JPWO2013140885A1 - 有機エレクトロルミネッセンス素子及び照明装置 - Google Patents
有機エレクトロルミネッセンス素子及び照明装置 Download PDFInfo
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- JPWO2013140885A1 JPWO2013140885A1 JP2014506070A JP2014506070A JPWO2013140885A1 JP WO2013140885 A1 JPWO2013140885 A1 JP WO2013140885A1 JP 2014506070 A JP2014506070 A JP 2014506070A JP 2014506070 A JP2014506070 A JP 2014506070A JP WO2013140885 A1 JPWO2013140885 A1 JP WO2013140885A1
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Abstract
Description
L1<L2≦1.50eV<L3
2.前記正孔阻止層を構成する正孔阻止化合物のLUMOのエネルギー準位の絶対値L2が、1.10〜1.50eVの範囲内であることを特徴とする第1項に記載の有機エレクトロルミネッセンス素子。
4.加法混色により白色発光することを特徴とする第1項から第3項までのいずれか一項に記載の有機エレクトロルミネッセンス素子。
本発明の有機EL素子の構成層について説明する。本発明において、有機EL素子の層構成の好ましい具体例を以下に示すが、本発明はこれらに限定されない。
(ii)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
(iii)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
(iv)陽極//正孔輸送層/陽極バッファー層/発光層/正孔阻止層/電子輸送層/陰極バッファー層/陰極
複数の発光層が含まれる場合、該発光層間に非発光性の中間層を有してもよい。また、上記層構成の内、陽極及び陰極を除く発光層を含む有機化合物層を1つの発光ユニットとし、複数の発光ユニットを積層することが可能である。該複数の積層された発光ユニットにおいては、発光ユニット間に非発光性の中間層を有していてもよく、更に中間層は電荷発生層を含んでいてもよい。
本発明の有機EL素子においては、発光層を構成するホスト化合物のLUMO(最低空分子軌道)のエネルギー準位の絶対値をL1(eV)、正孔阻止層を構成する正孔阻止化合物(以下、正孔阻止材料ともいう)のLUMOのエネルギー準位の絶対値をL2(eV)、電子輸送層を構成する電子輸送化合物(以下、電子輸送材料ともいう)のLUMOのエネルギー準位の絶対値をL3(eV)としたとき、それぞれのLUMOのエネルギー準位(絶対値)がL1<L2≦1.50eV<L3の関係にあることを特徴とし、上記関係を満たすように、発光層を構成するホスト化合物、正孔阻止層を構成する正孔阻止化合物及び電子輸送層を構成する電子輸送化合物を選択する。
本発明に係る正孔阻止層とは、広い意味では後述する電子輸送層の機能を有し、電子を輸送する機能を有しつつ、正孔を輸送する能力が著しく小さい材料から構成され、電子を輸送しつつ正孔を阻止することで、電子と正孔の再結合確立を向上させることができる。
本発明の有機EL素子においては、正孔阻止層が下記一般式(1)で表される化合物を含有することを特徴とする。
本発明に係る発光層は、電極又は電子輸送層、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、少なくともホスト化合物とリン光発光性化合物を含有することを特徴とする。発光層において、上記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。
(1:リン光発光性化合物)
本発明に係るリン光発光性化合物は、励起三重項からの発光が観測される化合物であり、具体的には室温(25℃)にてリン光発光する化合物であり、リン光量子収率が、25℃において0.01以上の化合物であると定義されるが、好ましいリン光量子収率は0.10以上である。
本発明に係るリン光発光ドーパントAの形成に好ましく用いられる上記一般式(A)〜(C)で各々表される化合物について説明する。
また、本発明に係るリン光発光性化合物としては、複数種の化合物を併用して用いてもよく、構造の異なるリン光ドーパント同士の組み合わせや、リン光ドーパントと蛍光ドーパントを組み合わせて用いてもよい。
本発明に係るホスト化合物は、LUMO(最低空分子軌道)のエネルギー準位の絶対値をL1(eV)としたとき、正孔阻止層を構成する正孔阻止化合物のLUMOのエネルギー準位の絶対値L2(eV)と、電子輸送層を構成する電子輸送化合物のLUMOのエネルギー準位の絶対値L3(eV)との関係が、L1<L2≦1.50eV<L3の条件を満たす化合物であることを特徴とする。
注入層は必要に応じて設け、電子注入層(陰極バッファー層)と正孔注入層(陽極バッファー層)があり、上記の如く陽極と発光層又は正孔輸送層の間、及び陰極と発光層又は電子輸送層との間に存在させてもよい。
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。正孔輸送層は単層又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。電子輸送層は単層もしくは複数層を設けることができる。
電子阻止層とは広い意味では正孔輸送層の機能を有し、正孔を輸送する機能を有しつつ電子を輸送する能力が著しく小さい材料からなり、正孔を輸送しつつ電子を阻止することで電子と正孔の再結合確率を向上させることができる。
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−スズの複合酸化物(以下、ITOと略記。)、SnO2、ZnO等の導電性透明材料が挙げられる。
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。
本発明の有機EL素子に用いることのできる支持基板(以下、基体、基板、基材、支持体等ともいう。)としては、ガラス、プラスチック等、種類には特に限定はなく、また透明であっても不透明であってもよい。支持基板側から光を取り出す場合には、支持基板は透明であることが好ましい。
有機EL素子の製造方法の一例として、陽極/正孔注入層/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(電子注入層)/陰極からなる有機EL素子の製造方法について説明する。
本発明の有機EL素子は、陽極、陰極、及び陰極と陽極との間にある有機EL層を外気から遮断するため、封止材料で外部環境と遮断して封止しておくことが好ましい。
有機層を挟み支持基板と対向する側の前記封止膜、あるいは前記封止用フィルムの外側に、素子の機械的強度を高めるために保護膜、あるいは保護板を設けてもよい。特に封止が前記封止膜により行われている場合には、その機械的強度は必ずしも高くないため、このような保護膜、保護板を設けることが好ましい。
有機EL素子は空気よりも屈折率の高い(屈折率が1.7〜2.1程度)層の内部で発光し、発光層で発生した光のうち15%から20%程度の光しか取り出せないことが一般的に言われている。これは、臨界角以上の角度θで界面(透明基板と空気との界面)に入射する光は、全反射を起こし素子外部に取り出すことができないことや、透明電極ないし発光層と透明基板との間で光が全反射を起こし、光が透明電極ないし発光層を導波し、結果として光が素子側面方向に逃げるためである。
本発明の有機EL素子では、基板の光取り出し側に、マイクロレンズアレイ状の構造を設けるように加工する、あるいは所謂集光シートと組み合わせることにより、特定方向、例えば、素子発光面に対し正面方向に集光することにより、特定方向上の輝度を高めることができる。
本発明の有機EL素子は、表示デバイス、ディスプレイ、各種発光光源として用いることができる。発光光源として、例えば、照明装置(家庭用照明、車内照明)、時計や液晶用バックライト、看板広告、信号機、光記憶媒体の光源、電子写真複写機の光源、光通信処理機の光源、光センサーの光源等が挙げられるがこれに限定するものではないが、特に液晶表示装置のバックライト、照明用光源としての用途に有効に用いることができる。
本発明の表示装置について説明する。本発明の表示装置は、本発明の有機EL素子を具備したものである。
本発明の照明装置について説明する。本発明の照明装置は、本発明の有機EL素子を具備する。
本発明の有機EL素子を具備した本発明の照明装置の一態様について説明する。
〔有機EL素子1の作製〕
以下に示す手順に従って、白色発光の有機EL素子1を作製した。
上記有機EL素子1の作製において、発光層及び正孔阻止層の構成材料を、表1に記載した化合物に変更した以外は同様にして、白色発光の有機EL素子2〜24を作製した。
〔照明装置の作製〕
上記作製した各有機EL素子の非発光面をガラスカバーで覆い、ガラスカバーと有機EL素子が作製されたガラス基板とが接触するガラスカバー側の周囲にシール剤としてエポキシ系光硬化型接着剤(東亞合成社製、ラクストラックLC0629B)を用いて、これを有機EL素子の陰極側に重ねて前記透明支持基板と密着させ、ガラス基板側から有機EL素子を除いた部分にUV光を照射して硬化させて封止し、図5及び図6に示す構成からなる白色発光の照明装置1〜20を作製した。
上記作製した各照明装置について、下記の各評価を行った。
各照明装置について、2.5mA/cm2の定電流条件で連続発光を行った際の発光色を目視で判定した。白色であれば「○」、白色以外の発光である場合には「×」と判定した。
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、各照明装置を構成する有機EL素子の正面輝度及び輝度角度依存性を測定し、正面輝度1000cd/m2における電力効率を求めた。
各照明装置を、23℃、50%RHの環境下で、2.5mA/cm2の定電流条件による連続発光を行い、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、初期輝度の半分の輝度になるのに要する時間(半減期:τ1/2)を測定した。なお、発光寿命の評価は、有機EL素子1の半減期(時間)を100とする相対値で表示した。数値が大きいほど、発光寿命が長いことを表す。
〈耐熱性の評価〉
各照明装置を85℃、20%RHの環境下で500時間の加熱処理を行った後、加熱処理前と加熱処理の各有機EL素子の正面輝度におけるCIE1931、x、y値を測定し、各x、y値の変動距離Δx、Δyを求め、下式に従って変動最大距離ΔEを算出し、これを耐熱性の尺度とした。表2には、有機EL素子1のΔEを100とする相対値を求めた。値が小さいほど、高温環境に晒された後でも、色度変動が少なく、白色発光からの色変動が少なく色度安定性(耐熱性)が良好であることを意味する。なお、正面輝度の測定については分光放射輝度計CS−1000(コニカミノルタセンシング社製)を用いた。
〈環境変動安定性の評価〉
各照明装置を、1)25℃、55%RHの環境下で6時間、次いで2)80℃、20%RHの環境下で6時間、次いで3)40℃、80%RHの環境下で6時間、次いで4)−5℃、20%RHの環境下で6時間保存し、これを1サイクルとして、計30サイクル(30日)の環境変動試験を行った。
各照明装置を構成する有機EL素子に対し、25℃、55%RHの環境下で、UV光(波長365nm、220mW/cm2)を5時間照射した後、UV光照射前後における各有機EL素子の正面輝度におけるCIE1931、x、y値を測定し、各x、y値の変動距離Δx、Δyを求め、耐熱性の評価と同様にして変動最大距離ΔEを算出し、これを耐光性の尺度とした。表2には、有機EL素子1のΔEを100とする相対値を求めた。値が小さいほど、UV光を照射された後でも、色度変動が少なく、白色発光からの色変動が少なく色度安定性(耐光性)が良好であることを意味する。なお、正面輝度の測定については分光放射輝度計CS−1000(コニカミノルタセンシング社製)を用いた。
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ー
12 駆動トランジスター
13 コンデンサー
A 表示部
B 制御部
101 有機EL素子
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 (5)
- 陽極と陰極との間に、正孔輸送層、ホスト化合物とリン光発光性化合物とを含有する発光層、正孔阻止層及び電子輸送層を有する有機エレクトロルミネッセンス素子であって、前記発光層を構成する前記ホスト化合物のLUMO(最低空分子軌道)のエネルギー準位の絶対値をL1(eV)とし、前記正孔阻止層を構成する正孔阻止化合物のLUMOのエネルギー準位の絶対値をL2(eV)とし、前記電子輸送層を構成する電子輸送化合物のLUMOのエネルギー準位の絶対値をL3(eV)としたとき、下式(I)で示す関係を満たし、かつ前記正孔阻止層が下記一般式(1)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。
式(I)
L1<L2≦1.50eV<L3
- 前記正孔阻止層を構成する正孔阻止化合物のLUMOのエネルギー準位の絶対値L2が、1.10〜1.50eVの範囲内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。
- 前記発光層が含有するリン光発光性化合物が、下記一般式(A)〜(C)で表される化合物から選ばれる少なくとも1種の化合物であることを特徴とする請求項1又は請求項2に記載の有機エレクトロルミネッセンス素子。
- 加法混色により白色発光することを特徴とする請求項1から請求項3までのいずれか一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から請求項4までのいずれか一項に記載の有機エレクトロルミネッセンス素子が具備されていることを特徴とする照明装置。
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