1314248 玖、發明說明： 【發明所屬之技術領域】 本發明係關於光阻顯影劑組合物，特定言之，係關於在 製造一薄膜電晶體液晶顯示元件（TFT-LCD)或一半導體 時，用以形成光阻圖案之一光阻顯影劑組合物。 【先前技術】BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photoresist developer composition, and more particularly to the manufacture of a thin film transistor liquid crystal display device (TFT-LCD) or a semiconductor. To form a photoresist developer composition of the photoresist pattern. [Prior Art]
一微電路圖案，諸如一 TFT-LCD電路、一半導體積體 電路等，大致以下列步驟形成。首先，塗布一光阻組合物， 以形成一光阻層於基板之絕緣層上或一傳導金屬層上，並 硬烤塗布之光阻組合物'而此光阻組合物包含一黏合劑、 一光聚合單體、一起始劑、一有機溶劑等。而後，具有預 定電路圖案之罩幕係設於光阻層上，並以UV輻射線、電 子束（E-beam)、或諸如 X輻射線之電子束加以照射光阻 層。曝光區域與未曝光區域在顯影劑組合物中具有不同溶 解度。因此，藉由顯影劑組合物顯影曝光區域或未曝光區 域而形成欲求的光阻圖案。最後，蝕刻去除藉由已顯影光 阻圖案而曝光之絕緣層或傳導金屬層，以形成目標電路圖 案。 光阻顯影步驟是形成欲求精密細光阻圖案之一非常重 要的步驟。光阻圖案的形狀與線寬及光阻的溶解度，取決 於顯影劑組合物的形式與pH值及顯影劑組合物内界面活 性劑種類與含量。傳統顯影劑組合物係混合非離子或離子 界面活性劑與有機或無機鹼性水溶液。有機顯影劑组合物 包含有機鹼性化合物，諸如四曱基銨氫氧化物、膽鹼等。 3 1314248A microcircuit pattern, such as a TFT-LCD circuit, a semiconductor integrated circuit, or the like, is formed substantially in the following steps. First, a photoresist composition is applied to form a photoresist layer on the insulating layer of the substrate or a conductive metal layer, and the photoresist composition is hard-baked. The photoresist composition comprises a binder, Photopolymerizable monomer, a starter, an organic solvent, and the like. Then, a mask having a predetermined circuit pattern is attached to the photoresist layer, and the photoresist layer is irradiated with UV radiation, an electron beam (E-beam), or an electron beam such as X-ray. The exposed areas and the unexposed areas have different degrees of solubility in the developer composition. Therefore, the desired photoresist pattern is formed by developing the exposed or unexposed regions of the developer composition. Finally, an insulating layer or a conductive metal layer exposed by the developed photoresist pattern is etched away to form a target circuit pattern. The photoresist development step is a very important step in forming one of the fine photoresist patterns. The shape of the photoresist pattern and the solubility of the line width and photoresist depend on the form and pH of the developer composition and the type and amount of interfacial activator in the developer composition. Conventional developer compositions are mixed with a nonionic or ionic surfactant and an aqueous organic or inorganic solution. The organic developer composition contains an organic basic compound such as tetradecylammonium hydroxide, choline or the like. 3 1314248
然而，有機顯影劑組合物對光阻具有低的滲透性及低的溶 解性，此將增加顯影光阻的時間並破壞光阻輪廓的形狀及 光阻圖案尺寸的精確度。因此，一無機顯影劑組合物，其 混合非離子或離子界面活性劑與無機鹼水溶液（包含氫氧 化鉀、氫氧化鈉、磷酸鈉、矽酸鈉、碳酸鈉、碳酸氫鈉等）， 較廣泛地為業界採用。由於無機顯影劑組合物對水的高溶 解度及其高鹼濃度，故其對於光阻層具有較佳的滲透性。 因此，無機顯影劑組合物較有機顯影劑組合物更利於顯影 光阻圖案。然而，無機顯影劑組合物的滲透性依據其成分 不全然滿足需求，且光阻剩餘物會在顯影步驟後遺留。故， 亟需一種顯影劑組合物，其對光阻層具有足夠的滲透性， 及較佳的顯影特性，以建立欲求的精密光阻圖案，而無留 下或留下較少剩餘物。 【發明内容】However, the organic developer composition has low permeability to light and low solubility, which increases the time for developing the photoresist and destroys the shape of the photoresist profile and the accuracy of the size of the photoresist pattern. Therefore, an inorganic developer composition is mixed with a nonionic or ionic surfactant and an aqueous solution of an inorganic alkali (including potassium hydroxide, sodium hydroxide, sodium phosphate, sodium citrate, sodium carbonate, sodium hydrogencarbonate, etc.). The land is adopted by the industry. The inorganic developer composition has a better permeability to the photoresist layer due to its high solubility to water and its high alkali concentration. Therefore, the inorganic developer composition is more advantageous for developing the photoresist pattern than the organic developer composition. However, the permeability of the inorganic developer composition does not fully satisfy the requirements depending on its composition, and the photoresist residue remains after the development step. Therefore, there is a need for a developer composition which has sufficient permeability to the photoresist layer and better development characteristics to create the desired precision photoresist pattern without leaving or leaving less residue. [Summary of the Invention]
因此，本發明之一目的係提供一種光阻顯影劑組合物， 其對光阻層具有足夠滲透性與溶解度，且可形成一欲求精 密光阻圖案。本發明另一目的係提供一種光阻顯影劑組合 物，其之成分間具有較佳相容度，以在顯影步驟後降低剩 餘物的產生。本發明又一目的係提供一種光阻顯影劑組合 物，其可依據顯影製程的條件，在以水稀釋後加以使用。 為了達到該些與其它目的，本發明提供一種光阻顯影劑 組合物，在全部顯影劑組合物内，至少包含1.0至1 0.0重 量百分比之一無機鹼化合物、〇·1至3.0重量百分比之有機 溶劑、1.0至2 0.0重量百分比之界面活性劑及6 7至9 7.9 4 1314248 與離 utf 齊 ¥ 性與 活劑 面性 界活 子面 離界 陰子 為離 佳陰 較而 劑’ 性物 活合 面混 界的 ο 劑 水性 之活 比面 分界 百 子 量離 重非 子界面活性劑的重量比例為1 : 10至1 : 10 0。 【實施方式】 參考以下詳細描述，可更完整理解本發明以及所伴隨之 許多優點。本發明之光阻顯影劑組合物包含一無機驗化合 物、一有機溶劑、一界面活性劑與水。無機驗化合物可選 自氫氧化鉀、氫氧化鈉、磷酸鈉、矽酸鈉、碳酸鈉、碳酸 氫納、及其混合物。在全部顯影劑組合物内，無機驗化合 物含量較佳為1.0至10.0重量百分比，更佳為1.0至5.0 重量百分比。當無機驗化合物含量少於1.0重量百分比， 光阻顯影劑組合物滲透入光阻層聚合物成分的滲透度係不 足夠，而欲顯影的光阻區域無充足地溶解於光阻顯影劑組 合物内。當無機鹼化合物含量大於10.0重量百分比，光阻 顯影劑組合物的滲透度過度地增加，而顯影步驟後欲留下 的光阻區域係部分地建立或腐蝕，而使顯影的光阻輪廓形 狀惡化。 本發明之光阻顯影劑組合物中，有機溶劑較佳包含一對 水有足夠相容性且可溶解光阻層的有機化合物。示範有機 溶劑包含甲醇、乙醇、1_丙醇、2 -丙醇、丁醇、二丙酮醇、 乙二醇單曱基醚、乙二醇單乙基醚、乙二醇單丁基醚、二 乙二醇單甲基醚、二乙二醇單乙基醚、二丙二醇單曱基醚、 二丙二醇單乙基醚、及其混合物。在全部顯影劑組合物内， 有機溶劑含量較佳為〇. 1至3.0重量百分比，更佳為0 · 5 5 !314248 至2.0重量百分比，當有機溶劑含量小於〇·丨重量百分比， 光阻層低分子量樹脂的溶解度係降低。當有機溶劑含量大 於3.0重量百分比，鹼化合物的解離度係不欲求地降低。 本發明光阻顯影劑組合物中，較佳界面活性劑包含陰離 子界面活性劑與非離子界面活性劑。丨範非離子界面活性 劑包含聚氧基烷基醚諸如聚氧基乙基醚1氧基丙基喊、 聚氧基乙基辛基苯基Μ、聚氧基丙基辛基苯基_、聚氧、基 乙基丙基趟、$氧基&基丙基辛基苯基喊、及其混合物。 而示範陰離子界面活性劑包合护其坊絲〜a ⑷匕3烷基硫酸鈉諸如月桂基硫酸 鈉（sodium laurate sulfate)#。鉍社 ^ β . )寻較佳界面活性劑係與水及有 機溶劑相容，且容於水及右A、々也 有機；谷劑内。陰離子界面活性刺 增加水及有機溶劑的溶解疮 .. 各解度。在全部顯影劑組合物中，界 面活性劑含量較佳為1 〇至 2〇.〇重罝百分比，而陰離子界 面活性劑與非離子界面活性 王劑的重篁比例較佳為1 : 1 〇至 1 : 1 0 0。當界面活性劑合I w 量小於1.0重量百分比，顯影劑 組合物對光阻層的水满性除^ "、降低’而對光阻層的顯影能力降 低。當界面活性劑含詈士认、 . ;20·0重量百分比，顯影劑組合 物的水濕性過度增加， . 在顯影步驟後部分地顯影或腐蝕 欲留下的光阻區域，且不 力要的剩餘物甚至在清洗顯影光 阻圖案傻留在光阻圖銮卜 , ' ^陰離子界面活性劑與非離子 界面活性劑的重量比例小 ,.於1 : 10，對光阻層的顯影能力 不欲求地降低。當比 _ ;1.10〇，顯影劑組合物之成分 間的相容性係降低。 本發明之光阻顯影组人 ’ D物包含水，較佳為純水（去離子 6 1314248 水），其以離子交換樹脂過濾。更佳的 18Mega-0hm(ii)之特定阻抗的純水。在全力水為具有大於 中，水含量較佳為67至97.9重量百分J :影劑組合物 67重量百分比’在顯影光阻圖案後，較難、均水含量低於 的廢物。當水含量大於97.9重量百分比，“處理顯影產生 儲存成本係不欲求地增加， 顯影劑的運送與 明光阻顯影劑組合物可以適用於 如光阻層形式、其它製造TFT-LCD或半導影製程條件（諸 的水加以稀釋。當使用稀釋的顯影劑組體的製程條件） 顯影劑組合物含量在最終顯影劑組合 ’本發明光阻 量百分屮 m ^0·5至5.0重 董為刀比。在最終顯影劑組合物中，當 置 物含I 你Λ C & 明顯影劑組合 於0.5重量百分比，最終顯影劑 力俜不；？热· a 13物之顯影能 刀係不足夠，當本發明之顯影組合物含 . 大於5·〇重量百 才比，在顯影光阻圖案後係難以處理顯影產生的廢物。 之後，提供本發明較佳示範例，以更理解本發明。然而， 以下實例僅用以說明本發明，但本發明無偈限於此。’、在以 下實例中，若無特別申明’百分比與比例係分別為重量百 分比與重量比例。 測試片之預備：傳統彩色光阻組合物係旋轉塗布於LCD 玻璃之鉻遮光層（black matrix)上，以製造厚度為1·5μιη的 光阻層。光阻層以熱板在90 C預硬烤9〇秒’而罩幕設於 光阻層上。以電子束曝光（2〇mj/cm2)光陴層以製造一測試 片0 1314248 顯影劑組合物之預備：藉由調整無機鹼化合物、有機溶 劑、界面活性劑與水之含量與種類，而製備示範例1 _ 8及 比較示範例1 - 4的顯影劑組合物，如第1表所示。 (a)無機鹼化合物 (b)有機溶剤 (c)界面活性劑 〔d)水 示範例 KOH NaOH N212CO3 MeOH EtOH EGEE dpgme POEO ES 水 1 1.0 L0 10.0 0.8 87.2 2 3.0 1.0 10.0 0.5 85.5 3 5.0 1.0 5.0 0.3 88.7 4 8.0 1.0 5.0 0.1 85.9 5 3.0 1.0 10.0 0.8 85.2 6 8.0 1.0 5.0 0.3 85.7 7 2.0 1.0 10,0 0.8 86.2 8 5.0 1.0 5.0 0.3 88.7 ⑷無杉 免鹼化合物 (b)有機溶劑 (C)界面 活性劑 ⑷水 比較示 範例 KOH TMAH MtOH EtOH EGEE DPGME POEO ES 水 1 0.5 2.0 5.0 0.1 92.4 2 5.0 5.0 0.5 89.4 3 3.0 3.0 10.0 0.5 83.5 4 8.0 1.0 5.0 0.3 83.7 在表1中，KOH為氫氧化鉀，Na〇H為氫氧化鈉，他2(：〇3 為碳酸納，MeOH為甲醇，Et〇H為乙醇，邱抑為乙二醇 早乙基_ ’ DPGME為二丙二醇單甲基謎，p〇E〇為聚氧基 乙基辛基苯基醚’ ES為月桂基硫酸鈉，而TMAH為四曱 基銨氩氧化物。 1314248 將第 1表所示之示範例與比較示範例之顯影劑組合物 噴灑於暴露光阻層上1 00秒，並以去離子水（D.I.水）清洗光 阻層，並乾燥。以裸視及電子顯微鏡（製造者LEIC A公司， 行號FTM-2 0 0)觀察已顯影的光阻層，並根據顯影區域與未 顯影區域所形成的光阻圖案表面條件與形狀來決定顯影光 阻層的「好」或「壞」。結果示於第2表。 表2 觀察方法 裸視觀察 電子顯微鏡觀察 示範例1 好 好 示範例2 好 好 示範例3 好 好 示範例4 好 好 示範例5 好 好 示範例6 好 好 示範例7 好 好 示範例8 好 好 比較示範例1 好 壞 比較示範例2 好 壞 比較示範例3 壞 壞 比較示範例4 壞 壞 如第2表所示，以本發明示範例之光阻顯影劑組合物完 成的顯影步驟，已曝光的剩下圖案區域與未曝光的顯影區 域係形成欲求輪廓。然而，以比較示範例之光阻顯影劑組 合物完成的顯影步驟，其留下的圖案形狀係非欲求且品質 9 1314248 較差。亦即，本發明之光阻顯影劑組合物在曝光光阻區域 的表面無引起腐蝕，且對於非曝光區域具有較佳顯影特性 而無留下剩餘物。 'Accordingly, it is an object of the present invention to provide a photoresist developer composition which has sufficient permeability and solubility to the photoresist layer and which forms a desired photoresist pattern. Another object of the present invention is to provide a photoresist developer composition having a preferred compatibility between components to reduce the generation of residuals after the development step. Another object of the present invention is to provide a photoresist developer composition which can be used after being diluted with water depending on the conditions of the development process. In order to achieve such other and other objects, the present invention provides a photoresist developer composition comprising at least 1.0 to 10.0% by weight of an inorganic base compound, from 1 to 3.0% by weight of the total of the entire developer composition. Solvent, 1.0 to 20.0% by weight of surfactant and 6 7 to 9 7.9 4 1314248 and utf ¥ 性 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 与 为 为 为 为 为 为 为 为 为 为 为 为 为The ratio of the weight of the water to the surface of the blended surface is 1:10 to 1:10. [Embodiment] The present invention and many of the attendant advantages will be more fully understood from the following detailed description. The photoresist developer composition of the present invention comprises an inorganic compound, an organic solvent, a surfactant and water. Inorganic compounds are selected from the group consisting of potassium hydroxide, sodium hydroxide, sodium phosphate, sodium citrate, sodium carbonate, sodium hydrogencarbonate, and mixtures thereof. The inorganic compound content is preferably from 1.0 to 10.0% by weight, more preferably from 1.0 to 5.0% by weight, based on the total developer composition. When the inorganic compound content is less than 1.0% by weight, the penetration of the photoresist composition into the polymer component of the photoresist layer is insufficient, and the photoresist region to be developed is not sufficiently dissolved in the photoresist developer composition. Inside. When the inorganic base compound content is more than 10.0% by weight, the permeability of the photoresist developer composition is excessively increased, and the photoresist region to be left after the development step is partially established or corroded, and the developed photoresist profile shape is deteriorated. . In the photoresist developer composition of the present invention, the organic solvent preferably contains an organic compound which is sufficiently compatible with water and which dissolves the photoresist layer. Exemplary organic solvents include methanol, ethanol, 1-propanol, 2-propanol, butanol, diacetone alcohol, ethylene glycol monodecyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, two Ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monodecyl ether, dipropylene glycol monoethyl ether, and mixtures thereof. The organic solvent content in the entire developer composition is preferably from 0.1 to 3.0% by weight, more preferably from 0.55 to 314248 to 2.0% by weight, when the organic solvent content is less than 〇·丨 by weight, the photoresist layer The solubility of the low molecular weight resin is reduced. When the organic solvent content is more than 3.0% by weight, the degree of dissociation of the alkali compound is undesirably lowered. In the photoresist developer composition of the present invention, it is preferred that the surfactant comprises an anionic surfactant and a nonionic surfactant. The nonionic surfactants include polyoxyalkyl ethers such as polyoxyethyl ether 1-oxypropyl, polyoxyethyl octylphenyl hydrazine, polyoxypropyl octyl phenyl _, Polyoxyl, ethethyl propyl hydrazine, oxy group & propyl octyl phenyl fluorene, and mixtures thereof. The exemplary anionic surfactant is encapsulated with a square wire of a ~ 4 (4) 匕 3 alkyl sulfate such as sodium laurate sulfate #.铋社 ^β .) Finding better surfactants is compatible with water and organic solvents, and is suitable for water and right A, 々 also organic; Anionic interfacial activity thorn increases the solubilization of water and organic solvents. In all the developer compositions, the surfactant content is preferably from 1 〇 to 2 〇. 〇 罝 ,, and the ratio of the anionic surfactant to the nonionic surfactant is preferably 1: 1 〇 to 1 : 1 0 0. When the amount of the surfactant I w is less than 1.0% by weight, the developer composition is reduced in water saturation of the photoresist layer, and the developing ability of the photoresist layer is lowered. When the surfactant contains a gentleman, .20% by weight, the water wettability of the developer composition is excessively increased, partially developing or etching the photoresist region to be left after the development step, and is not desirable. The residue even in the cleaning and developing photoresist pattern is stupid in the photoresist pattern, ' ^ anionic surfactant and nonionic surfactant weight ratio is small, at 1: 10, the development ability of the photoresist layer is not desired Reduced ground. When the ratio is _; 1.10 Torr, the compatibility between the components of the developer composition is lowered. The photoresist development group of the present invention contains water, preferably pure water (deionized 6 1314248 water), which is filtered with an ion exchange resin. Better 18Mega-0hm(ii) pure water with a specific impedance. In the case where the full strength water is greater than, the water content is preferably 67 to 97.9 weight percent J: the toner composition 67 weight percent' waste after the development of the photoresist pattern is less difficult and the water content is lower. When the water content is more than 97.9 weight percent, "the processing development results in an undesired increase in the storage cost, and the developer transport and bright photoresist developer composition can be applied in the form of, for example, a photoresist layer, other fabrication TFT-LCD or semi-transparent film processes. Conditions (diluted water is diluted. When the process conditions of the diluted developer body are used) The developer composition content is in the final developer combination 'The photoresist amount of the present invention is ^m ^0·5 to 5.0. In the final developer composition, when the storage contains I, Λ C & clear developer is combined at 0.5% by weight, the final developer is not strong; the heat of a 13 developing knives is not enough, when The developing composition of the present invention contains more than 5% by weight, and it is difficult to handle the waste generated by development after developing the resist pattern. Hereinafter, preferred embodiments of the present invention are provided to better understand the present invention. The examples are only intended to illustrate the invention, but the invention is not limited thereto. ' In the following examples, unless otherwise stated, 'percentage and ratio are respectively weight percent to weight ratio. Preparation: The conventional color resist composition is spin-coated on a black matrix of LCD glass to produce a photoresist layer having a thickness of 1.5 μm. The photoresist layer is pre-baked at 90 C with a hot plate. The leap seconds' and the mask are placed on the photoresist layer. The electron beam is exposed (2〇mj/cm2) to produce a test piece. 0 1314248 Preparation of the developer composition: by adjusting the inorganic base compound, organic solvent The developer compositions of Examples 1 to 8 and Comparative Examples 1 to 4 were prepared as shown in Table 1, (a) inorganic base compound (b) organic solvent ( c) Surfactant [d) Water Example KOH NaOH N212CO3 MeOH EtOH EGEE dpgme POEO ES Water 1 1.0 L0 10.0 0.8 87.2 2 3.0 1.0 10.0 0.5 85.5 3 5.0 1.0 5.0 0.3 88.7 4 8.0 1.0 5.0 0.1 85.9 5 3.0 1.0 10.0 0.8 85.2 6 8.0 1.0 5.0 0.3 85.7 7 2.0 1.0 10,0 0.8 86.2 8 5.0 1.0 5.0 0.3 88.7 (4) Unsalted compound (b) Organic solvent (C) surfactant (4) Water comparison example KOH TMAH MtOH EtOH EGEE DPGME POEO ES Water 1 0.5 2.0 5.0 0.1 92.4 2 5.0 5.0 0.5 89.4 3 3.0 3.0 10.0 0.5 83.5 4 8.0 1.0 5.0 0.3 83.7 In Table 1, KOH is potassium hydroxide, Na〇H is sodium hydroxide, and 2 (:〇3 is Sodium carbonate, MeOH is methanol, Et〇H is ethanol, Qiu is ethylene glycol early ethyl _ ' DPGME is dipropylene glycol monomethyl mystery, p〇E〇 is polyoxyethyl octyl phenyl ether ' ES It is sodium lauryl sulfate, and TMAH is tetradecyl ammonium argon oxide. 1314248 The developer composition of the example shown in Table 1 and the comparative example were sprayed onto the exposed photoresist layer for 100 seconds, and the photoresist layer was washed with deionized water (D.I. water) and dried. The developed photoresist layer was observed by naked vision and electron microscopy (manufacturer LEIC A, line number FTM-2 0 0), and development was determined according to the surface condition and shape of the photoresist pattern formed by the developed region and the undeveloped region. "good" or "bad" of the photoresist layer. The results are shown in Table 2. Table 2 Observation method naked observation electron microscope observation example 1 good example 2 good example 3 good example 4 good example 5 good example 6 good example 7 good example 8 good comparison example 1 good and bad comparison demonstration Example 2 Good or bad Comparative Example 3 Bad comparison Example 4 Bad as shown in Table 2, the development step performed with the photoresist developer composition of the exemplary embodiment of the present invention, the remaining pattern area exposed and unexposed The development area forms the desired contour. However, in the development step which was carried out in the comparative example of the photoresist developer composition, the pattern shape left was undesired and the quality 9 1314248 was inferior. That is, the photoresist developer composition of the present invention does not cause corrosion on the surface of the exposed photoresist region, and has better developing characteristics for the non-exposed regions without leaving a residue. '
如上所述，本發明之光阻顯影劑組合物排除傳統顯影劑 I 組合物的缺點，諸如難以清洗、腐蝕曝光光阻區域的表面 等。此外，本發明之光阻顯影劑組合物對於光阻層具有較 佳滲透性、較佳顯影與溶解能力、及較佳水濕性。因此本 發明之組合物可形成欲求之高精密光阻圖案，且降低顯影 步驟後剩餘物的產生。 ® 【圖式簡單說明】 無 【元件代表符號簡單說明】 無As described above, the photoresist developer composition of the present invention eliminates the disadvantages of the conventional developer I composition, such as difficulty in cleaning, etching the surface of the exposed photoresist region, and the like. Further, the photoresist developer composition of the present invention has better permeability to the photoresist layer, better development and dissolution ability, and better water wettability. Therefore, the composition of the present invention can form a desired high-precision photoresist pattern and reduce the generation of residues after the development step. ® [Simple diagram description] None [Simple description of component symbol] None
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