emitting device. <P>SOLUTION: The phosphor comprises a compound of garnet structure represented by general formula (I) M<SP>1</SP><SB>a</SB>M<SP>2</SP><SB>b</SB>X<SB>c</SB>M<SP>3</SP><SB>d</SB>M<SP>4</SP><SB>3</SB>O<SB>e</SB>[M<SP>1</SP>is Na and/or Li; M<SP>2</SP>is a divalent metal element; X is a metal element of luminescent central ion consisting essentially of Ce; M<SP>3</SP>is a trivalent metal element except X; M<SP>4</SP>is a tetravalent metal element; a, b, c, d and e are each a number to satisfy 0.001&le;a&le;0.5, 2.5&le;b&le;3.3, 0.005&le;c&le;0.5, 1.5&le;d&le;2.5 and e=ä(a+b)&times;2+(c+d)&times;3+12}/2] as a matrix in which a metal element of luminescent central ion is contained. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a phosphor in which a base compound contains a metal element mainly composed of cerium (Ce) as an emission center ion, and a light emitting device using the phosphor. Specifically, as a wavelength conversion material, a phosphor that absorbs light in a range from ultraviolet light to visible light and emits longer wavelength visible light, and a light source such as a light emitting diode (LED) or a laser diode (LD) The present invention relates to a phosphor capable of obtaining a light-emitting device having high color rendering properties and high brightness by being combined, and a light-emitting device using the phosphor. Furthermore, the present invention relates to an image display device and a lighting device that contain the light emitting device.

A white light emitting device configured by combining a gallium nitride (GaN) blue light emitting diode as a semiconductor light emitting element and a phosphor as a wavelength conversion material has low power consumption and a long lifetime. Therefore, it has been attracting attention as a light source for image display devices and illumination devices.
In this light emitting device, the phosphor used therein absorbs the visible light in the blue region emitted by the GaN-based blue light emitting diode and emits yellow light. Therefore, the phosphor used with the blue light of the light emitting diode not absorbed by the phosphor White light emission can be obtained by mixing colors. As the phosphor, typically, a phosphor having yttrium / aluminum composite oxide (Y 3 Al 5 O 12 ) as a base and containing cerium (Ce) as a luminescent center ion in the base is known. It has been. However, this phosphor is not easy to manufacture due to a high firing temperature and is not satisfactory in terms of temperature characteristics.

As an alternative yellow phosphor, the present inventors invented a phosphor having a basic structure of Ca 3 Sc 2 Si 3 O 12 : Ce 3+ (hereinafter abbreviated as “CSS phosphor”). A patent application was filed (see Patent Document 1).
That is, the phosphor is characterized in that a compound having a garnet crystal structure represented by the following general formula is used as a base, and a luminescent center ion is contained in the base.

M 1 ′ a ′ M 2 ′ b ′ M 3 ′ c ′ O d ′
[Wherein, M 1 ′ represents a divalent metal element, M 2 ′ represents a trivalent metal element, M 3 ′ represents a tetravalent metal element, and a ′ represents 2.7 to 3.3, b ′. 1.8 to 2.2, c ′ is 2.7 to 3.3, and d ′ is a number in the range of 11.0 to 13.0. ]
Patent Document 1 discloses Ca as a divalent metal element M 1 ′ , and further discloses a phosphor in which a part of Ca is substituted with Mg, Zn or the like. This CSS phosphor emits light from green to yellow depending on the composition, and is a high-quality phosphor that can also be used as a green phosphor of a light emitting device combining a GaN-based blue light emitting diode, a green phosphor and a red phosphor. is there.
JP 2003-64358 A

According to studies by the present inventors, the phosphor disclosed in Patent Document 1 can constitute a lighting device with high color rendering when used as a light emitting device combined with a GaN-based blue light emitting diode. As in [1] to [3], it has been found that the luminance is not satisfactory.
[1] Since the emission spectrum of the CSS phosphor does not match the standard relative luminous sensitivity curve (“Phosphor Handbook”, published by Ohm Co., Ltd., page 422), the luminance of the CSS phosphor does not exceed the luminous efficiency. It has the problem of being low. [2] When a light emitting device containing a CSS phosphor is used as a backlight of a liquid crystal display, the emission peak wavelength of the CSS phosphor is in a wavelength region where the green color transmittance of a conventional color filter for liquid crystal displays is high. Since they do not match, the brightness as a liquid crystal display tends to decrease. [3] When a light emitting device containing a CSS phosphor is used as illumination, energy efficiency tends to decrease because the ratio of blue-green light (510 nm or less) with low visibility is large. is there.

  The present invention has been made in view of the above-described problems, and uses a phosphor that emits light from green to yellow, which has a high luminance and color rendering properties, and can provide a high-luminance light-emitting device, and the phosphor. It is an object of the present invention to provide a light emitting device, and an image display device and an illumination device including the light emitting device.

As a result of intensive studies to solve the above problems, the present inventors have added an alkali metal in the base composition of the CSS phosphor, in particular, by adding Na and / or Li, the shape of the emission spectrum and The inventors have found that the peak wavelength can be changed, and have reached the present invention.

That is, the present invention comprises the following gist.
(1) A phosphor comprising a compound represented by the following general formula (I) containing a compound having a garnet structure as a host and containing a metal element of a luminescent center ion in the host.

M 1 a M 2 b X c M 3 d M 4 3 O e (I)
[In formula (I), M 1 is Na and / or Li, M 2 is a divalent metal element in which Ca occupies 50 mol% or more of M 2 , X is a luminescent center in which Ce occupies 50 mol% or more of X M 3 represents a trivalent metal element in which Sc , excluding X occupies 50 mol% or more of M 3 , and M 4 represents a tetravalent metal element in which Si occupies 50 mol% or more of M 4. , A, b, c, d, and e are numbers satisfying the following expressions, respectively.
0.001 ≦ a ≦ 0.5
2.5 ≦ b ≦ 3.3
0.005 ≦ c ≦ 0.5
1.5 ≦ d ≦ 2.5
e = {(a + b) × 2 + (c + d) × 3 + 12} / 2]
(2) The phosphor according to (1), wherein 0.001 ≦ a ≦ 0.3 in the general formula (I).
(3) The phosphor according to (1) or (2), wherein 0.02 ≦ c ≦ 0.1 in the general formula (I).
(4) In the general formula (I), any one of (1) to (3), wherein M 2 is at least one divalent metal element selected from the group consisting of Mg, Ca, Sr, Ba and Zn The phosphor according to claim 1.
(5) In the general formula (I), M 3 is at least one trivalent metal element selected from the group consisting of Al, Sc, Ga, Y, In, L, Gd and Lu (1) Thru | or the fluorescent substance in any one of (4).
(6) In the general formula (I), M 4 is at least one tetravalent metal element selected from the group consisting of Si, Ti, Ge, Zr, Sn and Hf (1) to (5) The phosphor according to any one of the above.
(7) In general formula (I), the metal element X of the luminescent center ion other than Ce is at least one metal element selected from Mn, Fe, Pr, Nd, Sm, Eu, Gb, Tb and Tm The phosphor according to any one of (1) to (6).
(8) The phosphor according to any one of (1) to (7), wherein in the general formula (I), M 1 is Na.
(9) The phosphor according to any one of (1) to (8), wherein in the general formula (I), X is Ce.
(10) The fluorescence according to (1), wherein in general formula (I), X is Ce, M 1 is Na and / or Li, M 2 is Ca or Ca and Mg , M 3 is Sc, and M 4 is Si. body.
(11) The phosphor according to any one of (1) to (10), wherein a metal element of Na and / or Li and a trivalent emission center ion is present at a position occupied by a divalent metal element of a garnet structure.
( 12 ) The phosphor according to any one of (1) to ( 11 ), wherein the weight median diameter of the phosphor is 5 μm to 30 μm.
( 13 ) A phosphor-containing composition comprising the phosphor according to any one of (1) to ( 12 ) and a liquid medium.
( 14 ) A light source that emits light in a range from ultraviolet light to visible light, and at least one phosphor that converts wavelength of at least part of the light from the light source and emits light in a longer wavelength region than the light from the light source. a light-emitting device and a phosphor-containing portion having more species, the comprises as a phosphor a phosphor of any crab described (1) to (12), or according to (13) as the phosphor-containing part the light emitting device characterized by having a phosphor-containing composition.
( 15 ) The light emitting device according to claim 14 , which emits white light.
( 16 ) An image display device comprising the light-emitting device according to ( 14 ) or ( 15 ).
( 17 ) An illumination device comprising the light-emitting device according to ( 14 ) or ( 15 ).

  According to the present invention, it is possible to provide a phosphor that emits light from green to yellow, which has a high luminance and color rendering properties and can provide a light-emitting device with high luminance. Furthermore, by using the phosphor of the present invention, it is possible to provide an image display device and an illumination device with high color rendering properties and high luminance.

Hereinafter, although an embodiment of the present invention is described in detail, the present invention is not limited to the following embodiment. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
The relationship between the color name and the chromaticity coordinates in the specification is all based on the JIS standard (JISZ8110).

[Phosphor]
The phosphor of the present invention comprises a compound represented by the following general formula (I) containing a metal element mainly composed of cerium (Ce) as a luminescent center ion in a matrix having a compound having a garnet structure. It is characterized by.
M 1 a M 2 b X c M 3 d M 4 3 O e (I)
[In the formula (I), M 1 is Na and / or Li, M 2 is a divalent metal element, X is a metal element of an emission center ion mainly composed of Ce, M 3 is a trivalent metal element excluding X , M 4 each represents a tetravalent metal element, and a, b, c, d, and e are numbers satisfying the following expressions, respectively.

0.001 ≦ a ≦ 0.5
2.5 ≦ b ≦ 3.3
0.005 ≦ c ≦ 0.5
1.5 ≦ d ≦ 2.5
e = {(a + b) × 2 + (c + d) × 3 + 12} / 2]
In the general formula (I), M 1 is Na and / or Li, but the ionic radius of Na is
Since it is close to the ionic radius of Ca, which is a particularly preferable element of M 2 to be described later, Na is preferable from the viewpoint that element substitution at the position of M 2 is easily performed effectively.

Further, M 2 representing a divalent metal element is preferably at least one selected from the group consisting of Mg, Ca, Sr, Ba and Zn, and in particular, Ca is 50 mol% or more of M 2. It is preferable to occupy 95 mol% or more. In addition, Mg and / or Zn may contain 0.001 mol or more and 0.5 mol or less in terms of the number of moles in the notation of the general formula (I) (M 4 molar ratio is 3). This is preferable in terms of compensation of the charge balance.

In the general formula (I), M 3 representing a trivalent metal element excluding the metal element X of the luminescent center ion is selected from the group consisting of Al, Sc, Ga, Y, In, La, Gd, and Lu. And at least one selected from the group consisting of Al, Sc, Y, and Lu is more preferable. Further, it is preferable that Sc occupies 50 mol% or more of M 3 , the remainder is preferably Y and / or Lu, and Sc is 10 of M 3 .
It is particularly preferred to occupy 0 mol%.

In the general formula (I), M 4 representing a tetravalent metal element includes Si, Ti, Ge, Z
It is preferably at least one selected from the group consisting of r, Sn, and Hf, and more preferably at least one selected from the group consisting of Si, Ge, and Sn. Further, Si preferably occupies 50 mol% or more of M 4 , particularly preferably 100 mol%.

In the general formula (I), as X representing the metal element of the luminescent center ion mainly composed of Ce, Ce preferably accounts for 50 mol% or more of X, more preferably 70 mol% or more, It is more preferable to occupy 90% or more, and 100 mol% is particularly preferable.
Ce 3+ ions absorb visible light in a wavelength region of 400 nm to 500 nm and emit green, yellow-green, yellow, and orange light. The phosphor of the present invention has an addition amount of Ce and addition of M 1 ions. By adjusting both the amounts, the emission color can be adjusted to the desired color.

Examples of the metal element of the luminescent center ion other than Ce include one or more of Mn, Fe, Pr, Nd, Sm, Eu, Gb, Tb, and Tm. For example, when Pr is contained as the metal element of the luminescent center ion, the light emitted from the Pr 3+ ion appears in the vicinity of 620 nm together with the light emitted from the Ce 3+ ion. Can be adjusted closer.

The compound represented by the general formula (I) has a garnet structure represented by the general formula A 3 B 2 C 3 O 12 [A is a divalent metal element, B is a trivalent metal element, and C is a tetravalent metal. It is a crystal structure of a body-centered cubic crystal represented by an element] and represented by a space group symbol Ia3d . A, B, and C ions are located at 12, 8, and tetrahedrally coordinated sites, respectively, and oxygen atoms are coordinated by 8, 6, and 4, respectively, and the natural mineral garnet has. It is the same structure as the crystal structure. In the phosphor of the present invention, preferably, the divalent metal element M 2 mainly composed of Ca occupies the A ion position in the general formula A 3 B 2 C 3 O 12, and the trivalent trivalent element mainly composed of Sc. The metal element M 3 occupies the C ion position and the Si-based tetravalent metal element M 4 contains the Ce-based metal element X as the luminescent center ion, and the monovalent metal element of Na and / or Li Is included.

  In the general formula (I), a is essential to be 0.001 or more, preferably 0.01 or more, and particularly preferably 0.03 or more. Further, a must be 0.5 or less, preferably 0.3 or less, particularly preferably 0.1 or less. If a is less than 0.001, it is difficult to increase the luminance when this phosphor is used in a light emitting device. On the other hand, if it exceeds 0.5, the emission intensity will decrease.

In the said general formula (I), b is 2.5-3.3, Preferably it is 2.6-3.2, More preferably, it is 2.7-3.1. The coefficient of the A ion in the general formula A 3 B 2 C 3 O 12 is 3
In the present invention, b takes a value close to “3”. Moreover, the position occupied in the crystal of Ce as the main luminescent center ion is not clear, but since the ionic radius of the Ce 3+ ion is very close to the ionic radius of the Ca 2+ ion, Ce has the position of the A ion. If it occupies, b will take the value close | similar to "3-c". Meanwhile, M 1, and and when a part of M 2 of the divalent metal element is present in addition to the A ion position, M 4 of M 3 and tetravalent metal elements of trivalent metal elements in the reverse of the present invention It is also conceivable that a monovalent metal element added as a part or a flux described later is present at the A ion position. It is also conceivable that Ce as the main luminescent center ion exists at the B ion position. Considering these, if b1 is 2.5 to 3.3, a desired phosphor can be obtained.

In the general formula (I), c must be 0.005 or more, preferably 0.01 or more, and particularly preferably 0.03 or more. Further, c is 0.5 and Der Turkey as essential or less, preferably at 0.3 or less, particularly preferably 0.1 or less. In both cases where c is less than 0.001 and exceeds 0.5, it is difficult to increase the luminance when the phosphor is used in a light emitting device.

In the said general formula (I), d is 1.5-2.5, Preferably it is 1.7-2.4. In the general formula A 3 B 2 C 3 O 12 , the coefficient of B ion is 2, and d is a value close to “2-c” when the metal element X of the luminescent center ion in the present invention occupies the B ion position. Take. Similarly to the coefficient b, in consideration of the presence of the B ion position of a metal element other than the trivalent metal element, a desired phosphor can be obtained if d is 1.5 to 2.5.

In the general formula (I), e indicating the coordination number of the oxygen atom is difficult to measure accurately. Therefore, it is assumed that the oxygen ion has a charge of −2, and the M 1 constituting the cation.
, M 2 , X, M 3 , and M 4 , and a, b, c, d, and 3 as coefficients thereof, the calculation is performed so that the charge balance is maintained. That is, e = {(a + b) × 2 + (c + d) × 3 + 12} / 2.

Among the phosphors represented by the general formula (I),
Na 0.015 Ca 2.97 Ce 0.015 Sc 2 Si 3 O 12 ,
Na 0.03 Ca 2.94 Ce 0.03 Sc 2 Si 3 O 12 ,
Na 0.05 Ca 2.9 Ce 0.05 Sc 2 Si 3 O 12 ,
Na 0.08 Ca 2.9 Ce 0.05 Sc 2 Si 3 O 11.985 ,
Na 0.07 Ca 2.9 Ce 0.03 Sc 2 Si 3 O 11.98 ,
Na 0.05 Ca 2.92 Ce 0.03 Sc 2 Si 3 O 11.99 ,
Na 0.03 Ca 2.92 Ce 0.05 Sc 2 Si 3 O 12.01 ,
Li 0.015 Ca 2.97 Ce 0.015 Sc 2 Si 3 O 12 ,
Li 0.03 Ca 2.94 Ce 0.03 Sc 2 Si 3 O 12 ,
Li 0.05 Ca 2.9 Ce 0.05 Sc 2 Si 3 O 12
Li 0.015 Ca 2.92 Ce 0.02 Sc 2 Si 3 O 12.003,
A phosphor that can be represented by Li 0.02 Ca 2.92 Ce 0.03 Sc 2 Si 3 O 12.005 and the like is preferable. Among these,
Na 0.08 Ca 2.9 Ce 0.05 Sc 2 Si 3 O 11.985 ,
Li 0.015 Ca 2.92 Ce 0.02 Sc 2 Si 3 O 12.003,
A phosphor that can be expressed by, for example, is preferable.

The phosphor of the present invention is composed of a compound containing a metal element mainly composed of Ce as an emission center ion in a base crystal having a garnet structure. However, when the composition ratio of a compound as a production raw material is slightly changed, There may be cases where crystals other than the base compound coexist. In that case, the coexistence of the phosphors is allowed as long as the amount of the phosphors is not impaired. Examples of such coexisting compounds include Sc 2 O 3 as an unreacted raw material, and by-products such as Ca 2 MgSi 2 O 7 and Ce 4.67 (SiO 4 ) 3 O.

The phosphor of the present invention is a trivalent metal element excluding the M 1 that is Na and / or Li, the M 2 that is a divalent metal element, and Ce, as long as the effects of the present invention are not impaired. Elements other than M 3 , M 4 which is a tetravalent metal element, and metal element X mainly composed of Ce as a luminescent center ion may be included. Examples of these elements include alkali metal elements such as K, Rb, Cs, and the like derived from alkali halides added as a crystal growth accelerator (flux) during the production of the phosphor, such as Nb, Ta, Sb. And other metal elements such as Bi and halogen elements.

As described above, in the phosphor of the present invention, the divalent metal element M 2 mainly composed of Ca occupies the A ion position in the general formula A 3 B 2 C 3 O 12 having a garnet structure, and the B ion position is trivalent metal element M 3 occupies the Sc mainly with the C ion position tetravalent metal elements M 4 of Si mainly accounted contains a metal element of Ce mainly as a luminescent center ion, further Na and / or Li The monovalent metal element M 1 is included. Here, the monovalent metal element is expected to be present at the A ion position. The ionic radius of Ce as the main component of the metal element X of the luminescent center ion is a divalent metal occupying the A ion position rather than the ionic radius of Sc as the main component of the trivalent metal element M 3 occupying the B ion position. Since it is close to the ionic radius of Ca as the main component of the element M 2 , most of Ce is considered to exist at the A ion position. Thus, the balance of charges is maintained by the presence of both the monovalent metal element M 1 and the trivalent Ce at the A ion position occupied by Ca as the main component of the divalent metal element M 2 . It is considered a thing. That is, there is an excess of positive charge caused by the presence of trivalent Ce at the divalent Ca position, and a shortage of positive charge due to the presence of monovalent Na and / or Li at the divalent Ca position. This cancels out the charge balance of the entire crystal. Monovalent metal element M 1 and trivalent C
Although the content in the phosphor of the luminescent center ion metal element mainly composed of e does not always match, the charge balance in this case is considered to be compensated by various lattice defects.

The excess of positive charge caused by substitution of Ce at the A ion position where divalent Ca is mainly present is due to the fact that Na and / or Li are present at the same Ca position, in addition to the divalent metal element M. Compensation can also be made when Mg and / or Zn as 2 is present at the B ion position where trivalent Sc is mainly present. The ion radii of Mg and Zn are Sc ions as the main component of the trivalent metal element M 3 occupying the B ion position, rather than the ionic radius of Ca as the main component of the divalent metal element M 2 occupying the A ion position. Since it is close to the radius, it is considered highly likely that most of Mg and Zn are present at the B ion position. As described above, Mg and / or Zn can be allowed to coexist in the phosphor of the present invention as the divalent metal element M 2 , and in this case, the charge imbalance is an element in which positions having different valences are substituted. It is estimated that the whole is compensated.

The phosphor of the present invention contains monovalent ions of Na and / or Li, and at the same time, by increasing the content of Ce as a luminescent ion, or if necessary, 2 of Mg and / or Zn. By including the valence ion, the coordination state around the Ce 3+ ion as the main component of the emission center ion is changed. And it is thought that the emission wavelength shifted to the long wavelength side due to the decrease of the energy of the 5d level, which is the excited state of Ce 3+ ions.

Even if a long wavelength shift of the emission wavelength occurs, the increase of the emission peak intensity is not so large, and when the shift width is increased, the emission peak intensity is decreased. However, since the long wavelength shift of the emission wavelength increases the overlap with the standard relative luminous sensitivity curve, the luminance can be greatly improved by adjusting the emission wavelength so that the emission peak intensity does not decrease so much.
When the content of Ce in the crystal was examined, it was found that the content of Ce in the crystal tends to increase by adding Na and / or Li. This indicates that Na and / or Li and Ce are present together in the crystal according to the above mechanism. Conversely, it can be said that the addition of Na and / or Li promotes solid solution at the Ca position in the Ce crystal. The long wavelength shift of the emission spectrum due to the addition of Na and / or Li originates from the change in the crystal field due to the presence of Na and / or Li as described above, and at the same time in the crystal. It is thought that this is because the energy level of Ce ions is shifted due to the interaction between Ce due to the increase of Ce contained. That is, the additive showing the effect of the present invention is not limited to monovalent ions such as Na and / or Li that can substitute the Ca position, but also divalent ions that can substitute the Sc position such as Mg and Zn, and Si positions. Trivalent ions such as Al, Ti, and B that can be substituted for have the same effect. Therefore, these effective elements can be added together with monovalent ions such as Na and / or Li. In particular, it is preferable to coexist Mg and Na and / or Li.

[Phosphor production method]
The phosphor of the present invention is a compound of M 1 source that is Na and / or Li in the general formula (I), a compound of M 2 source that is a divalent metal element, and M 3 that is a trivalent metal element. Source compound,
And tetravalent metal element M 4 source compound, and metal element X such as Ce as luminescent center ion
It is produced by reacting a pulverized mixture prepared from each raw material compound by heat treatment.

The pulverized mixture can be prepared by various methods such as a dry method and a wet method.
(1) In the dry method, the above compounds are pulverized using a dry pulverizer such as a hammer mill, roll mill, ball mill, jet mill, etc., and then mixed by a blender such as a ribbon blender, V-type blender or Henschel mixer. Alternatively, after mixing the above compounds, the mixture is pulverized using a dry pulverizer.
(2) In the wet method, the above compound is added to a medium such as water and pulverized and mixed using a wet pulverizer such as a medium stirring pulverizer, or the above compound is pulverized with a dry pulverizer. Then, the slurry prepared by adding and mixing in a medium such as water is dried by spray drying or the like.

Among these methods for preparing the pulverized mixture, the wet source method using a liquid medium is preferred because the element source compound of the luminescent center ion needs to mix and disperse a small amount of compound uniformly throughout. Also, other element source compounds are preferably wet methods from the viewpoint of obtaining uniform mixing throughout.
In the mixing, a compound containing a metal element or an anion not included in the general formula (I), so-called flux, is added for the purpose of promoting crystal growth of the phosphor and controlling the particle size. May be. Examples of the flux include alkali metal halides, ammonium halides, various borate compounds, alkaline earth metal halides, alkali metal carbonates, and various phosphates. Specific examples of the compounds are listed as LiF, LiCl, NaF, NaCl, KCl, KF, NH 4 F, NH 4 Cl, Li 2 CO 3 , Na 2 CO 3 , Li 3 PO 4 , Na 3 PO 4 , Na 2 HPO 4 , NaHPO 4 , K 3 PO 4 , K 2 HPO 4 , KH 2 PO 4 , H 3 BO 3 , B 2 O 3 , Na 2 B 4 O 7 , MgF 2 , CaF 2 , SrF 2 , BaF 2 , MgCl 2 , CaCl 2 , SrCl 2 , BaCl 2 , AlF 3 , YF 3 and the like. Of these, fluorides, chlorides, and phosphates are preferable in terms of particle size control and reactivity improvement, and CaCl 2 is particularly preferable.

The weight median diameter (D 50 ) of the phosphor of the present invention is usually 2 μm to 50 μm, preferably 5 μm to 30 μm, more preferably 10 μm to 25 μm, and most preferably 15 μm to 20 μm. If the weight median diameter is too small, the absorption efficiency of the excitation light is reduced, so that the brightness of the phosphor may be lowered, and if the weight median diameter is too large, the phosphor will settle in the resin. The brightness may be lowered.

Firing is preferably performed using a heat-resistant container such as a crucible or tray made of alumina or quartz, or a metal container such as platinum or tantalum. If necessary, a container coated with boron nitride can also be used. Regarding the firing temperature, firing can usually be carried out in the range of 1000 ° C to 1600 ° C, preferably 1200 ° C to 1500 ° C, and particularly preferably 1400 ° C to 1500 ° C. The firing atmosphere is usually a single or mixed atmosphere of gases such as air, oxygen, carbon monoxide, carbon dioxide, nitrogen, hydrogen, and argon. The heating time is 10 minutes to 24 hours, preferably 30 minutes to 12 hours, and may be performed a plurality of times as necessary. At that time, after the first heating, pulverization, dispersion and the like may be performed again.

  After the heat treatment of the phosphor, post-treatment such as washing, dispersion, classification, drying, and surface coating is performed as necessary. The cleaning treatment is performed using water, an inorganic acid such as hydrochloric acid, nitric acid, and acetic acid, an aqueous solution of ammonia, an aqueous solution of sodium hydroxide, and the like. The dispersion process is performed using a ball mill, a jet mill, a hammer mill, or the like. In addition, the classification treatment is performed by wet classification such as chickenpox treatment, dry classification using an airflow disperser, or a combination thereof. Surface coating is a method in which fine particles such as silica and alumina are deposited on the surface of the phosphor particles by wet using these sols, and calcium phosphate is deposited on the surface of the phosphor particles by the reaction between ammonium phosphate and a calcium compound. The method of making it take is taken.

  Further, after these post treatments, reheating can be performed at a temperature lower than the heat treatment temperature for the purpose of reducing crystal defects of the phosphor. The heating atmosphere at that time is preferably a reducing atmosphere such as nitrogen, argon, nitrogen containing a small amount of hydrogen, or nitrogen containing a small amount of carbon monoxide. Further, prior to heating in the reducing atmosphere, it is more preferable to heat at a temperature of 800 ° C. to 1300 ° C. in an oxidizing atmosphere such as air.

A compound of M 1 source that is Na and / or Li in the general formula (I) and a compound of M 2 source that is a divalent metal element, and a trivalent metal element that is used for the production of the phosphor of the present invention. A compound of a certain M 3 source, a compound of a tetravalent metal element M 4 source, and a raw material compound of a metal element X source such as Ce as an emission center ion include M 1 , M 2 , M 3 , and Oxides, hydroxides, carbonates, nitrates, sulfates, oxalates, carboxylates, halides and the like of each metal element of M 4 and X can be mentioned. Among these, reactivity to the composite oxide, and NO x during firing
, SO x and other non-generating factors are selected.

Among the source compounds of M 1 that are Na and / or Li, as the Li source compound, for example,
Examples include Li 2 CO 3 , Li (NO 3 ), LiCl, LiOH, LiCH 3 COO.2H 2 O, Li 2 (C 2 O 4 ), LiF, LiBr, etc. Examples of the Na source compound include Na 2. CO 3 , Na (NO 3 ), NaCl, NaOH, NaCH 3 COO.3H 2 O, Na 2 (C 2 O 4 ), NaF, NaBr can be mentioned.

Of the source compounds of Mg, Ca, Sr, Ba, and Zn that are preferable as M 2 that is a divalent metal element, examples of Mg source compounds include MgO, Mg (OH) 2 , MgCO 3 , Mg (OH ) 2 · 3MgCO 3 · 3H 2 O, Mg (NO 3 ) 2 · 6H 2 O, MgSO 4 , Mg (
OCO) 2 · 2H 2 O, Mg (OCOCH 3 ) 2 · 4H 2 O, MgCl 2 , MgF 2, etc.
Examples of source compounds include CaO, Ca (OH) 2 , CaCO 3 , Ca (NO 3 ) 2 .4H 2 O, CaSO 4 .2H 2 O, Ca (OCO) 2 .H 2 O, Ca (OCOCH 3). ) 2 · H 2 O, CaCl 2 , CaF 2, etc. are Sr source compounds such as SrO, Sr (OH) 2 , Sr
Examples of Ba source compounds include CO 3 , Sr (NO 3 ) 2 , SrSO 4 , Sr (OCO) 2 .H 2 O, Sr (OCOCH 3 ) 2 .4H 2 O, SrCl 2 .6H 2 O and the like. , BaO, Ba (O
H) 2 , BaCO 3 , Ba (NO 3 ) 2 , BaSO 4 , Ba (OCO) 2 .2H 2 O, Ba (O
COCH 3 ) 2 .H 2 O, BaCl 2 .2H 2 O, and the like, and examples of the Zn source compound include ZnO, Zn (OH) 2 , ZnCO 3 , Zn (NO 3 ) 2 , and Zn (OCO). 2 , Zn (OC
And OCH 3 ) 2 , ZnCl 2 , ZnF 2 and the like.

Among the source compounds of Al, Sc, Y, and Lu that are preferable as M 3 that is a trivalent metal element, examples of the Al source compound include Al 2 O 3 , Al (OH) 3 , AlOOH, A
l (NO 3 ) 3 .9H 2 O, Al 2 (SO 4 ) 3 , AlCl 3 , AlF 3 and the like are Sc source compounds such as Sc 2 O 3 , Sc (OH) 3 , Sc 2 (CO 3 ) 3 , Sc (NO 3 ) 3 , Sc 2 (
SO 4 ) 3 , Sc 2 (OCO) 6 , Sc (OCOCH 3 ) 3 , ScCl 3 , ScF 3 and the like are Y source compounds such as Y 2 O 3 , Y (OH) 3 , Y 2 (CO 3 ) 3 , Y (NO 3 ) 3 , Y 2 (S
O 4 ) 3 , Y 2 (OCO) 6 , YCl 3 , YF 3 and the like, and examples of the Lu source compound include Lu 2 O 3 , Lu 2 (SO 4 ) 3 , LuCl 3 , LuF 3 and the like. , Respectively.

Among Si, Ge, and Sn raw material compounds preferred as M 4 which is a tetravalent metal element, examples of Si source compounds include SiO 2 , H 4 SiO 4 , Si (OC 2 H 5 ) 4 , CH 3 Si (OCH 3 ) 3 , CH 3 Si (OC 2 H 5 ) 3 , Si (OCOCH 3 ) 4 and the like are Ge source compounds, for example, GeO 2 , Ge (OH) 4 , Ge (OCOCH 3). ) 4 , GeCl 4 and the like, and examples of the Sn source compound include SnO 2 , SnO 2 .nH 2 O, and Sn (NO 3 ) 4.
, Sn (OCOCH 3 ) 4 , SnCl 4 and the like.

Examples of the Ce source compound mainly used as the metal element X of the luminescent center ion include Ce 2.
O 3 , CeO 2 , Ce (OH) 3 , Ce (OH) 4 , Ce 2 (CO 3 ) 3 , Ce (NO 3 ) 3 , C
Examples include e 2 (SO 4 ) 3 , Ce (SO 4 ) 2 , Ce 2 (OCO) 6 , Ce (OCOCH 3 ) 3 , CeCl 3 , CeCl 4 , and CeF 3 .
Any of these raw material compounds may be used alone or in combination of two or more.

[Combination of phosphor]
As the phosphor in the light emitting device of the present invention, the phosphor of the present invention may be used alone, or two or more kinds may be used in any combination and ratio. In addition to the phosphor of the present invention, a phosphor that emits light in red, orange, yellow, or the like is used in combination, whereby a light emitting device with higher color rendering properties can be obtained. At that time, the phosphor used in combination is preferably a phosphor that emits light in a wavelength region of 580 nm to 780 nm. For example, when divalent Eu is used as a luminescent center ion, sulfide phosphors such as CaS: Eu 2+ and SrS: Eu 2+ , Ca 2 Si 5 N 8 : Eu 2+ , Sr 2 Si 5 N 8: Eu 2+, Ba 2 Si 5 N 8: Eu 2+, CaAlSiN 3: Eu 2+, SrAlSiN 3: Eu 2+, (Ca x ", Sr 1-x") AlSiN 3: Eu 2+ (0 ≦ x
”≦ 1), nitride phosphors such as LaSi 3 N 5: Eu 2+ , and Sr 2 Si 3 Al 2 N 6 O 2 : E
u 2+ , Ca x ″ (Si y ″ , Al 1-y ″ ) 12 (O z ″ , N 1-z ″ ) 16 : Eu 2+ (0 ≦ x ″ ≦ 1
Oxynitride phosphors such as 0 ≦ y ″ ≦ 1, 0 ≦ z ″ ≦ 1) are preferable. In addition, when trivalent Eu is used as the luminescent center ion, oxysulfide phosphors such as La 2 O 2 S: Eu 3+ , Y 2 O 2 S: Eu 3+ , and trivalent Eu are used. Preference is given to coordination compound phosphors coordinated with acetylacetone, thenoyltrifluoroacetone and the like. In the case of using tetravalent Mn as the luminescent center ion, 3.5MgO.0.5MgF 2 .GeO 2 : Mn 4+ or the like is preferable. Among these, sulfide-based phosphors and nitride-based phosphors having Eu 2+ as the luminescent center ion are particularly preferable because of high emission intensity. In particular, preferable examples of the red phosphor include, for example, CaAlSiN 3 : Eu 2+ , (Sr, Ca) AlSiN 3 : Eu 2+ , M 2 Si 5 N 8 as described in WO2005 / 052087A1 pamphlet. Eu 2+ (M is at least one selected from the group consisting of Ca, Sr and Ba), Sr 2 Si 3 Al 2 N 6 O 2 : Eu 2+ , LaSi 3 N 5 : Eu 2+, etc. Nitride-based or oxynitride-based phosphors are preferred.
[Phosphor-containing part]
In the light emitting device of the present invention, a phosphor-containing portion including the phosphor of the present invention and, if necessary, another phosphor (for example, a red phosphor) as described above may be disposed on the light source. In this case, the red phosphor does not necessarily have to be mixed in the same part as the other phosphors. For example, a layer containing the red phosphor is laminated on the layer containing the phosphor of the present invention. May be.

In the light-emitting device of the present invention, the phosphor-containing portion can be provided on the light source. The phosphor-containing part can be provided as a contact layer between the light source and the sealing material part, as a coating layer outside the sealing material part, or as a coating layer inside the outer cap. Moreover, it can also be set as the form which contained the fluorescent substance in the sealing material.
As a sealing material used, a thermoplastic resin, a thermosetting resin, a photocurable resin, etc. are mentioned normally. Specifically, for example, methacrylic resin such as polymethylmethacrylate; styrene resin such as polystyrene and styrene-acrylonitrile copolymer; polycarbonate resin; polyester resin; phenoxy resin; butyral resin; polyvinyl alcohol; Cellulose resins such as cellulose acetate butyrate; epoxy resins; phenol resins; silicone resins. Further, an inorganic material such as a siloxane bond formed by solidifying a solution obtained by hydrolytic polymerization of a solution containing an inorganic material such as a metal alkoxide, ceramic precursor polymer or metal alkoxide by a sol-gel method, or a combination thereof. An inorganic material can be used.

Although the usage-amount of the fluorescent substance with respect to a sealing material is not specifically limited, Usually, 0.01-100 weight part with respect to 100 weight part of sealing materials, Preferably it is 0.1-80 weight part, Preferably 1 to 60 parts by weight.
[Phosphor-containing layer]
The phosphor-containing composition of the present invention includes the phosphor of the present invention, and, if necessary, another phosphor (for example, a red phosphor) as described above and a liquid medium. The liquid medium is not particularly limited as long as the phosphor can be dispersed. For example, a solution of a thermosetting resin, a photocurable resin, an inorganic material, or the like before curing can be used. Specifically, a methacrylic resin-containing solution such as methyl polymethacrylate; an epoxy resin-containing solution; a silicone resin-containing solution; a solution containing a metal alkoxide, a ceramic precursor polymer, or a metal alkoxide is hydrolyzed by a sol-gel method Examples include a solution obtained by polymerization.

Moreover, additives, such as a viscosity modifier, can also be contained in a fluorescent substance containing composition as needed.
[Light Emitting Device / Surface Emitting Lighting Device]
A light-emitting device according to the present invention is a light-emitting device having at least a light source such as a semiconductor light-emitting element and a phosphor that emits visible light having a longer wavelength by absorbing light in a range from ultraviolet light to visible light emitted from the light source. is there. It is a light emitting device with high color rendering properties, and is suitable as a light source for image display devices such as a color liquid crystal display and lighting devices such as surface light emission.

  The light emitting device of the present invention will be described with reference to the drawings. FIG. 1 is a schematic cross-sectional view showing an embodiment of a light-emitting device composed of the phosphor of the present invention as a wavelength conversion material and a light source. FIG. 2 is a schematic cross-sectional view showing an embodiment of a surface emitting illumination device incorporating the light emitting device shown in FIG. 1 and 2, 1 is a light emitting device, 2 is a mount lead, 3 is an inner lead, 4 is a light source, 5 is a phosphor containing portion, 6 is a conductive wire, 7 is a mold member, and 8 is a surface emitting illumination. An apparatus, 9 is a diffusion plate, and 10 is a holding case.

  The light-emitting device 1 of the present invention has a general bullet shape, for example, as shown in FIG. A light source 4 made of a GaN blue light emitting diode or the like is bonded to the upper cup of the mount lead 2. The phosphor of the present invention and, if necessary, another phosphor (for example, a red light-emitting phosphor) are mixed and dispersed in a sealing material such as an epoxy resin, an acrylic resin, or a silicone resin, and poured into the cup, thereby containing the phosphor. Part 5 is formed. The light source 4 is covered and fixed by the phosphor-containing portion 5. On the other hand, the light source 4 and the mount lead 2, and the light source 4 and the inner lead 3 are electrically connected by conductive wires 6 and 6, respectively, and are entirely covered and protected by a mold member 7 made of epoxy resin or the like.

  Moreover, the surface emitting illumination device 8 incorporating this light-emitting device 1 is shown in FIG. A large number of light emitting devices 1 are provided on the bottom surface of a rectangular holding case 10 whose inner surface is light-opaque, such as a white smooth surface, and a power source and circuits for driving the light emitting device 1 are provided outside (not shown). ) And arrange. In order to make the light emission uniform, a diffusion plate 9 such as an acrylic plate made of milky white is fixed to a portion corresponding to the lid portion of the holding case 10.

  Then, the surface emitting illumination device 8 is driven to apply blue voltage to the light source 4 of the light emitting device 1 to emit blue light or the like. Part of the emitted light is absorbed in the phosphor-containing portion 5 by the phosphor of the present invention, which is a wavelength conversion material, and another phosphor added as necessary, and converted into light having a longer wavelength. The color rendering is high due to color mixing with blue light or the like that has not been absorbed, and high luminance light emission is obtained. This light passes through the diffusion plate 9 and is emitted upward in the drawing, and illumination light with uniform brightness is obtained within the surface of the diffusion plate 9 of the holding case 10.

Here, the light source 4 is a light source that emits excitation light of the phosphor contained in the phosphor-containing portion 5, and is also a light source for emitting light as one component of light emitted from the light emitting device 1. . That is, part of the light emitted from the light source 4 is absorbed as excitation light by the luminescent material in the phosphor-containing portion 5, and another part is emitted from the light emitting device 1. .
The type of the light source 4 is arbitrary, and an appropriate one can be selected according to the application and configuration of the display device. However, it is usually necessary to use a light source that has no bias in light distribution and emits light widely. preferable.

  For example, a light-emitting diode (hereinafter referred to as “LED” as appropriate), an edge-emitting or surface-emitting laser diode, an electroluminescence element, and the like can be given, but an inexpensive LED is usually preferable. Specific examples of the LED include an LED using an InGaN-based, GaAlN-based, InGaAlN-based, ZnSeS-based semiconductor, or the like crystal-grown on a substrate such as silicon carbide, sapphire, or gallium nitride by a method such as MOCVD. .

Moreover, when using LED as the light source 4 in this way, there is no restriction | limiting in the shape, but in order to improve the extraction efficiency of light, it is preferable to make the side surface into a taper shape.
Furthermore, the material of the LED package is also arbitrary, and for example, ceramics, PPA (polyphthalamide), or the like can be used as appropriate. However, from the viewpoint of improving color reproducibility, the color of the package is preferably white or silver. From the viewpoint of increasing the light emission efficiency of the light emitting device 1, it is preferable that the reflectance of light is increased.

  Moreover, when attaching the light source 4 to the mount lead 2, the specific method is arbitrary, For example, it can attach using solder | pewter. The type of solder is arbitrary, but, for example, AuSn, AgSn, or the like can be used. Moreover, when using solder, it is also possible to supply electric power from the electrode formed on the mount lead 2 through the solder. In particular, when a large current type LED or laser diode, for which heat dissipation is important, is used as the light source 4, it is effective to use solder for installing the light source 4 because the solder exhibits excellent heat dissipation.

  Further, when the light source 4 is attached to the mount lead 2 by means other than solder, for example, an adhesive such as an epoxy resin, an imide resin, or an acrylic resin may be used. In this case, by using a paste in which conductive fillers such as silver particles and carbon particles are mixed with the adhesive, the adhesive can be energized to supply power to the light source as in the case of using solder. It is also possible to make it. Furthermore, it is preferable to mix these conductive fillers because heat dissipation is improved.

  Furthermore, the power supply method to the light source 4 is also arbitrary. In addition to energizing the solder and adhesive described above, the light source 4 and the electrode may be connected by wire bonding to supply power. At this time, the wire used is not limited, and the material, dimensions, etc. are arbitrary. For example, metals such as gold and aluminum can be used as the wire material. Moreover, although the thickness of the wire can be normally 20 micrometers-40 micrometers, a wire is not limited to this.

Another example of a method for supplying power to the light source is a method for supplying power to the light source by flip chip mounting using bumps.
One light source may be used alone, or two or more light sources may be used in combination. Furthermore, the light source 4 may be used alone or in combination of two or more.
Moreover, the light source 4 may share the one light source 4 with the fluorescent substance containing part 5 containing two or more types of fluorescent substances. It is also possible to produce two or more phosphor-containing portions 5 and provide the light source 4 for each.

  The light source 4 in the light emitting device 1 is not particularly limited as long as it emits light in the range from ultraviolet light to visible light, but preferably emits light in the wavelength region of 380 nm to 550 nm. . Among these, 400 nm or more is more preferable, and 420 nm or more is particularly preferable. Moreover, 520 nm or less is still more preferable, and 500 nm or less is especially preferable. Among these, when a light source that emits light in a wavelength region of 430 nm to 480 nm is used, a light emitting device having particularly high color rendering properties can be obtained.

When the phosphor of the present invention is used alone for the phosphor-containing portion 5, a light-emitting device of light yellowish green, light green, and light blue-green can be obtained. Further, by combining the phosphor of the present invention with an arbitrary red phosphor, a white light emitting device having an arbitrary color temperature can be configured.
For example, the phosphor of the present invention and the red phosphor are used as the phosphor contained in the phosphor-containing portion 5. The phosphor-containing portion 5 absorbs part of the light from the ultraviolet to blue region emitted from the light source 4 and emits light in the green region and red region. Using this phosphor-containing portion 5 in the light emitting device 1 and / or the surface emitting illumination device 8 having the above-described configuration, the blue light emitted from the light source 4 and the green light and red light of the phosphor are mixed. Thus, the light emitting device 1 and / or the surface emitting lighting device 8 that emits white light with high color rendering properties is provided. The light-emitting device and / or the surface-emitting illumination device can emit light in, for example, a light bulb color, a daylight white color, and a daylight color according to JIS standards. Here, the light bulb color, the daylight white color, and the daylight color indicate light emission in the chromaticity range defined as the light source color of the fluorescent lamp defined in JIS Z9112.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist.
Example 1
The following raw materials were placed in an agate mortar with a small amount of ethanol, mixed well, and then dried in an oven at 120 ° C.

CaCO 3 : 0.0295 mol Sc 2 O 3 : 0.01 mol SiO 2 : 0.03 mol Ce (NO 3 ) 3 (aqueous solution): 0.0005 mol Na 2 CO 3 : 0.0005 mol The raw material mixture was wrapped in platinum foil, fired by heating at 1450 ° C. under atmospheric pressure for 3 hours while circulating nitrogen gas containing 4% by volume of hydrogen, followed by pulverization. Then, it was immersed in 1 mol / L hydrochloric acid, stirred, and left for 12 hours to remove hydrochloric acid-soluble impurities. The phosphor and the hydrochloric acid solution that did not dissolve were separated, and then washed with water (repeating the water, stirring, and then repeating the solid-liquid separation step). Subsequently, after drying, a classification process was performed to manufacture a phosphor.

FIG. 16 shows JCPD of garnet Ca 3 Sc 2 Si 3 O 12 and scandium oxide Sc 2 O 3 .
3 is a chart showing a comparison between a standard pattern of S and a powder X-ray diffraction pattern of the phosphor obtained in Example 1. As a result of analysis by powder X-ray diffraction, the obtained phosphor was confirmed to be a compound having a garnet crystal structure as shown in FIG. FIG. 10 shows a powder X-ray diffraction pattern of this phosphor.

Moreover, the composition of the obtained phosphor was measured by the following method.
<Measurement of content of Ca, Sc, Si, Ce, and Mg>
The phosphor sample was melted with 30 times the amount of sodium carbonate, dissolved and diluted with dilute hydrochloric acid to obtain a measurement solution, and quantified by an inductively coupled plasma emission analysis (ICP-AES) method. The calibration curve solution was prepared using a commercially available standard solution so as to have the same salt concentration as the sample solution.

<Measurement of alkali metal content>
Add 50 times the amount of perchloric acid and hydrofluoric acid (HF) to the phosphor sample, heat and treat with white smoke, add hydrochloric acid, heat and dilute to obtain a measurement solution, and use the atomic absorption (AAS) method. Na was quantified by inductively coupled plasma optical emission spectrometry (ICP-AES). The calibration curve solution was prepared using a commercially available standard solution so as to have the same acid concentration as the sample solution.

From these measurement results, the ratio of each component atom in the phosphor was determined with a silicon ratio of 3, and the results are shown in Table 1.
Next, the emission spectrum of this phosphor was measured by the following method, and the results are shown in FIG. The peak wavelengths are shown in Table 2.
<Measurement of emission spectrum>
In a fluorescence measuring apparatus (manufactured by JASCO Corporation), a 150 W xenon lamp was used as an excitation light source. The light from the xenon lamp was passed through a 10 cm diffraction grating spectrometer, and only the light having a wavelength of 455 nm was irradiated to the phosphor through the optical fiber. The light generated by the irradiation of the excitation light was dispersed with a 25 cm diffraction grating spectrometer, and the emission intensity of each wavelength of 300 nm to 800 nm was measured with a multichannel CCD detector (“C7041” manufactured by Hamamatsu Photonics). Subsequently, an emission spectrum was obtained through signal processing such as sensitivity correction by a personal computer.

In addition, from the data in the wavelength region of 480 nm to 800 nm of the emission spectrum, JIS
The chromaticity coordinates x and y in the XYZ color system defined by Z8701 were calculated, and the results are shown in Table 2. Further, from the stimulus value Y in the XYZ color system calculated in accordance with JIS Z8724, the relative luminance with the stimulus value Y of the phosphor obtained in Comparative Example 1 described later as 100% is calculated, and the result is It is shown in Table 2. Further, the relative emission peak intensity was calculated with the emission peak intensity of the phosphor obtained in Comparative Example 1 as 100%, and the results are shown in Table 2.

<Measurement of weight median diameter (D 50 ) of phosphor>
Measurement was performed using a laser diffraction particle size distribution analyzer LA-300 manufactured by HORIBA, Ltd.
(Comparative Example 1)
Phosphor production raw materials were CaCO 3 : 0.0297 mol as an M 2 source compound, Sc 2 O 3 : 0.01 mol as an M 3 source compound, and SiO 2 : 0.03 mol as an M 4 source compound, and X Except that the source compound was Ce (NO 3 ) 3 (aqueous solution): 0.0003 mol, phosphors were produced in the same manner as in Example 1, evaluated in the same manner, and the results are shown in Tables 1 and 2 and FIG. It was shown to.

(Examples 2 to 5)
Except that the phosphor production raw material was used so that the phosphor composition became the composition shown in Table 1, the phosphor was produced in the same manner as in Example 1 and evaluated in the same manner. Shown in FIGS. The emission spectra of the phosphors obtained in Examples 2 to 5 are shown in FIGS.
FIG. 8 is a graph simply showing the relationship between the relative luminance and the relative emission peak intensity due to the addition of Na or Li from the data of the examples. The x-value of the CIE chromaticity coordinate is shown on the horizontal axis, and the relative light emission peak intensity and the relative luminance are shown on the vertical axis. In FIG. 8, ♦ indicates relative brightness when Li or Na is not added, ▲ indicates relative brightness when Na is added, black square indicates relative brightness when Li is added, and ◇ indicates that Li or Na is not added. Relative emission peak intensity in the case, Δ indicates the relative emission peak intensity when Na is added, and □ indicates the relative emission peak intensity when Li is added. As the chromaticity coordinate value x increases with the addition of Na or Li, that is, as the emission peak shifts to a longer wavelength, both the relative emission peak intensity and the relative luminance increase. It was larger than the increase in strength. This is thought to be due to an increase in luminance compared to the increase in peak intensity due to an increase in the overlap between the standard relative luminous sensitivity curve and the emission spectrum.

  FIG. 9 is a graph in which all CIE chromaticity coordinates of Examples 1 to 4 and Comparative Example 1 are plotted. As shown in FIG. 9, it is plotted on almost one straight line. It can be seen that, due to the addition of Li or Na and the accompanying increase in the amount of Ce present in the crystal, x increases and y decreases, and the emission color increases redness.

It is typical sectional drawing which shows one Example of the light-emitting device comprised from the fluorescent substance of this invention as a wavelength conversion material, and a light source. It is typical sectional drawing which shows one Example of the surface emitting illumination device incorporating the light-emitting device shown in FIG. It is an emission spectrum of the phosphor obtained in Example 1 (however, the vicinity of the excitation light wavelength (455 nm) is omitted). It is an emission spectrum of the phosphor obtained in Example 2 (however, the vicinity of the excitation light wavelength (455 nm) is omitted). It is an emission spectrum of the phosphor obtained in Example 3 (however, the vicinity of the excitation light wavelength (455 nm) is omitted). It is an emission spectrum of the phosphor obtained in Example 4 (however, the vicinity of the excitation light wavelength (455 nm) is omitted). It is an emission spectrum of the phosphor obtained in Example 5 (however, the vicinity of the excitation light wavelength (455 nm) is omitted). It is the graph which showed the relationship of the relative brightness | luminance with respect to the shift of the light emission peak wavelength by addition of Na or Li, and the relative light emission peak intensity from the data of the Example (the horizontal axis is made into x value of CIE chromaticity coordinate). It is the graph which plotted all the CIE chromaticity coordinates of the fluorescent substance obtained in Examples 1-4 and the comparative example 1. FIG. 2 is a powder X-ray diffraction pattern of the phosphor obtained in Example 1. FIG. 3 is a powder X-ray diffraction pattern of the phosphor obtained in Example 2. FIG. 3 is a powder X-ray diffraction pattern of the phosphor obtained in Example 3. FIG. 4 is a powder X-ray diffraction pattern of the phosphor obtained in Example 4. FIG. 6 is a powder X-ray diffraction pattern of the phosphor obtained in Example 5. FIG. 3 is a powder X-ray diffraction pattern of the phosphor obtained in Comparative Example 1. FIG. 4 is a chart showing a comparison between a JCPDS standard pattern of garnet Ca 3 Sc 2 Si 3 O 12 and scandium oxide Sc 2 O 3 and a powder X-ray diffraction pattern of the phosphor obtained in Example 1. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Light-emitting device 2 Mount lead 3 Inner lead 4 Light source 5 Phosphor containing part 6 Conductive wire 7 Mold member 8 Surface emitting illumination device 9 Diffusion plate 10 Holding case 11 LED
12 Phosphor-containing part 13 Frame 14 Conductive wire 15 Terminal 16 Terminal

Claims (17)

  1. A phosphor comprising a compound represented by the following general formula (I) containing a compound having a garnet structure as a base and containing a metal element of a luminescent center ion in the base.
    M 1 a M 2 b X c M 3 d M 4 3 O e (I)
    [In formula (I), M 1 is Na and / or Li, M 2 is a divalent metal element in which Ca occupies 50 mol% or more of M 2 , X is a luminescent center in which Ce occupies 50 mol% or more of X M 3 represents a trivalent metal element in which Sc , excluding X occupies 50 mol% or more of M 3 , and M 4 represents a tetravalent metal element in which Si occupies 50 mol% or more of M 4. , A, b, c, d, and e are numbers satisfying the following expressions, respectively.
    0.001 ≦ a ≦ 0.5
    2.5 ≦ b ≦ 3.3
    0.005 ≦ c ≦ 0.5
    1.5 ≦ d ≦ 2.5
    e = {(a + b) × 2 + (c + d) × 3 + 12} / 2]
  2.   The phosphor according to claim 1, wherein in the general formula (I), 0.001 ≦ a ≦ 0.3.
  3.   The phosphor according to claim 1 or 2, wherein 0.02 ≦ c ≦ 0.1 in the general formula (I).
  4. The general formula (I), wherein M 2 is at least one divalent metal element selected from the group consisting of Mg, Ca, Sr, Ba and Zn. Phosphor.
  5. In the general formula (I), M 3 is at least one trivalent metal element selected from the group consisting of Al, Sc, Ga, Y, In, L, Gd, and Lu. The phosphor according to any one of the above.
  6. 6. The general formula (I), wherein M 4 is at least one tetravalent metal element selected from the group consisting of Si, Ti, Ge, Zr, Sn, and Hf. The phosphor according to 1.
  7.   In the general formula (I), the metal element X of the luminescent center ion other than Ce is at least one metal element selected from Mn, Fe, Pr, Nd, Sm, Eu, Gb, Tb and Tm. Item 7. The phosphor according to any one of Items 1 to 6.
  8. The phosphor according to any one of claims 1 to 7, wherein in the general formula (I), M 1 is Na.
  9.   The phosphor according to any one of claims 1 to 8, wherein in the general formula (I), X is Ce.
  10. The phosphor according to claim 1, wherein, in the general formula (I), X is Ce, M 1 is Na and / or Li, M 2 is Ca or Ca and Mg , M 3 is Sc, and M 4 is Si.
  11. The phosphor according to any one of claims 1 to 10, wherein Na and / or Li and a metal element of a trivalent emission center ion are present at a position occupied by a divalent metal element of a garnet structure.
  12. The phosphor according to any one of claims 1 to 11 weight median diameter of the phosphor (D 50) is 5 m to 30 m.
  13. A phosphor-containing composition comprising the phosphor according to any one of claims 1 to 12 and a liquid medium.
  14. A light source that emits light in the range from ultraviolet light to visible light, and at least one phosphor that converts wavelength of at least part of the light from the light source and emits light in a longer wavelength region than the light from the light source It is a light-emitting device provided with a fluorescent substance containing part , Comprising: The fluorescent substance of any one of Claims 1 thru | or 12 is included as said fluorescent substance, or the fluorescent substance of Claim 13 as said fluorescent substance containing part A light-emitting device comprising the composition .
  15. The light emitting device according to claim 14 , which emits white light.
  16. An image display device which comprises a light-emitting device according to claim 14 or 15.
  17. Lighting apparatus comprising a light-emitting device according to claim 14 or 15.
JP2006053557A 2005-04-18 2006-02-28 Phosphor, light-emitting device using the same, image display device, and lighting device Expired - Fee Related JP4972957B2 (en)

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JP5075552B2 (en) * 2007-09-25 2012-11-21 株式会社東芝 Phosphor and LED lamp using the same
KR101265833B1 (en) 2007-12-07 2013-05-20 도시바 마테리알 가부시키가이샤 Phosphor and led light-emitting device using the same
JP6341480B2 (en) * 2014-04-16 2018-06-13 株式会社豊田自動織機 Garnet-type oxide, method for producing the same, and solid electrolyte for secondary battery and secondary battery using the same
JPWO2015166999A1 (en) * 2014-05-01 2017-04-20 株式会社 東北テクノアーチ Luminescent body and radiation detector
US20180163127A1 (en) * 2015-07-22 2018-06-14 Panasonic Intellectual Property Management Co., Ltd. Garnet compound and method for producing same, light emitting device and decorative article using garnet compound, and method of using garnet compound

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