200406276 玫、發明說明 [1¾明所屬之技術領域] 本發明係關於雷解力口 jq + 、电斛加工用的電極，更具體而言關於加 工基材用的加工電極及/或在使用流體，特別是純水，之電 解加工期間用以供給基材的供料電極（feeding eiectrode)。 本發明亦關於使用該電極之電解加工裝置及方法。本發明 亦關於能將液體解離成離子 I万法，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’有利用具有低電阻率及高電遷移阻抗的銅(Cu) 更換用在半導體晶圓等基材 T上用方；形成内連線電路充當金 屬材料之鋁或鋁合金的趨勢。 “ 奶内連線（interconnection) 通吊錯由將銅填入基材表面中 卸甲形成的精細凹部而形成。 於形成銅内連線的方法， πνη、 A 匕便用的有化學氣相沈積 (CVD)、濺鍍及鍍敷。任一 敕袖I * 万法宁寺銅胰貫質上形成於 正個基材表面上之後，不雲 ， 移除。 …’5稭由化學機械研磨（CMP) 第1A至1C圖顯示在基材w中形成銅 例。如第1A圖所示，將9 良的戶'鈿 將、七緣朕2，例如Si〇,之氧 低k材料之薄膜，、十择仏4 *·乳化或 …専“於彼上已形成有半導體裝置之半導 月豆基底1上的導電層]μ ^ 上。猎由^影蝕刻技術在絕緣腺9 中形成接觸孔3和内連崎、羞描Λ . 、彖朕- Κ '、果溝槽4。然後，在絕緣膜？ 成由丁aN等製成之阻障層 “上形 早智5，亚糟由濺鍍、cvd箄士 1各 阻障層5上形成晶種層7，兮s鍤恳 寻方法在 疏日日種層7係用作為電鍍用的 填充層。 接著，如第 1 B 一 使接觸孔3及⑽— 1域㈣基材”表面俾 膜6。之後，、以槽4填滿銅並在絕緣膜2上形成銅 以移除絕緣膜I上化學機械研磨(CMP)研磨基材W的表面 槽4中的銅膜、的銅膜6 ’使填入接觸孔3和内連線溝 如第1C圖所八 、貝/、絕緣膜2的表面平齊。因此，200406276 Rose, description of invention [Technical field to which Mingming belongs] The present invention relates to the electrode for processing jq +, and more specifically to the processing electrode for processing substrates and / or the fluid in use, In particular, pure water is a feeding electrode used to feed substrates during electrolytic processing. The invention also relates to an electrolytic processing device and method using the electrode. The invention also relates to a method capable of dissociating a liquid into ions, and more particularly to a method capable of dissociating a liquid into ions during electrolytic processing. [Prior art] In recent years, there has been replacement of copper (Cu) with low resistivity and high electromigration resistance for use on substrates T such as semiconductor wafers; aluminum or aluminum alloys that form interconnect circuits as metal materials the trend of. "Interconnections are formed by filling copper into the fine recesses formed by removing nails from the surface of the substrate. For the method of forming copper interconnections, πνη and A are used for chemical vapor deposition. (CVD), sputter plating and plating. Any of the sleeves I * Wan Faning Temple copper pancreas was formed on the surface of the substrate, it was clouded and removed.… '5 The straw was ground by chemical mechanical ( CMP) Figures 1A to 1C show examples of the formation of copper in the substrate w. As shown in Figure 1A, 9 good households, shovels and seven margins, such as a thin film of oxygen low-k materials such as Si0, , Ten choices 仏 4 * · emulsified or ... 専 "on the conductive layer on the semiconducting moon bean substrate 1 on which a semiconductor device has been formed] μ ^. The formation of the contact hole 3 and the interconnected ridges, the shale Λ., 彖 朕 -κ ′, and the fruit groove 4 in the insulating gland 9 is performed by the etching technique. Then, in the insulating film? A barrier layer made of Ding aN, etc. is formed on the early wisdom 5, and the seed layer 7 is formed on each of the barrier layers 5 by sputtering, cvd fighter 1 and so on. The seed layer 7 is used as a filling layer for electroplating. Next, as described in Section 1B, the contact hole 3 and the ⑽-1 domain ㈣ substrate "surface 俾 film 6 are formed. After that, copper is filled with the groove 4 and copper is formed on the insulating film 2 to remove the copper film and the copper film 6 ′ from the surface groove 4 of the chemical mechanical polishing (CMP) polishing substrate W on the insulating film I. The surface of the in-contact hole 3 and the interconnecting groove are flush with the surface of the insulating film 2 as shown in FIG. 1C. therefore,
近二二中形成含銅膜6之内連線。 高的準確性。在並、中的令件都變得更加精細且需要更 質受到機械加工：：使用次微米製造技術之時，材料的性 理方式破壞卫件所1^影響極大、。在此情況之下，在以物 傳統的機械加工方：：理的部分並以工具自其表面移除之 缺陷，而使該工件：機械加工的結果可能產生大量的 牛的性質衰退。因此， 使材料的性皙妄 仃機械加工而不 |貝哀退係重要的。 已經研究出一此★丁士、上The interconnects of the copper-containing film 6 are formed in the last two or two. High accuracy. The parts in the union and the middle have become more delicate and need to be more mechanically processed: When using the sub-micron manufacturing technology, the physical way of the material destroys the health part. In this case, in the traditional mechanical processing side of the object: the defects that are removed from the surface by the tool and the tool, so that the workpiece: the result of mechanical processing may produce a large number of degradation of the nature of cattle. Therefore, it is important to make the material's sexuality rather than mechanical processing. Already researched this. Ding Shi, Shang
^ , 二方法，例如化學研磨、雷彳卜與抄 械加工和電解 兒化學機 題。相對於值"ec 10lytlc P〇lishing)，以解決上述問 处相對於傳統物理 解離反庫淮~你& 此寺方法經由化學 久4進仃移除加工 形變彳丨叔 u此此寺方法不會遇到塑型 丨起之父錯層⑷…以laye〇和位錯之升，成算夕杜 陷，而加 t B又形成寺之缺 2工旎在不使材料性質衰退下進行。 在電化學機械加工製程中，特別是 水的電仆與说^ 尺用純水或超純 -化學機械加工製程中，使用如 換纖維笠夕叫7 1 換腰或雄子父 、-之雒子父換器以增加加工速率。純 的電随率為ο·1ΜΩ· cm咬更大白^ ^ U日在25CBf 飞更大的水，而超純水指在75t 315115 6 200406276 1的電时為1()ΜΩ•⑽或更大的水。離子交換器通常包 έ #子乂換基團，例如磺酸根、羧基、四價銨基卜Ν + = )或 二價或更低價的胺|，之離子交換樹脂或離子交換膜係鍵 f至基底材料’如苯乙稀和二乙烯基苯之共聚合物，或氣 树月曰。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圖為颁示使用傳統離子交換器之電解加工裝置的 才叉各圖4如第2圖所不，該電解加工裝置含有電源供應 器800,連至該電源供應器8〇〇的陽極（電極）81〇，及連: 該電源供應器800的陰極（電極）82〇。陽極81〇含接至陽極 810表面之離子交換器83〇，且陰極82〇含接到陰極 表面之喊子父換器84〇。將純水或超純水等流體㈣供至 电極810、820和工件85〇(例如，銅膜)之間。然後，使工 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由电源供應器800將電壓施於陽極8丨〇和陰極 8 20之間m 86Q中的水分子會被離子交換器咖、州 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㈣的表面。因此在工件85〇附近之氯氧離子的 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850表面層之移除。從而認為離子交換器830、84〇 具有將流體860中的水分子分解成氫氧離子和氫離 化作用。 然而，當電極8] 0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 3]5]】5 7 200406276 83 0和840無法分別地配置於電極81〇和82〇的表面 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㈣和陰極820之間的距離l丨小於電 極81 0,820和充當工件850之金屬（例如，銅）之間的距離 L2時，在妹81之間流通的電流會大於電極^, Two methods, such as chemical grinding, thorium and mechanical processing, and electrochemistry. (Relative to the value " ec 10lytlc P〇lishing) to solve the above problems compared to the traditional understanding Li Kuihuai ~ you & this temple method removes the processing deformation by chemical long time 仃 uncle this this temple method You will not encounter the father's staggering sculpting from the shape ... With the rise of laye0 and dislocations, it will be considered as a depression, and the addition of t B will form the lack of the temple. 2 The work will be performed without degrading the material properties. In the electrochemical mechanical processing process, especially the electric power of water, the ruler uses pure water or ultra-pure-chemical mechanical processing processes, such as changing the fiber 笠 Xi Jiao 7 1 waist or male son,-雒 子Parent converter to increase processing rate. The pure electric follow-up rate is ο · 1MΩ · cm. The bite is more white ^ ^ U day flies larger water at 25CBf, while ultrapure water refers to 1 () MΩ • ⑽ or greater at 75t 315115 6 200406276 1 Water. Ion exchangers usually include a #substitution group, such as a sulfonate, carboxyl group, tetravalent ammonium group (N + =) or a divalent or lower amine |, an ion exchange resin or an ion exchange membrane bond f To the substrate material 'such as a copolymer of styrene and divinylbenzene, or Qi Shuyue. Furthermore, it is known that ion exchange groups are introduced into the nonwoven fabric by graft polymerization in the ion exchange fiber. Fig. 2 is a diagram showing an electrolysis processing device using a conventional ion exchanger. Fig. 4 is not shown in Fig. 2. The electrolysis processing device includes a power supply 800 connected to an anode of the power supply 800 ( Electrode) 81 °, and connected: The cathode (electrode) of the power supply 800 is 82 °. The anode 810 contains an ion exchanger 83o connected to the surface of the anode 810, and the cathode 820 contains a shouting parent converter 84o connected to the surface of the cathode. A fluid such as pure water or ultrapure water is supplied between the electrodes 810 and 820 and the workpiece 850 (for example, a copper film). Then, the workpiece 850 is brought into contact with or in close proximity to the ion exchangers 83 0 and 8 2 on the surface of the ion exchanger 83 0 840. The power supply 800 applies a voltage between the anode 8 and the cathode 8 20 and the water molecules in m 86Q will It is dissociated into hydroxide ions and hydrogen ions by the ion exchanger. For example, the generated hydroxide ions are supplied to the surface of the workpiece. Therefore, the concentration of chloride ions in the vicinity of the workpiece 850 is increased 'and the atoms and hydroxide ions in the workpiece 850 react with each other to remove the surface layer of the workpiece 850. Therefore, it is considered that the ion exchangers 830 and 840 have the function of decomposing water molecules in the fluid 860 into hydroxide ions and hydrogen ionization. However, when the electrodes 8] and 820 are small in size (ie, small diameter), compared to the conventional ion exchange resin or ion exchange fiber, the ion exchanger 3] 5]] 5 7 200406276 83 0 and 840 cannot be respectively The grounds are disposed on the surfaces of the electrodes 810 and 820. Therefore, the anode 810 and the cathode 820 must be covered with an ion exchanger over the anode 8 10 and the cathode 8 2. In this example, if the distance between the anode ㈣ and the cathode 820 is smaller than the distance L2 between the electrode 81 0,820 and the metal (for example, copper) serving as the workpiece 850, the current flowing between the sister 81 will be greater than the electrode
卿〇和工件㈣之間流通的電流。因此，電極8 之間的距離£1必須設定使更大於電極_〇和工件 850之間的距離l2。 干 :而’離子交換器83〇,84〇的厚度能防止電極81〇 82〇 和工件850之間的距離匕2被充分地縮短。 ， 口此，較佳為陽極8 1 〇 此。結果，陽極810和险極82 配置太靠近彼 再者m 的形狀等將有所限制。 者傳、洗_子交換纖維的問％ ^ μ 維可能會由離子交換器 ：電解過程中，纖 質隨時間而變化。所 減，准以成加工性 度造成影響。由此可見;;、誠維可能會對工件的表面粗糖 將網到離子的離子交換纖维：：整個工件表面平垣，嘗試 到圓筒狀的電極。然而不織布四周纟將不織布接 古玄工件声而沾工 子父換器具有不均一的犀声 4工件表面的平坦度 的；度， 所影響。 匕曰又到離子交換器不均一的厚度 [發明内容] 有ι糸上述缺點而完成本笋明田 個目的在於提供電解加 。α此，本發明的第一 °电極，該電極能達到穩定的 3】51]5 /0 /0 種電極形狀。 解加工裝置及使用該 加工性能並可彈性地處理小電極和各 本發明的第二個目的在於提供電 電極的方法。 本赉明的第三個目的在於提 方法，嗲ϋ π a 疋彳，、此使液體解離成離子的 万去忒方法能達到穩定的加工性能。 為了達成第一個目的，根據本 電解加工用的雷朽X月乐一個恶樣，提供 川曰7电極。該電極含有命 團的有機化合物。输仆入，“才料及含離子交換基 電材料的表面。 ”化予的方式鍵結至導 根據本發明，且有一 接地鍵結至導電材：：的離子交換材料可羞 可作為電解加工用& + 4 子父換材料的導電材剩 之間的距離，進而此配置，可縮短電極和工件 之間的距離。因此，… 4和作為陰極之電極 根據本發明的電極可 極和各種電極形狀。 早性地處理小電 冉者，因為離子交換；y· -r \ , 結至作為陽極之導 子又換材科可分別地鍵 防止陽極和陰極之 勺岭兒材料，所以可 ^ 之間產生洩漏電流。 该有機化合物可 可包含磺酸m 子或二硫化物。離子交換基團 電材料可包括金、^、四^叙基及胺基之至少-者。該導 (ΠΙ)之至少一者。 鉑銅、砷化鎵、硫化鎘及氧化銦 該導電材料較倍庙入 以有效地分解水一自:5有師孔’因為該篩孔可讓水通過 件表面可能會產生f加工期間當工件與電極接觸時，工 1痕。由此可見’所欲為電解加工期間 315J15 9 200406276 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 今道+ nc 于解雖g月匕基。该導電碳材的表面 T 、糟由雒子解離官能基以化學方式加以改質。 利用該電極，雷托主二θ “ "極表面具有將水分子分解成離子的催 化作用。因此，可缔在帝 作… 牛之間的距離，進而縮短The current flowing between Qing 0 and workpiece ㈣. Therefore, the distance £ 1 between the electrodes 8 must be set to be larger than the distance l2 between the electrode_0 and the workpiece 850. Dry: The thickness of the 'ion exchanger 83,84,84 prevents the distance between the electrode 81,82,0 and the workpiece 850 from being sufficiently shortened. In this case, the anode 8 1 0 is preferred. As a result, the shapes of the anodes 810 and the dangerous poles 82 arranged too close to each other and the like will be limited. It is reported that the% ^ μ dimension of the ion exchange fiber may be caused by the ion exchanger: during the electrolysis process, the fiber changes with time. The reduction may affect the workability. It can be seen that ;; Chengwei may have coarse sugar on the surface of the workpiece. The ion exchange fiber that meshes to the ions :: The entire surface of the workpiece is flat, trying to reach a cylindrical electrode. However, around the non-woven fabric, the non-woven fabric will be attached to the sound of the ancient mysterious workpiece and the son-in-law converter has uneven rhino sound. The flatness of the surface of the workpiece is affected by the degree. The thickness of the ion exchanger is not uniform. [Summary of the Invention] The above disadvantages have been accomplished and the purpose of the present invention is to provide electrolytic addition. α This is the first electrode of the present invention. The electrode can achieve a stable 3] 51] 5/0/0 electrode shape. A dismantling device and a method for processing small electrodes with flexibility and a second object of the present invention are to provide an electric electrode. The third purpose of the present invention is to provide a method, 嗲 ϋ π a 、. This method of dissociating the liquid into ions can achieve stable processing performance. In order to achieve the first objective, according to this evil electrolytic X Yuele used for electrolytic processing, a Chuan Yue 7 electrode is provided. The electrode contains an organic compound of a corpuscle. Input, "the material and the surface of the ion-exchange-based electrical material." The ion exchange material is bonded to the conductive material according to the present invention, and there is a ground bond to the conductive material: The ion exchange material can be used for electrolytic processing. & + 4 The distance between the conductive material and the remaining material of the son-for-child replacement material, and further this configuration can shorten the distance between the electrode and the workpiece. Therefore, ... 4 and the electrode as a cathode The electrode according to the present invention can have various electrodes and various electrode shapes. Those who deal with small electric cells early because of ion exchange; y · -r \, which can be used as the anode's guide and the material can be bonded separately to prevent the anode and cathode from being formed, so it can be generated between ^ Leakage current. The organic compound may include a sulfonic acid or a disulfide. The ion-exchange group electrical material may include at least one of gold, tetra, tetra, and amine groups. At least one of the guides (ΠΙ). Platinum, copper, gallium arsenide, cadmium sulfide, and indium oxide This conductive material is more efficient to decompose water effectively: 5 There are holes in the division because the sieve holes can allow water to pass through the surface of the part. When it comes in contact with the electrode, it will be scratched. It can be seen that 'what is desired during electrolytic processing 315J15 9 200406276 The workpiece does not come into contact with the electrode. • According to a second aspect of the present invention ', an electrode for electrolytic processing is provided. The electrode contains a conductive carbon material and an ionic solution. The surface T of the conductive carbon material is chemically modified by the cleavage dissociation functional group. With this electrode, Reto ’s main θ "" electrode surface has a catalytic effect of decomposing water molecules into ions. Therefore, the distance between cattle and cattle can be shortened, thereby shortening
^ 為陰極之電極之間的距離。因此，舻 據本發明的電極可彈性地處 Χ 去m盔从达 地里J兒極和各種電極形狀。再 之電極和作為陰極之電極之中各者皆具 ’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 四價銨基和三價或更低<.胺:土子解離官能基可包含 掮忒更低&胺基之至少一者。該導命#妯叮 包含玻璃碳、富勒铳n / V电石厌材可 歸（u]]eiene)或奈米碳管。 根據本發明第三個態樣， 電極具有含鹼全屈夕.徒仏电角干加工用的電極。該 啕S如孟屬之石墨嵌入化合物。 利用該電極，咸認為藉由石 使水分子分解赤μ工 土層之間肷入的鹼金屬得 雜 因此’可縮短電極和工件之… ，進而縮短作為陽極之電 b1 離。因此，根據本發明之電極可彈性地之間的距 料狀。再者，因為作為陽極之電 口種 之中各者都具有催化作用 卞為陰極之電極 電流。 防止除極和陰極之間的洩漏 為了達到本發明之第二個目的，根披 ^ 榡，提供含有加 ^杳明第四個態 “加工，極和供料電極之加工裝置以供給工 315115 10 200406276 件。該電解加工裝置亦含有固定工 加工電榀田 、’使工件接觸或靠近 '極用的工件固定器。該電解加工裝置… 極和供祖杂 > 、置匕括在加工電 包極之間施加電壓用的電源 ^ 供至工件和Λ ^% ，、μ态，以及將流體 件和加工電極之間的流體供應單元。 供料電極之 μ加工％極和 芏/ 者使用上述電極之任_者。 根據本發明第五個態樣’提供電 料電極供仏工杜 午力工方法。透過供 、、，σ 件。在供料電極和加工雷搞+ pg 流體供於工件和加工電極之間。使接之間施加電屢。 極。加工電極和供料電極萄或靠近加工電 者。 者使用上述電極之任一 為了達到本發明的第三個目 樣，提供經以化學方式鍵結含離子六=本發明第六個態 」♦兒材枓促使液體解離成離子的方法。 w 該有機化合物可包含硫醇或二炉 團可包含石黃酸根、緩基、四價 :°该離子交換基 材料包括金、銀、鉬、銅 者。 銦（III)之中至少一者。 、’豕、、化鎘及氧化 由以下的說明參照以實施例方式 ▲ 體例的附圖時將使本發明之 、δ明之較佳具 更為顯著。 处和其他目的、特徵和優點^ Is the distance between the electrodes of the cathode. Therefore, the electrodes according to the present invention can be flexibly placed in a helmet and a variety of electrode shapes. Further, each of the electrode and the electrode serving as a cathode can prevent leakage current between the anode and the cathode. The ion dissociating functional group may include at least one of a tetravalent ammonium group and a trivalent or lower <. amine: soil dissociation functional group. The guide # 妯 叮 contains glassy carbon, Fuller's n / V calcium carbide disgusting (u)] eiene) or nano carbon tube. According to a third aspect of the present invention, the electrode has an electrode for alkali dry processing of an electric angle. The 啕 S is a graphite-embedded compound of the genus Mon. Using this electrode, Xian believes that the water molecules can be decomposed by the stone to decompose the alkali metal intercalated between the red soil layer. Therefore, the electrode and the workpiece can be shortened, and the ionization b1 of the anode can be shortened. Therefore, the electrode according to the present invention can be elastically spaced. In addition, because each of the anodes has a catalytic effect, the anode is the cathode current. To prevent leakage between the depolarizing electrode and the cathode In order to achieve the second object of the present invention, a processing device including a processing state, a processing electrode, and a feeding electrode is provided to supply the working electrode 315115 10 200406276 pieces. The electrolytic processing device also contains a fixed work processing electric field, a workpiece holder for 'contacting or approaching the workpiece'. The electrolytic processing device ... poles and ancestors > The power supply for applying a voltage between the electrodes is supplied to the workpiece and Λ ^%, the μ state, and the fluid supply unit between the fluid part and the processing electrode. The μ processing% electrode of the supply electrode and the electrode are used. According to the fifth aspect of the present invention, the method of providing electrical material electrodes for masonry and labor is provided. Through the supply, processing, and σ pieces. + Pg fluid supply to the workpiece and processing electrode Electricity is applied between the electrodes. The processing electrode and the feed electrode may be close to the processing electrode. In order to achieve the third aspect of the present invention, any one of the electrodes is used to provide chemical bonding. Contain A sixth state "♦ child member Tu = Subsix method of the present invention causes the liquid solution is separated into ions. w The organic compound may contain a thiol or the second furnace may contain lutein, a retarder, and a tetravalent: The ion-exchange-based materials include gold, silver, molybdenum, and copper. At least one of indium (III). , 以下,, cadmium, and oxidation From the following description with reference to the drawings of the embodiment ▲ system will make the better of the present invention, δ is better. And other purposes, features and advantages
[貫施方式J Ύ將I H兄明電極和使用根據本發明呈雕制 電極的電解加工裝置。以下沾目 毛月具肢例之 乂 F的具體例中， 件並以電解加工裝置加工。铁 土弋作為工 …〉’本發明亦可應用於該基 η 315115 ZUU4UbZ/b 材之外的任何工件。 實施例之概：：：使用根據本發明之電極的電解加工裳置 -對電解加工用… 圖所不，該電解加工裝置含有 充當基底材料+ # 。亥电極1和2分別地含有 < 了十之導電材料〗a 分別地連接到電源供應 广刪[Implementation Mode J: The electrode is an electrode and an electrolytic processing apparatus using the electrode formed according to the present invention. In the following specific examples of the 月 F of the hairy limbs, the pieces are processed by an electrolytic processing device. Ferroconcrete as a tool ...> 'The present invention can also be applied to any workpiece other than the base η 315115 ZUU4UbZ / b material. Summary of the examples: :: Electrolytic processing clothes using electrodes according to the present invention-For electrolytic processing ... As shown in the figure, the electrolytic processing device contains + # serving as a base material. The electrodes 1 and 2 each contain < a conductive material of ten, a respectively connected to a power supply.
團之有機化合物係以化學的方二：陰：。含離子交換基 俾於導電材料1 a 、，.結至導電材料1 a表面 離子交換基團之有機H上形成離子交換㈣η，並且含 土圓 < 有機化合物# 與 料2a表面俾於 、予◊方式鍵結至導電材 2“如純水或心：〜的表面上形成離子交換材料 八-飞超純水等流體5 如於基材上形成的銅膜)之間。‘=，2和工件:(例 離子交換材料！ b和2b 4接觸或罪近 導電碳材！…之間 二…“極1，2中的 得藉由離子交換材料：加㈣。流體5中的水分子 舉例來說，將… 解離成氫氧離子和氫離子。 』來"所產生的氫氧離子供 工件4附近的氫氧離子濃 的表面。因此 風氣離子會相互相反應巾的原子和 根據本發明，且有離子 的表面層之移除。 社力 八碓子交換功能的離子交換 接鍵結至充當基底材料之導+ n 又換材科可直 ^ ¥電材料。因此，如第3 R仏一 含離子交換材料之導電松粗π p 弟3圖所不， 料可作為電解加工用的帝 用此配置，可縮短電極]〇 、电極。利 而^ …和工件（基材）4之間的距雜，、隹 而、、伯短作為陽極之電極】和作為陰極 i 離。因此，電解加工裝置可彈性地處理 ^間的距 (j $極和各種電極 315135 12 200406276 形狀。再者’因為離子交換材料可分 極和陰極之間，亦即，電搞 所以可防止陽 如上所述，各電極都“:二間’”漏電流。 s啕雖子交換材讳 交換基團之有機化合物# n ^ ^ 、 〃 ，八中含離子 語「鍵結」表示含離子二：：：方式鍵結至該電極。術 非藉由黏著㈣，鍵結至導ΐ =材料係藉由化學鍵，而 中，含離子交換基團的材料係「鍵/ =離子交換樹脂 有機物質。 、°」至该樹脂所包含的 所欲為經鍵結有機化合物之導電材 如，晶格圖案或衝孔的金屬， 列 效地分解水。 口為“孔可讓水通過以有 該電極可依以下的方式製造。說…The organic compounds of the group are chemically two: Yin :. The ion-exchange group is formed on the conductive material 1a, and the organic H bound to the ion-exchange groups on the surface of the conductive material 1a forms an ion-exchange ion η, and contains a soil circle <organic compound # and the surface of the material 2a on the surface. ◊ way bonding to conductive material 2 "such as pure water or heart: fluids such as ionic exchange material eight-fly ultrapure water 5 are formed on the surface of 5 ~ such as copper film formed on the substrate). '=, 2 and Workpiece: (eg ion exchange material! B and 2b 4 are in contact with or near conductive carbon material! ... between the two ... "The poles 1 and 2 are obtained by the ion exchange material: plus tritium. Examples of water molecules in fluid 5 Said, will dissociate into hydroxide ions and hydrogen ions. "The" hydroxide ions produced are supplied to the surface where the hydroxide ions near the workpiece 4 are concentrated. Therefore, the wind ions will react with each other and the atoms of the towel, And the surface layer with ions is removed. The ion-exchange function of the social force octopon exchange function is bonded to serve as the guide of the base material + n and the material can be changed directly ^ ¥ electric material. Therefore, as in the third R 仏 一The conductive bulky π p with ion exchange material is not shown in Fig. 3. It can be used as This configuration is used for electrolytic processing, which can shorten the electrode], the electrode. The distance between the electrode and the workpiece (substrate) 4, and the electrode as the anode], and as The cathode is separated from the cathode. Therefore, the electrolytic processing device can elastically handle the distance between the electrode and the shape of various electrodes 315135 12 200406276. Furthermore, because the ion exchange material can be separated between the pole and the cathode, that is, it can be electrically To prevent positivity, as mentioned above, each electrode has a ": two between" leakage current. S 啕 Although organic compounds # n ^ ^ and 〃 of the exchange group, the ions in the word "bond" means ions. 2 ::: The method is bonded to the electrode. The technique is not bonded to ㈣, bonded to the lead ΐ = the material is through chemical bonding, and the material containing ion exchange groups is "bond / = ion exchange resin organic substance ”, °” to the conductive material included in the resin that is a bonded organic compound, such as a lattice pattern or a punched metal, effectively decomposes water. The mouth is “holes that allow water to pass through to have the electrode It can be made in the following way. Say ...
鈉（HSC3H6-S〇3Na)作為有含離 ；，L ^ 有3碓子父換基團的有機化合物 ^妾地鍵結至舶㈣基材以製造電極之實施例。以石备酸 鈉（硫醇）。 成卜丙硫醇_3_硫酸 百先’ t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 _。藉由硫酸和過氧化气水 =液將翻基材表面上㈣機物f移除。㈣，將#基材沈 浸：丙硫醇-3-硫酸鈉的水溶液中，該水溶液的濃度為數 個毫莫耳/公升’、約12小時。卜丙硫醇·3_疏酸納在宫能基 只S义根之衫#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 13 3)5]]5 200406276 性的而使硫醇將鍵結至該鉑基材的表面。 此，可製成平 坦的勤電極（Pt-SC3H6_S〇3Na)，言亥電極具有摧化作 解離功能）。 隹子 在經由1-丙硫醇-3-硫酸鈉改質的鉑 ,r. ^ Λ 1工’俊文中稱 為瓜醇鉬電極，測量水分子解離反應中的催化作用。且雕 =:將如上述製造之硫醇翻電極設置於含平行板電= 貫驗裝置中，利用超純水進行電解作 /只J里Μ下各例早 的电流-電壓性質。再者，測量以一般鉑電極作為陽極和吟 極之比較實驗的電流-電壓性質。 在 極 極⑴以硫醇翻電極作為陽極’並以—般的翻電極作為陰 ⑺以-般的始電極料陽極，纟以硫醇紐電極作為陰 /將氟樹脂片配置於電極之間。相互面對之電極 係設定於約〇 · 4 c m2。藉由兮蠢抖0匕 貝 精由忒齓树脂之厚度調整電極之間的 距離。在電極之間的距離為50 測量。 一條件下進行 第4A圖為顯示電極之間的距離為]之實驗 的圖形，而第4B圖為電極之間 ' …果 』此蠘為5 〇 μ m之實士 y形。由第4A和化圖顯示若以碳醇始電極 ^ ί陰與：㈣電極作為陽極和陰極之情況相比時， 龟角午黾流將提咼數倍至數十炉（导古 。 阿5〇倍）。由此，以硫醇 4白電極作為將水解離成離子 子的觸媒。經促使解離的液體並 不限於水。 1 315115 14 uoz/o 由第4A和4B圖可見到當雷 ^ ^ , 極之間的距離減小時，電 角牛電流會變大。具體而言， ^ 電解雷&佶1 之間的距離為1 2 // m， 缺而电拉之約5〇倍大（見第4A圖）。 …、、而，右黾極之間的距離為5〇 ^ ^ ^ ? # m，電解電流值為使用一 觳鉑兒極例子之約5倍大（見第4B圖）。 上述實施例中，以鉑作為莫泰 ” 电材料，將有機化合物鍵 結至该導電材料。然而，該導 上八， 电材科並不限於鉑。例如， 如孟、銀或銅等金屬皆可作為導 粗叮a k八 材料。或者’該導電材 枓可匕括έ Αιι膜之玻璃基材， 仆鋁、、T rw〆 A GaAs(砷化鎵）、CdS(硫 化Μ Ιη203(氧化銦（111))、碳 P石έ切卢你m人 土）寺寺。根據另一實驗， 述之電、*…所 破离基材的例子中可達到類似上 其笪古德+ 有女々、本胺為主的材料或奈米碳 =美園h材料皆可作為導電材料。具體而言，含離子 父換基團㈣機化合物可直接地鐽結至有機導電材料。 =知例中’以硫醇作為鍵結至導電材料之有機化 3物。然而，該有機化合物並 万、石爪S子。舉例來說，二 硫化物或聚笨胺為主的材料，太 一 、 十A不未石厌官等有機導電材料皆 可作為有機化合物。再者今 冉者切子交換I團並不限於上述Sodium (HSC3H6-S03Na) is an example of an organic compound containing ions, and L ^ has a 3 dyne group, which is bonded to the base material to manufacture an electrode. Prepare sodium acid (thiol). Propyl mercaptan_3_ sulfuric acid Baixian't prepares a flat turning substrate, for example, having a length of 34 mm, a width of 12.5 mm, and a thickness of 0.05 mm. Sulfuric acid and peroxide gas water were used to remove the substrate f on the surface of the turning substrate. That is, the #substrate is immersed in an aqueous solution of propyl mercaptan-3-sodium sulfate, and the concentration of the aqueous solution is several millimoles / liter 'for about 12 hours. Bupropion mercaptan. Sodium 3-sulfosulfate is hydrophilic under the Gong Nengji Syigen shirt. Therefore, if the surface of the platinum substrate is hydrophobic before immersion, the surface of the platinum substrate becomes hydrophilic after immersion 13 3) 5]] 5 200406276 and the thiol will be bonded to the surface of the platinum substrate . Therefore, a flat electrode (Pt-SC3H6_S〇3Na) can be made, and the electrode has a disintegrating function). Gardenia is called platinum citritol electrode modified by 1-propanethiol-3-sodium sulfate in platinum, r. ^ Λ 1 engineering, and measures the catalytic effect of water molecule dissociation reaction. And carving =: The thiol flip electrode manufactured as described above was set in a parallel-plate-containing electric testing device, and electrolysis was performed using ultrapure water / early current-voltage characteristics of each case. Furthermore, the current-voltage characteristics of a comparative experiment using a general platinum electrode as the anode and the anode were measured. In the electrode, a thiol flip electrode is used as the anode 'and a general flip electrode is used as the cathode. A normal electrode electrode is used as the anode, and a thiol button electrode is used as the cathode. The fluororesin sheet is arranged between the electrodes. The electrodes facing each other were set at about 0.4 cm. The distance between the electrodes is adjusted by the thickness of the resin with the tremor. The distance between the electrodes is measured at 50. Performed under a condition. Fig. 4A is a graph showing an experiment in which the distance between the electrodes is [], and Fig. 4B is a graph between the electrodes. "..." This is a real y-shape of 50 μm. Figure 4A and Figure 4 show that if the carbon alcohol is used as the starting electrode, and the cathode is used as the anode and cathode, the turtle horn nodal flow will increase several times to dozens of furnaces (Guogu. A 5 〇 倍). As a result, a thiol 4 white electrode is used as a catalyst for ionization by hydrolysis. The dissociated liquid is not limited to water. 1 315115 14 uoz / o It can be seen from Figures 4A and 4B that when the distance between the poles ^ ^, and the poles decrease, the electric horn current will increase. Specifically, the distance between the electrolytic mine & 佶 1 is 1 2 // m, which is about 50 times larger than the electric pull (see Figure 4A). …, And the distance between the right poles is 50 ^ ^ ^? # M, and the electrolytic current value is about 5 times as large as the one using a platinum pole pole (see Figure 4B). In the above embodiments, platinum is used as the "Matter" electrical material, and an organic compound is bonded to the conductive material. However, in the above description, the Department of Electrical Materials is not limited to platinum. For example, metals such as Meng, silver, or copper may be used. It can be used as a guide material, or 'the conductive material can be a glass substrate of aluminum film, aluminum, T rw〆A GaAs (gallium arsenide), CdS (sulfide M Ιη203 (indium oxide (111 )), Carbon, stone, stone, cut, you, man, and earth) temple. According to another experiment, the electric substrate described by *, * ... can be similar to the above-mentioned good + + son-in-law, this amine The main materials or nano-carbon = Meiyuan h materials can be used as conductive materials. Specifically, organic compounds containing parent-exchange groups can be directly bonded to organic conductive materials. = In the known examples, thiol is used as An organic compound that is bonded to a conductive material. However, the organic compound does not contain 10,000, stone claws. For example, materials based on disulfide or polybenzylamine, Taiyi, Shiyabuweishi, etc. Organic conductive materials can be used as organic compounds. In addition, the exchange of I group is not limited On the above
的石黃酸根。舉例來今、，勤1 I 牛彳〗；。兄，羧基、四價銨基及胺基皆可作為離 子交換基團。根據實驗，已確 U隹W以羧基作為硫醇的離子交 換基圑時將可達到類似上述的效果。 广據亡發明之電極可應用於第5至7圖所示的電解加 …置帛5圖為喊不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 3】5115 15 200406276 解加工裝置的主要架二μ 主要加描 一 弟？圖為顯示第6圖所示之 要木：14的主要部分之透視圖。 1〇 化裝置22及高厂堅超純水供超純水循環/純 裝置22含有廢水禅μ ^早兀28。該超純水循環/純水 20 H" 超純水循環/純化段I 8和高壓泵Lutein. For example, today, Qin 1 I 牛 彳;. Brother, carboxyl group, tetravalent ammonium group and amine group can be used as ion exchange groups. According to experiments, it has been confirmed that when U 隹 W uses a carboxyl group as a mercaptan ion exchange group, the effect similar to the above can be achieved. The electrode according to the invention can be applied to the electrolytic addition shown in Figs. 5 to 7 ... Fig. 5 is a schematic illustration of an embodiment of an electrolytic processing device that does not use the electrode according to the present invention, and Fig. 6 is a display Electricity 3 shown in Figure 5] 5115 15 200406276 The main frame of the disassembly processing device 2 μ Mainly add a description? The figure is a perspective view showing the main part of the main wood: 14 shown in FIG. 6. The chemistry unit 22 and Gaochangjian ultra-pure water supply for ultra-pure water circulation / pure unit 22 contains wastewater Zen ^ Zaowu28. The ultrapure water circulation / pure water 20 H " ultrapure water circulation / purification section I 8 and high pressure pump
«亥阿昼超純水供應單元28 器26。舉例來說，該機械加工室12;由基栗24和屢力傳送 如第5圖 2 &由不錢鋼製造而成。 ”30以#: 该主要架構】4含有工件固定器(固定 口）3〇以便能藉由吸引作用依 （疋 定半導體晶圓等工#w 1 方向以可拆卸的方式固 工室12中並且右γ 。该工件固定器3〇係置於機械加 至2中亚具有ΧΥ^自由度。具體 次於超純水〗〇之中日丰， 田件W沈 依X和Υ方向水y 器30固定的工件料 上循著Θ二二(見第7圖)並且可在該水平面 軸（2軸）奴轉。工件固定器3〇 提供電流至工件w。舉例來說，該工件固並且 :造而成並且含有厚度為^之鑛紐表面:。:“ 益30係使用超純水以靜水軸承32依輻射和，固疋 以支撐（見第5圖）。 ”’力力方向加 如第7圖所示’將管柱型或圓柱型 於工件固定器3…該加工電極34具 極34設置 ⑽。該加工電極34係由根據本發明之電極所：伸的轴心 而言’在管柱型或圓柱型導電材料％上’成°具體 換功能的離子交換材料34b，將含離举=有離子交 又渙基團的有機化 3]5115 16 200406276 合物以化學& t 子的方式鍵結至該導電材 中的導t Μ祖u . 將该加工電極34 材枓34a連至電源供應器％。 34b作為將 °亥硪子父換材料 于力工电極3 4和工件w夕戸弓+ 解離成气#L + i ^ Β 、超純水之水分子 Α虱離子和氣離子用的觸媒。 將加工電極34連至沿著軸心〇_〇 的旋轉軸36。由此，該加工雷“ L伸之可垂直移動 口〆加工電極3 4可仿日π女a 土土 轉而循荽鉍、^ ^ J依知旋轉軸36之旋 僱者軸心〇·〇旋轉。該加工電極34 調整加工雷搞q 4 4 垂直地移動以 包柽34和由工件固定器3〇 的距離。兮工杜陌^ _ 疋之工件W之間 口亥工件固疋器30使用超純 以輻射和驅動六Μ女& 由硭水軸承（未圖示） 動力的方向加以支擇 電極34 4k + 疋订包解製程時，加工 4运降低，使該離子交換材料 靠近工件g $ % π & n 3仆的下端部分接觸或 仔固疋态3 0所固定的工件。 該電解加工裝置含有在加工 30所固定之工件W之門+厂 34和由工件固定件 具體例“ 加笔壓用的電源供應器38。此 至^1。了進行工件銅的電解製程，加工電極34係連 “、供應裔38之陰極，且工件(銅) 至 38之陽極。然而，視工件的類型而定，;^還應器 i章$ + 疋该加工電極3 4可«Haia day ultra-pure water supply unit 28 device 26. By way of example, the machining room 12; is made of Chiryu 24 and repeatedly conveyed as shown in Figure 5 & 2 is made of stainless steel. “30 以 #: The main structure] 4 contains a workpiece holder (fixing port) 3 so as to be able to be detachably fixed in the laboratories 12 in the direction of (the predetermined semiconductor wafer etc. #w 1 direction) and Right γ. The workpiece holder 30 is placed on the machine plus 2 Central Asia with XΥ ^ degrees of freedom. It is inferior to ultrapure water. ○ Zhongrifeng, field pieces W Shenyi X and Y direction water device 30 The fixed workpiece follows Θ 22 (see Figure 7) and can be slaved on the horizontal axis (2 axes). The workpiece holder 30 provides current to the workpiece w. For example, the workpiece is fixed and made: The surface of the mine button with a thickness of ^ :: "Yi 30 series uses ultrapure water and the hydrostatic bearing 32 is radiated and solidified to support it (see Figure 5)." 'Force direction plus as As shown in FIG. 7, 'the column or column type is placed on the workpiece holder 3 ... the processing electrode 34 is provided with a pole 34. The processing electrode 34 is formed by the electrode according to the present invention: in terms of the axis of the extension. The column-type or column-type conductive material is an ion-exchange material 34b with a specific conversion function, which will contain ion lift = ion-crosslinking group Organic 3] 5115 16 200406276 The compound is chemically bonded to the conductive substrate in the conductive material. The processing electrode 34 material 枓 34a is connected to the power supply%. 34b is used as ° The son-in-law changes materials to the mechanics electrode 3 4 and the workpiece w XI 戸 arch + dissociated into gas #L + i ^ Β, the ultra pure water water molecule A lice ions and catalysts for gas ions. Will process the electrode 34 is connected to the rotation axis 36 along the axis 〇_〇. Thus, the processing mine "L Nobuyuki can move the mouth vertically to process the electrode 3 4 can imitate π female a soil and turn to bismuth, ^ ^ J It is known that the axis of the spinner of the rotating shaft 36 rotates. The machining electrode 34 adjusts the machining lead q 4 4 and moves vertically to cover the distance between the 34 and the workpiece holder 30. Xiong Du Mo ^ _ The workpiece holder 30 between the workpiece W uses ultra-pure to radiate and drive six M women & the electrode is supported by the direction of the motive force of the water bearing (not shown) 34 4k + Reduce the processing time, and bring the ion exchange material close to the workpiece g $% π & n 3 The lower end part of the contact or the solid state 3 0 is fixed This electrolytic processing device includes a gate of the workpiece W fixed in the processing 30 + the factory 34 and a specific example of the workpiece fixture "power supply 38 for pen pressure application. Here to ^ 1. The electrolytic process of copper of the workpiece is performed. The processing electrode 34 is connected to the cathode of the supply electrode 38 and the anode of the workpiece (copper) to 38. However, depending on the type of workpiece, ^ also the processing device Chapter $ + 疋 The processing electrode 3 4 可
連至電源供應器38之陽極，且工 T 38之陰極。 件W可連至電源供應器 如上所述，該工件固定器3〇可 加工帝朽〇 4叮％ # L工土 者垂直轴旋轉，且 兒極j4可循者水平軸旋轉。 帝杈， 件固定器30和加工 -極34分別依特定方向旋轉，使得超純水 〜 由工件固定器30所固定的工件从7和 ^ 、者付。在 壓供應超純水用的超純水供應嗜冑/工電極34之間以高 、貝麵4〇係設置於旋轉方向 315115 17 200406276 的上游倒。在旋轉該加工電極34和工件w之至 轉：由旋轉方向的上游側供應純超水〗。至該加工電： d和工件W之間以有效 乜 可夕I示J月匕殘留在加工電極u 工件W之間的氣泡或機械加工產物。 :第5圖所示，藉由超純水循環/純化襄置22中的純 口 7循％/純化段18純化超純水，由高屡超 Μ中的壓力傳送器26加壓， '應早兀Connected to the anode of power supply 38 and the cathode of T38. The piece W can be connected to a power supply. As described above, the workpiece holder 30 can process the imperfections. The worker's vertical axis can be rotated, and the child pole j4 can be rotated along the horizontal axis. The emperor, the piece holder 30 and the processing pole 34 are respectively rotated in a specific direction, so that the ultra-pure water ~ workpieces fixed by the workpiece holder 30 are paid from 7 and ^. The ultra-pure water supply osmotic / working electrode 34 for pressure-supplying ultra-pure water is arranged upstream of the rotation direction 315115 17 200406276 with a high and low surface 40 series. When the processing electrode 34 and the workpiece w are rotated, pure super water is supplied from the upstream side in the rotation direction. To the processing electric power: d and the workpiece W are effective 乜 乜 I shows the air bubbles or mechanical processing products remaining between the processing electrode u and the workpiece W. : As shown in FIG. 5, ultrapure water is purified by ultrapure water circulation / purification in the pure port 7 through% in the purification section 22 / purification section 18, and is pressurized by the pressure transmitter 26 in the high repeat ultra M, Early
喷嘴40. U “活基泵24供入超純水供應 貝备〇中。再者，如第5圖所示，機械加工室η中成壯 的超純水1〇溢流而儲存於廢水槽16中。然後，超純：： 於超純水循環/純化裝置22中 " 械加工室12。將走”…π I精由-昼泵2〇抽回機 將起純水10之一部分供至靜水軸承32。 定工^由此建構的電解加工裝置，以工件固定器3〇固 ，亚降低加工電極；34使加工電極34的 材料3 4 b 立· 子乂換 接觸或罪近工件w的表面。在此情形之下，以和 純水循環/ y儿扯卜 超 並盾：衣置22純化機械加工室12内的超純水1〇 並使工：展。將加工電極34連至電源供應器38的陰極， W接觸電源供應器3 8的陽極，俾將+ 工電極34 4 1早將電壓施於加 和工件W之間。同時，工件固 極34同時俨好— i和加工電 了依付疋方向旋轉使超純水1 〇亦跟著 置於旋轉大 考3疋轉。由設 水供方向上游側之超純水供應噴嘴40以高壓將超纯 料綱電極34和工件w之間。藉由該離子交換材 ” J b固體表面上發生的化學反應製造 氧離子以進行…表面層之移除。此例中·：：和氣 之流體係认u 超純水1 〇 於機械加工室]2中形成並通過離子交換材料34b 315115 18 200406276 、衣&大量的氫離子和氫氧離。 或氫氧離子供至工件w 由此，將大量的氣離子 程。 表面上以有效地進行電解製 如上所述，使該工件固定哭Nozzle 40. The U-based pump 24 is fed into the ultrapure water supply equipment. Furthermore, as shown in FIG. 5, the mature ultrapure water 10 in the machining chamber η overflows and is stored in the waste water tank. 16. Then, ultra-pure :: in ultra-pure water circulation / purification device 22 " machine processing room 12. will go "... π I fine by-day pump 20 Drawback machine will start to supply a part of pure water 10 To the hydrostatic bearing 32. The electromagnetism processing device thus constructed is fixed by the workpiece holder 30, and the processing electrode is lowered; 34 makes the material 3 4 b of the processing electrode 34 stand in contact with or near the surface of the workpiece w. Under this circumstance, the pure water is circulated with the ultra-thin shield: the clothes set 22 purifies the ultra-pure water 10 in the machining room 12 and the workmanship is expanded. The processing electrode 34 is connected to the cathode of the power supply 38, W contacts the anode of the power supply 38, and the + working electrode 34 41 applies a voltage between the voltage and the workpiece W in the early stage. At the same time, the workpiece solid state 34 is simultaneously rotated—i and the machining electrode are rotated in the direction of rotation to make the ultrapure water 10 align with the rotation test 3 times. An ultrapure water supply nozzle 40 provided on the upstream side of the water supply direction places the ultrapure material electrode 34 and the workpiece w at a high pressure. Oxygen ions are produced by the chemical reaction occurring on the solid surface of the ion exchange material "J b to remove ... the surface layer. In this example :: The flow system of the gas recognizes ultrapure water 1 in the machining room] A large amount of hydrogen ions and hydrogen ions are formed and passed through the ion exchange material 34b 315115 18 200406276 in 2 or the hydrogen ions are supplied to the workpiece w, thereby a large amount of gas ions pass. The surface can be effectively electrolyzed System as described above, make the workpiece cry
上游你I力如 疋轉。由設置於旋轉大A 側之超純水供應噴嘴40以 專方向 雪；K。/1 N I將超純水供岸$ ^ 电極34和工件w之間。因此 \仏[、至加工 3 4之η从Α 在於工件W和加工命托 μ之間的超純水1〇可有 电椏 由電解制、止邮立i 」用新的超純水取代，所以 -解衣造所產生之氣體和機械加斤以 實現穩定的電解製程。 物可有效地移除而 根據本發明之電極亦可應 裝置。第8圖所示 =圖所…解加工 解加工裂置，… 衣置不同於第7圖所示之電 加工電極丨34，導+ '或球面。若降低 134b之下端部分將=料134?卜表面上的離子交換材料 生點接觸。在此产：M工件固“ 30所固定的工件W發 器30同時旋轉。㈣加卫電極⑴和工件固定 之結構的相同。的結構與弟7圖所示之電解加工裝置 利用此電解加工裝置，因為 純水1 0將可輕易祕似 刀的面和減少，超 在穩定的條件下進^Λ該加。工部分的周圍部分。因此，可 供應噴嘴40射出。：兒解製程。超純水可能不需由超純水 超純水的槽體並使^來說’該電解加工裝置可使用盛裝 射超純水。 电極和工件沈浸於超純水中，而不用喷 315115 19 200406276 因為除了超純水以外，任何化學材料，包括研磨粒子 和稠密的化學液體，皆未用於該電解加工裝置，所以該機 械加工室14僅可能受到電化學加工期間產生的反應產物 所污染。由此，可簡化或免掉該電解製程之後基材的清潔 製程。該純水的循環可減少廢水的量。再者，因為不需要 處理任何化學液體，所以可顯著地降低操作成本。 # 上述的具體例中，含離子基團的有機化合物係以化學 =方式鍵結至電極的表面俾於電極的表面上形成離子交換 八月丘而5，金、銀、鉑、銅、化 :(導電材料)，而硫醇、二硫化物等係作為含二 化合物。該有機化合物係以化學的方式鍵 俾將離子交換基團引入電極材料中。導電碳材:； 表面可精由離子解離官能基以 人材的 該電極。具體而言，以導電 气文貝’而不使用 機反岸吉技“ 反材作為電極材料，並藉由盔 反尤直接將碘子解離官能基有效 … 面中。在該例中，由於電 ¥…之碳表 交換基團）之間的有機化合物，所~s ▲基（或離子 低化學改質層之厚度，並可改盖離=碳鍵。因此，可降 (或耐移除性)和導電性。離官能基的持久性 弟9 ϋ為顯示使用該電極的電工 不。如第9圖所示，電解加工 &置之概略圖 2()2° 該電極 201 * 2G2 2〇1 和 之陽極和陰極的導電碳材2〇 至電源供應器2〇3 能基2〇]b以化學的方式 ：广利用離子解離官 〜兔材料201a的表 315 ] ] 5 20 200406276 利用離子解離官能基202b以化學的方式改質該導電碳材 2〇2a的表面。將純水或超純水等流體205供至電極2〇1、 202和工件2〇4(例如，在基材上形成之銅膜）之間。然後， 使工件204罪近電極2〇1、2〇2中的離子解離官能基mu、 2〇2b。藉由電源供應器203在電極201、202中的導電碳材 2〇la和202a之間施加電壓。藉由離子解離官能基2〇1匕、 2〇几將流體2〇5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綱表面。藉此將 件204附近的氫氧離子的濃度提高，並使工件2⑽中的 原子與氫氧離子柄互反應而進行工件綱表面層之移除。 距％由;^ \可縮短電極20 1、202與工件（基材）204之間的 、而鈿紐作為陽極之電極2〇1和作為陰極之電極汕2 夂勺距_。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。$ & 、 』毛^ 者，因為作為陽極之導電碳材20 1 a 和作為陰極邋恭 式改 ’笔厌材2〇2&分別地鍵結至(或以化學的方 貝）_子解離官能基2〇lb、2〇 陽極之間，亦卽^ LJ此了防止陰極和 八、旨予 兒極201和202之間產生洩漏電流。 3 ¥電碳材並藉由 該導電碳材h 基以化學方式改質 i反材表面之電極作 例的電解加1裝置， "、"至 7圖所示之具體 結至導’而不使用有機化合物以化學的方式鍵 命屯材枓表面之電極。 以化學的方式改命 包含四價敍美或」 之離子解離官能基 性基團。、’ 價或更低價胺基等驗性基團或叛基等酸 315Π5 2] ZUU4U0Z/t> 若該電極係用以處理約lcm 導電碳材較佳應包含具有平μ平滑表大·^大面積時，該 咼準確度之形狀的碳材 ' 可加工成具有 進行1…小於 勒烯或奈米碳管月”’田加工蚪，較佳應使用富 孔，因為該篩孔可使水、^^為μ蛉毛衩材含有篩 、 ]使水通過而有效地分解水。 以化學方式改質合 a 之導電碳材的方二子父換基團等離子解離官能基 人柯的方法包括使導電 氣相中放電處理導希石U 又；化學液體中，於 材。 电及，並於電解溶液中電鍍導電碳 中，導，關於使導電碳材沈浸於化學液體之方法 分毛石反材係沈浸於硝酸耸气 該導電碳材的表面…利用此方法， 化學的方式改質。 地糟由緩基等離子解離官能基以 中，二例來成’關於於氣相中放電加工導電碳材的方法 #曰首RF放電（13·25ΜΗΖ)在含氧氣的氣體中形成電漿， 材=電碳材暴露於該電t底下。利用此方法，該導電碳 所。=可藉由叛基等離子解離官能基以化學方式加以改 %水可藉由放電在氮氣環境中形成，導電碳材可暴露Upstream you are as strong as a turn. The ultra-pure water supply nozzle 40 provided on the side of the rotating large A snows in a specific direction; K. / 1 N I supplies ultrapure water between the electrode 34 and the workpiece w. Therefore, the ultra-pure water 10 from Α to processing 3 4 from A lies between the workpiece W and the processing life μ may have electricity. It is produced by electrolysis and is not replaced by new ultra-pure water. Therefore-the gas and mechanical weight produced by the undressing process are used to achieve a stable electrolytic process. The object can be effectively removed and the electrode according to the present invention can also be applied. As shown in Fig. 8 = In the figure ... Dismantling dismantling, ... The disposition is different from the electromachining electrode 34, + + or spherical surface shown in Fig. 7. If the lower end of 134b is lowered, the ion exchange material on the surface of material 134b will make point contact. Produced here: M work piece fixed 30 Work piece fixed by W Whipper 30 rotates at the same time. ㈣Jawei electrode ⑴ and the work piece fixed structure is the same. The structure is the same as the electrolytic processing device shown in Figure 7 using this electrolytic processing device Because pure water 10 can easily resemble the surface of a knife and reduce, super under the stable conditions ^ Λ should be added. The surrounding part of the working part. Therefore, the nozzle 40 can be supplied for injection .: Child solution process. Ultra pure Water may not need to be made of ultrapure water from the ultrapure water tank and it is said that the electrolytic processing device can be used to contain ultrapure water. Electrodes and workpieces are immersed in ultrapure water without spraying 315115 19 200406276 because Except for ultrapure water, any chemical materials, including abrasive particles and dense chemical liquids, are not used in the electrolytic processing device, so the machining room 14 may only be contaminated by reaction products generated during electrochemical processing. Can simplify or eliminate the cleaning process of the substrate after the electrolytic process. The circulation of pure water can reduce the amount of waste water. Furthermore, because there is no need to deal with any chemical liquid, the operation can be significantly reduced Cost. # In the above specific example, the organic compound containing an ionic group is chemically bonded to the surface of the electrode, and an ion-exchanged August hill is formed on the surface of the electrode. 5, gold, silver, platinum, copper, : (Conductive material), and thiols, disulfides, etc. are used as dicompounds. The organic compounds are chemically bonded to introduce ion-exchange groups into the electrode material. Conductive carbon materials: The surface can be refined by ions The electrode that dissociates functional groups is made of human material. Specifically, it is effective to use conductive gas instead of organic materials as electrode materials, and to directly dissociate iodine from functional groups by means of a helmet ... in. In this example, because of the organic compounds between the carbon table exchange groups of electricity ¥ ..., the thickness of the ~ s ▲ group (or the ionic low-chemical modification layer) can be changed to cover = carbon bonds. Degradation (or resistance to removal) and electrical conductivity. Permanence from functional groups 9 ϋ is not shown for electricians using this electrode. As shown in Figure 9, the outline of electrolytic processing & 2 () 2 ° The electrode 201 * 2G2 201 and the conductive carbon material 20 of the anode and cathode to the power supply 203 energy base 2] b chemically: widely use ion dissociation officer ~ Rabbit material 201a Table 315] ] 5 20 200406276 The surface of the conductive carbon material 002a is chemically modified by the ion dissociation functional group 202b. A fluid 205 such as pure water or ultrapure water is supplied to the electrode 201, 202, and the workpiece 204 ( For example, a copper film formed on a substrate). Then, the workpiece 204 is dissociated from the functional groups mu and 202b in the electrodes 201 and 202. The power supply 203 is applied to the electrode 201 A voltage is applied between the conductive carbon materials 201a and 202a in 202 and 202. The functional groups 201a and 20a will be dissociated in the fluid 205 by ion dissociation. The molecules are dissociated into hydroxide ions and hydrogen ions. For example, 'the generated hydroxide ions are supplied to the surface of the workpiece. By this, the concentration of hydroxide ions near the part 204 is increased, and the atoms and hydrogen in the workpiece 2⑽ The oxygen ion handle interacts with each other to remove the surface layer of the workpiece. The distance% by; ^ \ can shorten the electrode between the electrode 20 1, 202 and the workpiece (substrate) 204, and the electrode as the anode electrode 201 and As the cathode electrode, the distance is 2 mm. Therefore, the electrolytic processing device can elastically handle small electrodes and various electrode shapes. The &邋 Gong-style modification 'penis material 2 0 2 & respectively bonded to (or by chemical square shell) _ ion dissociation functional group between 20 lb, 2 0 anode, also 卽 LJ this to prevent the cathode and eight The purpose is to generate a leakage current between the electrodes 201 and 202. 3 ¥ Electrolytic plus 1 device using an electric carbon material and chemically modifying the electrode on the surface of the reverse material by using the conductive carbon material as the base, ", " To the specific junction shown in Figure 7 without using organic compounds to chemical The electrode on the surface of the metal bond is chemically changed. The ion-dissociative functional group containing quaternary succinic or ionic groups is chemically changed. An oxidative group such as an amine group of a valence or a lower price or a rebel group, etc. Acid 315Π5 2] ZUU4U0Z / t > If the electrode is used to process about 1cm conductive carbon material, it should preferably include a flat carbon material with a flat μ smooth surface and a large area. For 1 ... less than lenene or nano carbon tube, "field processing", it is better to use rich pores, because the sieve holes can make water Ground decomposes water. The method of chemically modifying the conductive carbon material of a and dissolving the functional group by the plasma exchange of the radicals of the two sons and fathers includes the method of discharging the conductive gas phase in the conductive gas phase; and the chemical liquid in the material. Electricity, and electroplating conductive carbon in electrolytic solution, the method of immersing conductive carbon material in chemical liquid is divided into woolen material and immersed in nitric acid to elevate the surface of conductive carbon material ... using this method, chemical Modification. The ground ditch is formed by the dissociation of functional groups by a slow plasma. Two examples are used to describe the method of electrical discharge processing of conductive carbon materials in the gas phase. #First RF discharge (13 · 25M25Z) forms a plasma in an oxygen-containing gas. = The electric carbon material is exposed under the electric t. With this method, the conductive carbon is replaced. = Can be chemically modified by dissociating functional groups with a radical plasma.% Water can be formed by discharge in a nitrogen environment, and conductive carbon can be exposed.
於該電％ & T H "’。该例子中，可將具有鹼性的離子解離官能 土加入該導電碳材内。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。參見S. S.Wong, Α· T. W 〇 〇 1 e v ττ τ ’ oselevich，C· Μ· Leiber，Chem. Phys. Lett.，第 306 卷 0 999 年），第 219 頁。 22 3Ι5Π5 200406276 、，電解溶液中電鐘導電碳材之方法中，導電碳材通常 作^陽極。麵（Pt)、金（Au)、錯（Pb)和辞办）等金屬以及任 何碳材料皆可作為陰極。參見h Wandass， j. a G^ella5 N. L. Weinberg, M. E. Bolster, L. Salvati, /In the electricity% & T H " ’. In this example, an ion dissociating functional clay having basicity can be added to the conductive carbon material. These methods are suitable for chemically modifying conductive carbon materials by dissociating functional groups with ions. See S. S. Wong, Α · T. W 〇 〇 1 e v ττ τ ′ oselevich, C.M. Leiber, Chem. Phys. Lett., Vol. 306 0 999), p. 219. 22 3Ι5Π5 200406276, In the method of conducting carbon materials for electric clocks in electrolytic solutions, conductive carbon materials are usually used as anodes. Metals such as Pt, Au, Pb, and resignation, and any carbon material can be used as the cathode. See h Wandass, j. A G ^ ella5 N. L. Weinberg, M. E. Bolster, L. Salvati, /
Ele〇trochem. s〇c. , ^ 134 4(1 987 ^), ^ 2734 f 0 :溶液可包含石肖酸、硫酸、碟酸、氫氯酸、氫漠酸或含此 寺酸中所含之離子的鹽類，類包括鋰、納和鉀等之鹼 金屬鹽，！美、飼和鎖等驗土金屬鹽，錢鹽、❹、鱗鹽， 以及卜、CU和㈣金屬鹽。實際上使用單-電解溶液或 此，員包解〉谷液之混合物。儘管所欲為電解電流密度約1至 物mAW，但該方法並不限於此等條件。利用此方法， 石反材的表面係藉由羧基以化學的方式加以改質。 根據在氣相中放電加工導電碳材的方法，導電碳材中 姆基之電極係製造如下。使二支以水潤 ㈣隔約3-。在電極之間施加謂之交流電壓。將： 水潤淫過的碳棒(導電碳材)插入電極之間。在大氣中產生 電弧放電以藉由該電孤放電處理該碳棒的表面俾將緩基加 =碳棒（導電碳材）的表面中。該碳棒係由直徑“之石 率為〜:⑽的。所用的水為超純水’電阻 ^經^處理之碳棒作為陽極，且紐板作為陰極之實驗 "'則置電流-電壓性質。該實驗裝置含亞克力製容器， :純水盛於其中’而該超純水具有電阻率Η.·· ♦ 該碳棒和該紐板在容器中彼此面對。以測微器調整碳棒和 315Π5 23 200406276 兔棒和鉑板之間時， 測量流通的電流。將 鉬板之間的距離之後，在超純水供至 在棒和拍板之間施加電壓。同時， 碳棒和鉑板之間的距離設為1 5 // m。 再者，比較實驗中以類似於上述之方法測量電流_電舞 處理之前的碳棒料 陽極，並以鉑板作為陰極。 …Ele〇trochem. Soc., ^ 134 4 (1 987 ^), ^ 2734 f 0: The solution may contain lithocholic acid, sulfuric acid, discic acid, hydrochloric acid, hydroxamic acid, or the content contained in this temple acid. Salts of ions, including alkali metal salts of lithium, sodium and potassium, etc.! Soil test metal salts such as beauty, forage and locks, money salts, tinctures, scale salts, as well as Bu, CU and tritium metal salts. In practice, a single-electrolytic solution or a mixture thereof is used. Although the electrolytic current density is desired to be about 1 mA mAW, the method is not limited to these conditions. With this method, the surface of the stone material is chemically modified by the carboxyl group. According to a method of electric discharge processing of a conductive carbon material in a gas phase, an m-based electrode system in the conductive carbon material is manufactured as follows. Let the two sticks be hydrated and separated by about 3-. A so-called alternating voltage is applied between the electrodes. Insert: Hydrated carbon rod (conductive carbon material) between the electrodes. An arc discharge is generated in the atmosphere to treat the surface of the carbon rod by the electric solitary discharge, and the substrate is added to the surface of the carbon rod (conductive carbon material). The carbon rod has a diameter of ~: ⑽. The water used is ultra-pure water. The resistance ^ treated carbon rod is used as the anode, and the button plate is used as the cathode. &Quot; Properties. The experimental device contains an acrylic container: pure water is contained in it, and the ultrapure water has resistivity Η .. · ♦ The carbon rod and the button face each other in the container. Adjust the carbon with a micrometer Measure the current flowing between the rod and the 315Π5 23 200406276 between the rabbit rod and the platinum plate. After the distance between the molybdenum plates, the ultra-pure water is supplied to apply a voltage between the rod and the clapper plate. At the same time, the carbon rod and platinum plate The distance between them is set to 1 5 // m. Furthermore, in the comparison experiment, the carbon rod anode before the current measurement was measured in a similar manner to the method described above, and a platinum plate was used as the cathode ...
第10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時具有 夂 流。 有十七或更多倍之提高電 根據在電解溶液中電鑛導電碳材的方法，導電碳材中 加入緩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/cm2之2〇重量％ 溶液中電 鐘^分鐘。以翻板（Pt)作為對向電極（facing electr〇de)。 4石厌棒仏由直6mm之石墨製成。該碳棒各端皆為圓的。 該電㈣棒之電流·電壓性質在類似於上述實施例的條件 下測里肸妷棒和鉑板之間的距離設為丨5 # m。 乂方員似於上述貫施例的方法測量以電鍍進行表 面處理之Μ的碳棒作為陽極，並以舶板作為陰極之比較實 驗的電流-電壓性質。 … 固"、員示上述貫驗的結果。由第11圖可見到相較 於未加入竣臭夕 & _ I棒’藉由電鍍作用將緩基加入其中的碳 棒具^十倍或更多倍之提高電流。 筹眚由電^# ^ ^將竣基加入其中之碳棒係用作為加工電極 24 315115 200406276 以進行在矽基材上形成銅膜之電解製程。該電解製程係於 60V之電壓和1.07mA之電流時進行10秒，而電極之間的 距離為 2 5 // m。電解製程的結果，最大的加工深度為 1 4 4 n m。同時，電流效率約 4 8 %。電流效率表示用於加工 該銅膜之電流置對所有通過的電流置之比率。電流效率係 假設銅係以二價離子或二價離子化合物的形式洗提而計 算。 未經電鍍加入魏基之碳棒係用作加工電極以進行在 矽基材上形成銅膜之電解製程。該電解製程係於60V之電 壓和0.0 4 3 m A之電流時進行6 0秒。電解製程的結果，最 大的加工深度為12nm。同時，電流效率約3.3%。 由此可見到與未加入羧基之碳棒相比時，藉由電鍍加 入緩基之碳棒在電解製程期間具有提南的電流及提南的電 流效率。 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電 極。通常希望以高度取向的熱解石墨（HOPG)作為石墨嵌入 化合物中的石墨（碳材）。然而，若以鈉作為鹼金屬嵌入於 石墨層之間時，希望以低取向的石墨作為石墨嵌入化合物 中的石墨。該石墨嵌入化合物較佳應含有篩孔，因為該篩 孔可使水通過俾有效地分解水。 第1 2圖為顯示使用該電極之電解加工裝置的概略圖 示。如第]2圖所示，該電解加工裝置含有一對連至電源供 應器3 03的陽極和陰極之電極3 0 1和3 02。該電極3 0】和 25 3]5115 200406276 302係由含鹼金屬之石墨歲入化合物製成。純水或超純水 等流體305係供至電極（石墨嵌人化合物）3qi、_和工件 3〇4(例如’在基材上形成之銅膜）之&1。然後，使工件3〇4 靠近電極3G1、3G2。藉由電源供應器303在電極3()1和3〇2 之間細加電S。错由石墨嵌入化合物製成的電極術和如 將流體3 0 5中的水公j&严 笊刀子解雔成虱氧離子和氫離子。舉例來 說，將所產生的氯氧離子供至工件304表面。藉此將工件 304附近的氫氧離子的濃度提高，並使工件3 與氯氧離子相互反應而進行工件3CM表面層之移除 由此’可縮短電極301、3〇2與工件（基 距離，進而縮短作Α嗒 Ί …、°电極3 0 1和作為陰極之電極3 02 之間的距每隹〇因此，今兩 ^ ^^ 电解加工裝置可彈性地處理小電極 和各種電極形狀。再者， 、」包乜 陰極之電極3〇2皆且有催化^作為陽極之電極301和作為 之n b ’所以可防止陰極和陽極 間^即’電極如和加之間產生茂漏電流。 :二’包括含鹼金屬之石墨嵌入化合物，可用 圖所示之具體例的電解加工裝置中，而不用有 仏物：化學方式鍵結至導電材料表面之電極。 石墨肷入化合物之合成方、丰勺扭々4 相接觸反應法、固相加2法包括现相值慶反應法、液 包含將驗金屬和石墨置=權。該氣卿反應法 6 、破祸官的不同位置處，在直空下 二：並在控制的溫度時加熱該石墨和驗金屬。驗 位置和驗金屬嵌入的量可藉由控制驗金屬和石 墨的〉皿度而加以調整。舉例來說，當钟嵌入Η 315JI5 26 200406276 度係設定於約25Ot：。該液相接觸反應法包含使液相中含 鹼金屬的化合物直接與石墨接觸而相互反應。該固相加壓 法包含使鹼金屬與石墨接觸，將石墨加壓至約5至約汕 大氣壓（約0.5至約2MPa)，並將該石墨加熱至約2〇〇t。 該溶劑法包含將驗金屬溶於錄溶劑等溶劑，並使 於該溶劑中。 土况反 根據該液相接觸反應法，由含鹼金屬之石墨 物製成的：極係製造(合成)如下。藉由燃燒器在_中： 熱並使硝馱鈉熔融，該硝酸鈉之熔 長度為〜、寬度為34mm且厚：J〇84 融的硝酸鈉當中，並在其中加熱2 、、a 沈’又於熔 堝中移出石墨板並在空氣中冷卻 力&然後’自掛 墨層之間的石墨嵌入化合物製成之泰此衣广由含鈉嵌入石 圖所示之實驗裝置中測量電流-電厣 接著在乐13 亞竞力制交哭”η 之14貝。該實驗裝置含有 亞克力衣合DO 〇 20和一對平行板電 w *3 2 】和 3 9 9。,、，丄 墨嵌入化合物製成的電極作為電極 、， 由石 極322。將此等電極321和322分 ：乂勤板作為電 之陽極和陰極。在超純水325中測旦^至電源供應器323 純水的電阻率為i8·2ΜΩ. cm。同日士 $ : M性質’該超 間的距離係設定於12/im，且相/ ’電極321和322之 的面積係設定於約o.W。互面對之電極切和322 再者，以相似於上述之方法測量余 性質’其中以石墨層之間未嵌入 了、驗之電流-電屢 ^ 勺石墨板作丸兩搞 弟]4圖顯示上述實驗的結杲。 ·.'、电。 由弟14圖可見到由含 3J51J5 27 200406276 #Figure 10 shows the results of the above experiment. It can be seen from Fig. 10 that, compared with carbon rods to which carboxyl groups are not added, the surface treatment is performed by arc discharge. The carbon rods to which carboxyl groups are added have a swill current at 60V. Seventeen or more times higher electricity. According to the method of electrosizing a conductive carbon material in an electrolytic solution, an electrode system with a slow base added to the conductive carbon material is manufactured as follows. A carbon rod (conductive carbon material) was used as the anode, and the electric current was applied for a minute in a 20% by weight solution having a current density of 12.5 mA / cm2. A flip plate (Pt) is used as a facing electrode. The 4-stone disgusting rod is made of 6mm graphite. The ends of the carbon rod are round. The electric current and voltage properties of the electric rod are measured under conditions similar to those in the above embodiment, and the distance between the rod and the platinum plate is set to 5 # m. The panelists seem to measure the current-voltage characteristics of the comparative experiments using carbon rods of M that are surface-treated by electroplating as the anode and the board as the cathode by the method described in the above embodiment. … Solid, "the staff show the results of the above-mentioned tests. It can be seen from Fig. 11 that compared with the carbon rod which does not include the endurance & The carbon rods used to add the finished base to the chip are used as processing electrodes 24 315115 200406276 to perform the electrolytic process of forming a copper film on a silicon substrate. The electrolytic process was performed at a voltage of 60 V and a current of 1.07 mA for 10 seconds, and the distance between the electrodes was 2 5 // m. As a result of the electrolytic process, the maximum processing depth is 144 nm. At the same time, the current efficiency is about 48%. The current efficiency represents the ratio of the current set used to process the copper film to all the current sets passed. The current efficiency is calculated on the assumption that copper is eluted in the form of a divalent ion or a divalent ion compound. Carbon rods added to Wyke without electroplating are used as an electrode for the electrolytic process of forming a copper film on a silicon substrate. The electrolytic process was performed at a voltage of 60 V and a current of 0.0 4 3 m A for 60 seconds. As a result of the electrolytic process, the maximum processing depth is 12 nm. At the same time, the current efficiency is about 3.3%. It can be seen that compared with carbon rods to which no carboxyl group is added, carbon rods having a retarder group added by electroplating have a south current and a current efficiency during the electrolytic process. A graphite-embedded compound containing a test metal can be used as an electrode without using an electrode that chemically modifies the surface of a conductive carbon material by dissociating functional groups with ions. It is generally desirable to use highly oriented pyrolytic graphite (HOPG) as the graphite (carbon material) in which graphite is embedded in the compound. However, when sodium is used as an alkali metal to be intercalated between the graphite layers, it is desirable to use low-oriented graphite as the graphite in the graphite-intercalation compound. The graphite embedding compound should preferably contain sieve openings because the sieve openings allow water to pass through the concrete effectively to decompose the water. Fig. 12 is a schematic diagram showing an electrolytic processing apparatus using the electrode. As shown in FIG. 2, the electrolytic processing apparatus includes a pair of electrodes 3 0 1 and 30 2 connected to an anode and a cathode of a power supply 30 03. The electrodes 3 0] and 25 3] 5115 200406276 302 are made of graphite compounds containing alkali metals. A fluid 305 such as pure water or ultrapure water is supplied to the electrode (graphite embedded compound) 3qi, _, and workpiece 304 (for example, 'a copper film formed on a substrate) & 1. Then, the workpiece 30 is brought close to the electrodes 3G1 and 3G2. Fine power S is applied between the electrodes 3 () 1 and 302 by the power supply 303. Electrode technology made of graphite-embedded compounds, and for example, the water squeegee j & Yan in the fluid 305 can be decomposed into oxygen ions and hydrogen ions. For example, the generated chloride ions are supplied to the surface of the workpiece 304. Thereby, the concentration of hydroxide ions near the workpiece 304 is increased, and the workpiece 3 and the chloride ions react with each other to remove the surface layer of the workpiece 3CM. This can shorten the distance between the electrodes 301, 302 and the workpiece (base Furthermore, the distance between the electrode 301, the electrode 301, and the electrode 302, which is the cathode, is shortened. Therefore, the current two ^^^ electrolytic processing devices can elastically handle small electrodes and various electrode shapes. The "3" and the "3" of the cathode include a catalyst ^ as the anode electrode 301 and as the nb 'so it can prevent the occurrence of leakage current between the cathode and the anode ^ that is, between the electrode such as and plus.: 2' The graphite-containing compound containing alkali metal can be used in the electrolytic processing device of the specific example shown in the figure, without using a substance: an electrode that is chemically bonded to the surface of the conductive material. 々4 phase contact reaction method, solid phase addition 2 method includes the current phase value reaction method, the liquid contains the metal test and graphite = right. The Qi Qing reaction method 6, in different positions of the disaster officer, under direct air Two: and at a controlled temperature The graphite and metal inspection are heated. The inspection position and the amount of metal inspection can be adjusted by controlling the degree of metal inspection and graphite. For example, when the clock is embedded Η 315JI5 26 200406276, the degree is set to about 25Ot :. The liquid-phase contact reaction method includes directly contacting a compound containing an alkali metal in a liquid phase with graphite to react with each other. The solid-phase pressurization method includes contacting an alkali metal with graphite to pressurize the graphite to about 5 to about atmospheric pressure ( (About 0.5 to about 2 MPa), and the graphite is heated to about 2000 t. The solvent method includes dissolving a test metal in a solvent such as a recording solvent and placing the solvent in the solvent. The soil condition is based on the liquid-phase contact reaction method. , Made of graphite containing alkali metal: The polar system is manufactured (synthesized) as follows. By the burner in _: heat and melt the sodium nitrate, the melting length of this sodium nitrate is ~, the width is 34mm and the thickness : J〇84 melted in sodium nitrate, and heated in it 2, and a sink 'and then removed the graphite plate in the melting pot and cooled in air & then' self-hanging graphite intercalation graphite compound Zhitai Clothing Co., Ltd In the experimental device, the current-electricity measurement was performed at Le 13, and 14 lbs. Η was included. The experimental device contained acrylic clothing DO 〇20 and a pair of parallel plate electric w * 3 2] and 3 9 9 An electrode made of the ink-insertion compound is used as the electrode, and the electrode 322 is composed of these electrodes. The electrodes 321 and 322 are divided into two parts: the anode plate and the cathode are used for electricity. It is measured in ultrapure water 325. The resistivity of the power supply 323 pure water is i8 · 2MΩ. Cm. Same as the same: M: 'The distance between the super is set to 12 / im, and the area of the phase /' electrodes 321 and 322 is set to about oW. Electrodes facing each other and 322. Also, measure the remaining properties in a similar way to the above. 'Among the graphite layers that are not embedded, the tested current-electricity is repeated. ^ A graphite plate is used as a pill.] 4 The figure shows the results of the above experiment. ·.',Electricity. From the picture of the younger brother, you can see from the figure 3J51J5 27 200406276 #
納族入石墨層之間的石墨嵌入化合物製造的電極在i5〇v 時能提供稍低於50mA之電流（電流密度為 因此與鈉未嵌入石墨層之間的石墨板相比時，具有約π 倍之提高電流。因此，咸認為納嵌入石墨層之間的石墨嵌 入化合物可促使㈣水解離錢料錢氧離子。 上述實施例中，石墨係沈浸於使 液體中。然而，該石墨可沈浸 二，、：… 之鹽類中。 s双孟屬，如硝酸鉀， 稀釋的化學液體可你盘、、夭上 說，2丙g^TPA、 、'小σ物添加至純水。舉例來 Α丙％ (ΙΡΑ)可添加至 牛妁不 儘管已純水的極性。 已，，，、員不並砰細說明本發明 要瞭解其中仍可進行夂 二啟佺的具體例，但 專利範圍之範·。 ° 和修飾而不會悻離後附申請 本發明可應用於電極， 工電極及/或在使用流體，特係作為加工基材用之加 以供給基材之供料電極。 疋’屯水’之電解製程期間用 [圖式簡單說明] 〜第1A至1C圖為顯示在基 的實施例之圖示； 、中“第2圖為顯示使用傳統離子交換- 概略圖示； 又換裔之電解加工裝置 弟3圖為顯示使用 略圖示； & 的銅内連線之形成製程 的 明之電極的電解加工裝置 之概 3】5 ]】5 28 200406276 第4A和4B圖為顯示利用 ¥電材料且含離子交拖I 團之有機化合物以化學方式鍵換基 電解製程時之電流-電壓性質圖形;〜材料之電極進行 第5圖為顯示使用根據本發 例的概略圖示； 電解加工裝置之實施 第6圖為顯示第5圖所示之泰 的截面圖示； 电午加工裝置之主要架構 第7圖為顯示第6圖之電 加工電極之透視圖； 工衣置中的固定部件和 弟8圖為顯示根據本發明另〜 部件：加工電極之透視圖；〜電解加工裳置中的固定 罘9圖為顯示包含根據本發一 工哀置的概略圖示； 頒型電極之電解力π 罘1〇圖為顯示第9圖所示之泰 圖形； 兔亟的電流-電壓性質 第]1圖為顯示第9圖所示 圖形； 毛極的電流-電壓忮賢夂 第圖為顯示含根據本發明 加工衣置之實施例的概略圖示； 碩型電極夂電 第13圖為顯示用於測量根 歷性質之實驗裝置的概略圖示； 第14圖為顯示第12圖-- 據本發 明史電 極的電 % % 200406276 la，2a，34a，134a 導電材料 1 b’2b’34b, 1 34b 離子交換材料 接觸孔 2 絕緣膜 4 溝槽 6 銅膜 5,205,305,860 流體 7 晶種層An electrode made of a graphite-embedded compound between a nano-group and a graphite layer can provide a current of slightly less than 50 mA at i50v (the current density is therefore about π when compared with a graphite plate where sodium is not embedded between the graphite layers). Therefore, Xian believes that the graphite intercalation compounds that are intercalated between the graphite layers can promote the hydrolysis of ions and oxygen ions. In the above embodiment, the graphite is immersed in the liquid. However, the graphite can be immersed in the liquid. In the salt of s ..., shuangmeng, such as potassium nitrate, diluted chemical liquids can be added on the plate, 2 丙 TPA, 'small σ added to pure water. For example, Α C% (ΙΡΑ) can be added to burdock despite the polarity of pure water. The specific examples of the present invention are to be understood by the present invention, but the scope of patent scope °° and modification without separation The attached application can be applied to an electrode, a working electrode and / or a feed electrode which is used as a processing substrate to supply a substrate when a fluid is used. 'Electrolytic process used during the [simple diagram Ming] ~ Figures 1A to 1C are diagrams showing the embodiment of the base; "The second picture is a schematic diagram showing the use of traditional ion exchange-a schematic diagram; and another electrolytic process device is shown in Figure 3. Illustration; & outline of the electrolytic processing device for the formation of bright electrodes of copper interconnects 3] 5]] 5 28 200406276 Figures 4A and 4B show the use of ¥ electric materials and the organic group containing ionic cross-linking I group The current-voltage property pattern of the compound when the compound is chemically exchanged for the base electrolysis process; ~ The electrode of the material is shown in Fig. 5 which is a schematic diagram showing the use of this example; the implementation of the electrolytic processing device is shown in Fig. 6 which is shown in Fig. 5 A cross-sectional view of the Thai shown; the main structure of the electro-processing device is shown in FIG. 7 is a perspective view showing the electro-processing electrode of FIG. 6; the fixing part in the work clothes and the figure 8 are shown in accordance with the present invention ~ Parts: perspective view of the processing electrode; ~ Figure 9 shows the outline of the fixed electrode in electrolytic processing; Figure 9 shows the electrolytic force of the electrode. Thai graphic shown; rabbit urgent Current-Voltage Properties [Figure 1] shows the graph shown in Figure 9; Current-Voltage of the Hairy Pole [Figure 5] is a schematic diagram showing an embodiment including a processing device according to the present invention; Fig. 13 is a schematic diagram showing an experimental device for measuring the properties of the root calendar; Fig. 14 is a diagram showing Fig. 12-Electricity of an electrode according to the history of the present invention% 200406276 la, 2a, 34a, 134a Conductive material 1 b '2b'34b, 1 34b Ion exchange material contact hole 2 Insulation film 4 Trench 6 Copper film 5,205,305,860 Fluid 7 Seed layer
1 0,325 超純水 丨2 14電解加工裝置的主要架構 16 廢水槽 20 高壓泵 24 活塞泵 28 高壓純水供應單 32 靜水軸承 36 旋轉幸由 38?2035303?323 8ΩΠ ^ 40 超純水供應噴嘴 機械加工g 18 超純水循環/純化段 22 超純水循環/純化裝置 26 壓力傳送器 30 工件固定器 3 4，1 3 4 加工電極 5 毛源供應器 ^ 201，202,301，302 電極 基材1 0,325 Ultrapure water 丨 2 14 Main structure of electrolytic processing device 16 Wastewater tank 20 High-pressure pump 24 Piston pump 28 High-pressure pure water supply single 32 Hydrostatic bearing 36 Rotating by 38? 2035303? 323 8ΩΠ ^ 40 Ultrapure water supply nozzle Machining g 18 Ultra-pure water circulation / purification section 22 Ultra-pure water circulation / purification device 26 Pressure transmitter 30 Work piece holder 3 4, 1 3 4 Processing electrode 5 Hair source supplier ^ 201, 202, 301, 302 Electrode substrate
W 201a，202a導電碳材 204,304,850 工件 321?322 平行板電極 8 2 0 陰極 L】 陽極和陰極 足間的距離 電極和工〆斗二 工件之間的距離 20 1 b,202b 離子解離官能基 320亞克力製容器 810 陽極 8 3 0，8 4 0 離子交換器 X5Y，O-〇，0 軸 315115 30W 201a, 202a Conductive carbon materials 204, 304, 850 Workpieces 321 to 322 Parallel plate electrodes 8 2 0 Cathode L] Distance between anode and cathode feet Distance between electrode and workpiece 2 20 1 b, 202b Ion dissociation functional group 320 acrylic Container 810 anode 8 3 0, 8 4 0 ion exchanger X5Y, O-〇, 0 shaft 315 115 30
| 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 |
|---|---|
| TW200406276Atrue TW200406276A (en) | 2004-05-01 |
| TWI288681B 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 |
|---|---|
| TW (1) | TWI288681B (en) |
| WO (1) | WO2004033765A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS511673B2 (en)* | 1972-09-30 | 1976-01-19 | ||
| JPS6014610B2 (en)* | 1979-11-17 | 1985-04-15 | 株式会社荏原製作所 | Pre-coating method for powdered ion exchange resin |
| US5948265A (en)* | 1996-07-05 | 1999-09-07 | Tosoh Corporation | Ion-exchanger, process for production thereof, and process for removal of multiply charged anions employing the ion-exchanger |
| JP3837783B2 (en)* | 1996-08-12 | 2006-10-25 | 森 勇蔵 | Processing method with hydroxyl groups in ultrapure water |
| US6652658B1 (en)* | 1998-12-07 | 2003-11-25 | Japan Science And Technology Corporation | Method for machining/cleaning by hydroxide ion in ultrapure water |
| JP2001064799A (en)* | 1999-08-27 | 2001-03-13 | Yuzo Mori | Electrolytic working method and device |
| JP4513145B2 (en)* | 1999-09-07 | 2010-07-28 | ソニー株式会社 | Semiconductor device manufacturing method and polishing method |
| Publication number | Publication date |
|---|---|
| WO2004033765A1 (en) | 2004-04-22 |
| TWI288681B (en) | 2007-10-21 |
| Publication | Publication Date | Title |
|---|---|---|
| CN105731429B (en) | Graphene manufacturing equipment and manufacturing method | |
| TW201128696A (en) | Cleaning method, cleaning system, and method for manufacturing microstructure | |
| CN110316729B (en) | Method for preparing graphene based on high-concentration organic salt aqueous solution electrochemical intercalation | |
| JPH1058236A (en) | Machining method using hydroxyl group in ultrapure water | |
| CN103769700A (en) | Electrolysis machining method for surface texture of high potential inert metal template | |
| CN104404566B (en) | A kind of to modify TiO 2nano-tube array is the ti-lead dioxide anode in middle layer and preparation method thereof and application | |
| TW200936816A (en) | Method of electrolysis | |
| CN112981471B (en) | High-localization three-dimensional electrodeposition device and method | |
| TWI277474B (en) | Electrolytic processing apparatus | |
| TW200303801A (en) | Method and device for regenerating ion exchanger, and electrolytic processing apparatus | |
| CN104769161B (en) | Electrolytic cell equipped with microelectrodes | |
| Mandler et al. | Microelectrochemistry on surfaces with the scanning electrochemical microscope (SECM) | |
| TWI271246B (en) | Electrolytic processing apparatus and method | |
| TW200406276A (en) | Electrode for electrolytic processing | |
| CN102251270B (en) | Method for stripping metallic thin film plated on surface of material | |
| CN206052186U (en) | Perforation Copper Foil foil machine | |
| KR20110065971A (en) | Graphene Oxide Manufacturing Method | |
| CN115449872B (en) | Ultrasonic auxiliary cathode plasma electrolytic deposition coating and surface treatment method and device | |
| JP3980518B2 (en) | Wet cleaning processing apparatus and wet cleaning processing method | |
| JP3995463B2 (en) | Electrolytic processing method | |
| CN112975011A (en) | High-localization micro-groove electrolytic machining device and method | |
| Jiao et al. | Metal-assisted chemical etching of silicon 3D nanostructure using direct-alternating electric field | |
| CN112680752B (en) | Chemically strengthened bonding method suitable for endoscope structure | |
| TW200536643A (en) | Electrolytic processing apparatus | |
| JP2004299046A (en) | Electrode for electrochemical machining, and electrochemical machining device and method |
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |