1254359 九、發明說明 【發明所屬之技術領域】 特別是有關 與大面積基 本發明是有關於一種奈米壓印圖案化技術， 於一種逆式壓印圖案化技術，並應用於3D圖案 板上之圖案製作。 【先前技術】1254359 IX. Description of the invention [Technical field to which the invention pertains] In particular, it relates to a large-area basic invention relating to a nanoimprint patterning technique for a reverse imprint patterning technique and applied to a 3D pattern board. Pattern making. [Prior Art]
半導體積體電路產業歷經了許多不同世代之材料鱼役 §十上的進步，功能密度（例如，每單位晶片面積中内連線= 件的數量）逐漸增加’而特徵尺寸（例如，使用建㈣程所 ΐ創造出的最小元件與線路）逐漸降低。在此-積體電路的 次進過程中，傳統的光微影蝕刻技術仍是現今業 線寬之圖案化製程中最普遍使料技術。 ^ f而，傳統的光微影蝕刻技術也存在多項缺點，例如 又備〒貝、製程繁靖㈣題，且對於在奈米線寬下，會有紫 光射的限制，對於較大尺寸的基材也會產生照光不均句 的問題’另外對於可撓曲塑膠板，也會產生光阻劑旋轉塗佈 =g的現象。因此為了改善此—問題’轉而使用壓印技術製 作圖案’尤其在奈米尺度與三維空間的圖案化製程中，壓印 圖案化技術尤其佔有技術優勢。 然而，目前所有壓印技術製作圖案之製程，係將已圖 :化之模板做抗黏著層處理，並將熱塑性材料旋轉塗佈於所 欲圖幸化$ | 44* , 〃 土才上，並在高溫高壓的環境下，與模板對壓， P可將模板之圖案轉移至基材的阻劑上。 1254359 不過’傳統壓印圖案化製程之缺點是必須操作在高溫 與高壓下，易對基材造成傷害，尤其對於塑膠可撓曲基板， 右圖案或深寬比不均勻時，會產生圖案轉移不完整的問題。 另外，若是施加的壓力不夠或是所選擇的阻劑（resist)不 適當，會造成殘留層（residual丨r)過厚而 成圖案變形或收縮的現象。 易去除成疋- 逆式壓印圖案化技術（reversal micro-nanoimprinting mh〇graphy)提供了解決圖案轉移不完整或蝕刻障礙層之殘 留層太厚等問題的方法’逆式壓印圖案化技術，與傳統壓印 ㈣製程的順序相反’是利用較低分子量㈣刻阻劑，並選 擇適合之溶劑將之溶解，並旋轉塗佈於已圖案化之模板上， 再利用壓P接觸的方式將圖案轉移至所使欲圖案化之基材 (尤其可使用於塑膠可撓曲基板）。 然而，逆式壓 圖案化技術之問題， 處理（具有脫模層） 同之深寬比之問題。 印圖案化技術雖然有助於解決傳統壓印 不過卻有蝕刻阻劑不易填入經過抗黏著 之模板溝槽内，導致無法得到與模板相 圖案：=式壓印圖案化改質脫模層，以及逆式壓印 内\盖：’使仵低分子量的蝕刻阻劑易於填入模板溝槽 内’改善半導體奈米壓印圖案化製程深寬比不k問題 【發明内容】 案化：質脫::：的目的就疋在提供-種新型的逆式壓印圖 、、a日’以及㈣此―改質脫模層所進行之逆式塵 1254359 印圖案化製程。 在本發明的第一與第二實施例之中，利用界面活性劑 (surfactant )於模板之抗黏著層作表面改質處理，使蝕刻 之阻劑可以完全的填入模板溝槽内部，並非常完整的轉印出 模板上的圖幵> 與深度，大幅提昇逆式壓印技術的良率。 本發明的第二與第三實施例係運用以上所述之逆式壓 印圖案化技術，將圖案化製程之圖案以逆式壓印的方式轉印 貼合在基材上的蝕刻阻劑，並以蝕刻阻劑作為罩幕（仿“㈠ 對基材進行圖案化。 本發明係透過一改質脫模層，使模板的表面具有親水 的特性，其表面的水接觸角降至8〇度以下，蝕刻阻劑可以 完全的填入模板溝槽内部，並將模板上的圖形與深度完整的 轉印到所欲使用之基材上，以得到微奈米尺寸之線寬。因此 不僅可以取代現有的微影蝕刻技術所面臨昂貴之製程嗖備 的限制，ϋ且可以提供較溫和的製程環境，剌於各種基材 之圖案化。 【實施方式】The semiconductor integrated circuit industry has experienced many advances in the material dynasty of different generations, and the functional density (for example, the number of interconnects per unit wafer area = the number of pieces) has gradually increased 'and the feature size (for example, the use of construction (4) The smallest components and lines created by Cheng Zuojun are gradually reduced. In this sub-integration process of integrated circuits, the conventional photolithographic etching technology is still the most common material-making technology in today's line-width patterning process. ^ f, the traditional photolithography etching technology also has a number of shortcomings, such as the preparation of mussels, process versatile (four) questions, and for the nanowire line width, there will be a limit of purple light, for larger size base The material also produces the problem of uneven illumination. In addition, for flexible plastic sheets, the phenomenon of photoresist spin coating = g is also produced. Therefore, in order to improve this problem, the printing technique is used to produce a pattern. In particular, in the nano-scale and three-dimensional space patterning process, the imprint patterning technique is particularly advantageous. However, at present, all the imprinting techniques for making patterns are to make the anti-adhesive layer treatment of the template, and spin-coat the thermoplastic material to the desired image for $ | 44*, In a high temperature and high pressure environment, pressing against the template, P can transfer the pattern of the template to the resist of the substrate. 1254359 However, the shortcoming of the traditional imprinting process is that it must be operated under high temperature and high pressure, which is easy to cause damage to the substrate. Especially for plastic flexible substrates, when the right pattern or the aspect ratio is not uniform, the pattern transfer will not occur. Complete question. In addition, if the applied pressure is insufficient or the selected resist is not appropriate, the residual layer may be too thick to be deformed or shrunk. Reversal micro-nanoimprinting mh〇graphy provides a method for solving the problem of incomplete pattern transfer or excessively thick residual layer of etch barrier layer. In contrast to the traditional embossing (four) process, the lower molecular weight (four) etchant is used, and the appropriate solvent is selected to dissolve it, and it is spin-coated on the patterned template, and then the pattern is pressed by the pressure P contact. Transfer to the substrate to be patterned (especially for plastic flexible substrates). However, the problem of the reverse pressure patterning technique is that the treatment (with the release layer) has the same aspect ratio. Although the printing pattern technology helps to solve the traditional imprinting, but the etching resist is not easy to be filled into the anti-adhesive template groove, the pattern with the template can not be obtained: = embossed patterned modified release layer, And reverse stamping inside the lid: 'Let the low molecular weight etch resist easy to fill into the template trench' to improve the semiconductor nanoimprint patterning process aspect ratio non-k problem [invention content] Case: quality The purpose of ::: is to provide a new type of reverse embossing, a day 'and (d) this modified release layer of the reverse dust 1254359 printing process. In the first and second embodiments of the present invention, a surfactant is applied to the anti-adhesive layer of the template for surface modification treatment, so that the etching resist can be completely filled into the template trench, and is very The complete transfer of the pattern on the stencil> with depth greatly increases the yield of the reverse embossing technique. The second and third embodiments of the present invention use the reverse imprint patterning technique described above to transfer the pattern of the patterning process to the etch resist adhered to the substrate in a reverse embossing manner. The etching resist is used as a mask (similar to "(1) patterning the substrate. The invention passes through a modified release layer, so that the surface of the template has a hydrophilic property, and the water contact angle of the surface is reduced to 8 degrees. In the following, the etch resist can be completely filled into the interior of the stencil trench, and the pattern and depth on the stencil can be completely transferred onto the substrate to be used to obtain the line width of the micro-nano size. Therefore, it can not only replace The existing lithography etching technology is faced with the limitation of expensive process equipment, and can provide a milder process environment and is suitable for patterning various substrates.
本發明的目的就是在提供一插紅相丨, L 圾仏種新型的逆式壓印圖案化 改質脫模層，來大幅提昇逆式壓印姑 叩技術的良率。並以逆式壓 印技術將模板上已圖案化的蝕刻阻劑轉移至基材之上，完 基材之圖案化製程。 70 更明顯易懂，本說明 作詳細説明。 為讓本發明之技術特徵與優勢能 書將以較佳實施例，並配合所附圖示 1254359 在本《明所提供之逆式屡印圖案化改質脫模層，係在 :有:米或疋微米的線寬圖案之任意材質模板上先形成一 ^黏者層，再將具有親水性之官能基之改㈣塗佈於抗黏著 «之上使模板的表面具有親水的特性。之後利用旋轉塗佈 ^沈浸的方式，將有機或是無機材料之蝕刻阻劑均勻塗佈於 模板上’即可將㈣阻劑完全地填人模板溝槽内部。隨後再 將模板與基材彼此互相貼合並同時施以適當的堡力與溫度 即可將在模板上已圖案化的阻劑層轉移貼合至基材上。利用 濕式蝕刻或是反應性電衆蝕刻移除阻劑殘留層，而將基材聂 =其：後以姓刻阻劑為軍幕，利用乾式或濕式蚀刻技術 圖累化基材。 °月參恥弟1圖’第1圖係根據本發明之第一實施例所 繪示之逆式壓印圖案化之改質脫模層1〇〇之剖面示意圖。在 本發明的弟-實施例之中，改f脫㈣⑽至少包括抗 層m以及界面層102。其中抗黏著層1〇1位於具有壓印圖 案·之逆式壓印㈣103之一側，而界面層1〇2則位於 抗黏著層H)…在本發明的第一實施例之中，抗黏著芦 1(H較佳係位於壓印模板103與界面層i 2 兩者接觸。 刀⑺興 抗黏著層1〇1較佳係由-薄膜沉積製程所形成之一镇 =睡其中此一薄膜層，例如’類鑽碳膜、鐵氟龍薄膜、全 屬薄膜以及上述材料之組合’厚度切刚·在本發明的 第-實施例之中’抗黏著層m較佳係—金（Μ)質薄膜。 請參照第2圖’第2圖係根據本發明之第一實施例所繪 1254359 不之界面層102抗黏著層i 〇丨之表面吸附示意圖。界面層 1〇2至少包括一碳分子長鏈202以及一親水性官能基2〇4。 碳分子長鏈202至少具有八個碳分子，其中一端藉由分子間 之物理作用力吸附於抗黏著層1〇1之上；親水性官能基2〇4 則位於碳分子長鏈2〇2遠離抗黏著層1〇1之一端，可以使改 貪脫模層100之表面具有親水性。其中親水性官能基204 •係選自於由羧基（-COOH)、亞硫酸根（_s〇3)、羥基（_〇H)、胺 基（-NH2)、硫醇基（_SH)、以及以上所述之組合所組成之一 群。在本發明的第一實施例之中，界面層102較佳係使用界 面活〖生知]例如丨_十二碳硫醇（1_ Dodecanethiol)、與1_ 辛硫醇（1-0CTANETHI0L)，以及揮發性溶劑，以旋塗或浸 泡之方式形成於抗黏著層101上之一薄膜。 月多、弟3圖，弟3圖係根據本發明之第二實施例所繪 示之逆式壓印圖案化之改質脫模層3〇〇之剖面示意圖。本發 月之第實鼽例與第二實施例之結構大致類似，皆具有一抗 黏著層以及一界面層，最主要的差別在於抗黏著層之材質以 _ 及所形成的方法有所不同。 在本發明的第二實施例之中，改質脫模層3〇〇至少包括 抗黏著層3〇1以及界面層302。其中抗黏著層3〇1位於具有 壓印圖案303P之逆式壓印模板3〇3之一側，而界面層3〇2 、=位於抗黏著層301上。在本發明的第二實施例之中，抗黏 著層301較佳係位於壓印模板3〇3與界面層3⑽之間，且分 別與兩者接觸。 抗黏著層3 01，較佳係利用化學鍵結方法所形成之一高 1254359 分子層。其中此一高分子層，至少包括一長鏈碳氫高分子化 合物。在本發明的第一實施例之中，抗黏著層30丨較佳係至 少具有八個以上碳分子之長鏈碳氫高分子化合物，例如十 八烧基三氣石夕烧（Octyldecyltrichlorosilane，OTS)、六甲美 二石夕醚（Hexamethyldisiloxane，HMDSO)、類金剛石石户 (Diamond-Like Carbon，DLC)膜、以及上述任意組合。 明參照苐4圖’第4圖係根據本發明之第二實施例所繪 示之界面層302與抗黏著層301之表面吸附示意圖。界面層 3 02至少包括一碳分子長鏈402以及一親水性官能基4〇4。 碳分子長鏈402至少具有八個碳分子以上，其中一端藉由分 子間之物理作用力吸附於抗黏著層3〇1之上；親水性官能基 404則位於該碳分子長鏈4〇2遠離抗黏著層3〇1之一端，可 以使改質脫模層300之表面具有親水性。其中親水性官能基 404係選自於由羧基（_c〇〇H) '亞硫酸根（_s〇3)、經基 (-0H)、胺基（-NH2)、硫醇基（_SH)、以及上述材料之組合 所組成之一群。在本發明的第一實施例之中，界面層 較佳係使用界面活性劑，例如丨_十二碳硫醇（ι_ Dodecanethiol)、與 1-辛硫醇（1_〇CTANETHI〇L)，以及揮 發性溶劑，以旋塗或浸泡之方式形成於抗黏著層3〇1上之一 薄膜。 本發明之第三實施例，係藉由本發明所提供之逆式壓印 圖案化改質脫模層進行圖案化製程之方法。此一逆式壓印圖 案化之方法，首先提供一基材S。基材s的種類並無特別限 制’例如，半導體基材、可撓性塑化基材、金屬基材、玻璃 1254359 基材、或以上所述之組合。在本發明之第三實施例之中，係 使用可撓性塑化基材。 接著，提供任意材質且具有㈣圖案之逆式壓印模板 3〇3 ’並在逆式壓印模板3〇3上’具有—壓印圖案3〇3p之 ^卜提供& f脫膜層鳩。在本發明的第三實施例中， 較佳係採用本發明U二實施例所提供之改質脫膜層 300。其中’改質脫模層3〇〇的形成，至少包括在逆式^ 模板3G3 i，具有料圖案騰之—側形成一抗黏著層 3〇1 ;以及在抗黏著層301上，相對於壓印模板3〇3的另一 側形成一界面層302 (請參照第3圖）。 抗黏著層301較佳係利用化學鍵結方法所形成之一高 分子層。#中此一高分子層，至少包括一長鏈碳氫高分子:匕 合物。在本發明的第三實施例之中，抗黏著層3〇ι較佳係至 少具有八個以上碳分子之長鏈碳氫高分子化合物，例如十 八烷基三氯矽烷（〇CtyldeCyltrichl〇r〇silane，〇Ts)、六甲基 二石夕鍵（Hexamethyldisiloxane，HMDS〇)、類金剛石碳 (Diamond-Like Carbon，DLC)膜、以及上述任意組合。 請參照第4圖，界面層3〇2至少包括一碳分子長鏈 402，以及一親水性官能基4〇4，例如羧基（_c〇〇H)、亞硫 酸根（-S03)、羥基（-oh)、硫醇基（_SH)、胺基（-NH2)。碳分 子長鏈402至少具有八個碳分子，其中一端藉由分子間之物 理作用力吸附於抗黏著層301之上；親水性官能基4〇4則位 於碳分子長鏈402遠離抗黏著層3〇1之一端，以使改質脫模 層3 00之表面具有親水性。在本發明的第三實施例之中，界 12 1254359 面層3 02較佳係使用界面活性劑，例如1 _十二碳硫醇（1 _SUMMARY OF THE INVENTION The object of the present invention is to provide a new type of reverse embossed patterned modified release layer for inserting red phase L, L 仏, to greatly improve the yield of reverse embossing technology. The patterned etch resist on the template is transferred to the substrate by reverse imprinting to complete the patterning process of the substrate. 70 is more obvious and easy to understand, and this note is explained in detail. In order to make the technical features and advantages of the present invention will be described in the preferred embodiment, and in conjunction with the attached figure 1254359, the reverse-printing pattern-reformed release layer provided by the present invention is: Or any material template of the micron line width pattern is first formed with a layer of adhesive, and then the hydrophilic (4) functional group is coated on the anti-adhesive layer to make the surface of the template hydrophilic. Thereafter, the etching resist of the organic or inorganic material is uniformly applied to the template by spin coating immersion, and the (4) resist is completely filled inside the template trench. The patterned and resistive layer on the stencil can then be transferred to the substrate by attaching the stencil to the substrate and bonding them to each other while applying the appropriate barrier force and temperature. The residual layer of the resist is removed by wet etching or reactive plasma etching, and the substrate is negated. After the resist is used as a military curtain, the substrate is pulverized by a dry or wet etching technique. Fig. 1 is a schematic cross-sectional view of a reverse-embossed patterned modified release layer 1 according to a first embodiment of the present invention. In the disciple-embodiment of the present invention, at least (4) (10) includes at least the anti-layer m and the interface layer 102. Wherein the anti-adhesion layer 1〇1 is located on one side of the reverse imprint (4) 103 having an imprint pattern, and the interface layer 1〇2 is located on the anti-adhesion layer H)... In the first embodiment of the invention, anti-adhesion Lu 1 (H is preferably located in contact between the imprint template 103 and the interface layer i 2 . The knife (7) anti-adhesive layer 1 〇 1 is preferably formed by a thin film deposition process = sleep in which the film layer For example, 'Diamond-like carbon film, Teflon film, all-film, and a combination of the above materials' thickness cut-on · In the first embodiment of the present invention, 'anti-adhesive layer m is better - gold (Μ) Referring to Fig. 2, Fig. 2 is a schematic view showing the surface adsorption of the anti-adhesion layer i of the interface layer 102 of the first layer according to the first embodiment of the present invention. The interface layer 1〇2 includes at least one carbon molecule. The chain 202 and a hydrophilic functional group 2〇4. The carbon molecule long chain 202 has at least eight carbon molecules, one end of which is adsorbed on the anti-adhesion layer 1〇1 by physical interaction between molecules; the hydrophilic functional group 2 〇4 is located at one end of the carbon molecule long chain 2〇2 away from the anti-adhesive layer 1〇1, which can make the greedy mold The surface of 100 is hydrophilic, wherein the hydrophilic functional group 204 is selected from a carboxyl group (-COOH), a sulfite (_s〇3), a hydroxyl group (-〇H), an amine group (-NH2), a mercaptan. A group consisting of a group (_SH) and a combination of the above. In the first embodiment of the present invention, the interface layer 102 is preferably an interface using a living property such as 丨_dodecyl mercaptan (1_). Dodecanethiol), with 1_ octyl mercaptan (1-0CTANETHI0L), and a volatile solvent, formed by spin coating or soaking on a film on the anti-adhesion layer 101. Yue Duo, Di 3, Tu 3 A schematic cross-sectional view of a reverse-imprinted patterned modified release layer 3〇〇 according to a second embodiment of the present invention. The first embodiment of the present month is substantially similar to the structure of the second embodiment, each having a The most important difference between the anti-adhesion layer and the interfacial layer is that the material of the anti-adhesion layer differs depending on the method formed. In the second embodiment of the present invention, the modified release layer 3〇〇 includes at least Anti-adhesion layer 3〇1 and interface layer 302. wherein anti-adhesion layer 3〇1 is located with embossed pattern 303P One side of the stamping template 3〇3, and the interface layer 3〇2, = are located on the anti-adhesion layer 301. In the second embodiment of the invention, the anti-adhesion layer 301 is preferably located in the stamping template 3〇. 3 and the interface layer 3 (10), and are in contact with the two. The anti-adhesion layer 3 01 is preferably formed by a chemical bonding method to form a high layer of 1,254,359 molecules, wherein the polymer layer comprises at least one long-chain carbon. Hydrogen polymer compound. In the first embodiment of the present invention, the anti-adhesion layer 30 is preferably a long-chain hydrocarbon polymer compound having at least eight carbon molecules, such as an octadecyl triphos (Octyldecyltrichlorosilane, OTS), Hexamethyldisiloxane (HMDSO), Diamond-Like Carbon (DLC) film, and any combination thereof. 4 is a schematic view showing the surface adsorption of the interface layer 302 and the anti-adhesion layer 301 according to the second embodiment of the present invention. The interface layer 302 includes at least a carbon molecular long chain 402 and a hydrophilic functional group 4〇4. The carbon molecular long chain 402 has at least eight carbon molecules, one end of which is adsorbed on the anti-adhesion layer 3〇1 by physical interaction between molecules; the hydrophilic functional group 404 is located at a long chain of the carbon molecule 4〇2 One end of the anti-adhesion layer 3〇1 can make the surface of the modified release layer 300 hydrophilic. Wherein the hydrophilic functional group 404 is selected from the group consisting of a carboxyl group (_c〇〇H) 'sulfite (_s〇3), a mercapto group (-0H), an amine group (-NH2), a thiol group (_SH), and A combination of the above materials. In the first embodiment of the present invention, the interface layer is preferably a surfactant such as 丨_dodecanethiol, and 1-octylmercaptan (1_〇CTANETHI〇L), and A volatile solvent is formed on one of the anti-adhesion layers 3〇1 by spin coating or soaking. A third embodiment of the present invention is a method of performing a patterning process by a reverse imprinting patterned modified release layer provided by the present invention. In this method of reverse imprinting, a substrate S is first provided. The type of the substrate s is not particularly limited, for example, a semiconductor substrate, a flexible plasticized substrate, a metal substrate, a glass 1254359 substrate, or a combination thereof. In a third embodiment of the invention, a flexible plasticized substrate is used. Next, a reverse imprint template 3〇3' having any material and having a (four) pattern is provided and 'with the imprint pattern 3〇3p' on the reverse imprint template 3〇3 provides & f stripping layer鸠. In the third embodiment of the present invention, the modified release layer 300 provided by the U embodiment of the present invention is preferably used. Wherein the formation of the modified release layer 3〇〇 comprises at least an inverse template 3G3 i having an anti-adhesion layer 3〇1 on the side of the material pattern; and an anti-adhesion layer 301 on the anti-adhesion layer 301 The other side of the stamp template 3〇3 forms an interface layer 302 (refer to Fig. 3). The anti-adhesion layer 301 is preferably a high molecular layer formed by a chemical bonding method. #中中 Polymer layer, comprising at least one long-chain hydrocarbon polymer: a chelating compound. In the third embodiment of the present invention, the anti-adhesion layer 3 is preferably a long-chain hydrocarbon polymer compound having at least eight carbon molecules, such as octadecyltrichloromethane (〇CtyldeCyltrichl〇r〇). Silane, 〇Ts), Hexamethyldisiloxane (HMDS), Diamond-Like Carbon (DLC) film, and any combination thereof. Referring to FIG. 4, the interface layer 3〇2 includes at least one carbon molecular long chain 402, and a hydrophilic functional group 4〇4, such as a carboxyl group (_c〇〇H), a sulfite group (-S03), a hydroxyl group (- Oh), thiol group (_SH), amine group (-NH2). The carbon molecular long chain 402 has at least eight carbon molecules, one end of which is adsorbed on the anti-adhesion layer 301 by physical interaction between molecules; the hydrophilic functional group 4〇4 is located at the carbon molecule long chain 402 away from the anti-adhesive layer 3 One end of the crucible 1 is such that the surface of the modified release layer 300 is hydrophilic. In a third embodiment of the invention, the boundary layer 12 2254359 is preferably a surfactant, such as 1 - dodecyl mercaptan (1 _
Dodecanethiol)、與 1_ 辛硫醇（i_〇CTANETHIOL)，以及揮 發性溶劑’以旋塗或浸泡之方式形成於抗黏著層3 〇 1上之一 薄膜。其中，形成界面層302之步驟，更至少包括溫度低於 80°C之一低溫烘烤步驟，以除去揮發性溶劑。 之後，以旋塗或浸泡之方式將一蝕刻阻劑，例如聚甲基 丙浠酸甲酯（Poly-methylmethacrylate，PMMA )、聚苯乙稀 (POLY STYRENE ， PS)、聚甲基矽氧燒 (P〇lydimethylsil〇xane，PDMS)塗佈於脫膜層 3〇〇 之上相 對於壓印模板303之另外一側，以形成一蝕刻阻劑層R，其 中，蝕刻阻劑層R —部分填充於壓印模板3〇3之壓印圖案 3〇3P所形成之凹室3〇3S内，另一部分則覆蓋在凹室“Μ T外之區域上，其中覆蓋在凹室3〇3S外之蝕刻阻劑層r的 厚度範圍介於20nm到l〇〇nm之間。然後，再進行一烤軟+ 驟。 請參照第5圖，第5圖係根據本發明第三實施例之製程 步驟，將具有蝕刻阻劑層R之改質脫模層300壓印於基材s 上所繪示之結構剖面圖。將逆式壓印模板3〇3之具有壓印圖 案2〇3P之一側，貼合並壓印於基材S之上（壓印方向如圖中 所軚不之箭號）；並將逆式壓印模板3〇3與基材s分離，使 餘刻阻劑層R貼合於基材S之上。 請參照第6®’第6圖係根據本發明之製程步驟，將钱 刻阻劑層R貼合於基材S，並形成圖案化罩幕層卩後所繪示 之結構剖面圖。在此一步驟之中，更至少包括將壓印溫度控 13 1254359 制在小於120°c，以及使用足以將蝕刻阻劑層R貼合於基材 S之壓力。 接著，藉由等向性蝕刻，例如反應離子蝕刻（ReactiveDodecanethiol), a film formed on the anti-adhesion layer 3 〇 1 by spin coating or soaking with 1_ octyl mercaptan (i_〇CTANETHIOL), and a volatile solvent'. Wherein, the step of forming the interface layer 302 further comprises at least one low temperature baking step at a temperature lower than 80 ° C to remove the volatile solvent. Thereafter, an etch resist such as poly-methylmethacrylate (PMMA), polystyrene (POLY STYRENE, PS), polymethyloxoxime (Poly-methylmethacrylate, PS) is spin-coated or immersed ( P〇lydimethylsil〇xane, PDMS) is applied on the other side of the release layer 3 opposite to the imprint template 303 to form an etch resist layer R, wherein the etch resist layer R is partially filled The embossing pattern of the embossing template 3〇3 is formed in the recess 3〇3S formed by the embossing pattern 3〇3P, and the other part is covered on the area outside the recess “ΜT, wherein the etching resistance covering the outside of the recess 3〇3S The thickness of the agent layer r ranges from 20 nm to 10 nm. Then, a baking soft + step is performed. Referring to FIG. 5, FIG. 5 is a process step according to a third embodiment of the present invention, which will have A modified cross-sectional view of the modified release layer 300 of the etch resist layer R is embossed on the substrate s. The reverse embossing template 3 〇 3 has an embossed pattern 2 〇 3P side, paste and merge Embossed on the substrate S (the embossing direction is as shown in the figure); and the reverse embossing template 3〇3 is separated from the substrate s, so that The resist layer R is adhered to the substrate S. Referring to the 6th '6th drawing, according to the manufacturing process of the present invention, the money resist layer R is attached to the substrate S, and a patterned mask is formed. A cross-sectional view of the structure shown in the layer. In this step, at least the stamping temperature control 13 1254359 is made at less than 120 ° C, and the etching resist layer R is applied to the substrate S. The pressure is then followed by isotropic etching, such as reactive ion etching (Reactive
Ion Etch ; RIE)移除一部份之蝕刻阻劑層R，以形成一圖案 化罩幕層602，使基材S暴露出來。其中，圖案化罩幕層 602之圖案係與逆式壓印模板3〇3之壓印圖案3〇3p相同， 可以是一規則立體圖案或一不規則之立體圖案。 隶後，以一乾式或濕式鍅刻製程圖案化基材s。 本發明之第四實施例，係藉由本發明所提供之逆式壓印 圖案化改質脫模層進行圖案化製程之方法。此一逆式壓印圖 案化之方法’首先提供—基材8。基材8的種類並無特別限 制，例如，半導體基材、可撓性塑化基材、金屬基材、玻璃 基材、或以上所述之組合。在本發明之第四實施例之中，係 使用可撓性塑化基材。 者，提供任意材質具有壓印圖案之逆式壓印模板 並在逆式壓印模才反103上，具有一壓印圖_ ι〇3ρ之 -側，提供-改質脫模層100。在本發明的第四實施例中， 較佳係採用本發明之第一實施例所提供之改質脫膜層 100°其中’改質脫模層⑽的形成至少包括在逆式壓印模 板二’具有壓印圖案103P之一側形成-抗黏著層101: 以及在抗黏著層101上，相對於壓印模板103的另 一界面層102 (請參照第1圖）。 /成 抗黏著層101，較佳係由沉積技 鐵氟龍薄膜、金屬薄膜，或由 /卖員鑽碳膜、 A由以上所4之組合所形成的薄膜 1254359 曰在本毛明的第四實施例之中，抗黏著層i 0 i係由化學氣 相沉積製程所形成之厚度小於l〇〇nm的金(Au)質薄膜。 請參照第2圖，界面層1G2至少包括—碳分子長鏈 乂及親水性官能機204，例如鲮基（_c〇〇H)、亞硫 酸根Gs〇3)、羥基（_0H)、胺基（"Η2)或硫醇基（_sh)。碳= 子長鏈202至少具有八個碳分子，其中一端藉由分子間之物 里作用力吸附於抗黏著層！ 〇!之上;親水性官能機綱則位 於該碳分子長鏈202遠離抗黏著層ι〇1之一端，可以使改質 脫模層100之表面具有親水性。在本發明的第四實施例之 中界面層1 02車父佳係使用界面活性劑，例如卜十二碳硫 享（1 Dodecanethiol)、與 1-辛硫醇（bQCTANETj^oL)， 以及揮發性溶劑，以旋塗或浸泡之方式形成於抗黏著層ι〇ι 上之一薄膜°丨中，形成改冑102之步•驟，更至少包括溫度 低於80°C之一低溫烘烤步驟，以除去揮發性溶劑。 之後，以旋塗或浸泡之方式將一蝕刻阻劑，例如聚甲基 丙烯1曱酉曰、聚苯乙烯、聚甲基矽氧烷塗佈於脫膜層 之上相對於該壓印模板103之另外一側，以形成一蝕刻阻劑 層R。其中，蝕刻阻劑層R —部分填充於壓印模板1〇3之 壓印圖案103P所形成之凹室103S内，另一部份則覆蓋在 凹至103S外之區域上，其中覆蓋在凹室1〇3s外之蝕刻阻 劑層R的厚度範圍介於2〇nm到1〇〇nm之間。然後，再進 行一烤軟步驟。 睛參照第7圖，第7圖係根據本發明第四實施例之製程 步驟，將具有蝕刻阻劑層R之逆式壓印圖案化改質脫模層 15 1254359 100壓印於基材S上所繪示之結構剖面圖。將逆式壓印模板 103 ’具有壓印圖案103P之一側，貼合並壓印於基材S之 上（壓印方向如圖中所標示之箭號）；並將逆式壓印模板1 03 與基材S分離，使蝕刻阻劑層R貼合於基材S之上。 明參照弟8圖，第8圖係根據本發明之製程步驟，將姓 刻阻劑層R貼合於基材s，並形成圖案化罩幕層以後所繪示 之、、、口構剖面圖。在此一步驟之中，更至少包括將壓印溫度控 制在j於12 〇 c，以及使用足以將钱刻阻劑層r貼合於基材 S之壓力。 接著’藉由等向性蝕刻，例如反應離子蝕刻移除一部份 之蝕刻阻劑層R，以形成一圖案化阻劑層802，使基材S暴 路出來。其中，圖案化阻劑層8〇2之圖案係與逆式壓印模板 之C印圖案1 〇3p相同，可以是一規則立體圖案或一不 規則之立體圖案。Ion Etch; RIE) removes a portion of the etch resist layer R to form a patterned mask layer 602 that exposes the substrate S. The pattern of the patterned mask layer 602 is the same as the embossing pattern 3〇3p of the reverse imprint template 3〇3, and may be a regular three-dimensional pattern or an irregular three-dimensional pattern. Thereafter, the substrate s is patterned in a dry or wet engraving process. A fourth embodiment of the present invention is a method for performing a patterning process by inverse imprinting a patterned release layer provided by the present invention. This method of reverse imprinting is first provided - substrate 8. The type of the substrate 8 is not particularly limited, and is, for example, a semiconductor substrate, a flexible plasticized substrate, a metal substrate, a glass substrate, or a combination thereof. In a fourth embodiment of the invention, a flexible plasticized substrate is used. A reverse embossing stencil of any material having an embossed pattern is provided, and on the reverse embossing embossing 103, an embossing _ ι 〇 3 ρ - side is provided, and the modified release layer 100 is provided. In a fourth embodiment of the present invention, the modified release layer provided by the first embodiment of the present invention is preferably 100°, wherein the formation of the modified release layer (10) is at least included in the reverse imprint template 2 'One side of the embossed pattern 103P is formed - the anti-adhesion layer 101: and the other interfacial layer 102 on the anti-adhesion layer 101 with respect to the imprint template 103 (please refer to FIG. 1). / anti-adhesive layer 101, preferably by deposition technique Teflon film, metal film, or by the carbon film of the seller, A film of the combination of the above 4, 1254359 曰 in the fourth of the hair In the embodiment, the anti-adhesion layer i 0 i is a gold (Au) film formed by a chemical vapor deposition process and having a thickness of less than 10 nm. Referring to FIG. 2, the interface layer 1G2 includes at least a long-chain carbon molecule and a hydrophilic functional device 204, such as a sulfhydryl group (_c〇〇H), a sulfite Gs〇3, a hydroxyl group (_0H), an amine group ( "Η2) or thiol (_sh). Carbon = Sub-long chain 202 has at least eight carbon molecules, one of which is adsorbed to the anti-adhesion layer by the force in the molecules between the molecules! Above; the hydrophilic functional machine is located at one end of the carbon molecular long chain 202 away from the anti-adhesion layer ι〇1, so that the surface of the modified release layer 100 can be made hydrophilic. In the fourth embodiment of the present invention, the interface layer 102 uses a surfactant such as 1 Dodecanethiol, 1-octylthiol (bQCTANETj^oL), and volatility. The solvent is formed by spin coating or soaking on one of the anti-adhesive layers ι〇ι to form a step 102 of changing the sputum 102, and at least one step of baking at a temperature lower than 80 ° C, To remove volatile solvents. Thereafter, an etch resist such as polymethacryl 1 曱酉曰, polystyrene, polymethyl decane is applied onto the release layer by spin coating or immersion on the embossing template 103. The other side is formed to form an etch resist layer R. Wherein, the etching resist layer R is partially filled in the recess 103S formed by the imprint pattern 103P of the imprint template 1〇3, and the other portion is covered on the area outside the recess 103S, wherein the recess is covered in the recess The thickness of the etch resist layer R outside 1 〇 3 s ranges from 2 〇 nm to 1 〇〇 nm. Then, proceed to a soft baking step. Referring to FIG. 7, FIG. 7 is a process of the fourth embodiment of the present invention, in which a reverse imprinted patterned modified release layer 15 1254359 100 having an etch resist layer R is imprinted on a substrate S. A cross-sectional view of the structure depicted. The reverse embossing template 103' has one side of the embossed pattern 103P, and is embossed and embossed on the substrate S (the embossing direction is indicated by the arrow in the figure); and the reverse embossing template is 103 The substrate S is separated from the substrate S so that the etching resist layer R is bonded to the substrate S. Referring to FIG. 8 , FIG. 8 is a cross-sectional view of the mouth structure after the pattern of the mask layer is formed by laminating the resist layer R on the substrate s according to the manufacturing process of the present invention. . In this step, at least the pressure is controlled to be at 12 〇 c, and a pressure sufficient to bond the resist layer r to the substrate S is used. A portion of the etch resist layer R is then removed by isotropic etching, such as reactive ion etching, to form a patterned resist layer 802 that causes the substrate S to exit. The pattern of the patterned resist layer 8〇2 is the same as the C-print pattern 1 〇3p of the reverse imprint template, and may be a regular three-dimensional pattern or an irregular three-dimensional pattern.
最後，以圖案化阻劑層802為罩幕，藉由一乾式或濕 蝕刻製程圖案化基材s。 …、I 、，因=，根據以上說明書所詳述之實施例，本發明所提供 :::壓印圖案化改質脫模層’可將具有奈米或是微米的線 寬圖案之任意材質之模板作抗黏著改良，使得蝕刻阻劑可以 =填入模板溝槽内部，以大幅提昇逆式壓印圖案化技術 良率。不僅可以取代現有的微影㈣技術所面臨昂貴之製 的限制’並且可以提供較溫和的製程環境，適用於各 種基材之圖案化達成本發明之目的。 雖然本發明已以一較佳實施例揭露如上，然其並非用以 16 1254359 ::本發明’任何熟習此技藝者’在不脫離本發明之精神和 =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。 【圖式簡單說明】 一透過以上說明書之詳細描述，並配合附圖之說明，讀者 將會對本發明所揭露之内容有更多的了解。必須強調的1， 本說明書之附圖形均未按照比例尺繪圖。事實上為了清楚地 說明，附圖中不同的構件都有可能被任意地擴大或縮小。 弟1圖係根據本發明之第一實施例所緣示之逆式壓印 圖案化之改質脫模層之剖面示意圖。 第2圖係根據本發明之第一實施例所繪示之界面層抗 霉占著層之表面吸附示意圖。 第3圖係根據本發明之第二實施例所繪示之逆式壓印 圖案化之改質脫模層之剖面示意圖。 第4圖係根據本發明之第二實施例所繪示之界面層與 抗黏著層之表面吸附示意圖。 第5圖係根據本發明第三實施例之製程少驟，將逆式麗 印圖案化改質脫模層壓印於基材上所繪示之結構剖面圖。 第6圖係根據本發明第三實施例之製程梦驟，將蝕刻阻 劑層貼合於基材，並形成圖案化罩幕層以後所繪示之結構剖 面圖。 第7圖係根據本發明第四實施例之製程少驟，將逆式壓 印圖案化改質脫模層壓印於基材上所纟會禾之結構剖面圖。 17 1254359 第8圖係根據本發明第四實施例之製程步驟，將蝕刻阻 劑層貼合於基材，並形成圖案化罩幕層以後所繪示之結構剖 面圖。 【主要元件符號說明】 100、300 :改質脫模層 102、302 :界面層 103P、303P ··壓印圖案 204、404 :親水性官能機 R :蝕刻阻劑層 103S 、 303S :凹室 101、301 :抗黏著層 103、303 :模板 202、402 :碳分子長鏈 602、802 :圖案化罩幕層 S :基材Finally, with the patterned resist layer 802 as a mask, the substrate s is patterned by a dry or wet etch process. ..., I,, =, according to the embodiment detailed in the above description, the present invention provides:: imprinting patterned modified release layer 'any material having a line width pattern of nano or micron The template is anti-adhesively modified so that the etch resist can be filled into the interior of the stencil trench to greatly improve the yield of the reverse embossing patterning technique. Not only can it replace the limitations of the existing lithography (four) technology, and it can provide a milder process environment, and is suitable for the patterning of various substrates to achieve the object of the present invention. Although the present invention has been disclosed above in a preferred embodiment, it is not intended to be used in the teachings of the present invention, and the invention may be modified and retouched without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention is defined by the scope of the appended claims. BRIEF DESCRIPTION OF THE DRAWINGS The reader will be more aware of the disclosure of the present invention by the detailed description of the specification and the accompanying drawings. Must be emphasized 1, the drawings of this specification are not drawn according to the scale. In fact, in order to clearly illustrate, various components in the drawings may be arbitrarily enlarged or reduced. Figure 1 is a schematic cross-sectional view of a modified imprinted patterned release layer in accordance with a first embodiment of the present invention. Fig. 2 is a schematic view showing the surface adsorption of the interface layer against the mold according to the first embodiment of the present invention. Fig. 3 is a schematic cross-sectional view showing a modified imprinted patterned release layer according to a second embodiment of the present invention. Fig. 4 is a schematic view showing the surface adsorption of the interface layer and the anti-adhesion layer according to the second embodiment of the present invention. Fig. 5 is a cross-sectional view showing the structure of a reverse embossed pattern-modified embossed laminate printed on a substrate according to a third embodiment of the present invention. Fig. 6 is a cross-sectional view showing the structure of the etching resist layer after laminating the etching resist layer to the substrate according to the third embodiment of the present invention. Fig. 7 is a cross-sectional view showing the structure of a reverse-embossed patterned modified release laminate printed on a substrate according to a fourth embodiment of the present invention. 17 1254359 Fig. 8 is a cross-sectional view showing the structure of the etching resist layer after laminating the etching resist layer to the substrate according to the fourth embodiment of the present invention. [Main component symbol description] 100, 300: modified release layer 102, 302: interface layer 103P, 303P · embossed pattern 204, 404: hydrophilic functional machine R: etching resist layer 103S, 303S: alcove 101 301: anti-adhesion layer 103, 303: template 202, 402: carbon molecular long chain 602, 802: patterned mask layer S: substrate
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