1252520 九、發明說明 【發明所屬之技術領域】 本發明是有關於一種逆忒 λΛ· /χτ 見式试奈米壓印製程（Reversal icr〇/Nano_Imprinting Process)， 且特別疋有關於一種無阻 d殘召層之逆式微奈米壓印努 【先前技術】 •、在半導體製程中’傳統之微影餘刻技術係先將光阻劑旋 轉塗佈於欲使用之基板上，再利轉直之紫外光照射光罩， 而將所欲之圖案轉移至基板上之光阻财，接下來以此圖案 化之光阻劑作為罩幕（Mask)，並以離子反應性餘刻 Ion Etching ’ RIE)或是酸式钱刻將光阻劑之圖案轉移至基板 中。这樣傳統之微影蝕刻技術之缺點在於：除了整個製程皆 必須在黃光室製作以外，對於在奈米尺寸線寬下，會有紫外 光繞射的限制以及具準直性之紫外光設備昂貴等問題；而且 • 對於較大尺寸之基板，也會有照光不均勻之缺失；另外對於 可撓曲塑膠板，也會產生光阻劑旋轉塗佈不均的現象。 近年來，在傳統曝光顯影技術的製程繁雜，且隨著圖案 線寬尺寸的日益縮減下，產生紫外光繞射之限制，並且設備 一 成本也隨之提高許多。有鑑於此，目前有許多研究極力開發 ^ 足以取代傳統微影的技術，其中以微奈米壓印技術 (Nano/Micro Imprinting Lithography)為公認最具有潛力的 取代技術之一，尤其在奈米尺度與三維空間圖案的製作上， 微奈米壓印技術有其優勢。 6 1252520 壓印技術係在已圖案化之模板的表面上做抗黏著的處 理’並於所欲使用之基板上旋轉塗佈熱塑性阻劑，再於高溫 高壓(Force)的環境下，將模板之圖案化表面與基板上之埶 塑性阻劑對壓，即可將模板之圖案轉移至基板之熱塑性阻劑 上。此Μ印技#之缺點在於：為了增加阻劑之流動性與降低 阻劑殘餘層之厚度’此製程必須在高溫的環境與大的工作壓 ^下操作’因此容易對基板造成傷害，尤其是對可撓取之塑 膠基板而έ，係無法在高溫下進行，如此將無法將圖案完整 轉移。另外’若是施加的壓力不夠，或者是所選擇之阻劑不 適當，會造成阻劑殘留層過厚不易去除、或是圖案變形或收 縮的現象。 另外’更發展出-種逆㈣技術。目前之逆壓印技術係 =低分子量之阻劑’並選擇適合之溶劑將阻劑予以溶解 後方疋轉塗佈於模柄之 、板之已圖案化表面上，再利用壓印方式將模 之阻劑圖案轉移至所使欲使用之基板。此一傳統之逆麼 點在於:適用之低分子量的阻劑不易取得或是價 二ρ貝且無法將阻劑完全填入模板之圖案開口中，因 =各易得到與模板圖案相同之深寬比。另外，傳統之逆屋 =限於阻劑的選擇’所以其製程視窗（ρ刚ess Win 2狹窄，且製程彈性不佳。並且，在壓印程序後，轉移至 二制上之阻劑圖案具有一定厚度的殘留層，且此殘留層不易 . 之後必須再利用蝕刻方式來去除阻劑殘留層， =旦的一個動作會對阻劑的選擇與製程動作的方便性造成 又衫響，進而導致需不斷地調整製程參數。 1252520 【發明内容】 因此，本發明之目的就是在提供一盔 奈米壓印製程，在壓印步驟德益"“、、殘邊層之逆式微 留層控制問題，可提升製程彈性。 ”，、阻蜊殘 本發明之另一目的是在提供一 米麼印製程，因為無阻劑殘留声，因此之-式微奈 外利用蝕刻步驟來移除阻 〜臭額 丰璁工， …戈W層如此一來，可簡化製裎 广’，可提升製程可靠度，並可降低製程成本。 米壓=:之:二的是在提供-種無殘留層之逆式微奈 十‘ P“，由於無阻劑殘留層，因此阻劑的選擇 性，可擴大製程窗。 /、泮 ”本t月之再一目的是在提供一種無殘留層之逆式微奈 米壓印製程’無須在高溫與高工作壓下進行，因此除了可應 用在硬質基板上，更可適用於軟質之可撓曲基板上，具有相 當廣泛之應用性。 根據本發明之上述目的，提出一種無殘留層之逆式微奈 米壓P製）包括：先提供一具有一微米或奈米尺度圖 案之模板，且Η案具有至少H π區。以真空沈積或是化學 鍵…之方式形成一脫膜層覆蓋在上述模板之表面上。再利用 界面活性劑在此表面上作表面處理，使之形成一界面活性層 覆蓋在此脫膜層上。並移除模板表面上之開口區外的界面活 性層。接著，進行一阻劑塗佈步驟，使阻劑填入開口區中。 隨後提供一任意基板，進行接觸壓印步驟，而將模板之表面 1252520 與基板之表面完全貼合’藉此將模板圖案完全的 之表面上，而且沒有阻劑殘留層之問題。 基板 依照本發明一較佳實施例，上述之脫膜層係 層’且此單分子層之表面具有複數個疏水官能基 刀 :活性層至少包括具有雙官能基之複數個高分子，且每j :刀子之-端為一疏水基，另一端為一親水基，每一個高分 之疏水基與單分子層之疏水官能基產生物理性之弱吸 附’而使每一個高分子之親水基朝外。其中，這些高分子之 親水基為具有親水性之官能基’例如績酸基經基 (_〇H)、或胺基（_随2)等。 工土 。在本發明之另一較佳實施例中，脫膜層係一單分子層， 且單分子層具有與阻劑之極性差異大之官能基。換言之，脫 膜層係一抗黏著層，且此抗黏著層可為含氣類鑽碳鐵氟 龍膜薄或數十奈米厚之金屬薄膜等。此外，進行接觸壓印步 驟時之壓印溫度約控制在阻劑之玻璃軟化點左右。 藉由在模板表面上之開口的側壁面與底面形成界面活 性層，阻劑可輕易填入開口，因此可完整轉移圖案。此外， 由於界面活性層最終僅形成在模板之開口的側壁面與底面 上’因此壓印程序後無阻劑殘留層。如此一來，壓印程序後 無須進行額外之蝕刻來移除阻劑殘留層，故不僅可簡化製程 步驟，阻劑的選擇更具彈性，而可達到提升製程可靠度、降 低製程成本以及擴大製程窗的目的。 【實施方式】 9 1252520 本I明揭露一種益殘留® >、系《V、士 印步驟後無阻劑殘Μ ^ 卩製程，於壓 盘軟質基板，星： 在低溫下進行，而適用於硬質 、土 ^有極廣泛之應用性。為了使本發日月t翁、f # 加詳盡與完備，可夂日…" "吏奉毛月之敘述更 示。 > π下列描述並配合第1圖至第9圖之圖 明參知第1圖至第9圖，其繪示依照本發明-較佳實施 例的一種無殘留層逆式 、 ^ 延式被奈米屋印製程之製程剖面圖，呈 中弟2圖係界面活性南丨盥 八 與杈板表面吸附示意圖。進行無殘留 曰之逆式H Μ印製程時，先提供模板⑽，其中此模板 二〇之-表面11〇已設有欲壓印之圖案，且模板⑽可由任 意材質所組成。此模板100之表面11〇上的圖案可為具各種 尺寸線寬的圖案，例如微米或奈米線寬圖案。在此較佳實施 例中，板100之表面11()上係設有微奈米尺寸之線寬的圖 案。模板100之表面110上的壓印圖案係由至少一平面 以及至；一開p i 06所組成。在本較佳實施例中，模板⑽ 之表面110係由多個平面108與多個開口 1〇6所組成。 接下來，形成脫膜層1〇2覆蓋在模板100具有壓印圖案 之表面m上。其中，脫膜層102可為利用例如自我組裝 (Self-assembling)的方式鍵結一層具有疏水官能基單分子 層、或者具有與後續填入開口 106之阻劑的極性差異很大之 官能基的單分子層，例如十八烷基三氯矽甲烷(0ctadecyI Tri-chlorosilane)。在本發明之一較佳實施例中，脫膜層ι〇2 係由具有疏水官能基之單分子122所組成，如第2圖^示。 在本發明之其他實施例中，脫膜層102亦可利用例如沉積方 10 12525201252520 IX. INSTRUCTIONS OF THE INVENTION [Technical Field to Be Invented by the Invention] The present invention relates to a reverse 忒λΛ· /χτ See-Real icr〇/Nano_Imprinting Process, and particularly relates to an unrestrained d-residue The reverse micro-nano embossing of the layer [previous technology] • In the semiconductor process, the traditional lithography technology is to spin-coat the photoresist on the substrate to be used, and then turn the ultraviolet light. The reticle is used to transfer the desired pattern to the photo-resistance on the substrate, followed by the patterned photoresist as a mask and ion-reactive Ion Etching 'RIE or acid The pattern of the photoresist is transferred into the substrate. The disadvantage of such conventional lithography etching technology is that in addition to the entire process, it must be fabricated in the yellow light chamber, and for the nanometer size line width, there is a limitation of ultraviolet light diffraction and a collimating ultraviolet light device. Expensive and other problems; and • For larger substrates, there will be a lack of illumination unevenness; in addition, for flexible plastic sheets, uneven coating of the photoresist will also occur. In recent years, the process of the conventional exposure and development technology is complicated, and as the line width of the pattern is increasingly reduced, the limitation of ultraviolet light diffraction is generated, and the cost of the device is also greatly increased. In view of this, many studies have been devoted to the development of technologies that are sufficient to replace traditional lithography, among which Nano/Micro Imprinting Lithography is recognized as one of the most promising replacement technologies, especially at the nanometer scale. With the production of three-dimensional patterns, micro-nano imprint technology has its advantages. 6 1252520 Imprint technology is anti-adhesive treatment on the surface of the patterned template' and spin-coated the thermoplastic resist on the substrate to be used, and then in the high temperature and high pressure (Force) environment, the template The patterned surface is pressed against the tantalum plastic resist on the substrate, and the pattern of the template is transferred to the thermoplastic resist of the substrate. The disadvantages of this Μ印技# are: in order to increase the fluidity of the resist and reduce the thickness of the residual layer of the resister. This process must be operated under high temperature environment and large working pressure, so it is easy to cause damage to the substrate, especially The squeezing of the flexible plastic substrate cannot be performed at a high temperature, so that the pattern cannot be completely transferred. In addition, if the applied pressure is insufficient or the selected resist is not appropriate, the residual layer of the resist is too thick to be easily removed, or the pattern is deformed or shrunk. In addition, the development of the reverse (four) technology. At present, the reverse imprint technology is a low molecular weight resistant' and a suitable solvent is selected to dissolve the resist, and then applied to the patterned surface of the mold, and then the stamp is used. The resist pattern is transferred to the substrate to be used. The inverse of this tradition is that the applicable low molecular weight resist is not easy to obtain or the price is not priced and the resist can not be completely filled into the pattern opening of the template, because each of them can easily obtain the same width and width as the template pattern. ratio. In addition, the traditional inverse housing = limited to the choice of resisting 'so its process window (ρ just ess Win 2 narrow, and the process flexibility is not good. And, after the imprinting process, the resist pattern transferred to the second system has a certain Residual layer of thickness, and this residual layer is not easy. Afterwards, the etching method must be used to remove the residual layer of the resist. One action of =1 will cause the choice of the resist and the convenience of the process to cause the shirt to ring, which leads to constant demand. Adjusting the process parameters. 1252520 [Description of the Invention] Therefore, the object of the present invention is to provide a helmet nano-imprint process, in the embossing step Deyi ",, the residual micro-remaining layer control problem of the residual layer, Improve the flexibility of the process.",,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, , ... Go W layer so that it can simplify the system, can improve the process reliability, and reduce the cost of the process. Meter pressure =: it: the second is in the provision of - no residual layer of the reverse micro-nine ' P", In the residual layer of the non-resistive agent, the selectivity of the resister can expand the process window. /, 泮" Another purpose of this month is to provide a reverse micro-nano imprint process without residual layer 'no need to be high temperature and high The work is carried out under pressure, so that it can be applied to a flexible substrate, and is applicable to a flexible flexible substrate, and has a wide range of applicability. According to the above object of the present invention, a reverse micro-nano layer without a residual layer is proposed. Pressing P) includes first providing a template having a one-micron or nano-scale pattern, and the file has at least a H π region. A release layer is formed on the surface of the above-mentioned template by vacuum deposition or chemical bonding. The surfactant is then surface treated on the surface to form an interface active layer overlying the release layer. And removing the interface active layer outside the open area on the surface of the template. Next, a resist coating step is performed to fill the open region in the resist. An optional substrate is then provided to perform the contact imprinting step, while the surface 1252520 of the stencil is completely conformed to the surface of the substrate' thereby leaving the stencil pattern on the finished surface without the problem of a residual layer of resist. Substrate According to a preferred embodiment of the present invention, the above-mentioned stripping layer is a layer and the surface of the monolayer has a plurality of hydrophobic functional knives: the active layer comprises at least a plurality of polymers having a bifunctional group, and each j The end of the knife is a hydrophobic group, and the other end is a hydrophilic group. Each of the high-dividing hydrophobic groups and the hydrophobic functional groups of the monolayer form a physical weak adsorption, and the hydrophilic group of each polymer faces outward. . Here, the hydrophilic group of these polymers is a hydrophilic functional group such as a benzyl group (_〇H) or an amine group (_2). Working soil. In another preferred embodiment of the invention, the release layer is a monolayer, and the monolayer has a functional group that differs greatly from the polarity of the resist. In other words, the release layer is an anti-adhesive layer, and the anti-adhesion layer may be a thin film of a gas-like diamond-like carbon tetrafluorocarbon film or a metal film of several tens of nanometers thick. Further, the imprinting temperature at the time of the contact imprinting step is controlled to be about the softening point of the glass of the resist. By forming an interface active layer on the side wall surface and the bottom surface of the opening on the surface of the stencil, the resist can be easily filled into the opening, so that the pattern can be completely transferred. In addition, since the interface active layer is finally formed only on the side wall surface and the bottom surface of the opening of the template, there is no resist remaining layer after the imprinting process. In this way, no additional etching is required after the imprinting process to remove the residual layer of the resist, so that the process steps can be simplified, the selection of the resist is more flexible, and the process reliability can be improved, the process cost can be reduced, and the process can be expanded. The purpose of the window. [Embodiment] 9 1252520 This disclosure discloses a kind of residual residue >, "V, the non-resistance residue after the step of printing" ^ 卩 process, on the soft substrate of the pressure plate, star: at low temperature, and suitable for hard , soil ^ has a wide range of applications. In order to make this day and month t Weng, f # add detailed and complete, you can see the following day...""> π The following description and the drawings of Figs. 1 to 9 show the first to ninth drawings, which show a residual layer-free inverse type, ^ extended type according to the preferred embodiment of the present invention. The process profile of the nano-house printing process is shown in the schematic diagram of the adsorption of the interface between the Nandian and the scorpion. In the case of a reverse-free H-print process without residue, a template (10) is first provided, wherein the template has a pattern to be imprinted, and the template (10) can be composed of any material. The pattern on the surface 11 of the template 100 may be a pattern having a line width of various sizes, such as a micron or nano line width pattern. In the preferred embodiment, the surface 11() of the panel 100 is provided with a pattern of line widths of micronano dimensions. The embossed pattern on the surface 110 of the stencil 100 is composed of at least one plane and to; an opening p i 06. In the preferred embodiment, the surface 110 of the template (10) is comprised of a plurality of flat faces 108 and a plurality of openings 1〇6. Next, the release layer 1 2 is formed to cover the surface m of the template 100 having the embossed pattern. Wherein, the stripping layer 102 may be a layer of a monofunctional layer having a hydrophobic functional group or a functional group having a polarity different from that of a resist which is subsequently filled in the opening 106 by, for example, self-assembly. A monolayer, such as Octadecyl Tri-chlorosilane. In a preferred embodiment of the invention, the release layer ι 2 is comprised of a single molecule 122 having a hydrophobic functional group, as shown in Figure 2. In other embodiments of the invention, the release layer 102 can also utilize, for example, a deposition side 10 1252520
為含氟類鑽碳膜、鐵氟龍膜薄或數十奈米厚的金屬薄It is a fluorine-based diamond carbon film, a thin Teflon film or a thin metal of several tens of nanometers thick.
界面活性劑薄膜所組成，此界面活性劑具有眾多雙官能基之 φ 高分子I28，每一個高分子 一端為一親水基126，如第 上二。< 觸狗一顽_水暴124，另 2圖所示。高分子128之疏水基 U8之一端為一疏水基124， 124具有中、長之純碳鏈，例如至少具有八個以上碳分子之 長鏈碳高分子化合物。高分子128之親水基126為具有親水 性之官能基，例如磺酸基、羥基、或胺基等。界面活性層 1〇4之高分子128的疏水端124與模板1〇〇上之脫膜層1〇2 中單为子122的疏水基產生物理性的弱吸附，如此一來，利 用此物理吸附現象而可將界面活性層1 〇4吸附於脫膜層 102上，並可使鬲分子128另一端之親水基ΐ2ό朝外，如第 2圖所示。因此，可將模板1〇〇之表面11〇予以改質，而使 模板1〇〇之表面110具有親水的特性。完成界面活性層1〇4 之塗佈後，更可先對模板丨〇〇進行低溫烘乾步驟，以烘乾模 板100上之界面活性層104。 接著’提供平板112，其中此平板112之材質可例如為 塑膠，如第3圖所示。在此平板112之一表面上塗覆有一層 黏著材料或親水性材料，在本實施例中，平板112之表面係 塗覆一層黏著層114，例如黏膠。隨後，如第4圖所示，將 1252520 模板H)0倒覆在平才反112上，藉以使模板ι〇〇之表面ιι〇 與平板H2緊貼，如此可分別利用沾黏方式或物理吸附方 式，使模板100之表面110的平面1〇8部分上之界面活性層 附著在平112之黏著材料（例如黏著| ιΐ4)或親水 材料上。將模才反1〇〇從平方反112上移開後，模才反之表面 110的平φ 1 08 4分上之界面活性| i 〇4b附著在平板112 之上方，如第5圖所示。於是’移除了模板1〇〇上開口 1〇6 以外之界面活性層104b’而在模板1〇〇之表φ ιι〇的開口 1〇6内部之侧壁面與底面仍保有界面活性&心。也就是 說’界面活性層104a中具雙官能基之高分子仍吸附在模板 100之表面110上之開口 106的側壁面與底面上，而模板 之表面110的開口 106依舊具有親水的特性。如此，模板 100之表面110的平面108部分為疏水性，而圖案開口 1〇6 内為親水性。 完成模板100之表面110的改質處理後，隨即可利用例 如旋轉塗佈或是沈浸的方式，形成阻劑116填入表面110 之開口 106中，如第6圖所示。其中，阻劑116之材質可例 如為有機材料或無機材料，阻劑116之材料可例如選用聚甲 基丙烯酸甲酯（PMMA)、聚苯乙烯（PS)或無機膠質溶液等。 於阻劑116塗佈完成後，可進一步對阻劑116進行軟烤處 理。軟烤處理之反應溫度視阻劑丨16之材料而定，而軟烤處 理之反應時間則視阻劑丨16之材料與反應溫度而定。在本發 明之一較佳實施例中，軟烤處理之反應溫度較佳係控制在介 於約80。(：至約90°C之間，且軟烤處理之反應時間較佳係控 12 1252520 制在介於約5分鐘至約1 0分鐘之間。 本發明之一特徵在於，由於模板1 0 0表面1 1 〇上之開口 1〇6覆蓋有界面活性層1〇4，因此開口 1〇6之内侧面與底面 已佈滿緻氆之親水官能基，而阻劑116中之阻劑分子1 3 〇 又到這些親水官能基的吸引，如第2圖所示，如此一來使阻 , ㈣116可70全填入模板1 〇〇表面110之開口 106中，但阻劑 U 6卻不致形成在模板1 〇〇表面110之平面108上。此外， # 不同阻劑的使用，可以利用上述之原理輕易的找到適合之界 面活性劑。 *然後，提供欲圖案化之基板118，其中此基板118可為 軟為基板或硬質基板，例如矽基板或可撓取塑膠基板等。在 進行壓印程序前，可選擇性地先對基板118之表面進行清潔 與電漿活化處理，以增加基板118之表面的活性，並藉此提 升阻劑116與基板118之間的附著力。在本發明之一較佳實 施例中，係利用氧電聚來進行基板118表面之清潔與活化、。 • 接下來，再次倒覆模板100,並使模板1〇〇之表面ιι〇緊貼 在基板118欲圖案化之表面上，來進行壓印程序，如第7 圖所示。在壓印程序中，利用接觸熱屋印之方式，將模板 100之® _印至基板118之表面上’其中壓印過程之反應 溫度約控制在阻劑116之玻璃軟化點（Tg)左右，且所施加之 力只需要將模板100與基板118表面完全貼合即可。待反應 溫度低於阻劑116之玻璃軟化點之後，可輕易地將模板100 與基板118分離，如此即可得到無阻劑殘留層之阻劑圖案 122於基板118之欲圖案化表面上，如第8圖所示。 13 1252520 本發明之另一特徵在於，由於壓印程序僅需在控制在阻 J 11 6的玻璃軟化點左右，而所施加的壓力只需要將模板與 基板表面疋全貼合即可，因此無需在高溫與高壓下進行，如 此來’對於軟質可撓曲之塑膠基板或其他無法在高溫高壓 力下適用之基板，仍可適用，應用性相當廣。 ^ 本發明之再一特徵在於，由於阻劑116並未形成在模板 100之表面110的平® 108部分上，因此於壓印程序後，並 籲無阻劑殘留層在基板118上。如此一來，可省卻以餘刻去除 阻劑殘留層的動作，亦可避免因阻劑殘留層所引發之圖案變 形的問題。 、 將阻劑圖案122轉移至基板118上後，可依不同需求 直接使用此有阻劑圖案122之基板118、或者以此阻劑圖窝 I、22作為_罩幕，利關如反應性料_(RIE)的方3 或酉夂式㈣的方式㈣基板118，而將阻劑圖帛轉移至 基板118巾。然後’利用例如濕式剝除的方式，並以適” 溶劑移除殘留之阻劑116，即可使基板118之表面具有^ 板100圖案相對應之圖案120，如第9圖所示。 由上述本發明較佳實施例可知，本發明之一優點就是因 為本發明之無殘留層之逆式微奈米壓印製程，㈣印程序後 無阻劑殘留層，因此無阻劑殘留層控制問題，而更可避免因 阻劑殘留層所引發之圖案變形或收縮、以及殘留層不易去除 的問題，進而可提升製程之彈性。 因為 由上述本發明較佳實施例可知 本發明之無殘留層之逆式微奈 ’本發明之另一優點就是 米壓印製程無阻劑殘留 14 1252520 層，於疋無需在壓印步驟^ ^ ^ ^ ^ ^ ^ 留層。因此，可達…ί 刻步驟來移除阻劑殘 達到間化製程步驟、提升 降低製程成本之目的。 杈开λ釭可罪度、以及 因為本發Si -£ρ 1" -#i ^ ^ 彈性度較高，而可擴大=窗機的阻劑，因此阻劑的選擇的 这本毛明較佳實施例可知，本發明 因為本發明之盔殘留声之、$ 路太上p 极..沾就疋 ，”、殘@層之逆式乂奈錢印製程，無須在高溫 = 入進行，因此可適用於任何材質之模板與基板 (13可撓曲之塑膠基板），應用性相當廣泛。 由上述本發明較佳實施例可知，本發明之再一 以非常完整的轉印出模板上的圖形與深度，並可在同1塊基 板上同時製作不同深寬比的立體圖案’且不需使用多道重複 製紅此外，本發明無須昂貴的設備，且製程簡單，製程操 作彈性大，而且對於奈米尺度之線寬沒有設備限制、模板可 重複使用，因而可取代現有的微影蝕刻技術（包含微奈米壓 印與曝光顯影），且更容易轉移奈米等級之線寬圖案於大尺 寸的任意基板上（四吋以上）。 本發明可應用在半導體廠與平面顯示器之基板的圖案 化上。對於現今之顯示器的製作上，可利用此逆式無阻劑殘 留層之壓印技術直接製作面板，例如薄膜電晶體液晶顯示器 (TFT-LCD)、場發射型顯示器（FED)、以及有機發光二極体 (OLED)，之陰極間壁（Cathode Separator or RIB)與液晶顯示 15 1252520 為之液晶層間隙壁（Spaeer)。 雖然本發明已以-較佳實施例揭露如上 :定本發明，任何熟習此技藝者，在不脫離本發明 !!圍内’當可作各種之更動與潤飾，因此本發明之保護範圍 虽視後附之申請專利範圍所界定者為準。 已圍 【圖式簡單說明】 第1圖至第9圖係繪示依照本發明一較 么 貫施例的一種 無殘留層之逆式微奈米壓印製程之製程剖面圖，其中第 圖係界面活性劑與模板表面吸附示意圖。 2 主要元件符號說明 100 :模板 102 ： 脫膜層 1 〇 4 :界面活性層 104a :界面活七 1 0 4 b :界面活性層 106 ： 開口 108 :平面 110 : 表面 112 :平板 114 ： 黏著層 11 6 :阻劑 118 ： 基板 120 :圖案 122 ： 單分子 124 :疏水基 126 ： 親水基 128 :高分子 130 ： 阻劑分子 16It is composed of a surfactant film having a plurality of bifunctional φ polymers I28, one end of each polymer being a hydrophilic group 126, as shown in the above second. < Touch the dog a stubborn _ water storm 124, the other 2 shows. One of the hydrophobic groups of the polymer 128 is a hydrophobic group 124, and 124 has a medium and long pure carbon chain, for example, a long-chain carbon polymer compound having at least eight carbon molecules. The hydrophilic group 126 of the polymer 128 is a hydrophilic functional group such as a sulfonic acid group, a hydroxyl group, an amine group or the like. The hydrophobic end 124 of the polymer 128 of the interface active layer 1〇4 and the hydrophobic group of the single layer 122 in the release layer 1〇2 on the template 1〇〇 are physically weakly adsorbed, and thus the physical adsorption is utilized. As a result, the interface active layer 1 〇 4 can be adsorbed on the release layer 102, and the hydrophilic group 另一 2 另一 at the other end of the ruthenium molecule 128 can be made outward as shown in FIG. 2 . Therefore, the surface 11 of the template 1 can be modified, and the surface 110 of the template 1 has a hydrophilic property. After the application of the interface active layer 1〇4 is completed, the template crucible may be subjected to a low-temperature drying step to dry the interface active layer 104 on the template 100. Next, a flat panel 112 is provided, wherein the material of the flat panel 112 can be, for example, a plastic, as shown in Fig. 3. One of the surfaces of the flat plate 112 is coated with an adhesive material or a hydrophilic material. In the present embodiment, the surface of the flat plate 112 is coated with an adhesive layer 114 such as an adhesive. Subsequently, as shown in Fig. 4, the 1252520 template H)0 is overlaid on the flat surface 112, so that the surface of the template ι〇〇 is closely attached to the flat plate H2, so that the adhesion or physical adsorption can be utilized separately. In a manner, the interface active layer on the plane 1〇8 portion of the surface 110 of the template 100 is attached to the adhesive material (for example, adhesive | ι 4) or the hydrophilic material of the flat 112. After the modulo is removed from the square anti-112, the interface is opposite to the flat φ 1 08 4 of the surface 110. The interface activity | i 〇 4b is attached above the flat plate 112, as shown in Fig. 5. Thus, the interface active layer 104b' other than the opening 1〇6 of the template 1〇〇 is removed, and the side wall surface and the bottom surface of the opening 1〇6 of the surface φ ιι〇 of the template 1〇〇 still retain the interface activity & heart . That is, the polymer having a difunctional group in the interface active layer 104a is still adsorbed on the side wall surface and the bottom surface of the opening 106 on the surface 110 of the template 100, and the opening 106 of the surface 110 of the template still has a hydrophilic property. Thus, the portion 108 of the surface 110 of the template 100 is hydrophobic and the pattern opening 1〇6 is hydrophilic. After the modification of the surface 110 of the template 100 is completed, the resist 116 is formed into the opening 106 of the surface 110 by, for example, spin coating or immersion, as shown in Fig. 6. The material of the resist 116 may be, for example, an organic material or an inorganic material, and the material of the resist 116 may be, for example, polymethyl methacrylate (PMMA), polystyrene (PS) or an inorganic colloidal solution. After the coating of the resist 116 is completed, the resist 116 may be further subjected to a soft baking treatment. The reaction temperature of the soft baking treatment depends on the material of the resistive agent ,16, and the reaction time of the soft baking treatment depends on the material of the resist 丨16 and the reaction temperature. In a preferred embodiment of the invention, the reaction temperature of the soft bake process is preferably controlled to be about 80. (: to about 90 ° C, and the reaction time of the soft bake treatment is preferably controlled by 12 1252520 between about 5 minutes and about 10 minutes. One of the features of the present invention is that, due to the template 1 0 0 The opening 1〇6 of the surface 1 1 is covered with the interface layer 1〇4, so the inner side and the bottom surface of the opening 1〇6 are filled with the hydrophilic functional group of the cerium, and the resist molecule 13 in the resist 116 The attraction of these hydrophilic functional groups, as shown in Fig. 2, is such that the resistance (4) 116 can be completely filled into the opening 106 of the template 1 〇〇 surface 110, but the resist U 6 is not formed in the template. 1 平面 surface 108 on the plane 108. In addition, # different resists can be used to easily find a suitable surfactant using the above principles. * Then, the substrate 118 to be patterned is provided, wherein the substrate 118 can be Soft as a substrate or a rigid substrate, such as a ruthenium substrate or a flexible plastic substrate, etc. The surface of the substrate 118 may be selectively cleaned and plasma activated prior to the embossing process to increase the surface of the substrate 118. Active, and thereby between the resist 116 and the substrate 118 Adhesion. In a preferred embodiment of the invention, oxygen cleaning is used to clean and activate the surface of the substrate 118. Next, the template 100 is overturned again and the surface of the template 1 is ιι〇 The imprinting process is performed on the surface to be patterned on the substrate 118, as shown in Fig. 7. In the imprinting process, the ® of the template 100 is printed onto the substrate 118 by means of contact hot stamping. On the surface, the reaction temperature of the imprinting process is controlled to be about the glass softening point (Tg) of the resist 116, and the applied force only needs to completely adhere the template 100 to the surface of the substrate 118. The reaction temperature is lower than After the glass softening point of the resist 116, the template 100 can be easily separated from the substrate 118, so that the resist pattern 122 of the residual layer of the resistless agent can be obtained on the surface to be patterned of the substrate 118, as shown in FIG. 13 1252520 Another feature of the present invention is that since the imprinting process only needs to be controlled around the softening point of the glass of the resistor J 11 6 , and the applied pressure only needs to fit the template to the surface of the substrate, it is not necessary Under high temperature and high pressure Therefore, it is still applicable to a flexible flexible plastic substrate or other substrate which cannot be applied under high temperature and high pressure, and has a wide applicability. ^ A further feature of the present invention is that the resist 116 is not formed. On the flat portion 108 of the surface 110 of the template 100, after the imprinting process, the resist is left on the substrate 118. This eliminates the need to remove the residual layer of the resist. The problem of pattern deformation caused by the residual layer of the resist is avoided. After the resist pattern 122 is transferred onto the substrate 118, the substrate 118 having the resist pattern 122 can be directly used according to different requirements, or the resist can be used as the resist. I, 22 as a _ mask, such as the reactive material _ (RIE) side 3 or 酉夂 (4) way (four) substrate 118, and the resist pattern 帛 transferred to the substrate 118 towel. Then, by using, for example, wet stripping, and removing the residual resist 116 with a suitable solvent, the surface of the substrate 118 has a pattern 120 corresponding to the pattern of the panel 100, as shown in Fig. 9. According to the preferred embodiment of the present invention, one of the advantages of the present invention is that because of the reverse micro-nano imprint process without residual layer of the present invention, (4) the residual layer without a resist after the printing process, the problem of the residual layer control of the resistless agent is further improved. The problem of deformation or shrinkage of the pattern caused by the residual layer of the resist and the difficulty of removing the residual layer can be avoided, and the elasticity of the process can be improved. Since the preferred embodiment of the present invention described above, the reverse-type micro-remaining layer without residual layer of the present invention can be known. Another advantage of the present invention is that there is no residue of 14 1252520 in the embossing process of the rice embossing process, and it is not necessary to leave the layer in the embossing step ^ ^ ^ ^ ^ ^ ^. Therefore, it is possible to remove the resist residue. Achieve the process of inter-process, improve the cost of reducing the process. Open the 釭 釭 釭 、 以及, and because the current Si - £ ρ 1 " - #i ^ ^ high elasticity, can be expanded = window machine resistance So resist According to the preferred embodiment of the present invention, the present invention is not necessary because of the residual sound of the helmet of the present invention, the road is too p-polar, the smear is smear, and the residual layer is reversed. It is applied at high temperature = so it can be applied to any material template and substrate (13 flexible plastic substrate), and it is widely used. According to the preferred embodiment of the present invention, the present invention furtherly transfers the pattern and depth on the template in a very complete manner, and can simultaneously produce three-dimensional patterns of different aspect ratios on the same substrate. In addition, the invention does not require expensive equipment, and has a simple process, large process flexibility, and no device limitation for the line width of the nanometer scale, and the template can be reused, thereby replacing the existing lithography etching technology ( It includes micro-nano embossing and exposure development, and it is easier to transfer the nano-scale line width pattern on any large substrate (four 吋 or more). The invention is applicable to the patterning of substrates in semiconductor plants and flat panel displays. For the production of today's displays, panels can be directly fabricated using this reverse-resistance residual layer imprinting technique, such as thin film transistor liquid crystal displays (TFT-LCDs), field emission displays (FEDs), and organic light-emitting diodes. The body (OLED), the cathode wall (Cathode Separator or RIB) and the liquid crystal display 15 1252520 are liquid crystal layer spacers (Spaeer). Although the present invention has been disclosed in the preferred embodiment as described above, it will be apparent to those skilled in the art that various modifications and refinements can be made without departing from the invention. The scope defined in the patent application is subject to change. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 to FIG. 9 are cross-sectional views showing a process of a reverse micro-imprint process without a residual layer according to a comparative embodiment of the present invention, wherein the first interface is Schematic diagram of the adsorption of the active agent and the template surface. 2 Main component symbol description 100: template 102: release layer 1 〇 4 : interface active layer 104a : interface active seven 1 0 4 b : interface active layer 106 : opening 108 : plane 110 : surface 112 : flat plate 114 : adhesive layer 11 6 : Resistor 118 : substrate 120 : pattern 122 : single molecule 124 : hydrophobic group 126 : hydrophilic group 128 : polymer 130 : resist molecule 16