201039487 4 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種具奈米結構之電極製作方法，特 別是關於一種可有效提高靈敏度及訊雜比（S/N ratio)的 具奈米結構之鈀電極製作方法。 【先前技術】 毛細管電泳(capillary electrophoresis，CE)的偵測方 〇 法因具有分析時間短、所需樣品量少及攜帶方便等優點 在近年來蓬勃發展，當使用微機電的製作技術時，更可 以設計出各種微通道，並整合其他化學或是生醫反應原 理，以在單一晶片上完成樣品的進料、分離與偵測的實 驗流程，眾多的優點使得毛細管電泳晶片成為一項重要 的分析技術。 一般常被應用在毛細管電泳的偵測方法有紫外光/ 可見光吸收侦測法(UV/visible absorption detection)、雷 ❹ 射激發螢光摘測法（laser induced fluorescence，LIF)、質 譜偵測法(mass spectrometric detection)及電化學偵測法 (electrochemical detection)，其中以雷射激發螢光摘測 法較常用且靈敏度最高，但該偵測法需要體積龐大且價 錢昂貴的光學偵測系統。相較之下，電化學偵測法不但 有相當良好的靈敏度及可調變的選擇性，且其另具有設 備系統價格低、所需樣品量少及功率消耗低等多項優 點。安培偵測法為一種電化學偵測法，其原理為將微電 201039487 極置於毛細管内（off-column)或將微電極置於毛細管出 口端（end-column)，然後於微電極上施加一固定電位， 偵測經管道分離出的樣本於電極表面之氧化還原t 流。由於安培偵測法易於操作且背景電流值小，因此常 被應用在毛細管電泳的偵測系統中。 然而’毛細管所施加的分離電壓其產生的電泳電、凉 通常遠大於微電極所測得的分析物之氧化或還原電 流。因此’為了避免偵測器受到影響，Ewing及 Wallingford在1987年利用一多孔性玻璃管做為導電界 面（electric decoupler)連接分離毛細管及偵測毛細管，高 電壓的電泳電流可由此界面導出，自成一個分離的^ 路，降低對安培偵測器所造成的干擾(Ewing，A.G &201039487 4 VI. Description of the Invention: [Technical Field] The present invention relates to a method for fabricating an electrode having a nanostructure, and more particularly to a nanometer having an effective sensitivity and a signal-to-noise ratio (S/N ratio) A method for fabricating a palladium electrode. [Prior Art] Capillary electrophoresis (CE) detection method has been booming in recent years due to its short analysis time, low sample volume and convenient carrying. When using MEMS manufacturing technology, It is possible to design a variety of microchannels and integrate other chemical or biomedical reaction principles to complete the experimental flow of sample feeding, separation and detection on a single wafer. Numerous advantages make capillary electrophoresis wafers an important analysis. technology. Commonly used in capillary electrophoresis detection methods are UV/visible absorption detection, laser induced fluorescence (LIF), mass spectrometry ( Mass spectrometric detection and electrochemical detection, in which laser-excited fluorescence extraction is more common and sensitive, but the detection method requires a bulky and expensive optical detection system. In contrast, electrochemical detection has not only good sensitivity and variable selectivity, but also has many advantages such as low equipment system price, low sample volume and low power consumption. Amperometric detection is an electrochemical detection method. The principle is to place the micro-electricity 201039487 pole in the capillary (off-column) or place the microelectrode on the end-column of the capillary, and then apply it on the microelectrode. A fixed potential detects the redox flow of the sample separated by the tube at the surface of the electrode. Since the amperometric detection method is easy to operate and has a small background current value, it is often used in a capillary electrophoresis detection system. However, the separation voltage applied by the capillary produces electrophoresis, which is usually much larger than the oxidation or reduction current of the analyte measured by the microelectrode. Therefore, in order to avoid the impact of the detector, Ewing and Wallingford used a porous glass tube as an electric decoupler to connect the separation capillary and the detection capillary in 1987. The high-voltage electrophoretic current can be derived from this interface. In a separate path, reducing the interference caused by the Ampere detector (Ewing, AG &
Wallingford，R.A. Analyt. Chem. 59, 1762, 1987.)。此界 面之後的分析物，雖然已經沒有電滲流的推動，仍因慣 性的作用以原來具備的速度流到毛細管末端之工作電 極處，並以微電極偵測之，此方法可降低分離電壓對樣 品偵測所造成的干擾。此外，分離電壓因其高電場電解 水，可能會在接地端形成氫氣(h2)聚集而阻斷電泳迴路 的現象，而使得整個電泳迴路或電泳電流會分流到工作 電極，造成背景電流增大，以致雜亂訊號增加，而不利 於降低偵測極限最小值或提高電極的訊雜比（S/N ratio)。因此，為了避免氣泡的產生與聚集，可選擇利 用飽(Pd)具有㈣氫氣的性f，統作為電泳晶片安培 债測之導電界面’有效的導掉接地端表面因高電壓作用 201039487 而產生的氫氣，使電泳電流對於工作電極的干擾降到最 小0 一般傳統的平面電極在電極面上會產生一層擴散 層’電極的整個表面形成全部重疊（total overlap)的形 式’如此電極面的擴散現象是為線性擴散，所以一般產 生的電流訊號靈敏度較差。目前已知的鈀金屬平面電極 可見於：中華民國公告第1223064號發明專利，其揭示 一生物感測器使用金或鈀等作為電極及使用聚對苯二 曱酸乙二醇脂等絕緣性樹脂做為基板；中華民國公告第 1235831號發明專利，其揭示一生物感測器使用白金、 金、把等作為電極及使用聚酯系樹脂膜做為基板；中華 民國公告第1269033號發明專利，其揭示一電化學生物 感測器使用碳漿、銀漿、金漿、鉑漿、鈀漿等作為電極 及使用聚氯乙烯等做為工作電極基材；中華民國公告第 508229號發明專利’其揭示一拋棄式生物感測器使用 碳膠、金膠、鈀膠等作為電極及使用聚氯乙烯等做為絕 緣基質；中華民國公告第1301852號發明專利，其揭示 一微流裝置使用鉑、金、銅、鈀等作為陽極室與陰極室 中的電極之材料，以吸收氫氣；美國公開第 2008/0128285號發明專利，其揭示一電化學氣體感測器 使用銀、金、鉑、鈀等作為電極及使用矽等做為基板； 美國公告第7,357,852號發明專利，其揭示一電化學裝 置使用鈀金屬作為無氣泡電極；以及，美國公開第 2003/0213693號發明專利，其揭示一電泳裝置使用鈀作 6 201039487 為電極及使用矽、玻璃等做為基板。 發明人於先前發表之研究（c. M. Chen，G. L. Chang， and C. H. Lin, Journal of Chromatography A, v〇l. 1194, pp. 231-236, 2008.)發現奈米組合電極可較平面電極更 有效地將電泳電流接地，可降低雜訊，因而有利於降低 偵測極限最小值及提高電極的訊雜比。然而，目前已知 的奈米組合電極設計皆有其缺點。例如：中華民國公告 第546670號發明專利雖提及在基材上行鈀金屬無電極 ® 沈積及上圖案之方法，不過其必需先於基材上接枝有機 層再沈積觸媒層，使得製程過於繁複。再者，美國公告 第7,226,856號發明專利雖提及所製作之奈米陣列電極 所使用之基材為具導通孔(via)之矽基材，但其價格昂貴 且所使用之製程繁複。另外，美國公開第2004/0149578 號發明專利雖提及-利用灌模之方式製作奈米電極，不 過此法是利用導電之塑膠材料做為電極，鈀金屬電極無 ❹ 法利用此方式製作。美國公開第2006/0213259號發明 專利雖提及利用微機電方式製作出一深寬比約為 1 ’半徑約為5G奈米之懸臂樑電極，可用於原子力顯微 鏡及掃描式電化學顯微鏡。然而，此法單次只能製作出 -根奈米電極’不利於製作具多個電極之列式電極。 故有必要提供一種更佳的具奈米結構之電極製作 方法，以解決習知技術所存在的問題。 【發明内容】 7 201039487 本發明之主要目的在於提供一種具奈米結構之電極 製作方法’其係利用無電鍍技術沈積鈀金屬於具有奈米 孔z同之薄膜基材内成長把奈米柱，做為纪奈米電極’進 而有利於增加吸附氫氣的表面積、產生較低且穩定的背 景電流’以增加電極靈敏度、降低偵測極限最小值、提 雨電極的訊雜比(S/N ratio)及提高分析物偵測準破率。 本發明之次要目的在於提供一種具奈米結構之電極 〇 製作方法’其係在沈積鈀金屬於薄膜基材之表面及内部 後’去除表面之鈀金屬層及去除部分薄膜基材，以便裸 露出免奈米柱的一部分柱體，進而有利於更進一步提高 吸附氫氣的表面積及增加電極靈敏度等優點。 本發明之另一目的在於提供一種具奈米結構之電極 製作方法，其係利用無電鍍技術沈積鈀金屬於具有奈米 孔洞之薄膜基材内成長出鈀奈米柱，進而有利於降低鈀 奈米電極之製造成本及簡化其製程。 〇 為達上述之目的，本發明提供一種具奈米結構之電 極製作方法，其包含：將具有奈米孔洞之一薄膜基材浸 於一潤濕液中，以潤濕及擴張該薄膜基材之表面及奈米 孔洞之孔壁表面；將該薄膜基材取出並浸入一表面活化 液以/舌化該薄膜基材之表面及該奈来孔洞之孔壁表 面；以及，將該薄膜基材取出並浸入一鈀金屬無電鍍液 中，並加入一無電鍍還原劑，使該薄膜基材之表面鍍上 絶金屬層及在各該奈米孔洞内形成一把奈米柱。 在本發明之一實施例中，該薄膜基材選自高分子聚 8 201039487 合物基材、半導體基材或金屬基材。該尚分子聚合物基 材選自聚碳酸酯（polycarbonate，PC)、聚曱基丙烯酸甲酯 (亦即壓克力 poly-methylmethacrylate，PMMA)、聚丙烯(poly propylene)、聚苯乙稀(polystyrene ’ PS)、聚四氟乙烯 (polytetrafluoroethylene，PTFE)或聚酿亞胺(polyimide，PI)。該 半導體基材選自梦。該金屬基材選自銅、銘、金、銀、 不鐘鋼或其合金。 在本發明之一實施例中，該薄膜基材之奈米孔洞係 利用化學蝕刻加工而成。該奈米孔洞之孔徑在10微米 (nm)至500微米之間。該奈米孔洞相對於該薄膜基材之 深寬比係不大於2000。該奈米孔洞係貫穿該薄膜基材 之貫穿孔。 在本發明之一實施例中，該潤濕液係一低張力溶 液。該低張力溶液選自醇類或其水溶液。該醇類選自曱 醇、乙醇、異丙醇或其組合。 在本發明之一實施例中，該表面活化液包含核種成 分及安定劑成分。該核種成分選自氯化鈀及氣化亞錫或 是硝酸銀及氣化亞錫。該安定劑成分選自氣化氳、氨 水、三氟醋酸或其組合。該表面活化液另包含醇類，其 選自曱醇、乙醇、異丙醇或其組合。 在本發明之一實施例中，該鈀金屬無電鍍液包含氣 -化鈀及錯合劑。該錯合劑選自氯化氫、氨水、乙二胺四 醋酸鈉、氯化銨或其組合。 在本發明之一實施例中，該無電鍍還原劑選自次亞 9 201039487 磷酸鈉、甲醛、聯氨或其組合。 在本發明之一實施例中，在形成該鈀奈米柱之後， 另包含：去除該薄膜基材之其甲一表面上的叙金屬層， 使s亥把奈米柱之頂端裸露於該表面上。 在本發明之一實施例中，將一膠帶黏貼在該薄膜基 材之其中一表面上’再撕除膠帶，以去除該表面上的鈀 金屬詹。 在本發明之一實施例中，利用化學蝕刻去除該薄膜 基材之其中一表面上的把金屬層。 在本發明之一實施例中’在去除該薄膜基材之其中 一表面上的把金屬層之後，另包含：姓刻去除該薄膜美 材之該表面的部分基材，以便裸露出該鈀奈米柱的—部 分柱體。 在本發明之一實施例中，該薄膜基材選自聚碳酸 醋’及其钮刻使用之姓刻液選自驗性溶液或有機溶液。 該鹼性溶液選自聯氨、氨水或其組合；該有機溶液選自 至少一種含氯烷類。該含氯烷類選自三氯甲燒、二氣乙 烧或其組合。 在本發明之一實施例中，利用乾式蝕刻方式進行姓 刻去除該薄膜基材之該表面的部分基材。 在本發明之一實施例中’具有該鈀奈米柱的薄膜基 材係做為電化學偵測器或燃料電池之電極。 【實施方式】 201039487 、優點能更 並靶合所附 為了讓本發明之上述及其他目的、特徵 明顯易懂，下文將特舉本發明較佳實施例， 圖式，作詳細說明如下。 s月爹，…弟.一 ^叫"^、，个赞明較住貫施 ❹Wallingford, R.A. Analyt. Chem. 59, 1762, 1987.). The analyte after this interface, although there is no push of electroosmotic flow, still flows to the working electrode at the end of the capillary at the original speed due to the inertia, and is detected by the microelectrode. This method can reduce the separation voltage to the sample. Detect the interference caused. In addition, the separation voltage may be due to the high electric field electrolyzing water, which may form hydrogen gas (h2) at the grounding end to block the electrophoresis circuit, so that the entire electrophoresis circuit or electrophoresis current will be shunted to the working electrode, causing the background current to increase. As a result, the clutter signal is increased, which is not conducive to reducing the detection limit minimum or increasing the signal ratio (S/N ratio) of the electrode. Therefore, in order to avoid the generation and aggregation of bubbles, it is possible to select the use of saturated (Pd) (4) hydrogen gas f, which is used as the conductive interface of the electrophoresis wafer ampere measurement, which effectively leads to the grounding surface caused by the high voltage effect 201039487. Hydrogen, the interference of the electrophoretic current to the working electrode is minimized. Generally, the conventional planar electrode generates a diffusion layer on the electrode surface. The entire surface of the electrode forms a form of total overlap. The diffusion phenomenon of the electrode surface is For linear diffusion, the current signal generated is generally less sensitive. The currently known palladium metal planar electrode can be found in the invention patent of the Republic of China Publication No. 1223064, which discloses that a biosensor uses gold or palladium as an electrode and an insulating resin such as polyethylene terephthalate. As a substrate; the invention patent of the Republic of China Announcement No. 1228531, which discloses that a biosensor uses platinum, gold, etc. as an electrode and a polyester resin film as a substrate; and the Republic of China Announcement No. 1280903 invention patent, It is disclosed that an electrochemical biosensor uses a carbon paste, a silver paste, a gold paste, a platinum paste, a palladium paste or the like as an electrode and a polyvinyl chloride or the like as a working electrode substrate; the Republic of China Announcement No. 508229 invention patent discloses A disposable biosensor uses carbon glue, gold glue, palladium glue or the like as an electrode and uses polyvinyl chloride as an insulating substrate; the Republic of China Announces Patent No. 1301852, which discloses that a microfluidic device uses platinum, gold, Copper, palladium or the like as a material of an electrode in an anode chamber and a cathode chamber to absorb hydrogen; and an invention patent of US Publication No. 2008/0128285, which discloses an electrochemical gas The detector uses silver, gold, platinum, palladium or the like as an electrode and uses ruthenium or the like as a substrate; US Pat. No. 7,357,852, which discloses an electrochemical device using palladium metal as a bubble-free electrode; and, US Publication No. 2003/ Patent No. 0213693 discloses an electrophoresis apparatus using palladium as 6 201039487 as an electrode and using ruthenium, glass or the like as a substrate. The inventors found in previously published studies (c. M. Chen, GL Chang, and CH Lin, Journal of Chromatography A, v〇l. 1194, pp. 231-236, 2008.) that nano-composite electrodes can be compared to planar electrodes. Grounding the electrophoresis current more effectively reduces noise, which helps to reduce the minimum detection limit and increase the signal-to-noise ratio of the electrode. However, currently known nanocomposite electrode designs have their disadvantages. For example, the invention patent of the Republic of China Bulletin No. 546670 mentions the method of depositing and patterning the palladium metal without electrode on the substrate, but it is necessary to graft the organic layer on the substrate to redeposit the catalyst layer, so that the process is too complicated. Further, U.S. Patent No. 7,226,856 mentions that the substrate used for the fabricated nano Array electrode is a ruthenium substrate having a via, but it is expensive and complicated in the process used. Further, although the invention patent of U.S. Patent Publication No. 2004/0149578 mentions that a nano electrode is produced by means of a filling method, the method uses a conductive plastic material as an electrode, and a palladium metal electrode is produced by this method. U.S. Patent Publication No. 2006/0213259 discloses the use of a microelectromechanical method to fabricate a cantilever beam having an aspect ratio of about 1 Å and a radius of about 5 G nanometers, which can be used for atomic force microscopy and scanning electrochemical microscopy. However, this method can only produce a -nano electrode in a single step, which is disadvantageous for fabricating a column electrode having a plurality of electrodes. Therefore, it is necessary to provide a better electrode fabrication method with a nanostructure to solve the problems of the prior art. SUMMARY OF THE INVENTION 7 201039487 The main object of the present invention is to provide a method for fabricating an electrode having a nanostructure, which uses an electroless plating technique to deposit a palladium metal in a thin film substrate having a nanopore and grow a nano column. As a Kenneth electrode', it is beneficial to increase the surface area of hydrogen adsorption, resulting in a lower and stable background current' to increase electrode sensitivity, reduce the minimum detection limit, and the signal-to-noise ratio (S/N ratio) of the raining electrode. And improve the detection rate of analytes. A secondary object of the present invention is to provide a method for fabricating an electrode crucible having a nanostructure, which is characterized in that after depositing palladium metal on the surface and inside of the film substrate, the surface of the palladium metal layer is removed and a portion of the film substrate is removed to expose the substrate. Part of the column of the nano column is facilitated, which further improves the surface area of adsorbing hydrogen and increases the sensitivity of the electrode. Another object of the present invention is to provide a method for fabricating an electrode having a nanostructure, which is characterized in that palladium metal is deposited by an electroless plating technique to grow a palladium nano column in a film substrate having a nanopore, thereby facilitating the reduction of palladium. The manufacturing cost of the rice electrode and the simplification of its manufacturing process. In order to achieve the above object, the present invention provides a method for fabricating an electrode having a nanostructure, comprising: immersing a film substrate having a nanopore in a dampening solution to wet and expand the film substrate a surface of the pore wall of the nanopore; the film substrate is taken out and immersed in a surface activation liquid to/tongue the surface of the film substrate and the surface of the pore wall of the nanopore; and the film substrate The silicon metal electroless plating solution is taken out and immersed, and an electroless plating reducing agent is added to coat the surface of the film substrate with a metallization layer and a nano column is formed in each of the nanometer holes. In one embodiment of the invention, the film substrate is selected from the group consisting of a polymeric poly 8 201039487 composite substrate, a semiconductor substrate, or a metal substrate. The molecular polymer substrate is selected from the group consisting of polycarbonate (PC), polymethyl methacrylate (PMMA), polypropylene, and polystyrene. 'PS), polytetrafluoroethylene (PTFE) or polyimide (PI). The semiconductor substrate is selected from the group consisting of dreams. The metal substrate is selected from the group consisting of copper, ingot, gold, silver, stainless steel, or alloys thereof. In one embodiment of the invention, the nanopore of the film substrate is processed by chemical etching. The nanopore has a pore size between 10 micrometers (nm) and 500 micrometers. The aspect ratio of the nanopore to the film substrate is not more than 2,000. The nanoholes extend through the through holes of the film substrate. In one embodiment of the invention, the wetting fluid is a low tension solution. The low tension solution is selected from the group consisting of alcohols or aqueous solutions thereof. The alcohol is selected from the group consisting of decyl alcohol, ethanol, isopropanol or a combination thereof. In one embodiment of the invention, the surface active liquid comprises a core component and a stabilizer component. The core component is selected from the group consisting of palladium chloride and vaporized stannous or silver nitrate and vaporized stannous. The stabilizer component is selected from the group consisting of gasified hydrazine, ammonia, trifluoroacetic acid, or a combination thereof. The surface activating liquid further comprises an alcohol selected from the group consisting of decyl alcohol, ethanol, isopropanol or a combination thereof. In one embodiment of the invention, the palladium metal electroless plating bath comprises gas-palladium and a dopant. The binder is selected from the group consisting of hydrogen chloride, aqueous ammonia, sodium ethylenediaminetetraacetate, ammonium chloride or a combination thereof. In one embodiment of the invention, the electroless plating reducing agent is selected from the group consisting of sub-salt 9 201039487 sodium phosphate, formaldehyde, hydrazine or a combination thereof. In an embodiment of the present invention, after forming the palladium nano column, the method further comprises: removing the metal layer on the surface of the film substrate, so that the top of the nano column is exposed on the surface on. In one embodiment of the invention, a tape is adhered to one of the surfaces of the film substrate to remove the tape to remove the palladium metal on the surface. In one embodiment of the invention, the metal layer on one of the surfaces of the film substrate is removed by chemical etching. In an embodiment of the invention, after removing the metal layer on one of the surfaces of the film substrate, the method further comprises: partially removing the surface of the surface of the film material to expose the palladium The column of the meter column. In one embodiment of the invention, the film substrate is selected from the group consisting of polycarbonates and their engravings are selected from an assay solution or an organic solution. The alkaline solution is selected from the group consisting of hydrazine, ammonia or a combination thereof; the organic solution is selected from at least one chloroalkane. The chloroalkane is selected from the group consisting of trichloromethane, sulphur dioxide or a combination thereof. In one embodiment of the invention, a portion of the substrate of the surface of the film substrate is removed by dry etching. In one embodiment of the invention, the film substrate having the palladium nanocolumn is used as an electrode of an electrochemical detector or fuel cell. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In order to make the above and other objects and features of the present invention more obvious, the preferred embodiments of the present invention will be described in detail below. s month 爹, ... brother. a ^ called "^,, a tribute to live more than 施
米結構之電極製作方法主要包含下列步驟：將具二 孔洞11之一薄膜基材1浸於一潤濕液2 中，二”乎 擴張該薄膜基材1之表面及奈米孔洞11之孔、L…、及 將該薄膜基材1取出並浸入一表面活化液3，^ 薄膜基材1之表面及該奈米孔洞n之孔壁表Μ活化該 薄膜基材1取出並浸入一鈀金屬無電鍍液4中，、將該 一無電鍍還原劑5，使該薄膜基材i之表面鍍並加入 屬層61及在各該奈米孔、祠u Θ形成一^把金 去除該薄膜基材1之其中-表面上祕金屬層 該鈀奈米柱62之頂端裸露於該表面上；以及，61，使 除該薄膜基材1之該表面的部分歸，以 ^刻去 奈米柱62。上述加工處理後之具有該把奈米 薄臈基材1係可應祕做為各種電化學偵測器或燃料 電池之電極’其有利於增加吸附氫氣的表面積、產▲較 低且穩定的背景電流，以增加電極靈敏度、降低谓測極 限最小值、提高電極的訊雜比（S/N ratio)及提高分析物 Ϊ貞測準’本發明製做之電極並不限於上述應 用’其亦可錢用於做為其他微型感應器（圆沉)之電 極本發明將於下文以第（至6圖詳細說明本發明具奈 米結構之f㈣作方糾各個㈣。 201039487 請參照第1及1A圖所示，本發明較佳實施例之具 奈米結構之電極製作方法第一步驟係：將具有奈米孔洞 11之一薄膜基材1浸於一潤濕液2中，以潤濕及擴張 該薄膜基材1之表面及奈米孔洞11之孔壁表面。在本 步驟中，首先準備具有奈米孔洞11之薄膜基材1。在 本發明中，該薄膜基材1之材料可選自高分子聚合物基 材、半導體基材或金屬基材，其中該r%分子聚合物基材 較佳選自聚礙酸酯(polycarbonate，PC)、聚曱基丙婦酸曱 酯(亦即壓克力 poly-methylmethacrylate，PMMA)、聚丙浠(poly propylene)、聚苯乙烯（polystyrene，PS)、聚四氟乙浠 (polytetrafluoroethylene，PTFE)或聚醯亞胺(polyimide，PI);該 半導體基材較佳選自碎(Si);該金屬基材較佳選自銅、 紹、金、銀、不鑛鋼或其合金。在本實施例中，該薄膜 基材1係以聚碳酸酯為例，但並不限於此。再者，該薄 膜基材1之奈来孔洞11較佳係利用化學触刻加工而 成’但亦可能利用電漿進行蝕刻加工，或利用其他方式 形成數個該奈米孔洞11。 在第1及1A圖中，該奈米孔洞11係概略示意成貫 穿該薄膜基材1之垂直貫穿孔，但該奈米孔洞11貫穿 該薄膜基材1之角度實際上可能相互不同，因而形成各 種傾斜狀之貫穿孔，且相鄰之奈米孔洞11之間可能相 互連通或不連通，其實際形狀將另於下文詳細說明。值 得注意的是’在本發明中，該奈米孔洞Η之孔徑較佳 維持在10微米（nm)至500微米之間，例如在20微米至 201039487 100微米之間，特別是约50微米；而該奈米孔洞u相 對於該薄膜基材1之深寬比較佳係不大於2000 ,例如 在10至100之間，特別是約20。在本發明中，該薄膜 基材1之厚度或該奈米孔洞11之密度並不加以限制， 但在本實施例中，該薄膜基材1之厚度大致介於5微米 至20微米之間’例如約6微米。 再者，在第一步驟中，該潤濕液2係選自一低張力 溶液，特別是對該薄膜基材1之材質具有高度親和性之 〇 低張力溶液。在本發明中’該低張力溶液（潤濕液2)係 可選自醇類或其水溶液’而該醇類較佳選自甲醇、乙 醇、異丙醇或其組合，特別是選自曱醇或其水溶液。在 本實施例中，該潤濕液2選自甲醇及乙醇之混合水溶 液，其混合比例可依產品加以選擇變化’並不加以限 制。在本發明將具有奈米孔洞11之薄膜基材1浸於該 潤濕液2中約3小時後’將可潤濕及擴張該薄膜基材i ❹ 之表面及奈米孔洞11之孔壁表面’特別是能使該奈米 孔洞11内充滿液體而沒有存在氣泡，以利進行後續步 驟。在一實施例中’本發明亦可在潤濕期間選擇搭配使 用超音波震盪處理，以增加潤濕效果。 請參照第2及2A圖所示’本發明較佳實施例之具 奈米結構之電極製作方法第二步驟係：將該薄膜基材1 取出並浸入一表面活化液3 ’以活化該薄膜基材1之表 面及該奈米孔洞11之孔壁表面。在本步驛中，該表面 活化液3係包含核種（nucleation seed)成分及安定劑 13 201039487 (stabilizer)成分。在本發明中，該核種成分較佳選自氯 化IE及氯化亞錫，或是碗酸銀及氯化亞錫，而該安定劑 成分較佳選自氯化氫'氨水、三氟醋酸或其組合，其中 該安定劑成分用以維持該核種成分呈穩定離子態。再 者，該表面活化液3另可包含醇類，例如選自曱醇、乙 醇、異丙醇或其組合。在本實施例中，該表面活化液3 係包含甲醇、氣化鈀、氯化亞錫、氯化氫、氨水、硝酸 D 銀及三氟醋酸之混合水溶液，其混合比例可依產品加以 選擇變化，並不加以限制。在將該薄膜基材丨由該潤濕 液2中取出後’使該薄膜基材1另浸入該表面活化液3 約20分鐘。此時，該核種成分之氯化鈀、硝酸銀及氯 化亞錫將反應形成二價錫離子與銀金屬或鈀金屬，因而 在該薄膜基材1之表面及該奈米孔洞11之孔壁表面上 形成數個核種31(即銀金屬或鈀金屬核種），藉以活化上 述表面，以利進行後續無電鍍製程。 〇 請參照第3及3A圖所示，本發明較佳實施例之具 奈米結構之電極製作方法第三步驟係：將該薄膜基材1 取出並浸入一鈀金屬無電鍍液4中，並加入一無電鍍還 原劑5，使該薄膜基材1之表面錢上一飽金屬層61及 在各該奈米孔洞11内一形成鈀奈米柱62。在本步驟 中，該鈀金屬無電鍍液4較佳包含氯化鈀及錯合劑。該 錯合劑較佳選自氯化氫、氨水、乙二胺醋酸鈉、氯化銨 或其組合，其用以緩衝該鈀金屬無電鍍液4之鈀離子活 性及調節溶液之酸酴值。再者，該無電鍍還原劑5選自 201039487 次亞構酸納（Sodium hypophosphite monohydrate)、甲酸 (formaldehyde)、聯氨(hydrazine)或其組合。在本實施例 中’該鈀金屬無電鍍液4係包含氯化鈀、氯化氫、氨水、 乙二胺醋酸鈉及氣化銨之混合水溶液，其混合比例可依 產品加以選擇變化，並不加以限制。該無電鍍還原劑5 係選自次亞構酸納、曱酸或聯氨之溶液，其濃度可依產 品加以選擇變化，並不加以限制。在將該薄膜基材i由 該表面活化液3取出後，使該薄膜基材丨另浸入該鈀金 屬無電鐘液4中，並加入該無電鑛還原劑5，於4°C的 低溫下反應約3小時。此時，該抱金屬無電鍍液4中的 氯化把將與次亞鱗酸鈉、曱搭或聯氨反應，並以第2A 圖之核種31為基礎在該薄膜基材1之表面上形成一紀 金屬層61’及在各該奈米孔洞η内形成一把奈米柱 62。在完成第三步驟後，具有該鈀金屬層61及鈀奈米 柱62之薄膜基材1實質上已可做為一鈀奈米電極，該 薄膜基材1之其中一表面上的鈀金屬層61即可用以做 為一把奈采電極的反應侧。 請參照第4、4A及4B圖所示，本發明較佳實施例 之具奈米結構之電極製作方法第四步驟係：去除該薄膜 基材1之其中一表面上的鈀金屬層61，使該鈀奈米柱 62之頂端裸4於該表面上。本發明第四步驟係一選擇 性實施之步驟，其係可依產品需求選擇實施或不實施。 在本步驟中’本發明可選擇利用化學餞刻或膠帶等化學 或物理方式去除該薄膜基材1之其中一表面上的鈀金 15 201039487 屬層Μ。在本實施财，本發明即先彻— 貼在該薄膜基材1之f由 主/帶 黏 以去，、中_表面上’再撕除該谬帶7， 除該表面上_金屬層6卜並使糾奈米柱62之 頂端稞露於該表面上，其實際表面結構係可參考第4B 圖^子顯微照相圖，其中位於各該奈米孔洞U的位 置處德金屬層61裸露出奈米等級之表面積，而 -奈米叙電極結構。此時，該薄㈣材ι㈣該_米 ΟThe electrode manufacturing method of the rice structure mainly comprises the following steps: immersing a film substrate 1 having two holes 11 in a dampening solution 2, and expanding the surface of the film substrate 1 and the pores of the nano hole 11, L... and removing the film substrate 1 and immersing it in a surface activation liquid 3, the surface of the film substrate 1 and the pore wall surface of the nanohole n are activated to remove the film substrate 1 and immersed in a palladium metal electroless plating solution. 4, the electroless plating reducing agent 5, the surface of the film substrate i is plated and added to the genus layer 61 and a gold is formed in each of the nanopores, 祠u 去除 to remove the film substrate 1 Wherein the top surface of the palladium nano-column 62 is exposed on the surface; and 61, the portion of the surface of the film substrate 1 is subjected to the engraving of the nano-pillar 62. After treatment, the nano-ply substrate 1 can be used as an electrode of various electrochemical detectors or fuel cells, which is beneficial to increase the surface area of hydrogen adsorption, and produce a low and stable background current to increase Electrode sensitivity, lowering the minimum value of the measured limit, increasing the signal-to-noise ratio of the electrode S/N ratio) and improvement of analytes. The electrode made by the present invention is not limited to the above application. It can also be used as an electrode for other micro-sensors (round sinks). The first step of the method for fabricating the electrode having the nano structure according to the preferred embodiment of the present invention is shown in FIG. 1 to FIG. 6 for detailing the f (four) of the nano structure of the present invention. The film substrate 1 having a nano hole 11 is immersed in a dampening solution 2 to wet and expand the surface of the film substrate 1 and the surface of the hole wall of the nanohole 11. In this step, First, a film substrate 1 having a nanohole 11 is prepared. In the present invention, the material of the film substrate 1 may be selected from a polymer substrate, a semiconductor substrate or a metal substrate, wherein the r% molecular polymer The substrate is preferably selected from the group consisting of polycarbonate (PC), poly-methylmethacrylate (PMMA), polypropylene, polystyrene (polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene, polystyrene PS), polytetrafluoroethylene (PTFE) or polyimine (polyimide, PI); the semiconductor substrate is preferably selected from the group consisting of copper (Si); the metal substrate is preferably selected from the group consisting of copper, gold, silver, non-mineral steel or alloys thereof. In this embodiment, the film The substrate 1 is exemplified by polycarbonate, but is not limited thereto. Further, the pores 11 of the film substrate 1 are preferably processed by chemical contact etching, but may be etched by plasma. Alternatively, a plurality of the nanoholes 11 are formed by other means. In the first and first aspects, the nanoholes 11 are schematically illustrated as penetrating through the vertical through holes of the film substrate 1, but the nanoholes 11 are penetrated therethrough. The angles of the film substrate 1 may actually be different from each other, thereby forming various inclined through holes, and the adjacent nanoholes 11 may or may not communicate with each other, and the actual shape thereof will be described in detail below. It is noted that in the present invention, the pore diameter of the nanopore is preferably maintained between 10 micrometers (nm) and 500 micrometers, for example between 20 micrometers and 201039487 100 micrometers, especially about 50 micrometers; The depth of the nanopore u relative to the film substrate 1 is preferably no more than 2000, such as between 10 and 100, especially about 20. In the present invention, the thickness of the film substrate 1 or the density of the nanoholes 11 is not limited, but in the present embodiment, the film substrate 1 has a thickness of approximately between 5 μm and 20 μm. For example about 6 microns. Further, in the first step, the dampening solution 2 is selected from a low tension solution, particularly a low tension solution having a high affinity for the material of the film substrate 1. In the present invention, the low-tension solution (wetting liquid 2) may be selected from an alcohol or an aqueous solution thereof, and the alcohol is preferably selected from the group consisting of methanol, ethanol, isopropanol or a combination thereof, particularly selected from the group consisting of sterols. Or an aqueous solution thereof. In the present embodiment, the wetting liquid 2 is selected from a mixed aqueous solution of methanol and ethanol, and the mixing ratio thereof may be selected and changed depending on the product' without limitation. In the present invention, after immersing the film substrate 1 having the nanoholes 11 in the dampening solution 2 for about 3 hours, the surface of the film substrate i ❹ and the surface of the pore walls of the nanoholes 11 will be wettable and expanded. In particular, the nanopore 11 can be filled with liquid without the presence of air bubbles for subsequent steps. In one embodiment, the invention may also be selected to match the ultrasonic oscillating treatment during wetting to increase the wetting effect. Referring to FIGS. 2 and 2A, a second step of the method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention is: taking out the film substrate 1 and immersing it in a surface activation liquid 3' to activate the film substrate. The surface of the material 1 and the surface of the pore wall of the nanohole 11 . In this step, the surface activation liquid 3 contains a nucleation seed component and a stabilizer 13 201039487 (stabilizer) component. In the present invention, the core component is preferably selected from the group consisting of chlorinated IE and stannous chloride, or silver stannate and stannous chloride, and the stabilizer component is preferably selected from the group consisting of hydrogen chloride 'ammonia water, trifluoroacetic acid or its A combination wherein the stabilizer component is used to maintain the nucleus component in a stable ionic state. Further, the surface activating liquid 3 may further contain an alcohol, for example, selected from the group consisting of decyl alcohol, ethanol, isopropyl alcohol or a combination thereof. In this embodiment, the surface activation liquid 3 comprises a mixed aqueous solution of methanol, vaporized palladium, stannous chloride, hydrogen chloride, ammonia water, D-nickel nitrate and trifluoroacetic acid, and the mixing ratio thereof may be selected according to the product, and No restrictions. After the film substrate was taken out from the wetting liquid 2, the film substrate 1 was further immersed in the surface activation liquid 3 for about 20 minutes. At this time, the palladium chloride, silver nitrate and stannous chloride of the core component are reacted to form a divalent tin ion and a silver metal or a palladium metal, thereby forming a surface of the film substrate 1 and a pore wall surface of the nanohole 11 A plurality of nuclear species 31 (ie, silver metal or palladium metal core species) are formed thereon to activate the surface to facilitate subsequent electroless plating. Referring to Figures 3 and 3A, a third step of the method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention is: taking out the film substrate 1 and immersing it in a palladium metal electroless plating solution 4, and An electroless plating reducing agent 5 is added, so that the surface of the film substrate 1 is filled with a saturated metal layer 61 and a palladium nano column 62 is formed in each of the nanoholes 11. In this step, the palladium metal electroless plating solution 4 preferably contains palladium chloride and a binder. Preferably, the binder is selected from the group consisting of hydrogen chloride, aqueous ammonia, sodium ethylenediamine acetate, ammonium chloride or a combination thereof for buffering the palladium ion activity of the palladium metal electroless plating solution 4 and adjusting the acid enthalpy of the solution. Further, the electroless plating reducing agent 5 is selected from the group consisting of 201039487 Sodium hypophosphite monohydrate, formaldehyde, hydrazine or a combination thereof. In the present embodiment, the palladium metal electroless plating solution 4 comprises a mixed aqueous solution of palladium chloride, hydrogen chloride, ammonia water, sodium ethylenediamine acetate and ammonium sulfate, and the mixing ratio thereof can be selected and changed according to the product, and is not limited. . The electroless plating reducing agent 5 is selected from the group consisting of sub-sub- succinate, citric acid or hydrazine, and the concentration thereof can be selected and changed depending on the product, and is not limited. After the film substrate i is taken out from the surface activation liquid 3, the film substrate is further immersed in the palladium metal electroless clock liquid 4, and the electroless ore reducing agent 5 is added to react at a low temperature of 4 ° C. About 3 hours. At this time, the chlorination in the metal-free electroless plating solution 4 will be reacted with sodium hyposulfite, ruthenium or hydrazine, and formed on the surface of the film substrate 1 based on the core species 31 of FIG. 2A. A first metal layer 61' and a nano column 62 are formed in each of the nanoholes η. After the third step is completed, the film substrate 1 having the palladium metal layer 61 and the palladium nano column 62 can be substantially used as a palladium nano electrode, and a palladium metal layer on one surface of the film substrate 1 61 can be used as the reaction side of a nevus electrode. Referring to FIGS. 4, 4A and 4B, a fourth step of the method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention is: removing the palladium metal layer 61 on one surface of the film substrate 1 so that The top end of the palladium nanocolumn 62 is bare 4 on the surface. The fourth step of the present invention is a step of selective implementation which may or may not be implemented depending on the needs of the product. In this step, the present invention may optionally remove palladium on one of the surfaces of the film substrate 1 by chemical or physical means such as chemical engraving or tape. In the present invention, the present invention is first adhered to the film substrate 1 and the main/belt is adhered, and the enamel tape 7 is 'removed' on the surface, except for the metal layer 6 on the surface. And the top surface of the snare column 62 is exposed on the surface, and the actual surface structure thereof can be referred to the photomicrograph of FIG. 4B, wherein the German metal layer 61 is exposed at the position of each of the nanoholes U. The surface area of the nanometer grade, and the nanometer electrode structure. At this time, the thin (four) material ι (four) the _ m Ο
柱62之頂端的表面實質上即可心做為^奈米電極 的反應侧。 請參照第5、5A及5B圖所示，本發明較佳實施例 之具奈米結構之電極製作方法第五步驟係：制去除該 薄膜基材1之該表面的部分基材，以便裸露出減奈米 柱62的-部分柱體。本發明第五步驟係-選擇性實施 之步驟，其係可依產品需求選擇實施或不實施。在本步 驟中’本發明係依該薄膜基材^材質選擇適當的链刻 液8滴於該'福基材1之該表面，以_纟面進行# 刻Q或者’亦可選擇將該薄膜基村i局部或整個浸入該 蚀刻液8内，以對該表面進行飯刻，此時該薄膜基材i 之另一表面因具有該把金屬層61的保護而不致遭受蝕 刻。例如，在本實施例中，當該薄膜基材χ選自聚碳酸 酉旨時，餘刻使用之蚀刻液8係可選自鹼性溶液或有機溶 液，該鹼性溶液選自聯氨、氨水或其組合；該有機溶液 選自至少一種含氯烷類，例如選自三氣甲烷、二氯乙烷 或其組合。另外，本發明另可能選擇利用乾式蝕刻方式 16 201039487 (例如電漿)進行_去除該薄膜基材1之該表面的部分 基材在進行钱刻a寺，該餘刻液8僅會去除該薄 膜基材 1裸露該t奈米柱62之頂端的表面側的部分基材，因 而得以裸露出該把奈米柱62的一部分柱體，其實際表 面結構係可參考第SB圖之電子顯微照相圖，其中柱體 裸露的長度比例可依產品加以選擇變化，並不加以限 制。再者，雖第5A圖之奈米孔洞旧系概略示意成貫穿 〇 該薄膜基材1之垂直貫穿孔，但如第5B圖所示，該奈 米孔洞11貫穿該薄臈基材〗之角度實際上可能相互不 同，因而形成各種傾斜狀之貫穿孔，且相鄰之奈米孔洞 11之間可能相互連通或不連通。此時，該薄膜基材1 裸露該鈀奈米柱62的表面實質上即可用以做為一鈀奈 米電極的反應侧。 請參照第6圖所示’本發明較佳實施例利用各種不 同的工作電極（包含本發明之鈀奈米電極Pd-NEE、金 〇 奈米電極GNEE、傳統鈀平面電極Pd、傳統金平面電極The surface of the top end of the column 62 is substantially the center of the reaction of the nano electrode. Referring to FIGS. 5, 5A and 5B, a fifth step of the method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention is to remove a portion of the substrate on the surface of the film substrate 1 so as to be exposed. The column of the nanometer column 62 is reduced. The fifth step of the present invention is the step of selectively performing, which may or may not be implemented depending on the product requirements. In this step, the present invention selects an appropriate chain engraving liquid according to the material of the film substrate, and drops 8 drops on the surface of the 'fusible substrate 1 to perform the engraving on the surface of the substrate 1 or to select the film. The base portion i is partially or entirely immersed in the etching liquid 8 to carry out the cooking of the surface, at which time the other surface of the film substrate i is not subjected to etching by the protection of the metal layer 61. For example, in the present embodiment, when the film substrate is selected from the group consisting of polycarbonates, the etching solution 8 used in the past may be selected from an alkaline solution or an organic solution selected from the group consisting of hydrazine and ammonia. Or a combination thereof; the organic solution is selected from at least one chloroalkane, for example selected from the group consisting of tri-gas methane, dichloroethane or a combination thereof. In addition, the present invention may further select to use a dry etching method 16 201039487 (for example, plasma) to remove a portion of the substrate of the surface of the film substrate 1 in the process of engraving, the residual liquid 8 only removes the film. The substrate 1 exposes a part of the substrate on the surface side of the top end of the t-nano column 62, thereby exposing a part of the column of the nano column 62, and the actual surface structure thereof can be referred to the electron micrograph of FIG. In the figure, the proportion of the length of the exposed column can be changed according to the product, and is not limited. Furthermore, although the old hole of the nano-hole in FIG. 5A is schematically illustrated as a vertical through hole penetrating the film substrate 1, as shown in FIG. 5B, the nano-hole 11 penetrates through the thin substrate. They may be different from each other, and thus various inclined through holes are formed, and adjacent nanoholes 11 may or may not communicate with each other. At this time, the surface of the film substrate 1 exposed to the palladium nano column 62 can be used substantially as a reaction side of a palladium nanoelectrode. Referring to Figure 6, a preferred embodiment of the present invention utilizes various different working electrodes (including the palladium nanoelectrode Pd-NEE of the present invention, the gold nanotube electrode GNEE, the conventional palladium planar electrode Pd, a conventional gold planar electrode).
Au、傳統白金平面電極Pt)分別以丨M硫酸水溶液為 樣本進行循環伏安法（cyclic voltammetry)之量測（量剛 之掃描速率：50mV/s)。由圖得知，由於傳統白金平面 電極Pt及金平面電極Au不具吸氫效果，故電極易受氫 氣影響’以致無法量得明顯之分析物氧化或還原電流訊 號’·再者’金奈米電極GNEE具良好之電催化效應，故 相較之下’可量得分析物之氧化或還原電流訊號；另 外，傳統鈀平面電極Pd因具有良好的吸氫效果，所以 201039487 在o v左右仍可量得明顯之分析物氧化或還原電流訊 號。相較之下，本發明之把奈米電極pd_NEE所量得之 訊號又較傳統把平面電極Pd更進一步提升了量測靈敏 度。本發明之叙奈米電極Pd-NEE不僅於安培偵測法中 做為接地電極有良好效能，其更可結合吸氫與奈米結構 之性質’應用於各種相關技術領域，例如應用於做為各 種電化學偵測器或燃料電池之電極。 如上所述’相較於傳統纪平面電極雖具有吸氫性 質’卻無法再進一步提升量測靈敏度等缺點’第2至6 圖之本發明利用無電鍍技術沈積鈀金屬於具有該奈米 同11之薄膜基材1内成長該把奈米柱62 ’做為把奈 米電極，進而有利於增加吸附氫氣的表面積、產生較低 且穩定的背景電流’以增加電極靈敏度、降低偵測極限 =J值k尚電極的訊雜比（s/n ratio)及提高分析物侦 測準確率。再者，本發明可選擇在沈積鈀金屬於該薄膜 基，1之表面及内部後，去除表面之鈀金屬層61及去 =部分薄膜基材卜以便裸露出該把奈求柱62的一部 刀柱體，進而有利於更進—步提高吸附氫氣的表面積及 増加電極靈敏度等優點。另外，本發明係利用無電鐘技 術沈積絶金屬於具有奈米孔洞π之賴基材i内成長 出該鈀奈米柱62，進而有利於降低鈀奈米電極之製造 成本及簡化其製程。 雖然本發明已以較佳實施例揭露，然其並非用以限 制本發明，任何熟習此項技藝之人士，在不脫離本發明 201039487 種更動與修飾，因此本發明 專利範圍所界定者為準。 之精神和範圍内，當可作各 之保護範圍當視後附之申請 【圓式簡單說明】 ί二Γ第圖It發明較佳實施例之具奈米結構之電極 1作方步驟之示意圖及局部放大圖。 =2A圖·本發明較佳實施例之具奈米The Au, conventional platinum planar electrode Pt) was measured by cyclic voltammetry using a 丨M aqueous solution of sulfuric acid as a sample (scanning rate of the amount: 50 mV/s). It can be seen from the figure that since the conventional platinum plane electrode Pt and the gold plane electrode Au do not have hydrogen absorption effect, the electrode is easily affected by hydrogen 'so that the analyte is not oxidized or reduced current signal'. GNEE has a good electrocatalytic effect, so the oxidation or reduction current signal of the analyte can be measured in comparison. In addition, the traditional palladium planar electrode Pd has a good hydrogen absorption effect, so 201039487 can still be measured around ov. Obvious analyte oxidation or reduction current signal. In contrast, the signal obtained by the nano electrode pd_NEE of the present invention further improves the measurement sensitivity than the conventional planar electrode Pd. The Snae electrode Pd-NEE of the invention not only has good performance as a grounding electrode in the amperometric detection method, but also can be combined with the properties of hydrogen absorption and nanostructures to be applied to various related technical fields, for example, as Various electrochemical detectors or electrodes for fuel cells. As described above, 'the hydrogen absorption property of the conventional planar electrode is not able to further improve the measurement sensitivity and the like.' The second to sixth embodiments of the present invention utilize electroless plating techniques to deposit palladium metal with the same nano 11 The growth of the nano-pillar 62' as a nano-electrode in the film substrate 1 is advantageous for increasing the surface area of adsorbing hydrogen and generating a low and stable background current to increase the sensitivity of the electrode and reduce the detection limit = J The value of k is the s/n ratio of the electrode and improves the accuracy of analyte detection. Furthermore, in the present invention, after depositing palladium metal on the surface and inside of the film substrate, the surface of the palladium metal layer 61 and the portion of the film substrate are removed to expose a portion of the column 62. The cylinder body is further beneficial to further improve the surface area of the adsorbed hydrogen gas and the sensitivity of the electrode. Further, in the present invention, the palladium nanocolumn 62 is grown by depositing a base metal in a substrate i having a nanopore π by an electroless clock technique, thereby contributing to a reduction in the manufacturing cost of the palladium nanoelectrode and a simplification thereof. While the present invention has been disclosed in its preferred embodiments, it is not intended to limit the invention, and those skilled in the art, without departing from the scope of the present invention, will be modified. In the spirit and scope, when the scope of protection can be used as a subsidiary application, the circular application is a schematic diagram of the electrode 1 of the nanostructured structure of the preferred embodiment of the present invention. Partially enlarged view. = 2A · The preferred embodiment of the invention has a nanometer
製作方法第二步驟之*意圖及局部放大圖。 第3及3A圖：本發明較佳實施例之具奈米結構之電極 製作方法第二步驟之示意圖及局部放大圖。 第4及4A圖·本發明較佳實施例之具奈米結構之電極 製作方法第四步驟之示意圖及局部放大圖。 第4B圖：本發明較佳實施例第四步驟製備之鈀奈米電 極之電子顯微照相圖。 第5及5A圖：本發明較佳實施例之具奈米結構之電極 製作方法第五步驟之示意圖及局部放大圖。 第5B圖：本發明較佳實施例第五步驟製備之鈀奈米電 極之電子顯微照相圖。 第6圖··本發明較佳實施例製備之鈀奈米電極與各種不 同工作電極量測1M硫酸水溶液之循環伏安（cyclic voltammetry)圖。 【主要元件符號說明】 1 薄膜基材 11 奈米孔洞 19 201039487 2 潤濕液 3 表面活化液 31 核種 4 鈀金屬無電鍍液 5 無電鍍還原劑 61 把金屬層 62 鈀奈米柱 7 膠帶 8 蝕刻液 Ο 20The intent and partial enlargement of the second step of the production method. 3 and 3A are schematic views and partial enlarged views of a second step of a method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention. 4 and 4A are schematic views and partial enlarged views of a fourth step of the method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention. Figure 4B is an electron micrograph of a palladium nanoelectrode prepared in a fourth step of the preferred embodiment of the invention. 5 and 5A are schematic views and partial enlarged views of a fifth step of the method for fabricating an electrode having a nanostructure according to a preferred embodiment of the present invention. Figure 5B is an electron micrograph of a palladium nanoelectrode prepared in a fifth step of the preferred embodiment of the invention. Fig. 6 is a cyclic voltammetry diagram of a 1 M aqueous solution of sulfuric acid measured by a palladium nanoelectrode prepared in accordance with a preferred embodiment of the present invention and various different working electrodes. [Main component symbol description] 1 Film substrate 11 Nano hole 19 201039487 2 Wetting liquid 3 Surface activation liquid 31 Nuclear species 4 Palladium metal electroless plating solution 5 Electroless plating reducing agent 61 Metal layer 62 Palladium nano column 7 Tape 8 etching Liquid helium 20