200945412 九、發明說明： 【發明所屬之技術領域】 本發明係有關於一種選擇性區域改質之方法，且特別 有關於一種利用電漿進行選擇性區域改質及形成圖案之方 法。 【先前技術】 © 為了將元件體積微型化或執行更為精密的功能，卉米 科技已然成為當前域的發展技術之―，而奈米 = 技術亦將隨著各種功能元件的製作或整合需求而更加 發展，以應用於奈米電子、奈米光電元件、奈米機電、、分 子電子70件、資料儲存、感測器及生物晶片等重要領域二 一直至目如，光學微影技術(photography)仍是製作功能 凡件之主流的圖案化技術，然而由於其在奈米科技的應用 〇 ，展上具有光學繞射的物理極限、以及設備和製作成^高 昂等缺點，因而近來發展出不受光學繞射極限所限制，^ 具有加工解析度高、速度快和成本低廉等特色的奈米壓印 技術(nan〇imprint)以及軟微影技術(s〇ft lith〇graphy)等製作 奈米圖案的方法。 ^述奈米壓印技術主要利用一具有奈米圖案的剛性膜 板，藉由機械力將此奈米圖案壓印至一特定之軟質的高分 子材料上，接著再將此軟質的高分子材料固化，以形成所 200945412 需的奈米圖案。而軟徵影技術則主要利用一軟質圖章作為 模板’其代表性技術之一為微接觸印刷法（microcontact printing)’亦即類似一般蓋圖章的方式，先沾上特定材料作 為印泥’接著與基板表面的特殊材質接觸以形成圖案，例 如將沾有硫醇分子的軟質圖章與基板的鍍金表面接觸，以 形成圖案化之可抵抗化學腐蝕的自組裝單層膜 (Self-Assembly Monolayer; SAM)。 儘管上述奈米壓印技術及微接觸印刷法均利用模板輔 助以進行圖案轉印，具有製作圖案快速、簡易及低成本等 ，點，然而面對完整的微奈米結構複製及量產技術的挑 ^奈米壓印技術需考量壓印機台的平行度與均壓性、壓 :骐板的脫膜技術以年高分子材料的特性等眾多影響因 定材=接觸印刷關需制可和基板表面材質作用^特 不印泥’且使用上容易因印泥擴以造成解析度 ❿ 析度求其他製程條件較為寬鬆且解 【發明内容】 本發明之一目的為提供一種選擇性 、可於〜樣品表面上形成一由改皙區域文質之方法， ί之圖案。上述改質區域和未改質區域所構 %連—步進行後㈣處理，心_=== 200945412 應 所選擇的化學、生物分子或金餘子進行反 圖案=之供-種選擇性區域改質及形成 元件。 步用以製作體積微型化及可執行精密功能的 本"發"明·^又一 n φ 圖案之方法，其可=為提供—種選擇性區域改質及形成 杜人 5越不同尺寸層級的需求，以製诰；^ 士 整合不同尺寸層級的功能元件。 、及/或 握月之另—目的為提供—種可同時進行大面積的、g 擇性區域改質及形由国也 即積的選 時間和成本。&圖案之方法’以節省複製圖案的製程 本發明之再又^〜 成圖案之方法，C供一種選擇性區域改質及形 度，且舰口表面的平整度和缺陷具有容忍 子樣〇口表面材貝的選擇性等製程條件有較佳 性，並可避免傷及樣品之表面。 叼弹 '本發明之再另-目的為提供一種選擇性區域改質及 成圖案之方法’其可結合自組裝技術的應用而使得形^ 案的膜層具有較佳的均句度、選擇度及解析度。 種 為達上述與其他目的，本發明一實施例主要提供 200945412 選擇性區域改質之方法，其包括提供一樣品，將一模板緊 貼於此樣品之一表面，以及提供一電漿，並利用上述模板 選擇性地隔離此電漿，使上述電漿僅接觸於樣品之表面的 部分區域以進行改質。 本發明之另一實施例提供了一種形成圖案之方法，其 包括提供一樣品，將一包含一通道之軟質圖章緊貼於此樣 品之一表面，以及提供一電漿，利用上述軟質圖章選擇性 0 地隔離此電漿，使電漿僅接觸並改質上述樣品之表面的部 分區域以形成一改質區域，而電漿未接觸樣品之表面的區 ； 域則為一未改質區域。其中，上述電漿經由軟質圖章之通 道而與樣品之表面接觸並進行改質，使上述改質區域包含 可對映至軟質圖章之通道的圖案。 本發明之又另一實施例提供了一種形成圖案之方法， 其包括提供一樣品，將一包含一通道之軟質圖章緊貼於此 _ 樣品之一表面，提供一電漿，利用上述軟質圖章選擇性地 隔離此電漿，使電漿接觸並改質樣品之表面的部分區域以 形成一改質區域，而電漿未接觸樣品之表面的區域則為一 未改質區域。接著可提供一自組裝分子以選擇性地作用於 樣品表面的一特定區域，並且將樣品浸泡於包含一物質的 溶液中，使此物質選擇性地與上述自組裝分子進行作用。 為讓本發明之上述和其他目的、特徵、和優點能更明 顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳 200945412 細說明如下： 【實施方式】 本發明係舉列-些實施例詳迷如下，其内文中相關之 圖式並未依據實際比例繪製，其作用僅在於表達本發明之 結構特徵。另，除了所提出之實施例外，本發明亦可廣泛 地施行於其他種實施例中，亦即，本發明的範圍乃不受實 施例限定，而以本發明所提出之申請專利範圍為準。 首先，本發明主要利用電漿對樣品表面進行改質，例 如進行表面活化（surface activation)、電漿聚合（plasma polymerization)、電漿鑛膜(plasma deposition)、電漿誘導接 枝(plasma induced grafting)或電漿餘刻（plasma etching)等 作用。由於電漿為離子化的氣體，其具有高度的活性和極 佳的流動性，因此可適於處理不同材料、形狀和尺寸的樣 品’並能在短時間内，於不影響樣品本體材料的性能下而 0 僅針對樣品表面進行改質，例如改變樣品表面的官能基或 化學組成，影響樣品表面之潤溼性、金屬附著性、染色性、 折射指數、硬度、化學純化性、潤滑性，以及生物相容性 等特性。 由於利用電漿改質樣品表面具有上述諸多優點，因此 本發明之一實施例主要利用電漿作為技術手段而提供一種 選擇性區域改質之方法，其包括提供一樣品，將一模板緊 貼於此樣品之一表面，以及提供一電漿，並利用上述模板 200945412 ，擇性地隔離此電漿，使上述電漿僅接觸於樣品表面的部 77區域以進仃改質。亦即，本實施例主要利用電漿搭配模 板、’=根據不同需求而設計或選擇所使用的電聚種類和所 欲進行改質的區域’並保護樣品表面不需進行改質的區域 不與電漿接觸以維持其原本的官能基、化學組成或性質。 上述改質區域和未改質區域可分別具有不同的性質，以便 於樣品表面構成一整合不同功能的圖案。 ® 上述杈板可緊貼於樣品之表面以形成一流道，而電漿 則可流經於此流道中，使樣品表面與上述流道中 的電漿接 而改質。上述模板或樣品之表面可具有一凹槽圖案，當 模板緊貼於樣品之表面時，則此凹槽圖案可構成上述流道 則乍為電漿之流經路徑，而模板的侧邊或上方則可包含至 y孔洞以供電漿流入上述流道中。然而，本實施例所提 f之換板亦可具有-穿透模板之鏤空圖案，使電漿可經由 杈板的鏤空圖案而直接與樣品表面接觸以進行選擇性區域 ❺的改質。 由於模板的作用係用以隔離電漿，使其僅針對樣品表 面的部分區域進行改質，因此模板較佳由不會受到所使用 的電漿而破壞之材料製成，以便可重複進行使用。 此外’由於剛性材質的模板較無法與樣品表面作緊密 的貼合’因此電漿恐滲入模板與樣品間的空隙而造成功能 圖案失真的現象。本實施例所使用之模板可較佳由具有彈 200945412 性之軟質材料所製成’例如聚二曱基石夕氧尸 (PolyDiMethylSiloxane;PDMS);如此一來，模板對於樣= 表面的平整度和缺陷將具有較佳的容忍度，且模板可緊^ 貼合於樣品之表面，進而能形成具有較佳解析度的改質區 域，並且避免傷及樣品之表面。 然而’在線寬和解析度專要求較不嚴苛的情況下，本 實施例亦可使用如聚氨酯（p〇lyurethanes)、聚亞醯胺 ❹（polyimides)或交聯酚醛樹脂（cross_iinked Novolac resins) 等其他材質作為模板之材料。 本發明之另一實施例則提供了一種形成圖案之方法。 首先，第一 A圖至第一 C圖為根據本發明另一實施例所提 供製作一包含通道之軟質圖章的流程圖式。參照第一 A 圖’先在3吋的矽晶圓1〇上塗佈SU-8光阻12[Microchem， product no. SU-8 2035]，並利用一般的半導體微影製程，使 φ 經過顯影後之SU-8光阻12,形成與光罩14上的圖形16呈 一定比例對映關係之圖案18,以作為製作軟質圖章的模 子’如第一 B圖所示。接著，將PDMS主劑[SYLGARD， 184A]及副劑[sylGARD, 184B]以10:1的比例均勻混 合，並將PDMS膠液放入腔室中且利用幫浦減壓將氣泡抽 出’進而得到無氣泡的PDMS膠液。將所得到之無氣泡的 PDMS膠液20倒入上述具有圖案18的SU-8光阻12’模子 後，送入烤箱以攝氏1〇〇度烘烤30分鐘，當PDMS膠液 20硬化成彈性體後，將其脫膜即可得到具有與光阻圖案18 11 200945412 成對映關係之圖案18，的通道 . ^ c ^ ^ 7 m ρομΓΛ , Γ2Γ! Γ22 ^ 層早分子败其極彳水，轉pdms^ 面上- 形後，即絲易在_巾崎脫模。、 在烘烤成 本實施例接著根據不同功能圖案 合適的電浆種類，例如-般的高分子 Ο ^會在其表面導人極性官能基以具有親水特性而= 氣乳電__會使其過 :;圖，22緊貼於-樣品之表面，將上述軟質實二= 區域：漿改質樣品之表面的部分 則為-域 i4而與樣品表面接觸並進行改質，使改質區域包含 章22之通道24的圖案。 軟質圖200945412 IX. INSTRUCTIONS: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method for modifying a selective region, and more particularly to a method for selectively modifying and patterning a region using plasma. [Prior Art] © In order to miniaturize the component volume or perform more precise functions, Huimi Technology has become the development technology of the current domain, and nano = technology will also be produced with the integration or integration of various functional components. More development, for nanoelectronics, nano-optical components, nano-electromechanical, molecular electronics 70, data storage, sensors and bio-chips and other important areas until the end, optical lithography (photography) It is still the mainstream patterning technology for the production of functional parts. However, due to its application in nanotechnology, it has the physical limitations of optical diffraction, as well as the disadvantages of equipment and fabrication. Limited by the diffraction limit, ^ nanoimprinting technology (nan〇imprint) and soft lithography (s〇ft lith〇graphy) with high resolution, high speed and low cost, etc. method. The nano-imprint technique mainly uses a rigid film with a nano pattern to imprint the nano pattern onto a specific soft polymer material by mechanical force, and then cure the soft polymer material. To form the nano pattern required by 200945412. Soft imaging technology mainly uses a soft stamp as a template. One of its representative technologies is microcontact printing, which is similar to the general stamp, first stained with a specific material as the inkpad. The special material of the surface is contacted to form a pattern, for example, a soft stamp with thiol molecules is brought into contact with the gold-plated surface of the substrate to form a patterned chemical-resistant Self-Assembly Monolayer (SAM). Although the above-mentioned nano imprinting technology and micro-contact printing method both use template assisting for pattern transfer, the patterning is fast, simple, and low-cost, etc., but facing the complete micro-nano structure replication and mass production technology. Picking the nano imprint technology needs to consider the parallelism and pressure equalization of the imprinting machine, pressure: the release technology of the slab is based on the characteristics of the annual polymer material, etc. The material of the surface of the substrate is not particularly suitable for printing. It is easy to use due to the expansion of the ink to cause resolution. The other process conditions are more relaxed and solved. [Inventive] One of the objects of the present invention is to provide a selectivity and can be sampled. On the surface, a method of changing the texture of the area, ί, is formed. The above-mentioned modified region and unmodified region are connected in a step-by-step (four) process, and the heart _=== 200945412 should be selected by the selected chemical, biomolecule or gold remnant = the supply-selective region change Quality and formation of components. The method used to make the volume miniaturization and the execution of the precise function of this "fat" Ming·^ another n φ pattern, which can be used to provide a selective region modification and the formation of Du Ren 5 different sizes Hierarchical requirements to make 诰; ^ 士 integrate functional elements of different size levels. And/or the other part of the moon – the purpose is to provide the time and cost of simultaneous large-area, g-selective regional upgrading and the shape of the country. & pattern method 'to save the reproduction of the pattern of the process of the present invention again ~ ~ into a pattern method, C for a selective area modification and shape, and the smoothness and defects of the ship's surface have tolerated sample 〇 The process conditions such as the selectivity of the mouth surface material are preferred, and the surface of the sample can be prevented from being damaged. The present invention is directed to providing a method for selective region modification and patterning, which can be combined with the application of self-assembly techniques to provide a film having a better uniformity and selectivity. And resolution. In order to achieve the above and other objects, an embodiment of the present invention mainly provides a method for modifying a selective region of 200945412, which comprises providing a sample, attaching a template to a surface of the sample, and providing a plasma and utilizing The template selectively isolates the plasma such that the plasma contacts only a portion of the surface of the sample for modification. Another embodiment of the present invention provides a method of forming a pattern, comprising providing a sample, a soft stamp comprising a channel is adhered to a surface of the sample, and providing a plasma, using the soft stamp selective The plasma is isolated such that the plasma only contacts and reforms a portion of the surface of the sample to form a modified region, and the plasma does not contact the surface of the sample; the domain is an unmodified region. Wherein, the plasma is brought into contact with the surface of the sample via a soft stamp channel and modified such that the modified region includes a pattern that can be mapped to a passage of the soft stamp. Still another embodiment of the present invention provides a method of forming a pattern, comprising: providing a sample, a soft stamp comprising a channel is adhered to a surface of the sample, providing a plasma, using the soft stamp to select The plasma is selectively isolated such that the plasma contacts and reforms a portion of the surface of the sample to form a modified region, and the region where the plasma does not contact the surface of the sample is an unmodified region. A self-assembling molecule can then be provided to selectively act on a particular region of the surface of the sample, and the sample is immersed in a solution containing a substance to selectively interact with the self-assembling molecules described above. The above and other objects, features, and advantages of the present invention will become more apparent and understood. The embodiments are described in detail below, and the related drawings are not drawn to actual scales, and are only intended to express the structural features of the present invention. In addition, the present invention is not limited to the embodiments, and the scope of the present invention is not limited by the embodiments, and the scope of the claims of the present invention shall prevail. First, the present invention mainly uses plasma to modify the surface of the sample, for example, surface activation, plasma polymerization, plasma deposition, plasma induced grafting. ) or plasma etching and other effects. Since the plasma is an ionized gas, it has high activity and excellent fluidity, so it can be applied to samples of different materials, shapes and sizes' and can not affect the performance of the sample body material in a short time. Down and 0 only modify the surface of the sample, such as changing the functional group or chemical composition of the sample surface, affecting the wettability, metal adhesion, dyeability, refractive index, hardness, chemical purity, lubricity, and Characteristics such as biocompatibility. Since the surface of the sample is modified by using plasma to have the above-mentioned advantages, an embodiment of the present invention mainly provides a method for selective region modification by using plasma as a technical means, which comprises providing a sample and adhering a template to the template. One surface of the sample, as well as a plasma, was used to selectively isolate the plasma using the template 200945412 described above such that the plasma contacted only the portion 77 of the sample surface for tampering. That is to say, this embodiment mainly uses the plasma matching template, '= designing or selecting the type of electropolymer used and the area to be modified according to different needs' and protecting the surface of the sample without modification. The plasma is contacted to maintain its original functional group, chemical composition or properties. The modified region and the unmodified region may have different properties, respectively, so that the surface of the sample constitutes a pattern that integrates different functions. ® The above-mentioned fascia plate can be placed close to the surface of the sample to form a first-class tract, and the plasma can flow through the flow path, so that the surface of the sample is modified with the plasma in the above-mentioned flow channel. The surface of the template or the sample may have a groove pattern. When the template is in close contact with the surface of the sample, the groove pattern may constitute the flow path and then flow through the path of the plasma, and the side or the top of the template may be It may be included in the y hole to supply the slurry into the above flow channel. However, the change plate of the embodiment may also have a hollow pattern of the through-template, so that the plasma can directly contact the surface of the sample via the hollow pattern of the seesaw to perform the modification of the selective region. Since the template is used to isolate the plasma so that it is only modified for a portion of the surface of the sample, the template is preferably made of a material that is not damaged by the plasma used, so that it can be reused. In addition, since the template of the rigid material is less able to be closely adhered to the surface of the sample, the plasma may infiltrate into the gap between the template and the sample to cause distortion of the functional pattern. The template used in this embodiment may preferably be made of a soft material having a 200945412 property, such as PolyDiMethyl Siloxane (PDMS); thus, the template is suitable for the flatness and defects of the surface. It will have a better tolerance, and the template can be closely attached to the surface of the sample, thereby forming a modified region with better resolution and avoiding damage to the surface of the sample. However, in the case where the online width and resolution are less demanding, the present embodiment may also use, for example, polyurethanes, polyimides or cross_iinked Novolac resins. Other materials are used as materials for the template. Another embodiment of the present invention provides a method of forming a pattern. First, the first to first C diagrams are flow chart diagrams for making a soft stamp containing a channel in accordance with another embodiment of the present invention. Referring to the first A drawing, SU-8 photoresist 12 [Microchem, product no. SU-8 2035] is first coated on a 3 矽 wafer, and the φ is developed by a general semiconductor lithography process. The subsequent SU-8 photoresist 12 forms a pattern 18 that is in a proportional relationship with the pattern 16 on the mask 14 as a mold for making a soft stamp as shown in FIG. Next, the PDMS main agent [SYLGARD, 184A] and the auxiliary agent [sylGARD, 184B] were uniformly mixed in a ratio of 10:1, and the PDMS glue was placed in the chamber and the bubble was extracted by the decompression of the pump. Bubble-free PDMS glue. The obtained bubble-free PDMS glue 20 is poured into the above-mentioned SU-8 photoresist 12' mold having the pattern 18, and then sent to the oven for baking at a temperature of 1 degree Celsius for 30 minutes, when the PDMS glue 20 is hardened into elasticity. After the body is removed, the film is obtained by having a pattern 18 in an opportunistic relationship with the photoresist pattern 18 11 200945412. ^ c ^ ^ 7 m ρομΓΛ , Γ 2Γ! Γ 22 ^ layer early molecular failure is extremely hydrophobic, After turning pdms^ on the surface - after the shape, the silk is easy to release in the _ towel. In the baking cost example, according to the different types of plasma according to different functional patterns, for example, the general polymer Ο will lead a polar functional group on its surface to have a hydrophilic property = 气 电 _ _ will make it :; Fig. 22 is closely attached to the surface of the sample, and the soft surface is replaced by the surface of the sample. The part of the surface of the modified sample is - domain i4 and is in contact with the surface of the sample and modified to make the modified region contain the chapter. The pattern of channel 24 of 22. Soft map
_在此實施例中，上述改質區域和未改質區域可根據不 同需求而分別具有不同的性質，以提供一特定物質選擇性 地作用於樣品表面之特定區域。上述特定物質可包含一能 於此特定區域行自組裝反應之分子，藉由例如將樣品浸泡 於一包含特定的化學、生物分子或金屬粒子等物質的溶液 中’使其藉由分子間的凡得瓦力（Van der Wads force)、氫 鍵(hydrogen bonding)、庫侖靜電力（Coulomb electrostatic force)、偶極_偶極力（dip〇ie_dip〇le interaction)等方式而選擇 12 200945412 性地吸附於改質區域或未改質 成-整合不同功能的圖案。而由於“且：八=當，:構 其特定的官能基與特定的樣品表面進行用 較佳解析度的圖案。本實施層’進而可形成具有 大的組裝方，圖案，夂=== ❹ ❹ 子兀件’並且^時處理大量物件，具有極佳的發展潛力刀。 儘管本實施例乃利用一般丰 章的模子，然而本發明並非微影製程形成軟質圖 微影技術或聚焦離子束《==可利用電子束 所提供模子的線m軟質成模子，且根據 :通道、奈米通道及/或其他尺寸層級之 二： k及/或整合不同尺寸層級的魏元件。另 用/製 亦可根據實際需求而製成適當的夫 、 質圖早22 面積的選擇性區域改質及形成圖案之方:便= 圖案的製程時間及成本。 4硬製 =，儘管本實關之軟f圖章22㈣道24為位於 ” 22之—表面的凹槽圖案，然、而本發明並非以此為 限，當把PDMS膠液倒在軟質圖章的模子上並以 = 時’其可形成PDMS低於模子厚度的軟質圖章22 = 來’通道24即包含了-穿透軟f圖章22之鏤空圖案 電聚則可經由此具有鏤空®案的通道22而與樣品表 觸並進行改質。 接 200945412 此外，本實施例所使用之軟質圖章並非以聚二甲基矽 氧，為限，而亦可包含其他具有彈性之軟質材料，以便可 緊密貼合於樣品之表面，進而形成具有較佳解析度的改質 區域，並且避免傷及樣品之表面。又，本實施例之軟質圖 章可較佳由不會受到所使用的電漿所破壞之材料所製成， 如此一來則可便於重覆使用。 ❹ 第二A圖至第二B圖為根據本發明又另一實施例於一 樣品表面之自組裝單分子膜層形成圖案的流程圖式，其係 利用上述實施例所提供之軟質圖章22進行後續的製程，而 本實施例所使用的軟質圖章22為具有5微米線寬尺寸之通 道24 〇 首先提供樣品30，本實施例係以一矽基板為例，由於 矽基板的表面容易在含有氧氣和水的環境下自然氧化成薄 ⑩的氧化矽層，亦或經由電漿處理或硫酸浸泡等活化製程可 使矽基板樣品30表面包含一氫氧基官能基，進而可提供矽 烷類的分子於其表面形成均勻的自組裝單分子膜。在此實 施例中，將矽基板依序使用丙酮、乙醇以及去離子水進行 清洗，接著將清洗完後的矽基板先以功率12 W的大氣電 漿(air plasma)在0.6托爾（torr)的壓力下處理1〇分鐘以將其 表面活性化，接著再將表面已活化的矽基板浸泡在0.5 mM 濃度之十八烧基三氣梦烧（OctadecylTrichloroSilane; OTS)[H3C(CH2)17SiCl3，Aldrich，product ηο·104817]的甲苯 14 200945412 溶液中2分鐘，使OTS分子於活化後的矽基板表面行自組 裝反應而形成一層OTS單分子臈32，如第二A圖所示。 之後，將此矽基板樣品3〇依序利用乙醇及去離子水進行清 洗。本實施例所使用之樣品3〇並非以矽基板為限，其亦可 包含其他如玻璃、氧化銦錫（IndiU]n Tin Oxide; ITO)或氧化 鋁等氧化物基板，以提供矽烷類的分子行自組裝反應。 所製作完成的PDMS軟質圖章22可依序利用丙酮、乙 ❹醇以及去離子水進行清洗。接著，將PDMS軟質圖章22 與前述表面具有OTS單分子膜32的矽基板樣品30緊密貼 合，並且置於一真空之電漿反應室中，以功率12 w的大 氣電漿33在0.6托爾的壓力下處理3分鐘。由於電漿反應 室内的氣壓極低，因此上述大氣電漿33可經由軟質圖章 22侧邊的孔洞A和B作為出入口，而自然擴散至由具有通 道24之軟質圖章22與樣品30所貼合構成的流道36中。 如此一來，曝露在大氣電漿33中的〇TS單分子膜32，將 0會因大氣電漿33的鬲活性而使其原有表面的甲烷基官能 基被改質為具有氫軋基的官能基，而沒有與大氣電漿接觸 的OTS單分子膜32，例如被PDMS軟質圖章22所直接貼 合處’則可保存原有的曱烷基官能基特性，如第二B圖所 示。 在此實施例中，由於電漿33的出入口孔洞人和B係 位於軟質圖章22的侧邊，因此會形成具有開口 Α^σΒ，的 開放式圖案，然而，上述電漿33的出入口孔洞亦可視需要 15 200945412 而設計於軟質圖章22的上方並連接於通道24，如此一來 則可形成一封閉式的圖案。此外，由於軟質圖章22為具有 彈性之軟質材料所製成，因此可和樣品30表面緊密地貼 合，並保護樣品30表面的OTS單分子膜32。 電漿處理完後’可將PDMS軟質圖章22自樣品30上 取下’再將樣品30依序使用丙酮、乙醇以及去離子水進行 清洗’即可得到具有未改質區域34和改質區域34,的OTS 0 分子膜32’之樣品30。 第三圖為完整的OTS分子膜在大氣電漿處理不同的時 間下，利用X射線光電子光譜儀（X_ray Ph〇t〇eiectr〇n Spectroscopy; XPS)檢測其表面碳原子内層電子的束縛能 (binding energy)，其中a表示0TS分子膜未經電漿處理的 XPS能譜線’而b、c、d和e則分別表示〇TS分子膜經由 功率12W的大氣電聚在〇.6托爾的壓力下各處理^秒、3 ❹秒、5秒和1〇秒後的XPS能譜分佈。經由第三圖的比較可 清楚顯示OTS分子膜在和大氣電漿短時間的接觸下，其表 面碳原子内層電子的束缚能會隨著與大氣電漿反應時間的 增長而往高能量處偏移，顯示0TS分子膜的表面已漸有改 質的現象。 第四A圖和第四B圖分別為上述〇TS分子膜未經電漿 處理以及經由大氣電漿處理10秒後，其表面碳原子内層電 子的xps此a番圖，其中未經電漿處理的〇ts分子膜只能解 16 200945412In this embodiment, the modified region and the unmodified region may have different properties depending on different requirements to provide a specific substance to selectively act on a specific region of the surface of the sample. The above specific substance may comprise a molecule capable of self-assembly reaction in this specific region, by, for example, immersing the sample in a solution containing a substance such as a specific chemical, biomolecule or metal particle. Van der Wads force, hydrogen bonding, Coulomb electrostatic force, dip 〇 di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di di The quality area has not been remodeled into a pattern that integrates different functions. And because "and: eight = when, the specific functional group is configured with a specific resolution of the sample surface with a better resolution. This embodiment layer can be formed with a large assembly, pattern, 夂 === ❹ The 兀 兀 ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' == can be used to soften the mold m of the mold provided by the electron beam, and according to: channel, nanochannel and / or other size level two: k and / or integration of different size level of Wei components. According to the actual needs, the appropriate area of the 22-area selective area can be modified and patterned: the process time and cost of the pattern. 4 Hard = even though the soft f stamp of the actual 22 (4) Road 24 is a groove pattern located on the surface of "22", but the invention is not limited thereto, when the PDMS glue is poured on the mold of the soft stamp and when =, it can form PDMS lower than the mold Thickness of the soft stamp 22 = come The channel 24 contains a hollow pattern that penetrates the soft f stamp 22. The electropolymer can be surface-touched and modified by the channel 22 having the hollowed out case. In addition, the soft stamp used in this embodiment is not limited to polydimethyl oxime, but may also contain other soft materials having elasticity so as to be closely adhered to the surface of the sample, thereby forming a better one. Resolve the modified area of the resolution and avoid damage to the surface of the sample. Further, the soft stamp of the present embodiment can be preferably made of a material which is not damaged by the used plasma, so that it can be easily reused. ❹ FIGS. 2A to 2B are flow chart diagrams for patterning a self-assembled monomolecular film layer on the surface of a sample according to still another embodiment of the present invention, which is performed by using the soft stamp 22 provided in the above embodiment. The subsequent process, and the soft stamp 22 used in this embodiment is a channel 24 having a line width of 5 micrometers. First, the sample 30 is provided. In this embodiment, a germanium substrate is taken as an example, since the surface of the germanium substrate is easily contained in oxygen. Naturally oxidized into a thin 10 yttrium oxide layer in a water environment, or via an activation process such as plasma treatment or sulfuric acid immersion, the surface of the ruthenium substrate sample 30 may contain a hydroxyl functional group, thereby providing a decane-like molecule. A uniform self-assembled monomolecular film is formed on the surface. In this embodiment, the ruthenium substrate is sequentially washed with acetone, ethanol, and deionized water, and then the cleaned ruthenium substrate is first subjected to an air plasma of 0.6 W at 0.6 torr (torr). The surface was activated for 1 以 minutes to activate the surface, and then the surface-activated ruthenium substrate was immersed in a 0.5 mM concentration of Octadecyl TrichloroSilane (OTS) [H3C(CH2)17SiCl3, Aldrich , product ηο·104817] toluene 14 200945412 solution for 2 minutes, the OTS molecule self-assembly reaction on the surface of the activated ruthenium substrate to form a layer of OTS single molecule 臈32, as shown in Figure A. Thereafter, the ruthenium substrate sample 3 was sequentially washed with ethanol and deionized water. The sample 3 used in the present embodiment is not limited to the germanium substrate, and may also include other oxide substrates such as glass, indium tin oxide (IndiU)n Tin Oxide; ITO) or alumina to provide molecules of decane. Self-assembly reaction. The completed PDMS soft stamp 22 can be washed sequentially with acetone, acetol and deionized water. Next, the PDMS soft stamp 22 is closely attached to the ruthenium substrate sample 30 having the OTS monomolecular film 32 on the surface, and placed in a vacuum plasma reaction chamber at a power of 12 w of atmospheric plasma 33 at 0.6 Torr. Treat under pressure for 3 minutes. Since the gas pressure in the plasma reaction chamber is extremely low, the above-mentioned atmospheric plasma 33 can pass through the holes A and B on the side of the soft stamp 22 as an entrance and exit, and naturally diffuses to be bonded by the soft stamp 22 having the passage 24 and the sample 30. In the runner 36. As a result, the 〇TS monomolecular film 32 exposed in the atmospheric plasma 33 changes the methyl group functional group of the original surface to a hydrogen-rolled base due to the enthalpy activity of the atmospheric plasma 33. The functional group, without the OTS monomolecular film 32 in contact with the atmospheric plasma, for example, directly attached to the PDMS soft stamp 22, preserves the original decyl functional group characteristics, as shown in Figure B. In this embodiment, since the entrance and exit holes of the plasma 33 and the B-series are located on the side of the soft stamp 22, an open pattern having an opening ,^σΒ is formed, however, the entrance and exit holes of the plasma 33 are also visible. It is required to be 15 200945412 and is designed above the soft stamp 22 and connected to the channel 24, so that a closed pattern can be formed. Further, since the soft stamp 22 is made of a flexible soft material, it can be closely adhered to the surface of the sample 30 and protect the OTS monomolecular film 32 on the surface of the sample 30. After the plasma treatment, the PDMS soft stamp 22 can be removed from the sample 30, and then the sample 30 is sequentially washed with acetone, ethanol and deionized water to obtain an unmodified region 34 and a modified region 34. , OTS 0 molecular film 32' sample 30. The third figure shows the binding energy of the inner layer of carbon atoms on the surface of a complete OTS molecular film at different times of atmospheric plasma treatment using X-ray photoelectron spectroscopy (X_ray Ph〇t〇eiectr〇n Spectroscopy; XPS). ), where a represents the XPS energy spectrum of the 0TS molecular film without plasma treatment, while b, c, d and e respectively represent that the 〇TS molecular film is electrically concentrated under the pressure of 〇.6 Torr by the power of 12W. The XPS spectrum distribution after each treatment of ^ second, 3 sec, 5 sec, and 1 〇 second. It can be clearly seen from the comparison of the third figure that the OTS molecular film is in contact with the atmospheric plasma for a short time, and the binding energy of the inner layer of carbon atoms on the surface of the carbon atom shifts to the high energy as the reaction time with the atmospheric plasma increases. It shows that the surface of the 0TS molecular film has gradually changed. The fourth A map and the fourth B graph are the xps of the inner layer of carbon atoms in the surface of the 〇TS molecular film without plasma treatment and after being treated by atmospheric plasma for 10 seconds, respectively, without plasma treatment. The 〇ts molecular film can only solve 16 200945412
析出c-c鍵的訊號’而使用大氣電聚處理1〇秒後的〇TS 分子膜則除了可解析對應出原本〇TS分子即有的C_C鍵， 另外還有C-Ο鍵、C=0鍵和COOH鍵等訊號，表示〇TS 分子膜的表面已受到含有氧自由基的大氣電漿改質而形成 含氧官能基。 經由上述實驗顯示，本實施例所提供之樣品3〇表面的 OTS分子膜32’之未改質區域34的表面仍為甲烷基37官 ❹能基，而〇TS分子膜32’之電漿改質區域34,表面原有的曱 烧基官能基則將被改質為例如包含羥基(hydroxyl)3 8、幾基 (carbonyl)40及/或羧基(carb〇xyl)42等官能基群，如第五圖 所示。 第六A圖和第六B圖為本實施例具有未改質區域34 和改質區域34’的OTS分子膜32’之樣品30經由掃描式光 電子能譜顯微鏡（Scanning Photoemission φ Spectromicroscopy，SPEM)檢測之結果。將χ射線光電子光 譜儀入射的X-ray聚焦至約300奈米’然後利用奈米位移 掃描台移動樣品以進行樣品的二維空間微動掃描，並藉由 16個電子訊號偵測裝置平均檢測束缚能範圍介於 290.5eV-278.5eV的光電子能譜訊號，以將樣品上所掃描到 每一個像素(pixel)後所得到的光電子能譜訊號經組合而成 像。第六A圖和第六B圖分別為本實施例之樣品3〇表面 的OTS分子膜32’經大氣電漿進行選擇性區域改質後的 SPEM影像，其中第六A圖所檢測的束縛能範圍為287 5〇_ 17 200945412 286.75eV，而第六B圖所檢測的束缚能範圍則為 285.25-284.50eV。由於第六A圖取得影像的束缚能範圍約 在C-O鍵、C=0鍵的範圍，因此OTS分子膜32,在改質區 域34’的影像訊號比其在未改質區域34要強，這是因為未 改質區域34的OTS分子膜32’不具有C-O鍵、〇0鍵和 COOH鍵的組成，所以未改質區域34的OTS分子膜32, 在束缚能範圍287.50- 286.75eV不會有訊號強度；第六b 圖取得影像的束缚能範圍主要為C-C鍵的範圍，由於改質 Q 區域34’之OTS分子膜32,的C-C鍵會被電漿蝕刻掉，因 此OTS分子膜32’在改質區域34,的影像訊號反而比其在未 改質區域34還要弱。 將上述具有由未改質區域34和改質區域34,構成圖案 的OTS分子膜32,之樣品30利用掃描式電子顯微鏡 (Scanning Electron Microscope; SEM)[Zeiss，Ultra 55]以及 掃描式凱文探針顯微鏡(Scanning Kelvin Probe Microscope， ❹ SKPM)[Seiko Instruments, SPA-300HV](使用探針 MikroMasch，CSC37/Cr-Au)進行檢視，所得到的結果則分 別如第七A圖及第七B圖所示。由於電漿改質區域34,的 OTS分子膜32,表面具有羥基、羰基及/或羧基等官能基 群’其表面電位較未改質區域34的表面電位低，因此由圖 式可清楚顯示改質區域34,呈現較暗的顏色，而未改質區域 34則呈現了較亮的顏色，且其中改質區域34,包含了軟質 圖章22之通道24的圖案。 18 200945412 以上實驗結果均可映證本實施例利用電漿搭配軟質圖 章確可於樣品表面有效進行改擇性區域的改質，然而本實 施例所使用之電漿亦可包含其他具有氧成分的電襞源，例 如氧氣電漿或水氣電漿，或可根據不同的設計和需求而<吏 用它種型態的電漿，本發明並非以此為限。 此外，參照第八圖’其顯示OTS分子在基板上行自植 裝反應時會先以島狀結構逐漸擴大，最後再形成單分子 ❾膜。本實驗在OTS分子形成島狀結構而尚未吸附滿一層分 子膜時’利用大氣電漿與OTS分子的碳鏈進行反應蝕刻， 將樣品使用電聚每處理3秒後，利用原子力顯微鏡(AtomicThe signal of the cc bond is precipitated, and the 〇TS molecular film after 1 sec. of treatment using atmospheric electropolymerization can resolve the C_C bond corresponding to the original 〇TS molecule, in addition to the C-Ο bond, C=0 bond and A signal such as a COOH bond indicates that the surface of the 〇TS molecular film has been modified by an atmospheric plasma containing oxygen radicals to form an oxygen-containing functional group. Through the above experiments, the surface of the unmodified region 34 of the OTS molecular film 32' on the surface of the sample provided by the present embodiment is still a methyl group 37 bureaucratic energy group, and the plasma of the 〇TS molecular film 32' is modified. In the region 34, the original sulfhydryl functional group on the surface will be modified to, for example, a functional group including a hydroxyl group 38, a carbonyl 40 and/or a carboxy group (carb 〇 xyl 42), such as The fifth picture is shown. 6A and 6B show that the sample 30 of the OTS molecular film 32' having the unmodified region 34 and the modified region 34' is detected by Scanning Photoemission φ Spectromicroscopy (SPEM). The result. The X-ray incident on the X-ray photoelectron spectrometer is focused to about 300 nm. Then the sample is moved by a nanometer displacement scanning table to perform two-dimensional spatial micro-motion scanning of the sample, and the binding energy is detected on average by 16 electronic signal detecting devices. Photoelectron spectroscopy signals ranging from 290.5 eV to 278.5 eV are combined to image the photoelectron spectroscopy signals obtained after scanning each pixel on the sample. 6A and 6B are respectively SPEM images of the OTS molecular film 32' on the surface of the sample 3 of the present embodiment subjected to selective modification of the atmosphere by atmospheric plasma, wherein the binding energy detected in FIG. The range is 287 5〇_ 17 200945412 286.75eV, and the bound energy range detected in Figure 6B is 285.25-284.50eV. Since the binding energy range of the image obtained in the sixth image is about the range of the CO bond and the C=0 key, the image signal of the OTS molecular film 32 in the modified region 34' is stronger than that in the unmodified region 34. Because the OTS molecular film 32' of the unmodified region 34 does not have the composition of the CO bond, the 〇0 bond, and the COOH bond, the OTS molecular film 32 of the unmodified region 34 does not have a binding energy range of 287.50 - 286.75 eV. Signal strength; the bound energy range of the image obtained by the sixth b diagram is mainly the range of the CC bond. Since the CC bond of the OTS molecular film 32 of the modified Q region 34' is etched away by the plasma, the OTS molecular film 32' is The image signal of the modified region 34 is weaker than that of the unmodified region 34. The above-described OTS molecular film 32 having a pattern formed by the unmodified region 34 and the modified region 34 is subjected to Scanning Electron Microscope (SEM) [Zeiss, Ultra 55] and scanning Kevin. A needle microscope (Scanning Kelvin Probe Microscope, ❹ SKPM) [Seiko Instruments, SPA-300HV] (using the probe MikroMasch, CSC37/Cr-Au) was used for the inspection, and the results obtained were as shown in the seventh and seventh panels, respectively. Shown. Since the surface of the OTS molecular film 32 having the plasma reforming region 34 has a functional group such as a hydroxyl group, a carbonyl group and/or a carboxyl group, the surface potential thereof is lower than that of the unmodified region 34, so that the pattern can be clearly changed. The texture region 34 exhibits a darker color, while the unmodified region 34 exhibits a brighter color, and wherein the modified region 34 includes a pattern of channels 24 of the soft stamp 22. 18 200945412 The above experimental results can be used to demonstrate that this embodiment can effectively modify the modified area on the surface of the sample by using the plasma with soft stamp. However, the plasma used in this embodiment can also contain other oxygen-containing components. The power source, such as oxygen plasma or water vapor plasma, may be used according to different designs and requirements, and the invention is not limited thereto. Further, referring to the eighth figure, it is shown that the OTS molecules are gradually enlarged in an island-like structure when the substrate is self-planted, and finally a monomolecular ruthenium film is formed. In this experiment, when the OTS molecule forms an island structure and has not yet adsorbed a layer of molecular film, the atmospheric plasma is used to react with the carbon chain of the OTS molecule, and the sample is electropolymerized for 3 seconds after each treatment, using an atomic force microscope (Atomic).
Force Microscope; AFM)[Seiko Instruments, SPA-300HV，使 用探針 MikroMascli，CSC37/Cr-Au coating]的輕敲模式 (tapping mode)取得OTS分子島狀結構與基板高度差的影 像’進而求得OTS分子膜的厚度與電漿處理時間的關係 圖，如第九圖所示。由第九圖可觀察到樣品電漿處理在〇 ❹秒到27秒時’ OTS分子膜的厚度隨電漿處理的時間呈線性 減短，但在27秒之後’ OTS分子膜的厚度則大抵不再減 少’這是因為OTS分子是由碳鏈(C-C)與末端的矽烷基 (~SiCl3)組成’其中碳鏈可和大氣電漿反應成水(h2〇)與二 氧化碳(C〇2)，之後在真空電漿腔中被帶走而造成〇Ts分 子的碳鏈減短，但與基板連結之石夕烧端的Si則不會和電漿 反應成氣體或液體產物而被帶走，因此OTS分子膜的厚度 在與電漿反應一段時間後則大抵不再變動。 19 200945412 第九圖顯示ots分子的碳鏈容易與電漿中的含氡自由 基反應而逐漸分解，因此改質區域34’之OTS分子膜32’ 的厚度將會隨著電漿處理時間的增長而減少，而這也表示 藉由控制電漿與分子膜的反應時間可進行官能基的改質並 /或打斷其碳鏈而進行移除。 之後，本實施例可提供一自組裝分子以選擇性地作用 於樣品30之表面的一特定區域，將上述表面具有已進行區 Φ 域性改質的OTS分子膜32’之樣品30浸泡在3-氨丙基三甲 氧基梦烧（3-AminoPropylTriMethoxySilane; APTMS) [H2N(CH2)3Si(OCH3)3，Aldrich，product no.281778]濃度為 97%的溶液中24小時。參照第十A圖所示，由於電漿改質 區域34’的OTS分子膜32,表面包含羥基、羧基等具有氫氧 I ' 基的官能基群，因此矽烷類的APTMS分子44可接附在電 漿改質區域34’的OTS分子末端處而形成一層ApTMS分子 膜’而OTS分子膜32’表面未被電漿改質區域34則將保持 ❿其原有的甲烷基官能基特性，因此APTMS分子無法在上 面形成自組裝單分子膜。將樣品3〇取出ApTMS溶液後， 使用去離子水清洗乾淨後，即可得到電漿改質區域34，具有 OTS/APTMS之雙層結構的樣品3〇。由於未改質區域％的 OTS分子膜32’之表面具有甲烧基官能基，因此具有疏水 特性’ *改質區域34,具有ApTMS分子44之表面則具有 極性的官能基，因此具有親水性，當未改質區域％和改質 區域34’的面積㈣時’其可藉由察視樣品3()上親斥水的 差異情況而觀察樣品3G表面〇TS或APTMS分子的吸附情 20 200945412 形。 將吸附有APTMS分子44的樣品30浸泡於含有直徑 約為10奈米（nm)的金奈米粒子[Sigma，product no.G1527] 膠體水溶液中30分鐘，因APTMS分子44的末端官能基 胺基(-NH2)在金奈米粒子的水溶液中將有部份轉變成帶有 正電荷之質子化的胺基(-NH3+)官能基，因此能與帶有負電 荷的金奈米粒子46產生電性吸附，而之後可得到分佈於改 q 質區域34’的金奈米粒子/APTMS/OTS之多層結構，如第十 B圖所示。而第十一圖則顯示本實施例所提供之金奈米粒 子/APTMS/OTS多層結構的掃描式電子顯微影像圖，由圖 式中可清楚看到金奈米粒子46呈現了高密度且均勻 佈。 由於現有的一些製程很難得到尺度均勻的奈米&子 然而若以化學方法進行，則可在一膠體溶液中大量’ ©度為1〜1000奈米且大小均勻的膠體粒子，亦β 製尺 ^人 1膠體板子w 包含奈米級粒子。本實施例利用自組裝單分子膜作、τ J 層，藉由分子膜的電荷與膠體粒子相反，因而能為連接 奈米膠體粒子，而於二維平面上形成均勻分佈$ =附金屬 粒子陣列’其用途可包含奈米觸媒、化學和生物屬奈米 米光子學等應用。 > 則及奈 電荷的胺基官 於選擇性， 另’由於APTMS分子的末端含有帶正 能基’因此除了吸附金屬粒子外，其亦可用 21 200945412 其他帶有負電荷的物質，例如蛋白質、抗原、抗體、核糖 核酸或去氧核糖核酸等生物分子。 此外，本發明亦能根據實際需求而於一樣品上重複進 行改質，並可結合自組裝的技術應用，以形成一疊層或圖 案交錯的結構，並可在樣品以及透明的pDMS軟質圖章上 形成對準標記，以便利用一般的光學攝影機進行對準標記 的重疊檢查及定位。 ❹ 雖然本發明已以數個較佳實施例揭露如上，然其並非 用以限定本發明，任何熟習此技藝者，在未脫離本發明所 揭示之精神下所完成之等效改變或修飾，均應包含在下述 之申請專利範圍内。 【圖式簡單說明】 第一 A圖至第一 C圖為本發明另一實施例製作軟質圖 章的流程圖式； © 第二入圖至第二B圖為本發明又另一實施例於一樣品 表面形成圖案的流程圖式； 第三圖為OTS分子膜與電漿反應不同的時間下之xps 圖； 第四A圖為OTS分子膜未經電漿處理的XPS能譜圖； 第四B圖為〇ts分子膜經大氣電漿處理1〇秒後的xpS 能譜圖； 第五圖為本發明又另一實施例之〇 T S分子膜經電漿改 22 200945412 質後的示意圖； 第六A圖和第六B圖為本發明又另一實施例之OTS 分子膜經電漿改質後的SPEM圖； 第七A圖為本發明又另一實施例之OTS分子膜經電漿 改質後的SEM圖； 第七B圖為本發明又另一實施例之OTS分子膜經電漿 改質後的SKPM圖； 第八圖為OTS分子在行自組裝反應過程中所顯示的圖Force Microscope; AFM) [Seiko Instruments, SPA-300HV, probe MikroMascli, CSC37/Cr-Au coating] tapping mode to obtain an image of OTS molecular island structure and substrate height difference' and then obtain OTS A graph of the relationship between the thickness of the molecular film and the plasma treatment time, as shown in the ninth figure. From the ninth figure, it can be observed that the plasma treatment of the sample is from leptosecond to 27 seconds. The thickness of the OTS molecular film decreases linearly with the plasma treatment time, but after 27 seconds, the thickness of the OTS molecular film is not large. Then reduce 'this is because the OTS molecule is composed of a carbon chain (CC) and a terminal decyl group (~SiCl3)' in which the carbon chain can react with atmospheric plasma to form water (h2〇) and carbon dioxide (C〇2), after which It is taken away in the vacuum plasma chamber to cause the carbon chain of the 〇Ts molecule to be shortened, but the Si of the stagnation end connected to the substrate does not react with the plasma to form a gas or liquid product, so the OTS molecule is removed. The thickness of the film does not change much after reacting with the plasma for a period of time. 19 200945412 The ninth graph shows that the carbon chain of the ots molecule is easily decomposed by reacting with the ruthenium-containing radical in the plasma, so the thickness of the OTS molecular film 32' in the modified region 34' will increase with the plasma treatment time. With the reduction, this also means that the functional group can be modified and/or its carbon chain can be removed by controlling the reaction time of the plasma with the molecular film. Thereafter, the present embodiment can provide a self-assembling molecule to selectively act on a specific region of the surface of the sample 30, and immerse the sample 30 having the OTS molecular film 32' having undergone the region Φ domain modification on the surface. -AminoPropyl TriMethoxySilane; APTMS [H2N(CH2)3Si(OCH3)3, Aldrich, product no.281778] A solution having a concentration of 97% for 24 hours. Referring to FIG. 10A, since the surface of the OTS molecular film 32 of the plasma reforming region 34' contains a functional group having a hydroxyl group such as a hydroxyl group or a carboxyl group, the ATMTM molecule 44 of the decane can be attached thereto. At the end of the OTS molecule of the plasma modification region 34', a layer of ApTMS molecular film is formed, and the surface of the OTS molecular film 32' is not protected by the plasma modification region 34, and the original methyl group functional group property is maintained, so APTMS The molecule cannot form a self-assembled monomolecular film thereon. After the sample 3 was taken out of the ApTMS solution, it was washed with deionized water to obtain a plasma-modified region 34, and a sample having a double-layer structure of OTS/APTMS. Since the surface of the unmodified region % of the OTS molecular film 32' has a methyl group functional group, it has a hydrophobic property '*modified region 34, and the surface having the ApTMS molecule 44 has a polar functional group, and thus has hydrophilicity. When the area of the unmodified region and the area of the modified region 34' (four) are 'when it can be observed by the difference in the water on the sample 3 (), the adsorption of the surface of the sample 3G 〇TS or APTMS molecules is observed 20 200945412 . The sample 30 to which the APTMS molecule 44 was adsorbed was immersed in a colloidal aqueous solution of a gold nanoparticle [Sigma, product no. G1527] having a diameter of about 10 nm (nm) for 30 minutes due to the terminal functional amino group of the APTMS molecule 44. (-NH2) will partially convert into a positively charged protonated amine (-NH3+) functional group in an aqueous solution of the gold nanoparticles, thereby generating electricity with the negatively charged gold nanoparticles 46. Sexual adsorption, and then a multilayer structure of gold nanoparticles/APTMS/OTS distributed in the modified q-region 34' can be obtained, as shown in FIG. The eleventh image shows a scanning electron micrograph of the gold nanoparticle/APTMS/OTS multilayer structure provided in the present embodiment, and it is clear from the drawing that the gold nanoparticle 46 exhibits high density and Evenly cloth. Because some existing processes are difficult to obtain a uniform size of nano & However, if chemically carried out, a large amount of colloidal particles with a uniformity of 1 to 1000 nm and a uniform size can be obtained in a colloidal solution. The ruler ^ human 1 colloidal plate w contains nano-sized particles. In this embodiment, a self-assembled monomolecular film is used as the τ J layer, and the charge of the molecular film is opposite to that of the colloidal particles, so that the nanocolloid particles can be connected to form a uniform distribution on the two-dimensional plane. 'The use can include nanocatalysts, chemical and biological applications such as nanometer photonics. > Then the amine group of the Nai charge is selective, and 'Because the end of the APTMS molecule contains a positive energy group', in addition to adsorbing the metal particles, it can also use 21 200945412 other negatively charged substances, such as proteins, Biomolecules such as antigens, antibodies, ribonucleic acids or deoxyribonucleic acids. In addition, the present invention can also be repeatedly modified on a sample according to actual needs, and can be combined with self-assembly technology to form a laminated or pattern staggered structure, and can be used on samples and transparent pDMS soft stamps. Alignment marks are formed to perform overlay inspection and positioning of the alignment marks using a general optical camera. Although the present invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and any equivalent changes or modifications may be made without departing from the spirit of the invention. It should be included in the scope of the patent application below. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A to FIG. 1C are flow chart diagrams for making a soft stamp according to another embodiment of the present invention; © second to second B are the same as another embodiment of the present invention The flow chart of the surface of the product is formed; the third figure is the xps diagram at different times of the OTS molecular film and the plasma reaction; the fourth picture is the XPS spectrum of the OTS molecular film without plasma treatment; The figure shows the xpS energy spectrum of the 〇ts molecular film treated by atmospheric plasma for 1 〇 second; the fifth figure is a schematic diagram of the 分子TS molecular film after the plasma modification of the 2009TS molecular film 22 200945412; FIG. 6 and FIG. 6B are SPEM diagrams of the OTS molecular film after plasma modification according to still another embodiment of the present invention; FIG. 7A is a plasma modification of the OTS molecular film according to still another embodiment of the present invention; The latter SEM image; the seventh B is a SKPM diagram of the OTS molecular film after plasma modification according to still another embodiment of the present invention; and the eighth figure is a diagram of the OTS molecule during the self-assembly reaction process.
第九圖為OTS分子的碳鏈容易與電漿中的含氧自由基 反應示意圖； 第十A圖為本發明又另一實施例之OTS分子膜經電漿 選擇性區域改質後吸附APTMS分子的示意圖； 第十B圖為本發明又另一實施例所提供之 OTS/APTMS/金奈米粒子構造的示意圖；及 第十一圖為本發明又另一實施例所提供吸附金奈米粒 φ 子的樣品之SEM圖。 【主要元件符號說明】 10〜矽晶圓； 12〜光阻； 12’〜經過顯影後之光阻； 14〜光罩； 16〜光罩的圖形； 18〜光阻的圖案； 23 200945412 18’〜與光阻的圖案成對映關係之圖案； 20〜膠液； 22〜軟質圖章； 24〜通道； 3 0/"樣品， 32〜單分子膜； 32’〜改質後之單分子膜； 33〜電漿； ❾ 34〜未改質區域； 34’〜改質區域； 36〜流道； 37〜曱烷基； 38〜羥基； 40〜羰基； 42〜羧基； 44〜APTMS分子； ❹ 46〜金奈米粒子； A、B〜出入口孔洞； A’和B’〜開口； a〜OTS分子膜未經電漿處理的XPS能譜線； b〜OTS分子膜經大氣電漿處理1秒後的XPS能譜線; c〜OTS分子膜經大氣電漿處理3秒後的XPS能譜線; d〜OTS分子膜經大氣，電漿處理5秒後的XPS能譜線; e〜OTS分子膜經大氣電漿處理10秒後的XPS能譜 線。 24The ninth figure is a schematic diagram of the reaction of the carbon chain of the OTS molecule with the oxygen-containing radical in the plasma; FIG. 10A is another embodiment of the invention, the OTS molecular film is modified by the selective region of the plasma to adsorb the APTMS molecule. FIG. 10B is a schematic view showing the structure of OTS/APTMS/Gold Nanoparticles provided by still another embodiment of the present invention; and FIG. 11 is a view showing the adsorption of gold nanoparticles φ according to still another embodiment of the present invention. SEM image of the sample of the child. [Main component symbol description] 10~矽 wafer; 12~ photoresist; 12'~ developed photoresist; 14~ reticle; 16~ reticle pattern; 18~ photoresist pattern; 23 200945412 18' ~ pattern in contrast with the pattern of the photoresist; 20~ glue; 22~ soft stamp; 24~ channel; 3 0/" sample, 32~monomolecular film; 32'~ modified monolayer 33~plasma; ❾ 34~unmodified region; 34'~modified region; 36~channel; 37~decyl; 38~hydroxy; 40~carbonyl; 42~carboxy; 44~APTMS molecule; 46~Henna nanoparticles; A, B~ inlet and outlet holes; A' and B'~ openings; a~OTS molecular film without plasma treatment of XPS energy lines; b~OTS molecular film treated by atmospheric plasma for 1 second After XPS energy line; XPS line of c~OTS molecular film treated by atmospheric plasma for 3 seconds; d~OTS molecular film by atmospheric, plasma treatment for 5 seconds after XPS line; e~OTS molecule The XPS energy spectrum of the membrane after 10 seconds of atmospheric plasma treatment. twenty four