201248330 六、發明說明： 【發明所屬之技術領域】 本發明係關於光阻下層膜形成用組成物及圖型形成方 法。 【先前技術】 半導體裝置之基板係使用所希望之圖型經圖型化者。 此基板之圖型化步驟係具有如以下之步驟者，例如使稱之 爲光阻組成物之感光性物質堆積於基板上而形成光阻膜之 步驟、對上述光阻膜之既定領域進行曝光之步驟、將光阻 膜顯像並去除曝光部或未曝光部而得到形成有既定圖型之 光阻圖型的步驟、將所得之上述光阻圖型作爲蝕刻光罩並 對基板進行乾式蝕刻之步驟等。 此般圖型化步驟中，使光阻膜曝光用之曝光光源係使 用ArF準分子雷射等之紫外光線，但最近對大規模積體電 路（LSI)之微細化之要求逐步提高，而所必要之解像度亦逐 漸成爲在曝光之光（紫外光線）之波長以下。因此，所必要 之解像度若在曝光之光的波長以下時，曝光量容許度、焦 點容許度等之曝光製程容許度則變得不足。爲了彌補此般 曝光製程容許度之不足，將光阻膜之膜厚變薄而使解像性 提升之方式雖爲有效，但膜厚若變薄，則有變得難以確保 在基板之鈾刻時所必要之光阻膜厚之憂慮。 因此，亦進行檢討著關於在基板與光阻膜之間形成光 阻下層膜，將光阻圖型暫且轉印於下層膜而形成下層膜圖 -5- 201248330 型後’將此下層膜圖型作爲蝕刻光罩而將圖型轉印至基板 之步驟。 作爲形成上述光阻下層膜用之組成物，係以由具有蝕 刻耐性之成分所構成者爲佳，例如已提案有，含有熱硬化 苯酚酚醛清漆等之碳含有量爲多且具有吸收蝕刻中之能量 之芳香族環之聚合物的組成物、含有具有乙烯合萘骨架之 聚合物的組成物等（參照特開20(H-40293號公報及特開 2000- 1 43 93 7號公報）。又，亦提案有含有苯乙烯衍生物或 烯丙基苯衍生物與Nortricyclene衍生物之共聚物的組成 物等（參照特開2 0 0 8 - 6 5 3 0 3號公報）。 然而，藉由上述般以往之下層膜形成用組成物所形成 之光阻下層膜，有在193nm下之折射率η爲低，且消光係 數k變大之傾向。因此，在藉由含有具有芳香族環之聚合 物的組成物形成光阻下層膜，並於此光阻下層膜上形成以 丙烯酸系爲主成分之光阻膜時，與光阻膜相比光阻下層膜 之反射率變高，而有無法形成良好光阻圖型之不良情形。 因此，爲了減低光阻下層膜之反射率，則有必要使光 阻下層膜之折射率η變高之同時亦使消光係數k變小。作 爲解決此之計策，已知有對下層膜形成用組成物加入丙烯 酸系之添加劑。但，若對光阻下層膜形成用組成物添加丙 烯酸系之添加劑，則有使光阻下層膜之蝕刻耐性大幅降低 之不良情形。 [先前技術文獻] [專利文獻] -6- 201248330 [專利文獻1]日本特開2001-40293號公報 [專利文獻2]日本特開2000_143937號公報 [專利文獻3]日本特開2008_653〇3號公報 【發明內容】 [發明所欲解決之課題] 本發明係有鑑於如以上般之情事所完成者，本發明之 目的爲提供可形成蝕刻耐性優良，反射率經降低（即，折 射率η爲高’消光係數k爲小）之光阻下層膜之光阻下層 膜形成用組成物，及使用其之圖型形成方法。 [用以解決課題之手段] 爲了解決上述課題所完成之本發明係如以下者。 一種光阻下層膜形成用組成物，其係含有[A]含有下 述式（1 )所表示之重複單位之聚合物（以下，亦稱爲r 聚 合物」）及[B ]溶劑。201248330 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a composition for forming a photoresist underlayer film and a pattern forming method. [Prior Art] The substrate of the semiconductor device is patterned using a desired pattern. The patterning step of the substrate has a step of, for example, a step of depositing a photosensitive material called a photoresist composition on a substrate to form a photoresist film, and exposing a predetermined field of the photoresist film. a step of developing a photoresist film and removing the exposed portion or the unexposed portion to obtain a photoresist pattern having a predetermined pattern, and using the obtained photoresist pattern as an etching mask and dry etching the substrate Steps, etc. In the patterning step, the exposure light source for exposing the photoresist film uses ultraviolet light such as an ArF excimer laser, but recently, the demand for miniaturization of a large-scale integrated circuit (LSI) has been gradually increased. The necessary resolution also gradually becomes below the wavelength of the exposure light (ultraviolet light). Therefore, if the resolution required is below the wavelength of the light to be exposed, the exposure process tolerance such as the exposure tolerance and the focus tolerance becomes insufficient. In order to compensate for the lack of tolerance of the exposure process, it is effective to reduce the film thickness of the photoresist film and improve the resolution. However, if the film thickness is thin, it is difficult to ensure uranium engraving on the substrate. The worry of the thickness of the photoresist film necessary. Therefore, a review was made on the formation of a photoresist underlayer film between the substrate and the photoresist film, and the photoresist pattern was temporarily transferred to the underlying film to form an underlying film. Figure-5-201248330 After this, the underlying film pattern was formed. The step of transferring the pattern to the substrate as an etch mask. The composition for forming the photoresist underlayer film is preferably composed of a component having etching resistance. For example, it has been proposed to contain a thermosetting phenol novolac or the like having a large carbon content and having an absorption etching. A composition of a polymer of an aromatic ring of energy, a composition containing a polymer having a vinyl naphthalene skeleton, and the like (see JP-A-H20293 and JP-A-2000-143A). A composition containing a styrene derivative or a copolymer of an allylbenzene derivative and a Nortricyclene derivative is also proposed (refer to Japanese Laid-Open Patent Publication No. 2000-65-103). The photoresist underlayer film formed by the composition for forming a layer film has a tendency that the refractive index η at 193 nm is low and the extinction coefficient k tends to be large. Therefore, by containing a polymer having an aromatic ring When the composition forms a photoresist underlayer film and forms a photoresist film containing an acrylic resin as a main component on the underlayer film, the reflectance of the photoresist under the photoresist film becomes higher than that of the photoresist film, and the film may not be formed. Good photoresist pattern Therefore, in order to reduce the reflectance of the photoresist underlayer film, it is necessary to increase the refractive index η of the photoresist underlayer film while also reducing the extinction coefficient k. As a solution to this problem, a sublayer film is known. Addition of an acrylic additive to the composition for forming a composition. However, when an additive of an acrylic type is added to the composition for forming a photoresist underlayer film, there is a problem that the etching resistance of the underlayer film of the photoresist is greatly lowered. [Prior Art Document] [ [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-143937 (Patent Document 3) Japanese Laid-Open Patent Publication No. 2000-143937 (Patent Document 3) OBJECTS TO BE SOLVED BY THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide excellent etching resistance and a low reflectance (that is, a refractive index η is high - an extinction coefficient k is small) a composition for forming a photoresist underlayer film of a photoresist film and a pattern forming method using the same. [Means for Solving the Problem] The present invention has been completed to solve the above problems. A composition for forming a photoresist underlayer film, which comprises [A] a polymer (hereinafter, also referred to as r polymer) containing a repeating unit represented by the following formula (1), and [B] Solvent.
(式（1)中’R1爲羥基、碳數1〜6之烷基、碳數1〜6之院 201248330 氧基、碳數2〜10之醯基或碳數6〜14之芳基。η爲0〜5 之整數。但，η爲2以上時，複數之R1可爲相同亦可爲相 異。X爲碳數1〜20之2價烴基、或碳數1〜20之烷二基 氧基。m爲1〜7之整數。m爲2以上時，複數之X可爲 相同亦可爲相異。又，滿足n + m爲7以下之條件。R2爲 單鍵或碳數1〜4之烷二基。R3爲碳數4〜20之脂環式基 或碳數6〜30之伸芳基。但，上述R3具有之氫原子之一 部分或全部亦可被羥基、碳數1〜6之烷基、烷氧基、醯 基或羥烷基所取代。） 上述式（1)係以下述式（1-1)所表示者爲佳。 【化2】(In the formula (1), 'R1 is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, a 201248330 oxy group having a carbon number of 1 to 6, an fluorenyl group having 2 to 10 carbon atoms or an aryl group having 6 to 14 carbon atoms. It is an integer of 0 to 5. However, when η is 2 or more, the plural R1 may be the same or different. X is a divalent hydrocarbon group having a carbon number of 1 to 20 or an alkanediyloxy group having a carbon number of 1 to 20. The base m is an integer of 1 to 7. When m is 2 or more, the complex X may be the same or different, and satisfy the condition that n + m is 7 or less. R2 is a single bond or a carbon number of 1 to 4. R3 is an alicyclic group having 4 to 20 carbon atoms or an extended aryl group having 6 to 30 carbon atoms. However, some or all of the hydrogen atoms of the above R3 may be partially or wholly by a hydroxyl group and having a carbon number of 1 to 6. The alkyl group, alkoxy group, mercapto group or hydroxyalkyl group is substituted.) The above formula (1) is preferably represented by the following formula (1-1). [Chemical 2]
(式（1-1)中，R1、R2、X、m及η係與上述式（1)同義。R4 爲羥基、碳數1〜6之烷基、碳數1〜6之烷氧基、碳數2 〜6之醯基、或碳數1〜6之羥烷基。1爲0〜3之整數。 但，1爲2以上時，複數之R4可爲相同亦可爲相異。） [Α]聚合物之重量平均分子量係以500〜8，000爲佳。 201248330 該光阻下層膜形成用組成物係以更含有[C]酸產生劑 爲佳。 該光阻下層膜形成用組成物係以更含有[D]交聯劑爲 佳。 本發明之圖型形成方法係具有如下述之步驟，於被加 工基板上塗佈該光阻下層膜形成用組成物而形成光阻下層 膜之步驟、於上述形成有光阻下層膜之被加工基板上使用 光阻組成物形成光阻圖型之步驟、及蝕刻光阻下層膜與被 加工基板之步驟。 [發明之效果] 藉由本發明之光阻下層膜形成用組成物，因蝕刻耐性 優良、折射率η爲高且消光係數k爲小，而可形成反射率 經減低之光阻下層膜。又，依據本發明之圖型形成方法， 可再現性良好地形成圖型形狀優良之圖型。 【實施方式】 以下，說明關於本發明之實施形態，但本發明並非係 受到以下之實施形態所限定者。 <光阻下層膜形成用組成物> 本發明之光阻下層膜形成用組成物係含有[A]聚合物 及[B]溶劑。又，該光阻下層膜形成用組成物係以更含有 [C]酸產生劑、[D]交聯劑爲佳。並且，在不損及本發明之 -9- 201248330 效果內’亦可含有其他任意成分。以下 < [A]聚合物〉 [A]聚合物係含有上述式（丨）所表示之 亦稱爲「重複單位（I)」）的聚合物。 <重複單位（I) > 上述式（1)中，R1爲羥基、碳數1〜6 〜6之烷氧基、碳數2〜10之醯基或碳數 爲0〜5之整數。但，n爲2以上時，複！ 亦可爲相異。X爲碳數1〜20之2價烴2 之垸二基氧基。111爲1〜7之整數。m爲 之X可爲相同亦可爲相異。又，n + m爲 爲單鍵或碳數1〜4之烷二基。R3爲碳數 基或碳數6〜30之伸芳基。但，上述R3 一部分或全部亦可被羥基、碳數1〜6之 醯基或羥烷基所取代。 上述式（1)中，R1所表示之碳數1〜6 舉出甲基、乙基、丙基、異丙基、丁基、 基等。 上述R1所表示之碳數1〜6之烷氧基 氧基、乙氧基、丙氧基、異丙氧基、丁氧 tert-丁氧基等。 詳述關於各成分 重複單位（以下， 之烷基、碳數1 6〜14之芳基。η 玫之R1可爲相同 g、或碳數1〜20 2以上時，複數 1〜7之整數》R2 4〜20之脂環式 具有之氫原子之 烷基、烷氧基、 之烷基，例如可 異 丁基、tert-丁 ，例如可舉出甲 基、異丁氧基、 -10- 201248330 上述R1所表示之碳數2〜10之醯基’例如可舉出乙 醯基等之脂肪族醯基、芳香族醯基等。 上述R1所表示之碳數6〜14之芳基，例如可舉出苯 基、萘基等。 又，上述R1具有之氫原子之一部分或全部亦可被取 代基所取代。上述取代基例如可舉出硝基、胺基、羧基、 磺酸基、锍基、羥甲基、酯基、環氧基等。 上述式（1)中，R1係以羥基爲佳。 上述式（1)中，X所表示之2價之烴基，例如可舉出烷 二基、伸芳基等。又，上述烴基亦可具有取代基。此般取 代基亦可適用上述之R1所亦可具有之取代基之說明。 上述烷二基，例如可舉出亞甲基、伸乙基等。 上述伸芳基係以碳數6〜1 4之伸芳基爲佳，例如可舉 出伸苯基、伸萘基等。 上述X所表示之碳數1〜20之烷二基氧基，例如可舉 出亞甲氧基、乙烯氧基等。 上述式（1)中，R2所表示之烷二基，例如可舉出亞甲 基、伸乙基等。 上述式（1)中，R3所表示之碳數4〜20之脂環式基， 例如可舉出環丁烷二基、環戊烷二基等。 上述R3所表示之碳數6〜30之伸芳基，例如可舉出 伸苯基、伸萘基等。上述脂環式基及伸芳基可具有之取代 基係以羥基爲佳。 上述式ο)中，-r2-r3所表示之基，係以下述式所表示 -11 - 201248330 之基爲佳。尙且，式中*係表示與芳香環之接合部位。 【化3】(In the formula (1-1), R1, R2, X, m and η are synonymous with the above formula (1). R4 is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a fluorenyl group having 2 to 6 carbon atoms or a hydroxyalkyl group having 1 to 6 carbon atoms. 1 is an integer of 0 to 3. However, when 1 is 2 or more, the plural R4 may be the same or different. The weight average molecular weight of the polymer is preferably from 500 to 8,000. 201248330 The composition for forming a photoresist underlayer film preferably contains a [C] acid generator. The composition for forming a photoresist underlayer film preferably contains a [D] crosslinking agent. The pattern forming method of the present invention has the steps of forming the photoresist underlayer film forming composition on the substrate to be processed to form a photoresist underlayer film, and processing the photoresist underlayer film as described above. The step of forming a photoresist pattern using a photoresist composition on the substrate, and the step of etching the photoresist underlayer film and the substrate to be processed. [Effects of the Invention] The composition for forming a photoresist underlayer film of the present invention is excellent in etching resistance, has a high refractive index η, and has a small extinction coefficient k, thereby forming a photoresist underlayer having a reduced reflectance. Further, according to the pattern forming method of the present invention, a pattern having an excellent pattern shape can be formed with good reproducibility. [Embodiment] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments. <Component for forming a photoresist underlayer film> The composition for forming a photoresist underlayer film of the present invention contains the [A] polymer and the [B] solvent. Further, the composition for forming a photoresist underlayer film preferably contains a [C] acid generator and a [D] crosslinking agent. Further, it may contain other optional components without damaging the effects of the present invention -9-201248330. The following <A polymer> The polymer [A] contains a polymer represented by the above formula (丨), which is also referred to as "repeating unit (I)"). <Repeating unit (I) > In the above formula (1), R1 is a hydroxyl group, an alkoxy group having 1 to 6 to 6 carbon atoms, a mercapto group having 2 to 10 carbon atoms, or an integer having a carbon number of 0 to 5. However, when n is 2 or more, it is complex! Can also be different. X is a decyloxy group of a divalent hydrocarbon 2 having 1 to 20 carbon atoms. 111 is an integer of 1 to 7. m is X which may be the same or different. Further, n + m is a single bond or an alkanediyl group having 1 to 4 carbon atoms. R3 is a carbon number group or a aryl group having a carbon number of 6 to 30. However, a part or all of the above R3 may be substituted by a hydroxyl group or a mercapto group having 1 to 6 carbon atoms or a hydroxyalkyl group. In the above formula (1), the carbon numbers 1 to 6 represented by R1 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a group, and the like. The alkoxy group having 1 to 6 carbon atoms represented by the above R1, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy-tert-butoxy group or the like. The repeating unit of each component (hereinafter, an alkyl group and an aryl group having a carbon number of 16 to 14 may be used. When R1 of η rose may be the same g or a carbon number of 1 to 20 2 or more, an integer of 1 to 7) The alkyl group, the alkoxy group or the alkyl group of the hydrogen atom of R2 4 to 20, for example, isobutyl or tert-butyl, for example, methyl, isobutoxy, -10- 201248330 Examples of the fluorenyl group having 2 to 10 carbon atoms represented by the above R1 include an aliphatic fluorenyl group such as an acetamyl group, an aromatic fluorenyl group, etc. The aryl group having 6 to 14 carbon atoms represented by the above R1 may be, for example. Further, a part or all of a hydrogen atom of the above R1 may be substituted with a substituent. Examples of the substituent include a nitro group, an amine group, a carboxyl group, a sulfonic acid group, and a fluorenyl group. In the above formula (1), R1 is preferably a hydroxyl group. In the above formula (1), the divalent hydrocarbon group represented by X may, for example, be an alkanediyl group. Further, the above-mentioned hydrocarbon group may have a substituent. Such a substituent may also be applied to the description of the substituent which the above R1 may have. Examples of the group include a methylene group and an ethylidene group. The above-mentioned aryl group is preferably a aryl group having 6 to 14 carbon atoms, and examples thereof include a phenylene group and an extended naphthyl group. In the above formula (1), the alkanediyl group represented by R2 may, for example, be a methylene group, and the alkylene group represented by R2. In the above formula (1), the alicyclic group having 4 to 20 carbon atoms represented by R3 may, for example, be a cyclobutanediyl group or a cyclopentanediyl group. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group and a naphthyl group. The alicyclic group and the aryl group may have a substituent such as a hydroxyl group. In the above formula ο), - The base represented by r2-r3 is preferably a group represented by the following formula: -11 - 201248330. Further, in the formula, * represents a joint portion with an aromatic ring. [化3]
重複單位（I)係以上述式（1-1)所表示者爲佳。 上述式（1-1)中，R1、R2、X、m及η係與上述式（1)同 義。R4爲羥基、碳數1〜6之烷基或羥烷基。1爲〇〜3之 整數。但，1爲2以上時，複數之R4可爲相同亦可爲相異 〇 上述式（1-1)中，R4所表示之碳數1〜6之烷基，例如 可舉出甲基、乙基、丙基、丁基等。 上述R4所表示之碳數1〜6之烷氧基，例如可舉出與 作爲上述式（1)中之R1所表示之碳數1〜6之烷氧基所例示 -12- 201248330 之基相同之基。 上述R4所表示之碳數2〜6之醯基，例如可舉出乙醯 基等之脂肪族醯基、芳香族醯基等。 上述R4所表示之碳數1〜6之羥烷基，例如可舉出作 爲上述碳數1〜6之烷基中例示之基所具有之氫原子之一 部分或全部被羥基所取代之基等。 上述式（1 -1)中，R4係以羥基、羥甲基爲佳。1係以〇 〜2爲佳。 [A]聚合物之由凝膠滲透層析法（GPC)所得之以聚苯乙 烯換算之重量平均分子量（Mw)係以500〜8,000爲佳，以 1，000〜3,000爲較佳，以1,500〜2,500爲更佳。Mw若未 滿5 00時，而有在光阻下層膜燒成時，其成分揮發而無法 得到所期望之膜厚之情況。另一方面，若Mw超過8,000 時，則有對[B]溶劑之溶解性降低之情況。 < [A]聚合物之合成方法> [A]聚合物之合成方法可舉出，使萘衍生物、醛類及 下述式（2)所表示之醇類在酸觸媒之存在下，在無溶劑或溶 劑中進行加熱之方法、對聚合後之聚合物在酸觸媒存在下 導入下述式（2)所表示之醇之方法等。又，聚合前之單量體 亦可使用例如使萘酚與下述式（2)所表示之醇類反應所得之 以-R2-R3所表示之基受到懸掛之萘酚化合物進行聚合。 HO-R2-R3 · . . (2) -13- 201248330 上述式（2)中，R2及R3係與上述式（1)同義。 上述式（2)所表示之醇類係以1 -金剛烷醇、1 -金剛烷 甲醇、1，3-金剛烷二甲醇、〗，3-金剛烷二醇、1,3,5-金剛烷 三甲醇、1，3,5-金剛烷三醇爲佳。 上述醛類例如可舉出甲醛、多聚甲醛、乙醛、丙醛等 之飽和脂肪族醛類；丙烯醛、甲基丙烯醛等之不飽和脂肪 族醛類；糠醛等之雜環式醛類；苄醛、萘甲醛、蒽醛等之 芳香族醛類等。此等之中以甲醛、多聚甲醛、糠醛爲佳。 尙且，此等可單獨使用1種或將2種以上混合使用。 上述合成方法中之醛類、醇類之使用量係相對於萘衍 生物100質量份，以醛類爲10〜100質量份、醇類爲10〜 1〇〇質量份爲佳。 上述合成方法中所使用之酸觸媒，例如可舉出硫酸、 磷酸、過氯酸等之礦酸類：P-甲苯磺酸等之有機磺酸類； 蟻酸、草酸等之羧酸類等。又，酸觸媒之使用量係根據所 使用之酸類之種類而分別選擇。例如，相對於乙烯合萘_ 1〇〇質量份，以 0.001〜1 0,000質量份爲佳，以 0.01〜 1，000質量份爲更佳。 上述合成方法中之反應溫度係以40 °c〜200 °c爲佳。 反應時間係根據反應溫度而分別選擇，以3 0分〜72小時 爲佳。 本發明之光阻下層膜形成用組成物中，[Α]聚合物之 含有量係將[Α]聚合物與[Β]溶劑之合計作爲100質量％時 -14- 201248330 ，以8〜30質量％爲佳。 < [B ]溶劑〉 本發明之光阻下層膜形成用組成物含有溶解[A]聚合 物之[B ]溶劑。本發明之光阻下層膜形成用組成物所使用 之溶劑，只要係能溶解[A]聚合物者則無特別限定’例如 可舉出乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單-η·丙 基醚、乙二醇單- η-丁基醚等之乙二醇單烷基醚類； 乙二醇單甲基醚乙酸酯、乙二醇單乙基醚乙酸酯、乙 二醇單-η-丙基醚乙酸酯、乙二醇單-η-丁基醚乙酸酯等之 乙二醇單烷基醚乙酸酯類； 二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇 二-η-丙基醚、二乙二醇二-η-丁基醚等之二乙二醇二烷基 醚類； 三乙二醇二甲基醚、三乙二醇二乙基醚等之三乙二醇 二烷基醚類； 丙二醇單甲基醚、丙二醇單乙基醚、丙二醇單-η-丙基 醚、丙二醇單-η-丁基醚等之丙二醇單烷基醚類； 丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二-η-丙基 醚、丙二醇二-η-丁基醚等之丙二醇二烷基醚類； 丙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、丙 二醇單-η -丙基醚乙酸酯、丙二醇單-η -丁基醚乙酸酯等之 丙二醇單烷基醚乙酸酯類； 乳酸甲酯、乳酸乙酯、乳酸η-丙酯、乳酸i·丙酯、乳 -15- 201248330 酸η-丁酯、乳酸i-丁酯等之乳酸酯類； 甲酸甲酯、甲酸乙酯、甲酸η-丙酯、甲酸i-丙酯、甲 酸η-丁酯、甲酸i-丁酯、甲酸η-戊酯、甲酸i-戊酯、乙酸 甲酯、乙酸乙酯、乙酸η-丙酯、乙酸i_丙酯、乙酸η-丁酯 、乙酸i-丁酯、乙酸η-戊酯 '乙酸i-戊酯、乙酸η-己酯、 丙酸甲酯、丙酸乙酯、丙酸η-丙酯、丙酸i-丙酯 '丙酸η-丁酯、丙酸i-丁酯、丁酸甲酯、丁酸乙酯、丁酸η-丙酯、 丁酸i-丙酯、丁酸η-丁酯、丁酸i-丁酯等之脂肪族羧酸酯 類； 羥基乙酸乙酯、2-羥基-2-甲基丙酸乙酯、3-甲氧基-2-甲基丙酸甲酯、2-羥基-3-甲基丁酸甲酯、甲氧基乙酸乙 酯、乙氧基乙酸乙酯、3 -甲氧基丙酸甲酯、3 -乙氧基丙酸 乙酯、3-甲氧基丙酸乙酯、3-甲氧基丙基乙酸酯、3-甲氧 基丁基乙酸酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、3-甲基-3-甲氧基丁基丁酸酯、乙醯乙 酸甲酯、丙酮酸甲酯、丙酮酸乙酯等之其他酯類； 甲苯、茬等之芳香族烴類； 甲基乙基酮、甲基- η-丙基酮、甲基-η-丁基酮' 2_庚 酮、3_庚酮、4-庚酮、環己酮等之酮類； Ν-甲基甲醯胺、Ν，Ν-二甲基甲醯胺、Ν-甲基乙醯胺、 Ν，Ν-二甲基乙醯胺、Ν-甲基吡咯啶酮等之醯胺類； γ-丁內酯等之內酯類等，可適宜選擇使用此等。 此等[Β]溶劑之中，係以丙二醇單甲基醚、丙二醇甲 基醚乙酸酯、乙二醇單乙基醚乙酸酯、乳酸乙酯、乙酸η- -16- 201248330 丁酯、3-乙氧基丙酸乙酯、3-甲氧基丙酸甲酯、2-庚酮、 環己酮、γ-丁內酯爲佳。尙且，此等[B]溶劑係可單獨使用 或將2種以上混合使用。 作爲[Β]溶劑之使用量係以所得之組成物之固形分濃 度成爲5〜80質量％之量爲佳，較佳係成爲5〜40質量％ ，更佳係成爲1 0〜3 0質量％之量。尙且，在此「固形分」 係指本發明之光阻下層膜形成用組成物之溶劑以外之成分 < [C]酸產生劑〉 該光阻下層膜形成用組成物可含有適宜成分之[C]酸 產生劑。[C]酸產生劑係因曝光或加熱而產生酸之成分。 因曝光而產生酸之酸產生劑（以下，稱爲「光酸產生 劑」），例如可舉出二苯基鎭三氟甲烷磺酸鹽、二苯基碘 九氟-Π-丁烷磺酸鹽、二苯基碘芘磺酸鹽、二苯基鎭η-十 二基苯磺酸鹽、二苯基鎳10-樟腦磺酸鹽、二苯基鎮萘磺 酸鹽、二苯基碘六氟銻酸鹽、 雙（4-t-丁基苯基）捵三氟甲烷磺酸鹽、雙（4-t-丁基苯 基）碘九氟-η-丁烷磺酸鹽、雙（4-t-丁基苯基）鐄n-十二基苯 磺酸鹽、雙（4-t-丁基苯基）鎭10-樟腦磺酸鹽、雙（4-t-丁基 苯基）捵萘磺酸鹽、雙（4-t-丁基苯基）鈹六氟銻酸鹽、 三苯基锍三氟甲烷磺酸鹽、三苯基銃九氟- η-丁烷磺酸 鹽、三苯基鏑n-十二基苯磺酸鹽、三苯基毓萘磺酸鹽、三 苯基鏑10-樟腦磺酸鹽 '三苯基锍六氟銻酸鹽、 -17- 201248330 4-羥基苯基·苯基·甲基毓p-甲苯 基·苄基•甲基锍P-甲苯磺酸鹽、 環己基•甲基· 2-側氧基環己基鏑 2 -側氧基環己基二環己基锍三氟甲烷磺 己基二甲基锍三氟甲烷磺酸鹽、 1-萘基二甲基毓三氟甲烷磺酸鹽、 氟甲烷磺酸鹽、4-氰基-1-萘基二甲基鏑 4-氰基-1-萘基二乙基鏑三氟甲烷磺酸丨 二甲基鏑三氟甲烷磺酸鹽、4·硝基-1-萘 烷磺酸鹽、4 -甲基-1-萘基二甲基鏑三氟 基-1-萘基二乙基鏑三氟甲烷磺酸鹽、< 基鏑三氟甲烷磺酸鹽、4-羥基-1-萘基二 酸鹽、 1-(4-羥基萘-1-基）四氫噻吩鑰三氟 甲氧基萘_1_基）四氫噻吩鑰三氟甲烷磺 萘-1-基）四氫噻吩鑰三氟甲烷磺酸鹽、 萘-1-基）四氫噻吩鑰三氟甲烷磺酸鹽、 萘-1-基）四氫噻吩鑰三氟甲烷磺酸鹽、 1-〔 4-(1-甲氧基乙氧基）萘-1-基〕 烷磺酸鹽、1-〔 4-(2-甲氧基乙氧基）萘. 三氟甲烷磺酸鹽、1-(4-甲氧基羰氧基赛 三氟甲烷磺酸鹽、1-(4-乙氧基羰氧基碧 三氟甲烷磺酸鹽、1-(4-η-丙氧基羰氧基 鎗三氟甲烷磺酸鹽、 :磺酸鹽、4-羥基苯 三氟甲烷磺酸鹽、 酸鹽、2-側氧基環 1-萘基二乙基鏑三 三氟甲烷磺酸鹽、 鹽、4-硝基-1-萘基 基二乙基鏑三氟甲 甲烷磺酸鹽、4-甲 羥基-1-萘基二甲 乙基鏑三氟甲烷磺 甲烷磺酸鹽、1-(4-酸鹽、1-(4-乙氧基 卜（4-甲氧基甲氧基 1-(4-乙氧基甲氧基 四氫噻吩鑰三氟甲 .1 -基〕四氫噻吩鎗 ? -1 -基）四氫噻吩鑰 卜1 -基）四氫噻吩鑰 ;萘-1·基）四氫噻吩 -18- 201248330 l-(4-i-丙氧基羰氧基萘-1-基）四氫噻吩鑰三氟甲烷磺 酸鹽、l-(4-n-丁氧基羰氧基萘-1-基）四氫噻吩鎰三氟甲烷 磺酸鹽、1-(4-t-丁氧基羰氧基萘-1-基）四氫噻吩鑰三氟甲 烷磺酸鹽、1-〔 4-(2-四氫呋喃氧基）萘-1-基〕四氫噻吩鎗 三氟甲烷磺酸鹽、1-〔4-(2-四氫吡喃氧基）萘-1-基〕四氫 噻吩鎗三氟甲烷磺酸鹽、 1-(4-苄氧基）四氫噻吩鑰三氟甲烷磺酸鹽、1_(萘基乙 醯甲基）四氫噻吩鑰三氟甲烷磺酸鹽 等之鑰鹽系光酸產生劑類； 苯基雙（三氯甲基）-s-三嗪、4-甲氧基苯基雙（三氯甲基 )-s-三嗪、1-萘基雙（三氯甲基）-s-三嗪等之含鹵素化合物 系光酸產生劑類； 1，2-重氮萘醌-4-磺醯氯、1，2-重氮萘醌-5-磺醯氯、 2,3,4,4’-四羥基二苯甲酮之1，2-重氮萘醌-4-磺酸酯或1，2-重氮萘醌-5-磺酸酯等之重氮酮化合物系光酸產生劑類； 4-參苯甲醯甲基颯、荚基苯甲醯甲基颯、雙（苯基磺醯 基）甲烷等之碾化合物系光酸產生劑類： 安息香酸甲苯磺醯鹽、五倍子酚之參（三氟甲烷磺酸 鹽）、硝基苄基-9,10-二乙氧基蔥-2-磺酸鹽 '三氟甲烷磺醯 基雙環[2,2，1]庚-5-烯-2,3-二碳二醯胺、N-羥基丁二醯亞 胺三氟甲烷磺酸鹽、1，8-萘二羧酸醯亞胺三氟甲烷磺酸鹽 等之磺酸化合物系光酸產生劑類等。 此等光酸產生劑之中，以二苯基鐫三氟甲烷磺酸鹽、 二苯基鎮九氟-η-丁烷磺酸鹽、二苯基鋏芘磺酸鹽、二苯基 -19- 201248330 碘η-十二基苯磺酸鹽、二苯基鎮10-樟腦磺酸鹽、二苯基 鎖萘磺酸鹽、雙（4-1-丁基苯基）碘三氟甲烷磺酸鹽、雙（4-t-丁基苯基）碘九氟-η-丁烷磺酸鹽、雙（4-t-丁基苯基）碘n-十二基苯磺酸鹽、雙（4-t-丁基苯基）鎮10-樟腦磺酸鹽、雙 (4-t-丁基苯基）锁萘磺酸鹽爲佳。上述光酸產生劑可單獨 使用或將2種以上混合使用。 因加熱而產生酸之酸產生劑（以下，稱爲「熱酸產生 劑j )，例如可舉出2,4,4,6-四溴環己二烯酮、安息香酸甲 苯磺醯鹽、2-硝基苄基甲苯磺醯鹽、烷基磺酸鹽類等。此 等熱酸產生劑可單獨使用或將2種以上混合使用。 尙且，亦可倂用光酸產生劑與熱酸產生劑作爲[C]酸 產生劑。 [C]酸產生劑之配合量係對每光阻下層膜形成用組成 物之固形分100質量份而言，以10質量份以下爲佳，以 〇. 1〜5質量份爲更佳。本發明之光阻下層膜形成用組成物 藉由含有[C]酸產生劑，可有效地引起包含常溫之較低溫 下之各聚合物之分子鏈間的交聯反應。 < [D]交聯劑〉 該光阻下層膜形成用組成物可含有適宜成分之[D]交聯 劑。[D]交聯劑係具有防止使下層膜形成用組成物硬化所得 之光阻下層膜與形成於此光阻下層膜之上之光阻被膜之間 之互混’並具有防止光阻下層膜之龜裂之作用的成分。此 般[D]交聯劑可使用多核酚類，各種市售之硬化劑等。 -20- 201248330 上述多核酚類例如可舉出4,4’-聯苯基二醇、4,4:-亞 甲基雙酚、4,4’-亞乙基雙酚、雙酚A等之2核酚類； 4,4’，4”-亞甲基參酚、4,4’-〔 1- { 4-(1-[4-羥基苯基]-1-甲 基乙基）苯基}亞乙基〕雙酚等之3核酚類；酚醛清漆等 之聚酚類等。此等多核酚類之中，可舉出4,4’-〔卜[4- (1-[4·羥基苯基]-1-甲基乙基）苯基丨亞乙基〕雙酚、酚醛 清漆等。上述多核酚類可單獨使用或將2種以上混合使用 〇 又，上述硬化劑例如可舉出2,3·甲伸苯基二異氰酸酯 、2,4-甲伸苯基二異氰酸酯、3,4-甲伸苯基二異氰酸酯、 3,5-甲伸苯基二異氰酸酯、4，4’-二苯基甲烷二異氰酸酯、 六亞甲基二異氰酸酯、1，4-環己烷二異氰酸酯等之二異氰 酸酯類等。 市售品例如可舉出Epikote 812、同815、同826、同 828、同 834、同 836、同 871、同 1001、同 1004、同 1 007、同 1 009、同 1031(以上、Yuka Shell Epoxy 公司製） 、Araldite 6600、同 6700、同 68 00、同 5 0 2、同 607 1、 同 6084、同 6097、同 6099(以上、Ciba-Geigy 公司製）、 D.E.R.331、同 332、同 333、同 661、同 644、同 667(以 上、Dow Chemicals公司製）等之環氧化合物；Cymel 300 、同 301、同 303、同 350、同 370、同 771、同 325、同 327、同 703、同 7 12' 同 701、同 272、同 202、M y c o a t 506、同5 08(以上、三井氰胺公司製）等之三聚氰胺系硬化 齊ij ； Cymel 1123、同 1123-10、同 1128、Mycoat 102、 -21 - 201248330 同105、同106、同130(以上、三井氰胺公司製）等之 胍胺系硬化劑；C y m e 1 1 1 7 0、同1 1 7 2 (以上、三井 公司製）、Nikalac N-2702(三和化學公司製）等之乙炔 硬化劑等。此等硬化劑之中係以三聚氰胺系硬化劑、 脲系硬化劑等爲佳。上述硬化劑可單獨使用或將2種 混合使用。又，亦可倂用多核酌類與硬化劑作爲交聯， 交聯劑之配合量係對每光阻下層膜形成用組成物 形分1 〇 0質量份而言，以5 0質量份以下爲佳。 <其他之任意成分> 本發明之下層膜形成用組成物可含有[A]聚合物， 溶劑、[C]酸產生劑及[D]交聯劑以外之其他之任意成 其他之任意成分係以具有防止光阻下層膜與光阻被膜 之互混、提升下層膜形成用組成物之塗佈性等之作用 分爲佳。上述其他之任意成分例如可舉出黏合劑樹脂 射線吸收劑、界面活性劑等。 上述黏合劑樹脂可使用各種熱可塑性樹脂或熱硬 樹脂。 上述熱可塑性樹脂，例如可舉出 聚乙烯、聚丙烯、聚-1-丁烯、聚-1-戊烯、聚-1_ 、聚-1-庚嫌、聚-1-辛稀、聚-1-癸儲、聚-1-十一嫌、 1-十四烯、聚-1-十六烯、聚-1-十八烯、聚乙烯環烷 α -烯烴系聚合物類：聚-I，4 -戊二烯、聚-1，4 -己二烯、 1，5-己二烯等之非共役二烯系聚合物類； 苯並 氰胺 脲系 乙炔 以上 刹。 之固 .[Β] 分。 之間 之成 、放 化性 己烯 聚-等之 聚_ -22- 201248330 α，β-不飽和醛系聚合物類；聚（甲基乙烯酮）、聚（芳香 族乙烯酮）、聚（環狀乙烯酮）等之α,β-不飽和酮系聚合物類 ;(甲基）丙烯酸、α-氯丙烯酸、（甲基）丙烯酸鹽、（甲基）丙 烯酸酯、（甲基）丙烯酸鹵化物等之α，β-不飽和羧酸或其衍 生物之聚合物類；聚（甲基）丙烯酸酐、無水馬來酸之共聚 物等之α，β-不飽和羧酸酐之聚合物類；亞甲基丙二酸二酯 、伊康酸二酯等之不飽和多元性羧酸酯之聚合物類； 山梨酸酯、黏康酸酯等之二烯烴羧酸酯之聚合物類； (甲基）丙烯酸硫酯、α-氯丙烯酸硫酯等之α，β-不飽和羧酸 硫酯之聚合物類；（甲基）丙烯腈、α-氯丙烯腈等之（甲基） 丙烯腈或其衍生物之聚合物類；（甲基）丙烯醯胺、Ν，Ν·二 甲基（甲基）丙烯醯胺等之（甲基）丙烯醯胺或其衍生物之聚 合物類；苯乙烯基金屬化合物之聚合物類；乙烯氧金屬化 合物之聚合物類； 聚亞胺類：聚苯醚、聚-1，3-二氧戊環、聚環氧乙烷、 聚四氫呋喃、聚四氫吡喃等之聚醚類；聚硫化物類；聚磺 醯胺類；聚狀類；耐綸66、耐綸1〜耐綸12等之聚醯胺 類；脂肪族聚酯、芳香族聚酯、脂環族聚酯、聚碳酸酯等 之聚酯類：聚脲類；聚颯類；聚吖嗪類；聚胺類；聚芳香 族酮類；聚醯亞胺類；聚苯并咪唑類；聚苯并惡唑類；聚 苯并噻唑類；聚胺基三唑類：聚噁二唑類；聚吡唑類；聚 四唑類；聚喹喔啉類；聚三嗪類；聚苯並嗪酮類；聚喹啉 類；聚二氮蔥類等。 又，上述熱硬化性樹脂係因加熱而硬化而變得不溶於 -23- 201248330 溶劑，具有防止所得之光阻下層膜，與於其上形成之光阻 被膜之間之互混之作用的成分，亦可較佳地使用作爲黏合 劑樹脂。此般熱硬化性樹脂，例如可舉出熱硬化性丙烯酸 系樹脂類、酚樹脂類、脲樹脂類、三聚氰胺樹脂類、胺基 系樹脂類、芳香族烴樹脂類、環氧樹脂類、醇酸樹脂類等 。此等熱硬化性樹脂之中，以脲樹脂類、三聚氰胺樹脂類 、芳香族烴樹脂類等爲佳。 上述黏合劑樹脂可單獨使用或將2種以上混合使用。 黏合劑樹脂之配合量係對每光阻下層膜形成用組成物之固 形分1 00質量份而言，以20質量份以下爲佳，以1 0質量 份以下爲佳。 上述放射線吸收劑，例如可舉出油溶性染料、分散 染料、鹼性染料、次甲基系染料、吡唑系染料、咪唑系 染料、羥偶氮系染料等之染料類；胭脂木酯衍生物、降 胭脂木酯、芪、4,4’-二胺基底衍生物、香豆素衍生物、 吡唑啉衍生物等之螢光增白劑類；羥偶氮系染料、 TINUVIN 23 4(Ciba-Geigy 公司製）、TINUVIN 1130(Ciba-Geigy公司製）等之紫外線吸收劑類；蔥衍生物、蒽醌衍生 物等之芳香族化合物等。此等放射線吸收劑可單獨使用或 將2種以上混合使用。放射線吸收劑之配合量係對每光阻 下層膜形成用組成物之固形分1 〇〇質量份而言，以1 00質 量份以下爲佳，以50質量份以下爲更佳。 上述界面活性劑係具有改良塗佈性、條紋性、濕潤性 、顯像性等之作用的成分。此般界面活性劑，例如可舉出 -24- 201248330 聚氧乙烯月桂醚、聚氧乙烯硬脂酸醚、聚氧乙烯油醇醚、 聚氧乙烯-η-辛基苯基醚、聚氧乙烯-η-壬基苯基醚、聚乙 二醇二月桂酸酯、聚乙二醇二硬脂酸酯等之非離子系界面 活性劑等。 市售品可舉出例如ΚΡ341(信越化學工業公司製）、 Polyflow Νο.75、同No.9 5(以上、共榮社油脂化學工業公 司製）、Eft op EF101 ' 同 EF204、同 EF303 ' 同 EF352(以 上，Tokem Products 公司製）、Megafac F171、同 F172、 同 Fl*73(以上，大日本油墨化學工業公司製）、Fluorad FC430、同 FC431、同 FC135、同 FC93(以上，住友 3M 公 司製）、Asahiguide AG710、Suflon S382、同 SC101、同 SCI 02 ' 同 SC103、同 SC104、同 SC105、同 SC106(以上 ，旭硝子公司製）等。此等界面活性劑可單獨使用或將2 種以上混合使用。界面活性劑之配合量係對每光阻下層膜 形成用組成物之固形分100質量份而言，以15質量份以 下爲佳，以1 0質量份以下爲更佳。 並且，作爲上述以外之其他之任意成分，例如可舉出 保存安定劑、消泡劑、接著助劑等。 <圖型形成方法> 本發明之圖型形成方法係具有下述步驟，（1)於被加工 基板上塗佈如請求項1之光阻下層膜形成用組成物而形成 光阻下層膜之步驟、（2)於形成有上述光阻下層膜之被加工 基板上使用光阻組成物形成光阻圖型之步驟、及（3)蝕刻光 -25- 201248330 阻下層膜與被加工基板之步驟。以下，詳細說明關於各個 步驟。 [步驟（1)] 基板例如可使用矽晶圓、以鋁被覆之晶圓等。下層膜 組成物之塗佈可以旋轉塗佈、流延塗佈、輥塗佈等之適宜 之方法實施。其後，藉由曝光及/或加熱使塗膜硬化。曝 光之放射線可因應所使用之光酸產生劑之種類，而適宜選 自可見光線、紫外線、遠紫外線、X線、電子線、γ線、 分子線、離子束等。在下層膜組成物含有光酸產生劑且進 行曝光之情況時，在常溫下亦可有效地使塗膜硬化。又， 加熱溫度係於90°C〜3 50°C之程度爲佳，更佳爲200°C〜 300°c之程度。在下層膜組成物含有熱酸產生劑之情況時 ，例如，即使於90°c〜1 50°c之程度下亦可有效地使塗膜 硬化。本步驟所形成之光阻下層膜之膜厚係以0.1 μηι〜 5 μ m爲佳。 [步驟（2)] 光阻圖型形成步驟中，在藉上述光阻下層膜形成步驟 所形成之光阻下層膜上使用光阻組成物溶液進行圖型形成 。此般圖型形成步驟可舉出具有如下述步驟者，例如，（2-1)塗佈光阻組成物，將所得之塗膜預烘烤而形成光阻被膜 之光阻被膜形成步驟、（2-2)使上述光阻被膜經由光罩選擇 性地進行曝光之曝光步驟、（2-3)對已曝光之光阻被膜進行 -26- 201248330 顯像之顯像光阻被膜形成步驟。以下說明關於上述圖型形 成步驟所具有之上述各步驟。 (2-1)光阻被膜形成步驟 在光阻下層膜上，使光阻被膜能成爲既定之膜厚般塗 佈光阻組成物溶液。其後，進行預烘烤使溶劑揮發而形成 光阻被膜。此時預烘烤之溫度係可因應光阻組成物之種類 等而適宜調整，以3 0 °C〜2 0 (TC之程度爲佳，以5 0 °C:〜 150°C爲更佳。 上述光阻組成物例如可舉出，含有光酸產生劑之正型 或負型之化學增幅型光阻組成物、由鹼可溶性樹脂與醌二 叠氮化物系感光劑所構成之正型光阻組成物、由鹼可溶性 樹脂與交聯劑所構成之負型光阻組成物等。 使光阻被膜形成於光阻下層膜上時所使用之光阻組成 物，其固形分濃度係以5〜50質量％之程度爲佳，於光阻 被膜之形成前，例如以孔徑〇.2μιη程度之濾器進行過濾。 尙且，本步驟中亦可直接使用市售之光阻組成物。 (2-2)曝光步驟 曝光所用之放射線，可因應光阻組成物所使用之光酸 產生劑之種類而適宜選自可見光線、紫外線、遠紫外線、 X線、電子線、γ線、分子線、離子束等，較佳爲遠紫外 線，特別以 KrF準分子雷射（24 8nm)、ArF準分子雷射 (193nm)、F2準分子雷射（波長157nm)、Kr2準分子雷射（ -27- 201248330 波長147nm)、ArKr準分子雷射（波長134nm)、極紫外線（ 波長13nm等）等爲佳。 (2-3)顯像步驟 藉由將曝光後之光阻被膜顯像、洗淨、乾燥，使既定 之光阻圖型形成。本步驟中，爲了使解像度、圖型輪廓、 顯像性等提升，於曝光後且顯像前亦可進行後烘烤。 本步驟所使用之顯像液可因應使用之光阻組成物之種 類而適宜選擇，作爲正型化學增幅型光阻組成物或含有鹼 可溶性樹脂之正型光阻組成物之情況時之顯像液，例如可 舉出氫氧化鈉、氫氧化鉀、碳酸鈉、矽酸鈉、偏矽酸鈉、 氨、乙基胺、η-丙基胺、二乙基胺 '二-n-丙基胺、三乙基 胺、甲基二乙基胺、二甲基.乙醇胺、三乙醇胺、氫氧化 四甲基銨、氫氧化四乙基銨、吡咯、哌啶、膽鹼、1 ,8 -二 吖雙環[5·4·0]-7-~|--烯、1，5-二吖雙環[4.3·0]-5-壬烯等之 鹼性水溶液。又’亦可對此等鹼性水溶液適量添加水溶性 有機溶劑’例如甲醇、乙醇等之醇類，或界面活性劑。 尙且’作爲圖型形成步驟，可使用經由上述（2-2)曝光 步驟多次後於上述（2-3)顯像步驟中使用複數之顯像液形成 微細圖型之方法（例如，參照特開2 0 0 8 - 2 9 2 9 7 5號公報）， 或經由複數次上述（2-1)〜（2-3)之步驟而形成微細圖型之 方法（例如，參照特開20 1 1 -05 3 643號公報）。又，亦可使 用不經由奈米壓印微影法等之上述（2-3)顯像步驟的圖型形 成方法（例如’參照特開2 0 1 0 - 2 6 2 9 8 0號公報）。 -28- 201248330 [蝕刻步驟（iii)] 將所得之光阻圖型作爲光罩，使用例如氧電獎等之氣 體電漿’進行光阻下層膜之蝕刻。並且，將上述光阻下層 膜作爲光罩而進行基板之蝕刻。藉此，可得到既定之圖型 [實施例] 以下，基於實施例及比較例具體地說明本發明，但本 發明並非係受到此等實施例及比較例所限定者。 [重量平均分子量（Mw)]:The repeating unit (I) is preferably represented by the above formula (1-1). In the above formula (1-1), R1, R2, X, m and η are the same as the above formula (1). R4 is a hydroxyl group, an alkyl group having 1 to 6 carbon atoms or a hydroxyalkyl group. 1 is an integer of 〇~3. However, when 1 is 2 or more, the plural R4 may be the same or may be a different alkyl group having 1 to 6 carbon atoms represented by R4 in the above formula (1-1), and examples thereof include methyl group and ethyl group. Base, propyl, butyl, and the like. The alkoxy group having 1 to 6 carbon atoms represented by the above R4 is, for example, the same as the group of -12-201248330 exemplified as the alkoxy group having a carbon number of 1 to 6 represented by R1 in the above formula (1). The basis. The fluorenyl group having 2 to 6 carbon atoms represented by the above R4 may, for example, be an aliphatic fluorenyl group such as an acetyl group or an aromatic fluorenyl group. The hydroxyalkyl group having 1 to 6 carbon atoms represented by the above R4 is, for example, a group in which one or all of the hydrogen atoms which are exemplified in the alkyl group having 1 to 6 carbon atoms is substituted with a hydroxyl group. In the above formula (1 -1), R4 is preferably a hydroxyl group or a hydroxymethyl group. The 1 series is preferably 〇 〜2. [A] The weight average molecular weight (Mw) of the polymer obtained by gel permeation chromatography (GPC) in terms of polystyrene is preferably 500 to 8,000, preferably 1,000 to 3,000, and preferably 1,500. ~2,500 is better. When the Mw is less than 50,000, and the film is fired under the photoresist, the components are volatilized and the desired film thickness cannot be obtained. On the other hand, when Mw exceeds 8,000, the solubility in the [B] solvent may be lowered. <[A] Method for synthesizing polymer> [A] A method for synthesizing a polymer, wherein a naphthalene derivative, an aldehyde, and an alcohol represented by the following formula (2) are present in the presence of an acid catalyst A method of heating in a solvent-free or solvent-free manner, a method of introducing an alcohol represented by the following formula (2) in the presence of an acid catalyst, and the like. In addition, for example, a naphthol compound obtained by reacting an anthracene represented by -R2-R3 with a naphthol compound obtained by reacting an alcohol represented by the following formula (2) with a naphthol may be used. HO-R2-R3 · (2) -13- 201248330 In the above formula (2), R2 and R3 are synonymous with the above formula (1). The alcohol represented by the above formula (2) is 1-adamantanol, 1-adamantane methanol, 1,3-adamantane dimethanol, ruthenium, 3-adamantanediol, 1,3,5-adamantane. Trimethanol, 1,3,5-adamantane triol is preferred. Examples of the aldehydes include saturated aliphatic aldehydes such as formaldehyde, paraformaldehyde, acetaldehyde, and propionaldehyde; unsaturated aliphatic aldehydes such as acrolein and methacrolein; and heterocyclic aldehydes such as furfural. An aromatic aldehyde such as benzaldehyde, naphthaldehyde or furfural. Among them, formaldehyde, paraformaldehyde, and furfural are preferred. In addition, these may be used alone or in combination of two or more. The amount of the aldehydes and alcohols used in the above synthesis method is preferably 10 to 100 parts by mass based on 100 parts by mass of the naphthalene derivative, and 10 to 1 part by mass of the alcohol. Examples of the acid catalyst used in the above-mentioned synthesis method include mineral acids such as sulfuric acid, phosphoric acid, and perchloric acid; organic sulfonic acids such as P-toluenesulfonic acid; and carboxylic acids such as formic acid and oxalic acid. Further, the amount of the acid catalyst used is selected depending on the type of the acid to be used. For example, it is preferably 0.001 to 1,000,000 parts by mass, more preferably 0.01 to 1,000 parts by mass, per part by mass of the ethylene naphthalene. The reaction temperature in the above synthesis method is preferably from 40 ° C to 200 ° C. The reaction time is selected depending on the reaction temperature, preferably from 30 minutes to 72 hours. In the composition for forming a photoresist underlayer film of the present invention, the content of the [Α] polymer is a total of [Α] polymer and [Β] solvent as 100% by mass - 14 to 201248330, and is 8 to 30 mass. % is better. <[B] Solvent> The composition for forming a photoresist underlayer film of the present invention contains a solvent [B] in which the [A] polymer is dissolved. The solvent used for the composition for forming a photoresist underlayer film of the present invention is not particularly limited as long as it can dissolve the [A] polymer, and examples thereof include ethylene glycol monomethyl ether and ethylene glycol monoethyl ether. Ethylene glycol monoalkyl ethers such as ethylene glycol mono-η·propyl ether, ethylene glycol mono-η-butyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl Ethylene acetate, ethylene glycol mono-η-propyl ether acetate, ethylene glycol mono-η-butyl ether acetate, etc. ethylene glycol monoalkyl ether acetate; diethylene glycol II Diethylene glycol dialkyl ethers such as methyl ether, diethylene glycol diethyl ether, diethylene glycol di-η-propyl ether, diethylene glycol di-η-butyl ether; Triethylene glycol dialkyl ethers such as diol dimethyl ether and triethylene glycol diethyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-η-propyl ether, propylene glycol single a propylene glycol monoalkyl ether such as η-butyl ether; a propylene glycol dialkyl group such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol di-η-propyl ether or propylene glycol di-η-butyl ether; Ethers; propylene glycol monomethyl ether acetate Propylene glycol monoethyl ether acetate, propylene glycol mono-η-propyl ether acetate, propylene glycol mono-η-butyl ether acetate, etc.; propylene glycol monoalkyl ether acetate; methyl lactate, lactate B Esters, lactic acid η-propyl ester, lactic acid i. propyl ester, milk -15- 201248330 acid η-butyl ester, lactate i-butyl ester and other lactate; methyl formate, ethyl formate, η-propyl formate, I-propyl formate, η-butyl formate, i-butyl formate, η-amyl formate, i-amyl formate, methyl acetate, ethyl acetate, η-propyl acetate, i-propyl acetate, Η-butyl acetate, i-butyl acetate, η-pentyl acetate 'i-pentyl acetate, η-hexyl acetate, methyl propionate, ethyl propionate, η-propyl propionate, propionic acid i -propyl ester y-butyl propionate, i-butyl propionate, methyl butyrate, ethyl butyrate, η-propyl butyrate, i-propyl butyrate, η-butyl butyrate, butyl An aliphatic carboxylic acid ester such as i-butyl ester; ethyl hydroxyacetate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxy-2-methylpropionate, 2-hydroxyl Methyl 3-methylbutanoate, ethyl methoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Ester, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-methoxypropyl acetate, 3-methoxybutyl acetate, 3-methyl-3 -Methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, methyl acetate, pyruvic acid Other esters such as methyl ester and ethyl pyruvate; aromatic hydrocarbons such as toluene and hydrazine; methyl ethyl ketone, methyl-η-propyl ketone, methyl-η-butyl ketone' 2_g Ketones such as ketone, 3-hexanone, 4-heptanone, cyclohexanone, etc.; Ν-methylformamide, hydrazine, hydrazine-dimethylformamide, hydrazine-methylacetamide, hydrazine, hydrazine - a decylamine such as dimethylacetamide or hydrazine-methylpyrrolidone; a lactone such as γ-butyrolactone, or the like, which can be appropriately selected and used. Among these [Β] solvents, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, ethylene glycol monoethyl ether acetate, ethyl lactate, acetic acid η- -16-201248330 butyl ester, Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, and γ-butyrolactone are preferred. Further, these [B] solvents may be used singly or in combination of two or more. The amount of the solvent used is preferably from 5 to 80% by mass, preferably from 5 to 40% by mass, more preferably from 10 to 30% by mass, based on the amount of the solid content of the obtained composition. The amount. In addition, the "solid content" refers to a component other than the solvent of the composition for forming a photoresist underlayer film of the present invention. [C] Acid generator> The composition for forming a photoresist underlayer film may contain an appropriate component. [C] Acid generator. The [C] acid generator is a component which generates an acid due to exposure or heating. An acid generator (hereinafter referred to as a "photoacid generator") which generates an acid by exposure, and examples thereof include diphenylsulfonium trifluoromethanesulfonate and diphenyliodonium nonafluorofluorene-butanesulfonic acid. Salt, diphenyl iodonium sulfonate, diphenyl 鎭 η-dodecyl benzene sulfonate, diphenyl nickel 10-camphorsulfonate, diphenyl sulfonate, diphenyl iodine Fluoride, bis(4-t-butylphenyl)phosphonium trifluoromethanesulfonate, bis(4-t-butylphenyl)iodohexafluoro-η-butanesulfonate, double (4 -t-butylphenyl)鐄n-dodecylbenzenesulfonate, bis(4-t-butylphenyl)indole 10-camphorsulfonate, bis(4-t-butylphenyl)phosphonium Naphthalene sulfonate, bis(4-t-butylphenyl)phosphonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium nonafluoro-n-butanesulfonate, three Phenylindole n-dodecylbenzenesulfonate, triphenylsulfonium naphthalenesulfonate, triphenylsulfonium 10-camphorsulfonate triphenylsulfonium hexafluoroantimonate, -17- 201248330 4-hydroxyl Phenyl phenyl·methyl 毓 p-tolyl benzyl • methyl hydrazine P-toluene sulfonate, cyclohexyl • methyl • 2-oxocyclohexyl fluorene 2 - side oxygen Cyclohexyldicyclohexylfluorenetrifluoromethanesulfonyldimethyltrifluoromethanesulfonate, 1-naphthyldimethyltrifluoromethanesulfonate, fluoromethanesulfonate, 4-cyano-1- Naphthyldimethylhydrazine 4-cyano-1-naphthyldiethylsulfonium trifluoromethanesulfonate dimethyl dimethyl trifluoromethanesulfonate, 4·nitro-1-naphthene sulfonate, 4 -Methyl-1-naphthyldimethylsulfonium trifluoro-1-naphthyldiethylphosphonium trifluoromethanesulfonate, <-based trifluoromethanesulfonate, 4-hydroxy-1-naphthyl Diacid salt, 1-(4-hydroxynaphthalen-1-yl)tetrahydrothiophene trifluoromethoxynaphthalene-1-yl)tetrahydrothiophene fluorotrifluoromethane-1-yl)tetrahydrothiophene Fluoromethanesulfonate, naphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, naphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, 1-[4-(1-methoxy Ethyloxy)naphthalen-1-yl]alkanesulfonate, 1-[4-(2-methoxyethoxy)naphthalene. Trifluoromethanesulfonate, 1-(4-methoxycarbonyloxyl Kesai trifluoromethanesulfonate, 1-(4-ethoxycarbonyloxybitrifluoromethanesulfonate, 1-(4-η-propoxycarbonyloxy gun trifluoromethanesulfonate, : Sulfonate, 4-hydroxyl Benzene trifluoromethanesulfonate, acid salt, 2-sided oxy ring 1-naphthyldiethyl fluorene trifluoromethane sulfonate, salt, 4-nitro-1-naphthyldiethyl sulfonium Fluoromethanesulfonate, 4-methylhydroxy-1-naphthalenyldimethylethyltrifluoromethanesulfonate, 1-(4-acidate, 1-(4-ethoxyb (4-A) Oxymethoxy-methoxy 1-(4-ethoxymethoxytetrahydrothiophene trifluoromethyl-1-indolyl)tetrahydrothiophene gun? -1 -yl)tetrahydrothiophene-di- 1 -yl)tetrahydrothiophene Key; naphthalene-1·yl)tetrahydrothiophene-18- 201248330 l-(4-i-propoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene trifluoromethanesulfonate, l-(4- N-butoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene fluorinated trifluoromethanesulfonate, 1-(4-t-butoxycarbonyloxynaphthalen-1-yl)tetrahydrothiophene Methanesulfonate, 1-[4-(2-tetrahydrofuranyloxy)naphthalen-1-yl]tetrahydrothiophene trifluoromethanesulfonate, 1-[4-(2-tetrahydropyranyloxy)naphthalene -1-yl]tetrahydrothiophene trifluoromethanesulfonate, 1-(4-benzyloxy)tetrahydrothiophene trifluoromethanesulfonate, 1-(naphthylethylidenemethyl)tetrahydrothiophene Key salt of fluoromethanesulfonate Photoacid generators; phenylbis(trichloromethyl)-s-triazine, 4-methoxyphenylbis(trichloromethyl)-s-triazine, 1-naphthylbis(trichloro) a halogen-containing compound such as methyl)-s-triazine or the like; a photoacid generator; 1,2-diazonaphthoquinone-4-sulfonium chloride, 1,2-diazonaphthoquinone-5-sulfonyl chloride, 1,3,4,4'-tetrahydroxybenzophenone 1,2-diazonaphthoquinone-4-sulfonate or 1,2-diazonaphthoquinone-5-sulfonate The compound is a photoacid generator; a 4-guanidinium methylhydrazine, a podent benzamidine methyl hydrazine, a bis(phenylsulfonyl)methane or the like; the milled compound is a photoacid generator: benzoic acid toluene Sulfonium salt, gallic phenolic ginseng (trifluoromethanesulfonate), nitrobenzyl-9,10-diethoxy onion-2-sulfonate 'trifluoromethanesulfonylbicyclo[2,2, 1]hept-5-ene-2,3-dicarbodiamine, N-hydroxybutylimine trifluoromethanesulfonate, 1,8-naphthalene dicarboxylate, imidium trifluoromethanesulfonate The sulfonic acid compound is a photoacid generator or the like. Among these photoacid generators, diphenyl sulfonium trifluoromethane sulfonate, diphenyl hydride nonafluoro-η-butane sulfonate, diphenyl sulfonate, diphenyl-19 - 201248330 Iodine η-dodecylbenzenesulfonate, diphenyl Zhen 10-camphorsulfonate, diphenylsernaphthalenesulfonate, bis(4-1-butylphenyl)iodotrifluoromethanesulfonic acid Salt, bis(4-t-butylphenyl)iodo nonafluoro-η-butane sulfonate, bis(4-t-butylphenyl)iodo-n-dodecylbenzenesulfonate, double (4 -t-butylphenyl) is preferably a 10-camphorsulfonate or a bis(4-t-butylphenyl)sodium naphthalenesulfonate. These photoacid generators may be used singly or in combination of two or more. An acid generator which generates an acid by heating (hereinafter referred to as "thermal acid generator j") may, for example, be 2,4,4,6-tetrabromocyclohexadienone or benzoic acid toluenesulfonate, 2 - Nitrobenzyl toluene sulfonium salt, alkyl sulfonate, etc. These thermal acid generators may be used singly or in combination of two or more kinds thereof, and may be produced by using a photoacid generator and a thermal acid. The agent is used as the [C] acid generator. [C] The amount of the acid generator is preferably 10 parts by mass or less, based on 100 parts by mass of the composition per layer of the underlayer film forming composition. It is more preferable that the composition for forming a photoresist underlayer film of the present invention can effectively cause cross-linking between molecular chains of each polymer containing a normal temperature at a lower temperature by containing a [C] acid generator. [D] Crosslinking agent> The composition for forming a photoresist underlayer film may contain a [D] crosslinking agent as a suitable component. [D] The crosslinking agent has a property of preventing formation of a composition for forming an underlayer film. The mutual interference between the underlying film of the photoresist and the photoresist film formed on the underlying film of the photoresist and has a crack preventing the underlayer of the photoresist For the [D] crosslinking agent, polynuclear phenols, various commercially available curing agents, etc. can be used. -20- 201248330 The above polynuclear phenols include, for example, 4,4'-biphenyl diol, 4 , 4:-methylene bisphenol, 4,4'-ethylene bisphenol, bisphenol A, etc. 2 core phenols; 4,4',4"-methylene phenol, 4,4'- a 3-nuclear phenol such as 1-{4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl}ethylidene bisphenol; a polyphenol such as a novolak or the like. Among these polynuclear phenols, 4,4'-[Bu [4-(1-[4-hydroxyphenyl]-1-methylethyl)phenyl fluorene] bisphenol, phenolic Varnish, etc. The above-mentioned polynuclear phenols may be used singly or in combination of two or more kinds thereof. Examples of the above-mentioned curing agent include 2,3·methylphenylene diisocyanate, 2,4-methylphenylene diisocyanate, and 3,4-. Diisocyanate such as methyl phenyl diisocyanate, 3,5-methylphenyl diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexane diisocyanate Classes, etc. Commercial products include, for example, Epikote 812, 815, 826, 828, 834, 836, 871, 1001, 1004, 007, 009, 1031 (above, Yuka Shell Epoxy Company system), Araldite 6600, the same 6700, the same 68 00, the same 5 0 2, the same 607 1, the same 6084, the same 6097, the same 6099 (above, Ciba-Geigy company), DER331, the same 332, the same 333, Epoxy compounds such as 661, 644, 667 (above, Dow Chemicals); Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 7 12' Same as 701, 272, 202, M ycoat 506, 508 (above, Mitsui Cyanamide), etc. Melamine-based hardening qi; Cymel 1123, same 1123-10, same 1128, Mycoat 102, -21 - 201248330 A amide-based hardener such as 105, 106, and 130 (above, Mitsui Cyanamide); C yme 1 1 1 7 0, same as 1 1 7 2 (above, manufactured by Mitsui Co., Ltd.) An acetylene hardener such as Nikalac N-2702 (manufactured by Sanwa Chemical Co., Ltd.). Among these hardeners, a melamine-based curing agent, a urea-based curing agent, and the like are preferred. The above hardeners may be used singly or in combination of two. Further, a multi-core type and a curing agent may be used as a crosslinking agent, and the amount of the crosslinking agent is not more than 50 parts by mass per part of the composition for forming the underlayer film for the photoresist. good. <Other optional components> The composition for forming a layer film of the present invention may contain any other optional components other than the [A] polymer, the solvent, the [C] acid generator, and the [D] crosslinking agent. It is preferable to have an effect of preventing the mutual adhesion of the photoresist underlayer film and the photoresist film, and improving the coatability of the composition for forming the underlayer film. Examples of the other optional components include a binder resin radiation absorber, a surfactant, and the like. As the above binder resin, various thermoplastic resins or thermosetting resins can be used. Examples of the thermoplastic resin include polyethylene, polypropylene, poly-1-butene, poly-1-pentene, poly-1_, poly-1-glycan, poly-1-octyl, poly-1. - 癸, poly-1-11, 1-tetradecene, poly-1-hexadecene, poly-1-octadecene, polyethylene cycloalkane α-olefin polymer: poly-I, Non-co-diene diene polymers such as 4-pentadiene, poly-1,4-hexadiene, 1,5-hexadiene, etc.; benzocyanamide urea-based acetylene. Solid [[]] points. Interpolymerization, radionization, hexene polymerization, etc. _ -22- 201248330 α,β-unsaturated aldehyde polymer; poly(methyl ketene), poly(aromatic ketene), poly( α,β-unsaturated ketone polymers such as cyclic ketene; (meth)acrylic acid, α-chloroacrylic acid, (meth) acrylate, (meth) acrylate, (meth) acrylate halogenated a polymer of α,β-unsaturated carboxylic acid or a derivative thereof; a polymer of α,β-unsaturated carboxylic anhydride such as a copolymer of poly(meth)acrylic anhydride or anhydrous maleic acid; a polymer of an unsaturated polycarboxylic acid ester such as a methylene malonic acid diester or an itaconic acid diester; a polymer of a diolefin carboxylate such as a sorbate or a mucic acid ester; a polymer of α,β-unsaturated carboxylic acid thioester such as acrylate acrylate or α-chloro acrylate, or (meth) acrylonitrile such as (meth)acrylonitrile or α-chloroacrylonitrile or a polymer of a derivative thereof; a (meth) acrylamide or a derivative thereof (meth) acrylamide, hydrazine, hydrazine dimethyl (meth) acrylamide or the like Biopolymers; polymers of styryl metal compounds; polymers of ethylene oxide metal compounds; polyimines: polyphenylene ether, poly-1,3-dioxolane, polyethylene oxide Polyethers such as polytetrahydrofuran and polytetrahydropyran; polysulfides; polysulfonamides; polycondensation; polyamines such as nylon 66, nylon 1 to nylon 12; aliphatic Polyesters such as polyester, aromatic polyester, alicyclic polyester, polycarbonate, etc.: polyureas; polyfluorenes; polypyridazines; polyamines; polyaromatic ketones; polyimine Polybenzimidazoles; polybenzoxazoles; polybenzothiazoles; polyaminotriazoles: polyoxadiazoles; polypyrazoles; polytetrazoles; polyquinoxalines; Polytriazines; polybenzoxazinones; polyquinolines; polydiazoonium and the like. Further, the thermosetting resin is hardened by heating and is insoluble in the solvent of -23-201248330, and has a component for preventing the resulting photoresist from being intermingled with the photoresist film formed thereon. It can also be preferably used as a binder resin. Examples of the thermosetting resin include thermosetting acrylic resins, phenol resins, urea resins, melamine resins, amine resins, aromatic hydrocarbon resins, epoxy resins, and alkyds. Resin and the like. Among these thermosetting resins, urea resins, melamine resins, aromatic hydrocarbon resins and the like are preferred. These binder resins may be used singly or in combination of two or more. The amount of the binder resin to be added is preferably 20 parts by mass or less, and more preferably 10 parts by mass or less, based on 100 parts by mass of the solid content of the composition for forming a film under the photoresist. Examples of the radiation absorbing agent include dyes such as oil-soluble dyes, disperse dyes, basic dyes, methine dyes, pyrazole dyes, imidazole dyes, and hydroxyazo dyes; Fluorescent whitening agents such as carmine ester, anthraquinone, 4,4'-diamine base derivatives, coumarin derivatives, pyrazoline derivatives, etc.; hydroxyazo dyes, TINUVIN 23 4 (Ciba - an ultraviolet absorber such as a Geigy company, a TINUVIN 1130 (manufactured by Ciba-Geigy Co., Ltd.), an aromatic compound such as an onion derivative or an anthracene derivative, or the like. These radiation absorbers may be used singly or in combination of two or more. The amount of the radiation absorbing agent is preferably 1 part by mass or less, more preferably 50 parts by mass or less, per part by mass of the solid content of the composition for forming a lower layer film. The above surfactant has a component which has an effect of improving coatability, streaking property, wettability, and developing property. Such a surfactant may, for example, be -24-201248330 polyoxyethylene lauryl ether, polyoxyethylene stearate, polyoxyethylene oleyl ether, polyoxyethylene-η-octylphenyl ether, polyoxyethylene a nonionic surfactant such as η-nonylphenyl ether, polyethylene glycol dilaurate or polyethylene glycol distearate. Commercially available products include, for example, ΚΡ341 (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow Νο.75, the same as No. 9 5 (above, Kyoei Oil & Fat Chemical Co., Ltd.), Eft op EF101 'with EF204, and EF303'. EF352 (above, manufactured by Tokem Products), Megafac F171, same as F172, same as Fl*73 (above, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), Fluorad FC430, FC431, FC135, and FC93 (above, Sumitomo 3M) ), Asahiguide AG710, Suflon S382, SC101, SCI 02', SC103, SC104, SC105, SC106 (above, Asahi Glass Co., Ltd.). These surfactants may be used singly or in combination of two or more. The amount of the surfactant to be added is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, per 100 parts by mass of the solid content of the composition for forming the underlayer film. Further, examples of the other optional components other than the above include a storage stabilizer, an antifoaming agent, and a secondary auxiliary agent. <Graphic Forming Method> The pattern forming method of the present invention has the following steps: (1) applying a photoresist underlayer film forming composition of claim 1 to a substrate to be processed to form a photoresist underlayer film a step of (2) forming a photoresist pattern on the substrate on which the photoresist underlayer film is formed, using a photoresist composition, and (3) etching light - 25-201248330 underlayer film and substrate to be processed step. Hereinafter, the respective steps will be described in detail. [Step (1)] For the substrate, for example, a germanium wafer, a wafer coated with aluminum, or the like can be used. The application of the underlayer film composition can be carried out by a suitable method such as spin coating, cast coating, roll coating or the like. Thereafter, the coating film is cured by exposure and/or heating. The radiation of exposure may be selected from visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular line, ion beam, etc. depending on the type of photoacid generator to be used. When the underlying film composition contains a photoacid generator and is exposed to light, the coating film can be effectively cured at normal temperature. Further, the heating temperature is preferably from 90 ° C to 3 50 ° C, more preferably from 200 ° C to 300 ° C. In the case where the underlayer film composition contains a thermal acid generator, for example, the coating film can be effectively cured even at a temperature of from 90 ° C to 150 ° C. The film thickness of the photoresist underlayer film formed in this step is preferably 0.1 μηι to 5 μm. [Step (2)] In the photoresist pattern forming step, pattern formation is performed using a photoresist composition solution on the photoresist underlayer film formed by the above-mentioned photoresist underlayer film forming step. In the pattern forming step, for example, a step of forming a photoresist film by pre-baking the resulting coating film to form a photoresist film, such as (2-1) coating a photoresist composition, is exemplified ( 2-2) an exposure step of selectively exposing the photoresist film through a photomask, and (2-3) a developing photoresist film forming step of performing -26-201248330 development on the exposed photoresist film. The above respective steps relating to the above-described pattern forming step will be described below. (2-1) Photoresist film forming step On the photoresist underlayer film, the photoresist film can be coated with a photoresist composition as a predetermined film thickness. Thereafter, prebaking is performed to volatilize the solvent to form a photoresist film. The prebaking temperature at this time may be appropriately adjusted depending on the type of the photoresist composition, etc., preferably from 30 ° C to 2 0 (the degree of TC is preferably 50 ° C: 150 ° C is more preferable). Examples of the photoresist composition include a positive- or negative-type chemically amplified photoresist composition containing a photo-acid generator, and a positive-type photoresist composed of an alkali-soluble resin and a quinonediazide-based sensitizer. a composition, a negative-type photoresist composition composed of an alkali-soluble resin and a crosslinking agent, etc. The photoresist composition used when the photoresist film is formed on the photoresist underlayer film has a solid concentration of 5~ The degree of 50% by mass is preferably such that it is filtered by a filter having a pore size of about 2 μm before the formation of the photoresist film. Further, a commercially available photoresist composition can be directly used in this step. The radiation used for the exposure step exposure may be selected from the group consisting of visible light, ultraviolet light, far ultraviolet light, X-ray, electron beam, γ-ray, molecular line, ion beam, etc. depending on the type of photo-acid generator used in the photoresist composition. , preferably far ultraviolet, especially with KrF excimer laser (24 8 Nm), ArF excimer laser (193 nm), F2 excimer laser (wavelength 157 nm), Kr2 excimer laser (-27-201248330 wavelength 147 nm), ArKr excimer laser (wavelength 134 nm), extreme ultraviolet (wavelength) (13), etc. (2-3) The developing step is to form a predetermined photoresist pattern by developing, cleaning, and drying the exposed photoresist film. In this step, in order to make the resolution and the image Type contour, development, etc., can be post-baked after exposure and before development. The developing solution used in this step can be selected according to the type of photoresist composition used as positive chemical growth. Examples of the developing solution in the case of a resist composition or a positive resist composition containing an alkali-soluble resin include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium citrate, sodium metasilicate, and ammonia. , ethylamine, η-propylamine, diethylamine 'di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide Ammonium, tetraethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-dioxabicyclo[5·4·0]-7-~|--ene, 1,5- An alkaline aqueous solution of bisbicyclo[4.3.0]-5-pinene or the like. It is also possible to add a water-soluble organic solvent such as an alcohol such as methanol or ethanol or a surfactant in an appropriate amount to the alkaline aqueous solution. And 'as a pattern forming step, a method of forming a fine pattern using a plurality of developing liquids in the above (2-3) developing step after the (2-2) exposure step a plurality of times (for example, reference Open 2 0 0 8 - 2 9 2 9 7 5), or a method of forming a fine pattern by the above steps (2-1) to (2-3) (for example, refer to the special opening 20 1 1 -05 3 643 bulletin). Further, a pattern forming method that does not pass the above-described (2-3) developing step such as a nanoimprint lithography method (for example, 'refer to Japanese Patent Publication No. 2 0 1 0 - 2 6 2 9 8 0) may be used. . -28-201248330 [Etching step (iii)] The obtained photoresist pattern is used as a mask, and the photoresist underlayer film is etched using a gas plasma such as an oxygen award. Further, the underlayer of the photoresist is used as a mask to etch the substrate. Thus, a predetermined pattern can be obtained. [Examples] Hereinafter, the present invention will be specifically described based on examples and comparative examples, but the present invention is not limited by the examples and comparative examples. [Weight average molecular weight (Mw)]:
Mw係使用東曹公司製之GPC管柱（G2000HXL: 2支 、G3000HXL: 1支），在流量：l.OmL/分，溶出溶劑：四 氫呋喃，管柱溫度：4 0 °C之分析條件下，藉由以單分散聚 苯乙烯爲標準之凝膠滲透層析法（檢測器：示差折射計）而 測定。 < [A]成分之合成〉 [合成例1] 對具備溫度計之可拆式燒瓶，在氮環境下，添加2:7-二羥基萘1〇〇質量份、福馬林 30質量份、p-甲苯磺酸1 質量份、及丙二醇單甲基醚150質量份，進行攪拌之同時 並以80°C使其聚合6小時而得到反應溶液。對反應溶液添 -29- 201248330 加1·金剛烷醇43質量份，在80°C下攪拌24小 J時。其後’Mw system uses GPC pipe column (G2000HXL: 2 pieces, G3000HXL: 1 piece) made by Tosoh Corporation, under the condition of flow rate: 1.0 mL/min, dissolution solvent: tetrahydrofuran, column temperature: 40 °C. It was determined by gel permeation chromatography (detector: differential refractometer) using monodisperse polystyrene as a standard. <Synthesis of [A] component> [Synthesis Example 1] A separable flask equipped with a thermometer was added with 2 parts by mass of 2:7-dihydroxynaphthalene, 30 parts by weight of fumarin, and p- in a nitrogen atmosphere. 1 part by mass of toluenesulfonic acid and 150 parts by mass of propylene glycol monomethyl ether were stirred and polymerized at 80 ° C for 6 hours to obtain a reaction solution. To the reaction solution, -29-201248330 plus 43 mass portions of 1-adamantanol was added, and the mixture was stirred at 80 ° C for 24 hours. Subsequent’
將反應溶液以乙酸η-丁酯1 〇〇質量份稀釋，L 以多量之水/ 甲醇（質量比：1/2)混合溶劑洗禮有機層。其後，將溶劑餾 除而得到聚合物（A-1)。聚合物（A-1)之Mw爲1 800。 [合成例2〜7 ] 除了將表1中記載之萘衍生物及醇以既定量配合以外 ，與合成例1與同樣地操作而得到聚合物（A-2)〜（A-6)及 (a-1 )。將所得之各聚合物之Mw總合揭載於表1。 表1 [Α] 成分 萘衍生物 醇 物性値 種類 使用量 (質量份） 種類 使用量 (質量份) Mw 合成例1 Α-1 2,7-二羥基萘 100 1-金剛烷醇 43 1,800 合成例2 Α-2 2,7-二羥基萘 100 1，3·金剛烷二醇 43 1,900 合成例3 Α-3 2J-二羥基萘 100 1,3,5-金剛烷三醇 43 2,000 合成例4 Α-4 2,7-二羥基萘 100 1-金剛烷甲醇 43 2,200 合成例5 Α-5 2,7-二羥基萘 100 1,3-金剛院二甲醇 43 1,900 合成例6 Α-6 2,7-二羥基萘 100 1，3,5-金岡IJ院三甲醇 43 2,000 合成例7 a-1 2,7-二羥基萘 100 1,800 < ArF用光阻組成物之調製> [合成例8] 對裝有迴流管之可拆式燒瓶，在氮氣流下，添加8-甲 基-8-1-丁氧基羰基甲氧基羰基四環[4.4.0.I2’5.〗7’1 Q]十二- 3-烯（單量體（a))29份、8-甲基-8-羥基四環[4·4·0.12’5·17’1()] -30- 201248330 十二-3-烯（單量體（b))l〇份、無水馬來酸（單量體（£；))18份 、2,5 -二甲基-2,5 -己二醇二丙烯酸酯4份、t -十二基硫醇 1份、偶氮雙異丁腈4份、及1，2 -二乙氧基乙烷60份，進 行攪拌之同時並以70°C使其聚合6小時。其後，將反應溶 液注入於大量之η-己烷/i·丙醇（質量比=1/1)混合溶劑中而 使樹脂凝固。將已凝固樹脂以該混合溶劑數次洗淨後，進 行真空乾燥。源自上述單量體（a)、（b)及（c)之各重複單位 之莫耳比爲64: 18: 18，Mw爲27,000(收率60%)。 <光阻下層膜形成用組成物之調製> [實施例1 ] 使聚合物（A-l)10份溶解於丙二醇單甲基醚1〇〇份而 得到混合溶液。其後，藉由將此混合溶液以孔徑〇. 1 μιη之 膜濾器進行過濾而得到光阻下層膜形成用組成物。將此光 阻下層膜形成用組成物作爲塗佈液使用並進行以下之各種 評價。 [實施例2〜6及比較例1] 除了取到聚合物（Α-1)而使用了表2中記載之聚合物 成分以外，與實施例1同樣地進行操作而得到各光阻下層 膜形成用組成物。將所得之光阻下層膜形成用組成物作爲 塗佈液使用並進行以下之各種評價。 [實施例7] -31 - 201248330 使聚合物（A-1)10份、作爲[C]酸產生劑之（cd)二苯基 鎮三氟甲烷磺酸鹽5份、作爲[D]交聯劑之（D-l)Nikalac N-2702(三和化學公司製）1〇份溶解於丙二醇單甲基醚ι〇〇 份而得到混合溶液。其後，藉由將此混合溶液以孔徑 〇 · 1 μηι之膜濾器過濾而得到光阻下層膜形成用組成物。將 此光阻下層膜形成用組成物作爲塗佈液使用並進行以下之 各種評價。 [實施例8〜9] 除了取代聚合物（Α-1)而使用了表2中記載之聚合物 成分以外’與實施例7同樣進行操作而得到各光阻下層膜 形成用組成物。將得之光阻下層膜形成用組成物作爲塗佈 液使用並進行以下之各種評價。 <光阻圖型之形成> 於直徑8吋之矽晶圓上，將各光阻下層膜形成用組成 物以旋轉塗佈法進行塗佈。其次，在加熱板上以1 8 0 °C加 熱60秒鐘。接著，以3 5 0°C加熱60秒鐘，而形成膜厚 0.3 μπι之下層膜。其次，於此下層膜上旋轉塗佈3層光阻 製程用中間層組成物溶液（NFC SOG0 8 0、JSR公司製）後， 在加熱板上以200°C加熱60秒鐘。接著，以30(TC加熱60 秒鐘，而形成膜厚〇.〇5 μηι之中間層被膜。其次，在此中 間層被膜上旋轉塗佈上述調製所得之光阻組成物，在加熱 板上以130°C預烘烤90秒鐘，而形成膜厚0.2μιη之光阻被 -32- 201248330 膜。 其次，使用NIKON公司製之ArF準分子雷射曝光裝 置（透鏡開口數〇·78、曝光波長193nm)，經由光罩圖型， 以最佳曝光時間進行曝光。其次，在1 3 0°C之加熱板上預 烘烤90秒鐘後，使用2.38質量％濃度之氫氧化四甲蕋銨 水溶液，將光阻被膜以25°C顯像1分鐘。其後，進行水洗 、乾燥，而得到形成有正型光阻圖型之光阻被膜。 <評價> [圖型形狀] 藉由掃描型電子顯微鏡觀察形成有正型光阻圖型之光 阻被膜中之圖型形狀並藉由以下之基準進行評價。被觀察 之圖型形狀爲矩形之情況時則爲良好（A)，爲矩形以外之 形狀（例如T-top、浮渣等）時則爲不良（B)。 [防駐波效果] 藉由掃描型電子顯微鏡觀察有無對形成有正型光阻圖 型之上述光阻被膜之駐波之影響，並藉由以下之基準評價 防駐波效果。在圖型側面上若無發現來自下層膜之反射所 成之駐波之情況時爲良好（A)，發現駐波之情況時則爲不 良（B)。 [光學特性] 於直徑8吋之矽晶圓上旋轉塗佈各光阻下層膜形成用 -33- 201248330 組成物。其後，在加熱板上以3 00 °C加熱120秒鐘’而形成 膜厚0.3μΐΏ之下層膜。對於此下層膜，使用J.A.WOOLLAM 公司製之分光橢圓偏光計VUV-VASE，測定波長193 nm中 之折射率（η)與吸光度（消光係數（k))。 [蝕刻耐性] 藉由旋轉塗佈法，於直徑8吋之矽晶圓上，旋轉塗佈 光阻下層膜形成用組成物，而形成膜厚3 00nm之下層膜。 其後，對此下層膜進行蝕刻處理（壓力：〇.〇3T〇rr、高頻電 力：3000W' Ar/CF4 = 40/100 seem、基板溫度：20°C)，並 測定蝕刻處理後之下層膜之膜厚。且，由膜厚之減少量與 處理時間之關係算出蝕刻速率（nm/分）。尙且，蝕刻速率 爲時評價爲蝕刻耐性優良。 尙且，折射率（η)若在1 .40以上1.60以下之範圍內， 於ArF曝光光阻步驟中，作爲防反射膜可判斷爲具有充分 機能者。又，消光係數（k)若在0.25以上0.40以下之範圍 內，於ArF曝光光阻步驟中，作爲防反射膜可判斷爲具有 充分機能者。 -34- 201248330 表2 [A] [C] 成分 [D] 成分 評價 圖型 形狀 防駐波 效果 折射率 ⑹ 消光係數 (k) 蝕刻速率 (nm/分） 實施例1 A-1 A A 1.49 0.39 0.90 實施例2 A-2 - - A A 1.47 0.40 0.91 實施例3 A-3 - - A A 1.46 0.38 0.90 實施例4 A-4 - - A A 1.50 0.39 0.89 實施例5 A-5 - A A 1.48 0.40 0.91 實施例6 A-6 - - A A 1.50 0.39 0.90 實施例7 A-1 C-1 D-1 A A 1.51 0.40 0.89 實施例8 A-2 C-1 D-1 A A 1.48 0.41 0.90 實施例9 A-3 C-1 D-1 A A 1.47 0.39 0.89 比較例1 a-1 - B B 1.38 0.45 1.00 由表2可清楚得知，實施例1〜9之光阻下層膜形成 用組成物與比較例1之光阻下層膜形成用組成物相比，可 形成蝕刻耐性優良’且經反射率減低（即，折射率η爲高 ，消光係數k爲小）之光阻下層膜。又，與比較例1相比 ’使用實施例1〜9之光阻下層膜形成用組成物所形成之 光阻圖型，其圖型形狀更爲優良。 [產業上之可利用性] 本發明之光阻下層膜形成用組成物係可適宜作爲形成 於微影製程中之微細加工，特別係高積體電路元件之製造 中較適宜之多層光阻製程中所使用之下層膜用之材料。又 ，本發明之圖型形成方法係可適宜作爲微影製程中之微細 加工，特別係高積體電路元件之製造中較佳之多層光阻製 -35- 201248330 程中之圖型形成方法。 -36-The reaction solution was diluted with 1 part by mass of η-butyl acetate, and the organic layer was washed with a large amount of water/methanol (mass ratio: 1/2) mixed solvent. Thereafter, the solvent was distilled off to obtain a polymer (A-1). The Mw of the polymer (A-1) was 1,800. [Synthesis Examples 2 to 7] Polymers (A-2) to (A-6) and (in the same manner as in Synthesis Example 1) were obtained, except that the naphthalene derivatives and alcohols described in Table 1 were blended in a quantitative manner. A-1). The Mw sum of the obtained polymers is shown in Table 1. Table 1 [Α] Component Naphthalene Derivative Alcohol Property 使用 Species Usage (Parts by mass) Species Usage (Parts by mass) Mw Synthesis Example 1 Α-1 2,7-Dihydroxynaphthalene 100 1-adamantanol 43 1,800 Synthesis Example 2 Α-2 2,7-dihydroxynaphthalene 100 1,3·adamantanediol 43 1,900 Synthesis Example 3 Α-3 2J-dihydroxynaphthalene 100 1,3,5-adamantane triol 43 2,000 Synthesis Example 4 Α -4 2,7-dihydroxynaphthalene 100 1-adamantane methanol 43 2,200 Synthesis Example 5 Α-5 2,7-dihydroxynaphthalene 100 1,3-golden dimethanol 43 1,900 Synthesis Example 6 Α-6 2,7 -Dihydroxynaphthalene 100 1,3,5-Jinoka IJ Institute Trimethanol 43 2,000 Synthesis Example 7 a-1 2,7-Dihydroxynaphthalene 100 1,800 <Preparation of photoresist composition for ArF> [Synthesis Example 8] For a separable flask equipped with a reflux tube, 8-methyl-8-1-butoxycarbonylmethoxycarbonyltetracyclo[4.4.0.I2'5. 7'1 Q] was added under a nitrogen stream. Twelve 3-ene (singly (a)) 29 parts, 8-methyl-8-hydroxytetracyclo[4·4·0.12'5·17'1()] -30- 201248330 12-3 - alkene (singly (b)), aliquots, anhydrous maleic acid (single amount (£;)) 18 parts, 2,5-dimethyl-2,5-hexanediol diacrylate 4 parts , t - Two parts of a mercaptan, 4 parts of azobisisobutyronitrile, and 1,2 - diethoxyethane 60 parts, the feed line while stirring at 70 ° C and polymerized for 6 hours. Thereafter, the reaction solution was poured into a mixed solvent of a large amount of η-hexane/i·propanol (mass ratio = 1/1) to solidify the resin. The solidified resin was washed several times with the mixed solvent, and then vacuum dried. The molar ratio derived from each of the above units (a), (b) and (c) was 64:18:18 and Mw was 27,000 (yield 60%). <Preparation of composition for forming a photoresist underlayer film> [Example 1] 10 parts of the polymer (A-1) was dissolved in 1 part of propylene glycol monomethyl ether to obtain a mixed solution. Then, the mixed solution was filtered through a membrane filter having a pore size of 1 μm to obtain a composition for forming a photoresist underlayer film. The composition for forming a photoresist underlayer film was used as a coating liquid, and the following various evaluations were carried out. [Examples 2 to 6 and Comparative Example 1] In the same manner as in Example 1, except that the polymer component described in Table 2 was used as the polymer (Α-1), the formation of each resist underlayer film was obtained. Use the composition. The obtained composition for forming a photoresist underlayer film was used as a coating liquid, and various evaluations were performed as follows. [Example 7] -31 - 201248330 10 parts of the polymer (A-1) and 5 parts of (cd) diphenyltrifluoromethanesulfonate as the [C] acid generator, as [D] crosslinked (Dil) Nikalac N-2702 (manufactured by Sanwa Chemical Co., Ltd.) was dissolved in propylene glycol monomethyl ether oxime to obtain a mixed solution. Then, the mixed solution was filtered through a membrane filter having a pore size of 〇 1 μm to obtain a composition for forming a photoresist underlayer film. The composition for forming a photoresist underlayer film was used as a coating liquid, and various evaluations were carried out as follows. [Examples 8 to 9] In the same manner as in Example 7 except that the polymer component described in Table 2 was used instead of the polymer (Α-1), each of the resist underlayer film forming compositions was obtained. The composition for forming a photoresist film under the photoresist was used as a coating liquid, and various evaluations were carried out as follows. <Formation of photoresist pattern> Each of the photoresist underlayer film forming compositions was applied by spin coating on a wafer having a diameter of 8 Å. Next, it was heated at 180 ° C for 60 seconds on a hot plate. Subsequently, it was heated at 350 ° C for 60 seconds to form a film having a film thickness of 0.3 μm. Then, three layers of the intermediate layer composition solution for photoresist (NFC SOG0 80, manufactured by JSR) were spin-coated on the underlayer film, and then heated at 200 ° C for 60 seconds on a hot plate. Next, the intermediate layer film having a film thickness of 〇.5 μηι was formed by heating at 30 °C for 60 seconds. Next, the photoresist composition obtained by the above-mentioned preparation was spin-coated on the intermediate layer film, and the composition was heated on a hot plate. The film was pre-baked at 130 ° C for 90 seconds, and a photoresist having a film thickness of 0.2 μm was formed into a film of -32 - 201248330. Next, an ArF excimer laser exposure device manufactured by NIKON Co., Ltd. (lens opening number 〇 78, exposure wavelength) was used. 193 nm), exposure was performed at the optimum exposure time via a mask pattern. Secondly, after prebaking on a hot plate at 130 ° C for 90 seconds, a 2.38 mass % aqueous solution of tetramethylammonium hydroxide was used. The resist film was developed at 25 ° C for 1 minute. Thereafter, it was washed with water and dried to obtain a photoresist film having a positive resist pattern. <Evaluation> [Graph shape] by scanning The pattern shape in the resist film formed with the positive resist pattern was observed by a type electron microscope and evaluated by the following criteria. When the shape of the pattern to be observed is a rectangle, it is good (A), which is a rectangle. Other shapes (such as T-top, dross, etc.) are bad (B) [Anti-Standing Effect] The influence of the standing wave of the photoresist film on which the positive resist pattern is formed is observed by a scanning electron microscope, and the anti-standing wave effect is evaluated by the following criteria. It is good (A) if no standing wave is formed from the reflection of the underlying film on the side surface, and is bad (B) when the standing wave is found. [Optical characteristics] on a wafer having a diameter of 8 吋The composition of -33-201248330 for forming a lower layer of each photoresist was spin-coated, and then heated at 300 ° C for 120 seconds on a hot plate to form a film having a film thickness of 0.3 μΐΏ. For the underlayer film, use JAWOOLLAM company's spectroscopic ellipsometer VUV-VASE, measuring the refractive index (η) and absorbance (extinction coefficient (k)) at a wavelength of 193 nm. [etching resistance] by spin coating method, diameter 8 吋On the crucible wafer, a composition for forming a photoresist underlayer film is spin-coated to form a film having a film thickness of 300 nm. Thereafter, the underlayer film is etched (pressure: 〇.〇3T〇rr, high-frequency power) :3000W' Ar/CF4 = 40/100 seem, substrate temperature: 20 ° C), and measured The film thickness of the underlayer film after the etching treatment was performed, and the etching rate (nm/min) was calculated from the relationship between the amount of decrease in film thickness and the processing time. Moreover, the etching rate was evaluated as excellent in etching resistance. (n) in the range of 1.40 or more and 1.60 or less, in the ArF exposure resist step, it can be judged that it has sufficient function as an antireflection film. Further, the extinction coefficient (k) is in the range of 0.25 or more and 0.40 or less. In the ArF exposure resist step, it can be judged that it has sufficient function as an antireflection film. -34- 201248330 Table 2 [A] [C] Component [D] Component evaluation pattern shape anti-standing wave effect refractive index (6) extinction coefficient (k) etching rate (nm/min) Example 1 A-1 AA 1.49 0.39 0.90 Example 2 A-2 - - AA 1.47 0.40 0.91 Example 3 A-3 - - AA 1.46 0.38 0.90 Example 4 A-4 - - AA 1.50 0.39 0.89 Example 5 A-5 - AA 1.48 0.40 0.91 Example 6 A-6 - - AA 1.50 0.39 0.90 Example 7 A-1 C-1 D-1 AA 1.51 0.40 0.89 Example 8 A-2 C-1 D-1 AA 1.48 0.41 0.90 Example 9 A-3 C-1 D-1 AA 1.47 0.39 0.89 Comparative Example 1 a-1 - BB 1.38 0.45 1.00 It is clear from Table 2 that the photoresist underlayer film forming compositions of Examples 1 to 9 and the photoresist underlayer film of Comparative Example 1 were formed. A photoresist underlayer film having excellent etching resistance and having a reduced reflectance (that is, a refractive index η is high and an extinction coefficient k is small) can be formed as compared with the composition. Further, in comparison with Comparative Example 1, the photoresist pattern formed by using the composition for forming a photoresist underlayer film of Examples 1 to 9 has a more excellent pattern shape. [Industrial Applicability] The composition for forming a photoresist underlayer film of the present invention can be suitably used as a microfabrication process formed in a lithography process, particularly a multilayer photoresist process suitable for the manufacture of a high-integral circuit component. The material used for the underlying film. Further, the pattern forming method of the present invention can be suitably used as a microfabrication process in a lithography process, and is particularly a pattern forming method in a multilayer photoresist process in the manufacture of a high-integral circuit component. -36-