1322331 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種立體壓印技術’特別係關於一種在曲面 基材上進行立體壓印之技術。 【先前技術】1322331 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD OF THE INVENTION The present invention relates to a three-dimensional imprint technique', particularly to a technique for performing three-dimensional imprinting on a curved substrate. [Prior Art]
目前於曲面基材上之壓印技術是先以高分子層塗佈在曲 材上’顧離子束及光罩進行曝光之步驟，經顯影後 咼=子層即具有一定的圖案。利用反應離子蝕刻之方式蝕刻具 有南分子層随之;ε英基材’使®雜紅^英紐上。再以 此有圖案且具曲面之石英基材當作壓印模具進行曲面之壓印 步驟。但該技術有以下缺點，1·該技術需要複雜且昂貴的設 備’例如離f束，2.石英及基材之#面_近，但製備具 有曲面之;5英基材不但需湘離子束源，而且難赠準控制曲 成本Ϊ貝也热法大夏生產。因此，若要將此技術應用於 -業」，ί字無法於大部分產業界所使用之光微影製程設備進 最終勢必需縣新設備’因而增加成本，也此 瘙t的闲Μ。 為解決上述習知技術之缺點，本發曰月提供一種不需要特殊 特殊壓印機台設備之具曲面複合壓印模*，其較石 於非平整表面(如曲面）上之壓印，更可製作較具 變化且大面積之壓印 5 (S) 1322331 【發明内容】 立 辦mint主要目的係提供—種在曲面上藉由壓印形成 體圖案之方法，财法主要包括下列步驟： a. 在石夕晶圓上形成立體結構； b. 形成具曲面之複合壓印模具；以及 c. 壓印形成立體圖案。At present, the imprint technique on the curved substrate is a step of exposing the polymer layer to the curved material by the ion beam and the reticle. After development, the 咼=sublayer has a certain pattern. Etching with a reactive ion etch has a southern molecular layer followed by an ε-infrared substrate. The patterned and curved quartz substrate is used as an imprinting mold for the imprinting process of the curved surface. However, this technology has the following disadvantages: 1. This technology requires complicated and expensive equipment 'for example, from the f-beam, 2. quartz and substrate #面_近, but the preparation has a curved surface; the 5-inch substrate not only needs the ion beam Source, and it is difficult to give the right to control the cost of the mussels and also the hot summer production. Therefore, if this technology is to be applied to the industry, the lithography cannot be used in most of the industry's optical lithography process equipment to enter the final state of the new equipment, thus increasing costs, and so on. In order to solve the above-mentioned shortcomings of the prior art, the present invention provides a curved composite stamping die* which does not require special special stamping machine equipment, and which is more imprinted on a non-flat surface (such as a curved surface), It can produce a embossing with a large area and a large area. 5 (S) 1322331 [Summary of the Invention] The main purpose of the establishment of the mint is to provide a method for forming a body pattern by embossing on a curved surface, and the financial method mainly comprises the following steps: a Forming a three-dimensional structure on the Shi Xi wafer; b. forming a composite imprint mold with a curved surface; and c. embossing to form a three-dimensional pattern.
其中在矽晶圓上形成立體結構之方法已在2〇〇5年4 台灣智慧啦局提出專财請。而本發明之另—目的在提供 一種具曲面之複合壓印模具，其包括一 pDMS壓印模板、二 PDMS塊材，其中該pDMS壓印模板與該pMS塊材係為一體 形；該複合壓印模具之形成方法如下： ⑻幵）成聚一甲基石夕氧炫（polydimethylsiloxane， PDMS)壓印模板：係於相對於立體結構澆入 PDMS ’並交聯得到pDMS壓印模板： (b) 形成PDMS塊材：係以曲面基材為模板，澆入 PDMS，並交聯得到PDMS塊材；Among them, the method of forming a three-dimensional structure on a silicon wafer has been proposed in the 2nd and 5th years. Another object of the present invention is to provide a composite imprinting mold having a curved surface, comprising: a pDMS imprint template, two PDMS blocks, wherein the pDMS imprint template is integral with the pMS block; the composite pressure The formation method of the printing mold is as follows: (8) 幵) Polydimethylsiloxane (PDMS) imprint template: is poured into the PDMS with respect to the three-dimensional structure and cross-linked to obtain the pDMS imprint template: (b) Forming a PDMS block: using a curved substrate as a template, pouring PDMS, and crosslinking to obtain a PDMS block;
(c) 形成複合壓印模具·將PDMS麗印模板貼附於 PDMS塊材，使其成為一體之結構，完成具有與曲 面基材相同曲面之複合壓印模具。 待上述複合壓印模具形成後，本發明之另一目的係提供 一種於曲面基材上之立體壓印方法，該方法包括下列步驟：' ⑻選取基材.取一塗佈有聚甲基丙稀酸曱醋 (Polymethyl Methacrylate，PMMA)之曲面基材； (b)曲面壓印：加熱基材後，將上述複合壓印模具貼合 於曲面基材並進行壓印； ~ 〇 6 1322331 (c)冷卻脫模：持溫持壓30分鐘後，待基材冷卻後脫模 即於曲面基材上得到立體圖案。 【實施方式】 一以了將結合附圖對本發明作進一步之詳細說明。請參考第 盆一圖為本發明於曲面基材上之立體壓印技術之流程， ;J^含⑦晶®上形成立體結構⑽υ、形成具曲面之複合 ^換具⑽2) ’以及騎形成立翻#(SG3)。其詳細實施方 式如下： 1.在矽晶圓上形成立體結構(s〇1) 請-併參考圖二及圖三，圖二a及圖二b為具 ^陣圖案之示意圖，圖三a、圖三b為經二次反應離子^ <之立體圖案示意圖。在本發明中是先選取二種抗化學敍刻性 及抗物理_性不同之光阻，在此發明中是選用—般負型光阻 ϋ型光阻，首先藉負型光阻，树晶片上製作線陣圖案 U11) ’使用之負型光阻為SU8，為市販之光阻劑，將負型光阻 轉塗佈的方式塗佈於碎晶片上，經曝光、顯影後產生線陣 =。接下來藉由正型光阻’在已具有負型絲L所製作之線陣 ，案石夕晶片上，製作與負型光阻之線_案垂直的正型光阻線 陣圖案(S12)。使用之正型光阻為S1818，亦為市販之光阻劑， 同樣地將正型光阻以旋轉塗佈的方式塗佈於已具有負型光阻 所製作之線陣圖案上，經曝光、顯影後，得到與負型光阻所製 作之線陣垂直的正型絲線_#。接著將具有二垂直線陣圖 案的石夕晶片以反應離子蝕刻(Reactive I〇n EtcWng，機進行 f二次的蝕刻後，用丙酮將正型光阻Sl818去除(S13);再進 行第二次的蝕刻’再以Piraha溶液(硫酸及雙氧水之混合溶液） 將SU8負型光阻去除（S14)’即可以在矽晶片上製作出具有高 ，差不同之立體圖案(315)。圖二1)為以掃描式電子顯微鏡⑽M) 觀察矽晶片^之光阻圖案之側視影像照片，其結構就如圖二a 之示意圖所示，具有兩組光阻線陣圖案且互相垂直相交，惟兩 組光阻線陣圖案之寬度不同。負型光阻SU8之線陣圖案寬 10/im’正型光阻S1818之線陣圖案寬度為2#m。圖北為以# 齡矽晶片上之圖案之俯視影像照片， 丨F i看ί ^片上具有高低不同之立體®案，（30)為未 ^。I域’（31)為經-次韻刻區域，⑽為經二次姓刻之區 2.具曲面之複合壓印模具之製作(s〇2) 序可細分*三個部分’—是製作立體圖案之PDMS廢 （f21 ) ’二是製作具有與彎曲基材相同曲面之PDMS塊材 c ’三是將壓印模板貼附於PDMS塊材上，組合成一具曲面 之複合壓印模具(S23)。 a.製作具立體圖案之即似壓印模板(S21)(c) Forming a composite imprint mold • Attaching a PDMS stencil to the PDMS block to form a unitary structure, and completing a composite embossing mold having the same curved surface as the curved substrate. After the above composite imprinting mold is formed, another object of the present invention is to provide a three-dimensional imprinting method on a curved substrate, the method comprising the following steps: ' (8) selecting a substrate. taking a coating with polymethyl propyl Curved substrate of Polymethyl Methacrylate (PMMA); (b) Surface imprint: After heating the substrate, the above composite imprinting mold is attached to the curved substrate and embossed; ~ 〇6 1322331 (c Cooling and demoulding: After holding the temperature for 30 minutes, after the substrate is cooled, the mold is released to obtain a three-dimensional pattern on the curved substrate. [Embodiment] The present invention will be further described in detail with reference to the accompanying drawings. Please refer to the first basin for the three-dimensional imprinting technology on the curved substrate of the invention; J^ contains 7 crystals to form a three-dimensional structure (10), forming a composite with a curved surface (10) 2) 'and riding a standing Turn #(SG3). The detailed implementation is as follows: 1. Form a three-dimensional structure on the germanium wafer (s〇1) - and refer to FIG. 2 and FIG. 3, and FIG. 2a and FIG. 2b are schematic diagrams of the pattern, FIG. 3a. Figure 3b is a schematic diagram of a three-dimensional pattern of the secondary reaction ions. In the present invention, two kinds of photoresists with different chemical resistance and physical resistance are selected first. In this invention, a negative photoresist type photoresist is selected, and the negative photoresist is first used. The line pattern U11) is used. The negative photoresist used is SU8, which is a photoresist of the market. The negative photoresist is applied to the broken wafer, and the line array is formed after exposure and development. . Next, a positive photoresist pattern (S12) perpendicular to the line of the negative photoresist is formed on the case array of the negative-type photoresist by the positive-type photoresist 'on the line array made of the negative-type wire L. . The positive photoresist used is S1818, which is also a commercially available photoresist. Similarly, the positive photoresist is applied by spin coating to a line pattern made of negative photoresist, after exposure, After development, a positive type wire _# perpendicular to the line array made of the negative photoresist was obtained. Then, the stone wafer having the two vertical line pattern is subjected to reactive ion etching (Reactive I〇n EtcWng, after performing the second etching, the positive photoresist S118 is removed by acetone (S13); The etching is further performed by removing the SU8 negative photoresist (S14) with a Piraha solution (a mixed solution of sulfuric acid and hydrogen peroxide) to produce a three-dimensional pattern (315) having a high and a difference on the germanium wafer. Figure 2) In order to observe a side view image of the photoresist pattern of the tantalum wafer by a scanning electron microscope (10) M), the structure is as shown in the schematic diagram of FIG. 2a, and has two sets of photoresist line patterns and perpendicularly intersect each other, but the two groups The width of the photoresist line pattern is different. The line pattern width of the negative photoresist SU8 is 10# im' positive type resist S1818 has a line pattern width of 2#m. The north of the picture is a bird's-eye view of the pattern on the # 矽 矽 wafer, 丨F i see ί ^ on the film with different heights of the stereoscopic case, (30) is not ^. The I domain '(31) is the warp-timed engraved area, (10) is the area of the second surname engraved 2. The composite imprinting mold with curved surface (s〇2) The sequence can be subdivided * three parts' - is the production of three-dimensional Pattern PDMS waste (f21) 'The second is to make a PDMS block with the same curved surface as the curved substrate c'. The third is to attach the imprint template to the PDMS block and combine it into a curved composite imprinting mold (S23) . a. Producing a three-dimensional pattern that resembles an imprint template (S21)
請參考圖四，以矽晶圓上之立體圖案為模仁(41)，並將此模仁 =1)置於一容器内，於本發明中，此容器為塑膠容器（4〇)，材 貝為PS，直徑約為9〇mm，高約為i5mm ,此塑膠容器具有不與 PDMS互相沾黏之特性，故易於脫模。將未交聯之pDMS (polydimethylsiloxane)與 lg 交聯劑（curing agent)混合， 兩者混合重量比例為10 :；[。充分攪拌混合後，將此混合溶液 (42)倒入已放置模仁(41)之塑膠容器内（4〇)，靜置12小時後 置入60°C之烘箱使其能完全交聯。以此方法可將模仁（41)之 立體圖案轉移至PDMS模板上，經與模仁(41)及塑膠容器（40) 脫模後’即得到具立體圖案之PDMS壓印模板(43)，此PDMS壓 印模板(43)厚度小於〇. 5腿。請參考圖五a及圖五b，此兩張 圖為以掃描式電子顯微鏡觀察PDMS壓印模板(43)上之立體圖 案之影像照片，此PDMS壓印模板(43)上之立體圖案為以複製 矽晶片上之立體圖案得到，故圖案之高低起伏與矽晶片之圖案 完全相反。 1322331 b. 製作具有與彎曲基材相同曲面之pdms塊材(S22) 請參考圖六’將彎曲基材放置於塑膠容器内，此塑膠容器 之大小及材質與製作立體圖案之PDMS壓印模板(43)中所使用 之塑膠谷器相同’本實施例中使用之彎曲基材為一具有曲面之 玻璃基材（61)，此玻璃基材（61)已預先做過表面處理，故不與 PDMS互相沾黏，利於脫模。表面處理之方法為將此玻璃基材（6j) 浸泡於 OTS(n-Octadecyltrichlorosilane)及環己院 (cyclohexane)之混合溶液内，〇TS及環己烷之體積比例約為 1 . 100。取 30g 未交聯之 pDMS( polydimethyl si loxane )與 3g交聯劑混合’兩者混合重量比例為1〇 :丨。充分攪拌混合後， 將此混合溶液（62)倒入已放置玻璃基材（61)之塑膠容器内 (60) ’靜置12小時後置入6〇。(：之烘箱使其能完全交聯。經脫 模後’即得到一具有與彎曲基材相同曲面之PDMS塊材（63)。 c. 將壓印模板貼附於PDMS塊材上，組合成一具曲面之複合壓 印模具(S23) ^請參考圖七，因為在a中提到之具立體圖案之PDMS壓印 模，(43)其厚度小於0.5腿，故不需其他之黏著劑或其他器具 固_定就可與b中之PDMs塊材（63)直接結合，亦即將PDMS壓印 巧板(43)貼附於pdms塊材（63)上，形成一具曲面之複合壓印 模具(73)。推測此為靜電力之作用使pDMS壓印模板(43)及 PDMS塊材（63)可緊密結合。 而實際將立體壓印技術用於曲面基材上之流程如圖八， L取一塗佈有向分子PMMA(81)的曲面基材，本發明選用玻璃 基材(80)。 2·玻璃基材(80)加熱後’將複合壓印模具(7〇)貼合於曲面基 材並進行壓印。持溫持Μ 30分鐘後’待基板冷卻舰模，即 可於曲面基材上得到ΡΜΜΑ之立體結構。請參考圖九，圖九 10 1322331 為以掃描式電子顯微鏡觀察曲面基材上之PMMA立體圖案之影 像照片。此PMMA立體圖案是藉由具有圖五所示之微結構之壓 印模具經由壓印之過程所得到，故圖案之高低起伏與圖五所 示之圖案為完全相反。 11 1322331 【圖式簡單說明】 圖一.於曲面基材上之立體壓印技術之流程 圖二a.具有二垂直光阻線陣圖案之立體示意圖 圖二b.具有二垂直光阻線陣圖案之SEM側視圖 圖三a.經二次反應離子蝕刻後矽晶片上之立體 圖案示意圖 圖三b.經二次反應離子蝕刻後矽晶片上之立體 圖案SEM俯視圖 圖四.立體圖案之PDMS壓印模板製作方式 圖五a. PDMS壓印模板上之立體圖案之SEM圖 圖五b. PDMS壓印模板上之立體圖案之SEM圖 圖六.具有與彎曲基材相同曲面之PDMS塊材製作方式 圖七.具曲面之複合壓印模具製作之示意圖 圖八.立體壓印技術應用於曲面基材上之示意圖 圖九曲面基材上之BMA立體圖案之SEM圖。 【主要元件符號說明】 30未經蝕刻區域 31經一次蝕刻區域 32經二次钱刻區域 40塑膠容器 41模仁 42混合溶液 43 PDMS壓印模板 60塑膠容器 61玻璃基材 62混合溶液 63 PDMS塊材 70複合壓印模具 80曲面基材 81高分子PMMA層 12Referring to FIG. 4, the three-dimensional pattern on the wafer is used as a mold core (41), and the mold core = 1) is placed in a container. In the present invention, the container is a plastic container (4 inch). The shell is PS, the diameter is about 9〇mm, and the height is about 5mm. The plastic container has the characteristics of not sticking to the PDMS, so it is easy to demould. The uncrosslinked pDMS (polydimethylsiloxane) is mixed with the lg crosslinking agent, and the weight ratio of the two is 10:; After thoroughly stirring and mixing, the mixed solution (42) was poured into a plastic container (4 Torr) in which the mold core (41) was placed, and allowed to stand for 12 hours, and then placed in an oven at 60 ° C to be completely crosslinked. In this way, the three-dimensional pattern of the mold core (41) can be transferred to the PDMS template, and after being demolded from the mold core (41) and the plastic container (40), a PDMS imprint template (43) having a three-dimensional pattern is obtained. The thickness of the PDMS imprint template (43) is less than 〇. 5 legs. Please refer to FIG. 5a and FIG. 5b. The two figures are the images of the three-dimensional pattern on the PDMS imprint template (43) observed by a scanning electron microscope. The three-dimensional pattern on the PDMS imprint template (43) is The three-dimensional pattern on the ruthenium wafer is reproduced, so that the height of the pattern is completely opposite to the pattern of the ruthenium wafer. 1322331 b. Making a pdms block with the same curved surface as the curved substrate (S22) Please refer to Figure 6 for placing the curved substrate in a plastic container. The size and material of the plastic container and the PDMS imprint template for making a three-dimensional pattern ( The plastic grain used in 43) is the same. 'The curved substrate used in this embodiment is a curved glass substrate (61). This glass substrate (61) has been surface treated in advance, so it is not compatible with PDMS. Stick to each other, which is good for demoulding. The surface treatment method is to immerse the glass substrate (6j) in a mixed solution of OTS (n-Octadecyltrichlorosilane) and cyclohexane, and the volume ratio of 〇TS to cyclohexane is about 1.100. 30 g of uncrosslinked pDMS (polydimethyl si loxane ) was mixed with 3 g of a crosslinking agent. The mixing ratio of the two was 1 〇 : 丨. After thoroughly stirring and mixing, the mixed solution (62) was poured into a plastic container (60) on which the glass substrate (61) was placed, and left to stand for 12 hours, and then placed 6 inches. (: The oven allows it to be completely crosslinked. After demolding, a PDMS block (63) having the same curved surface as the curved substrate is obtained. c. The imprint template is attached to the PDMS block and combined into one Composite imprinting mold with curved surface (S23) ^Please refer to Figure 7. Because the PDMS imprinting mold with three-dimensional pattern mentioned in a, (43) its thickness is less than 0.5 leg, no other adhesive or other adhesive is needed. The fixture can be directly combined with the PDMs block (63) in b, that is, the PDMS stamping plate (43) is attached to the pdms block (63) to form a curved composite imprinting die ( 73) It is speculated that this is the effect of electrostatic force to make the pDMS imprint template (43) and the PDMS block (63) can be tightly combined. The actual process of using the three-dimensional imprint technique on the curved substrate is as shown in Fig. 8. A curved substrate coated with a molecular PMMA (81), the glass substrate (80) is selected in the present invention. 2. After the glass substrate (80) is heated, the composite imprinting mold (7〇) is attached to the curved base. The material is embossed. After holding the temperature for 30 minutes, the substrate will be cooled by the substrate, and the three-dimensional structure of the crucible can be obtained on the curved substrate. Please refer to Figure IX. Nine 10 1322331 is a photo image of a PMMA stereoscopic pattern on a curved substrate observed by a scanning electron microscope. The PMMA three-dimensional pattern is obtained by an imprinting process having the microstructure shown in FIG. The height of the pattern is exactly the opposite of the pattern shown in Figure 5. 11 1322331 [Simple illustration of the diagram] Figure 1. Flow chart of the three-dimensional imprinting technique on the curved substrate. a. Two vertical photoresist line pattern FIG. 2 is a side view of a SEM having a pattern of two perpendicular photoresist lines. FIG. 3 is a schematic diagram of a three-dimensional pattern on a wafer after secondary reactive ion etching. FIG. 3 is a diagram of a wafer after secondary reactive ion etching. SEM top view of the three-dimensional pattern on the top. Figure 4. Manufacture of the PDMS imprint template of the three-dimensional pattern. Figure a. SEM image of the three-dimensional pattern on the PDMS imprint template. Figure b. SEM image of the three-dimensional pattern on the PDMS imprint template The fabrication method of PDMS block with the same curved surface as the curved substrate. Figure 7. Schematic diagram of the composite imprinting mold with curved surface. Figure 8. Schematic diagram of the three-dimensional imprinting technique applied to the curved substrate. SEM image of the BMA three-dimensional pattern on the surface. [Main component symbol description] 30 unetched region 31 after one etching region 32 by double money engraving area 40 plastic container 41 mold core 42 mixed solution 43 PDMS imprint template 60 plastic container 61 Glass substrate 62 mixed solution 63 PDMS block 70 composite imprinting mold 80 curved substrate 81 polymer PMMA layer 12