1288681 玖、發明說明 [發明所屬之技術領域] 不發明係關於電解加 -% w/又丹體而言關於加 工基材用的加工電極及/或在佶 人仕使用流體，特別是純水，之電 解加工期間用以供給基材的供料恭托“ ^ J 1、科电極（feedmg eiectro(je) 〇 本發明亦關於使用該電極之雷鉉 心玉解加工裝置及方法。本發明 亦關於能將液體解離成離子 心方居’更具體而言關於電解 加工期間能將液體解離成離子之方法。 [先前技術] 近年來’有利用具有低雷玄 &罨阻率及尚電遷移阻抗的銅（Cu) 更換用在半導體晶圓等基封 土材上用於形成内連線電路充當金 屬材料之鋁或鋁合金的趨勢。 ^ 另 銅内連線（interconnection) 通常藉由將銅填入基材表中 衣1^ τ形成的精細凹部而形成。至 於形成銅内連線的方法，^ ^ ^ ^ ^ ^ ^ ^ ^ 已便用的有化學氣相沈積 (CVD)、濺鍍及鍍敷。々 — 方法中’寻銅膜貫質上形成於 整個基材表面上之祛Τ + 吏不而要的銅藉由化學機械研磨（CMP) 移除。 ’ 第1A至1C圖題+ +贫』上…丄 卜 貝不在基材w中形成銅内連線的實施 ^ 士第1 A圖所不’將絕緣膜2，例如Si02之氧化膜或 低k材料之薄膜’沈積於彼上已形成有半導體裝置之半導 體基底1上的墓雷js Ί 一 私㈢la上。藉由微影蝕刻技術在絕緣膜2 中七成接觸孔3和内連線溝槽4 n，在絕緣膜2上形 成由TaN等衣成之阻障層5，並藉由濺鍍、。vD等方法在 ㈣層5上形成晶種層7，該晶種層7係用作為電錢用的 315115 5 1288681 填充層。 接著，如第 使接觸孔3及 圖所示，以銅鍍敷該基材W的表面俾 膜6。之後，^連線'冓槽4填滿銅並在絕緣膜2上形成銅 以移除絕緣骐错2由化學機械研磨（CMP)研磨基材W的表面 槽4中的鋼心2上的鋼膜6，使填人接觸孔3和内連線溝 如第ic圖所干、面實質上與絕緣膜2的表面平齊。因此， 近來，各：，二絕緣層2中形成含銅膜6之内連線。 高的準確性。在並裝置中的零件都變得更加精細且需要更 質受到機械加工2使用次微米製造技術之時，材料的性 理方式破壞工件戶 響極大。在此情況之下，在以物 傳統的機械加工方 八自八表面移除之 缺陷，而使該工件的性質衰退。因此，進行;：大里的 使材料的性質衰退係重要的。 進-機械加工而不 已經研究出—些加工方法，例如化學研磨 械加工和電解研磨 電化子機 μ ϋ μ ρ shing)，以解決上述問 逑才子於傳統物理機械加工的方法，此 解離反應進行移除加工等/由化學 & _ £丨土 \此寺方法不會遇到塑型 t ▲交錯層一）和位錯之形成等之缺 細，而加工旎在不使材料性質衰退下進行。 、 :電化學機械加工製程中，特別是在使用純水 水的笔化學機械加工製程中，使用如離子 ： 換纖維等之離子交換器以增加加工速率。純水指、在25:: 的電阻率為〇.圓.⑽或更A的水，而超純水指在说 315115 6 1288681 時的電阻率為1 ΟΜΩ · cm或更大的水。離子交換器通常包 含離子交換基團，例如磺酸根、羧基、四價銨基卜n+”或 三價或更低價的胺基，之離子交換樹脂或離子交換膜係鍵 結至基底材料，如苯乙烯和二乙烯基苯之共聚合物，或氟 樹脂。再者，已知離子交換纖維中藉由接枝聚合作用將離 子交換基引入不織布内。 第2圖為顯示使用傳統離子交換 概略圖式。如第2圖所示，該電解加 器之電解加工裝置的 工裝置含有電源供應1288681 玖, invention description [Technical field to which the invention pertains] The invention is not related to electrolysis plus -% w/dan body for processing electrodes for processing substrates and/or for using fluids, especially pure water, The supply for supplying the substrate during the electrolytic processing is "^ J 1, the electrode (feedmg eiectro (je) 〇 The present invention also relates to the device and method for using the electrode." Regarding the ability to dissociate a liquid into an ionic core, more specifically, a method for dissociating a liquid into ions during electrolytic processing. [Prior Art] In recent years, there has been a use of a low-density & anti-corrosion rate and electromigration. Impedance copper (Cu) replacement is used on base-seal materials such as semiconductor wafers to form an interconnect wire circuit that acts as a metal or aluminum alloy. ^ Another copper interconnect is usually filled with copper. Formed into the fine recess formed by the coating 1^ τ in the substrate table. As for the method of forming the copper interconnect, ^ ^ ^ ^ ^ ^ ^ ^ ^ has been used for chemical vapor deposition (CVD), sputtering and Plating. 々 - Method of 'seeking copper film The copper that is formed on the entire surface of the substrate is removed by chemical mechanical polishing (CMP). '1A to 1C's problem + + lean'...The 丄bbe is not in the substrate w The formation of the copper interconnect is not the first to deposit an insulating film 2, such as an oxide film of SiO 2 or a thin film of low-k material, onto a tombstone on a semiconductor substrate 1 on which a semiconductor device has been formed. Js Ί a private (three) la. By the lithography etching technique, a contact hole 3 and an interconnect trench 4 n are formed in the insulating film 2, and a barrier layer 5 made of TaN or the like is formed on the insulating film 2, and A seed layer 7 is formed on the (four) layer 5 by sputtering, vD, or the like, and the seed layer 7 is used as a filling layer for 315115 5 1288681 for electricity money. Next, as shown in FIG. The surface film 6 of the substrate W is plated with copper. Thereafter, the wire 4 is filled with copper and copper is formed on the insulating film 2 to remove the insulation. 2 is chemically polished (CMP). The steel film 6 on the steel core 2 in the surface groove 4 of the substrate W is such that the filling contact hole 3 and the interconnecting groove are dry as shown in the ic diagram, and the surface is substantially flush with the surface of the insulating film 2. Therefore, recently, each: the inner wiring of the copper-containing film 6 is formed in the two insulating layers 2. High accuracy. The parts in the parallel device become finer and need to be more mechanically processed. At the time of technology, the materiality of the material destroys the workpiece very loudly. Under this circumstance, the defect of the workpiece is degraded by the conventional mechanical processing. : Dali's decline in the nature of the material is important. In-machine processing has not been developed - some processing methods, such as chemical polishing and electrolytic grinding of the electrochemical machine μ ϋ μ ρ shing), to solve the above problem In the traditional physics and mechanical processing method, the dissociation reaction is removed and processed, etc. / by the chemical & _ 丨 丨 \ 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 此 寺 寺 寺 寺 寺 寺 寺 寺 寺 寺And the processing of the crucible is carried out without deteriorating the properties of the material. : In the electrochemical machining process, especially in a pen chemical machining process using pure water, an ion exchanger such as ion: fiber is used to increase the processing rate. Pure water refers to water with a resistivity of 〇.circle (10) or A at 25::, and ultra-pure water refers to water with a resistivity of 1 ΟΜΩ · cm or more at 315115 6 1288681. The ion exchanger typically comprises an ion exchange group, such as a sulfonate, carboxyl, tetravalent ammonium group, n+" or a trivalent or lower amine group, and the ion exchange resin or ion exchange membrane is bonded to the substrate material, such as a copolymer of styrene and divinylbenzene, or a fluororesin. Further, ion exchange groups are known to introduce ion exchange groups into the nonwoven fabric by graft polymerization. Fig. 2 is a schematic view showing the use of conventional ion exchange. As shown in Fig. 2, the working device of the electrolytic processing device of the electrolytic device contains a power supply
窃800，連至该電源供應器8〇〇的陽極（電極）8 ，及連至 該電源供應器800的陰極（電極）82〇。陽極81〇含接至陽極 81〇表面之離子交換器830,且陰極82〇含接到陰極82〇 表面之離子父換盗84〇。將純水或超純水等流體86〇供至 電極810、820和工件850(例如，銅膜）之間。然後，使工The tamper 800 is connected to the anode (electrode) 8 of the power supply 8 , and to the cathode (electrode) 82 该 of the power supply 800. The anode 81 has an ion exchanger 830 attached to the surface of the anode 81, and the cathode 82 contains an ion-exchanger 84 接到 attached to the surface of the cathode 82. A fluid 86 such as pure water or ultrapure water is supplied between the electrodes 810, 820 and the workpiece 850 (e.g., copper film). Then, make work
件850接觸或接近接到電極81〇、82〇表面之離子交換器 83 0、840。由電源供應器8〇〇將電壓施於陽極和陰極 820之間。流體86〇中的水分子會被離子交換器㈣、請 解離成氫氧離子和氫離子。舉例來說，生成的氫氧離子係 供至工件850的表面。因此在工件85〇附近之氫氧離子的 濃度提高，且工件850中的原子和氫氧離子互相反應以進 行工件請表面層之移除。從而認為離子交換器830、840 具有將流體860中的水分子分解成氫氧離子和氫離子之催 化作用。 &The member 850 contacts or is in proximity to the ion exchangers 83 0, 840 that are attached to the surfaces of the electrodes 81, 82. A voltage is applied between the anode and the cathode 820 by the power supply 8'. The water molecules in the fluid 86〇 will be dissociated into hydrogen ions and hydrogen ions by the ion exchanger (4). For example, the generated hydroxide ions are supplied to the surface of the workpiece 850. Therefore, the concentration of hydroxide ions in the vicinity of the workpiece 85 is increased, and the atoms in the workpiece 850 and the hydroxide ions react with each other to remove the surface layer of the workpiece. It is thus believed that the ion exchangers 830, 840 have a catalytic effect of decomposing water molecules in the fluid 860 into hydroxide ions and hydrogen ions. &
然而，當電極810和820為小尺寸（亦即，小直徑）時， 相對於傳統的離子交換樹脂或離子交換纖維，離子交換器 315115 7 1288681 830和840無法分別地配置於電極81〇和82〇的表面上。 因此，陽極810和陰極820必需以離子交換器覆蓋超過陽 極8 1 0和陰極8 2 0。 該例中，若陽極81〇和陰極820之間的距離q小於電 極81〇,82〇和充當工件850之金屬（例如，銅）之間的距離 L2時，在電極810和820之間流通的電流會大於電極 8HM20和工件850之間流通的電流。因此，㈣和 820之間的距離L]必須設定使更大於電極mu" 850之間的距離l2。 然而，離子交換器83〇,840的厚度能防止電極81〇82〇 和工件850之間的距離L被充分地縮短。 口此較佳為&極8 I 〇和陰極8 9 ^ 此“士要^ ’“5 820不得配置太靠近彼 =’％極_和陰極82G的形狀等將有所限制。 傳統離子交換纖維的問題在於電解過程 ，准可月“由離子交換器移出致使經移 " m g± bb ^ m 〕，截、准k成加工性 貝Ik守間而.交化。所以擔心纖維可能合 度造成影響。由此可見，為了使整個：@表面粗糙 將網到離子的離子交換纖維包在不、=垣，嘗試 該工件表面的平坦度可能會受到厚度，However, when the electrodes 810 and 820 are small in size (i.e., small diameter), the ion exchangers 315115 7 1288681 830 and 840 cannot be disposed on the electrodes 81A and 82, respectively, with respect to the conventional ion exchange resin or ion exchange fiber. On the surface of the cockroach. Therefore, anode 810 and cathode 820 must cover the anode 8 1 0 and cathode 820 with an ion exchanger. In this example, if the distance q between the anode 81 〇 and the cathode 820 is smaller than the distance L2 between the electrodes 81 〇, 82 〇 and the metal (for example, copper) serving as the workpiece 850, the flow between the electrodes 810 and 820 is circulated. The current will be greater than the current flowing between the electrode 8HM20 and the workpiece 850. Therefore, the distance L between (4) and 820 must be set to be larger than the distance l2 between the electrodes mu" However, the thickness of the ion exchangers 83A, 840 prevents the distance L between the electrodes 81A and 82b from being sufficiently shortened. The mouth is preferably & pole 8 I 〇 and cathode 8 9 ^ This "should be ^" "5 820 must not be placed too close to one = '% pole _ and the shape of the cathode 82G, etc. will be limited. The problem with the traditional ion-exchange fiber lies in the electrolysis process. The quasi-monthly "removal by the ion exchanger causes the shift [quot; mg± bb ^ m]), and the cut-off and quasi-k become the processability of the shell Ik. It is possible that the degree of influence may be affected. It can be seen that in order to make the whole: @surface rough, the mesh-to-ion ion-exchanged fiber is wrapped in no, =垣, the flatness of the surface of the workpiece may be subjected to thickness,
所影響。 又換抑不均一的厚度 [發明内容;J 因此，本發明的第_ 該電極能達到穩定的 有鑑於上述缺點而完成本發明 個目的在於提供雷自 1、电解加工用的電極 315115 8 1288681 加工性能並可彈性地卢 也處理小笔極和各種電極形狀。 本务明的第二個目 電極的方法。 目的在於&供電解加工裝置及使用該 本發明的第三個s 方法m ; 的在於提供能使液體解離成離子的 5亥方法能達到穩定的加工性能。 為了達成弟一個目的i 電解加工用的電極第一個態樣，提供 團的有機化合物。哕右播外人/ ”十及3離子乂換基 電材料的表面。 化予的方式鍵結至導 根據本發明，且古 接地鍵結至導電材料。田換功能的離子交換材料可直 可作為電解加工用的/此，含離子交換材料的導電材料 之門…肖的電極。經此配置，可縮短電極和工件 '^間的距離，谁而# ^1 1卞 之門的距Μ π 為陽極之電極和作為陰極之電極 <間的距離。因此，4 % ^ 根據本^明的電極可彈性地處理小带 極和各種電極形狀。 ，阳 J ^ 結至作為陽炻夕、* 為離子父換材料可分別地鍵 、 ^電材料和作為陰極的導電;^ # 防止陽極和陰極之4 ^ 包材枓，所以可 ^ I間產生洩漏電流。 吕亥有機化合物可白人 S瓜醇或一硫化物。離子交拖|固 可包含磺酸根、羧其 胳 雕于乂換基團 竣基、四價銨基及胺基之至 電材料可包括金、銀、 者该導 (III)之至少一者。 瓜化“及虱化銦 該導電材料較祛處人士 Μ , τ平乂仏應含有篩孔，因為該篩 以有效地分解水。雷鉉4 # i 了讓水通過 电％加工期間當工件與電 件表面可能會產生刦广丄 接觸時，工 生句痕。由此可見，所欲為電解加工期間 315115 9 1288681 工件不會與電極相接觸。 根據本發明第二個態樣，提供電解加工用的電極。該 電極含有導電碳材和離子解離官能基。該導電碳材的表面< 係藉由離子解離官能基以化學方式加以改質。 " 化作Π亥電極’電極表面具有將水分子分解成離子的催 化作用。因此，可縮短電極和工件之間的距離，進而縮短 作為陽極之電極和作為陰極之電極之間的距離。因此 f本發明的電極可彈性地處理小電極和各種電極形狀。再 二因為作為陽極之電極和作為陰極之電極之中各者皆具 匕作用’可防止陽極和陰極之間產生洩漏電流。 離子解離官能基可包含㈣。離子解離官能基可包含 四 <貝叙基和三價$ —供# a # 包含玻心= 基之至少—者。料電碳材可 匕3玻璃n㈣⑽Ierene)或奈米碳管。 電極發明第三個態樣，提供電解加工用的電極。該 电極具有含驗金屬之石墨嵌人化合物。 使水極，咸認為藉由石墨層之間嵌入的驗金屬得 離，進而二:成離t °因此’可縮短電極和工件之間的距 離。因此為陽極之電極和作為陰極之電極之間的距 電極=:::本:::電極可彈性地處堙小— 之中各者都具有催化作用陽極之，極和作為陰極之電極 電流。，可防止陽極和陰極之間的洩漏 為了達到本發明夕楚_ 樣，提供含有加工i/r ，根據本發明第四個態 -电極和供料電極之加工裝置以供給工 315115 10 1288681 件。该電解加工裝 加工電… 有固定工件並使工件接觸或靠近 力u丄电極用的工株阑 时 極和供料電極之.ΓΓ 解加υ包括在加工電 ώ σ电壓用的電源供應器，以及將流體 :件和加工電極之間的流體供應單元。該 供枓電極之至少—者使用上述電極之任一者。 根據本發明第五個態樣，提供電解加 料電極供蛉1^ u 、、古 於、σ 。在供料電極和加工電極之間施加電壓。 :、工件和加工電極之間。使工件接觸或靠近加工電 加工電極和供料電極之至少—者使用上述電極之任一 者0 · t了達到本發明的第三個目的，根據本發明第六個態 :提供經以化學方式鍵結含離子交換基團之有機化合物 的V電材料促使液體解離成離子的方法。 6亥有機化合物可包含硫醇或二硫化物。該離子交換美 團可包含姐根、縣、四㈣基及胺基之中至少一者: 該導電材料包括金、銀、#、銅、砂化鎵、硫化録及氧化 銦（III)之中至少一者。 由以下的說明參照以實施例方式說明本發明之較佳具 體例的附圖時將使本發明之上述和其他目％、特徵和^點 更為顯著。 [實施方式] 以下將參照附圖說明電極和使用根據本發明具體例之 電極的電解加工裝置。以下的具體例中，以_基材作為工 件並以電解加工裝置加工。然而，本發明亦可應用於該基 315115 11 1288681 材之外的任何工件。 —第3圖為顯示使用根據本發明之電極的電解加 貫施例之概略圖示。如坌 裝置 口丁如弟3圖所示，該電解加工裝 一對電解加工用的雪衣置S有 用的电極1和2。該電極！和2分別 充當基底材料之導電枒粗 也3有 绎电材枓la和h。該導電材料 分別地連接到電源供庫 和2a 电斤仏應為3之陽極和陰極。含 團之有機化合物俜以化風&+ 1 3碓子父換基 物係以化學的方式鍵結至導電 俾於導電材料1的矣 竹ia表面 ' 上形成離子交換材料lb，並且人 離子交換基團之有機化合物 a 祖ο ^ 初係以化學的方式鍵結至導電封 h表面俾於導電材料^的表面上形成離子交換材料 b。如純水或超純水等流體5係供至電件： 如於基材上形成的銅膜)之間。然後，使工件4接觸：:(： 離子交拖M 1 k 3 m @ 4 *近 ,t 1 。以電源供應器3在電極中的 V電碳材1 a和2 a之問恭颅 ’中的 / 間电壓施加電壓。流體5中的氽八2 侍稭由離子交換材料lb 刀子 伽 D解转隹成虱虱離子和筒雜工 舉例來說，將所產生 “雄子。 工杜h 子供至工件4的表面。因此 工件4附近的氫氧離子濃度會提高，且 =此 氫氧離子會相互相反應中的原子和 根據本發明，且有離子二 層之移除。 〃有離子父換功能的離子交 接鍵結至充當基底材料之導電材料 、二 令雜工-丨丨 X乐3圖所不， 乂換材料之導電材料可作兔+ 用士， 作為^解加工用的電極。利 乂置’可縮短電極】，2和工件(基材)4之間的距離 4㈣為陽極之電極丨和作為陰極之電極 離。阳+ 之間的距 1解加工裝置可彈性地處理小電極和各種電極 3I5JJ5 12 1288681 形狀。再者’因為離子交換 之導雷姑料1 a 44 j刀別地鍵結至作為陽極 之V電材料la和作為陰極之導_ 2a，所 極和陰極之間，亦即’電極i % ,.^ # 2之間，的洩漏電流。 ;L “極都含有離子交換材料，A中含離子 交換基團之有機化合物係以化學的 1、中3離子 語「鍵結」表示含離子交換 :’、Ά亥電極。術 dt从丄+ 又換基團之材料係藉由化學鍵，而 非精由黏著劑等，鍵結至導電材料。平 中，含離子交換基團的材料俜「 父、樹脂 有機物質。 鍵結」至該樹脂所包含的 所欲為經鍵結有趟、彳卜人仏> 1 _ 。百機化合物之導電材料含有篩孔， 如’晶格圖案或衝孔的金屬， Μ 、’屬因為5亥師孔可讓水通過以右 效地分解水。 該電極可依以下的方彳制、止 〕方式衣仏。說明以卜丙硫醇_3•硫酿 納（HSC3H6 - S03Na)作為右冬虚隹；^4杰甘 、， 厂卜馬有3離子父換基團的有機化合物 並直接地鍵結至鉑其士士 制 基材以製造電極之實施例。以磺酸 根的鈉鹽取代1-丙硫醇之1 子之3 -立而…占而形成1 -丙硫醇-3 -硫酸 鈉（硫醇）。 、百先，製備平坦的翻基材，例如，長度為34 _，寬 度為12.5 mm ’且厚度為〇·5 mm。藉由硫酸和過氧化氫水 /合液將鉑基材表面上的有機物質移除。然後，將鉑基材沈 v又方、j丙&醇硫酸鈉的水溶液中，該水溶液的濃度為數 4 4莫耳/ A升，約12小時。卜丙硫醇_ 3 -硫酸鈉在官能基 磺酸根之影響之下具有親水性。因此，在沈浸之前若鉑基 材的表面為疏水性的，經沈浸之後鉑基材的表面變成親水 315115 1288681 性的而使硫醇將鍵結至該鉑基 N〜衣面。因此，可制屮 坦的鉑電極（Pt_SC w ςη Mj衣成千 也 π vri W3H6_S〇3Na)， 解離功能）。 玉柽具有催化作用（離子 在經由1 -丙硫醇_3_硫酸鈉 .^ ^ 貝的翻電極上，後文中避 刀于解離反應中的催化作用。且赞 •給… 電極設置於含平行板電極之 的雷、、古雷颅从所 电解作用。測罝以下各例子 的電Μ -電壓性質。再者，測量 ^ lL 叙麵電極作為陽極和險 極之比較貫驗的電流_電壓性質。 $陰 (1)以硫醇鉑電極作為陽極， 極。 並以一般的鉑電極作為陰 極 ⑺以-般㈣電極作騎極，並以硫醇_極作為陰 配置於電極之間。相互面對之電極 約。.4cm。藉由該氣樹脂之厚度調整電極之間的 距雔。在電極之間的距離為50 測量。 …口 二條件下進行 第4八圖—為顯示電極之間的距離為η ”之實驗結果 、圖形，而第4β圖為電極之間的距 — 果的圖形。由第4Α和4Β _ \ 之貫驗結 或陰極時，* —般㈣Μ ^ 電極作為陽極 …：又’極作為陽極和陰極之情況相比時， 二將提高數倍至數十倍(最高5。倍）。*此， 不限於水。 子的觸媒。經促使解離的液體並 3151J5 14 1288681 由第4A和4B圖可g A馬 _ ^ ^ ^ 見幻备琶極之間的距離減小時，電 解龟流會變大。具體而言， ^ A 右玉極之間的距離為1 2 // m， 電解笔流值為使用一般始雷托 ^ 又自電極之约50倍大（見第4A圖）。 :、、、：而’若電極之間的距雜炎 ㈣距離為50// m’電解電流值為使用一 般勒電極例子之·約5倍大（見第4B圖）。 上述實施例中，以鉑作A逡命 ^ ., T為¥电材料，將有機化合物鍵 結至該導電材料。然而， 4 ¥憲材枓並不限於鉑。例如， 如金、銀或鋼等金屬皆可作 蜀S 了作為導電材料。或者，該導電材 料可包括含Au膜之玻璃基材，或—坤化鎵)、⑽(硫 化録）、In2〇3(氧化銦⑽）、碳（石墨）等等。根據另-實驗， 已確自忍在使用含Au腺 膘之玻璃基材的例子中可達到類似上 述之電流-電壓性質。爯去，上取# , 一 『貝再者，如聚苯胺為主的材料或奈米碳 :等有機導電材料皆可作為導電材料。具體而言，含離子 交換基團的有機化合物可直接地鍵結至有機導電材料。 上述實施例中，以硫醇作為鍵結至導電材料之有機化 口物然而，β亥有機化合物並不限於硫醇。舉例來說，二 、化物或聚本胺為主的材料或奈米碳管等有機導電材料皆 可作為有機化合物。再者’該離子交換基團並不限於上述 的石黃酸根。舉例來說，叛基、四價鍵基及胺基皆可作為離 子交換基團。根據實驗，已確認以羧基作為硫醇的離子交 換基團時將可達到類似上述的效果。 根據本發明之電極可應用於第5至7圖所示的電解加 工裝置。第5圖為顯示使用根據本發明之電極的電解加工 裝置之實施例的概略圖示，第6圖為顯示第5圖所示之電 315115 15 1288681 解加工裴置的主要架構14，而第7圖為顯示第6圖所示之 主要架構14的主要部分之透視圖。 如第5圖所示，該電解加工裝置主要包括含盛裝超純 K 用的機械加工室12之主要架構14、超純水循環/純 化1置22及高壓超純水供應單元28。該超純水循環/純水 裝置含有廢水槽16、超純水循環/純化段18和高壓泵 '亥阿壓超純水供應單元28含有活塞泵24和壓力傳送 益26。舉例來說’該機械加工t 12係由不錢鋼製造而成。 如第5圖所示’該主要架構14含有工件固定器(固定 台）3〇以便能藉由吸引作用依水平方向以可拆卸的方式固 定半導體晶圓等工件W。該工件固定器3〇係置於機械加 工室12中並具有ΧΥΘ三自由度。具體而言當工件^尤 汉於超純水Η)之中時，由工件固定器3G固定的工件料 方向水平式地移動(見第7圖)並且可在該水平面 上循者0軸（Z軸）旋轉。工件固 1千1-1疋夯3〇可固定工件|並且 提供電流至工件w。舉例來今 _ m j來成，该工件固定器30係由鈦 Γ而成並且含有厚度為1…鍍勤表面。該工件固定 态30係使用超純水以靜水 以支撐（見第5圖）。 纟32依輪射和驅動力方向加 於二7圖所示，將管柱型或圓柱型加工電極34設置 於工件固定器3 〇上。哕， 又置 〇 〇 ,, , ^ 4加卫電極34具有水平延伸的軸心 一加工電極34係由根據本發明之電極所形Η 而言，在管柱型或陳型導電材料^上形成具有離^ 換功能的離子交換材料3仆 又 將3硪子父換基團的有機化 315115 16 1288681 ^、胃化予的方式鍵結至該導電材料。將該加工電極3 4 、' “料3 4a連至電源供應器3 8。以該離子交換材料 3 4 b作為將加工帝ϋ。< 、 包極3 4和工件w之間的超純水之水分子 解離成氫氧離子和氫離子用的觸媒。 艟 私極34連至沿著軸心0-0延伸之可垂直移動 鑪^ ^36。由此’該加工電極34可依照旋轉軸36之旋 轉而循著軸心〇_〇始絲 ^ _ ^ 轉。该加工電極Μ可垂直地移動以 調正加工電極34和 的距離。該工件固二Γ:::所固定之工件w之間 以輻射和驅動力的： 水由靜水軸承(未圖示） …“ 加以支撐。進行電解製程時，加工 靠近工/□降低’使該離子交換材料地的下端部分接觸或 罪近二件固定器30所固定的工件。 飞 書亥電解加工裝晉+古+ 1 且心由a 之間她加電麼用的電源供應器38。此 八肢例中，為了進行工件 至電源供應器38之陰枝曰广衣私加工電極34係連 U之陽極 '然而，視:件（銅）W係連至電源供應器 連至電源供應器38之陽力…4可 38之陰極。 件W可連至電源供應器 如上所述’該工件因 π 加工電極34可循著水平軸旋：3。°广盾著垂：軸旋轉，且 電極34分別依特定方向旋轉=，固定器30和加工 由工件固定器3。所固定的純水10跟著轉。在 “應超純水用的超純水 和力二電㈣之間以高 〜贺鳥40係設置於旋轉方向 315115 17 1288681 的j游側。在旋轉該加工電極34和工件W之至少一者旋 轉時，由旋轉方向的上游側供應純超水1〇至該加工電極 34和工件W之間以有效地移除可能殘留在加工電極34和 工件W之間的氣泡或機械加工產物。 女第5圖所示，藉由超純水循環/純化裝置22中的純 超尺循ί衣/純化& 1 8純化超純水，由高壓超純水供應單元 28 ^的慶力傳送器26加壓，由活塞泵24供入超純水供應 贺嘴4〇中。再者，如第5圖所示，機械加工室12中盛裳 的超砘水1 〇溢流而儲存於廢水槽！ 6中。然後，超純水係 於超純水循環/純化褒置22中純化並藉由高壓果2〇抽回機 械加工室12。將超純水1()之—部分供至靜水軸承u。 利用由此建構的電解加工裝置，以工件固定器3〇固 ::二並降低加工電極34使加工電咖 "、7四妾觸或#近工件w的表面。在此情形之下，以超 、屯化裝置22純化機械加工室12内的超純水10 j[E力口以4盾3¾。 、、， 將加工電極34連至電源供應器38的陰極， 並使工件w接觸電源供應器38的陽極，俾將電壓施於加 工電極34和工件W之間。同時，工件固定器30和加工電 極34同時依牯令士人从μ 77 ^ 、疋方向紅轉使超純水1 〇亦跟著旋轉。 ί = Ϊ力方向上游側之超純水供應㈣40以高壓將超純 料_二電:二:;:：· 氧離子以進行工= 應製造氯離子和氫 之流體係於_層之移除。此例中，超純水10 棧械加工室12中形成並通過離子交換材料34b 315115 18 1288681 以製造大量的氫離子和氫氧離子。由此，將大量的氫離子 或氫氧離子供至工件w的表面上以有效地進行電解製 程。 如上所述，使該工件固定器30和加工電極34同時依 特定方向旋轉使超純水10亦跟著旋轉。由設置於旋轉方向 上游側之超純水供應噴嘴40以高壓將超純水供應至加工 電極34和工件W之間。因此，存在於工件W和加工電木 34之間的超純水10可有效地利用新的超純水取代，所r 由電解製造所產生之氣艚釦嬙只4 ^ — 之轧體和機械加工產物可有效地移除汗 貫現穩定的電解製程。 ”Affected. Further, the thickness of the non-uniformity is changed. [Inventive content; J Therefore, the electrode of the present invention can be stabilized. In view of the above disadvantages, the object of the present invention is to provide an electrode for electrode processing, 315115 8 1288681 for processing. Performance and flexibility also handle small pen poles and various electrode shapes. The second method of the electrode of this task. The aim is to & the power supply processing apparatus and the third s method m of the present invention; the method of providing a method capable of dissociating a liquid into ions can achieve stable processing performance. In order to achieve the first aspect of the electrode for electrolytic processing, a group of organic compounds is provided.哕 Right broadcast outsider / "10 and 3 ion 乂 乂 基 基 基 。 。 。 。 。 。 。 。 。 。 。 。 。 。 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据 根据Electrolytic processing / this, the electrode of the conductive material containing the ion exchange material ... Xiao electrode. With this configuration, the distance between the electrode and the workpiece can be shortened, and the distance π of the gate of #^1 1卞 is The distance between the electrode of the anode and the electrode as the cathode. Therefore, 4% ^ according to the electrode of the present invention, the small strip and various electrode shapes can be elastically processed. The yang J ^ knot is as the yang 炻 、, * is The ion parent material can be separately bonded, ^ electrical material and conductive as a cathode; ^ # prevents the anode and cathode from being 4 ^ cladding material, so that leakage current can be generated between the two. Lu Hai organic compound can be white s-melanol or Monosulfide. Ion cross-linking|solid-containing sulfonate, carboxylic acid, ruthenium group, quaternary ammonium group and amine group. The electrophysical material may include gold, silver, and (III) At least one of the melons and the indium antimonide Μ , τ 平乂仏 should contain a mesh because the sieve effectively breaks down water. Thunder 4 # i Let the water pass through the electricity during the % machining process when the workpiece and the surface of the electric device may be in contact with each other. It can be seen that the workpiece is not in contact with the electrode during the electrolytic machining process 315115 9 1288681. According to a second aspect of the invention, an electrode for electrolytic processing is provided. The electrode contains a conductive carbon material and an ionic dissociation functional group. The surface of the conductive carbon material is chemically modified by ionic dissociation functional groups. " Turning into the electrode of the electrode” The electrode surface has a catalytic effect of decomposing water molecules into ions. Therefore, the distance between the electrode and the workpiece can be shortened, thereby shortening the distance between the electrode as the anode and the electrode as the cathode. Therefore, the electrode of the present invention can elastically process small electrodes and various electrode shapes. Further, since each of the electrode as the anode and the electrode as the cathode has a 匕 effect, leakage current between the anode and the cathode can be prevented. The ionic dissociation functional group may comprise (iv). The ionic dissociation functional group may comprise four < Beschuyl and trivalent $ - for # a # containing a glass core = at least the base. The electrical carbon material can be 匕3 glass n (four) (10) Ierene or carbon nanotubes. The third aspect of the invention of the electrode provides an electrode for electrolytic processing. The electrode has a graphite-embedded compound containing a metal. It is considered that the water electrode and the salt are separated by the metal intercalation between the graphite layers, and the second is that the distance between the electrode and the workpiece can be shortened. Therefore, the distance between the electrode of the anode and the electrode as the cathode =::: The::: electrode can be elastically small - each of which has a catalytic anode, a pole and an electrode current as a cathode. Preventing leakage between the anode and the cathode. In order to attain the present invention, a processing apparatus including a processing i/r, a fourth state-electrode and a supply electrode according to the present invention is provided to supply a worker 315115 10 1288681 pieces. . The electrolytic processing and processing electric... has a fixed workpiece and makes the workpiece contact or close to the force 丄 electrode and the supply electrode. ΓΓ The solution is included in the power supply for processing the electric σ σ voltage. And a fluid supply unit between the fluid: piece and the processing electrode. At least one of the electrodes is used for the supply of the electrodes. According to a fifth aspect of the present invention, an electrolytic feed electrode is provided for ^1^u, 古, σ. A voltage is applied between the feed electrode and the process electrode. : between the workpiece and the machining electrode. Bringing the workpiece into contact with or close to at least the processing of the electromachining electrode and the feed electrode - using any of the above electrodes 0 t to achieve the third object of the invention, according to the sixth aspect of the invention: providing chemically A method of bonding a V-electrode material of an organic compound containing an ion-exchange group to cause the liquid to dissociate into ions. The organic compound may contain a thiol or a disulfide. The ion exchange mass group may include at least one of a Siegen, a county, a tetrakis, and an amine group: the conductive material includes gold, silver, #, copper, gallium sulphide, sulphide, and indium(III) oxide. At least one. The above and other objects, features, and advantages of the present invention will become more apparent from the description of the appended claims. [Embodiment] An electrode and an electrolytic processing apparatus using an electrode according to a specific example of the present invention will be described below with reference to the drawings. In the following specific examples, the _ base material is used as a workpiece and processed by an electrolytic processing apparatus. However, the present invention is also applicable to any workpiece other than the base 315115 11 1288681. - Figure 3 is a schematic representation showing an electrolytically applied embodiment using an electrode according to the present invention. As shown in Fig. 3 of the apparatus, the electrolytic processing unit is equipped with a pair of electrodes 1 and 2 for use in the snow-coating system for electrolytic processing. The electrode! And 2, respectively, act as a base material, and also have electrical materials 枓la and h. The conductive material is separately connected to the power supply reservoir and the anode and cathode of the 2a battery. The organic compound containing a group of hydrazines is chemically bonded to the conductive enthalpy on the surface of the bismuth ia of the conductive material 1 to form a ion exchange material lb, and a human ion The organic compound a of the exchange group is chemically bonded to the surface of the conductive seal h to form an ion exchange material b on the surface of the conductive material. Fluids such as pure water or ultrapure water are supplied to the electrical components: such as copper films formed on the substrate. Then, the workpiece 4 is brought into contact:: (: ion exchange drag M 1 k 3 m @ 4 * near, t 1 . with the power supply 3 in the electrode of the V electric carbon material 1 a and 2 a The voltage is applied between the / voltages. The 氽8 2 in the fluid 5 is converted from the ion exchange material lb knife DD to the 虱虱 ion and the tube handicraft, for example, the resulting "male. The surface of 4. Therefore, the concentration of hydroxide ions in the vicinity of the workpiece 4 is increased, and = the atoms in which the hydroxide ions will react with each other and according to the present invention, and the removal of the ion layer is removed. Ion-bonding is bonded to the conductive material that acts as the base material, and the second-handed--X-X3 diagram is not used. The conductive material of the 乂-changing material can be used as a rabbit for use as a solution for processing. The electrode can be shortened, the distance between the 2 and the workpiece (substrate) 4 is 4 (4), the electrode of the anode and the electrode as the cathode. The distance between the positive and the 1 processing device can elastically process the small electrode and various electrodes 3I5JJ5 12 1288681 Shape. Again, because of the ion exchange guide, the scorpion 1 a 44 j knife The ground is bonded to the V-electrode material la as the anode and the cathode _ 2a as the cathode, and between the pole and the cathode, that is, the leakage current between the electrodes i % , .^ # 2 ; Ion exchange material, the organic compound containing ion exchange group in A is characterized by chemical 1, 1, 3 ion "bonding" for ion exchange: ', Ά 电极 electrode. d dt from 丄 + and change the material of the group It is bonded to a conductive material by a chemical bond, not by an adhesive, etc. In a flat, a material containing an ion exchange group 俜 "parent, resin organic substance. Bonding" to the desired content of the resin There are 键, 彳 仏 仏 1 1 1 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电 导电Efficiently decompose water. The electrode can be made according to the following method: 以 丙 硫 硫 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ The factory has a 3 element ion-changing organic compound and is directly bonded to a platinum-based substrate to make electricity. Examples: Substituting a sodium salt of a sulfonate for a 1-mer of a 1-propanethiol to form a 1-propanethiol-3-sulfate (thiol). Turn the substrate, for example, to a length of 34 _, a width of 12.5 mm ' and a thickness of 〇·5 mm. The organic matter on the surface of the platinum substrate is removed by sulfuric acid and hydrogen peroxide water/combination. Then, The concentration of the aqueous solution in the aqueous solution of the platinum substrate is a number of 4 4 mol / A liter, about 12 hours. The propyl mercaptan _ 3 - sodium sulfate in the functional sulfonate It is hydrophilic under the influence of it. Therefore, if the surface of the platinum substrate is hydrophobic before immersion, the surface of the platinum substrate becomes hydrophilic after immersion to make the thiol bond to the platinum-based N~coat. Therefore, it is possible to produce a platinum electrode (Pt_SC w ς η Mj, also π vri W3H6_S 〇 3Na), dissociation function). Zea has a catalytic effect (the ions are on the flip electrode via 1-propanol _3_sodium sulfate. ^ ^ Bei, and the catalysis in the dissociation reaction is avoided in the following. And the electrode is set in parallel The thunder and the Gu Lei skull of the plate electrode are electrolyzed from the electrolysis. The electric Μ-voltage properties of the following examples are measured. Furthermore, the measured current is used as a comparison of the current and voltage properties of the anode and the dangerous pole. $ (1) with a thiol platinum electrode as the anode, and a general platinum electrode as the cathode (7) with a general (four) electrode as the riding pole, and a thiol _ pole as the negative between the electrodes. The electrode is about .4 cm. The distance between the electrodes is adjusted by the thickness of the gas resin. The distance between the electrodes is 50. Under the condition of the mouth 2, the 4th figure is shown - for the display between the electrodes The distance is the experimental result and graph of η ”, and the 4β graph is the graph of the distance between the electrodes. When the junction is 4 or 4 Β _ \ or the cathode, the * (4) Μ ^ electrode acts as the anode...: And when the pole is compared as the anode and the cathode, the second will improve. Up to tens of times (up to 5. times). *This, not limited to water. Substance of the catalyst. The liquid that promotes dissociation and 3151J5 14 1288681 by the 4A and 4B diagram can be g A horse _ ^ ^ ^ see the magic When the distance between the bungee poles decreases, the electrolytic turtle flow will become larger. Specifically, the distance between ^ A and the right jade pole is 1 2 // m, and the electrolysis pen flow value is the general starting Thunder ^ and the self-electrode It is about 50 times larger (see Figure 4A). :,,,: and 'If the distance between the electrodes is (50), the distance between the electrodes is 50// m'. The electrolysis current value is about 5 times larger than the example of the general Le electrode. (See Fig. 4B.) In the above embodiment, platinum is used as the A., T is an electric material, and an organic compound is bonded to the conductive material. However, the material is not limited to platinum. Metals such as gold, silver or steel may be used as the conductive material. Alternatively, the conductive material may include a glass substrate containing an Au film, or - gallium, (10) (vulcanized), In2〇3 (Indium oxide (10)), carbon (graphite), etc. According to another experiment, it has been possible to achieve similar results in the case of using a glass substrate containing Au adenine. Flow-voltage properties. 爯去,上取#, a "beibei, such as polyaniline-based materials or nanocarbon: organic conductive materials can be used as conductive materials. Specifically, containing ion exchange groups The organic compound may be directly bonded to the organic conductive material. In the above embodiment, the mercaptan is used as an organic carboxylate bonded to the conductive material. However, the β-organic compound is not limited to a mercaptan. For example, a compound Or a polyamine-based material or an organic conductive material such as a carbon nanotube can be used as an organic compound. Further, the ion exchange group is not limited to the above-described rhein. For example, a thiol group and a tetravalent bond. Both a base group and an amine group can serve as an ion exchange group. According to experiments, it has been confirmed that an effect similar to the above can be attained when a carboxyl group is used as an ion exchange group of a thiol. The electrode according to the present invention can be applied to the electrolytic processing apparatus shown in Figures 5 to 7. Fig. 5 is a schematic view showing an embodiment of an electrolytic processing apparatus using an electrode according to the present invention, and Fig. 6 is a view showing a main structure 14 of the electric processing apparatus 315115 15 1288681 shown in Fig. 5, and the seventh The figure shows a perspective view of the main part of the main architecture 14 shown in Fig. 6. As shown in Fig. 5, the electrolytic processing apparatus mainly includes a main structure 14 including a machining chamber 12 for ultrapure K, an ultrapure water circulation/purification 1 and a high pressure ultrapure water supply unit 28. The ultrapure water circulation/pure water unit contains a wastewater tank 16, an ultrapure water circulation/purification section 18, and a high pressure pump 'Hai pressure ultrapure water supply unit 28 containing a piston pump 24 and a pressure transfer 26 . For example, the machining t 12 is made of stainless steel. As shown in Fig. 5, the main structure 14 includes a workpiece holder (fixing table) 3 so that the workpiece W such as a semiconductor wafer can be detachably fixed in a horizontal direction by suction. The workpiece holder 3 is placed in the mechanical processing chamber 12 and has a three degrees of freedom. Specifically, when the workpiece is in the ultra-pure water raft, the workpiece material fixed by the workpiece holder 3G is horizontally moved (see Fig. 7) and can be rotated to the 0-axis on the horizontal plane (Z). Axis) rotation. The workpiece is fixed at 1 1-1 疋夯 3 〇 to fix the workpiece | and supply current to the workpiece w. For example, the workpiece holder 30 is made of titanium and has a thickness of 1 ... plated surface. The workpiece fixed state 30 is supported by still water using ultrapure water (see Figure 5). The cymbal 32 is placed on the workpiece holder 3 依 in the direction of the wheel and the driving force as shown in Fig. 7 and the cylindrical or cylindrical machining electrode 34 is placed.哕, 〇〇,, , ^ 4 Guard electrode 34 has a horizontally extending axis. The processing electrode 34 is formed on the column type or the stylus type conductive material by the shape of the electrode according to the present invention. The ion exchange material 3 having the function of changing the function is bonded to the conductive material by means of organicization 315115 16 1288681 ^, which is formed by gastricization. The processing electrode 3 4 , ' the material 3 4a is connected to the power supply 3 8 . The ion exchange material 3 4 b is used as the ultrapure water to be processed. < , the pole 3 4 and the workpiece w The water molecule dissociates into a catalyst for hydroxide ions and hydrogen ions. The niobium pole 34 is connected to a vertically movable furnace ^^36 extending along the axis 0-0. Thus, the machining electrode 34 can be rotated according to the axis of rotation The rotation of 36 follows the axis 〇 〇 丝 ^ ^ ^ ^ ^. The machining electrode Μ can be moved vertically to adjust the distance of the machining electrode 34. The workpiece is fixed two::: the fixed workpiece w Between radiation and driving force: Water is supported by a hydrostatic bearing (not shown) ... ". When the electrolysis process is performed, the processing is close to the work/□ reduction, the lower end portion of the ion exchange material is brought into contact or the workpiece fixed by the two holders 30 is fixed. Fei Shuhai electrolytic processing equipment Jin + ancient + 1 and the heart is powered by a power supply 38 between her. In the case of the eight limbs, in order to carry out the workpiece to the power supply 38, the pendulum private processing electrode 34 is connected to the anode of the U. However, the component (copper) W is connected to the power supply to the power supply. The positive force of 38...the cathode of 4 can be 38. The piece W can be connected to the power supply as described above. The workpiece can be rotated by a horizontal axis due to the π machining electrode 34: 3. ° Guang shield is hanging: the shaft rotates, and the electrodes 34 are respectively rotated in a specific direction =, the holder 30 and the workpiece holder 3 are machined. The fixed pure water 10 is followed by a turn. Between "ultra-pure water for ultrapure water and force two electric (four)", the high-heeled bird 40 series is disposed on the j-side of the rotation direction 315115 17 1288681. At least one of the machining electrode 34 and the workpiece W is rotated. When rotating, pure super water 1 is supplied from the upstream side in the rotational direction to between the processing electrode 34 and the workpiece W to effectively remove bubbles or machined products which may remain between the processing electrode 34 and the workpiece W. As shown in Fig. 5, the pure ultra-pure water is purified by the ultra-pure water circulation/purification device 22, and the ultra-pure water is supplied from the high-pressure ultrapure water supply unit 28 ^ The pressure is supplied to the ultrapure water supply by the piston pump 24. In addition, as shown in Fig. 5, the super-slung water 1 in the machining chamber 12 overflows and is stored in the waste water tank! Then, the ultrapure water is purified in the ultrapure water circulation/purification device 22 and is withdrawn to the machining chamber 12 by the high pressure fruit 2, and the ultrapure water 1 () is supplied to the still water bearing u. Using the thus constructed electrolytic processing apparatus, the workpiece holder 3 is tamped: and the processing electrode 34 is lowered to make the processing electric coffee ", 7 Touch or # near the surface of the workpiece w. Under this circumstance, the ultra-pure water in the machining chamber 12 is purified by the super-deuteration device 22 10 [E-force to 4 shields 33⁄4. 34 is connected to the cathode of the power supply 38, and the workpiece w is brought into contact with the anode of the power supply 38, and a voltage is applied between the processing electrode 34 and the workpiece W. At the same time, the workpiece holder 30 and the processing electrode 34 are simultaneously ordered. The scholar turns red from μ 77 ^ and 疋, so that ultra-pure water 1 〇 also rotates. ί = Ultra-pure water supply on the upstream side of the force direction (4) 40 super high-purity _ two electricity: two:;::· Oxygen ions are used to perform the process of removing the chloride ion and hydrogen stream system. In this example, ultrapure water 10 is formed in the processing chamber 12 and passed through the ion exchange material 34b 315115 18 1288681 to manufacture a large amount of Hydrogen ions and hydroxide ions. Thereby, a large amount of hydrogen ions or hydroxide ions are supplied to the surface of the workpiece w to efficiently perform the electrolysis process. As described above, the workpiece holder 30 and the processing electrode 34 are simultaneously specified. The direction rotation causes the ultrapure water 10 to also rotate. It is set in the rotation direction. The side ultrapure water supply nozzle 40 supplies ultrapure water between the machining electrode 34 and the workpiece W at a high pressure. Therefore, the ultrapure water 10 existing between the workpiece W and the processing bakelite 34 can effectively utilize the new super Pure water is substituted, and the pneumatically produced and produced products produced by electrolytic production can effectively remove the sweat-stable and stable electrolytic process."
根據本發明之電極亦可應用於 ^ ^ 乐8圖所不之電解加J 裝置。苐8圖所示之電解加工裝 解加工驻罢甘士丄 个1、弟7圖所不之| 解加工扁置，其中加工電極134係栌 上 ^ 丁壬備面或球面。若降也 加工电極134，導電材料134a外 - 134b之下端邙八將n 上的離子交換材申 下鳊口P刀將會與工件固定器3() 生點接觸。在此情形之 疋的工件W潑 旧k ，使该加工雷糕， 器30同時旌隸。包桮134和工件固定 "日“疋轉。其他的結構與第7 之結構的相同。 丁之电解加工裝置 利用此電解加工裝置，因為加 純水10將可輕易地 Q面和減少，超 t、至该加工部分的周八 在穩定的條件下谁γ 4 固口Ρ刀。因此，可 料下進仃電解製程。超純水 供應喷嘴40射出。兴 j月匕不品由超純水 ㈣舉例來說，該電解加 超純水的槽體並使命 x置可使用盛裝 卫便电極和工件沈浸於超 射超純水。 . 4水中，而不用喷 315Π5 19 1288681 為除了超純水以外，任何化學材料，包括研磨粒 和，密的化學液體，皆未用於該電解加工裝置，所以該梢 =工室僅可能受到電化學加工期間產生的反應產物 由此’可簡化或免掉該電解製程之後基材的清潔 A、屯水的循％可減少廢水的量。再者，因為不需要 处理任何化學液體’所以可顯著地降低操作成本。 述的具體財，含離子基團的有機化合物係以化學 Γ式鍵結至電極的表面俾於電極的表面上形成離子交換 粗 、、、4、銅、氧化銦等係作為電極材 枓（導電材料），而硫醇、-访外仏Μ 付 g, ^ ^ ^ ^ ^ 一 ”物專係作為含離子交換基 圏之有機化合物。該有機脊八 -朽从一 機化5物係以化學的方式鍵結至該 私極材料俾將離子交換 # 換基團引入電極材料中。導電碳材的 表面可猎由離子解離官能其 化學的方式改質，而不使用 该電極。具體而言， +使用 搡5⑨士 ¥电反材作為電極材料，並藉由盔 機反應直接將離子解籬 上精由無 面中。在該例中由:：有效地引入導電碳材之碳表 交換基團)之間的有機化合物，所以：二“基_ 低化學改質層之厚度，並可改 \ ®此’可降 (或耐移除性)和導電性。 ° 冑離官能基的持久性 第9圖為顯示使用該電極 示。如第9圖所示， 解力裝置之概略圖 202。該電極201和2〇2八右八 电極201和 夕胳托4S有刀別地連至電源供瘅哭 之％極和陰極的導電碳 …时203 台匕其9ΓΠΚ 何〇la和2〇2a。利用離子 月匕基201b以化學的方式 卞％離吕 貝¥笔碳材料2〇la的表面，並 3】5Π5 20 1288681 利用離子解離官能基202b以化學的方式改質該導電碳材 202a的表面。將純水或超純水等流體205供至電極201、 202和工件204(例如，在基材上形成之銅膜）之間。然後， 使工件204靠近電極201、202中的離子解離官能基2〇lb、 202b。藉由電源供應器2〇3在電極2〇1、2〇2中的導電碳材 201a和202a之間施加電壓。藉由離子解離官能基2〇lb、 2〇2b將流體205中的水分子解離成氫氧離子和氫離子。舉 例來說，將所產生的氫氧離子供至工件2〇4表面。藉此將 工件204附近的氫氧離子的濃度提高，並使工件2〇4中的 原子與氫氧離子相互反應而進行工件2〇4表面層之移除。 由此，可縮短電極201、2〇2與工件（基材）2〇4之間的 距離，進而縮短作為陽極之電極2〇1和作為陰極之電極 之間的距離。目此，該電解加工裝置可彈性地處理小電極 和各種電極形狀。再者，因為作為陽極之導電碳材201a 和作為陰極之導電碳材202a分別地鍵結至（或以化學的方 式改質）離子解離官能美 〇 n θ 犯暴201b、202b，因此可防止陰極和 陽極之間，亦gp，+ 电極201和202之間產生洩漏電流。 )、含導電碳材並藉由離子解離官能基以化學方式改質 各亥導電奴材表面之恭 、 囬艾电極可作為上述第5至7 例的電解加工裝置，吓 ”體 衣置而不使用有機化合物以化學的方式鍵 、、’口 蛉免材料表面之電極。 勺八^予的方式改質導電碳材表面之離子解離官能 〇 3四價錄基或三價 貝次炅低彳貝胺基寺鹼性基團或羧基等 性卷團。 315115 21 1288681 若4電極係用以處理約丨cm2或更大之較大面積時，該 導電碳材較佳應包含具有平坦且平滑表面且可加工成具有 问準確度之形狀的碳材料，例如玻璃碳。若該電極係用以 、亍# m或小於1 # m專級之精細加工時，較佳應使用富 勒烯或奈米碳管作為導電碳材。所欲為該導電碳材含有篩 孔’因為該篩孔可使水通過而有效地分解水。 以化學方式改質含離子交換基團等離子解離官能基 之‘電铁材的方法包括使導電碳材沈浸於化學液體中，於 氣相中放電處理導電碳材，並於電解溶液中電鍍導電碳 材。 舉例來說，關於使導電碳材沈浸於化學液體之方法 中，導電碳材係沈浸於硝酸等氧化溶液之中。利用此方法， 該導電碳材的表面可輕易地藉由㈣等離子解離官能基以 化學的方式改質。 舉例來說，關於於氣相令放電加工導電碳材的方法 中藉由RF放電（13.25MHz)在含氧氣的氣體中形成電漿， 並使導電碳材暴露於該電漿底下。利用此方法，該導電碳 材的表面可错由羧基等離子解離官能基以化學方式加以改 質。電聚可藉由放電在氮氣環境中形成，^電碳材可暴露 於該電漿底了。該例子中，彳將具有驗性的離子解離官能 基加入該導電碳材内。此等方法適用於藉由離子解離官能 基以化學的方式改質導電性碳材。參I s s w〇ng，A τ W〇〇ley，E. J〇Selevich，C. M. Leiber，以⑽ phys山“，第 306 卷（1999 年），第 219 頁。 315115 22 1288681 鉑板之間的距離之後，在超純水供至碳棒和鉑板之間時， 在碳棒和鉑板之間施加電壓。同時，測量流通的電流。將 碳棒和翻板之間的距離設為1 5 // m。 所再者，比較實驗中以類似於上述之方法測量電流-電壓 (生貝，其中以電弧放電進行碳棒表面處理之前的碳棒作為 陽極，並以鉑板作為陰極。 · 第1〇圖顯示上述實驗的結果。由第10圖可見到相較 於未加入羧基之碳棒，利用電弧放電進行表面處理俾將羧 基加入其中的碳棒在60V肖具有十倍或更多倍之 流。 电 根據在電解溶液中電鍍導電碳材的方法，導電碳材中 幾基之電極係製造如下。以碳棒（導電碳材）作為陽極 亚在電流密度為12.5mA/cm22 2〇重量％仏8〇4溶液中電 二 刀釦以鉑板（Pt)作為對向電極（facing electrode)。 及反棒係由直控6_之石墨製成。該碳棒各端皆為圓的。 該電，碳棒之電流·電壓性質在類似於上述實施例的條件 下測里。將碳棒和鉑板之間的距離設為1 5 // m。 X顯似於上述貫施例的方法測量以電錄進行表 面處理之前的碳棒作為陽極，並以翻板作為陰極之: 驗的電流-電壓性質。 貝 ^第11圖頦不上述實驗的結果。由第11圖可見到相較 方、未加人緩基之碳棒’藉由電鑛作用將叛基加人 棒具有十倍或更多倍之提高電流。 /、中的反 藉由電鑛將缓基加入其中之碳棒係㈣為加工電極 315115 24 1288681 以進行在石夕基材上形成鋼膜之電解製程。該電解製程係於 60V之電壓H.G7mA之電流時進行iq秒而電極之間的 距離為25”。電解製程的結果，最大的加工深度為 144腿。同時，電流效率約48%。電流效率表示用於加工 該銅膜之電流量對所有通過的電流量之比_。⑽㈣# Ϊ設銅係以二價離子或二價離子化合物的形式洗提而計 算。 未經電鑛加人叛基之碳棒係用作加工電極以進行在 石夕基材上形成銅膜之電解製程。該電解製程係於卿 壓和0.043mA之電流時進行6Q秒。電解製程的結果 大的加工深度為12nm。同時，電流效率約3 。 由此可見到與未加入叛基之碳棒相比時，藉由電鐘加 二=之碳棒在電解製程期間具有提高的電流及提高的電 可以含驗金屬之石墨嵌入化合物作為電極，而不使用 藉由離子解離官能基以化學方式改質導電碳材之表面的希 極。通常希望以高度取向的熱解石墨⑽pG)作為石墨嵌: 化口物中的石墨（碳材）。然而，若以納作為驗金屬嵌入於 石墨層之間時’希望以低取向的石墨作為石墨故人化合物 中的石墨。該石墨嵌入化合物較佳應含有篩孔，因為 孔可使水通過俾有效地分解水。 “、、師 一第斤12圖為顯示使用該電極之電解加工裝置的概略 示。如第12圖所示，該電解加工裝置含有一對連至 1 應器3〇3的陽極和陰極之電極3〇1和302。該電極3〇1、和 3]5115 25 1288681 3 02係由s驗金屬之石墨嵌入化合物製成。純水或超純水 等*體3 05係供至電極（石墨後入化合物）3 〇工、逝和工件 3 〇4(例如，在基材上形成之銅膜）之間。然後，使工件3⑸ 罪近電極301、302。藉由電源供應器3〇3在電極3〇1和3〇2 之間施加電壓。藉由石墨嵌入化合物製成的電極3〇1和3〇2 將l體305中的水分子解離成氫氧離子和氯離子。舉例來 說’將所產生的氫氧離子供至工件3〇4表面。藉此將工件 3〇=附近的氫氧離子的濃度提高，並使工件304中的原子 與氫氧離子相互反應而進行工# 3〇4纟面層之移除。 由此，可縮短電極301、302與工件（基材）3〇4之間的 距離，進而縮短作為陽極之電極3〇1和作為陰極之電極Μ] 之間的距離。因此，該電解加工裝置可彈性地處理小電極 和各種電極形狀。再者，因為作為陽極之電極期和作為 陰極之電極302皆具有催化作用，所以可防止陰極和陽極 之門亦即，電極301和302之間產生洩漏電流。 該電極 述第5至7 機化合物以 石墨敌 相接觸反應 包含將驗金 密封玻璃管 金屬嵌入的 墨的溫度而 入化合物，可用於上 工裝置中，而不用有 表面之電極。 氣相恆壓反應法、液 。該氣相恆壓反應法 同位置處，在真空下 該石墨和驗金屬。驗 藉由控制驗金屬和石 鉀嵌入HOPG時，溫 ’包括含驗金屬之石墨嵌 圖所示之具體例的電解加 化學方式鍵結至導電材料 入化合物之合成方法包括 法、固相加壓法和溶劑法 屬和石墨置於玻璃管的不 並在控制的溫度時加熱 位置和驗金屬嵌入的量可 加以調整。舉例來說，當 315115 26 1288681 度係設定於約250°C。該液相接觸反應法包含使液相中含 驗金屬的化合物直接與石墨接觸而相互反應。該固相加壓 法包含使驗金屬與石墨接觸’將石墨加壓至約5至約2〇 大氣壓（約〇·5至約2MPa)，並將該石墨加熱至約2〇(Γ(：。 該溶劑法包含將驗金屬溶於銨溶劑等溶劑，並使石墨沈、、君 於該溶劑中。 根據該液相接觸反應法，由含鹼金屬之石墨嵌入化人 物製成的電極係製造（合成）如下。藉由燃燒器在坩瑪中加 熱並使硝酸鈉熔融，該硝酸鈉之熔點為3〇8^。使石墨板， 長度為12.5mm、寬度為34mm且厚度為〇.5mm，沈浸於熔 融的硝酸鈉當中，並在其中加熱2至3分鐘。然後，自掛 堝中移出石墨板並在空氣中冷卻。藉此製造由含鈉嵌入石 墨層之間的石墨嵌入化合物製成之電極。接著，在第^ 圖所示之貫驗裝置中測量電流-電壓性質。該實驗裝置含有 亞克力製容器320和一對平行板電極321和322。以由石 墨嵌入化合物製成的電極作為電極321，並以鉑板作為電 極322。將此等電極321和322分別地連至電源供應器323 之陽極和陰極。 電流-電壓性質，該超 在超純水325中測量The electrode according to the present invention can also be applied to an electrolysis plus J device which is not shown in Fig. 8.电解8 Figure shows the electrolytic processing and assembly processing stationed in the Ganshi 丄 1 1, the brother 7 figure is not | the processing flat, in which the processing electrode 134 is on the ^ 壬 壬 壬 or spherical surface. If the electrode 134 is also machined, the lower end of the conductive material 134a - 134b will be the same as the ion exchange material on the n. The P knife will contact the workpiece holder 3 (). In this case, the workpiece W is splashed with the old k, so that the processing cake, the device 30 is simultaneously smashed. The cup 134 and the workpiece are fixed. The other structure is the same as that of the seventh structure. The electrolytic processing device of Ding uses this electrolytic processing device because the addition of pure water 10 can be easily Q-faced and reduced. t, to the processing part of the week under stable conditions, who is γ 4 fixed-mouth boring tool. Therefore, it is possible to enter the 仃 electrolysis process. Ultra-pure water supply nozzle 40 is injected. Xing j Yue 匕 not from ultra-pure water (4) For example, the tank with electrolysis plus ultrapure water and the mission x can be used to immerse the toilet electrode and the workpiece in the super-shot ultrapure water. 4 water, instead of spraying 315Π5 19 1288681 is in addition to ultrapure water In addition, any chemical materials, including abrasive particles and dense chemical liquids, are not used in the electrolytic processing unit, so the tip = the chamber may only be subjected to reaction products generated during electrochemical processing, thereby simplifying or eliminating After the electrolysis process, the cleaning of the substrate A and the percentage of the hydrophobic water can reduce the amount of waste water. Furthermore, since no chemical liquid is required to be processed, the operation cost can be remarkably reduced. The specific wealth, ionic group-containing Organic The system is chemically bonded to the surface of the electrode to form an ion exchange rough, 4, copper, indium oxide, etc. as an electrode material (conductive material), and the mercaptan, Μ pay g, ^ ^ ^ ^ ^ a "specialist" as an organic compound containing an ion exchange group. The organic ridges are chemically bonded to the cryptomaterial from the organic chemistry, and the ion exchange group is introduced into the electrode material. The surface of the conductive carbon material can be modified by the chemical separation of the ionic dissociation function without using the electrode. Specifically, + use 搡59士 ¥ electric counter material as the electrode material, and directly detach the ion from the surface by the helmet reaction. In this case, the organic compound between: the carbon exchange group of the conductive carbon material is effectively introduced, so: the thickness of the second "base_low chemically modified layer, and can be changed \ ® this can be reduced ( Or resistance to removal) and conductivity. ° Persistence of functional groups. Figure 9 shows the use of the electrode. As shown in Figure 9, a schematic diagram of the force-relief device 202. The electrodes 201 and 2〇2 Eight right eight electrodes 201 and 夕 托 4S have a knife connected to the power supply for the crying of the pole and the cathode of the conductive carbon... when 203 Taiwan 匕 9ΓΠΚ He〇la and 2〇2a. Using ion Moon base 201b Chemically 卞% from the surface of Lubei ¥ pen carbon material 2〇la, and 3]5Π5 20 1288681 chemically modify the surface of the conductive carbon material 202a by ion dissociation functional group 202b. Pure water or super A fluid 205 such as pure water is supplied between the electrodes 201, 202 and the workpiece 204 (e.g., a copper film formed on the substrate). Then, the workpiece 204 is brought close to the ions in the electrodes 201, 202 to dissociate the functional groups 2, lb, 202b. A voltage is applied between the conductive carbon materials 201a and 202a in the electrodes 2〇1, 2〇2 by the power supply 2〇3. The water molecules in the fluid 205 are dissociated into hydroxide ions and hydrogen ions by the ionic dissociation functional groups 2〇lb, 2〇2b. For example, the generated hydroxide ions are supplied to the surface of the workpiece 2〇4. The concentration of hydroxide ions in the vicinity of the workpiece 204 is increased, and the atoms in the workpiece 2〇4 are reacted with the hydroxide ions to remove the surface layer of the workpiece 2〇4. Thereby, the electrodes 201, 2〇2 and The distance between the workpiece (substrate) 2〇4 further shortens the distance between the electrode 2〇1 as the anode and the electrode as the cathode. Accordingly, the electrolytic processing apparatus can elastically process the small electrode and various electrode shapes. Furthermore, since the conductive carbon material 201a as the anode and the conductive carbon material 202a as the cathode are respectively bonded (or chemically modified) to the ion dissociation functional 〇n θ violent 201b, 202b, the cathode can be prevented Between the anode and the anode, a leakage current is also generated between the gp and the electrodes 201 and 202. The conductive carbon material is chemically modified by the ion dissociation functional group to chemically modify the surface of each of the conductive substrates. Extremely as the above 5th to 7th examples Solution processing means scared "garment facing body without using an organic compound in the manner of a chemical bond ,, 'Free lacewing port surface of the electrode material. The ionic dissociation function of the surface of the conductive carbon material is modified by the method of spoon 8 予 3 quaternary or trivalent 炅 炅 炅 彳 碱性 碱性 寺 寺 寺 碱性 basic group or carboxyl group. 315115 21 1288681 If the 4-electrode is used to process a large area of about 丨cm2 or larger, the conductive carbon material should preferably comprise a carbon material having a flat and smooth surface and capable of being processed into a shape having an accuracy of accuracy, for example Glassy carbon. If the electrode is used for fine processing of 亍#m or less than 1 #m, it is preferred to use fullerene or carbon nanotubes as the conductive carbon material. It is desirable to have a mesh hole for the conductive carbon material because the mesh hole allows water to pass through and effectively decomposes water. A method for chemically modifying an 'electrical iron material containing an ion exchange group plasma dissociation functional group includes immersing the conductive carbon material in a chemical liquid, discharging the conductive carbon material in a gas phase, and plating the conductive carbon in the electrolytic solution material. For example, in the method of immersing a conductive carbon material in a chemical liquid, the conductive carbon material is immersed in an oxidizing solution such as nitric acid. With this method, the surface of the conductive carbon material can be easily chemically modified by the (iv) plasma dissociation functional group. For example, in the method of electrically discharging a conductive carbon material in a gas phase, a plasma is formed in an oxygen-containing gas by RF discharge (13.25 MHz), and the conductive carbon material is exposed to the bottom of the plasma. With this method, the surface of the conductive carbon material can be chemically modified by a carboxyl group plasma dissociation functional group. Electropolymerization can be formed by a discharge in a nitrogen atmosphere, and the electric carbon material can be exposed to the bottom of the plasma. In this example, hydrazine incorporates an illustrative ionic dissociation functional group into the electrically conductive carbon material. These methods are suitable for chemically modifying a conductive carbon material by ionic dissociation of a functional group. See I ssw〇ng, A τ W〇〇ley, E. J〇Selevich, CM Leiber, (10) Phys Mountain, Vol. 306 (1999), p. 219. 315115 22 1288681 After the distance between the platinum plates When ultrapure water is supplied between the carbon rod and the platinum plate, a voltage is applied between the carbon rod and the platinum plate. At the same time, the current flowing is measured. The distance between the carbon rod and the flap is set to 1 5 // m. In the comparative experiment, the current-voltage (raw shell) was measured in a similar manner to the above method, in which the carbon rod before the surface treatment of the carbon rod by arc discharge was used as the anode, and the platinum plate was used as the cathode. The results of the above experiment are shown. It can be seen from Fig. 10 that the carbon rod to which the carboxyl group is added is subjected to a surface treatment by arc discharge as compared with a carbon rod to which no carboxyl group is added, and the carbon rod having a carboxyl group added thereto has a flow of ten or more times at 60 V. According to the method of electroplating a conductive carbon material in an electrolytic solution, the electrodes of several groups in the conductive carbon material are manufactured as follows. The carbon rod (conductive carbon material) is used as an anode sub-current density of 12.5 mA/cm22 2 〇% by weight 仏8〇 4 The electric two-knife buckle in the solution is made of platinum plate (Pt) The facing electrode and the anti-rod are made of graphite directly controlled by 6_. The carbon rods are round at each end. The current and voltage properties of the carbon rod are similar to those of the above embodiment. In the measurement, the distance between the carbon rod and the platinum plate is set to 1 5 // m. X is similar to the method of the above-mentioned embodiment, and the carbon rod before the surface treatment by electro-recording is used as the anode, and the flap is used as the anode. Cathode: The current-voltage property of the test. Fig. 11 is not the result of the above experiment. It can be seen from Fig. 11 that the carbon rods that are compared with the square and the unheated base are used to rebel. The human rod has an electric current of ten times or more. /, the reverse of the carbon rod system (4) by which the electric ore is added to the slow-base is processed electrode 315115 24 1288681 to form a steel film on the stone substrate. The electrolysis process is performed at a current of 60 V at a current of H.G7 mA for iq seconds and the distance between the electrodes is 25". As a result of the electrolysis process, the maximum processing depth is 144 legs. Meanwhile, the current efficiency is about 48%. Current efficiency represents the amount of current used to process the copper film for all passed currents The ratio _.(10)(4)# The copper system is calculated by eluting in the form of divalent ions or divalent ionic compounds. The carbon rods that are not repelled by the electric ore are used as processing electrodes for performing on the Shixi substrate. An electrolytic process for forming a copper film. The electrolytic process is performed for 6Q seconds at a voltage of 0.043 mA. The result of the electrolytic process is a large processing depth of 12 nm. At the same time, the current efficiency is about 3. When the carbon rod is compared with the carbon rod, the electric current is increased by the electric clock and the carbon rod is increased during the electrolysis process, and the increased conductivity of the metal can be performed by using the graphite intercalation compound as the electrode instead of using the ion dissociation functional group. Chemically modifying the surface of the conductive carbon material. It is generally desirable to use highly oriented pyrolytic graphite (10) pG) as graphite in the graphite (carbon material) in the mouth. However, if the nano-doped metal is intercalated between the graphite layers, it is desirable to use graphite having a low orientation as the graphite in the graphite compound. Preferably, the graphite intercalation compound will contain a mesh opening because the pores allow water to efficiently decompose water through the crucible. ",,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, 3〇1 and 302. The electrodes 3〇1, and 3]5115 25 1288681 3 02 are made of graphite graphite embedded compound. Pure water or ultrapure water, etc. 3 body is supplied to the electrode (after graphite) Into the compound) 3 is completed and passed between the workpiece 3 〇 4 (for example, a copper film formed on the substrate). Then, the workpiece 3 (5) is sinned near the electrodes 301, 302. The power supply 3 〇 3 at the electrode A voltage is applied between 3〇1 and 3〇2. The electrodes 3〇1 and 3〇2 made of graphite intercalation compound dissociate the water molecules in the l body 305 into hydroxide ions and chloride ions. For example, 'will The generated hydroxide ions are supplied to the surface of the workpiece 3〇4, thereby increasing the concentration of the hydroxide ions in the vicinity of the workpiece 3〇=, and reacting the atoms in the workpiece 304 with the hydroxide ions to perform the work #3〇4 The removal of the surface layer can thereby shorten the distance between the electrodes 301, 302 and the workpiece (substrate) 3〇4, thereby shortening the The distance between the electrode of the anode 3〇1 and the electrode 作为 as the cathode. Therefore, the electrolytic processing apparatus can elastically process the small electrode and various electrode shapes. Furthermore, since the electrode phase as the anode and the electrode 302 as the cathode They all have a catalytic action, so that the cathode and anode gates, that is, the leakage current between the electrodes 301 and 302, can be prevented. The electrode of the fifth to seventh organic compounds in the graphite enemy phase reaction involves embedding the gold-filled sealing glass tube metal. The temperature of the ink enters the compound and can be used in the working device without the surface electrode. Gas phase constant pressure reaction method, liquid. The gas phase constant pressure reaction method is at the same position, the graphite and the metal under vacuum When the test is carried out by controlling the metal and the potassium is embedded in the HOPG, the temperature includes a specific example shown in the graphite inlay of the test metal, and the chemical synthesis method is used to bond the conductive material to the compound. The synthesis method includes a method, a solid phase addition. The pressure and solvent method and the amount of graphite placed in the glass tube at a controlled temperature and the amount of metal embedding can be adjusted. For example, when 315 115 26 1288681 The degree is set at about 250 ° C. The liquid phase contact reaction method comprises reacting a metal-containing compound in the liquid phase directly with graphite to react with each other. The solid phase pressing method comprises contacting the metal with graphite. Pressurizing the graphite to a pressure of about 5 to about 2 Torr (about 〇·5 to about 2 MPa), and heating the graphite to about 2 〇 (Γ. The solvent method comprises dissolving the test metal in a solvent such as an ammonium solvent, The graphite is precipitated in the solvent. According to the liquid phase contact reaction method, an electrode system made of an alkali metal-containing graphite-embedded person is manufactured (synthesized) as follows. The burner is heated in the gamma. The sodium nitrate is melted, and the melting point of the sodium nitrate is 3〇8^. The graphite plate, having a length of 12.5 mm, a width of 34 mm and a thickness of 〇.5 mm, was immersed in molten sodium nitrate and heated therein for 2 to 3 minutes. Then, the graphite plate was removed from the hanging raft and cooled in the air. Thereby an electrode made of a graphite intercalation compound between the sodium-containing inlaid graphite layers is produced. Next, the current-voltage characteristics are measured in the inspection apparatus shown in Fig. The experimental apparatus contains an acrylic container 320 and a pair of parallel plate electrodes 321 and 322. An electrode made of a graphite-embedded compound was used as the electrode 321, and a platinum plate was used as the electrode 322. These electrodes 321 and 322 are connected to the anode and cathode of the power supply 323, respectively. Current-voltage properties, the super is measured in ultrapure water 325
Cm。同時，電極321和322之 ，且相互面對之電極321和322 純水的電阻率為18.2ΜΩ · 間的距離係設定於1 2 // m 的面積係設定於約〇.4cm2 再者，以相似於上述之方法測量比較實驗之電流-電壓 性質：其巾以石墨層之間未嵌入納的石以作為電極。 第14圖顯示上述實驗的結果。由第14圖可見到由含 315115 27 1288681 鈉嵌入石墨層之間的石墨嵌入化合物製造的電極在15 〇v 時能提供稍低於50mA之電流（電流密度為125mA· m2)， 因此與鈉未嵌入石墨層之間的石墨板相比時，具有約5〇 倍之提高電流。因此，咸認為鈉嵌入石墨層之間的石墨嵌 入化合物可促使超純水解離成氫離子或氫氧離子。 上述實施例中，石墨係沈浸於使硝酸鈉受熱並熔融之 液體中。然而，該石墨可沈浸於任何含鹼金屬，如硝酸鉀， 之鹽類中。 稀釋的化學液體可作為添加物添加至純水。舉例來 說，2-丙醇（IPA)可添加至純水以調整純水的極性。 儘管已顯示並詳細說明本發明某些較佳的具體例，但 要瞭解其中仍可進行各種變化 矛L飾而不會悻離後附申請 專利範圍之範轉。 I畫可利用姓 ，该電極係作為加工基材用之加 特別疋純水，之電解製程期間用Cm. At the same time, the resistivity of the electrodes 321 and 322 and the mutually facing electrodes 321 and 322 of pure water is 18.2 Μ Ω. The distance between the electrodes is set at 1 2 // m, which is set at about 〇.4 cm 2 The current-voltage properties of the comparative experiments were measured similarly to the above method: the towels were not embedded with stones between the graphite layers as electrodes. Figure 14 shows the results of the above experiment. It can be seen from Fig. 14 that an electrode made of a graphite intercalation compound containing 315115 27 1288681 sodium intercalated between graphite layers can provide a current of slightly less than 50 mA (current density of 125 mA·m 2 ) at 15 〇v, so When compared to a graphite plate embedded between graphite layers, it has an increase current of about 5 times. Therefore, it is believed that the graphite intercalation compound between the sodium intercalated graphite layers promotes ultrapure hydrolysis to form hydrogen ions or hydroxide ions. In the above embodiment, the graphite is immersed in a liquid which causes sodium nitrate to be heated and melted. However, the graphite can be immersed in any salt containing an alkali metal such as potassium nitrate. The diluted chemical liquid can be added to the pure water as an additive. For example, 2-propanol (IPA) can be added to pure water to adjust the polarity of pure water. While certain preferred embodiments of the present invention have been shown and described in detail, it is understood that various modifications can be made therein without departing from the scope of the appended claims. I can use the surname of the painting, and the electrode is used as a processing substrate with special pure water, which is used during the electrolysis process.
本發明可應用於電極 工電極及/或在使用流體， 以供給基材之供料電極。 [圖式簡單說明J 的鋼内連線之形成製程 第1A至1C圖為顯示在基材中 的實施例之圖示； 第 概略圖 2圖為顯示使用傳統離子 不 ， 交換器之電解加工裝置的 第 略圖示The invention can be applied to an electrode electrode and/or a feed electrode that uses a fluid to supply a substrate. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A to FIG. 1C are diagrams showing an embodiment of a steel interconnect in J. The schematic diagram of FIG. 2 shows an electrolytic processing apparatus using a conventional ion, exchanger. Slightly icon
圖為顯示使用本發明之泰A 兔極的電解加工裝置之概 315115 28 Ϊ288681 第4A和4B圖為顯示利用含導 =機化合物以化學方式鍵結至該導電=基 电％ 4程時之電流_電壓性質圖形； •進仃 第5圖為顯示使用根據本發明之電解 例的概略圖示； 才罝之貝轭 弟6圖為顯示弟5圖所示之電解加 的截面圖示； 第7圖為顯示第6 工裝置之主要架構 圖之電解加工裝置巾❹定部件和 加工電極之透視圖； 立第8圖為顯示根據本發明另一電解加工裝置中 部件和加工電極之透視圖； 第9圖為顯示包含根據本發明另一類型電極 工裝置的概略圖示； 第10圖為顯示第9圖所示之電極的電流_ 的固定 之電解加 圖形； 電壓性質 之 第Η圖為顯示第9圖所示之電極的電流 圖形； 電壓性質 之 第12圖為顯示含根據本發明之另一類型電極之 加工裝置之實施例的概略圖示； 第13圖為顯示用於測量根據本發明之電極的電流-爺 壓性質之實驗裝置的概略圖示； ^ ^ 第14圖為顯示第12圖所示之電極的電流-電壓性質之 圖形’該t流-電壓性質係藉由帛13目之實驗裝心。 315Π5 29The figure shows an electrolytic processing apparatus using the Thai A rabbit pole of the present invention. 315115 28 Ϊ 288681 Figs. 4A and 4B are diagrams showing the current when chemically bonded to the conductive = base electric power using a derivative containing a derivative compound _voltage property pattern; • Fig. 5 is a schematic diagram showing the use of an electrolytic example according to the present invention; Fig. 5 is a cross-sectional illustration showing the electrolytic addition shown in Fig. 5; BRIEF DESCRIPTION OF THE DRAWINGS FIG. 8 is a perspective view showing a portion of an electrolytic processing device and a processing electrode of a main structural view of a sixth working device; FIG. 8 is a perspective view showing a component and a processing electrode of another electrolytic processing apparatus according to the present invention; 9 is a schematic view showing another type of electrode apparatus according to the present invention; FIG. 10 is a diagram showing a fixed electrolysis pattern of the current_ of the electrode shown in FIG. 9; Figure 9 is a current diagram of an electrode; Figure 12 of the nature of the voltage is a schematic representation showing an embodiment of a processing apparatus comprising another type of electrode according to the invention; Figure 13 is a diagram showing the measurement according to the invention. A schematic diagram of the experimental device for the current-voltage characteristics of the electrode; ^ ^ Figure 14 is a graph showing the current-voltage properties of the electrode shown in Fig. 12. The t-flow-voltage property is obtained by 帛13 mesh. Experimental heart. 315Π5 29
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002295421AJP3953400B2 (en) | 2002-10-08 | 2002-10-08 | Ion dissociation promotion method, electrode for electrolytic processing, electrolytic processing method and apparatus |
| JP2003070898 | 2003-03-14 |
| Publication Number | Publication Date |
|---|---|
| TW200406276A TW200406276A (en) | 2004-05-01 |
| TWI288681Btrue TWI288681B (en) | 2007-10-21 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW092127739ATWI288681B (en) | 2002-10-08 | 2003-10-07 | Electrode for electrolytic processing, and electrolytic processing apparatus and electrolytic processing method using the same |
| Country | Link |
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| TW (1) | TWI288681B (en) |
| WO (1) | WO2004033765A1 (en) |
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