201031690 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用苯並環丁烯樹脂，而且藉由熱 藉由壓印之圖型形成方法。 - 【先前技術】 " 近年來’伴隨著半導體元件之微細化，有各式各樣的 φ 蝕刻方式被提出’開發正持續進行中。特別是關於5 Onm 以下的蝕刻技術，將波長193 nm之ArF準分子雷射與液浸 技術組合的液浸ArF準分子雷射方式、波長13.5nm之極 端紫外線（EUV )曝光方式、以及光束徑爲5nm以下之電 子束（EB)曝光方式的硏究正在發展中。然而，光源波長 的短波長化，會使得高價的新型曝光裝置成爲必要，被認 爲是進一步微細加工方面有力技術的EB曝光方式，生產 率卻低，而難以量產奈米元件。 φ 此處，由Chou等人提出奈米壓印蝕刻法作爲微細圖 . 型的形成方法（參照專利文獻1 )。奈米壓印蝕刻法，係 指對於在表面形成有樹脂層的基板按壓形成有既定圖型的 模具，將模具的圖型轉印至樹脂層的技術。 最初由Chou .等人提出的奈米壓印蝕刻法，係將熱塑 性樹脂的的聚甲基丙烯酸甲酯（PMMA )使用於樹脂層， 在使樹脂層變形之前進行加熱而使樹脂軟化。然後，按壓 模具使樹脂層變形，其後使樹脂層冷卻而固化，由於經過 此步驟，因此被稱爲「熱循環奈米壓印」。然而，對於「 -5- 201031690 熱循環奈米壓印」而言，由於樹脂層之昇溫、冷卻需要時 間，因此會有生產率低的這種問題，或者有溫度差造成圖 型尺寸變化這樣的問題。 附帶一提，作爲多晶片模組、液晶顯示元件等所使用 的有機材料、以及LSI等半導體元件的鈍化膜，一般而言 ’已知有聚醯亞胺系樹脂以及丙烯酸系樹脂。近年來，爲 了替代該等樹脂，正在硏究使用光學的、電子特性以及耐 程序性良好的苯並環丁烯樹脂（參照專利文獻2)。 在如前述的用途之中，苯並環丁烯樹脂，係以在矽或 玻璃等板上形成其樹脂層，並使所形成的樹脂層圖型化的 方式使用。一般就苯並環丁烯樹脂層的圖型化方法而言， 係使用電漿蝕刻裝置的乾式蝕刻；與使用有機溶劑等蝕刻 劑’對添加光反應劑的負型感光性苯並環丁烯樹脂配合組 成物進行蝕刻的濕式蝕刻。 乾式触刻之情況，一般係在基板上所形成的苯並環丁 烯樹脂層上形成光阻或金屬等層作爲光罩材料，以使除去 苯並環丁烯樹脂層之處露出的方式，使該光罩材料圖型化 ’在〇2、CF4等蝕刻氣體環境下’對電極施加高頻率而產 生電漿，使所產生的電漿與光罩材料開口部的苯並環丁烯 樹脂進行反應而氣化，除去開口部的苯並環丁烯樹脂，以 進行圖型化。 另一方面’在以往的濕式鈾刻中，一般係使含有雙疊 氮化合物等感光劑而成爲負型感光性的苯並環丁烯樹脂層 形成於基板上’以可使該負型感光性苯並環丁烯樹脂層形 -6 - 201031690 成圖型之方式進行曝光，藉由光反應使曝光部分硬化，藉 由有機溶劑等除去未曝光的苯並環丁烯樹脂部分，以進行 圖型化（參照專利文獻3 )。 進一步還有不使用感光性苯並環丁烯樹脂，藉由濕式 鈾刻形成圖型的方法。該方法，係在形成於基板上且經過 B階段化的苯並環丁烯樹脂層上形成光阻層，使此光阻層 圖型化之後’以所形成的光阻圖型作爲光罩，對該苯並環 Φ 丁嫌樹脂層實施由有機溶劑進行的濕式蝕刻處理，最後， 除去不需要的光阻圖型，以進行圖型形成的方法（參照專 利文獻4 )。 然而’於苯並環丁烯樹脂層形成光阻層，進行電漿蝕 刻或濕式蝕刻的方法，係步驟繁雜，在進行電漿蝕刻的情 況’由於光罩材料與苯並環丁烯樹脂之蝕刻選擇比爲 1.5程度’因此考慮到電漿蝕刻時的膜減少，有必要使光 阻等光罩材料的厚度成爲1.5〜2倍程度，會有曝光時間 〇 增加或光阻的解像度降低等缺點存在。進行濕式蝕刻的情 況’由於苯並環丁烯樹脂層會往橫方向（膜面方向）及縱 方向（膜的深度方向）等方性地蝕刻，因此會有縱橫比較 高，難以得到垂直的圖型這樣的缺點。 另一方面’在使用感光性苯並環丁烯樹脂的濕式蝕刻 方法中’由於使用添加感光性光反應劑的苯並環丁烯樹脂 ’因此’此苯並環丁烯樹脂具有由紫外線區域至可見光區 域的光線吸收，所以著色的情形很多。對如此的材料而言 ’使用於例如液晶顯示元件的情況，會有妨礙背光源的光 201031690 線透過，導致光利用效率降低等問題。 [先前技術文獻] [專利文獻] 專利文獻1:美國專利第5772905號說明書 專利文獻2:日本特公平05-073756號公報 專利文獻3:日本特表平11_5〇3248號公報 專利文獻4:日本特開平11-016883號公報 ❹ 【發明內容】 [發明所欲解決之課題] 於是’本發明係基於上述情況而完成，其欲解決的課 題爲提供一種方法’係使用熱壓印蝕刻技術，形成含有苯 並環丁烯樹脂之層之圖型。亦即提供一種含有苯並環丁烯 樹脂之層之圖型形成方法，不使用感光性苯並環丁烯、阻 劑、以及顯像液等’可容易地形成苯並環丁烯樹脂之圖型 ’且尺寸沒有變化或變化很少。 ^ [用於解決課題之方法] 本發明人等潛心硏究的結果，發現了藉由在特定的加 熱溫度下’使用模具對含有苯並環丁烯樹脂之層加壓，可 解決上述課題’而完成了本發明。 亦即本發明係，一種藉由壓印之圖型形成方法，具有 將含有使下述式（1 ) -8 - 201031690 [化1]201031690 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a pattern forming method using a benzocyclobutene resin and by embossing by heat. - [Prior Art] In recent years, with the miniaturization of semiconductor devices, various types of φ etching methods have been proposed, and development is continuing. Especially for etching technology below 5 Onm, liquid immersion ArF excimer laser method combining ArF excimer laser and liquid immersion technology with wavelength of 193 nm, extreme ultraviolet (EUV) exposure mode with wavelength of 13.5 nm, and beam diameter Research on electron beam (EB) exposure methods below 5 nm is under development. However, the short wavelength of the wavelength of the light source necessitates a new expensive exposure apparatus, which is considered to be a powerful EB exposure method for further fine processing, and the production rate is low, and it is difficult to mass-produce the nano component. φ Here, Chou et al. propose a nanoimprint etch method as a fine pattern (see Patent Document 1). The nanoimprint etching method is a technique in which a mold having a predetermined pattern is pressed against a substrate having a resin layer formed on the surface thereof, and a pattern of the mold is transferred to the resin layer. The nanoimprint etching method originally proposed by Chou et al. uses a polymethyl methacrylate (PMMA) of a thermoplastic resin in a resin layer, and heats the resin layer before it is deformed to soften the resin. Then, the resin layer is pressed by pressing the mold, and then the resin layer is cooled and solidified. This step is called "thermal cycle nanoimprint". However, for "-5-201031690 thermal cycle nanoimprint", since the temperature rise and cooling of the resin layer take time, there is a problem that the productivity is low, or there is a problem that the temperature difference causes the pattern size to change. . Incidentally, as an organic material used for a multi-wafer module, a liquid crystal display element, or the like, and a passivation film of a semiconductor element such as an LSI, generally, a polyimide-based resin and an acrylic resin are known. In recent years, in order to replace these resins, benzocyclobutene resins having excellent optical properties, electronic properties, and process resistance have been studied (see Patent Document 2). In the above-mentioned use, the benzocyclobutene resin is used in such a manner that a resin layer is formed on a sheet such as ruthenium or glass, and the formed resin layer is patterned. In general, a patterning method of a benzocyclobutene resin layer is a dry etching using a plasma etching apparatus; and a negative photosensitive benzocyclobutene to which a photoreactive agent is added using an etchant such as an organic solvent. The resin is blended with the composition to perform wet etching of the etching. In the case of dry lithography, a layer of photoresist or metal is formed as a mask material on the benzocyclobutene resin layer formed on the substrate to expose the benzocyclobutene resin layer. The mask material is patterned to 'apply a high frequency to the electrode in an etching gas environment such as 〇2 and CF4 to generate a plasma, and the generated plasma and the benzocyclobutene resin in the opening portion of the mask material are subjected to The reaction was gasified, and the benzocyclobutene resin in the opening portion was removed to carry out patterning. On the other hand, in the conventional wet uranium engraving, a benzocyclobutene resin layer containing a sensitizer such as a bisazide compound and a negative photosensitive property is generally formed on a substrate to enable the negative sensitization. Benzene cyclobutene resin layer form -6 - 201031690 Exposure is carried out in a pattern, and the exposed portion is hardened by photoreaction, and the unexposed benzocyclobutene resin portion is removed by an organic solvent or the like to perform patterning Forming (refer to Patent Document 3). Further, there is a method of forming a pattern by wet uranium engraving without using a photosensitive benzocyclobutene resin. In the method, a photoresist layer is formed on a B-staged benzocyclobutene resin layer formed on a substrate, and after the photoresist layer is patterned, the photoresist pattern is formed as a mask. The benzo ring Φ susceptor resin layer is subjected to a wet etching treatment with an organic solvent, and finally, an unnecessary photoresist pattern is removed to form a pattern (see Patent Document 4). However, the method of forming a photoresist layer on a benzocyclobutene resin layer and performing plasma etching or wet etching is complicated in the case of performing plasma etching because of the photomask material and the benzocyclobutene resin. The etching selection ratio is about 1.5. Therefore, in consideration of the film reduction at the time of plasma etching, it is necessary to make the thickness of the mask material such as photoresist 1.5 to 2 times, and there is a disadvantage that the exposure time 〇 is increased or the resolution of the photoresist is lowered. presence. In the case of wet etching, since the benzocyclobutene resin layer is etched in the lateral direction (film surface direction) and the vertical direction (depth direction of the film), the aspect ratio is relatively high, and it is difficult to obtain vertical. The shortcomings of the pattern. On the other hand, 'in the wet etching method using a photosensitive benzocyclobutene resin, 'by using a benzocyclobutene resin to which a photosensitive photoreactive agent is added', the benzocyclobutene resin has an ultraviolet region. Light is absorbed into the visible light region, so there are many cases of coloring. When such a material is used in, for example, a liquid crystal display element, there is a problem that the light of the backlight 201010690 is prevented from being transmitted, resulting in a decrease in light use efficiency. [Prior Art Document] [Patent Document 1] Patent Document 1: U.S. Patent No. 5,772,905, Patent Document 2: Japanese Patent Publication No. Hei 05-073756, Patent Document 3: Japanese Patent Publication No. 11_5〇3248, Patent Document 4: Japanese Special Japanese Patent Application Laid-Open No. Hei 11-016883A SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] The present invention has been completed based on the above-described circumstances, and a problem to be solved is to provide a method of forming a content by using a hot stamping etching technique. A pattern of layers of benzocyclobutene resin. That is, a pattern forming method of a layer containing a benzocyclobutene resin, which does not use a photosensitive benzocyclobutene, a resist, a developing solution, etc., can be easily formed into a benzocyclobutene resin. Type 'and no change in size or little change. ^ [Method for Solving the Problem] As a result of intensive research by the present inventors, it has been found that the above problem can be solved by pressurizing a layer containing a benzocyclobutene resin using a mold at a specific heating temperature. The present invention has been completed. That is, the present invention is a pattern forming method by imprinting, which has a formula (1) -8 - 201031690 [Chemical 1]
(式中，R1係互相獨立，表示碳原子數1至6之烷基 、乙稀基或苯基；R2係互相獨立，表示碳原子數1至6之 烷基或甲氧基；R3係互相獨立，表示碳原子數1至6之烷 ® 基；係互相獨立，表示〇或i;n係表示1至3之 整數） 所表示之二乙烯基矽氧烷_雙苯並環丁烯經聚合所得 之苯並環丁烯樹脂之層形成於基板上之步驟； 於前述含有苯並環丁烯樹脂之層一邊加熱以及加壓一 邊按壓模具，使圖型形成於該含有苯並環丁烯樹脂之層之 步驟；以及 在冷卻後，使形成有前述圖型之含有苯並環丁烯樹脂 參 之層由前述模具脫模之步驟， 而前述加熱之溫度係150t至3 50°C。 [發明之效果] 藉由本發明，能夠不使用阻劑等濕式蝕刻用光罩以及 蝕刻液，可簡便地形成所希望的圖型。另外，藉由本發明 中以壓印方式進行的圖型形成方法而形成圖型的層，由於 並未使用感光性苯並環丁烯樹脂’因此透光度高、透明性 優異。 -9 - 201031690 【實施方式】 本發明係一種藉由壓印之圖型形成方法，具有： 以例如下述式（2 ) [化2](wherein R1 is independently of each other and represents an alkyl group having 1 to 6 carbon atoms, an ethylene group or a phenyl group; and R2 is independently of each other, and represents an alkyl group or a methoxy group having 1 to 6 carbon atoms; and R3 is mutually Independent, representing an alkyl group having 1 to 6 carbon atoms; independently of each other, representing 〇 or i; n is an integer from 1 to 3) represented by divinyl decane-bisbenzocyclobutene polymerized a step of forming a layer of the obtained benzocyclobutene resin on a substrate; and pressing the mold while heating and pressurizing the layer containing the benzocyclobutene resin to form a pattern containing the benzocyclobutene resin a step of laminating; and, after cooling, a step of demolding the layer containing the benzocyclobutene resin component of the above pattern from the mold, and the heating is performed at a temperature of 150 t to 350 °C. [Effects of the Invention] According to the present invention, it is possible to easily form a desired pattern without using a mask for wet etching such as a resist and an etching solution. Further, in the pattern forming method by the imprint method in the present invention, the pattern-forming layer is formed, and since the photosensitive benzocyclobutene resin is not used, the transmittance is high and the transparency is excellent. -9 - 201031690 [Embodiment] The present invention is a pattern forming method by imprinting, having: for example, the following formula (2) [Chemical 2]
所表示之二乙嫌基砂氧院一雙苯並環丁烯作爲前述式 (1)所表示之二乙烯基矽氧烷一雙苯並環丁烯， 將含有使該二乙烯基矽氧烷-雙苯並環丁烯經聚合所 得之苯並環丁烯樹脂之層形成於基板上之步驟； 於前述含有苯並環丁烯樹脂之層一邊加熱以及加壓一 邊按壓模具’使圖型形成於該含有苯並環丁烯樹脂之層之 步驟；以及 在冷卻後，使形成有前述圖型的含有苯並環丁烯樹脂 之層由前述模具脫模之步驟， 前述加熱之溫度係1 5 0 °c至3 5 0 °c。 以下對於本發明作詳細說明。 前述苯並環丁烯樹脂，係例如B階段化苯並環丁烯樹 脂。此處，B階段化意指半硬化狀態（硬化中間狀態）。 此狀態之樹脂加熱即軟化，若接觸某種溶劑則變成膨潤或 熔融或溶解的狀態。由於苯並環丁烯樹脂在如此的狀態，The double benzocyclobutene represented by the above formula (1), which is represented by the above formula (1), will contain the divinyl fluorene oxide. a step of forming a layer of a benzocyclobutene resin obtained by polymerization of a bisbenzocyclobutene onto a substrate; and pressing the mold while heating and pressurizing the layer containing the benzocyclobutene resin to form a pattern a step of the layer containing the benzocyclobutene resin; and, after cooling, a step of demolding the layer containing the benzocyclobutene resin of the above pattern from the mold, the temperature of the heating is 1 5 0 °c to 3 50 °c. The invention is described in detail below. The aforementioned benzocyclobutene resin is, for example, a B-staged benzocyclobutene resin. Here, the B-stage means a semi-hardened state (hardened intermediate state). The resin in this state is softened by heating, and becomes swelled or melted or dissolved when it contacts a certain solvent. Since the benzocyclobutene resin is in such a state,
所以變得容易使用壓印裝置形成所希望的圖型。另外，B 階段化苯並環丁烯樹脂，換言之亦爲預聚合物。 -10- 201031690 可供參考的是，熱硬化性樹脂之未硬化狀態表現爲A 階段，熱硬化性樹脂硬化步驟的最終階段表現爲C階段。 B階段，係指並非A階段亦並非C階段的狀態。 前述苯並環丁烯樹脂之重量平均分子量，通常爲 5 0,000 〜500,000，或是 1 00,000 〜400,000 ° 另外，重量平 均分子量，係藉由凝膠滲透層析（GPC )，使用聚苯乙烯 作爲標準試樣所得到之値。 0 前述含有苯並環丁烯樹脂之層，係藉由例如將該含有 苯並環丁烯樹脂以及可使其溶解之有機溶劑的壓印用膜形 成組成物塗佈於前述基板上，使前述有機溶劑蒸發而形成 。就其有機溶劑而言，可列舉例如甲苯、二甲苯、三甲苯 等烷基芳香族類、環戊酮、環己酮等環狀酮類、二乙醚、 二丙二醇二甲醚、四氫呋喃（THF )等醚類、醋酸丁酯、 1-甲基-2-吡咯烷酮（NMP)、二甲亞碾（DMSO)。另外 ，往前述基板上的塗佈，可採用旋轉塗佈法、浸漬法、噴 % 霧法等周知的塗佈法。 在本發明中，前述加壓係以例如1 MP a至1 OMP a之條 件下進行。關於前述加熱溫度，若超過3 5 0°C，則由於苯 並環丁烯樹脂分解，因此有在3 50 °C以下加熱的必要。相 反地，在低於150°C的溫度（例如120°C )，無法或難以 在含有苯並環丁烯樹脂之層形成所希望的圖型。形成前述 圖型的步驟之後的冷卻，並不一定要降至室溫。是因爲脫 模亦可在高於室溫的溫度進行之故。在本說明書中，將23 °C視爲室溫。 -11 - 201031690 在本發明中，前述模具，係指在表面形成有凹凸的圖 型，由石英、矽、碳化矽（Sic )、鎳、鉅等材料所構成 的"模"。在本發明中，可使用藉由塗佈市售的脫模劑（例 如OPTOOL[註冊商標]HD)進行表面處理後的或於表面 形成有薄膜的模具。藉由事前對模具進行如此的處理，變 得容易使苯並環丁烯樹脂由模具脫模。 另外，在本發明中，由前述模具脫模的步驟之後，可 因應必要進一步具有將前述基板以250 °C至350 °C之溫度 進行加熱的步驟。藉由此加熱步驟，苯並環丁烯樹脂會發 生硬化（交聯），而成爲三維聚合物化。由於在超過350 °C的溫度，苯並環丁烯樹脂會分解’因此有必要在35CTC 以下加熱。 [實施例] 以下列舉實施例對本發明進行說明，而本發明並不會 受到該等範例所限定。 ©- <比較例1以及實施例1至實施例4 > 使用旋轉塗佈機以2500rpm將4ml的苯並環丁烯樹脂 溶液（The Dow Chemical Company 製，商品名： CYCLOTENE[註冊商標]3022-35)在4英吋矽基板上塗佈 3 0秒鐘，於熱板上以9 0。(：烘烤9 0秒鐘。其後’將4英吋 矽基板切成約邊長3 cm方形尺寸的晶片’得到比較例1以 及實施例1至實施例4所使用的試樣。於所得到之試樣（ -12- 201031690 晶片），形成有苯並環丁烯樹脂層。 <實施例5至實施例7 > 使用旋轉塗佈機以1500rpm將4ml的苯並環丁嫌樹脂 溶液（The Dow Chemical Company 製’商品名： CYCLOTENE[註冊商標]3022-63 )在4英吋矽基板上塗佈 *' 30秒鐘，於熱板上以90°C烘烤90秒鐘。其後，將4英吋 φ 矽基板切成約邊長3 cm方形尺寸的晶片’得到實施例5至 實施例7所使用的試樣。於所得到之試樣（晶片）’形成 有苯並環丁烯樹脂層。 <實施例8至實施例1 1 > 調製將 4ml的苯並環丁烯樹脂溶液（The Dow Chemical Company 製，商品名：CYCLOTENE[註冊商標] 3〇22-35)以三甲苯（1,3,5-三甲苯）稀釋1〇倍的樹脂溶 液，使用旋轉塗佈機以3000rpm將此樹脂溶液在4英吋矽 . 基板上塗佈3 0秒鐘，在熱板上以90°C烘烤90秒鐘。其後 ，將4英吋矽基板切成約邊長3 cm方形尺寸的晶片’得到 實施例8至實施例1 1所使用的試樣。於所得到之試樣（ 晶片），形成有苯並環丁烯樹脂層。 <實施例1 2以及實施例1 3 > 使用旋轉塗佈機，以2000rpm將4ml的苯並環丁烯樹 脂溶液（The Dow Chemical Company 製，商品名： -13- 201031690 CYCLOTENE[註冊商標]3022-3 5 )在4英吋矽基板上塗佈 30秒鐘，在熱板上以90 °C烘烤90秒鐘。其後，將4英吋 矽基板切成約邊長3 cm方形尺寸的晶片，得到在實施例 1 2以及實施例1 3所使用的試樣。於所得到之試樣（晶片 )，形成有苯並環丁烯樹脂層。 [圖型形成] 使用壓印裝置（Litho Tech Japan股份有限公司製， _ LTNIP-5000 )，使圖型形成於苯並環丁烯樹脂層。亦即， 將準備好的上述試樣（晶片）配置於壓印裝置，以既定加 溫、加壓條件（記載於表1)，將模具按壓至苯並環丁烯 樹脂層而形成圖型，冷卻後，由壓印裝置取出該試樣（晶 片），在大致室溫使形成有圖型的苯並環丁烯樹脂層由模 具脫模，得到比較例1以及實施例1至實施例4之結果。 所使用之模具爲石英製，並且於事前以脫模劑（OPTOOL[Therefore, it becomes easy to form a desired pattern using an imprint apparatus. In addition, the B-staged benzocyclobutene resin, in other words, the prepolymer. -10- 201031690 For reference, the uncured state of the thermosetting resin is represented by the A stage, and the final stage of the thermosetting resin hardening step is represented by the C stage. Stage B refers to a state that is not A stage or C stage. The weight average molecular weight of the benzocyclobutene resin is usually from 5,000 to 500,000, or from 1,00,000 to 400,000 °. Further, the weight average molecular weight is determined by gel permeation chromatography (GPC) using polystyrene as a standard. The sample obtained from the sample. The layer containing the benzocyclobutene resin is applied to the substrate by, for example, coating the benzocyclobutene resin and the organic solvent capable of dissolving the organic solvent. The organic solvent is formed by evaporation. Examples of the organic solvent include alkyl aromatics such as toluene, xylene, and trimethylbenzene, cyclic ketones such as cyclopentanone and cyclohexanone, diethyl ether, dipropylene glycol dimethyl ether, and tetrahydrofuran (THF). Ethers, butyl acetate, 1-methyl-2-pyrrolidone (NMP), dimethyl amide (DMSO). Further, the coating on the substrate may be a known coating method such as a spin coating method, a dipping method, or a spray mist method. In the present invention, the above-mentioned pressurization is carried out under the conditions of, for example, 1 MP a to 1 OMP a. When the heating temperature exceeds 550 ° C, the benzocyclobutene resin is decomposed, so that it is necessary to heat at 550 ° C or lower. Conversely, at temperatures below 150 ° C (e.g., 120 ° C), it is not possible or difficult to form the desired pattern in the layer containing the benzocyclobutene resin. The cooling after the step of forming the aforementioned pattern does not necessarily have to be lowered to room temperature. This is because demolding can also be carried out at temperatures above room temperature. In the present specification, 23 ° C is regarded as room temperature. -11 - 201031690 In the present invention, the mold refers to a pattern in which irregularities are formed on the surface, and is composed of quartz, tantalum, strontium carbide (Sic), nickel, giant, and the like. In the present invention, a mold which is surface-treated or coated with a film on the surface by coating a commercially available release agent (e.g., OPTOOL [registered trademark] HD) can be used. By subjecting the mold to such a treatment in advance, it becomes easy to release the benzocyclobutene resin from the mold. Further, in the present invention, after the step of demolding the mold, it is necessary to further have a step of heating the substrate at a temperature of from 250 ° C to 350 ° C as necessary. By this heating step, the benzocyclobutene resin is hardened (crosslinked) to become a three-dimensional polymerized. Since the benzocyclobutene resin decomposes at a temperature exceeding 350 °C, it is necessary to heat it below 35 CTC. [Examples] The present invention is illustrated by the following examples, but the present invention is not limited by the examples. ©- <Comparative Example 1 and Example 1 to Example 4> 4 ml of a benzocyclobutene resin solution (manufactured by The Dow Chemical Company, trade name: CYCLOTENE [registered trademark] 3022 was used at 2500 rpm using a spin coater. -35) Coating on a 4 inch substrate for 30 seconds, and on a hot plate at 90. (: Baking for 90 seconds. Thereafter, '4 Å substrate was cut into wafers having a side length of 3 cm square size'. The samples used in Comparative Example 1 and Examples 1 to 4 were obtained. The obtained sample (-12-201031690 wafer) was formed with a benzocyclobutene resin layer. <Example 5 to Example 7> 4 ml of benzocyclobutene resin solution was used at 1500 rpm using a spin coater (The Dow Chemical Company's 'trade name: CYCLOTENE [registered trademark] 3022-63) was coated on a 4 inch substrate for * 30 seconds, and baked on a hot plate at 90 ° C for 90 seconds. The 4 inch φ 矽 substrate was cut into wafers having a square size of about 3 cm in side length. The samples used in Examples 5 to 7 were obtained. The obtained sample (wafer) was formed with benzocyclobutene. (Ethylene Resin Layer) <Example 8 to Example 1 1> 4 ml of a benzocyclobutene resin solution (manufactured by The Dow Chemical Company, trade name: CYCLOTENE [registered trademark] 3〇22-35) was prepared in three Toluene (1,3,5-trimethylbenzene) was diluted 1 times the resin solution, using a spin coater at 3000 rpm to make the resin solution at 4 inches. The plate was coated for 30 seconds, and baked on a hot plate at 90 ° C for 90 seconds. Thereafter, the 4 inch substrate was cut into wafers having a square length of about 3 cm squares. [Example 8 to Implementation The sample used in Example 1 1. A benzocyclobutene resin layer was formed on the obtained sample (wafer). <Example 1 2 and Example 1 3 > Using a spin coater at 2000 rpm 4 ml of a benzocyclobutene resin solution (manufactured by The Dow Chemical Company, trade name: -13-201031690 CYCLOTENE [registered trademark] 3022-3 5) was coated on a 4 inch substrate for 30 seconds on a hot plate. The film was baked at 90 ° C for 90 seconds. Thereafter, the 4 inch substrate was cut into a wafer having a square shape of about 3 cm in length, and the samples used in Example 12 and Example 13 were obtained. A benzocyclobutene resin layer was formed on the obtained sample (wafer). [Form Formation] An image was formed on benzo by using an imprint apparatus (Litho Tech Japan Co., Ltd., _LTNIP-5000). a cyclobutene resin layer, that is, the prepared sample (wafer) is placed in an imprinting apparatus under predetermined heating and pressing conditions (remembering In Table 1), the mold is pressed to the benzocyclobutene resin layer to form a pattern. After cooling, the sample (wafer) is taken out by an imprint apparatus, and the patterned benzocyclobutene is formed at approximately room temperature. The olefin resin layer was released from the mold to obtain the results of Comparative Example 1 and Examples 1 to 4. The mold used is made of quartz and is pre-released with a release agent (OPTOOL[
註冊商標]HD)進行過表面處理者。 H 使用壓印裝置（明昌機工股份有限公司製，NM-0801HB)，藉由與上述相同之方法，使圖型形成於苯並環 丁烯樹脂層。亦即，將準備好的上述試樣（晶片）配置於 壓印裝置，以既定的加溫、加壓條件（記載於表2 )，將 模具按壓至苯並環丁烯樹脂層而形成圖型，冷卻後，由壓 印裝置取出該試樣（晶片），在大致室溫使形成有圖型的 苯並環丁烯樹脂層由模具脫模，得到實施例5至實施例1 3 之結果。所使用的模具爲矽製，並且於事前以脫模劑（ -14 - 201031690 OP TOOL[註冊商標]HD)進行過表面處理者。 圖型形成的有無，係以剖面觀察SEM (日立High-Technologies 股份 有限公 司製， S4800) ， 觀察圖 型的剖 面而作判斷。將其結果表示於下述表1以及表2。圖型有 形成的情況表示爲”〇”，圖型並未形成的情況表示爲。 關於表2所記載之加溫條件1，係以1 °C /秒鐘使其昇溫。Registered Trademark] HD) has been surface treated. H The pattern was formed on the benzocyclobutene resin layer by the same method as described above using an imprint apparatus (manufactured by Mingchang Machinery Co., Ltd., NM-0801HB). In other words, the prepared sample (wafer) is placed in an imprint apparatus, and the mold is pressed to the benzocyclobutene resin layer to form a pattern under predetermined heating and pressing conditions (described in Table 2). After cooling, the sample (wafer) was taken out by an imprint apparatus, and the patterned benzocyclobutene resin layer was released from the mold at room temperature to obtain the results of Examples 5 to 13. The mold used was tantalum, and was subjected to surface treatment with a release agent (-14 - 201031690 OP TOOL [registered trademark] HD). The presence or absence of the pattern formation was judged by a cross-sectional observation SEM (manufactured by Hitachi High-Technologies Co., Ltd., S4800), and a cross-section of the pattern was observed. The results are shown in Table 1 and Table 2 below. The case where the pattern is formed is expressed as "〇", and the case where the pattern is not formed is expressed as. The heating condition 1 described in Table 2 was raised at 1 ° C / sec.
膜厚 壓印條件[加熱溫度(時間)] 壓印條件 結果 開始時溫度 加溫條件1 加溫條件2 伽壓） 比較例1 26μιη 120°C 120°C保持(200秒鐘) 一 2.5MPa X 實施例1 26μιη 150°C 1501保持(200秒鐘) — 2.5MPa 〇 實施例2 26μιη 170°C 17〇°C保持(200秒鐘） — 2.5MPa 〇 實施例3 26μιη 150。。 150〇C保持(200秒鐘) — 5MPa 〇 實施例4 26μηι 200°C 200〇C保持(200秒鐘） — 5MPa 〇 -15- 201031690 [表2] 表2 膜厚 壓印條件[加熱溫度(時間)] 壓印條件(加壓） 結果 開始時 溫度 加溫條件1 加溫條件2 實施例5 20μιη 150°C 15(TC—280°C 昇溫 (130秒鐘） 保持280°C (120秒鐘） lOMPa 〇 實施例6 20μιη 150。。 150。。—280。(：昇溫 (130秒鐘） 保持28(TC (120秒鐘） 5MPa 〇 實施例7 20μπι 150°C 150°C->280°C 昇溫 (130秒鐘） 保持280〇C (120秒鐘） IMPa 〇 實施例8 100nm 150°C 150。。—280。。昇溫 (130秒鐘） 保持280〇C (60秒鐘） lOMPa 〇 實施例9 lOOnm 150°C 150°C->280〇C 昇溫 (130秒鐘） 保持28CTC (60秒鐘） 5MPa 〇 實施例10 lOOnm 150°C 150X^280。。昇溫 (130秒鐘） 保持280〇C (60秒鐘） 3MPa 〇 實施例11 lOOnm 150。。 150°C—280°C 昇溫 (130秒鐘） 保持280°C (60秒鐘） IMPa 〇 實施例12 2μηι 150°C 150°C—280°C 昇溫 (130秒鐘） 保持28(TC (60秒鐘） 3MPa 〇 實施例13 2μτη 150°C 150°C—280°C 昇溫 (130秒鐘） 保持280°C (60秒鐘） IMPa 〇 如同表1以及表2所表示般，實施例1至實施例1 3 之方式，壓印時在1 50°C以上進行加熱的試樣，圖型可形 成。另一方面，如表1所表示的比較例1般，在1 2 0°C壓 印的試樣，圖型不可能形成。將爲了得到實施例5至實施 例13之結果所使用的模具（矽製模具）之剖面SEM影像 表示於圖1 ;將形成有圖型的實施例1 1之試樣之剖面 -16- 201031690 SEM影像表示於圖2。 [尺寸精密度之測定] 對於形成有圖型的實施例9至實施例11之試樣之圖 型尺寸，以及所使用的模具之圖型尺寸進行了測定。測定 係使用剖面觀察SEM (日立High-Technologies股份有限 公司製’ SM 00 )的長度測定機能，從各圖型排列的任意 φ 處選擇3點進行測定。將其結果表示於下述表3。 [表3] 表3 圖型1 圖型2 圖型3 平均 幅寬(nm) 深度(nm) 幅寬(nm) 深度(nm) 幅寬(nm) 深度㈣ 幅寬(nm) 深度(nm) 模具 119 340 116 349 117 346 117 345 實施例9 116 349 117 346 114 349 116 348 實施例10 116 340 116 349 114 345 115 345 實施例11 120 346 119 351 120 351 120 349 由表3所表示的結果看來，相對於所使用模具的圖型 尺寸而以平均値來計，圖型幅寬在±3nm以內、圖型 深度在±4nm以內。因此，圖型誤差在±3%以內，尺寸精 密度非常良好。亦即’顯示出幾乎沒有尺寸變化的壓印是 可進行的。進一步而言，由實施例9至實施例1 1之圖型 尺寸平均値爲幅寬：117nm、深度：347nm，可知縱橫比 成爲347/117= 3.0’獲得較大縱橫比的圖型化是可進行的 -17- 201031690 【圖式簡單說明】 圖1係表示壓印用模具之剖面SEM影像。 圖2係表示使用了實施例1 1之方法，所得到的試樣 其剖面之SEM影像。 -18-Film thickness imprint condition [heating temperature (time)] Imprinting condition start temperature temperature heating condition 1 heating condition 2 galvanic pressure) Comparative Example 1 26μιη 120°C 120°C hold (200 seconds) One 2.5MPa X Example 1 26 μm 150 ° C 1501 hold (200 seconds) - 2.5 MPa 〇 Example 2 26 μηη 170 ° C 17 ° ° C hold (200 seconds) - 2.5 MPa 〇 Example 3 26 μιη 150. . 150 〇C hold (200 seconds) — 5 MPa 〇 Example 4 26μηι 200°C 200〇C hold (200 seconds) — 5MPa 〇-15- 201031690 [Table 2] Table 2 Film thickness embossing conditions [heating temperature ( Time)] Imprint condition (pressurization) Temperature at the beginning of the result Condition 1 Heating condition 2 Example 5 20μηη 150°C 15 (TC-280°C temperature rise (130 seconds) Hold 280°C (120 seconds) lOMPa 〇Example 6 20μιη 150. 150--280. (: Temperature rise (130 seconds) Hold 28 (TC (120 seconds) 5MPa 〇 Example 7 20μπι 150°C 150°C->280° C Temperature rise (130 seconds) Hold 280 〇C (120 seconds) IMPa 〇Example 8 100nm 150°C 150. —280. Temperature rise (130 seconds) Maintain 280〇C (60 seconds) lOMPa 〇Implementation Example 9 lOOnm 150 ° C 150 ° C -> 280 ° C temperature rise (130 seconds) to maintain 28 CTC (60 seconds) 5 MPa 〇 Example 10 lOOnm 150 ° C 150X ^ 280. Temperature (130 seconds) Maintain 280 〇C (60 seconds) 3MPa 〇Example 11 lOOnm 150. 150°C-280°C Temperature rise (130 seconds) Hold 280°C (60 seconds) IMPa 〇Example 12 2μηι 150°C 150°C —280°C Temperature rise (130 seconds) Hold 28 (TC (60 seconds) 3MPa 〇Example 13 2μτη 150°C 150°C—280°C Temperature rise (130 seconds) Hold 280°C (60 seconds) As shown in Table 1 and Table 2, IMPa® can be formed in a sample which is heated at 150° C. or higher at the time of imprinting, as shown in Table 1 and Table 2. The pattern can be formed. In the case of Comparative Example 1 shown, it was impossible to form a pattern imprinted at 120 ° C. The cross-section SEM of the mold (twisted mold) used to obtain the results of Examples 5 to 13 The image is shown in Fig. 1; the cross-section of the sample of Example 11 in which the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of the pattern of The pattern size of the sample of Example 11 and the pattern size of the mold used were measured. The measurement was performed by using a cross-sectional observation SEM ("SM 00" manufactured by Hitachi High-Technologies Co., Ltd.). Three points are selected at any φ of the type arrangement for measurement. The results are shown in Table 3 below. [Table 3] Table 3 Pattern 1 Pattern 2 Pattern 3 Average Width (nm) Depth (nm) Width (nm) Depth (nm) Width (nm) Depth (4) Width (nm) Depth (nm) Mold 119 340 116 349 117 346 117 345 Example 9 116 349 117 346 114 349 116 348 Example 10 116 340 116 349 114 345 115 345 Example 11 120 346 119 351 120 351 120 349 From the results shown in Table 3 The pattern width is within ±3 nm and the pattern depth is within ±4 nm, based on the average size of the pattern size of the mold used. Therefore, the pattern error is within ±3% and the dimensional precision is very good. That is, an imprint showing that there is almost no dimensional change is possible. Further, the average size of the pattern from the embodiment 9 to the embodiment 11 is the width: 117 nm and the depth: 347 nm, and it can be seen that the aspect ratio is 347/117 = 3.0', and the pattern of obtaining a large aspect ratio is available. -17- 201031690 [Simplified illustration of the drawings] Fig. 1 is a cross-sectional SEM image of a mold for imprinting. Fig. 2 is a SEM image showing the cross section of the obtained sample by the method of Example 11. -18-