567736 玖、發明說明 【發明所屬之技術領域】 本發明係爲具有電致發光（以下，也有簡稱爲el的情況） 層的EL元件，是關於藉由光微影法形成該有機EL層的 EL元件的製造方法。 【先前技術】 EL元件係爲使從對向之電極注入的電洞及電子在發光 層內耦合，利用該能量激發發光層中的螢光物質，以進行 對應該螢光物質之顏色的發光者，其作爲自發光的面狀元 件受到廣泛的注目。其中，將有機物質用作爲發光材料的 有機薄膜EL顯示器，即使施加電壓約爲1 〇V也可實現高 亮度的發光等，其發光效率相當的高，且可以單純的元件 構造發光，因而在發光顯示特定圖案的廣告及其他低價的 簡易顯示之顯示器的應用上日益受到期待。 使用此種EL元件的顯示器的製造，一般採用有電極層 及有機EL層的圖案處理。該EL元件的圖案處理方法，具 有介由陰罩蒸鍍發光材料的方法、噴墨塗敷方法、藉紫外 線照射破壞特定的發光色素的方法及網版印刷法等。然 而，此等方法中，並無法提供可完全實現高發光效率、高 取光效率、製造步驟的簡易化及高精細的圖案形成的 元件的製造方法。 作爲解決此等問題的方法’提出有藉由使用光微影法圖 案處理發光層形成的EL元件的製造方法。根據該方法， 與習知利用蒸鍍的圖案處理法比較，因其不需要備有高精 3Π/發明專利說明書(補件)/92-〇2/91134595 5 567736 度的調節機構的真空設備等’因而可較爲容易且廉價地製 造。另一方面，與利用噴墨方式的圖案處理法比較’其具 有在無需對於輔助圖案處理的構造物及基體進彳了則處理等 方面較爲理想，更且從噴墨頭的吐出精度的關係上考慮， 藉由光微影法者可形成更爲高精度的圖案而較爲理想的優 點。 藉由此種光微影法形成多數發光部的方法’如有圖5所 示方法之提案。 首先，如圖5(a)所示，於基材31上形成圖案處理後的第 1電極層32，再於其上全面塗敷第丨發光層用塗工液33。 接著，如圖5(b)所示，全面塗敷正型光阻34 ’如圖5(c)所 示，由光罩3 5僅遮蔽形成第1發光部的部分，由紫外線 3 6對該部分以外的部分曝光。 藉由光阻顯影液將此顯影’藉由水洗’如圖5 (d)所不除 去曝光部的光阻。再藉由發光層的溶媒顯影’如圖5(e)所 示，除去裸露的第1發光層3 3，餘下光阻與由光阻覆被的 第1發光部3 3 ’。 接著，與形成第1發光部33’相同，如圖5(f)所示，全面 塗敷第2發光層用塗工液37。此時，從圖5(f)明顯可知， 上述全面塗敷之第2發光層用塗工液37與第1發光部33’ 產生接觸部分。也就是說，如上述，殘留於基材3 1上的第 1發光部3 3 ’雖於其表面覆被有正型光阻，但藉發光層顯影 液所顯影的端部a卻成爲被曝露的狀態。據此，若於其上 塗敷上述第2發光層用塗工液3 7，則於該端部a上，第1 6 312/發明專利說明書(補件)/92-02/91134595 567736 發光部3 3 ’與第2發光層用塗工液形成接觸。此時，因第丄 發光部溶入第2發光層用塗工液，即會有產生混色、畫素 稀薄等不利因素的問題。 又，如圖5(g)所示，全面塗敷正型光阻34，如圖5(h)所 示，由光覃35僅遮蔽形成第1及第2發光部的部分，由紫 外線3 6對該部分以外的部分曝光。 藉由光阻顯影液將此顯影，進行水洗，若再藉由發光.層 的溶媒顯影’如圖5 (i)所示僅除去裸露的第2發光層3 7， 形成由光阻34覆被的第2發光部37’。 又，與形成第1及第2發光部相同，如圖5(j)所示，全 塗敷第3發光層用塗工液3 8。此時，也從圖5 (j)明顯可知’ 於最初形成之第1發光部3 3 ’的端部a上，第1發光部與 第3發光層用塗工液接觸，又於第2發光部3 7 ’的端部b 上，第2發光部與第3發光層用塗工液接觸。此時，也同 樣因爲第1發光部33’及第2發光部37’溶入第3發光層用 塗工液中，即會有產生混色、畫素稀薄等不利因素的問題 的可能。 再全面塗敷正型光阻34，如圖5(k)所示，由光罩35遮 蔽形成第1、第2及第3發光部的部分，由紫外線36對該 部分以外的部分曝光。 藉由光阻顯影液將此等顯影，進行水洗’若再藉由發光 層的溶媒進行顯影，如圖5(1)所示僅除去裸露的第3發光 層3 8，餘下被光阻覆被的部分。當再藉由光阻剝離液作剝 離處理時，則從光阻形成部分將其上層剝離’如圖5(m)所 312/發明專利說明書(補件)/92-02/91134595 567736 示，裸露形成第1發光部33’、第2發光部37’及第3發光 部3 8 5之3色的發光部。 最後，如圖5(n)所示，只要再於此等發光部上形成第2 電極層39,即可製造圖下方之放射EL發光40的EL元件。 如上所述，根據該光微影法，由於未藉由光阻層覆被已 圖案處理過的第1發光部的端部a及第2發光部的端部b， 因而，再塗敷後續之發光層用塗工液時，於其端部上因被 圖案處理過的發光部溶入隨後塗敷之發光層用塗工液中， φ 即會有產生混色、畫素稀薄等不利因素的問題的可能。 【發明內容】 本;發明係鑒於上述問題點而開發者，其主要目的在於提 供，不僅具有發光效率及取光效率高、製造步驟簡便及形 成高精細圖案的所謂光微影法擁有的優點，同時，可防止 圖案形成後的發光部的端部與隨後被沉積的不同發光層的 混色，還可防止像素稀薄的藉光微影法的EL元件的製造 方法。 _ 爲達成上述目的，本發明係爲藉由於形成電極層的基材 上，採用光微影法經多次圖案處理種類互異的發光層，於 上述基材上形成多種類的發光部的EL元件的製造方法， 其特徵爲：具備於上述基材上以此順序形成發光層及光阻 層的步驟；以使相當於指定發光部部分的光阻層殘留的狀 態，對上述光阻層進行圖案曝光後，再進行顯影的步驟； 藉由除去經去除上述光阻層而曝露的發光層，形成表面由 光阻層覆被的發光部的步驟；於上述基材上以覆被上述發 312/發明專利說明_補件)/92-02/91134595 567736 光部的狀態形成光阻層的步驟；及以使上述發光部及其端 部成爲不被曝露的狀態，圖案曝光上述光阻層後，再進行 顯影的步驟。 本發明中，因以使圖案處理後的發光部的端部成爲不被 曝露的狀態而由光阻層進行覆被，該已形成的發光部與隨 後塗敷的發光層用塗工液未形成接觸，因而可防止因該發 光部與發光層用塗工液的接觸造成的像素稀薄及混色。 本發明中’以在形成上述發光部後，進行剝離殘留於發 光部上的光阻層的步驟，接著進行形成光阻層的步驟爲 佳。這是因爲若於先形成的光阻層上重疊塗敷隨後的光阻 層，則有不易形成良好的光阻層的情況。據此，採用在預 先除去光阻層後，再全面形成光阻層。 此外，本發明係爲藉由於形成電極層的基材上，採用光 微影法經多次圖案處理種類互異的發光層，於上述基材上 形成多種類的發光部的EL元件的製造方法，其特徵爲： 具備於上述基材上以此順序形成發光層及光阻層的步驟； 以使相當於所有發光部部分的光阻層殘留的狀態，對上述 光阻層進行圖案曝光後，再進行顯影的步驟；藉由除去經 去除上述光阻層而曝露的發光層，形成表面由光阻層覆被 的發光部的步驟；於上述基材上以覆被上述發光部的狀態 形成光阻層的步驟；以使指定發光部及其端部成爲不被曝 露的狀態，圖案曝光上述光阻層後，再進行顯影的步驟； 及除去經去除上述光阻層而曝露的發光部的步驟。 該情況也與上述情況相同，因以使圖案處理後的發光部 9 312/發明專利說明書(補件)/92-02/91134595 567736 的端部成爲不被曝露的狀態而由光阻層進行覆被，該已形 成的發光部與隨後塗敷的發光層用塗工液未形成接觸，因 而可防止因該發光部與發光層用塗工液的接觸造成的像素 稀薄及混色。於是，於再顯影光阻層時，電極層常時保持 在由發光部所覆被的狀態。據此，即使於電極層上形成有 緩衝層等的有機EL層的情況，由於此種有機EL層與光阻 層的顯影液不接觸，因而具有即使使用可溶於光阻層的溶 媒及顯影液的有機EL層亦無妨的優點。 φ 此時，以在形成上述發光部的步驟後，進行剝離殘留於 所有發光部上的光阻層的步驟，接著進行形成光阻層的步 驟爲佳。這與上述情況相同，是因爲若於先形成的光阻層 上重疊塗敷隨後的光阻層，則有不易形成良好光阻層的情 況，其可解消因未形成良好光阻層所產生的不適性的情況。 此外，上述任一 E L元件的製造方法中，其除去經去除 上述光阻層而曝露的發光層或發光部的步驟，以乾式蝕刻 進行去除的步驟爲佳。如此，藉由採用以乾式蝕刻去除此 鲁 光阻層的方法，可形成更爲高精細的圖案。 根據本發明，因以使圖案處理後的發光部的端部成爲不 被曝露的狀態而由光阻層進行覆被，該已形成的發光部與 隨後塗敷的發光層用塗工液未形成接觸，因而可獲得防止 因該發光部與發光層用塗工液的接觸造成的像素稀薄及混 色的功效。 【實施方式】 本發明之EL元件之製造方法，可分爲兩大類的實施態 10 312/發明專利說明書(補件)/92-02/9113幻95 567736 樣。以下，按各實施態樣詳細說明本發明之EL元件之製 造方法。 A ·第1實施態樣 本發明之第1實施態樣，係爲藉由於形成電極層的基材 上’採用光微影法經多次圖案處理種類互異的發光層，於 上述基材上形成多種類的發光部的E L元件的製造方法， 其至少具有如下各步驟。 (1 )於基材上以此順序形成發光層及光阻層的步驟（發光 層及一次光阻層形成步驟）； (2) 以使相當於指定發光部部分的光阻層殘留的狀態，對 上述光阻層進行圖案曝光後，再進行顯影的步驟（一次光阻 層顯影步驟）； (3) 藉由除去經去除上述光阻層而曝露的發光層，形成表 面由光阻層覆被的發光部的步驟（發光層顯影步驟）； (4) 於上述基材上以覆被上述發光部的狀態形成光阻層 的步驟（二次光阻層形成步驟）； (5) 以使上述發光部及其端部成爲不被曝露的狀態，圖案 曝光上述光阻層後，再進行顯影的步驟（二次光阻層顯影步 驟）。 關於此等各步驟，首先，使用圖1所示本實施形態的第 1例，簡單說明第1發光部的形成（圖1(a)〜（〇)。 本實施態樣之第1例中，首先，如圖1(a)所示，於基材 1上經圖案處理後的第1電極層2及形成於其上的緩衝層3 上，使用旋塗法等全面塗敷第1發光層用塗工液。藉由將 11 312/發明專利說明書(補件)/92-02/91134595 567736 被全面塗敷的第1發光層用塗工液乾燥而使其硬化，形成 第1發光層4。然後，於該第1發光層4上全面塗敷正型 光阻，形成一次光阻層5(發光層及一次光阻層形成步驟）。 接著’令相當於第1發光部的部分形成未曝光的狀態使 用一次光罩6圖案照射紫外線7 (圖1 (a))。然後，藉由光阻 顯影液顯影一次光阻層5的曝光部分，藉由水洗，除去曝 光部分的一次光阻層5 (—次光阻層顯影步驟）。 再藉由發光層顯影液的顯影，僅除去未被一次光阻層5 ^ 所覆被部分的發光層4(圖1(b)、發光層顯影步驟）。 然後，如圖1 (c)所示，再於其上重疊全面塗敷正型光阻， 形成二次光阻層5 ’（二次光阻層形成步驟）。 接著，使用較遮蔽圖1(a)所示一次光阻層的一次光罩6 更爲寬幅的二次光罩6’，藉由紫外線7進行曝光（圖1(d))。 然後，再藉由光阻顯影液顯影二次光阻層5 ’的曝光部分， 藉由水洗，如圖1(e)所示，形成覆被第1發光部4’及其端 部a的二次光阻層5 ’（二次光阻層顯影步驟）。 鲁 如此，於圖案處理一個發光層時，藉由進行一次光阻層 及二次光阻層的2次光阻層顯影步驟，即可在由光阻層覆 被第1發光部4 ’的端部a的狀態下，進行下一第2發光 部形成用的第2發光層用塗工液的塗敷步驟。據此，即使 塗敷下一第2發光層用塗工液，也無混色等的問題產生。 圖2爲顯示本實施態樣之第2例之第1發光部的形成完 成者（圖2(a)〜（e))。該例中，至圖1(b)之步驟、亦即一次 光阻層5之顯影、第1發光層之顯影的步驟（發光層顯影步 12 312/發明專利說明書(補件)/92-02/91134595 567736 驟）爲止，完全相同（參照圖2(b))。該例中’進行剝離下一 被顯影的一次光阻層5的步驟（一次光阻剝離步驟、參照圖 2(c))。接著，完全除去一次光阻層，於曝露第1發光部4’ 的基材上，全面形成二次光阻層5 ’，與圖1所示例相同， 藉由使用二次光罩6’進行曝光（圖2(d))，更寬幅地形成二 次光阻層5 ’，使其成爲由該二次光阻層5 ’覆被而不致將第 1發光部4’的端部a曝露的狀態（圖2(e))。 該例之方法中，於發光層顯影步驟及二次光阻層形成步 驟間，有另外進行光阻層剝離步驟的必要，但是，並未再 度於如圖1所示例中已形成的光阻層上形成光阻層，因而 具有容易形成二次光阻層的優點。 其次，使用圖1所示第1例，說明有關第2發光部的形 成（圖1(f)〜ϋ))。第2發光部也可藉由對第2發光層進行 與上述第1發光部的形成方法相同的步驟來形成，此時’ 可在已覆被第1發光部的端部a及第2發光部的端部b的 狀態下，塗敷第3發光層用塗工液，從而可防止混色。 也就是說，首先，藉由相同的旋塗法等形成第2發光層 8，然後，進行形成一次光阻層5的步驟（發光層及一次光 阻層形成步驟、圖1 (0)。隨後，使用一次光阻6對相當於 第1發光部的部分及第2發光部的部分進行圖案曝光（圖 1(f))。然後，藉由光阻顯影液顯影一次光阻層（一次光阻層 顯影步驟），顯影暴露的第2發光層（發光層顯影步驟、圖 1(g))。隨後，重疊形成二次光阻層5’（二次光阻層形成步 驟、（圖1(h))。於是，藉由使用更爲寬幅的二次光罩6’進 13 312/發明專利說明書(補件)/92-02/91134595 567736 行圖案曝光、顯影’形成由二次光阻層5 ’覆被第1發光部 4，的端部a及第2發光部8 ’的端部b的狀態（二次光阻層顯 影步驟、（圖l(j)) °據此，於下一塗敷第3發光層用塗工 液形成第3發光層時（圖l(k)) ’不會於第1發光部及第2 發光部產生混色。 再者，說明有關上述第2發光部的形成的第2例（圖2(f) 〜（j))。第2例中，第2發光部的形成情況也與第1發光部 的情況相同’爲於發光層顯影步驟及二次光阻層顯影步驟 之間，進行光阻層剝離步驟者。 首先，與第1例相同，進行第2發光層8及一次光阻層 5的步驟（圖2(f))，一次光阻層顯影步驟及進行第2發光層 顯影步驟的狀態爲圖2(§)(相當於圖Ug))。在該狀態下將 一次光阻層5及二次光阻層5 ’剝離（光阻層剝離步驟、圖 2(h))。隨後，形成二次光阻層5’，藉由使用更爲寬幅的二 次光罩6’進行曝光、顯影（圖2(i))，形成由二次光阻層5’ 覆被到端部a的第1發光部4 ’及覆被到端部b的第2發光 部8 ’（二次光阻層形成步驟、二次光阻層顯影步驟（圖 2 (j ))。 在圖2所示之第2例中，與上述第1發光層的情況相同， 由於在預先進行光阻層剝離步驟後，才進行二次光阻層形 成步驟，因而，如圖1所示，並無於形成之一次光阻層上 再沉積二次光阻層的情況。據此，具有可容易形成二次光 阻層的優點。 最後，圖1所示例及圖2所示例相同，均進行形成第3 14 312/發明專利說明書(補件)/92-02/91134595 567736 發光層9及光阻5的發光層形成步驟及光阻形成步驟（圖 1 (k)、圖2(k))。於是，在進行光阻的曝光、顯影、進行第 3發光層顯影步驟後，藉由剝離光阻，形成第1發光部4 ’、 第2發光部8’及第3發光部9’（圖1(1))。最後，如圖l(m) 所示，於此等發光部上形成第2電極層10,即可製造出圖 下方之放射EL發光的EL元件。 以下，詳細說明有關此種本實施態樣之EL元件的製造 方法。 φ 1.發光層及一次光阻層形成步驟 本實施態樣中，首先進行發光層及光阻層形成步驟。如 上述圖1及圖2所示，在發光層爲第1發光層的情況，於 形成正常電極層的基材上塗敷第1發光層用塗工液，形成 第1發光層。 用於上述實施態樣的基材，可採用如此般至少形成電極 層者，但是，本實施態樣中並不限定於此，也可採用形成 緩衝層等的其他有機EL層者。 · 但是，本實施態樣中，如圖1(d)至圖1(0所示，於二次 光阻層5 ’之顯影時，有在曝露緩衝層3的狀態下進行顯影 的必要。據此，本實施態樣中，形成於該位置的緩衝層等 的有機E L層，以不會溶入光阻層的顯影液及溶媒的有機 EL層爲佳。具體而言，可列舉出使用溶膠-凝膠反應液、 光硬化性樹脂及熱硬化性樹脂的緩衝層。也就是說，可爲 於未硬化狀態的溶膠-凝膠反應液、光硬化性樹脂或熱硬 化性樹脂，添加發揮緩衝層功能用的添加劑’用以作爲緩 15 312/發明專利說明書(補件)/92-02/91134595 567736 衝層形成用塗工液者，或是、藉由將溶膠-凝膠反應液、 光硬化性樹脂或熱硬化性樹脂本身變性，使用可作爲緩衝 層之功能的緩衝層形成用塗工液’藉由將該種緩衝層形成 用塗工液硬化，而作爲不溶入溶媒的緩衝層者等。 以下，具體說明用於此種發光層及光阻層形成步驟之各 構成。 a.基材 用於本實施態樣之基材，只要爲具高透明性者並無任何 φ 特別限定，可使用玻璃等的無基.材料或透明樹脂等。 上述透明樹脂只要爲可形成薄膜狀者並無任何特別限 定，但是，以具高透明性、耐溶媒性、耐熱性較高的高分 子材料爲佳。具體而言，可列舉出聚醚ijt(PES)、聚對苯 二甲乙脂（PET)、聚碳酸酯（PC)、聚醚醚酮（PEEK)、聚氟乙 烯（PVF)、聚丙烯酸酯（PA)、聚丙烯（PP)、聚乙烯（PE)、非 晶質聚烯烴、或氟樹脂等。 b .電極層 上述基材上如上述般形成電極層。此種電極層只要爲正 常之EL元件即可，並無任何特別的限定。又，可稱如此 先設於基材上的電極層爲第1電極層，設於有機EL層形 成後的電極層爲第2電極層。此等電極層係由陽極及陰極 所構成，陽極及陰極的哪一方爲透明或半透明，陽極以易 注入電洞的工作函數大的導電性材料爲佳。此外，也可混 合多種材料。任一電極層均以電阻盡可能小者爲佳，一般， 採用金屬材料，但也可採用有機物或無機化合物。 16 312/發明專利說明書(補件)/92-02/91134595 567736 c•發光層用塗工液 本貫施Is樣中’係於至少形成有上述電極層的基材上塗 敷發光層用塗工液，藉由乾燥於基材上形成發光層。 此種發光層用塗工液一般由發光材料、溶媒及摻雜劑等 的添加劑所構成。又，本實施態樣中，係經由藉光微影法 經多次圖案處理種類各異的發光層，於基材上形成多數種 類的發光部的E L元件的製造方法，來形成多色的發光層 者。據此，使用多數種類的發光層用塗工液。 對如此之基材上塗敷發光層用塗工液的方法，只要爲可 全面塗敷的塗敷方法，並無任何特別的限定，例如，可採 用旋塗法、澆塗法、浸漬法、桿式塗敷法、刮板式塗敷法、 滾筒式塗敷法、凹印塗敷法、苯胺印刷法、噴塗法等的塗 敷方法塗敷。 所塗敷的發光層用塗工液係藉由正常加熱等乾燥·固化 而形成發光層。以下，說明有關此等發光層用塗工液的各 構成材料。 I ·發光材料 關於本實施態樣所使用的發光材料，只要爲含有發射螢 光之材料進行發光者，並無任何特別的限定，此外，也可 爲發光功能、電洞傳輸功能及電子傳輸功能兼備者。本實 施態樣中，如後述，從藉由光微影法進行發光層的圖案處 理的關係上考慮，其形成發光層的材料，以使用不會溶入 後述之光阻溶媒、光阻顯影液及光阻剝離液的材料爲佳。 此外’該情況，藉由光微影法圖案處理發光層時所使用的 17 312/發明專利說明書(補件)/92-02/91134595 567736 光阻’也以使用不會溶入發光層形成用之溶媒的材料爲佳。 此種發光材料可列舉出，色素系材料、金屬錯體系材 料、及高分子系材料。 ① 色素系材料 色素材料可列舉甲環戊丙胺衍生物、四苯基丁二烯衍生 物、三苯胺衍生物、巧二唑衍生物、吡唑並喹啉衍生物、 二苯乙烯基苯衍生物、二苯乙烯基伸芳基衍生物、Silol衍 生物、噻吩環化合物、吡啶環化合物、周酮衍生物、此衍 生物、低聚噻吩衍生物、三富馬胺衍生物、$二唑二聚物、 吡唑啉二聚物等。 ② 金屬錯體系材料 金屬錯合物系材料可列舉D奎啉醇鋸錯合物、苯並D奎啉醇 鈹錯合物、苯並D奎唑鋅錯合物、苯並g唑鋅錯合物、苯並 噻哩鋅錯合物、偶氮甲基鋅錯合物、4 4冬鋅錯合物、銪錯 合物等、於中心金屬具有Al、. Zn、Be等、或Tb、Eu、Dy 等稀土金屬，且於配位基具有g二唑、噻二唑、苯基毗啶、 苯基苯並咪唑、喹啉等構造。 ③ 高分子材料 高分子系材料可列舉聚對伸苯基伸乙烯基衍生物、聚噻 吩衍生物、聚對伸苯基衍生物、聚矽烷衍生物、聚乙炔衍 生物、聚芴衍生物、聚乙烯基咔唑衍生物、上述色素體、 金屬錯合物系發光材料予以高分子化之材料等。 本實施態樣中’從發揮使用發光層用塗工液，藉由光微 影法可形成精度良好的發光層的利處的觀點出發，發光材 18 312/發明專利說明書(補件)/92-02/91134595 567736 料還是以使用上述高分子系材料者爲最佳。 π .溶媒 從上述圖1及圖2所示例明顯可知，有將發光層用塗工 液塗敷於光阻層上的情況。據此，作爲用於該發光層用塗 工液的溶媒，以選擇對於光阻的溶解度在2 5 °C、1大氣壓 下爲0.001(g/g溶媒）以下的溶媒爲佳，若選擇0.000 1 (g/g 溶媒）以下的溶媒則更佳。例如，在將後述之緩出層溶解於 水系或DMF、DMSO、乙醇等的極性溶媒，且光阻物爲一 0 般的酚醛淸漆系光阻物之情形，可使用苯、甲苯、二甲苯 之各異構物其混合物、三甲基苯、四氫化$、對-繳花烴、 枯烯、乙基苯、二乙基苯、丁基苯、氯苯、二氯苯之各異 構物及其混合物等爲首之芳香族系溶劑、茴香醚、苯乙醚、 丁基苯醚、四氫呋喃、2-丁酮、1，4-二碎烷、二乙醚、二 異丙醚、二苯醚、二苄醚、乙二醇二甲醚等爲首之醚系溶 劑、二氯甲烷、1，1-二氯乙烷、1,2 -二氯乙烷、三氯乙烯、 四氯乙烯、氯仿、四氯化碳、1-氯基萘等之氯系溶劑、環 鲁 己酮等，若爲滿足條件之其他溶劑則亦可使用，且亦可爲 二種以上之混合溶劑。 此外，如後述，在使用可溶於溶媒的緩衝層的情況，爲 了於發光層的成膜時可防止緩衝層與發光層材料的混合或 溶解、保持發光材料本身的發光特性，以緩衝層不溶解者 爲佳。 從該觀點出發，發光層用塗工液之溶媒，以選擇對於緩 衝層材料的溶解度在25 °C、1大氣壓下爲0.001 (g/g溶媒） 19 312/發明專利說明書(補件)/92-02/91134595 567736 以下的溶媒爲佳，而若選擇0.000 i(g/g溶媒）以下的溶媒則 更佳。 .添加劑 本貫施態樣中使用的發光層用塗工液內，除上述發光材 料及溶媒外，還可添加各種的添加劑。例如於提高發光層 中之發光效率、令發光波長變化之目的下，可進行摻混。 此摻混材料可列舉例如炎衍生物、香豆素衍生物、紅螢烯 衍生物、鸣Dy酮衍生物、角鯊减衍生物、斗p碎衍生物、苯 乙燒系色素、並四苯衍生物、吡唑啉衍生物、十環烯、吩畊 酮等。 d.光阻 本實施態樣中，對於形成上述發光層的基材，藉由全面 塗敷光阻’形成一次光阻層。 此時之光阻的塗敷方法，一般只要爲可全面塗敷塗工液 的塗敷方法，並無任何特別的限定，具體而言，可採用旋 塗法、澆塗法、浸漬法、桿式塗敷法、刮板式塗敷法、滾 筒式塗敷法、凹印塗敷法、苯胺印刷法、噴塗法等的塗敷 方法塗敷。 本實施態樣係爲如此般於發光層上形成一次光阻層，藉 由光微影法圖案處理發光層者。該光微影法係爲利用藉光 照射而使膜的光照射部的溶解性產生變化的性質，形成響 應光照射圖案的任意圖案的方法。 本實施態樣可使用的光阻，即可爲正型也可爲負型，並 無任何特別限定，但以不溶於發光層等的有機E L層形成 20 312/發明專利說明書(補件)/92-〇2/91134595 567736 用的溶媒者爲佳。 作爲可具體使用的光阻，可列舉出酚醛淸漆樹脂系、橡 膠+雙疊氮系等。 e ·光阻溶媒 本實施態樣中，作爲塗敷上述光阻時所使用的光阻溶 媒’爲防止光阻成膜時發光層等的上述有機el層與光阻 材料混合、溶解，保持原來的發光特性，以採用不溶解發 光層材料等的有機EL層材料者爲佳。考慮到該點，作爲 可用於本實施態樣之光阻溶媒，對於發光層形成用材料等 的有機E L層形成用的材料的溶解度，以選擇在2 5 °c、1 大氣壓下爲0.001 (g/g溶媒）以下的溶媒爲佳，而若選擇 0.000 1 (g/g溶媒）以下的溶媒則更佳。 可列舉丙酮、甲基乙基酮爲首之酮類、丙二醇單乙醚醋 酸酯、丙二醇單甲醚醋酸酯、乙二醇單甲醚醋酸酯、乙二 醇單乙醚醋酸酯爲首之溶纖劑醋酸酯類、丙二醇單乙醚、 丙二醇單甲醚、乙二醇單甲醚、乙二醇單乙醚爲首之溶纖 劑類、甲醇、乙醇、1 - 丁醇、2 - 丁醇、環己醇爲首之醇類、 醋酸乙酯、醋酸丁酯等之酯系溶劑、環己烷、萘烷等，若 爲滿足條件之其他溶劑則亦可使用，且亦可爲二種以上之 混合溶劑。 2 . —次光阻層顯影步驟 再者，本實施態樣中，進行以使相當於指定發光部部分 的光阻層殘留的狀態，對一次光阻層進行圖案曝光後，再 進行顯影的一次光阻層顯影步驟。 21 312/發明專利說明書(補件)/92-〇2/91134595 567736 該步驟中，首先，介由光罩將一次光阻層曝光。關於該 曝光方法等’因與習知曝光方法相同，故，在此省略此項 說明，光罩係使用形成爲可使形成有第1發光部部分的光 阻層殘留的狀態的光罩。具體而言，在圖1或圖2所示例 中，因係使用正型光阻，因此使用可遮蔽相當於第1發光 部部分的光阻，相反，使用正型光阻的情況，則使用僅使 相當於上述第1發光部部分曝光的光阻。 又，還可考慮如藉由雷射光等的描繪而曝光爲圖案狀的 $ 情況，本實施態樣也包括此種情況。 於是，在圖案曝光後，進行第1光阻層的顯影，其結果， 以第1發光部上殘留有第1光阻層的狀態，進行光阻層的 圖案處理。 以下，說明有關用於該步驟之光阻層的圖案處理的顯影 液。 (光阻層顯影液） ： 可用於本實施態樣之光阻層顯影液，只要爲不溶解於形 鲁 成上述發光層的材料者，並無任何特別的限定。具體而言， 可使用一般所使用的有機鹼系顯影液，除此以外，還可使 用無機鹼、或是可進行光阻層的顯影的水溶液。在光阻層 的顯影後，最好以水洗淨。 作爲可用於本實施態樣之光阻層顯影液，其對於發光層 形成用材料的溶解度，以選擇在2 5 °C、1大氣壓下爲 o.ooWg/g顯影液）以下的顯影液爲佳，而若選擇〇.〇〇〇1(g/g 顯影液）以下的顯影液則更佳。 22 312/發明專利說明書(補件)/92-02/91134595 567736 3 ·發光層顯影步驟 本實施態樣中，進行藉由除去經如此般去除一次光阻層 而曝露的發光層，形成表面由光阻層覆被的發光部的步驟。 該發光層顯影步驟可採用，使用溶解發光層的溶媒的濕 式法、及使用乾式鈾刻的乾式法，本實施態樣中，以使用 無混色等的不適性的乾式法爲佳。以下，說明此等各種方 法。 (濕式法） 0 該情況下的濕式法係爲使用不剝離光阻，而可溶解或剝 離發光層的溶媒，使發光層溶解並加以去除的方法。·作爲 此時可使用的溶媒，除可使用上述發光層用塗工液的溶媒 外’只要爲能滿足上述條件的溶媒，還可選擇其他的溶媒。 此外，使用該溶媒之除去時也可在超音波浴中進行。藉 由使用此種超音波浴，是因爲其無發光層的圖案稀薄或發 光層的流出等的不適，且可形成高精度圖案的原因，其在 短時間可形成高精度的圖案方面較爲理想。 修 本實施態樣中，用於該超音波浴的超音波的條件，以在 25°C、20〜ΙΟΟΚΗζ的震盪頻率、0.1〜60秒間的條件下進 行爲佳，在如此之條件下，即可在短時間形成高精度的圖 案。 (乾式法） 此外’乾式法係爲使用乾式蝕刻除去所去除之光阻部分 的發光層的方法。 一般’因光阻層較發光層形成厚度差較大的膜厚，因而 23 312/發明專利說明書(補件)/92·〇2/91134595 567736 藉由全體進行乾式蝕刻，即可除去發光層。 該情況，光阻層的膜厚以〇 · 1〜1 0 // m的範圍內爲佳， 而以0 · 5〜5 /i m的範圍內更佳。利用如此之膜厚，在可確 保光阻的抗蝕功能的基礎上，還可獲得高加工精度的乾式 蝕刻。 如此，若使用乾式蝕刻，由於可進一步將鈾刻的端部蝕 去，因而，可減窄存在於圖案端部的膜厚不均區域的寬度， 其結果，可獲得形成更高加工精度的圖案的效果。 φ 作爲用於本實施態樣之乾式法，其乾式蝕刻以反應性離 子蝕刻爲佳。藉由使用反應性離子蝕刻，是因爲有機膜受 到化學反應，成爲分子量小的化合物，可被氣化、蒸發而 從基材上除去，致使高蝕刻精度、且短時間的加工成爲可 能的原因。 此外，本實施態樣中，於上述乾式蝕刻時，以使用氧氣 單體或含氧的氣體爲佳。藉由使用氧氣單體或含氧的氣 體，可進行藉有機物的氧化反應的分解去除，可除去基材 肇 上不需要的有機物，使得高蝕刻精度、且短時間的加工成 爲可能。此外，該條件下，由於不會蝕刻正常所使用的IT 0 等的氧化物透明導電膜，因而不會損及電極特性，在可淨 化電極表面方面也非常有效。 又，本實施態樣中，對於上述乾式鈾刻，以使用大氣壓 電漿爲佳。藉由使用大氣壓電漿，可使正常必須要有真空 裝置之乾式蝕刻，在大氣壓下進行，因而，可縮短處理時 間及降低成本。該情況，鈾刻可利用藉由電漿化之大氣中 24 312/發明專利說明書(補件)/92-02/91134595 567736 的氧氣而與有機物進行的氧化分解，但也可藉由氣體的變 換及循環任意調整反應氣體內的氣體組成。 4 .光阻層剝離步驟 本實施態樣中，在進行上述光阻層顯影步驟後，還可進 行剝離被顯影後的一次光阻層的步驟。具體而言，如圖2 (b) 至2(c)所示，爲一藉由剝離殘留於基材上的一次光阻層， 使發光部曝露，隨後，進行後述之二次光阻層形成步驟的 方法。 在殘留有一次光阻層的狀態下，在較難於其上沉積以形 成二次光阻層的情況，或是，藉由沉積光阻層造成膜厚變 厚，而於隨後的發光層形成時產生問題的情況等中，如此 般，以從暫時將基材上的光阻層剝離的狀態，進行二次光 阻層的形成爲佳。 (光阻剝離液） 進行如此之光阻層剝離的情況，係使用光阻剝離液。作 爲可用於本實施態樣之光阻剝離液，並非爲溶解上述發光 層者，而是有溶解光阻層的必要，因而可直接使用如上述 的光阻的溶媒。此外，在使用正形光阻的情況，在進行UV 曝光後，也可使用作爲顯影液而被列舉出的液體進行剝離。 此外，也可使用強鹼水溶液、二甲基甲醯胺、二甲基乙 醯胺、二甲亞硕、N-甲基-2-四氫吡咯酮等的溶媒，及此等 混合物、市售的光阻剝離液。光阻剝離後以2-丙醇等進行 漂洗，也可以水沖洗。 5 .二次光阻層形成步驟 25 312/發明專利說明書(補件)/92-02/91134595 567736 在進行了上述發光層顯影步驟後，進行於上述基材上以 覆被上述發光部的狀態形成光阻層的步驟。 在此所使用的二次光阻層，可使用與上述一次光阻層相 同的材料，故，在此省略此項之說明。 本實施態樣中，可爲一次光阻層與二次光阻層使用相同 光阻層的情況，也可爲使用不同光阻層的情況。在進行上 述光阻層剝離步驟的情況，由於係將一次光阻層與二次光 阻層分開使用，因而，考慮到步驟的簡便性上的理由，以 φ 使用相同光阻層爲佳。 另一方面，在進行上述光阻層剝離步驟的情況，由於必 須於一次光阻層上形成二次光阻層，因而，根據情況也可 採用互異的光阻。 6 .二次光阻層顯影步驟 被圖案處理後的發光部的端部a，在圖1(b)及圖2(b)的 階段，未藉由一次光阻層覆被而呈曝露的狀態。若從該狀 態再進行下一發光層用塗工液的塗敷，則發光層材料容易 鲁 從端部a及b等溶入被塗敷的發光層用塗工液內，結果產 生混色及像素稀薄的問題點。 爲解決該問題點，係於二次光阻層的曝光、顯影步驟 中，以較一次光阻層的曝光、顯影步驟中殘留的一次光阻 層的寬幅還大的寬幅覆被發光部的狀態進行圖案處理°也 就是說，不僅覆被發光部的端部，同時，以不會涉及鄰接 之發光部的大小對二次光阻層進行曝光、顯影。 又，關於其他方面，因與上述一次光阻層顯影步驟相 26 312/發明專利說明書(補件)/92-02/91134595 567736 同，故，在此省略此項說明。 7.其他 本實施態樣中，在重複進行2次上述1至6步驟後，如 上述圖1所示例之說明，再度進行發光層形成步驟及光阻 層形成步驟，在進行形成之光阻層的曝光、顯影步驟、形 成之發光層的顯影步驟後，藉由進行光阻層的剝離步驟， 即可形成3色的發光部。 隨後，在形成第2電極及保護層後，藉由封裝即可製成 E L元件。 B ·第2實施態樣 以下’說明有關本發明之EL元件的製造方法的第2實 施態樣。 本實施態樣，係爲藉由於形成電極層的基材上，採用光 微影法經多次圖案處理種類互異的發光層，於上述基材上 形成多種類的發光部的EL元件的製造方法，其至少具有 如下各步驟。 (1 )於上述基材上以此順序形成發光層及光阻層的步驟 (發光層及一次光阻層形成步驟）； (2) 以使相當於所有發光部部分的光阻層殘留的狀態，對 上述光阻層進行圖案曝光後，再進行顯影的步驟（一次光阻 層顯影步驟）； (3) 藉由除去經去除上述光阻層而曝露的發光層，形成表 面由光阻層覆被的發光部的步驟（發光層顯影步驟1 ); (4) 於上述基材上以覆被上述發光部的狀態形成光阻層 27 312/發明專利說明書(補件)/92-02/91134595 567736 的步驟（二次光阻層形成步驟）； (5 )以使指定發光部及其端部成爲不被曝露的狀態，圖案 曝光上述光阻層後，再進行顯影的步驟（二次光阻層顯影步 驟）。 (6)除去經去除上述光阻層而曝露的發光部的步驟（發光 部顯影步驟2); 關於此等各步驟，首先，使用圖3所示第1例，簡單說 明第1發光部的形成（圖3(a)〜（f))。 0 圖3爲顯不本實施態樣之第1例者。如圖3 (a)所示，與 上述圖1所示情況相同，於形成電極層2及緩衝層3的基 材1上形成第1發光層4及一次光阻層5(發光層及一次光 阻層形成步驟）。 接著，曝光該一次光阻層5進行顯影（一次光阻層顯影步 驟）。本實施態樣與上述第1實施態樣的最大差異在於，於 該一次光阻層顯影步驟中，本實施態樣係以於形成所有發 光部的區域殘留一次光阻層的狀態，形成光罩6(圖3(a))， φ 藉由如此之光罩6進行曝光後，再進行顯影之點。 以於形成所有發光部的區域殘留一次光阻層的狀態，進 行顯影所曝露之第1發光層4的步驟（發光層顯影步驟1、 圖 3(b))。 然後，以覆被上述基材上的發光部的狀態，形成二次光 阻層（二次光阻層形成步驟·、圖3(c))。 接著，使用形成爲較一次光罩6更爲寬幅的二次光罩 6’，僅對指定的發光部進行圖案曝光（圖3(d))、顯影（二次 28 312/發明專利說明書(補件)/92-〇2/91134595 光阻層顯影步驟、圖3(e))。 最後，藉由顯影殘留於其他發光部上的發光層，即 爲使第1發光部4 ’上其端部a未被曝露，而形成二次 層5’的狀態（發光部顯影步驟2、圖3(f))。 本實施態樣中，也於圖案處理一發光層時，藉由進 次光阻層及二次光阻層的二次光阻顯影步驟，即可在 阻層覆被第1發光部4 ’的端部a的狀態下，進行下一 發光層用塗工液的塗敷步驟。據此，即使塗敷下一第 光層用塗工液，也無混色等的問題產生。 此外，本實施態樣之特徵爲，於二次光阻層顯影 中，在由第1發光層4覆被緩衝層3的狀態下顯影二 阻層。也就是說，雖於圖3(d)中進行圖案曝光後，對 光阻層進行顯影，但此時，因緩衝層上存在有第1發 4(圖3(e))，因此，光阻層顯影液不會直接與緩衝層接 據此，本實施態樣中，還具有即使爲可溶於光阻層顯 的材料的緩衝層，也可予以使用的優點。 圖4爲顯示本實施態樣之第2例之第1發光部的形 成者（圖4(a)〜（〇)。該例中，具有至圖3(b)之步驟、 一次光阻層5之顯影、第1發光層之顯影的步驟（發光 影步驟1)爲止，完全相同（參照圖4(b))，進行剝離下 顯影的一次光阻層5的步驟（一次光阻剝離步驟、參 4(c))等方面的特徵。 接著，完全除去一次光阻層，於曝露第1發光部4’ 材上，全面形成二次光阻層5 ’，與圖3所示例相同， 312/發明專利說明書(補件)/92·02/91134595 可成 光阻 行一 由光 .第2 2發 步驟 次光 二次 光層 觸。 影液 成完 亦即 層顯 一被 照圖 的基 藉由 29 567736 使用二次光罩6’更寬幅地形成二次光阻層5，，使其成爲由 該二次光阻層5 ’覆被而不致將第1發光部4 ’的端部a曝露 的狀態（圖4(f))。 該第2方法中，於發光層顯影1步驟及二次光阻層形成 步驟間，有另外進行光阻層剝離步驟的必要，但是，並未 再度於如圖3所示例中已形成的光阻層上形成光阻層，其 容易形成二次光阻層，此外，膜厚並未大幅增加，因而有 可形成均勻發光層的優點。 此外，該第2方法中，與第1方法相同顯影一次光阻層 時（圖4(d))，因存在發光層4(圖4(e))，緩衝層3不會直接 與光阻顯影液接觸。據此，具有即使爲可溶於光阻顯影液 的緩衝層，也可予以使用的優點。 本實施態樣也與上述第1實施態樣情況相同，藉由於第 2發光層進行相同的步驟（圖3(g)〜（k))，可在已覆被第1 發光部4 ’的端部a及第2發光部8 ’的端部b的狀態下，塗 敷第3發光層用塗工液（圖3(1))，從而可防止混色。又’ 與上述第1發光部的形成步驟相同，於二次光阻層顯影步 驟時，於緩衝層上存在第2發光層8(圖3 (j))，然後，進行 發光層顯影步驟2 (圖3(k))。據此，於第2發光部形成時’ 緩衝層3也不會直接與光阻顯影液接觸。 此外，本實施態樣之第2例中，可同樣於第2發光層進 行相同的步驟（圖4 (g)〜（k))。 隨後，於形成第3發光層及光阻層後，藉由進行曝光（圖 3(1)及圖4(1))、顯影，形成第1發光部4’、第2發光部8’ 30 312/發明專利說明書(補件)/92-02/91134595 567736 &第3發光部9 ’。於是，最後於此等發光部上形成第2電 極層’即可製造出圖下方之放射EL發光的EL元件。 &下，詳細說明有關如此之本實施態樣之EL元件的製 ^方法。又，本實施態樣中所使用的材料及形成方法等， * &下之說明中，關於除特別指摘之點以外的事項，因與 1述第1實施態樣說明之情況相同，故，省略以下各步驟 之說明。 I發光層及一次光阻層形成步驟 0 本實施態樣中，與第1實施態樣相同，首先，於基材上 @行按此順序形成發光層及光阻層的發光層及一次光阻層 形成步驟。 又，本實施態樣中，如後述，上述電極層上即使爲可溶 於光阻顯影液的有機EL層、如緩衝層，也可形成。說明 有關此種緩衝層。 (緩衝層） 本實施態樣之緩衝層，係爲使對發光層之電荷注入容易 φ 進行，而設於陽極與發光層間或陰極與發光層間，含有有 機物、尤其是含有有機導電體等的膜層。例如，可爲具有 增高對發光層的電洞注入效率，將電極等之凹凸平坦化之 功能的導電性高分子。 用於本實施態樣之緩衝層，在其導電性高的情況，爲保 持元件的二極體特性、防止串擾，而以被圖案處理者爲佳。 又，在緩衝層之電阻高的情況等也有即使未被圖案處理亦 可的情況，此外，在省去緩衝層之元件的情況也有不設緩 31 312/發明專利說明書(補件)/92·〇2/91134595 567736 衝層亦可的情況。 本實施態樣中，在藉由光微影法圖案處理形成緩衝層及 發光層兩者的情況，形成緩衝層的材料，以選、擇不溶於光 阻溶媒及發光層形成用溶媒者爲佳，而形成緩衝層的材 料’以選擇不溶於光阻剝離液的材料的情況爲更佳。 作爲形成用於本實施態樣之緩衝層的材料，雖具體可列 舉出聚烷基邊吩衍生物、聚苯胺衍生物、三苯胺等的電洞 傳輸性物質的聚合體、無機氧化物的溶膠-凝膠膜、三氟 0 甲烷等的有機物的聚合膜、含有路易士酸的有機化合物膜 等’但只要滿足如上述之溶解性的條件，並無任何特別的 限定，也可於成膜後藉由聚合或燃燒等來滿足上述條件。 此外，本實施態樣中，作爲形成緩衝層時所使用的溶 媒，只要能將緩衝層分散或溶解即可，並無任何特別的限 定，但於全彩圖案等中，在有多次成膜之必要的情況，有 使用不溶解光阻材料的緩衝層溶媒的必要，又以不溶解發 光層的緩衝層溶媒爲佳。 鲁 作爲可用於本實施態樣之緩衝層溶媒，以選擇光阻材料 的溶解度，在25 °c、1大氣壓下爲0.001 (g/g溶媒）以下的 溶媒爲佳，而若選擇0.000 1 (g/g溶媒）以下的溶媒則更佳。 作爲緩衝層溶媒，又以發光層構成材料的溶解度’在2 5 °C、1大氣壓下爲0.0 0 1 ( g/ g溶媒）以下的溶媒爲佳，而若 選擇0.00 0 1 (g/g溶媒）以下的溶媒則更佳。 具體可列舉出，水、甲醇、以乙醇爲主的酒精類、二甲 基甲醯胺、二甲基乙醯胺、二甲亞石腹、N-甲基·2 -四氫D比略 發明專利說明書(補件)/92-〇2/91134595 32 567736 酮等的溶媒，其他也只要爲滿足條件的溶媒即可使用。此 外，也可混合2種以上的溶媒予以使用。 2 · —次光阻層顯影步驟 再者，進行以使相當於所有發光部部分的光阻層殘留的 狀態，對形成之光阻層進行圖案曝光後，再進行顯影的一 次光阻層顯影步驟。 該步驟爲與第1實施態樣差異極大的步驟，對於第1實 施態樣係使相當於指定的發光部部分的光阻層殘留，而本 應567736 发明 Description of the invention [Technical field to which the invention belongs] The present invention relates to an EL element having an electroluminescence (hereinafter also referred to as "el") layer, and relates to an EL in which the organic EL layer is formed by a photolithography method. Element manufacturing method. [Prior art] The EL element couples holes and electrons injected from the opposing electrode in the light-emitting layer, and uses the energy to excite the fluorescent substance in the light-emitting layer to emit light corresponding to the color of the fluorescent substance. It has attracted wide attention as a self-luminous planar element. Among them, organic thin-film EL displays using organic substances as light-emitting materials can achieve high-brightness light emission even when a voltage of about 10 V is applied. The light-emitting efficiency is relatively high, and light can be emitted only by a simple element structure. Applications that display specific pattern advertisements and other low-cost, simple-display displays are increasingly expected. Generally, a display using such an EL element is patterned with an electrode layer and an organic EL layer. The pattern processing method of the EL element includes a method of vapor-depositing a luminescent material through a shadow mask, an inkjet coating method, a method of destroying a specific luminescent pigment by ultraviolet irradiation, and a screen printing method. However, these methods do not provide a method for manufacturing a device that can fully realize high light emitting efficiency, high light extraction efficiency, simplification of manufacturing steps, and high-definition pattern formation. As a method for solving these problems, a method of manufacturing an EL element formed by processing a light-emitting layer using a photolithography pattern is proposed. According to this method, compared with the conventional pattern processing method using vapor deposition, it does not require a vacuum device equipped with a high-precision 3Π / Invention Patent Specification (Supplement) / 92-〇2 / 91134595 5 567736 degree adjustment mechanism, etc. 'It can therefore be manufactured relatively easily and cheaply. On the other hand, compared with the pattern processing method using the inkjet method, it has an ideal relationship with the structure and the substrate that do not need to be processed for auxiliary pattern processing, and it is more suitable for processing, and it also has a relationship of ejection accuracy from the inkjet head. In view of the above, the photolithography method can form a pattern with higher accuracy, which is an ideal advantage. A method of forming a plurality of light emitting portions by such a photolithography method is proposed as the method shown in FIG. 5. First, as shown in FIG. 5 (a), a patterned first electrode layer 32 is formed on a substrate 31, and then a coating solution 33 for a first light-emitting layer is entirely coated thereon. Next, as shown in FIG. 5 (b), a positive photoresist 34 'is applied in its entirety, as shown in FIG. 5 (c). Exposure to parts other than parts. This photoresist is developed with a photoresist developing solution by washing with water as shown in Fig. 5 (d) without removing the photoresist in the exposed portion. Then, the light-emitting layer is developed with a solvent, as shown in FIG. 5 (e). The exposed first light-emitting layer 3 3 is removed, and the remaining photoresist and the first light-emitting portion 3 3 covered with the photo-resist are left. Next, as in the case where the first light-emitting portion 33 'is formed, as shown in Fig. 5 (f), a coating liquid 37 for the second light-emitting layer is entirely applied. At this time, it is obvious from FIG. 5 (f) that the coating liquid 37 for the second light-emitting layer that has been completely coated as described above makes contact with the first light-emitting portion 33 '. That is, as described above, although the first light-emitting portion 3 3 ′ remaining on the substrate 31 is covered with a positive photoresist on its surface, the end portion a developed by the light-emitting layer developing solution is exposed. status. Accordingly, if the above-mentioned coating liquid 37 for a second light-emitting layer is applied thereon, on the end portion a, the first 6 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 light-emitting portion 3 3 'comes into contact with the coating liquid for the second light-emitting layer. In this case, since the third light-emitting part is dissolved in the coating liquid for the second light-emitting layer, there are problems such as color mixing, thin pixels, and the like. Also, as shown in FIG. 5 (g), the positive photoresist 34 is coated on the entire surface, and as shown in FIG. 5 (h), only the portions where the first and second light emitting portions are formed are shielded by the light beam 35, and ultraviolet rays 3 6 are used. Expose parts other than this part. This is developed by a photoresist developing solution, washed with water, and then emitted by light. As shown in FIG. 5 (i), only the exposed second light-emitting layer 37 is removed, and a second light-emitting portion 37 'covered with a photoresist 34 is formed. Also, as in forming the first and second light-emitting portions, as shown in Fig. 5 (j), a coating liquid 38 for a third light-emitting layer is entirely applied. At this time, it is also apparent from FIG. 5 (j) that 'on the end portion a of the first light-emitting portion 3 3' formed first, the first light-emitting portion is in contact with the coating liquid for the third light-emitting layer and emits light on the second At the end portion b of the portion 37 ', the second light-emitting portion is in contact with the coating liquid for the third light-emitting layer. In this case, the first light-emitting portion 33 'and the second light-emitting portion 37' are dissolved in the coating liquid for the third light-emitting layer, which may cause problems such as color mixing and thin pixels. Then, as shown in FIG. 5 (k), the positive photoresist 34 is coated on the entire surface, and portions where the first, second, and third light-emitting portions are formed are shielded by a mask 35, and portions other than the portions are exposed by ultraviolet rays 36. These are developed with a photoresist developing solution and washed with water. If the development is performed by the solvent of the light emitting layer, as shown in FIG. 5 (1), only the exposed third light emitting layer 38 is removed, and the rest is covered with photoresist. part. When the photoresist stripping solution is used for the peeling treatment, the upper layer is peeled off from the photoresist forming portion, as shown in Figure 5 (m) 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736, exposed Light emitting sections of three colors of the first light emitting section 33 ', the second light emitting section 37', and the third light emitting section 38.5 are formed. Finally, as shown in FIG. 5 (n), as long as the second electrode layer 39 is formed on these light-emitting portions, an EL element that emits EL light emission 40 below the figure can be manufactured. As described above, according to this photolithography method, since the end portion a of the first light-emitting portion and the end portion b of the second light-emitting portion are not covered with the photoresist layer, subsequent coating is performed. When the coating liquid for the light-emitting layer is dissolved in the coating liquid for the light-emitting layer to be applied after the pattern-treated light-emitting portion is dissolved in the end portion, φ may cause problems such as color mixing and thin pixels. Possible. [Summary] The present invention was developed in view of the above problems, and its main purpose is to provide the advantages of the so-called photolithography method, which not only has high luminous efficiency and light extraction efficiency, simple manufacturing steps, and high-definition patterns, At the same time, the end portion of the light-emitting portion after pattern formation can be prevented from being mixed with different light-emitting layers that are subsequently deposited, and a method of manufacturing an EL element using thin lithography by thin pixels can also be prevented. _ In order to achieve the above-mentioned object, the present invention is to form various types of ELs of light-emitting portions on the substrate by forming a light-emitting layer with different types of light-emitting layers through photolithography on the substrate forming the electrode layer. A method for manufacturing an element, comprising: forming a light-emitting layer and a photoresist layer on the substrate in this order; and performing the photoresist layer in a state where a photoresist layer corresponding to a designated light-emitting portion remains. After the pattern is exposed, a development step is performed; a step of forming a light-emitting portion whose surface is covered with a photoresist layer by removing the light-emitting layer exposed by removing the photoresist layer; and coating the hair 312 on the substrate / Invention patent description_ Supplement) / 92-02 / 91134595 567736 The step of forming a photoresist layer in the state of the light portion; and after the light emitting portion and its end portion are not exposed, pattern exposure of the photoresist layer , And then the development step. In the present invention, the end portion of the light-emitting portion after patterning is covered with a photoresist layer so that the formed light-emitting portion and the subsequent coating liquid for the light-emitting layer are not formed. The contact prevents the thinning and color mixing of pixels caused by the contact between the light-emitting portion and the coating liquid for a light-emitting layer. In the present invention, it is preferable to perform the step of peeling off the photoresist layer remaining on the light emitting portion after forming the light emitting portion, and then the step of forming the photoresist layer. This is because if a subsequent photoresist layer is overlaid on the previously formed photoresist layer, it may be difficult to form a good photoresist layer. Based on this, the photoresist layer is completely formed after the photoresist layer is removed in advance. In addition, the present invention is a manufacturing method of an EL element in which a plurality of types of light-emitting portions are formed on the above-mentioned substrate by using a light lithography method to repeatedly pattern light-emitting layers on the substrate forming the electrode layer. , Characterized in that: the method comprises the steps of forming a light emitting layer and a photoresist layer on the substrate in this order; and performing pattern exposure on the photoresist layer in a state where the photoresist layer corresponding to all light emitting portions remains, The development step is further performed; a step of forming a light-emitting portion whose surface is covered with the photoresist layer by removing the light-emitting layer exposed by removing the photoresist layer; and forming light on the substrate in a state of covering the light-emitting portion. A step of resisting the layer; a step of developing the exposed portion of the photoresist layer by pattern exposure so that the designated light emitting portion and its end portions are not exposed; and a step of removing the light emitting portion exposed by removing the photoresist layer . This case is also the same as the above case, so that the end portion of the light-emitting portion 9 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 after patterning is not exposed, and is covered with a photoresist layer. Because the formed light-emitting portion is not in contact with the coating liquid for a light-emitting layer to be subsequently applied, it is possible to prevent thinning and color mixing of pixels caused by the contact between the light-emitting portion and the coating liquid for a light-emitting layer. Therefore, when the photoresist layer is re-developed, the electrode layer is always maintained in a state covered by the light emitting portion. According to this, even when an organic EL layer such as a buffer layer is formed on the electrode layer, since the organic EL layer is not in contact with the developing solution of the photoresist layer, the organic EL layer has a solvent and development that is soluble in the photoresist layer. A liquid organic EL layer is also advantageous. φ In this case, it is preferable to perform the step of peeling off the photoresist layer remaining on all the light emitting portions after the step of forming the light emitting portion, and then the step of forming the photoresist layer. This is the same as the above case, because if the subsequent photoresist layer is overlaid on the previously formed photoresist layer, it may not be easy to form a good photoresist layer, which can eliminate the problems caused by not forming a good photoresist layer. Discomfort. In addition, in any of the above-mentioned EL device manufacturing methods, the step of removing the light-emitting layer or the light-emitting portion exposed by removing the photoresist layer is preferably a step of removing by dry etching. In this way, by using a method of removing the photoresist layer by dry etching, a more fine pattern can be formed. According to the present invention, the end portion of the light-emitting portion after patterning is covered with a photoresist layer so that the formed light-emitting portion and the subsequent coating liquid for the light-emitting layer are not formed. The contact prevents the thinning and color mixing of the pixels caused by the contact between the light-emitting portion and the coating liquid for a light-emitting layer. [Embodiment] The manufacturing method of the EL element of the present invention can be divided into two types of embodiments 10 312 / Invention Patent Specification (Supplement) / 92-02 / 9113 Magic 95 567736. Hereinafter, the manufacturing method of the EL element of the present invention will be described in detail for each embodiment. A · The first embodiment of the first embodiment of the sample invention is that the light-emitting layers of different types are formed on the substrate by using the photolithography method after being subjected to multiple patterning processes on the substrate forming the electrode layer. There are at least the following steps in a method of manufacturing an EL element of various types of light-emitting portions. (1) a step of forming a light-emitting layer and a photoresist layer on the substrate in this order (a step of forming a light-emitting layer and a primary photoresist layer); (2) leaving the photoresist layer corresponding to the designated light-emitting portion in a state where After pattern exposure is performed on the photoresist layer, a development step (a photoresist layer development step) is performed; (3) the light-emitting layer exposed by removing the photoresist layer is removed to form a surface covered with the photoresist layer (4) a step of forming a photoresist layer on the substrate in a state of covering the light emitting portion (a step of forming a second photoresist layer); (5) a step of forming the above The light-emitting portion and its end portions are not exposed. After the pattern is exposed to the photoresist layer, a development step (second photoresist layer development step) is performed. Regarding these steps, first, the formation of the first light-emitting portion will be briefly described using the first example of this embodiment shown in FIG. 1 (FIGS. 1 (a) to (0). In the first example of this embodiment, First, as shown in FIG. 1 (a), a patterned first electrode layer 2 and a buffer layer 3 formed on the substrate 1 are used to fully coat the first light-emitting layer by a spin coating method or the like. Coating liquid: The first light-emitting layer 11 11312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 is dried by a coating liquid and hardened to form a first light-emitting layer 4. Then, the first light-emitting layer 4 is entirely coated with a positive-type photoresist to form a primary photoresist layer 5 (the light-emitting layer and the primary photoresist layer forming step). Next, the portion corresponding to the first light-emitting portion is formed to be unexposed. In the state, the primary photoresist layer 6 is irradiated with ultraviolet rays 7 (Fig. 1 (a)). Then, the exposed portion of the photoresist layer 5 is developed with a photoresist developing solution, and the exposed photoresist layer 5 is removed by water washing. (— Secondary photoresist layer development step). Then, only the portion not covered by the primary photoresist layer 5 ^ is removed by the development of the light-emitting layer developing solution. Light emitting layer 4 (FIG. 1 (b), light emitting layer developing step). Then, as shown in FIG. 1 (c), a positive photoresist is coated on the entire surface to form a secondary photoresist layer 5 '( Step of forming a secondary photoresist layer). Next, a secondary photomask 6 'which is wider than the primary photomask 6 that shields the primary photoresist layer shown in FIG. 1 (a) is exposed with ultraviolet light 7 (Fig. 1 (d)). Then, the exposed portion of the secondary photoresist layer 5 'is developed with a photoresist developing solution, and then washed with water, as shown in Fig. 1 (e), to form a coating of the first light emitting portion 4' and The secondary photoresist layer 5 'at its end a (second photoresist layer development step). In this way, when patterning a light-emitting layer, the secondary photoresist layer and the secondary photoresist layer are processed twice. In the resist development step, the application step of the second light-emitting layer coating liquid for forming the next second light-emitting portion can be performed with the photoresist layer covering the end portion a of the first light-emitting portion 4 '. According to this, even if the next coating liquid for the second light-emitting layer is applied, no problems such as color mixing occur. FIG. 2 shows the completion of the formation of the first light-emitting portion of the second example of this embodiment (FIG. 2) ( a) ~ (e)). In this example, the steps to FIG. 1 (b), that is, the development of the photoresist layer 5 and the development of the first light-emitting layer (the light-emitting layer development step 12 312 / invention patent specification) (Supplement) / 92-02 / 91134595 567736 steps), it is exactly the same (refer to Figure 2 (b)). In this example, the step of 'releasing the first developed photoresist layer 5 (the photoresist peeling step) (See Figure 2 (c)). Next, the primary photoresist layer is completely removed, and a secondary photoresist layer 5 'is formed on the substrate on which the first light-emitting portion 4' is exposed, as in the example shown in Figure 1. The secondary photomask 6 'is used for exposure (FIG. 2 (d)), and the secondary photoresist layer 5' is formed wider so that it is covered with the secondary photoresist layer 5 'without causing the first light emission. A state in which the end portion a of the portion 4 'is exposed (Fig. 2 (e)). In the method of this example, it is necessary to separately perform a photoresist layer peeling step between the light-emitting layer developing step and the secondary photoresist layer forming step, but it is not repeated with the photoresist layer already formed in the example shown in FIG. 1. A photoresist layer is formed thereon, and therefore has the advantage of being easy to form a secondary photoresist layer. Next, the formation of the second light-emitting section will be described using the first example shown in Fig. 1 (Figs. 1 (f) to ϋ). The second light-emitting portion can also be formed by performing the same steps on the second light-emitting layer as in the method for forming the first light-emitting portion. At this time, the end portion a of the first light-emitting portion and the second light-emitting portion may be covered. In the state of the end portion b, the coating liquid for the third light-emitting layer is applied to prevent color mixture. That is, first, the second light-emitting layer 8 is formed by the same spin coating method or the like, and then a step of forming the primary photoresist layer 5 (the light-emitting layer and the primary photoresist layer forming step, FIG. 1 (0) is performed. , Using a photoresist 6 to pattern-expose the portion corresponding to the first light-emitting portion and the portion corresponding to the second light-emitting portion (Fig. 1 (f)). Then, a photoresist layer is developed with a photoresist developing solution (a photoresist Layer development step) to develop the exposed second light-emitting layer (light-emitting layer development step, FIG. 1 (g)). Subsequently, a secondary photoresist layer 5 'is formed by overlapping (second photoresist layer formation step, (FIG. 1 (h )). So, by using a wider secondary photomask 6 'into 13 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 line pattern exposure, development' to form a secondary photoresist layer The state of 5 'covering the end portion a of the first light-emitting portion 4 and the end portion b of the second light-emitting portion 8' (secondary photoresist layer development step, (Fig. L (j))) When the coating liquid for the third light-emitting layer is applied to form the third light-emitting layer (Fig. 1 (k)), "color will not be mixed in the first light-emitting portion and the second light-emitting portion. In addition, the description will be made about The second example of the formation of the second light-emitting portion (FIG. 2 (f) to (j)) is described. In the second example, the formation of the second light-emitting portion is also the same as that of the first light-emitting portion. The photoresist layer peeling step is performed between the step and the second photoresist layer development step. First, as in the first example, the steps of the second light emitting layer 8 and the first photoresist layer 5 are performed (FIG. 2 (f)), The state of the primary photoresist layer development step and the second light emitting layer development step is shown in FIG. 2 (§) (equivalent to FIG. Ug). In this state, the primary photoresist layer 5 and the secondary photoresist layer 5 'are peeled off ( Photoresist layer peeling step, Fig. 2 (h)). Then, a secondary photoresist layer 5 'is formed, and exposure and development are performed by using a wider secondary photomask 6' (Fig. 2 (i)). Forming the first light-emitting portion 4 'covered with the second photoresist layer 5' to the end portion a and the second light-emitting portion 8 'covered with the end b (the second photoresist layer formation step, the second photoresist layer Development step (Fig. 2 (j)). In the second example shown in Fig. 2, as in the case of the first light-emitting layer, the second photoresist layer is formed after the photoresist layer peeling step is performed in advance. Steps, thus As shown in FIG. 1, there is no case where a second photoresist layer is deposited on the formed first photoresist layer. Accordingly, there is an advantage that a second photoresist layer can be easily formed. Finally, the example and diagram shown in FIG. The example shown in 2 is the same, and the steps of forming the light-emitting layer and the photoresist of the light-emitting layer 9 and the photoresist 5 of the 3rd 14 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 are performed (Fig. 1 (k) (2 (k)). Then, after the photoresist is exposed, developed, and the third light-emitting layer is developed, the first light-emitting portion 4 ', the second light-emitting portion 8', and the first light-emitting portion are formed by peeling off the photoresist. 3 light emitting section 9 '(Fig. 1 (1)). Finally, as shown in FIG. 1 (m), a second electrode layer 10 is formed on these light-emitting portions, and an EL element that emits EL light under the figure can be manufactured. Hereinafter, a method for manufacturing the EL element according to this embodiment will be described in detail. φ 1. Steps of Forming the Light-Emitting Layer and the Primary Photoresist Layer In this embodiment, the steps of forming the light-emitting layer and the photoresist layer are performed first. As shown in Figs. 1 and 2 above, when the light-emitting layer is the first light-emitting layer, a coating solution for the first light-emitting layer is coated on the base material forming the normal electrode layer to form the first light-emitting layer. The substrate used in the above embodiment may be formed of at least an electrode layer as described above. However, this embodiment is not limited to this, and other organic EL layers such as a buffer layer may be used. · However, in this embodiment, as shown in FIG. 1 (d) to FIG. 1 (0), when the secondary photoresist layer 5 'is developed, it is necessary to perform development in a state where the buffer layer 3 is exposed. According to Therefore, in this embodiment, the organic EL layer such as the buffer layer formed at the position is preferably an organic EL layer that does not dissolve in the developing solution and the solvent of the photoresist layer. Specifically, a sol is used. -Buffer layer for gel reaction solution, photocurable resin and thermosetting resin. That is, it can be added to the sol-gel reaction solution, photocurable resin or thermosetting resin in an uncured state to provide a buffer. Additives for layer functions' are used as a retarder 15 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 Coating fluid for flushing layer formation, or by applying a sol-gel reaction solution, light The hardening resin or the thermosetting resin itself is denatured, and a buffer layer-forming coating liquid that can function as a buffer layer is used as the buffer layer that does not dissolve in the solvent by hardening the buffer layer-forming coating liquid. The following is a detailed description of the light-emitting layer and photoresist Each step of forming configuration. A. Substrate The substrate used in this embodiment is not particularly limited as long as it has high transparency, and can be used without substrate such as glass. Material or transparent resin. The transparent resin is not particularly limited as long as it can be formed into a thin film, but it is preferably a high molecular material having high transparency, solvent resistance, and high heat resistance. Specifically, polyether ijt (PES), polyethylene terephthalate (PET), polycarbonate (PC), polyether ether ketone (PEEK), polyvinyl fluoride (PVF), polyacrylate ( PA), polypropylene (PP), polyethylene (PE), amorphous polyolefin, or fluororesin. b. Electrode layer An electrode layer is formed on the substrate as described above. Such an electrode layer is not particularly limited as long as it is a normal EL element. The electrode layer provided on the base material in this way is referred to as a first electrode layer, and the electrode layer provided on the organic EL layer is referred to as a second electrode layer. These electrode layers are composed of an anode and a cathode. Which of the anode and the cathode is transparent or translucent, and the anode is preferably a conductive material having a large work function that is easy to inject holes. In addition, multiple materials can be mixed. Any electrode layer is preferably the one having the lowest resistance. Generally, a metal material is used, but an organic or inorganic compound may also be used. 16 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 c • The coating solution for the light-emitting layer In the conventional application of Is, the coating material for coating the light-emitting layer on the substrate on which at least the electrode layer is formed The liquid is dried on the substrate to form a light-emitting layer. Such a coating solution for a light emitting layer is generally composed of additives such as a light emitting material, a solvent, and a dopant. In addition, in this embodiment, a multi-color light-emitting device is formed by a method of manufacturing an EL element in which a plurality of types of light-emitting portions are formed on a substrate by patterning multiple types of light-emitting layers through a light lithography method. Layers. Accordingly, many types of coating liquids for light-emitting layers are used. The method for applying the coating liquid for a light-emitting layer to such a substrate is not particularly limited as long as it is a coating method that can be fully applied. For example, a spin coating method, a pouring method, a dipping method, a rod, or the like can be used. It is applied by a coating method such as a pad coating method, a doctor blade coating method, a roll coating method, a gravure coating method, an flexographic printing method, or a spray coating method. The applied coating liquid for a light-emitting layer is dried and cured by normal heating or the like to form a light-emitting layer. Hereinafter, each constituent material of the coating liquid for these light emitting layers will be described. I. Luminescent material The luminescent material used in this embodiment is not particularly limited as long as it emits light containing a material that emits fluorescence. In addition, it can also have a luminescent function, a hole transmission function, and an electron transmission function. Both. In this embodiment, as described later, in consideration of the relationship between the patterning of the light-emitting layer by the photolithography method, the material for forming the light-emitting layer uses a photoresist solvent and a photoresist developer that will not dissolve in the photoresist solution described later. And the material of the photoresist peeling liquid is preferable. In addition, in this case, the photoresist 17 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 photoresist used when patterning the light-emitting layer by photolithography is also used to form the light-emitting layer. The material of the solvent is preferred. Examples of such a light-emitting material include a pigment-based material, a metal complex material, and a polymer-based material. ① Pigment-based materials Examples of the pigment materials include methylcyclopentylamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, cladiazole derivatives, pyrazoloquinoline derivatives, and distyrylbenzene derivatives. , Distyryl arylidene derivative, Silol derivative, thiophene ring compound, pyridine ring compound, perionone derivative, this derivative, oligothiophene derivative, trifumaramine derivative, $ diazole dimer , Pyrazoline dimer and so on. ② Metal complex system materials Metal complex system materials include Dquinol alcohol saw complex, benzo Dquinol alcohol beryllium complex, benzo D quinazole zinc complex, and benzogazole zinc complex Compounds, benzothiazole zinc complexes, azomethyl zinc complexes, 44 winter zinc complexes, europium complexes, etc., have Al in the center metal. Zn, Be, and the like, or rare earth metals such as Tb, Eu, and Dy, and have a structure such as g-diazole, thiadiazole, phenylpyrimidine, phenylbenzimidazole, and quinoline in the ligand. ③ Polymer materials Polymer-based materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, and polyethylene A carbazole derivative, a pigment body, and a material in which a metal complex-based light-emitting material is polymerized. In this embodiment, the light-emitting material 18 312 / Invention Patent Specification (Supplement) / 92 is used from the viewpoint that the coating liquid for the light-emitting layer is used, and a light-lithography method can form a light-emitting layer with high accuracy. -02/91134595 567736 is still best to use the above polymer materials. π. Solvent It is clear from the examples shown in Figs. 1 and 2 that the coating solution for the light-emitting layer may be applied to the photoresist layer. Accordingly, as a solvent for the coating liquid for the light-emitting layer, the solubility for the photoresist was selected to be 0 at 25 ° C and 1 atmosphere. The solvent below 001 (g / g solvent) is better, if you choose 0. Solvents below 000 1 (g / g solvent) are more preferred. For example, in the case where the retardation layer described later is dissolved in a polar solvent such as water-based or DMF, DMSO, ethanol, and the photoresist is a 0-type phenolic lacquer-based photoresist, benzene, toluene, xylene can be used. Each of its isomers, its mixtures, trimethylbenzene, tetrahydro $, p-crofane, cumene, ethylbenzene, diethylbenzene, butylbenzene, chlorobenzene, dichlorobenzene And its mixtures are led by aromatic solvents, anisole, phenyl ether, butyl phenyl ether, tetrahydrofuran, 2-butanone, 1,4-dipalane, diethyl ether, diisopropyl ether, diphenyl ether, Ether-based solvents such as dibenzyl ether, ethylene glycol dimethyl ether, dichloromethane, 1,1-dichloroethane, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene, chloroform, Chlorinated solvents such as carbon tetrachloride, 1-chloronaphthalene, cyclohexanone, etc. may be used as long as they satisfy other conditions, or they may be a mixture of two or more solvents. In addition, as described later, when a buffer layer that is soluble in a solvent is used, in order to prevent mixing or dissolution of the buffer layer and the light-emitting layer material during film formation of the light-emitting layer, and to maintain the light-emitting characteristics of the light-emitting material itself, the buffer layer does not Dissolved is better. From this point of view, the solvent of the coating liquid for the light-emitting layer is selected so that the solubility of the buffer layer material is 0 at 25 ° C and 1 atmosphere. 001 (g / g solvent) 19 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 The solvent below is better, and if you choose 0. Solvents below 1000 i (g / g solvent) are more preferred. . Additives In addition to the above-mentioned luminescent materials and solvents, various additives may be added to the coating liquid for a light-emitting layer used in the present embodiment. For example, mixing may be performed for the purpose of improving the light emitting efficiency in the light emitting layer and changing the light emitting wavelength. Examples of such blending materials include inflammatory derivatives, coumarin derivatives, rubrene derivatives, dynazone derivatives, squalane derivatives, scutellar derivatives, acetophenone-based pigments, and tetracene Derivatives, pyrazoline derivatives, decacyclene, phenenone and the like. d. Photoresist In this embodiment, a primary photoresist layer is formed by coating the photoresist 'on the substrate forming the light emitting layer. The coating method of the photoresist at this time is generally not limited as long as it is a coating method capable of fully coating the coating fluid. Specifically, a spin coating method, a pouring method, a dipping method, or a rod can be used. It is applied by a coating method such as a pad coating method, a blade coating method, a roll coating method, a gravure coating method, an flexographic printing method, or a spray coating method. In this embodiment, a photoresist layer is formed on the light-emitting layer in this way, and the light-emitting layer is patterned by a photolithography method. This photolithography method is a method of forming an arbitrary pattern in response to a light irradiation pattern by utilizing the property that the solubility of the light irradiation portion of the film is changed by irradiation with light. The photoresist that can be used in this embodiment can be either a positive type or a negative type, and is not particularly limited, but is formed with an organic EL layer insoluble in a light-emitting layer, etc. 20 312 / Invention Patent Specification (Supplement) / 92-〇2 / 91134595 567736 is preferred. Specific examples of the photoresist that can be used include a phenolic lacquer resin system, a rubber + diazide system, and the like. e. Photoresist Solvent In this embodiment, the photoresist solvent used when the above photoresist is applied is to prevent the above-mentioned organic el layer such as the light-emitting layer during photoresist film formation from mixing and dissolving with the photoresist material, keeping the original The light-emitting characteristics are preferably those using an organic EL layer material such as an insoluble light-emitting layer material. With this in mind, as a photoresist solvent that can be used in this embodiment, the solubility of the organic EL layer-forming material, such as the material for forming the light-emitting layer, is selected to be 0 at 25 ° C and 1 atmosphere. Solvents below 001 (g / g solvent) are preferred, and if 0 is selected. Solvents below 1,000 1 (g / g solvent) are more preferred. Examples include acetone, methyl ethyl ketone-based ketones, propylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether cellulose-based fibrinolytic agents. Acetic acid esters, propylene glycol monoethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether as a cellosolve, methanol, ethanol, 1-butanol, 2-butanol, cyclohexanol The leading alcohols, ester solvents such as ethyl acetate, butyl acetate, cyclohexane, decalin, etc. can also be used if they satisfy other conditions, and they can also be a mixture of two or more solvents. 2 . -Secondary photoresist layer development step Further, in this embodiment, the photoresist layer corresponding to the designated light-emitting portion remains in a state, and the photoresist layer is subjected to pattern exposure, and then the primary photoresist is developed. Layer development step. 21 312 / Invention Patent Specification (Supplement) / 92-〇2 / 91134595 567736 In this step, first, a photoresist layer is exposed through a photomask. Since this exposure method and the like are the same as the conventional exposure method, this description is omitted here, and the photomask is a photomask that is formed in a state where the photoresist layer on which the first light-emitting portion is formed can remain. Specifically, in the example shown in FIG. 1 or FIG. 2, since a positive type photoresist is used, a photoresist that can shield the portion corresponding to the first light-emitting portion is used. Conversely, when a positive type photoresist is used, only the photoresist is used. Photoresist for exposing a portion corresponding to the first light-emitting portion. In addition, it is also possible to consider the case where the pattern is exposed by drawing by laser light or the like, and this embodiment also includes this case. Then, after the pattern exposure, the development of the first photoresist layer is performed. As a result, the photoresist layer is patterned in a state where the first photoresist layer remains on the first light-emitting portion. The following describes the developer used for the pattern processing of the photoresist layer in this step. (Photoresist layer developing solution): The photoresist layer developing solution that can be used in this embodiment is not particularly limited as long as it is insoluble in the material forming the light-emitting layer. Specifically, an organic alkali-based developer generally used may be used. In addition, an inorganic alkali or an aqueous solution capable of developing a photoresist layer may be used. After the photoresist layer is developed, it is preferably washed with water. As the photoresist layer developing solution that can be used in this embodiment, the solubility of the material for forming the light-emitting layer is selected to be o at 25 ° C and 1 atmosphere. ooWg / g developer) is better than the developer, and if selected. Developers below 0.0001 (g / g developer) are more preferred. 22 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 3 · Developing step of light emitting layer In this embodiment, the light emitting layer exposed by removing the photoresist layer once in this way is removed, and the surface is formed by A step of covering the light-emitting portion with a photoresist layer. This light-emitting layer development step may be a wet method using a solvent that dissolves the light-emitting layer and a dry method using dry uranium engraving. In this embodiment, a dry method without discomfort such as color mixing is preferred. These various methods are described below. (Wet method) 0 The wet method in this case is a method of dissolving and removing the light-emitting layer using a solvent that can dissolve or peel the light-emitting layer without peeling off the photoresist. • As the solvent usable at this time, in addition to the solvent that can be used for the coating liquid for a light-emitting layer, as long as it is a solvent that satisfies the above conditions, another solvent can be selected. In addition, removal using this solvent can also be performed in an ultrasonic bath. The use of such an ultrasonic bath is because it has no discomfort such as thinness of the light-emitting layer pattern or the outflow of the light-emitting layer, and it can form a high-precision pattern. . In this embodiment, the ultrasonic conditions for the ultrasonic bath are set at an oscillation frequency of 25 ° C, 20 ~ ΙΟΟΚΗζ, 0. Under the conditions of 1 to 60 seconds, the performance is good. Under these conditions, high-precision patterns can be formed in a short time. (Dry method) The dry method is a method of removing the light-emitting layer of the removed photoresist portion using dry etching. Generally, because the photoresist layer has a larger film thickness difference from the light emitting layer, 23 312 / Invention Patent Specification (Supplement) / 92 · 〇2 / 91134595 567736 The light emitting layer can be removed by dry etching the entirety. In this case, the film thickness of the photoresist layer is preferably in a range of 0. 1 to 1 0 // m, and more preferably in a range of 0. 5 to 5 / i m. With such a film thickness, in addition to ensuring the resist function of photoresist, dry etching with high processing accuracy can be obtained. In this way, if dry etching is used, the end portion of the uranium etch can be further etched, so that the width of the uneven thickness region existing at the end portion of the pattern can be narrowed. As a result, a pattern with higher processing accuracy can be obtained Effect. φ As the dry method used in this embodiment, the dry etching is preferably a reactive ion etching. The use of reactive ion etching is because the organic film undergoes a chemical reaction and becomes a compound with a small molecular weight, which can be removed from the substrate by vaporization and evaporation, which may cause high etching accuracy and short-time processing. In the present embodiment, it is preferable to use an oxygen monomer or an oxygen-containing gas during the dry etching. By using an oxygen monomer or an oxygen-containing gas, decomposition and removal by an oxidation reaction of an organic substance can be performed, and an unnecessary organic substance can be removed from the substrate, thereby making high-etching accuracy and short-time processing possible. In addition, under this condition, since the oxide transparent conductive film such as IT 0 which is normally used is not etched, the electrode characteristics are not impaired, and it is also very effective in cleaning the electrode surface. In the present embodiment, it is preferable to use an atmospheric pressure plasma for the dry uranium etching. By using an atmospheric piezoelectric slurry, dry etching, which normally requires a vacuum device, can be performed at atmospheric pressure, and therefore, processing time can be shortened and costs can be reduced. In this case, uranium can be oxidized and decomposed with organic matter by oxygen in plasma-derived atmosphere 24 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736, but it can also be changed by gas And the circulation adjusts the gas composition in the reaction gas at will. 4. Photoresist layer peeling step In this embodiment, after performing the photoresist layer developing step described above, a step of peeling the primary photoresist layer after being developed may be further performed. Specifically, as shown in FIGS. 2 (b) to 2 (c), the light-emitting portion is exposed by peeling the primary photoresist layer remaining on the substrate, and then forming a secondary photoresist layer described later Step by step method. In the state where the primary photoresist layer remains, it is more difficult to deposit on it to form a secondary photoresist layer, or the film thickness becomes thicker by depositing the photoresist layer, and when the subsequent light emitting layer is formed In the case where a problem occurs, the secondary photoresist layer is preferably formed in such a state that the photoresist layer on the substrate is temporarily peeled. (Photoresist peeling liquid) When peeling such a photoresist layer, a photoresist peeling liquid is used. As the photoresist stripping solution that can be used in this embodiment, it is not necessary to dissolve the light-emitting layer, but it is necessary to dissolve the photoresist layer. Therefore, the above-mentioned photoresist solvent can be used directly. In the case of using a regular photoresist, after UV exposure, peeling may be performed using a liquid listed as a developing solution. In addition, solvents such as a strong alkaline aqueous solution, dimethylformamide, dimethylacetamide, dimethylasyl, N-methyl-2-tetrahydropyrrolidone, etc., and these mixtures are commercially available. Photoresist stripping solution. After photoresist peeling, rinse with 2-propanol or the like, or rinse with water. 5. Secondary photoresist layer formation step 25 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 After the light emitting layer development step is performed, light is formed on the substrate to cover the light emitting portion. Barrier step. The secondary photoresist layer used here can be made of the same material as the above-mentioned primary photoresist layer. Therefore, the description of this item is omitted here. In this aspect, the same photoresistive layer may be used for the primary photoresistive layer and the second photoresistive layer, or a case where different photoresistive layers are used. In the case where the photoresist layer peeling step is performed, the primary photoresist layer and the secondary photoresist layer are used separately. Therefore, considering the simplicity of the steps, it is preferable to use the same photoresist layer at φ. On the other hand, in the case where the above-mentioned photoresist layer peeling step is performed, since a secondary photoresist layer must be formed on the primary photoresist layer, a different photoresist may be used depending on the situation. 6. Secondary photoresist layer development step The end portion a of the light-emitting portion after patterning is exposed at the stage of FIG. 1 (b) and FIG. 2 (b) without being covered by the primary photoresist layer. If the coating liquid for the next light-emitting layer is applied from this state, the material of the light-emitting layer is easily dissolved into the coating liquid for the light-emitting layer from the ends a and b, etc., resulting in color mixing and pixels. Thin problem points. In order to solve this problem, the light-emitting portion is covered with a wider width than that of the primary photoresist layer remaining in the exposure and development steps of the primary photoresist layer in the secondary photoresist layer exposure and development steps. The pattern is processed in a state of °, that is, not only the ends of the light-emitting portions are covered, but also the secondary photoresist layer is exposed and developed in a size that does not involve adjacent light-emitting portions. In other respects, since it is the same as the above-mentioned photoresist layer development step 26 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736, this description is omitted here. 7. In other aspects of this embodiment, after repeating the above steps 1 to 6 twice, as described in the example shown in FIG. 1 above, the light emitting layer forming step and the photoresist layer forming step are performed again, and the formed photoresist layer is exposed. After the developing step and the developing step of the formed light-emitting layer, a three-color light-emitting portion can be formed by performing a peeling step of the photoresist layer. Subsequently, after the second electrode and the protective layer are formed, the EL device can be fabricated by packaging. B. Second Embodiment A second embodiment of the method for manufacturing an EL device according to the present invention will be described below. This embodiment is a method of manufacturing an EL element in which a plurality of types of light-emitting portions are formed on the above-mentioned substrate by using a light lithography method on the substrate forming the electrode layer and performing multiple patterning processes on the substrate. A method having at least the following steps. (1) a step of forming a light emitting layer and a photoresist layer on the above substrate in this order (a step of forming a light emitting layer and a primary photoresist layer); (2) leaving the photoresist layer equivalent to all light emitting portions After the pattern exposure of the photoresist layer, the development step (a photoresist layer development step) is performed; (3) forming a surface covered with the photoresist layer by removing the light-emitting layer exposed by removing the photoresist layer; Step of the light-emitting part to be covered (light-emitting layer developing step 1); (4) forming a photoresist layer on the substrate in a state of covering the light-emitting part 27 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 Step 567736 (secondary photoresist layer forming step); (5) In order to prevent the designated light-emitting part and its end portion from being exposed, pattern the photoresist layer and then develop it (secondary photoresist) Layer development step). (6) A step of removing the light-emitting portion exposed by removing the photoresist layer (light-emitting portion developing step 2); For each of these steps, first, using the first example shown in FIG. 3, the formation of the first light-emitting portion is briefly described. (Figures 3 (a) to (f)). 0 Figure 3 shows the first example of this embodiment. As shown in FIG. 3 (a), as in the case shown in FIG. 1 described above, a first light-emitting layer 4 and a primary photoresist layer 5 (light-emitting layer and primary light) are formed on the substrate 1 on which the electrode layer 2 and the buffer layer 3 are formed. Barrier layer forming step). Next, the primary photoresist layer 5 is exposed for development (primary photoresist layer development step). The biggest difference between this embodiment and the first embodiment described above is that in this one-time development step of the photoresist layer, the present embodiment forms a photomask in a state where the photoresist layer remains in the region where all the light emitting portions are formed. 6 (Fig. 3 (a)), φ is the point where exposure is performed by such a mask 6 and then development is performed. In a state where the photoresist layer is left once in the region where all the light emitting portions are formed, a step of developing the exposed first light emitting layer 4 is performed (light emitting layer developing step 1, Fig. 3 (b)). Then, a secondary photoresist layer is formed in a state in which the light-emitting portion on the substrate is covered (secondary photoresist layer formation step ·, Fig. 3 (c)). Next, using a secondary mask 6 ′ formed wider than the primary mask 6, pattern exposure (FIG. 3 (d)) and development (secondary 28 312 / Invention Patent Specification ( Supplement) / 92-〇2 / 91134595 Photoresist layer development step, Fig. 3 (e)). Finally, by developing the light-emitting layer remaining on the other light-emitting portions, the end portion a of the first light-emitting portion 4 'is not exposed, and a state of the secondary layer 5' is formed (the light-emitting portion developing step 2, FIG. 3 (f)). In this embodiment, when a light emitting layer is pattern-processed, the first light emitting portion 4 ′ can be coated on the resistance layer by performing a second photoresist development step of the photoresist layer and the second photoresist layer. In the state of the end part a, the application process of the coating liquid for the next light emitting layer is performed. Accordingly, even if the coating liquid for the next light layer is applied, there is no problem such as color mixing. Moreover, this embodiment is characterized in that in the development of the second photoresist layer, the second resist layer is developed in a state where the buffer layer 3 is covered with the first light emitting layer 4. In other words, although the photoresist layer is developed after pattern exposure in FIG. 3 (d), at this time, the first shot 4 exists on the buffer layer (FIG. 3 (e)), so the photoresist The layer developing solution does not directly contact the buffer layer. In this embodiment, there is also an advantage that the buffer layer can be used even if it is a buffer layer that is soluble in the material of the photoresist layer. FIG. 4 shows the creator of the first light-emitting portion (FIGS. 4 (a) to ()) showing a second example of this embodiment. In this example, a step up to FIG. 3 (b) and a primary photoresist layer 5 are provided. The steps of developing the first light-emitting layer (light-emitting shadow step 1) are completely the same (refer to FIG. 4 (b)), and the step of developing the primary photoresist layer 5 under peeling (one photoresist peeling step, reference 4 (c)), etc. Next, the primary photoresist layer is completely removed, and the secondary photoresist layer 5 'is formed on the material exposed to the first light-emitting portion 4', which is the same as the example shown in Fig. 3, 312 / Invention Patent Specification (Supplement) /92.02/91134595 can be made into photoresistance by light. Step 2 2nd step Secondary light Secondary light layer touch. After the shadow solution is completed, that is, the layer is displayed, the second photoresist layer 5 is formed wider by using the second photomask 6 'through 29 567736, so that it becomes the second photoresist layer 5' A state in which the end portion a of the first light-emitting portion 4 'is exposed without being covered (FIG. 4 (f)). In this second method, it is necessary to perform a photoresist layer peeling step between the light-emitting layer developing step 1 and the secondary photoresist layer forming step, but the photoresist formed in the example shown in FIG. 3 is not used again. A photoresist layer is formed on the layer, which is easy to form a secondary photoresist layer. In addition, the film thickness is not greatly increased, so there is an advantage that a uniform light emitting layer can be formed. In addition, in this second method, when the photoresist layer is developed once in the same manner as in the first method (Fig. 4 (d)), the buffer layer 3 is not directly developed with the photoresist because of the light emitting layer 4 (Fig. 4 (e)). Fluid contact. This has the advantage that it can be used even if it is a buffer layer soluble in a photoresist developer. This embodiment is also the same as that of the first embodiment described above. Since the second light-emitting layer performs the same steps (FIG. 3 (g) to (k)), the end of the first light-emitting portion 4 'can be covered. In the state of the portion a and the end portion b of the second light-emitting portion 8 ′, the third light-emitting layer coating liquid is applied (FIG. 3 (1)), thereby preventing color mixture. It is the same as the above-mentioned step of forming the first light-emitting portion. In the second photoresist layer development step, a second light-emitting layer 8 is present on the buffer layer (FIG. 3 (j)), and then the light-emitting layer development step 2 ( Figure 3 (k)). This prevents the buffer layer 3 from directly contacting the photoresist developer when the second light-emitting portion is formed. In addition, in the second example of this embodiment, the same steps can be performed in the same manner as in the second light-emitting layer (Fig. 4 (g) to (k)). Subsequently, after the third light-emitting layer and the photoresist layer are formed, the first light-emitting portion 4 ′ and the second light-emitting portion 8 ′ 30 312 are formed by exposure (FIGS. 3 (1) and 4 (1)) and development. / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 & 3rd light emitting section 9 '. Then, finally, a second electrode layer 'is formed on these light-emitting portions, so that an EL element that emits EL light under the figure can be manufactured. & The method of manufacturing the EL element according to this embodiment will be described in detail. In addition, the materials and forming methods used in the present embodiment, * & In the description below, matters other than the points specifically pointed out are the same as those described in the first embodiment as described above. The description of each step below is omitted. I Light-emitting layer and primary photoresist layer formation step 0 In this embodiment, the same as the first embodiment, first, on the substrate @row in this order to form the light-emitting layer and photoresist layer light-emitting layer and primary photoresist Layer formation step. In this embodiment, as described later, the electrode layer can be formed even if it is an organic EL layer that is soluble in a photoresist developing solution, such as a buffer layer. Note about this type of buffer layer. (Buffer layer) The buffer layer of this embodiment is a film provided between the anode and the light-emitting layer or between the cathode and the light-emitting layer in order to facilitate charge injection into the light-emitting layer φ. The film contains an organic substance, especially an organic conductor. Floor. For example, it may be a conductive polymer having a function of increasing hole injection efficiency into a light emitting layer and flattening unevenness of an electrode or the like. In the case where the buffer layer used in this embodiment has high conductivity, it is preferable to be a patterned person in order to maintain the diode characteristics of the device and prevent crosstalk. In addition, when the resistance of the buffer layer is high, there may be cases in which it is not patterned. In addition, in the case of omitting the components of the buffer layer, there may be no delay. 31 312 / Invention Patent Specification (Supplement) / 92 · 〇2 / 91134595 567736 It is also possible to punch. In this embodiment, in the case of forming both the buffer layer and the light-emitting layer by photolithography pattern processing, the material of the buffer layer is preferably selected and selected insoluble in the photoresist solvent and the light-emitting layer forming solvent. It is more preferable to select a material that is insoluble in the photoresist stripping solution as the material forming the buffer layer. Specific examples of the material for forming the buffer layer used in this embodiment include a polymer of a hole-transporting substance such as a polyalkyl edge phene derivative, a polyaniline derivative, and triphenylamine, and a sol of an inorganic oxide. -Gel film, polymer film of organic matter such as trifluoromethane, organic compound film containing Lewis acid, etc. 'As long as the solubility conditions as described above are satisfied, it is not particularly limited, and may be used after film formation. The above conditions are satisfied by polymerization, combustion, or the like. In addition, in this embodiment, the solvent used when forming the buffer layer is not particularly limited as long as it can disperse or dissolve the buffer layer. However, in full-color patterns and the like, there are multiple film formations. If necessary, it is necessary to use a buffer layer solvent that does not dissolve the photoresist material, and a buffer layer solvent that does not dissolve the light emitting layer is preferred. Lu as the buffer layer solvent that can be used in this embodiment to select the solubility of the photoresist material, which is 0 at 25 ° C and 1 atmosphere. A solvent below 001 (g / g solvent) is preferred, and if 0 is selected. Solvents below 1,000 1 (g / g solvent) are more preferred. As a buffer layer solvent, the solubility of the light-emitting layer constituting material is 0 at 25 ° C and 1 atmosphere. Solvents below 0 0 1 (g / g solvent) are preferred, and if 0 is selected. Solvents below 0 0 1 (g / g solvent) are more preferred. Specific examples include water, methanol, ethanol-based alcohols, dimethylformamide, dimethylacetamide, dimethylsulfite, and N-methyl · 2-tetrahydro D. Patent specification (supplement) / 92-〇2 / 91134595 32 567736 A solvent such as ketone can be used as long as the solvent satisfies the conditions. In addition, two or more solvents may be mixed and used. 2 · — Secondary photoresist layer development step Further, a photoresist layer development step is performed after pattern exposure is performed on the formed photoresist layer in a state where the photoresist layer corresponding to all light emitting portions remains. . This step is a step that is very different from the first embodiment. For the first embodiment, the photoresist layer corresponding to the designated light-emitting portion is left, and should be
' W 實施態樣係以使相當於所有發光部部分的光阻層殘留的狀 態，對形成之光阻層進行圖案曝光、顯影。 3 .發光層顯影步驟1 然後，進行藉由除去經如上述去除一次光阻層而曝露的 發光層，形成表面由光阻層覆被的發光層顯影步驟 如此，進行一次光阻層形成步驟後，藉由進行發光層顯 影步驟1，即可除去由一次光阻層所覆被的相當於發光部 部分之間存在的發光層。 Φ 上述2之步驟及本步驟中，藉由於如此之發光部、亦即 緩衝層存在部分殘留發光層，同時，除去存在於其間的發 光層，即可使由下一步驟中形成的二次光阻層來覆被發光 部的端部，同時，又可於隨後的二次光阻層顯影步驟中由 發光層來保護緩衝層。 4 .光阻層剝離步驟 本實施態樣中，與第1實施態樣相同，在進行上述光阻 層顯影步驟後，還可進行剝離被顯影後的一次光阻層的步 33 312/發明專利說明書(補件)/92-02/91134595 567736 驟。在殘留有一次光阻層的狀態下，在較難於其上沉積以 形成二次光阻層的情況，或是，藉由沉積光阻層造成膜厚 變厚，而於隨後的發光層形成時產生問題的情況等中，如 此般，以從暫時將基材上的光阻層剝離的狀態，進行二次 光阻層的形成爲佳。 5 .二次光阻層形成步驟 再者，進行於上述基材上以覆被上述發光部的狀態形成 光阻層的二次光阻層形成步驟。藉此，可如上述藉由二次 光阻層覆被發光部的端部。 6 .二次光阻層顯影步驟 然後，使指定的發光部及其端部不被曝露狀，將上述光 阻層曝光後，進行顯影之二次光阻層顯影步驟。本步驟中， 於顯影二次光阻層時，位於電極層上、亦即位於形成發光 部的區域的緩衝層，因爲由發光層所覆被，因而不會直接 與二次光阻層顯影步驟所使用的光阻層顯影液接觸。據 此，本實施態樣中，也可使用如上述之可溶於光阻層顯影 液等的緩衝層。 7 .發光層顯影步驟2 * 隨後，進行除去經去除上述光阻層而曝露的發光部的發 光部顯影步驟。 本實施態樣中，如此般藉由重複進行2次發光層顯影步 驟，於光阻層顯影步驟中，可使緩衝層成爲由發光層覆被 而不被曝露者。 本實施態樣若與第1實施態樣比較，確實爲有多進行一 34 312/發明專利說明書(補件)/92-02/91134595 567736 次發光層顯影步驟者。然而，爲了提高發光效率等，也有 必須要形成可溶於溶媒的緩衝層的情況，本實施態樣爲適 用此種情況的態樣。 又’本發明中，並不限於上述實施形態。上述實施形態 僅爲例示’只要爲與本發明之申請專利範圍所記載之技術 思想實質相同的構成，且可獲得相同作用效果者，無論何 種構成均含於本發明之技術範圍內。 [實施例] 以下’參照實施例更爲詳細地說明本發明。 (實施例1) (實施例） (緩衝層之成膜） 將6英吋□、板厚l.lmm的被圖案處理過的IT0基板洗 淨’用作爲基材及第1電極層。取0 · 5 m 1的緩衝層塗敷液 (BAYER公司（德）製；Baytronp、由如下之化學式（1)所示）， 滴落於基材的中心部，進行旋塗。以轉速25 OOrpm保持20 秒形成膜層。其結果，膜厚形成爲8 00埃。'W The embodiment is a pattern exposure and development of the formed photoresist layer in a state where the photoresist layer corresponding to all the light emitting portions remains. 3. Light-emitting layer development step 1 Then, the light-emitting layer exposed by removing the photoresist layer once as described above is formed to form a light-emitting layer whose surface is covered with the photoresist layer. The development step is such that after performing the photoresist layer formation step once By performing the light-emitting layer developing step 1, the light-emitting layer existing between the portions corresponding to the light-emitting portion covered by the primary photoresist layer can be removed. Φ In the above 2 step and this step, the secondary light formed in the next step can be made by removing the light emitting layer existing therebetween due to the presence of a partial light emitting layer in the light emitting portion, that is, the buffer layer. The resist layer covers the end of the light emitting part, and at the same time, the buffer layer can be protected by the light emitting layer in the subsequent secondary photoresist layer development step. 4. Photoresist layer peeling step In this embodiment, the same as the first embodiment, after performing the photoresist layer development step described above, step 33 312 / invention patent of peeling the developed photoresist layer can also be performed. Instruction (Supplement) / 92-02 / 91134595 567736 steps. In the state where the primary photoresist layer remains, it is more difficult to deposit on it to form a secondary photoresist layer, or the film thickness becomes thicker by depositing the photoresist layer, and when the subsequent light emitting layer is formed In the case where a problem occurs, the secondary photoresist layer is preferably formed in such a state that the photoresist layer on the substrate is temporarily peeled. 5. Secondary photoresist layer forming step Further, a secondary photoresist layer forming step of forming a photoresist layer on the substrate in a state of covering the light emitting portion is performed. Thereby, the end portion of the light emitting portion can be covered with the secondary photoresist layer as described above. 6. Secondary photoresist layer development step Then, the designated light emitting part and its end are not exposed. After exposing the above photoresist layer, a secondary photoresist layer development step of development is performed. In this step, when developing the second photoresist layer, the buffer layer located on the electrode layer, that is, in the area where the light emitting portion is formed, is not covered with the second photoresist layer directly because it is covered by the light emitting layer. The photoresist developer used was in contact. Accordingly, in the present embodiment, a buffer layer which is soluble in a photoresist layer developing solution or the like as described above can also be used. 7. Light-emitting layer development step 2 * Subsequently, a light-emitting portion development step of removing the light-emitting portion exposed by removing the photoresist layer is performed. In this aspect, by repeating the light-emitting layer development step twice, in the photoresist layer development step, the buffer layer can be covered by the light-emitting layer without being exposed. If this embodiment is compared with the first embodiment, it is indeed that there is one more light emitting layer developing step 34 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 times. However, in order to improve the luminous efficiency, etc., it may be necessary to form a buffer layer that is soluble in a solvent, and this embodiment is a mode in which this case is applied. The present invention is not limited to the above embodiment. The above-mentioned embodiment is merely an example. As long as it has substantially the same structure as the technical idea described in the scope of patent application of the present invention, and can obtain the same effect, any kind of structure is included in the technical scope of the present invention. [Examples] Hereinafter, the present invention will be described in more detail with reference to examples. (Example 1) (Example) (Film formation of a buffer layer) A pattern-treated ITO substrate cleaned 6 'square plate having a thickness of 1.1 mm was used as a substrate and a first electrode layer. A buffer coating solution (manufactured by BAYER Co., Ltd .; Baytronp, represented by the following chemical formula (1)) of 0.5 m 1 was taken, dropped on the center portion of the substrate, and spin-coated. A film layer was formed by holding at a rotation speed of 25 OO rpm for 20 seconds. As a result, the film thickness was set to 800 Angstroms.
312/發明專利說明書(補件)/92-02/91134595 35 567736 (第1發光層之成膜） 作爲第1發光層’於緩衝層上取1 m 1紅色發光有機材料 之塗敷液（聚乙烯基咔唑衍生物70重量部、邊二唑30重量 部、二氰化甲基吡喃1重量部、氯苯4 9 0 0重量部），滴落 於基材的中心部，進行旋塗。以轉速2 0 0 0 r p m保持1 0秒 形成膜層。其結果，膜厚形成爲8 00埃。 取2ml正型光阻液（東京應化公司製；〇FPR-8〇〇)，滴落 於基材的中心部，進行旋塗。以轉速5 OOrpm保持1 0秒， 隨後以轉速2000rpm保持20秒形成膜層。其結果，膜厚 可形成約爲1 // m。以8 0 °C進行3 0分鐘預烘。隨後，與曝 光光罩同時設定於對準曝光機，以紫外線曝光欲除去緩衝 層及發光層之部分。由光阻顯影液（東京應化公司製； N M D - 3 )顯影2 0秒後，進行水洗，除去曝光部的光阻層。 以1 2 0 °C進行3 0分鐘後續烘烤後，藉由使用氧電漿的反應 性離子蝕刻，除去被除去光阻層部分的緩衝層及發光層。 利用丙酮全部除去光阻層後，再度，取2 m 1正型光阻液（東 京應化公司製；OFPR- 8 00)，滴落於基材的中心部，進行 旋塗。以轉速5 00rpm保持1 0秒，隨後以轉速2000rpm保 持2 0秒形成膜層。其結果，膜厚約形成爲i y m。以8 (TC 進行3 0分鐘預烘。隨後，與曝光光罩同時設定於對準曝光 機，以紫外線曝光，藉以形成殘留較第1發光部的寬幅各 大1 〇 // m寬度的光阻層。由光阻顯影液（東京應化公司製； NMD-3)顯影20秒後，進行水洗，除去曝光部的光阻層。 以120°C進行30分鐘後續烘烤，獲得第1發光部被具有較 36 312/發明專利說明書(補件)/92-02/91134595 567736 第1發光部的寬幅各大1 ο // m寬度的光阻層保護的基材。 (第2緩衝層之成膜） 於所獲得的基材上，取〇.5ml的緩衝層塗敷液（BAYER 公司（德）製；Baytronp)，滴落於基材的中心部，進行旋塗。 以轉速2 5 0 Orpm保持20秒形成膜層。其結果，膜厚形成 爲8 00埃。 (第2發光層之成膜） 作爲第2發光層，於緩衝層上取1 ml綠色發光有機材料 $ 之塗敷液（聚乙烯基咔唑7 0重量部、巧二唑3 0重量部、α -苯并礼喃酮6爲1重量部、氯苯4900重量部），滴落於基 材的中心部，進行旋塗。以轉速2000rpm保持1 0秒形成 膜層。其結果，膜厚形成爲800埃。 取2ml正型光阻液（東京應化公司製；OFPR-800)，滴落 於基材的中心部，進行旋塗。以轉速5 0 0 r p m保持1 0秒， 隨後以轉速2 00 Orpm保持20秒形成膜層。其結果，膜厚 可形成約爲1 // m。以8 0 °C進行3 0分鐘預烘。隨後，與曝 鲁 光光罩同時設定於對準曝光機，以紫外線曝光欲除去第1 發光部及第2發光部以外之發光層之部分。由光阻顯影液 (東京應化公司製；NMD-3)顯影20秒後，進行水洗，除去 曝光部的光阻層。以1 2 0 °C進行3 0分鐘後續烘烤後，藉由 使用氧電漿的反應性離子蝕刻，除去被除去光阻層部分的 緩衝層及發光層。利用丙酮全部除去光阻後，再度，取2m 1 正型光阻液（東京應化公司製；〇FPR-8 00)，滴落於基材的 中心部，進行旋塗。以轉速5 00rpm保持10秒，隨後，以 37 312/發明專利說明書(補件)/92·02/91134595 567736 轉速2000rpm保持20秒形成膜層。其結果，膜厚約形成 爲l//m。以80 °C進行30分鐘預烘。隨後，與曝光光罩同 時設定於對準曝光機，以紫外線曝光，藉以形成殘留較第 1發光部及第2發光部的寬幅各大i〇//m寬度的光阻層。312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 35 567736 (film formation of the first light-emitting layer) As the first light-emitting layer, take 1 m 1 of a red light-emitting organic material coating solution on the buffer layer (poly 70 parts by weight of vinylcarbazole derivative, 30 parts by side diazole, 1 part by weight of dicyanomethylpyran, and 4900 part by weight of chlorobenzene) were dropped on the center of the substrate and spin-coated . A film layer was formed by holding at a rotation speed of 2 0 0 0 r p m for 10 seconds. As a result, the film thickness was set to 800 Angstroms. 2 ml of a positive-type photoresist (manufactured by Tokyo Yinghua Co., Ltd .; 〇FPR-8〇〇) was dropped onto the center portion of the substrate and spin-coated. The film was maintained at a rotation speed of 500 rpm for 10 seconds, and then maintained at a rotation speed of 2000 rpm for 20 seconds. As a result, the film thickness can be approximately 1 // m. Pre-bake at 80 ° C for 30 minutes. Subsequently, it is set at the same time as the exposure mask with the exposure mask, and the portion where the buffer layer and the light emitting layer are to be removed is exposed with ultraviolet rays. After developing with a photoresist developing solution (manufactured by Tokyo Inka Co., Ltd .; NM D-3) for 20 seconds, it was washed with water to remove the photoresist layer in the exposed portion. After 30 minutes of subsequent baking at 120 ° C, the buffer layer and the light emitting layer from which the photoresist layer has been removed are removed by reactive ion etching using an oxygen plasma. After the photoresist layer was completely removed with acetone, 2 m 1 of a positive-type photoresist solution (manufactured by Toyo Inka Co., Ltd .; OFPR-8 00) was taken and dropped on the center of the substrate to perform spin coating. The film was maintained at a rotation speed of 500 rpm for 10 seconds, and then maintained at a rotation speed of 2000 rpm for 20 seconds. As a result, the film thickness is approximately i y m. Pre-bake at 8 ° C for 30 minutes. Then, set it to the alignment exposure machine at the same time as the exposure mask, and expose it with ultraviolet rays to form residual light that is larger than the width of the first light-emitting portion by 1 // m. Barrier layer. After developing for 20 seconds with a photoresist developer (manufactured by Tokyo Inka Co., Ltd .; NMD-3), it was washed with water to remove the photoresist layer in the exposed part. After baking at 120 ° C for 30 minutes, the first luminescence The substrate is protected by a photoresist layer having a width larger than that of 36 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 1 ο // m width. (Second buffer layer (Film formation) On the obtained substrate, 0.5 ml of a buffer layer coating solution (BAYER (Germany); Baytronp) was dripped onto the center of the substrate and spin-coated. The rotation speed was 2 5 The film layer was formed by holding it at 0 Orpm for 20 seconds. As a result, the film thickness was 800 angstroms. (Film formation of the second light-emitting layer) As the second light-emitting layer, 1 ml of the green light-emitting organic material $ was applied on the buffer layer. Liquid (70 parts by weight of polyvinylcarbazole, 30 parts by weight of dioxazol, 1 part by weight of α-benzolione 6 and 4,900 parts by weight of chlorobenzene), The coating was dropped on the center of the substrate and spin-coated. A film layer was formed at a rotation speed of 2000 rpm for 10 seconds. As a result, the film thickness was 800 angstroms. 2 ml of a positive photoresist solution (manufactured by Tokyo Chemical Co., Ltd .; OFPR-800) was formed. ), Was dropped on the center of the substrate, and was spin-coated. The film was held at a rotation speed of 500 rpm for 10 seconds, and then maintained at a rotation speed of 200 Orpm for 20 seconds. As a result, the film thickness was approximately 1 / / m. Pre-bake at 30 ° C for 30 minutes. Then, set it to the alignment exposure machine at the same time as the exposure mask, and expose with ultraviolet light to remove the light-emitting layers other than the first light-emitting part and the second light-emitting part. Part. It is developed with a photoresist developer (manufactured by Tokyo Inka Co., Ltd .; NMD-3) for 20 seconds, and then washed with water to remove the photoresist layer in the exposed part. After 30 minutes at 120 ° C, it is borrowed. The reactive ion etching using an oxygen plasma is used to remove the buffer layer and the light-emitting layer from which the photoresist layer has been removed. After all the photoresist is removed with acetone, take 2m 1 of a positive photoresist (manufactured by Tokyo Chemical Co., Ltd .; 〇FPR-8 00), dripped on the center of the substrate, spin-coated. Hold at 500 rpm for 10 seconds, then The film layer was formed at 37 312 / Invention Patent Specification (Supplement) / 92 · 02/91134595 567736 and kept at 2000 rpm for 20 seconds. As a result, the film thickness was approximately 1 // m. Pre-baking at 80 ° C for 30 minutes Then, it is set at the alignment exposure machine at the same time as the exposure mask, and is exposed to ultraviolet rays to form a photoresist layer with a width larger than the width of the first light-emitting portion and the second light-emitting portion by i0 // m.
由光阻顯影液（東京應化公司製；NMD-3)顯影20秒後，進 行水洗，除去曝光部的光阻。以1 2 CTC進行3 0分鐘後續烘 烤，獲得第1發光部被具有較第1發光部及第2發光部的 寬幅各大l〇//m寬度的光阻層保護的基材。 I (第3緩衝層之成膜） 於所獲得的基材上，取〇.5ml的緩衝層塗敷液（BAYER 公司（德）製；B a y t r ο η p )，滴落於基材的中心部，進行旋塗。 以轉速25 OOrpm保持20秒形成膜層。其結果，膜厚形成 爲8 00埃。 (第3發光層之成膜） 作爲第3發光層，於緩衝層上取1 ml藍色發光有機材料 之塗敷液（聚乙烯基咔唑7 〇重量部、巧二唑3 0重量部、二 _ 萘嵌苯1重量部、氯苯4900重量部），滴落於基材的中心 部，進行旋塗。以轉速200 Orpm保持10秒形成膜層。其 結果，膜厚形成爲800埃。 取2ml正型光阻液（東京應化公司製；OFPR- 800)，滴落 於基材的中心部，進行旋塗。以轉速50〇rpm保持10秒， 隨後以轉速20 OOrpm保持20秒形成膜層。其結果，膜厚 可形成約爲1 // m。以8 0 °C進行3 0分鐘預烘。隨後，與曝 光光罩同時設定於對準曝光機，以紫外線曝光欲除去第1 38 312/發明專利說明書(補件)/92-02/91134595 567736 發光部、第2發光部、以及第3發光部以外之發光層之部 分。由光阻顯影液（東京應化公司製；NMD-3)顯影20秒後， 進行水洗，除去曝光部的光阻。以1 2 0 °C進行3 0分鐘後續 烘烤後，藉由使用氧電漿的反應性離子蝕刻，除去被除去 光阻層部分的緩衝層及發光層，獲得第1發光部、第2發 光部及第3發光部受到光阻保護的基材。隨後，利用丙酮 全部除去光阻後，露出圖案處理後之發光層。 以1 00 °C進行1小時乾燥後，於所獲得的基材上，作爲 第2電極層（上部電極）以5 00埃之厚度蒸鍍Ca，又，作爲 保護層以2 5 0 0埃之厚度蒸鍍Ag，製作EL元件。 (EL元件之發光特性之評價） 將ITO電極側連接於正極，將Ag電極側連接於負極， 藉由源儀表施加直流電流。於施加1 0V時，分別從第1發 光部、第2發光部及第3發光部分辨出發光。 (比較例） 於第1發光層及第2發光層的顯影步驟後，除未進行光 阻層的剝離步驟及藉二次光阻層的形成、曝光、及顯影步 驟的’發光層的再保護外，與實施例1相同製作EL元件。 其於第2發光層及第3發光層之顯影時，已有圖案處理過 的發光層溶出，因而產生像素稀薄。 【圖式簡單說明】 圖1(a)〜（m)爲顯示本發明之EL元件之製造方法之第1 實施形態的第1例的步驟圖。 圖2(a)〜（k)爲顯示本發明之EL元件之製造方法之第1 39 312/發明專利說明書(補件)/92-〇2/91134595 567736 實施形態的第2例的步驟圖。 圖3(a)〜（1)爲顯示本發明之EL元件之製造方法之第2 實施形態的第1例的步驟圖。 圖4(a)〜（1)爲顯示本發明之EL元件之製造方法之第2 實施形態的第2例的步驟圖。 圖5 (a)〜（η)爲顯示習知EL元件之製造方法的步驟圖。 元件符號說明 1 基 材 2 第 1 電 極 層 3 緩 衝 層 4 第 1 發 光 層 4， 第 1 發 光 部 5 一 次 光 阻 層 5， 二 次 光 阻 層 6 一 次 光 罩 6， 二 次 光 罩 7 紫 外 線 8 第 2 發 光 層 8， 第 2 發 光 部 9 第 3 發 光 層 9， 第 3 發 光 部 10 第 2 電 極 層 a 端 部 b 端 部 312/發明專利說明書(補件)/92-02/91134595 40 567736 3 1 基材 32 第1電極層 3 3 第1發光層用塗工液 3 3’ 第1發光部 34 正型光阻 3 5 光罩 36 紫外線 37 第2發光層用塗工液 3 7’ 第2發光部 38 第3發光層用塗工液 3 8’ 第3發光部 39 第2電極層 40 EL發光 312/發明專利說明書(補件)/92-02/91134595After developing with a photoresist developer (manufactured by Tokyo Inka Co., Ltd .; NMD-3) for 20 seconds, it was washed with water to remove the photoresist in the exposed portion. Subsequent baking was performed at 12 CTC for 30 minutes to obtain a substrate in which the first light-emitting portion was protected by a photoresist layer having a width larger than each of the first light-emitting portion and the second light-emitting portion by 10 // m. I (film formation of the third buffer layer) On the obtained substrate, 0.5 ml of a buffer layer coating solution (BAYER company (Germany); Bayytr ο η p) was taken and dropped on the center of the substrate Spin coating. A film layer was formed by holding at a rotation speed of 25 OO rpm for 20 seconds. As a result, the film thickness was 800 Angstroms. (Film Formation of the Third Light-Emitting Layer) As the third light-emitting layer, 1 ml of a blue light-emitting organic material coating solution (polyvinylcarbazole 70% by weight, cladiazole 30% by weight, _ 1 part by weight of naphthalene and 4900 by weight of chlorobenzene), dripped on the center of the substrate, and spin-coated. A film layer was formed by holding at a rotation speed of 200 Orpm for 10 seconds. As a result, the film thickness was 800 angstroms. 2 ml of a positive-type photoresist (manufactured by Tokyo Yinghua Co., Ltd .; OFPR-800) was dropped on the center of the substrate and spin-coated. The film was maintained at a rotation speed of 50 rpm for 10 seconds, and then maintained at a rotation speed of 2000 rpm for 20 seconds. As a result, the film thickness can be approximately 1 // m. Pre-bake at 80 ° C for 30 minutes. Then, set it to the alignment exposure machine at the same time as the exposure mask, and expose the first 38 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 567736 light emitting section, second light emitting section, and third light emitting with ultraviolet exposure. The part of the light-emitting layer other than the part. After developing with a photoresist developer (manufactured by Tokyo Inka Co., Ltd .; NMD-3) for 20 seconds, it was washed with water to remove the photoresist in the exposed portion. After 30 minutes of subsequent baking at 120 ° C, the buffer layer and the light-emitting layer from which the photoresist layer has been removed are removed by reactive ion etching using an oxygen plasma to obtain a first light-emitting portion and a second light-emitting portion. And the third light-emitting portion are protected by a photoresist. Subsequently, the photoresist was completely removed with acetone, and then the light-emitting layer after patterning was exposed. After drying at 100 ° C for 1 hour, Ca was vapor-deposited on the obtained substrate as a second electrode layer (upper electrode) at a thickness of 500 angstroms, and as a protective layer at 2500 angstroms. Ag was vapor-deposited to produce an EL element. (Evaluation of the light-emitting characteristics of the EL element) The ITO electrode side was connected to the positive electrode, the Ag electrode side was connected to the negative electrode, and a direct current was applied by a source meter. When 10 V is applied, light emission is recognized from the first light emitting section, the second light emitting section, and the third light emitting section, respectively. (Comparative example) After the development steps of the first light emitting layer and the second light emitting layer, except for the photoresist layer peeling step and the formation, exposure, and development steps of the second photoresist layer, the light emitting layer was reprotected. An EL element was fabricated in the same manner as in Example 1. During the development of the second light-emitting layer and the third light-emitting layer, the light-emitting layer that has been subjected to the pattern treatment is eluted, resulting in thin pixels. [Brief description of the drawings] Figs. 1 (a) to (m) are step diagrams showing a first example of a first embodiment of a method for manufacturing an EL element of the present invention. 2 (a) to (k) are step diagrams showing a second example of the first embodiment of the method for manufacturing an EL device of the present invention, which is No. 1 39 312 / Invention Patent Specification (Supplement) / 92-〇2 / 91134595 567736. 3 (a) to (1) are step diagrams showing a first example of the second embodiment of the method of manufacturing the EL element of the present invention. 4 (a) to (1) are step diagrams showing a second example of the second embodiment of the manufacturing method of the EL element of the present invention. 5 (a) to (η) are step diagrams showing a method for manufacturing a conventional EL element. Element symbol description 1 base material 2 first electrode layer 3 buffer layer 4 first light emitting layer 4, first light emitting portion 5 primary photoresistive layer 5, secondary photoresistive layer 6 primary photomask 6, secondary photomask 7 ultraviolet 8 2nd light-emitting layer 8, 2nd light-emitting portion 9, 3rd light-emitting layer 9, 3rd light-emitting portion 10, 2nd electrode layer a end portion b end portion 312 / Invention Patent Specification (Supplement) / 92-02 / 91134595 40 567736 3 1 Substrate 32 First electrode layer 3 3 Coating liquid for the first light-emitting layer 3 3 'First light-emitting portion 34 Positive photoresist 3 5 Photomask 36 Ultraviolet 37 Coating liquid for the second light-emitting layer 3 7' Second 2 Light-emitting section 38 Coating liquid for the third light-emitting layer 3 8 'Third light-emitting section 39 Second electrode layer 40 EL light-emitting 312 / Invention patent specification (Supplement) / 92-02 / 91134595