201241237 τι t 六、發明說明： 【發明所屬之技術領域】 本發明是有關於一種對硫酸進行電解而生成過硫酸的 電解方法及電解裝置。 【先前技術】 對硫酸溶液進行電性分解而生成過氧二硫酸 (peroxydisulfuric acid )及過氧單硫酸（per〇Xym〇nosuifuric acid，以下統稱為過硫酸），並用於半導體材料的清洗等的 方法已為人所知。 ^作為對硫酸進行電性分解而生成過硫酸的方法之一 疋一面於電解單元内使硫酸溶液通過電極間，一面於電? 中的陽極與陰極之間施加直流電壓而進行轉。作為該, 解皁兀的構造，有單極單元（一對陽極、陰極）、使用了 4 的複極單元等’而—對陽極、陰極的關係相同 為了脾距離保持為固定而通常使用間隔件（spacer) 造的電使用0形環等的密封構件。就細 照專利文獻Γ)。5，例如有本案發明人提出的電解單元“ 電解單元的概要表示於圖7 ( ”之間配置間隔件22而確 :間^ 在入口側形成有入液孔22a，在出 =件22中， 該些入液孔22a、出液孔2 4 液孔22b : 的流路。而且，在間隔件2223相比相當狭小 構件的—確保了流路：：著作為密封 4 201241237 [先前技術文獻] [專利文獻] [專利文獻1]日本專利特開細_262531號公報 然而’若將鑛轉’料常會於陰極t產生 乂 就該點而言，以前便已為人所知。 戍成為0抒二北轉貝會在電極面、尤其在電極周端部 的部分生成硫或與硫生成相關的化學 細的S粒子在電極面附著、成長，則有產生如 久後其會自電極剝落且伴隨電解液的流動 而移動’並附著、蓄積在電解單元出液孔或電解單元入液 ’不久後引起閉塞。認為該問題在硫酸 電流密度高的情況下、及極間電壓高的 況。^測。形神或出液孔附近蓄積硫的情 動不久糾二所讀硫析出，最終析出物剝離而移 =】圖中❹所示使單元出口或單元入口閉塞。 的雷：二ίΓ:的目的在於提供一種防止伴隨硫酸溶液 的電解而析出的硫的蓄積、及防止因硫析出物㈣起的系 統内的閉塞的電解方法及電解裝置。 Μ 方法'酸電解方法+的第1發明為—種電解 上在至少包含陽極與陰極的多個電極 中的上物極與上述陰極之間，一面流通70wt%(重量百 5 201241237 zizpif I、fL 溶液’—面進行電解從而生成過硫酸， 土，極與陰極至少接液面包含導電性金剛石； 方法，特徵在於：進行通常動作，該通常動作是對上 =的，極與陰極之間施加順向輕而進行上述電解 ϊ轉=_rh作期r施加至上述陽嶋 逆轉的換極（pole change)動作，使於 成的賴物於上述換極動㈣:= 電解，並將經電解的上述硫酸溶液排出至上述電解 中，麵法砂第1發縣第2發明 的滞留^解早兀内，具有供流通的上述硫酸溶液滯留 任』:發^?方:是於第1發明至第3發明的 狹小流路^ 早^具有供上述硫酸溶液流動的 第5發明的硫酸電解 極間配置著確保炉西〜％、第3發明中，於上述電 該間=件與其他構二二^=^件，由該間隔件或 極與上電解:法士:第5發明中 ’於上述電 封構件形成上述滞置考密封構件，且至少由該密 6 201241237 第7刺__財奸料 中，於上述間隔件形成有作為狹小流路部而^^ 液通過的出液孔。 仏上述石瓜I洛 第8發明的硫酸電解方法是於第5發明 任一個中，於上述間隔件形成有作為狹小流路部而::】： 硫酸溶液通過的入液孔。 抓路。卩而供上述 第9發明的硫酸電解方法是於第 任-個中’設置著自上述電解單元的出口連== 單元的入口為的循環線，於該循 亡述電解 留部的上游侧具有狹小流路部。〜S电解早兀的滞 第1〇發明的硫酸電解方法是於第丨發明 ::卜藉由將通常動作持續規定的時間而執心 第11發_硫酸電解方法是於第i發明 =;個中’根據上述硫的析出狀態的判定來執行上』 的任H的硫酸電解方法是如第1發明至第心明 :任一個，滿足以下的條件(a)〜條件㈦中的至少一 上；（a)上述電解單元内的上述硫酸的濃度為^游。以 (b)上述電解單元人口的硫酸溫度為7叱以上； ，）上述電解中的電流密度為5GA/dm2以上。’ 第13本發明的硫酸電解裝置，其特徵在於包括： 7 201241237 ’可進行硫酸溶液的流入與流出； 此的間隙通過的二2】解::内;:亡述硫酸溶液於彼 極與陰巍少接液面包含導電陽極與陰極，該陽 間件，確保上述電極間的間隙； 有的上述硫酸溶議 雷、^攻電解早凡進行硫酸溶液的輸送； 電壓；H ’上述電極的上述陽極與上述陰極之間施加 =原控制部’對上述電源部進行如下控制，即，於通 1於預上述陽極與上述陰極之間施加順向電壓，並 的電心::執行將施加至上述陽極與上述陰極之間 f14本發明的硫酸電解裝置，其魏在於包括： 電解單元，可進行硫酸騎的流人與流出； 此的間隙通過的解::亡述硫酸溶液於彼 極與陰極至少接液二=石含陽極與陰極’該陽 間隔件，確保上述電極間的間隙； 述硫用該間隔件或該間隔件與其他構件而供上 電壓電ίΓ對上述電極的上述陽極與上述陰極之間施加 即，執行 電源控制部，對上述電源部進行如下控制， 8 201241237 SI::電解時施加至上述陽極與上述陰極之間的電壓 本發明，於藉由在電極間流it硫酸溶液並通電， ^在^表面或0形環的背面等蓄積固體硫或其前驅物 進仃換極而使其電極面具有氧雜並以―定時間以 或效地使固體硫或其前驅物變回為硫酸 一者二馱離子。換極動作可持續10小時〜100小時左右。 垆』：以一定的間隔（mterval)重複該操作，而可防止 積、單元的閉塞。就間隔的決定方法而言，可設為 於經驗的一定的運轉時間或進行清洗等的處理片數 :、疋的方法’但若硫蓄積’則流過規定電流所需的電壓 =間電壓）上升，因而在利用電流控制進行通電時始終 進行監視，直至電壓上歧規定值為止，藉此可開 :換極動作。而且，亦可於執行上述換極時對電壓進行監 現，直至該電壓下降至規定值為止停止目前的換極動作。 以下表示電解時的反應形態。 電解液中硫酸或水分子以如下方式解離，存在s〇42-、 ®04·、H+等的離子。 H2S〇4<^>HS〇4+H+ hso4^ so42+h+ h2o<^> oh+h+ 其中，H+ (與H3〇+同義）及hs〇4_濃度以硫酸濃度 0 wt%〜80 wt%作為峰值，在更高濃度側則降低，另一方 9 201241237 *tl / i z,pif 面，未解離的硫酸分子ΗΘ〇4 (aq)的濃度急遽上升。而 且’因高濃度的硫酸溶液為強酸性’故〇Η·的濃度低。 陰極中H+被牽引，如下述反應式所示獲取電子而成為 氫氣H2。 2H++2e_—H2 陽極中HSCV或SO?·被牽引’如下述反應式所示釋放 電子而成為過硫酸H2S2O8。 2HSO，—S2082>2H++2e· 2S〇42->S2〇82'+2e 而且，陽極中，如下述反應式所示亦會引起水的電性 分解而產生氧氣〇2。 20H—02+2H++4e- 關於引起與硫酸或水相關的電極反應的氧化還原電 位，圖4、圖5所示的波貝克斯（Pourbaix)的線圖已為人 所知。 根據Pourbaix的線圖，若描綠且一併表示硫酸濃度=92 wt%、溫度=60°C時的硫酸與水的電位（potential)，則成為 圖6(a)及圖6(b)所示。圖中的式編號是基於圖4、圖 5所示的線圖上的式編號。 因電解單元中使用的硫酸為高濃度，故pH值大致為 -2。表示於陽極側亦以按照〇2 > 〇3 > h2〇2 > h2S208的順序 變低的電位而生成，但實際上〇2多，其次生成H2S208。 陰極中的電位為S>H2>H2S的順序。實際的單元中H2為 主要的產物，但就電位而言，S的生成亦有可能充分。若 201241237 生成的s不滯留在電極等的表面，貞彳 質反應而再次變回為硫酸，如果有 令與氧化性物 滯留部中。 ^ ’則s蓄積在該 若考慮到過硫酸的生成效率， 的電子中的80〇/〇〜9〇〇/0的電子與〇、田；貫際通過陽極 10〇/〇〜20%有助於過硫_二2、生成有㈣’剩餘的 且過硫酸被用於氧化反應後成為硫=出，統外 循環使用液體，則在對硫酸進行 2 方式 水而硫酸濃度變濃。 97早兀中會消耗 如上述般，在原理上，在陰極中完全 為困難’可藉由陽極中生成的氧化性物質（過較 硫氧化而變回為硫酸。在液體滞留 二將 留部的硫除^ _近生成過硫酸，從而將滞 本發賴料於t料^具有 r。就滯留部而言，並未示出電解單元的特=的：201241237 τι t VI. Description of the Invention: [Technical Field] The present invention relates to an electrolysis method and an electrolysis apparatus for electrolyzing sulfuric acid to produce persulfuric acid. [Prior Art] A method in which a sulfuric acid solution is electrically decomposed to produce peroxydisulfuric acid and peroxymonosulfuric acid (hereinafter referred to as persulfate), and is used for cleaning semiconductor materials and the like. It is already known. ^ As one of the methods for producing persulfuric acid by electrochemical decomposition of sulfuric acid, a sulfuric acid solution is passed between the electrodes in the electrolytic cell, and a direct current voltage is applied between the anode and the cathode in the electricity to be rotated. As a structure of the saponin, there are a monopolar unit (a pair of anodes and a cathode), a repolarization unit using 4, etc., and the relationship between the anode and the cathode is the same. In order to keep the spleen distance constant, a spacer is usually used. (The spacer) The electric power used is a sealing member such as an O-ring. Take a closer look at the patent documentΓ). 5. For example, there is an electrolysis unit proposed by the inventor of the present invention. "The outline of the electrolysis unit is shown in Fig. 7 (the spacers 22 are arranged between the two), and the liquid inlet holes 22a are formed on the inlet side, and in the outlet member 22, The flow paths of the liquid inlet holes 22a and the liquid outlet holes 4 4 and the liquid holes 22b: and the relatively narrow members of the spacers 2223 ensure the flow path: the work is a seal 4 201241237 [Prior Art Document] [ [Patent Document 1] Japanese Patent Laid-Open No. 262 531. However, if the "mine to turn" material is often generated at the cathode t, it has been known before. This is known as 0. In the north, the sulphur or the chemically fine S particles related to the formation of sulfur on the electrode surface, especially at the end portion of the electrode, adhere to and grow on the electrode surface, and then it will be peeled off from the electrode and accompanying electrolysis. The flow of the liquid moves and accumulates, accumulates in the discharge port of the electrolysis cell, or the electrolyte unit enters the liquid, and then causes occlusion. This problem is considered to be caused when the sulfuric acid current density is high and the interelectrode voltage is high. The accumulation of sulfur near the shape or the liquid hole Soon after the correction, the sulfur is precipitated, and finally the precipitate is peeled off and moved. 】 The 出口: Γ Γ 的 使 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元 单元An electrolysis method and an electrolysis apparatus for preventing accumulation of sulfur and preventing clogging in a system due to sulfur precipitates (4). Μ Method The first invention of the acid electrolysis method + is a plurality of electrodes including at least an anode and a cathode. Between the upper electrode pole and the cathode, 70 wt% (weight: 5 201241237 zizpif I, fL solution '-electrolysis is performed to generate persulfuric acid, soil, and at least the liquid contact surface of the pole and cathode contains conductive diamond; It is characterized in that a normal operation is performed, and the normal operation is performed on the upper side, and the polarity is applied between the pole and the cathode to perform the above-described electrolysis rotation = _rh period r is applied to the above-mentioned impotence reversal pole change The action is such that the sublimation of the Ue is in the above-mentioned reversal (4): = electrolysis, and the electrolyzed sulfuric acid solution is discharged to the electrolysis, and the surface of the first method of the first method of the first method is In the narrow flow path of the first invention to the third invention, the small-sized flow path of the first invention to the third invention is disposed between the sulfuric acid electrolysis electrodes of the fifth invention in which the sulfuric acid solution flows. In the west of the furnace, in the third invention, in the above-mentioned electrical and other components, the spacer or the pole and the upper electrolysis: in the fifth invention, the above-mentioned electric sealing member The stagnation test sealing member is formed, and at least the liquid permeable hole is formed in the spacer as a narrow flow path portion through the stagnation of the stagnation test. In the sulfuric acid electrolysis method according to any one of the fifth inventions, the spacer is formed as a narrow flow path portion: a liquid permeation hole through which the sulfuric acid solution passes. Grab the road. The sulfuric acid electrolysis method according to the ninth invention is the circulation line in which the inlet of the outlet unit of the electrolysis unit is connected to the unit of the electrolysis unit, and the upstream side of the electrolysis leaving portion is provided. Narrow flow path. ~S electrolysis early stagnation of the first sulphuric acid electrolysis method is based on the third invention:: by the usual action for a predetermined period of time and the heart of the eleventh _ sulfuric acid electrolysis method is in the i-th invention =; The sulfuric acid electrolysis method of the above-described "H" according to the determination of the precipitation state of the sulfur is at least one of the following conditions (a) to (7); a) The concentration of the above sulfuric acid in the above electrolytic unit is ^. (b) The sulfuric acid temperature of the population of the electrolytic cell is 7 叱 or more; and the current density in the above electrolysis is 5GA/dm 2 or more. A sulfuric acid electrolysis apparatus according to a thirteenth aspect of the present invention, comprising: 7 201241237 'the inflow and outflow of a sulfuric acid solution; the gap of the gap passed by 2: 2]: the inside; the sulfuric acid solution in the cathode and the cathode The squeezing liquid surface comprises a conductive anode and a cathode, and the anode member ensures a gap between the electrodes; some of the above-mentioned sulfuric acid dissolving thunder and ^ attack electrolysis are used for transporting a sulfuric acid solution; voltage; H 'the above anode of the electrode The power supply unit is controlled to be applied to the power supply unit between the anode and the cathode, that is, a core is applied between the anode and the cathode, and a core is applied to the anode. Between the above cathode and the above-mentioned cathode, the sulfuric acid electrolysis device of the present invention comprises: an electrolysis unit, which can perform the flow and the outflow of the sulfuric acid ride; the solution of the gap passage: the sulfuric acid solution is at least connected to the cathode and the cathode Liquid 2 = stone containing anode and cathode 'the positive spacer ensures the gap between the electrodes; the sulfur is supplied with the voltage by the spacer or the spacer and other members. When the anode is applied between the anode and the cathode, the power supply control unit is executed, and the power supply unit is controlled as follows. 8 201241237 SI:: voltage applied between the anode and the cathode during electrolysis. The present invention is flowed between electrodes. The sulfuric acid solution is energized, and the solid sulfur or its precursor is accumulated on the surface of the surface or the back of the O-ring, etc., and the electrode surface is made to have oxygen and the solid sulfur or the solid sulfur thereof or The precursor changes back to sulfuric acid, one of the diterpene ions. The pole changing action can last from 10 hours to 100 hours.垆 』: This operation is repeated at a certain interval (mterval) to prevent occlusion of the product and the unit. In the method of determining the interval, it is possible to set the number of processed pieces for a certain period of time or the number of processed pieces for cleaning, etc.: the method of 疋, but the voltage required to flow a predetermined current = if the sulphur accumulates. Since it rises, it is always monitored when the current is supplied by the current control until the voltage is higher than the predetermined value, thereby enabling the switching operation. Further, the voltage can be monitored when the above-described pole change is performed, and the current pole-changing operation is stopped until the voltage drops to a predetermined value. The form of the reaction at the time of electrolysis is shown below. The sulfuric acid or water molecules in the electrolyte are dissociated in the following manner, and ions of s〇42-, ®04·, H+, and the like are present. H2S〇4<^>HS〇4+H+ hso4^ so42+h+ h2o<^> oh+h+ where H+ (synonymous with H3〇+) and hs〇4_ concentration with sulfuric acid concentration 0 wt%~80 wt % as the peak, decreased on the higher concentration side, and the other 9 201241237 *tl / iz, pif surface, the concentration of undissociated sulfuric acid molecule ΗΘ〇 4 (aq) increased sharply. Moreover, the concentration of 〇Η· is low because the sulfuric acid solution having a high concentration is strongly acidic. In the cathode, H+ is pulled, and electrons are obtained as shown in the following reaction formula to become hydrogen H2. 2H++2e_—H2 The HSCV or SO? in the anode is pulled. The electrons are released as shown in the following reaction formula to become persulfate H2S2O8. 2HSO, -S2082>2H++2e·2S〇42->S2〇82'+2e Further, in the anode, as shown in the following reaction formula, electrical decomposition of water is caused to generate oxygen enthalpy. 20H—02+2H++4e— The redox potential of the electrode reaction causing sulfuric acid or water is known. The line diagram of Pourbaix shown in Figs. 4 and 5 is known. According to the Pourbaix line diagram, if the green color is combined and the potential of sulfuric acid and water at the temperature of sulfuric acid = 92 wt% and temperature = 60 ° C is shown, it becomes as shown in Fig. 6 (a) and Fig. 6 (b). Show. The equation numbers in the figure are based on the equation numbers on the line graphs shown in Figs. 4 and 5 . Since the sulfuric acid used in the electrolysis unit has a high concentration, the pH is approximately -2. It is shown that the anode side is also generated at a potential lowering in the order of 〇2 > 〇3 > h2〇2 > h2S208, but actually 〇2 is more, and secondly, H2S208 is generated. The potential in the cathode is the order of S > H2 > H2S. In the actual unit, H2 is the main product, but in terms of potential, the generation of S is also likely to be sufficient. If the s generated by 201241237 does not remain on the surface of the electrode or the like, the enamel reacts and returns to sulfuric acid again, and if it is in the oxidized substance retention portion. ^ ' Then s accumulates in the electrons of 80 〇 / 〇 ~ 9 〇〇 / 0 in the electrons taking into account the formation efficiency of persulfuric acid, and 〇, Tian; through the anode 10 〇 / 〇 ~ 20% help In the case of persulfate _ 2 2, (4) is formed, and persulfuric acid is used for the oxidation reaction to become sulphur = effluent, and the liquid is used for the external circulation, the sulphuric acid is subjected to 2 modes of water and the sulfuric acid concentration is increased. In the early morning, it will be consumed as described above. In principle, it is completely difficult in the cathode. 'The oxidizing substance generated in the anode can be converted back to sulfuric acid by oxidation of sulfur. Sulfur removal ^ _ near the formation of persulfuric acid, so that the lag is in the t material ^ has r. In terms of the retention, does not show the special = of the electrolytic unit:
的：::=:=::£S 極或間隔件的交又部等。 /、電 在電解單元具有流路剖面積比其他部分相對小 部ϊ情況下’析出物堵塞而流路容易閉塞，因 此在八有狹小流路部的電解單元中本發明尤其有益。狹小 201241237 HI / ΙΖ,ρΐΙ 電解單元内的下游側’例如在出液孔等中更容 易成為問心且亦有可能引起如下問題：滞留部中蓄積而 剝離的析出物隨同硫酸溶液流動1上述析出_著 ，在電解單元的域μ，不續發线料祕礙硫酸 >谷液的流動。 根據么明者等人的至今為止的研究，於硫酸濃度為％ 感以上、電流密度為5GA/dm2以上的情況下硫容易析 出、蓄積。在硫酸濃度更高的情況下，必_電流密度設 定得低。^且，以單元人口溫度達到贼〜抓的方式進 行運轉。然而，認為若硫析出而通電電阻上升，則單元内 電阻增加、單元溫度上升，從而硫的析出加速。定性上認 為這是因為使水分的揮發加速，尤其在圖7(a)及圖7(b) 所示的滞留部等中濃度顯著上升所導致。尤其單元入口溫 度超過70°C的運轉欠佳。 根據以上，硫析出物的問題在滿足以下3個條件中的 任一個以上時容易發生，在此類條件下實施本發明尤其理 想0 (a) 電解單元内的硫酸濃度為85wt%以上； (b) 電解單元入口的硫酸溫度為7〇。〇以上； (c) 電流密度為50A/dm2以上。 在利用硫酸電解液進行的電子材料清洗中，清洗後的 總有機碳（Total Organic Carbon，TOC)濃度為 〇 mg/1 〜 l〇mg/l ’幾乎不存在有機物。 [發明的效果] 12 201241237 ηι / a厶μιι 單元^ 根縣發明，於將雜溶液在電解 = =免硫析出物或前驅物蓄積而出現 【實施方式】獲付可持，進行穩定的電解的效果。 (實施形態1) 以下根據隨附圖式對具備本發明每 裝置的清洗系統進行說明。月的a施形_電解 電解裳置1如圖1所示且有雷觫 為無隔膜型，將包含金動二有電解早70 2。電解單元2 隔開而配陽極及陰極不利用隔膜 3上連接著對施加至上述陽極、陰極的Ϊ i的：向進行控制的電源控制部4 件等，㈣構件例如具備切換器 從直流電源3對陽極及陰極施加電壓的路徑。換 電解單元2如圖7 (a)所+ m -ir± 20 ^ ^ -己置間隔件22而在陽極2G、陰二 剛石電極而言，較佳為使用如下的金 薄膜形成為基板狀，並且相對 /·將孟剛石 電性。 〇,000啊的乾圍内摻雜蝴而賦予導 極的元包含作為電 陰極以外’亦可包含雙極性作）電極的陽極、 Γ生電極。而且，作為電解單元， 13 201241237 Hi /IZpif 亦可以彼此具有_:的方切電極配置為多層 ，從而於各 電極間流通硫酸溶液並進行電解。 、間隔件22中’在入口側形成有入液孔22a，在出口側 形成有出液孔22b’該些入液孔瓜、出液孔22b包含與流 路23相比相g狹小的流路，入液孔22a、出液孔挪相當 於本發明的狹小姐部H闕隔件22與陽極2〇及 陰極21之間’配置著作為密封構件的◦形環24以確保流 路23的密封性。作為構成間隔件η的材冑，較理想的是 具有絕緣性、财腐純的材料（例如為聚四氣乙稀 (polytetrafluorethylene )製）。 上述電解單元2中，電極2〇、電極21的内面與間隔 件22的角部或〇形壞24的内面側成為阻礙硫酸溶液的通 過的滯留部25。電解單元2以向上流動的方式將入口側配 置為下方，出口側配置為上方。 上述電解單元2經由第！循環線5而連接著電解液蓄 積槽1〇 ’於電解單元2與電驗蓄職1G之間可進行硫 Ϊ溶液的循環流通。即，第1猶環線5的輸送側以與電解 單7L 2的入口側連通的方式連接於電解單元2，第1循環 線5的返回側讀轉單元2的^ 口側連通的方式連接 電解單元2。 #第1循環線5的返回侧插入設置著氣液分離槽6。該 ，液分離槽6收容包含氣體的硫酸溶液並將硫酸溶液中的 氣體分離而排出至系統外’可使用已知的構成，本發明只 要可進行氣液分離，則對其構成不作特別限定。 201241237 而且’於第1循環線5的輸送側插入設置著使硫駿溶 液循裱的循環泵7、及將硫酸溶液冷卻的冷卻器8。第^ 循環線5及循觀7相#於本發明的送液部。冷卻器 ，酸溶液冷卻而成為贼〜贼等適合於電解的液: 發明亚未對該構成作出特別限定。本發明的電解勺人 ^述電解單元2、直流電源3、電源控制部4、^循= 5、軋液分離槽6、循環泵7、冷卻器8。 2循，上述電解液f積槽1G經由驗泵12而連接第 2循裱線11的輸送側。 钱弟 連接於單片式清洗裝置15。讀u的达液方向前端侧 上述加熱n 13具有石英製的管路 加熱器將硫酸溶液短暫式Μ ^ ^由近紅外線 内以硫酸溶液獲得15(TC〜2;於早片“洗裝置15 液進行急速加熱。 c的液溫的方式對硫酸溶 上述單片式清洗裝置15 φ 戴置於旋轉台等而加賴定，1 =電子材料基板100 從噴嘴流至半導體材料上過硫酸的硫酸溶液 另外，本實施形態中， 2二 明，但本發明中清洗裝置的種=3尸片式進行了說 次式的清洗裝置。 、’不限疋於此，亦可為批 單片式清洗裝置15上連接英 側。在第2循環線n的返回 ^循環線11的返回 ，/D考返回方向而依次插入 201241237 41/l^pif 設置著泵16、反應槽17、送液幻8、冷卻器19，且第2 循1:'的，向前端側連接於上述電解液蓄積㈣。 ίο 85；；^96 wt/。、液溫度贼〜8叱的俩溶液。 循環栗7並騎第1循縣4輸送，冷 為適合於電解的溫度（40t〜7(rc)後導 ；： 的入液側，並自入液孔22a流入至流路23内。解早凡2 電解單元2巾，藉由直流電源3對陽極 =電壓’從而導入至電解單元2内的硫酸溶= 解另卜，错由該電解，電解單元2中，於陽極側生成包 tiS的氧化性物質並產生氧氣，於陰極側產生氫氣。 質與，與上述硫酸溶液混合存在繼 ί ί經流路23的硫酸溶液通過出液孔22b 過第1、循产綠循％線、5,。自出液孔22b送出的硫酸溶液通 續。另5而被运至氣液分離槽6，從而上述氣體被 “ r ί固上述氣體被排出至本系統系統外而藉由觸媒 裝置（未1示）#進行安全處理。 ，隹而液分離槽6分離氣體的硫酸溶液包含過硫酸， 後，il、·!痛環線5的返回侧而回到電解液蓄積槽10 至電解單元2且藉由電解而提高過硫酸的 液農度適度’則電解液蓄積槽ig内的硫酸溶 二熱器;幹過送第2循環線"的輸送側並藉由送液果12 201241237 ~r A / Α —加熱$ 13中’包含過硫酸的硫酸溶液—面通過流路— 面藉由近紅外線加熱H而加熱。較理想的是，送液時以如 下=式對硫酸溶液調整流量，即，自加熱器13的入口至用 於單片式清洗裝置I5為止的通液時間小於丨分鐘，較佳為 =於20秒，更佳為小於1〇秒。另外，單片式清洗裝置u ’ =500 mL/min.〜2000 mL/min·下的流量設為適量，於 ，仙·量中’以上述通液時間小於1分鐘的方式，設定加熱 -13的流路的長度、流路剖面積及其下游綱帛2循環線 U的線長、流路剖面積等。於單片式清洗裝置15内，當 電子材料基板1〇〇被供給硫酸溶液時具有15〇。〇〜22〇。 範圍的液溫。 主於單片式清洗裝置15巾’⑦晶圓等的半導體材料成為 >月洗6對象’該石夕晶圓上設置著例如以 xl〇16at〇ms/cm2進行了離子注入的抗蝕劑。 使該電子材料基板100於未圖示的旋轉台上旋轉，並 ^自未圖示的喷嘴每次少量地包含過硫酸的高溫的硫 酸溶液等而進行接觸，藉此可將電子材料基板剛上的抗 飯劑等的污染物有效地剝離除去。 、#清洗中使用的硫酸溶液自單片式清洗裝置15排出，通 ，第2循環線u的返回側並藉由泵16向反應槽17輸送並 蓄積於其反應槽17中蓄積的硫酸溶液中包含由單片式 /月洗裝置15清洗的抗蝕劑等的殘留有機物，於蓄積在反應 槽17期間，殘留有機物藉由硫酸溶液中所包含的氧化性物 質而氧化分解。另外，反應槽17中的上述硫酸溶液的蓄積 17 201241237The :::=:=::£S pole or the intersection of the partition and so on. /Electricity In the case where the electrolytic cell has a cross-sectional area of the flow path which is relatively smaller than the other portions, the precipitate is clogged and the flow path is easily blocked. Therefore, the present invention is particularly advantageous in an electrolytic unit having a narrow flow path portion. Narrow 201241237 HI / ΙΖ, ρ 下游 The downstream side in the electrolytic cell is more likely to be a problem, for example, in a liquid discharge hole, and may cause a problem that precipitates which are accumulated and accumulated in the retention portion flow along with the sulfuric acid solution 1 precipitate as described above_ In the field of the electrolysis unit μ, the flow of the sulfuric acid > valley liquid is not continued. According to the research conducted by the Japanese and the like, sulfur is likely to be precipitated and accumulated when the sulfuric acid concentration is more than % and the current density is 5GA/dm2 or more. In the case of a higher sulfuric acid concentration, the current density must be set low. ^ And, the unit population temperature reaches the thief ~ grasp the way to run. However, it is considered that if sulfur is deposited and the electric resistance increases, the internal resistance of the unit increases and the unit temperature rises, so that the precipitation of sulfur is accelerated. Qualitatively, this is because the volatilization of water is accelerated, and the concentration is remarkably increased particularly in the retention portion shown in Figs. 7(a) and 7(b). In particular, the operation of the unit inlet temperature exceeding 70 ° C is not good. According to the above, the problem of the sulfur precipitates easily occurs when any one or more of the following three conditions are satisfied, and it is particularly preferable to carry out the invention under such conditions. (a) The sulfuric acid concentration in the electrolytic unit is 85 wt% or more; The temperature of the sulfuric acid at the inlet of the electrolysis unit is 7 〇. 〇 Above; (c) Current density is 50A/dm2 or more. In the cleaning of the electronic material by the sulfuric acid electrolyte, the total organic carbon (TOC) concentration after washing is 〇 mg/1 to l〇mg/l ', and there is almost no organic matter. [Effects of the Invention] 12 201241237 ηι / a厶μιι Unit ^ The invention of the root zone is made by accumulating the miscellaneous solution in the electrolysis = = sulfur-free precipitate or precursor. [Embodiment] It is acceptable to carry out stable electrolysis. effect. (Embodiment 1) Hereinafter, a cleaning system including each device of the present invention will be described with reference to the accompanying drawings. The month's a shape_electrolytic electrolysis set 1 is shown in Figure 1 and there is a thunder without a diaphragm type, which will contain gold and two electrolysis early 70 2 . The electrolysis unit 2 is provided with an anode and a cathode, and the separator 3 is connected to the power supply control unit 4 for controlling the 施加 i applied to the anode and the cathode, and the (4) member is provided with a switch from the DC power source 3, for example. A path for applying a voltage to the anode and cathode. The electrolysis unit 2 is preferably formed of a gold thin film using the following gold film in the anode 2G or the cathode electrode as shown in Fig. 7 (a) + m - ir ± 20 ^ ^ - spacer 20 And relative / · will be Meng Gangshi electrical. The element of the 〇, 000 掺杂 掺杂 而 而 而 而 而 而 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 赋予 。 。 。 。 。 。 。 Further, as the electrolysis unit, 13 201241237 Hi /IZpif may be arranged in a plurality of layers having _: square cut electrodes, thereby flowing a sulfuric acid solution between the electrodes and performing electrolysis. In the spacer 22, a liquid inlet hole 22a is formed on the inlet side, and a liquid outlet hole 22b' is formed on the outlet side. The liquid inlet hole and the liquid outlet hole 22b include a flow path narrower than the flow path 23. The liquid inlet hole 22a and the liquid outlet hole are equivalent to the ◦-shaped ring 24 disposed between the anode portion H阙 spacer 22 and the anode 2〇 and the cathode 21 of the present invention to ensure the sealing of the flow path 23. Sex. As the material constituting the spacer η, a material having an insulating property and a pure ruthenium (for example, made of polytetrafluorethylene) is preferable. In the above-described electrolytic cell 2, the electrode 2A, the inner surface of the electrode 21, the corner portion of the spacer 22, or the inner surface side of the flaw 24 are blocked portions 25 that block the passage of the sulfuric acid solution. The electrolysis unit 2 is configured such that the inlet side is disposed downward and the outlet side is disposed upward. The above electrolysis unit 2 is via the first! The circulation line 5 is connected to the electrolyte storage tank 1 〇 ', and the sulfonium solution can be circulated between the electrolytic unit 2 and the electric charge storage 1G. In other words, the transport side of the first loop line 5 is connected to the electrolysis unit 2 so as to communicate with the inlet side of the electrolysis unit 7L 2 , and the electrolysis unit is connected to the side of the return side read/return unit 2 of the first circulation line 5 2. The gas-liquid separation tank 6 is inserted into the return side of the #1 cycle line 5. In the liquid separation tank 6, a sulfuric acid solution containing a gas is contained and the gas in the sulfuric acid solution is separated and discharged to the outside of the system. A known configuration can be used. The present invention is not particularly limited as long as it can be subjected to gas-liquid separation. 201241237 Further, a circulation pump 7 for circulating the sulfur solution and a cooler 8 for cooling the sulfuric acid solution are inserted into the transport side of the first circulation line 5. The second circulation line 5 and the observation 7 phase are in the liquid supply portion of the present invention. The cooler and the acid solution are cooled to become a liquid suitable for electrolysis such as a thief or a thief: The invention is not particularly limited to the constitution. The electrolysis unit of the present invention is an electrolysis unit 2, a DC power source 3, a power source control unit 4, a cycle = 5, a rolling liquid separation tank 6, a circulation pump 7, and a cooler 8. In the second step, the electrolyte solution f-groove 1G is connected to the transport side of the second circulation line 11 via the test pump 12. Qiandi is connected to the one-chip cleaning device 15. Reading the front end side of the liquid in the direction of the liquid, the above-mentioned heating n 13 has a line heater made of quartz, and the sulfuric acid solution is transiently Μ ^ ^ from the near-infrared ray to obtain 15 (TC 2 in sulfuric acid solution; in the early film "washing device 15 liquid Rapid heating. The liquid temperature of c is applied to the sulfuric acid solution. The monolithic cleaning device 15 φ is placed on a rotating table or the like, and 1 = the electronic material substrate 100 flows from the nozzle to the sulfuric acid solution of persulfuric acid on the semiconductor material. Further, in the present embodiment, although the second embodiment of the cleaning device of the present invention is a sub-type cleaning device, "there is no limitation to this, and it may be a batch-type single-piece cleaning device. 15 is connected to the British side. On the return line of the second loop line n, the return of the loop line 11, /D is returned in the direction of the return and is inserted into the 201241237 41/l^pif. The pump 16, the reaction tank 17, the liquid supply phantom 8, and the cooling are provided. The second 19 is followed by a second cycle of 1:', and is connected to the electrolyte at the front end side (4). ίο 85;; ^96 wt /., liquid temperature thief ~ 8 叱 two solutions. Cycle chest 7 and ride the first According to the county 4 transport, the cold is suitable for the temperature of electrolysis (40t~7(rc) rear guide;: the liquid inlet side, and The self-injection hole 22a flows into the flow path 23. The solution of the electrolysis unit 2 into the electrolysis unit 2 by the DC power source 3 and the anode=voltage is eliminated. In the electrolytic unit 2, an oxidizing substance containing tiS is generated on the anode side to generate oxygen gas, and hydrogen gas is generated on the cathode side. The sulfuric acid solution which is mixed with the above sulfuric acid solution and flows through the flow path 23 passes through the liquid outlet hole 22b. After passing through the first, the green line is followed by the % line, 5, and the sulfuric acid solution sent from the liquid outlet hole 22b is continuously passed. The other 5 is transported to the gas-liquid separation tank 6, so that the gas is discharged by the "r The system is safely processed by the catalyst device (not shown) # outside the system. The sulfuric acid solution separating the gas from the liquid separation tank 6 contains persulfuric acid, and then the return side of the ul, ·! pain ring line 5 Returning to the electrolyte accumulating tank 10 to the electrolysis unit 2, and improving the liquidity of the persulfuric acid by electrolysis, the sulfuric acid dissolving heat exchanger in the electrolyte accumulating tank ig; the conveying of the second circulating line Side and by sending liquid fruit 12 201241237 ~r A / Α - heating $ 13 in 'included The acid sulfuric acid solution-surface is heated by the flow path - the surface is heated by the near-infrared heating H. Preferably, the flow rate is adjusted to the sulfuric acid solution by the following formula when the liquid is supplied, that is, from the inlet of the heater 13 to the single The liquid passing time until the sheet cleaning device I5 is less than 丨 minute, preferably = 20 seconds, more preferably less than 1 〇 second. In addition, the single-chip cleaning device u ' = 500 mL / min. ~ 2000 mL / min・The flow rate in the lower part is set to an appropriate amount, and the length of the flow path of the heating-13, the cross-sectional area of the flow path, and the downstream path of the downstream cycle 2 are set in the case where the liquid passing time is less than 1 minute. Line length, flow path sectional area, etc. In the one-chip cleaning apparatus 15, when the electronic material substrate 1 was supplied with a sulfuric acid solution, it had 15 Torr. 〇~22〇. The range of liquid temperatures. The semiconductor material which is mainly used for the single-chip cleaning device 15 and the '7 wafers' is a <month wash 6 object'. The resist is ion-implanted at x1 〇 16 at 〇 / cm 2 on the ray wafer. . The electronic material substrate 100 is rotated on a rotating table (not shown), and is brought into contact with a high-temperature sulfuric acid solution containing persulfuric acid every time from a nozzle (not shown), whereby the electronic material substrate can be immediately placed thereon. Contaminants such as anti-rice agents are effectively peeled off and removed. The sulfuric acid solution used for the cleaning is discharged from the single-chip cleaning device 15, and is passed through the return side of the second circulation line u, and is sent to the reaction tank 17 by the pump 16 and accumulated in the sulfuric acid solution accumulated in the reaction tank 17. The residual organic matter such as a resist which is cleaned by the one-piece/month washing apparatus 15 is accumulated in the reaction tank 17, and the residual organic matter is oxidatively decomposed by the oxidizing substance contained in the sulfuric acid solution. Further, the accumulation of the above sulfuric acid solution in the reaction tank 17 201241237
Hi/izpif 調 今自早片‘洗裝置15持續地供給高溫 硫酸溶液，反應槽17維持為適當的溫度。 夂的 液,中’所含有的殘留有機物氧化分解的硫酸溶 二t :並通過插入設置在第2循環線11上的冷 部器19，而回流至電解液蓄積槽1〇。 7 電解:Ϊ = 硫酸溶液回流至電解液蓄積槽10，則 促产的硫酸溶液中的過硫酸的分解被 Γ〇?卢Ξ=ί 液藉由冷卻器19而冷卻至贼〜 入5=適§溫度後，被導入至電解液蓄積槽10内。導 送側而槽的硫酸溶液藉由第1循環線5的輸 Λ送且藉由電解而生成過鑛，且藉 中。！返_而再次被送至電紐蓄積槽10 中猎由重稷该循環而持續地生成過硫酸。 藉由上述動作’包含過硫酸的硫酸溶液被輸送並 藉此可舰關的單以清衫置15_地供給包 3同濃度的過硫酸的高溫的清洗液。 17 ΑΠ’以上雖未進行說明，但亦可構成為：於反應槽 ’將排液線分支連接於第2循環線11，並於適 备時f硫酸毅減至系統相不駐反應槽17。 %而藉由f排液線k日摘經過1^每次少量排出硫酸溶液’ 1每防止系統内的溶液中蓄積的抗钱劑摻雜元素或其他尚 _ :刀解的物負蓄積至高漠度為止。該動作可藉由設置 在回^線或排液線的開關的開閉控财來進行。 18 201241237 於上述清洗系統帽續運轉狀態，藉此於電解單元2 内’匕如上述般在電極面、尤其在電極周端部或成為〇形環 的背面的部分的滞留部25生成硫或與硫生成相關的化學 物質。若對該化學物質置之不理，則該化學物質會；;= 般逐漸成長，從而引起剝離或狹小流路的閉塞。 對此，本發明中，在電解的持續時間達到規定時 情況下或電子材料基板刚的處理片數達到規定片數的 況下、判定硫成分的析出達到某程度的情況下等，藉 f控制部4的控制，而進行使自直流電源3施加至陽極2〇 與陰極21間的電壓逆轉的換極動作，並進行電解。 ，極21附近等析出的硫的析出物，會被在換極後作曰 =揮功能的陰極21附近生成的氧化性物質所溶解： 溶液一併移動。藉由將換極動作持續一定程度，而 消除硫析錢或減小硫析出物，然後可持續進行^ 解。消除硫析出物或減小硫析出物後以該㈣持續運轉電 並於換極後的陰極蓄積硫析出物或其前驅物之前再次 換極’從而使向逆方向施加i陽極2〇與陰極以之 壓逆轉而向順方向施加電壓並進行電解。 曰、 若重複上述動作，則可長時間持續進行穩定的電解。 -般而言’為應對有機物崎而 ^極不同而換極時間受到限制，但本實施形態㈣g 金岡=電極’故在換極的狀態下可長時 勺為Hi/izpif is adjusted from the early film "washing device 15" to the high temperature sulfuric acid solution, and the reaction tank 17 is maintained at an appropriate temperature. In the liquid of the crucible, the residual organic matter contained in the medium is dissolved in sulfuric acid, which is oxidatively decomposed, and is passed through the cold unit 19 provided on the second circulation line 11 to be returned to the electrolytic solution storage tank 1〇. 7 Electrolysis: Ϊ = The sulfuric acid solution is returned to the electrolyte accumulating tank 10, and the decomposition of persulfuric acid in the promoted sulfuric acid solution is decomposed. Lulu = ί liquid is cooled by the cooler 19 to the thief ~ 5 = suitable After the temperature, the temperature is introduced into the electrolyte accumulating tank 10. The sulfuric acid solution on the transfer side and the trough is sent by the transport of the first circulation line 5 and is produced by electrolysis, and is borrowed. ! The _ is again sent to the electric current accumulating tank 10, and the sulphur is continuously generated by repeating the cycle. By the above-mentioned action, a sulfuric acid solution containing persulfuric acid is transported, whereby a high-temperature cleaning liquid of the same concentration of persulfuric acid of the package 3 is supplied to the clearing plate. 17 ΑΠ' is not described above, but may be configured such that the liquid discharge line is branched and connected to the second circulation line 11 in the reaction tank, and the sulfuric acid is reduced to the system phase non-reserved reaction tank 17 when it is suitable. % by the f discharge line k day picking through 1 ^ each time a small amount of sulfuric acid solution '1 per anti-moist agent doping element accumulated in the solution to prevent accumulation of the system or other _: knife solution negative accumulation to the high desert So far. This action can be performed by opening and closing the switch provided on the return line or the drain line. 18 201241237 In the above-described washing system cap operation state, sulfur or the like is generated in the electrolytic unit 2 as described above on the electrode surface, particularly at the electrode peripheral end portion or the portion of the back surface of the beak ring. Sulfur-related chemicals. If the chemical is left untreated, the chemical will gradually grow, causing detachment of the peeling or narrow flow path. On the other hand, in the case where the duration of electrolysis reaches a predetermined level or when the number of processed sheets of the electronic material substrate reaches a predetermined number of sheets, and the precipitation of the sulfur component is determined to be a certain degree, the control is performed by f control. The control of the unit 4 performs a pole-changing operation for reversing the voltage applied from the DC power source 3 to the anode 2 and the cathode 21, and performs electrolysis. The precipitate of sulfur precipitated in the vicinity of the pole 21 is dissolved by the oxidizing substance generated in the vicinity of the cathode 21 which is subjected to the enthalpy after the pole switching: the solution moves together. Eliminate sulfur precipitation or reduce sulfur precipitates by continuing the pole-changing action to a certain extent, and then continue to work. After removing the sulfur precipitates or reducing the sulfur precipitates, the electricity is continuously operated by the (4) and the poles are re-polarized before the cathodes after the poles are accumulated to accumulate the sulfur precipitates or their precursors, thereby applying the anodes 2 and cathodes in the opposite direction. The pressure is reversed and a voltage is applied in the forward direction and electrolysis is performed.曰 If the above operation is repeated, stable electrolysis can be continued for a long time. Generally speaking, in order to cope with the organic matter, the polarity change time is extremely different, but in the present embodiment (4) g Jingang = electrode ', the state can be long when the pole is changed.
小時）進行通常運轉。 Ί T 另外’就持續換極後的運轉的時間而言，可設為通常 19 201241237 41 /l^pif 的電解時間達到預定的規定時間的情況。規定時間可考廣 累積的通電量或硫酸溶液的濃度、溫度、通液速度等來^ 定，而且也可實驗性地求出。而且，在清洗的電子材料義 板⑽的片數達到規定片數的情況下亦可執行換極動作: 亦可使換極後的運轉的持續時間不固定，但在 面以均等的厚度積層金剛石層時，為了使伴隨運 =金剛石的磨耗變得均等，較理想的是將持續時間設為 而^作為執行換極動作的其他時序，可利用推測電 的析出程度的結果。即，於推測的硫的析出 程；可=二的程度的情況下’執行換極動作。硫的析出 電流進行電解時上升的電解電 若5亥電壓達到預定的電解電壓，貞彳# 為硫的析出加重而進行換極動作。㈣ϋ則硯 (實施形態2) 洗槽解裝置1應用於批次式清 與上述實施料7： 2進行說明。另外，本實施形態2中對 化說明。目同的構成附上相同的符號並省略或簡 上述電解單元2姑山& 積槽10。在第=第1循環線5喊接著電解液蓄 6，在第1循環線5 =t、的返回側插入設置著氣液分離槽 卻器8。 輸送側依次插入設置著循環泵7、冷 批次式清洗槽 利用第2循環線31連接著排液側與 20 201241237 =器：^；f設置著送液栗32 内的硫酸騎巾L _批:_洗槽30 等剝離清洗。此時，藉由 方式進行控制並使硫酸溶液循環。又‘、、〜i9〇c的 3循二ΓΓΛ32的下游側且加熱器33的上游側，返回第 循％線35分支連接於第2循環線3卜返回第 的=端側經由冷卻器37而連接於 ^ 電解液蓄積槽1〇經由详油石α ±苗價〜丄υ 環㈣。輸送第3循;連接著輸送第3循 循環線3i合流而連接Γ在加熱器％的下游側與第2 述加熱II 33可設為與上述加熱器13相同的構成。 八次’對包含上述構成的清洗系統的動作進行說明。 於電解液蓄積槽10中，蓄積著硫酸濃度85㈣〜％ =、液體溫度坑〜啊的硫酸溶液，將該硫 =環泵7並通過第1循環線5而輸送，且利用冷卻器错8 =整為適合於電解的溫度（贼〜贼）後自電解單元2 的入液孔22a導入至流路23。 電解早tg2中，藉由直流電源3對陽極、陰極間向順 方向施加電壓’從而導人至電解單元2内的硫酸溶液被電 ，。經電解的硫酸溶液通過出液孔创而被送至第i循環 線5，且利用氣液分離槽6將氣體分離。 已由氣液分離槽6分離氣體的上述硫酸溶液通過第1 201241237 循線5的返回你丨而n n + 至電解單元2 * σ 1電解液蓄積槽10後’被重複地送 酸濃度適度，則二藉由電解而提高過硫酸的濃度。若過硫 過輸送第3抵I® ώ液蓄積槽1〇内的硫酸溶液的一部分通 的下游側的in34並藉由送液泵36而被送向加熱器33 液合流。祕3卜J'與第2循環線31的硫酸溶 而且:„液被導人至批次式清洗槽30内。 並通過第2 先槽3Q内的硫酸溶液藉由送液泵32 導入至批次式以=環。此時由加熱器33加熱且被 力口敎器33 ψ 人 面藉由力而^有過魏的硫酸溶液—面通過流路一 輸送的硫酸溶^；： °此時與由上述輸送第3循環線34 具有靴〜^給錄次式清洗槽3G内時，以 於批a★支c的範圍的液溫的方式進行加熱。 所使用的==内清洗電子材料基板⑽。清洗中 加軌哭33 ^於第魏線31上—部分進行循環並由 利用i回第°3=向批次式清洗# 30返送’並且剩餘部分 時，以冷卻号/f線35而返回到電解液蓄積槽1〇中。此 7〇χ： 〇 37冷卻硫酸溶液至適合於電解的4〇ΐ〜 電解液蓄積槽1〇中，硫酸溶液 由循環泵7而被送至電解 線5且猎 電解液蓄簡1G巾。 生成過贿，並回到 藉由重複上述硫酸溶液的循環，而可於 定的狀態下進行電子材料基板刚的清洗。農度穩 22 201241237 ?肉於上述清㈣統中持續運轉狀態，而於電解單元 學物質°。留巾部25中生成硫或與硫生成相關的化 間的雷上Ϊ 流電源3施加至陽極20與陰極2! Ρ極附、轉的換極動作，並制地進行轉。藉此，於 ^草析出的硫的析出物被溶解。藉由將換極動作持 :進行“的ί:消除或減小硫析出部，藉此之後可持續 (比較例） ，例除於實施形態2中不具有電源控制部4 且 貫=態！相同的構成，且根據圖3來進行說明。電 順芦二：由直流電源3 一直對陽極側與陰極側施加 順向電£，攸而可進行硫酸溶液的電解。 尊』：2:硫酸溶液電解而可有效地清洗半導體基板 專的被>月洗材料。然而’隨時間經過於電解單元内會生成 ^硫析出物使電解單元2的狹小流路部 閉塞相導致清洗能力降低，或使清洗自身變得困難。而 且’若剝離的硫析出物到達電解單元的入液孔等的狭小流 路，則會發生流路閉塞或流動性變差的問題。 以上，根據上述實施形態對本發明進行了說明，但本 發明並不限定於上述實施形態的内容，只要不脫離本發明 則可進行適當的變更。 [實例] 其1 :對使用了圖1所示的單片式清洗系統的實例進 23 201241237 /i^pir 仃說明 於硫酸濃度=92 wt%、電解單元入口液體 =密度=35A/dm2條件下持續進行運:二C 時電解後便進行換極，將持續50小時重複^f、.\50巧 極後=單=行内部檢查，結果未看到^ 行說明。憤用了圖2所示的批次式清洗系統的實^ _度，dm2條件下_進彳爾 二位f處理’對每4。批次進行換極 開早7G來進油部檢查’結果未看到任何硫的附著。 (比較例） 使用圖3所示的不具備換極功能的批次式清洗 於硫酸濃度=85wt%、電解單元人口液體溫度=耽 密度=5GA/dm2條件下觸騎運轉，#超過1⑻批次後^ 壓便開始上升，麟量亦緩慢降低。·^ 1單元的液流量減 半後，打開單元來進行檢查，結果在單元出口部流路 因硫而引起的閉塞。 【圖式簡單說明】 圖1是表示具備本發明的一實施形態的電解單元的單 片式清洗糸統的圖。 圖2是表示具備本發明的一實施形態的電解單元的批 夂式清洗糸統的圖。 圖3是表示使用了不具備換極功能的電解單元的批次 24 201241237 Τ 1 / 1 ζ-ρι 丄 式清洗糸統的圖。 圖4是表示波貝克斯（Pourbaix )的線圖的圖。 圖5是表示波貝克斯（Pourbaix)的線圖的圖。 圖6 (a)及圖6 (b)是根據波貝克斯（Pourbaix)的 線圖而表示硫酸濃度92 wt%、溫度60°C的硫酸與水的電 位的曲線。 圖7 (a)及圖7 (b)是表示電解單元的構造與硫的蓄 積狀態的圖。 【主要元件符號說明】 1 :電解裝置 2:電解單元 3:直流電源 4:電源控制部 5:第1循環線 6 :氣液分離槽 7 :循環泵 8、19、37 :冷卻器 10 :電解液蓄積槽 11、 31 :第2循環線 12、 32、36 :送液泵 13、 33 :加熱器 15 :單片式清洗裝置 16 :泵 17 :反應槽 25 201241237 斗1 /izpif 18 :送液泵 20 :陽極 21 :陰極 22 :間隔件 22a :入液孔 22b :出液孔 23 :流路 24 : Ο形環 25 :滞留部 30 :批次式清洗槽 34 :輸送第3循環線 35 :返回第3循環線 100 :電子材料基板 A ·硫析出 B:單元出口或單元入口閉塞 26Hour) Perform normal operation. Ί T In addition, the time during which the operation after the pole change is continued can be set as the case where the electrolysis time of the usual 19 201241237 41 /l^pif reaches a predetermined predetermined time. The predetermined time can be determined by the cumulative amount of energization, the concentration of the sulfuric acid solution, the temperature, the flow rate, and the like, and can also be experimentally determined. Further, when the number of sheets of the electronic material board (10) to be cleaned reaches a predetermined number of sheets, the pole-changing operation can be performed: the duration of the operation after the pole-changing can be made not constant, but the diamond is laminated on the surface with an equal thickness. In the case of the layer, in order to equalize the wear of the accompanying diamond = diamond, it is preferable to use the duration as the other timing for performing the pole-changing operation, and the result of estimating the degree of precipitation of the electricity can be utilized. That is, in the case where the estimated sulfur is precipitated; if it is possible to be two, the step of performing the pole-changing operation is performed. Sulfur precipitation current Electrolytic power that rises during electrolysis If the voltage of 5 hp reaches a predetermined electrolysis voltage, 贞彳# is subjected to a pole-changing action by increasing the precipitation of sulfur. (4) ϋ 砚 (Embodiment 2) The rinsing and dissolving device 1 is applied to batch cleaning and the above-described embodiment 7: 2 will be described. Further, in the second embodiment, the explanation will be given. The same components are denoted by the same reference numerals, and the above-mentioned electrolytic unit 2, Gushan & On the first = first circulation line 5, the electrolyte is stored, and the gas-liquid separation tank 8 is inserted in the return side of the first circulation line 5 = t. The circulation side is sequentially inserted into the circulation pump 7, and the cold batch type cleaning tank is connected to the liquid discharge side by the second circulation line 31 and 20 201241237 = device: ^; f is provided with the sulfuric acid riding towel L_ batch in the liquid supply pump 32 :_ Wash tank 30 and other strip cleaning. At this time, control is performed by means and the sulfuric acid solution is circulated. Further, on the downstream side of the three-passer 32 of the ', ～i9〇c, and on the upstream side of the heater 33, the return-to-counter % line 35 is branched and connected to the second loop line 3, and the returning end side is via the cooler 37. Connected to the electrolyte storage tank 1 through the detailed oil stone α ± Miao ~ 丄υ ring (four). The third transport is carried out; the third transport line 3i is connected to the transport line, and the downstream side of the heater is connected to the second side of the heater, and the second heating unit (III) is the same as the heater 13. Eight times, the operation of the cleaning system including the above configuration will be described. In the electrolyte storage tank 10, a sulfuric acid solution having a sulfuric acid concentration of 85 (four) to % = and a liquid temperature pit is accumulated, and the sulfur = ring pump 7 is transported through the first circulation line 5, and the cooler is used to be 8 = The temperature (thief-thief) suitable for electrolysis is introduced into the flow path 23 from the liquid inlet hole 22a of the electrolysis unit 2. In the electrolysis early tg2, the sulfuric acid solution introduced into the electrolysis unit 2 is electrically charged by applying a voltage ' between the anode and the cathode to the direct current source 3. The electrolyzed sulfuric acid solution is sent to the i-th cycle line 5 through the outlet hole, and the gas is separated by the gas-liquid separation tank 6. The above-mentioned sulfuric acid solution which has been separated from the gas by the gas-liquid separation tank 6 passes through the return of the first 201241237 line 5, and nn + to the electrolytic unit 2 * σ 1 after the electrolyte storage tank 10 is 'repeatedly sent acid concentration moderately, then Second, the concentration of persulfuric acid is increased by electrolysis. When the sulfur is over-transferred, the in34 of the downstream side of the sulfuric acid solution in the third I/ sputum storage tank 1 is sent to the heater 33 to be liquefied by the liquid feeding pump 36. The sulfur solution of the secret 3b J' and the second circulation line 31 is dissolved and the liquid is introduced into the batch cleaning tank 30. The sulfuric acid solution in the second first tank 3Q is introduced into the batch by the liquid feeding pump 32. The sub-type is = ring. At this time, it is heated by the heater 33 and is immersed in the sulphuric acid solution by the force port 33 by the force of the force port 33. When the third circulation line 34 is transported to the recording cleaning tank 3G, the liquid is heated in the range of the batch a*c. The used == internal cleaning electronic material substrate (10). During the cleaning, add the cry 33 ^ on the Wei Wei line 31 - part of the cycle and return by the use of i back ° = = to the batch cleaning # 30 'and the rest, with the cooling number / f line 35 Returning to the electrolyte storage tank 1〇. This 7〇χ: 〇37 cools the sulfuric acid solution to 4〇ΐ~ electrolyte storage tank 1适合 suitable for electrolysis, and the sulfuric acid solution is sent to the electrolysis line 5 by the circulation pump 7. And the electrolyte is stored in a 1G towel. The bribe is generated and returned to the electronic material by repeating the circulation of the above sulfuric acid solution. The material substrate has just been cleaned. The agricultural degree is stable 22 201241237. The meat is continuously operated in the above-mentioned clear (four) system, and the material is in the electrolysis unit. The sulfur is generated in the towel portion 25 or the thunder is associated with the formation of sulfur. The flow source 3 is applied to the anode 20 and the cathode 2! The pole-extinguishing action of the drain and the turn is performed, and the ground is rotated. Thereby, the precipitate of sulfur precipitated in the grass is dissolved. In the second embodiment, the power supply control unit 4 is not provided in the embodiment 2, and the power supply control unit 4 is not provided in the second embodiment. The same configuration will be described with reference to Fig. 3 . Electric Shulu 2: The direct current power supply 3 always applies the forward electricity to the anode side and the cathode side, and the electrolysis of the sulfuric acid solution can be performed.尊』: 2: Electrolytic solution of sulfuric acid can effectively clean the semiconductor substrate. However, the formation of sulfur precipitates in the electrolytic cell over time occludes the narrow flow path portion of the electrolytic cell 2, resulting in a decrease in cleaning ability or difficulty in cleaning itself. Further, if the separated sulfur precipitates reach a narrow flow path such as a liquid inlet hole of the electrolytic cell, the flow path is blocked or the fluidity is deteriorated. The present invention has been described above based on the above embodiments, but the present invention is not limited to the above embodiments, and can be appropriately modified without departing from the invention. [Examples] 1 : For an example using the one-piece cleaning system shown in Fig. 1, 23 201241237 /i^pir 仃 is described in the case of sulfuric acid concentration = 92 wt%, electrolytic unit inlet liquid = density = 35 A / dm 2 Continue to carry out the operation: after the second C, the pole is changed after electrolysis, and it will repeat for 50 hours. ^f, .\50, and then = single = line internal inspection, the result is not seen. Indignantly used the actual cleaning system of the batch cleaning system shown in Figure 2, under the condition of dm2, the two-position f treatment was performed on every 4th. The batch was changed to the pole and opened 7G early to the oil inlet inspection. As a result, no sulfur adhesion was observed. (Comparative Example) Using the batch type cleaning without the polarity changing function shown in Fig. 3, the contact operation was carried out under the conditions of sulfuric acid concentration = 85 wt%, electrolytic cell population liquid temperature = enthalpy density = 5GA/dm2, #1 more than 1 (8) batch After the pressure began to rise, the amount of Lin also slowly decreased. • After the liquid flow rate of the unit is reduced by half, the unit is opened for inspection, and the flow path due to sulfur is blocked at the outlet of the unit. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a one-piece cleaning system including an electrolytic cell according to an embodiment of the present invention. Fig. 2 is a view showing a batch type cleaning system including an electrolytic cell according to an embodiment of the present invention. Fig. 3 is a view showing a batch 24 201241237 Τ 1 / 1 ζ-ρι 丄 type cleaning system using an electrolytic unit which does not have a pole-changing function. Fig. 4 is a view showing a line graph of Pourbaix. Fig. 5 is a view showing a line graph of Pourbaix. Fig. 6 (a) and Fig. 6 (b) are graphs showing the potential of sulfuric acid and water at a sulfuric acid concentration of 92 wt% and a temperature of 60 °C according to a line diagram of Pourbaix. Fig. 7 (a) and Fig. 7 (b) are views showing the structure of the electrolytic cell and the state of accumulation of sulfur. [Explanation of main component symbols] 1: Electrolytic device 2: Electrolysis unit 3: DC power supply 4: Power supply control unit 5: First circulation line 6: Gas-liquid separation tank 7: Circulating pump 8, 19, 37: Cooler 10: Electrolysis Liquid storage tanks 11, 31: second circulation line 12, 32, 36: liquid supply pump 13, 33: heater 15: single-piece cleaning device 16: pump 17: reaction tank 25 201241237 bucket 1 /izpif 18 : liquid supply Pump 20: anode 21: cathode 22: spacer 22a: liquid inlet 22b: liquid outlet 23: flow path 24: Ο ring 25: stagnation part 30: batch type cleaning tank 34: conveying the third circulation line 35: Return to the third circulation line 100: electronic material substrate A · sulfur deposition B: unit outlet or unit inlet occlusion 26