JP2006237113A - White LED - Google Patents
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Abstract
【課題】
ＬＥＤおよび１種の蛍光体でも白色光を発することが可能な白色ＬＥＤを提供する。
【解決手段】
ＬＥＤと該ＬＥＤからの発光の少なくとも一部により励起され発光する蛍光体とを有する白色ＬＥＤにおいて、該蛍光体が式Ｍ1 2（Ｍ2 1-xＥｕx）Ｍ3Ｏ4（式中のＭ1はＬｉ、Ｎａ、Ｋ、ＲｂおよびＣｓからなる群より選ばれる１種以上の元素であり、Ｍ2はＣａ、Ｓｒ、Ｂａ、ＭｇおよびＺｎからなる群より選ばれる１種以上の元素であり、Ｍ3はＳｉおよび／またはＧｅであって、ｘは０を超え１以下の範囲である。）で表される化合物から実質的になることを特徴とする白色ＬＥＤ。
【選択図】 なし
【Task】
Provided is a white LED capable of emitting white light even with the LED and one kind of phosphor.
[Solution]
In a white LED having an LED and a phosphor that emits light by being excited by at least part of the light emitted from the LED, the phosphor has the formula M 1 2 (M 2 1−x Eu x ) M 3 O 4 (wherein M 1 is one or more elements selected from the group consisting of Li, Na, K, Rb and Cs, and M 2 is one or more elements selected from the group consisting of Ca, Sr, Ba, Mg and Zn. And M 3 is Si and / or Ge, and x is in the range of more than 0 and 1 or less).
[Selection figure] None
Description
本発明は、白色ＬＥＤに関するものである。 The present invention relates to a white LED.
白色ＬＥＤは、ＬＥＤと該ＬＥＤからの発光の少なくとも一部により励起され発光する蛍光体とを組み合わせることによってなり、白色光を発することができる。例えば、特許文献１には、ＬＥＤとしてのＩｎＧａＮチップと蛍光体としての（Ｂａ0.49Ｓｒ0.49）2ＳｉＯ4：Ｅｕ0.02およびＳｒ2Ｓｉ5Ｎ8：Ｅｕとを含む白色ＬＥＤが、具体的に開示されている。 The white LED is a combination of an LED and a phosphor that emits light by being excited by at least a part of light emitted from the LED, and can emit white light. For example, Patent Document 1 specifically discloses a white LED including an InGaN chip as an LED and (Ba 0.49 Sr 0.49 ) 2 SiO 4 : Eu 0.02 and Sr 2 Si 5 N 8 : Eu as phosphors. Has been.
本発明の目的は、ＬＥＤおよび１種の蛍光体でも白色光を発することが可能な白色ＬＥＤを提供することにある。 An object of the present invention is to provide a white LED capable of emitting white light even with an LED and one kind of phosphor.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、意外にもＬＥＤと蛍光体として下記式で示される特定の化合物とを用いることにより、十分な白色光を発する白色ＬＥＤを実現できることを見出し、さらに種々の検討を加え、本発明を完成するに至った。 As a result of intensive studies to solve the above-mentioned problems, the present inventors have unexpectedly realized a white LED that emits sufficient white light by using an LED and a specific compound represented by the following formula as a phosphor. As a result, the present invention has been completed.
すなわち本発明は、下記の白色ＬＥＤを提供するものである。
＜１＞ＬＥＤと該ＬＥＤからの発光の少なくとも一部により励起され発光する蛍光体とを有する白色ＬＥＤにおいて、該蛍光体が式Ｍ1 2（Ｍ2 1-xＥｕx）Ｍ3Ｏ4（式中のＭ1はＬｉ、Ｎａ、Ｋ、ＲｂおよびＣｓからなる群より選ばれる１種以上の元素であり、Ｍ2はＣａ、Ｓｒ、Ｂａ、ＭｇおよびＺｎからなる群より選ばれる１種以上の元素であり、Ｍ3はＳｉおよび／またはＧｅであって、ｘは０を超え１以下の範囲である。）で表される化合物から実質的になることを特徴とする白色ＬＥＤ。
＜２＞前記蛍光体が、さらに付活剤としてＳｃ、Ｙ、Ｌａ、Ｇｄ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、ＬｕおよびＢｉからなる群より選ばれる１種以上の元素を含有する前記の白色ＬＥＤ。
＜３＞前記蛍光体が、さらにＦ、Ｃｌ、ＢｒおよびＩからなる群より選ばれる１種以上の元素を蛍光体重量に対して３０ｐｐｍ以上１００００ｐｐｍ以下含有する前記いずれかに記載の白色ＬＥＤ。
＜４＞ＬＥＤが青色ＬＥＤである前記いずれかに記載の白色ＬＥＤ。
That is, the present invention provides the following white LED.
<1> In a white LED having an LED and a phosphor that emits light by being excited by at least a part of light emitted from the LED, the phosphor has the formula M 1 2 (M 2 1-x Eu x ) M 3 O 4 ( M 1 in the formula is one or more elements selected from the group consisting of Li, Na, K, Rb and Cs, and M 2 is one or more elements selected from the group consisting of Ca, Sr, Ba, Mg and Zn Wherein M 3 is Si and / or Ge, and x is in the range of more than 0 and 1 or less.)
<2> The phosphor is further selected from the group consisting of Sc, Y, La, Gd, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Bi as an activator. Said white LED containing 1 or more types of elements.
<3> The white LED according to any one of the above, wherein the phosphor further contains at least one element selected from the group consisting of F, Cl, Br, and I at 30 ppm to 10,000 ppm with respect to the weight of the phosphor.
<4> The white LED according to any one of the above, wherein the LED is a blue LED.
本発明によれば、従来と比べ、実質的に蛍光体１種のみでも十分な白色光を発することができる白色ＬＥＤを実現できるため、工業的に極めて重要である。 According to the present invention, compared with the prior art, a white LED capable of emitting sufficient white light can be realized with substantially only one type of phosphor, which is extremely important industrially.
本発明の白色ＬＥＤは、ＬＥＤと該ＬＥＤからの発光の少なくとも一部により励起され発光する蛍光体とを有するものであり、該蛍光体が式（１）で表される化合物から実質的になる。
Ｍ1 2（Ｍ2 1-xＥｕx）Ｍ3Ｏ4 （１）
式（１）中のＭ1はＬｉ、Ｎａ、Ｋ、ＲｂおよびＣｓからなる群より選ばれる１種以上の元素であり、Ｍ2はＣａ、Ｓｒ、Ｂａ、ＭｇおよびＺｎからなる群より選ばれる１種以上の元素であり、Ｍ3はＳｉおよび／またはＧｅであって、ｘは０を超え１以下の範囲である。
The white LED of the present invention has an LED and a phosphor that emits light by being excited by at least a part of light emitted from the LED, and the phosphor substantially consists of a compound represented by the formula (1). .
M 1 2 (M 2 1-x Eu x ) M 3 O 4 (1)
M 1 in the formula (1) is one or more elements selected from the group consisting of Li, Na, K, Rb and Cs, and M 2 is selected from the group consisting of Ca, Sr, Ba, Mg and Zn. It is one or more elements, M 3 is Si and / or Ge, and x is in the range of more than 0 and 1 or less.
ここでＭ1は、Ｌｉ、ＮａおよびＫからなる群より選ばれる１種以上の元素であることが好ましく、より好ましくはＬｉである。またＭ2は、ＣａおよびＳｒからなる１種以上の元素であることが好ましく、より好ましくはＣａおよびＳｒである。またＭ3は、Ｓｉであることが好ましい。Ｍ1、Ｍ2、Ｍ3を前記のような元素とすることで、本発明の白色ＬＥＤはより高い発光強度を示す。また、ここで、ｘは０．００１以上０．５以下の範囲が好ましく、より好ましくは０．０１以上０．３以下の範囲である。ｘを前記のような範囲とすることで、本発明の白色ＬＥＤはより高い発光強度を示す。 Here, M 1 is preferably one or more elements selected from the group consisting of Li, Na, and K, and more preferably Li. M 2 is preferably at least one element composed of Ca and Sr, and more preferably Ca and Sr. M 3 is preferably Si. By using M 1 , M 2 , and M 3 as described above, the white LED of the present invention exhibits higher emission intensity. Here, x is preferably in the range of 0.001 to 0.5, and more preferably in the range of 0.01 to 0.3. By setting x in the above range, the white LED of the present invention exhibits higher emission intensity.
また、前記の蛍光体は、Ｅｕ以外の付活剤を第２の付活剤として含有してもよい。Ｅｕ以外の付活剤としては、例えば、Ｓｃ、Ｙ、Ｌａ、Ｇｄ、Ｃｅ、Ｐｒ、Ｎｄ、Ｓｍ、Ｔｂ、Ｄｙ、Ｈｏ、Ｅｒ、Ｔｍ、Ｙｂ、ＬｕおよびＢｉからなる群より選ばれる１種以上の元素が挙げられる。 The phosphor may contain an activator other than Eu as the second activator. Examples of the activator other than Eu include one selected from the group consisting of Sc, Y, La, Gd, Ce, Pr, Nd, Sm, Tb, Dy, Ho, Er, Tm, Yb, Lu, and Bi. The above elements are mentioned.
さらに、前記の蛍光体が、Ｆ、Ｃｌ、ＢｒおよびＩからなる群より選ばれる１種以上の元素を蛍光体重量に対して３０ｐｐｍ以上１００００ｐｐｍ以下含有することが好ましく、より好ましくは５０ｐｐｍ以上１０００ｐｐｍ以下である。Ｆ、Ｃｌ、ＢｒおよびＩからなる群より選ばれる１種以上の元素を上記のように含有することで、本発明の白色ＬＥＤはより高い発光強度を示す。 Furthermore, it is preferable that the phosphor contains one or more elements selected from the group consisting of F, Cl, Br and I in an amount of 30 ppm to 10,000 ppm, more preferably 50 ppm to 1,000 ppm. It is. By including at least one element selected from the group consisting of F, Cl, Br and I as described above, the white LED of the present invention exhibits higher emission intensity.
また、前記の蛍光体は温度上昇に伴う発光強度の低下が少ないため、本発明の白色ＬＥＤも温度上昇に伴う発光強度の低下が少ない。 In addition, since the phosphor has a small decrease in emission intensity due to a temperature increase, the white LED of the present invention has a small decrease in emission intensity due to a temperature increase.
また、前記ＬＥＤとしては、波長が２００ｎｍ〜４１０ｎｍの範囲である光を発する紫外ＬＥＤ、波長が４１０ｎｍ〜５５０ｎｍの範囲である光を発する青色ＬＥＤ等が挙げられるが、青色ＬＥＤであることが好ましい。青色ＬＥＤを用いることで、本発明の白色ＬＥＤはより良好な白色を発することができる。 Examples of the LED include an ultraviolet LED that emits light having a wavelength in the range of 200 nm to 410 nm, a blue LED that emits light having a wavelength in the range of 410 nm to 550 nm, and the like, and is preferably a blue LED. By using the blue LED, the white LED of the present invention can emit a better white color.
次に、本発明の白色ＬＥＤの製造方法について説明する。 Next, the manufacturing method of white LED of this invention is demonstrated.
本発明の白色ＬＥＤを構成する蛍光体は、例えば次のようにして製造することができる。該蛍光体は、焼成により式（１）で表される化合物から実質的になる蛍光体となる金属化合物混合物を焼成することにより製造することができる。すなわち、対応する金属元素を含有する化合物を所定の組成となるように秤量し混合した後に得られた金属化合物混合物を焼成することにより製造することができる。例えば、好ましい化合物の一つである式Ｌｉ2（Ｓｒ0.98Ｅｕ0.02）ＳｉＯ4で表される化合物は、Ｌｉ2ＣＯ3、ＳｒＣＯ3、Ｅｕ2Ｏ3、ＳｉＯ2をＬｉ：Ｓｒ：Ｅｕ：Ｓｉのモル比は２．０：０．９８：０．０２：１．０となるように秤量し、混合した後に焼成することにより製造することができる。 The phosphor constituting the white LED of the present invention can be manufactured, for example, as follows. The phosphor can be produced by firing a metal compound mixture that becomes a phosphor substantially consisting of the compound represented by the formula (1) by firing. That is, it can be produced by firing a metal compound mixture obtained after weighing and mixing a compound containing a corresponding metal element to have a predetermined composition. For example, a compound represented by the formula Li 2 (Sr 0.98 Eu 0.02 ) SiO 4 , which is one of the preferred compounds, is Li 2 CO 3 , SrCO 3 , Eu 2 O 3 , SiO 2 and Li: Sr: Eu: Si. Can be manufactured by weighing the mixture so that the molar ratio is 2.0: 0.98: 0.02: 1.0, mixing, and firing.
前記の金属元素を含有する化合物としては、リチウム、ナトリウム、カリウム、ルビジウム、セシウム、カルシウム、ストロンチウム、バリウム、マグネシウム、亜鉛、ケイ素、ゲルマニウム、スカンジウム、イットリウム、ランタン、ガドリニウム、セリウム、プラセオジム、ネオジム、サマリウム、ユウロピウム、テルビウム、ジスプロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウム、マンガン、ビスマスの化合物で、例えば、酸化物を用いるか、または水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解および／または酸化して酸化物になりうるものを用いることができる。 Examples of the compound containing the metal element include lithium, sodium, potassium, rubidium, cesium, calcium, strontium, barium, magnesium, zinc, silicon, germanium, scandium, yttrium, lanthanum, gadolinium, cerium, praseodymium, neodymium, and samarium. , Europium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, manganese, bismuth compounds, for example, using oxides or high temperatures such as hydroxides, carbonates, nitrates, halides, oxalates, etc. Those that can be decomposed and / or oxidized into oxides can be used.
前記金属元素を含有する化合物の混合には、例えばボールミル、Ｖ型混合機、攪拌機等の通常工業的に用いられている装置を用いることができる。また、湿式混合、乾式混合のいずれによってもよい。 For the mixing of the compound containing the metal element, for example, a generally industrially used apparatus such as a ball mill, a V-type mixer or a stirrer can be used. Also, either wet mixing or dry mixing may be used.
前記金属化合物混合物を、例えば７００℃〜１６００℃の温度範囲にて１〜１００時間保持して焼成することにより本発明の白色ＬＥＤを構成する蛍光体が得られる。金属化合物混合物に水酸化物、炭酸塩、硝酸塩、ハロゲン化物、シュウ酸塩など高温で分解および／または酸化して酸化物になりうるものが含有されている場合、焼成の前に、金属化合物混合物を、例えば焼成温度よりも低い温度で保持して仮焼することにより、酸化物としたり、結晶水を除去することも可能である。また、仮焼後に粉砕を行うこともできる。 The phosphor constituting the white LED of the present invention is obtained by holding and firing the metal compound mixture in a temperature range of 700 ° C. to 1600 ° C. for 1 to 100 hours, for example. If the metal compound mixture contains hydroxides, carbonates, nitrates, halides, oxalates, etc. that can decompose and / or oxidize at high temperatures to form oxides, before firing, the metal compound mixture It is possible to obtain an oxide or remove crystal water by, for example, maintaining the material at a temperature lower than the firing temperature and calcining. Moreover, it can also grind | pulverize after calcination.
焼成時の雰囲気としては、窒素、アルゴン等の不活性ガス雰囲気や空気、酸素、酸素含有窒素、酸素含有アルゴン等の酸化性雰囲気、水素を０．１から１０体積％含有する水素含有窒素、水素を０．１から１０体積％含有する水素含有アルゴン等の還元性雰囲気等が挙げられる。また強い還元性の雰囲気で焼成する場合には適量の炭素を上記の金属化合物混合物に添加して焼成してもよい。また、得られる蛍光体の結晶性を高めるために、焼成または仮焼時に金属化合物混合物の中に適量の反応促進剤を存在させると蛍光体の発光強度が高まることがある。反応促進剤としては、例えば、ＬｉＦ、ＮａＦ、ＫＦ、ＬｉＣｌ、ＮａＣｌ、ＫＣｌ、Ｌｉ2ＣＯ3、Ｎａ2ＣＯ3、Ｋ2ＣＯ3、ＮａＨＣＯ3、ＮＨ4Ｃｌ、ＮＨ4Ｉなどを挙げることができる。 The atmosphere during firing is an inert gas atmosphere such as nitrogen or argon, an oxidizing atmosphere such as air, oxygen, oxygen-containing nitrogen, oxygen-containing argon, hydrogen-containing nitrogen containing 0.1 to 10% by volume of hydrogen, hydrogen And reducing atmospheres such as hydrogen-containing argon containing 0.1 to 10% by volume. When firing in a strong reducing atmosphere, an appropriate amount of carbon may be added to the metal compound mixture and fired. In addition, in order to increase the crystallinity of the obtained phosphor, the emission intensity of the phosphor may be increased if an appropriate amount of reaction accelerator is present in the metal compound mixture during firing or calcination. Examples of the reaction accelerator include LiF, NaF, KF, LiCl, NaCl, KCl, Li 2 CO 3 , Na 2 CO 3 , K 2 CO 3 , NaHCO 3 , NH 4 Cl, NH 4 I, and the like. it can.
以上の方法により得られた蛍光体を、例えばボールミルやジェットミル等を用いて粉砕することができる。また、洗浄、分級することができる。また、焼成を２回以上行うこともできる。 The phosphor obtained by the above method can be pulverized using, for example, a ball mill or a jet mill. It can also be washed and classified. Moreover, baking can also be performed twice or more.
また本発明の白色ＬＥＤを構成する青色ＬＥＤ、紫外ＬＥＤ等のＬＥＤは、上記の蛍光体を励起させ発光させるための光を発するものであるが、例えば、特開平６−１７７４２３号公報、特開平１１−１９１６３８号公報に開示されているような公知の技術により製造することができる。ＬＥＤは発光層としてＧａＮ、ＩｎiＧａ1-iＮ（０＜ｉ＜１）、ＩｎiＡｌjＧａ1-i-jＮ（０＜ｉ＜１、０＜ｊ＜１、ｉ＋ｊ＜１）等の層を有する半導体が用いられる。該発光層の組成を変化させることにより、発光波長を変化させることができる。 Further, LEDs such as a blue LED and an ultraviolet LED constituting the white LED of the present invention emit light for exciting and emitting the above phosphor. For example, Japanese Patent Laid-Open Nos. 6-177423 and It can be produced by a known technique as disclosed in Japanese Patent Application Laid-Open No. 11-191638. The LED has a light emitting layer such as GaN, In i Ga 1-i N (0 <i <1), In i Al j Ga 1-ij N (0 <i <1, 0 <j <1, i + j <1), etc. A semiconductor having a layer is used. The emission wavelength can be changed by changing the composition of the light emitting layer.
本発明の白色ＬＥＤは、上記の蛍光体およびＬＥＤを用いて、例えば、特開平５−１５２６０９号公報などに開示されているような公知の方法によって製造することができる。すなわち、上記の蛍光体をエポキシ樹脂、ポリカーボネート、シリコンゴムなどの透光性樹脂中に分散させ、その蛍光体を分散させた樹脂で、青色ＬＥＤを取り込むように成形することにより、本発明の白色ＬＥＤを製造することができる。 The white LED of the present invention can be manufactured by using a known method as disclosed in, for example, JP-A-5-152609, using the phosphor and the LED. That is, the above phosphor is dispersed in a light-transmitting resin such as epoxy resin, polycarbonate, silicon rubber, etc., and the white phosphor of the present invention is formed by taking in the blue LED with the resin in which the phosphor is dispersed. LEDs can be manufactured.
次に、本発明を実施例によりさらに詳しく説明するが、本発明はこれらの実施例に限定されるものではない。
なお、蛍光体の発光強度の測定は蛍光分光測定装置(ジョバンイボン社製ＳＰＥＸ Ｆｌｕｏｒｏｇ−３)を用いて行った。
EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.
Measurement of the emission intensity of the phosphor was performed using a fluorescence spectrometer (SPEX Fluorog-3 manufactured by Joban Yvon).
実施例１
炭酸リチウム（関東化学株式会社製、純度９９％）、炭酸ストロンチウム（堺化学工業株式会社製、純度９９％以上）、酸化ユウロピウム（信越化学工業株式会社製、純度９９．９９％）、二酸化珪素（日本アエロジル株式会社製：純度９９．９９％）の各原料をＬｉ：Ｓｒ：Ｅｕ：Ｓｉのモル比が２．０：０．９８：０．０２：１．０となるように秤量し、イソプロピルアルコールを用いた湿式ボールミルにより４時間混合してスラリーを得た。得られたスラリーをエバポレーターにより乾燥し、得られた金属化合物混合物を、大気雰囲気中において９００℃の温度で１２時間保持して焼成し、その後室温まで徐冷した。次いで、メノウ乳鉢により十分すり潰した後、２体積％Ｈ2含有Ｎ2雰囲気中で９００℃の温度で１２時間保持して焼成し、その後室温まで徐冷して、組成式がＬｉ2（Ｓｒ0.98Ｅｕ0.02）ＳｉＯ4で表される化合物からなる蛍光体１を得た。蛍光体１の塩素量は７ｐｐｍであった。
Example 1
Lithium carbonate (manufactured by Kanto Chemical Co., Inc., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), silicon dioxide ( Each material of Nippon Aerosil Co., Ltd. (purity: 99.99%) was weighed so that the molar ratio of Li: Sr: Eu: Si was 2.0: 0.98: 0.02: 1.0, and isopropyl The slurry was obtained by mixing for 4 hours by a wet ball mill using alcohol. The obtained slurry was dried by an evaporator, and the obtained metal compound mixture was baked by being held in an air atmosphere at a temperature of 900 ° C. for 12 hours, and then gradually cooled to room temperature. Next, after sufficiently ground in an agate mortar, the mixture is calcined by holding at a temperature of 900 ° C. for 12 hours in a N 2 atmosphere containing 2% by volume of H 2 , and then gradually cooled to room temperature, so that the composition formula is Li 2 (Sr 0.98 Eu 0.02 ) Phosphor 1 comprising a compound represented by SiO 4 was obtained. The amount of chlorine in phosphor 1 was 7 ppm.
蛍光体１に波長４６０ｎｍの光を照射して得られる発光強度で、室温（２５℃）の強度を１００とすると、５０℃では１００、７５℃で９８、１００℃で９８、１２０℃で９５であった。 The emission intensity obtained by irradiating the phosphor 1 with light having a wavelength of 460 nm. When the intensity at room temperature (25 ° C.) is 100, 100 at 50 ° C., 98 at 75 ° C., 98 at 100 ° C., 95 at 120 ° C. there were.
さらに、Ｉｎ0.3Ｇａ0.7Ｎからなる発光層を有する青色ＬＥＤを作製し、該青色ＬＥＤを取り込むように蛍光体１を塗布して作製した発光装置を発光させると、青色ＬＥＤからの光とそれにより蛍光体１が励起され発する光との混色によって白色光を発した。 Further, when a blue LED having a light emitting layer made of In 0.3 Ga 0.7 N is manufactured and the light emitting device manufactured by applying the phosphor 1 so as to incorporate the blue LED is caused to emit light, light from the blue LED and thereby White light was emitted by color mixing with the light emitted from the phosphor 1.
実施例２
炭酸リチウム（関東化学株式会社製、純度９９％）、炭酸ストロンチウム（堺化学工業株式会社製、純度９９％以上）、酸化ユウロピウム（信越化学工業株式会社製、純度９９．９９％）、二酸化珪素（日本アエロジル株式会社製：純度９９．９９％）、塩化アンモニウム（和光純薬工業株式会社製：純度９９％）の各原料をＬｉ：Ｓｒ：Ｅｕ：Ｓｉ：Ｃｌのモル比が２．０：０．９８：０．０２：１．０：０．０５となるように秤量し、イソプロピルアルコールを用いた湿式ボールミルにより４時間混合してスラリーを得た。得られたスラリーをエバポレーターにより乾燥後、得られた金属化合物混合物を、大気雰囲気中において９００℃の温度で１２時間保持して焼成し、その後室温まで徐冷した。次いで、メノウ乳鉢による粉砕後、２体積％Ｈ2含有Ｎ2雰囲気中で９００℃の温度で１２時間保持して焼成し、その後室温まで徐冷し、さらに純水で洗浄を行い、乾燥して、組成式がＬｉ2（Ｓｒ0.98Ｅｕ0.02）ＳｉＯ4で表される化合物からなる蛍光体２を得た。蛍光体２の塩素量は１００ｐｐｍであった。
Example 2
Lithium carbonate (manufactured by Kanto Chemical Co., Inc., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), europium oxide (manufactured by Shin-Etsu Chemical Co., Ltd., purity 99.99%), silicon dioxide ( Nippon Aerosil Co., Ltd .: Purity 99.99%) and ammonium chloride (Wako Pure Chemical Industries, Ltd .: Purity 99%) raw materials have a molar ratio of Li: Sr: Eu: Si: Cl of 2.0: 0. .98: 0.02: 1.0: 0.05 and weighed for 4 hours with a wet ball mill using isopropyl alcohol to obtain a slurry. The obtained slurry was dried by an evaporator, and the obtained metal compound mixture was baked by being held in an air atmosphere at a temperature of 900 ° C. for 12 hours, and then gradually cooled to room temperature. Next, after pulverization with an agate mortar, it is fired by holding at a temperature of 900 ° C. for 12 hours in an N 2 atmosphere containing 2% by volume of H 2 , then gradually cooled to room temperature, further washed with pure water, and dried. A phosphor 2 composed of a compound represented by the composition formula Li 2 (Sr 0.98 Eu 0.02 ) SiO 4 was obtained. The amount of chlorine in phosphor 2 was 100 ppm.
蛍光体２に波長４６０ｎｍの光を照射して得られる発光強度で、室温（２５℃）の強度を１００とすると、５０℃では１０１、７５℃で１００、１００℃で１００、１２０℃で９７であった。 The emission intensity obtained by irradiating the phosphor 2 with light having a wavelength of 460 nm. When the intensity at room temperature (25 ° C.) is 100, 101 at 50 ° C., 100 at 75 ° C., 100 at 100 ° C., 97 at 120 ° C. there were.
さらに、Ｉｎ0.3Ｇａ0.7Ｎからなる発光層を有する青色ＬＥＤを取り込むように蛍光体２を塗布して作製した発光装置を発光させると、青色ＬＥＤからの光とそれにより蛍光体２が励起され発する光との混色によって白色光を発した。 Further, when a light emitting device manufactured by applying the phosphor 2 so as to capture a blue LED having a light emitting layer made of In 0.3 Ga 0.7 N is caused to emit light, the phosphor 2 is excited and emitted by the light from the blue LED. White light was emitted by mixing with light.
実施例３
炭酸リチウム（関東化学株式会社製、純度９９％）、炭酸ストロンチウム（堺化学工業株式会社製、純度９９％以上）、炭酸カルシウム（宇部マテリアルズ株式会社製：純度９９．９％）、酸化ユウロピウム（信越化学工業株式会社製、純度９９．９９％）、二酸化珪素（日本アエロジル株式会社製：純度９９．９９％）、塩化アンモニウム（和光純薬工業株式会社製：純度９９％）の各原料をＬｉ：Ｓｒ：Ｃａ：Ｅｕ：Ｓｉ：Ｃｌのモル比が２．０：０．８８：０．１：０．０２：１．０：０．０５となるように秤量した以外は実施例２と同様の操作を行い、組成式がＬｉ2（Ｓｒ0.88Ｃａ0.1Ｅｕ0.02）ＳｉＯ4で表される化合物からなる蛍光体３を得た。蛍光体３の塩素量は１３０ｐｐｍであった。
Example 3
Lithium carbonate (manufactured by Kanto Chemical Co., Ltd., purity 99%), strontium carbonate (manufactured by Sakai Chemical Industry Co., Ltd., purity 99% or more), calcium carbonate (manufactured by Ube Materials Co., Ltd .: purity 99.9%), europium oxide ( Each material of Shin-Etsu Chemical Co., Ltd., purity 99.99%), silicon dioxide (Nippon Aerosil Co., Ltd .: purity 99.99%), ammonium chloride (Wako Pure Chemical Industries, Ltd .: purity 99%) is made of Li. : Sr: Ca: Eu: Si: Cl The same as Example 2 except that the molar ratio was 2.0: 0.88: 0.1: 0.02: 1.0: 0.05. Thus, phosphor 3 made of a compound represented by the composition formula Li 2 (Sr 0.88 Ca 0.1 Eu 0.02 ) SiO 4 was obtained. The amount of chlorine in phosphor 3 was 130 ppm.
蛍光体３に波長４６０ｎｍの光を照射して得られる発光強度で、室温（２５℃）の強度を１００とすると、５０℃では１００、７５℃で１００、１００℃で９９、１２０℃で９７であった。 The emission intensity obtained by irradiating the phosphor 3 with light having a wavelength of 460 nm. When the intensity at room temperature (25 ° C.) is 100, 100 at 50 ° C., 100 at 75 ° C., 99 at 100 ° C., 97 at 120 ° C. there were.
さらに、Ｉｎ0.3Ｇａ0.7Ｎからなる発光層を有する青色ＬＥＤを取り込むように蛍光体３を塗布して作製した発光装置を発光させると、青色ＬＥＤからの光とそれにより蛍光体３が励起され発する光との混色によって白色光を発した。 Further, when a light emitting device manufactured by applying the phosphor 3 so as to capture a blue LED having a light emitting layer made of In 0.3 Ga 0.7 N is caused to emit light, the phosphor 3 is excited and emitted by the light from the blue LED. White light was emitted by mixing with light.
実施例４
室温（２５℃）において、蛍光体１に波長４６０ｎｍの光を照射して得られる発光強度を１００とすると、蛍光体２の発光強度は１１０、蛍光体３の発光強度は１３４であった。
Example 4
Assuming that the emission intensity obtained by irradiating the phosphor 1 with light having a wavelength of 460 nm at room temperature (25 ° C.) is 100, the emission intensity of the phosphor 2 is 110, and the emission intensity of the phosphor 3 is 134.
Claims (4)
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| TW095105247A TW200644283A (en) | 2005-02-23 | 2006-02-16 | Fluorescent substance and light-emitting apparatus and white light emitting diode |
| KR1020077021419A KR101261076B1 (en) | 2005-02-23 | 2006-02-20 | Phosphor, light emitting device and white light emitting diode |
| PCT/JP2006/303515 WO2006090865A1 (en) | 2005-02-23 | 2006-02-20 | Phosphor, light emitting device and white light emitting diode |
| CN2006800054414A CN101124295B (en) | 2005-02-23 | 2006-02-20 | Phosphor, light emitting device and white light emitting diode |
| CN2011100303693A CN102154006B (en) | 2005-02-23 | 2006-02-20 | Phosphor, light emitting device and white light emitting diode |
| DE112006000429T DE112006000429T5 (en) | 2005-02-23 | 2006-02-20 | Fluorescent, lighting system and white light emitting diode |
| US11/815,130 US20100155753A1 (en) | 2005-02-23 | 2006-02-20 | Phosphor, light emitting device and white light emitting diode |
| US13/313,183 US20120080708A1 (en) | 2005-02-23 | 2011-12-07 | Phosphor, lighting system and white light emitting diode |
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