Classifications

• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/62—Detectors specially adapted therefor
  • G01N30/72—Mass spectrometers
  • G01N30/7206—Mass spectrometers interfaced to gas chromatograph
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/62—Detectors specially adapted therefor
  • G01N30/72—Mass spectrometers
  • G01N30/7233—Mass spectrometers interfaced to liquid or supercritical fluid chromatograph
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/30—Imagewise removal using liquid means
  • G03F7/32—Liquid compositions therefor, e.g. developers
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/86—Signal analysis
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/26—Processing photosensitive materials; Apparatus therefor
  • G03F7/42—Stripping or agents therefor
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N2030/022—Column chromatography characterised by the kind of separation mechanism
  • G01N2030/025—Gas chromatography
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/88—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
  • G01N2030/8809—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
  • G01N2030/884—Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample organic compounds
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/04—Preparation or injection of sample to be analysed
  • G01N30/06—Preparation
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
  • G01N30/02—Column chromatography
  • G01N30/62—Detectors specially adapted therefor
  • G01N30/72—Mass spectrometers

Definitions

• the present invention relates to a treatment liquid assay method and a treatment liquid production method.
• Patent Document 1 discloses that a resist film is treated using a developer or rinse containing an aliphatic hydrocarbon solvent, but the line width of the resist pattern obtained after the treatment is The inventors have found that there may be variations.
• a method for testing a treatment liquid containing an aliphatic hydrocarbon solvent Step A1 of obtaining measurement data of the content of at least one acid component selected from the group consisting of a carboxylic acid having a hydrocarbon group of 1 to 3 carbon atoms and formic acid in the treatment liquid; and a step A2 of determining whether or not the measurement data obtained in step A1 is within a preset allowable range.
• the aliphatic hydrocarbon solvent contains at least one selected from the group consisting of nonane, decane, undecane, dodecane and methyldecane.
• Step B1 of obtaining measurement data of the mass ratio of the content of the ester solvent to the content of the aliphatic hydrocarbon solvent in the treatment liquid comprising a step B2 of determining whether or not the measurement data obtained in the step B1 is within a preset allowable range.
• the ester solvent is butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, ethyl butyrate, ethyl isobutyrate, amyl formate, isoamyl formate.
• Step C1 of acquiring measurement data of the content of aromatic hydrocarbons in the treatment liquid The process liquid test method according to any one of [1] to [8], comprising a step C2 of determining whether or not the measurement data obtained in the step C1 is within a preset allowable range. .
• a step D1 of acquiring measurement data of the alcohol content in the treatment liquid comprising a step D2 of determining whether or not the measurement data obtained in the step D1 is within a preset allowable range.
• a processing liquid testing method for determining whether or not a processing liquid can form a resist pattern with suppressed line width variation when used as a developer or rinse liquid. Further, according to the present invention, it is possible to provide a method for producing a treatment liquid.
• a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
• the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
• the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
• the amount of each component in the treatment liquid is the total amount of the plurality of substances present in the treatment liquid unless otherwise specified when there are a plurality of substances corresponding to each component in the treatment liquid.
• ppm means “parts-per-million ( 10-6 )
• ppb means “parts-per-billion ( 10-9 )
• ppt means means “parts-per-trillion ( 10-12 )”
• ppq means “parts-per-quadrillion ( 10-15 )”.
• 1 ⁇ (angstrom) corresponds to 0.1 nm.
• the notation that does not describe substituted or unsubstituted includes not only those without substituents but also those with substituents, as long as the effects of the present invention are not impaired. It includes.
• the term "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). . This is also the same for each compound.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam), etc.
• light means actinic rays or radiation.
• exposure means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams, and It also includes drawing with particle beams such as ion beams. In the present specification, a combination of two or more preferred aspects is a more preferred aspect.
• the processing liquid test method of the present invention (hereinafter also referred to as “this test method”) is a test method for a processing liquid containing an aliphatic hydrocarbon solvent, wherein the processing liquid has 1 to 3 carbon atoms. and a step A1 of obtaining measurement data of the content of at least one acid component (hereinafter also referred to as “specific acid component”) selected from the group consisting of a carboxylic acid having a hydrocarbon group of and formic acid; and a step A2 of determining whether or not the measurement data obtained in the step A1 is within a preset allowable range.
• this test method is a test method for a processing liquid containing an aliphatic hydrocarbon solvent, wherein the processing liquid has 1 to 3 carbon atoms. and a step A1 of obtaining measurement data of the content of at least one acid component (hereinafter also referred to as “specific acid component”) selected from the group consisting of a carboxylic acid having a hydrocarbon group of and formic acid; and a step A2 of
• the line width variation of the resist pattern processed using this processing liquid can be detected. Without actually measuring the line width of the resist pattern, it can be determined with high accuracy whether or not the line width varies. Although the details of the reason for this have not yet been clarified, the variation in the line width of the resist pattern is closely related to the content of the specific acid component contained in the processing solution (developer or rinse solution) used to form the resist pattern. It is presumed to be related. Although the details are unknown, the presence of the specific acid component in a predetermined amount can suppress an increase in line width variation due to the specific acid component itself, and can interact with other components that can cause line width variation. It is inferred that the variation in line width is suppressed by the occurrence of
• Treatment liquid In the following, components contained in the treatment liquid (hereinafter also referred to as “main treatment liquid”) used in this assay method and components that may be contained therein will be described.
• the treatment liquid contains an aliphatic hydrocarbon solvent.
• the aliphatic hydrocarbon-based solvent is a component contained in the treatment liquid as an organic solvent.
• the organic solvent is an organic solvent contained in a content of 8000 ppm by mass or more with respect to the total mass of the treatment liquid. Also, an organic solvent contained in a content of less than 8000 ppm by mass with respect to the total mass of the treatment liquid corresponds to organic impurities and does not correspond to organic solvent.
• the aliphatic hydrocarbon solvent may be linear, branched or cyclic (monocyclic or polycyclic), preferably linear.
• the aliphatic hydrocarbon-based solvent may be either a saturated aliphatic hydrocarbon or an unsaturated aliphatic hydrocarbon.
• the number of carbon atoms in the aliphatic hydrocarbon-based solvent is often 2 or more, preferably 5 or more, and more preferably 9 or more.
• the upper limit is preferably 30 or less, more preferably 20 or less, still more preferably 15 or less, and particularly preferably 13 or less.
• the aliphatic hydrocarbon-based solvent preferably has 11 carbon atoms.
• aliphatic hydrocarbon solvents examples include pentane, isopentane, hexane, isohexane, cyclohexane, ethylcyclohexane, methylcyclohexane, heptane, octane, isooctane, nonane, decane, methyldecane, undecane, dodecane, tridecane, tetradecane, pentadecane, and hexadecane.
• hepradecan 2,2,4-trimethylpentane and 2,2,3-trimethylhexane.
• the aliphatic hydrocarbon-based solvent preferably contains an aliphatic hydrocarbon having 5 or more carbon atoms (preferably 20 or less carbon atoms) in terms of better functions as a developer and a rinse solution, and preferably contains 9 or more carbon atoms (preferably 20 or less carbon atoms). More preferably, it contains an aliphatic hydrocarbon having 13 or less carbon atoms), more preferably at least one selected from the group consisting of nonane, decane, undecane, dodecane and methyldecane, and more preferably contains undecane. Particularly preferred, and most preferred is undecane.
• the aliphatic hydrocarbon-based solvents may be used singly or in combination of two or more.
• the content of the aliphatic hydrocarbon-based solvent is preferably 1% by mass or more and less than 100% by mass, and 2 to 70% by mass, based on the total mass of the present processing liquid, in terms of better functions as a developer and a rinse liquid. %, more preferably 5 to 30% by mass.
• the treatment liquid may contain a specific acid component.
• the specific acid component means a carboxylic acid having a hydrocarbon group of 1 to 3 carbon atoms and formic acid, as described above.
• the specific acid component may ionize and exist as ions in the treatment liquid.
• the specific acid component may be contained in a raw material (for example, an organic solvent) used in the production of the present treatment liquid, may be intentionally added in the production process of the present treatment liquid, or may be may be transferred (so-called contamination) from the manufacturing apparatus of the present treatment liquid in the manufacturing process of .
• carboxylic acids having a hydrocarbon group of 1 to 3 carbon atoms include fatty acids having an alkyl group of 1 to 3 carbon atoms, such as acetic acid, propionic acid, and n-butyric acid (butyric acid), and malon. Acids, succinic acid, glutaric acid, maleic acid, polyvalent carboxylic acids having a hydrocarbon group of 1 to 3 carbon atoms such as fumaric acid, and fatty acids having an alkyl group of 1 to 3 carbon atoms are preferred. Only one type of the specific acid component may be contained, or two or more types may be contained.
• the content of the specific acid component is not particularly limited, it is preferably 1 to 2000 ppm by mass, more preferably 3 to 1200 ppm by mass, and even more preferably 10 to 30 ppm by mass relative to the total mass of the treatment liquid.
• the treatment liquid may contain at least one metal element selected from the group consisting of Fe, Ni, and Cr (hereinafter also referred to as "specific metal element").
• the specific metal element may be contained in the present treatment liquid in the form of particles (metal-containing particles) or may be contained in the present treatment liquid in the form of ions (metal ions). It may be contained in the present treatment liquid in the form of
• the specific metal impurities may be contained in raw materials (for example, organic solvents) used in the production of the present treatment liquid, may be intentionally added in the production process of the present treatment liquid, or may be may be transferred (so-called contamination) from the manufacturing apparatus of the present treatment liquid in the manufacturing process of .
• the content of the specific metal element is not particularly limited, but is preferably 0.03 to 100 mass ppt, more preferably 3 to 60 mass ppt, and even more preferably 3 to 25 mass ppt, relative to the total mass of the treatment liquid. . Only one kind of specific metal element may be contained, or two or more kinds thereof may be contained. When two or more specific metal elements are included, the total content is within the above range.
• the processing liquid preferably further contains an ester-based solvent, which is a type of organic solvent, from the viewpoint of better functions as a developer and a rinse liquid.
• the ester solvent may be linear, branched or cyclic (monocyclic or polycyclic), preferably linear.
• the carbon number of the ester solvent is often 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 6 or more.
• the upper limit is often 20 or less, preferably 10 or less, more preferably 8 or less, and particularly preferably 7 or less. Specifically, the number of carbon atoms in the ester solvent is preferably 6.
• ester solvents include butyl acetate, isobutyl acetate, tert-butyl acetate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, hexyl acetate, methoxybutyl acetate, amyl acetate, isoamyl acetate, methyl formate, ethyl formate, Butyl formate, propyl formate, amyl formate, isoamyl formate, methyl lactate, ethyl lactate, butyl lactate, propyl lactate, methyl 2-hydroxyisobutyrate, ethyl butyrate, ethyl isobutyrate, ethyl propionate, propyl propionate, isopropyl propionate, butyl propionate and isobutyl propionate.
• Ester solvents include butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, ethyl butyrate, ethyl isobutyrate, amyl formate, and isoamyl formate. It preferably contains at least one selected from the group consisting of, more preferably butyl acetate, and still more preferably butyl acetate. Only one kind of the ester solvent may be contained, or two or more kinds thereof may be contained.
• the content of the ester solvent is preferably 30 to 99% by mass, more preferably 30 to 98% by mass, more preferably 30 to 98% by mass, based on the total mass of the present processing liquid, in terms of better functions as a developer and a rinse solution. ⁇ 95% by mass is more preferred.
• the treatment liquid may further contain water.
• Water is not particularly limited, and examples thereof include distilled water, ion-exchanged water, and pure water. Water may be added to the treatment liquid, or may be unintentionally mixed in the treatment liquid during the manufacturing process of the treatment liquid. Cases where water is unintentionally mixed in the manufacturing process of the present processing liquid include, for example, the case where water is contained in the raw material (for example, organic solvent) used in the manufacture of the present processing liquid, and the case where water is included in the present processing liquid. Mixing in the manufacturing process (for example, contamination) is included, but is not limited to the above.
• the content of water is not particularly limited, but is preferably 1 to 1000 ppm by mass, more preferably 5 to 100 ppm by mass, relative to the total mass of the treatment liquid.
• the treatment liquid may further contain an aromatic hydrocarbon.
• Aromatic hydrocarbons are not included in the above-mentioned organic solvents and correspond to organic impurities. In other words, the content of aromatic hydrocarbons is less than 8000 mass ppm with respect to the total mass of the treatment liquid.
• the organic impurities may be added to the present processing liquid, or may be unintentionally mixed during the manufacturing process of the present processing liquid. Examples of cases where organic impurities are unintentionally mixed in the manufacturing process of the present processing liquid include the case where organic impurities are contained in the raw materials (e.g., organic solvents) used in the manufacture of the present processing liquid, and the case where the present processing liquid is manufactured. Mixing in the process (for example, contamination) is included, but is not limited to the above.
• the number of carbon atoms in the aromatic hydrocarbon is preferably 6-30, more preferably 6-20, even more preferably 10-12.
• the aromatic ring possessed by the aromatic hydrocarbon may be either monocyclic or polycyclic.
• the number of ring members of the aromatic ring of the aromatic hydrocarbon is preferably 6-12, more preferably 6-8, and still more preferably 6.
• the aromatic ring of the aromatic hydrocarbon may further have a substituent. Examples of the substituents include alkyl groups, alkenyl groups, and groups in which these groups are combined.
• the alkyl group and alkenyl group may be linear, branched or cyclic.
• the number of carbon atoms in the alkyl group and the alkenyl group is preferably 1-10, more preferably 1-5.
• aromatic hydrocarbon examples include a benzene ring that may have a substituent, a naphthalene ring that may have a substituent, and an anthracene ring that may have a substituent.
• a benzene ring optionally having a substituent is preferred. In other words, benzene, which may have a substituent, is preferable as the aromatic hydrocarbon.
• the aromatic hydrocarbon preferably contains at least one selected from the group consisting of C10H14 , C11H16 and C10H12 .
• a compound represented by formula (c) is also preferable as the aromatic hydrocarbon.
• R c represents a substituent.
• c represents an integer of 0 to 6;
• R c represents a substituent.
• the substituent represented by Rc is preferably an alkyl group or an alkenyl group.
• the alkyl group and alkenyl group may be linear, branched or cyclic.
• the number of carbon atoms in the alkyl group and the alkenyl group is preferably 1-10, more preferably 1-5.
• the R c may be the same or different, and the R c may combine with each other to form a ring.
• R c in the case where a plurality of R c are present, some or all of the plurality of R c ) may be condensed with the benzene ring in the formula (c) to form a condensed ring.
• c represents an integer of 0 to 6; c is preferably an integer of 1-5, more preferably an integer of 1-4.
• the molecular weight of the aromatic hydrocarbon is preferably 50 or more, more preferably 100 or more, even more preferably 120 or more.
• the upper limit is preferably 1000 or less, more preferably 300 or less, even more preferably 150 or less.
• aromatic hydrocarbons examples include 1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene and 1-ethyl-2 C 10 H 14 such as , 4-dimethyl-benzene; C 11 H 16 such as 1-methyl-4-(1-methylpropyl)-benzene and (1-methylbutyl)-benzene; 1-methyl-2-(2- C 10 H 12 such as propenyl)-benzene and 1,2,3,4-tetrahydro-naphthalene.
• aromatic hydrocarbons examples include 1,2,4,5-tetramethyl-benzene, 1-ethyl-3,5-dimethyl-benzene, 1,2,3,5-tetramethyl-benzene, 1-methyl-4-( 1-methylpropyl)-benzene and C 10 H 12 are preferred, and 1-ethyl-3,5-dimethyl-benzene or 1,2,3,5-tetramethyl-benzene are more preferred. Only one type of aromatic hydrocarbon may be contained, or two or more types may be contained.
• the content of the aromatic hydrocarbon is not particularly limited, but is preferably 1 to 2000 ppm by mass, more preferably 10 to 1200 ppm by mass, and even more preferably 60 to 360 ppm by mass relative to the total mass of the treatment liquid.
• the treatment liquid may further contain alcohol, which is one type of organic impurities. Alcohol is not included in the above-mentioned organic solvents and corresponds to organic impurities. In other words, the alcohol content is less than 8000 ppm by weight relative to the total weight of the treatment liquid.
• the number of carbon atoms in the alcohol is preferably 1-20, more preferably 1-5, and even more preferably 2-5.
• Alcohols are the group consisting of ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, 2-pentanol, 3-pentanol and 2-methyl-1-butanol It preferably contains at least one selected from, more preferably 1-butanol, 2-butanol, tert-butanol, and still more preferably 1-butanol. Only one kind of alcohol may be contained, or two or more kinds thereof may be contained.
• the alcohol content is not particularly limited, it is preferably 1 to 5000 ppm by mass, more preferably 10 to 400 ppm by mass, and even more preferably 20 to 60 ppm by mass, relative to the total mass of the treatment liquid.
• the present treatment liquid may contain other components than those described above.
• Other components include organic solvents such as ketone-based solvents, amide-based solvents and ether-based solvents, surfactants, sulfur-containing components, and the like.
• This treatment liquid is preferably used as a developer or rinse used in the manufacturing process of semiconductor devices.
• this processing solution is used for processing (especially, developing ) is also preferably used.
• the present treatment liquid can also be used as a pre-wet liquid used in the manufacturing process of semiconductor devices.
• the present processing liquid can also be used as a cleaning liquid for the end face and peripheral inclined portions (bevels) of the wafer, and as a backside cleaning liquid (cleaning liquid for the surface of the wafer opposite to the side on which the semiconductor substrate is formed).
• the treatment liquid can also be used as a cleaning liquid for various manufacturing equipment, coating treatment equipment, and transfer containers.
• This test method comprises a step A1 of obtaining measurement data of the content of the specific acid component in the treatment liquid, and determining whether or not the measurement data obtained in step A1 is within a preset allowable range. and a step A2.
• step A1 the identification of the type of the specific acid component in the treatment liquid and the measurement of the content can be performed using a GCMS (gas chromatography mass spectrometry).
• the allowable range in step A2 is set in advance by the time step A1 is carried out. Based on this allowable range, if the measurement data obtained in step A1 falls within the allowable range, it is judged as "acceptable”, and if it does not fall within the allowable range, it is judged as "failed”.
• a treatment liquid determined to be acceptable by this test method can form a resist pattern in which variations in line width are suppressed.
• the allowable range used in step A2 can be set as follows. First, a plurality of processing solutions having different specific acid component contents are prepared, and the resist film is processed (developed or rinsed) using each of the processing solutions. to obtain a resist pattern. Next, the variation in line width of each resist pattern obtained is measured, and the processing liquid used for forming the resist pattern is selected for which the variation in line width is within an allowable range. Then, based on the content of the specific acid component in the selected treatment liquid, the range of the content of the specific acid component in the treatment liquid is set and set as the allowable range.
• the content of the specific acid component that can be within the allowable range is preferably 2000 ppm by mass or less, more preferably 1200 ppm by mass or less, and even more preferably 30 ppm by mass or less, relative to the total mass of the treatment liquid.
• step A2 of determining whether or not the above measurement data is within the allowable range is performed by, for example, a processing device configured using hardware such as a computer.
• a processing device configured using hardware such as a computer.
• An example of the configuration of a processing device that performs the determination of step A2 will be described below, but step A2 is not limited to that performed by the following processing device.
• the processing device has an input unit, a processing unit, a storage unit, and an output unit.
• the memory has a memory that can store data from the outside and a ROM (Read Only Memory).
• the processing device may be configured by a computer in which each part functions by executing a program stored in a ROM, or may be a dedicated device in which each part is configured by a dedicated circuit. Note that the program is supplied in the form of computer software, for example.
• the input unit is a part having a function of inputting the measurement data obtained in step A1, and may be, for example, various input devices such as a mouse and keyboard, or may be a measuring device that performs step A1. .
• the processing unit is a part that performs the determination of step A2. More specifically, the measurement data obtained in step A1 is received from the input unit, the allowable range stored in the storage unit is read, the measurement data is compared with the allowable range, and the measured data is within the allowable range. Determine whether or not it is included.
• the processing unit performs predetermined control on the output unit according to the determination result according to a preset program. Also, the processing unit causes the storage unit to store the measurement data input from the input unit.
• the processing unit calculates and stores new reference data and tolerance based on data selected from the group consisting of measurement data input from the input unit and past measurement data stored in the storage unit. store in the department.
• the output unit is a part having a function of outputting the determination result of step A2, for example, a display device such as a display that displays the determination result, a device such as a printer that displays the determination result on an output medium, and a sound that outputs an alarm. Examples include an output device and communication means for informing the user of the determination result.
• step A2 if the measurement data obtained in step A1 is not included in the allowable range (if the judgment result is unacceptable), the processing unit displays the unacceptable judgment result (display on the display device and The output unit may be controlled to perform processing selected from display on an output medium, etc.) and execution of warnings to the user (warning and notification, etc.). As a result, the user is notified that the measurement data acquired in step A1 is not within the allowable range, and the production of the treatment liquid is stopped and the treatment liquid of the same lot as the treatment liquid from which the measurement data was acquired is discarded or purified. can be prompted to the user.
• the processing unit displays the judgment result of acceptance (display on the display device and display on the output medium). etc.) and the output unit may be controlled to perform processing selected from notifications to the user.
• the processing apparatus may have a manufacturing unit (manufacturing apparatus) that manufactures the processing liquid, and the processing unit may be connected to the manufacturing unit through an electric circuit.
• the processing unit controls the manufacturing unit to stop manufacturing the treatment liquid.
• the manufacturing department may be controlled to continue manufacturing the treatment liquid.
• the manufacturing unit is not particularly limited in configuration as long as it can manufacture the treatment liquid, and a known manufacturing apparatus can be used as appropriate.
• This assay method may further have steps other than steps A1 and A2. Other steps include steps B1 and B2, steps C1 and C2, steps D1 and D2, steps E1 and E2, steps F1 and F2.
• step B1 for obtaining measurement data of the mass ratio of the content of the ester solvent to the content of the aliphatic hydrocarbon solvent in the treatment liquid, and the measurement data obtained in step B1 are set in advance. and a step B2 of determining whether or not it is included in the determined allowable range.
• step B1 for obtaining measurement data of the mass ratio of the content of the ester solvent to the content of the aliphatic hydrocarbon solvent in the treatment liquid are set in advance.
• a step B2 of determining whether or not it is included in the determined allowable range As a result, it is possible to accurately determine whether the processing liquid has excellent sensitivity (ratio to the set sensitivity) without actually processing the resist film with the processing liquid.
• step B1 identification of the type of aliphatic hydrocarbon solvent and ester solvent in the treatment liquid, measurement of the content, and measurement of the mass ratio are performed by GCMS (gas chromatography mass spectrometry).
• GCMS gas chromatography mass spectrometry
• the allowable range in step B2 is set in advance by the time step B1 is carried out. Based on this allowable range, if the measurement data obtained in step B1 is within the allowable range, it is judged as "passed", and if it is not within the allowable range, it is judged as "failed”. It can be said that a processing liquid that has been judged as acceptable by this test method is a processing liquid that has an excellent ratio to the set sensitivity.
• the allowable range used in step B2 can be set as follows. First, the mass ratio of the content of the ester solvent to the content of the aliphatic hydrocarbon solvent is known, and a plurality of processing solutions having different mass ratios are prepared, and each processing solution is used to prepare a resist film. (development or rinsing) to obtain a resist pattern. Next, the sensitivity is measured for each of the obtained resist patterns, and the treatment liquid used for forming the resist pattern is selected for which the ratio to the set sensitivity is within an allowable range. Then, based on the mass ratio in the selected treatment liquid, the range of the mass ratio in the treatment liquid is set and set as the allowable range.
• the mass ratio that can be within the acceptable range is preferably 0.4 to 99.0, more preferably 2.3 to 49.0, still more preferably 2.3 to 19.0, particularly 8.1 to 10.1 preferable.
• step B2 The processing equipment and the like used in step B2 are the same as the processing equipment described in step A2, so description thereof will be omitted.
• This test method comprises a step C1 of acquiring measurement data of the content of aromatic hydrocarbons in the treatment liquid, and determining whether or not the measurement data obtained in step C1 is within a preset allowable range. You may have the process C2 which carries out. As a result, whether or not a resist pattern with few bridging defects can be formed can be accurately determined without actually treating the resist film with the present treatment liquid.
• the bridge defect means a bridging defect that connects patterns in the formed resist pattern.
• step C1 identification of the type of aromatic hydrocarbons in the treatment liquid and measurement of the content can be performed using a GCMS (gas chromatography mass spectrometry).
• GCMS gas chromatography mass spectrometry
• the permissible range in process C2 is set in advance by the time process C1 is performed. Based on this allowable range, if the measurement data obtained in step C1 is within the allowable range, it is judged as "acceptable”, and if it is not within the allowable range, it is judged as "failed”. A processing solution that is judged to be acceptable by this test method can form a resist pattern with few bridging defects.
• the allowable range used in step C2 can be set as follows. First, a plurality of processing liquids having a known aromatic hydrocarbon content and different aromatic hydrocarbon contents are prepared, and the resist film is processed (developed or rinsed) using each processing liquid. to obtain a resist pattern. Next, the bridging defects of each obtained resist pattern are measured, and the processing solution used for forming the resist pattern having the bridging defect within the allowable range is selected. Based on the content of aromatic hydrocarbons in the selected liquid to be treated, the range of the content of aromatic hydrocarbons in the liquid to be treated is set and set as the allowable range. The content of aromatic hydrocarbons that can be within the allowable range is preferably 2000 ppm by mass or less with respect to the total mass of the treatment liquid.
• processing equipment and the like used in process C2 are the same as the processing equipment described in process A2, so description thereof will be omitted.
• This test method includes a step D1 of acquiring measurement data of the alcohol content in the treatment liquid, and a step D2 of determining whether the measurement data obtained in step D1 is within a preset allowable range. and may have As a result, whether or not a resist pattern with few defects can be obtained can be accurately determined without actually treating the resist film with the present treatment liquid.
• step D1 identification of the type of alcohol in the treatment liquid and measurement of the content can be performed using GCMS (gas chromatography mass spectrometry).
• the allowable range in process D2 is set in advance by the time process D1 is performed. Based on this allowable range, if the measurement data obtained in step D1 is within the allowable range, it is judged as "accepted”, and if it is not within the allowable range, it is judged as "failed”. A processing liquid determined to be acceptable by this test method can form a resist pattern with few defects.
• the allowable range used in step D2 can be set as follows. First, a plurality of processing liquids with different alcohol contents are prepared and the alcohol content is known, and the resist film is processed (developed or rinsed) using each processing liquid to form a resist pattern. get Next, the number of defects in each of the obtained resist patterns is measured, and the processing liquid used for forming the resist pattern having the allowable number of defects is selected. Then, based on the content of alcohol in the selected processing liquid, the range of alcohol content in the processing liquid is set and set as the allowable range.
• the content of alcohol that can be within the allowable range is preferably 5000 ppm by mass or less, more preferably 150 ppm by mass or less, and even more preferably 60 ppm by mass or less, relative to the total mass of the treatment liquid.
• processing equipment and the like used in process D2 are the same as the processing equipment described in process A2, so description thereof will be omitted.
• the test method includes a step E1 of acquiring measurement data of the water content in the treatment liquid, and a step E2 of determining whether the measurement data obtained in step E1 is within a preset allowable range. and may have As a result, it is possible to accurately determine whether or not a resist pattern in which pattern collapse is suppressed can be formed without actually treating the resist film with the present treatment liquid.
• step E1 the water content in the treatment liquid can be measured using an apparatus based on the Karl Fischer moisture measurement method.
• the allowable range in step E2 is set in advance by the time step E1 is carried out. Based on this allowable range, if the measurement data obtained in step E1 is within the allowable range, it is determined as "accepted”, and if it is not within the allowable range, it is determined as "failed”. A treatment liquid that is judged to be acceptable by this test method can form a resist pattern in which pattern collapse is suppressed.
• the allowable range used in step E2 can be set, for example, as follows. First, a plurality of processing liquids having different water contents are prepared and the water content is known, and the resist film is processed (developed or rinsed) using each processing liquid to form a resist pattern. get Next, the pattern collapse of each of the obtained resist patterns is measured, and the treatment liquid used for forming the resist pattern having the pattern collapse within an allowable range is selected. Then, based on the content of water in the selected treatment liquid, the range of water content in the treatment liquid is set and set as the allowable range.
• the content of water that can be within the allowable range is preferably 1000 ppm by mass or less, more preferably 100 ppm by mass or less, relative to the total mass of the treatment liquid.
• the processing equipment and the like used in the process E2 are the same as the processing equipment described in the process A2, so the description thereof will be omitted.
• This test method includes a step F1 of acquiring measurement data of the content of the specific metal element in the treatment liquid, and determining whether or not the measurement data obtained in step F1 is within a preset allowable range. and a step F2. As a result, whether or not a resist pattern with few defects containing metal elements (defects containing metal) can be formed can be accurately determined without actually processing the resist film with the present processing liquid.
• the type and content of the specific metal element can be measured using an apparatus based on the measurement principle of ICP-MS (inductively coupled plasma mass spectrometry).
• ICP-MS inductively coupled plasma mass spectrometry
• the content of the metal element to be measured is measured regardless of its existence form.
• the specific metal impurity is contained in the present treatment liquid in the form of metal-containing particles
• the content of the specific metal element in the metal-containing particles is measured.
• the specific metal impurity is contained in the present treatment liquid in the form of metal ions
• the content of the specific metal element corresponding to the metal ions is measured.
• the content of the specific metal element in the metal-containing particles and the specific metal corresponding to the metal ion is measured.
• devices for the ICP-MS method include Agilent 8900 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, Inc., and the method described in the Examples. can be measured by Other devices than the above include NexION350S manufactured by PerkinElmer, and Agilent 8800 manufactured by Agilent Technologies.
• the allowable range in process F2 is set in advance by the time process F1 is performed. Based on this allowable range, if the measurement data obtained in step F1 is within the allowable range, it is judged as "accepted”, and if it is not within the allowable range, it is judged as "failed”.
• a processing solution determined to be acceptable by this test method can form a resist pattern with few metal-containing defects.
• the allowable range used in step F2 can be set as follows. First, a plurality of processing liquids having a known content of the specific metal element and different contents of the specific metal element are prepared, and the resist film is processed (developed or rinsed) using each of the processing liquids. to obtain a resist pattern. Next, the number of metal-containing defects in each of the obtained resist patterns is measured, and the treatment liquid used for forming the resist pattern having the number of metal-containing defects within an allowable range is selected. Then, based on the content of the specific metal element in the selected treatment liquid, the range of the content of the specific metal element in the treatment liquid is set and set as the allowable range.
• the content of the specific metal element that can be within the allowable range is preferably 100 mass ppt or less, more preferably 60 mass ppt or less, and even more preferably 30 mass ppt or less, relative to the total mass of the treatment liquid.
• process F2 The processing equipment and the like used in process F2 are the same as the processing equipment described in process A2, so description thereof will be omitted.
• the method for producing the present treatment liquid is not particularly limited, but in addition to the above-described steps, it may have a filtering step of filtering a substance to be purified containing an organic solvent using a filter.
• the material to be purified used in the filtration process may be procured through purchase, etc., or may be obtained by reacting raw materials. It is preferable that the material to be purified has a low impurity content.
• Commercially available products of such substances to be purified include, for example, commercial products called “high-purity grade products”.
• the method of reacting raw materials to obtain a substance to be purified is not particularly limited, and known methods can be used.
• a method of obtaining an organic solvent by reacting one or more raw materials in the presence of a catalyst.
• the method for producing the present treatment liquid according to the embodiment of the present invention has a filtering step of obtaining the present treatment liquid by filtering the material to be purified using a filter.
• the method of filtering the substance to be purified using a filter is not particularly limited, but the substance to be purified is passed through a filter unit having a housing and a filter cartridge housed in the housing under pressure or without pressure ( It is preferable to allow the liquid to pass through.
• Pore size of filter The pore size of the filter is not particularly limited, and a filter having a pore size commonly used for filtering substances to be purified can be used.
• the pore diameter of the filter is preferably 200 nm or less, more preferably 20 nm or less, and further preferably 10 nm or less, in that the number of particles (metal-containing particles, etc.) that can be contained in the treatment liquid can be easily controlled within a desired range. 5 nm or less is particularly preferred, and 3 nm or less is most preferred.
• the lower limit is not particularly limited, but generally 1 nm or more is preferable from the viewpoint of productivity.
• the pore size and pore size distribution of the filter refer to isopropanol (IPA) or HFE-7200 (“Novec 7200”, manufactured by 3M, hydrofluoroether, C 4 F 9 OC 2 H 5 ) means pore size and pore size distribution as determined by the bubble point.
• IPA isopropanol
• HFE-7200 Novec 7200, manufactured by 3M, hydrofluoroether, C 4 F 9 OC 2 H 5
• the pore size of the filter is 5.0 nm or less, since the number of particles contained in the treatment liquid can be easily controlled.
• a filter with a pore size of 5 nm or less is also referred to as a "micropore size filter”.
• the fine pore size filter may be used alone, or may be used together with filters having other pore sizes. Among them, it is preferable to use a filter having a larger pore size from the viewpoint of better productivity. In this case, clogging of the micropore filter can be prevented by allowing the substance to be purified, which has been previously filtered through a filter having a larger pore size, to pass through the micropore filter. That is, when one filter is used, the pore size of the filter is preferably 5.0 nm or less, and when two or more filters are used, the filter having the smallest pore size has a pore size of 5.0 nm. The following are preferred.
• the material for the filter is not particularly limited, and known materials for the filter can be used. Specifically, when it is a resin, polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; polyimide; polyamideimide; Polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene propene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, and polyvinyl such as polyvinyl fluoride fluorocarbon; polyvinyl alcohol; polyester; cellulose; cellulose acetate and the like.
• polyamides such as nylon (e.g., 6-nylon and 6,6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene;
• nylon (among them, 6,6-nylon is preferable) and polyolefin (among them, polyethylene is preferable) in that they have better solvent resistance and the resulting treatment liquid has more excellent defect suppression performance.
• poly(meth)acrylates and polyfluorocarbons (preferably polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA)). These polymers can be used individually or in combination of 2 or more types. In addition to resin, diatomaceous earth, glass, and the like may also be used.
• a polymer nylon-grafted UPE, etc. obtained by graft-copolymerizing a polyolefin (UPE, etc. described later) with a polyamide (eg, nylon such as nylon-6 or nylon-6,6) may be used as the filter material.
• the filter may be a surface-treated filter.
• the surface treatment method is not particularly limited, and known methods can be used. Examples of surface treatment methods include chemical modification treatment, plasma treatment, hydrophilic/hydrophobic treatment, coating, gas treatment, and sintering.
• Plasma treatment is preferable because it makes the surface of the filter hydrophilic.
• the water contact angle on the surface of the filter material hydrophilized by plasma treatment is not particularly limited, but the static contact angle at 25 ° C. measured with a contact angle meter is preferably 60 ° or less, more preferably 50 ° or less. , 30° or less are particularly preferred.
• a method of introducing an ion exchange group into the base material is preferable. That is, as the filter, a filter obtained by introducing an ion-exchange group into the base material of each of the above-mentioned materials is preferable. Filters comprising a layer comprising a substrate containing ion-exchange groups on the surface of the substrate are typically preferred.
• the surface-modified substrate is not particularly limited, and a filter obtained by introducing an ion-exchange group into the above polymer is preferable because it is easier to manufacture.
• cation-exchange groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups
• anion-exchange groups include quaternary ammonium groups.
• the method of introducing the ion-exchange group into the polymer is not particularly limited, but typically includes a method of grafting by reacting a compound containing an ion-exchange group and a polymerizable group with the polymer.
• the method for introducing the ion-exchange group is not particularly limited, but the fibers of the above resin are irradiated with ionizing radiation ( ⁇ -rays, ⁇ -rays, ⁇ -rays, X-rays, electron beams, etc.) to introduce active moieties ( radicals).
• ionizing radiation ⁇ -rays, ⁇ -rays, ⁇ -rays, X-rays, electron beams, etc.
• active moieties radicals
• the irradiated resin is immersed in a monomer-containing solution to graft polymerize the monomer onto the substrate. As a result, a polymer is produced in which this monomer is attached to the polyolefin fiber as a grafted side chain.
• the resulting resin containing the polymer as a side chain is contacted with a compound containing an anion-exchange group or a cation-exchange group to introduce an ion-exchange group into the graft-polymerized side chain polymer to obtain a final product. can get.
• the filter may be configured by combining a woven fabric or non-woven fabric on which ion exchange groups are formed by a radiation graft polymerization method and a conventional filter material of glass wool, woven fabric or non-woven fabric.
• the material of the filter containing ion-exchange groups is not particularly limited, but examples thereof include polyfluorocarbons and materials obtained by introducing ion-exchange groups into polyolefin, and materials obtained by introducing ion-exchange groups into polyfluorocarbons are more preferable.
• the pore size of the filter containing ion exchange groups is not particularly limited, but is preferably 1 to 200 nm, more preferably 1 to 30 nm, and even more preferably 3 to 20 nm.
• the filter containing ion-exchange groups may also serve as the filter having the minimum pore size already described, or may be used separately from the filter having the minimum pore size.
• a filter containing ion-exchange groups and a filter having no ion-exchange groups and having a minimum pore size are used in order to obtain the treatment liquid exhibiting the superior effects of the present invention.
• the material of the filter having the smallest pore size already described is not particularly limited, but from the viewpoint of solvent resistance and the like, in general, at least one selected from the group consisting of polyfluorocarbons and polyolefins is preferable, and polyolefin is more preferred.
• two or more filters made of different materials may be used as the filter used in the filtration step. Two or more selected from the group consisting of may be used.
• Pore structure of filter The pore structure of the filter is not particularly limited, and may be appropriately selected according to the components in the substance to be purified.
• the pore structure of a filter means the pore size distribution, the positional distribution of pores in the filter, the shape of the pores, etc., and is typically controlled by the manufacturing method of the filter. It is possible.
• a porous membrane can be obtained by sintering a powder such as a resin, and a fiber membrane can be obtained by electrospinning, electroblowing, meltblowing, or the like. These have different pore structures.
• porous membrane is a membrane that retains components in an object to be purified, such as gels, particles, colloids, cells, and poly-oligomers, but allows components that are substantially smaller than the pores to pass through the pores.
• Retention of components in the material to be purified by porous membranes can depend on operating conditions such as surface velocity, use of surfactants, pH, and combinations thereof, and the pore size of the porous membrane, It can depend on the structure and the size and structure of the particles to be removed (hard particles or gels, etc.).
• non-sieving membranes include, but are not limited to, nylon membranes such as nylon-6 membranes and nylon-6,6 membranes.
• non-sieving retention mechanisms refer to retention that occurs through mechanisms such as obstruction, diffusion and adsorption that are not related to filter pressure drop or pore size.
• Non-sieving retention includes retention mechanisms such as hindrance, diffusion and adsorption that remove target particles in the material to be purified regardless of filter pressure drop or filter pore size.
• Adsorption of particles to the filter surface can be mediated, for example, by intermolecular van der Waals and electrostatic forces.
• a jamming effect occurs when particles traveling in a non-sieving membrane layer with a tortuous path are not able to change direction fast enough to avoid contact with the non-sieving membrane.
• Particle transport by diffusion results primarily from random or Brownian motion of small particles, which creates a certain probability of particles colliding with the filter media.
• Non-sieve retention mechanisms can be active when there is no repulsive force between the particles and the filter.
• UPE (ultra high molecular weight polyethylene) filters are typically sieve membranes.
• Sieve membrane means a membrane that traps particles primarily via a sieve retention mechanism or a membrane that is optimized for trapping particles via a sieve retention mechanism.
• Typical examples of sieve membranes include, but are not limited to, polytetrafluoroethylene (PTFE) membranes and UPE membranes.
• PTFE polytetrafluoroethylene
• the "sieve retention mechanism” refers to the retention of the result due to the particles to be removed being larger than the pore diameter of the porous membrane.
• Sieve retention is enhanced by forming a filter cake (a clump of particles to be removed on the surface of the membrane). The filter cake effectively performs the function of a secondary filter.
• the material of the fiber membrane is not particularly limited as long as it is a polymer capable of forming a fiber membrane.
• polymers include polyamides.
• Polyamides include, for example, nylon 6 and nylon 6,6.
• the polymer forming the fiber membrane may be poly(ethersulfone).
• the surface energy of the fiber membrane is preferably higher than the polymer from which the porous membrane is made on the secondary side.
• Such combinations include, for example, the fiber membrane material being nylon and the porous membrane being polyethylene (UPE).
• the method for producing the fiber membrane is not particularly limited, and known methods can be used. Examples of methods for producing fiber membranes include electrospinning, electroblowing, and meltblowing.
• the pore structure of the porous membrane is not particularly limited, but examples of the shape of the pores include lace, string, and node. be done.
• the size distribution of pores in the porous membrane and the distribution of their positions in the membrane are not particularly limited. The size distribution may be smaller and the distribution position in the membrane may be symmetrical. Moreover, the size distribution may be larger and the distribution position in the membrane may be asymmetrical (the above membrane is also referred to as an "asymmetric porous membrane").
• the pore size varies throughout the membrane, typically increasing in pore size from one surface of the membrane to the other surface of the membrane.
• an asymmetric porous membrane is a membrane in which the pore size is minimized at a certain position within the thickness of the membrane (this is also referred to as an "hourglass shape").
• an asymmetric porous membrane with larger sized pores on the primary side in other words an open side on the primary side, can produce a pre-filtration effect.
• the porous membrane may comprise a thermoplastic polymer such as PESU (polyethersulfone), PFA (perfluoroalkoxyalkane, copolymer of ethylene tetrafluoride and perfluoroalkoxyalkane), polyamide, and polyolefin. , polytetrafluoroethylene, and the like.
• PESU polyethersulfone
• PFA perfluoroalkoxyalkane, copolymer of ethylene tetrafluoride and perfluoroalkoxyalkane
• polyamide polyolefin
• ultra-high molecular weight polyethylene is preferable as the material for the porous membrane.
• Ultra-high molecular weight polyethylene means a thermoplastic polyethylene with very long chains and preferably has a molecular weight of 1 million or more, typically 2-6 million.
• filters used in the filtration process two or more filters with different pore structures may be used, and a porous membrane filter and a fiber membrane filter may be used in combination.
• a specific example is a method using a nylon fiber membrane filter and a UPE porous membrane filter.
• the filter it is preferable to wash the filter thoroughly before use. If an unwashed filter (or a filter that has not been sufficiently washed) is used, the impurities contained in the filter are likely to be carried into the present treatment liquid. Impurities contained in the filter include, for example, the above-described organic impurities, and if the filtration step is performed using an unwashed filter (or a filter that has not been sufficiently washed), the organic impurities in the treatment liquid can be content may exceed the allowable range for this treatment liquid. For example, when polyolefins such as UPE and polyfluorocarbons such as PTFE are used for filters, the filters tend to contain alkanes having 12 to 50 carbon atoms as impurities.
• UPE polyolefins
• polyfluorocarbons such as PTFE
• a method for washing the filter includes, for example, a method of immersing the filter in an organic solvent having a low impurity content (for example, an organic solvent purified by distillation (PGMEA, etc.)) for one week or longer.
• the liquid temperature of the organic solvent is preferably 30 to 90°C.
• the material to be purified may be filtered using a filter adjusted to the degree of washing, and the resulting treated liquid may be adjusted to contain the desired amount of filter-derived organic impurities.
• the filtration step may be a multistage filtration step in which the substance to be purified is passed through two or more filters in which at least one selected from the group consisting of filter materials, pore sizes, and pore structures is different. Moreover, the substance to be purified may be passed through the same filter a plurality of times, or may be passed through a plurality of filters of the same type.
• the filtration route is not particularly limited, and one-pass filtration may be used, or a circulation route may be formed for circulation filtration.
• the material of the wetted part of the refining device used in the filtration process is not particularly limited, but non-metallic materials (fluororesin etc.), and at least one selected from the group consisting of electrolytically polished metal materials (stainless steel, etc.) (hereinafter these are also collectively referred to as “corrosion resistant materials”).
• non-metallic materials fluororesin etc.
• electrolytically polished metal materials stainless steel, etc.
• the nonmetallic material is not particularly limited, and known materials can be used.
• nonmetallic materials include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, and fluororesin (e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene- Propylene hexafluoride copolymer resin, ethylene tetrafluoride-ethylene copolymer resin, ethylene trifluoride chloride-ethylene copolymer resin, vinylidene fluoride resin, ethylene trifluoride chloride copolymer resin, and vinyl fluoride resin etc.), but is not limited thereto.
• fluororesin e.g., tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene- Propylene hexafluoride copoly
• the metal material is not particularly limited, and known materials can be used.
• metal materials include metal materials in which the total content of chromium and nickel is more than 25% by mass with respect to the total mass of the metal material, and more preferably 30% by mass or more.
• the upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90% by mass or less.
• Metal materials include, for example, stainless steel and nickel-chromium alloys.
• the stainless steel is not particularly limited, and known stainless steel can be used. Among them, an alloy containing 8% by mass or more of nickel is preferable, and an austenitic stainless steel containing 8% by mass or more of nickel is more preferable.
• austenitic stainless steel include SUS (Steel Use Stainless) 304 (Ni content 8% by mass, Cr content 18% by mass), SUS304L (Ni content 9% by mass, Cr content 18% by mass), SUS316 ( Ni content of 10% by mass, Cr content of 16% by mass), SUS316L (Ni content of 12% by mass, Cr content of 16% by mass), and the like.
• Nickel-chromium alloys are not particularly limited, and known nickel-chromium alloys can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75% by mass and a chromium content of 1 to 30% by mass is preferable. Examples of nickel-chromium alloys include Hastelloy (product name, the same applies hereinafter), Monel (product name, the same applies hereinafter), and Inconel (product name, the same applies hereinafter).
• Hastelloy C-276 Ni content 63% by mass, Cr content 16% by mass
• Hastelloy-C Ni content 60% by mass, Cr content 17% by mass
• Hastelloy C-22 Ni content of 61% by mass, Cr content of 22% by mass
• the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, etc. in addition to the alloys described above, if necessary.
• the method for electropolishing a metal material is not particularly limited, and known methods can be used. For example, the methods described in paragraphs [0011] to [0014] of JP-A-2015-227501 and paragraphs [0036] to [0042] of JP-A-2008-264929 can be used.
• the metal material has a higher chromium content in the passivation layer on the surface than the chromium content in the matrix due to electropolishing. Therefore, it is presumed that the metal-containing particles are less likely to flow out into the material to be purified when a refining apparatus in which the liquid-contacting portion is formed of an electrolytically polished metal material is used.
• the metal material may be buffed.
• the buffing method is not particularly limited, and any known method can be used.
• the size of the abrasive grains used for the buffing finish is not particularly limited, but #400 or less is preferable in that the irregularities on the surface of the metal material are likely to be smaller. Buffing is preferably performed before electropolishing.
• the method for producing the treatment liquid may include steps such as a distillation step, a reaction step, and a static elimination step.
• the distillation step is a step of distilling a substance to be purified containing an organic solvent to obtain a distilled substance to be purified.
• the method for distilling the substance to be purified is not particularly limited, and known methods can be used.
• the wetted portion of the distillation column is not particularly limited, but is preferably made of the corrosion-resistant material already described.
• the reaction step is a step of reacting raw materials to produce a substance to be purified containing an organic solvent as a reactant.
• the method for producing the substance to be purified is not particularly limited, and known methods can be used. Typically, there is a method of arranging a reaction tank on the primary side of a manufacturing tank (or distillation column) of a refiner subjected to a filtration step and introducing a reactant into the manufacturing tank (or distillation column). At this time, the wetted portion of the production tank is not particularly limited, but is preferably made of the corrosion-resistant material already described.
• the static elimination step is a step of removing static electricity from the object to be purified to reduce the charge potential of the object to be purified.
• the static elimination method is not particularly limited, and a known static elimination method can be used.
• Examples of the static elimination method include a method of bringing the object to be purified into contact with a conductive material.
• the contact time for bringing the material to be purified into contact with the conductive material is preferably 0.001 to 60 seconds, more preferably 0.001 to 1 second, and particularly preferably 0.01 to 0.1 second.
• Conductive materials include stainless steel, gold, platinum, diamond, glassy carbon, and the like.
• As a method for bringing the substance to be purified into contact with the conductive material for example, there is a method of arranging a grounded mesh made of a conductive material inside the pipeline and passing the substance to be purified through the mesh.
• the clean room is preferably a class 4 or higher clean room defined by the international standard ISO14644-1:2015 defined by the International Organization for Standardization. Specifically, it preferably satisfies any of ISO Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably satisfies ISO Class 1 or ISO Class 2, and satisfies ISO Class 1. is particularly preferred.
• the storage temperature of the present treatment liquid is not particularly limited, the storage temperature is 4° C. in that the trace amounts of impurities contained in the present treatment liquid are less likely to be eluted, and as a result, more excellent effects of the present invention can be obtained.
• the above is preferable.
• a dehydration process may be carried out as a process other than the above.
• the dehydration step can be performed using, for example, distillation and molecular sieves.
• ⁇ Specific acid component> ⁇ Acetic acid: Kanto Chemical Co., Ltd. ultra-pure chemicals
• ⁇ Propionic acid Wako special grade manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.
• ⁇ Butyric acid Wako special grade manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.
• ⁇ Formic acid Wako special grade manufactured by FUJIFILM Wako Pure Chemical Co., Ltd.
• ⁇ Water> ⁇ Ultrapure water Water sampled from an ultrapure water system manufactured by Nomura Microscience Co., Ltd.
• ⁇ Content of specific metal element The content of specific metal elements (Fe, Ni and Cr) in the treatment solution (total content of each element of Fe, Ni and Cr) was measured using an Agilent 8900 triple quadrupole ICP-MS (for semiconductor analysis, option #200 ) under the following measurement conditions.
• the sample introduction system used a quartz torch, a coaxial PFA (perfluoroalkoxyalkane) nebulizer (for self-priming), and a platinum interface cone.
• the measurement parameters for the cool plasma conditions are as follows.
• the water content (water content) in the treatment liquid was measured using an apparatus (Kyoto Denshi Kogyo Karl Fischer Moisture Meter MKA-610) based on the Karl Fischer moisture measurement method.
• Examples 1-1 to 1-7 Using the developers of Examples 1-1 to 1-7 in which the content of the specific acid component was changed, the content of the specific acid component in the developer containing the aliphatic hydrocarbon solvent was used to determine the line width of the resist pattern. We verified whether there is a correlation with variability.
• the developers of Examples 1-1 to 1-7 were prepared as follows. First, the organic solvent (aliphatic hydrocarbon solvent and ester solvent) is purified by low-temperature distillation in a Teflon (registered trademark) closed container and filter filtration, and the content of the specific metal element (described later The purification was repeated until the mpg (measured by ICP-MS method) was less than 1 mass ppt. Next, after mixing the purified aliphatic hydrocarbon solvent and the ester solvent so that the content shown in the table below is obtained, the components other than the organic solvent were added so that the content shown in Table 1 was obtained. . Thus, developers of Examples 1-1 to 1-7 were obtained.
• the preparation of each component was carried out in an ISO class 3 clean booth.
• the containers and equipment used for the preparation of each component and the measurement of the content, etc. select those with wetted parts made of Teflon (registered trademark), glass, or electropolished stainless steel, and The liquid portion was thoroughly washed in advance using FN-DP001 manufactured by Fuji Film Electronic Materials Co., Ltd. before use.
• filters used for filter filtration a 7 nm PTFE filter manufactured by Nippon Entegris, a 10 nm PE (polyethylene) filter manufactured by Nippon Entegris, and a 5 nm nylon filter manufactured by Nippon Pall were used alone or in combination.
• a mixed solution was prepared by mixing the following components.
• Polymer 1 54 parts by mass Photoacid generator 31 parts by mass Acid diffusion control agent 15 parts by mass Propylene glycol monomethyl ether acetate 3430 parts by mass Propylene glycol monomethyl ether 1470 parts by mass
• Polymer 1 was a polymer having the following two repeating units, had a weight average molecular weight of 8700, and had a dispersity (Mw/Mn) of 1.23.
• the molar ratio between the repeating unit represented by U-01 and the repeating unit represented by U-19 was 1:1.
• the obtained silicon wafer having the resist film was subjected to pattern irradiation using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). rice field.
• EUV exposure apparatus Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36.
• rice field As a reticle, a photomask having a line size of 22 nm and a line:space ratio of 1:1 was used.
• the developer of Examples 1-1 to 1-7 was developed by puddling for 30 seconds, and the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds.
• a line-and-space pattern of 28-50 nm was obtained. The obtained pattern was observed at 100 points and the wiring width was measured, and the variation was determined by the deviation.
• Examples 2-1 to 2-10> Using the developers of Examples 2-1 to 2-10 in which the mass ratio of the content of the ester solvent to the content of the aliphatic hydrocarbon solvent in the developer was changed, the aliphatic hydrocarbon in the developer It was verified whether the mass ratio of the content of the ester solvent to the content of the solvent has a correlation with the sensitivity of the resist pattern.
• the developers of Examples 2-1 to 2-10 were prepared in the same manner as in Examples 1-1 to 1-7, except that the content of each component was adjusted to the value shown in Table 2. bottom. Further, patterns were formed on a 12-inch substrate in the same manner as in Examples 1-1 to 1-7 using the developing solutions of Examples 2-1 to 2-10.
• Examples 3-1 to 3-2 Using the developers of Examples 3-1 and 3-2 in which the content of the aromatic hydrocarbon was varied, whether the content of the aromatic hydrocarbon in the developer correlates with the bridging defects of the resist pattern. verified.
• the developers of Examples 3-1 and 3-2 were prepared in the same manner as in Examples 1-1 to 1-7, except that the content of each component was adjusted to the value shown in Table 3. bottom.
• Examples 4-1 to 4-3 Using the developers of Examples 4-1 to 4-3 with different alcohol contents, it was verified whether the alcohol content in the developer has a correlation with coating defects in the resist pattern.
• the developers of Examples 4-1 to 4-3 were prepared in the same manner as in Examples 1-1 to 1-7, except that the content of each component was adjusted to the value shown in Table 4. bottom.
• Examples 5-1 to 5-2> Using the developers of Examples 5-1 and 5-2 with different water contents, it was verified whether the water content in the developer has a correlation with pattern collapse of the resist pattern.
• the developers of Examples 5-1 to 5-2 were prepared in the same manner as in Examples 1-1 to 1-7, except that the content of each component was adjusted to the value shown in Table 5. bottom.
• Examples 6-1 to 6-2 Using the developers of Examples 6-1 and 6-2 in which the content of the specific metal element was varied, whether the content of the specific metal element in the developer correlates with the metal-containing defects in the resist pattern. verified.
• the developers of Examples 6-1 to 6-2 were prepared in the same manner as in Examples 1-1 to 1-7, except that the content of each component was adjusted to the value shown in Table 6. bottom.
• Examples 7-1 to 7-7 Using the rinsing solutions of Examples 7-1 to 7-7 in which the content of the specific acid component was changed, the content of the specific acid component in the rinsing solution containing the aliphatic hydrocarbon solvent was the line width of the resist pattern. We verified whether there is a correlation with variability.
• the rinse solutions of Examples 7-1 to 7-7 were prepared in the same manner as in Examples 1-1 to 1-7, except that the contents of each component were adjusted to the values shown in Table 7. bottom.
• the line width variation of the resist pattern changed depending on the content of the specific acid component in the rinse liquid. This proves that the content of the specific acid component in the rinse liquid is closely related to the line width variation of the resist pattern. According to the above verification results, for example, when it is desired to obtain a resist pattern in which the deviation of the line width variation is within ⁇ 1.0, the content of the specific acid component in the rinse solution should be 2000 ppm by mass or less. The treatment liquid can be tested by setting it within the allowable range.
• Examples 8-1 to 8-10 Using the rinse liquids of Examples 8-1 to 8-10 in which the mass ratio of the content of the ester solvent to the content of the aliphatic hydrocarbon solvent in the rinse liquid was changed, the aliphatic hydrocarbon in the rinse liquid It was verified whether the mass ratio of the content of the ester solvent to the content of the solvent has a correlation with the sensitivity of the resist pattern.
• the rinse solutions of Examples 8-1 to 8-10 were prepared in the same manner as in Examples 1-1 to 1-7, except that the contents of each component were adjusted to the values shown in Table 8. bottom.
• Example 6-3 was used as the set sensitivity, and the sensitivity difference with respect to it was obtained as a ratio for evaluation.
• Examples 9-1 to 9-2 Using the rinsing solutions of Examples 9-1 and 9-2 in which the content of the aromatic hydrocarbon was varied, whether the content of the aromatic hydrocarbon in the rinsing solution correlates with bridging defects in the resist pattern. verified.
• the rinse solutions of Examples 9-1 to 9-2 were prepared in the same manner as in Examples 1-1 to 1-7, except that the contents of each component were adjusted to the values shown in Table 9. bottom.
• the evaluation results of bridging defects changed depending on the content of aromatic hydrocarbons in the rinse liquid. From this, it was demonstrated that the content of aromatic hydrocarbons in the rinse liquid is closely related to the evaluation result of bridging defects. According to the above verification results, for example, when it is desired to obtain a resist pattern in which bridging defects are not confirmed until the line width reaches 14 nm or more, the aromatic hydrocarbon content in the rinse liquid should be 2000 ppm by mass or less. A certain case may be set as an allowable range and the rinse solution may be tested.
• Examples 10-1 to 10-3 Using the rinsing solutions of Examples 10-1 to 10-3 with different alcohol contents, it was verified whether the alcohol content in the rinsing solutions correlated with coating defects in the resist pattern.
• the rinse solutions of Examples 10-1 to 10-3 were prepared in the same manner as in Examples 1-1 to 1-7, except that the contents of each component were adjusted to the values shown in Table 10. bottom.
• Verification was performed in the same manner as in Examples 4-1 to 4-3, except that the rinse liquids of Examples 10-1 to 10-3 were used.
• the evaluation results of coating defects changed depending on the content of alcohol in the rinse liquid. From this, it was demonstrated that the alcohol content in the rinse liquid is closely related to the coating defect evaluation results. According to the above verification results, for example, when it is desired to obtain a resist pattern with 100 or less coating defects, the alcohol content in the rinse liquid is set to 5000 ppm by mass or less as the allowable range. , the test of the rinse solution should be performed.
• Examples 11-1 to 11-2 Using the rinsing solutions of Examples 11-1 and 11-2 with different water contents, it was verified whether the water content in the rinsing solutions correlated with pattern collapse of the resist pattern.
• the rinse solutions of Examples 11-1 to 11-2 were prepared in the same manner as in Examples 1-1 to 1-7, except that the contents of each component were adjusted to the values shown in Table 11. bottom.
• Examples 12-1 to 12-2 Using the rinse solutions of Examples 12-1 and 12-2 in which the content of the specific metal element was varied, it was determined whether the content of the specific metal element in the rinse solution correlated with the metal-containing defects in the resist pattern. verified.
• the rinse solutions of Examples 12-1 to 12-2 were prepared in the same manner as in Examples 1-1 to 1-7, except that the contents of each component were adjusted to the values shown in Table 12. bottom.
• Verification was performed in the same manner as in Examples 6-1 and 6-2, except that the rinse liquids of Examples 12-1 and 12-2 were used.

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