200813639 九、發明說明： L發明所屑技術領域】 發明領域 本發明係與-種形成微形圖案之樹脂組成物有關，其 5係可以被用來減少在半導體微影術製程中之凹枰邹、、 積或寬度。 77 ^ C先前技術]| 發明背景 近幾年來，半導體裝置的高度整合性已經 10體裝置的製造中之導線寬度，以及在該、隹牛v 丄，4導線之間的距籬 大幅地減少。研發半導體裝置所需之一般製程η 、、 分為微影術、姓刻作用、清潔作用'離 σ χ被大略 雕卞植入、薄臌# 金屬導線佈線以及其他製程等等類型。在這此/、 ” 圖案化技術是微影製程中最重要的並且2技術之中’ 15之極大型積體電路提供發展動力。 、丨半^體裝置 八型的微影術製程包含將一對光照 圖案的方式曝光於-成像光照下㈣感光阻以經過 20 層。該影像接著係藉著將該經過曝光—案化光阻 (典型地為-水性驗類成像劑）接觸，、埋㈣物貝 該光阻層移除，而將該所㈣圖案顯、性地將部分的 會藉著將在雜圖案化絲層的開。j销案接著 -底層材料上。在該轉移作用完成之後，$料#刻而轉移 被移除。 ’殘留的光阻層將 微影技術需要使用具有較短波長之 九照，同時高解析 5 200813639 度光阻材料之成像作用係依據該光照作用的特性而有不 同。然而，曝光系統的改良需要縮短光的波長，因此將產 生相當多的費用。除此之外，要發展因應用於曝光作用之 短波長光照的光阻材料並不容易。 5 特別是，傳統的微影技術會因為用於曝光作用的光照 之波長有限制，因此其在以微形圖案化作用來改良積體整 合程度方面將受到侷限。一些嘗試已經被提出以克服這些 侷限。舉例來說，日本專利第3,071，401號說明一種微形圖 案形成材料，其係使用一種水溶性樹脂而在酸存在下與一 10 光阻產生交聯反應，以藉著自該光阻圖案所提供之酸而於 該光阻圖案與該微形圖案形成材料之間的界面形成一經交 聯的薄膜，並將該未經交聯的部分剝離。 然而，當該材料被用來形成一圖案時，該光阻圖案可 能會因為在交聯反應期間所導致之該樹脂體積的縮減，而 15 產生之應力之作用而變形。因此，目前需要有一種能夠克 服傳統材料的侷限之微形圖案形成材料，其具有一種新類 型的機制。 C發明内容3 發明概要 20 本案發明係考量習知技藝的問題來製造，並且本發明 的一個目的係要提供一種具有新類型的機制之微形圖案形 成材料，其能夠在一例如一獨立圖案或孔洞圖案中之圖案 的小型化作用中克服波長之限制。 本案發明人已經認真地而且密集地進行研究來達成該 6 200813639 目的。結果，本案發明人已經發現一水性醇類或鹼性溶液 可以被用來誘使光阻圖案層膨脹，並且一水溶性聚合物係 被用來誘發該在該經過膨脹的光阻圖案層與該水溶性聚合 物之間的纏結現象，以使得該光阻圖案層的凹槽部分之寬 5 度可以被減少。本發明係基於此一發現而達成。 依據本發明，其提供一種包含有一水溶性聚合物與一 溶劑之形成微形圖案的樹脂組成物，其中一微形圖案係藉 著將該樹脂組成物塗覆於一光阻圖案層上，誘使該光阻圖 案層的表面膨脹而形成一經膨脹的光阻圖案層，在該經膨 10 服的光阻圖案層與該形成微形圖案的樹脂組成物之間的界 面誘發纏結現象，並使用一顯像溶液來移除該水溶性聚合 物除了該纏結部分之外的部分而形成。 在本發明的一具體例中，該溶劑可能是一水性醇類或 是驗性溶液。 15 在本發明的一進一步具體例中，該水溶性聚合物可以 是一親水性單體單元或是一種由二或更多個親水性單體單 元的共聚物所組成的一均質聚合物。 在本發明的另一具體例中，該水溶性聚合物可以是由 至少一親水性單體單元與至少一單體單元所組成的共聚 20 物，該單體單元係選自於由乙烯基吡啶、乙烯基噻吩、苯 乙稀、乙稀基^卡唾、乙烯基苯并味唾、乙烯基甲基味唾、 乙稀基二氨基三味唾、乙晞基三味嗤以及乙浠基四啼嗤所 構成的群組。 在本發明的另一具體例中，該水溶性聚合物可以是由 7 200813639 植成的妓1物早體衫與至少—（甲基)丙烯酸單體單元所 燒基、：:;=(甲基)丙稀酸單體單元具有選自於由金剛 官能基降冰片基以及異冰片基所構成的群組之 5 10 15 20 單體ΐ二=有另一具體例中，該水溶性聚合物的親水性 氨美、雜八至4—選自於由經基、《基、醯氨基、 群組之官能基。 〜及續酸基所構成的 單體ί本糾的另—具體例中，該水溶性聚合物的親水性 選自於由乙烯醇類、乙烯基賴、丙稀酸、 = 氧乙燒、乙稀基經基乙基甲基丙稀酸醋、 喊、乙烯基规嗣、乙稀氨、稀丙氨、乙烯 土^、乙烯基嚼姆，以及其等之組合所構成的群組。 比上的另一具體例中該親水性單體單元的數量 “ >、一早體單元的數量之比率係介於i:㈣糾： 其\該至少—單體單元係選自於由乙烯基^定、乙烯 :塞吩、本乙稀、乙稀基味唾、乙稀基苯并味唾、乙稀基 基㈣' 乙烯基二氨基三味。坐、乙稀基三味唾以及乙烯 基四咪唑所構成的群組。 在本心月的另-具體例中，該親水性單體翠元的數量 比上該（甲基）丙烯酸3旨單體單元的數量之比率係介於！： 0.01和1: 0.5之間’該（甲基)丙烯酸酯單體單元係且有選自 於由金剛烧基、三環癸基、降冰片基以及異冰片基所構成 的群組之官能基。 8 200813639 在本發明的另一具體例中，該水溶性聚合物可以具有 一係為5,000-1，000,000之重量平均分子量(Mw)。 在本發明的另一具體例中，該醇類可以選自於由甲 醇、乙醇、異丙醇、乙二醇、環己醇、氫化安息香以及其 5 等之混合物。 在本發明的另一具體例中，該鹼可以能是一有機氨類 或一羥化銨鹽。 在本發明的另一具體例中，該鹼類可以選自於由2-(2-氨基乙基氨基）乙醇、1，1，3,3-四（甲氧基甲基)尿素、乙二氨、 10 二亞乙基三氨、吡啶、烯丙氨、氨基乙醇、三乙氨以及其 等之混合物所構成的群組。 在本發明的另一具體例中，該形成微形圖案的樹脂組 成物可以包含有係為重量的50至99%的水性醇類或鹼性溶 液，以及係為重量的1至50%之水溶性聚合物。 15 在本發明的又另一具體例中，該水溶液在以100份的重 量之水的基礎下，可以包含有重量為0.1-5份之醇類或者鹼 類。 依據本發明，其亦提供一種形成微形圖案的方法，該 方法包含有以下步驟：a)在一基材上形成光阻樹脂層，b) 20 將該光阻樹脂層曝光並顯像以形成一光阻圖案層，c)將該 形成微形圖案的樹脂組成物施加於該光阻圖案層的表面， d)誘發該光阻圖案層的表面之膨脹以形成一經膨脹的光 阻圖案層，e)在該經膨脹的光阻圖案層與和該形成微形圖 案的樹脂組成物之間的界面誘發纏結作用，並且〇使用包 9 200813639 含有機溶劑的水、一水性鹼性溶液 ^水洛液，來移除該 經纏結部分之外的該水溶性聚合物。 依據本發明，其也提供由該方法所形成的微形圖案。 依據本發明，其也有提供一種包含有—使用該微形圖 案之圖案的半導體積體電路裝置。 圖式簡單說明 本發明之上述與其他目的、特徵以及其他優點將可以 由下列的詳細描述以及隨附圖式而被更清楚地理解，其中·· 第1圖顯示例示說明一種形成微形圖案之方法的各別 10步驟，其係藉著將本發明的—形成微形圖案之樹脂組成物 施加至一光阻圖案層的表面而達成。200813639 IX. INSTRUCTIONS: FIELD OF THE INVENTION The present invention relates to a resin composition for forming a micropattern, and the 5 series can be used to reduce the concavity in the semiconductor lithography process. , , product or width. BACKGROUND OF THE INVENTION In recent years, the high degree of integration of semiconductor devices has led to a reduction in the width of the wires in the manufacture of the 10-body device, and the distance between the yak v 丄 and the 4-wire. The general process η required for the development of semiconductor devices is divided into lithography, surname, cleaning action, σ, χ, 卞, 金属, 金属, metal wire routing, and other processes. In this case, the "patterning technology is the most important in the lithography process and the 2 technology" 15 maximal integrated circuit provides the driving force for development. The 微 ^ 体 device 8 lithography process contains one Exposure to the illumination pattern is performed under - imaging illumination (4) Photoresistance to pass through 20 layers. The image is then contacted by the exposed-cased photoresist (typically - aqueous inspection imaging agent), buried (4) The photoresist layer is removed, and the (4) pattern is displayed, and a portion of the pattern is then applied to the underlying material. After the transfer is completed, The material is removed and removed. 'The residual photoresist layer requires lithography to use nine shots with shorter wavelengths, while the high resolution 5 imaging effect of the 200813639 photoresist is based on the characteristics of the illumination. There are differences. However, the improvement of the exposure system requires shortening the wavelength of light, and therefore it will incur considerable expense. In addition, it is not easy to develop a photoresist material for short-wavelength illumination applied to exposure. ,traditional The lithography technique is limited by the wavelength of the illumination used for the exposure, so it will be limited in terms of micropatterning to improve the integration of the integration. Some attempts have been made to overcome these limitations. For example, Japanese Patent No. 3,071,401 describes a micropatterning material which uses a water-soluble resin to generate a crosslinking reaction with a photoresist in the presence of an acid to thereby provide an acid from the photoresist pattern. Forming a crosslinked film at the interface between the photoresist pattern and the micro pattern forming material, and peeling off the uncrosslinked portion. However, when the material is used to form a pattern, the photoresist The pattern may be deformed by the reduction of the volume of the resin caused during the crosslinking reaction and the stress generated by 15. Therefore, there is a need for a micropatterning material capable of overcoming the limitations of conventional materials, which has a A new type of mechanism. C SUMMARY OF THE INVENTION 3 SUMMARY OF THE INVENTION The present invention is made in consideration of the problems of the prior art, and one object of the present invention is Provided is a micropatterning material having a new type of mechanism capable of overcoming the limitation of wavelength in miniaturization of a pattern such as in a separate pattern or a hole pattern. The inventors have conducted research intensively and intensively. Achieved the purpose of 6 200813639. As a result, the inventors of the present invention have found that an aqueous alcohol or alkaline solution can be used to induce the expansion of the photoresist pattern layer, and a water-soluble polymer is used to induce the expansion. The entanglement phenomenon between the photoresist pattern layer and the water-soluble polymer such that the width of the groove portion of the photoresist pattern layer can be reduced by 5 degrees. The present invention has been achieved based on this finding. According to the present invention, Providing a resin composition comprising a water-soluble polymer and a solvent to form a micro-pattern, wherein a micro-pattern is induced by applying the resin composition to a photoresist pattern layer The surface of the pattern layer is expanded to form an expanded photoresist pattern layer between the stretched photoresist pattern layer and the micropatterned resin composition The interface induces entanglement and is formed using a developing solution to remove a portion of the water-soluble polymer other than the entangled portion. In one embodiment of the invention, the solvent may be an aqueous alcohol or an assay solution. In a further embodiment of the invention, the water-soluble polymer may be a hydrophilic monomer unit or a homogeneous polymer composed of a copolymer of two or more hydrophilic monomer units. In another embodiment of the present invention, the water-soluble polymer may be a copolymerized 20 composed of at least one hydrophilic monomer unit and at least one monomer unit selected from the group consisting of vinyl pyridine , vinyl thiophene, styrene, ethyl carbene, vinyl benzoate, vinyl methyl saliva, ethylene diamino trisodium salicylate, ethyl sulfonium triterpenoid, and ethyl hydrazine The group formed. In another embodiment of the present invention, the water-soluble polymer may be an alkali-based shirt and a base of at least a (meth)acrylic acid monomer planted by 7 200813639, ::; The acrylic acid monomer unit has 5 10 15 20 monomer selected from the group consisting of an amanta functional group norbornyl group and an isobornyl group. In another specific example, the water-soluble polymer Hydrophilic ammonia, hetero 8 to 4 - selected from the group consisting of a thiol group, a thiol group, a hydrazone group, and a group. And the monomer composed of the acid group. In another specific example, the hydrophilicity of the water-soluble polymer is selected from the group consisting of vinyl alcohol, vinyl lysine, acrylic acid, oxyethylene hydride, and A group consisting of dilute base methyl methacrylate vinegar, shout, vinyl oxime, ethylene dilute, dilute propylamine, vinyl terephthalate, vinyl chelate, and combinations thereof. In another specific example, the number of the hydrophilic monomer units ">, the ratio of the number of the early body units is between i: (4) correction: the \ at least - the monomer unit is selected from the group consisting of vinyl ^, ethylene: phenophene, the present ethylene, ethylene-based saliva, ethylene benzoate saliva, ethylene base (four) 'vinyl diamino three flavor. Sitting, ethylene-like saliva and vinyl tetraimidazole In the other specific example of the present month, the ratio of the number of the hydrophilic monomeric elements to the number of the monomer units of the (meth)acrylic acid is between :: 0.01 and 1: 0.5 between the (meth) acrylate monomer units and having a functional group selected from the group consisting of an adamantyl group, a tricyclic fluorenyl group, a norbornyl group, and an isobornyl group. 8 200813639 In another embodiment of the present invention, the water-soluble polymer may have a weight average molecular weight (Mw) of from 5,000 to 1,000,000. In another embodiment of the present invention, the alcohol may be selected from A mixture of methanol, ethanol, isopropanol, ethylene glycol, cyclohexanol, hydrogenated benzoin, and the like. In another embodiment of the present invention, the base may be an organic ammonia or a monohydroxyammonium salt. In another embodiment of the present invention, the base may be selected from the group consisting of 2-(2-amino). Ethylamino)ethanol, 1,1,3,3-tetrakis(methoxymethyl)urea, ethylenediamine, 10 diethylenetriamine, pyridine, allylamine, aminoethanol, triethylamine, and In another embodiment of the present invention, the resin composition forming the micropattern may comprise 50 to 99% by weight of an aqueous alcohol or an alkaline solution, and a system 1 to 50% by weight of a water-soluble polymer. 15 In still another embodiment of the present invention, the aqueous solution may comprise from 0.1 to 5 parts by weight based on 100 parts by weight of water. Or a base. According to the present invention, there is also provided a method of forming a micropattern comprising the steps of: a) forming a photoresist resin layer on a substrate, b) 20 exposing the photoresist resin layer And developing to form a photoresist pattern layer, c) applying a resin pattern forming the micro pattern to the photoresist pattern a surface of the layer, d) inducing expansion of the surface of the photoresist pattern layer to form an expanded photoresist pattern layer, e) between the expanded photoresist pattern layer and the resin composition forming the micro pattern The interface induces entanglement, and the water-soluble polymer other than the entangled portion is removed according to the present invention by using water containing an organic solvent, a water-based alkaline solution, in accordance with the present invention. It also provides a micropattern formed by the method. According to the present invention, there is also provided a semiconductor integrated circuit device including a pattern using the micropattern. The drawings briefly illustrate the above and other objects of the present invention. The features and other advantages will be more clearly understood from the following detailed description and the accompanying drawings in which: FIG. 1 shows a exemplification of a respective 10 steps of a method of forming a micropattern by The resin composition forming the micropattern of the present invention is applied to the surface of a photoresist pattern layer.
C資施方式J 較佳實施例之詳細說明 本發明現在將被描述更詳細地。 15纟發明係與—種塗覆在—光阻圖案上之形成微形圖案 的樹脂組成物有關。本發明之形成微形圖案的樹脂組成物 包含有一水性醇類或是鹼性溶液以及一水溶性聚合物。 忒水性醇類或鹼性溶液可被用來誘發一光阻圖案層之 表面的膨脹現象，並且該與光阻圖案層的表面接觸之水溶 20性聚合物，係被用來誘發在該經膨脹的光阻圖案層以及該 形成微形圖案的樹脂組成物之間的界面之纏結，以形成一 不會溶解的薄膜。形成微形圖案的樹脂組成物之沒有誘發 纏結的部分，係被包含有一被用來作為顯像溶液的有機溶 劑之水、一水性鹼性溶液或一水溶液所移除。 200813639 該水溶性聚合物係為一親水性單體單元或一具有一或 更多親水性單體單元之共聚物所組成的均質聚人物 該水溶性聚合物的親水性單體單元係較佳地具有至小 一選自於由減、紐基、醯氨基、氨基、—基、、=少 酯基、縮醛基以及磺酸基所構成的群組之官能美。更明確 地說，乙烯醇、乙烯基醣類、乙烯基羥基乙 乂 «t. -Λ·' -fch ΑΛ· 土土丙 酸 =或^4之類似物，可以被料作為該具有—經基之單 體，丙稀酸、甲基丙稀酸、苯并丙烯酸酸或其等之類似物 可以被用來作為該具有一羧酸基之單體； ^ 10 15 20 氨或其等之類似物，可以被用來作為該具有二，烯丙 體；並且乙烯基鱗院酉同、乙烯基喔0坐琳、早 其等之類似物，可以被用來作為該具有 4土^坐或 環氧乙烧也可以被用來作為該親水性單體單元土之單體。 一種由該等親水性的單體單元中之— 聚合物，以及-種由該等親水性的單_ 2、、且成的均質 一種由該等親水性的單體單元_之至少—、 對構成該光阻圖案的樹脂具有親和力者以及一種 共聚物，係可以被用來作為該水溶性7早謂組成的 中，該對構成該光阻圖案的樹脂具有親：„兄 可以依據該光阻圖案層_型而決定。11之早體單元， 之 舉例來說’在該光阻圖案層係由包 KrF光阻所形成的情況中，對構成科_=:= 11 200813639 有親和力之單體單元係可以選自於由乙烯基吡啶、乙烯基 噻吩、苯乙烯、乙烯基咔唑、乙烯基苯并咪唑、乙烯基甲 基咪唑、乙烯基二氨基三咪唑、乙烯基三咪唑、乙烯基四 咪唑，以及其等之混合物所構成的群組。 5 在該光阻圖案層係由包含有脂環族化合物之ArF光 阻所形成的情況中，對構成該光阻圖案的樹脂具有親和力 之單體單元可以至少係為一具有選自於由金剛烷基、三環 癸基、降冰片基以及異冰片基所構成的群組之官能基的 (甲基）丙烯酸單體單元。 10 只要不會損害該水溶性聚合物的水溶性，該親水性的 單體單元可以與對在各種不同的圖案中構成該光阻圖案的 樹脂具有親和力之單體單元進行共聚反應，舉例來說隨機 共聚反應、區塊共聚反應以及接枝共聚反應。隨機共聚反 應係為較佳。 15 在該水溶性聚合物係由該親水性單體單元以及一對構 成該光阻圖案的樹脂具有親和力之單體單元所組成的情況 中，該親水性單體單元的數量與該對構成該光阻圖案的樹 脂具有親和力之單體單元的數量之比例係較佳地介於1 : 0.01和1 : 0.5之間。如果該對構成該光阻圖案的樹脂具有親 20 和力之單體單元係以相對較小的數量來運用的話，在該可 溶性聚合物與光阻樹脂之間的纏結作用並不會被輕易地誘 發。同時，如果為該對構成該光阻圖案的樹脂具有親和力 之單體單元係以相對較大的數量來運用的話，則會有水溶 性聚合物的水溶性被損害的問題。 12 200813639 只要不會損害本發明的效果，該水溶性聚合物的分子 量可以被任意地決定。為了要使得在該可溶性聚合物與光 阻樹脂之間的纏結效果在施加後最大化，而同時確保該水 溶性聚合物之有效水溶性與可塗覆性，該水溶性聚合物的 5重量平均分子量(Mw)係較佳地被調整到5,〇〇〇至1，000,000 的範圍之間，更佳地被調整到30,000至1〇〇,〇〇〇的範圍之 間。當該水溶性聚合物具有一低於5,〇〇〇的重量平均分子量 (Mw)時，該水溶性聚合物與該經膨脹的光阻樹脂之間的纏 結現象並不足夠。同時，當該水溶性聚合物具有一高於 ⑺1，_，GGG的重量平均分子量(Mw)時，該水溶性聚合物的水 ’合解度係較差，而且該水溶性聚合物的聚集現象會在施加 時發生，而形成一不均勻的塗層。 15 20 可以構成光阻圖案之任何的感光性樹脂都可以被用於 本么月舉例來。兒，在KrF光阻包含有聚經基苯乙稀的情況 中，該聚減苯乙烯_基中之-部分係以乙基乙稀基醚 基I來取代，作為對酸中不安定的保護基團。在KrF光阻 ，含有-脂壞化合物的情況中，該脂環化合物係以對酸不 ==團來取代。該Μ光阻和ArF光阻係為非水溶 在化兩種清况中，因為在一經圖案化層的表面上之該 非水溶性有機聚合物的—部份會被去保護，該等聚人物可 =被溶解在―高滚度水性_或驗性溶液中。^如下 下所=制=阻_的表面可以在沒有完全被溶解 水性醇類或驗性溶液中之醇類或驗類含量 13 200813639 而膨脹。 =控制醇類或驗類的内容的之外，該水溶性聚合物 5 10 15 20 現象所.諸°被調控U改變該水溶性聚合物由於該纏結 H致㈣水雜之程度，並且結果可雜制在該等 2案化μ之間的距離以及孔洞開口的大小的縮減程度。 一來§兄’在下列的具體财—具有大約胤之重量平均分 t量的水溶性聚合物，係被用來減少m約4〇 nm: 見度的光阻圖案層之凹槽部分的寬度。 …本發明的水雜樹脂組成物包含有-水性醇類或驗性 洛液。該水性醇類或驗性溶液會穿透過該構成一光阻圖案 層的樹脂之表面而使得該樹脂膨脹。因此，該類型的水性 =驗性溶液並未被特一於溶解在水中的只醇類 2域«柄基_之切㈣，可以被用 選自於由甲醇、乙醇、異丙醇：_類係較佳地 息香以及其等之混合物所構成的群:&⑽、氫化安 -例減錢、科氨或二氨、技—削 機氰，可以被用來作為包含在該水溶液中之之有 說，該驗係較佳地選自於由化學心 /確地 乙醇、化學式2的u，3,3,(甲氧基甲基)尿素 = 乙二基气氨基） :基二氨、二亞乙基三氨，定、歸丙氨、氨基乙 乙虱以及其等之混合物所構成的群組。 一 TO , , MW. m ⑴ 14 200813639C. MODE FOR CARRYING OUT THE INVENTION Detailed Description of the Preferred Embodiment The present invention will now be described in more detail. The invention is related to a resin composition which is coated on a photoresist pattern to form a micropattern. The micropattern-forming resin composition of the present invention comprises an aqueous alcohol or an alkaline solution and a water-soluble polymer. A hydrophobic alcohol or an alkaline solution can be used to induce swelling of the surface of a photoresist pattern layer, and the water-soluble 20-polymer which is in contact with the surface of the photoresist pattern layer is used to induce expansion in the layer. The interface between the photoresist pattern layer and the resin composition forming the micro pattern is entangled to form a film that does not dissolve. The portion of the resin composition forming the micropattern which does not induce entanglement is removed by containing water, an aqueous alkaline solution or an aqueous solution which is used as an organic solvent of the developing solution. 200813639 The water-soluble polymer is a hydrophilic monomer unit or a homogeneous polymer composed of a copolymer having one or more hydrophilic monomer units. Preferably, the hydrophilic monomer unit of the water-soluble polymer is preferably a hydrophilic monomer unit. It has a functional beauty selected from the group consisting of a minus, a neokyl group, a fluorenylamino group, an amino group, a — group, a = less ester group, an acetal group, and a sulfonic acid group. More specifically, vinyl alcohol, vinyl saccharide, vinyl hydroxyacetamyl «t. - Λ · ' - fch ΑΛ · soil propionic acid = or ^ 4 analog, can be expected to be used as the Monomer, acrylic acid, methyl methic acid, benzoacrylic acid or the like can be used as the monomer having a monocarboxylic acid group; ^ 10 15 20 ammonia or the like , can be used as the analog having two, allenes; and vinyl scales, vinyl 喔 0 sit, early, etc., can be used as the 4 soil or epoxy Ethylene can also be used as a monomer for the hydrophilic monomer unit. a polymer from the hydrophilic monomer units, and a homogeneous one of the hydrophilic monomers, and at least one of the hydrophilic monomer units The resin constituting the photoresist pattern has an affinity and a copolymer which can be used as the water-soluble 7 composition, the pair of resins constituting the photoresist pattern have a pro: The pattern layer _ type is determined. The early body unit of 11, for example, in the case where the photoresist pattern layer is formed by a package KrF photoresist, the monomer having an affinity for the composition _=:= 11 200813639 The unit system may be selected from the group consisting of vinyl pyridine, vinyl thiophene, styrene, vinyl carbazole, vinyl benzimidazole, vinyl methyl imidazole, vinyl diamino triimidazole, vinyl triimidazole, vinyl four a group consisting of imidazole, and a mixture thereof, etc. 5 In the case where the photoresist pattern layer is formed of an ArF photoresist containing an alicyclic compound, the affinity for the resin constituting the photoresist pattern is single. Body unit can be at least Is a (meth)acrylic monomer unit having a functional group selected from the group consisting of adamantyl, tricyclodecyl, norbornyl and isobornyl. 10 as long as the water-soluble polymerization is not impaired Water-soluble, the hydrophilic monomer unit can be copolymerized with a monomer unit having affinity for a resin constituting the photoresist pattern in various patterns, for example, random copolymerization, block copolymerization, and Graft copolymerization reaction. Random copolymerization is preferred. 15 In the case where the water-soluble polymer is composed of the hydrophilic monomer unit and a pair of monomer units having affinity for the resin constituting the photoresist pattern, The ratio of the number of the hydrophilic monomer units to the number of monomer units having an affinity for the resin constituting the photoresist pattern is preferably between 1:0.01 and 1:0.5. If the pair constitutes the light If the resin of the resist pattern has a relatively small amount of the monomer unit and the force, the entanglement between the soluble polymer and the photoresist resin is not easily At the same time, if the monomer unit having affinity for the resin constituting the resist pattern is used in a relatively large amount, the water solubility of the water-soluble polymer may be impaired. 12 200813639 The effect of the present invention is not impaired, and the molecular weight of the water-soluble polymer can be arbitrarily determined in order to maximize the entanglement effect between the soluble polymer and the photoresist resin after application, while ensuring the water solubility. The effective water solubility and coatability of the polymer, the 5-weight average molecular weight (Mw) of the water-soluble polymer is preferably adjusted to a range of 5, 〇〇〇 to 1,000,000, more preferably Adjusted to between 30,000 and 1 〇〇, between the ranges of 〇〇〇. When the water-soluble polymer has a weight average molecular weight (Mw) of less than 5, 〇〇〇, the water-soluble polymer and the swell The entanglement between the photoresist resins is not sufficient. Meanwhile, when the water-soluble polymer has a weight average molecular weight (Mw) higher than (7) 1, _, GGG, the water-complexity of the water-soluble polymer is poor, and the aggregation of the water-soluble polymer is Occurs upon application to form a non-uniform coating. 15 20 Any photosensitive resin that can form a photoresist pattern can be used for this month. In the case where the KrF photoresist contains polystyrene styrene, the portion of the polystyrene-based group is substituted with ethyl ethyl ether group I as an unstable protection against acid. Group. In the case of a KrF photoresist containing a -lipid compound, the alicyclic compound is substituted with an acid === group. The bismuth photoresist and the ArF photoresist are in a non-water-soluble condition because the portion of the water-insoluble organic polymer on the surface of the patterned layer is deprotected, and the poly-character can = is dissolved in the "high rolling water" or the test solution. ^ The following surface = system = resistance _ surface can be swelled in the alcohol or test content of the water alcohol or the test solution is not completely dissolved 13 200813639. = controlling the content of the alcohol or the test, the water-soluble polymer 5 10 15 20 phenomenon is controlled by U to change the degree of water-soluble polymer due to the entanglement of H (four) water, and the result The distance between the two μs and the reduction in the size of the opening of the hole can be mixed. One of the § brothers' in the following specific financials - a water-soluble polymer having an average weight fraction of about 胤 is used to reduce m by about 4 〇 nm: the width of the groove portion of the photoresist pattern layer of visibility . The water-containing resin composition of the present invention contains an aqueous alcohol or an aqueous solution. The aqueous alcohol or the test solution penetrates the surface of the resin constituting the photoresist pattern layer to cause the resin to swell. Therefore, this type of aqueous test solution is not specifically selected from the alcohol-only domain 2, which is dissolved in water, and can be used in selected from methanol, ethanol, and isopropanol: Preferably, a mixture of aromas and mixtures thereof: & (10), hydrogenated anthracene, reduced ammonia, co-amine or diamine, and cyanide, can be used as contained in the aqueous solution. It is said that the test system is preferably selected from the group consisting of chemically/accurately ethanol, u, 3, 3, (methoxymethyl) urea of the formula 2, ethylenediylamino: pyrithione, A group consisting of diethylene triamine, a mixture of dimethylamine, aminoethyl hydrazine, and the like. A TO , , MW. m (1) 14 200813639
本發明之形成微形圖案的樹脂組成物係較佳地包含有 為重里的50至99%之該水性醇類或驗性溶液，以及為重量 的10至50%之該水溶性聚合物。當該水溶性聚合物係以少 5於重里的1%的含量存在時，其係它不足以與—光阻樹脂形 成纏結。同時，當該水溶性聚合物係以超過5〇%的含量存 在時，則會有在該形成微形圖案的樹脂組成物不能夠輕易 地塗覆於該光阻圖案層的表面上之問題。 該水溶液在以水的重量為1〇〇份基礎下，係較佳地包含 10有為0.1-5份重量之醇類或者驗類，且其更佳地為⑴份的 重里。使用少於G.1份的重量之醇類或驗類會使得構成一光 阻圖案層之樹脂無法形成令人滿意之膨騰作用。同時，使 用超過5份的重量之醇類或鹼類可能會使得該構成一光阻 圖案層之樹脂的溶解，而倒致該圖案的崩潰。 15 本發明係為一種形成一微形圖案的方法，該方法包含 有以下步驟：a)在一基材上形成光阻樹脂層，b)將該光阻 樹脂層曝光並顯像以形成一光阻圖案層，c)將該形成微形 圖案的樹脂組成物施加於該光阻圖案層的表面，d)誘發該 光阻圖案層的表面之膨脹以形成一經膨脹的光阻圖案層， 20 e)在該經膨脹的光阻圖案層與和該形成微形圖案的樹脂 組成物之間的界面誘發纏結作用，並且〇使用包含有機溶 劑的水、-水性驗性溶液或-水溶液，來移除該經纏結部 15 200813639 分之外的該水溶性聚合物。 以下，本發明的方法將參照例示說明使用一KrF光阻來 形成微形圖案的第1圖而明確地解說。 第1圖顯示例示說明藉著將本發明的該形成微形圖案 5 的樹脂組成物施加至一KrF光阻圖案層的表面上，以誘發構 成該光阻圖案層之樹脂的膨脹現象以及在該可溶解聚合物 與該經膨脹光阻樹脂層之間的纏結現象的方法之各別的步 驟(a)到⑴。 如在第1圖中所示，該KrF光阻樹脂層2係被形成在一例 10如半導體基材之基材1上（步驟a)。然後，該光阻樹脂層2係 利用一光罩（未顯示）而以一 KrF準分子雷射作為光源來進 行照射、曝光與顯像，以形成一光阻圖案層3(步驟b)。本發 明之該形成微形圖案之樹脂組成物係被施加至該光阻圖案 層3以形成一塗覆層4(步驟c)。包含在該塗覆層4中的該水性 醇類或鹼性溶液，會誘發該光阻圖案層3表面的一種膨脹現 象，以形成一經膨脹的光阻圖案層5(步驟d)。此時，在該形 成微形圖案的樹脂組成物之水溶性聚合物的分子鏈與該塗 覆層之間的纏結現象係被誘發，以在該塗覆層4與經膨脹的 光阻圖案層5(步驟e)之間的界面形成一纏結層6。接著，部 2〇 分沒有被誘發該纏結作用的該塗覆層4係被以包含有機溶 劑之水、一水性鹼液或是一水溶液所移除，以形成一其中 該光阻圖案層之凹槽部分的寬度(CDA)會減少之微形圖案 (步驟f)。 該方法所形成的微形圖案可以被用來製造一半導體積 16 200813639 體電路裝置。明確地說，在一微形圖案藉著該方法而形成 於一例如矽晶圓的基材上之後，圖案化作用係以該微形圖 案作為一光阻圖案而在該基材上形成一圖案。I虫刻作用可 被用用於該圖案化作用。 $ 本發明提供一種包含使用該微形圖案而形成的圖案之 半導體積體電路裝置。 在下述中，本發明將被參照下列的具體例而更詳細地 說明。然而，這些具體例為僅係用於例示說明而非用來侷 限制本發明。 10 具體例 [合成具體例1](水溶性聚合物l(Mw = 5K)的合成）3〇〇 毫升的異丙醇係被置入500毫升的三頸燒瓶内，於一氮氣環 境下攪拌一小時的並在7〇°c下迴流。71.94克的N-乙烯基吡 洛烧酮、13.60克的4-乙烯基吡啶、2.56克的二甲基-2,2，-二 15 丙酸甲酯以及5〇毫升的異丙醇係加至該到燒瓶。該混合 務被攪拌4小時。該反應溶液被冷卻至室溫並藉著在真空中 蒸餾而濃縮至少於最初體積之一半。5〇〇毫升的二乙醚係被 加至该濃縮液以得到一沈澱物。該沈澱物係以二乙醚來過 濾、洗滌與純化三次並在一烤箱中乾燥，可以得到肋幻克 20之化學式3的聚（乙烯基吡咯烷酮-共-乙烯基吡啶）。The micropattern-forming resin composition of the present invention preferably comprises from 50 to 99% by weight of the aqueous alcohol or test solution, and from 10 to 50% by weight of the water-soluble polymer. When the water-soluble polymer is present in an amount of less than 1% by weight, it is insufficient to form an entanglement with the photoresist. Meanwhile, when the water-soluble polymer is present in an amount of more than 5% by mass, there is a problem that the resin composition forming the micro pattern cannot be easily applied to the surface of the photoresist pattern layer. The aqueous solution preferably contains 10 to 0.1 to 5 parts by weight of the alcohol or the like, and more preferably (1) parts by weight based on 1 part by weight of water. The use of an alcohol or a test having a weight of less than G.1 part causes the resin constituting a resist pattern layer to fail to form a satisfactory tumbling effect. At the same time, the use of more than 5 parts by weight of an alcohol or a base may cause dissolution of the resin constituting the photoresist pattern layer, which may cause collapse of the pattern. The present invention is a method of forming a micropattern comprising the steps of: a) forming a photoresist resin layer on a substrate, b) exposing and developing the photoresist resin layer to form a light a resist pattern layer, c) applying a resin pattern forming the micro pattern to the surface of the photoresist pattern layer, d) inducing expansion of the surface of the photoresist pattern layer to form an expanded photoresist pattern layer, 20 e The entanglement is induced at the interface between the expanded resist pattern layer and the resin composition forming the micro pattern, and the hydrazine is removed using water containing an organic solvent, an aqueous test solution or an aqueous solution. The water-soluble polymer except the entangled portion 15 200813639. Hereinafter, the method of the present invention will be specifically explained with reference to a first diagram in which a KrF photoresist is used to form a micropattern. 1 is a view showing the application of the resin composition forming the micropattern 5 of the present invention to the surface of a KrF photoresist pattern layer to induce the expansion phenomenon of the resin constituting the photoresist pattern layer and Each of the steps (a) to (1) of the method of dissolving the entanglement phenomenon between the polymer and the expanded photoresist resin layer. As shown in Fig. 1, the KrF photoresist resin layer 2 is formed on a substrate 1 such as a semiconductor substrate (step a). Then, the photoresist resin layer 2 is irradiated, exposed, and developed with a KrF excimer laser as a light source by a photomask (not shown) to form a photoresist pattern layer 3 (step b). The resin composition forming the micropattern of the present invention is applied to the photoresist pattern layer 3 to form a coating layer 4 (step c). The aqueous alcohol or alkaline solution contained in the coating layer 4 induces an expansion phenomenon of the surface of the photoresist pattern layer 3 to form an expanded photoresist pattern layer 5 (step d). At this time, the entanglement phenomenon between the molecular chain of the water-soluble polymer of the resin composition forming the micro pattern and the coating layer is induced to be in the coating layer 4 and the expanded resist pattern. The interface between layer 5 (step e) forms an entangled layer 6. Then, the portion 2 is not removed by the coating layer 4 which is not induced by the entanglement, and is removed by water containing an organic solvent, an aqueous alkali solution or an aqueous solution to form a photoresist pattern layer therein. The width of the groove portion (CDA) is reduced by the micropattern (step f). The micropattern formed by the method can be used to fabricate a semiconductor device. Specifically, after a micro pattern is formed on a substrate such as a germanium wafer by the method, the patterning is performed by forming the pattern on the substrate by using the micro pattern as a photoresist pattern. . I insect engraving can be used for this patterning. $ The present invention provides a semiconductor integrated circuit device including a pattern formed using the micropattern. In the following, the invention will be explained in more detail with reference to the following specific examples. However, these specific examples are for illustrative purposes only and are not intended to limit the invention. 10 Specific Example [Synthesis Specific Example 1] (Synthesis of Water-Soluble Polymer 1 (Mw = 5K)) 3 ml of isopropanol was placed in a 500 ml three-necked flask and stirred under a nitrogen atmosphere. Hour and reflux at 7 ° C. 71.94 g of N-vinylpironone, 13.60 g of 4-vinylpyridine, 2.56 g of dimethyl-2,2,-di-15 propionic acid methyl ester and 5 ml of isopropanol were added to The to the flask. The mixture was stirred for 4 hours. The reaction solution was cooled to room temperature and concentrated by at least one half of the original volume by distillation in a vacuum. 5 ml of diethyl ether was added to the concentrate to obtain a precipitate. The precipitate was filtered, washed and purified three times with diethyl ether and dried in an oven to obtain a poly(vinylpyrrolidone-co-vinylpyridine) of the formula 3 of the rib.
〇 ^ (3) 所里彳于之该共聚物的重量平均分子量為5K。 17 200813639 [合成具體例2](水溶性聚合物2(Mw = 10K)的合成）除 了 1.5克的二甲基-2,2’-二丙酸甲酯係被用來作為起始劑 之外，80.53克的聚（乙烯基吡咯烷酮·共-乙烯基吡啶)係以與 合成具體例1相同的方法來合成。所量得之該共聚物的重量 5 平均分子量為10K ° [合成具體例4](水溶性聚合物4(Mw = 70K)的合成）除 了 〇·2克的二甲基-2,2f-二-2-丙酸甲酯係被用來作為起始劑 之外’ 78.43克的聚（乙稀基u比σ各烧酮·共-乙稀基η比σ定)係以與 合成具體例1相同的方法來合成。所量得之該共聚物的重量 10 平均分子量為70Κ。 [合成具體例5](水溶性聚合物5(Mw = 150Κ)的合成）除 了 0·1克的二甲基_2,2’-二-2-丙酸甲酯係被用來作為起始劑 之外80.33克的聚（乙烯基吼。各烧酮_共_乙烯基^比咬)係以與 合成具體例1相同的方法來合成。所量得之該共聚物的重量 15 平均分子量為150Κ。 [一成/、體例6](水溶性聚合物6(mw = 70Κ)的合成）除 了 〇·7克的二甲美9 〇，《 、 ，2·二-2-丙酸甲酯係被用來作為起始劑 、使用7·3克的乙烯基味唾之外，110.5克的聚乙烯基口米唑 ⑷子<4)係以與合成具體例^相同的方法來合成。共聚物 ^ (3) The copolymer has a weight average molecular weight of 5K. 17 200813639 [Synthesis Specific Example 2] (Synthesis of Water-Soluble Polymer 2 (Mw = 10K)) In addition to 1.5 g of methyl dimethyl-2,2'-dipropionate was used as a starter 80.53 g of poly(vinylpyrrolidone·co-vinylpyridine) was synthesized in the same manner as in Synthesis Example 1. The weight of the copolymer was measured and the average molecular weight was 10 K ° [Synthesis Specific Example 4] (synthesis of water-soluble polymer 4 (Mw = 70 K)) except 〇·2 g of dimethyl-2,2f-di Methyl-2-propionate was used as a starting agent in addition to '78.43 g of poly(ethylene-based 比 σ ketone ketone·co-ethylene η ratio σ) to synthesize specific example 1 The same method to synthesize. The weight of the copolymer obtained was 10 and the average molecular weight was 70 Å. [Synthesis Specific Example 5] (Synthesis of Water-Soluble Polymer 5 (Mw = 150 Å)) In addition to 0.1 g of dimethyl 2,2'-di-2-propionic acid methyl ester was used as a starting point 80.33 g of poly(vinyl anthracene, each ketone-co-vinyl group) was synthesized in the same manner as in Synthesis Example 1 except for the agent. The weight of the copolymer obtained was 15 and the average molecular weight was 150 Å. [1% /, Example 6] (Synthesis of water-soluble polymer 6 (mw = 70 Κ)) In addition to 〇·7 g of dimethyl hydrazine 9 , " , 2 , 2 - 2-propionic acid methyl ester was used In addition to 7.3 g of a vinyl-flavored saliva as a starter, 110.5 g of a polyvinyl-trimazole (4) sub- <4) was synthesized in the same manner as in the synthesis of the specific examples.
(4) 所量得之兮取 Γ人、 &物的重量平均分子量為70Κ 〇 [a成具體例 水溶性聚合物7(Mw二70K)的合成）除 18 200813639 了 0.7克的二甲基-2,2’-二-2-丙酸甲酯係被用來作為起始劑 並使用167.5克的羥基乙基甲基丙烯酸酯之外，155.85克的 聚羥基乙基甲基丙烯酸酯（化學式5)係以與合成具體例1相 同的方法來合成。(4) The weight average molecular weight of the obtained sputum and & substance is 70 Κ 〇 [a specific example of the synthesis of water-soluble polymer 7 (Mw 2 70K)) except 18 200813639 0.7 g of dimethyl -2,2'-di-2-propionic acid methyl ester was used as a starter and used as 167.5 g of hydroxyethyl methacrylate, 155.85 g of polyhydroxyethyl methacrylate (chemical formula 5) It was synthesized in the same manner as in Synthesis Example 1.
0、 /0 5 (5) 所量得之該聚合物的重量平均分子量為70K。 [具體例1-12] 依據在表1中所指出組成成分，在合成具體例1-7所製 備的水溶性聚合物係被用來製備形成微形圖案的樹脂組成 10 物。 表1 具體例 編號 水溶性聚合物 2-(2-氨基乙基氨 基）乙醇 1，1，3,3-四（甲氧基 甲基)尿素 水分 1 l〇g， 合成具體例1 Ig lOOg 2 log， 合成具體例1 - 1 g lOOg 3 log， 合成具體例2 1 g - lOOg 4 10g， 合成具體例2 - 1 g lOOg 5 log， 合成具體例3 1 g - lOOg 6 log， 合成具體例3 - 1 g lOOg 7 l〇g， 合成具體例4 Ig - lOOg 8 l〇g， 合成具體例4 - Ig lOOg 9 l〇g， 合成具體例5 1 g - lOOg 10 10g， 合成具體例5 - 1 g lOOg 11 10g， 合成具體例6 1 g - lOOg 12 l〇g， 合成具體例7 1 g - lOOg 19 200813639 [比較例1和2] 如在表2中所指出的，1〇克之在合成具體例4中的該水 溶性聚合物’ 100克的水分，以及不同含量(㈣5克與1〇克) 的2-(2-氨基乙基氨基）乙醇，係被用來製備形成微形圖案的 5 樹脂組成物。 表2 水，聚合物2-(2盆1基氨曱素氧基水分 1 合體例4 0 05 8 - 100g 2 l〇g 9 合成具體例4 108 - 100g [具體例13-24] 微影術實驗係依據以下製程使用在具體例丨_丨2中所製 備之各個形成微形圖案的樹脂組成物來進行。 10 首先，一有機ARC係被塗覆於一石夕晶圓上。一 光阻 係被塗覆在石夕晶圓上，利用曝光系統(ASML800，NA 0.93) 來進行曝光並顯像，以獲得一其上形成了具有最少為179 nm且袁大為183nm的CD0之L/S圖案的經圖案化基材。 接著，在具體例1-12中所製備的每個形成微形圖案之 15樹脂組成物係被塗覆於該經圖案化的基材上，接著被加以 乾燥。 之後，顯像作用係藉著將該經塗覆的基材浸潰於蒸餾 水中來進行。該圖案的臨界尺寸(CD)係以一FE_SEM來加以 /則里，而δ亥專數值係被表示為cda(CD〇係為該經圖案化的 20基材在以每一種形成微形圖案的樹脂組成物來加以塗覆之 前的CD值）。所得到的結果係被顯示在表3中。 20 200813639 樣本 表3 CDO (nm) CDA (nm) 具體例13 179 175 具體例14 181 174 具體例15 183 164 具體例16 180 160 具體例17 182 154 具體例18 183 150 具體例19 179 140 具體例20 181 141 具體例21 183 137 具體例22 183 136 具體例23 182 155 具體例24 180 15? 如在表2的結果所示，水溶性聚合物之分子量的增加對 於微形圖案的形成提供了較大的貢獻。其可被歸因於隨著 水溶性聚合物的分子量逐漸增加而增強之纏結效應。 5 因為本發明的樹脂組成物(舉例來說，在具體例23和24 中製備的樹脂組成物)並未包含會導製交聯的單元，該微形 圖案的凹槽部分之寬度的縮減係來自於與已知的化學交聯 機制不同之新穎類型的機制。那是指，這種現象係被歸因 於水溶性聚合物主鏈之間在一分子層級上的物理性連結。 10前述具體例清楚地支持對於水溶性聚合物之分子量的控制 所產生的CDA數值變化，係與该光阻樹脂的膨脹現象以及 在該光阻樹脂和該水溶性聚合物之間的纏結現象所導致物 理機制，而非一化學交聯機制有關。 [比較例3和4] 15 除了在比較具體例1和2中所製備的每個形成微形圖案 21 200813639 之樹脂組成物在係被塗覆於—基材上，而非在具體例7中所 製備的形成微形圖案之樹脂組成物之外，該具體例19的製 程係被再次進行。 比較例3 比較例4 表4 CDO (nm) 180 179 CDA (nm) 178 5 ，如表4的結果所證實的，使用在比較具體例！中所製備 之形成微形圖案的樹脂組成物所形成的圖案（比較例3)，會 在ID值上顯不出微幅的減少（2 nm)，而使用在比較具體例2 所製備之形成微形圖案的樹脂組成物所形成的圖案（比較 例4)則會坍塌，而使其無法測量該圖案的^^^值。 10 這些結果可以導出使用相對於為100份的重量之水少 於0.1份的重量之驗類，對於微形圖案的形成僅會有一點影 響，而使用超過5份重量的驗類則會使得圖案崩潰的結論。 雖然該L/S圖案已經參照前面的具體例來加以解釋，但 是本發明並不侷限於此而可以被應用於包括電洞圖案的各 15種不同類型之圖案的形成。 自上述的描述中可以了解，當本發明之形成微形圖案的 樹脂組成物被用於一微影術製程被的時候，該那水性醇類或 鹼性溶液係被用來誘發一光阻圖案層的膨脹現象，而該水溶 性聚合物係被用來誘發在該經膨脹的光阻圖案層與水溶性 20聚合物之間的纏結現象，而導致在該光阻寬度圖案層中之凹 槽部分的寬度縮減。因此，依據本發明之該形成微形圖案之 樹脂組成物的使用，會形成可以克服波長限制的微形圖案。 22 200813639 I：圖式簡單說明3 第1圖顯示例示說明一種形成微形圖案之方法的各別 步驟，其係藉著將本發明的一形成微形圖案之樹脂組成物 施加至一光阻圖案層的表面而達成。 5 【主要元件符號說明】 ' 1…基材 2…KrF光阻樹脂層 3…光阻圖案層 4…塗覆層 5…經膨脹的光阻圖案層 6…纏結層 230, /0 5 (5) The weight average molecular weight of the polymer was 70 K. [Specific Example 1-12] According to the constituents indicated in Table 1, the water-soluble polymer prepared in Synthesis of Specific Examples 1 to 7 was used to prepare a resin composition 10 which forms a micropattern. Table 1 Specific examples No. Water-soluble polymer 2-(2-aminoethylamino)ethanol 1,1,3,3-tetrakis(methoxymethyl)urea Moisture 1 l〇g, Synthesis Specific Example 1 Ig lOOg 2 Log, synthesis specific example 1 - 1 g lOOg 3 log, synthesis specific example 2 1 g - lOOg 4 10g, synthesis specific example 2 - 1 g lOOg 5 log, synthesis specific example 3 1 g - lOOg 6 log, synthesis specific example 3 - 1 g lOOg 7 l〇g, Synthesis Specific Example 4 Ig - lOOg 8 l〇g, Synthesis Specific Example 4 - Ig lOOg 9 l〇g, Synthesis Specific Example 5 1 g - lOOg 10 10g, Synthesis Specific Example 5 - 1 g lOOg 11 10g, Synthesis Specific Example 6 1 g - lOOg 12 l〇g, Synthesis Specific Example 7 1 g - lOOg 19 200813639 [Comparative Examples 1 and 2] As indicated in Table 2, 1 gram of synthesis is specific The water-soluble polymer in Example 4 '100 g of water, and different contents ((iv) 5 g and 1 g) of 2-(2-aminoethylamino)ethanol were used to prepare a micropattern 5 Resin composition. Table 2 Water, polymer 2-(2 pots 1 base aminopurine oxygen water 1 complex Example 4 0 05 8 - 100g 2 l〇g 9 Synthesis specific example 4 108 - 100g [Specific examples 13-24] lithography The experiment was carried out according to the following process using each of the resin compositions forming the micropattern prepared in the specific example 丨_丨2. 10 First, an organic ARC system was coated on a ray wafer. It was coated on a Shixi wafer and exposed and developed using an exposure system (ASML800, NA 0.93) to obtain an L/S pattern on which a CD0 having a minimum of 179 nm and a length of 183 nm was formed. Patterned Substrate Next, each of the 15 resin compositions forming the micropattern prepared in Specific Examples 1-12 was applied to the patterned substrate, followed by drying. The imaging effect is carried out by immersing the coated substrate in distilled water. The critical dimension (CD) of the pattern is expressed by a FE_SEM, and the numerical value of δHai is expressed as Cda (CD〇 is the patterned 20 substrate before being coated with each of the resin compositions forming the micropattern CD value) The results obtained are shown in Table 3. 20 200813639 Sample Table 3 CDO (nm) CDA (nm) Specific Example 13 179 175 Concrete Example 14 181 174 Concrete Example 15 183 164 Concrete Example 16 180 160 Specific Example 17 182 154 Specific Example 18 183 150 Specific Example 19 179 140 Specific Example 20 181 141 Specific Example 21 183 137 Specific Example 22 183 136 Specific Example 23 182 155 Specific Example 24 180 15? As shown in the results of Table 2, water-soluble The increase in the molecular weight of the polymer provides a large contribution to the formation of the micropattern. It can be attributed to the entanglement effect which is enhanced as the molecular weight of the water-soluble polymer is gradually increased. 5 Because of the resin composition of the present invention The materials (for example, the resin compositions prepared in Specific Examples 23 and 24) did not contain a unit which would lead to crosslinking, and the width of the groove portion of the micro pattern was reduced from known chemistry. A novel type of mechanism that differs in the cross-linking mechanism. That means that this phenomenon is attributed to the physical linkage at the molecular level between the water-soluble polymer backbones. 10 The foregoing specific examples clearly support water solubility. polymerization The change in the molecular weight produced by the control of the molecular weight is caused by the swelling phenomenon of the photoresist resin and the entanglement between the photoresist resin and the water-soluble polymer, rather than a chemical crosslinking mechanism. [Comparative Examples 3 and 4] 15 In addition to the resin composition forming each of the micropatterns 21 200813639 prepared in Comparative Examples 1 and 2, the resin composition was applied to the substrate instead of the specific example. The process of this specific example 19 was repeated except for the resin composition forming the micropattern prepared in 7. Comparative Example 3 Comparative Example 4 Table 4 CDO (nm) 180 179 CDA (nm) 178 5 , as confirmed by the results of Table 4, used in a comparative example! The pattern formed by the resin composition forming the micropattern prepared in Comparative Example (Comparative Example 3) showed no slight decrease in the ID value (2 nm), but was formed using the preparation prepared in Comparative Example 2. The pattern formed by the resin composition of the micro pattern (Comparative Example 4) collapsed, making it impossible to measure the value of the pattern. 10 These results can be derived using a test with a weight of less than 0.1 part by weight relative to 100 parts by weight, with only a slight effect on the formation of the pico pattern, while using a test of more than 5 parts by weight will result in a pattern The conclusion of the crash. Although the L/S pattern has been explained with reference to the foregoing specific examples, the present invention is not limited thereto and can be applied to the formation of 15 different types of patterns including the hole pattern. As can be understood from the above description, when the resin composition forming the micropattern of the present invention is used in a lithography process, the aqueous alcohol or alkaline solution is used to induce a photoresist pattern. The phenomenon of swelling of the layer, and the water-soluble polymer is used to induce entanglement between the expanded photoresist pattern layer and the water-soluble 20 polymer, resulting in a concave in the photoresist width pattern layer. The width of the groove portion is reduced. Therefore, the use of the resin composition forming the micropattern according to the present invention forms a micropattern which can overcome the wavelength limitation. 22 200813639 I: BRIEF DESCRIPTION OF THE DRAWINGS 3 FIG. 1 shows an exemplary step of illustrating a method of forming a micropattern by applying a resin pattern forming a micropattern of the present invention to a photoresist pattern. The surface of the layer is achieved. 5 [Description of main component symbols] '1...substrate 2...KrF photoresist resin layer 3...resist pattern layer 4...coating layer 5...expanded photoresist pattern layer 6...tangled layer 23