TWI578399B - Method for producing nanowires - Google Patents
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本發明係關於一種以核酸作為過渡支撐結構之製造奈米線之方法。本方法係將一金屬-DNA複合物薄膜施用於固態支撐物上。藉由控制咖啡漬圈環效應之毛細管力並刮除該核酸金屬奈米粒子薄膜,使奈米粒子聚積於切除區之邊緣,從而製造出微米至奈米尺度之金屬線。在其他實施例中,本發明係以酵素水解法去除核酸以取得最終之金屬線。本發明另提供包含以本方法製成之電路之晶片。 This invention relates to a method of making nanowires using nucleic acids as a transitional support structure. The method applies a metal-DNA complex film to a solid support. The micron to nanometer-scale metal wires are fabricated by controlling the capillary force of the coffee ring effect and scraping the nucleic acid metal nanoparticle film to accumulate the nanoparticles at the edge of the cut-out region. In other embodiments, the invention removes nucleic acids by enzymatic hydrolysis to obtain the final metal wire. The invention further provides a wafer comprising a circuit made by the method.
去氧核糖核酸(DNA)模板法在過去數十年中已被用於製造微米至奈米級之金屬線。此製造方法雖十分有效,但單位時間產出量及可控性始終偏低。本發明提出一種以劃線或「書寫」之方式在矽(Si)晶圓上利用天然毛細管力製造微米至奈米級銀(Ag)線之新穎方法。因毛細管力而產生之咖啡漬圈環乾燥效應使帶有銀之DNA分子朝劃線區之邊緣擴散,進而沿著劃線而成之圖案沉積。之後再利用以酵素輔助之蝕刻法去除DNA過渡支撐結構,留下晶圓上之銀線。此項技術可望改良目前以DNA輔助之金屬奈米圖案及奈米結構成形法,使其得以應用於奈米電子學。 Deoxyribonucleic acid (DNA) template methods have been used to fabricate micron to nanoscale metal lines for the past several decades. Although this manufacturing method is very effective, the output per unit time and controllability are always low. The present invention provides a novel method for fabricating micron to nanoscale silver (Ag) lines on a germanium (Si) wafer using natural capillary forces in a scribing or "writing" manner. The drying effect of the coffee ring caused by the capillary force causes the DNA molecules with silver to diffuse toward the edge of the scribe region and deposit along the scribed pattern. The DNA transition support structure is then removed using an enzyme-assisted etching method to leave the silver lines on the wafer. This technology is expected to improve the current DNA-assisted metal nanopattern and nanostructure forming method, enabling it to be applied to nanoelectronics.
近幾年,以DNA輔助之微米及奈米結構成形法已被廣泛研究,期能應用於各種不同領域。此種包括金屬線(例如銀線)之結構展現極佳之空間解析度與靈活性。探究上述特性之成因為:當吾人以成股DNA 作為金屬奈米粒子之成形模板時,成股DNA之高專一性可使金屬奈米粒子沿著DNA之骨幹成形[4]。因此,DNA分子可使金屬選擇性地與之結合,因而提供靈活且為奈米級之模板成形效果。針對解析度為傳統微電子學所無法達成之導線製程,DNA電子學可發揮其自補性以提供適當工具。然而,以DNA輔助之金屬線圖案成形法仍無法在工業化過程中解決單位時間產出量偏低之問題。重點在於,必須先處理靈活「書寫」之能力及可控性,再談如何降低相關製程之成本與複雜度。近來有人提出若干可克服上述問題之簡潔設計結構,強調可操控圖案之對準方式及再現性。但該等方法仍缺少達成工業級可控性與精準度所需之決定性步驟,因而不具有實際投入生產之商業可行性。 In recent years, DNA-assisted micron and nanostructure forming methods have been extensively studied and can be applied to various fields. This structure, including metal wires (such as silver wires), exhibits excellent spatial resolution and flexibility. Exploring the above characteristics: When I am a strand of DNA As a template for forming metal nanoparticles, the high specificity of stranded DNA allows metal nanoparticles to be formed along the backbone of DNA [4]. Thus, the DNA molecule allows the metal to selectively bind to it, thereby providing a flexible and nano-sized template forming effect. For wire processes where resolution is not possible with traditional microelectronics, DNA electronics can be self-compensating to provide the right tools. However, the DNA-assisted metal wire patterning method still cannot solve the problem of low output per unit time in the industrialization process. The point is that we must first deal with the ability and controllability of flexible "writing" and then talk about how to reduce the cost and complexity of related processes. Recently, a number of concise design structures have been proposed which overcome the above problems, emphasizing the alignment and reproducibility of the steerable patterns. However, these methods still lack the decisive steps required to achieve industrial-level controllability and precision, and thus do not have the commercial viability of actual production.
承上,本發明之一目的係以具有商業可行性之方式製造以DNA過渡支撐結構為基礎之金屬奈米線,詳言之則係提供一種可將奈米線以受控方式施用於固態支撐物表面之方法,使吾人得以在固態支撐物上設計及製造電路,進而製造出矽晶片。 In view of the above, one of the objects of the present invention is to manufacture a metal nanowire based on a DNA transition support structure in a commercially viable manner, in particular to provide a nanowire in a controlled manner for solid support. The method of the surface allows us to design and fabricate circuits on solid supports to create tantalum wafers.
為解決上述問題,本發明之第一態樣提供一種可於一支撐材料上製造微米至奈米線之方法,其包含下列步驟:(a)提供一固態支撐材料;(b)將一包含核酸與金屬奈米粒子之液態組合物施用於該支撐材料之表面,藉以取得一固態支撐材料,其表面之至少一個區域係由該液態組合物覆蓋,且至少一個區域未被該液態組合物覆蓋,從而在該液態組合物所覆蓋之區域與該液態組合物所未覆蓋之區域間之邊緣處製造出 微米至奈米線;及(c)若有需要,可去除該核酸。 In order to solve the above problems, a first aspect of the present invention provides a method of fabricating a micron to nanowire on a support material, comprising the steps of: (a) providing a solid support material; (b) providing a nucleic acid comprising A liquid composition with metal nanoparticle is applied to the surface of the support material to obtain a solid support material having at least one region of the surface covered by the liquid composition and at least one region not covered by the liquid composition. Thereby producing at the edge between the area covered by the liquid composition and the area not covered by the liquid composition Micron to nanowire; and (c) the nucleic acid can be removed if desired.
較佳者,該金屬係選自白金、鐵、鈷、鎳、金、銀、銅、氧化鐵、氧化銅、氧化鋅,及其合金,若為銀(Ag)則更佳。 Preferably, the metal is selected from the group consisting of platinum, iron, cobalt, nickel, gold, silver, copper, iron oxide, copper oxide, zinc oxide, and alloys thereof, and more preferably silver (Ag).
在較佳實施例中,該核酸係選自單股(ss)或雙股(ds)之DNA、PNA或RNA,若為雙股DNA則更佳。 In a preferred embodiment, the nucleic acid is selected from the group consisting of single-stranded (ss) or double-stranded (ds) DNA, PNA or RNA, and more preferably double-stranded DNA.
在一較佳實施例中則必須執行步驟(c)。較佳者,執行步驟(c)之方式係透過酵素蝕刻,若使用核酸酶則更佳,尤佳者係使用去氧核糖核酸酶。 In a preferred embodiment, step (c) must be performed. Preferably, the step (c) is carried out by enzyme etching, preferably using a nuclease, and particularly preferably using a ribozyme.
就本發明而言,該固態支撐材料之一較佳實施例為矽(Si),若為一矽晶圓則更佳。 For the purposes of the present invention, one preferred embodiment of the solid support material is bismuth (Si), more preferably a wafer.
在另一實施例中,該液態組合物中添加有一表面張力降低劑,較佳者為一表面活性劑。 In another embodiment, a surface tension reducing agent, preferably a surfactant, is added to the liquid composition.
就步驟(b)而言,此步驟最好包含下列次步驟:將該液態組合物施用於該固態支撐材料,然後從該固態支撐材料之表面去除該液態組合物之若干部分以取得一固態支撐材料,其表面之至少一個區域係由該液態組合物覆蓋,且至少一個區域未被該液態組合物覆蓋。執行所述去除之理想方式係刮除、切除或藉由劃線去除該液態組合物。在本發明中,刮除、切除或藉由劃線去除意指去除該液態組合物時,去除之深度直達該固態支撐材料。 In the case of step (b), the step preferably comprises the step of applying the liquid composition to the solid support material and then removing portions of the liquid composition from the surface of the solid support material to achieve a solid support The material, at least one region of its surface is covered by the liquid composition, and at least one region is not covered by the liquid composition. The desired way of performing the removal is to scrape, cut or remove the liquid composition by scribing. In the present invention, scraping, cutting, or by scribing removal means removing the liquid composition to a depth that is as direct as the solid support material.
因此,本發明之方法提供一種可將金屬奈米線之預定圖案施用於固態支撐物(例如矽晶圓)之簡單方式,下文對此將有進一步說明。 若使用刮除法,該預定圖案之一較佳實施例為一線路,例如電路。 Thus, the method of the present invention provides a simple way to apply a predetermined pattern of metal nanowires to a solid support, such as a tantalum wafer, as will be further explained below. If a scraping method is used, one preferred embodiment of the predetermined pattern is a line such as a circuit.
在該方法之一實施例之步驟(b)中,將該液態組合物施用於該固態支撐材料之表面後,尚須使該液態組合物乾燥以取得一位於該固態支撐材料之表面上且包含該等金屬奈米粒子與該核酸之凝膠狀薄膜。為促進所述乾燥,可添加一乾燥劑,例如一溶劑,較佳者為乙醇。例如,所述乾燥可為風乾,較佳者係風乾至少1、2、3、4、5、6、7小時或更久。所述乾燥之一替代做法係將該液態組合物以凝膠或薄膜之形式施用於該固態支撐材料。使用該核酸/金屬奈米粒子之凝膠狀或薄膜狀組合物之優點在於,該種薄膜可自表面輕易刮除,因而製造出一受控邊緣。此邊緣之形狀即為後續製成之奈米線之模板。因此,該邊緣愈銳利,該固態支撐材料上之奈米線密度就可能愈高。 In step (b) of an embodiment of the method, after applying the liquid composition to the surface of the solid support material, the liquid composition is still dried to obtain a surface on the solid support material and comprising A gel-like film of the metal nanoparticles and the nucleic acid. To facilitate the drying, a desiccant, such as a solvent, preferably ethanol, may be added. For example, the drying can be air drying, preferably air drying for at least 1, 2, 3, 4, 5, 6, 7 hours or longer. One alternative to the drying is to apply the liquid composition to the solid support material in the form of a gel or film. An advantage of using the gel-like or film-like composition of the nucleic acid/metal nanoparticle is that the film can be easily scraped off from the surface, thereby producing a controlled edge. The shape of this edge is the template for the subsequently prepared nanowire. Thus, the sharper the edge, the higher the nanowire density on the solid support material.
以下將詳細說明本發明之原理。概括言之,所述微米至奈米線之製造方式係令該核酸/金屬奈米粒子擴散至所述邊緣。該核酸-金屬材料朝所述邊緣擴散時,便聚積於所述邊緣並形成線料結構。促成所述擴散之原理係所謂「咖啡漬圈環效應」。 The principles of the invention are described in detail below. In summary, the micron to nanowire is fabricated in such a manner that the nucleic acid/metal nanoparticle diffuses to the edge. As the nucleic acid-metal material diffuses toward the edge, it accumulates at the edge and forms a strand structure. The principle that contributes to the diffusion is the so-called "coffee stain ring effect".
本發明所欲解決之問題尚可由一種用以製造具有微米至奈米線之矽晶圓之方法加以解決,該方法包含下列步驟:(a)提供一矽晶圓;(b)提供一包含核酸與金屬奈米粒子複合物之液態組合物;(c)將該液態組合物施用於該矽晶圓之表面;(d)使該矽晶圓乾燥以取得一表面上具有一核酸/金屬奈米粒子薄膜之矽晶圓; (e)從該矽晶圓之表面去除該核酸/金屬奈米粒子薄膜之若干部分,藉以為該矽晶圓之表面上之薄膜製造邊緣;及(f)若有需要,可以水解法去除該核酸,較佳者係使用酵素水解法,若使用去氧核糖核酸酶則更佳。 The problem to be solved by the present invention can be solved by a method for fabricating a germanium wafer having micron to nanowires, the method comprising the steps of: (a) providing a germanium wafer; and (b) providing a nucleic acid comprising a liquid composition with a metal nanoparticle composite; (c) applying the liquid composition to the surface of the tantalum wafer; (d) drying the tantalum wafer to obtain a nucleic acid/metal nanoparticle on a surface a wafer of particle film; (e) removing portions of the nucleic acid/metal nanoparticle film from the surface of the germanium wafer, thereby fabricating an edge for the film on the surface of the germanium wafer; and (f) removing the solvent if necessary The nucleic acid is preferably an enzyme hydrolysis method, and more preferably a deoxyribonuclease.
較佳者,步驟(e)包含從該矽晶圓之表面刮除或藉由劃線去除該薄膜(如前述)。 Preferably, step (e) comprises scraping off the surface of the germanium wafer or removing the film by scribing (as described above).
同樣如前文所述,最好必須執行步驟(f)。 Also as described above, it is preferable to perform step (f).
本發明之他種態樣係關於一種以本文所述之方法製成之固態支撐物或矽晶圓。 Other aspects of the invention pertain to a solid support or tantalum wafer made by the methods described herein.
本發明另提供一種製造一電路晶片之方法,其包含執行前述之一方法。 The present invention further provides a method of fabricating a circuit wafer comprising performing one of the foregoing methods.
本發明之另一態樣係關於一種電腦,其包含本發明之固態支撐物、矽晶圓或晶片。 Another aspect of the invention pertains to a computer comprising the solid support, tantalum wafer or wafer of the present invention.
本發明之又一態樣係關於一種以本發明方法製成之微米至奈米線。 Yet another aspect of the invention pertains to a micron to nanowire made by the method of the invention.
以上已根據特定較佳實施例明確描述本發明之內容。以下範例僅供例示之用,並非用於將本發明限縮在其最廣義解讀及等效構型之原理及範圍內。 The content of the present invention has been explicitly described above in accordance with certain preferred embodiments. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention to the principles and scope of the invention.
第1圖:原子力顯微鏡(AFM)成像。接觸型之AFM成像顯示:(a)酵素蝕刻前之光學影像、(b)酵素蝕刻後之光學影像、(c)高度變化及(c)銀 線之三維結構。 Figure 1: Atomic Force Microscopy (AFM) imaging. Contact type AFM imaging shows: (a) optical image before enzyme etching, (b) optical image after enzyme etching, (c) height change, and (c) silver The three-dimensional structure of the line.
第2圖:元素成分分析。影像(a)、(b)及(c)顯示銀奈米粒子在矽晶圓上之分布。圖中銀分布之量測位置為綠點處(代表晶圓基材內之不同位置點)、薄膜內部、線料上及切除區。 Figure 2: Elemental composition analysis. Images (a), (b), and (c) show the distribution of silver nanoparticles on the germanium wafer. The measurement position of the silver distribution in the figure is at the green point (representing the different points in the wafer substrate), the inside of the film, the line material and the cutting area.
在本發明中,發明人係以兩種創新概念克服前述問題,概念一係以毛細管力誘使DNA-銀分子朝受控之劃線處流動,概念二係對矽晶圓上之DNA過渡支撐結構進行酵素蝕刻。本發明所提出之技術係於劃線前利用DNA-銀奈米粒子(NP)薄膜之自組裝特性,劃線後則透過「乾燥」效應所產生之毛細管力誘使奈米粒子移往劃線處,進而在薄膜上形成金屬-DNA圖案。 In the present invention, the inventor overcomes the aforementioned problems with two innovative concepts, the concept of which is to induce DNA-silver molecules to flow toward a controlled scribe line by capillary force, and the concept second is to support the DNA transition on the 矽 wafer. The structure is subjected to enzyme etching. The technique proposed by the present invention utilizes the self-assembly property of DNA-silver nanoparticle (NP) film before scribing, and the capillary force generated by the "drying" effect after scribing induces the nanoparticle to move to the scribing. At the same time, a metal-DNA pattern is formed on the film.
之後再以酵素蝕刻法去除不需要之DNA材料,使晶圓上僅生成銀線。原子力顯微鏡(AFM)之量測結果確認上述成果,並顯示一粒狀線料結構。掃描式電子顯微鏡-能量色散X射線分析(SEM-EDX)則證實線料上沉積有顯著較大量之銀奈米粒子。以上觀察結果確認表面掃描之金屬區,並顯示銀總成之次微米至奈米尺度。因此,本方法之潛在應用包括可用於製造可圖案化金屬線之微米至奈米級解析度。發明人相信,此應用可徹底縮小元件間距,並以受控方式提高配線密實度,以滿足電子裝置微型化之所需。 The unwanted DNA material is then removed by enzyme etching to produce only silver lines on the wafer. The results of the atomic force microscopy (AFM) confirmed the above results and showed a granular strand structure. Scanning electron microscopy-energy dispersive X-ray analysis (SEM-EDX) confirmed the deposition of significantly larger amounts of silver nanoparticles on the strands. The above observations confirm the metal area of the surface scan and show the submicron to nanometer scale of the silver assembly. Thus, potential applications of the method include micron to nanoscale resolution that can be used to fabricate patterned metal lines. The inventor believes that this application can completely reduce the component pitch and improve the wiring density in a controlled manner to meet the miniaturization of electronic devices.
材料與方法Materials and Methods
矽晶圓基材之製備Preparation of germanium wafer substrate
尺寸為20英吋x0.5公厘之矽晶圓(單面拋光,<100>,n型, 無摻雜)係購自英國Sigma公司,使用前保持冷藏(約4℃)。本實驗所用之晶圓僅使用一次,且係直接自供應商取得,因此不需額外加以清理。 Wafers measuring 20 inches x 0.5 mm (single-sided polished, <100>, n-type, Undoped) was purchased from Sigma, UK and kept refrigerated (about 4 ° C) before use. The wafers used in this experiment were used only once and were obtained directly from the supplier, so no additional cleaning was required.
銀奈米粒子之培養Cultivation of silver nanoparticles
將取自大腸桿菌RR1(英國Sigma公司)且經冷凍乾燥之pBR322 DNA(MW 2.9x106 Da)裝入小瓶內,加入0.5毫升之去離子水(18.2MΩ.cm)予以混合。將此DNA溶液400微升與400微升之銀奈米粒子分散液(粒徑大小為10奈米,濃度為0.2mg.mL-1)在水性緩衝液(英國Sigma公司)中混合,形成一混合溶液。對此溶液進行隔夜培養,以利金屬銀聚集體與DNA分子結合。 The freeze-dried pBR322 DNA (MW 2.9 x 106 Da) from Escherichia coli RR1 (Sigma, UK) was placed in a vial and mixed with 0.5 ml of deionized water (18.2 MΩ.cm). 400 μL of this DNA solution and 400 μl of silver nanoparticle dispersion (particle size of 10 nm, concentration of 0.2 mg.mL -1 ) were mixed in an aqueous buffer (Sigma, UK) to form a mixture. This solution was cultured overnight to facilitate metal silver aggregates to bind to DNA molecules.
DNA-銀奈米粒子線之製造Manufacture of DNA-silver nanoparticle lines
利用微量吸管,將50微升之DNA-銀奈米粒子溶液滴在矽晶圓上。15分鐘後,將一滴(10微升)乙醇滴在上述液滴上,放置隔夜,靜待風乾。以外科手術刀劃線後,可觀察到在視覺上產生分離現象(即形成切除區)。然後以酵素水解法去除DNA過渡支撐結構。將含有DNA-銀奈米粒子薄膜之晶圓浸入10毫升之1mM磷酸鉀緩衝溶液(pH 7.4,其含有取自牛胰臟且濃度為2mg.mL-1之去氧核糖核酸酶I(英國Sigma公司)及濃度為2mM之氯化鎂(英國Sigma公司))中,靜待酵素發揮作用。 50 microliters of the DNA-silver nanoparticle solution was dropped onto the tantalum wafer using a micropipette. After 15 minutes, a drop (10 μl) of ethanol was dropped on the above droplets, left overnight, and allowed to air dry. After scribing with a surgical knife, it was observed that a separation phenomenon was visually observed (i.e., a cut-out region was formed). The DNA transition support structure is then removed by enzyme hydrolysis. The wafer containing the DNA-silver nanoparticle film was immersed in 10 ml of a 1 mM potassium phosphate buffer solution (pH 7.4, which contained a deoxyribonuclease I (concentrated in 2 mg.mL -1 from bovine pancreas). The company and the concentration of 2mM magnesium chloride (Sigma, UK), wait for the enzyme to work.
AFM成像AFM imaging
以AFM探針執行AFM表面及電成像(Veeco Dimension 3100),該探針具有接觸型尖端(型號為SCM-PIC,且含有以銻(n)摻雜之矽)。 AFM surface and electrical imaging (Veeco Dimension 3100) was performed with an AFM probe having a contact tip (model SCM-PIC and containing germanium doped with antimony (n)).
SEM-EDX量測SEM-EDX measurement
以SEM-EDX儀器(型號為Verios 460,美國FEI公司製造)進行元素分析。 Elemental analysis was carried out by a SEM-EDX instrument (model Verios 460, manufactured by FEI, USA).
範例1:銀微米線之製造Example 1: Manufacturing of Silver Microwires
製程包含三個主要階段:DNA-銀奈米粒子懸浮液之自組裝、以劃線或書寫方式形成線路,以及以酵素水解法去除DNA[8]。第一階段係將一滴(50微升)上述懸浮液滴在乾淨之矽晶圓上,然後施用約10微升之乙醇,靜待風乾。乙醇之作用係將DNA濃縮及脫水,使其在晶圓上展現機械穩定性[9]。水分子經隔夜乾燥而蒸發後,觀察到凝膠狀之薄膜殘餘物。之後以劃線法形成切除區,切除深度直達晶圓,藉以將切除區之邊緣有效分開。此混合薄膜之凝膠狀特性使DNA-銀奈米粒子朝切除區靈活移動。此現象可由第1a圖中較高之材料密度獲得證明,其成因則為源自切除區邊緣之毛細管流。之後對DNA過渡支撐結構進行酵素蝕刻,所用酵素為去氧核糖核酸酶[8]。光學影像可顯示蝕刻前後之差別:基材經酵素處理後變得更加乾淨,如第1b圖所示。 The process consists of three main stages: self-assembly of DNA-silver nanoparticle suspensions, formation of lines by scribing or writing, and removal of DNA by enzymatic hydrolysis [8]. In the first stage, a drop (50 microliters) of the above suspension was dropped onto a clean crucible wafer, and then about 10 microliters of ethanol was applied and allowed to air dry. The role of ethanol is to concentrate and dehydrate the DNA to exhibit mechanical stability on the wafer [9]. After the water molecules were dried overnight and evaporated, a gel-like film residue was observed. The cut-out area is then formed by scribing, and the depth of the cut is directly to the wafer, thereby effectively separating the edges of the cut-out area. The gel-like nature of this mixed film allows the DNA-silver nanoparticles to move flexibly toward the resection zone. This phenomenon is evidenced by the higher material density in Figure 1a, which is caused by capillary flow from the edge of the ablation zone. The DNA transition support structure is then subjected to enzymatic etching, and the enzyme used is DNase [8]. The optical image shows the difference between before and after etching: the substrate becomes cleaner after being treated with enzyme, as shown in Figure 1b.
範例2:銀線之表面形態Example 2: Surface morphology of silver wire
第1圖清楚顯示以本發明方法製成之銀線結構。光學影像顯示,劃線處之兩側邊緣均出現較高之材料密度(第1a圖)。此觀察結果與溶液液滴乾燥時因毛細管力而產生之「咖啡漬圈環」效應[10]吻合,最終則形成連續之粒狀線料結構(第1c及1d圖)。量測結果顯示平均高度為約200至400奈米,其中偶有最高可達800奈米之突起,寬度量測值則小於10微米。以上數值證明本實驗已成功製造出次微米至奈米級之尺度。 Figure 1 clearly shows the silver wire structure produced by the method of the present invention. The optical image shows a higher material density on both sides of the scribe line (Fig. 1a). This observation coincides with the "coffee ring" effect [10] produced by the capillary force when the solution droplets are dried, and finally forms a continuous granular strand structure (Figs. 1c and 1d). The measurement results show an average height of about 200 to 400 nm, with occasional protrusions up to 800 nm and width measurements less than 10 microns. The above values demonstrate that this experiment has successfully produced sub-micron to nanoscale scales.
範例3:SEM-EDX分析Example 3: SEM-EDX Analysis
發明人另沿著晶圓基材之不同區域進行元素成分分析以證明本實驗已成功製造出銀線(第2圖)。分析結果顯示,線料結構沿線之銀百分比顯著高於其他區域之銀百分比。第2圖特別顯示銀在線料上之分布(a)、銀在薄膜內之分布(b),及銀在切除區之分布。一如預期,在毛細管力之作用下,金屬奈米粒子僅沿著線料結構沉積,其他兩區幾乎未見任何沉積。 The inventors performed elemental composition analysis along different regions of the wafer substrate to prove that the silver wire was successfully fabricated in this experiment (Fig. 2). The results of the analysis show that the percentage of silver along the strand structure is significantly higher than the percentage of silver in other regions. Figure 2 particularly shows the distribution of silver on the wire (a), the distribution of silver in the film (b), and the distribution of silver in the ablation zone. As expected, under the action of capillary forces, the metal nanoparticles were deposited only along the strand structure, and almost no deposition was observed in the other two regions.
本文所說明之技術提出兩項創新做法,期能突破當前以DNA輔助之金屬微米至奈米線製程之主要發展瓶頸。相較於其他方法,本發明方法之主要優點在於,善用天然毛細管力驅使DNA-銀奈米粒子朝向以物理方式形成之切割區或劃線區擴散,之後再以去氧核糖核酸酶進行DNA過渡支撐結構之生化酵素蝕刻即可產生純粹之銀線結構。上述第二步驟對於如何製備乾淨、僅包含線料,且可整合於奈米電子架構之基材做出重大貢獻。上述第一步驟則透過使用毛細管力而提高金屬線「書寫」過程之可控性及靈活度,此與文獻中製造任意線料及圖案時之情況不同[6,7,11-13]。 The technology described in this paper proposes two innovative approaches that will break through the major development bottlenecks of current DNA-assisted metal micron to nanowire processes. Compared with other methods, the main advantage of the method of the present invention is that the natural capillary force is used to drive the DNA-silver nanoparticles to diffuse toward the physically formed cleavage region or scribe region, and then DNA is carried out by DNase. Biochemical enzyme etching of the transition support structure produces a pure silver wire structure. The second step described above makes a significant contribution to how to make a clean, only wire material that can be integrated into the substrate of the nanoelectronics architecture. The first step described above improves the controllability and flexibility of the "writing" process of the metal wire by using capillary force, which is different from the case where any wire and pattern are produced in the literature [6, 7, 11-13].
毛細管力之產生係因水分自邊緣蒸發時,主體內之水分對邊緣處之水分補充速率會隨液滴內之位置不同而有所差異。基於此一現象,DNA分子將銀奈米粒子朝邊緣方向「拖曳」,而銀奈米粒子沉積後便形成線料。蒸發之過程亦可能在液滴內引發馬倫哥尼(Marangoni)流,但此流況不利於DNA-銀奈米粒子沿著邊緣沉積[14]。強勁之馬倫哥尼流可使粒子重新分布並返回中心位置。添加表面張力降低劑可擾亂馬倫哥尼流,或許能藉此促進DNA-銀奈米粒子沿著線料區沉積,進而改良銀線之結構與電氣性質。 The capillary force is generated when the water is evaporated from the edge, and the rate of water replenishment at the edge of the body varies with the position within the droplet. Based on this phenomenon, the DNA molecules "drag" the silver nanoparticles toward the edge, and the silver nanoparticles form a strand after deposition. The evaporation process may also induce Marangoni flow in the droplets, but this flow condition is not conducive to the deposition of DNA-silver nanoparticles along the edges [14]. The powerful Marangoni flow allows the particles to redistribute and return to the center. The addition of a surface tension reducing agent can disturb the Marangoni flow, which may thereby promote the deposition of DNA-silver nanoparticles along the strand region, thereby improving the structural and electrical properties of the silver wire.
「書寫」之解析度亦可透過使用微影技術及其他奈米尺度之技術而獲得大幅改善並輕易加以操控[15-16]。以此方法可輕易完成圖案之書寫,而線料之奈米級解析度甚至可能有助於單分子電子學之研究。此外,相較於文獻記載[1-3,6,7,11-13],本發明所提出之組裝及圖案化程序可在成本及製程複雜度均較低之情況下提供靈活度。因此,發明人期待上述之新近發現及書寫寬度之減縮可加速推動一般奈米圖案化及奈米電子學之發展。 The resolution of "writing" can also be greatly improved and easily manipulated through the use of lithography and other nanoscale technologies [15-16]. The pattern can be easily written in this way, and the nanometer resolution of the strands may even contribute to the study of single molecule electronics. In addition, the assembly and patterning procedure proposed by the present invention provides flexibility in terms of low cost and process complexity compared to the literature [1-3, 6, 7, 11-13]. Therefore, the inventors expect that the above-mentioned recent discovery and reduction in writing width can accelerate the development of general nano patterning and nanoelectronics.
參考文獻: references:
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4. Braun, E. et al., DNA-templated assembly and electrode attachment of a conducting silver wire. Nat. Lett. 391, 775-778 (1998). 4. Braun, E. et al., DNA-templated assembly and electrode attachment of a conducting silver wire. Nat. Lett. 391, 775-778 (1998).
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9. Peng, et al., Self-assembly of λ-DNA networks/Ag nanoparticles: Hybrid architecture and active-SERS substrate. J. Coll. & Interf. Sci. 317, 183-190 (2008). 9. Peng, et al., Self-assembly of λ-DNA networks/Ag nanoparticles: Hybrid architecture and active-SERS substrate. J. Coll. & Interf. Sci. 317, 183-190 (2008).
10. Deegan, et al., Contact line deposits in an evaporating drop. Phy. Rev. E 68, 042601-1 (2003). 10. Deegan, et al., Contact line deposits in an evaporating drop. Phy. Rev. E 68, 042601-1 (2003).
11. Russel, C., et al., Gold Nanowire Based Electrical DNA Detection Using Rolling Circle Amplification. ACS Nano 8(2), 1147-1153 (2014). 11. Russel, C., et al., Gold Nanowire Based Electrical DNA Detection Using Rolling Circle Amplification. ACS Nano 8(2), 1147-1153 (2014).
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