TWI397770B - Positive type photoresist, method of manufacturing patterna and electronic part - Google Patents

Description

正型光阻組成物、圖案的製造方法以及電子零件Positive photoresist composition, pattern manufacturing method, and electronic component

本發明是關於一種具有耐熱性之正型光阻組成物、及使用其之起伏圖案(relief pattern)的製造方法。又，本發明是關於一種半導體裝置(device)等電子零件，其具有使用上述正型光阻組成物而形成之表面保護膜、層間絕緣膜等。The present invention relates to a positive resistive composition having heat resistance and a method for producing a relief pattern using the same. Moreover, the present invention relates to an electronic component such as a semiconductor device having a surface protective film, an interlayer insulating film, or the like formed using the positive resist composition.

因聚醯亞胺(polyimide)樹脂具有耐熱性優良之性質，故而廣泛使用於半導體元件等領域中。尤其是，將聚醯亞胺樹脂用作層間絕緣膜，或者是設置於密封劑(sealing agent)與半導體晶片(chip)之間的表面保護膜(緩衝膜，buffer coat)。Polyimide resins are widely used in the field of semiconductor devices and the like because of their excellent heat resistance. In particular, a polyimide resin is used as an interlayer insulating film or a surface coater (buffer coat) provided between a sealing agent and a semiconductor chip.

此處，表面保護膜(緩衝膜)是指起下述作用之膜，亦即是，防止以前製程中所形成之鋁薄膜電路或氧化膜在其後製程之操作中受損，或者是防止半導體晶片封裝後，由於密封材料與矽之熱膨脹係數不同而產生裂縫(crack)。由聚醯亞胺樹脂構成之表面保護膜，不僅如上所述可保護晶片不受外界損傷，而且因其α線阻止能較高，故而亦具有保護晶片不受放射線損傷之能力，因此受到矚目。而且，聚醯亞胺樹脂亦可作為簡單且可靠地進行圖案化加工的工具而受到矚目。Here, the surface protective film (buffer film) refers to a film which functions to prevent the aluminum thin film circuit or the oxide film formed in the prior process from being damaged in the subsequent process, or to prevent the semiconductor After the wafer is packaged, cracks are generated due to the difference in thermal expansion coefficient between the sealing material and the crucible. The surface protective film made of a polyimide resin not only protects the wafer from external damage as described above, but also has an ability to protect the wafer from radiation damage because of its high α-bar blocking energy, and thus has attracted attention. Further, the polyimide resin can also be attracting attention as a tool for performing patterning processing simply and reliably.

近來，為縮短半導體製造程序，如下所述之感光性聚醯亞胺正在成為主流，其藉由對聚醯亞胺前驅物之酸性官能基加成或混合具有感光基之化合物的方法，而賦予聚醯 亞胺樹脂感光性，且可藉由塗布、曝光、顯影而易形成起伏圖案(例如，參照日本專利特開昭54-109828號公報及日本專利特開平4-204945號公報)。Recently, in order to shorten the semiconductor manufacturing process, the photosensitive polyimine as described below is becoming a mainstream, and it is imparted by a method of adding or mixing a compound having a photosensitive group to an acidic functional group of a polyimide precursor. Poly The imine resin is photosensitive, and it is easy to form an undulating pattern by coating, exposure, and development (for example, refer to Japanese Laid-Open Patent Publication No. SHO 54-109828 and Japanese Patent Laid-Open No. Hei-4-204945).

又，近來，就材料成本及保護環境之觀點而言，鹼性水溶液顯影之要求日漸提高。故而，現在提出有將含有酸性官能基之聚苯幷噁唑(polybenzoxazole)前驅物作為基質樹脂的感光性樹脂等，當作層間絕緣膜或表面保護膜(緩衝膜)(例如，參照日本專利特開平1-46862號公報)。Moreover, recently, the demand for alkaline aqueous solution development has been increasing from the viewpoint of material cost and environmental protection. Therefore, a photosensitive resin or the like which uses a polybenzoxazole precursor containing an acidic functional group as a matrix resin has been proposed as an interlayer insulating film or a surface protective film (buffer film) (for example, refer to Japanese Patent) Kaiping No.1-46862).

然而，先前之聚醯亞胺系樹脂存在對廣泛用作半導體材料之銅及銅合金等金屬有腐蝕性之問題。上述問題的原因在於，作為聚醯亞胺前驅物的聚醯胺酸之結構中所含有之酸性官能基的羧基，與銅及銅合金等金屬產生化學反應。However, the prior polyilylimine-based resin has a problem of being corrosive to metals such as copper and copper alloy which are widely used as semiconductor materials. The reason for the above problem is that the carboxyl group of the acidic functional group contained in the structure of the polyaminic acid as the precursor of the polyimine is chemically reacted with a metal such as copper or a copper alloy.

換句話說，例如在形成有由銅或銅合金構成之金屬布線或金屬層的基板上塗布聚醯亞胺前驅物清漆(varnish)，以形成多層布線板用層間絕緣膜之情形時，該聚醯亞胺前驅物清漆所含有的聚醯胺酸結構中包含之羧基(carboxyl group)，會對上述銅或銅合金產生腐蝕作用，進而亦產生銅離子。如此一來，會造成絕緣不佳、斷線、短路(short)、金屬部位生銹、膜之密著性下降、膜之物性惡化等各種問題。In other words, for example, when a polyimide film precursor varnish is coated on a substrate on which a metal wiring or a metal layer composed of copper or a copper alloy is formed to form an interlayer insulating film for a multilayer wiring board, The carboxyl group contained in the polyamic acid structure contained in the polyimide precursor varnish causes corrosion to the copper or copper alloy, and copper ions are also generated. As a result, various problems such as poor insulation, disconnection, short circuit, rust of metal parts, deterioration of adhesion of the film, deterioration of physical properties of the film, and the like are caused.

另外，在形成有由銅或銅合金構成之金屬布線或金屬層之基板上，使用感光性聚醯亞胺前驅物以形成光阻膜之情形，感光性聚醯亞胺前驅物之羧基與上述銅或銅合金之間產生化學反應，因此於顯影時，會存在著未完全除去未 曝光部分之聚醯亞胺膜而產生殘膜之問題。為解決該問題，提出有使聚醯亞胺系樹脂中含有1H-四唑或其等衍生物(參照日本專利特開平8-286374號公報)。然而，於該方法中，亦未能充份改善密著性，尤其是於加熱加壓等嚴酷條件下之密著性。Further, in the case where a photosensitive polyimide precursor is used to form a photoresist film on a substrate on which a metal wiring or a metal layer composed of copper or a copper alloy is formed, the carboxyl group of the photosensitive polyimide precursor is A chemical reaction occurs between the above copper or copper alloy, so there is an incomplete removal during development. The polyimide portion of the polyimide film is exposed to cause a problem of residual film. In order to solve this problem, it is proposed to contain a 1H-tetrazole or a derivative thereof in the polyimide-based resin (refer to Japanese Laid-Open Patent Publication No. Hei 8-286374). However, in this method, the adhesion is not sufficiently improved, especially under severe conditions such as heat and pressure.

又，上述聚苯幷噁唑前驅物因具有苯酚性羥基(phenol hydroxyl)作為酸性官能基，故而與聚醯亞胺前驅物同樣，會對銅或銅合金引起腐蝕作用，其結果，引起絕緣不佳、斷線、短路、金屬部位生銹、膜之密著性下降、膜之物性惡化等各種問題。Further, since the polybenzoxazole precursor has a phenol hydroxyl group as an acidic functional group, it causes corrosion to copper or a copper alloy as a polyimine precursor, and as a result, insulation is not caused. Good, broken wires, short circuits, rusting of metal parts, deterioration of adhesion of the film, deterioration of physical properties of the film, and the like.

本發明是用以解決如上所述之先前課題開發而成者，本發明之目的在於提供一種不會使金屬布線或金屬層等銅及銅合金產生腐蝕，且具有膜密著效果、尤其是加熱加壓下等嚴酷條件下之膜密著效果的可靠性優良的電子材料用正型光阻組成物，圖案的製造方法及電子零件。又，本發明之其他目的在於提供一種除上述效果以外，亦具有防殘膜效果、靈敏度亦良好的電子材料用感光性樹脂組成物，圖案的製造方法及電子零件。The present invention has been made to solve the above problems as described above, and an object of the present invention is to provide a film adhesion effect, in particular, without causing corrosion of copper and a copper alloy such as a metal wiring or a metal layer. A positive resist composition for an electronic material, a method for producing a pattern, and an electronic component, which are excellent in reliability of a film adhesion effect under severe conditions such as heat and pressure. Further, another object of the present invention is to provide a photosensitive resin composition for an electronic material which has an anti-resistance effect and a good sensitivity in addition to the above effects, a method for producing a pattern, and an electronic component.

本發明者等鑒於上述情形銳意研究之結果發現，藉由使含有(A)聚苯幷噁唑前驅物及(B)溶劑之正型光阻組成物中，含有(C)四唑衍生物及(D)藉由光而產生酸之化合物，可解決上述各種問題。The inventors of the present invention have found that a positive resistive composition containing (A) a polybenzoxazole precursor and (B) a solvent contains a (C) tetrazole derivative and (D) A compound which generates an acid by light can solve the above various problems.

即，本發明之正型光阻組成物，其特徵在於包括：(A) 聚苯幷噁唑前驅物，其具有以下述通式(I)所表示之結構；(B)溶劑；(C)四唑衍生物；及(D)藉由光而產生酸之化合物， That is, the positive resist composition of the present invention is characterized by comprising: (A) a polybenzoxazole precursor having a structure represented by the following formula (I); (B) a solvent; (C) a tetrazole derivative; and (D) a compound which generates an acid by light,

(式中，X是2價有機基；Y是4價有機基；R₁ 是氫或1價有機基；m是2~500之整數，表示聚合物之重複單元數)。(wherein X is a divalent organic group; Y is a tetravalent organic group; R ₁ is hydrogen or a monovalent organic group; and m is an integer of 2 to 500, which represents the number of repeating units of the polymer).

又，本發明之正型光阻組成物，其特徵在於：於上述(A)以通式(I)所表示之聚苯幷噁唑前驅物之兩末端部，分別具有未含有反應性不飽和鍵之環式鍵、反應性不飽和鍵或非環式飽和鍵。Further, the positive resist composition of the present invention is characterized in that the both end portions of the polybenzoxazole precursor represented by the above formula (I) have no reactive unsaturated group. A ring bond, a reactive unsaturated bond, or an acyclic saturated bond.

又，本發明之正型光阻組成物，其特徵在於：上述(A)以通式(I)所表示之聚苯幷噁唑前驅物中之X及Y，分別是一個、或兩個或兩個以上之環式脂肪族基或芳香族基，上述兩個或兩個以上之環式脂肪族基或芳香族基藉由單鍵、有機基或選自氧、硫、氮、矽所構成之群之至少一種雜原子(hetero atom)相互鍵結。Further, the positive resist composition of the present invention is characterized in that (X) X and Y in the polybenzoxazole precursor represented by the formula (I) are one, or two or Two or more cyclic aliphatic groups or aromatic groups, the above two or more cyclic aliphatic groups or aromatic groups are composed of a single bond, an organic group or an oxygen, sulfur, nitrogen, or lanthanum group At least one hetero atom of the group is bonded to each other.

又，本發明之正型光阻組成物，其特徵在於：上述(D)藉由光而產生酸之化合物是鄰二疊氮醌(o-quinone diazide) 化合物。Further, the positive resist composition of the present invention is characterized in that (D) the compound which generates an acid by light is o-quinone diazide. Compound.

又，本發明之圖案的製造方法，其特徵在於包括：塗布乾燥製程，其將上述正型光阻組成物塗布於支持基板上而加以乾燥；曝光製程，其將藉由上述塗布、乾燥所獲得之感光性樹脂膜曝光為特定圖案；顯影製程，其使用鹼性水溶液使上述曝光後之感光性樹脂膜顯影；及加熱處理製程，其加熱處理上述顯影後之感光性樹脂膜。Moreover, the method for producing a pattern of the present invention includes: a coating drying process for applying the positive-type photoresist composition onto a support substrate to be dried; and an exposure process which is obtained by the coating and drying described above. The photosensitive resin film is exposed to a specific pattern; a developing process is performed by developing the exposed photosensitive resin film using an alkaline aqueous solution; and a heat treatment process for heat-treating the developed photosensitive resin film.

又，本發明之電子零件，其特徵在於：具有藉由上述圖案的製造方法所獲得之圖案層。Moreover, the electronic component of the present invention is characterized in that it has a pattern layer obtained by the above-described method for producing a pattern.

本發明之正型光阻組成物，不會使金屬布線或金屬層等銅及銅合金產生腐蝕，且膜密著性、尤其是加熱加壓下等嚴酷條件下之膜密著效果、靈敏度亦良好。又，除上述效果以外，還具有防殘膜效果，靈敏度亦良好，可靠性優良。The positive-type photoresist composition of the present invention does not cause corrosion of copper and a copper alloy such as a metal wiring or a metal layer, and has a film adhesion property, particularly a film adhesion effect and sensitivity under severe conditions such as heat and pressure. Also good. Moreover, in addition to the above effects, it has an anti-resistance effect, and is excellent in sensitivity and excellent in reliability.

又，根據本發明之圖案的製造方法，藉由使用上述正型光阻組成物，可獲得析像度高、形狀良好之圖案。Moreover, according to the method for producing a pattern of the present invention, by using the above-described positive-type resist composition, a pattern having a high resolution and a good shape can be obtained.

進而，本發明之電子零件可發揮下述效果，即具有形狀良好、密著性及耐熱性優良之起伏圖案，且可靠性較高。Further, the electronic component of the present invention has an effect of having an undulating pattern excellent in shape, adhesion, and heat resistance, and having high reliability.

為讓本發明之上述和其他目的、特徵和優點能更明顯易懂，下文特舉較佳實施例，並配合所附圖式，作詳細說明如下。The above and other objects, features and advantages of the present invention will become more <RTIgt;

以下，根據圖式詳細說明本發明之正型光阻組成物、 圖案的製造方法及電子零件之一實施例。再者，本發明並非限定於以下實施例。Hereinafter, the positive resist composition of the present invention will be described in detail based on the drawings. An embodiment of a method of manufacturing a pattern and an electronic component. Furthermore, the invention is not limited to the following examples.

[正型光阻組成物][Positive photoresist composition]

本發明之正型光阻組成物，其特徵在於包括：(A)聚苯幷噁唑前驅物，其具有以下述通式(I)所表示之結構；(B)溶劑；(C)含氮雜環化合物；及(D)藉由光而產生酸之化合物， The positive resist composition of the present invention comprises: (A) a polybenzoxazole precursor having a structure represented by the following formula (I); (B) a solvent; (C) a nitrogen-containing compound a heterocyclic compound; and (D) a compound which generates an acid by light,

(式中，X是2價有機基；Y是4價有機基；R₁ 是氫或1價有機基；m是2~500之整數，其表示聚合物之重複單元數)。(wherein X is a divalent organic group; Y is a tetravalent organic group; R ₁ is hydrogen or a monovalent organic group; and m is an integer of 2 to 500, which represents the number of repeating units of the polymer).

(A)聚苯幷噁唑前驅物(A) polybenzoxazole precursor

本發明之上述(A)聚苯幷噁唑前驅物(以下，稱為「(A)成分」)，例如可列舉使二羧酸(dicarboxylic acid)與雙胺基苯酚(bis-aminophenol)反應所得之前驅物。該等聚合物於其結構內含有苯酚性羥基等酸性官能基及/或其衍生取代基。The (A) polybenzoxazole precursor (hereinafter referred to as "(A) component") of the present invention may, for example, be obtained by reacting a dicarboxylic acid with a bis-aminophenol. Before the drive. These polymers contain an acidic functional group such as a phenolic hydroxyl group and/or a derivative thereof derived therefrom.

上述聚苯幷噁唑前驅物具有以通式(I)所表示之結構，其原因在於可獲得良好之膜特性。The above polybenzoxazole precursor has a structure represented by the general formula (I) because good film properties can be obtained.

(式中，X是2價有機基；Y是4價有機基；R₁ 是氫或1價有機基；m是2~500之整數，表示聚合物之重複單元數)。(wherein X is a divalent organic group; Y is a tetravalent organic group; R ₁ is hydrogen or a monovalent organic group; and m is an integer of 2 to 500, which represents the number of repeating units of the polymer).

上述通式(I)中之X是2價有機基，且是具有直鏈、支鏈、環狀結構之脂肪族基或芳香族基。X in the above formula (I) is a divalent organic group and is an aliphatic group or an aromatic group having a linear, branched or cyclic structure.

上述脂肪族基例如是，烷基鏈(alkyl chain)、環戊基(cyclopentyl)環、環己基(cyclohexyl)環、環辛基(cyclooctyl)環及其他二環(bicyclo)等。另外，亦可於該脂肪族基上含有取代基。而且，於該等脂肪族基之骨架上亦可含有氧(oxygen)、硫(sulfur)、氮(nitrogen)、矽(silicon)等雜原子(hetero atom)，或者例如是酮(ketone)、酯(ester)、醯胺(amide)等有機基。又，亦可藉由單鍵或氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(alkylidene)(亦包含藉由氟原子等鹵素原子取代氫原子者)等有機基鍵結兩個或兩個以上之脂肪族基。The above aliphatic group is, for example, an alkyl chain, a cyclopentyl ring, a cyclohexyl ring, a cyclooctyl ring, and other bicyclo groups. Further, a substituent may be contained on the aliphatic group. Further, a skeleton of the aliphatic group may also contain a hetero atom such as oxygen, sulfur, nitrogen or silicon, or a ketone or an ester, for example. (ester), amide and other organic groups. Further, it may be a single bond or a hetero atom such as oxygen, sulfur, nitrogen or hydrazine, or a ketone, an ester, a decylamine or an alkylidene (including a halogen atom substituted by a halogen atom such as a fluorine atom). The organic group is bonded to two or more aliphatic groups.

又，上述芳香族基例如可列舉，苯環、萘環等。另外，亦可於其芳香族基上含有取代基，而取代基中亦可包含氧、硫、氮、矽等雜原子。又，亦可藉由單鍵或氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(亦包含藉 由氟原子等鹵素原子取代氫原子者)等有機基而鍵結兩個或兩個以上之芳香族環。Further, examples of the aromatic group include a benzene ring and a naphthalene ring. Further, a substituent may be contained in the aromatic group, and a hetero atom such as oxygen, sulfur, nitrogen or hydrazine may be contained in the substituent. Further, it may also be a single bond or a hetero atom such as oxygen, sulfur, nitrogen or hydrazine, or such as a ketone, an ester, a guanamine or an alkylene group (also included An organic group such as a hydrogen atom such as a fluorine atom is substituted with an organic group to bond two or more aromatic rings.

為合成以上述通式(I)所表示之聚苯幷噁唑前驅物，例如，一般知悉有使用具有上述通式(I)中之X的二羧酸之方法。In order to synthesize the polybenzoxazole precursor represented by the above formula (I), for example, a method of using a dicarboxylic acid having X in the above formula (I) is generally known.

具有上述有機基X之二羧酸化合物，就脂肪族二羧酸化合物而言，例如可列舉丙二酸(malonic acid)、甲基丙二酸(methyl malonic acid)、二甲基丙二酸(dimethyl malonic acid)、丁基丙二酸(butyl malonic acid)、琥珀酸(succinaic acid)、戊二酸(glutaric acid)、2,2-二甲基戊二酸、己二酸(adipic acid)、衣康酸(itaconic acidate)、順丁烯二酸(maleic acid)、四氟順丁烯二酸(tetrafluoro maleic acid)、二甘醇酸(diglycol acid)、1,1-環丁烷二羧酸(1,1-cyclobutane dicarboxylic acid)、1,2-環戊烷二羧酸、3,3-四亞甲基戊二酸(3,3-tetramethylene glutaric acid)、樟腦酸(camphor acid)、1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、1,3-金剛烷二羧酸(1,3-adamantane dicarboxylic acid)、5-降冰片烯-2,3-二羧酸(5-norbornene-2,3-dicarboxylic acid)、1,2-伸苯基二乙酸(1,2-phenylene diacetate)、1,3-伸苯基二乙酸、1,4-伸苯基二乙酸、全氟軟木酸(perfluoro suberic acid)等。The dicarboxylic acid compound having the above organic group X, and examples of the aliphatic dicarboxylic acid compound may, for example, be malonic acid, methyl malonic acid, or dimethylmalonic acid ( Dimethyl malonic acid, butyl malonic acid, succinaic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, Itaconic acidate, maleic acid, tetrafluoro maleic acid, diglycol acid, 1,1-cyclobutanedicarboxylic acid (1,1-cyclobutane dicarboxylic acid), 1,2-cyclopentanedicarboxylic acid, 3,3-tetramethylene glutaric acid, camphoric acid, 1 , 2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantane dicarboxylic acid , 5-norbornene-2,3-dicarboxylic acid, 1,2-phenylene diacetate, 1,3-stretch Phenyldiacetic acid, 1,4-phenylenediacetic acid, perfluoro-pericic acid (perfluoro suberic) Acid) and so on.

進而，含有上述有機基X之二羧酸化合物，就耐熱性之方面而言，更好的是芳香族基者。芳香族二羧酸化合物例如可列舉，鄰苯二甲酸(phthalic acid)、3-氟鄰苯二甲酸、 4-氟鄰苯二甲酸、3,4,5,6-四氟鄰苯二甲酸、間苯二甲酸(isophthalic acid)、2-氟間苯二甲酸、4-氟間苯二甲酸、5-氟間苯二甲酸、2,4,5,6-四氟間苯二甲酸、對苯二甲酸(terephthalic acid)、2,2-雙(4-羧基苯基)丙烷(2,2-bis(4-carboxy phenyl)propane)、2,2-雙(4-羧基苯基)六氟丙烷、4,4'-二羧基二苯醚(4,4'-dicarboxy diphenyl ether)、4,4'-二羧基二苯基碸(4,4'-dicarboxy diphenyl sulfone)、4,4'-二羧基二苯基硫醚(4,4'-dicarboxy diphenyl thioether)、4,4'-二羧基二苯甲酮(4,4'-dicarboxy benzophenone)、2,2'-雙(三氟甲基)-4,4'-聯苯基二羧酸(2,2'-bis(trifluoromethyl)-4,4'-biphenyl dicarboxylic acid)、5-硝基間苯二甲酸(5-nitroisophthalic acid)、1,4-萘二羧酸(1,4-naphthalene dicarboxylic acid)、2,6-萘二羧酸、4,4'-聯苯二羧酸等。上述二羧酸可單獨使用或組合兩種或兩種以上使用。Further, the dicarboxylic acid compound containing the above organic group X is more preferably an aromatic group in terms of heat resistance. Examples of the aromatic dicarboxylic acid compound include phthalic acid and 3-fluorophthalic acid. 4-fluorophthalic acid, 3,4,5,6-tetrafluorophthalic acid, isophthalic acid, 2-fluoroisophthalic acid, 4-fluoroisophthalic acid, 5- Fluorine isophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)propane (2,2-bis ( 4-carboxyphenyl)propane), 2,2-bis(4-carboxyphenyl)hexafluoropropane, 4,4'-dicarboxy diphenyl ether, 4,4'- 4,4'-dicarboxy diphenyl sulfone, 4,4'-dicarboxy diphenyl thioether, 4,4'-dicarboxydiphenyl 4,4'-dicarboxy benzophenone, 2,2'-bis(trifluoromethyl)-4,4'-biphenyldicarboxylic acid (2,2'-bis(trifluoromethyl)-4,4' -biphenyl dicarboxylic acid), 5-nitroisophthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4, 4'-biphenyldicarboxylic acid and the like. The above dicarboxylic acids may be used singly or in combination of two or more kinds.

通式(I)中之Y是4價有機基，且是具有直鏈、支鏈、環狀結構之脂肪族基或芳香族基。Y in the formula (I) is a tetravalent organic group and is an aliphatic group or an aromatic group having a linear, branched or cyclic structure.

上述脂肪族基例如有，烷基鏈、環戊基環、環己基環、環辛基環或其他二環等。另外，亦可於該脂肪族基上具有取代基。又，亦可於骨架上具有氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺等有機基。又，亦可藉由單鍵或氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(亦包含藉由氟原子等鹵素原子取代氫原子者)有機基等鍵結兩個或兩個以上之脂肪族基。Examples of the above aliphatic group include an alkyl chain, a cyclopentyl ring, a cyclohexyl ring, a cyclooctyl ring or other bicyclic ring. Further, a substituent may be added to the aliphatic group. Further, a hetero atom such as oxygen, sulfur, nitrogen or helium may be contained on the skeleton, or an organic group such as a ketone, an ester or a guanamine may be used. Further, it may be a single bond or a hetero atom such as oxygen, sulfur, nitrogen or helium, or an organic group such as a ketone, an ester, a guanamine or an alkylene group (including a halogen atom substituted by a halogen atom such as a fluorine atom). Bonding two or more aliphatic groups.

又，上述芳香族基例如可列舉，苯環、萘環等。另外，亦可於其芳香族基上具有取代基，其取代基亦可包含氧、硫、氮、矽等雜原子。又，亦可藉由單鍵或氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(亦包含藉由氟原子等鹵素原子取代氫原子者)等有機基鍵結兩個或兩個以上之芳香族環。就耐熱性方面而言，有機基Y較好的是芳香族基。Further, examples of the aromatic group include a benzene ring and a naphthalene ring. Further, it may have a substituent on the aromatic group, and the substituent may also contain a hetero atom such as oxygen, sulfur, nitrogen or hydrazine. Further, an organic group such as a single bond or a hetero atom such as oxygen, sulfur, nitrogen or helium or a ketone, ester, decylamine or alkylene group (including a halogen atom substituted by a halogen atom such as a fluorine atom) may be used. Two or more aromatic rings are bonded. In terms of heat resistance, the organic group Y is preferably an aromatic group.

為合成以上述通式(I)所表示之聚苯幷噁唑前驅物，例如，一般採用使用具有式中之Y的雙胺基苯酚之方法。In order to synthesize the polybenzoxazole precursor represented by the above formula (I), for example, a method of using a bisaminophenol having Y in the formula is generally employed.

具有上述有機基Y之雙胺基苯酚化合物，並無特別限定，例如可列舉4,4'-二胺基-3,3'-二羥基聯苯(4,4'-diamino-3,3'-dihydroxybiphenyl)、2,2-雙(3-胺基-4-羥基苯基)丙烷、2,2-雙(3-胺基-4-羥基苯基)六氟丙烷、3,3'-二胺基-4,4'-二羥基二苯醚、3,3'-二胺基-4,4'-二羥基二苯基碸、3,3'-二胺基-4,4'-二羥基二苯基硫醚、3,3'-二胺基-4,4'-二羥基二苯甲酮、1,4-二胺基-2,5-二羥基苯等。該等雙胺基苯酚可單獨使用或將兩種或兩種以上組合使用。The bisaminophenol compound having the above organic group Y is not particularly limited, and examples thereof include 4,4'-diamino-3,3'-dihydroxybiphenyl (4,4'-diamino-3, 3'. -dihydroxybiphenyl), 2,2-bis(3-amino-4-hydroxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3,3'-di Amino-4,4'-dihydroxydiphenyl ether, 3,3'-diamino-4,4'-dihydroxydiphenylanthracene, 3,3'-diamino-4,4'-di Hydroxydiphenyl sulfide, 3,3'-diamino-4,4'-dihydroxybenzophenone, 1,4-diamino-2,5-dihydroxybenzene, and the like. These bisaminophenols may be used singly or in combination of two or more.

以上述通式(I)所表示之聚苯幷噁唑前驅物，例如，可使具有有機基Y之二胺基化合物、與自具有有機基X之二羧酸所衍生之活性酯化合物或酸鹵化物於有機溶劑下產生反應，藉此合成。The polybenzoxazole precursor represented by the above formula (I), for example, a diamine compound having an organic group Y, and an active ester compound or acid derived from a dicarboxylic acid having an organic group X The halide is reacted in an organic solvent to be synthesized.

於合成以上述通式(I)所表示之聚苯幷噁唑前驅物之情形時，較好的是，使具有有機基X之二羧酸及具有有機基Y之二胺基化合物的當量比率為0.6<X/Y<1.5。當具 有有機基X之二羧酸與具有有機基Y之二胺基化合物的當量比率為上述範圍之外時，重量平均分子量會變小，而造成膜物性下降。In the case of synthesizing the polybenzoxazole precursor represented by the above formula (I), it is preferred to make an equivalent ratio of the dicarboxylic acid having the organic group X and the diamine compound having the organic group Y. It is 0.6<X/Y<1.5. When When the equivalent ratio of the organic group X dicarboxylic acid to the diamine group compound having the organic group Y is outside the above range, the weight average molecular weight becomes small, and the film physical properties are lowered.

又，如下所述，藉由於該範圍內改變上述當量比率，可使所得之聚苯幷噁唑前驅物之兩末端部為胺基或羧基。進而，藉由於該等胺基或羧基中導入官能基，可使聚苯幷噁唑前驅物之兩末端部分別成為各種具有不含有反應性不飽和鍵之環式鍵、反應性不飽和鍵或非環式飽和鍵之基。Further, as described below, by changing the above equivalent ratio within the range, both terminal portions of the obtained polybenzoxazole precursor can be an amine group or a carboxyl group. Further, by introducing a functional group into the amine group or the carboxyl group, the both end portions of the polybenzoxazole precursor can be various ring-type bonds or reactive unsaturated bonds having no reactive unsaturated bond or The base of the acyclic saturated bond.

又，藉由於通式(I)中之R₁ 內導入官能基，可控制顯影時之溶解性及/或利用光反應進行圖案加工。又，亦可藉由部分導入該等官能基來控制鹼可溶性。Further, by introducing a functional group into R ₁ in the general formula (I), it is possible to control the solubility during development and/or perform pattern processing by photoreaction. Further, alkali solubility can also be controlled by partially introducing the functional groups.

於通式(I)中之R₁ 內導入官能基之方法，可列舉羥由醚鍵或酯鍵進行導入之方法。具體之導入方法，可列舉利用與R₁ 為取代基之鹵素化合物或酸鹵化物之脫酸鹵化反應的加成反應、或與乙烯醚之加成反應等。R₁ 亦可於骨架上具有氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(亦包含藉由氟原子等鹵素原子取代氫原子者)等有機基。A method of introducing a functional group into R ₁ in the formula (I) includes a method of introducing a hydroxyl group by an ether bond or an ester bond. Specific examples of the introduction method include an addition reaction using a deacidification halogenation reaction with a halogen compound or an acid halide in which R ₁ is a substituent, or an addition reaction with a vinyl ether. R ₁ may have a hetero atom such as oxygen, sulfur, nitrogen or hydrazine on the skeleton, or an organic group such as a ketone, an ester, a decylamine or an alkylene group (including a halogen atom substituted by a halogen atom such as a fluorine atom).

就可良好地控制溶解性方面而言，較好的官能基是該官能基所含有之碳原子數為1~15者，例如可列舉甲基、乙基、丙基(propyl)、異丙基(isopropyl)、正丁基(n-butyl)、第二丁基、第三丁基、環丙基、環丁基、環戊基、環己基、環己基甲基、環丙烯基(cyclopropenyl)、環丁烯基、環戊烯基、環己烯基、降冰片基(norbornyl)、降冰片烯基 (norbornenyl)、金剛烷基、苄基(benzyl)、對硝基苄基、三氟甲基、甲氧基乙基(methoxyethyl)、乙氧基乙基、甲氧基甲基、乙氧基甲基、甲氧基乙氧基甲基、苯氧基甲基、乙氧基四氫吡喃基(ethoxy tetrahydropyranyl)、四氫呋喃基(tetrahydrofuranyl)、2-三甲矽烷基乙氧基甲基(2-trimethylsilyl ethoxymethyl)、三甲矽烷基、第三丁基二甲矽烷基、3-氧環己基、9-芴基甲基、苯基、甲苯醯基、二甲苯基、9,10-二氫蒽基(9,10-dihydroanthranyl)、三甲基苯基、五甲基苯基、聯苯基(biphenylyl)、聯三苯基(tarphenylyl)、聯四苯基(quarterphenylyl)、二甲基聯苯基、萘基、甲基萘基、芴基(fluorenyl)、氟苯基、氟聯苯基、異亞丙基聯苯基、四氟異亞丙基聯苯基、苄基苯基醚基、苯基醚基、甲氧基聯苯基、二甲氧基聯苯基、甲氧基萘基、二甲氧基萘基、硝基苯基等。又，並非必須限定於此處所列舉者。In terms of good control of solubility, a preferred functional group is one in which the number of carbon atoms of the functional group is from 1 to 15, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. (isopropyl), n-butyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, cyclopropenyl, Cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornyl, norbornene (norbornenyl), adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxylate Ethyl, methoxyethoxymethyl, phenoxymethyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethylsilyl Ethoxymethyl), trimethyldecyl, tert-butyldimethyloxy, 3-oxocyclohexyl, 9-fluorenylmethyl, phenyl, tolylhydryl, xylyl, 9,10-dihydroindenyl (9 , 10-dihydroanthranyl), trimethylphenyl, pentamethylphenyl, biphenylyl, tarphenylyl, quarterphenylyl, dimethylbiphenyl, naphthyl , methylnaphthyl, fluorenyl, fluorophenyl, fluorobiphenyl, isopropylidene biphenyl, tetrafluoroisopropylidene biphenyl, benzylphenyl ether, phenyl ether And methoxybiphenyl, dimethoxybiphenyl, methoxynaphthyl, dimethoxynaphthyl, nitrophenyl and the like. Further, it is not necessarily limited to those listed herein.

當具有通式(I)之有機基X之二羧酸與具有有機基Y之二胺基化合物的當量比率為0.6<X/Y<1時，所得之聚苯幷噁唑前驅物之兩末端部為胺基。當感光性樹脂組成物含有下述(D)藉由光而產生酸之化合物，末端部之胺基為一級胺之情形時，由於副反應而感光性樹脂組成物之穩定性產生惡化，故而於獲得作為感光性樹脂組成物之穩定性方面，較好的是以其他原子或其他官能基取代胺基上之兩個氫原子中之至少一個。於獲得充分之穩定性方面，更好的是其取代比例在30%~100%之範圍內。When the equivalent ratio of the dicarboxylic acid having the organic group X of the formula (I) to the diamine compound having the organic group Y is 0.6 < X / Y < 1, both ends of the obtained polybenzoxazole precursor The part is an amine group. When the photosensitive resin composition contains the following (D) a compound which generates an acid by light, and the amine group at the terminal part is a primary amine, the stability of the photosensitive resin composition deteriorates due to a side reaction, and thus In terms of stability as a photosensitive resin composition, it is preferred to substitute at least one of two hydrogen atoms on the amine group with another atom or other functional group. In terms of obtaining sufficient stability, it is better that the substitution ratio is in the range of 30% to 100%.

自胺基所衍生之聚苯幷噁唑前驅物之末端部，於獲得優良硬化樹脂性質之方面，較好的是以下述通式(Ⅱ)所表示之結構者。The terminal portion of the polybenzoxazole precursor derived from the amine group is preferably a structure represented by the following formula (II) in terms of obtaining the properties of the excellent hardening resin.

於上述通式(Ⅱ)中，R₂ 是1價有機基，且較好的是碳原子數為1~20者。Z是氧、硫或氮原子，當Z是氧原子或硫原子時，n=1；當是氮原子時，n=2。In the above formula (II), R ₂ is a monovalent organic group, and preferably has 1 to 20 carbon atoms. Z is an oxygen, sulfur or nitrogen atom, when Z is an oxygen atom or a sulfur atom, n=1; when it is a nitrogen atom, n=2.

R₂ 例如可列舉，甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、環丙基、環丁基、環戊基、環己基、環己基甲基、環丙烯基、環丁烯基、環戊烯基、環己烯基、降冰片基、降冰片烯基、金剛烷基、苄基、對硝基苄基、三氟甲基、甲氧基乙基、乙氧基乙基、甲氧基甲基、乙氧基甲基、甲氧基乙氧基甲基、苯氧基甲基、乙氧基四氫吡喃基、四氫呋喃基、2-三甲矽烷基乙氧基甲基、三甲矽烷基、第三丁基二甲矽烷基、3-氧環己基、9-芴基甲基、苯基、甲苯醯基、二甲苯基、9,10-二氫蒽基、三甲基苯基、五甲基苯基、聯苯基、聯三苯基、聯四苯基、二甲基聯苯基、萘基、甲基萘基、芴基、氟苯基、氟聯苯基、異亞丙基聯苯基、四氟異亞丙基聯苯基、苄基苯基醚基、苯基醚基、甲氧基聯苯基、二甲氧基聯苯基、甲氧基萘基、二甲 氧基萘基、硝基苯基等有機基。又，並非必須限定於此處所列舉者。R ₂ may, for example, be methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, t-butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclohexyl. Methyl, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, norbornyl, norbornene, adamantyl, benzyl, p-nitrobenzyl, trifluoromethyl, A Oxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, phenoxymethyl, ethoxytetrahydropyranyl, tetrahydrofuranyl, 2-trimethyldecyl ethoxymethyl, trimethyl decyl, tert-butyldimethyl dimethyl, 3-oxocyclohexyl, 9-fluorenylmethyl, phenyl, tolyl, xylyl, 9, 10-dihydroindenyl, trimethylphenyl, pentamethylphenyl, biphenyl, terphenyl, tetraphenyl, dimethylbiphenyl, naphthyl, methylnaphthyl, anthracenyl , fluorophenyl, fluorobiphenyl, isopropylidene biphenyl, tetrafluoroisopropylidene biphenyl, benzylphenyl ether, phenyl ether, methoxybiphenyl, dimethoxy Base phenyl, methoxynaphthyl, dimethoxynaphthyl, nitrobenzene And other organic groups. Further, it is not necessarily limited to those listed herein.

R₃ 是具有直鏈、支鏈、環狀結構的脂肪族基或芳香族基，而該結構可藉由使具有R₃ 之酸酐與胺反應而獲得。該酸酐(acid anhydride)可列舉，琥珀酸酐(succinic anhydride)、戊二酸酐(glutaric anhydride)、2,2-二甲基戊二酸酐、順丁烯二酸酐、1,2-環戊烷二羧酸酐、1,2-環己烷二羧酸酐、5-降冰片烯-2,3-二羧酸酐、鄰苯二甲酸酐、3-氟鄰苯二甲酸酐、4-氟鄰苯二甲酸酐、3,4,5,6-四氟鄰苯二甲酸酐等。又，並非必須限定於此處所列舉者。R ₃ is an aliphatic group or an aromatic group having a linear, branched or cyclic structure, and the structure can be obtained by reacting an acid anhydride having R ₃ with an amine. The acid anhydride may, for example, be succinic anhydride, glutaric anhydride, 2,2-dimethylglutaric anhydride, maleic anhydride, 1,2-cyclopentanedicarboxylate. Anhydride, 1,2-cyclohexanedicarboxylic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, phthalic anhydride, 3-fluorophthalic anhydride, 4-fluorophthalic anhydride , 3,4,5,6-tetrafluorophthalic anhydride, and the like. Further, it is not necessarily limited to those listed herein.

作為R₃ 中之上述脂肪族基，例如為，烷基鏈、環戊基環、環己基環、環辛基環、其他二環等，亦可於該脂肪族基上具有取代基。又，該等亦可於骨架上具有氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(亦包含藉由氟原子等鹵素原子取代氫原子者)等有機基。The aliphatic group in R ₃ may, for example, be an alkyl chain, a cyclopentyl ring, a cyclohexyl ring, a cyclooctyl ring or another bicyclic ring, and may have a substituent on the aliphatic group. Further, these may also have a hetero atom such as oxygen, sulfur, nitrogen or hydrazine on the skeleton, or an organic group such as a ketone, an ester, a decylamine or an alkylene group (including a halogen atom substituted by a halogen atom such as a fluorine atom). base.

又，作為R₃ 中之上述芳香族基，例如可列舉苯環、萘環等。該等亦可於其芳香族基上具有取代基，該取代基亦可包含氧、硫、氮、矽等雜原子。又，亦可藉由單鍵或氧、硫、氮、矽等雜原子，或例如酮、酯、醯胺、亞烷基(亦包含藉由氟原子等鹵素原子取代氫原子者)等有機基鍵結兩個或兩個以上之芳香族環。Moreover, examples of the aromatic group in R ₃ include a benzene ring and a naphthalene ring. These may also have a substituent on the aromatic group, and the substituent may also contain a hetero atom such as oxygen, sulfur, nitrogen or hydrazine. Further, an organic group such as a single bond or a hetero atom such as oxygen, sulfur, nitrogen or helium or a ketone, ester, decylamine or alkylene group (including a halogen atom substituted by a halogen atom such as a fluorine atom) may be used. Two or more aromatic rings are bonded.

以是否含有反應性不飽和鍵(碳-碳不飽和鍵)，將該等R₂ 及R₃ 分類，繼而，以是否具有環式結構(環狀結構)加以分類，可分類為以下(1)~(4)。Whether or not the reactive unsaturated bond (carbon-carbon unsaturated bond) is contained, the R ₂ and R _{3 are} classified, and then classified by the ring structure (cyclic structure), and classified into the following (1) ~(4).

(1)作為具有反應性不飽和鍵且具有環狀結構之基，可列舉環丙烯基、環丁烯基、環戊烯基、環己烯基、降冰片烯基、及作為上述通式(Ⅱ)中自右邊開始第二個所示之具有醯亞胺結構者的自順丁烯二酸酐所衍生之基等。又，於該分類中亦包含於環狀結構中未具有反應性不飽和鍵而於環狀結構以外具有反應性不飽和鍵之基，例如，具有苯環且於苯環外具有反應性不飽和雙鍵之基。(1) Examples of the group having a cyclic unsaturated structure having a reactive unsaturated bond include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a norbornene group, and the above formula ( II) A group derived from maleic anhydride having a quinone imine structure as shown in the second from the right. Further, the classification also includes a group having a reactive unsaturated bond in the cyclic structure and having a reactive unsaturated bond other than the cyclic structure, for example, having a benzene ring and having a reactive unsaturated group outside the benzene ring. The base of the double bond.

(2)作為具有反應性不飽和鍵且非環狀結構之基，可列舉具有上述通式(Ⅱ)中最右邊所示之結構且自順丁烯二酸酐所衍生之基等。(2) The group having a non-cyclic structure having a reactive unsaturated bond may, for example, be a group having a structure represented by the rightmost side in the above formula (II) and derived from maleic anhydride.

(3)作為不具有反應性不飽和鍵且具有環狀結構之基，可列舉：環丙基、環丁基、環戊基、環己基、環己基甲基、降冰片基、金剛烷基、乙氧基四氫吡喃基、四氫呋喃基、3-氧環己基等具有脂環式烴環狀結構之基，苄基、對硝基苄基、苯氧基甲基、9-芴基甲基、苯基、甲苯醯基、二甲苯基、9,10-二氫蒽基、三甲基苯基、五甲基苯基、聯苯基、聯三苯基、聯四苯基、二甲基聯苯基、萘基、甲基萘基、芴基、氟苯基、氟聯苯基、異亞丙基聯苯基、四氟異亞丙基聯苯基、苄基苯基醚基、苯基醚基、甲氧基聯苯基、二甲氧基聯苯基、甲氧基萘基、二甲氧基萘基、硝基苯基等具有芳香族烴環狀結構之基，及作為上述通式(且)中自右開始第二個所示之具有醯亞胺結構之環狀結構者的自琥珀酸酐、戊二酸酐、2,2-二甲基戊二酸酐、1,2-環戊烷二羧酸酐、1,2-環己烷二羧酸酐、5-降冰片烯-2,3-二羧酸 酐、二甲酸酐、3-氟鄰苯二甲酸酐、4-氟鄰苯二甲酸酐、3,4,5,6-四氟鄰苯二甲酸酐等酸酐所衍生之基等。(3) Examples of the group having a cyclic structure without a reactive unsaturated bond include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a norbornyl group, an adamantyl group, a group having an alicyclic hydrocarbon ring structure such as ethoxytetrahydropyranyl, tetrahydrofuranyl or 3-oxocyclohexyl, benzyl, p-nitrobenzyl, phenoxymethyl, 9-fluorenylmethyl , phenyl, tolylhydrazyl, xylyl, 9,10-dihydroindenyl, trimethylphenyl, pentamethylphenyl, biphenyl, terphenyl, tetraphenyl, dimethyl Biphenyl, naphthyl, methylnaphthyl, anthracenyl, fluorophenyl, fluorobiphenyl, isopropylidene biphenyl, tetrafluoroisopropylidene biphenyl, benzylphenyl ether, benzene a group having an aromatic hydrocarbon ring structure, such as an ether group, a methoxybiphenyl group, a dimethoxybiphenyl group, a methoxynaphthyl group, a dimethoxynaphthyl group, a nitrophenyl group, and the like a succinic anhydride, glutaric anhydride, 2,2-dimethylglutaric anhydride, 1,2-ring of the formula having the quinone imine structure shown in the second from the right (and) Pentanedicarboxylic anhydride, 1,2-cyclohexanedicarboxylic acid , 5-norbornene-2,3-dicarboxylic acid A group derived from an acid anhydride such as an anhydride, dicarboxylic anhydride, 3-fluorophthalic anhydride, 4-fluorophthalic anhydride or 3,4,5,6-tetrafluorophthalic anhydride.

(4)作為不具有反應性不飽和鍵且為非環狀結構(非環式飽和鍵)之基，可列舉甲基、乙基、丙基、異丙基、正丁基、第二丁基、第三丁基、三氟甲基、甲氧基乙基、乙氧基乙基、甲氧基甲基、乙氧基甲基、甲氧基乙氧基甲基、2-三甲矽烷基乙氧基甲基、三甲矽烷基、第三丁基二甲矽烷基、具有上述通式(Ⅱ)中最右邊所示之結構的自琥珀酸酐、戊二酸酐、2,2-二甲基戊二酸酐所衍生之基等。(4) Examples of the group which does not have a reactive unsaturated bond and which is an acyclic structure (acyclic saturated bond) may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group or a second butyl group. , tert-butyl, trifluoromethyl, methoxyethyl, ethoxyethyl, methoxymethyl, ethoxymethyl, methoxyethoxymethyl, 2-trimethylalkylene An oxymethyl group, a trimethyl decyl group, a tert-butyldimethyl dimethyl group, a succinic anhydride, a glutaric anhydride, a 2,2-dimethylpentane having the structure shown at the far right of the above formula (II) A group derived from an acid anhydride or the like.

再者，於本發明中，具有反應性不飽和鍵或非環式飽和鍵之基是指上述(1)、(2)及(4)所揭示之基。上述(3)是不具有反應性不飽和鍵之環式鍵、即不具有反應性不飽和鍵而具有環式飽和鍵之基。Further, in the present invention, the group having a reactive unsaturated bond or an acyclic saturated bond means the group disclosed in the above (1), (2) and (4). The above (3) is a cyclic bond having no reactive unsaturated bond, that is, a group having no cyclic unsaturated bond and having no reactive unsaturated bond.

於該等之中，就穩定性方面而言，較好的是不具有反應性不飽和鍵之環式鍵(3)及具有非環式飽和鍵之基(4)。Among these, in terms of stability, a cyclic bond (3) having no reactive unsaturated bond and a group (4) having an acyclic saturated bond are preferred.

當具有通式(I)之有機基X之二羧酸與具有有機基Y之二胺基化合物的當量比率為1<X/Y<1.5時，所得之聚苯幷噁唑前驅物之兩末端部為羧基。當為羧基時，亦可以其他官能基取代。When the equivalent ratio of the dicarboxylic acid having the organic group X of the formula (I) to the diamine compound having the organic group Y is 1 < X / Y < 1.5, both ends of the obtained polybenzoxazole precursor are obtained. The part is a carboxyl group. When it is a carboxyl group, it may be substituted with other functional groups.

作為於羧基導入官能基之具體方法，可藉由於合成聚苯幷噁唑前驅物時添加胺基化合物，而取代末端部。As a specific method of introducing a functional group into a carboxyl group, the terminal moiety can be replaced by adding an amino group compound when synthesizing the polybenzoxazole precursor.

作為上述胺基化合物，例如可列舉：乙基胺(ethyl amine)、丙基胺、異丙基胺、丁基胺、異丁基胺、第三丁基胺、二乙基胺、二丙基胺、二異丙基胺、二丁基胺、環 丙基胺、環丁基胺、環戊基胺、環己基胺、環己基甲基胺等脂肪族胺，苯胺(aniline)、鄰甲苯胺(o-toluidine)、間甲苯胺、對甲苯胺、鄰胺基苯酚(o-aminophenol)、間胺基苯酚、對胺基苯酚等芳香族胺等。又，並非必須限定於此處所列舉者。Examples of the above amine-based compound include ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, tert-butylamine, diethylamine, and dipropyl group. Amine, diisopropylamine, dibutylamine, ring Aliphatic amines such as propylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, cyclohexylmethylamine, aniline, o-toluidine, m-toluidine, p-toluidine, An aromatic amine such as o-aminophenol, m-aminophenol or p-aminophenol. Further, it is not necessarily limited to those listed herein.

以通式(I)所表示之聚苯幷噁唑前驅物，其分子量以重量平均分子量而計，較好的是在5,000至80,000之範圍內，更好的是在10,000至40,000之範圍內。重量平均分子量藉由凝膠滲透層析法加以測定，可藉由使用標準聚苯乙烯校準曲線加以換算而求得。The polybenzoxazole precursor represented by the formula (I) has a molecular weight in terms of a weight average molecular weight, preferably in the range of 5,000 to 80,000, more preferably in the range of 10,000 to 40,000. The weight average molecular weight is determined by gel permeation chromatography and can be obtained by conversion using a standard polystyrene calibration curve.

(B)溶劑(B) solvent

本發明中之上述(B)溶劑(以下，稱為「(B)成分」)，較好的是γ-丁內酯(γ-butyrolactone)、N-甲基-2-吡咯烷酮(N-methyl-2-pyrrolidone)、N-乙醯基-2-吡咯烷酮(N-acetyl-2-pyrrolidone)、N,N-二甲基乙醯胺、二甲基亞碸(dimethyl sulfoxide)、六甲基磷醯三胺(hexamethyl phosphoric triamide)、二甲基咪唑啉酮(dimethyl imidazolidinone)、N-乙醯基-ε-己內醯胺(N-acetyl-ε-caprolactam)等極性溶劑，此外，除該等極性溶劑以外，亦可使用酮類、酯類、內酯(lactone)類、醚類、鹵化烴(halogenated hydrocarbon)類、烴類，例如，丙酮、二乙基酮、甲基乙基酮、甲基異丁基酮、環己酮、乙酸甲酯、乙酸乙酯、乙酸丁酯、草酸二乙酯、丙二酸二乙酯、二***、乙二醇二甲醚、二乙二醇二甲醚、丙二醇單甲醚、 丙二醇單甲醚乙酸酯、四氫呋喃、二氯甲烷、1,2-二氯乙烷、1,4-二氯丁烷、三氯乙烷、氯苯、鄰二氯苯、己烷、庚烷、辛烷、苯、甲苯、二甲苯等。該等有機溶劑可單獨使用或將兩種或兩種以上組合使用。其中，若其為溶解本發明之感光性樹脂組成物者則並未特別限定於此種類。一般而言，以感光性樹脂組成物中為40~90 wt%之重量比使用溶劑。The above (B) solvent (hereinafter referred to as "(B) component") in the present invention is preferably γ-butyrolactone or N-methyl-2-pyrrolidone (N-methyl-). 2-pyrrolidone), N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphonium a polar solvent such as hexamethyl phosphoric triamide, dimethyl imidazolidinone, or N-acetyl-ε-caprolactam, in addition to the polarities In addition to the solvent, ketones, esters, lactones, ethers, halogenated hydrocarbons, hydrocarbons such as acetone, diethyl ketone, methyl ethyl ketone, methyl may also be used. Isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether Propylene glycol monomethyl ether, Propylene glycol monomethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane , octane, benzene, toluene, xylene, and the like. These organic solvents may be used singly or in combination of two or more. In particular, the photosensitive resin composition of the present invention is not particularly limited to this type. In general, a solvent is used in a weight ratio of 40 to 90% by weight in the photosensitive resin composition.

(C)四唑衍生物(C) tetrazole derivatives

作為本發明中之上述(C)四唑衍生物(以下，稱為「(C)成分」)，可列舉1H-四唑(1H-tetrazole)、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑、1-甲基-1H-四唑、5,5'-雙-1H-四唑等。又，並非必須限定於此處所列舉者。The (C) tetrazole derivative (hereinafter referred to as "(C) component") in the present invention includes 1H-tetrazole, 5-methyl-1H-tetrazole, 5- Phenyl-1H-tetrazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, 5,5'-bis-1H-tetrazole, and the like. Further, it is not necessarily limited to those listed herein.

該等(C)成分可單獨使用或將兩種或兩種以上組合使用。(C)成分之使用量相對於重量份(A)成分100而言，通常，一種時為0.1~10重量份，組合兩種或兩種以上時合計為0.1~10重量份。更好的是在0.2~5重量份之範圍內。若不足0.1重量份，則存有與金屬層之密著性的提高效果下降之傾向，若超過10重量份，則即使調配大於其之量，亦無法預期密著性大幅度提高。These (C) components may be used singly or in combination of two or more. The amount of the component (C) to be used is usually 0.1 to 10 parts by weight per one part by weight of the component (A), and 0.1 to 10 parts by weight in total of two or more types. More preferably, it is in the range of 0.2 to 5 parts by weight. When the amount is less than 0.1 part by weight, the effect of improving the adhesion to the metal layer tends to be lowered. When the amount is more than 10 parts by weight, even if the amount is more than the amount, the adhesion is not expected to be greatly improved.

(D)藉由光而產生酸之化合物(D) a compound which produces an acid by light

本發明之感光性樹脂組成物除上述(A)~(C)成分以外，亦添加(D)藉由光而產生酸之化合物(以下，稱為「(D)成分」)。(D)成分是感光劑，其具有產生酸，增大光照射部在鹼性水溶液中之可溶性的功能。本發明中所用之(D) 成分，只要是藉由光而產生酸之化合物即可，具體而言，例如可列舉鄰二疊氮醌化合物(o-quinone diazido)、芳基重氮鹽(aryl diazonium salt)、二芳基錪鹽(diaryl iodonium salt)、三芳基鎦鹽(triaryl sulfonium salt)等。In addition to the above components (A) to (C), the photosensitive resin composition of the present invention is also added with (D) a compound which generates an acid by light (hereinafter referred to as "(D) component"). The component (D) is a sensitizer which has an action of generating an acid and increasing the solubility of the light-irradiating portion in the alkaline aqueous solution. (D) used in the present invention The component may be a compound which generates an acid by light, and specific examples thereof include o-quinone diazido, aryl diazonium salt, and diaryl sulfonium. Diaryl iodonium salt, triaryl sulfonium salt, and the like.

上述鄰二疊氮醌化合物，例如，可藉由使鄰二疊氮醌磺醯氯類與羥基化合物、胺基化合物等在脫鹽酸劑之存在下進行縮合反應等而獲得。The above-mentioned ortho-diazide compound can be obtained, for example, by subjecting o-diazide sulfonium chloride to a condensation reaction with a hydroxy compound or an amine compound in the presence of a dehydrochlorinating agent.

上述鄰二疊氮醌磺醯氯類例如可列舉，苯醌-1,2-二疊氮基-4-磺醯氯(benzoquinone-1,2-dizide-4-sulfonyl chloride)、萘醌-1,2-二疊氮基-5-磺醯氯、萘醌-1,2-二疊氮基-4-磺醯氯等。Examples of the above-mentioned o-diazide sulfonium chlorides include benzoquinone-1, 2-dizide-4-sulfonyl chloride and naphthoquinone-1. , 2-diazido-5-sulfonyl chloride, naphthoquinone-1,2-diazido-4-sulfonyl chloride, and the like.

與上述鄰二疊氮醌磺醯氯類產生反應之化合物，於感光特性方面，較好的是羥基化合物。該羥基化合物例如可列舉，對苯二酚(hydroquinone)、間苯二酚(resorcinol)、鄰苯三酚(pyrogallol)、雙酚A(bisphenol A)、雙(2-羥基苯基)甲烷、雙(4-羥基苯基)甲烷、2-羥基苯基-4'-羥基苯基甲烷、2,2-雙(4-羥基苯基)六氟丙烷、2,3,4-三羥基二苯甲酮、2,3,4,4'-四羥基二苯甲酮、2,2',4,4'-四羥基二苯甲酮、2,3,4,2',3'-五羥基二苯甲酮、2,3,4,3',4',5'-六羥基二苯甲酮、雙(2,3,4-三羥基苯基)甲烷、雙(2,3,4-三羥基苯基)丙烷、2-(4-羥基苯基)-2-[4-[1,1-雙(4-羥基苯基)乙基]苯基]丙烷、4b,5,9b,10-四氫-1,3,6,8-四羥基-5,10-二甲基茚並[2,1-A]茚(4b,5,9b,10-tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethyl indeno[2,1-A]indene)、三(4-羥基 苯基)甲烷、1,1,1-三(4-羥基苯基)乙烷等。又，並非必須限定於此處所列舉者。The compound which reacts with the above-mentioned o-diazide sulfonium chloride is preferably a hydroxy compound in terms of photosensitivity. Examples of the hydroxy compound include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis(2-hydroxyphenyl)methane, and bisphenol. (4-hydroxyphenyl)methane, 2-hydroxyphenyl-4'-hydroxyphenylmethane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, 2,3,4-trihydroxydiphenyl Ketone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4,2',3'-pentahydroxydiene Benzene, 2,3,4,3',4',5'-hexahydroxybenzophenone, bis(2,3,4-trihydroxyphenyl)methane, bis(2,3,4-tris) Hydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propane, 4b,5,9b,10- Tetrahydro-1,3,6,8-tetrahydroxy-5,10-dimethylindolo[2,1-A]indole (4b,5,9b,10-tetrahydro-1,3,6,8- Tetrahydroxy-5,10-dimethyl indeno[2,1-A]indene), tris(4-hydroxyl) Phenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, and the like. Further, it is not necessarily limited to those listed herein.

又，上述芳基重氮鹽、二芳基錪鹽、三芳基鎦鹽，例如可列舉p-甲苯磺酸苯重氮鎓(benzene diazonium p-toluene sulfonate)、9,10-二甲氧基蒽-2-磺酸二苯基錪(diphenyl iodonium 9,10-dimethoxy anthracene-2-sulfonate)、三氟甲烷磺酸三(4-第三丁基苯基)鎦、N-三氟甲烷磺醯基二甲醯亞胺、對硝基苄基-9,10-二甲氧基蒽-2-磺酸鹽、4-甲氧基-α-[[[(4-甲基苯基)磺醯基]氧基]亞胺基]苯乙腈(4-methoxy-α-[[[(4-methyl phenyl)sulfonyl]oxy]imino]benzene acetonitrile)等。又，並非必須限定於此處所列舉者。Further, examples of the above aryldiazonium salt, diarylsulfonium salt and triarylsulfonium salt include benzene diazonium p-toluene sulfonate and 9,10-dimethoxyanthracene. Diphenyl iodonium 9,10-dimethoxy anthracene-2-sulfonate, tris(4-t-butylphenyl)phosphonium trifluoromethanesulfonate, N-trifluoromethanesulfonyl Dimethylimine, p-nitrobenzyl-9,10-dimethoxyindole-2-sulfonate, 4-methoxy-α-[[[(4-methylphenyl)sulfonyl) ]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]]] Further, it is not necessarily limited to those listed herein.

該等(D)成分可單獨使用或將兩種或兩種以上組合使用。(D)成分之使用量相對於100重量份(A)成分，通常，一種時為0.1~40重量份，組合兩種或兩種以上時合計為0.1~40重量份。更好的是在1~20重量份之範圍內。若不足0.1重量份，則存有無法充分實現作為感光劑之效果的傾向，若超過40重量份，則存有曝光樹脂層時無法充分曝光至底部之傾向。These (D) components may be used singly or in combination of two or more. The amount of the component (D) to be used is usually 0.1 to 40 parts by weight, based on 100 parts by weight of the component (A), and 0.1 to 40 parts by weight in combination of two or more kinds. More preferably, it is in the range of 1 to 20 parts by weight. When the amount is less than 0.1 part by weight, the effect as a sensitizer may not be sufficiently obtained. When the amount exceeds 40 parts by weight, the exposed resin layer may not be sufficiently exposed to the bottom.

(E)其他成分(E) Other ingredients

本發明之正型光阻組成物中，除上述必需成分((A)~(D)成分)以外，可使用矽烷偶合劑(silane coupling agent)作為對矽基板之接著性增強劑。又，使上述通式(I)中之Y來源於二胺基矽氧烷(diamino siloxane)，亦可使用將其改 性為基質聚合物者作為對矽基板之接著性增強劑。進而，亦可根據目的而調配溶解抑制劑、穩定劑等。In the positive resist composition of the present invention, in addition to the above-mentioned essential components (components (A) to (D)), a silane coupling agent may be used as an adhesion enhancer to the tantalum substrate. Further, the Y in the above formula (I) is derived from a diamino siloxane, and may be used instead. The matrix polymer is used as an adhesion enhancer to the ruthenium substrate. Further, a dissolution inhibitor, a stabilizer, or the like may be formulated depending on the purpose.

上述矽烷偶合劑，就反應性方面而言，較好的是烷氧基矽烷(alkoxysilane)類，例如可列舉乙烯基三甲氧基矽烷、N-(2-胺基乙基)-3-胺基丙基甲基三甲氧基矽烷、3-胺基丙基三甲氧基矽烷、N-甲基-3-胺基丙基三甲氧基矽烷、3-縮水甘油氧基丙基三甲氧基矽烷(3-glycidoxypropyl trimethoxysilane)、2-(3,4-環氧環己基)乙基三甲氧基矽烷、3-甲基丙烯醯氧基丙基三甲氧基矽烷、3-巰基丙基三甲氧基矽烷、N-(1,3-二甲基亞丁基)-3-(三乙氧基矽烷基)-1-丙烷胺、N,N-雙(3-(三甲氧基矽烷基)丙基)乙烯基二胺、N-(3-三甲氧基矽烷基丙基)吡咯(N-(3-trimethoxysilyl propyl)pyrrole)、3-醯脲丙基三甲氧基矽烷(3-ureidopropyl trimethoxysilane)、3-醯脲丙基三乙氧基矽烷、N-(3-三乙氧基矽烷基丙基)-第三胺基丁基甲酸酯、N-苯基-3-胺基丙基三甲氧基矽烷、雙(2-羥基乙基)-3-胺基丙基三乙氧基矽烷、3-異氰醯基丙基三乙氧基矽烷(3-isocyanato propyl triethoxysilane)、(糠氧基甲基)三乙氧基矽烷((furfuryloxy methyl)triethoxysilane)等。又，並非必須限定於此處所列舉者。The above decane coupling agent is preferably an alkoxysilane in terms of reactivity, and examples thereof include vinyltrimethoxynonane and N-(2-aminoethyl)-3-amino group. Propylmethyltrimethoxydecane, 3-aminopropyltrimethoxydecane, N-methyl-3-aminopropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane (3) -glycidoxypropyl trimethoxysilane), 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N -(1,3-Dimethylbutylene)-3-(triethoxydecyl)-1-propanamine, N,N-bis(3-(trimethoxydecyl)propyl)vinyl Amine, N-(3-trimethoxysilyl propyl)pyrrole, 3-ureidopropyl trimethoxysilane, 3-ureidopropion Triethoxy decane, N-(3-triethoxydecylpropyl)-third aminobutyl methacrylate, N-phenyl-3-aminopropyltrimethoxy decane, bis(2- Hydroxyethyl)-3-aminopropyltriethoxydecane, 3-isocyanopropylpropyltriethoxylate Silane (3-isocyanato propyl triethoxysilane), (bran yloxymethyl) triethoxysilane Silane ((furfuryloxy methyl) triethoxysilane) and the like. Further, it is not necessarily limited to those listed herein.

又，以提高溶解對比度為目的，可使用溶解促進劑(dissolution accelerant)。溶解促進劑例如可列舉含有酸性官能基之化合物，其中酸性官能基較好的是苯酚性羥基、羧基、磺醯基。上述之溶解促進劑例如可列舉，雙(2-羥基 苯基)甲烷、雙(4-羥基苯基)甲烷、2-羥基苯基-4'-羥基苯基甲烷、雙(2-羥基-4-甲基)甲烷、4,4'-二羥基二苯醚、2,2-雙(4-羥基-3-甲基苯基)丙烷、4,4-(1-苯基亞乙基)雙酚、5,5-(1-甲基亞乙基)雙(1,1-(聯苯)-2-醇)、三(4-羥基苯基)甲烷、1,1,1-三(4-羥基苯基)乙烷、2,6-雙((2-羥基-5-甲基苯基)甲基)-4-甲基苯酚、4,4-[1-[4-[1-(4-羥基苯基)-1-甲基乙基]苯基]亞乙基]雙酚、4,4'-二羥基二苯基碸、2-羥基-5-甲基-1,3-二羥甲基苯、3,3-亞甲基雙(2-羥基-5-甲基苯甲醇)、雙[4-羥基-3,5-雙(羥基甲基)]甲烷、2,2-雙[4-羥基-3,5-雙(羥基甲基)]丙烷、2,2-雙[4-羥基-3.5-雙(羥基甲基)]六氟丙烷、水楊酸、丙二酸、甲基丙二酸、二甲基丙二酸、丁基丙二酸、琥珀酸、戊二酸、2,2-二甲基戊二酸、己二酸、衣康酸、順丁烯二酸、四氟順丁烯二酸、二甘醇酸、1,1-環丁烷二羧酸、1,2-環戊烷二羧酸、3,3-四亞甲基戊二酸、樟腦酸、1,2-環己烷二羧酸、1,3-環己烷二羧酸、1,4-環己烷二羧酸、1,3-金剛烷二羧酸、5-降冰片烯-2,3-二羧酸、1,2-伸苯基二乙酸、1,3-伸苯基二乙酸、1,4-伸苯基二乙酸、全氟軟木酸、2-氟間苯二甲酸、4-氟間苯二甲酸、5-氟間苯二甲酸、3-氟鄰苯二甲酸、4-氟鄰苯二甲酸、2,4,5,6-四氟間苯二甲酸、3,4,5,6-四氟鄰苯二甲酸、4,4'-六氟異亞丙基二苯基二羧酸、2,2'-雙(三氟甲基)-4,4'-伸聯苯基二羧酸、對苯二甲酸、間苯二甲酸、4,4'-氧基二苯基二羧酸、5-硝基間苯二甲酸、1,4-萘二羧酸、2,6-萘二羧酸、4,4-聯苯基二羧酸、4-羥基苯磺酸等。又，並非必須限定於此處所列舉者。該等溶解 促進劑可單獨使用或將兩種或兩種以上組合使用。Further, a dissolution accelerant can be used for the purpose of improving the dissolution contrast. The dissolution promoter may, for example, be a compound having an acidic functional group, and among them, the acidic functional group is preferably a phenolic hydroxyl group, a carboxyl group or a sulfonyl group. The above dissolution promoter may, for example, be bis(2-hydroxyl) Phenyl)methane, bis(4-hydroxyphenyl)methane, 2-hydroxyphenyl-4'-hydroxyphenylmethane, bis(2-hydroxy-4-methyl)methane, 4,4'-dihydroxy Phenyl ether, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 4,4-(1-phenylethylidene)bisphenol, 5,5-(1-methylethylene Bis(1,1-(biphenyl)-2-ol), tris(4-hydroxyphenyl)methane, 1,1,1-tris(4-hydroxyphenyl)ethane, 2,6-bis ( (2-hydroxy-5-methylphenyl)methyl)-4-methylphenol, 4,4-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl] Phenyl]ethylidene]bisphenol, 4,4'-dihydroxydiphenylanthracene, 2-hydroxy-5-methyl-1,3-dimethylolbenzene, 3,3-methylenebis ( 2-hydroxy-5-methylbenzyl alcohol), bis[4-hydroxy-3,5-bis(hydroxymethyl)]methane, 2,2-bis[4-hydroxy-3,5-bis(hydroxymethyl) )]propane, 2,2-bis[4-hydroxy-3.5-bis(hydroxymethyl)]hexafluoropropane, salicylic acid, malonic acid, methylmalonic acid, dimethylmalonic acid, butyl Malonic acid, succinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, itaconic acid, maleic acid, tetrafluoromaleic acid, diglycolic acid, 1 , 1-cyclobutanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 3,3-tetramethylenepenta , camphoric acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-adamantane dicarboxylic acid, 5-nor Borneene-2,3-dicarboxylic acid, 1,2-phenylenediacetic acid, 1,3-phenylenediacetic acid, 1,4-phenylenediacetic acid, perfluorocortinoic acid, 2-fluorine Phthalic acid, 4-fluoroisophthalic acid, 5-fluoroisophthalic acid, 3-fluorophthalic acid, 4-fluorophthalic acid, 2,4,5,6-tetrafluoroisophthalic acid , 3,4,5,6-tetrafluorophthalic acid, 4,4'-hexafluoroisopropylidene diphenyl dicarboxylic acid, 2,2'-bis(trifluoromethyl)-4,4 '-Extended biphenyl dicarboxylic acid, terephthalic acid, isophthalic acid, 4,4'-oxydiphenyldicarboxylic acid, 5-nitroisophthalic acid, 1,4-naphthalene dicarboxylate Acid, 2,6-naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, 4-hydroxybenzenesulfonic acid, and the like. Further, it is not necessarily limited to those listed herein. Such dissolution The accelerators may be used singly or in combination of two or more.

[圖案的製造方法][Method of manufacturing pattern]

繼而，就使用本發明之正型光阻組成物之圖案的製造方法加以說明。Next, a method of manufacturing the pattern of the positive resist composition of the present invention will be described.

首先，利用浸漬法(soaking method)、噴霧法(spray method)、網版印刷法(screen print method)、旋轉塗布法(spin coating method)等，將本發明之感光性樹脂組成物塗布於矽晶圓、金屬基板、陶瓷基板等基材之支持基板上。繼而，對所得之感光性樹脂塗膜進行適度加熱乾燥，使感光性樹脂塗膜無黏著性。然後，於感光性樹脂塗膜上塗布光阻，並通過描繪有預期圖案之光罩(mask)而照射活性光線或化學線，進行曝光處理。First, the photosensitive resin composition of the present invention is applied to twin crystal by a soaking method, a spray method, a screen print method, a spin coating method, or the like. On a support substrate of a substrate such as a circle, a metal substrate or a ceramic substrate. Then, the obtained photosensitive resin coating film is appropriately dried by heating to make the photosensitive resin coating film non-adhesive. Then, a photoresist is applied onto the photosensitive resin coating film, and an active light or a chemical line is irradiated by a mask in which a desired pattern is drawn, and exposure treatment is performed.

上述，所照射之活性光線或化學線，可利用使用超高壓水銀燈之接觸式(contact)/近接式(proximity)曝光機、鏡像投影式(mirror projection)曝光機、i線步進機、g線步進機、其他紫外線、可見光源、X線或電子線。其後，根據需要進行曝光後加熱(PEB，post exposure bake，曝後烤)處理，進行顯影。可藉由以顯影液溶解除去曝光部，而獲得預期之正片圖案。In the above, the active light or chemical line to be irradiated may be a contact/proximity exposure machine using a super high pressure mercury lamp, a mirror projection exposure machine, an i line stepper, a g line. Stepper, other ultraviolet, visible light, X-ray or electronic wire. Thereafter, post-exposure heating (PEB, post exposure bake) treatment is performed as needed to perform development. The desired positive pattern can be obtained by dissolving the exposed portion with a developing solution.

顯影液可使用鹼性水溶液，例如，可使用苛性鉀、苛性鈉等鹼金屬氫氧化物之水溶液，四甲基氫氧化銨(tetramethyl ammonium hydroxaide)、四乙基氫氧化銨、膽鹼(choline)等氫氧化四級銨，乙醇胺(ethanol amine)、丙基胺(propyl amine)、乙二胺(ethylene diamine)等胺水溶液 等。另外，顯影後可根據需要以水或不良溶劑(poor solvent)進行洗滌。洗滌液例如可使用，甲醇、乙醇、異丙醇、苯、甲苯、二甲苯、甲基溶纖劑(methyl cellosolve)、水等。其後，除去光阻，藉由加熱所得之圖案，而除去溶劑、或溶劑及感光劑，可獲得穩定之高耐熱性聚苯幷噁唑圖案。An alkaline aqueous solution can be used as the developing solution. For example, an aqueous solution of an alkali metal hydroxide such as caustic potash or caustic soda, tetramethyl ammonium hydroxaide, tetraethylammonium hydroxide or choline can be used. Ammonium hydroxide such as ammonium hydride, ethanol amine, propyl amine, ethylene diamine Wait. Further, after development, it may be washed with water or a poor solvent as needed. As the washing liquid, for example, methanol, ethanol, isopropanol, benzene, toluene, xylene, methyl cellosolve, water or the like can be used. Thereafter, the photoresist is removed, and the solvent or the solvent and the sensitizer are removed by heating the obtained pattern to obtain a stable high heat-resistant polybenzoxazole pattern.

上述加熱溫度較好的是設為150~500℃，更好的是設為200~400℃。若該加熱溫度不足150℃，則存有膜之機械特性及熱特性下降之傾向；若加熱溫度超過500℃，則會存在膜之機械特性及熱特性下降之傾向。The heating temperature is preferably from 150 to 500 ° C, more preferably from 200 to 400 ° C. When the heating temperature is less than 150 ° C, the mechanical properties and thermal properties of the film tend to decrease. When the heating temperature exceeds 500 ° C, the mechanical properties and thermal properties of the film tend to decrease.

又，加熱時間較好的是設為0.05~10小時。若該加熱時間不足0.05小時，則存有膜之機械特性及熱特性下降之傾向；若加熱時間超過10小時，則會存在膜之機械特性及熱特性下降之傾向。Further, the heating time is preferably set to 0.05 to 10 hours. When the heating time is less than 0.05 hours, the mechanical properties and thermal properties of the film tend to decrease. When the heating time exceeds 10 hours, the mechanical properties and thermal properties of the film tend to decrease.

[電子零件][electronic parts]

本發明之正型光阻組成物及圖案的製造方法可用於半導體裝置或多層布線板等電子零件中，具體而言，可用於形成半導體裝置之表面保護膜層或層間絕緣膜層、多層布線板之層間絕緣膜層等。本發明之電子零件具有使用上述正型光阻組成物而形成之表面保護膜層及/或層間絕緣膜層，除此以外並無特別限制，其可採用各種結構。又，電子零件包括半導體裝置或多層布線板、各種電子裝置等。The method for producing a positive photoresist composition and a pattern of the present invention can be used in an electronic device such as a semiconductor device or a multilayer wiring board, and specifically, can be used to form a surface protective film layer or an interlayer insulating film layer of a semiconductor device, or a multilayer cloth. An interlayer insulating film layer of a wire board or the like. The electronic component of the present invention has a surface protective film layer and/or an interlayer insulating film layer formed using the above-described positive resist composition, and is not particularly limited, and various structures can be employed. Further, the electronic component includes a semiconductor device, a multilayer wiring board, various electronic devices, and the like.

繼而，以下就本發明之電子零件之一例的半導體裝置製造製程之一例加以說明。圖1~圖5是用來說明多層布線結構之半導體裝置之製造製程圖的概況剖面圖，自圖1 至圖5分別表示自第1製程至第5製程之一系列製程。Next, an example of a manufacturing process of a semiconductor device which is an example of the electronic component of the present invention will be described below. 1 to 5 are schematic cross-sectional views showing a manufacturing process diagram of a semiconductor device having a multilayer wiring structure, from FIG. Figure 5 shows a series of processes from the first process to the fifth process.

於這些圖中，含有電路元件(未圖示)之矽(Si)基板等半導體基板1，以矽氧化膜等保護膜2等被覆電路元件之特定部分以外的部分，且於露出之電路元件上形成有第一導體層3。然後，使用旋塗法等，於上述半導體基板1上形成層間絕緣膜層4(第1製程，圖1)。In the above-mentioned drawings, the semiconductor substrate 1 such as a bismuth (Si) substrate including a circuit component (not shown) is covered with a protective film 2 such as a tantalum oxide film or the like, and is exposed on the exposed circuit component. A first conductor layer 3 is formed. Then, an interlayer insulating film layer 4 is formed on the semiconductor substrate 1 by a spin coating method or the like (first process, FIG. 1).

隨後，使用旋塗法於上述層間絕緣膜層4上形成氯化橡膠系、酚醛(phenol novolac，PN)系等感光性樹脂層5，其作為光罩。然後，藉由眾所周知之照相蝕刻技術(photolithography，光微影法)設置開口6A，而露出特定部分之層間絕緣膜層4(第2製程，圖2)。Subsequently, a photosensitive resin layer 5 such as a chlorinated rubber or phenol novolac (PN) system is formed on the interlayer insulating film layer 4 by spin coating, and this is used as a photomask. Then, the opening 6A is provided by a well-known photolithography method to expose a specific portion of the interlayer insulating film layer 4 (second process, FIG. 2).

接著，藉由使用氧、四氟化碳等氣體之乾式蝕刻方法，自上述露出層間絕緣膜層4之開口6A進行選擇性蝕刻，以打開開口6B。繼而，使用不會腐蝕開口6B底部露出之第一導體層3、而僅腐蝕感光性樹脂層5之蝕刻溶液，完全除去感光性樹脂層5(第3製程，圖3)。Next, the opening 6A of the exposed interlayer insulating film layer 4 is selectively etched by a dry etching method using a gas such as oxygen or carbon tetrafluoride to open the opening 6B. Then, the photosensitive resin layer 5 is completely removed by using the etching solution which does not corrode the first conductor layer 3 exposed at the bottom of the opening 6B and etches only the photosensitive resin layer 5 (third process, FIG. 3).

繼之，使用眾所周知之照相蝕刻技術，形成第二導體層7，以與第一導體層3完全電性連接(第4製程，圖4)。於形成三層以上之多層布線結構之情形時，可重複進行上述製程而形成各層。Next, a second conductor layer 7 is formed to be fully electrically connected to the first conductor layer 3 using a well-known photolithography technique (Process 4, Figure 4). In the case of forming a multilayer wiring structure of three or more layers, the above process may be repeated to form each layer.

隨後，形成表面保護膜層8。於圖1~圖5之例中，以旋塗法塗布、乾燥上述感光性樹脂組成物，自於特定部分描繪有形成開口6C之圖案的光罩上照射光後，以鹼性水溶液加以顯影形成圖案，進行加熱而製成表面保護膜層 8(第5製程，圖5)。該表面保護膜層8可保護導體層不受到來自外部之應力及α線等，如此可使所得之半導體裝置可靠性優良。再者，於上述實施例中，亦可使用本發明之正型光阻組成物來形成層間絕緣膜層4。Subsequently, a surface protective film layer 8 is formed. In the example of FIGS. 1 to 5, the photosensitive resin composition is applied and dried by a spin coating method, and is irradiated with light from a mask on which a pattern of the opening 6C is formed in a specific portion, and then developed by using an alkaline aqueous solution. Pattern, heated to form a surface protective film layer 8 (5th process, Figure 5). The surface protective film layer 8 protects the conductor layer from external stress and α-ray, etc., so that the obtained semiconductor device can be excellent in reliability. Further, in the above embodiment, the interlayer insulating film layer 4 may be formed using the positive resist composition of the present invention.

以下，根據實驗例及比較例加以進一步具體說明本發明。再者，本發明並非限定於下述實驗例。Hereinafter, the present invention will be further specifically described based on experimental examples and comparative examples. Furthermore, the present invention is not limited to the following experimental examples.

合成例1Synthesis Example 1

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器之燒瓶中，放入75 g乾燥N-甲基吡咯烷酮(N-methylpyrrolidone，NMP)及12.9 g(0.05 mol)4,4'-二苯醚二羧酸(4,4’-diphenyl ether dicarboxylic acid)。然後，將該燒瓶冷卻至5℃後，滴加11.9 g(0.1 mol)亞硫醯氯(thionyl chloride)，且滴加後進行攪拌30分鐘，以獲得反應溶液A-1。繼而，於其他具備攪拌機、溫度計及氮氣導入管之密閉反應容器中，添加105 g乾燥N-甲基吡咯烷酮、22.0 g(0.06 mol)2,2-雙(3-胺基-4-羥基苯基)六氟丙烷及3.28 g(0.02 mol)5-降冰片烯-2,3-二羧酸酐(用於形成聚合物末端)，攪拌溶解後，再添加15.8 g(0.2 mol)吡啶，進行攪拌溶解。將上述溶液冷卻至0℃，接著在30分鐘內滴加剛才所得之反應溶液A-1，之後於室溫下攪拌30分鐘。繼之，於2.0升離子交換水中劇烈攪拌該反應混合物並且進行處理。進而，以離子交換水洗淨析出之固形物，於阻擋濾片上進行吸引乾燥，然後進行減壓乾燥，以獲得聚合物P-1。聚合物P-1之含水率為0.8 wt%，重量平均分子量為 22,800，分散度為1.8。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 75 g of dry N-methylpyrrolidone (NMP) and 12.9 g (0.05 mol) of 4,4'-diphenyl ether were placed. 4,4'-diphenyl ether dicarboxylic acid. Then, after the flask was cooled to 5 ° C, 11.9 g (0.1 mol) of thionyl chloride was added dropwise, and the mixture was stirred for 30 minutes to obtain a reaction solution A-1. Then, in another closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 105 g of dry N-methylpyrrolidone and 22.0 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) were added. Hexafluoropropane and 3.28 g (0.02 mol) of 5-norbornene-2,3-dicarboxylic anhydride (used to form polymer ends), stirred and dissolved, and then added 15.8 g (0.2 mol) of pyridine to stir and dissolve . The solution was cooled to 0 ° C, and then the reaction solution A-1 just obtained was added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. Following that, the reaction mixture was vigorously stirred in 2.0 liters of ion-exchanged water and treated. Further, the precipitated solid matter was washed with ion-exchanged water, subjected to suction drying on a barrier filter, and then dried under reduced pressure to obtain a polymer P-1. The water content of the polymer P-1 is 0.8 wt%, and the weight average molecular weight is 22,800 with a dispersion of 1.8.

合成例2Synthesis Example 2

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器之燒瓶中，放入75 g乾燥N-甲基吡咯烷酮及12.9 g(0.05 mol)4,4'-二苯醚二羧酸。然後，將該燒瓶冷卻至5℃後，滴加11.9 g(0.1 mol)亞硫醯氯，滴加後攪拌30分鐘，以獲得反應溶液A-1。繼而，於其他具備攪拌機、溫度計及氮氣導入管之密閉反應容器中，添加105 g乾燥N-甲基吡咯烷酮、22.0 g(0.06 mol)2,2-雙(3-胺基-4-羥基苯基)六氟丙烷及1.96 g(0.02 mol)順丁烯二酸酐(用於形成聚合物末端)，攪拌溶解後，添加15.8 g(0.2 mol)吡啶，進行攪拌溶解。隨後，將該溶液冷卻至0℃，花費30分鐘滴加剛才所得之反應溶液A-1後，於室溫下攪拌30分鐘。接著，於2.0升離子交換水中劇烈攪拌該反應混合物，並且加以處理。進而，以離子交換水洗淨析出之固形物，於阻擋濾片上進行吸引乾燥，進而進行減壓乾燥，而獲得聚合物P-2。該聚合物P-2之含水率為1.0 wt%，重量平均分子量為20,500，分散度為1.8。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 75 g of dry N-methylpyrrolidone and 12.9 g (0.05 mol) of 4,4'-diphenyl ether dicarboxylic acid were placed. Then, after the flask was cooled to 5 ° C, 11.9 g (0.1 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 30 minutes to obtain a reaction solution A-1. Then, in another closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 105 g of dry N-methylpyrrolidone and 22.0 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) were added. Hexafluoropropane and 1.96 g (0.02 mol) of maleic anhydride (used to form a polymer end) were stirred and dissolved, and then 15.8 g (0.2 mol) of pyridine was added and stirred to dissolve. Subsequently, the solution was cooled to 0 ° C, and the reaction solution A-1 just obtained was added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. Next, the reaction mixture was vigorously stirred in 2.0 liters of ion-exchanged water and treated. Further, the precipitated solid matter was washed with ion-exchanged water, suction-dried on a barrier filter, and further dried under reduced pressure to obtain a polymer P-2. The polymer P-2 had a water content of 1.0 wt%, a weight average molecular weight of 20,500, and a degree of dispersion of 1.8.

合成例3Synthesis Example 3

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器中之燒瓶中，放入100 g乾燥N-甲基吡咯烷酮及20.7 g(0.08 mol)4,4'-二苯醚二羧酸。然後，將該燒瓶冷卻至5℃後，滴加19.0 g(0.16 mol)亞硫醯氯，滴加後攪拌30分鐘，獲得反應溶液A-2。繼而，於其他具備攪拌機、溫度計及氮氣 導入管之密閉反應容器中，添加105 g乾燥N-甲基吡咯烷酮及23.2 g(0.09 mol)2,2-雙(3-胺基-4-羥基苯基)丙烷，進行攪拌溶解，添加2.29 g(0.02 mol)甲烷磺醯氯(用於形成聚合物末端)，攪拌溶解後，添加25.3 g(0.32 mol)吡啶，進行攪拌溶解。將該溶液冷卻至0℃，花費30分鐘滴加剛才所得之反應溶液A-2後，於室溫下攪拌30分鐘。接著，於2.0升離子交換水中劇烈攪拌該反應混合物，並且加以處理。進而，以離子交換水洗淨析出之固形物，於阻擋濾片上進行吸引乾燥，接著進行減壓乾燥獲得聚合物P-3。該聚合物P-3之含水率為0.7 wt%，重量平均分子量為20,800，分散度為1.7。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 100 g of dry N-methylpyrrolidone and 20.7 g (0.08 mol) of 4,4'-diphenyl ether dicarboxylic acid were placed. Then, after cooling the flask to 5 ° C, 19.0 g (0.16 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 30 minutes to obtain a reaction solution A-2. Then, with other mixers, thermometers and nitrogen In a closed reaction vessel of the introduction tube, 105 g of dry N-methylpyrrolidone and 23.2 g (0.09 mol) of 2,2-bis(3-amino-4-hydroxyphenyl)propane were added, stirred and dissolved, and 2.29 g was added. (0.02 mol) methanesulfonium chloride (used to form a polymer end), and after stirring and dissolved, 25.3 g (0.32 mol) of pyridine was added and stirred to dissolve. The solution was cooled to 0 ° C, and the reaction solution A-2 just obtained was added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. Next, the reaction mixture was vigorously stirred in 2.0 liters of ion-exchanged water and treated. Further, the precipitated solid matter was washed with ion-exchanged water, subjected to suction drying on a barrier filter, and then dried under reduced pressure to obtain a polymer P-3. The polymer P-3 had a water content of 0.7 wt%, a weight average molecular weight of 20,800, and a degree of dispersion of 1.7.

合成例4Synthesis Example 4

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器之燒瓶中，放入75 g乾燥N-甲基吡咯烷酮、10.3 g(0.04 mol)4,4'-二苯醚二羧酸及17.2 g(0.01 mol)1,4-環己烷二羧酸，將該燒瓶冷卻至5℃後，滴加11.9 g(0.1 mol)亞硫醯氯，滴加後攪拌30分鐘，獲得反應溶液A-3。繼而，於其他具備攪拌機、溫度計及氮氣導入管之密閉反應容器中，添加105 g乾燥N-甲基吡咯烷酮、22.0 g(0.06 mol)2,2-雙(3-胺基-4-羥基苯基)六氟丙烷及3.28 g(0.02 mol)5-降冰片烯-2,3-二羧酸酐(用於形成聚合物末端)，攪拌溶解後，添加15.8 g(0.2 mol)吡啶，進行攪拌溶解。將該溶液至冷卻0℃，花費30分鐘滴加剛才所得之反應溶液A-3後，於室溫下攪拌30分鐘。於2.0升離子交換水中劇烈攪拌該 反應混合物並且加以處理。進而，以離子交換水洗淨析出之固形物，於阻擋濾片上進行吸引乾燥，接著進行減壓乾燥獲得聚合物P-4。該聚合物P-4之含水率為0.8 wt%，重量平均分子量為20,300，分散度為1.8。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 75 g of dry N-methylpyrrolidone, 10.3 g (0.04 mol) of 4,4'-diphenyl ether dicarboxylic acid and 17.2 g (0.01) were placed. Mol) 1,4-cyclohexanedicarboxylic acid, the flask was cooled to 5 ° C, and 11.9 g (0.1 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 30 minutes to obtain a reaction solution A-3. Then, in another closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 105 g of dry N-methylpyrrolidone and 22.0 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) were added. Hexafluoropropane and 3.28 g (0.02 mol) of 5-norbornene-2,3-dicarboxylic anhydride (used to form a polymer end) were stirred and dissolved, and then 15.8 g (0.2 mol) of pyridine was added and stirred to dissolve. The solution was cooled to 0 ° C, and the reaction solution A-3 just obtained was added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. Stirring vigorously in 2.0 liters of ion-exchanged water The reaction mixture was treated and treated. Further, the precipitated solid matter was washed with ion-exchanged water, subjected to suction drying on a barrier filter, and then dried under reduced pressure to obtain a polymer P-4. The polymer P-4 had a water content of 0.8 wt%, a weight average molecular weight of 20,300, and a degree of dispersion of 1.8.

合成例5Synthesis Example 5

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器之燒瓶中，放入75 g乾燥N-甲基吡咯烷酮及8.31 g(0.05 mol)間苯二甲酸，將該燒瓶冷卻至5℃後，滴加11.9 g(0.1 mol)亞硫醯氯，滴加後攪拌30分鐘，獲得反應溶液A-4。繼而，於其他具備攪拌機、溫度計及氮氣導入管之密閉反應容器中，添加105 g乾燥N-甲基吡咯烷酮、22.0 g(0.06 mol)2,2-雙(3-胺基-4-羥基苯基)六氟丙烷及3.28 g(0.02 mol)5-降冰片烯-2,3-二羧酸酐(用於形成聚合物末端)，攪拌溶解後，添加15.8 g(0.2 mol)吡啶，進行攪拌溶解。將該溶液冷卻至0℃，花費30分鐘滴加剛才所得之反應溶液A-4後，於室溫下攪拌30分鐘。於2.0升離子交換水中劇烈攪拌該反應混合物並且加以處理。進而以離子交換水洗淨析出之固形物，於阻擋濾片上進行吸引乾燥，進而進行減壓乾燥獲得聚合物P-5。該聚合物P-5之含水率為0.7 wt%，重量平均分子量為18,800，分散度為1.8。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 75 g of dry N-methylpyrrolidone and 8.31 g (0.05 mol) of isophthalic acid were placed, and the flask was cooled to 5 ° C and then added dropwise. 11.9 g (0.1 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 30 minutes to obtain a reaction solution A-4. Then, in another closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 105 g of dry N-methylpyrrolidone and 22.0 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) were added. Hexafluoropropane and 3.28 g (0.02 mol) of 5-norbornene-2,3-dicarboxylic anhydride (used to form a polymer end) were stirred and dissolved, and then 15.8 g (0.2 mol) of pyridine was added and stirred to dissolve. The solution was cooled to 0 ° C, and the reaction solution A-4 just obtained was added dropwise over 30 minutes, followed by stirring at room temperature for 30 minutes. The reaction mixture was stirred vigorously in 2.0 liters of ion-exchanged water and treated. Further, the precipitated solid matter was washed with ion-exchanged water, suction-dried on a barrier filter, and further dried under reduced pressure to obtain a polymer P-5. The polymer P-5 had a water content of 0.7 wt%, a weight average molecular weight of 18,800, and a degree of dispersion of 1.8.

合成例6Synthesis Example 6

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器之燒瓶中，放入100 g乾燥N-甲基吡咯烷酮及26.6 g(0.09 mol)4,4'-二苯醚二羧酸二氯化物，攪拌溶解，獲得溶液A -5。繼而，於其他具備攪拌機、溫度計及氮導入管之密閉反應容器中，攪拌溶解105 g乾燥N-甲基吡咯烷酮、2.18 g(0.02 mol)間胺基苯酚(用於形成聚合物末端)及20.7 g(0.08 mol)2,2-雙(3-胺基-4-羥基苯基)丙烷。將該溶液冷卻至0℃，花費30分鐘滴加剛才所得之反應溶液A-5後，於室溫下30攪拌分鐘。於2.0升離子交換水中劇烈攪拌該反應混合物並且加以處理。進而以離子交換水洗淨析出之固形物，於阻擋濾片上進行吸引乾燥，進而進行減壓乾燥獲得聚合物P-6。該聚合物P-6之含水率為0.7 wt%，重量平均分子量為23,000，分散度為1.7。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 100 g of dry N-methylpyrrolidone and 26.6 g (0.09 mol) of 4,4'-diphenyl ether dicarboxylic acid dichloride were added and stirred. Dissolve, obtain solution A -5. Then, in a closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen introduction tube, 105 g of dry N-methylpyrrolidone, 2.18 g (0.02 mol) of m-aminophenol (for forming a polymer end) and 20.7 g were stirred and dissolved. (0.08 mol) 2,2-bis(3-amino-4-hydroxyphenyl)propane. The solution was cooled to 0 ° C, and the reaction solution A-5 just obtained was added dropwise over 30 minutes, and stirred at room temperature for 30 minutes. The reaction mixture was stirred vigorously in 2.0 liters of ion-exchanged water and treated. Further, the precipitated solid matter was washed with ion-exchanged water, suction-dried on a barrier filter, and further dried under reduced pressure to obtain a polymer P-6. The polymer P-6 had a water content of 0.7 wt%, a weight average molecular weight of 23,000, and a degree of dispersion of 1.7.

合成例7Synthesis Example 7

於具備攪拌機、溫度計及氮氣導入管之密閉反應容器之燒瓶中，放入75 g乾燥N-甲基吡咯烷酮及12.9 g(0.05 mol)4,4'-二苯醚二羧酸，將該燒瓶冷卻至5℃後，滴加11.9 g(0.1 mol)亞硫醯氯，滴加後攪拌30分鐘，獲得反應溶液A-1。繼而，於其他具備攪拌機、溫度計及氮氣導入管之密閉反應容器中，添加105 g乾燥N-甲基吡咯烷酮、22.0 g(0.06 mol)2,2-雙(3-胺基-4-羥基苯基)六氯丙烷及2.09 g(0.02 mol)環丙基甲醯氯(Cyclopropane carbonyl chloride)(用於形成聚合物末端)，攪拌溶解後，添加15.8 g(0.2 mol)吡啶，進行攪拌溶解。將該溶液冷卻至0℃，花費30分鐘滴加剛才所得之反應溶液A-1，於室溫下攪拌30分鐘。於2.0升離子交換水中劇烈攪拌該反應混合物並，且加以處理。進而，以離子交換水洗淨析出之固形物， 於阻擋濾片上進行吸引乾燥，接著進行減壓乾燥獲得聚合物P-7。該聚合物P-7之含水率為0.8 wt%，重量平均分子量為19,800，分散度為1.7。In a flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, 75 g of dry N-methylpyrrolidone and 12.9 g (0.05 mol) of 4,4'-diphenyl ether dicarboxylic acid were placed, and the flask was cooled. After 5 ° C, 11.9 g (0.1 mol) of sulfinium chloride was added dropwise, and the mixture was stirred for 30 minutes to obtain a reaction solution A-1. Then, in another closed reaction vessel equipped with a stirrer, a thermometer and a nitrogen inlet tube, 105 g of dry N-methylpyrrolidone and 22.0 g (0.06 mol) of 2,2-bis(3-amino-4-hydroxyphenyl) were added. Hexachloropropane and 2.09 g (0.02 mol) of Cyclopropane carbonyl chloride (used to form a polymer end) were stirred and dissolved, and then 15.8 g (0.2 mol) of pyridine was added and stirred to dissolve. The solution was cooled to 0 ° C, and the reaction solution A-1 just obtained was added dropwise over 30 minutes, and stirred at room temperature for 30 minutes. The reaction mixture was stirred vigorously in 2.0 liters of ion-exchanged water and treated. Further, the precipitated solid matter is washed with ion-exchanged water, The suction drying was carried out on a barrier filter, followed by drying under reduced pressure to obtain a polymer P-7. The polymer P-7 had a water content of 0.8 wt%, a weight average molecular weight of 19,800, and a degree of dispersion of 1.7.

實驗例1Experimental example 1

於具備攪拌機、溫度計及氮氣導入管之三口燒瓶中，攪拌混合10 g合成例1中所得之聚合物P-1及15 g γ-丁內酯，且使之溶解後，加入使2-(4-羥基苯基)-2-[4-[1,1-雙(4-羥基苯基)乙基]苯基]丙烷與萘醌-1,2-二疊氮基-5-磺醯氯以1/2.5之莫耳比反應所得之1.50 g的化合物、0.10 g 1H-四唑，以及0.20 g雙(2-羥基乙基)-3-胺基丙基三乙氧基矽烷。於室溫下攪拌一夜使其溶解後，進行過濾而獲得正型光阻組成物溶液。接著，於5英吋矽基板上，濺鍍形成約200 Å厚之TIN膜，且於其上濺鍍形成約5000 Å厚之Cu膜而製成晶圓(以下，稱為「Cu晶圓」)。然後，將該正型光阻組成物溶液旋塗於該晶圓上，之後進行加熱乾燥，以形成10.0 μm之塗膜。其後，使用i線步進機，將曝光量設為700 mJ/cm² ，經由光罩進行曝光。使用2.38%四甲基氫氧化銨水溶液，使其進行泥漿式顯影(paddle development)時，可獲得良好之起伏圖案。進而，以經氮置換之烘箱於300℃加熱1小時，獲得膜厚為7 μm之硬化膜。In a three-necked flask equipped with a stirrer, a thermometer, and a nitrogen introduction tube, 10 g of the polymer P-1 and 15 g of γ-butyrolactone obtained in Synthesis Example 1 were stirred and mixed, and after being dissolved, 2-(4) was added. -hydroxyphenyl)-2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propane and naphthoquinone-1,2-diazido-5-sulfonyl chloride The 1.50 g of the compound obtained by the molar ratio of 1/2.5, 0.10 g of 1H-tetrazole, and 0.20 g of bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane. After stirring at room temperature overnight to dissolve, it was filtered to obtain a positive resist composition solution. Next, a TIN film of about 200 Å thick was formed by sputtering on a 5 inch substrate, and a Cu film of about 5000 Å thick was formed thereon to form a wafer (hereinafter, referred to as "Cu wafer"). ). Then, the positive resist composition solution was spin-coated on the wafer, followed by heat drying to form a coating film of 10.0 μm. Thereafter, the exposure was set to 700 mJ/cm ² using an i-line stepper, and exposure was performed via a photomask. When a 2.38% tetramethylammonium hydroxide aqueous solution was used for paddle development, a good undulation pattern was obtained. Further, the film was heated at 300 ° C for 1 hour in an oven substituted with nitrogen to obtain a cured film having a film thickness of 7 μm.

使用所得之晶圓上之硬化膜，進行柱栓下拉試驗(stud pull test)作為密著性試驗。於柱栓下拉試驗中，使用Phototechnica股份公司製造之型號為901106(2.7 mm)之柱螺栓銷(stud pin)(帶有環氧接著劑之Al)。於150℃之烘 箱內硬化1小時，藉此進行柱螺栓銷及硬化膜之接著。其結果，顯示68.6 MPA之接著力，對Cu膜有充分之密著性。又，使用壓力鍋，於121℃/0.20 MPA之條件下對與上述同樣已進行硬化之晶圓進行100小時處理後(以下，稱為「PCT處理後」)，同樣進行柱栓下拉試驗。其結果，顯示66.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。Using the obtained cured film on the wafer, a stud pull test was performed as the adhesion test. In the column plug-down test, a stud pin (Al with an epoxy adhesive) of Model 901106 (2.7 mm) manufactured by Phototechnica Co., Ltd. was used. Bake at 150 ° C The inside of the box was hardened for 1 hour, whereby the stud pin and the cured film were adhered to. As a result, an adhesion of 68.6 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the wafer which had been hardened as described above was treated for 100 hours under the conditions of 121 ° C / 0.20 MPA using a pressure cooker (hereinafter referred to as "after PCT treatment"), the plug pull-down test was carried out in the same manner. As a result, the adhesion of 66.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

實驗例2Experimental example 2

使用聚合物P-2代替聚合物P-1，使用醯脲丙基三乙氧基矽烷代替雙(2-羥基乙基)-3-胺基丙基三乙氧基矽烷，除此以外，以與實驗例1相同之組成製作正型光阻組成物溶液。除將曝光量設為800 mJ/cm² 以外，與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以800 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1進行同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示66.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示64.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。Using polymer P-2 in place of polymer P-1, using guanidinopropyltriethoxydecane instead of bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane, in addition to A positive resist composition solution was prepared in the same composition as in Experimental Example 1. The positive resist composition solution was treated in the same manner as in Experimental Example 1 except that the exposure amount was set to 800 mJ/cm ² , and the test was carried out. As a result, a good undulating pattern was obtained at an exposure amount of 800 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 66.7 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT treatment, the adhesion of 64.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

實驗例3Experimental example 3

使用P-3代替聚合物P-1，使用1.0 g使三(4-羥基苯基)甲烷及萘醌-1,2-二疊氮基-5-磺醯氯以1/2.8之莫耳比反應所得之化合物代替1.50 g使2-(4-羥基苯基)-2-[4-[1,1-雙(4-羥基苯基)乙基]苯基]丙烷與萘醌-1,2-二疊氮基-5-磺醯氯以1/2.5之莫耳比反應所得之化合物，除此以外，以 與實驗例1相同之組成製作正型光阻組成物溶液。除將曝光量設為500 mJ/cm² 以外，與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以500 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示70.6 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示67.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。Using P-3 instead of polymer P-1, using 1.0 g to make tris(4-hydroxyphenyl)methane and naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/2.8 The compound obtained by the reaction replaces 1.50 g of 2-(4-hydroxyphenyl)-2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl]propane with naphthoquinone-1,2 A positive-type resist composition solution was prepared in the same manner as in Experimental Example 1, except that the compound obtained by the reaction of the molar ratio of 1/2.5 of the diazide-5-sulfonyl chloride was used. The positive resist composition solution was treated in the same manner as in Experimental Example 1 except that the exposure amount was changed to 500 mJ/cm ² , and the test was carried out. As a result, a good undulation pattern was obtained at an exposure amount of 500 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 70.6 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT treatment, the adhesion of 67.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

實驗例4Experimental example 4

使用聚合物P-4代替聚合物P-1，使用萘醌-1,2-二疊氮基-4-磺醯氯代替萘醌-1,2-二疊氮基-5-磺醯氯，使用醯脲丙基三乙氧基矽烷代替雙(2-羥基乙基)-3-胺基丙基三乙氧基矽烷，除此以外，以與實驗例1相同之組成製作正型光阻組成物溶液。與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以700 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示65.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示66.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。The polymer P-4 was used instead of the polymer P-1, and naphthoquinone-1,2-diazido-4-sulfonyl chloride was used instead of naphthoquinone-1,2-diazido-5-sulfonyl chloride. A positive resist composition was prepared in the same manner as in Experimental Example 1, except that guanidinopropyltriethoxydecane was used instead of bis(2-hydroxyethyl)-3-aminopropyltriethoxydecane. Solution. The positive resist composition solution was treated in the same manner as in Experimental Example 1 and tested. As a result, a good undulation pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 65.7 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT treatment, the adhesion of 66.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

實驗例5Experimental example 5

使用聚合物P-5代替聚合物P-3，使用1.5 g使2-(4-羥基苯基)-2-[4-[1,1-雙(4-羥基苯基)乙基]苯基]丙烷及萘醌-1,2-二疊氮基-4-磺醯氯以1/2.5之莫耳比反應所得之化合 物代替1.0 g使三(4-羥基苯基)甲烷及萘醌-1,2-二疊氮基-5-磺醯氯以1/2.8之莫耳比反應所得之化合物，除此以外，以與實驗例3相同之組成製作正型光阻組成物溶液。與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以700 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示62.8 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示64.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。Using polymer P-5 instead of polymer P-3, using 1.5 g to make 2-(4-hydroxyphenyl)-2-[4-[1,1-bis(4-hydroxyphenyl)ethyl]phenyl Propane and naphthoquinone-1,2-diazido-4-sulfonyl chloride replaced by 1.0 g of a compound obtained by a molar ratio of 1/2.5 to tris(4-hydroxyphenyl)methane and naphthoquinone-1 A positive resist composition solution was prepared in the same manner as in Experimental Example 3 except that the compound obtained by the reaction of the 2-diazido-5-sulfonyl chloride at a molar ratio of 1/2.8 was used. The positive resist composition solution was treated in the same manner as in Experimental Example 1 and tested. As a result, a good undulation pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 62.8 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT treatment, the adhesion of 64.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

實驗例6Experimental example 6

除使用聚合物P-6代替聚合物P-5以外，以與實施例5相同之組成製作正型光阻組成物溶液。與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以700 mJ/cm² 之曝光量可得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示63.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示64.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。A positive resist composition solution was prepared in the same composition as in Example 5 except that the polymer P-6 was used instead of the polymer P-5. The positive resist composition solution was treated in the same manner as in Experimental Example 1 and tested. As a result, a good undulating pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 63.7 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT treatment, the adhesion of 64.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

實驗例7Experimental example 7

除使用聚合物P-7代替聚合物P-1以外，以與實驗例1相同之組成製作正型光阻組成物溶液。與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以700 mJ/cm² 之曝光量可得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯 示62.8 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示63.7 MPA之接著力，對Cu膜之密著性於進行PCT處理後亦幾乎未產生惡化。A positive resist composition solution was prepared in the same manner as in Experimental Example 1, except that the polymer P-7 was used instead of the polymer P-1. The positive resist composition solution was treated in the same manner as in Experimental Example 1 and tested. As a result, a good undulating pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 62.8 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT treatment, the adhesion of 63.7 MPA was exhibited, and the adhesion to the Cu film hardly deteriorated after the PCT treatment.

比較例1Comparative example 1

除未調配1H-四唑以外，與實驗例1同樣進行試驗時，以700 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實施例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示66.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後，顯示9.81 MPA之接著力，由於PCT處理而接著力下降。When the test was carried out in the same manner as in Experimental Example 1 except that 1H-tetrazole was not prepared, a good undulation pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the cured film obtained in the same manner as in Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 66.7 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT processing, an adhesion force of 9.81 MPA is displayed, and the force is lowered by the PCT processing.

比較例2Comparative example 2

除未添加1H-四唑以外，與實驗例2同樣進行試驗時，以800 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示65.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後，顯示12.7 MPA之接著力，由於PCT處理而接著力下降。When the test was carried out in the same manner as in Experimental Example 2 except that 1H-tetrazole was not added, a good undulation pattern was obtained at an exposure amount of 800 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 65.7 MPA was exhibited, and the Cu film was sufficiently adhered. Also, after the PCT processing, an adhesion of 12.7 MPA was displayed, and the force was decreased due to the PCT processing.

比較例3Comparative example 3

除未添加1H-四唑以外，與實驗例3同樣進行試驗時，以500 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實施例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示66.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後，顯示6.86 MPA之接著力，由於PCT處理而接著力下降。A test was carried out in the same manner as in Experimental Example 3 except that 1H-tetrazole was not added, and a favorable undulation pattern was obtained at an exposure amount of 500 mJ/cm ² . Further, the cured film obtained in the same manner as in Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 66.7 MPA was exhibited, and the Cu film was sufficiently adhered. Also, after the PCT processing, an adhesion force of 6.86 MPA is displayed, and the force is lowered due to the PCT processing.

比較例4Comparative example 4

除未添加1H-四唑以外，與實驗例4同樣進行試驗時，以700 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示64.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後，顯示10.8 MPA之接著力，由於PCT處理而接著力下降。When the test was carried out in the same manner as in Experimental Example 4 except that 1H-tetrazole was not added, a good undulation pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 64.7 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT processing, an adhesion force of 10.8 MPA was displayed, and the force was decreased due to the PCT processing.

比較例5Comparative Example 5

除未添加1H-四唑以外，與實驗例5同樣進行試驗時，以700 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示63.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後，顯示9.81 MPA之接著力，由於PCT處理而接著力下降。When the test was carried out in the same manner as in Experimental Example 5 except that 1H-tetrazole was not added, a good undulation pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 63.7 MPA was exhibited, and the Cu film was sufficiently adhered. Further, after the PCT processing, an adhesion force of 9.81 MPA is displayed, and the force is lowered by the PCT processing.

比較例6Comparative Example 6

作為調配物，使用10 g合成例1中所得之聚合物P-1、15 gγ-丁內酯、1.50 g使2-(4-羥基苯基)-2-[4-[1,1-雙(4-羥基苯基)乙基]苯基]丙烷與萘醌-1,2-二疊氮基-5-磺醯氯以1/2.5之莫耳比反應所得之化合物、0.10 g十二烷基硫醇、及0.20 g雙(2-羥基乙基)-3-胺基丙基三乙氧基矽烷，除此以外，與實驗例1完全相同進行處理時，由於顯影而使大部分之膜剝落，無法獲得良好之起伏圖案。因此，無法進行柱栓下拉試驗。As a formulation, 10 g of the polymer P-1 obtained in Synthesis Example 1, 15 g of γ-butyrolactone, and 1.50 g were used to make 2-(4-hydroxyphenyl)-2-[4-[1,1-double a compound obtained by reacting (4-hydroxyphenyl)ethyl]phenyl]propane with naphthoquinone-1,2-diazide-5-sulfonyl chloride at a molar ratio of 1/2.5, 0.10 g of dodecane When the thiol and the bis(2-hydroxyethyl)-3-aminopropyltriethoxy decane were used in the same manner as in Experimental Example 1, most of the film was formed by development. Peeling off, you can't get a good undulating pattern. Therefore, the stud pull-down test cannot be performed.

比較例7Comparative Example 7

除未添加1H-四唑以外，與實施例6同樣進行試驗時，以700 mJ/cm² 之曝光量可獲得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示62.8 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後，顯示14.7 MPA之接著力，由於PCT處理而接著力下降。When the test was carried out in the same manner as in Example 6 except that 1H-tetrazole was not added, a good undulation pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 62.8 MPA was exhibited, and the Cu film was sufficiently adhered. Also, after the PCT processing, an adhesion force of 14.7 MPA was displayed, and the force was decreased due to the PCT processing.

比較例8(***化合物之比較例)Comparative Example 8 (Comparative Example of Triazole Compound)

除使用苯幷***代替1H-四唑以外，以與實驗例1相同之組成製作正型光阻組成物溶液。與實驗例1同樣處理該正型光阻組成物溶液，進行試驗。其結果，以700 mJ/cm² 之曝光量可得良好之起伏圖案。又，對與實驗例1同樣處理而獲得之硬化膜進行柱栓下拉試驗。其結果，顯示66.7 MPA之接著力，對Cu膜有充分之密著性。又，於PCT處理後顯示1.96 MPA之接著力，由於PCT處理而接著力下降。A positive resist composition solution was prepared in the same manner as in Experimental Example 1, except that benzotriazole was used instead of 1H-tetrazole. The positive resist composition solution was treated in the same manner as in Experimental Example 1 and tested. As a result, a good undulating pattern was obtained at an exposure amount of 700 mJ/cm ² . Further, the hardened film obtained in the same manner as in Experimental Example 1 was subjected to a plug pull-down test. As a result, the adhesion of 66.7 MPA was exhibited, and the Cu film was sufficiently adhered. Also, after the PCT processing, the adhesion of 1.96 MPA was displayed, and the force was decreased due to the PCT processing.

將實驗例1~7及比較例1~8中之各聚合物、含氮雜環化合物之組合、及接著力之結果總括於表1。Table 1 shows the results of the combination of each of the polymers in the experimental examples 1 to 7 and the comparative examples 1 to 8, the nitrogen-containing heterocyclic compound, and the bonding force.

如上所述，本發明之感光性樹脂組成物，其耐熱性、密著性、尤其是加熱加壓下等嚴酷條件下之膜密著性、靈敏度、析像度、防殘膜效果優良，故而可獲得形狀良好之起伏圖案。因此，本發明之感光性樹脂組成物，可靠性優良，尤其適於製造電子零件。As described above, the photosensitive resin composition of the present invention is excellent in heat resistance, adhesion, and particularly excellent film adhesion, sensitivity, resolution, and anti-resistance effect under severe conditions such as heat and pressure. A well-shaped undulating pattern can be obtained. Therefore, the photosensitive resin composition of the present invention is excellent in reliability and is particularly suitable for the production of electronic parts.

雖然本發明已以較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作些許之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the present invention has been described in its preferred embodiments, the present invention is not intended to limit the invention, and the present invention may be modified and modified without departing from the spirit and scope of the invention. The scope of protection is subject to the definition of the scope of the patent application.

1‧‧‧半導體基板1‧‧‧Semiconductor substrate

2‧‧‧保護膜2‧‧‧Protective film

3‧‧‧第一導體層3‧‧‧First conductor layer

4‧‧‧層間絕緣膜層4‧‧‧Interlayer insulating film

5‧‧‧感光性樹脂層5‧‧‧Photosensitive resin layer

6A、6B、6C‧‧‧開口6A, 6B, 6C‧‧‧ openings

7‧‧‧第二導體層7‧‧‧Second conductor layer

8‧‧‧表面保護膜層8‧‧‧Surface protective film

圖1至圖5是說明本發明之實施例之具有多層布線結 構的半導體裝置之製造製程的概況剖面圖。1 to 5 are diagrams showing a multilayer wiring junction of an embodiment of the present invention A schematic cross-sectional view of a manufacturing process of a semiconductor device.

1‧‧‧半導體基板1‧‧‧Semiconductor substrate

2‧‧‧保護膜2‧‧‧Protective film

3‧‧‧第一導體層3‧‧‧First conductor layer

4‧‧‧層間絕緣膜層4‧‧‧Interlayer insulating film

6C‧‧‧開口6C‧‧‧ openings

7‧‧‧第二導體層7‧‧‧Second conductor layer

8‧‧‧表面保護膜層8‧‧‧Surface protective film

Claims (9)

一種正型光阻組成物，其特徵在於包括：(A)聚苯幷噁唑前驅物，其具有以下述通式(I)所表示之結構；(B)溶劑；(C)四唑衍生物；及(D)藉由光而產生酸之化合物， (式中，X是2價有機基；Y是4價有機基；R₁ 是氫或1價有機基；m是2~500之整數，其表示聚合物之重複單元數)。A positive resist composition characterized by comprising: (A) a polybenzoxazole precursor having a structure represented by the following formula (I); (B) a solvent; (C) a tetrazole derivative And (D) a compound that produces an acid by light, (wherein X is a divalent organic group; Y is a tetravalent organic group; R ₁ is hydrogen or a monovalent organic group; and m is an integer of 2 to 500, which represents the number of repeating units of the polymer). 如申請專利範圍第1項所述之正型光阻組成物，其中於上述(A)以通式(I)所表示之聚苯幷噁唑前驅物之兩末端部分別具有，未含有反應性不飽和鍵之環式鍵、反應性不飽和鍵或非環式飽和鍵。 The positive-type resist composition according to claim 1, wherein the polybenzoxazole precursor represented by the above formula (I) has (A) both end portions, respectively, and does not contain reactivity. A cyclic bond, a reactive unsaturated bond, or an acyclic saturated bond of an unsaturated bond. 如申請專利範圍第1項所述之正型光阻組成物，其中上述(A)以通式(I)所表示之聚苯幷噁唑前驅物中之X及Y分別是一個或、兩個或兩個以上之環式脂肪族基或芳香族基，上述兩個或兩個以上之環式脂肪族基或芳香族基藉由單鍵、有機基或選自氧、硫、氮、矽所構成之群之至少一種雜原子而相互鍵結。 The positive-type photoresist composition according to claim 1, wherein the (A) X and Y in the polybenzoxazole precursor represented by the formula (I) are one or two, respectively. Or two or more cyclic aliphatic or aromatic groups, the above two or more cyclic aliphatic or aromatic groups by a single bond, an organic group or selected from the group consisting of oxygen, sulfur, nitrogen, and hydrazine At least one hetero atom of the group formed is bonded to each other. 如申請專利範圍第1項所述之正型光阻組成物，其 中上述(D)藉由光而產生酸之化合物是鄰二疊氮醌化合物。 A positive photoresist composition as described in claim 1 of the patent application, The above (D) compound which generates an acid by light is an o-diazide compound. 如申請專利範圍第1項所述之正型光阻組成物，其中上述(C)四唑衍生物為1H-四唑、5-甲基-1H-四唑、5-苯基-1H-四唑、5-胺基-1H-四唑、1-甲基-1H-四唑、或5,5'-雙-1H-四唑。 The positive resist composition according to claim 1, wherein the (C) tetrazole derivative is 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetra Oxazole, 5-amino-1H-tetrazole, 1-methyl-1H-tetrazole, or 5,5'-bis-1H-tetrazole. 如申請專利範圍第1項所述之正型光阻組成物，更包含矽烷偶合劑。 The positive-type photoresist composition according to claim 1, further comprising a decane coupling agent. 如申請專利範圍第6項所述之正型光阻組成物，其中上述矽烷偶合劑為烷氧基矽烷。 The positive-type photoresist composition according to claim 6, wherein the decane coupling agent is an alkoxy decane. 一種圖案的製造方法，其特徵在於包括：塗布乾燥製程，其將如申請專利範圍第一項所述之正型光阻組成物塗布於支持基板上而加以乾燥；曝光製程，其將藉由上述塗布、乾燥所得之感光性樹脂膜曝光為特定圖案；顯影製程，其使用鹼性水溶液使上述曝光後之感光性樹脂膜顯影；以及加熱處理製程，其加熱處理上述顯影後之感光性樹脂膜。 A method for producing a pattern, comprising: a coating drying process for applying a positive photoresist composition as described in claim 1 of the patent application to a support substrate for drying; and an exposure process, which is The photosensitive resin film obtained by coating and drying is exposed to a specific pattern, a developing process for developing the exposed photosensitive resin film using an alkaline aqueous solution, and a heat treatment process for heat-treating the developed photosensitive resin film. 一種電子零件，其特徵在於：具有利用如申請專利範圍第8項所述之圖案的製造方法所獲得之圖案層。 An electronic component characterized by having a pattern layer obtained by a manufacturing method using a pattern as described in claim 8 of the patent application.