200921270 九、發明說明： 【發明所屬之技術領域】 本發明是有關於—種製 別是指-種結合表面修^ 専膜圖案之方法’特 之方法。 >飾轉印技術以製作氧化物薄骐圖案 【先前技術】 以往應用於半 作氧化物薄膜圖案的方法，是以傳統的黃光製 為主，然而，由於 07再光微衫蝕刻技術 阻及顯影液均為對人體有害備昂貴，且所用之光 操作人員的健康造成咸脅：：:::二:容易對現場 境生態造成嚴重的污_，所廢液也會對環 法實為重要課題。 所以發展新的氧化物薄膜圖案製 且其製程快速、成本低，：：一且大：積的金屬薄媒圖案， > '不茜一般黃光微影製程中昂貴的 所以ηΤΡ成為非傳紐刻技術t最㈣ = nTPM行時’是先於—個聚二甲㈣氧院（pdms) 之才吴具上披覆—待轉印的薄膜膜層，再將該模具與 一土^合’利用轉印方式將該膜層轉印至該基板上。 nTP目，j遭遇到的困難是無法製作由氧化物形成的 陶免材料圖案’主要是因為用一般的物理方式將陶㈣膜 :;MS模具上’會因為減鑛時產生的高溫而破壞PDMS 。、+面k成模具表面不平整。另一方面若用化學 200921270 溶=於模具上塗佈陶竟薄膜時，是以有機物質作為溶劑 去而有機溶劑乾燥時容易揮發，因此需進行多次塗 烤才能使膜層達到一定厚声。而Β、々@ " 又厚度而且溶劑揮發會造成塗佈溶 液體積收縮，使氧化物薄膜不易成型，並使後續轉印圖案 失真或是不連續。 /' 【發明内容】 因此，本發明之目的，即在提供一種快速簡便、低成 本且轉印圖案完整的表面修飾轉印技術製作氧化物薄膜 圖案之方法。 ' 於是，本發明表面修飾轉印技術製作氧化物薄膜圖案 之方法，包含： (Α)準備一模具與一基板； (Β)在該模具的一成型面上彼覆一個電解質單元； (C )利用液相沈積法於該電解質單元上彼覆一層氧化 物薄膜層； (D)在6亥基板表面披覆一層輔助轉印層；及 (Ε )使該模具之成型面與該氧化物薄膜層朝向該基板 ，並將模具與基板貼附壓合，原本位於模具上的氧化物薄 膜層會轉印附著於該輔助轉印層上，以形成氧化物薄膜圖 其中由於利用液相沈積法（liquid phase deposition, 簡稱LPD )來形成氧化物薄膜層時，是於具有親水性的表 面上較易形成薄膜，所以於步驟中，將電解質單元坡 覆於模具上可以將模具之成型面作表面修飾以完成親水處 200921270 理 且所述電解質單元是包括數 以利於後續LPD的進行。200921270 IX. DESCRIPTION OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a method of bonding a surface to a surface film. > Decorative transfer technology to produce oxide thin enamel pattern [Prior Art] The method used in the past for semi-doped oxide film pattern is based on traditional yellow light, however, due to the 07 re-light micro-etching technology And the developer is harmful to the human body and expensive, and the health of the light operator used causes salty threats::::: 2: It is easy to cause serious pollution to the site ecology _, the waste liquid will also be true for the important topic. Therefore, the development of a new oxide film pattern system and its rapid process, low cost, :: one and large: the accumulation of metal thin media pattern, > 'not the general yellow light lithography process is expensive, so ΤΡ ΤΡ become non-transfer technology t most (four) = nTPM line when 'before' - a polydimethyl (tetra) oxygen institute (pdms) only on the Wu-coating - the film layer to be transferred, and then the mold and a soil ^ use The film layer is transferred onto the substrate by printing. nTP, j encountered difficulties in the inability to fabricate the ceramic-free material pattern formed by the oxide 'mainly because of the general physical way to make the ceramic (four) film:; MS mold on the 'destruction of PDMS due to the high temperature generated during mining . , + face k into the mold surface is not flat. On the other hand, if chemistry 200921270 is used to dissolve the ceramic film on the mold, the organic substance is used as a solvent, and the organic solvent is easily volatilized when it is dried. Therefore, it is necessary to apply a plurality of times to make the film layer have a certain thick sound. However, 厚度, 々 @ " thickness and solvent volatilization will cause the coating solution to shrink in volume, making the oxide film difficult to shape and making the subsequent transfer pattern distorted or discontinuous. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a method for producing an oxide film pattern by providing a surface modification transfer technique which is fast, simple, and low in cost and complete in transfer pattern. Thus, the method of fabricating an oxide film pattern by the surface modification transfer technique of the present invention comprises: (Α) preparing a mold and a substrate; (Β) covering an electrolyte unit on a molding surface of the mold; (C) Applying an oxide film layer to the electrolyte unit by liquid deposition; (D) coating an auxiliary transfer layer on the surface of the 6-well substrate; and (Ε) forming the molding surface of the mold and the oxide film layer Orienting the substrate, and attaching the mold to the substrate, the oxide film layer originally located on the mold is transferred and attached to the auxiliary transfer layer to form an oxide film. Phase deposition (LPD) to form an oxide film layer is easier to form a film on a hydrophilic surface. Therefore, in the step, the molding surface of the mold can be surface-modified by coating the electrolyte unit on the mold. The hydrophilic portion is completed and the electrolyte unit is included to facilitate the subsequent LPD.
層不同高分子材料所製成的電解質層。 【實施方式】 S 有關本發月之月述及其他技術内容、特點與功效，在 以下配合參考圖式之—個較佳實施例的詳細說明中，將可 清楚的呈現。 參閱圖1、2、3 ’本發明表面修飾轉印技術製作氧化物 薄膜圖案之方法之較佳實施例，是配合—轉印設備來達成 所述轉印》又備包括-模具i，以及一個與該模具i對應設 置的基板2，該模具1包括數個突出部11，以及數個位於該 等突出部11間的凹陷# 12，且該等突出部u與凹陷部12 共同形成一上下凹突延伸的成型Φ 13，而該製作方法包含 以下步驟： 進行步驟61 :準備該模具丨，該模具i為具有彈 性的聚二曱基矽氧烷（PDMS )材料製成。An electrolyte layer made of different polymer materials. [Embodiment] S The description of the present invention and other technical contents, features and effects will be clearly described in the following detailed description of a preferred embodiment with reference to the drawings. Referring to Figures 1, 2, and 3, a preferred embodiment of the method for fabricating an oxide film pattern by the surface modification transfer technique of the present invention is a combination-transfer device for achieving the transfer, and includes a mold i, and a a substrate 2 corresponding to the mold i, the mold 1 includes a plurality of protrusions 11 and a plurality of depressions #12 located between the protrusions 11, and the protrusions u and the recesses 12 together form a concave and convex The process of forming Φ 13, and the manufacturing method comprises the following steps: Step 61: Preparing the mold 丨, the mold i is made of a material of polyacrylonitrile-based oxane (PDMS) having elasticity.
(2)進行步驟62 :在模具1的成型面〗3上，利用高 分子電解質材料披覆—電解質單A 3來將模具1作表面親 水性修飾。進行時，首先配製三種溶液分別為溶液a、b、c 办液a為濃度50 mM〜1〇〇 mM的聚丙稀胺鹽酸鹽（pAH )水’谷液，溶液b為2〇 mM〜5〇爪厘的聚苯乙稀磺酸鈉（ PSS)水溶液，溶液c為20 mM〜50 mM的聚二烯丙基二甲 基胺鹽酸鹽（PDDA)水溶液。 接著將模具1浸入溶液a中維持3〇〜6〇分鐘，再用去 離子水沖洗及吹乾後，使模具1之成型面13上形成一層第 200921270 一電解質層31。再將模具1浸入溶液b中維持i5〜3〇分鐘 ，再用去離子水沖洗及吹乾，以形成一層第二電解質層32 。將模具1浸人溶液C中維持15〜3〇分鐘，再用去離子水 沖洗及吹乾，以形成一層第三電解質層33 ,再將模具i重 覆浸入溶液b、c中三到五次，因此，本實施例之電解質單 元3是包括數層高分子材料製成的pAH/ (pss/pDDA) η多 廣電解質層3卜32、33結構（圖2只示意出五層電解㈣ 31、32、33 ’但實施時不以其膜層數目為限制）。 藉由多層正負電高分子電解質層31、32、33的修飾後 ，可以有效達到模具1的表面親水性處理。其中，使用 ΡΑΗ作為第-層電解質層31，是因為ρΑΗ為直鏈型分子與 PDMS模具1間的吸附力較小，故用ρΑΗ作為轉貼的犧牲 層’之後再以PSS及PDDA反覆修飾模具i。 (3)進行步驟63 :將該表面修飾後的PDMS模具1浸 入一液相沈積反應溶液中，本實施例的液相沈積反應溶液 疋鈦酸鉛薄膜反應溶液’藉由液相沈積法（叫⑽沖㈣ deposition)於電解質單a 3的表面披覆一層鈦酸鉛的氧化 物薄膜層4 °其中’液相沈積法為公知技術，且亦詳載於本 案申請人先前申請之證書號數第1233166號發明專利中，故 在此不再詳細說明。 (4 )進行步驟64 .準備該基板2，本實施例之基板2 疋由一種不同材質組成而形成三層結構故該基板2由上 至下包括-個金膜| 21、一個二氧化石夕層22，以及一個矽 層23。 200921270 (5) 進行步驟65 :將該Au/Si〇2/Si基板2浸入一個輔 助轉印層反應溶液中’本實施例之輔助轉印層反應溶液為 巯丙基三甲氧基矽烷（3_MPTS)的甲醇溶液，藉此使基板 2朝向该模具1的表面上形成一層由該3-MPTS曱醇溶液所 製成的輔助轉印層5。接著用甲醇沖洗基板2與輔助轉印層 5後，用氮氣吹乾輔助轉印層5與基板2。其中，本實施例 之基板2的最上層為金膜層21,而輔助轉印層5材料使用 3-MTPS ’是因為3-MTPS的硫醇末端官能基容易與金形成 化學鍵結，藉此使輔助轉印層5穩定披覆於基板2上。 (6) 進行步驟66 :將該模具！之成型面13與該等膜 層3、4朝向基板2，並將模具！與基板2貼附壓合，使位 ㈣具1之突出部U上的乳化物薄膜層4與該輔助轉印層 5貼靠’氧化物薄膜層4會與輔助轉印層5㈣氧烧官能基 產生鍵結，由於3_MPTS輔助轉印層5與基板2間的作用力 丄大於PAH電解質層31|^pDMS模具ι間的作用力，所以 田氧化物薄膜層4與該輔助轉印5的官能基鍵結後，即 可達成脫模轉印的效果。 需要說明的是，PAH電解質層31與！>DMS模具i的吸 :力:交小，所以該電解質單★ 3與氧化物薄膜層4對應於 大出4 11上的區塊’都會轉印形成於該辅助轉印層$上， ^由乳化物相層4形成氧化物薄膜圖案41。氧化物薄圖 物11成於4基板2上之後，加熱持温5分鐘以強化氧化 膜圖案41與金膜層21之間的化學鍵結，最後將模具^ 移開即完成製作。 200921270 由上述說明可知’該_轉印層5的功效是作為氧化 物薄膜層4脫模轉印時的黏著劑。由於不同基板2會有不 同的自我組裝（Self-assembly)特性，因此本發明在實施時 ，當基板2選用不同材質時’也需配合改變辅助轉印層5 的材質’以使基板2與輔助轉印層5的末端官能基之間能 產生良好的化學鍵結，當然，輔助轉印層5之材f也需配 合該氧化物薄膜層4的材質不同而作調整。 參閱圖4 &本發明之模具j以及氧化物薄膜圖案w 形成於基板2上的SEM圖片。圖中該模具ι的突出部^為 直線間隔排列的形式，故轉印形成的氧化物薄膜圖案Μ亦 為直線間隔排列。 參閱圖5為另種模具i態樣以及—個對應形成於基 板2上的氧化物薄膜圖案4卜目中該模具k凹陷部。為 數個圓形且間隔設置的凹穴’於該等凹陷部12間形成一個 連接成一體的突出冑11，因此’在轉印後該基板2上亦形 成與該突出部11對應的氧化物薄膜圖案41。 由以上說明可知’本發明主要是先於模具1表面沈積 該等電解質層31、32、33來作親水性的表面修飾處理，以 利於後續使用液相沈積法將氧化物_層4沈積於該模具i 上，以及圖案轉印的動作，因此本發明具有下列優點： (1)本發明不需要使用一般黃光微影蝕刻中複雜且昂 貴的曝光設備’所以可以達到製程成本低的優點。 ⑺本發明不需如傳統製程使用化學蝕刻液，所以可 以達到化學減廢及環境保護的目標。 10 200921270 (3)本發明透過電解質單元3將模具丨作表面修飾， 使氧化物薄膜層4可藉由液相沈積法披覆於模具丨上，由 於液相沈積法的製程溫度比以往使用濺鍍方式鍍膜的製程 溫度低，所以本發明成膜時不會破壞模具丨表面，此外， 利用液相沈積法披覆該氧化物薄膜層4時，大部分的揮發 物貝為水，且其揮發比例低，—般而言，在室溫加熱至75〇 C，其重1損失比其他化學溶液法來的小且損失的大多為 水，所以薄膜厚度的收縮量小，因此本發明改善以往使用 化學洛液法成膜時的有機溶劑揮發等問題。所以本發明可 以可以保持氧化物薄膜| 4的完整性、轉印圖案連續而不 失真’且S亥圖案轉印方式十分簡單快速’並實現氧化物薄 膜圖案41之轉印技術’故確實達到本發明之目的。 ^惟以上所述者，僅為本發明之較佳實施例而已，當不 &以此限定本發明實施之，即大凡依本發明中請專利 範圍及發明說明内容所作之簡單的等效變化與修飾，皆仍 屬本發明專利涵蓋之範圍内。 【圖式簡單說明】 圖1疋—流程示意圖，顯示本發明表面修飾轉印技術 作氧化物薄膜圖案之方法的-較佳實施例； 圖2疋與本發明配合使用的一模具與一電 局部放大圖； 貝平几旳 圖3是該較佳實施例的一流程圖； 圖4是利用掃描式電子顯微鏡（sem)拍下的圖片，圖 a顯不模具的俯視圖，圖4⑴是該模具的側視圖， 200921270 圖4(c)是氧化物薄膜圖案轉印於一基板上的圖片；及 圖5是利用掃描式電子顯微鏡（SEM)拍下的圖片，圖 5 ( a )顯示另一種型態之模具的俯視圖，圖5 ( b )是該模 具的立體圖，圖5(c)是氧化物薄膜圖案轉印於一基板上 的圖片。 12 200921270 【主要元件符號說明】 1 •…模具 3 ……電解質單元 11 ……突出部 31 •第一電解質層 12 …凹陷部 32- 第二電解質層 13 成型面 33 第三電解質層 2 , ••…基板 4 氧化物薄膜層 21 •…金膜層 41 ………氧化物薄膜圖案 22 ·- 二氧化矽層 5 ………輔助轉印層 23 … 矽層 61、 - 6 6…步驟 13(2) Step 62 is carried out: On the molding surface of the mold 1, the mold 1 is surface-hydrophilized by coating the electrolyte sheet A 3 with a high molecular electrolyte material. When proceeding, firstly prepare three kinds of solutions respectively for solution a, b, c, liquid a, polyacetamide hydrochloride (pAH) water's solution with concentration of 50 mM~1 mM, solution b is 2 〇 mM~5 An aqueous solution of sodium polystyrene sulfonate (PSS) in 〇 厘, solution c is a 20 mM to 50 mM aqueous solution of polydiallyldimethylamine hydrochloride (PDDA). Next, the mold 1 was immersed in the solution a for 3 Torr to 6 Torr, and then rinsed with deionized water and blown dry to form a layer of the electrolyte layer 31 of the 200921270 on the molding surface 13 of the mold 1. The mold 1 is further immersed in the solution b for i5 to 3 minutes, rinsed with deionized water and blown dry to form a second electrolyte layer 32. The mold 1 is immersed in the human solution C for 15 to 3 minutes, rinsed and dried with deionized water to form a third electrolyte layer 33, and the mold i is repeatedly immersed in the solutions b, c three to five times. Therefore, the electrolyte unit 3 of the present embodiment is composed of a plurality of layers of polymer material, pAH / (pss / pDDA) η multi-poly electrolyte layer 3 32, 33 structure (Figure 2 only shows five layers of electrolysis (four) 31, 32, 33 'But the implementation is not limited by the number of layers.) By the modification of the multilayer positive and negative electric polymer electrolyte layers 31, 32, and 33, the surface hydrophilic treatment of the mold 1 can be effectively achieved. Wherein, ΡΑΗ is used as the first-layer electrolyte layer 31 because ρΑΗ is a linear type molecule and the adsorption force between the PDMS mold 1 is small, so ρΑΗ is used as the sacrificial layer of the transfer, and then the mold is repeatedly modified by PSS and PDDA. . (3) performing step 63: immersing the surface modified PDMS mold 1 in a liquid phase deposition reaction solution, and the liquid phase deposition reaction solution of the present embodiment is a lead titanate thin film reaction solution 'by liquid phase deposition method (10) Rushing (4) deposition) coating a layer of an oxide film of lead titanate on the surface of the electrolyte single a 3 4 ° wherein the liquid phase deposition method is a well-known technique, and is also detailed in the certificate number previously applied for by the applicant of the present application. In the invention patent No. 1233166, it will not be described in detail herein. (4) Performing step 64. Preparing the substrate 2, the substrate 2 of the embodiment is composed of a different material to form a three-layer structure, so the substrate 2 includes a gold film from top to bottom | 21, a magnet dioxide eve Layer 22, and a layer of germanium 23. 200921270 (5) Performing step 65: immersing the Au/Si〇2/Si substrate 2 in an auxiliary transfer layer reaction solution. The auxiliary transfer layer reaction solution of the present embodiment is propylpropyltrimethoxydecane (3_MPTS). The methanol solution is thereby used to form the substrate 2 toward the surface of the mold 1 to form an auxiliary transfer layer 5 made of the 3-MPTS sterol solution. Next, after the substrate 2 and the auxiliary transfer layer 5 were washed with methanol, the auxiliary transfer layer 5 and the substrate 2 were blown off with nitrogen. Wherein, the uppermost layer of the substrate 2 of the present embodiment is the gold film layer 21, and the material of the auxiliary transfer layer 5 is 3-MTPS' because the thiol terminal functional group of 3-MTPS easily forms a chemical bond with gold, thereby The auxiliary transfer layer 5 is stably coated on the substrate 2. (6) Proceed to step 66: The mold! The molding surface 13 and the film layers 3, 4 face the substrate 2, and the mold! Attaching and pressing to the substrate 2, the emulsion film layer 4 on the protrusion U of the position (4) and the auxiliary transfer layer 5 are placed against the 'oxide film layer 4 and the auxiliary transfer layer 5 (4) oxygen-burning functional group The bond is generated, and since the force 丄 between the 3_MPTS auxiliary transfer layer 5 and the substrate 2 is greater than the force between the PAH electrolyte layer 31|^pDMS mold ι, the field oxide film layer 4 and the functional group of the auxiliary transfer 5 After the bond is completed, the effect of the release transfer can be achieved. It should be noted that the PAH electrolyte layer 31 and ! >DMS mold i suction: force: the intersection is small, so the electrolyte sheet * 3 and the oxide film layer 4 corresponding to the block on the large 4 11 'will be transferred on the auxiliary transfer layer $, ^ An oxide thin film pattern 41 is formed from the emulsion phase layer 4. After the oxide thin film 11 was formed on the four substrates 2, the film was heated and held for 5 minutes to strengthen the chemical bond between the oxide film pattern 41 and the gold film layer 21, and finally the mold was removed to complete the production. According to the above description, the effect of the transfer layer 5 is as an adhesive when the oxide film layer 4 is released by transfer. Since the different substrates 2 have different self-assembly characteristics, the present invention is also required to change the material of the auxiliary transfer layer 5 when the substrate 2 is made of different materials to enable the substrate 2 and the auxiliary. Good chemical bonding can be produced between the terminal functional groups of the transfer layer 5, and of course, the material f of the auxiliary transfer layer 5 is also adjusted in accordance with the material of the oxide thin film layer 4. Referring to Fig. 4 & SEM picture of the mold j of the present invention and the oxide film pattern w formed on the substrate 2. In the figure, the projections of the mold ι are in the form of a linearly spaced arrangement, so that the oxide film pattern 转印 formed by the transfer is also arranged in a straight line. Referring to Fig. 5, there is shown another embodiment of the mold i and a concave portion of the mold k corresponding to the oxide film pattern 4 formed on the substrate 2. A plurality of circular and spaced-apart recesses define an integral protrusion 11 between the recesses 12, so that an oxide film corresponding to the protrusions 11 is formed on the substrate 2 after the transfer. Pattern 41. It can be seen from the above description that the present invention mainly deposits the electrolyte layers 31, 32, and 33 on the surface of the mold 1 for hydrophilic surface modification treatment, so as to facilitate subsequent deposition of the oxide layer 4 by liquid phase deposition. On the mold i, and the action of pattern transfer, the present invention has the following advantages: (1) The present invention does not require the use of a complicated and expensive exposure apparatus in general yellow light lithography etching, so that the advantage of low process cost can be achieved. (7) The present invention does not require the use of a chemical etching solution as in the conventional process, so that the goal of chemical waste reduction and environmental protection can be achieved. 10 200921270 (3) The present invention modifies the mold by the electrolyte unit 3, so that the oxide film layer 4 can be coated on the mold by liquid deposition, because the process temperature of the liquid deposition method is more than that of the prior art. The plating process has a low process temperature, so that the film of the present invention does not damage the surface of the mold when formed, and further, when the oxide film layer 4 is coated by liquid deposition, most of the volatiles are water and volatilized. The ratio is low, generally, heating to 75 〇C at room temperature, the weight loss is smaller than that of other chemical solution methods, and most of the loss is water, so the shrinkage amount of the film thickness is small, so the present invention improves the past use. The problem of volatilization of the organic solvent during film formation by the chemical solution. Therefore, the present invention can maintain the integrity of the oxide film 4, the transfer pattern is continuous without distortion, and the transfer mode of the S-hai pattern is very simple and fast 'and realizes the transfer technology of the oxide film pattern 41'. The purpose of the invention. The above is only the preferred embodiment of the present invention, and is not intended to limit the simple equivalent changes made by the scope of the invention and the description of the invention in the present invention. And modifications are still within the scope of the invention patent. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart showing a method of surface modification transfer technology of the present invention as an oxide film pattern - a preferred embodiment; FIG. 2 is a mold and an electric part used in conjunction with the present invention. 3 is a flow chart of the preferred embodiment; FIG. 4 is a photograph taken by a scanning electron microscope (sem), and FIG. 4 is a top view of the mold, and FIG. 4 (1) is the mold. Side view, 200921270 Figure 4(c) is a picture of an oxide film pattern transferred onto a substrate; and Figure 5 is a picture taken with a scanning electron microscope (SEM), and Figure 5 (a) shows another pattern A top view of the mold, Fig. 5(b) is a perspective view of the mold, and Fig. 5(c) is a picture in which the oxide film pattern is transferred onto a substrate. 12 200921270 [Description of main component symbols] 1 • Mold 3 ... Electrolyte unit 11 ... Projection 31 • First electrolyte layer 12 ... Depression 32 - Second electrolyte layer 13 Molding surface 33 Third electrolyte layer 2 , •• ...substrate 4 oxide film layer 21 •...gold film layer 41 .... oxide film pattern 22 ·- ceria layer 5 .... auxiliary transfer layer 23 ... 矽 layer 61, - 6 6...Step 13