1230975 玖、發明說明： 【發明所屬之技術領域】 本發明是有關於微米/奈米級結構以及藉逆轉印刻而形 成這種結構的方法。 【先前技術】 需要快速且經濟的製造出奈米級結構是發展奈米科學 與奈米技術時的主要驅動力。也稱作熱浮凸微影蝕刻的奈 米印刻微影蝕刻（NIL)，是經由圖案硬質模具的浮凸處理， 藉讓聚合物光阻變形而產生厚度減小，該技術提供許多決 定性的技術優點，尤其是定義出奈米級圖案的低成本方法 (S. Y. Chou, P〇 R. Krauss and P. J. Renstrom, Science, 272, 85(1996), S.Y· Chou，美國專利編號第5772905案）。已經證實NIL能定 義出具有橫向解析度小於6 nm的圖案特點（8.丫.〇1〇11，？· R. Krauss, W. Zhang, L. J. Guo and L. Zhuang, J. Vac. Sci. Technol. B，15, 2897(1997); S. Y_ Chou P. R· Krauss，Microelectron· Eng” 355 237(1997); B〇 Heidarl, I. Maximov and L. Montelius, J. Vac〇 Sci. Technol· B，18，3557(2000); A· Lebib，Y· Chen，J. Boumeix，F。 Carcenac，E. Cambrill, L. Couraud and H. Launois, Microelectron, Eng.，46, 319(1999))。在傳統的NIL中，基板在能用硬質模具 進行浮凸處理之前，便先需要用聚合物層做旋轉塗佈。 Borzenko等人提出一種結合方法，其中基板與模具是用聚 合物進行旋轉塗佈處理（T. Borzenko, M. Tormen，G· Schmidt5 L· W. Molenkamp and H. Janssen，Appl· Phys· Lett” 79, 2246(2001)) 〇 雖然目前有一些奈米印刻技術可用，但是這些技術都 85347.doc -6- 1230975 有或夕個缺點。現在，對於能夠使用的基板種類有很 嚴秸的限制，常常只有平板型硬質基板表面可以進行印 二J處理。此外，常常需要過度的高溫及/或壓力，會限制 由许多有潛力之基板上所產生的奈米結構種類。 /已經證實，NIL是具有高解析度，高產量以及低成本的 微〜蝕刻技術。然而，為了延伸該技術的應用範圍，能 隹平面表面上進行二維結構的奈米印刻處理是很吸引 人的，因為複雜的顯微裝置以及新的應用常常需要如 此。< 則已經使用許多技術來研究非平面表面的印刻處 "攻等技術都疋憑藉用厚聚合物層對非平面表面進行 平一化以及夕層光阻方法（X· Sun，L· Zhuang and S· Y· Chou，J. Vac。Sci.Technol· B 16,（1998))。這些技術不只需要許多處理 步驟，而且還牽涉到深蝕刻，以去除掉在形成期間所產 生的厚平坦化聚合物層，常常讓所形成之最終圖案或結 構的解析度以及精確度變差。 本發明人等已經開發出一種一新式的印刻技術，適合 許多不同的基板以及基板組合物。本發明可以在比目前 肌中所使用還低的溫度與低的壓力下進行。比起傳統的 NIL，依據本發明的逆轉印刻方法提供許多獨特的優點， 讓非平面基板以及不容易用聚合物薄膜進行旋轉塗佈的 基板都能進行印刻處理，比如撓性聚合物基板。此外， 都能藉控制製程條件，使用逆轉印刻而製造出模具的正 向或負向複製物。 【發明内容】 85347.doc 1230975 在第一特點中，本發明提供一種在基板上印刻出微米/ 奈米結構的方法，該方法包括： (a) 提供一種包含顯微結構所需的圖案或離隙的模具； (b) 將1合物塗佈層塗佈到該模具上；以及 (C)在適當溫度與壓力條件下，從該模具上將聚合物塗 佈層轉移到基板上，以形成具有所需微米/奈米結構的印 刻基板。 取好，該模具是硬質模具，該硬質模具是由半導體， 介電質，金屬以及其組合物所構成的群組來形成。通常， 咸模具疋在矽（Si)晶圓上的si〇2或Si中形成，並用光學微 影蝕刻技術或電子束微影蝕刻技術以及後續的乾蝕刻來 定義出圖案。將會了解到，其它模具種類也可以給本發 明用。 與包括熱塑性聚合物，熱/輻射可熟化預聚合物以及玻 璃或陶瓷前驅質的模具比較起來，適合在本發明中使用 的聚合物是由非常軟的材料來構成。已經發現到分子量 土 V 15000的聚甲基丙晞酸甲酯（pMMA)特別適合本發 明。然而將會了解到，其它材料也可以使用。 為了 #助聚合物從模具上脫離開到基板上，該模具在 知水5物塗佈上去之前，便可以先用一個或多個表面活 性劑來處理。已經發現到111，111，2氏211_全氟癸基_三氯矽 甲烷的表面活性劑特別適合本發明。然而將會了解到， 興所使用之聚合物相容的其它表面活性劑也可以使用。 遠聚合物最好是用旋轉塗佈而塗佈到模具上。這種旋 85347.doc 1230975 轉塗佈的塗佈技術是眾所周知的，而且可以在不同的傳 統微影㈣技術中發現到適當的實例。要達到在表面活 性劑所塗佈的模具上有本質均勻的聚合物塗佈，溶劑的 選擇將會很重要。在極性溶劑中的聚合物溶液通常不會 在表面活性劑處理模具上形成連續性薄膜。已經發現到 甲苯溶劑特別適合本發明。然而，與所使用之聚合物相 容的其它非極性溶劑也適用。實例包括二甲苯與四氫 喃’但不受限於此。 已經發現到拋光的Si晶圓以及撓性聚乙醯胺薄膜 (Kapton®)是本發明很適合的基板。然而將了解到，其它 基板也可適合。實例包括聚合物，半導體，介電質，金 屬以及其組合體，但不受限於此。 本發明的方法可應用於平面與非平面基板，包括已經 匕έ有些圖案或離隙的基板。該方法能應用到已經包 含有一層或多層聚合物塗佈的基板上。例如，該方法可 以用來產生晶格結構，其中多層聚合物（比如聚合物格狀 物）是在基板上形成。 步驟（c)最好是在所需壓力與溫度下的預熱壓機中進 行所使用的壓力與溫度將取決於所選取的模具，基板 以及聚合物。通常，使用比約i 〇 MPa還小的壓力。已經 發現到約5 MPa或更小的壓力很適合逆轉印刻pMMA聚 合物。本發明中可以使用從低到約30°C至聚合物玻璃轉 移溫度（Tg)以上約9〇°c的溫度。 視溫度與聚合物塗佈層的平坦化程度，可以達到不同 85347.doc 1230975 的印刻效應。 因此，本發明的較佳實施例包括一種用於印刻出微米/ 奈米結構到基板上的方法（如上所述），其中所塗佈上去的 聚合物塗佈層在本質上是非平面&，而且該溫度在本質 上是比聚合物的玻璃轉移溫度（Tg)還高。在這些條件下， 逆轉印刻的行為是類似於傳統的NIL，因為有相當多的聚 合物流體會依據模具的形狀，隨著聚合物的移動而發 生。而且，最終的模具聚合物塗体層是該模具的負向複 製物。 依據本發明的另—實施例，所塗佈上去的聚合物塗佈 層在本吳上是非平面型，而且溫度在本質上是等於或低 於聚合物的玻璃轉移溫度（Tg)。在本實施例中，通常只有 在該模具凸出區域上的薄膜部分會被轉移到基板上。以 廷種万式，本實施例的方法是類似於甩液體墨水的的蓋 P方去。本實施例的方法造成具有正向模具複製品的模 具聚合物塗佈層。 依據本發明的另一實施例，所塗佈上去的聚合物塗佈 層在本貝上是平面型，而且溫度在本質上是等於或低於 聚合物的破璃轉移溫度（Tg)。在本實施例中，會發生印刻 而不會有任何本質上橫向聚合物的移動，而且整個塗佈 水a物層被轉移到基板上。在本發明的實施例下，最終 模具聚合物塗佈層是負向模具複製品。在該實施例中， 整個聚合物塗佈層被轉移到基板上，進一步的優點是達 到較低的殘餘厚度。 85347.doc 1230975 ~本發明的方法也可以使用相同的基板進行許多次，使 得具多層聚合物層的層狀結構能夠形成。例如，每個聚 一物㈢可以包含一些平行條紋（亦即形成格狀圖案），橫貫 過（比如成直角）相鄰聚合物層的平行條紋。藉此最終結構 會具有晶格形態。 在第=特點中，本發明提供一種基板，包含有藉依據 :發明罘一特點之方法所產生的印刻微米/奈米結構。該 微米/奈米結構可以是由單_印刻聚合物層所形成。另一 万式疋，可以由-些造成三維結構的聚合物層來形成， 比如晶格結構。 該微米/奈米結構適合使用於微影蚀刻，積體電路，量 t磁性儲存裝置，雷射，生物感測器1感測器，顯微 電子機械系統（MEMS)，生物MEMS以及分子電子裝置。 在第三特點中，本發明提供使用依據本發明第一特點 的万法’以便在非平面或撓性基板上形成微米/奈米結構。 在整個說明書中，除非文中有需要，否則，，包括，，的用 字或比如“包含，，或“含有，，的變化都將被解讀成隱含所提 及，早H字或步驟’或是單I數字或步驟的群組， 但是並不排除任何單元、數字或步驟，或是單元、數字 或步驟的群組。 已-包3在本說明書内的任何文件，行動，材料，裝 置，文獻或類似物件的討論，都只是為了提供本發明的 說明文件而已。任何戎阱女、上 任仃或所有這些形成先前技術基礎或是 與本發明相關領域中的一般 ^ 叙知滅都不應被視為可允許 85347.doc 1230975 的’如同在本說明書中每個主張之優先權日期之前便已 存在。 為了更清楚了解本發明，將會說明較佳的形式，並參 閱以下圖式以及實例。 【實施方式】 用以進行本發明的模式 實驗 本研究中使用二種圖案模具。該等模具是在矽（Si)晶圓 上的Si〇2做成’並用光學微影蚀刻且接著進行乾姓刻處 理而定義出圖案。模具的特點是從2至50μπι變動，且公稱 深度為190 nm。其它模具都具有700 nm週期且180至650 nm深度範圍的均勻格狀物。所有模具都用ih，ih，2H，2H-全氟癸基-三氯矽甲烷的表面活性劑進行處理，以提升聚 合物的脫離。所使用的基板是拋光的（1〇〇)si晶圓並且是 才九性的’ 50 μηι厚的聚乙酸胺薄膜（Kapton®)。分子量 15000的聚甲基丙烯酸甲酯（pMMA)使用於印刻處理。在 典型的逆轉印刻實驗中，用PMM A甲苯溶液，在旋轉速率 3000rpm下持續30秒對模具進行旋轉塗佈，並接著在105 °C下加熱5分鐘以去除掉殘餘的溶劑。在預熱壓機中讓塗 佈的模具在基板上以5 MPa的壓力持續5分鐘進行擠壓。 孩壓力一直持續，直到溫度下降到5〇它以下為止。最後 讓該模具與基板脫離並隔離開。 結果與討論 在傳統的NIL中，聚合物薄膜在用硬質模具進行印刻處 85347.doc -12- 1230975 理之前，便先需要塗佈到基板上。然而，旋轉塗佈很難 在撓性基板上進行，比如聚合物薄膜，限制傳統nil對這 種基板定義出圖案的處理能力。此外，傳統的nil視黏滯 聚合物流體來讓聚合物薄膜變形並產生厚度對比，而且 都需要上升的溫度與壓力（1-1.1^>^6〇1^11，11.8(：111行，（^· David, J. Gobrecht and T. Schweizer, Microelectron. Eng., 54, 229(2000); H. C. Scheer, H. Schulz, T. Hoffmann and C. M. S. Torres, J. Vac. Sci. Technol. B, 16，3917(1998); S. Zankovych，T. Hoffmann，J. Seekamp, J. U. Bruch and C. M. S. Torres，Nanotechnology，12, 91(2001))。為了 達到可 靠的圖案轉移，通常是在Tg(玻璃轉移溫度）以上的70至90 1溫度下且在高達1〇 MPa的壓力下進行印刻處理（L· J. Heyderman，H. Schift，C. David，J. Gobrecht and T. Schweizer，Microelectron· Eng.，54，229(2000); H. C. Scheer，H. Schulz，T. Hoffmann and C. M. S. Torres，J. Vac。 Sci. Technol. B， 16， 3917( 1998);F. Gottschalch, T.1230975 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to a micro / nano-scale structure and a method for forming such a structure by reverse transfer engraving. [Previous technology] The need to quickly and economically manufacture nanoscale structures is the main driving force in the development of nanoscience and nanotechnology. Nano-imprint lithography (NIL), also known as thermal embossing lithography, is embossed through a patterned hard mold to reduce the thickness of the polymer by deforming the photoresist of the polymer. This technology provides many decisive techniques Advantages, especially low-cost methods for defining nanoscale patterns (SY Chou, POR. Krauss and PJ Renstrom, Science, 272, 85 (1996), SY · Chou, US Patent No. 5772905). It has been confirmed that NIL can define patterns with a lateral resolution of less than 6 nm (8. ya.〇101〇, R. Krauss, W. Zhang, LJ Guo and L. Zhuang, J. Vac. Sci. Technol B, 15, 2897 (1997); S. Y_Chou P. R. Krauss, Microelectron · Eng "355 237 (1997); B〇Heidarl, I. Maximov and L. Montelius, J. Vac〇Sci. Technol · B, 18, 3557 (2000); A. Lebib, Y. Chen, J. Boumeix, F. Carcenac, E. Cambrill, L. Couraud and H. Launois, Microelectron, Eng., 46, 319 (1999)). In traditional NIL, the substrate needs to be spin-coated with a polymer layer before the substrate can be embossed with a hard mold. Borzenko et al. Proposed a combination method in which the substrate and the mold are spin-coated with a polymer Processing (T. Borzenko, M. Tormen, G. Schmidt5, L. W. Molenkamp and H. Janssen, Appl. Phys. Lett "79, 2246 (2001)) 〇 Although some nano-imprinting techniques are currently available, these techniques Both 85347.doc -6- 1230975 have some disadvantages. At present, there are strict restrictions on the types of substrates that can be used, and often only the surface of a flat-type rigid substrate can be printed. In addition, excessive high temperatures and / or pressures are often required, limiting the types of nanostructures that can be created on many potential substrates. / It has been confirmed that NIL is a micro-etching technology with high resolution, high yield, and low cost. However, in order to extend the application of this technology, nano-imprinting capable of performing two-dimensional structures on flat surfaces is attractive because complex microscopy devices and new applications often require this. < Many techniques have been used to study the imprinting of non-planar surfaces " Technologies such as tapping rely on the use of thick polymer layers to flatten non-planar surfaces and photoresist methods (X · Sun, L. S. Y. Chou, J. Vac. Sci. Technol. B 16, (1998)). These techniques not only require many processing steps, but also involve deep etching to remove the thick planarized polymer layer produced during formation, often degrading the resolution and accuracy of the final pattern or structure formed. The present inventors have developed a new type of engraving technology suitable for many different substrates and substrate compositions. The present invention can be carried out at a lower temperature and lower pressure than currently used in muscles. Compared with the conventional NIL, the reverse transfer engraving method according to the present invention provides many unique advantages, such that non-planar substrates and substrates that are not easily spin-coated with polymer films can be imprinted, such as flexible polymer substrates. In addition, by controlling the process conditions, the reverse transfer engraving can be used to produce positive or negative replicas of the mold. [Summary of the Invention] 85347.doc 1230975 In a first feature, the present invention provides a method for imprinting a micro / nano structure on a substrate, the method comprising: (a) providing a required pattern or separation including a microstructure Gap mold; (b) applying a compound coating layer to the mold; and (C) transferring the polymer coating layer from the mold to the substrate under appropriate temperature and pressure conditions to form Imprint substrate with desired micro / nano structure. Taken well, the mold is a hard mold, and the hard mold is formed by a group consisting of a semiconductor, a dielectric, a metal, and a combination thereof. Generally, a salt mold is formed in SiO 2 or Si on a silicon (Si) wafer, and the pattern is defined using optical lithography or electron beam lithography and subsequent dry etching. It will be appreciated that other types of molds may be used for the present invention. Compared to molds including thermoplastic polymers, heat / radiation-curable prepolymers, and glass or ceramic precursors, polymers suitable for use in the present invention are composed of very soft materials. Polymethylpropionate (pMMA) having a molecular weight of earth V 15000 has been found to be particularly suitable for the present invention. It will be appreciated, however, that other materials may be used. In order to release the polymer from the mold to the substrate, the mold can be treated with one or more surfactants before the water is coated. It has been found that 111,111,2's 211_perfluorodecyl_trichlorosilylmethane surfactant is particularly suitable for the present invention. It will be appreciated, however, that other surfactants compatible with the polymers used may also be used. The remote polymer is preferably applied to a mold by spin coating. This spin coating technique is well known, and suitable examples can be found in different traditional lithography techniques. To achieve a substantially uniform polymer coating on a surfactant-coated mold, the choice of solvent will be important. Polymer solutions in polar solvents usually do not form a continuous film on a surfactant-treated mold. A toluene solvent has been found to be particularly suitable for the present invention. However, other non-polar solvents compatible with the polymer used are also suitable. Examples include but are not limited to xylene and tetrahydro '. It has been found that polished Si wafers and flexible polyethylenimine films (Kapton®) are very suitable substrates for the present invention. It will be appreciated, however, that other substrates may be suitable. Examples include, but are not limited to, polymers, semiconductors, dielectrics, metals, and combinations thereof. The method of the present invention can be applied to planar and non-planar substrates, including substrates that have been patterned or have gaps. This method can be applied to substrates that already contain one or more polymer coatings. For example, this method can be used to produce a lattice structure in which multilayer polymers (such as polymer lattices) are formed on a substrate. Step (c) is preferably performed in a preheating press at the required pressure and temperature. The pressure and temperature used will depend on the mold, substrate and polymer chosen. Generally, a pressure smaller than about 10 MPa is used. Pressures of about 5 MPa or less have been found to be suitable for reverse transfer engraved pMMA polymers. In the present invention, temperatures ranging from as low as about 30 ° C to about 90 ° C above the polymer glass transition temperature (Tg) can be used. Depending on the temperature and the degree of planarization of the polymer coating layer, different imprinting effects of 85347.doc 1230975 can be achieved. Therefore, the preferred embodiment of the present invention includes a method for imprinting a micro / nano structure onto a substrate (as described above), wherein the applied polymer coating layer is non-planar in nature, Moreover, this temperature is substantially higher than the glass transition temperature (Tg) of the polymer. Under these conditions, the behavior of reverse transfer engraving is similar to that of traditional NIL, because a considerable amount of polymer fluid will occur according to the shape of the mold, as the polymer moves. The final polymer coating layer of the mold is a negative copy of the mold. According to another embodiment of the present invention, the applied polymer coating layer is non-planar on the surface, and the temperature is substantially equal to or lower than the glass transition temperature (Tg) of the polymer. In this embodiment, usually only the thin film portion on the protruding area of the mold is transferred to the substrate. In this way, the method of this embodiment is similar to the cap P of the liquid ink. The method of this example results in a mold polymer coating layer with a forward mold replica. According to another embodiment of the present invention, the applied polymer coating layer is flat on the substrate, and the temperature is substantially equal to or lower than the glass transition temperature (Tg) of the polymer. In this embodiment, engraving occurs without any movement of the polymer in the transverse direction, and the entire coating layer is transferred to the substrate. Under embodiments of the present invention, the final mold polymer coating is a negative mold replica. In this embodiment, the entire polymer coating layer is transferred to the substrate, a further advantage is that a lower residual thickness is achieved. 85347.doc 1230975 ~ The method of the present invention can also be performed many times using the same substrate, so that a layered structure with multiple polymer layers can be formed. For example, each aggregate may contain parallel stripes (ie, forming a grid pattern), and parallel stripes (eg, at right angles) across adjacent polymer layers. As a result, the final structure will have a lattice morphology. In a third feature, the present invention provides a substrate including an imprinted micro / nano structure produced by a method based on the first feature of the invention. The micro / nano structure may be formed from a single-imprinted polymer layer. Another example is that it can be formed from some polymer layers that create a three-dimensional structure, such as a lattice structure. The micro / nano structure is suitable for lithographic etching, integrated circuits, magnetic t storage devices, lasers, biosensor 1 sensors, micro-electro-mechanical systems (MEMS), bio-MEMS and molecular electronic devices . In a third feature, the present invention provides the use of a method according to the first feature of the present invention to form a micro / nano structure on a non-planar or flexible substrate. Throughout this specification, unless required by the text, words including, or variations such as "include," or "including," will be interpreted as implied references, early H characters or steps' or It is a group of single I numbers or steps, but does not exclude any unit, number or step, or a group of units, numbers or steps. Any discussion of documents, actions, materials, devices, literature, or similar items in this specification is intended to provide a description of the invention. Any riser, predecessor, or all of them that form the basis of the prior art or are generally relevant in the field related to the present invention should not be considered as allowing 85347.doc 1230975 to be 'as in every claim in this specification Existed before the priority date. For a clearer understanding of the present invention, the preferred form will be explained, and refer to the following drawings and examples. [Embodiment] Mode experiment for carrying out the present invention In this study, two kinds of pattern molds were used. These molds are made of SiO2 on a silicon (Si) wafer, and are etched by optical lithography, followed by dry-cut engraving to define a pattern. The mold is characterized by a variation from 2 to 50 μm and a nominal depth of 190 nm. Other molds have a uniform lattice with a period of 700 nm and a depth range of 180 to 650 nm. All molds were treated with ih, ih, 2H, 2H-perfluorodecyl-trichlorosilyl surfactants to enhance polymer release. The substrate used is a polished (100) si wafer and is a unique ' 50 μηι thick polyacetate film (Kapton®). Polymethylmethacrylate (pMMA) with a molecular weight of 15,000 is used for imprinting. In a typical reverse transfer engraving experiment, the mold is spin-coated with a PMM A toluene solution at a rotation rate of 3000 rpm for 30 seconds, and then heated at 105 ° C for 5 minutes to remove the residual solvent. The coated mold was pressed on the substrate at a pressure of 5 MPa for 5 minutes in a preheating press. The child's stress continues until the temperature drops below 50 ° C. Finally, the mold is separated from the substrate and isolated. Results and Discussion In conventional NIL, polymer films need to be coated on substrates before they are stamped with a hard mold. 85347.doc -12-1230975. However, spin coating is difficult to perform on flexible substrates, such as polymer films, limiting the traditional nil's ability to define patterns on such substrates. In addition, traditional nil sees viscous polymer fluids to deform polymer films and produce thickness contrast, and both require rising temperature and pressure (1-1.1 ^ > ^ 6〇1 ^ 11, 11.8 (: line 111, (^ · David, J. Gobrecht and T. Schweizer, Microelectron. Eng., 54, 229 (2000); HC Scheer, H. Schulz, T. Hoffmann and CMS Torres, J. Vac. Sci. Technol. B, 16 , 3917 (1998); S. Zankovych, T. Hoffmann, J. Seekamp, JU Bruch and CMS Torres, Nanotechnology, 12, 91 (2001)). To achieve reliable pattern transfer, usually at Tg (glass transition temperature) Imprinting is performed at a temperature of 70 to 90 1 above and a pressure of up to 10 MPa (L. J. Heyderman, H. Schift, C. David, J. Gobrecht and T. Schweizer, Microelectron. Eng., 54, 229 (2000); HC Scheer, H. Schulz, T. Hoffmann and CMS Torres, J. Vac. Sci. Technol. B, 16, 3917 (1998); F. Gottschalch, T.
Hoffmann，C. M. S. Torres，H. Schulz and H. Scheer, Solid-State Electron·，43, 1079(1999))。對傳統NIL技術的 某些改變，比如由Borzenko等人所開發的聚合物键結方 法（T. Bornzeko，M. Tormen，G· Schmidt，L. W. Molenkamp and H. Jassen，Appl· Phys. Lett·，79，2246 (2001))，會大 幅的降低溫度與壓力的需求。然而，Borzenko等人的聚 合物鍵結方法會有額外的缺點，即印刻處理後較厚的殘 餘層，讓後續的圖案轉移變得很複雜。 85347.doc -13 - 1230975 與傳統的NIL不同，依據本發明的逆轉印刻技術是一種 對撓性基板定義出圖案的方便且可靠的方法。此外，視 聚合物塗佈模具的平坦化程度以及印刻的溫度而定，可 以觀祭到三種獨立的圖案移模式。可以在Tg以下低到約 30 C的溫度下，且在壓力低到約i MpaT，達到成功且可 靠的圖案轉移。 圖1是以示意圖的方式顯示出與傳統NIL做比較的三種 逆轉印刻模式。在傳統的NIL(圖i(a))中，是在遠高於Tg 的溫度下將模具壓在平面聚合物薄膜上。在印刻期間， 著材料依據模具形狀而變形，會發生相當多的聚合物 /瓜to 在返回於的溫度下，類似的聚合物流體也會在 逆轉印刻中發生。即使聚合物薄膜並不是平坦化，如圖 1(b)所不，在模具凸出區域上的材料可以在印刻處理時被 擠壓到周圍的凹洞中。在這種條件下，逆轉印刻的行為 是非常類似於傳統的NIL。因為在此情形下的用於印刻處 理的襯底機構是聚合物黏滯性流體，所以我們稱這種印 刻模式為，，浮凸印刻”。 逆轉印刻比起傳統印刻的獨特優點是，也可以在以附 近或甚至稍微低於Tg的溫度下將圖案轉移到基板上。在 此/皿度範圍中，印刻結果是大幅的取決於對模具進行旋 轉塗佈處理後的平坦化程度。對於具有非平坦化塗佈的 模/、 /、有模具凸出區域上的薄膜會被轉移到基板上， 浚圖1 (C)所示。因為該方法類似於用液體墨水的蓋印方 法，所以這種印刻模式稱作“塗墨印刻，，。與浮凸印刻不 85347.doc -14- 1230975 同的是，塗墨印刻會產生正向圖案。 然而，如果塗佈聚合物薄膜在旋轉塗佈後是稍微的平 面時，則整個塗佈聚合物薄膜都可以在Tg附近下進行印 刻處理時轉移到基板上，而不需要大尺寸的橫向聚合物 移動（圖1(d))。我們稱這種印刻模式為“整層轉移，，。類似 於浮凸印刻模式，整層轉移模式也會造成模具的負向複 製物。 從以上討論中，很清楚的，塗佈聚合物薄膜的表面平 坦化程度以及印刻溫度是決定最後印刻結果的很重要因 素。在底下的段落中，會討論印刻條件與最後結果之間 的定量相關性。 旋轉塗佈後的表面平坦化 在傳統NIL中一般是採用抗黏著劑對模具進行處理，以 提升聚合物的脫離。最好是在逆轉印刻中改變模具的表 面能量，以便改善聚合物層轉移到基板上。在本研究中 使用一種在傳統印刻（T. Nishino, M. Megur〇, κ.歸咖狀， M. Matsushita and Y. Ueda, Langmuir, 15, 4321 (1999))t ? 當作脫模劑的1H，1 H，2H，2H-全氟癸基_三氯珍甲燒來當作 脫模劑用。然而，需要開發出一種用於將pMMA旋轉塗佈 到抗黏著劑處理模具上的技術。因為處理模具的低表面 能量，讓極性溶劑中的PMMA溶液，比如氯苯，在旋轉塗 佈後將不會形成連續性薄膜。對照上來說，甲苯中的 PMMA溶液可以成功的旋轉塗佈到經表面活性劑處理過 的模具上。對於未經處理的表面來說，將pmma甲苯溶液 85347.doc -15- 1230975 万疋轉塗佈到經表面活性劑處理過的表面上，會有相類似 的薄膜品質與厚度。 由於一般模具的形態，必須檢視旋轉塗佈聚合物層的 平坦化程度。對於具有較大尺寸的模具，很難得到平坦 化的聚合物層。在通常的條件下，對丨9〇 nm深具微米尺 寸特點的模具進行旋轉塗佈處理，通常會造成模具上的 一致性塗佈層。如果是次微米格狀模具，則平坦化程度 疋從轉塗佈中所使用之溶液濃度的強烈函數，決定塗佈 薄膜的厚度。塗佈薄膜的一般原子力顯微複製（AFM)斷面 分析顯示於圖2中。在旋轉塗佈之後，塗佈模具的步階高 度疋取決於模具深度以及薄膜厚度。如圖2所示，我們用 塗佈模具的平均尖峰至凹谷高度，Rmax，來描述平坦化程 度。圖3摘要出Rmax變化是當作不同深度之格狀模具中溶 液濃度的函數。對於給定的特定深度，較高溶液濃度會 有較厚的薄膜，並造成較低的Rmax或較高的平坦化程度。 圖3中不同的平坦化程度已經是與最後的印刻結果有 相關性。在105°C的印刻溫度下，與pMMA的Tg溫度相 同，當Rmax低到〜155 nm時，會發生整層轉移模式，而塗 墨印刻模式則疋在Rmax為〜1 68 nm以上時發生。對於1 5 5 至16S nm之間的Rmax，會發生這二種模式的結合。i〇5〇c 下不同印刻模式的區域是標示於圖3中。 不同的逆轉印刻模式 當考慮到二重要的印刻參數時，亦即平坦化程度與印 刻溫度，建構出印刻模式的圖式，如圖4所示。這些符號 85347.doc -16 - 1230975 疋表不不同模式與不同薄膜厚度的實驗資料。三個主要 區域疋義出每個印刻模式發生時所必要的條件。在過渡 品或中曰發生一個或多個模式的組合。雖然傳統的NIL 通第/、有在返向於Tg的溫度下才會成功，但是依據本發 明的逆轉印刻可以用使用於比Tg還低且比Tg還高的較寬 溫度範圍中。我們已展示出在低到75°c下發生塗墨印刻 與整層轉移，該溫度是比PMMA的Tg還低30°C。 圖4顯示出在l〇5°C下，當Rmax比約155 nm還低時會發整 層轉移。這種印刻圖案的實例是顯示於圖5中。可以達到 具非常少缺陷的可靠圖案轉移。整層轉移模式的重要特 點是一殘餘厚度（在圖5中遠低於1〇〇 nm)。當使用具相同 濃度的溶液時，Tg附近溫度下逆轉印刻後的殘餘厚度是 相當於在更高溫度下的傳統NIL。此外，可靠的整層轉移 也已經用低到1 MPa的壓力達到。 雖然整層轉移模式需要足夠的塗佈模具的表面平坦 化，但是在塗佈後較大的步階高度對於成功的塗墨模式 來說是優點。這是因為當步階高度小時，該特點之側壁 上的薄膜通常會相當厚。當這種薄膜被塗上墨水後，將 側壁附近的聚合物薄膜撕下會造成不平整邊緣的印刻特 性。圖6顯示出在105 °C且步階高度305 nm下塗墨印刻的 結果。藉650 nm深格狀模具，具有很薄的塗佈層（6%溶 液），形成這一種較大的步階高度。在此條件下，模具中 凹陷處侧壁上的薄膜會非常薄，而且很容易在印刻處理 時斷裂開。結果，能得到具相當平滑邊緣的可靠圖案轉 85347.doc -17- 1230975 移。 將PMMA逆轉印刻至撓性基板上 在逆轉印刻處理中，不需要將聚合物層旋轉塗佈到基 板上。這種獨特的特性讓某些不容易進行旋轉塗佈的基 板上可能可以產生圖案，例如撓性聚合物基板。我們很 成功的使用該逆轉奈米印刻技術來將PMMA圖案轉移到 50 μΠ1厚的聚乙醯胺薄膜（KaPt〇n®)上，該薄膜被廣泛的 當作撓性電路中的基板。圖7顯示出用7%溶液對35〇 深格狀模具進行旋轉塗佈後在175它下進行逆轉印刻處 理所產生的PMMA圖撓性基板上的印刻顯#出在整個 與整層轉移模式也會在撓性基板上發生 印刻區域(〜2.5…上有很少缺陷的高度均勻性。圖7所 示的特定結果是在浮凸模式下進行印刻處理。塗墨模式 而且印刻結果 類似於在Si基板上所得到的。 將PMMA逆轉印刻至塗案基板上 本發明可以用來便於在㈣面表面上進行奈米印刻， 而不需要平坦化。之前用於非平面表面上奈米印刻微影 蝕刻的技術一般是憑靠厚聚合物層之非平面表面的平坦 化以及多層光阻方法。這些技術都需要許多步驟，並牵 涉到深㈣，以去除掉厚的平坦化聚合物層（這會讓印刻 微影蚀刻技術中的解析度與可信度變差)。本發明能用來 便於在非平面表面上進行奈米印刻，而不需任合平坦化 處理。 構之表 面上進行印 圖8顯示出使用本發明在有明顯結 85347.doc -18 - 1230975 刻處理的示意圖。圖8(a)顯*出塗体到圖案表面之前便先 旋轉塗佈到模具上的PMMA。然後在適當溫度與壓力條件 下將塗佈模具塗佈到圖案結構上（圖8(b))。當釋放開模具 時’基板便具有貼附到已存在之圖案基板上的聚合物圖 案。 圖9顯示出轉移到非平面基板上的聚合物圖案。該基板 是700 run週期的Si〇2格狀物，具有丨5 μιη深度。該模具也 具有相同週期以及350 nm深度的格狀圖案’而且被塗佈 上表面活性劑。PMMA被旋轉塗佈到模具上，並且在圖案 基板上用5 MPa壓力在9(TC下進行擠壓。具有模具格狀圖 案的整個PMMA層會被轉移到基板上，因*pMMA到基板 上的黏接性由於界面上表面能量的較大差異，所以是比 到模具上的黏接力還要更強。可以觀察到良好的圖案轉 移，而且殘餘的PMMA很薄，如從二不同角度所拍攝的 SEM顯微鏡圖所示（圖9)。用〇2RIE方法，如同一般奈米印 刻微影蝕刻技術中所使用到的，直接去除掉任何的薄殘 餘PMMA層。 圖9所顯示的方法可以重複許多次，藉以造成多層結 構。聚合物的每個連續層（包含有模具格狀圖案）都能以直 角塗佈到先前的薄層上。這會形成多層晶格結構。 由於圖9顯示出塗佈上圖案聚合物層而使得格狀物與 基板的格狀物是成直角，所以也可能讓聚合物格狀物塗 佈到基板的格狀物上，並且與基板的格狀物對齊。這會 讓格狀物的深度依所需要的做變化（比如增加）。 85347.doc -19· 1230975 如果將PMMA塗佈肖具印刻到格狀基板4 m# 到175°C時，殘餘層便會消失。這是由於聚合物^面活 性劑塗佈表面上的去除溼潤行為。 該聚合物印刻技術解決了非平面表面上奈米印刻微影 ㈣所遭遇到的問題。該技術可以延伸到到產生不同的 三維結構。 摘要 我們已經成功的展示出一種逆轉印刻方法，將旋轉塗 怖聚合物層從硬質模具上轉㈣基板上。三種不同的圖 术轉移挺式’亦即浮凸轉移，塗墨轉移與整層轉移，都 可以藉控制印刻溫度以及旋轉塗佈模具的表面平坦化程 度來達成。正向或複向的模具複製物可以在印刻處理後 仔到。藉通當程度的平坦化，可以在低到⑽下的㈣ 以及1 MPa壓力下，分财塗墨與整層轉移模式中成功的 達成圖木轉移。這是比起傳統nil很重要的優點，該傳統 NIL需要遠高於Tg的印刻溫度。此外，因為在這二種圖案 轉移模式中需要微小的聚合物移動，所以逆轉印刻對於 與聚合物流體有關的問冑比較不敏感。 本發明人等已經開發出一種新的印刻技術，避免對基 板上万疋轉塗佈聚合物層的需要。聚合物層是直接被旋轉 塗佈到k具上’而且藉在適當溫度與壓力下的印刻處理 而被轉移基板上。依據本發明的逆轉印刻方法比起傳統 的NIL，提供一項您& 貝獨特的優點，讓無法輕易的用聚合物薄 膜進行旋轉塗伟處理的基板能被印刻上，比如撓性聚合 85347.doc -20- 1230975 物基板。 將nil塗佈到非平面表面上的先前努力常常是憑靠厚 永合物層之非平面表面的平坦化。這些技術牽涉到多個 技術步驟。此外，去除掉厚平坦化層的深蝕刻步騾會讓 解析度與可信度變差。目前的發明提供簡單的技術Y對 非平面表面進行圖案處理，而不需要平坦化步騾。在適 當的處理條件下，能很方便的製造出三維結構。 熟知該技術的人士將會了解到，可以在不偏離本發明 的精神與範圍下，對特定實施例中所示的本發明進行許 多的變動及/或改變，如同以廣範圍的方式所說明的一 般。因此該等實施例在所有方面上都被視為解說性而非 限定性。 【圖式簡單說明】 圖1顯示出在（a)傳統奈米印刻；（b)高出Tg溫度以上的 逆轉印刻；（c)在玻璃轉移溫度（Tg)附近之溫度下用非平 面模具的“塗墨”處理；（d)在Tg附近用平坦性模具的“整層 轉移”中圖案轉移處理的示意圖表示。 圖2顯示出在3000 rpm下被塗佈上6〇/0ρΜΜΑ溶液的300 nm深格狀模具的原子力顯微複製（AFM)斷面分析。 圖3顯示出在不同溶液3000 rpm下的旋轉塗佈處理後， 具不同深度之格狀模具中平均尖峰對凹谷的步階高度。 標定出l〇5C下的不同圖案轉移模式區域，虛線是表示二 模式之間的過渡區域。 圖4顯示出逆轉印刻模式對於印刻溫度以及塗佈模具 85347.doc -21 - 1230975 之步階高度的關係。符號是實驗資料，實線是不同模式 的外插邊界。 圖5顯示出105°C下使用具7%PMMA塗佈之350 nm深格 狀模具的逆轉印刻的掃描電子顯微鏡圖。印刻前的Rmax 是7 5 nm，而且會發生整層轉移模式。 圖6顯示出，105°C下具6%塗佈以及Rmax=305 nm之650 nm深格狀模具的塗墨處理結果的掃描電子顯微鏡圖。 圖7顯示出175°C下在50 μηι厚Kapton薄膜上進行逆轉 印刻所產生之PMMA圖案的掃描電子顯微鏡圖。用7°/〇溶 液對350 nm深的模具進行旋轉塗佈處理。 圖8顯示出在結構表面上使用本發明的印刻處理示意 圖：（a)在塗佈到圖案基板上之前旋轉塗佈到模具上的 PMMA ; (b)低於Tg之溫度下對圖案結構進行印刻處理； (c)轉移到基板上的PMMA圖案。 圖9顯示出垂直於圖案1.5 μιη深通道Si02基板表面的印 刻PMMA格狀物的掃描電子顯微鏡圖（SEM): (a)沿著轉移 PMMA格狀物來看；（b)沿著基板上底下Si02格狀圖案來 看。 圖10顯示出在175°c下轉移到圖案基板上的PMMA格狀 物的SEM圖，其中去除水分的處理已經去除掉殘餘的 PMMA 層。 85347.doc -22-Hoffmann, C. M. S. Torres, H. Schulz and H. Scheer, Solid-State Electron., 43, 1079 (1999)). Some changes to traditional NIL technology, such as the polymer bonding method developed by Borzenko et al. (T. Bornzeko, M. Tormen, G. Schmidt, LW Molenkamp and H. Jassen, Appl. Phys. Lett., 79 , 2246 (2001)), will greatly reduce the temperature and pressure requirements. However, the polymer bonding method of Borzenko et al. Has the additional disadvantage that the thicker residual layer after the imprinting process complicates the subsequent pattern transfer. 85347.doc -13-1230975 Unlike the conventional NIL, the reverse transfer engraving technique according to the present invention is a convenient and reliable method for defining a pattern on a flexible substrate. In addition, depending on the flatness of the polymer coating mold and the temperature of the engraving, three independent pattern shift modes can be observed. Successful and reliable pattern transfer can be achieved at temperatures as low as about 30 C below Tg and as low as about i MpaT. Fig. 1 is a schematic diagram showing three reverse transfer engraving modes compared with the conventional NIL. In conventional NIL (Figure i (a)), the mold is pressed onto a flat polymer film at a temperature much higher than Tg. During the engraving, the material deforms according to the shape of the mold, and a considerable amount of polymer / melon will occur. At similar temperatures, similar polymer fluids will also occur during reverse transfer engraving. Even if the polymer film is not flattened, as shown in Figure 1 (b), the material on the protruding area of the mold can be squeezed into the surrounding recesses during the imprinting process. Under these conditions, the behavior of reverse transfer engraving is very similar to traditional NIL. Because the substrate mechanism used for imprinting in this case is a polymer viscous fluid, we call this imprinting mode, embossed imprinting. ”The unique advantage of reverse transfer engraving over traditional imprinting is that it can also The pattern is transferred to the substrate at a temperature near or even slightly below Tg. In this range, the result of the imprinting is greatly dependent on the degree of flattening after the spin coating process is performed on the mold. The film on the flattened coating mold /, /, with the mold protruding area will be transferred to the substrate, as shown in Figure 1 (C). Because this method is similar to the stamping method with liquid ink, this kind of The engraving mode is called "Ink engraving,". The same as embossing 85347.doc -14-1230975, the ink printing will produce a positive pattern. However, if the coated polymer film is slightly flat after spin coating, the entire coated polymer film can be transferred to the substrate during the imprinting process near Tg, without the need for large-sized lateral polymers. Move (Figure 1 (d)). We call this engraving mode "full-layer transfer." Similar to the embossed engraving mode, the full-layer transfer mode also causes negative copies of the mold. From the discussion above, it is clear that the coating of polymer film The degree of surface flatness and the engraving temperature are important factors that determine the final engraving result. In the following paragraphs, the quantitative correlation between the engraving conditions and the final result will be discussed. Surface flattening after spin coating is generally used in traditional NIL The anti-adhesive agent is used to process the mold to improve the release of the polymer. It is best to change the surface energy of the mold in the reverse transfer engraving in order to improve the transfer of the polymer layer to the substrate. In this study, a traditional engraving ( T. Nishino, M. Megur〇, κ. Guicai, M. Matsushita and Y. Ueda, Langmuir, 15, 4321 (1999)) t 1H, 1 H, 2H, 2H-all as release agents Fluorodecyl_trichlorocarpentine is used as a release agent. However, a technology for spin coating pMMA onto an anti-adhesive treatment mold needs to be developed. Because of the low surface energy of the treatment mold, the polarity Dissolve PMMA solution in the solvent, such as chlorobenzene, will not form a continuous film after spin coating. In contrast, PMMA solution in toluene can be successfully spin-coated onto a surfactant-treated mold. For For the untreated surface, the pmma toluene solution 85347.doc -15-1230975 million 疋 is re-coated on the surface treated with surfactant, which will have similar film quality and thickness. Because of the general mold shape It is necessary to check the flatness of the spin-coated polymer layer. For molds with larger sizes, it is difficult to obtain a flattened polymer layer. Under normal conditions, molds with a micron size characteristic of 90nm deep The spin coating process usually results in a uniform coating layer on the mold. If it is a sub-micron grid mold, the degree of planarization is determined by a strong function of the concentration of the solution used in the transfer coating, which determines the coating film. Thickness. A general atomic force microscopy (AFM) cross-sectional analysis of the coating film is shown in Figure 2. After spin coating, the step height of the coating mold depends on the mold depth and And film thickness. As shown in Figure 2, we use the average peak to valley height of the coating mold, Rmax, to describe the degree of flattening. Figure 3 summarizes the change in Rmax as the concentration of the solution in the grid-shaped mold with different depths. Function. For a given specific depth, a higher solution concentration will result in a thicker film and result in a lower Rmax or a higher degree of planarization. The different degree of planarization in Figure 3 is already related to the final imprinting result. Correlation. At the marking temperature of 105 ° C, it is the same as the Tg temperature of pMMA. When Rmax is as low as ~ 155 nm, the whole-layer transfer mode will occur, while the inking marking mode will be at Rmax above ~ 1 68 nm. Occurs from time to time. For Rmax between 1 5 5 and 16S nm, a combination of these two modes occurs. The areas of the different imprinting modes under i50c are marked in Figure 3. Different reverse transfer engraving modes When two important engraving parameters are considered, that is, the degree of flattening and the engraving temperature, a pattern of the engraving mode is constructed, as shown in FIG. 4. These symbols 85347.doc -16-1230975 represent experimental data for different modes and different film thicknesses. Three main areas define the conditions necessary for each engraving pattern to occur. A combination of one or more patterns occurs in a transition product or medium. Although the conventional NIL can be successful only at the temperature returning to Tg, the reverse transfer engraving according to the present invention can be used in a wider temperature range lower than Tg and higher than Tg. We have shown that ink engraving and full-layer transfer occur at temperatures as low as 75 ° C, which is 30 ° C lower than the Tg of PMMA. Figure 4 shows that at 105 ° C, a full-layer transfer occurs when Rmax is lower than about 155 nm. An example of such an engraved pattern is shown in FIG. 5. Reliable pattern transfer with very few defects can be achieved. An important feature of the full-layer transfer mode is a residual thickness (well below 100 nm in Figure 5). When a solution with the same concentration is used, the residual thickness after reverse transfer engraving at a temperature near Tg is equivalent to the conventional NIL at a higher temperature. In addition, reliable whole-layer transfers have also been achieved with pressures as low as 1 MPa. Although the full-layer transfer mode requires sufficient surface flattening of the coating mold, a large step height after coating is an advantage for a successful ink coating mode. This is because when the step height is small, the film on the sidewall of this feature is usually quite thick. When this film is coated with ink, tearing off the polymer film near the side walls can cause uneven edge printing characteristics. Figure 6 shows the results of inking at 105 ° C and a step height of 305 nm. With a 650 nm deep grid mold, it has a very thin coating layer (6% solution) to form this larger step height. Under this condition, the film on the side wall of the recess in the mold will be very thin and easily break during the imprinting process. As a result, a reliable pattern with fairly smooth edges can be obtained. PMMA reverse transfer engraving on flexible substrates In the reverse transfer engraving process, it is not necessary to spin-coat a polymer layer onto a substrate. This unique feature makes it possible to create patterns on some substrates that are not easily spin-coated, such as flexible polymer substrates. We have successfully used this reverse nanoimprinting technique to transfer PMMA patterns to a 50 μΠ1 thick polyethylene film (KaPton®), which is widely used as a substrate in flexible circuits. Figure 7 shows the PMMA image of a 35 ° deep grid mold spin-coated with a 7% solution after spin coating at 175mm. The imprint on the flexible substrate is marked on the flexible substrate. Marked areas (~ 2.5 ... with a high degree of uniformity with few defects will occur on the flexible substrate. The specific result shown in Figure 7 is the embossing mode. The ink application mode and the results are similar to those in Si Obtained on the substrate. PMMA reverse transfer engraved on the coated substrate. The invention can be used to facilitate nanoprinting on the surface of the mask without planarization. Previously used for nanoprint lithography on non-planar surfaces. The technology is generally based on the planarization of non-planar surfaces of thick polymer layers and multilayer photoresistive methods. These technologies require many steps and involve deep knowledge to remove the thick planarized polymer layer (this will make the imprint The resolution and reliability in the lithography etching technology become worse.) The present invention can be used to facilitate nano-imprinting on non-planar surfaces without any planarization treatment. Printing on the surface of the structure Fig. 8 shows a schematic diagram of the treatment using the present invention at a marked knot 85347.doc -18-1230975. Fig. 8 (a) shows the PMMA spin-coated onto the mold before the coating is applied to the pattern surface. The coating mold is applied to the pattern structure under temperature and pressure conditions (Figure 8 (b)). When the mold is released, the substrate has a polymer pattern attached to an existing pattern substrate. Figure 9 shows Polymer pattern transferred to a non-planar substrate. The substrate is a Si02 grid with a 700 run cycle and a depth of 5 μm. The mold also has a grid pattern with the same period and a depth of 350 nm and is coated Upper surfactant. PMMA is spin-coated onto the mold and extruded on the pattern substrate with a pressure of 5 MPa at 9 ° C. The entire PMMA layer with the mold grid pattern will be transferred to the substrate, because * The adhesion of pMMA to the substrate is stronger than the adhesion to the mold due to the large difference in surface energy on the interface. A good pattern transfer can be observed, and the residual PMMA is very thin, such as from Taken from different angles The SEM micrograph is shown (Figure 9). Using the 02RIE method, as is commonly used in nanolithographic etching techniques, any thin residual PMMA layer is directly removed. The method shown in Figure 9 can be repeated many times This results in a multilayer structure. Each successive layer of the polymer (containing the mold lattice pattern) can be applied at a right angle to the previous thin layer. This will form a multilayer lattice structure. As Figure 9 shows the pattern applied The polymer layer makes the grid at right angles to the grid of the substrate, so it is also possible to apply the polymer grid to the grid of the substrate and align with the grid of the substrate. This will make the grid The depth of the object is changed as needed (such as increased). 85347.doc -19 · 1230975 If the PMMA coating tool is printed on the grid substrate 4 m # to 175 ° C, the residual layer will disappear. This is due to the dewetting behavior on the polymer-coated surface. This polymer imprinting technology solves the problems encountered by nanoimprint lithography on non-planar surfaces. The technique can be extended to produce different three-dimensional structures. Abstract We have successfully demonstrated a reverse transfer engraving method that transfers a spin-coated polymer layer from a hard mold to a substrate. Three different types of graphic transfer lifts, namely embossed transfer, ink transfer and full layer transfer, can be achieved by controlling the engraving temperature and the degree of surface flattening of the spin coating mold. Reproduced molds in the forward or reverse direction can be obtained after the imprinting process. Through the flatness of the current level, the transfer of money can be successfully achieved in the mode of dividing ink and coating and the whole layer transfer at a pressure as low as ⑽ and a pressure of 1 MPa. This is an important advantage over traditional nil, which requires a marking temperature much higher than Tg. In addition, since minute polymer movement is required in these two pattern transfer modes, reverse transfer engraving is less sensitive to problems associated with polymer fluids. The inventors have developed a new engraving technology that avoids the need for a polymer layer to be coated on the substrate. The polymer layer is spin-coated directly onto the tool, and it is transferred to the substrate by an imprinting process at an appropriate temperature and pressure. Compared with the traditional NIL, the reverse transfer engraving method according to the present invention provides you with a unique advantage that substrates that cannot be spin-coated with a polymer film can be easily printed, such as flexible polymerization 85347. doc -20- 1230975 object substrate. Previous efforts to apply nil to non-planar surfaces have often relied on the planarization of non-planar surfaces with thick layers of permanent compounds. These technologies involve multiple technical steps. In addition, deep etching steps that remove the thick planarization layer degrade the resolution and reliability. The current invention provides a simple technique Y for patterning non-planar surfaces without the need for a planarization step. Under appropriate processing conditions, three-dimensional structures can be easily manufactured. Those skilled in the art will appreciate that many variations and / or changes can be made to the invention shown in the specific embodiments without departing from the spirit and scope of the invention, as illustrated in a wide range of ways. general. These embodiments are therefore to be considered in all respects illustrative and not restrictive. [Schematic description] Figure 1 shows (a) traditional nano-printing; (b) reverse transfer engraving above Tg temperature; (c) using a non-planar mold at a temperature near the glass transition temperature (Tg) "Ink coating" process; (d) Schematic representation of the pattern transfer process in "whole layer transfer" with a flat mold near Tg. Fig. 2 shows an atomic force microscopy (AFM) cross-sectional analysis of a 300 nm deep lattice mold coated with a 60/0 pMMA solution at 3000 rpm. Figure 3 shows the step heights of the average spikes to valleys in a grid-shaped mold with different depths after spin coating treatment at 3000 rpm in different solutions. The different pattern transfer mode regions under 105C are calibrated, and the dotted line indicates the transition region between the two modes. Figure 4 shows the relationship between the reverse transfer engraving mode and the engraving temperature and the step height of the coating mold 85347.doc -21-1230975. Symbols are experimental data, and solid lines are extrapolated boundaries for different modes. Figure 5 shows a scanning electron microscope image of reverse transfer engraving at 105 ° C using a 350 nm deep grid mold with 7% PMMA coating. The Rmax before imprinting is 7 5 nm, and a full-layer transfer mode occurs. Fig. 6 shows a scanning electron microscope image of the results of 6% coating at 105 ° C and the ink coating process of a 650 nm deep grid mold with Rmax = 305 nm. Figure 7 shows a scanning electron microscope image of the PMMA pattern produced by reverse printing on a 50 μm thick Kapton film at 175 ° C. Spin coating was performed on a 350 nm deep mold using a 7 ° / 0 solution. Figure 8 shows a schematic view of the imprinting process using the present invention on the surface of the structure: (a) PMMA spin-coated onto a mold before being applied to a pattern substrate; (b) imprinting the pattern structure at a temperature below Tg Processing; (c) PMMA pattern transferred to the substrate. Figure 9 shows a scanning electron microscope (SEM) image of a PMMA grid imprinted perpendicular to the surface of a patterned 1.5 μm deep channel Si02 substrate: (a) seen along the transfer PMMA grid; Look at the Si02 grid pattern. Figure 10 shows an SEM image of the PMMA grids transferred to the pattern substrate at 175 ° C, in which the moisture removal treatment has removed the remaining PMMA layer. 85347.doc -22-