TWI338822B - - Google Patents

Description

1338822 九、發明說明： 【發明所屬之技術領域】1338822 IX. Description of the invention: [Technical field to which the invention belongs]

本發明係有關於一種光阻清洗劑，尤指一種包含乙酸 丙二醇單曱基醚酯（pr〇pylene glycol mono_methyl ether acetate, PGMEA)或其衍生化合物與環己酮 (Cyc 1 ohexanone，AN0NE)或其衍生化合物成分之光阻清 洗劑；此光阻清洗劑命名為"E Z s e r i e s "溶劑， 之後以EZ s ο 1 v e η 1;稱之。 【先前技術】 為製造液晶顯示器（L C D )電路或半導體積體電 :路内所用的微小電路圖案，在基板上之一絕緣體層或導電 ；-金屬層上均勻覆蓋或塗敷一種包括聚合物樹脂，感光化合 物與溶劑之光阻組合物’覆蓋或塗敷的基板經溫焙以蒸發 溶劑，溫焙過之基板選擇地曝露於某些型式之輻射如势外 線，電子威X 一射線，曝露過的基板再經熱烤，隨後 、熱烤基板㈣影產生所預期®案’顯影之基板再以餘刻脫 除絕緣體廣或導電金屬層，並移去餘留的光阻劑層以完成 微小圖案移轉於基板表面上。 由於基板邊上総漏比料H較不均勻，所以 要除去晶片中糾衫阻·或珠粒（*均勾的光阻劑 塊所形成），旅清洗此基板。目前已有機械的與化學的方 法可脫除不均勻之過多光阻劑或殊粗，但此種方法離期望 甚遠。若固^匕覆蓋經機械到削清理則會造成些許物理損傷 5 1338822 附帶脫除材料幾屬必然。或者，固化覆層經化學方法如洗 條、清潔或用清洗劑弄薄，習知光阻清洗劑通常為曱基異 丁基曱 S同（Methyl isobutyl ketone，MIBK)。此化合物 : 雖具有清洗光阻之充分能力，但對人與環境有毒，故其使 用受到IS014000環境管理認證所限制。因此，有必要以 其他物質替代曱基異丁基曱酮的使用。 美國專利4，9 8 3，4 9 0號揭露一種光阻清洗劑，組成成 分包括1-10份重量丙二醇單曱基鱗（Propylene glycol 、mono-methyl ether，PGME)與卜1〇份重量乙酸丙二醇 單曱基醚酯（Propylene glycol mono-methyl ether acetate，PGMEA)。不過此光阻清洗劑清洗部分光阻劑的 : 能力差’且光阻清洗劑溶解度及蒸發速度均為低；另外， 二尚有多種的光阻清洗劑在美國專利5, 814, 433號、 * 5, 849, 467 號、6, 1 17, 623 號、6, 524, 775 號被揭露。目 前為業界大量使用的光阻清洗劑（或被稱為ACS，Array clean solvent)，除前述包含PGME和PGMEA的混合成分 •I·外，尚有如單獨成分的醋酸正丁酯（nBAc，n-ButylThe present invention relates to a photoresist cleaning agent, and more particularly to a method comprising pr〇pylene glycol mono-methyl ether acetate (PMMEA) or a derivative thereof and cyclohexanone (Cyc 1 ohexanone, AN0NE) or A photoresist cleaner derived from a compound component; this photoresist cleaner is named "EZ series " solvent, and is then referred to as EZ s ve 1 ve η 1; [Prior Art] To fabricate a liquid crystal display (LCD) circuit or a semiconductor integrated circuit: a microcircuit pattern used in a circuit, an insulating layer or a conductive layer on a substrate; or a metal layer uniformly covering or coating a polymer resin The photoresist composition of the photosensitive compound and the solvent is covered or coated with a substrate to be heated to evaporate the solvent, and the substrate which is warmly baked is selectively exposed to certain types of radiation such as an external line, and the electron is exposed to X-ray. The substrate is then thermally baked, and then the substrate is thermally baked (4) to produce the desired substrate of the developed substrate, and then the insulator or conductive metal layer is removed, and the remaining photoresist layer is removed to complete the micro pattern. Transfer to the surface of the substrate. Since the leakage on the side of the substrate is less uniform than the material H, the substrate is removed by removing the correction resistors or beads (formed by the photoresist blocks). There are mechanical and chemical methods available to remove uneven photoresist or excessive thickness, but this method is far from expected. If the solid cover is mechanically removed, it will cause some physical damage. 5 1338822 It is inevitable that the material is removed. Alternatively, the cured coating is chemically cleaned, cleaned or thinned with a cleaning agent. The conventional photoresist is usually Methyl isobutyl ketone (MIBK). This compound: Although it has sufficient ability to clean photoresist, it is toxic to humans and the environment, so its use is limited by IS014000 environmental management certification. Therefore, it is necessary to replace the use of decyl isobutyl fluorenone with other substances. U.S. Patent No. 4,9,8,3,099 discloses a photoresist cleaning agent comprising 1-10 parts by weight of propylene glycol mono-methyl ether (PGME) and 1 part by weight of acetic acid. Propylene glycol mono-methyl ether acetate (PGMEA). However, this photoresist cleaning agent cleans part of the photoresist: poor ability 'and the photoresist cleaning agent solubility and evaporation rate are low; in addition, there are a variety of photoresist cleaning agents in US patents 5, 814, 433, * 5, 849, 467, 6, 1 17, 623, 6, 524, 775 are disclosed. Currently used in the industry as a photoresist cleaner (or ACS, Array clean solvent), in addition to the above-mentioned mixed components containing PGME and PGMEA, there is still a separate component of n-butyl acetate (nBAc, n- Butyl

Acetate)、乙酸異戊酷（IAAc，Isoamyl acetate)及包 含PGME、PGMEA和nBAc混合成分的光阻清洗劑，其被使 用於塗佈機清洗（Coaterc叩rinse)、玻璃基板邊緣清洗 (EBR ， Glass substrate for edge bead remover)、機 台管路清洗（tube clean in equipment)等用途。 除考慮價格等因素外，光阻清洗劑尚須考慮對人類無 毒性，不影響社會生態，且無令人不愉快氣味，亦能迅速 1338822 地完全去除基板上固化的或未熟的光阻劑層，對不同光阻 混合的相容性極佳且不會對其產生污染及損傷。 【發明内容】 本發明之主要目的在於提供了一種光阻清洗劑，其對 人體具極低毒性，使用上具安全性，且無令人不愉快氣味。 本發明之另一目的在於提供了一種光阻清洗劑，其不 會對環境造成污染，且其廢液及廢水容易處理。Acetate), IAAc, Isoamyl acetate, and photoresist cleaner containing PGME, PGMEA and nBAc blends, used in coater cleaning (Coaterc叩rinse), glass substrate edge cleaning (EBR, Glass) Substrate for edge bead remover), tube clean in equipment, etc. In addition to considering the price and other factors, the photoresist cleaning agent must be considered to be non-toxic to humans, does not affect the social ecology, and has no unpleasant odor. It can also completely remove the cured or immature photoresist layer on the substrate by 1338822. Excellent compatibility with different photoresist combinations without contamination and damage. SUMMARY OF THE INVENTION A primary object of the present invention is to provide a photoresist cleaning agent which has extremely low toxicity to human body, is safe to use, and has no unpleasant odor. Another object of the present invention is to provide a photoresist cleaning agent which does not pollute the environment and which is easy to handle waste liquid and waste water.

本發明之再一目的在於提供了一種光阻清洗劑，其對 光阻層具有良好的溶解度，適宜的揮發性，優越的清洗能 力0 本發明之又一目的在於提供了一種光阻清洗劑，其能 於室溫儲存，成本低廉，且不需更換習用設備與生產條件。 本發明之進一目的在於提供了一種光阻清洗劑，對不 同光阻混合物有良好之相容性，對製程更換過程不會有不 可預期的不良效果。 根據以上所述之目的，本發明提供了 一種光阻清洗 劑，包含乙酸丙二醇單曱基醚酯（PGMEA)或其衍生化合物 與環己酮（ANONE)或其衍生化合物。 根據上述構想，其中ANONE可用ANONE的衍生化合物取 代，其結構係自[式二]選出。 根據上述構想，其中PGMEA可用PGMEA的衍生化合物取 代，其結構係自[式一]選出。 根據上述構想，其中PGMEA與ANONE的重量百分組成比 7 1338822 從5% : 95%至 95% : 5〇/〇。 根據上述構想’其中PGMEA與ANONE的較佳重量百分組 ' 成比從50% : 50%至90% : 10%。 根據上述構想，其中該光阻清洗劑可應用於下列場 合’基板邊緣清洗、塗佈機殘留光阻清洗和機台管路殘留 光阻清洗。 根據上述構想，其中該基板邊緣清洗所使用的基板係 從下列中選出：矽晶圓、玻璃基板、包含金屬層之破j离基 板、包含氧化石夕層之玻璃基板、包含氮化矽層之玻璃基板 和包含石夕層之玻璃基板。 根據上述構想，其中該光阻清洗劑可用於清洗正光阻 . 及負光阻。 【實施方式】 為能使貴審查委員清楚本發明之主要技術内容， 以及實施方式，茲配合圖式說明如下：A further object of the present invention is to provide a photoresist cleaning agent which has good solubility to a photoresist layer, suitable volatility, and superior cleaning ability. A further object of the present invention is to provide a photoresist cleaning agent. It can be stored at room temperature, is inexpensive, and does not require replacement of conventional equipment and production conditions. A further object of the present invention is to provide a photoresist cleaning agent which has good compatibility with different photoresist mixtures and which does not have unpredictable adverse effects on the process replacement process. In accordance with the above objects, the present invention provides a photoresist cleaning agent comprising propylene glycol monodecyl ether ester (PGMEA) or a derivative thereof and cyclohexanone (ANONE) or a derivative thereof. According to the above concept, ANONE can be substituted with a derivative compound of ANONE, and its structure is selected from [Formula 2]. According to the above concept, wherein PGMEA can be substituted with a derivative compound of PGMEA, the structure is selected from [Formula 1]. According to the above concept, the weight percentage composition ratio of PGMEA to ANONE is 7 1338822 from 5%: 95% to 95%: 5〇/〇. According to the above concept, 'the preferred weight percentage group of PGMEA and ANONE' is from 50%: 50% to 90%: 10%. According to the above concept, the photoresist cleaning agent can be applied to the following field substrate edge cleaning, coater residual photoresist cleaning, and machine line residual photoresist cleaning. According to the above concept, the substrate used for the edge cleaning of the substrate is selected from the group consisting of a germanium wafer, a glass substrate, a broken substrate including a metal layer, a glass substrate including an oxide layer, and a tantalum nitride layer. A glass substrate and a glass substrate comprising a stone layer. According to the above concept, the photoresist cleaning agent can be used for cleaning positive photoresist and negative photoresist. [Embodiment] In order to enable the reviewing committee members to understand the main technical contents and implementation modes of the present invention, the following description is in conjunction with the drawings:

光阻劑可區分為正光阻（positive photoresist)及 負光阻（negative photoresist)，視其于顯影清洗後所保 留的圖案而定。光阻劑可經普通塗覆技術諸如浸潰，喷 霧’旋轉及自轉等步驟塗覆在半導體基板或LCD基板上。 基板材料可包含石夕晶圓（Si wafer)、玻璃基板（glass)、 包含金屬層之玻璃基板（metal film 〇n glass)、包含氧 化石夕層之玻璃基板（SiOx f i lm on glass)、包含氮化石夕層 之玻璃基板（SiNx fi lm on glass)和包含石夕層之玻璃基板 1338822 (Si film on glass)等。當光阻劑塗覆於基板上，特別經 ' 自轉塗覆時其不均勻部分例如基板上的珠粒等係因光阻 胃劑塊引起。 ' 本發明光阻清洗劑能喷霧於基板上使珠粒溶解，製得 均勻光阻劑層，清洗步驟亦可在其後溫焙步驟或熱烤步驟 之後執行，經光阻塗覆的基板於20至100度加熱進行溫培 步驟，此步驟容許溶劑蒸發而不高溫分解光阻劑中固體成 分，進行至溶劑大多蒸發使基板上產生光阻劑之薄塗覆 今^層。 其次，塗覆光阻劑層的基板經選擇地曝露於一種輻射 諸如紫外光，電子或X —射線與一適當光罩獲得所需圖 : 案，曝曬過之基板隨後浸入一含鹼性顯影液中直到任意已 / 曝露或未曝露的光阻劑（視光阻劑屬於正光阻或負光阻型 ' 式而定）完全或幾乎全部溶解，然後自顯影液中取出己曝 曬或未曝露之光阻劑脫除基板，隨後經熱處理以改善黏附 並提升光阻劑層之抗化學物性，此步驟稱熱烤步驟。已顯 影的基板以一濕刻触或電漿触刻已曝露部分’接下來為處 理保護遮蔽基板區之殘留光阻，利用一洗提劑（Str ipper) 脫除蝕刻後的基板中光阻劑層以完全轉移圖案於基板表 面上。 表1毒性試驗 溶劑 毒物學資料 MIBK LD50/口服/ 鼠：2080mg/kg LC5()/吸入/大鼠：4000ppm 9 1338822 nBAc LD50/口服/大鼠：13100mg/kg LC5。/吸入/大鼠：2000ppm(4小時) PGMEA LDs。/口服/大鼠：8532mg/kg LD5〇/皮下/大鼠：5000mg/kg 1X5。/吸入/大鼠：4345ppm(6小時) ANONE LD50/口服/大鼠：1535mg/l(g LC5。/吸入/大鼠：8000ppm(6小時)The photoresist can be classified into a positive photoresist and a negative photoresist depending on the pattern retained after development cleaning. The photoresist can be applied to a semiconductor substrate or an LCD substrate by conventional coating techniques such as dipping, spraying, rotation and spinning. The substrate material may include a Si wafer, a glass substrate, a metal film metaln glass, a SiOx fi lm on glass, and the like. a glass substrate (SiNx fi lm on glass) of a nitride layer and a glass substrate 1338822 (Si film on glass) containing a shisha layer. When the photoresist is applied to the substrate, particularly in the case of 'rotation coating, its uneven portion such as beads on the substrate is caused by the photoresist stomach block. The photoresist cleaning agent of the present invention can be sprayed on a substrate to dissolve the beads to obtain a uniform photoresist layer, and the cleaning step can also be performed after the subsequent warm baking step or the hot baking step, and the photoresist coated substrate Heating at 20 to 100 degrees is carried out by a temperature-increasing step which allows the solvent to evaporate without decomposing the solid component of the photoresist at a high temperature, until the solvent is mostly evaporated to cause a thin coating of the photoresist on the substrate. Secondly, the substrate coated with the photoresist layer is selectively exposed to a radiation such as ultraviolet light, electrons or X-rays and a suitable mask to obtain the desired pattern: the exposed substrate is then immersed in an alkaline developing solution. Dissolve completely or almost completely until any exposed or unexposed photoresist (depending on whether the photoresist is of positive or negative photoresist type), and then remove the exposed or unexposed light from the developer. The resist removes the substrate and is subsequently heat treated to improve adhesion and enhance the chemical resistance of the photoresist layer. This step is referred to as the hot bake step. The developed substrate is exposed to the exposed portion by a wet touch or plasma. The photoresist is then removed to remove the residual photoresist. The photoresist is removed from the etched substrate by a stripper. The layer is on the surface of the substrate in a complete transfer pattern. Table 1 Toxicity test Solvent Toxicological information MIBK LD50/oral/rat: 2080 mg/kg LC5 ()/inhalation/rat: 4000 ppm 9 1338822 nBAc LD50/oral/rat: 13100 mg/kg LC5. / Inhalation/rat: 2000 ppm (4 hours) PGMEA LDs. /Oral/rat: 8532 mg/kg LD5 〇/subcutaneous/rat: 5000 mg/kg 1X5. /Inhalation/rat: 4345 ppm (6 hours) ANONE LD50/oral/rat: 1535 mg/l (g LC5./inhalation/rat: 8000 ppm (6 hours)

LD50(致命劑量50):對50%試驗動物致命之物質劑量。 L C 5 0 (低致命濃度）：對人類或動物作2 4小時以下曝露時期 曾經報告致死的空氣内物質量低濃度。LD50 (fatal dose 50): A material dose that is lethal to 50% of the test animals. L C 5 0 (low lethal concentration): exposure to humans or animals for less than 24 hours The low concentration of airborne matter has been reported to be lethal.

考慮合適的光阻清洗劑需對人體具極低毒性，使用上 具安全性，無令人不愉快氣味，且不會對環境造成污染， 其廢液及廢水容易處理。表1與表2分別為習知包含曱基異 丁基甲酮（MIBK，傳統光阻清洗劑），醋酸正丁酯（η B A c )，乙酸乙二醇丁醚酯（PGMEA)，環己酮（ANONE)各種不 同的溶劑，其實行毒性試驗及***測試的結果。 表2著火與***試驗 溶劑 蒸氣壓 (mmHg)/溫 度(。。） 閃火點 cc) 沸點(°C) ***限度 (%) MIBK 16/20 18 115 1.4-7.5 nBAc 7.8/20 22 126 1.7-15 PGMEA 3.8/20 42 146 1.5-7 ANONE 4.0/20 44 156 1.1-9.4 10 1338822 表3為包含乙酸丙二醇單曱基醚酯（PGMEA)，環已鲖 (ANONE)及醋酸正丁酯（nBAc)各種不同的溶劑，其毒性、 ***及化學特性測试的結果。由表1〜3可知，本發明所用 ANONE與PGMEA表現有較良好生物學及物理化學安全特性。 表3毒性、***及化學特性測試 溶劑 LD50 LC50 閃火點 沸點(°C) 揮發點(°C) ----- 黏度(CST) nBAc 13100 2000 22 126 15 0.7 PGMEA 8532 4345 42 146 3.8 1.1 ’ANONE 1535 8000 44 155 4 4 • 表4為利用表3中2種溶劑PGMEA和ΛΝΟΝΕ形成6種不同 ·-重量百分組成的光阻清洗劑。而表5為測試表4的光阻清洗Considering a suitable photoresist cleaning agent, it needs to be extremely toxic to the human body. It is safe to use, has no unpleasant odor, and does not pollute the environment. Its waste liquid and waste water are easy to handle. Tables 1 and 2 respectively contain conventionally known fluorenyl isobutyl ketone (MIBK, conventional photoresist cleaner), n-butyl acetate (η BA c ), ethylene glycol butyl ether acetate (PGMEA), cyclohexanone ( ANONE) A variety of solvents that perform the results of toxicity tests and explosion tests. Table 2 Ignition and Explosion Test Solvent Vapor Pressure (mmHg) / Temperature (..) Flash Point cc) Boiling Point (°C) Explosion Limit (%) MIBK 16/20 18 115 1.4-7.5 nBAc 7.8/20 22 126 1.7- 15 PGMEA 3.8/20 42 146 1.5-7 ANONE 4.0/20 44 156 1.1-9.4 10 1338822 Table 3 contains propylene glycol monodecyl ether ester (PGMEA), ring 鲖 (ANONE) and n-butyl acetate (nBAc) A variety of solvents, the results of toxicity, explosion and chemical properties testing. It can be seen from Tables 1 to 3 that the ANONE and PGMEA used in the present invention exhibit better biological and physicochemical safety characteristics. Table 3 Toxicity, Explosion, and Chemical Properties Test Solvent LD50 LC50 Flash Point Boiling Point (°C) Volatile Point (°C) ----- Viscosity (CST) nBAc 13100 2000 22 126 15 0.7 PGMEA 8532 4345 42 146 3.8 1.1 ' ANONE 1535 8000 44 155 4 4 • Table 4 shows the use of the two solvents PGMEA and the bismuth in Table 3 to form six different weight percent cleaning agents. And Table 5 is the photoresist cleaning of test table 4.

A : 劑對已經應用於LCD製程上的三種商業化光阻劑的溶解能 力結果。我們可以發現編號2至編號6為利用PGMEA和ANONE 組成的配方，編號1為純PGMEA。A: The dissolution ability of the three commercial photoresists that have been applied to the LCD process. We can find that numbers 2 to 6 are formulations using PGMEA and ANONE, number 1 is pure PGMEA.

表4光阻清洗劑的溶劑重量百分組成 編號 PGMEA ANONE 1 100 0 2 90 10 3 85 15 4 80 20 5 70 30 1338822 6 50 50 另外’由於光阻劑包含感光化合物（pAC，Ph〇toactive compound)，其易殘留在基板上無法清除而導致污染後續 製程’本發明之包含PGMEA和ΑΝ0ΝΕ組成的配方之光阻清洗 劑，在常溫常壓下，對PAC之溶解度佳，實驗發現，在包 含4〜6% PAC(% ’重量百分組成）濃度的光阻劑，PGMEA和 ΑΝ0ΝΕ組成的配方可將其完全溶解。Table 4 Solvent weight percent composition of photoresist cleaner Composition number PGMEA ANONE 1 100 0 2 90 10 3 85 15 4 80 20 5 70 30 1338822 6 50 50 Also 'Because the photoresist contains photosensitive compound (pAC, Ph〇toactive compound ), which is easy to remain on the substrate and cannot be removed to cause contamination. The subsequent process of the present invention comprises a photoresist composition comprising a composition of PGMEA and ΑΝ0ΝΕ, which has good solubility to PAC under normal temperature and pressure, and is found to contain 4 ~6% PAC (% 'weight percent composition) concentration of photoresist, PGMEA and ΑΝ0ΝΕ formula can completely dissolve it.

表5光阻洗清劑溶解能力測試 編號 第一種光阻 第二種光阻 第三種光阻 溶解率(埃/秒） 溶解率(埃/秒) 溶解率(埃/秒） 1 2311.4 3473.7 3657.4 2 2379.6 3647.8 3624.2 3 2529.5 4020.4 3837.9 4 3014.4 4644.7 4134.8 _____ '' 5 3537.0 5657.4 5424.1 6 3730.6 5446.5 5389.2 表6溶解速率比較表 溶解速率快慢數值表示法：（1)〉（ 2 ) > (3 ) > (4) > (5 )Table 5: Resistance of Photoresist Cleaning Agent Test No. First Resistance Second Resistance Third Resistivity Dissolution Rate (A/sec) Dissolution Rate (A/sec) Dissolution Rate (A/sec) 1 2311.4 3473.7 3657.4 2 2379.6 3647.8 3624.2 3 2529.5 4020.4 3837.9 4 3014.4 4644.7 4134.8 _____ '' 5 3537.0 5657.4 5424.1 6 3730.6 5446.5 5389.2 Table 6 Comparison of dissolution rates Table of dissolution rate Value representation: (1) > ( 2 ) > (3 ) &gt ; (4) > (5)

Photo-Resist PGMEA/ANONE PGMEA 一 High Color R (3) (5) 1338822 (βΐ m. (5) (5)_ (5) %Photo-Resist PGMEA/ANONE PGMEA A High Color R (3) (5) 1338822 (βΐ m. (5) (5)_ (5) %

Saturation G (3) B (3) Middle Color Saturation R (3) G (3) B (3) Photo Spacer TYPE1 (3) Photo Spacer TYPE2 (3) MVA TYPE1 (3) MVA TYPE2 (3) (5)Saturation G (3) B (3) Middle Color Saturation R (3) G (3) B (3) Photo Spacer TYPE1 (3) Photo Spacer TYPE2 (3) MVA TYPE1 (3) MVA TYPE2 (3) (5)

表7解決Gel和Particle效能比較表Table 7 resolves the comparison of Gel and Particle performance

Photo-Resist _ _ —-- pgmea/anone PGMEA High Color Saturation R ◎ Δ G ◎ △ B ◎ Δ Middle Color Saturation R ◎ Δ _ G ◎ △__ B ◎ ZaIJPhoto-Resist _ _ —-- pgmea/anone PGMEA High Color Saturation R ◎ Δ G ◎ △ B ◎ Δ Middle Color Saturation R ◎ Δ _ G ◎ △__ B ◎ ZaIJ

◎ : GOOD △ : BAD 由於光阻清洗劑另一個特性是溶解速率’針對不同白勺 機台設備和製程，會有不同的要求，有時需要快’有時$ 要慢，在表6中我們比較負型及正型光陴在不同清洗劍$ 方下的溶解速率，其中MVA為正型光限，其它為負型’只 驗結果顯示，本發明之PGMEA和AN0NE組成的配方之溶解遗 率比pure PGMEA快，因LCD製程有一定的生產時間限制’ 所以pure PGMEA的條件較不適合量產應用同日寺在表7 13 1338822 結果也顯示，本發明之PGMEA和ANONE組成的配方之解決 Gel和Particle效能也比pure PGMEA良好。 要注意的是，雖然上述是以乙酸丙二醇單甲基醚酯 * (PGMEA)與環己酮（ANONE)組成之光阻清洗劑進行的實驗 結果，但是也可以利用乙酸丙二醇單曱基醚酯（PGMEA)的 衍生化合物與環己酮（ANONE)的衍生化合物來作為光阻清 洗劑組成成分。 %乙酸丙二醇單曱基醚酯（PGMEA)與其衍生化合物之部分結 構如式一所表示： [式一]◎ : GOOD △ : BAD Since the other characteristic of the photoresist cleaner is the dissolution rate, there are different requirements for different machine equipment and processes, sometimes it needs to be fast 'sometimes too slow, in Table 6 Compare the dissolution rates of negative and positive diaphragms under different cleaning swords, where MVA is a positive light limit and the others are negative. The results only show the dissolution rate of the formulation of PGMEA and AN0NE of the present invention. It is faster than pure PGMEA, because LCD process has a certain production time limit' so the condition of pure PGMEA is less suitable for mass production application. The same day temple in Table 7 13 1338822 The result also shows that the formulation of the PGMEA and ANONE of the present invention solves Gel and Particle. Performance is also better than pure PGMEA. It should be noted that although the above results are based on a photoresist cleaning agent consisting of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (ANONE), it is also possible to use propylene glycol monodecyl ether ester ( A derivative compound of PGMEA) and a derivative compound of cyclohexanone (ANONE) are used as a component of the photoresist cleaner. The partial structure of % propylene glycol monodecyl ether acetate (PGMEA) and its derivative compounds is expressed as in Formula 1: [Formula 1]

PGMEA 衍生物：Rl，R2 = Hydrogen or Cl to C3 AlkylPGMEA Derivative: Rl, R2 = Hydrogen or Cl to C3 Alkyl

環己酮（ANONE)與其衍生化合物之部分結構如式二所表 不. 14 1338822 [式二] 〇The partial structure of cyclohexanone (ANONE) and its derivative compounds is shown in formula II. 14 1338822 [Formula 2] 〇

Cyclohexanone ANONE 衍生物：R3, R4 = Hydrogen or Cl to C3 Alkyl group.Cyclohexanone ANONE derivatives: R3, R4 = Hydrogen or Cl to C3 Alkyl group.

本發明之特徵主要在於提供了 一種包含乙酸丙二醇 單甲基醚酯（PGMEA)或其衍生化合物與環己酮（AN0NE)或 其衍生化合物成分之光阻清洗劑，其中PGMEA與AN0NE的重 量百分組成比是從5% : 95%至95% : 5%，而較佳重量百分組 成比為從50% : 50%至90% : 10%，具有下列特點：（1)對人 體具極低毒性，使用上具安全性，且無令人不愉快氣味， 1338822 (2)不會對環境造成污染，且其廢液及廢水容易處理，（3) * 對光阻層具有良好的溶解度，適宜的揮發性，優越的清洗 能力，（4)能於室溫儲存，成本低廉，且不需更換習用設 ' 備與生產條件。 即使本發明係藉由舉出數個較佳實施例來描述，但是 本發明並不限定於所舉出之實施例。先前雖舉出與敘述之 特定實施例，但是顯而易見地，其它未脫離本發明所揭示 之精神下，所完成之等效改變或修飾，均應包含在本發明 %之申請專利範圍内。此外，凡其它未脫離本發明所揭示之 精神下，所完成之其他類似與近似改變或修飾，也均包含 在本發明之申請專利範圍内。同時應以最廣之定義來解釋 本發明之範圍，藉以包含所有的修飾與類似結構。 摯 '【圖式簡單說明】 【主要元件符號說明】The invention is mainly characterized by providing a photoresist cleaning agent comprising propylene glycol monomethyl ether acetate (PGMEA) or a derivative thereof and cyclohexanone (AN0NE) or a derivative thereof, wherein the weight percentage of PGMEA and AN0NE The composition ratio is from 5%: 95% to 95%: 5%, and the preferred weight percentage composition ratio is from 50%: 50% to 90%: 10%, with the following characteristics: (1) Very low to the human body Toxic, safe to use, and unpleasant odor, 1338822 (2) will not pollute the environment, and its waste liquid and wastewater are easy to handle, (3) * Good solubility to the photoresist layer, suitable Volatile, superior cleaning ability, (4) can be stored at room temperature, low cost, and no need to replace the customary equipment and production conditions. The present invention has been described by way of a few preferred embodiments, but the invention is not limited to the illustrated embodiments. While the invention has been described with respect to the specific embodiments thereof, it is obvious that the equivalents and modifications may be included in the scope of the invention. In addition, other similar and approximate changes or modifications that are made without departing from the spirit of the invention are also included in the scope of the invention. At the same time, the scope of the invention should be construed in the broadest definition, and all modifications and similar structures are included.挚 '[Simple diagram description] [Main component symbol description]

1616

Claims (1)

13388221338822 十、申請專利範圍： 1、一種用於基板邊緣清洗、塗佈機殘留光阻清洗和 機台管路殘留光阻清洗的光阻清洗劑，其由乙酸丙二醇單 曱基醚 S旨（Propylene glycol mono-methyl ether acetate，PGMEA)與環己酮（Cyclohexanone，ANONE)所 組成，其中乙酸丙二醇單曱基醚酯與環己酮的重量百分組 成比為 80% : 20%至 70% : 30%。 2、如請求項1所述之光阻清洗劑，其中該基板邊緣 % 清洗所使用的基板係從下列中選出：矽晶圓（Si wafer)、 玻璃基板（glass)、包含金屬層之玻璃基板（metal film on glass)、包含氧化矽層之玻璃基板（Si〇x film 〇n glass)、包含氮化石夕層之玻璃基板（siΝχ film 〇n glass) 和包含矽層之玻璃基板（Si filin on glass)。 3、如請求項i所述之光阻清洗劑，其中該光阻清洗 劑可用於清洗正光阻（positiVe ph〇t〇resist)及負光阻 (negative photoresist)。X. Patent application scope: 1. A photoresist cleaning agent for substrate edge cleaning, coating machine residual photoresist cleaning and machine tube residual photoresist cleaning, which is made of propylene glycol monodecyl ether S (Propylene glycol) Mono-methyl ether acetate, PGMEA) and cyclohexanone (ANONE), wherein the weight percent composition ratio of propylene glycol monodecyl ether ester to cyclohexanone is 80%: 20% to 70%: 30% . 2. The photoresist cleaning agent according to claim 1, wherein the substrate used for cleaning the edge of the substrate is selected from the group consisting of: a silicon wafer, a glass substrate, and a glass substrate including a metal layer. (metal film on glass), a glass substrate comprising a ruthenium oxide layer, a glass substrate comprising a nitride layer, and a glass substrate comprising a ruthenium layer (Si filin on Glass). 3. The photoresist cleaning agent of claim i, wherein the photoresist cleaning agent is used for cleaning positive photoresists (positiVe ph〇t〇resist) and negative photoresists. 1717