JP2004327357A - Manufacturing method and device of functional element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a manufacturing method of a functional element capable of forming a flat functional part in a good manufacturing efficiency by using a discharging method like an ink-jet method. <P>SOLUTION: The manufacturing method of the functional element has a functional layer forming process dropping a functional layer forming liquid containing a solvent on a functional layer forming area on a substrate where the functional layer is to be formed by a discharging method, and drying and solidifying the layer afterwards. Temperature of the functional layer forming liquid after dropping is controlled so as to satisfy Tmax/Tmin≤2, wherein, Tmax is a maximum thickness of the layer in the functional area of the effective area used as the functional part of the functional element, and Tmin is a minimum thickness thereof. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

ただし、ｎは２以上の整数であり、Ｒ^１，Ｒ^２はそれぞれ炭素数１〜１０の置換もしくは非置換のアルキル、アルケニル、アリールあるいはシアノアルキル基であり、モル比で全体の４０％以下がビニル、フェニル、ハロゲン化フェニルである。また、Ｒ^１、Ｒ^２がメチル基のものが表面エネルギーが最も小さくなるので好ましく、モル比でメチル基が６０％以上であることが好ましい。また、鎖末端もしくは側鎖には、分子鎖中に少なくとも１個以上の水酸基等の反応性基を有する。
【００９３】
また、上記のオルガノポリシロキサンとともに、ジメチルポリシロキサンのような架橋反応をしない安定なオルガノシリコン化合物をバインダに混合してもよい。
【００９４】
ｃ．分解物質
上記第２の形態および第３の形態においては、さらにエネルギー照射による光触媒の作用により分解され、これにより濡れ性変化層上の濡れ性を変化させることができる分解物質を濡れ性変化層に含有させる必要がある。すなわち、バインダ自体に濡れ性変化層上の濡れ性を変化させる機能が無い場合、およびそのような機能が不足している場合に、上述したような分解物質を添加して、上記濡れ性変化層上の濡れ性の変化を起こさせる、もしくはそのような変化を補助させるようにするのである。
【００９５】
このような分解物質としては、光触媒の作用により分解し、かつ分解されることにより濡れ性変化層表面の濡れ性を変化させる機能を有する界面活性剤を挙げることができる。具体的には、日光ケミカルズ（株）製ＮＩＫＫＯＬ ＢＬ、ＢＣ、ＢＯ、ＢＢの各シリーズ等の炭化水素系、デュポン社製ＺＯＮＹＬ ＦＳＮ、ＦＳＯ、旭硝子（株）製サーフロンＳ−１４１、１４５、大日本インキ化学工業（株）製メガファックＦ−１４１、１４４、ネオス（株）製フタージェントＦ−２００、Ｆ２５１、ダイキン工業（株）製ユニダインＤＳ−４０１、４０２、スリーエム（株）製フロラードＦＣ−１７０、１７６等のフッ素系あるいはシリコーン系の非イオン界面活性剤を挙げることができ、また、カチオン系界面活性剤、アニオン系界面活性剤、両性界面活性剤を用いることもできる。
【００９６】
また、界面活性剤の他にも、ポリビニルアルコール、不飽和ポリエステル、アクリル樹脂、ポリエチレン、ジアリルフタレート、エチレンプロピレンジエンモノマー、エポキシ樹脂、フェノール樹脂、ポリウレタン、メラミン樹脂、ポリカーボネート、ポリ塩化ビニル、ポリアミド、ポリイミド、スチレンブタジエンゴム、クロロプレンゴム、ポリプロピレン、ポリブチレン、ポリスチレン、ポリ酢酸ビニル、ナイロン、ポリエステル、ポリブタジエン、ポリベンズイミダゾール、ポリアクリルニトリル、エピクロルヒドリン、ポリサルファイド、ポリイソプレン等のオリゴマー、ポリマー等を挙げることができる。
【００９７】
ｄ．フッ素の含有
また、本態様においては、濡れ性変化層がフッ素を含有し、さらにこの濡れ性変化層表面のフッ素含有量が、濡れ性変化層に対しエネルギーを照射した際に、上記光触媒の作用によりエネルギー照射前に比較して低下するように上記濡れ性変化層が形成されていることが好ましい。
【００９８】
このような特徴を有する濡れ性変化層であれば、エネルギーをパターン照射することにより、後述するように容易にフッ素の含有量の少ない部分からなるパターンを形成することができる。ここで、フッ素は極めて低い表面エネルギーを有するものであり、このためフッ素を多く含有する物質の表面は、臨界表面張力がより小さくなる。したがって、フッ素の含有量の多い部分の表面の臨界表面張力に比較してフッ素の含有量の少ない部分の臨界表面張力は大きくなる。これはすなわち、フッ素含有量の少ない部分はフッ素含有量の多い部分に比較して親液性領域となっていることを意味する。よって、周囲の表面に比較してフッ素含有量の少ない部分からなるパターンを形成することは、撥液性域内に親液性領域のパターンを形成することとなる。
【００９９】
したがって、このような濡れ性変化層を用いた場合は、エネルギーをパターン照射することにより、上記機能性層形成用塗工液を塗布し、高精細な機能性層を形成することが可能となるからである。
【０１００】
上述したような、フッ素を含む濡れ性変化層中に含まれるフッ素の含有量としては、エネルギーが照射されて形成されたフッ素含有量が低い親液性領域におけるフッ素含有量が、エネルギー照射されていない部分のフッ素含有量を１００とした場合に１０以下、好ましくは５以下、特に好ましくは１以下であることが好ましい。
【０１０１】
このような範囲内とすることにより、エネルギー照射部分と未照射部分との親液性に大きな違いを生じさせることができる。したがって、このような濡れ性変化層に、例えば上記機能性層形成用塗工液を塗布することにより、フッ素含有量が低下した親液性領域のみに正確に機能性層を形成することが可能となるからである。なお、この低下率は重量を基準としたものである。
【０１０２】
このような濡れ性変化層中のフッ素含有量の測定は、一般的に行われている種々の方法を用いることが可能であり、例えばＸ線光電子分光法（Ｘ−ｒａｙ Ｐｈｏｔｏｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ， ＥＳＣＡ（Ｅｌｅｃｔｒｏｎ Ｓｐｅｃｔｒｏｓｃｏｐｙ ｆｏｒ Ｃｈｅｍｉｃａｌ Ａｎａｌｙｓｉｓ）とも称される。）、蛍光Ｘ線分析法、質量分析法等の定量的に表面のフッ素の量を測定できる方法であれば特に限定されるものではない。
【０１０３】
また、本態様においては、光触媒として上述したように二酸化チタンが好適に用いられるが、このように二酸化チタンを用いた場合の、濡れ性変化層中に含まれるフッ素の含有量としては、Ｘ線光電子分光法で分析して定量化すると、チタン（Ｔｉ）元素を１００とした場合に、フッ素（Ｆ）元素が５００以上、このましくは８００以上、特に好ましくは１２００以上となる比率でフッ素（Ｆ）元素が濡れ性変化層表面に含まれていることが好ましい。
【０１０４】
フッ素（Ｆ）が濡れ性変化層にこの程度含まれることにより、濡れ性変化層上における臨界表面張力を十分低くすることが可能となることから表面における撥液性を確保でき、これによりエネルギーをパターン照射してフッ素含有量を減少させたパターン部分における表面の親液性領域との濡れ性の差異を大きくすることができるからである。
【０１０５】
さらに、エネルギーをパターン照射して形成される親インク領域におけるフッ素含有量が、チタン（Ｔｉ）元素を１００とした場合にフッ素（Ｆ）元素が５０以下、好ましくは２０以下、特に好ましくは１０以下となる比率で含まれていることが好ましい。
【０１０６】
濡れ性変化層中のフッ素の含有率をこの程度低減することができれば、機能性層を形成するためには十分な親液性を得ることができ、上記エネルギーが未照射である部分の撥液性との濡れ性の差異により、機能性層を精度良く形成することが可能となる。
【０１０７】
ｅ．濡れ性変化層の製造方法
上述したようにオルガノポリシロキサンをバインダとして用いた場合は、上記濡れ性変化層は、光触媒とバインダであるオルガノポリシロキサンとを必要に応じて他の添加剤とともに溶剤中に分散して塗布液を調製し、この塗布液を基材上に塗布することにより形成することができる。使用する溶剤としては、エタノール、イソプロパノール等のアルコール系の有機溶剤が好ましい。塗布はスピンコート、スプレーコート、ディッブコート、ロールコート、ビードコート等の公知の塗布方法により行うことができる。バインダとして紫外線硬化型の成分を含有している場合、紫外線を照射して硬化処理を行うことにより、濡れ性変化層を形成することができる。
【０１０８】
（２）基材
次に、本態様に用いられる基材について説明する。本態様に用いられる基材は、上記濡れ性変化層が形成可能であれば、特に限定されるものではなく、製造される機能性素子の種類や用途により適宜選択されるものである。また、透明性や可撓性についても適宜選択されるものである。
【０１０９】
なお、本態様においては、基材表面と上記濡れ性変化層等との密着性を向上させるために、基材上にアンカー層を形成するようにしてもよい。このようなアンカー層としては、例えば、シラン系、チタン系のカップリング剤等を挙げることができる。
【０１１０】
（３）親液性領域（機能性層形成用領域）の形成
次に、親液性領域（機能性層形成用領域）の形成について説明する。本態様においては、エネルギー照射に伴う光触媒の作用により、上述した濡れ性変化層の濡れ性を変化させ、機能性層を形成する領域である機能性層形成用領域を親液性領域とする。
【０１１１】
本態様における上記親液性領域の形成は、例えば図６に示すように、上記基材１１上に形成された上記濡れ性変化層１２に、例えばフォトマスク１３等のマスクを用いてエネルギー１４を照射する（図６（ａ））。これにより、エネルギー照射された領域の濡れ性変化層１２上の濡れ性が変化し、親液性領域とされた機能性層形成用領域１５とすることができるのである（図６（ｂ））。
【０１１２】
なお、本態様でいうエネルギー照射（露光）とは、上記濡れ性変化層の濡れ性を変化させることが可能ないかなるエネルギー線の照射をも含む概念であり、可視光の照射に限定されるものではない。
【０１１３】
通常このようなエネルギー照射に用いる光の波長は、４００ｎｍ以下の範囲、好ましくは３８０ｎｍ以下の範囲から設定される。これは、上述したように光触媒に二酸化チタンが好ましく用いられ、この二酸化チタンにより光触媒作用を活性化させるエネルギーとして、上述した波長の光が好ましいからである。
【０１１４】
このようなエネルギー照射に用いることができる光源としては、水銀ランプ、メタルハライドランプ、キセノンランプ、エキシマランプ、その他種々の光源を挙げることができる。
【０１１５】
上述したような光源を用い、フォトマスクを介したパターン照射により行う方法の他、エキシマ、ＹＡＧ等のレーザを用いてパターン状に描画照射する方法を用いることも可能である。
【０１１６】
また、エネルギー照射に際してのエネルギーの照射量は、濡れ性変化層が光触媒の作用により濡れ性が変化するのに必要な照射量とする。
【０１１７】
この際、上記濡れ性変化層を加熱しながらエネルギー照射することにより、感度を上昇させことが可能となり、効率的な濡れ性の変化を行うことができる点で好ましい。具体的には３０℃〜８０℃の範囲内で加熱することが好ましい。
【０１１８】
（第２の態様）
次に、上記機能性層形成用領域の外周部に、隔壁が設けられており、この隔壁により機能性層形成用領域と、機能性層を形成しない領域とが区切られている場合について説明する。本態様は、例えば図７に示すように、基板１上に、隔壁６が設けられており、この隔壁６により上記機能性層形成用領域ｂと、機能性層を形成しない領域とが区切られているものである。上記隔壁は、上記機能性層形成用領域と、上記機能性層を形成しない領域とを区切るものであれば、特に限定されるものではなく、例えばカラーフィルタにおけるブラックマトリックス等であってもよい。ここで、本態様においては、例えば図８に示すように、隔壁６の高さｃが、形成された機能性層４の最大膜厚Ｔｍａｘより低い場合には、隔壁６は親液性であっても撥液性であってもよいが、例えば図９に示すように、隔壁６の高さｃが、形成された機能性層４の最大膜厚Ｔｍａｘより高い場合には、隔壁６は撥液性であることが必要とされる。これは、形成された機能性層の最大膜厚より、高さが高い隔壁が親液性である場合には、隔壁と隔壁との間に塗布された機能性層形成用塗工液が、隔壁による影響を受けるため、上記温度調整によって、上記機能性層形成用塗工液中に含有される溶媒の揮発速度に伴うフローを制御することが困難となり、本発明の効果を期し難いからである。なお、ここでいう親液性および撥液性とは、上記第１の態様で説明した親液性領域における親液性、および撥液性領域における撥液性と同様であるので、ここでの説明は省略する。
【０１１９】
またこの際、上記機能性層形成用領域は親液性であることが好ましい。上記機能性層形成用領域が撥液性である場合には、機能性層形成用塗工液をはじいてしまい、均一な機能性層を形成することが困難となる。またさらに、機能性層形成用塗工液の撥液性の影響を受けることにより、上述した温度調整によって、上記機能性層形成用塗工液中に含有される溶媒の揮発速度に伴うフローを制御することが困難となる場合があるからである。
【０１２０】
Ｂ．有機ＥＬ素子の製造方法
次に、本発明の有機ＥＬ素子の製造方法について説明する。本発明の有機ＥＬ素子の製造方法は、上述した機能性素子の製造方法により製造される上記機能性部が、少なくとも発光層を有する有機ＥＬ層であることを特徴とするものである。本発明によれば、有機ＥＬ素子における有機ＥＬ層が、上述した機能性素子の製造方法により製造されることにより、有機ＥＬ層の膜厚を均一なものとすることができ、色ムラやデバイス寿命の短命化等の少ない、高品質な有機ＥＬ素子とすることができるのである。
【０１２１】
本発明における有機ＥＬ素子の製造方法は、例えば図１０に示すように、透明基材１上に、第１電極層１５をフォトリソグラフィー法等によりパターン状に形成し、その第１電極層１５の端部を覆うように絶縁層５を形成する。その後、絶縁層より幅が狭くなるように撥液性の隔壁６を形成する（図１０（ａ））。
【０１２２】
続いて、例えばインクジェット装置３によりＲ、Ｇ、Ｂ各色の発光層形成用塗工液２を、上記第１電極層１５上である、上記隔壁６間に塗布し（図１０（ｂ））、上述した温度調整を行うことにより、平坦な発光層４を形成する（図１０（ｃ））。さらに、その発光層４上に第２電極層１６を形成することにより有機ＥＬ素子とする（図１０（ｄ））方法等とすることができる。
【０１２３】
本発明により製造される有機ＥＬ素子は、上記の有機ＥＬ素子に限定されるものではなく、例えば第１電極層上に正孔注入層を形成するものであってもよく、また発光層形成後に、電子注入層や電子輸送層、電荷ブロッキング層等を形成するものであってもよい。
【０１２４】
また、上記「Ａ．機能性素子の製造方法」で説明した濡れ性変化層等が形成されているものであってもよい。
【０１２５】
なお、本発明に用いられる有機ＥＬ素子の各構成等に用いられる材料等は、通常有機ＥＬ素子の製造方法に用いられる材料を用いることが可能であるので、ここでの説明は省略する。
【０１２６】
Ｃ．インクジェット装置
次に、本発明のインクジェット装置について説明する。本発明のインクジェット装置には、２つの態様がある。第１の態様は、インクを吐出する吐出部および上記インクが吐出される基板を保持する基板保持部とを有するインクジェット装置であって、上記インクの温度を調整するインク温度調整機構を有するものであり、第２の態様は、インクを吐出する吐出部および上記インクが吐出される基板を保持する基板保持部とを有するインクジェット装置であって、上記基板の温度を調整する基板温度調整機構を有するものである。
【０１２７】
上記どちらの態様においても、吐出部により吐出されたインクの温度を調整することが可能となる。これにより、上記インクジェット装置により塗布されたインクの溶剤の揮発速度を調整することが可能となり、形成された膜の形状を制御することが可能となるのである。
【０１２８】
以下、それぞれの態様についてわけて説明する。
【０１２９】
１．第１の態様
まず、本発明のインクジェット装置の第１の態様について説明する。本発明のインクジェット装置の第１の態様は、インクを吐出する吐出部および上記インクが吐出される基板を保持する基板保持部とを有するインクジェット装置であって、上記インクの温度を調整するインク温度調整機構を有するものである。
【０１３０】
本態様のインクジェット装置は、上記インクジェット装置から吐出されるインクの温度を調整することにより、吐出されたインクの温度の調整をすることに特徴を有するものである。以下、本態様のインクジェット装置の各構成について説明する。
【０１３１】
（吐出部）
まず、本態様のインクジェット装置における吐出部について説明する。本態様に用いられる吐出部は、インクを吐出する部材であり、通常インクジェット装置に用いられる吐出部を用いることが可能である。
【０１３２】
本発明におけるインクの吐出方法としては、特に限定されるものではなく、例えば帯電したインクを連続的に噴射し磁場によって制御する方法、圧電素子を用いて間欠的にインクを噴射する方法、インクを加熱しその発泡を利用して間欠的に噴射する方法等の各種の方法を用いることが可能である。
【０１３３】
（基板保持部）
次に、本発明のインクジェット装置に用いられる基板保持部について説明する。本発明のインクジェット装置に用いられる基板保持部は、上述した吐出部より吐出されたインクを塗布する対象である基板を保持するものである。本発明においては、基板を保持することが可能であれば特に限定されるものではなく、通常上記吐出部と、Ｘ、Ｙ、Ｚ方向に相対的に移動可能なものとされる。
【０１３４】
（インク温度調整機構）
次に、本態様のインクジェット装置に用いられるインク温度調整機構について説明する。本態様に用いられるインク温度調整機構は、上記吐出部から吐出されるインクの温度を目的とする温度に保持することが可能であれば、特に限定されるものではなく、例えば上記吐出部にインクを供給するためにインクを保持する例えばタンク等の温度を調整する機構であってもよく、また上記吐出部の温度を所定の温度に保持し、吐出されるインクの温度を調整するものであってもよい。
【０１３５】
２．第２の態様
次に、本発明のインクジェット装置における第２の態様について説明する。本発明のインクジェット装置における第２の態様は、インクを吐出する吐出部および上記インクが吐出される基板を保持する基板保持部とを有するインクジェット装置であって、上記基板の温度を調整する基板温度調整機構を有するものである。
【０１３６】
本発明によれば、上記吐出部より吐出される機能性層形成用塗工液の液滴は十分小さい。従って上記基板温度調整機構により、基板の温度を目的とする温度に保持することによって、上記機能性層形成用塗工液が着弾する際に、基板と機能性層形成用塗工液とを等しい温度とすることができ、上記機能性層形成用塗工液を目的とする温度とすることが可能となるのである。
【０１３７】
以下、本態様のインクジェット装置の基板温度調整機構について説明する。なお、吐出部および基板保持部については、上述した第１の態様と同様であるので、ここでの説明は省略する。
【０１３８】
（基板温度調整機構）
本態様のインクジェット装置に用いられる基板温度調整機構について説明する。本態様に用いられる基板温度調整機構は、上記吐出部から吐出された基板の温度を目的とする温度に保持することが可能であれば、特に限定されるものではなく、例えば水やペルチェ素子により冷却する冷却機構および加熱機構を有するものが挙げられる。
【０１３９】
３．その他
本発明のインクジェット装置は、上記インク温度調整機構および基板温度調整機構を有するものであってもよい。
【０１４０】
なお、本発明は、上記実施形態に限定されるものではない。上記実施形態は例示であり、本発明の特許請求の範囲に記載された技術的思想と実質的に同一な構成を有し、同様な作用効果を奏するものは、いかなるものであっても本発明の技術的範囲に包含される。
【０１４１】
【実施例】
以下に実施例を示し、本発明をさらに説明する。
【０１４２】
［実施例１］
（基板の作製）
２００μｍの厚さのＰＥＴ上にＩＴＯをスパッタにより成膜し、８０μｍの線幅のＩＴＯを２０μｍの間隔でパターニングした後、ＩＴＯパターンのエッジを被うようにＩＴＯの間を厚さ１μｍの絶縁層をフォトリソグラフィー法により形成した。絶縁層にはレジストとしてＺＰＰ−１８５０（日本ゼオン（株））を用いた。
【０１４３】
次に、下記組成の光触媒含有層用の塗布液を調整した。

上記の光触媒含有層塗液を上記基板上に塗布し、１５０℃、１０分間の乾燥処理後、加水分解、重縮合反応を進行させて、光触媒がオルガノシロキサン中に強固に固定された透明な光触媒含有層を厚み２０ｎｍに形成した。
【０１４４】
続いて、上記の光触媒含有層にマスクを介して水銀灯（波長３６５ｎｍ）により７０ｍＷ／ｃｍ^２の照度で５０秒間パターン照射を行い、照射部位と非照射部位との水に対する接触角を接触角測定器（協和界面科学（株）製ＣＡ−Ｚ型）を用いて測定した結果（マイクロシリンジから水滴を滴下して３０秒後）、非照射部位における水の接触角は１４２°であるのに対し、照射部位における水の接触角は１０°以下であり、照射部位と非照射部位との濡れ性の相違によるパターン形成が可能なことが確認された。
【０１４５】
（発光層形成用塗工液の準備）
次に、発光層として以下の組成物を発光層形成用塗工液として準備した。
・ポリビニルカルバゾール ７重量部
・発光色素（Ｒ，Ｇ，Ｂ） ０．１重量部
・オキサジアゾール化合物 ３重量部
・テトラリン ９９０重量部
上記発光層形成用塗工液の濃度を測定したところ、粘度は１２ｍ・Ｐａ・ｓであった。
【０１４６】
（発光層形成用塗工液の塗布）
次に、チラーによる水冷式冷却機構、加熱機構および温度制御機構を持つ基板ステージ上に上述した基板をセットした。このとき、室温は２１℃であった。
【０１４７】
続いて、上述した基板温度を１８℃に保持しながら、インクジェット法により前記発光層形成用塗工液（Ｒ、Ｇ、Ｂ）のインクを発光層形成用領域である親液性領域にそれぞれ形成した。目視により溶剤乾燥を確認した後、膜中残留溶剤を除去するため、窒素中で１００℃、１時間乾燥を行った。
【０１４８】
（評価）
次に、以下の２つの評価を実施し、上記発光層領域（画素内）での平坦性の評価を実施した。
【０１４９】
＜評価１＞
上記基板上に第２電極として真空蒸着装置により、Ｃａを１０００Å、保護電極としてＡｌを２０００Å成膜した。第１電極側を正極、第２電極側を負極に接続し、ソースメーターにより直流電流を印可し、画素部の発光エリアの面積測定を、複数の印加電圧により行った。また、面積測定は印加電圧による（発光部の面積）／（開口部の面積）（ＩＴＯ部）により計算を行った。表１に各温度での発光面積を示す。
【０１５０】
＜評価２＞
各基板を第２電極を形成しないで、インク塗布領域での発光層膜厚分布を触針式段差計により測定を行った。表２に各温度での画素内膜厚の最大値／最小値を示し、図１１に各温度での画素内膜厚プロファイルを示す。
【０１５１】
［実施例２］
上記基板の温度を１５℃とした以外は、実施例１と同様に行った。
【０１５２】
［実施例３］
上記基板の温度を１２℃とした以外は、実施例１と同様に行った。
【０１５３】
［比較例１］
上記基板の温度を２１℃とした以外は、実施例１と同様に行った。
【０１５４】
［比較例２］
上記基板の温度を３５℃とした以外は、実施例１と同様に行った。
【０１５５】
【表１】

【０１５６】
【表２】

【０１５７】
［評価結果］
上記比較例１および比較例２の、室温（２１℃）以上での膜形成では、画素内の膜厚分布が大きく、また、発光面積についても、発光開始電圧直後は非常に狭い領域しか発光しておらず、印加電圧が増加するにつれ発光面積は増加した。
【０１５８】
一方、実施例１から実施例３までの室温（２１℃）以下での膜形成では、画素内膜厚は緩和する傾向が観察された。特に、実施例２および実施例３の、基板温度が１５℃以下では非常に平坦であり、発光面積は開口部のほとんどの部分が発光部であった。また、発光開始電圧から電圧増加に伴う発光領域変化はほとんど観察されずほぼ一定であった。
【０１５９】
［実施例４］
（基板の調整）
ガラス基板上に第１電極としてＩＴＯが１００μｍピッチ（ＩＴＯ幅８０μｍ，スペース幅２０μｍ）でパターニングされた基板を準備した。
【０１６０】
次に、絶縁層としてポジ型感光成材料であるＯＦＰＲ−８００（東京応化社製）を基板全面にスピンコーティング法により膜厚１．５μｍとなるように成膜し、第１電極開口部が幅７０μｍ、高さ７０μｍの矩形になるように開口部が設計されたフォトマスクを用いて、露光を行い、アルカリ現像液（ＮＭＤ−３東京応化社製）により現像を行った。続いて、２５０℃、３０分間加熱硬化処理を行い絶縁層とした。
【０１６１】
次に、撥インク性隔壁として、ポジ型感光性材料ＯＦＰＲ−８００中に撥インク性を有するモノマーであるモディパー（日本油脂社製）を２ｗｔ％混合した溶液を基板全面に塗布した。続いて、第１電極が露出した領域よりも若干広い部分が開口部となるように設計されたフォトマスクを介して露光、現像を行い撥インク性隔壁を絶縁層よりも内側に形成し、２５０℃、３０分間加熱硬化処理を行い撥インク性隔壁とした。撥インク性隔壁に対するインク接触角は６４°、第１電極および絶縁層に対するインク接触角は１０°以下であった。
【０１６２】
次に、正孔注入層として、Ｂａｙｔｒｏｎ Ｐ（バイエル社製）をインクジェット法により第１電極上に吐出し、２００℃、１時間乾燥を行い膜中水分を完全に除去した。
【０１６３】
（発光層形成用塗工液の準備）
発光層として以下の組成物を発光層形成用塗工液として準備した。
・ポリビニルカルバゾール ７重量部
・発光色素（Ｒ，Ｇ，Ｂ） ０．１重量部
・オキサジアゾール化合物 ３重量部
・シクロヘキシルベンゼン ９９０重量部
上記発光層形成用塗工液の濃度を測定したところ、粘度は１４ｍ・Ｐａ・ｓであった。
【０１６４】
（発光層形成用塗工液の塗布）
次に、チラーによる水冷式冷却機構、加熱機構および温度制御機構を持つ基板ステージ上に上述した基板をセットした。このとき、室温は２１℃であった。
【０１６５】
続いて、上述した基板温度を３５℃に保持しながら、インクジェット法により前記発光層形成用塗工液（Ｒ、Ｇ、Ｂ）のインクを発光層形成用領域である親液性領域にそれぞれ形成した。目視により溶剤乾燥を確認した後、膜中残留溶剤を除去するため、窒素中で１００℃、１時間乾燥を行った。
【０１６６】
（評価）
次に、以下の２つの評価を実施し、上記発光層領域（画素内）での平坦性の評価を実施した。
【０１６７】
＜評価１＞
上記基板上に第２電極として真空蒸着装置により、Ｃａを１０００Å、保護電極としてＡｌを２０００Å成膜した。第１電極側を正極、第２電極側を負極に接続し、ソースメーターにより直流電流を印可し、画素部の発光エリアの面積測定を、複数の印加電圧により行った。また、面積測定は印加電圧による（発光部の面積）／（開口部の面積）（ＩＴＯ部）により計算を行った。表３に各温度での発光面積を示す。
【０１６８】
＜評価２＞
各基板を第２電極を形成しないで、インク塗布領域での発光層膜厚分布を触針式段差計により測定を行った。表４に各温度での画素内膜厚の最大値／最小値を示し、図１２に各温度での画素内膜厚プロファイルを示す。
【０１６９】
［実施例５］
上記基板の温度を３０℃とした以外は、実施例４と同様に行った。
【０１７０】
［比較例３］
上記基板の温度を２１℃とした以外は、実施例４と同様に行った。
【０１７１】
［比較例４］
上記基板の温度を１３℃とした以外は、実施例４と同様に行った。
【０１７２】
［比較例５］
上記基板の温度を４５℃とした以外は、実施例４と同様に行った。
【０１７３】
【表３】

【０１７４】
【表４】

【０１７５】
［評価結果］
上記比較例３および比較例４の室温以下での膜形成では、画素内の膜厚分布は中心部が厚く周辺部が薄いプロファイルとなり、また、発光面積は画素の周囲のみが発光する結果となった。
【０１７６】
一方、比較例５での膜形成では、膜厚分布は中心部が薄く、周辺部が厚いプロファイルとなり膜厚分布が増加した。
【０１７７】
実施例４および実施例５においては、非常に平坦であり、発光面積は開口部のほとんどの部分が発光部であった。また、発光開始電圧から電圧増加に伴う発光領域変化はほとんど観察されずほぼ一定であった。
【０１７８】
【発明の効果】
本発明によれば、吐出法により滴下された後の機能性層形成用塗工液の温度を調整することにより、上記機能性層形成用塗工液の溶媒の揮発速度を調整することが可能となり、機能性部として用いられる有効領域の膜厚の最大膜厚と最小膜厚との比が上記範囲内となるように形成することができる。これにより、特別な装置等が必要なく、例えばインクジェット法等によって効率よく、平坦な機能性部を有する機能性素子を製造することが可能となるのである。
【図面の簡単な説明】
【図１】本発明の機能性素子の製造方法の一例を示す工程図である。
【図２】本発明の機能性素子の製造方法における機能性層形成用塗工液の乾燥速度の一例を示す概略断面図である。
【図３】本発明の機能性素子の製造方法における有効領域を説明するための図である。
【図４】凹形状に形成された機能性層の一例を示す概略断面図である。
【図５】凸形状に形成された機能性層の一例を示す概略断面図である。
【図６】本発明の機能性素子の製造方法に用いられる基板の形成方法の一例を示した図である。
【図７】本発明の機能性素子の製造方法に用いられる基板の一例を示した概略断面図である。
【図８】本発明に用いられる隔壁の一例を示す概略断面図である。
【図９】本発明に用いられる隔壁の他の例を示す概略断面図である。
【図１０】本発明の有機ＥＬ素子の製造方法の一例を示す工程図である。
【図１１】本発明の実施例および比較例の膜厚プロファイルを示したグラフである。
【図１２】本発明の実施例および比較例の膜厚プロファイルを示したグラフである。
【図１３】機能性素子の製造方法の従来技術を示す工程図である。
【図１４】インクジェット法による膜形成の際の乾燥速度およびインクのフローを説明するための図である。
【符号の説明】
１ … 基板
２ … 機能性層形成用塗工液
３ … インクジェット装置
４ … 機能性層
ａ … 有効領域
Ｔｍａｘ… 有効領域における最大膜厚
Ｔｍｉｎ… 有効領域における最小膜厚[0001]
TECHNICAL FIELD OF THE INVENTION
INDUSTRIAL APPLICABILITY The present invention provides a function excellent in flatness which can be used for an organic semiconductor, an organic electroluminescent (hereinafter sometimes abbreviated as organic EL) element, a display device such as a color filter for liquid crystal, an electronic device, or the like. The present invention relates to a method for manufacturing a functional element having a functional part, and an ink jet device used in the method.
[0002]
[Prior art]
In recent years, a technique of forming a thin film required for a display device such as an organic semiconductor, an organic EL element, a color filter for a liquid crystal, and an electronic device by an inkjet method has attracted attention. Fabricating such a device by an ink-jet method is considered to be a promising technique from the viewpoints of simplification of a manufacturing apparatus, reduction of running cost, and the like, and is particularly promising as a method of manufacturing an organic EL element. .
[0003]
In an organic EL device, holes and electrons injected from counter electrodes located on both sides of a thin film, which is both a semiconductor layer and a light emitting layer, are combined in the light emitting layer, and the energy thereof excites a fluorescent substance in the light emitting layer. Light emission of a color corresponding to the substance can be obtained. Such an organic EL element has advantages such as a very simple device structure that is a self-luminous device, and is expected as a next-generation display device succeeding a liquid crystal display element.
[0004]
The method of manufacturing the organic EL element is roughly classified into two methods, a method of manufacturing a low molecular material by a vacuum process, and a method of manufacturing a high molecular material by a wet process. Above all, the latter method of making the organic EL material soluble in a solvent and forming it by a wet process has attracted attention in terms of simplification of the manufacturing method and apparatus. Various methods are known as a method for manufacturing an organic EL element by a wet process, but a manufacturing method based on an ink-jet method is mainly used in view of simplification of a manufacturing apparatus and high material use efficiency. As a method of manufacturing such an organic EL element, for example, as shown in FIG. 13A, first, an electrode layer 15, an inorganic insulating layer 5 (ink-philic), and an organic partition layer 6 ( And oxygen plasma and CF₄Plasma processing is performed continuously. Where CF₄When the surface is fluorinated by plasma, the surface of the inorganic material (the first electrode layer 15 and the inorganic insulating layer 5) is not fluorinated by setting the treatment time because the surface of the inorganic material is less likely to be fluorinated than the surface of the organic material. It is possible to selectively perform a surface treatment so that the ink affinity is maintained and only the surface of the organic partition layer 6 is fluorinated and becomes ink-repellent. Next, the ink is ejected between the organic partition walls 6 by an ink-jet method, so that the ejected ink does not adhere to the ink-repellent organic partition walls 6, and the first electrode layer 15 having ink affinity and the inorganic insulating layer It can land on layer 5. As a result, the film 4 can be formed (see FIG. 13B, Patent Document 1). However, in this method, as shown in, for example, FIGS. 13B and 13B, the thin film 4 has a concave shape (FIG. 13 b)) or a convex shape (FIG. 13B ') in many cases, and it was difficult to form a flat film.
[0005]
In order to solve such a problem, for example, a method in which ink is ejected many times to the same location and the solid content concentration is reduced (Patent Document 2), or a method in which ink is ejected onto a substrate A method in which drying is performed under a rapid reduced pressure (Patent Document 3), a method in which ink is ejected onto a substrate and then the substrate is rocked (Patent Document 4), and a partition structure for holding ink is applied to ink. There is known a method of forming from a layer having an affinity for a layer and a layer having a non-affinity (Patent Document 5).
[0006]
However, in any of the methods, it is impossible to avoid an increase in the number and complexity of the processes or the complexity of the manufacturing apparatus, and there is a problem in terms of an increase in manufacturing cost and a decrease in throughput. For example, in Patent Literature 2, it is necessary to discharge ink to the same pixel many times, and thus there is a problem that the cost increases and the throughput decreases. Further, in the above-mentioned Patent Documents 3 and 4, a distinctive property in the case where the ink is ejected onto a substrate by an ink jet method leads to a clear decrease in throughput. This is because the solvent used for the ink for ink jet is generally a high boiling point solvent in many cases in order to prevent the ink from drying in the device section. However, when used for applications such as organic semiconductors and organic EL devices, the film to be formed is on the order of submicrons, so even if such a high boiling point solvent is used, the ink volume on the substrate is on the order of picoliters ( 1 × 10^-121) It is very small and dry in a short time. Therefore, even when a slow drying solvent having a vapor pressure at room temperature of 10 mmHg or less, which is a solvent that does not normally dry for several hours or more, is used for several tens of seconds when it is ejected by inkjet. ~ Dry in about a few minutes. In other words, when the same ink is ejected in a large number of places in a substrate such as a color filter or an organic EL element, the ink ejected before that is dried while ejecting the ink to a certain place. It becomes. Therefore, when performing vacuum drying and substrate swinging after ink ejection as a film forming process, these methods need to be performed immediately after ink ejection. And the manufacturing time becomes very long.
[0007]
Further, in the case of Patent Document 5, it is necessary that the partition structure for holding the ink has a high degree of control of the multilayer structure having affinity and non-affinity for the ink as one continuous partition, It has been very difficult to mass-produce such partition walls in manufacturing.
[0008]
Here, although the mechanism of the occurrence of the concave and convex film thickness distributions in the above-mentioned ink application region is not clear, some studies have been made on these. For example, Non-Patent Document 1 discusses the mechanism of generating “coffee stains” for millimeter-sized droplets whose order is larger than the amount of droplets produced by the inkjet method.
[0009]
This will be described with reference to FIG. When the ink droplet is formed on the substrate such that the cross section of the droplet is a circle having a radius R, a part of a circle, or an arc shape, as shown in FIG. ) And near the end (position r), the amount of solvent per unit area is different, so the solvent drying speed (J) is different. At this time, since the ink is in the form of a circle, a part of a circle, or an arc, the drying speed (J) becomes faster toward the end. At this time, the ink ends are fixed on the substrate unless the substrate is extremely wet or has extremely high ink repellency. Therefore, a liquid flows from the center of the droplet to the outside so as to compensate for the liquid lost near the edge of the substrate in order to maintain the film (FIG. 14B). The flow velocity (V) of the liquid to the outside is proportional to the drying velocity (Jr) at a distance r from the center. Therefore, since the drying speed is high near the end, the outward flow speed (V) also increases. At this time, the solute, which is a dissolved component, moves outward together with the liquid, and the dissolved component concentrates at the end with the drying of the liquid component. Finally, for example, as shown in FIG. It is to be noted that a concave film having a high end thickness is formed.
[0010]
Another interpretation of the difference in the drying speed depending on the position of the droplet is described in Non-Patent Document 2. This is because the appropriate amount of liquid existing above the unit area per unit bottom area differs depending on the position of the liquid droplet (the center and the end). As a result, a liquid flows from the center to the outside in order to maintain the film at the edge where drying is relatively fast.
[0011]
In any case, the flow of the liquid from the center of the droplet to the outside is the cause of the film thickness distribution, and this is due to the difference in the drying speed between the center and the outside, especially the fast drying in the outside. Probable cause.
[0012]
On the other hand, the case where the central portion is thick and the peripheral portion is thin is not clearly described in the above-mentioned literature, but is often seen empirically when a high boiling point solvent is used. In this case, it is presumed that this occurs when the drying speed is high irrespective of the boiling point of the solvent. This is probably because the drying rate is faster than the flow rate of the material to the outside, and the material flow to the peripheral portion cannot catch up.
[0013]
In any of the concave and convex shapes, it is considered that the film thickness distribution occurs in the ink drying step. However, when the inkjet method is used, the drying time of the ejected ink is extremely fast as described above. However, although the drying step which affects the film thickness distribution as described above occurs in a very short time after ink ejection, there is a problem that it is difficult to control the shape of the film thickness.
[0014]
In addition, when the above-mentioned film having a large thickness distribution is used as the functional part of the functional element, for example, in an optical device such as an organic EL element or a color filter, display unevenness, color unevenness, and device life in a pixel are shortened. In an electronic device such as an organic semiconductor or an organic EL element, there is a problem that a difference occurs in electronic characteristics between a thin portion and a thick portion.
[0015]
[Patent Document 1]
JP 2000-323276 A
[Patent Document 2]
JP 2001-291584 A
[Patent Document 3]
JP 2001-276726 A
[Patent Document 4]
JP 2001-237067 A
[Patent Document 5]
Japanese Patent Application Laid-Open No. H11-329741
[Non-patent document 1]
Nature, 389, 827, 1997
[Non-patent document 2]
Surface Science Vol. 24, N0.2, pp. 90-97, 2003
[0016]
[Problems to be solved by the invention]
In view of the above, it is desired to provide a method for manufacturing a functional element that can form a flat functional portion with high manufacturing efficiency by using an ejection method such as an inkjet method.
[0017]
[Means for Solving the Problems]
The present invention provides a functional layer-forming coating solution containing a solvent, which is dropped onto a functional layer-forming region, which is a region where a functional layer is formed, by a discharge method, and then dried and solidified. In the method for producing a functional element having a functional layer forming step of forming a layer, the maximum film thickness in an effective region in the functional layer, which is a region used as a functional part of the functional element, is Tmax, and the minimum film is When the thickness is Tmin,
Tmax / Tmin ≦ 2
A method for producing a functional element, characterized in that the temperature of the functional layer-forming coating liquid after dropping is adjusted so that
[0018]
According to the present invention, it is possible to adjust the volatilization rate of the solvent of the functional layer-forming coating liquid by adjusting the temperature of the functional layer-forming coating liquid after being dropped by the discharge method. It can be formed so that the ratio of the maximum thickness to the minimum thickness of the effective region used as the functional portion is within the above range. As a result, a special device or the like is not required, and a functional element having a flat functional portion can be efficiently manufactured by, for example, an ink-jet method.
[0019]
In the above invention, the adjustment of the temperature is performed by inspecting the shape of the functional layer when the functional layer forming step is performed at a predetermined temperature, and when the center of the functional layer is concave, the temperature is adjusted. In the case where the central part of the functional layer has a convex shape, the temperature is preferably increased. Thereby, the ratio between the maximum film thickness and the minimum film thickness in the effective region can be set within the above range.
[0020]
In the present invention, it is preferable that the adjustment of the temperature is performed by changing the temperature of the substrate. Thereby, the temperature of the functional layer forming coating liquid can be easily adjusted.
[0021]
Furthermore, in the present invention, it is preferable that the substrate is lyophobic and the functional layer forming region is a lyophilic region. Thereby, it is possible to easily apply the functional layer-forming coating liquid only to the functional layer-forming region, which is a lyophilic region, by an ejection method such as an inkjet method. .
[0022]
In the above invention, the substrate is formed on the substrate and the substrate, and has a photocatalyst and a binder, and a wettability changing layer in which a contact angle with a liquid is reduced by the action of the photocatalyst with energy irradiation. It is preferable that the functional layer forming region is a lyophilic region by irradiating the wettability changing layer with energy. Since the substrate is composed of the base material and the wettability changing layer, it is possible to easily form a functional layer forming region that is a lyophilic region in a target pattern by energy irradiation. Because it becomes.
[0023]
The present invention provides a method for producing an organic electroluminescent device, wherein the functional portion produced by the method for producing a functional device described above is an organic electroluminescent layer having at least a light emitting layer. provide.
[0024]
According to the present invention, a flat organic EL layer can be formed by the above-described method for producing a functional element, and a high-quality organic EL layer having less color unevenness and a shorter device life due to a difference in thickness of the organic EL layer can be obtained. An EL element can be manufactured.
[0025]
According to another aspect of the present invention, there is provided an inkjet apparatus having an ejection unit for ejecting ink and a substrate holding unit for holding a substrate from which the ink is ejected, and having an ink temperature adjustment mechanism for adjusting the temperature of the ink. An ink jet device is provided.
[0026]
According to the present invention, since the ink temperature adjusting mechanism is provided, it is possible to adjust the temperature of the ink ejected from the ejection section. Thereby, the evaporation rate of the solvent contained in the ink can be adjusted, and the shape of the formed film can be controlled.
[0027]
According to another aspect of the present invention, there is provided an inkjet apparatus having an ejection unit for ejecting ink and a substrate holding unit for holding a substrate from which the ink is ejected, the inkjet device having a substrate temperature adjustment mechanism for adjusting the temperature of the substrate. An ink jet device is provided.
[0028]
According to the present invention, since the substrate temperature adjusting mechanism is provided, it is possible to adjust the temperature of the ink to a target temperature when the ink ejected from the ejection section lands on the substrate. Thereby, the evaporation rate of the solvent contained in the ink can be adjusted, and the shape of the formed film can be controlled.
[0029]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention relates to a method for manufacturing a functional element capable of efficiently forming a flat functional portion using a discharge method such as an ink jet method, and an ink jet apparatus that can be used in the method. Hereinafter, each will be described separately.
[0030]
A. Method for manufacturing functional element
In the method for producing a functional element of the present invention, a functional layer-forming coating liquid containing a solvent is dropped on a substrate by a discharge method onto a functional layer-forming region that is a region where a functional layer is formed. In a method for producing a functional element having a functional layer forming step of drying and solidifying to form a functional layer, the maximum in the effective area in the functional layer, which is an area used as a functional part of the functional element When the film thickness is Tmax and the minimum film thickness is Tmin,
Tmax / Tmin ≦ 2
The method is characterized in that the temperature of the functional layer-forming coating liquid after dropping is adjusted so that
[0031]
In the method for manufacturing a functional element of the present invention, for example, as shown in FIG. 1, a functional layer forming coating liquid 2 is dropped on a substrate 1 by, for example, an ink jet device 3 (FIG. 1A). Then, the functional layer 4 is formed by drying and solidifying to form the functional layer 4 (FIG. 1B). Among the functional layers 4 formed in the functional layer forming step, the functional layer 4 is formed. Adjusting the temperature of the functional layer-forming coating liquid 2 so that the ratio between the maximum film thickness Tmax and the minimum film thickness Tmin within the effective region a used as a part falls within a predetermined range. Features.
[0032]
According to the present invention, when the functional layer is formed by a discharge method, for example, by adjusting the temperature of the functional layer forming coating liquid after being dropped from a nozzle or the like of an ink jet device, the functional layer is formed. It becomes possible to adjust the volatilization rate of the solvent contained in the coating liquid for application. That is, when the temperature of the functional layer-forming coating liquid is adjusted to be low, for example, as shown in FIG. 2, the solvent in the functional layer-forming coating liquid 4 applied on the substrate 1 is volatilized. The speed (solid arrow) can be made slower than the volatilization speed (dotted arrow) when temperature adjustment is not performed. Thereby, the flow of the coating liquid for forming a functional layer from the center to the outside in the region for forming a functional layer can be suppressed, and the film thickness of the center and the end of the formed functional layer can be suppressed. Can be reduced.
[0033]
By adjusting the temperature of the functional layer-forming coating liquid, it becomes possible to control the shape of the functional layer formed by volatilization of the solvent in the functional layer-forming coating liquid, and the formed function The ratio between the maximum film thickness and the minimum film thickness in the effective region used as the functional portion in the functional layer can be set to be within a predetermined range. Further, in the present invention, there is no need to go through a special device or complicated steps, and there is no need to change the composition of the functional layer-forming coating solution to be dropped. Therefore, it can be preferable in terms of manufacturing efficiency and cost, and is applied to a method for manufacturing a functional element having various functional parts such as an organic EL layer in an organic EL element and a pixel part of a color filter. It is possible to do.
[0034]
Hereinafter, the temperature adjustment, which is a feature of the method for manufacturing a functional element of the present invention, will be described first, and then each component used in the functional layer forming step of the present invention will be described.
[0035]
1. Temperature control
First, temperature adjustment in a method for manufacturing a functional element, which is a feature of the present invention, will be described. The temperature adjustment in the method for producing a functional element of the present invention is performed by adjusting the temperature of a functional layer-forming coating liquid dropped by a discharge method when forming a functional layer described below. is there. By adjusting the temperature of the functional layer-forming coating liquid, it is possible to adjust the volatilization rate and the like of the solvent contained in the functional layer-forming coating liquid, and to form the formed functional layer. Can be controlled.
[0036]
Here, the temperature adjustment in the present invention is performed by the maximum film thickness (Tmax) and the minimum film thickness (Tmax) in the effective region, which is a region used as a functional portion, in the functional layer formed in the functional layer forming step described later. Tmin)
Tmax / Tmin ≦ 2
It is performed so that it becomes. In the present invention,
Tmax / Tmin ≦ 1.5
In particular
Tmax / Tmin ≦ 1.2
It is preferable that Thus, when the functional element manufactured according to the present invention is an optical device, unevenness in display and color in a pixel due to a difference in film thickness of the functional portion, reduction in device life, and the like are caused. This is because, when the manufactured functional element is an electronic device, it is possible to prevent a difference in electric characteristics or the like from occurring due to a difference in film thickness of the functional portion.
[0037]
Here, the effective region is, for example, a region a in the formed functional layer 4 which actually functions as a functional portion in a functional element, as shown in FIG. For example, as shown in FIG. 3, when the functional layer is a light emitting layer in an organic EL device, the light emitting layer 4 is provided on the substrate 1 together with the insulating layer 5 and the like. In this case, the normal light emitting layer 4 is formed so as to cover the insulating layer 5 and the like, and the effective area that actually functions as the light emitting section (functional section) is the area a shown in the drawing. Further, even when the functional layer produced by the present invention is a colored layer in a color filter, the colored layer is usually formed so as to cover the black matrix. Therefore, in the present invention, it is not necessary that the entire region of the functional layer has flatness, and it is sufficient that the functional layer has flatness in an effective region used as a functional portion. Note that the present invention also includes a device in which the entire region of the functional layer is an effective region depending on the type of the functional element to be manufactured.
[0038]
Here, as a method of adjusting the temperature of the functional layer-forming coating liquid in the present invention, when discharging the functional layer-forming coating liquid, may be a method of adjusting the temperature, Further, the coating liquid for forming the functional layer may be discharged from a discharge device and the temperature may be adjusted when the coating liquid lands on the substrate. Further, these may be performed in combination.
[0039]
In the present invention, among the above, in the case where the temperature is adjusted when the temperature is adjusted when the coating liquid for forming a functional layer is ejected from the ejection device and lands on the substrate, that is, the temperature of the substrate is adjusted. It is preferable that this is performed by performing The droplets of the functional layer-forming coating liquid discharged from the discharge device are sufficiently small, and by maintaining the substrate temperature at a target temperature, when the functional layer-forming coating liquid lands, The temperature of the substrate and the coating liquid for forming a functional layer can be made equal, and the temperature of the coating liquid for forming a functional layer can be set to a target temperature. The temperature adjustment of the substrate does not require a special device or the like, and the viscosity change caused by the temperature adjustment of the functional layer forming coating liquid is not required to adjust the ejection device and the like. This is because it can be easily performed.
[0040]
Here, in the method for manufacturing a functional element of the present invention, the temperature to be adjusted in the above temperature adjustment differs depending on the shape of the functional layer formed at a predetermined temperature. Therefore, before manufacturing a functional element by the method for manufacturing a functional element of the present invention, first, at a predetermined temperature, on the substrate used in the present invention, a functional layer forming region for forming a functional layer, After the functional layer forming coating liquid is dropped by a discharge method, a functional layer forming step of drying and solidifying (described in detail later) is performed, and the shape of the formed functional layer is inspected. According to the inspection, the shape of the formed functional layer is, for example, as shown in FIG. 4, when the center of the functional layer is concave, and as shown in FIG. 5, for example, the center of the functional layer is It is divided into the case of convex shape. Hereinafter, the temperature adjustment in each case will be described.
[0041]
Note that the predetermined temperature in the present invention refers to the temperature of the environment in which the functional element is manufactured, and is usually set to the same temperature as room temperature, specifically, 0 ° C to 50 ° C. Is usually set within the range.
[0042]
(When the center is concave)
First, the temperature adjustment when the center of the functional layer has a concave shape by the above inspection will be described. According to the above inspection, when the central portion of the functional layer formed at a predetermined temperature has a concave shape, the adjustment of the temperature in the method of manufacturing a functional element of the present invention is performed after the dropping of the functional layer. This is performed by lowering the temperature of the coating liquid. This is because, at a predetermined temperature, when the coating liquid for forming a functional layer is applied on the region for forming a functional layer, the coating liquid for forming a functional layer at an end of the region for forming a functional layer is formed. The volatilization rate in the working liquid is high, and the liquid flows from the center to the outside as described above. Therefore, by lowering the temperature of the functional layer forming coating liquid dropped by the discharge method, the volatilization rate of the solvent in the functional layer forming coating liquid at the end of the functional layer forming region is reduced. Therefore, the flow of the liquid from the central portion of the functional layer forming region to the outside can be suppressed, and the thickness of the functional layer can be made flat.
[0043]
The temperature of the functional layer-forming coating liquid after the temperature adjustment is appropriately selected depending on the type and viscosity of the functional layer-forming coating liquid, room temperature, and the like. The temperature is lower than the temperature, and is usually in the range of 1 ° C. to 30 ° C. lower than the predetermined temperature, especially 3 ° C. to 15 ° C. lower. Here, the temperature of the functional layer forming coating liquid is a temperature at which the coating liquid lands on the substrate.
[0044]
Examples of a method for setting the temperature of the functional layer forming coating liquid within the above range include a method using an ejection device having an ink temperature adjustment mechanism when the temperature adjustment is performed in an ejection portion of the ejection device. Can be In the case where the temperature adjustment is performed by adjusting the temperature of the substrate, a method of cooling the substrate holding portion that holds the substrate with water, a method of cooling the substrate holding portion with a Peltier element, and the like can be given. In the present invention, as described above, it is preferable to perform the temperature adjustment by adjusting the temperature of the substrate, and among the above methods, a method using a Peltier element is preferable. In addition, the temperature of the substrate at this time is usually preferably 1 ° C. to 30 ° C. lower than a predetermined temperature, particularly preferably 3 ° C. to 15 ° C. lower.
[0045]
Further, in the present invention, it is also possible to carry out using an ink temperature adjusting mechanism described below, an inkjet apparatus having a substrate temperature adjusting mechanism, the temperature adjustment, and the application of the functional layer-forming coating liquid. Can be performed by the same device, and it is preferable to use an ink jet device described later. In this case, the temperature adjustment is preferably performed in an atmosphere of nitrogen gas or dry air in order to suppress the occurrence of dew condensation.
[0046]
In addition, it is preferable that the above-mentioned temperature is normally maintained while the above-mentioned coating liquid for forming a functional layer is dried and cured.
[0047]
(When the center is convex)
Next, a description will be given of temperature adjustment in the case where the center of the functional layer has a convex shape by the above inspection. According to the above inspection, when the central part of the functional layer formed at a predetermined temperature has a convex shape, the temperature adjustment in the method of manufacturing a functional element of the present invention is performed by the coating for forming the functional layer after dripping. This is performed by raising the temperature of the working liquid. This is because, at a predetermined temperature, when the coating liquid for forming a functional layer is applied on the region for forming a functional layer, the flow of the liquid from the center of the region for forming a functional layer to the outside is reduced. being insufficient. Therefore, by increasing the temperature of the functional layer forming coating liquid dropped by the discharge method, the flow of the liquid from the center of the functional layer forming region to the outside is promoted, and the thickness of the functional layer is reduced. Can be made flat.
[0048]
The temperature of the functional layer-forming coating liquid after the temperature adjustment is appropriately selected depending on the type, viscosity, room temperature, and the like of the functional layer-forming coating liquid. The temperature is higher than the temperature and is usually in the range of 1 ° C. to 30 ° C. higher than a predetermined temperature, especially 3 ° C. to 15 ° C. higher.
[0049]
Examples of a method for setting the temperature of the functional layer forming coating liquid within the above range include a method using an ejection device having an ink temperature adjustment mechanism when the temperature adjustment is performed in an ejection portion of the ejection device. Can be In the case where the temperature adjustment is performed by adjusting the temperature of the substrate, a method using a hot plate, a Peltier element, or the like may be used. Also in this case, as described above, it is preferable to perform the temperature adjustment by adjusting the temperature of the substrate, and among the above methods, a method using a Peltier element is preferable. Further, the temperature of the substrate at this time is usually preferably a temperature higher by 1 ° C. to 30 ° C. than the predetermined temperature, particularly preferably a temperature higher by 3 ° C. to 15 ° C.
[0050]
Further, in the present invention, it is also possible to carry out using an ink temperature adjusting mechanism described below, an inkjet apparatus having a substrate temperature adjusting mechanism, the temperature adjustment, and the application of the functional layer-forming coating liquid. It is preferable to use an ink jet device described later from the viewpoint that the same device can be used.
[0051]
In addition, it is preferable that the said temperature is normally hold | maintained while the said coating liquid for functional layer formation dries and hardens.
[0052]
2. Functional layer forming process
Next, a functional layer forming step in the method for producing a functional element of the present invention will be described. The functional layer forming step in the method for producing a functional element according to the present invention includes, on a substrate, a functional layer forming coating solution containing a solvent, and a functional layer forming region which is a region where a functional layer is formed. This is a step of drying and solidifying after dripping by a discharge method. Hereinafter, the functional layer forming step will be described for each configuration.
[0053]
(substrate)
First, the substrate used in the present invention will be described. The substrate used in the present invention is a substrate on which a functional layer forming coating liquid described later is applied to form a functional layer. In the present invention, as long as it is possible to apply the functional layer-forming coating liquid to the functional layer-forming region, which is the region where the functional layer is formed, the type of the substrate is particularly limited. Instead, it is appropriately selected depending on the type and use of the functional element to be manufactured. Further, transparency, flexibility, and the like are appropriately selected.
[0054]
Here, the region for forming a functional layer is a region where a functional layer is formed on the substrate. In the present invention, it is preferable that the region for forming a functional layer has a property different from that of a region where the functional layer is not formed, since the functional layer can be formed with high definition. In the present invention, it is particularly preferable that the wettability is different, and it is preferable that the substrate be a lyophobic region and the functional layer forming region be a lyophilic region. Thereby, when the coating liquid for forming a functional layer is applied by a discharge method described below, the coating liquid for forming a functional layer is not repelled and adheres on the substrate, and the lyophilic region is formed. This is because the coating liquid for forming a functional layer is applied only to the region for forming a functional layer, and the functional layer can be easily formed in a desired shape.
[0055]
Here, the lyophilic region is a region having a small contact angle with the liquid, and refers to a region having good wettability with a functional part composition and the like described later. Further, the lyophobic region is a region having a large contact angle with a liquid, and is a region having poor wettability with a composition for a functional part described later.
[0056]
In the present invention, when the contact angle with the liquid is 1 ° or more lower than the contact angle with the liquid in the adjacent region, the lyophilic region, the contact angle with the liquid in the adjacent region, When the contact angle is higher than 1 °, the liquid repellent region is set.
[0057]
Here, the contact angle between the lyophilic region and the lyophobic region with respect to the coating liquid for forming a functional layer described later differs by at least 1 ° or more, preferably 5 ° or more, particularly preferably 10 ° or more. .
[0058]
The method of setting the liquid repellent region on the base material and the functional layer forming region as the lyophilic region as described above will be described later in the section “3. Others”. Omitted.
[0059]
Further, in the present invention, a partition is provided at an outer peripheral portion of the functional layer forming region, and the partition separates the functional layer forming region from a region where the functional layer is not formed. It may be. Since this partition is also described later, the description is omitted here.
[0060]
Furthermore, various members such as an insulating layer in an organic EL element may be formed on the substrate used in the present invention, depending on the type of the functional element and the necessity.
[0061]
(Discharge method)
Next, the ejection method used in the present invention will be described. In the present invention, a coating liquid for forming a functional layer, which will be described later, is applied onto the functional layer forming region by a discharge method. The ejection method used in the present invention is not particularly limited, and examples thereof include a dispenser method and an ink jet method. In the present invention, the ink jet method is particularly preferable. Thereby, the functional layer can be easily formed in a target pattern, and it is preferable in terms of simplification of a manufacturing apparatus, running cost, and the like.
[0062]
Note that, in the present invention, it is preferable to use an ink jet apparatus having an ink temperature adjusting mechanism or a substrate temperature adjusting mechanism described later. Thereby, the above-described temperature adjustment can be performed by the same apparatus as that for applying the functional layer forming coating liquid.
[0063]
(Coating liquid for forming functional layer)
Next, the coating liquid for forming a functional layer used in the present invention will be described. The functional layer-forming coating liquid used in the present invention contains a solvent, and is dropped on the functional layer-forming region for forming the functional layer on the above-described base material by the discharge method. After that, it is dried and solidified to form a functional layer.
[0064]
Here, the coating liquid for forming a functional layer used in the present invention is appropriately selected depending on the type of the functional layer in the functional element to be manufactured. Examples of the coating liquid include a coating liquid for forming a layer and a coating liquid for forming a colored layer that forms a colored layer in a color filter.
[0065]
In the present invention, it is particularly preferable to apply by an inkjet method among the above-described ejection methods, and the properties of the functional layer forming coating liquid used in such an inkjet method include a solvent, a low viscosity, It has a high boiling point. By using the coating liquid for forming a functional layer having the above properties, the coating liquid can be quickly discharged from the nozzle opening without any delay, and the coating liquid is prevented from remaining on the inner wall of the nozzle. This is because the application accuracy of the inkjet method can be improved from the side of the liquid.
[0066]
The type of the solvent contained in such a functional layer-forming coating liquid is not particularly limited, and is appropriately selected depending on the type of the intended functional layer. It may be. Further, a fast-drying solvent having a saturated vapor pressure of 10 mmHg or more at a predetermined temperature or a slow-drying solvent having a saturated vapor pressure of 10 mmHg or less at a predetermined temperature may be used, or a combination of these may be used.
[0067]
(Dry solidification)
Next, in the present invention, the coating liquid for forming a functional layer formed on the above-described region for forming a functional layer is dried and solidified (or cured). In the present invention, the drying and solidification of the coating liquid for forming a functional layer is performed at the temperature described in the section of the temperature adjustment. In the present invention, the method is not particularly limited as long as the solvent in the coating liquid for forming a functional layer can be volatilized, and is usually used for drying a film formed by a discharge method. It is possible to use the methods described.
[0068]
3. Other
In the present invention, as described above, the functional layer-forming region has a property different from that of the region where the functional layer is not formed, from the viewpoint that the functional layer can be formed with high definition. It is particularly preferable that the wettability is different. In the present invention, in order to realize that regions having different wettability can be formed, the substrate is formed on the base material and the base material, and has a photocatalyst and a binder. A layer having a wettability changing layer in which a contact angle with a liquid is reduced by the action of the photocatalyst, and the functional layer forming region is made a lyophilic region by irradiating the wettability changing layer with energy ( First embodiment) is preferable. Thereby, it is possible to easily form the functional layer forming region, which is a lyophilic region, in a desired pattern by energy irradiation.
[0069]
Further, in the present invention, a partition is provided at an outer peripheral portion of the functional layer forming region, and the partition separates the functional layer forming region from a region where the functional layer is not formed. (Second embodiment). In any of the above embodiments, when the functional layer forming coating liquid is applied on the functional layer forming region of the substrate described above, the functional layer forming coating liquid is formed with high precision in a target pattern. It becomes possible to apply. Hereinafter, each embodiment will be described.
[0070]
(First aspect)
First, the substrate comprises a substrate and a wettability changing layer formed on the substrate, having a photocatalyst and a binder, and having a contact angle with a liquid reduced by the action of the photocatalyst with energy irradiation. The case where the functional layer forming region is a lyophilic region by irradiating the wettability changing layer with energy will be described. In this aspect, since the substrate is formed from the base material and the wettability changing layer formed on the base material, the surface is easily wetted by performing energy irradiation. And a lyophilic region can be formed. That is, by irradiating energy only to the functional layer forming region on the wettability changing layer, the functional layer forming region can be easily made a lyophilic region.
[0071]
Hereinafter, each configuration used in this embodiment will be described.
[0072]
(1) wettability changing layer
The wettability changing layer used in the present embodiment is formed on a base material described later, and has a photocatalyst and a binder, particularly if the contact angle with a liquid decreases due to the action of the photocatalyst with energy irradiation. It is not limited.
[0073]
Among the wettability changing layers used in the present embodiment, the contact angle with a liquid of 40 mN / m has a contact angle of 10 ° or more, preferably a surface tension of 30 mN / m, in a portion not irradiated with energy, that is, in a lyophobic region. It is preferable that the contact angle with the liquid is 10 ° or more, particularly the contact angle with the liquid having a surface tension of 20 mN / m is 10 ° or more. This is because the portion that is not irradiated with energy is a portion that requires liquid repellency, so if the contact angle with the liquid is small, the liquid repellency is not sufficient, and the coating for forming the functional layer is not performed. This is because when the liquid is applied, there is a possibility that the coating liquid for forming a functional layer may adhere to the lyophobic region.
[0074]
The wettability changing layer has a contact angle with a liquid having a surface tension of less than 9 °, preferably a liquid having a surface tension of 50 mN / m, in a portion irradiated with energy, that is, a lyophilic region. Is preferably a layer having a contact angle of 10 ° or less, particularly a liquid having a surface tension of 60 mN / m. When the contact angle with the liquid in the energy-irradiated portion, that is, the lyophilic region, is high, the coating liquid for forming a functional layer may be repelled in the lyophilic region, and the functional layer may be formed. This is because the coating liquid for application may not be sufficiently spread and may make it difficult to form a functional layer.
[0075]
In addition, the contact angle with the liquid referred to here is a contact angle with a liquid having various surface tensions measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.) (from the micro syringe to the liquid). 30 seconds after dropping) and obtained from the results or as a graph. In this measurement, wetting index standard solutions manufactured by Junsei Chemical Co., Ltd. were used as liquids having various surface tensions.
[0076]
The wettability changing layer used in the present embodiment contains fluorine in the wettability changing layer, and furthermore, the fluorine content on the surface of the wettability changing layer, when the wettability changing layer is irradiated with energy, The wettability changing layer may be formed so as to be reduced by the action of the photocatalyst as compared to before the energy irradiation, or decomposed by the action of the photocatalyst by the energy irradiation, thereby reducing the wettability on the wettability changing layer. It may be formed to include a decomposable substance that can be changed.
[0077]
The mechanism of action of a photocatalyst represented by titanium dioxide as described later in the wettability changing layer as described above is not necessarily clear, but carriers generated by light irradiation are directly reacted with nearby compounds. Alternatively, it is considered that active oxygen species generated in the presence of oxygen and water change the chemical structure of an organic substance. In the present embodiment, it is considered that the carrier acts on the binder compound in the wettability changing layer to change the wettability of the surface.
[0078]
Hereinafter, the photocatalyst, the binder, and other components constituting such a wettability changing layer will be described.
[0079]
a. photocatalyst
First, the photocatalyst used in the present embodiment will be described. As the photocatalyst used in the present embodiment, for example, titanium dioxide (TiO 2) known as an optical semiconductor₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)₃), Tungsten oxide (WO₃), Bismuth oxide (Bi₂O₃), And iron oxide (Fe₂O₃), And one or more of them may be used in combination.
[0080]
In this embodiment, titanium dioxide is particularly preferably used because it has a high band gap energy, is chemically stable, has no toxicity, and is easily available. Titanium dioxide includes anatase type and rutile type, and any of them can be used in this embodiment. Anatase type titanium dioxide is preferable. Anatase type titanium dioxide has an excitation wavelength of 380 nm or less.
[0081]
Examples of such anatase-type titanium dioxide include, for example, anatase-type titania sol of peptized hydrochloric acid (STS-02 (average particle size: 7 nm) manufactured by Ishihara Sangyo Co., Ltd .; ST-K01 manufactured by Ishihara Sangyo Co., Ltd.); Glue-type anatase titania sol (TA-15 (average particle diameter: 12 nm) manufactured by Nissan Chemical Industries, Ltd.) and the like can be mentioned.
[0082]
The smaller the particle size of the photocatalyst is, the more effective the photocatalytic reaction takes place. The average particle size is preferably 50 nm or less, more preferably 20 nm or less.
[0083]
The content of the photocatalyst in the wettability changing layer used in this embodiment can be set in the range of 5 to 60% by weight, preferably 20 to 40% by weight. Further, the thickness of the wettability changing layer is preferably in the range of 0.05 to 10 μm.
[0084]
b. Binder
Next, the binder used in this embodiment will be described. In the present embodiment, when the wettability on the wettability changing layer is changed by the action of the photocatalyst on the binder itself (first embodiment), the wettability is changed by the action of the photocatalyst due to energy irradiation, thereby changing the wettability. There are three cases: a case where the decomposition property can be changed by incorporating a decomposable substance capable of changing the wettability on the layer into the wettability changing layer (second embodiment); and a case where these are combined (third embodiment). It can be divided into forms. The binder used in the first embodiment and the third embodiment needs to have a function of changing the wettability on the wettability changing layer by the action of a photocatalyst. No special functions are required.
[0085]
Hereinafter, the binder used in the second embodiment, that is, the binder that does not particularly require a function of changing the wettability on the wettability changing layer by the action of a photocatalyst, will be described. Next, the first embodiment and the third embodiment will be described. , That is, a binder having a function of changing the wettability on the wettability changing layer by the action of a photocatalyst will be described.
[0086]
The binder used in the second embodiment, which does not particularly require the function of changing the wettability on the wettability changing layer by the action of the photocatalyst, has a high binding energy such that the main skeleton is not decomposed by the photoexcitation of the photocatalyst. It is not particularly limited as long as it has. Specific examples include polysiloxanes having no organic substituents or having some organic substituents, and these can be obtained by hydrolysis and polycondensation of tetramethoxysilane, tetraethoxysilane, and the like. .
[0087]
When such a binder is used, a decomposed substance capable of changing the wettability on the wettability changing layer is decomposed by the action of a photocatalyst due to energy irradiation as an additive, and is contained in the wettability changing layer. It is essential.
[0088]
Next, a binder used in the first and third embodiments, which requires a function of changing the wettability on the wettability changing layer by the action of a photocatalyst, will be described. As such a binder, those having a high binding energy such that the main skeleton is not decomposed by the photoexcitation of the photocatalyst described above, and those having an organic substituent that is decomposed by the action of the photocatalyst are preferable. (1) Organopolysiloxane which exhibits high strength by hydrolyzing and polycondensing chloro or alkoxysilane etc. by sol-gel reaction, etc. (2) Organopolysiloxane cross-linked with reactive silicone excellent in water repellency and oil repellency And the like.
[0089]
In the case of the above (1), the general formula:
Y_nSix_(4-n)
(Here, Y represents an alkyl group, a fluoroalkyl group, a vinyl group, an amino group, a phenyl group, or an epoxy group, X represents an alkoxyl group, an acetyl group, or a halogen. N is an integer of 0 to 3. )
Is preferably an organopolysiloxane which is one or more hydrolytic condensates or cohydrolytic condensates of the silicon compound represented by Here, the carbon number of the group represented by Y is preferably in the range of 1 to 20, and the alkoxy group represented by X is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. preferable.
[0090]
Further, as the binder, a polysiloxane containing a fluoroalkyl group can be particularly preferably used. Specifically, one or more hydrolyzed condensates and co-hydrolyzed condensates of the following fluoroalkylsilanes are preferably used. For example, those generally known as a fluorine-based silane coupling agent can be used.
CF₃(CF₂)₃CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₄CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si (OCH₃)₃;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si (OCH₃)₃;
CF₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₅(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₇(C₆H₄) C₂H₄Si (OCH₃)₃;
CF₃(CF₂)₃CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₅CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₇CH₂CH₂SiCH₃(OCH₃)₂;
CF₃(CF₂)₉CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₄CH₂CH₂SiCH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₆CH₂CH₂Si CH₃(OCH₃)₂;
(CF₃)₂CF (CF₂)₈CH₂CH₂Si CH₃(OCH₃)₂;
CF₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₅(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₇(C₆H₄) C₂H₄SiCH₃(OCH₃)₂;
CF₃(CF₂)₃CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₅CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₉CH₂CH₂Si (OCH₂CH₃)₃;
CF₃(CF₂)₇SO₂N (C₂H₅) C₂H₄CH₂Si (OCH₃)₃
By using a polysiloxane containing a fluoroalkyl group as described above as a binder, the liquid repellency of the energy non-irradiated portion of the wettability changing layer is greatly improved, and the adhesion of the functional layer forming coating liquid is prevented. Express function.
[0091]
Examples of the reactive silicone of the above (2) include compounds having a skeleton represented by the following general formula.
[0092]
Embedded image

Here, n is an integer of 2 or more, and R¹, R²Is a substituted or unsubstituted alkyl, alkenyl, aryl or cyanoalkyl group having 1 to 10 carbon atoms, and the vinyl, phenyl or halogenated phenyl accounts for 40% or less of the whole in a molar ratio. Also, R¹, R²Is preferably a group having a methyl group since the surface energy is minimized, and the molar ratio of the methyl group is preferably 60% or more. Further, the chain terminal or the side chain has at least one or more reactive group such as a hydroxyl group in the molecular chain.
[0093]
In addition, a stable organosilicon compound that does not undergo a cross-linking reaction such as dimethylpolysiloxane may be mixed with the binder together with the above-mentioned organopolysiloxane.
[0094]
c. Decomposition material
In the second and third embodiments, the wettability changing layer further contains a decomposed substance capable of changing the wettability on the wettability changing layer by being decomposed by the action of the photocatalyst due to energy irradiation. There is a need. That is, when the binder itself does not have a function of changing the wettability on the wettability changing layer, and when such a function is insufficient, the above-described decomposing substance is added, and the wettability changing layer is added. The above-mentioned change in wettability is caused or assisted in such change.
[0095]
Examples of such a decomposed substance include a surfactant that is decomposed by the action of a photocatalyst and has a function of changing the wettability of the surface of the wettability changing layer by being decomposed. Specifically, hydrocarbons such as NIKKOL BL, BC, BO and BB series manufactured by Nikko Chemicals Co., Ltd .; ZONYL FSN and FSO manufactured by DuPont; Asahi Glass Co., Ltd. Surflon S-141, 145; Megafac F-141 and 144 manufactured by Ink Chemical Industry Co., Ltd., Futagent F-200 and F251 manufactured by Neos Co., Ltd., Unidyne DS-401 and 402 manufactured by Daikin Industries, Ltd., and FLORAD FC-170 manufactured by 3M Co., Ltd. 176 and the like, and a fluorine-based or silicone-based nonionic surfactant, and a cationic surfactant, an anionic surfactant, and an amphoteric surfactant can also be used.
[0096]
In addition to the surfactant, polyvinyl alcohol, unsaturated polyester, acrylic resin, polyethylene, diallyl phthalate, ethylene propylene diene monomer, epoxy resin, phenol resin, polyurethane, melamine resin, polycarbonate, polyvinyl chloride, polyamide, polyimide And oligomers and polymers such as styrene-butadiene rubber, chloroprene rubber, polypropylene, polybutylene, polystyrene, polyvinyl acetate, nylon, polyester, polybutadiene, polybenzimidazole, polyacrylonitrile, epichlorohydrin, polysulfide, and polyisoprene.
[0097]
d. Contains fluorine
Further, in this embodiment, when the wettability changing layer contains fluorine, and the fluorine content on the surface of the wettability changing layer is irradiated with energy to the wettability changing layer, energy irradiation is performed by the action of the photocatalyst. It is preferable that the wettability changing layer is formed so as to be lower than before.
[0098]
With a wettability changing layer having such characteristics, a pattern composed of a portion having a small fluorine content can be easily formed by pattern irradiation with energy as described later. Here, fluorine has an extremely low surface energy, so that the surface of a substance containing a large amount of fluorine has a smaller critical surface tension. Therefore, the critical surface tension of the portion having a low fluorine content is higher than the critical surface tension of the portion having a high fluorine content. This means that a portion having a low fluorine content is a lyophilic region as compared with a portion having a high fluorine content. Therefore, forming a pattern composed of a portion having a smaller fluorine content than the surrounding surface forms a pattern of a lyophilic region in the lyophobic region.
[0099]
Therefore, when such a wettability changing layer is used, it is possible to form the high-definition functional layer by applying the above-mentioned functional layer-forming coating liquid by pattern irradiation with energy. Because.
[0100]
As described above, as the content of fluorine contained in the fluorine-containing wettability changing layer, the fluorine content in the lyophilic region having a low fluorine content formed by irradiation with energy is the energy irradiation. When the fluorine content of the non-existing portion is 100, it is preferably 10 or less, more preferably 5 or less, and particularly preferably 1 or less.
[0101]
By setting it in such a range, a large difference can be made in the lyophilicity between the energy-irradiated portion and the non-irradiated portion. Therefore, for example, by applying the functional layer-forming coating liquid to such a wettability changing layer, it is possible to accurately form the functional layer only in the lyophilic region where the fluorine content is reduced. This is because In addition, this reduction rate is based on weight.
[0102]
For the measurement of the fluorine content in such a wettability changing layer, it is possible to use various methods which are generally performed, and for example, X-ray photoelectron spectroscopy (X-ray Photoelectron Spectroscopy, ESCA (Electron)) The method is also not particularly limited as long as it is a method capable of quantitatively measuring the amount of fluorine on the surface, such as spectroscopy for chemical analysis), fluorescent X-ray analysis, mass spectrometry, and the like.
[0103]
Further, in this embodiment, titanium dioxide is suitably used as described above as the photocatalyst, and when titanium dioxide is used in this manner, the content of fluorine contained in the wettability changing layer may be X-ray When analyzed by photoelectron spectroscopy and quantified, when the titanium (Ti) element is taken as 100, the fluorine (F) element has a fluorine (F) element ratio of 500 or more, preferably 800 or more, and particularly preferably 1200 or more. It is preferable that the element F) is contained on the surface of the wettability changing layer.
[0104]
When fluorine (F) is contained in the wettability changing layer to this extent, the critical surface tension on the wettability changing layer can be sufficiently reduced, so that the liquid repellency on the surface can be ensured, and energy can thereby be saved. This is because the difference in wettability with the lyophilic region on the surface in the pattern portion where the fluorine content has been reduced by pattern irradiation can be increased.
[0105]
Further, the fluorine content in the ink-affinity region formed by pattern irradiation with energy is 50 or less, preferably 20 or less, particularly preferably 10 or less when the titanium (Ti) element is 100. It is preferable that they are contained at a ratio such that
[0106]
If the content of fluorine in the wettability changing layer can be reduced to this extent, sufficient lyophilicity can be obtained to form a functional layer, and the liquid repellency of a portion where the above energy is not irradiated can be obtained. Due to the difference in wettability with the properties, it is possible to form the functional layer with high accuracy.
[0107]
e. Method for producing wettability variable layer
When the organopolysiloxane is used as a binder as described above, the wettability changing layer disperses the coating solution by dispersing the photocatalyst and the organopolysiloxane as a binder together with other additives as necessary. It can be formed by preparing and applying this coating solution onto a substrate. As the solvent to be used, alcohol-based organic solvents such as ethanol and isopropanol are preferable. The coating can be performed by a known coating method such as spin coating, spray coating, dip coating, roll coating, and bead coating. When an ultraviolet-curable component is contained as a binder, a wettability changing layer can be formed by performing a curing treatment by irradiating ultraviolet rays.
[0108]
(2) Substrate
Next, the base material used in the present embodiment will be described. The substrate used in the present embodiment is not particularly limited as long as the wettability changing layer can be formed, and is appropriately selected depending on the type and use of the functional element to be manufactured. Also, transparency and flexibility are appropriately selected.
[0109]
In this embodiment, an anchor layer may be formed on the substrate in order to improve the adhesion between the surface of the substrate and the wettability changing layer and the like. Examples of such an anchor layer include silane-based and titanium-based coupling agents.
[0110]
(3) Formation of lyophilic region (functional layer forming region)
Next, formation of the lyophilic region (region for forming a functional layer) will be described. In this embodiment, the wettability of the above-described wettability changing layer is changed by the action of the photocatalyst accompanying the energy irradiation, and the region for forming the functional layer, which is the region where the functional layer is formed, is defined as the lyophilic region.
[0111]
As shown in FIG. 6, for example, the formation of the lyophilic region in this embodiment is performed by applying energy 14 to the wettability changing layer 12 formed on the base material 11 using a mask such as a photomask 13. Irradiation (FIG. 6A). As a result, the wettability of the region irradiated with the energy on the wettability changing layer 12 changes, and the functional layer forming region 15 can be used as the lyophilic region (FIG. 6B). .
[0112]
The term “energy irradiation (exposure)” in the present embodiment is a concept including irradiation with any energy ray capable of changing the wettability of the wettability changing layer, and is limited to visible light irradiation. is not.
[0113]
Usually, the wavelength of light used for such energy irradiation is set in a range of 400 nm or less, preferably in a range of 380 nm or less. This is because, as described above, titanium dioxide is preferably used for the photocatalyst, and light having the above-mentioned wavelength is preferable as the energy for activating the photocatalysis by the titanium dioxide.
[0114]
Examples of the light source that can be used for such energy irradiation include a mercury lamp, a metal halide lamp, a xenon lamp, an excimer lamp, and various other light sources.
[0115]
In addition to the above-described method using a light source and irradiating a pattern through a photomask, a method of drawing and irradiating a pattern using a laser such as excimer or YAG can also be used.
[0116]
Further, the energy irradiation amount at the time of the energy irradiation is an irradiation amount necessary for the wettability changing layer to change the wettability by the action of the photocatalyst.
[0117]
At this time, by irradiating energy while heating the wettability changing layer, the sensitivity can be increased, which is preferable in that the wettability can be changed efficiently. Specifically, it is preferable to heat in the range of 30 ° C to 80 ° C.
[0118]
(Second aspect)
Next, a case will be described in which a partition is provided on an outer peripheral portion of the functional layer forming region, and the functional layer forming region and a region where the functional layer is not formed are separated by the partition. . In this embodiment, for example, as shown in FIG. 7, a partition 6 is provided on the substrate 1, and the partition 6 separates the functional layer forming region b from a region where the functional layer is not formed. Is what it is. The partition is not particularly limited as long as it separates the region for forming the functional layer from the region where the functional layer is not formed, and may be, for example, a black matrix in a color filter. Here, in the present embodiment, as shown in FIG. 8, for example, when the height c of the partition 6 is lower than the maximum thickness Tmax of the formed functional layer 4, the partition 6 is lyophilic. For example, as shown in FIG. 9, when the height c of the partition 6 is higher than the maximum thickness Tmax of the formed functional layer 4, as shown in FIG. It is required to be liquid. This is, than the maximum thickness of the formed functional layer, if the height of the partition is lyophilic, the functional layer-forming coating liquid applied between the partition and the partition, Because of the influence of the partition walls, it is difficult to control the flow of the solvent contained in the functional layer-forming coating liquid according to the volatilization rate due to the temperature adjustment, and it is difficult to achieve the effects of the present invention. is there. Note that the lyophilicity and lyophobic property here are the same as the lyophilicity in the lyophilic area and the lyophobic property in the lyophobic area described in the first embodiment. Description is omitted.
[0119]
In this case, the functional layer forming region is preferably lyophilic. When the functional layer forming region is liquid repellent, the functional layer forming coating liquid is repelled, and it is difficult to form a uniform functional layer. Further, by being affected by the liquid repellency of the functional layer forming coating liquid, the above-described temperature adjustment causes a flow accompanying the volatilization rate of the solvent contained in the functional layer forming coating liquid. This is because it may be difficult to control.
[0120]
B. Manufacturing method of organic EL device
Next, a method for manufacturing the organic EL device of the present invention will be described. The method of manufacturing an organic EL device according to the present invention is characterized in that the functional portion manufactured by the above-described method of manufacturing a functional element is an organic EL layer having at least a light emitting layer. According to the present invention, since the organic EL layer in the organic EL element is manufactured by the above-described method for manufacturing a functional element, the film thickness of the organic EL layer can be made uniform, and color unevenness and device Thus, a high-quality organic EL element with a reduced life expectancy can be obtained.
[0121]
In the method of manufacturing an organic EL device according to the present invention, for example, as shown in FIG. 10, a first electrode layer 15 is formed in a pattern on a transparent substrate 1 by a photolithography method or the like. An insulating layer 5 is formed so as to cover the end. Thereafter, the liquid-repellent partition 6 is formed so as to have a width smaller than that of the insulating layer (FIG. 10A).
[0122]
Subsequently, for example, the light emitting layer forming coating liquid 2 of each color of R, G, and B is applied between the partition walls 6 on the first electrode layer 15 by an ink jet device 3 (FIG. 10B). By performing the above-described temperature adjustment, a flat light emitting layer 4 is formed (FIG. 10C). Further, by forming the second electrode layer 16 on the light emitting layer 4, an organic EL element can be formed (FIG. 10D).
[0123]
The organic EL device manufactured according to the present invention is not limited to the above-mentioned organic EL device. For example, the organic EL device may be one in which a hole injection layer is formed on the first electrode layer. , An electron injection layer, an electron transport layer, a charge blocking layer, and the like.
[0124]
Further, the layer having the wettability changing layer described in “A. Manufacturing method of functional element” may be formed.
[0125]
It should be noted that the materials and the like used for each configuration of the organic EL element used in the present invention can be the same as those usually used in the method for manufacturing an organic EL element, and therefore the description thereof is omitted here.
[0126]
C. Ink jet device
Next, the ink jet device of the present invention will be described. The ink jet device of the present invention has two modes. A first aspect is an ink jet apparatus having an ejection unit for ejecting ink and a substrate holding unit for holding a substrate from which the ink is ejected, and having an ink temperature adjustment mechanism for adjusting the temperature of the ink. According to a second aspect, there is provided an inkjet apparatus having an ejection unit for ejecting ink and a substrate holding unit for holding a substrate from which the ink is ejected, and having a substrate temperature adjustment mechanism for adjusting the temperature of the substrate. Things.
[0127]
In either of the above modes, it is possible to adjust the temperature of the ink ejected by the ejection unit. This makes it possible to adjust the volatilization rate of the solvent of the ink applied by the above-mentioned ink jet device, and to control the shape of the formed film.
[0128]
Hereinafter, each mode will be described separately.
[0129]
1. First aspect
First, a first embodiment of the ink jet device of the present invention will be described. A first aspect of the ink jet apparatus according to the present invention is an ink jet apparatus having a discharge unit for discharging ink and a substrate holding unit for holding a substrate from which the ink is discharged, wherein an ink temperature for adjusting the temperature of the ink is provided. It has an adjustment mechanism.
[0130]
The ink jet device of this aspect is characterized in that the temperature of the ink ejected is adjusted by adjusting the temperature of the ink ejected from the ink jet device. Hereinafter, each configuration of the inkjet apparatus of the present embodiment will be described.
[0131]
(Discharge part)
First, the ejection unit in the ink jet device according to the present embodiment will be described. The ejection unit used in the present embodiment is a member that ejects ink, and an ejection unit that is usually used in an inkjet apparatus can be used.
[0132]
The method of ejecting ink in the present invention is not particularly limited. For example, a method of continuously ejecting charged ink and controlling the same with a magnetic field, a method of intermittently ejecting ink using a piezoelectric element, Various methods such as a method of intermittently injecting by heating and utilizing the foaming can be used.
[0133]
(Substrate holder)
Next, the substrate holding unit used in the ink jet device of the present invention will be described. The substrate holding unit used in the inkjet apparatus of the present invention holds a substrate to which the ink ejected from the above-described ejection unit is applied. In the present invention, there is no particular limitation as long as the substrate can be held, and it is generally possible to relatively move in the X, Y, and Z directions with respect to the discharge unit.
[0134]
(Ink temperature adjustment mechanism)
Next, an ink temperature adjusting mechanism used in the ink jet device of the present embodiment will be described. The ink temperature adjustment mechanism used in the present embodiment is not particularly limited as long as the temperature of the ink ejected from the ejection unit can be maintained at a target temperature. For example, a mechanism for adjusting the temperature of a tank or the like that holds the ink to supply the ink may be used, or the temperature of the ejection unit may be adjusted to maintain the temperature of the ejection unit at a predetermined temperature. May be.
[0135]
2. Second aspect
Next, a second embodiment of the ink jet device of the present invention will be described. A second aspect of the inkjet apparatus according to the present invention is an inkjet apparatus having an ejection unit for ejecting ink and a substrate holding unit for holding a substrate from which the ink is ejected, wherein a substrate temperature for adjusting the temperature of the substrate is provided. It has an adjustment mechanism.
[0136]
According to the present invention, the droplets of the functional layer forming coating liquid discharged from the discharge section are sufficiently small. Therefore, by holding the substrate temperature at a target temperature by the substrate temperature adjusting mechanism, when the functional layer forming coating liquid lands, the substrate and the functional layer forming coating liquid are equal. The temperature can be adjusted to a desired temperature for the functional layer-forming coating liquid.
[0137]
Hereinafter, the substrate temperature adjusting mechanism of the ink jet device of the present embodiment will be described. Note that the ejection unit and the substrate holding unit are the same as those in the above-described first embodiment, and a description thereof will not be repeated.
[0138]
(Substrate temperature adjustment mechanism)
The substrate temperature adjusting mechanism used in the ink jet device of the present embodiment will be described. The substrate temperature adjusting mechanism used in the present aspect is not particularly limited as long as it can maintain the temperature of the substrate discharged from the discharge unit at a target temperature, for example, by water or a Peltier element. One having a cooling mechanism and a heating mechanism for cooling is included.
[0139]
3. Other
The inkjet device of the present invention may have the above-described ink temperature adjustment mechanism and substrate temperature adjustment mechanism.
[0140]
Note that the present invention is not limited to the above embodiment. The above embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and has the same effect. Within the technical scope of
[0141]
【Example】
Hereinafter, the present invention will be further described with reference to Examples.
[0142]
[Example 1]
(Preparation of substrate)
After depositing ITO on a 200 μm thick PET by sputtering, patterning an 80 μm line width ITO at 20 μm intervals, a 1 μm thick insulating layer is formed between the ITOs so as to cover the edges of the ITO pattern. Was formed by photolithography. For the insulating layer, ZPP-1850 (Zeon Corporation) was used as a resist.
[0143]
Next, a coating solution for a photocatalyst-containing layer having the following composition was prepared.

The above-mentioned photocatalyst containing layer coating liquid is applied on the above-mentioned substrate, and after a drying treatment at 150 ° C. for 10 minutes, a hydrolysis and polycondensation reaction are allowed to proceed, so that the transparent photocatalyst is firmly fixed in organosiloxane. The containing layer was formed to a thickness of 20 nm.
[0144]
Subsequently, the above photocatalyst-containing layer was irradiated with a mercury lamp (wavelength 365 nm) to 70 mW / cm through a mask.²The pattern irradiation was performed for 50 seconds at an illuminance of, and the contact angle of water between the irradiated portion and the non-irradiated portion was measured using a contact angle measuring device (CA-Z type manufactured by Kyowa Interface Science Co., Ltd.). 30 seconds after dropping the water droplet), the contact angle of water at the non-irradiated part is 142 °, whereas the contact angle of water at the irradiated part is 10 ° or less, and the wetting between the irradiated part and the non-irradiated part It was confirmed that pattern formation was possible due to differences in gender.
[0145]
(Preparation of coating liquid for forming light emitting layer)
Next, the following composition was prepared as a light emitting layer as a coating liquid for forming a light emitting layer.
・ 7 parts by weight of polyvinyl carbazole
-0.1 parts by weight of luminescent dye (R, G, B)
・ Oxadiazole compound 3 parts by weight
・ 990 parts by weight of tetralin
When the concentration of the coating solution for forming a light emitting layer was measured, the viscosity was 12 m · Pa · s.
[0146]
(Application of coating liquid for forming light emitting layer)
Next, the above-described substrate was set on a substrate stage having a water-cooled cooling mechanism using a chiller, a heating mechanism, and a temperature control mechanism. At this time, the room temperature was 21 ° C.
[0147]
Subsequently, while maintaining the above-mentioned substrate temperature at 18 ° C., the inks of the light emitting layer forming coating liquids (R, G, B) are formed in the lyophilic areas, which are the light emitting layer forming areas, by the ink jet method. did. After visually confirming solvent drying, the film was dried at 100 ° C. for 1 hour in nitrogen to remove the solvent remaining in the film.
[0148]
(Evaluation)
Next, the following two evaluations were performed to evaluate the flatness in the light emitting layer region (in the pixel).
[0149]
<Evaluation 1>
On the substrate, a film of Ca was formed as a second electrode and a film of Al was formed as a protective electrode at a thickness of 2000 ° by a vacuum evaporation apparatus. The first electrode side was connected to the positive electrode, the second electrode side was connected to the negative electrode, a direct current was applied by a source meter, and the area of the light emitting area of the pixel portion was measured with a plurality of applied voltages. In addition, the area was calculated by (applied voltage) (area of light emitting portion) / (area of opening portion) (ITO portion). Table 1 shows the light emitting area at each temperature.
[0150]
<Evaluation 2>
Without forming the second electrode on each substrate, the thickness distribution of the light emitting layer in the ink application region was measured by a stylus type profilometer. Table 2 shows the maximum value / minimum value of the in-pixel film thickness at each temperature, and FIG. 11 shows the in-pixel film thickness profile at each temperature.
[0151]
[Example 2]
The operation was performed in the same manner as in Example 1 except that the temperature of the substrate was set to 15 ° C.
[0152]
[Example 3]
The operation was performed in the same manner as in Example 1 except that the temperature of the substrate was set to 12 ° C.
[0153]
[Comparative Example 1]
The operation was performed in the same manner as in Example 1 except that the temperature of the substrate was set to 21 ° C.
[0154]
[Comparative Example 2]
The operation was performed in the same manner as in Example 1 except that the temperature of the substrate was set to 35 ° C.
[0155]
[Table 1]

[0156]
[Table 2]

[0157]
[Evaluation results]
In the film formation at room temperature (21 ° C.) or higher in Comparative Examples 1 and 2, the film thickness distribution in the pixel is large, and the light emitting area emits light only in a very narrow area immediately after the light emission start voltage. However, the emission area increased as the applied voltage increased.
[0158]
On the other hand, in the film formation at a room temperature (21 ° C.) or lower in Examples 1 to 3, a tendency was observed that the thickness in the pixel was reduced. In particular, in Example 2 and Example 3, when the substrate temperature was 15 ° C. or less, the substrate was extremely flat, and the light emitting area was almost the light emitting portion of the opening. In addition, a change in the light emission region from the light emission start voltage with an increase in the voltage was hardly observed and was almost constant.
[0159]
[Example 4]
(Adjustment of substrate)
A substrate in which ITO was patterned at a pitch of 100 μm (ITO width: 80 μm, space width: 20 μm) as a first electrode on a glass substrate was prepared.
[0160]
Next, OFPR-800 (manufactured by Tokyo Ohka Co., Ltd.), which is a positive photosensitive material, is formed as an insulating layer on the entire surface of the substrate so as to have a thickness of 1.5 μm by a spin coating method. Exposure was performed using a photomask in which an opening was designed to be a rectangle having a size of 70 μm and a height of 70 μm, and development was performed using an alkali developing solution (NMD-3 manufactured by Tokyo Ohka Co., Ltd.). Subsequently, a heat curing treatment was performed at 250 ° C. for 30 minutes to form an insulating layer.
[0161]
Next, as an ink-repellent partition wall, a solution in which 2% by weight of Modiper (manufactured by Nippon Oil & Fats Co., Ltd.), which is a monomer having ink repellency, was mixed in a positive photosensitive material OFPR-800 was applied to the entire surface of the substrate. Subsequently, exposure and development are performed through a photomask designed so that a portion slightly larger than the region where the first electrode is exposed becomes an opening, and an ink-repellent partition is formed inside the insulating layer. A heat curing treatment was performed at 30 ° C. for 30 minutes to obtain an ink-repellent partition wall. The ink contact angle with the ink-repellent partition was 64 °, and the ink contact angle with the first electrode and the insulating layer was 10 ° or less.
[0162]
Next, as a hole injection layer, Baytron P (manufactured by Bayer) was discharged onto the first electrode by an inkjet method, and dried at 200 ° C. for 1 hour to completely remove moisture in the film.
[0163]
(Preparation of coating liquid for forming light emitting layer)
The following composition was prepared as a light emitting layer as a coating liquid for forming a light emitting layer.
・ 7 parts by weight of polyvinyl carbazole
-0.1 parts by weight of luminescent dye (R, G, B)
・ Oxadiazole compound 3 parts by weight
・ 990 parts by weight of cyclohexylbenzene
When the concentration of the coating solution for forming a light emitting layer was measured, the viscosity was 14 m · Pa · s.
[0164]
(Application of coating liquid for forming light emitting layer)
Next, the above-described substrate was set on a substrate stage having a water-cooled cooling mechanism using a chiller, a heating mechanism, and a temperature control mechanism. At this time, the room temperature was 21 ° C.
[0165]
Subsequently, while maintaining the above-mentioned substrate temperature at 35 ° C., the inks of the light emitting layer forming coating liquids (R, G, B) are formed in the lyophilic areas, which are the light emitting layer forming areas, by the ink jet method. did. After visually confirming solvent drying, the film was dried at 100 ° C. for 1 hour in nitrogen to remove the solvent remaining in the film.
[0166]
(Evaluation)
Next, the following two evaluations were performed to evaluate the flatness in the light emitting layer region (in the pixel).
[0167]
<Evaluation 1>
On the substrate, a film of Ca was formed as a second electrode and a film of Al was formed as a protective electrode at a thickness of 2000 ° by a vacuum evaporation apparatus. The first electrode side was connected to the positive electrode, the second electrode side was connected to the negative electrode, a direct current was applied by a source meter, and the area of the light emitting area of the pixel portion was measured with a plurality of applied voltages. In addition, the area was calculated by (applied voltage) (area of light emitting portion) / (area of opening portion) (ITO portion). Table 3 shows the light emitting area at each temperature.
[0168]
<Evaluation 2>
Without forming the second electrode on each substrate, the thickness distribution of the light emitting layer in the ink application region was measured by a stylus type profilometer. Table 4 shows the maximum value / minimum value of the in-pixel film thickness at each temperature, and FIG. 12 shows the in-pixel film thickness profile at each temperature.
[0169]
[Example 5]
The procedure was performed in the same manner as in Example 4 except that the temperature of the substrate was set to 30 ° C.
[0170]
[Comparative Example 3]
The operation was performed in the same manner as in Example 4 except that the temperature of the substrate was set to 21 ° C.
[0171]
[Comparative Example 4]
The operation was performed in the same manner as in Example 4 except that the temperature of the substrate was set to 13 ° C.
[0172]
[Comparative Example 5]
The operation was performed in the same manner as in Example 4 except that the temperature of the substrate was set to 45 ° C.
[0173]
[Table 3]

[0174]
[Table 4]

[0175]
[Evaluation results]
In the film formation at room temperature or lower in Comparative Example 3 and Comparative Example 4, the film thickness distribution in the pixel is such that the central portion is thick and the peripheral portion is thin, and the light emitting area is such that only the periphery of the pixel emits light. Was.
[0176]
On the other hand, in the film formation in Comparative Example 5, the film thickness distribution became thinner in the central portion and thicker in the peripheral portion, and the film thickness distribution increased.
[0177]
In Example 4 and Example 5, the light emitting area was very flat, and the light emitting area was almost the light emitting part of the opening. In addition, a change in the light emission region from the light emission start voltage with an increase in the voltage was hardly observed and was almost constant.
[0178]
【The invention's effect】
According to the present invention, it is possible to adjust the volatilization rate of the solvent of the functional layer-forming coating liquid by adjusting the temperature of the functional layer-forming coating liquid after being dropped by the discharge method. It can be formed so that the ratio of the maximum thickness to the minimum thickness of the effective region used as the functional portion is within the above range. As a result, a special device or the like is not required, and a functional element having a flat functional portion can be efficiently manufactured by, for example, an ink-jet method.
[Brief description of the drawings]
FIG. 1 is a process chart showing an example of a method for producing a functional element of the present invention.
FIG. 2 is a schematic sectional view showing an example of a drying rate of a coating liquid for forming a functional layer in the method for producing a functional element of the present invention.
FIG. 3 is a diagram for explaining an effective area in the method for manufacturing a functional element of the present invention.
FIG. 4 is a schematic sectional view showing an example of a functional layer formed in a concave shape.
FIG. 5 is a schematic sectional view showing an example of a functional layer formed in a convex shape.
FIG. 6 is a diagram illustrating an example of a method for forming a substrate used in the method for manufacturing a functional element of the present invention.
FIG. 7 is a schematic cross-sectional view showing an example of a substrate used in the method for manufacturing a functional element of the present invention.
FIG. 8 is a schematic sectional view showing an example of a partition used in the present invention.
FIG. 9 is a schematic sectional view showing another example of the partition wall used in the present invention.
FIG. 10 is a process chart showing an example of a method for manufacturing an organic EL device of the present invention.
FIG. 11 is a graph showing a film thickness profile of an example of the present invention and a comparative example.
FIG. 12 is a graph showing a film thickness profile of an example of the present invention and a comparative example.
FIG. 13 is a process chart showing a conventional technique of a method for manufacturing a functional element.
FIG. 14 is a diagram for explaining a drying speed and a flow of ink when a film is formed by an inkjet method.
[Explanation of symbols]
1 ... substrate
2. Coating liquid for forming functional layer
3. Inkjet device
4 ... Functional layer
a ... Effective area
Tmax: Maximum film thickness in the effective area
Tmin: minimum film thickness in the effective region

Claims (8)

On a substrate, a functional layer-forming coating liquid containing a solvent is dropped by a discharge method onto a functional layer-forming region, which is a region for forming a functional layer, and then dried and solidified to form a functional layer. In the method of manufacturing a functional element having a functional layer forming step, the maximum film thickness in an effective region in the functional layer, which is a region used as a functional part of the functional element, is Tmax, and the minimum film thickness is Tmin. if you did this,
Tmax / Tmin ≦ 2
Adjusting the temperature of the functional layer-forming coating liquid after dropping so as to obtain a functional element. The adjustment of the temperature is to inspect the shape of the functional layer when the functional layer forming step is performed at a predetermined temperature, and to lower the temperature when the central part of the functional layer is concave. The method according to claim 1, wherein the temperature is increased when the central part of the functional layer has a convex shape. The method according to claim 1, wherein the adjusting of the temperature is performed by changing a temperature of the substrate. 4. The functionality according to claim 1, wherein the substrate is liquid-repellent, and the functional layer forming region is a lyophilic region. Device manufacturing method. The substrate, a substrate, formed on the substrate, and having a photocatalyst and a binder, comprising a wettability changing layer in which the contact angle with a liquid is reduced by the action of the photocatalyst with energy irradiation, The method for producing a functional element according to claim 4, wherein the region for forming a functional layer is formed as a lyophilic region by irradiating the wettability changing layer with energy. The functional part manufactured by the method for manufacturing a functional element according to any one of claims 1 to 5, wherein the functional part is an organic electroluminescent layer having at least a light emitting layer. Of manufacturing an organic electroluminescent device. What is claimed is: 1. An inkjet apparatus comprising: a discharge unit configured to discharge ink; and a substrate holding unit configured to hold a substrate onto which the ink is discharged, wherein the apparatus includes an ink temperature adjustment mechanism configured to adjust a temperature of the ink. What is claimed is: 1. An ink jet apparatus, comprising: a discharge unit that discharges ink; and a substrate holding unit that holds a substrate onto which the ink is discharged, comprising: a substrate temperature adjustment mechanism that adjusts a temperature of the substrate.

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