TWI746419B - Photoresist stripper solutions - Google Patents
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本申請案係於2013年2月5日提出申請之美國申請案第13/759,237號之部分繼續，該13/759,237案係於2006年10月24日提出申請之12/091,808之繼續，該12/091,808案係於2005年10月28日提出申請之美國申請案第11/260,912號之部分繼續，該等申請案各自以全文引用方式併入本文中。 This application is part of the continuation of U.S. Application No. 13/759,237 filed on February 5, 2013. The 13/759,237 case is a continuation of 12/091,808 filed on October 24, 2006. The 12 The /091,808 case is a continuation of the U.S. Application No. 11/260,912 filed on October 28, 2005, each of which is incorporated herein by reference in its entirety.
本揭示內容概言之係關於能夠自基板有效除去光阻劑之組合物及其使用方法。該等所揭示組合物係用於除去光阻劑之剝離溶液，該等溶液能夠在低於正常室溫之溫度以及運輸及倉儲中通常遇到之溫度下保持液體且另外具有所除去光阻劑材料之有利負載容量。具有減少之水含量之剝離溶液已證實在清潔地除去光阻劑、提供低銅蝕刻速率及增加光阻劑於剝離溶液中之溶解度(如藉由較低粒子計數證明)中尤其有效。 This disclosure generally relates to a composition capable of effectively removing photoresist from a substrate and its use method. The disclosed compositions are stripping solutions for removing photoresist. These solutions can maintain liquids at temperatures below normal room temperature and temperatures commonly encountered in transportation and storage, and additionally have the removed photoresist Favorable load capacity of the material. Stripping solutions with reduced water content have proven to be particularly effective in removing photoresist cleanly, providing low copper etch rates, and increasing the solubility of the photoresist in the stripping solution (as evidenced by lower particle counts).
寬泛而言，本揭示內容之第一態樣提供自基板有效除去或剝離光阻劑之光阻劑剝離溶液，其具有尤其高之抗蝕劑材料負載容量，且當經受可能在運輸、倉儲及用於一些製造設施中遇到之低於正常室溫之溫度時能夠保持液體。本揭示內容之組合物可在低至約-20℃至約+15℃之溫度下保持液體。本揭示內容之組合物可含有二甲基亞碸
(DMSO)、氫氧化四級銨及烷醇胺。一個較佳實施例含有約20%至約90%二甲基亞碸、約1%至約7%氫氧化四級銨及約1%至約75%烷醇胺(具有至少兩個碳原子、至少一個胺基取代基及至少一個羥基取代基，胺基及羥基取代基可附接至烷醇胺之兩個不同的碳原子)。四級基團可包括(C1-C8)烷基、芳基烷基及其組合。氫氧化四級銨之實例係四甲基氫氧化銨。1,2-烷醇胺可包括下式之化合物：
其中R1可為H、C1-C4烷基或C1-C4烷基胺基。式I之烷醇胺可具有為H或-CH2CH2NH2之R1.本揭示內容之溶液亦可包括另一或第二溶劑。例如，第二溶劑可包括二醇、二醇醚及諸如此類。在另一實例中，第二溶劑可包括醇。具體而言，第二溶劑可包括具有兩個或更多個羥基之多羥基化合物。合意地，至少一個羥基係一級羥基，或至少兩個羥基係一級羥基。 Wherein R 1 can be H, C 1 -C 4 alkyl or C 1 -C 4 alkylamino. The alkanolamine of formula I may have R 1 which is H or -CH 2 CH 2 NH 2. The solution of the present disclosure may also include another or second solvent. For example, the second solvent may include glycol, glycol ether, and the like. In another example, the second solvent may include alcohol. Specifically, the second solvent may include a polyhydroxy compound having two or more hydroxyl groups. Desirably, at least one hydroxyl group is a primary hydroxyl group, or at least two hydroxyl groups are a primary hydroxyl group.
本揭示內容之第二態樣提供使用本文所闡述之剝離溶液自基板除去光阻劑及相關聚合材料之方法。可藉由以下方式自其上具有光阻劑之所選基板除去光阻劑：使基板與剝離溶液接觸達足以除去期望量之光阻劑之時間，自剝離溶液除去基板，用溶劑自基板沖洗剝離溶液並乾燥基板。 The second aspect of the present disclosure provides a method for removing photoresist and related polymeric materials from the substrate using the stripping solution described herein. The photoresist can be removed from the selected substrate with photoresist thereon by the following methods: contact the substrate with the stripping solution for a time sufficient to remove the desired amount of photoresist, remove the substrate from the stripping solution, and rinse the substrate with the solvent The solution is peeled off and the substrate is dried.
本揭示內容之第三態樣包括藉由所揭示之新穎方法製造之電子裝置。 The third aspect of the present disclosure includes electronic devices manufactured by the disclosed novel method.
本揭示內容之第四態樣包括含有二甲基亞碸、氫氧化四級銨、烷醇胺、具有減少量之水之可選第二溶劑之較佳剝離溶液。該等溶液
可具有至少約1之乾度係數。該等溶液亦可具有至少約1.8之乾度係數，其中乾度係數(DC)係藉由以下方程式來定義：
本揭示內容之第五態樣包括用本文所闡述之剝離溶液自基板除去光阻劑之方法。該方法涉及選擇光阻劑沈積於其上之基板，使包括光阻劑之基板與剝離溶液(含有二甲基亞碸、氫氧化四級銨、烷醇胺、可選第二溶劑，其中剝離溶液具有至少約1之乾度係數)接觸，使基板遠離不再接觸剝離溶液及自基板沖洗剝離溶液。 The fifth aspect of the present disclosure includes the method of removing the photoresist from the substrate using the stripping solution described herein. The method involves selecting the substrate on which the photoresist is deposited, so that the substrate including the photoresist and the stripping solution (containing dimethyl sulfoxide, quaternary ammonium hydroxide, alkanolamine, optional second solvent The solution has a dryness coefficient of at least about 1) contact, keep the substrate away from no longer contacting the stripping solution and rinse the stripping solution from the substrate.
本揭示內容之第六態樣包括部分地藉由上文所闡述方法製備之電子裝置。 The sixth aspect of the present disclosure includes an electronic device prepared in part by the method described above.
本揭示內容之第七態樣包括提供乾式組合物之方法，該組合物包括二甲基亞碸、氫氧化四級銨、烷醇胺、可選第二溶劑，其中溶液具有至少約1之乾度係數。 The seventh aspect of the present disclosure includes a method of providing a dry composition, the composition comprising dimethyl sulfoxide, quaternary ammonium hydroxide, alkanolamine, and an optional second solvent, wherein the solution has a dryness of at least about 1 Degree factor.
本揭示內容之第八態樣包括獲得具有減少之水含量之氫氧化四級銨之方法，其係藉由以下方式達成：形成氫氧化四級銨、不期望之水及犧牲溶劑之溶液，及利用輕微升溫使溶液經受減壓。在處理期間，除去一部分犧牲溶劑及水。在該製程期間，應避免過度加熱以防止氫氧化物分解。如有需要，可重複犧牲溶劑以及水之添加及除去，直至水含量充分減少為止。 The eighth aspect of the present disclosure includes a method of obtaining quaternary ammonium hydroxide with reduced water content, which is achieved by forming a solution of quaternary ammonium hydroxide, undesired water, and sacrificial solvent, and The solution was subjected to reduced pressure using a slight temperature increase. During the treatment, a portion of the sacrificial solvent and water are removed. During this process, excessive heating should be avoided to prevent decomposition of the hydroxide. If necessary, the addition and removal of sacrificial solvent and water can be repeated until the water content is sufficiently reduced.
本揭示內容之第九態樣包括使剝離溶液維持低水含量之方法。該方法涉及選擇乾式剝離溶液，在剝離溶液與分子篩之間建立接觸，及維持與篩之接觸直至利用剝離溶液為止。此方法尤其可用於在製造後、在儲存及/或船運期間及在溶液之容器打開後將剝離溶液維持於乾燥形式。 The ninth aspect of the present disclosure includes a method of maintaining a low water content in the stripping solution. The method involves selecting a dry stripping solution, establishing contact between the stripping solution and the molecular sieve, and maintaining contact with the sieve until the stripping solution is used. This method is particularly useful for maintaining the peeling solution in a dry form after manufacturing, during storage and/or shipping, and after the container of the solution is opened.
出於促進瞭解所主張內容之目的，現將參考所說明實施例並將使用特定語言來闡述該等實施例。然而應瞭解，不欲由此限制所主張內容之範圍，如同熟習本揭示內容所涉及領域技術者通常可想到一般，涵蓋該等所主張內容中所說明之該等改變及其他修改及其原理之該等其他應用。 For the purpose of facilitating understanding of the claimed content, reference will now be made to the illustrated embodiments and specific language will be used to illustrate these embodiments. However, it should be understood that it is not intended to limit the scope of the claimed content, as those skilled in the field involved in this disclosure can usually imagine, covering the changes and other modifications described in the claimed content and their principles. These other applications.
本揭示內容之組合物包括二甲基亞碸(DMSO)、氫氧化四級銨及烷醇胺。烷醇胺可具有至少兩個碳原子、至少一個胺基取代基及至少一個羥基取代基，其中胺基及羥基取代基附接至烷醇胺之兩個不同的碳原子。四級取代基可包括(C1-C8)烷基、苯甲基及其組合。組合物可具有小於約-20℃至最高約+15℃之凝固點及約15cm3/公升至多達約90cm3/公升之負載容量。對於乾式剝離溶液而言，四級取代基可包括C1-C4烷基、芳基烷基或其組合。 The composition of the present disclosure includes dimethyl sulfide (DMSO), quaternary ammonium hydroxide, and alkanolamine. The alkanolamine may have at least two carbon atoms, at least one amine group substituent, and at least one hydroxy substituent, wherein the amine group and the hydroxy substituent are attached to two different carbon atoms of the alkanolamine. The quaternary substituents may include (C 1 -C 8 )alkyl, benzyl, and combinations thereof. The composition can have less than about + -20 ℃ up to about the freezing point of 15 deg.] C and about 15cm 3 / well was raised up to about 90cm 3 / liter of the load capacity. For dry stripping solutions, the quaternary substituents may include C 1 -C 4 alkyl groups, aryl alkyl groups, or combinations thereof.
具有增加之烷醇胺含量之配方對碳鋼尤其無腐蝕性，且較其他剝離溶液對典型廢物處理系統及輔助設備之傷害更小。組合物可包括具有下式之1,2-烷醇胺：
其中R1係氫、(C1-C4)烷基或(C1-C4)烷基胺基。溶液之配方可另外包括第二溶劑。溶液之配方可包括約2%至約75%之第二溶劑。第二溶劑可包括二醇及其於下文更詳細闡述之烷基或芳基醚。另外，在一些情形中，第二溶劑可包括醇。具體而言，第二溶劑可包括具有兩個或 更多個羥基之多羥基化合物。配方可具有充分低於25℃之凝固點以在運輸及倉儲期間使凝固減至最少。配方亦可具有低於約15℃之凝固點。由於剝離溶液可在低溫下保持液體，故可消除或最小化在可使用溶液前液化在寒冷氣候期間接收或儲存於未加熱倉庫中之剝離溶液之凝固滾筒之需要。用來溶化凝固剝離溶液之滾筒加熱器之使用耗費時間，需要額外處置且可造成不完全溶化及溶化溶液組合物之改質。 Wherein R 1 is hydrogen, (C 1 -C 4 )alkyl or (C 1 -C 4 )alkylamino. The formulation of the solution may additionally include a second solvent. The formulation of the solution may include about 2% to about 75% of the second solvent. The second solvent may include glycols and their alkyl or aryl ethers described in more detail below. In addition, in some cases, the second solvent may include alcohol. Specifically, the second solvent may include a polyhydroxy compound having two or more hydroxyl groups. The formulation may have a freezing point sufficiently lower than 25°C to minimize freezing during transportation and storage. The formulation can also have a freezing point below about 15°C. Since the peeling solution can keep the liquid at low temperature, it can eliminate or minimize the need to liquefy the solidification roller of the peeling solution received during cold weather or stored in an unheated warehouse before the solution can be used. The use of the roller heater for melting the solidified peeling solution is time-consuming, requires additional treatment, and can cause incomplete melting and modification of the melting solution composition.
另外，本揭示內容之組合物展現高負載容量，從而能夠使得組合物能除去較高含量之光阻劑而不沉降固體。負載容量定義為在材料再沈積於晶圓上之前或在殘餘物保留於晶圓上之前，每公升剝離溶液可除去之光阻劑或雙層材料之cm3數。例如，若在發生再沈積或殘餘物保留於晶圓上之前，20公升剝離溶液可除去300cm3光阻劑，則負載容量為300cm3/20公升=15cm3/公升。 In addition, the composition of the present disclosure exhibits a high loading capacity, thereby enabling the composition to remove a higher content of photoresist without sedimentation of solids. Loading capacity is defined as the number of cm 3 of photoresist or double-layer material that can be removed per liter of stripping solution before the material is redeposited on the wafer or before the residue remains on the wafer. For example, if 20 liters of stripping solution can remove 300 cm 3 of photoresist before redeposition occurs or residues remain on the wafer, the load capacity is 300 cm 3 /20 liters = 15 cm 3 / liter.
組合物通常含有約55%至約95%溶劑，其中所有或大部分溶劑為DMSO。在說明性實例中，溶液可包括包含於溶液總重量之約70重量%至約90重量%範圍內之量的DMSO。另外，組合物可包括約2%至約10%氫氧化四級銨。在一些情形中，溶液可包括包含於溶液總重量之約1重量%至約7重量%範圍內之量的氫氧化四級銨。四級取代基可包括(C1-C8)烷基、苯甲基及其組合。 The composition generally contains about 55% to about 95% solvent, with all or most of the solvent being DMSO. In an illustrative example, the solution may include DMSO in an amount included in the range of about 70% by weight to about 90% by weight of the total weight of the solution. Additionally, the composition may include about 2% to about 10% quaternary ammonium hydroxide. In some cases, the solution may include quaternary ammonium hydroxide in an amount ranging from about 1% to about 7% by weight of the total weight of the solution. The quaternary substituents may include (C 1 -C 8 )alkyl, benzyl, and combinations thereof.
當使用時，第二溶劑通常佔組合物之約2%至約35%。在說明性實例中，溶液可包括包含於溶液總重量之約5重量%至約20重量%範圍內之量的第二溶劑。剝離配方亦可含有可選表面活性劑，其含量通常在溶液總重量之約0.01重量%至約3重量%之範圍內。適宜量之烷醇胺可在組合物之約2%至約75%之範圍內。例如，溶液中烷醇胺之量可包括在溶液總重量之約3重量%至約15重量%之範圍內。由於剝離溶液組份中之一些組份可作為水溶液提供，故組合物可視情況含有少量水。本文提供之所有%皆為基於組合物之重量之重量%。 When used, the second solvent usually constitutes about 2% to about 35% of the composition. In an illustrative example, the solution may include the second solvent in an amount included in the range of about 5 wt% to about 20 wt% of the total weight of the solution. The release formulation may also contain optional surfactants, the content of which is usually in the range of about 0.01% to about 3% by weight of the total weight of the solution. A suitable amount of alkanolamine can range from about 2% to about 75% of the composition. For example, the amount of alkanolamine in the solution can be included in the range of about 3% to about 15% by weight of the total weight of the solution. Since some of the components of the stripping solution can be provided as an aqueous solution, the composition may contain a small amount of water as appropriate. All% provided herein are weight% based on the weight of the composition.
氫氧化四級銨可包括烷基氫氧化銨。例如，氫氧化四級銨可包括四甲基氫氧化銨、二乙基二甲基氫氧化銨、二丙基二甲基氫氧化銨、乙基三甲基氫氧化銨、四丁基氫氧化銨、苯甲基三甲基氫氧化銨。在說明性實例中，溶液可包括四甲基氫氧化銨、二甲基二丙基氫氧化銨或甲基三乙基氫氧化銨中之一或多者。 The quaternary ammonium hydroxide may include alkyl ammonium hydroxide. For example, quaternary ammonium hydroxide may include tetramethyl ammonium hydroxide, diethyl dimethyl ammonium hydroxide, dipropyl dimethyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, tetrabutyl ammonium hydroxide Ammonium, benzyl trimethyl ammonium hydroxide. In an illustrative example, the solution may include one or more of tetramethylammonium hydroxide, dimethyldipropylammonium hydroxide, or methyltriethylammonium hydroxide.
烷醇胺可具有至少兩個碳原子且可使胺基及羥基取代基位於不同的碳原子上。適宜烷醇胺包括(但不限於)乙醇胺、N-甲基乙醇胺、N-乙基乙醇胺、N-丙基乙醇胺、N-丁基乙醇胺、二乙醇胺、三乙醇胺、N-甲基二乙醇胺、N-乙基二乙醇胺、異丙醇胺、二異丙醇胺、三異丙醇胺、N-甲基異丙醇胺、N-乙基異丙醇胺、N-丙基異丙醇胺、2-胺基丙烷-1-醇、N-甲基-2-胺基丙烷-1-醇、N-乙基-2-胺基丙烷-1-醇、1-胺基丙烷-3-醇、N-甲基-1-胺基丙烷-3-醇、N-乙基-1-胺基丙烷-3-醇、1-胺基丁烷-2-醇、N-甲基-1-胺基丁烷-2-醇、N-乙基-1-胺基丁烷-2-醇、2-胺基丁烷-1-醇、N-甲基-2-胺基丁烷-1-醇、N-乙基-2-胺基丁烷-1-醇、3-胺基丁烷-1-醇、N-甲基-3-胺基丁烷-1-醇、N-乙基-3-胺基丁烷-1-醇、1-胺基丁烷-4-醇、N-甲基-1-胺基丁烷-4-醇、N-乙基-1-胺基丁烷-4-醇、1-胺基-2-甲基丙烷-2-醇、2-胺基-2-甲基丙烷-1-醇、1-胺基戊烷-4-醇、2-胺基-4-甲基戊烷-1-醇、2-胺基己烷-1-醇、3-胺基庚烷-4-醇、1-胺基辛烷-2-醇、5-胺基辛烷-醇、1-胺基丙烷-2,3-多羥基化合物、2-胺基丙烷-1,3-多羥基化合物、叁(氧基甲基)胺基甲烷、1,2-二胺基丙烷-3-醇、1,3-二胺基丙烷-2-醇及2(2-胺基乙氧基)乙醇。 The alkanolamine can have at least two carbon atoms and the amine group and the hydroxyl substituent can be located on different carbon atoms. Suitable alkanolamines include (but are not limited to) ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-butylethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N -Ethyldiethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, N-methyl isopropanolamine, N-ethyl isopropanolamine, N-propyl isopropanolamine, 2-aminopropane-1-ol, N-methyl-2-aminopropane-1-ol, N-ethyl-2-aminopropane-1-ol, 1-aminopropane-3-ol, N-methyl-1-aminopropane-3-ol, N-ethyl-1-aminopropan-3-ol, 1-aminobutane-2-ol, N-methyl-1-amino Butane-2-ol, N-ethyl-1-aminobutan-2-ol, 2-aminobutan-1-ol, N-methyl-2-aminobutan-1-ol, N-ethyl-2-aminobutane-1-ol, 3-aminobutane-1-ol, N-methyl-3-aminobutane-1-ol, N-ethyl-3- Aminobutan-1-ol, 1-aminobutane-4-ol, N-methyl-1-aminobutane-4-ol, N-ethyl-1-aminobutane-4-ol Alcohol, 1-amino-2-methylpropane-2-ol, 2-amino-2-methylpropane-1-ol, 1-aminopentane-4-ol, 2-amino-4-ol Methylpentane-1-ol, 2-aminohexane-1-ol, 3-aminoheptan-4-ol, 1-aminooctane-2-ol, 5-aminooctane-ol , 1-aminopropane-2,3-polyhydroxy compound, 2-aminopropane-1,3-polyhydroxy compound, tris(oxymethyl)aminomethane, 1,2-diaminopropane-3 -Alcohol, 1,3-diaminopropan-2-ol and 2(2-aminoethoxy)ethanol.
第二溶劑可包括二醇醚溶劑、醇或多羥基化合物或該等化合物中之兩者或更多者之組合。 The second solvent may include a glycol ether solvent, an alcohol or a polyhydroxy compound, or a combination of two or more of these compounds.
二醇醚溶劑可包括(但不限於)二乙二醇、三乙二醇、乙二醇單甲醚、乙二醇單***、乙二醇單丁醚、乙二醇二甲醚、乙二醇二***、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丙醚、二乙二醇單異 丙醚、二乙二醇單丁醚、二乙二醇單異丁醚、二乙二醇單苯甲醚、二乙二醇二***、三乙二醇單甲醚、三乙二醇二甲醚、聚乙二醇單甲醚、二乙二醇甲基***、三乙二醇、乙二醇單甲醚乙酸酯、乙二醇乙酸單乙酯、二丙二醇、三丙二醇、丙二醇單甲醚、丙二醇二甲醚、丙二醇單丁醚、二丙二醇單甲醚、二丙二醇單丙醚、二丙二醇單異丙醚、二丙二醇單丁醚、二丙二醇二甲醚、二丙二醇二丙醚、二丙二醇二異丙醚、三丙二醇及三丙二醇單甲醚、1-甲氧基-2-丁醇、2-甲氧基-1-丁醇、2-甲氧基-2-甲基-2-丁醇、3-甲氧基-3-甲基-1-丁醇、二噁烷、三噁烷、1,1-二甲氧基乙烷、四氫呋喃、冠醚及諸如此類。 Glycol ether solvents may include (but are not limited to) diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol Alcohol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monoiso Propyl ether, diethylene glycol monobutyl ether, diethylene glycol monoisobutyl ether, diethylene glycol monoanisole, diethylene glycol diethyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether Ether, polyethylene glycol monomethyl ether, diethylene glycol methyl ethyl ether, triethylene glycol, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl acetate, dipropylene glycol, tripropylene glycol, propylene glycol monomethyl Ether, propylene glycol dimethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoisopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol dipropyl ether, two Propylene glycol diisopropyl ether, tripropylene glycol and tripropylene glycol monomethyl ether, 1-methoxy-2-butanol, 2-methoxy-1-butanol, 2-methoxy-2-methyl-2- Butanol, 3-methoxy-3-methyl-1-butanol, dioxane, trioxane, 1,1-dimethoxyethane, tetrahydrofuran, crown ether and the like.
第二溶劑醇及多羥基化合物具有兩個或更多個羥基且不含有酯、胺或醚基團。醇或多羥基化合物可為脂肪族化合物、脂環族化合物、環狀化合物或芳香族化合物，但合意地為脂肪族化合物或脂環族化合物。醇或多羥基化合物可為飽和或不飽和化合物，且合意地具有一或少於一個不飽和鍵，或沒有不飽和鍵。醇及多羥基化合物合意地不含有雜原子。醇及多羥基化合物合意地僅含有碳及氫原子。 The second solvent alcohol and polyhydroxy compound have two or more hydroxyl groups and do not contain ester, amine or ether groups. The alcohol or polyhydroxy compound may be an aliphatic compound, an alicyclic compound, a cyclic compound, or an aromatic compound, but is desirably an aliphatic compound or an alicyclic compound. The alcohol or polyhydroxy compound may be a saturated or unsaturated compound, and desirably has one or less than one unsaturated bond, or no unsaturated bond. Alcohols and polyhydroxy compounds desirably contain no heteroatoms. Alcohols and polyhydroxy compounds desirably contain only carbon and hydrogen atoms.
作為第二溶劑之實例，醇可提及直鏈及具支鏈及芳香族化合物醇。為進行說明，溶液之醇可包括甲醇、乙醇、丙醇、異丙基醇、丁醇、第三-丁基醇、第三-戊基醇、3-甲基-3-戊醇、1-辛醇、1-癸醇、1-十一醇、1-十二醇、1-十三醇、1-十四醇、1-十五醇、1-十六醇、9-十六烯-1-醇、1-十七醇、1-十八醇、1-十九醇、1-二十醇、1-二十一醇、1-二十二醇、13-二十二烯-1-醇、1-二十四醇、1-二十六醇、1-二十七醇、1-二十八醇、1-三十醇、1-三十二醇、1-三十四醇、鯨蠟硬脂醇、糠醇、四氫糠醇。在說明性實例中，溶液可包括糠醇、四氫糠醇、第三-丁基醇或3-甲基-3-戊醇中之一或多者。 As an example of the second solvent, the alcohol can mention linear and branched chain and aromatic compound alcohols. For illustration, the alcohol of the solution may include methanol, ethanol, propanol, isopropyl alcohol, butanol, tertiary-butyl alcohol, tertiary-pentyl alcohol, 3-methyl-3-pentanol, 1- Octanol, 1-decanol, 1-undecyl alcohol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 9-hexadecene- 1-alcohol, 1-heptadecanol, 1-octadecyl alcohol, 1-nonadecanol, 1-eicosanol, 1-eicosanol, 1-docosyl alcohol, 13-docosene-1 -Alcohol, 1-Ticosanol, 1-Dihexanol, 1-Dihexanol, 1-Dioctacosanol, 1-Triacontanol, 1-Triacontanol, 1-Tritetracosanol , Cetearyl alcohol, furfuryl alcohol, tetrahydrofurfuryl alcohol. In an illustrative example, the solution may include one or more of furfuryl alcohol, tetrahydrofurfuryl alcohol, tertiary-butyl alcohol, or 3-methyl-3-pentanol.
如上文所提及，第二溶劑可為具有兩個或更多個羥基之多羥基化合物。多羥基化合物之分子量合意地不超過500，或不超過400，或 不超過350，或不超過300，或不超過275，或不超過250，或不超過225，或不超過200，或不超過175，或不超過150，或不超過125，或不超過100，或不超過75。 As mentioned above, the second solvent may be a polyhydroxy compound having two or more hydroxyl groups. The molecular weight of the polyhydroxy compound desirably does not exceed 500, or does not exceed 400, or No more than 350, or no more than 300, or no more than 275, or no more than 250, or no more than 225, or no more than 200, or no more than 175, or no more than 150, or no more than 125, or no more than 100, or Not more than 75.
作為第二溶劑之多羥基化合物可包括乙二醇、1,2-丙二醇(丙二醇)、1,3-丙二醇，1,2,3-丙三醇、1,2-丁二醇、1,3-丙二醇、2,3-丁二醇、1,4-丁二醇、1,2,3-丁三醇、1,2,4-丁三醇、1,2-戊二醇、1,3-戊二醇、1,4-戊二醇、2,3-戊二醇、2,4-戊二醇、3,4-戊二醇、1,2,3-戊三醇、1,2,4-戊三醇、1,2,5-戊三醇、1,3,5-戊三醇、驅蚊醇(etohexadiol)、對甲烷-3,8-多羥基化合物、2-甲基-2,4-戊二醇、2,2-二甲基-1,3-丙二醇、甘油、三羥甲丙烷、木糖醇、***糖醇、1,2-或1,3-環戊二醇、1,2-或1,3-環己二醇、2,3-降莰烷二醇、1,8-辛二醇、1,2-環己烷-二甲醇、1,3-環己烷二甲醇、1,4-環己烷二甲醇、2,2,4-三甲基-1,3-戊二醇、羥基新戊酸羥基新戊醯基酯、2-甲基-1,3-丙二醇、2-丁基-2-乙基-1,3-丙二醇、2-乙基-2-異丁基-1,3-丙二醇、1,6-己二醇、2,2,4,4-四甲基-1,6-己二醇、1,10-癸二醇、1,4-苯二甲醇、氫化雙酚A、1,1,1-三羥甲基丙烷、1,1,1-三羥甲基乙烷、新戊四醇、赤藻糖醇、蘇糖醇、二新戊四醇、山梨糖醇及諸如此類，及上述多羥基化合物中之2者或多者之組合。 The polyhydroxy compound as the second solvent may include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2,3-propanetriol, 1,2-butanediol, 1,3 -Propylene glycol, 2,3-butanediol, 1,4-butanediol, 1,2,3-butanetriol, 1,2,4-butanetriol, 1,2-pentanediol, 1,3 -Pentanediol, 1,4-pentanediol, 2,3-pentanediol, 2,4-pentanediol, 3,4-pentanediol, 1,2,3-pentanetriol, 1,2 ,4-Pentanetriol, 1,2,5-Pentanetriol, 1,3,5-Pentanetriol, etohexadiol, p-methane-3,8-polyol, 2-methyl- 2,4-pentanediol, 2,2-dimethyl-1,3-propanediol, glycerin, trimethylolpropane, xylitol, arabitol, 1,2- or 1,3-cyclopentanediol , 1,2- or 1,3-cyclohexanediol, 2,3-norbornanediol, 1,8-octanediol, 1,2-cyclohexane-dimethanol, 1,3-cyclohexane Alkyl dimethanol, 1,4-cyclohexane dimethanol, 2,2,4-trimethyl-1,3-pentanediol, hydroxypivalic acid hydroxypivaloyl ester, 2-methyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 1,6-hexanediol, 2,2,4 ,4-Tetramethyl-1,6-hexanediol, 1,10-decanediol, 1,4-benzenedimethanol, hydrogenated bisphenol A, 1,1,1-trimethylolpropane, 1, 1,1-Trimethylolethane, neopentylerythritol, erythritol, threitol, dineopentitol, sorbitol and the like, and one of two or more of the above-mentioned polyhydroxy compounds combination.
在說明性實例中，溶液可包括乙二醇、1,2-丙二醇(丙二醇)、1,3-丙二醇、1,4-戊二醇、1,2-丁二醇或1,3-丁二醇之第二多羥基溶劑中之一或多者。 In an illustrative example, the solution may include ethylene glycol, 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,4-pentanediol, 1,2-butanediol, or 1,3-butanediol One or more of the second polyhydroxy solvents of alcohol.
組合物亦可視情況含有一或多種腐蝕抑制劑。適宜腐蝕抑制劑包括(但不限於)芳香族羥基化合物，例如鄰苯二酚；烷基鄰苯二酚(例如甲基鄰苯二酚、乙基鄰苯二酚及第三丁基鄰苯二酚)、苯酚及五倍子酚；芳香族***，例如苯并***；烷基苯并***；羧酸，例如甲酸、乙酸、丙酸、丁酸、異丁酸、草酸、丙二酸、琥珀酸、戊二酸、 馬來酸、富馬酸、苯甲酸、鄰苯二甲酸、1,2,3-苯三甲酸、乙醇酸、乳酸、蘋果酸、檸檬酸、乙酸酐、鄰苯二甲酸酐、馬來酸酐、琥珀酸酐、水楊酸、沒食子酸及沒食子酸酯(例如沒食子酸甲酯及沒食子酸丙酯)；上述含羧基之有機化合物之有機鹽、鹼性物質(例如乙醇胺、三甲胺、二乙胺及吡啶(例如2-胺基吡啶及諸如此類))；及螯合化合物，例如基於磷酸之螯合化合物(包括1,2-丙二胺四亞甲基膦酸及羥基乙烷膦酸)、基於羧酸之螯合化合物(例如乙二胺四乙酸及其鈉及銨鹽、二羥乙基甘胺酸及次氮基三乙酸)、基於胺之螯合化合物(例如聯吡啶、四苯基卟啉及啡啉)，及基於肟之螯合化合物(例如二甲基乙二醛二肟及二苯基乙二醛二肟)。可使用腐蝕抑制劑或可使用腐蝕抑制劑之組合。腐蝕抑制劑已證實在約1ppm至約10%範圍內之含量有用。 The composition may optionally contain one or more corrosion inhibitors. Suitable corrosion inhibitors include, but are not limited to, aromatic hydroxy compounds such as catechol; alkyl catechol (such as methyl catechol, ethyl catechol and tertiary butyl catechol) Phenol), phenol and gallic phenol; aromatic triazoles, such as benzotriazole; alkyl benzotriazole; carboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, oxalic acid, malonic acid, Succinic acid, glutaric acid, Maleic acid, fumaric acid, benzoic acid, phthalic acid, trimellitic acid, glycolic acid, lactic acid, malic acid, citric acid, acetic anhydride, phthalic anhydride, maleic anhydride, Succinic anhydride, salicylic acid, gallic acid and gallic acid esters (such as methyl gallate and propyl gallate); organic salts and alkaline substances of the above-mentioned organic compounds containing carboxyl groups (such as ethanolamine) , Trimethylamine, diethylamine and pyridine (such as 2-aminopyridine and the like); and chelating compounds, such as phosphoric acid-based chelating compounds (including 1,2-propylenediaminetetramethylenephosphonic acid and hydroxyl Ethane phosphonic acid), carboxylic acid-based chelating compounds (e.g. ethylenediaminetetraacetic acid and its sodium and ammonium salts, dihydroxyethylglycine and nitrilotriacetic acid), amine-based chelating compounds (e.g. Bipyridine, tetraphenylporphyrin and phenanthroline), and oxime-based chelating compounds (such as dimethylglyoxime and diphenylglyoxime). Corrosion inhibitors can be used or a combination of corrosion inhibitors can be used. Corrosion inhibitors have proven useful at levels ranging from about 1 ppm to about 10%.
另外，溶液可視情況包括一或多種表面活性劑，例如氟表面活性劑。可包括於溶液中之氟表面活性劑之一個實例係DuPont FSO(具有聚乙二醇(50%)、乙二醇(25%)、1,4-二噁烷(<0.1%)、水(25%)之氟化短鏈聚合物B單醚)。 In addition, the solution may optionally include one or more surfactants, such as fluorosurfactants. An example of a fluorosurfactant that can be included in the solution is DuPont FSO (with polyethylene glycol (50%), ethylene glycol (25%), 1,4-dioxane (<0.1%), water ( 25%) fluorinated short-chain polymer B monoether).
可使用至少50℃之溫度來接觸基板，而對於大多數應用而言，可利用約50℃至約75℃之溫度。對於基板敏感或需要較長除去時間之具體應用而言，較低接觸溫度較為適當。例如，當再加工基板時，可適當地使剝離溶液在至少20℃之溫度下維持較長時間以除去光阻劑且避免損壞基板。若完全除去抗蝕劑需要較長接觸時間，則在剝離溶液上方放置乾燥氮覆蓋層可減少自大氣吸收水且可維持乾式剝離溶液之改良性能。 A temperature of at least 50°C can be used to contact the substrate, and for most applications, a temperature of about 50°C to about 75°C can be used. For specific applications where the substrate is sensitive or requires a longer removal time, a lower contact temperature is more appropriate. For example, when reprocessing the substrate, the peeling solution can be appropriately maintained at a temperature of at least 20° C. for a long time to remove the photoresist and avoid damaging the substrate. If a longer contact time is required to completely remove the resist, placing a dry nitrogen coating on the stripping solution can reduce water absorption from the atmosphere and maintain the improved performance of the dry stripping solution.
當浸沒基板時，組合物之攪動另外有助於光阻劑除去。可藉由機械攪拌、循環或藉由使惰性氣體鼓泡通過組合物實現攪動。在除去期望量之光阻劑後，使基板遠離不再接觸剝離溶液並利用水或醇進行 沖洗。例如，可使用去離子(DI)水來沖洗基板。在另一實例中，可使用異丙醇來沖洗基板。對於使組份經受氧化之基板而言，可在惰性氣氛下實施沖洗。本揭示內容之剝離溶液可具有與當前商業產品相比有所改良之光阻劑材料負載容量，且利用給定體積之剝離溶液能夠處理較大數量之基板。 When the substrate is immersed, the agitation of the composition additionally aids the removal of the photoresist. The agitation can be achieved by mechanical agitation, circulation, or by bubbling inert gas through the composition. After removing the desired amount of photoresist, keep the substrate away from the stripping solution and use water or alcohol. rinse. For example, deionized (DI) water can be used to rinse the substrate. In another example, isopropanol can be used to rinse the substrate. For substrates that subject the components to oxidation, rinsing can be performed under an inert atmosphere. The stripping solution of the present disclosure can have an improved photoresist material loading capacity compared with current commercial products, and a larger number of substrates can be processed with a given volume of the stripping solution.
可使用本揭示內容中提供之剝離溶液來除去存於單一層或某些類型之雙層抗蝕劑中之聚合抗蝕劑材料。例如，雙層抗蝕劑通常具有由第二聚合層覆蓋之第一無機層或可具有兩個聚合層。利用本文所闡述之方法，可自具有單一聚合物層之標準晶圓有效除去聚合抗蝕劑之單一層。亦可使用相同方法自具有由第一無機層及第二或外部聚合物層構成之雙層之晶圓除去單一聚合物層。最後，可自具有由兩個聚合層構成之雙層之晶圓有效除去兩個聚合物層。可使用乾式剝離溶液來除去一個、兩個或更多個抗蝕劑層。 The stripping solution provided in the present disclosure can be used to remove the polymeric resist material present in a single layer or some types of double-layer resists. For example, a two-layer resist usually has a first inorganic layer covered by a second polymer layer or may have two polymer layers. Using the method described in this article, a single layer of polymer resist can be effectively removed from a standard wafer with a single polymer layer. The same method can also be used to remove a single polymer layer from a wafer having a double layer consisting of a first inorganic layer and a second or outer polymer layer. Finally, two polymer layers can be effectively removed from a wafer having a double layer composed of two polymer layers. A dry stripping solution can be used to remove one, two or more resist layers.
乾式剝離溶液可包括二甲基亞碸、氫氧化四級銨、烷醇胺、可選第二溶劑及少於約3wt.%之水。第二溶劑可包括二醇醚、醇及/或多羥基化合物。乾式剝離溶液亦可包括二甲基亞碸、氫氧化四級銨、烷醇胺、二醇醚溶劑、多羥基第二溶劑，及至少約1.8之乾度係數。乾式剝離溶液亦可包括二甲基亞碸、氫氧化四級銨、烷醇胺、第二溶劑(例如醇或多羥基第二溶劑)，及至少約1.8之乾度係數。 The dry stripping solution may include dimethyl sulfide, quaternary ammonium hydroxide, alkanolamine, optional second solvent, and less than about 3 wt.% water. The second solvent may include glycol ethers, alcohols, and/or polyhydroxy compounds. The dry stripping solution may also include dimethyl sulfide, quaternary ammonium hydroxide, alkanolamine, glycol ether solvent, polyhydroxy second solvent, and a dryness coefficient of at least about 1.8. The dry stripping solution may also include dimethyl sulfide, quaternary ammonium hydroxide, alkanolamine, a second solvent (such as an alcohol or a polyhydroxy second solvent), and a dryness coefficient of at least about 1.8.
乾式光阻劑剝離溶液之用途類似於上文針對具有低凝固點之剝離溶液所闡述者。然而，其有助於在使用前將剝離溶液維持於乾燥形式且可在其使用期間藉由在涉及除去抗蝕劑之區域中維持通常乾燥之環境使水吸收減至最少。可藉由在儲存、運輸期間及在剝離溶液使用前在打開容器後維持剝離溶液與活性分子篩間之接觸將剝離溶液維持於乾燥狀態。 The use of the dry photoresist stripping solution is similar to that described above for the stripping solution with a low freezing point. However, it helps to maintain the stripping solution in a dry form before use and can minimize water absorption during its use by maintaining a normally dry environment in the area involved in the removal of the resist. The peeling solution can be maintained in a dry state by maintaining the contact between the peeling solution and the active molecular sieve after opening the container during storage, transportation and before using the peeling solution.
本文所闡述之乾式剝離溶液應儘可能自乾式組份來製備。由於 氫氧化四級銨為吸濕性的且通常可作為水溶液或其水合物獲得，故通常必須除去含於溶液中或與水合物結合之水以提供乾度係數為至少約1之乾式剝離溶液。在升高之溫度下獲得乾燥氫氧化四級銨及達到乾燥狀態之工作通常導致氫氧化物之分解。已驚奇地發現，可預乾燥於揮發性溶劑中之氫氧化四級銨以得到水含量有所減少且不分解之溶劑濕性膏糊。可藉由以下方式來製備含有氫氧化四級銨之乾式剝離溶液：預乾燥氫氧化四級銨並使其與其他實質上乾燥之組份合併以維持低水含量，或隨後乾燥自含水組份形成之初始經風扇處理之濕剝離溶液。 The dry stripping solution described in this article should be prepared from the dry component as much as possible. because Quaternary ammonium hydroxide is hygroscopic and is usually available as an aqueous solution or its hydrate, so it is usually necessary to remove the water contained in the solution or combined with the hydrate to provide a dry stripping solution with a dryness coefficient of at least about 1. The work of obtaining dry quaternary ammonium hydroxide and reaching a dry state at elevated temperatures usually results in the decomposition of the hydroxide. It has been surprisingly discovered that quaternary ammonium hydroxide in a volatile solvent can be pre-dried to obtain a solvent wet paste with reduced water content and no decomposition. The dry stripping solution containing quaternary ammonium hydroxide can be prepared by pre-drying the quaternary ammonium hydroxide and combining it with other substantially dry components to maintain a low water content, or subsequently drying from the water-containing component The initial formation of a fan-treated wet stripping solution.
可藉由利用非常輕微之升溫使水合或以其他方式濕潤之形式的氫氧化四級銨經受減壓獲得預乾燥形式之氫氧化四級銨。可在使氫氧化物經受減壓前藉由將氫氧化四級銨溶解於諸如醇等溶劑中來幫助水之除去。基於目前為止利用甲醇實施之工作，在處理期間，除去很大一部分水及醇以提供氫氧化四級銨之醇濕性膏糊。端視期望之乾燥程度，可將額外乾式醇添加至初始處理之氫氧化物中並將於減壓下之處理重複一或多次。可在約0.001mmhg至約30mmhg之壓力下及在高達至少約35℃之溫度下實施處理而不大量分解氫氧化四級銨。亦可在約0.01mmhg至約10mmhg之壓力下實施處理。 The quaternary ammonium hydroxide in a pre-dried form can be obtained by subjecting the quaternary ammonium hydroxide in a hydrated or otherwise wet form to a reduced pressure using a very slight temperature increase. The removal of water can be aided by dissolving quaternary ammonium hydroxide in a solvent such as alcohol before subjecting the hydroxide to reduced pressure. Based on the work done so far using methanol, during the treatment, a large part of the water and alcohol are removed to provide an alcohol wet paste of quaternary ammonium hydroxide. Depending on the desired degree of dryness, additional dry alcohol can be added to the initial treated hydroxide and the treatment under reduced pressure can be repeated one or more times. The treatment can be carried out under a pressure of about 0.001 mmhg to about 30 mmhg and at a temperature up to at least about 35° C. without decomposing the quaternary ammonium hydroxide in a large amount. The treatment can also be carried out under a pressure of about 0.01 mmhg to about 10 mmhg.
對於具有或沒有第二溶劑之濕配方而言，可在添加所有組份後藉由使剝離溶液與固體乾燥劑(例如分子篩、氫化鈣、硫酸鈣或乾燥劑之組合)接觸對剝離溶液實施乾燥。實例乾燥劑可包括活化之3A或4A分子篩。對於含有第二溶劑之乾式剝離溶液而言，可將氫氧化四級銨與任何其他濕組份合併，使所得溶液與諸如分子篩等活性乾燥劑接觸，使乾式溶液與所消耗乾燥劑分離並將任何剩餘乾燥組份添加至乾式溶液中。可藉由任一已知方法與分子篩或其他固體乾燥劑接觸，例如利用乾燥劑漿液化溶液並過濾乾式漿液。類似地，可藉由在管柱 中將濕溶液通過糰粒化活化之分子篩或其他乾燥劑乾燥上文所闡述之任一濕溶液。適宜分子篩包括3A、4A及5A型篩。 For wet formulations with or without a second solvent, the stripping solution can be dried by contacting the stripping solution with a solid desiccant (for example, a combination of molecular sieve, calcium hydride, calcium sulfate or desiccant) after adding all the components . Example desiccants may include activated 3A or 4A molecular sieves. For dry stripping solutions containing a second solvent, quaternary ammonium hydroxide can be combined with any other wet components, and the resulting solution can be contacted with an active desiccant such as molecular sieve to separate the dry solution from the consumed desiccant and Any remaining dry components are added to the dry solution. Contact with molecular sieves or other solid desiccants can be done by any known method, for example, the desiccant is used to slurry the solution and filter the dry slurry. Similarly, you can use the string The wet solution is passed through agglomerated activated molecular sieve or other desiccant to dry any of the wet solutions described above. Suitable molecular sieves include 3A, 4A and 5A type sieves.
亦可使用分子篩作為乾燥劑(drying agent或desiccant)將剝離溶液維持於乾燥狀態。例如，可使用糰粒形式，此乃因其容許藉由簡單傾析除去乾式剝離溶液。然而，對於傾析不提供足夠分離之應用而言，可將分子篩(無論粉末或糰粒)納入「茶袋」佈置中從而將容許與溶液之平衡，但不容許任何篩粒子污染溶液。可在已打開容器後將含分子篩之乾式剝離溶液維持於乾燥狀態達延長之時段，此短視剝離溶液所包括之分子篩之量、周圍濕度及打開容器之時間之量而定。 Molecular sieves can also be used as a drying agent (or desiccant) to maintain the peeling solution in a dry state. For example, the pellet form can be used because it allows the dry stripping solution to be removed by simple decantation. However, for applications where decantation does not provide sufficient separation, molecular sieves (whether powder or pellets) can be included in a "tea bag" arrangement that will allow equilibrium with the solution, but will not allow any sieve particles to contaminate the solution. The dry stripping solution containing molecular sieves can be maintained in a dry state for an extended period of time after the container has been opened, depending on the amount of molecular sieve included in the stripping solution, the surrounding humidity, and the amount of time to open the container.
在攪拌下單獨合併列示於表I中之反應物，從而得到14種均質剝離溶液中之每一者。測定凝固點且亦提供於表I中。實例1-14之組合物可視情況在無表面活性劑之情況下經調配且經調配以包括腐蝕抑制劑。 The reactants listed in Table I were separately combined under stirring to obtain each of the 14 homogeneous stripping solutions. The freezing point was determined and is also provided in Table I. The compositions of Examples 1-14 may optionally be formulated without surfactants and formulated to include corrosion inhibitors.
將其上具有光阻劑之矽晶圓浸沒於實例1之剝離溶液中，在攪拌下在約70℃之溫度下維持約30分鐘至約60分鐘。除去晶圓，用DI水沖 洗並進行乾燥。對晶圓之檢查將指示實質上所有光阻劑之除去。對於一些應用而言，可藉由在不進行攪拌下將晶圓浸沒於剝離溶液中及/或將晶圓浸沒長達150分鐘獲得優良結果。可在不進行過度實驗下易於確定自晶圓除去光阻劑之較佳方式。此方法可用於除去聚合光阻劑之單一層或存於具有兩個聚合物層之雙層抗蝕劑中之兩個聚合層。 The silicon wafer with the photoresist thereon was immersed in the peeling solution of Example 1, and maintained at a temperature of about 70° C. for about 30 minutes to about 60 minutes with stirring. Remove the wafer and rinse with DI water Wash and dry. Inspection of the wafer will indicate the removal of virtually all photoresist. For some applications, good results can be obtained by immersing the wafer in the stripping solution and/or immersing the wafer for up to 150 minutes without stirring. The best way to remove the photoresist from the wafer can be easily determined without undue experimentation. This method can be used to remove a single layer of polymerized photoresist or two polymerized layers present in a double-layer resist with two polymer layers.
將其上具有光阻劑之矽晶圓安裝於標準噴霧裝置中並利用實例2之剝離溶液噴霧，在約50℃下維持。可視情況在惰性氣氛下或視情況在活性氣體(例如氧、氟或矽烷)存在下實施噴霧。可週期性地除去晶圓並進行檢查以確定何時除去足夠光阻劑。當已除去足夠光阻劑時，可利用異丙醇沖洗晶圓並進行乾燥。此方法可用於除去聚合光阻劑之單一層或存於具有兩個聚合物層之雙層抗蝕劑中之兩個聚合層。 The silicon wafer with photoresist on it was mounted in a standard spray device and sprayed with the stripping solution of Example 2, and maintained at about 50°C. The spray may be implemented in an inert atmosphere or in the presence of an active gas (such as oxygen, fluorine or silane) as appropriate. The wafers can be removed periodically and inspected to determine when enough photoresist is removed. When enough photoresist has been removed, the wafer can be rinsed with isopropanol and dried. This method can be used to remove a single layer of polymerized photoresist or two polymerized layers present in a double-layer resist with two polymer layers.
使用實例f4中闡述之方法自下表II中闡述之晶圓除去光阻劑。使用20公升體積之三種剝離溶液直至光阻劑聚合物之殘餘物保留於晶圓上為止或直至聚合物或其降解產物再沈積至晶圓上為止，此時達到溶液負載容量。利用此方法，確定於上述實例1及2中闡述之兩種剝離溶液及當前商業剝離溶液之一般典型比較實例之負載容量。 The method described in Example f4 was used to remove the photoresist from the wafer described in Table II below. Use the three stripping solutions in a volume of 20 liters until the photoresist polymer remains on the wafer or until the polymer or its degradation products are deposited on the wafer again, at which point the solution loading capacity is reached. Using this method, the load capacity of the two stripping solutions described in the above Examples 1 and 2 and the general typical comparative example of the current commercial stripping solution were determined.
合併二甲基亞碸(85.5g)、二乙二醇單甲醚(6.0g)、胺基乙基乙醇胺(2.7g)及四甲基氫氧化銨五水合物(5.5g)，從而得到含有約3wt.%水及乾度係數為約0.9之剝離溶液。藉由輕微攪動混合物有助於氫氧化物五水合物之溶解。溶液中約3wt.%之水實質上來自五水合物。 Combine dimethyl sulfite (85.5g), diethylene glycol monomethyl ether (6.0g), aminoethylethanolamine (2.7g) and tetramethylammonium hydroxide pentahydrate (5.5g) to obtain A peeling solution with about 3wt.% water and a dryness coefficient of about 0.9. Agitate the mixture slightly to help dissolve the hydroxide pentahydrate. About 3wt.% of the water in the solution is essentially derived from the pentahydrate.
將活性3A分子篩添加至根據實例17之方法製備之剝離溶液之三種不同試樣中並在環境溫度下維持與剝離溶液之接觸達72小時。藉由過濾除去該等篩並藉由卡爾費雪法(Karl Fischer method)確定初始及乾式溶液之水分含量。將乾式剝離溶液儲存於封閉容器中。可乾燥已消耗篩以便再使用或將其丟棄。於下表III中將此實驗之具體細節製成表 格。 Active 3A molecular sieves were added to three different samples of the peeling solution prepared according to the method of Example 17, and the contact with the peeling solution was maintained at ambient temperature for 72 hours. The sieves were removed by filtration and the moisture content of the initial and dry solution was determined by the Karl Fischer method. Store the dry stripping solution in a closed container. The spent sieve can be dried for reuse or discarded. Tabulate the specific details of this experiment in Table III below grid.
將其上於銅區上方放置基於負性丙烯酸酯聚合物之乾燥膜光阻劑(120/μm)之三種矽晶圓單獨浸沒於在實例18中製備之三種乾式剝離溶液中，並在70℃下維持60分鐘。除去該等試樣並用去離子水沖洗一分鐘。利用LiQuilaz SO5粒子分析器分析所得剝離溶液之懸浮於該等溶液中之光阻劑之粒子數，並測定每一晶圓之銅蝕刻速率。在下文提供之表IV中將結果製成表格。LiQuilaz係Particle Measuring Systems公司5475 Airport Blvd.,Boulder,Colorado,80301之註冊商標。 Three silicon wafers with dry film photoresist based on negative acrylate polymer (120/μm) placed on the copper area were individually immersed in the three dry stripping solutions prepared in Example 18 and kept at 70°C Maintain for 60 minutes. Remove the samples and rinse with deionized water for one minute. A LiQuilaz SO5 particle analyzer was used to analyze the number of particles of the photoresist suspended in the solution in the stripping solution, and to determine the copper etching rate of each wafer. The results are tabulated in Table IV provided below. LiQuilaz is a registered trademark of Particle Measuring Systems, Inc. 5475 Airport Blvd., Boulder, Colorado, 80301.
可在約70℃至約80℃範圍內之溫度下實施如上文所闡述之光阻劑除去而無需採取任何排除水分之措施。然而，當在小於約70℃之較低溫度下實施光阻劑除去時，可有助於採取措施以將自大氣之水分吸收減至最少。在小於約70℃下維持之剝離溶液上方提供乾燥氮之覆蓋層已證實可在剝離溶液較長時間暴露於潮濕氣氛時有效地將水吸收減至最少。上文所闡述之乾式剝離溶液溶解較大量光阻劑並將分散於剝離溶液中之粒子之數量減至最少之能力可延長剝離溶液有效壽命並減 少總體成本。 The photoresist removal as described above can be carried out at a temperature in the range of about 70°C to about 80°C without taking any measures to remove water. However, when the photoresist removal is performed at a relatively low temperature of less than about 70°C, it can be helpful to take measures to minimize the absorption of moisture from the atmosphere. Providing a cover layer of dry nitrogen over the stripping solution maintained at less than about 70°C has proven to be effective in minimizing water absorption when the stripping solution is exposed to a humid atmosphere for a longer period of time. The ability of the dry stripping solution described above to dissolve a larger amount of photoresist and minimize the number of particles dispersed in the stripping solution can extend the effective life of the stripping solution and reduce Less overall cost.
製備四甲基氫氧化銨五水合物存於甲醇中之25wt.%溶液並在水浴中使40.8克溶液升溫至約30℃且在約0.01mmhg之壓力下維持約75分鐘。在用液氮冷卻之杜瓦瓶(Dewar flask)中收集冷凝物。在約75分鐘後，使水浴之溫度上升至約35℃並在該溫度下再維持105分鐘。產生白色膏糊。破壞真空並添加85.8g乾式DMSO以溶解白色固體，此後添加6.0g二乙二醇單甲醚及2.7g胺基乙基乙醇胺，從而得到實例1表1中闡述之實質上乾燥形式之剝離溶液。藉由卡爾費雪法發現乾式剝離溶液之水含量為0.71%且該溶液含有少於1%之甲醇。可藉由添加額外甲醇至白色膏糊中並將所得溶液在減壓下再維持2小時至5小時獲得較低含量之水。 A 25wt.% solution of tetramethylammonium hydroxide pentahydrate in methanol was prepared, and 40.8 g of the solution was heated to about 30°C in a water bath and maintained at a pressure of about 0.01 mmhg for about 75 minutes. The condensate was collected in a Dewar flask cooled with liquid nitrogen. After about 75 minutes, the temperature of the water bath was raised to about 35°C and maintained at this temperature for another 105 minutes. A white paste is produced. The vacuum was broken and 85.8 g of dry DMSO was added to dissolve the white solid, and then 6.0 g of diethylene glycol monomethyl ether and 2.7 g of aminoethylethanolamine were added to obtain the peeling solution in a substantially dry form as set forth in Table 1 of Example 1. The Karl Fischer method found that the water content of the dry stripping solution was 0.71% and the solution contained less than 1% methanol. Lower water content can be obtained by adding additional methanol to the white paste and maintaining the resulting solution under reduced pressure for another 2 to 5 hours.
利用活性分子篩充填適當量之闡述於實例18中之類型之乾式剝離溶液，以將剝離溶液在乾燥條件下維持較長時段。對於維持於封閉及密封容器中之每100g剝離溶液，添加約5克至約10克活性篩。較佳者係呈糰粒形式之分子篩。然而，若在使用前藉由過濾加以除去或若少量微粒物質不干擾乾式剝離溶液之使用，則可使用粉末狀篩。 An appropriate amount of dry peeling solution of the type described in Example 18 was filled with active molecular sieves to maintain the peeling solution under dry conditions for a longer period of time. For every 100 g of peeling solution maintained in a closed and sealed container, add about 5 grams to about 10 grams of active sieves. The preferred ones are molecular sieves in the form of pellets. However, if it is removed by filtration before use or if a small amount of particulate matter does not interfere with the use of the dry peeling solution, a powdered sieve can be used.
儘管已參考上述具體實施例提供申請者之揭示內容，但應瞭解彼等實踐此項技術者可作出所揭示實施例中之修改及改變而不背離本揭示內容之精神及範圍。意欲涵蓋所有該等修改及改變。 Although the applicant's disclosure content has been provided with reference to the above specific embodiments, it should be understood that those who practice the technology can make modifications and changes in the disclosed embodiments without departing from the spirit and scope of the disclosure. It is intended to cover all such modifications and changes.
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