TW202116996A - Treating liquid, kit, method for producing treating liquid, method for cleaning substrate and method for treating substrate - Google Patents

Treating liquid, kit, method for producing treating liquid, method for cleaning substrate and method for treating substrate Download PDF

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TW202116996A
TW202116996A TW109127573A TW109127573A TW202116996A TW 202116996 A TW202116996 A TW 202116996A TW 109127573 A TW109127573 A TW 109127573A TW 109127573 A TW109127573 A TW 109127573A TW 202116996 A TW202116996 A TW 202116996A
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treatment liquid
organic solvent
treatment
aforementioned
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TW109127573A
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高橋智威
清水哲也
水谷篤史
杉島泰雄
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日商富士軟片股份有限公司
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    • C—CHEMISTRY; METALLURGY
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    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—Ethers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
    • B08B3/04—Cleaning involving contact with liquid
    • B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
    • C—CHEMISTRY; METALLURGY
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    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/08—Liquid soap, e.g. for dispensers; capsuled
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    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
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    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
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    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
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    • C11D7/3272—Urea, guanidine or derivatives thereof
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    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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    • G03F7/42—Stripping or agents therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
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    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
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Abstract

The present invention addresses the problem of providing a treatment liquid that is for semiconductor devices and that provides excellent corrosion prevention performance to a metal layer. In addition, the present invention addresses the problem of providing a kit, a production method for the treatment liquid, a substrate cleaning method using the treatment liquid, and a substrate treatment method using the treatment liquid. The treatment liquid according to the present invention is for semiconductor devices, and contains water and an organic solvent, wherein the organic solvent has a pH of not less than 5, and includes at least a combination that comprises organic solvent A and organic solvent B and that is one of specific combinations 1-6.

Description

處理液、試劑盒、處理液的製造方法、基板的清洗方法、基板的處理方法Processing liquid, reagent kit, processing liquid manufacturing method, substrate cleaning method, substrate processing method

本發明係關於一種處理液、試劑盒、處理液的製造方法、基板的清洗方法及基板的處理方法。The present invention relates to a processing liquid, a reagent kit, a method for manufacturing a processing liquid, a method for cleaning a substrate, and a method for processing a substrate.

使用光微影技術，在基板上形成微細的電子電路圖案來製造CCD（Charge-Coupled Device，電荷耦合器件）及記憶體等半導體器件。半導體器件例如藉由在基板上配置作為配線材料之金屬層及具有蝕刻停止膜及層間絕緣膜之積層體，在該積層體上形成光阻膜，並實施光微影步驟及乾式蝕刻步驟（例如，電漿蝕刻處理）來製造。 具體而言，在光微影步驟中，將所獲得之光阻膜作為遮罩，藉由乾式蝕刻處理對基板上的金屬層及/或層間絕緣膜進行蝕刻。 此時，來自於金屬層及/或層間絕緣膜等的殘渣有時附著於基板、金屬層及/或層間絕緣膜。為了去除該附著之殘渣，多為進行使用處理液之清洗。 又，關於蝕刻時用作遮罩之光阻膜，之後藉由基於灰化（Ashing）的乾式方法（乾灰化）或濕式方法等而從積層體去除。使用乾灰化方法來去除阻劑之積層體中有時附著來自於光阻膜等的殘渣。為了去除該附著之殘渣，通常多為進行使用處理液之清洗。Using photolithography technology, a fine electronic circuit pattern is formed on the substrate to manufacture CCD (Charge-Coupled Device) and semiconductor devices such as memory. For semiconductor devices, for example, a metal layer as a wiring material and a laminate having an etching stop film and an interlayer insulating film are arranged on a substrate, a photoresist film is formed on the laminate, and a photolithography step and a dry etching step (such as , Plasma etching treatment) to manufacture. Specifically, in the photolithography step, the obtained photoresist film is used as a mask, and the metal layer and/or the interlayer insulating film on the substrate is etched by a dry etching process. At this time, residues from the metal layer and/or the interlayer insulating film may adhere to the substrate, the metal layer, and/or the interlayer insulating film. In order to remove the adhered residue, cleaning with a treatment liquid is often performed. In addition, the photoresist film used as a mask during etching is then removed from the laminate by a dry method (dry ashing) or a wet method based on ashing. The dry ashing method is used to remove residues from the photoresist film, etc. sometimes attached to the laminate of the resist. In order to remove the adhering residue, cleaning with a treatment liquid is usually performed.

另一方面，作為用於去除光阻膜的濕式方法，可舉出使用處理液來去除光阻膜之態樣。 如上所述，處理液在半導體器件製造步驟中用於去除殘渣（蝕刻殘渣及灰化殘渣）及/或光阻膜等。On the other hand, as a wet method for removing the photoresist film, an aspect in which the photoresist film is removed using a treatment liquid can be cited. As described above, the treatment liquid is used to remove residues (etching residues and ashing residues) and/or photoresist films in the semiconductor device manufacturing steps.

例如，在專利文獻1中公開了一種包含氧化還原劑、2種螯合劑、金屬腐蝕抑制劑、有機溶劑、水及所期望的pH調節劑之清洗用組成物。For example, Patent Document 1 discloses a cleaning composition containing a redox agent, two types of chelating agents, a metal corrosion inhibitor, an organic solvent, water, and a desired pH adjuster.

[專利文獻1]美國專利第9562211號說明書[Patent Document 1] Specification of US Patent No. 9562211

本發明人等對專利文獻1中所記載之處理液（清洗組成物）進行研究之結果，明確了關於上述處理液具有對成為配線材料及插塞材料等之金屬層（例如，包含鈷之金屬層等）之耐腐蝕性具有進一步改善之空間。The inventors of the present invention conducted research on the treatment liquid (cleaning composition) described in Patent Document 1, and found that the treatment liquid has a metal layer (for example, a metal containing cobalt) that becomes a wiring material and a plug material. The corrosion resistance of layers, etc.) has room for further improvement.

因此，本發明的課題為提供一種半導體器件用處理液，前述半導體器件用處理液係相對於金屬層之耐腐蝕性優異之處理液。 又，本發明的課題為提供一種試劑盒、上述處理液的製造方法、使用上述處理液之基板的清洗方法及使用上述處理液之基板的處理方法。Therefore, the subject of the present invention is to provide a processing solution for a semiconductor device, wherein the processing solution for a semiconductor device is a processing solution having excellent corrosion resistance with respect to a metal layer. Furthermore, the subject of the present invention is to provide a kit, a method of manufacturing the above-mentioned processing liquid, a method of cleaning a substrate using the above-mentioned processing liquid, and a method of processing a substrate using the above-mentioned processing liquid.

本發明人等為了解決上述課題而進行深入研究之結果，發現了能夠藉由處理液包含特定的有機溶劑的組合來解決上述課題，從而完成了本發明。 亦即，發現了藉由以下的結構能夠解決上述課題。The inventors of the present invention conducted intensive studies in order to solve the above-mentioned problems, and found that the above-mentioned problems can be solved by a combination of a treatment liquid containing a specific organic solvent, and completed the present invention. That is, it was found that the above-mentioned problem can be solved by the following structure.

〔1〕一種處理液，其係半導體器件用處理液，其係包含水及有機溶劑，有機溶劑係由有機溶劑A及有機溶劑B構成之組合，且至少包含後述之組合1～6中的任一個之組合，pH係5以上。 〔2〕如〔1〕所述之處理液，其中 作為組合1～6而包含於處理液中之有機溶劑A及有機溶劑B滿足有機溶劑A的含量與有機溶劑B的含量之比例以質量比計係1.0～1.0×104 的條件。 〔3〕如〔1〕或〔2〕所述之處理液，其係還包含去除劑。 〔4〕如〔3〕所述之處理液，其中 去除劑包含選自包括氫氟酸、氟化銨、氟化四甲基銨、多元羧酸及聚胺基羧酸之群組中之至少1種。 〔5〕如〔1〕至〔4〕之任一項所述之處理液，其係還包含pH調節劑。 〔6〕如〔5〕所述之處理液，其中 pH調節劑包含選自包括含氮脂環化合物、氫氧化銨、水溶性胺、四級銨鹽、硫酸、鹽酸及乙酸之群組中之至少1種。 〔7〕如〔1〕至〔6〕之任一項所述之處理液，其係還包含鈷離子。 〔8〕如〔7〕所述之處理液，其中 鈷離子係來源於選自包括氟化鈷、氯化鈷、氫氧化鈷、氧化鈷及硫酸鈷之群組中之至少1種鈷離子源之鈷離子。 〔9〕如〔7〕或〔8〕所述之處理液，其中 有機溶劑A的含量與鈷離子的含量之比例以質量比計係1.0×106 ～1.0×1010 。 〔10〕如〔7〕至〔9〕之任一項所述之處理液，其中 水的含量相對於處理液的總質量係10.0～98.0質量%，有機溶劑的總含量相對於處理液的總質量係1.0～90.0質量%，鈷離子的含量相對於處理液的總質量係0.001～1000質量ppb。 〔11〕如〔1〕至〔10〕之任一項所述之處理液，其中 處理液中的Ca成分的含量與Na成分的含量之比例以質量比計係0.8～1.2。 〔12〕如〔1〕至〔11〕之任一項所述之處理液，其係還包含選自包括羥胺、羥胺衍生物及該等鹽之群組中之至少1種羥胺化合物。 〔13〕如〔1〕至〔12〕之任一項所述之處理液，其係還包含防腐蝕劑。 〔14〕如〔13〕所述之處理液，其中 防腐蝕劑包含選自包括由後述之式（A）表示之化合物、由後述之式（B）表示之化合物、由後述之式（C）表示之化合物及經取代或未經取代之四唑之群組中之至少1種化合物。 〔15〕如〔1〕至〔14〕之任一項所述之處理液，其用作用於去除蝕刻殘渣的清洗液、用於去除圖案形成中所使用之光阻膜的溶液、用於從化學機械研磨後的基板去除殘渣的清洗液或蝕刻液。 〔16〕如〔1〕至〔11〕之任一項所述之處理液，其係還包含選自包括羥胺、羥胺衍生物及該等鹽之群組中之至少1種羥胺化合物以及螯合劑。 〔17〕如〔16〕所述之處理液，其中 與聚胺基聚羧酸不同，螯合劑包含具有至少2個含氮之基團之含氮螯合劑。 〔18〕如〔17〕所述之處理液，其中 含氮螯合劑係選自由後述之式（I）～式（IV）表示之化合物及它們的鹽之化合物。 〔19〕一種試劑盒，其係用於製備〔16〕至〔18〕之任一項所述之處理液，前述試劑盒中具備包含羥胺化合物之第1液及包含螯合劑中的至少1種之第2液，水、有機溶劑A及有機溶劑B分別包含於第1液及第2液中的至少一者中。 〔20〕一種試劑盒，其係具備〔1〕至〔18〕之任一項所述之處理液及選自包括水、異丙醇及包含氫氧化銨之溶劑之群組中之稀釋液。 〔21〕一種處理液的製造方法，其係製造〔16〕至〔18〕之任一項所述之處理液之方法，前述製造方法包括： 金屬去除步驟，從包含螯合劑之原料去除金屬來獲得包含螯合劑之純化物；及 處理液製備步驟，使用純化物來製備處理液。 〔22〕如〔21〕所述之處理液的製造方法，其中 金屬去除步驟包括使原料通過選自包括螯合樹脂及離子交換樹脂之群組中之至少一個樹脂之步驟。 〔23〕如〔21〕或〔22〕所述之處理液的製造方法，其中 純化物中的每個金屬成分的各金屬元素的含量與螯合劑的含量之比例以質量比計均係1.0×10-7 以下。 〔24〕一種基板的清洗方法，其係包括清洗步驟，前述清洗步驟使用〔1〕至〔18〕之任一項所述之處理液，對具備包含選自包括鈷、鎢及銅之群組中之至少1種金屬之金屬層之基板進行清洗。 〔25〕如〔24〕所述之清洗方法，其中 基板還具備包含選自包括銅、鈷、鈷合金、鎢、鎢合金、釕、釕合金、鉭、鉭合金、氧化鋁、氮化鋁、氮氧化鋁、鈦鋁、鈦、氮化鈦、氧化鈦、氧化鋯、氧化鉿、氧化鉭、氧化鑭及釔合金之群組中之至少1種成分之金屬硬遮罩。 〔26〕如〔24〕或〔25〕所述之清洗方法，其還包括沖洗步驟，前述沖洗步驟在清洗步驟之後，用水或包含異丙醇之沖洗液沖洗基板。 〔27〕如〔26〕所述之清洗方法，其中 沖洗液還包含氫氧化銨。 〔28〕如〔26〕或〔27〕所述之清洗方法，其還包括乾燥步驟，前述乾燥步驟在沖洗步驟之後，加熱基板而使其乾燥。 〔29〕一種基板的處理方法，其係對在表面具有金屬層之基板進行處理，前述基板的處理方法包括： 步驟P，實施液處理、使臭氧氣體與基板接觸之臭氧處理、基板在氧氣環境下的加熱處理或使用氧氣之基板的電漿處理，使金屬層的表層氧化而形成氧化金屬層，前述液處理係使選自包括水、過氧化氫水、氨水與過氧化氫水的混合水溶液、氟酸與過氧化氫水的混合水溶液、硫酸與過氧化氫水的混合水溶液、鹽酸與過氧化氫水的混合水溶液、溶氧水以及臭氧溶解水之群組中之藥液與基板的表面接觸；及步驟Q，使〔1〕至〔18〕之任一項所述之處理液與在步驟P中形成之氧化金屬層的表面接觸並且去除氧化金屬層。 〔30〕如〔29〕所述之處理方法，其係依序反覆實施步驟P及步驟Q。 〔31〕如〔29〕或〔30〕之任一項所述之處理方法，其中 金屬層包含鈷、銅、鎢、鈦或鋁。 [發明效果][1] A treatment liquid, which is a treatment liquid for semiconductor devices, which contains water and an organic solvent, and the organic solvent is a combination of organic solvent A and organic solvent B, and at least contains any of combinations 1 to 6 described later A combination of one, the pH is 5 or higher. [2] The treatment liquid as described in [1], wherein the organic solvent A and the organic solvent B contained in the treatment liquid as combinations 1 to 6 satisfy the ratio of the content of the organic solvent A to the content of the organic solvent B in terms of mass ratio count based condition 1.0 ~ 1.0 × 10 4 in. [3] The treatment liquid as described in [1] or [2], which further contains a removing agent. [4] The treatment liquid according to [3], wherein the removing agent comprises at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, polycarboxylic acid and polyaminocarboxylic acid 1 kind. [5] The treatment liquid according to any one of [1] to [4], which further contains a pH adjuster. [6] The treatment liquid as described in [5], wherein the pH adjusting agent comprises a group selected from the group consisting of nitrogen-containing alicyclic compounds, ammonium hydroxide, water-soluble amines, quaternary ammonium salts, sulfuric acid, hydrochloric acid and acetic acid At least one. [7] The treatment liquid according to any one of [1] to [6], which further contains cobalt ions. [8] The treatment solution according to [7], wherein the cobalt ion is derived from at least one cobalt ion source selected from the group consisting of cobalt fluoride, cobalt chloride, cobalt hydroxide, cobalt oxide and cobalt sulfate The cobalt ion. [9] The treatment liquid as described in [7] or [8], wherein the ratio of the content of the organic solvent A to the content of cobalt ion is 1.0×10 6 to 1.0×10 10 in terms of mass ratio. [10] The treatment liquid according to any one of [7] to [9], wherein the content of water is 10.0-98.0% by mass relative to the total mass of the treatment liquid, and the total content of organic solvents is relative to the total mass of the treatment liquid. The mass is 1.0-90.0% by mass, and the content of cobalt ion is 0.001-1000 ppb by mass relative to the total mass of the treatment liquid. [11] The treatment liquid according to any one of [1] to [10], wherein the ratio of the content of the Ca component to the content of the Na component in the treatment liquid is 0.8 to 1.2 in terms of mass ratio. [12] The treatment liquid according to any one of [1] to [11], which further contains at least one hydroxylamine compound selected from the group consisting of hydroxylamine, hydroxylamine derivatives, and these salts. [13] The treatment liquid according to any one of [1] to [12], which further contains an anticorrosive agent. [14] The treatment liquid according to [13], wherein the anticorrosive agent is selected from the group consisting of a compound represented by the formula (A) described later, a compound represented by the formula (B) described later, and a compound represented by the formula (C) described later And at least one compound in the group of substituted or unsubstituted tetrazole. [15] The treatment solution described in any one of [1] to [14], which is used as a cleaning solution for removing etching residues, a solution for removing photoresist films used in pattern formation, and for removing A cleaning solution or etching solution for removing residues from the substrate after chemical mechanical polishing. [16] The treatment liquid according to any one of [1] to [11], which further comprises at least one hydroxylamine compound selected from the group consisting of hydroxylamine, hydroxylamine derivatives and the salts, and a chelating agent . [17] The treatment liquid according to [16], wherein, unlike the polyamine-based polycarboxylic acid, the chelating agent includes a nitrogen-containing chelating agent having at least two nitrogen-containing groups. [18] The treatment liquid according to [17], wherein the nitrogen-containing chelating agent is selected from compounds represented by formula (I) to (IV) and their salts, which will be described later. [19] A kit for preparing the treatment solution described in any one of [16] to [18], the kit having a first solution containing a hydroxylamine compound and at least one of a chelating agent In the second liquid, water, organic solvent A and organic solvent B are respectively contained in at least one of the first liquid and the second liquid. [20] A kit comprising the treatment liquid described in any one of [1] to [18] and a diluent selected from the group consisting of water, isopropanol, and a solvent containing ammonium hydroxide. [21] A method for producing a treatment liquid, which is a method for producing the treatment liquid described in any one of [16] to [18], the aforementioned production method comprising: a metal removal step, removing metals from a raw material containing a chelating agent Obtaining a purified product containing the chelating agent; and a processing liquid preparation step, using the purified product to prepare the processing liquid. [22] The method for producing the treatment liquid described in [21], wherein the metal removal step includes a step of passing the raw material through at least one resin selected from the group consisting of chelating resins and ion exchange resins. [23] The method for producing the treatment liquid as described in [21] or [22], wherein the ratio of the content of each metal element of each metal component in the purified product to the content of the chelating agent is 1.0× in terms of mass ratio 10 -7 or less. [24] A method for cleaning a substrate, which includes a cleaning step. The aforementioned cleaning step uses the treatment solution described in any one of [1] to [18], and is provided with a substrate selected from the group consisting of cobalt, tungsten, and copper. At least one metal of the metal layer of the substrate is cleaned. [25] The cleaning method according to [24], wherein the substrate further includes a substrate selected from the group consisting of copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, A metal hard mask of at least one component from the group of aluminum oxynitride, titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy. [26] The cleaning method as described in [24] or [25], which further includes a rinsing step. After the rinsing step, the substrate is rinsed with water or a rinsing solution containing isopropanol. [27] The cleaning method as described in [26], wherein the rinse solution further contains ammonium hydroxide. [28] The cleaning method as described in [26] or [27], which further includes a drying step. After the washing step, the drying step heats the substrate to dry it. [29] A substrate processing method, which is to process a substrate with a metal layer on the surface. The foregoing substrate processing method includes: Step P: liquid processing, ozone processing in which ozone gas is in contact with the substrate, and the substrate in an oxygen environment Under heat treatment or plasma treatment of the substrate using oxygen, the surface layer of the metal layer is oxidized to form an oxidized metal layer. The aforementioned liquid treatment is selected from the group consisting of water, hydrogen peroxide water, ammonia water and a mixed aqueous solution of hydrogen peroxide water. , Mixed aqueous solution of hydrofluoric acid and hydrogen peroxide water, mixed aqueous solution of sulfuric acid and hydrogen peroxide water, mixed aqueous solution of hydrochloric acid and hydrogen peroxide water, dissolved oxygen water and ozone dissolved water in the group of chemical solutions and the surface of the substrate Contacting; and step Q, contacting the treatment solution described in any one of [1] to [18] with the surface of the metal oxide layer formed in step P and removing the metal oxide layer. [30] The processing method described in [29], in which step P and step Q are repeated in sequence. [31] The processing method according to any one of [29] or [30], wherein the metal layer contains cobalt, copper, tungsten, titanium or aluminum. [Effects of the invention]

依據本發明，能夠提供一種半導體器件用處理液，前述處理液相對於金屬層之耐腐蝕性優異。 又，本發明能夠提供一種試劑盒、上述處理液的製造方法、使用上述處理液之基板的清洗方法及使用上述處理液之基板的處理方法。According to the present invention, it is possible to provide a treatment liquid for a semiconductor device in which the treatment liquid phase has excellent corrosion resistance to a metal layer. In addition, the present invention can provide a kit, a method of manufacturing the above-mentioned processing liquid, a method of cleaning a substrate using the above-mentioned processing liquid, and a method of processing a substrate using the above-mentioned processing liquid.

以下，對本發明進行詳細說明。 以下所記載之構成要件的說明有時根據本發明的代表性的實施態樣來完成，但是本發明並不限制於該等的實施態樣。 另外，在本說明書中，用“～”來表示之數值範圍係指將記載於“～”前後之數值作為下限值及上限值而包括之範圍。 又，在本說明書中稱為“準備”時，除了合成及調合特定的材料等而具備以外，亦包含藉由購入等獲得特定的材料者。 又，在本說明書中，“ppm”係指“parts-per-million（10-6 ），百萬分之一”， “ppb”係指“parts-per-billion（10-9 ），十億分之一”，“ppt”係指“parts-per-trillion（10-12 ），萬億分之一”。 又，在本說明書中，1Å（Angstrom）相當於0.1nm。 又，本說明書中的基團（原子團）的標記中，未標註經取代及未經取代之標記係在不損害本發明的效果之範圍內與不具有取代基者一同還包含具有取代基者之標記。例如“烴基”不僅包含不具有取代基之烴基（未經取代之烴基），亦包含具有取代基之烴基（經取代的烴基）。在此，關於各化合物的含義亦相同。 又，本說明書中的“放射線”係指例如以水銀燈的明線光譜、準分子雷射為代表之遠紫外線、極紫外線（EUV光）、X射線或電子束。又，本說明書中光係指光化射線或放射線。本說明書中的“曝光”只要沒有特別說明，不僅包括以水銀燈、準分子雷射為代表之基於遠紫外線、X射線或EUV光之曝光，基於電子束或離子束等粒子束之描繪亦包括在曝光中。Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be completed based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. In addition, in this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as the lower limit and the upper limit. In addition, when it is referred to as "preparation" in this specification, in addition to synthesizing and blending specific materials, it also includes those who obtain specific materials through purchase or the like. In addition, in this specification, "ppm" means "parts-per-million (10 -6 ), one part per million", and "ppb" means "parts-per-billion (10 -9 ), one billion One part", "ppt" means "parts-per-trillion (10 -12 ), one part per trillion". In addition, in this specification, 1Å (Angstrom) is equivalent to 0.1nm. In addition, in the label of the group (atomic group) in this specification, the label that does not indicate substituted and unsubstituted is included in the range that does not impair the effect of the present invention, together with those that do not have substituents, and those that have substituents. mark. For example, "hydrocarbyl" includes not only unsubstituted hydrocarbyl groups (unsubstituted hydrocarbyl groups), but also substituted hydrocarbyl groups (substituted hydrocarbyl groups). Here, the meaning of each compound is also the same. In addition, the "radiation" in this specification refers to, for example, extreme ultraviolet, extreme ultraviolet (EUV light), X-rays, or electron beams represented by the bright-ray spectrum of a mercury lamp and excimer lasers. In addition, in this specification, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in this specification includes not only exposure based on extreme ultraviolet, X-ray or EUV light represented by mercury lamps and excimer lasers, but also descriptions based on particle beams such as electron beams or ion beams. Exposing.

[處理液] 本發明的處理液包含水及有機溶劑，並且作為有機溶劑A及有機溶劑B的組合，至少包含後述之組合1～6中的任一種。 作為處理液的特徵點，可舉出作為有機溶劑而包含由後述之有機溶劑A及B構成之特定的組合中的任一種之方面。可推測為藉由成為配線材料及插塞材料等之金屬層的處理中所使用之處理液中存在由有機溶劑A及B構成之特定的組合，在金屬層的表面形成緻密且更疏水的有機膜。認為形成這樣的有機膜之結果，由於抑制了金屬從金屬層溶出，因此處理液相對於金屬層之耐腐蝕性優異（以下亦記載為“本發明的效果優異”）。[Treatment liquid] The treatment liquid of the present invention contains water and an organic solvent, and as a combination of the organic solvent A and the organic solvent B, it contains at least any one of combinations 1 to 6 described later. As a characteristic point of a processing liquid, the aspect which contains any one of the specific combination which consists of organic solvent A and B mentioned later as an organic solvent is mentioned. It can be presumed that by the presence of a specific combination of organic solvents A and B in the treatment liquid used in the treatment of metal layers such as wiring materials and plug materials, a dense and more hydrophobic organic solvent is formed on the surface of the metal layer. membrane. It is considered that, as a result of forming such an organic film, since the elution of the metal from the metal layer is suppressed, the treatment liquid phase has excellent corrosion resistance to the metal layer (hereinafter also described as "the effect of the present invention is excellent").

〔水〕 本發明的處理液包含水。 水的含量並無特別限制，相對於處理液的總質量例如係1～97質量%，10～98質量%為較佳，10～97質量%為更佳。 作為水，用於半導體器件製造中之超純水為較佳。 作為水，尤其較佳為減少無機陰離子及金屬離子等之水，其中，減少來自於Fe、Co、Na、K、Ca、Cu、Mg、Mn、Li、Al、Cr、Ni及Zn的金屬原子的離子濃度為更佳，用於製備處理液時，調整成ppt級或其以下（一形態中，金屬含有率小於0.001質量ppt）者為進一步較佳。作為調整的方法，使用過濾膜或離子交換膜之純化或利用蒸餾之純化為較佳。作為調整的方法，例如可舉出日本特開2011-110515號公報[0074]～[0084]段中所記載之方法及日本特開2007-254168號公報中所記載之方法等。〔water〕 The treatment liquid of the present invention contains water. The content of water is not particularly limited, and it is, for example, 1 to 97% by mass relative to the total mass of the treatment liquid, preferably 10 to 98% by mass, and more preferably 10 to 97% by mass. As the water, ultrapure water used in the manufacture of semiconductor devices is preferred. As water, it is particularly preferable to reduce inorganic anions and metal ions. Among them, reduce metal atoms derived from Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn. The ion concentration of is more preferable, and when used in the preparation of the treatment liquid, it is more preferable to adjust it to ppt level or below (in one form, the metal content is less than 0.001 mass ppt). As a method of adjustment, purification using filtration membranes or ion exchange membranes or purification using distillation is preferred. As the method of adjustment, for example, the method described in paragraphs [0074] to [0084] of Japanese Patent Application Publication No. 2011-110515, the method described in Japanese Patent Application Publication No. 2007-254168, and the like can be cited.

另外，用於本發明的實施形態之水如上述般獲得之水為較佳。又，從顯著獲得本發明的所期望的效果之觀點考慮，上述之水不僅用於處理液亦用於收容容器的清洗為更佳。又，上述之水亦用於處理液的製造步驟、處理液的成分測量及處理液的評價的測量等為較佳。In addition, the water used in the embodiment of the present invention is preferably water obtained as described above. In addition, from the viewpoint of remarkably obtaining the desired effect of the present invention, the above-mentioned water is preferably used not only for the treatment liquid but also for washing the storage container. In addition, it is preferable that the above-mentioned water is also used in the manufacturing steps of the treatment liquid, the measurement of the components of the treatment liquid, and the measurement of the evaluation of the treatment liquid.

〔有機溶劑〕 本發明的處理液包含有機溶劑。有機溶劑係由有機溶劑A及有機溶劑B構成之組合並且至少包含下述的組合1～6中的任一個之組合。〔Organic solvents〕 The treatment liquid of the present invention contains an organic solvent. The organic solvent is a combination composed of an organic solvent A and an organic solvent B, and includes at least any one of the following combinations 1 to 6.

（組合1） 組合1係如下組合：有機溶劑A係乙二醇單丁醚（EGBE：Ethylene Glycol Monobutyl Ether），有機溶劑B係選自包括1-二級丁氧基丁烷、1-（2-丁氧基乙氧基）乙烷-1-醇、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、（2-丁氧基乙氧基）乙酸、3,6,9,12-四氧十六烷-1-醇、甘油、十八醇及二（2-丁氧基）甲烷之群組B1中之至少1種。 亦即，組合1的情況下，處理液包含EGBE作為有機溶劑A，並且包含選自群組B1中之至少1種化合物作為有機溶劑B。 作為組合1而包含在處理液中之有機溶劑B，從缺陷抑制性更優異之觀點考慮，1-二級丁氧基丁烷、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、3,6,9,12-四氧十六烷-1-醇、甘油、十八醇或二（2-丁氧基）甲烷為較佳，從本發明的效果、相對於包含SiOx（x表示1～3的整數）之層（以下亦記載為“SiOx層”）之耐腐蝕性及殘渣去除性更優異之觀點考慮，1-二級丁氧基丁烷、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、3,6,9,12-四氧十六烷-1-醇、甘油或二（2-丁氧基）甲烷為更佳，二（2-丁氧基）甲烷為進一步較佳。(Combination 1) Combination 1 is the following combination: Organic solvent A is Ethylene Glycol Monobutyl Ether (EGBE: Ethylene Glycol Monobutyl Ether), organic solvent B is selected from the group including 1-secondary butoxybutane, 1-(2-butoxy) Ethoxy) ethane-1-ol, 1-((2-butoxyethoxy)methoxy)butane, 1-(2-(ethoxymethoxy)ethoxy)butane , (2-butoxyethoxy)acetic acid, 3,6,9,12-tetraoxetane-1-ol, glycerin, stearyl alcohol and bis(2-butoxy)methane group B1 At least one of them. That is, in the case of combination 1, the treatment liquid contains EGBE as the organic solvent A, and contains at least one compound selected from the group B1 as the organic solvent B. The organic solvent B contained in the treatment liquid as the combination 1, from the viewpoint of better defect suppression, 1-secondary butoxybutane, 1-((2-butoxyethoxy)methoxy ) Butane, 1-(2-(ethoxymethoxy)ethoxy)butane, 3,6,9,12-tetraoxyhexadecane-1-ol, glycerin, stearyl alcohol or di( 2-Butoxy)methane is preferred. From the effect of the present invention, the corrosion resistance and residue removal properties relative to a layer containing SiOx (x represents an integer of 1 to 3) (hereinafter also referred to as "SiOx layer") For more excellent points of view, 1-second-butoxybutane, 1-((2-butoxyethoxy)methoxy)butane, 1-(2-(ethoxymethoxy)ethyl Oxy)butane, 3,6,9,12-tetraoxetane-1-ol, glycerol or bis(2-butoxy)methane is more preferred, and bis(2-butoxy)methane is further Better.

（組合2） 組合2係如下組合：有機溶劑A係二乙二醇單丁醚（DEGBE：Diethylene Glycol Monobutyl Ether），有機溶劑B係選自包括1-二級丁氧基丁烷、1-（2-丁氧基乙氧基）乙烷-1-醇、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、（2-丁氧基乙氧基）乙酸、3,6,9,12-四氧十六烷-1-醇、甘油、十八醇及二（2-丁氧基）甲烷之群組B2中之至少1種。 亦即，組合2的情況下，處理液包含DEGBE作為有機溶劑A，並且包含選自群組B2中之至少1種化合物作為有機溶劑B。 作為組合2而包含在處理液中之有機溶劑B，十八醇或二（2-丁氧基）甲烷為較佳。(Combination 2) Combination 2 is the following combination: Organic solvent A is Diethylene Glycol Monobutyl Ether (DEGBE: Diethylene Glycol Monobutyl Ether), and organic solvent B is selected from the group including 1-second-butoxybutane, 1-(2-butoxy) Ethoxy) ethane-1-ol, 1-((2-butoxyethoxy)methoxy)butane, 1-(2-(ethoxymethoxy)ethoxy)butane The group of alkanes, (2-butoxyethoxy) acetic acid, 3,6,9,12-tetraoxetane-1-ol, glycerin, stearyl alcohol and bis(2-butoxy)methane At least one of B2. That is, in the case of combination 2, the treatment liquid contains DEGBE as the organic solvent A and contains at least one compound selected from the group B2 as the organic solvent B. As the organic solvent B contained in the treatment liquid as the combination 2, stearyl alcohol or bis(2-butoxy)methane is preferred.

（組合3） 組合3係如下組合：有機溶劑A係二甲基亞碸（DMSO：Dimethyl Sulfoxide），有機溶劑B係選自包括二甲基二硫醚、二甲基硫醚及二甲基碸二甲基二硫醚之群組B3中之至少1種。 亦即，組合3的情況下，處理液包含DMSO作為有機溶劑A，並且包含選自群組B3中之至少1種化合物作為有機溶劑B。 作為組合3而包含在處理液中之有機溶劑B，二甲基硫醚為較佳。(Combination 3) Combination 3 is the following combination: organic solvent A is dimethyl sulfide (DMSO: Dimethyl Sulfoxide), organic solvent B is selected from the group including dimethyl disulfide, dimethyl sulfide and dimethyl sulfide dimethyl sulfide At least one of the group B3 of thioethers. That is, in the case of combination 3, the treatment liquid contains DMSO as the organic solvent A and contains at least one compound selected from the group B3 as the organic solvent B. As the organic solvent B contained in the treatment liquid as the combination 3, dimethyl sulfide is preferred.

（組合4） 組合4係如下組合：有機溶劑A係環丁碸，有機溶劑B係選自包括3-環丁烯碸及二甲基亞碸（DMSO）之群組B4中之至少1種。 亦即，組合4的情況下，處理液包含環丁碸作為有機溶劑A，並且包含選自群組B4中之至少1種化合物作為有機溶劑B。 作為組合4而包含在處理液中之有機溶劑B，從本發明的效果更優異之觀點考慮，3-環丁烯碸為較佳，又，從相對於SiOx層之耐腐蝕性更優異之觀點考慮，DMSO為較佳。(Combination 4) Combination 4 is the following combination: the organic solvent A is cyclobutane, and the organic solvent B is at least one selected from the group B4 including 3-cyclobutene and dimethylsulfide (DMSO). That is, in the case of combination 4, the treatment liquid contains cyclobutene as the organic solvent A, and contains at least one compound selected from the group B4 as the organic solvent B. The organic solvent B contained in the treatment liquid as the combination 4 is preferably 3-cyclobutene from the viewpoint that the effect of the present invention is more excellent, and from the viewpoint that the corrosion resistance relative to the SiOx layer is more excellent In consideration, DMSO is better.

（組合5） 組合5係如下組合：有機溶劑A係丙二醇（PG：Propylene Glycol），有機溶劑B係甘油。 亦即，組合5的情況下，處理液包含PG作為有機溶劑A，並且包含甘油作為有機溶劑B。(Combination 5) Combination 5 is the following combination: organic solvent A is propylene glycol (PG: Propylene Glycol), organic solvent B is glycerin. That is, in the case of combination 5, the treatment liquid contains PG as the organic solvent A and glycerin as the organic solvent B.

（組合6） 組合6係如下組合：有機溶劑A係伸己基二醇（HG：Hexylene Glycol），有機溶劑B係選自包括丙酮及二丙酮醇之群組B6中之至少1種。 亦即，組合6的情況下，處理液包含HG而作為有機溶劑A，並且包含選自群組B6中之至少1種化合物作為有機溶劑B。 作為組合6而包含在處理液中之有機溶劑B，從殘渣去除性優異之觀點考慮，丙酮為較佳。(Combination 6) Combination 6 is the following combination: organic solvent A is Hexylene Glycol (HG: Hexylene Glycol), and organic solvent B is at least one selected from the group B6 including acetone and diacetone alcohol. That is, in the case of combination 6, the treatment liquid contains HG as the organic solvent A, and contains at least one compound selected from the group B6 as the organic solvent B. The organic solvent B contained in the treatment liquid as the combination 6 is preferably acetone from the viewpoint of excellent residue removability.

處理液可以僅包含上述組合1～6中的1個組合，亦可以包含2個以上的組合。 處理液所包含之有機溶劑A及B的組合可以為組合1～6中的任一種，但是從含鈷層的耐腐蝕性優異之觀點考慮，組合1或組合2為較佳，組合1為更佳。The treatment liquid may contain only one combination of the above-mentioned combinations 1 to 6, or may contain two or more combinations. The combination of organic solvents A and B contained in the treatment liquid may be any of combinations 1 to 6, but from the viewpoint of excellent corrosion resistance of the cobalt-containing layer, combination 1 or combination 2 is preferable, and combination 1 is more good.

本說明書中，分別將在上述說明中作為有機溶劑A及有機溶劑B而舉出之化合物中的處理液中所包含且構成組合1～6中的任一種之化合物記載為“特定有機溶劑A”及“特定有機溶劑B”。亦即，處理液包含特定有機溶劑A之情況下，處理液係指與特定有機溶劑A一同且必須包含構成組合1～6中的任一種之特定有機溶劑B。In this specification, the compounds included in the treatment liquid of the compounds listed as the organic solvent A and the organic solvent B in the above description and constituting any one of combinations 1 to 6 are described as "specific organic solvent A" And "Specific Organic Solvent B". That is, when the treatment liquid contains the specific organic solvent A, the treatment liquid means the specific organic solvent B together with the specific organic solvent A and must contain any one of the composition combinations 1 to 6.

處理液中，從本發明的效果更優異之觀點考慮，特定有機溶劑A的含量與特定有機溶劑B的含量之比例以質量比計係1.0以上為較佳，1.0×101 以上為更佳，1.0×102 以上為進一步較佳。 又，從殘渣的去除性及缺陷抑制性更優異之觀點考慮，特定有機溶劑A的含量與特定有機溶劑B的含量之比例以質量比計係1.0×105 以下為較佳，1.0×104 以下為更佳。 另外，組合1～4及6中，處理液中所包含之特定有機溶劑B可以單獨使用1種，亦可以併用2種以上。處理液包含2種以上的特定有機溶劑B之情況下，上述比例中的特定有機溶劑B的含量係2種以上的特定有機溶劑B的總含量。In the treatment liquid, from the viewpoint that the effect of the present invention is more excellent, the ratio of the content of the specific organic solvent A to the content of the specific organic solvent B is preferably 1.0 or more by mass ratio, and more preferably 1.0×10 1 or more. 1.0×10 2 or more is more preferable. In addition, from the viewpoint of more excellent residue removal and defect suppression, the ratio of the content of the specific organic solvent A to the content of the specific organic solvent B is preferably 1.0×10 5 or less by mass ratio, which is 1.0×10 4 The following is better. In addition, in combinations 1 to 4 and 6, the specific organic solvent B contained in the treatment liquid may be used alone or in combination of two or more. When the treatment liquid contains two or more specific organic solvents B, the content of the specific organic solvent B in the above ratio is the total content of the two or more specific organic solvents B.

處理液中的特定有機溶劑A的含量並無特別限制，從本發明的效果與殘渣去除性及缺陷抑制性的平衡更優異之觀點考慮，相對於處理液的總質量係0.05～98.0質量%為較佳，0.5～85.0質量%為更佳，2.0～75.0質量%為進一步較佳。The content of the specific organic solvent A in the treatment liquid is not particularly limited. From the viewpoint of the effect of the present invention, the balance of residue removal properties and defect suppression properties, it is 0.05-98.0% by mass relative to the total mass of the treatment liquid Preferably, 0.5-85.0% by mass is more preferable, and 2.0-75.0% by mass is still more preferable.

處理液中的特定有機溶劑B的含量（2種以上的情況下係總含量）並無特別限制，從本發明的效果更優異之觀點考慮，相對於處理液的總質量係0.00001質量%以上為較佳，0.0001質量%以上為更佳，0.0005質量%以上為進一步較佳。又，從殘渣去除性及缺陷抑制性更優異之觀點考慮，特定有機溶劑B的含量相對於處理液的總質量係10.0質量%以下為較佳，1.0質量%以下為更佳，0.3質量%以下為進一步較佳。The content of the specific organic solvent B in the treatment liquid (the total content in the case of two or more types) is not particularly limited. From the viewpoint of the more excellent effect of the present invention, it is 0.00001 mass% or more with respect to the total mass of the treatment liquid Preferably, 0.0001 mass% or more is more preferable, and 0.0005 mass% or more is even more preferable. In addition, from the viewpoint of more excellent residue removal and defect suppression, the content of the specific organic solvent B relative to the total mass of the treatment liquid is preferably 10.0% by mass or less, 1.0% by mass or less is more preferably, and 0.3% by mass or less To be further preferred.

處理液可以包含除了特定有機溶劑A及特定有機溶劑B以外的有機溶劑。亦即，處理液可以包含選自包括成對之有機溶劑B不存在於處理液中之有機溶劑A、成對之有機溶劑A不存在於處理液中之有機溶劑B以及除了有機溶劑A及有機溶劑B之有機溶劑之群組中之至少1種溶劑（以下亦記載為“其他有機溶劑”。）。The treatment liquid may contain organic solvents other than the specific organic solvent A and the specific organic solvent B. That is, the treatment liquid may include organic solvent A in which a pair of organic solvent B does not exist in the treatment liquid, an organic solvent B in which a pair of organic solvent A does not exist in the treatment liquid, and an organic solvent other than organic solvent A and organic solvent A. At least one solvent in the group of organic solvents for solvent B (also described as "other organic solvents" below).

作為其他有機溶劑，並無特別限制，親水性有機溶劑為較佳。另外，本說明書中親水性有機溶劑係指25℃的條件下在100g的水中溶解0.1g以上之有機溶劑。作為親水性有機溶劑，能夠以任意比例與水均勻地混合之有機溶劑為較佳。 作為親水性有機溶劑，選自包括二醇系溶劑、二醇醚系溶劑、醯胺系溶劑、醇系溶劑及亞碸系溶劑之群組中之至少1種為較佳。There are no particular restrictions on other organic solvents, and hydrophilic organic solvents are preferred. In addition, the hydrophilic organic solvent in this specification refers to an organic solvent that dissolves more than 0.1 g in 100 g of water at 25°C. As the hydrophilic organic solvent, an organic solvent that can be uniformly mixed with water in any ratio is preferred. As the hydrophilic organic solvent, at least one selected from the group consisting of glycol-based solvents, glycol ether-based solvents, amide-based solvents, alcohol-based solvents, and arsenic-based solvents is preferred.

作為二醇系溶劑並無特別限制，例如可舉出乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇及四乙二醇。The glycol solvent is not particularly limited, and examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

作為二醇醚系溶劑並無特別限制，例如可舉出二醇單醚。 作為二醇單醚，例如可舉出乙二醇單甲醚、乙二醇單乙醚、乙二醇單正丙醚、乙二醇單異丙醚、乙二醇單正丁醚、二乙二醇單甲醚、二乙二醇單乙醚、二乙二醇單丁醚、三乙二醇單甲醚、三乙二醇單乙醚、三乙二醇單丁醚、1-甲氧基-2-丙醇、2-甲氧基-1-丙醇、1-乙氧基-2-丙醇、2-乙氧基-1-丙醇、丙二醇單正丙醚、二丙二醇單甲醚、二丙二醇單乙醚、二丙二醇單正丙醚、三丙二醇單乙醚、三丙二醇單甲醚、乙二醇單苄醚及二乙二醇單苄醚。The glycol ether-based solvent is not particularly limited, and, for example, glycol monoether can be mentioned. Examples of glycol monoethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, and diethylene diethyl ether. Alcohol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2 -Propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, two Propylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether and diethylene glycol monobenzyl ether.

作為醯胺系溶劑並無特別限制，可舉出N,N-二甲基甲醯胺、1-甲基-2-吡咯啶酮、2-吡咯啶酮、1,3-二甲基-2-咪唑啶酮、甲醯胺、N-甲基甲醯胺、乙醯胺、N-甲基乙醯胺、N,N-二甲基乙醯胺、N-甲基丙醯胺及六甲基磷醯三胺。The amide-based solvent is not particularly limited, and N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2 -Imidazolidinone, Formamide, N-Methyl Formamide, Acetamide, N-Methyl Acetamide, N,N-Dimethyl Acetamide, N-Methyl Acetamide and Hexamethyl Base phosphatidylamine.

作為醇系溶劑並無特別限制，但是可舉出烷二醇、烷氧基醇、飽和脂肪族一元醇及不飽和非芳香族一元醇。 作為烷二醇，例如可舉出二醇、2-甲基-1,3-丙烷二醇、1,3-丙烷二醇、2,2-二甲基-1,3-丙烷二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇及頻那醇。 作為烷氧基醇，例如可舉出3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、1-甲氧基-2-丁醇及二醇單醚。 作為飽和脂肪族一元醇，例如可舉出甲醇、乙醇、正丙醇、異丙醇（Isopropyl alcohol）、1-丁醇、2-丁醇、異丁醇、第三丁醇、2-戊醇、第三戊醇及1-己醇。 作為不飽和非芳香族一元醇，例如可舉出烯丙醇、炔丙基醇、2-丁烯醇、3-丁烯醇及4-戊烯-2-醇。 作為包含環結構之低分子量的醇，例如可舉出四氫糠醇、糠醇及1,3-環戊烷二醇。The alcohol-based solvent is not particularly limited, but alkanediol, alkoxy alcohol, saturated aliphatic monohydric alcohol, and unsaturated non-aromatic monohydric alcohol may be mentioned. Examples of alkanediols include diols, 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1 ,4-butanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol and pinacol. Examples of alkoxy alcohols include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, 1-methoxy-2-butanol, and diols Monoether. Examples of saturated aliphatic monohydric alcohols include methanol, ethanol, n-propanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutanol, tertiary butanol, 2-pentanol , Tertiary amyl alcohol and 1-hexanol. Examples of unsaturated non-aromatic monohydric alcohols include allyl alcohol, propargyl alcohol, 2-butenol, 3-butenol, and 4-penten-2-ol. Examples of the low molecular weight alcohol containing a ring structure include tetrahydrofurfuryl alcohol, furfuryl alcohol, and 1,3-cyclopentanediol.

作為亞碸系溶劑，例如可舉出二甲亞碸等。As the sulfenite-based solvent, for example, dimethyl sulfenite and the like can be given.

作為親水性有機溶劑，從本發明的效果更優異之觀點考慮，二醇醚系溶劑為較佳。As the hydrophilic organic solvent, a glycol ether-based solvent is preferable from the viewpoint that the effect of the present invention is more excellent.

其他有機溶劑可以單獨使用1種，亦可以併用2種以上。 處理液包含其他有機溶劑之情況下，其他有機溶劑的含量（存在2種以上之情況下係其總含量）相對於處理液的總質量係0.05～80質量%為較佳，1～55質量%為更佳。Other organic solvents may be used singly or in combination of two or more kinds. When the treatment liquid contains other organic solvents, the content of the other organic solvents (the total content when there are more than two) is preferably 0.05 to 80% by mass relative to the total mass of the treatment liquid, and 1 to 55% by mass For better.

處理液中的有機溶劑的含量（特定有機溶劑A、特定有機溶劑B及其他有機溶劑的總含量）並無特別限制，相對於處理液的總質量係0.05～99.0質量%為較佳，1.0～90.0質量%為更佳，2.0～80.0質量%為進一步較佳。The content of the organic solvent in the treatment liquid (the total content of the specific organic solvent A, the specific organic solvent B and other organic solvents) is not particularly limited, and is preferably 0.05-99.0% by mass relative to the total mass of the treatment liquid, 1.0- 90.0% by mass is more preferable, and 2.0 to 80.0% by mass is still more preferable.

〔任意成分〕 處理液還可以包含除了上述之成分以外的成分。以下，對處理液能夠包含之任意成分進行詳細說明。〔Arbitrary ingredients〕 The treatment liquid may also contain components other than the above-mentioned components. Hereinafter, the optional components that can be contained in the treatment liquid will be described in detail.

＜去除劑＞ 處理液包含去除劑為較佳。 去除劑只要為具有去除蝕刻殘渣及灰化殘渣等殘渣之功能之化合物，則並無特別限制，例如可舉出螯合劑、含氟化合物及羥胺化合物。＜Removing agent＞ It is preferable that the treatment liquid contains a removing agent. The removing agent is not particularly limited as long as it is a compound having a function of removing residues such as etching residues and ashing residues, and examples thereof include chelating agents, fluorine-containing compounds, and hydroxylamine compounds.

（螯合劑） 處理液包含螯合劑而作為去除劑為較佳。 螯合劑具有與包含於殘渣中之經氧化之金屬進行螯合化之功能。其結果，處理液具有優異之殘渣去除性及缺陷抑制性。(Chelating agent) The treatment liquid contains a chelating agent and is preferably used as a removing agent. The chelating agent has the function of chelating with the oxidized metal contained in the residue. As a result, the treatment liquid has excellent residue removal properties and defect suppression properties.

作為螯合劑，例如可舉出聚胺基聚羧酸、聚羧酸及與聚胺基聚羧酸不同且具有至少2個含氮之基團（含氮原子之基團）之含氮螯合劑（以下亦記載為“特定含氮螯合劑”）。As the chelating agent, for example, polyamine-based polycarboxylic acid, polycarboxylic acid, and nitrogen-containing chelating agent that are different from polyamine-based polycarboxylic acid and have at least two nitrogen-containing groups (groups containing nitrogen atoms) (Hereinafter, it is also described as "specific nitrogen-containing chelating agent").

-聚胺基聚羧酸- 聚胺基聚羧酸係在1個分子中具有複數個胺基及複數個羧酸基之化合物，例如可舉出單-或聚伸烷基聚胺聚羧酸、聚胺基烷聚羧酸、聚胺基烷醇聚羧酸及羥基烷醚聚胺聚羧酸等。-Polyaminopolycarboxylic acid- Polyaminopolycarboxylic acid is a compound having plural amine groups and plural carboxylic acid groups in one molecule, for example, mono- or polyalkylene polyamine polycarboxylic acid, polyaminoalkyl polycarboxylic acid , Polyaminoalkanol polycarboxylic acid and hydroxyalkyl ether polyamine polycarboxylic acid, etc.

作為聚胺基聚羧酸，例如可舉出丁二胺四乙酸、二乙烯三胺五乙酸（DTPA）、乙二胺四丙酸、三乙四胺六乙酸、1,3-二胺基-2-羥基丙烷-N,N,N’,N’-四乙酸、丙二胺四乙酸、乙二胺四乙酸（EDTA）、反式-1,2-二胺基環己烷四乙酸（Cy-DTA）、乙二胺二乙酸、乙二胺二丙酸、1,6-六亞甲基-二胺-N,N,N’,N’-四乙酸、N,N-雙（2-羥基苄基）乙二胺-N,N-二乙酸、二胺基丙烷四乙酸、1,4,7,10-四氮雜環十二烷-四乙酸、二胺基丙醇四乙酸及（羥基乙基）乙二胺三乙酸等。 其中，二乙烯三胺五乙酸（DTPA）、乙二胺四乙酸（EDTA）或反式-1,2-二胺基環己烷四乙酸（Cy-DTA）為較佳。As the polyamino polycarboxylic acid, for example, butanediaminetetraacetic acid, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetraaminehexaacetic acid, 1,3-diamino- 2-Hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, ethylenediaminetetraacetic acid (EDTA), trans-1,2-diaminocyclohexanetetraacetic acid (Cy -DTA), ethylenediaminediacetic acid, ethylenediaminedipropionic acid, 1,6-hexamethylene-diamine-N,N,N',N'-tetraacetic acid, N,N-bis(2- Hydroxybenzyl) ethylenediamine-N,N-diacetic acid, diaminopropanetetraacetic acid, 1,4,7,10-tetraazacyclododecane-tetraacetic acid, diaminopropanoltetraacetic acid and ( Hydroxyethyl) ethylenediaminetriacetic acid and so on. Among them, diethylenetriaminepentaacetic acid (DTPA), ethylenediaminetetraacetic acid (EDTA) or trans-1,2-diaminocyclohexanetetraacetic acid (Cy-DTA) are preferred.

-聚羧酸- 聚羧酸係在1個分子中具有複數個羧酸基之化合物。其中，上述之聚胺基聚羧酸不包含於聚羧酸中。 作為聚羧酸，例如可舉出丙二酸、順丁烯二酸、丁二酸、蘋果酸、酒石酸及檸檬酸。-Polycarboxylic acid- The polycarboxylic acid is a compound having a plurality of carboxylic acid groups in one molecule. Among them, the above-mentioned polyamine-based polycarboxylic acid is not included in the polycarboxylic acid. Examples of polycarboxylic acids include malonic acid, maleic acid, succinic acid, malic acid, tartaric acid, and citric acid.

-特定含氮螯合劑- 特定含氮螯合劑係具有至少2個含氮之基團之化合物，係與上述聚胺基聚羧酸不同之化合物。 從本發明的效果（尤其，包含W之金屬層的耐腐蝕性）更優異之觀點考慮，處理液包含特定含氮螯合劑為較佳。 作為特定含氮螯合劑，例如可舉出具有至少2個含氮之基團之單羧酸及具有至少2個含氮之基團且不具有羧基之化合物。-Specific nitrogen-containing chelating agents- The specific nitrogen-containing chelating agent is a compound having at least two nitrogen-containing groups, and is a compound different from the above-mentioned polyamine-based polycarboxylic acid. From the viewpoint of the effect of the present invention (especially, the corrosion resistance of the metal layer containing W) is more excellent, it is preferable that the treatment liquid contains a specific nitrogen-containing chelating agent. As a specific nitrogen-containing chelating agent, the monocarboxylic acid which has at least 2 nitrogen-containing groups, and the compound which has at least 2 nitrogen-containing groups and does not have a carboxyl group are mentioned, for example.

作為具有至少2個含氮之基團之單羧酸，包含一級胺基或二級胺基及至少一個追加的含氮之基團之單羧酸為較佳。作為追加的含氮之基團，可舉出咪唑基、三唑基、苯并三唑基、哌𠯤基（piperazinyl group）、吡咯基、吡咯啶基、吡唑基、哌啶基、胍基、咔唑基、肼基、半咔肼基、胺基胍基、一級胺基（較佳為碳數1～10的一級胺基）及二級胺基（較佳為碳數1～10的二級胺基）。該等含氮之基團除了二級胺基以外，還可以經低級烷基等取代基進行取代。As the monocarboxylic acid having at least two nitrogen-containing groups, a monocarboxylic acid containing a primary amine group or a secondary amine group and at least one additional nitrogen-containing group is preferred. Examples of additional nitrogen-containing groups include imidazolyl, triazolyl, benzotriazolyl, piperazinyl group, pyrrolyl, pyrrolidinyl, pyrazolyl, piperidinyl, and guanidyl , Carbazole group, hydrazine group, semicarbazide group, aminoguanidine group, primary amine group (preferably one with 1 to 10 carbons) and secondary amine group (preferably with 1 to 10 carbons) Secondary amino group). In addition to secondary amino groups, these nitrogen-containing groups may also be substituted with substituents such as lower alkyl groups.

其中，由下述式（I）表示之化合物或其鹽為更佳。 （R3 NH）C（R1 ）（R2 ）CO2 H   （I） 式（I）中，R1 及R2 分別獨立地表示氫原子、碳數1～4的烷基或具有至少一個含氮基之基團，R3 表示氫原子、碳數1～10的烷基或具有至少一個含氮基之基團。 其中，R1 、R2 及R3 中的至少一個表示具有至少一個含氮基之基團。Among them, a compound represented by the following formula (I) or a salt thereof is more preferable. (R 3 NH)C(R 1 )(R 2 )CO 2 H (I) In formula (I), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group with 1 to 4 carbon atoms, or at least one For nitrogen-containing groups, R 3 represents a hydrogen atom, a C 1-10 alkyl group, or a group having at least one nitrogen-containing group. Among them, at least one of R 1 , R 2 and R 3 represents a group having at least one nitrogen-containing group.

作為由R1 、R2 及R3 中的至少一個表示之具有至少一個含氮基之基團，可以藉由胺基、胍基或咪唑基進行取代亦可以藉由羥基進行進一步取代之碳數1～10的烷基為較佳。The group having at least one nitrogen-containing group represented by at least one of R 1 , R 2 and R 3 may be substituted by an amino group, a guanidine group or an imidazole group or may be further substituted by a hydroxyl group. An alkyl group of 1-10 is preferred.

式（I）中，R1 表示具有至少一個含氮基之基團之情況下，R2 表示氫原子或碳數1～10的烷基，並且R3 表示氫原子、碳數1～10的烷基或具有至少一個含氮基之基團為較佳。 式（I）中，R3 表示具有至少一個含氮基之基團之情況下，R1 及R2 分別獨立地表示氫原子或碳數1～4的烷基為較佳。In formula (I), when R 1 represents a group having at least one nitrogen-containing group, R 2 represents a hydrogen atom or an alkyl group having 1 to 10 carbons, and R 3 represents a hydrogen atom, a carbon number of 1 to 10 An alkyl group or a group having at least one nitrogen-containing group is preferred. In the formula (I), when R 3 represents a group having at least one nitrogen-containing group, it is preferable that R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

作為由式（I）表示之化合物的具體例，可舉出下述化合物。 R1 表示具有至少一個含氮基之基團，R2 及R3 表示氫原子之化合物：賴胺酸、2,3-二胺基酪酸、2,4-二胺基酪酸、鳥胺酸、2,3-二胺基丙酸、2,6-二胺基庚烷酸、4-甲基賴胺酸、3-甲基賴胺酸、5-羥基賴胺酸、3-甲基-L-精胺酸、精胺酸、高精胺酸、N5 -單甲基-L-精胺酸、N5 -[亞胺基（甲基胺基）甲基]-D-鳥胺酸、刀豆胺酸及組胺酸。 R1 及R2 表示氫原子、R3 表示具有至少一個含氮基之基團之化合物：N-（2-胺基乙基）甘胺酸及N-（2-胺基丙基）甘胺酸。 R1 表示具有至少一個含氮基之基團、R2 表示氫原子、R3 表示碳數1～10的烷基之化合物：N2 -甲基賴胺酸及N2 -甲基-L-精胺酸。 R1 及R3 表示具有至少一個含氮基之基團、R2 表示氫原子之化合物：N2 -（2-胺基乙基）-D-精胺酸及N2 -（2-胺基乙基）-L-精胺酸。 R1 表示碳數1～4的烷基、R2 表示具有至少一個含氮基之基團、R3 表示氫原子之化合物：包含2-甲基賴胺酸及2-甲基-L-精胺酸，但是並不限定於該等。As specific examples of the compound represented by formula (I), the following compounds can be given. R 1 represents a group having at least one nitrogen-containing group, and R 2 and R 3 represent compounds with hydrogen atoms: lysine, 2,3-diaminobutyric acid, 2,4-diaminobutyric acid, ornithine, 2,3-diaminopropionic acid, 2,6-diaminoheptanoic acid, 4-methyllysine, 3-methyllysine, 5-hydroxylysine, 3-methyl-L -Arginine, arginine, perarginine, N 5 -monomethyl-L-arginine, N 5 -[imino(methylamino)methyl]-D-ornithine, Concanavalin and histidine. R 1 and R 2 represent a hydrogen atom, R 3 represents a compound having at least one nitrogen-containing group: N-(2-aminoethyl)glycine and N-(2-aminopropyl)glycamine acid. R 1 represents a compound having at least one nitrogen-containing group, R 2 represents a hydrogen atom, and R 3 represents an alkyl group having 1 to 10 carbon atoms: N 2 -methyl lysine and N 2 -methyl-L- Arginine. R 1 and R 3 represent a group having at least one nitrogen-containing group, and R 2 represents a compound with a hydrogen atom: N 2 -(2-aminoethyl)-D-arginine and N 2 -(2-amino group) Ethyl)-L-arginine. R 1 represents an alkyl group having 1 to 4 carbon atoms, R 2 represents a group having at least one nitrogen-containing group, and R 3 represents a compound containing a hydrogen atom: including 2-methyllysine and 2-methyl-L-fine Amino acid, but it is not limited to these.

作為包含一級胺基或二級胺基及至少一個追加的含氮之基團之單羧酸化合物且除了上述式（I）表示之化合物以外的化合物，可舉出3,4-二胺基酪酸及3-胺基-5-[（胺基亞胺基甲基）甲基胺基]戊烷酸。As the monocarboxylic acid compound containing a primary or secondary amino group and at least one additional nitrogen-containing group and other than the compound represented by the above formula (I), 3,4-diaminobutyric acid may be mentioned And 3-amino-5-[(aminoiminomethyl)methylamino]pentanoic acid.

作為具有特定含氮螯合劑中的至少2個含氮之基團且不具有羧基之化合物，可舉出選自包括具有雙胍基之化合物及其鹽之群組中之至少1種雙胍化合物。 雙胍化合物所具有之雙胍基的數並無特別限制，可以具有複數個雙胍基。Examples of the compound having at least two nitrogen-containing groups in the specific nitrogen-containing chelating agent and not having a carboxyl group include at least one biguanide compound selected from the group consisting of compounds having a biguanide group and salts thereof. The number of biguanide groups possessed by the biguanide compound is not particularly limited, and it may have a plurality of biguanide groups.

作為雙胍化合物，例如可舉出由下述式（II）表示之化合物及其鹽。As a biguanide compound, the compound represented by following formula (II) and its salt are mentioned, for example.

[化學式1]

Figure 02_image001
[Chemical formula 1]
Figure 02_image001

式（II）中，R10 、R11 、R12 及R13 分別獨立地表示氫原子、或選自包括經取代或未經取代之芳基、經取代或未經取代之碳數3～10的環狀烷基及經取代或未經取代之碳數1～10的直鏈狀或支鏈狀烷基之群組中之基團。 R14 表示氫原子。 其中，R10 、R11 、R12 及R13 中的至少一個表示經取代或未經取代之芳基或者作為取代基而具有芳基之基團，並且R10 、R11 、R12 及R13 中的至少2個表示氫原子。 又，R13 與R14 可以彼此鍵結而形成咪唑環。 另外，由R10 、R11 、R12 及R13 中的至少一個表示之“作為取代基而具有芳基之基團”係指，選自包括具有芳基之碳數3～10的環狀烷基及具有芳基之碳數1～10的直鏈狀或者支鏈狀烷基之群組中之至少1種。In the formula (II), R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom, or are selected from the group including substituted or unsubstituted aryl groups, substituted or unsubstituted carbon numbers 3-10 The cyclic alkyl group and the substituted or unsubstituted linear or branched chain alkyl group with 1-10 carbon atoms. R 14 represents a hydrogen atom. Wherein, at least one of R 10 , R 11 , R 12 and R 13 represents a substituted or unsubstituted aryl group or a group having an aryl group as a substituent, and R 10 , R 11 , R 12 and R At least two of 13 represent hydrogen atoms. In addition, R 13 and R 14 may be bonded to each other to form an imidazole ring. In addition, the "group having an aryl group as a substituent" represented by at least one of R 10 , R 11 , R 12 and R 13 refers to a group selected from the group including cyclic groups having an aryl group and having 3 to 10 carbon atoms. At least one of an alkyl group and a C1-C10 linear or branched alkyl group having an aryl group.

作為由R10 ～R13 表示之芳基，可舉出苯基、萘基及蒽基，苯基或萘基為較佳，苯基為更佳。 作為芳基可具有之取代基，可舉出鹵素原子（例如，Cl、Br或F）、碳數1～10的直鏈狀或支鏈狀烷基、碳數3～10的環狀烷基、碳數1～10的直鏈狀或支鏈狀烷氧基、碳數3～10的環狀烷氧基、硝基、硫醇基（-SH）、二羥丙基及經取代或未經取代之苯基，鹵素原子或碳數1～4的直鏈狀或者支鏈狀烷基為較佳。 從缺陷抑制性之觀點考慮，作為由R10 ～R13 表示之芳基，未經取代之苯基為較佳。Examples of the aryl group represented by R 10 to R 13 include a phenyl group, a naphthyl group, and an anthryl group. A phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. Examples of the substituent that the aryl group may have include a halogen atom (for example, Cl, Br, or F), a linear or branched alkyl group having 1 to 10 carbons, and a cyclic alkyl group having 3 to 10 carbons. , Linear or branched alkoxy with 1 to 10 carbons, cyclic alkoxy with 3 to 10 carbons, nitro, thiol (-SH), dihydroxypropyl and substituted or unsubstituted The substituted phenyl group is preferably a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. From the viewpoint of defect suppression properties, the aryl group represented by R 10 to R 13 is preferably an unsubstituted phenyl group.

作為由R10 ～R13 表示之碳數3～10的環狀烷基，可舉出環丁基、環戊基、環己基、環庚基及降莰基以及氫化伸萘基等2環式烷基。 作為由R10 ～R13 表示之碳數3～10的環狀烷基可具有之取代基，可舉出鹵素原子（例如，Cl、Br或F）、碳數1～10的直鏈狀或支鏈狀烷基、碳數3～10的環狀烷基及經取代或未經取代之苯基。Examples of the cyclic alkyl group having 3 to 10 carbon atoms represented by R 10 to R 13 include bicyclic groups such as cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, norbornyl, and hydronaphthyl alkyl. Examples of substituents that the cyclic alkyl group having 3 to 10 carbons represented by R 10 to R 13 may have include a halogen atom (for example, Cl, Br, or F), a straight chain having 1 to 10 carbons, or A branched alkyl group, a cyclic alkyl group having 3 to 10 carbon atoms, and a substituted or unsubstituted phenyl group.

作為由R10 ～R13 表示之碳數1～10的直鏈狀或支鏈狀烷基，可舉出甲基、乙基、丙基、丁基、戊基、己基、辛基、異丙基、異丁基、三級丁基、辛基、1,1,2,2-四甲基丙基及癸基。 作為由R10 ～R13 表示之碳數1～10的直鏈狀或支鏈狀烷基可具有之取代基，可舉出鹵素原子（例如，Cl、Br或F）、碳數1～10的直鏈狀或支鏈狀烷氧基、碳數1～10的直鏈狀或支鏈狀氟烷氧基、碳數3～10的環狀烷氧基及經取代或未經取代之芳基。Examples of linear or branched alkyl groups having 1 to 10 carbon atoms represented by R 10 to R 13 include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and isopropyl. Base, isobutyl, tertiary butyl, octyl, 1,1,2,2-tetramethylpropyl and decyl. Examples of substituents that the linear or branched alkyl group having 1 to 10 carbons represented by R 10 to R 13 may have include halogen atoms (for example, Cl, Br, or F), and 1 to 10 carbons. Linear or branched alkoxy groups, linear or branched fluoroalkoxy groups with 1 to 10 carbons, cyclic alkoxy groups with 3 to 10 carbons, and substituted or unsubstituted aromatic groups base.

作為R10 ～R13 的組合，R10 ～R13 中的1個或2個表示經取代或未經取代之芳基（更佳為經取代或未經取代之苯基），其餘表示氫原子之組合為較佳，R10 ～R13 中的1個表示經取代或未經取代之芳基（更佳為未經取代之苯基），其餘表示氫原子之組合為更佳。 又，R13 及R14 為彼此鍵結而未形成咪唑環為較佳。As the combination of R 10 ~ R 13, R 10 ~ R 13 is 1 or 2 represents a substituted or non-substituted aryl group (more preferably a substituted or non-substituted phenyl), and the remaining represents a hydrogen atom The combination is preferable, one of R 10 to R 13 represents a substituted or unsubstituted aryl group (more preferably, an unsubstituted phenyl group), and the others represent a combination of hydrogen atoms. In addition, it is preferable that R 13 and R 14 are bonded to each other without forming an imidazole ring.

作為由式（II）表示之化合物的具體例，可舉出1-苯基雙胍、1-（鄰甲苯基）雙胍、1-（3-甲基苯基）雙胍、1-（4-甲基苯基）雙胍、1-（2-氯苯基）雙胍、1-（4-氯苯基）雙胍、1-（2,3-二甲基苯基）雙胍、1-（2,6-二甲基苯基）雙胍、1-（1-萘基）雙胍、1-（4-甲氧基苯基）雙胍、1-（4-硝基苯基）雙胍、1,1-二苯基雙胍、1,5-二苯基雙胍、1,5-雙（4-氯苯基）雙胍、1,5-雙（3-氯苯基）雙胍、1-（4-氯）苯基-5-（4-甲氧基）苯基雙胍、1,1-雙（3-氯-4-甲氧基苯基）雙胍、1,5-雙（3,4-二氯苯基）雙胍、1,5-雙（3,5-二氯苯基）雙胍及1,5-雙（4-溴苯基）雙胍。Specific examples of the compound represented by the formula (II) include 1-phenyl biguanide, 1-(o-tolyl) biguanide, 1-(3-methylphenyl) biguanide, 1-(4-methyl) Phenyl) biguanide, 1-(2-chlorophenyl) biguanide, 1-(4-chlorophenyl) biguanide, 1-(2,3-dimethylphenyl) biguanide, 1-(2,6-di Methylphenyl) biguanide, 1-(1-naphthyl) biguanide, 1-(4-methoxyphenyl) biguanide, 1-(4-nitrophenyl) biguanide, 1,1-diphenyl biguanide , 1,5-Diphenyl biguanide, 1,5-bis(4-chlorophenyl) biguanide, 1,5-bis(3-chlorophenyl) biguanide, 1-(4-chloro)phenyl-5- (4-Methoxy) phenyl biguanide, 1,1-bis(3-chloro-4-methoxyphenyl) biguanide, 1,5-bis(3,4-dichlorophenyl) biguanide, 1, 5-bis(3,5-dichlorophenyl) biguanide and 1,5-bis(4-bromophenyl) biguanide.

又，作為雙胍化合物中的2個具有雙胍基之化合物，可舉出由下述式（III）表示之化合物及其鹽。In addition, as the compound having two biguanide groups among the biguanide compounds, a compound represented by the following formula (III) and a salt thereof can be exemplified.

[化學式2]

Figure 02_image003
[Chemical formula 2]
Figure 02_image003

式（III）中，m表示1～10的整數。 R20 、R21 、R22 及R23 分別獨立地表示氫原子、或選自包括經取代或未經取代之芳基、經取代或未經取代之碳數3～10的環狀烷基及經取代或未經取代之碳數1～10的直鏈狀或支鏈狀烷基之群組中之基團。 R24 表示氫原子、或選自包括經取代或未經取代之芳基、經取代或未經取代之苯基乙基及經取代或未經取代之苄基烷基之群組中之基團。 m係2以上的整數之情況下，複數個R24 可以相同亦可以不同。 其中，R20 、R21 、R22 、R23 及R24 中的至少一個表示經取代或未經取代之芳基或者表示作為取代基而具有芳基之基團，並且R20 、R21 、R22 及R23 中的至少2個表示氫原子。 另外，由R20 、R21 、R22 、R23 及R24 中的至少一個表示之“作為取代基而具有芳基之基團”係指，選自包括具有芳基之碳數3～10的環狀烷基及具有芳基之碳數1～10的直鏈狀或者支鏈狀烷基之群組中之至少1種。In formula (III), m represents an integer of 1-10. R 20 , R 21 , R 22 and R 23 each independently represent a hydrogen atom, or are selected from the group consisting of a substituted or unsubstituted aryl group, a substituted or unsubstituted cyclic alkyl group having 3 to 10 carbon atoms, and A group of substituted or unsubstituted linear or branched alkyl groups having 1 to 10 carbon atoms. R 24 represents a hydrogen atom, or a group selected from the group consisting of substituted or unsubstituted aryl, substituted or unsubstituted phenylethyl, and substituted or unsubstituted benzylalkyl . When m is an integer of 2 or more, a plurality of R 24 may be the same or different. Wherein, at least one of R 20 , R 21 , R 22 , R 23 and R 24 represents a substituted or unsubstituted aryl group or a group having an aryl group as a substituent, and R 20 , R 21 , At least two of R 22 and R 23 represent a hydrogen atom. In addition, the "group having an aryl group as a substituent" represented by at least one of R 20 , R 21 , R 22 , R 23, and R 24 means a group selected from the group including those having an aryl group having 3 to 10 carbon atoms At least one of the cyclic alkyl group and the linear or branched chain alkyl group having 1 to 10 carbon atoms having an aryl group.

由R20 ～R24 表示之經取代或未經取代之芳基的具體例、由R20 ～R23 表示之經取代或未經取代之碳數3～10的環狀烷基的具體例及由R20 ～R23 表示之經取代或未經取代之碳數1～10的直鏈狀或支鏈狀烷基的具體例均包含由上述式（II）中的R10 ～R13 表示之各基團及其較佳的態樣且相同。 又，作為由R24 表示之苯基乙基及苄基烷基可具有之取代基，可舉出由上述式（II）中的R10 ～R13 表示之芳基可具有之取代基。Specific examples of substituted or unsubstituted aryl groups represented by R 20 to R 24 , specific examples of substituted or unsubstituted cyclic alkyl groups having 3 to 10 carbons represented by R 20 to R 23, and Specific examples of the substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms represented by R 20 to R 23 include those represented by R 10 to R 13 in the above formula (II) Each group and its preferred aspect are the same. And, as phenylethyl and benzyl groups represented by the sum of R 24 may have a substituent group, include a in the above formula (II) R 10 ~ R 13 represents a group of the aryl group may have the substituent.

作為R20 ～R23 ，表示氫原子或者經取代或未經取代之芳基為較佳。其中，R20 及R22 表示可以經鹵素原子或碳數1～4的直鏈狀或者支鏈狀烷基取代之苯基，R21 及R23 表示氫原子之組合為更佳。 作為R24 ，氫原子為較佳。 作為m，2～8為較佳，4～8為更佳，6為進一步較佳。R 20 to R 23 preferably represent a hydrogen atom or a substituted or unsubstituted aryl group. Among them, R 20 and R 22 represent a phenyl group which may be substituted with a halogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms. It is more preferable that R 21 and R 23 represent a combination of hydrogen atoms. As R 24 , a hydrogen atom is preferred. As m, 2 to 8 are preferable, 4 to 8 are more preferable, and 6 is still more preferable.

作為由式（III）表示之化合物的具體例，可舉出亞乙基二雙胍、伸丙基二雙胍、四亞甲基二雙胍、五亞甲基二雙胍、六亞甲基二雙胍、七亞甲基二雙胍、八亞甲基二雙胍、1,1’-六亞甲基雙（5-（對氯苯基）雙胍）（洛赫西定）、2-（苄氧基甲基）戊烷-1,5-雙（5-己基雙胍）、2-（苯硫基甲基）戊烷-1,5-雙（5-苯乙基雙胍）、3-（苯硫基）己烷-1,6-雙（5-己基雙胍）、3-（苯硫基）己烷-1,6-雙（5-環己基雙胍）、3-（苄硫基）己烷-1,6-雙（5-己基雙胍）及3-（苄硫基）己烷-1,6-雙（5-環己基雙胍）。As specific examples of the compound represented by the formula (III), ethylene bibiguanide, propylene bibiguanide, tetramethylene bibiguanide, pentamethylene bibiguanide, hexamethylene bibiguanide, seven Methylene bisbiguanide, Octamethylene bisbiguanide, 1,1'-hexamethylene bis(5-(p-chlorophenyl)biguanide) (loxidine), 2-(benzyloxymethyl) Pentane-1,5-bis(5-hexyl biguanide), 2-(phenylthiomethyl)pentane-1,5-bis(5-phenethyl biguanide), 3-(phenylthio)hexane -1,6-bis(5-hexyl biguanide), 3-(phenylthio)hexane-1,6-bis(5-cyclohexyl biguanide), 3-(benzylthio)hexane-1,6- Bis(5-hexyl biguanide) and 3-(benzylthio)hexane-1,6-bis(5-cyclohexyl biguanide).

作為具有2個雙胍基之雙胍化合物且除了由上述式（III）表示之化合物以外的化合物，可舉出苯基二雙胍、萘基二雙胍、吡啶基二雙胍、哌𠯤基二雙胍、鄰苯二甲醯二雙胍、1,1’-[4-（十二烷氧基）-間伸苯基]二雙胍、2-（癸基硫甲基）戊烷-1,5-雙（5-異丙基雙胍）、2-（癸基硫甲基）戊烷-1,5-雙（5,5-二乙基雙胍）及由下述結構式表示之二雙胍。 [化學式3]

Figure 02_image005
Examples of the biguanide compound having two biguanide groups other than the compound represented by the above formula (III) include phenylbibiguanide, naphthylbibiguanide, pyridylbibiguanide, piperidine bisbiguanide, and o-benzene Metformin, 1,1'-[4-(dodecyloxy)-metaphenyl]bibiguanide, 2-(decylthiomethyl)pentane-1,5-bis(5- Isopropyl biguanide), 2-(decylthiomethyl)pentane-1,5-bis(5,5-diethyl biguanide), and the bis biguanide represented by the following structural formula. [Chemical formula 3]
Figure 02_image005

作為具有複數個雙胍基之雙胍化合物，可舉出高分子雙胍化合物。 作為高分子雙胍化合物，例如可舉出由下述式（IV）表示之化合物。 [化學式4]

Figure 02_image007
式（IV）中，n表示2以上的整數。複數個R25 分別獨立地表示氫原子或者經取代或未經取代之碳數1～6的烷基。複數個R26 分別獨立地表示經取代或未經取代之碳數1～20的伸烷基。Examples of the biguanide compound having a plurality of biguanide groups include a polymer biguanide compound. As a polymer biguanide compound, the compound represented by following formula (IV) is mentioned, for example. [Chemical formula 4]
Figure 02_image007
In formula (IV), n represents an integer of 2 or more. A plurality of R 25 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. A plurality of R 26 each independently represents a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms.

作為R25 ，氫原子或未經取代之碳數1～6的烷基為較佳，氫原子為更佳。As R 25 , a hydrogen atom or an unsubstituted alkyl group having 1 to 6 carbon atoms is preferred, and a hydrogen atom is more preferred.

作為由R26 表示之碳數1～20的伸烷基，碳數4～10的伸烷基為較佳，碳數6的伸烷基（伸己基）為更佳。 作為由R26 表示之碳數1～20的伸烷基可具有之取代基，可舉出碳數1～10的直鏈狀或支鏈狀烷基、碳數3～10的環狀烷基、經取代或未經取代之苯基、碳數1～10的直鏈狀或支鏈狀烷氧基、碳數3～10的環狀烷氧基、硝基、羥基、硫醇基、鹵素原子、胺基、二羥丙基、雙胍基、氰基、羧基及磺酸基。As the alkylene group having 1 to 20 carbon atoms represented by R 26 , an alkylene group having 4 to 10 carbon atoms is preferred, and an alkylene group having 6 carbon atoms (hexylene) is more preferred. Examples of substituents that the alkylene group having 1 to 20 carbons represented by R 26 may have include linear or branched alkyl groups having 1 to 10 carbons, and cyclic alkyl groups having 3 to 10 carbons , Substituted or unsubstituted phenyl, linear or branched alkoxy with 1 to 10 carbons, cyclic alkoxy with 3 to 10 carbons, nitro, hydroxyl, thiol, halogen Atom, amine group, dihydroxypropyl group, biguanide group, cyano group, carboxyl group and sulfonic acid group.

作為n，只要為2以上的整數則並無特別限制，5以上的整數為較佳，30以上的整數為更佳，從使用試劑盒A而製備之處理液的殘渣去除性及/或缺陷抑制性更優異之觀點考慮，150以上的整數為進一步較佳。上限並無特別限制，6000以下的整數為較佳，1000以下的整數為更佳，500以下的整數為進一步較佳。As n, there is no particular limitation as long as it is an integer of 2 or more. An integer of 5 or more is preferable, and an integer of 30 or more is more preferable. The residue removability and/or defect suppression of the treatment solution prepared using kit A From the viewpoint of more excellent performance, an integer of 150 or more is more preferable. The upper limit is not particularly limited. An integer of 6000 or less is preferred, an integer of 1000 or less is more preferred, and an integer of 500 or less is even more preferred.

又，作為高分子雙胍，可舉出在側鏈上具有側基雙胍部分之高分子雙胍。作為具有這樣的側基雙胍部分之高分子雙胍，例如可舉出聚（乙烯基雙胍）、聚（N-乙烯基雙胍）、聚（烯丙基雙胍）及它們的共聚物等雙胍取代α-烯烴單體的聚合物。在該等聚合物中，調整每個聚合鏈的側基雙胍部分的數時，適當調整與雙胍取代α-烯烴單體共聚之烯烴單體的種類及量即可。In addition, examples of the macromolecular biguanide include a macromolecular biguanide having a side chain biguanide moiety. Examples of the macromolecular biguanide having such a side group biguanide moiety include biguanide substituted α-biguanide such as poly(vinyl biguanide), poly(N-vinyl biguanide), poly(allyl biguanide), and their copolymers. Polymers of olefin monomers. In these polymers, when adjusting the number of side group biguanide moieties per polymer chain, the type and amount of the olefin monomer copolymerized with the biguanide-substituted α-olefin monomer may be appropriately adjusted.

雙胍化合物可以為上述之具有雙胍基之化合物的鹽。 作為具有雙胍基之化合物的鹽，可舉出有機酸鹽及無機酸鹽。 作為形成無機酸鹽之無機酸，可舉出鹽酸、氫氟酸、氫溴酸、氫碘酸、膦酸、磷酸、磺酸及硫酸，鹽酸為較佳。 作為形成有機酸鹽之有機酸，可舉出乙酸、丙酸、酪酸、戊酸、己酸、辛酸、2-辛烯酸、月桂酸、5-十二碳烯酸、肉荳蔻酸、十五烷酸、棕檁酸、油酸、硬脂酸、二十烷酸、十七烷酸、棕櫚油酸、蓖麻油酸、12-羥基硬脂酸、16-羥基十六烷酸、2-羥基己酸、12-羥基十二烷酸、5-羥基十二烷酸、5-羥基癸烷酸、4-羥基癸烷酸、葡萄糖酸、十二烷二酸、十一烷二酸、癸二酸、苯甲酸、羥基苯甲酸及對苯二甲酸。 作為具有雙胍基之化合物的鹽，鹽酸鹽、乙酸鹽或葡萄糖酸鹽為較佳。The biguanide compound may be a salt of the above-mentioned compound having a biguanide group. Examples of the salt of the compound having a biguanide group include organic acid salts and inorganic acid salts. Examples of the inorganic acid forming the inorganic acid salt include hydrochloric acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, phosphonic acid, phosphoric acid, sulfonic acid, and sulfuric acid, with hydrochloric acid being preferred. Examples of organic acids that form organic acid salts include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, 2-octenic acid, lauric acid, 5-dodecenoic acid, myristic acid, and pentadecenoic acid. Alkanoic acid, palmulic acid, oleic acid, stearic acid, eicosanic acid, heptadecanoic acid, palmitoleic acid, ricinoleic acid, 12-hydroxystearic acid, 16-hydroxyhexadecanoic acid, 2-hydroxy Caproic acid, 12-hydroxydodecanoic acid, 5-hydroxydodecanoic acid, 5-hydroxydecanoic acid, 4-hydroxydecanoic acid, gluconic acid, dodecanedioic acid, undecanedioic acid, sebacic acid Acid, benzoic acid, hydroxybenzoic acid and terephthalic acid. As the salt of the compound having a biguanide group, hydrochloride, acetate, or gluconate is preferred.

作為除了上述化合物以外的特定含氮螯合劑，例如可舉出乙二胺、丙二胺、丁二胺、伸己基二胺、二乙三胺、三伸乙四胺及具有至少2個含氮之基團之聚乙烯亞胺等的伸烷基二胺。 又，作為特定含氮螯合劑而舉出之化合物所具有之伸烷基部分中的至少一個亞甲基單元（-CH2 -）中，經-O-、-NH-、-S-等雜原子取代之化合物亦包括在特定含氮螯合劑中。As specific nitrogen-containing chelating agents other than the above-mentioned compounds, for example, ethylenediamine, propylenediamine, butanediamine, hexylenediamine, diethylenetriamine, triethylenetetramine and having at least two nitrogen-containing The group of polyethyleneimine and other alkylene diamines. In addition, in at least one methylene unit (-CH 2 -) in the alkylene moiety of the compound exemplified as a specific nitrogen-containing chelating agent, the compound has a heterogeneous group such as -O-, -NH-, -S-, etc. Atom-substituted compounds are also included in specific nitrogen-containing chelating agents.

作為特定含氮螯合劑，選自包括由上述式（I）～（IV）表示之化合物及它們的鹽之群組中之化合物為較佳，從本發明的效果及相對於SiOx層之耐腐蝕性更優異之觀點考慮，選自包括由上述式（II）～（IV）表示之化合物及它們的鹽之群組中之雙胍化合物為更佳，由上述式（III）表示之化合物或其鹽為進一步較佳。As the specific nitrogen-containing chelating agent, a compound selected from the group consisting of the compounds represented by the above formulas (I) to (IV) and their salts is preferred. From the effect of the present invention and the corrosion resistance relative to the SiOx layer From the viewpoint of more excellent performance, the biguanide compound selected from the group including the compounds represented by the above formulas (II) to (IV) and their salts is more preferred, and the compound represented by the above formula (III) or the salts thereof To be further preferred.

特定含氮螯合劑可以單獨使用1種，亦可以併用2種以上。 特定含氮螯合劑的含量（存在2種以上之情況下係其總計）並無特別限制，相對於處理液的總質量係0.0001質量%以上為較佳，從本發明的效果更優異之觀點考慮，0.003質量%以上為更佳，0.01質量%以上為進一步較佳。上限並無特別限制，10質量%以下為較佳，3.0質量%為更佳，2.0質量%以下為進一步較佳。A specific nitrogen-containing chelating agent may be used individually by 1 type, and may use 2 or more types together. The content of the specific nitrogen-containing chelating agent (the total when there are two or more) is not particularly limited, but it is preferably 0.0001% by mass or more relative to the total mass of the treatment liquid, and the effect of the present invention is more excellent. , 0.003% by mass or more is more preferable, and 0.01% by mass or more is still more preferable. The upper limit is not particularly limited, but 10% by mass or less is preferable, 3.0% by mass or less is more preferable, and 2.0% by mass or less is still more preferable.

螯合劑可以單獨使用1種，亦可以併用2種以上。 螯合劑的含量（存在2種以上之情況下係其總計）並無特別限制，相對於處理液的總質量係0.01～10質量%為較佳，0.01～3.0質量%為更佳。A chelating agent may be used individually by 1 type, and may use 2 or more types together. The content of the chelating agent (the total when there are two or more) is not particularly limited, but it is preferably 0.01 to 10% by mass, and more preferably 0.01 to 3.0% by mass relative to the total mass of the treatment liquid.

作為螯合劑，使用實施純化處理而成之螯合劑為較佳。 作為螯合劑的純化處理方法並無特別限制，例如可舉出過濾、離子交換、蒸餾、吸附純化、再結晶、再沉澱、升華及使用管柱之純化等公知的方法以及該等方法的組合。其中，對含有螯合劑之原料實施後述之金屬去除步驟而獲得包含螯合劑之純化物之方法為較佳。As the chelating agent, it is preferable to use a chelating agent that has been purified. The purification treatment method of the chelating agent is not particularly limited, and examples thereof include well-known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column, and combinations of these methods. Among them, a method of performing the metal removal step described later on the raw material containing the chelating agent to obtain a purified product containing the chelating agent is preferred.

（含氟化合物） 作為含氟化合物，例如可舉出氫氟酸（氟酸）、氟化銨、氟化四甲基銨及氟化四丁基銨，氫氟酸、氟化銨或氟化四甲基銨為較佳。含氟化合物在處理液中具有去除殘渣之功能。其結果，處理液包含含氟化合物之情況下，殘渣去除性更加優異。 作為含氟化合物，氫氟酸為較佳。(Fluorine-containing compound) Examples of fluorine-containing compounds include hydrofluoric acid (fluoric acid), ammonium fluoride, tetramethylammonium fluoride, and tetrabutylammonium fluoride. Hydrofluoric acid, ammonium fluoride or tetramethylammonium fluoride is Better. The fluorine-containing compound has the function of removing residue in the treatment liquid. As a result, when the treatment liquid contains a fluorine-containing compound, the residue removability is more excellent. As the fluorine-containing compound, hydrofluoric acid is preferred.

含氟化合物可以單獨使用1種，亦可以併用2種以上。 在處理液中，上述含氟化合物（存在2種以上之情況下係其總計）的含量相對於處理液的總質量係0.01～5.0質量%為較佳，0.1～2.0質量%為更佳。A fluorine-containing compound may be used individually by 1 type, and may use 2 or more types together. In the treatment liquid, the content of the above-mentioned fluorine-containing compound (in the case of two or more kinds, the total amount) is preferably 0.01 to 5.0% by mass, and more preferably 0.1 to 2.0% by mass relative to the total mass of the treatment liquid.

處理液中，作為去除劑包含選自包括氫氟酸、氟化銨、氟化四甲基銨、多元羧酸及聚胺基羧酸之群組中之至少1種為較佳。In the treatment liquid, it is preferable that the removing agent contains at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, polycarboxylic acid, and polyaminocarboxylic acid.

（羥胺化合物） 從本發明的效果及殘渣去除性優異之觀點考慮，處理液中作為去除劑包含選自包括羥胺（NH2 OH）、羥胺衍生物及該等鹽之群組中之至少1種含有羥胺化合物亦較佳。羥胺化合物具有促進殘渣的分解及可溶化並且去除蝕刻殘渣及灰化殘渣等的殘渣之功能。(Hydroxyamine compound) From the viewpoint of the effect of the present invention and the excellent residue removal ability, the treatment liquid contains at least one selected from the group consisting of hydroxylamine (NH 2 OH), hydroxylamine derivatives, and these salts as a removing agent Compounds containing hydroxylamine are also preferred. The hydroxylamine compound has the function of promoting the decomposition and solubilization of the residue, and removing residues such as etching residue and ashing residue.

作為羥胺衍生物並無特別限制，例如可舉出O-甲基羥胺、O-乙基羥胺、N-甲基羥胺、N,N-二甲基羥胺、N,O-二甲基羥胺、N-乙基羥胺、N,N-二乙基羥胺、N,O-二乙基羥胺、O,N,N-三甲基羥胺、N,N-二羧基乙基羥胺及N,N-二磺基乙基羥胺等。The hydroxylamine derivative is not particularly limited, and examples include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, N,O-dimethylhydroxylamine, N -Ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-dicarboxyethylhydroxylamine and N,N-disulfonic acid Group ethyl hydroxylamine and so on.

羥胺（NH2 OH）及羥胺衍生物的鹽係上述之羥胺（NH2 OH）及羥胺衍生物的無機酸鹽或有機酸鹽為較佳，Cl、S、N或P等非金屬原子與氫原子鍵結而成之無機酸的鹽為更佳，鹽酸、硫酸或硝酸中的任一種酸的鹽為進一步較佳。 作為羥胺（NH2 OH）及羥胺衍生物的無機酸鹽，其中，硝酸羥胺、硫酸羥胺、鹽酸羥胺、磷酸羥胺、硫酸N,N-二乙基羥胺、硝酸N,N-二乙基羥胺或該等的混合物為較佳。 又，作為羥胺（NH2 OH）及羥胺衍生物的有機酸鹽，例如可舉出羥基銨檸檬酸鹽、羥基銨草酸鹽及羥基銨偏二氟等。 從殘渣去除性更優異之觀點考慮，作為羥胺化合物，羥胺（NH2 OH）為較佳。Hydroxylamine (NH 2 OH) of the above-described hydroxylamine and hydroxylamine salt type derivative (NH 2 OH) and an inorganic or organic acid salts of the hydroxylamine derivatives are preferred, Cl, S, N, or P and other non-metallic atomic hydrogen and A salt of an inorganic acid formed by bonding atoms is more preferable, and a salt of any acid of hydrochloric acid, sulfuric acid, or nitric acid is more preferable. As an inorganic acid salt of hydroxylamine (NH 2 OH) and hydroxylamine derivatives, among them, hydroxylamine nitrate, hydroxylamine sulfate, hydroxylamine hydrochloride, hydroxylamine phosphate, N,N-diethylhydroxylamine sulfate, N,N-diethylhydroxylamine nitrate or These mixtures are preferred. In addition, examples of organic acid salts of hydroxylamine (NH 2 OH) and hydroxylamine derivatives include hydroxylammonium citrate, hydroxylammonium oxalate, and hydroxylammonium metadifluoride. From the viewpoint of more excellent residue removability, as the hydroxylamine compound, hydroxylamine (NH 2 OH) is preferred.

羥胺化合物可以單獨使用1種，亦可以併用2種以上。 羥胺化合物的含量（存在2種以上之情況下係其總計）並無特別限制，相對於處理液的總質量係0.01～30質量%為較佳。從缺陷抑制性優異之觀點考慮，其下限相對於處理液的總質量係2.0質量%以上為更佳，3.0質量%以上為進一步較佳。羥胺化合物的含量的上限相對於處理液的總質量係10.0質量%以下為較佳。A hydroxylamine compound may be used individually by 1 type, and may use 2 or more types together. The content of the hydroxylamine compound (when two or more types are present, the total amount) is not particularly limited, but it is preferably 0.01 to 30% by mass relative to the total mass of the treatment liquid. From the viewpoint of excellent defect suppression properties, the lower limit is more preferably 2.0% by mass or more with respect to the total mass of the treatment liquid, and more preferably 3.0% by mass or more. The upper limit of the content of the hydroxylamine compound is preferably 10.0% by mass or less with respect to the total mass of the treatment liquid.

＜pH調節劑＞ 為了調節處理液的pH，處理液可以包含pH調節劑。 作為pH調節劑，可舉出鹼性化合物及酸性化合物。＜pH adjuster＞ In order to adjust the pH of the treatment liquid, the treatment liquid may contain a pH adjuster. Examples of the pH adjuster include basic compounds and acidic compounds.

（鹼性化合物） 處理液中作為pH調節劑包含鹼性化合物為較佳。鹼性化合物係指1g溶解於100g的水時溶液的pH成為9以上之化合物。 另外，在本說明書中，上述之去除劑中所包含之化合物不包括在鹼性化合物中。(Basic compound) The treatment liquid preferably contains a basic compound as a pH adjuster. The basic compound refers to a compound whose solution pH becomes 9 or higher when 1 g is dissolved in 100 g of water. In addition, in this specification, the compound contained in the above-mentioned remover is not included in the basic compound.

作為鹼性化合物並無特別限制，從殘渣去除性更優異且本發明的效果亦更優異之觀點考慮，含氮脂環化合物、氫氧化銨、水溶性胺或四級銨氫氧化物為較佳，含氮脂環化合物、水溶性胺或四級銨氫氧化物為更佳。 以下，分別對含氮脂環化合物、氫氧化銨、水溶性胺及四級銨鹽進行詳細說明。The basic compound is not particularly limited. From the standpoint of more excellent residue removal and the effect of the present invention, nitrogen-containing alicyclic compound, ammonium hydroxide, water-soluble amine or quaternary ammonium hydroxide are preferred , Nitrogen-containing alicyclic compounds, water-soluble amines or quaternary ammonium hydroxides are more preferred. Hereinafter, the nitrogen-containing alicyclic compound, ammonium hydroxide, water-soluble amine, and quaternary ammonium salt will be described in detail.

-含氮脂環化合物- 作為含氮脂環化合物，例如可舉出1,8-二吖雙環[5.4.0]-7-十一烯（DBU）、ε-己內醯胺、下述化合物1、下述化合物2、下述化合物3、1,4-二吖雙環[2.2.2]辛烷（DABCO）、四氫糠胺、N-（2-胺基乙基）哌𠯤、羥基乙基哌𠯤、哌𠯤、2-甲基哌𠯤、反式-2,5-二甲基哌𠯤、順式-2,6-二甲基哌𠯤、2-哌啶甲醇、環己基胺及1,5-二吖雙環[4,3,0]-5-壬烯等。-Nitrogen-containing alicyclic compound- Examples of nitrogen-containing alicyclic compounds include 1,8-diazebicyclo[5.4.0]-7-undecene (DBU), ε-caprolactam, the following compound 1, the following compound 2, The following compound 3, 1,4-diazbicyclo[2.2.2]octane (DABCO), tetrahydrofurfurylamine, N-(2-aminoethyl) piper, hydroxyethyl piper, piper, 2-methylpiperidine, trans-2,5-dimethylpiperidine, cis-2,6-dimethylpiperidine, 2-piperidine methanol, cyclohexylamine, and 1,5-diazabicyclo [4,3,0]-5-nonene and so on.

[化學式5]

Figure 02_image009
[Chemical formula 5]
Figure 02_image009

其中，從殘渣去除性更優異且本發明的效果亦更優異之觀點考慮，作為含氮脂環化合物，1,8-二吖雙環[5.4.0]-7-十一烯（DBU）、四氫糠胺、N-（2-胺基乙基）哌𠯤或1，4-二吖雙環[2.2.2]辛烷（DABCO）為較佳，DBU為更佳。Among them, from the viewpoint that the residue removability is more excellent and the effect of the present invention is also more excellent, as the nitrogen-containing alicyclic compound, 1,8-diazebicyclo[5.4.0]-7-undecene (DBU), tetrakis Hydrofurfurylamine, N-(2-aminoethyl)piperidine, or 1,4-diazebicyclo[2.2.2]octane (DABCO) is preferred, and DBU is more preferred.

含氮脂環化合物可以單獨使用1種，亦可以併用2種以上。 含氮脂環化合物的含量（存在2種以上之情況下係其總計）並無特別限制，相對於處理液的總質量係0.01～10質量%為較佳，0.05～5.0質量%為更佳。A nitrogen-containing alicyclic compound may be used individually by 1 type, and may use 2 or more types together. The content of the nitrogen-containing alicyclic compound (when two or more types are present, the total amount) is not particularly limited, but 0.01 to 10% by mass relative to the total mass of the treatment liquid is preferable, and 0.05 to 5.0% by mass is more preferable.

-氫氧化銨- 作為鹼性化合物，包含氫氧化銨（NH4 OH）之情況下，其含量並無特別限制，相對於處理液的總質量係0.01～10質量%為較佳，0.05～5.0質量%為更佳。-Ammonium hydroxide- As the basic compound, when ammonium hydroxide (NH 4 OH) is included, its content is not particularly limited, but 0.01-10% by mass relative to the total mass of the treatment liquid is preferably, 0.05-5.0 The quality% is better.

-水溶性胺- 在本說明書中，水溶性胺係指能夠在1L的水中溶解50g以上的胺。又，上述含氮脂環化合物及氫氧化銨均不包括在水溶性胺中。 作為水溶性胺，例如可舉出在分子內具有一級胺基（-NH2 ）之一級胺、在分子內具有二級胺基（＞NH）之二級胺、在分子內具有三級胺基（＞N-）之三級胺及它們的鹽。又，水溶性胺可以為在分子內具有至少一個羥基烷基之化合物（胺基醇）。-Water-soluble amine- In this specification, water-soluble amine refers to an amine that can dissolve 50g or more in 1L of water. In addition, neither the aforementioned nitrogen-containing alicyclic compound nor ammonium hydroxide is included in the water-soluble amine. Examples of water-soluble amines include primary amines having a primary amine group (-NH 2 ) in the molecule, secondary amines having a secondary amine group (>NH) in the molecule, and a tertiary amine group in the molecule. (>N-) tertiary amines and their salts. In addition, the water-soluble amine may be a compound (amino alcohol) having at least one hydroxyalkyl group in the molecule.

作為水溶性胺中的一級胺，例如可舉出甲基胺、乙胺、丙胺、丁胺、戊胺、單乙醇胺（MEA）、單丙醇胺、單丁醇胺、甲氧基乙胺、甲氧基丙胺及2-胺基-2-甲基-1-丙醇（AMP）。 作為二級胺，例如可舉出二甲基胺、二乙胺、二丙胺、二丁胺（DBA）、2,2’-亞胺基二乙醇及N-（2-胺基乙基）乙醇胺（AEEA）。 作為三級胺，例如可舉出三甲基胺、三乙胺及三丁胺（TBA）。Examples of primary amines in water-soluble amines include methylamine, ethylamine, propylamine, butylamine, pentylamine, monoethanolamine (MEA), monopropanolamine, monobutanolamine, methoxyethylamine, Methoxypropylamine and 2-amino-2-methyl-1-propanol (AMP). Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine (DBA), 2,2'-iminodiethanol, and N-(2-aminoethyl)ethanolamine (AEEA). Examples of tertiary amines include trimethylamine, triethylamine, and tributylamine (TBA).

水溶性胺的含量並無特別限制，相對於處理液的總質量係0.01～10質量%為較佳，0.1～5.0質量%為更佳。The content of the water-soluble amine is not particularly limited, but it is preferably 0.01-10% by mass relative to the total mass of the treatment liquid, and more preferably 0.1-5.0% by mass.

-四級銨鹽- 作為四級銨鹽，可舉出四級銨氫氧化物。 作為四級銨氫氧化物，例如可舉出由下述式（a1）表示之化合物。-Quaternary ammonium salt- Examples of the quaternary ammonium salt include quaternary ammonium hydroxide. As a quaternary ammonium hydroxide, the compound represented by following formula (a1) is mentioned, for example.

[化學式6]

Figure 02_image011
[Chemical formula 6]
Figure 02_image011

上述式（a1）中，Ra1 ～Ra4 分別獨立地表示碳數1～16的烷基、碳數6～16的芳基、碳數7～16的芳烷基或碳數1～16的羥基烷基。Ra1 ～Ra4 中的至少2個可以彼此鍵結而形成環狀結構。In the above formula (a1), R a1 to R a4 each independently represent an alkyl group having 1 to 16 carbons, an aryl group having 6 to 16 carbons, an aralkyl group having 7 to 16 carbons, or an aralkyl group having 1 to 16 carbons. Hydroxyalkyl. At least two of Ra1 to Ra4 may be bonded to each other to form a cyclic structure.

作為由上述式（a1）表示之化合物，從容易獲得之觀點考慮，選自包括氫氧化四甲銨（TMAH）、氫氧化四乙銨（TEAH）、氫氧化四丙銨、四丁基氫氧化銨（TBAH）、氫氧化甲基三丙銨、氫氧化甲基三丁銨、氫氧化乙基三甲銨、氫氧化二甲基二乙銨、苄基三甲基氫氧化銨（BzTMAH）、氫氧化十六烷基三甲銨、氫氧化（2-羥基乙基）三甲銨及氫氧化螺-（1,1’）-聯吡咯啶鎓之群組中之至少1種為較佳，TMAH、TEAH、TBAH、BzTMAH為更佳，氫氧化四甲銨（TMAH）、四丁基氫氧化銨（TBAH）或苄基三甲基氫氧化銨（BzTMAH）為進一步較佳。The compound represented by the above formula (a1) is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide, and tetrabutylhydroxide from the viewpoint of easy availability. Ammonium (TBAH), methyl tripropyl ammonium hydroxide, methyl tributyl ammonium hydroxide, ethyl trimethyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, benzyl trimethyl ammonium hydroxide (BzTMAH), hydrogen At least one of the group of cetyltrimethylammonium oxide, (2-hydroxyethyl)trimethylammonium hydroxide, and spiro-(1,1')-bipyrrolidinium hydroxide is preferred, TMAH, TEAH , TBAH and BzTMAH are more preferred, and tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH) or benzyltrimethylammonium hydroxide (BzTMAH) are further preferred.

四級銨鹽可以單獨使用1種，亦可以併用2種以上。 四級銨鹽的含量相對於處理液的總質量係0.01～15質量%為較佳，0.1～10質量%為更佳。The quaternary ammonium salt may be used alone or in combination of two or more kinds. The content of the quaternary ammonium salt is preferably 0.01 to 15% by mass relative to the total mass of the treatment liquid, and more preferably 0.1 to 10% by mass.

（酸性化合物） 清洗液中作為pH調節劑可以包含酸性化合物。 酸性化合物可以為無機酸，亦可以為有機酸（但是上述之螯合劑除外）。 作為無機酸，可舉出硫酸、鹽酸、乙酸、硝酸及磷酸，硫酸、鹽酸或乙酸為較佳。作為有機酸，可舉出甲酸、乙酸、丙酸及酪酸等低級（碳數1～4）脂肪族單羧酸。又，上述之螯合劑亦可以兼具作為酸性化合物的作用。(Acid compound) The cleaning liquid may contain an acidic compound as a pH adjuster. The acidic compound can be an inorganic acid or an organic acid (except for the above-mentioned chelating agent). Examples of the inorganic acid include sulfuric acid, hydrochloric acid, acetic acid, nitric acid, and phosphoric acid, with sulfuric acid, hydrochloric acid, or acetic acid being preferred. Examples of organic acids include lower (carbon number 1 to 4) aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, and butyric acid. In addition, the above-mentioned chelating agent may also serve as an acidic compound.

pH調節劑可以單獨使用1種，亦可以組合2種以上而使用。 關於pH調節劑的種類及含量，適當選擇所使用之pH調節劑的種類來調節含量即可，以使處理液的pH在後述之較佳之範圍內。 處理液包含pH調節劑之情況下，其含量相對於處理液的總質量係0.01～20質量%為較佳，0.01～10質量%為更佳。A pH adjuster may be used individually by 1 type, and may be used in combination of 2 or more types. Regarding the type and content of the pH adjuster, it is sufficient to appropriately select the type of the pH adjuster to be used and adjust the content so that the pH of the treatment liquid is within the preferable range described later. When the treatment liquid contains a pH adjuster, the content thereof is preferably 0.01 to 20% by mass relative to the total mass of the treatment liquid, and more preferably 0.01 to 10% by mass.

＜金屬成分＞ 處理液可以包含金屬成分。 作為金屬成分，可舉出金屬粒子及金屬離子。例如，稱為金屬成分的含量時，表示金屬粒子及金屬離子的總含量。 處理液可以包含金屬粒子及金屬離子中的任一者，亦可以包含兩者。＜Metal composition＞ The treatment liquid may contain metal components. Examples of the metal component include metal particles and metal ions. For example, when it is called the content of the metal component, it means the total content of metal particles and metal ions. The treatment liquid may contain any one of metal particles and metal ions, or may contain both.

作為金屬成分中所含有之金屬原子，例如可舉出選自包括Ag、Al、As、Au、Ba、Ca、Cd、Co、Cr、Cu、Fe、Ga、Ge、K、Li、Mg、Mn、Mo、Na、Ni、Pb、Sn、Sr、Ti及Zn之群組中之金屬原子。 金屬成分可以含有1種金屬原子，亦可以含有2種以上。 金屬粒子可以為單體亦可以為合金，金屬亦可以以與有機物結合之形態存在。 金屬成分可以為不可避免地包含在處理液所包含之各成分（原料）中之金屬成分，亦可以為在處理液的製造、儲存及/或移送時不可避免地包含之金屬成分，還可以有意添加。Examples of metal atoms contained in the metal component include those selected from Ag, Al, As, Au, Ba, Ca, Cd, Co, Cr, Cu, Fe, Ga, Ge, K, Li, Mg, Mn Metal atoms in the group of, Mo, Na, Ni, Pb, Sn, Sr, Ti and Zn. The metal component may contain one type of metal atom or two or more types. The metal particles can be a monomer or an alloy, and the metal can also exist in a form combined with organic matter. The metal component may be a metal component that is inevitably included in each component (raw material) contained in the treatment liquid, or may be a metal component that is inevitably included during the manufacture, storage, and/or transfer of the treatment liquid, or it may be intentionally included. Add to.

處理液含有金屬成分之情況下，多為金屬成分的含量相對於處理液的總質量係0.01質量ppt～10質量ppm的情況，0.1質量ppt～1質量ppm為較佳，0.1質量ppt～100質量ppb為更佳。When the treatment liquid contains metal components, the content of the metal component is usually 0.01 mass ppt-10 mass ppm relative to the total mass of the treatment liquid. 0.1 mass ppt-1 mass ppm is better, 0.1 mass ppt-100 mass ppb is better.

又，處理液含有Ca成分及Na成分之情況下，從本發明的效果、殘渣去除性及缺陷抑制性均平衡良好且優異之觀點考慮，在處理液中，Ca成分的含量與Na成分的含量之比例以質量比計係0.8～1.2為較佳，0.9～1.2為更佳。In addition, when the treatment liquid contains the Ca component and the Na component, from the viewpoint that the effects of the present invention, the residue removal properties, and the defect suppression properties are well-balanced and excellent, the content of the Ca component and the content of the Na component in the treatment liquid The ratio is preferably 0.8-1.2 in terms of mass ratio, more preferably 0.9-1.2.

另外，處理液中的金屬成分的種類及含量能夠藉由SP-ICP-MS法（Single Nano Particle Inductively Coupled Plasma Mass Spectrometry，單奈米粒子感應耦合電漿質譜法）來測量。 其中，SP-ICP-MS法使用與ICP-MS法（感應耦合電漿質譜法）相同的裝置，而只有資料分析不同。SP-ICP-MS法的資料分析能夠藉由市售的軟體來實施。 ICP-MS法中，作為測量對象之金屬成分的含量與其存在形態無關地進行測量。從而，作為測量對象之金屬粒子與金屬離子的總計質量作為金屬成分的含量來定量。 另一方面，SP-ICP-MS法中，能夠測量金屬粒子的含量。從而，藉由從試樣中的金屬成分的含量減去金屬粒子的含量，能夠計算出試樣中的金屬離子的含量。In addition, the type and content of metal components in the treatment solution can be measured by SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). Among them, the SP-ICP-MS method uses the same equipment as the ICP-MS method (inductively coupled plasma mass spectrometry), but only the data analysis is different. Data analysis of the SP-ICP-MS method can be implemented with commercially available software. In the ICP-MS method, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of the metal particles and metal ions as the measurement target is quantified as the content of the metal component. On the other hand, in the SP-ICP-MS method, the content of metal particles can be measured. Therefore, by subtracting the content of metal particles from the content of metal components in the sample, the content of metal ions in the sample can be calculated.

作為基於SP-ICP-MS法之測量方法，例如能夠使用Agilent Technologies Japan, Ltd製、Agilent 8800 三重四極ICP-MS（Inductively Coupled Plasma Mass Spectrometry、半導體分析用、選項#200），並且藉由實施例中所記載之方法來測量。作為除了上述以外的其他裝置，除PerkinElmer Co., Ltd.製NexION350S以外，還能夠使用Agilent Technologies Japan,Ltd製Agilent 8900。As a measurement method based on the SP-ICP-MS method, for example, Agilent Technologies Japan, Ltd., Agilent 8800 triple quadrupole ICP-MS (Inductively Coupled Plasma Mass Spectrometry, for semiconductor analysis, option #200) can be used. Measured by the method described in. As a device other than the above, in addition to NexION350S manufactured by PerkinElmer Co., Ltd., Agilent 8900 manufactured by Agilent Technologies Japan, Ltd. can also be used.

處理液中的各金屬成分的含量的調節方法並無特別限制。例如，藉由進行從處理液及/或包含用於製備處理液之各成分之原料去除金屬之公知的處理，能夠降低處理液中的金屬成分的含量。又，藉由向處理液添加包含金屬離子之化合物，能夠增加處理液中的金屬成分的含量。The method of adjusting the content of each metal component in the treatment liquid is not particularly limited. For example, it is possible to reduce the content of the metal component in the treatment liquid by performing a known treatment for removing metals from the treatment liquid and/or the raw materials containing the respective components used for the preparation of the treatment liquid. In addition, by adding a compound containing metal ions to the treatment liquid, the content of the metal component in the treatment liquid can be increased.

〔鈷離子〕 其中，處理液包含鈷離子為較佳。 處理液包含鈷離子之情況下，藉由化學平衡抑制金屬從金屬層溶出，其結果，認為本發明的效果更優異。尤其，金屬層包含Co時的耐腐蝕性更優異。又，藉由處理液包含鈷離子，提高缺陷抑制性。 處理液包含鈷離子之情況下，從本發明的效果及缺陷抑制性更優異之觀點考慮，鈷離子的含量相對於處理液的總質量係0.001～1000質量ppb為較佳，0.3～1000質量ppt為更佳，1.0～200質量ppt為進一步較佳。〔Cobalt ion〕 Among them, the treatment liquid preferably contains cobalt ions. When the treatment liquid contains cobalt ions, the chemical balance suppresses the elution of the metal from the metal layer. As a result, the effect of the present invention is considered to be more excellent. In particular, the corrosion resistance when the metal layer contains Co is more excellent. In addition, since the treatment liquid contains cobalt ions, the defect suppression properties are improved. When the treatment liquid contains cobalt ions, the content of cobalt ions relative to the total mass of the treatment liquid is preferably 0.001-1000 mass ppb, and 0.3-1000 mass ppt, from the viewpoint of more excellent effects and defect suppression properties of the present invention It is more preferable, and 1.0-200 mass ppt is still more preferable.

處理液中的鈷離子的含量係指按照上述SP-ICP-MS法（Single Nano Particle Inductively Coupled Plasma Mass Spectrometry，單奈米粒子感應耦合電漿質譜法）測量之鈷離子的含量。 如上述，ICP-MS中，與其存在形態無關地，對作為測量對象之金屬成分的含量進行測量。從而，鈷粒子與鈷離子的總計質量作為鈷成分的含量來定量。 另一方面，SP-ICP-MS中，測量鈷粒子的含量。從而，藉由從試樣中的鈷成分的含量減去鈷粒子的含量，能夠計算出試樣中的鈷離子的含量。The content of cobalt ions in the treatment solution refers to the content of cobalt ions measured according to the aforementioned SP-ICP-MS method (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry). As mentioned above, in ICP-MS, the content of the metal component to be measured is measured regardless of its existence form. Therefore, the total mass of cobalt particles and cobalt ions is quantified as the content of the cobalt component. On the other hand, in SP-ICP-MS, the content of cobalt particles is measured. Therefore, by subtracting the content of cobalt particles from the content of cobalt components in the sample, the content of cobalt ions in the sample can be calculated.

製備處理液時，鈷離子的導入方法並無特別限制。其中，從本發明的效果及相對於SiOx層之耐腐蝕性更優異之觀點考慮，處理液中的鈷離子係來源於選自包括氟化鈷、氯化鈷、氫氧化鈷、氧化鈷及硫酸鈷之群組中之至少1種鈷離子源之鈷離子為較佳。作為鈷離子源，從本發明的效果及相對於SiOx層之耐腐蝕性更優異之觀點考慮，選自包括氫氧化鈷、氧化鈷及硫酸鈷之群組中之至少1種為更佳。When preparing the treatment solution, the method of introducing cobalt ions is not particularly limited. Among them, from the viewpoint of the effect of the present invention and the better corrosion resistance relative to the SiOx layer, the cobalt ion in the treatment solution is derived from the group consisting of cobalt fluoride, cobalt chloride, cobalt hydroxide, cobalt oxide, and sulfuric acid. At least one cobalt ion source in the cobalt group is preferably cobalt ion. As the cobalt ion source, at least one selected from the group consisting of cobalt hydroxide, cobalt oxide, and cobalt sulfate is more preferable from the viewpoint of the effect of the present invention and the better corrosion resistance with respect to the SiOx layer.

又，從本發明的效果及缺陷抑制性均更優異之觀點考慮，上述之有機溶劑A（存在2種以上之情況下係其總含量）與鈷離子之比例以質量比計係1.0×104 ～1.0×1012 為較佳，1.0×105 ～1.0×1011 為更佳，1.0×106 ～1.0×1010 為進一步較佳。In addition, from the viewpoint that the effects of the present invention and defect suppression properties are more excellent, the ratio of the above-mentioned organic solvent A (the total content when there are more than two types) to the cobalt ion is 1.0×10 4 by mass ratio. ~1.0×10 12 is preferable, 1.0×10 5 to 1.0×10 11 is more preferable, and 1.0×10 6 to 1.0×10 10 is still more preferable.

處理液包含鈷離子之情況下，從本發明的效果、殘渣去除性及缺陷抑制性均更優異之觀點考慮，處理液的處方中，上述水的含量相對於處理液的總質量係10.0～98.0質量%，上述有機溶劑的總含量相對於處理液的總質量係1.0～90.0質量%（更佳為2.5～80.0質量%），上述鈷離子的含量相對於處理液的總質量係0.001～1000質量ppb為較佳。When the treatment liquid contains cobalt ions, from the viewpoint of the effects of the present invention, residue removal properties, and defect suppression properties, the content of the above water in the treatment liquid formulation is 10.0-98.0 relative to the total mass of the treatment liquid. Mass %, the total content of the organic solvent relative to the total mass of the treatment liquid is 1.0-90.0 mass% (more preferably 2.5-80.0 mass%), and the content of the cobalt ion relative to the total mass of the treatment liquid is 0.001-1000 mass ppb is preferred.

＜防腐蝕劑＞ 處理液包含防腐蝕劑為較佳。 防腐蝕劑具有藉由與作為半導體器件的配線等之金屬層（尤其含Co之層）的表面配位而形成膜並且防止因過度蝕刻等而引起之金屬層的腐蝕之功能。 另外，在本說明書中，上述螯合劑（具有螯合能力之化合物）不包括在防腐蝕劑中。＜Anti-corrosion agent＞ The treatment liquid preferably contains an anti-corrosion agent. The anti-corrosion agent has a function of forming a film by coordinating with the surface of a metal layer (especially a layer containing Co) as a wiring of a semiconductor device, and preventing corrosion of the metal layer caused by excessive etching or the like. In addition, in this specification, the above-mentioned chelating agents (compounds with chelating ability) are not included in the corrosion inhibitors.

作為防腐蝕劑並無特別限制，例如可舉出1,2,4-三唑（TAZ）、5-胺基四唑（ATA）、5-胺基-1,3,4-噻二唑-2-硫醇、3-胺基-1H-1,2,4-三唑、3,5-二胺基-1,2,4-三唑、甲苯基三唑、3-胺基-5-巰基-1,2,4-三唑、1-胺基-1,2,4-三唑、1-胺基-1,2,3-三唑、1-胺基-5-甲基-1,2,3-三唑、3-巰基-1,2,4-三唑、3-異丙基-1,2,4-三唑、萘三唑、1H-四唑-5-乙酸、2-巰基苯并噻唑（2-MBT）、1-苯基-2-四唑啉-5-硫酮、2-巰基苯并咪唑（2-MBI）、4-甲基-2-苯基咪唑、2-巰基噻唑啉、2,4-二胺基-6-甲基-1,3,5-三𠯤、噻唑、咪唑、苯并咪唑、三𠯤、甲基四唑、試鉍硫醇I、1,3-二甲基-2-咪唑啶酮、1,5-五亞甲基四唑、1-苯基-5-巰基四唑、二胺基甲基三𠯤、咪唑啉硫酮、4-甲基-4H-1,2,4-三唑-3-硫醇、5-胺基-1,3,4-噻二唑-2-硫醇、苯并噻唑、磷酸三甲苯基、吲唑、腺嘌呤、胞嘧啶、鳥嘌呤、胸腺嘧啶、磷酸鹽抑制劑、胺類、吡唑類、丙烷硫醇、矽烷類、二級胺類、苯并羥肟酸類、雜環式氮抑制劑、檸檬酸、抗壞血酸、硫脲、1,1,3,3-四甲基脲、脲、脲衍生物類、脲酸、乙基黃原酸鉀、甘胺酸、十二烷膦酸、亞胺基二乙酸、酸、硼酸、丙二酸、丁二酸、氮基三乙酸、環丁碸、2,3,5-三甲基吡𠯤、2-乙基-3,5-二甲基吡𠯤、喹㗁啉、乙醯基吡咯、嗒𠯤、組胺酸（histadine）、吡𠯤、麩胱甘肽（還元型）、半胱胺酸、胱胺酸、噻吩、巰基吡啶N-氧化物、硫胺HCl、二硫化四乙胺甲硫醯基、2,5-二巰基-1,3-噻二唑抗壞血酸、抗壞血酸、兒茶酚、三級丁基鄰苯二酚、苯酚及五倍子酚。The corrosion inhibitor is not particularly limited, and examples include 1,2,4-triazole (TAZ), 5-aminotetrazole (ATA), and 5-amino-1,3,4-thiadiazole-2 -Thiol, 3-amino-1H-1,2,4-triazole, 3,5-diamino-1,2,4-triazole, tolyltriazole, 3-amino-5-mercapto -1,2,4-triazole, 1-amino-1,2,4-triazole, 1-amino-1,2,3-triazole, 1-amino-5-methyl-1, 2,3-triazole, 3-mercapto-1,2,4-triazole, 3-isopropyl-1,2,4-triazole, naphthalenetriazole, 1H-tetrazole-5-acetic acid, 2- Mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazolin-5-thione, 2-mercaptobenzimidazole (2-MBI), 4-methyl-2-phenylimidazole, 2 -Mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-tris, thiazole, imidazole, benzimidazole, tris, methyltetrazole, bismuth mercaptan I, 1 ,3-Dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, diaminomethyl tris, imidazoline thione, 4- Methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2-thiol, benzothiazole, tricresyl phosphate, indazole , Adenine, cytosine, guanine, thymine, phosphate inhibitors, amines, pyrazoles, propane mercaptan, silanes, secondary amines, benzohydroxamic acids, heterocyclic nitrogen inhibitors, Citric acid, ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, potassium ethylxanthogenate, glycine, dodecylphosphonic acid, imine Diacetic acid, acid, boric acid, malonic acid, succinic acid, nitrotriacetic acid, cyclobutane, 2,3,5-trimethylpyridine, 2-ethyl-3,5-dimethylpyridine 𠯤, quinoline, acetylpyrrole, pyrrole, histadine, pyridine, glutathione (reduction type), cysteine, cystine, thiophene, pyrithione N-oxide , Thiamine HCl, tetraethylamine disulfide methionyl, 2,5-dimercapto-1,3-thiadiazole ascorbic acid, ascorbic acid, catechol, tertiary butyl catechol, phenol and gallic phenol .

另外，從本發明的效果更優異之觀點考慮，作為防腐蝕劑，包含經取代或未經取代之苯并三唑（以下亦記載為“苯并三唑化合物”）亦較佳。作為取代型苯并三唑，經烷基、芳基、鹵素基、胺基、硝基、烷氧基或羥基取代之苯并三唑為較佳。取代型苯并三唑中亦包含經1以上的芳基（例如，苯基）或雜芳基融合者。In addition, from the viewpoint that the effect of the present invention is more excellent, it is also preferable to include a substituted or unsubstituted benzotriazole (hereinafter also referred to as a "benzotriazole compound") as an anticorrosive agent. As the substituted benzotriazole, benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amino group, a nitro group, an alkoxy group or a hydroxyl group is preferred. Substituted benzotriazoles also include those fused with 1 or more aryl groups (for example, phenyl) or heteroaryl groups.

作為適合於防腐蝕劑之苯并三唑化合物，例如可舉出苯并三唑（BTA）、5-胺基四唑、1-羥基苯并三唑、5-苯硫基-苯并三唑、5-氯苯并三唑、4-氯苯并三唑、5-溴苯并三唑、4-溴苯并三唑、5-氟苯并三唑、4-氟苯并三唑、萘三唑、甲苯基三唑、5-苯基-苯并三唑、5-硝基苯并三唑、4-硝基苯并三唑、3-胺基-5-巰基-1,2,4-三唑、2-（5-胺基-戊基）-苯并三唑、1-胺基-苯并三唑、5-甲基-1H-苯并三唑（5MBTA）、苯并三唑-5-羧酸、4-甲基苯并三唑、4-乙基苯并三唑、5-乙基苯并三唑、4-丙基苯并三唑、5-丙基苯并三唑、4-異丙基苯并三唑、5-異丙基苯并三唑、4-正丁基苯并三唑、5-正丁基苯并三唑、4-異丁基苯并三唑、5-異丁基苯并三唑、4-戊基苯并三唑、5-戊基苯并三唑、4-己基苯并三唑、5-己基苯并三唑、5-甲氧基苯并三唑、5-羥基苯并三唑、二羥基丙基苯并三唑、1-[N,N-雙（2-乙基己基）胺基甲基]-苯并三唑、5-三級丁基苯并三唑、5-（1’,1’-二甲基丙基）-苯并三唑、5-（1’,1’,3’-三甲基丁基）苯并三唑、5-正辛基苯并三唑及5-（1’,1’,3’,3’-四甲基丁基）苯并三唑。 又，作為苯并三唑化合物，亦可以舉出2,2’-｛[（4-甲基-1H-苯并三唑-1-基）甲基]亞胺基｝雙乙醇、2,2’-｛[（5-甲基-1H-苯并三唑-1-基）甲基]亞胺基｝雙乙醇、2,2’-｛[（4-甲基-1H-苯并三唑-1-基）甲基]亞胺基｝雙乙烷或2,2’-｛[（4-甲基-1H-苯并三唑-1-基）甲基]亞胺基｝雙丙烷及N,N-雙（2-乙基己基）-（4或5）-甲基-1H-苯并三唑-1-甲基胺。As benzotriazole compounds suitable for corrosion inhibitors, for example, benzotriazole (BTA), 5-aminotetrazole, 1-hydroxybenzotriazole, 5-phenylthio-benzotriazole, 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthalene triazole Azole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 3-amino-5-mercapto-1,2,4- Triazole, 2-(5-amino-pentyl)-benzotriazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole (5MBTA), benzotriazole- 5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzotriazole, 5-ethylbenzotriazole, 4-propylbenzotriazole, 5-propylbenzotriazole, 4-isopropylbenzotriazole, 5-isopropylbenzotriazole, 4-n-butylbenzotriazole, 5-n-butylbenzotriazole, 4-isobutylbenzotriazole, 5-isobutylbenzotriazole, 4-pentylbenzotriazole, 5-pentylbenzotriazole, 4-hexylbenzotriazole, 5-hexylbenzotriazole, 5-methoxybenzene Triazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole, 5-triazole -Butyl benzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl)benzotriazole Azole, 5-n-octylbenzotriazole and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole. In addition, as the benzotriazole compound, 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol, 2,2 '-{[(5-methyl-1H-benzotriazol-1-yl)methyl]imino} diethanol, 2,2'-{[(4-methyl-1H-benzotriazole -1-yl)methyl]imino}bisethane or 2,2'-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}bispropane and N,N-bis(2-ethylhexyl)-(4 or 5)-methyl-1H-benzotriazole-1-methylamine.

從本發明的效果更優異之觀點考慮，防腐蝕劑包含選自包括由下述式（A）表示之化合物、由下述式（B）表示之化合物、由下述式（C）表示之化合物及經取代或未經取代之四唑之群組中之至少1種化合物為較佳。From the viewpoint that the effect of the present invention is more excellent, the anti-corrosion agent includes a compound selected from the group consisting of a compound represented by the following formula (A), a compound represented by the following formula (B), a compound represented by the following formula (C), and At least one compound in the group of substituted or unsubstituted tetrazole is preferred.

[化學式7]

Figure 02_image013
[Chemical formula 7]
Figure 02_image013

上述式（A）中，R1A ～R5A 分別獨立地表示氫原子、經取代或未經取代之烴基、羥基、羧基或者經取代或未經取代之胺基。其中，在結構中包含至少一個選自羥基、羧基及經取代或未經取代之胺基之基團。 上述式（B）中，R1B ～R4B 分別獨立地表示氫原子或者經取代或未經取代之烴基。 上述式（C）中，R1C 、R2C 及RN 分別獨立地表示氫原子或者經取代或未經取代之烴基。又，R1C 可以與R2C 鍵結而形成環。In the above formula (A), R 1A to R 5A each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amine group. Among them, the structure contains at least one group selected from a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amine group. In the above formula (B), R 1B to R 4B each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. In the above formula (C), R 1C , R 2C and RN each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. In addition, R 1C may bond with R 2C to form a ring.

上述式（A）中，作為由R1A ～R5A 表示之烴基，可舉出烷基（碳數1～12為較佳，碳數1～6為更佳，碳數1～3為進一步較佳）、烯基（碳數2～12為較佳，2～6為更佳）、炔基（碳數2～12為較佳，碳數2～6為更佳）、芳基（碳數6～22為較佳，碳數6～14為更佳，碳數6～10為進一步較佳）及芳烷基（碳數7～23為較佳，碳數7～15為更佳，碳數7～11為進一步較佳）。 又，作為取代烴基時的取代基，例如可舉出羥基、羧基及經取代或未經取代之胺基（作為取代胺基時的取代基，碳數1～6的烷基為較佳，碳數1～3的烷基為更佳）。 另外，式（A）中，在結構中包含至少一個選自羥基、羧基及經取代或未經取代之胺基（作為取代胺基時的取代基，碳數1～6的烷基為較佳，碳數1～3的烷基為更佳）之基團。In the above formula (A), examples of the hydrocarbon groups represented by R 1A to R 5A include alkyl groups (the carbon number is preferably 1 to 12, the carbon number is more preferably 1 to 6, and the carbon number is more preferably. Good), alkenyl (the carbon number is preferably 2 to 12, and 2 to 6 is more preferable), alkynyl (the carbon number is preferably 2 to 12, and the carbon number is more preferably 2 to 6), aryl (carbon number 6-22 is preferred, carbon number 6-14 is more preferred, carbon number 6-10 is more preferred) and aralkyl group (carbon number 7-23 is preferred, carbon number 7-15 is more preferred, carbon number is more preferred) The number 7-11 is more preferable). In addition, as the substituent when substituting the hydrocarbon group, for example, a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amine group (as a substituent for a substituted amine group, an alkyl group having 1 to 6 carbon atoms is preferred, and carbon An alkyl group of 1 to 3 is more preferable). In addition, in formula (A), the structure contains at least one selected from hydroxyl, carboxyl, and substituted or unsubstituted amine group (as the substituent of the substituted amine group, an alkyl group with 1 to 6 carbon atoms is preferred , C1-C3 alkyl group is more preferred).

式（A）中，作為由R1A ～R5A 表示之經取代或未經取代之烴基，例如可舉出經羥基、羧基或胺基取代之碳數1～6的烴基。 作為由式（A）表示之化合物，例如可舉出1-硫甘油、L-半胱胺酸及巰丁二酸。In the formula (A), the substituted or unsubstituted hydrocarbon group represented by R 1A to R 5A includes, for example, a hydrocarbon group having 1 to 6 carbons substituted with a hydroxyl group, a carboxyl group, or an amino group. Examples of the compound represented by the formula (A) include 1-thioglycerin, L-cysteine, and mercaptosuccinic acid.

式（B）中，由R1B ～R4B 表示之經取代或未經取代之烴基的含義與由上述之式（A）的R1A ～R5A 表示之經取代或未經取代之烴基的含義相同。 作為由R1B ～R4B 表示之經取代或未經取代之烴基，例如可舉出甲基、乙基、丙基及三級丁基等碳數1～6的烴基。 作為由式（B）表示之化合物，例如可舉出兒茶酚及三級丁基鄰苯二酚。In formula (B), the meaning of substituted or unsubstituted hydrocarbon groups represented by R 1B to R 4B and the meaning of substituted or unsubstituted hydrocarbon groups represented by R 1A to R 5A of formula (A) above the same. Examples of the substituted or unsubstituted hydrocarbon groups represented by R 1B to R 4B include hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, and tertiary butyl. Examples of the compound represented by the formula (B) include catechol and tertiary butylcatechol.

式（C）中，作為由R1C 、R2C 及RN 表示之經取代或未經取代之烴基，與由上述之式（A）的R1A ～R5A 表示之經取代或未經取代之烴基的含義相同。 作為由R1C 、R2C 及RN 表示之經取代或未經取代之烴基，例如可舉出甲基、乙基、丙基、丁基等碳數1～6的烴基。 又，R1C 可以與R2C 鍵結而形成環。作為R1C 與R2C 鍵結而形成之環，例如可舉出苯環。R1C 與R2C 鍵結而形成環之情況下，還可以具有取代基（例如，碳數1～5的烴基）。 作為由式（C）表示之化合物，例如可舉出1H-1,2,3-三唑、苯并三唑、5-甲基-1H-苯并三唑、甲苯基三唑、2,2’-｛[（4-甲基-1H-苯并三唑-1-基）甲基]亞胺基｝雙乙醇（產品名“IRGAMET 42”、BASF公司製）、N,N-雙（2-乙基己基）-（4或5）-甲基-1H-苯并三唑-1-甲基胺（產品名“IRGAMET 39”、BASF公司製）等，從本發明的效果更優異之觀點考慮，苯并三唑、5-甲基-1H-苯并三唑或甲苯基三唑為較佳，5-甲基-1H-苯并三唑為更佳。Formula (C), as represented by the sum of R 1C, R 2C, and R N of a substituted or unsubstituted hydrocarbon group, represented by the sum of the R in the above formula (A) of 1A ~ R 5A of a substituted or unsubstituted The meaning of the hydrocarbyl group is the same. As represented by the sum of R 1C, R 2C, and R N of a substituted or unsubstituted hydrocarbon group, a hydrocarbon group having a carbon number e.g. methyl, ethyl, propyl, butyl, etc. having 1 to 6 may be exemplified. In addition, R 1C may bond with R 2C to form a ring. Examples of the ring formed by bonding R 1C and R 2C include a benzene ring. When R 1C and R 2C are bonded to form a ring, they may have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms). As the compound represented by the formula (C), for example, 1H-1,2,3-triazole, benzotriazole, 5-methyl-1H-benzotriazole, tolyltriazole, 2,2 '-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino} diethanol (product name "IRGAMET 42", manufactured by BASF), N,N-bis(2 -Ethylhexyl)-(4 or 5)-methyl-1H-benzotriazole-1-methylamine (product name "IRGAMET 39", manufactured by BASF Corporation), etc., from the viewpoint that the effect of the present invention is more excellent In consideration, benzotriazole, 5-methyl-1H-benzotriazole or tolyltriazole are preferred, and 5-methyl-1H-benzotriazole is even more preferred.

作為經取代或未經取代之四唑，例如可舉出作為取代基具有無取代四唑及羥基、羧基或者經取代或未經取代之胺基之四唑。其中，作為取代胺基時的取代基，碳數1～6的烷基為較佳，碳數1～3的烷基為更佳。As the substituted or unsubstituted tetrazole, for example, tetrazole having an unsubstituted tetrazole, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group as a substituent can be mentioned. Among them, as the substituent when the amino group is substituted, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred.

處理液中的防腐蝕劑的含量相對於處理液的總質量係0.01～5質量%為較佳，0.05～5質量%為更佳，0.1～3質量%為進一步較佳。 防腐蝕劑可以單獨使用亦可以組合2種以上而使用。組合2種以上而使用防腐蝕劑的情況下，其總量在上述範圍內為較佳。The content of the anti-corrosion agent in the treatment liquid is preferably 0.01 to 5% by mass relative to the total mass of the treatment liquid, more preferably 0.05 to 5% by mass, and still more preferably 0.1 to 3% by mass. The corrosion inhibitor may be used alone or in combination of two or more kinds. When using a combination of two or more kinds of anticorrosive agents, the total amount is preferably within the above-mentioned range.

防腐蝕劑使用高純度的水準者為較佳，進一步純化而使用為更佳。 防腐蝕劑的純化方法並無特別限制，例如可使用過濾、離子交換、蒸餾、吸附純化、再結晶、再沉澱、升華及使用管柱的純化等公知的方法，亦能夠組合該等方法而應用。It is better to use a high purity level of the anticorrosive agent, and it is better to use it for further purification. The method for purifying the anticorrosive agent is not particularly limited. For example, well-known methods such as filtration, ion exchange, distillation, adsorption purification, recrystallization, reprecipitation, sublimation, and purification using a column can be used, and these methods can also be used in combination.

處理液可以包含除了上述成分以外的添加劑。作為添加劑，例如可舉出界面活性劑、消泡劑、防銹劑及防腐劑。The treatment liquid may contain additives other than the above-mentioned components. Examples of additives include surfactants, defoamers, rust inhibitors, and antiseptics.

〔處理液的物性〕 ＜pH＞ 本發明的處理液的pH係5以上。藉由pH係5以上，可獲得殘渣去除性優異之處理液。 處理液的pH係5～14為較佳，6～11為更佳。藉由處理液的pH係5～14，即使金屬層由公知的配線材料（例如，Co、Cu及W等）中的任一材料形成，亦能夠以更優異之水準兼顧本發明的效果及殘渣去除性。 處理液的pH係使用公知的pH計在25℃下進行測量而獲得之值。〔Physical properties of treatment liquid〕 ＜pH＞ The pH of the treatment liquid of the present invention is 5 or higher. With a pH of 5 or higher, a treatment solution with excellent residue removal properties can be obtained. The pH of the treatment liquid is preferably 5-14, and more preferably 6-11. With the pH of the treatment solution being 5-14, even if the metal layer is formed of any of the known wiring materials (for example, Co, Cu, W, etc.), the effects and residues of the present invention can be achieved at a more excellent level. Removal. The pH of the treatment liquid is a value obtained by measuring at 25°C using a known pH meter.

＜粗大粒子＞ 處理液實質上不包含粗大粒子為較佳。 粗大粒子例如係指將粒子的形狀視為球體之情況下直徑0.2μm以上的粒子。又，實質上不包含粗大粒子係指進行了使用光散射式液中粒子測量方式中的市售的測量裝置之處理液的測量時處理液1mL中的0.2μm以上的粒子係10個以下。 另外，包含於處理液之粗大粒子係在原料中作為雜質包含之塵、埃、有機固體物質及無機固體物質等粒子以及在處理液的製備中作為污染物被帶入之塵、埃、有機固體物質及無機固體物質等粒子等，相當於在最終處理液中未溶解而作為粒子存在者。 存在於處理液中之粗大粒子的量能夠利用將雷射作為光源之光散射式液中粒子測量方式中的市售的測量裝置並在液相中進行測量。 作為粗大粒子的去除方法，例如可舉出過濾等處理。＜Coarse particles＞ It is preferable that the treatment liquid does not substantially contain coarse particles. Coarse particles refer to particles having a diameter of 0.2 μm or more when the shape of the particles is regarded as a sphere, for example. In addition, the fact that coarse particles are not substantially included means that there are 10 or less particles of 0.2 μm or more in 1 mL of the treatment liquid when the treatment liquid is measured using a commercially available measuring device in the light scattering type particle in-liquid measurement method. In addition, the coarse particles contained in the treatment liquid are dust, dust, organic solid materials, and inorganic solid materials contained as impurities in the raw materials, and dust, dust, and organic solids that are carried in as pollutants during the preparation of the treatment liquid. Particles such as substances and inorganic solid substances are equivalent to those that are not dissolved in the final treatment liquid and exist as particles. The amount of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device in the light scattering type particle measurement method in the liquid using a laser as a light source. As a method of removing coarse particles, for example, treatment such as filtration can be cited.

[試劑盒及濃縮液] 上述處理液可以設為用於將其原料分割成複數個而製備處理液的試劑盒。雖並無特別限制，但是作為將處理液作為試劑盒之具體的方法，例如可舉出處理液包含水、有機溶劑（包含構成組合1～6中的任一種之有機溶劑A及B）及羥胺化合物之情況下，作為第1液準備包含水及羥胺化合物之液體組成物，作為第2液準備包含有機溶劑之液體組成物之態樣。[Kit and Concentrate] The above-mentioned treatment liquid can be used as a kit for preparing the treatment liquid by dividing the raw material into a plurality of pieces. Although there is no particular limitation, as a specific method of using the treatment liquid as a kit, for example, the treatment liquid contains water, an organic solvent (including organic solvents A and B of any one of the composition combinations 1 to 6), and hydroxylamine In the case of a compound, a liquid composition containing water and a hydroxylamine compound is prepared as the first liquid, and a liquid composition containing an organic solvent is prepared as the second liquid.

又，處理液包含螯合劑及羥胺化合物之情況下，作為用於製備處理液的試劑盒，具備包含羥胺化合物之第1液及包含螯合劑中的至少1種之第2液並且水及有機溶劑（包含構成組合1～6中的任一種之有機溶劑A及B）中分別包含在第1液及第2液中的至少一者中之試劑盒（以下，亦記載為“試劑盒A”。）為較佳。In addition, when the treatment liquid contains a chelating agent and a hydroxylamine compound, as a kit for preparing the treatment liquid, it includes a first liquid containing a hydroxylamine compound and a second liquid containing at least one of the chelating agent, and water and an organic solvent (Including the organic solvents A and B of any one of the composition combinations 1 to 6) A kit contained in at least one of the first liquid and the second liquid (hereinafter, also referred to as "kit A"). ) Is better.

試劑盒A的第1液至少包含羥胺化合物，亦可以包含水及/或有機溶劑。從更容易製備處理液之觀點考慮，試劑盒A的第1液至少包含水或有機溶劑為較佳。又，試劑盒A的第1液可以包含除了羥胺化合物、水及有機溶劑以外的成分，但是關於使用試劑盒A製備之處理液，從本發明的效果及殘渣去除性優異之觀點考慮，不包含特定含氮螯合劑為較佳。The first solution of the kit A contains at least a hydroxylamine compound, and may also contain water and/or an organic solvent. From the viewpoint of easier preparation of the treatment solution, the first solution of the kit A preferably contains at least water or an organic solvent. In addition, the first solution of the kit A may contain components other than the hydroxylamine compound, water, and organic solvent, but regarding the treatment solution prepared using the kit A, from the viewpoint of the effect of the present invention and the excellent residue removal property, it does not include Specific nitrogen-containing chelating agents are preferred.

試劑盒A的第2液包含處理液中所包含之螯合劑中的至少1種，亦可以包含水及/或有機溶劑。作為第2液中所包含之螯合劑，從使用所製備之處理液進行金屬層的處理時的本發明的效果及殘渣去除性優異之觀點考慮，特定含氮螯合劑為較佳。又，從更容易製備處理液之觀點考慮，試劑盒A的第2液至少包含水或有機溶劑為較佳。試劑盒A的第2液可以包含除了螯合劑、水及有機溶劑以外的成分，但是不包含羥胺化合物為較佳。The second liquid of the kit A contains at least one of the chelating agents contained in the treatment liquid, and may also contain water and/or an organic solvent. As the chelating agent contained in the second liquid, a specific nitrogen-containing chelating agent is preferred from the viewpoint of the effect of the present invention when the metal layer is treated using the prepared treatment liquid and the excellent residue removability. In addition, from the viewpoint of easier preparation of the treatment liquid, it is preferable that the second liquid of the kit A contains at least water or an organic solvent. The second solution of the kit A may contain components other than the chelating agent, water, and organic solvent, but preferably does not contain the hydroxylamine compound.

試劑盒所具備之第1液及第2液中所包含之各成分的含量並無特別限制，混合第1液及第2液而製備之處理液中的各成分的含量係成為上述較佳含量之量為較佳。 試劑盒所具備之第1液及第2液的pH並無特別限制，以混合第1液及第2液而製備之處理液的pH成為5以上的方式調節各自的pH即可。The content of each component contained in the first liquid and the second liquid included in the kit is not particularly limited, and the content of each component in the treatment liquid prepared by mixing the first liquid and the second liquid becomes the above-mentioned preferable content The amount is better. The pH of the first liquid and the second liquid included in the kit is not particularly limited, and the pH of each of the treatment liquids prepared by mixing the first liquid and the second liquid may be adjusted to be 5 or more.

試劑盒A的第1液中的羥胺化合物的含量並無特別限制，相對於第1液的總質量係0.01～50質量%為較佳，1.0～30質量%為更佳。 試劑盒A的第1液包含有機溶劑之情況下，有機溶劑的含量並無特別限制，相對於第1液的總質量係0.05～99.0質量%為較佳，1.0～90.0質量%為更佳，2.0～80.0質量%為進一步較佳。 試劑盒A的第1液中的水的含量係除了羥胺化合物及任意所包含之羥胺化合物以外的成分的殘餘部分即可，並無特別限制。The content of the hydroxylamine compound in the first solution of the kit A is not particularly limited, and it is preferably 0.01-50% by mass relative to the total mass of the first solution, and more preferably 1.0-30% by mass. In the case where the first solution of the kit A contains an organic solvent, the content of the organic solvent is not particularly limited. It is preferably 0.05-99.0% by mass relative to the total mass of the first solution, and more preferably 1.0-90.0% by mass. 2.0 to 80.0% by mass is more preferable. The content of water in the first solution of the kit A may be the remainder of the components other than the hydroxylamine compound and any contained hydroxylamine compounds, and is not particularly limited.

試劑盒A的第2液中的螯合劑的含量並無特別限制，相對於第2液的總質量係0.01～70質量%為較佳，0.1～50質量%為更佳。 試劑盒A的第2液中的水的含量係除了螯合劑及任意所包含之螯合劑以外的成分的殘餘部分即可，並無特別限制。The content of the chelating agent in the second liquid of the kit A is not particularly limited, and it is preferably 0.01 to 70% by mass relative to the total mass of the second liquid, and more preferably 0.1 to 50% by mass. The content of water in the second liquid of the kit A should just be the remainder of the components other than the chelating agent and any included chelating agents, and is not particularly limited.

又，處理液亦可以作為濃縮液來準備。該情況下，使用時能夠由稀釋液進行稀釋來使用。又，從缺陷去除性更優異之觀點考慮，濃縮液係由選自包括包含水、異丙醇、水與異丙醇的混合液及氫氧化銨之溶劑（更佳為水、異丙醇或水與異丙醇的混合液）之群組中之稀釋液進行稀釋為較佳。亦即，還可以設為作為濃縮液的形態的具有上述處理液及上述稀釋液之試劑盒。In addition, the treatment liquid can also be prepared as a concentrated liquid. In this case, it can be used after being diluted with a diluent at the time of use. Also, from the viewpoint of better defect removal, the concentrated liquid is selected from a solvent containing water, isopropanol, a mixture of water and isopropanol, and ammonium hydroxide (more preferably water, isopropanol or It is better to dilute the diluent in the group of mixed liquid of water and isopropanol. That is, it can also be set as a kit which has the said processing liquid and the said diluent in the form of a concentrated liquid.

[用途] 接著，對上述實施態樣之處理液的用途進行說明。 上述處理液係半導體器件用處理液。在本說明書中，“半導體器件用”係指製造半導體器件時所使用。上述處理液能夠在用於製造半導體器件的任一步驟中使用，例如能夠用於存在於基板上之絕緣膜、阻劑、防反射膜、蝕刻殘渣及灰化殘渣等的處理。另外，在本說明書中，將蝕刻殘渣及灰化殘渣總括而稱為殘渣。又，上述處理液可以用於化學機械研磨後的基板的處理，亦可以用作蝕刻液。 具體而言，處理液可用作在使用感光化射線性或感放射線性組成物來形成光阻膜之步驟之前，為了從半導體基板去除如下物質而使用之溶液（例如，去除液及剝離液等）等，亦即，為了改善組成物的塗佈性而塗佈於基板上之預濕液、用於去除附著於金屬層上之殘渣等之清洗液、用於去除圖案形成用各種光阻膜之溶液（例如，去除液及剝離液等）及永久膜（例如，濾色器、透明絕緣膜及樹脂製透鏡）等。另外，去除永久膜後的半導體基板有時會再次在半導體器件的使用中所使用，因此永久膜的去除亦包含於半導體器件的製造步驟中。 又，上述處理液亦能夠用作用於從化學機械研磨後的基板去除金屬雜質或微粒子等殘渣之清洗液。 又，上述處理液亦能夠用作相對於氧化鈷及氧化銅等金屬氧化物（包含由複數個金屬氧化物構成之複合氧化物）之蝕刻液。 上述用途中，尤其能夠較佳地用作用於去除蝕刻殘渣的清洗液、用於去除圖案形成中所使用之光阻膜的溶液、用於從化學機械研磨後的基板去除殘渣的清洗液或蝕刻液。 處理液在上述用途中可以僅用於1個用途，亦可以用於2個以上的用途。[use] Next, the use of the treatment liquid of the above-mentioned embodiment will be described. The above-mentioned treatment liquid is a treatment liquid for semiconductor devices. In this specification, "for semiconductor devices" refers to those used when manufacturing semiconductor devices. The above-mentioned treatment liquid can be used in any step for manufacturing a semiconductor device, and can be used, for example, for the treatment of insulating films, resists, anti-reflection films, etching residues, and ashing residues present on the substrate. In addition, in this specification, etching residue and ashing residue are collectively referred to as residue. In addition, the above-mentioned treatment liquid may be used for the treatment of a substrate after chemical mechanical polishing, or may be used as an etching liquid. Specifically, the treatment liquid can be used as a solution used to remove the following substances from the semiconductor substrate before the step of forming a photoresist film using a sensitized radiation or radiation-sensitive composition (for example, a removing liquid, a stripping liquid, etc.) ) Etc., that is, pre-wetting liquid applied on the substrate to improve the coating properties of the composition, cleaning liquid used to remove residues attached to the metal layer, etc., used to remove various photoresist films for pattern formation Solution (for example, removing liquid and stripping liquid, etc.) and permanent film (for example, color filter, transparent insulating film and resin lens), etc. In addition, the semiconductor substrate after the permanent film is removed is sometimes used again in the use of the semiconductor device, so the removal of the permanent film is also included in the manufacturing step of the semiconductor device. In addition, the above-mentioned treatment liquid can also be used as a cleaning liquid for removing residues such as metal impurities and fine particles from a substrate after chemical mechanical polishing. In addition, the above-mentioned treatment liquid can also be used as an etching liquid for metal oxides (including composite oxides composed of a plurality of metal oxides) such as cobalt oxide and copper oxide. Among the above uses, it can be particularly preferably used as a cleaning solution for removing etching residues, a solution for removing photoresist films used in pattern formation, and a cleaning solution or etching solution for removing residues from a substrate after chemical mechanical polishing. liquid. The treatment liquid may be used for only one use among the above-mentioned uses, or may be used for two or more uses.

上述處理液亦能夠用於半導體器件具備包含Co之金屬層之基板、半導體器件具備包含W之金屬層之基板或半導體器件具備包含Cu之金屬層之基板的處理。進而，上述處理液具有相對於層間絕緣膜之優異之耐腐蝕性，因此亦能夠用於例如半導體器件具備包含選自包括SiOx、SiN及SiOC（x表示1～3的數。）之群組中之至少1種之層之基板的處理。The above-mentioned treatment liquid can also be used for the treatment of a substrate in which a semiconductor device has a metal layer including Co, a substrate in which a semiconductor device has a metal layer including W, or a substrate in which a semiconductor device has a metal layer including Cu. Furthermore, the above-mentioned treatment liquid has excellent corrosion resistance with respect to the interlayer insulating film, and therefore can also be used in, for example, a semiconductor device equipped with a group selected from the group consisting of SiOx, SiN, and SiOC (x represents a number from 1 to 3). At least one layer of substrate processing.

[處理液、濃縮液、試劑盒之製造方法] ＜處理液製備步驟＞ 作為上述處理液的製造方法並無特別限制，能夠使用公知的製造方法。作為上述處理液的製造方法，例如可舉出至少具有混合上述各成分而製備處理液之處理液製備步驟之方法。 處理液製備步驟中，混合各成分之順序並無特別限制。關於濃縮液及試劑盒所具備之各液亦藉由與上述相同的方法來製造為較佳。 試劑盒的製作方法並無特別限制，例如藉由分別製備上述第1液及第2液之後將第1液及第2液分別收容於不同之容器來製作用於製備處理液之試劑盒即可。[Manufacturing method of treatment liquid, concentrated liquid, and reagent kit] <Processing liquid preparation steps> There are no particular limitations on the manufacturing method of the above-mentioned treatment liquid, and a known manufacturing method can be used. As a manufacturing method of the said processing liquid, the method which has at least the processing liquid preparation process which mixes the said each component and prepares a processing liquid is mentioned, for example. In the process liquid preparation step, the order of mixing the components is not particularly limited. It is also preferable that the concentrates and the liquids included in the kit are prepared by the same method as described above. The method of making the kit is not particularly limited. For example, the first solution and the second solution are prepared separately and then the first solution and the second solution are stored in separate containers to prepare a kit for preparing the treatment solution. .

＜金屬去除步驟＞ 在用於處理液製備步驟之前，對各成分進行從包含各成分之原料去除金屬而獲得包含各成分之純化物之金屬去除步驟為較佳。對各成分實施金屬去除步驟，並且使用所獲得之純化物中所包含之各成分來製備處理液，藉此能夠進一步降低處理液中所包含之金屬成分的含量。 作為從包含各成分之原料（以下亦稱為“被純化物”）去除金屬之方法並無特別限制，能夠應用使被純化物通過選自包括螯合樹脂及離子交換樹脂之群組中之至少一個樹脂之方法以及使被純化物通過金屬離子吸附過濾器之方法等公知的方法。＜Metal removal procedure＞ Before being used in the treatment liquid preparation step, it is preferable to perform a metal removal step for each component to remove metals from the raw material containing each component to obtain a purified product containing each component. The metal removal step is performed on each component, and each component contained in the obtained purified product is used to prepare the treatment liquid, thereby further reducing the content of the metal component contained in the treatment liquid. There is no particular limitation on the method for removing metals from the raw material containing each component (hereinafter also referred to as the "purified product"), and it can be applied to pass the purified product through at least one selected from the group consisting of chelating resins and ion exchange resins. A resin method and a method of passing the purified material through a metal ion adsorption filter are well-known methods.

作為金屬去除步驟的對象物之成分，只要為上述的處理液中所包含之成分（但是，金屬成分除外）則並無特別限制。處理液包含螯合劑之情況下，與其他成分相比，有包含螯合劑之原料中所包含之金屬成分的含量較多的傾向，因此使用包含對包含螯合劑之原料實施金屬去除步驟而獲得之螯合劑之純化物來製備處理液為更佳。 實施金屬去除步驟之被純化物可以包含除了對象物以外的化合物，包含溶劑為較佳。作為溶劑，可舉出水及有機溶劑，水為較佳。 被純化物中的對象物的含量能夠適當依據對象物的種類及具體的金屬去除處理，例如相對於被純化物的總質量可以為1～100質量%，10～50質量%為較佳。The target component of the metal removal step is not particularly limited as long as it is the component contained in the above-mentioned treatment liquid (except for the metal component). When the treatment liquid contains a chelating agent, compared with other components, the content of the metal component contained in the raw material containing the chelating agent tends to be higher. Therefore, the material containing the chelating agent is obtained by performing a metal removal step on the raw material containing the chelating agent. It is better to prepare the treatment liquid with the purified product of the chelating agent. The object to be purified to be subjected to the metal removal step may contain a compound other than the target object, and preferably contains a solvent. Examples of the solvent include water and organic solvents, and water is preferred. The content of the object in the purified product can appropriately depend on the type of the object and the specific metal removal treatment. For example, it can be 1-100% by mass relative to the total mass of the purified product, and preferably 10-50% by mass.

作為使被純化物通過選自包括螯合樹脂及離子交換樹脂之群組中之至少一個樹脂之方法並無特別限制，可舉出使被純化物通過填充於容器之螯合樹脂及/或離子交換樹脂之方法。 使被純化物通過之螯合樹脂及/或離子交換樹脂可以單獨使用1種，亦可以使用2種以上。又，亦可以使被純化物通過2次以上相同的螯合樹脂及/或離子交換樹脂。 金屬去除步驟中，可以使用螯合樹脂及離子交換樹脂這兩者。該情況下，亦可以在複數床或混床中使用螯合樹脂及離子交換樹脂。 作為容器，只要為能夠填充螯合樹脂及/或離子交換樹脂並且使被純化物通過所填充之螯合樹脂及/或離子交換樹脂則並無特別限制，例如可舉出管柱、芯及填充塔。The method for passing the purified object through at least one resin selected from the group consisting of chelating resins and ion exchange resins is not particularly limited. Examples include passing the purified object through the chelating resin and/or ion filled in the container. The method of exchanging resin. The chelating resin and/or ion exchange resin through which the object to be purified passes may be used singly, or two or more types may be used. In addition, the object to be purified may be passed through the same chelating resin and/or ion exchange resin twice or more. In the metal removal step, both chelating resin and ion exchange resin can be used. In this case, chelating resins and ion exchange resins can also be used in multiple beds or mixed beds. The container is not particularly limited as long as it can be filled with a chelating resin and/or ion exchange resin and allows the purified product to pass through the filled chelating resin and/or ion exchange resin. Examples include column, core, and packing. tower.

作為用於金屬去除步驟之離子交換樹脂，可舉出陽離子交換樹脂及陰離子交換樹脂。陽離子交換樹脂可以在單床中使用，亦可以在複數床或混床中使用陽離子交換樹脂及陰離子交換樹脂。 作為陽離子交換樹脂，能夠使用公知的陽離子交換樹脂，例如可舉出磺酸型陽離子交換樹脂及羧酸型陽離子交換樹脂。陽離子交換樹脂的材質並無特別限制，凝膠型陽離子交換樹脂為較佳。 作為陽離子交換樹脂，能夠使用市售品，例如可舉出Amberlite（註冊商標，以下相同）IR-124、Amberlite IR-120B、Amberlite IR-200CT、Orlite（註冊商標，以下相同）DS-1及Orlite DS-4（以上為ORGANO CORPORATION製）；Duolite（註冊商標，以下相同）C20J、Duolite C20LF、DuoliteC255LFH及DuoliteC-433LF（以上為Sumika Chemtex Company, Limited製）；DIAION（註冊商標，以下相同）SK-110、DIAION SK1B及DIAION SK1BH（以上、Mitsubishi Chemical Corporation.製）；以及Purolite（註冊商標，以下相同）S957及Purolite S985（以上為Purolite公司製）等。Examples of ion exchange resins used in the metal removal step include cation exchange resins and anion exchange resins. The cation exchange resin can be used in a single bed, and cation exchange resin and anion exchange resin can also be used in multiple beds or mixed beds. As the cation exchange resin, known cation exchange resins can be used, and examples thereof include sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins. The material of the cation exchange resin is not particularly limited, and gel-type cation exchange resins are preferred. As the cation exchange resin, commercially available products can be used, such as Amberlite (registered trademark, the same hereinafter) IR-124, Amberlite IR-120B, Amberlite IR-200CT, Orlite (registered trademark, the same hereinafter) DS-1 and Orlite DS-4 (the above is manufactured by ORGANO CORPORATION); Duolite (registered trademark, the same below) C20J, Duolite C20LF, Duolite C255LFH and Duolite C-433LF (the above are manufactured by Sumika Chemtex Company, Limited); DIAION (registered trademark, the same below) SK- 110, DIAION SK1B and DIAION SK1BH (above, manufactured by Mitsubishi Chemical Corporation.); and Purolite (registered trademark, the same below) S957 and Purolite S985 (above manufactured by Purolite), etc.

螯合樹脂只要為含有具有與金屬進行螯合化之功能之螯合基之樹脂則並無特別限制。 作為螯合基，例如可舉出亞胺基二乙酸基、亞胺基丙酸基、胺基亞甲基膦酸基（-NH-CH3 -PO3 H2 ）等胺基膦酸基、多胺基、N-甲基葡萄糖胺基等葡萄糖胺基、胺基羧酸基、二硫卡巴胺酸基、硫醇基、醯胺肟基及吡啶基，亞胺基二乙酸基或胺基膦酸基為較佳，胺基膦酸基為更佳。 該等螯合基可以與抗衡離子一同形成鹽，但是從進一步降低金屬含量之觀點考慮，不形成鹽為較佳。亦即，螯合樹脂係H型螯合樹脂為較佳。H型螯合樹脂藉由使Na型、Ca型及Mg型等金屬離子型螯合樹脂與鉱酸接觸而進行酸處理來獲得。 螯合樹脂的基體並無特別限制，例如可舉出苯乙烯-二乙烯基苯共聚物及苯乙烯-乙基苯乙烯-二乙烯基苯共聚物。The chelating resin is not particularly limited as long as it contains a chelating group having a function of chelating with a metal. Examples of the chelating group include amino phosphonic acid groups such as imino diacetoxy group, imino propionic acid group, amino methylene phosphonic acid group (-NH-CH 3 -PO 3 H 2 ), etc. Glucosamine groups such as polyamino groups and N-methylglucosamine groups, amino carboxylic acid groups, dithiocarbamic acid groups, thiol groups, amidoxime groups and pyridyl groups, imino diacetoxy groups or amino groups A phosphonic acid group is preferred, and an amino phosphonic acid group is more preferred. These chelating groups can form a salt together with the counter ion, but from the viewpoint of further reducing the metal content, it is better not to form a salt. That is, the chelate resin-based H-type chelate resin is preferable. The H-type chelating resin is obtained by contacting metal ion-type chelating resins such as Na-type, Ca-type, and Mg-type with oxalic acid to perform acid treatment. The matrix of the chelating resin is not particularly limited, and examples include styrene-divinylbenzene copolymers and styrene-ethylstyrene-divinylbenzene copolymers.

作為螯合樹脂，能夠使用市售品，例如可舉出Duolite ES371N、Duolite C467、Duolite C747UPS、Sumichelate（註冊商標，以下相同）MC760、Sumichelate MC230、Sumichelate MC300、Sumichelate MC850、Sumichelate MC640、Sumichelate MC900及Sumichelate MC960（以上為Sumika Chemtex Company, Limited製）；Purolite S106、Purolite S910、Purolite S914、Purolite S920、Purolite S930、Purolite S950、Purolite S957及Purolite S985（以上為Purolite公司製）；以及Orlite DS-21、Amberlite IRC748及Amberlite IRC747（以上為ORGANO CORPORATION製）。As the chelating resin, commercially available products can be used, for example, Duolite ES371N, Duolite C467, Duolite C747UPS, Sumichelate (registered trademark, the same hereinafter) MC760, Sumichelate MC230, Sumichelate MC300, Sumichelate MC850, Sumichelate MC640, Sumichelate MC900 and Sumichelate MC960 (manufactured by Sumika Chemtex Company, Limited above); Purolite S106, Purolite S910, Purolite S914, Purolite S920, Purolite S930, Purolite S950, Purolite S957 and Purolite S985 (manufactured by Purolite Company); and Orlite DS-21, Amberlite IRC748 and Amberlite IRC747 (the above are manufactured by ORGANO CORPORATION).

處理液包含螯合劑之情況下，從能夠進一步降低處理液中的金屬成分的含量之觀點考慮，對含有螯合劑之原料進行之金屬去除步驟包括使被純化物通過選自包括螯合樹脂及離子交換樹脂之群組中之至少一個樹脂之步驟為較佳，包括使被純化物通過螯合樹脂之步驟為更佳。其中，從能夠進一步降低含有螯合劑之原料中所包含之Ca及/或Zn的含量之觀點考慮，包括使被純化物通過具有胺基膦酸基之螯合樹脂之步驟為進一步較佳。 作為具有胺基膦酸基之螯合樹脂的市售品，可舉出Duolite C467、Duolite C747UPS、Sumichelate MC960、Purolite S950、Orlite DS-21及Amberlite IRC747，Orlite DS-21為較佳。 另外，Orlite DS-21係向由苯乙烯-乙基苯乙烯-二乙烯基苯共聚物構成之基材導入作為螯合基之胺基甲基膦酸基而成之H型螯合樹脂，以包含30～45質量%的上述螯合樹脂及55～70質量%的水之狀態進行市售。When the treatment liquid contains a chelating agent, from the viewpoint of further reducing the content of the metal component in the treatment liquid, the metal removal step for the raw material containing the chelating agent includes passing the purified material through a group consisting of chelating resins and ions. The step of exchanging at least one resin in the group of resins is preferable, and it is more preferable to include the step of passing the purified substance through the chelating resin. Among them, from the viewpoint of being able to further reduce the content of Ca and/or Zn contained in the raw material containing the chelating agent, it is more preferable to include a step of passing the purified product through a chelating resin having an aminophosphonic acid group. Commercial products of the chelating resin having an aminophosphonic acid group include Duolite C467, Duolite C747UPS, Suumichelate MC960, Purolite S950, Orlite DS-21, and Amberlite IRC747, with Orlite DS-21 being preferred. In addition, Orlite DS-21 is an H-type chelating resin formed by introducing aminomethylphosphonic acid groups as chelating groups to a substrate composed of styrene-ethylstyrene-divinylbenzene copolymers. The state containing 30 to 45% by mass of the above-mentioned chelating resin and 55 to 70% by mass of water is commercially available.

使被純化物通過離子交換樹脂時的條件並無特別限制，按照公知的方法進行即可。 被純化物與離子交換樹脂接觸的同時通過時的空間速度（SV：Space Velocity）係1～20為較佳，1～10為更佳。 與離子交換樹脂接觸之被純化物的溫度係10～40℃為較佳，15～30℃為更佳。There are no particular restrictions on the conditions for passing the purified product through the ion exchange resin, and it may be carried out in accordance with a known method. It is preferable that the space velocity (SV: Space Velocity) of the material to be purified while passing through contact with the ion exchange resin is 1-20, and more preferably 1-10. The temperature of the purified product in contact with the ion exchange resin is preferably 10-40°C, more preferably 15-30°C.

作為被純化物的金屬去除步驟，可以實施記載於國際公開第2012/043496號之使用碳化矽之金屬成分的吸附純化處理步驟，該記載被編入到本說明書中。 又，作為被純化物的金屬去除步驟，可以使用用作後述之過濾步驟中之過濾器舉出之過濾器來去除被純化物中所包含之金屬粒子。As the metal removal step of the product to be purified, an adsorption purification treatment step using a metal component of silicon carbide described in International Publication No. 2012/043496 can be implemented, which description is incorporated in this specification. In addition, as the metal removal step of the object to be purified, a filter exemplified as a filter in the filtration step described later can be used to remove metal particles contained in the object to be purified.

藉由金屬去除步驟從被純化物去除之金屬並無特別限制，可舉出Li、Na、Mg、Al、K、Ca、Cr、Mn、Fe、Ni、Zn及Pb等金屬。與被純化物相比，藉由金屬去除步驟獲得之純化物的上述金屬含量降低。 純化物中的金屬的含量並無特別限制，例如包含螯合劑之純化物中的每個金屬成分的各金屬元素的含量與螯合劑的含量之比例以質量比計均係1.0×10-6 以下為較佳，1.0×10-7 以下為更佳，1.0×10-8 以下為進一步較佳。 又，在包含藉由金屬去除步驟獲得之螯合劑之純化物中，Ca成分的含量與Na成分的含量之比例以質量比計係1.0以上（Ca成分的含量多於Na成分的含量）為較佳，1.1以上為更佳，1.2以上為進一步較佳。上限並無特別限制，Ca成分的含量與Na成分的含量之比例以質量比計係50以下為較佳。 另外，被純化物及純化物中的金屬的種類及含量能夠按照作為處理液中的金屬成分的種類及含量的測量方法而記載之方法來進行測量。The metal to be removed from the object to be purified by the metal removal step is not particularly limited, and examples include Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Ni, Zn, and Pb. Compared with the purified product, the metal content of the purified product obtained by the metal removal step is reduced. The content of the metal in the purified product is not particularly limited. For example, the ratio of the content of each metal element of each metal component in the purified product containing the chelating agent to the content of the chelating agent is 1.0×10 -6 or less by mass ratio. Preferably, 1.0×10 -7 or less is more preferable, and 1.0×10 -8 or less is even more preferable. In addition, in the purified product containing the chelating agent obtained by the metal removal step, the ratio of the content of the Ca component to the content of the Na component is 1.0 or more by mass ratio (the content of the Ca component is more than the content of the Na component). Preferably, 1.1 or more is more preferable, and 1.2 or more is still more preferable. The upper limit is not particularly limited, and the ratio of the content of the Ca component to the content of the Na component is preferably 50 or less in terms of mass ratio. In addition, the type and content of the metal in the purified product and the purified product can be measured according to the method described as the method of measuring the type and content of the metal component in the treatment liquid.

＜過濾步驟＞ 上述製造方法中包括為了從液中去除異物及粗大粒子等而對液體進行過濾之過濾步驟為較佳。 作為過濾的方法並無特別限制，能夠使用公知的過濾方法。其中，使用過濾器之過濾為較佳。<Filtering steps> The above-mentioned manufacturing method preferably includes a filtration step of filtering the liquid in order to remove foreign substances, coarse particles, and the like from the liquid. The filtering method is not particularly limited, and a known filtering method can be used. Among them, filtration using a filter is preferable.

用於過濾之過濾器只要為以往用於過濾用途等者，則能夠無特別限制地使用。作為構成過濾器之材料，例如可舉出PTFE（聚四氟乙烯）等氟樹脂、尼龍等聚醯胺系樹脂以及聚乙烯及聚丙烯（PP）等聚烯烴樹脂（包含高密度、超高分子量）等。其中，聚醯胺系樹脂、PTFE及聚丙烯（包含高密度聚丙烯）為較佳。 使用藉由該等原材料形成之過濾器，藉此能夠更加有效地從處理液去除容易成為缺陷的原因的極性高的異物。The filter used for filtering can be used without particular limitation as long as it is used for filtering purposes etc. in the past. Examples of materials constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins such as polyethylene and polypropylene (PP) (including high-density and ultra-high molecular weight). )Wait. Among them, polyamide resins, PTFE, and polypropylene (including high-density polypropylene) are preferred. The use of filters made of these raw materials can more effectively remove foreign materials with high polarity that are likely to cause defects from the treatment liquid.

作為過濾器的臨界表面張力，作為下限值70mN/m以上為較佳，作為上限值95mN/m以下為較佳。尤其，過濾器的臨界表面張力係75～85mN/m為較佳。 另外，臨界表面張力的值係製造商的標稱值。藉由使用臨界表面張力在上述範圍的過濾器，能夠更加有效地從處理液去除容易成為缺陷的原因的極性高的異物。As the critical surface tension of the filter, the lower limit is preferably 70 mN/m or more, and the upper limit is 95 mN/m or less. In particular, the critical surface tension of the filter is preferably 75 to 85 mN/m. In addition, the value of the critical surface tension is the manufacturer's nominal value. By using a filter with a critical surface tension in the above range, it is possible to more effectively remove foreign materials with high polarity that are likely to cause defects from the treatment liquid.

過濾器的孔徑係0.001～1.0μm左右為較佳，0.02～0.5μm左右為更佳，0.01～0.1μm左右為進一步較佳。藉由將過濾器的孔徑設為上述範圍，能夠抑制過濾堵塞且確實地去除處理液中所包含之微細的異物。The pore diameter of the filter is preferably about 0.001 to 1.0 μm, more preferably about 0.02 to 0.5 μm, and more preferably about 0.01 to 0.1 μm. By setting the pore size of the filter within the above-mentioned range, it is possible to suppress clogging of the filter and reliably remove the fine foreign matter contained in the treatment liquid.

使用過濾器時，可以組合不同的過濾器。此時，第1過濾器的過濾可以僅進行1次，亦可以進行2次以上。組合不同之過濾器來進行2次以上過濾之情況下，各過濾器可以為彼此相同種類者，亦可以為彼此不同種類者，但是種類彼此不同為較佳。典型的是，第1過濾器及第2過濾器的孔徑及構成原材料中的至少一個不同為較佳。 第2次以後的孔徑與第1次過濾的孔徑相同或比第1次過濾的孔徑小為較佳。又，亦可以組合在上述範圍內孔徑不同之第1過濾器。其中的孔徑能夠參閱過濾器廠商的標稱值。作為市售的過濾器，例如能夠從由NIHON PALL LTD.、Advantec Toyo Kaisha, Ltd.、Nihon Entegris K.K.（Formerly Nippon Mykrolis Corporation）或KITZ MICROFILTER CORPORATION等提供之各種過濾器中選擇。又，亦能夠使用聚醯胺製“P-尼龍過濾器（孔徑0.02μm、臨界表面張力77mN/m）”；（NIHON PALL LTD.製）、高密度聚乙烯製“PE・清潔過濾器（孔徑0.02μm）”；（NIHON PALL LTD.製）及高密度聚乙烯製“PE・清潔過濾器（孔徑0.01μm）”；（NIHON PALL LTD.製）。When using filters, different filters can be combined. At this time, the filtration of the first filter may be performed only once, or may be performed two or more times. In the case of combining different filters to perform filtering twice or more, the filters may be of the same type or different types, but it is preferable that the types are different from each other. Typically, it is preferable that at least one of the pore diameters and constituent materials of the first filter and the second filter is different. It is preferable that the pore size after the second time is the same as or smaller than the pore diameter of the first time filtration. In addition, it is also possible to combine first filters having different pore diameters within the above-mentioned range. The pore size can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it can be selected from various filters provided by NIHON PALL LTD., Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (Formerly Nippon Mykrolis Corporation), KITZ MICROFILTER CORPORATION, and the like. In addition, polyamide-made "P-nylon filter (pore size 0.02μm, critical surface tension 77mN/m)"; (manufactured by NIHON PALL LTD.), high-density polyethylene "PE・clean filter (pore size) 0.02μm)” (manufactured by NIHON PALL LTD.) and high-density polyethylene “PE cleaning filter (pore size 0.01μm)”; (manufactured by NIHON PALL LTD.).

第2過濾器能夠使用由與上述之第1過濾器相同的材料形成之過濾器。能夠使用與上述之第1過濾器相同的孔徑者。使用第2過濾器的孔徑小於第1過濾器者之情況下，第2過濾器的孔徑與第1過濾器的孔徑之比（第2過濾器的孔徑/第1過濾器的孔徑）係0.01～0.99為較佳，0.1～0.9為更佳，0.3～0.9為進一步較佳。藉由將第2過濾器的孔徑設為上述範圍，更加確實地去除混入處理液之微細的異物。As the second filter, a filter made of the same material as the above-mentioned first filter can be used. The same pore size as the above-mentioned first filter can be used. When the pore size of the second filter is smaller than that of the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (the pore size of the second filter/the pore size of the first filter) is 0.01 to 0.99 is preferred, 0.1 to 0.9 is more preferred, and 0.3 to 0.9 is even more preferred. By setting the pore diameter of the second filter in the above range, fine foreign matter mixed in the treatment liquid can be removed more reliably.

例如，亦可以由包含處理液的一部分成分之混合液進行第1過濾器的過濾，並向其中混合剩餘的成分而製備處理液之後，進行第2過濾。For example, the first filter may be filtered from a mixed liquid containing a part of the components of the treatment liquid, and the remaining components may be mixed therewith to prepare the treatment liquid, and then the second filtration may be performed.

又，所使用之過濾器在過濾處理液之前進行處理為較佳。該處理中所使用之液體並無特別限制，但是包含處理液、濃縮液及處理液中含有之成分之液體為較佳。In addition, the filter used is preferably processed before filtering the processing liquid. The liquid used in this treatment is not particularly limited, but a liquid containing a treatment liquid, a concentrated liquid, and components contained in the treatment liquid is preferable.

進行過濾之情況下，過濾時的溫度的上限值係室溫（25℃）以下為較佳，23℃以下為更佳，20℃以下為進一步較佳。又，過濾時的溫度的下限值係0℃以上為較佳，5℃以上為更佳，10℃以上為進一步較佳。 過濾中，能夠去除粒子性的異物及/或雜質，但是若在上述溫度中進行，則溶解於處理液中之粒子性的異物及/或雜質的量變少，因此更加有效地進行過濾。In the case of filtration, the upper limit of the temperature during filtration is preferably room temperature (25°C) or lower, more preferably 23°C or lower, and more preferably 20°C or lower. In addition, the lower limit of the temperature during filtration is preferably 0°C or higher, more preferably 5°C or higher, and more preferably 10°C or higher. In filtration, particulate foreign matter and/or impurities can be removed, but if it is performed at the above temperature, the amount of particulate foreign matter and/or impurities dissolved in the treatment liquid is reduced, so filtration is performed more effectively.

＜除電步驟＞ 上述製造方法還可以包括對選自包括處理液、濃縮液及試劑盒之群組中之至少1種進行除電之除電步驟。另外，關於除電的具體方法在後面敘述。＜Static elimination procedure＞ The above-mentioned manufacturing method may further include a neutralization step of neutralizing at least one selected from the group consisting of a treatment solution, a concentrated solution, and a kit. In addition, the specific method of removing electricity will be described later.

另外，上述製造方法之所有步驟在無塵室內進行為較佳。無塵室滿足14644-1無塵室基準為較佳。滿足ISO（國際標準化機構）水準1、ISO水準2、ISO水準3、ISO水準4中的任一個為較佳，滿足ISO水準1或ISO水準2為更佳，滿足ISO水準1為進一步較佳。In addition, all the steps of the above-mentioned manufacturing method are preferably carried out in a clean room. It is better for the clean room to meet the 14644-1 clean room standard. It is better to satisfy any of ISO (International Organization for Standardization) Level 1, ISO Level 2, ISO Level 3, and ISO Level 4, it is more preferable to satisfy ISO Level 1 or ISO Level 2, and it is even more preferable to satisfy ISO Level 1.

＜容器＞ 作為收容上述之處理液、濃縮液或試劑盒之容器，只要液體腐蝕性不成問題，則無特別限制，能夠使用公知的容器。 作為上述容器，用於以半導體用途時容器內的清潔度高且雜質的溶出少者為較佳。 作為上述容器的具體例，例如可舉出AICELLO CHEMICAL CO., LTD.製“Clean-Bottle”系列及KODAMA PLASTICS Co.,Ltd.製“Pure bottle”等。又，以防止雜質混入（污染）原材料及藥液為目的，使用由6種樹脂構成容器內壁之6層結構亦即多層容器、由6種樹脂構成容器內壁之7層結構亦即多層容器亦較佳。作為該等容器，例如可舉出日本特開2015-123351號公報中記載之容器，但是並不限制於該等。 上述容器的內壁由選自包括聚乙烯樹脂、聚丙烯樹脂及聚乙烯-聚丙烯樹脂之群組中之1種以上的樹脂、與它們不同之樹脂以及不銹鋼、赫史特合金、英高鎳合金及蒙乃爾合金等金屬形成或塗覆為較佳。＜Container＞ As a container for storing the above-mentioned treatment liquid, concentrated liquid, or reagent kit, as long as the corrosiveness of the liquid is not a problem, there is no particular limitation, and a known container can be used. As the above-mentioned container, when it is used for a semiconductor, the cleanliness in the container is high and the elution of impurities is small, preferably. As a specific example of the said container, the "Clean-Bottle" series manufactured by AICELLO CHEMICAL CO., LTD., the "Pure bottle" manufactured by KODAMA PLASTICS Co., Ltd., etc. are mentioned, for example. In addition, for the purpose of preventing impurities from entering (contaminating) the raw materials and chemical liquids, the 6-layer structure that is the inner wall of the container made of 6 kinds of resins, that is, the multilayer container, and the 7-layer structure that is the inner wall of the container made of 6 kinds of resins, the multi-layered container are used Also better. Examples of these containers include those described in JP 2015-123351 A, but they are not limited to these. The inner wall of the container is made of one or more resins selected from the group consisting of polyethylene resin, polypropylene resin and polyethylene-polypropylene resin, resins different from them, stainless steel, Hester alloy, Inconel It is preferable to form or coat metals such as alloys and Monel alloys.

作為上述不同之樹脂，能夠較佳地使用氟系樹脂（全氟樹脂）。如此，與使用內壁由聚乙烯樹脂、聚丙烯樹脂或聚乙烯-聚丙烯樹脂形成或塗覆之容器之情況相比，藉由使用容器的內壁由氟系樹脂形成或由氟樹脂塗覆之容器，能夠抑制乙烯或丙烯的寡聚物的溶出此等不良情況的產生。 作為具有該種內壁之容器的具體例，例如可舉出Entegris,Inc.製FluoroPurePFA複合管柱等。又，亦能夠使用日本特表平3-502677號公報的第4頁等、國際公開第2004/016526號小冊子的第3頁等及國際公開第99/046309號小冊子的第9頁及16頁等中記載之容器。As the above-mentioned different resins, fluorine-based resins (perfluororesins) can be preferably used. In this way, compared with the case of using a container whose inner wall is formed or coated with polyethylene resin, polypropylene resin, or polyethylene-polypropylene resin, by using a container whose inner wall is formed or coated with fluorine resin The container can prevent the occurrence of such problems as the elution of ethylene or propylene oligomers. As a specific example of a container having such an inner wall, for example, a FluoroPurePFA composite column manufactured by Entegris, Inc. can be cited. In addition, it is also possible to use page 4 of Japanese Special Publication No. 3-502677, page 3 of International Publication No. 2004/016526 Pamphlet, etc., and pages 9 and 16 of International Publication No. 99/046309 Pamphlet, etc. The container recorded in.

又，容器的內壁除了上述之氟系樹脂以外，亦較佳地使用石英及經電解研磨之金屬材料（亦即，已電解研磨的金屬材料）。 用於上述經電解研磨之金屬材料的製造之金屬材料包含選自包括鉻及鎳之群組中之至少1種，鉻及鎳的含量的總計相對於金屬材料總質量超過25質量%之金屬材料為較佳，例如可舉出不銹鋼及鎳-鉻合金等。 金屬材料中的鉻及鎳的含量的總計相對於金屬材料總質量係25質量%以上為較佳，30質量%以上為更佳。 另外，作為金屬材料中的鉻及鎳的含量的總計的上限值並無特別限制，90質量%以下為較佳。In addition to the above-mentioned fluorine-based resin, the inner wall of the container preferably uses quartz and electrolytically polished metal materials (that is, electrolytically polished metal materials). The metal material used in the production of the electrolytically ground metal material includes at least one selected from the group consisting of chromium and nickel, and the total content of chromium and nickel exceeds 25% by mass relative to the total mass of the metal material Preferably, for example, stainless steel, nickel-chromium alloy, etc. can be mentioned. The total content of chromium and nickel in the metal material is preferably 25% by mass or more with respect to the total mass of the metal material, and more preferably 30% by mass or more. In addition, the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but 90% by mass or less is preferable.

作為不銹鋼，並無特別限制，能夠使用公知的不銹鋼。其中，包含8質量%以上的鎳之合金為較佳，包含8質量%以上的鎳之奧氏體系不銹鋼為更佳。作為奧氏體系不銹鋼，例如可舉出SUS（Steel Use Stainless）304（Ni的含量：8質量%、Cr的含量：18質量%）、SUS304L（Ni的含量：9質量%、Cr的含量：18質量%）、SUS316（Ni的含量：10質量%、Cr的含量：16質量%）及SUS316L（Ni的含量：12質量%、Cr的含量：16質量%）等。As stainless steel, there is no restriction|limiting in particular, A well-known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable. Examples of austenitic stainless steels include SUS (Steel Use Stainless) 304 (Ni content: 8% by mass, Cr content: 18% by mass), SUS304L (Ni content: 9% by mass, Cr content: 18% by mass), SUS316 (content of Ni: 10% by mass, content of Cr: 16% by mass), and SUS316L (content of Ni: 12% by mass, content of Cr: 16% by mass), etc.

作為鎳-鉻合金，並無特別限制，能夠使用公知的鎳-鉻合金。其中，鎳的含量係40～75質量%、鉻的含量係1～30質量%的鎳-鉻合金為較佳。 作為鎳-鉻合金，例如可舉出赫史特合金（產品名以下相同。）、蒙乃爾合金（產品名以下相同）及英高鎳合金（產品名以下相同）等。更具體而言，可舉出赫史特合金C-276（Ni的含量：63質量%、Cr的含量：16質量%）、赫史特合金-C（Ni的含量：60質量%、Cr的含量：17質量%）、赫史特合金C-22（Ni的含量：61質量%、Cr的含量：22質量%）等。 又，鎳-鉻合金依據需要除了上述之合金以外，亦可以包含硼、矽、鎢、鉬、銅及鈷等。The nickel-chromium alloy is not particularly limited, and a well-known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable. As the nickel-chromium alloy, for example, Hester alloy (the same product name and below), Monel (the same product name and below), and Inconel (the same product name and below), etc. can be cited. More specifically, there are Hearst alloy C-276 (Ni content: 63% by mass, Cr content: 16% by mass), Hearst alloy-C (Ni content: 60% by mass, Cr Content: 17% by mass), Hearst alloy C-22 (content of Ni: 61% by mass, content of Cr: 22% by mass), etc. In addition, the nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc., in addition to the above-mentioned alloys as required.

作為對金屬材料進行電解研磨之方法並無特別限制，能夠使用公知的方法。例如，能夠使用日本特開2015-227501號公報的[0011]-[0014]段及日本特開2008-264929號公報的[0036]-[0042]段等中所記載之方法。There is no particular limitation on the method of electrolytic polishing of the metal material, and a known method can be used. For example, the methods described in paragraphs [0011]-[0014] of Japanese Patent Application Publication No. 2015-227501 and paragraphs [0036]-[0042] of Japanese Patent Application Publication No. 2008-264929 can be used.

可推測金屬材料藉由進行電解研磨，表面的鈍化層中的鉻的含量變得多於母相的鉻的含量。因此，從由經電解研磨之金屬材料塗覆之內壁難以向處理液中流出金屬元素，因此可推測能夠獲得特定金屬元素減少之處理液。 另外，金屬材料經拋光為較佳。拋光方法並無特別限制，能夠使用公知的方法。用於精拋之研磨粒的尺寸並無特別限制，從金屬材料的表面的凹凸更容易變小之觀點考慮，#400以下為較佳。 另外，拋光在電解研磨之前進行為較佳。 又，金屬材料亦可以組合1或2個以上的改變研磨粒的尺寸等粗細來進行之複數個階段的拋光、酸清洗及磁性流體研磨等來進行處理。It can be inferred that the content of chromium in the passivation layer on the surface of the metal material becomes more than the content of chromium in the parent phase by electrolytic polishing. Therefore, it is difficult for metal elements to flow out of the treatment liquid from the inner wall coated with the electrolytically polished metal material. Therefore, it can be presumed that a treatment liquid with reduced specific metal elements can be obtained. In addition, the metal material is preferably polished. The polishing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for fine polishing is not particularly limited. From the viewpoint that the unevenness on the surface of the metal material is more likely to be reduced, #400 or less is preferable. In addition, polishing is preferably performed before electrolytic polishing. In addition, the metal material can also be processed by combining 1 or 2 or more stages of polishing, acid cleaning, magnetic fluid polishing, etc., which are performed by changing the size of the abrasive grains and other thicknesses.

該等容器在填充前清洗容器內部為較佳。用於清洗之液體依據用途適當選擇即可，但是包含上述處理液、對上述處理液進行了稀釋之液體或添加到上述處理液之成分中的至少1種之液體為較佳。It is better to clean the inside of these containers before filling. The liquid used for cleaning may be appropriately selected depending on the application, but a liquid containing at least one of the above-mentioned treatment liquid, a liquid diluted with the above-mentioned treatment liquid, or components added to the above-mentioned treatment liquid is preferable.

以防止保管時的處理液中的成分的變化之目的，亦可以將容器內替換成純度99.99995體積%以上的惰性氣體（氮氣或氬氣等）。尤其，含水率少的氣體為較佳。又，液體收容體的輸送、保管時，可以為常溫，但是為了防止變質，亦可以將溫度控制在-20℃至20℃的範圍內。For the purpose of preventing changes in the composition of the processing liquid during storage, the container can also be replaced with an inert gas (nitrogen or argon, etc.) with a purity of 99.99995% by volume or more. In particular, a gas with a low water content is preferable. In addition, when the liquid container is transported and stored, the temperature may be normal, but in order to prevent deterioration, the temperature may be controlled within the range of -20°C to 20°C.

[基板的處理方法] 使用本發明的處理液之基板的處理方法（以下，簡稱為“本處理方法”。）中，上述處理液典型的能夠與作為具有含有金屬之材料之金屬系材料之基板接觸而使用。此時，基板可以含有複數種金屬系材料。又，處理液係溶解可以含有複數種之金屬系材料中的至少1種亦較佳。[Processing method of substrate] In a substrate processing method using the processing liquid of the present invention (hereinafter referred to as "this processing method"), the processing liquid can typically be used in contact with a substrate of a metal-based material that is a material containing a metal. In this case, the substrate may contain a plurality of metal-based materials. In addition, it is also preferable that the treatment liquid dissolves at least one of a plurality of types of metal-based materials.

金屬系材料具有金屬原子（鈷（Co）、釕（Ru）、鉬（Mo）、鋁（Al）、銅（Cu）、鈦（Ti）、鎢（W）及/或鉭（Ta）等）即可，例如可舉出單體金屬、合金、金屬氧化物（可以為複合氧化物）及金屬氮化物（可以為複合氮化物）。又，作為基板中所包含之金屬系材料，亦可舉出包含選自包括單體金屬、合金、金屬氧化物及金屬氮化物之群組中之至少一個及選自包括作為摻雜劑的碳、氮、硼及磷之群組中之至少一個元素之材料。 金屬系材料中的金屬原子的含量相對於金屬系材料的總質量係30～100質量%為較佳，40～100質量%為更佳，52～100質量%為進一步較佳。 金屬系材料包含上述摻雜劑之情況下，金屬原子的摻雜劑的含量相對於金屬系材料的總質量係0.1～50質量%為較佳，10～40質量%為更佳。又，該情況下，金屬系材料中的金屬原子的含量相對於金屬系材料的總質量係30～99.9質量%為較佳，60～90質量%為更佳。Metal-based materials have metal atoms (cobalt (Co), ruthenium (Ru), molybdenum (Mo), aluminum (Al), copper (Cu), titanium (Ti), tungsten (W) and/or tantalum (Ta), etc.)) That is, for example, single metals, alloys, metal oxides (may be composite oxides), and metal nitrides (may be composite nitrides) are mentioned. In addition, as the metal-based material contained in the substrate, at least one selected from the group consisting of single metals, alloys, metal oxides, and metal nitrides and selected from the group consisting of carbon as a dopant can also be mentioned. A material of at least one element from the group of, nitrogen, boron and phosphorus. The content of metal atoms in the metal-based material is preferably 30-100% by mass relative to the total mass of the metal-based material, more preferably 40-100% by mass, and still more preferably 52-100% by mass. When the metal-based material contains the above-mentioned dopant, the content of the metal atom dopant is preferably 0.1-50% by mass relative to the total mass of the metal-based material, and more preferably 10-40% by mass. Moreover, in this case, the content of the metal atoms in the metal-based material is preferably 30 to 99.9% by mass, and more preferably 60 to 90% by mass relative to the total mass of the metal-based material.

[第1態樣：基板的清洗方法] 作為本處理方法的第1態樣，可舉出包括使用上述處理液對規定的基板進行清洗之清洗步驟B之基板的清洗方法。上述基板的清洗方法亦可以包含在清洗步驟B之前製備上述處理液之處理液製備步驟A。 以下基板的清洗方法的說明中，將在清洗步驟B之前實施處理液製備步驟A之情況作為一例來表示，但是並不限定於此，基板的清洗方法亦可以使用預先準備之上述處理液來進行。[First Aspect: Cleaning Method of Substrate] As a first aspect of this processing method, a substrate cleaning method including a cleaning step B of cleaning a predetermined substrate using the above-mentioned processing liquid can be exemplified. The cleaning method of the above-mentioned substrate may also include a treatment liquid preparation step A of preparing the above-mentioned treatment liquid before the cleaning step B. In the following description of the substrate cleaning method, the case where the processing liquid preparation step A is performed before the cleaning step B is shown as an example, but it is not limited to this. The substrate cleaning method can also be performed using the above-mentioned processing liquid prepared in advance. .

〔清洗對象物〕 清洗方法的清洗對象物只要為具備金屬層之基板則並無特別限制，具備選自包括包含Co之金屬層、包含W之金屬層及包含Cu之金屬層之群組中之至少1種層為較佳，具備包含Co之金屬層為更佳。又，作為清洗對象物，除了金屬層以外還具備SiOx層之基板亦較佳。 作為上述清洗對象物，例如可舉出在基板上至少依序具備金屬層、層間絕緣膜、金屬硬遮罩之積層體。積層體還可以藉由經由乾式蝕刻步驟等，具有以露出金屬層的表面的方式從金屬硬遮罩的表面（開口部）朝向基板形成之孔。 如上述的具有孔之積層體之製造方法並無特別限制，可舉出如下方法，亦即，將金屬硬遮罩用作遮罩來對依序具有基板、金屬層、層間絕緣膜及金屬硬遮罩之處理前積層體實施乾式蝕刻步驟，並以露出金屬層的表面的方式對層間絕緣膜進行蝕刻，藉此設置貫穿金屬硬遮罩及層間絕緣膜內之孔。 另外，金屬硬遮罩之製造方法並無特別限制，例如可舉出如下方法，亦即，首先在層間絕緣膜上形成含有特定成分之金屬層，並在該金屬層上形成特定圖案的光阻膜。接著，將光阻膜用作遮罩，對金屬層進行蝕刻，藉此製造金屬硬遮罩（亦即，金屬層被圖案化之膜）。 又，積層體可以具有除了上述層以外的層，例如可舉出蝕刻停止膜、防反射層等。〔Object to be cleaned〕 The cleaning target of the cleaning method is not particularly limited as long as it is a substrate provided with a metal layer, and at least one layer selected from the group consisting of a metal layer containing Co, a metal layer containing W, and a metal layer containing Cu is provided. Preferably, it is more preferable to have a metal layer containing Co. Moreover, as the cleaning object, a substrate having an SiOx layer in addition to the metal layer is also preferable. Examples of the object to be cleaned include a laminate having at least a metal layer, an interlayer insulating film, and a metal hard mask in this order on a substrate. The laminate may have a hole formed from the surface (opening portion) of the metal hard mask toward the substrate through a dry etching step or the like so as to expose the surface of the metal layer. The method for manufacturing the laminated body with holes as described above is not particularly limited, and the following method may be mentioned. That is, a metal hard mask is used as a mask to provide a substrate, a metal layer, an interlayer insulating film, and a metal hard mask in this order. Before the mask is processed, the laminate is subjected to a dry etching step, and the interlayer insulating film is etched to expose the surface of the metal layer, thereby providing holes penetrating the metal hard mask and the interlayer insulating film. In addition, the manufacturing method of the metal hard mask is not particularly limited. For example, the following method may be mentioned. That is, first, a metal layer containing a specific composition is formed on the interlayer insulating film, and a photoresist with a specific pattern is formed on the metal layer. membrane. Next, the photoresist film is used as a mask, and the metal layer is etched, thereby manufacturing a metal hard mask (that is, a film in which the metal layer is patterned). In addition, the layered body may have layers other than the above-mentioned layers, and examples thereof include an etching stop film and an anti-reflection layer.

圖1中示出表示上述基板的清洗方法的清洗對象物亦即積層體的一例之剖面示意圖。 圖1所示之積層體10在基板1上依序具備金屬層2、蝕刻停止層3、層間絕緣膜4及金屬硬遮罩5，藉由經由乾式蝕刻步驟等，在特定位置形成有露出金屬層2之孔6。亦即，圖1所示之清洗對象物係如下積層體：依序具備基板1、金屬層2、蝕刻停止層3、層間絕緣膜4及金屬硬遮罩5，在金屬硬遮罩5的開口部的位置上具備從其表面貫穿到金屬層2的表面之孔6。孔6的內壁11以由蝕刻停止層3、層間絕緣膜4及金屬硬遮罩5組成之截面壁11a及由被露出之金屬層2組成之底壁11b構成，並附著有乾式蝕刻殘渣12。FIG. 1 shows a schematic cross-sectional view of an example of a laminate that is a cleaning target that shows the above-mentioned substrate cleaning method. The laminate 10 shown in FIG. 1 is provided with a metal layer 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 in this order on a substrate 1, and exposed metal is formed at a specific position by a dry etching step, etc. Hole 6 of layer 2. That is, the cleaning object shown in FIG. 1 is a laminate as follows: a substrate 1, a metal layer 2, an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5 are provided in this order, and the openings of the metal hard mask 5 The position of the part is provided with a hole 6 penetrating from the surface to the surface of the metal layer 2. The inner wall 11 of the hole 6 is composed of a cross-sectional wall 11a composed of an etching stop layer 3, an interlayer insulating film 4, and a metal hard mask 5, and a bottom wall 11b composed of the exposed metal layer 2, and a dry etching residue 12 is attached. .

上述基板的清洗方法能夠較佳地用於以該等乾式蝕刻殘渣12的去除為目的之清洗。亦即，乾式蝕刻殘渣12的去除性能（殘渣去除性）優異且相對於清洗對象物的內壁11（例如，金屬層2等）之耐腐蝕性亦優異。 又，上述基板的清洗方法亦可以在乾式蝕刻步驟之後實施於進行了乾灰化步驟之積層體。 以下，對上述之積層體的各層構成材料進行說明。The above-mentioned cleaning method of the substrate can be preferably used for cleaning for the purpose of removing the dry etching residue 12. That is, the dry etching residue 12 has excellent removal performance (residue removability) and also excellent corrosion resistance with respect to the inner wall 11 (for example, the metal layer 2 etc.) of the cleaning target. In addition, the above-mentioned cleaning method of the substrate may also be implemented on the laminated body subjected to the dry ashing step after the dry etching step. Hereinafter, the constituent materials of each layer of the above-mentioned laminate will be described.

＜金屬硬遮罩＞ 金屬硬遮罩包含至少1種選自包括銅、鈷、鈷合金、鎢、鎢合金、釕、釕合金、鉭、鉭合金、氧化鋁、氮化鋁、氮氧化鋁、鈦鋁、鈦、氮化鈦、氧化鈦、氧化鋯、氧化鉿、氧化鉭、氧化鑭及釔合金（較佳為YSiOx）之群組中之成分為較佳。其中，x、y分別係由x=1～3、y=1～2表示之數為較佳。 作為上述金屬硬遮罩的材料，例如可舉出TiN、WO2 及ZrO2 等。<Metal hard mask> The metallic hard mask contains at least one selected from copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum oxynitride, Components in the group of titanium aluminum, titanium, titanium nitride, titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy (preferably YSiOx) are preferred. Among them, x and y are preferably numbers represented by x=1 to 3 and y=1 to 2, respectively. Examples of the metal hard mask material, for example, include TiN, WO 2, and ZrO 2 and the like.

＜層間絕緣膜＞ 層間絕緣膜的材料並無特別限制，例如可較佳地舉出介電常數k係3.0以下、更佳為2.6以下者。 作為具體的層間絕緣膜的材料，可舉出SiOx、SiN、SiOC及聚醯亞胺等有機系聚合物等。另外，x係由1～3表示之數為較佳。＜Interlayer insulating film＞ The material of the interlayer insulating film is not particularly limited. For example, a dielectric constant k is preferably 3.0 or less, more preferably 2.6 or less. Specific examples of the material of the interlayer insulating film include organic polymers such as SiOx, SiN, SiOC, and polyimide. In addition, x is preferably a number represented by 1 to 3.

＜蝕刻停止層＞ 蝕刻停止層的材料並無特別限制。作為具體的蝕刻停止層的材料，可舉出SiN、SiON、SiOCN系材料及AlOx等金屬氧化物。＜Etching stop layer＞ The material of the etching stop layer is not particularly limited. Specific examples of the material of the etching stop layer include SiN, SiON, SiOCN-based materials, and metal oxides such as AlOx.

＜金屬層＞ 形成作為配線材料及/或插塞材料之金屬層之材料並無特別限制，包含選自包括鈷、鎢及銅之群組中之1個以上為較佳。又，形成金屬層之材料可以為鈷、鎢或銅與其他金屬的合金。 金屬層還可以包含除了鈷、鎢及銅以外的金屬、氮化金屬及/或合金。作為除了金屬層可以包含之鈷、鎢及銅以外的金屬，例如可舉出鈦、鈦-鎢、氮化鈦、鉭、鉭化合物、鉻、鉻氧化物及鋁。 金屬層除了選自包括鈷、鎢及銅之群組中之1個以上以外，還可以包含選自包括碳、氮、硼及磷之群組中之至少一個摻雜劑。＜Metal layer＞ The material for forming the metal layer as the wiring material and/or the plug material is not particularly limited, and preferably contains one or more selected from the group consisting of cobalt, tungsten, and copper. In addition, the material forming the metal layer may be an alloy of cobalt, tungsten, or copper and other metals. The metal layer may also include metals other than cobalt, tungsten, and copper, metal nitrides, and/or alloys. Examples of metals other than cobalt, tungsten, and copper that may be contained in the metal layer include titanium, titanium-tungsten, titanium nitride, tantalum, tantalum compounds, chromium, chromium oxide, and aluminum. In addition to one or more selected from the group including cobalt, tungsten, and copper, the metal layer may also include at least one dopant selected from the group including carbon, nitrogen, boron, and phosphorus.

＜基板＞ 此處所述之“基板”中例如包括由單層組成之半導體基板及由多層組成之半導體基板。 構成由單層組成之半導體基板之材料並無特別限制，通常由矽、矽鍺、如GaAs的第III-V族化合物或該等的任意組合構成為較佳。 為由多層組成之半導體基板之情況下，其結構並無特別限制，例如亦可以在上述矽等半導體基板上具有如金屬線及介電材料的互連結構（interconnect features）等露出之積體電路結構。作為用於互連結構之金屬及合金，可舉出鋁、與銅合金化之鋁、銅、鈦、鉭、鈷、矽、氮化鈦、氮化鉭及鎢，但是並不限制於該等。又，亦可以在半導體基板上具有層間介電質層、氧化矽、氮化矽、碳化矽及碳摻雜的氧化矽等層。＜Substrate＞ The "substrate" mentioned here includes, for example, a semiconductor substrate composed of a single layer and a semiconductor substrate composed of multiple layers. The material of the semiconductor substrate composed of a single layer is not particularly limited, and it is usually preferably composed of silicon, silicon germanium, group III-V compounds such as GaAs, or any combination of these. In the case of a semiconductor substrate composed of multiple layers, the structure is not particularly limited. For example, it is also possible to have exposed integrated circuits such as metal wires and interconnect features of dielectric materials on the above-mentioned silicon and other semiconductor substrates. structure. Metals and alloys used in interconnect structures include aluminum, aluminum, copper, titanium, tantalum, cobalt, silicon, titanium nitride, tantalum nitride, and tungsten alloyed with copper, but they are not limited to these . In addition, it is also possible to have an interlayer dielectric layer, silicon oxide, silicon nitride, silicon carbide, and carbon-doped silicon oxide layers on the semiconductor substrate.

以下，按步驟對基板的清洗方法進行說明。Hereinafter, the cleaning method of the substrate will be described step by step.

〔處理液製備步驟A〕 處理液製備步驟A係製備上述處理液之步驟。本步驟中所使用之各成分如上所述。 本步驟的順序並無特別限制，例如可舉出藉由攪拌混合特定成分來製備處理液之方法。另外，各成分可以總括添加，亦可以分成複數次添加。 又，包含於處理液之各成分使用分類成半導體水準者或分類成以其為基準之高純度水準者，並使用進行基於過濾之異物去除及/或基於離子交換樹脂等之離子成分減少者為較佳。又，混合原料成分之後，還進行基於過濾之異物去除及/或基於離子交換樹脂等之離子成分減少為較佳。[Processing solution preparation step A] The treatment liquid preparation step A is the step of preparing the above-mentioned treatment liquid. The ingredients used in this step are as described above. The order of this step is not particularly limited. For example, a method of preparing a treatment liquid by stirring and mixing specific components can be mentioned. In addition, each component may be added collectively or divided into multiple additions. In addition, the components contained in the treatment liquid are classified into semiconductor level or high purity level based on it, and the use of foreign matter removal based on filtration and/or reduction of ion components based on ion exchange resins is used. Better. Furthermore, after mixing the raw material components, it is preferable to also perform foreign matter removal by filtration and/or reduction of ion components by ion exchange resin or the like.

又，將處理液設為濃縮液之情況下，在實施清洗步驟B之前，將濃縮液稀釋成5～2000倍而獲得稀釋液之後，使用該稀釋液實施清洗步驟B。作為稀釋濃縮液之溶劑，水或異丙醇為較佳。Furthermore, when the treatment liquid is a concentrated liquid, before the washing step B is carried out, the concentrated liquid is diluted 5-2000 times to obtain a diluted liquid, and then the washing step B is carried out using the diluted liquid. As the solvent for diluting the concentrate, water or isopropanol is preferred.

〔清洗步驟B〕 作為在清洗步驟B中進行清洗之清洗對象物，可舉出上述之積層體，更具體而言，可舉出具備包含選自包括Co、W及Cu之群組中之至少1種金屬之金屬層之基板。又，作為清洗對象物，可例示如上述實施乾式蝕刻步驟來形成孔之積層體10（參閱圖1）。另外，該積層體10在孔6內附著有乾式蝕刻殘渣12。 另外，亦可以在乾式蝕刻步驟之後，將進行了乾灰化步驟之積層體設為清洗對象物。[Cleaning step B] Examples of the cleaning object to be cleaned in the cleaning step B include the above-mentioned laminates, and more specifically, include a metal containing at least one metal selected from the group consisting of Co, W, and Cu Layer of the substrate. Moreover, as a cleaning object, the laminated body 10 (refer FIG. 1) which performs a dry etching process as mentioned above and forms a hole can be illustrated. In addition, in the layered body 10, dry etching residue 12 adheres to the hole 6. In addition, after the dry etching step, the laminate that has been subjected to the dry ashing step may be used as a cleaning target.

使處理液與清洗對象物接觸之方法並無特別限制，例如可舉出在放入罐中之處理液中浸漬清洗對象物之方法、在清洗對象物上對處理液進行噴霧之方法、在清洗對象物上流過處理液之方法及該等的任意組合。從殘渣去除性之觀點考慮，將清洗對象物浸漬於處理液中之方法為較佳。The method of bringing the treatment liquid into contact with the cleaning object is not particularly limited. For example, a method of immersing the cleaning object in the treatment liquid put in a tank, a method of spraying the treatment liquid on the cleaning object, and The method of passing the treatment liquid on the object and any combination of these. From the viewpoint of residue removability, the method of immersing the cleaning object in the treatment liquid is preferable.

處理液的溫度係90℃以下為較佳，25～80℃為更佳，30～75℃為進一步較佳，40～65℃為特佳。The temperature of the treatment liquid is preferably 90°C or lower, more preferably 25 to 80°C, more preferably 30 to 75°C, and particularly preferably 40 to 65°C.

清洗時間能夠依據所使用之清洗方法及處理液的溫度來調整。 用分批浸漬方式（在處理槽內浸漬複數片清洗對象物來進行處理之分批方式）進行清洗之情況下，清洗時間例如係60分鐘以內，1～60分鐘為較佳，3～20分鐘為更佳，4～15分鐘為進一步較佳。The cleaning time can be adjusted according to the cleaning method used and the temperature of the treatment liquid. In the case of washing by batch immersion method (a batch method in which plural pieces of cleaning objects are immersed in a processing tank to process), the washing time is, for example, within 60 minutes, preferably 1-60 minutes, 3-20 minutes More preferably, 4 to 15 minutes is even more preferable.

用單片方式進行清洗之情況下，清洗時間例如係10秒鐘～5分鐘，15秒鐘～4分鐘為較佳，15秒鐘～3分鐘為更佳，20秒鐘～2分鐘為進一步較佳。In the case of single-chip cleaning, the cleaning time is, for example, 10 seconds to 5 minutes, preferably 15 seconds to 4 minutes, 15 seconds to 3 minutes is more preferable, and 20 seconds to 2 minutes is further good.

另外，為了更加增進處理液的清洗能力，亦可以使用機械攪拌方法。 作為機械攪拌方法，例如可舉出使處理液在清洗對象物上循環之方法、使處理液在清洗對象物上流過或噴霧之方法及用超聲波或兆頻攪拌處理液之方法等。In addition, in order to further enhance the cleaning ability of the treatment liquid, a mechanical stirring method can also be used. As the mechanical stirring method, for example, a method of circulating the treatment liquid on the cleaning object, a method of flowing or spraying the treatment liquid on the cleaning object, and a method of agitating the treatment liquid by ultrasonic or megafrequency.

〔沖洗步驟B2〕 基板的清洗方法在清洗步驟B之後，還可以具有繼續用溶劑洗淨清洗對象物之步驟（以下稱為“沖洗步驟B2”。）。 沖洗步驟B2與清洗步驟B連續進行，係用沖洗溶劑（沖洗液）歷時5秒鐘～5分鐘進行沖洗之步驟為較佳。沖洗步驟B2亦可以使用上述機械攪拌方法來進行。[Rinse step B2] The cleaning method of the substrate may have a step of continuing to clean the object to be cleaned with a solvent after the cleaning step B (hereinafter referred to as "rinsing step B2"). The rinsing step B2 and the rinsing step B are carried out continuously, and it is preferable to use a rinsing solvent (rinsing liquid) for rinsing for 5 seconds to 5 minutes. The rinsing step B2 can also be performed using the above-mentioned mechanical stirring method.

作為沖洗溶劑，例如可舉出脫離子（DI：De Ionized）水、甲醇、乙醇、異丙醇、N-甲基吡咯啶酮、γ-丁內酯、二甲亞碸、乳酸乙酯及丙二醇單甲醚乙酸酯。 作為沖洗液的溶劑，DI水、甲醇、乙醇、異丙醇或該等混合液為較佳，DI水、異丙醇或DI水與異丙醇的混合液為更佳。 沖洗液作為溶劑而包含水之情況下，從SiOx層中的處理液去除性優異之觀點考慮為較佳。又，沖洗液作為溶劑而包含異丙醇之情況下，從本發明的效果優異之觀點考慮為較佳。亦即，沖洗液具有包含水及異丙醇之混合溶劑之情況下，從本發明的效果及SiOx層中的處理液去除性的平衡優異之觀點考慮為較佳。 沖洗液的溶劑係DI水與異丙醇的混合液之情況下，異丙醇的含量相對於混合液的總量係5質量%以上為較佳，從相對於Co膜之耐腐蝕性更優異之觀點考慮，30質量%以上為更佳。上限並無特別限制，95質量%以下為較佳。Examples of rinsing solvents include deionized (DI: De Ionized) water, methanol, ethanol, isopropanol, N-methylpyrrolidone, γ-butyrolactone, dimethylsulfoxide, ethyl lactate, and propylene glycol. Monomethyl ether acetate. As the solvent of the rinsing liquid, DI water, methanol, ethanol, isopropanol or these mixed liquids are preferable, and DI water, isopropanol, or a mixed liquid of DI water and isopropanol is more preferable. When the rinse liquid contains water as a solvent, it is preferable from the viewpoint of excellent removal of the treatment liquid in the SiOx layer. Moreover, when the rinse liquid contains isopropyl alcohol as a solvent, it is preferable from a viewpoint of the excellent effect of this invention. That is, when the rinse liquid has a mixed solvent containing water and isopropanol, it is preferable from the viewpoint of the effect of the present invention and the excellent balance of the removal property of the treatment liquid in the SiOx layer. When the solvent of the rinse liquid is a mixed liquid of DI water and isopropanol, the content of isopropanol is preferably 5% by mass or more relative to the total amount of the mixed liquid, and the corrosion resistance relative to the Co film is more excellent. From this point of view, 30% by mass or more is more preferable. The upper limit is not particularly limited, but 95% by mass or less is preferable.

又，從相對於Co膜之耐腐蝕性優異之觀點考慮，沖洗液包含氫氧化銨等鹼性化合物為較佳。沖洗液中的鹼性化合物的含量並無特別限制，從相對於Co膜之耐腐蝕性更優異之觀點考慮，相對於溶液的總質量係5質量%以上為較佳。 尤其，沖洗液包含水與異丙醇的混合溶劑之情況下，從Co膜中的處理液去除性更優異之觀點考慮，包含氫氧化銨等鹼性化合物為較佳。從SiOx層中的處理液去除性優異之觀點考慮，該情況下的鹼性化合物的含量相對於混合溶劑的總質量係50質量ppm以上為較佳。In addition, from the viewpoint of excellent corrosion resistance with respect to the Co film, it is preferable that the rinse solution contains a basic compound such as ammonium hydroxide. The content of the basic compound in the rinsing solution is not particularly limited, but from the viewpoint of better corrosion resistance with respect to the Co film, it is preferably 5% by mass or more with respect to the total mass of the solution. In particular, when the rinse liquid contains a mixed solvent of water and isopropanol, it is preferable to contain a basic compound such as ammonium hydroxide from the viewpoint that the removal of the treatment liquid in the Co film is more excellent. From the viewpoint of excellent removal of the treatment liquid in the SiOx layer, the content of the basic compound in this case is preferably 50 mass ppm or more with respect to the total mass of the mixed solvent.

作為使沖洗溶劑與清洗對象物接觸之方法，亦能夠相同地應用使上述之處理液與清洗對象物接觸之方法。 沖洗步驟B2中的沖洗溶劑的溫度係16～27℃為較佳。As a method of bringing the washing solvent into contact with the object to be cleaned, the method of bringing the above-mentioned treatment liquid into contact with the object to be cleaned can also be applied in the same way. The temperature of the rinsing solvent in the rinsing step B2 is preferably 16-27°C.

〔乾燥步驟B3〕 基板的清洗方法亦可以在沖洗步驟B2之後，具有使清洗對象物乾燥之乾燥步驟B3。 作為乾燥方法並無特別限制。作為乾燥方法，例如可舉出旋轉乾燥法、使乾性氣體流過清洗對象物上之方法、藉由如加熱板或紅外線燈的加熱機構對基板進行加熱之方法、馬蘭哥尼乾燥法、諾塔哥尼乾燥法、IPA（異丙醇）乾燥法及該等的任意組合。 乾燥步驟B3中的乾燥時間取決於所使用之特定的方法，但是20秒鐘～5分鐘為較佳。[Drying step B3] The cleaning method of the substrate may have a drying step B3 of drying the cleaning object after the rinsing step B2. The drying method is not particularly limited. Examples of drying methods include spin drying, a method of flowing dry gas over the object to be cleaned, a method of heating a substrate by a heating mechanism such as a hot plate or an infrared lamp, Marangoni drying method, and Nota Konecranes drying method, IPA (isopropanol) drying method and any combination of these. The drying time in the drying step B3 depends on the specific method used, but 20 seconds to 5 minutes is preferred.

作為乾燥步驟B3，從SiOx層中的處理液去除性優異之觀點考慮，藉由加熱機構來加熱基板，藉此對其進行乾燥為較佳。 該情況下的加熱溫度並無特別限制，但是從SiOx層中的處理液去除性與Co膜及SiOx層中的膜削減的平衡更優異之觀點考慮，50～350℃為較佳，超過100℃且小於400℃為更佳，從Co膜及SiOx層中的處理液去除性更優異之觀點考慮，150～250℃為進一步較佳。As the drying step B3, it is preferable to dry the substrate by heating the substrate by a heating mechanism from the viewpoint of excellent removal of the treatment liquid in the SiOx layer. The heating temperature in this case is not particularly limited, but from the viewpoint that the balance between the removal of the treatment liquid in the SiOx layer and the film reduction in the Co film and the SiOx layer is more excellent, 50-350°C is preferable, and more than 100°C And it is more preferable to be less than 400 degreeC, and 150-250 degreeC is more preferable from a viewpoint that the removal property of the processing liquid in a Co film and a SiOx layer is more excellent.

〔粗大粒子去除步驟H〕 上述基板的清洗方法在上述處理液製備步驟A之後且在上述清洗步驟B之前，具有去除處理液中的粗大粒子之粗大粒子去除步驟H為較佳。 藉由減少或去除處理液中的粗大粒子，能夠減少殘留於經清洗步驟B之後的清洗對象物上之粗大粒子的量。其結果，能夠抑制因清洗對象物上的粗大粒子而引起之圖案損害，亦能夠抑制元件的產率降低及可靠性降低帶來的影響。 作為用於去除粗大粒子的具體的方法，例如可舉出使用特定除粒徑的除粒子膜對經處理液製備步驟A之處理液進行過濾純化之方法等。 另外，關於粗大粒子的定義，如上所述。〔Step H for removing coarse particles〕 In the method for cleaning the substrate, after the processing liquid preparation step A and before the cleaning step B, it is preferable to have a coarse particle removal step H for removing coarse particles in the processing liquid. By reducing or removing the coarse particles in the treatment liquid, the amount of the coarse particles remaining on the cleaning object after the cleaning step B can be reduced. As a result, it is possible to suppress pattern damage caused by the coarse particles on the cleaning object, and it is also possible to suppress the influence of the decrease in the yield of the device and the decrease in reliability. As a specific method for removing coarse particles, for example, a method of filtering and purifying the treatment solution in the treatment solution preparation step A using a particle removal membrane with a specific particle size can be cited. In addition, the definition of coarse particles is as described above.

〔除電步驟I、J〕 上述基板的清洗方法包含選自包括在上述處理液製備步驟A之前，對用於製備處理液之水進行除電之除電步驟I及上述處理液製備步驟A之後且上述清洗步驟B之前，對上述處理液進行除電之除電步驟J之群組中之至少1種步驟為較佳。 用於對清洗對象物供給處理液的接液部的材質由相對於處理液不會溶出金屬的材料形成或塗覆為較佳。作為上述的材料，例如可舉出作為能夠用於液體收容體之容器的內壁之材料進行了說明之材料等。 另外，上述材料可以為樹脂。上述材料係樹脂之情況下，樹脂多為導電率較低且為絕緣性。因此，例如將上述處理液在內壁由樹脂形成或塗覆之配管上通液之情況或藉由樹脂製除粒子膜及樹脂製離子交換樹脂膜進行了過濾純化之情況下，處理液的帶電電位增加而有引起靜電災害之虞。 因此，基板的清洗方法中，實施上述除電步驟I及除電步驟J的至少一個步驟，降低處理液的帶電電位為較佳。又，藉由進行除電，能夠更加抑制異物（粗大粒子等）對基板的附著及/或對清洗對象物的損害（腐蝕）。 作為除電方法，具體而言，可舉出使水及/或處理液與導電性材料接觸之方法。 使水及/或處理液與導電性材料接觸之接觸時間係0.001～1秒鐘為較佳，0.01～0.1秒鐘為更佳。 作為樹脂的具體例，可舉出高密度聚乙烯（HDPE）、高密度聚丙烯（PP）、6,6-尼龍、四氟乙烯（PTFE）、四氟乙烯與全氟烷基乙烯醚的共聚物（PFA）、聚氯三氟乙烯（PCTFE）、乙烯-氯三氟乙烯共聚物（ECTFE）、乙烯-四氟化乙烯共聚物（ETFE）及四氟化乙烯-六氟化丙烯共聚物（FEP）。 作為導電性材料，可舉出不銹鋼、金、鉑、鑽石及玻璃碳。〔Steps I and J of neutralization〕 The method for cleaning the substrate includes a method selected from the group consisting of removing electricity from the water used to prepare the treatment solution before the treatment solution preparation step A, and after the treatment solution preparation step A and before the cleaning step B, the treatment At least one step in the group of the static elimination step J in which the liquid is neutralized is preferable. The material of the liquid contact part for supplying the treatment liquid to the cleaning object is preferably formed or coated with a material that does not elute metal with respect to the treatment liquid. Examples of the above-mentioned materials include materials described as materials that can be used for the inner wall of the container of the liquid container. In addition, the above-mentioned material may be resin. In the case of the above-mentioned material-based resin, the resin is often low in conductivity and insulating. Therefore, for example, when the above-mentioned treatment liquid is made of resin on the inner wall or passed through a pipe coated with resin, or when the resin particle removal membrane and resin ion exchange resin membrane are filtered and purified, the charging of the treatment liquid Potential increase may cause static electricity disaster. Therefore, in the substrate cleaning method, it is better to implement at least one of the above-mentioned neutralization step I and the neutralization step J to reduce the charged potential of the treatment liquid. In addition, by performing static elimination, it is possible to further suppress adhesion of foreign matter (coarse particles, etc.) to the substrate and/or damage (corrosion) to the cleaning object. As a method of neutralization, specifically, the method of bringing water and/or a treatment liquid into contact with a conductive material is mentioned. The contact time for bringing the water and/or the treatment liquid into contact with the conductive material is preferably 0.001 to 1 second, and more preferably 0.01 to 0.1 second. Specific examples of resins include high-density polyethylene (HDPE), high-density polypropylene (PP), 6,6-nylon, tetrafluoroethylene (PTFE), copolymerization of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), polychlorotrifluoroethylene (PCTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE) and tetrafluoroethylene-hexafluoropropylene copolymer ( FEP). Examples of conductive materials include stainless steel, gold, platinum, diamond, and glassy carbon.

基板的清洗方法具有：處理液製備步驟A、清洗步驟B、回收在清洗步驟B中使用之處理液的排液之排液回收步驟C、使用所回收之處理液的排液清洗新準備之具備特定層之基板之清洗步驟D及回收在上述清洗步驟D中所使用之上述處理液的排液之排液回收步驟E，亦可以為反覆實施上述清洗步驟D及上述排液回收步驟E來回收上述處理液的排液之基板的清洗方法。The substrate cleaning method includes: treatment liquid preparation step A, cleaning step B, drain recovery step C to recover the drain of the treatment liquid used in cleaning step B, and new preparation for drain cleaning using the recovered treatment solution. The cleaning step D of the substrate of the specific layer and the drain recovery step E of recovering the drain of the treatment liquid used in the cleaning step D can also be repeated by repeating the cleaning step D and the drain recovery step E to recover The above-mentioned method of cleaning the substrate for the discharge of the treatment liquid.

上述基板的清洗方法中，處理液製備步驟A、清洗步驟B的態樣如上述。又，再利用上述排液之態樣中亦具有在上述之態樣中說明之粗大粒子去除步驟H及除電步驟I、J為較佳。又，亦可以在清洗步驟B之前具有在上述之態樣中說明之處理液製備步驟A。In the above-mentioned substrate cleaning method, the processing liquid preparation step A and the cleaning step B are as described above. In addition, it is preferable that the state of reusing the above-mentioned draining liquid also has the coarse particle removal step H and the neutralization steps I, J described in the above-mentioned aspect. In addition, before the cleaning step B, the treatment liquid preparation step A described in the above aspect may be provided.

使用回收之處理液的排液實施基板的清洗之清洗步驟D的態樣如上所述。 排液回收步驟C、E中的排液回收機構並無特別限制。回收之排液保存於上述除電步驟J中上述之容器為較佳，此時亦可以進行與除電步驟J相同的除電步驟。又，亦可以設置對回收之排液實施過濾等而去除雜質之步驟。The state of the cleaning step D of the substrate cleaning using the drained liquid of the recovered processing liquid is as described above. The drainage recovery mechanism in the drainage recovery steps C and E is not particularly limited. It is preferable that the recovered drained liquid be stored in the above-mentioned container in the above-mentioned neutralization step J. At this time, the same neutralization step as that of the neutralization step J can also be performed. In addition, it is also possible to provide a step of filtering the recovered drainage to remove impurities.

[第2態樣] 作為本處理方法的具體的例，可舉出使含有金屬含有物（尤其鈷含有物）之被處理物與上述處理液接觸來溶解金屬含有物（尤其鈷含有物）之方法。將這樣的被處理物的處理方法亦稱為本處理方法的第2態樣。 使被處理物與處理液接觸之方法並無特別限制，例如可舉出在放入罐中之處理液中浸漬被處理物之方法、在被處理物上對處理液進行噴霧之方法、在被處理物上流過處理液之方法及該等的任意組合。其中，將被處理物浸漬於處理液之方法為較佳。[Second aspect] As a specific example of the present treatment method, a method of dissolving the metal-containing material (especially cobalt-containing material) by contacting a to-be-processed object containing a metal-containing material (especially a cobalt-containing material) with the above-mentioned treatment liquid. The processing method of such a to-be-processed object is also called the 2nd aspect of this processing method. There are no particular restrictions on the method of contacting the treated object with the treatment liquid. For example, the method of immersing the treated object in the treatment liquid put in the tank, the method of spraying the treatment liquid on the treated object, and the method of The method of flowing the treatment liquid on the treatment object and any combination of these. Among them, the method of immersing the object to be treated in the treatment liquid is preferred.

另外，為了更加增進處理液的清洗能力，亦可以使用機械式攪拌方法。 作為機械式攪拌方法，例如可舉出使處理液在被處理物上循環之方法、使處理液在被處理物上流過或噴霧之方法及用超聲波或兆頻攪拌處理液之方法。In addition, in order to further enhance the cleaning ability of the treatment liquid, a mechanical stirring method can also be used. As the mechanical stirring method, for example, a method of circulating the processing liquid on the object to be processed, a method of flowing or spraying the processing liquid on the object to be processed, and a method of agitating the processing liquid by ultrasonic or megafrequency.

被處理物與處理液的接觸時間能夠適當調整。 處理時間（處理液與被處理物的接觸時間）並無特別限制，0.25～10分鐘為較佳，0.5～2分鐘為更佳。 處理時的處理液的溫度並無特別限制，20～75℃為較佳，20～60℃為更佳。The contact time between the processed object and the processing liquid can be adjusted appropriately. The treatment time (the contact time between the treatment liquid and the object to be treated) is not particularly limited, and 0.25 to 10 minutes is preferred, and 0.5 to 2 minutes is more preferred. The temperature of the treatment liquid during the treatment is not particularly limited, but 20 to 75°C is preferable, and 20 to 60°C is more preferable.

藉由實施本處理，溶解被處理物中的金屬含有物（尤其鈷含有物）。By performing this treatment, the metal-containing material (especially cobalt-containing material) in the processed object is dissolved.

[第3態樣] 作為本處理方法的另一態樣，可舉出以下第3態樣。 亦即，包括如下步驟之被處理物的處理方法：步驟P，對含有金屬層之被處理物（基板）實施氧化處理使上述金屬層的表層氧化而製得金屬氧化層；及步驟Q，使處理液與在上述步驟P中形成之被處理物的金屬氧化層的表面接觸來溶解上述金屬氧化層。 第3態樣可以為第2態樣的一形態。[3rd aspect] As another aspect of this processing method, the following 3rd aspect is mentioned. That is, the processing method of the object to be processed includes the following steps: step P, performing oxidation treatment on the object (substrate) containing the metal layer to oxidize the surface layer of the metal layer to obtain a metal oxide layer; and step Q, making The treatment liquid is brought into contact with the surface of the metal oxide layer of the object to be treated formed in the above step P to dissolve the metal oxide layer. The third aspect may be a form of the second aspect.

上述金屬層係指金屬系材料的一形態且能夠進行氧化之金屬系材料。金屬層例如係金屬的單體或合金為較佳。又，金屬層係鈷含有物（鈷單體或鈷合金等）、釕含有物（釕單體或釕合金等）、鉬含有物（鉬單體或鉬合金等）、鋁含有物（鋁單體或鋁合金等）或銅含有物（銅單體或銅合金等）為較佳，鈷含有物（鈷單體或鈷合金等）為更佳。The above-mentioned metal layer refers to a form of a metal-based material and a metal-based material that can be oxidized. The metal layer is preferably a single metal or an alloy of metal. In addition, the metal layer-based cobalt-containing material (cobalt monomer or cobalt alloy, etc.), ruthenium-containing material (ruthenium monomer or ruthenium alloy, etc.), molybdenum-containing material (molybdenum monomer or molybdenum alloy, etc.), aluminum-containing material (aluminum single It is preferable to use a copper alloy or an aluminum alloy, etc.) or a copper-containing substance (a copper monomer or a copper alloy, etc.), and a cobalt-containing substance (a cobalt monomer or a cobalt alloy, etc.) is more preferable.

上述金屬氧化層係指上述金屬層的表層被氧化而成之層，亦稱為金屬系材料的一形態。金屬層的表層的一部分可以成為金屬氧化層，金屬層的表層的整個表面亦可以成為金屬氧化層。 金屬氧化層係金屬單體或合金的氧化物，由鈷氧化物、鈷合金的氧化物、釕氧化物、釕合金的氧化物、鉬氧化物、鉬合金的氧化物、鋁氧化物、鋁合金的氧化物、銅氧化物或銅合金的氧化物構成之層為較佳，由鈷氧化物或鈷合金的氧化物構成之層為更佳，由鈷氧化物構成之層為進一步較佳。 金屬氧化層的厚度例如係1～10原子層分。另外，金屬及氧化金屬的1原子層的厚度係1nm以下（例如，0.3nm～0.4nm）。 金屬氧化層多為比金屬層相對於處理液溶解性高（容易進行蝕刻）。 亦即，在第3態樣中，將步驟P中金屬層的表面作為薄的金屬氧化層， 在步驟Q中使用處理液僅去除上述金屬氧化層（及存在於金屬氧化層的下層之金屬層能夠不可避免地溶解之部分），藉此能夠僅去除被處理物所含有之金屬層之極其薄的表面。 另外，藉由交替地反覆實施步驟P及步驟Q，能夠高精度地控制蝕刻量。 作為交替地進行步驟P及步驟Q時的各步驟的實施次數，例如將步驟P及步驟Q組合為1循環，1～20循環即可。從凹陷量的控制優異之觀點考慮，交替地進行步驟P及步驟Q時的各步驟的實施次數係3循環以上為較佳，5循環以上為更佳。The above-mentioned metal oxide layer refers to a layer formed by oxidizing the surface layer of the above-mentioned metal layer, and is also referred to as a form of metal-based material. A part of the surface layer of the metal layer may become a metal oxide layer, and the entire surface of the surface layer of the metal layer may also become a metal oxide layer. The metal oxide layer is the oxide of a single metal or an alloy, consisting of cobalt oxide, cobalt alloy oxide, ruthenium oxide, ruthenium alloy oxide, molybdenum oxide, molybdenum alloy oxide, aluminum oxide, aluminum alloy A layer composed of oxide, copper oxide or copper alloy oxide is preferable, a layer composed of cobalt oxide or cobalt alloy oxide is more preferable, and a layer composed of cobalt oxide is even more preferable. The thickness of the metal oxide layer is, for example, 1 to 10 atomic layers. In addition, the thickness of one atomic layer of metal and metal oxide is 1 nm or less (for example, 0.3 nm to 0.4 nm). The metal oxide layer is often more soluble in the treatment liquid than the metal layer (easy to be etched). That is, in the third aspect, the surface of the metal layer in step P is used as a thin metal oxide layer, and in step Q, the treatment solution is used to remove only the metal oxide layer (and the metal layer existing in the lower layer of the metal oxide layer). The part that can be inevitably dissolved), by which only the extremely thin surface of the metal layer contained in the object to be processed can be removed. In addition, by alternately performing step P and step Q repeatedly, the etching amount can be controlled with high accuracy. As the number of times each step is performed when Step P and Step Q are alternately performed, for example, Step P and Step Q may be combined into 1 cycle, and 1 to 20 cycles may be used. From the viewpoint of excellent control of the amount of depression, it is preferable that the number of executions of each step when the steps P and Q are alternately performed is 3 cycles or more, and more preferably 5 cycles or more.

能夠應用第3態樣之被處理物可以單獨含有1種金屬層，亦可以含有2種以上。又，第3態樣能夠應用之被處理物可以含有除了金屬層或金屬氧化層以外的金屬系材料，亦可以經過步驟P及步驟Q而有意或不可避免地去除這樣的金屬系材料的一部分或整體。The object to be processed to which the third aspect can be applied may contain one type of metal layer alone, or may contain two or more types. In addition, the to-be-processed object to which the third aspect can be applied may contain metal-based materials other than the metal layer or metal oxide layer, and may also undergo steps P and Q to intentionally or inevitably remove a part or part of such metal-based materials. overall.

步驟P係對含有上述金屬層之被處理物實施氧化處理而使上述金屬層的表層氧化來製得金屬氧化層之步驟。Step P is a step of oxidizing the surface layer of the metal layer to obtain a metal oxide layer by oxidizing the object to be processed containing the metal layer.

並不限定於用於使金屬層的表層氧化來製得金屬氧化層的氧化處理的方法，例如能夠藉由實施如下而實施：使氧化液與上述被處理物接觸之液處理、使氧化氣體與上述被處理物接觸之氣體處理（使後述的臭氧氣體與基板接觸之臭氧處理或在氧氣環境下進行加熱之氧氣中加熱處理等）或使用氧氣之電漿處理。 氧化處理可以實施1種，亦可以實施2種以上。It is not limited to the method of oxidation treatment for oxidizing the surface layer of the metal layer to produce a metal oxide layer, and it can be carried out, for example, by carrying out the following: The gas treatment (ozone treatment in which the ozone gas described later is brought into contact with the substrate or the heating treatment in oxygen by heating in an oxygen atmosphere) or plasma treatment using oxygen. One type of oxidation treatment may be performed, or two or more types may be performed.

其中，作為氧化處理，至少實施使規定的氧化液與上述被處理物接觸之液處理為較佳。 上述氧化液只要為使上述金屬層的表層氧化之藥液即可。另外，氧化液係除了本發明的處理液以外為較佳。Among them, as the oxidation treatment, it is preferable to perform liquid treatment in which at least a predetermined oxidation liquid is brought into contact with the above-mentioned to-be-processed object. The above-mentioned oxidizing solution may be a chemical solution that oxidizes the surface layer of the above-mentioned metal layer. In addition, the oxidizing liquid system is preferable in addition to the treatment liquid of the present invention.

作為上述氧化液，選自包括水、過氧化氫水、氨與過氧化氫的混合水溶液（APM）、氟酸與過氧化氫水的混合水溶液（FPM）、硫酸與過氧化氫水的混合水溶液（SPM）、鹽酸與過氧化氫水的混合水溶液（HPM）、溶氧水、臭氧溶解水、高氯酸以及硝酸之群組中之藥液（以下亦記載為“特定藥液”）為較佳。 過氧化氫水的組成例如H2 O2 的含量相對於過氧化氫水的總質量係0.5～31質量%，3～15質量%為更佳。 APM的組成例如在“氨水:過氧化氫水:水=1:1:1”～“氨水:過氧化氫水:水=1:3:45”的範圍內（質量比）為較佳。 FPM的組成例如在“氟酸:過氧化氫水:水=1:1:1”～“氟酸:過氧化氫水:水=1:1:200”的範圍內（質量比）為較佳。 SPM的組成例如在“硫酸:過氧化氫水:水=3:1:0”～“硫酸:過氧化氫水:水=1:1:10”的範圍內（質量比）為較佳。 HPM的組成例如在“鹽酸:過氧化氫水:水=1:1:1”～“鹽酸:過氧化氫水:水=1:1:30”的範圍內（質量比）為較佳。 另外，該等較佳之組成比的記載係指氨水係28質量%氨水、氟酸係49質量%氟酸、硫酸係98質量%硫酸、鹽酸係37質量%鹽酸、過氧化氫水係30質量%過氧化氫水時的組成比。 又，體積比以室溫下的體積為基準。 作為較佳範圍的[“A:B:C=x:y:z”～“A:B:C=X:Y:Z”]等之記載表示滿足[“A:B=x:y”～“A:B=X:Y”]、[“B:C=y:z”～“B:C=Y:Z”]及[“A:C=x:z”～“A:C=X:Z”]的範圍內的至少一個（較佳為2個、更佳為整個表面）為較佳。 溶氧水的組成例如係O2 的含量相對於溶氧水的總質量係20～500質量ppm之水溶液。 臭氧溶解水的組成例如係O3 的含量相對於臭氧溶解水的總質量係1～60質量ppm之水溶液。 高氯酸例如係HClO4 的含量相對於溶液的總質量係0.001～60質量%的水溶液。 硝酸例如係HNO3 的含量相對於溶液的總質量係0.001～60質量%的水溶液。As the above-mentioned oxidizing liquid, selected from the group consisting of water, hydrogen peroxide water, mixed aqueous solution of ammonia and hydrogen peroxide (APM), mixed aqueous solution of hydrofluoric acid and hydrogen peroxide water (FPM), and mixed aqueous solution of sulfuric acid and hydrogen peroxide water (SPM), a mixed aqueous solution of hydrochloric acid and hydrogen peroxide (HPM), dissolved oxygen water, ozone-dissolved water, perchloric acid and nitric acid (also referred to as "specific chemical solution" below) are more good. The composition of the hydrogen peroxide water, for example , the content of H 2 O 2 relative to the total mass of the hydrogen peroxide water is 0.5 to 31% by mass, and more preferably 3 to 15% by mass. The composition of APM is preferably within the range (mass ratio) of "ammonia water: hydrogen peroxide water: water=1:1:1" to "ammonia water: hydrogen peroxide water: water=1:3:45". For example, the composition of FPM is preferably within the range (mass ratio) of "fluoric acid: hydrogen peroxide water: water=1:1:1" to "fluoric acid: hydrogen peroxide water: water=1:1:200" . The composition of SPM is preferably within the range (mass ratio) of "sulfuric acid:hydrogen peroxide water:water=3:1:0" to "sulfuric acid:hydrogen peroxide water:water=1:1:10". The composition of HPM is preferably in the range (mass ratio) of "hydrochloric acid:hydrogen peroxide water:water=1:1:1" to "hydrochloric acid:hydrogen peroxide water:water=1:1:30", for example. In addition, the description of these preferable composition ratios refers to ammonia water 28% by mass, hydrofluoric acid 49% by mass, hydrofluoric acid, sulfuric acid 98% by mass, sulfuric acid, hydrochloric acid, 37% by mass, hydrochloric acid, and hydrogen peroxide, 30% by mass. The composition ratio of hydrogen peroxide water. In addition, the volume ratio is based on the volume at room temperature. As the preferred range ["A:B:C=x:y:z"～"A:B:C=X:Y:Z"] and the like indicate that it satisfies ["A:B=x:y"～ "A:B=X:Y"], ["B:C=y:z"～"B:C=Y:Z"] and ["A:C=x:z"～"A:C=X At least one (preferably two, more preferably the entire surface) within the range of :Z"] is preferred. The composition of the oxygen-dissolved water is, for example, an aqueous solution in which the content of O 2 is 20 to 500 ppm by mass relative to the total mass of the oxygen-dissolved water. The composition of ozone-dissolved water is, for example, an aqueous solution in which the content of O 3 is 1 to 60 mass ppm relative to the total mass of ozone-dissolved water. Perchloric acid is, for example, an aqueous solution in which the content of HClO 4 is 0.001 to 60% by mass relative to the total mass of the solution. Nitric acid is, for example, an aqueous solution in which the content of HNO 3 is 0.001 to 60% by mass relative to the total mass of the solution.

液處理中，使被處理物與氧化液（較佳為特定藥液）接觸之方法並無特別限制，例如可舉出在放入罐之氧化液中浸漬被處理物之方法、在被處理物上噴霧氧化液之方法、在被處理物上流過氧化液之方法及該等的任意組合。 被處理物與氧化液的接觸時間例如係0.25～10分鐘為較佳，0.5～5分鐘為更佳。 氧化液的溫度係20～75℃為較佳，20～60℃為更佳。In the liquid treatment, the method of contacting the object to be treated with an oxidizing solution (preferably a specific chemical solution) is not particularly limited. For example, a method of immersing the object to be treated in the oxidizing solution put in a tank, The method of spraying the oxidizing liquid, the method of flowing the oxidizing liquid on the object to be treated, and any combination of these. The contact time between the processed object and the oxidizing solution is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. The temperature of the oxidizing solution is preferably 20 to 75°C, more preferably 20 to 60°C.

氣體處理中，作為與被處理物接觸之氧化氣體，例如可舉出乾空氣、氧氣、臭氧氣體及該等混合氣體。氧化氣體可以含有除了上述氣體以外的氣體。 氣體處理中，與被處理物接觸之氧化氣體係氧氣或臭氧氣體為較佳。使氧氣或臭氧氣體與被處理物接觸之情況下，在氧氣環境下、臭氧環境下或氧氣與臭氧的混合氣體環境下接觸亦較佳。In the gas treatment, examples of the oxidizing gas that comes into contact with the object to be treated include dry air, oxygen, ozone gas, and these mixed gases. The oxidizing gas may contain gases other than the above-mentioned gases. In the gas treatment, oxygen or ozone gas, which is an oxidizing gas system in contact with the object to be treated, is preferred. In the case where oxygen or ozone gas is brought into contact with the object to be processed, the contact is preferably in an oxygen environment, an ozone environment, or a mixed gas environment of oxygen and ozone.

氣體處理中，使氧化氣體接觸的同時加熱（例如在40～200℃下的加熱）被處理物之態樣亦較佳。 其中，氣體處理係使臭氧氣體與被處理物接觸之臭氧處理或在氧氣環境下進行加熱之氧氣中加熱處理為較佳。 在上述臭氧處理中，可以在臭氧環境下使臭氧氣體與被處理物接觸，亦可以在臭氧氣體與其他氣體（例如氧氣）的混合氣體環境下使臭氧氣體與被處理物接觸。又，臭氧處理可以為使臭氧氣體接觸的同時加熱被處理物之處理。In the gas treatment, it is also preferable to heat the object to be treated while contacting the oxidizing gas (for example, heating at 40 to 200°C). Among them, the gas treatment is preferably ozone treatment in which ozone gas is brought into contact with the object to be treated, or heating treatment in oxygen in which heating is performed in an oxygen environment. In the above-mentioned ozone treatment, the ozone gas can be brought into contact with the object to be treated in an ozone environment, or the ozone gas can be brought into contact with the object to be treated in a mixed gas environment of ozone gas and other gases (for example, oxygen). In addition, the ozone treatment may be a treatment in which the object to be treated is heated while contacting ozone gas.

步驟P（尤其進行液處理之情況）中，被處理物可以含有除了藉由氧化處理進行氧化而表層成為金屬氧化層之金屬層以外的金屬系材料，亦可以藉由步驟P（尤其液處理）而有意或不可避免地去除這樣的金屬系材料的一部分或整體。 又，步驟P（尤其進行液處理之情況）中，可以有意或不可避免地去除被處理物的金屬層的一部分。In step P (especially in the case of liquid treatment), the object to be treated may contain metal materials other than the metal layer whose surface layer becomes a metal oxide layer by oxidation by oxidation treatment, or it may be subjected to step P (especially liquid treatment) However, a part or the whole of such metal-based materials is intentionally or unavoidably removed. In addition, in step P (especially in the case of liquid treatment), a part of the metal layer of the object can be removed intentionally or unavoidably.

步驟Q係包括使在上述步驟P中獲得之被處理物與處理液接觸而溶解上述金屬氧化層之步驟Q之被處理物的處理方法。 步驟Q中使被處理物與處理液接觸之方法並無特別限制，可舉出和使被處理物與氧化液接觸之方法相同的例子。 被處理物與處理液的接觸時間例如係0.25～10分鐘為較佳，0.5～5分鐘為更佳。 處理液的溫度係20～75℃為較佳，20～60℃為更佳。Step Q is a method of processing the object to be processed in step Q that includes contacting the object to be processed obtained in step P with a processing liquid to dissolve the metal oxide layer. The method of bringing the object to be processed into contact with the processing liquid in step Q is not particularly limited, and the same example as the method of bringing the object to be processed into contact with the oxidizing liquid can be given. The contact time between the treated object and the treatment liquid is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. The temperature of the treatment liquid is preferably 20 to 75°C, more preferably 20 to 60°C.

步驟Q中，金屬氧化層的去除可以局部進行亦可以整體進行。 步驟Q中，亦可以有意或不可避免地去除金屬層（例如，進行覆蓋表面之金屬氧化層的去除而暴露於表層之金屬層）的一部分或整體。 步驟Q中，被處理物可以含有除了在金屬氧化層及表面形成有金屬氧化層之金屬層以外的其他金屬系材料，亦可以有意或不可避免地去除這樣的金屬系材料的一部分或整體。 另外，有意不溶解上述金屬層及/或上述其他金屬系材料之情況下，不可避免地溶解上述金屬層及/或上述其他金屬系材料之量少為較佳。In step Q, the removal of the metal oxide layer can be performed locally or as a whole. In step Q, a part or the whole of the metal layer may also be removed intentionally or unavoidably (for example, removing the metal oxide layer covering the surface and exposing the metal layer on the surface layer). In step Q, the processed object may contain other metal-based materials other than the metal oxide layer and the metal layer on which the metal oxide layer is formed, and a part or the whole of such metal-based materials may be intentionally or unavoidably removed. In addition, in the case where the metal layer and/or the other metal-based material is intentionally not dissolved, it is preferable that the amount of the metal layer and/or the other metal-based material inevitably dissolved is small.

對提供於步驟Q之處理液預先進行脫氣處理等，可以降低溶解氧量。藉由處理液去除金屬氧化層而露出之金屬層，由處理液中的溶解氧進行氧化而成為新的金屬氧化層，這樣的金屬氧化層進而藉由處理液被去除，其結果能夠藉由降低處理液的溶解氧量來抑制過量的金屬層的去除。 [實施例]Degassing the treatment liquid provided in step Q in advance can reduce the amount of dissolved oxygen. The metal oxide layer is removed by the treatment solution and the exposed metal layer is oxidized by the dissolved oxygen in the treatment solution to become a new metal oxide layer. Such a metal oxide layer is further removed by the treatment solution. As a result, it can be reduced by The amount of dissolved oxygen in the treatment liquid suppresses the removal of the excessive metal layer. [Example]

以下，基於實施例對本發明進行進一步詳細的說明。以下實施例所示之材料、使用量、比例、處理內容及處理順序等只要不脫離本發明的主旨便能夠適當變更。然而，本發明的範圍並非係藉由以下所示之實施例限定地解釋者。Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amount, ratio, processing content, processing order, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. However, the scope of the present invention is not limitedly interpreted by the examples shown below.

[實施例1～31、比較例1～7] 〔處理液的製備〕 以表1中所記載之配方混合表1中所記載之各成分，製備了實施例及比較例的各處理液。另外，各處理液中，各種成分的含量（均為質量基準）如表中所述。 其中，示於表1之各種成分均使用分類成半導體水準者或分類成以其為基準之高純度水準者。[Examples 1 to 31, Comparative Examples 1 to 7] 〔Preparation of treatment liquid〕 Each component described in Table 1 was mixed with the formulation described in Table 1 to prepare each treatment liquid of Examples and Comparative Examples. In addition, the contents of various components (all on a quality basis) in each treatment liquid are as described in the table. Among them, the various components shown in Table 1 are classified into semiconductor level or classified into high purity level based on it.

以下示出表1中所記載之各種成分。The various components described in Table 1 are shown below.

＜水＞ ・超純水＜Water＞ ·Ultra-pure water

＜有機溶劑A＞ ・EGBE：乙二醇單正丁醚 ・DEGBE：二乙二醇單丁醚 ・DMSO：二甲亞碸 ・環丁碸 ・PG：丙二醇 ・HG：伸己基二醇＜Organic Solvent A＞ ・EGBE: ethylene glycol mono-n-butyl ether ・DEGBE: Diethylene glycol monobutyl ether ・DMSO: dimethyl subsulfate ・Ring Dingzhu ・PG: Propylene Glycol ・HG: Hexylene Glycol

＜有機溶劑B＞ ・b-1：1-二級丁氧基丁烷（包含在組合B1或組合2中。） ・b-2：1-（（2-丁氧基乙氧基）甲氧基）丁烷（包含在組合1或組合2中。） ・b-3：1-（2-（乙氧基甲氧基）乙氧基）丁烷（包含在組合1或組合2中。） ・b-4：3,6,9,12-四氧十六烷-1-醇（包含在組合1或組合2中。） ・b-5：二（2-丁氧基）甲烷（包含在組合1或組合2中。） ・b-6：甘油（包含在組合1、組合2或組合5中。） ・b-7：十八醇（包含在組合1或組合2中。） ・b-8：（2-丁氧基乙氧基）乙酸（包含在組合1或組合2中。） ・b-9：二甲基二硫化物（DMDS）（包含在組合3中。） ・b-10：3-環丁烯碸（包含在組合4中。） ・b-11：二甲基亞碸（DMSO）（包含在組合4中。） ・b-12：丙酮（包含在組合6中。） ・b-13：二丙酮醇（包含在組合6中。）＜Organic solvent B＞ ・B-1: 1-Secondary butoxybutane (included in combination B1 or combination 2.) ・B-2: 1-((2-Butoxyethoxy)methoxy)butane (included in combination 1 or combination 2.) ・B-3: 1-(2-(ethoxymethoxy)ethoxy)butane (included in combination 1 or combination 2.) ・B-4: 3,6,9,12-tetraoxetane-1-ol (included in combination 1 or combination 2.) ・B-5: Bis(2-butoxy)methane (included in combination 1 or combination 2.) ・B-6: Glycerin (included in combination 1, combination 2 or combination 5.) ・B-7: Stearyl alcohol (included in combination 1 or combination 2.) ・B-8: (2-Butoxyethoxy) acetic acid (included in combination 1 or combination 2.) ・B-9: Dimethyl disulfide (DMDS) (included in Combination 3.) ・B-10: 3-Cyclobutene (included in Combination 4.) ・B-11: Dimethyl sulfide (DMSO) (included in Combination 4.) ・B-12: Acetone (included in set 6.) ・B-13: Diacetone alcohol (included in set 6.)

＜去除劑＞ ・DTPA：二乙烯三胺五乙酸（相當於螯合劑。） ・HF：氟化氫（相當於含氟化合物。） ・Cy-DTA：反式-1,2-環己烷二胺四乙酸（相當於螯合劑。） ・HA：羥胺（NH2 OH）（相當於羥胺化合物。）<Removing agent> ・DTPA: Diethylenetriaminepentaacetic acid (equivalent to chelating agent.) ・HF: Hydrogen fluoride (equivalent to fluorine-containing compound.) ・Cy-DTA: trans-1,2-cyclohexanediamine tetra Acetic acid (equivalent to chelating agent.) ・HA: Hydroxylamine (NH 2 OH) (equivalent to hydroxylamine compound.)

＜鹼性化合物＞ ・DBU：1,8-二吖雙環[5.4.0]-7-十一烯（相當於含氮脂環化合物。） ・TMAH：氫氧化四甲銨（相當於四級銨氫氧化物。） ・NH4 OH：氫氧化銨 ・AEEA：N-（2-胺基乙基）乙醇胺（相當於二級胺。）＜Basic compound＞ ・DBU: 1,8-diazebicyclo[5.4.0]-7-undecene (equivalent to nitrogen-containing alicyclic compound.) ・TMAH: tetramethylammonium hydroxide (equivalent to quaternary ammonium Hydroxide.) ・NH 4 OH: Ammonium hydroxide ・AEEA: N-(2-aminoethyl)ethanolamine (equivalent to secondary amine.)

＜Co離子源＞ ・Co（OH）2 ：氫氧化鈷（II）＜Co ion source＞ ・Co(OH) 2 : Cobalt hydroxide(II)

＜防腐蝕劑＞ ・5MBTA：5-甲基-1H-苯并三唑（相當於由式（C）表示之化合物。） ・IRGAMET 42：2,2’-｛[（4-甲基-1H-苯并三唑-1-基）甲基]亞胺基｝雙乙醇（相當於由式（C）表示之化合物。） ・BTA：苯并三唑（相當於由式（C）表示之化合物。） ・TTA：甲苯基三唑（相當於由式（C）表示之化合物。）＜Anti-corrosion agent＞ ・5MBTA: 5-methyl-1H-benzotriazole (equivalent to the compound represented by formula (C).) ・IRGAMET 42: 2,2’-{[(4-methyl-1H-benzotriazol-1-yl)methyl]imino}diethanol (equivalent to the compound represented by formula (C).) ・BTA: Benzotriazole (equivalent to the compound represented by formula (C).) ・TTA: Tolyltriazole (equivalent to the compound represented by formula (C).)

〔各種定量〕 關於處理液中所包含之微量的成分，藉由下述方法進行了定量。〔Various quantitative〕 The trace components contained in the treatment liquid were quantified by the following method.

＜有機溶劑B的含量＞ 測量時使用了氣相色譜質譜分析裝置（產品名“GCMS-2020”、Shimadzu Corporation製、測量條件如下所述）。＜Content of organic solvent B＞ A gas chromatography mass spectrometer (product name "GCMS-2020", manufactured by Shimadzu Corporation, measurement conditions are as follows) was used for the measurement.

（測量條件） 毛細管柱：InertCap 5MS/NP 0.25mm I.D. ×30m df=0.25μm 試樣導入法：分流 75kPa 壓力恆定氣化室溫度：230℃ 管柱烘箱溫度：80℃（2min）-500℃（13min）升溫速度15℃/min 載氣：氦氣 隔墊吹掃流量：5mL/min 分流比：25:1 接口溫度：250℃ 離子源溫度：200℃ 測量模式：Scan m/z=85～500 試樣導入量：1μL(Measurement conditions) Capillary column: InertCap 5MS/NP 0.25mm I.D. ×30m df=0.25μm Sample introduction method: split 75kPa Constant pressure vaporization chamber temperature: 230℃ Column oven temperature: 80°C (2min) -500°C (13min) heating rate 15°C/min Carrier gas: helium Septum purge flow: 5mL/min Split ratio: 25:1 Interface temperature: 250℃ Ion source temperature: 200℃ Measurement mode: Scan m/z=85～500 Sample introduction volume: 1μL

＜鈷離子含量＞ 測量時使用了Agilent 8800 三重四極ICP-MS（半導體分析用、選項#200）。以測量結果為基礎，求出了鈷離子的含量。＜Cobalt ion content＞ The Agilent 8800 Triple Quadrupole ICP-MS (for semiconductor analysis, option #200) was used for the measurement. Based on the measurement results, the content of cobalt ions was determined.

・測量條件 樣品導入系統使用了石英火炬與同軸型PFA（全氟烷氧基烷烴）霧化器（自吸用）及鉑錐介面。冷電漿條件的測量動作參數如下所述。 ・RF（Radio Frequency）輸出（W）：600 ・載氣流量（L/min）：0.7 ・尾吹氣流量（L/min）：1 ・取樣深度（mm）：18・Measurement conditions The sample introduction system uses a quartz torch and a coaxial PFA (perfluoroalkoxy alkane) atomizer (for self-priming) and a platinum cone interface. The measurement operation parameters of the cold plasma conditions are as follows. ・RF (Radio Frequency) output (W): 600 ・Carrier gas flow rate (L/min): 0.7 ・Makeup gas flow rate (L/min): 1 ・Sampling depth (mm): 18

〔評價〕 ＜耐腐蝕性＞ （相對於Co膜之耐腐蝕性評價） 準備由Co構成之膜（配線模型，以下亦稱為“Co膜”。），依據其蝕刻速度，評價了處理液的耐腐蝕性。Co膜的膜厚係1000Å。蝕刻速度較低之情況下，耐腐蝕性優異，蝕刻速度較高之情況下，耐腐蝕性較差。 使用實施例及比較例的各處理液，進行了Co膜的蝕刻處理。具體而言，實施例及比較例的處理液中，將Co膜浸漬10分鐘，依據處理液的浸漬前後的Co膜的膜厚差，計算出了蝕刻速度（Å/分鐘）。 另外，關於處理前後的Co膜的膜厚，使用橢圓偏光法（分光橢圓偏振計、產品名“Vase”、J.A. Woollam Japan Co.,Inc.製）在測量範圍250～1000nm、測量見方度70度及75度的條件下進行了測量。 又，準備由SiO2 構成之膜，以與上述相同的方式計算出蝕刻速度。 另外，結果依據以下基準對每個膜的種類進行評價，在表1中總括表示測量結果及評價。[Evaluation] <Corrosion resistance> (Evaluation of corrosion resistance relative to Co film) A film made of Co (wiring model, also referred to as "Co film" hereinafter) was prepared, and the etching rate was used to evaluate the performance of the treatment solution. Corrosion resistance. The thickness of the Co film is 1000Å. When the etching rate is low, the corrosion resistance is excellent, and when the etching rate is high, the corrosion resistance is poor. The etching treatment of the Co film was performed using each treatment liquid of the example and the comparative example. Specifically, in the treatment solutions of the Examples and Comparative Examples, the Co film was immersed for 10 minutes, and the etching rate (Å/min) was calculated based on the difference in the thickness of the Co film before and after the immersion of the treatment solution. In addition, regarding the thickness of the Co film before and after the treatment, the ellipsometric method (spectroscopic ellipsometer, product name "Vase", manufactured by JA Woollam Japan Co., Inc.) was used in a measurement range of 250 to 1000 nm and a measurement squareness of 70 degrees. And the measurement was carried out under the condition of 75 degrees. In addition, a film made of SiO 2 was prepared, and the etching rate was calculated in the same manner as described above. In addition, the results were evaluated for each type of film based on the following criteria, and Table 1 collectively shows the measurement results and evaluations.

（評價基準） “S”：0.5Å/分鐘以下（耐腐蝕性尤其優異） “A”：超過0.5Å/分鐘且1.0Å/分鐘以下（耐腐蝕性優異） “B”：超過1.0Å/分鐘且2.0Å/分鐘以下（實用上能夠使用的水準） “C”：超過2.0Å/分鐘且3.0Å/分鐘以下（耐腐蝕性存在問題並無法使用之水準） “D”：超過3.0Å/分鐘（對象層溶解並無法使用之水準）(Evaluation criteria) "S": 0.5Å/min or less (especially excellent in corrosion resistance) "A": More than 0.5Å/min and 1.0Å/min or less (excellent corrosion resistance) "B": More than 1.0Å/min and 2.0Å/min or less (a practically usable level) "C": More than 2.0 Å/min and less than 3.0 Å/min (a level at which there is a problem with corrosion resistance and cannot be used) "D": more than 3.0Å/min (a level at which the target layer dissolves and cannot be used)

＜殘渣去除性＞ 形成了在基板（Si）上依序具備Co膜、SiN膜、SiO2 膜及具有特定開口部之金屬硬遮罩（TiN）之積層體（相當於處理前積層體）。使用所獲得之積層體，將金屬硬遮罩作為遮罩實施電漿蝕刻，進行SiN膜及SiO2 膜的蝕刻直至露出Co膜表面，形成孔而製造了試樣1（參閱圖1）。當藉由掃描型電子顯微鏡照片（SEM：Scanning Electron Microscope）確認該積層體的截面時，在孔壁面觀察到了電漿蝕刻殘渣。 並且，以如下述順序評價了殘渣去除性。首先，將已準備之上述試樣1的切片（約2.0cm×2.0cm）浸漬於調節成60℃溫度之各處理液。自開始浸漬至經過了5分鐘之後取出試樣1的切片，立即用超純水進行水洗並且進行了N2 乾燥。之後，藉由SEM觀察經浸漬之試樣1的切片的表面，確認了有無電漿蝕刻殘渣。同樣地，分別對進行了8分鐘及10分鐘的浸漬之試樣1的切片用超純水進行水洗及N2 乾燥之後，藉由SEM觀察各切片的表面，確認有無電漿蝕刻殘渣。 從各試樣1的切片的觀察結果，依據下述判斷基準，評價了電漿蝕刻殘渣的去除性（“殘渣去除性”）。 “S”：藉由5分鐘的浸漬，完全去除了電漿蝕刻殘渣。 “A”：以5分鐘的浸漬未完全去除電漿蝕刻殘渣，藉由8分鐘的浸漬完全去除了電漿蝕刻殘渣。 “B”：以8分鐘的浸漬未完全去除電漿蝕刻殘渣，藉由10分鐘的浸漬完全去除了電漿蝕刻殘渣。 “C”：即使以10分鐘的浸漬亦未完全去除電漿蝕刻殘渣，但是功能沒有問題。 “D”：即使以10分鐘的浸漬亦未完全去除電漿蝕刻殘渣，導致功能受到影響。<Removability of residue> A laminated body (equivalent to a pre-processed laminated body) having a Co film, a SiN film, an SiO 2 film, and a metal hard mask (TiN) with specific openings in this order is formed on the substrate (Si). Using the obtained laminate, plasma etching was performed using a metal hard mask as a mask, and the SiN film and the SiO 2 film were etched until the surface of the Co film was exposed, and a hole was formed to manufacture sample 1 (see FIG. 1). When the cross-section of the laminate was confirmed with a scanning electron microscope photograph (SEM: Scanning Electron Microscope), plasma etching residue was observed on the hole wall surface. In addition, the residue removability was evaluated in the following procedures. First, the prepared slice (approximately 2.0 cm × 2.0 cm) of the above-mentioned sample 1 was immersed in each treatment liquid adjusted to a temperature of 60°C. After 5 minutes from the start of the immersion, the section of sample 1 was taken out, washed with ultrapure water immediately, and dried with N 2. After that, the surface of the slice of the impregnated sample 1 was observed by SEM to confirm the presence or absence of plasma etching residue. Similarly, after the sections of Sample 1 immersed for 8 minutes and 10 minutes were washed with ultrapure water and dried with N 2 , the surface of each section was observed by SEM to confirm the presence or absence of plasma etching residues. From the observation results of the sections of each sample 1, the removability of plasma etching residues (“residue removability”) was evaluated based on the following judgment criteria. "S": After 5 minutes of immersion, the plasma etching residue was completely removed. "A": The plasma etching residue was not completely removed by the immersion for 5 minutes, and the plasma etching residue was completely removed by the immersion for 8 minutes. "B": The plasma etching residue was not completely removed by the immersion for 8 minutes, and the plasma etching residue was completely removed by the immersion for 10 minutes. "C": The plasma etching residue was not completely removed even by immersion for 10 minutes, but there was no problem in the function. "D": Even with 10 minutes of immersion, the plasma etching residue was not completely removed, which affected the function.

＜缺陷抑制性＞ 藉由晶圓表面檢查裝置（SP-5、KLA-Tencor Corporation Corporation製），測量了存在於直徑300mm的矽基板表面之直徑32nm以上的異物數及各異物的地址。 然後，在旋轉晶圓處理裝置（Ekc Technologies,Inc.製）上設置了測量出存在於矽基板表面之異物數之晶圓。 接著，在設置之晶圓的表面以1.5L/min的流量吐出了1分鐘的實施例及比較例的各處理液。之後，進行了晶圓的旋轉乾燥。 針對所獲得之乾燥後的晶圓，使用晶圓表面檢查裝置測量了晶圓上的異物數及地址。 按照以下的評價基準評價了所獲得之粒子的數。將結果示於表1中。 “S”：直徑32nm以上的粒子的數係0個以上且小於100個。 “A”：直徑32nm以上的粒子的數係100個以上且小於500個。 “B”：直徑32nm以上的粒子的數係500個以上且小於1000個。 “C”：直徑32nm以上的粒子的數係1000個以上。<Defect Inhibition> Using a wafer surface inspection device (SP-5, manufactured by KLA-Tencor Corporation), the number of foreign objects with a diameter of 32 nm or more on the surface of a silicon substrate with a diameter of 300 mm and the address of each foreign object were measured. Then, a rotating wafer processing device (manufactured by Ekc Technologies, Inc.) was set up to measure the number of foreign objects present on the surface of the silicon substrate. Next, the respective processing liquids of the Examples and Comparative Examples were discharged at a flow rate of 1.5 L/min for 1 minute on the surface of the installed wafer. After that, the wafer was spin-dried. For the obtained dried wafer, a wafer surface inspection device was used to measure the number and address of foreign matter on the wafer. The number of particles obtained was evaluated according to the following evaluation criteria. The results are shown in Table 1. "S": The number of particles with a diameter of 32 nm or more is 0 or more and less than 100. "A": The number of particles with a diameter of 32 nm or more is 100 or more and less than 500. "B": The number of particles with a diameter of 32 nm or more is 500 or more and less than 1,000. "C": The number of particles with a diameter of 32 nm or more is 1000 or more.

以下，在表1中示出了各實施例及各比較例中所使用之處理液的組成及各評價結果。 表1中，“量（%）”欄表示所對應之化合物的含量（單位：質量%），“量（ppt）”欄表示所對應之化合物的含量（單位：質量ppt）。 表1中，“比例1”欄表示以組合1～6成對且處理液中所包含之有機溶劑A及B中有機溶劑A的含量與有機溶劑B的含量之比例（質量比）。 表1中，“比例2”欄表示相對於有機溶劑A的總質量之鈷離子的含量（質量ppm）。 表1中，“Co離子”係指鈷離子，“HA化合物”係指羥胺化合物。 另外，下述表中，例如“5.0E+02”等標記係指5.0×10的2次方。Below, Table 1 shows the composition of the treatment liquid used in each example and each comparative example and each evaluation result. In Table 1, the "quantity (%)" column represents the content of the corresponding compound (unit: mass %), and the "quantity (ppt)" column represents the content of the corresponding compound (unit: mass ppt). In Table 1, the “ratio 1” column indicates the ratio (mass ratio) of the content of the organic solvent A and the content of the organic solvent B in the organic solvents A and B contained in the treatment liquid in a combination of 1 to 6. In Table 1, the “ratio 2” column indicates the content of cobalt ion (mass ppm) relative to the total mass of the organic solvent A. In Table 1, "Co ion" refers to cobalt ion, and "HA compound" refers to hydroxylamine compound. In addition, in the following table, symbols such as "5.0E+02" refer to 5.0×10 to the second power.

[表1] 表1 處理液的組成 水 有機溶劑A 有機溶劑B 組合 比例1 化合物 量（%） 化合物 量（%） 化合物 量（%） 化合物 量（%） 實施例1 94.8% EGBE 5.0%     b-1 0.01%     1 5.0E+02 實施例2 94.8% EGBE 5.0%     b-2 0.01%     1 5.0E+02 實施例3 94.8% EGBE 5.0%     b-3 0.01%     1 5.0E+02 實施例4 94.8% EGBE 5.0%     b-4 0.01%     1 5.0E+02 實施例5 94.8% EGBE 5.0%     b-5 0.01%     1 5.0E+02 實施例6 94.8% EGBE 5.0%     b-6 0.01%     1 5.0E+02 實施例7 93.8% EGBE 5.0%     b-5 0.01%     1 5.0E+02 實施例8 88.6% EGBE 5.0%     b-5 0.01%     1 5.0E+02 實施例9 88.6% EGBE 5.0%     b-5 0.01%     1 5.0E+02 實施例10 88.4% EGBE 5.0%     b-5 0.01%     1 5.0E+02 實施例11 88.4% EGBE 5.0%     b-5 0.001%     1 5.0E+03 實施例12 88.4% EGBE 5.0%     b-5 0.001% b-3 0.001% 1 5.0E+03 實施例13 88.4% EGBE 5.0%     b-5 0.001% b-8 0.001% 1 5.0E+03 實施例14 88.4% EGBE 5.0%     b-5 0.001%     1 5.0E+03 實施例15 88.4% EGBE 5.0%     b-5 0.001%     1 5.0E+03 實施例16 88.4% EGBE 5.0%     b-7 0.01%     1 5.0E+02 實施例17 88.4% EGBE 5.0%     b-8 0.01%     1 5.0E+02 實施例18 86.4% DEGBE 7.0%     b-7 0.01%     2 7.0E+02 實施例19 24.9% DEGBE 60.0% DMSO 15.0% b-9 0.10%     3 7.5E+02 實施例20 24.7% DEGBE 60.0% DMSO 15.0% b-9 0.10%     3 7.5E+02 實施例21 24.8% DEGBE 60.0% DMSO 15.0% b-9 0.01%     3 7.5E+03 實施例22 47.6% 環丁碸 50.0%     b-10 0.03%     4 1.67E+03 實施例23 47.6% 環丁碸 50.0%     b-11 0.05%     4 1.0E+03 實施例24 22.5% PG 50.0% 環丁碸 25.0% b-6 0.05%     5 1.5E+03 實施例25 22.5% PG 50.0% 環丁碸 25.0% b-10 0.05%     3 1.5E+03 實施例26 29.5% HG 65.0%     b-12 0.05%     6 1.3E+03 實施例27 29.5% HG 65.0%     b-13 0.05%     6 1.3E+03 實施例28 52.5% PG 20.0% DMSO 25.0% b-6 0.01%     5 4.5E+03 實施例29 94.3% EGBE 5.0%     b-5 0.01%     1 5.0E+02 實施例30 92.3% DEGBE 7.0%     b-5 0.01%     2 7.0E+02 實施例31 92.8% EGBE 5.0%     b-1 2.00%     1 2.5E+00 比較例1 94.8% EGBE 5.0%     -       - - 比較例2 24.8% DEGBE 60.0% DMSO 15.0% -       - - 比較例3 22.5% PG 50.0% 環丁碸 25.0% -       - - 比較例4 29.5% HG 65.0%     -       - - 比較例5 47.6% 環丁碸 50.0%     -       - - 比較例6 24.6% EGME 75.0%     -       - - 比較例7 94.0% EGBE 5.0%     b-1 0.01%     1 5.0E+02 [Table 1] Table 1 Composition of treatment liquid water Organic solvent A Organic solvent B combination Scale 1 Compound the amount(%) Compound the amount(%) Compound the amount(%) Compound the amount(%) Example 1 94.8% EGBE 5.0% b-1 0.01% 1 5.0E+02 Example 2 94.8% EGBE 5.0% b-2 0.01% 1 5.0E+02 Example 3 94.8% EGBE 5.0% b-3 0.01% 1 5.0E+02 Example 4 94.8% EGBE 5.0% b-4 0.01% 1 5.0E+02 Example 5 94.8% EGBE 5.0% b-5 0.01% 1 5.0E+02 Example 6 94.8% EGBE 5.0% b-6 0.01% 1 5.0E+02 Example 7 93.8% EGBE 5.0% b-5 0.01% 1 5.0E+02 Example 8 88.6% EGBE 5.0% b-5 0.01% 1 5.0E+02 Example 9 88.6% EGBE 5.0% b-5 0.01% 1 5.0E+02 Example 10 88.4% EGBE 5.0% b-5 0.01% 1 5.0E+02 Example 11 88.4% EGBE 5.0% b-5 0.001% 1 5.0E+03 Example 12 88.4% EGBE 5.0% b-5 0.001% b-3 0.001% 1 5.0E+03 Example 13 88.4% EGBE 5.0% b-5 0.001% b-8 0.001% 1 5.0E+03 Example 14 88.4% EGBE 5.0% b-5 0.001% 1 5.0E+03 Example 15 88.4% EGBE 5.0% b-5 0.001% 1 5.0E+03 Example 16 88.4% EGBE 5.0% b-7 0.01% 1 5.0E+02 Example 17 88.4% EGBE 5.0% b-8 0.01% 1 5.0E+02 Example 18 86.4% DEGBE 7.0% b-7 0.01% 2 7.0E+02 Example 19 24.9% DEGBE 60.0% DMSO 15.0% b-9 0.10% 3 7.5E+02 Example 20 24.7% DEGBE 60.0% DMSO 15.0% b-9 0.10% 3 7.5E+02 Example 21 24.8% DEGBE 60.0% DMSO 15.0% b-9 0.01% 3 7.5E+03 Example 22 47.6% Ring Dingzhu 50.0% b-10 0.03% 4 1.67E+03 Example 23 47.6% Ring Dingzhu 50.0% b-11 0.05% 4 1.0E+03 Example 24 22.5% PG 50.0% Ring Dingzhu 25.0% b-6 0.05% 5 1.5E+03 Example 25 22.5% PG 50.0% Ring Dingzhu 25.0% b-10 0.05% 3 1.5E+03 Example 26 29.5% HG 65.0% b-12 0.05% 6 1.3E+03 Example 27 29.5% HG 65.0% b-13 0.05% 6 1.3E+03 Example 28 52.5% PG 20.0% DMSO 25.0% b-6 0.01% 5 4.5E+03 Example 29 94.3% EGBE 5.0% b-5 0.01% 1 5.0E+02 Example 30 92.3% DEGBE 7.0% b-5 0.01% 2 7.0E+02 Example 31 92.8% EGBE 5.0% b-1 2.00% 1 2.5E+00 Comparative example 1 94.8% EGBE 5.0% - - - Comparative example 2 24.8% DEGBE 60.0% DMSO 15.0% - - - Comparative example 3 22.5% PG 50.0% Ring Dingzhu 25.0% - - - Comparative example 4 29.5% HG 65.0% - - - Comparative example 5 47.6% Ring Dingzhu 50.0% - - - Comparative example 6 24.6% EGME 75.0% - - - Comparative example 7 94.0% EGBE 5.0% b-1 0.01% 1 5.0E+02

[表2] 表1（續） 處理液的組成 去除劑 鹼性化合物 Co離子 比例2 防腐蝕劑 化合物 量 （%） 化合物 量 （%） 化合物 量 （%） Co離子源 量 （ppt） 化合物 量（%） 實施例1 DTPA 0.08%     DBU 0.10%           實施例2 DTPA 0.08%     DBU 0.10%           實施例3 DTPA 0.08%     DBU 0.10%           實施例4 DTPA 0.08%     DBU 0.10%           實施例5 DTPA 0.08%     DBU 0.10%           實施例6 DTPA 0.08%     DBU 0.10%           實施例7 DTPA 0.08% HA 1.00% DBU 0.10%           實施例8 DTPA 0.60% HA 5.00% DBU 0.76%           實施例9 DTPA 0.60% HA 5.00% DBU 0.76% Co（OH）2 10.0 1.0E+09     實施例10 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例11 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例12 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例13 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例14 DTPA 0.60% HA 5.00% DBU 0.76%       IRGAMET 42 0.20% 實施例15 DTPA 0.60% HA 5.00% DBU 0.76% Co（OH）2 10.0 1.0E+08 IRGAMET 42 0.20% 實施例16 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例17 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例18 DTPA 0.60% HA 5.00% DBU 0.76%       5MBTA 0.20% 實施例19                       實施例20                   BTA 0.20% 實施例21                   BTA 0.20% 實施例22 Cy-DTA 0.70%     TMAH 1.70%           實施例23 Cy-DTA 0.70%     TMAH 1.70%           實施例24         TMAH 2.50%           實施例25         TMAH 2.50%           實施例26     HA 5.00% AEEA 0.50%           實施例27     HA 5.00% AEEA 0.50%           實施例28         TMAH 2.00%       IRGAMET 42 0.50% 實施例29 HF 0.05%     NH4 OH 0.10%       TTA 0.50% 實施例30 HF 0.05%     NH4 OH 0.10%       TTA 0.50% 實施例31 DTPA 0.08%     DBU 0.10%           比較例1 DTPA 0.08%     DBU 0.10%           比較例2                   BTA 0.20% 比較例3         TMAH 2.50%           比較例4     HA 5.00% AEEA 0.50%           比較例5 Cy-DTA 0.70%     TMAH 1.70%           比較例6 HF 0.10%     NH4 OH 0.30%           比較例7 DTPA 1.00%                   [Table 2] Table 1 (continued) Composition of treatment liquid Remover Basic compound Co ion Scale 2 Anti-corrosion agent Compound the amount(%) Compound the amount(%) Compound the amount(%) Co ion source Quantity (ppt) Compound the amount(%) Example 1 DTPA 0.08% DBU 0.10% Example 2 DTPA 0.08% DBU 0.10% Example 3 DTPA 0.08% DBU 0.10% Example 4 DTPA 0.08% DBU 0.10% Example 5 DTPA 0.08% DBU 0.10% Example 6 DTPA 0.08% DBU 0.10% Example 7 DTPA 0.08% HA 1.00% DBU 0.10% Example 8 DTPA 0.60% HA 5.00% DBU 0.76% Example 9 DTPA 0.60% HA 5.00% DBU 0.76% Co(OH) 2 10.0 1.0E+09 Example 10 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 11 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 12 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 13 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 14 DTPA 0.60% HA 5.00% DBU 0.76% IRGAMET 42 0.20% Example 15 DTPA 0.60% HA 5.00% DBU 0.76% Co(OH) 2 10.0 1.0E+08 IRGAMET 42 0.20% Example 16 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 17 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 18 DTPA 0.60% HA 5.00% DBU 0.76% 5MBTA 0.20% Example 19 Example 20 BTA 0.20% Example 21 BTA 0.20% Example 22 Cy-DTA 0.70% TMAH 1.70% Example 23 Cy-DTA 0.70% TMAH 1.70% Example 24 TMAH 2.50% Example 25 TMAH 2.50% Example 26 HA 5.00% AEEA 0.50% Example 27 HA 5.00% AEEA 0.50% Example 28 TMAH 2.00% IRGAMET 42 0.50% Example 29 HF 0.05% NH 4 OH 0.10% TTA 0.50% Example 30 HF 0.05% NH 4 OH 0.10% TTA 0.50% Example 31 DTPA 0.08% DBU 0.10% Comparative example 1 DTPA 0.08% DBU 0.10% Comparative example 2 BTA 0.20% Comparative example 3 TMAH 2.50% Comparative example 4 HA 5.00% AEEA 0.50% Comparative example 5 Cy-DTA 0.70% TMAH 1.70% Comparative example 6 HF 0.10% NH 4 OH 0.30% Comparative example 7 DTPA 1.00%

[表3] 表1（續） 處理液的pH 耐腐蝕性 殘渣去除性 缺陷抑制性 Co SiO2 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 實施例1 5.2 1.5 B 1.2 B B B 實施例2 5.1 1.2 B 1.2 B B B 實施例3 5.3 1.3 B 1.1 B B B 實施例4 5.3 1.1 B 1.4 B B B 實施例5 5.2 1.4 B 1.3 B B B 實施例6 5.4 1.6 B 1.5 B B B 實施例7 5.1 0.6 A 0.7 A A B 實施例8 8.2 0.8 A 0.8 A A A 實施例9 8.5 0.5 A 0.6 A A S 實施例10 8.6 0.2 S 0.2 S S S 實施例11 8.5 0.3 S 0.1 S S S 實施例12 8.5 0.1 S 0.1 S S S 實施例13 8.5 0.2 S 0.1 S S S 實施例14 8.6 0.6 A 0.9 A S S 實施例15 8.5 0.1 S 0.1 S S S 實施例16 8.5 0.3 S 0.8 A A S 實施例17 8.6 0.2 S 0.9 A A A 實施例18 8.5 0.3 S 0.7 A A A 實施例19 6.4 1.2 B 1.5 B B A 實施例20 5.5 0.6 A 0.5 A B B 實施例21 5.4 0.6 A 0.7 A A A 實施例22 11.4 0.6 A 1.4 B B B 實施例23 11.6 1.2 B 0.8 A B B 實施例24 13.8 1.1 B 1.8 B B B 實施例25 14.1 1.3 B 1.7 B B B 實施例26 10.4 0.6 A 1.3 B A B 實施例27 10.7 0.8 A 1.4 B B B 實施例28 14.0 1.1 B 1.9 B B B 實施例29 5.2 1.9 B 1.1 B B B 實施例30 5.6 1.8 B 1.2 B B B 實施例31 7.9 1.3 B 1.3 B B B 比較例1 5.3 11.3 D 1.4 B C C 比較例2 5.1 2.1 C 2.4 C C C 比較例3 14.0 2.8 C 2.9 C C C 比較例4 10.6 2.3 C 2.5 C C C 比較例5 13.7 4.5 D 2.2 C C C 比較例6 5.1 21.4 D 34.1 D C C 比較例7 3.0 13.4 D 2.5 C C C [table 3] Table 1 (continued) PH of the treatment solution Corrosion resistance Residue removal Defect inhibition Co SiO 2 Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Example 1 5.2 1.5 B 1.2 B B B Example 2 5.1 1.2 B 1.2 B B B Example 3 5.3 1.3 B 1.1 B B B Example 4 5.3 1.1 B 1.4 B B B Example 5 5.2 1.4 B 1.3 B B B Example 6 5.4 1.6 B 1.5 B B B Example 7 5.1 0.6 A 0.7 A A B Example 8 8.2 0.8 A 0.8 A A A Example 9 8.5 0.5 A 0.6 A A S Example 10 8.6 0.2 S 0.2 S S S Example 11 8.5 0.3 S 0.1 S S S Example 12 8.5 0.1 S 0.1 S S S Example 13 8.5 0.2 S 0.1 S S S Example 14 8.6 0.6 A 0.9 A S S Example 15 8.5 0.1 S 0.1 S S S Example 16 8.5 0.3 S 0.8 A A S Example 17 8.6 0.2 S 0.9 A A A Example 18 8.5 0.3 S 0.7 A A A Example 19 6.4 1.2 B 1.5 B B A Example 20 5.5 0.6 A 0.5 A B B Example 21 5.4 0.6 A 0.7 A A A Example 22 11.4 0.6 A 1.4 B B B Example 23 11.6 1.2 B 0.8 A B B Example 24 13.8 1.1 B 1.8 B B B Example 25 14.1 1.3 B 1.7 B B B Example 26 10.4 0.6 A 1.3 B A B Example 27 10.7 0.8 A 1.4 B B B Example 28 14.0 1.1 B 1.9 B B B Example 29 5.2 1.9 B 1.1 B B B Example 30 5.6 1.8 B 1.2 B B B Example 31 7.9 1.3 B 1.3 B B B Comparative example 1 5.3 11.3 D 1.4 B C C Comparative example 2 5.1 2.1 C 2.4 C C C Comparative example 3 14.0 2.8 C 2.9 C C C Comparative example 4 10.6 2.3 C 2.5 C C C Comparative example 5 13.7 4.5 D 2.2 C C C Comparative example 6 5.1 21.4 D 34.1 D C C Comparative example 7 3.0 13.4 D 2.5 C C C

從表1的結果確認到，本發明的處理液具有相對於Co膜及SiO2 膜之優異之耐腐蝕性，並且殘渣去除性及缺陷抑制性優異。From the results of Table 1, it was confirmed that the treatment solution of the present invention has excellent corrosion resistance with respect to the Co film and the SiO 2 film, and also has excellent residue removal properties and defect suppression properties.

確認到處理液包含組合1之情況下，若處理液作為特定有機溶劑B而包含1-二級丁氧基丁烷、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、3,6,9,12-四氧十六烷-1-醇、甘油、十八醇或二（2-丁氧基）甲烷，則缺陷抑制性更優異（實施例1～6、16及17的比較），確認到若包含1-二級丁氧基丁烷、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、3,6,9,12-四氧十六烷-1-醇、甘油或二（2-丁氧基）甲烷，則相對於SiO2 膜之耐腐蝕性及殘渣去除性更優異（實施例1～6、16及17的比較）。When it is confirmed that the treatment liquid contains combination 1, if the treatment liquid contains 1-secondary butoxybutane and 1-((2-butoxyethoxy)methoxy)butane as the specific organic solvent B , 1-(2-(ethoxymethoxy)ethoxy)butane, 3,6,9,12-tetraoxhexadecane-1-ol, glycerol, stearyl alcohol or bis(2-butane Oxy)methane has more excellent defect suppression (comparison of Examples 1 to 6, 16 and 17). It was confirmed that if 1-secondary butoxybutane, 1-((2-butoxyethoxy Group) methoxy) butane, 1-(2-(ethoxymethoxy) ethoxy) butane, 3,6,9,12-tetraoxetane-1-ol, glycerol or two (2-Butoxy)methane is more excellent in corrosion resistance and residue removal properties with respect to the SiO 2 film (comparison of Examples 1 to 6, 16 and 17).

確認到處理液包含組合4之情況下，處理液作為特定有機溶劑B而包含3-環丁烯碸，則相對於Co膜之耐腐蝕性更優異，若作為特定有機溶劑B而包含DMSO，則相對於SiO2 膜之耐腐蝕性更優異（實施例22及23的比較）。When it is confirmed that the treatment liquid contains the combination 4, the treatment liquid contains 3-cyclobutene as the specific organic solvent B, and the corrosion resistance to the Co film is more excellent. If DMSO is included as the specific organic solvent B, It is more excellent in corrosion resistance than the SiO 2 film (comparison of Examples 22 and 23).

確認到處理液包含組合6之情況下，處理液作為特定有機溶劑B而包含丙酮，則殘渣去除性優異（實施例26及27的比較）。When it was confirmed that the treatment liquid contained the combination 6, and the treatment liquid contained acetone as the specific organic solvent B, the residue removability was excellent (comparison of Examples 26 and 27).

確認到處理液包含鈷離子之情況下，相對於Co膜及SiO2 膜之耐腐蝕性以及缺陷抑制性更優異（實施例8及9的比較、實施例14及15的比較）。It was confirmed that when the treatment liquid contained cobalt ions, the corrosion resistance and defect suppression properties with respect to the Co film and the SiO 2 film were more excellent (comparison of Examples 8 and 9, and comparison of Examples 14 and 15).

確認到處理液包含羥胺化合物之情況下，相對於Co膜及SiO2 膜之耐腐蝕性及殘渣去除性更優異（實施例5及7的比較）。 又，確認到羥胺化合物的含量相對於處理液的總質量係2.0質量%以上之情況下，缺陷抑制性更優異（實施例7及8的比較）。It was confirmed that when the treatment liquid contained a hydroxylamine compound, the corrosion resistance and the residue removal property with respect to the Co film and the SiO 2 film were more excellent (comparison of Examples 5 and 7). In addition, it was confirmed that when the content of the hydroxylamine compound is 2.0% by mass or more with respect to the total mass of the treatment liquid, the defect suppression properties are more excellent (comparison of Examples 7 and 8).

確認到處理液包含防腐蝕劑之情況下，相對於Co膜及SiO2 膜之耐腐蝕性更優異（實施例8、10及14的比較、實施例19及20的比較），確認到處理液作為防腐蝕劑而包含5-甲基-1H-苯并三唑（5MBTA）之情況下，相對於Co膜及SiO2 膜之耐腐蝕性更優異（實施例10及14的比較）。 又，確認到處理液包含組合1之情況下，若處理液包含防腐蝕劑，則殘渣去除性更優異（實施例8、10及14的比較）。When it was confirmed that the treatment liquid contained an anti-corrosion agent, the corrosion resistance to the Co film and the SiO 2 film was superior (comparison of Examples 8, 10 and 14, and comparison of Examples 19 and 20), and it was confirmed that the treatment liquid was When the corrosion inhibitor contains 5-methyl-1H-benzotriazole (5MBTA), the corrosion resistance is more excellent than that of the Co film and the SiO 2 film (comparison of Examples 10 and 14). In addition, it was confirmed that when the treatment liquid contained the combination 1, if the treatment liquid contained the anticorrosive agent, the residue removability was more excellent (comparison of Examples 8, 10, and 14).

又，準備由Cu構成之膜，按照上述之相對於Co膜之耐腐蝕性評價，評價了相對於由Cu構成之膜之實施例及比較例的各處理液的耐腐蝕性。其結果，獲得了與相對於Co膜之耐腐蝕性大致相等的評價結果。Furthermore, a film made of Cu was prepared, and the corrosion resistance of each treatment solution in the examples and comparative examples of the film made of Cu was evaluated in accordance with the above-mentioned corrosion resistance evaluation with respect to the Co film. As a result, an evaluation result approximately equal to the corrosion resistance with respect to the Co film was obtained.

實施例7中，將DTPA變更為以質量比計7:3包含DTPA及Cy-DTA之混合液，除此以外，按照實施例7製備處理液，進行了評價之結果，獲得了與實施例7同樣的效果。In Example 7, the DTPA was changed to a mixed liquid containing DTPA and Cy-DTA in a mass ratio of 7:3. Otherwise, the treatment liquid was prepared in accordance with Example 7, and the result of evaluation was obtained. The same effect.

實施例7中，將HA變更為羥胺硫酸鹽，除此以外，按照實施例7製備處理液，進行了評價之結果，獲得了與實施例7同樣的效果。In Example 7, except that HA was changed to hydroxylamine sulfate, a treatment solution was prepared in accordance with Example 7 and evaluated. As a result, the same effect as in Example 7 was obtained.

[實施例101～109：沖洗液評價] 按照上述（相對於Co膜之耐腐蝕性評價）中所記載之方法，使用實施例13的處理液，進行了Co膜的蝕刻處理。將經蝕刻處理之Co膜浸漬於具有表2所示之組成之各沖洗液中0.5分鐘，藉此進行了Co膜的沖洗處理。 藉由以下的方法，評價了Co膜的沖洗處理中的Co膜表面的處理液剩餘及沖洗液的耐腐蝕性。[Examples 101 to 109: Evaluation of Rinsing Solution] According to the method described in the above (Evaluation of Corrosion Resistance with respect to Co Film), the etching treatment of the Co film was performed using the treatment solution of Example 13. The etched Co film was immersed in each rinsing solution having the composition shown in Table 2 for 0.5 minutes, thereby performing the rinsing treatment of the Co film. The following method evaluated the remaining treatment liquid on the surface of the Co film and the corrosion resistance of the rinse liquid during the rinsing treatment of the Co film.

〔處理液剩餘〕 藉由X射線光電子分光分析對經沖洗處理之Co膜的表面進行分析，測量了上述Co膜的表面上的相對於所有原子數之來自於實施例13的處理液之氮原子的數。從測量結果，依據下述基準，評價了使用各沖洗液之沖洗處理的處理液剩餘。 以下示出了X射線光電子分光分析的測量條件及處理液剩餘的評價基準。〔Remaining treatment liquid〕 The surface of the rinse-treated Co film was analyzed by X-ray photoelectron spectroscopy, and the number of nitrogen atoms from the treatment liquid of Example 13 on the surface of the Co film was measured relative to the total number of atoms. From the measurement results, the remaining treatment liquid of the rinsing treatment using each rinsing liquid was evaluated based on the following criteria. The measurement conditions of X-ray photoelectron spectroscopy and the evaluation criteria for the remaining processing liquid are shown below.

（測量條件） ・裝置：ULVAC-PHI, INCORPORATED.製Quantera SXMTM ・X射線源：單色化Al Kα射線 ・X射線光束直徑：φ200μm ・訊號的擷取角度：45°(Measurement conditions) ・Device: Quantera SXMTM manufactured by ULVAC-PHI, INCORPORATED. ・X-ray source: monochromatic Al Kα rays ・X-ray beam diameter: φ200μm ・Signal acquisition angle: 45°

（評價基準） “S”：氮原子的數係檢測極限以下（相對於所有原子數係檢測極限以下），處理液完全從Co膜的表面去除。 “A”：氮原子的數超過檢測極限，相對於所有原子數係1atom%以下。 “B”：氮原子的數相對於所有原子數超過1atom%且2atom%以下。 “C”：氮原子的數相對於所有原子數超過2atom%。(Evaluation criteria) "S": The number system of nitrogen atoms is below the detection limit (relative to all atomic number systems below the detection limit), and the treatment solution is completely removed from the surface of the Co film. "A": The number of nitrogen atoms exceeds the detection limit and is 1 atom% or less relative to all atomic numbers. "B": The number of nitrogen atoms is more than 1 atom% and 2 atom% or less with respect to the total number of atoms. "C": The number of nitrogen atoms exceeds 2 atom% relative to the number of all atoms.

〔耐腐蝕性〕 依據上述之處理液的耐腐蝕性評價，評價了沖洗液的耐腐蝕性。具體而言，依據沖洗處理前後的Co膜的膜厚差，計算出蝕刻速度（Å/分鐘），從所計算出之蝕刻速度，依據下述基準，評價了各沖洗液的耐腐蝕性。〔Corrosion resistance〕 Based on the above-mentioned corrosion resistance evaluation of the treatment liquid, the corrosion resistance of the rinse liquid was evaluated. Specifically, the etching rate (Å/min) was calculated based on the difference in the thickness of the Co film before and after the rinsing treatment, and from the calculated etching rate, the corrosion resistance of each rinsing solution was evaluated based on the following criteria.

（評價基準） “A”：1.0Å/分鐘以下 “B”：超過1.0Å/分鐘且3.0Å/分鐘以下 “C”：超過3.0Å/分鐘且10.0Å/分鐘以下 “D”：超過10.0Å/分鐘(Evaluation criteria) "A": 1.0Å/min or less "B": More than 1.0Å/min and 3.0Å/min or less "C": more than 3.0Å/min and 10.0Å/min or less "D": more than 10.0Å/min

又，準備由SiO2 構成之膜，以與上述Co膜相同的方式評價了處理液剩餘及耐腐蝕性。In addition, a film made of SiO 2 was prepared, and the remaining treatment solution and corrosion resistance were evaluated in the same manner as the Co film described above.

表2中總括示出在各實施例中使用之沖洗液的組成以及處理液剩餘及耐腐蝕性的評價結果。 表2中，“DI水（%）”欄及“IPA（%）”欄分別表示相對於沖洗液中所包含之溶劑的總質量之脫離子水及異丙醇的含量（單位：質量%）。又，“NH4 OH（ppm）”欄表示相對於沖洗液中所包含之溶劑的總質量之氫氧化銨的含量（單位：質量ppm）。Table 2 collectively shows the composition of the rinse liquid used in each example, the remaining treatment liquid, and the evaluation results of corrosion resistance. In Table 2, the "DI water (%)" column and the "IPA (%)" column respectively indicate the content of deionized water and isopropanol relative to the total mass of the solvent contained in the rinse solution (unit: mass %) . In addition, the "NH 4 OH (ppm)" column indicates the content of ammonium hydroxide (unit: mass ppm) relative to the total mass of the solvent contained in the rinse liquid.

[表4] 表2 處理液 沖洗液 處理液剩餘 耐腐蝕性 DI水 （%） IPA （%） NH4 OH （ppm） Co SiO2 Co SiO2 實施例101 實施例13 100 0 - A A C A 實施例102 實施例13 0 100 - A B A A 實施例103 實施例13 100 0 145 A A A A 實施例104 實施例13 100 0 30 A A A A 實施例105 實施例13 100 0 3 A A B A 實施例106 實施例13 10 90 15 S A A A 實施例107 實施例13 90 10 131 S S A A 實施例108 實施例13 10 90 - A A A A 實施例109 實施例13 90 10 - A A B A [Table 4] Table 2 Treatment liquid Rinsing fluid Treatment liquid remaining Corrosion resistance DI water (%) IPA (%) NH 4 OH (ppm) Co SiO 2 Co SiO 2 Example 101 Example 13 100 0 - A A C A Example 102 Example 13 0 100 - A B A A Example 103 Example 13 100 0 145 A A A A Example 104 Example 13 100 0 30 A A A A Example 105 Example 13 100 0 3 A A B A Example 106 Example 13 10 90 15 S A A A Example 107 Example 13 90 10 131 S S A A Example 108 Example 13 10 90 - A A A A Example 109 Example 13 90 10 - A A B A

從表2的結果，確認到沖洗液作為溶劑而包含水之情況下，SiO2 膜中的處理液去除性優異（實施例102與實施例108的比較）。 確認到沖洗液作為溶劑而包含異丙醇之情況下，相對於Co膜之耐腐蝕性優異（實施例101與實施例109的比較）。 確認到沖洗液包含水與異丙醇的混合溶劑之情況下，SiO2 膜中的處理液去除性與相對於Co膜之耐腐蝕性的平衡優異（實施例101、102、108與109的比較），確認到沖洗液包含水與異丙醇的混合溶劑並且異丙醇的含量相對於溶劑的總質量係30質量%以上之情況下，相對於Co膜之耐腐蝕性更優異（實施例108與實施例109的比較）。From the results of Table 2, it was confirmed that when the rinse liquid contained water as a solvent , the removal of the treatment liquid in the SiO 2 film was excellent (comparison of Example 102 and Example 108). It was confirmed that when the rinse liquid contained isopropanol as a solvent, the corrosion resistance with respect to the Co film was excellent (comparison between Example 101 and Example 109). It was confirmed that when the rinse solution contains a mixed solvent of water and isopropanol, the removal of the treatment solution in the SiO 2 film and the corrosion resistance relative to the Co film are excellent in the balance (comparison of Examples 101, 102, 108 and 109 ), it was confirmed that the rinse solution contains a mixed solvent of water and isopropanol and the content of isopropanol is 30% by mass or more relative to the total mass of the solvent, the corrosion resistance relative to the Co film is more excellent (Example 108 Comparison with Example 109).

又，確認到沖洗液包含水溶性銨之情況下，相對於Co膜之耐腐蝕性優異（實施例101與實施例105的比較），確認到水溶性銨的含量相對於溶劑的總質量係5質量%以上之情況下，相對於Co膜之耐腐蝕性更優異（實施例104與實施例105的比較）。 確認到沖洗液包含水與異丙醇的混合溶劑之情況下，包含水溶性銨時，Co膜中的處理液去除性更優異（實施例106～109的比較），確認到相對於溶劑的總質量包含50質量ppm以上的水溶性銨時，SiO2 膜中的處理液去除性更優異（實施例107與109的比較）。In addition, it was confirmed that when the rinse solution contained water-soluble ammonium, the corrosion resistance to the Co film was excellent (comparison between Example 101 and Example 105), and it was confirmed that the content of water-soluble ammonium relative to the total mass of the solvent was 5 In the case of mass% or more, the corrosion resistance relative to the Co film is more excellent (comparison between Example 104 and Example 105). When it was confirmed that the rinsing liquid contained a mixed solvent of water and isopropanol, when it contained water-soluble ammonium, the removal of the treatment liquid in the Co film was more excellent (comparison of Examples 106 to 109). When the mass contains 50 mass ppm or more of water-soluble ammonium, the removal of the treatment liquid in the SiO 2 film is more excellent (comparison of Examples 107 and 109).

[實施例201～205：乾燥處理評價] 依據實施例102的方法，使用實施例13的處理液進行了Co膜的蝕刻處理之後，作為沖洗液使用異丙醇進行了Co膜的沖洗處理。 使用加熱板對經沖洗處理之Co膜進行藉由加熱（烘烤）之乾燥處理（實施例202～205）或不進行藉由加熱之乾燥處理（實施例201），獲得了評價用Co膜。表3中示出了各實施例的乾燥處理中的加熱溫度。 依據相對於經上述沖洗處理之Co膜之處理液剩餘及耐腐蝕性的評價方法，對所獲得之Co膜進行了沖洗處理及乾燥處理後的處理液剩餘、沖洗處理及乾燥處理前後的耐腐蝕性的評價。各評價的評價基準亦相同。[Examples 201 to 205: Evaluation of drying treatment] According to the method of Example 102, after the Co film was etched using the processing solution of Example 13, the Co film was rinsed using isopropanol as the rinse solution. Using a hot plate, the rinse-treated Co film was dried by heating (baking) (Examples 202 to 205) or without heating (Example 201) to obtain a Co film for evaluation. Table 3 shows the heating temperature in the drying treatment of each example. According to the evaluation method of the remaining treatment liquid and the corrosion resistance of the Co film after the above-mentioned rinsing treatment, the remaining treatment liquid after the rinsing and drying treatment of the obtained Co film, the corrosion resistance before and after the rinsing treatment and the drying treatment Sexual evaluation. The evaluation criteria for each evaluation are also the same.

表3中總括示出了各實施例的處理液剩餘及耐腐蝕性的評價結果。Table 3 collectively shows the evaluation results of the remaining treatment liquid and the corrosion resistance of each example.

[表5] 表3 處理液 沖洗液 乾燥處理 處理液剩餘 耐腐蝕性 有無 溫度〔℃〕 Co SiOx Co SiOx 實施例201 實施例13 IPA 無 - A B A A 實施例202 實施例13 IPA 有 100 A A A A 實施例203 實施例13 IPA 有 200 S S A A 實施例204 實施例13 IPA 有 300 A A A A 實施例205 實施例13 IPA 有 400 A A C B [table 5] table 3 Treatment liquid Rinsing fluid Dry treatment Treatment liquid remaining Corrosion resistance With or without Temperature〔℃〕 Co SiOx Co SiOx Example 201 Example 13 IPA no - A B A A Example 202 Example 13 IPA Have 100 A A A A Example 203 Example 13 IPA Have 200 S S A A Example 204 Example 13 IPA Have 300 A A A A Example 205 Example 13 IPA Have 400 A A C B

從表3所示之結果確認到，在進行沖洗步驟後進行加熱並且乾燥之乾燥步驟之情況下，SiO2 膜中的處理液去除性優異（實施例201與實施例202的比較）。 確認到乾燥步驟中的加熱溫度係350℃以下之情況下，相對於Co膜及SiO2 膜之耐腐蝕性優異（實施例204與實施例205的比較）。 確認到乾燥步驟中的加熱溫度係50～350℃之情況下，SiO2 膜中的處理液去除性與相對於Co膜及SiO2 膜之耐腐蝕性的平衡更優異（實施例201、202、204與205的比較），乾燥步驟中的加熱溫度係150～250℃之情況下，Co膜及SiO2 膜中的處理液去除性更優異（實施例202～204的比較）。From the results shown in Table 3, it was confirmed that in the case of the drying step of heating and drying after the rinsing step, the removal of the treatment liquid in the SiO 2 film was excellent (comparison between Example 201 and Example 202). It was confirmed that when the heating temperature in the drying step was 350° C. or lower, the corrosion resistance to the Co film and the SiO 2 film was excellent (comparison of Example 204 and Example 205). The heating temperature in the drying step was confirmed lines 50 ~ 350 ℃ case where the treatment liquid SiO 2 film with more excellent removability (Example 201, 202 with respect to the balance of the corrosion resistance of the Co film and the film 2 SiO, Comparison of 204 and 205), when the heating temperature in the drying step is 150 to 250°C, the removal of the treatment liquid in the Co film and the SiO 2 film is more excellent (comparison of Examples 202 to 204).

[實施例301～309：凹蝕評價] 準備了藉由CVD（化學蒸鍍，Chemical Vapor Deposition）法在市售的矽晶圓（直徑：12英吋）的其中一者的表面上形成金屬鈷層之基板。金屬鈷層的厚度為20nm。 作為實施例301，進行了在40℃下將所獲得之基板浸漬於超純水中1分鐘之處理（步驟P）之後，進行了在40℃下浸漬上述（相對於Co膜之耐腐蝕性評價）中所記載之實施例10的處理液30秒鐘之處理（步驟Q）。步驟P及步驟Q的處理的次數為1次（亦即，1循環）。 藉由掃描型電子顯微鏡（Hitachi High-Technologies CorporationS-4800）觀察50處所獲得之基板的金屬鈷層的表面，計算出各區域中的金屬鈷層的膜厚的偏差（標準偏差），依據以下的基準進行了評價。 “S”：1nm以下 “A”：超過1nm且3nm以下 “B”：超過3nm且5nm以下 “C”：超過5nm[Examples 301 to 309: Evaluation of etchback] A substrate with a metal cobalt layer formed on the surface of one of the commercially available silicon wafers (diameter: 12 inches) by the CVD (Chemical Vapor Deposition) method was prepared. The thickness of the metallic cobalt layer is 20 nm. As Example 301, after immersing the obtained substrate in ultrapure water at 40°C for 1 minute (step P), the above-mentioned (corrosion resistance evaluation with respect to Co film) was immersed at 40°C. 30 seconds of treatment with the treatment solution of Example 10 described in) (step Q). The number of times of processing of step P and step Q is one time (that is, one cycle). Observe the surface of the metallic cobalt layer of the substrate obtained at 50 locations with a scanning electron microscope (Hitachi High-Technologies Corporation S-4800), and calculate the thickness deviation (standard deviation) of the metallic cobalt layer in each area, based on the following Benchmarks were evaluated. "S": Below 1nm "A": More than 1nm and less than 3nm "B": more than 3nm and less than 5nm "C": more than 5nm

使用表4中所記載之藥液進行步驟P的液處理並且將步驟P及Q組合為1循環時的步驟P及Q的處理的次數設為表4的“循環數”欄中所記載之次數，除此以外，依據實施例301的方法，進行了金屬鈷層的處理（實施例302～308）。 又，代替步驟P進行了使用了氧氣之電漿處理，除此以外，依據實施例301的方法，進行了金屬鈷層的處理（實施例309）。其中，藉由SUMCO公司製 RIE-101iPH，對形成有金屬鈷層之基板噴射氧氣50ml/分鐘的同時施加10秒鐘的120W的偏壓，藉此進行了氧化金屬鈷層的表面之電漿處理。When the liquid treatment of step P is performed with the chemical solution described in Table 4 and the number of treatments of step P and Q when steps P and Q are combined into one cycle is set to the number described in the "number of cycles" column of Table 4 In addition, according to the method of Example 301, the metal cobalt layer was processed (Examples 302 to 308). In addition, instead of Step P, plasma treatment using oxygen was performed. Otherwise, the metal cobalt layer was treated according to the method of Example 301 (Example 309). Among them, by RIE-101iPH manufactured by SUMCO, the substrate with the metal cobalt layer was sprayed with 50ml/min of oxygen gas while applying a bias voltage of 120W for 10 seconds, thereby performing plasma treatment on the surface of the metal cobalt oxide layer. .

[表6] 表4 步驟P 處理液 循環數 凹陷量 實施例301 超純水 實施例10 1 B 實施例302 超純水 實施例10 3 A 實施例303 超純水 實施例10 5 S 實施例304 超純水 實施例10 7 S 實施例305 超純水 實施例10 10 S 實施例306 氨與過氧化氫的混合水溶液 實施例10 5 A 實施例307 氟酸與過氧化氫水的混合水溶液 實施例10 1 B 實施例308 臭氧溶解水 實施例10 3 S 實施例309 使用氧氣之電漿處理 實施例10 1 A [Table 6] Table 4 Step P Treatment liquid Number of cycles Depression Example 301 Ultra-pure water Example 10 1 B Example 302 Ultra-pure water Example 10 3 A Example 303 Ultra-pure water Example 10 5 S Example 304 Ultra-pure water Example 10 7 S Example 305 Ultra-pure water Example 10 10 S Example 306 Mixed aqueous solution of ammonia and hydrogen peroxide Example 10 5 A Example 307 Mixed aqueous solution of hydrofluoric acid and hydrogen peroxide Example 10 1 B Example 308 Ozone dissolved water Example 10 3 S Example 309 Plasma treatment using oxygen Example 10 1 A

從表4所示之結果確認到，本發明的處理液的金屬氧化物含有層的凹陷量與膜厚的偏差性優異。From the results shown in Table 4, it was confirmed that the metal oxide-containing layer of the treatment liquid of the present invention has excellent unevenness in the amount of depression and the film thickness.

[實施例B-1～B-19] 〔試劑盒的製作〕 混合水、作為有機溶劑A的EGBE、作為有機溶劑B的化合物b-7、作為螯合劑的DTPA、作為羥胺化合物的HA、作為鹼性化合物的DBU及作為防腐蝕劑的5MBTA，製備第1液，又，混合水及作為螯合劑的CDC-G（洛赫西定葡萄糖酸鹽），製備第2液，從而製作了具備用於製備處理液之第1液及第2液之試劑盒。經製作之實施例B-1的試劑盒相當於上述試劑盒A。 另外，第1液及第2液的製備中，調節了第1液及第2液中所包含之各成分的含量，以使混合第1液及第2液而獲得之處理液中所包含之各成分具有表5所示之含量（均為相對於處理液的總質量之質量基準）[Examples B-1 to B-19] [Making of the kit] Mix water, EGBE as the organic solvent A, compound b-7 as the organic solvent B, DTPA as the chelating agent, HA as the hydroxylamine compound, DBU as the basic compound, and 5MBTA as the corrosion inhibitor to prepare the first liquid, In addition, water and CDC-G (loxidine gluconate) as a chelating agent were mixed to prepare the second solution, thereby producing a kit including the first solution and the second solution for preparing the treatment solution. The prepared kit of Example B-1 is equivalent to the above-mentioned kit A. In addition, in the preparation of the first liquid and the second liquid, the content of each component contained in the first liquid and the second liquid was adjusted so that the processing liquid obtained by mixing the first liquid and the second liquid contained Each component has the content shown in Table 5 (all are quality standards relative to the total mass of the treatment liquid)

〔處理液的製備〕 混合經製備之第1液及第2液，從而製備了實施例B-1的處理液。實施例B-1的處理液中的各成分的含量（均為相對於處理液的總質量之質量基準）如表5中所記載。〔Preparation of treatment liquid〕 The prepared first liquid and second liquid were mixed to prepare the treatment liquid of Example B-1. The content of each component in the treatment liquid of Example B-1 (all are mass standards relative to the total mass of the treatment liquid) are as described in Table 5.

〔實施例B-2～B-19〕 將第1液及第2液的組成變更為表5中所記載之組成，除此以外，依據實施例B-1的方法，製作具備第1液及第2液之試劑盒，使用所獲得之試劑盒製備了處理液。所製作之實施例B-2～B-19的試劑盒均相當於上述試劑盒A。 表5中，“水”的“第1液”欄及“第2液”欄分別表示處理液中所包含之水中的第1液及第2液中所包含之水的含量（均為相對於處理液的總量之質量基準）。 又，表5中，除了水以外的各成分的“試劑盒”欄中的標記表示其成分是否包含在第1液及第2液中的任一個。亦即，“試劑盒”欄中標記成“1”之成分包含在第1液，“試劑盒”欄中標記成“2”之成分包含在第2液。[Examples B-2～B-19] The composition of the first liquid and the second liquid was changed to the composition described in Table 5. Otherwise, according to the method of Example B-1, a kit with the first liquid and the second liquid was prepared, and the obtained The kit prepared a treatment solution. The prepared kits of Examples B-2 to B-19 are all equivalent to the above-mentioned kit A. In Table 5, the "1st liquid" and "2nd liquid" columns of "water" respectively indicate the content of water contained in the first liquid and the second liquid in the water contained in the treatment liquid (both are relative to The quality standard of the total amount of treatment liquid). In addition, in Table 5, the mark in the "kit" column of each component other than water indicates whether the component is contained in either the first liquid or the second liquid. That is, the component marked "1" in the "kit" column is included in the first liquid, and the component marked "2" in the "kit" column is included in the second liquid.

示於表5之各成分均使用分類成半導體水準者或分類成以其為基準之高純度水準者。 在實施例B-1～B-19中，除了實施例1～31中的任一個中使用之上述成分以外，使用了下述成分。The components shown in Table 5 are classified into semiconductor level or classified into high purity level based on it. In Examples B-1 to B-19, in addition to the above-mentioned components used in any of Examples 1 to 31, the following components were used.

＜去除劑（螯合劑）＞ ・CDC-G：洛赫西定葡萄糖酸鹽（相當於由上述式（III）表示之化合物） ・CDC-Cl：洛赫西定鹽酸鹽（相當於由上述式（III）表示之化合物）＜Removing agent (chelating agent)＞ ・CDC-G: Loxidine gluconate (equivalent to the compound represented by the above formula (III)) ・CDC-Cl: Lohxidine hydrochloride (equivalent to the compound represented by the above formula (III))

・精胺酸（具有至少2個含氮之基團之單羧酸） [化學式8]

Figure 02_image014
・Arginine (monocarboxylic acid with at least 2 nitrogen-containing groups) [Chemical formula 8]
Figure 02_image014

・PBG：苯基雙胍（相當於由上述式（II）表示之化合物） [化學式9]

Figure 02_image016
・PBG: Phenyl biguanide (equivalent to the compound represented by the above formula (II)) [Chemical formula 9]
Figure 02_image016

・TBG：1-（鄰甲苯基）雙胍 [化學式10]

Figure 02_image018
・TBG: 1-(o-tolyl) biguanide [Chemical formula 10]
Figure 02_image018

又，表5中所記載之高分子1～6由上述之式（IV）表示並且具有下述表所示之n、R25 及R26 之高分子雙胍。 ―――――――――――――――――――――――――――――― 高分子編號  R25 R26 n ―――――――――――――――――――――――――――――― 1    H   碳數4的伸烷基   10 2    H   碳數8的伸烷基   15 3    H   碳數10的伸烷基   20 4    H   碳數6的伸烷基   100 5    H   碳數6的伸烷基   200 6    H   碳數6的伸烷基   300 ――――――――――――――――――――――――――――――In addition, polymers 1 to 6 described in Table 5 are represented by the above-mentioned formula (IV) and have a polymer biguanide having n, R 25 and R 26 shown in the following table. ――――――――――――――――――――――――――――――Polymer No. R 25 R 26 n ―――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――—— ――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――‖ Alkylene with 6 carbon 100 5 H Alkylene with 6 carbon 200 6 H Alkylene with 6 carbon 300 ―――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――――― ――――――――

＜鹼性化合物＞ ・TBAH：四丁基氫氧化銨（相當於四級銨氫氧化物。） ・MEA：單乙醇胺（相當於一級胺。） ・AMP：2-胺基-2-甲基-1-丙醇（相當於一級胺。） ・DBA：二丁胺（相當於二級胺。） ・TBA：三丁胺（相當於三級胺。） ・BzTMAH：苄基三甲基氫氧化銨（相當於四級銨氫氧化物。）＜Basic compound＞ ・TBAH: Tetrabutylammonium hydroxide (equivalent to quaternary ammonium hydroxide.) ・MEA: Monoethanolamine (equivalent to primary amine.) ・AMP: 2-Amino-2-methyl-1-propanol (equivalent to a primary amine.) ・DBA: Dibutylamine (equivalent to secondary amine.) ・TBA: Tributylamine (equivalent to tertiary amine.) ・BzTMAH: Benzyl trimethyl ammonium hydroxide (equivalent to quaternary ammonium hydroxide.)

〔評價〕 依據實施例1～31中所記載之方法，對所製備之實施例B-1～B-19的處理液評價了耐腐蝕性、殘渣去除性及缺陷抑制性。 另外，在實施例B-1～B-19中，準備由W構成之膜，以與實施例1（相對於Co膜之耐腐蝕性評價）相同的方式，進行了基於蝕刻速度的計算與蝕刻速度的計算結果之耐腐蝕性的評價。 表5中示出了耐腐蝕性的測量結果以及耐腐蝕性、殘渣去除性及缺陷抑制性的評價結果。〔Evaluation〕 According to the methods described in Examples 1 to 31, the prepared treatment solutions of Examples B-1 to B-19 were evaluated for corrosion resistance, residue removal properties, and defect suppression properties. In addition, in Examples B-1 to B-19, films composed of W were prepared, and calculations based on the etching rate and etching were performed in the same manner as in Example 1 (evaluation of corrosion resistance with respect to the Co film). Evaluation of the corrosion resistance of the calculation result of the speed. Table 5 shows the measurement results of corrosion resistance and the evaluation results of corrosion resistance, residue removal properties, and defect suppression properties.

[表7] 表5 處理液的組成 水 有機溶劑A 有機溶劑B 比例1 去除劑 螯合劑 HA化合物 第1液 第2液 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 實施例B-1 87.43% 1.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G 0.001% 2 HA 5.00% 1 實施例B-2 85.96% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 實施例B-3 88.66% 0.10% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G 0.025% 2 HA 5.00% 1 實施例B-4 68.64% 20.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 實施例B-5 68.34% 20.00% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 精胺酸 0.300% 2 HA 5.00% 1 實施例B-6 80.80% 5.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 實施例B-7 82.79% 5.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 TBG 0.700% 2 HA 5.00% 1 實施例B-8 86.86% 1.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子5 0.100% 2 HA 5.00% 1 實施例B-9 83.61% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 2 高分子6 0.100% 2 HA 5.00% 1 實施例B-10 87.41% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.025% 2 HA 5.00% 1 實施例B-11 87.34% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子1 0.100% 2 HA 5.00% 1 實施例B-12 83.29% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子2 0.100% 2 HA 5.00% 1 實施例B-13 78.34% 10.00% EGBE 5.0% 2 b-5 0.001% 2 5.0E+03 DTPA 0.60% 1 高分子3 0.100% 2 HA 5.00% 1 實施例B-14 83.40% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子4 0.100% 2 HA 5.00% 1 實施例B-15 87.45% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 實施例B-16 87.14% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子5 0.050% 2 HA 5.00% 1 實施例B-17 58.80% 30.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.050% 2 HA 5.00% 1 實施例B-18 78.75% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 實施例B-19 78.80% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 [Table 7] table 5 Composition of treatment liquid water Organic solvent A Organic solvent B Scale 1 Remover Chelating agent HA compound The first solution The second solution Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Example B-1 87.43% 1.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G 0.001% 2 HA 5.00% 1 Example B-2 85.96% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 Example B-3 88.66% 0.10% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G 0.025% 2 HA 5.00% 1 Example B-4 68.64% 20.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 Example B-5 68.34% 20.00% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 Arginine 0.300% 2 HA 5.00% 1 Example B-6 80.80% 5.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 Example B-7 82.79% 5.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 TBG 0.700% 2 HA 5.00% 1 Example B-8 86.86% 1.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 5 0.100% 2 HA 5.00% 1 Example B-9 83.61% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 2 Polymer 6 0.100% 2 HA 5.00% 1 Example B-10 87.41% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.025% 2 HA 5.00% 1 Example B-11 87.34% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 1 0.100% 2 HA 5.00% 1 Example B-12 83.29% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 2 0.100% 2 HA 5.00% 1 Example B-13 78.34% 10.00% EGBE 5.0% 2 b-5 0.001% 2 5.0E+03 DTPA 0.60% 1 Polymer 3 0.100% 2 HA 5.00% 1 Example B-14 83.40% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 4 0.100% 2 HA 5.00% 1 Example B-15 87.45% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 Example B-16 87.14% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 5 0.050% 2 HA 5.00% 1 Example B-17 58.80% 30.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.050% 2 HA 5.00% 1 Example B-18 78.75% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1 Example B-19 78.80% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G 0.050% 2 HA 5.00% 1

[表8] 表5 （續） 處理液的組成 處理液的pH 耐腐蝕性 殘渣 去除性 缺陷 抑制性 鹼性化合物 Co離子 比例2 防腐蝕劑 Co W SiO2 化合物 量 （%） 試劑盒 Co離子源 量 （%） 試劑盒 化合物 量 （%） 試劑盒 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 實施例B-1 DBU 0.76% 1         5MBTA 0.20% 1 8.5 0.1 S 0.6 A 0.1 S S S 實施例B-2 TBAH 1.24% 1         5MBTA 0.20% 1 8.7 0.2 S 0.2 S 0.3 S S S 實施例B-3 MEA 0.41% 1         5MBTA 0.20% 1 8.6 0.1 S 0.1 S 0.2 S S S 實施例B-4 TMAH 0.51% 1 Co（OH）2 10.0 1 1.0E+08 5MBTA 0.20% 1 8.9 0.2 S 0.1 S 0.3 S S S 實施例B-5 AMP 0.55% 1         5MBTA 0.20% 1 7.5 0.1 S 1.0 A 0.8 A S S 實施例B-6 AEEA 2.40% 1         5MBTA 0.20% 1 8.0 0.1 S 0.2 S 0.2 S S S 實施例B-7 DBU 0.70% 2         5MBTA 0.20% 1 7.5 0.1 S 0.9 A 0.2 S S A 實施例B-8 TBAH 1.24% 1         5MBTA 0.20% 1 8.1 0.1 S 0.1 S 0.3 S S S 實施例B-9 TMAH 0.49% 2         5MBTA 0.20% 1 8.2 0.1 S 0.1 S 0.2 S S S 實施例B-10 DBU 0.76% 2         5MBTA 0.20% 1 8.2 0.1 S 0.1 S 0.2 S S S 實施例B-11 DBU 0.76% 1 Co（OH）2 20.0 2 5.0E+07 5MBTA 0.20% 1 8.5 0.1 S 0.1 S 0.2 S S A 實施例B-12 DBU 0.81% 1         5MBTA 0.20% 1 8.2 0.1 S 0.2 S 0.2 S S A 實施例B-13 DBU 0.76% 1         5MBTA 0.20% 1 8.7 0.1 S 0.2 S 0.2 S A S 實施例B-14 DBU 0.70% 1         5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S A S 實施例B-15 DBA 0.70% 1         5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S S S 實施例B-16 TBA 1.01% 1         5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S S S 實施例B-17 BzTMAH 0.35% 2         5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S S S 實施例B-18 TBAH 0.40% 1         5MBTA 0.20% 1 7.7 0.1 S 0.2 S 0.1 S S S 實施例B-19 TMAH 0.35% 1         5MBTA 0.20% 1 7.5 0.1 S 0.2 S 0.1 S S S [Table 8] Table 5 (continued) Composition of treatment liquid PH of the treatment solution Corrosion resistance Residue removal Defect inhibition Basic compound Co ion Scale 2 Anti-corrosion agent Co W SiO 2 Compound the amount(%) Reagent test kit Co ion source the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Example B-1 DBU 0.76% 1 5MBTA 0.20% 1 8.5 0.1 S 0.6 A 0.1 S S S Example B-2 TBAH 1.24% 1 5MBTA 0.20% 1 8.7 0.2 S 0.2 S 0.3 S S S Example B-3 MEA 0.41% 1 5MBTA 0.20% 1 8.6 0.1 S 0.1 S 0.2 S S S Example B-4 TMAH 0.51% 1 Co(OH) 2 10.0 1 1.0E+08 5MBTA 0.20% 1 8.9 0.2 S 0.1 S 0.3 S S S Example B-5 AMP 0.55% 1 5MBTA 0.20% 1 7.5 0.1 S 1.0 A 0.8 A S S Example B-6 AEEA 2.40% 1 5MBTA 0.20% 1 8.0 0.1 S 0.2 S 0.2 S S S Example B-7 DBU 0.70% 2 5MBTA 0.20% 1 7.5 0.1 S 0.9 A 0.2 S S A Example B-8 TBAH 1.24% 1 5MBTA 0.20% 1 8.1 0.1 S 0.1 S 0.3 S S S Example B-9 TMAH 0.49% 2 5MBTA 0.20% 1 8.2 0.1 S 0.1 S 0.2 S S S Example B-10 DBU 0.76% 2 5MBTA 0.20% 1 8.2 0.1 S 0.1 S 0.2 S S S Example B-11 DBU 0.76% 1 Co(OH) 2 20.0 2 5.0E+07 5MBTA 0.20% 1 8.5 0.1 S 0.1 S 0.2 S S A Example B-12 DBU 0.81% 1 5MBTA 0.20% 1 8.2 0.1 S 0.2 S 0.2 S S A Example B-13 DBU 0.76% 1 5MBTA 0.20% 1 8.7 0.1 S 0.2 S 0.2 S A S Example B-14 DBU 0.70% 1 5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S A S Example B-15 DBA 0.70% 1 5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S S S Example B-16 TBA 1.01% 1 5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S S S Example B-17 BzTMAH 0.35% 2 5MBTA 0.20% 1 8.4 0.1 S 0.2 S 0.2 S S S Example B-18 TBAH 0.40% 1 5MBTA 0.20% 1 7.7 0.1 S 0.2 S 0.1 S S S Example B-19 TMAH 0.35% 1 5MBTA 0.20% 1 7.5 0.1 S 0.2 S 0.1 S S S

從表5的結果確認到，使用具備包含羥胺化合物之第1液及包含螯合劑中的至少1種之第2液之試劑盒製備之處理液具有相對於Co膜、W膜及SiO2 膜之優異之耐腐蝕性，並且殘渣去除性及缺陷抑制性優異。From the results in Table 5, it was confirmed that the treatment solution prepared using the kit provided with the first solution containing the hydroxylamine compound and the second solution containing at least one of the chelating agent has a higher value than that of the Co film, W film, and SiO 2 film. Excellent corrosion resistance, and excellent residue removal and defect suppression.

確認到具備包含羥胺化合物之第1液及包含特定含氮螯合劑之第2液之試劑盒中，特定含氮螯合劑的含量相對於處理液的總質量係0.003質量%以上之情況下，相對於W膜之耐腐蝕性更優異（實施例B-1與實施例B-3的比較）。 又，確認到具備包含羥胺化合物之第1液及包含特定含氮螯合劑之第2液之試劑盒中，特定含氮螯合劑係選自包括由上述式（II）～（IV）表示之雙胍化合物及它們的鹽之群組中之化合物之情況下，相對於W膜及SiO2 膜之耐腐蝕性更優異（實施例B-2、B-3及B-9～B-17與實施例B-5的比較）。 確認到具備包含羥胺化合物之第1液及包含特定含氮螯合劑之第2液之試劑盒中，特定含氮螯合劑係選自包括由上述式（II）～（IV）表示之雙胍化合物及它們的鹽之群組中之化合物之情況下，相對於W膜及SiO2 膜之耐腐蝕性更優異（實施例B-2、B-3及B-9～B-17與實施例B-5的比較）。It was confirmed that in the kit with the first liquid containing hydroxylamine compound and the second liquid containing specific nitrogen-containing chelating agent, when the content of the specific nitrogen-containing chelating agent is 0.003% by mass or more relative to the total mass of the treatment liquid, relative The corrosion resistance of the W film is more excellent (comparison of Example B-1 and Example B-3). In addition, it was confirmed that in the kit provided with the first solution containing the hydroxylamine compound and the second solution containing the specific nitrogen-containing chelating agent, the specific nitrogen-containing chelating agent is selected from the group consisting of the biguanides represented by the above formulas (II) to (IV) In the case of compounds in the group of compounds and their salts, the corrosion resistance compared to the W film and the SiO 2 film is more excellent (Examples B-2, B-3, and B-9 to B-17 and Examples B-5 comparison). It was confirmed that in the kit provided with the first solution containing the hydroxylamine compound and the second solution containing the specific nitrogen-containing chelating agent, the specific nitrogen-containing chelating agent is selected from the group consisting of the biguanide compounds represented by the above formulas (II) to (IV) and In the case of compounds in the group of their salts, they are more excellent in corrosion resistance than W film and SiO 2 film (Examples B-2, B-3, and B-9 to B-17 and Example B- Comparison of 5).

確認到具備包含羥胺化合物之第1液及作為螯合劑包含由上述式（II）表示之化合物或其鹽之第2液之試劑盒中，由上述式（II）中的R10 ～R13 表示之芳基係非取代苯基之情況下，缺陷抑制性更優異（實施例B-6與實施例B-7的比較）。 確認到具備包含羥胺化合物之第1液及作為螯合劑包含由上述式（IV）表示之化合物或其鹽之第2液之試劑盒中，上述式（IV）中的n係150以上的整數之情況下，殘渣去除性及/或缺陷抑制性更優異（實施例B-8及B-9與實施例B-11～B-14的比較）。It was confirmed that a kit provided with a first liquid containing a hydroxylamine compound and a second liquid containing a compound represented by the above formula (II) or a salt thereof as a chelating agent is represented by R 10 to R 13 in the above formula (II) In the case where the aryl group is a non-substituted phenyl group, the defect inhibitory property is more excellent (comparison between Example B-6 and Example B-7). It was confirmed that in a kit provided with a first solution containing a hydroxylamine compound and a second solution containing a compound represented by the above formula (IV) or a salt thereof as a chelating agent, n in the above formula (IV) is an integer of 150 or more In this case, the residue removability and/or defect suppression properties are more excellent (comparison between Examples B-8 and B-9 and Examples B-11 to B-14).

實施例B-1～B-19中，代替W膜分別使用了由向鎢添加選自包括碳、氮、硼及磷之群組中之1個元素之鎢系金屬材料構成之膜，除此以外，依據上述方法，對實施例B-1～B-19的處理液評價了耐腐蝕性。其結果確認到，關於實施例B-1～B-19的處理液，相對於由鎢中包含上述各元素之鎢系金屬材料構成之各個膜之耐腐蝕性亦與W膜同樣優異。In Examples B-1 to B-19, instead of the W film, a film made of a tungsten-based metal material in which one element selected from the group consisting of carbon, nitrogen, boron, and phosphorus is added to tungsten was used, except for this In addition, according to the above-mentioned method, the corrosion resistance of the treatment liquids of Examples B-1 to B-19 was evaluated. As a result, it was confirmed that the treatment liquids of Examples B-1 to B-19 were also excellent in corrosion resistance with respect to the respective films composed of the tungsten-based metal material containing the aforementioned elements in tungsten, as well as the W film.

[實施例C-1～C-5] 〔處理液的製備〕 以表6中所記載之配方混合表6中所記載之各成分，從而製備了實施例C-1～C-5的各處理液。另外，各處理液中，各種成分的含量（均為質量基準）如表中所述。 示於表6之各種成分均使用分類成半導體水準者或分類成以其為基準之高純度水準者。[Examples C-1 to C-5] 〔Preparation of treatment liquid〕 Each component described in Table 6 was mixed with the formulation described in Table 6 to prepare each treatment liquid of Examples C-1 to C-5. In addition, the contents of various components (all on a quality basis) in each treatment liquid are as described in the table. The various components shown in Table 6 are classified into semiconductor level or classified into high purity level based on it.

在實施例C-1～C-5中，除了在實施例1～31及實施例B-1～B-19中的任一個中使用之上述成分以外，使用了下述成分。 ＜鹼性化合物＞ ・TEAH：氫氧化四乙銨（相當於四級銨氫氧化物。）In Examples C-1 to C-5, in addition to the above-mentioned components used in any of Examples 1 to 31 and Examples B-1 to B-19, the following components were used. ＜Basic compound＞ ・TEAH: Tetraethylammonium hydroxide (equivalent to quaternary ammonium hydroxide.)

〔評價〕 依據實施例B-1～B-19中所記載之方法，對經製備之實施例C-1～C-5的處理液評價了耐腐蝕性、殘渣去除性及缺陷抑制性。 表6中示出了耐腐蝕性的測量結果以及耐腐蝕性、殘渣去除性及缺陷抑制性的評價結果。〔Evaluation〕 According to the methods described in Examples B-1 to B-19, the prepared treatment solutions of Examples C-1 to C-5 were evaluated for corrosion resistance, residue removal properties, and defect suppression properties. Table 6 shows the measurement results of corrosion resistance and the evaluation results of corrosion resistance, residue removal properties, and defect suppression properties.

[表9] 表6 處理液的組成 水 有機溶劑A 有機溶劑B 比例1 去除劑 螯合劑 HA化合物 量 （%） 化合物 量 （%） 化合物 量 （%） 化合物 量 （%） 化合物 量 （%） 化合物 量 （%） 實施例C-1 88.39% EGBE 5.0% b-7 0.010% 5.0E+02 DTPA 0.40% CDC-G 0.010% HA 5.00% 實施例C-2 88.50% EGBE 5.0% b-5 0.001% 5.0E+03 DTPA 0.40%     HA 5.00% 實施例C-3 89.03% EGBE 5.0% b-5 0.010% 5.0E+02 DTPA 0.40% CDC-G 0.025% HA 5.00% 實施例C-4 89.05% EGBE 5.0% b-5 0.010% 5.0E+02 DTPA 0.40%     HA 5.00% 實施例C-5 88.90% EGBE 5.0% b-5 0.010% 5.0E+02 DTPA 0.40% PBG 0.010% HA 5.00% [Table 9] Table 6 Composition of treatment liquid water Organic solvent A Organic solvent B Scale 1 Remover Chelating agent HA compound the amount(%) Compound the amount(%) Compound the amount(%) Compound the amount(%) Compound the amount(%) Compound the amount(%) Example C-1 88.39% EGBE 5.0% b-7 0.010% 5.0E+02 DTPA 0.40% CDC-G 0.010% HA 5.00% Example C-2 88.50% EGBE 5.0% b-5 0.001% 5.0E+03 DTPA 0.40% HA 5.00% Example C-3 89.03% EGBE 5.0% b-5 0.010% 5.0E+02 DTPA 0.40% CDC-G 0.025% HA 5.00% Example C-4 89.05% EGBE 5.0% b-5 0.010% 5.0E+02 DTPA 0.40% HA 5.00% Example C-5 88.90% EGBE 5.0% b-5 0.010% 5.0E+02 DTPA 0.40% PBG 0.010% HA 5.00%

[表10] 表6 （續） 處理液的組成 處理液的pH 耐腐蝕性 殘渣去除性 缺陷抑制性 鹼性化合物 防腐蝕劑 Co W SiO2 化合物 量 （%） 化合物 量 （%） 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 實施例C-1 TBAH 0.99% 5MBTA 0.20% 8.9 0.2 S 0.1 S 0.1 S S S 實施例C-2 TBAH 0.90% TTA 0.20% 8.3 0.1 S 0.5 A 0.2 S S S 實施例C-3 TMAH 0.34% Iragamet 42 0.20% 8.5 0.2 S 0.2 S 0.1 S S S 實施例C-4 TMAH 0.34% 5MBTA 0.20% 8.5 0.1 S 0.5 A 0.2 S S S 實施例C-5 TEAH 0.48% 5MBTA 0.20% 8.6 0.3 S 0.3 S 0.1 S S S [Table 10] Table 6 (continued) Composition of treatment liquid PH of the treatment solution Corrosion resistance Residue removal Defect inhibition Basic compound Anti-corrosion agent Co W SiO 2 Compound the amount(%) Compound the amount(%) Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Example C-1 TBAH 0.99% 5MBTA 0.20% 8.9 0.2 S 0.1 S 0.1 S S S Example C-2 TBAH 0.90% TTA 0.20% 8.3 0.1 S 0.5 A 0.2 S S S Example C-3 TMAH 0.34% Iragamet 42 0.20% 8.5 0.2 S 0.2 S 0.1 S S S Example C-4 TMAH 0.34% 5MBTA 0.20% 8.5 0.1 S 0.5 A 0.2 S S S Example C-5 TEAH 0.48% 5MBTA 0.20% 8.6 0.3 S 0.3 S 0.1 S S S

從表6的結果確認到，本發明的處理液具有相對於Co膜、W膜及SiO2 膜之優異之耐腐蝕性，並且殘渣去除性及缺陷抑制性優異。 又，確認到處理液包含特定含氮螯合劑之情況下，相對於W膜之耐腐蝕性更優異（實施例C-1～C-5的比較）。It was confirmed from the results in Table 6 that the treatment solution of the present invention has excellent corrosion resistance with respect to the Co film, W film, and SiO 2 film, and also has excellent residue removal properties and defect suppression properties. In addition, it was confirmed that when the treatment liquid contained a specific nitrogen-containing chelating agent, the corrosion resistance with respect to the W film was more excellent (comparison of Examples C-1 to C-5).

實施例C-1～C-5中，代替W膜分別使用了由向鎢添加選自包括碳、氮、硼及磷之群組中之1個元素之鎢系金屬材料構成之膜，除此以外，依據上述方法，對實施例C-1～C-5的處理液評價了耐腐蝕性。其結果確認到，關於實施例C-1～C-5的處理液，相對於由鎢中包含上述各元素之鎢系金屬材料構成之各個膜之耐腐蝕性亦與W膜同樣優異。In Examples C-1 to C-5, instead of the W film, a film made of a tungsten-based metal material in which one element selected from the group consisting of carbon, nitrogen, boron, and phosphorus is added to tungsten was used, except for this In addition, according to the above-mentioned method, the corrosion resistance of the treatment liquids of Examples C-1 to C-5 was evaluated. As a result, it was confirmed that the treatment liquids of Examples C-1 to C-5 also had excellent corrosion resistance with respect to the respective films composed of the tungsten-based metal material containing the aforementioned elements in tungsten, as well as the W film.

[實施例401～405：凹蝕評價] 使用表7中所記載之藥液進行步驟P的液處理並且將步驟P及Q組合為1循環時的步驟P及Q的處理的次數設為表7的“循環數”欄中所記載之次數，除此以外，依據實施例301的方法，進行了金屬鈷層的處理。 表7中示出了分別對實施例401～405在步驟P的液處理中使用之氧化液、在步驟Q中使用之處理液、循環數及凹蝕評價（金屬鈷層的膜厚的偏差）的結果。[Examples 401 to 405: Evaluation of etchback] When the liquid treatment of step P is performed using the chemical solution described in Table 7 and the number of treatments of step P and Q when steps P and Q are combined into one cycle is set to the number described in the "number of cycles" column of Table 7 In addition, according to the method of Example 301, the metal cobalt layer was processed. Table 7 shows the oxidizing solution used in the liquid treatment of step P, the treatment solution used in step Q, the number of cycles, and the etchback evaluation (variation of the thickness of the metallic cobalt layer) for Examples 401 to 405, respectively. the result of.

[表11] 表7 步驟P 處理液 循環數 凹陷量 實施例401 超純水 實施例C-1 5 S 實施例402 超純水 實施例C-2 3 A 實施例403 超純水 實施例C-3 2 S 實施例404 氨與過氧化氫的混合水溶液 實施例C-4 4 A 實施例405 氨與過氧化氫的混合水溶液 實施例C-5 5 S [Table 11] Table 7 Step P Treatment liquid Number of cycles Depression Example 401 Ultra-pure water Example C-1 5 S Example 402 Ultra-pure water Example C-2 3 A Example 403 Ultra-pure water Example C-3 2 S Example 404 Mixed aqueous solution of ammonia and hydrogen peroxide Example C-4 4 A Example 405 Mixed aqueous solution of ammonia and hydrogen peroxide Example C-5 5 S

從表7所示之結果確認到，本發明的實施例401～405的處理液的金屬氧化物含有層的凹陷量與膜厚的偏差性優異。 又，確認到處理液包含特定含氮螯合劑之情況下，金屬氧化物含有層的凹陷量與膜厚的偏差性更優異（實施例402與實施例403的比較、實施例405與實施例306的比較等）。From the results shown in Table 7, it was confirmed that the treatment solutions of Examples 401 to 405 of the present invention have excellent variations in the amount of depression and film thickness of the metal oxide-containing layer. In addition, it was confirmed that when the treatment liquid contained the specific nitrogen-containing chelating agent, the deviation of the amount of depression and the film thickness of the metal oxide-containing layer was more excellent (comparison between Example 402 and Example 403, Example 405 and Example 306 Comparison, etc.).

[實施例D-1～D-19] 〔金屬去除步驟：試驗例1～13〕 作為試驗例1～13，製作具備用於製備處理液的第1液及第2液之試劑盒之前，實施了使用螯合樹脂從包含特定的螯合劑之原料去除金屬之金屬去除步驟。[Examples D-1 to D-19] [Metal removal procedure: Test examples 1-13] As Test Examples 1-13, before producing a kit equipped with the first liquid and the second liquid for preparing the treatment liquid, a metal removal step was performed to remove metals from a raw material containing a specific chelating agent using a chelating resin.

在各試驗例中，製備了分別包含實施例B-1～B-19中使用之螯合劑中的第2液的製備中所使用之CDC-G、CDC-Cl、精胺酸、PDG、TDG及高分子1～6之被純化物。又，在各試驗例中，使用了以下所示之螯合樹脂。樹脂1～3均係作為螯合基包含胺基甲基膦酸基之螯合樹脂。 ・樹脂1：ORGANO CORPORATION製“Orlite DS-21” ・樹脂2：Sumika Chemtex Company, Limited製“Sumichelate MC960” ・樹脂3：Purolite公司製“Purolite S950” 表8中示出了在各試驗例中使用之螯合劑與螯合樹脂的組合。In each test example, CDC-G, CDC-Cl, arginine, PDG, TDG used in the preparation of the second liquid in the chelating agent used in Examples B-1 to B-19 were prepared. And polymers 1 to 6 to be purified. In addition, in each test example, the chelating resin shown below was used. Resins 1 to 3 are all chelating resins containing aminomethylphosphonic acid groups as chelating groups. ・Resin 1: "Orlite DS-21" manufactured by ORGANO CORPORATION ・Resin 2: "Sumichelate MC960" manufactured by Sumika Chemtex Company, Limited ・Resin 3: "Purolite S950" manufactured by Purolite Table 8 shows the combination of the chelating agent and the chelating resin used in each test example.

以下，以試驗例1為例，示出了使用螯合樹脂而實施之金屬去除步驟的詳細的順序。 首先，製備了包含CDC-G之被純化物。此時，添加水（超純水）調節成被純化物中的CDC-G的含量相對於被純化物的總質量成為20質量%。 向直徑2cm的管柱填充25ml的樹脂1之後，繼續向管柱內通過鹽酸1%水溶液50ml及超純水100ml，藉此清洗了樹脂1。之後，使包含CDC-G之被純化物通過管柱內的樹脂1，實施從被純化物去除金屬之處理，從而獲得了包含CDC-G且金屬含量降低之純化物。另外，被純化物的溫度係20～25℃，通過螯合樹脂之被純化物的速度（流速）係SV（空間速度）=10。 使用表8中所記載之螯合劑及螯合樹脂，除此以外，以與上述試驗例1相同的方式實施了試驗例2～13。Hereinafter, using Test Example 1 as an example, the detailed procedure of the metal removal step performed using the chelating resin is shown. First, a purified product containing CDC-G was prepared. At this time, the added water (ultrapure water) was adjusted so that the content of CDC-G in the purified product was 20% by mass relative to the total mass of the purified product. After filling 25 ml of resin 1 into a column with a diameter of 2 cm, 50 ml of a 1% hydrochloric acid aqueous solution and 100 ml of ultrapure water were continuously passed into the column to wash the resin 1. After that, the purified product containing CDC-G is passed through the resin 1 in the column, and the metal is removed from the purified product, thereby obtaining a purified product containing CDC-G with a reduced metal content. In addition, the temperature of the object to be purified is 20-25°C, and the speed (flow rate) of the object to be purified through the chelating resin is SV (space velocity)=10. Except that the chelating agent and the chelating resin described in Table 8 were used, Test Examples 2 to 13 were carried out in the same manner as Test Example 1 described above.

各試驗例中，依據作為實施例1～31中處理液所包含之鈷離子含量的測量方法記載之方法，測量了藉由螯合樹脂進行純化之前的被純化物中的金屬含量及進行純化之後的純化物中的金屬含量。表8中分別示出了純化之前的被純化物中的金屬含量及純化之後的純化物中的金屬含量的測量結果。In each test example, in accordance with the method described as the method for measuring the content of cobalt ion contained in the treatment liquid in Examples 1 to 31, the metal content in the purified substance before purification by chelating resin and after purification were measured The metal content of the purified substance. Table 8 shows the measurement results of the metal content in the purified product before purification and the metal content in the purified product after purification, respectively.

[表12] 表8 螯合劑 螯合樹脂 純化前/純化後 金屬含量（ppb） 種類 含量（%） Na Mg Al K Ca Cr Mn Fe Ni Zn Pb Li 試驗例1 CDC-G 20 樹脂1 純化前 223 64 23 18 213 3 3 21 2 638 1 3 純化後 2 3 6 3 8 4 0 6 0 1 0 2 試驗例2 CDC-Cl 20 樹脂2 純化前 320 80 50 40 320 10 5 30 5 106 3 10 純化後 7 16 7 14 10 7 17 5 2 4 11 1 試驗例3 精胺酸 20 樹脂2 純化前 376 217 189 196 288 100 296 600 363 262 329 142 純化後 4 5 9 7 10 13 14 8 3 7 18 11 試驗例4 PBG 20 樹脂3 純化前 399 359 211 258 274 370 292 187 112 148 234 394 純化後 8 17 11 1 10 18 11 5 10 13 7 3 試驗例5 TBG 20 樹脂1 純化前 154 396 204 332 218 365 108 299 129 195 382 344 純化後 3 19 16 14 4 9 14 9 18 1 15 1 試驗例6 高分子1 20 樹脂3 純化前 111 254 323 219 204 132 369 242 169 395 388 333 純化後 4 16 4 11 6 16 7 8 8 19 14 20 試驗例7 高分子2 20 樹脂2 純化前 189 284 194 319 253 188 199 315 228 326 338 397 純化後 7 4 11 3 12 6 8 1 1 7 4 2 試驗例8 高分子3 20 樹脂1 純化前 206 184 389 360 371 245 140 264 230 388 230 317 純化後 10 6 12 18 15 11 10 3 8 19 18 19 試驗例9 高分子4 20 樹脂2 純化前 143 118 125 200 313 345 330 149 141 246 383 268 純化後 10 17 7 4 14 6 6 3 20 2 12 5 試驗例10 高分子5 20 樹脂3 純化前 188 244 219 330 320 212 330 105 237 165 147 270 純化後 10 15 5 9 14 16 6 13 20 17 13 17 試驗例11 高分子6 20 樹脂1 純化前 266 341 111 187 186 137 231 122 350 130 295 280 純化後 15 6 9 18 18 8 3 6 18 11 6 18 試驗例12 CDC-G 20 樹脂2 純化前 223 64 23 18 213 3 3 21 2 638 1 3 純化後 6 19 7 5 19 12 5 7 15 18 18 5 試驗例13 CDC-G 20 樹脂3 純化前 223 64 23 18 213 3 3 21 2 638 1 3 純化後 6 18 8 4 20 16 7 17 5 20 18 12 [Table 12] Table 8 Chelating agent Chelating resin Before purification/After purification Metal content (ppb) species content(%) Na Mg Al K Ca Cr Mn Fe Ni Zn Pb Li Test example 1 CDC-G 20 Resin 1 Before purification 223 64 twenty three 18 213 3 3 twenty one 2 638 1 3 After purification 2 3 6 3 8 4 0 6 0 1 0 2 Test example 2 CDC-Cl 20 Resin 2 Before purification 320 80 50 40 320 10 5 30 5 106 3 10 After purification 7 16 7 14 10 7 17 5 2 4 11 1 Test example 3 Arginine 20 Resin 2 Before purification 376 217 189 196 288 100 296 600 363 262 329 142 After purification 4 5 9 7 10 13 14 8 3 7 18 11 Test example 4 PBG 20 Resin 3 Before purification 399 359 211 258 274 370 292 187 112 148 234 394 After purification 8 17 11 1 10 18 11 5 10 13 7 3 Test Example 5 TBG 20 Resin 1 Before purification 154 396 204 332 218 365 108 299 129 195 382 344 After purification 3 19 16 14 4 9 14 9 18 1 15 1 Test Example 6 Polymer 1 20 Resin 3 Before purification 111 254 323 219 204 132 369 242 169 395 388 333 After purification 4 16 4 11 6 16 7 8 8 19 14 20 Test Example 7 Polymer 2 20 Resin 2 Before purification 189 284 194 319 253 188 199 315 228 326 338 397 After purification 7 4 11 3 12 6 8 1 1 7 4 2 Test Example 8 Polymer 3 20 Resin 1 Before purification 206 184 389 360 371 245 140 264 230 388 230 317 After purification 10 6 12 18 15 11 10 3 8 19 18 19 Test Example 9 Polymer 4 20 Resin 2 Before purification 143 118 125 200 313 345 330 149 141 246 383 268 After purification 10 17 7 4 14 6 6 3 20 2 12 5 Test Example 10 Polymer 5 20 Resin 3 Before purification 188 244 219 330 320 212 330 105 237 165 147 270 After purification 10 15 5 9 14 16 6 13 20 17 13 17 Test Example 11 Polymer 6 20 Resin 1 Before purification 266 341 111 187 186 137 231 122 350 130 295 280 After purification 15 6 9 18 18 8 3 6 18 11 6 18 Test Example 12 CDC-G 20 Resin 2 Before purification 223 64 twenty three 18 213 3 3 twenty one 2 638 1 3 After purification 6 19 7 5 19 12 5 7 15 18 18 5 Test Example 13 CDC-G 20 Resin 3 Before purification 223 64 twenty three 18 213 3 3 twenty one 2 638 1 3 After purification 6 18 8 4 20 16 7 17 5 20 18 12

從表8的結果確認到，實施使用螯合樹脂從包含特定的螯合劑之原料去除金屬之金屬去除步驟，藉此獲得了金屬含量顯著降低之純化物。尤其，確認到作為試驗例1～13實施之金屬處理步驟中所獲得之任意純化物中的Ca的含量均高於Na的含量。It was confirmed from the results in Table 8 that a metal removal step of removing metals from raw materials containing specific chelating agents using chelating resins was performed, thereby obtaining a purified product with a significantly reduced metal content. In particular, it was confirmed that the content of Ca in any purified product obtained in the metal treatment steps implemented as Test Examples 1 to 13 was higher than the content of Na.

〔試劑盒的製作〕 使用在上述金屬去除步驟中獲得之純化物，製備了包含水及各螯合劑之第2液，除此以外，依據實施例B-1～B-19中所記載之方法，製作了具備用於製備處理液之第1液及第2液之試劑盒。所製作之試劑盒均相當於上述試劑盒A。 另外，第1液及第2液的製備中，調節了第1液及第2液中所包含之各成分的含量，以使混合第1液及第2液而獲得之處理液中所包含之各成分具有表9所示之含量（均為相對於處理液的總質量之質量基準）。 又，表9中，關於“螯合劑”的“化合物”欄的“CDC-G（1）”、“CDC-G（2）”及“CDC-G（3）”，在各實施例中示出藉由上述試驗例1、12及13獲得之純化物中所包含之CDC-G製備處理液。[Making of the kit] Using the purified product obtained in the above metal removal step, a second liquid containing water and each chelating agent was prepared. In addition, according to the method described in Examples B-1 to B-19, A kit for preparing the first solution and the second solution of the treatment solution. The kits made are equivalent to kit A mentioned above. In addition, in the preparation of the first liquid and the second liquid, the content of each component contained in the first liquid and the second liquid was adjusted so that the processing liquid obtained by mixing the first liquid and the second liquid contained Each component has the content shown in Table 9 (all are quality standards relative to the total mass of the treatment liquid). In addition, in Table 9, the "CDC-G(1)", "CDC-G(2)" and "CDC-G(3)" in the "compound" column of the "chelating agent" are shown in each example. The CDC-G preparation treatment liquid contained in the purified product obtained by the above test examples 1, 12, and 13 was prepared.

〔處理液的製備〕 混合經製備之第1液及第2液，分別製備了實施例D-1～D-19的處理液。各處理液中的各成分的含量（均為相對於處理液的總質量之質量基準）如表9中所記載。 示於表9之各成分均使用分類成半導體水準者或分類成以其為基準之高純度水準者。〔Preparation of treatment liquid〕 The prepared first liquid and second liquid were mixed to prepare the treatment liquids of Examples D-1 to D-19, respectively. The content of each component in each treatment liquid (all are quality standards relative to the total mass of the treatment liquid) are as described in Table 9. Each component shown in Table 9 is classified into a semiconductor level or a high purity level based on it.

表9中，“金屬成分”的“Na（ppb）”欄及“Ca（ppb）”欄表示處理液中所包含之Na成分及Ca成分的含量（單位：質量ppb）。 表9中，“比例3”欄表示Ca成分的含量與Na成分的含量之比例（Ca成分/Na成分、質量比）。 除了表9中的上述以外的欄的含義分別與表5中所對應之欄的含義相同。In Table 9, the "Na (ppb)" column and the "Ca (ppb)" column of the "metal component" indicate the content (unit: mass ppb) of the Na component and the Ca component contained in the treatment liquid. In Table 9, the “ratio 3” column indicates the ratio of the content of the Ca component to the content of the Na component (Ca component/Na component, mass ratio). The meanings of the columns other than the above in Table 9 are the same as those of the corresponding columns in Table 5.

〔評價〕 關於經製備之實施例D-1～D-19的處理液，以與實施例B-1～B-19相同的方式評價了耐腐蝕性、殘渣去除性及缺陷抑制性。 表9中示出了耐腐蝕性的測量結果以及耐腐蝕性、殘渣去除性及缺陷抑制性的評價結果。〔Evaluation〕 Regarding the prepared treatment liquids of Examples D-1 to D-19, corrosion resistance, residue removal properties, and defect suppression properties were evaluated in the same manner as in Examples B-1 to B-19. Table 9 shows the measurement results of corrosion resistance and the evaluation results of corrosion resistance, residue removal properties, and defect suppression properties.

[表13] 表9 處理液的組成 水 有機溶劑A 有機溶劑B 比例1 去除劑 螯合劑 HA化合物 第1液 第2液 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 化合物 量 （%） 試劑盒 實施例D-1 87.43% 1.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G（1） 0.001% 2 HA 5.00% 1 實施例D-2 81.96% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 實施例D-3 88.66% 0.10% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G（1） 0.025% 2 HA 5.00% 1 實施例D-4 68.64% 20.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G（1） 0.050% 2 HA 5.00% 1 實施例D-5 68.34% 20.00% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 精胺酸 0.300% 2 HA 5.00% 1 實施例D-6 80.80% 5.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 實施例D-7 82.79% 5.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 TBG 0.700% 2 HA 5.00% 1 實施例D-8 86.86% 1.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子5 0.100% 2 HA 5.00% 1 實施例D-9 83.61% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子6 0.100% 2 HA 5.00% 1 實施例D-10 87.41% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.025% 2 HA 5.00% 1 實施例D-11 87.34% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子1 0.100% 2 HA 5.00% 1 實施例D-12 83.29% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子2 0.100% 2 HA 5.00% 1 實施例D-13 78.34% 10.00% EGBE 5.0% 2 b-5 0.001% 2 5.0E+03 DTPA 0.60% 1 高分子3 0.100% 2 HA 5.00% 1 實施例D-14 83.40% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子4 0.100% 2 HA 5.00% 1 實施例D-15 87.45% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G（2） 0.050% 2 HA 5.00% 1 實施例D-16 87.14% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 高分子5 0.050% 2 HA 5.00% 1 實施例D-17 58.80% 30.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.050% 2 HA 5.00% 1 實施例D-18 78.75% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G（1） 0.050% 2 HA 5.00% 1 實施例D-19 78.80% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G（3） 0.050% 2 HA 5.00% 1 [Table 13] Table 9 Composition of treatment liquid water Organic solvent A Organic solvent B Scale 1 Remover Chelating agent HA compound The first solution The second solution Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Compound the amount(%) Reagent test kit Example D-1 87.43% 1.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G (1) 0.001% 2 HA 5.00% 1 Example D-2 81.96% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 Example D-3 88.66% 0.10% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 CDC-G (1) 0.025% 2 HA 5.00% 1 Example D-4 68.64% 20.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G (1) 0.050% 2 HA 5.00% 1 Example D-5 68.34% 20.00% EGBE 5.0% 1 b-5 0.010% 1 5.0E+02 DTPA 0.60% 1 Arginine 0.300% 2 HA 5.00% 1 Example D-6 80.80% 5.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 PBG 1.000% 2 HA 5.00% 1 Example D-7 82.79% 5.00% EGBE 5.0% 1 b-7 0.010% 1 5.0E+02 DTPA 0.60% 1 TBG 0.700% 2 HA 5.00% 1 Example D-8 86.86% 1.00% EGBE 5.0% 1 b-9 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 5 0.100% 2 HA 5.00% 1 Example D-9 83.61% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 6 0.100% 2 HA 5.00% 1 Example D-10 87.41% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.025% 2 HA 5.00% 1 Example D-11 87.34% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 1 0.100% 2 HA 5.00% 1 Example D-12 83.29% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 2 0.100% 2 HA 5.00% 1 Example D-13 78.34% 10.00% EGBE 5.0% 2 b-5 0.001% 2 5.0E+03 DTPA 0.60% 1 Polymer 3 0.100% 2 HA 5.00% 1 Example D-14 83.40% 5.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 4 0.100% 2 HA 5.00% 1 Example D-15 87.45% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G (2) 0.050% 2 HA 5.00% 1 Example D-16 87.14% 1.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 Polymer 5 0.050% 2 HA 5.00% 1 Example D-17 58.80% 30.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-Cl 0.050% 2 HA 5.00% 1 Example D-18 78.75% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G (1) 0.050% 2 HA 5.00% 1 Example D-19 78.80% 10.00% EGBE 5.0% 1 b-5 0.001% 1 5.0E+03 DTPA 0.60% 1 CDC-G (3) 0.050% 2 HA 5.00% 1

[表14] 表9 （續） 處理液的組成 處理液的pH 鹼性化合物 Co離子 比例2 防腐蝕劑 金屬成分 化合物 量 （%） 試劑盒 Co離子源 量 （ppt） 試劑盒 化合物 量 （%） 試劑盒 Na （ppb） Ca （ppb） 比例3 （Ca/Na） 實施例D-1 DBU 0.76% 1         5MBTA 0.20% 1 0.9 0.3 0.3 8.5 實施例D-2 TBAH 1.24% 1         5MBTA 0.20% 1 0.8 0.9 1.1 8.7 實施例D-3 MEA 0.41% 1         5MBTA 0.20% 1 0.9 0.9 1.0 8.6 實施例D-4 TMAH 0.51% 1 Co（OH）2 10.0 1 1.0E+08 5MBTA 0.20% 1 1.2 1.1 0.9 8.9 實施例D-5 AMP 0.55% 1         5MBTA 0.20% 1 1.5 0.7 0.5 7.5 實施例D-6 AEEA 2.40% 1         5MBTA 0.20% 1 0.9 1 1.1 8.0 實施例D-7 DBU 0.70% 2         5MBTA 0.20% 1 2.1 1.1 0.5 7.5 實施例D-8 TBAH 1.24% 1         5MBTA 0.20% 1 1.3 1.3 1.0 8.1 實施例D-9 TMAH 0.49% 2         5MBTA 0.20% 1 1.1 1.1 1.0 8.2 實施例D-10 DBU 0.76% 2         5MBTA 0.20% 1 0.9 0.75 0.8 8.2 實施例D-11 DBU 0.76% 1 Co（OH）2 20.0 2 5.0E+07 5MBTA 0.20% 1 1.5 5 3.3 8.5 實施例D-12 DBU 0.81% 1         5MBTA 0.20% 1 1.5 15 10.0 8.2 實施例D-13 DBU 0.76% 1         5MBTA 0.20% 2 2.5 0.3 0.1 8.7 實施例D-14 DBU 0.70% 1         5MBTA 0.20% 1 0.4 0.1 0.3 8.4 實施例D-15 DBA 0.70% 1         5MBTA 0.20% 1 0.6 0.7 1.2 8.4 實施例D-16 TBA 1.01% 1         5MBTA 0.20% 1 0.8 0.7 0.9 8.4 實施例D-17 BzTMAH 0.35% 2         5MBTA 0.20% 1 0.9 0.8 0.9 8.4 實施例D-18 TBAH 0.40% 1         5MBTA 0.20% 1 1.2 1.2 1.0 7.7 實施例D-19 TMAH 0.35% 1         5MBTA 0.20% 1 1.3 1.4 1.1 7.5 [Table 14] Table 9 (continued) Composition of treatment liquid PH of the treatment solution Basic compound Co ion Scale 2 Anti-corrosion agent Metal composition Compound the amount(%) Reagent test kit Co ion source Quantity (ppt) Reagent test kit Compound the amount(%) Reagent test kit Na (ppb) Ca (ppb) Ratio 3 (Ca/Na) Example D-1 DBU 0.76% 1 5MBTA 0.20% 1 0.9 0.3 0.3 8.5 Example D-2 TBAH 1.24% 1 5MBTA 0.20% 1 0.8 0.9 1.1 8.7 Example D-3 MEA 0.41% 1 5MBTA 0.20% 1 0.9 0.9 1.0 8.6 Example D-4 TMAH 0.51% 1 Co(OH) 2 10.0 1 1.0E+08 5MBTA 0.20% 1 1.2 1.1 0.9 8.9 Example D-5 AMP 0.55% 1 5MBTA 0.20% 1 1.5 0.7 0.5 7.5 Example D-6 AEEA 2.40% 1 5MBTA 0.20% 1 0.9 1 1.1 8.0 Example D-7 DBU 0.70% 2 5MBTA 0.20% 1 2.1 1.1 0.5 7.5 Example D-8 TBAH 1.24% 1 5MBTA 0.20% 1 1.3 1.3 1.0 8.1 Example D-9 TMAH 0.49% 2 5MBTA 0.20% 1 1.1 1.1 1.0 8.2 Example D-10 DBU 0.76% 2 5MBTA 0.20% 1 0.9 0.75 0.8 8.2 Example D-11 DBU 0.76% 1 Co(OH) 2 20.0 2 5.0E+07 5MBTA 0.20% 1 1.5 5 3.3 8.5 Example D-12 DBU 0.81% 1 5MBTA 0.20% 1 1.5 15 10.0 8.2 Example D-13 DBU 0.76% 1 5MBTA 0.20% 2 2.5 0.3 0.1 8.7 Example D-14 DBU 0.70% 1 5MBTA 0.20% 1 0.4 0.1 0.3 8.4 Example D-15 DBA 0.70% 1 5MBTA 0.20% 1 0.6 0.7 1.2 8.4 Example D-16 TBA 1.01% 1 5MBTA 0.20% 1 0.8 0.7 0.9 8.4 Example D-17 BzTMAH 0.35% 2 5MBTA 0.20% 1 0.9 0.8 0.9 8.4 Example D-18 TBAH 0.40% 1 5MBTA 0.20% 1 1.2 1.2 1.0 7.7 Example D-19 TMAH 0.35% 1 5MBTA 0.20% 1 1.3 1.4 1.1 7.5

[表15] 表9 （續） 耐腐蝕性 殘渣去除性 缺陷抑制性 Co W SiO2 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 測量值 （Å/分鐘） 評價 實施例D-1 0.1 S 0.5 A 0.1 S S S 實施例D-2 0.2 S 0.1 S 0.3 S S S 實施例D-3 0.1 S 0.05 S 0.2 S S S 實施例D-4 0.2 S 0.05 S 0.3 S S S 實施例D-5 0.1 S 0.8 A 0.8 A S S 實施例D-6 0.1 S 0.1 S 0.2 S S S 實施例D-7 0.1 S 0.7 A 0.2 S S A 實施例D-8 0.1 S 0.05 S 0.3 S S S 實施例D-9 0.1 S 0.05 S 0.2 S S S 實施例D-10 0.1 S 0.05 S 0.2 S S S 實施例D-11 0.1 S 0.05 S 0.2 S S A 實施例D-12 0.1 S 0.1 S 0.2 S S A 實施例D-13 0.1 S 0.1 S 0.2 S A S 實施例D-14 0.1 S 0.1 S 0.2 S A S 實施例D-15 0.1 S 0.15 S 0.2 S S S 實施例D-16 0.1 S 0.1 S 0.2 S S S 實施例D-17 0.1 S 0.1 S 0.2 S S S 實施例D-18 0.1 S 0.1 S 0.2 S S S 實施例D-19 0.1 S 0.15 S 0.2 S S S [Table 15] Table 9 (continued) Corrosion resistance Residue removal Defect inhibition Co W SiO 2 Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Measurement value (Å/min) Evaluation Example D-1 0.1 S 0.5 A 0.1 S S S Example D-2 0.2 S 0.1 S 0.3 S S S Example D-3 0.1 S 0.05 S 0.2 S S S Example D-4 0.2 S 0.05 S 0.3 S S S Example D-5 0.1 S 0.8 A 0.8 A S S Example D-6 0.1 S 0.1 S 0.2 S S S Example D-7 0.1 S 0.7 A 0.2 S S A Example D-8 0.1 S 0.05 S 0.3 S S S Example D-9 0.1 S 0.05 S 0.2 S S S Example D-10 0.1 S 0.05 S 0.2 S S S Example D-11 0.1 S 0.05 S 0.2 S S A Example D-12 0.1 S 0.1 S 0.2 S S A Example D-13 0.1 S 0.1 S 0.2 S A S Example D-14 0.1 S 0.1 S 0.2 S A S Example D-15 0.1 S 0.15 S 0.2 S S S Example D-16 0.1 S 0.1 S 0.2 S S S Example D-17 0.1 S 0.1 S 0.2 S S S Example D-18 0.1 S 0.1 S 0.2 S S S Example D-19 0.1 S 0.15 S 0.2 S S S

另外，實施例D-1～D-19的處理液中所包含之金屬成分的含量的總計係5～100質量ppb。 關於實施例D-1～D-19的處理液中的各金屬成分的含量，依據作為實施例1～31中處理液所包含之鈷離子含量的測量方法記載之方法測量。In addition, the total content of the metal components contained in the treatment liquids of Examples D-1 to D-19 was 5-100 mass ppb. The content of each metal component in the treatment liquids of Examples D-1 to D-19 was measured according to the method described as the method for measuring the content of cobalt ion contained in the treatment liquids of Examples 1 to 31.

從表9確認到，使用具備包含羥胺化合物之第1液及含有螯合劑中的至少1種之第2液之試劑盒製備之實施例D-1～D-19的處理液亦與實施例B-1～B-19的處理液相同地，具有相對於Co膜、W膜及SiO2 膜之優異之耐腐蝕性，並且殘渣去除性及缺陷抑制性優異。It was confirmed from Table 9 that the treatment solutions of Examples D-1 to D-19 prepared using the kit provided with the first solution containing the hydroxylamine compound and the second solution containing at least one of the chelating agents are also the same as those of Example B Similarly, the treatment liquids of -1 to B-19 have excellent corrosion resistance with respect to the Co film, W film, and SiO 2 film, and are excellent in residue removal and defect suppression.

又，從表5及表9確認到，實施了使用螯合樹脂從包含螯合劑之原料去除金屬之金屬去除步驟，並使用所獲得之純化之後的螯合劑製備之處理液相對於W膜之耐腐蝕性更優異（實施例D-1～D-19與實施例B-1～B-19的比較）。In addition, from Tables 5 and 9, it was confirmed that the metal removal step of removing metals from the raw material containing the chelating agent using a chelating resin was implemented, and the treatment liquid phase prepared using the obtained purified chelating agent was resistant to the W film. Corrosion is more excellent (comparison of Examples D-1 to D-19 and Examples B-1 to B-19).

1:基板 2:金屬層 3:蝕刻停止層 4:層間絕緣膜 5:金屬硬遮罩 6:孔 10:積層體 11:內壁 11a:截面壁 11b:底壁 12:乾式蝕刻殘渣1: substrate 2: metal layer 3: Etch stop layer 4: Interlayer insulating film 5: Metal hard mask 6: Hole 10: Laminated body 11: inner wall 11a: Sectional wall 11b: bottom wall 12: Dry etching residue

圖1係表示作為基板的清洗方法的清洗對象物之積層體的一例之剖面示意圖。Fig. 1 is a schematic cross-sectional view showing an example of a laminate of a cleaning target as a substrate cleaning method.

1:基板1: substrate

2:金屬層2: metal layer

3:蝕刻停止層3: Etch stop layer

4:層間絕緣膜4: Interlayer insulating film

5:金屬硬遮罩5: Metal hard mask

6:孔6: Hole

10:積層體10: Laminated body

11:內壁11: inner wall

11a:截面壁11a: Sectional wall

11b:底壁11b: bottom wall

12:乾式蝕刻殘渣12: Dry etching residue

Claims (31)

一種處理液，其係半導體器件用處理液，其係包含水及有機溶劑， 前述有機溶劑係由有機溶劑A及有機溶劑B構成之組合，且至少包含下述的組合1～組合6中的任一個之組合， pH係5以上， 組合1：前述有機溶劑A係乙二醇單丁醚，前述有機溶劑B係選自包括1-二級丁氧基丁烷、1-（2-丁氧基乙氧基）乙烷-1-醇、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、（2-丁氧基乙氧基）乙酸、3,6,9,12-四氧十六烷-1-醇、甘油、十八醇及二（2-丁氧基）甲烷之群組B1中之至少1種之組合， 組合2：前述有機溶劑A係二乙二醇單丁醚，前述有機溶劑B係選自包括1-二級丁氧基丁烷、1-（2-丁氧基乙氧基）乙烷-1-醇、1-（（2-丁氧基乙氧基）甲氧基）丁烷、1-（2-（乙氧基甲氧基）乙氧基）丁烷、（2-丁氧基乙氧基）乙酸、3,6,9,12-四氧十六烷-1-醇、甘油、十八醇及二（2-丁氧基）甲烷之群組B2中之至少1種之組合， 組合3：前述有機溶劑A係二甲基亞碸，前述有機溶劑B係選自包括二甲基二硫醚、二甲基硫醚及二甲基碸二甲基二硫醚之群組B3中之至少1種之組合， 組合4：前述有機溶劑A係環丁碸，前述有機溶劑B係選自包括3-環丁烯碸及二甲基亞碸之群組B4中之至少1種之組合， 組合5：前述有機溶劑A係丙二醇，前述有機溶劑B係甘油之組合， 組合6：前述有機溶劑A係伸己基二醇，前述有機溶劑B係選自包括丙酮及二丙酮醇之群組B6中之至少1種之組合。A treatment liquid, which is a treatment liquid for semiconductor devices, which contains water and an organic solvent, The aforementioned organic solvent is a combination of organic solvent A and organic solvent B, and includes at least any one of the following combinations 1 to 6, pH is above 5, Combination 1: The aforementioned organic solvent A is ethylene glycol monobutyl ether, and the aforementioned organic solvent B is selected from the group including 1-secondary butoxybutane, 1-(2-butoxyethoxy)ethane-1- Alcohol, 1-((2-butoxyethoxy)methoxy)butane, 1-(2-(ethoxymethoxy)ethoxy)butane, (2-butoxyethoxy) A combination of at least one of the group B1 of acetic acid, 3,6,9,12-tetraoxyhexadecane-1-ol, glycerin, stearyl alcohol and bis(2-butoxy)methane, Combination 2: The aforementioned organic solvent A is diethylene glycol monobutyl ether, and the aforementioned organic solvent B is selected from the group consisting of 1-secondary butoxybutane and 1-(2-butoxyethoxy)ethane-1 -Alcohol, 1-((2-butoxyethoxy)methoxy)butane, 1-(2-(ethoxymethoxy)ethoxy)butane, (2-butoxyethyl) A combination of at least one of the group B2 of oxy)acetic acid, 3,6,9,12-tetraoxyhexadecane-1-ol, glycerin, stearyl alcohol and bis(2-butoxy)methane, Combination 3: The aforementioned organic solvent A is dimethyl sulfide, and the aforementioned organic solvent B is selected from the group B3 including dimethyl disulfide, dimethyl sulfide and dimethyl sulfide dimethyl disulfide A combination of at least one of them, Combination 4: The aforementioned organic solvent A is cyclobutane, and the aforementioned organic solvent B is a combination of at least one selected from the group B4 including 3-cyclobutene and dimethyl sulfide, Combination 5: The combination of the aforementioned organic solvent A is propylene glycol and the aforementioned organic solvent B is glycerin, Combination 6: The aforementioned organic solvent A is hexylene glycol, and the aforementioned organic solvent B is a combination of at least one selected from the group B6 including acetone and diacetone alcohol. 如請求項1所述之處理液，其中 作為前述組合1～組合6而包含於處理液中之前述有機溶劑A及前述有機溶劑B滿足前述有機溶劑A的含量與前述有機溶劑B的含量之比例以質量比計係1.0～1.0×104 之條件。The treatment liquid according to claim 1, wherein the organic solvent A and the organic solvent B contained in the treatment liquid as the combination 1 to 6 satisfy the ratio of the content of the organic solvent A to the content of the organic solvent B In terms of mass ratio, it is the condition of 1.0～1.0×10 4. 如請求項1或請求項2所述之處理液，其係還包含去除劑。The treatment liquid described in claim 1 or claim 2, which further contains a remover. 如請求項3所述之處理液，其中 前述去除劑包含選自包括氫氟酸、氟化銨、氟化四甲基銨、多元羧酸及聚胺基羧酸之群組中之至少1種。The treatment liquid described in claim 3, wherein The aforementioned remover includes at least one selected from the group consisting of hydrofluoric acid, ammonium fluoride, tetramethylammonium fluoride, polycarboxylic acid, and polyaminocarboxylic acid. 如請求項1或請求項2所述之處理液，其係還包含pH調節劑。The treatment liquid according to claim 1 or claim 2, which further contains a pH adjusting agent. 如請求項5所述之處理液，其中 前述pH調節劑包含選自包括含氮脂環化合物、氫氧化銨、水溶性胺、四級銨鹽、硫酸、鹽酸及乙酸之群組中之至少1種。The treatment liquid according to claim 5, wherein The aforementioned pH adjuster includes at least one selected from the group consisting of nitrogen-containing alicyclic compounds, ammonium hydroxide, water-soluble amines, quaternary ammonium salts, sulfuric acid, hydrochloric acid, and acetic acid. 如請求項1或請求項2所述之處理液，其係還包含鈷離子。The treatment liquid described in claim 1 or claim 2, which further contains cobalt ions. 如請求項7所述之處理液，其中 鈷離子係來源於選自包括氟化鈷、氯化鈷、氫氧化鈷、氧化鈷及硫酸鈷之群組中之至少1種鈷離子源之鈷離子。The treatment liquid described in claim 7, wherein The cobalt ion is derived from at least one cobalt ion source selected from the group consisting of cobalt fluoride, cobalt chloride, cobalt hydroxide, cobalt oxide, and cobalt sulfate. 如請求項7所述之處理液，其中 前述有機溶劑A的含量與前述鈷離子的含量之比例以質量比計係1.0×106 ～1.0×1010 。The treatment liquid according to claim 7, wherein the ratio of the content of the organic solvent A to the content of the cobalt ion is 1.0×10 6 to 1.0×10 10 in terms of mass ratio. 如請求項7所述之處理液，其中 前述水的含量相對於前述處理液的總質量係10.0質量%～98.0質量%， 前述有機溶劑的總含量相對於前述處理液的總質量係1.0質量%～90.0質量%， 前述鈷離子的含量相對於前述處理液的總質量係0.001質量ppb～1000質量ppb。The treatment liquid described in claim 7, wherein The content of the water is 10.0% to 98.0% by mass relative to the total mass of the treatment liquid, The total content of the aforementioned organic solvent is 1.0% to 90.0% by mass relative to the total mass of the aforementioned treatment liquid, The content of the cobalt ion is 0.001 mass ppb to 1,000 mass ppb relative to the total mass of the treatment liquid. 如請求項1或請求項2所述之處理液，其中 前述處理液中的Ca成分的含量與Na成分的含量之比例以質量比計係0.8～1.2。The treatment liquid described in claim 1 or claim 2, wherein The ratio of the content of the Ca component to the content of the Na component in the treatment liquid is 0.8 to 1.2 in terms of mass ratio. 如請求項1或請求項2所述之處理液，其係還包含選自包括羥胺、羥胺衍生物及該等鹽之群組中之至少1種羥胺化合物。The treatment liquid according to claim 1 or claim 2, which further contains at least one hydroxylamine compound selected from the group consisting of hydroxylamine, hydroxylamine derivatives, and these salts. 如請求項1或請求項2所述之處理液，其係還包含防腐蝕劑。The treatment liquid described in claim 1 or claim 2, which further contains an anti-corrosion agent. 如請求項13所述之處理液，其中 前述防腐蝕劑包含選自包括由下述式（A）表示之化合物、由下述式（B）表示之化合物、由下述式（C）表示之化合物及經取代或未經取代之四唑之群組中之至少1種化合物，
Figure 03_image020
式（A）中，R1A ～R5A 分別獨立地表示氫原子、經取代或未經取代之烴基、羥基、羧基或者經取代或未經取代之胺基，其中，結構中包含至少一個選自羥基、羧基及經取代或未經取代之胺基之基團， 式（B）中，R1B ～R4B 分別獨立地表示氫原子或者經取代或未經取代之烴基， 式（C）中，R1C 、R2C 及RN 分別獨立地表示氫原子或者經取代或未經取代之烴基，又，R1C 可以與R2C 鍵結而形成環。The treatment liquid according to claim 13, wherein the anticorrosive agent is selected from the group consisting of a compound represented by the following formula (A), a compound represented by the following formula (B), and a compound represented by the following formula (C) And at least one compound in the group of substituted or unsubstituted tetrazole,
Figure 03_image020
In formula (A), R 1A to R 5A each independently represent a hydrogen atom, a substituted or unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amine group, wherein the structure contains at least one selected from Groups of hydroxyl group, carboxyl group and substituted or unsubstituted amine group. In formula (B), R 1B to R 4B each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group. In formula (C), R 1C , R 2C and R N each independently represent a hydrogen atom or a substituted or unsubstituted hydrocarbon group, and R 1C may bond with R 2C to form a ring. 如請求項1或請求項2所述之處理液，其用作用於去除蝕刻殘渣的清洗液、用於去除圖案形成中所使用之光阻膜的溶液、用於從化學機械研磨後的基板去除殘渣的清洗液或蝕刻液。The processing solution described in claim 1 or claim 2, which is used as a cleaning solution for removing etching residues, a solution for removing photoresist films used in pattern formation, and for removing from a substrate after chemical mechanical polishing Residue cleaning solution or etching solution. 如請求項1或請求項2所述之處理液，其係還包含選自包括羥胺、羥胺衍生物及該等鹽之群組中之至少1種羥胺化合物以及螯合劑。The treatment liquid according to claim 1 or claim 2, which further contains at least one hydroxylamine compound selected from the group consisting of hydroxylamine, hydroxylamine derivatives, and these salts, and a chelating agent. 如請求項16所述之處理液，其中 與聚胺基聚羧酸不同，前述螯合劑包含具有至少2個含氮之基團之含氮螯合劑。The treatment liquid according to claim 16, wherein Different from the polyamine-based polycarboxylic acid, the aforementioned chelating agent includes a nitrogen-containing chelating agent having at least two nitrogen-containing groups. 如請求項17所述之處理液，其中 前述含氮螯合劑係選自由下述式（I）～式（IV）表示之化合物及它們的鹽之化合物， （R3 NH）C（R1 ）（R2 ）CO2 H   （I） 式（I）中，R1 及R2 分別獨立地表示氫原子、碳數1～4的烷基或具有至少一個含氮基之基團，R3 表示氫原子、碳數1～10的烷基或具有至少一個含氮基之基團，其中，R1 、R2 及R3 中的至少一個表示具有至少一個含氮基之基團，
Figure 03_image022
式（II）中，R10 、R11 、R12 及R13 分別獨立地表示氫原子、或選自包括經取代或未經取代之芳基、經取代或未經取代之碳數3～10的環狀烷基及經取代或未經取代之碳數1～10的直鏈狀或支鏈狀烷基之群組中之基團，R14 表示氫原子，其中，R10 、R11 、R12 及R13 中的至少一個表示經取代或未經取代之芳基或者表示作為取代基而具有芳基之基團，並且R10 、R11 、R12 及R13 中的至少2個表示氫原子，又，R13 與R14 可以彼此鍵結而形成咪唑環，
Figure 03_image024
式（III）中，m表示1～10的整數，R20 、R21 、R22 及R23 分別獨立地表示氫原子、或選自包括經取代或未經取代之芳基、經取代或未經取代之碳數3～10的環狀烷基及經取代或未經取代之碳數1～10的直鏈狀或支鏈狀烷基之群組中之基團，R24 表示氫原子、或選自包括經取代或未經取代之芳基、經取代或未經取代之苯基乙基及經取代或未經取代之苄基烷基之群組中之基團，m係2以上的整數之情況下，複數個R24 可以相同亦可以不同，其中，R20 、R21 、R22 、R23 及R24 中的至少一個表示經取代或未經取代之芳基或者表示作為取代基而具有芳基之基團，並且R20 、R21 、R22 及R23 中的至少2個表示氫原子，
Figure 03_image026
式（IV）中，n表示2以上的整數，複數個R25 分別獨立地表示氫原子或者經取代或未經取代之碳數1～6的烷基，複數個R26 分別獨立地表示經取代或未經取代之碳數1～20的伸烷基。The treatment liquid according to claim 17, wherein the nitrogen-containing chelating agent is selected from compounds represented by the following formulas (I) to (IV) and their salts, (R 3 NH)C(R 1 ) (R 2 ) CO 2 H (I) In formula (I), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a group having at least one nitrogen-containing group, and R 3 represents A hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a group having at least one nitrogen-containing group, wherein at least one of R 1 , R 2 and R 3 represents a group having at least one nitrogen-containing group,
Figure 03_image022
In the formula (II), R 10 , R 11 , R 12 and R 13 each independently represent a hydrogen atom, or are selected from the group including a substituted or unsubstituted aryl group, and a substituted or unsubstituted carbon number of 3-10 In the group of the cyclic alkyl group and the substituted or unsubstituted linear or branched chain alkyl group having 1 to 10 carbon atoms, R 14 represents a hydrogen atom, wherein R 10 , R 11 , At least one of R 12 and R 13 represents a substituted or unsubstituted aryl group or a group having an aryl group as a substituent, and at least two of R 10 , R 11 , R 12 and R 13 represent A hydrogen atom, and R 13 and R 14 can bond to each other to form an imidazole ring,
Figure 03_image024
In formula (III), m represents an integer of 1-10, and R 20 , R 21 , R 22 and R 23 each independently represent a hydrogen atom, or are selected from the group including substituted or unsubstituted aryl groups, substituted or unsubstituted A group in the group of substituted cyclic alkyl groups having 3 to 10 carbon atoms and substituted or unsubstituted linear or branched chain alkyl groups having 1 to 10 carbon atoms, where R 24 represents a hydrogen atom, Or a group selected from the group including substituted or unsubstituted aryl, substituted or unsubstituted phenylethyl and substituted or unsubstituted benzylalkyl, m is 2 or more In the case of an integer, a plurality of R 24 may be the same or different, wherein at least one of R 20 , R 21 , R 22 , R 23 and R 24 represents a substituted or unsubstituted aryl group or represents a substituent group And a group having an aryl group, and at least two of R 20 , R 21 , R 22 and R 23 represent a hydrogen atom,
Figure 03_image026
In the formula (IV), n represents an integer of 2 or more, a plurality of R 25 each independently represents a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbons, and a plurality of R 26 each independently represents a substituted Or unsubstituted alkylene having 1 to 20 carbons. 一種試劑盒，其係用於製備請求項16至請求項18之任一項所述之處理液，前述試劑盒中具備包含前述羥胺化合物之第1液及包含前述螯合劑中的至少1種之第2液， 水、前述有機溶劑A及前述有機溶劑B分別包含於前述第1液及前述第2液中的至少一者中。A kit for preparing the treatment solution described in any one of Claims 16 to 18, wherein the kit includes a first solution containing the hydroxylamine compound and at least one of the aforementioned chelating agents The second solution, Water, the organic solvent A, and the organic solvent B are contained in at least one of the first liquid and the second liquid, respectively. 一種試劑盒，其係具備請求項1至請求項18之任一項所述之處理液及選自包括水、異丙醇及包含氫氧化銨之溶劑之群組中之稀釋液。A kit is provided with the treatment liquid described in any one of claim 1 to claim 18 and a diluent selected from the group consisting of water, isopropanol, and a solvent containing ammonium hydroxide. 一種處理液的製造方法，其係製造請求項16至請求項18之任一項所述之處理液之方法，前述製造方法包括： 金屬去除步驟，從包含螯合劑之原料去除金屬來獲得包含前述螯合劑之純化物；及 處理液製備步驟，使用前述純化物中所包含之前述螯合劑來製備前述處理液。A method for manufacturing a treatment liquid, which is a method for manufacturing the treatment liquid described in any one of claim 16 to claim 18, the foregoing manufacturing method comprising: The metal removal step is to remove metals from the raw material containing the chelating agent to obtain a purified product containing the aforementioned chelating agent; and In the treatment liquid preparation step, the aforementioned chelating agent contained in the aforementioned purified product is used to prepare the aforementioned treatment liquid. 如請求項21所述之處理液的製造方法，其中 前述金屬去除步驟包括使前述原料通過選自包括螯合樹脂及離子交換樹脂之群組中之至少一個樹脂之步驟。The manufacturing method of the treatment liquid according to claim 21, wherein The aforementioned metal removal step includes a step of passing the aforementioned raw material through at least one resin selected from the group consisting of a chelating resin and an ion exchange resin. 如請求項21或請求項22所述之處理液的製造方法，其中 前述純化物中的每個前述金屬成分的各金屬元素的含量與螯合劑的含量之比例以質量比計均係1.0×10-7 以下。The method for producing a treatment liquid according to claim 21 or claim 22, wherein the ratio of the content of each metal element of each of the aforementioned metal components in the aforementioned purified product to the content of the chelating agent is 1.0×10 by mass ratio. -7 or less. 一種基板的清洗方法，其係包括清洗步驟，前述清洗步驟使用請求項1至請求項18之任一項所述之處理液，對具備包含選自包括鈷、鎢及銅之群組中之至少1種金屬之金屬層之基板進行清洗。A method for cleaning a substrate, which includes a cleaning step. The aforementioned cleaning step uses the treatment solution described in any one of claim 1 to claim 18, and is provided with at least one selected from the group consisting of cobalt, tungsten, and copper. Clean the substrate of the metal layer of 1 metal. 如請求項24所述之清洗方法，其中 前述基板還具備包含選自包括銅、鈷、鈷合金、鎢、鎢合金、釕、釕合金、鉭、鉭合金、氧化鋁、氮化鋁、氮氧化鋁、鈦鋁、鈦、氮化鈦、氧化鈦、氧化鋯、氧化鉿、氧化鉭、氧化鑭及釔合金之群組中之至少1種成分之金屬硬遮罩。The cleaning method according to claim 24, wherein The aforementioned substrate further includes a substrate selected from the group consisting of copper, cobalt, cobalt alloy, tungsten, tungsten alloy, ruthenium, ruthenium alloy, tantalum, tantalum alloy, aluminum oxide, aluminum nitride, aluminum oxynitride, titanium aluminum, titanium, titanium nitride, A metallic hard mask of at least one component from the group of titanium oxide, zirconium oxide, hafnium oxide, tantalum oxide, lanthanum oxide, and yttrium alloy. 如請求項24或請求項25所述之清洗方法，其還包括沖洗步驟，前述沖洗步驟在前述清洗步驟之後，用水或包含異丙醇之沖洗液沖洗前述基板。The cleaning method according to claim 24 or claim 25, which further includes a rinsing step. After the rinsing step, the substrate is rinsed with water or a rinsing solution containing isopropanol. 如請求項26所述之清洗方法，其中 前述沖洗液還包含氫氧化銨。The cleaning method according to claim 26, wherein The aforementioned rinse liquid also contains ammonium hydroxide. 如請求項26所述之清洗方法，其還包括乾燥步驟，前述乾燥步驟在前述沖洗步驟之後，加熱前述基板而使其乾燥。The cleaning method according to claim 26, which further includes a drying step, and the drying step is followed by the rinsing step, heating the substrate to dry it. 一種基板的處理方法，其係對在表面具有金屬層之基板進行處理，前述基板的處理方法包括： 步驟P，實施液處理、使前述臭氧氣體與基板接觸之臭氧處理、前述基板在氧氣環境下的加熱處理或使用氧氣之前述基板的電漿處理，使前述金屬層的表層氧化而形成氧化金屬層，前述液處理係使選自包括水、過氧化氫水、氨水與過氧化氫水的混合水溶液、氟酸與過氧化氫水的混合水溶液、硫酸與過氧化氫水的混合水溶液、鹽酸與過氧化氫水的混合水溶液、溶氧水以及臭氧溶解水之群組中之藥液與前述基板的表面接觸；及 步驟Q，使請求項1至請求項18之任一項所述之處理液與在前述步驟P中形成之前述氧化金屬層的表面接觸且去除前述氧化金屬層。A method for processing a substrate, which is to process a substrate with a metal layer on the surface. The above-mentioned substrate processing method includes: Step P: Perform liquid treatment, ozone treatment in which the ozone gas is brought into contact with the substrate, heat treatment of the substrate in an oxygen atmosphere, or plasma treatment of the substrate using oxygen to oxidize the surface of the metal layer to form an oxide metal layer The aforementioned liquid treatment system is selected from the group consisting of water, hydrogen peroxide water, a mixed aqueous solution of ammonia and hydrogen peroxide, a mixed aqueous solution of hydrofluoric acid and hydrogen peroxide, a mixed aqueous solution of sulfuric acid and hydrogen peroxide, hydrochloric acid and peroxide The chemical solution in the group of a mixed aqueous solution of hydrogen oxide water, dissolved oxygen water, and ozone-dissolved water is in contact with the surface of the aforementioned substrate; and In step Q, the treatment liquid described in any one of claim 1 to claim 18 is brought into contact with the surface of the metal oxide layer formed in the step P, and the metal oxide layer is removed. 如請求項29所述之處理方法，其係依序反覆實施前述步驟P及前述步驟Q。The processing method described in claim 29 is to repeatedly implement the aforementioned step P and the aforementioned step Q in sequence. 如請求項29或請求項30所述之處理方法，其中 前述金屬層包含鈷、銅、鎢、鈦或鋁。The processing method described in claim 29 or 30, wherein The aforementioned metal layer includes cobalt, copper, tungsten, titanium, or aluminum.
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