TW201542715A - Composition of an alkaline etch mask agent, and an etching method - Google Patents
Composition of an alkaline etch mask agent, and an etching method Download PDFInfo
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Description
本發明係關於鹼蝕刻遮罩劑組成物、及使用其之矽基板之鹼蝕刻方法。 The present invention relates to an alkali etching mask composition and an alkali etching method using the same.
半導體，特別是太陽電池之製造步驟中，例如係進行藉由將矽基板予以部分選擇性地蝕刻處理，對基板表面施以紋理加工，來提高光電轉換效率。如此之紋理加工時的蝕刻處理，係有使用利用了氫氧化鈉或氫氧化鉀等之鹼水溶液之結晶方位的各向異性蝕刻之方法(以下稱為「鹼蝕刻」)。 In the manufacturing process of a semiconductor, particularly a solar cell, for example, the surface of the substrate is subjected to a texture process by partially etching the germanium substrate to improve the photoelectric conversion efficiency. In the etching treatment during the texturing process, an anisotropic etching method (hereinafter referred to as "alkali etching") using a crystal orientation of an aqueous alkali solution such as sodium hydroxide or potassium hydroxide is used.
以往，對矽基板選擇性地進行鹼蝕刻之方法，一般而言為藉由熱氧化或CVD(化學氣相蒸鍍)法，於基板一面形成氧化膜，藉由光微影法將該氧化膜一部分開窗後，將該部分予以選擇性地蝕刻的方法。例如，專利文獻1中，揭示於基板表面藉由熱氧化或CVD法形成耐蝕刻膜，於該耐蝕刻膜上形成撥水膜之導件後，形成 聚烯烴系之遮罩圖型，進行鹼蝕刻。 Conventionally, a method of selectively performing alkali etching on a tantalum substrate is generally an oxide film formed on one side of a substrate by thermal oxidation or CVD (chemical vapor deposition), and the oxide film is formed by photolithography. After a part of the window is opened, the portion is selectively etched. For example, in Patent Document 1, it is disclosed that an etching resistant film is formed on a surface of a substrate by thermal oxidation or CVD, and a guide of a water-repellent film is formed on the etching resistant film to form A polyolefin-based mask pattern is subjected to alkali etching.
但是，如此之以往的方法，會造成製造製程之步驟數增加，進一步地會伴隨著多量的設備投資，因此生產性非常低。 However, such a conventional method causes an increase in the number of steps in the manufacturing process, and further involves a large amount of equipment investment, so productivity is extremely low.
對基板部分選擇性地進行蝕刻時，係使用遮罩劑(蝕刻遮罩劑)，亦可認為例如藉由使用印刷型之鹼蝕刻遮罩，可改善上述鹼蝕刻處理所伴隨的問題。 When the substrate portion is selectively etched, a masking agent (etching masking agent) is used, and it is considered that the problem associated with the above-described alkali etching treatment can be improved by, for example, etching a mask using a printing type alkali.
然而，對蝕刻液之鹼水溶液具有優良耐性(鹼耐性)之鹼蝕刻遮罩劑尚未為人所知，即使於矽基板上將遮罩劑形成圖型，遮罩劑會因鹼蝕刻處理而溶解，對遮罩劑下之矽基板的蝕刻會進行，無法有效地施以蝕刻為所期望之圖型。 However, an alkali-etching masking agent having excellent resistance (alkali resistance) to an aqueous alkali solution of an etching solution is not known, and even if a masking agent is formed on a germanium substrate, the masking agent is dissolved by an alkali etching treatment. The etching of the substrate under the masking agent is performed, and etching is not effectively applied to a desired pattern.
[專利文獻1]日本特開2011-192921號公報 [Patent Document 1] Japanese Laid-Open Patent Publication No. 2011-192921
本發明係有鑑於如上述實情而為者，其目的為提供可形成具有優良鹼耐性之鹼蝕刻遮罩的鹼蝕刻遮罩劑組成物、及使用該鹼蝕刻遮罩劑組成物之鹼蝕刻方法。 The present invention has been made in view of the above circumstances, and an object thereof is to provide an alkali etching mask composition capable of forming an alkali etching mask having excellent alkali resistance, and an alkali etching method using the alkali etching mask composition .
本發明者等人為了解決上述課題重複努力探討的結果，發現藉由使用含有具有特定構造單位之聚矽氧烷，且相對於聚矽氧烷中之全部構造單位而言含有特定比例之該特定構造單位的鹼蝕刻遮罩劑組成物，會提高所得遮罩之鹼耐性，而完成了本發明。 As a result of repeated efforts to solve the above problems, the inventors of the present invention found that by using a polyoxyalkylene having a specific structural unit and containing a specific ratio with respect to all structural units in the polyoxyalkylene. The alkali etching mask composition of the structural unit improves the alkali resistance of the resulting mask, and the present invention has been completed.
本發明之第1態樣，係一種鹼蝕刻遮罩劑組成物，其含有具有下述通式(a1)表示之構造單位的聚矽氧烷，且相對於該聚矽氧烷中之全部構造單位而言，通式(a1)表示之構造單位的含量為15~100莫耳%。 According to a first aspect of the invention, there is provided an alkali-etching masking composition comprising a polyoxyalkylene having a structural unit represented by the following formula (a1), and all of the structures in the polyoxyalkylene In terms of unit, the content of the structural unit represented by the formula (a1) is 15 to 100 mol%.
本發明之第2態樣，係一種矽基板之蝕刻方法，其係包含於矽基板上，選擇性地形成由上述鹼蝕刻遮罩劑組成物所構成之組成物層的組成物層形成步驟、將該組成物層乾燥而於矽基板上形成鹼蝕刻遮罩之鹼蝕刻遮罩形成步驟、與將形成有鹼蝕刻遮罩之矽基板以鹼蝕刻液處 理之鹼蝕刻步驟。 According to a second aspect of the present invention, there is provided a method for forming a ruthenium substrate, comprising: a composition layer forming step of selectively forming a composition layer composed of the alkali etch mask composition; An alkali etching mask forming step of drying the composition layer to form an alkali etching mask on the germanium substrate, and an alkali etching solution for the germanium substrate on which the alkali etching mask is to be formed The base etching step.
依照本發明之鹼蝕刻遮罩劑組成物，可形成具有優良鹼耐性之鹼蝕刻遮罩。此外，藉由於基板上將使用該鹼蝕刻遮罩劑組成物所得到之遮罩形成圖型，可對該基板有效地施以蝕刻處理為所期望之圖型。 According to the alkali etching mask composition of the present invention, an alkali etching mask having excellent alkali resistance can be formed. Further, by forming a mask pattern on the substrate by using the alkali etching mask composition, the substrate can be effectively subjected to etching treatment to a desired pattern.
10‧‧‧矽基板 10‧‧‧矽 substrate
20‧‧‧組成物層 20‧‧‧Composed layers
20A‧‧‧鹼蝕刻遮罩 20A‧‧‧Alkaline etching mask
[圖1]用以說明鹼蝕刻方法之步驟流程之圖。 [Fig. 1] A diagram for explaining a flow of steps of an alkali etching method.
以下說明本發明之具體的實施形態。再者，本發明不限定於以下實施形態，可於不變更本發明要旨的範圍內進行各種變更。 Specific embodiments of the present invention will be described below. The present invention is not limited to the embodiments described below, and various modifications can be made without departing from the spirit and scope of the invention.
本發明之鹼蝕刻遮罩劑組成物，含有具有下述通式(a1)表示之構造單位的聚矽氧烷，且相對於該聚矽氧烷中之全部構造單位而言，下述通式(a1)表示之構造單位的含量為15~100莫耳%。 The alkali etching mask composition of the present invention contains a polyoxyalkylene having a structural unit represented by the following formula (a1), and the following formula is used with respect to all structural units in the polyoxyalkylene. The content of the structural unit represented by (a1) is 15 to 100 mol%.
式(a1)中，R1為單鍵或碳數1~5之伸烷基，R2為可具有烷基、烷氧基、鹵素原子、鹵化烷基、芳基、氰基、及/或胺基作為取代基之碳數6~20之芳基。 In the formula (a1), R 1 is a single bond or an alkylene group having 1 to 5 carbon atoms, and R 2 may have an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, an aryl group, a cyano group, and/or An amine group having 6 to 20 carbon atoms as a substituent.
依照如此之鹼蝕刻遮罩劑組成物，使用由該組成物所構成之油墨藉由印刷所形成之蝕刻遮罩會成為具有優良鹼耐性者。藉此，藉由施以使用該蝕刻遮罩之鹼蝕刻處理，可僅將遮罩圖型以外之部分有效地蝕刻。又，可不需如以往的將以熱氧化或CVD法所形成之氧化膜以光微影法將一部分開窗而選擇性地蝕刻之方法，可不增大製造製程之步驟數或設備投資地，對矽基板施以有效率的鹼蝕刻處理。 According to such an alkali-etching mask composition, an etching mask formed by printing using an ink composed of the composition becomes an excellent alkali resistance. Thereby, by applying the alkali etching treatment using the etching mask, only a portion other than the mask pattern can be effectively etched. Moreover, it is not necessary to selectively etch a portion of the oxide film formed by thermal oxidation or CVD by a photolithography method, and the number of steps of the manufacturing process or equipment investment may be increased. The crucible substrate is subjected to an efficient alkali etching treatment.
此處，本發明之鹼蝕刻遮罩劑組成物中，較佳為於組成物中不含有二氧化矽等無機填料。組成物中存在有無機填料時，可能無法充分得到藉由印刷所形成之鹼蝕刻遮罩的鹼耐性。再者，藉由含有無機填料，可提高由鹼蝕刻遮罩劑組成物所構成之油墨的黏性，但藉由在不含無機填料之狀態下依需要含有搖變劑，可輕易地增黏，可藉由適合的印刷方法來形成遮罩圖型。 Here, in the alkali-etching mask composition of the present invention, it is preferred that the composition does not contain an inorganic filler such as cerium oxide. When an inorganic filler is present in the composition, the alkali resistance of the alkali etching mask formed by printing may not be sufficiently obtained. Furthermore, by containing an inorganic filler, the viscosity of the ink composed of the alkali-etching masking agent composition can be improved, but it can be easily thickened by containing a rocking agent as needed without the inorganic filler. The mask pattern can be formed by a suitable printing method.
<聚矽氧烷> <polyoxane>
如上所述，本發明之鹼蝕刻遮罩劑組成物，含有具有上述通式(a1)表示之構造單位的聚矽氧烷。 As described above, the alkali etching mask composition of the present invention contains a polyoxyalkylene having a structural unit represented by the above formula (a1).
上述通式(a1)中，R1為單鍵或碳數1~5之伸烷基，R1為單鍵較佳。又，R1為伸烷基時，較佳為碳數1~4之伸烷基。再者，R1為伸烷基時的具體例子，可列舉亞甲基、1,2-伸乙基、1,1-伸乙基、丙烷-1,3-二基、丙烷-1,2-二基、丙烷-1,1-二基、丙烷-2,2-二基、丁烷-1,4-二基、丁烷-1,3-二基、丁烷-1,2-二基、丁烷-1,1-二基、丁烷-2,2-二基、丁烷-2,3-二基、戊烷-1,5-二基、戊烷-1,4-二基。 In the above formula (a1), R 1 is a single bond or an alkylene group having 1 to 5 carbon atoms, and R 1 is preferably a single bond. Further, when R 1 is an alkylene group, an alkylene group having 1 to 4 carbon atoms is preferred. Further, specific examples of the case where R 1 is an alkylene group include a methylene group, a 1,2-extended ethyl group, a 1,1-extended ethyl group, a propane-1,3-diyl group, and a propane-1,2. -diyl, propane-1,1-diyl, propane-2,2-diyl, butane-1,4-diyl, butane-1,3-diyl, butane-1,2-di Base, butane-1,1-diyl, butane-2,2-diyl, butane-2,3-diyl, pentane-1,5-diyl, pentane-1,4-di base.
上述通式(a1)中，R2為可具有取代基之碳數6~20之芳基，就可價格便宜地合成之觀點而言，較佳為可具有取代基之碳數6~10之芳基。又，該芳基可具有的取代基，係甲基、乙基、丙基、異丙基等之烷基；甲氧基、乙氧基、丙氧基、丁氧基等之烷氧基；氟、氯、碘、溴等之鹵素原子；氟化烷基等之上述烷基的氫原子之一部分或全部被鹵素原子取代之鹵化烷基；苯基、萘基等之芳基；氰基、及/或胺基。R2之具體上較佳者，可列舉例如苯基、乙基苯基、甲氧基苯基、萘基、甲基萘基等。 In the above formula (a1), R 2 is an aryl group having 6 to 20 carbon atoms which may have a substituent, and from the viewpoint of being inexpensively synthesized, it is preferably a carbon number of 6 to 10 which may have a substituent. Aryl. Further, the substituent which the aryl group may have is an alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a halogen atom such as fluorine, chlorine, iodine or bromine; a halogenated alkyl group in which a part or all of a hydrogen atom of the above alkyl group such as a fluorinated alkyl group is substituted with a halogen atom; an aryl group such as a phenyl group or a naphthyl group; And / or amine groups. Specific examples of R 2 include a phenyl group, an ethylphenyl group, a methoxyphenyl group, a naphthyl group, a methylnaphthyl group and the like.
聚矽氧烷，係相對於該聚矽氧烷中之全部構造單位而言，以15~100莫耳%之比例含有上述通式(a1)表示之構造單位者。又，更佳為以40~100莫耳%之比例含有上述通式(a1)表示之構造單位。藉由使上述 通式(a1)表示之構造單位的含量為15~100莫耳%，可有效地提高使用由本發明之鹼蝕刻遮罩劑組成物所構成之油墨所形成之蝕刻遮罩的鹼耐性。 The polyoxyalkylene contains the structural unit represented by the above formula (a1) in a ratio of 15 to 100 mol% based on all structural units in the polyoxyalkylene. Further, it is more preferable to contain the structural unit represented by the above formula (a1) in a ratio of 40 to 100 mol%. By making the above The content of the structural unit represented by the formula (a1) is 15 to 100 mol%, and the alkali resistance of the etching mask formed by using the ink composed of the alkali-etching mask composition of the present invention can be effectively improved.
聚矽氧烷之質量平均分子量(Mw)，只要不損及本發明之效果，無特殊限定，例如較佳為500~30000、更佳為1000~10000、特佳為1000~5000。再者，本說明書中，質量平均分子量(Mw)係指藉由凝膠滲透層析(GPC)所測定，以標準聚苯乙烯換算者。 The mass average molecular weight (Mw) of the polyoxyalkylene is not particularly limited as long as it does not impair the effects of the present invention, and is, for example, preferably from 500 to 30,000, more preferably from 1,000 to 10,000, particularly preferably from 1,000 to 5,000. In the present specification, the mass average molecular weight (Mw) means a standard polystyrene converted by gel permeation chromatography (GPC).
又，聚矽氧烷較佳為下述通式(a2)表示之聚矽氧烷。 Further, the polyoxyalkylene is preferably a polyoxyalkylene represented by the following formula (a2).
上述式(a2)中，R1及R2係如上述。又，R3為可具有取代基之碳數1~6之烷基。取代基係為甲基、乙基、丙基、異丙基等之烷基；甲氧基、乙氧基、丙氧基、丁氧基等之烷氧基；氟、氯、碘、溴等之鹵素原子；氟化烷基等之上述烷基之氫原子的一部分或全部被鹵素原子取代之鹵化烷基；氰基；胺基；乙烯基(vinyl)、烯丙基、丁烯基、乙烯基(ethenyl)、丙炔基等之烯基；環氧基、環氧丙氧基、丙烯醯氧基、及/或甲基丙烯醯氧基。再 者，下標字p及q，代表相對於聚矽氧烷中之全部構造單位而言，附有下標字之構造單位的莫耳百分率，p為15~100莫耳%、q為0~85莫耳%、p及q之合計為100莫耳%。 In the above formula (a2), R 1 and R 2 are as described above. Further, R 3 is an alkyl group having 1 to 6 carbon atoms which may have a substituent. The substituent is an alkyl group such as a methyl group, an ethyl group, a propyl group or an isopropyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a fluorine, a chlorine, an iodine, a bromine or the like; a halogen atom; a halogenated alkyl group in which a part or all of a hydrogen atom of the above alkyl group such as a fluorinated alkyl group is substituted with a halogen atom; a cyano group; an amine group; a vinyl group, an allyl group, a butenyl group, an ethylene group; An alkenyl group of ethenyl, propynyl or the like; an epoxy group, a glycidoxy group, an acryloxy group, and/or a methacryloxy group. Furthermore, the subscripts p and q represent the percentage of moles of the structural unit with the subscript, relative to all structural units in the polyoxane, p is 15 to 100 mol%, q is 0. The total of ~85 mole %, p and q is 100 mole %.
再者，上述式(a2)表示之聚矽氧烷中，該聚矽氧烷中之各構造單位，可分別具有2種以上之不同的R1~R3之構造單位。包含R1~R2之構造單位為2種以上時，較佳係R1為單鍵與碳數1~5之伸烷基的構成單位之組合、或R2為無取代之芳基與R2中具有上述取代基之芳基的構成單位之組合。又，包含R3之構造單位為2種以上時，較佳係R3為無取代之碳數1~6之烷基與R3中具有上述取代基之碳數1~6之烷基的構成單位之組合。 Further, in the polyoxyalkylene represented by the above formula (a2), each structural unit of the polyoxyalkylene may have two or more structural units of R 1 to R 3 . When the structural unit containing R 1 to R 2 is two or more kinds, it is preferred that R 1 is a combination of a single bond and a constituent unit of a C 1 to 5 alkyl group, or R 2 is an unsubstituted aryl group and R. 2 having the composition of the constituent units of the above-described aryl group substituents. When the structural unit containing R 3 is two or more kinds, it is preferred that R 3 is an unsubstituted alkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms having the above substituent in R 3 . The combination of units.
本發明之鹼蝕刻遮罩劑組成物之固體成分中，該聚矽氧烷之含有比例，並無特殊限定，較佳為於固體成分中為85質量%以上之比例。藉由使聚矽氧烷在固體成分中之含量為85質量%以上，可形成具有更優良鹼耐性之蝕刻遮罩，可更有效地防止於遮罩劑下對矽基板之蝕刻的進行。 In the solid content of the alkali-etching masking agent composition of the present invention, the content ratio of the polyoxyalkylene is not particularly limited, and is preferably a ratio of 85% by mass or more based on the solid content. By setting the content of the polyoxyalkylene in the solid content to 85% by mass or more, an etching mask having more excellent alkali resistance can be formed, and the etching of the substrate can be more effectively prevented under the masking agent.
<有機溶劑> <organic solvent>
本發明之鹼蝕刻遮罩劑組成物，較佳為將上述聚矽氧烷、或後述之添加劑等之全部成分溶解於適當之有機溶劑，以溶液(油墨)之形態使用。該有機溶劑可1種單獨或組合2種以上使用。 In the alkali etching mask composition of the present invention, it is preferred to use all of the components of the above polysiloxane or an additive described later in an appropriate organic solvent to be used in the form of a solution (ink). These organic solvents may be used alone or in combination of two or more.
具體而言，有機溶劑可列舉例如甲醇、乙醇、丙醇、n-丁醇等之醇類；乙二醇、二乙二醇、丙二醇、二丙二醇等之多元醇類；丙酮、甲基乙基酮、環己酮、甲基-n-戊基酮、甲基異戊基酮、2-庚酮等之酮類；乙二醇單乙酸酯、二乙二醇單乙酸酯、丙二醇單乙酸酯、或二丙二醇單乙酸酯等之具有酯鍵之化合物、多元醇類或具有酯鍵之化合物之單甲基醚、單乙基醚、單丙基醚、單丁基醚等之單烷基醚或單苯基醚等之具有醚鍵之化合物等之多元醇類之衍生物；二噁烷等之環狀醚類；乳酸甲酯、乳酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丁酯、丙酮酸甲酯、丙酮酸乙酯、甲氧基丙酸甲酯、乙氧基丙酸乙酯等之酯類；苯甲醚、乙基苄基醚、甲苯酚基甲基醚、二苯基醚、二苄基醚、苯乙酮、丁基苯基醚、乙基苯、二乙基苯、戊基苯、異丙基苯、甲苯、二甲苯、異丙基甲苯、均三甲苯等之芳香族系有機溶劑等。其中尤以使用二乙二醇單乙基醚乙酸酯、丙二醇單甲基酮乙酸酯(PGMEA)、丙二醇單甲基醚(PGME)、n-丁醇較佳。 Specific examples of the organic solvent include alcohols such as methanol, ethanol, propanol, and n-butanol; and polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; acetone and methyl ethyl Ketones such as ketone, cyclohexanone, methyl-n-amyl ketone, methyl isoamyl ketone, 2-heptanone, etc.; ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol a compound having an ester bond such as an acetate or a dipropylene glycol monoacetate, a monomethyl ether, a monoethyl ether, a monopropyl ether, a monobutyl ether or the like of a compound having a polyester bond or a compound having an ester bond. a derivative of a polyhydric alcohol such as a compound having an ether bond such as a monoalkyl ether or a monophenyl ether; a cyclic ether such as dioxane; methyl lactate, ethyl lactate, methyl acetate, and ethyl acetate , esters of butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxy propionate, etc.; anisole, ethyl benzyl ether, cresyl methyl Ether, diphenyl ether, dibenzyl ether, acetophenone, butyl phenyl ether, ethyl benzene, diethyl benzene, pentyl benzene, cumene, toluene, xylene, isopropyl An aromatic organic solvent such as benzene or mesitylene. Among them, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ketone acetate (PGMEA), propylene glycol monomethyl ether (PGME), and n-butanol are particularly preferably used.
有機溶劑之摻合量並無特殊限定，較佳為上述聚矽氧烷之濃度成為0.1~50質量%左右之量、更佳成為1~40質量%左右之量、又更佳成為1~30質量%左右之量。 The amount of the organic solvent to be blended is not particularly limited, and the concentration of the polysiloxane is preferably from about 0.1 to 50% by mass, more preferably from about 1 to 40% by mass, even more preferably from 1 to 30. The amount of mass is around.
<其他成分> <Other ingredients>
本發明之鹼蝕刻遮罩劑組成物，亦可依需要，於上述 聚矽氧烷、有機溶劑以外，含有其他成分。其他成分可列舉例如界面活性劑、搖變劑，但不限於此。 The alkali etching mask composition of the present invention may also be as described above In addition to polyoxyalkylene and organic solvents, other components are contained. The other component may, for example, be a surfactant or a shaker, but is not limited thereto.
(界面活性劑) (surfactant)
具體而言，作為界面活性劑，無特殊限定，可使用公知者。例如可使用矽系、丙烯酸系、氟系之界面活性劑。藉由添加如此之界面活性劑，於對矽基板印刷鹼蝕刻遮罩劑組成物(油墨)時，可抑制於基板上相對於所期望之印刷圖型寬度而言，實際上印刷之圖型寬度較大之所謂印刷模糊等之發生，而提高印刷安定性。 Specifically, the surfactant is not particularly limited, and a known one can be used. For example, a fluorene-based, acrylic-based, or fluorine-based surfactant can be used. By adding such a surfactant, when the alkali etch mask composition (ink) is printed on the ruthenium substrate, the width of the pattern actually printed on the substrate relative to the desired print pattern width can be suppressed. Larger so-called printing blurs occur, and print stability is improved.
矽系之界面活性劑，可列舉例如SF8421EG(東麗道康寧(股)製)、以聚酯改質聚二甲基矽氧烷為主成分之BYK-310(BYK chemie(股)製)、以芳烷基改質聚甲基烷基矽氧烷為主成分之BYK-323(BYK chemie(股)製)、以聚醚改質含羥基之聚二甲基矽氧烷為主成分之BYK-SILCLEAN3720(BYK chemie(股)製)、以聚醚改質甲基聚矽氧烷為主成分之KF-353(信越化學工業(股)製)等。又，丙烯酸系之界面活性劑，可列舉例如BYK-354(BYK chemie(股)製)等。又，氟系之界面活性劑，可列舉例如KL-600(共榮社化學製)等。此等之中尤以添加矽系之界面活性劑較佳。 Examples of the surfactants of the oxime system include, for example, SF8421EG (manufactured by Toray Dow Corning Co., Ltd.) and BYK-310 (manufactured by BYK Chemie Co., Ltd.) containing polyester modified polydimethyl siloxane as a main component. BYK-323 (BYK chemie Co., Ltd.) containing aralkyl modified polymethyl alkyl decane as main component and BYK- based on polyether modified polydimethyl methoxy oxane containing hydroxyl group SILCLEAN 3720 (manufactured by BYK chemie Co., Ltd.) and KF-353 (manufactured by Shin-Etsu Chemical Co., Ltd.) containing polyether modified methyl polyoxyalkylene as a main component. Further, examples of the acrylic surfactant include BYK-354 (manufactured by BYK Chemie Co., Ltd.). Further, examples of the fluorine-based surfactant include KL-600 (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, a surfactant of a lanthanoid system is particularly preferred.
界面活性劑之添加量並無特殊限定，例如較佳為0.001~1.0質量%左右、更佳為0.01~0.3質量%左右。 The amount of the surfactant to be added is not particularly limited, and is, for example, preferably about 0.001 to 1.0% by mass, more preferably about 0.01 to 0.3% by mass.
(搖變劑) (shake agent)
搖變劑，可作為所謂流變性控制劑來添加，其有效地使鹼蝕刻遮罩劑組成物增黏，圖型印刷時可藉由網版印刷等之方法形成遮罩圖型。特別地，本發明之鹼蝕刻遮罩劑組成物中，如上述般較佳為不含有無機填料，因此藉由不含有無機填料，組成物之黏度容易降低。此時，藉由添加搖變劑作為添加劑，會有效地提高組成物之黏度，可藉由網版印刷等之適合的印刷方法來形成遮罩圖型。 The rocking agent can be added as a so-called rheology control agent, which effectively thickens the alkali-etching masking agent composition, and can form a mask pattern by screen printing or the like in pattern printing. In particular, in the alkali-etching mask composition of the present invention, as described above, it is preferred that the inorganic filler is not contained. Therefore, the viscosity of the composition is liable to be lowered by not containing the inorganic filler. At this time, by adding a rocking agent as an additive, the viscosity of the composition is effectively increased, and a mask pattern can be formed by a suitable printing method such as screen printing.
具體而言，搖變劑並無特殊限定，可使用公知之市售品。例如，作為搖變劑，係有BYK-405、BYK-410、BYK-430(各為BYK chemie(股)公司製)等被市售。 Specifically, the rocking agent is not particularly limited, and a known commercial product can be used. For example, as a rocking agent, BYK-405, BYK-410, and BYK-430 (each manufactured by BYK Chemie Co., Ltd.) are commercially available.
如以上所述，本發明之鹼蝕刻遮罩劑組成物，含有具有上述通式(a1)表示之構造單位之聚矽氧烷，且相對於聚矽氧烷中之全部構造單位而言，上述通式(a1)表示之構造單位的含量為15~100莫耳%。依照如此之鹼蝕刻遮罩劑組成物，可極為有效地提高藉由印刷所形成之鹼蝕刻遮罩對鹼蝕刻液之耐性(鹼耐性)。藉此，與如以往般，藉由熱氧化或CVD法等形成氧化膜，將所形成之氧化膜藉由光微影法一部分開窗後選擇性地進行蝕刻的情況不同地，可抑制製造製程之步驟數或設備投資之增大，以高的生產性來進行鹼蝕刻處理。 As described above, the alkali-etching mask composition of the present invention contains the polyoxyalkylene having the structural unit represented by the above formula (a1), and the above-mentioned all structural units in the polyoxyalkylene, The content of the structural unit represented by the formula (a1) is 15 to 100 mol%. According to such an alkali-etching mask composition, the alkali etching solution (alkali resistance) by the alkali etching mask formed by printing can be extremely effectively improved. As a result, an oxide film is formed by thermal oxidation or CVD, and the formed oxide film is selectively etched by a photolithography method to selectively etch the oxide film, thereby suppressing the manufacturing process. The number of steps or equipment investment is increased, and the alkali etching treatment is performed with high productivity.
接著說明使用上述鹼蝕刻遮罩劑組成物之鹼蝕刻方法。圖1係用以說明本發明之鹼蝕刻方法之步驟流程的示意圖。 Next, an alkali etching method using the above-described alkali etching mask composition will be described. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the flow of steps of the alkali etching method of the present invention.
如圖1(A)~(C)所示，本發明之鹼蝕刻方法，具有於矽基板上選擇性地形成組成物層之組成物層形成步驟、將所形成之組成物層乾燥而形成鹼蝕刻遮罩之鹼蝕刻遮罩形成步驟、與將該矽基板以鹼蝕刻液處理之鹼蝕刻步驟。 As shown in FIGS. 1(A) to (C), the alkali etching method of the present invention has a composition layer forming step of selectively forming a composition layer on a tantalum substrate, and drying the formed composition layer to form a base. An alkali etching mask forming step of etching the mask and an alkali etching step of treating the germanium substrate with an alkali etching solution.
<組成物層形成步驟> <Composition layer formation step>
組成物層形成步驟中，如圖1(A)所示，係於矽基板10上選擇性地形成組成物層20。更具體而言，本發明之鹼蝕刻方法中，係將由含有具有上述通式(a1)表示之構造單位之聚矽氧烷，且相對於聚矽氧烷中之全部構造單位而言，上述通式(a1)表示之構造單位的含量為15~100莫耳%的鹼蝕刻遮罩劑組成物所構成之油墨，於矽基板10上選擇性地進行圖型印刷而塗佈，形成由該組成物所構成之層(組成物層20)。 In the composition layer forming step, as shown in FIG. 1(A), the composition layer 20 is selectively formed on the tantalum substrate 10. More specifically, in the alkali etching method of the present invention, the above-mentioned pass is composed of a polyoxyalkylene having a structural unit represented by the above formula (a1) and with respect to all structural units in the polyoxyalkylene. An ink comprising an alkali-etching masking agent composition having a structural unit content of 15 to 100 mol% represented by the formula (a1) is selectively applied to the ruthenium substrate 10 by pattern printing to form a composition. The layer formed by the object (composition layer 20).
由上述鹼蝕刻遮罩劑組成物所構成之油墨之圖型印刷方法，並無特殊限定，例如可使用網版印刷法、噴墨印刷法、輥塗佈印刷法、凸版印刷法、凹版印刷法、平版印刷法等之印刷法來形成遮罩圖型。 The pattern printing method of the ink composed of the alkali etching mask composition is not particularly limited, and for example, a screen printing method, an inkjet printing method, a roll coating printing method, a letterpress printing method, or a gravure printing method can be used. A printing method such as a lithography method forms a mask pattern.
組成物層形成步驟中形成之組成物層20的厚 度(膜厚)，並無特殊限定，例如較佳為5~100μm左右、更佳為10~50μm左右。 Thickness of the composition layer 20 formed in the composition layer forming step The degree (film thickness) is not particularly limited, and is, for example, preferably about 5 to 100 μm, more preferably about 10 to 50 μm.
再者，該組成物層形成步驟中，在於矽基板10上形成組成物層20之前，亦可依需要對矽基板10進行各種前處理。前處理可列舉例如對矽基板之洗淨處理、或撥液性層之形成處理等。關於撥液性層之形成處理，可列舉例如日本特開2009-253145號公報記載之方法。 Further, in the composition layer forming step, before the composition layer 20 is formed on the tantalum substrate 10, various pre-treatments may be performed on the tantalum substrate 10 as needed. Examples of the pretreatment include a washing treatment for a ruthenium substrate, a formation treatment of a liquid repellency layer, and the like. The method of forming the liquid-repellent layer is, for example, a method described in JP-A-2009-253145.
<鹼蝕刻遮罩形成步驟> <Alkaline etching mask forming step>
接著，鹼蝕刻遮罩形成步驟中，如圖1(B)所示，係將於矽基板10上圖型選擇性地形成的組成物層20乾燥，於該矽基板10上形成鹼蝕刻遮罩20A(亦單稱為「遮罩20A」)。 Next, in the alkali etching mask forming step, as shown in FIG. 1(B), the composition layer 20 selectively formed on the germanium substrate 10 is dried, and an alkali etching mask is formed on the germanium substrate 10. 20A (also referred to as "Mask 20A").
組成物層20之乾燥(Bake)處理之條件並無特殊限定，可依組成物層20之膜厚或鹼蝕刻遮罩劑組成物之成分等來適當設定。具體而言，例如可於150~200℃之溫度條件進行約3分鐘之乾燥處理。藉由如此方式處理，於矽基板10上所形成之組成物層20中的溶劑會乾燥，可於矽基板10上形成鹼蝕刻遮罩20A。 The conditions of the Bake treatment of the composition layer 20 are not particularly limited, and may be appropriately set depending on the film thickness of the composition layer 20 or the composition of the alkali-etching masking agent composition. Specifically, for example, drying treatment can be carried out for about 3 minutes at a temperature of 150 to 200 °C. By treating in this manner, the solvent in the composition layer 20 formed on the tantalum substrate 10 is dried, and the alkali etching mask 20A can be formed on the tantalum substrate 10.
又，該鹼蝕刻遮罩形成步驟中，對組成物層20施以乾燥處理後，亦可施以燒成(Cure)處理。燒成處理之條件並無特殊限定，可依組成物層20之膜厚或鹼蝕刻遮罩劑組成物之成分等來適當設定。具體而言，例如可於250~400℃之溫度條件進行約15分鐘之燒成處理。 再者，燒成處理中之溫度過高時(例如600℃以上)，會有組成物層20中所含之聚矽氧烷的有機基消失，對後述鹼蝕刻液無法充分得到鹼耐性的可能性。 Further, in the alkali etching mask forming step, the composition layer 20 may be subjected to a drying treatment after being subjected to a drying treatment. The conditions of the firing treatment are not particularly limited, and may be appropriately set depending on the film thickness of the composition layer 20 or the composition of the alkali-etching masking agent composition. Specifically, for example, the firing treatment can be carried out at a temperature of 250 to 400 ° C for about 15 minutes. In addition, when the temperature in the baking treatment is too high (for example, 600 ° C or higher), the organic group of the polyoxyalkylene contained in the composition layer 20 disappears, and the alkali etching solution to be described later may not sufficiently obtain alkali resistance. Sex.
<鹼蝕刻步驟> <alkali etching step>
然後，鹼蝕刻步驟中，如圖1(C)所示，係將形成有鹼蝕刻遮罩20A之矽基板10以鹼蝕刻液處理。亦即，於矽基板10上對形成有鹼蝕刻遮罩20A之部分以外進行蝕刻處理。 Then, in the alkali etching step, as shown in FIG. 1(C), the tantalum substrate 10 on which the alkali etching mask 20A is formed is treated with an alkali etching solution. That is, an etching treatment is performed on the tantalum substrate 10 except for the portion where the alkali etching mask 20A is formed.
鹼蝕刻步驟中使用之鹼蝕刻液(鹼浸蝕劑)，並無特殊限定，可使用公知者。具體而言，例如可使用由氫氧化鉀(KOH)：2質量%、異丙基醇(IPA)：8質量%、水(H2O)：90質量%之組成所成之蝕刻液；由氫氧化鉀(KOH)：10質量%、水(H2O)：90質量%之組成所成之蝕刻液等來進行。 The alkali etching solution (alkaline etching agent) used in the alkali etching step is not particularly limited, and a known one can be used. Specifically, for example, an etching liquid composed of a composition of potassium hydroxide (KOH): 2% by mass, isopropyl alcohol (IPA): 8 mass%, and water (H 2 O): 90% by mass can be used; An etching solution made of a composition of potassium hydroxide (KOH): 10% by mass and water (H 2 O): 90% by mass is used.
又，關於鹼蝕刻條件，亦無特殊限定，可依對形成有鹼蝕刻遮罩20A之部分以外的矽基板10之所期望的蝕刻深度等來適當設定。具體而言，例如可藉由使鹼蝕刻液之液溫為80℃、將矽基板10浸漬於鹼蝕刻液1~30分鐘等來進行。 Further, the alkali etching conditions are not particularly limited, and may be appropriately set depending on the desired etching depth of the tantalum substrate 10 other than the portion in which the alkali etching mask 20A is formed. Specifically, for example, the liquid temperature of the alkali etching solution can be 80 ° C, and the tantalum substrate 10 can be immersed in an alkali etching solution for 1 to 30 minutes.
再者，如上述般進行過鹼蝕刻處理後，將鹼蝕刻遮罩20A去除。去除方法並無特殊限定，可列舉例如藉由使用丙酮等之有機溶劑或市售之剝離液等，室溫下於該剝離液中，浸漬矽基板5~10分左右而剝離之方法等。 Further, after the alkali etching treatment as described above, the alkali etching mask 20A is removed. The removal method is not particularly limited, and examples thereof include a method of immersing the ruthenium substrate for about 5 to 10 minutes at a room temperature by using an organic solvent such as acetone or a commercially available release liquid, and the like.
如以上方式，於矽基板10上形成鹼蝕刻遮罩20A，且對形成有遮罩20A之矽基板10施以鹼蝕刻處理，藉此可僅將未形成有遮罩20A之部分予以選擇性地蝕刻。亦即，本發明之鹼蝕刻方法中，藉由將該遮罩20A以由含有具有上述通式(a1)表示之構造單位之聚矽氧烷，且相對於聚矽氧烷中之全部構造單位而言上述通式(a1)表示之構造單位的含量為15~100莫耳%的鹼蝕刻遮罩劑組成物所構成之油墨來形成，可成為具有優良鹼耐性之遮罩20A。藉此，可有效防止鹼蝕刻液對形成有遮罩20A之部分(遮罩劑下)之矽基板10的溶解，有效地進行蝕刻處理。 As described above, the alkali etching mask 20A is formed on the crucible substrate 10, and the crucible substrate 10 on which the mask 20A is formed is subjected to an alkali etching treatment, whereby only the portion in which the mask 20A is not formed can be selectively selected. Etching. That is, in the alkali etching method of the present invention, the mask 20A is made of a polyoxyalkylene having a structural unit represented by the above formula (a1), and is relative to all structural units in the polyoxyalkylene. The above-described formula (a1) is formed by forming an ink composed of an alkali-etching masking agent composition having a structural unit content of 15 to 100 mol%, and can be a mask 20A having excellent alkali resistance. Thereby, the dissolution of the alkali etching liquid on the crucible substrate 10 in which the mask 20A is formed (under the masking agent) can be effectively prevented, and the etching treatment can be effectively performed.
以下顯示實施例，以進一步詳細說明本發明，但本發明不受此等實施例限定。 The examples are shown below to further illustrate the invention, but the invention is not limited by the examples.
(鹼蝕刻遮罩劑組成物之配製) (Formulation of alkali-etched masking agent composition)
如下述表1所示，將聚矽氧烷、有機溶劑、與依需要之添加劑予以混合，配製鹼蝕刻遮罩劑組成物。再者，表1中之成分表示中所示之括弧『( )』內的數字，表示組成物中之含量(摻合量)。 As shown in the following Table 1, a polyoxyalkylene oxide, an organic solvent, and an additive as needed were mixed to prepare an alkali-etching masking agent composition. Further, the numbers in parentheses "( )" shown in the component numbers in Table 1 indicate the contents (mixing amounts) in the composition.
具體而言，係配製由鹼蝕刻遮罩劑組成物所 構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：含有100莫耳%之比例之下述式(a3)表示之構造單位的聚矽氧烷(以下稱為「(A)-3」)且質量平均分子量Mw為500~1500者40質量%、二乙二醇單乙基醚乙酸酯(以下稱為「(S)-1」)54.7質量%、作為添加劑(1)之界面活性劑(製品名：SF8421EG、東麗道康寧(股)製)(以下稱為「SF8421EG」)0.3質量%、作為添加劑(2)之搖變劑(製品名：BYK-430、BYK chemie(股)製)(以下稱為「BYK430」)5質量%之比例。 Specifically, it is formulated by an alkali-etching masking agent composition. The ink constituting the alkali etch mask composition contains a polysiloxane (hereinafter referred to as "(A)-3") having a structural unit represented by the following formula (a3) in a ratio of 100 mol%. And the mass average molecular weight Mw is 40 to 1500% by mass, and diethylene glycol monoethyl ether acetate (hereinafter referred to as "(S)-1") is 54.7 mass%, and the interface activity as the additive (1) (product name: SF8421EG, manufactured by Toray Dow Corning Co., Ltd.) (hereinafter referred to as "SF8421EG") 0.3% by mass, as a modifier (2), a shaker (product name: BYK-430, BYK chemie) (hereinafter referred to as "BYK430") is a ratio of 5 mass%.
(蝕刻遮罩之形成) (formation of etching mask)
將如上述方式配製之油墨，於矽基板上使用500μm之線圖型之版來進行網版印刷。再者，網版印刷係於25 ℃之溫度、300mm/s、乳劑厚度10μm之條件進行。 The ink prepared as described above was screen-printed on a ruthenium substrate using a 500 μm line pattern. Furthermore, screen printing is at 25 The temperature of °C, 300 mm/s, and the thickness of the emulsion were 10 μm.
接著，於200℃之加熱板使溶劑乾燥(Bake)3分鐘。之後，進行400℃-15分鐘之燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩。 Next, the solvent was dried (Bake) on a hot plate at 200 ° C for 3 minutes. Thereafter, a firing treatment (Cure) at 400 ° C for 15 minutes was performed to form an alkali etching mask on the tantalum substrate.
(鹼蝕刻處理) (alkali etching treatment)
將如上述方式形成有鹼蝕刻遮罩之燒成處理基板(矽基板)，對鹼蝕刻液(KOH：2質量%、IPA：8質量%、H2O：90質量%)以80℃-30分鐘之蝕刻條件浸漬，進行鹼蝕刻處理。 A baking treatment substrate (tantalum substrate) having an alkali etching mask formed as described above, and an alkali etching solution (KOH: 2% by mass, IPA: 8 mass%, H 2 O: 90% by mass) at 80 ° C - 30 The etching conditions were immersed in a minute, and an alkali etching treatment was performed.
實施例2中，除了將聚矽氧烷((A)-3)之含量設為30質量%、將二乙二醇單乙基醚乙酸酯((S)-1)之含量設為64.7質量%以外，係與實施例1相同方式配製由鹼蝕刻遮罩劑組成物所構成之油墨，形成蝕刻遮罩。 In Example 2, the content of polyoxyalkylene oxide ((A)-3) was set to 30% by mass, and the content of diethylene glycol monoethyl ether acetate ((S)-1) was set to 64.7. An ink composed of an alkali-etched masking agent composition was prepared in the same manner as in Example 1 except for % by mass to form an etching mask.
實施例3中，除了將聚矽氧烷((A)-3)之含量設為20質量%、將二乙二醇單乙基醚乙酸酯((S)-1)之含量設為74.7質量%、且不添加添加劑(2)之搖變劑以外，係與實施例1相同方式配製由鹼蝕刻遮罩劑組成物所構成之油墨。 In Example 3, the content of polyoxyalkylene oxide ((A)-3) was set to 20% by mass, and the content of diethylene glycol monoethyl ether acetate ((S)-1) was set to 74.7. An ink composed of an alkali-etched masking agent composition was prepared in the same manner as in Example 1 except that the rocking agent of the additive (2) was not added in mass.
而實施例3中，係使用如此方式配製的油 墨，藉由噴墨印刷法於矽基板上印刷遮罩圖型。 In Example 3, the oil formulated in this manner was used. Ink, the mask pattern is printed on the ruthenium substrate by inkjet printing.
實施例4中，除了於蝕刻遮罩形成時、乾燥(Bake)處理之後，進行250℃-15分鐘之燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩以外，係與實施例1相同。 In the fourth embodiment, in addition to the formation of the etching mask and the Bake treatment, a baking treatment (Cure) of 250 ° C for 15 minutes is performed, and an alkali etching mask is formed on the tantalum substrate. the same.
實施例5中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：含有100莫耳%之比例之上述式(a3)表示之構造單位的聚矽氧烷((A)-3)且質量平均分子量Mw為30000者(再者，下述表1中係表述為「(A)-3[Mw：30000]」)40質量%、二乙二醇單乙基醚乙酸酯((S)-1)54.9質量%、添加劑(1)之界面活性劑(SF8421EG)0.1質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。使用該油墨，與實施例1同樣方式地藉由網版印刷來進行圖型印刷，形成蝕刻遮罩，施以鹼蝕刻處理。 In the embodiment 5, an ink composed of an alkali-etching masking agent composition containing a structural unit represented by the above formula (a3) in a ratio of 100 mol% is prepared. Polyoxane ((A)-3) and having a mass average molecular weight Mw of 30,000 (again, in Table 1 below, it is expressed as "(A)-3 [Mw: 30000]") 40% by mass, two Diol monoethyl ether acetate ((S)-1) 54.9 mass%, additive (1) surfactant (SF8421 EG) 0.1 mass%, additive (2) shake agent (BYK430) 5 mass% proportion. Using this ink, pattern printing was carried out by screen printing in the same manner as in Example 1, and an etching mask was formed and subjected to an alkali etching treatment.
實施例6中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：含有100莫耳%之比例之下述式(a4)表示之構造單位的聚矽氧烷(Mw：2000~4000)(以下稱為「(A)-4」)40質量%、 二乙二醇單乙基醚乙酸酯((S)-1)54.9質量%、添加劑(1)之界面活性劑(SF8421EG)0.1質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。使用該油墨，與實施例1同樣方式地藉由網版印刷來進行圖型印刷，形成蝕刻遮罩，施以鹼蝕刻處理。 In the sixth embodiment, an ink composed of an alkali-etching masking agent composition containing a structural unit represented by the following formula (a4) having a ratio of 100 mol% is prepared. Polyoxane (Mw: 2000~4000) (hereinafter referred to as "(A)-4") 40% by mass, Diethylene glycol monoethyl ether acetate ((S)-1) 54.9 mass%, additive (1) surfactant (SF8421EG) 0.1% by mass, additive (2) shaker (BYK430) 5 mass The proportion of %. Using this ink, pattern printing was carried out by screen printing in the same manner as in Example 1, and an etching mask was formed and subjected to an alkali etching treatment.
實施例7中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：下述式(a5)表示之聚矽氧烷(Mw：4500)(以下稱為「(A)-5」)40質量%、二乙二醇單乙基醚乙酸酯((S)-1)54.9質量%、添加劑(1)之界面活性劑(SF8421EG)0.1質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。使用該油墨，與實施例1同樣方式地藉由網版印刷來進行圖型印刷，形成蝕刻遮罩，施以鹼蝕刻處理。 In the seventh embodiment, an ink composed of an alkali-etching masking agent composition containing a polyoxyalkylene (Mw: 4500) represented by the following formula (a5) is prepared. Hereinafter, it is referred to as "(A)-5") 40% by mass, diethylene glycol monoethyl ether acetate ((S)-1) 54.9% by mass, and the additive (1) surfactant (SF8421EG) 0.1 mass. %, the ratio of the shaker (BYK430) of the additive (2) to 5 mass%. Using this ink, pattern printing was carried out by screen printing in the same manner as in Example 1, and an etching mask was formed and subjected to an alkali etching treatment.
實施例8中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：聚矽氧烷((A)-3)40質量%、二乙二醇單乙基醚乙酸酯((S)-1)54.7質量%、作為添加劑(1)之界面活性劑(製品名：KL401、共榮社化學(股)製)(以下稱為「KL401」)0.3質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。 In the eighth embodiment, an ink composed of an alkali-etching masking agent composition containing: polyoxyalkylene ((A)-3) 40% by mass, two ethylene is prepared. Alcohol monoethyl ether acetate ((S)-1) 54.7 mass%, a surfactant (1) of the additive (product name: KL401, Kyoeisha Chemical Co., Ltd.) (hereinafter referred to as "KL401") ) A ratio of 0.3% by mass of the additive (2) to a rocking agent (BYK430) of 5% by mass.
使用該油墨，與實施例1同樣方式地藉由網版印刷來進行圖型印刷後，實施例8中，於鹼蝕刻處理時，將基板對鹼蝕刻液(KOH：10質量%、H2O：90質量%)以80℃-5分鐘之蝕刻條件浸漬，施以鹼蝕刻處理。 Using this ink, pattern printing was carried out by screen printing in the same manner as in Example 1, and in Example 8, the substrate was subjected to an alkali etching solution (KOH: 10% by mass, H 2 O) during the alkali etching treatment. : 90% by mass) was immersed under an etching condition of 80 ° C to 5 minutes, and subjected to an alkali etching treatment.
實施例9中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：聚矽氧烷((A)-3)30質量%、二乙二醇單乙基醚乙酸酯((S)-1)64.7質 量%、添加劑(1)之界面活性劑(SF8421EG)0.3質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。 In the embodiment 9, an ink composed of an alkali-etching masking agent composition containing: polyoxyalkylene ((A)-3) 30% by mass, two ethylene is prepared. Alcohol monoethyl ether acetate ((S)-1) 64.7 The ratio of the amount %, the surfactant (1) of the additive (1) to 0.3% by mass, and the amount of the modifier (2) of the shaker (BYK430) of 5 mass%.
實施例9中，使用該油墨，於矽基板上藉由網版印刷來形成圖型並乾燥(Bake)後，不進行燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩，施以鹼蝕刻處理。再者，關於乾燥處理等或遮罩形成後之蝕刻處理，係與實施例1相同之條件。 In Example 9, after the ink was formed on the ruthenium substrate by screen printing and dried (Bake), the baking treatment (Cure) was not performed, and an alkali etching mask was formed on the ruthenium substrate. Alkali etching treatment. Further, the etching treatment after the drying treatment or the like or the mask formation is the same as in the first embodiment.
實施例10~15中，係使下述通式(a6)表示之聚矽氧烷(Mw：2500)、與作為有機溶劑之丙二醇單甲基醚乙酸酯(PGMEA)以質量比成為10：90的方式混合，配製由鹼蝕刻遮罩劑組成物所構成之油墨。 In Examples 10 to 15, the polyoxyalkylene (Mw: 2500) represented by the following formula (a6) and the propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent were 10 in mass ratio: The method of 90 is mixed to prepare an ink composed of an alkali-etched masking agent composition.
具體而言，實施例10~15中，作為上述通式(a6)表示之聚矽氧烷，分別含有以下者。亦即， Specifically, in Examples 10 to 15, the polysiloxanes represented by the above formula (a6) each contain the following. that is,
實施例10聚矽氧烷[A](上述式中，p1：59、q1：1、r1：40) Example 10 Polyoxane [A] (in the above formula, p1: 59, q1:1, r1: 40)
實施例11聚矽氧烷[B](上述式中，p1：19、q1：1、r1：80) Example 11 Polyoxane [B] (in the above formula, p1: 19, q1:1, r1: 80)
實施例12聚矽氧烷[C](上述式中，p1：39、q1：1、r1：60) Example 12 Polyoxane [C] (in the above formula, p1: 39, q1:1, r1: 60)
實施例13聚矽氧烷[D](上述式中，p1：69、q1：1、r1：30) Example 13 polyoxyalkylene [D] (in the above formula, p1: 69, q1:1, r1: 30)
實施例14聚矽氧烷[E](上述式中，p1：79、q1：1、r1：20) Example 14 Polyoxane [E] (in the above formula, p1: 79, q1:1, r1: 20)
實施例15聚矽氧烷[F](上述式中，p1：84、q1：1、r1：15) Example 15 Polyoxane [F] (in the above formula, p1: 84, q1:1, r1:15)
使用如此方式配製之油墨，與實施例1同樣方式地藉由網版印刷來進行圖型印刷，形成蝕刻遮罩，施以鹼蝕刻處理。 Using the ink prepared in this manner, pattern printing was carried out by screen printing in the same manner as in Example 1, and an etching mask was formed and subjected to an alkali etching treatment.
比較例1中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：下述式(b1)表示之聚矽氧烷(Mw：2400)(以下稱為「(B)-1」)40質量%、二乙二醇單乙基醚乙酸酯((S)-1)54.7質量%、添加劑(1)之界面活性劑(SF8421EG)0.3質量%、添加劑 (2)之搖變劑(BYK430)5質量%之比例。 In Comparative Example 1, an ink composed of an alkali-etching masking agent composition containing a polyoxyalkylene represented by the following formula (b1) (Mw: 2400) was prepared. Hereinafter, it is referred to as "(B)-1") 40% by mass, diethylene glycol monoethyl ether acetate ((S)-1) 54.7% by mass, and the additive (1) surfactant (SF8421EG) 0.3 mass. %,additive (2) The ratio of the rocking agent (BYK430) of 5 mass%.
使用該油墨，於矽基板上藉由網版印刷來形成圖型並乾燥(Bake)後，不進行燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩，施以鹼蝕刻處理。再者，關於乾燥處理等或遮罩形成後之蝕刻處理，係與實施例1相同之條件。 Using this ink, a pattern was formed on the tantalum substrate by screen printing and dried (Bake), and then an alkali etching mask was formed on the tantalum substrate without performing a baking treatment (Cure), and an alkali etching treatment was performed. Further, the etching treatment after the drying treatment or the like or the mask formation is the same as in the first embodiment.
比較例2中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：下述式(b2)表示之聚矽氧烷(Mw：2000)(以下稱為「(B)-2」)40質量%、二乙二醇單乙基醚乙酸酯((S)-1)54.7質量%、添加劑(1)之界面活性劑(SF8421EG)0.3質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。 In Comparative Example 2, an ink composed of an alkali-etching masking agent composition containing a polyoxyalkylene represented by the following formula (b2) (Mw: 2000) was prepared. Hereinafter, it is referred to as "(B)-2") 40% by mass, diethylene glycol monoethyl ether acetate ((S)-1) 54.7% by mass, and the additive (1) surfactant (SF8421EG) 0.3 mass. %, the ratio of the shaker (BYK430) of the additive (2) to 5 mass%.
使用該油墨，於矽基板上藉由網版印刷來形成圖型並乾燥(Bake)後，不進行燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩，施以鹼蝕刻處理。再者，關於乾燥處理等或遮罩形成後之蝕刻處理，係與實施例1相同之條件。 Using this ink, a pattern was formed on the tantalum substrate by screen printing and dried (Bake), and then an alkali etching mask was formed on the tantalum substrate without performing a baking treatment (Cure), and an alkali etching treatment was performed. Further, the etching treatment after the drying treatment or the like or the mask formation is the same as in the first embodiment.
比較例3中，係配製由鹼蝕刻遮罩劑組成物所構成之油墨，該鹼蝕刻遮罩劑組成物，係含有：下述式(b3)表示之聚矽氧烷(Mw：7000)(以下稱為「(B)-3」)40質量%、二乙二醇單乙基醚乙酸酯((S)-1)54.7質量%、添加劑(1)之界面活性劑(SF8421EG)0.3質量%、添加劑(2)之搖變劑(BYK430)5質量%之比例。 In Comparative Example 3, an ink composed of an alkali-etching masking agent composition containing a polyoxyalkylene (Mw: 7000) represented by the following formula (b3) was prepared. Hereinafter, it is referred to as "(B)-3") 40% by mass, diethylene glycol monoethyl ether acetate ((S)-1) 54.7% by mass, and the additive (1) surfactant (SF8421EG) 0.3 mass. %, the ratio of the shaker (BYK430) of the additive (2) to 5 mass%.
使用該油墨，於矽基板上藉由網版印刷來形成圖型並乾燥(Bake)後，不進行燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩，施以鹼蝕刻處理。再者，關於乾燥處理等或遮罩形成後之蝕刻處理，係與實施例1相同之條件。 Using this ink, a pattern was formed on the tantalum substrate by screen printing and dried (Bake), and then an alkali etching mask was formed on the tantalum substrate without performing a baking treatment (Cure), and an alkali etching treatment was performed. Further, the etching treatment after the drying treatment or the like or the mask formation is the same as in the first embodiment.
比較例4中，係配製由與比較例3相同之鹼蝕刻遮罩劑組成物所構成之油墨，使用該油墨形成蝕刻遮罩時，於乾燥(Bake)處理後，進行400℃-15分鐘之燒成處理(Cure)，於矽基板上形成鹼蝕刻遮罩。再者，其以外之條件係與比較例3相同。 In Comparative Example 4, an ink composed of the alkali-etching masking agent composition similar to that of Comparative Example 3 was prepared, and when an etching mask was formed using the ink, it was subjected to a Bake treatment at 400 ° C for 15 minutes. A baking treatment (Cure) forms an alkali etching mask on the tantalum substrate. Further, the other conditions were the same as in Comparative Example 3.
比較例5、6中，係使上述通式(a6)表示之聚矽氧烷(Mw：2500)、與作為有機溶劑之丙二醇單甲基醚乙酸酯(PGMEA)以質量比成為10：90的方式混合，配製由鹼蝕刻遮罩劑組成物所構成之油墨。 In Comparative Examples 5 and 6, the polyoxane (Mw: 2500) represented by the above formula (a6) and the propylene glycol monomethyl ether acetate (PGMEA) as an organic solvent were 10:90 by mass ratio. The method is mixed to prepare an ink composed of an alkali-etched masking agent composition.
具體而言，比較例5、6中，作為上述通式(a6)表示之聚矽氧烷，係分別含有以下者。亦即， Specifically, in Comparative Examples 5 and 6, the polysiloxanes represented by the above formula (a6) each contain the following. that is,
比較例5聚矽氧烷[G](上述式中，p1：90、q1：10、r1：0) Comparative Example 5 polyoxyalkylene [G] (in the above formula, p1: 90, q1: 10, r1: 0)
比較例6聚矽氧烷[H](上述式中，p1：89、q1：1、r1：10) Comparative Example 6 polyoxyalkylene [H] (in the above formula, p1: 89, q1:1, r1: 10)
使用如此方式所配製之油墨，與實施例1同樣方式地藉由網版印刷來進行圖型印刷，形成蝕刻遮罩，施以鹼蝕刻處理。 Using the ink prepared in this manner, pattern printing was carried out by screen printing in the same manner as in Example 1, and an etching mask was formed and subjected to an alkali etching treatment.
如以上般，對於各實施例、比較例中施以鹼蝕刻處理之基板，確認印刷圖型(遮罩劑)之有無、印刷圖型下(遮罩劑下)之Si蝕刻進行之有無，評估蝕刻遮罩之鹼蝕刻耐性。鹼蝕刻耐性之評估，具體而言係如以下方式分類來評估。下述表1顯示各實施例、比較例之評估結果。 As described above, in the substrates subjected to the alkali etching treatment in each of the examples and the comparative examples, the presence or absence of the printing pattern (masking agent) and the presence or absence of the Si etching under the printing pattern (under the masking agent) were evaluated. Alkali etching resistance of the etch mask. The evaluation of alkali etching resistance, specifically, is classified as follows in the following manner. Table 1 below shows the evaluation results of the respective examples and comparative examples.
『○』：有印刷圖型、無印刷圖型下之Si蝕刻進行。 『○』: Si etching is performed under a printed pattern and a non-printing pattern.
『×』：印刷圖型之至少一部分溶解而消失、且有印刷圖型下之Si蝕刻進行。 『×』: At least a part of the printing pattern is dissolved and disappears, and Si etching is performed under the printing pattern.
如表1所示，使用含有具有上述通式(a1)表示之構造單位的聚矽氧烷之組成物且相對於該聚矽氧烷中之全部構造單位而言上述通式(a1)表示之構造單位的含量為15~100莫耳%的鹼蝕刻遮罩組成物，於矽基板上形成鹼蝕刻遮罩之實施例1~15中，對鹼蝕刻處理顯示優良的鹼耐性，於遮罩劑下之蝕刻全無進行。 As shown in Table 1, a composition containing a polysiloxane having a structural unit represented by the above formula (a1) is used, and the above formula (a1) is represented with respect to all structural units in the polyoxyalkylene. The alkali etching mask composition having a structural unit content of 15 to 100 mol%, and the alkali etching mask formed on the tantalum substrate, in Examples 1 to 15, showed excellent alkali resistance to the alkali etching treatment, and the masking agent The etching underneath is not carried out at all.
相對於此，使用了含有不具有上述通式(a1)表示之構造單位的聚矽氧烷之組成物的比較例1~4、以及使用了含有雖具有上述通式(a1)表示之構造單位，但相對於該聚矽氧烷中之全部構造單位而言上述通式(a1)之構造單位的含量未達15莫耳%之聚矽氧烷的組成物之比較例5及6中，對於鹼蝕刻處理，於遮罩劑下之Si蝕刻有進行。此可認為亦即所形成之鹼蝕刻遮罩的鹼耐性弱，因此遮罩之一部分溶解，結果於遮罩劑下之Si蝕刻會進行。 On the other hand, Comparative Examples 1 to 4 containing a composition of polysiloxane having a structural unit represented by the above formula (a1) and a structural unit having the above-described formula (a1) were used. However, in Comparative Examples 5 and 6 in which the composition of the polysiloxane of the above formula (a1) is less than 15 mol% with respect to all the structural units of the polyoxyalkylene, The alkali etching treatment is performed by Si etching under the masking agent. It can be considered that the alkali etching resistance of the formed alkali etching mask is weak, so that one part of the mask is partially dissolved, and as a result, Si etching under the masking agent proceeds.
10‧‧‧矽基板 10‧‧‧矽 substrate
20‧‧‧組成物層 20‧‧‧Composed layers
20A‧‧‧鹼蝕刻遮罩 20A‧‧‧Alkaline etching mask
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