201128697 六、發明說明： 【發明所屬之技術領域】 [0001] 本發明係有關於一種使用含草酸的蝕刻液，來蝕刻形成 有氧化銦錫膜之基板之蝕刻方法。 【先前技術】 [0002] 在製造半導體晶圓、液晶玻璃基板、光罩用基玻璃基板 、光碟用基板之各種基板之步驟，有使用蝕刻液來將該 等基板姓刻之步驟。 0 [⑻03] 而且’作為用以實施如此的步驟之蝕刻裝置，先前，例 如已知在特開2 0 0 0 - 9 6 2:6 4號公報所揭示者、該蚀刻裝置 係具備： 儲存槽，其係儲存蝕刻液； 蝕刻機構’其係使用蝕刻液來蝕刻基板；及 蝕刻用循環機構，其將儲存槽内的蝕刻液供給至蝕刻機 構’同時將所供給的蝕刻液回收至儲存槽内，且使姓刻 液在儲存槽與蝕刻機構之間循環。 〇 [0004] 前述蚀刻機構係具備： 處理室； 複數搬運輥，其係配設在處理室内，來搬運基板；及 複數噴嘴體，其係配設在處理室内，來將蝕刻液朝向基 板上面吐出，前述蝕刻用循環機構係由下列構成： 供給管’其係連接儲存槽與各噴嘴體； 供給泵，其係透過供給管而將蝕刻液供給至各噴嘴體； 及 100101551 回收管，其係連接處理室的底部與儲存槽。 表早編號 A0I01 ^ 〇 -§ /1» λμ s 1003052484-0 201128697 [0005] [0006] [0007] [0008] ’在該麵刻裝置’被供給至各喷嘴 刻液，係朝向藉•運輥搬運的基板之上/子槽内的 並藉由被吐出的_液來則基板。又，被/吐出， 上面的軸液係藉由回收管而被回收至錯存^至基板 =是，當作軸對象之基板，例如在上㈣二: 錫膜之基板時，將該基板 有乳化姻 銦及錫係溶㈣n彡缝銦錫膜之 之上述的循環裝Γ:儲:：，在使〜而使用 子及錫離子）的濃度係慢慢地上升而產生㈣速 洛之問題、和無法高精確度地崎基板之問題。 因此’上祕㈣置_定誠交換儲錢㈣姓刻液 ’而敍刻液的交換所需要㈣用（❹完畢後的㈣液之 廢棄費用、和新_液的購入費用）致使處理成本上升。 在蚀亥J液的交換作業中係無法使麵刻裝置運轉，因 此，處理成本亦提高。 因此，本申請人提案揭示一種鈇刻裝置（參照特開 2008-252049號公報），其係將銦籬子及錫離子從蝕刻液 除去而能夠將該蝕刻液再生。該蝕刻裝置係除了上述構 成以外，更具備： 吸附塔，其係在内部填充有吸附銦離子及錫離子之甜合 劑；及 除去用循環機構’其係使儲存槽内的钱刻液通液至吸附 塔内，同時使通液後的蝕刻液回流至儲存槽内，並且使 餘刻液在儲存槽與吸附塔之間循環。 100101551 表單編號Α0101 第4頁/共27頁 1003052484-0 201128697 [0009] 而且，在此種蝕刻裝置，因為藉由蝕刻液在儲存槽與吸 附塔之間循環，並藉由吸附塔的鉗合劑來吸附、除去蝕 刻液中的銦離子及錫離子，能夠抑制在儲存槽内的蝕刻 液所包含的銦離子及錫離子的濃度上升，所以能夠防止 如上述的問題。 [0010] [先前技術文獻] [專利文獻] [專利文獻1]特開2000-96264號公報 ^ [專利文獻2]特開2008-252049號公報 〇 【發明内容】 [0011] [發明所欲解決之課題] 但是，本發明者等重複專心研究的結果，清楚明白即便 使蝕刻液在儲存槽與吸附塔之間循環而吸附、除去在蝕 刻液所含有的銦離子及錫離子之情況，特別是關於銦離 子的濃度，必須將其管理為適當的濃度。這是因為銦離 子的濃度超過一定水準時，蝕刻液中的銦離子會與蝕刻 Q 液中的草酸鍵結且結晶化成為草酸銦之緣故。 [0012] 例如在因蝕刻液而經常濕潤的部分，該結晶化係不容易 產生，例如在鄰接在内部有蝕刻液吐出之處理室且内部 空間係與處理室的空間連通之室（chamber)(鄰接室）的 内壁、和被配置在鄰接至内之基板搬運用輥、將處理室 的基板搬入口或基板搬出口開閉之開閉器等，草酸銦會 析出。更具體地，在基板搬入時或搬出時，開閉器打開 時，霧狀的蝕刻液會從處理室内透過基板搬入口或基板 搬出口而流入至鄰接室内並黏附在前述内壁、基板搬運 100101551 表單編號A0101 第5頁/共27頁 1003052484-0 201128697BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching method for etching a substrate on which an indium tin oxide film is formed by using an etching solution containing oxalic acid. [Prior Art] [0002] In the steps of manufacturing various substrates of a semiconductor wafer, a liquid crystal glass substrate, a photomask base glass substrate, and a disc substrate, there is a step of using an etching liquid to name the substrate. 0 [(8)03] and as an etching apparatus for carrying out such a procedure, as disclosed in Japanese Laid-Open Patent Publication No. 2000-96:6, the etching apparatus is provided with: a storage tank The etching mechanism stores an etching solution; the etching mechanism etches the substrate using an etching solution; and an etching cycle mechanism that supplies the etching liquid in the storage tank to the etching mechanism while recovering the supplied etching liquid into the storage tank And circulating the surname engraving between the storage tank and the etching mechanism. 0004 [0004] The etching mechanism includes: a processing chamber; a plurality of conveying rollers disposed in the processing chamber to transport the substrate; and a plurality of nozzle bodies disposed in the processing chamber to discharge the etching liquid toward the substrate The etching cycle mechanism is composed of: a supply pipe 'connecting the storage tank and each nozzle body; a supply pump that supplies the etching liquid to each nozzle body through the supply pipe; and a 100101551 recovery pipe that is connected The bottom of the processing chamber is connected to the storage tank. Table early number A0I01 ^ 〇-§ /1» λμ s 1003052484-0 201128697 [0005] [0007] [0008] The device in the face is supplied to each nozzle engraving, facing the borrowing roller The substrate is placed on the substrate/sub-tank in the carrier and by the discharged liquid. Further, it is discharged/discharged, and the upper shaft liquid is recovered by the recovery pipe to the substrate. = Yes, the substrate serving as the axis object, for example, in the case of the upper (four) two: tin film substrate, the substrate has The above-mentioned cyclic device of the emulsified indium and tin-based (four) n-stitched indium tin film: storage:: the concentration of the used and tin ions is gradually increased to cause (four) speed problem, And the problem of the substrate that cannot be highly accurate. Therefore, 'Supreme (four) set _ Dingcheng exchange of money (four) surname engraved 'and the exchange of the etched liquid needs (four) with (after the completion of the (four) liquid waste costs, and the purchase of new _ liquid costs) resulting in increased processing costs . In the exchange operation of the Eclipse J liquid, the surface engraving device cannot be operated, and therefore the processing cost is also increased. Therefore, the applicant's proposal discloses an etching apparatus (refer to Japanese Laid-Open Patent Publication No. 2008-252049), which is capable of regenerating the etching liquid by removing the indium fence and tin ions from the etching liquid. In addition to the above configuration, the etching apparatus further includes: an adsorption tower filled with a sweetener that adsorbs indium ions and tin ions; and a recycling mechanism for removing the money in the storage tank to In the adsorption tower, the etched liquid after the liquid passing is simultaneously returned to the storage tank, and the residual liquid is circulated between the storage tank and the adsorption tower. 100101551 Form No. 101 0101 Page 4 / Total 27 Page 1003052484-0 201128697 [0009] Moreover, in such an etching apparatus, since the etching liquid circulates between the storage tank and the adsorption tower, and the chelating agent of the adsorption tower By adsorbing and removing indium ions and tin ions in the etching liquid, it is possible to suppress an increase in the concentration of indium ions and tin ions contained in the etching liquid in the storage tank, and thus it is possible to prevent the above problems. [PRIOR ART DOCUMENT] [Patent Document 1] JP-A-2000-96264 (Patent Document 2) JP-A-2008-252049A SUMMARY OF THE INVENTION [0011] [Invented to solve However, the inventors of the present invention have repeatedly studied the results of intensive studies, and have clearly understood that even when the etching liquid is circulated between the storage tank and the adsorption tower, the indium ions and tin ions contained in the etching liquid are adsorbed and removed, in particular, Regarding the concentration of indium ions, it must be managed to an appropriate concentration. This is because when the concentration of the indium ions exceeds a certain level, the indium ions in the etching solution are bonded to the oxalic acid in the etching Q liquid and crystallized into indium oxalate. [0012] For example, in a portion which is often wetted by an etching liquid, the crystallization is not easily generated, for example, a chamber adjacent to a processing chamber in which an etching liquid is discharged inside and an internal space is in communication with a space of the processing chamber ( In the case of the inner wall of the adjacent chamber, and the substrate transporting roller disposed adjacent to the inside, the substrate carrying inlet of the processing chamber, or the shutter for opening and closing the substrate carrying port, indium oxalate is precipitated. More specifically, when the shutter is opened or when the shutter is opened, the mist-like etching liquid flows into the adjacent chamber through the substrate loading port or the substrate carrying port from the processing chamber, and adheres to the inner wall, and the substrate conveys 100101551. A0101 Page 5 of 27 1003052484-0 201128697
用輥及開閉器，所黏附之铋Μ、产A 接玄內“”神〜 中水分，係因為在鄰 未在處理室内有姓刻液被吐出，所以容 ’水分蒸發時，-液中的銦離子之濃度提高，職和 ::會以草酸銦的形式析出。又，-旦草酸銦析出 時結晶會以此為核而成長。 [0013] [0014] [0015] 100101551 此進仃料銦結晶化時，由於黏附在基板搬運用概 之結晶致使基板受傷，或是造成開閉器的動作不良。又 ’卓酸銦的結晶掉落至被回收至儲存槽内之仙液時， 因班為與㈣液同時揭環，亦成為將塵埃等的不純物從循 ,的蝕刻液除去之過濾器堵塞的原因。為了防止此種問 題雖然除去黏附在前述内壁、基板搬運用挺及開閉器 等之結晶、或交換即可，但是定錄進行此種維 修作業時，該㈣裝置的運轉效率會低落。而且，草酸 銦的結晶係與僅是草酸的結晶不同，因為即便掉落至蚀 刻液中亦難以溶解’而以結晶狀態被包含在㈣液中。 如此’即便使㈣合劑來將銦離子及錫離子 從蝕刻液吸 附 '除去之情況’關於銦離子㈣度，亦有必要將其管 理為適當的濃度。 本發明係本發明者等重複專心研究之結果，且係將提供 #能约將在钱刻液所含有的銦離子及錫離子之中、特 ~銦離子n维持在適當的濃度之關方法設為其 目的。 [解決課題之手段] 為了達成上述目的’本發明係—種蚀刻方法其係含有 d V驟及金屬除去步驟之姓刻方法，該触刻步驟係從 表單編號A0101 第Κ π 0 頁/共 27 頁 1003052484-0 201128697 ·=噴嘴雜並藉由從該噴嘴雜一= 破吐出的姓刻液從 J時將則述 Ο [0016] Ο [0017] =去步驟係使在前述儲存槽内所儲存的钱刻液通 =料充有朗崎子絲離子⑽合劑之吸附 ，來將因蝕刻而被包含在蝕刻液令的銦離子及錫 子吸附、除去，同時使吸附、除去_離子及錫離子後 的麵刻液回流至前述儲存槽内；其中 在前述金屬除去步驟，係以被儲存在前述儲存槽内的蝕 幻液的鋼離子濃度為被維持在26Oppm以下的方式進行吸 附、除去銦離子及錫離子。 依照該方法，藉由含草酸的钱刻液，在儀刻形成有氧化 銦錫膜的基板時，係實施蝕刻步驟及金屬除去步驟，該 餘刻步驟係使儲存槽内的鈞刻液邊循環邊使其從噴嘴體 吐出來蝕刻基板；而 該金屬除去步驟係使儲存槽内化钱刻液邊循環邊使用吸 附容器内的鉗合劑來吸附、除去姓刻液中的銦離子及錫 離子，而且在前述金屬除去步驟’係以在前述儲存槽内 的蝕刻液所含有的銦離子濃度為被維持在260ppm以下的 方式進行吸附、除去銦離子及錫離子。 如上述，特別是關於铜離子’其濃度超過一定水準時， 例如在鄰接在内部有蝕刻液吐出之處理室且内部空間係 與處理室的空間連通之室（鄰接室）的内壁 '和被配置在 鄰接至内之基板搬運用輥、將處理室的基板搬入口或基 100101551 表單編號A0101 第7頁/共27頁 1003052484-0 201128697 板搬出口開閉之開閉器等’草酸銦會結晶化，且由於黏 附在基板搬運用輥之結晶致使基板受傷Ή造成開閉 器的動作不良，或是由於草酸銦的結晶掉落而含有在被 回^至儲存槽内之_液中’致使將塵埃等的不純物從 循裱的蝕刻液除去之過濾器產生堵塞之 防止此種問題’進行除去黏附在前述内壁'基板搬運用 親及開閉器等之結晶、或交換過渡器時，由於此種維修 作業致使蝕刻的處理效率低落。 [0018] [0019] =痒本料料錢各種實狀以，得縣姻離子 的浪度（質量濃度）為細侧以下時，在前述内壁、基板 搬運用輥及開閉器等，草酸銦不會析出之知識。 二在本發明，係以被儲存在前迷錯存槽内的钱刻液 的銦離子濃度為被維持在260ppm以下的方式― 及T。藉此，實地防：： 因此’不會產^於·在基她 致使基板受傷，或是造成開閉器的 m之…日 r的結晶掉落-有在被回收至::槽:::： 致使將塵埃等的不純物從循環的㈣液除去之 =產生堵塞之問題，而且亦不必進行除去軸在前= 内壁 '基板搬運用輥及開閉器等之結晶和交換過遽 維修。 100101551 [0020] 而且’為了將姆子濃度維持在26()卿以下亦可經常 將儲存槽内祕刻液通液至吸附容器内，使錄存槽内的 1刻液通液錢附容H内而_子毅下降時，可暫 時停止通液至吸附容器内，而且通液至吸附容器内之二 表單編號A0101 第8頁/共27頁 1003052484-0 201128697 法係不受任何限定。 [0021] 又，鉗合劑係通常具備平衡濃度越高平衡吸附量鵡多 特性，說明平衡濃度及平衡吸附量與銦離子的吸附 係時，所謂平衡濃度係相當於使其通液至吸附容器關 蝕刻液的銦離子濃度，而所謂平衡吸附量 之 叫田於使用 平均單位重量鉗合劑能夠吸附之最大銦量。 [0022] Ο 因此，使其通液至吸附容器内之蝕刻液的銦離子濃度越 高，相較於較低時，能夠使較多的銦離子吸附於鉗人， ,能夠增加至被鉗合劑吸附的銦離子達到飽和狀離σ , 板處理片數。從如此的觀點，在儲存槽内的蝕刻液 有的銦離子之濃度，係以在不生成結晶物之26Qp:3下 的犯圍盡可能高濃度純。但是’銦離子濃度為 以上時，因為能夠確保被鉗合劑吸附的銦離子連到飽和 狀態之基板處理片數為-定水準以上，不會損害經濟性 〇 - ---!: : .With the roller and the shutter, the adhered enamel, the production A is connected to the sinusoidal "" God ~ middle water, because the neighboring sputum is spit out in the processing room, so the water is evaporated, in the liquid The concentration of indium ions is increased, and the occupation:: will precipitate in the form of indium oxalate. Further, when indole oxalate is precipitated, crystals grow as a core. [0015] [0015] 100101551 When the indium is crystallized, the substrate is adhered to the substrate for crystallization, and the substrate is injured or the operation of the shutter is poor. In addition, when the crystal of the indium sulphate is dropped to the liquid in the storage tank, the filter is blocked by the etchant which removes impurities such as dust and the like. the reason. In order to prevent such a problem, the crystals adhered to the inner wall, the substrate conveyance, and the shutter may be removed or exchanged. However, when such maintenance work is scheduled, the operation efficiency of the device (4) is lowered. Further, the crystal form of indium oxalate is different from the crystal which is only oxalic acid, and is hardly dissolved even if it is dropped into the etching liquid, and is contained in the (iv) liquid in a crystalline state. Thus, even if the (four) mixture is used to remove the indium ions and tin ions from the etching solution, it is necessary to manage the indium ions (four degrees) to an appropriate concentration. The present invention is the result of repeated intensive studies by the inventors of the present invention, and is provided to provide a method for maintaining the optimum concentration of indium ions and tin ions in the indium ions and tin ions contained in the money engraving liquid. For its purpose. [Means for Solving the Problem] In order to achieve the above object, the present invention relates to an etching method which comprises a method of surzing a d V and a metal removing step, the tracing step being from the form number A0101 Κ π 0 page / total 27 Page 1003052484-0 201128697 ·=Nozzle miscellaneous and will be described by J from the nozzle one = the spit of the surname from the J. [0016] 去 [0017] = the step is to store in the aforementioned storage tank The money engraved liquid is filled with the adsorption of the Langqizi silk ion (10) mixture to adsorb and remove the indium ions and tin contained in the etching solution by etching, and simultaneously adsorb and remove the ions and tin ions. The subsequent surface liquid is returned to the storage tank; wherein in the metal removal step, the indium ion is adsorbed and removed by maintaining the steel ion concentration of the eclipse liquid stored in the storage tank at 26Oppm or less. And tin ions. According to the method, when the substrate having the indium tin oxide film is formed by etching the oxalic acid-containing money engraving, an etching step and a metal removing step are performed, and the remaining step is to circulate the engraving liquid in the storage tank. The metal substrate is ejected from the nozzle body to etch the substrate; and the metal removal step is performed by using the chelating agent in the adsorption container to adsorb and remove the indium ions and tin ions in the surname solution while circulating the liquid in the storage tank. In the metal removal step, adsorption and removal of indium ions and tin ions are performed so that the concentration of indium ions contained in the etching liquid in the storage tank is maintained at 260 ppm or less. As described above, in particular, when the concentration of the copper ions exceeds a certain level, for example, the inner wall of the chamber (adjacent chamber) that is adjacent to the processing chamber in which the etching liquid is discharged and the internal space communicates with the space of the processing chamber is configured and configured. The substrate transfer roller adjacent to the inside, the substrate transfer port of the processing chamber, or the base 100101551, the form number A0101, page 7 / 27 pages 1003052484-0 201128697, the opening and closing of the plate opening and closing device, etc. 'Indium oxalate crystallizes, and The adhesion of the substrate to the substrate transporting roller causes the substrate to be damaged, causing malfunction of the shutter, or the crystal of the indium oxalate is dropped and contains the impurities in the liquid that is returned to the storage tank. The clogging of the filter which is removed from the etched etching liquid prevents such a problem. When removing the crystallization of the inner wall of the substrate, the transfer of the substrate, or the exchange of the transition device, the etching operation is caused by such maintenance work. The processing efficiency is low. [0019] In the case where the wave (mass concentration) of the county ion is less than the fine side, the indium oxalate is not present in the inner wall, the substrate transport roller, and the shutter, etc. Will analyze the knowledge. In the present invention, the indium ion concentration of the money etchant stored in the front erroneous storage tank is maintained at 260 ppm or less - and T. In this way, the field defense:: Therefore, 'will not produce ^ in the base, causing the substrate to be injured, or causing the opening of the m... the crystal of the r is falling - there is being recycled to:: trough:::: The problem of clogging is caused by the removal of impurities such as dust from the circulating (four) liquid, and it is not necessary to perform the crystallization and exchange over-dismansion maintenance of the roller, the shutter, and the like for removing the shaft before the inner wall. 100101551 [0020] Moreover, in order to maintain the concentration of the larvae below 26 (), the secret solution in the storage tank can be frequently passed to the adsorption container, so that the 1 liquid in the recording tank is filled with liquid H When the internal pressure drops, the liquid can be temporarily stopped in the adsorption container, and the liquid is passed to the adsorption container. Form No. A0101 Page 8 / Total 27 pages 1003052484-0 201128697 The system is not subject to any restrictions. [0021] Further, when the chelating agent is generally provided with a higher equilibrium concentration and a higher equilibrium adsorption amount, and an equilibrium concentration and an equilibrium adsorption amount and an adsorption system of indium ions, the equilibrium concentration is equivalent to passing the liquid to the adsorption container. The concentration of indium ions in the etching solution, and the so-called equilibrium adsorption amount is called the maximum amount of indium that can be adsorbed using the average unit weight of the clamping agent. [0022] Therefore, the higher the concentration of indium ions in the etching liquid which is passed through to the adsorption container, the higher the indium ions can be adsorbed to the clamper, and can be increased to the clamped agent. The adsorbed indium ions reach saturation σ and the number of sheets processed. From such a viewpoint, the concentration of indium ions in the etching liquid in the storage tank is as high as possible at a concentration of 26 Qp:3 which does not generate crystals. However, when the indium ion concentration is at least the above, it is possible to ensure that the number of substrate-treated sheets in which the indium ions adsorbed by the chelating agent are connected to a saturated state is equal to or higher than the predetermined level, and the economical efficiency is not impaired -- - ---:: : .
[0023] G 又，在前述金屬除去步驟，係至少‘用2個前述吸附容器 ，並對該等各吸附容器的任一者，選擇性地使蝕刻液通 液，並且使通液後的蝕刻液回流至前述儲存槽内亦可， 此時，例如判斷被鉗合劑吸附的銦離子及/或錫離子係達 到大致飽和狀態時，藉由將被供給似彳液之吸附容器切 換，lb夠將甜合劑的吸附能力維持一定。又，被供給敍 刻液之吸附容器被切換且被停止供給蝕刻液後之吸附容 器的鉗合劑，係使用使銦離子及錫離子洗出之洗提液而 適當地被再生。 100101551 表單編號A0101 第9頁/共27頁 1003052484-0 201128697 [0024] [0025] 如上述，在因蝕刻液而經常濕潤的部分，草酸銦的結晶 化係不谷易產生，在鄰接處理室且内部空間係與處理室 的空間連通之室的内壁、和黏附在該室内的構造體之钱 刻液中的水分蒸發，銦離子的濃度提高，致使過飽和的 銦以草酸銦的形式析出。因此，若對鄰接前述處理室之 至的内壁及配設在該室的内部之構造體的至少—方澆 灑前述蝕刻液或純水時，能夠防止前述黏附的蝕刻液之 水分蒸發致使銦離子的濃度升高至飽和濃度以上。藉此 ，能夠更4實地防止草酸銦析出。而且，#刻液或純水 係可以定期地澆灑，亦可不定期地澆灑，且亦可以經常洗灑。 [發明之效果] 如以上，依照本發明的㈣方法，因為能夠將由於姓刻 基板而溶解於蝕刻液之銦及錫（銦離子及錫離子）之中、 特別是姻離子的濃度維持在適當的濃度，所以能夠防止 生成析出物。 [0026] :實施方式】 以下 ，基於附加圖式來說明本發明的具體實施形離。又 ’在本實施形態’係舉出使用如第1圖所表示的㈣裝置 1，且使用卓酸濃度（重量濃度）為3 4%的钱她來^面形成有氧化鋼锡膜之基《的情況為—個例子來說 [0027] 首先’說明前述蝕刻裝詈1 衣置1该蝕刻裝置丨係如 示，係由下列等所構成： 儲存槽11，其係健W㈣L· = 第1圖所表 100101551 表單編號A0101 第10頁/共27頁 1003052484-0 201128697 餘刻機構12 ’其係使用姓刻液L來姓刻基板Κ ; 相循％機構2G ’纟係使钱刻液[在儲存槽丨丨與姓刻機 構之間循環； °附機構31 ’其係吸附、除去溶解於触刻液l之姻及錫； “去用循％機構34 ’其係使钱刻液[在儲存槽丨丨與吸附機 構31之間循環； 控制農置28 ’其係控制㈣機構12、侧用循環機構2〇 及除去用循環機構34之運轉。 ¢) 闕前述蝕刻機構12係具備下列等： 處理至13，其係具備封閉空間) 複數個搬魏14 ’其係配設在纽，將基板κ水平 支撐且在預足方向（箭號所表示方向）搬運； 流通管15 ’其係配設在處理室13内的上部，來流通藉由 姓刻用循環機構20所供給的蝕刻液l ; 複數個噴霧喷嘴體16 ,其仙設在流通管15，來將姓刻 液L朝向藉由搬運輥14搬運之基板κ的上面吐出； 〇 狹縫喷嘴體，其係配設在處理113内且比噴霧喷嘴體 16更基板搬運方向上游侧，來將蝕刻液L朝向藉由搬運輥 14所搬運的基板K之上面吐出；及 擺錘式基板檢測傳感器18，其係配設在處理室13内。 剛X，在前述處理室13，係各自形成有基板搬入口 l3a及基 板搬出口 13b，基板搬入口 13a能夠藉由開閉器19間閉。 又，在處理室13的底面係形成有排出口 13c,處理室13内 的#刻液L係從該排出口 13c被排出至外部。 [0030] 100101551 又，前述蝕刻機構12係具備被配置在鄰接處理室13且基 表單編號A0101 第11頁/共27頁 1003052484-0 201128697 5運方向上游側及下游側之室5G、55。前述室50的内 二間係連接前述基板搬入口 13a且與處理室13的内部空 在至50内係没置有前述搬運輕η。 [0031] v至55的内部空間係連接基板搬出口 1扑而與處理室a 的内σ卩空間連通，在室5 5内係設置： 前述搬運輥14 ;及 Κ狹縫噴嘴體56，其係朝向藉由搬運輥14所搬運的基板 上面吐出空氣。又，在室55，係形成有藉由開閉器 2之基板搬出口 55a '及用以將室55内的餘刻液L排出 卜。P之排出口 55b 〇而且，狹縫噴嘴體56係從供給部58 給管59 ’且能夠切換為空氣及純水的任一方而供 給〇 [0032] ，在前述各室13、50、55 ’係設置有喷嘴觸，其係 將從未圖示的供給賴供給的純水㈣—部分的搬運概 i U、開閉器19、57、議、於的内壁及狹縫噴嘴體17、 66的外面吐出。又，在基板檢_感器】8的可動部係透 過未圖示的供給管而經常被供給前述蝕刻液L。 [0033] 則述蚀刻用循環機構2〇係由下列等所構成. 供給管2卜錢-端職接，且另—端側分枝 而連接至流通管1 5及狹縫噴嘴體17 ; 供給果22，其係將敍刻液L透過供給管21而供給至流通管 15内及狹縫喷嘴體17 ; 回收管23 ’其係-端側分枝而連接至處理室13的排出口 13c及室55的排出D55b’而他端側係連接至儲存槽^。 100101551 表單編號A0101 第頁/共27頁 1003052484-0 201128697 [0034] W述吸附機構3丨係具備至少2個在内部填充有钳合劑（未 圖不）之吸附容器（第1吸附容器32及第2吸附容器33)， 甜& 係吸附銦及錫（銦離子及錫離子），而該銦及鎮 係在蝕刻機構1 2由於蝕刻處理而溶解於蝕刻液l且被該蝕 j液。而且，前述鉗合劑係具備將钢離子及錫離子 之金屬離子„及附且被吸附的金屬係使用特定溶液來洗出 之十生質。又， 、、、 、 ，作為前述钳合劑，係至少能夠吸附銦離子 及錫離子者即可，沒有特別限定。 〇 剛環機構34係由下列所構成： 供、’口 S 35，其係一端侧連接至儲存槽η，他端側分枝而 連接至各吸附容器32、33 ; 、°果36，其係'透過供給管35將姓刻液L供給至各吸附容 器32、33的内部； 吸附合 回收管 3 7 ,甘 丨I端側連接至儲存槽1卜他端側分枝而 奂至各吸附容器32、33 ; 0 $排出側切換閥4G及第2排出側切換_，其係各自設 置在回收管37的他側端。 侧二::::觸當以供給側切㈣㈣排出 換_= 2供給側切換闕39及第2排出側切 排出側切換閥4〇關閉、且第2供給側切換間39及第2 如此進開啟時係對第2吸附器33供給钱刻液L， 仃储存槽11内的敍刻液L係透過供給管35而能 100101551 表單塢號A0101 第13頁/共27頁 1003052484-0 201128697 而被回收至儲存槽u内 [0036] 前述控制裝置28係實行下列處理： 控制供給系22而使餘刻液L循環在儲存槽j 之間之處理； 1與蝕刻機構12 [0037] 控制供給部58而將空氣及純水的任—方供給至狹縫喷嘴 體5 6之處理。 ' 隨後，說明制如以上構成钱㈣置卜來連續地触刻 複數基板K之方法。又’在儲存槽⑽，係儲存完全不含 有銦離子及錫離子之新的蝕刻液L。 [0038] 首先，進行蝕刻步驟，在該韻刻步驟，從前步驟所供給 的基板K係依照順序通過室50、處理.室13及室η内並乂 被排出至後步驟的方式使用破運輥14將基板κ在預定方向 I 搬運。又，使用供給泵22將在儲存槽U所儲存的蝕刻液^ 供給至各噴霧噴嘴體16及狹縫噴嘴體17，並使其從該等 喷嘴體16、17朝向基板K的上面吐出，同時將吐出至基板 K的上面之蝕刻液L，使其從處理室13的排出口 i3c流通至 回收管23内並回收至儲存槽11内。而且，將空氣從供給 部58供給至狹縫喷嘴體56且使其吐出。 [0039] 而且，基板K係在通過處理室13内時，被從各噴霧噴嘴體 100101551 表單編號A0101 第14頁/共27頁 1003052484-0 201128697 [0040] 16及狹縫噴嘴體17所吐出的蝕刻液[(蝕刻液匕中的草酸） 蚀刻，由於該餘刻’基板K的氧化钢錫膜係溶解於钱刻液 L，而循環的蝕刻液L係包含銦離子及錫離子◊又，基板κ 通過室55内時，藉由從狹縫噴嘴體56所吐出的空氣，蝕 刻液L被從基板K除去，被除去的姓刻液L係從室的排出 口55b通過回收管23而回流至儲存槽丨丨内。 隨後，由於氧化銦錫膜溶解，循環中的蝕刻液[中的銦離 子及錫離子的濃上升而達到一定濃度時，開始金屬除去 ❹ [0041] 步驟。 在該金屬除去步驟，係將在储存槽11所儲存的蚀刻液L， 從供給系36透過供給管35而供給至吸附容器32、33之任 一者，並將流通吸附容器32、33内後的蝕刻液[透過回收 管37回收至儲存槽η内。如此進行，使用吸附容器μ、 33内的钳合劑將被包含有姓刻液^之銦離子及錫離子吸附 除去，來將在儲存槽11内的姓刻液L所含有的銦離子及 錫離子之濃度抑制在一定漆度以下。 Ο [0042] 又’姓刻液l所含有的銦離子:i錫離子之濃度是否達到一 定濃度’例如能夠藉由基於從前述基板檢測傳感器18所 得到的輸出信號，來計算通過處理室13之基板κ的片數、 亦即計數在蝕刻機構12已被蝕刻的基板κ片數，並推定所 計算的片數是否達到預先設定的片數（推定銦離子及錫離 子的濃度為達到前記一定濃度之片數）來判斷。又，針對 姻離子，前述一定濃度係能夠在l〇〇ppm以上、260ppm以 下的濃度（質量濃度）任意地設定。 100101551 表單編號A0101 第15頁/共27頁 1003052484-0 201128697 闕隨後，被供給姓刻液L之吸附容器32、33的封合劑之吸附 能力降低，而難以將在健存槽n内的餘刻液l所含有的姻 離子及錫離子的濃度抑制在—定濃度以下時，亦即，基 於從前述基板檢測傳❹18所制的輸出信號，來計算 在钱刻機構12已被姓刻的基板K片#t，所計算的片數達到 預先設^的片數，且被鉗合劑吸_銦離子及錫離子係 達到大致飽和狀態之推定片數時，將被供給敍刻液l之吸 附容器32、33切換而使餘刻液l循環。 _讀，在每次在㈣機構12已㈣刻的基板κ之片數係成 為設定片數時（每次被鉗合舰__子及錫離子係達 到大致飽和狀態之推定片數時），邊交替地切換吸附容器 32、33，邊將在儲存槽11所儲存的餘刻液L供給至吸附容 器32、33之任一方。 [0045] [0046] 100101551 如此，在金屬除去步驟，係•附容⑽、33”_ 換而邊將鉗合劑的吸附能力維拉也 _ 、马—疋，邊使蝕刻液L循 環’藉此’能夠將在儲存_内的_胤所含有的铜離 子及锡離子維持在4濃度以下（銦離子物0卿以上、 260ppm以下）。 又’關於㈣㈣器32、33㈣換而被停止供給姓刻液L 之吸附容器32、33亦即使用完畢的㈣ 與未使用（再生完畢）的（在*合劑未吸附銦及錫）吸附容 器32、33交換。或是將用以洗出被细合劑所吸附的銦及 錫之洗提液縣至彳^畢…及附容⑽、Μ，將姻及 錫洗出至減提賴，㈣叫㈣㈣洗淨液通液來 洗掉在吸附容②32、33内部殘留的洗提液，如此進行而 表單編號A0101 第16頁/共27頁 201128697 [0047] Ο [0048] Ο 月b夠再使用吸附容器32、33(再生）。 又，在基板檢挪傳感器㈣可動部，係透過供給管（未圖 不）而經常供給健存槽u内的钱刻液L，而且定期地、不 定期地或經倾噴嘴體60朝向-部分的搬運輥14、開閉 器19、57、至5Q、55的内壁及狹縫喷嘴體17、56的外面 吐出純水’同_供給部㈣純水供給至狹縫噴嘴體56 如此進仃’係為了防止則液L中的銦與㈣液L中的 草酸鍵結而以草酸銦的形式結晶化。而且，在將純水供 給至=縫噴嘴體56時，為了使純水不會流人儲存槽n， 、 在回收官23之未圖示的闕切換而被回收至適當 的回收部。 §特别疋針對銦離子，其濃度超過一定水準時，蝕 ^ a &中的鋼與餘刻液[中的草酸鍵結而以草酸銦的形式 —雖然在因餘刻液L而經常濕潤的部分，該結晶化 、 易產生’但是開閉器19打開時，從處理室13内透 過基板搬人0 1 <5 A a a而流入室:g〇内之霧狀的蝕刻液L、和從 ㈣過基板搬 出a 1:3b雨濟入室55之霧狀的蝕刻 、所點附之室5〇、55的内壁、配置在室50、55内之一 P刀的基板搬運用親14、開閉器19、57及狹縫喷嘴體56 的外面等，所黏附之蝕刻液L·中的水分因為蒸發而蝕刻液 的離子之濃度提高，過飽和的銦離子會以草酸銦的 $式析出。又’關於狹縫噴嘴體17，因為霧狀的蝕刻液L Ιέ附在其外面，與上述同樣地草酸銦析出。而且，關 於基板檢測傳感器18的可動部，其係配置在基板Κ的下側 ，因為蝕刻液L洗灑不多而容易乾燥，草酸銦容易析出。 100101551 表單編號A〇l〇i 第Ρ頁/共27頁 1003052484-0 201128697 而且，-旦草酸銦析出時，結晶會以此為核而成長。 [0049] 如此進行，草酸銦結晶化時由於黏附在搬運用輥Η之 結晶造成基板κ受傷’或是造成開閉器19、57的動作不良 #基板檢測傳感器18的錯誤彳貞測，或是堵塞狹縫喷嘴體 56的開口 σ(5而空氣無法均勻地被吐出，致使在液體除去 處理時產生不均。又’草酸銦的結晶掉落至被回收至儲 存槽11内之蝕刻液L時，會成為將塵埃等的不純物從循環 的蝕刻液L除去之過濾器堵塞的原因。另一方面，為了防 止此種問題，而進行除去黏附在前述室50、55的内壁、 配置在室50、55内之一部分的搬運用輥14、開閉器Η、 57、狹縫噴嘴體17、56的外面及基板檢測傳感器is的可 動部等之結晶、或交換過濾器時，為了此種維修作業， 該蝕刻裝置1的運轉效率會低落。而且，草酸銦的結晶係 與僅是草酸的結晶不同，因為即便掉落至蝕刻液L中亦難 以溶解’而以結晶狀態被包含在钱刻液中。 [0050] 因此’本發明者等重複各種實驗之結果，得到下列知識 :銦離子的濃度為26 Oppm以下時’在前述室5〇 ' 55的内 壁、配置在室50、55内之一部分的搬運親14、開閉器19 、5 7、狭縫喷嘴體1 7、5 6的外面及基板檢測傳感器18的 可動部等，草酸銦不會析出。 [0051] 因而，本例的蝕刻方法係以被儲存在前述儲存槽丨丨内的 蝕刻液L的銦離子濃度為被維持在26Oppm以下的方式進行 吸附、除去在前述金屬除去步驟之姓刻液L中的銦離子及 錫離子。藉此，能夠確實地防止草酸銦的析出。因此， 100101551 下列問題不會產生： 表單煸號A0101 第18頁/共27頁 1003052484-0 201128697 由於黏附在搬運用輥14之結晶造成基板1(受傷，或是造成 開閉器19、57的動作不良和基板檢測傳感器18的錯誤偵 測，或是從循環的蝕刻液[除去塵埃等的不純物之過濾器 堵塞，或是狹縫噴嘴體56的開口部被堵塞致使在液體除 去處理時產生不均之問題’而且亦無進行除去黏附在前 述室50、55的内壁、配置在室5〇、55内之一部分的搬運 用輥14、開閉器19、57、狹縫喷嘴體17 ' 56的外面及基 板檢測傳感器18的可動部等之結晶、和交換過濾器的維 修之必要。 Ο [0052] 又，因為本例係將飯刻液L供給至基板檢測傳感器18的可 動部，且朝向—部分的搬運輥14、開閉㈣、”、室 、55的内壁及狹縫嘴嘴競17、56的外面吐出純水能夠 能破實地防止gj該等的乾燥致使草酸銦析I又，藉由 將純水供給至狹縫料體56_部，錢触掉並除去 在開口部所黏附的草酸銦。 [0053] Ο 常已头俯合劑係具有如第2圖所表示之吸附特性 。該第2圖係顯不平衡濃度與平衡吸附量（mg/L ) 的關係之圖表（_等溫線），制平衡濃度及平衡吸附 1與娜子㈣附之關係時，所謂平衡濃度係表示使其 通液至吸附容器32、33内之㈣液L的銦離子濃度，所謂 平衡㈣量係指使用平均單位重量甜合劑能夠吸附之最 大銦量（mg/g)。 [0054] 叩i，從弟z園可得知 100101551 1尤/、通欣主吸附容器32、33内之 韻刻液L的銦離子濃度越高，相較於較低時，能夠使較多 的銦離子吸附於甜匈。因此在 表單編號麵第19頁/共27頁槽U内的#刻液[的 1003052484-0 201128697 銦離子之濃度，係以在260ppm以下的範圍盡可能高濃度 為佳，如此進行時，能夠增加被鉗合劑吸附的銦離子達 到飽和狀態之基板蝕刻片數，而且能夠増長吸附容器32 '33的切換周期，乃是經濟的。 [0055] [0056] 另一方面，第3圖係將銦離子濃度例如維持在25(^⑽、 200ppm、l50Ppm及looppm時，求得在儲存槽内所儲存 的蝕刻液L之銦離子濃度與基板κ的蝕刻片數之關係之圖 表。在該圖式例，係開始蝕刻步驟後，當儲存槽u内的 铟離子濃度成為25〇ppm、200ppm、150ppm及 1〇〇1)1)111時 ’開始金屬除去步驟，邊切換吸附容器32、33，邊使餘 刻液L循環而將儲存槽11内的銦離子濃度維持為約 250ppm、200ppm、I50ppm及lOOppm。又，將儲存槽η 内的銦離子濃度維持為25〇ppm、200ppm、15〇ppm及 lOOppm時之吸附容器32、33的切換周期係各自為約9〇〇〇 片、7950片、6800片及5450片，相較於維持在25〇ppm 時’維持在l〇〇ppm時係較少約40%左右。 ：；. . 從該第3圖可得知，儲存槽】！内的蝕刻液L的銦離子濃度 越高，被鉗合劑吸附的銦離子達到飽和狀態之基板蝕刻 片數增加，而吸附容器32、33的切換周期增長。但是， 即便將儲存槽11内的銦離子濃度維持為1〇〇ppm時亦能 夠確保係維持25〇ppm時之約60%左右的切換周期，係可 容許的水準。因此，從經濟上的觀點，在儲存槽Η内的 蝕刻液所含有的銦離子之濃度，係以盡可能維持高濃度 為佳，但是銦離子濃度為100ppln以上時，能夠將吸附容 器32、33的的切換周期增長炱一定水準以上，能夠抑制 100101551 表單煸號A0101 第20頁/共27真 1003052484-0 201128697 [0057] [0058] θ [0059] 〇 [0060] 甜合劑的再生所需要的成本。 以上’说明了本發明的—實施形態，但是本發明能夠採 用的具體性態樣，係完全不被此限定。 在上例，係將被供給蝕刻液L之吸附容器32、33的切換， 以基板Κ的㈣片數來控制，但是不被此限定，亦可以在 預定的時間間隔、亦即在被甜合劑吸附的銦離子及錫離 子係達到大致飽和狀態之推定時間間隔將被供給蝕刻液[ 之吸附谷器32、33切換’而且亦可以測定被儲存在儲存 槽11之蝕刻液L的銦離子濃度及/或錫離子濃度，並基於 該測定的濃度來切換吸附容器3 ^ 又，使蝕刻液L通液至吸附容器32、33内之態樣，係不被 上述的態樣限定，而是任何態樣均可。例如在上例係金 屬除去步驟後，經常將儲存槽丨丨内的蝕刻液L通液至吸附 容器32、33，但是亦可以當銦離子濃度及錫離子濃度下 降時’暫時停止通液至吸‘容器32：、33姻，直到銦離子 濃度及錫離子濃度再次達到二定濃為止。 【圖式簡單說明】 第1圖係顯不用以實施本發明一實施形態的蝕刻方法之蝕 刻裝置的概略構成之構成圖。 第2圖係顯示平衡濃度與平衡吸附量的關係之圖表（吸附 等溫線）。 第3圖係顯示將銦離子濃度維持在25〇ppm、2〇〇ppm、 150ppm及lOOppm時，在儲存槽内所儲存的餘刻液之銦離 子濃度與基板的餘刻片數之關係之圖表。 100101551 表單編號A0101 第21頁/共27頁 1003052484-0 201128697 【主要元件符號說明】 [0061] 1 蝕刻裝置 11 儲存槽 12 蝕刻機構 13 處理室 13a 基板搬入口 13b、 55a 基板搬出口 13c、55b 排出口 14 搬運輥 15 流通管 16 喷霧噴嘴體 17、56 狹縫喷嘴體 18 基板檢測傳感器 19、57 開閉器 20 蝕刻用循環機 構 21 ' 35 ' 59 供給管 22、36 供給泵 23 ' 37 回收管 28 控制裝置 31 吸附機構 32 第1吸附容器 33 第2吸附容器 34 除去用循環機構 38、39、 40、41 切換閥 50、55 室(chamber) 58 供給部 60 喷嘴體 K 基板 L 姓刻液 100101551 表單編號A0101 第22頁/共27頁 1003052484-0[0023] Further, in the metal removing step, at least two of the adsorption containers are used, and the etching liquid is selectively passed through the respective adsorption containers, and the etching after the liquid passing is performed. The liquid may be returned to the storage tank. In this case, for example, when it is determined that the indium ions and/or the tin ions adsorbed by the chelating agent are substantially saturated, the sorption tank that is supplied with the sputum is switched, and lb is sufficient. The adsorption capacity of the sweet mixture is maintained constant. In addition, the squeezing agent of the adsorption container after the adsorption container to which the clarification liquid is supplied is stopped and the etching liquid is stopped is appropriately regenerated by using an eluent which washes indium ions and tin ions. 100101551 Form No. A0101 Page 9 of 27 1003052484-0 201128697 [0025] As described above, in the portion which is often wetted by the etching liquid, the crystallization of indium oxalate is not easily generated in the adjacent processing chamber. The inner wall of the chamber that communicates with the space of the processing chamber and the water in the money engraving of the structure adhered to the chamber evaporate, and the concentration of indium ions is increased, so that the supersaturated indium is precipitated as indium oxalate. Therefore, when the etching liquid or the pure water is poured on at least the inner wall of the processing chamber adjacent to the processing chamber and the structure disposed inside the chamber, the evaporation of the adhered etching liquid can be prevented from causing the indium ion. The concentration is raised above the saturation concentration. Thereby, the precipitation of indium oxalate can be prevented more effectively. Moreover, the #刻液 or pure water system can be poured regularly, or can be sprinkled from time to time, and can also be washed frequently. [Effects of the Invention] As described above, according to the method (4) of the present invention, it is possible to dissolve the concentration of the indium and tin (indium ions and tin ions) in the etching liquid due to the substrate of the surname, in particular, the concentration of the ion ions is appropriately maintained. The concentration is such that it is possible to prevent the formation of precipitates. Embodiments Hereinafter, specific embodiments of the present invention will be described based on additional drawings. Further, in the present embodiment, the apparatus (1) shown in Fig. 1 is used, and the base of the oxidized steel tin film is formed by using the acid concentration (weight concentration) of 34%. The case is as an example [0027] First, the description of the etching apparatus 1 is performed. The etching apparatus is as shown, and is composed of the following: a storage tank 11, which is a W (four) L· = 1 Table 100101551 Form No. A0101 Page 10 / Total 27 Page 1003052484-0 201128697 The engraving mechanism 12 'The system uses the surname L to name the substrate Κ; the phase according to the agency 2G '纟系使钱刻液 [in storage Circulation between the trough and the surname mechanism; ° Attachment mechanism 31 'The system is adsorbed and removed from the contact engraving liquid l and tin; "Go to the use of the % mechanism 34 'the system to make money engraving [in the storage tank丨丨 丨丨 丨丨 吸附 ; ; ; ; ; ; 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制 控制To 13, the system has a closed space) a plurality of moving Wei 14 'the system is set in the New Zealand, the substrate κ The flat support is carried in the pre-foot direction (the direction indicated by the arrow); the flow tube 15' is disposed in the upper portion of the processing chamber 13 to circulate the etching liquid 1 supplied by the circulation mechanism 20; The spray nozzle body 16 is disposed in the flow tube 15 to discharge the surname liquid L toward the upper surface of the substrate κ transported by the transport roller 14; the slit nozzle body is disposed in the process 113 and is The spray nozzle body 16 is further disposed on the upstream side in the substrate conveyance direction to discharge the etching liquid L toward the upper surface of the substrate K conveyed by the conveyance roller 14; and the pendulum substrate detection sensor 18 is disposed in the processing chamber 13. In the processing chamber 13, a substrate loading port 13a and a substrate carrying port 13b are formed in the processing chamber 13, and the substrate carrying port 13a can be closed by the shutter 19. Further, a discharge port 13c is formed in the bottom surface of the processing chamber 13. The #刻液 L in the processing chamber 13 is discharged to the outside from the discharge port 13c. [0030] Further, the etching mechanism 12 is disposed adjacent to the processing chamber 13 and has a base form number A0101 page 11 / total 27 pages 1003052484-0 201128697 5 direction The chambers 5G and 55 on the side of the swimming side and the downstream side. The inside of the chamber 50 is connected to the substrate carrying-in port 13a, and the inside of the processing chamber 13 is vacant within 50, and the transporting light η is not provided. [0031] The internal space of the connection space of 55 is connected to the inner σ space of the processing chamber a, and the inside of the chamber 55 is provided with the transport roller 14 and the slit nozzle body 56, which are oriented by The upper surface of the substrate conveyed by the conveyance roller 14 discharges air. Further, in the chamber 55, a substrate carrying port 55a' by the shutter 2 and a residual liquid L in the chamber 55 are formed. The discharge port 55b of the P is further provided, and the slit nozzle body 56 is supplied from the supply unit 58 to the tube 59' and can be switched to either air or pure water to supply the crucible [0032] in each of the chambers 13, 50, 55' A nozzle contact is provided, which is a pure water (four) supplied from a supply (not shown) - a part of the conveyance, a shutter 19, 57, an inner wall, and an outer surface of the slit nozzle body 17, 66. Spit out. Further, the movable portion of the substrate detector 8 is often supplied with the etching liquid L through a supply tube (not shown). [0033] The etching cycle mechanism 2 is composed of the following: the supply pipe 2 is connected to the end, and the other end is branched and connected to the flow pipe 15 and the slit nozzle body 17; Fruit 22, which supplies the engraving liquid L into the flow tube 15 and the slit nozzle body 17 through the supply tube 21; the collection tube 23' is branched to the discharge port 13c of the processing chamber 13 and The chamber 55 is discharged D55b' and the other end side is connected to the storage tank. 100101551 Form No. A0101 Page/Total 27 Page 1003052484-0 201128697 [0034] The adsorption mechanism 3 includes at least two adsorption containers (not shown) filled with a clamping agent (not shown) (first adsorption container 32 and 2 adsorption container 33), sweet & adsorbs indium and tin (indium ions and tin ions), and the indium and the town are dissolved in the etching solution 1 by the etching process in the etching mechanism 12 and are etched. Further, the tongs agent is provided with a metal ion which is a metal ion of a steel ion and a tin ion, and a metal which is adsorbed and eluted with a specific solution. Further, as a chelating agent, at least The indium ion and the tin ion can be adsorbed, and the ruthenium ring mechanism 34 is composed of the following: a supply, 'port S 35, which is connected to the storage tank η at one end side and connected to the other end side by a branch To each of the adsorption containers 32, 33, and 36, the product is supplied to the inside of each of the adsorption containers 32 and 33 through the supply pipe 35; the adsorption recovery pipe 3 7 is connected to the end of the Gansu I end. The storage tank 1 is branched to the respective adsorption containers 32, 33; 0 $ discharge side switching valve 4G and second discharge side switching_, which are respectively disposed at the other side of the recovery pipe 37. Side 2: ::: When the supply side cut (4) (4) discharge change _= 2 supply side switching 阙 39 and the second discharge side cut discharge side switching valve 4 〇 closed, and the second supply side switching chamber 39 and the second such as open The second adsorber 33 is supplied with the money engraving liquid L, and the engraving liquid L in the crucible storage tank 11 is transmitted through the supply pipe 35. Can be 100101551 Form Dock A0101 Page 13 / Total 27 Page 1003052484-0 201128697 and is recycled to the storage tank u [0036] The aforementioned control device 28 performs the following processes: Control the supply system 22 to circulate the residual liquid L in storage Processing between the grooves j; 1 and the etching mechanism 12 [0037] The supply portion 58 is controlled to supply any of the air and the pure water to the slit nozzle body 56. ' Subsequently, the description is as follows. The method of continuously engraving the plurality of substrates K. In the storage tank (10), a new etching liquid L containing no indium ions and tin ions is stored. [0038] First, an etching step is performed, in which the rhyme is performed. In the step, the substrate K supplied from the previous step is transported in the predetermined direction I by the break roller 14 so as to pass through the chamber 50, the processing chamber 13 and the chamber η in the order of the subsequent steps. The supply pump 22 supplies the etching liquid stored in the storage tank U to the respective spray nozzle bodies 16 and the slit nozzle bodies 17, and discharges them from the nozzle bodies 16 and 17 toward the upper surface of the substrate K, and simultaneously discharges them to the same. The etching liquid L on the upper surface of the substrate K, The discharge port i3c of the processing chamber 13 flows into the recovery pipe 23 and is recovered in the storage tank 11. Further, air is supplied from the supply unit 58 to the slit nozzle body 56 and discharged. [0039] Further, the substrate K is attached to When passing through the processing chamber 13, the etching liquid is ejected from each of the spray nozzle bodies 100101551, the form number A0101, the 14th page, the 27th page, the 1003052484-0201128697, and the slit nozzle body 17 (in the etching solution) Oxalic acid) etching, because the etched steel tin film of the substrate K is dissolved in the money engraving liquid L, and the circulating etching liquid L contains indium ions and tin ions, and when the substrate κ passes through the chamber 55, The air ejected from the slit nozzle body 56 is removed from the substrate K, and the removed radical L is returned from the chamber discharge port 55b through the recovery pipe 23 to the storage tank. Subsequently, the metal removal ❹ [0041] step is started when the indium tin oxide film is dissolved and the concentration of indium ions and tin ions in the circulating etching solution reaches a certain concentration. In the metal removal step, the etching liquid L stored in the storage tank 11 is supplied from the supply system 36 through the supply pipe 35 to any of the adsorption containers 32 and 33, and is passed through the adsorption containers 32 and 33. The etching solution is [recovered into the storage tank η through the recovery pipe 37. In this way, the indium ions and tin ions contained in the surname liquid L in the storage tank 11 are adsorbed and removed by using the chelating agent in the adsorption containers μ and 33 to remove the indium ions and tin ions containing the surname liquid. The concentration is suppressed below a certain degree of lacquer. 004 [0042] Further, whether or not the concentration of indium ions contained in the surname 1 : i tin ions reaches a certain concentration can be calculated, for example, by the processing chamber 13 based on an output signal obtained from the substrate detecting sensor 18 The number of substrates κ, that is, the number of substrates κ that have been etched by the etching mechanism 12 is counted, and it is estimated whether or not the calculated number of sheets reaches a predetermined number of sheets (the concentration of indium ions and tin ions is estimated to be a certain concentration before reaching) The number of pieces) to judge. Further, the concentration of the above-mentioned constant concentration can be arbitrarily set at a concentration (mass concentration) of 1 〇〇 ppm or more and 260 ppm or less. 100101551 Form No. A0101 Page 15 of 27 1003052484-0 201128697 阙 Subsequently, the adsorption capacity of the sealing agent supplied to the adsorption containers 32 and 33 of the surname L is lowered, and it is difficult to leave the remaining in the storage tank n When the concentration of the ion and the tin ion contained in the liquid 1 is suppressed to a constant concentration or lower, that is, based on the output signal prepared from the substrate detection pass 18, the substrate K which has been surnamed in the engraving mechanism 12 is calculated. Sheet #t, when the number of sheets counted is up to the number of sheets set in advance, and the amount of the estimated amount of the inhaled ions indium ions and tin ions reaches a substantially saturated state, the adsorption container 32 of the engraving liquid 1 is supplied. 33 is switched to circulate the remaining liquid. _Read, each time the number of the substrates κ in the (four) mechanism 12 is set to the number of sheets (when the clamped ship__ and the tin ion system reach the estimated number of sheets in a substantially saturated state), While the adsorption containers 32 and 33 are alternately switched, the residual liquid L stored in the storage tank 11 is supplied to either one of the adsorption containers 32 and 33. [0046] 100101551 In this way, in the metal removal step, the system is attached (10), 33"_, and the adsorption capacity of the tongs is replaced by _, horse-疋, while the etching liquid L is circulated. 'The copper ions and tin ions contained in the _ 储存 in the storage _ can be maintained at 4 or less (indium ionics 0 qing or more, 260 ppm or less). Further, the (4) (4) devices 32, 33 (4) are stopped and supplied with the surname. The adsorption containers 32 and 33 of the liquid L are also exchanged between the used (4) and the unused (regenerated) (injected non-adsorbed indium and tin) adsorption containers 32, 33, or used to wash out the fine agent. Adsorbed indium and tin eluent in the county to 彳 ^ Bi... and attached (10), Μ, will be married and tin washed out to reduce the rai, (four) called (four) (four) washing liquid through the liquid to wash away in the adsorption capacity 232, 33 The internal residual eluent is thus performed and Form No. A0101 Page 16 of 27 201128697 [0047] Ο [0048] Ο Month b is enough to reuse the adsorption containers 32, 33 (regeneration). (4) The movable part is often supplied to the money engraving liquid L in the storage tank u through the supply pipe (not shown), and Periodically, irregularly, or through the outer surface of the conveying roller 14, the inner walls of the shutters 19, 57, to 5Q, 55 and the slit nozzle bodies 17, 56 which are directed toward the portion of the nozzle body 60, the pure water is discharged. (4) The pure water is supplied to the slit nozzle body 56. In order to prevent the indium in the liquid L from being bonded to the oxalic acid in the liquid (liquid) L, it is crystallized in the form of indium oxalate. Further, pure water is supplied to = When the nozzle body 56 is sewn, in order to prevent pure water from flowing into the storage tank n, it is switched to an appropriate recovery portion by switching between the unillustrated crucibles of the recovery officer 23. §Specially, the concentration of indium ions exceeds a certain value. At the level of time, the steel in the etch and the residual liquid [the oxalic acid bond in the form of indium oxalate - although in the part which is often wetted by the residual liquid L, the crystallization is easy to produce 'but opening and closing When the device 19 is opened, it flows through the substrate from the processing chamber 13 through the substrate 0 1 < 5 A aa and flows into the chamber: the mist-like etching liquid L in the chamber, and the (a) through-substrate a 1:3b rain-in chamber 55 The mist-like etching, the inner walls of the chambers 5〇 and 55 to be attached, and the substrate transport of the P-knife disposed in the chambers 50 and 55 The temperature of the ions of the etching liquid is increased by the evaporation of the water in the etching liquid L· which is adhered to the outside of the shutters 19 and 57 and the slit nozzle body 56, and the supersaturated indium ions are in the form of indium oxalate. In the slit nozzle body 17, the etched liquid L Ιέ is attached to the outer surface of the slit nozzle body 17 in the same manner as described above, and the movable portion of the substrate detecting sensor 18 is disposed on the substrate Κ. On the lower side, since the etching liquid L is not easily washed, it is easy to dry, and indium oxalate is easily precipitated. 100101551 Form No. A〇l〇i Page / Total 27 pages 1003052484-0 201128697 Moreover, when indium oxalate is precipitated, crystallization will occur. Use this as a core to grow. [0049] In this manner, when the indium oxalate crystallizes, the substrate κ is damaged due to adhesion to the crystal of the transport roller, or the malfunction of the shutters 19 and 57 is caused. </ </ RTI> erroneous detection of the substrate detecting sensor 18, or clogging The opening σ of the slit nozzle body 56 (5, and the air cannot be uniformly discharged, causing unevenness in the liquid removal process. Further, when the crystal of indium oxalate falls to the etching liquid L recovered in the storage tank 11, It is a cause of clogging of the filter in which impurities such as dust are removed from the circulating etching liquid L. On the other hand, in order to prevent such a problem, the inner wall of the chambers 50 and 55 is removed and adhered to the chambers 50 and 55. When one of the inner conveying rollers 14, the shutters 57, 57, the outer surfaces of the slit nozzle bodies 17, 56, and the movable portion of the substrate detecting sensor is, or the filter is exchanged, the etching is performed for such maintenance work. The operation efficiency of the device 1 is low. Moreover, the crystal form of indium oxalate is different from the crystal of only oxalic acid, because it is difficult to dissolve even if it falls into the etching liquid L, and is contained in the crystal engraving liquid in a crystalline state. [0050] Therefore, the inventors of the present invention repeated the results of various experiments, and obtained the following knowledge: when the concentration of indium ions is 26 Oppm or less, 'the inner wall of the chamber 5〇' 55 is disposed in one of the chambers 50, 55. The transfer of the parent 14, the shutters 19, 57, the outer surfaces of the slit nozzle bodies 177, 596, and the movable portion of the substrate detecting sensor 18, etc., does not precipitate indium oxalate. [0051] Thus, the etching method of this example is The indium ion concentration of the etching liquid L stored in the storage tank is maintained so as to be maintained at 26 ppm or less, and the indium ions and tin ions in the surrogate liquid L in the metal removal step are removed. It is possible to surely prevent the precipitation of indium oxalate. Therefore, the following problems do not occur in 100101551: Form No. A0101 Page 18 of 27 1003052484-0 201128697 Substrate 1 due to adhesion of the roller 14 of the conveyance roller (injured, or The malfunction of the shutters 19 and 57 and the erroneous detection of the substrate detecting sensor 18 are caused, or the circulating etching liquid [the filter which removes impurities such as dust is clogged, or the opening of the slit nozzle body 56 is blocked. The plug causes a problem of unevenness in the liquid removal process, and the removal of the inner wall of the chambers 50 and 55 and the conveyance rollers 14 and the shutters 19 and 57 which are disposed in one of the chambers 5 and 55 are not removed. The outer surface of the slit nozzle body 17'56 and the crystal of the movable portion of the substrate detecting sensor 18, and the maintenance of the exchange filter are required. [0052] Further, since this example supplies the rice cooking liquid L to the substrate detecting sensor The movable portion of the movable portion of the first portion, the opening and closing (four), the inner wall of the chamber, the inner wall of the chamber 55, and the outer surface of the slit mouth, the outer water of the nozzles, the nozzles, and the spouts, can effectively prevent the drying of the gj from causing oxalic acid. Indium analysis I, in addition, by supplying pure water to the portion of the slit body 56, the money touches off and removes the indium oxalate adhered to the opening. [0053] The 俯 often already has a adsorption property as shown in Fig. 2. Fig. 2 is a graph showing the relationship between the unbalanced concentration and the equilibrium adsorption amount (mg/L) (_ isotherm). When the equilibrium concentration and equilibrium adsorption 1 are related to Nazi (4), the equilibrium concentration is expressed. The indium ion concentration of the liquid (liquid) L which is passed through to the adsorption containers 32 and 33, and the balance (four) amount means the maximum amount of indium (mg/g) which can be adsorbed using the average unit weight of the sweetener. [0054] 叩i, from the younger Z Park, it can be seen that the higher the indium ion concentration of the rhyme L in the main adsorption containers 32 and 33 of the Tongxin main adsorption container 32, 33, the more the lower the concentration The indium ions are adsorbed to the sweet hung. Therefore, the concentration of indium in the #10305/484#201128697 in the slot No. on page 19 of the form numbering surface is preferably as high as possible in the range of 260 ppm or less. It is economical that the number of etched substrates of the indium ions adsorbed by the chelating agent reaches a saturated state, and the switching period of the adsorption container 32'33 can be lengthened. [0056] On the other hand, in the third graph, when the indium ion concentration is maintained at 25 (^, 10, 200 ppm, 150 Ppm, and looppm, for example, the indium ion concentration of the etching liquid L stored in the storage tank is determined. A graph showing the relationship between the number of etched sheets of the substrate κ. In this figure, when the indium ion concentration in the storage tank u is 25 〇 ppm, 200 ppm, 150 ppm, and 1 〇〇 1) 1) 111 after the etching step is started. The starting metal removal step was performed while the adsorption containers 32 and 33 were switched, and the residual liquid L was circulated to maintain the indium ion concentration in the storage tank 11 at about 250 ppm, 200 ppm, I50 ppm, and 100 ppm. Further, when the concentration of the indium ions in the storage tank η is maintained at 25 〇 ppm, 200 ppm, 15 〇 ppm, and 100 ppm, the switching periods of the adsorption containers 32 and 33 are each about 9 、, 7,950, and 6,800, and 5450 tablets are less than about 40% less than 'maintained at l〇〇ppm when maintained at 25 〇ppm. :;. . As you can see from the third picture, the storage tank]! The higher the indium ion concentration of the etching liquid L in the inside, the higher the number of substrate etching sheets in which the indium ions adsorbed by the clamp agent are saturated, and the switching period of the adsorption containers 32 and 33 increases. However, even when the concentration of indium ions in the storage tank 11 is maintained at 1 〇〇 ppm, it is possible to ensure a switching period of about 60% when the temperature is maintained at 25 〇 ppm, which is an acceptable level. Therefore, from the viewpoint of economy, the concentration of the indium ions contained in the etching liquid in the storage tank is preferably as high as possible, but when the indium ion concentration is 100 ppln or more, the adsorption containers 32 and 33 can be used. The switching cycle is increased to a certain level or higher, and can be suppressed. 100101551 Form No. A0101 Page 20/Total 27 True 1003052484-0 201128697 [0058] [0059] 〇 [0060] Cost required for regeneration of the sweet mixture . The above describes the embodiment of the present invention, but the specific aspects that can be employed in the present invention are not limited at all. In the above example, the switching of the adsorption containers 32, 33 to which the etching liquid L is supplied is controlled by the number of (four) sheets of the substrate, but it is not limited thereto, and may be at a predetermined time interval, that is, in a sweetener. The estimated time interval at which the adsorbed indium ions and tin ions reach a substantially saturated state is supplied to the etching liquid [the adsorption pastes 32, 33 are switched" and the indium ion concentration of the etching liquid L stored in the storage tank 11 can also be measured. / or tin ion concentration, and based on the measured concentration to switch the adsorption container 3 ^, and the etching liquid L is passed into the adsorption containers 32, 33, is not defined by the above-mentioned aspect, but any state Can be sampled. For example, after the above-described metal removal step, the etching liquid L in the storage tank is often passed to the adsorption containers 32 and 33, but it is also possible to temporarily stop the liquid supply to the suction when the indium ion concentration and the tin ion concentration are lowered. 'Container 32:, 33 marriage, until the indium ion concentration and the tin ion concentration reached the second concentration again. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing a schematic configuration of an etching apparatus which does not require an etching method according to an embodiment of the present invention. Fig. 2 is a graph showing the relationship between the equilibrium concentration and the equilibrium adsorption amount (adsorption isotherm). Figure 3 is a graph showing the relationship between the indium ion concentration of the residual solution stored in the storage tank and the number of sheets of the substrate when the indium ion concentration is maintained at 25 〇 ppm, 2 〇〇 ppm, 150 ppm, and 100 ppm. . 100101551 Form No. A0101 Page 21/Total 27 Page 1003052484-0 201128697 [Description of Main Components] [0061] 1 Etching Apparatus 11 Storage Tank 12 Etching Mechanism 13 Processing Chamber 13a Substrate Carrying Ports 13b, 55a Substrate Carrying Out Ports 13c, 55b Outlet 14 Transport roller 15 Flow tube 16 Spray nozzle body 17, 56 Slot nozzle body 18 Substrate detecting sensor 19, 57 Shutter 20 Etching cycle mechanism 21 ' 35 ' 59 Supply pipe 22, 36 Supply pump 23 ' 37 Recovery pipe 28 control device 31 adsorption mechanism 32 first adsorption container 33 second adsorption container 34 removal circulation mechanism 38, 39, 40, 41 switching valve 50, 55 chamber 58 supply unit 60 nozzle body K substrate L surname liquid 100101551 Form No. A0101 Page 22 / Total 27 Page 1003052484-0