JP4517569B2 - Manufacturing method of display panel - Google Patents

Description

【００４６】
次いで、透明基板１２に例えば窒素ガスといった不活性ガスを吹き付けて、シラザン系溶液の溶媒を蒸発させることで、シラザン化合物がアノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面に堆積した状態となる。
【００４７】
次いで、透明基板１２を１０〜３０分間放置すると、雰囲気中の水分によってシラザン化合物が加水分解・重合するとともに保護絶縁膜１８及び仕切り壁２０と化学的に結合する。これにより、図３（ｃ）に示すように、フッ素を含む官能基が結合した重合体からなる化合物層１４’が、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０全体を覆うように、透明基板１２の一方の面１２ａ一面に成膜される。化合物層１４’に含まれる重合体は、次の一般式（２２）で表される。
【化２】

【００４８】
一般式（２２）において、Ｒｆは上述したようにフッ素を含む官能基であって撥液性を示す官能基であり、Ｘはシラザン化合物と結合したアノード１３、保護絶縁膜１８若しくは仕切り壁２０の原子又は原子団、或いははアノード１３、保護絶縁膜１８若しくは仕切り壁２０の表面と結合したシラザン化合物の一部の原子又は原子団、又は化学構造式（21）におけるＮＨ基を置換した基を構成する原子又は原子団のいずれかであり、ｎは１００以上の整数である。シラザン化合物が一般式（２０）で表されるシラザンオリゴマーの場合には、ＲｆはＣ₈Ｆ₁₇Ｃ₂Ｈ₄となり、ＸがＯとなる。シラザン化合物は活性が高く、アノード１３、保護絶縁膜１８及び仕切り壁２０にも吸着しやすいから、化合物層１４’がアノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面に化学吸着した状態で成膜される。従って、化合物層１４’においては、シラザン化合物の単分子ユニットにおける主鎖であるＲｆ−Ｓｉ−Ｘ−基又はＲｆ−Ｓｉ−基が、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面に対して略垂直方向に配列するとともに隣接する単分子ユニットのＳｉが、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面に沿った方向に対して加水分解により酸素をエーテル結合の状態で重合されている。つまり、シラザン化合物は、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面の面方向に重合されるとともに、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面に形成された、単分子ユニットにおける主鎖であるＲｆ−Ｓｉ−Ｘ−基又はＲｆ−Ｓｉ−基の上方に、更に単分子ユニットにおける主鎖Ｒｆ−Ｓｉ−Ｘ−基又はＲｆ−Ｓｉ−基が積み重なるということが殆どなくなる。このため、化合物層１４’の厚さは、実質的に単分子ユニットにおける主鎖（ここでは重合体としての側鎖に相当。）であるＲｆ−Ｓｉ−Ｘ−基又はＲｆ−Ｓｉ−基の長さに等しくなる。またこの化合物層１４’は、フッ素を含む官能基Ｒｆを、単分子ユニットにおける主鎖の先端、すなわち化合物層１４’の表面に配置するように重合されているから、有機化合物含有液に対して撥液性を示す。
【００４９】
次いで、透明基板１２を放置した後に、透明基板１２の表面１２ａ側をｍ−キシレンヘキサフロイド液ですすぐことで、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁１９の表面に積もった未反応のシラザン化合物を洗い流す。
【００５０】
次いで、図３（ｄ）に示すように、透明基板１２にフォトマスク基板４０を対向させて更にフォトマスク基板４０に活性光線を透過させて化合物層１４’に活性光線を部分的に照射することで、化合物層１４’がパターン膜１４となる。活性光線としては、可視光線、紫外線、赤外線等があるが、後述する光触媒膜４３を励起するものである。
【００５１】
ここで、フォトマスク基板４０について説明する。フォトマスク基板４０は活性光線を透過する透明基板４１を有し、この透明基板４１の一方の面４１ａには、囲繞領域１９，１９に相当するパターンに開口部を有するマスク４２が網目状に形成され、約０．２μｍ厚の光触媒膜４３がマスク４２全体を被覆するように一方の面４１ａ上に成膜されている。つまりマスク４２は、保護絶縁膜１８及び仕切り壁２０に対応するパターンに形成されている。
【００５２】
マスク４２は活性光線を反射したり、吸収したりし、活性光線を透過しない。光触媒膜４３は、酸化チタン（ＴｉＯ₂）、酸化亜鉛（ＺｎＯ）、酸化スズ（ＳｎＯ₂）、チタン酸ストロンチウム（ＳｒＴｉＯ₃）、酸化タングステン（ＷＯ₃）、酸化ビスマス（Ｂｉ₂Ｏ₃）及び酸化鉄（Ｆｅ₂Ｏ₃）の中から選ばれる一種又は二種以上の物質で形成されている。ここでは、酸化チタンを光触媒膜４３として用いる。酸化チタンは、アナターゼ型とルチル型があり本発明では何れも使用することができるが、アナターゼ型の酸化チタンは励起波長が３８０ｎｍ以下であるからより好ましい。
【００５３】
以上のようなフォトマスク基板４０を用いて、透明基板４１の裏面４１ｂに活性光線を入射させる。マスク４２では活性光線が遮蔽されるが、マスク４２の間が囲繞領域１９に重なっており、活性光線が囲繞領域１９に重なった光触媒膜４３を透過する。活性光線が光触媒膜４３を透過する際に活性酸素種（・ＯＨ）が生成され、この活性酸素種が化合物層１４’と化学反応を引き起こす。ここで、化合物層１４’において、囲繞領域１９，１９，…には光触媒膜４３を透過した活性酸素種が入射し、保護絶縁膜１８及び仕切り壁２０に重なった領域ではマスク４２によって遮蔽されることで活性酸素種が届かない。場合によっては囲繞領域１９，１９，…よりやや外側にも活性酸素種が拡散されるように露光条件を設定してもよい。
【００５４】
以上のフォトマスク基板４０において、マスク４２の平面視した形状は仕切り壁２０の平面視した形状とほぼ同じであり、この場合にはフォトマスク基板４０を透明基板１２に近接させることで、マスク４２の影が仕切り壁２０に重なるように投影される。
【００５５】
化合物層１４’は、マスク４２と重ならない領域において、光触媒の作用により生成された活性酸素種（・ＯＨ）により撥液性を示すＲｆ基が、親水性を示す水酸基に置換され、一般式（２３）に示すよう親液性膜１４ａになる。
【化３】

つまり、マスク４２と重ならない領域に相当する親液性膜１４ａは、フッ素を含む官能基（上記Ｒｆ）が分解・離脱し、水酸基に置換されるために、有機化合物含有液に対して親液性を示し、後述するＥＬ層１５を構成する材料が含まれる液体をはじくことなくこの液体を親液性膜１４ａの表面に均一に成膜することが可能になる。このように光触媒の作用は、光触媒膜４３に活性光線が入射することによって、活性酸素種が発生し、活性酸素種がフォトマスク基板４０と化合物層１４’との間の気相を拡散し、化合物層１４’に到達した活性酸素が化合物層１４’の化学構造を変化させる。
【００５６】
更に、親液性膜１４ａにおいては、珪素と酸素からなる重合体における主鎖がアノード１３，１３，…の表面に沿った状態で形成され、且つ、撥液性を示すフッ素を含む官能基が水酸基に置換されるため、膜厚も単分子ユニットにおける主鎖（ここでは重合体としての側鎖に相当。）であるＨＯ−Ｓｉ−Ｘ−基又はＨＯ−Ｓｉ−基の長さに等しく、１ｎｍ以下と非常に薄くすることができる。そのため、活性酸素種が生成された領域であるアノード１３，１３，…上では、パターン膜１４の膜厚が非常に薄くなり、親液性膜１４ａ自体が正孔等の電荷の注入、輸送に支障をきたすことはほとんどない。
そして、パターン膜１４において、マスク４２と重ならない領域に相当する撥液性膜１４ｂは、親液性膜１４ａと連続して成膜されているとともに親液性膜１４ａよりもほぼフッ素を含む官能基Ｒｆの分だけ厚くなり、且つ後述するＥＬ層１５を構成する材料が含まれる液体に対して撥液性を示す。
【００５７】
以上のように化合物層１４’を部分的に露光することによってパターン膜１４を形成した後、それぞれの囲繞領域１９内にＥＬ層１５を成膜する。ＥＬ層１５，１５，…の成膜は、液滴吐出技術（インクジェット技術）を応用して行う。つまり、図４（ｅ）に示すように、ＥＬ層１５の構成材料を含有した有機化合物含有液を吐出することのできるノズル７０を透明基板１２に対向させて、駆動装置によって透明基板１２に対して相対的にノズル７０を水平面に沿って移動させつつ、ノズル７０が囲繞領域１９上に位置した時にノズル７０から有機化合物含有液を液滴として一回又は複数回吐出する。これにより、有機化合物含有液の液滴が囲繞領域１９内においてパターン膜１４上に着弾する。なお、有機化合物含有液を赤、緑、青の色ごとに準備し、隣接する画素毎に異なる発光色のＥＬ層１５，１５，…として塗り分けることができる。
【００５８】
着弾した液滴が囲繞領域１９内で広がって膜になり、そしてその膜が固化することによって、ＥＬ層１５が形成される。パターン膜１４は囲繞領域１９内において親液性膜１４ａとなっているため、着弾した液滴が濡れやすいとともに滲みやすく、有機化合物含有液が囲繞領域１９内全体にいきわたる。特に囲繞領域１９よりやや外側にも活性光線が入射して親液性となっていると、有機化合物含有液が確実に囲繞領域１９内全体にいきわたる。そのため、ＥＬ層１５が均等な厚さで成膜されるとともに、ＥＬ層１５とパターン膜１４との間に剥離が生じることなく、またアノード１３とカソード１６間でのショートを引き起こすこともない。
さらに、囲繞領域１９内に着弾した液滴が囲繞領域１９の周囲の仕切り壁２０の方に跳ね返っても、仕切り壁２０上の撥液性膜１４ｂが有機化合物含有液をはじくのでアノード１３上に滑り落ち、有機化合物含有液を効率よく利用することが可能となる。また、仕切り壁２０の頭頂部より高くなるような大量の有機化合物含有液が囲繞領域１９内に吐出された場合でも、有機化合物含有液が仕切り壁２０上に滲むことがないため、隣り合う二つの画素の有機化合物含有液同士が仕切り壁２０上で混ざりあって互いの囲繞領域１９内に有機化合物含有液を流出、流入することがない。したがって、常に均等な厚さで成膜でき、隣り合う二つの画素が互いに異なる発光色の有機化合物含有液の場合に色純度の高い発色ができる。
【００５９】
なお、ＥＬ層１５が積層構造である場合には、それぞれの層について有機化合物含有液を準備し、囲繞領域１９内にそれぞれの有機化合物含有液を順にノズルで吐出することでそれぞれの層を積層していく。例えば、ＥＬ層１５が正孔注入層、狭義の発光層からなる二層構造の場合には、正孔注入層の有機化合物含有液（正孔注入層を構成する有機化合物が水系溶媒に分散した分散液）を各囲繞領域１９内に吐出することで正孔注入層を成膜し、次いで、狭義の発光層の有機化合物含有液（狭義の発光層を構成する有機化合物が例えばトルエン、キシレン、テトラリンといった有機溶媒に溶解した溶液）を各囲繞領域１９内に吐出することでＥＬ層１５を成膜する。この場合でも、パターン膜１４は、各囲繞領域１９内において正孔注入層の有機化合物含有液に対してなじみ、保護絶縁膜１８及び仕切り壁２０に重なった領域において正孔注入層の有機化合物含有液をはじく。
【００６０】
次いで、蒸着やスパッタ等のＰＶＤ法及びＣＶＤ法といった成膜方法によって、ＥＬ層１５，１５，…を被覆するようにしてカソード１６を一面に成膜する。ＥＬ層１５は囲繞領域１９内全体にいきわたって形成されているから、カソード１６が直接アノード１３に接触することもない。カソード１６の成膜後、封止樹脂、封止ガラスといった封止材でこれらＥＬ素子１１，１１，…を封止する。
【００６１】
以上のように製造された有機ＥＬ表示パネル１０では、画素回路が信号線５１及び走査線５２を介して入力した信号に従ってＥＬ素子１１に電流を流す。ＥＬ素子１１では、アノード１３からＥＬ層１５へ正孔が注入され且つカソード１６からＥＬ層１５へ電子が注入されることで、電流が流れる。そして、ＥＬ層１５において正孔及び電子が輸送されて、ＥＬ層１５にて正孔及び電子が再結合することによってＥＬ層１５で発光する。アノード１３，１３，…及び透明基板１２が透明であるため、ＥＬ層１５で発した光は透明基板１２の裏面１２ｂから出射し、裏面１２ｂが表示面となる。
【００６２】
以上のように、本実施の形態では、シラザン化合物を加水分解・重合させることで化合物層１４’を成膜し、珪素と酸素で構成された重合体としての主鎖がアノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０の表面に沿った状態で全面に形成され、各囲繞領域１９内において親液性膜１４ａの実質的な厚さが、化合物層１４’の単分子ユニットにおける主鎖からフッ素を含む官能基Ｒｆを除く厚さとなり非常に薄い。従って、アノード１３とＥＬ層１５との間にパターン膜１４が介在してもパターン膜１４の絶縁性を無視することができ、アノード１３からＥＬ層１５へ正孔が注入されることが阻害されない。
【００６３】
また、化合物層１４’を成膜する前に酸素プラズマ洗浄又は紫外線／オゾン洗浄を行い、その後更に純水で洗浄するから、撥液性を有する非常に薄い化合物層１４’を簡単に成膜することができる。特に、純水で洗浄したため、仕切り壁２０上に撥液性の化合物層１４’を確実に成膜することができる。これは、純水で洗浄しなかった場合には仕切り壁２０上に撥液性の化合物層１４’を充分に成膜することができないこともあるので、純水洗浄によって仕切り壁２０の表層に付着させた水分子でシラザン化合物の加水分解重合反応を起こさせている。
【００６４】
また、本実施形態では、化合物層１４’内に光触媒を含有させないで、フォトマスク基板４０を通じて化合物層１４’に活性酸素種を照射することで、化合物層１４’を部分的に反応させている。光触媒の部分だけ親液性膜１４ａになるから、アノード１３からＥＬ層１５へ正孔が注入されることは阻害されないとともに、パターン膜１４がＥＬ層１５に化学的に影響を与えることもない。
【００６５】
また、ＥＬ層１５は囲繞領域１９全体にいきわたって均一に成膜されているため、アノードとカソードの間でショートが生じない。また、ＥＬ層１５とパターン膜１４との間に剥離が生じにくいから、発光したＥＬ層１５にダークスポットが発生しにくい。
【００６６】
また、フッ化物プラズマを照射することなく、撥液性を有する化合物層１４’を仕切り壁２０上に成膜したため、露出している保護絶縁膜１８はエッチングされず、保護絶縁膜１８が損傷しない。このため、保護絶縁膜１８がエッチングされた隙間に充分ＥＬ層１５が成膜できずにアノードとカソードの間でショートしてしまうといった問題を防止できる。
【００６７】
なお、上述の説明では液滴吐出法によって複数のＥＬ層１５，１５，…をパターニングしていた。しかしながら、パターン膜１４では親液性の領域がマトリクス状にパターニングされているため、有機化合物含有液をパターン膜１４に塗布して透明基板１２を回転させること（スピンコート法）によって複数のＥＬ層１５，１５，…をマトリクス状にパターニングすることもできる。また、ディップコート法でも複数のＥＬ層１５，１５，…をマトリクス状にパターニングすることができる。
また、上述の説明ではディップコート法によって化合物層１４’を成膜したが、スピンコート法、刷毛塗り法又は蒸着法によって化合物層１４’を成膜しても良い。
また、仕切り壁２０を形成しなくても良い。この場合、アノード１３，１３，…及び保護絶縁膜１８全体を被覆するように化合物層１４’を成膜し、保護絶縁膜１８によって囲繞された囲繞領域１９，１９，…に対してフォトマスク基板４０を介して活性酸素種を供給する。
また、フッ素を含む官能基を有するシラン化合物として、シラザン化合物を挙げたが、シランカップリング剤（加水分解重合可能なフルオロアルキル基含有珪素化合物）といった他のシラン化合物やその他の撥液性を示す官能基でもよく、置換される官能基は水酸基以外の親液性の官能基であっても良い。
【００６８】
〔第二の実施の形態〕
第一実施形態の有機ＥＬ表示パネル１０とは別の有機ＥＬ表示パネルについて説明する。図５は、第二実施形態における有機ＥＬ表示パネル１１０を示した断面図である。
【００６９】
図５に示された有機ＥＬ表示パネル１１０と図２に示された有機ＥＬ表示パネル１０の異なることは、有機ＥＬ表示パネル１０にはパターン膜１４が形成されていたのに対して、有機ＥＬ表示パネル１１０にはパターン膜が形成されていない。つまり、有機ＥＬ表示パネル１１０では、ＥＬ層１５がパターン膜を介せずに直接アノード１３上に成膜されている。有機ＥＬ表示パネル１１０の他の構成要素は第一実施形態の有機ＥＬ表示パネル１０の構成要素と同様であり、有機ＥＬ表示パネル１１０については、第一実施形態における有機ＥＬ表示パネル１０と同様の構成要素に同様の符号を付して詳細な説明を省略する。
【００７０】
有機ＥＬ表示パネル１１０の製造方法について説明する。
第一実施形態の場合と同様に、透明基板１２上に信号線５１，５１，…及び走査線５２，５２，…をパターニング形成するとともに、画素ごとにアノード１３及びトランジスタ２１，２１を透明基板１２の表面１２ａ上にパターニング形成し（図３（ａ））、その後、保護絶縁膜１８及び仕切り壁２０を形成する（図３（ｂ））。
【００７１】
次に、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０ごと透明基板１２をフッ素ガス雰囲気に曝露する。具体的には、チャンバーを用い、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０等が形成された透明基板１２をチャンバーに入れるとともに、チャンバー内の雰囲気について窒素ガスを含む大気圧のフッ素ガス雰囲気とし、透明基板１２をチャンバー内において数分放置する。フッ素ガス雰囲気下においては、仕切り壁２０の表層でフッ素のラジカル種（活性種）が反応し、仕切り壁２０の表層にフッ化物（主にフッ素と炭素の化合物）が形成される。従って、仕切り壁２０の表層が撥液性を示す。純水に対する接触角の変化を表１に示す。ポリイミドからなる仕切り壁２０は、フッ化処理の前では接触角が７１°であったのに対し、フッ化処理後では接触角が９６°になった。なお、ＩＴＯからなるアノード１３も、フッ化処理によって接触角が５８°から９４°になった。
【表１】

【００７２】
フッ化処理だけではアノード１３，１３，…も撥液性となっているため、フッ化処理後に、大気圧未満の減圧下において酸素プラズマをアノード１３，１３，…及び仕切り壁２０に約二分間照射する。これにより、アノード１３，１３，…及び仕切り壁２０の表層に形成されたフッ化物がアッシングされて、アノード１３，１３，…及び仕切り壁２０の撥液性が低下する。しかしながら、仕切り壁２０の撥液性の低下は、アノード１３の撥液性の低下ほど顕著ではない。表１から明らかなように、酸素プラズマ処理後では、アノード１３の接触角は２１．２°になってアノード１３は親液性であるのに対して、仕切り壁２０の接触角は６２．６°になって仕切り壁２０は依然として高い撥液性である。なお、フッ化物のアッシングは、減圧酸素プラズマ照射によって行ったが、大気圧酸素プラズマ照射によって行っても良いし、紫外線／オゾン洗浄によって行っても良いし、その他の表面酸化法によって行っても良い。
【００７３】
次いで、第一実施形態の場合と同様に、それぞれの囲繞領域１９内にＥＬ層１５を成膜する。ＥＬ層１５は、液滴吐出法によって成膜しても良いし、スピンコート法によって成膜しても良いし、ディップコート法によって成膜しても良い。
次いで、第一実施形態の場合と同様に、ＥＬ層１５，１５，…全てを被覆するようにしてカソード１６を一面に成膜し、封止樹脂、封止ガラスといった封止材でこれらＥＬ素子１１，１１，…を封止する。
【００７４】
以上のように、本実施形態では、フッ化物プラズマを照射することなく、仕切り壁２０の表層を撥液性とするため、保護絶縁膜１８がエッチングされず、保護絶縁膜１８が損傷することがない。
また、アノード１３，１３，…の表層をアッシングしているため、アノード１３，１３，…の表面に不純物等が付着していない。そのため、アノード１３，１３，…が絶縁性となっていない上ＥＬ層１５がアノード１３に直接接し、アノード１３からＥＬ層１５へ正孔が注入されることは阻害されない。
また、アノード１３，１３，…の表面に不純物等が付着していないから、アノード１３，１３，…は親液性となる。従って、ＥＬ層１５が均等な厚さで成膜されるとともに、ＥＬ層１５とパターン膜１４との間に剥離した部分が無い。 また、仕切り壁２０の頭頂部より高くなるような大量の有機化合物含有液が囲繞領域１９内に吐出された場合でも、仕切り壁２０の表面が撥液性となっているため、有機化合物含有液が仕切り壁２０上に滲むことがない。そのため、隣り合う二つの画素の有機化合物含有液同士が仕切り壁２０上で混ざることがない。
【００７５】
〔第三の実施の形態〕
第一実施形態の有機ＥＬ表示パネル１０とは別のＥＬ表示パネルについて説明する。図６は、第三実施形態における有機ＥＬ表示パネル２１０を示した断面図である。
【００７６】
図６に示された有機ＥＬ表示パネル２１０と図２に示された有機ＥＬ表示パネル１０の異なることは、有機ＥＬ表示パネル１０にはパターン膜１４が形成されていたのに対して、有機ＥＬ表示パネル２１０にはパターン膜が形成されていない。つまり、有機ＥＬ表示パネル２１０では、ＥＬ層１５がパターン膜を介せずに直接アノード１３上に成膜されている。また、有機ＥＬ表示パネル２１０では、撥液性の撥液層２１４が仕切り壁２０上に形成されている。そして、カソード１６は、仕切り壁２０と重なる領域においては撥液層２１４を介して仕切り壁２０上に形成されている。有機ＥＬ表示パネル２１０の他の構成要素は第一実施形態の有機ＥＬ表示パネル１０の構成要素と同様であり、有機ＥＬ表示パネル２１０については、第一実施形態における有機ＥＬ表示パネル１０と同様の構成要素に同様の符号を付して詳細な説明を省略する。
【００７７】
有機ＥＬ表示パネル２１０の製造方法について説明する。
第一実施形態の場合と同様に、透明基板１２上に信号線５１，５１，…及び走査線５２，５２，…をパターニング形成するとともに、画素ごとにアノード１３及びトランジスタ２１，２１を透明基板１２の表面１２ａ上にパターニング形成し（図３（ａ））、その後、保護絶縁膜１８及び仕切り壁２０を形成する（図３（ｂ））。
【００７８】
次に、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０等が形成された透明基板１２の表面１２ａ側に、減圧下において酸素プラズマを照射する。これにより、アノード１３，１３，…及び仕切り壁２０の表層に付着した不純物がアッシングされて、アノード１３，１３，…及び仕切り壁２０の親液性が向上する。なお、不純物のアッシングは、減圧酸素プラズマ照射によって行ったが、大気圧酸素プラズマ照射によって行っても良いし、紫外線／オゾン洗浄によって行っても良いし、その他の表面酸化法によって行っても良い。次いで、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０等が形成された透明基板１２を純水で洗浄し、乾燥させる。
【００７９】
次に、アノード１３，１３，…、保護絶縁膜１８及び仕切り壁２０等が形成された透明基板１２を蒸着装置内にセッティングし、図７に示すように、蒸着装置内の坩堝２２０に蒸着原料２２１を収容する。蒸着原料２２１は、例えばフッ素を含む官能基を有するシラン化合物が良く、特に低分子量のシラン化合物が良い。フッ素を含む官能基としてはフルオロアルキル基がある。
【００８０】
更に、図７に示すように、それぞれの囲繞領域１９に対向するようにマスク２２３をアノード１３に被覆する。そして、電子ビーム、ヒータ等で蒸着原料２２１を加熱・蒸発させることで、仕切り壁２０の表面にシラン化合物が蒸着し、シラン化合物からなる撥液層２１４が成膜される。
【００８１】
次いで、第一実施形態の場合と同様に、それぞれの囲繞領域１９内にＥＬ層１５を成膜する。ＥＬ層１５は、液滴吐出法によって成膜しても良いし、スピンコート法によって成膜しても良いし、ディップコート法によって成膜しても良い。
次いで、第一実施形態の場合と同様に、ＥＬ層１５，１５，…を被覆するようにしてカソード１６を一面に成膜し、封止樹脂、封止ガラスといった封止材でこれらＥＬ素子１１，１１，…を封止する。
【００８２】
以上のように、本実施の形態では、フッ化物プラズマを照射することなく、フッ素を含む官能基を有したシラン化合物の撥液層２１４を仕切り壁２０の表面に形成しているため、保護絶縁膜１８がエッチングされず、保護絶縁膜１８が損傷することがない。
また、アノード１３，１３，…の表層をアッシングしているため、アノード１３，１３，…の表面に不純物等が付着していない。更に蒸着の際にアノード１３，１３，…をマスクしているため、フッ素を含む官能基を有したシラン化合物がアノード１３，１３，…の表面に付着しない。そのため、アノード１３，１３，…が絶縁性となっていないうえ、ＥＬ層１５がアノード１３に直接接し、アノード１３からＥＬ層１５へ正孔が注入されることは阻害されない。
また、アノード１３，１３，…の表面にシラン化合物や不純物が付着していないから、アノード１３，１３，…は親液性となる。従って、ＥＬ層１５が均等な厚さで成膜されるとともに、ＥＬ層１５とパターン膜１４との間に剥離した部分が無い。
また、仕切り壁２０の頭頂部より高くなるような大量の有機化合物含有液が囲繞領域１９内に吐出された場合でも、仕切り壁２０の表面が撥液性となっているため、有機化合物含有液が仕切り壁２０上に滲むことがない。そのため、隣り合う二つの画素の有機化合物含有液同士が仕切り壁２０上で混ざることがない。
【００８３】
なお、本発明は上記各実施の形態に限定されることなく、本発明の趣旨を逸脱しない範囲において、種々の改良並びに設計の変更を行っても良い。
例えば、上記各実施形態の表示パネルをページプリンタといった画像形成装置の線走査機構に用いることができる。
また、上記各実施形態では、カソード１６が全ての有機ＥＬ素子１１，１１，…について共通しているが、カソードとアノードの配置を代えて有機ＥＬ素子１１各画素ごとにカソードを形成しても良い。
また、板状の透明基板１２の代わりにシート状の透明なフィルム基板であっても良い。
【００８４】
【発明の効果】
請求項１に記載の発明によれば、フッ素ガス雰囲気に基板を曝露することによって仕切り壁の表面にはフッ化物が形成されるから、仕切り壁の表面が撥液性となる。
【００８５】
仕切り壁の表面が撥液性となっているため、有機化合物含有液が仕切り壁上に滲むことがない。そのため、隣り合う二つの画素の有機化合物含有液同士が仕切り壁上で混ざることがない。
【図面の簡単な説明】
【図１】本発明を適用した有機ＥＬ表示パネルを示した平面図である。
【図２】図１に示された有機ＥＬ表示パネルの断面図である。
【図３】図１に示された有機ＥＬ表示パネルの製造工程を示した図面である。
【図４】図１に示された有機ＥＬ表示パネルの製造工程を示した図面である。
【図５】図１に示された有機ＥＬ表示パネルとは別の有機ＥＬ表示パネルを示した断面図である。
【図６】図１、図５に示された有機ＥＬ表示パネルとは別の有機ＥＬ表示パネルを示した断面図である。
【図７】図６に示された有機ＥＬ表示パネルの製造工程を示した図面である。
【符号の説明】
１０、１１０、２１０ 有機ＥＬ表示パネル（表示パネル）
１１ ＥＬ素子（発光素子）
１２ 透明基板（基板）
１２ａ 表面
１３ アノード（第一電極、電極）
１４’ 化合物層
１４ パターン膜
１４ａ 親液性膜
１４ｂ 撥液性膜
１５ ＥＬ層
１６ カソード（第二電極）
１９ 囲繞領域（電極露出領域）
２０ 仕切り壁
４３ 光触媒膜
２１４ 撥液層
２２３ マスク[0001]
BACKGROUND OF THE INVENTION
  The present invention relates to a display panel in which an optical element, in particular, a plurality of organic EL (Electro Luminescence) elements are arranged on a substrate.LeIt relates to a manufacturing method.
[0002]
[Prior art]
The organic EL element has a laminated structure in which an anode, an EL layer made of an organic compound, and a cathode are laminated in this order. When a positive bias voltage is applied between the anode and the cathode, the EL layer emits light. An organic EL display panel that displays images by arranging such organic EL elements as pixels in a matrix on a substrate and emitting each organic EL element with a predetermined gradation luminance is realized.
[0003]
In an active matrix driving organic EL display panel, one of the anode and the cathode can be a common electrode common to all pixels, but it is necessary to pattern at least the other electrode and the EL layer for each pixel. is there. Conventional semiconductor device manufacturing techniques can be applied to the method of patterning the anode and cathode for each pixel. That is, the anode and the cathode can be patterned for each pixel by appropriately performing a film forming process by a PVD method or a CVD method, a mask process by a photolithography method, or a thin film shape processing process by an etching method or the like.
[0004]
The method for forming the EL layer can be broadly classified into a dry vapor deposition method and a wet coating method according to conditions such as materials. In the case of using a dry evaporation method, an EL layer formed by evaporation by using a metal mask can be patterned for each pixel. On the other hand, when the wet coating method is used, patterning can be performed for each pixel by applying an inkjet technique, for example. That is, the EL layer can be patterned for each pixel by discharging, for each pixel, a droplet of an organic solution obtained by dissolving the material that becomes the EL layer with an organic solvent.
[0005]
By the way, in order to provide an organic EL display panel that performs high-resolution image display, the EL layer must be formed in a fine pattern. In the inkjet method, since the particle size of the droplet of the organic solution is very small, it is possible to form the EL layer with a fine pattern. However, since the droplet bleeds between the landing of the droplet and the solidification, it is adjacent. There is a risk of mixing with the EL layer droplets of the matching pixels. Therefore, after finely patterning a mesh-like partition wall that has been partitioned for each pixel in advance on the substrate, droplets are ejected to the area surrounded by the partition wall, so that the droplets of adjacent pixels are mixed. A technique for preventing this has been proposed (see, for example, Patent Document 1).
[0006]
In the method of manufacturing an organic EL display panel described in Patent Document 1, a thin film transistor is formed on one surface for each pixel, and these thin film transistors are coated with a protective insulating film such as silicon nitride and silicon oxide. A substrate is used. A plurality of anodes are formed in a matrix on such a substrate, and a partition wall is formed on the substrate so as to surround each anode. Then, fluoride (CF) is directed toward the surface on which the plurality of anodes and partition walls are formed._Four) Make the surface of the partition wall liquid repellent by irradiating with plasma. Thereafter, an organic solution is applied to each anode by an inkjet method to form an EL layer on each anode. By making the surface of the partition wall liquid repellent, it is possible to efficiently prevent the liquid droplets of adjacent pixels from being mixed.
[0007]
[Patent Document 1]
JP 2000-353594 A
[0008]
[Problems to be solved by the invention]
By the way, a thin film transistor is required for each pixel in order to drive the organic EL display panel in an active matrix, and a protective insulating film is also required to protect the thin film transistor. However, when the fluoride plasma is irradiated, the protective insulating film is etched. In some cases, the thin film transistor may be further deteriorated. This is considered because fluoride plasma reacts with silicon in the protective insulating film.
[0009]
Also, when fluoride plasma is irradiated toward the surface on which a plurality of anodes and partition walls are formed, fluoride radical species are also polymerized on the surface of the anode, and fluorine and carbon compounds are formed on the anode surface. Will also become liquid repellent. If the anode becomes liquid repellent, droplets of the organic solution do not bleed on the anode, and the thickness of the EL layer may not be uniform, or peeling may occur between the EL layer and the anode. . Further, since a compound layer of fluorine and carbon is formed on the surface of the anode and the compound layer has an insulating property, the EL layer does not emit light even when a positive bias voltage is applied between the anode and the cathode.
[0010]
  Therefore, an object of the present invention is to provide a display panel that can suppress damage to the protective insulating film formed on the substrate, and can suppress the surface of the electrode formed on the substrate from being insulative.LeIt is to provide a manufacturing method.
[0011]
[Means for Solving the Problems]
  In order to solve the above-described problems, the first electrode, the EL layer, and the second electrode, which are indium oxide, zinc oxide, tin oxide, or a mixture containing at least one of them, according to claim 1, are sequentially provided. In a display panel manufacturing method for manufacturing a display panel in which a plurality of stacked optical elements are arranged on a substrate,
  A partition wall made of an organic compound is formed on the one surface of the substrate on which the plurality of first electrodes are spaced apart from each other so as to surround each of the first electrodes. Process,
  The substrate together with the partition wall and the plurality of first electrodes is nitrided.ElementaryExposing the partition wall and the plurality of first electrodes to liquid repellency by exposing to a fluorine gas atmosphere having a gas and a fluorine gas;
  After the liquid repellency step, reducing the liquid repellency of the surface layers of the plurality of first electrodes by oxygen plasma treatment;
  Forming the EL layer on the first electrode;
  It is characterized by including.
[0012]
  In the said invention, since the fluoride is formed in the surface of a partition wall by exposing a board | substrate to fluorine gas atmosphere, the surface of a partition wall becomes liquid repellency.
[0013]
  Further, although fluoride is also formed on the surface of the electrode, the fluoride formed on the surface of the electrode is removed by ashing the surface layer of the electrode. Since the fluoride is removed, there is no insulating film or the like between the electrode and the organic layer.
[0014]
  Moreover, since the electrode becomes lyophilic by removing the fluoride, when such a manufacturing method is applied to the formation of the EL layer, the organic compound-containing liquid for forming the applied EL layer bleeds in the electrode, Repels at the partition wall. Therefore, the organic compound-containing liquid is not mixed between adjacent electrodes.
[0015]
  Further, since the organic compound-containing liquid oozes on the electrode, the thickness of the EL layer becomes uniform, and no peeling occurs between the EL layer and the electrode.
[0016]
  The oxygen plasma treatment may be a reduced pressure oxygen plasma treatment or an atmospheric pressure oxygen plasma treatment.
[0017]
  A protective insulating film may be disposed below the partition wall.
[0018]
The protective insulating film may be silicon oxide or silicon nitride.
[0019]
  The partition wall may be polyimide.
[0020]
  The first electrode is indium oxide, zinc oxide, tin oxide or a mixture containing at least one of them.Ru.
[0021]
  Forming the second electrode on the EL layer;
  May be included.
[0022]
  The step of forming the EL layer may be a droplet discharge method, a spin coating method, or a dip coating method.
[0023]
  A method for manufacturing a display panel includes a plurality of first electrodes, EL layers, and second electrodes, which are indium oxide, zinc oxide, tin oxide, or a mixture containing at least one of them, each sequentially stacked.lightIn a method for manufacturing a display panel for manufacturing a display panel in which academic elements are arranged on a substrate,
  A partition wall made of an organic compound is formed on the one surface of the substrate on which the plurality of first electrodes are spaced apart from each other so as to surround each of the first electrodes. Process,
  The substrate together with the partition wall and the plurality of first electrodes is nitrided.ElementaryExposing the partition wall and the plurality of first electrodes to liquid repellency by exposing to a fluorine gas atmosphere having a gas and a fluorine gas;
  After the liquid repellency step, reducing the liquid repellency of the surface layers of the plurality of first electrodes by ultraviolet ozone cleaning treatment;
  Forming the EL layer on the first electrode;
  It is characterized by including.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, specific embodiments of the present invention will be described with reference to the drawings. However, the scope of the invention is not limited to the illustrated examples. Further, in the following description, “in plan view” means “seen in a direction perpendicular to the transparent substrate 12 (described later)”.
[0025]
[First embodiment]
FIG. 1 is a plan view of an organic EL display panel 10 to which the present invention is applied, and FIG. 2 is a cross-sectional view taken along the cutting line S1-S2 shown in FIG.
[0026]
The organic EL display panel 10 has pixels arranged in a matrix in plan view, and performs matrix display by an active matrix driving method. That is, the organic EL display panel 10 includes one EL element 11 and one pixel circuit for driving the EL element 11 for each pixel. The pixel circuit is a peripheral driver (not shown). A signal is input from the signal line 51 and the scanning line 52, and the current flowing through the EL element 11 is turned on / off according to the input signal, or the current value is maintained during the light emission period of the EL element 11 11 emission luminance is kept constant. Each pixel circuit is composed of at least one transistor, and a capacitor may be added as appropriate. In FIG. 1, for example, the pixel circuit is composed of two transistors 21 and 21. To do.
[0027]
The organic EL display panel 10 has a flat transparent substrate 12, and a plurality of signal lines 51, 51,... Extending in the vertical direction are formed on the surface 12 a of the transparent substrate 12. The signal lines 51, 51,... Are arranged in parallel with each other at substantially equal intervals in plan view. The signal lines 51, 51,... Have conductivity and are covered with a gate insulating film 23 formed on the entire surface 12 a of the transparent substrate 12. A plurality of scanning lines 52, 52,... Extending in the lateral direction are formed on the gate insulating film 23, and the scanning lines 52, 52,. They are orthogonal to each other. The scanning lines 52, 52,... Are also arranged in parallel with each other at substantially equal intervals in plan view.
[0028]
A plurality of transistors 21, 21,... Are formed on the surface 12 a of the transparent substrate 12. Each transistor 21 includes a gate electrode 22, a gate insulating film 23, a semiconductor film 24, impurity semiconductor films 25 and 26, a drain electrode 27, and a source electrode 28, and is a MOS field effect thin film transistor in which these are stacked. is there. The gate insulating film 23 is formed on the entire surface of the transparent substrate 12, and is a common layer for all the transistors 21, 21,.
[0029]
The transistors 21, 21,... Are covered with a protective insulating film 18. The protective insulating film 18 is formed in a mesh shape in plan view. When the protective insulating film 18 is formed in a mesh shape in a plan view, a plurality of surrounding regions 19, 19,... Surrounded by the protective insulating film 18 are arranged in a matrix on the transparent substrate 12. It is formed. The protective insulating film 18 is made of silicon oxide (SiO₂) And silicon nitride (SiN). A partition wall 20 is formed on the protective insulating film 18 so as to overlap the protective insulating film 18, and the partition wall 20 is also formed in a mesh shape in plan view like the protective insulating film 18. The width of the partition wall 20 is narrower than the width of the protective insulating film 18, and the protective insulating film 18 extends from both wall surfaces of the partition wall 20 in plan view. Further, the width of the partition wall 20 increases as the distance from the transparent substrate 12 approaches. The partition wall 20 has an insulating property and is formed of an organic compound such as a photosensitive resin such as a polyimide resin.
[0030]
Next, the EL element 11 that is an optical element will be described. The EL element 11 has a laminated structure in which an anode 13 as a first electrode, a pattern film 14, an EL layer 15, and a cathode 16 as a second electrode are laminated in this order from the transparent substrate 12 side. The anode 13 is transmissive to visible light and conductive. The anode 13 has a relatively high work function. The anode 13 is formed of, for example, indium oxide, zinc oxide, tin oxide, or a mixture containing at least one of them (for example, tin-doped indium oxide (ITO), zinc-doped indium oxide).
[0031]
In plan view, the anode 13 is disposed in each region surrounded by the signal lines 51, 51,... And the scanning lines 52, 52,..., And the plurality of anodes 13, 13,. Further, they are arranged in a matrix on the gate insulating film 23.
[0032]
Further, in plan view, the anodes 13 respectively face the surrounding area 19, the area of the surrounding area 19 is smaller than the area of the anode 13, and the surrounding area 19 is disposed in the anode 13. The outer peripheral part of the protective layer is covered with a part of the protective insulating film 18 and the partition wall 20. In this example, the anode 13 is connected to the source electrode 28 of the transistor 21, but the anode 13 may be connected to another transistor or capacitor depending on the circuit configuration of the pixel circuit.
[0033]
A pattern film 14 is formed on the anodes 13, 13,. The pattern film 14 is formed on the entire surface of the transparent substrate 12 and covers the partition wall 20 together with the anodes 13, 13,. The pattern film 14 conforms to the organic compound-containing liquid in a region overlapping the anodes 13, 13,..., And has a surface property (hereinafter referred to as “lyophilic”) having a contact angle with these liquids of 40 ° or less. And the lyophilic film 14a provided with the organic compound-containing liquid in the region overlapping with the protective insulating film 18 and the partition wall 10, and the surface properties with a contact angle exceeding 40 ° with these liquids. (Hereinafter, referred to as “liquid repellency”) and a liquid repellent film 14 b having a pattern. At this time, the organic compound-containing liquid may be oleophilic like an organic material or hydrophilic like water. That is, in the pattern film 14, the liquid repellent region is formed in a mesh shape in plan view, and the lyophilic region is formed in a matrix so as to be surrounded by the liquid repellent region. Has been. The lyophilic film 14a of the pattern film 14 is very thin and has a thickness greater than 0.0 nm and 1 nm or less. The organic compound-containing liquid is a liquid containing an organic compound constituting the EL layer 15 or a precursor thereof, and even if the organic compound constituting the EL layer 15 or a precursor thereof is dissolved in a solvent as a solute. Alternatively, a dispersion liquid in which the organic compound constituting the EL layer 15 or a precursor thereof is dispersed in a liquid may be used.
[0034]
In a plan view, these EL layers 15, 15,... Are arranged in a matrix and are formed on the pattern film 14 so as to be disposed in each surrounding region 19 and to overlap each anode 13. It is a membrane. That is, the EL layer 15 is formed on the lyophilic region of the pattern film 14.
[0035]
Each EL layer 15 is a layer formed of a light-emitting material that is an organic compound, and generates excitons by recombining holes injected from the anode 13 and electrons injected from the cathode 16, This layer emits light in red, blue, or green. Further, each EL layer 15 may be appropriately mixed with an electron transporting substance, may be appropriately mixed with a hole transporting substance, or may be mixed with an electron transporting substance and a hole transporting substance. Substances may be mixed as appropriate.
[0036]
Each EL layer 15 has a three-layer structure that becomes a hole transport layer, a light-emitting layer in a narrow sense, and an electron transport layer in order from the anode 13, or a two-layer structure that becomes a hole transport layer and a light-emitting layer in a narrow sense in order from the anode 13. Or a single layer structure composed of a light-emitting layer in a narrow sense, or a laminated structure in which an electron or hole injection layer is interposed between appropriate layers in these layer structures. The EL layer 15 is formed by applying an organic compound-containing liquid (that is, a wet application method).
[0037]
The cathode 16 is continuously formed on the entire surface of the transparent substrate 12 so as to cover all the EL layers 15, 15. The cathode 16 includes at least a material having a low work function, and is specifically formed of a simple substance made of magnesium, calcium, lithium, barium, or a rare earth, or an alloy containing at least one of these simple substances. Further, the cathode 16 may have a laminated structure, for example, a laminated structure in which a film formed of a low work function material as described above is coated with a high work function and low resistivity material such as aluminum or chromium. But it ’s okay. The cathode 16 desirably has a light blocking property with respect to visible light, and further desirably has a high reflectivity with respect to visible light emitted from the EL layer 15. That is, the cathode 16 acts as a mirror surface that reflects visible light, so that the light use efficiency can be improved.
[0038]
As described above, the pattern film 14 and the cathode 16 are layers that are continuously common to all the EL elements 11, 11,..., And the anode 13 and the EL layer 15 are provided for each EL element 11 (that is, for each pixel). ) Is formed independently.
[0039]
Next, a method for manufacturing the organic EL display panel 10 will be described with reference to FIGS.
First, the signal lines 51, 51,... And the scanning lines 52, by appropriately performing film forming processes such as sputtering, PVD and CVD, mask processes such as photolithography, and thin film shape processing such as etching. .. Are patterned and the anode 13 and the transistors 21 and 21 are patterned on the surface 12a of the transparent substrate 12 for each pixel (FIG. 3A). Here, when the anode 13 and the transistor 21 are formed by patterning, they are masked with a resist so that the source electrode 28 of the transistor 21 and the anode 13 are connected.
[0040]
After forming the anodes 13, 13,... And the transistors 21, 21,..., A film forming process such as a PVD method and a CVD method, a mask process such as a photolithography method, and a thin film shape processing process such as an etching method are performed. A net-like protective insulating film 18 is formed so as to surround the anode 13. Next, a photosensitive resin film made of a photosensitive resin such as polyimide is formed on one surface of the transparent substrate 12, and after the photosensitive resin film is partially exposed, a developer is applied to the photosensitive resin film. Then, the photosensitive resin film is processed into a mesh shape. As a result, a mesh-like partition wall 20 made of a photosensitive resin is formed, and surrounding areas 19, 19,... Surrounded by the protective insulating film 18 and the partition wall 20 are formed, and the anode 13 is exposed in each surrounding area 19. (FIG. 3B). Therefore, each surrounding area 19 becomes an electrode exposed area, and the partition wall 20 that partitions each surrounding area 19 becomes a non-electrode exposed area. When exposing the photosensitive resin film, if the photosensitive resin film is a negative type, light is irradiated to a portion overlapping the protective insulating film 18, and conversely, if the photosensitive resin film is a positive type. Irradiates the region surrounded by the protective insulating film 18 with light.
[0041]
Next, the surface 12 a side of the transparent substrate 12, that is, the surfaces of the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20 are cleaned. The cleaning may be oxygen plasma cleaning under reduced pressure below atmospheric pressure, or ultraviolet / ozone cleaning. Thereafter, the surface 12a side of the transparent substrate 12 is washed with pure water. Next, an inert gas such as nitrogen gas is sprayed on the transparent substrate 12 to dry the transparent substrate 12.
[0042]
Next, a film made of a silane compound having a functional group containing fluorine, in particular, a silazane compound having a functional group containing fluorine, is coated on the surface 12 a side of the transparent substrate 12. Specifically, the surface of the transparent substrate 12 is obtained by immersing the transparent substrate 12 in a solution containing a silazane compound having a functional group containing fluorine (hereinafter referred to as a silazane-based solution) and then pulling up the transparent substrate 12. A silazane solution is applied to the entire surface of the 12a side (dip coating method).
[0043]
Here, the “silazane compound having a functional group containing fluorine” is a compound having a Si—N—Si bond, and a functional group containing fluorine bonded to N or / and Si. The oligomer or polymer represented by Formula (1) is mentioned.
RfSi (NH)_3/2  ... (1)
In the general formula (1), Rf is a functional group containing fluorine.
The “functional group containing fluorine” includes a fluoroalkyl group, and examples thereof include functional groups represented by the following general formulas (2) to (19).
-(CH₂)_a(CF₂)_bCF_Three  ... (2)
-(CH₂)_a(CF₂)_bCF (CF_Three)₂  ... (3)
-(CH₂)_a(CF₂)_bC (CF_Three)_Three  (4)
-(CF₂)_aCF_Three  ... (5)
-(CF₂)_aCF (CF_Three)₂  (6)
-(CF₂)_aC (CF_Three)_Three  ... (7)
-(CF₂)_a(C (CF_Three)₂)_bCF_Three  ... (8)
-(CF₂)_a(C (CF_Three)₂)_bCF (CF_Three)₂  ... (9)
-(CF₂)_a(C (CF_Three)₂)_bC (CF_Three)_Three  (10)
-(CF₂)_a(C (CF_Three)₂)_b(CF₂)_cCF_Three  ... (11)
-(CF₂)_a(C (CF_Three)₂)_b(CF₂)_cCF (CF_Three)₂  (12)
-(CF₂)_a(C (CF_Three)₂)_b(CF₂)_cC (CF_Three)_Three  ... (13)
-(C (CF_Three)₂)_aCF_Three  ... (14)
-(C (CF_Three)₂)_aCF (CF_Three)₂  ... (15)
-(C (CF_Three)₂)_aC (CF_Three)_Three  ... (16)
-(C (CF_Three)₂)_a(CF₂)_bCF_Three  ... (17)
-(C (CF_Three)₂)_a(CF₂)_bCF (CF_Three)₂  ... (18)
-(C (CF_Three)₂)_a(CF₂)_bC (CF_Three)_Three  ... (19)
In general formulas (2) to (19), a, b, and c are all integers.
[0044]
Examples of the solvent for the silazane solution include a fluorine solvent.
[0045]
Here, as the silazane compound, a silazane oligomer (KP-801M: manufactured by Shin-Etsu Chemical Co., Ltd.) represented by the following general formula (20) and chemical structural formula (21) is used. In the dip coating step described above, the transparent substrate 12 is immersed for about one minute in a silazane-based solution (concentration: 3 wt%) obtained by dissolving the silazane oligomer as a solute in an m-xylene hexafluoride solvent.
C₈F₁₇C₂H_FourSi (NH)_3/2  ... (20)
[Chemical 1]

[0046]
Next, an inert gas such as nitrogen gas is blown onto the transparent substrate 12 to evaporate the solvent of the silazane-based solution, whereby silazane compounds are deposited on the surfaces of the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20. It will be in the state.
[0047]
Next, when the transparent substrate 12 is left for 10 to 30 minutes, the silazane compound is hydrolyzed and polymerized by moisture in the atmosphere and chemically bonded to the protective insulating film 18 and the partition wall 20. As a result, as shown in FIG. 3C, the compound layer 14 ′ made of a polymer to which a functional group containing fluorine is bonded so as to cover the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20 as a whole. In addition, a film is formed on one surface 12 a of the transparent substrate 12. The polymer contained in the compound layer 14 'is represented by the following general formula (22).
[Chemical 2]

[0048]
In the general formula (22), Rf is a functional group containing fluorine as described above and exhibiting liquid repellency, and X is the anode 13, the protective insulating film 18 or the partition wall 20 bonded to the silazane compound. Consists of an atom or atomic group, or a group of atoms or atomic groups of a silazane compound bonded to the surface of the anode 13, the protective insulating film 18 or the partition wall 20, or an NH group in the chemical structural formula (21). N is an integer of 100 or more. When the silazane compound is a silazane oligomer represented by the general formula (20), Rf is C₈F₁₇C₂H_FourAnd X becomes O. Since the silazane compound has high activity and is easily adsorbed to the anode 13, the protective insulating film 18 and the partition wall 20, the compound layer 14 ′ is chemically adsorbed on the surfaces of the anodes 13, 13,. In this state, the film is formed. Therefore, in the compound layer 14 ′, the Rf—Si—X— group or the Rf—Si— group, which is the main chain in the monomolecular unit of the silazane compound, has the anodes 13, 13,. Of the single molecular unit which is arranged in a direction substantially perpendicular to the surface of the anode and is adjacent to the surface of the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20 by hydrolysis. Polymerized in an ether bond state. That is, the silazane compound is polymerized in the surface direction of the surfaces of the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20, and on the surfaces of the anodes 13, 13,. The main chain Rf-Si-X- group or Rf-Si- group in the single molecule unit is further formed above the Rf-Si-X- group or Rf-Si- group that is the main chain in the single molecule unit. There is almost no accumulation. For this reason, the thickness of the compound layer 14 ′ is substantially the same as that of the Rf—Si—X— group or the Rf—Si— group which is the main chain (here, corresponds to a side chain as a polymer) in a single molecular unit. Equal to the length. Further, this compound layer 14 ′ is polymerized so that the functional group Rf containing fluorine is arranged at the tip of the main chain in the single molecular unit, that is, on the surface of the compound layer 14 ′. Shows liquid repellency.
[0049]
Next, after leaving the transparent substrate 12 to stand, the surface 12a side of the transparent substrate 12 is rinsed with m-xylene hexafloid liquid, so that the surface of the anode 13, 13,..., The protective insulating film 18 and the partition wall 19 is not accumulated. Wash away the silazane compound of the reaction.
[0050]
Next, as shown in FIG. 3 (d), the photomask substrate 40 is opposed to the transparent substrate 12, and the active light is transmitted through the photomask substrate 40 to partially irradiate the compound layer 14 'with active light. Thus, the compound layer 14 ′ becomes the pattern film 14. Active light includes visible light, ultraviolet light, infrared light, and the like, and excites a photocatalytic film 43 described later.
[0051]
Here, the photomask substrate 40 will be described. The photomask substrate 40 has a transparent substrate 41 that transmits actinic rays. On one surface 41a of the transparent substrate 41, a mask 42 having openings in patterns corresponding to the surrounding regions 19 and 19 is formed in a mesh shape. Then, a photocatalyst film 43 having a thickness of about 0.2 μm is formed on one surface 41 a so as to cover the entire mask 42. That is, the mask 42 is formed in a pattern corresponding to the protective insulating film 18 and the partition wall 20.
[0052]
The mask 42 reflects or absorbs actinic rays and does not transmit actinic rays. The photocatalytic film 43 is made of titanium oxide (TiO₂), Zinc oxide (ZnO), tin oxide (SnO)₂), Strontium titanate (SrTiO)_Three), Tungsten oxide (WO_Three), Bismuth oxide (Bi₂O_Three) And iron oxide (Fe₂O_Three1) or two or more kinds of substances selected from among the above. Here, titanium oxide is used as the photocatalytic film 43. Titanium oxide includes anatase type and rutile type, and both can be used in the present invention, but anatase type titanium oxide is more preferable because the excitation wavelength is 380 nm or less.
[0053]
Using the photomask substrate 40 as described above, actinic rays are incident on the back surface 41 b of the transparent substrate 41. Actinic rays are shielded by the mask 42, but the space between the masks 42 overlaps the surrounding region 19, and the actinic rays pass through the photocatalytic film 43 that overlaps the surrounding region 19. When active light passes through the photocatalytic film 43, active oxygen species (.OH) are generated, and this active oxygen species causes a chemical reaction with the compound layer 14 '. Here, in the compound layer 14 ′, the active oxygen species that have passed through the photocatalyst film 43 are incident on the surrounding regions 19, 19,..., And the region that overlaps the protective insulating film 18 and the partition wall 20 is shielded by the mask 42. The reactive oxygen species cannot reach. In some cases, the exposure conditions may be set so that the active oxygen species are diffused slightly outside the surrounding areas 19, 19,.
[0054]
In the photomask substrate 40 described above, the shape of the mask 42 in plan view is substantially the same as the shape of the partition wall 20 in plan view. In this case, the photomask substrate 40 is brought close to the transparent substrate 12, thereby allowing the mask 42. Are projected so as to overlap the partition wall 20.
[0055]
In the compound layer 14 ′, the Rf group exhibiting liquid repellency is substituted with a hydroxyl group exhibiting hydrophilicity by the active oxygen species (.OH) generated by the action of the photocatalyst in a region that does not overlap with the mask 42. 23) becomes the lyophilic film 14a.
[Chemical Formula 3]

That is, the lyophilic film 14a corresponding to the region that does not overlap with the mask 42 has a lyophilic property to the organic compound-containing liquid because the functional group containing fluorine (the above Rf) is decomposed and separated and replaced with a hydroxyl group. This liquid can be uniformly formed on the surface of the lyophilic film 14a without repelling the liquid containing the material constituting the EL layer 15 described later. As described above, the action of the photocatalyst is that active oxygen species are generated by the incidence of active light on the photocatalyst film 43, and the active oxygen species diffuse in the gas phase between the photomask substrate 40 and the compound layer 14 ′, The active oxygen that has reached the compound layer 14 'changes the chemical structure of the compound layer 14'.
[0056]
Further, in the lyophilic film 14a, the main chain of the polymer composed of silicon and oxygen is formed in a state along the surface of the anodes 13, 13,. Since it is substituted with a hydroxyl group, the film thickness is also equal to the length of the HO—Si—X— group or HO—Si— group, which is the main chain in this single molecular unit (corresponding to a side chain as a polymer here), It can be very thin as 1 nm or less. Therefore, on the anodes 13, 13,... Where the active oxygen species are generated, the pattern film 14 is very thin, and the lyophilic film 14a itself is used for injection and transport of charges such as holes. There is almost no hindrance.
In the pattern film 14, the liquid repellent film 14 b corresponding to a region that does not overlap the mask 42 is formed continuously with the lyophilic film 14 a and contains more fluorine than the lyophilic film 14 a. It becomes thicker by the amount of the base Rf and exhibits liquid repellency with respect to a liquid containing a material constituting the EL layer 15 described later.
[0057]
After forming the pattern film 14 by partially exposing the compound layer 14 ′ as described above, the EL layer 15 is formed in each surrounding area 19. The EL layers 15, 15,... Are formed by applying a droplet discharge technique (inkjet technique). That is, as shown in FIG. 4E, the nozzle 70 that can discharge the organic compound-containing liquid containing the constituent material of the EL layer 15 is opposed to the transparent substrate 12, and the driving device applies the transparent substrate 12 to the transparent substrate 12. The nozzle 70 is moved relatively along the horizontal plane, and when the nozzle 70 is positioned on the surrounding area 19, the organic compound-containing liquid is discharged from the nozzle 70 as a droplet once or a plurality of times. As a result, the droplet of the organic compound-containing liquid lands on the pattern film 14 in the surrounding area 19. In addition, the organic compound containing liquid can be prepared for each color of red, green, and blue, and can be applied separately as EL layers 15, 15,.
[0058]
The landed droplet spreads in the surrounding area 19 to become a film, and the film is solidified, whereby the EL layer 15 is formed. Since the pattern film 14 is the lyophilic film 14 a in the surrounding area 19, the landed droplets are easily wetted and oozed, and the organic compound-containing liquid spreads throughout the surrounding area 19. In particular, when an actinic ray is incident slightly outside the surrounding area 19 and becomes lyophilic, the organic compound-containing liquid surely spreads throughout the surrounding area 19. Therefore, the EL layer 15 is formed with a uniform thickness, and no peeling occurs between the EL layer 15 and the pattern film 14 and no short circuit occurs between the anode 13 and the cathode 16.
Further, even if the droplets that have landed in the surrounding area 19 bounce back toward the partition wall 20 around the surrounding area 19, the liquid repellent film 14 b on the partition wall 20 repels the organic compound-containing liquid, so It slides down and it becomes possible to use an organic compound containing liquid efficiently. Even when a large amount of the organic compound-containing liquid that is higher than the top of the partition wall 20 is discharged into the surrounding area 19, the organic compound-containing liquid does not bleed onto the partition wall 20. The organic compound-containing liquids of two pixels are not mixed with each other on the partition wall 20 and the organic compound-containing liquids do not flow out and flow into the surrounding area 19. Therefore, it is possible to form a film with a uniform thickness at all times, and to develop a color with high color purity when two adjacent pixels are organic compound-containing liquids having different emission colors.
[0059]
In addition, when the EL layer 15 has a laminated structure, an organic compound-containing liquid is prepared for each layer, and each organic compound-containing liquid is sequentially ejected into the surrounding area 19 with a nozzle to laminate each layer. I will do it. For example, when the EL layer 15 has a two-layer structure including a hole injection layer and a light-emitting layer in a narrow sense, the organic compound-containing liquid of the hole injection layer (the organic compound constituting the hole injection layer is dispersed in an aqueous solvent. The hole injection layer is formed by discharging the dispersion liquid into each surrounding region 19, and then the organic compound-containing liquid of the narrowly defined light-emitting layer (the organic compound constituting the narrowly-defined light-emitting layer is, for example, toluene, xylene, The EL layer 15 is formed by discharging a solution dissolved in an organic solvent such as tetralin into each surrounding region 19. Even in this case, the pattern film 14 is compatible with the organic compound-containing liquid in the hole injection layer in each surrounding region 19, and contains the organic compound in the hole injection layer in the region overlapping the protective insulating film 18 and the partition wall 20. Repel the liquid.
[0060]
Next, the cathode 16 is formed on one surface so as to cover the EL layers 15, 15,... By a film forming method such as PVD method or CVD method such as vapor deposition or sputtering. Since the EL layer 15 is formed over the entire surrounding region 19, the cathode 16 does not directly contact the anode 13. After forming the cathode 16, the EL elements 11, 11,... Are sealed with a sealing material such as sealing resin and sealing glass.
[0061]
In the organic EL display panel 10 manufactured as described above, a current flows through the EL element 11 in accordance with a signal input by the pixel circuit via the signal line 51 and the scanning line 52. In the EL element 11, a current flows by injecting holes from the anode 13 into the EL layer 15 and injecting electrons from the cathode 16 into the EL layer 15. Then, holes and electrons are transported in the EL layer 15, and the holes and electrons are recombined in the EL layer 15, whereby the EL layer 15 emits light. Since the anodes 13, 13,... And the transparent substrate 12 are transparent, the light emitted from the EL layer 15 is emitted from the back surface 12b of the transparent substrate 12, and the back surface 12b becomes the display surface.
[0062]
As described above, in the present embodiment, the silazane compound is hydrolyzed and polymerized to form the compound layer 14 ′, and the main chain as a polymer composed of silicon and oxygen is the anodes 13, 13,. The lyophilic film 14a is formed on the entire surface along the surfaces of the protective insulating film 18 and the partition wall 20, and the substantial thickness of the lyophilic film 14a in each surrounding region 19 is the main molecular unit of the compound layer 14 ′. The thickness is very thin, excluding the functional group Rf containing fluorine from the chain. Therefore, even if the pattern film 14 is interposed between the anode 13 and the EL layer 15, the insulation of the pattern film 14 can be ignored, and injection of holes from the anode 13 to the EL layer 15 is not hindered. .
[0063]
Further, since oxygen plasma cleaning or ultraviolet / ozone cleaning is performed before forming the compound layer 14 ′, and further cleaning is performed with pure water, a very thin compound layer 14 ′ having liquid repellency is easily formed. be able to. In particular, since it is washed with pure water, the liquid repellent compound layer 14 ′ can be reliably formed on the partition wall 20. This is because the liquid-repellent compound layer 14 ′ may not be sufficiently formed on the partition wall 20 if it is not washed with pure water, so that the surface layer of the partition wall 20 is washed by pure water. The hydropolymerization reaction of the silazane compound is caused by the attached water molecules.
[0064]
In the present embodiment, the compound layer 14 ′ is partially reacted by irradiating the compound layer 14 ′ with the active oxygen species through the photomask substrate 40 without containing the photocatalyst in the compound layer 14 ′. . Since only the photocatalyst portion becomes the lyophilic film 14a, injection of holes from the anode 13 to the EL layer 15 is not hindered, and the pattern film 14 does not affect the EL layer 15 chemically.
[0065]
Further, since the EL layer 15 is uniformly formed over the entire surrounding region 19, no short circuit occurs between the anode and the cathode. Further, since peeling does not easily occur between the EL layer 15 and the pattern film 14, dark spots are not easily generated in the emitted EL layer 15.
[0066]
Further, since the liquid repellent compound layer 14 ′ is formed on the partition wall 20 without being irradiated with fluoride plasma, the exposed protective insulating film 18 is not etched and the protective insulating film 18 is not damaged. . For this reason, it is possible to prevent a problem that the EL layer 15 cannot be sufficiently formed in the gap where the protective insulating film 18 is etched and a short circuit occurs between the anode and the cathode.
[0067]
In the above description, the plurality of EL layers 15, 15,... Are patterned by the droplet discharge method. However, since the lyophilic region is patterned in a matrix in the pattern film 14, a plurality of EL layers are formed by applying an organic compound-containing liquid to the pattern film 14 and rotating the transparent substrate 12 (spin coating method). 15 can be patterned in a matrix. In addition, the plurality of EL layers 15, 15,... Can be patterned in a matrix by dip coating.
In the above description, the compound layer 14 'is formed by the dip coating method. However, the compound layer 14' may be formed by the spin coating method, the brush coating method, or the vapor deposition method.
Further, the partition wall 20 may not be formed. In this case, the compound layer 14 ′ is formed so as to cover the anodes 13, 13,... And the entire protective insulating film 18, and the photomask substrate is formed on the surrounding regions 19, 19,. 40 to supply active oxygen species.
Moreover, although the silazane compound was mentioned as a silane compound which has a functional group containing a fluorine, other silane compounds, such as a silane coupling agent (hydroalkyl-polymerizable silicon compound containing hydrolytic polymerization), and other liquid repellency are shown. It may be a functional group, and the substituted functional group may be a lyophilic functional group other than a hydroxyl group.
[0068]
[Second Embodiment]
An organic EL display panel different from the organic EL display panel 10 of the first embodiment will be described. FIG. 5 is a cross-sectional view showing the organic EL display panel 110 in the second embodiment.
[0069]
The difference between the organic EL display panel 110 shown in FIG. 5 and the organic EL display panel 10 shown in FIG. 2 is that the organic EL display panel 10 is formed with the pattern film 14 whereas the organic EL display panel 10 is different from the organic EL display panel 10 shown in FIG. A pattern film is not formed on the display panel 110. That is, in the organic EL display panel 110, the EL layer 15 is formed directly on the anode 13 without a pattern film. Other components of the organic EL display panel 110 are the same as those of the organic EL display panel 10 of the first embodiment, and the organic EL display panel 110 is the same as the organic EL display panel 10 of the first embodiment. The same reference numerals are given to the constituent elements, and detailed description will be omitted.
[0070]
A method for manufacturing the organic EL display panel 110 will be described.
As in the case of the first embodiment, the signal lines 51, 51,... And the scanning lines 52, 52,... Are patterned on the transparent substrate 12, and the anode 13 and the transistors 21, 21 are connected to the transparent substrate 12 for each pixel. Then, patterning is formed on the surface 12a (FIG. 3A), and then the protective insulating film 18 and the partition wall 20 are formed (FIG. 3B).
[0071]
Next, the transparent substrate 12 is exposed to the fluorine gas atmosphere together with the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20. More specifically, the chamber is used to put the transparent substrate 12 on which the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20 are formed into the chamber, and the atmosphere in the chamber is an atmospheric pressure containing nitrogen gas. The atmosphere is fluorine gas, and the transparent substrate 12 is left in the chamber for several minutes. Under a fluorine gas atmosphere, fluorine radical species (active species) react on the surface layer of the partition wall 20, and fluoride (mainly a compound of fluorine and carbon) is formed on the surface layer of the partition wall 20. Therefore, the surface layer of the partition wall 20 exhibits liquid repellency. Table 1 shows changes in contact angle with pure water. The partition wall 20 made of polyimide had a contact angle of 71 ° before the fluorination treatment, whereas the contact angle became 96 ° after the fluorination treatment. The contact angle of the anode 13 made of ITO was also changed from 58 ° to 94 ° by the fluorination treatment.
[Table 1]

[0072]
Since the anodes 13, 13,... Are also liquid repellent only by the fluorination treatment, oxygen plasma is applied to the anodes 13, 13,... Irradiate. Thereby, the fluoride formed in the surface layer of anode 13, 13, ... and the partition wall 20 is ashed, and the liquid repellency of the anode 13, 13, ... and the partition wall 20 falls. However, the decrease in liquid repellency of the partition wall 20 is not as significant as the decrease in liquid repellency of the anode 13. As is apparent from Table 1, after the oxygen plasma treatment, the contact angle of the anode 13 is 21.2 ° and the anode 13 is lyophilic, whereas the contact angle of the partition wall 20 is 62.6. At this time, the partition wall 20 is still highly liquid repellent. The ashing of fluoride was performed by reduced-pressure oxygen plasma irradiation, but may be performed by atmospheric-pressure oxygen plasma irradiation, ultraviolet / ozone cleaning, or other surface oxidation methods. .
[0073]
Next, as in the case of the first embodiment, the EL layer 15 is formed in each surrounding region 19. The EL layer 15 may be formed by a droplet discharge method, may be formed by a spin coating method, or may be formed by a dip coating method.
Next, as in the case of the first embodiment, the cathode 16 is formed on one surface so as to cover all the EL layers 15, 15,..., And these EL elements are formed using a sealing material such as sealing resin and sealing glass. 11, 11, ... are sealed.
[0074]
As described above, in this embodiment, since the surface layer of the partition wall 20 is made liquid repellent without irradiating fluoride plasma, the protective insulating film 18 is not etched, and the protective insulating film 18 may be damaged. Absent.
Further, since the surface layers of the anodes 13, 13,... Are ashed, impurities and the like are not attached to the surfaces of the anodes 13, 13,. Therefore, the anodes 13, 13,... Are not insulative, and the EL layer 15 is in direct contact with the anode 13 and injection of holes from the anode 13 to the EL layer 15 is not hindered.
Further, since no impurities or the like are attached to the surfaces of the anodes 13, 13,..., The anodes 13, 13,. Therefore, the EL layer 15 is formed with a uniform thickness, and there is no peeled portion between the EL layer 15 and the pattern film 14. Even when a large amount of the organic compound-containing liquid that is higher than the top of the partition wall 20 is discharged into the surrounding area 19, the surface of the partition wall 20 is liquid repellent. Does not bleed on the partition wall 20. Therefore, the organic compound-containing liquids of two adjacent pixels are not mixed on the partition wall 20.
[0075]
[Third embodiment]
An EL display panel different from the organic EL display panel 10 of the first embodiment will be described. FIG. 6 is a cross-sectional view showing an organic EL display panel 210 in the third embodiment.
[0076]
The difference between the organic EL display panel 210 shown in FIG. 6 and the organic EL display panel 10 shown in FIG. 2 is that the organic EL display panel 10 is formed with the pattern film 14 whereas the organic EL display panel 10 is different from the organic EL display panel 10. A pattern film is not formed on the display panel 210. That is, in the organic EL display panel 210, the EL layer 15 is formed directly on the anode 13 without a pattern film. In the organic EL display panel 210, a liquid repellent liquid repellent layer 214 is formed on the partition wall 20. The cathode 16 is formed on the partition wall 20 via the liquid repellent layer 214 in a region overlapping with the partition wall 20. Other components of the organic EL display panel 210 are the same as those of the organic EL display panel 10 of the first embodiment, and the organic EL display panel 210 is the same as the organic EL display panel 10 of the first embodiment. The same reference numerals are given to the constituent elements, and detailed description will be omitted.
[0077]
A method for manufacturing the organic EL display panel 210 will be described.
As in the case of the first embodiment, the signal lines 51, 51,... And the scanning lines 52, 52,... Are patterned on the transparent substrate 12, and the anode 13 and the transistors 21, 21 are connected to the transparent substrate 12 for each pixel. Then, patterning is formed on the surface 12a (FIG. 3A), and then the protective insulating film 18 and the partition wall 20 are formed (FIG. 3B).
[0078]
Next, the surface 12a side of the transparent substrate 12 on which the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20 are formed is irradiated with oxygen plasma under reduced pressure. Thereby, impurities adhering to the surface layers of the anodes 13, 13,... And the partition wall 20 are ashed, and the lyophilicity of the anodes 13, 13,. The ashing of impurities is performed by low-pressure oxygen plasma irradiation, but may be performed by atmospheric pressure oxygen plasma irradiation, ultraviolet / ozone cleaning, or other surface oxidation methods. Next, the transparent substrate 12 on which the anodes 13, 13,..., The protective insulating film 18 and the partition wall 20 are formed is washed with pure water and dried.
[0079]
Next, the transparent substrate 12 on which the anodes 13, 13,..., The protective insulating film 18, the partition wall 20 and the like are formed is set in a vapor deposition apparatus, and as shown in FIG. 221 is accommodated. The vapor deposition raw material 221 is preferably, for example, a silane compound having a functional group containing fluorine, particularly a low molecular weight silane compound. A functional group containing fluorine includes a fluoroalkyl group.
[0080]
Further, as shown in FIG. 7, a mask 223 is coated on the anode 13 so as to face the surrounding regions 19. Then, by heating and evaporating the deposition raw material 221 with an electron beam, a heater or the like, a silane compound is deposited on the surface of the partition wall 20, and a liquid repellent layer 214 made of the silane compound is formed.
[0081]
Next, as in the case of the first embodiment, the EL layer 15 is formed in each surrounding region 19. The EL layer 15 may be formed by a droplet discharge method, may be formed by a spin coating method, or may be formed by a dip coating method.
Next, as in the case of the first embodiment, the cathode 16 is formed on one surface so as to cover the EL layers 15, 15,..., And these EL elements 11 are sealed with a sealing material such as sealing resin and sealing glass. , 11,... Are sealed.
[0082]
As described above, in this embodiment, since the liquid-repellent layer 214 of the silane compound having a functional group containing fluorine is formed on the surface of the partition wall 20 without irradiation with fluoride plasma, The film 18 is not etched, and the protective insulating film 18 is not damaged.
Further, since the surface layers of the anodes 13, 13,... Are ashed, impurities and the like are not attached to the surfaces of the anodes 13, 13,. Further, since the anodes 13, 13,... Are masked during vapor deposition, the silane compound having a functional group containing fluorine does not adhere to the surfaces of the anodes 13, 13,. Therefore, the anodes 13, 13,... Are not insulative, and the EL layer 15 is in direct contact with the anode 13 and injection of holes from the anode 13 to the EL layer 15 is not hindered.
Further, since no silane compound or impurities are attached to the surfaces of the anodes 13, 13,..., The anodes 13, 13,. Therefore, the EL layer 15 is formed with a uniform thickness, and there is no peeled portion between the EL layer 15 and the pattern film 14.
Even when a large amount of the organic compound-containing liquid that is higher than the top of the partition wall 20 is discharged into the surrounding area 19, the surface of the partition wall 20 is liquid repellent. Does not bleed on the partition wall 20. Therefore, the organic compound-containing liquids of two adjacent pixels are not mixed on the partition wall 20.
[0083]
The present invention is not limited to the above-described embodiments, and various improvements and design changes may be made without departing from the spirit of the present invention.
For example, the display panel of each of the above embodiments can be used for a line scanning mechanism of an image forming apparatus such as a page printer.
In each of the above embodiments, the cathode 16 is common to all the organic EL elements 11, 11,..., But the cathode and the anode may be replaced to form a cathode for each pixel of the organic EL element 11. good.
Further, instead of the plate-like transparent substrate 12, a sheet-like transparent film substrate may be used.
[0084]
【The invention's effect】
  According to the first aspect of the present invention, since the fluoride is formed on the surface of the partition wall by exposing the substrate to a fluorine gas atmosphere, the surface of the partition wall becomes liquid repellent.
[0085]
  Since the surface of the partition wall is liquid repellent, the organic compound-containing liquid does not bleed onto the partition wall. For this reason, the organic compound-containing liquids of two adjacent pixels are not mixed on the partition wall.
[Brief description of the drawings]
FIG. 1 is a plan view showing an organic EL display panel to which the present invention is applied.
FIG. 2 is a cross-sectional view of the organic EL display panel shown in FIG.
3 is a view showing a manufacturing process of the organic EL display panel shown in FIG. 1;
4 is a view showing a manufacturing process of the organic EL display panel shown in FIG. 1;
5 is a cross-sectional view showing an organic EL display panel different from the organic EL display panel shown in FIG.
6 is a cross-sectional view showing an organic EL display panel different from the organic EL display panel shown in FIGS. 1 and 5. FIG.
7 is a view showing a manufacturing process of the organic EL display panel shown in FIG. 6;
[Explanation of symbols]
10, 110, 210 Organic EL display panel (display panel)
11 EL element (light emitting element)
12 Transparent substrate (substrate)
12a surface
13 Anode (first electrode, electrode)
14 'compound layer
14 Pattern film
14a lyophilic membrane
14b Liquid repellent film
15 EL layer
16 Cathode (second electrode)
19 Go area (electrode exposure area)
20 partition wall
43 Photocatalytic membrane
214 Liquid repellent layer
223 mask

Claims (8)

A display in which a plurality of optical elements in which indium oxide, zinc oxide, tin oxide, or a mixture containing at least one of them are sequentially laminated are arranged on a substrate. In a manufacturing method of a display panel for manufacturing a panel,
A partition wall made of an organic compound is formed on the one surface of the substrate on which the plurality of first electrodes are spaced apart from each other so as to surround each of the first electrodes. Process,
The partition wall and the plurality of each first electrode and the substrate, a step of the partition wall and the plurality of first electrode exposed to the fluorine gas atmosphere having nitrogen gas and fluorine gas to lyophobic,
After the liquid repellency step, reducing the liquid repellency of the surface layers of the plurality of first electrodes by oxygen plasma treatment;
Forming the EL layer on the first electrode;
A display panel manufacturing method comprising:   2. The method of manufacturing a display panel according to claim 1, wherein the oxygen plasma treatment is a reduced pressure oxygen plasma treatment or an atmospheric pressure oxygen plasma treatment.   The method for manufacturing a display panel according to claim 1, wherein a protective insulating film is disposed below the partition wall.   The method for manufacturing a display panel according to claim 3, wherein the protective insulating film is silicon oxide or silicon nitride.   The method for manufacturing a display panel according to claim 1, wherein the partition wall is made of polyimide. Forming the second electrode on the EL layer;
The method for manufacturing a display panel according to claim 1, comprising:   The method for manufacturing a display panel according to claim 6, wherein the step of forming the EL layer is a droplet discharge method, a spin coating method, or a dip coating method. Indium oxide, the first electrode is a mixture comprising at least one of zinc oxide or tin oxide or their, EL layer, a plurality of light optical element which the second electrode are sequentially stacked, respectively, which are arranged on a substrate In a display panel manufacturing method for manufacturing a display panel,
A partition wall made of an organic compound is formed on the one surface of the substrate on which the plurality of first electrodes are spaced apart from each other so as to surround each of the first electrodes. Process,
The partition wall and the plurality of each first electrode and the substrate, a step of the partition wall and the plurality of first electrode exposed to the fluorine gas atmosphere having nitrogen gas and fluorine gas to lyophobic,
After the liquid repellency step, reducing the liquid repellency of the surface layers of the plurality of first electrodes by ultraviolet ozone cleaning treatment;
Forming the EL layer on the first electrode;
A display panel manufacturing method comprising:

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