JP6970499B2 - 発光素子、発光装置、電子機器及び照明装置 - Google Patents
発光素子、発光装置、電子機器及び照明装置 Download PDFInfo
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- JP6970499B2 JP6970499B2 JP2016232228A JP2016232228A JP6970499B2 JP 6970499 B2 JP6970499 B2 JP 6970499B2 JP 2016232228 A JP2016232228 A JP 2016232228A JP 2016232228 A JP2016232228 A JP 2016232228A JP 6970499 B2 JP6970499 B2 JP 6970499B2
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- 150000003918 triazines Chemical class 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Description
<発光素子の構成例>
まず、本発明の一態様の発光素子の構成について、図1(A)(B)及び(C)を用いて、以下説明する。
まず、発光素子150の発光機構について、以下説明を行う。
(α)直接生成過程
(β)TTA過程
まず、EL層100が有する発光層130においてキャリア(電子または正孔)が再結合し、一重項励起子が形成される場合を説明する。
次に、発光層130におけるキャリアの再結合過程において形成された三重項励起子によって、一重項励起子が形成される場合について、説明する。
・Host(131):ホスト材料131
・Guest(132):ゲスト材料132(蛍光材料)
・SFH:ホスト材料131のS1準位
・TFH:ホスト材料131のT1準位
・SFG:ゲスト材料132(蛍光材料)のS1準位
・TFG:ゲスト材料132(蛍光材料)のT1準位
3H*+3H* → 3(HH)* → 3H**+H → 3H*+H (G2)
上記のように、TTAによって、一重項励起子の生成確率を向上させ、発光素子の発光効率を向上させることが可能となるが、高い発光効率を得るためには、TTAが生じる確率(TTA効率ともいう)を高めることが重要である。すなわち、発光素子が呈する発光のうち、TTAによる遅延蛍光成分の占める割合が高いことが重要である。
例えば、ホスト材料として一般的に用いられているアントラセン化合物を有する青色の発光を呈する発光素子において、発光のうちTTAによる遅延蛍光成分の占める割合が10%程度である。なお、本明細書において遅延蛍光は、発光層への定常的なキャリア注入を遮断した後も、定常的にキャリアが注入されている時の発光強度に対して、0.01以上の強度比が、1×10−6sec以上持続して得られるような発光とする。
電子輸送層118が有する材料と発光効率の関係については上述の通りである。次に、正孔輸送層112が有する材料と発光効率の関係について説明する。
次に、発光層130に生じた三重項励起エネルギーを発光層130に留め、発光層130の外部に移動することを抑制することについて説明する。
発光層からの発光における遅延蛍光成分を評価する方法について、その一例を説明する。
有機ELでは、キャリアが発光層に供給され、発光層中でキャリアの再結合が生じることにより発光層に含まれるゲスト材料から発光が生じるが、該発光は等方的ではない場合、すなわち発光強度に角度依存性がある場合がある。該発光は該ゲスト材料の遷移双極子モーメントに垂直な方向に生じる。よって遷移双極子モーメントの向きが、発光の角度依存性に影響を及ぼすことになる。有機分子の遷移双極子モーメントの向きは、有機分子の分子配向に影響を受けるため、該ゲスト分子の分子配向に起因して該ゲスト材料からの発光が異方性を有する場合がある。
次に、本発明の一態様に係わる発光素子の構成要素の詳細について、以下説明を行う。
発光層130中では、ホスト材料131が少なくともゲスト材料132より重量比で多く存在し、ゲスト材料132(蛍光材料)は、ホスト材料131中に分散される。発光層130において、ホスト材料131に用いることができる材料としては、呈する発光のうち三重項−三重項消滅(TTA)による遅延蛍光成分の占める割合が高い有機化合物が好ましい。具体的には、TTAによる遅延蛍光成分の占める割合が20%以上である有機化合物が好ましい。また、発光層130において、ホスト材料131は、一種の化合物から構成されていても良く、複数の化合物から構成されていても良い。
電極101及び電極102は、発光層130へ正孔と電子を注入する機能を有する。電極101及び電極102は、金属、合金、導電性化合物、およびこれらの混合物や積層体などを用いて形成することができる。金属としてはアルミニウムが典型例であり、その他、銀、タングステン、クロム、モリブデン、銅、チタンなどの遷移金属、リチウムやセシウムなどのアルカリ金属、カルシウム、マグネシウムなどの第2族金属を用いることができる。遷移金属としてイッテルビウム(Yb)などの希土類金属を用いても良い。合金としては、上記金属を含む合金を使用することができ、例えばMgAg、AlLiなどが挙げられる。導電性化合物としては、酸化インジウム−酸化スズ(Indium Tin Oxide)などの金属酸化物が挙げられる。導電性化合物としてグラフェンなどの無機炭素系材料を用いても良い。上述したように、これらの材料の複数を積層することによって電極101及び電極102の一方または双方を形成しても良い。
正孔注入層111は、一対の電極の一方(電極101または電極102)からのホール注入障壁を低減することでホール注入を促進する機能を有し、例えば遷移金属酸化物、フタロシアニン誘導体、あるいは芳香族アミンなどによって形成される。遷移金属酸化物としては、モリブデン酸化物やバナジウム酸化物、ルテニウム酸化物、タングステン酸化物、マンガン酸化物などが挙げられる。フタロシアニン誘導体としては、フタロシアニンや金属フタロシアニンなどが挙げられる。芳香族アミンとしてはベンジジン誘導体やフェニレンジアミン誘導体などが挙げられる。ポリチオフェンやポリアニリンなどの高分子化合物を用いることもでき、例えば自己ドープされたポリチオフェンであるポリ(エチレンジオキシチオフェン)/ポリ(スチレンスルホン酸)などがその代表例である。
正孔輸送層112は正孔輸送性材料を含む層であり、正孔注入層111の材料として例示した材料を使用することができる。正孔輸送層112は正孔注入層111に注入された正孔を発光層130へ輸送する機能を有するため、正孔注入層111の最高被占軌道(Highest Occupied Molecular Orbital、HOMOともいう)準位と同じ、あるいは近いHOMO準位を有することが好ましい。
電子輸送層118は、電子注入層119を経て一対の電極の他方(電極101または電極102)から注入された電子を発光層130へ輸送する機能を有する。電子輸送性材料としては、正孔よりも電子の輸送性の高い材料を用いることができ、1×10−6cm2/Vs以上の電子移動度を有する材料であることが好ましい。具体的には、キノリン配位子、ベンゾキノリン配位子、オキサゾール配位子、あるいはチアゾール配位子を有する金属錯体、オキサジアゾール誘導体、トリアゾール誘導体、フェナントロリン誘導体、ピリジン誘導体、ビピリジン誘導体、ピリミジン誘導体などが挙げられる。
電子注入層119は電極102からの電子注入障壁を低減することで電子注入を促進する機能を有し、例えば第1族金属、第2族金属、あるいはこれらの酸化物、ハロゲン化物、炭酸塩などを用いることができる。また、先に示す電子輸送性材料と、これに対して電子供与性を示す材料の複合材料を用いることもできる。電子供与性を示す材料としては、第1族金属、第2族金属、あるいはこれらの酸化物などを挙げることができる。
また、発光素子150は、ガラス、プラスチックなどからなる基板上に作製すればよい。基板上に作製する順番としては、電極101側から順に積層しても、電極102側から順に積層しても良い。
本実施の形態では実施の形態1で説明した本発明の一態様に係る発光素子の構成例について図5乃至図7を用いて以下に説明する。
本発明の一態様に係る発光素子の構成例について、図5を用いて、以下説明を行う。図5は、本発明の一態様の発光素子を示す断面図である。
次に、図5に示す発光素子と異なる構成例について、図6(A)(B)を用いて、以下説明を行う。
さらに、発光素子252及び発光素子254は、マイクロキャビティ構造を有する。
本実施の形態においては、実施の形態1および実施の形態2に示す構成と異なる構成の発光素子、及び当該発光素子の発光機構について、図7及び図8を用いて、以下説明を行う。
図7(A)は、発光素子450の断面模式図である。
発光層420の発光機構としては、図1(A)に示す発光層130と同様の発光機構である。
次に、発光層430の発光機構について、以下説明を行う。
・Host(431_1):有機化合物431_1(ホスト材料)
・Assist(431_2):有機化合物431_2(アシスト材料)
・Guest(432):ゲスト材料432(燐光材料)
・Exciplex:励起錯体
・SPH:有機化合物431_1の一重項励起状態の最も低い準位
・TPH:有機化合物431_1の三重項励起状態の最も低い準位
・TPG:ゲスト材料432(燐光材料)の三重項励起状態の最も低い準位
・SE:励起錯体の一重項励起状態の最も低い準位
・TE:励起錯体の三重項励起状態の最も低い準位
次に、発光層420及び発光層430に用いることのできる材料について、以下説明する。
発光層420に用いることのできる材料としては、先の実施の形態1に示す発光層130に用いることのできる材料を援用すればよい。
発光層430中では、有機化合物431_1(ホスト材料)が重量比で最も多く存在し、ゲスト材料432(燐光材料)は、有機化合物431_1(ホスト材料)中に分散される。
次に、図7に示す発光素子と異なる構成例について、図8(A)(B)を用いて、以下説明を行う。
発光層420の発光機構としては、図1(A)に示す発光層130と同様の発光機構である。
発光層430の発光機構としては、図7(A)に示す発光層430と同様の発光機構である。
発光層420及び発光層430のそれぞれの発光機構について、既に説明したが、発光素子452に示すように、発光層420と、発光層430とが互いに接する構成を有する場合、発光層420と発光層430の界面において、励起錯体から発光層420のホスト材料421へのエネルギー移動(とくに三重項励起準位のエネルギー移動)が起こったとしても、発光層420にて上記三重項励起エネルギーを発光に変換することができる。
・Fluorescence EML(420):蛍光発光層(発光層420)
・Phosphorescence EML(430):燐光発光層(発光層430)
・SFH:ホスト材料421の一重項励起状態の最も低い準位
・TFH:ホスト材料421の三重項励起状態の最も低い準位
・SFG:ゲスト材料422(蛍光材料)の一重項励起状態の最も低い準位
・TFG:ゲスト材料422(蛍光材料)の三重項励起状態の最も低い準位
・SPH:ホスト材料(有機化合物431_1)の一重項励起状態の最も低い準位
・TPH:ホスト材料(有機化合物431_1)の三重項励起状態の最も低い準位
・TPG:ゲスト材料432(燐光材料)の三重項励起状態の最も低い準位
・SE:励起錯体の一重項励起状態の最も低い準位
・TE:励起錯体の三重項励起状態の最も低い準位
次に、発光層420及び発光層430に用いることのできる材料について、以下説明する。
発光層420中では、ホスト材料421が重量比で最も多く存在し、ゲスト材料422(蛍光材料)は、ホスト材料421中に分散される。ホスト材料421のS1準位は、ゲスト材料422(蛍光材料)のS1準位よりも高く、ホスト材料421のT1準位は、ゲスト材料422(蛍光材料)のT1準位よりも低いことが好ましい。
発光層430中では、ホスト材料(有機化合物431_1または有機化合物431_2)が重量比で最も多く存在し、ゲスト材料432(燐光材料)は、ホスト材料(有機化合物431_1及び有機化合物431_2)中に分散される。発光層430のホスト材料(有機化合物431_1及び有機化合物431_2)のT1準位は、発光層420のゲスト材料422(蛍光材料)のT1準位よりも高いことが好ましい。
本実施の形態では、本発明の一態様の発光素子を有する表示装置について、図9を用いて説明を行う。
図9(A)に示す表示装置は、表示素子の画素を有する領域(以下、画素部802という)と、画素部802の外側に配置され、画素を駆動するための回路を有する回路部(以下、駆動回路部804という)と、素子の保護機能を有する回路(以下、保護回路806という)と、端子部807と、を有する。なお、保護回路806は、設けない構成としてもよい。
図9(A)に示す複数の画素回路801は、例えば、図9(B)に示す構成とすることができる。
本実施の形態においては、本発明の一態様の発光素子を有する表示装置、及び該表示装置に入力装置を取り付けた電子機器について、図10乃至図14を用いて説明を行う。
なお、本実施の形態において、電子機器の一例として、表示装置と、入力装置とを合わせたタッチパネル2000について説明する。また、入力装置の一例として、タッチセンサを用いる場合について説明する。
次に、図11(A)を用いて、表示装置2501の詳細について説明する。図11(A)は、図10(B)に示す一点鎖線X1−X2間の断面図に相当する。
次に、図11(C)を用いて、タッチセンサ2595の詳細について説明する。図11(C)は、図10(B)に示す一点鎖線X3−X4間の断面図に相当する。
次に、図12(A)を用いて、タッチパネル2000の詳細について説明する。図12(A)は、図10(A)に示す一点鎖線X5−X6間の断面図に相当する。
次に、タッチパネルの駆動方法の一例について、図13を用いて説明を行う。
また、図13(A)ではタッチセンサとして配線の交差部に容量2603のみを設けるパッシブマトリクス型のタッチセンサの構成を示したが、トランジスタと容量とを有するアクティブマトリクス型のタッチセンサとしてもよい。アクティブマトリクス型のタッチセンサに含まれるセンサ回路の一例を図14に示す。
本実施の形態では、本発明の一態様の発光素子を有する表示モジュール及び電子機器について、図15及び図16を用いて説明を行う。
図15に示す表示モジュール8000は、上部カバー8001と下部カバー8002との間に、FPC8003に接続されたタッチセンサ8004、FPC8005に接続された表示装置8006、フレーム8009、プリント基板8010、バッテリ8011を有する。
図16(A)乃至図16(G)は、電子機器を示す図である。これらの電子機器は、筐体9000、表示部9001、スピーカ9003、操作キー9005(電源スイッチ、又は操作スイッチを含む)、接続端子9006、センサ9007(力、変位、位置、速度、加速度、角速度、回転数、距離、光、液、磁気、温度、化学物質、音声、時間、硬度、電場、電流、電圧、電力、放射線、流量、湿度、傾度、振動、におい又は赤外線を測定する機能を含むもの)、マイクロフォン9008、等を有することができる。
本実施の形態では、本発明の一態様である発光素子を適用した照明装置の一例について、図17を用いて説明する。
まず、ガラス製の基板900上に酸化珪素を含むインジウム錫酸化物(ITO)をスパッタリング法により成膜し、陽極として機能する第1の電極901を形成した。なお、その膜厚は70nmとし、電極面積は2mm×2mmとした。
作製した発光素子1乃至発光素子8(各4つ)について、測定にはピコ秒蛍光寿命測定システム(浜松ホトニクス社製)を用いた。本測定では、発光素子における蛍光発光の寿命を測定するため、発光素子に矩形パルス電圧を印加し、その電圧の立下りから減衰していく発光をストリークカメラにより時間分解測定した。パルス電圧は10Hzの周期で印加し、繰り返し測定したデータを積算することにより、S/N比の高いデータを得た。また、測定は室温(300K)で、印加パルス電圧が3V前後、印加パルス時間幅が100μsec、負バイアス電圧が−5V、測定時間範囲が50μsecの条件で行った。
まず、測定対象の発光素子9の作成について図18を用いて説明する。まず、ガラス製の基板900上に酸化珪素を含むインジウム錫酸化物(ITO)をスパッタリング法により成膜し、陽極として機能する第1の電極901を形成した。なお、その膜厚は70nmとし、電極面積は2mm×2mmとした。
次に、測定について説明する。検出器には、マルチチャネル分光光度計として浜松ホトニクス製「PMA−12」を用いた。発光素子9から検出器への光路にEdmund optics社製偏光プリズムを設置し、観測方向に対して平行な偏光成分のみが検出器に到達するようにした。偏光プリズムを通過した光は「PMA−12」(マルチチャネル分光光度計:浜松ホトニクス製)にて検出され、発光スペクトルを得た。この時、基板の発光面の正面を0度とし、0度から80度まで1度刻みに基板を回転させ、各角度において発光スペクトルを測定しスペクトルの面積強度をプロットした。
次に計算について説明する。計算はCYBERNET社製の有機デバイスシミュレータ「setfos」を使用した。パラメータとして、素子の積層構造と膜厚、各層の屈折率nと消衰係数k、発光位置、発光スペクトルをそれぞれ設定し、発光分子の遷移双極子モーメントの配向度合を変動パラメータとしてフィッティングを行った(後述のパラメータa)。なお、発光位置は正孔輸送層/発光層界面近傍と仮定した。また、各層の膜厚はサンプル作製時の蒸着機の水晶振動子(レートモニタ)の値、屈折率nと消衰係数kは各層薄膜の分光エリプソメトリーの解析結果から求めた。また、発光スペクトルは薄膜の光励起スペクトル(PL)を使用した。
図29に角度依存特性の実測プロットと計算結果を示す。計算はa=0(遷移双極子モーメントが完全水平)、a=0.16、a=0.33(遷移双極子モーメントがランダム配向)、a=1(遷移双極子モーメントが完全垂直)における結果を図に示す。角度依存特性の実測プロットと、計算の結果を合わせると、遷移双極子モーメントの84%の成分が発光層に平行方向の成分であり、16%が垂直方向の成分である状態(a=0.16)の計算結果が、実測プロットと良く対応した。そのため、発光素子9の発光層913が有する発光分子の遷移双極子モーメントは、84%の成分が発光層913に平行方向の成分であり、遷移双極子モーメントの多くは発光層の垂直方向から傾いた状態で配向していると推定された。
101 電極
101a 導電層
101b 導電層
102 電極
103 電極
103a 導電層
103b 導電層
104 電極
104a 導電層
104b 導電層
111 正孔注入層
112 正孔輸送層
113 電子輸送層
114 電子注入層
115 電荷発生層
116 正孔注入層
117 正孔輸送層
118 電子輸送層
119 電子注入層
123B 発光層
123G 発光層
123R 発光層
130 発光層
131 ホスト材料
132 ゲスト材料
140 隔壁
150 発光素子
160 発光層
170 発光層
170a 発光層
170b 発光層
180 検出器の観測方向
181 遷移双極子モーメントの成分
182 遷移双極子モーメントの成分
183 遷移双極子モーメントの成分
185 検出器
200 基板
220 基板
221B 領域
221G 領域
221R 領域
222B 領域
222G 領域
222R 領域
223 遮光層
224B 光学素子
224G 光学素子
224R 光学素子
250 発光素子
252 発光素子
254 発光素子
400 EL層
401 電極
402 電極
411 正孔注入層
412 正孔輸送層
413 電子輸送層
414 電子注入層
416 正孔注入層
417 正孔輸送層
418 電子輸送層
419 電子注入層
420 発光層
421 ホスト材料
422 ゲスト材料
430 発光層
431 ホスト材料
431_1 有機化合物
431_2 有機化合物
432 ゲスト材料
441 発光ユニット
442 発光ユニット
445 電荷発生層
450 発光素子
452 発光素子
801 画素回路
802 画素部
804 駆動回路部
804a 走査線駆動回路
804b 信号線駆動回路
806 保護回路
807 端子部
852 トランジスタ
854 トランジスタ
862 容量素子
872 発光素子
900 基板
901 第1の電極
902 EL層
903 第2の電極
911 正孔注入層
912 正孔輸送層
913 発光層
914 電子輸送層
915 電子注入層
2000 タッチパネル
2001 タッチパネル
2501 表示装置
2502R 画素
2502t トランジスタ
2503c 容量素子
2503g 走査線駆動回路
2503t トランジスタ
2509 FPC
2510 基板
2510a 絶縁層
2510b 可撓性基板
2510c 接着層
2511 配線
2519 端子
2521 絶縁層
2528 隔壁
2550R 発光素子
2560 封止層
2567BM 遮光層
2567p 反射防止層
2567R 着色層
2570 基板
2570a 絶縁層
2570b 可撓性基板
2570c 接着層
2580R 発光モジュール
2590 基板
2591 電極
2592 電極
2593 絶縁層
2594 配線
2595 タッチセンサ
2597 接着層
2598 配線
2599 接続層
2601 パルス電圧出力回路
2602 電流検出回路
2603 容量
2611 トランジスタ
2612 トランジスタ
2613 トランジスタ
2621 電極
2622 電極
8000 表示モジュール
8001 上部カバー
8002 下部カバー
8003 FPC
8004 タッチセンサ
8005 FPC
8006 表示装置
8009 フレーム
8010 プリント基板
8011 バッテリ
8501 照明装置
8502 照明装置
8503 照明装置
8504 照明装置
9000 筐体
9001 表示部
9003 スピーカ
9005 操作キー
9006 接続端子
9007 センサ
9008 マイクロフォン
9050 操作ボタン
9051 情報
9052 情報
9053 情報
9054 情報
9055 ヒンジ
9100 携帯情報端末
9101 携帯情報端末
9102 携帯情報端末
9200 携帯情報端末
9201 携帯情報端末
Claims (15)
- 請求項1または請求項2において、
前記EL層が呈する発光において、三重項−三重項消滅による遅延蛍光成分の占める割合が全体の15%以上である、発光素子。 - 請求項1乃至請求項3のいずれか一項において、
前記第1の材料が、ジアジン骨格又はトリアジン骨格を有する縮合複素芳香環骨格を含む物質である発光素子。 - 請求項1乃至請求項3のいずれか一項において、
前記第1の材料が、ピラジン骨格又はピリミジン骨格を有する物質である発光素子。 - 請求項1乃至請求項5のいずれか一項において、
前記第1の材料の三重項励起エネルギーが、前記発光層に含まれる材料のうち最も三重項励起エネルギーの高い物質の三重項励起エネルギーに比べ、0.2eV以上高い、発光素子。 - 請求項1乃至請求項6のいずれか一項において、
前記発光層に接する正孔輸送層を有し、
前記正孔輸送層は、第2の材料を有し、
前記第2の材料のLUMO準位が、前記ホスト材料のLUMO準位よりも高い、発光素子。 - 請求項1乃至請求項6のいずれか一項において、
前記発光層に接する正孔輸送層を有し、
前記正孔輸送層は、第2の材料を有し、
前記第2の材料の三重項励起エネルギーが、前記発光層に含まれる材料のうち最も三重項励起エネルギーの高い物質の三重項励起エネルギーに比べ、0.2eV以上高い、発光素子。 - 請求項1乃至請求項8のいずれか一項において、
前記発光層は蛍光材料をさらに含む発光素子。 - 請求項9において、
前記蛍光材料の三重項励起エネルギーが、前記ホスト材料の三重項励起エネルギーよりも高い、発光素子。 - 請求項9または請求項10において、
前記蛍光材料のLUMO準位は前記ホスト材料のLUMO準位と同じか、それよりも高い、発光素子。 - 請求項1乃至請求項11のいずれか一項において、
前記発光層が青色の発光を呈する発光素子。 - 請求項1乃至請求項12のいずれか一項に記載の発光素子と、
トランジスタ、または、基板と、を有する発光装置。 - 請求項13に記載の発光装置と、
センサ、操作ボタン、スピーカ、または、マイクと、を有する電子機器。 - 請求項13に記載の発光装置と、筐体と、を有する照明装置。
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US10573837B2 (en) | 2020-02-25 |
US20170155072A1 (en) | 2017-06-01 |
US20210391553A1 (en) | 2021-12-16 |
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US11050032B2 (en) | 2021-06-29 |
TW202211510A (zh) | 2022-03-16 |
WO2017093843A1 (en) | 2017-06-08 |
JP2022009708A (ja) | 2022-01-14 |
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