來清除光阻的 顯示裝置的製 釋劑組合物，特 過程中用來清除 1309757 玖、發明說明 【發明所屬之技術領域】 本發明係關於一種用 別是在半導體裝置或液晶 光阻的稀釋劑組合物。 【先前技術】 在TFT-LCD製備過程中的TFT-陣列 餘刻微影的料導體冑程。《蚀刻微影製 基材上沉積一光敏層、形成一光罩圖案、 得一電路的製程》 —TFT-陣列係形成於一基材上，以藉 程來製造一 TFT-LCD。在此製程中，如果 渗透該光阻介面的話，將對後續包括蝕刻 的製程有不利的影響。此將會降低整體製 這類滲入光敏層介面的現象可能導致 曝光過程失焦，因而降低該TFT-LCD製儀 與石夕晶圓邊緣會產生離心力不同的是 玻璃基材乃是方形的，因此藉由旋轉來移f 移除：移除邊緣部位的光阻）幾乎是不可敍 玻璃基材是固定的，且喷嘴係沿著玻璃基 移動’因此即使邊緣的光阻已被移除，如 物並未被迅速揮發的話，仍可能發生自光 的情況。此係與旋轉移除EBR不同，在為 法：’類似使用光 程乃是利用在一 顯影及蝕刻後獲 由光蝕刻微影製 該稀釋劑組合物 、離子植入等等 程的產率。 在供.烤製程後的 (過程的產率。 ，一 TFT-LCD 的 & EBR(邊緣珠粒 ί的。此外，由於 板的四個平面來 果該稀釋劑組合 阻邊緣渗入介面 色轉移除EBR的 1309757 情況下，矽晶圓係以高速轉動且自光阻邊緣滲入介面的情 況會被大幅降低’即使該稀釋劑組合物並未被迅速揮發。 亦即，因為該LCD玻璃基材係固定的，且只有稀釋劑嗔嘴 會移動，使用習知高溶解度稀釋劑可能會在清洗邊緣時導 致滲入光阻介面的現象’因而降低整體製程的產率。 習知稀釋劑組合物係如下述。 曰本專利公開號Sho 63-69563揭示以一稀釋劑接觸基 材來移除不欲求光阻的方法。在此方法中，一清潔用的有 機溶劑，例如醚類和醚類乙酸酯，例如溶纖（cellosolve)、 溶纖乙酸酯、丙二醇醚、丙二醇醚乙酸酯等；酮類例如丙 酮、甲乙酮、甲異丁酮、環己酮等；或酯類例如乳酸甲酯、 乳酸乙酯、乙酸曱酯、乙酸乙酯、乙酸丁酯等，均可當作 稀釋劑使用。曰本專利公開號Hei 4-4993 8揭示以丙二醇 甲基謎乙酸醋（propylene glycol methyl ether acetate， PGMEA)作為稀釋劑；且日本專利公開號Hei 4-42523揭示 以烷氧基丙酸烷基酯作為稀釋劑。 這些溶劑係可單獨使用或在考慮過其物理性質與安全 性後可合併使用。與基材係被固定且使用線性 EBR的 TFT-LCD製備過程不同的是，這類溶劑係用於相當高旋轉 速度下的轉動式EBR製程中。 但是，其並無法解決滲入光阻介面的問題。 【發明内容】 本發明一目的係提供一種可清除光敏性光阻的稀釋劑 4 1309757 組合物，其係能用來防止滲入用於製造液晶顯示裝置之基材 (特別疋用於一有機EL顯示裝置的大型玻璃板）邊緣光阻介 面，及於短時間内有效移除光阻。 【實施方式】 為達上述目的’本發明提供一種可清除光阻的稀釋劑組 合物’其包含a) —丙二醇單基醚；b) —乙醇酸烷基酯；及 c)一·環_類。 較佳是，該稀釋劑組合物包含a) 1 0份至90份重量份的 丙二醇單基醚，b) 10份至70份重量份的乙醇酸烧基酯’及 c) 1份至70份重量份的環酮類。 1 ·本發明的稀釋劑組合物可更包含至少一種選自下列 群組的化合物，包括d) —氟化的丙烯酸共聚物，及e) 一 聚環氧乙烷縮聚物。 較佳是，該稀釋劑組合物包含a) 1 0份至9〇份重量份的 丙二醇單基醚，b)l〇份至7〇份重量份的乙醇酸燒基醋，C) 1份至70份重量份的環酮類，及d) 〇.001份主1伤重置伤的 氟化的丙烯酸共聚物° β 此外，該稀釋劑組合物玎包含a) 1 〇份直9〇伤重置伤的 丙二醇單基醚，b)H)份至7G份重量㈣旨’ e) i份至70份重量份的環嗣類，及d)〇·001份直1份重量份的 90份重量份的丙二 醇酸烷基酯’ c) 1 環氧乙烷縮聚物。 該稀釋劑組合物也可包含a)1〇份至 醇單基醚，b) 10份至70份重量份的乙 1309757 份至70份重量份的環酮類，d) 〇.〇〇 1份至1份重量份的氟化 的丙烯酸共聚物’及e) 0.001份至1份重量份的環氧乙烷縮 聚物。 以下，將詳細說明本發明。 本發明特徵為能有效防止滲入光阻介面’因此能用來製 造半導體裝置或液晶顯示裝置。 本發明用來清除光阻的稀釋劑組合物至少包一丙二醇 單烷基醚、一乙醇酸烷基酯及一環酮類。 該丙二醇單烷基醚、乙醇酸烷基酯及環酮類之每—者係 選用超純半導體等級者。在VLSI階段，係選用能通過〇,丨μιη 濾膜者。 琢丙二醇皁烷基醚的烷基 言之，該丙二醇單烷基醚較佳是至少一選自下列的物質，包 括丙：醇單f基醚、丙二醇單乙基醚、丙二醇單丙基醚及： 二醇單丁基醚。在這些化合物中，較佳是選用對聚合物具有 玉佳溶解能力的丙二醇單甲基醚。 生傷：:::：：基_露於空氣中時’並不會對人類產 傷口且在人體中會被快速分 服施用至人類的毒性報告，其百分五十:及二醇。依據-口 克/公斤。且其會因水解而迅速分解。為4.4 點（以密封杯法測量）為饥弗點為132.8C，閃 J篁）马32 C，黏度（25°c、炎， 張力為26.5達因/平大八八 ）為1.86 cps，表面 因+方公分’溶解係數為1〇4 較么疋’每100份重量份的組合 重量份之該丙二醇單院基如果該二含1。份至9。份 〜醇單烷基醚的重量 6 1309757 份低於1 0份’則其溶解光阻的能力將下降。相反的，如果 該丙二醇單烷基醚的重量份超過90份，其揮發性將降低， 使得乾燥後仍有稀釋劑殘存於表面上。 此外’該乙醇酸烧基S旨'的烧基團較佳是具有1至4個碳 原子，詳言之，該乙醇酸烷基酯係選自由乙醇酸曱酯、乙醇 酸乙酯、乙醇酸異丙酯、乙醇酸正丙酯及乙醇酸丁酯所組成 之族群中的至少一者。在這些溶劑中，較佳是選用乙醇酸異 丙酯、乙醇酸正丙酯及乙醇酸丁酯，其具有足夠的揮發性及 低黏度。較佳是’每1 〇 0份重量份的組合物中包含1 〇份至 70份重量份之乙醇酸烷基酯。如果該乙醇酸烷基酯的重量份 低於10份，稀釋劑將變得不易揮發，使得乾燥後仍有稀釋 劑殘存於表面上。相反的，如果該乙醇酸烷基酯的重量份超 過70份’稀釋劑的溶解力將降低。 乙醇酸烷基酯之一的乙醇酸丁酯，對多種樹脂都具有極 佳的溶解力’表面張力特別低，且揮發性極佳，因此只要少 量添加於稀釋劑中即可提供極佳的介面性質。依據一 口服施 用至人類的毒性報告，乙醇酸丁酯的百分五十致死量（LD5〇〕 為7.0克/公斤。且其會因水解而迅速分解。其沸點為ι C ’閃點（以密封杯法測量）為23-C，黏度（25。(：）為〇_74 cps , 表面張力為25達因/平方公分。 所選用的環酮類可以是環戊酮、環己酮及環庚酮等等。 1二；谷劑中’較佳是選用對多種樹脂具有極佳溶解度的環 己_]。 較佳是’每1 〇〇份重量份的組合物中包含1份至70份 1309757 重量份之竦酮類。如果環酮類的重量份低於丨份，其移除數· 種光阻的能力將降低。相反的，如果該環酮類的重量份超過 70份，其溶解特定光阻層的能力將下降。 本發明稀釋劑組合物可更包含至少一種選自下列群組 的化合物，包括一氟化的丙烯酸共聚物；及一聚環氧乙烷縮 聚物。 該氟化的丙烯酸共聚物對水及許多種溶劑均具有相當 好的溶解度。目前市售的氟化的丙烯酸共聚物商品的例子為A release agent composition for removing a photoresist display device for use in the process of removing 1309757 玖. Description of the Invention [Technical Field of the Invention] The present invention relates to a thinner which is used in a semiconductor device or a liquid crystal photoresist combination. [Prior Art] The TFT-array in the preparation process of the TFT-LCD is a material conductor process of the lithography. The process of depositing a photosensitive layer on a lithographic substrate to form a mask pattern to obtain a circuit is formed by forming a TFT-LCD on a substrate. In this process, if the photoresist interface is infiltrated, it will adversely affect subsequent processes including etching. This will reduce the overall phenomenon of infiltration into the photosensitive layer interface, which may lead to defocusing during the exposure process. Therefore, the difference between the TFT-LCD device and the edge of the wafer substrate is that the centrifugal force is different, that is, the glass substrate is square, so By rotating to remove f: remove the photoresist at the edge) Almost the unspeakable glass substrate is fixed, and the nozzle moves along the glass base' so even if the edge photoresist has been removed, Self-lighting may still occur if it is not rapidly evaporated. This is in contrast to the spin-removal of the EBR, which is a similar process: the yield of the thinner composition, ion implantation, etc., obtained by photolithography after a development and etching. After the baking process (the yield of the process., a TFT-LCD & EBR (edge bead ί. In addition, due to the four planes of the plate, the thinner combination barrier edge infiltration interface color transfer) Except for EBR's 1309757, the enamel wafers are rotated at high speed and penetrate the interface from the photoresist edge, which is greatly reduced' even if the thinner composition is not rapidly evaporated. That is, because the LCD glass substrate is Fixed, and only the diluent nozzle will move, the use of conventional high solubility diluents may cause the phenomenon of penetration into the photoresist interface when cleaning the edges' thus reducing the overall process yield. Conventional thinner compositions are as follows A method for removing undesired photoresist by contacting a substrate with a diluent is disclosed in Japanese Patent Publication No. Sho 63-69563. In this method, a cleaning organic solvent such as an ether and an ether acetate, For example, cellosolve, cellosolve acetate, propylene glycol ether, propylene glycol ether acetate, etc.; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; or esters such as methyl lactate, lactate B ester, The acid ester, ethyl acetate, butyl acetate, etc. can be used as a diluent. The disclosure of the patent publication No. Hei 4-4993 8 discloses dilution with propylene glycol methyl ether acetate (PMMEA). And Japanese Patent Publication No. Hei 4-42523 discloses the use of alkyl alkoxypropionates as diluents. These solvents may be used singly or in combination with their physical properties and safety. Unlike the TFT-LCD fabrication process, which is fixed and uses linear EBR, this type of solvent is used in a rotary EBR process at a relatively high rotational speed. However, it does not solve the problem of penetrating the photoresist interface. An object of the present invention is to provide a thinner 4 1309757 composition capable of removing photosensitivity photoresist, which can be used to prevent penetration into a substrate for manufacturing a liquid crystal display device (particularly for a large-sized organic EL display device) Glass plate) edge photoresist interface, and effective removal of photoresist in a short time. [Embodiment] For the above purpose, the present invention provides a thinner group capable of removing photoresist Implants comprising a) - propylene glycol monoethyl ether; b) - alkyl esters of glycolic acid; and c) a ring-type _. Preferably, the thinner composition comprises a) from 10 parts to 90 parts by weight of propylene glycol monoether, b) from 10 parts to 70 parts by weight of glycolic acid ester 'and c) from 1 part to 70 parts Parts by weight of cyclic ketones. 1) The thinner composition of the present invention may further comprise at least one compound selected from the group consisting of d) - a fluorinated acrylic copolymer, and e) a polyethylene oxide polycondensate. Preferably, the thinner composition comprises a) from 10 parts to 9 parts by weight of propylene glycol monoether, b) from 1 part to 7 parts by weight of glycolic acid vinegar, and 1) to 70 parts by weight of a cyclic ketone, and d) 001. 001 parts of a primary wounded fluorinated acrylic copolymer ° β In addition, the thinner composition a contains a) 1 part of a straight 9 〇 wound weight Damaged propylene glycol monoether, b) H) to 7G parts by weight (4) for 'e) part to 70 parts by weight of ring oxime, and d) 〇·001 parts by 1 part by weight of 90 parts by weight Parts of alkyl propylene glycol ' c) 1 ethylene oxide polycondensate. The thinner composition may also comprise a) 1 part to an alcohol monoether, b) 10 parts to 70 parts by weight of B 1309757 parts to 70 parts by weight of a cyclic ketone, d) 〇. To 1 part by weight of the fluorinated acrylic copolymer 'and e) from 0.001 part by weight to 1 part by weight of the ethylene oxide polycondensate. Hereinafter, the present invention will be described in detail. The present invention is characterized in that it can effectively prevent penetration into the photoresist interface' and thus can be used to fabricate a semiconductor device or a liquid crystal display device. The thinner composition for removing photoresist of the present invention comprises at least one propylene glycol monoalkyl ether, monoglycolic acid alkyl ester and one cyclic ketone. Each of the propylene glycol monoalkyl ether, the alkyl glycolate and the cyclic ketone is selected from the group consisting of ultrapure semiconductor grades. In the VLSI stage, those who pass the 〇, 丨μιη filter are selected. The alkyl propylene glycol monoalkyl ether is preferably at least one selected from the group consisting of propane: alcohol mono-f-ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and : diol monobutyl ether. Among these compounds, propylene glycol monomethyl ether having a solubility in a polymer is preferably used. Injury::::::Base _ when exposed to the air' does not cause human wounds and will be quickly administered to humans for toxicity reports in humans, 50%: and diol. According to - mouth / kg. And it will decompose rapidly due to hydrolysis. For 4.4 points (measured by the sealed cup method), the hungry point is 132.8C, the flash is J篁), the horse is 32 C, and the viscosity (25°c, inflammation, tension is 26.5 dyne/flat eight) is 1.86 cps. Since the + square centimeter 'solution coefficient is 1 〇 4 疋 疋 'per 100 parts by weight of the combined weight part of the propylene glycol single yard base if the two contains 1. Share to 9. The weight of the alcohol-monoalkyl ether 6 1309757 parts less than 10 parts' will reduce its ability to dissolve the photoresist. Conversely, if the propylene glycol monoalkyl ether is present in an amount of more than 90 parts by weight, the volatility will be lowered so that the diluent remains on the surface after drying. Further, the calcined group of the glycolic acid group S preferably has 1 to 4 carbon atoms. In particular, the alkyl glycolate is selected from the group consisting of decyl glycolate, ethyl glycolate, and glycolic acid. At least one of a group consisting of isopropyl ester, n-propyl glycolate, and butyl glycolate. Among these solvents, isopropyl glycolate, n-propyl glycolate and butyl glycolate are preferred, which have sufficient volatility and low viscosity. Preferably, the composition comprises from 1 part by weight to 70 parts by weight of the alkyl glycolate per 1 part by weight of the composition. If the weight percentage of the alkyl glycolate is less than 10 parts, the diluent will become less volatile, so that the diluent remains on the surface after drying. Conversely, if the weight ratio of the alkyl glycolate exceeds 70 parts, the solvency of the diluent will decrease. Butyl glycolate, one of the glycolic acid esters, has excellent solubility for a variety of resins. 'The surface tension is extremely low and the volatility is excellent, so a small amount of addition to the diluent provides an excellent interface. nature. According to a toxicity report for oral administration to humans, the 50% lethal dose of butyl glycolate (LD5〇) is 7.0 g/kg, and it will decompose rapidly due to hydrolysis. Its boiling point is ι C 'flash point (in terms of The sealed cup method is measured by 23-C, the viscosity (25. (:) is 〇_74 cps, and the surface tension is 25 dynes/cm 2 . The selected cyclic ketones may be cyclopentanone, cyclohexanone and ring. Heptone and the like. 1 2; in the granules, it is preferred to use a cyclohexene having excellent solubility for a plurality of resins.] Preferably, the composition contains 1 part to 70 parts per 1 part by weight of the composition. 1309757 parts by weight of anthrone. If the weight fraction of the cyclic ketone is lower than that of the oxime, the ability to remove the number of photoresists will be reduced. Conversely, if the weight fraction of the cyclic ketone exceeds 70 parts, it dissolves. The ability of the particular photoresist layer will decrease. The thinner composition of the present invention may further comprise at least one compound selected from the group consisting of a fluorinated acrylic copolymer; and a polyethylene oxide polycondensate. Acrylic copolymers have a fairly good solubility in water and many solvents. An example of a commercially available fluorinated acrylic copolymer product is
Danippon Ink and Chemicals 的 Megaface R_〇8。 較佳疋’每100份重量份的組合物中包含〇.〇〇l份至1 份重量份之該氟化的丙烯酸共聚物。如果該氟化的丙烯酸共 聚物的重量份低於0.001份，其溶解光阻的能力將顯著的降 低。相反的’如果該氟化的丙烯酸共聚物的重量份超過1份， 其移除能力將隨著介面處變動的表面張力的下降而改善，但 液體高度感應器卻會因泡沫過多而無法正常操作。 對氟化的丙烯酸共聚物而言，較佳是其平均重量分子量 介於3000至1〇,〇00間，其閃點（以密封杯法測量）為20〇°c， 比重為1.10克/毫升（25。(：），黏度（20°c )為2100 cps，在乳酸 乙酯上的表面張力為24_0毫達因/平方公尺。較佳是，其係 於乳酸乙酯中稀釋使用。 該聚環氧乙烷縮聚物係作為一種非離子型介面活性 劑。明確的說，該縮聚物乃是由具有6到1 2個碳原子的直 鏈或支鏈烷基團的烷基苯酚以每1莫耳烷基苯酚與5到25 莫耳的環氧乙烷進行縮合聚合後所得的產物。該烷基笨酚的 8 1309757 燒基係衍生自丙蝉、二異丁稀、辛稀、或壬稀。縮聚.物的例 子為壬基苯酚，其係獲自每Γ莫耳笨酚與約9.5莫耳環氧己 燒縮聚後產物；十二烷基笨酚，其係獲自每1莫耳苯紛與約 12莫耳環氧乙烧縮聚後產物；二異辛基苯酚，其係獲自每i 莫耳苯紛與約15莫耳環氡乙烷縮聚後產物等等。這些化合 物對水及許多種溶劑均具有相當好的溶解度。其可降低當稀 釋劑接觸光阻層時的介面間隙。一種商業上可用的例子為東 進化學公司出品的非離子型Monopol系列。 較佳是’每100份重量份的組合物中包含〇 〇〇1份至1 份重量份之該聚環氧乙娱;縮聚物。如果該聚環氧乙烷縮聚物 的重量份低於0.001份，基材邊緣處稀釋劑的揮發性及清除 能力將顯著的降低。相反的，如果該聚環氧乙烷縮聚物的重 量份超過1份’將產生過多的泡沫而無法正常操作。 在使用塗層機於基材上施加一光阻層後，基材邊緣及背 面之不欲求的光阻可藉由滴落或喷灑稀釋劑來加以移除。可 視光阻層的種類及膜層厚度來控制所滴落或喷灑之本發明 稀釋劑的量。該量較佳是介於5至100毫升/分鐘間。在喷灌 了稀釋劑後，可藉後續光蝕刻微影製程來形成一微電路圖 案。 如上述，本發明用來清除光阻的稀釋劑組合物可有效、 迅迷的清除黏附在用來製造液晶顯示裝置之基材（特別是用 於有機EL顯示裝置之大型玻璃基板）邊緣及背面之不欲求光 阻，降低介面間隙，及防止滲入光阻介面。因此，其提供一 種經濟有效、簡單的製程，同時還可改善產率。 9 1309757 該等實施例係供 限於所揭示實施 以下，將藉由實施例詳細說明。但是， 闡述本發明内容之用，本發明範疇並不僅 例0 實施例 以下列方式製備一基材試樣。 使用一直徑為8英吋的二氧化梦基材。該基材係於包括 過氧化氫及硫酸的兩種溶液中清洗，分別浸泡於每一溶液中 5分鐘’然後再以超純水清洗。此過程係以特殊清潔設備來 執行。之後，以旋乾機（VERTEQ之SRD 1 800-6)將基材旋乾。 以旋塗機（韓國半導體系統之EBR TRACKER)在基材上塗佈 —層預定厚度的光阻。 旋塗製程如下。將10毫升的光阻層組合物滴在靜止的 基材中央。之後，旋塗機以5〇〇rpm的速度旋轉3秒的方式 進行塗佈。接著，在2000至4000 rpm速度下旋轉以獲得具 欲求厚度的光阻層，旋轉時間為20至30秒。 例]S 7 每一實施例1 -7及比較實施例丨_5之稀釋劑組合物的組 成及其含量如表1所示（單仅：重量份）。 10 1309757 [表i] 分類 PGME1 PGME A2 n-PE3 CXN4 GBL5 OP-101 566 R-087 實施例 1 60 - 30 10 - - - 2 20 - 10 70 - _ - 3 80 - 10 10 - _ - 4 1 0 - 70 20 - - - 5 60 30 10 0.01 6 60 30 10 0.5 - 7 60 30 10 0.5 0.01 比較實施 例 1 - 60 30 1 0 - 50 - 2 60 - - 10 30 - - 3 70 30 - - - - 4 50 - 50 - - - - 5 50 - - 50 - - 0.01 註）Megaface R_〇8 from Danippon Ink and Chemicals. Preferably, the fluorinated acrylic copolymer is contained in an amount of from 0.1 part by weight to 1 part by weight per 100 parts by weight of the composition. If the fluorinated acrylic copolymer is less than 0.001 parts by weight, its ability to dissolve the photoresist is remarkably lowered. Conversely, if the fluorinated acrylic copolymer is more than one part by weight, the removal ability will be improved as the surface tension at the interface changes, but the liquid height sensor will not operate properly due to excessive foaming. . For the fluorinated acrylic copolymer, it is preferred that the average weight molecular weight is between 3,000 and 1 〇, 〇00, and the flash point (measured by the sealed cup method) is 20 〇 ° C, and the specific gravity is 1.10 g / ml. (25. (:), viscosity (20 ° c) is 2100 cps, and the surface tension on ethyl lactate is 24 _0 millidyne/m 2 . Preferably, it is diluted in ethyl lactate. A polyethylene oxide polycondensate is used as a nonionic surfactant. Specifically, the polycondensate is an alkylphenol having a linear or branched alkyl group having 6 to 12 carbon atoms per a product obtained by condensation polymerization of a molar alkyl phenol with 5 to 25 moles of ethylene oxide. The 8 1309757 alkyl group of the alkyl phenol is derived from acetamidine, diisobutylene, nitrite, or An example of a polycondensation. The polycondensation is a nonylphenol obtained from a polycondensation product of about 9.5 moles of epoxidized hexanol; a dodecyl phenol, which is obtained from every 1 mole. The product of polycondensation of benzene with about 12 moles of epoxy ethene; diisooctylphenol, which is obtained from polycondensation of each mole of urethane with about 15 moles of enamel These compounds have a fairly good solubility in water and many solvents. They reduce the interfacial gap when the diluent contacts the photoresist layer. A commercially available example is the nonionic Monopol from Dongjin Chemical Company. Preferably, the composition comprises: from 1 part to 1 part by weight per 100 parts by weight of the composition of the polyepylene; a polycondensate. If the polyethylene oxide polycondensate has a low weight fraction At 0.001 parts, the volatility and scavenging ability of the diluent at the edge of the substrate will be significantly reduced. Conversely, if the weight fraction of the polyethylene oxide polycondensate exceeds 1 part, too much foam will be produced and it will not function properly. After applying a photoresist layer on the substrate using a coating machine, the undesired photoresist on the edges and back of the substrate can be removed by dropping or spraying a thinner. The type of visible photoresist layer and the film The layer thickness is used to control the amount of the diluent of the present invention dripped or sprayed. The amount is preferably between 5 and 100 ml/min. After spraying the diluent, it can be formed by a subsequent photo-etching lithography process. a microcircuit pattern. The thinner composition for removing photoresist in the present invention can effectively and quickly remove the adhesion to the edges and the back of a substrate for manufacturing a liquid crystal display device, particularly a large glass substrate for an organic EL display device. It does not require photoresist, reduces interface gap, and prevents penetration into the photoresist interface. Therefore, it provides a cost-effective and simple process while improving yield. 9 1309757 These embodiments are limited to the disclosed embodiments below, DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS However, the contents of the present invention are explained, and the scope of the present invention is not limited to the embodiment of the present invention. A substrate sample is prepared in the following manner. A dream substrate of 8 inches in diameter is used. The substrate was washed in two solutions including hydrogen peroxide and sulfuric acid, each immersed in each solution for 5 minutes' and then washed with ultrapure water. This process is performed with special cleaning equipment. Thereafter, the substrate was spin-dried by a spin dryer (VERDQ SRD 1 800-6). A photoresist of a predetermined thickness is coated on the substrate by a spin coater (EBR TRACKER of the Korean semiconductor system). The spin coating process is as follows. 10 ml of the photoresist layer composition was dropped in the center of the stationary substrate. Thereafter, the spin coater was applied by being rotated at 5 rpm for 3 seconds. Next, it is rotated at a speed of 2000 to 4000 rpm to obtain a photoresist layer having a desired thickness, and the rotation time is 20 to 30 seconds. Example 7 S 7 The composition of each of Examples 1-7 and Comparative Example 丨5, and the contents thereof are shown in Table 1 (single: only parts by weight). 10 1309757 [Table i] Classification PGME1 PGME A2 n-PE3 CXN4 GBL5 OP-101 566 R-087 Example 1 60 - 30 10 - - - 2 20 - 10 70 - _ - 3 80 - 10 10 - _ - 4 1 0 - 70 20 - - - 5 60 30 10 0.01 6 60 30 10 0.5 - 7 60 30 10 0.5 0.01 Comparative Example 1 - 60 30 1 0 - 50 - 2 60 - - 10 30 - - 3 70 30 - - - - 4 50 - 50 - - - - 5 50 - - 50 - - 0.01 Note)
1. PGME =丙二醇單曱醚 2. PGMEA =丙二醇單乙醚乙酸酯 3· n-PE =乙醇酸正丙酯 4. CXN =環己酮 5. GBL = γ-丁内酯 6. ΟΡ-1015=東進半導體之 MonopolOP-1015，一種 經由縮聚5莫耳環氧乙烷與每1莫耳辛基笨酚而得的縮聚物 7. R-0 8 = Danippon Ink and Chemicals 的 Megaface ll 1309757 R-08，一種氟化的丙烯酸共聚物 清除不键^求 將-光阻層組合物塗佈在8英吋的二氧化矽基材上。以 實施例1 i 7及比較實施例】i 5的稀釋劑組合物分別來清 除基材邊緣的光阻層（邊緣珠粒清除測試（Edge bead1. PGME = propylene glycol monoterpene ether 2. PGMEA = propylene glycol monoethyl ether acetate 3. n-PE = n-propyl glycolate 4. CXN = cyclohexanone 5. GBL = γ-butyrolactone 6. ΟΡ-1015 = Monogon OP-1015 from Dongjin Semiconductor, a polycondensate obtained by polycondensation of 5 moles of ethylene oxide per mole of phenol, R. 8 = Danippon Ink and Chemicals, Megaface ll 1309757 R-08, A fluorinated acrylic acid copolymer removes the photoresist layer composition onto a 8 inch ruthenium dioxide substrate. The thin film composition of Example 1 i 7 and Comparative Example] i 5 was used to remove the photoresist layer at the edge of the substrate (edge bead removal test (Edge bead)
removing test) ··以下簡稱eBR測試）。在eBR測試中，使用 塗佈光阻層時相同的旋塗機。 經由EBR喷嘴將表1的每一稀釋劑組合物於表3所示的 條件下噴在已塗了表2所示光阻層組合物的基材上。每一稀 釋Μ組合物係由一配有加壓閥的加壓桶中餵入喷嘴中。壓力 Λ定為1 .OKgf且自EBR噴嘴離開的稀釋劑組合物的流速設 定為每分鐘10至20毫升。 每一組合物的EBR_測試結果示於表4中。 [表2]Removing test) ··hereinafter referred to as eBR test). In the eBR test, the same spin coater was used when applying the photoresist layer. Each of the thinner compositions of Table 1 was sprayed on the substrate to which the photoresist layer composition shown in Table 2 was applied under the conditions shown in Table 3 via an EBR nozzle. Each of the diluted hydrazine compositions is fed into a nozzle from a pressurized barrel equipped with a pressurizing valve. The pressure setting is set to 1. OKgf and the flow rate of the diluent composition leaving the EBR nozzle is set to 10 to 20 ml per minute. The EBR_ test results for each composition are shown in Table 4. [Table 2]
及膜層厚度 ----- ------ ±m 組合物種麴 組合物製造商 膜層厚度（μιη) 光阻 g -線正型 DTFR-2000 1.5 g-線負型 DNR-H100PL 4 有機ELPI DL-1003 1.5 12 1309757 [表3] EBR測試條件 分類 旋塗速度（rpm) 時間（秒） 懸垂型 500 3 旋塗型 依據光阻層厚度來決定 EBR條件 400 7 400 10 500 7 500 10 [表4] EBR測試結果 分類 EBR條件 實施例 比較實施例 1 2 3 4 5 6 7 1 2 3 4 5 g-線正型 400 rpm，7 秒 0 Δ Δ 0 ◎ 0 ◎ Δ Δ X Δ X 500 rpm，7 秒 ◎ 0 0 0 ◎ ◎ ◎ Δ Δ Δ 0 Δ 500 rpm，10 秒 ◎ 0 0 ◎ ◎ ◎ ◎ 0 0 Δ 0 Δ g-線負型 400 rpm，7 粆 0 Δ Δ 0 ◎ 0 ◎ Δ Δ X Δ X 500 rpm，7 秒 0 0 0 0 ◎ ◎ ◎ Δ Δ X Δ Δ 500 rpm，10 秒 ◎ 0 0 ◎ ◎ ◎ ◎ 0 0 Δ 0 Δ 有機ELPI 300 rpm，10 秒 0 0 Δ 0 ◎ 0 ◎ Δ Δ X Δ X 400 rpm，10 秒 0 0 0 ◎ ◎ ◎ ◎ Δ Δ X Δ X 500 rpm，10 秒 ◎ 0 0 ◎ ◎ ◎ ◎ 0 0 Δ 0 Δ 在表4中，” ◎”代表在EBR測試中沒有出現滲入光阻 13 1309757 "面的現象。”0”代表· 80%或以上出現滲入光阻介面者具有 —欲求的線性形狀。”Δ”代表50%或以上出現滲入光阻介面者 具有—欲求的線性形狀。，，χ”代表20%或以上出現滲入光阻 介面者具有一欲求的線性形狀且膜層邊緣出現懸垂尾部。 如表4所示’本發明所有的稀釋劑組合物（實施例丄至 7)對所有光阻層都展現出極佳的ebr能力（邊緣报乾淨）。特 別是，實施例5和7的稀釋劑組合物顯示了極佳的Ebr能力 及防止滲入能力。目此，本發明包含了一聚環氧乙烷縮聚 物、-氟化的丙烯酸共聚物、或其之混合物的稀釋劑組合物 可提供優異的清除光阻能力。 相反的’比較實施例4 5具有更差的防止渗入能力。 其會降低後續製程中一半導體裝置或一液晶顯示裝置的產 率。 習知技藝人士從上述說明中可輕易了解本發明特徵， 不棒離本發明料T,可對本發明作不同程度的％化或修 改’以達本發明所揭示的相同目@。該等變化或修改仍應 為本發明附隨申請專利範圍所定義的範疇。 14And film thickness----------- ±m combination species 麴 composition manufacturer film thickness (μιη) photoresist g-line positive DTFR-2000 1.5 g-line negative DNR-H100PL 4 Organic ELPI DL-1003 1.5 12 1309757 [Table 3] EBR test conditions Classification Spin coating speed (rpm) Time (seconds) Suspended type 500 3 Spin coating type Determines the EBR condition according to the thickness of the photoresist layer 400 7 400 10 500 7 500 10 [Table 4] EBR test result classification EBR condition Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 5 g-line positive type 400 rpm, 7 seconds 0 Δ Δ 0 ◎ 0 ◎ Δ Δ X Δ X 500 Rpm, 7 seconds ◎ 0 0 0 ◎ ◎ ◎ Δ Δ Δ 0 Δ 500 rpm, 10 seconds ◎ 0 0 ◎ ◎ ◎ ◎ 0 0 Δ 0 Δ g-line negative type 400 rpm, 7 粆0 Δ Δ 0 ◎ 0 ◎ Δ Δ X Δ X 500 rpm, 7 seconds 0 0 0 ◎ ◎ ◎ Δ Δ X Δ Δ 500 rpm, 10 seconds ◎ 0 0 ◎ ◎ ◎ ◎ 0 0 Δ 0 Δ Organic ELPI 300 rpm, 10 seconds 0 0 Δ 0 ◎ 0 ◎ Δ Δ X Δ X 400 rpm, 10 seconds 0 0 ◎ ◎ ◎ ◎ Δ Δ X Δ X 500 rpm, 10 seconds ◎ 0 0 ◎ ◎ ◎ ◎ 0 0 Δ 0 Δ In Table 4, “ ◎” The representative did not have an EBR test Now infiltration resist 131,309,757 " phenomenon surface. "0" represents that 80% or more of the infiltrated photoresist interface has a linear shape to be desired. "Δ" represents 50% or more of the infiltrated photoresist interface having a linear shape desired. , χ" represents 20% or more of the infiltrated photoresist interface has a desired linear shape and a dangling tail appears at the edge of the film layer. As shown in Table 4, all of the thinner compositions of the present invention (Examples 丄 to 7) Excellent photo-resistance is exhibited for all photoresist layers (edges are clean). In particular, the thinner compositions of Examples 5 and 7 exhibit excellent Ebr capabilities and ability to prevent penetration. Accordingly, the present invention encompasses A thinner composition of a polyethylene oxide polycondensate, a fluorinated acrylic copolymer, or a mixture thereof provides excellent light-blocking resistance. The opposite 'Comparative Example 45 has worse penetration prevention. It can reduce the yield of a semiconductor device or a liquid crystal display device in a subsequent process. Those skilled in the art can easily understand the features of the present invention from the above description, and the present invention can be used to different degrees. % 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。