201005076 九、發明說明 【發明所屬之技術領域】 本發明係有關去除含 刻的磷酸蝕刻處理液中所 刻處理液再生之蝕刻處理 再生方法。 • 【先前技術】 用於MOS型LSI之 ，針對氮化矽膜與氧化矽 刻時，通常使用含有加熱 ，其氮矽化與磷酸進行反 矽係呈溶解於蝕刻液中之 氧化矽被析出，使晶圓受 之問題產生。爲解決該問 Φ 解量之前、或之後，立刻 磷酸，所需更換蝕刻液之 操作時間之問題產生，由 想。 因此，被揭示各種關 該技術之一者如：於蝕刻 物與氟化氫反應作成氟化 去除之技術（參照專利文 使蝕刻處理液經由冷卻， 有用於氧化矽膜、氮化矽膜之蝕 含之矽化合物，適用於爲了使鈾 液再生方法等之含磷酸處理液之 生產之羅克斯（LOCOS)法等中 膜，爲使氮化矽膜進行選擇性蝕 之磷酸蝕刻液。氮化矽膜蝕刻時 應後分解於氮矽化與氨。該氧化 狀態，惟超出飽和溶解量後，該 損，造成阻塞爲去除雜質之濾器 題，先行技術中，於超出飽和溶 更換飩刻液進行之，惟大量廢棄 時間過於浪費，出現裝置之停止 其環境面及經濟面之觀點均不理 於蝕刻處理液之再生技術。作爲 處理液中加入氟化氫，使矽化合 物，此經加熱，與水同時蒸發後 獻1)。又，作爲另一技術者， 析出矽化合物，以濾器過濾去除 -5- 201005076 該矽化合物後，再度加熱再行利用之技術（專利文獻2) 亦爲公知者。 [專利文獻1] 專利第3 072876號公報 [專利文獻2] 專利第3609 1 86號公報 惟，氟化氫爲與矽、矽化合物進行反應，使用氟化氫 φ 之技術時，於蝕刻再生液中殘留氟化氫，使晶圓受損，恐 大幅影響蝕刻選擇比，爲避免此現象，務必經常監視•調 整氟化氫之濃度。且，氟化氫係可溶於蝕刻液中，故不易 去除，易殘留於蝕刻再生液中。 又，本發明進一步試驗後，經由冷卻蝕刻處理液，析 出矽化合物後去除之技術中，其去除效率並不高。 【發明內容】 0 因此，欲解決本發明課題係提供一種相較於先行技術 之經由其他物質之殘留，使對於含磷酸再生液之氮化矽之 反應性，選擇性出現變化之問題的產生，而本發明可於低 能量下可有效再生含磷酸處理液之含磷酸處理液的再生方 法。 本發明者爲解決該課題，進行了精密硏討。其結果發 現，將藉由氮化矽處理所產生之含磷酸處理液，一旦與含 有特定之有機磷化合物之疏水性有機溶媒混合後使其相分 離後，使含磷酸處理液中之矽化合物可由含磷酸處理液析 -6- 201005076 出分離，藉由去除該矽化合物，可極容易，且高效率降低 含磷酸處理液中之矽化合物濃度，此經確定後，進而完成 本發明。 亦即，本發明該含磷酸處理液之再生方法係使藉由氮 化矽處理所產生之含磷酸處理液進行再生之方法，其特徵 係藉由使下述一般式 鬌 Y-P = 〇 (1) Ζ (式中，X、γ、ζ係各自獨立地代表烷基、烷氧基或 羥基，惟X、γ、ζ均爲羥基者除外）所示之含有機磷化 合物之疏水性有機溶媒與該含磷酸處理液一旦混合後使其 相分離，使該含磷酸處理液中之矽化合物由含磷酸處理液 析出分離，之後，回收含磷酸之再生液。 以下，明細書中，上式（1 )所示之有機磷化合物僅 以「有機磷化合物」示之。 本發明該含磷酸處理液之再生方法中，使藉由氮化矽 處理所產生之含磷酸處理液與含有機磷化合物之疏水性有 機溶媒一旦混合後進行相分離後，可由含磷酸處理液析出 分離含磷酸處理液中之矽化合物，因此，經由去除該矽化 合物後，可極容易且高效率的降低含磷酸處理液中之矽化 合物濃度。又，作爲去除矽化合物之物質者，係使用難溶 於含磷酸再生液中之有機磷化合物與疏水性有機溶媒，故 可幾乎完全輕易去除，且即使殘留亦不致影響含磷酸再生 201005076 液之反應性、選擇性。 特別是，該氮化矽之處理爲氮化矽膜之之蝕刻時，作 爲去除矽化合物之物質者，如上述，因使用難溶於含磷酸 蝕刻液中之有機磷化合物與疏水性有機溶媒，故可幾乎完 全輕易去除’且即使殘留亦不致影響蝕刻再生液之性能。 藉由離心分離法促進相分離後，可更有效進行含磷酸 處理液之再生。回收含磷酸再生液後，只要以濾器過濾去 Φ 除此微含於該含磷酸再生液之析出殘渣，即可進一步有效 去除矽化合物。使有機相於含磷酸處理液之再生中進行再 利用後’可削減廢棄量。藉由調整所回收之含磷酸再生液 之濃度及/或溫度’可進行長期、連續性之含磷酸處理液 之再生•使用。 【實施方式】 [發明實施之最佳形態] 以下，有關本發明該含磷酸處理液之再生方法，以氮 化矽膜之蝕刻中所使用之含磷酸之鈾刻處理液之再生方法 爲例進行詳細說明，而本發明之範圍並未受限於此，有關 &下示例以外，在不損及本發明主旨之範圍下，亦可適度 進行變更實施。 圖1係代表本發明實施形態之一例，槪略顯示蝕刻裝 置。 首先，針對蝕刻部A進行說明。蝕刻槽10中置滿蝕 亥!1液，其中浸漬氧化矽膜及氮化矽膜所形成之晶圓〗1後 -8 - 201005076 ，選擇性蝕刻氮化矽膜。經由蝕刻槽1 〇之外圍所設置之 加熱器（未示圖），蝕刻液之溫度維持於高溫（150〜170 °C)。設置溢流閘12於蝕刻槽10之上外圍，滯留於該溢 流閘1 2之蝕刻液係藉由泵1 4等之作用，由設於溢流閘1 2 底部之排出口通過經路部13，導入作爲蝕刻處理液之蝕刻 液再生部B。 蝕刻液再生部B中，首先，通過該經路部13所導入 φ 之蝕刻處理液貯存於蝕刻處理液貯存槽20。 由該蝕刻處理液貯存槽20，使經由開關活門2 1所調 整之特定量蝕刻處理液往混合方式之混合處理槽30流入 。另外，由另途所設置之有機溶媒貯存槽40與蝕刻處理 液相同，流入經由開關活門41所調整之特定量之含有機 磷化合物之疏水性有機溶媒。如此，於混合處理槽3 0使 兩溶液進行混合。 如上述，有機磷化合物係下述一般式 X、 Y—P = 0 (1) zy (式中，X、Y、Z係各自獨立地代表烷基、烷氧基或 羥基。惟，x、Y、z均爲羥基者除外）。 所示者，而該烷基亦可爲直鏈狀、或支鏈狀’其碳數並未 特別限定’ 一般如：1〜2〇者宜’更佳者爲4〜10。有關 該烷氧基中’與氧原子鍵結之烷基亦相同。 具體而言’作爲該有機磷化合物者’如：二-2-乙基己 -9- 201005076 基次膦酸、2-乙基己基膦酸2-乙基己酯、磷酸三辛酯、磷 酸三丁酯、三辛基膦氧化物、辛基次膦酸等例，此等可使 用1種或2種以上組合者。 作爲該疏水性有機溶媒者，並未特別受限，一般如： 月桂烷、己烷、煤油等之脂肪族烴基、甲苯等之芳香族烴 基、環己烷等之脂環式烴基、氯仿、二氯甲烷等之鹵素溶 媒等例，此等可單1種使用，或合倂2種以上之使用。 φ 對於疏水性有機溶媒之有機磷化合物之含有比例並未 特別受限，一般可使疏水性有機溶媒中之有機磷化合物之 濃度作成0.0001〜10M、較佳者爲0.005〜1M。 該混合處理槽3 0，並未特別受限，一般如：具備攪拌 機、振盪機等（未示圖）。爲作爲適於所使用之有機磷化 合物、疏水性有機溶媒之溫度的目的下，且爲維持蝕刻液 之溫度的目的下，於由鈾刻處理液貯存槽20至混合處理 槽30之經路途中、混合處理槽30之外圍等配置冷卻器、 • 加熱器等（未示圖）之溫度調節方式亦可。並不一定要限 定，而通常於〇〜15(TC、更佳者於15〜50°C下進行混合 。攪拌時間如：0.5〜60分鐘者宜，更佳者爲5〜15分鐘 〇 該混合之蝕刻處理液與含有機磷化合物之疏水性有機 溶媒之比例，以體積比計，蝕刻處理液：有機溶媒=1 : 0.001〜100者宜，更佳者爲1: 0.2〜20。 於該混合處理槽3 0混合兩溶液後，爲使蝕刻再生液 進行分離回收，以相分離方式之相分離處理槽50進行相 -10- 201005076 分離。相分離係隨時間的經過同時自發性進行’上層有 相5 1，下層水相5 4，而兩相之界面出現由矽化合物所 之析出物5 3。經由所使用之疏水性有機溶媒’除有機 51、析出物53、水相54之外’於有機相51、與析出物 之間，被推斷亦出現由磷酸、有機磷化合物、矽化合物 成之高黏度中間相52。由如此分離的有機相51、（中 相5 2 )、析出物5 3、水相5 4，水相5 4作爲鈾刻再生液 被回收。 此時，有機相51亦進行另途回收，爲可於鈾刻處 液之再生中再利用，亦可具備重覆使用疏水性有機溶媒 循環系。本發明者硏究中，確定於回收後之有機相51 幾乎未含矽化合物。因此，重覆使用疏水性有機溶媒時 無需進行爲去除矽化合物之濾器過濾，直接使用回收液 不會出現問題。而，有機相5 1中之有機磷化合物係由 刻處理液析出分離矽化合物時被消耗，故於再利用前， Φ 可調整有機磷化合物之濃度。設定該循環系，重覆回收 水性有機溶媒再利用後，可削減有機物之廢棄量，可降 成本，抑制環境污染。 該回收之水相54係去除大部分之矽化合物，具有 充份再利用氮化矽膜之蝕刻的性能；而進一步以濾器過 55去除些微含於水相54之析出殘渣後，則可更有效去 矽化合物。另外，經由該回收操作，於濾器過濾前去除 部份之矽化合物，於濾器過濾55中，不會頻繁出現濾 之阻塞。 機 成 相 53 所 間 而 理 之 中 亦 蝕 亦 疏 低 可 濾 除 大 器 -11 - 201005076 更亦可多次進行此混合•分離•回收之一連串操作去 除矽化合物。具體而言’如圖示地，將該回收之水相54 由經路部5 6導入混合處理槽3 0 (流量係以開關活門5 7進 行調整）’將含有機磷化合物之疏水性有機溶媒進行添加 混合’於相分離處理槽50再度進行相分離後，使蝕刻處 理液中之矽化合物析出分離，可回收進一步降低矽化合物 濃度之水相5 4。並未特別限定，一般如：使該一連串的混 0 合•分離•回收操作進行1〜3次者宜。 該回收之水相54係通過蝕刻再生液供應部60，導入 蝕刻部A。於蝕刻再生液供應部60之前，設置調整部70 則更爲理想。該調整部7 0中，爲於蝕刻中再利用，故進 行蝕刻再生液之濃度、溫度之調整。亦即，設置調整部70 ，則該相分離中其部份磷酸移行至中間相52後，降低磷 酸濃度時，或爲作成適於與該疏水性有機溶媒混合之溫度 ，一旦冷卻蝕刻處理液時，使其調整爲所期待之濃度、溫 # 度後，均可維持蝕刻性能，可實現連續性蝕刻及蝕刻處理 液之再生。本發明中，不同於先行技術，爲達成高度去除 矽化合物之效率，並無需過度冷卻蝕刻處理液，因此，設 置該調整部70，仍可經由此微熱能進行調整濃度、溫度， 簡便且成本低廉。 藉由並行該一連串的步驟後，可連續進行鈾刻與蝕刻 處理液之再生。 上述實施形態中，分別設置蝕刻處理液貯存槽20、混 合處理槽30、相分離處理槽50’而亦可於1個槽進行全 -12- 201005076 部處理，或進行混合處理與相分離處理。又，亦可不設置 蝕刻處理液貯存槽2 0，使由蝕刻部A排出之蝕刻處理液 ’直接流入混合處理槽30。更可使用離心分離器取代該相 分離處理槽50作爲相分離方式亦可。藉由此，可取得更 有效的相分離。經由該離心分離法之相分離，如：以5 00 〜2000rpm，進行0.5〜15分鐘者宜。 又，該實施形態中，亦可設置爲了補充添加新的蝕刻 φ 液之蝕刻新液供應部。 另外，水相54中，僅殘留些微的有機磷化合物、有 機溶媒等之有機物，惟此等有機物並不會如先行技術之影 響蝕刻性能。且，有機溶媒多半爲低沸點，故於蝕刻再生 液用於蝕刻部時揮發。有機磷化合物爲高沸點，故於蝕刻 時無法揮發而殘留，可能附著於晶圓，通常，於蝕刻後進 行之晶圓的濕潤步驟被去除。惟，爲更確實去除有機磷化 合物，亦可混合水相54與有機溶媒（不含有機磷化合物 # )，由水相萃取有機磷化合物，去除之。 [實施例] 以下，以實施例及比較例爲例，進行本發明更具體的 說明。另外，％意指重量％，ppm意指mg/kg。 以下代表實施例之測定方法。 <矽化合物濃度（S i濃度）之測定> 蝕刻液中之矽化合物濃度（S i濃度）（ppm )係利用 -13- 201005076BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an etching treatment regeneration method for removing regeneration of a treatment liquid in an etching-containing phosphoric acid etching treatment liquid. • [Prior Art] For MOS-type LSIs, when ruthenium nitride film and ruthenium oxide are etched, yttrium oxide containing ruthenium and phosphoric acid is dissolved in the etchant is usually precipitated. Wafers are subject to problems. In order to solve this problem, the problem of the operation time of the phosphoric acid required to replace the etching solution before or after the Φ solution is generated is considered. Therefore, it has been disclosed that one of the various technologies is such that the etchant reacts with hydrogen fluoride to form a fluorination removal technique (refer to the patent, the etching treatment liquid is cooled, and there is an etch for the ruthenium oxide film or the tantalum nitride film). The ruthenium compound is suitable for a film such as a LOCOS method for producing a phosphoric acid-containing treatment liquid such as a uranium liquid regeneration method, and is a phosphoric acid etching solution for selectively etching a tantalum nitride film. During the etching, it should be decomposed into nitrogen and ammonia. The oxidation state, except for the saturated dissolved amount, causes the damage to be a filter problem for removing impurities. In the prior art, the etching solution is replaced by a saturated solution. A large amount of waste time is too wasteful, and the viewpoint of stopping the environmental and economic aspects of the device is ignored by the regeneration technology of the etching treatment liquid. Hydrogen fluoride is added as a treatment liquid, and the cerium compound is heated and evaporated simultaneously with water. 1). Further, as another skilled person, a technique in which a ruthenium compound is precipitated and removed by a filter to remove the ruthenium compound by a filter, and then reheated and reused (Patent Document 2) is also known. [Patent Document 1] Japanese Patent No. 3 609 876 [Patent Document 2] Japanese Patent No. 3609 1 86, except that hydrogen fluoride is a reaction with ruthenium and osmium compounds, and when hydrogen fluoride φ is used, hydrogen fluoride remains in the etching regeneration liquid. Damage to the wafer may greatly affect the etching selectivity. To avoid this, it is important to monitor and adjust the concentration of hydrogen fluoride. Further, since hydrogen fluoride is soluble in the etching liquid, it is difficult to remove and easily remains in the etching regeneration liquid. Further, after the further test of the present invention, the removal efficiency is not high in the technique in which the ruthenium compound is precipitated and removed by cooling the etching treatment liquid. SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a problem in which the selectivity to a tantalum nitride containing a phosphoric acid-regenerating liquid is changed depending on the residue of other substances in the prior art. The present invention can effectively regenerate a phosphoric acid-containing treatment solution containing a phosphoric acid treatment solution at a low energy. The inventors of the present invention have conducted sophisticated discussions to solve this problem. As a result, it has been found that the phosphoric acid-containing treatment liquid produced by the treatment of tantalum nitride can be separated from the hydrophobic organic solvent containing a specific organophosphorus compound and then separated, and then the antimony compound in the phosphoric acid-containing treatment liquid can be made The phosphoric acid-containing liquid liquefaction -6-201005076 is separated, and by removing the ruthenium compound, the concentration of the ruthenium compound in the phosphoric acid-containing treatment liquid can be extremely easily and efficiently reduced, and after the determination, the present invention is completed. That is, the method for regenerating the phosphoric acid-containing treatment liquid of the present invention is a method for regenerating a phosphoric acid-containing treatment liquid produced by treatment with tantalum nitride, which is characterized by the following general formula 鬌YP = 〇(1)疏水 (wherein X, γ, and fluorene each independently represent an alkyl group, an alkoxy group, or a hydroxyl group, except that X, γ, and oxime are all hydroxyl groups), and a hydrophobic organic solvent containing an organic phosphorus compound Once the phosphoric acid-containing treatment liquid is mixed, the phases are separated, and the ruthenium compound in the phosphoric acid-containing treatment liquid is separated and separated from the phosphoric acid-containing treatment liquid, and then the phosphoric acid-containing regeneration liquid is recovered. Hereinafter, in the detailed list, the organophosphorus compound represented by the above formula (1) is shown only by "organophosphorus compound". In the method for regenerating the phosphoric acid-containing treatment liquid of the present invention, the phosphoric acid-containing treatment liquid produced by the treatment of tantalum nitride and the hydrophobic organic solvent containing the organic phosphorus compound are mixed and separated, and then precipitated from the phosphoric acid-containing treatment liquid. Since the ruthenium compound in the phosphoric acid-containing treatment liquid is separated, the concentration of the ruthenium compound in the phosphoric acid-containing treatment liquid can be extremely easily and efficiently reduced by removing the ruthenium compound. Further, as a substance for removing a ruthenium compound, an organic phosphorus compound which is hardly soluble in a phosphoric acid-containing regenerating liquid and a hydrophobic organic solvent are used, so that it can be almost completely removed, and even if it remains, it does not affect the reaction of the phosphoric acid-regenerating 201005076 liquid. Sex, selectivity. In particular, when the treatment of the tantalum nitride is performed by etching a tantalum nitride film, as the substance for removing the antimony compound, as described above, the organic phosphorus compound and the hydrophobic organic solvent which are hardly soluble in the phosphoric acid-containing etching solution are used. Therefore, it can be removed almost completely 'and even if it does not affect the performance of the etching regeneration liquid. After the phase separation is promoted by the centrifugal separation method, the regeneration of the phosphoric acid-containing treatment liquid can be performed more efficiently. After recovering the phosphoric acid-containing regenerating liquid, it is possible to further effectively remove the cerium compound by filtering it with a filter to remove Φ from the precipitation residue contained in the phosphoric acid-containing regenerating liquid. After the organic phase is reused in the regeneration of the phosphoric acid-containing treatment liquid, the amount of waste can be reduced. The long-term, continuous phosphoric acid-containing treatment liquid can be regenerated and used by adjusting the concentration and/or temperature of the recovered phosphoric acid-containing regeneration liquid. [Embodiment] [Best Mode for Carrying Out the Invention] Hereinafter, the method for regenerating the phosphoric acid-containing treatment liquid of the present invention is carried out by taking a regeneration method of a uranium-containing etching solution for phosphoric acid used in the etching of a tantalum nitride film as an example. The scope of the present invention is not limited thereto, and the scope of the present invention is not limited thereto, and modifications may be appropriately made without departing from the scope of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing an embodiment of an embodiment of the present invention, showing an etching apparatus. First, the etching portion A will be described. The etching bath 10 is filled with a etched liquid, and the wafer formed by immersing the yttrium oxide film and the tantalum nitride film is etched into a yttrium nitride film. The temperature of the etching solution is maintained at a high temperature (150 to 170 ° C) via a heater (not shown) provided on the periphery of the etching bath 1 . The overflow gate 12 is disposed on the periphery of the etching tank 10, and the etching liquid retained in the overflow gate 12 is passed through the passage portion through the discharge port provided at the bottom of the overflow gate 12 by the action of the pump 14 or the like. 13. An etching liquid regeneration unit B as an etching treatment liquid is introduced. In the etching liquid regeneration unit B, first, an etching treatment liquid into which φ is introduced through the passage portion 13 is stored in the etching treatment liquid storage tank 20. The etching treatment liquid storage tank 20 causes the specific amount of the etching treatment liquid adjusted by the switching shutter 21 to flow into the mixing processing tank 30 of the mixing mode. Further, the organic solvent storage tank 40 provided in the other way is the same as the etching treatment liquid, and flows into a specific amount of the hydrophobic organic solvent containing the organic phosphorus compound adjusted by the switching shutter 41. Thus, the two solutions are mixed in the mixing treatment tank 30. As described above, the organophosphorus compound is represented by the following general formula X, Y-P = 0 (1) zy (wherein, X, Y, and Z each independently represent an alkyl group, an alkoxy group or a hydroxyl group. However, x, Y Except that z is a hydroxyl group). As shown, the alkyl group may be linear or branched, and the carbon number thereof is not particularly limited. Generally, it is preferably 1 to 2, and more preferably 4 to 10. The alkyl group bonded to the oxygen atom in the alkoxy group is also the same. Specifically, 'as the organophosphorus compound', such as: di-2-ethylhex-9- 201005076, phosphinic acid, 2-ethylhexylphosphonate 2-ethylhexyl ester, trioctyl phosphate, phosphoric acid Examples of the butyl ester, the trioctylphosphine oxide, and the octylphosphinic acid may be used alone or in combination of two or more. The hydrophobic organic solvent is not particularly limited, and is generally an aliphatic hydrocarbon group such as linaloline, hexane or kerosene, an aromatic hydrocarbon group such as toluene, an alicyclic hydrocarbon group such as cyclohexane, or the like. Examples of the halogen solvent such as methyl chloride may be used alone or in combination of two or more. The content ratio of φ to the organophosphorus compound of the hydrophobic organic solvent is not particularly limited, and the concentration of the organophosphorus compound in the hydrophobic organic solvent can be generally made 0.0001 to 10 M, preferably 0.005 to 1 M. The mixing treatment tank 30 is not particularly limited, and generally includes a stirrer, a shaker, and the like (not shown). The purpose of the uranium engraving treatment liquid storage tank 20 to the mixing treatment tank 30 is for the purpose of maintaining the temperature of the organophosphorus compound or the hydrophobic organic solvent to be used, and for maintaining the temperature of the etching liquid. The temperature adjustment method of a cooler, a heater, etc. (not shown) may be disposed on the periphery of the mixing tank 30, and the like. It is not necessarily limited, but it is usually mixed at 〇15 (TC, more preferably at 15~50 °C. The stirring time is as follows: 0.5~60 minutes, more preferably 5~15 minutes 〇 the mixture The ratio of the etching treatment liquid to the hydrophobic organic solvent containing the organic phosphorus compound is, in terms of volume ratio, the etching treatment liquid: organic solvent = 1: 0.001 to 100, more preferably 1: 0.2 to 20. After mixing the two solutions in the treatment tank 30, in order to separate and recover the etching regeneration liquid, the phase separation treatment tank 50 in the phase separation manner performs phase separation from -10-201005076. The phase separation system spontaneously proceeds with the passage of time. Phase 5 1, the lower aqueous phase is 5 4, and the precipitate of the ruthenium compound is present at the interface between the two phases. The hydrophobic organic solvent used 'except the organic 51, the precipitate 53 and the aqueous phase 54' Between the organic phase 51 and the precipitate, it is presumed that a high-viscosity intermediate phase 52 composed of phosphoric acid, an organic phosphorus compound, or a ruthenium compound also appears. The organic phase 51, the intermediate phase 5 2 , and the precipitate 5 3 thus separated , the water phase 5 4, the water phase 5 4 is returned as the uranium enrichment liquid At this time, the organic phase 51 is also recovered separately, and may be reused in the regeneration of the uranium engraved liquid, or may be repeatedly used in a hydrophobic organic solvent circulation system. The organic phase 51 contains almost no antimony compound. Therefore, when the hydrophobic organic solvent is repeatedly used, it is not necessary to carry out filtration for removing the deuterium compound, and there is no problem in directly using the recovery liquid. However, the organic phosphorus compound in the organic phase 51 When the ruthenium compound is separated and deposited by the engraved treatment liquid, the concentration of the organophosphorus compound can be adjusted by Φ before reuse. By setting the cycle system and recycling the aqueous organic solvent, the amount of organic matter can be reduced. The cost can be reduced to suppress environmental pollution. The recovered aqueous phase 54 removes most of the antimony compound and has the property of fully utilizing the etching of the tantalum nitride film; and further removes some of the micro-containing water phase 54 by the filter 55. After the residue is precipitated, the compound can be removed more efficiently. In addition, a part of the ruthenium compound is removed before the filter is filtered through the recovery operation, and filtered in a filter 55. There will be no frequent blockage of the filter. The machine is in phase 53 and the eclipse is also low. The filter can be filtered out. -11 - 201005076 It is also possible to carry out this mixing, separation and recycling one after another. Specifically, as shown in the figure, the recovered aqueous phase 54 is introduced into the mixing treatment tank 30 via the road portion 56 (the flow rate is adjusted by the switching valve 57) to contain the hydrophobicity of the organic phosphorus compound. The organic solvent is added and mixed. After the phase separation treatment tank 50 is again subjected to phase separation, the ruthenium compound in the etching treatment liquid is precipitated and separated, and the aqueous phase 5 which further reduces the concentration of the ruthenium compound can be recovered. It is not particularly limited. Generally, it is preferable to carry out the series of mixing, separation, and recovery operations for 1 to 3 times. The recovered aqueous phase 54 is introduced into the etching portion A by etching the regenerant supply unit 60. It is more preferable to provide the adjustment unit 70 before etching the regenerant supply unit 60. In the adjustment portion 70, in order to reuse it during etching, the concentration and temperature of the etching regeneration liquid are adjusted. That is, when the adjustment portion 70 is provided, when the partial phosphoric acid in the phase separation is transferred to the intermediate phase 52, when the phosphoric acid concentration is lowered, or when the temperature is suitable for mixing with the hydrophobic organic solvent, once the etching treatment liquid is cooled, By adjusting it to the desired concentration and temperature of # degrees, the etching performance can be maintained, and continuous etching and regeneration of the etching treatment liquid can be realized. In the present invention, unlike the prior art, in order to achieve high efficiency of removing the ruthenium compound, it is not necessary to excessively cool the etching treatment liquid. Therefore, by providing the adjustment portion 70, the concentration and temperature can be adjusted through the micro-heat energy, which is simple and inexpensive. . By continuing the series of steps in parallel, the regeneration of the uranium engraving and etching treatment liquid can be continuously performed. In the above embodiment, the etching treatment liquid storage tank 20, the mixing treatment tank 30, and the phase separation treatment tank 50' are provided, and all of the treatments may be performed in one tank, or the mixing treatment and the phase separation treatment may be performed. Further, the etching treatment liquid storage tank 20 may be omitted, and the etching treatment liquid ' discharged from the etching portion A may be directly flowed into the mixing treatment tank 30. Instead of the phase separation treatment tank 50, a centrifugal separator may be used as the phase separation method. Thereby, a more efficient phase separation can be achieved. The phase separation by the centrifugation method, for example, is carried out at 500 to 2000 rpm for 0.5 to 15 minutes. Further, in this embodiment, an etching fresh liquid supply portion for adding a new etching φ liquid may be provided. Further, in the aqueous phase 54, only a small amount of organic substances such as an organic phosphorus compound or an organic solvent remain, but these organic substances do not affect the etching performance as in the prior art. Further, since the organic solvent is mostly low in boiling point, it is volatilized when the etching regeneration liquid is used for the etching portion. Since the organophosphorus compound has a high boiling point, it does not volatilize and remains during etching, and may adhere to the wafer. Usually, the wetting step of the wafer after etching is removed. However, in order to more reliably remove the organophosphorus compound, the aqueous phase 54 and the organic solvent (excluding the organophosphorus compound #) may be mixed, and the organophosphorus compound may be extracted from the aqueous phase to remove it. [Examples] Hereinafter, the present invention will be more specifically described by way of examples and comparative examples. In addition, % means % by weight, and ppm means mg/kg. The measurement methods of the examples are represented below. <Measurement of cerium compound concentration (S i concentration)> 矽 compound concentration (S i concentration) in the etching solution (ppm) is utilized -13- 201005076
高周波電獎發光分析裝置（「IRIS Intrepid II XDL/DOU 型」、熱電子公司製）進行測定。 作爲標準液者，使和光純藥工業公司製之矽標準液（ lOOOppm、0.2mol/卜 Na2Si03)爲稀釋 85%磷酸成 10 倍之 溶液’使用調製成〇mg/L、0.1mg/L、lmg/L、10mg/L之濃 度者。又，蝕刻液中之Si濃度測定係使蝕刻液稀釋成10 倍後進行之。 ❹ [實施例1] 作爲蝕刻所使用之蝕刻處理液者，使用含有矽化合物 26ppm之85 %磷酸，於攪拌槽（賦予緩衝板）中，使該蝕 刻處理液與含有三辛基膦氧化物（TOP Ο、Aldrich公司製 )之月桂烷（TOOP濃度；0.1M)以1 : 1 (體積比）之比 例進行投入，於機械攪拌器進行攪拌15分鐘。攪拌後， 利用離心分離器進行相分離。僅回收水相，進行濾器過瀘 Q 。濾器過濾後之水相進行回收後，進一步重覆進行相同之 攪拌•分離•回收之一連串的操作。 此操作於25°C下進行。 藉由上述測定方法，測定濾器過濾後之蝕刻再生液中 之Si濃度後結果爲6ppm。 [實施例2] 作爲鈾刻所使用之蝕刻處理液者，使用含有矽化合物 24ppm之85%磷酸，於攪拌槽（賦予緩衝板）中，使該触 -14- 201005076 刻處理液與含有2 -乙基己基膦2 -乙基己酯（PC-88A，大 八化學公司製）之甲苯（PC-88A濃度；0.1M)以1: 1 ( 體積比）之比例進行投入，於機械攪拌器進行攪拌60分 鐘。攪拌後，利用離心分離器，進行相分離。僅回收水相 ’進行濾器過濾。使濾器過濾後之水相進行回收後，進一 步重覆2次進行相同之攪拌•分離•回收之一連串的操作 〇 φ 此操作於2 5 °C下進行。 藉由上述測定方法，測定濾器過濾後之蝕刻再生液中 之Si濃度後結果爲2.1 ppm。 [實施例3] 作爲蝕刻所使用之蝕刻處理液者，使用含有矽化合物 49PPm之85%磷酸，於攪拌槽（賦予緩衝板）中，使該蝕 刻處理液與含有三辛基膦氧化物（TOP Ο、Aldrich公司製 )之月桂烷（τ Ο Ο P濃度；〇. 1 Μ )以1 : 1 (體積比）之比 例下進行投入’於機械攪拌器進行攪拌5分鐘。攪拌後， 利用離心分離器，進行相分離。僅回收水相，進行濾器過 濾。使濾器過濾後之水相進行回收後，進一步重覆2次同 樣的攪拌•分離•回收之一連串的操作。 此操作於25 °C下進行之。 藉由_h述測I定方法，將濾器過濾後之蝕刻再生液中之 Si濃度分別針對第1次、第2次、第3次進行測定。結果 示於表1。 -15- 201005076 [表l] 初期濃度 第1次 第2次 第3次 s i 濃度（p p m) 49 23 12 7 去除率（％) 53 48 42 合計去除率（％) - 53 75 86 [實施例4] 作爲蝕刻所使用之蝕刻處理液者，使用含有矽化合物 φ 79ppm之85%磷酸，於攪拌槽（賦予緩衝板）中，將該蝕 刻處理液與含有三辛基膦氧化物（TOPO、Aldrich公司製 )之月桂烷（TOOP濃度；0.005M)以1: 0.5(體積比） 之比例下進行投入，於機械攪拌器進行攪拌10分鐘。攪 拌後，利用離心分離器，進行相分離。僅回收水相，進行 濾器過濾。使濾器過濾後之水相進行回收後，進一步重覆 相同之攪拌•分離•回收之一連串的操作。 此操作於25°C下進行之。 φ 藉由上述測定方法，測定濾器過濾後之蝕刻再生液中 之Si濃度後結果爲9.1ppm。 [實施例5] 作爲蝕刻所使用之蝕刻處理液者，使用含有矽化合物 49ppm之85%磷酸，於攪拌槽（賦予緩衝板）中，將該蝕 刻處理液與含有2-乙基己基膦酸2-乙基己酯（PC-88A， 大八化學公司製）之甲苯（PC-88A濃度；0.1M)以1:1 (體積比）之比例，進行投入，於機械攪拌器進行攪拌1 5 -16- 201005076 分鐘。攪拌後，利用離心分離器進行相分離。僅回收水相 ，進行濾器過濾。將濾器過濾後之水相進行回收，進一步 重覆2次相同的攪拌•分離•回收之一連串的操作。 該操作於2 5 °C下進行之。 藉由該測定方法，將濾器過濾後之蝕刻再生液中之Si 濃度，分別進行第1次、第2次、第3次之測定。結果示 於表2。 初期濃度 第1次 第2次 第3次 Si 濃度（ppm) 42 19 10 6.3 去除率（％) 55 47 37 合計去除率（％) - 55 76 85 [比較例1] 作爲蝕刻所使用之蝕刻處理液者，將含有加熱至1 5 0 °(：之矽化合物79?1)111之85%磷酸，冷卻至25°(：後，進行 濾器過濾。 藉由該測定方法，測定濾器過濾後之蝕刻再生液中之 Si濃度之結果爲52ppm。 [比較例2] 作爲蝕刻所使用之蝕刻處理液者，將含有加熱至1 5 0 °C之矽化合物124ppm之8 5%磷酸冷卻至25 °C後，進行濾 器過濾。 藉由該測定方法，測定濾器過濾後之蝕刻再生液中之 -17- 201005076The high-frequency electric power luminescence analyzer ("IRIS Intrepid II XDL/DOU type", manufactured by Thermal Electronics Co., Ltd.) was used for measurement. As a standard solution, the standard solution (100Oppm, 0.2mol/bu Na2Si03) made by Wako Pure Chemical Industries Co., Ltd. is a solution that is diluted 10 times with 85% phosphoric acid. The dosage is adjusted to 〇mg/L, 0.1mg/L, lmg. /L, the concentration of 10mg / L. Further, the Si concentration in the etching solution was measured by diluting the etching solution to 10 times.实施 [Example 1] As an etching treatment liquid used for etching, 85% phosphoric acid containing 26 ppm of an antimony compound was used, and the etching treatment liquid and trioctylphosphine oxide were contained in a stirring tank (provided to a buffer plate). The urethane (TOOP concentration; 0.1 M) of TOP Ο, manufactured by Aldrich Co., Ltd. was put at a ratio of 1:1 (volume ratio), and stirred in a mechanical stirrer for 15 minutes. After stirring, the phase separation was carried out using a centrifugal separator. Only the aqueous phase is recovered and the filter is passed through Q. After the filtered aqueous phase is recovered, it is further repeated for the same series of stirring, separation and recovery operations. This operation was carried out at 25 °C. According to the above measurement method, the Si concentration in the etching regeneration liquid after the filter filtration was measured and found to be 6 ppm. [Example 2] As an etching treatment liquid used for uranium engraving, 85% phosphoric acid containing 24 ppm of an antimony compound was used, and in the stirring tank (provided to a buffer plate), the treatment liquid of the contact-14-201005076 was contained and contained 2 - Ethylhexylphosphine 2-ethylhexyl ester (PC-88A, manufactured by Daiha Chemical Co., Ltd.) toluene (PC-88A concentration; 0.1 M) was put at a ratio of 1:1 (volume ratio) and was subjected to mechanical stirrer. Stir for 60 minutes. After stirring, phase separation was carried out using a centrifugal separator. Only the aqueous phase is recovered' for filter filtration. After the water phase filtered by the filter is recovered, it is further repeated twice for the same stirring, separation, and recovery. 〇 φ This operation is carried out at 25 °C. The Si concentration in the etching regeneration liquid after the filter filtration was measured by the above measurement method and found to be 2.1 ppm. [Example 3] As an etching treatment liquid used for etching, 85% phosphoric acid containing ruthenium compound 49 ppm was used, and the etching treatment liquid and trioctylphosphine oxide (TOP) were added to a stirring tank (provided to a buffer plate). The sulphate (τ 1 Ο P concentration; 〇. 1 Μ) manufactured by Aldrich Co., Ltd. was put into a mechanical stirrer at a ratio of 1:1 (volume ratio) for 5 minutes. After stirring, the phase separation was carried out using a centrifugal separator. Only the aqueous phase is recovered and filtered through a filter. After the water phase filtered by the filter is recovered, the same operation of stirring, separating, and recycling is repeated twice. This operation was carried out at 25 °C. The Si concentration in the etching regeneration liquid after the filter was filtered was measured for the first time, the second time, and the third time by the _h method. The results are shown in Table 1. -15- 201005076 [Table l] Initial concentration 1st 2nd 3rd si concentration (ppm) 49 23 12 7 Removal rate (%) 53 48 42 Total removal rate (%) - 53 75 86 [Example 4] In the etching treatment liquid used for the etching, 85% phosphoric acid containing yttrium compound φ 79 ppm was used, and the etching treatment liquid and trioctylphosphine oxide (TOPO, Aldrich) were used in the stirring tank (provided to the buffer plate). The lauryl (TOOP concentration; 0.005 M) was charged at a ratio of 1:0.5 (volume ratio), and stirred for 10 minutes in a mechanical stirrer. After the agitation, the phase separation was carried out using a centrifugal separator. Only the aqueous phase is recovered and filtered through a filter. After the filtered aqueous phase is recovered, the same series of stirring, separation, and recovery operations are repeated. This operation was carried out at 25 °C. φ The Si concentration in the etching regeneration liquid after the filter filtration was measured by the above measurement method and found to be 9.1 ppm. [Example 5] As an etching treatment liquid used for etching, 85% phosphoric acid containing 49 ppm of a cerium compound was used, and the etching treatment liquid and 2-ethylhexylphosphonic acid 2 were contained in a stirring tank (provided to a buffer plate). -ethylhexyl ester (PC-88A, manufactured by Daiba Chemical Co., Ltd.) toluene (PC-88A concentration; 0.1 M) was charged at a ratio of 1:1 (volume ratio), and stirred in a mechanical stirrer. 16-201005076 minutes. After stirring, the phase separation was carried out using a centrifugal separator. Only the aqueous phase is recovered and filtered through a filter. The water phase filtered by the filter is recovered, and the same stirring, separation, and recycling are repeated twice for a series of operations. This operation was carried out at 25 °C. According to this measurement method, the Si concentration in the etching regeneration liquid after the filter was filtered was measured for the first time, the second time, and the third time, respectively. The results are shown in Table 2. Initial concentration 1st 2nd 3rd Si concentration (ppm) 42 19 10 6.3 Removal rate (%) 55 47 37 Total removal rate (%) - 55 76 85 [Comparative example 1] The etching treatment liquid used for etching It will contain 85% phosphoric acid heated to 150 ° (: 矽 compound 79? 1) 111, and cooled to 25 ° (:, then filter is filtered. By this measurement method, the filter regenerated regr The result of the Si concentration was 52 ppm. [Comparative Example 2] As an etching treatment liquid used for etching, 85% of phosphoric acid containing 124 ppm of a ruthenium compound heated to 150 ° C was cooled to 25 ° C, and then it was carried out. Filtration of the filter. By the measurement method, the etch regeneration liquid after filtering the filter is measured -17-201005076
Si濃度後結果爲52ppm。 [評定] 由實施例1〜5證明，本發明可以極高效率去除矽化 合物，特別是，由表1、表2所見，經由重覆處理後’顯 不去除效率提昇，最後可確定去除85%以上之去除砍化合 物之明顯效果。 ❹ 僅經由冷卻至室溫後，析出磷酸中之矽化合物，之後 ，由去除瀘器過濾所析出物之比較例1、2之結果算出其 各自的去除效率後，比較例1爲34%、比較例2爲58%， 提昇其以上之去除效率時，則務必進一步進行冷卻。因此 ，相較於實施例1〜5，其去除效率較差，爲達到相同於實 施例1〜5之去除效率，進一步進行冷卻時，爲使蝕刻再 生液再行使用，考量之後的非再加熱不可之觀點下’務必 耗費相當大的熱能，經濟面極差。 參 [產業上可利用性] 本發明該含磷酸處理液之再生方法係由氮化矽之處理 所產生之含磷酸處理液，去除矽化合物’適用於回收含磷 酸再生液之方法，特別是，針對氮化矽膜與氧化矽膜’爲 使氮化矽膜進行選擇性蝕刻，利用含加熱之磷酸之鈾刻液 時，適用於爲使鈾刻處理液再生之方法。 【圖式簡單說明】 -18- 201005076 圖1係代表本發明一實施例之蝕刻裝置的模式圖。 【主要元件符號說明】 A :蝕刻部 B :蝕刻液再生部 I 〇 :蝕刻槽 II :晶圓 φ 20 :蝕刻處理液貯存槽 3 0 ‘·混合處理槽 40 :有機溶媒貯存槽 5 0 :相分離處理槽 5 1 :有機相 52 :中間相 5 3 :析出物 54 :水相 φ 55 :濾器過濾 5 7 :活門 60 :蝕刻再生液供應部 70 :調整部 -19-The result after Si concentration was 52 ppm. [Evaluation] It is proved by Examples 1 to 5 that the present invention can remove the ruthenium compound with extremely high efficiency, in particular, as seen from Tables 1 and 2, after the repeated treatment, the efficiency of the removal is not improved, and finally 85% can be determined. The above obvious effect of removing the chopping compound. ❹ Only after cooling to room temperature, the ruthenium compound in the phosphoric acid was precipitated, and then the respective removal efficiencies were calculated from the results of Comparative Examples 1 and 2 in which the precipitate was filtered by the eliminator, and Comparative Example 1 was 34%. In Example 2, it is 58%. When the removal efficiency is increased above, it is necessary to further cool. Therefore, compared with Examples 1 to 5, the removal efficiency is inferior, and in order to achieve the same removal efficiency as in Examples 1 to 5, in the case of further cooling, in order to reuse the etching regeneration liquid, the non-reheating after the consideration is not possible. From the point of view, 'must consume a considerable amount of heat, and the economy is extremely poor. [Industrial Applicability] The method for regenerating the phosphoric acid-containing treatment liquid of the present invention is a method for recovering a phosphoric acid-containing regeneration liquid by using a phosphoric acid-containing treatment liquid produced by treatment of tantalum nitride, and removing the antimony compound, in particular, For the tantalum nitride film and the hafnium oxide film, in order to selectively etch the tantalum nitride film and use the uranium engraving liquid containing heated phosphoric acid, it is suitable for a method for regenerating the uranium engraving treatment liquid. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic view showing an etching apparatus according to an embodiment of the present invention. [Description of main component symbols] A: etching portion B: etching liquid regeneration portion I 〇: etching groove II: wafer φ 20 : etching treatment liquid storage tank 3 0 '· mixing processing tank 40: organic solvent storage tank 5 0 : phase Separation treatment tank 5 1 : Organic phase 52 : Intermediate phase 5 3 : Precipitate 54 : Water phase φ 55 : Filter filtration 5 7 : Valve 60 : Etching regeneration liquid supply unit 70 : Adjustment portion -19-