Classifications

• • 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
  • 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
  • G03F7/325—Non-aqueous compositions
• • 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
  • G03F7/422—Stripping or agents therefor using liquids only
• • 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
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices

Definitions

• the present invention relates to a treatment liquid and a treatment liquid container.
• a film is formed from an actinic ray- or radiation-sensitive composition (also referred to as a "resist composition”), and then the resulting film is exposed to light, developed with a developer, and washed with a rinse solution after development.
• an actinic ray- or radiation-sensitive composition also referred to as a "resist composition”
• Patent Document 1 discloses a developer composition used in the development treatment of an organometallic patterning layer, which contains at least 55 volume % of a solvent having a Hansen solubility parameter ⁇ H+ ⁇ P value of about 16 (J/cm 3 ) 1/2 or less, and at least 0.25 to 45 volume % of a solvent having a Hansen solubility parameter ⁇ H+ ⁇ P value of about 16 (J/cm 3 ) 1/2 .
• the present inventors have studied the developer composition disclosed in Patent Document 1 and have found that when the developer composition is used as a developer or rinse for a metal resist, at least one of the following is deteriorated: suppression of occurrence of pattern defects (hereinafter, also simply referred to as “suppression of pattern defects”), pattern resolution, suppression of defects derived from the processing solution after storage at elevated and lowered temperatures, and pattern resolution after storage at elevated and lowered temperatures, and that there is room for improvement.
• suppression of pattern defects hereinafter, also simply referred to as "suppression of pattern defects”
• pattern resolution suppression of defects derived from the processing solution after storage at elevated and lowered temperatures
• pattern resolution after storage at elevated and lowered temperatures
• suppression of defects derived from the processing liquid after storage at elevated and decreased temperatures and “deterioration of pattern resolution after storage at elevated and decreased temperatures” refer to a phenomenon in which, when a processing liquid that has been stored at elevated and decreased temperatures for a certain period of time (e.g., one month) is used while repeating a procedure of storing the processing liquid at a high temperature (e.g., 85°C) for a certain period of time (e.g., one hour) and then storing the processing liquid at a low temperature (e.g., 5°C) for a certain period of time (e.g., one hour), the suppression of defects derived from the processing liquid and the pattern resolution are deteriorated compared to before and after the storage at elevated and decreased temperatures, and it is preferable that the above phenomenon is suppressed.
• a high temperature e.g. 85°C
• a low temperature e.g., 5°C
• an object of the present invention is to provide a processing liquid which, when used as a developer or rinsing liquid for a metal resist, is excellent in all of the following: suppression of pattern defects, pattern resolution, suppression of defects derived from the processing liquid after storage at elevated and lowered temperatures, and pattern resolution after storage at elevated and lowered temperatures.
• Another object of the present invention is to provide a treatment liquid container that contains the treatment liquid.
• a treatment liquid containing propylene glycol monomethyl ether acetate, water, and an organic acid The content of the propylene glycol monomethyl ether acetate is 60% by mass or more based on the total mass of the treatment liquid, the water content is 1 to 100 ppm by mass based on the total mass of the treatment liquid, the content of the organic acid is 1.00% by mass or more and less than 40.00% by mass with respect to the total mass of the treatment liquid, The treatment liquid has a mass ratio of the organic acid content to the water content of 100 to 100,000.
• the treatment liquid according to [1], wherein a mass ratio of the content of the organic acid to the content of the water is 1,000 to 10,000.
• the content of the propylene glycol monomethyl ether acetate is 80% by mass or more based on the total mass of the treatment liquid,
• the compound contains a boron atom, The treatment liquid according to any one of [1] to [4], wherein the content of the boron atoms is 0.001 to 100 ppt by mass, based on the total mass of the treatment liquid.
• it contains Pb atoms, The treatment liquid according to any one of [1] to [5], wherein the content of the Pb atoms is 0.001 to 10 ppt by mass with respect to the total mass of the treatment liquid.
• the processing liquid according to any one of [1] to [6] which is used as a developer or a rinse liquid for a metal resist.
• a treatment liquid container comprising a container and the treatment liquid according to any one of items [1] to [7] contained in the container.
• non-metallic material is at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin, and vinyl fluoride resin.
• the non-metallic material is at least one selected from the group consisting of polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, te
• the present invention it is possible to provide a processing solution which, when used as a developer or rinsing solution for a metal resist, is excellent in all of the following: suppression of pattern defects, pattern resolution, suppression of defects derived from the processing solution after storage at elevated and lowered temperatures, and pattern resolution after storage at elevated and lowered temperatures.
• the present invention can also provide a treatment liquid container that contains the treatment liquid.
• a numerical range expressed using “ ⁇ ” means a range that includes the numerical values written before and after " ⁇ " as the lower and upper limits.
• actinic rays or “radiation” refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light: extreme ultraviolet), X-rays, and electron beams (EB: electron beam), etc.
• light refers to actinic rays or radiation.
• exposure includes not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams.
• the substituents are preferably monovalent substituents, unless otherwise specified.
• the bonding direction of the divalent group described in this specification is not limited unless otherwise specified.
• Y when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-.
• the above compound may be "X-CO-O-Z" or "X-O-CO-Z".
• examples of halogen atoms include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• solid content refers to components that form a metal resist film, and does not include solvents (e.g., organic solvents, water, etc.).
• any component that forms a metal resist film is considered to be a solid content even if it is in a liquid state.
• the “content” of the component means the total content of those two or more components.
• ppm means “parts-per-million (10 -6 )
• ppb means “parts-per-billion (10 -9 )
• ppt means “parts-per-trillion (10 -12 ).
• the treatment liquid, treatment liquid container, pattern formation method, and electronic device manufacturing method of the present invention will be described below in order.
• the treatment liquid of the present invention contains propylene glycol monomethyl ether acetate (hereinafter also referred to as "PGMEA”), water, and an organic acid, in which the PGMEA content is 60 mass% or more, relative to the total mass of the treatment liquid, the water content is 1 to 100 mass ppm, relative to the total mass of the treatment liquid, the organic acid content is 1.00 mass% or more and less than 40.00 mass%, relative to the total mass of the treatment liquid, and the mass ratio of the organic acid content to the water content (hereinafter also referred to as "specific mass ratio”) is 100 to 100,000.
• PGMEA propylene glycol monomethyl ether acetate
• the treatment liquid exhibits excellent pattern resolution by containing a predetermined amount of PGMEA, which is an organic solvent capable of dissolving the metal resist in the unexposed area, and an organic acid that promotes dissolution of the metal resist in the unexposed area. Furthermore, by controlling the content of water, the physical properties of the treatment liquid can be appropriately adjusted, and the occurrence of pattern defects can be suppressed.
• PGMEA is an organic solvent capable of dissolving the metal resist in the unexposed area
• an organic acid that promotes dissolution of the metal resist in the unexposed area.
• the treatment liquid will provide the desired effect when used as a developer or rinse solution for the metal resist.
• being superior in at least one of the suppression of pattern defects, the pattern resolution, the suppression of defects caused by the processing liquid after storage at elevated and lowered temperatures, and the pattern resolution after storage at elevated and lowered temperatures is also referred to as "the effect of the present invention being superior.”
• the treatment liquid includes PGMEA.
• the content of PGMEA is 60% by mass or more, preferably 65% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total mass of the treatment liquid, in order to obtain a more excellent pattern resolution.
• the upper limit of the content of PGMEA is preferably less than 99% by mass, and more preferably 95% by mass or less, based on the total mass of the treatment liquid. If the content of PGMEA is less than 60% by mass based on the total mass of the treatment liquid, the ability of the treatment liquid to dissolve the metal resist film decreases, which is undesirable in that the pattern resolution decreases.
• the treatment liquid includes water.
• the lower limit of the water content is 1 ppm by mass or more, preferably 3 ppm by mass or more, and more preferably 5 ppm by mass or more, based on the total mass of the treatment liquid.
• the upper limit of the water content is 100 ppm by mass or less, preferably 80 ppm by mass or less, and more preferably 50 ppm by mass or less, relative to the total mass of the treatment solution.
• the water content within the above range improves the suppression of pattern defects, it is speculated that this is because the electrical conductivity of the treatment liquid is increased, suppressing the generation of sparks that cause dielectric breakdown in materials that come into contact with the liquid, and ultimately suppressing the intrusion of foreign matter that causes defects.
• defects caused by water for example, watermark defects
• unintended reactions of components of the processing solution during storage at elevated and lowered temperatures can be suppressed.
• the water content can be measured using a device that uses the Karl Fischer moisture measurement method as its measurement principle.
• a Karl Fischer moisture meter product name "MKC-710M", manufactured by Kyoto Electronics Manufacturing Co., Ltd., Karl Fischer coulometric titration type
• MKC-710M manufactured by Kyoto Electronics Manufacturing Co., Ltd., Karl Fischer coulometric titration type
• water examples include distilled water, ion-exchanged water, pure water, and ultrapure water, with ultrapure water being preferred.
• Water may be either intentionally added, unavoidably contained in the raw materials of the treatment liquid, or unavoidably contained during the production, storage, and/or transportation of the treatment liquid.
• the method for adjusting the water content is not particularly limited, but examples include a method of removing water from the treatment liquid and/or the raw materials used in preparing the treatment liquid, a method of adding water, and a combination of these.
• a method for removing water a known dehydration method can be used, for example, dehydration using a water adsorbent, distillation, and dehydration using a dehydrating membrane.
• the water adsorbent include zeolite (such as molecular sieves), sodium sulfate, magnesium sulfate, silica gel, calcium chloride, anhydrous zinc chloride, fuming sulfuric acid, and soda lime.
• Dehydration methods using dehydration membranes include membrane dehydration by pervaporation (PV) or vapor permeation (VP).
• PV pervaporation
• VP vapor permeation
• a membrane made of a polymeric material such as a polyimide-based, cellulose-based, or polyvinyl alcohol-based material, or an inorganic material such as zeolite can be used.
• the treatment liquid contains an organic acid.
• the organic acid may be dissociated in the treatment liquid, or may form a salt.
• the content of the organic acid is 1.00% by mass or more based on the total mass of the treatment liquid, and from the viewpoint of obtaining better pattern resolution, it is preferably 3.00% by mass or more, and more preferably 5.00% by mass or more.
• the content of the organic acid is less than 40.00% by mass based on the total mass of the treatment liquid, and from the viewpoint of obtaining better pattern resolution, it is preferably less than 30.00% by mass, and more preferably less than 20.00% by mass.
• the content of the organic acid is less than 1.00% by mass or equal to or greater than 40.00% by mass relative to the total mass of the treatment liquid, the dissolving ability of the treatment liquid for the metal resist decreases, undesirably deteriorating the pattern resolution.
• the content of propylene glycol monomethyl ether acetate is 80 mass % or more, relative to the total mass of the treatment liquid, and the content of the organic acid is 1.00 mass % or more and less than 20.00 mass %, relative to the total mass of the treatment liquid.
• the mass ratio of the organic acid content to the PGMEA content is preferably from 0.03 to 0.5, and more preferably from 0.03 to 0.2.
• organic acids examples include carboxylic acid organic acids such as aliphatic carboxylic acid organic acids and aromatic carboxylic acid organic acids, and phosphonic acid organic acids, with carboxylic acid organic acids being preferred and monocarboxylic acids being more preferred.
• the carboxylic acid organic acid is a compound having one or more carboxy groups.
• the carboxylic acid-based organic acid may further have a hydroxy group in addition to a carboxy group.
• the number of carboxy groups contained in the carboxylic acid-based organic acid is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1.
• aliphatic carboxylic acid organic acids include acetic acid, formic acid, propionic acid, butyric acid, glycolic acid, lactic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, sebacic acid, maleic acid, malic acid, citric acid, tartaric acid, and gluconic acid.
• aromatic carboxylic acid organic acids include phthalic acid, isophthalic acid, terephthalic acid, gallic acid, trimellitic acid, mellitic acid, and cinnamic acid.
• Examples of phosphonic acid-based organic acids include the compounds described in paragraphs [0026] to [0036] of WO 2018/020878 and the compounds described in paragraphs [0031] to [0046] of WO 2018/030006, the contents of which are incorporated herein by reference.
• the melting point of the organic acid is preferably 20°C or lower, more preferably 18°C or lower, and even more preferably 16°C or lower.
• the lower limit is preferably -20°C or higher.
• the organic acid preferably includes at least one organic acid selected from the group consisting of formic acid, acetic acid, propionic acid, butyric acid, and lactic acid.
• the organic acids may be used alone or in combination of two or more.
• the specific mass ratio of the treatment liquid is from 100 to 100,000, preferably from 500 to 50,000, and more preferably from 1,000 to 10,000.
• the treatment liquid may contain propylene glycol monomethyl ether (hereinafter, also referred to as "PGME").
• PGME propylene glycol monomethyl ether
• the content of PGME is preferably 0.0001 mass % or more, based on the total mass of the treatment solution, and is more preferably 0.0005 mass % or more, and even more preferably 0.001 mass % or more, in that it is more effective in suppressing pattern defects and in suppressing deterioration of pattern resolution after storage at elevated temperatures and reduced temperatures.
• the content of PGMEA is preferably 0.1 mass % or less, based on the total mass of the treatment solution, and is more preferably 0.05 mass % or less, and even more preferably 0.02 mass % or less, in that it provides better suppression of pattern defects and can further suppress deterioration of defect suppression properties after storage at elevated and lowered temperatures.
• the total content of PGMEA, water, and organic acid in the treatment liquid is preferably 95% by mass or more, more preferably 99% by mass or more, even more preferably 99.9% by mass or more, and particularly preferably 99.99% by mass or more, based on the total mass of the treatment liquid.
• the upper limit is 100% by mass or less, and is often less than 100% by mass.
• the total content of PGMEA, water, organic acid, and PGME in the treatment liquid is preferably 95% by mass or more, more preferably 99% by mass or more, even more preferably 99.9% by mass or more, and particularly preferably 99.99% by mass or more, based on the total mass of the treatment liquid.
• the upper limit is 100% by mass or less, and is often less than 100% by mass.
• the treatment liquid may contain boron atoms.
• the treatment liquid preferably contains boron atoms in that defects derived from alkali metals and alkaline earth metals can be reduced.
• the form of the boron atom in the treatment liquid is not particularly limited, and examples thereof include boron-containing compounds such as inorganic boron compounds and organic boron compounds, and elemental boron.
• the boron atom may be present as an ion in the treatment liquid.
• the inorganic boron compound include boric acid (H 3 BO 3 ), borates, and metal borides.
• the boron atom is often in the form of boric acid or borate salts, such as alkali metal salts, such as sodium salts and potassium salts, and alkaline earth metal salts, such as calcium salts and magnesium salts.
• the boron atoms may be either those that are intentionally added, those that are inevitably contained in the raw materials of the treatment liquid, or those that are inevitably contained during the production, storage, and/or transportation of the treatment liquid.
• the method for adjusting the content of boron atoms is not particularly limited, but examples thereof include a method of removing boron atoms from the treatment liquid and/or raw materials used in preparing the treatment liquid, a method of adding a component containing boron atoms (boron atom source), and a combination of these.
• removing boron atoms from the treatment liquid and/or the raw materials used in preparing the treatment liquid includes, for example, removing boron-containing compounds, elemental boron, and ions containing boron atoms from the treatment liquid and/or the raw materials used in preparing the treatment liquid.
• the method of adding a boron atom source to a mixture of raw materials from which boron atoms have been removed is preferred because it allows easy control of the composition.
• the method for removing boron atoms may be appropriately selected from known methods depending on the form of boron atoms in the treatment liquid and/or the raw materials used for preparing the treatment liquid.
• the method include purification treatments such as ion removal treatment and filtration treatment described below, and anion exchange treatment is preferred.
• the boron atom source is not particularly limited, and for example, elemental boron and the above-mentioned boron-containing compounds can be used, with elemental boron, boric acid, or a borate being preferred.
• the content of boron atoms is preferably 0.001 to 100 ppt by mass relative to the total mass of the treatment solution, more preferably 0.002 to 85 ppt by mass, even more preferably 0.01 to 75 ppt by mass, and particularly preferably 0.05 to 50 ppt by mass, in that defects resulting from alkali metals and alkaline earth metals can be reduced.
• the boron atomic content is measured by ICP-MS (Inductively Coupled Plasma Mass Spectroscopy).
• ICP-MS Inductively Coupled Plasma Mass Spectroscopy
• devices that can be used to perform ICP-MS include Agilent 8900 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, NexION350S manufactured by PerkinElmer, and Agilent 8800 manufactured by Agilent Technologies.
• the treatment liquid When measuring the content of boron atoms, the treatment liquid may be concentrated before the measurement.
• the treatment liquid is concentrated according to the following procedure.
• the container used for concentration is made of polytetrafluoroethylene.
• ultrapure water is added to the processing solution in which the quantity of boron atoms is to be determined.
• the content of boron atoms in the ultrapure water is measured in advance.
• the treatment liquid to which the ultrapure water has been added is heated to convert the boron present in the treatment liquid into the form of boric acid.
• Concentration is performed on the treatment liquid that has been subjected to the above heat treatment.
• the treatment liquid to which ultrapure water has been added is heated, it is heated at a temperature of 100° C. for one hour under reflux conditions.
• the concentration is carried out, the organic solvent and water contained in the treatment liquid are removed at 160 to 180°C.
• the content of boron atoms in ultrapure water may be measured after concentrating the ultrapure water.
• the method for concentrating ultrapure water can be found in the above method for concentrating the treatment liquid.
• the content of boron atoms in the chemical solution is calculated for each concentration ratio changed from 10 to 1000 times. If a positive correlation (positive linear correlation) is observed between the concentration ratio and the value of the content of boron atoms, it can be confirmed that the content of boron atoms in the chemical solution can be quantified by the above method.
• the treatment liquid may contain at least one type of metal atom (hereinafter also referred to as a "specific metal atom") selected from the group consisting of Pb (lead), Fe (iron), Cr (chromium), Ni (nickel), and Sn (tin).
• the specific metal atoms preferably include Pb atoms. It is preferable that the treatment liquid contains a specific metal atom, since this suppresses the occurrence of defects originating from the coating liquid when the treatment liquid is applied to a substrate (hereinafter, this may also be referred to simply as “better suppression of defects originating from the treatment liquid”).
• the form of the specific metal atoms in the treatment liquid is not particularly limited, and they may be contained as metal particles or metal ions.
• the metal particles may be in the form of a simple substance of the specific metal atom, an alloy of the specific metal atom with another metal atom, or an association of the specific metal atom with an organic substance.
• the metal ions may form a salt and/or a complex.
• the specific metal atoms may be either those that are intentionally added, those that are inevitably contained in the raw materials of the treatment liquid, or those that are inevitably contained during the production, storage, and/or transportation of the treatment liquid.
• the method for adjusting the content of the specific metal atom is not particularly limited, but examples include a method of removing the specific metal atom from the treatment liquid and/or the raw materials used in preparing the treatment liquid, a method of adding a component containing the specific metal atom (a specific metal atom source), and a combination of these.
• removing specific metal atoms from the treatment liquid and/or the raw materials used to prepare the treatment liquid includes, for example, removing metal particles, metal ions, and the like from the raw materials.
• the method of adding a specific metal atom source to a mixture of raw materials from which the specific metal atoms have been removed is preferred because it allows easy control of the composition.
• the method for removing the specific metal atoms may be appropriately selected from known methods depending on the form of the specific metal atoms in the treatment liquid and/or the raw materials used to prepare the treatment liquid, and examples of such methods include purification treatments such as ion removal treatment and filtration treatment, which will be described later.
• purification treatments such as ion removal treatment and filtration treatment, which will be described later.
• filtration treatment is preferred, and when the specific metal atoms are in the form of metal ions, ion removal treatment is preferred.
• the specific metal atom source is not particularly limited, and examples thereof include metal particles such as metal nanoparticles, metal oxide particles, and compounds containing metal ions such as metal salts (e.g., metal halides) and organometallic complexes, with metal nanoparticles being preferred.
• metal particles such as metal nanoparticles, metal oxide particles, and compounds containing metal ions such as metal salts (e.g., metal halides) and organometallic complexes, with metal nanoparticles being preferred.
• the treatment liquid may contain one type of specific metal atom alone or two or more types of specific metal atoms.
• the content of the specific metal atom is preferably 0.001 ppt by mass or more, more preferably 0.005 ppt by mass or more, even more preferably 0.01 ppt by mass or more, and particularly preferably 0.05 ppt by mass or more, relative to the total mass of the treatment liquid.
• the content of specific metal atoms within the above range provides excellent suppression of defects caused by the treatment liquid, it is speculated that this is because the specific metal atoms function as carriers for charges generated by frictional charging, etc., thereby suppressing the generation of sparks that cause dielectric breakdown in materials that come into contact with the liquid, and ultimately suppressing the introduction of foreign matter that causes defects.
• the content of the specific metal atom is preferably 200 ppt by mass or less, more preferably 10 ppt by mass or less, even more preferably 7.5 ppt by mass or less, and particularly preferably 5 ppt by mass or less, relative to the total mass of the treatment liquid.
• the content of the specific metal atom is preferably from 0.001 to 7.5 ppt by mass, more preferably from 0.05 to 7.5 ppt by mass, and even more preferably from 0.01 to 5.0 ppt by mass, relative to the total mass of the treatment liquid.
• the type and content of the specific metal atom can be measured by ICP-MS.
• the device that can be used for ICP-MS is as described above.
• the treatment liquid may be concentrated before the measurement.
• the treatment liquid can be concentrated in the same manner as in the concentration procedure for measuring the content of boron atoms described above.
• the treatment liquid may contain other components in addition to those mentioned above.
• examples of other components include surfactants.
• surfactant known surfactants can be used, and examples thereof include nonionic surfactants and fluorine-based surfactants.
• the surfactant for example, the compounds exemplified in paragraph [0126] of WO 2022/044893 can be used.
• the treatment liquid preferably contains no more than 1000 mass ppt of metal atoms (e.g., Co, Na, Cu, Mg, Mn, Li, Al, and Ag) other than the specific metal atoms described above, and more preferably no more than 500 mass ppt.
• metal atoms e.g., Co, Na, Cu, Mg, Mn, Li, Al, and Ag
• the content of metal atoms other than the specific metal atoms be less than 500 mass ppt, particularly preferably no more than 150 mass ppt, and most preferably less than 100 mass ppt.
• the lower limit is preferably 0.
• Methods for reducing metal atoms other than the specific metal atoms include, for example, purification treatments such as filtration, ion removal, and distillation, which will be described later.
• Other examples include a method of using a container that is less likely to leach metal components as a container for containing the raw materials or the produced treatment liquid, and a method of lining the inner walls of piping with a fluororesin to prevent metal components from leaching from the piping during the production of the treatment liquid.
• the treatment liquid may contain coarse particles, but it is preferable that the content of coarse particles is low.
• coarse particles refers to particles whose diameter (particle size) when considered as a sphere is 1 ⁇ m or more.
• the coarse particles contained in the treatment liquid include particles such as dust, dirt, organic solids, and inorganic solids that are contained as impurities in the raw materials, as well as particles such as dust, dirt, organic solids, and inorganic solids that are brought in as contaminants during the preparation of the treatment liquid, and which ultimately exist as particles in the treatment liquid without dissolving.
• the content of particles having a particle diameter of 1 ⁇ m or more per 1 mL of the treatment liquid is preferably 100 or less, more preferably 50 or less.
• the content of coarse particles present in the treatment liquid can be measured in the liquid phase using a commercially available measuring device that employs a light scattering liquid particle measuring method using a laser as a light source. Examples of a method for removing coarse particles include a purification process such as a filtration process described below.
• the above-mentioned processing liquid is suitably used as a developer or rinse liquid for a metal resist.
• Other uses include, for example, metal resist cleaners such as edge bead removers, filter cleaners, pipe cleaners and tank cleaners.
• the "solubility of the metal resist film" possessed by the developer or rinsing liquid is an index showing the ease with which the metal resist film dissolves in the developer or rinsing liquid.
• the processing liquid that dissolves the smaller amount of metal resist film (volume reduction) per unit time out of the two types of processing liquid is the processing liquid that has a relatively smaller solubility for the metal resist film.
• a developer has a solubility that does not dissolve the metal resist film in the exposed area, but if a rinse solution with a higher solubility than the developer is used, the metal resist film in the exposed area may dissolve, causing concern that the pattern shape may collapse.
• the polymerization reaction may not proceed as easily as in other areas of the resist film in the exposed area, and these areas may become more soluble in organic solvents.
• the solubility of the metal resist film is the same in the rinse solution and the developer, there is a concern that this area may dissolve slightly, causing the pattern shape to collapse. Therefore, it is speculated that the collapse of the pattern can be suppressed by using a treatment solution with a lower solubility of the metal resist film than the developer as the rinse solution.
• the rinse solution is not particularly limited as long as it is a processing solution or rinse solution that has a lower solubility for the metal resist film than the developer.
• the rinse liquid may be a mixture of two or more types of organic solvents.
• examples of the rinse liquid include 2-heptanone, methyl isobutyl carbinol (MIBC), PGMEA, PGME (propylene glycol monomethyl ether), a mixture of PGMEA and PGME, and nBA (n-butyl acetate).
• the rinse liquid may be purified by a purification method for various components contained in the treatment liquid, which will be described later.
• the treatment liquid can be produced by a known method. For example, it can be produced by mixing the above-mentioned components to a predetermined concentration.
• the order in which the components are mixed is not particularly limited. In order to remove excess components and/or impurities, the raw material of the treatment liquid and/or the mixture thereof may be subjected to a purification treatment. In particular, it is preferable to produce the treatment liquid using PGMEA, water, and organic acid obtained by subjecting a product to purification treatment containing each component.
• a purification treatment on the product to be purified containing each component (PGMEA, water, and organic acid) as described above to reduce impurities such as boron atoms and specific metal atoms, and then supply a predetermined amount of boron atoms and/or specific metal atoms to the mixed liquid obtained by mixing the obtained raw materials to produce a treatment liquid containing the predetermined components.
• impurities other than boron atoms and specific metal atoms can also be reduced.
• the above-mentioned purification target material may be procured by purchase or the like, or may be obtained by synthesis through reaction of a precursor. It is preferable that the product to be purified has a low impurity content. Examples of commercially available products of such products include those called "high purity grade products.”
• the method for synthesizing the product to be purified by reacting the precursors is not particularly limited, and any known method can be used. For example, there is a method for reacting one or more raw materials in the presence of a catalyst to obtain the reaction product PGME or PGMEA. As a method for synthesizing the product to be purified containing PGME, for example, the method described in JP-A-2011-509998 can be used.
• PGMEA As a method for synthesizing a product to be purified that contains PGMEA, there is a method in which PGME and acetic acid are reacted as raw materials under an acid catalyst, specifically, the methods described in JP-A-59-176232 and JP-T-2001-521918 can be used. Since PGMEA may undergo a decomposition reaction when the ion removal treatment described below is repeatedly performed, it is preferable to use a raw material (specifically, PGME) used in the synthesis of a PGMEA-containing purification product that has been previously subjected to an ion removal treatment.
• PGME a raw material used in the synthesis of a PGMEA-containing purification product that has been previously subjected to an ion removal treatment.
• the material to be purified can be purified by any known method, such as filtration, ion removal, and distillation.
• the purification method of the target substance may be carried out by combining a plurality of processes selected from the group consisting of a filtration process, an ion removal process, and a distillation process.
• a primary purification process may be carried out by distilling the target substance, and then a secondary purification process may be carried out by passing the target substance through an ion exchange resin and/or a filter.
• a primary purification process may be carried out by passing the target substance through an ion exchange resin and/or a filter, and then a secondary purification process may be carried out by distilling the target substance.
• each purification treatment may be carried out multiple times.
• the method of the filtration treatment is not particularly limited, and a known method can be used. Among them, filtering the material to be purified using a filter is preferred.
• the components to be removed by the filtration treatment are not particularly limited, but examples thereof include metal particles and coarse particles.
• the filter used for filtering is not particularly limited, and any known filter can be used.
• the material for the filter include fluororesins such as PTFE (polytetrafluoroethylene) and PFA (perfluoroalkoxyalkane), polyamide resins such as 6-nylon and 6,6-nylon, polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene, diatomaceous earth, and glass.
• fluororesins such as PTFE (polytetrafluoroethylene) and PFA (perfluoroalkoxyalkane)
• polyamide resins such as 6-nylon and 6,6-nylon
• polyolefin resins including high density and ultra-high molecular weight
• polyethylene and polypropylene diatomaceous earth
• PTFE polyamide resins
• UPE ultra-high density polyethylene
• HDPE high density polyethylene
• HDPP ultra-high density polypropylene
• the critical surface tension of the filter is preferably 70 to 95 mN/m, more preferably 75 to 85 mN/m.
• the nominal value of the manufacturer can be used as the critical surface tension value.
• the pore size of the filter is preferably 0.1 nm to 1.0 ⁇ m, more preferably 0.5 nm to 0.1 ⁇ m, and even more preferably 1.0 to 50.0 nm.
• the filter may be surface-treated.
• the surface treatment method is not particularly limited, and known methods can be used. Examples of the surface treatment include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering, and chemical modification treatment or plasma treatment is preferred.
• the chemical modification treatment is preferably a treatment for introducing an ion exchange group, that is, the filter may be an ion exchange filter. Examples of the ion exchange group include a sulfonic acid group, a carboxyl group, and a phosphate group as a cation exchange group, and a quaternary ammonium group as an anion exchange group.
• the method for introducing the ion exchange group into the filter is not particularly limited, and examples thereof include a method in which a compound containing an ion exchange group and a polymerizable group is reacted with a polymer contained in the filter to perform grafting.
• the filtering may be a multi-stage filtration process in which the material to be purified is passed through two or more types of filters that are different in at least one aspect selected from the group consisting of the filter material, pore size, and pore structure.
• the material to be purified may be passed through the same filter multiple times, or through multiple filters of the same type.
• a circulating filtration process is preferred in which the solution is passed through the filters multiple times using a filtration device that combines multiple filters and return paths.
• the number of circulation times in the circulating filtration treatment is not particularly limited and may be appropriately selected depending on the desired purity and impurities, but is preferably 2 to 100 times, more preferably 20 to 80 times, and even more preferably 30 to 70 times.
• the number of filters to be combined is not particularly limited, but is preferably 1 to 10, and more preferably 2 to 5.
• the pore size of the filter that comes into contact with the liquid first is preferably equal to or larger than the pore size of the filter that comes into contact with the liquid last.
• the nominal value of the filter manufacturer can be referred to for the pore size.
• filters can be selected from a variety of filters provided by, for example, Nippon Pall Corporation, Advantec Toyo Co., Ltd., Nippon Integris Co., Ltd., or Kitz Microfilter Co., Ltd.
• the temperature during filtering is preferably 25°C or less, more preferably 23°C or less, and even more preferably 20°C or less.
• the lower limit is preferably 0°C or more, more preferably 5°C or more, and even more preferably 10°C or more.
• the ion removal process is a process in which the product to be purified is subjected to ion exchange or ion adsorption by a chelating group.
• Components removed by the ion removal process are not particularly limited, but examples thereof include acids and metal ions.
• the method of ion exchange treatment is not particularly limited, and known methods can be used.
• a method of contacting the material to be purified with an ion exchange resin can be mentioned, and a method of passing the material to be purified through a packing part filled with an ion exchange resin is preferable.
• the material to be purified may be passed through the same ion exchange resin multiple times, or the material to be purified may be passed through different ion exchange resins.
• Ion exchange resins include anion exchange resins and cation exchange resins. When both a cation exchange resin and an anion exchange resin are used, the mixture may be passed through a packed section filled with a mixed resin containing both resins, or may be passed through multiple packed sections filled with each resin.
• anion exchange resin a known anion exchange resin can be used, and it is preferable to use a gel-type anion exchange resin.
• anion exchange resins include strongly basic anion exchange resins having a quaternary ammonium group and weakly basic anion exchange resins having an amino group.
• anion exchange resin commercially available products can be used, such as Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, and ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, and Duolite A-375LF (manufactured by Sumika Chemtex Corporation), and DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (manufactured by Mitsubishi Chemical Corporation).
• the anion exchange resin described in JP-A-2009-155208 can also be used.
• cation exchange resin known cation exchange resins can be used, and gel-type cation exchange resins are preferred.
• Specific examples of the cation exchange resin include sulfonic acid type cation exchange resins and carboxylic acid type cation exchange resins.
• cation exchange resin commercially available products can be used, such as Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, ORLITE DS-4 (all manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, Duolite C-433LF (all manufactured by Sumika Chemtex Corporation), DIAION SK-110, DIAION SK1B, and DIAION SK1BH (all manufactured by Mitsubishi Chemical Corporation), Purolite S957, and Purolite S985 (all manufactured by Purolite Corporation), and the like.
• Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, ORLITE DS-4 all manufactured by Organo Corporation
• the ion adsorption treatment using a chelating group is not particularly limited, and a known method can be used, for example, a method in which the material to be purified is passed through a packing portion packed with a chelating resin having a chelating group.
• the ion removal treatment may involve passing the material to be purified through the same chelating resin multiple times, or may involve passing the material to be purified through different chelating resins.
• Chelating resins include chelating groups or resins with chelating ability, such as amidoxime groups, thiourea groups, thiouronium groups, iminodiacetic acid, amidophosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, alkylamino groups, pyridine rings, cyclic cyanines, phthalocyanine rings, and cyclic ethers.
• chelating groups or resins with chelating ability such as amidoxime groups, thiourea groups, thiouronium groups, iminodiacetic acid, amidophosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, alkylamino groups, pyridine rings, cyclic cyanines, phthalocyanine rings, and cyclic ethers.
• the ion removal process may be combined with the above-mentioned filtration process.
• a column filled with ion exchange resin may be incorporated into the above-mentioned circulation filtration device, and the water may be passed continuously through the ion exchange resin-filled section and the filter.
• the method of distillation is not particularly limited, and known methods can be used.
• a method using a distillation column can be used.
• the components removed by the distillation step are not particularly limited, and examples thereof include acids, organic compounds, and water.
• the liquid-contacting parts of the distillation column are not particularly limited, but are preferably made of a corrosion-resistant material.
• corrosion-resistant materials include materials used as treatment liquid containers, which will be described later.
• the material to be purified may be passed through the same distillation column multiple times, or the material to be purified may be passed through different distillation columns.
• a crude distillation process is performed by passing the material to be purified through a distillation column to remove low-boiling point acids, etc.
• a rectification process is performed by passing the material to a distillation column different from the crude distillation process to remove acid components and other organic compounds, etc.
• the distillation column in the crude distillation process may be a plate distillation column
• the distillation column in the rectification process may be at least one of a plate distillation column and a reduced pressure plate distillation column.
• the number of theoretical plates is preferably 50 or more, more preferably 100 or more. There is no particular upper limit, but it is often 200 or less. In order to achieve both thermal stability during distillation and high purification accuracy, reduced pressure distillation may be used.
• the distillation process may be used in combination with at least one selected from the above-mentioned filtration process and ion removal process.
• a distillation column may be placed on the primary side of the purification device used for the above-mentioned filtration process, and the distilled product to be purified may be introduced into the purification device.
• a dehydration treatment may be carried out.
• the dehydration treatment for example, the above-mentioned water removal methods can be used.
• a preferred method for producing the treatment liquid is to prepare purification materials each containing PGMEA, water, and an organic acid, subject each of the purification materials to a purification process, and mix the resulting purification materials that have been subjected to the purification processes to produce the treatment liquid.
• the purification treatment is preferably a purification treatment including at least the distillation treatment and the filtration treatment.
• the order of the distillation treatment and the filtration treatment is not particularly limited, and the filtration treatment may be performed after the distillation treatment, or the distillation treatment may be performed after the filtration treatment.
• the filtration process it is preferable to use at least one first filter selected from the group consisting of ion exchange filters and filters containing polyamide resins (e.g., Nylon filters) and at least one second filter selected from the group consisting of PTFE filters and UPE filters.
• the first filter can mainly remove ionic impurities
• the second filter can mainly remove particles (metal particles, organic fine particles, etc.).
• a plurality of first filters and a plurality of second filters may be used.
• the filtration process may be a circulating filtration process. The number of times the circulating filtration process is performed is as described above, but it is preferable that the number of times is 30 or more.
• distillation treatment it is preferable to pass the product to be purified through different distillation columns.
• the clean room is preferably a clean room with a cleanliness of class 4 or higher as defined by the international standard ISO14644-1:2015 established by the International Organization for Standardization. Specifically, it is preferable that the clean room satisfies any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, it is more preferable that the clean room satisfies ISO class 1 or ISO class 2, and it is particularly preferable that the clean room satisfies ISO class 1.
• the treatment liquid In order to maintain stable performance for a long period of time, it is preferable to handle, manufacture, refine, contain, and store the treatment liquid at 30°C or less.
• the lower limit is preferably 5°C or more, and more preferably 10°C or more.
• the treatment liquid may be stored in a container.
• the container and the processing solution contained in the container are collectively referred to as a processing solution container.
• the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% by volume or higher.
• an inert gas a gas with a low moisture content is preferable.
• the solution may be stored at room temperature, but the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.
• any known container can be used as the container for containing the treatment liquid, and it is preferable that the container is designed for semiconductor applications, has a high degree of cleanliness within the container, and is less susceptible to the elution of impurities.
• containers include the "Clean Bottle” series (manufactured by Aicello Chemical Co., Ltd.) and the “Pure Bottle” (manufactured by Kodama Resin Industry Co., Ltd.)
• a multi-layer container having an inner wall of six layers made of six types of resins, or a multi-layer container having a seven-layer structure made of seven types of resins. Examples of multi-layer containers include those described in JP 2015-123351 A, the contents of which are incorporated herein by reference.
• the liquid-contacting parts of the container that come into contact with the processing liquid are preferably made of a non-metallic material to prevent contamination.
• the non-metallic material is not particularly limited, and known materials can be used.
• Examples include polyethylene resin, polypropylene resin, polyethylene-polypropylene resin, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkylvinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-ethylene copolymer resin, trifluorochloroethylene-ethylene copolymer resin, vinylidene fluoride resin, trifluorochloroethylene copolymer resin, and vinyl fluoride resin.
• containers whose inner walls are made of fluororesin include FluoroPure PFA composite drums manufactured by Entegris Inc.
• containers described on page 4 of JP-A-3-502677, page 3 of WO 2004/016526, and pages 9 and 16 of WO 99/046309 can also be used.
• the inner wall is made of a non-metallic material, it is preferable that the elution of organic components in the non-metallic material into the solution is suppressed.
• the liquid contact portion may be made of a metal material.
• the metal material is not particularly limited, but is preferably a metal material containing more than 25 mass % of chromium based on the total mass of the metal material.
• Examples of the metal material include stainless steel and nickel-chromium alloys, with stainless steel being preferred.
• the stainless steel is not particularly limited, and any known stainless steel can be used. Among them, an alloy containing 8% or more by mass of nickel is preferable, and an austenitic stainless steel containing 8% or more by mass 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 10% by mass, Cr content 16% by mass), and SUS316L (Ni content 12% by mass, Cr content 16% by mass), etc.
• the nickel-chromium alloy is not particularly limited, and a known nickel-chromium alloy can be used.
• nickel-chromium alloys include Hastelloy (trade name, the same applies below), Monel (trade name, the same applies below), and Inconel (trade name, the same applies below). More specifically, Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), and Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%) can be mentioned.
• the nickel-chromium alloy may further contain silicon, tungsten, molybdenum, copper, cobalt, and the like, in addition to the above-mentioned alloy, as required.
• the metallic material is electropolished, more preferably electropolished stainless steel.
• the electrolytic polishing method a known method can be used. For example, the methods described in [0011] to [0014] of JP-A-2015-227501 and [0036] to [0042] of JP-A-2008-264929 can be used.
• the metal material may be buffed to prevent contamination.
• the method of buffing is not particularly limited, and known methods can be used.
• the size of the polishing grains used for finishing the buffing is not particularly limited, but #400 or less is preferable because it tends to reduce the unevenness of the surface of the metal material. It is preferable that the buffing is performed before electrolytic polishing.
• the metal material may be treated by one or a combination of two or more of multiple steps of buff polishing using different grit sizes of polishing abrasive grains, acid washing, and magnetic fluid polishing.
• the inside of the container is preferably washed before filling it with the treatment liquid.
• the liquid used for washing is preferably the treatment liquid or a diluted version of the treatment liquid.
• the treatment liquid of the present invention can be used, for example, in the following pattern forming method.
• the pattern formation method includes a step 1 of forming a metal resist film on a substrate using an actinic ray- or radiation-sensitive composition (hereinafter also referred to as a "metal resist composition") containing a metal compound (hereinafter also referred to as a "specific metal compound”) having at least one bond selected from the group consisting of a metal-carbon bond and a metal-oxygen bond, a step 2 of exposing the metal resist film to light, and a step 3 of developing the exposed metal resist film using a developer to remove unexposed areas to obtain a pattern.
• the pattern formation method may further include a step 4 of washing the pattern using a rinse solution after the step 3. Each step will be described in detail below.
• Step 1 is a step of forming a metal resist film using a metal resist composition.
• methods for forming a metal resist film using the metal resist composition include a method of applying the metal resist composition onto a substrate and a method of depositing a metal resist component onto a substrate. The metal resist composition will be described later.
• methods for applying the metal resist composition onto a substrate include methods in which the metal resist composition is applied onto a substrate (e.g., silicon) used in the manufacture of semiconductor devices such as integrated circuits, using an apparatus such as a spinner or coater.
• the coating method is preferably spin coating using a spinner, and the rotation speed during spin coating is preferably 1000 to 3000 rpm.
• the substrate coated with the metal resist composition may be dried to form a metal resist film.
• the drying method may be, for example, heating (PreBake).
• Heating a means provided in a known exposure machine and/or a known development machine may be used, and a hot plate may also be used.
• the heating temperature is preferably 80 to 150° C., more preferably 80 to 140° C., and even more preferably 80 to 130° C.
• the heating time is preferably 30 to 1000 seconds, more preferably 30 to 800 seconds, and even more preferably 40 to 600 seconds. Heating may be performed two or more times.
• the thickness of the metal resist film is preferably 10 to 90 nm, more preferably 10 to 65 nm, and even more preferably 15 to 50 nm, in order to form fine patterns with higher precision.
• an undercoat film (for example, an inorganic film, an organic film, an anti-reflection film, etc.) may be formed between the substrate and the metal resist film.
• the undercoat film can be formed using a known organic or inorganic material.
• the composition for forming the undercoat film include AL412 (manufactured by Brewer Science) and the SHB series (eg, SHB-A940, etc., manufactured by Shin-Etsu Chemical Co., Ltd.).
• the thickness of the undercoat film is preferably from 10 to 90 nm, more preferably from 10 to 50 nm, and even more preferably from 10 to 30 nm.
• a top coat may be formed on the surface of the metal resist film opposite the substrate using a top coat composition. It is preferable that the top coat composition does not mix with the metal resist film and can be applied uniformly to the surface of the metal resist film opposite the substrate.
• the topcoat composition preferably comprises a resin, an additive and a solvent. Examples of the method for forming the top coat include known top coat forming methods, specifically, the top coat forming methods described in [0072] to [0082] of JP2014-059543A.
• the metal resist composition contains a specific metal compound.
• the specific metal compound is a metal compound having at least one bond selected from the group consisting of a metal-carbon bond (MC) and a metal-oxygen bond (MO), where M represents a metal atom.
• the metal-carbon bond refers to a state in which a metal atom and at least one carbon atom are bonded together by a covalent bond, a coordinate bond, an ionic bond, a van der Waals bond, or the like.
• the covalent bond may be any of a single bond, a double bond, and a triple bond.
• the metal-oxygen bond refers to a state in which at least one metal atom and at least one oxygen atom in a specific metal compound are bonded together by a covalent bond, a coordinate bond, an ionic bond, a van der Waals bond, or the like.
• the covalent bond may be any of a single bond and a double bond.
• the specific metal compound has a metal-carbon bond
• the specific metal compound is a so-called organometallic compound.
• the number of bonds selected from the above group that the specific metal compound has is preferably 2 or more, more preferably 3 or more.
• the upper limit is preferably 10 or less, more preferably 5 or less.
• Examples of the metal atom constituting the specific metal compound include metal atoms of Groups 3 to 16 in the periodic table, and preferably tin, antimony, tellurium, indium, hafnium, tartan, tungsten, bismuth, titanium, cobalt, nickel, zirconium, or palladium, and more preferably tin.
• silicon atoms are included in the metal atoms.
• An example of a specific metal compound is a compound represented by formula (1).
• M represents a metal atom.
• M include metal atoms constituting the specific metal compound.
• M is tin, antimony, tellurium, indium, hafnium, tartan, tungsten, bismuth, titanium, cobalt, nickel, zirconium, or palladium, and more preferably, M is tin.
• R 1 represents an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• the alkyl group may be linear, branched, or cyclic.
• the number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 16, and still more preferably 1 to 5.
• the alkyl group represented by R1 is an alkyl group having a substituent, the number of carbon atoms in the substituent is also included in the number of carbon atoms in the alkyl group.
• Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, and an aromatic ring group.
• the aromatic ring group is preferably a phenyl group.
• the alkyl group having a phenyl group is preferably a benzyl group.
• the aliphatic unsaturated hydrocarbon group is an aliphatic hydrocarbon group having an unsaturated group therein. Examples of the unsaturated group include a double bond and a triple bond.
• the aliphatic unsaturated hydrocarbon group may be any of linear, branched, and cyclic.
• the number of carbon atoms in the aliphatic unsaturated hydrocarbon group is preferably 2 to 30, more preferably 2 to 16, and even more preferably 2 to 5.
• the number of carbon atoms includes the number of carbon atoms of the substituent.
• the aliphatic unsaturated hydrocarbon group is preferably a vinyl group or an allyl group.
• Examples of the substituent that the aliphatic unsaturated hydrocarbon group may have include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, and an aromatic ring group.
• the aryl group may be either monocyclic or polycyclic.
• the number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 12, and still more preferably 6 to 8.
• the aryl group represented by R1 is an aryl group having a substituent
• the number of carbon atoms in the substituent is also included in the number of carbon atoms in the substituent.
• the aryl group is preferably a phenyl group or a naphthyl group.
• substituent that the aryl group may have include an alkyl group, a halogen atom, a hydroxyl group, a cyano group, a nitro group, an amino group, and an aromatic ring group.
• R 2 represents -OCOR r1 or -OR r2 .
• R r1 represents a hydrogen atom, an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• R r2 represents an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• -OCOR r1 is preferable.
• Examples of the alkyl group which may have a substituent, the aliphatic unsaturated hydrocarbon group which may have a substituent, and the aryl group which may have a substituent represented by R r1 or R r2 include the groups represented by R 1 above.
• n1+m1 represents the valence of the metal atom represented by M.
• n1+m1 is appropriately selected according to the possible valence of the metal atom represented by M.
• n1 is preferably an integer of 0 to 2, and more preferably 1.
• m1 is preferably an integer of 0 to 4, and more preferably 3.
• R 1 's When a plurality of R 1 's are present, the R 1 's may be the same or different.
• the R 2 's may be the same or different.
• Specific metal compounds include compounds represented by formula (2) and condensates thereof.
• R3 represents a hydrocarbon group which may have a substituent.
• the hydrocarbon group include an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, and an aryl group which may have a substituent.
• the preferred embodiments of the alkyl group, the aliphatic unsaturated hydrocarbon group, and the aryl group are the same as the preferred embodiments of each group represented by R1 .
• the R 3 's may be the same or different.
• z and x represent numbers that satisfy the relationship in formula (2-1) and the relationship in formula (2-2).
• the specific metal compound also includes a compound represented by formula (3).
• M represents a metal atom.
• M include the metal atom represented by M in formula (1).
• R4 and R6 each independently represent an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• R4 and R6 include the groups represented by R1 above.
• R5 and R7 each independently represent -OCORr3 or -ORr4 .
• Rr3 represents a hydrogen atom, an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• Rr4 represents an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• R r3 and R r4 include the groups represented by R r1 and R r2 above, respectively.
• R5 and R7 include the groups represented by R2 above.
• the R4 's may be the same or different.
• the R5 's may be the same or different.
• the R6's may be the same or different.
• L represents a single bond or a divalent linking group.
• the divalent linking group include an alkylene group and an arylene group.
• n2+m2 and n3+m3 each independently represent the valence of the metal atom represented by M minus 1.
• Specific metal compounds include the compound represented by formula (4), its hydrolysate, and condensates of the hydrolysate.
• R 8 represents a hydrocarbon group which may have a substituent.
• the hydrocarbon group include the groups represented by R1 above.
• X represents a hydrolyzable group. nz represents 1 or 2.
• Examples of X include -NHR x1 , -NR x1 R x2 , -OSiR x1 R x2 R x3 , -N(SiR x1 3 )(R x2 ), -N(SiR x1 3 )(SiR x2 3 ), azide group, -C ⁇ CR x1 , -NH(COR x1 ), -NR x1 (COR x2 ), -NR x1 C(NR x2 )R x3 (amidinate group) and imide group, with -NHR x1 or -NR x1 R x2 being preferred.
• R x1 to R x3 each independently represent a hydrocarbon group having 1 to 10 carbon atoms.
• R x1 to R x3 are preferably alkyl groups having 1 to 10 carbon atoms.
• the R 8 's may be the same or different.
• the X's may be the same or different.
• the specific metal compound is preferably a compound represented by formula (5).
• R 9 represents an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• R 10 represents -OCOR r5 or -OR r6 .
• R r5 represents a hydrogen atom, an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• R r6 represents an alkyl group which may have a substituent, an aliphatic unsaturated hydrocarbon group which may have a substituent, or an aryl group which may have a substituent.
• R 9 , R 10 , R r5 and R r6 have the same meanings as R 1 , R 2 , R r1 and R r2 in formula (1), respectively, and the preferred embodiments are also the same.
• a plurality of R 10 's may be the same or different.
• the specific metal compound preferably includes at least one selected from the group consisting of a compound represented by formula (1), a compound represented by formula (2), and a condensate thereof, more preferably includes at least one selected from the group consisting of a compound represented by formula (5), a compound represented by formula (2), and a condensate thereof, and even more preferably includes at least one selected from the group consisting of a compound represented by formula (2) and a condensate thereof.
• Specific metal compounds include, for example, those described in JP 2021-047426 A, JP 2021-179606 A, Japanese Patent No. 6805244, and WO 2019/111727.
• the specific metal compounds may be used alone or in combination of two or more.
• the content of the specific metal compound is preferably from 50 to 100% by mass, and more preferably from 80 to 100% by mass, based on the total solid content of the metal resist composition.
• the metal resist composition may contain an organic acid.
• organic acid include carboxylic acids, sulfonic acids, sulfinic acids, organic phosphinic acids, organic phosphonic acids, phenols, enols, thiols, imido acids, oximes, and sulfonamides, with carboxylic acids being preferred.
• carboxylic acid examples include monocarboxylic acids such as formic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, 2-ethylhexanoic acid, oleic acid, acrylic acid, methacrylic acid, trans-2,3-dimethylacrylic acid, stearic acid, linoleic acid, linolenic acid, arachidonic acid, salicylic acid, benzoic acid, p-aminobenzoic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid, pentafluoropropionic acid, gallic acid, and shikimic acid; dicarboxylic acids such as oxalic acid, malonic acid, maleic acid, methylmalonic acid, fumaric acid, adipic acid
• the organic acids may be used alone or in combination of two or more.
• the content of the organic acid is preferably from 0 to 10 mass %, and more preferably from 1 to 5 mass %, based on the total solid content of the metal resist composition.
• the metal resist composition may contain an organic solvent, such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, or a hydrocarbon-based solvent.
• an organic solvent such as a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amide-based solvent, an ether-based solvent, or a hydrocarbon-based solvent.
• Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonylalcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate, with cyclohexanone, 2-heptanone, or diisobutylketone being preferred.
• Ester solvents include, for example, methyl acetate, butyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 1-methoxy-2-propyl acetate, and 3-methyl-3-methoxybutyl acetate.
• alcohol-based solvents examples include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, 4-methyl-2-pentanol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol.
• amide solvents include N,N-dimethylformamide, 1-methyl-2-pyrrolidone, 2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ⁇ -caprolactam, formamide, N-methylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methylpropanamide, and hexamethylphosphoric triamide.
• ether solvents examples include dioxane, tetrahydrofuran, anisole, and diisobutyl ether, with diisobutyl ether being preferred.
• hydrocarbon solvents include saturated aliphatic hydrocarbon solvents such as pentane, hexane, octane, nonane, decane, undecane, dodecane, hexadecane, 2,2,4-trimethylpentane, and 2,2,3-trimethylhexane, as well as aromatic hydrocarbon solvents such as mesitylene, cumene, pseudocumene, 1,2,4,5-tetramethylbenzene, p-cymene, toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene, ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene.
• Saturated aliphatic hydrocarbon solvents are preferred, with octane, nonane, decane,
• the metal resist composition may contain other additives such as a surfactant, water, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (e.g., a phenol compound having a molecular weight of 1000 or less, and an alicyclic or aliphatic compound containing a carboxylic acid group).
• a surfactant water
• a dissolution inhibiting compound e.g., a dye having a molecular weight of 1000 or less, and an alicyclic or aliphatic compound containing a carboxylic acid group.
• the surfactant is preferably a fluorine-based surfactant or a silicon-based surfactant, and for example, the surfactants described in paragraphs [0218] and [0219] of WO 2018/193954 can be used.
• Step 2 is a step of exposing the metal resist film to light.
• the exposure may be performed as a full-surface exposure or a pattern-wise exposure.
• Step 2 is preferably a step of performing pattern exposure through a photomask.
• the photomask may be, for example, a known photomask.
• the photomask may be in contact with a metal resist film.
• Examples of the exposure light for exposing the metal resist film include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams.
• the wavelength of the exposure light is preferably 250 nm or less, more preferably 220 nm or less, and even more preferably 1 to 200 nm.
• KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), F2 excimer laser (wavelength 157 nm), X-ray, EUV (wavelength 13 nm), or electron beam is preferred
• KrF excimer laser, ArF excimer laser, EUV, or electron beam is more preferred
• EUV or electron beam is even more preferred.
• the amount of exposure is not particularly limited as long as the solubility of the exposed metal resist film in a developer containing an organic solvent is reduced.
• the exposure method may be immersion exposure. Step 2 may be carried out once or more than once.
• Step 3 is a step of developing the exposed metal resist film using a developer, which removes the unexposed areas of the exposed metal resist film to form a pattern.
• a known developing method can be used. Specifically, there are a method of immersing the exposed metal resist film in a tank filled with a developing solution for a certain period of time (dip method), a method of piling up the developing solution on the surface of the exposed metal resist film by surface tension and leaving it still for a certain period of time to develop (paddle method), a method of spraying the developing solution on the surface of the exposed metal resist film (spray method), and a method of continuously discharging the developing solution while scanning a nozzle that discharges the developing solution at a constant speed onto a substrate having an exposed metal resist film rotating at a constant speed (dynamic dispense method).
• dip method immersing the exposed metal resist film in a tank filled with a developing solution for a certain period of time
• spray method a method of spraying the developing solution on the surface of the exposed metal resist film
• dynamic dispense method
• a step of stopping the development using a solvent other than the developer may be carried out.
• the development time is preferably from 10 to 300 seconds, and more preferably from 20 to 120 seconds.
• the temperature of the developer during development is preferably from 0 to 50°C, and more preferably from 15 to 35°C.
• the processing solution of the present invention can be used as a developer in step 3.
• the developer in step 3 is the treatment liquid of the present invention described above.
• the developing liquid in step 3 may be either the treatment liquid of the present invention described above or another chemical liquid different from the treatment liquid of the present invention.
• the other chemicals are different from the processing solution of the present invention, and known developing solutions and rinsing solutions can be used.
• the other chemical liquid includes an organic solvent.
• the organic solvent included in the other chemical liquid include ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. Specific examples include organic solvents that may be included in the metal resist.
• the other chemical solution may contain one type of organic solvent alone or two or more types in combination.
• the other chemicals may contain organic solvents other than those mentioned above, water, a surfactant, and the like.
• Step 4 is a step of cleaning the pattern obtained in step 3 (development step) with a rinsing liquid.
• Examples of the rinsing method include the same methods as the developing method in the above step 3 (for example, a dipping method, a puddle method, a spray method, a dynamic dispensing method, etc.).
• the treatment time is preferably from 10 to 300 seconds, more preferably from 10 to 120 seconds.
• the temperature of the rinse solution is preferably from 0 to 50°C, more preferably from 15 to 35°C.
• the rinse liquid in step 4 is preferably the above-mentioned processing liquid of the present invention.
• the rinsing solution in step 4 may be either the above-mentioned processing solution of the present invention or another chemical solution.
• the other chemical liquids that may be used as the rinsing liquid have the same meaning as the other chemical liquids that may be used in the developer described above, and the preferred embodiments are also the same.
• the pattern formation method may further include steps other than the above steps 1 to 4.
• Other steps include, for example, a post-exposure bake step, a post-bake step, an etching step, and a purification step.
• the pattern formation method preferably includes a post-exposure bake (PEB) step after performing step 2 (exposure step) and before performing step 3 (development step).
• the heating temperature for post-exposure baking is preferably from 80 to 200° C., more preferably from 80 to 180° C., and even more preferably from 80 to 150° C.
• the heating time is preferably from 10 to 1,000 seconds, more preferably from 10 to 180 seconds, and even more preferably from 30 to 120 seconds.
• the post-exposure bake may be performed using a means provided in a known exposure machine and/or a development machine, or a hot plate.
• the post-exposure bake may be performed once or twice or more times.
• the pattern forming method preferably includes a step of heating the pattern (post-baking step) after step 4 (rinsing step).
• the post-baking (PB) step can remove the developer and rinsing solution remaining between and inside the patterns, and can improve the surface roughness of the pattern.
• the heating temperature in the post-baking step is preferably from 40 to 250°C, and more preferably from 80 to 200°C.
• the heating time in the post-bake step is preferably from 10 to 180 seconds, and more preferably from 30 to 120 seconds.
• the pattern forming method may include an etching step of etching the substrate using the formed pattern as a mask.
• the etching method may be, for example, a known etching method, such as those described in the Proceedings of the International Society of Optics and Electronics (Proc. of SPIE) Vol. 6924, 692420 (2008), "Chapter 4: Etching" of "Semiconductor Processing Textbook, 4th Edition, published in 2007, published by SEMI Japan,” and JP-A-2009-267112.
• the pattern formation method may include a purification step of purifying the metal resist composition, the developer, the rinse solution, and/or other various components (e.g., a composition for forming an undercoat film, a composition for forming a top coat, etc.) used in the pattern formation method.
• the purification method may be, for example, a known purification method, and a method using filtering or an adsorbent is preferred.
• the method for producing an electronic device of the present invention includes a step of using the treatment liquid of the present invention described above.
• a preferred embodiment of the present invention includes a method for producing an electronic device, which includes a step of forming a pattern using the treatment liquid of the present invention according to the pattern formation method described above.
• the electronic device is suitably mounted in electric and electronic equipment (for example, home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment).
• PGME-containing purification material was synthesized using the method described in JP-A-2011-050988. Next, the obtained product was subjected to circulation filtration and purification using a filtration device in which the following ion exchange resins and filters were connected in series from the upstream to the downstream, and further equipped with a return path from the most downstream to the most upstream. The circulation number was 50 times. The details of each component of the filtration device will be described below, starting from the upstream side.
• Anion exchange resin anion exchange resin described in Production Example 1 of paragraph 0028 of JP-T-2009-1552078
• Ion exchange filter Pall Corporation, IonKleen SL
• Nylon filter Pall Corporation, Asymmetric, pore size 5 nm
• UPE filter Integris, Purasol SP/SN solvent purifier
• PTFE filter Pall Corporation, XpressKLEEN, pore size 3 nm
• UPE filter Integris, Microgard, pore size 3 nm
• an operation of passing the purified material from the most upstream purification member to the most downstream purification member is counted as one circulation cycle.
• distillation purification was carried out starting from the first plate distillation tower, and PGME was obtained for use as a raw material for the treatment liquid.
• Organic acids acetic acid (manufactured by Kanto Chemical Co., Ltd.), formic acid (manufactured by Kanto Chemical Co., Ltd.), propionic acid (manufactured by Sigma-Aldrich Co., Ltd.), butyric acid (manufactured by Sigma-Aldrich Co., Ltd.), and lactic acid (manufactured by Sigma-Aldrich Co., Ltd.), were purified by circulating filtration. The number of circulations was 50 times.
• distillation purification was carried out using the same method as for distillation purification of PGME.
• a PGMEA-containing purification product was synthesized by ester synthesis using the PGME synthesized and purified by recycling filtration according to the above-mentioned method, and the acetic acid synthesized and purified by recycling filtration according to the above-mentioned method as raw materials.
• the above ester synthesis was carried out by the method described in JP-A-2001-521918.
• the obtained purified product was dehydrated by a column method using Molecular Sieve 3A (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). Next, distillation purification was carried out in the same manner as in the distillation purification of PGME. Furthermore, a filtration device in which the filters shown below were connected in series from the upstream side and further provided with a return line from the most downstream side to the most upstream side was used to perform circulation filtration and purification to obtain PGMEA to be used as a raw material for the treatment liquid. The circulation number was set to 50 times. The details of each component of the filtration device will be described below, starting from the upstream side.
• Nylon filter Pall Corporation, Asymmetric, pore size 5 nm
• UPE filter Integris, Purasol SP/SN solvent purifier
• - PTFE filter Pall Corporation, XpressKLEEN, pore size 3 nm
• UPE filter Integris, Microgard, pore size 3 nm
• PGMEA, PGME, and acetic acid were obtained, each of which had a water content reduced to below the detection limit and a boron atom content and a Pb atom content each of which was less than 0.0001 ppt by mass.
• the water content was measured using the above-mentioned Karl Fischer moisture meter (product name "MKC-710M", manufactured by Kyoto Electronics Manufacturing Co., Ltd., Karl Fischer coulometric titration type).
• the water detection limit of the above-mentioned device was 1 ppm by mass.
• the boron atom content was measured using the above-mentioned ICP-MS (apparatus used: Agilent 8900 triple quadrupole ICP-MS).
• the detection limit of the boron atom content of the above-mentioned apparatus was 0.6 ppt by mass (unconcentrated).
• the content of Pb atoms was measured using the above-mentioned ICP-MS (apparatus used: Agilent 8900 triple quadrupole ICP-MS).
• the detection limit of the content of Pb atoms using the above-mentioned apparatus was 0.1 ppt by mass (unconcentrated).
• the boron atom content and the Pb atom content in PGMEA, PGME, and acetic acid were measured using the above-mentioned device after concentrating them in the same manner as in the measurement method for the treatment liquid described below.
• the boron atom content was 0.0001 ppt by mass or less
• the Pb atom content was 0.0001 ppt by mass or less.
• the contents of transition elements measurable by ICP-MS other than Pb atoms measured by the above-mentioned device were all less than 0.0001 ppt by mass.
• the boron atom source was added by immersing solid high-purity boron (manufactured by Tokuyama Corporation) in the treatment liquid for a predetermined time, and dissolving boron into the treatment liquid so that the boron atom content reached a predetermined value.
• the amount and time of immersion of high purity boron in the treatment solution were set so that the final content of boron atoms in the treatment solution was a predetermined value, based on a calibration curve of the amount of elution of boron atoms versus the surface area and immersion time of high purity boron.
• the content of boron atoms in the treatment solution was measured by ICP-MS using an Agilent 8900 triple quadrupole ICP-MS (manufactured by Agilent Technologies, for semiconductor analysis, option #200).
• the boron atom (boron) content in the treatment liquid was quantified according to the following procedure.
• ultrapure water standard product
• the content of boron atoms in the added ultrapure water was 0.0001 ppt by mass relative to the total mass of the added ultrapure water.
• the ultrapure water was concentrated 10,000 times and measured in the same manner as described above.
• the treatment liquid to which ultrapure water was added was heated under reflux conditions at 100°C for 1 hour to convert the boron present in the treatment liquid into the form of boric acid. Thereafter, the organic solvent and water contained in the treatment liquid were removed at 160-180°C to concentrate the non-volatile components contained in the treatment liquid, and the content of boron atoms was quantified using the above-mentioned device. The content of boron atoms contained in the treatment liquid was calculated taking into account the mass of boron atoms contained in the ultrapure water.
• the Pb atom source was added by adding a PGMEA solution of Pb nanoparticles (American Elements, (5N) 99.999% Lead Oxide Nanopowder) adjusted to a specified concentration to the treatment liquid.
• PGMEA solution of Pb nanoparticles American Elements, (5N) 99.999% Lead Oxide Nanopowder
• a base film-forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto a silicon wafer having a diameter of 300 mm, and baked at 205° C. for 60 seconds to form a base film having a thickness of 20 nm.
• a metal resist composition was applied onto the obtained base film, and baked at 100° C. for 90 seconds to form a metal resist film having a thickness of 22 nm. In this way, a silicon wafer having a metal resist film was formed.
• the silicon wafer having the metal resist film was pattern-exposed with a minimum exposure dose at the limiting resolution described below using an EUV scanner NXE3400 (NA 0.33, ASML).
• a pillar pattern with a pitch of 45 nm and an opening size of 25 nm was used as the reticle. Then, the wafer was post-exposure baked (PEB) at 150° C. for 90 seconds. Next, in Examples 1 to 131 and Comparative Examples 1 to 44, a development process was performed by puddling the treatment solution of each Example or Comparative Example for 30 seconds, and the wafer was dried by rotating at 4000 rpm for 30 seconds to obtain a pillar pattern with a pitch of 45 nm. In Examples 132 to 138 and Comparative Examples 45 to 48, a development process was performed by puddling for 30 seconds with the developer of Comparative Example 3.
• a rinse process was performed by pouring the treatment solution of each Example and Comparative Example for 10 seconds while rotating the wafer at 1000 rpm, and the wafer was dried by rotating at 4000 rpm for 30 seconds to obtain a pillar pattern with a pitch of 45 nm.
• a silicon substrate having a diameter of 300 mm was prepared, and a surface defect inspection device (KLA, SurfScan SP7) was used to irradiate laser light onto the silicon substrate surface and measure the scattered light, thereby measuring the position and size of defects on the silicon substrate.
• the silicon substrate was coated with the treatment solution of each of the Examples and Comparative Examples using a coating and developing apparatus (CLEAN TRACK LITHIUS PRO Z, manufactured by Tokyo Electron Ltd.) After that, the substrate was spin-dried at 2000 rpm for 30 seconds, and the positions and sizes of defects on the silicon substrate were measured by the above-mentioned method using a surface defect inspection apparatus (SurfScan SP7, manufactured by KLA Corporation).
• Defects caused by the processing liquid were extracted from the defect positions, number and size before and after application of the processing liquid, and the suppression of defects caused by the processing liquid was evaluated according to the following evaluation criteria. The fewer the number of defects caused by the processing solution, the more preferable.
• A The number of defects of 20 nm or less caused by the treatment liquid is 10 or less.
• B The number of defects of 20 nm or less caused by the treatment liquid is more than 10 and less than 20.
• C The number of defects of 20 nm or less caused by the treatment liquid is more than 20 and less than 50.
• D The number of defects of 20 nm or less caused by the treatment liquid is more than 50.
• A The resolution limit is 14 nm or less.
• B The resolution limit is more than 14 nm and less than 15 nm.
• C The resolution limit is more than 15 nm and less than 16 nm.
• D The resolution limit is more than 16 nm.
• the number of defects of 20 nm or less derived from the processing liquid before and after storage at elevated and lower temperatures was compared, and the resistance of the processing liquid to deterioration in the ability to suppress defects derived from the processing liquid due to storage at elevated and lower temperatures was evaluated according to the following evaluation criteria. The smaller the increase in the number of defects before and after storage at elevated and lower temperatures, the less deterioration of the processing solution due to storage, and the more preferable.
• A The increase in the number of defects is 10 or less.
• B The increase in the number of defects is more than 10 and less than 20.
• C The increase in the number of defects is more than 20 and less than 30.
• D The increase in the number of defects is more than 30.
• the number of defects containing an alkali metal element or an alkaline earth metal element (hereinafter also referred to as a "specific element") (specific element-containing defects) was calculated and evaluated according to the following evaluation criteria. The fewer the number of specific element-containing defects, the more preferable.
• A The number of defects containing a specific element is 1 or less.
• B The number of defects containing a specific element is more than 1 and 3 or less.
• C The number of defects containing a specific element is more than 3 and 5 or less.
• D The number of defects containing a specific element is more than 5.
• A The number of boron-containing defects is 1 or less.
• B The number of boron-containing defects is more than 1 and 3 or less.
• C The number of boron-containing defects is more than 3 and 5 or less.
• D The number of boron-containing defects is more than 5.
• Tables 1 to 8 show the composition of the treatment liquid, the use of the treatment liquid, and the evaluation results of each of the examples and comparative examples.
• the use column indicates whether the processing liquid was used as a developer or a rinse liquid.
• the definition of "organic acid/water” (specific mass ratio) is as described above.
• the column “Defect suppression (pattern)” shows the evaluation results of suppression of pattern defects
• the column “Defect suppression (defects due to processing liquid)” shows the evaluation results of suppression of defects due to processing liquid.
• the column “resolution” means pattern resolution.
• the column “specific element-containing defects” shows the evaluation results of "defects derived from alkali metals and/or alkaline earth metals”
• the column “boron-containing defects” shows the evaluation results of "defects derived from boron atoms.”
• the "balance" in the "PGMEA” column means that the balance other than the organic acid, PGME, water, boron, and Pb described in the table is made up of PGMEA. In each example, the content of PGMEA was 60 mass% or more based on the total mass of the treatment solution.
• Example 1 From a comparison between Example 1 and Examples 13 to 19, it was further confirmed that when the specific mass ratio is 500 to 50,000, the deterioration of the suppression ability of defects originating from the processing solution after storage at elevated temperatures and the deterioration of the pattern resolution after storage at elevated temperatures and the like can be further suppressed, and when the specific mass ratio is 1,000 to 10,000, the deterioration of the suppression ability of defects originating from the processing solution after storage at elevated temperatures and the deterioration of the pattern resolution after storage at elevated temperatures and the like can be further suppressed.
• the specific mass ratio is 500 to 50,000, the deterioration of the suppression ability of defects originating from the processing solution after storage at elevated temperatures and the deterioration of the pattern resolution after storage at elevated temperatures and the like can be further suppressed, and when the specific mass ratio is 1,000 to 10,000, the deterioration of the suppression ability of defects originating from the processing solution after storage at elevated temperatures and the deterioration of the pattern resolution after storage at elevated temperatures and the like can be further suppressed.
• the treatment liquid of each example was used as a metal resist cleaning liquid (eg, edge bead removal liquid).
• the following metal resist composition (2.5 mL) in the above-mentioned [Pattern formation] was applied onto a 12-inch silicon wafer, and a Sn resist film was formed by spin coating.
• the treatment solution (10 mL) of Examples 201 to 226 and Comparative Examples 201 to 209 was applied onto the Sn resist film, and the silicon wafer was rotated at 1500 rpm for 45 seconds until it dried. After repeating this cleaning operation 10 times, defects (particularly edge beat defects) on the silicon wafer were measured by the above-mentioned method using a surface defect inspection device (KLA Corporation, SurfScan SP7), and the cleaning performance was evaluated according to the following evaluation criteria.
• Metal resist removal ability The following metal resist composition (2.5 mL) in the above-mentioned [Pattern formation] was applied onto a 12-inch silicon wafer, and a Sn resist film was formed by spin coating. Next, the treatment solution (10 mL) of each Example was applied onto the silicon wafer on which the Sn resist film had been formed, and the silicon wafer was rotated at 1500 rpm for 45 seconds until it dried. This cleaning operation was repeated 10 times. Next, the amount of remaining Sn (atom/cm 2 ) was measured by ChemTrace (registered trademark) using vapor phase decomposition-inductively coupled plasma-mass spectrometry (VPD-ICP-MS).
• VPD-ICP-MS vapor phase decomposition-inductively coupled plasma-mass spectrometry
• A The amount of remaining Sn is 1 ⁇ 50 10 atom/cm 2 or less.
• B The amount of remaining Sn is greater than 1 ⁇ 50 10 atom/cm 2 and less than 1 ⁇ 10 11 atom/cm 2.
• C The amount of remaining Sn is greater than 1 ⁇ 10 11 atom/cm 2 and less than 1 ⁇ 50 11 atom/cm 2.
• D The amount of remaining Sn is greater than 1 ⁇ 50 11 atom/cm 2.
• A The increase in the number of defects is 10 or less.
• B The increase in the number of defects is more than 10 and less than 20.
• C The increase in the number of defects is more than 20 and less than 30.
• D The increase in the number of defects is more than 30.
• the amount of remaining Sn before and after temperature increasing and decreasing storage was compared, and the ratio of the amount of remaining Sn (amount of remaining Sn after temperature increasing and decreasing storage/amount of remaining Sn before temperature increasing and decreasing storage) was calculated, and the resistance of the metal resist removability of the treatment liquid to deterioration due to temperature increasing and decreasing storage was evaluated according to the evaluation criteria below.
• A The residual Sn ratio is 1.1 or less.
• B The residual Sn ratio is more than 1.1 and less than 1.5.
• C The residual Sn ratio is more than 1.5 and less than 2.0.
• D The residual Sn ratio is more than 2.0.
• Table 9 shows the composition of the treatment liquid, the use of the treatment liquid, and the evaluation results of each of the examples and comparative examples.
• each notation has the same meaning as each notation in Tables 1 to 8.
• the treatment liquid of the present invention is also useful as a metal resist cleaning liquid.
• a rinse process was performed by pouring one type of rinse liquid selected from methyl isobutyl carbinol (MIBC), 2-heptanone, PGMEA, PGME, and nBA (n-butyl acetate) for 10 seconds while rotating the wafer at 1000 rpm, and the wafer was dried by rotating at 4000 rpm for 30 seconds, thereby obtaining a pillar pattern with a pitch of 45 nm.
• MIBC methyl isobutyl carbinol
• PGMEA 2-heptanone
• PGME nBA
• nBA n-butyl acetate

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