1263263 (1) 九、發明說明 【發明所屬之技術領域】 本發明係有關照相石版技術領域中圖型微細化用之被 覆形成劑及使用其之微細圖型之形成方法。更詳細者係有 關因應近年來半導體裝置之集成化、微小化所得之圖型微 細化用之被覆形成劑及使用其之微細圖型之形成方法。 Φ 【先前技術】 半導體裝置、液晶裝置等電子零件之製造中，於基板 上進行蝕刻處理時，利用活性放射線之感應亦即敏放射線 光阻於基板上設置被膜（光阻層），再將此以活性放射線 選擇性進行照射，曝光後，進行顯像處理，使光阻層選擇 性溶解去除後，於基板上形成畫像圖型（光阻圖型），以 此做爲保護層（外罩圖型），於基板上形成通孔圖型、溝 道圖型等、接觸用圖型等各種圖型之照相凸版技術被使用 ⑩之。 近年來，提高半導體裝置之集成化、微小化傾向，有 關此等圖型之彤成亦積極微細化，目前被要求圖型寬度爲 0·20μηι以下之超微細加工者，外罩圖型形成所使用之活 性光線亦利用KrF、ArF、F2準分子雷射光、雷子線等短 波長之照射光，有關做爲外罩圖型形成材料之光阻材料亦 進行硏究•開發具有因應此等照射光之物性者。 除因應此光阻材料面之照超微細化之對策外，亦由圖 型形成方法之面進行硏究·開發超越具光阻材料解像度界 -5- (2) 1263263 限之圖型微細化技術。 如：特開平5 — 1 667 1 7號公報（專利文獻1 )中被揭 示於塗佈於基板上之圖型形成用光阻形成脫膜圖型後，將 該圖型形成用光阻與混合之混合生成用光阻塗佈於基板全 面後，使混合層形成於圖型形成用光阻側壁〜表面後，去 除該混合生成用光阻之非混合部份，意圖使該混合層尺寸 份微細化之脫模圖型形成方法。又，特開平5 — 24 1 3 48號 φ 公報（專利文獻2 )中揭示，於形成含有酸產生劑之光阻 圖型之基板上，於酸之存在下使不溶化樹脂進行被覆後， 熱處理之後，於該樹脂由光阻擴散酸後於樹脂與光阻圖型 界面附近形成一定厚度之光阻後，顯像之後，去除酸來擴 散之樹脂部份，意圖使上述一定尺寸厚度份之微細化圖型 形成方法。 惟，此等方法不易調整形成於光阻圖型側壁之層的厚 度，晶圓面內之熱依存性爲十數nm/°C之極大數者，目前 •半導體裝置製造所使用之加熱裝置中極不易使晶圓面內均 勻保持，圖型尺寸明顯不均之問題產生。 另外，以熱處理等使光阻圖型流動化進行圖型尺寸微 細化之方法亦爲公知者。如：特開平i _ 3 〇 7 2 2 8號公報（ 專利文獻3 )中被揭示於基板上形成光阻圖型後，熱處理 之後’使光阻圖型之截面形狀變形後，形成微細圖型之方 法。又，特開平4 — 3 64 02 1號公報（專利文獻4 )中揭示 β成光阻圖型後’於其軟化溫度程度下進行加熱，藉由光 阻之流動化後’變更其圖型尺寸形成微細圖型之方法。 •6 - (3) 1263263 此等方法其晶圓面內之熱依存性爲數nm厂C，此點並 無多大問題，惟，藉由熱處理之光阻的變形、流動控制上 有困難’因此，於晶圓面內不易設定光阻圖型之問題存在 〇 進一步發展上述方法之方法者如：特開平 7— 45510 號公報（專利文獻5 )中揭示於基板上形成光阻圖型後， 爲防止基板上過於流動光阻圖型而形成停止閥之樹脂，再 φ 進行熱處理後，使光阻流動化後，變更圖型尺寸之後，去 除樹脂形成微細圖型之方法。做爲上述樹脂者如：水溶性 樹脂’具體而言以單獨使用聚乙烯醇者，惟，聚乙烯醇單 獨使用時’其對水溶解性爲不足者，因此，不易以水洗完 全去除’不易形成理想之外觀圖型，又，不一定能滿足經 時性之安定性面之外，塗佈性亦不良等問題存在，極爲不 實用者。 爲解決此等先行技術之問題，本申請人於特開2003 -參084459號公報、特開2003— 084460號公報、特開2003 — 1 077 5 2號公報、特開2003 — 1 423 8 1號公報、特開2003 — 195527號公報、特開2003— 202679號公報（專利文獻6 - 1 1 )等中提出有關圖型微細化用被覆形成劑及微細圖型 之形成方法之技術。此等專利文獻6〜1 1等所示之技術可 取得於圖型尺寸控制性、良好外觀、半導體裝置具備所要 求特性之微細圖型。 使用此微細圖型化用之被覆形成劑之微細圖型形成技 術中，首先，於基板上設置光阻層，使此進行曝光、顯像 -7- (4) 1263263 後’形成光阻圖型。再於基板全面進行被覆圖型微細化用 之被覆形成劑後，進行加熱後，利用該圖型微細化用之被 覆形成劑之熱收縮作用後，擴大光阻圖型，藉此縮小光阻 圖型之間隔，該光阻圖型間隔亦縮小所畫定之圖型（通孔 圖型、溝道圖型等各種圖型）之寬度，而取得微細化圖型 〇 亦即，該圖型微細化中，受光阻圖型形成階段（第1 # 階段）與圖型微細化用之被覆形成劑的熱收縮階段（第2 階段）之2個階段下圖型尺寸控制之影響。利用此法形成 光阻圖型中務必使第1階段所形成之圖型形狀於第2階段 之熱收縮步驟中，維持圖型形狀之同時以均勻熱收縮率進 行收縮。特別是形成橢圓形狀等、非圓形之通孔圖型時， 務必保持高度熱收縮率、維持橢圓之短軸徑與長軸徑比率 狀態下進行熱收縮，取得微細化之橢圓形通孔圖型。本申 請發明係爲解決該課題者。 # 另外，特開200 1 — 28 1 886號公報（專利文獻12 )中 揭示於光阻圖型表面被覆含有水溶性樹脂之光阻圖型縮小 化材料所成之酸性被膜，使光阻圖型表面層轉換成鹼可溶 性，再以鹼性溶液去除該表面層與酸性被膜後，縮小光阻 圖型之方法，又，於特開2002 — 1 8467 3號公報（專利文 獻1 3中揭示，基板上形成光阻圖型與該光阻圖型上形成 含有水溶性膜形成成份之塗膜，將此等光阻圖型與塗膜進 行熱處理後，於四甲基銨氫氧化物水溶液進行浸水後，未 經乾蝕刻步驟形成微細化光阻圖型之方法，惟，此等均 -8- (5) 1263263 使光阻圖型自行微細化之方法者，與本申請發明之目的完 全相異。 專利文獻1 :特開平5 — 1 6 6 7 1 7號公報 專利文獻2 :特開平5 — 24 1 3 4 8號公報 專利文獻3 :特開平1 — 3 0722 8號公報 專利文獻4 :特開平4 — 3 6402 1號公報 專利文獻5 :特開平7 — 4 5 5 1 0號公報 專利文獻6:特開2003— 084459號公報 專利文獻7:特開2003— 084460號公報 專利文獻8:特開2003 — 107752號公報 專利文獻9 :特開2003 — 142381號公報 專利文獻10 :特開2003 — 1 95 527號公報 專利文獻11 :特開2003 — 202679號公報 專利文獻12:特開2001 - 281886號公報 專利文獻13:特開2002 - 184673號公報 【發明內容】 本發明鑑於上述問題，其目的爲提供一種企圖於維持 圖型形狀下以均勻熱收縮率進行收縮形成圖型者，特別是 於橢圓形狀之通孔圖型形成中，可保持高度熱收縮率，同 時維持橢圓之短軸徑與長軸徑之比率狀態下進行熱收縮後 ，取得微細化之橢圓形通孔圖型之圖型微細化用被覆形成 劑及使用其之微細圖型形成方法者。 本發明爲解決上述課題，提供一種被覆於具有光阻圖 -9- 1263263 (6) 型之基板上，利用該被覆之熱收縮作用，縮小光阻圖型間 隔後’爲實質上完全去除該被覆後形成微細圖型所使用之 被覆形成劑者，以含有（a )水溶性聚合物與（b )同一環 內至少具有2個以上之氮原子雜環化合物之單體爲其特徵 之圖型微細化用之被覆形成劑。 又’本發明係提供一種含有於具有光阻圖型之基板上 被覆該圖型微細化用之被覆形成劑後，藉由熱處理使該被 •覆形成劑進行熱收縮劑用其熱收縮作用而縮小光阻圖型間 之間隔’再使該圖型微細化用被覆形成劑實質上完去除之 步驟之微細圖型的形成方法。 上述中，使熱處理於基板上之光阻圖型中以不產生熱 流動之溫度下進行加熱者宜。 於具有光阻圖型之基板上設置被覆形成劑（塗膜）， 利用此塗膜之收縮力縮小光阻圖型之間隔，再於利用去除 上述塗膜之微細圖型的形成方法技術中，特別是形成橢圓 着形狀之通孔圖型中，可維持高度熱收縮率，於維持橢圓之 短軸徑與長軸徑之比率狀態下進行熱收縮後，可取得微細 圖型化之橢圓形通孔圖型之圖型微細化用之被覆形成劑及 使用此之微細圖型形成方法。 【實施方式】 本發明圖型微細化用之被覆形成劑係被覆於設置光阻 圖型（外罩圖型）之基板上，藉由該被覆之熱收縮作用使 光阻圖型幅度擴大，藉由此使光阻圖型間隔所畫定之通孔 -10- (7) 1263263 圖型、溝道圖型之寬度縮小後’貫質上完全去除該被覆後 ，用於形成微細圖形者。 其中「實質上完全去除被覆」係指，利用該圖型微細 化用被覆形成劑之熱收縮作用，縮小光阻圖型間隔後，與 光阻圖型之界面上，使該圖型微細化用被覆形成劑無有意 義之殘留厚度份，完全去除之意。因此，本發明未含有使 該圖型微細化用被覆形成劑殘留一定厚度於光阻圖型界面 φ 附近後，使該僅殘留所定厚度份之圖型進行微細化等方法 〇 該本發明圖型微細化用之被覆形成劑係含有（a )水 溶性聚合物與（b )同一環內至少具有2個以上氮原子之 雜環式化合物。 做爲該（a )成份之水溶性聚合物只要於室溫下溶於 水後所得之聚合物即可，並未特別限定，通常可使用丙烯 酸系聚合物、乙烯系聚合物、纖維素系衍生物、伸烷基二 #醇系聚合物、脲系聚合物、蜜胺系聚合物、環氧系聚合物 、醯胺系聚合體等。 丙烯酸系聚合物例者如：以丙烯酸、丙烯酸甲酯、甲 基丙烯酸、甲基丙烯酸甲酯、N，N—二甲基丙烯醯胺、N ，N—二甲基胺基丙基甲基丙烯醯胺、n，n-二甲基胺基 丙基丙儀醯胺、N-甲基丙烯醯胺、二丙酮丙烯醯胺、n ’ N—二甲基胺基乙基甲基丙烯酸酯、n，n-二乙基胺基 乙基甲基丙；1¾酸酯、N，N—二甲基胺基乙基丙烯酸酯、 丙燦醯嗎啉等單體做爲構成成份之聚合物或共聚物例。 -11 - (8) 1263263 乙烯系聚合物例如：以N —乙烯吡咯烷酮、 二酮、醋酸乙烯酯等單體做爲構成成份之聚合物 例。 做爲纖維素系衍生物例者如：羥丙基甲基纖 酯、羥丙基甲基纖維素乙酸酯酞酸酯、羥丙基甲 六氫酞酸酯、羥丙基甲基纖維素乙酸酯琥珀酸酯 甲基纖維素、羥丙基纖維素、羥乙基纖維素、纖 • 乙酯六氫酞酸酯、羧甲基纖維素、乙基纖維素、 素等例。 做爲伸烷基二醇系聚合物例者如：乙二醇、 加成聚合物或加成共聚物等例。 脲系聚合物之例者如：以羥甲基化脲、二羥 、乙烯脲等做爲構成成份之例。 蜜胺系聚合物例者如：以甲氧基甲基化蜜胺 甲基化異丁氧基甲基化蜜胺、甲氧基乙基化蜜胺 成成份之例。 更可使用於環氧系聚合物、醯胺系聚合物等 性者。 其中又以含有至少1種選自伸烷基二醇系聚 維素系聚合物、乙烯系聚合物、丙烯系聚合物所 ，特別以丙烯系聚合物其易於調整pH面爲最理 有丙稀系聚合物與丙烯系聚合物以外之水溶性聚 聚物於加熱處理時，可維持光阻圖型之形狀，同 光阻圖型間隔之收縮效率面更爲理想。（a )成份 乙烯咪唑 或共聚物 維素酞酸 基纖維素 、羥丙基 維素乙酸 甲基纖維 丙二醇等 甲基化脲 、甲氧基 等做爲構 中爲水溶 合物、纖 構成者宜 想者。更 合物之共 時可提高 可使用1 -12- 12632631263263 (1) Description of the Invention [Technical Field] The present invention relates to a coating forming agent for pattern miniaturization in the technical field of lithographic printing plates and a method for forming a fine pattern using the same. More specifically, it relates to a coating forming agent for pattern miniaturization obtained by integration and miniaturization of a semiconductor device in recent years, and a method for forming a fine pattern using the same. Φ [Prior Art] In the manufacture of electronic components such as semiconductor devices and liquid crystal devices, when etching is performed on a substrate, a film (photoresist layer) is provided on the substrate by induction of active radiation, that is, a sensitive radiation. The radiation is selectively irradiated with active radiation, and after exposure, the development process is performed, and the photoresist layer is selectively dissolved and removed, and then an image pattern (resist pattern) is formed on the substrate to serve as a protective layer (cover pattern). A photo relief technique in which various patterns such as a via pattern, a channel pattern, and the like are formed on a substrate is used. In recent years, the integration and miniaturization of semiconductor devices have been increasing, and the development of these patterns has been actively and miniaturized. At present, ultra-fine processors with a pattern width of 0·20 μηι or less are required, and the pattern of the cover is used. The active light is also irradiated with short-wavelength light such as KrF, ArF, F2 excimer laser light or thunder line, and the photoresist material used as the material for forming the pattern of the cover is also studied and developed to cope with such illumination. Physical property. In addition to the countermeasures for the ultra-fine refinement of the surface of the photoresist material, the research and development of the pattern formation method is beyond the resolution of the photoresist material -5- (2) 1263263 . For example, in Japanese Unexamined Patent Application Publication No. Hei No. Hei No. Hei. No. Hei. After the mixture is formed on the entire surface of the substrate by the photoresist, the mixed layer is formed on the sidewalls of the pattern forming photoresist to the surface, and the non-mixed portion of the photoresist for mixing is removed, and the mixed layer is intended to have a fine size. The method of forming a demoulding pattern. Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. After the photoresist is diffused by the photoresist, a photoresist having a certain thickness is formed in the vicinity of the interface between the resin and the resist pattern, and after the image is developed, the acid-diffused resin portion is removed, and the thickness of the certain size is destined to be miniaturized. Pattern formation method. However, these methods are not easy to adjust the thickness of the layer formed on the sidewall of the photoresist pattern, and the thermal dependence in the wafer surface is an extremely large number of ten nm/° C. Currently, in the heating device used in the manufacture of semiconductor devices It is extremely difficult to uniformly maintain the inside of the wafer, and the problem of apparently uneven pattern size is generated. Further, a method of fluidizing a photoresist pattern by heat treatment or the like to refine the pattern size is also known. For example, in Japanese Patent Publication No. _3 〇7 2 2 8 (Patent Document 3), after forming a photoresist pattern on a substrate, after heat treatment, the cross-sectional shape of the photoresist pattern is deformed to form a fine pattern. The method. Further, Japanese Laid-Open Patent Publication No. Hei 4-3 64 02 1 (Patent Document 4) discloses that after the β is formed into a photoresist pattern, heating is performed at a softening temperature thereof, and the pattern size is changed by fluidization of the photoresist. A method of forming a fine pattern. • 6 - (3) 1263263 The thermal dependence of the wafer surface in these methods is a few nm of factory C. This is not a problem at all, but the deformation and flow control of the photoresist by heat treatment is difficult. The problem that the photoresist pattern is not easily set in the wafer surface is disclosed in the Japanese Patent Application Laid-Open No. Hei 7-45510 (Patent Document 5). The method of preventing the resin from forming a stop valve by over-flowing the photoresist pattern on the substrate, and then heat-treating the photoresist after φ is heat-treated, and then changing the pattern size, removes the resin to form a fine pattern. As the above-mentioned resin, such as a water-soluble resin, specifically, polyvinyl alcohol is used alone, but when polyvinyl alcohol is used alone, it is insufficient in water solubility, and therefore, it is difficult to completely remove it by washing, and it is difficult to form. The ideal appearance pattern does not necessarily satisfy the problem of stability over time, and the problem of poor coatability is extremely unpractical. In order to solve the problems of such prior art, the applicant is disclosed in Japanese Laid-Open Patent Publication No. 2011-045, JP-A-2003-084460, JP-A-2003-017742, and JP-A-2003- 1 423 8 A technique for forming a coating forming agent for pattern miniaturization and a method of forming a fine pattern is proposed in Japanese Laid-Open Patent Publication No. 2003-199527, No. 2003-202679 (Patent Document No. 6-1). The techniques shown in the above-mentioned Patent Documents 6 to 11 and the like can be obtained in a pattern having a dimensional controllability, a good appearance, and a semiconductor device having a desired pattern. In the fine pattern forming technique using the coating forming agent for fine patterning, first, a photoresist layer is provided on a substrate, and exposure and development are performed -7-(4) 1263263 to form a photoresist pattern. . After the coating agent for coating the pattern refining is completely applied to the substrate, after heating, the heat-shrinking action of the coating forming agent for refining the pattern is used, and then the resist pattern is enlarged to reduce the photoresist pattern. At the interval of the pattern, the interval of the photoresist pattern also reduces the width of the pattern (the pattern of the through hole pattern, the channel pattern, and the like), and the micro pattern is obtained, that is, the pattern is refined. Among them, the influence of pattern size control in the two stages of the heat shrinkage stage (second stage) of the photoresist pattern formation stage (the first # stage) and the pattern formation miniaturization. In the photoresist pattern formed by this method, the pattern shape formed in the first step must be shrunk at the uniform heat shrinkage rate while maintaining the pattern shape in the heat shrinking step of the second step. In particular, when forming a non-circular through-hole pattern such as an elliptical shape, it is necessary to maintain a high thermal shrinkage rate and maintain heat shrinkage while maintaining the ratio of the minor axis diameter to the major axis diameter of the ellipse, thereby obtaining a microscopic elliptical through hole pattern. type. This application is intended to solve the problem. In addition, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The surface layer is converted into an alkali-soluble, and the surface layer and the acidic film are removed by an alkaline solution, and the photoresist pattern is reduced. Further, the substrate is disclosed in Japanese Laid-Open Patent Publication No. 2002-186763 (Patent Document 13) Forming a photoresist pattern on the upper surface and forming a coating film containing a water-soluble film forming component on the photoresist pattern, and heat-treating the photoresist pattern and the coating film after immersing in a tetramethylammonium hydroxide aqueous solution The method of forming a fine photoresist pattern without a dry etching step, however, the method of making the photoresist pattern self-micronizing by the method of -8-(5) 1263263 is completely different from the object of the present invention. Patent Document 1: Japanese Laid-Open Patent Publication No. Hei No. Hei 5: 1 6 6 7 1 7 Patent Document 2: Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. 4 — 3 6402 Publication No. 1 Patent Document 5: Special Kaiping 7 — 4 5 Japanese Laid-Open Patent Publication No. 2003- 074459 (Patent Document No. JP-A-2003- No. [Patent Document 10] Japanese Laid-Open Patent Publication No. JP-A No. 2001- 208 The present invention has been made in view of the above problems, and an object thereof is to provide an attempt to form a pattern by shrinking at a uniform heat shrinkage rate in a pattern shape, and particularly to form a through hole pattern in an elliptical shape, and maintain a high heat shrinkage rate while When the heat shrinkage is performed while maintaining the ratio of the short axis diameter to the long axis diameter of the ellipse, the pattern forming agent for refining the elliptical through hole pattern and the fine pattern forming method using the same are obtained. In order to solve the above problems, the present invention provides a coating on a substrate having a photoresist pattern of the model 9- 1263263 (6), and uses the heat shrinkage action of the coating to reduce the interval of the photoresist pattern. The capping agent used for forming the fine pattern after the coating is completely removed, and the monomer containing (a) the water-soluble polymer and (b) the heterocyclic compound having at least two or more nitrogen atoms in the same ring is Further, the present invention provides a coating forming agent for coating a pattern having a resist pattern on a substrate having a resist pattern, and then subjecting the coating to a coating by heat treatment. The forming agent performs a method of forming a fine pattern in which the heat shrinking agent shrinks the interval between the photoresist patterns by the heat shrinkage action, and the pattern forming agent is substantially removed by the process of miniaturizing the pattern forming agent. In the above, it is preferable to heat the substrate in the photoresist pattern which is heat-treated on the substrate at a temperature at which no heat is generated. Providing a coating forming agent (coating film) on a substrate having a resist pattern, reducing the interval of the resist pattern by the contraction force of the coating film, and further adopting a technique for forming a fine pattern of the coating film. In particular, in the through hole pattern in which the elliptical shape is formed, the high heat shrinkage rate can be maintained, and after the heat shrinkage is maintained while maintaining the ratio of the short axis diameter to the long axis diameter of the ellipse, a micropatterned elliptical pass can be obtained. A coating forming agent for pattern miniaturization of a hole pattern type and a fine pattern forming method using the same. [Embodiment] The coating forming agent for pattern miniaturization of the present invention is coated on a substrate on which a photoresist pattern (outer pattern) is provided, and the resist pattern is enlarged by the heat shrinkage action of the coating. Therefore, the through hole -10- (7) 1263263 pattern of the photoresist pattern interval is narrowed, and the width of the channel pattern is reduced, and the fine pattern is formed after the coating is completely removed. The term "substantially completely removes the coating" means that the pattern is miniaturized by the heat shrinkage action of the coating forming agent, and the pattern of the resist pattern is reduced, and the pattern is miniaturized at the interface with the resist pattern. The coating forming agent has no significant residual thickness portion and is completely removed. Therefore, the present invention does not include a method of miniaturizing the pattern in which only a predetermined thickness portion remains after a predetermined thickness of the pattern forming agent for the pattern refining remains in the vicinity of the resist pattern interface φ. The coating forming agent for miniaturization contains (a) a water-soluble polymer and (b) a heterocyclic compound having at least two or more nitrogen atoms in the same ring. The water-soluble polymer as the component (a) is not particularly limited as long as it is soluble in water at room temperature, and an acrylic polymer, a vinyl polymer, or a cellulose derivative can be usually used. An alkyl group polymer, a urea polymer, a melamine polymer, an epoxy polymer, a guanamine polymer or the like. Examples of acrylic polymers are: acrylic acid, methyl acrylate, methacrylic acid, methyl methacrylate, N,N-dimethyl acrylamide, N,N-dimethylaminopropyl methacryl Indoleamine, n, n-dimethylaminopropyl propylamine, N-methyl acrylamide, diacetone acrylamide, n 'N-dimethylaminoethyl methacrylate, n , n-diethylaminoethyl methyl propyl; 13⁄4 acid ester, N,N-dimethylaminoethyl acrylate, propylene cannon morpholine and other monomers as a constituent polymer or copolymer example. -11 - (8) 1263263 A vinyl polymer is exemplified by a polymer having a monomer such as N-vinylpyrrolidone, diketone or vinyl acetate as a constituent component. Examples of cellulose-based derivatives such as hydroxypropylmethylcellulose, hydroxypropylmethylcellulose acetate phthalate, hydroxypropylmethylhexahydrophthalate, hydroxypropylmethylcellulose Examples of acetate succinate methylcellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, cellulose ethyl hexahydrophthalate, carboxymethyl cellulose, ethyl cellulose, and the like. Examples of the alkylene glycol-based polymer include ethylene glycol, an addition polymer, and an addition copolymer. Examples of the urea-based polymer include an example in which a methylolated urea, a dihydroxy group, a vinyl urea or the like is used as a constituent component. Examples of the melamine-based polymer include an example in which a methoxymethylated melamine methylated isobutoxymethylated melamine or a methoxyethylated melamine is used. Further, it can be used for an epoxy polymer or a guanamine polymer. In addition, it contains at least one selected from the group consisting of an alkylene glycol-based orvidin-based polymer, a vinyl-based polymer, and a propylene-based polymer, and particularly a propylene-based polymer, which is easy to adjust the pH surface. When the water-soluble polymer other than the polymer and the propylene-based polymer is heated, the shape of the resist pattern can be maintained, and the shrinkage efficiency surface of the photoresist pattern interval is more desirable. (a) a component such as vinylimidazole or a copolymer of retinoic acid-based cellulose, hydroxypropyl veganacetic acid, methyl propylene glycol or the like, methylated urea, methoxy, etc., which are preferably composed of a water-soluble compound and a fiber. Think of it. The total time of the compound can be improved. It can be used 1 -12 - 1263263
種或2種以上。 (a )成份做爲共聚物使用時，其構成成份之配合比 未並特別限定，惟，對於經時安定性特別重視時，使丙烯 系聚合物之配合比爲多於此外之其他構成聚合物者宜。另 外，提昇經時安定性除配合如上述過剩之丙烯系聚合物之 外，亦可藉由添加P -甲苯磺酸、月桂基苯磺酸等酸性化 合物進行解決。 做爲本發明該（b )成份者係以使用於至少同一環內 具有2個以上氮原子之雜環化合物單體者爲其特徵。 做爲（b )成份例者如：吡唑、3，4 —二甲基吡唑、2 一吡唑啉、吡唑啉—5 一酮、3 —甲基一1 一苯基一吡唑啉 —5—酮、2，3-二甲基一1 一苯基—吡唑啉一 5一酮、2, 3 —二甲基一 4 —二甲胺一 1 一苯基一吡唑啉一 5 一酮、苯並 吡唑等吡唑系化合物；咪唑、甲基咪唑、2，4，5 一三苯 基咪唑、4一（2 —胺乙基）咪唑、2 —胺基—3 -（4一咪 哩基）丙酸等咪唑系化合物、2，4，5一三苯基—2 一咪口坐 啉、2 —（1 一萘甲基）一 2 一咪唑啉等咪唑啉系化合物； 咪唑嗪、2—咪唑酮、2，4一咪唑嗪二酮、丨―甲基一 2，4 咪嗤嗪一 _、甲基一 2，4一咪Π坐嗪二酮、5 —經基— 2，4 —咪唑嗪二酮一 5 一羧酸、5 一脲基—2，4 一咪唑嗪二 酮、2—亞胺—i 一甲基一4一咪唑酮、2一硫代一4一咪唑 酮等之咪唑嗪系化合物；苯並咪唑、2一苯基苯並咪唑、2 一苯並咪唑酮等之苯並咪唑系化合物；】，2 一二嗪、1，3 嗪 4 一 二嗪、2，5 — 甲基吡嗪等之二嗪系化合 -13- (10) 1263263 物；2，4 ( 1H，3H )嘧啶二酮、5 —甲基尿嘧啶、5 一乙 基—5—苯基—4，6-過氫嘧啶二酮、2 -硫化一 4— (1H ，311)—喃!1定酮、4一亞胺一2(111，311)嚼啶、2，4，6 (1 Η，3 Η，5 Η ) -嘧啶三酮等氫化嘧啶系化合物；噌啉 、酞嗪、喹諾索啉、喹喔啉、魯米諾、等苯並二嗪系化合 物；苯並噌啉、吩嗪、5，10 —二氫吩嗪等之二苯並二嗪 系化合物；1Η— 1，2，3 —三D坐、1Η— 1，2，4 —三哗、4 φ 一胺基—1，2，4 —三唑等三唑系化合物；苯並三唑、5 — 甲基苯並三唑等之苯並三唑系化合物；1，3，5-三嗪、1 ，3，5 —三嗪一 2，4，6 —三醇、2，4，6—三甲氧基一1 ，3，5 —三嗪、1，3，5-三嗪—2，4，6—三硫醇、1，3 ，5- 三嗪—2，4，6 —三胺、4，6— 二胺基—1，3，5-三嗪一 2 —醇等三嗪系化合物例，惟，並非僅限於此。 其中由易於使用，更易於取得面等觀點視之，又以咪 唑系化合物之單體爲較佳者，特別以咪唑爲最理想者。 (b)成份之配合量爲對於本發明（a)成份時爲1〜 1 5質量％者宜，更佳者爲2〜1 0質量％。當未達1質量％ 時，將不易取得本發明所期待之效杲，反之，超出1 5質 量％時則不但未能取得本發明所期待效果，同時異物產生 之危險亦變大。 本發明圖型微細化用之被覆形成劑以固形份濃度時使 用3〜50質量％濃度之水溶液者宜，特別以5〜20質量％ 濃度之水溶液之使用爲最佳。當濃度未達3質量％時’恐 對於基板之被覆不良，反之，超出5 0質量％則未隨著濃度 -14- (11) 1263263 之提昇而提昇效果，使用性亦不佳。 又，本發明圖型微細化用之被覆形成劑通常如上述之 以水做爲溶媒使用後做成水溶液後使用之，亦可使用水與 醇系溶媒之混合溶媒者。做爲醇系溶媒例者如：甲基醇、 乙醇、丙醇、異丙醇、甘油、乙二醇、丙二醇、I，2 -丁 二醇、1，3 — 丁二醇、2，3-丁二醇等例。此等醇系溶媒 針對水時，以3 0質量％做爲上限進行混合使用之。 i 本發明圖型微細化用之被覆形成劑中，加入該（a ) 成份、（b )成份後，更，依所期待配合水溶性胺、界面 活性劑等亦可。 做爲水溶性胺者，如：25 °C水溶液中pKa (酸解離定 數）爲7.5〜13之胺類例者。具體例如：單乙醇胺、二乙 醇胺、三乙醇胺、2— (2—胺基乙氧基）乙醇、N，N- 二甲基乙醇胺、N，N—二乙基乙醇胺、N，N —二丁基乙 醇胺、N—甲基乙醇胺、N-乙基乙醇胺、N—丁基乙醇胺 Φ 、N —甲基二乙醇胺、單異丙醇胺、二異丙醇胺、三異丙 醇胺等烷醇胺類；二乙烯三胺、三乙烯四胺、丙烯二胺、 N，N —二乙基乙烯二胺、1，4 - 丁二胺、N —乙基一乙烯 二胺、1，2—丙二胺、1，3 —丙二胺、1，6 —己二胺等聚 伸烷基聚胺類；2 -乙基一己胺、二辛胺、三丁胺、三丙 胺、三烯丙胺、庚胺、環己胺等之脂肪族胺；苄胺、二苯 胺等之芳香族胺類等例。其中又以沸點1 40 °C以上（ 7 6 0mmHg)者爲較佳，如··單乙醇胺、三乙醇胺等爲理想 使用者。水溶性胺之添加對於防止不純物之產生’ PH調 -15- (12) 1263263 整等爲有效者。 配合水溶性胺時，當對於圖型微細化用之被覆形成劑 (固形份）時’以〇 . 1〜3 0質量％之比例進行配合者宜’ 特別以2〜15質量％爲更佳者。若未達0.1質量％則恐藉由 經時產生液劣化，反之，超出3 0質量％則恐出現光阻圖型 形狀劣化。 做爲界面活性劑者並未特別限定，通常，對於含於本 #發明之（a )成份務必具有高度溶解性，不出現懸浮等特 性。使用滿足此特性之界面活性劑後，特別於塗佈被覆用 材料時可抑制氣泡（microfoam)產生，可意圖防止關係 著該微氣泡產生之異物出現。 由上述觀點視之，以至少1種選启N —烷基吡咯烷酮 系界面活性劑、季銨鹽系界面活性劑、及聚環氧乙烷之磷 酸酯系界面活性劑使用者宜。 做爲N -烷基吡咯烷酮系界面活性劑者，以下述一般 ♦式（I )Kind or more than two. When the component (a) is used as a copolymer, the compounding ratio of the components is not particularly limited. However, when the stability is particularly important for the stability over time, the blending ratio of the propylene-based polymer is more than the other constituent polymers. Suitable. Further, the improvement of the stability over time can be solved by adding an acidic compound such as P-toluenesulfonic acid or laurylbenzenesulfonic acid in addition to the above-mentioned excess propylene-based polymer. The component (b) of the present invention is characterized by being used in a heterocyclic compound monomer having at least two nitrogen atoms in the same ring. As (b) components such as: pyrazole, 3,4-dimethylpyrazole, 2-pyrazoline, pyrazoline-5-one, 3-methyl-1-phenyl-pyrazoline 5-ketone, 2,3-dimethyl-1-phenyl-pyrazol-5-one, 2,3-dimethyl-4-dimethylamine-1-phenyl-pyrazoline-5 Pyrazole-based compounds such as monoketone and benzopyrazole; imidazole, methylimidazole, 2,4,5-triphenylimidazole, 4-(2-aminoethyl)imidazole, 2-amino-3-(4) Imidazolyl compound such as propionate, imidazoline compound such as propionic acid, imidazoline compound such as 2,4,5-triphenyl-2-indolizine, 2-(1-naphthylmethyl)-2-imidazolium; imidazole Pyrazine, 2-imidazolidone, 2,4-imidazolidinedione, hydrazine-methyl-2,4 imiprazine-, methyl-2,4-m-oxazindione, 5-amino group-2 , 4 - imidazolidinedione-5 carboxylic acid, 5-ureido-2,4-imidazolidinedione, 2-imine-i-methyl-4-imidazolidinone, 2-thio-tetraimidazole An imidazolidinium compound such as a ketone; a benzoxazole such as benzimidazole, 2-phenylbenzimidazole or 2-benzimidazolone Imidazole compound;], diazide, 1,3, 4-diazine, 2,5-methylpyrazine, etc. diazide compound-13-(10) 1263263; 2,4 (1H, 3H Pyrimidinedione, 5-methyluracil, 5-ethyl-5-phenyl-4,6-perhydropyrimidinedione, 2-vulcanized 4-(1H,311)-anthracene-1, 4-imine-2 (111,311) chelate, 2,4,6 (1 Η,3 Η,5 Η)-pyrimidinetrione and other hydrogenated pyrimidine compounds; porphyrin, pyridazine, quinololine, Quinoxaline, luminol, and other benzodiazepine compounds; benzoporphyrin, phenazine, 5,10-dihydrophenazine, etc.; dibenzodioxazine compounds; 1Η-1,2,3 — a triazole compound such as tris(R), 1,2,4,3,3,4,4,3,3,3-triazole, etc.; benzotriazole, 5-methylbenzotriazole, etc. Benzotriazole-based compound; 1,3,5-triazine, 1,3,5-triazine-2,4,6-triol, 2,4,6-trimethoxy-1,3,5 — Triazine, 1,3,5-triazine-2,4,6-trithiol, 1,3,5-triazine-2,4,6-triamine, 4,6-diamino-1 3,5-triazine An example of a triazine-based compound such as an alcohol is not limited thereto. Among them, the monomer of the imidazole compound is preferred from the viewpoints of ease of use, ease of obtaining the surface, and the like, and imidazole is particularly preferable. The amount of the component (b) is preferably from 1 to 15% by mass, more preferably from 2 to 10% by mass, based on the component (a) of the invention. When the amount is less than 1% by mass, the effect expected by the present invention is not easily obtained. On the other hand, when it exceeds 15% by mass, the desired effect of the present invention is not obtained, and the risk of foreign matter is also increased. The coating forming agent for refining the pattern of the present invention is preferably used in an aqueous solution having a concentration of 3 to 50% by mass in a solid concentration, and particularly preferably an aqueous solution having a concentration of 5 to 20% by mass. When the concentration is less than 3% by mass, the substrate may be poorly coated. On the other hand, if it exceeds 50% by mass, the effect is not improved with the increase of the concentration of -14-(11) 1263263, and the usability is also poor. Further, the coating forming agent for refining the pattern of the present invention is usually used as an aqueous solution after using water as a solvent, and a mixed solvent of water and an alcohol-based solvent may be used. Examples of alcohol-based solvents such as methyl alcohol, ethanol, propanol, isopropanol, glycerin, ethylene glycol, propylene glycol, I,2-butanediol, 1,3-butanediol, 2,3- Examples of butanediol and the like. When these alcohol-based solvents are used for water, they are mixed at an upper limit of 30% by mass. i In the coating forming agent for refining the pattern of the present invention, after the components (a) and (b) are added, a water-soluble amine, an surfactant or the like may be blended as desired. As a water-soluble amine, for example, an amine having a pKa (acid dissociation number) of 7.5 to 13 in an aqueous solution at 25 °C. Specific examples are: monoethanolamine, diethanolamine, triethanolamine, 2-(2-aminoethoxy)ethanol, N,N-dimethylethanolamine, N,N-diethylethanolamine, N,N-dibutyl Alkanolamines such as ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanolamine Φ, N-methyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine Diethylenetriamine, triethylenetetramine, propylene diamine, N,N-diethylethylenediamine, 1,4-diamine, N-ethyl-ethylenediamine, 1,2-propylenediamine , 1,3 - propylenediamine, 1,6-hexanediamine and other polyalkylene polyamines; 2-ethylhexylamine, dioctylamine, tributylamine, tripropylamine, triallylamine, heptylamine, An aliphatic amine such as cyclohexylamine; an aromatic amine such as benzylamine or diphenylamine; and the like. Among them, those having a boiling point of 140 ° C or higher (760 mmHg) are preferred, such as monoethanolamine or triethanolamine, which are ideal users. The addition of a water-soluble amine prevents the generation of impurities. PH adjustment -15- (12) 1263263 is equally effective. When the water-soluble amine is blended, when the coating forming agent (solid content) for refining the pattern is used, it is preferable to carry out the blending at a ratio of 〜1 to 30% by mass, particularly preferably 2 to 15% by mass. . If it is less than 0.1% by mass, it is feared that the liquid is deteriorated over time, and if it exceeds 30% by mass, the shape of the resist pattern may be deteriorated. The surfactant is not particularly limited. Usually, it is required to have high solubility in the component (a) contained in the present invention, and no suspension or the like is present. When a surfactant which satisfies this property is used, the generation of microfoam can be suppressed particularly when the coating material is applied, and it is intended to prevent the occurrence of foreign matter associated with the microbubble. From the above viewpoints, it is preferred to use at least one N-alkylpyrrolidone surfactant, a quaternary ammonium salt surfactant, and a polyethylene oxide phosphate surfactant. As an N-alkylpyrrolidone surfactant, the following general formula ♦ (I)
(式中，Ri爲碳原子數6以上之烷基） 所示者宜。 做爲該N -烷基吡咯烷酮系界面活性劑例者，其具體 例如：N -己基一 2 - D比略院酮、N —戊基一 2 —吼咯院酮 、N -辛基—2 —吡咯烷酮、N —壬基一 2 -吡咯烷酮'N — -16- (13) 1263263 癸基一 2-吼咯院酮、N-癸基一 2—D[t咯院酮、N-十一 基一 2 —卩比略院嗣、N —月桂基一 2 — D比略院嗣、N—十三 基一 2—吡略院酮、N —十四基一 2—吡咯院酮、N-十五 基—2—吡略烷酮、N—十六基一 2 —吡咯烷酮、N—庚癸 基一 2 — D[t咯院酮、N —庚癸基一 2 — D|t咯院酮、N —辛癸 基一 2 —吡咯烷酮等例。其中又以N-辛基一 2 —吡咯烷酮 (「surfadone LP100」；ISP公司製）爲較佳使用者。 做爲季胺鹽系界面活性劑者爲下述一般式（II ) R3一N一R5 .X· (II)(wherein, Ri is an alkyl group having 6 or more carbon atoms) is preferred. As an example of the N-alkylpyrrolidone-based surfactant, specifically, for example, N-hexyl-2-D-dosterol, N-pentyl-2-merolenone, N-octyl-2 Pyrrolidone, N-fluorenyl-2-pyrrolidone 'N - -16- (13) 1263263 fluorenyl- 2-indolyl ketone, N-mercapto- 2-D[t-roleone, N-eleven-based 2—卩比略院嗣, N—月桂基1-2 — D 比略院嗣, N—13基一二—Pyloxolone, N-14, 2-pyrrolidone, N-fifteen Benzyl-2-pyrrolidone, N-hexadecyl-2-pyrrolidone, N-heptyl-2-yl-D[t-roxenone, N-heptanyl-2, D|t-roleone, N - Examples of octenyl 2-pyrrolidone. Among them, N-octyl-2-pyrrolidone ("surfadone LP100"; manufactured by ISP) was preferred. As a quaternary ammonium salt surfactant, the following general formula (II) R3 - N - R5 .X · (II)
FUFU
[式中，R2、R3、R4、R5分別爲獨立之烷基或羥烷基（而 ，其中至少1個爲碳原子數6以上之烷基或羥烷基）；X 爲氫氧化物離子或鹵離子] |所示者宜。 做爲該季銨鹽系界面活性劑者，其具體例如：月桂基 三甲銨氫氧化物、十三基三甲銨氫氧化物、十四基三甲銨 氫氧化物、十五基三甲銨氫氧化物、己癸基三甲胺氫氧化 物、庚癸基三甲銨氫氧化物、辛癸基三甲銨氫氧化物等例 。其中又以己癸基三甲銨氫氧化物爲較佳使用者。 做爲聚環氧乙烷之碳酸酯系界面活性劑例者以下述一 般式（III) -17- (14) 1263263 0R7 R60-^CH2CH2O)TrR^ (III)Wherein R 2 , R 3 , R 4 and R 5 are each independently an alkyl group or a hydroxyalkyl group (wherein at least one of them is an alkyl group having 6 or more carbon atoms or a hydroxyalkyl group); and X is a hydroxide ion or Halide ion] | As the quaternary ammonium salt-based surfactant, specifically, for example, lauryl trimethylammonium hydroxide, tridecyltrimethylammonium hydroxide, tetradecyltrimethylammonium hydroxide, and fifteen-based trimethylammonium hydroxide Examples of hexamethylene trimethylamine hydroxide, heptyltrimethylammonium hydroxide, and octyltrimethylammonium hydroxide. Among them, hexamethylenetrimethylammonium hydroxide is preferred as the user. As a carbonate-based surfactant of polyethylene oxide, the following general formula (III) -17-(14) 1263263 0R7 R60-^CH2CH2O) TrR^ (III)
II OH 〇 (式中，R6爲碳原子數1〜10之烷基或烷基烯丙基；r7 爲氫原子或（ch2ch2o ) r6 (其中r6如上述所定義者） ;η爲1〜20之整數） 所示者宜。 做爲該聚環氧乙烷之磷酸酯系界面活性劑例者其具體 例可適用「？1丫511^人212£」、「？1丫511^人210〇」（以上 均爲第一工業製藥（股份）製）等之市售者。 配合界面活性劑時，其配合量對於圖型微細化用之被 覆形成劑（固形份）時以〇·1〜10質量％者宜，特別是0.2 〜2質量％爲更佳者。藉由配合界面活性劑後，可提昇其 塗佈性，使面內呈均一性、防止圖型收縮率之不均、防止 氣泡產生、防止異物出現等。 本發明之微細圖型形成方法係包括於具有光阻圖型之 基板上被覆該圖型微細化用之被覆形成劑後，藉由熱處理 使該圖型微細化用之被覆形成劑進行熱收縮，藉由該熱收 縮作用縮小光阻圖型間之間隔，再使該圖型微細化用被覆 形成劑實質完全去除之步驟。 製作具有光阻圖型之基板並未特別限定，通常以半導 體裝置、液晶顯示元件、磁頭或微透鏡等之製造中經常使 用之常法進行之。如··於聚矽氧晶圓等基板上，以轉子等 塗佈化學增幅型等光阻組成物、乾燥後形成光阻層之後， -18- (15) 1263263 藉由縮小投影曝光裝置等，經由所期待之外罩圖型進行照 射紫外線，deep — UV、準分子雷射光等活性光線、或藉由 電子線描繪後，進行加熱，再利用顯像液，如：1〜1 0質 量％四甲銨氫氧化物（TMAH )水溶液等鹼性水溶液進行6 此之顯像處理後，可於基板上形成光阻圖型。 又，做爲光阻圖型材料之光阻組成物例者並未特別限 定，一般可使用i線、g線用光阻組成物、KrF、ArF、F2 φ 等準分子雷射用光阻組成物，更可使用ΕΒ、EUV (電子 線）用光阻組成物爲特，廣泛受大眾使用之光阻組成物。 其中又以特別於形成光阻圖型時，於該光阻圖型與本 發明之圖型微細化用被覆形成劑之界面附近未形成混合層 之光阻組成物爲較理想者。混合層之形成後，將如上述先 行技術所載易產生異物，更且，基板面內之熱依存性達十 數nm等爲不理想者。 通常，使用i線、g線用光阻組成物（如含漆用酚醛 樹脂與萘喹啉二氮雜系感光劑之正型光阻組成物、等）時 ，無上述問題產生之虞，因此，無其之顧忌，使用含有準 分子雷射用光阻組成物，電子線用光阻組成物等，藉由曝 光產生酸之化合物（酸產生劑）之化學增幅型光阻組成物 時，藉由此酸產生劑所產生之酸於被覆形成劑與光阻圖型 之界面附近形成混合層，因此，務必考量此點。混合層之 形成將藉由酸產生劑所產生酸之擴散長度（擴散距離）， 所添加鹼性物質之添加量等之影響。因此’使用準分子雷 射用光阻組成物、電子線用光阻組成物等時’以選用無產 -19- (16) 1263263 生該混合層之光阻組成物者宜。 a·圖型微細化用被覆形成劑塗佈步驟 於具有此外罩圖型之光阻圖型之整體基板上進行塗佈 型微細化用被覆形成劑被覆之。又，塗佈圖型微細化用被 覆形成劑後，再度以80〜100 °C之溫度於基板上進行預焙 燒3 0〜9 0秒亦可。 P 被覆方法可以先行技術之熱流動過程中之一般所進行 之方法進行之。亦即，如：藉由轉子等將該圖型微細化用 被覆形成劑之水溶液塗佈於基板上。 b·熱處理（熱收縮）步驟 進行熱處理後，使圖型微細化用之被覆形成劑所成之 塗膜進行收縮。受此塗膜熱收縮力之影響後，連接於該塗 膜之光阻圖型之尺寸其塗膜熱收縮份變得極大，光阻圖型 鲁之幅度擴大、光阻圖型間之間隔縮小。此光阻圖型間之間 隔亦即，由所規定最終取得圖型之直徑、寬度，藉此使通 孔圖型之直徑、溝道圖型之寬度縮小化，可縮小寬度，進 行圖型之微細化。 加熱溫度係使圖型微細化用之被覆形成劑所成塗膜引 起熱收縮之溫度，只要可充份進行圖型之微細化之溫度者 ’並未特別限定，而，最好以於光阻圖型未引起熱流動之 溫度下進行加熱爲宜。於光阻圖型未引起熱流動之溫度係 指未形成圖型微細化用被覆形成劑所成塗膜，使僅形成光 -20- (17) 1263263 阻圖型之基板進行加熱時，於該光阻圖型未產生尺寸變化 之溫度。藉由此溫度之加熱處理後，可進行更有效之外觀 良好之微細圖型的形成，特別是晶圓面內之佔空比（Duty )，亦即，對於晶圓面內之圖型間隔可減少其依存性等面 爲極有效者。考量目前之照相石版技術中所使用之各種光 阻組成物之軟化點後，一般理想之加熱處理爲8 0〜1 6 0 °C 之溫度範圍下，惟其光阻於未引起熱流動之溫度下進行3 0 φ 〜9 0秒者。 做爲圖型微細化用之被覆形成劑所成塗膜之厚度者以 與光阻圖型相同高度者、或覆蓋其之高度者宜。 c.圖型微細化用之被覆形成劑去除步驟 此後，殘留於圖型之圖型微細化用被覆形成劑所成塗 膜可藉由水系溶劑，較佳者爲純水進行1 0〜60秒洗淨去 除之。又，亦可於水洗去除之前，預先以所期待之鹼水溶 •液（如：四甲銨氫氧化物（TMAH )、膽鹼等）進行去除 處理之。本發明之圖型微細化用被覆形成劑極易以水去除 洗淨’且’可完全由基板及光阻圖型去除之。 於基板_h，寬度擴大之光阻圖型間被畫是取得具有微 細化圖型之基板。 藉由本發明所取得之微細圖型具有比具光阻材料之解 像界限更微細之圖型尺寸，同時，具有良好外觀，兼備充 份滿足所期待要求特性之物性者。 另外’該a〜c步驟可多數次重覆進行之。重覆多數 -21 - (18) 1263263 次進行此a〜c步驟後，可使光阻圖型（外罩圖型）漸漸 擴大寬度。 做爲適用於本發明之技術領域者並未限定於半導體領 域，亦可用於廣範之液晶顯示元件、磁型製造、更可適用 於微透鏡製造等。 以下，藉由實施例進行本發明更詳細之說明，惟，本 發明並未受限於此等例者。又，配合量未特別指示下爲質 ⑩量％者。 [實施例] 以下，藉由實施例進行本發明更詳細之說明，惟’本 發明並未受限於此等例者。又，配合量未特別指示下爲質 量 〇/〇 〇 (實施例1 ) 將3g丙烯酸與乙烯吡咯烷酮之共聚物（聚合比=2: 1 )、0.12g咪唑、及0.03g聚環氧乙烷之磷酸酯系界面活 性劑（「plysurf A2 10G」；第一工業製藥（股份）製）溶 於4 Og水中，進行調製圖型微細化用之被覆形成劑。 另外，於基板上使正型光阻之「TArF — 7 a — 7 OEM」 (東京應化工業（股份）製）進行旋轉塗佈後，於95 °C下 進行焙燒處理90秒，形成膜厚0.25 μπι之光阻層。 對於該光阻層利用曝光裝置（「NSR—S 3 06」；nikon (股份）製）進行曝光處理，於85°C下進行加熱處理90 -22- (19) 1263263 秒，利用2.38質量％TMAH (四甲銨氫氧化物）水 行顯像處理後形成光阻圖型。此光阻圖型之形成後 長軸徑188nm、短軸徑102ιιπι之楕圓形通孔圖型（ :短軸徑=1 . 8 5 : 1 )。 再於具有此通孔圖型之基板上進行塗佈該圖型 用之被覆形成劑後，於1 45 °C進行加熱處理60秒後 該通孔圖型之微細化處理。又於23 °C下利用純水去 Φ 微細化用之被覆形成劑。此時之通孔圖型爲長軸徑 、短軸徑86tim之楕圓形通孔圖型（長軸徑：短軸ί :1 )，可直接以初期之楕圓形狀進行微細化處理 圖型形狀爲保持截面短形性之理想者。 (比較例1 ) 將3g丙烯酸與乙烯吡咯烷酮之共聚物（聚合1： )、0.18g三乙胺、及0.03g聚環氧乙烷之磷酸酯 φ活性劑（「plysurf A2 10G」；第一工業製藥（股份 溶於4 0 g水中，調製被覆形成劑。 再與實施例1同法於所形成之楕圓形通孔圖型 徑 188nm、短軸徑 102nm、長軸徑：短軸徑=1.85 : 進行行塗佈該被覆形成劑，於1 5 5 t下進行加熱處驾 後，進行該通孔圖型之微細化處理。又於2 3 °C下利 去除被覆形成劑。此時之通孔圖型其圖型截面形狀 好者，惟，所形成之楕圓形狀爲長軸徑147nm、 8 6nm之楕圓形通孔圖型（長軸徑：短軸徑=1·71 : 溶液進 ，形成 長軸徑 微細化 ，進行 除圖型 1 5 9nm g =1 .85 0又， 匕=2 : 1 系界面 )製） (長軸 1 )上 | 60秒 用純水 面爲良 短軸徑 1 )， -23- (20) 1263263 並無法保持初期之楕圓形狀者。 [產業上可利用性] 如上述，本發明圖型微細用之被覆形成劑及微細圖型 之形成方法可維持圖型形狀且以均勻之熱收縮率進行收縮 之圖型形成者，特別是於楕圓形狀之通孔圖型形成中，保 持高度熱收縮率，且維持楕圓之短軸徑與長軸徑比率之狀 #態下進行熱收縮，取得微細化之楕圓形通孔圖型，因應近 年之半導體裝置集成化、微小化，可有效取得微細圖型之 形成。II OH 〇 (wherein R 6 is an alkyl group having 1 to 10 carbon atoms or an alkylallyl group; r 7 is a hydrogen atom or (ch 2 ch 2 o ) r 6 (wherein r 6 is as defined above); η is 1 to 20 Integer) The one shown is appropriate. As a specific example of the phosphate ester-based surfactant of the polyethylene oxide, "?1丫511^人212£" and "?1丫511^人210〇" (the above are all the first industries) A marketer such as a pharmaceutical (share) system. When the surfactant is blended, the amount of the coating agent (solid content) for the micronization of the pattern is preferably from 1 to 10% by mass, particularly preferably from 0.2 to 2% by mass. By blending the surfactant, the coating property can be improved, the in-plane uniformity can be prevented, the pattern shrinkage rate can be prevented from being uneven, the generation of bubbles can be prevented, and foreign matter can be prevented from occurring. The method for forming a fine pattern of the present invention includes coating a coating agent for refining the pattern on a substrate having a resist pattern, and then thermally shrinking the coating forming agent for refining the pattern by heat treatment. By the heat shrinkage action, the interval between the photoresist patterns is reduced, and the pattern is further refined by the step of substantially completely removing the coating forming agent. The substrate having the photoresist pattern is not particularly limited, and is usually carried out by a usual method which is often used in the manufacture of a semiconductor device, a liquid crystal display device, a magnetic head or a microlens. For example, on a substrate such as a polyfluorene wafer, a photoresist composition such as a chemically amplified type is coated with a rotor or the like, and after drying to form a photoresist layer, -18-(15) 1263263 is reduced by a projection exposure apparatus or the like. The ultraviolet light is irradiated through the expected outer mask pattern, and the active light such as deep-UV or excimer laser light or the electron beam is drawn, and then heated, and then the developing liquid is used, for example, 1 to 10% by mass. After an alkali aqueous solution such as an aqueous solution of ammonium hydroxide (TMAH) is subjected to development processing, a photoresist pattern can be formed on the substrate. Further, the photoresist composition of the photoresist pattern material is not particularly limited, and generally, it is possible to use a photoresist composition for i-line or g-line, a photoresist for excimer laser such as KrF, ArF, or F2 φ. For the material, it is also possible to use a photoresist composition for enamel and EUV (electronic wire), which is widely used by the public as a photoresist composition. Further, in particular, when a photoresist pattern is formed, it is preferable that a photoresist composition in which a mixed layer is not formed in the vicinity of the interface between the photoresist pattern and the coating composition for refining the pattern of the present invention. After the formation of the mixed layer, foreign matter is easily generated as described in the above-mentioned prior art, and further, the heat dependency in the surface of the substrate is not more than several nm. In general, when a photoresist composition for i-line or g-line (such as a positive-type photoresist composition containing a phenol resin for lacquer and a naphthoquinone diazonium sensitizer, etc.) is used, the above problem does not occur, so , without any scruples, using a photoresist composition containing a quasi-molecular laser, a photoresist composition for an electron beam, etc., by exposure to a chemically amplified photoresist composition of an acid-producing compound (acid generator) The acid generated by the acid generator forms a mixed layer in the vicinity of the interface between the coating agent and the photoresist pattern, and therefore, it is necessary to consider this point. The formation of the mixed layer is affected by the diffusion length (diffusion distance) of the acid generated by the acid generator, the addition amount of the added basic substance, and the like. Therefore, when a photoresist composition for a pseudo-molecular laser, a photoresist composition for an electron beam, or the like is used, it is preferable to use a photo-resist composition of the mixed layer of -19-(16) 1263263. a. Coating Forming Agent Coating Step The coating type fine coating is coated with a coating forming agent on a whole substrate having a resist pattern of a mask pattern. Further, after coating the pattern forming agent for refining the pattern, it may be pre-baked on the substrate at a temperature of 80 to 100 ° C for 30 to 90 seconds. The P-coating method can be carried out by a method generally performed in the heat flow process of the prior art. In other words, for example, the pattern is made fine by a rotor or the like to apply an aqueous solution of the coating forming agent onto the substrate. b. Heat treatment (heat shrinkage) step After the heat treatment, the coating film formed by the coating forming agent for refining the pattern is shrunk. After being affected by the heat shrinkage force of the coating film, the size of the photoresist pattern connected to the coating film becomes extremely large, and the heat shrinkage of the coating film becomes extremely large, and the range of the photoresist pattern is enlarged, and the interval between the photoresist patterns is reduced. . The interval between the photoresist patterns is such that the diameter and the width of the pattern are finally obtained, thereby reducing the diameter of the through-hole pattern and the width of the channel pattern, thereby reducing the width and patterning. Micro-fine. The heating temperature is a temperature at which the coating film formed by the coating forming agent for forming a pattern is thermally contracted, and the temperature at which the pattern can be sufficiently refined is not particularly limited, but is preferably used for the photoresist. It is preferred that the pattern is heated at a temperature that does not cause heat to flow. The temperature at which the photoresist pattern does not cause heat flow means that the coating film formed by the coating forming agent for pattern miniaturization is not formed, and when only the substrate of the light-20-(17) 1263263 resistance pattern is heated, The photoresist pattern does not produce a temperature change in size. By the heat treatment of the temperature, a more effective appearance of the fine pattern can be performed, in particular, the duty ratio (Duty) in the wafer surface, that is, the pattern interval in the wafer surface can be It is extremely effective to reduce the dependence and other aspects. Considering the softening point of various photoresist compositions used in the current lithographic techniques, it is generally desirable to heat the treatment at a temperature range of 80 to 160 ° C, except that the photoresist is at a temperature that does not cause heat flow. Perform 3 0 φ ~ 9 0 seconds. The thickness of the coating film formed by the coating forming agent for pattern miniaturization is preferably the same as or higher than the height of the photoresist pattern. c. Coating forming agent removing step for pattern miniaturization, the coating film formed by the pattern forming agent for pattern refining remaining in the pattern may be subjected to an aqueous solvent, preferably pure water, for 10 to 60 seconds. Wash and remove it. Further, it may be removed in advance by a desired alkaline water solution (e.g., tetramethylammonium hydroxide (TMAH), choline, etc.) before washing with water. The coating-forming agent for pattern miniaturization of the present invention is easily removed by water and washed and removed completely from the substrate and the photoresist pattern. A substrate having a fine pattern is drawn between the substrate_h and the photoresist pattern having an enlarged width. The fine pattern obtained by the present invention has a pattern size which is finer than the resolution of the photoresist material, and has a good appearance and a physical property which satisfies the desired characteristics. In addition, the steps a to c can be repeated many times. Repeating the majority -21 - (18) 1263263 times After this a~c step, the photoresist pattern (cover pattern) can be gradually enlarged. The technical field to which the present invention is applied is not limited to the semiconductor field, and can be applied to a wide range of liquid crystal display elements, magnetic type fabrication, and more suitable for microlens manufacturing. Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Further, the amount of the compound is not more than 10% by mass. [Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto. Further, the blending amount is not particularly indicated as mass 〇/〇〇 (Example 1) 3 g of a copolymer of acrylic acid and vinylpyrrolidone (polymerization ratio = 2:1), 0.12 g of imidazole, and 0.03 g of polyethylene oxide. A phosphate ester surfactant ("plysurf A2 10G"; manufactured by Daiichi Kogyo Co., Ltd.) was dissolved in 4 Og of water to prepare a coating agent for refining the pattern. In addition, "TARF-7 7-7 OEM" (manufactured by Tokyo Ohka Kogyo Co., Ltd.) of the positive resist was spin-coated on the substrate, and then baked at 95 ° C for 90 seconds to form a film thickness. 0.25 μπι photoresist layer. The photoresist layer was subjected to exposure treatment by an exposure apparatus ("NSR-S 3 06"; manufactured by Nikon Co., Ltd.), and heat-treated at 85 ° C for 90 -22 - (19) 1263263 seconds, using 2.38 mass% TMAH. (Tetramethylammonium hydroxide) After the water treatment, a photoresist pattern is formed. After the formation of the photoresist pattern, the long-axis diameter of 188 nm and the short-axis diameter of 102 ιιπι are circular through-hole patterns (: short-axis diameter = 1. 8 5 : 1 ). Further, after coating the coating forming agent for the pattern on the substrate having the through-hole pattern, heat treatment was performed at 145 ° C for 60 seconds, and the through-hole pattern was miniaturized. Further, at 23 ° C, pure coating water was used to remove the coating agent for pulverization. At this time, the through hole pattern is a circular through hole pattern with a long axis diameter and a short axis diameter of 86 tim (long axis diameter: short axis ί : 1 ), and can be directly miniaturized in the initial round shape. The shape is ideal for keeping the cross section short. (Comparative Example 1) 3 g of a copolymer of acrylic acid and vinylpyrrolidone (polymerization 1:), 0.18 g of triethylamine, and 0.03 g of a phosphate ester φ active agent of polyethylene oxide ("plysurf A2 10G"; first industry Pharmaceutical (the stock was dissolved in 40 g of water to prepare a coating forming agent. The same method as in Example 1 was used to form a circular through-hole pattern with a diameter of 188 nm, a short-axis diameter of 102 nm, and a long-axis diameter: short-axis diameter = 1.85. : The coating forming agent is applied in a row, and after heating at 155 Torr, the through-hole pattern is miniaturized, and the coating forming agent is removed at 23 ° C. The hole pattern has a good cross-sectional shape, but the formed circular shape is a circular through hole pattern with a long axis diameter of 147 nm and 8.6 nm (long axis: short axis diameter = 1.71: solution into , the formation of the long axis diameter is refined, and the pattern is divided into 1 5 9nm g = 1.85 0, 匕 = 2 : 1 system interface) (long axis 1) | 60 seconds with pure water surface for good short axis diameter 1), -23- (20) 1263263 It is not possible to maintain the initial round shape. [Industrial Applicability] As described above, the pattern forming agent for fine pattern of the present invention and the method for forming a fine pattern can maintain the pattern shape and form a pattern which shrinks at a uniform heat shrinkage rate, particularly In the formation of the through-hole pattern of the circular shape, the thermal contraction rate is maintained, and the thermal contraction is performed while maintaining the ratio of the short-axis diameter to the long-axis diameter of the round, and the rounded through-hole pattern is obtained. In view of the integration and miniaturization of semiconductor devices in recent years, the formation of fine patterns can be effectively achieved.
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