JP5631745B2 - 透光性セラミックプレートを備える発光装置 - Google Patents
透光性セラミックプレートを備える発光装置 Download PDFInfo
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- JP5631745B2 JP5631745B2 JP2010547760A JP2010547760A JP5631745B2 JP 5631745 B2 JP5631745 B2 JP 5631745B2 JP 2010547760 A JP2010547760 A JP 2010547760A JP 2010547760 A JP2010547760 A JP 2010547760A JP 5631745 B2 JP5631745 B2 JP 5631745B2
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- emitting device
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- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
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Description
本出願は、2008年2月21日付の米国特許仮出願第61/030496号および2009年2月17日付の米国特許仮出願第61/153227号の優先権を主張し、これらの仮出願はいずれも、その全体がここでの言及によって本明細書に援用される。
R=((ns−1)/(ns+1))2 T=1−R
上面および下面の両方の反射を考慮し、理論全光線透過率を、以下の式を使用して計算することができる。
理論全光線透過率=(1/T+1/T−1)−1
<誘導結合RF熱プラズマ熱分解を用いた原料粉末の作成>
0.14923mol(14.29g)の硝酸イットリウム(III)六水和物(純度99.9%、Sigma−Aldrich)、0.25mol(23.45g)の硝酸アルミニウム九水和物(純度99.97%、Sigma−Aldrich)、および0.015mol(0.081g)の硝酸セリウム(III)六水和物(純度99.99%、Sigma−Aldrich)を250mlの脱イオン水に溶かし、その後30分間の超音波処理を行って、透明な前駆体溶液を作成した。0.4Mのこの前駆体溶液を、液体ポンプを使用して霧化プローブ経由でプラズマ反応チャンバへと輸送した。
焼結セラミックプレートを、YAG:Ce蛍光体ナノ粉末を使用して作製した。上述の方法によって作成した4gのナノ粉末、0.21gのポリ(ビニルブチラール−コ−ビニルアルコール−コ−酢酸ビニル)(平均Mwが90,000〜120,000の粉末、Sigma−Aldrich)、0.012gのヒュームドシリカ粉末(CAB−O−SIL(登録商標)HS−5、Cabot Corporation)、および10mlのメタノールを、混合物のスラリー溶液がきわめて滑らかになるまで、乳鉢と乳棒によってよく混合した。ドライヤで高温の空気を吹き付け、乳棒を動かし続けることによって、メタノールを完全に除去して、乾燥粉末を得た。得られた乾燥粉末の導入量を45.0、47.5、50.0、および52.5mgと変えて、3mmの直径を有するダイセット(製品番号: 0012−6646、3mm KBr Die Set、International Crystal Laboratories, Inc)へと広げ、その後に油圧プレスを用いて4000psiの圧力を加えた。次いで、得られたプレートを、空気雰囲気のもとで箱形電気炉を使用して1500℃で5時間(加熱速度は、5℃/分)にわたって焼結した。この方法を用いて、YAG:Ce蛍光体材料の4つの焼結セラミックプレートサンプルを作成した。得られたサンプルは黄色であった。XRDによって、すべてのセラミックプレートサンプルの結晶相が、イットリウム・アルミニウム・ガーネットであることが明らかになった。セラミックプレートの厚さを、従来のマイクロメータによって測定した結果を表1にまとめた。
これら4つのセラミックプレートサンプルを、2.9V、DC10mAの動作条件のもとで、青色LEDチップへと1つずつ取り付けた。各々のステップにおいて、積分球を備える光検出器(MCPD 7000、大塚電子社)を用いて、白色光のスペクトルを取得した。セラミックプレートとLEDチップとの間の空隙を取り除くために、空隙をパラフィン油で満たした。これらの測定においては、同一のLEDチップおよび動作条件を使用した。これらの放射スペクトルから、CIEカラー色度(x、y)を計算したところ、表1にまとめたとおり、および図15にプロットしたとおりであった。青色LEDの(x、y)値も、図15にプロットされている。セラミックプレートの厚さが増加するにつれ、放射される光の色は、青みがかった色から黄色みがかった色へと変化した。とりわけ、サンプル1−3の放射が白色光に近く、その放射スペクトルは図16に示されている。
RFプラズマにより合成した状態のままのナノ粉末に代えて、アニールしたナノ粉末を使用して焼結セラミックプレートのサンプルを作製した。先に述べたRFプラズマ法によって作製したナノ粒子を、石英管炉(MTI Corporation GSL−1600X)を使用して、1atm、H2/N2=3%/97%の雰囲気で、2時間にわたって1200℃でアニールした。温度上昇速度は、10℃/分であった。アニール後に、黄色みがかった色の粉末が得られ、XRDによって、イットリウム・アルミニウム・ガーネットの結晶相が確認された。BET測定から求められたアニール後の平均直径は、129nmであった。
比較のために、ミクロンサイズのYAG:Ce粉末/シリコーン樹脂の複合材料層を、作成した。0.4gのミクロンサイズのYAG:Ce蛍光体粉末(P46−Y3、Davg 6.6μm、化成オプトニクス社)および0.6gのシリコーン樹脂を混ぜ合わせた。混合物を厚さ0.55mmのスライドガラスへキャストした後、ホットプレートを使用して150℃で1時間にわたってシリコーン樹脂を硬化させ、ミクロンサイズのYAG:Ce粉末/シリコーン樹脂の複合材料層を得た。スライドガラス上の複合材料層の厚さは、約1mmであった。複合材料層を備えるスライドガラスを、複合材料層の側がLEDチップに面するように、実施例1において説明したのと同一の動作条件を有する同一のLEDチップへと取り付けた。複合材料層とLEDチップとの間の空隙を、パラフィン油で満たした。最初は、白色光を生成するには複合材料層が厚すぎるために、LEDサンプルからの放射光の色は黄色みがかっていた。放射される色が白色になるまで、サンドペーパを用いて複合材料層を削って厚さを調節した。最終的に、複合材料層の厚さが148μmのときに、CIEカラー色度(x、y)=(0.322、0.378)を有する白色の放射が得られた。
ミクロンサイズのYAG:Ce蛍光体粉末を用いて焼結セラミックプレートを作製した。粒子サイズが大きすぎるため、ダイセットを使用して約100〜200μmの厚さを有する安定かつ平坦なプレートを作成することは、不可能であった。破損したプレートの一部分を、実施例1において使用したのと同一の条件下で焼結した。得られたセラミックプレートのかけらは、黄色を呈していたが、黄色の紙のようにきわめて拡散的であるように見受けられた。セラミックプレートの厚さは、概ね150μmであり、550nmにおける全光線透過率は、およそ23%であった。このセラミックプレートも青色LEDへと取り付けて、放射スペクトルを得た。しかしながら、放射の色は、セラミックプレートの強力な散乱特性に起因して、(0.383、0.578)という(x、y)値を有し、ほぼ黄色であった。セラミックプレートの厚さを100μmを下回るまで調節しても白色光は得られなかった。
焼結を1500℃ではなくて1200℃で実行した点を除き、実施例1と同じサンプルを作成した。平坦なプレートを上手く作成することができたが、プレートはかなり不透明である。比較例2と同様、たとえセラミック層の厚さが100μm未満でも白色は実現されなかった。約95μmの厚さを有するセラミックプレートの530nmにおける全光線透過率は、約27%であり、得られた(x、y)値は、(0.369、0.545)であった。
図18は、サンプル1〜3、サンプル2〜4、および比較例1を青色LEDへと取り付けた際のLEDサンプルからの白色の放射のCIEカラーチャートを示している。重要な特性を、表3にまとめている。同じ動作条件下でのLEDサンプルの白色の放射スペクトルを、図19に示す。
多相焼結セラミックプレート:サンプル3−1を、実施例1において説明したRFプラズマ法を使用して作製した。0.14923mol(14.29g)の硝酸イットリウム(III)六水和物(純度99.9%、Sigma−Aldrich)、0.25625mol(24.03g)の硝酸アルミニウム九水和物(純度99.97%、Sigma−Aldrich)、および0.015mol(0.081g)の硝酸セリウム(III)六水和物(純度99.99%、Sigma−Aldrich)を、250mlの脱イオン水に溶かし、その後に30分間の超音波処理を行って、前駆体溶液を作成した。この前駆体溶液を使用して作成されたナノ粉末は、第2相を形成するための追加の材料Al2O3を有している。ナノ粉末を、H2/N2=3%/97%の雰囲気で2時間にわたって1200℃でアニールした。昇温速度は、5℃/分であった。アニールの後に、黄色みがかった色の粉末が得られ、XRDより、イットリウム・アルミニウム・ガーネットの結晶相と同定された。Alリッチな組成の第2相の材料の量に応じて、Al2O3相の小さなXRDピークも検出された。
Claims (24)
- 440nm〜470nmの第1のピーク波長を有する光を放射する発光部材、および前記発光部材の上方に位置する少なくとも1つの焼結セラミックプレートを備え、
前記少なくとも1つの焼結セラミックプレートは多相材料を含んでおり、該多相材料は、85体積%〜99.99体積%の放射相と15体積%〜0.01体積%の第2相とを含み、
前記少なくとも1つの焼結セラミックプレートは、前記発光部材から放射される光の少なくとも一部分を吸収し、第2のピーク波長の光を発することができるとともに、該第2のピーク波長において40%よりも大きい全光線透過率を有しており、
前記少なくとも1つの焼結セラミックプレートは、1000nm未満の平均粒子サイズを有するナノサイズの原料セラミック粉末を使用することによって作成されたものである発光装置。 - 前記多相材料が、95体積%〜99.5体積%の放射相と5体積%〜0.5体積%の第2相とを含む請求項1に記載の発光装置。
- 前記多相材料が、98体積%〜99.5体積%の放射相と2体積%〜0.05体積%の第2相とを含む請求項1に記載の発光装置
- 前記少なくとも1つの焼結セラミックプレートが、0.05重量%〜5重量%の焼結助剤をさらに含む請求項1〜3のいずれか1項に記載の発光装置。
- 前記焼結助剤が、MgO、SiO2、およびオルトケイ酸テトラエチルからなる群から選択される請求項4に記載の発光装置。
- 前記放射相が、蛍光体材料を含む請求項1〜5のいずれか1項に記載の発光装置。
- 前記蛍光体材料が、式A3B5O12によって表わされるガーネットを含んでおり、AおよびBが、三価の金属であって、Aが、Y、Gd、La、およびTbから選択され、Bが、Al、Ga、およびInから選択される請求項6に記載の発光装置。
- 前記ガーネットが、少なくとも1つの希土類金属でドープされている請求項7に記載の発光装置。
- 前記希土類金属が、Ce、Gd、La、Tb、Pr、およびEuから選択される請求項8に記載の発光装置。
- 前記蛍光体材料が、Y3Al5O12:Ce3+を含む請求項6〜9のいずれか1項に記載の発光装置。
- 前記第2相が、Y2O3、Al2O3、YAP、およびYAMからなる群から選択される材料を含む請求項1〜10のいずれか1項に記載の発光装置。
- 前記第2相が、Al2O3またはY2O3である請求項1〜11のいずれか1項に記載の発光装置。
- 発光装置の輝度を改善するための方法であって、発光部材を準備するステップ、および多相材料を含む少なくとも1つの焼結セラミックプレートを、前記発光部材の上方に配置するステップを有し、
前記多相材料が、85体積%〜99.99体積%の放射相と15体積%〜0.01体積%の第2相とを含んでおり、前記少なくとも1つの焼結セラミックプレートが、ピーク透過波長において少なくとも40%の透過率を有し、前記少なくとも1つの焼結セラミックプレートが、1000nm未満の平均粒子サイズを有するナノサイズの原料セラミック粉末を使用することによって作成されたものである、当該発光装置から白色光が出射される方法。 - 前記多相材料が、95体積%〜99.5体積%の放射相と5体積%〜0.5体積%の第2相とを含む請求項13に記載の方法。
- 前記多相材料が、98体積%〜99.5体積%の放射相と2体積%〜0.5体積%の第2相とを含む請求項13に記載の方法。
- 前記少なくとも1つの焼結セラミックプレートが、0.05重量%〜5重量%の焼結助剤をさらに含む請求項13〜15のいずれか1項に記載の方法。
- 前記焼結助剤が、MgO、SiO2、およびオルトケイ酸テトラエチルからなる群から選択される請求項16に記載の方法。
- 前記放射相が、蛍光体材料を含む請求項13〜17のいずれか1項に記載の方法。
- 前記蛍光体材料が、式A3B5O12によって表わされるガーネットを含んでおり、AおよびBが、三価の金属であって、Aが、Y、Gd、La、およびTbから選択され、Bが、Al、Ga、およびInから選択される請求項18に記載の方法。
- 前記ガーネットが、少なくとも1つの希土類金属でドープされている請求項19に記載の方法。
- 前記希土類金属が、Ce、Gd、La、Tb、Pr、およびEuから選択される請求項20に記載の方法。
- 前記蛍光体材料が、Y3Al5O12:Ce3+を含む請求項18〜21のいずれか1項に記載の方法。
- 前記第2相が、Y2O3、Al2O3、YAP、およびYAMからなる群から選択される材料を含む請求項13〜22のいずれか1項に記載の発光装置。
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PCT/US2009/034574 WO2009105581A1 (en) | 2008-02-21 | 2009-02-19 | Light emitting device with translucent ceramic plate |
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