JP6195836B2 - 光学スタック、及びプロセス - Google Patents
光学スタック、及びプロセス Download PDFInfo
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- JP6195836B2 JP6195836B2 JP2014535956A JP2014535956A JP6195836B2 JP 6195836 B2 JP6195836 B2 JP 6195836B2 JP 2014535956 A JP2014535956 A JP 2014535956A JP 2014535956 A JP2014535956 A JP 2014535956A JP 6195836 B2 JP6195836 B2 JP 6195836B2
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- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/115—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising active inorganic nanostructures, e.g. luminescent quantum dots
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Description
光がOLEDなどの多層デバイススタック中を進む場合、その光の光学挙動は、そのデバイススタック中の少なくとも1層、またはそれ以上、典型的にはすべての層による影響を受け得る。例えば、光が高屈折率の媒体からより低い屈折率のものへと進むとき、その入射光の角度に依存してある程度の反射がそれら2媒体間の界面で起こるだろう。ボトムエミッション型OLEDの場合、内部で発生した光は、出射するために有機層から進み、そして透明下部電極、その後、基板を通って進まなければならない。従来、一体化ITO/有機層は、ガラス基板の屈折率(n2≒1.5)よりはるかに高い屈折率(n1≒1.8)を有するので、相当な量の光がそのITO/有機層内で導波され得る。同様に、基板(n2≒1.5)から空気(n3≒1)に進む光もまたその基板および有機/ITO層内で導波されるだろう(図2参照)。
ナノ構造層は、従来のトップエミッション型OLEDにおけるITO層の代用にも適している。
ナノ構造層(126)を含むドナーフィルム(136)を転写フィルム(140)上に設ける工程(該ナノ構造層は、マトリックス(144)中に場合によっては分散されている複数のナノ構造体(128)を含む);および
前記ドナーフィルム(136)のナノ構造層(126)を前記部分光学スタック(130)の上面(134)に接触させる工程
を含む方法を提供する。
(i)複数のナノ構造体(128)を剥離ライナ(144)上に堆積させる工程;
(ii)マトリックス(148)を複数のナノ構造体(128)上に形成する工程(該マトリックスは、上面(150)を有する);
(iii)転写フィルム(152)をマトリックス(148)の上面(150)に接触させる工程;および
(iv)剥離ライナ(144)を除去して、ナノ構造体表面(156)を露出させる工程
によってドナーフィルム(160)を設ける工程;
基板(116)と、基板(116)上に配置されたカソード(120)と、カソード(120)上に配置された有機スタック(124)とを含む部分光学スタック(130)を設ける工程(該部分光学スタックは上面(134)を有する);
ナノ構造体表面(156)によりドナーフィルム(160)を前記部分光学スタックの上面(134)に接触させる工程
を含む。
(i)マトリックス(148)を剥離ライナ(144)上に形成する工程(該マトリックスは上面(150)を有する);
(ii)複数のナノ構造体(128)をマトリックス(148)の上面(150)上に堆積させる工程;
(iii)転写フィルム(152)を複数のナノ構造体(128)上に塗布する工程;
(iv)マトリックス(148)を再流動化させて再流動化マトリックスを形成する工程;
(v)転写フィルム(152)に圧力を印加して、転写フィルム(152)の下に位置するナノ構造体(128)を前記再流動化マトリックスに、該転写フィルムが該マトリックス(148)の上面(150)と接触するように圧入する工程;および
(vi)転写フィルム(152)を除去して上面(150)を露出させる工程
によってドナーフィルム(160)を設ける工程;
基板(116)と、基板(116)上に配置されたカソード(120)と、カソード(120)上に配置された有機スタック(124)とを含む部分光学スタック(130)を設ける工程(該部分光学スタックは上面(134)を有する);
ドナーフィルム(160)の上面(150)を部分光学スタック(130)の上面(134)と接触させる工程
を含む。
従来のボトムエミッション型デバイスでは、固体金属カソードが典型的に上部電極として使用される(図1参照)。その金属と有機スタックの界面では、表面プラズモンポラリトン(SPP)または双極子相互作用のためにエネルギー損失が起こり得る。かかるエネルギー損失は、そのデバイスの効率を低下させる。より高い金属表面粗度がこの界面でのエネルギー損失を低減させることは証明されている、例えば、Kooら、Nature Photonics 4、222(2010)またはAnら、Optics Express 8(5)、4041頁(2010)を参照されたし。
さらなる実施形態では、OLEDデバイスにおける光取り出しを、そのOLEDデバイスにおける散乱中心の効率を最大化することによってさらに増進させることができる。光は有機スタックを移動するとき、1つ以上のモードで伝搬する。伝搬光の挙動、とりわけ、別様に導波された光の挙動に干渉するように、散乱中心を戦略的に位置決めすることができる。詳細には、散乱中心を持たない光学スタック内では導波されたであろう光のエネルギー密度を、その光学スタックに散乱中心を含めることによって低減させることができる。しかし、高屈折率層(例えば、OLEDの有機層またはOPVセルの有機光活性層)を含む光学スタックについては、導波光は、散乱中心との、散乱中心を効率的に利用できないような量の相互作用を有するだろう。
一般的に言うと、本明細書に記載する透明導電体は、導電性ナノ構造体の薄い導電性膜である。前記透明導電体内で、1つ以上の電気伝導路が前記ナノ構造体間の連続的物理的接触によって確立される。電気的パーコレーション閾値に達するために十分なナノ構造体が存在すると、ナノ構造体の導電性網が形成される。したがって、電気的パーコレーション閾値は重要な値であり、この値より上で長期接続性を実現することができる。
一般に、ナノ構造層またはコーティングは、本明細書に記載する光/電気デバイスにおいて透明電極として動作する。ナノ構造層(透明導電体層とも呼ばれる)は、液体担体と複数の導電性ナノ構造体とを含む分散液(またはコーティング組成物)を堆積する工程、および前記液体担体を乾燥させる工程によって形成される。ナノ構造層を先ず転写フィルム上に形成し、その後、その光/電気デバイス内の下に位置する層に転写してもよい。
「マトリックス」は、金属ナノワイヤが分散されるまたは埋め込まれる固体状態材料を指す。ナノワイヤの光子がマトリックスから飛び出して導電性網への表面アクセスを可能にすることができる。マトリックスは、金属ナノワイヤのホストであり、および導電性層の1つの物理的形態を提供するものである。マトリックスは、金属ナノワイヤを有害環境因子、例えば、腐食および摩耗から保護する。詳細には、マトリックスは、その環境内の腐食要素、例えば水分、微量の酸、酸素、硫黄およびこれらに類するもの、の浸透性を有意に低下させる。
反射防止層は、屈折率整合原理に基づくレイリー膜(Rayleigh’s film)の形をとる場合もあり、または弱め合う干渉に基づく干渉膜である場合もある。
発光層は、1つの実施形態によると、OLED内の有機スタックの一成分である。発光層は、電流をアノード(30)とカソードの間に流したときに光を放射することができる有機材料であり得る。好ましくは、発光層は、リン光放射性材料を含有するが、蛍光放射性材料を使用することもできる。リン光材料は、かかる材料と関連づけられるより高い発光効率のため好ましい。発光層はまた、電子、正孔および/または励起子を捕捉することができる放射性材料がドープされた、電子および/または正孔を輸送することができるので、励起子は、該放射性材料から光電子放射メカニズムによって緩和する。発光層は、単一の材料、すなわち輸送特性と放射特性を併せ持つ材料を含むことができる。
光活性層は、光を電気に直接変換するPVセルの光吸収成分である、有機スタックの1タイプでもある。
本明細書において用いる場合、散乱中心は、光散乱を生じさせる不活性材料である光散乱材料によって形成される。前記光散乱材料としては、例えば、微粒子状散乱媒体または散乱促進剤(例えば、前駆体)が挙げられる。
従来のOLEDに適する任意の基板が本開示の様々な実施形態にも適する。硬質基板の例としては、ガラス、ポリカーボネート、アクリル樹脂、およびこれらに類するものが挙げられる。
銀ナノワイヤを、例えばY.Sun、B.Gates、B.Mayers、およびY.Xia、「Crystalline silver nanowires by soft solution processing」、Nanoletters 2(2):165−168、2002に記載されている「ポリオール」法に従って、ポリ(ビニルピロリドン)(PVP)の存在下でエチレングリコールに溶解した硝酸銀を還元することにより合成した。同時係属の共有米国特許出願第11/766,552号明細書に記載されている改良ポリオール法は、従来の「ポリオール」法でより高収率でより均一な銀ナノワイヤを生成する。この出願は、その全体が参照により本明細書に援用されている。結果として得られるナノワイヤは、主として約13μmから約17μmの長さおよび約34nmから約44nmの直径を有した。
金属ナノワイヤを堆積させるための典型的なコーティング組成物は、重量で、0.0025%から0.1%界面活性剤(例えば、好ましい範囲は、ZONYL(登録商標)FSO−100については0.0025%から0.05%である)、0.02%から4%粘度調整剤(例えば、好ましい範囲は、ヒドロキシプロピルメチルセルロール(HPMC)については0.02%から0.5%である)、94.5%から99.0%溶媒、および0.05%から1.4%金属ナノワイヤを含む。
ポリイミドコーティング溶液(例えば、SUNEVERポリイミド(0821型))を先ず基板上に堆積させ、1500rpmで回転させ、その後、90℃で乾燥させ、30分間、200℃で硬化させた。得られたサンプルのヘイズおよび透過率は、それぞれ0.1%および92.1%であった。1.2マイクロメートルの膜厚が測定された。
銀ナノワイヤを反射防止層、例えばポリイミド膜、上に堆積させて、導電性膜を形成した。標準ナノワイヤ懸濁液(0.4%AgNW、0.4%LMw HPMC、250ppm Triton X)を実施例2に従って先ず調製した。そのポリイミド膜上のコーティング溶液を1000rpmで回転させ、その後、90秒間、50℃で乾燥させ、90秒間、140℃でアニールした。得られたシート抵抗は、9オーム/sqであり、透過率は87.5%およびヘイズは3.9%である。
Claims (11)
- 光学スタックであって、
第一の電極と、
前記第一の電極の下に位置する有機スタックと、
該有機スタックの下に位置するナノ構造層(該ナノ構造層は複数の金属ナノ構造体を含む)と、
該ナノ構造層の下に位置する高インデックス層と、
該高インデックス層の下に位置する基板と
を含み、該高インデックス層が、該有機層と同じまたはそれより高い屈折率を有し、そして該ナノ構造層が第二の電極を形成するものであり、
前記光学スタック中の導波光をエネルギー密度分布曲線によって表したとき、前記ナノ構造層が、該エネルギー密度分布曲線の少なくとも10%と重なり合うように位置決めされる、光学スタック。 - 前記ナノ構造層が、高インデックスマトリックスを含み、該高インデックスマトリックスが、前記有機層と同じまたはそれより高い屈折率を有する、請求項1に記載の光学スタック。
- 前記ナノ構造層が、低インデックスマトリックスを含み、該低インデックスマトリックスが、前記有機層より低い屈折率を有する、請求項1に記載の光学スタック。
- 基板と、該基板上に配置されたカソードと、該カソード上に配置された有機スタックとを含む部分光学スタックを設ける工程(該部分光学スタックは上面を有する);
ナノ構造層を含むドナーフィルムを転写フィルム上に設ける工程(該ナノ構造層は、アノードを形成し、かつ、マトリックス中に場合によっては分散されている複数のナノ構造体を含む);および
該ドナーフィルムの該ナノ構造層を該部分光学スタックの該上面に接触させる工程
を含むプロセス。 - 前記転写フィルムを除去する工程をさらに含む、請求項4に記載のプロセス。
- (i)複数のナノ構造体を剥離ライナ上に堆積させる工程;
(ii)マトリックスを該複数のナノ構造体上に形成する工程(該マトリックスは、上面を有する);
(iii)転写フィルムを該マトリックスの該上面に接触させる工程;および
(iv)該剥離ライナを除去して、ナノ構造体表面を露出させる工程によってドナーフィルムを設ける工程(該ナノ構造体は、アノードを形成する);
基板と、該基板上に配置されたカソードと、該カソード上に配置された有機スタックとを含む部分光学スタックを設ける工程(該部分光学スタックは上面を有する);および
該ナノ構造体表面により該ドナーフィルムを該部分光学スタックの該上面に接触させる
工程
を含むプロセス。 - 前記転写フィルムを除去する工程をさらに含む、請求項6に記載のプロセス。
- (i)マトリックスを剥離ライナ上に形成する工程(該マトリックスは上面を有する);
(ii)アノードを形成する複数のナノ構造体を該マトリックスの上面に堆積させる工程;
(iii)該マトリックスを再流動化させて、再流動化マトリックスを形成する工程;
(iv)該ナノ構造体を該再流動化マトリックスに、該転写フィルムが該マトリックスの該上面に接触するように圧入する工程;
(v)該転写フィルムを除去して、該上面を露出させる工程
によってドナーフィルムを設ける工程;
基板と、該基板上に配置されたカソードと、該カソード上に配置された有機スタックとを含む部分光学スタックを設ける工程(該部分光学スタックは上面を有する);および
該ドナーフィルムの該上面を該部分光学スタックの該上面と接触させる工程
を含むプロセス。 - 前記ナノ構造体を前記再流動化マトリックスに圧入する工程が、該ナノ構造体を圧延する工程を含む、請求項8に記載のプロセス。
- 転写フィルムを前記複数のナノ構造体上に塗布する工程;および該転写フィルムに圧力を印加して、該ナノ構造体を該再流動化マトリックスに圧入する工程をさらに含む、請求項8に記載のプロセス。
- 前記剥離ライナを除去する工程をさらに含む、請求項8〜10のいずれか一項に記載のプロセス。
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