TW201732914A - Method of storing process liquid for semiconductor device, and container filled with process liquid - Google Patents

Method of storing process liquid for semiconductor device, and container filled with process liquid Download PDF

Info

Publication number
TW201732914A
TW201732914A TW105140731A TW105140731A TW201732914A TW 201732914 A TW201732914 A TW 201732914A TW 105140731 A TW105140731 A TW 105140731A TW 105140731 A TW105140731 A TW 105140731A TW 201732914 A TW201732914 A TW 201732914A
Authority
TW
Taiwan
Prior art keywords
treatment liquid
processing liquid
group
mass
storage container
Prior art date
Application number
TW105140731A
Other languages
Chinese (zh)
Other versions
TWI716510B (en
Inventor
室祐継
高橋智美
高橋智威
清水哲也
吉井朗子
Original Assignee
富士軟片股份有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=59013161&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=TW201732914(A) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by 富士軟片股份有限公司 filed Critical 富士軟片股份有限公司
Publication of TW201732914A publication Critical patent/TW201732914A/en
Application granted granted Critical
Publication of TWI716510B publication Critical patent/TWI716510B/en

Links

Classifications

    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02299—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment
    • H01L21/02307—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer pre-treatment treatment by exposure to a liquid
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0073—Anticorrosion compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • H01L21/02104—Forming layers
    • H01L21/02107—Forming insulating materials on a substrate
    • H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
    • H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
    • H01L21/02343—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment treatment by exposure to a liquid
    • 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
    • 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
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3065—Plasma etching; Reactive-ion etching
    • 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
    • H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
    • H01L21/67005—Apparatus not specifically provided for elsewhere
    • H01L21/67011—Apparatus for manufacture or treatment
    • H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/22—Electronic devices, e.g. PCBs or semiconductors

Landscapes

  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plasma & Fusion (AREA)
  • Cleaning Or Drying Semiconductors (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Drying Of Semiconductors (AREA)
  • Weting (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)

Abstract

The objective of the present invention is to provide: a method for storing a treatment liquid for semiconductor devices containing at least one substance selected from among hydroxylamine and hydroxylamine salts, which is not susceptible to deterioration of the residue removal performance of the treatment liquid even if temperature environment change between cold storage and standing at room temperature is repeated; and a treatment-liquid containing body. A method for storing a treatment liquid for semiconductor devices according to the present invention stores a treatment liquid for semiconductor devices, which contains at least water and at least one substance selected from among hydroxylamine and hydroxylamine salts, in a storage container. According to this method for storing a treatment liquid for semiconductor devices, the void ratio within the storage container is set to 0.01-30% by volume. In this connection the void ratio is obtained by the following formula (1). Formula (1): Void ratio = {1 - (volume of treatment liquid for semiconductor devices within storage container)/(container volume of storage container)} * 100.

Description

半導體元件用處理液的保管方法、處理液收容器Storage method of processing liquid for semiconductor element, processing liquid container

本發明是有關於一種半導體元件用處理液的保管方法、處理液收容器。The present invention relates to a method for storing a processing liquid for a semiconductor element and a processing liquid container.

電荷耦合元件（Charge-Coupled Device，CCD）、記憶體等半導體元件是使用光微影技術，於基板上形成微細的電子電路圖案來製造。具體而言，將抗蝕劑膜塗佈於形成在基板上的成為配線材料的金屬膜（例如Co、W）、層間絕緣膜等的積層膜上，並經過光微影步驟・乾式蝕刻步驟（例如電漿蝕刻處理）來製造。 另外，視需要，於乾式蝕刻步驟後，藉由乾式灰化步驟（例如電漿灰化處理）等剝離手段，實施用以剝離主要源自光阻劑等有機物的成分的光阻劑剝離步驟。Semiconductor elements such as a charge-coupled device (CCD) and a memory are manufactured by forming a fine electronic circuit pattern on a substrate using photolithography. Specifically, the resist film is applied onto a laminated film of a metal film (for example, Co, W) to be a wiring material formed on a substrate, an interlayer insulating film, or the like, and subjected to a photolithography step and a dry etching step ( For example, plasma etching treatment) is manufactured. Further, if necessary, after the dry etching step, a photoresist peeling step for peeling off a component mainly derived from an organic substance such as a photoresist is performed by a peeling means such as a dry ashing step (for example, plasma ashing treatment).

經過乾式蝕刻步驟的基板於其金屬膜及層間絕緣膜上附著有作為含有金屬的殘渣物成分的乾式蝕刻殘渣物。因此，通常進行藉由具有強還原力、且可使金屬溶解化的處理液來洗淨去除該殘渣物的處理。 例如，於專利文獻1中揭示有一種於處理液中含有羥基胺作為還原劑的組成物。 [現有技術文獻] [專利文獻]The substrate subjected to the dry etching step has a dry etching residue as a metal-containing residue component adhered to the metal film and the interlayer insulating film. Therefore, the treatment for removing the residue by a treatment liquid having a strong reducing power and dissolving the metal is usually performed. For example, Patent Document 1 discloses a composition containing a hydroxylamine as a reducing agent in a treatment liquid. [Prior Art Document] [Patent Literature]

[專利文獻1]日本專利特開2012-195590號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2012-195590

[發明所欲解決之課題] 另一方面，本發明者等人對專利文獻1中所記載的含有羥基胺的處理液的經時性能進行研究的結果，發現存在殘渣物去除性能劣化的情況。 更具體而言，通常處理液於不使用時在規定溫度下冷藏保管，於使用時自冷藏保管取出處理液並恢復成室溫來使用。本發明者等人發現當重複實施將處理液冷藏保管規定時間後，將處理液於室溫下靜置規定時間的一連串的操作時，存在處理液的殘渣物去除性能劣化的情況。 因此，期望一種如即便存在如上所述的溫度環境變化，處理液的殘渣物去除性能的劣化亦得到抑制的保管方法。[Problems to be Solved by the Invention] On the other hand, the inventors of the present invention have studied the time-dependent performance of the hydroxylamine-containing treatment liquid described in Patent Document 1, and found that the residue removal performance is deteriorated. More specifically, the treatment liquid is usually stored at a predetermined temperature when not in use, and is taken out from the refrigerator at the time of use, and is returned to room temperature. The present inventors have found that when a series of operations in which the treatment liquid is allowed to stand at room temperature for a predetermined period of time after repeatedly storing the treatment liquid for a predetermined period of time is repeated, the residue removal performance of the treatment liquid may be deteriorated. Therefore, a storage method in which deterioration of the residue removal performance of the treatment liquid is suppressed even if there is a temperature environment change as described above is desired.

因此，本發明的課題在於提供一種半導體元件用處理液的保管方法、及處理液收容器，所述保管方法是含有選自羥基胺及羥基胺鹽中的任一種的半導體元件用處理液的保管方法，且即便重複冷藏保管及室溫靜置這一溫度環境變化，於處理液中亦難以產生殘渣物去除性能的劣化。 [解決課題之手段]In view of the above, it is an object of the present invention to provide a method for storing a processing liquid for a semiconductor element, and a processing liquid container for storing a processing liquid for a semiconductor element selected from any one of a hydroxylamine and a hydroxylamine salt. According to the method, even if the temperature environment changes during refrigerating storage and room temperature standing, the deterioration of the residue removal performance is less likely to occur in the treatment liquid. [Means for solving the problem]

本發明者等人為了達成所述課題而努力研究的結果，發現處理液的殘渣物去除性能的劣化與收容該處理液的保管容器內的空隙率相關，從而完成了本發明。 即，發現可藉由以下的構成來達成所述目的。As a result of intensive studies in order to achieve the above-mentioned problems, the present inventors have found that the deterioration of the residue removal performance of the treatment liquid is related to the void ratio in the storage container in which the treatment liquid is stored, and completed the present invention. That is, it was found that the object can be achieved by the following constitution.

（1） 一種半導體元件用處理液的保管方法，其於保管容器內保管至少含有選自羥基胺及羥基胺鹽中的至少任一種與水的半導體元件用處理液，且 將所述保管容器內的空隙率設為0.01體積%～30體積%。 再者，空隙率藉由以下的式（1）來求出。 式（1）：空隙率＝{1－（所述保管容器內的所述半導體元件用處理液的體積/所述保管容器的容器體積）}×100 （2） 如（1）所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有防腐蝕劑。 （3） 如（1）或（2）所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有選自水溶性有機溶劑及烷醇胺類中的至少一種。 （4） 如（1）至（3）中任一項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有四級氫氧化銨類。 （5） 如（1）至（4）中任一項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有氟化物。 （6） 如（1）至（5）中任一項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有螯合劑。 （7） 如（2）至（6）中任一項所述的半導體元件用處理液的保管方法，其中所述防腐蝕劑為選自由以下述式（A）～式（C）所表示的化合物所組成的群組中的至少一種。 （8） 如（1）至（7）中任一項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液的pH為6～11。 （9） 如（1）至（8）中任一項所述的半導體元件用處理液的保管方法，其中所述處理液中，相對於處理液總質量，所述選自羥基胺及羥基胺鹽中的至少任一種的總含量為1質量%～30質量%。 （10） 如（1）至（9）中任一項所述的半導體元件用處理液的保管方法，其中所述處理液中，Fe離子的含量為10質量ppt～10質量ppm。 （11） 一種處理液收容器，其包括保管容器、以及收容於所述保管容器內的至少含有選自羥基胺及羥基胺鹽中的至少任一種與水的半導體元件用處理液，且所述保管容器內的空隙率為0.01體積%～30體積%。 再者，空隙率藉由以下的式（1）來求出。 式（1）：空隙率＝{1－（所述保管容器內的所述半導體元件用處理液的體積/所述保管容器的容器體積）}×100 （12） 如（11）所述的處理液收容器，其中所述保管容器的內壁的材質為樹脂。 （13） 如（11）或（12）所述的處理液收容器，其中所述保管容器的內壁的材質為選自高密度聚乙烯、高密度聚丙烯、6,6-尼龍、四氟乙烯、四氟乙烯與全氟烷基乙烯基醚的共聚物、聚氯三氟乙烯、乙烯・氯三氟乙烯共聚物、乙烯・四氟乙烯共聚物、及四氟乙烯・六氟丙烯共聚物中的一種以上的樹脂。 （14） 如（11）至（13）中任一項所述的處理液收容器，其中所述保管容器的內壁的材質為分子內含有氟原子的氟系樹脂。 （15） 如（11）至（14）中任一項所述的處理液收容器，其中所述保管容器具有多個開口部。 [發明的效果](1) A method of storing a processing liquid for a semiconductor element, comprising storing a processing liquid for a semiconductor element containing at least one selected from the group consisting of hydroxylamine and hydroxylamine salt and water in a storage container, and storing the processing liquid in the storage container The void ratio is set to be 0.01% by volume to 30% by volume. Further, the void ratio is obtained by the following formula (1). (1): void ratio = {1 - (the volume of the processing liquid for semiconductor elements in the storage container / the container volume of the storage container)} × 100 (2) The semiconductor as described in (1) A method of storing a processing liquid for a device, wherein the processing liquid for a semiconductor element further contains an anticorrosive agent. (3) The method for storing a processing liquid for a semiconductor device according to the above aspect, wherein the processing liquid for a semiconductor element further contains at least one selected from the group consisting of a water-soluble organic solvent and an alkanolamine. (4) The method for storing a processing liquid for a semiconductor device according to any one of the above aspects, wherein the processing liquid for a semiconductor element further contains a quaternary ammonium hydroxide. (5) The method of storing a processing liquid for a semiconductor device according to any one of the invention, wherein the processing liquid for a semiconductor element further contains a fluoride. (6) The method of storing a processing liquid for a semiconductor device according to any one of the invention, wherein the processing liquid for a semiconductor element further contains a chelating agent. The method for storing a processing liquid for a semiconductor device according to any one of the above aspects, wherein the anticorrosive agent is selected from the group consisting of compounds represented by the following formulas (A) to (C) At least one of the group consisting of. The method for storing a processing liquid for a semiconductor device according to any one of the above aspects, wherein the pH of the processing liquid for a semiconductor device is 6 to 11. (9) The method of storing a processing liquid for a semiconductor device according to any one of (1) to (8), wherein the treatment liquid is selected from the group consisting of hydroxylamine and hydroxylamine with respect to the total mass of the treatment liquid. The total content of at least one of the salts is from 1% by mass to 30% by mass. (10) The method of storing a processing liquid for a semiconductor device according to any one of the invention, wherein the content of Fe ions in the treatment liquid is from 10 mass% to 10 mass ppm. (11) A treatment liquid container comprising: a storage container; and a treatment liquid for a semiconductor element containing at least one selected from the group consisting of hydroxylamine and hydroxylamine salt and water contained in the storage container, and The porosity in the storage container is from 0.01% by volume to 30% by volume. Further, the void ratio is obtained by the following formula (1). Formula (1): void ratio = {1 - (the volume of the processing liquid for semiconductor elements in the storage container / the container volume of the storage container)} × 100 (12) Processing as described in (11) The liquid container, wherein the inner wall of the storage container is made of a resin. (13) The treatment liquid container according to (11) or (12), wherein the inner wall of the storage container is made of a material selected from the group consisting of high density polyethylene, high density polypropylene, 6,6-nylon, and tetrafluoroethylene. Copolymer of ethylene, tetrafluoroethylene and perfluoroalkyl vinyl ether, polychlorotrifluoroethylene, ethylene/chlorotrifluoroethylene copolymer, ethylene/tetrafluoroethylene copolymer, and tetrafluoroethylene/hexafluoropropylene copolymer More than one of the resins. The processing liquid container according to any one of (11) to (13), wherein the material of the inner wall of the storage container is a fluorine-based resin containing fluorine atoms in the molecule. The treatment liquid container according to any one of (11) to (14), wherein the storage container has a plurality of openings. [Effects of the Invention]

根據本發明，可提供一種半導體元件用處理液的保管方法、及處理液收容器，所述保管方法是含有選自羥基胺及羥基胺鹽中的任一種的半導體元件用處理液的保管方法，且即便重複冷藏保管及室溫靜置這一溫度環境變化，於處理液中亦難以產生殘渣物去除性能的劣化。According to the present invention, there is provided a method of storing a processing liquid for a semiconductor element, and a processing liquid container, wherein the storage method is a method of storing a processing liquid for a semiconductor element selected from any one of a hydroxylamine and a hydroxylamine salt. Further, even if the temperature environment changes such as refrigerating storage and room temperature standing, the deterioration of the residue removal performance is less likely to occur in the treatment liquid.

以下，對本發明進行詳細說明。 以下所記載的構成要件的說明有時基於本發明的具有代表性的實施形態來進行，但本發明並不限定於此種實施形態。 再者，於本說明書中，使用「～」來表示的數值範圍是指包含「～」的前後所記載的數值作為下限值及上限值的範圍。 於本發明中，乾式蝕刻殘渣物是藉由進行乾式蝕刻（例如電漿蝕刻）所產生的副產物，例如是指源自光阻劑的有機物殘渣物、含有Si的殘渣物、及含有金屬的殘渣物。再者，於以下的說明中，有時亦將乾式蝕刻殘渣物簡稱為「殘渣物」。 另外，於本發明中，乾式灰化殘渣物是藉由進行乾式灰化（例如電漿灰化）所產生的副產物，例如是指源自光阻劑的有機物殘渣物、含有Si的殘渣物、及含有金屬的殘渣物。 另外，於本說明書中的基（原子群）的表述中，在無損本發明的效果的範圍內，未記載經取代及未經取代的表述包含不具有取代基的基（原子群），並且亦包含具有取代基的基（原子群）。例如，所謂「烴基」，不僅包含不具有取代基的烴基（未經取代的烴基），亦包含具有取代基的烴基（經取代的烴基）。各化合物的含義亦同樣如此。 另外，於本說明書中，當談及「準備」時，是指除對特定的材料進行合成或調合等來準備以外，包含藉由購入等來籌措規定的物質。Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be performed based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the present specification, the numerical range expressed by "~" means a range including the numerical values described before and after "~" as the lower limit and the upper limit. In the present invention, the dry etching residue is a by-product produced by dry etching (for example, plasma etching), and is, for example, an organic residue derived from a photoresist, a residue containing Si, and a metal-containing residue. Residue. Further, in the following description, the dry etching residue may be simply referred to as "residue". Further, in the present invention, the dry ashing residue is a by-product produced by dry ashing (for example, plasma ashing), for example, an organic residue derived from a photoresist, and a residue containing Si. And residues containing metals. Further, in the expression of the group (atomic group) in the present specification, in the range in which the effects of the present invention are not impaired, it is not described that the substituted and unsubstituted expressions include a group having no substituent (atomic group), and A group (atomic group) having a substituent is contained. For example, the "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). The same is true for each compound. In addition, in the present specification, the term "preparation" refers to a substance that is prepared by purchasing or the like in addition to preparation or blending of a specific material.

[半導體元件用處理液的保管方法] 本發明的半導體元件用處理液（以下亦稱為「處理液」）的保管方法是於保管容器內收容並保管至少含有選自羥基胺及羥基胺鹽中的至少任一種與水的半導體元件用處理液，且 將所述保管容器內的空隙率設為0.01體積%～30體積%者。 再者，空隙率藉由所述式（1）來求出。於後段中對（1）進行詳述。[Storage method of the processing liquid for semiconductor device] The method for storing the processing liquid for semiconductor device (hereinafter also referred to as "treatment liquid") in the storage container is stored in the storage container and contains at least one selected from the group consisting of hydroxylamine and hydroxylamine salt. At least one of the treatment liquids for the semiconductor element and the water is used, and the porosity in the storage container is set to 0.01% by volume to 30% by volume. Further, the void ratio is obtained by the above formula (1). (1) is described in detail in the following paragraph.

根據本發明的半導體元件用處理液的保管方法，即便重複冷藏保管及室溫靜置這一溫度環境變化，亦可抑制處理液的殘渣物去除性能的劣化。 雖然其詳細原因並不明確，但如以下般進行推測。 可認為處理液中的羥基胺（或羥基胺鹽）不僅藉由處理液中所含有的氧，亦藉由收容有處理液的保管容器中的無處理液的上部的空間中（或處理液與上部空間的界面）的氧而產生部分分解，並於處理液中生成規定的分解物（以後，亦稱為分解物X）。推斷藉由該分解物X以某種量存在於處理液中，而具有防止處理液的殘渣物去除性能的下降的效果。再者，雖然於後段中進行詳述，但處理液的殘渣物去除性能的下降可藉由製作構成殘渣物的成分的膜模型（model membrane），並觀察由處理液所引起的蝕刻速率的下降來確認。 於所述空隙率未滿0.01%的情況下，因原本不怎麼促進分解物X的生成，故作為結果，處理液中的分解物X的量少，而難以抑制處理液的性能下降。另一方面，推測於空隙率超過30%的情況下，雖然比較會生成分解物X，但所獲得的分解物X進一步分解，而容易變成其他分解物，若變成其他分解物，則無法獲得本發明的效果。 再者，如上所述，推測雖然重複冷藏保管與室溫靜置的處理來使用處理液的情況多，但於此種溫度環境變化的情況下，由所述空隙率所產生的影響特別大，容易產生處理液的性能差。According to the method for storing a processing liquid for a semiconductor device of the present invention, even if the temperature environment changes such as refrigerating storage and room temperature standing are repeated, deterioration of the residue removal performance of the processing liquid can be suppressed. Although the detailed reason is not clear, it is estimated as follows. It is considered that the hydroxylamine (or hydroxylamine salt) in the treatment liquid is not only the oxygen contained in the treatment liquid but also the space in the upper portion of the storage container in which the treatment liquid is contained (or the treatment liquid and Oxygen is partially decomposed at the interface of the upper space, and a predetermined decomposition product (hereinafter, also referred to as decomposition product X) is generated in the treatment liquid. It is estimated that the decomposition product X is present in the treatment liquid in a certain amount, and has an effect of preventing a decrease in the residue removal performance of the treatment liquid. Further, although detailed in the later stage, the deterioration of the residue removal performance of the treatment liquid can be obtained by forming a model membrane of the components constituting the residue, and observing the decrease in the etching rate caused by the treatment liquid. To confirm. When the porosity is less than 0.01%, the generation of the decomposition product X is not promoted originally, and as a result, the amount of the decomposition product X in the treatment liquid is small, and it is difficult to suppress the deterioration of the performance of the treatment liquid. On the other hand, when the porosity is more than 30%, it is presumed that the decomposition product X is formed in comparison, but the obtained decomposition product X is further decomposed and easily becomes another decomposition product, and if it becomes another decomposition product, the product cannot be obtained. The effect of the invention. In addition, as described above, it is presumed that there are many cases in which the treatment liquid is used in the process of refrigerating storage and standing at room temperature, but when the temperature environment changes, the influence of the void ratio is particularly large. It is easy to produce poor performance of the treatment liquid.

以下，對本發明中的處理液、保管容器及保管條件進行詳細說明。 （處理液） 本發明的處理液含有選自羥基胺及羥基胺鹽中的至少一種與水。Hereinafter, the treatment liquid, the storage container, and the storage conditions in the present invention will be described in detail. (Processing Liquid) The treatment liquid of the present invention contains at least one selected from the group consisting of hydroxylamine and hydroxylamine salt and water.

＜水＞ 本發明的處理液含有水作為溶劑。相對於處理液整體的質量，水的含量較佳為60質量%～98質量%，更佳為70質量%～95質量%。 作為水，較佳為用於半導體製造的超純水。雖然並無特別限定，但較佳為Fe、Co、Na、K、Ca、Cu、Mg、Mn、Li、Al、Cr、Ni、及Zn的金屬元素的離子濃度降低者，當用於本發明的處理液的調液時，較佳為調整成ppt級或其以下者。作為調整的方法，可列舉日本專利特開2011-110515號公報段落[0074]～段落[0084]中所記載的方法。<Water> The treatment liquid of the present invention contains water as a solvent. The content of water is preferably 60% by mass to 98% by mass, and more preferably 70% by mass to 95% by mass based on the mass of the entire processing liquid. As water, ultrapure water for semiconductor manufacturing is preferred. Although not particularly limited, it is preferred that the ion concentration of the metal elements of Fe, Co, Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn is lowered, and is used in the present invention. When the liquid of the treatment liquid is adjusted, it is preferably adjusted to a ppt level or lower. As a method of adjustment, the method described in paragraph [0074] to paragraph [0084] of JP-A-2011-110515 can be cited.

＜羥基胺化合物＞ 本發明的處理液含有選自羥基胺及羥基胺鹽中的至少一種。羥基胺及其鹽促進殘渣物的分解及可溶解化，進而具有處理對象物的防腐蝕效果。<Hydroxyamine Compound> The treatment liquid of the present invention contains at least one selected from the group consisting of a hydroxylamine and a hydroxylamine salt. Hydroxylamine and its salts promote the decomposition and solubilization of the residue, and further have an anticorrosive effect on the object to be treated.

此處，本發明的處理液的羥基胺及羥基胺鹽的「羥基胺」是指包含經取代或未經取代的烷基羥基胺等的廣義的羥基胺類，不論何者，均可獲得本申請案的效果。 作為羥基胺，並無特別限定，作為較佳的形態，可列舉未經取代的羥基胺及羥基胺衍生物。 作為羥基胺衍生物，並無特別限定，例如可列舉：O-甲基羥基胺、O-乙基羥基胺、N-甲基羥基胺、N,N-二甲基羥基胺、N,O-二甲基羥基胺、N-乙基羥基胺、N,N-二乙基羥基胺、N,O-二乙基羥基胺、O,N,N-三甲基羥基胺、N,N-二羧基乙基羥基胺、及N,N-二磺基乙基羥基胺等。 羥基胺的鹽較佳為所述羥基胺的無機酸鹽或有機酸鹽，更佳為Cl、S、N、及P等非金屬與氫進行鍵結而成的無機酸的鹽，特佳為選自由鹽酸、硫酸、及硝酸所組成的群組中的任一種酸的鹽。 作為用於形成本發明的處理液的羥基胺的鹽，較佳為羥基銨硝酸鹽（hydroxylammonium nitrate，亦稱為HAN）、羥基銨硫酸鹽（hydroxylammonium sulfate，亦稱為HAS）、羥基銨鹽酸鹽（hydroxylammonium chlorhydrate，亦稱為HAC）、羥基銨磷酸鹽、N,N-二乙基羥基銨硫酸鹽、N,N-二乙基羥基銨硝酸鹽、及該些的混合物。 另外，亦可使用羥基胺的有機酸鹽，可例示：羥基銨檸檬酸鹽、羥基銨草酸鹽、及氟化羥基銨等。 再者，本發明的處理液亦可為同時含有羥基胺及其鹽的形態。 羥基胺或羥基胺鹽可單獨使用，亦可適宜組合兩種以上來使用。 所述之中，就可顯著地獲得本發明的所期望的效果的觀點而言，較佳為羥基胺、或羥基銨硫酸鹽，更佳為羥基銨硫酸鹽。Here, the "hydroxylamine" of the hydroxylamine and the hydroxylamine salt of the treatment liquid of the present invention means a generalized hydroxylamine containing a substituted or unsubstituted alkylhydroxylamine, etc., and the present application can be obtained by any of the above. The effect of the case. The hydroxylamine is not particularly limited, and preferred examples thereof include an unsubstituted hydroxylamine and a hydroxylamine derivative. The hydroxylamine derivative is not particularly limited, and examples thereof include O-methylhydroxylamine, O-ethylhydroxylamine, N-methylhydroxylamine, N,N-dimethylhydroxylamine, and N,O- Dimethylhydroxylamine, N-ethylhydroxylamine, N,N-diethylhydroxylamine, N,O-diethylhydroxylamine, O,N,N-trimethylhydroxylamine, N,N-di Carboxyethylhydroxylamine, and N,N-disulfoethylhydroxylamine. The salt of the hydroxylamine is preferably a mineral acid salt or an organic acid salt of the hydroxylamine, more preferably a salt of a mineral acid in which a non-metal such as Cl, S, N, or P is bonded to hydrogen, particularly preferably A salt of any one of the groups consisting of hydrochloric acid, sulfuric acid, and nitric acid is selected. As the salt of the hydroxylamine for forming the treatment liquid of the present invention, preferred are hydroxylammonium nitrate (also referred to as HAN), hydroxylammonium sulfate (also known as HAS), and hydroxyammonium hydrochloride. Hydroxylammonium chlorhydrate (also known as HAC), hydroxyammonium phosphate, N,N-diethylhydroxyammonium sulfate, N,N-diethylhydroxyammonium nitrate, and mixtures thereof. Further, an organic acid salt of a hydroxylamine can also be used, and examples thereof include a hydroxylammonium citrate, a hydroxyammonium oxalate, and a fluorinated ammonium hydroxyphosphate. Further, the treatment liquid of the present invention may be in the form of a hydroxylamine and a salt thereof. The hydroxylamine or hydroxylamine salt may be used singly or in combination of two or more. Among them, from the viewpoint of remarkably obtaining the desired effect of the present invention, a hydroxylamine or a hydroxyammonium sulfate is preferred, and a hydroxyammonium sulfate is more preferred.

處理液中的羥基胺及其鹽的含量並無特別限制，但相對於本發明的處理液的總質量，較佳為0.01質量%～40質量%的範圍內，更佳為1質量%～30質量%，進而更佳為4質量%～25質量%，特佳為12質量%～18質量%。The content of the hydroxylamine and the salt thereof in the treatment liquid is not particularly limited, but is preferably in the range of 0.01% by mass to 40% by mass, and more preferably 1% by mass to 30% by mass based on the total mass of the treatment liquid of the present invention. The mass%, more preferably 4% by mass to 25% by mass, particularly preferably 12% by mass to 18% by mass.

＜氟化物＞ 本發明的處理液可含有氟化物。氟化物促進殘渣物的分解及可溶解化。 作為氟化物，並無特別限定，可列舉：氫氟酸（HF）、氟矽酸（H2 SiF6 ）、氟硼酸、氟矽酸銨鹽（(NH4 )2 SiF6 ）、六氟磷酸四甲基銨、氟化銨、氟化銨鹽、氟化氫銨鹽、由式NR4 BF4 所表示的四氟硼酸四級銨（例如四氟硼酸四甲基銨、四氟硼酸四乙基銨、四氟硼酸四丙基銨、及四氟硼酸四丁基銨（TBA-BF4 ）等）、及由式PR4 BF4 所表示的四氟硼酸四級鏻等。 氟化物可單獨使用，亦可適宜組合兩種以上來使用。 再者，於所述由式NR4 BF4 所表示的四氟硼酸四級銨及由式PR4 BF4 所表示的四氟硼酸四級鏻中，R相互可相同或不同。作為R，可列舉氫，直鏈、分支、或環狀的碳數1～6的烷基（例如甲基、乙基、丙基、丁基、戊基、及己基等），及碳數6～10的芳基等。該些可進一步含有取代基。 氟化物可單獨使用，亦可適宜組合兩種以上來使用。 所述之中，較佳為氟化銨、或氟矽酸。 當處理液含有氟化物時，相對於本發明的處理液的總質量，其含量較佳為0.01質量%～10質量%的範圍內，更佳為0.1質量%～5質量%，進而更佳為0.1質量%～1質量%。<Fluoride> The treatment liquid of the present invention may contain a fluoride. Fluoride promotes decomposition and solubilization of the residue. The fluoride is not particularly limited, and examples thereof include hydrofluoric acid (HF), fluoroantimonic acid (H 2 SiF 6 ), fluoroboric acid, ammonium fluoroantimonate ((NH 4 ) 2 SiF 6 ), and hexafluorophosphate. Tetramethylammonium, ammonium fluoride, ammonium fluoride salt, ammonium hydrogen fluoride salt, tetraammonium tetrafluoroborate represented by the formula NR 4 BF 4 (for example, tetramethylammonium tetrafluoroborate, tetraethylammonium tetrafluoroborate) And tetrapropylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate (TBA-BF 4 ), and the like, and tetradecyl tetrafluoroborate represented by the formula PR 4 BF 4 . Fluoride may be used singly or in combination of two or more. Further, in the quaternary ammonium tetrafluoroborate represented by the formula NR 4 BF 4 and the quaternary phosphonium tetrafluoroborate represented by the formula PR 4 BF 4 , R may be the same or different from each other. Examples of R include hydrogen, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, etc.), and a carbon number of 6 ～10 aryl and the like. These may further contain a substituent. Fluoride may be used singly or in combination of two or more. Among them, ammonium fluoride or fluoroantimonic acid is preferred. When the treatment liquid contains a fluoride, the content thereof is preferably in the range of 0.01% by mass to 10% by mass, more preferably 0.1% by mass to 5% by mass, even more preferably the total mass of the treatment liquid of the present invention. 0.1% by mass to 1% by mass.

＜Fe離子＞ 本發明者等人發現本發明的處理液中所含有的Fe離子的含量對各種性能具有大的影響。尤其，藉由選自羥基胺及其鹽中的至少任一種與Fe離子相互作用，本發明的所期望的效果變得顯著。通常，較佳為金屬離子少，但於本發明中，較佳為含有特定量的Fe離子。 本發明的處理液中，相對於本發明的處理液的總質量，Fe離子的含量較佳為10質量ppt～10質量ppm，更佳為1質量ppb～1質量ppm，進而更佳為1質量ppb～50質量ppb，特佳為1質量ppb～5質量ppb。 藉由在所述範圍內含有Fe離子，處理液的經時後的殘渣物去除性能的下降進一步得到抑制。 進而，以質量比計，相對於選自羥基胺及其鹽中的至少一種的含量（含有多種選自羥基胺及其鹽中的化合物時為其合計量），Fe離子的含量較佳為5×10-2 ～5×10-10 ，更佳為5×10-4 ～5×10-10 ，進而更佳為5×10-6 ～5×10-7 。藉由設為所述構成，處理液的殘渣物去除性能進一步提昇。<Fe ion> The inventors of the present invention found that the content of Fe ions contained in the treatment liquid of the present invention has a large influence on various properties. In particular, the desired effect of the present invention becomes remarkable by interacting with Fe ions by at least any one selected from the group consisting of hydroxylamines and salts thereof. In general, it is preferred that the metal ions are small, but in the present invention, it is preferred to contain a specific amount of Fe ions. In the treatment liquid of the present invention, the content of Fe ions is preferably from 10 mass% to 10 mass ppm, more preferably from 1 mass ppb to 1 mass ppm, and even more preferably 1 mass, based on the total mass of the treatment liquid of the present invention. Ppb ~ 50 mass ppb, particularly good for 1 mass ppb ~ 5 mass ppb. By containing Fe ions in the above range, the deterioration of the residue removal performance of the treatment liquid over time is further suppressed. Further, in terms of a mass ratio, the content of Fe ions is preferably 5 with respect to the content of at least one selected from the group consisting of hydroxylamines and salts thereof (including a plurality of compounds selected from the group consisting of hydroxylamines and salts thereof). ×10 -2 to 5 × 10 -10 , more preferably 5 × 10 -4 to 5 × 10 -10 , still more preferably 5 × 10 -6 to 5 × 10 -7 . With this configuration, the residue removal performance of the treatment liquid is further improved.

Fe離子通常是可作為雜質而包含於溶劑及藥劑等中的成分。因此，藉由蒸餾及離子交換樹脂等手段來對處理液中所含有的溶劑及/或製備後的處理液進行精製，藉此可製備成所期望的量。 處理液中的Fe離子的量可藉由感應耦合電漿質量分析裝置（橫河分析系統（Yokogawa Analytical Systems）製造，安捷倫（Agilent）7500cs型）來測定。The Fe ion is usually a component which can be contained as an impurity in a solvent, a drug, or the like. Therefore, the solvent contained in the treatment liquid and/or the treatment liquid after preparation can be purified by means of distillation, ion exchange resin, or the like, thereby preparing a desired amount. The amount of Fe ions in the treatment liquid can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent Model 7500cs).

＜防腐蝕劑＞ 本發明的處理液較佳為含有防腐蝕劑。防腐蝕劑具有消除成為配線膜的金屬（例如Co、W）的過度蝕刻的功能。 作為防腐蝕劑，並無特別限定，例如可列舉：1,2,4-三唑（Triazole，TAZ）、5-胺基四唑（Aminotetrazole，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、萘并三唑、1H-四唑-5-乙酸、2-巰基苯并噻唑（2-Mercaptobenzothiazole，2-MBT）、1-苯基-2-四氮唑-5-硫酮、2-巰基苯并咪唑（2-Mercaptobenzimidazole，2-MBI）、4-甲基-2-苯基咪唑、2-巰基噻唑啉、2,4-二胺基-6-甲基-1,3,5-三嗪、噻唑、咪唑、苯并咪唑、三嗪、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、二胺基甲基三嗪、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、磷酸三甲苯酯、吲唑、腺嘌呤、胞嘧啶、鳥嘌呤、胸腺嘧啶、磷酸酯抑制劑、胺類、吡唑類、丙硫醇、矽烷類、二級胺類、苯甲羥肟酸類、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、尿酸、乙基黃原酸鉀、甘胺酸、十二基膦酸、亞胺基二乙酸、酸、硼酸、丙二酸、丁二酸、氮基三乙酸、環丁碸、2,3,5-三甲基吡嗪、2-乙基-3,5-二甲基吡嗪、喹噁啉、乙醯基吡咯、噠嗪、組胺酸（histadine）、吡嗪、麩胱甘肽（還原型）、半胱胺酸、胱胺酸、噻吩、巰基吡啶N-氧化物、硫胺素HCl、四乙基秋蘭姆二硫化物、2,5-二巰基-1,3-噻二唑抗壞血酸、兒茶酚、第三丁基兒茶酚、苯酚、及五倍子酚等。<Anticorrosive Agent> The treatment liquid of the present invention preferably contains an anticorrosive agent. The anticorrosive agent has a function of eliminating excessive etching of a metal (for example, Co, W) which becomes a wiring film. The anticorrosive agent is not particularly limited, and examples thereof 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-amine 5--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, naphthotriazole, 1H-tetrazole- 5-acetic acid, 2-mercaptobenzothiazole (2-MBT), 1-phenyl-2-tetrazol-5-thione, 2-mercaptobenzimidazole (2-MBI) ), 4-methyl-2-phenylimidazole, 2-mercaptothiazoline, 2,4-diamino-6-methyl-1,3,5-triazine, thiazole, imidazole, benzimidazole, three Pyrazine, methyltetrazole, test thiol I, 1,3-dimethyl-2-imidazolidinone, 1,5-pentamethylenetetrazole, 1-phenyl-5-mercaptotetrazole, two Aminomethyltriazine, imidazolinthione, 4-methyl-4H-1,2,4-triazole-3-thiol, 5-amino-1,3,4-thiadiazole-2- Mercaptan, benzothiazole, tricresyl phosphate, carbazole, Anthraquinone, cytosine, guanine, thymine, phosphate inhibitor, amine, pyrazole, propanethiol, decane, secondary amine, benzoxamic acid, heterocyclic nitrogen inhibitor, citric acid Ascorbic acid, thiourea, 1,1,3,3-tetramethylurea, urea, urea derivatives, uric acid, potassium ethyl xanthate, glycine, dodecylphosphonic acid, iminodiacetic acid , acid, boric acid, malonic acid, succinic acid, nitrogen triacetic acid, cyclobutyl hydrazine, 2,3,5-trimethylpyrazine, 2-ethyl-3,5-dimethylpyrazine, quin Minoline, acetylpyrrole, pyridazine, histadine, pyrazine, glutathione (reduced), cysteine, cystine, thiophene, mercapto N-oxide, thiamine HCl, tetraethyl thiuram disulfide, 2,5-dimercapto-1,3-thiadiazole ascorbic acid, catechol, tert-butylcatechol, phenol, and gallic phenol.

進而，含有經取代或未經取代的苯并三唑作為防腐蝕劑亦較佳。作為經取代的苯并三唑，例如較佳為經烷基、芳基、鹵基、胺基、硝基、烷氧基、或羥基取代的苯并三唑。再者，經取代的苯并三唑亦可縮合1個以上的芳基（例如苯基）或雜芳基。Further, it is also preferred to contain a substituted or unsubstituted benzotriazole as an anticorrosive agent. As the substituted benzotriazole, for example, a benzotriazole substituted with an alkyl group, an aryl group, a halogen group, an amine group, a nitro group, an alkoxy group or a hydroxyl group is preferred. Further, the substituted benzotriazole may also condense one or more aryl groups (for example, a phenyl group) or a heteroaryl group.

除所述者以外，經取代或未經取代的苯并三唑例如可列舉：苯并三唑（Benzotriazole，BTA）、1-羥基苯并三唑、5-苯基硫醇-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、萘并三唑、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、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、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-第三丁基苯并三唑、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)苯并三唑等。 防腐蝕劑可單獨使用，亦可適宜組合兩種以上來使用。In addition to the above, substituted or unsubstituted benzotriazoles include, for example, Benzotriazole (BTA), 1-hydroxybenzotriazole, 5-phenylthiol-benzotriazole , 5-chlorobenzotriazole, 4-chlorobenzotriazole, 5-bromobenzotriazole, 4-bromobenzotriazole, 5-fluorobenzotriazole, 4-fluorobenzotriazole, naphthalene And triazole, tolyltriazole, 5-phenyl-benzotriazole, 5-nitrobenzotriazole, 4-nitrobenzotriazole, 2-(5-amino-pentyl)-benzene And triazole, 1-amino-benzotriazole, 5-methyl-1H-benzotriazole, benzotriazole-5-carboxylic acid, 4-methylbenzotriazole, 4-ethylbenzene And triazole, 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-methoxybenzotriazole, 5-hydroxybenzotriazole, dihydroxypropylbenzotriene Iridazole, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-benzotriazole 5-t-butylbenzotriazole, 5-(1',1'-dimethylpropyl)-benzotriazole, 5-(1',1',3'-trimethylbutyl) Benzotriazole, 5-n-octylbenzotriazole, and 5-(1',1',3',3'-tetramethylbutyl)benzotriazole, and the like. The anticorrosive agent may be used singly or in combination of two or more.

作為防腐蝕劑，其中較佳為選自由以下述式（A）～式（C）所表示的化合物、及經取代或未經取代的四唑所組成的群組中的至少一種，更佳為選自由以下述式（A）～式（C）所表示的化合物所組成的群組中的至少一種。The anticorrosive agent is preferably at least one selected from the group consisting of a compound represented by the following formula (A) to formula (C) and a substituted or unsubstituted tetrazole, more preferably selected. At least one of the group consisting of the compounds represented by the following formulas (A) to (C) is free.

[化1] [Chemical 1]

所述式（A）中，R1A ～R5A 分別獨立地表示氫原子、取代基或未經取代的烴基、羥基、羧基、或者經取代或未經取代的胺基。其中，於結構中含有至少1個選自羥基、羧基、及經取代或未經取代的胺基中的基。 所述式（B）中，R1B ～R4B 分別獨立地表示氫原子、取代基或未經取代的烴基。 所述式（C）中，R1C 、R2C 及RN 分別獨立地表示氫原子、取代基或未經取代的烴基。另外，R1C 與R2C 可鍵結而形成環。In the formula (A), R 1A to R 5A each independently represent a hydrogen atom, a substituent or an unsubstituted hydrocarbon group, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amine group. Wherein the structure contains at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amine group. In the formula (B), R 1B to R 4B each independently represent a hydrogen atom, a substituent or an unsubstituted hydrocarbon group. In the formula (C), R 1C , R 2C and R N each independently represent a hydrogen atom, a substituent or an unsubstituted hydrocarbon group. Further, R 1C and R 2C may be bonded to form a ring.

所述式（A）中，作為R1A ～R5A 所表示的烴基，可列舉：烷基（碳數較佳為1～12，更佳為1～6，特佳為1～3）、烯基（碳數較佳為2～12，更佳為2～6）、炔基（碳數較佳為2～12，更佳為2～6）、芳基（碳數較佳為6～22，更佳為6～14，進而更佳為6～10）、及芳烷基（碳數較佳為7～23，更佳為7～15，進而更佳為7～11）。 另外，作為取代基，例如可列舉：羥基、羧基、或者經取代或未經取代的胺基（作為取代基，較佳為碳數1～6的烷基，更佳為碳數1～3的烷基）。 再者，式（A）中，於結構中含有至少1個選自羥基、羧基、及經取代或未經取代的胺基（作為取代基，較佳為碳數1～6的烷基，更佳為碳數1～3的烷基）中的基。In the above formula (A), examples of the hydrocarbon group represented by R 1A to R 5A include an alkyl group (having a carbon number of preferably 1 to 12, more preferably 1 to 6, particularly preferably 1 to 3), and an alkene. The base (the number of carbon atoms is preferably 2 to 12, more preferably 2 to 6), the alkynyl group (the number of carbon atoms is preferably 2 to 12, more preferably 2 to 6), and the aryl group (the number of carbon atoms is preferably 6 to 22). More preferably, it is 6 to 14, more preferably 6 to 10), and an aralkyl group (the carbon number is preferably 7 to 23, more preferably 7 to 15, and still more preferably 7 to 11). Further, examples of the substituent include a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group (preferably, the substituent is preferably an alkyl group having 1 to 6 carbon atoms, more preferably a carbon number of 1 to 3). alkyl). Further, in the formula (A), at least one selected from the group consisting of a hydroxyl group, a carboxyl group, and a substituted or unsubstituted amino group (as a substituent, preferably an alkyl group having 1 to 6 carbon atoms) is contained in the structure. It is preferably a group in the alkyl group having 1 to 3 carbon atoms.

式（A）中，作為由R1A ～R5A 所表示的取代基或未經取代的烴基，例如可列舉：未經取代的碳數1～6的烴基，及經羥基、羧基或胺基取代的碳數1～6的烴基等。 作為由式（A）所表示的化合物，例如可列舉：1-硫甘油、L-半胱胺酸、及硫代蘋果酸等。In the formula (A), examples of the substituent represented by R 1A to R 5A or the unsubstituted hydrocarbon group include an unsubstituted hydrocarbon group having 1 to 6 carbon atoms and a substitution with a hydroxyl group, a carboxyl group or an amine group. A hydrocarbon group having 1 to 6 carbon atoms or the like. Examples of the compound represented by the formula (A) include 1-thioglycerol, L-cysteine, and thiomalic acid.

式（B）中，作為由R1B ～R4B 所表示的烴基及取代基，其含義分別與所述式（A）的R1A ～R5A 所表示的烴及取代基相同。作為由R1B ～R4B 所表示的取代基或未經取代的烴基，例如可列舉：甲基、乙基、丙基、及第三丁基等碳數1～6的烴基。 作為由式（B）所表示的化合物，例如可列舉：兒茶酚、及第三丁基兒茶酚等。In the formula (B), the hydrocarbon group and the substituent represented by R 1B to R 4B have the same meanings as the hydrocarbon and the substituent represented by R 1A to R 5A of the formula (A), respectively. Examples of the substituent represented by R 1B to R 4B or the unsubstituted hydrocarbon group include a hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a third butyl group. Examples of the compound represented by the formula (B) include catechol and t-butylcatechol.

式（C）中，作為由R1C 、R2C 及RN 所表示的烴基及取代基，其含義分別與所述式（A）的R1A ～R5A 所表示的烴及取代基相同。作為由R1C 、R2C 及RN 所表示的經取代或未經取代的烴基，例如可列舉：甲基、乙基、丙基、及丁基等碳數1～6的烴基。 另外，R1C 與R2C 可鍵結而形成環，例如可列舉苯環。當R1C 與R2C 鍵結而形成環時，可進一步具有取代基（例如碳數1～5的烴基）。 作為由式（C）所表示的化合物，例如可列舉：1H-1,2,3-三唑、苯并三唑、及5-甲基-1H-苯并三唑等。 可列舉等。In the formula (C), the hydrocarbon group and the substituent represented by R 1C , R 2C and R N have the same meanings as the hydrocarbon and the substituent represented by R 1A to R 5A of the formula (A), respectively. Examples of the substituted or unsubstituted hydrocarbon group represented by R 1C , R 2C and R N include a hydrocarbon group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group and a butyl group. Further, R 1C and R 2C may be bonded to each other to form a ring, and examples thereof include a benzene ring. When R 1C is bonded to R 2C to form a ring, it may further have a substituent (for example, a hydrocarbon group having 1 to 5 carbon atoms). Examples of the compound represented by the formula (C) include 1H-1,2,3-triazole, benzotriazole, and 5-methyl-1H-benzotriazole. Can be listed.

作為經取代或未經取代的四唑，例如除未經取代的四唑以外，可列舉具有羥基、羧基、或者經取代或未經取代的胺基（作為取代基，較佳為碳數1～6的烷基，更佳為碳數1～3的烷基）作為取代基的四唑。Examples of the substituted or unsubstituted tetrazole include, for example, a hydroxyl group, a carboxyl group, or a substituted or unsubstituted amino group (as a substituent, preferably a carbon number of 1 to 4). The alkyl group of 6, more preferably an alkyl group having 1 to 3 carbon atoms, is a tetrazole as a substituent.

處理液中，相對於本發明的處理液的總質量，防腐蝕劑的含量較佳為0.01質量%～5質量%，更佳為0.05質量%～5質量%，進而更佳為0.1質量%～3質量%。The content of the anticorrosive agent in the treatment liquid is preferably from 0.01% by mass to 5% by mass, more preferably from 0.05% by mass to 5% by mass, even more preferably from 0.1% by mass to 3% by mass based on the total mass of the treatment liquid of the present invention. quality%.

＜螯合劑＞ 處理液可進而含有螯合劑。螯合劑與殘渣物中所含有的經氧化的金屬進行螯合化。 作為螯合劑，並無特別限定，但較佳為聚胺基多羧酸。 聚胺基多羧酸是具有多個胺基及多個羧酸基的化合物。作為聚胺基多羧酸，例如可列舉：單-或聚伸烷基聚胺多羧酸、聚胺基烷烴多羧酸、聚胺基烷醇多羧酸、及羥基烷基醚聚胺多羧酸。<Chelating Agent> The treatment liquid may further contain a chelating agent. The chelating agent is chelated with the oxidized metal contained in the residue. The chelating agent is not particularly limited, but is preferably a polyaminopolycarboxylic acid. The polyaminopolycarboxylic acid is a compound having a plurality of amine groups and a plurality of carboxylic acid groups. Examples of the polyaminopolycarboxylic acid include a mono- or polyalkylene polyamine polycarboxylic acid, a polyaminoalkane polycarboxylic acid, a polyaminoalkanol polycarboxylic acid, and a hydroxyalkyl ether polyamine. carboxylic acid.

作為聚胺基多羧酸，例如可列舉：丁二胺四乙酸、二乙三胺五乙酸（Diethylenetriamine Pentaacetic Acid，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（Ethylene Diamine Tetraacetic Acid，EDTA）、反式-1,2-二胺基環己烷四乙酸、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，較佳為乙二胺四乙酸（EDTA）、二乙三胺五乙酸（DTPA）、或反式-1,2-二胺基環己烷四乙酸。 螯合劑可單獨使用，亦可適宜組合兩種以上來使用。Examples of the polyaminopolycarboxylic acid include butanediaminetetraacetic acid, Diethylenetriamine Pentaacetic Acid (DTPA), ethylenediaminetetrapropionic acid, triethylenetetramine hexaacetic acid, and 1,3-. Diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid, propylenediaminetetraacetic acid, EDTA, trans-1,2-di Aminocyclohexanetetraacetic acid, 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, diaminopropanol Tetraacetic acid, and (hydroxyethyl) ethylenediaminetriacetic acid, and the like. Among them, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), or trans-1,2-diaminocyclohexanetetraacetic acid is preferred. The chelating agent may be used singly or in combination of two or more.

處理液中，相對於本發明的處理液的總質量，螯合劑的含量較佳為0.01質量%～5質量%，更佳為0.01質量%～3質量%。The content of the chelating agent in the treatment liquid is preferably from 0.01% by mass to 5% by mass, and more preferably from 0.01% by mass to 3% by mass based on the total mass of the treatment liquid of the present invention.

＜水溶性有機溶劑＞ 本發明的處理液較佳為含有水溶性有機溶劑。水溶性有機溶劑除促進添加成分及有機物殘渣物的可溶解化以外，可進一步提昇防腐蝕效果。 作為水溶性有機溶劑，並無特別限定，例如可列舉：水溶性醇、水溶性酮、水溶性酯、及水溶性醚（例如二醇二醚）等。<Water-Soluble Organic Solvent> The treatment liquid of the present invention preferably contains a water-soluble organic solvent. The water-soluble organic solvent can further enhance the anticorrosive effect in addition to the dissolution of the additive component and the organic residue. The water-soluble organic solvent is not particularly limited, and examples thereof include a water-soluble alcohol, a water-soluble ketone, a water-soluble ester, and a water-soluble ether (for example, glycol diether).

作為水溶性醇，例如可列舉：烷二醇（例如包含伸烷基二醇）、二醇、烷氧基醇（例如包含二醇單醚）、飽和脂肪族一元醇、不飽和非芳香族一元醇、及含有環結構的低分子量的醇。Examples of the water-soluble alcohol include an alkanediol (for example, an alkylene glycol), a glycol, an alkoxy alcohol (for example, a glycol monoether), a saturated aliphatic monohydric alcohol, and an unsaturated non-aromatic one. An alcohol, and a low molecular weight alcohol having a ring structure.

作為烷二醇，例如可列舉：2-甲基-1,3-丙二醇、1,3-丙二醇、2,2-二甲基-1,3-二醇、1,4-丁二醇、1,3-丁二醇、1,2-丁二醇、2,3-丁二醇、頻哪醇、及伸烷基二醇等。Examples of the alkanediol include 2-methyl-1,3-propanediol, 1,3-propanediol, 2,2-dimethyl-1,3-diol, and 1,4-butanediol. , 3-butanediol, 1,2-butanediol, 2,3-butanediol, pinacol, and alkylene glycol.

作為伸烷基二醇，例如可列舉：乙二醇、丙二醇、二乙二醇、二丙二醇、三乙二醇、及四乙二醇等。Examples of the alkylene glycol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, and tetraethylene glycol.

作為烷氧基醇，例如可列舉：3-甲氧基-3-甲基-1-丁醇、3-甲氧基-1-丁醇、及1-甲氧基-2-丁醇等。Examples of the alkoxy alcohol include 3-methoxy-3-methyl-1-butanol, 3-methoxy-1-butanol, and 1-methoxy-2-butanol.

作為二醇單醚，例如可列舉：乙二醇單甲基醚、乙二醇單乙基醚、乙二醇單正丙基醚、乙二醇單異丙基醚、乙二醇單丁基醚、乙二醇單正丁基醚、二乙二醇單甲基醚、二乙二醇單乙基醚、二乙二醇單丁基醚、三乙二醇單甲基醚、三乙二醇單乙基醚、三乙二醇單丁基醚、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-正丙基醚、二丙二醇單甲基醚、二丙二醇單乙基醚、二丙二醇單-正丙基醚、三丙二醇單乙基醚、三丙二醇單甲基醚及乙二醇單苄基醚、以及二乙二醇單苄基醚等。Examples of the glycol monoether include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, and ethylene glycol monobutyl. Ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol Alcohol 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol single Methyl ether and ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.

作為飽和脂肪族一元醇，例如可列舉：甲醇、乙醇、正丙醇、異丙醇、1-丁醇、2-丁醇、異丁醇、第三丁醇、2-戊醇、第三戊醇、及1-己醇等。Examples of the saturated aliphatic monohydric alcohol include methanol, ethanol, n-propanol, isopropanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 2-pentanol, and third pentane. Alcohol, 1-hexanol, etc.

作為不飽和非芳香族一元醇，例如可列舉：芳基醇、炔丙基醇、2-丁烯基醇、3-丁烯基醇、及4-戊烯-2-醇等。Examples of the unsaturated non-aromatic monohydric alcohol include an aryl alcohol, a propargyl alcohol, a 2-butenyl alcohol, a 3-butenyl alcohol, and 4-penten-2-ol.

作為含有環結構的低分子量的醇，例如可列舉：四氫糠醇、糠醇、及1,3-環戊二醇等。Examples of the low molecular weight alcohol having a ring structure include tetrahydrofurfuryl alcohol, decyl alcohol, and 1,3-cyclopentanediol.

作為水溶性酮，例如可列舉：丙酮（acetone）、丙酮（propanone）、環丁酮、環戊酮、環己酮、二丙酮醇、2-丁酮、5-己二酮、1,4-環己二酮、3-羥基苯乙酮、1,3-環己二酮、及環己酮等。Examples of the water-soluble ketone include acetone (acetone), acetone (propanone), cyclobutanone, cyclopentanone, cyclohexanone, diacetone alcohol, 2-butanone, 5-hexanedione, and 1,4- Cyclohexanedione, 3-hydroxyacetophenone, 1,3-cyclohexanedione, and cyclohexanone.

作為水溶性酯，可列舉：乙酸乙酯、乙二醇單乙酸酯、及二乙二醇單乙酸酯等二醇單酯，以及丙二醇單甲基醚乙酸酯、乙二醇單甲基醚乙酸酯、丙二醇單乙基醚乙酸酯、及乙二醇單乙基醚乙酸酯等二醇單醚單酯等。Examples of the water-soluble ester include glycol monoesters such as ethyl acetate, ethylene glycol monoacetate, and diethylene glycol monoacetate, and propylene glycol monomethyl ether acetate and ethylene glycol monomethyl ester. A glycol monoether monoester such as phenyl ether acetate, propylene glycol monoethyl ether acetate, or ethylene glycol monoethyl ether acetate.

水溶性有機溶劑可單獨使用，亦可適宜組合兩種以上來使用。 水溶性有機溶劑之中，就進一步提昇防腐蝕效果的觀點而言，較佳為水溶性醇，更佳為烷二醇、二醇、烷氧基醇，進而更佳為烷氧基醇，特佳為乙二醇單丁基醚、三丙二醇單甲基醚、或二乙二醇單乙基醚。The water-soluble organic solvent may be used singly or in combination of two or more. Among the water-soluble organic solvents, from the viewpoint of further enhancing the anticorrosive effect, a water-soluble alcohol is preferred, and an alkanediol, a diol, an alkoxy alcohol, and more preferably an alkoxy alcohol, is preferred. Preferably, ethylene glycol monobutyl ether, tripropylene glycol monomethyl ether, or diethylene glycol monoethyl ether.

處理液中，相對於本發明的處理液的總質量，水溶性有機溶劑的含量較佳為0.1質量%～15質量%，更佳為1質量%～10質量%。The content of the water-soluble organic solvent in the treatment liquid is preferably from 0.1% by mass to 15% by mass, and more preferably from 1% by mass to 10% by mass based on the total mass of the treatment liquid of the present invention.

＜pH調整劑＞ 本發明的處理液的pH並無特別限定，但較佳為羥基胺及羥基胺鹽的共軛酸的pKa以上。藉由本發明的處理液的pH為羥基胺及羥基胺鹽的共軛酸的pKa以上，殘渣物去除性飛躍性地提昇。換言之，當於處理液中羥基胺及羥基胺鹽以分子狀態存在的比率多時，可顯著地獲得本發明的效果。再者，例如羥基胺的共軛酸的pKa約為6。 就所述觀點而言，較佳為將本發明的處理液的pH設為6～11。為了使處理液的pH變成所述範圍，理想的是於處理液中含有pH調整劑。另外，若處理液的pH為所述範圍內，則腐蝕速度及殘渣物去除性能均更優異。 就洗淨性的觀點而言，處理液的pH的下限較佳為6.5以上，更佳為7以上，進而更佳為7.5以上。另一方面，就抑制腐蝕的觀點而言，其上限較佳為10.5以下，更佳為10以下，進而更佳為9.5以下，特佳為8.5以下。 作為pH的測定方法，可使用公知的pH計進行測定。<pH adjuster> The pH of the treatment liquid of the present invention is not particularly limited, but is preferably at least pKa of the conjugated acid of the hydroxylamine and the hydroxylamine salt. When the pH of the treatment liquid of the present invention is equal to or higher than the pKa of the conjugated acid of the hydroxylamine and the hydroxylamine salt, the residue removal property is drastically improved. In other words, when the ratio of the hydroxylamine and the hydroxylamine salt in the molecular state is large in the treatment liquid, the effects of the present invention can be remarkably obtained. Further, for example, the conjugate acid of the hydroxylamine has a pKa of about 6. From the above viewpoint, it is preferred to set the pH of the treatment liquid of the present invention to 6 to 11. In order to make the pH of the treatment liquid into the above range, it is desirable to contain a pH adjuster in the treatment liquid. Further, when the pH of the treatment liquid is within the above range, both the corrosion rate and the residue removal performance are more excellent. The lower limit of the pH of the treatment liquid is preferably 6.5 or more, more preferably 7 or more, and still more preferably 7.5 or more from the viewpoint of detergency. On the other hand, from the viewpoint of suppressing corrosion, the upper limit is preferably 10.5 or less, more preferably 10 or less, still more preferably 9.5 or less, and particularly preferably 8.5 or less. As a method of measuring the pH, measurement can be carried out using a known pH meter.

作為pH調整劑，可使用公知者，但通常較佳為不含金屬離子。 作為pH調整劑，例如可列舉：氫氧化銨、單胺類、亞胺類（例如1,8-二氮雜雙環[5.4.0]十一-7-烯、及1,5-二氮雜雙環[4.3.0]壬-5-烯等）、1,4-二氮雜雙環[2.2.2]辛烷、及胍鹽類（例如碳酸胍）等。其中，較佳為氫氧化銨、或亞胺類（例如1,8-二氮雜雙環[5.4.0]十一-7-烯、及1,5-二氮雜雙環[4.3.0]壬-5- 烯等）。 pH調整劑可單獨使用，亦可適宜組合兩種以上來使用。As the pH adjuster, a known one can be used, but it is usually preferable to contain no metal ions. Examples of the pH adjuster include ammonium hydroxide, monoamines, and imines (for example, 1,8-diazabicyclo [5.4.0] undec-7-ene, and 1,5-diaza Bicyclo[4.3.0]non-5-ene, etc.), 1,4-diazabicyclo[2.2.2]octane, and phosphonium salts (for example, cesium carbonate). Among them, preferred are ammonium hydroxide or imines (for example, 1,8-diazabicyclo[5.4.0]undec-7-ene, and 1,5-diazabicyclo[4.3.0]壬-5 - alkene, etc.). The pH adjuster may be used singly or in combination of two or more.

只要可使處理液達成所期望的pH，則pH調整劑的含量並無特別限定，但通常於處理液中，相對於處理液總質量，理想的是設為0.1質量%～5質量%，更理想的是設為0.1質量%～2質量%。The content of the pH adjuster is not particularly limited as long as the desired pH of the treatment liquid can be achieved, but it is usually 0.1% by mass to 5% by mass based on the total mass of the treatment liquid in the treatment liquid. It is preferably set to 0.1% by mass to 2% by mass.

＜四級氫氧化銨類＞ 另外，本發明的處理液較佳為含有四級氫氧化銨類。藉由添加四級氫氧化銨類，除可進一步提昇殘渣物去除性能以外，亦可作為pH調整劑發揮功能。 作為四級氫氧化銨類，較佳為由下述通式（4）所表示的化合物。<Four-grade ammonium hydroxides> Further, the treatment liquid of the present invention preferably contains a quaternary ammonium hydroxide. By adding a fourth-grade ammonium hydroxide, in addition to further improving the residue removal performance, it can also function as a pH adjuster. The fourth-order ammonium hydroxide is preferably a compound represented by the following formula (4).

[化2] [Chemical 2]

（式（4）中，R4A ～R4D 分別獨立地表示碳數1～6的烷基、碳數1～6的羥基烷基、苄基、或芳基）(In the formula (4), R 4A to R 4D each independently represent an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms, a benzyl group or an aryl group)

式（4）中，R4A ～R4D 分別獨立地表示碳數1～6的烷基（例如甲基、乙基、及丁基等）、碳數1～6的羥基烷基（例如羥基甲基、羥基乙基、及羥基丁基等）、苄基、或芳基（例如苯基、萘基（naphthyl group）、及萘基（naphthalene group）等）。其中，較佳為烷基、羥基乙基、或苄基。In the formula (4), R 4A to R 4D each independently represent an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, and a butyl group) or a hydroxyalkyl group having 1 to 6 carbon atoms (for example, a hydroxyl group). A benzyl group or an aryl group (for example, a phenyl group, a naphthyl group, a naphthalene group, etc.). Among them, an alkyl group, a hydroxyethyl group, or a benzyl group is preferred.

作為由式（4）所表示的化合物，具體而言，較佳為選自由氫氧化四甲基銨、氫氧化四丁基銨、氫氧化四乙基銨、氫氧化三甲基羥基乙基銨、氫氧化甲基三(羥基乙基)銨、氫氧化四(羥基乙基)銨、氫氧化三甲基苄基銨、及膽鹼所組成的群組中的至少一種四級氫氧化銨類，其中，於本發明中，更佳為氫氧化四甲基銨、氫氧化四乙基銨、氫氧化苄基三甲基銨、膽鹼、或氫氧化四丁基銨。 四級氫氧化銨類可單獨使用，亦可使用兩種以上的組合。As the compound represented by the formula (4), specifically, it is preferably selected from tetramethylammonium hydroxide, tetrabutylammonium hydroxide, tetraethylammonium hydroxide, and trimethylhydroxyethylammonium hydroxide. At least one quaternary ammonium hydroxide of the group consisting of methyltris(hydroxyethyl)ammonium hydroxide, tetrakis(hydroxyethyl)ammonium hydroxide, trimethylbenzylammonium hydroxide, and choline Among them, in the present invention, tetramethylammonium hydroxide, tetraethylammonium hydroxide, benzyltrimethylammonium hydroxide, choline or tetrabutylammonium hydroxide is more preferred. The quaternary ammonium hydroxides may be used singly or in combination of two or more.

處理液中，相對於本發明的處理液的總質量，四級氫氧化銨類的含量較佳為0.1質量%～15質量%，更佳為1質量%～10質量%。The content of the quaternary ammonium hydroxides in the treatment liquid is preferably from 0.1% by mass to 15% by mass, and more preferably from 1% by mass to 10% by mass based on the total mass of the treatment liquid of the present invention.

＜烷醇胺類＞ 就促進添加成分及有機物殘渣物的可溶解化，並且防腐蝕的觀點而言，處理液較佳為含有烷醇胺類。 烷醇胺類可為一級胺、二級胺、及三級胺的任一種，較佳為單胺、二胺、或三胺，更佳為單胺。胺的烷醇基較佳為具有1個～5個碳原子。 於本發明的處理液中，較佳為由下述式（5）所表示的化合物。 式（5）：R1 R2 -N-CH2 CH2 -O-R3 （式（5）中，R1 及R2 分別獨立地表示氫原子、甲基、乙基、或羥基乙基，R3 表示氫原子、或羥基乙基。其中，式中含有至少1個烷醇基） 作為烷醇胺類，具體而言，例如可列舉：單乙醇胺、二乙醇胺、三乙醇胺、第三丁基二乙醇胺、異丙醇胺、2-胺基-1-丙醇、3-胺基-1-丙醇、異丁醇胺、2-胺基-2-乙氧基-丙醇、及亦作為二甘醇胺而為人所知的2-胺基-2-乙氧基-乙醇。 烷醇胺類可單獨使用，亦可使用兩種以上的組合。<Alkanolamines> From the viewpoint of promoting the dissolution of the additive component and the organic residue, and preventing corrosion, the treatment liquid preferably contains an alkanolamine. The alkanolamines may be any of a primary amine, a secondary amine, and a tertiary amine, preferably a monoamine, a diamine, or a triamine, more preferably a monoamine. The alkanol group of the amine preferably has from 1 to 5 carbon atoms. In the treatment liquid of the present invention, a compound represented by the following formula (5) is preferred. Formula (5): R 1 R 2 -N-CH 2 CH 2 -OR 3 (In the formula (5), R 1 and R 2 each independently represent a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group, R 3 is a hydrogen atom or a hydroxyethyl group, wherein at least one alkanol group is contained in the formula.) Examples thereof include alkanolamines, and specific examples thereof include monoethanolamine, diethanolamine, triethanolamine, and tert-butylene. Ethanolamine, isopropanolamine, 2-amino-1-propanol, 3-amino-1-propanol, isobutanolamine, 2-amino-2-ethoxy-propanol, and also as two 2-Amino-2-ethoxy-ethanol known as glycolamine. The alkanolamines may be used singly or in combination of two or more.

處理液中，相對於本發明的處理液的總質量，烷醇胺類的含量較佳為0.1質量%～80質量%，更佳為0.5質量%～60質量%，進而更佳為0.5質量%～20質量%。The content of the alkanolamine in the treatment liquid is preferably from 0.1% by mass to 80% by mass, more preferably from 0.5% by mass to 60% by mass, even more preferably 0.5% by mass, based on the total mass of the treatment liquid of the present invention. ～20% by mass.

＜其他添加劑＞ 於取得本發明的效果的範圍內，本發明的處理液中亦可含有其他添加劑。作為其他添加劑，例如可列舉：界面活性劑、及消泡劑等。<Other Additives> The treatment liquid of the present invention may contain other additives insofar as the effects of the present invention are obtained. Examples of other additives include a surfactant, an antifoaming agent, and the like.

＜處理液的適宜形態＞ 作為本發明的處理液的較佳的形態，可列舉以下的形態，但並不特別限定於此。 （1）含有選自羥基胺及羥基胺鹽中的至少一種羥基胺化合物、水、防腐蝕劑、螯合劑、以及水溶性有機溶劑的處理液。 （2）含有選自羥基胺及羥基胺鹽中的至少一種羥基胺化合物、水、防腐蝕劑、以及水溶性有機溶劑及/或烷醇胺類的處理液。 （3）含有選自羥基胺及羥基胺鹽中的至少一種羥基胺化合物、四級氫氧化銨類、水、防腐蝕劑、以及水溶性有機溶劑及/或烷醇胺類的處理液。 （4）含有選自羥基胺及羥基胺鹽中的至少一種羥基胺化合物、水、以及氟化物的處理液。 （5）含有選自羥基胺及羥基胺鹽中的至少一種羥基胺化合物，水，以及選自由以下述式（A）～式（C）所表示的化合物（式中的各定義如上所述）、及經取代或未經取代的四唑所組成的群組中的至少一種的處理液。<Appropriate Form of Treatment Liquid> The preferred embodiment of the treatment liquid of the present invention includes the following aspects, but is not particularly limited thereto. (1) A treatment liquid containing at least one hydroxylamine compound selected from the group consisting of hydroxylamine and hydroxylamine salt, water, an anticorrosive agent, a chelating agent, and a water-soluble organic solvent. (2) A treatment liquid containing at least one hydroxylamine compound selected from the group consisting of hydroxylamine and hydroxylamine salt, water, an anticorrosive agent, and a water-soluble organic solvent and/or an alkanolamine. (3) A treatment liquid containing at least one of a hydroxylamine compound selected from a hydroxylamine and a hydroxylamine salt, a quaternary ammonium hydroxide, water, an anticorrosive, and a water-soluble organic solvent and/or an alkanolamine. (4) A treatment liquid containing at least one hydroxylamine compound selected from the group consisting of hydroxylamine and hydroxylamine salt, water, and fluoride. (5) at least one hydroxylamine compound selected from the group consisting of hydroxylamine and hydroxylamine salt, water, and a compound selected from the group consisting of the following formulas (A) to (C) (each definition of the formula is as described above) And a treatment liquid of at least one of the group consisting of substituted or unsubstituted tetrazole.

[化3] [Chemical 3]

（6）於所述（1）～所述（5）的各個處理液中，Fe離子含量較佳為所述含量，另外，Fe離子的含量與羥基胺化合物的含量（含有多種選自羥基胺及其鹽中的化合物時為其合計量）的含有比率（質量比）較佳為所述含有比率。(6) In each of the treatment liquids of the above (1) to (5), the Fe ion content is preferably the content, and the content of Fe ions and the content of the hydroxylamine compound (containing a plurality of selected from the group consisting of hydroxylamines) The content ratio (mass ratio) of the compound in the salt thereof and the total amount thereof is preferably the content ratio.

＜過濾＞ 本發明的處理液較佳為以去除異物及減少缺陷等為目的，利用過濾器進行過濾而成者。 作為過濾器的材質，只要是自先前以來用於過濾用途等者，則可無特別限定地使用，例如可列舉：聚四氟乙烯（Polytetrafluoroethylene，PTFE）等氟樹脂，尼龍等聚醯胺系樹脂，以及聚乙烯及聚丙烯（Polypropylene，PP）等聚烯烴樹脂（包含高密度及超高分子量）等。該些材質之中，較佳為聚丙烯（包含高密度聚丙烯）或尼龍。 過濾器的孔徑合適的是0.001 μm～1.0 μm左右，較佳為0.02 μm～0.5 μm左右，更佳為0.01 μm～0.1 μm左右。藉由設為該範圍，可抑制過濾堵塞，並可確實地去除液中所含有的雜質及凝聚物等微細的異物。 當使用過濾器時，亦可將不同的過濾器加以組合。 利用各個過濾器的過濾可僅進行1次，亦可進行2次以上。該2次以上的過濾例如是指使液體循環，並利用同一個過濾器進行2次以上的過濾的情況。<Filtering> The treatment liquid of the present invention is preferably a filter which is filtered by a filter for the purpose of removing foreign matter and reducing defects. The material of the filter is not particularly limited as long as it has been used for filtration purposes, and examples thereof include a fluororesin such as polytetrafluoroethylene (PTFE) and a polyamine resin such as nylon. And polyolefin resins (including high density and ultrahigh molecular weight) such as polyethylene and polypropylene (Polypropylene, PP). Among these materials, polypropylene (including high density polypropylene) or nylon is preferred. The pore diameter of the filter is suitably from about 0.001 μm to about 1.0 μm, preferably from about 0.02 μm to about 0.5 μm, more preferably from about 0.01 μm to about 0.1 μm. By setting it as this range, it is possible to suppress clogging of the filter, and it is possible to surely remove fine foreign matter such as impurities and aggregates contained in the liquid. Different filters can also be combined when using filters. Filtration by each filter may be performed only once or twice or more. The filtration of the second or more times is, for example, a case where the liquid is circulated and the filtration is performed twice or more by the same filter.

如上所述，亦可將不同的過濾器加以組合來實施過濾。當將不同的過濾器加以組合來進行2次以上的過濾時，較佳為第2次以後的孔徑等同於或大於第1次的過濾的孔徑。另外，亦可於所述範圍內將孔徑不同的第1種過濾器加以組合。此處的孔徑可參照過濾器生產商的標稱值。作為市售的過濾器，例如可自日本頗爾（Pall）股份有限公司、愛多邦得科東洋（Advantec Toyo）股份有限公司、日本英特格（Nihon Entegris）股份有限公司（原日本密科理（Mykrolis）股份有限公司）、及北澤微濾器（Kitz Microfilter）股份有限公司等所提供的各種過濾器中進行選擇。 第2種過濾器可使用以與所述第1種過濾器相同的材質等所形成的過濾器。第2種過濾器的孔徑合適的是0.01 μm～1.0 μm左右，較佳為0.1 μm～0.5 μm左右。藉由設為該範圍，當於液中含有成分粒子時，可於使該成分粒子殘存的狀態下，去除混入至液中的異物。 例如，事先僅混合最終所製備的處理液的一部分的成分來製備混合液，對該混合液實施利用第1種過濾器的過濾後，向所述利用第1種過濾器的過濾後的混合液中添加用以構成處理液的剩餘的成分，並對該混合液進行第2次過濾。As described above, different filters can also be combined to perform filtration. When two or more filters are combined by using different filters, it is preferable that the pore diameter after the second time is equal to or larger than the pore diameter of the first filtration. Further, the first type of filters having different pore diameters may be combined in the above range. The aperture here can be referred to the nominal value of the filter manufacturer. As a commercially available filter, for example, from Japan Pall Co., Ltd., Advantec Toyo Co., Ltd., Japan Nihon Entegris Co., Ltd. (formerly Japan Mico) Choose from various filters provided by Mykrolis Co., Ltd. and Kitz Microfilter Co., Ltd. As the second filter, a filter formed of the same material or the like as that of the first filter can be used. The pore size of the second filter is suitably from about 0.01 μm to about 1.0 μm, preferably from about 0.1 μm to about 0.5 μm. By setting this range, when the component particles are contained in the liquid, the foreign matter mixed in the liquid can be removed while the component particles remain. For example, a mixed liquid is prepared by mixing only a part of the finally prepared processing liquid, and the mixed liquid is filtered by the first type of filter, and then filtered to the filtered mixture using the first type of filter. The remaining components constituting the treatment liquid were added thereto, and the mixture was subjected to the second filtration.

＜雜質及粗大粒子＞ 本發明的處理液鑒於其使用用途，較佳為液中的雜質，例如金屬成分等少。尤其，較佳為液中的Na離子濃度、K離子濃度、及Ca離子濃度處於5ppm（質量基準）以下的範圍內。 另外，較佳為於處理液中，實質上不含粗大粒子。 再者，處理液中所含有的粗大粒子是指作為雜質而包含於原料中的塵土、塵埃、有機固形物、及無機固形物等粒子，以及於處理液的製備中作為污染物而混入的塵土、塵埃、有機固形物、及無機固形物等粒子等，相當於最終不溶解於處理液中而作為粒子存在者。處理液中所存在的粗大粒子數可利用將雷射作為光源的光散射式液中粒子測定方式中的市售的測定裝置，於液相下進行測定。<Impurity and coarse particles> The treatment liquid of the present invention is preferably an impurity in a liquid, for example, a metal component, etc., in view of its use. In particular, it is preferable that the Na ion concentration, the K ion concentration, and the Ca ion concentration in the liquid are within a range of 5 ppm (mass basis) or less. Further, it is preferred that substantially no coarse particles are contained in the treatment liquid. In addition, the coarse particles contained in the treatment liquid are particles such as dust, dust, organic solids, and inorganic solids contained in the raw material as impurities, and dust mixed as a contaminant in the preparation of the treatment liquid. Particles such as dust, organic solids, and inorganic solids correspond to those that are not dissolved in the treatment liquid and are present as particles. The number of coarse particles present in the treatment liquid can be measured in a liquid phase by using a commercially available measurement device in a light scattering liquid particle measurement method using a laser as a light source.

＜金屬濃度＞ 本發明的處理液較佳為作為雜質而包含於液中的除Fe以外的金屬（Na、K、Ca、Cu、Mg、Mn、Li、Al、Cr、Ni、及Zn的金屬元素）的離子濃度均為5 ppm以下（較佳為1 ppm以下）。尤其，於最頂尖的半導體元件的製造中，因設想需要更高的純度的處理液，故其金屬濃度更佳為比ppm級更低的值，即ppb級以下，進而更佳為ppt級（所述濃度均為質量基準），特佳為實質上不含所述金屬。<Metal concentration> The treatment liquid of the present invention is preferably a metal other than Fe (Na, K, Ca, Cu, Mg, Mn, Li, Al, Cr, Ni, and Zn) contained in the liquid as an impurity. The ion concentration of the element) is 5 ppm or less (preferably 1 ppm or less). In particular, in the manufacture of the most advanced semiconductor devices, since it is assumed that a treatment liquid having a higher purity is required, the metal concentration is preferably a value lower than the ppm level, that is, a ppb level or lower, and more preferably a ppt level ( The concentrations are all based on mass basis, and particularly preferably substantially free of the metal.

（保管容器及保管條件） 就無金屬溶出這一觀點而言，收容處理液的保管容器的材質（即，接觸處理液的部位）更佳為樹脂。收容處理液的保管容器特佳為所述保管容器的收容處理液的收容部的內壁的材質為樹脂。 作為樹脂的具體例，可列舉：高密度聚乙烯（High Density Polyethylene，HDPE）、高密度聚丙烯（PP）、6,6-尼龍、四氟乙烯（Polytetrafluoroethylene，PTFE）、四氟乙烯與全氟烷基乙烯基醚的共聚物（Perfluoroalkoxy，PFA）、聚氯三氟乙烯（Polychlorotrifluoroethylene，PCTFE）、乙烯・氯三氟乙烯共聚物（Ethylene Chlorotrifluoroethylene，ECTFE）、乙烯・四氟乙烯共聚物（Ethylene Tetrafluoroethylene，ETFE）、及四氟乙烯・六氟丙烯共聚物（Fluorinated Ethylene Propylene，FEP）等。其中，關於收容部的內壁的材質，較佳為分子內含有氟原子的氟系樹脂。 作為收容部的內壁的材質為氟系樹脂的容器的具體例，例如可列舉：英特格（Entegris）公司製造的氟潔淨（FluoroPure）PFA複合桶等。另外，亦可使用日本專利特表平3-502677號公報的第4頁、國際公開第2004/016526號手冊的第3頁、以及國際公開第99/46309號手冊的第9頁及第16頁等中所記載的容器。(Storage Container and Storage Conditions) The material of the storage container in which the treatment liquid is stored (that is, the portion contacting the treatment liquid) is more preferably a resin from the viewpoint of no metal elution. The storage container for accommodating the treatment liquid is particularly preferably a resin of the inner wall of the storage portion for accommodating the treatment liquid in the storage container. Specific examples of the resin include high density polyethylene (HDPE), high density polypropylene (PP), 6,6-nylon, polytetrafluoroethylene (PTFE), tetrafluoroethylene, and perfluorocarbon. Perfluoroalkoxy (PFA), Polychlorotrifluoroethylene (PCTFE), Ethylene Chlorotrifluoroethylene (ECTFE), Ethylene Tetrafluoroethylene , ETFE), and tetrafluoroethylene/hexafluoropropylene copolymer (Fluorinated Ethylene Propylene, FEP). Among these, the material of the inner wall of the accommodating portion is preferably a fluorine-based resin containing fluorine atoms in the molecule. Specific examples of the container made of a fluorine-based resin as the inner wall of the accommodating portion include, for example, a Fluoro Pure PFA composite drum manufactured by Entegris. In addition, the fourth page of the Japanese Patent Publication No. 3-502677, the third page of the International Publication No. 2004/016526, and the pages 9 and 16 of the International Publication No. 99/46309 can also be used. The container described in the above.

保管容器中，保管容器內的壓力較佳為大氣壓附近壓力，更佳為96000 Pa～106000 Pa，進而更佳為99000 Pa～103300 Pa。In the storage container, the pressure in the storage container is preferably a pressure in the vicinity of atmospheric pressure, more preferably 96000 Pa to 106000 Pa, and still more preferably 99,000 Pa to 103,300 Pa.

另外，為了容易控制空隙率，保管容器較佳為於容器上部具有多個可藉由蓋部及閥等來密封的開口部。即，藉由卸除蓋部及閥等，可透過開口部對保管容器內的氣體與大氣進行交換。 另外，較佳為所述多個開口部之中，至少1個開口部為具備排氣功能的排氣口，更佳為於所述排氣口具有排氣閥。排氣閥可為與容器的開口部一體的形態（方法），亦可為不同於開口部且可於使用時安裝的形態（方法）。Further, in order to easily control the void ratio, it is preferable that the storage container has a plurality of openings at the upper portion of the container which can be sealed by a lid portion, a valve or the like. In other words, by removing the cover portion, the valve, or the like, the gas in the storage container can be exchanged with the atmosphere through the opening. Further, it is preferable that at least one of the plurality of openings is an exhaust port having an exhaust function, and more preferably an exhaust valve is provided at the exhaust port. The exhaust valve may be in a form (method) that is integral with the opening of the container, or may be a form (method) that is different from the opening and that can be attached during use.

本發明的處理液中所含有的選自羥基胺及其鹽中的化合物有時於保管狀態下分解，並產生含有氮氧化物等的氣體。該分解更容易於二氧化碳的存在下、或高溫環境下產生。 因此，就維持本發明的效果的觀點而言，較佳為於後述的保管溫度下保管。 另外，本發明的處理液可於氮氣等惰性氣體的環境下保管。於此情況下，保管容器較佳為具備將惰性氣體填充至保管容器內的空隙中的機構的形態。 進而，較佳為利用具有將含有氮氧化物等的氣體排出至容器外的功能的保管容器來保管的形態，所述氮氧化物藉由選自羥基胺及其鹽中的化合物的分解而產生，如上所述，更佳為具有多個開口部的形態、及至少1個開口部為具備排氣功能的排氣口的形態，特佳為於所述排氣口具有排氣閥。The compound selected from the hydroxylamine and its salt contained in the treatment liquid of the present invention may be decomposed in a stored state to generate a gas containing nitrogen oxides or the like. This decomposition is more likely to occur in the presence of carbon dioxide or in a high temperature environment. Therefore, from the viewpoint of maintaining the effects of the present invention, it is preferably stored at a storage temperature to be described later. Further, the treatment liquid of the present invention can be stored in an atmosphere of an inert gas such as nitrogen. In this case, it is preferable that the storage container has a configuration in which an inert gas is filled in a space in the storage container. Further, it is preferably stored in a storage container having a function of discharging a gas containing nitrogen oxides or the like to the outside of the container, and the nitrogen oxide is produced by decomposition of a compound selected from a hydroxylamine and a salt thereof. As described above, it is more preferable that the plurality of openings are provided and the at least one opening is an exhaust port having an exhaust function, and it is particularly preferable that the exhaust port has an exhaust valve.

如上所述，於保管容器中收容處理液時的保管容器內的空隙率為0.01體積%～30體積%，就進一步抑制處理液的殘渣物去除性能的劣化的觀點而言，更佳為1體積%～25體積%，進而更佳為12體積%～20體積%。 藉由空隙率為0.01體積%～30體積%，本發明的效果變得顯著。 再者，空隙率藉由以下的式（1）來求出。 式（1）：空隙率＝{1－（保管容器內的半導體元件用處理液的體積/保管容器的容器體積）}×100 所述式中，所謂「保管容器的容器體積」，是指收容處理液的保管容器的體積。另外，所謂「保管容器內的處理液的體積」，是指保管容器內中所收容的處理液的體積。再者，於保管容器中的未充滿處理液的空間中含有包含氧的空氣。 另外，如上所述，就取得本發明的效果的觀點而言，保存容器內的處理液的液溫只要是室溫靜置（25℃附近，較佳為23℃～27℃）～冷藏保管（5℃附近，較佳為較佳為0℃～7℃）之間的溫度區域即可，更佳為0℃～5℃的溫度區域。本發明的處理液即便當於所述室溫靜置與冷藏保管中的熱循環環境下保存時，亦難以產生殘渣物去除性能的劣化。As described above, the porosity in the storage container when the processing liquid is stored in the storage container is 0.01% by volume to 30% by volume, and more preferably 1 volume from the viewpoint of further suppressing deterioration of the residue removal performance of the treatment liquid. From 5% to 25% by volume, more preferably from 12% by volume to 20% by volume. The effect of the present invention is remarkable by the void ratio of 0.01% by volume to 30% by volume. Further, the void ratio is obtained by the following formula (1). (1): void ratio = {1 (the volume of the processing liquid for semiconductor elements in the storage container / the container volume of the storage container)} × 100 In the above formula, the "container volume of the storage container" means accommodation. The volume of the storage container for the treatment liquid. In addition, the "volume of the treatment liquid in the storage container" means the volume of the treatment liquid contained in the storage container. Further, air containing oxygen is contained in a space in the storage container that is not filled with the treatment liquid. In addition, as described above, the liquid temperature of the treatment liquid in the storage container is left at room temperature (about 25 ° C, preferably 23 ° C to 27 ° C) from the viewpoint of obtaining the effect of the present invention. A temperature range between 5 ° C and preferably about 0 ° C to 7 ° C is preferable, and a temperature range of 0 ° C to 5 ° C is more preferable. When the treatment liquid of the present invention is stored in a heat cycle environment in which the room temperature is allowed to stand and stored in a refrigerator, it is difficult to cause deterioration of the residue removal performance.

另外，將處理液封入至保管容器時的溫度較佳為20℃～25℃。Further, the temperature at which the treatment liquid is sealed in the storage container is preferably from 20 ° C to 25 ° C.

[處理液收容器] 本發明的處理液收容器是具有保管容器、以及收容於保管容器內的至少含有選自羥基胺及羥基胺鹽中的至少任一種與水的半導體元件用處理液，且所述保管容器內的空隙率為0.01體積%～30體積%者。即，所謂處理液收容器，是指於保管容器內收容所述半導體元件用處理液而成者。再者，空隙率藉由所述式（1）來求出。 處理液收容器的適宜的形態及其效果與所述處理液的保管方法中所說明的形態相同。[Processing liquid container] The processing liquid container of the present invention includes a storage container and a processing liquid for a semiconductor element containing at least one selected from the group consisting of hydroxylamine and hydroxylamine salt and water contained in the storage container, and The void ratio in the storage container is from 0.01% by volume to 30% by volume. In other words, the processing liquid container is a container in which the processing liquid for a semiconductor element is accommodated in a storage container. Further, the void ratio is obtained by the above formula (1). A suitable form and effect of the treatment liquid container are the same as those described in the method for storing the treatment liquid.

（半導體元件用處理液的用途） 半導體元件用處理液是於製造半導體元件時的各步驟中適宜使用。例如，如上所述，可用作用以去除實施乾式蝕刻步驟後的殘渣物的洗淨液、以及用以剝離抗蝕劑膜及永久膜（例如彩色濾光片）等的剝離液。其中，可適宜地用作洗淨液。 另外，半導體元件用處理液亦可適宜地用作將金屬硬遮罩用作遮罩的乾式蝕刻步驟後的洗淨液。作為構成金屬硬遮罩的材料，例如較佳為含有Cu、Co、W、AlOx、AlN、AlOxNy、WOx、Ti、TiN、ZrOx、HfOx及TaOx的任一種以上。此處，x、y分別為由x＝1～3、y＝1～2所表示的數。 另外，亦可適宜地用於去除經過使用金屬硬遮罩的乾式蝕刻步驟後任意地進行的乾式蝕刻步驟（例如乾式灰化處理）所產生的乾式灰化殘渣物。 [實施例](Application of Process Liquid for Semiconductor Element) The process liquid for semiconductor elements is suitably used in each step in the process of manufacturing a semiconductor element. For example, as described above, it can be used as a cleaning liquid for removing the residue after the dry etching step, and a peeling liquid for peeling off the resist film and the permanent film (for example, a color filter). Among them, it can be suitably used as a washing liquid. Further, the processing liquid for a semiconductor element can also be suitably used as a cleaning liquid after a dry etching step using a metal hard mask as a mask. As a material constituting the metal hard mask, for example, it is preferable to contain at least one of Cu, Co, W, AlOx, AlN, AlOxNy, WOx, Ti, TiN, ZrOx, HfOx, and TaOx. Here, x and y are numbers represented by x=1 to 3 and y=1 to 2, respectively. Further, it can be suitably used for removing dry ashing residue generated by a dry etching step (for example, dry ashing treatment) which is arbitrarily performed after a dry etching step using a metal hard mask. [Examples]

以下根據實施例來更詳細地說明本發明。只要不脫離本發明的主旨，則以下的實施例中所示的材料、使用量、比例、處理內容、及處理程序等可適宜變更。因此，本發明的範圍不應由以下所示的實施例限定性地進行解釋。Hereinafter, the present invention will be described in more detail based on examples. The materials, the amounts used, the ratios, the processing contents, the processing procedures, and the like shown in the following examples can be appropriately changed without departing from the gist of the invention. Therefore, the scope of the invention should not be construed as being limited by the embodiments shown below.

（實施例A1～實施例A7、實施例B1～實施例B7、實施例C1～實施例C7、實施例D1～實施例D7、實施例E1～實施例E7、實施例F1～實施例F7、實施例G1～實施例G7、實施例H1～實施例H7、實施例I1～實施例I7、實施例J1～實施例J7、實施例K1～實施例K7、實施例L1～實施例L7、實施例M1～實施例M7，比較例A1、比較例A2、比較例B1、比較例B2、比較例C1、比較例C2、比較例D1、比較例D2、比較例E1、比較例E2、比較例F1、比較例F2、比較例G1、比較例G2、比較例H1、比較例H2、比較例I1、比較例I2、比較例J1、比較例J2、比較例K1、比較例K2、比較例L1、比較例L2、比較例M1、比較例M2）(Examples A1 to A7, Examples B1 to B7, Examples C1 to C7, Examples D1 to D7, Examples E1 to E7, and Examples F1 to F7) Examples G1 to G7, Examples H1 to H7, Examples I1 to I7, Examples J1 to J7, Examples K1 to K7, Examples L1 to L7, and Example M1 -Example M7, Comparative Example A1, Comparative Example A2, Comparative Example B1, Comparative Example B2, Comparative Example C1, Comparative Example C2, Comparative Example D1, Comparative Example D2, Comparative Example E1, Comparative Example E2, Comparative Example F1, Comparison Example F2, Comparative Example G1, Comparative Example G2, Comparative Example H1, Comparative Example H2, Comparative Example I1, Comparative Example I2, Comparative Example J1, Comparative Example J2, Comparative Example K1, Comparative Example K2, Comparative Example L1, Comparative Example L2 , Comparative Example M1, Comparative Example M2)

（1）處理液的製備 ＜水的精製＞ 使用日本專利特開2011-110515號公報段落[0074]～段落[0084]中所記載的方法準備用於以下的處理液的製備的水。再者，該方法包含金屬離子去除步驟。 所獲得的水的Fe離子的含量及Co離子的含量分別為1 ppt質量以下。再者，Fe離子、及Co離子的各含量可藉由感應耦合電漿質量分析裝置（橫河分析系統製造，安捷倫（Agilent）7500cs型）來測定。(1) Preparation of Treatment Liquid <Refining of Water> Water prepared for the following treatment liquid was prepared by the method described in paragraphs [0074] to [0084] of JP-A-2011-110515. Furthermore, the method comprises a metal ion removal step. The content of Fe ions and the content of Co ions in the obtained water were respectively 1 ppt or less. Further, the respective contents of Fe ions and Co ions can be measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical System, Agilent 7500cs type).

繼而，分別製備下述所示的處理液A～處理液M（pH均為7～11）。繼而，使所獲得的處理液穿過離子交換膜來進行精製，而實施處理液中的Fe離子的去除。 再者，於各處理中，所使用的各種成分的含量（質量%）如表中所記載般，殘部為藉由所述方式獲得的水。Then, the treatment liquid A to the treatment liquid M (pH 7 to 11) shown below were prepared separately. Then, the obtained treatment liquid is passed through an ion exchange membrane for purification, and the removal of Fe ions in the treatment liquid is performed. Further, in each treatment, the content (% by mass) of each component used was as described in the table, and the residue was water obtained by the above method.

以下表示用於處理液的各種成分。 ＜還原劑＞ HA：羥基胺（巴斯夫（BASF）公司製造） HAS：羥基銨硫酸鹽（巴斯夫公司製造）The various components for the treatment liquid are shown below. <Reducing agent> HA: Hydroxylamine (manufactured by BASF) HAS: Hydroxyammonium sulfate (manufactured by BASF Corporation)

＜防腐蝕劑＞ 1-硫甘油（相當於式（A），和光純藥公司製造） 5-甲基-1H-苯并三唑（5MBTA：相當於式（C），東京化成工業公司製造） 兒茶酚（相當於式（B），關東化學公司製造）<Anticorrosive agent> 1-thioglycerol (corresponding to formula (A), manufactured by Wako Pure Chemical Industries, Ltd.) 5-methyl-1H-benzotriazole (5MBTA: equivalent to formula (C), manufactured by Tokyo Chemical Industry Co., Ltd.) Tea phenol (equivalent to formula (B), manufactured by Kanto Chemical Co., Ltd.)

＜螯合劑＞ DPTA：二乙三胺五乙酸（中部吉利斯德（Chubu Chelest）公司製造）<chelating agent> DPTA: diethylenetriamine pentaacetic acid (manufactured by Chubu Chelest Co., Ltd.)

＜水溶性有機溶劑＞ EGBE：乙二醇單丁基醚（和光純藥公司製造） ＜pH調整劑＞ DBU：1,8-二氮雜雙環[5.4.0]十一-7-烯（三亞普羅（San-Apro）公司製造） NH4 OH：氫氧化銨（和光純藥公司製造） ＜四級氫氧化銨類＞ 膽鹼：三開（Sachem）公司製造 ＜氟化物＞ NH4 F：氟化銨（和光純藥公司製造）<Water-soluble organic solvent> EGBE: ethylene glycol monobutyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) <pH adjuster> DBU: 1,8-diazabicyclo[5.4.0]undec-7-ene (Sanya Made by San-Apro) NH 4 OH: Ammonium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) <Four grade ammonium hydroxides> Choline: manufactured by Sachem Corporation <Fluoride> NH 4 F: Fluorine Ammonium (made by Wako Pure Chemical Industries, Inc.)

＜烷醇胺類＞ 單乙醇胺（東京化成工業股份有限公司製造） 二甘醇胺（別名：2-(2-胺基乙氧基)乙醇，東京化成工業股份有限公司製造） TEA：三乙醇胺（東京化成工業公司製造）<Alkanolamines> Monoethanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.) Diethylene glycolamine (alias: 2-(2-aminoethoxy)ethanol, manufactured by Tokyo Chemical Industry Co., Ltd.) TEA: Triethanolamine ( Made by Tokyo Chemical Industry Co., Ltd.)

（2）評價 對以上所製備的各處理液進行下述所示的評價。再者，於以下的評價中，製作包含作為殘渣物的一種的TiO的膜模型，並評價其蝕刻速率，藉此評價殘渣物去除性能。即，可以說當蝕刻速率高時，殘渣物去除性能優異，當蝕刻速率低時，殘渣物去除性能欠佳。 （a）剛製成（Fresh）時的蝕刻速率（ERFr ） 準備於基板表面積層TiO膜而成的膜模型。針對處理液A～處理液M的各者，於剛製備處理液之後（剛組成處理液之後，剛製成（fresh）），使各處理液與TiO膜接觸，並實施TiO膜的蝕刻處理，將其蝕刻速率設為ERFr 。 （b）熱循環試驗後的蝕刻速率（ERAge ） 於25℃、大氣壓下，以分別變成表1～表13中所示的空隙率（空隙率（體積%）＝{1－（保管容器內的半導體元件用處理液的體積/保管容器的容器體積）}×100）的方式，將處理液A～處理液M分別封入至樹脂製容器中。樹脂製容器為愛塞璐化學（Aicello Chemical）製造的潔淨瓶，容器的總容量使用500毫升者。 繼而，對封入至容器中的各處理液實施如下的熱循環試驗：將於作為通常的冷藏保管溫度的5℃下8小時→於作為室溫的25℃下4小時→於作為通常的冷藏保管溫度的5℃下8小時→於作為室溫的25℃下4小時設為1個循環，並重複180日。繼而，使用所述熱循環試驗後的處理液對TiO膜進行蝕刻處理，將其蝕刻速率（蝕刻速度）設為ERAge 。(2) Evaluation Each of the treatment liquids prepared above was evaluated as shown below. In addition, in the following evaluation, a film model containing TiO as a kind of residue was prepared, and the etching rate was evaluated, thereby evaluating the residue removal performance. That is, it can be said that when the etching rate is high, the residue removal performance is excellent, and when the etching rate is low, the residue removal performance is poor. (a) Etching rate (ER Fr ) at the time of fresh (Fresh film) A film model prepared by preparing a TiO film on a substrate surface area. Each of the treatment liquid A to the treatment liquid M is immediately after the treatment liquid is prepared (just after the treatment liquid is formed), and each treatment liquid is brought into contact with the TiO membrane, and the TiO film is etched. The etch rate is set to ER Fr . (b) The etching rate (ER Age ) after the heat cycle test was changed to the void ratio shown in Tables 1 to 13 at 25 ° C and atmospheric pressure (void ratio (% by volume) = {1 (in the storage container) Each of the processing liquid A to the processing liquid M is sealed in a resin container so that the volume of the processing liquid for the semiconductor element/the container volume of the storage container is 100 × 100). The resin container was a clean bottle made by Aicello Chemical, and the total capacity of the container was 500 ml. Then, each of the treatment liquids sealed in the container was subjected to the following heat cycle test: 8 hours at 5 ° C as a normal storage temperature and 4 hours at 25 ° C as room temperature → as a normal refrigeration storage The temperature was 5 hours at 5 ° C → 1 cycle at 25 ° C as room temperature, and repeated for 180 days. Then, the TiO film was etched using the treatment liquid after the heat cycle test, and the etching rate (etching speed) was set to ER Age .

（c）蝕刻速率維持率的計算及評價 根據所獲得的蝕刻速率ERFr 及ERAge ，計算蝕刻速率的維持率（蝕刻速率維持率（%）＝ERAge /ERFr ×100），並藉由下述的評價基準來進行評價。 ＜蝕刻速率維持率（%）＞ 「1」：60%以下 「2」：超過60%～70%以下 「3」：超過70%～80%以下 「4」：超過80%～90%以下 「5」：超過90%～95%以下 「6」：超過95%～100%(c) Calculation and Evaluation of Etching Rate Maintenance Rate According to the obtained etching rates ER Fr and ER Age , the retention rate of the etching rate (etching rate maintenance ratio (%) = ER Age / ER Fr × 100) was calculated by The evaluation was performed based on the following evaluation criteria. <etch rate maintenance rate (%)>"1": 60% or less "2": more than 60% to 70% or less "3": more than 70% to 80% or less "4": more than 80% to 90% or less"5": More than 90% to 95% or less "6": more than 95% to 100%

（處理液A） HA             4質量% 水               96質量%(Processing liquid A) HA 4% by mass Water 96% by mass

[表1] [Table 1]

（處理液B） HAS                 4質量% NH4 OH             將pH調整成7.8所需的量 水                     殘量(Processing liquid B) HAS 4% by mass NH 4 OH Adjusting the pH to 7.8

[表2] [Table 2]

（處理液C） HA                  15質量% 水                     84質量% 1-硫甘油           1質量%(Processing liquid C) HA 15% by mass Water 84% by mass 1-thioglycerol 1% by mass

[表3] [table 3]

（處理液D） HA             20質量% 水               72.5質量% TEA            7.5質量%(Processing liquid D) HA 20% by mass Water 72.5% by mass TEA 7.5% by mass

[表4] [Table 4]

（處理液E） HA             20質量% 水               72.5質量% 膽鹼           7.5質量%(Processing liquid E) HA 20% by mass Water 72.5% by mass Choline 7.5% by mass

[表5] [table 5]

（處理液F） HA                  20質量% 水                     79質量% NH4 F                0.5質量% NH4 OH            0.5質量%(Processing liquid F) HA 20% by mass Water 79% by mass NH 4 F 0.5% by mass NH 4 OH 0.5% by mass

[表6] [Table 6]

（處理液G） HA              4質量% 水               89.4質量% EGBE          5質量% DBU           0.85質量% DTPA          0.5質量% 5MBTA       0.25質量%(Processing liquid G) HA 4% by mass Water 89.4% by mass EGBE 5% by mass DBU 0.85 mass% DTPA 0.5% by mass 5 MBTA 0.25 mass%

[表7] [Table 7]

（處理液H） HA                   15質量% 水                     83.5質量% 1-硫甘油           1質量% 5MBTA            0.5質量%(Processing liquid H) HA 15% by mass Water 83.5% by mass 1-thioglycerol 1% by mass 5MBTA 0.5% by mass

[表8] [Table 8]

（處理液I） HA                   20質量% 水                     72質量% TEA                 7.5質量% 5MBTA            0.5質量%(Processing liquid I) HA 20% by mass Water 72% by mass TEA 7.5% by mass 5MBTA 0.5% by mass

[表9] [Table 9]

（處理液J） HA                   20質量% 水                     72質量% 膽鹼                7.5質量% 5MBTA            0.5質量%(Processing liquid J) HA 20% by mass Water 72% by mass Choline 7.5% by mass 5MBTA 0.5% by mass

[表10] [Table 10]

（處理液K） HA                  20質量% 水                     78.5質量% NH4 F                0.5質量% NH4 OH             0.5質量% 5MBTA            0.5質量%(Processing liquid K) HA 20% by mass Water 78.5% by mass NH 4 F 0.5% by mass NH 4 OH 0.5% by mass 5 MBTA 0.5% by mass

[表11] [Table 11]

（處理液L） HA                  20質量% 水                     20質量% 二甘醇胺          55質量% 兒茶酚             5質量%(Processing liquid L) HA 20% by mass Water 20% by mass Diethylene glycolamine 55% by mass Catechol 5% by mass

[表12] [Table 12]

（處理液M） HA                  20質量% 水                     20質量% 單乙醇胺          55質量% 兒茶酚             5質量%(Processing liquid M) HA 20% by mass Water 20% by mass Monoethanolamine 55% by mass Catechol 5% by mass

[表13] [Table 13]

根據表1～表13中所示的結果，確認於使用任一種處理液的情況下，當將空隙率設為0.01體積%～30體積%（較佳為1體積%～25體積%，更佳為12體積%～20體積%）時，蝕刻速率的下降均得到抑制（換言之，蝕刻速率被良好地維持）。根據該些結果，可知若為規定的空隙率，則殘渣去除性能的劣化得到抑制。 另一方面，於空隙率脫離0.01體積%～30體積%的數值範圍的情況下，確認到蝕刻速率的下降。From the results shown in Tables 1 to 13, it was confirmed that when any of the treatment liquids is used, the void ratio is set to 0.01% by volume to 30% by volume (preferably 1% by volume to 25% by volume, more preferably When it is 12% by volume to 20% by volume, the decrease in the etching rate is suppressed (in other words, the etching rate is well maintained). From these results, it is understood that deterioration of the residue removal performance is suppressed by a predetermined void ratio. On the other hand, when the void ratio was out of the numerical range of 0.01% by volume to 30% by volume, the decrease in the etching rate was confirmed.

（實施例A11～實施例A17） 繼而，準備於處理液A的配方中，如表14所示般變更羥基胺量的處理液2A～處理液7A，將容器內的空隙率均設為15體積%，並藉由與實施例A1相同的方法來實施熱循環試驗。根據所獲得的蝕刻速率ERFr 及ERAge ，計算蝕刻速率維持率並進行評價。 將結果示於表14中。(Examples A11 to A17) In the formulation of the treatment liquid A, the treatment liquid 2A to the treatment liquid 7A having the hydroxylamine amount were changed as shown in Table 14, and the void ratio in the container was set to 15 volumes. %, and the heat cycle test was carried out by the same method as in Example A1. The etching rate maintenance rate was calculated and evaluated based on the obtained etching rates ER Fr and ER Age . The results are shown in Table 14.

[表14] [Table 14]

（實施例B11～實施例B17） 繼而，準備於處理液B的配方中，如表15所示般變更羥基胺鹽量的處理液2B～處理液7B，將容器內的空隙率均設為15體積%，並藉由與實施例B1相同的方法來實施熱循環試驗。根據所獲得的蝕刻速率ERFr 及ERAge ，計算蝕刻速率維持率並進行評價。 將結果示於表15中。(Examples B11 to B17) In the formulation of the treatment liquid B, the treatment liquid 2B to the treatment liquid 7B having the hydroxylamine salt amount were changed as shown in Table 15, and the void ratio in the container was set to 15 5% by volume, and the heat cycle test was carried out by the same method as in Example B1. The etching rate maintenance rate was calculated and evaluated based on the obtained etching rates ER Fr and ER Age . The results are shown in Table 15.

[表15] [Table 15]

根據表14及表15的結果，確認當相對於處理液總質量，將選自羥基胺及羥基胺鹽中的至少一種化合物的含量設為4質量%～25質量%（較佳為12質量%～18質量%）時，蝕刻速率的下降進一步得到抑制（換言之，蝕刻速率被良好地維持）。From the results of Tables 14 and 15, it was confirmed that the content of at least one compound selected from the group consisting of hydroxylamine and hydroxylamine salt is from 4% by mass to 25% by mass (preferably 12% by mass) based on the total mass of the treatment liquid. When it is ～18 mass%), the decrease in the etching rate is further suppressed (in other words, the etching rate is favorably maintained).

（實施例A21～實施例A27） 繼而，準備於處理液A的配方中，當使處理液穿過離子交換膜來進行精製時如表16般分別製備處理液中的Fe離子的含量（相對於處理液總質量的量）的處理液12A～處理液17A，將容器內的空隙率均設為15體積%，並藉由與實施例A1相同的方法來實施熱循環試驗。根據所獲得的蝕刻速率ERFr 及ERAge ，計算蝕刻速率維持率並進行評價。 再者，處理液中的相對於處理液總質量的Fe離子的含量藉由感應耦合電漿質量分析裝置（橫河分析系統製造，安捷倫（Agilent）7500cs型）來測定。 將結果示於表16中。(Examples A21 to A27) Next, in the formulation of the treatment liquid A, when the treatment liquid was passed through the ion exchange membrane for purification, the content of Fe ions in the treatment liquid was prepared as shown in Table 16 (relative to The treatment liquid 12A to the treatment liquid 17A of the total amount of the treatment liquid were subjected to a heat cycle test by the same method as in Example A1, in which the void ratio in the container was 15% by volume. The etching rate maintenance rate was calculated and evaluated based on the obtained etching rates ER Fr and ER Age . Further, the content of Fe ions in the treatment liquid relative to the total mass of the treatment liquid was measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent Model 7500cs). The results are shown in Table 16.

[表16] [Table 16]

（實施例A28） 製作以Fe濃度變成12質量ppm的方式製備以上所製備的處理液A而成的處理液28A，除此以外，以與實施例A21相同的條件進行評價，結果評價為5。(Example A28) The treatment liquid 28A prepared by preparing the treatment liquid A prepared in the above manner was prepared, and the evaluation was carried out under the same conditions as in Example A21.

根據表16及實施例A28的結果，確認藉由使Fe離子以10質量ppt～10質量ppm（較佳為1質量ppb～1質量ppm，更佳為1質量ppb～50質量ppb，進而更佳為1質量ppb～5質量ppb）的微量存在於處理液中，蝕刻速率的下降進一步得到抑制（換言之，蝕刻速率被良好地維持）。According to the results of Table 16 and Example A28, it was confirmed that Fe ions were 10 mass ppm to 10 mass ppm (preferably 1 mass ppb to 1 mass ppm, more preferably 1 mass ppb to 50 mass ppb, and thus more preferably A trace amount of 1 mass ppb to 5 mass ppb) is present in the treatment liquid, and the decrease in the etching rate is further suppressed (in other words, the etching rate is well maintained).

（實施例C11、實施例D11、實施例E11、實施例F11、實施例G11） 繼而，準備於處理液C～處理液G的配方中，當使處理液穿過離子交換膜來進行精製時如表17般分別將處理液中的Fe離子的含量（相對於處理液總質量的量）調整成5質量ppb的處理液2C～處理液2G，將容器內的空隙率均設為15體積%，並藉由與實施例A1相同的方法來實施熱循環試驗。根據所獲得的蝕刻速率ERFr 及ERAge ，計算蝕刻速率維持率並進行評價。 再者，處理液中的相對於處理液總質量的Fe離子的含量藉由感應耦合電漿質量分析裝置（橫河分析系統製造，安捷倫（Agilent）7500cs型）來測定。 將結果示於表17中。(Example C11, Example D11, Example E11, Example F11, and Example G11) Next, in the formulation of the treatment liquid C to the treatment liquid G, when the treatment liquid is passed through the ion exchange membrane for purification, In the same manner as in Table 17, the content of Fe ions in the treatment liquid (the amount relative to the total mass of the treatment liquid) was adjusted to 5 to ppb of the treatment liquid 2C to the treatment liquid 2G, and the void ratio in the container was set to 15% by volume. The heat cycle test was carried out by the same method as in Example A1. The etching rate maintenance rate was calculated and evaluated based on the obtained etching rates ER Fr and ER Age . Further, the content of Fe ions in the treatment liquid relative to the total mass of the treatment liquid was measured by an inductively coupled plasma mass spectrometer (manufactured by Yokogawa Analytical Systems, Agilent Model 7500cs). The results are shown in Table 17.

[表17] [Table 17]

根據表17的結果，確認於處理液C～處理液G的配方中，藉由使Fe離子以10質量ppt～10質量ppm（較佳為1質量ppb～1質量ppm，更佳為1質量ppb～50質量ppb，進而更佳為1質量ppb～5質量ppb）的微量存在於處理液中，蝕刻速率的下降亦進一步得到抑制（換言之，蝕刻速率被良好地維持）。According to the results of Table 17, it is confirmed that the Fe ions are in a mass of 10 to 15 mass ppm (preferably 1 mass ppb to 1 mass ppm, more preferably 1 mass ppb) in the formulation of the treatment liquid C to the treatment liquid G. A trace amount of -50 mass ppb, more preferably 1 mass ppb to 5 mass ppb) is present in the treatment liquid, and the decrease in the etching rate is further suppressed (in other words, the etching rate is favorably maintained).

（對於半導體基板的應用） （1）具有Co膜的積層物的製作 首先，於基板（Si）上形成依次具備Co膜、SiN膜、SiO2 膜、及具有規定的開口部的金屬硬遮罩（TiN）的積層物。 繼而，使用該積層物，將金屬硬遮罩作為遮罩來實施電漿蝕刻，進行SiN膜及SiO2 膜的蝕刻直至Co膜表面露出為止，而形成孔。若利用掃描型電子顯微鏡照片（SEM：Scanning Electron Microscope）確認形成有孔的積層物的剖面，則可於孔壁面上看見電漿蝕刻殘渣物。 （2）半導體基板的洗淨 準備於規定的空隙率條件下對以上所製備的處理液A進行所述熱循環試驗而成的各處理液（相當於實施例A1～實施例A7及比較例A1、比較例A2中所製備的各處理液），並評價附著於所獲得的半導體基板上的電漿蝕刻殘渣物的處理速度。(Application to Semiconductor Substrate) (1) Production of a laminate having a Co film First, a metal hard mask having a Co film, a SiN film, an SiO 2 film, and a predetermined opening portion in this order is formed on a substrate (Si). a laminate of (TiN). Then, using this laminate, plasma etching was performed using a metal hard mask as a mask, and etching of the SiN film and the SiO 2 film was performed until the surface of the Co film was exposed to form a hole. When the cross section of the layered product in which the hole is formed is confirmed by a scanning electron micrograph (SEM: Scanning Electron Microscope), the plasma etching residue can be seen on the wall surface of the hole. (2) Cleaning of the semiconductor substrate Each of the treatment liquids obtained by performing the thermal cycle test on the treatment liquid A prepared above under a predetermined porosity ratio (corresponding to Examples A1 to A7 and Comparative Example A1) The respective treatment liquids prepared in Comparative Example A2) were evaluated for the treatment rate of the plasma etching residue adhering to the obtained semiconductor substrate.

電漿蝕刻殘渣物的處理速度的評價亦藉由與所述蝕刻速率維持率相同的方法來進行。 具體而言，根據剛製成時的處理速度（處理速度Fr ）與熱循環試驗後的處理速度（處理速度age ），計算處理速度的維持率（處理速度的維持率（%）＝處理速度age /處理速度Fr ×100），並藉由與所述蝕刻速率維持率相同的評價基準來進行評價。 其結果，確認於將處理液A用作半導體基板的洗淨液的情況下，亦可獲得與實施例A1～實施例A7及比較例A1、比較例A2相同的結果，即，當於處理液的保存下將空隙率設為0.01體積%～30體積%（較佳為1體積%～25體積%，更佳為12體積%～20體積%）時，電漿蝕刻殘渣物的處理速度的下降得到抑制（電漿蝕刻殘渣物的處理速度被良好地維持）。 另外，關於代替處理液A的處理液B～處理液M，亦確認到相同的結果。The evaluation of the processing speed of the plasma etching residue is also performed by the same method as the etching rate maintenance rate. Specifically, the maintenance rate of the processing speed (the maintenance rate of the processing speed (%) = the processing speed age is calculated based on the processing speed (processing speed Fr ) immediately after the production and the processing speed (processing speed age ) after the thermal cycle test. /Processing speed Fr × 100), and evaluation was performed by the same evaluation criteria as the etching rate maintenance rate. As a result, when the treatment liquid A was used as the cleaning liquid for the semiconductor substrate, it was confirmed that the same results as in the examples A1 to A7, the comparative example A1, and the comparative example A2 were obtained, that is, when the treatment liquid was used When the porosity is set to 0.01% by volume to 30% by volume (preferably 1% by volume to 25% by volume, more preferably 12% by volume to 20% by volume), the processing speed of the plasma etching residue is lowered. It is suppressed (the processing speed of the plasma etching residue is well maintained). In addition, the same result was confirmed about the treatment liquid B to the treatment liquid M instead of the treatment liquid A.

另外，關於處理液C～處理液M，製作將HA替換成HAS而成的處理液，並進行相同的實驗的結果，均獲得相同的結果。In addition, regarding the treatment liquid C to the treatment liquid M, a treatment liquid obtained by replacing HA with HAS was produced, and the same experiment was carried out, and the same results were obtained.

於處理液J中，調整膽鹼的量，藉此調整pH。再者，於設為酸性的pH的情況下，添加草酸二水合物（和光純藥工業（股份）製造）來進行調整。如此，製作pH為5.0、6.0、7.0、7.5、及11.0的處理液N1～處理液N5。將容器內的空隙率設為15體積%，並藉由與實施例A1相同的方法來實施熱循環試驗。根據所獲得的蝕刻速率ERFr 及ERAge ，計算蝕刻速率維持率並進行評價。 評價的結果，處理液N1（pH為5.0）變成3，處理液N2變成4，處理液N3～處理液N5變成5。In the treatment liquid J, the amount of choline is adjusted, thereby adjusting the pH. In addition, in the case of pH which is acidic, oxalic acid dihydrate (made by Wako Pure Chemical Industries, Ltd.) is added and adjusted. Thus, the treatment liquid N1 to the treatment liquid N5 having a pH of 5.0, 6.0, 7.0, 7.5, and 11.0 were produced. The void ratio in the container was set to 15% by volume, and the heat cycle test was carried out by the same method as in Example A1. The etching rate maintenance rate was calculated and evaluated based on the obtained etching rates ER Fr and ER Age . As a result of the evaluation, the treatment liquid N1 (pH of 5.0) became 3, the treatment liquid N2 became 4, and the treatment liquid N3 to the treatment liquid N5 became 5.

將處理液N3封入至設置有排氣閥的容器中，將空隙率設為15體積%並於70℃下保管2日，除此以外，同樣地藉由與實施例A1相同的方法來計算蝕刻速率維持率並進行評價。 於設置有排氣閥的容器中無內壓變化等的影響，於保管前後未看到殘渣去除性能的變化。 根據該結果，期待即便於夏季的室外等高溫的保管環境下，只要是具有排氣閥的容器，則無內壓變化等的影響，可穩定地獲得本發明的效果。The treatment liquid N3 was sealed in a container provided with an exhaust valve, and the void ratio was set to 15% by volume and stored at 70 ° C for 2 days. Otherwise, the etching was calculated in the same manner as in Example A1. Rate maintenance rate and evaluation. There was no influence of internal pressure change or the like in the container provided with the exhaust valve, and no change in the residue removal performance was observed before and after storage. According to the results, it is expected that the effect of the present invention can be stably obtained without any influence of changes in internal pressure or the like as long as it is a container having an exhaust valve even in a high-temperature storage environment such as outdoors in the summer.

無no

無no

無no

Claims (15)

一種半導體元件用處理液的保管方法，其於保管容器內保管至少含有選自羥基胺及羥基胺鹽中的至少任一種與水的半導體元件用處理液，且 將所述保管容器內的空隙率設為0.01體積%～30體積%， 再者，空隙率藉由以下的式（1）來求出， 式（1）：空隙率＝{1－（所述保管容器內的所述半導體元件用處理液的體積/所述保管容器的容器體積）}×100。A method for storing a processing liquid for a semiconductor device, wherein a storage liquid for a semiconductor element containing at least one selected from the group consisting of hydroxylamine and hydroxylamine salt and water is stored in a storage container, and a void ratio in the storage container is stored In addition, the void ratio is obtained by the following formula (1), and the formula (1): void ratio = {1 (for the semiconductor element in the storage container) The volume of the treatment liquid / the container volume of the storage container)} × 100. 如申請專利範圍第1項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有防腐蝕劑。The method for storing a processing liquid for a semiconductor device according to the first aspect of the invention, wherein the processing liquid for a semiconductor element further contains an anticorrosive agent. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有水溶性有機溶劑及烷醇胺類的至少一者。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the processing liquid for a semiconductor device further contains at least one of a water-soluble organic solvent and an alkanolamine. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有四級氫氧化銨類。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the processing liquid for a semiconductor device further contains a quaternary ammonium hydroxide. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有氟化物。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the processing liquid for a semiconductor device further contains a fluoride. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液進而含有螯合劑。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the processing liquid for a semiconductor device further contains a chelating agent. 如申請專利範圍第2項所述的半導體元件用處理液的保管方法，其中所述防腐蝕劑為選自由以下述式（A）～式（C）所表示的化合物所組成的群組中的至少一種，所述式（A）中，R1A ～R5A 分別獨立地表示氫原子、烴基、羥基、羧基或胺基；其中，於結構中含有至少1個選自羥基、羧基及胺基中的基； 所述式（B）中，R1B ～R4B 分別獨立地表示氫原子或烴基； 所述式（C）中，R1C 、R2C 及RN 分別獨立地表示氫原子或烴基；另外，R1C 與R2C 可鍵結而形成環。The method for storing a processing liquid for a semiconductor device according to the second aspect of the invention, wherein the anticorrosive agent is at least selected from the group consisting of compounds represented by the following formulas (A) to (C). One kind, In the formula (A), R 1A to R 5A each independently represent a hydrogen atom, a hydrocarbon group, a hydroxyl group, a carboxyl group or an amine group; wherein the structure contains at least one group selected from the group consisting of a hydroxyl group, a carboxyl group and an amine group; In the formula (B), R 1B to R 4B each independently represent a hydrogen atom or a hydrocarbon group; in the formula (C), R 1C , R 2C and R N each independently represent a hydrogen atom or a hydrocarbon group; 1C and R 2C may be bonded to form a ring. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述半導體元件用處理液的pH為6～11。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the pH of the processing liquid for a semiconductor device is 6 to 11. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述處理液中，相對於處理液總質量，所述選自羥基胺及羥基胺鹽中的至少任一種的總含量為1質量%～30質量%。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the processing liquid is at least one selected from the group consisting of hydroxylamine and hydroxylamine salt with respect to the total mass of the treatment liquid. The total content of any one is from 1% by mass to 30% by mass. 如申請專利範圍第1項或第2項所述的半導體元件用處理液的保管方法，其中所述處理液中，Fe離子的含量為10質量ppt～10質量ppm。The method for storing a processing liquid for a semiconductor device according to the first or second aspect of the invention, wherein the content of Fe ions in the treatment liquid is from 10 mass% to 10 mass ppm. 一種處理液收容器，其包括保管容器、以及收容於所述保管容器內的至少含有選自羥基胺及羥基胺鹽中的至少任一種與水的半導體元件用處理液，且所述保管容器內的空隙率為0.01體積%～30體積%， 再者，空隙率藉由以下的式（1）來求出， 式（1）：空隙率＝{1－（所述保管容器內的所述半導體元件用處理液的體積/所述保管容器的容器體積）}×100。A processing liquid container including a storage container and a processing liquid for a semiconductor element containing at least one selected from the group consisting of hydroxylamine and hydroxylamine salt and water contained in the storage container, and the storage container The void ratio is from 0.01% by volume to 30% by volume, and the void ratio is obtained by the following formula (1): Formula (1): void ratio = {1 - (the semiconductor in the storage container) The volume of the processing liquid for the component / the container volume of the storage container)} × 100. 如申請專利範圍第11項所述的處理液收容器，其中所述保管容器的內壁的材質為樹脂。The treatment liquid container according to claim 11, wherein the inner wall of the storage container is made of a resin. 如申請專利範圍第11項或第12項所述的處理液收容器，其中所述保管容器的內壁的材質為選自高密度聚乙烯、高密度聚丙烯、6,6-尼龍、四氟乙烯、四氟乙烯與全氟烷基乙烯基醚的共聚物、聚氯三氟乙烯、乙烯・氯三氟乙烯共聚物、乙烯・四氟乙烯共聚物及四氟乙烯・六氟丙烯共聚物中的一種以上的樹脂。The processing liquid container according to claim 11 or 12, wherein the inner wall of the storage container is made of a material selected from the group consisting of high density polyethylene, high density polypropylene, 6,6-nylon, and tetrafluoroethylene. Copolymer of ethylene, tetrafluoroethylene and perfluoroalkyl vinyl ether, polychlorotrifluoroethylene, ethylene/chlorotrifluoroethylene copolymer, ethylene/tetrafluoroethylene copolymer and tetrafluoroethylene/hexafluoropropylene copolymer More than one resin. 如申請專利範圍第11項或第12項所述的處理液收容器，其中所述保管容器的內壁的材質為分子內含有氟原子的氟系樹脂。The processing liquid container according to the eleventh or twelfth aspect, wherein the material of the inner wall of the storage container is a fluorine-based resin containing fluorine atoms in the molecule. 如申請專利範圍第11項或第12項所述的處理液收容器，其中所述保管容器具有多個開口部。The treatment liquid container according to claim 11 or 12, wherein the storage container has a plurality of openings.
TW105140731A 2015-12-11 2016-12-09 Method of storing process liquid for semiconductor device, and container filled with process liquid TWI716510B (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015242707 2015-12-11
JP2015-242707 2015-12-11

Publications (2)

Publication Number Publication Date
TW201732914A true TW201732914A (en) 2017-09-16
TWI716510B TWI716510B (en) 2021-01-21

Family

ID=59013161

Family Applications (1)

Application Number Title Priority Date Filing Date
TW105140731A TWI716510B (en) 2015-12-11 2016-12-09 Method of storing process liquid for semiconductor device, and container filled with process liquid

Country Status (4)

Country Link
JP (1) JP6518788B2 (en)
KR (1) KR102067444B1 (en)
TW (1) TWI716510B (en)
WO (1) WO2017099121A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102455268B1 (en) * 2017-07-18 2022-10-17 후지필름 가부시키가이샤 Container, method for manufacturing container, and drug container
CN112805628A (en) * 2018-10-03 2021-05-14 富士胶片株式会社 Chemical solution, chemical solution container, resist pattern forming method, and semiconductor chip manufacturing method
CN114746536B (en) * 2019-11-25 2024-01-09 株式会社力森诺科 Method for producing decomposition cleaning composition
JPWO2021176913A1 (en) * 2020-03-04 2021-09-10

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4582602B2 (en) * 2000-03-24 2010-11-17 ビーエーエスエフ ソシエタス・ヨーロピア Hydroxylamine aqueous solution and process for producing the same
US7166419B2 (en) * 2002-09-26 2007-01-23 Air Products And Chemicals, Inc. Compositions substrate for removing etching residue and use thereof
JP2005236050A (en) * 2004-02-19 2005-09-02 Az Electronic Materials Kk Apparatus for supplying chemical solutions for manufacturing electronic device and method for exchanging solution vessel
US8357646B2 (en) * 2008-03-07 2013-01-22 Air Products And Chemicals, Inc. Stripper for dry film removal
US20130323588A1 (en) * 2010-12-28 2013-12-05 Jsr Corporation Electrode binder composition, electrode slurry, electrode, electrochemical device, method for producing electrode binder composition, and method for storing electrode binder composition
US8889609B2 (en) 2011-03-16 2014-11-18 Air Products And Chemicals, Inc. Cleaning formulations and method of using the cleaning formulations

Also Published As

Publication number Publication date
TWI716510B (en) 2021-01-21
JPWO2017099121A1 (en) 2018-08-30
JP6518788B2 (en) 2019-05-22
KR20180074755A (en) 2018-07-03
KR102067444B1 (en) 2020-01-17
WO2017099121A1 (en) 2017-06-15

Similar Documents

Publication Publication Date Title
KR102051346B1 (en) Processing liquid, substrate cleaning method and resist removal method
JP6629880B2 (en) Cleaning solution, substrate cleaning method, and semiconductor device manufacturing method
TWI611047B (en) Liquid cleaner for the removal of post-etch residues
JP6542392B2 (en) PROCESSING LIQUID, METHOD FOR CLEANING SUBSTRATE, AND METHOD FOR MANUFACTURING SEMICONDUCTOR DEVICE
TWI702286B (en) Process liquid, method for cleaning substrate, and method for manufacturing semiconductor device
TWI716510B (en) Method of storing process liquid for semiconductor device, and container filled with process liquid
JPWO2018061582A1 (en) Processing solution and method of processing laminate
JP7324290B2 (en) Processing liquid, kit, manufacturing method of processing liquid, cleaning method of substrate, processing method of substrate
TWI359866B (en) Cleaning composition and method
TW201736591A (en) Treatment solution, method of cleaning substrate and method of manufacturing semiconductor device
JP7065763B2 (en) Treatment method for chemicals and objects to be treated
WO2022024609A1 (en) Treatment liquid and substrate washing method
WO2022176663A1 (en) Cleaning liquid and method for cleaning semiconductor substrate
JP7273165B2 (en) Treatment liquid, treatment method for treated object
JP7297948B2 (en) Treatment liquid, treatment method for treated object
JP7340614B2 (en) cleaning method
WO2022163350A1 (en) Composition, and method for cleaning substrate
JP2005336342A (en) Cleaning composition
JP2005308872A (en) Resist stripping composition