JP2007123392A - 有機エレクトロルミネッセンス素子、表示装置及び照明装置 - Google Patents
有機エレクトロルミネッセンス素子、表示装置及び照明装置 Download PDFInfo
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- JP2007123392A JP2007123392A JP2005310975A JP2005310975A JP2007123392A JP 2007123392 A JP2007123392 A JP 2007123392A JP 2005310975 A JP2005310975 A JP 2005310975A JP 2005310975 A JP2005310975 A JP 2005310975A JP 2007123392 A JP2007123392 A JP 2007123392A
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- 230000001360 synchronised effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229940042055 systemic antimycotics triazole derivative Drugs 0.000 description 1
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- 150000003536 tetrazoles Chemical group 0.000 description 1
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- 229930192474 thiophene Natural products 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000004306 triazinyl group Chemical group 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
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Images
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
Abstract
Description
2.前記一般式(1)のM1がイリジウム原子であることを特徴とする1に記載の有機エレクトロルミネッセンス素子。
本発明の一般式(1)で表される燐光性化合物について説明する。
次に、一般式(2)で表される化合物について説明する。
次に、一般式(3)で表される化合物について説明する。
(ii)陽極/正孔輸送層/発光層/電子輸送層/陰極
(iii)陽極/正孔輸送層/発光層/正孔阻止層/電子輸送層/陰極
(iv)陽極/正孔輸送層/発光層/正孔阻止層/電子輸送層/陰極バッファー層/陰極
(v)陽極/陽極バッファー層/正孔輸送層/発光層/正孔阻止層/電子輸送層/陰極バッファー層/陰極
なお、正孔輸送層は陽極に隣接し、電子輸送層は陰極に隣接していることが好ましい。
有機EL素子における陽極としては、仕事関数の大きい(4eV以上)金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としてはAu等の金属、CuI、インジウムチンオキシド(ITO)、SnO2、ZnO等の導電性透明材料が挙げられる。また、IDIXO(In2O3−ZnO)等非晶質で透明導電膜を作製可能な材料を用いてもよい。陽極はこれらの電極物質を蒸着やスパッタリング等の方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、あるいはパターン精度をあまり必要としない場合は(100μm以上程度)、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。この陽極より発光を取り出す場合には、透過率を10%より大きくすることが望ましく、また陽極としてのシート抵抗は数百Ω/□以下が好ましい。さらに膜厚は材料にもよるが、通常10〜1000nm、好ましくは10〜200nmの範囲で選ばれる。
一方、陰極としては、仕事関数の小さい(4eV以下)金属(電子注入性金属と称する)、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム−カリウム合金、マグネシウム、リチウム、マグネシウム/銅混合物、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、インジウム、リチウム/アルミニウム混合物、希土類金属等が挙げられる。これらの中で、電子注入性及び酸化等に対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えば、マグネシウム/銀混合物、マグネシウム/アルミニウム混合物、マグネシウム/インジウム混合物、アルミニウム/酸化アルミニウム(Al2O3)混合物、リチウム/アルミニウム混合物、アルミニウム等が好適である。陰極はこれらの電極物質を蒸着やスパッタリング等の方法により薄膜を形成させることにより、作製することができる。また、陰極としてのシート抵抗は数百Ω/□以下が好ましく、膜厚は通常10nm〜5μm、好ましくは50〜200nmの範囲で選ばれる。なお、発光した光を透過させるため、有機EL素子の陽極または陰極のいずれか一方が、透明または半透明であれば発光輝度が向上し好都合である。
注入層は必要に応じて設け、電子注入層と正孔注入層があり、上記の如く陽極と発光層または正孔輸送層の間、及び陰極と発光層または電子輸送層との間に存在させてもよい。
阻止層は、上記の如く、有機化合物薄膜の基本構成層の他に必要に応じて設けられるものである。例えば、特開平11−204258号公報、同11−204359号公報、及び「有機EL素子とその工業化最前線(1998年11月30日エヌ・ティー・エス社発行)」の237頁等に記載されている正孔阻止(ホールブロック)層がある。
本発明に係る発光層は、電極または電子輸送層、正孔輸送層から注入されてくる電子及び正孔が再結合して発光する層であり、発光する部分は発光層の層内であっても発光層と隣接層との界面であってもよい。
本発明の有機EL素子の発光層には、以下に示すホスト化合物と燐光性化合物(燐光発光性化合物ともいう)が含有されることが好ましく、本発明においては、ホスト化合物として前述した一般式(2)で表される化合物を用いることが好ましい。これにより、より一層発光効率を高くすることができる。また、ホスト化合物として一般式(2)で表される化合物以外の化合物を含有してもよい。
発光層に使用される材料(以下、発光材料という)としては、上記のホスト化合物を含有すると同時に、燐光性化合物を含有することが好ましい。これにより、より発光効率の高い有機EL素子とすることができる。
正孔輸送層とは正孔を輸送する機能を有する正孔輸送材料からなり、広い意味で正孔注入層、電子阻止層も正孔輸送層に含まれる。正孔輸送層は単層または複数層設けることができる。
電子輸送層とは電子を輸送する機能を有する材料からなり、広い意味で電子注入層、正孔阻止層も電子輸送層に含まれる。電子輸送層は単層または複数層設けることができる。
本発明の有機EL素子は、基体上に形成されているのが好ましい。
本発明の有機EL素子の作製方法の一例として、陽極/正孔注入層/正孔輸送層/発光層/電子輸送層/電子注入層/陰極からなる有機EL素子の作製法について説明する。
本発明の有機EL素子は、照明用や露光光源のような1種のランプとして使用してもよいし、画像を投影するタイプのプロジェクション装置や、静止画像や動画像を直接視認するタイプの表示装置(ディスプレイ)として使用してもよい。動画再生用の表示装置として使用する場合の駆動方式は単純マトリックス(パッシブマトリックス)方式でもアクティブマトリックス方式でもどちらでもよい。または、異なる発光色を有する本発明の有機EL素子を3種以上使用することにより、フルカラー表示装置を作製することが可能である。または、一色の発光色、例えば、白色発光をカラーフィルターを用いてBGRにし、フルカラー化することも可能である。さらに有機ELの発光色を色変換フィルターを用いて他色に変換しフルカラー化することも可能であるが、その場合、有機EL発光のλmaxは480nm以下であることが好ましい。
《有機EL素子1−1〜1−20の作製》
陽極として100mm×100mm×1.1mmのガラス基板上にITO(インジウムチンオキシド)を100nm製膜した基板(NHテクノグラス社製NA45)にパターニングを行った後、このITO透明電極を設けた透明支持基板をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、UVオゾン洗浄を5分間行った。この透明支持基板を市販の真空蒸着装置の基板ホルダーに固定し、一方、モリブデン製抵抗加熱ボートにα−NPDを200mg入れ、別のモリブデン製抵抗加熱ボートにホスト化合物としてCBPを200mg入れ、別のモリブデン製抵抗加熱ボートにバソキュプロイン(BCP)を200mg入れ、別のモリブデン製抵抗加熱ボートに燐光性化合物として比較化合物1を100mg入れ、さらに別のモリブデン製抵抗加熱ボートにAlq3を200mg入れ、真空蒸着装置に取付けた。
以下のようにして、作製した有機EL素子1−1〜1−20の評価を行った。
分光放射輝度計CS−1000(コニカミノルタセンシング社製)を用いて輝度(cd/m2)を求めた。輝度の測定結果は、有機EL素子1−1の測定値を100とする相対値で表した。
作製した有機EL素子について、23℃、乾燥窒素ガス雰囲気下で2.5mA/cm2定電流を印加した時の外部取り出し量子効率(%)を測定した。なお測定には同様に分光放射輝度計CS−1000(コニカミノルタセンシング社製)を用いた。外部取りだし量子効率の測定結果は、有機EL素子1−1の測定値を100とする相対値で表した。
《有機EL素子2−1〜2−15の作製》
陽極として100mm×100mm×1.1mmのガラス基板上にITO(インジウムチンオキシド)を100nm製膜した基板(NHテクノグラス社製NA45)にパターニングを行った後、このITO透明電極を設けた透明支持基板をイソプロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、UVオゾン洗浄を5分間行った。この透明支持基板を市販の真空蒸着装置の基板ホルダーに固定し、一方モリブデン製抵抗加熱ボートにα−NPDを200mg入れ、別のモリブデン製抵抗加熱ボートに発光層のホスト化合物としてCBPを200mg入れ、別のモリブデン製抵抗加熱ボートに正孔阻止材料としてBCPを200mg入れ、別のモリブデン製抵抗加熱ボートに発光層の燐光性化合物として比較化合物1を100mg入れ、さらに別のモリブデン製抵抗加熱ボートにAlq3を200mg入れ、真空蒸着装置に取付けた。
実施例1と同様にして有機EL素子2−1〜2−15の輝度、外部取り出し量子効率の評価を行った。さらに下記に示す測定法に従って、寿命の評価を行った。
2.5mA/cm2の一定電流で駆動したときに、輝度が発光開始直後の輝度(初期輝度)の半分に低下するのに要した時間を測定し、これを半減寿命時間(τ0.5)として寿命の指標とした。なお測定には分光放射輝度計CS−1000(コニカミノルタセンシング社製)を用いた。
《有機EL素子3−1〜3−8の作製》
実施例1に記載の有機EL素子1−1の作製において、発光層のホスト化合物及び燐光性化合物を表3に記載の化合物に変更し、さらにBCPをB−Alqに変更した以外は同様にして、有機EL素子3−1〜3−8を作製した。
下記に示す測定法に従って、保存性の評価を行った。
各有機EL素子を85℃で24時間保存した後、保存前後における2.5mA/cm2の定電流駆動での各輝度を測定し、各輝度比を下式に従って求め、これを保存性の尺度とした。
以上により得られた結果を表3に示す。
《有機EL素子4−1〜4−8の作製》
実施例2に記載の有機EL素子2−1の作製において、発光層のホスト化合物(CBP)を、例示化合物2−1に変更し、さらに正孔阻止層の正孔阻止材料及び発光層の燐光性化合物を表4のように変更した以外は同様にして、有機EL素子4−1〜4−8を作製した。
実施例3と同様にして有機EL素子4−1〜4−8の保存性の評価を行い、得られた結果を表4に示す。
実施例1で作製した本発明の有機EL素子1−5と、実施例1で作製した本発明の有機EL素子1−5の燐光性化合物をIr−1に置き換えた以外は同様にして作製した緑色発光有機EL素子と、本発明の有機EL素子1−5の燐光性化合物をIr−9に置き換えた以外は同様にして作製した赤色発光有機EL素子を同一基板上に並置し、図1に示すアクティブマトリクス方式フルカラー表示装置を作製した。図2には作製したフルカラー表示装置の表示部Aの模式図のみを示した。即ち同一基板上に、複数の走査線5及びデータ線6を含む配線部と、並置した複数の画素3(発光の色が赤領域の画素、緑領域の画素、青領域の画素等)とを有し、配線部の走査線5及び複数のデータ線6はそれぞれ導電材料からなり、走査線5とデータ線6は格子状に直交して、直交する位置で画素3に接続している(詳細は図示せず)。前記複数の画素3は、それぞれの発光色に対応した有機EL素子、アクティブ素子であるスイッチングトランジスタと駆動トランジスタそれぞれが設けられたアクティブマトリクス方式で駆動されており、走査線5から走査信号が印加されると、データ線6から画像データ信号を受け取り、受け取った画像データに応じて発光する。このように各赤、緑、青の画素を適宜、並置することによって、フルカラー表示が可能となる。
《照明装置の作製》
実施例4で作製した青色発光、緑色発光及び赤色発光の有機EL素子各々の非発光面をガラスケースで覆い、照明装置とした。照明装置は、発光効率が高く、発光寿命の長い白色光を発する薄型の照明装置として使用することができた。図5は照明装置の概略図で、図6は照明装置の断面図である。有機EL素子101をガラスカバー102で覆った。105は陰極で106は有機EL層、107は透明電極付きガラス基板である。なおガラスカバー102内には窒素ガス108が充填され、捕水剤109が設けられている。
3 画素
5 走査線
6 データ線
7 電源ライン
10 有機EL素子
11 スイッチングトランジスタ
12 駆動トランジスタ
13 コンデンサ
A 表示部
B 制御部
102 ガラスカバー
105 陰極
106 有機EL層
107 透明電極付きガラス基板
108 窒素ガス
109 捕水剤
Claims (9)
- 一対の電極間に、少なくとも下記一般式(1)で表される燐光性化合物を含む発光層を含む構成層を有し、該構成層の少なくとも一層に、下記一般式(2)で表される化合物を含有することを特徴とする有機エレクトロルミネッセンス素子。
- 前記一般式(1)のM1がイリジウム原子であることを特徴とする請求項1に記載の有機エレクトロルミネッセンス素子。
- 前記一般式(1)のM1が白金原子であることを特徴とする請求項1に記載の有機エレクトロルミネッセンス素子。
- 前記発光層に前記一般式(2)で表される化合物を含有することを特徴とする請求項1〜3のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 前記構成層の少なくとも一層が正孔阻止層であり、該正孔阻止層に前記一般式(2)で表される化合物を含有することを特徴とする請求項1〜4のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 青色に発光することを特徴とする請求項1〜5のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 白色に発光することを特徴とする請求項1〜5のいずれか1項に記載の有機エレクトロルミネッセンス素子。
- 請求項1〜7に記載の有機エレクトロルミネッセンス素子を有することを特徴とする表示装置。
- 請求項1〜7に記載の有機エレクトロルミネッセンス素子を有することを特徴とする照明装置。
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