201239538 41890pif 六、發明說明： 【發明所屬之技術領域】 本發明是有關一種採用模具的奈米壓印方法，其中模 具在其表面上具有預定的凹凸圖案。 【先前技術】 在產生磁性記錄媒體（諸如離散磁軌媒體（DTM，201239538 41890pif VI. Description of the Invention: [Technical Field] The present invention relates to a nanoimprinting method using a mold in which a mold has a predetermined concave-convex pattern on its surface. [Prior Art] In the production of magnetic recording media (such as discrete track media (DTM,
Discrete Track Media )以及位元圖案媒體（bpm，BitDiscrete Track Media ) and bit pattern media (bpm, Bit)
Patterned Media))以及半導體元件的應用中，對於採用 奈米壓印方法以將圖案轉印至塗佈在待處理之物件上的光 阻上之圖案轉印技術的利用有著高度期望。 奈米壓印方法為熟知用以製造光碟之壓紋技術 (embossing technique)的發展。在奈米壓印方法中，對塗 佈於待處理之物件上的可固化樹脂以其上形成有凹凸圖案 的金屬模原器（original)(通常被稱為模具、印模或模板） 進行知:壓（press)。將模原器按壓至光阻上會使光阻機械 地變形或流動，以精確地轉印精細圖案。若產生模具一次， 則可以簡單方式重複性地模製奈米級精細結構。因此，奈 米壓印方法為經濟的轉印技術，其產生極小的有害廢物以 及排放。因此，對於在各種領域中應用奈米壓印方法存在 高的期望值。 傳統上，鑑於可固化樹脂上之圖案形成性質（根據設 計可在可固化樹脂上形成凹凸圖案的容易度）的觀點，在 凹凸圖案精細化的同時改善模具與光阻之間的釋放性 (release property )是門重要的課題。 4 201239538 41890pif 因此，利用-種在模具的表面上形成包括有機化合物 的脫模層（mold release !ayer)的方法，以減少模具與可固 化樹脂之間的吸附力，從而改善前述所提到的釋。 用來改善釋放性的另一方法為在基底的表面在欲以 可固化樹脂塗佈之前事先執行表面處理，如專利文獻i以 及專利文獻2中所揭露。表面處理涉及將矽烷耦合劑塗佈 至欲以可固化樹脂塗佈的基底的表面上。根據此方法，基 底與可固化樹脂之間的吸附力會因矽烷耦合層而增加。因 而相對地減少模具與可固化樹脂之間的吸附力，且可改善 模具與可固化樹脂之間的釋放性。在此情況下，由於矽烷 柄合劑相對於基底的鍵結力且鑑於成本的觀點，一般是採 用二曱氧基石夕院或三氣石夕烧作為石夕烧輕合劑。 [先前技術文獻] [專利文獻1] PCT曰本公開案第2010-526426號 [專利文獻2] 曰本未審查專利公開案第2010-152284號 然而’在執行使用三曱氧基矽烷或三氯矽烷的表面處 理的情況下，在基底上產生矽烷耦合劑的聚集體 (aggregate) ’且增加如圖3所繪示之在可固化樹脂膜上 產生缺陷D的問題。 本發明鑑於以上情況而開發。本發明之一目的在於提 供一種奈米壓印方法，其能使奈米壓印中的矽烷耦合劑的 聚集體的產生減少，其中奈米壓印包括藉由以矽烷耦合劑 5 201239538 41890pif 塗佈表面來處理基底表面的步驟。 【發明内容】 ，了達到以上目的，I赞明提供一種奈米壓印的7 法’ h用其表面上具有精細的凹凸圖案的模具，其中奈4 t印的方法的特徵在於包括如下步驟. 使用由以下式1表示之魏輕合難佈絲的表面 將可固化樹脂塗佈於塗佈有所述石夕烧輛合劑的所知 表面上以形成可固化樹脂膜； 所述模具以面向所述可固化樹脂膜之所述凹凸圖 案按壓於所述可固化樹脂臈； 固化所述可固化樹脂膜；以及 將所述模具與所述可固化樹脂膜分離。 Y—l—Si \ γ表干右嫵一 不烷暴，X表示無機官截 I表不有機官能基’ L表示連接（耻）發 : 基的連接基或連接鍵，以及η為1或2。’、、 在本發明之奈米壓印方法中， 甲基及/或乙基’且對於烧基而言， 在本發明之奈米壓印方法中， 對於燒基^言，較佳是 特別佳是甲基。 _^夕細合劑而言， 6 201239538 41890pif 較佳疋3-丙烯醯氧基丙基_二曱基曱氧基矽烷、3_丙烯醯氧 基丙基-甲基雙（三曱基矽氧基）矽烷、3丙烯醯氧基丙基 -曱基二氣矽烷或3-丙烯醯氧基丙基_曱基二曱氧基矽烷。 在本發明之奈米壓印方法中，對於可固化樹脂而言， 車乂佳疋含有丙烯酸異冰片酯、乙二醇二丙烯酸酯以及矽酮 單體化合物中的一者。 在本發明之奈米壓印方法中，對於石夕烧耦合劑而言， 較佳是藉由微觸印法（microcontactprin method)來 佈。 、本發明之奈米壓印方法採用由式1表示之矽烷耦合劑 作為欲塗佈於基底之表面上的⑦絲合劑，其巾基底之表 面上奴塗佈可固化概。從而，♦雜合劑與自身鍵結的 頻f降低。結果，可減少在奈米壓印法中由於魏搞合劑 之聚集體引起之可gj化樹賴巾的缺陷生，其中奈米 壓印法包括叫絲合祕理基絲面的步驟。 【實施方式】 下文中，將以參考附圖的方式來描述本發明之實施 ==而、’本發明不受限於以下所述之實施例。請注意， 篝计的理解，圖式中構成元件的尺寸規模比例 等並不必;、、丨地等同於真實規模比例。 驟圖ϋ簡1E為根縣實施·^奈米壓印方法的步 圖。®2A為繪示模具的示意截面圖，且圖 為圖2A之模具的經圖案化區域的橫截面的一部分 的放 大圖。 7 201239538 41890pif 如圖1A至圖IE所繪示，本實施例之奈米壓印方法為 一種採用其表面上具有精細的凹凸圖案13的模具丨的奈米 壓印方法。將由以下式1所表示之矽烷耦合劑3塗佈於基 底2的表面上（圖ία以及圖1B)。將包括丙烯酸異冰片 酉曰、乙一酵一丙稀酸S旨以及梦嗣早體化合物其中一者的光 可固化樹脂塗佈在塗佈有石夕烧辆合劑3的表面上，以形成 光可固化樹脂膜4 (圖1C)。將模具1以面向光可固化樹 脂膜4之精細的凹凸圖案13按壓於光可固化樹脂膜4(圖 1D)。使光可固化樹脂膜4曝光且固化。然後，將模具i 與經固化的光可固化樹脂膜4分離（圖ιέ)。In the application of Patterned Media) and semiconductor components, there is a high expectation for the use of a pattern transfer technique using a nanoimprint method to transfer a pattern onto a photoresist coated on an object to be processed. The nanoimprint method is a development of an embossing technique well known for manufacturing optical discs. In the nanoimprint method, the curable resin coated on the object to be processed is known as a metal mold (generally referred to as a mold, a stamp or a template) on which a concave-convex pattern is formed. : Press (press). Pressing the mold original onto the photoresist causes the photoresist to mechanically deform or flow to accurately transfer the fine pattern. If the mold is produced once, the nano-scale fine structure can be repeatedly molded in a simple manner. Therefore, the nanoimprint method is an economical transfer technique that produces very little hazardous waste and emissions. Therefore, there is a high expectation for applying the nanoimprint method in various fields. Conventionally, in view of pattern forming properties on a curable resin (according to the ease of forming a concavo-convex pattern on a curable resin according to design), the release between the mold and the photoresist is improved while the concavo-convex pattern is refined (release) Property ) is an important topic of the door. 4 201239538 41890pif Therefore, a method of forming a mold release layer comprising an organic compound on the surface of the mold to reduce the adsorption force between the mold and the curable resin is utilized, thereby improving the aforementioned release. Another method for improving the release property is to perform surface treatment in advance on the surface of the substrate before being coated with a curable resin, as disclosed in Patent Document 1 and Patent Document 2. The surface treatment involves coating a decane couplant onto the surface of a substrate to be coated with a curable resin. According to this method, the adsorption force between the substrate and the curable resin increases due to the decane coupling layer. Therefore, the adsorption force between the mold and the curable resin is relatively reduced, and the release property between the mold and the curable resin can be improved. In this case, due to the bonding force of the decane stalk mixture with respect to the substrate and in view of cost, it is generally used as a smectite light-lighting agent. [Prior Art Document] [Patent Document 1] PCT 曰 公开 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 In the case of the surface treatment of decane, an aggregate of decane coupling agent is generated on the substrate and the problem of producing a defect D on the curable resin film as shown in FIG. 3 is increased. The present invention has been developed in view of the above circumstances. It is an object of the present invention to provide a nanoimprinting method which can reduce the generation of aggregates of decane coupling agents in nanoimprinting, wherein nanoimprinting comprises coating by decane coupling agent 5 201239538 41890pif The step of treating the surface of the substrate with a surface. SUMMARY OF THE INVENTION In order to achieve the above object, I cite a method for providing a nanoimprint embossing method with a fine concave-convex pattern on its surface, wherein the method of nano-printing includes the following steps. Applying a curable resin to a known surface coated with the coating material to form a curable resin film using a surface of a Wei-light-disintegrating cloth represented by the following formula 1; The concave-convex pattern of the curable resin film is pressed against the curable resin crucible; the curable resin film is cured; and the mold is separated from the curable resin film. Y-l-Si \ γ dry 妩 不 不 不 , , , , , , , , , , 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机 无机. ', in the nanoimprint method of the present invention, methyl and/or ethyl' and for the alkyl group, in the nanoimprint method of the present invention, it is preferably Good is methyl. _^夕细合剂, 6 201239538 41890pif is preferably 3-propenyloxypropyl-didecyloxydecane, 3-propyleneoxypropyl-methylbis(tridecyloxyloxy) ) decane, 3 propylene methoxypropyl-mercaptodioxane or 3-propenyloxypropyl-decyl decyloxydecane. In the nanoimprint method of the present invention, for the curable resin, ruthenium contains one of isobornyl acrylate, ethylene glycol diacrylate, and anthrone monomer. In the nanoimprint method of the present invention, it is preferred to use a microcontacting method for the zeabolized coupling agent. The nanoimprinting method of the present invention employs a decane coupling agent represented by Formula 1 as a 7-meshing agent to be applied to the surface of a substrate, and the surface of the substrate of the towel is coated and cured. Thus, the frequency f of the hybrid agent and its own bond is lowered. As a result, it is possible to reduce the defects in the nanoimprinting method caused by the aggregation of the smear-inhibiting agent, wherein the nanoimprint method includes a step of merging the mycelial surface. [Embodiment] Hereinafter, the implementation of the present invention will be described with reference to the accompanying drawings. The invention is not limited to the embodiments described below. Please note that the understanding of the tricks, the size ratio of the constituent elements in the drawing, etc. are not necessary; and, 丨 is equivalent to the true scale. The sketch 1E is a step chart of the implementation of the ^Nim imprint method in the county. ® 2A is a schematic cross-sectional view of the mold and is an enlarged view of a portion of the cross-section of the patterned region of the mold of Figure 2A. 7 201239538 41890pif As shown in FIG. 1A to FIG. IE, the nanoimprint method of the present embodiment is a nanoimprint method using a mold crucible having a fine concavo-convex pattern 13 on its surface. The decane coupling agent 3 represented by the following formula 1 is applied onto the surface of the substrate 2 (Fig. 1A and Fig. 1B). Applying a photocurable resin comprising one of acrylic isobornyl hydrazine, ethyl acetate-acrylic acid S, and a nightmare compound to a surface coated with a mixture of ceramsite 3 to form light The resin film 4 is cured (Fig. 1C). The mold 1 is pressed against the photocurable resin film 4 with a fine concavo-convex pattern 13 facing the photocurable resin film 4 (Fig. 1D). The photocurable resin film 4 is exposed and cured. Then, the mold i is separated from the cured photocurable resin film 4 (Fig. 1).
Rn Y—L—Si’ \ 在式1中，R表不烷基，X表示無機官能基，Y表示 有機官能基，L表示連操矽原子與有機官能基的連接基或 連接鍵，以及η為1或2。 (模具） 舉例而言，如圖2Α以及圖2Β所繪示，模具丨是由支 持部12以及形成於支持部12表面上的精細的凹凸13圖案 13所構成。 支持部12的材料可以疋：金屬（例如：石夕、錄、|呂、 8 201239538 41890pif 鉻、鋼、鈕以及鎢）；其氧化物、氮化物以及碳化物。台地 類型（mesa type)基底10的材料的具體實例包括氧化矽、 氧化鋁、石英玻璃、派熱克斯玻璃（pyreXTM)、玻璃以及 鈉玻璃（soda glass)。 無特別限制精細的凹凸圖案13的形狀，且其可根據 奈米壓印模具之擬定用途來適當地選擇。典型圖案的實例 為圖2A以及圖2B中所繪示之線與間距的圖案。在線以及 間距的圖案中，適當地設定突起的長度、突起的寬度W1、 突起之間的距離W2以及從凹座（recess)底部算起之突起 的高度Η (凹座的深度）。舉例而言，線的寬度W1在10 奈米至100奈米的範圍内，更佳是在20奈米至7〇奈米的 範圍内’線之間的距離W2在1〇奈米至500奈米的範圍 内’更佳是在20奈米至100奈米的範圍内，以及突起的高 度Η在1〇奈米至500奈米的範圍内，更佳是在3〇奈米至 i〇〇奈米的範圍内。或者’精細的凹凸圖案13可有截面為 矩形、圓形、橢圓形等的點（dots)佈置於其中。 (脫模層） 為了改善模具1相對於光可固化樹脂膜4的釋放性， 較佳是在其上具有13的模具1的表面上提供脫模層。對於 脫模層而言’較佳是包括氟化合物。對於氟化合物而言， 較佳是全氟多醚（perfluoropolyether)。較佳的氟化合物的 實例包括由以下式2以及式3所表示之氟化合物。 式2 : 9 201239538 41890pif C3F7(OCF2CF2CF2)p〇C2F4C2H4-Si(OCH3)3 在式2中，p為1或大於1的整數，其中p表示聚合 度（degree of polymerization )。 式3 : (CH30)3Si-CH2CH2CH2-0-CH2CF2-(0CF2CF2)j-(0CF2)k- 0CF2CH2-0-CH2CH2CH2-Si(0CH3)3 在式3中，j以及k為1或大於1的整數，其中j以及 k表示聚合度。 舉例而言，可藉由採用由奥茲蒙特（Aujimcmt)生產 (目前為蘇威蘇萊克斯（SolvaySolexis)生產）的逢必靈 茲朵（FomblinZDOL)來製造式3的化合物。逄必靈兹朵 為由以下化學式3-1表示之化合物。 式 3-1 :Rn Y—L—Si′ \ In Formula 1, R represents an alkyl group, X represents an inorganic functional group, Y represents an organic functional group, and L represents a linking group or a linking bond of a linking atom and an organic functional group, and η It is 1 or 2. (Mold) For example, as shown in Fig. 2A and Fig. 2B, the mold 丨 is constituted by the support portion 12 and the fine uneven pattern 13 formed on the surface of the support portion 12. The material of the support portion 12 can be: metal (for example: Shi Xi, Lu, | Lu, 8 201239538 41890pif chromium, steel, button and tungsten); its oxides, nitrides and carbides. Specific examples of the material of the mesa type substrate 10 include cerium oxide, aluminum oxide, quartz glass, pyreXTM glass, glass, and soda glass. The shape of the fine concavo-convex pattern 13 is not particularly limited, and it can be appropriately selected depending on the intended use of the nanoimprinting mold. An example of a typical pattern is the pattern of lines and spaces depicted in Figures 2A and 2B. In the pattern of the line and the pitch, the length of the protrusion, the width W1 of the protrusion, the distance W2 between the protrusions, and the height Η (the depth of the recess) of the protrusion from the bottom of the recess are appropriately set. For example, the width W1 of the line is in the range of 10 nm to 100 nm, more preferably in the range of 20 nm to 7 N. The distance between the lines W2 is between 1 nm and 500 nm. Within the range of meters, it is better in the range of 20 nm to 100 nm, and the height of the protrusions is in the range of 1 〇 to 500 nm, and more preferably in the range of 3 〇 to i 〇〇 Within the range of nano. Alternatively, the 'fine concavo-convex pattern 13 may have dots in which a cross section is a rectangle, a circle, an ellipse or the like is disposed. (Release Layer) In order to improve the release property of the mold 1 with respect to the photocurable resin film 4, it is preferred to provide a release layer on the surface of the mold 1 having 13 thereon. For the release layer, it is preferred to include a fluorine compound. For the fluorine compound, perfluoropolyether is preferred. Examples of preferred fluorine compounds include fluorine compounds represented by the following formula 2 and formula 3. Formula 2: 9 201239538 41890pif C3F7(OCF2CF2CF2) p〇C2F4C2H4-Si(OCH3)3 In Formula 2, p is an integer of 1 or more, wherein p represents a degree of polymerization. Formula 3: (CH30)3Si-CH2CH2CH2-0-CH2CF2-(0CF2CF2)j-(0CF2)k- 0CF2CH2-0-CH2CH2CH2-Si(0CH3)3 In Formula 3, j and k are integers of 1 or greater , where j and k represent the degree of polymerization. For example, a compound of formula 3 can be produced by using Fomblin ZDOL produced by Aujimcmt (currently manufactured by Solvay Solexis).逄必灵兹朵 is a compound represented by the following Chemical Formula 3-1. Equation 3-1:
HO-CH2CF2-(OCF2CF2)j-(OCF2)k-〇CF2CH2-〇H 在式3-1中’j以及k為1或大於1的整數，复中· 以及k表示聚合度。化合物之數目平均分子量為大約 舉例而言’由式3表示之化合物可藉由以下 ° 得。首先，使氫化鈉（NaH)與由式3_丨表干之、冬驟來獲 朵反應，以使得末端的羥基變成氧化鈉。接著， 風^ 便务基填 201239538 41890pif 化物與末端處的氧化鈉反應，以芳基化（arylate)末端處 的經基。再者’在未飽合的化合物上使用三氯石夕烧（Sijjci3) 來進行石夕氳化反應（hydrosilylation)。最後，採用甲醇以 使用曱氧基來取代矽上的氣原子。 藉由使模具暴露於氟化合物來形成脫模層。具體而 言’如以下進行形成過程。 用經氟化的惰性溶劑將全氟多醚稀釋到濃度在〇 〇 J 重量％至10重量％的範圍内，較佳是濃度在〇 〇1重量％至 1重量％的範圍内，且更佳是濃度在0 01重量％至〇2重量 %的範圍内。也就是說，較佳是藉由將模具i浸潤於這種 經稀釋的溶液中來形成脫模層。經氟化的惰性溶劑的實例 包括.全氟己烧；全氟甲基環己烧；全氟_13二甲基環己 烷；以及二氣五氟丙烷（HCFC_225)。無特別限制浸潤期 間的溫度，但可在至10(TC的範圍内。對於浸潤所需要 的時間量是根據浸潤期_溫度來改變。然而，—般而古， 較偏好是10分鐘或少於10分鐘，且大約i分鐘便足夠。 #或者’在減少壓力的條件下，可藉由使模具1暴露於 全氟多越蒸氣來形成脫模層。無特別限制在此情況下的壓 f，.只要少於1大氣愿力且為0.1大氣壓力或大於0.1大 氣壓，即可。為了使模具j暴露於全氟多趟蒸氣，可將模 具1省在加熱或蒸氣化經稀釋的全氟多醚溶液的環境中。 或ί ’可將全氟多趟吹向模具1上。在此情況下，蒸氣的 溫度可在1〇〇。0：至25〇。(：的範圍内。 脫模層（包括塗層的疏度（Spar卿）和密度）的塗佈 201239538 41890pif 程度y藉由調整使模具丨暴露於經稀釋之氟化合物溶液的 時間里或是藉由調整經稀釋之溶液的濃度來適當地設定。 (基底） 在模具1具有光透射性質的情況下，無特別限制基底 2(其為製程中的標的物）的形狀、結構、尺寸、材料等， 但可根據擬定用途來適#地選擇。其上有轉印圖案之基底 2的表，為其上塗佈有可固化樹脂的表面。舉例而言，在 基底2是帛來製造f;料紀錄媒n ( data medium ) 的，况I，基底2的形狀一般將為碟型。關於基底的結構， 可採用單層基底，或可採用疊層（laminated)基底。關於 基底的材料，材料可選擇自f知的基底材料，例如：石夕、 组三f H這些金屬的氧化物以及氮化物、玻璃（諸如 :英以及樹脂。可單—地或是組合地使用這些材料。注 氧切、氮切以及石英較佳作為基底材料，且 無特別限制基底的厚度，但可根據擬定用途 然而，對於基底的厚度而言，較佳為0.05毫米或 念J· r I5毫米，且更佳為G·1毫米或大於αΐ毫米。若基 其麻膝yrGG5毫米則在基底與模具緊密接觸期間， r可此會撓曲（flex)，造成均勻緊密接觸的狀態不 淠同時’在模具1不具有光透射性質的情 撼撼全石央基底以能夠使光可固化樹脂膜4暴露。根 ’從具有紐射性料及厚度為0.3毫米或大 英A底的石英基底當中來適當地選擇石英基底。若石 夬土底厚度少於〇.3絲，變射能會在處理期間或在壓 201239538 41890pif 印期間因壓力而損壞。注意， 英基底。 較佳是由_石英來形成石 對於基底2而言’較佳是具有遮草層，其中遮星層力HO-CH2CF2-(OCF2CF2)j-(OCF2)k-〇CF2CH2-〇H In the formula 3-1, 'j and k are integers of 1 or more, and the complexes· and k represent the degree of polymerization. The number average molecular weight of the compound is about. For example, the compound represented by Formula 3 can be obtained by the following °. First, sodium hydride (NaH) is reacted with a dry form of the formula 3_丨 to obtain a sodium hydroxide. Next, the wind is filled with a 201239538 41890pif compound and reacted with sodium oxide at the end to arylate the radical at the end. Furthermore, the use of triclosan (Sijjci3) on the unsaturated compound was used for the hydrosilylation. Finally, methanol is used to replace the gas atom on the crucible with a decyloxy group. The release layer is formed by exposing the mold to a fluorine compound. Specifically, the formation process is performed as follows. The perfluoropolyether is diluted with a fluorinated inert solvent to a concentration in the range of from 9% by weight to 10% by weight, preferably in a range of from 1% by weight to 1% by weight, and more preferably It is in the range of from 0.01% by weight to 〇2% by weight. That is, it is preferred to form the release layer by dipping the mold i into the diluted solution. Examples of the fluorinated inert solvent include perfluorohexane; perfluoromethylcyclohexane; perfluoro-13 dimethylcyclohexane; and dipentafluoropropane (HCFC_225). The temperature during the infiltration is not particularly limited, but may be in the range of up to 10 (TC). The amount of time required for the infiltration is changed according to the infiltration period_temperature. However, in general, the preference is 10 minutes or less. 10 minutes, and about i minutes is sufficient. #或' Under the condition of reducing the pressure, the mold release layer can be formed by exposing the mold 1 to the perfluoro-poly vapor. The pressure f in this case is not particularly limited, As long as it is less than 1 atmosphere and is 0.1 atmosphere pressure or more than 0.1 atmosphere, in order to expose the mold j to the perfluoropolyhydrazine vapor, the mold 1 can be saved by heating or vaporizing the diluted perfluoropolyether. In the environment of the solution, or ί ', the perfluoropolythene can be blown onto the mold 1. In this case, the temperature of the vapor can be in the range of 1 〇〇 0: to 25 〇 (:: the release layer ( The coating including the coating's sparsity (Spar) and density) 201239538 41890pif degree y is adjusted by adjusting the time during which the mold is exposed to the diluted fluorine compound solution or by adjusting the concentration of the diluted solution. Ground setting (base) in the mold 1 with light penetration In the case of the nature, the shape, structure, size, material, and the like of the substrate 2, which is the subject matter in the process, are not particularly limited, but may be selected according to the intended use, and the substrate 2 on which the transfer pattern is applied The surface is a surface on which a curable resin is coated. For example, in the case where the substrate 2 is made of ;; the material medium n, the shape of the substrate 2 will generally be a dish type. Regarding the structure of the substrate, a single layer substrate may be employed, or a laminated substrate may be employed. Regarding the material of the substrate, the material may be selected from a base material such as: Shi Xi, Group III f H metal oxides And nitrides, glass (such as: English and resin. These materials can be used singly or in combination. Oxygen injection, nitrogen cutting and quartz are preferred as the base material, and the thickness of the substrate is not particularly limited, but can be formulated according to Use However, for the thickness of the substrate, it is preferably 0.05 mm or more, and is preferably J·r I5 mm, and more preferably G·1 mm or larger than αΐ mm. If the base is yGG5 mm, the substrate is in close contact with the mold. During the period, r can Flexing, resulting in a state of uniform close contact, while at the same time 'there is no light transmissive property in the mold 1 to completely expose the photocurable resin film 4. The root' has a new beam The quartz substrate is suitably selected from a quartz substrate having a thickness of 0.3 mm or a bottom A. If the thickness of the sarcophagus is less than 〇.3, the radiant energy may be due to pressure during processing or during the pressure of 201239538 41890pif. Damage. Note that the base plate is preferably formed of _quartz to form a stone for the substrate 2, preferably having a grass layer, wherein the star layer is
被蝕刻。選擇巡罩滑2b的材料使得遮罩層孔相對於光可 固化樹脂膜4的蝕刻選擇比變低。作為遮罩層北的材料， 較佳為金屬（例如：鉻、钽、鈦、鎳、銀、鉑以及金、這 些金屬的氧化物以及氮化物）。此外，對於遮罩層2b而言& 較佳是包括至少-層’其包括鉻、氧化鉻或氮化絡。° (矽烷耦合劑） 矽烷耦合劑作用在於增加基底與可固化樹脂之間的 吸附力。由式1表示在本發明中所利用之矽烷耦合劑，也 就是說’矽烷耦合劑具有鄰近於矽原子的丨個或2個烷基。 對於烧基R的碳數而言，較佳是在丨至6的範圍内。 對於烷基R而言，較佳是曱基或乙基。對於烧基R而言， 特別佳是曱基。這是因為烷基的長碳鏈將變成烷基與基底 鍵結的三維障礙。在n=2的情況下，烷基的其中一者可以 是曱基，且另一者可以是乙基。 無機官能基X為一種與無機材料反應的官能基。無機 官能基X的貫例主要包括：可水解基（例如：烧氧基（例 如：曱氧基以及乙氧基）、醯氧基（例如：乙醯氧基以及丙 13 201239538 41890pif 醯氧基））；以及齒素原子（氟原子、氯原子、溴原子以及 峨原子）。 有機官能基Y為一種與有機材料反應的官能基。有機 官能基Y的實例主要包括：胺基；羰基；羥基；醛基；硫 醇基；異氰酸酯基（isocyanate groups);異硫氰酸酯基 (isothiocyanate groups);環氧基；氰基；二曱基胺基；二 乙基胺基，朋基（hydrazyno groups);酿餅基（hydrazyde groups);乙烯基砜基；乙烯基；以及烷氧基。 連接基L是從以下選擇：烯基（較佳是碳數在1至20 的範圍内）；-0-; -S-;伸芳基；-C0_; -NH-; -S02-; -COO-; -CONH-;或這些基的組合。稀基較佳作為連接基l。同時， 在L是連接鍵的情況下’式1中的Y和石夕會直接連接。 對於矽烧耦合劑而言，特別佳是3-丙烯醯氧基丙基-二甲基甲氧基矽烧、3-丙烯醯氧基丙基-甲基雙（三甲基矽 氧基）矽烷、3-丙烯醯氧基丙基-甲基二氣矽烷或3_丙烯醯 氣基丙基-曱基二曱氧基石夕烧。 (塗佈矽烷耦合劑的方法） 無特別限制塗佈石夕烧搞合劑的方法，但可採用浸潰法 (dip method)、旋塗法等。圖1A以及圖1B繪示為藉由採 =印模（stamp) 5之微觸印法（wCP法）來塗佈矽烷耦合 劑的情況。在WCP法中準備橡膠，其中橡膠如同其表面上 =有精細的凹凸圖案的塑膠印模1顆粒（η—)貼 =於印模表面上之圖案的狄的頂端的表面。使頂端的上 面緊密地接觸基底，以形成具有對應於基底上之凹凸圖 201239538 41890pif 案之圖案的顆粒膜。在採用hcjp法的情況下，可將材料消 耗抑制到最小。 ^ 在本實施例中，為了增加凹凸圖案的突起之間的吸附 力（+其中將凹凸圖案轉印至光可固化膜4上），印模5具有 與杈具1上的凹凸圖案互補的凹凸圖案。也就是說，在印 模5之圖案中的凹凸（參照圖ίΑ)與在模具之圖案中的凹 凸是相反的H基魏絲佳作為印模5的樹脂材 枓。在執行採用由聚二甲基石夕氧烧構成之印模5的此ρ法 的情況下，對於每-次將#絲合劑塗胁印模5而言， 大約10次連續塗佈魏麵合劑之塗佈操作是合適的 法的詳細㈣勤是描祕日本切 2010-080865中。 幵】系弟 (可固化樹脂膜） „例中，藉由光可固化材料形成可固 膜。然而，本發明不受限於此組態，且可能採 之熱可固化樹脂。無論採用何種類型的可固化樹脂= 壓印方法是有效的。此外，相對於包括丙稀酸】 冰片西曰、乙一醇一丙烯酸醋以及石夕剩軍體化合物中 可固化樹脂’本發明之奈米壓印方法 構成光可固化樹脂的塊體材料包括牛例而5， 紐辦Μ., π Γ 丙稀酸異冰片醋；正- 二η ’乙二醇二丙烯酸醋；以及光 包括2-羥基-2-甲基小苯基-丙烧小 /、 加界面活性劑。 心’可適當地添 對於作為輯酸|旨組份的丙_異冰以旨㈤叫 15 201239538 41890pif 而言，較佳是構成大約塊體材料的47重量％，但可經調 為在20重量％至80重量％的範圍内。結果，光阻的& 性質主要是由IBOA而來。位於賓夕法尼亞州之埃克斯^ 的沙多馬公司（Sartomer Company，Inc.)為 lB〇A (其產。 名稱為SR506)的供應者。 σ 對於正丙烯酸己酯（η_ΗΑ)而言，較佳是構成大約 塊體材料的25重量％，但可經調整為在〇重量％至5〇重 量％的範圍内。在期望授予光阻更柔軟（pUable)的性質 的情況下，利用n_HA來將光阻的黏度降低且調整至2沙 至9cP的範圍内。位於威斯康辛州之密爾沃基的奥德里奇 化子么司（Aldrich Chemical Company )為 n-HA 的供應者。 對於為橋接（bridging)組份的乙二醇二丙烯酸酿 (EGDA)而言’較佳是構成大約塊體材料的25重量％， 但可經調整為在重量％至50重量％的範圍内》EGDa 有助於增加彈性（elasticity)以及剛性（rigidity)，且當聚 合塊體材料時，EGDA更作用於促進n-HA以及IBOA之 間的橋接。 對於為聚合反應起始劑的2-羥基-2-曱基_1_苯基-丙烷 -1-酿I而言’較佳是構成大約塊體材料的3重量％，但可經 調整為在1重量％至5重量％的範圍内。對聚合反應起始 劑有反應的化學射線為由中壓水銀燈所發出的寬帶（wide band)紫外線。聚合反應起始劑助於塊體材料的每一個組 份的橋接以及聚合反應。位於紐約之塔里敦的汽巴精化股 份有限公司（Ciba Specialty Chemicals)為2-羥基-2-甲基 201239538 41890pif -1-苯基-丙烷_；!_酮（其可得自產品名dar〇curtm U 的供應者。 (模具按壓步驟） 在減低模具1以及基底2之間的大氣壓力後藉由以模 具1按壓基底2 ’或是使模具i以及基底2之間的大氣成 為真空來減少殘餘氣體的量。然而，在真空環境中在固 化之前光固化樹脂將有可能將會揮發，造成維持均勻膜厚 度上，困難。因此，較佳是藉由使基底1以及模具2之間 的大氣為氦大氣或為經減壓的氦大氣來減少殘留氣體的 量。氦通過石英基底，於是殘留氣體（氦）的量將逐漸地 減少。由於氦通過石英基底需要時間，更佳是採用經減壓 的氦大氣。 β在1〇0千帕至10兆帕的範圍内的壓力下以模具1按 壓^底2。促使（promote)樹脂流動，壓縮殘留氣體，殘 留^體溶於光©化樹射，以及在更高壓力下促使氛通過 石英基底，使得生產效率改善。然而，若壓力過高，則當 模具1接觸基底2時，若模具1以及基底2之間有異物介 入，模具以及基底將有可能會損壞。據此，壓力較佳是在 1〇1千帕至10兆帕的範圍内，更佳是在1〇〇千帕至5兆帕 的範圍内，且最佳是在丨〇〇千帕至i兆帕的範圍内。壓力 的下限被設定在1〇〇千帕的原因是由於當在大氣内進行壓 印時’在模具以及基底之間的㈣被液體填滿的情況下， 模具以及基底之間的空間會因大氣壓力（大約1〇1千帕） 而受到按壓。 201239538 41890pif (脫模步驟） 在以模具1按壓基底2後且在光固化樹脂膜4上形成 凹凸圖案後’將模具1與光固化樹脂膜4分離。作為分離 方法的一實例，可固持模具i以及基底2之其中一者的外 邊緣部’而模具1以及基底2之另-者的背表面（rear surface)則以真空吸附來固持，且外邊緣的被固持部分或 是背表面的被固持部分可以相反於按壓方向的方向來相對 地移動。當進行此步驟時，可固化樹脂上之圖案中的突起 的寬度與模具1之精細的凹凸圖案13中的相鄰突起之間的 間隔W2相同。 下文中，將描述本發明之操作。因為矽烷耦合劑與自 身鍵結而在基底上產生石夕烧柄合劑聚集體，所以在光可固 化樹月曰膜中產生圖3中所繪示之缺陷d。據認為是由於聚 集體引起回彈（bounce off)的可固化樹脂而引起缺陷d 發生°據此，為了抑制可固化樹脂膜中之缺陷D的產生， 需要降低石夕烧_合劑與自身鍵結的頻率。當石夕烧搞合劑的 每一個分子的無機官能基X變成分離時，矽烷耦合劑與自 身鍵結發生’且矽原子經由氧原子而彼此鍵結。因此，本 發明利用由烷基R取代矽原子的連接鍵中的一者或兩者的 石夕烧耗合劑來抑制矽原子與彼此之間的鍵結。 如以上所述，本發明之奈米壓印法採用由式1表示矽 烧耗合劑作為待塗佈於基底表面上的矽烷耦合劑，其中基 底表面上待塗佈可固化樹脂。從而，矽烷耦合劑與自身鍵 結的頻率降低。結果，可減少在奈米壓印法中由於矽烧耦 201239538 41890pif 合劑之聚集體引起之可固化樹脂膜中的缺陷的產生，其令 奈米壓印法包括以矽烷耦合劑處理基底表面的步驟。 [實例] 本發明之奈米壓印方法之實行的實例將描述於以下。 <實例1> <光可固化樹脂的製備> 製備前文所提到的光可固化樹脂作為奈米壓印中欲 利用的光可固化樹脂。光可固化樹脂的具體組份如下。 光可固化樹脂： 丙浠酸異冰片酯（塊體材料的總重量的47重量％) 正-丙烯酸己醋（塊體材料的總重量的25重量％ ) 乙二醇二丙烯酸酯（塊體材料的總重量的25重量％) 2-羥基-2-曱基-1-苯基-丙烷酮（塊體材料的總重量 的3重量％) ZONYLTM (氟界面活性劑，少於塊體材料的總重量 1重量％) 、 <基底表面處理> 利用3-丙烯醯氧基丙基_二甲基甲氧基矽烷作為矽烷 耦合劑。為了處理矽基底的表面，以旋塗法將溶液（以 克的丙二醇單曱基喊乙酯（PGMEA)稀釋1克的石夕烧麵合 劑）塗佈於基底上。 ° <光可固化樹脂膜的製造> 首先，以旋塗法將光可固化樹脂塗佈於矽基底之經處 理的表面上。接著，在基底溫度1〇〇ΐ下烘烤光可固化樹 201239538 41890pif 脂10分鐘’以形成具有膜厚度為8〇奈米之光可固化樹脂 膜。 <評估方法> 以原子力顯微鏡（由數位儀器製造之Nanoscope 3) 來確⑽10微米.10微米見方内是否有缺陷存在於光可固 化樹脂膜中。若缺陷存在，則計算缺陷數。 <實例2> 除了利用3·丙烯醯氧基丙基·甲基雙（三甲基石夕氧基） 矽烷作為矽烷耦合劑外，以關於實例丨所述之步驟相同的 步驟來製造光可固化樹脂膜。以關於實例i所述之方式相 同的方式來確認是否有缺陷存在以及缺陷數。 〈實例3> 除了利用烯醯氧基丙基·甲基二録烧作為石夕烧 耦合劑外，以關於實例1所述之步驟相同的步驟來製造光 可固化樹脂臈。以關於實例丨所述之方式相同的方式來確 認是否有缺陷存在以及缺陷數。 〈實例4> 除了利用3-丙稀醯氧基丙基-甲基二甲氧基矽烷作為 矽烷耦合劑外，以關於實例1所述之步驟相同的步驟來製 造光可固化樹脂膜。以關於實例1所述之方式相同的方式 來確認是否有缺陷存在以及缺陷數。 <比較實例1> 除了利用3-丙稀醯氧基丙基-三甲氧基梦炫作為梦炫 耦合劑外，以關於實例1所述之步驟相同的步驟來製造光 20 201239538 41890pif 可固化樹脂膜。以關於實例1所述之方式相同的方式來確 認是否有缺陷存在以及缺陷數。 〈比較實例2> 除了利用3-丙烯酿氧基丙基-三氣矽烷作為矽烷耦合 劑外，以關於實例1所述之步驟相同的步驟來製造光可固 化樹脂膜。以關於實例1所述之方式相同的方式來確認是 否有缺陷存在以及缺陷數。 <比較實例3> 除了利用3-丙烯醯氧基丙基-參（三曱基石夕氧基）石夕 烧作為石夕烧耦合劑外’以關於實例1所述之步驟相同的步 驟來製造光可固化樹脂膜。以關於實例1所述之方式相同 的方式來確認是否有缺陷存在以及缺陷數。 <比較實例4> 除了利用乙烯基雙（三曱基氧基）矽烷 (bis(trimethoxy)silylethylene)作為石夕烧耦合劑外，以關於 實例1所述之步驟相同的步驟來製造光可固化樹脂膜。以 關於實例1所述之方式相同的方式來確認是否有缺陷存在 以及缺陷數。 <結果> 以下表1表示對於實例1至實例4以及比較實例1至 比較實例4的評估結果。這些評估結果確認如下··在其上 塗佈有可固化樹脂膜之基底的表面藉由以式1表示之矽烷 耦合劑來塗佈處理的情況下，可減少矽烷耦合劑聚集體的 產生且可製造更均勻的可固化樹脂膜。 21 201239538 41890pif 表1 樹脂膜中的缺陷齡 實例1 --— , - w -HAh. 2 實例2 12 實例3 10 實例4 3 比較實例1 ---~___ 40 比較實例2 35 比較實例3 52 比較實例4 60 ——.,—— <實例5> 製造由t一曱基石夕氧烧構成且具有互補於模具之圖 案之圖案的印模。接下來，將矽烷耦合劑貼附於印模圖案 之突起的頂端的表面。然後，藉由使頂端的表面與數個基 底緊密地接觸來將矽烷耦合劑連續地塗佈於數個基底上， 而無需額外地貼附石夕烧耦合劑。 <結果> 根據印模圖案來塗佈石夕烧搞合劑，甚至會塗佈到第1 〇 個基底上。 【圖式簡單說明】 圖1A為示意地繪示奈米壓印方法的步驟的截面圖， 其中奈米壓印方法包括以微觸法塗佈矽烷耦合劑的步驟。 22 201239538 41890pif 圖IB為示意地繪示奈米壓印方法的步驟的截面圖， 其中奈米壓印方法包括以微觸法塗佈矽烷耦合劑的步驟。 圖1C為示意地繪示奈米壓印方法的步驟的截面圖， 其中奈米壓印方法包括以微觸法塗佈矽烷耦合劑的步驟。 圖1D為示意地繪示奈米壓印方法的步驟的截面圖， 其中奈米壓印方法包括以微觸法塗佈矽烷耦合劑的步驟。 圖1E為示意地繪示奈米壓印方法的步驟的截面圖， 其中奈米壓印方法包括以微觸法塗佈矽烷耦合劑的步驟。 圖2A為繪示用於奈米壓印之模具的截面圖。 圖2B為繪示圖2A之模具的經圖案化區域的橫截面的 部分放大的視圖。 圖3為繪示在基底上之可固化樹脂膜中的缺陷示意 圖，其中基底的表面已以習知的矽烷耦合劑處理。 【主要元件符號說明】 1 :模具 2 :基底 2a :支持基底 2b :遮罩層 3 :石夕烧搞合劑 4:光可固化樹脂膜 5 :印模 12 :支持部 13 :精細的凹凸圖案 D :缺陷 23 201239538 41890pif H :高度 W1 :寬度 W2 :距離Etched. The material of the patrol slip 2b is selected such that the etching selectivity of the mask layer holes with respect to the photocurable resin film 4 becomes lower. As the material of the mask layer north, metals (e.g., chromium, ruthenium, titanium, nickel, silver, platinum, and gold, oxides and nitrides of these metals) are preferable. Further, for the mask layer 2b, & preferably comprises at least - layer 'which includes chromium, chromium oxide or nitrided. ° (Cane coupling agent) The decane coupling agent acts to increase the adsorption between the substrate and the curable resin. The decane coupling agent used in the present invention is represented by Formula 1, that is, the 'decane coupling agent has one or two alkyl groups adjacent to the ruthenium atom. For the carbon number of the base R, it is preferably in the range of 丨 to 6. For the alkyl group R, a mercapto group or an ethyl group is preferred. For the base R, a sulfhydryl group is particularly preferred. This is because the long carbon chain of the alkyl group will become a three-dimensional barrier to the bonding of the alkyl group to the substrate. In the case of n = 2, one of the alkyl groups may be a fluorenyl group, and the other may be an ethyl group. The inorganic functional group X is a functional group reactive with an inorganic material. The examples of the inorganic functional group X mainly include: hydrolyzable groups (for example, alkoxy groups (for example, decyloxy group and ethoxy group), decyloxy groups (for example, ethoxylated groups and C 13 13 395 387 41 890 pif decyloxy group) ); and dentate atoms (fluorine atoms, chlorine atoms, bromine atoms, and germanium atoms). The organofunctional group Y is a functional group reactive with an organic material. Examples of the organofunctional group Y mainly include: an amine group; a carbonyl group; a hydroxyl group; an aldehyde group; a thiol group; an isocyanate group; an isothiocyanate groups; an epoxy group; a cyano group; Amino group; diethylamino group, hydrazyno groups; hydrazyde groups; vinyl sulfone group; vinyl group; The linking group L is selected from the group consisting of alkenyl groups (preferably having a carbon number in the range of 1 to 20); -0-; -S-; exoaryl group; -C0_; -NH-; -S02-; -COO -; -CONH-; or a combination of these bases. A dilute group is preferred as the linking group 1. Meanwhile, in the case where L is a connection key, Y and Shi Xi in the equation 1 are directly connected. Particularly preferred for the calcining couplant is 3-propenyloxypropyl-dimethylmethoxyoxime, 3-propenyloxypropyl-methylbis(trimethyldecyloxy)decane 3-propenyloxypropyl-methyldioxane or 3-propenylhydrazinopropyl-decyldimethoxy oxylate. (Method of coating a decane coupling agent) There is no particular limitation on the method of coating the zeazone binder, but a dip method, a spin coating method, or the like can be employed. 1A and 1B illustrate the case where a decane coupling agent is coated by a micro-touch method (wCP method) using a stamping method. The rubber is prepared in the WCP method in which the rubber is like a surface of a plastic stamp 1 having a fine concave-convex pattern on its surface (η-) pasted on the surface of the top of the pattern on the surface of the stamp. The top surface of the top end is brought into close contact with the substrate to form a particle film having a pattern corresponding to the uneven pattern 201239538 41890pif on the substrate. In the case of the hcjp method, material consumption can be minimized. In the present embodiment, in order to increase the adsorption force between the protrusions of the concavo-convex pattern (+ where the concavo-convex pattern is transferred onto the photocurable film 4), the stamp 5 has a concavity and convexity complementary to the concavo-convex pattern on the cookware 1. pattern. That is, the unevenness in the pattern of the stamp 5 (refer to Fig. Α) is opposite to that of the concave pattern in the pattern of the mold, and the H-based weiss is preferable as the resin material of the stamp 5. In the case of performing this ρ method using the stamp 5 composed of polydimethyl oxalate, about 10 times of continuous application of the Wei noodle mixture for each of the # 丝 涂 涂 涂 涂The coating operation is the appropriate method of detail (four) is the secret of the Japanese cut 2010-080865.幵 系 系 (curable resin film) „ In the example, the photocurable material is formed into a solid film. However, the present invention is not limited to this configuration, and may be used as a heat curable resin. Type of Curable Resin = Imprinting Method Is Effective. In addition, the nanoimprint of the present invention is compared to the curable resin including acrylic acid, borneol, acetol-acrylic acid vinegar, and shixi remaining military compound. The bulk material constituting the photocurable resin includes bovine case 5, New Zealand Μ., π 丙 acrylic acid isobornic vinegar; n-di-n' ethylene glycol diacrylate vinegar; and light including 2-hydroxy-2 -Methyl small phenyl-acrylic acid small /, adding a surfactant. The heart ' can be appropriately added to the C acid as a solubilized acid| the purpose of the component is as follows: (5) is called 15 201239538 41890pif, preferably is composed About 47% by weight of the bulk material, but can be adjusted to be in the range of 20% by weight to 80% by weight. As a result, the & the nature of the photoresist is mainly derived from IBOA. Sartomer Company, Inc. is lB〇A (its production. The supplier is called SR506). σ For the hexyl acrylate (η_ΗΑ), it is preferably composed of about 25% by weight of the bulk material, but can be adjusted to be in the range of 〇% by weight to 5% by weight. In the case where it is desired to impart a pUable property to the photoresist, n_HA is used to reduce the viscosity of the photoresist and adjust it to a range of 2 to 9 cP. The Aldrich smear in Milwaukee, Wisconsin (Aldrich Chemical Company) is a supplier of n-HA. For ethylene glycol diacrylic acid (EGDA) for bridging components, 'preferably constitutes about 25% by weight of the bulk material, but can be Adjusted to range from wt% to 50% by weight "EGDa helps to increase elasticity and rigidity, and when polymerizing bulk materials, EGDA acts more to promote bridging between n-HA and IBOA. For 2-hydroxy-2-indolyl-1-phenyl-propane-1-broth I which is a polymerization initiator, 'preferably constitutes about 3% by weight of the bulk material, but can be adjusted to In the range of 1% by weight to 5% by weight. The reactive chemical ray is a wide band of ultraviolet light emitted by a medium pressure mercury lamp. The polymerization initiator aids in the bridging and polymerization of each component of the bulk material. The steam in Tarrytown, New York. Ciba Specialty Chemicals is 2-hydroxy-2-methyl 201239538 41890 pif -1-phenyl-propane _!!-ketone (available from the supplier of the product name dar〇curtm U). (Mold pressing step) After the atmospheric pressure between the mold 1 and the substrate 2 is reduced, the amount of residual gas is reduced by pressing the substrate 2' with the mold 1 or by vacuuming the atmosphere between the mold i and the substrate 2. However, it is likely that the photocurable resin will volatilize before curing in a vacuum environment, making it difficult to maintain a uniform film thickness. Therefore, it is preferred to reduce the amount of residual gas by making the atmosphere between the substrate 1 and the mold 2 a helium atmosphere or a decompressed helium atmosphere. The crucible passes through the quartz substrate, and the amount of residual gas (氦) is gradually reduced. Since it takes time to pass the quartz substrate, it is preferable to use a decompressed atmosphere. The β is pressed by the mold 1 under a pressure in the range of 1 〇 0 kPa to 10 MPa. Promoting the flow of the resin, compressing the residual gas, dissolving the residual body in the light, and pushing the atmosphere through the quartz substrate at a higher pressure, the production efficiency is improved. However, if the pressure is too high, when the mold 1 contacts the substrate 2, if foreign matter is introduced between the mold 1 and the substrate 2, the mold and the substrate may be damaged. Accordingly, the pressure is preferably in the range of from 1 〇 1 kPa to 10 MPa, more preferably in the range of from 1 kPa to 5 MPa, and most preferably in the range of 丨〇〇 kPa to MPa. Within the range of megapascals. The reason why the lower limit of the pressure is set at 1 kPa is because when the embossing is performed in the atmosphere, 'the space between the mold and the substrate is atmospheric due to the filling of the liquid between the mold and the substrate. Force (about 1 〇 1 kPa) and pressed. 201239538 41890pif (Mold release step) After the base 2 is pressed by the mold 1, and the uneven pattern is formed on the photo-curable resin film 4, the mold 1 and the photo-curable resin film 4 are separated. As an example of the separation method, the outer edge portion ' of one of the mold i and the substrate 2 may be held, and the other rear surface of the mold 1 and the substrate 2 is held by vacuum suction, and the outer edge is The held portion or the held portion of the back surface can be relatively moved opposite to the direction of the pressing direction. When this step is carried out, the width of the projections in the pattern on the curable resin is the same as the interval W2 between the adjacent projections in the fine concavo-convex pattern 13 of the mold 1. Hereinafter, the operation of the present invention will be described. Since the decane coupling agent and the self-bonding agent produce a cluster of shi stalk mixture on the substrate, the defect d depicted in Fig. 3 is produced in the photocurable tree decidua. It is considered that the defect d occurs due to the bounce off of the curable resin caused by the aggregate. Accordingly, in order to suppress the generation of the defect D in the curable resin film, it is necessary to reduce the bonding between the shi _ _ mixture and the self. Frequency of. When the inorganic functional group X of each molecule of the smelting agent becomes separated, the decane coupling agent and its own bond occur 'and the ruthenium atoms are bonded to each other via the oxygen atom. Accordingly, the present invention utilizes a combination of one or both of the linking bonds of the hydrazine atom substituted by the alkyl group R to inhibit the bonding of the ruthenium atoms to each other. As described above, the nanoimprint method of the present invention employs a ruthenium burn-up agent represented by Formula 1 as a decane coupling agent to be coated on the surface of a substrate, wherein a curable resin is to be coated on the surface of the substrate. Thereby, the frequency at which the decane coupling agent bonds to itself is lowered. As a result, the occurrence of defects in the curable resin film due to the aggregate of the ruthenium-coupled 201239538 41890pif mixture in the nanoimprint method can be reduced, and the nanoimprint method includes the step of treating the surface of the substrate with a decane couplant. [Examples] Examples of the practice of the nanoimprint method of the present invention will be described below. <Example 1><Preparation of Photocurable Resin> The photocurable resin mentioned above was prepared as a photocurable resin to be utilized in nanoimprinting. The specific components of the photocurable resin are as follows. Photocurable resin: isobornyl propionate (47% by weight of the total weight of the bulk material) n-acrylic acid vinegar (25% by weight of the total weight of the bulk material) ethylene glycol diacrylate (block material) 25% by weight based on the total weight of 2-hydroxy-2-mercapto-1-phenyl-propanone (3% by weight of the total weight of the bulk material) ZONYLTM (Fluorinated surfactant, less than total bulk material) Weight 1% by weight) <Base surface treatment> 3-Propoxypropyl propyl dimethyl methoxy decane was used as a decane coupling agent. In order to treat the surface of the ruthenium substrate, a solution (1 gram of Shihwa-baked dough mixture diluted with gram of propylene glycol monothioglycolate (PGMEA)) was applied to the substrate by spin coating. ° <Production of Photocurable Resin Film> First, a photocurable resin is applied onto the treated surface of the ruthenium substrate by a spin coating method. Next, the photocurable tree 201239538 41890 pif grease was baked at a substrate temperature of 1 Torr for 10 minutes to form a photocurable resin film having a film thickness of 8 Å. <Evaluation Method> An atomic force microscope (Nanoscope 3 manufactured by a digital instrument) was used to determine whether or not a defect was present in the photocurable resin film in a 10 μm.10 μm square. If the defect exists, the number of defects is calculated. <Example 2> A photocurable resin was produced in the same manner as in the procedure described in Example 除了 except that 3· propyleneoxypropyl·methyl bis(trimethylsulphonyl) decane was used as the decane coupling agent. membrane. It is confirmed in the same manner as described in Example i whether or not there is a defect and the number of defects. <Example 3> A photocurable resin oxime was produced in the same manner as in the procedure described in Example 1, except that the oximeoxypropyl group-methyl lanthanum was used as the ceramsite coupling agent. The presence of defects and the number of defects are confirmed in the same manner as described in the example. <Example 4> A photocurable resin film was produced in the same manner as the procedure described in Example 1 except that 3-propoxymethoxypropyl-methyldimethoxydecane was used as the decane coupling agent. It was confirmed in the same manner as described in Example 1 whether or not there was a defect and the number of defects. <Comparative Example 1> In addition to using 3-acryloxypropyl-trimethoxymethane as a dreaming coupling agent, light 20 was produced in the same procedure as that described in Example 1 2012 201238 41890 pif curable resin membrane. The presence of defects and the number of defects were confirmed in the same manner as described in Example 1. <Comparative Example 2> A photocurable resin film was produced in the same manner as the procedure described in Example 1, except that 3-propenyloxypropyl-trioxane was used as the decane coupling agent. It is confirmed in the same manner as described in Example 1 whether or not the defect exists and the number of defects. <Comparative Example 3> Manufactured in the same manner as the procedure described in Example 1 except that 3-propenyloxypropyl-parade (trimethyl decyloxy) was used as the stagnation agent A photocurable resin film. Whether or not the defect exists and the number of defects are confirmed in the same manner as described in relation to Example 1. <Comparative Example 4> Photocurable was produced in the same manner as the procedure described in Example 1, except that bis(trimethoxy)silylethylene was used as the scouring agent. Resin film. Whether or not the defect exists and the number of defects are confirmed in the same manner as described in the case of Example 1. <Results> Table 1 below shows the evaluation results for Examples 1 to 4 and Comparative Example 1 to Comparative Example 4. As a result of the evaluation, it is confirmed that the surface of the substrate on which the curable resin film is coated is coated by the decane coupling agent represented by Formula 1, and the generation of the decane coupling agent aggregate can be reduced. A more uniform curable resin film is produced. 21 201239538 41890pif Table 1 Defect age in resin film Example 1 --- , - w -HAh. 2 Example 2 12 Example 3 10 Example 4 3 Comparative Example 1 ---~___ 40 Comparative Example 2 35 Comparative Example 3 52 Comparison Example 4 60 ——., - <Example 5> An impression was constructed which was composed of t-mercapto-stone and had a pattern complementary to the pattern of the mold. Next, a decane coupling agent was attached to the surface of the tip end of the projection of the stamp pattern. Then, the decane coupling agent is continuously applied to the plurality of substrates by bringing the surface of the tip into close contact with the plurality of substrates without additionally attaching the ceramsite coupling agent. <Results> The coating was applied according to the stamp pattern, and even applied to the first substrate. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a cross-sectional view schematically showing the steps of a nanoimprint method, wherein the nanoimprint method includes a step of coating a decane coupling agent by a micro-touch method. 22 201239538 41890pif Figure IB is a cross-sectional view schematically showing the steps of the nanoimprint method, wherein the nanoimprint method includes the step of coating the decane coupling agent by a micro-touch method. 1C is a cross-sectional view schematically showing the steps of a nanoimprint method, wherein the nanoimprint method includes the step of coating a decane coupling agent by a micro-touch method. 1D is a cross-sectional view schematically showing the steps of a nanoimprint method, wherein the nanoimprint method includes the step of coating a decane coupling agent by a micro-touch method. 1E is a cross-sectional view schematically showing the steps of a nanoimprint method, wherein the nanoimprint method includes the step of coating a decane coupling agent by a micro-touch method. 2A is a cross-sectional view showing a mold for nanoimprinting. Figure 2B is a partially enlarged view showing a cross section of the patterned region of the mold of Figure 2A. Fig. 3 is a schematic view showing defects in a curable resin film on a substrate in which the surface of the substrate has been treated with a conventional decane coupling agent. [Description of main component symbols] 1 : Mold 2 : Substrate 2a : Support substrate 2b : Mask layer 3 : Shi Xi Burning agent 4 : Photocurable resin film 5 : Die 12 : Support portion 13 : Fine concave and convex pattern D : Defect 23 201239538 41890pif H : Height W1 : Width W2 : Distance