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JP2003321675A - Nitride fluorophor and method for producing the same - Google Patents

Nitride fluorophor and method for producing the same

Info

Publication number
JP2003321675A
JP2003321675A JP2002126566A JP2002126566A JP2003321675A JP 2003321675 A JP2003321675 A JP 2003321675A JP 2002126566 A JP2002126566 A JP 2002126566A JP 2002126566 A JP2002126566 A JP 2002126566A JP 2003321675 A JP2003321675 A JP 2003321675A
Authority
JP
Japan
Prior art keywords
phosphor
light emitting
emitting device
nitride
nitride phosphor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
JP2002126566A
Other languages
Japanese (ja)
Other versions
JP2003321675A5 (en
Inventor
Hiroto Tamaoki
寛人 玉置
Masatoshi Kameshima
正敏 亀島
Masaru Takashima
優 高島
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nichia Chemical Industries Ltd
Original Assignee
Nichia Chemical Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nichia Chemical Industries Ltd filed Critical Nichia Chemical Industries Ltd
Priority to JP2002126566A priority Critical patent/JP2003321675A/en
Priority to CA2447288A priority patent/CA2447288C/en
Priority to PCT/JP2003/003418 priority patent/WO2003080764A1/en
Priority to US10/478,598 priority patent/US7258816B2/en
Priority to SG2009037094A priority patent/SG185827A1/en
Priority to CNB038004542A priority patent/CN100430456C/en
Priority to KR1020097013179A priority patent/KR100983193B1/en
Priority to KR1020037015150A priority patent/KR100961324B1/en
Priority to EP03710450.2A priority patent/EP1433831B1/en
Priority to KR1020097013178A priority patent/KR100961322B1/en
Priority to AU2003221442A priority patent/AU2003221442A1/en
Priority to SG200600830-4A priority patent/SG155768A1/en
Priority to KR1020097013180A priority patent/KR100961342B1/en
Priority to SG2009037052A priority patent/SG173925A1/en
Priority to TW092106347A priority patent/TWI258499B/en
Priority to MYPI20030992 priority patent/MY148692A/en
Publication of JP2003321675A publication Critical patent/JP2003321675A/en
Publication of JP2003321675A5 publication Critical patent/JP2003321675A5/ja
Priority to US11/252,111 priority patent/US7297293B2/en
Priority to US11/905,725 priority patent/US7556744B2/en
Priority to US11/905,720 priority patent/US7597823B2/en
Priority to US12/453,535 priority patent/US7964113B2/en
Priority to US12/453,534 priority patent/US8058793B2/en
Priority to US12/453,587 priority patent/US8076847B2/en
Pending legal-status Critical Current

Links

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    • H01L2224/321—Disposition
    • H01L2224/32151—Disposition the layer connector connecting 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
    • H01L2224/32221—Disposition the layer connector connecting 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
    • H01L2224/32245—Disposition the layer connector connecting 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
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    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
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    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof
    • H01L2224/45138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron (B), silicon (Si), germanium (Ge), arsenic (As), antimony (Sb), tellurium (Te) and polonium (Po), and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
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    • H01L2224/4805—Shape
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    • H01L2224/48151—Connecting 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
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    • H01L2224/48247—Connecting 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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    • H01L2224/01—Means 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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
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    • H01L2224/48151—Connecting 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
    • H01L2224/48221—Connecting 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
    • H01L2224/48245—Connecting 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
    • H01L2224/48257—Connecting 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
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    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/49—Structure, shape, material or disposition of the wire connectors after the connecting process of a plurality of wire connectors
    • H01L2224/491—Disposition
    • H01L2224/49105—Connecting at different heights
    • H01L2224/49107—Connecting at different heights on the semiconductor or solid-state body
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    • H01L2224/73—Means 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
    • H01L2224/732—Location after the connecting process
    • H01L2224/73251—Location after the connecting process on different surfaces
    • H01L2224/73265—Layer and wire connectors
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01019—Potassium [K]
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
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    • H01L2924/181—Encapsulation

Landscapes

  • Led Device Packages (AREA)
  • Led Devices (AREA)
  • Luminescent Compositions (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a device emitting light of warm-colored white tinged with red, and to provide a nitride fluorophor having an emission spectrum in a yellow to red region and usable with a blue LED. <P>SOLUTION: The light-emitting device comprises a blue semiconductor lighting element 10 and a nitride fluorophor 11 having an emission spectrum of the yellow to red region and excited by the blue semiconductor lighting element 10, wherein the nitride fluorophor comprises basic component elements of Ca<SB>2</SB>Si<SB>5</SB>N<SB>7</SB>: Eu and B, Al, Cu, Mg or the like. <P>COPYRIGHT: (C)2004,JPO

Description

【発明の詳細な説明】Detailed Description of the Invention

【０００１】[0001]

【発明の属する技術分野】本発明は、ディスプレイ、液
晶用バックライト、蛍光ランプ等の照明に使用される発
光装置に関する。詳しくは、半導体発光素子（以下、
「ＬＥＤ」という。）と蛍光体とを組み合わせた発光装
置に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting device used for illumination of a display, a liquid crystal backlight, a fluorescent lamp and the like. Specifically, the semiconductor light emitting device (hereinafter,
It is called "LED". ) And a phosphor.

【０００２】[0002]

【従来の技術】ＬＥＤは、小型で電力効率が良く鮮やか
な色の発光をする。また、ＬＥＤランプに用いられるＬ
ＥＤチップは、半導体素子であるため球切れなどの心配
がない。さらに初期駆動特性が優れ、振動やオン・オフ
点灯の繰り返しに強いという特徴を有する。このような
優れた特性を有するため、ＬＥＤは、各種の光源として
利用されている。2. Description of the Related Art LEDs are small, power efficient and emit bright colors. In addition, L used for LED lamps
Since the ED chip is a semiconductor element, there is no fear of breaking the ball. Furthermore, it has excellent initial drive characteristics and is resistant to vibration and repeated on / off lighting. Due to such excellent characteristics, LEDs are used as various light sources.

【０００３】ＬＥＤの光の一部を蛍光体により波長変換
し、当該波長変換された光と波長変換されないＬＥＤの
光とを混合して放出することにより、ＬＥＤの光と異な
る発光色を発光する発光装置が製造されている。例え
ば、白色の発光装置の場合、発光源のチップ表面には、
蛍光体が薄くコーディングされている。該チップは、Ｉ
ｎＧａＮ系材料を使った青色ＬＥＤである。また、コー
ディング層には、（Ｙ，Ｇｄ）３（Ａｌ，Ｇａ）５Ｏ
１２の組成式で表されるＹＡＧ系蛍光体が使われてい
る。白色の発光装置の発光色は、光の混色の原理によっ
て得られる。チップから放出された青色光は、蛍光体層
の中へ入射した後、層内で何回かの吸収と散乱を繰り返
した後、外へ放出される。一方、蛍光体に吸収された青
色光は励起源として働き、黄色の蛍光を発する。この黄
色光と青色光が混ぜ合わされて人間の目には白色として
見える。A part of the light of the LED is wavelength-converted by a phosphor, and the wavelength-converted light and the light of the LED not wavelength-converted are mixed and emitted, thereby emitting a light emission color different from that of the LED. Light emitting devices are being manufactured. For example, in the case of a white light emitting device, on the chip surface of the light emitting source,
The phosphor is lightly coded. The chip is I
It is a blue LED using an nGaN-based material. Further, the coding layer includes (Y, Gd) 3 (Al, Ga) 5 O.
The YAG-based phosphor represented by the composition formula 12 is used. The emission color of the white light emitting device is obtained by the principle of color mixing of light. The blue light emitted from the chip enters the phosphor layer, is absorbed and scattered several times in the layer, and then is emitted to the outside. On the other hand, the blue light absorbed by the phosphor acts as an excitation source and emits yellow fluorescence. The yellow light and the blue light are mixed and appear as white to human eyes.

【０００４】[0004]

【発明が解決しようとする課題】しかし、公知の白色に
発光する発光装置は、可視光領域の長波長側の発光が得
られにくいため、やや青白い白色の発光装置となってい
た。特に、店頭のディスプレイ用の照明や、医療現場用
の照明などおいては、やや赤みを帯びた暖色系の白色の
発光装置が、強く求められている。また、ＬＥＤは、電
球と比べて、一般に寿命が長く、人の目にやさしいた
め、電球色に近い白色の発光装置が、強く求められてい
る。However, the known light-emitting device that emits white light has a slightly pale white light-emitting device because it is difficult to obtain light emission on the long wavelength side of the visible light region. Particularly in lighting for displays in stores, lighting for medical sites, etc., there is a strong demand for a slightly reddish warm white light emitting device. In addition, LEDs generally have a longer life and are easier on human eyes than light bulbs. Therefore, a white light emitting device that is close to a light bulb color is strongly demanded.

【０００５】従って、本発明は、やや赤みを帯びた暖色
系の白色の発光装置を提供することを目的とする。ま
た、青色ＬＥＤ等と組み合わせて使用する黄から赤領域
に発光スペクトルを有する窒化物蛍光体を提供すること
を目的とする。Therefore, an object of the present invention is to provide a slightly reddish warm-colored white light-emitting device. Another object of the present invention is to provide a nitride phosphor having an emission spectrum in the yellow to red region, which is used in combination with a blue LED or the like.

【０００６】[0006]

【課題を解決するための手段】上記課題を解決するため
に、本発明は、第１の発光スペクトルの少なくとも一部
を変換し、前記第１の発光スペクトルと異なる領域に第
２の発光スペクトルを少なくとも１以上有している、基
本構成元素に少なくとも窒素を含有する窒化物蛍光体で
あって、前記窒化物蛍光体は、ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｚ（Ｌは、Ｂｅ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｄ、ＨｇのＩＩ価からなる群
より選ばれる少なくとも１種以上を含有する。Ｍは、
Ｃ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ、ＨｆのＩＶ価から
なる群より選ばれる少なくとも１種以上を含有する。Ｚ
は、賦活剤である。）で表される基本構成元素を少なく
とも含有しており、かつ、Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｃ
ａ、Ｇａ、Ｉｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｌｉ、Ｎａ、
Ｋ、Ｒｅ、Ｎｉ、Ｃｒ、Ｍｏ、Ｏ及びＦｅからなる群よ
り選ばれる少なくとも１種以上を含有することを特徴と
する窒化物蛍光体に関する。上記基本構成元素及びＭ
ｎ、Ｂ等の成分構成元素を少なくとも含有することによ
り、発光輝度、エネルギー効率、量子効率等の発光効率
の向上を図ることができる。この理由は定かではない
が、上記基本構成元素にＭｎ、Ｂ等の成分構成元素を含
有させることにより粉体の粒径が均一かつ大きくなり、
結晶性が著しく良くなるためであると考えられる。結晶
性を良くすることにより、第１の発光スペクトルを高効
率に波長変換し、発光効率の良好な第２の発光スペクト
ルを有する窒化物蛍光体にすることができる。また、蛍
光体の残光特性を任意に調整することができる。ディス
プレイ、ＰＤＰ等のように表示が連続して繰り返し行わ
れるような表示装置では、残光特性が問題となる。その
ため、窒化物蛍光体の基本構成元素に、Ｂ、Ｍｇ、Ｃ
ｒ、Ｎｉ、Ａｌなどを微量に含有させることにより、残
光を抑えることができる。これにより、ディスプレイ等
の表示装置に本発明に係る窒化物蛍光体を使用すること
ができる。このように、蛍光体に含有されている基本構
成元素および成分構成元素を変えることによって、蛍光
体の粒径、結晶性、エネルギー伝達経路が変わり、吸
収、反射、散乱が変化し、発光及び光の取り出し、残光
などの発光装置における発光特性に大きく影響を及ぼす
からである。In order to solve the above-mentioned problems, the present invention converts at least a part of the first emission spectrum and sets the second emission spectrum in a region different from the first emission spectrum. A nitride phosphor containing at least one or more nitrogen as a basic constituent element, wherein the nitride phosphor is L X M Y N
(2 / 3X + 4 / 3Y) : Z (L is Be, Mg, C
It contains at least one selected from the group consisting of II valences of a, Sr, Ba, Zn, Cd, and Hg. M is
It contains at least one selected from the group consisting of IV values of C, Si, Ge, Sn, Ti, Zr and Hf. Z
Is an activator. ) Containing at least the basic constituent element represented by the formula (1) and Mg, Sr, Ba, Zn, C
a, Ga, In, B, Al, Cu, Mn, Li, Na,
The present invention relates to a nitride phosphor containing at least one selected from the group consisting of K, Re, Ni, Cr, Mo, O and Fe. The above basic constituent elements and M
By containing at least the component constituent elements such as n and B, it is possible to improve the luminous efficiency such as luminous brightness, energy efficiency, and quantum efficiency. The reason for this is not clear, but the particle diameter of the powder becomes uniform and large by adding the constituent constituent elements such as Mn and B to the above basic constituent elements.
It is considered that this is because the crystallinity is remarkably improved. By improving the crystallinity, the wavelength of the first emission spectrum can be converted with high efficiency, and the nitride phosphor having the second emission spectrum of good emission efficiency can be obtained. In addition, the afterglow characteristics of the phosphor can be adjusted arbitrarily. In a display device such as a display or PDP in which display is continuously and repeatedly performed, the afterglow characteristic becomes a problem. Therefore, B, Mg, and C are added to the basic constituent elements of the nitride phosphor.
Afterglow can be suppressed by containing a small amount of r, Ni, Al, or the like. As a result, the nitride phosphor according to the present invention can be used in a display device such as a display. In this way, by changing the basic constituent elements and constituent constituent elements contained in the phosphor, the particle size, crystallinity, and energy transfer path of the phosphor are changed, absorption, reflection, and scattering are changed, and light emission and light emission are changed. This is because the light emission characteristics of the light emitting device, such as light extraction and afterglow, are greatly affected.

【０００７】前記窒化物蛍光体は、ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｚ（Ｌは、Ｍｇ、Ｃａ、Ｓ
ｒ、ＢａのＩＩ価からなる群より選ばれる少なくとも１
種以上を含有する。Ｍは、Ｓｉである。Ｚは、賦活剤で
ある。）で表される基本構成元素を少なくとも含有して
おり、かつ、Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃ
ｕ、Ｍｎ、Ｃｒ、Ｏ及びＮｉからなる群より選ばれる少
なくとも１種以上を含有することが好ましい。Ｌを、Ｍ
ｇ、Ｃａ、Ｓｒ、Ｂａにすることにより、また、ＭをＳ
ｉにすることにより、分解し難い信頼性が高く結晶性の
良好な窒化物蛍光体を提供することができるからであ
る。これに伴い、ライフ特性の良好な発光装置を提供す
ることができるからである。この窒化物蛍光体は、第１
の発光スペクトルに４００〜４６０ｎｍの波長を有する
青色ＬＥＤを使用して、本発明に係る窒化物蛍光体に照
射すると５６０〜６８０付近にピーク波長を有する、白
色に発光する発光装置を製造することができる。The nitride phosphor is L X M Y N
(2 / 3X + 4 / 3Y) : Z (L is Mg, Ca, S
at least 1 selected from the group consisting of r and Ba II valences
Contains more than one seed. M is Si. Z is an activator. ) Containing at least the basic constituent element represented by the formula (1) and Mg, Sr, Ba, Zn, B, Al, C
It is preferable to contain at least one selected from the group consisting of u, Mn, Cr, O and Ni. L for M
By using g, Ca, Sr, and Ba, M can be changed to S
This is because by setting i, it is possible to provide a nitride phosphor that is difficult to decompose and has high reliability and good crystallinity. With this, it is possible to provide a light emitting device having good life characteristics. This nitride phosphor is the first
It is possible to manufacture a light emitting device which emits white light having a peak wavelength in the vicinity of 560 to 680 when the nitride phosphor according to the present invention is irradiated by using a blue LED having a wavelength of 400 to 460 nm in its emission spectrum. it can.

【０００８】前記Ｚで表される賦活剤は、Ｅｕであるこ
とが好ましい。これにより、２５０〜４８０ｎｍ付近の
第１の発光スペクトルを吸収し、該吸収により第１の発
光スペクトルと異なる領域、特に黄から赤領域に第２の
発光スペクトルを有することができるからである。具体
的には、４６０ｎｍに励起された第１の発光スペクトル
を窒化物蛍光体に照射すると、５８０から６２０ｎｍ近
傍に最大波長を示す窒化物蛍光体を提供することができ
るからである。これにより、青色ＬＥＤと本発明の窒化
物蛍光体とを組み合わせることにより、白色に発光する
発光装置を提供することができる。The activator represented by Z is preferably Eu. This makes it possible to absorb the first emission spectrum in the vicinity of 250 to 480 nm and to have the second emission spectrum in a region different from the first emission spectrum due to the absorption, particularly in the yellow to red region. Specifically, when the nitride phosphor is irradiated with the first emission spectrum excited at 460 nm, the nitride phosphor having the maximum wavelength in the vicinity of 580 to 620 nm can be provided. This makes it possible to provide a light emitting device that emits white light by combining the blue LED and the nitride phosphor of the present invention.

【０００９】前記Ｚで表される賦活剤は、Ｍｎ、Ｂ、Ｃ
ｅ、Ｍｇ、Ｃｕ、Ａｌ及びＥｕのうち少なくとも１種以
上を含有するものであることが好ましい。これにより、
賦活剤にＥｕのみを用いる場合と異なる領域に最大波長
を示す等、発光特性の良い窒化物蛍光体を提供すること
ができるからである。The activator represented by Z is Mn, B or C.
It is preferable that at least one of e, Mg, Cu, Al and Eu is contained. This allows
This is because it is possible to provide a nitride phosphor having good emission characteristics, such as having a maximum wavelength in a region different from the case where only Eu is used as an activator.

【００１０】前記Ｘ及びＹは、Ｘ＝２、Ｙ＝５であるこ
とが好ましい。つまり、基本構成元素は、Ｌ２Ｍ
５Ｎ８：Ｚで表される。これにより結晶性の良好な窒化
物蛍光体を提供することができるからである。但し、Ｌ
の一部はＺで置換されるため、ＬとＺとの合計モル数が
Ｘ＝２となる。つまり、Ｚ０．０３である場合、基本構
成元素は、Ｌ１．９７Ｚ０．０３Ｍ５Ｎ８と表される。It is preferable that X and Y are X = 2 and Y = 5. That is, the basic constituent element is L 2 M.
It is represented by 5 N 8 : Z. This is because it is possible to provide a nitride phosphor having good crystallinity. However, L
Is partially replaced with Z, the total number of moles of L and Z is X = 2. That is, when Z 0.03 , the basic constituent element is represented as L 1.97 Z 0.03 M 5 N 8 .

【００１１】前記Ｘ及びＹは、Ｘ＝１、Ｙ＝７であるこ
とが好ましい。つまり、基本構成元素は、ＬＭ
７Ｎ１０：Ｚで表される。これにより結晶性の良好な窒
化物蛍光体を提供することができるからである。It is preferable that X and Y are X = 1 and Y = 7. In other words, the basic constituent element is LM
It is represented by 7 N 10 : Z. This is because it is possible to provide a nitride phosphor having good crystallinity.

【００１２】前記Ｌと前記Ｚとは、Ｌ：Ｚ＝１：０．０
０１〜１のモル比の関係を有することが好ましい。ＬＸ
ＭＹＮ（２／３Ｘ＋４／３Ｙ）：Ｚで表される基本構成
元素中のＺの配合割合を上記範囲にすることにより、高
輝度の窒化物蛍光体を得ることができる。また、温度特
性が良好な窒化物蛍光体を提供することができる。より
好ましくは、Ｌ：Ｚ＝１：０．００３〜０．０５のモル
比の関係である。この範囲の時に、高輝度で、温度特性
の良好な窒化物蛍光体を提供することができるからであ
る。また、原料のＥｕの化合物が高価であるため、Ｅｕ
の化合物の配合比率を減少することにより、より低廉な
蛍光体を製造することが可能である。The L and the Z are L: Z = 1: 0.0
It is preferable to have the relationship of the molar ratio of 01 to 1. L X
By setting the compounding ratio of Z in the basic constituent element represented by M Y N (2 / 3X + 4 / 3Y) : Z within the above range, a high-luminance nitride phosphor can be obtained. Further, it is possible to provide a nitride phosphor having good temperature characteristics. More preferably, the relationship is a molar ratio of L: Z = 1: 0.003 to 0.05. This is because in this range, it is possible to provide a nitride phosphor having high brightness and good temperature characteristics. In addition, since the raw material Eu compound is expensive, Eu
By reducing the compounding ratio of the compound (1), it is possible to manufacture a cheaper phosphor.

【００１３】前記窒化物蛍光体は、平均粒径が０．１〜
１０μｍの大きさであることが好ましい。ＬＥＤやＬＥ
Ｄランプのような発光装置の場合、最適蛍光膜厚はほぼ
平均粒径に比例していて、粒径が小さいほど塗布量は少
なくてすむ。その一方、発光効率は一般に大粒径の方が
大きい。本発明は、発光輝度、エネルギー効率、量子効
率が高い発光特性の良好な窒化物蛍光体を提供できると
共に、取り扱いやすく塗布量を少なくすることができる
窒化物蛍光体を提供することができる。The nitride phosphor has an average particle size of 0.1 to 0.1.
The size is preferably 10 μm. LED and LE
In the case of a light emitting device such as a D lamp, the optimum fluorescent film thickness is almost proportional to the average particle size, and the smaller the particle size, the smaller the coating amount. On the other hand, the luminous efficiency is generally larger for larger particles. INDUSTRIAL APPLICABILITY The present invention can provide a nitride phosphor having high emission characteristics, high energy efficiency, and high quantum efficiency and good emission characteristics, and can also provide a nitride phosphor that is easy to handle and can reduce the coating amount.

【００１４】前記窒化物蛍光体は、黄から赤領域に第２
の発光スペクトルを少なくとも１以上有していることが
好ましい。青色ＬＥＤと黄から赤領域に第２の発光スペ
クトルを有する窒化物蛍光体とを組み合わせることによ
り、暖色系の白色に発光する発光装置を提供することが
できる。The nitride phosphor has a second region in the yellow to red region.
It is preferable to have at least one emission spectrum of. By combining the blue LED and the nitride phosphor having the second emission spectrum in the yellow to red region, it is possible to provide a light emitting device that emits warm white light.

【００１５】前記窒化物蛍光体は、５２０ｎｍから７８
０ｎｍの波長範囲に前記第２の発光スペクトルを少なく
とも１以上有していることが好ましい。４００〜４６０
ｎｍに励起された紫外又は青色ＬＥＤと５７０ｎｍから
７３０ｎｍの波長範囲に前記第２の発光スペクトルを有
する窒化物蛍光体とを組み合わせることにより、暖色系
の白色に発光する発光装置を提供することができる。The nitride phosphor is 520 nm to 78 nm.
It is preferable to have at least one second emission spectrum in the wavelength range of 0 nm. 400-460
It is possible to provide a light-emitting device that emits warm white light by combining an ultraviolet or blue LED excited by nm with a nitride phosphor having the second emission spectrum in the wavelength range of 570 nm to 730 nm. .

【００１６】本発明は、ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｚ（Ｌは、Ｂｅ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｄ、ＨｇのＩＩ価からなる群
より選ばれる少なくとも１種以上を含有する。Ｍは、
Ｃ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ、ＨｆのＩＶ価から
なる群より選ばれる少なくとも１種以上を含有する。Ｚ
は、賦活剤である。）で表される基本構成元素を少なく
とも含有しており、かつ、Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｃ
ａ、Ｇａ、Ｉｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｌｉ、Ｎａ、
Ｋ、Ｒｅ、Ｎｉ、Ｃｒ、Ｍｏ、Ｏ及びＦｅからなる群よ
り選ばれる少なくとも１種以上を含有する窒化物蛍光体
の製造方法であって、前記窒化物蛍光体の原料を、アン
モニア雰囲気中で焼成が行われる工程を有することを特
徴とする窒化物蛍光体の製造方法に関する。焼成工程に
おいて、還元ガスとして通常水素を数％含む窒素が使用
されるが、水素がるつぼ、炉等を浸食するため、浸食さ
れたるつぼ材質が蛍光体組成中に含まれるようになる。
このようなるつぼ材質は、不純物となり、発光輝度、量
子効率、エネルギー効率などの発光効率の低下を引き起
こす原因となる。このため、アンモニア雰囲気中で焼成
を行うことにより、るつぼを浸食せず、不純物を含まな
い発光効率の高い蛍光体を製造することができる。ま
た、反応性が向上し歩留りが極めて高い蛍光体を製造す
ることができる。The present invention is based on L X M Y N
(2 / 3X + 4 / 3Y) : Z (L is Be, Mg, C
It contains at least one selected from the group consisting of II valences of a, Sr, Ba, Zn, Cd, and Hg. M is
It contains at least one selected from the group consisting of IV values of C, Si, Ge, Sn, Ti, Zr and Hf. Z
Is an activator. ) Containing at least the basic constituent element represented by the formula (1) and Mg, Sr, Ba, Zn, C
a, Ga, In, B, Al, Cu, Mn, Li, Na,
A method for producing a nitride phosphor containing at least one selected from the group consisting of K, Re, Ni, Cr, Mo, O and Fe, wherein the raw material of the nitride phosphor is in an ammonia atmosphere. The present invention relates to a method for manufacturing a nitride phosphor, which has a step of firing. In the firing step, nitrogen containing a few% of hydrogen is usually used as a reducing gas, but since hydrogen erodes the crucible, the furnace, etc., the eroded crucible material is included in the phosphor composition.
Such a crucible material becomes an impurity and causes a decrease in luminous efficiency such as luminous brightness, quantum efficiency, and energy efficiency. Therefore, by performing the firing in an ammonia atmosphere, it is possible to manufacture a phosphor that does not corrode the crucible and that does not contain impurities and that has high luminous efficiency. Further, it is possible to manufacture a phosphor having improved reactivity and extremely high yield.

【００１７】前記焼成は、窒化ホウ素材質のるつぼを用
いて焼成を行うことが好ましい。モリブデンるつぼは、
発光を阻害したり、反応系を阻害したりするおそれがあ
る。一方、窒化ホウ素材質のるつぼを使用する場合は、
発光を阻害したり反応系を阻害したりすることがないた
め、極めて高純度の窒化物蛍光体を製造することができ
るからである。また、窒化ホウ素材質のるつぼは、水素
窒素中で分解するため、水素窒素雰囲気中での焼成に使
用することができない。The firing is preferably performed using a crucible made of boron nitride. Molybdenum crucible
There is a risk of blocking the light emission or the reaction system. On the other hand, when using a crucible made of boron nitride,
This is because it does not hinder the light emission or the reaction system, and therefore an extremely high-purity nitride phosphor can be manufactured. Moreover, since the crucible made of boron nitride decomposes in hydrogen nitrogen, it cannot be used for firing in a hydrogen nitrogen atmosphere.

【００１８】本発明は、第１の発光スペクトルを有する
半導体発光素子と、前記第１の発光スペクトルの少なく
とも一部を変換し、前記第１の発光スペクトルと異なる
領域に第２の発光スペクトルを少なくとも１以上有して
いる蛍光体と、を少なくとも有する発光装置であって、
前記蛍光体には、請求項１乃至１１の少なくともいずれ
か１項に記載の窒化物蛍光体が含有されていることを特
徴とする発光装置に関する。これにより暖色系の白色に
発光する発光装置を提供することができる。According to the present invention, a semiconductor light emitting device having a first emission spectrum and at least a part of the first emission spectrum are converted, and at least a second emission spectrum is provided in a region different from the first emission spectrum. What is claimed is: 1. A light emitting device comprising at least a phosphor having one or more,
A phosphor according to claim 1, wherein the phosphor contains the nitride phosphor according to any one of claims 1 to 11. This makes it possible to provide a light emitting device that emits warm white light.

【００１９】前記蛍光体には、セリウムで賦活されたイ
ットリウム・アルミニウム酸化物系蛍光物質が含有され
ていることが好ましい。ＹＡＧ系蛍光物質を含有するこ
とにより、所望の発光色に調節することができる。青色
ＬＥＤとＹＡＧ系蛍光体とを用いた発光装置では、色度
座標Ｘ＝０．３４８、Ｙ＝０．３６７、色温度４９３９
Ｋ、肉眼観察で青白い白色の発光が見られる。これに対
して、青色ＬＥＤと請求項１乃至１１の窒化物蛍光体及
びＹＡＧ系蛍光体とを混合した蛍光体とを用いた発光装
置では、色度座標Ｘ＝０．４５４、Ｙ＝０．４１６、色
温度２８２８Ｋ、肉眼観察で暖色系の白色の発光が見ら
れる。このように青色ＬＥＤと請求項１乃至１１の窒化
物蛍光体及びＹＡＧ系蛍光体とを混合した蛍光体とを用
いた発光装置を用いることにより、目に優しい暖色系の
白色の発光装置を提供することができる。特に、電球色
の発光装置を提供することができる。また、ＹＡＧ系蛍
光体に限られず、半導体発光素子と、発光特性の極めて
優れた蛍光体とを組み合わせることにより、青、緑、赤
の他、種々の色を発光することができる発光装置を提供
することができる。It is preferable that the phosphor contains a yttrium-aluminum oxide-based phosphor activated by cerium. By containing a YAG-based fluorescent substance, a desired emission color can be adjusted. A light emitting device using a blue LED and a YAG-based phosphor has chromaticity coordinates X = 0.348, Y = 0.369, and color temperature 4939.
K, pale white luminescence is observed by visual observation. On the other hand, in the light emitting device using the blue LED and the phosphor obtained by mixing the nitride phosphor and the YAG phosphor according to claims 1 to 11, chromaticity coordinates X = 0.454, Y = 0. 416, color temperature 2828K, warm-colored white light emission is observed by visual observation. By using the light emitting device using the blue LED and the phosphor obtained by mixing the nitride phosphor and the YAG phosphor according to any one of claims 1 to 11, a warm white light emitting device that is easy on the eyes is provided. can do. In particular, it is possible to provide a light emitting device having a light bulb color. Further, the present invention is not limited to YAG-based phosphors, and provides a light-emitting device that can emit various colors other than blue, green, and red by combining a semiconductor light-emitting element and a phosphor having extremely excellent light-emitting characteristics. can do.

【００２０】前記蛍光体に含有されている、前記セリウ
ムで賦活されたイットリウム・アルミニウム酸化物系蛍
光物質と前記請求項１乃至１１の少なくともいずれか１
項に記載の窒化物蛍光体との重量比率は、１〜１５対１
で混合されていることが好ましい。ＹＡＧ系蛍光体と請
求項１乃至１１に記載の窒化物蛍光体との配合量を変え
ることにより、色温度の微調節が可能となる。特に、上
記配合比率にすることにより、発光効率が良好な暖色系
の白色の発光を行う発光装置を提供することができる。The yttrium-aluminum oxide fluorescent substance activated by cerium contained in the fluorescent substance, and at least any one of claims 1 to 11.
The weight ratio with the nitride phosphor described in the item 1 to 15: 1.
It is preferable that they are mixed with each other. The color temperature can be finely adjusted by changing the compounding amounts of the YAG-based phosphor and the nitride phosphor according to any one of claims 1 to 11. In particular, with the above blending ratio, it is possible to provide a light emitting device that emits warm white light with good emission efficiency.

【００２１】前記第１の発光スペクトルは、３６０〜５
５０ｎｍに発光波長を有しており、前記第１の発光スペ
クトルの少なくとも一部が変換された光と、前記第１の
発光スペクトルの他の一部と、が混合されて放出される
ことにより白色系の発光が行われることが好ましい。第
１の発光スペクトルにＥＸ＝４６０ｎｍの発光波長を有
する青色ＬＥＤを使用することができる他、ＥＸ＝４０
０ｎｍの発光波長を有する紫外ＬＥＤも使用することが
できる。紫外ＬＥＤは、可視光線でないため、電流変化
に伴う発光の微小変化を人間（目）が感じることがない
ため、色変化がない。本発明に係る窒化物蛍光体は、３
６０〜４８０ｎｍ辺りの発光波長を吸収するため、ＥＸ
＝４００ｎｍの紫外ＬＥＤを使用することができる。従
って、３６０〜５５０ｎｍ付近の発光波長を有する第１
の発光スペクトルを有する白色の発光装置を提供するこ
とができる。The first emission spectrum is 360 to 5
A light having an emission wavelength of 50 nm, in which at least a part of the first emission spectrum is converted, and the other part of the first emission spectrum are mixed and emitted to emit white light. It is preferred that the system emits light. A blue LED having an emission wavelength of EX = 460 nm can be used in the first emission spectrum, and EX = 40
Ultraviolet LEDs with an emission wavelength of 0 nm can also be used. Since the ultraviolet LED is not visible light, humans (eyes) do not perceive a slight change in light emission due to a change in current, so that there is no color change. The nitride phosphor according to the present invention has 3
Since the emission wavelength around 60 to 480 nm is absorbed, EX
= 400 nm UV LED can be used. Therefore, the first light emitting device having an emission wavelength near 360 to 550 nm
It is possible to provide a white light emitting device having an emission spectrum of.

【００２２】前記蛍光体は、粉体又は粒体であって、光
透光性材料に含有されていることが好ましい。これによ
り、発光色の微調整を容易にでき、発光効率を高めるこ
とができる。The phosphor is a powder or granules, and is preferably contained in the light transmissive material. Thereby, fine adjustment of the emission color can be facilitated, and the emission efficiency can be improved.

【００２３】前記半導体発光素子は、ＩＩＩ族窒化物系
化合物半導体発光素子であることが好ましい。これによ
り、発光輝度を高め、信頼性の高い発光装置を提供する
ことができる。本発明に係る窒化物蛍光体で半導体発光
素子の全部又は一部を覆う場合、窒化物蛍光体と半導体
発光素子との境界面に生じる劣化、反発、剥離などの諸
問題を、同一系の材質を用いることで抑えられるからで
ある。前記発光装置は、平均演色評価数Ｒａが７５乃至
９５であり、色温度が２０００Ｋから８０００Ｋである
ことが好ましい。これにより暖色系の白色の発光装置を
提供することができる。特に、好ましくは色温度が３０
００Ｋから５０００Ｋであり、電球色の発光装置を提供
することができる。また、特殊演色性Ｒ９の値を高くす
ることにより赤み帯びた白色の発光装置を提供すること
ができる。以上のことから、本発明は、やや赤みを帯び
た暖色系の白色の発光装置を提供すること、青色ＬＥＤ
等と組み合わせて使用する黄から赤領域に発光スペクト
ルを有する窒化物蛍光体を提供することが可能であると
いう技術的意義を有する。The semiconductor light emitting device is preferably a group III nitride compound semiconductor light emitting device. Accordingly, it is possible to provide a highly reliable light emitting device with increased emission brightness. When covering all or a part of the semiconductor light emitting device with the nitride phosphor according to the present invention, various problems such as deterioration, repulsion, and peeling occurring at the boundary surface between the nitride phosphor and the semiconductor light emitting device are caused by the same material. This is because it can be suppressed by using. The light emitting device preferably has an average color rendering index Ra of 75 to 95 and a color temperature of 2000K to 8000K. As a result, a warm white light emitting device can be provided. Particularly preferably, the color temperature is 30.
It is from 00K to 5000K, and it is possible to provide a light emitting device having a bulb color. Further, by increasing the value of the special color rendering R9, a reddish white light emitting device can be provided. From the above, the present invention provides a slightly reddish warm white light emitting device, and a blue LED.
It has a technical significance that it is possible to provide a nitride phosphor having an emission spectrum in the yellow to red region, which is used in combination with the above.

【００２４】[0024]

【発明の実施の形態】以下、本発明に係る窒化物蛍光体
及びその製造方法、並びに発光装置を、発明の実施の形
態及び実施例を用いて説明する。だたし、本発明は、こ
の実施の形態及び実施例に限定されない。BEST MODE FOR CARRYING OUT THE INVENTION A nitride phosphor, a method for manufacturing the same, and a light emitting device according to the present invention will be described below with reference to embodiments and examples of the invention. However, the present invention is not limited to this embodiment and examples.

【００２５】本発明に係る発光装置は、第１の発光スペ
クトルを有する半導体発光素子と、前記第１の発光スペ
クトルの少なくとも一部を変換し、前記第１の発光スペ
クトルと異なる領域に第２の発光スペクトルを少なくと
も１以上有している蛍光体と、を少なくとも有する発光
装置である。具体的な発光装置の一例として、図１を用
いて説明する。図１は、本発明に係る発光装置を示す図
である。A light emitting device according to the present invention converts a semiconductor light emitting element having a first emission spectrum and at least a part of the first emission spectrum into a second region in a region different from the first emission spectrum. And a phosphor having at least one emission spectrum. An example of a specific light emitting device will be described with reference to FIG. FIG. 1 is a diagram showing a light emitting device according to the present invention.

【００２６】発光装置は、サファイア基板１の上部に積
層された半導体層２と、該半導体層２に形成された正負
の電極３から延びる導電性ワイヤ１４で導電接続された
リードフレーム１３と、該サファイア基板１と該半導体
層２とから構成される半導体発光素子１０の外周を覆う
ようにリードフレーム１３ａのカップ内に設けられた蛍
光体１１とコーティング部材１２と、該蛍光体１１及び
該リードフレーム１３の外周面を覆うモールド部材１５
と、から構成されている。The light emitting device includes a semiconductor layer 2 laminated on the sapphire substrate 1, a lead frame 13 conductively connected by conductive wires 14 extending from positive and negative electrodes 3 formed on the semiconductor layer 2, and A phosphor 11 and a coating member 12 provided in a cup of a lead frame 13a so as to cover the outer periphery of a semiconductor light emitting element 10 composed of a sapphire substrate 1 and the semiconductor layer 2, the phosphor 11 and the lead frame. Mold member 15 for covering the outer peripheral surface of 13
It consists of and.

【００２７】サファイア基板１上に半導体層２が形成さ
れ、該半導体層２の同一平面側に正負の電極３が形成さ
れている。前記半導体層２には、発光層（図示しない）
が設けられており、この発光層から出力される発光ピー
クは、青色領域にある４６０ｎｍ近傍の発光スペクトル
を有する。この半導体発光素子１０をダイボンダーにセ
ットし、カップが設けられたリードフレーム１３ａにフ
ェイスアップしてダイボンド（接着）する。ダイボンド
後、リードフレーム１３をワイヤーボンダーに移送し、
半導体発光素子の負電極３をカップの設けられたリード
フレーム１３ａに金線でワイヤーボンドし、正電極３を
もう一方のリードフレーム１３ｂにワイヤーボンドす
る。次に、モールド装置に移送し、モールド装置のディ
スペンサーでリードフレーム１３のカップ内に蛍光体１
１及びコーティング部材１２を注入する。蛍光体１１と
コーティング部材１２とは、予め所望の割合に均一に混
合しておく。蛍光体１１注入後、予めモールド部材１５
が注入されたモールド型枠の中にリードフレーム１３を
浸漬した後、型枠をはずして樹脂を硬化させ、図１に示
すような砲弾型の発光装置とする。A semiconductor layer 2 is formed on a sapphire substrate 1, and positive and negative electrodes 3 are formed on the same plane side of the semiconductor layer 2. The semiconductor layer 2 includes a light emitting layer (not shown).
Is provided, and the emission peak output from this emission layer has an emission spectrum near 460 nm in the blue region. The semiconductor light emitting device 10 is set in a die bonder, face-up to a lead frame 13a provided with a cup, and die bonded (bonded). After die bonding, transfer the lead frame 13 to the wire bonder,
The negative electrode 3 of the semiconductor light emitting element is wire-bonded to the lead frame 13a provided with the cup with a gold wire, and the positive electrode 3 is wire-bonded to the other lead frame 13b. Next, the phosphor 1 is transferred to a molding device and placed in a cup of the lead frame 13 by a dispenser of the molding device.
1 and the coating member 12 are injected. The phosphor 11 and the coating member 12 are uniformly mixed in a desired ratio in advance. After injecting the phosphor 11, the mold member 15 is previously formed.
After immersing the lead frame 13 in the mold frame in which was injected, the mold frame was removed and the resin was cured to obtain a shell type light emitting device as shown in FIG.

【００２８】以下、本発明に係る発光装置の構成部材に
ついて詳述する。The constituent members of the light emitting device according to the present invention will be described in detail below.

【００２９】（蛍光体）本発明に係る窒化物蛍光体は、
ＬＸＭＹＮ（２／３Ｘ＋４／３Ｙ）：Ｚで表される基本
構成元素を少なくとも含有しており、かつ、Ｍｇ、Ｓ
ｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｃｒ、Ｏ及び
Ｆｅ等からなる群より選ばれる少なくとも１種以上を含
有する窒化物蛍光体である。(Phosphor) The nitride phosphor according to the present invention is
L X M Y N (2 / 3X + 4 / 3Y) : contains at least a basic constituent element represented by Z, and Mg, S
A nitride phosphor containing at least one selected from the group consisting of r, Ba, Zn, B, Al, Cu, Mn, Cr, O and Fe.

【００３０】Ｌは、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚ
ｎ、Ｃｄ、ＨｇのＩＩ価からなる群より選ばれる少なく
とも１種以上を含有するものである。特に、分解し難い
信頼性の高い窒化物蛍光体を提供することができること
から、Ｍｇ、Ｃａ、Ｓｒ、Ｂａを用いることが好まし
い。これらの構成元素を、１種類のみ用いたものも使用
できるほか、該１種類の一部を他の構成元素で置換した
ものでも良い。L is Be, Mg, Ca, Sr, Ba, Z
It contains at least one selected from the group consisting of II-values of n, Cd, and Hg. In particular, it is preferable to use Mg, Ca, Sr, or Ba because a highly reliable nitride phosphor that is difficult to decompose can be provided. One of these constituent elements may be used alone, or one of the constituent elements may be partially replaced with another constituent element.

【００３１】Ｍは、Ｃ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚ
ｒ、ＨｆのＩＶ価からなる群より選ばれる少なくとも１
種以上を含有するものである。特に、ＭをＳｉにするこ
とにより安価で結晶性の良好な窒化物蛍光体を提供する
ことができる。M is C, Si, Ge, Sn, Ti, Z
at least 1 selected from the group consisting of r and Hf IV values
It contains more than one species. In particular, when M is Si, it is possible to provide an inexpensive nitride phosphor having good crystallinity.

【００３２】Ｚは、賦活剤であり、Ｅｕ、Ｃｒ、Ｍｎ、
Ｐｂ、Ｓｂ、Ｃｅ、Ｔｂ、Ｐｒ、Ｓｍ、Ｔｍ、Ｈｏ、Ｅ
ｒ、Ｙｂ、Ｎｄからなる群より選ばれる少なくとも一種
以上を含有する。このうち黄色から赤色領域で発光を行
うＥｕ、Ｍｎ、Ｃｅ等を用いて本発明を説明するが、こ
れに限定されない。ＺにＥｕを用い、希土類元素である
ユウロピウムＥｕを発光中心とする。ユウロピウムは、
主に２価と３価のエネルギー準位を持つ。本発明の窒化
物蛍光体は、母体のアルカリ土類金属系窒化ケイ素に対
して、Ｅｕ２＋を賦活剤として用いる。Ｅｕ２＋は、酸
化されやすく、３価のＥｕ２Ｏ３の組成で市販されてい
る。しかし、市販のＥｕ２Ｏ３では、Ｏの関与が大き
く、良好な蛍光体が得られにくい。そのため、Ｅｕ２Ｏ
３からＯを、系外へ除去したものを使用することが好ま
しい。たとえば、ユウロピウム単体、窒化ユウロピウム
を用いることが好ましい。Z is an activator and includes Eu, Cr, Mn,
Pb, Sb, Ce, Tb, Pr, Sm, Tm, Ho, E
It contains at least one or more selected from the group consisting of r, Yb, and Nd. Of these, the present invention is described using Eu, Mn, Ce, etc. that emit light in the yellow to red region, but the present invention is not limited to this. Eu is used for Z, and europium Eu, which is a rare earth element, is used as the emission center. Europium is
It mainly has divalent and trivalent energy levels. The nitride phosphor of the present invention uses Eu 2+ as an activator for the matrix alkaline earth metal-based silicon nitride. Eu 2+ is easily oxidized and is commercially available in the composition of trivalent Eu 2 O 3 . However, with commercially available Eu 2 O 3 , it is difficult to obtain a good phosphor because O is largely involved. Therefore, Eu 2 O
It is preferable to use the one obtained by removing O from 3 to the outside of the system. For example, it is preferable to use europium simple substance or europium nitride.

【００３３】窒化物蛍光体には、基本構成元素の他に、
Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｃａ、Ｇａ、Ｉｎ、Ｂ、Ａ
ｌ、Ｃｕ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ、Ｒｅ、Ｎｉ、Ｃｒ、
Ｍｏ、Ｏ及びＦｅからなる群より選ばれる少なくとも１
種以上を含有する。これらの元素は、粒径を大きくした
り、発光輝度を高めたりする等の作用を有している。ま
た、Ｂ、Ｍｇ、Ｃｒ、Ｎｉ、Ａｌは、残光を抑えること
ができるとういう作用を有している。通常、Ｂ、Ｍｇ、
Ｃｒ等の添加物が添加されていない蛍光体の方が、添加
物が添加されている蛍光体よりも残光を１／１０に要す
る時間を１／２から１／４程度まで短縮することができ
る。一方、Ｆｅ、Ｍｏは、発光効率を低下させるおそれ
があるため、系外に除去しておくことが好ましい。In the nitride phosphor, in addition to the basic constituent elements,
Mg, Sr, Ba, Zn, Ca, Ga, In, B, A
l, Cu, Mn, Li, Na, K, Re, Ni, Cr,
At least 1 selected from the group consisting of Mo, O and Fe
Contains more than one seed. These elements have actions such as increasing the particle size and increasing the emission brightness. Further, B, Mg, Cr, Ni, and Al have an effect of suppressing afterglow. Usually B, Mg,
It is possible to shorten the time required for 1/10 afterglow from 1/2 to 1/4 in a phosphor to which an additive such as Cr is not added, as compared with a phosphor in which an additive is added. it can. On the other hand, since Fe and Mo may reduce the luminous efficiency, it is preferable to remove them outside the system.

【００３４】窒化物蛍光体１１は、半導体発光素子１０
によって発光された青色光の一部を吸収して黄から赤色
領域の光を発光する。この窒化物蛍光体１１を上記の構
成を有する発光装置に使用して、半導体発光素子１０に
より発光された青色光と、窒化物蛍光体の赤色光とが混
色により暖色系の白色に発光する発光装置を提供する。The nitride phosphor 11 is used in the semiconductor light emitting device 10.
It absorbs a part of the blue light emitted by and emits light in the yellow to red region. This nitride phosphor 11 is used in a light emitting device having the above-described structure, and the blue light emitted by the semiconductor light emitting element 10 and the red light of the nitride phosphor are mixed to emit warm white light. Provide a device.

【００３５】特に蛍光体１１には、本発明に係る窒化物
蛍光体の他に、セリウムで賦活されたイットリウム・ア
ルミニウム酸化物蛍光物質が含有されていることが好ま
しい。前記イットリウム・アルミニウム酸化物蛍光物質
を含有することにより、所望の色度に調節することがで
きるからである。セリウムで賦活されたイットリウム・
アルミニウム酸化物蛍光物質は、半導体発光素子１０に
より発光された青色光の一部を吸収して黄色領域の光を
発光する。ここで、半導体発光素子１０により発光され
た青色光と、イットリウム・アルミニウム酸化物蛍光物
質の黄色光とが混色により青白い白色に発光する。従っ
て、このイットリウム・アルミニウム酸化物蛍光物質と
前記窒化物蛍光体とを透光性を有するコーティング部材
と一緒に混合した蛍光体１１と、半導体発光素子１０に
より発光された青色光とを組み合わせることにより暖色
系の白色の発光装置を提供することができる。この暖色
系の白色の発光装置は、平均演色評価数Ｒａが７５乃至
９５であり色温度が２０００乃至８０００Ｋである。特
に好ましいのは、平均演色評価数Ｒａ及び色温度が色度
図における黒体放射の軌跡上に位置する白色の発光装置
である。但し、所望の色温度及び平均演色評価数の発光
装置を提供するため、イットリウム・アルミニウム酸化
物蛍光物質及び窒化物蛍光体の配合量を、適宜変更する
こともできる。In particular, the phosphor 11 preferably contains, in addition to the nitride phosphor of the present invention, a cerium-activated yttrium aluminum oxide phosphor. This is because the chromaticity can be adjusted to a desired level by containing the yttrium aluminum oxide fluorescent substance. Yttrium activated with cerium
The aluminum oxide fluorescent material absorbs part of the blue light emitted by the semiconductor light emitting device 10 and emits light in the yellow region. Here, the blue light emitted by the semiconductor light emitting element 10 and the yellow light of the yttrium-aluminum oxide fluorescent substance are mixed to emit a pale white color. Therefore, by combining the phosphor 11 obtained by mixing the yttrium aluminum oxide phosphor and the nitride phosphor together with the translucent coating member, and the blue light emitted by the semiconductor light emitting device 10. A warm white light emitting device can be provided. This warm white light emitting device has an average color rendering index Ra of 75 to 95 and a color temperature of 2000 to 8000K. Particularly preferable is a white light emitting device whose average color rendering index Ra and color temperature are located on the locus of black body radiation in the chromaticity diagram. However, in order to provide a light emitting device having a desired color temperature and an average color rendering index, the compounding amounts of the yttrium-aluminum oxide fluorescent substance and the nitride fluorescent substance can be appropriately changed.

【００３６】（窒化物蛍光体の製造方法）次に、図２を
用いて、本発明に係る窒化物蛍光体の製造方法を説明す
る。(Manufacturing Method of Nitride Phosphor) Next, the manufacturing method of the nitride phosphor according to the present invention will be described with reference to FIG.

【００３７】原料のＬ及びＭｇ等を粉砕する（Ｐ１）。
原料のＬは、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃ
ｄ、ＨｇのＩＩ価からなる群より選ばれる少なくとも１
種以上を含有する。特に、原料のＬは、Ｂｅ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａのグループからなるアルカリ土類金属が
好ましく、さらにアルカリ土類金属単体が好ましいが、
２以上含有するものでもよい。原料のＬは、イミド化合
物、アミド化合物などを使用することもできる。また原
料Ｌには、Ｂ、Ａｌ、Ｃｕ、Ｍｇ、Ｍｎ、Ａｌ ２Ｏ３な
どを含有するものでもよい。原料のＬは、アルゴン雰囲
気中、グローブボックス内で粉砕を行う。粉砕により得
られたアルカリ土類金属は、平均粒径が約０．１μｍか
ら１５μｍであることが好ましいが、この範囲に限定さ
れない。Ｌの純度は、２Ｎ以上であることが好ましい
が、これに限定されない。より混合状態を良くするた
め、金属のＬ、金属のＭ、金属の賦活剤のうち少なくと
も１以上を合金状態としたのち、窒化し、粉砕後、原料
として用いることもできる。Raw materials such as L and Mg are crushed (P1).
The raw material L is Be, Mg, Ca, Sr, Ba, Zn, C
d, at least 1 selected from the group consisting of Hg II values
Contains more than one seed. In particular, the raw material L is Be, Mg, C
Alkaline earth metal consisting of a, Sr, Ba group
Preferably, a simple substance of alkaline earth metal is more preferable,
It may contain two or more. The raw material L is an imide compound
It is also possible to use a substance, an amide compound or the like. Again
The material L includes B, Al, Cu, Mg, Mn, and Al. TwoOThreeNa
Any may be included. Raw material L is in an argon atmosphere
Grind in air in a glove box. Obtained by crushing
The average particle size of the obtained alkaline earth metal is about 0.1 μm.
Is preferably 15 μm or more, but is not limited to this range
I can't. The purity of L is preferably 2N or more
However, it is not limited to this. For better mixing
Therefore, at least L of metal, M of metal, and activator of metal
After making 1 or more alloy state, nitriding and crushing, then raw material
Can also be used as

【００３８】原料のＳｉ及びＡｌ等を粉砕する（Ｐ
２）。基本構成元素ＬＸＭ
ＹＮ（２／３ Ｘ＋４／３Ｙ）：ＺのＭは、Ｃ、Ｓｉ、Ｇ
ｅ、ＳｎのＩＶ価からなる群より選ばれる少なくとも１
種以上を含有する。原料のＭは、イミド化合物、アミド
化合物などを使用することもできる。Ｍのうち安価で扱
いやすいため、Ｓｉを用いて製造方法を説明するが、こ
れに限定されない。Ｓｉ、Ｓｉ３Ｎ４、Ｓｉ（ＮＨ２）
２、Ｍｇ２Ｓｉなども使用することができる。Ａｌ２Ｏ
３の他、Ｍｇ、金属ホウ化物（Ｃｏ３Ｂ、Ｎｉ３Ｂ、Ｍ
ｏ２Ｂ）、酸化マンガン、Ｈ３ＢＯ３、Ｂ２Ｏ３、Ｃｕ
２Ｏ、ＣｕＯなどの化合物も含有されていてもよい。Ｓ
ｉも、原料のＬと同様に、アルゴン雰囲気中、若しく
は、窒素雰囲気中、グローブボックス内で粉砕を行う。
Ｓｉ化合物の平均粒径は、約０．１μｍから１５μｍで
あることが好ましい。Ｓｉの純度は、３Ｎ以上であるこ
とが好ましい。次に、原料のＬ及びＭｇ等を、窒素雰囲
気中で窒化する（Ｐ３）。この反応式を、化１に示す。
Ｍｇは、数１０〜１０００ｐｐｍオーダーであるため、
反応式に含めない。The raw materials Si and Al are crushed (P
2). Basic constituent element LXM
YN(2/3 X + 4 / 3Y): M of Z is C, Si, G
e, at least 1 selected from the group consisting of Sn IV values
Contains more than one seed. Raw material M is imide compound, amide
Compounds and the like can also be used. Handled cheaply out of M
Since it is easy to use, the manufacturing method will be explained using Si.
It is not limited to this. Si, SiThreeNFour, Si (NHTwo)
Two, MgTwoSi etc. can also be used. AlTwoO
ThreeIn addition to Mg, metal borides (CoThreeB, NiThreeB, M
oTwoB), manganese oxide, HThreeBOThree, BTwoOThree, Cu
TwoCompounds such as O and CuO may also be contained. S
i, like L as the raw material, was young in an argon atmosphere
Performs grinding in a glove box in a nitrogen atmosphere.
The average particle size of the Si compound is about 0.1 μm to 15 μm.
Preferably there is. The purity of Si must be 3N or more.
And are preferred. Next, the raw materials L, Mg, and the like are mixed in a nitrogen atmosphere.
Nitriding in air (P3). This reaction formula is shown in Chemical formula 1.
Since Mg is on the order of several 10 to 1000 ppm,
Not included in reaction formula.

【００３９】[0039]

【化１】３Ｌ ＋ Ｎ２ → Ｌ３Ｎ２ ＩＩ価のＬを、窒素雰囲気中、６００〜９００℃、約５
時間、窒化する。これにより、Ｌの窒化物を得ることが
できる。Ｌの窒化物は、高純度のものが好ましいが、市
販のものも使用することができる。[Image Omitted] 3L + N 2 → L 3 N 2 II-valent L is added in a nitrogen atmosphere at 600 to 900 ° C. for about 5
Nitriding for hours. Thereby, a nitride of L can be obtained. As the nitride of L, a high-purity one is preferable, but a commercially available one can also be used.

【００４０】原料のＳｉ及びＡｌ等を、窒素雰囲気中で
窒化する（Ｐ４）。この反応式を、化２に示す。また、
Ａｌも、数１０〜１０００ｐｐｍオーダーであるため、
反応式に含めない。The raw materials Si and Al are nitrided in a nitrogen atmosphere (P4). This reaction formula is shown in Chemical formula 2. Also,
Since Al is also in the order of several 10 to 1000 ppm,
Not included in reaction formula.

【００４１】[0041]

【化２】３Ｓｉ ＋ ２Ｎ２ → Ｓｉ３Ｎ４ ケイ素Ｓｉも、窒素雰囲気中、８００〜１２００℃、約
５時間、窒化する。これにより、窒化ケイ素を得る。本
発明で使用する窒化ケイ素は、高純度のものが好ましい
が、市販のものも使用することができる。Embedded image 3Si + 2N 2 → Si 3 N 4 silicon Si is also nitrided in a nitrogen atmosphere at 800 to 1200 ° C. for about 5 hours. Thereby, silicon nitride is obtained. The silicon nitride used in the present invention is preferably highly pure, but commercially available ones can also be used.

【００４２】Ｌ及びＭｇ等の窒化物を粉砕する（Ｐ
５）。Ｌ及びＭｇ等の窒化物を、アルゴン雰囲気中、若
しくは、窒素雰囲気中、グローブボックス内で粉砕を行
う。同様に、Ｓｉ及びＡｌ等の窒化物を粉砕する（Ｐ
６）。また、同様に、Ｅｕの化合物Ｅｕ２Ｏ３を粉砕す
る（Ｐ７）。基本構成元素ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：ＺのＺは、賦活剤であり、Ｅ
ｕ、Ｃｒ、Ｍｎ、Ｐｂ、Ｓｂ、Ｃｅ、Ｔｂ、Ｐｒ、Ｓ
ｍ、Ｔｍ、Ｈｏ、Ｅｒからなる群より選ばれる少なくと
も一種以上を含有する。Ｚのうち、赤色領域で発光波長
を示すＥｕを用いて本発明に係る製造方法を説明する
が、これに限定されない。Ｅｕの化合物として、酸化ユ
ウロピウムを使用するが、金属ユウロピウム、窒化ユウ
ロピウムなども使用可能である。このほか、原料のＺ
は、イミド化合物、アミド化合物を用いることもでき
る。酸化ユウロピウムは、高純度のものが好ましいが、
市販のものも使用することができる。粉砕後のアルカリ
土類金属の窒化物、窒化ケイ素及び酸化ユウロピウムの
平均粒径は、約０．１μｍから１５μｍであることが好
ましい。Nitride such as L and Mg is crushed (P
5). Nitride such as L and Mg is ground in a glove box in an argon atmosphere or a nitrogen atmosphere. Similarly, nitrides such as Si and Al are crushed (P
6). Similarly, the Eu compound Eu 2 O 3 is pulverized (P7). Basic constituent elements L X M Y N
(2 / 3X + 4 / 3Y) : Z of Z is an activator, and E
u, Cr, Mn, Pb, Sb, Ce, Tb, Pr, S
It contains at least one or more selected from the group consisting of m, Tm, Ho and Er. Of Z, the manufacturing method according to the present invention will be described by using Eu showing an emission wavelength in the red region, but the present invention is not limited to this. As the compound of Eu, europium oxide is used, but metal europium, europium nitride and the like can also be used. In addition, the raw material Z
It is also possible to use an imide compound or an amide compound. Europium oxide is preferably highly pure,
A commercially available product can also be used. The average particle size of the crushed alkaline earth metal nitride, silicon nitride and europium oxide is preferably about 0.1 μm to 15 μm.

【００４３】上記原料中には、Ｍｇ、Ｓｒ、Ｂａ、Ｚ
ｎ、Ｃａ、Ｇａ、Ｉｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｌｉ、
Ｎａ、Ｋ、Ｒｅ、Ｎｉ、Ｃｒ、Ｍｏ、Ｏ及びＦｅからな
る群より選ばれる少なくとも１種以上が含有されてい
る。また、Ｂ、Ａｌ、Ｍｎなどの群より選ばれる化合物
を以下の混合工程（Ｐ８）において、配合量を調節して
混合することもできる。これらの化合物は、単独で原料
中に添加することもできるが、通常化合物の形態で添加
される。この種の化合物には、Ｈ３ＢＯ３、Ｃｕ
２Ｏ３、ＭｇＣｌ２、ＭｇＯ・ＣａＯ、Ａｌ２Ｏ３、金
属ホウ化物（ＣｒＢ、Ｍｇ ３Ｂ２、ＡｌＢ２、Ｍｎ
Ｂ）、Ｂ２Ｏ３、Ｃｕ２Ｏ、ＣｕＯなどがある。また、
Ｍｎ、Ａｌなどは、焼成前の原料中に含有されており、
原料の一部が置換された化合物もある。Among the above raw materials, Mg, Sr, Ba, Z
n, Ca, Ga, In, B, Al, Cu, Mn, Li,
Made of Na, K, Re, Ni, Cr, Mo, O and Fe
Contains at least one selected from the group
It Further, a compound selected from the group consisting of B, Al and Mn
In the following mixing step (P8), adjust the compounding amount
It can also be mixed. These compounds are raw materials alone
Although it can be added to the inside, it is usually added in the form of a compound.
To be done. Compounds of this type include HThreeBOThree, Cu
TwoOThree, MgClTwo, MgO / CaO, AlTwoOThree,Money
Group borides (CrB, Mg ThreeBTwo, AlBTwo, Mn
B), BTwoOThree, CuTwoO, CuO, etc. Also,
Mn, Al, etc. are contained in the raw material before firing,
There are also compounds in which some of the raw materials are replaced.

【００４４】上記粉砕を行った後、Ｌ及びＭｇ等の窒化
物、Ｓｉ及びＡｌ等の窒化物、Ｅｕの化合物Ｅｕ２Ｏ３
等を混合する（Ｐ８）。これらの混合物は、酸化されや
すいため、Ａｒ雰囲気中、又は、窒素雰囲気中、グロー
ブボックス内で、混合を行う。最後に、Ｌ及びＭｇ等の
窒化物、Ｓｉ及びＡｌ等の窒化物、Ｅｕの化合物Ｅｕ２
Ｏ３等の混合物をアンモニア雰囲気中で、焼成する（Ｐ
９）。焼成により、Ｍｇ、Ａｌ等を含有するＬＸＳｉＹ
Ｎ（２／３Ｘ＋４／３Ｙ）：Ｅｕで表される蛍光体を得
ることができる（Ｐ１０）。この焼成による基本構成元
素の反応式を、化３に示す。上述と同様に、Ｍｇ、Ａ
ｌ、Ｈ３ＢＯ３等の添加物も、数１０〜１０００ｐｐｍ
オーダーであるため、反応式に含めない。After the above pulverization, nitrides such as L and Mg, nitrides such as Si and Al, a compound of Eu, Eu 2 O 3
Etc. are mixed (P8). Since these mixtures are easily oxidized, they are mixed in an Ar atmosphere or a nitrogen atmosphere in a glove box. Finally, nitrides such as L and Mg, nitrides such as Si and Al, Eu compound Eu 2
A mixture of O 3 and the like is fired in an ammonia atmosphere (P
9). By firing, L X Si Y containing Mg, Al, etc.
A phosphor represented by N (2 / 3X + 4 / 3Y) : Eu can be obtained (P10). The reaction formula of the basic constituent elements by this firing is shown in Chemical formula 3. Similar to the above, Mg, A
Additives such as 1, H 3 BO 3 and the like are also several 10 to 1000 ppm
Since it is an order, it is not included in the reaction formula.

【００４５】[0045]

【化３】１．９７／３Ｌ３Ｎ２ ＋ ５／３Ｓｉ３Ｎ４
＋ ０．０３／２Ｅｕ２Ｏ３→ Ｌ１．９７Ｅｕ
０．０３Ｓｉ５Ｎ７．９８Ｏ０．０４５ ただし、目的とする蛍光体の組成を変更することによ
り、各混合物の配合比率は、適宜変更することができ
る。基本構成元素ＬＸＳｉ
ＹＮ（２／３Ｘ＋４／３Ｙ ）：Ｚは、Ｌ２Ｓｉ５Ｎ８：
Ｅｕ、ＬＳｉ７Ｎ１０：Ｅｕが好ましいが、この配合量
に限定されない。Embedded image 1.97 / 3L 3 N 2 + 5 / 3Si 3 N 4
+ 0.03 / 2Eu 2 O 3 → L 1.97 Eu
0.03 Si 5 N 7.98 O 0.045 However, the compounding ratio of each mixture can be appropriately changed by changing the composition of the target phosphor. Basic constituent element L X Si
Y N (2 / 3X + 4 / 3Y ) : Z is L 2 Si 5 N 8 :
Eu and LSi 7 N 10 : Eu are preferable, but the compounding amount is not limited.

【００４６】焼成は、管状炉、小型炉、高周波炉、メタ
ル炉などを使用することができる。焼成温度は、１２０
０から１７００℃の範囲で焼成を行うことができるが、
好ましくは、１２００から１４００℃の焼成温度が好ま
しい。焼成は、徐々に昇温を行い１２００から１５００
℃で数時間焼成を行う一段階焼成を使用することが好ま
しいが、８００から１０００℃で一段階目の焼成を行
い、徐々に加熱して１２００から１５００℃で二段階目
の焼成を行う二段階焼成（多段階焼成）を使用すること
もできる。蛍光体１１の原料は、窒化ホウ素（ＢＮ）材
質のるつぼ、ボートを用いて焼成を行うことが好まし
い。窒化ホウ素材質のるつぼの他に、アルミナ（Ａｌ２
Ｏ３）材質のるつぼを使用することもできる。For the firing, a tubular furnace, a small furnace, a high frequency furnace, a metal furnace or the like can be used. The firing temperature is 120
Although firing can be performed in the range of 0 to 1700 ° C,
A firing temperature of 1200 to 1400 ° C. is preferable. Firing is performed by gradually raising the temperature from 1200 to 1500.
It is preferable to use a one-step calcination in which the calcination is performed at several degrees Celsius for several hours, but a two-step calcination is performed in which the first-step calcination is performed at 800 to 1000 deg. Firing (multi-step firing) can also be used. The raw material of the phosphor 11 is preferably fired using a crucible made of boron nitride (BN) and a boat. In addition to the crucible made of boron nitride, alumina (Al 2
It is also possible to use crucibles of O 3 ) material.

【００４７】以上の製造方法を使用することにより、目
的とする蛍光体を得ることが可能である。By using the above manufacturing method, it is possible to obtain the desired phosphor.

【００４８】（半導体発光素子）半導体発光素子１０
は、ＩＩＩ属窒化物系化合物半導体発光素子であること
が好ましい。半導体発光素子１０は、例えばサファイア
基板１上にＧａＮバッファ層を介して、Ｓｉがアンドー
プのｎ型ＧａＮ層、Ｓｉがドープされたｎ型ＧａＮから
なるｎ型コンタクト層、アンドープＧａＮ層、多重量子
井戸構造の発光層（ＧａＮ障壁層／ＩｎＧａＮ井戸層の
量子井戸構造）、Ｍｇがドープされたｐ型ＧａＮからな
るｐ型ＧａＮからなるｐクラッド層、Ｍｇがドープされ
たｐ型ＧａＮからなるｐ型コンタクト層が順次積層され
た積層構造を有し、以下のように電極が形成されてい
る。但し、この構成と異なる半導体発光素子１０も使用
できる。(Semiconductor Light-Emitting Element) Semiconductor Light-Emitting Element 10
Is preferably a group III nitride compound semiconductor light emitting device. The semiconductor light emitting device 10 includes an n-type GaN layer in which Si is undoped, an n-type contact layer made of Si-doped n-type GaN, an undoped GaN layer, and a multiple quantum well via a GaN buffer layer on the sapphire substrate 1, for example. Structure light emitting layer (GaN barrier layer / InGaN well layer quantum well structure), Mg-doped p-type GaN p-type GaN p-cladding layer, Mg-doped p-type GaN p-type contact It has a laminated structure in which layers are sequentially laminated, and electrodes are formed as follows. However, a semiconductor light emitting device 10 different from this structure can also be used.

【００４９】ｐオーミック電極は、ｐ型コンタクト層上
のほぼ全面に形成され、そのｐオーミック電極上の一部
にｐパッド電極３が形成される。The p ohmic electrode is formed on almost the entire surface of the p-type contact layer, and the p pad electrode 3 is formed on a part of the p ohmic electrode.

【００５０】また、ｎ電極は、エッチングによりｐ型コ
ンタクト層からアンドープＧａＮ層を除去してｎ型コン
タクト層の一部を露出させ、その露出された部分に形成
される。The n-electrode is formed on the exposed part by removing the undoped GaN layer from the p-type contact layer by etching to expose a part of the n-type contact layer.

【００５１】なお、本実施の形態では、多重量子井戸構
造の発光層を用いたが、本発明は、これに限定されるも
のではなく、例えば、ＩｎＧａＮを利用した単一量子井
戸構造としても良いし、Ｓｉ、ＺｎがドープされたＧａ
Ｎを利用しても良い。Although the light emitting layer having the multiple quantum well structure is used in the present embodiment, the present invention is not limited to this, and for example, a single quantum well structure using InGaN may be used. And Ga doped with Si and Zn
You may use N.

【００５２】また、半導体発光素子１０の発光層は、Ｉ
ｎの含有量を変化させることにより、４２０ｎｍから４
９０ｎｍの範囲において主発光ピークを変更することが
できる。また、発光波長は、上記範囲に限定されるもの
ではなく、３６０〜５５０ｎｍに発光波長を有している
ものを使用することができる。The light emitting layer of the semiconductor light emitting device 10 is I
By changing the content of n, from 420 nm to 4
The main emission peak can be changed in the range of 90 nm. Further, the emission wavelength is not limited to the above range, and one having an emission wavelength of 360 to 550 nm can be used.

【００５３】（コーティング部材）コーティング部材１
２（光透光性材料）は、リードフレーム１３のカップ内
に設けられるものであり半導体発光素子１０の発光を変
換する蛍光体１１と混合して用いられる。コーティング
部材１２の具体的材料としては、エポキシ樹脂、ユリア
樹脂、シリコーン樹脂などの温度特性、耐候性に優れた
透明樹脂、シリカゾル、ガラス、無機バインダーなどが
用いられる。また、蛍光体１１と共に拡散剤、チタン酸
バリウム、酸化チタン、酸化アルミニウムなどを含有さ
せても良い。また、光安定化剤や着色剤を含有させても
良い。(Coating member) Coating member 1
2 (light transmissive material) is provided in the cup of the lead frame 13, and is used by mixing with the phosphor 11 that converts the light emission of the semiconductor light emitting element 10. As a specific material for the coating member 12, a transparent resin such as an epoxy resin, a urea resin, or a silicone resin having excellent temperature characteristics and weather resistance, silica sol, glass, an inorganic binder, or the like is used. In addition, the phosphor 11 may contain a diffusing agent, barium titanate, titanium oxide, aluminum oxide, or the like. Further, a light stabilizer and a colorant may be contained.

【００５４】（リードフレーム）リードフレーム１３
は、マウントリード１３ａとインナーリード１３ｂとか
ら構成される。マウントリード１３ａは、半導体発光素
子１０を配置させるものである。マウントリード１３ａ
の上部は、カップ形状になっており、カップ内に半導体
発光素子１０をダイボンドし、該半導体発光素子１０の
外周面を、カップ内を前記蛍光体１１と前記コーティン
グ部材１２とで覆っている。カップ内に半導体発光素子
１０を複数配置しマウントリード１３ａを半導体発光素
子１０の共通電極として利用することもできる。この場
合、十分な電気伝導性と導電性ワイヤ１４との接続性が
求められる。半導体発光素子１０とマウントリード１３
ａのカップとのダイボンド（接着）は、熱硬化性樹脂な
どによって行うことができる。熱硬化性樹脂としては、
エポキシ樹脂、アクリル樹脂、イミド樹脂などが挙げら
れる。また、フェースダウン半導体発光素子１０などに
よりマウントリード１３ａとダイボンドすると共に電気
的接続を行うには、Ａｇ―エースと、カーボンペース
ト、金属バンプなどを用いることができる。また、無機
バインダーを用いることもできる。インナーリード１３
ｂは、マウントリード１３ａ上に配置された半導体発光
素子１０の電極３から延びる導電性ワイヤ１４との電気
的接続を図るものである。インナーリード１３ｂは、マ
ウントリード１３ａとの電気的接触によるショートを避
けるため、マウントリード１３ａから離れた位置に配置
することが好ましい。マウントリード１３ａ上に複数の
半導体発光素子１０を設けた場合は、各導電性ワイヤ同
士が接触しないように配置できる構成にする必要があ
る。インナーリード１３ｂは、マウントリード１３ａと
同様の材質を用いることが好ましく、鉄、銅、鉄入り
銅、金、白金、銀などを用いることができる。(Lead frame) Lead frame 13
Is composed of a mount lead 13a and an inner lead 13b. The mount lead 13a is for disposing the semiconductor light emitting element 10. Mount lead 13a
Has a cup shape, the semiconductor light emitting element 10 is die-bonded in the cup, and the outer peripheral surface of the semiconductor light emitting element 10 is covered with the phosphor 11 and the coating member 12 inside the cup. It is also possible to arrange a plurality of semiconductor light emitting elements 10 in the cup and use the mount lead 13a as a common electrode of the semiconductor light emitting element 10. In this case, sufficient electrical conductivity and connectivity with the conductive wire 14 are required. Semiconductor light emitting element 10 and mount lead 13
The die bonding (adhesion) with the cup of a can be performed with a thermosetting resin or the like. As a thermosetting resin,
Epoxy resin, acrylic resin, imide resin and the like can be mentioned. Further, Ag-ace, carbon paste, metal bumps, or the like can be used for die-bonding to the mount lead 13a by the face-down semiconductor light emitting device 10 or the like and for electrical connection. Also, an inorganic binder can be used. Inner lead 13
b is for electrical connection with the conductive wire 14 extending from the electrode 3 of the semiconductor light emitting element 10 arranged on the mount lead 13a. The inner lead 13b is preferably arranged at a position away from the mount lead 13a in order to avoid a short circuit due to electrical contact with the mount lead 13a. When a plurality of semiconductor light emitting elements 10 are provided on the mount lead 13a, it is necessary to have a configuration in which the conductive wires can be arranged so as not to contact each other. The inner lead 13b is preferably made of the same material as the mount lead 13a, and iron, copper, copper containing iron, gold, platinum, silver, or the like can be used.

【００５５】（導電性ワイヤ）導電性ワイヤ１４は、半
導体発光素子１０の電極３とリードフレーム１３とを電
気的に接続するものである。導電性ワイヤ１４は、電極
３とオーミック性、機械的接続性、電気導電性及び熱伝
導性が良いものが好ましい。導電性ワイヤ１４の具体的
材料としては、金、銅、白金、アルミニウムなどの金属
及びそれらの合金などが好ましい。(Conductive Wire) The conductive wire 14 electrically connects the electrode 3 of the semiconductor light emitting element 10 and the lead frame 13. The conductive wire 14 preferably has good ohmic properties, mechanical connectivity, electrical conductivity, and thermal conductivity with the electrode 3. As a specific material for the conductive wire 14, metals such as gold, copper, platinum, aluminum and alloys thereof are preferable.

【００５６】（モールド部材）モールド部材１５は、半
導体発光素子１０、蛍光体１１、コーティング部材１
２、リードフレーム１３及び導電性ワイヤ１４などを外
部から保護するために設けられている。モールド部材１
５は、外部からの保護目的の他に、視野角を広げたり、
半導体発光素子１０からの指向性を緩和したり、発光を
収束、拡散させたりする目的も併せ持っている。これら
の目的を達成するためモールド部材は、所望の形状にす
ることができる。また、モールド部材１５は、凸レンズ
形状、凹レンズ形状の他、複数積層する構造であっても
良い。モールド部材１５の具体的材料としては、エポキ
シ樹脂、ユリア樹脂、シリコーン樹脂、シリカゾル、ガ
ラスなどの透光性、耐候性、温度特性に優れた材料を使
用することができる。モールド部材１５には、拡散剤、
着色剤、紫外線吸収剤や蛍光物質を含有させることもで
きる。拡散剤としては、チタン酸バリウム、酸化チタ
ン、酸化アルミニウム等が好ましい。コーティング部材
１２との材質の反発性を少なくするため、屈折率を考慮
するため、同材質を用いることが好ましい。(Molding Member) The molding member 15 includes the semiconductor light emitting element 10, the phosphor 11, and the coating member 1.
2, the lead frame 13 and the conductive wire 14 are provided to protect them from the outside. Mold member 1
5 has a wide viewing angle in addition to the purpose of protecting from the outside,
It also has the purpose of relaxing the directivity from the semiconductor light emitting device 10 and converging and diffusing the emitted light. To achieve these ends, the mold member can be shaped as desired. The mold member 15 may have a convex lens shape, a concave lens shape, or a structure in which a plurality of layers are laminated. As a specific material for the mold member 15, a material having excellent light-transmitting property, weather resistance and temperature characteristics such as epoxy resin, urea resin, silicone resin, silica sol, glass, etc. can be used. The mold member 15 includes a diffusing agent,
A colorant, an ultraviolet absorber or a fluorescent substance can also be contained. As the diffusing agent, barium titanate, titanium oxide, aluminum oxide and the like are preferable. In order to reduce the resilience of the material of the coating member 12 and to consider the refractive index, it is preferable to use the same material.

【００５７】以下、本発明に係る窒化物蛍光体、発光装
置について実施例を挙げて説明するが、この実施例に限
定されるものではない。Hereinafter, the nitride phosphor and the light emitting device according to the present invention will be described with reference to examples, but the invention is not limited to these examples.

【００５８】なお、発光特性は、比較例１の輝度を１０
０％とする相対輝度で示す。残光は、励起時の発光強度
を基準に、励起停止後、輝度が１／１０まで低下するの
に要した時間で示す。温度特性は、２５℃の発光輝度を
１００％とする相対輝度で示す。As for the light emission characteristics, the luminance of Comparative Example 1 was 10
The relative brightness is set to 0%. The afterglow is indicated by the time required for the luminance to decrease to 1/10 after the excitation was stopped, based on the emission intensity at the time of excitation. The temperature characteristics are indicated by relative brightness with the emission brightness at 25 ° C. being 100%.

【００５９】[0059]

【実施例】＜実施例１〜６、比較例１〜２＞表１は、本
発明に係る窒化物蛍光体の実施例１〜６及び比較例１〜
２を示す。また、図３乃至５は、実施例２及び３の窒化
物蛍光体の発光特性を示したものである。図３は、実施
例２及び３の窒化物蛍光体をＥｘ＝４６０ｎｍで励起し
たときの発光スペクトルを示す図である。図４は、実施
例２及び３の窒化物蛍光体の励起スペクトルを示す図で
ある。図５は、実施例２及び３の窒化物蛍光体の反射ス
ペクトルを示す図である。図６は、実施例３の窒化物蛍
光体の粒径を撮影した写真である。EXAMPLES <Examples 1 to 6 and Comparative Examples 1 and 2> Table 1 shows Examples 1 to 6 and Comparative Examples 1 to 6 of the nitride phosphor according to the present invention.
2 is shown. 3 to 5 show the emission characteristics of the nitride phosphors of Examples 2 and 3. FIG. 3 is a diagram showing an emission spectrum when the nitride phosphors of Examples 2 and 3 were excited at Ex = 460 nm. FIG. 4 is a diagram showing excitation spectra of the nitride phosphors of Examples 2 and 3. FIG. 5 is a diagram showing the reflection spectra of the nitride phosphors of Examples 2 and 3. FIG. 6 is a photograph of the grain size of the nitride phosphor of Example 3.

【００６０】[0060]

【表１】 [Table 1]

【００６１】 [0061]

【００６２】 [0062]

【００６３】実施例１〜６は、本発明に係るＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：ＺにＢ、Ａｌ、Ｃｕ、Ｍｎ、
Ｃｏ、Ｎｉ、Ｍｏ、Ｏ及びＦｅからなる群より選ばれる
少なくとも１種以上を含有する窒化物蛍光体の化学的特
性や物理的特性を調べた結果である。窒化物蛍光体ＬＸ
ＭＹＮ（２／３Ｘ＋４／３Ｙ）：Ｚの基本構成元素のＬ
にはＣａを、ＭにはＳｉを、ＺにはＥｕを用いて、Ｃａ
２−ｔＥｕｔＳｉ５Ｎ ８で表す。実施例１〜６の窒化物
蛍光体に用いられるＣａの一部をＥｕで置換しており、
Ｅｕの配合割合をｔ、Ｃａの配合割合を２−ｔに表した
ものである。Ｓｉの５に対して、実施例１は、０．０
３、実施例２は、０．０１、実施例３は、０．０６で表
される配合割合のＥｕを含有している。Ｍｇ、Ｓｒ、Ｂ
ａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ及びＦｅのうち少なく
とも１種以上が数ｐｐｍから数百ｐｐｍ含有された窒化
カルシウム、窒化ケイ素、酸化ユウロピウムを、窒素雰
囲気中、グローブボックス内で混合する。実施例１にお
いて、原料の混合比率（モル比）は、窒化カルシウムＣ
ａ３Ｎ２：窒化ケイ素Ｓｉ ３Ｎ４：酸化ユウロピウムＥ
ｕ２Ｏ３＝１．９７：５：０．０３である。 窒化カルシウムＣａ３Ｎ２ １４．４７ｇ 窒化ケイ素Ｓｉ３Ｎ４ ３４．７５ｇ 酸化ユウロピウムＥｕ２Ｏ３ ０．７９ｇ 上記化合物を混合し、焼成を行う。焼成条件は、アンモ
ニア雰囲気中、窒化ホウ素るつぼに投入し、室温から約
５時間かけて徐々に昇温して、約１３５０℃で５時間、
焼成を行い、ゆっくりと５時間かけて室温まで冷却し
た。Examples 1 to 6 are L according to the present invention.XMYN
(2 / 3X + 4 / 3Y): Z to B, Al, Cu, Mn,
Selected from the group consisting of Co, Ni, Mo, O and Fe
Chemical characteristics of nitride phosphor containing at least one or more
It is the result of examining the sex and physical characteristics. Nitride phosphor LX
MYN(2 / 3X + 4 / 3Y): L which is the basic constituent element of Z
For Ca, Si for M and Eu for Z
2-tEutSi5N 8It is represented by. Nitride of Examples 1-6
A part of Ca used for the phosphor is replaced with Eu,
The compounding ratio of Eu was represented by t, and the compounding ratio of Ca was represented by 2-t.
It is a thing. In contrast to Si of 5, in Example 1, 0.0
3, Example 2 is 0.01, and Example 3 is 0.06.
It contains Eu in an appropriate mixing ratio. Mg, Sr, B
a, Zn, B, Al, Cu, Mn and Fe are less
Nitride containing one or more of several ppm to several hundred ppm
Calcium, silicon nitride, and europium oxide are placed in a nitrogen atmosphere.
Mix in a glove box in the atmosphere. In Example 1
The mixing ratio (molar ratio) of the raw materials is calcium nitride C
aThreeNTwo: Silicon nitride Si ThreeNFour: Europium oxide E
uTwoOThree= 1.97: 5: 0.03. Calcium nitride CaThreeNTwo    14.47g Silicon nitride SiThreeNFour        34.75 g Europium oxide EuTwoOThree    0.79g The above compounds are mixed and fired. The firing conditions are
Place in a boron nitride crucible in a near atmosphere, and from room temperature
Gradually raise the temperature over 5 hours at about 1350 ° C for 5 hours,
Bake and slowly cool to room temperature over 5 hours
It was

【００６４】表１より、実施例１の窒化物蛍光体には、
基本構成元素の他に、Ｏが０．８７重量％、そして、Ｍ
ｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ及びＦｅ
が数ｐｐｍ濃度含有されている。Ｓｉは、１００から上
記構成元素を差し引いた重量％が含有されている。この
焼成条件及びＭｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ
及びＭｎにより高い発光輝度を有する。一般に使用され
ている半導体発光素子は１００〜１５０℃まで温度上昇
するため、発光素子の表面に窒化物蛍光体を形成しよう
とする場合、該温度で安定であることが好ましく、本実
施例１乃至６の窒化物蛍光体の温度特性は極めて良好で
ある。この観点から実施例２は、極めて温度特性が良好
であるため、優れた技術的意義を有する。From Table 1, in the nitride phosphor of Example 1,
In addition to the basic constituent elements, O is 0.87% by weight, and M
g, Sr, Ba, Zn, B, Al, Cu, Mn and Fe
Is contained at a concentration of several ppm. Si contains 100 wt% of the above constituent elements. This firing condition and Mg, Sr, Ba, Zn, B, Al, Cu
And Mn have high emission brightness. Since the temperature of a semiconductor light emitting device that is generally used rises to 100 to 150 ° C., it is preferable that the temperature is stable at the temperature when a nitride phosphor is formed on the surface of the light emitting device. The temperature characteristics of the nitride phosphor of No. 6 are extremely good. From this point of view, Example 2 has an extremely good temperature characteristic and therefore has an excellent technical significance.

【００６５】実施例３は、実施例２と比較すると発光輝
度が高く、量子効率も高い。従って、実施例３は、極め
て良好な発光特性を示す。Example 3 has higher emission luminance and higher quantum efficiency than Example 2. Therefore, Example 3 exhibits extremely good emission characteristics.

【００６６】実施例１の粒径は１〜３μｍと粒径が大き
く発光輝度も高い。また、分散性も良く扱いやすい。The particle size of Example 1 is as large as 1 to 3 μm, and the emission brightness is also high. It also has good dispersibility and is easy to handle.

【００６７】実施例４は、焼成条件を変えて原料の焼成
を行った。２段階焼成であっても、実施例４は、実施例
１及び３と同様、高輝度、高量子効率、良好な温度特性
を示す。実施例に係る蛍光体は、窒化ホウ素材質のるつ
ぼを用い、アンモニア雰囲気中で焼成を行っている。こ
の焼成条件下では、炉及びるつぼが浸食されることはな
いため、焼成品に不純物が混入することはない。実施例
５は、原料にＢを含有させ焼成した場合の発光効率を示
している。実施例５の結果から、Ｂが多く含まれていた
場合であっても、発光効率は極めて高い状態を維持して
いる。このことは、炉及びＢＮるつぼが浸食され蛍光体
中にＢＮが含有した場合を想定したものであるが、発光
効率は低下していないので炉及びるつぼの浸食を問題と
することなく焼成を行うことができる。つまり、仮にこ
の条件下で焼成を行った結果、蛍光体中に浸食された窒
化ホウ素が含有した場合であっても、発光輝度を低下さ
せることはないため、極めて有用である。実施例６は、
アルミニウムを多く含有させた蛍光体の発光特性を示
す。ＢＮるつぼ以外に、アルミナるつぼを使用した場合
の、アルミナるつぼからの浸食を考慮したものである。
実施例６の結果より、アルミニウムが含有された蛍光体
であっても高い発光特性を示す。これによりアルミナる
つぼを使用する場合であっても、アルミナるつぼからの
汚染を問題とすることなく焼成を行うことができる。こ
れに対して比較例１は、モリブデンるつぼを使用する。
モリブデンるつぼを使用した場合、るつぼが浸食されモ
リブデンが蛍光体中に含有してくる。モリブデンを含有
する比較例１の蛍光体は、発光特性の低下を生じてい
る。従って、モリブデンるつぼを使用することはあまり
好ましいとはいえない。Ｍｏは発光特性を低下させるた
め、系外に除去しておくことが好ましい。比較例２は、
蛍光体中にＦｅを含有したものを製造した。モリブデン
るつぼ及び炉からの汚染により、Ｆｅが蛍光体中に含ま
れる場合もあるため、Ｆｅを蛍光体中に含有させたとき
の効果を測定した。その結果、Ｆｅも発光特性を低下さ
せるため、系外に除去しておくことが好ましい。In Example 4, raw materials were fired under different firing conditions. Even in the case of two-step firing, Example 4 exhibits high brightness, high quantum efficiency, and good temperature characteristics as in Examples 1 and 3. The phosphor according to the example uses a crucible made of boron nitride and is fired in an ammonia atmosphere. Under this firing condition, the furnace and crucible are not eroded, so that impurities are not mixed in the fired product. Example 5 shows the light emission efficiency when B is added to the raw material and fired. From the results of Example 5, even when a large amount of B is contained, the luminous efficiency is maintained at an extremely high state. This is based on the assumption that the furnace and the BN crucible are eroded and BN is contained in the phosphor, but since the luminous efficiency is not lowered, the firing is performed without causing the erosion of the furnace and the crucible to be a problem. be able to. That is, even if the phosphor contains eroded boron nitride as a result of performing the firing under these conditions, it does not reduce the emission brightness and is therefore extremely useful. Example 6 is
The luminescent characteristics of the phosphor containing a large amount of aluminum are shown. This is in consideration of erosion from the alumina crucible when the alumina crucible is used in addition to the BN crucible.
From the results of Example 6, even the phosphor containing aluminum shows high emission characteristics. As a result, even when an alumina crucible is used, firing can be performed without causing a problem of contamination from the alumina crucible. In contrast, Comparative Example 1 uses a molybdenum crucible.
When a molybdenum crucible is used, the crucible is eroded and molybdenum is contained in the phosphor. In the phosphor of Comparative Example 1 containing molybdenum, the emission characteristics are deteriorated. Therefore, the use of molybdenum crucibles is less preferred. Since Mo deteriorates the light emission characteristics, it is preferable to remove it outside the system. Comparative Example 2
A phosphor containing Fe was manufactured. Since Fe may be contained in the phosphor due to contamination from the molybdenum crucible and the furnace, the effect of including Fe in the phosphor was measured. As a result, Fe also deteriorates the light emission characteristics, so it is preferable to remove Fe outside the system.

【００６８】＜比較試験＞本発明の作用効果を明確にす
るため、さらに比較試験を行った。比較例３は、基本構
成元素のみを含有する窒化物蛍光体であるのに対し、実
施例１及び４は、基本構成元素及び成分構成元素を含有
する窒化物蛍光体である。その結果を、表２に示す。図
７は、実施例１及び比較例３の窒化物蛍光体を、Ｅｘ＝
４６０ｎｍで励起したときの発光スペクトルを示す図で
ある。<Comparative Test> In order to clarify the action and effect of the present invention, a comparative test was conducted. Comparative Example 3 is a nitride phosphor containing only basic constituent elements, while Examples 1 and 4 are nitride phosphors containing basic constituent elements and constituent constituent elements. The results are shown in Table 2. FIG. 7 shows the nitride phosphors of Example 1 and Comparative Example 3 as Ex =
It is a figure which shows the emission spectrum when excited at 460 nm.

【００６９】[0069]

【表２】 [Table 2]

【００７０】 [0070]

【００７１】比較例３の原料の配合比率は、窒化カルシ
ウムＣａ３Ｎ２：窒化ケイ素Ｓｉ３Ｎ４：酸化ユウロピ
ウムＥｕ２Ｏ３＝１．９７：５：０．０３であり、十分
に精製を行ったものを使用した。一方、実施例４の原料
の配合比率は、比較例３と同条件のものを用い、該原料
に実施例１と同濃度のＭｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａ
ｌ、Ｃｕ、Ｍｎ及びＦｅを数ｐｐｍ濃度含有する。実施
例４は、Ｍｎ等を含有する３化合物原料を、ＢＮるつぼ
に入れ、室温から徐々に昇温を行い約８００℃で３時
間、焼成を行い、さらに徐々に昇温を行い約１３５０℃
で５時間、焼成を行い、焼成後、ゆっくりと５時間をか
けて室温まで冷却した。比較例３は、Ｍｎ等を含有しな
い３化合物原料をモリブデンるつぼに入れ、水素／窒素
雰囲気中で焼成を行った。実施例４のアンモニアの流量
を１とした場合に、比較例３の水素／窒素の流量は、水
素：窒素＝０．１：３の割合である。一方、実施例１
は、アンモニア雰囲気中、徐々に昇温を行い約１３５０
℃で５時間焼成を行い、約５時間かけて室温まで徐々に
冷却を行った。The blending ratio of the raw materials of Comparative Example 3 was calcium nitride Ca 3 N 2 : silicon nitride Si 3 N 4 : europium oxide Eu 2 O 3 = 1.97: 5: 0.03, which was sufficiently purified. Used what was done. On the other hand, the mixing ratio of the raw material of Example 4 was the same as that of Comparative Example 3, and Mg, Sr, Ba, Zn, B, A of the same concentration as in Example 1 was used as the raw material.
1, containing several ppm concentration of Cu, Mn and Fe. In Example 4, three compound raw materials containing Mn and the like were placed in a BN crucible, gradually heated from room temperature and baked at about 800 ° C. for 3 hours, and further gradually heated to about 1350 ° C.
Calcination was performed for 5 hours, and after calcination, it was slowly cooled to room temperature over 5 hours. In Comparative Example 3, three compound raw materials containing no Mn or the like were placed in a molybdenum crucible and fired in a hydrogen / nitrogen atmosphere. When the flow rate of ammonia in Example 4 is 1, the flow rate of hydrogen / nitrogen in Comparative Example 3 is hydrogen: nitrogen = 0.1: 3. On the other hand, Example 1
Gradually raises the temperature in an ammonia atmosphere to about 1350
Firing was performed at 5 ° C. for 5 hours, and gradually cooled to room temperature over about 5 hours.

【００７２】表２及び図７から明らかなように、比較例
３の発光輝度は、９９．１％であるのに対し、実施例４
の発光輝度は、１２８．７％と、２９．６％も発光輝度
が向上した。この発光輝度の違いは、発光効率の観点か
ら、極めて重要な意義を持つ。比較例３のエネルギー効
率は、９９．１％であるのに対し、実施例４のエネルギ
ー効率は、１３１．１％と、３２％も向上した。さら
に、比較例３の量子効率は、１００．５％であるのに対
し、実施例４の量子効率は、１３６．８％と、３６．３
％も向上した。このように、雰囲気及びるつぼの材質を
変えることにより、極めて顕著な発光特性を得ることが
できる。また、Ｍｇ、Ｍｎ等を含有することにより、極
めて顕著な発光特性を得ることができる。こうした発光
特性の向上は、より鮮やかな白色に発光する発光材料を
提供することができる。また、発光特性の向上は、エネ
ルギー効率を高めるため、省電力化も図ることができ
る。As is clear from Table 2 and FIG. 7, the emission brightness of Comparative Example 3 is 99.1%, while that of Example 4
The emission brightness of 128.7% was improved to 29.6%. This difference in light emission brightness is extremely important from the viewpoint of light emission efficiency. The energy efficiency of Comparative Example 3 was 99.1%, whereas the energy efficiency of Example 4 was 131.1%, which was 32% higher. Further, while the quantum efficiency of Comparative Example 3 is 100.5%, the quantum efficiency of Example 4 is 136.8% and 36.3%.
% Has also improved. Thus, by changing the atmosphere and the material of the crucible, it is possible to obtain extremely remarkable light emission characteristics. Further, by containing Mg, Mn, or the like, extremely remarkable light emission characteristics can be obtained. Such improvement of the light emitting characteristics can provide a light emitting material that emits brighter white light. In addition, the improvement of the light emitting property improves the energy efficiency, so that the power saving can be achieved.

【００７３】さらに実施例１では、実施例４と比較して
焼成パターンの違い以外は、同条件で焼成を行った。実
施例１の焼成パターンは、室温から徐々に昇温を行い約
１３５０℃で５時間、焼成を行い、ゆっくりと５時間か
けて室温まで冷却した。このとき発光輝度は、１３５．
５％と、比較例３と比べて３６．４％も向上した。ま
た、エネルギー効率は、１３８％と、比較例３と比べて
３８．９％も向上した。さらに、量子効率は、１３８．
６％と、比較例３と比べて３８．１％も向上した。さら
に、室温を１００として被測定ロットの相対輝度変化で
温度特性を見てみると、比較例３では、温度２００℃で
は６２．８％であるのに対し、実施例１は、同温度で６
７．１％と、高い数値を示した。また３００℃では、比
較例３の１８．２％に対し、実施例１の２３．５％と、
高い数値を示した。この温度特性は、発光素子の表面に
該窒化物蛍光体を設けたとき、窒化物蛍光体の組成が変
化せずに、高い発光特性を示しているかを表すものであ
り、温度特性が高いものほど安定であることを示してい
る。表２の結果から本発明に係る窒化物蛍光体の方が、
比較例３よりも温度特性が良好であり、信頼性が高いこ
とが明確である。このように、実施例１及び４は、比較
例３と比べて極めて顕著な発光特性を示した。これによ
り従来解決されていなかった発光特性の向上を、極めて
容易に図ることができる。Further, in Example 1, firing was performed under the same conditions as in Example 4, except that the firing pattern was different. The firing pattern of Example 1 was such that the temperature was gradually raised from room temperature, firing was performed at about 1350 ° C. for 5 hours, and slowly cooled to room temperature over 5 hours. At this time, the emission brightness is 135.
This is 5%, which is an improvement of 36.4% as compared with Comparative Example 3. Further, the energy efficiency was 138%, which was 38.9% higher than that of Comparative Example 3. Furthermore, the quantum efficiency is 138.
6%, which is an improvement of 38.1% as compared with Comparative Example 3. Further, when the temperature characteristics are examined by the relative luminance change of the measured lot with the room temperature being 100, in Comparative Example 3, the temperature is 62.8% at 200 ° C., while in Example 1, the temperature characteristic is 6
The value was as high as 7.1%. In addition, at 300 ° C., 23.5% of the first embodiment, compared with 18.2% of the third comparative example,
It showed a high number. This temperature characteristic represents whether or not the nitride phosphor is provided on the surface of the light emitting device and exhibits high emission characteristics without changing the composition of the nitride phosphor. It shows that it is stable. From the results of Table 2, the nitride phosphor according to the present invention is
It is clear that the temperature characteristics are better and the reliability is higher than in Comparative Example 3. As described above, Examples 1 and 4 exhibited extremely remarkable light emission characteristics as compared with Comparative Example 3. As a result, it is possible to extremely easily improve the light emission characteristics that have not been solved in the past.

【００７４】＜実施例７〜９＞実施例７は、蛍光体の基
本構成元素がＳｒ１．９７Ｅｕ０．０３Ｓｉ５Ｎ８であ
る。原料の配合比率は、窒化カルシウムＳｒ３Ｎ２：窒
化ケイ素Ｓｉ３Ｎ４：酸化ユウロピウムＥｕ２Ｏ３＝
１．９７：５：０．０３である。この原料中には、Ｍ
ｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｃｏ及
びＦｅが２５０〜４００ｐｐｍ濃度含有されている。こ
の３化合物原料を、ＢＮるつぼに入れ、管状炉で、８０
０〜１０００℃で３時間焼成し、その後、１２５０〜１
３５０℃で５時間焼成を行い、５時間かけて室温まで、
徐々に冷却を行った。アンモニアガスは、１ｌ／ｍｉｎ
の割合で、終始流し続けた。この結果、実施例７の窒化
物蛍光体の２００℃における温度特性は、８７．７％と
極めて高い温度特性を示している。表３は、本発明に係
る窒化物蛍光体の実施例７〜９を示す。[0074] <Example 7-9> In Example 7, the basic constituent elements of the phosphor are Sr 1.97 Eu 0.03 Si 5 N 8 . The mixing ratio of the raw materials is as follows: calcium nitride Sr 3 N 2 : silicon nitride Si 3 N 4 : europium oxide Eu 2 O 3 =
It is 1.97: 5: 0.03. In this raw material, M
g, Sr, Ba, Zn, B, Al, Cu, Mn, Co and Fe are contained in a concentration of 250 to 400 ppm. The 3 compound raw materials were put into a BN crucible and heated in a tubular furnace at 80
Bake at 0-1000 ° C for 3 hours, then 1250-1
Bake at 350 ° C for 5 hours, and allow to reach room temperature over 5 hours.
Gradually cooled. Ammonia gas is 1 l / min
It kept flowing at all times. As a result, the temperature characteristic of the nitride phosphor of Example 7 at 200 ° C. is 87.7%, which is an extremely high temperature characteristic. Table 3 shows Examples 7 to 9 of the nitride phosphor according to the present invention.

【００７５】[0075]

【表３】 [Table 3]

【００７６】 [0076]

【００７７】実施例８は、蛍光体の基本構成元素はＳｒ
１．４Ｃａ０．６Ｓｉ５Ｎ８：Ｅｕである。この蛍光体
の原料、窒化ストロンチウム、窒化カルシウム、窒化ケ
イ素、金属ユウロピウムの中には、Ｍｇ、Ｓｒ、Ｂａ、
Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｃｏ及びＦｅが約２５０
〜３５０ｐｐｍ濃度含有されている。実施例８は、実施
例７と同様の焼成条件で焼成を行った。図８は、実施例
８を、Ｅｘ＝４６０ｎｍで励起したときの発光スペクト
ルを示す図である。図８から明らかなように、Ｅｘ＝４
６０ｎｍの発光スペクトルの光を照射したところ、ＩＩ
価のＳｒを単独で用いたときよりも、ＳｒとＣａを組み
合わせたときの方が、長波長側にシフトした。発光スペ
クトルのピークは、６５７ｎｍである。これにより、青
色発光素子と実施例８の蛍光体とを組み合わせると赤み
を帯びた白色に発光する蛍光体を得ることができる。ま
た、実施例８の蛍光体Ｓｒ１．４Ｃａ０．６Ｓｉ
５Ｎ８：Ｅｕの量子効率は、１５１．９％と、極めて良
好である。In Example 8, the basic constituent element of the phosphor is Sr.
It is 1.4 Ca 0.6 Si 5 N 8 : Eu. Among the raw materials of this phosphor, strontium nitride, calcium nitride, silicon nitride, and metal europium, Mg, Sr, Ba,
About 250 of Zn, B, Al, Cu, Mn, Co and Fe
The content is up to 350 ppm. In Example 8, firing was performed under the same firing conditions as in Example 7. FIG. 8 is a diagram showing an emission spectrum of Example 8 when excited at Ex = 460 nm. As is clear from FIG. 8, Ex = 4
When irradiated with light having an emission spectrum of 60 nm, II
The combination of Sr and Ca shifted to the longer wavelength side than the case where Sr of valency was used alone. The peak of the emission spectrum is 657 nm. Thus, by combining the blue light emitting element and the phosphor of Example 8, a phosphor emitting reddish white can be obtained. In addition, the phosphor of Example 8 Sr 1.4 Ca 0.6 Si
The quantum efficiency of 5 N 8 : Eu is 151.9%, which is extremely good.

【００７８】実施例９は、Ｅｕの配合割合を変えたもの
である。実施例９も他の実施例と同様、良好な発光特性
を示す。またＥｕ濃度を変えることにより発光波長は６
３７ｎｍとなる。温度特性は、２００℃で９７．９％と
高い数値を示していることから、高安定性を示す。In Example 9, the compounding ratio of Eu was changed. Similar to the other examples, the ninth example also exhibits good light emission characteristics. Also, the emission wavelength is changed to 6 by changing the Eu concentration.
It becomes 37 nm. The temperature characteristics show a high value of 97.9% at 200 ° C., and thus show high stability.

【００７９】＜実施例１０乃至２０＞実施例１０乃至２
０は、残光性の測定を行った。表４は、実施例１０乃至
２０の残光性を測定した結果を示す。図９は、実施例１
０の残光性を測定した測定結果を示す。<Examples 10 to 20> Examples 10 to 2
For 0, the afterglow property was measured. Table 4 shows the results of measuring the afterglow properties of Examples 10 to 20. FIG. 9 shows the first embodiment.
The measurement result which measured the afterglow property of 0 is shown.

【００８０】[0080]

【表４】 [Table 4]

【００８１】実施例１０乃至２０の測定は、２５４ｎｍ
の紫外線を照射し、照射を停止した直後の発光強度を１
とする。照射を停止した直後から発光強度が１／１０に
なるまでの時間を測定する。表４は、発光強度が１／１
０にまるまでに要した時間である。実施例１０乃至２０
は、実施例１の蛍光体と添加物を除き同組成である。つ
まり、蛍光体の基本構成元素がＣａ１．９７Ｅｕ
０．０３Ｓｉ５Ｎ８、成分構成元素がＭｇ、Ｓｒ、Ｂ
ａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｃｏ及びＦｅで、成
分構成元素が２５０〜４００ｐｐｍ濃度含有されてい
る。この実施例１の原料中にＢＮ、Ｈ３ＢＯ３、Ｍｇ３
Ｎ２を数重量％濃度含有する。Ｂ及びＭｇを含有した原
料を、ＢＮるつぼに入れ焼成を行った。実施例１０乃至
１３はＢＮを、実施例１４乃至１７はＨ３ＢＯ３を、実
施例１８乃至２０はＭｇ３Ｎ２を、所定の配合量使用す
る。比較対照として添加物を含有していない蛍光体を基
準値に用いた。その結果、残光は実施例１０乃至１３の
うち実施例１０が最も短かった。実施例１４乃至１７で
は、実施例１４が最も短かく、実施例１８乃至２０で
は、実施例１８も最も短かった。このように、Ｂ、Ｍｇ
を所定量添加することにより、残光特性を抑えることが
できる。The measurement of Examples 10 to 20 was 254 nm.
1 of the luminescence intensity immediately after irradiating the ultraviolet rays and stopping the irradiation
And The time immediately after the irradiation is stopped until the emission intensity becomes 1/10 is measured. Table 4 shows that the emission intensity is 1/1
It is the time required to reach 0. Examples 10 to 20
Has the same composition except for the phosphor of Example 1 and the additive. That is, the basic constituent element of the phosphor is Ca 1.97 Eu.
0.03 Si 5 N 8 , component constituent elements are Mg, Sr, B
a, Zn, B, Al, Cu, Mn, Co, and Fe, and the constituent elements are contained in a concentration of 250 to 400 ppm. BN, H 3 BO 3 , Mg 3 were added to the raw materials of this Example 1.
It contains N 2 in a concentration of several% by weight. The raw material containing B and Mg was put into a BN crucible and fired. BN is used in Examples 10 to 13, H 3 BO 3 is used in Examples 14 to 17, and Mg 3 N 2 is used in Examples 18 to 20 in predetermined amounts. As a comparative control, a phosphor containing no additive was used as a reference value. As a result, the afterglow was the shortest in Example 10 of Examples 10 to 13. In Examples 14 to 17, Example 14 was the shortest, and in Examples 18 to 20, Example 18 was also the shortest. Thus, B, Mg
Afterglow can be suppressed by adding a predetermined amount.

【００８２】＜他の実施例＞窒化物蛍光体の種々の実施
例を示す。本発明に係る窒化物蛍光体は、ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｚの基本構成元素にＭｇ、Ｓ
ｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｃｏ、Ｎｉ、
Ｍｏ、Ｏ及びＦｅからなる群より選ばれる少なくとも１
種以上が含有されている窒化物蛍光体である。該窒化物
蛍光体の基本構成元素である、Ｌは、Ｂｅ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｄ、ＨｇのＩＩ価からなる群
より選ばれる少なくとも１種以上を含有し、Ｍは、Ｃ、
Ｓｉ、Ｇｅ、ＳｎのＩＶ価からなる群より選ばれる少な
くとも１種以上を含有し、Ｚは、賦活剤である。賦活剤
Ｚは、Ｅｕが好ましいが、Ｃｒ、Ｍｎ、Ｐｂ、Ｓｂ、Ｃ
ｅ、Ｔｂ、Ｓｍ、Ｐｒ、Ｔｍ、Ｈｏ、Ｅｒなども使用す
ることができる。<Other Examples> Various examples of the nitride phosphor will be described. The nitride phosphor according to the present invention is L X M Y N
(2 / 3X + 4 / 3Y) : Mg and S as basic constituent elements of Z
r, Ba, Zn, B, Al, Cu, Mn, Co, Ni,
At least 1 selected from the group consisting of Mo, O and Fe
It is a nitride phosphor containing at least one species. The basic constituent element of the nitride phosphor, L is Be, Mg, C
a, Sr, Ba, Zn, Cd, Hg containing at least one selected from the group consisting of II valences, M is C,
It contains at least one selected from the group consisting of IV values of Si, Ge and Sn, and Z is an activator. The activator Z is preferably Eu, but Cr, Mn, Pb, Sb, C
e, Tb, Sm, Pr, Tm, Ho, Er and the like can also be used.

【００８３】窒化物蛍光体の基本構成元素は、Ｓｒ２Ｓ
ｉ５Ｎ８：Ｅｕ、Ｂａ２Ｓｉ５Ｎ８：Ｅｕ、Ｍｇ２Ｓｉ
５Ｎ８：Ｅｕ、Ｚｎ２Ｓｉ５Ｎ８：Ｅｕ、ＳｒＳｉ７Ｎ
１０：Ｅｕ、ＢａＳｉ７Ｎ１０：Ｅｕ、ＭｇＳｉ７Ｎ
１０：Ｅｕ、ＺｎＳｉ７Ｎ１０：Ｅｕ、Ｓｒ２Ｇｅ５Ｎ
８：Ｅｕ、Ｂａ２Ｇｅ５Ｎ８：Ｅｕ、Ｍｇ２Ｇｅ
５Ｎ８：Ｅｕ、Ｚｎ２Ｇｅ５Ｎ８：Ｅｕ、ＳｒＧｅ７Ｎ
１０：Ｅｕ、ＢａＧｅ７Ｎ１０：Ｅｕ、ＭｇＧｅ７Ｎ
１０：Ｅｕ、ＺｎＧｅ７Ｎ１０：Ｅｕ、Ｓｒ１．８Ｃａ
０ ．２Ｓｉ５Ｎ８：Ｅｕ、Ｂａ１．８Ｃａ０．２Ｓｉ５
Ｎ８：Ｅｕ、Ｍｇ１．８Ｃａ０．２Ｓｉ５Ｎ８：Ｅｕ、
Ｚｎ１．８Ｃａ０．２Ｓｉ５Ｎ８：Ｅｕ、Ｓｒ０． ８Ｃ
ａ０．２Ｓｉ７Ｎ１０：Ｅｕ、Ｂａ０．８Ｃａ０．２Ｓ
ｉ７Ｎ１０：Ｅｕ、Ｍｇ０．８Ｃａ０．２Ｓｉ
７Ｎ１０：Ｅｕ、Ｚｎ０．８Ｃａ０．２Ｓｉ７Ｎ１０：
Ｅｕ、Ｓｒ０．８Ｃａ０．２Ｇｅ７Ｎ１０：Ｅｕ、Ｂａ
０．８Ｃａ０．２Ｇｅ ７Ｎ１０：Ｅｕ、Ｍｇ０．８Ｃａ
０．２Ｇｅ７Ｎ１０：Ｅｕ、Ｚｎ０．８Ｃａ０ ．２Ｇｅ
７Ｎ１０：Ｅｕ、Ｓｒ０．８Ｃａ０．２Ｓｉ６ＧｅＮ
１０：Ｅｕ、Ｂａ ０．８Ｃａ０．２Ｓｉ６ＧｅＮ１０：
Ｅｕ、Ｍｇ０．８Ｃａ０．２Ｓｉ６ＧｅＮ １０：Ｅｕ、
Ｚｎ０．８Ｃａ０．２Ｓｉ６ＧｅＮ１０：Ｅｕ、Ｓｒ２
Ｓｉ５Ｎ８：Ｐｒ、Ｂａ２Ｓｉ５Ｎ８：Ｐｒ、Ｓｒ２Ｓ
ｉ５Ｎ８：Ｔｂ、ＢａＧｅ７Ｎ１０：Ｃｅなどが製造で
きる。但し、本発明は、この窒化物蛍光体に限定される
ものでない。The basic constituent element of the nitride phosphor is Sr.TwoS
i5N8: Eu, BaTwoSi5N8: Eu, MgTwoSi
5N8: Eu, ZnTwoSi5N8: Eu, SrSi7N
10: Eu, BaSi7N10: Eu, MgSi7N
10: Eu, ZnSi7N10: Eu, SrTwoGe5N
8: Eu, BaTwoGe5N8: Eu, MgTwoGe
5N8: Eu, ZnTwoGe5N8: Eu, SrGe7N
10: Eu, BaGe7N10: Eu, MgGe7N
10: Eu, ZnGe7N10: Eu, Sr1.8Ca
0 ． TwoSi5N8: Eu, Ba1.8Ca0.2Si5
N8: Eu, Mg1.8Ca0.2Si5N8: Eu,
Zn1.8Ca0.2Si5N8: Eu, Sr0. 8C
a0.2Si7N10: Eu, Ba0.8Ca0.2S
i7N10: Eu, Mg0.8Ca0.2Si
7N10: Eu, Zn0.8Ca0.2Si7N10:
Eu, Sr0.8Ca0.2Ge7N10: Eu, Ba
0.8Ca0.2Ge 7N10: Eu, Mg0.8Ca
0.2Ge7N10: Eu, Zn0.8Ca0 ． TwoGe
7N10: Eu, Sr0.8Ca0.2Si6GeN
10: Eu, Ba 0.8Ca0.2Si6GeN10:
Eu, Mg0.8Ca0.2Si6GeN 10: Eu,
Zn0.8Ca0.2Si6GeN10: Eu, SrTwo
Si5N8: Pr, BaTwoSi5N8: Pr, SrTwoS
i5N8: Tb, BaGe7N10: Ce is manufactured
Wear. However, the present invention is limited to this nitride phosphor
Not a thing.

【００８４】＜発光装置１＞図１０は、本発明に係る発
光装置１を示す図である。<Light Emitting Device 1> FIG. 10 is a view showing the light emitting device 1 according to the present invention.

【００８５】発光層として発光ピークが青色領域にある
４６０ｎｍのＩｎＧａＮ系半導体層を有する半導体発光
素子１０１を用いる。該半導体発光素子１０１には、ｐ
型半導体層とｎ型半導体層とが形成されており（図示し
ない）、該ｐ型半導体層とｎ型半導体層には、リード電
極１０２へ連結される導電性ワイヤ１０４が形成されて
いる。リード電極１０２の外周を覆うように絶縁封止材
１０３が形成され、短絡を防止している。半導体発光素
子１０１の上方には、パッケージ１０５の上部にあるリ
ッド１０６から延びる透光性の窓部１０７が設けられて
いる。該透光性の窓部１０７の内面には、本発明に係る
窒化物蛍光体１０８及びコーティング部材１０９の均一
混合物がほぼ全面に塗布されている。発光装置１では、
実施例１の窒化物蛍光体を使用する。パッケージ１０５
は、角部がとれた一辺が８ｍｍ〜１２ｍｍの正方形であ
る。As the light emitting layer, the semiconductor light emitting device 101 having an InGaN semiconductor layer of 460 nm whose emission peak is in the blue region is used. The semiconductor light emitting device 101 has p
A type semiconductor layer and an n-type semiconductor layer are formed (not shown), and a conductive wire 104 connected to the lead electrode 102 is formed on the p-type semiconductor layer and the n-type semiconductor layer. An insulating encapsulant 103 is formed so as to cover the outer periphery of the lead electrode 102 to prevent a short circuit. Above the semiconductor light emitting device 101, a translucent window portion 107 extending from a lid 106 on the package 105 is provided. A uniform mixture of the nitride phosphor 108 and the coating member 109 according to the present invention is applied on almost the entire inner surface of the translucent window 107. In the light emitting device 1,
The nitride phosphor of Example 1 is used. Package 105
Is a square with one side of which 8 mm to 12 mm is cut off.

【００８６】半導体発光素子１０１で青色に発光した発
光スペクトルは、反射板で反射した間接的な発光スペク
トルと、半導体発光素子１０１から直接射出された発光
スペクトルとが、本発明の窒化物蛍光体１０８に照射さ
れ、白色に発光する蛍光体となる。本発明の窒化物蛍光
体１０８に、緑色系発光蛍光体ＳｒＡｌ２Ｏ４：Ｅｕ、
Ｙ２ＳｉＯ５：Ｃｅ，Ｔｂ、ＭｇＡｌ１１Ｏ１９：Ｃ
ｅ，Ｔｂ、Ｓｒ７Ａｌ１ ２Ｏ２５：Ｅｕ、（Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａのうち少なくとも１以上）Ｇａ２Ｓ ４：
Ｅｕ、青色系発光蛍光体Ｓｒ５（ＰＯ４）３Ｃｌ：Ｅ
ｕ、（ＳｒＣａＢａ） ５（ＰＯ４）３Ｃｌ：Ｅｕ、（Ｂ
ａＣａ）５（ＰＯ４）３Ｃｌ：Ｅｕ、（Ｍｇ、Ｃａ、Ｓ
ｒ、Ｂａのうち少なくとも１以上）２Ｂ５Ｏ９Ｃｌ：Ｅ
ｕ，Ｍｎ、（Ｍｇ、Ｃａ、Ｓｒ、Ｂａのうち少なくとも
１以上）（ＰＯ４）６Ｃｌ２：Ｅｕ，Ｍｎ、赤色系発光
蛍光体Ｙ２Ｏ２Ｓ：Ｅｕ、Ｌａ２Ｏ２Ｓ：Ｅｕ、Ｙ２Ｏ
３：Ｅｕ、Ｇａ２Ｏ２Ｓ：Ｅｕなどをドープすることに
より、所望の発光スペクトルを得ることができる。The semiconductor light emitting device 101 emits blue light.
The light spectrum is the indirect emission spectrum reflected by the reflector.
And light emitted directly from the semiconductor light emitting device 101.
Of the spectrum of the nitride phosphor 108 of the present invention.
As a result, it becomes a phosphor that emits white light. Nitride fluorescence of the present invention
In the body 108, the green light emitting phosphor SrAlTwoOFour: Eu,
YTwoSiO5: Ce, Tb, MgAl11O19: C
e, Tb, Sr7Al1 TwoO25: Eu, (Mg, C
at least one of a, Sr, and Ba) GaTwoS Four:
Eu, blue light emitting phosphor Sr5(POFour)ThreeCl: E
u, (SrCaBa) 5(POFour)ThreeCl: Eu, (B
aCa)5(POFour)ThreeCl: Eu, (Mg, Ca, S
(At least one or more of r and Ba)TwoB5O9Cl: E
u, Mn, (Mg, Ca, Sr, Ba at least
1 or more) (POFour)6ClTwo: Eu, Mn, red emission
Phosphor YTwoOTwoS: Eu, LaTwoOTwoS: Eu, YTwoO
Three: Eu, GaTwoOTwoTo dope S: Eu
As a result, a desired emission spectrum can be obtained.

【００８７】以上のようにして形成された発光装置を用
いて白色ＬＥＤランプを形成すると、歩留まりは９９％
である。このように、本発明である発光ダイオードを使
用することで、量産性良く発光装置を生産でき、信頼性
が高く且つ色調ムラの少ない発光装置を提供することが
できる。When a white LED lamp is formed using the light emitting device formed as described above, the yield is 99%.
Is. As described above, by using the light emitting diode of the present invention, it is possible to produce a light emitting device with high mass productivity, and it is possible to provide a light emitting device having high reliability and less uneven color tone.

【００８８】＜発光装置２＞図１は、本発明に係る発光
装置２を示す図である。図１１は、本発明に係る発光装
置２の発光スペクトルを示す図である。図１２は、本発
明に係る発光装置２の色度座標を示す図である。<Light Emitting Device 2> FIG. 1 is a diagram showing a light emitting device 2 according to the present invention. FIG. 11 is a diagram showing an emission spectrum of the light emitting device 2 according to the present invention. FIG. 12 is a diagram showing chromaticity coordinates of the light emitting device 2 according to the present invention.

【００８９】発光装置２は、サファイア基板１上にｎ型
及びｐ型のＧａＮ層の半導体層２が形成され、該ｎ型及
びｐ型の半導体層２に電極３が設けられ、該電極３は、
導電性ワイヤ１４によりリードフレーム１３と導電接続
されている。半導体発光素子１０の上部は、蛍光体１１
及びコーティング部材１２で覆われ、リードフレーム１
３、蛍光体１１及びコーティング部材１２等の外周をモ
ールド部材１５で覆っている。半導体層２は、サファイ
ア基板１上にｎ＋ＧａＮ：Ｓｉ、ｎ−ＡｌＧａＮ：Ｓ
ｉ、ｎ−ＧａＮ、ＧａＩｎＮ ＱＷｓ、ｐ−ＧａＮ：Ｍ
ｇ、ｐ−ＡｌＧａＮ：Ｍｇ、ｐ−ＧａＮ：Ｍｇの順に積
層されている。該ｎ＋ＧａＮ：Ｓｉ層の一部はエッチン
グされてｎ型電極が形成されている。該ｐ−ＧａＮ：Ｍ
ｇ層上には、ｐ型電極が形成されている。リードフレー
ム１３は、鉄入り銅を用いる。マウントリード１３ａの
上部には、半導体発光素子１０を積載するためのカップ
が設けられており、該カップのほぼ中央部の底面に該半
導体発光素子１０がダイボンドされている。導電性ワイ
ヤ１４には、金を用い、電極３と導電性ワイヤ１４を導
電接続するためのバンプ４には、Ｎｉメッキを施す。蛍
光体１１には、実施例１の窒化物蛍光体とＹＡＧ系蛍光
体とを混合する。コーティング部材１２には、エポキシ
樹脂と拡散剤、チタン酸バリウム、酸化チタン及び前記
蛍光体１１を所定の割合で混合したものを用いる。モー
ルド部材１５は、エポキシ樹脂を用いる。この砲弾型の
発光装置２は、モールド部材１５の半径２〜４ｍｍ、高
さ約７〜１０ｍｍの上部が半球の円筒型である。発光装
置２に電流を流すと、おおよそ４６０ｎｍで励起する第
１の発光スペクトルを有する青色半導体発光素子１０が
発光し、この第１の発光スペクトルを、半導体層２を覆
う窒化物蛍光体１１が色調変換を行い、前記第１の発光
スペクトルと異なる第２の発光スペクトルを有する。ま
た、蛍光体１１中に含有されているＹＡＧ系蛍光体は、
第１の発光スペクトルにより、第３の発光スペクトルを
示す。この第１、第２及び第３の発光スペクトルが互い
に混色となり赤みを帯びた白色に発光する発光装置２を
提供することができる。表５は、本発明に係る発光装置
２の発光特性を示す。図１２、表５は、本発明に係る発
光装置２の比較対象として、ＹＡＧの蛍光体を用いた発
光装置の測定結果も併せて示す。In the light emitting device 2, an n-type and p-type semiconductor layer 2 of GaN layer is formed on a sapphire substrate 1, an electrode 3 is provided on the n-type and p-type semiconductor layer 2, and the electrode 3 is ,
A conductive wire 14 electrically connects to the lead frame 13. The upper part of the semiconductor light emitting device 10 is provided with a phosphor 11
And the lead frame 1 covered with the coating member 12.
3, the outer periphery of the phosphor 11, the coating member 12, etc. is covered with the mold member 15. The semiconductor layer 2 includes n + GaN: Si and n-AlGaN: S on the sapphire substrate 1.
i, n-GaN, GaInN QWs, p-GaN: M
g, p-AlGaN: Mg, and p-GaN: Mg are stacked in this order. A part of the n + GaN: Si layer is etched to form an n-type electrode. The p-GaN: M
A p-type electrode is formed on the g layer. The lead frame 13 uses copper containing iron. A cup for mounting the semiconductor light emitting element 10 is provided on the mount lead 13a, and the semiconductor light emitting element 10 is die-bonded to the bottom surface of substantially the center of the cup. Gold is used for the conductive wire 14, and the bump 4 for conductively connecting the electrode 3 and the conductive wire 14 is plated with Ni. In the phosphor 11, the nitride phosphor of Example 1 and the YAG-based phosphor are mixed. For the coating member 12, a mixture of an epoxy resin, a diffusing agent, barium titanate, titanium oxide, and the phosphor 11 in a predetermined ratio is used. The mold member 15 uses an epoxy resin. This cannonball type light emitting device 2 is a cylindrical type having a hemispherical upper part with a radius of 2 to 4 mm and a height of about 7 to 10 mm of the mold member 15. When a current is applied to the light emitting device 2, the blue semiconductor light emitting element 10 having a first emission spectrum excited at about 460 nm emits light, and the nitride phosphor 11 covering the semiconductor layer 2 produces a color tone with this first emission spectrum. The second emission spectrum is converted and has a second emission spectrum different from the first emission spectrum. Moreover, the YAG-based phosphor contained in the phosphor 11 is
The first emission spectrum shows a third emission spectrum. It is possible to provide the light emitting device 2 that emits reddish white light by mixing the first, second, and third emission spectra with each other. Table 5 shows the light emission characteristics of the light emitting device 2 according to the present invention. FIG. 12 and Table 5 also show the measurement results of a light emitting device using a YAG phosphor as a comparison target of the light emitting device 2 according to the present invention.

【００９０】[0090]

【表５】 [Table 5]

【００９１】 [0091]

【００９２】本発明に係る発光装置２の窒化物蛍光体
は、実施例１の窒化物蛍光体と、コーティング部材１２
と、セリウムで付活されたＹＡＧ（イットリウム・アル
ミニウム・ガーネット）蛍光物質とを混合した蛍光体１
１を用いる。これら蛍光体１１の重量比は、コーティン
グ部材：ＹＡＧ：実施例１の窒化物蛍光体＝２５：６：
３である。一方、青色半導体発光素子とＹＡＧの蛍光体
との組み合わせの発光装置の蛍光体は、コーティング部
材：ＹＡＧ＝２５：６の重量比で混合している。The nitride phosphor of the light emitting device 2 according to the present invention includes the nitride phosphor of Example 1 and the coating member 12.
And a cerium-activated YAG (yttrium-aluminum-garnet) fluorescent substance mixed phosphor 1
1 is used. The weight ratio of these phosphors 11 is as follows: coating member: YAG: nitride phosphor of Example 1 = 25: 6:
It is 3. On the other hand, the phosphors of the light emitting device in which the blue semiconductor light emitting element and the YAG phosphor are combined are mixed in a weight ratio of coating member: YAG = 25: 6.

【００９３】本発明に係る発光装置２と、青色半導体発
光素子及びＹＡＧの蛍光体とを用いた発光装置とを比較
する。このＹＡＧの蛍光体は、ピーク波長が４６３．４
７ｎｍであるのに対し、窒化物蛍光体のピーク波長は、
５９６．００ｎｍと異なる位置に発光スペクトルを有し
ている。色度座標においても、ＹＡＧの蛍光体のみを用
いた発光装置は、色調ｘ＝０．３４８、色調ｙ＝０．３
６７で表され比較的青白く発光する白色である。一方、
ＹＡＧ系蛍光体と窒化物蛍光体とを用いた発光装置２
は、色調ｘ＝０．４５４、色調ｙ＝０．４１６で表され
る赤みを帯びた白色である。色温度は、２８２７．９６
Ｋ、演色性Ｒａは、７６であり、電球色に近い発光特性
を有している。また、本発明に係る発光装置２は、２
４．８７ｌｍ／Ｗという高い発光効率を有している。こ
のことから、電球色に近い発光装置を製造することがで
きるという極めて重要な技術的意義を有する。The light emitting device 2 according to the present invention is compared with a light emitting device using a blue semiconductor light emitting element and a YAG phosphor. This YAG phosphor has a peak wavelength of 463.4.
While the peak wavelength of the nitride phosphor is 7 nm,
It has an emission spectrum at a position different from 596.00 nm. Also in the chromaticity coordinates, the light emitting device using only the YAG phosphor has a color tone x = 0.348 and a color tone y = 0.3.
It is white, which is represented by 67 and emits a relatively bluish white light. on the other hand,
Light emitting device 2 using YAG-based phosphor and nitride phosphor
Is a reddish white represented by color tone x = 0.454 and color tone y = 0.416. The color temperature is 2827.96.
The K and the color rendering index Ra are 76, and the light emitting characteristics are close to those of a light bulb. In addition, the light emitting device 2 according to the present invention is 2
It has a high luminous efficiency of 4.87 lm / W. From this, it has a very important technical significance that a light emitting device having a light bulb color can be manufactured.

【００９４】[0094]

【発明の効果】従って、本発明は、第１の発光スペクト
ルの一部を変換し、第１の発光スペクトルと異なる領域
に第２の発光スペクトルを有する発光輝度の高い蛍光体
を提供すること、具体的には、光源に紫外から青色領域
の発光スペクトルを有する半導体発光素子を使用し、該
半導体発光素子からの発光スペクトルを色調変換し、や
や赤みを帯びた暖色系の白色に発光する発光特性の優れ
た蛍光体を提供することができる。また、残光が短い蛍
光体を提供することができる。さらに、青色半導体発光
素子と該蛍光体とを組み合わせて白色に発光する発光装
置を提供することができる。Therefore, the present invention provides a phosphor having a high emission brightness, which converts a part of the first emission spectrum and has the second emission spectrum in a region different from the first emission spectrum. Specifically, a semiconductor light-emitting element having an emission spectrum in the ultraviolet to blue region is used as a light source, the emission spectrum from the semiconductor light-emitting element is color-tone-converted, and light emission characteristics that emits warm reddish white with a slight reddish color It is possible to provide an excellent phosphor of Further, it is possible to provide a phosphor having a short afterglow. Further, it is possible to provide a light emitting device that emits white light by combining a blue semiconductor light emitting element and the phosphor.

【００９５】本発明は、蛍光表示管、ディスプレイ、Ｐ
ＤＰ、ＣＲＴ、ＦＬ、ＦＥＤ及び投写管等、特に、青色
発光ダイオード又は紫外発光ダイオードを光源とする発
光装置、店頭のディスプレイ用の照明、医療現場用の照
明などの蛍光ランプに使用することができる。その他、
携帯電話のバックライト、発光ダイオード（ＬＥＤ）の
分野などにも応用することができる。このように、本発
明は、従来解決されなかった課題を解決するものであ
り、極めて優れた技術的意義を有する。The present invention includes a fluorescent display tube, a display, a P
It can be used for fluorescent lamps such as DP, CRT, FL, FED, and projection tubes, especially light emitting devices using blue light emitting diodes or ultraviolet light emitting diodes as light sources, lighting for displays in stores, and lighting for medical sites. . Other,
It can also be applied to the field of mobile phone backlights, light emitting diodes (LEDs), and the like. As described above, the present invention solves a problem that has not been solved in the past, and has an extremely excellent technical significance.

【図面の簡単な説明】[Brief description of drawings]

【図１】 本発明に係る発光装置２を示す図である。FIG. 1 is a diagram showing a light emitting device 2 according to the present invention.

【図２】 本発明に係る窒化物蛍光体の製造方法を示す
図である。FIG. 2 is a diagram showing a method for manufacturing a nitride phosphor according to the present invention.

【図３】 実施例２及び３の窒化物蛍光体をＥｘ＝４６
０ｎｍで励起したときの発光スペクトルを示す図であ
る。FIG. 3 shows the nitride phosphors of Examples 2 and 3 with Ex = 46.
It is a figure which shows the emission spectrum when excited by 0 nm.

【図４】 実施例２及び３の窒化物蛍光体の励起スペク
トルを示す図である。FIG. 4 is a diagram showing excitation spectra of the nitride phosphors of Examples 2 and 3.

【図５】 実施例２及び３の窒化物蛍光体の反射スペク
トルを示す図である。FIG. 5 is a diagram showing reflection spectra of the nitride phosphors of Examples 2 and 3.

【図６】 実施例３の窒化物蛍光体の粒径を撮影した写
真である。6 is a photograph of the grain size of the nitride phosphor of Example 3. FIG.

【図７】 実施例１及び比較例３の窒化物蛍光体を、Ｅ
ｘ＝４６０ｎｍで励起したときの発光スペクトルを示す
図である。FIG. 7 shows the nitride phosphors of Example 1 and Comparative Example 3
It is a figure which shows the emission spectrum when excited by x = 460 nm.

【図８】 実施例８の窒化物蛍光体をＥｘ＝４６０ｎｍ
で励起したときの発光スペクトルを示す図である。FIG. 8 shows the nitride phosphor of Example 8 with Ex = 460 nm.
It is a figure which shows the emission spectrum when excited by.

【図９】 実施例１０の残光性を測定した測定結果を示
す図である。9 is a diagram showing the measurement results of measuring the afterglow property of Example 10. FIG.

【図１０】 本発明に係る発光装置１の発光スペクトル
を示す図である。FIG. 10 is a diagram showing an emission spectrum of the light emitting device 1 according to the present invention.

【図１１】 本発明に係る発光装置２の発光スペクトル
を示す図である。FIG. 11 is a diagram showing an emission spectrum of the light emitting device 2 according to the present invention.

【図１２】 本発明に係る発光装置２の色度座標を示す
図である。FIG. 12 is a diagram showing chromaticity coordinates of the light emitting device 2 according to the present invention.

【符号の説明】[Explanation of symbols]

Ｐ１ 原料のＬ及びＭｇ等を粉砕する。 Ｐ２ 原料のＳｉ及びＡｌ等を粉砕する。 Ｐ３ 原料のＬ及びＭｇ等を、窒素雰囲気中で窒化す
る。 Ｐ４ 原料のＳｉ及びＡｌ等を、窒素雰囲気中で窒化
する。 Ｐ５ Ｌ及びＭｇ等の窒化物を粉砕する。 Ｐ６ Ｓｉ及びＡｌ等の窒化物を粉砕する。 Ｐ７ Ｅｕの化合物Ｅｕ２Ｏ３を粉砕する。 Ｐ８ Ｌ及びＭｇ等の窒化物、Ｓｉ及びＡｌ等の窒化
物、Ｅｕの化合物Ｅｕ２Ｏ３等を混合する。 Ｐ９ Ｌ及びＭｇ等の窒化物、Ｓｉ及びＡｌ等の窒化
物、Ｅｕの化合物Ｅｕ２Ｏ３等の混合物をアンモニア雰
囲気中で、焼成する。 Ｐ１０ Ｍｇ、Ａｌ等を含有するＬＸＳｉＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｅｕで表される蛍光体を得る
ことができる。 １ 基板 ２ 半導体層 ３ 電極 ４ バンプ １０ 半導体発光素子 １１ 蛍光体 １２ コーティング部材 １３ リードフレーム １３ａ マウントリード １３ｂ インナーリード １４ 導電性ワイヤ １５ モールド部材 １０１ 半導体発光素子 １０２ リード電極 １０３ 絶縁封止材 １０４ 導電性ワイヤ １０５ パッケージ １０６ リッド １０７ 窓部 １０８ 蛍光体 １０９ コーティング部材P1 Raw materials such as L and Mg are crushed. P2 Raw materials such as Si and Al are crushed. P3 raw material L, Mg, etc. are nitrided in a nitrogen atmosphere. P4 raw material such as Si and Al is nitrided in a nitrogen atmosphere. Grind P5 L and nitrides such as Mg. Grind nitrides such as P6 Si and Al. P7 grinding the compound Eu 2 O 3 of Eu. P8 L and a nitride such as Mg, a nitride such as Si and Al, and a compound of Eu such as Eu 2 O 3 are mixed. A mixture of nitrides such as P9L and Mg, nitrides such as Si and Al, and a compound of Eu such as Eu 2 O 3 is fired in an ammonia atmosphere. P10 Mg, Al, etc. containing L X Si Y N
(2 / 3X + 4 / 3Y) : A phosphor represented by Eu can be obtained. 1 Substrate 2 Semiconductor Layer 3 Electrode 4 Bump 10 Semiconductor Light-Emitting Element 11 Phosphor 12 Coating Member 13 Lead Frame 13a Mount Lead 13b Inner Lead 14 Conductive Wire 15 Mold Member 101 Semiconductor Light-Emitting Element 102 Lead Electrode 103 Insulation Sealant 104 Conductivity Wire 105 Package 106 Lid 107 Window 108 Phosphor 109 Coating Member

フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０９Ｋ 11/66 ＣＱＦ Ｃ０９Ｋ 11/66 ＣＱＦ 11/67 ＣＰＭ 11/67 ＣＰＭ 11/80 11/80 Ｈ０１Ｌ 33/00 Ｈ０１Ｌ 33/00 Ｎ Ｆターム(参考） 4H001 CA04 CA05 CA07 CF02 XA03 XA04 XA05 XA06 XA07 XA08 XA11 XA12 XA13 XA14 XA19 XA20 XA22 XA24 XA25 XA26 XA28 XA29 XA30 XA31 XA32 XA37 XA38 XA39 XA40 XA42 XA48 XA49 XA50 XA56 XA72 XA80 YA00 YA24 YA25 YA51 YA58 YA63 YA82 5F041 AA03 AA11 AA43 CA05 CA12 CA40 CA46 CB36 DA12 DA16 DA19 DA43 DA55 DA56 DA57 DA75 DB02 DB04 EE25 FF11 FF16 Front page continuation (51) Int.Cl. 7 Identification code FI theme code (reference) C09K 11/66 CQF C09K 11/66 CQF 11/67 CPM 11/67 CPM 11/80 11/80 H01L 33/00 H01L 33 / 00 NF Term (reference) 4H001 CA04 CA05 CA07 CF02 XA03 XA04 XA05 XA06 XA07 XA08 XA11 XA12 XA13 XA14 XA19 XA20 XA22 XA24 XA25 XA26 XA28 XA29 XA58 XA58 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 XA38 YA63 YA82 5F041 AA03 AA11 AA43 CA05 CA12 CA40 CA46 CB36 DA12 DA16 DA19 DA43 DA55 DA56 DA57 DA75 DB02 DB04 EE25 FF11 FF16

Claims (19)

【特許請求の範囲】[Claims] 【請求項１】 第１の発光スペクトルの少なくとも一部
を変換し、前記第１の発光スペクトルと異なる領域に第
２の発光スペクトルを少なくとも１以上有している、基
本構成元素に少なくとも窒素を含有する窒化物蛍光体で
あって、前記窒化物蛍光体は、ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｚ（Ｌは、Ｂｅ、Ｍｇ、Ｃ
ａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃｄ、ＨｇのＩＩ価からなる群
より選ばれる少なくとも１種以上を含有する。Ｍは、
Ｃ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔｉ、Ｚｒ、ＨｆのＩＶ価から
なる群より選ばれる少なくとも１種以上を含有する。Ｚ
は、賦活剤である。）で表される基本構成元素を少なく
とも含有しており、かつ、Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｃ
ａ、Ｇａ、Ｉｎ、Ｂ、Ａｌ、Ｃｕ、Ｍｎ、Ｌｉ、Ｎａ、
Ｋ、Ｒｅ、Ｎｉ、Ｃｒ、Ｍｏ、Ｏ及びＦｅからなる群よ
り選ばれる少なくとも１種以上を含有することを特徴と
する窒化物蛍光体。1. A basic constituent element containing at least nitrogen, which converts at least a part of a first emission spectrum and has at least one second emission spectrum in a region different from the first emission spectrum. Which is a nitride phosphor, wherein the nitride phosphor is L X M Y N
(2 / 3X + 4 / 3Y) : Z (L is Be, Mg, C
It contains at least one selected from the group consisting of II valences of a, Sr, Ba, Zn, Cd, and Hg. M is
It contains at least one selected from the group consisting of IV values of C, Si, Ge, Sn, Ti, Zr and Hf. Z
Is an activator. ) Containing at least the basic constituent element represented by the formula (1) and Mg, Sr, Ba, Zn, C
a, Ga, In, B, Al, Cu, Mn, Li, Na,
A nitride phosphor containing at least one selected from the group consisting of K, Re, Ni, Cr, Mo, O and Fe. 【請求項２】 前記窒化物蛍光体は、ＬＸＭＹＮ
（２／３Ｘ＋４／３Ｙ）：Ｚ（Ｌは、Ｍｇ、Ｃａ、Ｓ
ｒ、ＢａのＩＩ価からなる群より選ばれる少なくとも１
種以上を含有する。Ｍは、Ｓｉである。Ｚは、賦活剤で
ある。）で表される基本構成元素を少なくとも含有して
おり、かつ、Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｂ、Ａｌ、Ｃ
ｕ、Ｍｎ、Ｃｒ、Ｏ及びＮｉからなる群より選ばれる少
なくとも１種以上を含有することを特徴とする請求項１
に記載の窒化物蛍光体。2. The nitride phosphor is L X M Y N
(2 / 3X + 4 / 3Y) : Z (L is Mg, Ca, S
at least 1 selected from the group consisting of r and Ba II valences
Contains more than one seed. M is Si. Z is an activator. ) Containing at least the basic constituent element represented by the formula (1) and Mg, Sr, Ba, Zn, B, Al, C
2. At least one selected from the group consisting of u, Mn, Cr, O and Ni is contained.
The nitride phosphor according to 1. 【請求項３】 前記Ｚで表される賦活剤は、Ｅｕである
ことを特徴とする請求項１又は２のいずれかに記載の窒
化物蛍光体。3. The nitride phosphor according to claim 1, wherein the activator represented by Z is Eu. 【請求項４】 前記Ｚで表される賦活剤は、Ｍｎ、Ｂ、
Ｃｅ、Ｍｇ、Ｃｕ、Ａｌ及びＥｕのうち少なくとも１種
以上を含有するものであることを特徴とする請求項１又
は２のいずれかに記載の窒化物蛍光体。4. The activator represented by Z is Mn, B,
The nitride phosphor according to claim 1 or 2, which contains at least one kind of Ce, Mg, Cu, Al, and Eu. 【請求項５】 前記Ｘ及びＹは、Ｘ＝２、Ｙ＝５である
ことを特徴とする請求項１又は２のいずれかに記載の窒
化物蛍光体。5. The nitride phosphor according to claim 1, wherein X and Y are X = 2 and Y = 5. 【請求項６】 前記Ｘ及びＹは、Ｘ＝１、Ｙ＝７である
ことを特徴とする請求項１又は２のいずれかに記載の窒
化物蛍光体。6. The nitride phosphor according to claim 1, wherein X and Y are X = 1 and Y = 7. 【請求項７】 前記Ｌと前記Ｚとは、Ｌ：Ｚ＝１：０．
００１〜１のモル比の関係を有することを特徴とする請
求項１乃至４の少なくともいずれか一項に記載の窒化物
蛍光体。7. The L and the Z are L: Z = 1: 0.
The nitride phosphor according to at least any one of claims 1 to 4, wherein the nitride phosphor has a molar ratio relationship of 001 to 1. 【請求項８】 前記窒化物蛍光体は、平均粒径が０．１
〜１０μｍの大きさであることを特徴とする請求項１乃
至７の少なくともいずれか一項に記載の窒化物蛍光体。8. The nitride phosphor has an average particle size of 0.1.
The nitride phosphor according to at least any one of claims 1 to 7, which has a size of 10 µm. 【請求項９】 前記窒化物蛍光体は、黄から赤領域に第
２の発光スペクトルを少なくとも１以上有していること
を特徴とする請求項１乃至８の少なくともいずれか一項
に記載の窒化物蛍光体。9. The nitride phosphor according to claim 1, wherein the nitride phosphor has at least one second emission spectrum in a yellow to red region. Phosphor. 【請求項１０】 前記窒化物蛍光体は、５２０ｎｍから
７８０ｎｍの波長範囲に前記第２の発光スペクトルを少
なくとも１以上有していることを特徴とする請求項１乃
至８の少なくともいずれか一項に記載の窒化物蛍光体。10. The nitride phosphor has at least one of the second emission spectra in a wavelength range of 520 nm to 780 nm, and the nitride phosphor has at least one of the second emission spectra. The nitride phosphor described. 【請求項１１】 ＬＸＭＹＮ（２／３Ｘ＋４／３Ｙ）：
Ｚ（Ｌは、Ｂｅ、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｚｎ、Ｃ
ｄ、ＨｇのＩＩ価からなる群より選ばれる少なくとも１
種以上を含有する。Ｍは、Ｃ、Ｓｉ、Ｇｅ、Ｓｎ、Ｔ
ｉ、Ｚｒ、ＨｆのＩＶ価からなる群より選ばれる少なく
とも１種以上を含有する。Ｚは、賦活剤である。）で表
される基本構成元素を少なくとも含有しており、かつ、
Ｍｇ、Ｓｒ、Ｂａ、Ｚｎ、Ｃａ、Ｇａ、Ｉｎ、Ｂ、Ａ
ｌ、Ｃｕ、Ｍｎ、Ｌｉ、Ｎａ、Ｋ、Ｒｅ、Ｎｉ、Ｃｒ、
Ｍｏ、Ｏ及びＦｅからなる群より選ばれる少なくとも１
種以上を含有する窒化物蛍光体の製造方法であって、前
記窒化物蛍光体の原料を、アンモニア雰囲気中で焼成が
行われる工程を有することを特徴とする窒化物蛍光体の
製造方法。11. L X M Y N (2 / 3X + 4 / 3Y) :
Z (L is Be, Mg, Ca, Sr, Ba, Zn, C
d, at least 1 selected from the group consisting of Hg II values
Contains more than one seed. M is C, Si, Ge, Sn, T
It contains at least one or more selected from the group consisting of IV values of i, Zr, and Hf. Z is an activator. ) Contains at least the basic constituent element represented by
Mg, Sr, Ba, Zn, Ca, Ga, In, B, A
l, Cu, Mn, Li, Na, K, Re, Ni, Cr,
At least 1 selected from the group consisting of Mo, O and Fe
A method for producing a nitride phosphor containing at least one species, comprising the step of firing the raw material of the nitride phosphor in an ammonia atmosphere. 【請求項１２】 前記焼成は、窒化ホウ素材質のるつぼ
を用いて焼成が行われていることを特徴とする請求項１
１に記載の窒化物蛍光体の製造方法。12. The firing is performed by using a crucible made of a boron nitride material.
1. The method for producing a nitride phosphor according to 1. 【請求項１３】 第１の発光スペクトルを有する半導体
発光素子と、前記第１の発光スペクトルの少なくとも一
部を変換し、前記第１の発光スペクトルと異なる領域に
第２の発光スペクトルを少なくとも１以上有している蛍
光体と、を少なくとも有する発光装置であって、前記蛍
光体には、請求項１乃至１０の少なくともいずれか１項
に記載の窒化物蛍光体が含有されていることを特徴とす
る発光装置。13. A semiconductor light emitting device having a first emission spectrum and at least a part of the first emission spectrum are converted, and at least one second emission spectrum is provided in a region different from the first emission spectrum. A light emitting device having at least a phosphor having the phosphor, wherein the phosphor contains the nitride phosphor according to at least any one of claims 1 to 10. Light emitting device. 【請求項１４】 前記蛍光体には、セリウムで賦活され
たイットリウム・アルミニウム酸化物系蛍光物質が含有
されていることを特徴とする請求項１３に記載の発光装
置。14. The light emitting device according to claim 13, wherein the phosphor contains a yttrium-aluminum oxide phosphor material activated by cerium. 【請求項１５】 前記蛍光体に含有されている、前記セ
リウムで賦活されたイットリウム・アルミニウム酸化物
系蛍光物質と前記請求項１乃至１０の少なくともいずれ
か１項に記載の窒化物蛍光体との重量比率は、１〜１５
対１で混合されていることを特徴とする請求項１４に記
載の発光装置。15. The yttrium-aluminum oxide-based fluorescent material activated by cerium, which is contained in the fluorescent material, and the nitride fluorescent material according to any one of claims 1 to 10. Weight ratio is 1-15
The light emitting device according to claim 14, wherein the light emitting device is mixed in a pair. 【請求項１６】 前記第１の発光スペクトルは、３６０
〜５５０ｎｍに発光波長を有しており、前記第１の発光
スペクトルの少なくとも一部が変換された光と、前記第
１の発光スペクトルの他の一部と、が混合されて放出さ
れることにより白色系の発光が行われることを特徴とす
る請求項１３乃至１５の少なくともいずれか一項に記載
の発光装置。16. The first emission spectrum is 360
Light having an emission wavelength of ˜550 nm, at least a part of which is converted from the first emission spectrum, and the other part of the first emission spectrum being mixed and emitted. The light emitting device according to claim 13, wherein white light emission is performed. 【請求項１７】 前記蛍光体は、粉体又は粒体であっ
て、光透光性材料に含有されていることを特徴とする請
求項１３乃至１６の少なくともいずれか一項に記載の発
光装置。17. The light emitting device according to claim 13, wherein the phosphor is a powder or granules and is contained in a light transmissive material. . 【請求項１８】 前記半導体発光素子は、ＩＩＩ族窒化
物系化合物半導体発光素子であることを特徴とする請求
項１３乃至１７の少なくともいずれか一項に記載の発光
装置。18. The light emitting device according to claim 13, wherein the semiconductor light emitting element is a group III nitride compound semiconductor light emitting element. 【請求項１９】 前記発光装置は、平均演色評価数Ｒａ
が７５乃至９５であり、色温度が２０００Ｋから８００
０Ｋであることを特徴とする請求項１３乃至１８の少な
くともいずれか一項に記載の発光装置。19. The light emitting device has an average color rendering index Ra.
Is 75 to 95, and the color temperature is from 2000K to 800
19. The light emitting device according to claim 13, wherein the light emitting device has a value of 0K.
JP2002126566A 2002-03-22 2002-04-26 Nitride fluorophor and method for producing the same Pending JP2003321675A (en)

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KR1020097013180A KR100961342B1 (en) 2002-03-22 2003-03-20 Nitride Phosphor and Production Process Thereof, and Light Emitting Device
US10/478,598 US7258816B2 (en) 2002-03-22 2003-03-20 Nitride phosphor and method for preparation thereof, and light emitting device
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CNB038004542A CN100430456C (en) 2002-03-22 2003-03-20 Nitride phosphor and method for preparation thereof, and light emitting device
KR1020097013179A KR100983193B1 (en) 2002-03-22 2003-03-20 Nitride Phosphor and Production Process Thereof, and Light Emitting Device
KR1020037015150A KR100961324B1 (en) 2002-03-22 2003-03-20 Nitride Phosphor and Production Process Thereof, and Light Emitting Device
PCT/JP2003/003418 WO2003080764A1 (en) 2002-03-22 2003-03-20 Nitride phosphor and method for preparation thereof, and light emitting device
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