TWI440608B - Preparation of Alkaline Aqueous Solution - Google Patents
Preparation of Alkaline Aqueous Solution Download PDFInfo
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- TWI440608B TWI440608B TW096121859A TW96121859A TWI440608B TW I440608 B TWI440608 B TW I440608B TW 096121859 A TW096121859 A TW 096121859A TW 96121859 A TW96121859 A TW 96121859A TW I440608 B TWI440608 B TW I440608B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
- C01D1/04—Hydroxides
- C01D1/28—Purification; Separation
- C01D1/32—Purification; Separation by absorption or precipitation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/02—Preparation, purification or separation of ammonia
- C01C1/024—Purification
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D7/00—Carbonates of sodium, potassium or alkali metals in general
- C01D7/22—Purification
- C01D7/26—Purification by precipitation or adsorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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Description
本發明，係關於一種將鹼水溶液所含之金屬雜質的濃度、或視需要之矽化雜質及碳酸雜質的濃度，精製至非常低之濃度為止的鹼水溶液之精製方法。The present invention relates to a method for purifying an aqueous alkali solution obtained by purifying a concentration of a metal impurity contained in an aqueous alkali solution or, if necessary, a concentration of a halogenated impurity and a carbonic acid impurity to a very low concentration.
鹼，係使用於將製造矽晶圓時所生成之加工變質層除去之蝕刻製程、或為了pH調整及緩衝而與膠態氧化矽等研磨劑組合之研磨製程。又，鹼，於研磨製程後之晶圓洗淨亦常使用。於蝕刻製程，係使用氫氧化鈉或氫氧化鉀，於研磨製程，係使用氫氧化鈉、氫氧化鉀、氫氧化四甲銨、氨水、碳酸鈉、碳酸氫納、碳酸鉀及碳酸氫鉀，於洗淨製程，係使用氨水。The alkali is used in an etching process for removing a process-modified layer formed when a germanium wafer is produced, or a polishing process in combination with an abrasive such as colloidal cerium oxide for pH adjustment and buffering. Moreover, alkali is often used for wafer cleaning after the polishing process. In the etching process, sodium hydroxide or potassium hydroxide is used, and in the polishing process, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, ammonia water, sodium carbonate, sodium hydrogencarbonate, potassium carbonate and potassium hydrogencarbonate are used. In the washing process, ammonia water is used.
鹼，例如，氫氧化鈉係以食鹽的電解而製造，所生成之氫氧化鈉，含有數ppm等級之各種金屬雜質。該等金屬雜質中，例如，銅與鎳，會滲透至矽晶圓，殘存而使電氣特性改變等而阻害晶圓表面的平坦化。因此，含有該等金屬雜質之鹼水溶液，無法作為蝕刻劑使用。又，鈣、鎂、錳、鐵、鈷、鋅、鋁、鉛等金屬，雖難以擴散至矽晶圓之內部，但會殘留於表面成為殘渣，而阻害電氣特性等。因此，於鹼蝕刻製程或研磨製程所使用之藥液、研磨液中若含有該等金屬雜質，則該藥液、研磨液的使用會成為後段製程之洗淨製程的負荷。關於如銅、鎳等之容易擴散至晶圓內部之金屬、與鈣、鎂、錳、鐵、鈷、鋅、鋁、鉛等殘留於晶圓表面之金屬，當比較其濃度所造成之影響時，容易擴散之金屬濃度、與殘留於表面之金屬相比，有時有必需減低至1/10~1/1000的情形。The alkali, for example, sodium hydroxide is produced by electrolysis of a salt, and the produced sodium hydroxide contains various metal impurities of several ppm levels. Among these metal impurities, for example, copper and nickel permeate into the germanium wafer, and remain, and electrical characteristics are changed to prevent planarization of the wafer surface. Therefore, an aqueous alkali solution containing such metal impurities cannot be used as an etchant. Further, metals such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, and lead are difficult to diffuse into the interior of the germanium wafer, but remain on the surface as a residue, thereby impairing electrical characteristics. Therefore, if such a metal impurity is contained in the chemical liquid or the polishing liquid used in the alkali etching process or the polishing process, the use of the chemical liquid or the polishing liquid becomes a load of the cleaning process of the subsequent process. For metals such as copper and nickel that are easily diffused into the interior of the wafer, and metals such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, and lead that remain on the surface of the wafer, when comparing the effects of their concentrations The metal concentration which is easy to diffuse may be reduced to 1/10 to 1/1000 as compared with the metal remaining on the surface.
又，於鹼蝕刻，氫氧化鈉與氫氧化鉀，為了減低使用量以減低成本的目的下，會循環再利用。於該場合，由矽晶圓所溶出之矽或空氣環境氣氛中之氧，藉由溶解於鹼蝕刻液，例如，當鹼水溶液為氫氧化鈉時，會產生矽酸鈉(Na2 SiO3 )，而於晶圓表面殘存為殘渣，使後段的洗淨變得困難。為了防止其，有增加新鹼液的補充量使回收率降低的方法。Further, in alkali etching, sodium hydroxide and potassium hydroxide are recycled in order to reduce the amount of use and reduce the cost. In this case, sodium citrate (Na 2 SiO 3 ) is produced by dissolving the oxygen in the atmosphere of the crucible or the atmosphere in the air atmosphere by dissolving in the alkali etching solution, for example, when the aqueous alkali solution is sodium hydroxide. However, it remains as a residue on the surface of the wafer, making it difficult to clean the subsequent stage. In order to prevent this, there is a method of increasing the amount of replenishment of the new alkali liquor to lower the recovery rate.
再者，空氣環境氣氛中之二氧化碳，如下式所述容易溶解於鹼水溶液。Further, the carbon dioxide in the air atmosphere is easily dissolved in the aqueous alkali solution as described in the following formula.
NaOH＋CO2 → NaHCO3 2NaHCO3 → Na2 CO3 ＋H2 NaOH+CO 2 → NaHCO 3 2NaHCO 3 → Na 2 CO 3 +H 2
因此，原本作為鹼成分而必須保持其純度之NaOH變成Na2 CO3 ，而對蝕刻沒有幫助，故必須減低二氧化碳的溶解量。又，當然，若主成分之鹼金屬或氫氧化物等的濃度改變，則對蝕刻處理會產生很大的影響。Therefore, NaOH which is originally required to maintain its purity as an alkali component becomes Na 2 CO 3 and does not contribute to etching, so it is necessary to reduce the amount of carbon dioxide dissolved. Further, of course, if the concentration of the alkali metal or hydroxide of the main component is changed, the etching treatment is greatly affected.
然而，亦有如由研磨製程之漿料中即使混入Na2 SiO3 或Na2 CO3 亦幾乎不會產生影響的狀態、或必須而添加的狀態選擇性地僅減低鹼水溶液所含之金屬雜質的情形。精製鹼的手段，可舉例如再結晶法、蒸餾法等，但任一者皆需巨大的熱能量、裝置亦大規模、操作管理亦複雜。However, there is also a state in which the slurry of the polishing process hardly affects even if Na 2 SiO 3 or Na 2 CO 3 is mixed, or the state which must be added selectively selectively reduces only the metal impurities contained in the aqueous alkali solution. situation. The means for purifying the base may, for example, be a recrystallization method or a distillation method, but any one requires a large amount of heat energy, a large-scale apparatus, and complicated operation management.
相對於此，作為容易地以低成本精製鹼的手段，例如，曾提出將含金屬雜質之高濃度氫氧化鈉水溶液，與將椰子殼系活性碳以硝酸處理後賦活者接觸，以吸附除去金屬雜質之方法(日本特開2004－344715號公報)。然而，由於其必須準備專用的活性碳，故會導致成本的上昇。又，雖可將鐵精製至100ppb左右，但對於銅或鎳僅能精製至100ppb左右，並無法達到要求水準。又，活性碳會使原料中所含之鋅或鋁等金屬雜質溶出，該等即使以硝酸賦活亦難以減低。因此，若金屬雜質之除去要求項目僅限定於鐵即可，但難以使用於銅或鎳等多項目的情形。On the other hand, as a means for easily purifying a base at a low cost, for example, it has been proposed to contact a living body of a high-concentration sodium hydroxide containing metal impurities with a living body treated with nitric acid to remove carbon. Method of impurity (JP-A-2004-344715). However, since it must prepare dedicated activated carbon, it will lead to an increase in cost. Moreover, although iron can be refined to about 100 ppb, copper or nickel can only be purified to about 100 ppb, and the required level cannot be achieved. Further, the activated carbon dissolves metal impurities such as zinc or aluminum contained in the raw material, and it is difficult to reduce it even if it is activated by nitric acid. Therefore, if the requirement for removal of metal impurities is limited to iron, it is difficult to use it in a multi-item such as copper or nickel.
再者，作為減低氫氧化鈉水溶液所含金屬雜質之方法，已知有使用陽離子交換膜以氫氧化鈉水溶液之電解的精製方法(日本特開2002－317285號公報)。藉由該方法，氫氧化鈉水溶液中之金屬雜質，可減低至10ppb以下。然而，該方法，設備投資為高額、裝置複雜，故有精製成本高、難以操作管理的缺點。In addition, as a method of reducing the metal impurities contained in the aqueous sodium hydroxide solution, a method of purifying by electrolysis using a cation exchange membrane with an aqueous sodium hydroxide solution is known (JP-A-2002-317285). By this method, the metal impurities in the aqueous sodium hydroxide solution can be reduced to 10 ppb or less. However, this method has high equipment investment and complicated equipment, so it has the disadvantages of high refining cost and difficulty in operation and management.
再者，含有氫氧化鈉、氫氧化鉀、氫氧化四甲銨、氨水、碳酸鈉、碳酸氫鈉、碳酸鉀、碳酸氫鉀等之鹼水溶液，除單獨使用以外，例如，亦作為研磨用漿料之添加劑使用。然而，為了將金屬雜質假如減低至100ppb以下之高純度鹼水溶液至使用場所亦維持為高純度的狀態，鹼水溶液之製造工廠或液櫃卡車等運送手段、使用鹼水溶液之晶圓製造工廠或半導體元件製造工廠中，連接、供給配管或槽、桶等容器必須以金屬溶出少之氟樹脂等高價原料加襯、或使用該原料製造。又，欲將晶圓製造工廠或半導體元件製造工廠所使用之鹼水溶液再利用時，會因製造製程等之副產物之金屬等而受到汙染，而無法再使用，僅能廢棄。Further, an aqueous alkali solution containing sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, aqueous ammonia, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate or the like is used as a polishing slurry, for example, alone. Additives for the materials used. However, in order to reduce the metal impurities to a high-purity alkali aqueous solution of 100 ppb or less to a high purity state, a manufacturing method of an aqueous alkali solution or a liquid tank truck, a wafer manufacturing plant using an alkali aqueous solution, or a semiconductor In the component manufacturing plant, a container such as a connection, a supply pipe, a tank, or a tub must be lined with a high-priced raw material such as a fluororesin having a small amount of metal elution, or can be produced using the raw material. In addition, when an alkali aqueous solution used in a wafer manufacturing plant or a semiconductor component manufacturing plant is reused, it is contaminated by the metal of a by-product such as a manufacturing process, and cannot be reused, and can be disposed of.
又，以往，於金屬雜質之除去所使用之使用陽離子交換樹脂之水溶液的精製法，當含有高濃度之鹼成分時，鹼成分與金屬雜質同樣的會與樹脂反應，故無法選擇性地除去金屬雜質。因此，若無再施以適當的處理則主成分之鹼成分的濃度會有產生變化之虞。Further, in the conventional purification method using an aqueous solution of a cation exchange resin used for the removal of metal impurities, when a high concentration of an alkali component is contained, the alkali component reacts with the resin similarly to the metal impurity, so that the metal cannot be selectively removed. Impurities. Therefore, if the appropriate treatment is not applied, the concentration of the alkali component of the main component may change.
如上所述，以往之鹼水溶液，由於含有金屬雜質，為了使用於矽晶圓之蝕刻、研磨製程、洗淨製程等用途，僅以一般之製造方法(例如，電解法)製造者難以使用。因此，必須使用再結晶、蒸餾、或陽離子交換膜法等。然而，該等方法，能量效率差、裝置亦大型、複雜而不易操作管理、精製成本亦高。因此，期盼一種可特別極力減少鈣、鎂、錳、鐵、鈷、鋅、鋁、鉛等金屬雜質之簡便的鹼水溶液之精製方法的開發。又，必須不使主成分之鹼水溶液的濃度改變，並可選擇性地除去矽酸鹼、碳酸雜質、及金屬雜質。As described above, the conventional aqueous alkali solution contains metal impurities and is difficult to be used by a general manufacturing method (for example, an electrolytic method) for use in applications such as etching, polishing, and cleaning processes for tantalum wafers. Therefore, it is necessary to use a recrystallization, distillation, or cation exchange membrane method or the like. However, these methods are inefficient in energy efficiency, large in size, complicated in operation, and easy to operate and manage, and the refining cost is also high. Therefore, development of a method for purifying a simple aqueous alkali solution which is particularly effective in reducing metal impurities such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, and lead is desired. Further, it is necessary to selectively change the concentration of the aqueous alkali solution of the main component, and selectively remove the phthalic acid base, the carbonic acid impurities, and the metal impurities.
本發明，係用以解決上述以往之課題者，其目的在於提供一種使用於矽晶圓之蝕刻、研磨製程、洗淨製程等用途之能以簡便的方法快速除去較高濃度之鹼水溶液所含之金屬雜質之鹼水溶液之精製方法。鹼水溶液，可舉例如含有氫氧化鈉、氫氧化鉀、氫氧化四甲銨、氨水、碳酸鈉、碳酸氫鈉、碳酸鉀及碳酸氫鉀及其他鹼者。The present invention has been made to solve the above-mentioned problems, and an object thereof is to provide a method for rapidly removing a high-concentration aqueous alkali solution by a simple method for use in a ruthenium wafer etching, a polishing process, a cleaning process, or the like. A method for purifying an aqueous alkali solution of a metal impurity. Examples of the aqueous alkali solution include sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, aqueous ammonia, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, potassium hydrogencarbonate, and other bases.
本發明之鹼水溶液之精製方法，其特徵係，將含金屬雜質之鹼水溶液，接觸於選自纖維狀或珠狀之強鹼性陰離子交換體、弱鹼性陰離子交換體、螯合材料、以及賦活後與硝酸接觸之活性碳中之至少一種材料。The method for purifying an aqueous alkali solution according to the present invention, characterized in that an aqueous alkali solution containing a metal impurity is contacted with a strong basic anion exchanger selected from a fibrous or bead shape, a weakly basic anion exchanger, a chelating material, and At least one of activated carbon in contact with nitric acid after activation.
又，鹼水溶液(其中，以氫氧化鈉為代表者)，原本係作為強鹼性陰離子交換體及弱鹼性陰離子交換體等之再生劑使用。然而，本發明，其特徵係，藉由事先將強鹼性陰離子交換體及弱鹼性陰離子交換體之末端基處理成OH型，可除去鹼水溶液中之作為陰離子存在之多數金屬化學源(雜質)。Further, the aqueous alkali solution (wherein represented by sodium hydroxide) is originally used as a regenerating agent such as a strong basic anion exchanger and a weakly basic anion exchanger. However, the present invention is characterized in that a plurality of metal chemical sources (impurities) as anions in an aqueous alkali solution can be removed by previously treating the terminal groups of the strongly basic anion exchanger and the weakly basic anion exchanger into an OH type. ).
再者，處理成OH型之纖維狀或珠狀之強鹼性陰離子交換體，除作為陰離子存在之多數金屬雜質以外，亦可除去矽酸化合物、碳酸根、硫酸根、氯根等雜質。又，藉由接觸於選自纖維狀或珠狀之強鹼性陰離子交換體、弱鹼性陰離子交換體、螯合材料、以及賦活後與硝酸接觸之活性碳中之至少一種材料中，可由含矽化雜質、碳酸雜質與金屬雜質之鹼水溶液，僅除去金屬雜質。Further, the OH-type fibrous or bead-like strong basic anion exchanger can be removed, and impurities such as a phthalic acid compound, a carbonate, a sulfate, and a chloride can be removed in addition to a plurality of metal impurities existing as an anion. Further, by contacting with at least one of a strong basic anion exchanger selected from a fibrous or bead shape, a weakly basic anion exchanger, a chelating material, and activated carbon in contact with nitric acid after activation, An aqueous alkali solution of deuterated impurities, carbonic acid impurities and metal impurities removes only metal impurities.
將鹼水溶液，接觸於選自纖維狀或珠狀之強鹼性陰離子交換體、弱鹼性陰離子交換體、螯合材料、以及賦活後與硝酸接觸之活性碳中之至少一種、或視目的二種以上之材料，例如，可將該等材料充填於管柱或塔中，並使欲精製之鹼水溶液通過其中，或於收容有欲精製之鹼水溶液之反應槽中，添加該等材料並使欲精製之鹼水溶液流動後過濾。此時，纖維狀或珠狀之強鹼性陰離子交換體、弱鹼性陰離子交換體及螯合材料，亦可作為濾筒狀。The aqueous alkali solution is contacted with at least one selected from the group consisting of a strong basic anion exchanger selected from a fibrous or bead shape, a weakly basic anion exchanger, a chelating material, and activated carbon in contact with nitric acid after activation, or For the above materials, for example, the materials may be filled in a column or a column, and the aqueous alkali solution to be purified may be passed therethrough or added to the reaction tank containing the aqueous alkali solution to be refined, and the materials may be added and The aqueous alkali solution to be refined is filtered and filtered. In this case, the fibrous or beaded strong basic anion exchanger, the weakly basic anion exchanger, and the chelating material may also be used as a filter cylinder.
又，本發明，可適用於低濃度至高濃度(例如，鹼濃度0.01~50重量%)之鹼水溶液。Further, the present invention is applicable to an aqueous alkali solution having a low concentration to a high concentration (for example, an alkali concentration of 0.01 to 50% by weight).
本發明所使用之強鹼性陰離子交換體、弱鹼性陰離子交換體及螯合材料，可使用於耐鹼性之合成樹脂纖維或合成樹脂珠，將強鹼性陰離子交換體、弱鹼性陰離子交換體及螯合材料結合者。又，該等之構造，可舉例如凝膠型、多孔型、孔型、巨孔型或巨網狀型等，特別以比表面積大之多孔型、孔型、巨孔型或巨網狀型較佳。The strong basic anion exchanger, the weakly basic anion exchanger and the chelating material used in the present invention can be used for alkali-resistant synthetic resin fibers or synthetic resin beads, strong basic anion exchangers, weakly basic anions Exchanger and chelating material binder. Further, such a structure may, for example, be a gel type, a porous type, a pore type, a macroporous type or a giant network type, and particularly a porous type, a pore type, a macroporous type or a giant network type having a large specific surface area. Preferably.
耐鹼性之合成樹脂纖維或合成樹脂珠之基體的合成樹脂，可例示如聚乙烯乙醇、苯乙烯－二乙烯苯共聚物、聚碸、聚苯碸、聚羥基甲基丙烯酸酯、聚乙烯、聚丙烯、醯胺、PFA(四氟乙烯．全氟烷基乙烯醚共聚物)、PTFE(聚四氟乙烯)系樹脂等，而以泛用性、價格等觀點，以聚乙烯乙醇、苯乙烯－二乙烯苯共聚物、醯胺、聚碸、聚苯碸等為佳。該等之合成樹脂，對於高濃度之鹼水溶液(例如，50%氫氧化鈉水溶液)亦具有高耐性。該等，可單獨使用、亦可組合複數種類使用。Examples of the synthetic resin of the matrix of the alkali-resistant synthetic resin fiber or the synthetic resin bead include, for example, polyvinyl alcohol, styrene-divinylbenzene copolymer, polyfluorene, polyphenylene fluorene, polyhydroxymethacrylate, polyethylene, Polypropylene, decylamine, PFA (tetrafluoroethylene, perfluoroalkyl vinyl ether copolymer), PTFE (polytetrafluoroethylene) resin, etc., and in terms of versatility, price, etc., polyethylene ethanol, styrene - Divinylbenzene copolymer, decylamine, polyfluorene, polyphenyl hydrazine or the like is preferred. These synthetic resins are also highly resistant to high concentrations of aqueous alkali solutions (e.g., 50% aqueous sodium hydroxide solution). These may be used singly or in combination of plural types.
該等基體之鍵結於合成樹脂之強鹼性陰離子交換基，可例示如4級胺基，弱鹼性陰離子交換基，可例示如1級胺基、2級胺基、3級胺基等，螯合化基，可例示如乙烯二胺基三乙酸基等聚胺基聚羧酸基、亞胺基二乙酸基、亞胺基乙酸基、胺基磷酸基、磷酸基、聚胺基、硫代化合物類基等。The base is bonded to a strongly basic anion exchange group of a synthetic resin, and examples thereof include a 4-stage amine group and a weakly basic anion exchange group, and examples thereof include a 1-stage amine group, a 2-stage amine group, a 3-stage amine group, and the like. The chelating group may, for example, be a polyaminopolycarboxylic acid group such as an ethylenediaminetriacetoxy group, an imidodiacetic acid group, an imidoacetic acid group, an aminophosphoric acid group, a phosphoric acid group or a polyamine group. A thio compound group or the like.
本發明所使用之以硝酸處理之活性碳的碳材料，可為椰子殼、石炭、石油瀝青、酚醛樹脂等任一者，活性碳，可使用纖維狀或珠狀等形狀者。於本發明處理活性碳的硝酸濃度，以6.5N以上較佳，處理時間以與活性碳接觸1酚醛樹脂小時以上較佳。又，本發明所使用之纖維狀或珠狀之以硝酸處理的活性碳，亦可作成濾筒狀。The carbon material of the activated carbon treated with nitric acid used in the present invention may be any of coconut shell, charcoal, petroleum pitch, phenol resin, and the like, and the activated carbon may be in the form of a fiber or a bead. The nitric acid concentration of the activated carbon treated in the present invention is preferably 6.5 N or more, and the treatment time is preferably in contact with the activated carbon for 1 hour or more. Further, the fibrous or beaded nitric acid-treated activated carbon used in the present invention may be formed into a filter cylinder.
該等之使用方法，可舉例如下述者。可將選自強鹼性陰離子交換體、弱鹼性陰離子交換體、螯合化材料、以及以硝酸處理之活性碳中之1種或2種以上充填至管柱或塔中，當為2種以上時，係以混合或層合的形式充填，或分別充填2種以上於個別之管柱或塔中後連結，並使欲精製之鹼水溶液通過其中。Examples of such methods of use include the following. One or more selected from the group consisting of a strong basic anion exchanger, a weakly basic anion exchanger, a chelating material, and an activated carbon treated with nitric acid may be filled into a column or a column, and two or more types may be used. In the case of mixing or laminating, two or more kinds are separately filled in individual columns or columns, and then connected, and an aqueous alkali solution to be purified is passed therethrough.
又，亦可將選自強鹼性陰離子交換體、弱鹼性陰離子交換體、螯合材料、以及以硝酸處理之活性碳中之1種或2種以上層合或混合於同一反應槽內，使欲精製之鹼水溶液流動，接著以過濾器過濾。Further, one or two or more selected from the group consisting of a strong basic anion exchanger, a weakly basic anion exchanger, a chelating material, and an activated carbon treated with nitric acid may be laminated or mixed in the same reaction vessel. The aqueous alkali solution to be purified flows, followed by filtration through a filter.
本發明之方法，其特徵係，即使鹼水溶液之鹼為高濃度亦可使用，鹼的濃度為0.01重量%以上、特別是0.1重量%以上，亦可精製。The method of the present invention is characterized in that even if the base of the aqueous alkali solution is used in a high concentration, the concentration of the alkali is 0.01% by weight or more, particularly 0.1% by weight or more, and it can be purified.
藉由本發明之方法，可將進行金屬除去處理後之鹼水溶液中之金屬濃度，例如，鈣、鎂、錳、鐵、鈷、鋅、鋁、鉛等的濃度精製為50ppb以下。According to the method of the present invention, the concentration of the metal in the aqueous alkali solution after the metal removal treatment, for example, the concentration of calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, lead or the like can be refined to 50 ppb or less.
本發明之金屬雜質的去除，例如，於圖1所示之鹼的濃度為高濃度的情形下，金屬會形成負電荷之氫氧化物錯離子，故可使用陰離子交換體，並且，即使於存在於鹼水溶液中之多量的陰離子之氫氧化物離子的共存下，亦可選擇性地吸附除去與陰離子交換基親和性高的氫氧化物錯離子。In the removal of the metal impurities of the present invention, for example, in the case where the concentration of the base shown in FIG. 1 is a high concentration, the metal forms a negatively charged hydroxide wrong ion, so that an anion exchanger can be used, and even if present In the coexistence of a large amount of anion hydroxide ions in the aqueous alkali solution, hydroxide hydroxide ions having high affinity with the anion exchange group can be selectively adsorbed and removed.
此時，當為螯合化材料時，負電荷之氫氧化物錯離子，可考量為螯合化材料取代該氫氧化物錯離子與金屬離子鍵結而除去，而較佳為，使用具有較金屬離子與配位基之氫氧化物離子之鍵結更強螯合力之官能基。At this time, when it is a chelate material, a negatively charged hydroxide stray ion may be considered as a chelate material instead of the hydroxide dislocation ion and metal ion linkage to remove, and preferably, the use has A functional group having a stronger chelation force for the bonding of a metal ion to a hydroxide ion of a ligand.
藉由本發明，可將低濃度至高濃度之鹼水溶液中所含之金屬雜質，以簡便的方法快速地除去。According to the present invention, metal impurities contained in a low-concentration to high-concentration aqueous alkali solution can be quickly removed in a simple manner.
具體而言，當為銅及鎳時，可達成以除去率50%以上之至其濃度為3ppb以下、視條件為0.1ppb以下的除去。又，本發明，除實施例所示之氫氧化鈉、氫氧化鉀、碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、氨水、氫氧化四甲銨溶液以外，亦適用於氫氧化鋰、氫氧化銫等鹼金屬氫氧化物溶液或氫氧化鋇等鹼土類金屬氫氧化物溶液、纖維素等鹼性水溶性高分子水溶液、乙酸銨等有機鹼水溶液的精製。Specifically, in the case of copper or nickel, removal with a removal ratio of 50% or more to a concentration of 3 ppb or less and an apparent condition of 0.1 ppb or less can be achieved. Further, the present invention is also applicable to lithium hydroxide, in addition to sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, aqueous ammonia or tetramethylammonium hydroxide solution as shown in the examples. An alkali metal hydroxide solution such as barium hydroxide or an alkaline earth metal hydroxide solution such as barium hydroxide, an aqueous solution of an alkali water-soluble polymer such as cellulose, or an aqueous solution of an organic alkali such as ammonium acetate.
本發明之有效之鹼水溶液的濃度，較佳為，氫氧化鈉為0.01~50重量%、氫氧化鉀為0.01~50重量%、碳酸鈉為0.01~23重量%、碳酸鉀為0.01~50重量%、碳酸氫鈉為0.01~8重量%、碳酸氫鉀為0.01~50重量%、氨水為0.01~30重量%、氫氧化四甲銨為0.01~25重量%，更佳為，氫氧化鈉為0.1~50重量%、氫氧化鉀為0.1~50重量%、碳酸鈉為0.1~23重量%、碳酸鉀為0.1~50重量%、碳酸氫鈉為0.1~50重量%、碳酸氫鉀為0.1~50重量%、氨水為0.1~30重量%、氫氧化四甲銨為0.1~25重量%之濃度。特佳為，氫氧化鈉為5~50重量%、氫氧化鉀為5~50重量%、碳酸鈉為5~23重量%、碳酸鉀為5~50重量%、碳酸氫鈉為5~8重量%、碳酸氫鉀為5~50重量%、氨水為5~30重量%、氫氧化四甲銨為5~25重量%之高濃度範圍，此時，可發揮本發明之最佳效果。The concentration of the effective aqueous alkali solution of the present invention is preferably 0.01 to 50% by weight of sodium hydroxide, 0.01 to 50% by weight of potassium hydroxide, 0.01 to 23% by weight of sodium carbonate, and 0.01 to 50% by weight of potassium carbonate. %, sodium hydrogencarbonate is 0.01 to 8% by weight, potassium hydrogencarbonate is 0.01 to 50% by weight, ammonia water is 0.01 to 30% by weight, and tetramethylammonium hydroxide is 0.01 to 25% by weight, more preferably, sodium hydroxide is 0.1 to 50% by weight, potassium hydroxide is 0.1 to 50% by weight, sodium carbonate is 0.1 to 23% by weight, potassium carbonate is 0.1 to 50% by weight, sodium hydrogencarbonate is 0.1 to 50% by weight, and potassium hydrogencarbonate is 0.1 to 0.1% by weight. 50% by weight, ammonia water is 0.1 to 30% by weight, and tetramethylammonium hydroxide is 0.1 to 25% by weight. Particularly preferably, the sodium hydroxide is 5 to 50% by weight, the potassium hydroxide is 5 to 50% by weight, the sodium carbonate is 5 to 23% by weight, the potassium carbonate is 5 to 50% by weight, and the sodium hydrogencarbonate is 5 to 8 weight. %, potassium bicarbonate is 5 to 50% by weight, ammonia water is 5 to 30% by weight, and tetramethylammonium hydroxide is 5 to 25% by weight in a high concentration range. In this case, the best effect of the present invention can be exhibited.
接著，說明本發明之實施例。Next, an embodiment of the present invention will be described.
作為試樣用之鹼水溶液，使用旭硝子(股)製之50%氫氧化鈉水溶液、旭硝子(股)製之48%氫氧化鉀水溶液、和光純藥工業(股)製特級碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀、關東化學(股)製之28~30%之特級氨水、氫氧化四甲銨五水和物、纖維素、富山藥品工業(股)製之70%乙酸銨水溶液，以以下之方法精製。又，進行實驗時之溶解、稀釋等操作全部皆使用超純水。又，特別為了觀察濃度的依存性，隊進行稀釋使金屬雜質至少為0.1重量%及0.01重量%氫氧化鈉，以使探討對象之金屬分別為10ppb左右的方式添加以實施精製處理。As the aqueous alkali solution for the sample, a 50% aqueous sodium hydroxide solution manufactured by Asahi Glass Co., Ltd., a 48% potassium hydroxide aqueous solution manufactured by Asahi Glass Co., Ltd., and a special grade sodium carbonate and potassium carbonate manufactured by Wako Pure Chemical Industries Co., Ltd. Sodium bicarbonate, potassium bicarbonate, 28~30% special grade ammonia water made by Kanto Chemical Co., Ltd., tetramethylammonium hydroxide pentahydrate and cellulose, 70% ammonium acetate aqueous solution made by Toyama Pharmaceutical Industry Co., Ltd. It was refined by the following method. In addition, ultrapure water was used for all operations such as dissolution and dilution during the experiment. Further, in order to observe the concentration dependency, the team was diluted to have a metal impurity of at least 0.1% by weight and 0.01% by weight of sodium hydroxide, and the metal to be investigated was added to a concentration of about 10 ppb to perform a purification treatment.
金屬雜質之測定，係以ICP－MS(珀金埃爾默(PerkinElmer)公司製，ELANDRC－II)進行。又，矽化合物及無機碳酸的測定，矽化合物係以ICP－AES((股)理學製，CIROS120)、無機碳酸係以NDIR法((股)島津製作所製，TOC5000A)進行。又，以下之實施例及比較例所使用之處理裝置及處理體，係如以下所述者。The measurement of the metal impurities was carried out by ICP-MS (Perkin Elmer, ELANDRC-II). In addition, the ruthenium compound was measured by ICP-AES (CIROS 120), and the inorganic carbonic acid was produced by the NDIR method (TOC5000A, manufactured by Shimadzu Corporation). Moreover, the processing apparatus and the processing body used in the following examples and comparative examples are as follows.
處理裝置：處理體充填管柱3/4英吋PFA管柱200mm(PFA：四氟乙烯－全氟烷基乙烯醚共聚物)試驗系及使用筒之材質PTFE(聚四氟乙烯)泵((股)伊瓦基公司製伸縮泵FS－15HT)Treatment device: treatment body filling column 3/4 inch PFA column 200mm (PFA: tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer) test system and tube material PTFE (polytetrafluoroethylene) pump (( Shares) Iwaji company telescopic pump FS-15HT)
使用之處理體：(A)強鹼性陰離子交換纖維：製造商：(股)匿其比(Nitivy)商品名：IEF－SA母材：聚乙烯乙醇官能基：4級胺基形狀：直徑100 μm、長度2~5mm纖維狀(B)弱鹼性離子交換纖維：製造商：(股)匿其比商品名：IEF－WA母材：聚乙烯乙醇官能基：1級~3級胺基形狀：直徑100 μm、長度2~5mm纖維狀(C)弱鹼性陰離子交換樹脂：製造商：羅門哈斯日本(Rohm and Haas Japan)(股)商品名：DUOLITE A3780D母材：苯乙烯．二乙烯苯共聚物官能基：1級~3級胺基形狀：直徑400~650 μm之珠狀(D)乙烯二胺基三乙酸．亞胺基二乙酸混合螯合樹脂製造商：(股)日立先端技術商品名：NOBIAS CHELATE－PA1母材：聚羥基甲基丙烯酸酯官能基：乙烯二胺基三乙酸基、亞胺基二乙酸基形狀：45~90 μm之珠狀(E)螯合纖維：製造商：(股)匿其比商品名：IEF－IAc母材：聚乙烯乙醇官能基：亞胺基乙酸基形狀：直徑100 μm、長度2~5mm纖維狀(F)強鹼性陰離子交換樹脂：製造商：羅門哈斯日本(股)商品名：A201CL母材：苯乙烯．二乙烯苯共聚物官能基：4級胺基形狀：直徑500~750 μm之珠狀(G)強酸性陽離子交換樹脂：製造商：羅門哈斯日本(股)商品名：DUOLITE C255LFH母材：苯乙烯．二乙烯苯共聚物官能基：磺酸基形狀：粒徑550 μm之珠狀(H)活性碳：製造商：三菱化學卡爾岡(股)商品名：W 10－30母材：椰子殼系形狀：粒徑10~35mesh(I)活性碳：製造商：三菱化學卡爾岡(股)商品名：Filtrasorb 400母材：石炭系形狀：粒徑10~35mesh(J)超過濾膜：製造商：(股)阿德凡鐵克(Advantec)商品名：超過濾膜Q0100母材：聚碸分劃分子量MWCO 10000形狀：直徑76mm薄膜(K)活性碳過濾器：製造商：(股)羅其鐵克儂(Roki Techno)商品名：Micro Charcoal MCK型母材：纖維狀活性碳、椰子殼活性碳Treatment body used: (A) Strongly basic anion exchange fiber: Manufacturer: (share) Nitvy (Nitivy) Trade name: IEF-SA Base material: Polyethylene ethanol Functional group: Grade 4 Amine shape: Diameter 100 Mm, length 2~5mm fibrous (B) weakly basic ion exchange fiber: manufacturer: (share) stealing its trade name: IEF-WA base metal: polyethylene alcohol functional group: grade 1 ~ 3 amine shape : 100 μm diameter, length 2~5mm fibrous (C) weakly basic anion exchange resin: Manufacturer: Rohm and Haas Japan (stock) Trade name: DUOLITE A3780D base metal: styrene. Divinylbenzene copolymer functional group: Grade 1~3 amine shape: Beaded (D) ethylenediaminetriacetic acid with a diameter of 400~650 μm. Iminodiacetic acid mixed chelate resin manufacturer: (share) Hitachi apex technology trade name: NOBIAS CHELATE-PA1 base material: polyhydroxy methacrylate functional group: ethylene diamine triacetate, imido diacetic acid Base shape: 45~90 μm beaded (E) chelated fiber: manufacturer: (share) hide its trade name: IEF-IAc base metal: polyethylene alcohol functional group: iminoacetic acid base shape: diameter 100 Mm, length 2~5mm fibrous (F) strong basic anion exchange resin: manufacturer: Rohm and Haas Japan (stock) trade name: A201CL base material: styrene. Divinylbenzene copolymer Functional group: Grade 4 amine base shape: beaded (G) strong acid cation exchange resin with diameter 500~750 μm: manufacturer: Rohm and Haas Japan (stock) trade name: DUOLITE C255LFH base material: benzene Ethylene. Divinylbenzene copolymer Functional group: Sulfonic acid group shape: Beads with a particle size of 550 μm (H) Activated carbon: Manufacturer: Mitsubishi Chemical Kalkan (stock) Trade name: W 10-30 Base material: Coconut shell shape : Particle size 10~35mesh(I) Activated carbon: Manufacturer: Mitsubishi Chemical Calgon (share) Trade name: Filtrasorb 400 Base material: Carboniferous Shape: Particle size 10~35mesh (J) Ultrafiltration membrane: Manufacturer: ( Shares: Advantec Trade name: Ultrafiltration membrane Q0100 Base material: Polyfluorene molecular weight MWCO 10000 Shape: Diameter 76mm Film (K) Activated carbon filter: Manufacturer: (share) Roche Tieke Roki Techno Product Name: Micro Charcoal MCK Base Material: Fibrous Activated Carbon, Coconut Shell Activated Carbon
又，於以下之實施例及比較例中，所使用之處理體，係以上述(A)、(B)、...之簡稱表示。此處所使用之(A)、(B)、(C)、(F)之離子交換體，係使用末端基的90%以上為OH基者。Further, in the following examples and comparative examples, the treatment bodies used are indicated by the abbreviations of the above (A), (B), .... The ion exchangers of (A), (B), (C), and (F) used herein are those in which 90% or more of the terminal groups are OH groups.
(使用器具等之洗淨)為了排除金屬污染，事先將PTFE製筒(容積1200ml)、PFA製管柱(3/4英吋、長度200mm)、取樣用PE(聚乙烯)製容器(容積1000ml)全部，浸漬於1N硝酸1小時以上後，以超純水流水洗淨。洗淨所使用之硝酸，係關東化學(股)製之電子工業用等級(EL)，以超純水稀釋成約1N者。超純水，係以超純水製造系統所製造之金屬含量為各金屬1ppt以下、Si 50ppt以下、無機碳10ppb以下者。(washing with utensils, etc.) In order to eliminate metal contamination, a PTFE cylinder (1200 ml) and a PFA column are used in advance ( 3/4 inch, length 200 mm), and a PE (polyethylene) container (volume 1000 ml) for sampling was immersed in 1 N nitric acid for 1 hour or more, and then washed with ultrapure water. The nitric acid used for washing is an electronic industrial grade (EL) manufactured by Kanto Chemical Co., Ltd., and diluted to about 1N with ultrapure water. Ultrapure water is a metal content of an ultrapure water production system of 1 ppt or less, Si 50 ppt or less, and inorganic carbon of 10 ppb or less.
將以上述洗淨方法洗淨之器具以PTFE製筒、PFA管柱的順序以PFA配管連接。使超純水通過該系統，於PFA出口由PE容器接受時之試驗系作為空白試驗的分析結果，示於表1。由表1可知，該系統完全無污染。The apparatus which was washed by the above-described washing method was connected by a PFA pipe in the order of a PTFE cylinder or a PFA column. The test results obtained when the ultrapure water was passed through the system and accepted by the PE container at the PFA outlet as a blank test are shown in Table 1. As can be seen from Table 1, the system is completely free of pollution.
(處理操作)將對象物之鹼水溶液以成分濃度不改變的方式對末端基施以處理之(A)~(G)之各種吸附體，充填於PFA管柱(3/4英吋、長度200mm)。又，(H)、(I)之活性碳，係事先浸漬於6.5N硝酸中1小時以洗淨後使用。充填，係一邊以充分洗淨之PTFE製之擠壓棒輕輕地將吸附體押入，一邊緩緩地充填，並以使管柱內部為緊密的方式充填。(Processing operation) The various adsorbents of (A) to (G) are applied to the terminal base in such a manner that the concentration of the component does not change, and the alkali aqueous solution of the object is filled in the PFA column ( 3/4 inches, length 200mm). Further, the activated carbons of (H) and (I) were previously immersed in 6.5 N nitric acid for 1 hour to be washed and used. The filling was carried out while gently pushing the adsorbent into the PTFE-made extruded rod, and filling it slowly, so that the inside of the column was tightly packed.
於充填有吸附體之PFA管柱，使超純水以10ml/min沖提12小時以上，將溶出之金屬或有機物充分地洗淨流去。以使PTFE製筒之內部不殘留水滴的方式將水停掉，投入試樣之鹼水溶液之50%NaOH。將投入鹼水溶液之PTFE製筒與洗淨之充填有充填物之PFA管柱以1/4英吋之PFA管連接，並於PFA管柱出口設置取樣容器。The PFA column packed with the adsorbent was subjected to pulverization of ultrapure water at 10 ml/min for 12 hours or more, and the eluted metal or organic matter was sufficiently washed and discharged. The water was stopped so that no water droplets remained inside the PTFE cylinder, and 50% NaOH of the alkali aqueous solution of the sample was charged. The PTFE cylinder charged with the aqueous alkali solution and the washed PFA column packed with the filler were connected to a 1/4 inch PFA tube, and a sampling container was placed at the outlet of the PFA column.
由PTFE製筒的上部導入氮氣，將容器內部之壓力加壓至0.2MPa並操作流量調整閥以將由PFA管柱出口所流出之鹼水溶液的流出速度調整為5ml/min以下。將流出之鹼水溶液之pH以pH試紙測定，當與所供給之鹼水溶液相同時，將PFA管柱出口之液體以PE容器接收以取樣。又，以分析確定取樣係與所供給之鹼水溶液相同成分濃度(例如，氫氧化鈉係測定入口出口之Na濃度)。Nitrogen gas was introduced from the upper portion of the PTFE cylinder, and the pressure inside the vessel was pressurized to 0.2 MPa, and the flow rate adjusting valve was operated to adjust the flow rate of the aqueous alkali solution flowing out from the outlet of the PFA column to 5 ml/min or less. The pH of the aqueous alkali solution flowing out was measured by a pH test paper, and when it was the same as the supplied aqueous alkali solution, the liquid at the outlet of the PFA column was received as a sample in a PE container. Further, the concentration of the same component of the sample system and the supplied aqueous alkali solution is determined by analysis (for example, sodium hydroxide is used to measure the Na concentration of the inlet and outlet).
接收於PE容器內之鹼水溶液立即密封，並以ICP－MS、ICP－AES、NDIR法進行金屬、矽化合物及無機碳酸之分析。金屬分析項目，係銅、鎳等容易擴散至晶圓內部之金屬、與鈣、鎂、錳、鐵、鈷、鋅、鋁、鉛等殘留於晶圓表面之金屬。The aqueous alkali solution received in the PE container was immediately sealed, and analysis of the metal, cerium compound and inorganic carbonic acid was carried out by ICP-MS, ICP-AES, and NDIR methods. The metal analysis project is a metal that is easily diffused into the inside of the wafer such as copper or nickel, and a metal that remains on the surface of the wafer such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, or lead.
於ICP－MS之分析，作為分析器導入前之處理，可視需要以固相萃取法進行Na及K成分之除去。For the analysis by ICP-MS, as the treatment before the introduction of the analyzer, the Na and K components can be removed by solid phase extraction as needed.
又，本實施例、以下之各實施例及比較例之處理體量為40ml、試樣沖提速度為5ml/min以下、沖提液體量為1000ml、沖提皆為1次通過，並以20~25℃之溫度條件進行，但25℃以上之鹼水溶液只要使用構件具耐熱性亦可使用。Further, in the examples, the following examples and comparative examples, the amount of the treated body was 40 ml, the sample rinsing speed was 5 ml/min or less, the amount of the rinsing liquid was 1000 ml, and the rinsing was performed once, and was 20 It is carried out under the temperature condition of ~25 ° C, but the alkali aqueous solution of 25 ° C or more can be used as long as the member is heat-resistant.
結果示於表2。The results are shown in Table 2.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)(J)之超過濾膜係以超純水流通12小時洗淨後使用。又，(K)之活性碳過濾器，係事先浸漬於6.5N硝酸中1小時以進行洗淨，並以超純水流通12小時洗淨後使用。洗淨之過濾器，插入專用之匣內，以泵將鹼水溶液沖提後，以ICP－MS、ICP－AES、NDIR法測定過濾液之金屬、矽化合物及無機碳酸之濃度。金屬分析項目，係銅、鎳等容易擴散至晶圓內部之金屬、與鈣、鎂、錳、鐵、鈷、鋅、鋁、鉛等殘留於晶圓表面之金屬。(Processing operation) The ultrafiltration membrane of (J) was used after being purged for 12 hours in ultrapure water. Further, the activated carbon filter of (K) was washed by immersing in 6.5 N nitric acid for 1 hour in advance, and was washed with ultrapure water for 12 hours and then used. The washed filter was inserted into a special crucible, and the alkali aqueous solution was pumped out by a pump, and the concentrations of the metal, the cerium compound, and the inorganic carbonic acid of the filtrate were measured by ICP-MS, ICP-AES, and NDIR. The metal analysis project is a metal that is easily diffused into the inside of the wafer such as copper or nickel, and a metal that remains on the surface of the wafer such as calcium, magnesium, manganese, iron, cobalt, zinc, aluminum, or lead.
結果示於表2。The results are shown in Table 2.
以下之實施例10~47，係以實施例1~9中之特別對銅、鎳等容易擴散至晶圓內部之金屬可得良好之除去結果為對象進行試驗。過濾液之金屬分析項目，係以銅、鎳等容易擴散至晶圓內部之金屬、與鐵、鋅、鋁、鉛等容易殘留於晶圓表面而造成洗淨負擔之金屬為對象。In the following Examples 10 to 47, the results of the removal of the metal which is easily diffused into the inside of the wafer, such as copper or nickel, in Examples 1 to 9 were tested. The metal analysis item of the filtrate is a metal which is easily diffused into the inside of the wafer such as copper or nickel, and a metal which is likely to remain on the surface of the wafer such as iron, zinc, aluminum or lead to cause a cleaning load.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)與上述以相同方法，將實施例10之混合(A)強鹼性陰離子交換纖維及(B)弱鹼性陰離子交換纖維之試樣、實施例11之混合(A)及(D)乙烯二胺基三乙酸．亞胺基二乙酸混合螯合樹脂之試樣、實施例12之將(A)及(B)的混合體與(D)排成直列的試樣充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) The mixture of (A) strongly basic anion exchange fiber and (B) weakly basic anion exchange fiber of Example 10, and the mixture (A) and (D) of Example 11 were treated in the same manner as above. Ethylene diamine triacetic acid. A sample of the imidodiacetic acid mixed chelating resin, a mixture of (A) and (B) of Example 12, and (D) an inline sample are filled in the column, and Examples 1 to 8 The refining treatment was carried out in the same manner.
結果示於表3。The results are shown in Table 3.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)將處理對象之50%NaOH以經超純水稀釋之0.1%NaOH取代，將實施例13之混合(A)及(B)之試樣、實施例14之(C)弱鹼性陰離子交換樹脂、實施例15之將(A)及(B)的混合體與(D)排成直列的試樣、比較例4之(G)強酸性陽離子交換樹脂充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) 50% NaOH of the treated object was replaced with 0.1% NaOH diluted with ultrapure water, and the sample of the mixture of (A) and (B) of Example 13 and the weakly alkaline of Example (C) of Example 14 were used. The anion exchange resin, the mixture of (A) and (B) of Example 15 and (D) the in-line sample, and the (G) strong acid cation exchange resin of Comparative Example 4 were filled in a column, and were carried out. Examples 1 to 8 were subjected to purification treatment in the same manner.
結果示於表4。The results are shown in Table 4.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)將處理對象之50%NaOH以經超純水稀釋之0.01%NaOH取代，將實施例16之混合(A)及(B)之試樣、實施例17之(C)、實施例18之將(A)及(B)的混合體與(D)排成直列的試樣、比較例6之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) The 50% NaOH of the treatment object was replaced with 0.01% NaOH diluted with ultrapure water, and the sample of the mixture of (A) and (B) of Example 16, the (C) of Example 17, and the Example In the 18th, the mixture of (A) and (B) and the (D) in-line sample, and the comparative example 6 (G) were filled in the column, and the polishing treatment was carried out in the same manner as in Examples 1 to 8.
結果示於表5。The results are shown in Table 5.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例19~21將處理對象之鹼水溶液取代成48%KOH，將實施例19之混合(A)及(B)之試樣、實施例20之(C)、實施例21之將(A)及(B)的混合體與(D)排成直列的試樣、比較例8之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the examples 19 to 21, the aqueous alkali solution to be treated was replaced with 48% KOH, and the sample of the mixture of (A) and (B) of Example 19, (C) of Example 20, and Example 21 were used. The mixture of (A) and (B) and (D) the in-line sample and the comparative example 8 (G) were filled in the column, and the polishing treatment was carried out in the same manner as in Examples 1 to 8.
結果示於表6。The results are shown in Table 6.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例22~24將處理對象之鹼水溶液取代成23%Na2 CO3 ，將實施例22之混合(A)及(B)之試樣、實施例23之(C)、實施例24之將(A)及(B)的混合體與(D)排成直列的試樣、比較例10之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the examples 22 to 24, the aqueous alkali solution to be treated was replaced with 23% Na 2 CO 3 , and the sample of the mixture of (A) and (B) of Example 22, and (C) of Example 23, In the example 24, the mixture of (A) and (B) and (D) the in-line sample and the comparative example 10 (G) were filled in the column, and the samples were refined in the same manner as in Examples 1 to 8. deal with.
結果示於表7。The results are shown in Table 7.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例25~27將處理對象之鹼水溶液取代成50%K2 CO3 ，將實施例25之混合(A)及(B)之試樣、實施例26之(C)、實施例27之將(A)及(B)的混合體與(D)排成直列的試樣、比較例12之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the examples 25 to 27, the aqueous alkali solution to be treated was replaced with 50% K 2 CO 3 , and the sample of the mixture of (A) and (B) of Example 25, and (C) of Example 26, In Example 27, the mixture of (A) and (B) and (D) the in-line sample and the comparative example 12 (G) were filled in the column, and the same procedure as in Examples 1 to 8 was carried out. deal with.
結果示於表8。The results are shown in Table 8.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例28~30將處理對象之鹼水溶液取代成8%NaHCO3 ，將實施例28之混合(A)及(B)之試樣、實施例29之(C)、實施例32之將(A)及(B)的混合體與(D)排成直列的試樣、比較例14之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the examples 28 to 30, the aqueous alkali solution to be treated was replaced with 8% NaHCO 3 , the sample of the mixture of (A) and (B) of Example 28, and the (C) and Example of Example 29 were used. In the mixture of (A) and (B), the mixture of (A) and (B) and the (D) of Comparative Example 14 were filled in a column, and the same treatments as in Examples 1 to 8 were carried out in the same manner.
結果示於表9。The results are shown in Table 9.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例31~33將處理對象之鹼水溶液取代成50%KHCO3 ，將實施例31之混合(A)及(B)之試樣、實施例32之(C)、實施例33之將(A)及(B)的混合體與(D)排成直列的試樣、比較例16之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In Examples 31 to 33, the aqueous alkali solution to be treated was replaced with 50% KHCO 3 , and the samples of Examples (A) and (B) of Example 31, (C) of Example 32, and Examples were used. In the mixture of (A) and (B), the mixture of (A) and (B) and the (D) of Comparative Example 16 were filled in a column, and the same treatment as in Examples 1 to 8 was carried out in the same manner.
結果示於表10。The results are shown in Table 10.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例34~36將處理對象之鹼水溶液取代成28%之氨水，將實施例34之混合(A)及(B)之試樣、實施例35之(C)、實施例36之將(A)及(B)的混合體與(D)排成直列的試樣、比較例18之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the examples 34 to 36, the aqueous alkali solution to be treated was replaced with 28% aqueous ammonia, and the sample of the mixture of (A) and (B) of Example 34, (C) of Example 35, and Example In the mixture of (A) and (B), the mixture of (A) and (B) was placed in a line, and (G) of Comparative Example 18 was filled in a column, and the same treatments as in Examples 1 to 8 were carried out in the same manner.
結果示於表11。The results are shown in Table 11.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)於實施例37~39將處理對象之鹼水溶液取代成25%之氫氧化四甲銨水溶液，將實施例37之混合(A)及(B)之試樣、實施例38之(C)、實施例39之將(A)及(B)的混合體與(D)排成直列的試樣、比較例20之(G)充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the examples 37 to 39, the aqueous alkali solution to be treated was replaced with a 25% aqueous solution of tetramethylammonium hydroxide, and the sample of the mixture of (A) and (B) of Example 37, and Example 38 ( C), the mixture of (A) and (B) and the sample of (D) arranged in line in Example 39, and (G) of Comparative Example 20 were filled in the column, and were the same as Examples 1 to 8. The method is refined.
結果示於表12。The results are shown in Table 12.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)與實施例1~8以相同方法，將實施例40之將(C)及(F)的混合體與(A)及(B)的混合體以此順序排成直列的試樣、實施例41之將(A)及(B)的混合體與(C)及(F)的混合體以此順序排成直列的試樣、實施例42之將(K)、(C)及(F)的混合體與(A)及(B)的混合體以此順序排成直列的試樣充填於管柱中，與實施例1~8以相同方法進行精製處理。(Processing operation) In the same manner as in Examples 1 to 8, the mixture of (C) and (F) and the mixture of (A) and (B) of Example 40 were arranged in an in-line sample in this order. In the embodiment 41, the mixture of (A) and (B) and the mixture of (C) and (F) are arranged in parallel in this order, and (K) and (C) of Example 42 and The mixture of (F) and the mixture of (A) and (B) were packed in a column in this order, and the sample was filled in the same manner as in Examples 1 to 8.
結果示於表13。The results are shown in Table 13.
(使用器具之洗淨)為了排除金屬污染，事先將PTFE製筒(容積1200ml)、取樣用PE(聚乙烯)製容器(容積1000ml)全部，浸漬於1N硝酸1小時以上後，以超純水流水洗淨。(washing with an appliance) In order to eliminate metal contamination, a PTFE cylinder (volume: 1200 ml) and a sample PE (polyethylene) container (volume: 1000 ml) were all immersed in 1N nitric acid for 1 hour or more, and ultrapure water was used. Wash the water.
洗淨所使用之硝酸，係關東化學(股)製之電子工業用等級(EL)，以超純水稀釋成約1N者。超純水，係以超純水製造系統所製造之金屬含量為各金屬1ppt以下、Si 50ppt以下、無機碳10ppb以下者。The nitric acid used for washing is an electronic industrial grade (EL) manufactured by Kanto Chemical Co., Ltd., and diluted to about 1N with ultrapure water. Ultrapure water is a metal content of an ultrapure water production system of 1 ppt or less, Si 50 ppt or less, and inorganic carbon of 10 ppb or less.
(處理操作)作為實施例43、44，於PTFE製筒(容積1200ml)中，將50%NaOH及50%KOH分別與(C)接觸24小時，以批次法進行精製處理。(Processing operation) As Examples 43 and 44, 50% NaOH and 50% KOH were each contacted with (C) for 24 hours in a PTFE cylinder (volume: 1200 ml), and subjected to a purification treatment by a batch method.
結果示於表14。The results are shown in Table 14.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)作為實施例45~47，於PTFE製筒(容積1200ml)中貯留50%NaOH，投入4英吋晶圓，以80℃加熱3小時後，徐冷後者作為比較例10之鹼水溶液。將其與(A)接觸24小時以批次法及將(A)與(B)與實施例1~9同樣地以管柱進行精製處理。(Processing operation) As Examples 45 to 47, 50% NaOH was stored in a PTFE cylinder (volume: 1200 ml), and a 4-inch wafer was charged, and after heating at 80 ° C for 3 hours, the latter was used as the alkali aqueous solution of Comparative Example 10. . This was contacted with (A) for 24 hours, and the steps of the batch method and (A) and (B) were carried out in the same manner as in Examples 1 to 9 by a column.
結果示於表15。The results are shown in Table 15.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)作為實施例48~49、比較例22，將(A)強鹼性陰離子交換纖維、(E)螯合纖維及(G)強酸性陽離子交換樹脂20ml、與70%乙酸銨水溶液200ml，於PE製容器內混合，以批次法進行精製處理24小時。(Processing operation) As Examples 48 to 49 and Comparative Example 22, (A) strongly basic anion exchange fiber, (E) chelating fiber, and (G) strong acid cation exchange resin 20 ml, and 70% ammonium acetate aqueous solution 200 ml The mixture was mixed in a PE container and subjected to a batch process for 24 hours.
結果示於表16。The results are shown in Table 16.
(使用器具之洗淨)以與上述相同之方法將使用器具洗淨。(washing with an appliance) The appliance is washed in the same manner as described above.
(處理操作)作為實施例50、比較例24，將(E)螯合纖維及(G)強酸性陽離子交換樹脂20ml、與1%纖維素水溶液200ml，於PE製容器內混合，以批次法進行精製處理24小時。(Processing operation) As Example 50 and Comparative Example 24, 20 ml of (E) chelating fibers and (G) strongly acidic cation exchange resin and 200 ml of a 1% cellulose aqueous solution were mixed in a PE container by batch method. The refining treatment was carried out for 24 hours.
結果示於表17。The results are shown in Table 17.
於表2，使用比較例1所示之含金屬雜質之未處理之50%NaOH，進行實施例1~9之處理的結果，可確認金屬雜質之除去能力。但是，如實施例8或實施例9、實施例11，藉由與50%NaOH接觸亦可見金屬溶出的情形。In Table 2, the results of the treatments of Examples 1 to 9 were carried out using the untreated 50% NaOH containing the metal impurities shown in Comparative Example 1, and the ability to remove the metal impurities was confirmed. However, as in Example 8 or Example 9, Example 11, the dissolution of the metal was also observed by contact with 50% NaOH.
此處，如50%NaOH之強鹼溶液中，由於金屬作為陽離子化學源存在的比例低，故如比較例2所示，得到以一般之(G)強酸性陽離子交換樹脂無法除去金屬雜質之結果。另一方面，如實施例1~3、6，以陰離子交換樹脂或樹脂可有效地除去金屬雜質。特別是，如50%NaOH之易吸收碳酸雜質之容易時，可得弱鹼性陰離子交換基較強鹼性陰離子交換基更可有效地除去金屬雜質的結果。又，如實施例4及實施例5，具有特殊螯合官能基之纖維或樹脂亦可發揮金屬雜質之除去效果。Here, in the strong alkali solution of 50% NaOH, since the ratio of the metal as a cation chemical source is low, as shown in Comparative Example 2, the result that the general (G) strongly acidic cation exchange resin cannot remove the metal impurities is obtained. . On the other hand, as in Examples 1 to 3 and 6, metal impurities were effectively removed by an anion exchange resin or a resin. In particular, when 50% NaOH easily absorbs carbonic acid impurities, a weakly basic anion exchange group can be obtained, and a more basic anion exchange group can more effectively remove metal impurities. Further, as in Example 4 and Example 5, the fiber or resin having a specific chelating functional group can also exhibit the effect of removing metallic impurities.
然而，如比較例3使用超過濾法，亦無法除去微量的金屬雜質。However, as in Comparative Example 3, an ultrafiltration method was used, and a trace amount of metal impurities could not be removed.
於表3，組合於實施例1~9之試驗為良好之處理方法並調查其效果的結果，如實施例10~12顯示金屬雜質除去能力顯著地提昇。特別是對於銅與鎳，可除去至1.0ppb以下。In Table 3, the results of combining the tests of Examples 1 to 9 as good treatment methods and investigating the effects thereof, as in Examples 10 to 12, showed that the metal impurity removing ability was remarkably improved. Especially for copper and nickel, it can be removed to 1.0 ppb or less.
於表4及5，探討以與上述試驗特別良好之實施例3、實施例10及實施例12同樣的充填物實施、比較例4之使用(G)強酸性陽離子交換樹脂之情形。此處可知，於比較例4無法確認(G)之金屬除去能力，但於比較例6則有效地作用。亦即，於0.01重量%NaOH(pH＝11.4)以下，金屬亦作為陽離子化學源存在，可以習知法之陽離子交換法進行處理。然而，0.1重量%NaOH(pH＝12.4)左右之濃度，以習知法之陽離子交換法無法將金屬除去，而以本發明之精製方法為有效。In Tables 4 and 5, the case of using the same filling material as in Example 3, Example 10 and Example 12 in which the above tests were particularly excellent, and the case of using (G) strongly acidic cation exchange resin of Comparative Example 4 were examined. Here, it can be seen that the metal removal ability of (G) was not confirmed in Comparative Example 4, but it was effective in Comparative Example 6. That is, the metal is also present as a cation chemical source under 0.01% by weight of NaOH (pH = 11.4), and can be treated by a conventional cation exchange method. However, at a concentration of about 0.1% by weight of NaOH (pH = 12.4), the metal cannot be removed by a conventional cation exchange method, and the purification method of the present invention is effective.
以下之表6~12所示之實施例19~39，亦進行與以上處理相同之試驗，得到大致相同的結果。惟，使用碳酸鈉、碳酸鉀、碳酸氫鈉、碳酸氫鉀時，(A)強鹼性陰離子交換纖維會受到碳酸化學源的影響，可見除去能力多少有降低的傾向。又，表9及表10所示之碳酸氫鈉及碳酸氫鉀，由於係弱鹼性基，故以習知之陽離子交換法亦可得有效的結果。The same tests as in the above treatment were carried out in Examples 19 to 39 shown in Tables 6 to 12 below, and substantially the same results were obtained. However, when sodium carbonate, potassium carbonate, sodium hydrogencarbonate or potassium hydrogencarbonate is used, (A) the strongly basic anion exchange fiber is affected by the chemical source of carbonic acid, and the removal ability tends to be somewhat lowered. Further, since sodium hydrogencarbonate and potassium hydrogencarbonate shown in Tables 9 and 10 are weakly basic groups, effective results can be obtained by a conventional cation exchange method.
而於表13所示之實施例40~42，進行與以上處理相同之試驗的結果明白，當組合強鹼性陰離子交換纖維、弱鹼性陰離子纖維、強鹼性陰離子交換樹脂、弱鹼性陰離子交換樹脂時，具有特別優異之金屬雜質除去能力。Further, in the examples 40 to 42 shown in Table 13, the results of the same tests as those of the above treatment were understood, and when a strong basic anion exchange fiber, a weakly basic anion fiber, a strongly basic anion exchange resin, a weakly basic anion was combined, When the resin is exchanged, it has a particularly excellent metal impurity removing ability.
表14所示之以批次法之精製處理的實施例43及44，亦得到與實施例3及20同等或其以上之金屬雜質除去能力。Examples 43 and 44 which were subjected to the batch method as shown in Table 14 also obtained metal impurity removing ability equivalent to or higher than those of Examples 3 and 20.
表15所示之實施例45~47，進行與以上處理相同之試驗的結果明白，特別是矽化合物、無機碳酸可以強鹼性陰離子交換纖維除去精製。相反的，明白以弱鹼性陰離子交換纖維，並未除去矽化合物、無機碳酸。藉此，可知可視矽化合物及無機碳酸之除去精製之必要性的有無分別使用。In Examples 45 to 47 shown in Table 15, the results of the same tests as those of the above treatment were carried out, and it is understood that in particular, the ruthenium compound and the inorganic carbonic acid can be removed and purified by the strongly basic anion exchange fiber. On the contrary, it is understood that the weakly basic anion exchange fiber does not remove the ruthenium compound or inorganic carbonic acid. From this, it is understood that the necessity of removal and purification of the ruthenium compound and the inorganic carbonic acid can be used separately.
表16所示之70%乙酸銨水溶液(pH＝10.0)，以實施例48~49之(A)及(F)可確認效果，於比較例22之(G)無法確認效果。其理由，可考量為由於存在有高濃度之乙酸離子及銨離子，該等與金屬形成錯合物，而成為以(G)無法除去之金屬化學源存在。而負電荷之乙酸－金屬錯合物係以電氣吸附於(A)，而於(E)乙酸離子或銨離子則以更強之配位鍵結力吸附。The 70% aqueous ammonium acetate solution (pH = 10.0) shown in Table 16 was confirmed by the results (A) and (F) of Examples 48 to 49, and the effect was not confirmed in (G) of Comparative Example 22. The reason for this is that it is considered that there is a high concentration of acetate ions and ammonium ions, and these forms a complex with the metal, and are present as a metal chemical source which cannot be removed by (G). The negatively charged acetic acid-metal complex is electrically adsorbed to (A), while the (E) acetate ion or ammonium ion is adsorbed with a stronger coordination bond force.
表17所示之1%纖維素水溶液(pH＝11.0)，實施例50之(E)及比較例24之(G)可確認效果。由該結果，可考量為與比較例6同樣的金屬係亦作為陽離子化學源存在。The effect of the 1% aqueous cellulose solution (pH = 11.0) shown in Table 17, (E) of Example 50, and (G) of Comparative Example 24 was confirmed. From the results, it was considered that the same metal system as in Comparative Example 6 was also present as a cation chemical source.
本發明，可廣泛利用於含金屬雜質之鹼水溶液的精製。The present invention can be widely utilized for the purification of an aqueous alkali solution containing a metal impurity.
圖1，係顯示鹼水溶液中銅離子之存在狀態的圖。Fig. 1 is a view showing the state of existence of copper ions in an aqueous alkali solution.
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| JP5049528B2 (en) * | 2006-07-31 | 2012-10-17 | 東亞合成株式会社 | Method for producing high purity alkali metal hydroxide |
| JP5369440B2 (en) * | 2008-01-11 | 2013-12-18 | 東亞合成株式会社 | Method for producing high-purity alkali metal carbonate aqueous solution and continuous production method for high-purity alkali metal carbonate aqueous solution |
| JP2009167036A (en) * | 2008-01-11 | 2009-07-30 | Toagosei Co Ltd | Method for producing high purity alkali metal carbonate aqueous solution |
| JP2009167050A (en) * | 2008-01-15 | 2009-07-30 | Toagosei Co Ltd | Method for producing high purity alkali metal carbonate aqueous solution |
| JP5311227B2 (en) * | 2009-08-05 | 2013-10-09 | 野村マイクロ・サイエンス株式会社 | Anion exchanger, its pretreatment method and regeneration method, and purification method and purification apparatus of alkaline aqueous solution |
| JP2011051833A (en) * | 2009-09-02 | 2011-03-17 | Nomura Micro Sci Co Ltd | Method for purification of alkaline aqueous solution |
| JP2014188514A (en) * | 2013-03-28 | 2014-10-06 | Mitsubishi Chemicals Corp | Process for producing purified alkali metal aqueous solution |
| JP5648231B2 (en) * | 2013-05-22 | 2015-01-07 | 野村マイクロ・サイエンス株式会社 | Purification method of alkaline aqueous solution |
| CN112999694A (en) * | 2021-03-24 | 2021-06-22 | 沧州信联化工有限公司 | Raw material refining device for processing tetramethylammonium hydroxide and use method thereof |
| CN115744934B (en) * | 2022-11-29 | 2024-03-22 | 福建省龙德新能源有限公司 | Preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate |
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