1363935 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種光阻組成物，用以感應紫外線、遠 紫外線、X射線、電子線等粒子線等的放射線，其係使用時 具有優良的安全性、塗布性，顯影時具有優良的殘膜率，顯 影後之圖案具有優良的線寬均一性，同時在顯影時亦具有優 良的黏附性。 【先前技術】 在製造積體電路、彩色濾光器、液晶元件等時要求微細 加工，爲滿足如此要求，以往係採用光阻。一般而言，光阻 有正型和負型，通常都是溶解在溶劑中成爲溶液狀態之光阻 組成物。 該光阻組成物係在矽基板、玻璃基板等基板上使用旋 塗、輥塗等眾所周知的塗布法進行塗布後，預烘焙來形成光 阻膜，隨後按照光阻之感光波長範圍，藉由紫外線、遠紫外 線、X射線、電子線等之粒子線等加以曝光' 顯影後，按照 必要來施加乾蝕刻而形成所希望的光阻圖案。 上述光阻組成物所使用之溶劑，以往考慮溶解性、塗布 性‘感度、顯影性、以及形成圖案特性等而選擇使用種種溶 劑。例如，具有優良的上述溶解性、塗布性、光阻形成特性 等各種特性之溶劑，已知有乙二醇一乙醚乙酸酯。然而，近 年來因被指出有對人體安全性的問題，要求一種溶劑，安全 性高而且具有優良的樹脂溶解性、起始劑溶解性而能夠改善 光阻形成特性等性能。 1363935 有文獻掲示使用丙二醇一甲醚乙酸酯等來替代乙二醇 —乙醚乙酸酯作爲溶劑（例如專利文獻1 )作爲此等解決對 策。但是，此等與乙二醇一乙醚乙酸酯比較時被認爲安全性 較高之溶劑’有光阻形成特性及溶解性等特性不充分的問題 存在。例如丙二醇一甲醚乙酸酯時，將光阻塗布在基板上， 因爲成膜時之膜中殘存溶劑量多而使殘膜率、線寬均一性' 顯影時之光阻膜的黏附性等下降。 又’有掲示一種改良樹脂溶解性、起始劑溶解性之技 ® 術’係使用β型丙二醇一甲醚乙酸酯，但是就樹脂溶解性、 起始劑溶解性而言仍不充分（例如專利文獻2)。 [專利文獻1]特公平3-1659號公報 - [專利文獻2]特開平6-324483號公報 . 【發明內容】 本發明之目的係提供一種光阻組成物，具有優良的調製 光阻時之溶解性，不僅可以提升顯影時之光阻膜黏附性之特 性’亦可以提升光阻安定性，而且亦具有優良的安全性。 ® 本發明者等專心硏究結果，發現藉由使用特定的有機溶 劑可以達成上述的目的而完成了本發明。 亦即，本發明係提供一種光阻組成物，含有光阻成分及 有機溶劑，其特徵爲，該有機溶劑係選自於（a 1)烷基之碳數 爲2以上之一丙二醇烷基醚、（a2)二或三丙二醇烷基醚、（a3) ~ ’二或三丙二醇芳基醚、（a4)l，3-丁二醇或是甘油之烷基 醚、（bl)烷基之碳數爲3以上之一丙二醇烷基醚乙酸酯、（b2) 二或三丙二醇烷基醚乙酸酯、（b3)—、二或三丙二醇芳基醚 1363935 乙酸酯、（b4)l,3 -丁二醇或是甘油之烷基醚乙酸酯、以及 (b5)C3.4鏈烷多元醇乙酸酯之組成群中的至少1種。 此等光阻組成物之較佳態樣’有機溶劑係選自於（a D烷 基之碳數爲2以上之一丙二醇烷基醚' U2)二或三丙二醇烷 基醚、（a3)—，二或三丙二醇芳基醚、以及（a4)l,3 -丁二醇或 是甘油之烷基醚之組成群中的至少1種醚類’與選自於（b1’） 一丙二醇烷基醚乙酸酯、（b2)二或三丙二醇烷基醚乙酸酯、 (b3) —、二或三丙二醇芳基醚乙酸酯、（b4)l，3-丁二醇或是甘 ® 油之烷基醚乙酸酯、以及（b5)C3-4鏈烷多元醇乙酸酯之組成 • 群中的至少1種乙酸酯類之組合。 ' 又，前述光阻組成物之其他較佳態樣’有機溶劑係選自 - 於（al，）一丙二醇烷基醚、（a2)二或三丙二醇烷基醚、（a3) — . 二或三丙二醇芳基醚、以及（a4 )1,3-丁二醇或是甘油之烷基 醚之組成群中的至少1種醚類，與選自於（bl)烷基之碳數爲 3以上之一丙二醇烷基醚乙酸酯、（b 2)二或三丙二醇烷基醚 乙酸酯、（1)3)—、二或三丙二醇芳基醚乙酸酯、（b4) 1,3-丁二 ^ 醇或是甘油之烷基醚乙酸酯、以及（b5)C3_4鏈烷多元醇乙酸 酯之組成群中的至少1種乙酸酯類之組合。 前述光阻組成物亦可以含更有選自於羧酸燒基酯類及 脂肪族酮類中至少1種溶劑作爲有機溶劑。 又，在本說明書，「丙二醇」係包含α型丙二醇（1，2· 丙二醇）及β型丙二醇（1,3-丙二醇）。 依照本發明，係提供一種光阻組成物，可以提升調製光 阻時之溶解性、飛躍性地提升光阻安定性，同時可以減少光 1363935 阻成膜時光阻膜中之殘存溶劑量，提升殘膜率、線寬均一 性、顯影時之光阻膜黏附性等特性，而且具有高安全性。 【實施方式】 在本發明所使.用之有機溶劑係選自於（a n烷基之碳數 爲2以上之一丙二醇烷基醚、（a2)二或三丙二醇烷基醚、（a3) 一，二或三丙二醇芳基醚、（a4)1,3-丁二醇或是甘油之烷基 醚、（bl)烷基之碳數爲3以上之一丙二醇烷基醚乙酸酯、（b2) 二或三丙二醇烷基醚乙酸酯、（b3)~、二或三丙二醇芳基醚 • 乙酸酯、（b 4)1，3-丁二醇或是甘油之烷基醚乙酸酯、以及 • (b5)C3.4鏈烷多元醇乙酸酯之組成群中的至少1種溶劑。 此等有機溶劑除了可以各自單獨使用以外，可以用任意 -‘ 比例混合2種以上使用。特別是前述（ai)〜（a4)之酸類和前述 . (bl)〜（b5)之乙酸酯類係各自至少存在1種之混合系爲佳。 又’前述各有機溶劑之「烷基」以甲基、乙基、丙基、丁基 等碳數1~4之直鏈狀或是支鏈狀院基爲佳。 前述烷基之碳數2以上之一丙二醇烷基醚（ai)可以以舉 ® 出的有例如丙二醇-1-乙醚、丙二醇-1-正丙醚、丙二醇-1-正 丁醚等一丙二醇一烷基醚、以及對應之一丙二醇二烷基醚 (二個烷基可以相同亦可以不同）等。 前述二或三丙二醇烷基醚（a2)中，二丙二醇烷基醚可以 舉出的有二丙二醇-1-甲醚 '二丙二醇-1-乙醚、二丙二醇-1-正丙醚、二丙二醇-1-正丁醚等二丙二醇一烷基醚，以及對 .應之二丙二醇二烷基醚（二個烷基可以相同亦可以不同） 等。又，三丙二醇烷基醚可以舉出的有三丙二醇-1-甲醚、 1363935 三丙二醇-1-乙醚、三丙二醇-卜正丙醚、三丙二醇-1-正丁醚 等三丙二醇一烷基醚，以及對應之三丙二醇二烷基醚（二個 烷基可以相同亦可以不同）等。 前述一，二或三丙二醇芳基醚（a3)中，一丙二醇芳基醚 可以舉出的有一丙二醇一苯醚等一丙二醇一芳基醚，以及對 應之一丙二醇二芳基醚等。二丙二醇芳基酸可以舉出的有二 丙二醇一苯醚等二丙二醇一芳基醚，以及對應之二丙二醇二 芳基醚等。三丙二醇芳基醚可以舉出的有三丙二醇一苯醚等 • 三丙二醇一芳基醚，以及對應之三丙二醇二芳基醚等。 ' 前述1，3-丁二醇或是甘油之烷基醆（a4)中，1,3-丁二醇 • 烷基醚係一烷基醚和二烷基醚都可以使用。一烷基醚可以舉 - 出的有1,3-丁二醇一甲醚、1，3-丁二醇一乙醚、1,3-丁二醇 —正丙醚、1,3-丁二醇一正丁醚等。亡烷基醚可以例示的有 對應前述1,3-丁二醇一烷基醚之1,3-丁二醇二烷基醚（二個 烷基可以相同亦可以不同）。 甘油烷基醚含有甘油一烷基醚、甘油二烷基醚、甘油三 ^ 烷基醚。甘油烷基醚之代表性例子可以舉出的有甘油一甲 醚、甘油二甲醚、甘油三甲醚、甘油一乙醚、甘油二乙醚、 甘油三乙醚、甘油一正丙醚、甘油二正丙醚、甘油三正丙醚、 甘油一正丁醚、甘油二正丁醚、甘油三正丁醚等。 前述烷基之碳數爲3以上之一丙二醇烷基醚乙酸酯 (bl)，可以舉出的有丙二醇正丙醚乙酸酯 '丙二醇正丁醚乙 酸酯等。 前述二或三丙二醇烷基醚乙酸酯（b2)中，二丙二醇烷基 1363935 —Cm烷基醚、二丙二醇一甲酸.乙酸酯等二丙二醇~ Ch 烷基醚乙酸酯、丙二醇—丙醚等丙二醇—C3_4烷基醚、丙二 醇一丙醚乙酸酯等丙二醇一C3-4烷基醚乙酸酯、1,3-丁二醇 —乙醚等1，3-丁二醇一 Cm烷基醚、1,3-丁二醇一乙醚乙酸 酯等1，3-丁二醇一Cu烷基醚乙酸酯' 1，3-丁二醇二乙酸 酯、甘油三乙酸酯、丙二醇一苯醚等丙二醇苯醚類、丙二醇 苯醚乙酸酯等。 單獨使用可以得到優良效果之溶·劑，可以舉出的有二丙 C 二醇一甲醚等二丙二醇一-4烷基醚、丙二醇一丙醚等丙二 醇一 C3-4烷基醚、丙二醇一丙醚乙酸酯等丙二醇一C3-4烷 基酸乙酸酯、1,3 -丁二醇一乙酸等1，3 -丁二醇一.Ci-4院基 • 醚、1,3 -丁二醇二乙酸酯、甘油三乙酸酯等。 . 並用2種以上有機溶劑時之較佳組合，可以舉出的有（1) 選自於（al)烷基之碳數爲2以上之一丙二醇烷基醚、（a2)二 或三丙二醇烷基醚、U3)—，二或三丙二醇芳基醚、以及 (a4)l，3-丁二醇或是甘油之烷基醚之組成群中的至少1種醚 C 類（二醇醚類），與選自於（bl’）一丙二醇烷基醚乙酸酯、（b2) 二或三丙二醇烷基醚乙酸酯、（b 3)—、二或三丙二醇芳基酸 乙酸酯、（b4)1，3-丁二醇或是甘油之烷基醚乙酸酯、以及 (b5)C3_4鏈烷多元醇乙酸酯之組成群中的至少1種乙酸酯類 之組合，（2)選自於（al，）一丙二醇烷基醚、（a2)二或三丙二 醇烷基醚、（a3)—，二或三丙二醇芳基醚、以及（a4)l，3-丁二 醇或是甘油之烷基醚之組成群中的至少1種醚類（二醇^ 類），與選自於（bl)烷基之碳數爲3以上之一丙二醇烷基醚乙 -11- 1363935 酸酯、（b2)二或三丙二醇烷基醚乙酸酯、（b 3) —、二或三丙 二醇芳基醚乙酸酯、（b4)l,3-丁二醇或是甘油之烷基醚乙酸 酯、以及（b5)C3.4鏈烷多元醇乙酸酯之組成群中的至少1種 乙酸酯類之組合。 又，並用2種以上有機溶劑時之其他較佳組合可以舉出 的有（3)選自於（al’）_丙二醇烷基醚、（a2)二或三丙二醇烷基 醚、（a3)—，二或三丙二醇芳基醚、（a4)l，3-丁二醇或是甘油 之烷基醚、（bl’）一丙二醇烷基醚乙酸酯、（b2)二或三丙二醇 # 烷基醚乙酸酯、（b3)—、二或三丙二醇芳基醚乙酸酯、（b4)l，3- - 丁二醇或是甘油之烷基醚乙酸酯之組成群中的至少1種，與 (b5)C3-4鏈烷多元醇乙酸酯（特是C3_4鏈烷多元醇聚乙酸酯） . 之組合。 (al) 、 （a2) 、 （a3) 、 （a4) 、 （bl) 、 （b2) 、 （b3) 、 （b4) 、 （b5) 係與前述一樣。前述（al’）一丙二醇烷基醚係除了（al)所包含 的溶劑以外，可以舉出的有一丙二醇一甲醚、一丙二醇二甲 醚等。（bl’）一丙二醇烷基醚乙酸酯係除了（bl)所包含的溶劑 # 以外’可以舉出的有一丙二醇甲醚乙酸酯、一丙二醇一乙醚 乙酸酯等。 更具體的是2種以上的混合溶劑，可以舉出的有例如丙 二醇丙醚和丙二醇丙醚乙酸酯、二丙二醇丙醚和二丙二醇丙 醚乙酸酯、三丙二醇正丁醚和三丙二醇正丁醚乙酸酯、丙二 醇苯醚和丙二醇苯醚乙酸酯、1,3-丁二醇正丙醚和1,3-丁二 醇正丙醚乙酸酯、1，3-丙二醇甲醚乙酸酯和1，3-丙二醇甲醚 二乙酸酯、或是甘油一甲醚和甘油三甲醚。特別是以多元醇 -12- 1363935 本發明所使用之較佳光阻材料，可以舉出的有苯醌二疊 氮系感光劑和鹼可溶性樹脂所組成之物。苯醌二疊氮系感光 劑和鹼可溶性樹脂所組成之正型光阻，以往已知有各種之 物，該等在本發明都可以使用，沒有特別限定之物。 此等由苯醌二疊氮系感光劑和鹼可溶性樹脂所組成之 正型光阻所使用之苯醌二疊氮系感光劑的例子可以舉出的 有例如1,2-苯醌二疊氮-4-磺酸、1，2-萘醌二疊氮-4-磺酸、 1，2-萘醌二疊氮-5-磺酸、此等磺酸的酯或醯胺等。磺酸的酯 φ 或醯胺化合物可以藉由使該苯醌二疊氮磺酸或是苯醌二疊 氮磺醯氯與具有羥基之化合物或是具有胺基之化合進行縮 . 合反應來得到。 ^ 具有羥基的化合物可以舉出的有二羥基二苯基酮、三羥 基二苯基酮、四羥基Z：苯基酮、苯酚、萘酚、對甲氧基苯酚、 雙酚A、焦耳苯酚、焦掊酚、焦掊酚甲醚、間戊酮酸、α，(χ’，α”-參（4-羥基苯基）-1,3,5-三異丙基苯、參（羥基苯基）甲烷等， 又，具有胺基之化合物可以舉出的有苯胺、對胺基二苯基胺 Φ 等。此等苯醌二疊氮系感光劑可以單獨使用或是以2種以上 之混合物的形式來使用。 另一方面，鹼可溶性樹脂可以舉出的有例如酚醛清漆樹 脂、聚乙烯苯酚、聚乙烯醇、丙烯酸或是甲基丙烯酸之共聚 物等。 酚醛清漆樹脂可以舉出的有例如苯酚、鄰甲酚、間甲 酚、對甲酚、二甲苯酚、三甲基苯酚、三級丁基苯酚、乙基 苯酚、2-萘酚、1，3-二羥基萘等酚類之1種或2種以上與甲 -15- 1363935 醛、聚甲醛等醛類之縮聚生成物。此等酚醛清漆樹脂等鹼可 溶性樹脂可以按照必要組合2種以上來使用，而且爲了改善 皮膜形成性等，亦可以添加其他樹脂。又，亦可以使用酚類 和醛類或是酮類的縮聚物與苯醌二疊氮磺酸之酯來作爲苯 醌疊氮磺酸酯。 上述苯醌二疊氮系感光劑和鹼可溶性樹脂之使用比 例，具體上依照所使用之感光劑及鹼可溶性樹脂而有所不 同，通常重量比以1:1~1:20之範圍爲佳，但是本發明並未限 籲定於此。 又，化學增幅型光阻亦是本發明所可以使用之較佳正型 - 光阻。該化學增幅型光阻可以使用放射線照射來產生酸，藉 - 由該酸之催化作用所產生的化學變化，來使放射線照射部分 對顯影液產生溶解性變化而形成圖案，例如含有：酸產生化 合物，藉由放射線照射會產生酸；以及含有酸感應性基之樹 脂，在酸的存在下會分解而生成如酚性羥基或是羰基之鹼可 溶性基。 Φ 藉由照射上述放射線可以產生酸之酸產生化合物可以 舉出的有如雙（異丙基磺醯）重氮甲烷之雙磺醯重氮甲烷 類、如甲基磺醯對甲苯磺醯甲烷之雙磺醯烷類、如環己基磺 醯環己基羰基重氮甲烷之磺醯羰基重氮甲烷類、如2-甲基 -2-(4-甲基苯基磺醯）丙醯苯之磺醯-基烷類、如2-硝基苄基 對甲苯酸酯之硝基苄基磺酸酯類、如焦掊酚參甲烷磺酸酯之 烷基或芳基磺酸酯類、如苯偶姻甲苯磺酸酯之苯偶姻磺酸醋 類、如N-(三氟甲基磺醯羥基）酞醯亞胺之N-磺醯氧基醯亞 -16- 1363935 降低鹼可溶性樹脂的溶解性控制效果或是促進可溶性樹脂 的溶解性之化合物，如此之物亦可以使用。 此等光阻成分可以溶解在有機溶劑中來使用於本發明 的光阻組成物。光阻成分的比例可以按照所使用光阻的種 類、溶劑的種類而適當地設定，通常相對於光阻固體成分爲 100重量份，有機溶劑使用50~3 000重量份，以70〜20 00重 量份爲佳，以1〇〇~1〇〇〇重量份爲更佳。特別是使用1〇〇~500 重量份時，能夠充分顯示鹼可溶性樹脂的高溶解性。1363935 IX. Description of the Invention: [Technical Field] The present invention relates to a photoresist composition for sensing radiation such as ultraviolet rays, far ultraviolet rays, X-rays, electron beams, and the like, which are excellent in use. The safety and coating properties have an excellent residual film ratio during development, and the developed pattern has excellent line width uniformity and excellent adhesion at the time of development. [Prior Art] When manufacturing an integrated circuit, a color filter, a liquid crystal element, or the like, microfabrication is required, and in order to satisfy such a requirement, a photoresist is conventionally used. Generally, the photoresist has a positive type and a negative type, and is usually a photoresist composition which is dissolved in a solvent to be in a solution state. The photoresist composition is applied onto a substrate such as a tantalum substrate or a glass substrate by a well-known coating method such as spin coating or roll coating, and then prebaked to form a photoresist film, followed by ultraviolet light in accordance with the photosensitive wavelength range of the photoresist. A particle line or the like of a far ultraviolet ray, an X-ray, an electron beam, or the like is exposed. After development, dry etching is applied as necessary to form a desired photoresist pattern. In the solvent used for the above-mentioned photoresist composition, various solvents have been conventionally selected in consideration of solubility, applicability, sensitivity, developability, and patterning properties. For example, ethylene glycol monoethyl ether acetate is known as a solvent having various properties such as excellent solubility, coating properties, and photoresist forming properties. However, in recent years, it has been pointed out that there is a problem of human safety, requiring a solvent, high safety, excellent resin solubility, and solubility of an initiator to improve properties such as photoresist formation characteristics. 1363935 It has been reported in the literature that propylene glycol monomethyl ether acetate or the like is used instead of ethylene glycol-ether acetate as a solvent (for example, Patent Document 1) as such a solution. However, such a solvent which is considered to be safer when compared with ethylene glycol monoethyl ether acetate has a problem that characteristics such as photoresist formation characteristics and solubility are insufficient. For example, when propylene glycol monomethyl ether acetate is used, the photoresist is applied to the substrate, and the amount of residual solvent in the film at the time of film formation increases the residual film ratio and line width uniformity, and the adhesion of the photoresist film during development. decline. In addition, there is a technique for improving the solubility of a resin and the solubility of an initiator, which uses beta-propylene glycol monomethyl ether acetate, but it is still insufficient in terms of resin solubility and solubility of the initiator (for example) Patent Document 2). [Patent Document 1] Japanese Patent Laid-Open No. Hei 6-324483. SUMMARY OF THE INVENTION An object of the present invention is to provide a photoresist composition having excellent modulation photoresist. Solubility not only enhances the adhesion of the photoresist film during development, but also improves the stability of the photoresist, and it also has excellent safety. The inventors of the present invention have intensively studied the results and found that the above object can be attained by using a specific organic solvent. That is, the present invention provides a photoresist composition comprising a photoresist component and an organic solvent, characterized in that the organic solvent is selected from the group consisting of (a 1) an alkyl group having a carbon number of 2 or more and a propylene glycol alkyl ether. , (a2) di or tripropylene glycol alkyl ether, (a3) ~ 'di or tripropylene glycol aryl ether, (a4) l, 3-butanediol or alkyl ether of glycerol, (bl) alkyl carbon a number of 3 or more of propylene glycol alkyl ether acetate, (b2) di or tripropylene glycol alkyl ether acetate, (b3)-, di- or tripropylene glycol aryl ether 1363935 acetate, (b4)l, At least one of a composition group of 3-butanediol or an alkyl ether acetate of glycerin and (b5) a C3.4 alkane polyol acetate. Preferred Embodiments of Such Photoresist Compositions 'The organic solvent is selected from (a D alkyl group having a carbon number of 2 or more and one propylene glycol alkyl ether 'U2) di or tripropylene glycol alkyl ether, (a3)- , a di- or tri-propylene glycol aryl ether, and at least one ether in the group consisting of (a4) 1, 3-butanediol or an alkyl ether of glycerol, and an alkyl group selected from (b1')-propylene glycol Ether acetate, (b2) di or tripropylene glycol alkyl ether acetate, (b3)-, di- or tripropylene glycol aryl ether acetate, (b4) 1, 3-butanediol or glycerol® oil A combination of alkyl ether acetate and (b5) C3-4 alkane polyol acetate; at least one acetate in the group. 'Another preferred aspect of the foregoing photoresist composition' is an organic solvent selected from the group consisting of - (al,) propylene glycol alkyl ether, (a2) di or tripropylene glycol alkyl ether, (a3) - At least one ether selected from the group consisting of tripropylene glycol aryl ether and (a4) 1,3-butylene glycol or alkyl ether of glycerin, and carbon number selected from (bl) alkyl group is 3 or more One of propylene glycol alkyl ether acetate, (b 2) di or tripropylene glycol alkyl ether acetate, (1) 3), di or tripropylene glycol aryl ether acetate, (b4) 1,3- A combination of at least one of the constituent groups of butyl alcohol or glycerol alkyl ether acetate and (b5) C3_4 alkane polyol acetate. The photoresist composition may contain at least one solvent selected from the group consisting of carboxylic acid alkyl esters and aliphatic ketones as an organic solvent. Further, in the present specification, "propylene glycol" includes α-propylene glycol (1,2·propylene glycol) and β-propylene glycol (1,3-propanediol). According to the present invention, there is provided a photoresist composition which can improve the solubility in modulating a photoresist, and drastically improve the stability of the photoresist, and at the same time, can reduce the amount of residual solvent in the photoresist film when the light 1363935 is formed, and enhance the residual amount. It has high film properties, uniformity of line width, adhesion of photoresist film during development, and high safety. [Embodiment] The organic solvent used in the present invention is selected from the group consisting of (an alkyl group having a carbon number of 2 or more, one propylene glycol alkyl ether, (a2) di or tripropylene glycol alkyl ether, (a3) one , di or tripropylene glycol aryl ether, (a4) 1,3-butanediol or alkyl ether of glycerol, (bl) alkyl group having 3 or more propylene glycol alkyl ether acetate, (b2 Di- or tripropylene glycol alkyl ether acetate, (b3)~, di- or tri-propylene glycol aryl ether• acetate, (b 4) 1,3-butanediol or alkyl ether acetate of glycerol And (b5) at least one solvent in the group of C3.4 alkane polyol acetates. These organic solvents may be used alone or in combination of two or more kinds in any ratio. It is preferable that the acid of the above (ai) to (a4) and the acetate of the above (b1) to (b5) are each a mixture of at least one of the above-mentioned organic solvents. A linear or branched chain base having a carbon number of 1 to 4 such as an ethyl group, an ethyl group, a propyl group or a butyl group is preferred. The alkyl group having a carbon number of 2 or more and one propylene glycol alkyl ether (ai) may be mentioned.There are, for example, propylene glycol monoalkyl ether such as propylene glycol-1-ethyl ether, propylene glycol-1-n-propyl ether, propylene glycol-1-n-butyl ether, and one propylene glycol dialkyl ether (the two alkyl groups may be the same) In the above di- or tri-propylene glycol alkyl ether (a2), dipropylene glycol alkyl ether may be exemplified by dipropylene glycol-1-methyl ether 'dipropylene glycol-1-ethyl ether, dipropylene glycol-1-n-propyl Dipropylene glycol monoalkyl ether such as ether, dipropylene glycol-1-n-butyl ether, and dipropylene glycol dialkyl ether (the two alkyl groups may be the same or different), etc. Further, tripropylene glycol alkyl ether may be Tripropylene glycol monoalkyl ethers such as tripropylene glycol-1-methyl ether, 1363935 tripropylene glycol-1-ethyl ether, tripropylene glycol-bu-propyl ether, tripropylene glycol-1-n-butyl ether, and the corresponding tripropylene glycol dialkyl ether are mentioned. The ether (the two alkyl groups may be the same or different), etc. In the above-mentioned mono-, di- or tripropylene glycol aryl ether (a3), the monopropylene glycol aryl ether may be a propylene glycol monoaryl group such as propylene glycol monophenyl ether. Ether, and corresponding one of propylene glycol diaryl ether, etc. Dipropylene glycol aryl acid Examples thereof include dipropylene glycol monoaryl ether such as dipropylene glycol monophenyl ether, and corresponding dipropylene glycol diaryl ether. The tripropylene glycol aryl ether may, for example, be tripropylene glycol monophenyl ether or the like; • tripropylene glycol monoaryl ether And the corresponding tripropylene glycol diaryl ether, etc. 'In the above 1,3-butanediol or glycerol alkyl hydrazine (a4), 1,3-butanediol • alkyl ether is a monoalkyl ether and Dialkyl ethers can be used. Monoalkyl ethers can be exemplified by 1,3-butanediol monomethyl ether, 1,3-butanediol monoethyl ether, and 1,3-butylene glycol-n-propyl ether. 1,3-butanediol-n-butyl ether, etc. The alkyl ether can be exemplified by 1,3-butanediol dialkyl ether corresponding to the aforementioned 1,3-butanediol monoalkyl ether (two The alkyl groups may be the same or different). The glyceryl alkyl ether contains glyceryl monoalkyl ether, glycerin dialkyl ether, and glycerol trialkyl ether. Representative examples of the glyceryl alkyl ether include glyceryl monomethyl ether, glyceryl dimethyl ether, glyceryl trimethyl ether, monoethyl glycerol, glyceryl diethyl ether, triethyl glycerol, glycerol mono-n-propyl ether, and glycerol di-n-propyl ether. , triglyceride, glycerol mono-n-butyl ether, di-n-butyl glycerol, tri-n-butyl butyl ether and the like. The propylene glycol alkyl ether acetate (bl) having a carbon number of the alkyl group of 3 or more may be propylene glycol n-propyl ether acetate, propylene glycol n-butyl ether acetate or the like. In the above di- or tripropylene glycol alkyl ether acetate (b2), dipropylene glycol alkyl 1363935-Cm alkyl ether, dipropylene glycol monocarboxylic acid, acetate, etc. dipropylene glycol ~ Ch alkyl ether acetate, propylene glycol - C Propylene glycol such as ether, C3_4 alkyl ether, propylene glycol monopropyl ether acetate, etc., 1,3-butanediol-Cm alkyl group such as propylene glycol-C3-4 alkyl ether acetate, 1,3-butanediol-ether 1,3-butanediol-Cu alkyl ether acetate such as ether, 1,3-butanediol monoethyl ether acetate, 1,3-butanediol diacetate, triacetin, propylene glycol Propylene glycol phenyl ether such as monophenyl ether, propylene glycol phenyl ether acetate, and the like. A solvent which can obtain an excellent effect alone may, for example, be dipropylene glycol mono-4-alkyl ether such as dipropyl C diol monomethyl ether or propylene glycol mono-C3-4 alkyl ether such as propylene glycol monopropyl ether or propylene glycol. Propylene glycol such as propyl ether acetate-C3-4 alkyl acid acetate, 1,3-butanediol monoacetic acid, etc. 1,3 - butanediol-Ci-4, a base, ether, 1,3 - Diol diacetate, triacetin, and the like. Further preferred combinations of two or more organic solvents include (1) a propylene glycol alkyl ether selected from the group consisting of (al) alkyl groups having 2 or more carbon atoms, and (a2) di or tripropylene glycol alkane. At least one ether C (diol ether) of a group consisting of a group of ethers, U3)-, di- or tri-propylene glycol aryl ethers, and (a4) l,3-butanediol or an alkyl ether of glycerol And selected from (bl')-propylene glycol alkyl ether acetate, (b2) di or tripropylene glycol alkyl ether acetate, (b 3)-, di- or tripropylene glycol aryl acid acetate, ( B4) a combination of at least one of 1,3-butanediol or an alkyl ether acetate of glycerin and (b5) a C3_4 alkane polyol acetate, (2) selected From (al,) propylene glycol alkyl ether, (a2) di or tripropylene glycol alkyl ether, (a3)-, di- or tri-propylene glycol aryl ether, and (a4) l, 3-butanediol or glycerol At least one ether (diol type) in the group consisting of alkyl ethers, and one or more propylene glycol alkyl ethers B-11-1363935 acid ester having a carbon number selected from (bl) alkyl groups of 3 or more, (b2) di or tripropylene glycol alkyl ether acetate (b 3) —, di or tripropylene glycol aryl ether acetate, (b4) 1, 3-butanediol or alkyl ether acetate of glycerol, and (b5) C3.4 alkanol polyol B A combination of at least one acetate in the composition group of the acid ester. Further, in another preferred combination of two or more kinds of organic solvents, (3) is selected from (al')-propylene glycol alkyl ether, (a2) di or tripropylene glycol alkyl ether, (a3)- , di or tripropylene glycol aryl ether, (a4) 1, 3-butanediol or alkyl ether of glycerol, (bl') monopropylene glycol alkyl ether acetate, (b2) di or tripropylene glycol # alkyl At least one of a group consisting of ether acetate, (b3)-, di- or tri-propylene glycol aryl ether acetate, (b4) 1, 3-butanediol or alkyl ether acetate of glycerol And (b5) a combination of C3-4 alkane polyol acetate (specifically C3_4 alkane polyol polyacetate). (al), (a2), (a3), (a4), (bl), (b2), (b3), (b4), (b5) are as described above. The (al')-propylene glycol alkyl ether may, for example, be propylene glycol monomethyl ether or monopropylene glycol dimethyl ether, in addition to the solvent contained in (al). (bl') monopropylene glycol alkyl ether acetate is propylene glycol methyl ether acetate, monopropylene glycol monoethyl ether acetate, etc., other than the solvent # contained in (bl). More specifically, two or more kinds of mixed solvents include, for example, propylene glycol propyl ether and propylene glycol propyl ether acetate, dipropylene glycol propyl ether and dipropylene glycol propyl ether acetate, tripropylene glycol n-butyl ether, and tripropylene glycol. Butyl ether acetate, propylene glycol phenyl ether and propylene glycol phenyl ether acetate, 1,3-butylene glycol n-propyl ether and 1,3-butylene glycol n-propyl ether acetate, 1,3-propanediol methyl ether acetate And 1,3-propanediol methyl ether diacetate, or glycerol monomethyl ether and glyceryl trimethyl ether. In particular, a preferred photoresist material for use in the present invention is a polyhydric alcohol -12-1363935, which is exemplified by a benzoquinone diazide sensitizer and an alkali-soluble resin. A positive type resist composed of a benzoquinonediazide-based sensitizer and an alkali-soluble resin is known in the art, and these can be used in the present invention, and are not particularly limited. Examples of the benzoquinone diazide sensitizer used in the positive resist composed of the benzoquinonediazide sensitizer and the alkali-soluble resin include, for example, 1,2-benzoquinonediazide. 4-sulfonic acid, 1,2-naphthoquinonediazide-4-sulfonic acid, 1,2-naphthoquinonediazide-5-sulfonic acid, ester of such sulfonic acid or decylamine. The ester φ or decylamine compound of the sulfonic acid can be obtained by shrinking the benzoquinonediazidesulfonic acid or benzoquinonediazide sulfonium chloride with a compound having a hydroxyl group or having an amine group. . ^ A compound having a hydroxyl group may, for example, be dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxy Z: phenyl ketone, phenol, naphthol, p-methoxyphenol, bisphenol A, pyrophenol, Pyrogallol, pyrogallol, isovaleronic acid, α, (χ', α"-gin (4-hydroxyphenyl)-1,3,5-triisopropylbenzene, cis (hydroxyphenyl) Further, examples of the compound having an amine group include aniline and p-aminodiphenylamine Φ. These quinonediazide sensitizers may be used singly or in combination of two or more kinds. On the other hand, the alkali-soluble resin may, for example, be a novolac resin, a polyvinyl phenol, a polyvinyl alcohol, a copolymer of acrylic acid or methacrylic acid, etc. The novolak resin may, for example, be phenol. One of phenols such as o-cresol, m-cresol, p-cresol, xylenol, trimethylphenol, tert-butylphenol, ethylphenol, 2-naphthol, and 1,3-dihydroxynaphthalene Or a polycondensation product of two or more kinds of aldehydes such as a -15- 1363935 aldehyde or a polyoxymethylene. The soluble resin may be used in combination of two or more kinds as necessary, and other resins may be added for the purpose of improving film formation properties, etc. Further, a polycondensate of phenols and aldehydes or ketones and benzoquinonediazide may be used. The acid ester is used as the benzoquinone azide sulfonate. The ratio of the above benzoquinone diazide sensitizer and the alkali-soluble resin is specifically different depending on the sensitizer and the alkali-soluble resin to be used, and the usual weight ratio Preferably, the range of 1:1 to 1:20 is preferred, but the invention is not limited thereto. Further, the chemically amplified photoresist is also a preferred positive type-resistance which can be used in the present invention. The type of photoresist can be irradiated with radiation to generate an acid, and a chemical change caused by the catalytic action of the acid causes the radiation irradiating portion to form a pattern by changing the solubility of the developing solution, for example, containing an acid generating compound. The radiation generates an acid; and the resin containing an acid-sensitive group decomposes in the presence of an acid to form an alkali-soluble group such as a phenolic hydroxyl group or a carbonyl group. Φ By irradiating the above-mentioned radiation The acid generating acid of the acid can be exemplified by a bis-sulfonyldiazomethane such as bis(isopropylsulfonium)diazomethane, a disulfolane such as methylsulfonium-toluenesulfonate methane, a sulfonyl carbonyl diazomethane such as cyclohexylsulfonylcyclohexylcarbonyldiazomethane, such as 2-methyl-2-(4-methylphenylsulfonyl)propene benzene sulfonyl-alkane, such as Nitrobenzyl sulfonate of 2-nitrobenzyl p-toluate, alkyl or aryl sulfonate such as pyrogallol methanesulfonate, benzene such as benzoin tosylate Amaranthal sulfonic acid vinegar, such as N-(trifluoromethylsulfonylhydroxy) quinone imine N-sulfonyloxy sulfonium-16- 1363935 reduces the solubility control effect of alkali-soluble resin or promotes soluble resin The soluble compound can also be used. These photoresist components can be dissolved in an organic solvent for use in the photoresist composition of the present invention. The ratio of the photoresist component can be appropriately set according to the type of the resist to be used and the type of the solvent, and is usually 100 parts by weight based on the solid content of the resist, and 50 to 3,000 parts by weight of the organic solvent, and 70 to 200 00 by weight. It is preferably a part, preferably 1 part by weight to 1 part by weight. In particular, when it is used in an amount of from 1 to 500 parts by weight, the high solubility of the alkali-soluble resin can be sufficiently exhibited.
又，該等光阻組成物可以按照使用目的而適當地調配表 面活性劑、敏化劑等以往眾所周知之各種添加劑。又，若可 以溶解於水時亦可以添加水。 本發明之光阻組成物可以使用於半導體元件的製造或 是液晶顯示元件的製造等種種的用途，其中以作爲半導體元 件的製造或是液晶顯示元件的製造用之光阻組成物爲佳。使 用本發明之光阻組成物來形成光阻圖案，例如以下述之方式 進行。 首先，本發明之光阻組成物係藉由將光阻原料溶解在上 述溶劑中來製造，該製得之本發明的光阻組成物按照必要藉 由過濾器過濾來去除不溶物，可以使用旋塗、輥塗、逆輥塗 布、流延塗布、刮刀塗布等以往眾所知的塗布法在矽、玻璃 等基板上塗布，使預塗後的膜厚爲例如0.01〜1000微米。 塗布於基板上之光阻組成物，例如在熱板上進行預烘烤 來去除溶劑，形成光阻膜。預烘烤之溫度爲依照所使用的溶 劑或是光阻的種類而不同’通常爲3〇~2〇〇°c，以在50〜15〇t 1363935 程度之溫度進行爲佳。 在形成光阻膜進行後曝光，因爲依照所使用之光阻而有 各自有不同的感光區域，可以按照光阻的感光區域來使用曝 先光源進fr曝先。曝先可以使用例如闻壓水銀燈、齒素金屬 燈、超商壓水銀燈、KrF準分子雷射、ArF準分子雷射、F2 雷射、軟X射線照射裝置、電子線描繪裝置等眾所周知的照 射裝置，按照必要通過遮光罩，藉由紫外線、遠紫外線、X 射線、電子線等來進行預定圖案形狀之照射。曝光後，爲了 % 改善顯影性、解像度、圖案形狀等，按照必要進行後烘烤 後、進行顯影。又，顯影後若有必要時爲了去除反射防止膜， 藉由氣體電漿等來進行乾式蝕刻，形成光阻圖案。Further, these photoresist compositions can be appropriately blended with various conventionally known additives such as a surfactant and a sensitizer, depending on the purpose of use. Further, water may be added if it can be dissolved in water. The photoresist composition of the present invention can be used for the production of a semiconductor element or the production of a liquid crystal display element, and is preferably used as a semiconductor element or a photoresist composition for producing a liquid crystal display element. The photoresist pattern is formed using the photoresist composition of the present invention, for example, in the following manner. First, the photoresist composition of the present invention is produced by dissolving a photoresist material in the above solvent, and the obtained photoresist composition of the present invention is filtered by a filter to remove insoluble matter as necessary, and may be used. A conventionally known coating method such as coating, roll coating, reverse roll coating, cast coating, or doctor blade coating is applied to a substrate such as ruthenium or glass to have a film thickness of, for example, 0.01 to 1000 μm after precoating. The photoresist composition coated on the substrate is pre-baked on a hot plate to remove the solvent to form a photoresist film. The prebaking temperature is different depending on the type of solvent or photoresist used, and is usually 3 〇 to 2 〇〇 ° c, preferably at a temperature of 50 to 15 〇 t 1363935. After the photoresist film is formed for post-exposure, since there are different photosensitive regions depending on the photoresist used, the exposure light source can be used in accordance with the photosensitive region of the photoresist. Well-known illumination devices such as a smear-pressure mercury lamp, a dentate metal lamp, a super-compressed mercury lamp, a KrF excimer laser, an ArF excimer laser, an F2 laser, a soft X-ray irradiation device, and an electron beam drawing device can be used for exposure. The predetermined pattern shape is irradiated by ultraviolet rays, far ultraviolet rays, X rays, electron lines, or the like through a hood as necessary. After the exposure, in order to improve the developability, the resolution, the pattern shape, and the like, it is post-baked as necessary and developed. Further, in order to remove the antireflection film if necessary after the development, dry etching is performed by gas plasma or the like to form a photoresist pattern.
上述光阻顯影係使用通常的顯影液，係利用曝光區域和 未曝光區域之對溶劑之溶解性或是對鹼溶液之溶解性差來 進行。鹼性顯影液可以使用溶解有氫氧化鈉、氫氧化鉀、碳 酸鈉、矽酸鈉等無機鹼類、氨、乙胺、二乙胺' 三乙胺、二 乙基乙醇胺、三乙醇胺、苄胺等胺類、甲醯胺等胺類、氫氧 化四甲基銨（TMAH)、氫氧化四乙基銨、膽鹼等第4級銨鹽 類、吡咯、哌阱等環狀胺類等之水溶液或是水性溶液， [實施例] 以下’藉由實施例具體地說明本發明，但是本發明並不 限定於此》 實施例1〜1 2、比較例1〜3 將2克由1莫耳2,4,4,4四羥基二苯基酮與3莫耳萘醌 -1，2-二疊氮-5-磺醯氯進行酯化反應所得到的生成物、8克甲 -19- 1363935 PNP A:丙二醇一丙醚乙酸酯 1,3ΒΕΠ，3-丁二醇一乙醚 1，3ΒΕΑ:1,3-丁二醇一乙醚乙酸酯 GTA:甘油三乙酸酯 PGMEA:丙二醇甲醚乙酸酯 EL:乳酸乙酯 ΡΡΗΑ:丙二醇芳基醚乙酸酯 ΡΡΗ:丙二醇芳基醚In the above-mentioned resist development, a usual developer is used, and the solubility in a solvent and the solubility in an alkali solution in the exposed region and the unexposed region are used. The alkaline developer may be an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate or sodium citrate dissolved in ammonia, ethylamine, diethylamine 'triethylamine, diethylethanolamine, triethanolamine or benzylamine. An amine such as an amine or a carbenamide, an aqueous solution such as tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide or a fourth-order ammonium salt such as choline, or a cyclic amine such as pyrrole or a pipe trap. Or an aqueous solution, [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Examples 1 to 1 2, Comparative Examples 1 to 3 2 g by 1 mol 2 a product obtained by esterification of 4,4,4 tetrahydroxydiphenyl ketone with 3 mole naphthoquinone-1,2-diazide-5-sulfonyl chloride, 8 g of methyl-19-1363935 PNP A: propylene glycol monopropyl ether acetate 1,3 hydrazine, 3-butanediol monoethyl ether 1,3 hydrazine: 1,3-butanediol monoethyl ether acetate GTA: triacetin PGMEA: propylene glycol methyl ether acetate Ester EL: ethyl lactate ΡΡΗΑ: propylene glycol aryl ether acetate ΡΡΗ: propylene glycol aryl ether
3ΜΡΑ: 1,3-丙二醇甲醚乙酸酯（ = 3-甲氧基丙基乙酸酯） 1，3BGA:1,3-丁二醇乙酸酯 實施例13~23、比較例4~53ΜΡΑ: 1,3-propanediol methyl ether acetate (= 3-methoxypropyl acetate) 1,3BGA: 1,3-butanediol acetate Examples 13 to 23, Comparative Examples 4 to 5
將苯醌二疊氮感光劑（2,3，4,4’-四羥基二苯基酮與1,2-萘醌二疊氮-5-磺醯氯之酯化物）和酚醛清漆樹脂（間甲酚/對 甲酚=4/6與甲醛之縮聚物），使用相對於100重量份酚醛清 漆樹脂時24重量份苯醌二疊氮感光劑之比例，使用表2之 組成溶劑（數字爲重量比）來溶解，使此等固體成分爲25重 量％。 將如此調製之光阻組成物各取2.00克，將各光阻組成 物均勻地覆蓋在單一直徑之銘器皿的底面後，在100°c之熱 板上加熱30分鐘，測定各自的重量並依照下式算出殘留溶 劑率。結果如表.2所示。表中之略號與前述相同。又，因爲 所使用之光阻組成物爲2 _00克，固體成分濃度爲25重量％， 所以光阻固體成分重量爲0.5克，烘烤前之溶劑重量爲1.50 克。 -22- 1363935 到之樹脂的固體成分爲25重量％，在50°C加熱10分鐘，調 _ · 查樹脂的溶解速度（溶解性）時，結果器壁有粒狀的不溶樹脂 殘留。 本發明之光阻組成物具有優良的溶解性，因爲對人體安 全且安定性優良，所以係一種半導體元件和液晶顯示器等製 造用之有用的光阻組成物。 【圖式簡單說明】 第1圖係顯示在剖面形狀的評價試驗，在矽晶圓和光阻 ^ 圖案之接觸部分發生側蝕（undercut)之狀態（評價：X)之模式 . 圖。 【元件符號說明】 - 1 砍晶圓 . 2 光阻圖案 3 側蝕部a benzoquinone diazide sensitizer (an esterification of 2,3,4,4'-tetrahydroxydiphenyl ketone with 1,2-naphthoquinonediazide-5-sulfonyl chloride) and a novolak resin (between To the ratio of 24 parts by weight of benzoquinone diazide sensitizer to 100 parts by weight of the novolac resin, using the composition solvent of Table 2 (the number is the weight) The ratio was dissolved to make the solid components 25% by weight. 2.00 g of each of the photoresist compositions thus prepared was taken, and each photoresist composition was uniformly covered on the bottom surface of a single-diametered vessel, and then heated on a hot plate of 100 ° C for 30 minutes, and the respective weights were measured and The residual solvent ratio was calculated by the following formula. The results are shown in Table 2. The abbreviations in the table are the same as described above. Further, since the photoresist composition used was 2 _00 g and the solid content concentration was 25% by weight, the weight of the solid content of the photoresist was 0.5 g, and the weight of the solvent before baking was 1.50 g. -22- 1363935 The solid content of the resin was 25% by weight, and it was heated at 50 °C for 10 minutes to adjust the dissolution rate (solubility) of the resin. As a result, the insoluble resin remained in the wall. The photoresist composition of the present invention has excellent solubility and is excellent in human body safety and stability, and is a useful photoresist composition for semiconductor elements and liquid crystal displays. [Simple description of the drawing] Fig. 1 shows the mode in which the undercut shape is evaluated in the contact portion of the tantalum wafer and the photoresist pattern (evaluation: X). [Component Symbol Description] - 1 chopped wafer. 2 photoresist pattern 3 side etching
-24--twenty four-