JP2004088094A - Composite, film forming method and film forming apparatus, electro-optical device and its manufacturing method, and organic electro-luminescence device and its manufacturing method, and electronic apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite which can suppress a physical property change with time when materials for pattern forming are liquefied, and to provide a forming apparatus which can form film patterns with high productivity using the liquefied composite. <P>SOLUTION: This film forming apparatus is provided with a composite adjusting unit S which generates liquefied composite including an organic functional material, a solvent and an oxidization prevention agent, and a liquid-drop jet unit IJ which jets to a substrate P liquid drops composed of the liquefied composites generated in the composite adjusting unit S. <P>COPYRIGHT: (C)2004,JPO

Description

【００８０】
このような共役系高分子有機化合物は固体で強い蛍光を持ち、均質な固体超薄膜を形成することができる。しかも形成能に富みＩＴＯ電極との密着性も高い。さらに、このような化合物の前駆体は、硬化した後は強固な共役系高分子膜を形成することから、加熱硬化前においては前駆体溶液を後述する液滴吐出パターニングに適用可能な所望の粘度に調整することができ、簡便かつ短時間で最適条件の膜形成を行うことができる。
【００８１】
このような前駆体としては、例えばＰＰＶ（ポリ（パラ−フェニレンビニレン））またはその誘導体の前駆体が好ましい。ＰＰＶまたはその誘導体の前駆体は、水あるいは有機溶媒に可溶であり、また、ポリマー化が可能であるため光学的にも高品質の薄膜を得ることができる。さらに、ＰＰＶは強い蛍光を持ち、また二重結合のπ電子がポリマー鎖上で非極在化している導電性高分子でもあるため、高性能の有機ＥＬ素子を得ることができる。
【００８２】
このようなＰＰＶまたはＰＰＶ誘導体の前駆体として、例えば化学式（ＩＩ）に示すような、ＰＰＶ（ポリ（パラ−フェニレンビニレン））前駆体、ＭＯ−ＰＰＶ（ポリ（２，５−ジメトキシ−１，４−フェニレンビニレン））前駆体、ＣＮ−ＰＰＶ（ポリ（２，５−ビスヘキシルオキシ−１，４−フェニレン−（１−シアノビニレン）））前駆体、ＭＥＨ−ＰＰＶ（ポリ［２−メトキシ−５−（２’−エチルヘキシルオキシ）］−パラ−フェニレンビニレン）前駆体等が挙げられる。
【００８３】
【化２】

【００８４】
ＰＰＶまたはＰＰＶ誘導体の前駆体は、前述したように水に可溶であり、成膜後の加熱により高分子化してＰＰＶ層を形成する。前記ＰＰＶ前駆体に代表される前駆体の含有量は、組成物全体に対して０．０１〜１０．０ｗｔ％が好ましく、０．１〜５．０ｗｔ％がさらに好ましい。前駆体の添加量が少な過ぎると共役系高分子膜を形成するのに不十分であり、多過ぎると組成物の粘度が高くなり、インクジェット法による精度の高いパターニングに適さない場合がある。
【００８５】
さらに、発光層の形成材料としては、少なくとも１種の蛍光色素を含むのが好ましい。これにより、発光層の発光特性を変化させることができ、例えば、発光層の発光効率の向上、または光吸収極大波長（発光色）を変えるための手段としても有効である。すなわち、蛍光色素は単に発光層材料としてではなく、発光機能そのものを担う色素材料として利用することができる。例えば、共役系高分子有機化合物分子上のキャリア再結合で生成したエキシトンのエネルギーをほとんど蛍光色素分子上に移すことができる。この場合、発光は蛍光量子効率が高い蛍光色素分子からのみ起こるため、発光層の電流量子効率も増加する。したがって、発光層の形成材料中に蛍光色素を加えることにより、同時に発光層の発光スペクトルも蛍光分子のものとなるので、発光色を変えるための手段としても有効となる。
【００８６】
なお、ここでいう電流量子効率とは、発光機能に基づいて発光性能を考察するための尺度であって、下記式により定義される。
ηＥ　＝放出されるフォトンのエネルギー／入力電気エネルギー
そして、蛍光色素のドープによる光吸収極大波長の変換によって、例えば赤、青、緑の３原色を発光させることができ、その結果フルカラー表示体を得ることが可能となる。
さらに蛍光色素をドーピングすることにより、ＥＬ素子の発光効率を大幅に向上させることができる。
【００８７】
蛍光色素としては、赤色の発色光を発光する発光層を形成する場合、赤色の発色光を有するローダミンまたはローダミン誘導体を用いるのが好ましい。これらの蛍光色素は、低分子であるため水溶液に可溶であり、またＰＰＶと相溶性がよく、均一で安定した発光層の形成が容易である。このような蛍光色素として具体的には、ローダミンＢ、ローダミンＢベース、ローダミン６Ｇ、ローダミン１０１過塩素酸塩等が挙げられ、これらを２種以上混合したものであってもよい。
【００８８】
また、緑色の発色光を発光する発光層を形成する場合、緑色の発色光を有するキナクリドンおよびその誘導体を用いるのが好ましい。これらの蛍光色素は前記赤色蛍光色素と同様、低分子であるため水溶液に可溶であり、またＰＰＶと相溶性がよく発光層の形成が容易である。
【００８９】
さらに、青色の発色光を発光する発光層を形成する場合、青色の発色光を有するジスチリルビフェニルおよびその誘導体を用いるのが好ましい。これらの蛍光色素は前記赤色蛍光色素と同様、低分子であるため水・アルコール混合溶液に可溶であり、またＰＰＶと相溶性がよく発光層の形成が容易である。
【００９０】
また、青色の発色光を有する他の蛍光色素としては、クマリンおよびその誘導体を挙げることができる。これらの蛍光色素は、前記赤色蛍光色素と同様、低分子であるため水溶液に可溶であり、またＰＰＶと相溶性がよく発光層の形成が容易である。このような蛍光色素として具体的には、クマリン、クマリン−１、クマリン−６、クマリン−７、クマリン１２０、クマリン１３８、クマリン１５２、クマリン１５３、クマリン３１１、クマリン３１４、クマリン３３４、クマリン３３７、クマリン３４３等が挙げられる。
【００９１】
さらに、別の青色の発色光を有する蛍光色素としては、テトラフェニルブタジエン（ＴＰＢ）またはＴＰＢ誘導体を挙げることができる。これらの蛍光色素は、前記赤色蛍光色素等と同様、低分子であるため水溶液に可溶であり、またＰＰＶと相溶性がよく発光層の形成が容易である。
以上の蛍光色素については、各色ともに１種のみを用いてもよく、また２種以上を混合して用いてもよい。
【００９２】
これらの蛍光色素については、前記共役系高分子有機化合物の前駆体固型分に対し、０．５〜１０ｗｔ％添加するのが好ましく、１．０〜５．０ｗｔ％添加するのがより好ましい。蛍光色素の添加量が多過ぎると発光層の耐候性および耐久性の維持が困難となり、一方、添加量が少な過ぎると、前述したような蛍光色素を加えることによる効果が十分に得られないからである。
【００９３】
また、前記前駆体および蛍光色素については、極性溶媒に溶解または分散させて液状体組成物とし、この液状体組成物を液滴吐出ヘッド２０から吐出するのが好ましい。極性溶媒は、前記前駆体、蛍光色素等を容易に溶解または均一に分散させることができるため、液滴吐出ヘッド２０のノズル孔での発光層形成材料中の固型分が付着したり目詰りを起こすのを防止することができる。
【００９４】
このような極性溶媒として具体的には、水、メタノール、エタノール等の水と相溶性のあるアルコール、Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、Ｎ−メチルピロリドン（ＮＭＰ）、ジメチルイミダゾリン（ＤＭＩ）、ジメチルスルホキシド（ＤＭＳＯ）、キシレン、シクロヘキシルベンゼン、２，３−ジヒドロベンゾフラン等の有機溶媒または無機溶媒が挙げられ、これらの溶媒を２種以上適宜混合したものであってもよい。
【００９５】
発光層に添加する酸化防止剤としては、上述したラジカル連鎖禁止剤（一次酸化防止剤）、あるいは過酸化物分解剤（二次酸化防止剤）を用いることができる。発光層に添加する酸化防止剤の溶解パラメータも、７．０〜１３．０のものを用いることが好ましく、更に好ましくは溶解パラメータが７．５〜１０．５であるものを用いることが望ましい。このような酸化防止剤は、溶媒に対して高い溶解性・分散性を有するので、発光層形成用材料と相溶し、十分に分散され、成膜後においても相分離が生じない。そして、上記酸化防止剤を発光層に含有することにより、酸化防止剤が十分に分散されることによって発光ムラが生じるのを抑えることができる。
【００９６】
また、酸化防止剤の溶媒に対する溶解度は０．００１％以上好ましくは５％以上である酸化防止剤を用いることが望ましい。これにより、酸化防止剤は溶媒に溶解し、成膜後においても相分離が生じない。更に、酸化防止剤の添加量は発光層形成用材料に対して０．００１〜３０ｗｔ％好ましくは０．１〜１０ｗｔ％以下であることが望ましい。添加量を上記範囲に設定することにより、所望の酸化防止機能を得ることができるとともに、発光層自体の機能も損なうことがない。
【００９７】
また、発光層に含有する酸化防止剤も、透明あるいは半透明であることが好ましい。これにより、酸化防止剤による発光層の着色を防止し、発光色の変化や輝度の低下等、発光色に対する酸化防止剤の影響を抑えることができ、所望の発色状態を得ることができる。なお、発光層形成用材料に対する酸化防止剤の添加量が十分に少ない場合であれば、酸化防止剤が着色していても発光色に対する影響は少ない。
【００９８】
更に、前記形成用材料中に湿潤剤を添加しておくのが好ましい。これにより、形成用材料が液滴吐出ヘッド２０のノズル孔で乾燥・凝固することを有効に防止することができる。かかる湿潤剤としては、例えばグリセリン、ジエチレングリコール等の多価アルコールが挙げられ、これらを２種以上混合したものであってもよい。この湿潤剤の添加量としては、形成用材料の全体量に対し、５〜２０ｗｔ％程度とするのが好ましい。
なお、その他の添加剤、被膜安定化材料を添加してもよく、例えば、安定剤、粘度調整剤、老化防止剤、ｐＨ調整剤、防腐剤、樹脂エマルジョン、レベリング剤等を用いることができる。
【００９９】
このような発光層形成用材料を含む液状体組成物１１４Ｂを液滴吐出ヘッド２０から吐出すると、液状体組成物１１４Ｂは隔壁１５０内の正孔注入層１４０Ａ上に塗布される。
ここで、液状体組成物１１４Ｂの吐出による発光層の形成は、赤色の発色光を発光する発光層形成用材料を含む液状体組成物、緑色の発色光を発光する発光層形成用材料を含む液状体組成物、青色の発色光を発光する発光層形成用材料を含む液状体組成物を、それぞれ対応する画素７１に吐出し塗布することによって行う。なお、各色に対応する画素７１は、これらが規則的な配置となるように予め決められている。
【０１００】
このようにして各色の発光層形成用材料を含む液状体組成物１１４Ｂを吐出し塗布したら、液状体組成物１１４Ｂ中の溶媒を蒸発させることにより、図８（ｂ）に示すように正孔層注入層１４０Ａ上に固形の発光層１４０Ｂが形成され、これにより正孔層注入層１４０Ａと発光層１４０Ｂとからなる発光部１４０が得られる。ここで、発光層形成用材料を含む液状体組成物１１４Ｂ中の溶媒の蒸発については、必要に応じて加熱あるいは減圧等の処理を行うが、発光層形成用材料は通常乾燥性が良好で速乾性であることから、特にこのような処理を行うことなく、したがって各色の発光層形成用材料を順次吐出塗布することにより、その塗布順に各色の発光層１４０Ｂを形成することができる。
その後、図８（ｃ）に示すように、透明基板Ｐの表面全体に、あるいはストライプ状に反射電極１５４が形成される。こうして、有機ＥＬ素子が製造される。
【０１０１】
このような有機ＥＬ素子の製造方法において、正孔注入層１４０Ａや発光層１４０Ｂといった有機ＥＬ素子の構成要素となる薄膜は成膜装置（液滴吐出装置）ＩＪにより製造されるので、正孔注入層１４０Ａや発光層１４０Ｂの形成用材料となる液状体組成物のロスは少なく、正孔注入層１４０Ａや発光層１４０Ｂは比較的安価にしかも安定して形成される。
【０１０２】
なお、上記実施形態では、液状体組成物１１４Ｂ（１１４Ａ）に予め酸化防止剤を添加する構成であるが、酸化防止剤が添加されていない液状体組成物１１４Ｂ（１１４Ａ）を吐出して成膜した後、この膜に対して上記酸化防止剤を吐出し塗布するようにしてもよい。この場合、発光層形成用材料を含む膜を乾燥処理（熱処理）する前に、すなわち膜が濡れている状態で酸化防止剤を塗布することもできる。こうすることにより、基板Ｐ上において発光層形成用材料と酸化防止剤とを混合できる。もちろん、発光層形成用材料を含む膜を乾燥処理して溶媒を除いた後、この膜に対して酸化防止剤を塗布するようにしてもよい。この場合、発光層に隣接する酸化防止層が形成されることになる。
【０１０３】
また、酸化防止剤を塗布する際には、酸化防止剤のみ、酸化防止剤と溶媒とからなる第２の液状体組成物、及び酸化防止剤と溶媒とバインダ樹脂とからなる第２の液状体組成物のいずれかの形態のものを塗布することができる。
【０１０４】
更に、上記実施形態では、液滴吐出装置ＩＪを用いた液滴吐出法により有機機能材料を成膜するように説明したが、液滴吐出法に限らず、例えばスピンコート法など他の塗布方法を用いることもできる。また、上記第２の液状体組成物を塗布する際にも他の塗布方法を用いることができる。
【０１０５】
また、液状体組成物の生成工程や成膜工程は大気環境下で行ってもよいし、窒素ガス等の不活性ガス雰囲気下で行ってもよい。なお、組成物調整装置Ｓによる液状体組成物の生成工程や液滴吐出装置ＩＪによる成膜工程は、クリーンルーム内でパーティクル及びケミカル的にクリーン度を維持された環境下で行うのが望ましい。液状体組成物を大気環境下で生成する際には、例えば常温常湿（一例として温度２５℃、湿度３５〜４５％）環境下において、有機機能材料及び酸化防止剤を溶媒に溶解することにより液状体組成物を生成してもよいし、有機機能材料を溶媒に溶解後、この溶液中に酸化防止剤を添加するようにしてもよい。
【０１０６】
上記実施形態では、正孔注入層及び発光層のそれぞれに酸化防止剤を添加した構成であるが、正孔注入層又は発光層のうちいずれか一方のみに酸化防止剤が添加された構成でもよい。あるいは、有機ＥＬ素子を構成する複数の層のうち、正孔注入層及び発光層以外の他の層に酸化防止剤を添加してもよい。
【０１０７】
《実施例》
以下、液状体組成物の材料組成、液状体組成物生成工程及び成膜工程の例を示す。
＜正孔注入層形成用液状体組成物Ｐ１＞
・バイトロンＰ：８８．５ｗｔ％
・ポリスチレンスルフォン酸：１１．５ｗｔ％
＜発光層形成用液状体組成物Ｅ１＞
・Ｇ（緑）：化合物１（０．７６ｇ）、化合物２（０．２０ｇ）、化合物３（０．０４ｇ）
・Ｂ（青）：化合物１（１．００ｇ）
・Ｒ（赤）：化合物４（１．００ｇ）
上記ＲＧＢのそれぞれに溶媒としてキシレン１００ｍｌ、及び上述した酸化防止剤１ｍｇを加えた。
【０１０８】
なお、上記化合物１〜化合物４は以下の通りである。
【０１０９】
【化３】

【０１１０】
【化４】

【０１１１】
【化５】

【０１１２】
【化６】

【０１１３】
＜正孔注入層形成用液状体組成物Ｐ２＞
・バイトロンＰ：１１．０８ｗｔ％
・ポリスチレンスルフォン酸：１．４４ｗｔ％
・イソプロピルアルコール：１０ｗｔ％
・Ｎ−メチルピロリドン：２７．４７ｗｔ％
・１，３−ジメチル−イミダゾリノン：５０ｗｔ％
＜発光層形成用液状体組成物Ｅ２＞
・Ｇ（緑）：化合物１（０．７６ｇ）、化合物２（０．２０ｇ）、化合物３（０．０４ｇ）
・Ｂ（青）：化合物１（１．００ｇ）
・Ｒ（赤）：化合物４（１．００ｇ）
上記ＲＧＢのそれぞれに溶媒としてシクロヘキシルベンゼン４０ｍｌ、及び２，３−ジヒドロベンゾフラン６０ｍｌを加え、上述した酸化防止剤１ｍｇを加えた。
【０１１４】
＜液状体組成物生成工程１＞
（工程例１）クリーンルーム大気環境下（室温２５℃、湿度３５〜４５％）において発光層形成用材料及び酸化防止剤を溶媒に溶解し、上記組成物Ｅ１、Ｅ２を生成した。
（工程例２）クリームルーム大気環境下（室温２５℃、湿度３５〜４５％）において発光層形成用材料を溶媒に溶解後、この溶液中に酸化防止剤を添加して上記組成物Ｅ１、Ｅ２を生成した。
【０１１５】
＜成膜工程１＞
（工程例１）クリームルーム大気環境下（室温２５℃、湿度３５〜４５％）において、まず、上記組成物Ｐ１をスピンコート法により成膜した。次いで、組成物Ｐ１により形成された膜を、大気環境下で、２００℃１０分間焼成処理を行った。次いで、形成された正孔注入層上に上記組成物Ｅ１を大気環境下、室温においてスピンコート法により成膜した。
（工程例２）クリームルーム大気環境下（室温２５℃、湿度３５〜４５％）において、液滴吐出法により上記組成物Ｐ２を基板上に吐出した。次いで、クリーンルーム内の圧力を１Ｔｏｒｒ（１３３．３２２Ｐａ以下）の真空状態とし、室温で２０分間乾燥処理し成膜した。次いで、この膜を、大気環境下で、２００℃１０分間焼成処理を行った。次いで、形成された正孔注入層上に上記組成物Ｅ２を液滴吐出法により吐出した。次いで、組成物Ｅ２からなる膜を大気環境下で４５℃２０分間乾燥処理し成膜した。
【０１１６】
＜液状体組成物の生成工程２＞
（工程例１）グローブボックス窒素ガス雰囲気下（室温、水分濃度及び酸素濃度１ｐｐｍ以下）において発光層形成用材料及び酸化防止剤を溶媒に溶解し、上記組成物Ｅ１、Ｅ２を生成した。
（工程例２）グローブボックス窒素ガス雰囲気下（室温、水分濃度及び酸素濃度１ｐｐｍ以下）において発光層形成用材料を溶媒に溶解後、この溶液中に酸化防止剤を添加して上記組成物Ｅ１、Ｅ２を生成した。
【０１１７】
＜成膜工程２＞
（工程例１）水分濃度及び酸素濃度１ｐｐｍ以下の窒素ガス雰囲気下において、スピンコート法により上記組成物Ｐ１を成膜した。次いで、組成物Ｐ１により形成された膜を、窒素ガス雰囲気下で、２００℃１０分間焼成処理を行った。次いで、形成された正孔注入層上に上記組成物Ｅ１を窒素ガス雰囲気下、室温においてスピンコート法により成膜した。
（工程例２）水分濃度及び酸素濃度１ｐｐｍ以下の窒素ガス雰囲気下において、液滴吐出法により上記組成物Ｐ２を基板上に吐出した。次いで、１Ｔｏｒｒ（１３３．３２２Ｐａ以下）の真空条件下、室温で２０分間乾燥処理し成膜した。次いで、この膜を、窒素ガス雰囲気下で、２００℃１０分間焼成処理を行った。次いで、形成された正孔注入層上に上記組成物Ｅ２を液滴吐出法により吐出し、窒素ガス雰囲気下、４５℃２０分間乾燥処理した。
【０１１８】
図９〜図１２に、発光層に酸化防止剤を添加した場合と添加しない場合とのそれぞれにおける有機ＥＬ素子の特性試験結果を示す。図中、「Ａ」が本発明に係る酸化防止剤を添加した場合の試験結果、「Ｂ」が酸化防止剤を添加しない場合の試験結果である。図９は印加電圧と電流密度との関係を示すグラフであり、図１０は印加電圧と輝度との関係を示すグラフである。また、図１１は印加電圧と発光効率との関係を示すグラフであり、図１２は駆動時間と輝度との関係を示すグラフである。図９及び図１０に示すように、酸化防止剤が添加されている有機ＥＬ素子と添加されていない有機ＥＬ素子との素子特性はほぼ同じであり、発光層に酸化防止剤が添加されても素子機能は損なわれないことが分かる。また、図１１及び図１２に示すように、発光効率及び輝度半減寿命は酸化防止剤が添加されたことにより向上しており、酸化防止剤を添加することにより素子機能が向上することが分かる。
【０１１９】
本発明の液滴吐出装置ＩＪは、カラーフィルタの構成要素となる膜の形成にも用いることができる。図１３は基板Ｐ上に形成されるカラーフィルタを示す図であり、図１４はカラーフィルタの製造手順を示す図である。
図１３に示すように、本例では長方形形状の基板Ｐ上に、生産性を向上させる観点から複数個のカラーフィルタ領域３５１をマトリクス状に形成する。これらカラーフィルタ領域３５１は、後で基板Ｐを切断することにより、液晶表示装置に適合するカラーフィルタとして用いることができる。
【０１２０】
カラーフィルタ領域３５１は、Ｒ（赤）の液状体組成物、Ｇ（緑）の液状体組成物、及びＢ（青）の液状体組成物をそれぞれ所定のパターン、本例では従来公知のストライプ型で形成される。なお、この形成パターンとしては、ストライプ型の他に、モザイク型、デルタ型、あるいはスクウェア型などでもよい。そして、ＲＧＢそれぞれの液状体組成物には上述した酸化防止剤が添加されている。
【０１２１】
このようなカラーフィルタ領域３５１を形成するには、まず図１４（ａ）に示すように透明の基板Ｐの一方の面に対し、ブラックマトリクス３５２が形成される。このブラックマトリクス３５２の形成方法としては、光透過性のない樹脂（好ましくは黒色）を、スピンコート法などの方法で所定の厚さ（例えば２μｍ程度）に塗布することで行う。このブラックマトリクス３５２の格子で囲まれる最小の表示要素、すなわちフィルタエレメント３５３については、例えばＸ軸方向の幅を３０μｍ、Ｙ軸方向の長さを１００μｍ程度とする。
【０１２２】
次に、図１４（ｂ）に示すように、前記液滴吐出ヘッド２０から液状体組成物の液滴３５４が吐出され、フィルタエレメント３５３に着弾する。吐出する液滴３５４の量については、加熱工程における液状体組成物の体積減少を考慮した十分な量とする。
このようにして基板Ｐ上の全てのフィルタエレメント３５３に液滴３５４を充填したら、ヒータを用いて基板Ｐが所定の温度（例えば７０℃程度）となるように加熱処理される。この加熱処理により、液状体組成物の溶媒が蒸発して液状体組成物の体積が減少する。この体積現状の激しい場合には、カラーフィルタとして十分な膜厚が得られるまで、液滴吐出工程と加熱工程とを繰り返す。この処理により、液状体組成物に含まれる溶媒が蒸発して、最終的に液状体組成物に含まれる固形分のみが残留して膜化し、図１４（ｃ）に示すようなカラーフィルタ３５５となる。
【０１２３】
次いで、基板Ｐを平坦化し、且つカラーフィルタ３５５を保護するために、図１４（ｄ）に示すようにカラーフィルタ３５５やブラックマトリクス３５２を覆って基板Ｐ上に保護膜３５６を形成する。この保護膜３５６の形成にあたっては、スピンコート法、ロールコート法、リッピング法などの方法を採用することができるが、カラーフィルタ３５５と同様に、液滴吐出法により行うこともできる。
【０１２４】
次いで、図１４（ｅ）に示すようにこの保護膜３５６の全面に、スパッタ法や真空蒸着法などによって透明導電膜３５７を形成する。その後、透明導電膜３５７をパターニングし、図１４（ｆ）に示すように画素電極３５８をフィルタエレメント３５３に対応させてパターニングする。なお、液状表示パネルの駆動にＴＦＴ（Ｔｈｉｎ　Ｆｉｌｍ　Ｔｒａｎｓｉｓｔｏｒ）を用いる場合には、このパターニングは不用となる。
【０１２５】
また、本発明に係る成膜方法は、前記カラーフィルタ３５５を形成した基板Ｐを用いる液晶素子の構成要素となる膜を形成する際にも適用可能である。すなわち、前記基板Ｐを用いて公知の液晶セルを作製し液晶素子とすることにより、液晶装置を形成することができる。図１５は、このような液晶素子を形成するための液晶セルの構造を説明するための図であり、液晶装置は、前記カラーフィルタ（図１５には図示せず）を形成した基板である対向基板３６０を備えている。この対向基板３６０は、ＴＦＴ等を形成した回路基板（図示せず）と反対の側に配置されるものである。この対向基板３６０の内面側には、対向基板３６０側から入射する光を前記回路基板（図示せず）側に集光するためのマイクロレンズ３６１が多数設けられており、これらマイクロレンズ３６１を形成した側には、接着剤３６２によってカバーガラス３６３が貼着されている。
【０１２６】
このカバーガラス３６３の内面側には、前記マイクロレンズ３６１間の境界と対応する位置にそれぞれ遮光膜３６４が形成されており、さらにこれを覆った状態でカバーガラス３６３のほぼ全面にＩＴＯ等の透明導電性材料からなる対向電極３６５が形成されている。そして、この対向電極３６５の内面側にポリイミド薄膜などの有機薄膜からなる配向膜３６６が形成され、さらにこのように形成された対向基板３６０と前記回路基板との間に液晶３６７が封止されることにより、液晶装置が構成される。
このような構成からなる液晶装置の製造においても、その液晶素子における構成要素となる薄膜、例えば遮光膜３６４や配向膜３６６などを形成する際の液状体組成物に予め酸化防止剤を添加しておき、この液状体組成物を用いて成膜することができる。
【０１２７】
また、本発明に係る成膜方法は、少なくともチャネル部が有機膜で形成された有機ＴＦＴ素子（有機薄膜トランジスタ素子）の構成要素となる膜を形成する際にも適用可能である。この有機ＴＦＴ素子としては、例えば図１６に示すような構成のものがある。
図１６において、基板４５０上にはゲート電極４５１が形成されている。また、基板４５０上にはゲート電極４５１を覆った状態で高誘電率の絶縁体からなるゲート絶縁膜４５２が形成され、このゲート絶縁膜４５２上には有機半導体層４５３が形成されている。そして、この有機半導体層４５３上にソース電極４５４およびドレイン電極４５５が形成されることにより、有機ＴＦＴ素子（有機薄膜トランジスタ素子）が構成される。
【０１２８】
このような有機ＴＦＴ素子を製造するには、まず、基板４５０上にゲート電極材料が設けられゲート電極４５１が形成される。次に、このゲート電極４５１を覆った状態にゲート絶縁膜４５２が形成される。このゲート絶縁膜４５２の形成材料としては、限定されることなく種々のものが使用可能であるが、特に高誘電率の絶縁体として、金属酸化物薄膜、好ましくはチタン酸バリウムストロンチウム、ジルコニウム酸チタン酸バリウム、ジルコニウム酸チタン酸鉛、チタン酸鉛ランタン、チタン酸ストロンチウム、チタン酸バリウム、フッ化バリウムマグネシウム、チタン酸ビスマス、チタン酸ストロンチウムビスマス、タンタル酸ストロンチウムビスマス、タンタル酸ニオブ酸ビスマス、タンタル酸ニオブ酸ストロンチウムビスマス、ペントオキサイドタンタル、ジオキサイドチタン、トリオキサイドイットリウム、酸化タンタル、酸化バナジウム、酸化チタンなどの無機材料が好適に用いられる。また、ポリクロロピレン、ポリエチレンテレフタレート、ポリオキシメチレン、ポリビニルクロライド、ポリフッ化ビニリデン、シアノエチルプルラン、ポリメチルメタクリレート、ポリサルファン、ポリカーボネート、ポリイミド等の有機材料も使用可能である。なお、特に前記の無機材料によってゲート絶縁膜４５２を形成する場合には、成膜後、さらにこれに１５０〜４００℃の範囲の適宜な温度でアニール処理を行うのが、膜品質を改善し、誘電率を増大させることができ好ましい。
【０１２９】
次いで、このゲート絶縁膜４５２上に有機半導体層４５３が形成される。この有機半導体層４５３の形成にあたっては、液滴吐出装置ＩＪが好適に用いられる。有機半導体層４５３の形成材料としては、ゲート電圧が増加するにしたがって電界効果移動度の増大を示すポリマ半導体またはオリゴマー半導体が用いられ、具体的には、ナフタレン、アントラセン、テトラセン、ペンタセン、ヘキサセン、およびその誘導体や、ポリアセチレンのうちの１種以上が用いられる。
【０１３０】
また、特にｐ−チャネル用とされる場合には、２〜５個の炭素原子を介して結合された、オリゴ重合度が４以上８以下のチオフェンのオリゴマー；２〜５個の炭素原子を介して結合された、３〜６個のチオフェン環と末端基としてチオフェンを有するビニレンと、チエニレンとの交互共役オリゴマー；ベンゾ［１，２−ｂ：４，５’］ジチオフェンの線状ダイマー及びトリマー；末端のチオフェンの４個又は５個の炭素原子上に置換基（例えば、炭素原子を１〜２０個有するアルキル置換基）を有する前記オリゴマー；ポリマーマトリックス中のｐ、ｐ’−ジアミノビフェニル複合体なども使用可能であり、特にα−ヘキサチエニレン（α−６Ｔ）が好適に用いられる。さらに、ｐ−チャネル用とされる場合には、１，４，５，８−ナフタレンテトラカルボキシルジアンヒドライド（ＮＴＣＤＡ：ｎａｐｈｔｈａｌｅｎｅ　ｔｅｔｒａｃａｒｂｏｘｙｌｉｃ　ｄｉａｎｈｙｄｒｉｄｅ　）、１，４，５，８−ナフタレンテトラカルボキシルジイミド（ＮＴＣＤＩ：ｎａｐｈｔｈａｌｅｎｅ　ｔｅｔｒａｃａｒｂｏｘｙｌｉｃ　ｄｉｉｍｉｄｅ　）、１１，１１，１２，１２−テトラシアノナフト−２，６−キノジメタン（ＴＣＮＮＱＤ：ｔｅｔｒａｃｙａｎｏｎａｐｈｔｈｏ−２，６−ｑｕｉｎｏｄｉｍｅｔｈａｎｅ）なども使用可能である。
【０１３１】
このような有機半導体材料を前記の液滴吐出装置ＩＪによって成膜する場合、まず、有機半導体材料を溶媒に溶解するるとともに上述した酸化防止剤を添加することにより液状体組成物が生成される。そして、この液状体組成物が基板４５０のゲート絶縁膜４５２上に吐出され塗布される。そして、加熱あるいは減圧等による乾燥を適宜に行うことにより、溶媒を除去して有機半導体層４５３が形成される。その後、この有機半導体層４５３上にソース電極４５４およびドレイン電極４５５が形成され、有機ＴＦＴ素子が得られる。
【０１３２】
なお、本発明の液滴吐出装置やこれを備えた成膜装置、さらには本発明の液状体組成物は、上述した各実施形態に限定されることなく、種々の用途に使用可能である。例えば、銀コロイド溶液などを酸化防止剤とともに液状体組成物とし、これを基板上に吐出して塗布し、さらに加熱乾燥することにより、金属配線を直接パターニングすることができる。
【０１３３】
本発明の有機ＥＬ装置及び液晶装置を含む電気光学装置、あるいは本発明の有機ＴＦＴ素子を備えたデバイスは、表示部を備えた様々な電子機器に適用される。以下、本発明の電気光学装置を備えた電子機器の適用例について説明する。
【０１３４】
１．腕時計
本発明の電気光学装置を、腕時計に適用した例について説明する。図１７はこの腕時計の構成を示す斜視図であり、腕時計１１００は、本発明の電気光学装置を表示部１１０１として備える。
【０１３５】
２．モバイル型コンピュータ
本発明の電気光学装置を、モバイル型（ポータブル型）のパーソナルコンピュータに適用した例について説明する。図１８はこのパーソナルコンピュータの構成を示す斜視図であり、パーソナルコンピュータ１２００は、本発明の電気光学装置を表示部１２０１として備える。パーソナルコンピュータ１２００は、キーボード１２０３を備えた本体部１２０２を備えて構成されている。
【０１３６】
３．携帯電話
本発明の電気光学装置を、携帯電話に適用した例について説明する。図１９はこの携帯電話の構成を示す斜視図であり、携帯電話１３００は、本発明の電気光学装置を小サイズの表示部１３０１として備える。携帯電話１３００は、複数の操作ボタン１３０２、受話口１３０３、及び送話口１３０４を備えて構成されている。
【０１３７】
４．電子ペーパー
本発明の電気光学装置を、フレキシブルな電子ペーパーに適用した例について説明する。図２０はこの電子ペーパーの構成を示す斜視図であり、電子ペーパー１４００は、本発明の電気光学装置を表示部１４０１として備える。電子ペーパー１４００は、従来の紙と同様の質感及び柔軟性を有する書き換え可能なシートからなる本体１４０２を備えて構成されている。
また、図２１は、電子ノートの構成を示す斜視図であり、電子ノート１５００は、図２１で示した電子ペーパー１４００が複数枚束ねられ、カバー１５０１に挟まれているものである。カバー１５０１は、例えば外部の装置から送られる表示データを入力する不図示の表示データ入力手段を備える。これにより、その表示データに応じて、電子ペーパーが束ねられた状態のまま、表示内容を変更したり更新したりできる。
【０１３８】
５．表示装置
また、本発明の電気光学装置を、図２２（ａ）及び図２２（ｂ）に示すような表示装置１６０１に適用した例について説明する。表示装置１６０１のフレーム１６０１Ａには、表示ユニット１６０２が着脱自在に固定されている。表示ユニット１６０２は、極めて薄いシート状、すなわち紙状の記録媒体（いわゆる電子ペーパー）であり、搬送ローラ１６０４、１６０６に保持され、フレーム１６０１Ａ内の一方の側の所定の位置に配置されている。フレーム１６０１Ａのほぼ中央部は、窪んで形成されており、窪みには矩形状の孔１６０１Ｃが形成され、その孔１６０１Ｃにはガラス基板１６０７が取り付けられている。また、フレーム１６０１Ａには、表示ユニット１６０２が挿入され且つ取り外される挿入／脱着口１６０８が設けられている。表示ユニット１６０２の挿入方向の端部には端末ユニット１６１０が設けられている。端末ユニット１６１０は、フレーム１６０１Ａ内でソケット１６１２と電気的に接続され、これにより、フレーム１６０１Ａの他方の側に配置される制御器１６１３に接続される。
このような取り外し可能は表示ユニット１６０２は、携帯性に優れるとともに、厚くなくてかさばらないので取り扱いが容易である。そのため、例えば目的地のエリアに関する地図を表示させながら、表示ユニット１６０２だけを持ち歩くといった使い方が可能になる。
【０１３９】
なお、上述した例に加えて、他の例として、液晶テレビ、ビューファインダ型やモニタ直視型のビデオテープレコーダ、カーナビゲーション装置、ページャ、電子手帳、電卓、ワードプロセッサ、ワークステーション、テレビ電話、ＰＯＳ端末、タッチパネルを備えた機器等が挙げられる。本発明の電気光学装置は、こうした電子機器の表示部としても適用できる。
【０１４０】
【発明の効果】
以上説明したように、有機機能材料と溶媒とからなる溶液に酸化防止剤を添加して液状化したことにより、酸素に起因する物性変化や溶質の析出を抑えることができ、液状体組成物の安定性を向上できる。そして、この液状体組成物を用いて各種素子・装置を製造することにより、信頼性の高い優れた素子・装置を提供することができる。
【図面の簡単な説明】
【図１】本発明の膜の製造装置の一実施形態を示す概略構成図である。
【図２】液滴吐出ヘッドを示す図である。
【図３】液滴吐出ヘッドを示す図である。
【図４】有機ＥＬ装置の回路図である。
【図５】有機ＥＬ装置の一画素に対応した部分を説明するための図である。
【図６】有機ＥＬ装置の製造工程の一例を示す図である。
【図７】有機ＥＬ装置の製造工程の一例を示す図である。
【図８】有機ＥＬ装置の製造工程の一例を示す図である。
【図９】本発明に係る有機ＥＬ装置と従来の有機ＥＬ装置との特性試験結果を示す図である。
【図１０】本発明に係る有機ＥＬ装置と従来の有機ＥＬ装置との特性試験結果を示す図である。
【図１１】本発明に係る有機ＥＬ装置と従来の有機ＥＬ装置との特性試験結果を示す図である。
【図１２】本発明に係る有機ＥＬ装置と従来の有機ＥＬ装置との特性試験結果を示す図である。
【図１３】カラーフィルタを示す図である。
【図１４】カラーフィルタの製造工程の一例を示す図である。
【図１５】液晶装置を示す図である。
【図１６】有機ＴＦＴ素子を示す図である。
【図１７】本発明の電気光学装置が搭載された電子機器を示す図である。
【図１８】本発明の電気光学装置が搭載された電子機器を示す図である。
【図１９】本発明の電気光学装置が搭載された電子機器を示す図である。
【図２０】本発明の電気光学装置が搭載された電子機器を示す図である。
【図２１】本発明の電気光学装置が搭載された電子機器を示す図である。
【図２２】本発明の電気光学装置が搭載された電子機器を示す図である。
【符号の説明】
１１４Ａ、１１４Ｂ　　液状体組成物
１４０Ａ　　正孔注入層（材料層）
１４０Ｂ　　発光層（材料層）
ＩＪ　　液滴吐出装置（成膜装置、液状体吐出装置）
Ｓ　　組成物調整装置
ＳＴ　　ステージ装置[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a composition, a film forming method and a film forming apparatus, an electro-optical device and a method for manufacturing an electro-optical device, an organic electroluminescent device, a method for manufacturing an organic electroluminescent device, a device and a method for manufacturing a device, and an electronic apparatus. It is.
[0002]
[Prior art]
2. Description of the Related Art Conventionally, a photolithography method has been frequently used for forming a fine pattern such as a wiring pattern of a semiconductor device. In recent years, a pattern forming method using a droplet discharge method (a liquid material discharge method) has attracted attention. The droplet discharge method is a method in which a pattern forming material is liquefied (inked) with a solvent, and droplets (ink droplets) are discharged from a droplet discharge device to a substrate to form a pattern. The droplet discharge method is very effective, for example, in that it can cope with production of various kinds in small quantities. The following patent document discloses a technique relating to a droplet discharge method.
[0003]
[Patent Document 1]
JP-A-11-274671
[Patent Document 2]
JP-A-2000-216330
[0004]
[Problems to be solved by the invention]
Conventionally, a process for producing a composition (ink) containing a liquid has been performed in an air environment. In this case, the air (oxygen) causes problems such as a change in physical properties during production and storage of the liquid composition, and precipitation of a solute in the liquid composition. Here, the change in physical properties refers to a change in the molecular weight (or molecular weight distribution) before and after the production of the liquid composition, which causes a viscosity increase. When the physical property change or precipitation occurs in the liquid material composition, the discharge stability of the liquid droplet discharge device (liquid material discharge device) decreases. Furthermore, when a device is manufactured using this liquid composition, the device is deteriorated by aging or driving, and problems such as a decrease in the reliability of the device are caused.
[0005]
The present invention has been made in view of such circumstances, and a first object of the present invention is to provide a composition containing a liquid material that can suppress a change in physical properties over time when a material for pattern formation is liquefied. The purpose of.
A second object is to provide a film forming method and a film forming apparatus which can form a film pattern with high productivity using this composition.
Furthermore, by using this composition, a highly reliable electro-optical device and a method for manufacturing an electro-optical device, an organic electroluminescent device, a method for manufacturing an organic electroluminescent device, a device and a method for manufacturing a device, and these devices were mounted. A third object is to provide an electronic device.
[0006]
[Means for Solving the Problems]
In order to solve the above problems, the composition of the present invention is characterized in that an antioxidant is added to a liquid containing an organic functional material and a solvent.
According to the present invention, a liquid containing an organic functional material and a solvent is liquefied (inked) by adding an antioxidant, thereby suppressing changes in physical properties and solute precipitation caused by the atmosphere (oxygen). And the stability of the liquid composition (ink) can be improved. Here, as the solvent to be used, any solvent such as an organic solvent or an aqueous solvent can be appropriately selected depending on the physical properties of the organic functional material.
[0007]
In the composition of the present invention, a configuration in which the antioxidant is transparent or translucent is employed. According to this, when this composition is applied to the manufacture of a light-emitting device, the coloring by the antioxidant is suppressed, and the effect of the antioxidant on the light-emitting color, such as a change in the color of emitted light or a decrease in luminance, is suppressed. And a desired coloring state can be obtained. If the amount of the antioxidant added to the organic functional material is sufficiently small, even if the antioxidant is colored, the influence on the emission color is small.
[0008]
In this case, the antioxidant may be a radical chain inhibitor or a peroxide decomposer. Alternatively, an ultraviolet absorber, a metal deactivator, or the like can be used. Radical chain inhibitors include phenolic antioxidants, monophenolic, bisphenolic, and polymeric phenolic antioxidants. Examples of the peroxide decomposer include a sulfur-based antioxidant and a phosphorus-based antioxidant.
[0009]
In the composition of the present invention, a configuration is adopted in which the organic functional material is a light emitting material. According to this, when manufacturing a device by liquefying a light emitting material, it is possible to suppress a change in the physical properties of the liquid composition and the occurrence of precipitation, thereby exhibiting excellent light emitting performance.
In addition, in the composition of the present invention, the organic functional material may be configured to be a polymer material, or may be configured to be an organic electroluminescent material. Further, when the organic functional material is an organic electroluminescent material, the antioxidant is added to a hole injection material (a material for forming a hole injection layer) or a light emitting material (a material for forming a light emitting layer). can do.
[0010]
In the composition of the present invention, a configuration is adopted in which the solubility parameter of the antioxidant is 7.0 to 13.0. According to this, since the antioxidant has sufficient solubility in the solvent, it is compatible with the organic functional material, is sufficiently dispersed, and does not cause phase separation even after film formation. When the organic functional material is a light emitting material, it is possible to suppress the occurrence of uneven light emission due to sufficient dispersion of the antioxidant.
[0011]
Here, when the organic functional material is a hole injecting material (a material for forming a hole injecting layer) among organic electroluminescent materials, the dissolution parameter is 7.0 to 13.0, preferably 8.5 to 13. It is desirable to use an antioxidant that is zero. On the other hand, when the organic functional material is a light emitting material (a material for forming a light emitting layer) among the organic electroluminescent materials, the oxidation parameter having a solubility parameter of 7.0 to 13.0, preferably 7.5 to 10.5 is used. It is desirable to use inhibitors.
[0012]
In the liquid composition of the present invention, a configuration is employed in which the solubility of the antioxidant in the solvent is 0.001% or more. According to this, since the antioxidant has sufficient solubility in the solvent, it is compatible with the organic functional material, is sufficiently dispersed, and does not cause phase separation even after film formation. When the organic functional material is a light emitting material, it is possible to suppress the occurrence of uneven light emission due to sufficient dispersion of the antioxidant.
[0013]
Here, when the organic functional material is a hole injection material among the organic electroluminescent materials, it is desirable to use an antioxidant having a solubility in a solvent of 0.001% or more, preferably 5% or more. Also, when the organic functional material is a light emitting material among organic electroluminescent materials, it is desirable to use an antioxidant having a solubility in a solvent of 0.001% or more, preferably 5% or more.
[0014]
In the composition of the present invention, a configuration is employed in which the amount of the antioxidant to be added is 0.001 to 30% by weight based on the organic functional material. According to this, the composition exhibits a desired function while preventing oxidation.
[0015]
The film forming method of the present invention is to form a film by adding an antioxidant to a liquid containing an organic functional material and a solvent to prepare a composition, and providing the composition on a predetermined surface. Features.
According to the present invention, since an antioxidant is added to the composition, it is possible to suppress changes in physical properties and precipitation of the composition. Therefore, a uniform film can be manufactured with high productivity, and no phase separation or the like of the film occurs even after film formation.
[0016]
In the film forming method of the present invention, a configuration is adopted in which the organic functional material is a light emitting material. As a result, a film having good emission characteristics can be manufactured.
[0017]
In the film forming method of the present invention, the organic functional material may be a material for forming a component of an organic electroluminescence element, a material for forming a component of a color filter, or an organic thin film transistor. It may be a material for forming a component of an element or a material for forming a component of a liquid crystal element. By adding an antioxidant to each of these constituent element forming materials, each of the above-mentioned elements exhibits good performance.
[0018]
In the film forming method of the present invention, a configuration is employed in which the composition is formed by discharging the composition onto the predetermined surface by a liquid material discharging apparatus. That is, the composition of the present invention can be discharged onto a predetermined surface by a liquid discharge method (droplet discharge method) to form a film. In this case, since an antioxidant is added to the composition, changes in physical properties and generation of precipitation are suppressed. Therefore, the discharge operation from the liquid discharge device is stable, and a desired film pattern can be formed. Note that the film formation method using the composition of the present invention is not limited to the droplet discharge method, and another coating method (film formation method) such as a spin coating method may be used.
[0019]
The film forming method of the present invention is characterized in that a composition containing an organic functional material and a solvent is arranged on a predetermined surface to form a film, and an antioxidant is arranged on the film.
That is, the organic functional material may be liquefied (inked) with a solvent, a film may be formed with the liquid composition, and an antioxidant may be formed on the film.
Here, when providing the antioxidant, a second composition containing the antioxidant and a solvent is adjusted, and the composition is sent out to a liquid discharge device via a flow path, and the liquid discharge is performed. The antioxidant can be disposed on the film by discharging the film onto the film with an apparatus. By forming a film containing an antioxidant using a liquid material discharging device, an arbitrary film pattern containing an antioxidant can be easily formed. Here, it is desirable that the flow path is isolated from outside air.
After the liquid composition is provided on the substrate, the liquid composition on the substrate is subjected to a heat treatment (baking treatment) to remove the solvent, and then the second composition is discharged. The second composition may be discharged immediately after the composition is provided on the base material, that is, in a state where the liquid material composition on the base material is wet. By discharging the second composition while the composition on the substrate is wet, the composition and the second composition containing an antioxidant can be mixed on the substrate.
In this case, the second composition may be a solution comprising an antioxidant and a solvent, or a liquid comprising an antioxidant, a solvent and a synthetic resin as a binder. When the second composition is formed by the antioxidant, the solvent, and the synthetic resin, the organic functional material layer and the synthetic resin layer containing the antioxidant are laminated. Of course, the binder is not limited to a synthetic resin, and any material that does not affect the organic functional material can be used.
[0020]
The film forming apparatus of the present invention includes a composition adjusting device for adjusting a composition including an organic functional material, a solvent, and an antioxidant, and a liquid material including the composition adjusted by the composition adjusting device, which is discharged onto a predetermined surface. And a liquid ejecting device.
According to the present invention, since an antioxidant is added to the composition, it is possible to suppress a change in physical properties of the composition and the occurrence of precipitation. Therefore, a uniform film can be manufactured with high productivity, and the film after film formation does not not only phase-separate but also does not impair the function of the thin film. Since the film is formed using the droplet discharge device, an arbitrary film pattern can be easily formed.
Further, when the composition adjusted by the composition adjusting device is transported from the adjusting device to the liquid discharge device, for example, by preventing the composition from being exposed to the outside air, the oxidizing agent such as oxygen or the like, or the like, can be prevented from being mixed. be able to.
[0021]
The film forming apparatus of the present invention is a composition adjusting apparatus for adjusting a composition including an organic electroluminescent material, a solvent, and an antioxidant, and a composition adjusted by the composition adjusting apparatus, which is disposed on a predetermined surface. A film forming unit for forming a film.
According to the present invention, since an antioxidant is added to a composition containing an organic electroluminescent material, it is possible to suppress a change in physical properties of the composition and the occurrence of precipitation. Therefore, a uniform film can be manufactured with high productivity, and the film does not undergo phase separation even after film formation, so that an organic electroluminescent device having desired performance can be manufactured.
[0022]
In the film forming apparatus of the present invention, a configuration including a movable stage device while supporting the substrate having the predetermined surface is employed. According to this, the liquid composition can be provided on the predetermined surface while moving the substrate, and the film can be manufactured efficiently.
[0023]
An electro-optical device according to the present invention is an electro-optical device having a functional element, wherein the functional element contains an antioxidant.
According to the present invention, since the antioxidant is contained in the functional element, it is possible to suppress changes in physical properties and precipitation of the material in the functional element at the time of manufacturing the element, and also suppress deterioration over time. Thus, a high-performance electro-optical device is provided.
[0024]
The electro-optical device according to the present invention is characterized in that, in the electro-optical device having a functional element, an antioxidant layer containing an antioxidant is adjacent to the functional element.
That is, the antioxidant can be provided as an antioxidant layer or a film separate from the functional element, in addition to the configuration contained in the functional element.
[0025]
In the electro-optical device according to the aspect of the invention, the functional element may be a light-emitting element. That is, the functional element may be constituted by a material layer capable of emitting light. Thereby, an electro-optical device having good light emitting performance is provided.
Further, in the electro-optical device described above, the light-emitting element includes a light-emitting layer and a pair of electrodes sandwiching the light-emitting layer, a base supporting the light-emitting element, provided on the base, A configuration including an energization control unit that controls energization of the electrodes is employed. According to this, it is possible to supply a desired electric power to the light emitting layer via the electrode by the power supply control unit to emit light.
Further, in the electro-optical device according to the present invention, the functional element may be an organic electroluminescence element.
[0026]
The method for producing an electro-optical device according to the present invention is the method for producing an electro-optical device having a functional element, wherein an antioxidant is added to a solution containing the material for forming a functional element and a solvent to prepare a composition. And a step of providing the composition on a base material and forming a film that is a component of the functional element.
According to the present invention, since a liquid composition is generated by a functional element forming material, a solvent, and an antioxidant, it is possible to suppress a change in physical properties of the material and the occurrence of precipitation during production or storage of the liquid composition. it can. Since the film is formed using the liquid composition, the formed film does not cause phase separation or the like.
[0027]
In the method of manufacturing an electro-optical device according to the present invention, a configuration is employed in which the liquid containing the composition is discharged onto the base material by a liquid discharge device to form the film. Thereby, a desired film pattern can be easily formed.
[0028]
The method for manufacturing an electro-optical device according to the present invention is the method for manufacturing an electro-optical device having a functional element, wherein a composition including the functional element forming material and a solvent is provided on a base material, And a step of disposing an antioxidant on the film.
That is, it is also possible to adopt a configuration in which after forming a film to be a component of a functional element on a base material, an antioxidant is provided on the film.
Then, when the antioxidant is provided, a second composition including the antioxidant and a solvent is adjusted, and a liquid including the second composition is discharged to the film by a liquid discharge device. Is possible. Also in this case, a synthetic resin as a binder may be added to the second composition containing the antioxidant and the solvent, and the second composition containing the synthetic resin may be discharged. The functional element may be an organic electroluminescent element.
[0029]
The organic electroluminescence device according to the present invention is characterized in that, in the organic electroluminescence device having a plurality of material layers, at least one of the plurality of material layers contains an antioxidant.
ADVANTAGE OF THE INVENTION According to this invention, since the material layer which comprises an organic electroluminescent apparatus contains an antioxidant, deterioration of the organic electroluminescent apparatus by aging or driving can be prevented, and a highly reliable organic electroluminescent apparatus can be prevented. Can be provided.
[0030]
In this case, a configuration in which an antioxidant is contained in the light emitting layer among the material layers constituting the organic electroluminescence device is employed. Thereby, deterioration of the light emitting layer is suppressed, and an organic electroluminescence device having good light emitting characteristics is provided.
[0031]
In the organic electroluminescence device according to the present invention, in the organic electroluminescence device having a plurality of material layers, an antioxidant layer containing an antioxidant is formed between predetermined material layers among the plurality of material layers. It is characterized by.
That is, in addition to the configuration in which the material layer constituting the organic electroluminescence device contains an antioxidant, a layer made of the antioxidant can be interposed between the material layers.
[0032]
The method for manufacturing an organic electroluminescence device according to the present invention is a method for manufacturing an organic electroluminescence device having a plurality of material layers, wherein an antioxidant is added to a solution containing the material for forming a material layer and a solvent. And forming the material layer using the composition.
According to the present invention, an antioxidant is added to a material for forming a material layer when producing a liquid composition for producing an organic electroluminescence device, so that the composition is prepared during the production or storage of the composition. It is possible to suppress a change in physical properties of the material and the occurrence of solute precipitation. By forming a material layer using this composition, it is possible to suppress occurrence of problems such as phase separation. Therefore, a highly reliable organic electroluminescence device can be manufactured.
[0033]
In the method of manufacturing an organic electroluminescence device according to the present invention, a configuration is employed in which the material layer is formed by discharging a liquid containing the composition with a liquid discharge device. Since the material layer is formed by using the liquid material discharging method (droplet discharging method), the material layer can be formed with a simple configuration and with good workability.
[0034]
The method for manufacturing an organic electroluminescence device of the present invention is the method for manufacturing an organic electroluminescence device having a plurality of material layers, wherein the material layer is formed using a composition containing the material for forming a material layer and a solvent, An antioxidant is provided on the material layer.
That is, also in this case, a configuration in which a layer containing an antioxidant is formed adjacent to the material layer constituting the organic electroluminescence device is possible. Then, when the antioxidant is provided, a second composition is generated with the antioxidant and the solvent, and a liquid containing the second composition is discharged to the material layer by a liquid discharge device. Is possible.
[0035]
The device of the present invention is characterized by being manufactured using the composition described above. A method for manufacturing a device according to the present invention is characterized by using the above-described composition. Further, in the device manufacturing method of the present invention, a configuration including a step of discharging a liquid material composed of the composition by a liquid material discharging apparatus is employed. Thus, a highly reliable device can be provided.
[0036]
An electronic apparatus according to another aspect of the invention includes the electro-optical device described above. According to another aspect of the invention, an electronic apparatus includes the above-described organic electroluminescence device. Thus, an electronic device having excellent characteristics is provided.
[0037]
Here, the liquid material discharge device (droplet discharge device) in the present invention includes an ink jet device provided with an ink jet head (droplet discharge head). The ink jet head of the ink jet device is a device capable of quantitatively discharging the liquid composition by an ink jet method, for example, capable of quantitatively intermittently dropping 1 to 300 nanograms of the liquid composition per dot. Note that a dispenser device may be used as the droplet discharge device.
[0038]
Even if the droplet discharge method of the droplet discharge device is a piezo jet method in which the liquid composition is discharged by a change in the volume of the piezoelectric element, the vapor composition is suddenly generated by the application of heat and the liquid composition is discharged. May be ejected.
[0039]
The composition containing a liquid material (liquid material composition) refers to a medium having a viscosity capable of being discharged (dropped) from a nozzle of a discharge head of a droplet discharge device. It does not matter whether it is aqueous or oily. It is sufficient that the material has fluidity (viscosity) that can be discharged from a nozzle or the like. Further, the material contained in the liquid composition may be dissolved by being heated to a temperature equal to or higher than the melting point, or may be stirred as fine particles in a solvent, and other functional materials such as dyes and pigments may be added in addition to the solvent. It may be something. Further, the substrate may be a flat substrate or a curved substrate. Further, the hardness of the pattern forming surface does not need to be high, and may be a surface of a flexible material such as film, paper, rubber, etc. other than glass, plastic, and metal.
[0040]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, a film manufacturing apparatus of the present invention will be described with reference to the drawings. FIG. 1 is a schematic perspective view showing a droplet discharge device (film forming device) as a film manufacturing device of the present invention. 2 and 3 are views showing a droplet discharge head provided in the droplet discharge device.
In FIG. 1, a droplet discharge device IJ is a film forming device capable of setting a liquid composition on a surface (predetermined surface) of a substrate (base material) P, and is provided on a base 12 and on the base 12. A stage (stage device) ST supporting the substrate P, a first moving device 14 interposed between the base 12 and the stage ST and movably supporting the stage ST, and a substrate P supported by the stage ST On the other hand, a droplet discharge head 20 capable of quantitatively discharging (dropping) a liquid composition containing an organic functional material is provided, and a second moving device 16 movably supporting the droplet discharge head 20. The operation of the droplet discharging device IJ including the discharging operation of the liquid composition by the droplet discharging head 20 and the moving operations of the first moving device 14 and the second moving device 16 are controlled by the control device CONT.
[0041]
The first moving device 14 is installed on the base 12 and is positioned along the Y-axis direction. The second moving device 16 is mounted upright on the base 12 using the columns 16A, 16A, and is mounted on a rear portion 12A of the base 12. The X-axis direction of the second moving device 16 is a direction orthogonal to the Y-axis direction of the first moving device 14. Here, the Y-axis direction is a direction along the front portion 12B and the rear portion 12A of the base 12. On the other hand, the X-axis direction is a direction along the left-right direction of the base 12 and is horizontal. The Z-axis direction is a direction perpendicular to the X-axis direction and the Y-axis direction.
[0042]
The first moving device 14 is configured by, for example, a linear motor, and includes guide rails 40 and 40 and a slider 42 provided movably along the guide rail 40. The slider 42 of the first moving device 14 of the linear motor type can be positioned by moving in the Y-axis direction along the guide rail 40.
[0043]
Further, the slider 42 includes a motor 44 for rotating around the Z axis (θz). The motor 44 is, for example, a direct drive motor, and the rotor of the motor 44 is fixed to the stage ST. Thus, when the motor 44 is energized, the rotor and the stage ST rotate along the θz direction to index (rotate) the stage ST. That is, the first moving device 14 can move the stage ST in the Y-axis direction and the θz direction.
[0044]
The stage ST holds the substrate P and positions it at a predetermined position. The stage ST has a suction holding device 50, and the substrate P is sucked and held on the stage ST through the hole 46A of the stage ST by operating the suction holding device 50.
[0045]
The second moving device 16 is constituted by a linear motor, and is movable in the X-axis direction along the column 16B fixed to the columns 16A, 16A, the guide rail 62A supported by the column 16B, and the guide rail 62A. And a supported slider 60. The slider 60 can be positioned by moving in the X-axis direction along the guide rail 62A, and the droplet discharge head 20 is attached to the slider 60.
[0046]
The droplet discharge head 20 has motors 62, 64, 66, and 68 as swing positioning devices. By operating the motor 62, the droplet discharge head 20 can be moved up and down along the Z axis to be positioned. The Z axis is a direction (vertical direction) orthogonal to the X axis and the Y axis. When the motor 64 is operated, the droplet discharge head 20 can be positioned by swinging along the β direction around the Y axis. When the motor 66 is operated, the droplet discharge head 20 can be positioned by swinging in the γ direction around the X axis. When the motor 68 is operated, the droplet discharge head 20 can be positioned by swinging in the α direction around the Z axis. That is, the second moving device 16 supports the droplet discharge head 20 movably in the X-axis direction and the Z-axis direction, and supports the droplet discharge head 20 movably in the θx direction, the θy direction, and the θz direction. I do.
[0047]
As described above, the droplet discharge head 20 shown in FIG. 1 can be positioned by linearly moving in the Z-axis direction on the slider 60 and can be positioned by swinging along α, β, and γ. The position or orientation of the ejection surface 20P of the head 20 with respect to the substrate P on the stage ST side can be accurately controlled. A plurality of nozzles for discharging the liquid composition are provided on the discharge surface 20P of the droplet discharge head 20.
[0048]
FIG. 2 is an exploded perspective view showing the droplet discharge head 20. As shown in FIG. 2, the droplet discharge head 20 includes a nozzle plate 80 having a nozzle 81, a pressure chamber substrate 90 having a vibration plate 85, and a housing for fitting and supporting the nozzle plate 80 and the vibration plate 85. And a body 88. The main structure of the droplet discharge head 20 has a structure in which a pressure chamber substrate 90 is sandwiched between a nozzle plate 80 and a vibration plate 85 as shown in a perspective view and a partial cross-sectional view of FIG. In the nozzle plate 80, nozzles 81 are formed at positions corresponding to the cavities (pressure chambers) 81 when bonded to the pressure chamber substrate 90. The pressure chamber substrate 90 is provided with a plurality of cavities 81 each of which can function as a pressure chamber by etching a silicon single crystal substrate or the like. The cavities 81 are separated by side walls 92. Each cavity 81 is connected via a supply port 94 to a reservoir 93 which is a common flow path. The vibration plate 85 is made of, for example, a thermal oxide film. The diaphragm 85 is provided with a tank port 86 so that an arbitrary liquid composition can be supplied from a tank 30 as a liquid composition adjusting device S described later through a pipe (flow path) 31. A piezoelectric element 87 is formed at a position on the diaphragm 85 corresponding to the cavity 81. The piezoelectric element 87 has a structure in which a crystal of a piezoelectric ceramic such as a PZT element is sandwiched between an upper electrode and a lower electrode (not shown). The piezoelectric element 87 is configured to be able to generate a volume change in response to an ejection signal supplied from the control device CONT.
[0049]
In order to discharge the liquid composition from the droplet discharge head 20, first, the control device CONT supplies a discharge signal for discharging the liquid composition to the droplet discharge head 20. The liquid composition flows into the cavity 81 of the droplet discharge head 20, and in the droplet discharge head 20 to which the discharge signal is supplied, the piezoelectric element 87 is applied between the upper electrode and the lower electrode. The applied voltage causes a volume change. This volume change deforms the diaphragm 85 and changes the volume of the cavity 81. As a result, droplets of the liquid material composition are discharged from the nozzle holes 211 of the cavity 81. The liquid composition reduced by the discharge is newly supplied to the cavity 81 from which the liquid composition is discharged from the tank 30 described later.
[0050]
The droplet discharging head is configured to discharge the liquid composition by causing a volume change in the piezoelectric element. However, the liquid discharging head is configured to discharge liquid droplets by applying heat to a liquid material by a heating element and expanding the liquid material. A head configuration may be used.
[0051]
Returning to FIG. 1, the liquid composition provided on the substrate P is generated by the liquid composition adjusting device S. The liquid material composition adjusting device S includes a tank 30 capable of storing the liquid material composition, a temperature adjusting device 32 attached to the tank 30, and adjusting the temperature of the liquid material composition stored in the tank 30. A stirring device 33 for stirring the liquid composition contained in the tank 30 is provided. The temperature adjusting device 32 is configured by a heater, and adjusts the liquid composition in the tank 30 to an arbitrary temperature.
[0052]
In the present embodiment, the liquid material composition adjusting device S generates a liquid material composition by adding an antioxidant to a solution containing an organic functional material and a solvent. The tank 30 includes an organic functional material supply device (not shown) for supplying an organic functional material to the tank 30, a solvent supply device (not shown) for supplying a predetermined solvent to the tank 30, An antioxidant supply device (not shown) for supplying an agent is connected. Then, the organic functional material, the solvent, and the antioxidant supplied from each of these supply devices to the tank 30 are stirred by the stirrer 33, so that the liquid composition including the organic functional material, the solvent, and the antioxidant is provided. Things are created. The material contained in the liquid composition is uniformly dispersed by being stirred by the stirring device 33. Here, the temperature adjusting device 32 is controlled by the control device CONT, and the temperature of the liquid composition in the tank 30 is adjusted by the temperature adjusting device 32 so as to be adjusted to a desired viscosity.
[0053]
The tank 30 is connected to the droplet discharge head 20 via a pipe (flow path) 31, and the liquid composition discharged from the droplet discharge head 20 is supplied from the tank 30 via the pipe 31. The liquid composition flowing through the pipe 31 is controlled to a predetermined temperature by a pipe temperature controller (not shown) to adjust the viscosity. Further, the temperature of the liquid composition discharged from the droplet discharge head 20 is controlled by a temperature adjusting device (not shown) provided in the droplet discharge head 20 so as to be adjusted to a desired viscosity. .
[0054]
FIG. 1 shows only one droplet discharge head 20 and one composition adjustment device S. However, the droplet discharge device IJ includes a plurality of droplet discharge heads 20 and the composition adjustment device S. A liquid composition of a different type or the same type is discharged from each of the plurality of droplet discharge heads 20. Then, after discharging the first liquid composition from the first droplet discharge head among the plurality of droplet discharge heads 20 to the substrate P, the first liquid composition is baked or dried, and then the second liquid composition is discharged. After discharging the second liquid composition from the droplet discharge head to the substrate P, the second liquid composition is baked or dried, and the same process is performed using a plurality of droplet discharge heads. A plurality of material layers are stacked to form a multilayer pattern.
[0055]
Next, a method of forming a film pattern on the substrate P using the liquid composition generated by the composition adjusting device S will be described. Hereinafter, as an example, a case in which a film constituting an organic electroluminescence device (hereinafter, referred to as an “organic EL device”) is manufactured will be described.
The present invention is characterized in that a liquid composition is prepared by adding an antioxidant to a solution containing an organic functional material and a solvent, and a film is produced using the liquid composition. Hereinafter, a case where an antioxidant is added to each of the hole injection layer and the light emitting layer in the organic EL device will be described as an example. That is, using the composition adjusting device S, an antioxidant is added to each of the hole injection layer forming material (hole injection material) and the light emitting layer forming material (light emitting material) as the organic functional material. The case will be described. In addition, the procedure shown below and the material composition of the liquid composition are merely examples, and the present invention is not limited thereto.
[0056]
4 and 5 are diagrams for explaining a schematic configuration of an example of an organic EL display 70 as an organic EL device. FIG. 4 is a circuit diagram, and FIG. 5 is a diagram showing a planar structure of each pixel 71. FIG. 3 is an enlarged plan view showing a state where a reflection electrode and an organic EL element are removed. As shown in FIG. 4, the EL display 70 includes a plurality of scanning lines 131, a plurality of signal lines 132 extending in a direction intersecting the scanning lines 131, and a plurality of signal lines 132 arranged in parallel on a transparent substrate. , And a plurality of common power supply lines 133 extending in the same direction. Each pixel is provided with a pixel (pixel area element) 71 at each intersection of the scanning line 131 and the signal line 132.
[0057]
For the signal line 132, a data side drive circuit 72 including a shift register, a level shifter, a video line, and an analog switch is provided.
On the other hand, for the scanning line 131, a scanning side driving circuit 73 including a shift register and a level shifter is provided. In each of the pixel regions 71, a switching thin film transistor (a power supply control unit) 142 to which a scanning signal is supplied to a gate electrode via a scanning line 131, and an image supplied from a signal line 132 via the switching thin film transistor 142. The storage capacitor cap for holding the signal, the current thin film transistor 143 to which the image signal held by the storage capacitor cap is supplied to the gate electrode, and the common thin film transistor 143 when electrically connected to the common power supply line 133 via the current thin film transistor 143 A pixel electrode 141 into which a drive current flows from the power supply line 133 and a light emitting unit 140 sandwiched between the pixel electrode 141 and the reflective electrode 154 are provided.
[0058]
Under such a configuration, when the scanning line 131 is driven and the switching thin film transistor 142 is turned on, the potential of the signal line 132 at that time is held in the storage capacitor cap, and according to the state of the storage capacitor cap, The on / off state of the current thin film transistor 143 is determined. Then, a current flows from the common power supply line 133 to the pixel electrode 141 through the channel of the current thin film transistor 143, and furthermore, a current flows to the reflection electrode 154 through the light emitting unit 140, so that the light emitting unit 140 responds to the amount of current flowing therethrough. To emit light.
Here, as shown in FIG. 5, the planar structure of each pixel 71 is such that four sides of a rectangular pixel electrode 141 have a signal line 132, a common power supply line 133, a scanning line 131, and other pixel electrodes (not shown). Are surrounded by the scanning lines.
[0059]
Next, a method for manufacturing the organic EL element provided in the EL display 70 will be described with reference to FIGS. 6 to 8 show only a single pixel 71 for simplification of the description.
First, a substrate P is prepared. Here, in the organic EL element, light emitted by a light-emitting layer described later can be extracted from the substrate side, or can be configured to be extracted from the side opposite to the substrate. In the case of a configuration in which emitted light is extracted from the substrate side, a transparent or translucent material such as glass, quartz, or resin is used as the substrate material, and particularly inexpensive glass is suitably used.
[0060]
Further, a color filter film, a color conversion film containing a fluorescent substance, or a dielectric reflection film may be disposed on the substrate to control the emission color.
In the case of a configuration in which emitted light is extracted from the opposite side of the substrate, the substrate may be opaque. A curable resin, a thermoplastic resin, or the like can be used.
In this embodiment, a transparent substrate P made of glass or the like is used as the substrate as shown in FIG. On the other hand, if necessary, a base protective film (not shown) made of a silicon oxide film having a thickness of about 200 to 500 nm is formed by a plasma CVD method using TEOS (tetraethoxysilane), oxygen gas or the like as a raw material. You.
[0061]
Next, the temperature of the transparent substrate P is set to about 350 ° C., and a semiconductor film 200 made of an amorphous silicon film having a thickness of about 30 to 70 nm is formed on the surface of the base protective film by a plasma CVD method. Next, a crystallization step such as laser annealing or a solid phase growth method is performed on the semiconductor film 200, and the semiconductor film 200 is crystallized into a polysilicon film. In the laser annealing method, for example, a line beam having a long dimension of 400 mm using an excimer laser is used, and its output intensity is, for example, 200 mJ / cm. ² It is. With respect to the line beam, the line beam is scanned such that a portion corresponding to 90% of the peak value of the laser intensity in the short dimension direction overlaps each region.
[0062]
Next, as shown in FIG. 6B, the semiconductor film (polysilicon film) 200 is patterned to form an island-like semiconductor film 210, and the surface thereof is subjected to plasma CVD using TEOS, oxygen gas or the like as a raw material. A gate insulating film 220 made of a silicon oxide film or a nitride film having a thickness of about 60 to 150 nm is formed by the method. Note that the semiconductor film 210 serves as a channel region and a source / drain region of the current thin film transistor 143 shown in FIG. 5, but a semiconductor film serving as a channel region and a source / drain region of the switching thin film transistor 142 at different cross-sectional positions. Is also formed. That is, in the manufacturing process shown in FIGS. 6 to 8, two types of transistors 142 and 143 are formed at the same time. However, since they are formed by the same procedure, in the following description, only the current thin film transistor 143 will be described. The description of the switching thin film transistor 142 is omitted.
[0063]
Next, as shown in FIG. 6C, after a conductive film made of a metal film of aluminum, tantalum, molybdenum, titanium, tungsten, or the like is formed by a sputtering method, the conductive film is patterned to form a gate electrode 143A. Is done.
Next, high-concentration phosphorus ions are implanted in this state, so that the source / drain regions 143a and 143b are formed in the semiconductor film 210 in a self-aligned manner with respect to the gate electrode 143A. Note that a portion where the impurity is not introduced becomes the channel region 143c.
[0064]
Next, as shown in FIG. 6D, after the interlayer insulating film 230 is formed, contact holes 232 and 234 are formed, and the relay electrodes 236 and 238 are buried in the contact holes 232 and 234.
Next, as shown in FIG. 6E, a signal line 132, a common power supply line 133, and a scanning line (not shown in FIG. 6) are formed on the interlayer insulating film 230. Here, the relay electrode 238 and each wiring may be formed in the same step. At this time, the relay electrode 236 is formed of an ITO film described later.
[0065]
Then, an interlayer insulating film 240 is formed so as to cover the upper surface of each wiring, a contact hole (not shown) is formed at a position corresponding to the relay electrode 236, and an ITO film is formed so as to be embedded in the contact hole. The pixel electrode 141 which is electrically connected to the source / drain region 143a is formed at a predetermined position surrounded by the signal line 132, the common power supply line 133, and the scanning line (not shown) by patterning the ITO film. Is formed. Here, a portion sandwiched between the signal line 132, the common power supply line 133, and the scanning line (not shown) is a place where the hole injection layer and the light emitting layer are formed as described later.
[0066]
Next, as shown in FIG. 7A, a partition 150 is formed so as to surround the formation location. The partition 150 functions as a partition member, and is preferably formed of an insulating organic material such as polyimide. The thickness of the partition 150 is set, for example, to 1 to 2 μm. Further, it is preferable that the partition walls 150 have incompatibility with the liquid composition discharged from the droplet discharge head 20. In order to cause the partition 150 to exhibit incompatibility, for example, a method of surface-treating the surface of the partition 150 with a fluorine-based compound or the like is adopted. Examples of the fluorine compound include CF ₄ , SF ₅ , CHF ₃ The surface treatment includes, for example, a plasma treatment and a UV irradiation treatment.
Under such a configuration, a step 111 having a sufficient height is formed between the formation position of the hole injection layer and the light emitting layer, that is, between the application position of these forming materials and the surrounding partition 150. Is done.
[0067]
Next, as shown in FIG. 7B, the liquid composition 114A including the material for forming the hole injection layer is surrounded by the partition wall 150 by the droplet discharge head 20, with the upper surface of the substrate P facing upward. The coating is selectively applied in the applied position, that is, in the partition 150.
The liquid composition 114A for forming the hole injection layer is generated by the composition adjusting device S, and includes a material for forming a hole injection layer, a solvent, and an antioxidant.
[0068]
As a material for forming the hole injection layer, the polymer precursor is polyphenylenevinylene, which is polytetrahydrothiophenylphenylene, 1,1-bis- (4-N, N-ditolylaminophenyl) cyclohexane, tris (8-hydroxyquinolinol) Aluminum, Baytron P, polystyrene sulfonic acid, and the like.
As the solvent, a polar solvent such as isopropyl alcohol, N-methylpyrrolidone, 1,3-dimethyl-imidazolinone is used.
[0069]
As the antioxidant, a radical chain inhibitor (primary antioxidant) or a peroxide decomposer (secondary antioxidant) can be used.
The radical chain inhibitor is intended to inhibit a chain growth reaction, and includes, for example, a phenolic antioxidant and an amine antioxidant. Among them, examples of the phenol-based antioxidant include monophenol-based, bisphenol-based, and polymer-type phenol-based antioxidants.
The peroxide decomposer is intended to decompose peroxides, and includes, for example, a sulfur-based antioxidant and a phosphorus-based antioxidant.
[0070]
Among the phenolic antioxidants, stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (dissolution parameter: 7.3 to 12.9) is used as the monophenolic antioxidant. ), 2,6-di-t-butyl-4-ethylphenol (dissolution parameter: 7.3 to 12.9).
Examples of bisphenol-based antioxidants include 4,4'-butylidenebis (3-methyl-6-t-butylphenol) (dissolution parameter: 8.0 to 12.9) and 3,9-bis [1,1-dimethyl- 2- [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane (dissolution parameter: 8.5 To 11.5).
As the high molecular weight phenolic antioxidant, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene (dissolution parameter: 9.0) -11.0), tetrakis- [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane (dissolution parameter: 8.2-10.5), 1, 3,5-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) -S-tridian-2,4,6- (1H, 3H, 5H) trione (dissolution parameter: 8.8) To 10.5).
[0071]
Examples of the sulfur-based antioxidants include dilauryl 3,3′-thiodipropionate (dissolution parameter: 8.2 to 10.5) and distearyl 3,3′-thiodipropionate (dissolution parameter: 8). .2 to 10.5).
Examples of the phosphoric acid-based antioxidant include tris (2,4-di-t-butylphenyl) phosphite (dissolution parameter: 7.3 to 12.0) and cyclic neopentanetetraylbis (2,4-diphenyl). -T-butylphenyl) phosphite (dissolution parameter: 8.0 to 11.5), 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (dissolution parameter: 8.3 to 9) .5) and the like.
[0072]
The solubility parameters of the antioxidants are approximately 7.0 to 13.0. Since the antioxidant having a solubility parameter of 7.0 to 13.0 has high solubility and dispersibility in a solvent, it is compatible with a material for forming a hole injection layer as an organic functional material and is sufficiently dispersed. Thus, no phase separation occurs even after film formation. Here, when the hole injection layer contains an antioxidant, it is desirable to use an antioxidant having a solubility parameter of 8.5 to 13. It is desirable to use an antioxidant having a solubility in a solvent of at least 0.001%, preferably at least 5%. Thereby, the antioxidant is dissolved in the solvent, and no phase separation occurs even after film formation.
[0073]
The amount of the antioxidant to be added is preferably 0.001 to 30% by weight, and more preferably 0.1 to 10% by weight, based on the material for forming the hole injection layer. By setting the addition amount in the above range, a desired antioxidant function can be obtained, and the function of the hole injection layer itself is not impaired.
[0074]
Further, the antioxidant is preferably transparent or translucent. Thereby, the coloring of the hole injection layer by the antioxidant can be prevented, and the influence of the antioxidant on the luminescent color, such as a change in the luminescent color and a decrease in the luminance of the organic EL device, can be suppressed, and the desired coloring state can be reduced. Obtainable. Note that, when the amount of the antioxidant added to the hole injection layer is sufficiently small, even if the antioxidant is colored, the influence on the emission color is small.
[0075]
When the liquid composition 1114A containing the above-described material for forming a hole injection layer, a solvent, and an antioxidant is ejected from the droplet ejection head 20 onto the substrate P, it tends to spread in the horizontal direction because of high fluidity. However, since the partition 150 is formed so as to surround the applied position, the liquid material composition 114A is prevented from spreading beyond the partition 150 to the outside.
[0076]
Next, as shown in FIG. 7C, the solvent of the liquid composition 114A is evaporated by heating or light irradiation, and a solid hole injection layer 140A is formed on the pixel electrode 141. Alternatively, baking may be performed at a predetermined temperature and time (for example, 200 ° C., 10 minutes) in an air environment or a nitrogen gas atmosphere. Alternatively, the solvent may be removed by being placed in a pressure environment lower than the atmospheric pressure (in a vacuum environment).
[0077]
Next, as shown in FIG. 8A, with the upper surface of the substrate P facing upward, the light-emitting layer forming material (light-emitting material), a solvent, and an antioxidant are The liquid composition 114B is selectively applied onto the hole injection layer 140A in the partition 150.
[0078]
As the light emitting layer forming material which is a light emitting material, for example, a material containing a precursor of a conjugated polymer organic compound and a fluorescent dye for changing the light emitting characteristics of the obtained light emitting layer is suitably used.
The precursor of the conjugated high molecular organic compound is discharged from the droplet discharge head 20 together with a fluorescent dye or the like, formed into a thin film, and then heat-cured as shown in the following formula (I) to form a conjugated system. A material capable of forming a light emitting layer to be a polymer organic EL layer. For example, in the case of a precursor sulfonium salt, a sulfonium group is eliminated by heat treatment to form a conjugated polymer organic compound. .
[0079]
Embedded image

[0080]
Such a conjugated polymer organic compound is solid and has strong fluorescence, and can form a uniform solid ultrathin film. Moreover, it has high forming ability and high adhesion to the ITO electrode. Furthermore, since the precursor of such a compound forms a strong conjugated polymer film after being cured, the precursor solution before heating and curing has a desired viscosity applicable to droplet discharge patterning described later. The film formation under optimum conditions can be performed easily and in a short time.
[0081]
As such a precursor, for example, a precursor of PPV (poly (para-phenylenevinylene)) or a derivative thereof is preferable. The precursor of PPV or its derivative is soluble in water or an organic solvent, and can be polymerized, so that a high-quality optically thin film can be obtained. Furthermore, PPV is a conductive polymer having strong fluorescence and π electrons of a double bond are non-polarized on the polymer chain, so that a high-performance organic EL device can be obtained.
[0082]
As a precursor of such a PPV or PPV derivative, for example, a PPV (poly (para-phenylenevinylene)) precursor, MO-PPV (poly (2,5-dimethoxy-1,4) as shown in Chemical Formula (II)) -Phenylenevinylene)) precursor, CN-PPV (poly (2,5-bishexyloxy-1,4-phenylene- (1-cyanovinylene))) precursor, MEH-PPV (poly [2-methoxy-5- (2′-ethylhexyloxy)]-para-phenylene vinylene) precursor and the like.
[0083]
Embedded image

[0084]
The precursor of PPV or a PPV derivative is soluble in water as described above, and is polymerized by heating after film formation to form a PPV layer. The content of the precursor represented by the PPV precursor is preferably from 0.01 to 10.0 wt%, more preferably from 0.1 to 5.0 wt%, based on the whole composition. If the amount of the precursor is too small, it is insufficient to form a conjugated polymer film. If the amount is too large, the viscosity of the composition becomes high, and it may not be suitable for highly accurate patterning by an inkjet method.
[0085]
Further, the material for forming the light emitting layer preferably contains at least one kind of fluorescent dye. This makes it possible to change the light-emitting characteristics of the light-emitting layer, and is effective, for example, as a means for improving the light-emitting efficiency of the light-emitting layer or changing the light absorption maximum wavelength (emission color). That is, the fluorescent dye can be used not only as a light emitting layer material but also as a dye material having a light emitting function itself. For example, most of the energy of excitons generated by carrier recombination on the conjugated polymer organic compound molecule can be transferred to the fluorescent dye molecule. In this case, since light emission occurs only from the fluorescent dye molecules having high fluorescence quantum efficiency, the current quantum efficiency of the light emitting layer also increases. Therefore, when a fluorescent dye is added to the material for forming the light emitting layer, the emission spectrum of the light emitting layer becomes the same as that of the fluorescent molecule, which is also effective as a means for changing the emission color.
[0086]
Here, the current quantum efficiency is a scale for considering the light emitting performance based on the light emitting function, and is defined by the following equation.
ηE = emitted photon energy / input electrical energy
Then, by converting the maximum wavelength of light absorption by doping with a fluorescent dye, for example, three primary colors of red, blue, and green can be emitted, and as a result, a full-color display can be obtained.
Further, by doping a fluorescent dye, the luminous efficiency of the EL element can be greatly improved.
[0087]
When a light emitting layer that emits red color light is formed as the fluorescent dye, it is preferable to use rhodamine or a rhodamine derivative having red color light. Since these fluorescent dyes are low-molecular, they are soluble in an aqueous solution, have good compatibility with PPV, and can easily form a uniform and stable light-emitting layer. Specific examples of such a fluorescent dye include rhodamine B, rhodamine B base, rhodamine 6G, and rhodamine 101 perchlorate, and a mixture of two or more of these may be used.
[0088]
In the case of forming a light-emitting layer that emits green light, it is preferable to use quinacridone having green light and its derivative. These fluorescent dyes, like the red fluorescent dye, are low-molecular and soluble in an aqueous solution, and have good compatibility with PPV and facilitate formation of a light emitting layer.
[0089]
Further, in the case of forming a light-emitting layer that emits blue color light, it is preferable to use distyrylbiphenyl having blue color light and derivatives thereof. These fluorescent dyes, like the red fluorescent dye, are low-molecular and thus soluble in a mixed solution of water and alcohol, and have good compatibility with PPV and facilitate formation of a light emitting layer.
[0090]
Other fluorescent dyes having blue light emission include coumarin and its derivatives. These fluorescent dyes, like the red fluorescent dye, are low-molecular and thus soluble in an aqueous solution, and have good compatibility with PPV and facilitate formation of a light emitting layer. Specific examples of such fluorescent dyes include coumarin, coumarin-1, coumarin-6, coumarin-7, coumarin 120, coumarin 138, coumarin 152, coumarin 153, coumarin 311, coumarin 314, coumarin 334, coumarin 337, coumarin. 343 and the like.
[0091]
Further, as another fluorescent dye having blue light emission, tetraphenylbutadiene (TPB) or a TPB derivative can be given. These fluorescent dyes, like the red fluorescent dye and the like, have low molecular weight and are soluble in an aqueous solution, and have good compatibility with PPV and can easily form a light emitting layer.
With respect to the above fluorescent dyes, only one kind may be used for each color, or two or more kinds may be used in combination.
[0092]
These fluorescent dyes are preferably added in an amount of 0.5 to 10% by weight, more preferably 1.0 to 5.0% by weight, based on the solid content of the precursor of the conjugated polymer organic compound. If the amount of the fluorescent dye is too large, it is difficult to maintain the weather resistance and durability of the light-emitting layer, while if the amount is too small, the effect of adding the fluorescent dye as described above cannot be sufficiently obtained. It is.
[0093]
The precursor and the fluorescent dye are preferably dissolved or dispersed in a polar solvent to form a liquid composition, and the liquid composition is preferably discharged from the droplet discharge head 20. Since the polar solvent can easily dissolve or uniformly disperse the precursor, the fluorescent dye, and the like, solid components in the light emitting layer forming material at the nozzle holes of the droplet discharge head 20 adhere or clog. Can be prevented.
[0094]
Specific examples of such polar solvents include water, alcohols such as methanol and ethanol, which are compatible with water, N, N-dimethylformamide (DMF), N-methylpyrrolidone (NMP), dimethylimidazoline (DMI), Organic solvents or inorganic solvents such as dimethylsulfoxide (DMSO), xylene, cyclohexylbenzene, and 2,3-dihydrobenzofuran are listed, and a mixture of two or more of these solvents may be used.
[0095]
As the antioxidant added to the light emitting layer, the above-described radical chain inhibitor (primary antioxidant) or peroxide decomposer (secondary antioxidant) can be used. The solubility parameter of the antioxidant to be added to the light-emitting layer is preferably 7.0 to 13.0, more preferably 7.5 to 10.5. Since such an antioxidant has high solubility and dispersibility in a solvent, it is compatible with the light emitting layer forming material, is sufficiently dispersed, and does not cause phase separation even after film formation. By including the antioxidant in the light-emitting layer, it is possible to suppress the occurrence of uneven light emission due to sufficient dispersion of the antioxidant.
[0096]
It is desirable to use an antioxidant having a solubility of the antioxidant in the solvent of 0.001% or more, preferably 5% or more. Thereby, the antioxidant is dissolved in the solvent, and no phase separation occurs even after film formation. Further, the addition amount of the antioxidant is preferably 0.001 to 30% by weight, and more preferably 0.1 to 10% by weight or less based on the material for forming the light emitting layer. By setting the addition amount in the above range, a desired antioxidant function can be obtained, and the function of the light emitting layer itself is not impaired.
[0097]
Also, the antioxidant contained in the light emitting layer is preferably transparent or translucent. Thereby, coloring of the light emitting layer by the antioxidant can be prevented, and the influence of the antioxidant on the luminescent color, such as a change in the luminescent color and a decrease in luminance, can be suppressed, and a desired coloring state can be obtained. Note that if the amount of the antioxidant added to the light emitting layer forming material is sufficiently small, even if the antioxidant is colored, the effect on the emission color is small.
[0098]
Further, it is preferable to add a wetting agent to the material for forming. Thereby, it is possible to effectively prevent the forming material from drying and solidifying in the nozzle holes of the droplet discharge head 20. Examples of such a wetting agent include polyhydric alcohols such as glycerin and diethylene glycol, and a mixture of two or more of these may be used. The amount of the wetting agent added is preferably about 5 to 20% by weight based on the total amount of the forming material.
In addition, other additives and a film stabilizing material may be added, and for example, a stabilizer, a viscosity adjuster, an antioxidant, a pH adjuster, a preservative, a resin emulsion, a leveling agent and the like can be used.
[0099]
When the liquid composition 114B containing such a light emitting layer forming material is discharged from the droplet discharge head 20, the liquid composition 114B is applied onto the hole injection layer 140A in the partition 150.
Here, the formation of the light emitting layer by discharging the liquid composition 114B includes a liquid composition including a light emitting layer forming material that emits red coloring light, and a light emitting layer forming material that emits green coloring light. A liquid material composition and a liquid material composition containing a material for forming a light emitting layer that emits blue color light are discharged and applied to the corresponding pixels 71. The pixels 71 corresponding to each color are determined in advance so that they are arranged regularly.
[0100]
After the liquid composition 114B containing the light emitting layer forming material of each color is discharged and applied in this manner, the solvent in the liquid composition 114B is evaporated to form the hole layer as shown in FIG. A solid light emitting layer 140B is formed on the injection layer 140A, whereby the light emitting section 140 including the hole layer injection layer 140A and the light emitting layer 140B is obtained. Here, as for the evaporation of the solvent in the liquid composition 114B containing the material for forming the light emitting layer, a treatment such as heating or decompression is performed as necessary. However, the material for forming the light emitting layer usually has good drying property and quick drying. Since it is dry, the light emitting layer 140B of each color can be formed in the order of application by sequentially discharging and applying the light emitting layer forming material of each color without performing such treatment.
Thereafter, as shown in FIG. 8C, the reflective electrode 154 is formed on the entire surface of the transparent substrate P or in a stripe shape. Thus, an organic EL element is manufactured.
[0101]
In such a method for manufacturing an organic EL element, a thin film such as a hole injection layer 140A or a light emitting layer 140B, which is a component of the organic EL element, is manufactured by a film forming apparatus (droplet discharging apparatus) IJ. The loss of the liquid composition serving as a material for forming the layer 140A and the light emitting layer 140B is small, and the hole injection layer 140A and the light emitting layer 140B are formed relatively inexpensively and stably.
[0102]
In the above embodiment, the antioxidant is added to the liquid composition 114B (114A) in advance, but the liquid composition 114B (114A) to which no antioxidant is added is discharged to form a film. Then, the antioxidant may be discharged and applied to this film. In this case, the antioxidant can be applied before the film containing the light emitting layer forming material is subjected to the drying treatment (heat treatment), that is, in a state where the film is wet. By doing so, the light emitting layer forming material and the antioxidant can be mixed on the substrate P. Of course, after the film containing the light emitting layer forming material is subjected to a drying treatment to remove the solvent, an antioxidant may be applied to the film. In this case, an antioxidant layer adjacent to the light emitting layer is formed.
[0103]
When applying the antioxidant, the second liquid composition comprising the antioxidant alone, the antioxidant and the solvent, and the second liquid composition comprising the antioxidant, the solvent and the binder resin Any form of the composition can be applied.
[0104]
Furthermore, in the above embodiment, the organic functional material is formed by the droplet discharge method using the droplet discharge device IJ. However, the present invention is not limited to the droplet discharge method. Can also be used. Other application methods can also be used when applying the second liquid composition.
[0105]
The step of forming the liquid composition and the step of forming a film may be performed in an air environment or in an atmosphere of an inert gas such as nitrogen gas. The step of generating the liquid composition by the composition adjusting device S and the step of forming the film by the droplet discharge device IJ are preferably performed in a clean room under an environment in which particles and chemicals are kept clean. When the liquid composition is generated in an atmospheric environment, for example, by dissolving the organic functional material and the antioxidant in a solvent under normal temperature and normal humidity (for example, at a temperature of 25 ° C. and a humidity of 35 to 45%). A liquid composition may be formed, or an organic functional material may be dissolved in a solvent, and then an antioxidant may be added to the solution.
[0106]
In the above embodiment, the antioxidant is added to each of the hole injection layer and the light emitting layer. However, the antioxidant may be added to only one of the hole injection layer and the light emitting layer. . Alternatively, an antioxidant may be added to a layer other than the hole injection layer and the light emitting layer among a plurality of layers constituting the organic EL element.
[0107]
"Example"
Hereinafter, examples of the material composition of the liquid material composition, the liquid material composition generating step, and the film forming step will be described.
<Liquid composition P1 for forming a hole injection layer>
・ Baytron P: 88.5wt%
・ Polystyrene sulfonic acid: 11.5wt%
<Liquid composition E1 for forming light emitting layer>
G (green): Compound 1 (0.76 g), Compound 2 (0.20 g), Compound 3 (0.04 g)
B (blue): Compound 1 (1.00 g)
R (red): Compound 4 (1.00 g)
100 ml of xylene as a solvent and 1 mg of the above-described antioxidant were added to each of the above RGB.
[0108]
In addition, the said compound 1-compound 4 are as follows.
[0109]
Embedded image

[0110]
Embedded image

[0111]
Embedded image

[0112]
Embedded image

[0113]
<Liquid composition P2 for forming a hole injection layer>
・ Baytron P: 11.08 wt%
・ Polystyrene sulfonic acid: 1.44 wt%
・ Isopropyl alcohol: 10 wt%
-N-methylpyrrolidone: 27.47 wt%
-1,3-dimethyl-imidazolinone: 50 wt%
<Light Emitting Layer Forming Liquid Composition E2>
G (green): Compound 1 (0.76 g), Compound 2 (0.20 g), Compound 3 (0.04 g)
B (blue): Compound 1 (1.00 g)
R (red): Compound 4 (1.00 g)
To each of the above RGB, 40 ml of cyclohexylbenzene and 60 ml of 2,3-dihydrobenzofuran were added as solvents, and 1 mg of the above-mentioned antioxidant was added.
[0114]
<Liquid composition generating step 1>
(Step Example 1) Under a clean room atmosphere environment (room temperature 25 ° C, humidity 35 to 45%), the material for forming a light emitting layer and an antioxidant were dissolved in a solvent to produce the compositions E1 and E2.
(Process Example 2) Under a cream room atmosphere environment (room temperature 25 ° C., humidity 35 to 45%), after dissolving a light emitting layer forming material in a solvent, an antioxidant is added to this solution, and the above composition E1, E2 is added. Generated.
[0115]
<Deposition process 1>
(Process Example 1) First, the above composition P1 was formed into a film by a spin coating method in a cream room atmosphere environment (room temperature 25 ° C., humidity 35 to 45%). Next, the film formed of the composition P1 was subjected to a baking treatment at 200 ° C. for 10 minutes in an air environment. Next, the composition E1 was formed on the hole injection layer by spin coating at room temperature in an air environment.
(Process Example 2) Under a cream room atmosphere environment (room temperature 25 ° C., humidity 35 to 45%), the composition P2 was discharged onto a substrate by a droplet discharging method. Next, the pressure in the clean room was reduced to a vacuum of 1 Torr (133.322 Pa or less), and drying was performed at room temperature for 20 minutes to form a film. Next, this film was subjected to a baking treatment at 200 ° C. for 10 minutes in an air environment. Next, the composition E2 was discharged onto the formed hole injection layer by a droplet discharging method. Next, a film made of the composition E2 was dried at 45 ° C. for 20 minutes in an air environment to form a film.
[0116]
<Liquid composition generation step 2>
(Step Example 1) Under a nitrogen gas atmosphere of a glove box (room temperature, moisture concentration and oxygen concentration of 1 ppm or less), a material for forming a light emitting layer and an antioxidant were dissolved in a solvent to produce the above compositions E1 and E2.
(Process Example 2) Under a nitrogen gas atmosphere (room temperature, moisture concentration and oxygen concentration of 1 ppm or less) in a glove box, a material for forming a light-emitting layer was dissolved in a solvent, and an antioxidant was added to the solution to prepare the composition E1, E2 was generated.
[0117]
<Deposition process 2>
(Step Example 1) The composition P1 was formed by a spin coating method in a nitrogen gas atmosphere having a water concentration and an oxygen concentration of 1 ppm or less. Next, the film formed of the composition P1 was subjected to a baking treatment at 200 ° C. for 10 minutes in a nitrogen gas atmosphere. Next, the composition E1 was formed on the hole injection layer by spin coating at room temperature under a nitrogen gas atmosphere.
(Process Example 2) In a nitrogen gas atmosphere having a water concentration and an oxygen concentration of 1 ppm or less, the composition P2 was discharged onto a substrate by a droplet discharging method. Next, a film was formed by drying at room temperature under a vacuum condition of 1 Torr (133.322 Pa or less) for 20 minutes. Next, this film was subjected to a baking treatment at 200 ° C. for 10 minutes in a nitrogen gas atmosphere. Next, the composition E2 was discharged onto the formed hole injection layer by a droplet discharge method, and dried at 45 ° C. for 20 minutes in a nitrogen gas atmosphere.
[0118]
FIGS. 9 to 12 show characteristic test results of the organic EL element in the case where the antioxidant is added to the light emitting layer and in the case where it is not added. In the figure, “A” is a test result when the antioxidant according to the present invention is added, and “B” is a test result when no antioxidant is added. FIG. 9 is a graph showing the relationship between applied voltage and current density, and FIG. 10 is a graph showing the relationship between applied voltage and luminance. FIG. 11 is a graph showing the relationship between the applied voltage and the luminous efficiency, and FIG. 12 is a graph showing the relationship between the driving time and the luminance. As shown in FIGS. 9 and 10, the organic EL element to which the antioxidant is added has almost the same element characteristics as the organic EL element to which the antioxidant is not added. It can be seen that the device function is not impaired. In addition, as shown in FIGS. 11 and 12, the luminous efficiency and the luminance half-life are improved by adding the antioxidant, and it can be seen that the device function is improved by adding the antioxidant.
[0119]
The droplet discharge device IJ of the present invention can also be used for forming a film that is a component of a color filter. FIG. 13 is a diagram illustrating a color filter formed on the substrate P, and FIG. 14 is a diagram illustrating a procedure for manufacturing the color filter.
As shown in FIG. 13, in this example, a plurality of color filter regions 351 are formed in a matrix on a rectangular substrate P from the viewpoint of improving productivity. These color filter regions 351 can be used as color filters suitable for a liquid crystal display device by cutting the substrate P later.
[0120]
The color filter region 351 is formed by a predetermined pattern of a liquid composition of R (red), a liquid composition of G (green), and a liquid composition of B (blue), in this example, a conventionally known stripe type. Is formed. The pattern may be a mosaic pattern, a delta pattern, a square pattern, or the like, in addition to the stripe pattern. The above-mentioned antioxidants are added to the respective liquid compositions of RGB.
[0121]
To form such a color filter region 351, first, a black matrix 352 is formed on one surface of a transparent substrate P as shown in FIG. The black matrix 352 is formed by applying a resin having no light transmittance (preferably black) to a predetermined thickness (for example, about 2 μm) by a method such as spin coating. Regarding the smallest display element surrounded by the lattice of the black matrix 352, that is, the filter element 353, for example, the width in the X-axis direction is about 30 μm, and the length in the Y-axis direction is about 100 μm.
[0122]
Next, as shown in FIG. 14B, droplets 354 of the liquid composition are discharged from the droplet discharge head 20 and land on the filter element 353. The amount of the discharged droplets 354 is a sufficient amount in consideration of the volume reduction of the liquid composition in the heating step.
After all the filter elements 353 on the substrate P are filled with the droplets 354 in this manner, the substrate P is heated using a heater so as to reach a predetermined temperature (for example, about 70 ° C.). By this heat treatment, the solvent of the liquid composition evaporates and the volume of the liquid composition decreases. In the case where the volume is severe, the droplet discharging step and the heating step are repeated until a sufficient film thickness is obtained as a color filter. By this treatment, the solvent contained in the liquid composition evaporates, and finally only the solid content contained in the liquid composition remains to form a film, and the color filter 355 as shown in FIG. Become.
[0123]
Next, in order to flatten the substrate P and protect the color filters 355, a protective film 356 is formed on the substrate P so as to cover the color filters 355 and the black matrix 352 as shown in FIG. In forming this protective film 356, a method such as a spin coating method, a roll coating method, and a ripping method can be adopted, but similarly to the color filter 355, a droplet discharging method can be used.
[0124]
Next, as shown in FIG. 14E, a transparent conductive film 357 is formed on the entire surface of the protective film 356 by a sputtering method, a vacuum evaporation method, or the like. Thereafter, the transparent conductive film 357 is patterned, and the pixel electrode 358 is patterned so as to correspond to the filter element 353 as shown in FIG. When a TFT (Thin Film Transistor) is used for driving the liquid crystal display panel, this patterning becomes unnecessary.
[0125]
Further, the film forming method according to the present invention is also applicable when forming a film that is a component of a liquid crystal element using the substrate P on which the color filter 355 is formed. That is, a known liquid crystal cell is manufactured using the substrate P to form a liquid crystal element, whereby a liquid crystal device can be formed. FIG. 15 is a view for explaining a structure of a liquid crystal cell for forming such a liquid crystal element. The liquid crystal device is a substrate on which the color filter (not shown in FIG. 15) is formed. A substrate 360 is provided. This counter substrate 360 is arranged on the side opposite to the circuit substrate (not shown) on which TFTs and the like are formed. A large number of microlenses 361 for condensing light incident from the counter substrate 360 on the circuit board (not shown) side are provided on the inner surface side of the counter substrate 360, and these micro lenses 361 are formed. A cover glass 363 is stuck on the side with the adhesive 362.
[0126]
A light-shielding film 364 is formed on the inner surface side of the cover glass 363 at a position corresponding to the boundary between the microlenses 361, and a transparent film of ITO or the like is formed on almost the entire surface of the cover glass 363 in a state of covering the light-shielding film 364. A counter electrode 365 made of a conductive material is formed. Then, an alignment film 366 made of an organic thin film such as a polyimide thin film is formed on the inner surface side of the counter electrode 365, and a liquid crystal 367 is sealed between the thus formed counter substrate 360 and the circuit board. Thus, a liquid crystal device is configured.
Also in the manufacture of a liquid crystal device having such a configuration, an antioxidant is added in advance to a liquid composition for forming a thin film, such as a light-shielding film 364 or an alignment film 366, which is a constituent element of the liquid crystal element. Alternatively, a film can be formed using this liquid composition.
[0127]
Further, the film forming method according to the present invention is also applicable to forming a film which is a component of an organic TFT element (organic thin film transistor element) in which at least a channel portion is formed of an organic film. As this organic TFT element, for example, there is one having a configuration as shown in FIG.
In FIG. 16, a gate electrode 451 is formed over a substrate 450. In addition, a gate insulating film 452 made of a high-dielectric-constant insulator is formed over the substrate 450 so as to cover the gate electrode 451, and an organic semiconductor layer 453 is formed on the gate insulating film 452. Then, a source electrode 454 and a drain electrode 455 are formed on the organic semiconductor layer 453, whereby an organic TFT element (organic thin film transistor element) is formed.
[0128]
To manufacture such an organic TFT element, first, a gate electrode material is provided on a substrate 450, and a gate electrode 451 is formed. Next, a gate insulating film 452 is formed so as to cover the gate electrode 451. As a material for forming the gate insulating film 452, various materials can be used without limitation. In particular, as an insulator having a high dielectric constant, a metal oxide thin film, preferably barium strontium titanate or titanium zirconate titanate is used. Barium titanate, lead zirconate titanate, lanthanum lead titanate, strontium titanate, barium titanate, barium magnesium fluoride, bismuth titanate, strontium bismuth titanate, strontium bismuth tantalate, bismuth tantalate niobate, niobium tantalate Inorganic materials such as strontium bismuth acid, pentoxide tantalum, titanium dioxide, trioxide yttrium, tantalum oxide, vanadium oxide, and titanium oxide are preferably used. In addition, organic materials such as polychloropyrene, polyethylene terephthalate, polyoxymethylene, polyvinyl chloride, polyvinylidene fluoride, cyanoethyl pullulan, polymethyl methacrylate, polysulfane, polycarbonate, and polyimide can also be used. In particular, in the case where the gate insulating film 452 is formed using the above-described inorganic material, annealing the film at an appropriate temperature in the range of 150 to 400 ° C. after film formation improves film quality, It is preferable because the dielectric constant can be increased.
[0129]
Next, an organic semiconductor layer 453 is formed on the gate insulating film 452. In forming the organic semiconductor layer 453, a droplet discharge device IJ is preferably used. As a material for forming the organic semiconductor layer 453, a polymer semiconductor or an oligomer semiconductor which shows an increase in field-effect mobility as the gate voltage increases is used. Specifically, naphthalene, anthracene, tetracene, pentacene, hexacene, and One or more of its derivatives and polyacetylene are used.
[0130]
Moreover, especially when it is used for a p-channel, an oligomer of thiophene having an oligopolymerization degree of 4 or more and 8 or less bonded via 2 to 5 carbon atoms; Conjugated oligomers of vinylene having 3 to 6 thiophene rings and thiophene as a terminal group, and thienylene, bonded together; linear dimers and trimers of benzo [1,2-b: 4,5 ′] dithiophene; The oligomer having a substituent (eg, an alkyl substituent having 1 to 20 carbon atoms) on 4 or 5 carbon atoms of the terminal thiophene; a p, p′-diaminobiphenyl complex in a polymer matrix; Can also be used. In particular, α-hexathienylene (α-6T) is preferably used. Furthermore, when it is used for the p-channel, 1,4,5,8-naphthalene tetracarboxyl dianhydride (NTCDA), 1,4,5,8-naphthalene tetracarboxyl diimide (NTCDI: Naphthalene tetracarboxylic diimide), 11,11,12,12-tetracyanonaphth-2,6-quinodimethane (TCNNQD: tetracyananaptho-2,6-quinodimethane) and the like can also be used.
[0131]
When such an organic semiconductor material is formed into a film by the droplet discharge device IJ, first, a liquid composition is generated by dissolving the organic semiconductor material in a solvent and adding the above-described antioxidant. . Then, the liquid composition is discharged onto the gate insulating film 452 of the substrate 450 and applied. Then, the organic semiconductor layer 453 is formed by removing the solvent by appropriately performing drying by heating, reduced pressure, or the like. Thereafter, a source electrode 454 and a drain electrode 455 are formed on the organic semiconductor layer 453, and an organic TFT element is obtained.
[0132]
The droplet discharge device of the present invention, a film forming device provided with the same, and the liquid composition of the present invention can be used for various applications without being limited to the above-described embodiments. For example, a metal composition can be directly patterned by discharging a liquid composition from a silver colloid solution or the like together with an antioxidant, applying the liquid composition on a substrate, and further drying by heating.
[0133]
The electro-optical device including the organic EL device and the liquid crystal device of the present invention, or the device including the organic TFT element of the present invention is applied to various electronic devices including a display unit. Hereinafter, application examples of an electronic apparatus including the electro-optical device according to the invention will be described.
[0134]
1. Watches
An example in which the electro-optical device of the present invention is applied to a wristwatch will be described. FIG. 17 is a perspective view showing the configuration of this wristwatch. A wristwatch 1100 includes the electro-optical device of the present invention as a display unit 1101.
[0135]
2. Mobile computer
An example in which the electro-optical device of the present invention is applied to a mobile (portable) personal computer will be described. FIG. 18 is a perspective view showing the configuration of this personal computer. The personal computer 1200 includes the electro-optical device of the present invention as a display unit 1201. The personal computer 1200 includes a main body 1202 having a keyboard 1203.
[0136]
3. mobile phone
An example in which the electro-optical device of the present invention is applied to a mobile phone will be described. FIG. 19 is a perspective view showing a configuration of the mobile phone. A mobile phone 1300 includes the electro-optical device of the present invention as a small-sized display portion 1301. The mobile phone 1300 includes a plurality of operation buttons 1302, an earpiece 1303, and a mouthpiece 1304.
[0137]
4. Electronic paper
An example in which the electro-optical device of the present invention is applied to flexible electronic paper will be described. FIG. 20 is a perspective view illustrating a configuration of the electronic paper. The electronic paper 1400 includes the electro-optical device of the invention as a display unit 1401. The electronic paper 1400 includes a main body 1402 made of a rewritable sheet having the same texture and flexibility as conventional paper.
FIG. 21 is a perspective view showing a configuration of an electronic notebook. An electronic notebook 1500 is formed by bundling a plurality of electronic papers 1400 shown in FIG. The cover 1501 includes a display data input unit (not shown) for inputting display data sent from, for example, an external device. Thus, the display content can be changed or updated in accordance with the display data while the electronic paper is bundled.
[0138]
5. Display device
An example in which the electro-optical device of the present invention is applied to a display device 1601 as shown in FIGS. 22A and 22B will be described. A display unit 1602 is detachably fixed to a frame 1601A of the display device 1601. The display unit 1602 is an extremely thin sheet-shaped, that is, a paper-shaped recording medium (so-called electronic paper), is held by conveyance rollers 1604 and 1606, and is arranged at a predetermined position on one side in the frame 1601A. A substantially central portion of the frame 1601A is recessed, and a rectangular hole 1601C is formed in the recess, and a glass substrate 1607 is attached to the hole 1601C. Further, the frame 1601A is provided with an insertion / removal opening 1608 into which the display unit 1602 is inserted and removed. A terminal unit 1610 is provided at an end of the display unit 1602 in the insertion direction. The terminal unit 1610 is electrically connected to the socket 1612 in the frame 1601A, and is thereby connected to the controller 1613 disposed on the other side of the frame 1601A.
Such a detachable display unit 1602 is excellent in portability and is easy to handle because it is not thick and bulky. Therefore, for example, it is possible to use the display unit 1602 alone while displaying a map related to the destination area.
[0139]
In addition to the above examples, other examples include a liquid crystal television, a viewfinder type or a monitor direct-view type video tape recorder, a car navigation device, a pager, an electronic notebook, a calculator, a word processor, a workstation, a videophone, and a POS terminal. And a device equipped with a touch panel. The electro-optical device according to the invention can be applied to a display unit of such an electronic apparatus.
[0140]
【The invention's effect】
As described above, by adding an antioxidant to a solution composed of an organic functional material and a solvent and liquefying the mixture, it is possible to suppress changes in physical properties and solute precipitation caused by oxygen, and to improve the liquid composition. Stability can be improved. By manufacturing various elements and devices using this liquid composition, highly reliable and excellent elements and devices can be provided.
[Brief description of the drawings]
FIG. 1 is a schematic configuration diagram showing one embodiment of a film manufacturing apparatus of the present invention.
FIG. 2 is a diagram illustrating a droplet discharge head.
FIG. 3 is a diagram illustrating a droplet discharge head.
FIG. 4 is a circuit diagram of the organic EL device.
FIG. 5 is a diagram illustrating a portion corresponding to one pixel of the organic EL device.
FIG. 6 is a diagram illustrating an example of a manufacturing process of the organic EL device.
FIG. 7 is a diagram illustrating an example of a manufacturing process of the organic EL device.
FIG. 8 is a diagram illustrating an example of a manufacturing process of the organic EL device.
FIG. 9 is a diagram showing characteristic test results of an organic EL device according to the present invention and a conventional organic EL device.
FIG. 10 is a diagram showing characteristic test results of an organic EL device according to the present invention and a conventional organic EL device.
FIG. 11 is a diagram showing characteristic test results of an organic EL device according to the present invention and a conventional organic EL device.
FIG. 12 is a diagram showing characteristic test results of an organic EL device according to the present invention and a conventional organic EL device.
FIG. 13 is a diagram illustrating a color filter.
FIG. 14 is a diagram illustrating an example of a manufacturing process of a color filter.
FIG. 15 illustrates a liquid crystal device.
FIG. 16 is a view showing an organic TFT element.
FIG. 17 is a diagram illustrating an electronic apparatus on which the electro-optical device according to the invention is mounted.
FIG. 18 is a diagram illustrating an electronic apparatus on which the electro-optical device according to the invention is mounted.
FIG. 19 is a diagram illustrating an electronic apparatus on which the electro-optical device according to the invention is mounted.
FIG. 20 is a diagram illustrating an electronic apparatus on which the electro-optical device according to the invention is mounted.
FIG. 21 is a diagram illustrating an electronic apparatus on which the electro-optical device according to the invention is mounted.
FIG. 22 is a diagram illustrating an electronic apparatus on which the electro-optical device according to the invention is mounted.
[Explanation of symbols]
114A, 114B Liquid composition
140A hole injection layer (material layer)
140B Light emitting layer (material layer)
IJ droplet discharge device (film formation device, liquid material discharge device)
S composition adjusting device
ST stage device

Claims (44)

A composition comprising an antioxidant added to a liquid containing an organic functional material and a solvent. The composition according to claim 1, wherein the antioxidant is transparent or translucent. 3. The composition according to claim 1, wherein the antioxidant is a radical chain inhibitor. The composition according to claim 1, wherein the antioxidant is a peroxide decomposer. The composition according to any one of claims 1 to 4, wherein the organic functional material is a light emitting material. The composition according to claim 1, wherein the organic functional material is a polymer material. The composition according to any one of claims 1 to 4, wherein the organic functional material is an organic electroluminescent material. The composition according to claim 7, wherein the organic functional material is a hole injection material. The composition according to claim 7, wherein the organic functional material is a light emitting material. The composition according to any one of claims 1 to 9, wherein the solubility parameter of the antioxidant is 7.0 or more and 13.0 or less. A film formation method, comprising: adding an antioxidant to a liquid containing an organic functional material and a solvent to prepare a composition; and providing the composition on a predetermined surface to form a film. The film forming method according to claim 11, wherein the organic functional material is a light emitting material. The method according to claim 11, wherein the organic functional material is a material for forming a component of an organic electroluminescence element. The film forming method according to claim 11, wherein the organic functional material is a material for forming a component of a color filter. The film forming method according to claim 11, wherein the organic functional material is a material for forming a component of an organic thin film transistor element. The method according to claim 11, wherein the organic functional material is a material for forming a component of a liquid crystal element. 17. The film forming method according to claim 11, wherein the film is formed by discharging the composition onto the predetermined surface by a liquid material discharging device. A film formation method comprising: disposing a composition containing an organic functional material and a solvent on a predetermined surface to form a film; and disposing an antioxidant on the film. A second composition containing the antioxidant and the solvent is prepared, and the composition is delivered to a liquid discharge device through a flow path, and discharged to the film by the liquid discharge device, thereby oxidizing the composition. The method according to claim 18, wherein an inhibitor is disposed on the film. A composition adjusting device for adjusting a composition containing an organic functional material, a solvent, and an antioxidant,
A film discharging device for discharging a liquid containing the composition adjusted by the composition adjusting device to a predetermined surface. A composition adjusting device for adjusting a composition containing an organic electroluminescent material, a solvent, and an antioxidant,
A film forming unit for arranging the composition adjusted by the composition adjusting device on a predetermined surface to form a film. 22. The film forming apparatus according to claim 20, further comprising a stage device that can move while supporting the substrate having the predetermined surface. In an electro-optical device having a functional element,
An electro-optical device, wherein the functional element contains an antioxidant. In an electro-optical device having a functional element,
An electro-optical device, wherein an antioxidant layer containing an antioxidant is adjacent to the functional element. 25. The electro-optical device according to claim 23, wherein the functional element is a light emitting element. The light emitting element includes a light emitting layer and a pair of electrodes sandwiching the light emitting layer,
A substrate supporting the light emitting element,
The electro-optical device according to claim 25, further comprising: an energization control unit that is provided on the base material and that controls energization of the electrodes. 25. The electro-optical device according to claim 23, wherein the functional element is an organic electroluminescence element. In a method for manufacturing an electro-optical device having a functional element,
A step of adjusting the composition by adding an antioxidant to a solution containing the material for forming a functional element and a solvent,
Providing the composition on a substrate and forming a film that is a component of the functional element. The method for manufacturing an electro-optical device according to claim 28, wherein the film is formed by discharging a liquid material containing the composition onto the base material by a liquid material discharge device. In a method for manufacturing an electro-optical device having a functional element,
A step of providing a composition containing the material for forming a functional element and a solvent on a substrate to form a film that is a component of the functional element,
Arranging an antioxidant on the film. When the antioxidant is provided, a second composition containing the antioxidant and a solvent is prepared, and a liquid material containing the second composition is discharged onto the film by a liquid discharge device. The method for manufacturing an electro-optical device according to claim 30, wherein The method of manufacturing an electro-optical device according to any one of claims 28 to 31, wherein the functional element is an organic electroluminescence element. An organic electroluminescence device having a plurality of material layers,
An organic electroluminescent device, wherein at least one of the plurality of material layers contains an antioxidant. The organic electroluminescent device according to claim 33, wherein an antioxidant is contained in the light emitting layer of the material layers. An organic electroluminescence device having a plurality of material layers,
An organic electroluminescence device, wherein an antioxidant layer containing an antioxidant is formed between predetermined material layers among the plurality of material layers. In a method of manufacturing an organic electroluminescence device having a plurality of material layers,
Manufacturing an organic electroluminescence device, wherein an antioxidant is added to a solution containing the material for forming a material layer and a solvent to adjust a composition, and the material layer is formed using the composition. Method. The method for manufacturing an organic electroluminescence device according to claim 36, wherein the material layer is formed by discharging a liquid containing the composition with a liquid discharge device. In a method of manufacturing an organic electroluminescence device having a plurality of material layers,
A method for manufacturing an organic electroluminescence device, comprising: forming the material layer using a composition containing the material for forming a material layer and a solvent; and providing an antioxidant on the material layer. When the antioxidant is provided, a second composition is adjusted with the antioxidant and a solvent, and a liquid containing the second composition is discharged to the material layer by a liquid discharge device. The method for manufacturing an organic electroluminescence device according to claim 38, wherein A device manufactured using the composition according to any one of claims 1 to 10. A method for producing a device, comprising using the composition according to any one of claims 1 to 10. 42. The device manufacturing method according to claim 41, further comprising a step of discharging a liquid containing the composition by a liquid discharger. An electronic apparatus comprising the electro-optical device according to any one of claims 23 to 27. An electronic apparatus comprising the organic electroluminescence device according to claim 33.

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