JPH11246857A - Red light emitting phosphor, its production and led lamp - Google Patents
Red light emitting phosphor, its production and led lampInfo
- Publication number
- JPH11246857A JPH11246857A JP10048275A JP4827598A JPH11246857A JP H11246857 A JPH11246857 A JP H11246857A JP 10048275 A JP10048275 A JP 10048275A JP 4827598 A JP4827598 A JP 4827598A JP H11246857 A JPH11246857 A JP H11246857A
- Authority
- JP
- Japan
- Prior art keywords
- phosphor
- light
- red light
- light emitting
- emitting 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.)
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Links
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Luminescent Compositions (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は赤色発光蛍光体、そ
の製造方法およびＬＥＤランプに係り、特に波長３７０
nm付近の紫外線励起光を効率的に吸収して赤色光に変換
することが可能な赤色発光蛍光体、その効率的な製造方
法およびその蛍光体を使用した高輝度のＬＥＤランプに
関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a red light-emitting phosphor, a method for producing the same, and an LED lamp, and more particularly, to a wavelength of 370.
The present invention relates to a red light-emitting phosphor capable of efficiently absorbing ultraviolet excitation light in the vicinity of nm and converting it into red light, an efficient manufacturing method thereof, and a high-brightness LED lamp using the phosphor.
【０００２】[0002]
【従来の技術】発光ダイオード（ＬＥＤ：Light Emitti
ng Diode）は光を放射する半導体ダイオードであり、電
気エネルギーを可視光または赤外光に変換するものであ
る。特に可視光を利用するためにＧａＰやＧａＡｓＰ，
ＧａＡｌＡｓ等の発光材料で形成した発光チップを透明
樹脂等で封止したＬＥＤランプとして広く使用されてい
る。また発光材料をプリント基板や金属リードの上面に
固定し、数字や文字を形どった樹脂ケースで封止したデ
ィスプレイ型のＬＥＤランプも多用されている。2. Description of the Related Art Light emitting diodes (LEDs)
ng Diode) is a semiconductor diode that emits light and converts electric energy into visible light or infrared light. In particular, in order to use visible light, GaP or GaAsP,
It is widely used as an LED lamp in which a light emitting chip formed of a light emitting material such as GaAlAs is sealed with a transparent resin or the like. Display-type LED lamps, in which a light emitting material is fixed on the upper surface of a printed circuit board or a metal lead and sealed with a resin case in which numerals and characters are formed, are also frequently used.
【０００３】また、発光チップの表面ないし発光ダイオ
ードの樹脂中に各種の蛍光体粉末を含有させることによ
り、放射光の色を適正に調整することも可能である。す
なわち、発光ダイオードランプの発光色は、青色から赤
色まで各使用用途に応じた可視光領域の発光を再現する
ことができる。また、発光ダイオードは半導体素子であ
るため、寿命が長く信頼性も高く、光源として用いた場
合には、その交換作業も軽減化されることから、携帯通
信機器，パーソナルコンピュータ周辺機器，ＯＡ機器，
家庭用電気機器，オーディオ機器，各種スイッチ，バッ
クライト用光源表示板等の各種表示装置の構成部品とし
て広く使用されている。In addition, it is possible to appropriately adjust the color of emitted light by incorporating various phosphor powders into the surface of the light emitting chip or the resin of the light emitting diode. That is, the light emission color of the light-emitting diode lamp can reproduce light emission in a visible light region according to each use from blue to red. Further, since the light emitting diode is a semiconductor element, it has a long life and high reliability, and when used as a light source, the replacement work is reduced. Therefore, portable communication devices, personal computer peripheral devices, OA devices,
It is widely used as a component of various display devices such as household electric equipment, audio equipment, various switches, and light source display panels for backlights.
【０００４】[0004]
【発明が解決しようとする課題】しかしながら、最近で
は、上記各種表示装置の利用者の色彩感覚がさらに向上
し、各種表示装置においても、微妙な色合いをより高精
細に再現できる機能が要求されている。また、１個の発
光ダイオードによって白色ないし各種の中間色を再現す
る機能も強く求められている。However, recently, users of the above-mentioned various display devices have been further improved in color sensation, and various display devices have been required to have a function capable of reproducing fine colors with higher definition. I have. There is also a strong demand for a function of reproducing white or various intermediate colors with one light emitting diode.
【０００５】そのため、ＬＥＤランプの発光チップの表
面に、さらに青色，赤色，緑色発光蛍光体を塗布した
り、発光ダイオードを構成する樹脂中に上記各種蛍光体
粉末を含有させることにより、１個の発光ダイオードか
ら白色ないし任意の中間色を取り出すように構成するこ
とも試行されている。従来から発光ダイオードから放射
される３７０nm前後の波長の紫外線によって、効率的に
可視光を放射する青色発光蛍光体および緑色発光蛍光体
は数多く存在する。[0005] Therefore, a blue, red, or green light emitting phosphor is further applied to the surface of a light emitting chip of an LED lamp, or the above various phosphor powders are contained in a resin constituting a light emitting diode so that one light emitting chip is formed. Attempts have been made to construct white or any intermediate color from the light emitting diode. Conventionally, there are many blue light emitting phosphors and green light emitting phosphors that efficiently emit visible light by ultraviolet light having a wavelength of about 370 nm emitted from a light emitting diode.
【０００６】しかしながら、特に赤色発光蛍光体は、他
の青色，緑色発光蛍光体と比較して、波長３７０nm前後
の励起光（紫外線）に対して吸収が弱いという問題点が
あり、特に赤色発光に近い色合いの放射光を再現しよう
とすると、その発光輝度が大幅に低下してしまう問題点
があった。However, in particular, the red light-emitting phosphor has a problem that it is weaker in absorption of excitation light (ultraviolet light) having a wavelength of about 370 nm than other blue and green light-emitting phosphors. There is a problem that when trying to reproduce light having a close color tone, the light emission luminance is significantly reduced.
【０００７】本発明は上記問題点を解決するためになさ
れたものであり、発光ダイオードの励起波長３７０nm前
後において、効率的に紫外線を吸収して赤色発光を効率
よく放射でき、１個の発光ダイオードから白色ないし任
意の中間色を取り出すために、この発光ダイオードに実
用的に使用できる赤色発光蛍光体，その製造方法および
その蛍光体を使用したＬＥＤランプを提供することを目
的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problem, and it is possible to efficiently absorb ultraviolet rays and emit red light efficiently at an excitation wavelength of about 370 nm of a light-emitting diode, thereby enabling one light-emitting diode to be emitted. It is an object of the present invention to provide a red light-emitting phosphor that can be practically used for this light-emitting diode in order to extract white or any intermediate color from the light-emitting diode, a method of manufacturing the same, and an LED lamp using the phosphor.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、上記目的
を達成するため、種々の組成から成る赤色発光蛍光体を
調製し、この組成成分の種類および添加量が蛍光体の励
起スペクトル分布および発光輝度に及ぼす影響を実験に
より比較検討した。Means for Solving the Problems In order to achieve the above object, the present inventors have prepared red light-emitting phosphors having various compositions, and the kind and the amount of these components have been adjusted to the excitation spectrum distribution of the phosphor. The effect on light emission luminance was compared by experiments.
【０００９】その結果、ユーロピウム付活酸硫化ランタ
ン蛍光体に所定量のサマリウム（Ｓｍ）を添加配合する
ことにより励起スペクトル分布のピークが波長３７０nm
前後と長波長側にシフトでき、ＬＥＤランプの発光チッ
プの励起紫外線によって赤色発光を効率的に放射できる
ことが可能な赤色発光蛍光体が初めて得られるという知
見を得た。本発明は上記知見に基づいて完成されたもの
である。As a result, by adding a predetermined amount of samarium (Sm) to the europium-activated lanthanum oxysulfide phosphor, the peak of the excitation spectrum distribution becomes 370 nm.
It has been found that a red light-emitting phosphor that can be shifted back and forth and to a longer wavelength side and can efficiently emit red light by excitation ultraviolet rays of a light-emitting chip of an LED lamp is obtained for the first time. The present invention has been completed based on the above findings.
【００１０】すなわち本発明に係る赤色発光蛍光体は、
一般式（Ｌａ1-x-y Ｅｕx Ｓｍy ）2 Ｏ2 Ｓ（但し、
０．０１≦ｘ≦０．１５，０．０００１≦ｙ≦０．０
３）で表わされるユーロピウム・サマリウム付活酸硫化
ランタン蛍光体から成ることを特徴とする。また、励起
スペクトル分布におけるピーク波長が、３６０〜３８０
nmの紫外線波長領域に存在することを特徴とする。That is, the red light-emitting phosphor according to the present invention comprises:
Formula (La 1-xy Eu x Sm y) 2 O 2 S ( where,
0.01 ≦ x ≦ 0.15, 0.0001 ≦ y ≦ 0.0
It is characterized by comprising a europium-samarium-activated lanthanum oxysulfide phosphor represented by 3). The peak wavelength in the excitation spectrum distribution is 360 to 380.
It exists in the ultraviolet wavelength region of nm.
【００１１】さらに、一般式におけるユーロピウム（Ｅ
ｕ）の原子比（ｘ）が０．０３〜０．０８の範囲である
ことが、より好ましい。また、一般式におけるサマリウ
ム（Ｓｍ）の原子比（ｙ）が０．００１〜０．０１の範
囲であることが、より好ましい。Further, europium (E
More preferably, the atomic ratio (x) of u) is in the range of 0.03 to 0.08. Further, it is more preferable that the atomic ratio (y) of samarium (Sm) in the general formula is in the range of 0.001 to 0.01.
【００１２】さらに、Ｌａの３０ mol％以下を、Ｙおよ
びＧｄの少なくとも一方の元素で置換してもよい。ま
た、Ｌａに対するＹおよびＧｄの少なくとも一方の元素
の置換量が５〜２０ mol％であることが、より好まし
い。Further, 30 mol% or less of La may be replaced by at least one of Y and Gd. Further, the substitution amount of at least one element of Y and Gd with respect to La is more preferably 5 to 20 mol%.
【００１３】また、本発明に係る赤色発光蛍光体の製造
方法は、一般式（Ｌａ1-x-y ＥｕxＳｍy ）2 Ｏ2 Ｓ
（但し、０．０１≦ｘ≦０．１５，０．０００１≦ｙ≦
０．０３）で表わされる組成を有するように各原料粉末
を均一に配合して原料混合体を調製する工程と、得られ
た原料混合体を焼成する工程と、得られた焼成物を純水
にて洗浄して不要な可溶成分を除去する工程と、さらに
焼成物をｐＨ２以上の酸性液中で酸洗浄する工程と、酸
洗浄した焼成物を純水にて洗浄後、濾過・乾燥する工程
とを備えることを特徴とする。[0013] In the method of manufacturing the red-emitting phosphor according to the present invention have the general formula (La 1-xy Eu x Sm y) 2 O 2 S
(However, 0.01 ≦ x ≦ 0.15, 0.0001 ≦ y ≦
0.03) a step of preparing a raw material mixture by uniformly blending each raw material powder so as to have a composition represented by formula (3), a step of firing the obtained raw material mixture, and a step of purifying the obtained fired product with pure water. A step of removing unnecessary soluble components by washing at a temperature, a step of further acid-cleaning the calcined product in an acidic solution having a pH of 2 or more, and washing the acid-cleaned calcined product with pure water, followed by filtration and drying. And a step.
【００１４】さらに、本発明に係るＬＥＤランプは、発
光材料と組み合わされたＬＥＤチップに通電すことによ
り電気エネルギーを可視光または赤外光に変換する発光
ダイオード（ＬＥＤ）ランプにおいて、上記ＬＥＤチッ
プと組み合わされた発光材料が一般式（Ｌａ1-x-y Ｅｕ
x Ｓｍy ）2 Ｏ2 Ｓ（但し、０．０１≦ｘ≦０．１５，
０．０００１≦ｙ≦０．０３）で表わされるユーロピウ
ム・サマリウム付活酸硫化ランタン蛍光体であることを
特徴とする。Further, an LED lamp according to the present invention is a light emitting diode (LED) lamp that converts electric energy into visible light or infrared light by energizing an LED chip combined with a light emitting material. The combined luminescent material has the general formula (La 1-xy Eu)
x Sm y) 2 O 2 S ( where, 0.01 ≦ x ≦ 0.15,
It is characterized by being a europium-samarium-activated lanthanum oxysulfide phosphor represented by 0.0001 ≦ y ≦ 0.03).
【００１５】ここで、上記Ｅｕ（ユーロピウム）は蛍光
体の発光効率を高める活性体（付活剤）として作用し、
Ｌａ（ランタン）に対して原子比ｘで０．０１〜０．１
５の割合で添加される。添加割合が０．０１未満では輝
度が著しく低下し発光効率の改善効果が少ない。一方、
添加割合が０．１５を超えると、着色を生じ易くなり、
濃度消光のため輝度が著しく低下し蛍光体の発光効率を
却って阻害することになる。より好ましいＥｕの原子比
ｘは０．０３〜０．０８の範囲である。Here, Eu (Europium) acts as an activator (activator) for increasing the luminous efficiency of the phosphor,
Atomic ratio x with respect to La (lanthanum) is 0.01 to 0.1.
5 are added. If the addition ratio is less than 0.01, the luminance is significantly reduced and the effect of improving the luminous efficiency is small. on the other hand,
When the addition ratio exceeds 0.15, coloring is likely to occur,
Due to the concentration quenching, the luminance is remarkably reduced, and the luminous efficiency of the phosphor is rather hindered. A more preferable atomic ratio x of Eu is in the range of 0.03 to 0.08.
【００１６】また、Ｓｍ（サマリウム）は付活剤として
作用する他に、蛍光体の励起スペクトル波長を長波長側
にシフトする作用を有し、Ｌａ（ランタン）に対して、
０．０００１〜０．０３の割合で添加される。添加割合
が０．０００１未満では上記シフト効果が不十分である
一方、添加割合が０．０３を超えると、同様に蛍光体の
発光効率を却って阻害する。より好ましいＳｍの原子比
ｙは０．００１〜０．０１の範囲である。Sm (samarium), in addition to acting as an activator, has the effect of shifting the excitation spectrum wavelength of the phosphor to longer wavelengths.
It is added at a ratio of 0.0001 to 0.03. When the addition ratio is less than 0.0001, the shift effect is insufficient, while when the addition ratio exceeds 0.03, the luminous efficiency of the phosphor is similarly inhibited. The more preferable atomic ratio y of Sm is in the range of 0.001 to 0.01.
【００１７】上記組成範囲の赤色発光蛍光体は、励起ス
ペクトル分布におけるピーク波長が３６０〜３８０nmの
紫外線波長領域に存在することになり、ＬＥＤランプの
励起用紫外線によって効率的に赤色光を放射する。The red light-emitting phosphor having the above composition range has a peak wavelength in the excitation spectrum distribution in the ultraviolet wavelength region of 360 to 380 nm, and efficiently emits red light by the ultraviolet light for excitation of the LED lamp.
【００１８】また、Ｌａと一部置換して用いられるイッ
トリウム（Ｙ）およびガドリニウム（Ｇｄ）は、蛍光体
中に固溶することにより、赤色領域における発光エネル
ギーを高める効果を有し、Ｌａとの置換量は３０ mol％
以下とされる。置換量が３０mol％を超えるように過大
になると、結晶の歪みが無視できなくなり、発光強度が
不十分となるためである。より好ましい置換量は、５〜
２０ mol％の範囲である。In addition, yttrium (Y) and gadolinium (Gd) used as a partial replacement of La have the effect of increasing the emission energy in the red region by forming a solid solution in the phosphor. Replacement amount is 30 mol%
It is as follows. If the substitution amount exceeds 30 mol%, the crystal distortion cannot be ignored, and the emission intensity becomes insufficient. More preferred substitution amounts are 5 to
It is in the range of 20 mol%.
【００１９】本発明に係る赤色発光蛍光体は、例えば以
下の工程を経て製造される。すなわち、一般式（Ｌａ
1-x-y Ｅｕx Ｓｍy ）2 Ｏ2 Ｓ（但し、０．０１≦ｘ≦
０．１５，０．０００１≦ｙ≦０．０３）で表わされる
組成を有するようにＬａ2 Ｏ3，Ｅｕ2 Ｏ3 ，Ｓｍ2 Ｏ
3 ，Ｓなどの各原料粉末をＮａ2 ＣＯ3 やＬｉ3 ＰＯ4
などの融剤と均一に配合した後にボールミル等て十分に
混合して原料混合体を調製する工程と、得られた原料混
合体を、蓋付きのアルミナ坩堝等の焼成容器に収容して
大気中で１１００〜１４００℃の温度で３〜６時間焼成
する工程と、得られた焼成物を純水にて洗浄して不要な
可溶成分を除去する工程と、さらに焼成物をｐＨ２以上
の酸性液中で酸洗浄する工程と、酸洗浄した焼成物を純
水にて３〜５回洗浄後、濾過・乾燥する工程とを経て製
造される。The red light emitting phosphor according to the present invention is manufactured, for example, through the following steps. That is, the general formula (La
1-xy Eu x Sm y) 2 O 2 S ( where, 0.01 ≦ x ≦
0.15, 0.0001 ≦ y ≦ 0.03) so that La 2 O 3 , Eu 2 O 3 , Sm 2 O
3 and S are mixed with Na 2 CO 3 or Li 3 PO 4
A step of preparing a raw material mixture by mixing the mixture uniformly with a flux such as a ball mill or the like, and placing the obtained raw material mixture in a firing container such as an alumina crucible with a lid and placing it in the atmosphere. Baking at a temperature of 1100 ° C. to 1400 ° C. for 3 to 6 hours, a step of washing the obtained baking material with pure water to remove unnecessary soluble components, and furthermore, baking the baking product with an acidic liquid having a pH of 2 or more. The acid-washed baked product is washed with pure water three to five times, and then filtered and dried.
【００２０】ここで上記製造方法の酸洗浄工程におい
て、特に蛍光体粒子分散液をｐＨ２以上の酸性領域に維
持しながら洗浄することにより、蛍光体粒子中に混入し
た非発光成分を高い効率で除去できるとともに、蛍光体
粒子の製品歩留りを９０％以上に高めることができるな
ど、実用上顕著な効果が発揮される。なお、非発光成分
の除去効果と製品歩留りとを共に高くするためには、上
記酸洗浄時のｐＨは、２〜４の範囲に保持することが、
より好ましい。Here, in the acid washing step of the above-mentioned production method, non-light-emitting components mixed in the phosphor particles are removed with high efficiency, particularly by washing while maintaining the phosphor particle dispersion in an acidic region of pH 2 or more. In addition to the above, the product yield of the phosphor particles can be increased to 90% or more, so that practically remarkable effects are exhibited. In order to increase both the effect of removing non-light emitting components and the product yield, the pH at the time of the acid washing is preferably maintained in the range of 2 to 4.
More preferred.
【００２１】さらに、本発明に係るＬＥＤランプは、発
光材料と組み合わされたＬＥＤチップに通電すことによ
り電気エネルギーを可視光または赤外光に変換する発光
ダイオード（ＬＥＤ）ランプにおいて、上記ＬＥＤラン
プと組み合わされた発光材料が一般式（Ｌａ1-x-y Ｅｕ
x Ｓｍy ）2 Ｏ2 Ｓ（但し、０．０１≦ｘ≦０．１５，
０．０００１≦ｙ≦０．０３）で表わされるユーロピウ
ム・サマリウム付活酸硫化ランタン蛍光体であることを
特徴とする。Further, an LED lamp according to the present invention is a light emitting diode (LED) lamp that converts electric energy into visible light or infrared light by energizing an LED chip combined with a light emitting material. The combined luminescent material has the general formula (La 1-xy Eu)
x Sm y) 2 O 2 S ( where, 0.01 ≦ x ≦ 0.15,
It is characterized by being a europium-samarium-activated lanthanum oxysulfide phosphor represented by 0.0001 ≦ y ≦ 0.03).
【００２２】上記発光ダイオードランプを構成するＬＥ
Ｄチップは、特に限定されるものではないが、一般的に
ＩｎＧａＮ系材料，ＧａＰ系材料，ＧａＡｓＰ系材料，
ＧａＡｌＡｓ系材料等から成るチップが使用される。LE constituting the light emitting diode lamp
The D chip is not particularly limited, but generally includes an InGaN-based material, a GaP-based material, a GaAsP-based material,
A chip made of a GaAlAs-based material or the like is used.
【００２３】上記ＬＥＤランプによれば、ＬＥＤの励起
源となる紫外線波長領域において励起スペトクトルの高
いピークを有する赤色発光蛍光体を含有しているため、
赤色領域における発光輝度を大幅に高めることができ
る。According to the above-described LED lamp, since the LED lamp contains a red light-emitting phosphor having a high excitation spectrum peak in an ultraviolet wavelength region serving as an LED excitation source,
The emission luminance in the red region can be greatly increased.
【００２４】上記構成に係る赤色発光蛍光体によれば、
所定量のＳｍを添加して励起スペクトル波長をＬＥＤ励
起紫外線波長側にシフトしているため、波長３７０nm前
後の励起紫外線を効率よく吸収し赤色光に変換でき、赤
色領域における発光輝度を大幅に高めることができる。According to the red light emitting phosphor having the above structure,
Since the excitation spectrum wavelength is shifted to the LED excitation ultraviolet wavelength side by adding a predetermined amount of Sm, the excitation ultraviolet light having a wavelength of about 370 nm can be efficiently absorbed and converted into red light, and the emission luminance in the red region is greatly increased. be able to.
【００２５】また、赤色発光蛍光体と、他の青色，緑色
発光蛍光体との組合せを適正に選択することにより、任
意の色温度を有する白色光のみならず、紫色，桃色，青
緑色などの中間色をも高い精度で取り出すことが可能な
ＬＥＤランプを実現でき、優れた実用上の効果が得られ
る。Also, by appropriately selecting a combination of a red light emitting phosphor and another blue or green light emitting phosphor, not only white light having an arbitrary color temperature but also purple, pink, and blue-green can be obtained. An LED lamp capable of extracting intermediate colors with high accuracy can be realized, and excellent practical effects can be obtained.
【００２６】[0026]
【発明の実施の形態】次に本発明に実施形態について以
下の実施例に基づいて、より具体的に説明する。BEST MODE FOR CARRYING OUT THE INVENTION Next, embodiments of the present invention will be described more specifically based on the following examples.
【００２７】実施例１ 蛍光体構成原料としてのＬａ2 Ｏ3 粉末を２２９．７ｇ
と、Ｅｕ2 Ｏ3 粉末を１６．０１ｇと、Ｓｍ2 Ｏ3 粉末
を２．６４ｇと、Ｓ粉末を６１．３８ｇと、融剤として
のＮａ2 ＣＯ3 粉末を８６．９４ｇと、Ｌｉ3 ＰＯ4 粉
末を２４．８４ｇとを正確に秤量し、ボールミルを使用
して均一に混合して原料混合体とした。 Example 1 229.7 g of La 2 O 3 powder as a constituent material of a phosphor
16.01 g of Eu 2 O 3 powder, 2.64 g of Sm 2 O 3 powder, 61.38 g of S powder, 86.94 g of Na 2 CO 3 powder as a flux, and Li 3 PO 24.84 g of the 4 powders were accurately weighed and uniformly mixed using a ball mill to obtain a raw material mixture.
【００２８】次に、得られた原料混合体を、蓋付きのア
ルミナ坩堝内に収容して１２５０℃の温度で４時間焼成
した。得られた焼成物を純水にて十分に洗浄することに
より、不要な可溶成分を除去した。その後、ボールミル
により焼成物を細かく粉砕して蛍光体粒子とし、さらに
硫酸および硝酸を添加してｐＨ値が２．５の酸性領域に
維持しながら酸洗浄を行った後に、純水にて４回洗浄し
た。そして洗浄した蛍光体粒子を濾過・乾燥することに
より、（Ｌａ0.93Ｅｕ0.06Ｓｍ0.01）2 Ｏ2 Ｓなる組成
を有する実施例１に係る赤色発光蛍光体を調製した。Next, the obtained raw material mixture was accommodated in an alumina crucible with a lid and fired at a temperature of 1250 ° C. for 4 hours. Unnecessary soluble components were removed by sufficiently washing the obtained fired product with pure water. Thereafter, the fired product is finely pulverized by a ball mill into phosphor particles, and acid washing is performed while adding sulfuric acid and nitric acid to maintain the pH value in an acidic region of 2.5, and then four times with pure water. Washed. The washed phosphor particles were filtered and dried to prepare a red light-emitting phosphor according to Example 1 having a composition of (La 0.93 Eu 0.06 Sm 0.01 ) 2 O 2 S.
【００２９】得られた赤色発光蛍光体の励起スペクトル
分布を図１に示す一方、発光スペクトル分布を図２に示
す。図１から明らかなように、実施例１に係る蛍光体
は、波長３３０〜４００nmの紫外線により高い効率で赤
色を発光する。また、図２から明らかなように、実施例
１に係る蛍光体は、３８０nmの紫外線励起を行った場
合、波長６２５nm付近において発光のピークを有する赤
色発光蛍光体である。FIG. 1 shows the excitation spectrum distribution of the obtained red light-emitting phosphor, and FIG. 2 shows the emission spectrum distribution. As is clear from FIG. 1, the phosphor according to Example 1 emits red light with high efficiency by ultraviolet light having a wavelength of 330 to 400 nm. Further, as is apparent from FIG. 2, the phosphor according to Example 1 is a red light-emitting phosphor having an emission peak near a wavelength of 625 nm when ultraviolet light of 380 nm is excited.
【００３０】さらに、上記実施例１に係る赤色発光蛍光
体について、３８０nm励起下において従来の（Ｙ0.955
Ｅｕ0.045 ）2 Ｏ2 Ｓ蛍光体を標準にして輝度を測定し
たところ、１８０％という高い値が得られた。したがっ
て、本実施例に係る蛍光体の励起スペクトル分布は発光
ダイオード（ＬＥＤ）の放射エネルギーを効率良く赤色
光に変換できることが判明した。Further, with respect to the red light-emitting phosphor according to Example 1, the conventional (Y 0.955) was excited under the excitation of 380 nm.
When the luminance was measured using the Eu 0.045 ) 2 O 2 S phosphor as a standard, a high value of 180% was obtained. Therefore, it was found that the excitation spectrum distribution of the phosphor according to the present example can efficiently convert the radiant energy of the light emitting diode (LED) into red light.
【００３１】実施例２ 蛍光体構成原料としてのＬａ2 Ｏ3 粉末を２９１．５ｇ
と、Ｅｕ2 Ｏ3 粉末を２０．１４ｇと、Ｓｍ2 Ｏ3 粉末
を０．６７ｇと、Ｓ粉末を７７．１７ｇと、融剤として
のＮａ2 ＣＯ3 粉末を１０９．３ｇと、Ｋ3 ＰＯ4 粉末
を３１．２３ｇとを正確に秤量し、ボールミルを使用し
て均一に混合して原料混合体とした。 Example 2 291.5 g of La 2 O 3 powder as a constituent material of a phosphor
20.14 g of Eu 2 O 3 powder, 0.67 g of Sm 2 O 3 powder, 77.17 g of S powder, 109.3 g of Na 2 CO 3 powder as a flux, and K 3 PO 4 Powders were accurately weighed to 31.23 g and uniformly mixed using a ball mill to obtain a raw material mixture.
【００３２】次に、得られた原料混合体を、蓋付きのア
ルミナ坩堝内に収容して１１５０℃の温度で５時間焼成
した。得られた焼成物を純水にて十分に洗浄することに
より、不要な可溶成分を除去した。その後、ボールミル
により焼成物を細かく粉砕して蛍光体粒子とし、さらに
硫酸および硝酸を添加してｐＨ値が２．５の酸性領域に
維持しながら酸洗浄を行った後に、純水にて４回洗浄し
た。そして洗浄した蛍光体粒子を濾過・乾燥することに
より、（Ｌａ0.938 Ｅｕ0.060 Ｓｍ0.002 ）2Ｏ2 Ｓな
る組成を有する実施例２に係る赤色発光蛍光体を調製し
た。Next, the obtained raw material mixture was accommodated in an alumina crucible with a lid and fired at a temperature of 1150 ° C. for 5 hours. Unnecessary soluble components were removed by sufficiently washing the obtained fired product with pure water. After that, the fired product is finely pulverized by a ball mill into phosphor particles, and further, sulfuric acid and nitric acid are added thereto to perform acid washing while maintaining the pH value in an acidic region of 2.5, and then four times with pure water. Washed. Then, the washed phosphor particles were filtered and dried to prepare a red light emitting phosphor according to Example 2 having a composition of (La 0.938 Eu 0.060 Sm 0.002 ) 2 O 2 S.
【００３３】この実施例２に係る赤色発光蛍光体の輝度
を、実施例１と同様な方法で測定したところ、１８５％
という高い輝度が得られた。また、実施例２に係る蛍光
体の励起スペクトル分布および発光スペクトル分布は、
実施例１と基本的に同一形状であった。以上の結果か
ら、実施例２に係る赤色発光蛍光体についても、発光ダ
イオード（ＬＥＤ）の放射エネルギーを効率良く赤色光
に変換できることが判明した。The luminance of the red light-emitting phosphor according to the second embodiment was measured by the same method as in the first embodiment.
High brightness was obtained. Further, the excitation spectrum distribution and the emission spectrum distribution of the phosphor according to Example 2 are as follows:
The shape was basically the same as in Example 1. From the above results, it was found that the red light-emitting phosphor according to Example 2 could efficiently convert the radiant energy of the light emitting diode (LED) to red light.
【００３４】実施例３〜１１および比較例１〜４ 蛍光体組成が最終的に表１に示す組成となるように各蛍
光体原料粉末を秤量し、実施例１と同様な処理条件で焼
成，純水洗浄，粉砕した後に、表１に示すｐＨ値の酸性
領域に維持しながら酸洗浄を行い、さらに実施例１と同
一条件の純水洗浄，濾過，乾燥処理を実施することによ
り、実施例３〜１１および比較例１〜４に係る赤色発光
蛍光体をそれぞれ調製した。 Examples 3 to 11 and Comparative Examples 1 to 4 Each phosphor raw material powder was weighed so that the phosphor composition finally became the composition shown in Table 1, and was baked under the same processing conditions as in Example 1. After washing with pure water and pulverizing, acid washing is performed while maintaining the pH in the acidic region shown in Table 1, and further, washing with pure water, filtration and drying under the same conditions as in Example 1 are performed. Red light emitting phosphors according to 3 to 11 and Comparative Examples 1 to 4 were prepared, respectively.
【００３５】なお、比較例１はＳｍを含有しない従来の
ユーロピウム付活酸硫化イットリウム蛍光体であり、比
較例２はＳｍを過剰に含有する蛍光体であり、比較例３
はＳｍ含有量が過少である蛍光体であり、比較例４はＧ
ｄを過量に含有する蛍光体である。Comparative Example 1 is a conventional europium-activated yttrium oxysulfide phosphor containing no Sm, Comparative Example 2 is a phosphor containing excess Sm, and Comparative Example 3
Is a phosphor having an insufficient Sm content, and Comparative Example 4
This is a phosphor containing d in an excessive amount.
【００３６】こうして調製した各実施例および比較例に
係る赤色発光蛍光体について、波長３８０nmの励起紫外
線を照射してその輝度を測定した。なお、各蛍光体の輝
度は、比較例１に係る蛍光体の輝度を基準値（１００
％）として相対的に示した。測定結果を下記表１に示
す。The red light-emitting phosphors according to each of the examples and comparative examples thus prepared were irradiated with excitation ultraviolet light having a wavelength of 380 nm to measure the luminance. Note that the luminance of each phosphor is based on the luminance of the phosphor according to Comparative Example 1 as a reference value (100
%). The measurement results are shown in Table 1 below.
【００３７】[0037]
【表１】 [Table 1]
【００３８】上記表１に示す結果から明らかなように、
所定量のＳｍを添加した各実施例に係る赤色発光蛍光体
は、波長３８０nmの励起光（紫外線）を効率良く吸収し
赤色光に変換するため、比較例１〜４に示す従来組成を
有する蛍光体と比較して、赤色領域の発光輝度を大幅に
高められることが判明した。As is clear from the results shown in Table 1 above,
The red light-emitting phosphor according to each of the examples, to which a predetermined amount of Sm is added, efficiently absorbs excitation light (ultraviolet light) having a wavelength of 380 nm and converts it into red light. It has been found that the emission luminance in the red region can be significantly increased as compared with the body.
【００３９】また、各実施例に係る赤色発光蛍光体と、
他の青色，緑色発光蛍光体とを適正に組み合せることに
より、任意の色温度を有する白色光のみならず、紫色，
桃色，青緑色などの中間色をも高精度で取り出すことが
可能になった。Further, the red light emitting phosphor according to each of the embodiments,
By properly combining with other blue and green light emitting phosphors, not only white light having an arbitrary color temperature but also purple,
Intermediate colors such as pink and blue-green can be extracted with high precision.
【００４０】次に、蛍光体粒子を酸洗浄する際に、ｐＨ
条件が蛍光体の製品歩留りおよび不純物の除去効率に及
ぼす影響について、下記実施例１２に基づいて説明す
る。Next, when the phosphor particles are washed with an acid,
The influence of the conditions on the product yield of the phosphor and the efficiency of removing impurities will be described based on Example 12 below.
【００４１】実施例１２ 実施例１に係る赤色発光蛍光体の製造方法において、蛍
光体粒子を酸洗浄する工程における分散液のｐＨ値を、
表２に示すように、強酸領域（＜ｐＨ０．８），ｐＨ
１，ｐＨ２，ｐＨ４，ｐＨ６に維持しながら酸洗浄を実
施した場合における蛍光体粒子の製品歩留りと非発光成
分の除去効果を測定して下記表２に示す結果を得た。 Example 12 In the method for producing a red light-emitting phosphor according to Example 1, the pH value of the dispersion in the step of washing the phosphor particles with an acid was determined as follows.
As shown in Table 2, strong acid region (<pH 0.8), pH
The product yield of the phosphor particles and the effect of removing non-light-emitting components when acid cleaning was performed while maintaining the pH at 1, 2, 4 and 6 were measured, and the results shown in Table 2 below were obtained.
【００４２】[0042]
【表２】 [Table 2]
【００４３】上記表２に示す結果から明らかなように、
強酸領域およびｐＨ１の酸性条件下で酸洗浄を実施した
場合には、非発光成分の溶出による除去効果は高いが、
蛍光体粒子自体の溶出量も大きくなり製品歩留りが６０
〜７０％と低い値になった。一方、ｐＨ６の弱酸性領域
で酸洗浄を実施しても、非発光成分の除去効果はほとん
ど得られなかった。As is clear from the results shown in Table 2 above,
When acid washing is performed under a strong acid region and acidic conditions of pH 1, the removal effect by elution of non-luminescent components is high,
The elution amount of the phosphor particles themselves is also increased, and the product yield is 60
The value was as low as ~ 70%. On the other hand, even when the acid washing was performed in the weakly acidic region at pH 6, the effect of removing the non-light emitting component was hardly obtained.
【００４４】そしてｐＨ２〜４で酸洗浄を実施した場合
には、非発光成分の除去効果および製品歩留りが共に適
度であった。したがって、酸洗浄時のｐＨ値は２以上の
酸性領域に維持することが蛍光体の純度および製造コス
トを適正にする上で実用上非常に好ましいことが判明し
た。When the acid washing was carried out at pH 2 to 4, both the effect of removing non-light emitting components and the product yield were appropriate. Accordingly, it has been found that maintaining the pH value during acid washing in an acidic region of 2 or more is practically very preferable in order to optimize the purity and production cost of the phosphor.
【００４５】[0045]
【発明の効果】以上説明の通り本発明に係る赤色発光蛍
光体によれば、所定量のＳｍを添加して励起スペクトル
波長をＬＥＤ励起紫外線波長側にシフトしているため、
波長３７０nm前後の励起紫外線を効率よく吸収し赤色光
に変換でき、赤色領域における発光輝度を大幅に高める
ことができる。As described above, according to the red light emitting phosphor of the present invention, the excitation spectrum wavelength is shifted to the LED excitation ultraviolet wavelength side by adding a predetermined amount of Sm.
Excitation ultraviolet light having a wavelength of about 370 nm can be efficiently absorbed and converted into red light, and the emission luminance in the red region can be greatly increased.
【００４６】また、赤色発光蛍光体と、他の青色，緑色
発光蛍光体との組合せを適正に選択することにより、任
意の色温度を有する白色光のみならず、紫色，桃色，青
緑色などの中間色をも高い精度で取り出すことが可能な
ＬＥＤランプを実現でき、優れた実用上の効果が得られ
る。By properly selecting a combination of a red light-emitting phosphor and another blue or green light-emitting phosphor, not only white light having an arbitrary color temperature but also purple, pink, and blue-green can be obtained. An LED lamp capable of extracting intermediate colors with high accuracy can be realized, and excellent practical effects can be obtained.
【図１】本発明に係る赤色発光蛍光体の一実施例の励起
スペクトル分布を示すグラフ。FIG. 1 is a graph showing an excitation spectrum distribution of one embodiment of a red light emitting phosphor according to the present invention.
【図２】本発明に係る赤色発光蛍光体の一実施例の発光
スペクトル分布を示すグラフ。FIG. 2 is a graph showing an emission spectrum distribution of one example of a red light emitting phosphor according to the present invention.
Claims (8)
2 Ｓ（但し、０．０１≦ｘ≦０．１５，０．０００１≦
ｙ≦０．０３）で表わされるユーロピウム・サマリウム
付活酸硫化ランタン蛍光体から成ることを特徴とする赤
色発光蛍光体。1. A general formula (La 1-xy Eu x Sm y) 2 O
2 S (however, 0.01 ≦ x ≦ 0.15, 0.0001 ≦
A red-emitting phosphor comprising a europium-samarium-activated lanthanum oxysulfide phosphor represented by the following formula: y ≦ 0.03).
が、３６０〜３８０nmの紫外線波長領域に存在すること
を特徴とする請求項１記載の赤色発光蛍光体。2. The red light-emitting phosphor according to claim 1, wherein a peak wavelength in an excitation spectrum distribution is in an ultraviolet wavelength region of 360 to 380 nm.
原子比（ｘ）が０．０３〜０．０８の範囲であることを
特徴とする請求項１記載の赤色発光蛍光体。3. The red light-emitting phosphor according to claim 1, wherein the atomic ratio (x) of europium (Eu) in the general formula is in the range of 0.03 to 0.08.
子比（ｙ）が０．００１〜０．０１の範囲であることを
特徴とする請求項１記載の赤色発光蛍光体。4. The red light-emitting phosphor according to claim 1, wherein the atomic ratio (y) of samarium (Sm) in the general formula is in the range of 0.001 to 0.01.
の少なくとも一方の元素で置換したことを特徴とする請
求項１記載の赤色発光蛍光体。5. The method according to claim 5, wherein not more than 30 mol% of La is Y and Gd.
2. The red light-emitting phosphor according to claim 1, wherein said phosphor is substituted by at least one of the following elements.
一方の元素の置換量が５〜２０ mol％であることを特徴
とする請求項１記載の赤色発光蛍光体。6. The red light-emitting phosphor according to claim 1, wherein the substitution amount of at least one element of Y and Gd with respect to La is 5 to 20 mol%.
2 Ｓ（但し、０．０１≦ｘ≦０．１５，０．０００１≦
ｙ≦０．０３）で表わされる組成を有するように各原料
粉末を均一に配合して原料混合体を調製する工程と、得
られた原料混合体を焼成する工程と、得られた焼成物を
純水にて洗浄して不要な可溶成分を除去する工程と、さ
らに焼成物をｐＨ２以上の酸性液中で酸洗浄する工程
と、酸洗浄した焼成物を純水にて洗浄後、濾過・乾燥す
る工程とを備えることを特徴とする赤色発光蛍光体の製
造方法。7. A general formula (La 1-xy Eu x Sm y) 2 O
2 S (however, 0.01 ≦ x ≦ 0.15, 0.0001 ≦
y ≦ 0.03), a step of uniformly blending the respective raw material powders so as to have a composition represented by: y, a step of preparing a raw material mixture, a step of firing the obtained raw material mixture, and a step of firing the obtained fired product. A step of removing unnecessary soluble components by washing with pure water, a step of further acid-washing the calcined product in an acid solution having a pH of 2 or more, a step of washing the acid-cleaned calcined product with pure water, filtration, Drying the red light-emitting phosphor.
に通電することにより電気エネルギーを可視光または赤
外光に変換する発光ダイオード（ＬＥＤ）ランプにおい
て、上記ＬＥＤチップと組み合わされた発光材料が一般
式（Ｌａ1-x- y Ｅｕx Ｓｍy ）2 Ｏ2 Ｓ（但し、０．０
１≦ｘ≦０．１５，０．０００１≦ｙ≦０．０３）で表
わされるユーロピウム・サマリウム付活酸硫化ランタン
蛍光体であることを特徴とするＬＥＤランプ。8. A light emitting diode (LED) lamp that converts electric energy into visible light or infrared light by energizing an LED chip combined with a light emitting material, wherein the light emitting material combined with the LED chip has a general formula (La 1-x- y Eu x Sm y) 2 O 2 S ( however, 0.0
An LED lamp comprising a europium-samarium-activated lanthanum oxysulfide phosphor represented by the following formula: 1 ≦ x ≦ 0.15, 0.0001 ≦ y ≦ 0.03).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04827598A JP3950543B2 (en) | 1998-02-27 | 1998-02-27 | LED lamp |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP04827598A JP3950543B2 (en) | 1998-02-27 | 1998-02-27 | LED lamp |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005030861A Division JP4322824B2 (en) | 2005-02-07 | 2005-02-07 | Method for producing red-emitting phosphor |
| JP2005254040A Division JP4188350B2 (en) | 2005-09-01 | 2005-09-01 | Semiconductor diode and display device using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11246857A true JPH11246857A (en) | 1999-09-14 |
| JP3950543B2 JP3950543B2 (en) | 2007-08-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP04827598A Expired - Lifetime JP3950543B2 (en) | 1998-02-27 | 1998-02-27 | LED lamp |
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| Country | Link |
|---|---|
| JP (1) | JP3950543B2 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005067068A1 (en) * | 2004-01-02 | 2005-07-21 | Mediana Electronics Co., Ltd. | White led device comprising dual-mold and manufacturing method for the same |
| KR100512600B1 (en) * | 2003-06-23 | 2005-09-07 | 럭스피아 주식회사 | Red phosphor comprising samarium for light emitted diode |
| JP2005255885A (en) * | 2004-03-12 | 2005-09-22 | National Institute For Materials Science | Phosphor and its manufacturing method |
| US6982523B2 (en) | 2003-01-28 | 2006-01-03 | Kabushiki Kaisha Fine Rubber Kenkyuusho | Red light emitting phosphor, its production and light emitting device |
| WO2007037120A1 (en) * | 2005-09-29 | 2007-04-05 | Kabushiki Kaisha Toshiba | White light-emitting led lamp, backlight using same, and liquid crystal display |
| US7294956B2 (en) | 2001-10-01 | 2007-11-13 | Matsushita Electric Industrial Co., Ltd. | Semiconductor light emitting element and light emitting device using this |
| KR100853314B1 (en) * | 1999-09-27 | 2008-08-20 | 필립스 루미리즈 라이팅 캄파니 엘엘씨 | Tri-color, white light led lamps |
| US7646141B2 (en) | 2004-10-18 | 2010-01-12 | Lg Innotek Co., Ltd. | Phosphor, light emitting device by using the same and manufacturing method of the same |
| JP2010059429A (en) * | 2009-10-26 | 2010-03-18 | Mitsubishi Chemicals Corp | Phosphor, luminescent device using the same, image display and illuminating device |
| US20130010456A1 (en) * | 2008-02-25 | 2013-01-10 | Toshiba Materials Co., Ltd. | White led lamp, backlight, light emitting device, display device and illumination device |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100853314B1 (en) * | 1999-09-27 | 2008-08-20 | 필립스 루미리즈 라이팅 캄파니 엘엘씨 | Tri-color, white light led lamps |
| US7294956B2 (en) | 2001-10-01 | 2007-11-13 | Matsushita Electric Industrial Co., Ltd. | Semiconductor light emitting element and light emitting device using this |
| US6982523B2 (en) | 2003-01-28 | 2006-01-03 | Kabushiki Kaisha Fine Rubber Kenkyuusho | Red light emitting phosphor, its production and light emitting device |
| KR100512600B1 (en) * | 2003-06-23 | 2005-09-07 | 럭스피아 주식회사 | Red phosphor comprising samarium for light emitted diode |
| WO2005067068A1 (en) * | 2004-01-02 | 2005-07-21 | Mediana Electronics Co., Ltd. | White led device comprising dual-mold and manufacturing method for the same |
| JP2005255885A (en) * | 2004-03-12 | 2005-09-22 | National Institute For Materials Science | Phosphor and its manufacturing method |
| US7646141B2 (en) | 2004-10-18 | 2010-01-12 | Lg Innotek Co., Ltd. | Phosphor, light emitting device by using the same and manufacturing method of the same |
| JP5288792B2 (en) * | 2005-03-01 | 2013-09-11 | 株式会社東芝 | Light emitting device |
| WO2007037120A1 (en) * | 2005-09-29 | 2007-04-05 | Kabushiki Kaisha Toshiba | White light-emitting led lamp, backlight using same, and liquid crystal display |
| US7935975B2 (en) | 2005-09-29 | 2011-05-03 | Kabushiki Kaisha Toshiba | White LED lamp and backlight using the same, and liquid crystal display device using the backlight |
| US20130010456A1 (en) * | 2008-02-25 | 2013-01-10 | Toshiba Materials Co., Ltd. | White led lamp, backlight, light emitting device, display device and illumination device |
| US20150060926A1 (en) * | 2008-02-25 | 2015-03-05 | Kabushiki Kaisha Toshiba | White led lamp, backlight, light emitting device, display device and illumination device |
| US9039218B2 (en) * | 2008-02-25 | 2015-05-26 | Kabushiki Kaisha Toshiba | White LED lamp, backlight, light emitting device, display device and illumination device |
| US10886434B2 (en) * | 2008-02-25 | 2021-01-05 | Kabushiki Kaisha Toshiba | White LED lamp, backlight, light emitting device, display device and illumination device |
| JP2010059429A (en) * | 2009-10-26 | 2010-03-18 | Mitsubishi Chemicals Corp | Phosphor, luminescent device using the same, image display and illuminating device |
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|---|---|
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