JP5368985B2 - 蛍光体粒子群およびそれを用いた発光装置 - Google Patents
蛍光体粒子群およびそれを用いた発光装置 Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims description 124
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 118
- 229910052693 Europium Inorganic materials 0.000 claims description 18
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 18
- 229910003564 SiAlON Inorganic materials 0.000 claims description 16
- 150000004767 nitrides Chemical class 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical group [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- 229910052788 barium Inorganic materials 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 229910052738 indium Inorganic materials 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 3
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- 229910002601 GaN Inorganic materials 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 102100032047 Alsin Human genes 0.000 description 5
- 101710187109 Alsin Proteins 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
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- 230000018109 developmental process Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 229920001187 thermosetting polymer Polymers 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008393 encapsulating agent Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
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- 239000011347 resin Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- GEIAQOFPUVMAGM-UHFFFAOYSA-N ZrO Inorganic materials [Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
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Description
一般式:EuaSibAlcOdNe
(式中、0.005≦a≦0.4、b+c=12、d+e=16を満足する数である。)で実質的に表される柱状結晶体のβ型SiAlONである、2価のユーロピウム付活酸窒化物緑色系発光蛍光体粒子の粒子群であって、長径を短径で割った値が1.0を超えて3.0以下である蛍光体粒子から60%以上が構成されており、且つ、メディアン径が6〜20μmの範囲内である蛍光体粒子群と、
一般式:(MI 1−f Eu f )MIISiN 3
(式中、MIはアルカリ土類金属であり、Mg、Ca、SrおよびBaから選ばれる少なくとも1種の元素を示す。また上記式中、MIIは3価の金属元素であり、Al、Ga、In、Sc、Y、La、GdおよびLuから選ばれる少なくとも1種の元素を示す。fの値は、0.001≦f≦0.10を満足する数である。)で実質的に表される2価のユーロピウム付活窒化物赤色系発光蛍光体粒子の粒子群と、を少なくとも含む発光装置についても提供する。
上記式中、aの値は、0.005≦a≦0.4を満足する数であり、bおよびcの値はb+c=12を満足する数であり、dおよびeの値はd+e=16を満足する数である。上記式中、aの値が0.005未満であると、十分な明るさが得られないという不具合があり、またaの値が0.4を超えると、濃度消光などにより、明るさが大きく低下するという不具合がある。なお、Euの添加量が0.01未満である場合には、蛍光体粒子群にEuが含まれない蛍光体粒子が含まれる虞があり、また、Euの添加量が0.2を超える場合には、Euの偏析が生じてEuを多く含む蛍光体粒子が蛍光体粒子群に含まれてしまう虞があり、粉体特性としての安定性、母体の均一性の維持の観点からは、上記式中のaの値は、0.01≦a≦0.2を満足する数であるのが好ましい。
上記式中、MIはアルカリ土類金属であり、Mg、Ca、SrおよびBaから選ばれる少なくとも1種の元素を示す。また上記式中、MIIは3価の金属元素であり、Al、Ga、In、Sc、Y、La、GdおよびLuから選ばれる少なくとも1種の元素を示す。中でも、より一層高効率に赤色系を発光することができることから、MIIはAl、GaおよびInから選ばれる少なくとも1種の元素であることが好ましい。また上記式中、fの値は、0.001≦f≦0.10であり、0.005≦f≦0.05であるのが好ましい。fの値が0.001未満であると、十分な明るさが得られない傾向にあり、fの値が0.10を越えると、濃度消光などにより、明るさが大きく低下するという傾向にあるためである。
発光素子として、450nmにピーク波長を有する窒化ガリウム(GaN)系半導体を用いた。波長変換部には、Eu0.05Si11.50Al0.50O0.05N15.95(β型SiAlON)(D50値:7.8μm)なる組成を有する緑色系発光蛍光体粒子の粒子群であり、長径を短径で割った値が1.0を超えて3.0以下の粒子から85%が構成されている蛍光体粒子群を用いた。この蛍光体粒子群は、酸素濃度を最適化することによって調製されたものである。なお、粒度分布測定装置としては、LA−920(堀場製作所製)を用いた。この蛍光体粒子群を、所定の割合にて媒質としての熱硬化型のシリコーン樹脂製の封止材中に分散させて分散し、発光素子を封止して、波長変換部を作製し、実施例1の発光装置を作製した。このようにして作製した実施例1の発光装置について、順電流(IF)20mAにて点灯し、発光装置からの光出力(光電流)を測定して、その特性(明るさ)を評価した。
表2に示すような長径を短径で割った値が1.0を超えて3.0以下の粒子の割合(%)、D50値および発光素子を用いたこと以外は実施例1と同様にして、それぞれ実施例2〜7、比較例2〜7の発光装置を作製した。実施例1と同様にして測定した特性(明るさ)の結果とともに、表2に示す。表2から、実施例2〜7の発光装置は、比較例2〜7の発光装置と比し、特性(明るさ)が優れていることが分かる。
発光素子として、460nmにピーク波長を有する窒化ガリウム(GaN)系半導体を用いた。波長変換部には、Eu0.01Si11.80Al0.20O0.04N15.96(β型SiAlON)(D50値:10.5μm)なる組成を有する緑色系発光蛍光体粒子の粒子群であり、長径を短径で割った値が1.0を超えて3.0以下の粒子から85%が構成されている蛍光体粒子群と、(Ca0.99Eu0.01)AlSiN3(D50値:9.3μm)なる組成を有する2価のユーロピウム付活窒化物赤色系発光蛍光体とを用いた。上記蛍光体粒子群は、合成時の温度プロファイルを最適化することによって調製されたものである。なお、粒度分布測定装置としては、LA−920(堀場製作所製)を用いた。この蛍光体粒子群および赤色系発光蛍光体を、所定の割合にて媒質としての熱硬化型のシリコーン樹脂製の封止材中に分散させて分散し、発光素子を封止して、波長変換部を作製し、実施例8の発光装置を作製した。
Claims (6)
- 一般式:EuaSibAlcOdNe
(式中、0.005≦a≦0.4、b+c=12、d+e=16を満足する数である。)で実質的に表される柱状結晶体のβ型SiAlONである、2価のユーロピウム付活酸窒化物緑色系発光蛍光体粒子の粒子群であって、長径を短径で割った値が1.0を超えて3.0以下である蛍光体粒子(1)から60%以上が構成されており、且つ、メディアン径が6〜20μmの範囲内である、蛍光体粒子群。 - 長径を短径で割った値が1.0を超えて3.0以下である蛍光体粒子(1)から80%以上が構成されている、請求の範囲第1項に記載の蛍光体粒子群。
- 上記式中、0.01≦a≦0.2である請求の範囲第1項に記載の蛍光体粒子群。
- ピーク波長が430〜480nmの一次光を発する窒化ガリウム系半導体である発光素子(12)と、上記一次光の一部を吸収して、一次光の波長よりも長い波長を有する二次光を発する波長変換部(13)とを備え、混色により白色光を呈する発光装置(11)であって、前記波長変換部(13)は、
一般式:Eu a Si b Al c O d N e
(式中、0.005≦a≦0.4、b+c=12、d+e=16を満足する数である。)で実質的に表される柱状結晶体のβ型SiAlONである、2価のユーロピウム付活酸窒化物緑色系発光蛍光体粒子の粒子群であって、長径を短径で割った値が1.0を超えて3.0以下である蛍光体粒子から60%以上が構成されており、且つ、メディアン径が6〜20μmの範囲内である蛍光体粒子群と、
一般式:(MI 1−f Eu f )MIISiN 3
(式中、MIはアルカリ土類金属であり、Mg、Ca、SrおよびBaから選ばれる少なくとも1種の元素を示す。また上記式中、MIIは3価の金属元素であり、Al、Ga、In、Sc、Y、La、GdおよびLuから選ばれる少なくとも1種の元素を示す。fの値は、0.001≦f≦0.10を満足する数である。)で実質的に表される2価のユーロピウム付活窒化物赤色系発光蛍光体粒子の粒子群と、を少なくとも含む、発光装置(11)。 - 上記蛍光体粒子群が、長径を短径で割った値が1.0を超えて3.0以下である蛍光体粒子(1)から80%以上が構成されている、請求の範囲第4項に記載の発光装置(11)。
- 上記式中、0.01≦a≦0.2である請求の範囲第4項に記載の発光装置(11)。
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