Pattern Formation Method

Abstract

The present invention addresses the problem of providing a pattern formation method capable of forming a fine pattern which has a good pattern shape and in which defect generation is suppressed even when the pattern is formed by exposing an active light-sensitive or radiation-sensitive film having a thickness of 10 μm or more with KrF light.　This pattern formation method comprises: (i) a step for forming an active light-sensitive or radiation-sensitive film having a thickness of 10 μm or more using an active light-sensitive or radiation-sensitive resin composition; (ii) a step for irradiating the active light-sensitive or radiation-sensitive film with KrF light; and (iii) a step for forming a negative type pattern by developing the active light-sensitive or radiation-sensitive film irradiated with the KrF light using a developing solution. The developing solution contains an organic solvent and a minor component, and the developing solution contains, as the minor component, 100-3000 mass ppm compound bearing a hydroxyl group in total with respect to the total mass of the developing solution.

Description

[Technical field]

[0001] The present invention relates to a pattern forming method. [Background technology]

[0002] Miniaturization using the wavelength of the exposure light source is reaching its limit, and in the case of NAND memory (NOT AND memory), three-dimensional memory layers are becoming mainstream in order to increase capacity. To make the memory layer three-dimensional, an increase in the number of processing steps in the vertical direction is required, so the resist film must be thickened from the conventional nanometer order to the micrometer order. When thickening the resist film, it is required to obtain a pattern with excellent rectangularity in order to realize three-dimensional microfabrication. As a pattern formation method, not only a method using an alkaline developer but also a pattern formation method using an organic developer has been developed. This is because, in the manufacture of semiconductor devices and the like, there is a demand for the formation of patterns having various shapes such as lines, trenches, holes, etc., and in forming such patterns, a negative pattern formation method using an organic solvent as a developer may be advantageous in terms of optical contrast. Furthermore, by using an organic solvent with low surface tension as a developer, there is also the advantage that pattern collapse during drying of the substrate after development can be suppressed. For example, Patent Document 1 proposes a pattern forming method in which a predetermined resist film is exposed to i-line radiation and developed with a developer containing an organic solvent to form a pattern. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2019 / 044469 Summary of the Invention [Problem to be solved by the invention]

[0004] Incidentally, when a pattern is formed by exposure with KrF light, a pattern with higher contrast is more easily formed than when exposure is performed with g-line or i-line, and therefore the method of forming a pattern by exposure with KrF light is widely used. In addition, various demands for higher performance, such as larger memory capacity, have led to the use of step processing using a multi-stage etching process, high-energy ion implantation process, etc., and for example, even in applications requiring particularly fine resolution performance (for example, applications requiring resolution performance with a pattern width and / or space width of 1 μm or less), it has become necessary to form patterns using actinic ray- or radiation-sensitive films with a thickness of 10 μm or more. However, when an attempt is made to form a fine pattern with a thickness exceeding 10 μm, deterioration of the pattern shape and occurrence of defects may become significant. Therefore, an object of the present invention is to provide a pattern forming method which can form a fine pattern having a good pattern shape and suppressed occurrence of defects, even when an actinic ray-sensitive or radiation-sensitive film having a thickness of 10 μm or more is exposed to KrF light to form a pattern. [Means for solving the problem]

[0005] That is, the present inventors have found that the above problems can be solved by the following configuration.

[0006] [1] (i) forming an actinic ray-sensitive or radiation-sensitive film having a thickness of 10 μm or more using an actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray-sensitive or radiation-sensitive film with KrF light; and (iii) developing the actinic ray-sensitive or radiation-sensitive film irradiated with KrF light using a developer to form a negative pattern; A pattern forming method comprising the steps of: The developer contains an organic solvent and a trace component, The pattern forming method, wherein the developer contains, as the minor component, a compound having a hydroxyl group in a total amount of 100 to 3000 ppm by mass relative to the total mass of the developer. [2] The pattern formation method according to [1], wherein the developer contains the compound having a hydroxyl group in a total amount of 200 ppm by mass or more based on the total mass of the developer. [3] The pattern formation method according to [1] or [2], wherein the organic solvent is butyl acetate. [4] The pattern formation method according to any one of [1] to [3], wherein the compound having a hydroxyl group is one or more compounds selected from the group consisting of a carboxylic acid having 1 to 5 carbon atoms, an alcohol having 1 to 5 carbon atoms, and water. [5] The pattern formation method according to [4], wherein the total content of the carboxylic acids having 1 to 5 carbon atoms, the total content of the alcohols having 1 to 5 carbon atoms, and the content of the water in the developer are each independently 50 to 2000 ppm by mass with respect to the total mass of the developer. [6] The actinic ray-sensitive or radiation-sensitive resin composition is (A) a resin having a repeating unit having an aromatic group and a repeating unit having a group that is decomposed by the action of an acid to produce a polar group; (B) a compound that generates an acid when exposed to actinic rays or radiation, (C) a solvent, and (G) a cross-linking agent, the content of the repeating unit having an aromatic group is 15 mol % or more based on the total repeating units of the resin, The method for forming a pattern according to any one of [1] to [5], wherein the crosslinking agent has two crosslinkable groups in the molecule. [7] the developer further contains, as the trace components, a metal component containing one or more metal elements selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn; The method for forming a pattern according to any one of [1] to [6], wherein the total content of metal components in the developer is 10 ppt by mass to 1 ppb by mass. Effect of the Invention

[0007] According to the present invention, there is provided a pattern formation method which can form a fine pattern having a good pattern shape and suppressed occurrence of defects, even when an actinic ray-sensitive or radiation-sensitive film having a thickness of 10 μm or more is exposed to KrF light to form a pattern. [Brief description of the drawings]

[0008] [Figure 1] FIG. 2 is a schematic diagram of a system for measuring the charge amount of a developer. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, an embodiment of the present invention will be described in detail. In the description of groups (atomic groups) in this specification, when there is no indication of substituted or unsubstituted, the notation includes both unsubstituted and substituted groups. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). As used herein, an "organic group" refers to a group containing at least one carbon atom. In this specification, the term "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams (EB), etc. In addition, in the present invention, light refers to actinic rays or radiation. In addition, unless otherwise specified, the term "exposure" in this specification includes not only exposure to mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, EUV light, and the like, but also drawing with particle beams such as electron beams and ion beams. In this specification, the symbol "to" is used to mean that the numerical values ​​before and after it are included as the lower limit and upper limit.

[0010] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic.

[0011] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured using a gel permeation chromatography (GPC) device (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μl, column: TSK gel Multipore HXL-M (×4 columns) manufactured by Tosoh Corporation, column temperature: 40° C., flow rate: 1.0 mL / min, detector: refractive index (RI) detector).

[0012] In addition, in the present specification, when it is said that "may have a substituent", the type of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of the substituents may be, for example, one, two, three, or more. Examples of the substituents include monovalent nonmetallic atomic groups other than hydrogen atoms, and can be selected from, for example, the following substituent group T.

[0013] (substituent group T) Examples of the substituent group T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; aryloxy groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group. Examples of the alkyl group include a silyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; a carboxy group; a formyl group; a sulfo group; a cyano group; an alkylaminocarbonyl group; an arylaminocarbonyl group; a sulfonamide group; a silyl group; an amino group; a monoalkylamino group; a dialkylamino group; an arylamino group; and combinations thereof.

[0014] [Pattern formation method] The pattern forming method of the present invention comprises the steps of: (i) forming an actinic ray-sensitive or radiation-sensitive film having a thickness of 10 μm or more using an actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray-sensitive or radiation-sensitive film with KrF light; and (iii) developing the actinic ray-sensitive or radiation-sensitive film irradiated with KrF light using a developer to form a negative pattern; A pattern forming method comprising the steps of: The developer contains an organic solvent and a trace component, In the method for forming a pattern, the developer contains, as the minor component, a compound having a hydroxyl group in a total amount of 100 to 3000 ppm by mass relative to the total mass of the developer. Hereinafter, the developer used in the pattern forming method of the present invention will also be referred to as the developer of the present invention. Hereinafter, the actinic ray-sensitive or radiation-sensitive resin composition may be simply referred to as a composition. Furthermore, the composition used in the pattern forming method of the present invention may be also referred to as the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film is also called a resist film. The mechanism by which the above-mentioned configuration solves the problems of the present invention is not entirely clear, but the present inventors consider it as follows. First, the compound having a hydroxyl group is contained in a certain amount or more in the organic solvent, so that the charge in the organic solvent can be suppressed. Therefore, it is considered that the total content in the developer is a predetermined value or more, so that the charge amount of the developer when the developer is pumped is suppressed, and the generation of static electricity and the generation of defects associated therewith during pattern formation can be suppressed. In addition, since the total content in the developer is equal to or less than a predetermined value, it is believed that the compound having a hydroxyl group itself is prevented from causing deterioration of the pattern shape or the occurrence of defects during pattern formation.

[0015] [Developer] First, the developer used in the pattern forming method of the present invention will be described. The developer used in the pattern forming method of the present invention is a developer containing an organic solvent. Hereinafter, the developer used in the pattern forming method of the present invention will also be referred to as the developer of the present invention.

[0016] <Features of the developer> The vapor pressure of the developer is preferably 5 kPa or less, more preferably 3 kPa or less, and even more preferably 2 kPa or less at 20° C. By making the vapor pressure of the developer 5 kPa or less, evaporation of the developer on the wafer and / or in the developing cup is suppressed, improving the temperature uniformity within the wafer surface, and as a result, improving the dimensional uniformity within the wafer surface.

[0017] (Organic solvent) The developer contains an organic solvent. Examples of the organic solvent contained in the developer include polar solvents such as ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents, as well as hydrocarbon-based solvents. More specific examples of the organic solvent include the solvents described in paragraph

[0507] of JP2013-218223A, isoamyl acetate, butyl butanoate, and methyl 2-hydroxyisobutyrate. The organic solvents may be used in combination with a plurality of organic solvents, or may be used in combination with an organic solvent other than the above and / or water. The content of the organic solvent in the developer is preferably 51% by mass or more, more preferably 90% by mass or more, more preferably 99% by mass or more, and more preferably 99.5% by mass or more, based on the total mass of the developer. The upper limit of the content is, for example, 99.7% by mass or less and 99.99% by mass or less.

[0018] In particular, the developer preferably contains at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents, more preferably contains an ester-based solvent, and even more preferably contains an acetate solvent. The number of carbon atoms in the acetate ester is preferably 3 to 10, more preferably 5 to 6, and even more preferably 6. When the number of carbon atoms is within the above range, the affinity for the resist film to be developed is appropriate, and the effects of the present invention are more excellent. When the number of carbon atoms is equal to or less than a predetermined value, charging of the acetate ester is suppressed, and defects due to static electricity are less likely to occur. Among them, it is particularly preferable that the acetate ester includes butyl acetate, isopropyl acetate, and / or isopentyl acetate, and it is most preferable that the acetate ester includes butyl acetate. In the developer, the content of acetate ester (preferably one or more of the group consisting of butyl acetate, isopropyl acetate, and isopentyl acetate, more preferably butyl acetate) is preferably 51% by mass or more, more preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably 99.5% by mass or more, based on the total mass of the developer. The upper limit of the content is, for example, 99.7% by mass or less and 99.99% by mass or less.

[0019] (trace ingredients) In this specification, the term "trace component" refers to a component that is contained in an amount of more than 0 ppm by mass and not more than 10,000 ppm by mass per component relative to the total mass of the developer. For example, if the content in the developer is 10,000 ppm by mass or less, even if the component is an organic compound that is liquid at room temperature (e.g., 25°C), the component is not included in the organic solvent.

[0020] Compounds containing a hydroxyl group The developer of the present invention contains, as the minor components, compounds having a hydroxyl group in a total amount of 100 to 3000 ppm by mass based on the total mass of the developer. The total content of the compounds having a hydroxyl group is preferably 2500 mass ppm or less, more preferably 2000 mass ppm or less, and even more preferably 1000 mass ppm or less, based on the total mass of the developer. The content is preferably 120 mass ppm or more, more preferably 150 mass ppm or more, and even more preferably 200 mass ppm or more. Hereinafter, the compound having a hydroxyl group, which is a compound different from the organic solvent, will be simply referred to as a "compound having a hydroxyl group". A compound having a hydroxyl group may have one or more (e.g., 1 to 10) hydroxyl groups (-OH) in the compound. The hydroxyl group in the compound having a hydroxyl group may be present in a form contained in another group. For example, -OH contained in a carboxylic acid group (-COOH) is also considered to be a hydroxyl group. Water (H 2 O) is also considered a hydroxyl group.

[0021] Examples of the compound having a hydroxyl group include organic acids, alcohols, and water. The compound having a hydroxyl group is preferably one or more compounds selected from the group consisting of organic acids, alcohols, and water, and more preferably one or more compounds selected from the group consisting of carboxylic acids having 1 to 5 carbon atoms, alcohols having 1 to 5 carbon atoms, and water. For example, the total content of the organic acid (preferably a carboxylic acid having 1 to 5 carbon atoms), the alcohol (preferably an alcohol having 1 to 5 carbon atoms), and water is preferably from 100 to 3000 mass ppm, more preferably from 105 to 2500 mass ppm, further preferably from 110 to 2000 mass ppm, and particularly preferably from 115 to 1000 mass ppm, relative to the total mass of the developer.

[0022] The organic acid may be, for example, a compound having one or more (eg, 1 to 10) aromatic hydroxyl groups and / or carboxylic acid groups. Among them, the organic acid is preferably a carboxylic acid having 1 to 5 carbon atoms (a compound having a carboxylic acid group and having 1 to 5 carbon atoms). The organic acids may be used alone or in combination of two or more.

[0023] The alcohol is a compound having one or more (eg, 1 to 10) alcoholic hydroxyl groups. The alcoholic hydroxyl group is an -OH group in a structure in which a hydrogen atom in a hydrocarbon group other than the carbon atom constituting an aromatic ring is replaced with -OH. However, compounds that fall under the above organic acids are not included in the above alcohols. That is, for example, a compound having both a carboxylic acid group and an alcoholic hydroxyl group is classified as an organic acid and is not included in the alcohols. The alcohol is preferably an alcohol having 1 to 5 carbon atoms. The above alcohols may be used alone or in combination of two or more.

[0024] The water is H 2 It is O.

[0025] The total content of organic acids (preferably carboxylic acids having 1 to 5 carbon atoms), the total content of alcohols (preferably alcohols having 1 to 5 prime numbers), and the content of water are each independently preferably from 10 to 2500 ppm by mass, more preferably from 50 to 2000 ppm by mass, and further preferably from 50 to 1500 ppm by mass, relative to the total mass of the developer.

[0026] When the content of the compound having a hydroxyl group is equal to or less than the upper limit of the aforementioned range, excessive interaction with the acid group (such as a hydroxyl group contained in a repeating unit corresponding to hydroxystyrene) of the resist film during development is suppressed, and the occurrence of development defects and / or pattern collapse can be suppressed. When the content of the compound having a hydroxyl group is equal to or more than the lower limit of the above range, it is possible to suppress the amount of charge when the developer flows, and it is possible to suppress the generation of static electricity caused by charging and the occurrence of defects associated therewith. In particular, since the developer is often transported by passing it through fluororesin pipes in order to control the amount of metal impurities, and is often used under conditions in which charging is likely to occur, it is a great advantage that the developer has the property of being difficult to charge.

[0027] (Measurement method) Measurement method for compounds with hydroxyl groups other than water A gas chromatograph mass spectrometer (e.g., product name "GCMS-2020" manufactured by Shimadzu Corporation) can be used to measure the type and content of compounds having a hydroxyl group other than water (compounds having a hydroxyl group excluding water), such as organic acids and alcohols, in the developer.

[0028] How to measure water The water content in the developer can be measured using an apparatus that uses the Karl Fischer water content measurement method (coulometric titration method) as its measurement principle.

[0029] (Other Ingredients) The developer may contain other components in addition to those described above. The other components may be minor components other than the above-mentioned compounds having a hydroxyl group.

[0030] Metallic components The developer may contain, as a trace component, a metal component (also referred to as a specific metal component) containing one or more metal elements selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn. The specific metal component may be contained alone or in combination of two or more kinds. Here, the specific metal component may be in any form such as an ion, a complex compound, a metal salt, an alloy, etc. The specific metal component may also be in a particle state. The specific metal component may be a metal component that is inevitably contained in each component (raw material) contained in the developer, a metal component that is inevitably contained during the production of the developer, or a metal component that is intentionally added. The content of the specific metal component in the developer is preferably 1 mass ppt to 1 mass ppb, more preferably 10 mass ppt to 1 mass ppb, based on the total mass of the developer. When the content of the specific metal component is within the above range, the occurrence of defects in semiconductor devices can be suppressed. In addition, when the developer contains two or more specific metal components, the content of the specific metal component refers to the total content of the two or more specific metal components.

[0031] The content of the specific metal component in the developer is measured by ICP-MS (inductively coupled plasma mass spectrometry). The content of the specific metal component by ICP-MS can be measured using, for example, an apparatus similar to NexTON350 (product name, manufactured by PerkinElmer). In addition to the above-mentioned device, the content of the specific metal component in the developer can be measured using Agilent_8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, for semiconductor analysis, option #200) manufactured by Agilent Technologies, Inc. In addition, the content of the specific metal component in the developer can be measured using Agilent_8900 manufactured by Agilent Technologies, Inc. Here, in the ICP-MS method, the total mass of the specific metal components in the developer is quantified, that is, the combined mass (also referred to as the "total metal amount") of ionic metals (metal ions) and non-ionic metals (particulate specific metal components, i.e. metal particles). Therefore, in the present invention, when simply referring to "the content of the specific metal components in the developer," it refers to the total content (total metal amount) of the specific metal components in the developer, regardless of the form of the specific metal components described above. The specific metal component in the developer may contain a particulate specific metal component. In this case, the content of the particulate specific metal component (metal particles) in the developer is preferably 1 mass ppq to 1 mass ppb, more preferably 1 mass ppq to 30 mass ppt, even more preferably 1 mass ppq to 10 mass ppt, and particularly preferably 2 mass ppt to 10 mass ppt. By having the content of the particulate specific metal component within the above range, the occurrence of defects in semiconductor devices is further reduced. Here, the recently developed SP-ICP-MS method (Single Particle-Inductively Coupled Plasma-Mass Spectroscopy) makes it possible to measure the amount of metal elements present in a solution separately as metal ions (ionic metals) and metal particles (non-ionic metals). Metal particles (non-ionic metals) are components that do not dissolve in the solution (developer) and exist as a solid. The content of particulate specific metal components (metal particles) in the developer is measured by using the device mentioned in the ICP-MS method above and changing the software to that of the SP-ICP-MS method. That is, the ICP-MS method and the SP-ICP-MS method are performed using the same device, with only the data analysis being different. In addition, the above device can measure not only the total content of specific metal components, but also the content of each type of metal element constituting the specific metal components. The method for controlling the content of the specific metal component in the developer to fall within the predetermined range will be described later.

[0032] Surfactants If necessary, a suitable amount of a surfactant can be added to the developer. The surfactant is not particularly limited, but for example, ionic or non-ionic fluorine-based and / or silicon-based surfactants can be used. Examples of these fluorine- and / or silicon-based surfactants include those described in JP-A-62-036663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-062834, JP-A-9-054432, JP-A-9-005988, U.S. Pat. No. 5,405720, U.S. Pat. No. 5,360692, U.S. Pat. No. 5,529881, U.S. Pat. No. 5,296330, U.S. Pat. No. 5,436098, U.S. Pat. No. 5,576143, U.S. Pat. No. 5,294511, and U.S. Pat. No. 5,824451. Among these, the surfactant is preferably a nonionic surfactant. The non-ionic surfactant is not particularly limited, but a fluorine-based surfactant or a silicon-based surfactant is more preferable.

[0033] When the developer contains a surfactant, the content thereof is preferably from 50 to 2000 ppm by mass relative to the total mass of the developer.

[0034] Base components The organic developer may contain a basic compound. Examples of the basic compound that the developer may contain include the basic compounds in the acid diffusion controller (D) described below as a component that the composition may contain. When the developer contains a basic compound, the content thereof is preferably from 50 to 2000 ppm by mass relative to the total mass of the developer.

[0035] Other impurities The developer of the present invention may contain organic impurities as trace components. From the viewpoint of further suppressing the occurrence of defects in semiconductor devices, the content of organic impurities in the developer is preferably 10 ppb by mass to 0.5% by mass. Here, organic impurities refer to organic substances that do not fall under any of the above-mentioned compounds such as organic solvents and compounds having a hydroxyl group. Specifically, organic impurities include stabilizers and unreacted raw materials used in the production of organic solvents, structural isomers and by-products generated in the production of organic solvents, and eluted materials from components constituting the production equipment used in the production of organic solvents (for example, plasticizers eluted from rubber components such as O-rings). The content of organic impurities can be measured using a gas chromatograph mass spectrometer (for example, product name "GCMS-2020" manufactured by Shimadzu Corporation). In addition, when the organic impurities are high molecular weight compounds, the structure may be identified and the concentration may be quantified from the decomposition products by techniques such as, but not limited to, Py-QTOF / MS (pyrolyzer quadrupole time-of-flight mass spectrometry), PyIT / MS (pyrolyzer ion trap mass spectrometry), Py-Sector / MS (pyrolyzer magnetic field mass spectrometry), Py-FTICR / MS (pyrolyzer Fourier transform ion cyclotron mass spectrometry), Py-Q / MS (pyrolyzer quadrupole mass spectrometry), and Py-IT-TOF / MS (pyrolyzer ion trap time-of-flight mass spectrometry). For example, a device manufactured by Shimadzu Corporation or the like can be used for Py-QTOF / MS.

[0036] <Developing solution manufacturing method> The developer of the present invention can be obtained by carrying out the following purification step in order to adjust the contents of the above-mentioned components (particularly components having a hydroxyl group and / or metal components, etc.) within the desired range. In many cases, an organic solvent that has not been subjected to a purification treatment contains too much components having a hydroxyl group and / or metal components, etc., and is therefore difficult to use as the developer of the present invention as is. Therefore, it is preferable to carry out a purification treatment to adjust the contents of components having a hydroxyl group and / or metal components, etc., to a predetermined range before producing the developer of the present invention.

[0037] (purification process) The purification process is a process in which components that are mixed in during the production of each component and during mixing of each component (e.g., the above-mentioned water, organic acid, alcohol, and / or metal components, etc.) are purified to the desired content described above. The purification step may be carried out at any time. The purification step includes, for example, the following purification treatments I to IV. That is, the purification process I is a process for purifying raw materials (for example, raw materials used in the production of an organic solvent) before the production of components (for example, an organic solvent, etc.) used in the developer. The purification treatment II is a treatment for purifying components (such as an organic solvent) used in the production of the developer during and / or after production. The purification process III is a process in which each component is purified before two or more components (for example, two or more organic solvents) are mixed during production of a developer. The purification process IV is a process in which two or more components (for example, two or more organic solvents) are mixed together during the production of a developer, and then the mixture is purified. When two or more components are used in producing a developer, it is preferable to carry out at least both purification treatments III and IV among the above purification treatments I to IV, it is more preferable to carry out at least all of purification treatments I, III, and IV, and it is even more preferable to carry out all of purification treatments to IV. Each of the purification treatments I to IV may be carried out only once, or may be carried out two or more times (for example, 2 to 10 times). As the components (e.g., organic solvents) used in producing the developer, and as the raw materials for the components (e.g., organic solvents) used in producing the developer, high-purity grade products (particularly those with low contents of specific metal components, water, alkenes, organic acid components, etc.) can be purchased and further subjected to the above-mentioned purification treatment before use.

[0038] An example of the purification process is shown below. In the following description, the object to be purified in the purification step (i.e., the organic solvent used in the developer, etc.) will be collectively referred to simply as the "liquid to be purified." An example of a purification process includes a dehydration process (dehydration treatment) for removing water contained in the purified liquid, a distillation process (distillation treatment) for crude distillation of the purified liquid, an ion exchange process (ion removal process) for performing ion exchange treatment on the purified liquid, a distillation process (distillation treatment) for purification treatment of the purified liquid, and a filtration process (filtration treatment, filtering), which are carried out in this order.

[0039] (Dehydration treatment) In the purification step, a dehydration treatment may be carried out. The dehydration treatment can remove water from the liquid to be purified. In addition, when zeolite (particularly, molecular sieve (product name) manufactured by Union Showa Co., Ltd.) is used in the dehydration treatment, olefins can also be removed. Examples of dehydration means used in the dehydration treatment include a dehydration membrane, a water adsorbent that is insoluble in the liquid to be purified, an aeration replacement device using a dry inert gas, and a heating or vacuum heating device. When a dehydrating membrane is used, membrane dehydration is performed by pervaporation (PV) or vapor permeation (VP). The dehydrating membrane is configured, for example, as a water-permeable membrane module. As the dehydrating membrane, a membrane made of a polymer material such as polyimide, cellulose, or polyvinyl alcohol, or an inorganic material such as zeolite can be used. The water adsorbent is added to the liquid to be purified. Examples of the water adsorbent include zeolite, diphosphorus pentoxide, silica gel, calcium chloride, sodium sulfate, magnesium sulfate, anhydrous zinc chloride, fuming sulfuric acid, and soda lime.

[0040] One method for adjusting the water content in the developer to the desired range is to place the liquid to be purified in a desiccator whose interior has been purged with nitrogen gas, and heat the liquid to be purified in the desiccator while maintaining a positive pressure inside the desiccator.

[0041] (Distillation process) According to the distillation process, the ion exchange process described below can remove metal components, fine particles (including metal components in the form of fine particles), water in the purified liquid, and impurities dissolved in the purified liquid by other processes (such as impurities dissolved from the dehydration membrane described below). The distillation treatment is carried out, for example, by using a single-stage or multi-stage (for example, theoretical plate number 5 to 30) distillation apparatus. The distillation process may be carried out in a distillation apparatus for performing atmospheric distillation or in a distillation apparatus for performing reduced pressure distillation. The distillation process concentrates impurities in the distillation apparatus, etc., and in order to prevent some of the concentrated impurities from flowing out, it is preferable to provide the distillation means with a means for periodically or constantly discharging a portion of the liquid in which the impurities are concentrated to the outside. The distillation treatment may be carried out using a combination of distillation apparatuses of different types, or may be carried out using one or more single distillation apparatuses. The distillation process is preferably performed as at least one of the following: a crude distillation process performed on the liquid to be purified before the ion exchange process described below is performed, and a distillation process performed to further purify the liquid to be purified after the purification process such as the ion exchange process described below is performed, and it is more preferable to perform both.

[0042] (Ion exchange treatment) By carrying out the ion exchange process, ionic components (eg, metal components, etc.) in the liquid to be purified can be removed. Ion exchange treatment can remove impurities that have accumulated in the distillation apparatus and that may leak out, and can also remove eluted materials from pipes such as stainless steel (SUS) that are used as liquid delivery lines. In the ion exchange treatment, for example, an ion exchange means such as an ion exchange resin is used. The ion exchange resin may be any of a single bed of a cation exchange resin or an anion exchange resin, a double bed of a cation exchange resin and an anion exchange resin, and a mixed bed of a cation exchange resin and an anion exchange resin. The ion exchange resin may be used by filling a tower-shaped vessel with the ion exchange resin and passing the liquid to be purified through the filled ion exchange resin. In the ion exchange treatment, the liquid to be purified may be passed through the cation exchange resin and / or the anion exchange resin only once, or may be passed through two or more times (for example, 2 to 10 times). When both a cation exchange resin and an anion exchange resin are used in the ion exchange treatment, the liquid to be treated may be passed through the cation exchange resin and then the anion exchange resin, or the liquid may be passed through the anion exchange resin and then the cation exchange resin, or the liquid may be passed alternately through the cation exchange resin and the anion exchange resin, or the liquid may be passed through both the cation exchange resin and the anion exchange resin simultaneously, for example by passing the liquid through a mixture of the cation exchange resin and the anion exchange resin. Examples of ion exchange resins include the Orlite DS (trade name) series manufactured by Organo Corporation and the Diaion (trade name) series manufactured by Mitsubishi Chemical Corporation. In order to reduce water elution from the ion exchange resin, it is also preferable to use a dry resin that contains as little water as possible. Commercially available dry resins include Organo Corporation's 15 JS-HG·DRY (trade name, dry cation exchange resin, water content 2% or less) and MSPS2-1·DRY (trade name, mixed bed resin, water content 10% or less). An ion adsorption membrane may be used as the ion exchange means. The use of an ion adsorption membrane is preferable because it allows treatment at a high flow rate. An example of the ion adsorption membrane is Neocepta (trade name, manufactured by Astom Corporation).

[0043] (filtration process) The filtration process is a process in which the liquid to be purified is passed through at least one filter (preferably two or more, more preferably two to six). In the filtration process, it is also preferable to use a combination of two or more types of filters, which will be described later. The filtration treatment can be carried out, for example, in order to adjust the contents of metal components and water to desired ranges and to remove foreign matter, coarse particles, and the like. The filter used in the filtration process is not particularly limited as long as it is a filter that has been conventionally used for filtration, etc. Examples of materials constituting the filter include fluororesins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon, and polyolefin resins (including high density and ultra-high molecular weight) such as polyethylene and polypropylene (PP). Among these, polyamide resins, PTFE, polyethylene (including high density polyethylene and ultra-high molecular weight polyethylene), and polypropylene (including high density polypropylene and ultra-high molecular weight polypropylene) are preferred. By using a filter made of these materials, highly polar foreign matter that is likely to cause residue defects and particle defects can be more effectively removed, and the amount of specific metal components can be more efficiently reduced. The lower limit of the critical surface tension of the filter is preferably 70 mN / m or more, and the upper limit is preferably 95 mN / m or less. In particular, the critical surface tension of the filter is preferably 75 to 85 mN / m. The critical surface tension values ​​are the nominal values ​​provided by the manufacturers. By using a filter with a critical surface tension in the above range, highly polar foreign matter that is likely to cause residue defects and particle defects can be more effectively removed, and the amount of the specific metal component of the present invention can be more efficiently reduced.

[0044] The pore size of the filter is preferably 0.001 to 1.0 μm, more preferably 0.02 to 0.5 μm, and even more preferably 0.01 to 0.1 μm. By setting the pore size of the filter in the above range, it is possible to reliably remove fine foreign matter contained in the developer while suppressing filtration clogging. Furthermore, from the viewpoint of adjusting the amount of the specific metal component, it is also preferable to set the filter pore size to 0.05 μm or less. When adjusting the amount of the specific metal component, the filter pore size is more preferably 0.005 to 0.04 μm, and even more preferably 0.01 to 0.02 μm. Within the above range, the pressure required for filtration can be kept low, and filtration can be performed efficiently.

[0045] When using filters, different filters may be combined. In this case, filtration with the first filter may be performed only once or two or more times. When performing filtration two or more times using different filters, the filters may be of the same type or different types, but are preferably of different types. For example, a first filter and a second filter may be used, and typically the first filter and the second filter preferably differ in at least one of pore size and material of construction. The first filter and the second filter may each have the pore size and / or material as described above. Also, the filters described below may each be the first filter and / or the second filter. It is preferable that the pore size of the second or subsequent filtering steps is the same or smaller than that of the first filtering step. Filters with different pore sizes may be combined within the above-mentioned range. The pore size here can refer to the nominal value of the filter manufacturer. Commercially available filters can be selected from various filters provided by, for example, Nippon Pall Corporation, Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), and Kitz Microfilter Co., Ltd. In addition, a polyamide "P-nylon filter (pore size 0.02 μm, critical surface tension 77 mN / m)" (manufactured by Nippon Paul Co., Ltd.), a high-density polyethylene "PE clean filter (pore size 0.02 μm)" (manufactured by Nippon Paul Co., Ltd.), and a high-density polyethylene "PE clean filter (pore size 0.01 μm)" (manufactured by Nippon Paul Co., Ltd.) can also be used.

[0046] The second filter may be made of the same material as the first filter, or may be made of a different material, and may have the same or different pore size as the first filter. When the second filter has a smaller pore size than the first filter, the ratio of the pore size of the second filter to the pore size of the first filter (pore size of the second filter / pore size of the first filter) is preferably 0.01 to 0.99, more preferably 0.1 to 0.9, and even more preferably 0.3 to 0.9. By setting the pore size of the second filter within the above range, fine foreign matter mixed in the liquid to be purified can be more reliably removed.

[0047] In the case where the developer is a mixture of two or more components, for example, filtration with a first filter may be performed on a mixed liquid (liquid to be purified) containing some of the components of the developer, and the remaining components may be mixed with this to prepare a liquid to be purified, after which filtration with a second filter may be performed.

[0048] The upper limit of the temperature during the filtration process is preferably room temperature (25° C.) or lower, more preferably 23° C. or lower, and even more preferably 20° C. or lower. The lower limit of the temperature during the filtration is preferably 0° C. or higher, more preferably 5° C. or higher, and even more preferably 10° C. or higher. When the filtration process is carried out at the above-mentioned temperatures, the amount of particulate foreign matter and impurities dissolved in the liquid to be treated is reduced, so that the filtration is carried out more efficiently. In particular, in the case of a developer containing a small amount of specific metal components, it is preferable to filter at the above temperature. Although the mechanism is not clear, it is considered that most of the specific metal components are present in a particulate colloidal state. When filtering at the above temperature, a part of the specific metal components suspended in colloidal form will aggregate, and this aggregated material will be efficiently removed by filtering, so it is considered that the content of the specific metal components can be easily adjusted to the desired amount in the present application.

[0049] In addition, the filter used is preferably treated before carrying out the filtration process. The liquid used in this process is not particularly limited, but it is also preferable to use a liquid obtained by purifying an organic solvent to make the content of metal components within the same range as the developer of the present invention, a liquid that is the developer of the present invention itself, a liquid obtained by diluting the developer of the present invention, a liquid containing components contained in the developer, or a liquid obtained by further purifying these liquids to reduce specific metal components, impurities, coarse particles, etc. The liquid used to treat the filter is not particularly limited, but it is also preferable that the content of the specific metal components described above is less than 0.001 ppt by mass.

[0050] Filters with particle size of 20 nm or less It is also preferable to use a filter with a particle size of 20 nm or less. A filter with a particle removal diameter of 20 nm or less has the function of efficiently removing particles with a diameter of 20 nm or more from the liquid to be purified. The filter already described above and / or the filter described below may have the characteristics of a "filter with a particle exclusion diameter of 20 nm or less." The particle size of the filter is preferably 1 to 15 nm, and more preferably 1 to 12 nm. If the particle size is 15 nm or less, finer particles can be removed, and if the particle size is 1 nm or more, the filtration efficiency is improved. Here, the particle size means the minimum size of particles that can be removed by the filter. For example, if the particle size of a filter is 20 nm, it can remove particles with a diameter of 20 nm or more. Examples of materials for such filters include nylons such as 6-nylon and 6,6-nylon, polyethylene (high density polyethylene, ultra-high molecular weight polyethylene, etc.), polypropylene, polystyrene, polyimide, polyamideimide, and fluororesin. The polyimide and / or polyamideimide may have at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an NH-bond. In terms of solvent resistance, fluororesin, polyimide, and / or polyamideimide are excellent. In addition, from the viewpoint of adsorbing metal ions, nylons such as 6-nylon and 6,6-nylon are particularly preferable.

[0051] In the filtration process, multiple filters with a particle removal diameter of 20 nm or less may be used. In the filtration process, a filter other than the filter with a particle size of 20 nm or less may be used. In this case, the other filter (the filter with a particle size of 20 nm or less) is not particularly limited, but is preferably a filter with a particle size of 50 nm or more (for example, a microfiltration membrane for removing fine particles with a pore size of 50 nm or more). When the liquid to be treated contains fine particles other than colloidal impurities, particularly colloidal impurities having metal atoms such as iron or aluminum, the filtration efficiency of the filter with a particle removal diameter of 20 nm or less (e.g., a microfiltration membrane for removing fine particles with a pore size of 50 nm or more) is improved and the particle removal performance is further improved by filtering the liquid to be treated using a filter with a particle removal diameter of 50 nm or more (e.g., a microfiltration membrane with a pore size of 20 nm or less) before filtering using a filter with a particle removal diameter of 20 nm or less (e.g., a microfiltration membrane with a pore size of 20 nm or less).

[0052] Metal ion adsorption filter As the filter, it is also preferable to use a metal ion adsorption filter. The metal ion adsorption filter is not particularly limited, and examples thereof include known metal ion adsorption filters. Among them, the metal ion adsorption filter is preferably an ion-exchangeable filter, and the metal ions to be adsorbed are preferably the above-mentioned specific metal components, since they are likely to cause defects in semiconductor devices. From the viewpoint of improving the metal ion adsorption performance, the metal ion adsorption filter preferably has an acid group on the surface. Examples of the acid group include a sulfo group and a carboxy group. Examples of the substrate (material) constituting the metal ion adsorption filter include cellulose, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, fluororesin, etc. From the viewpoint of efficiency in adsorbing metal ions, nylon is particularly preferable. The metal ion adsorption filter may be made of a material containing polyimide and / or polyamideimide. Examples of the metal ion adsorption filter include the polyimide and / or polyamideimide porous membrane described in JP 2016-155121 A. The polyimide and / or polyamideimide porous film may have at least one selected from the group consisting of a carboxy group, a salt-type carboxy group, and an -NH- bond. When the metal ion adsorption filter is made of a fluororesin, a polyimide, and / or a polyamideimide, it has better solvent resistance.

[0053] Organic impurity adsorption filter It is also preferable to use an organic impurity adsorption filter as the filter. The organic impurity adsorption filter is not particularly limited, and examples thereof include known organic impurity adsorption filters. Among them, it is preferable that the organic impurity adsorption filter has an organic skeleton capable of interacting with organic impurities on its surface (in other words, the surface is modified by an organic skeleton capable of interacting with organic impurities) in terms of improving the adsorption performance of organic impurities. An example of an organic skeleton capable of interacting with organic impurities is a chemical structure that reacts with organic impurities to capture the organic impurities in the organic impurity adsorption filter. More specifically, when the organic impurities include n-long chain alkyl alcohol (a structural isomer when 1-long chain alkyl alcohol is used as the organic solvent), an example of the organic skeleton is an alkyl group. When the organic impurities include dibutylhydroxytoluene (BHT), an example of the organic skeleton is a phenyl group.

[0054] Examples of the substrate (material) constituting the organic impurity adsorption filter include cellulose carrying activated carbon, diatomaceous earth, nylon, polyethylene, polypropylene, polystyrene, and fluororesin. In addition, as the organic impurity adsorption filter, a filter in which activated carbon is fixed to a nonwoven fabric, as described in JP-A-2002-273123 and JP-A-2013-150979, can also be used. As for the organic impurity adsorption filter, in addition to the above-mentioned chemical adsorption (adsorption using an organic impurity adsorption filter having an organic skeleton on its surface capable of interacting with organic impurities), a physical adsorption method can also be applied. For example, when BHT is included as an organic impurity, the structure of BHT is larger than 10 angstroms (=1 nm). Therefore, by using an organic impurity adsorption filter with a pore size of 1 nm, BHT cannot pass through the pores of the filter. In other words, BHT is physically captured by the filter and removed from the purified liquid. In this way, organic impurities can be removed not only by chemical interactions but also by applying physical removal methods.

[0055] As an example of the purification process described above, the case where all of the treatments are performed has been shown, but the present invention is not limited to this, and each of the treatments may be performed alone or in combination. Furthermore, each of the treatments may be performed once or multiple times. In addition, other treatments such as a dehydration treatment, which will be described later, may also be carried out.

[0056] In the purification step, in addition to the above-mentioned treatments, the adsorption purification treatment of metal components using silicon carbide, as described in WO 2012 / 043496, may also be carried out. The purified solution obtained by each of these treatments can be used for producing the developer of the present invention, or can be used as the developer of the present invention itself.

[0057] It is also preferable that each of the above-mentioned treatments is carried out in a sealed state and in an inert gas atmosphere in which there is a low possibility of water being mixed into the liquid to be purified. In addition, each treatment is preferably carried out in an inert gas atmosphere with a dew point temperature of -70°C or lower in order to minimize the inclusion of moisture, if desired. This is because in an inert gas atmosphere at -70°C or lower, the moisture concentration in the gas phase is 2 mass ppm or lower, so there is a low possibility of moisture being mixed into the developer (liquid to be purified).

[0058] Other than the above purification step, a method for controlling the contents of metal components and water contained in the developer to be within a desired range may be to use a container that is less likely to elute impurities as a "container" for containing raw materials used in the production of the developer, as described below with respect to the container for containing the developer of the present invention. Another method may be to provide a fluororesin lining on the inner wall of "piping" during the production of the developer, so that metal components do not elute from the "piping" or the like.

[0059] The material of the liquid-contacting parts of the manufacturing equipment (such as equipment used to carry out the purification process of the liquid to be purified) used to manufacture the developer of the present invention is not particularly limited, but it is preferable that the parts be made of at least one material selected from the group consisting of non-metallic materials and electrolytically polished metallic materials, in order to obtain a developer having superior defect suppression performance. In this specification, the term "liquid contact portion" refers to a portion that may come into contact with a fluid (such as the liquid to be treated and the developing solution) (e.g., the inner surface of a tank and the inner surface of a pipeline), and refers to a region within a thickness of 100 nm from the surface.

[0060] The non-metallic material is not particularly limited, but is preferably a fluorine-containing resin material such as a polyethylene resin, a polypropylene resin, a polyethylene-polypropylene resin, or a perfluororesin, and is more preferably a fluorine-containing resin from the viewpoint of reducing the elution of metal atoms. Examples of fluorine-containing resins include perfluororesins, such as polytetrafluoroethylene resin (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer resin (FEP), tetrafluoroethylene-ethylene copolymer resin (ETFE), trifluorochloroethylene-ethylene copolymer resin (ECTFE), polyvinylidene fluoride resin (PVDF), trifluorochloroethylene copolymer resin (PCTFE), and polyvinyl fluoride resin (PVF). As the fluorine-containing resin, tetrafluoroethylene resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, or tetrafluoroethylene-hexafluoropropylene copolymer resin is preferable.

[0061] The metal material is not particularly limited, and known materials can be used. For example, the metal material is preferably a metal material in which the total content of chromium and nickel is more than 25 mass% relative to the total mass of the metal material, and more preferably a metal material in which the total content of chromium and nickel is 30 mass% or more. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90 mass% or less. Examples of metallic materials include stainless steel, carbon steel, alloy steel, nickel-chromium-molybdenum steel, chromium steel, chromium-molybdenum steel, manganese steel, and nickel-chromium alloy.

[0062] The stainless steel is not particularly limited, and known stainless steels 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. Examples of 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).

[0063] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferable. Examples of 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), etc. More specifically, examples include Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%), etc. In addition to the above-mentioned alloys, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, if necessary. The method for electrolytically polishing the metal material is not particularly limited, and any known method can be used, such as the methods described in paragraphs

[0011] to

[0014] of JP 2015-227501 A and paragraphs

[0036] to

[0042] of JP 2008-264929 A. It is presumed that the chromium content in the surface passive layer of the metal material is greater than the chromium content in the parent phase by electrolytic polishing, and therefore, it is presumed that a distillation column or the like having a liquid-contacting part formed from a metal material that has been electrolytically polished is less likely to release metal impurities containing metal atoms into an organic solvent, making it possible to obtain a distilled liquid to be treated with a reduced impurity content. The metal material may be buffed. 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. The buffing is preferably performed before the electrolytic polishing.

[0064] In order to obtain a developer having better defect suppression performance, it is preferable that the metal material of the liquid-contacting part is made of electrolytically polished stainless steel. In particular, when the manufacturing apparatus is equipped with a tank, it is more preferable that the liquid-contacting part of the tank is made of electrolytically polished stainless steel. The content mass ratio of the Cr content to the Fe content in the liquid-contacting part (hereinafter also referred to as "Cr / Fe") is not particularly limited, but is generally preferably 0.5 to 4, and more preferably more than 0.5 and less than 3.5, more preferably 0.7 to 3.0, in terms of less elution of metal impurities and / or organic impurities into the liquid to be treated. When Cr / Fe exceeds 0.5, metal elution from inside the tank can be suppressed, and when Cr / Fe is less than 3.5, peeling of the liquid-contacting part, which causes particles, is less likely to occur. The method for adjusting the Cr / Fe ratio in the above-mentioned metal material is not particularly limited, and examples thereof include a method for adjusting the content of Cr atoms in the metal material, and a method for making the chromium content in the passive layer of the polished surface greater than the chromium content in the parent phase by electrolytic polishing.

[0065] The metal material may be coated with a coating technique. Coating technologies are broadly divided into three types: metallic coatings (various platings), inorganic coatings (various chemical treatments, glass, concrete, ceramics, etc.), and organic coatings (rust-preventive oils, paints, rubber, or plastics). As the coating technique, surface treatment using rust-preventive oil, rust inhibitor, corrosion inhibitor, chelating compound, peelable plastic, lining agent, and the like are preferable. Among these, corrosion inhibitors such as various chromates, nitrites, silicates, phosphates, carboxylic acids such as oleic acid, dimer acid, naphthenic acid, etc., carboxylic acid metal soaps, sulfonates, amine salts, and esters (glycerol esters and phosphate esters of higher fatty acids), chelate compounds such as ethylenedianetetraacetic acid, gluconic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, and diethylenetriaminepentaacetic acid, or fluororesin linings are preferred, with phosphate treatment or fluororesin lining being more preferred.

[0066] The developer of the present invention may be obtained through a process of cleaning a production device with a cleaning liquid. In other words, it is also preferable that the production equipment used in the purification step is a production equipment that has been cleaned in advance with a cleaning liquid. The cleaning is carried out by supplying a cleaning liquid to the inside of the manufacturing apparatus. The amount of the cleaning liquid to be supplied is not particularly limited, but it is preferable that the amount is sufficient to clean the liquid-contacting parts of the manufacturing apparatus. The cleaning may be a circulation cleaning in which the cleaning liquid is circulated in the cleaning device, or a method in which the cleaning liquid is not circulated but is discharged outside the manufacturing device (batch cleaning). In the case of batch cleaning, a constant amount of the cleaning liquid may be intermittently supplied into the manufacturing device, or may be continuously supplied into the manufacturing device.

[0067] The cleaning liquid used for cleaning the production equipment is not particularly limited, and any known cleaning liquid can be used. Examples of the cleaning liquid include water, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate. Furthermore, as the cleaning liquid, for example, those described in JP 2016-057614 A, JP 2014-219664 A, JP 2016-138219 A, and JP 2015-135379 A may be used.

[0068] The cleaning solutions were propylene glycol monomethyl ether (PGME), cyclopentane (CyPe), cyclopentanone (CyPn), butyl acetate (nBA), propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone (CyHe), ethyl lactate (EL), 2-hydroxyisobutyrate methyl (HBM), cyclopentanone dimethyl acetal (DBCPN), Y-butyrolactone (YBL), dimethyl sulfoxide (DMSO), ethylene carbonate (EC), propylene carbonate (PC), 1-methyl-2-pyrrolidone (NMP), isoamyl acetate (iAA), 2-methylbutanol (2-methylbutanol), and 2-methylbutanol (2-methylbutanol). Preferably, the solvent contains at least one selected from the group consisting of 4-methyl-2-pentanol (MIBC), PGMEA, NMP, PGME, nBA, PC, CyHe, YBL, MIBC, EL, DMSO, iAA, MEK, PC, and CyPe, and more preferably, PGMEA, NMP, PGME, nBA, PC, CyHe, YBL, MIBC, EL, DMSO, iAA, MEK, PC, and CyPe. The cleaning solution may be used alone or in combination of two or more kinds.

[0069] In addition to the above, examples of the cleaning liquid include alcohols such as methanol, ethanol, propanol, butanol, methoxyethanol, butoxyethanol, methoxypropanol, and ethoxypropanol; ketone-based solvents such as acetone; ether-based solvents such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether; ester-based solvents such as ethyl acetate and ethyl cellosolve acetate; aromatic compounds such as benzene, toluene, and xylene; and chlorinated hydrocarbons such as dichloromethane, dichloroethane, dichloroethylene, and trichloroethylene.

[0070] <Kit> The developer of the present invention may be prepared as a kit to which other raw materials are added separately. In this case, as the other raw materials to be added separately when used, a different organic solvent to be further mixed with one organic solvent, and other compounds according to the purpose can be mixed and used. From the viewpoint of obtaining the effects of the present invention significantly, it is preferable that the organic solvent that can be used at this time has a content of a compound having a hydroxyl group and / or a metal component contained therein within the predetermined range of the developer of the present invention described above.

[0071] <Container (container)> The developer of the present invention can be filled into any container and stored, transported, and / or used, as long as corrosiveness, etc., does not pose a problem (regardless of whether it is a kit or not). As for the container, one that is highly clean inside the container and has little elution of impurities is preferable for semiconductor applications. Examples of containers that can be used include, but are not limited to, the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd. The inner wall of the container (i.e., the liquid-contacting part that comes into contact with the developer) is preferably formed from a non-metallic material (e.g., one or more resins selected from the group consisting of polyethylene resin, polypropylene resin, and polyethylene-polypropylene resin, as well as a resin other than these), or a metallic material that has been treated to prevent rust and metal elution, such as stainless steel, Hastelloy, Inconel, and Monel.

[0072] The different resin is preferably a fluororesin (perfluororesin). By using a container whose inner wall is made of a fluororesin, the occurrence of the problem of elution of ethylene or propylene oligomers can be suppressed compared to the case where a container whose inner wall is made of a polyethylene resin, a polypropylene resin, or a polyethylene-polypropylene resin is used. A specific example of the fluororesin is the "fluorine-containing resin" mentioned in the liquid-contacting portion of the manufacturing apparatus. A specific example of such a container whose inner wall is a fluororesin is FluoroPure PFA composite drum manufactured by Entegris. In addition, containers described in, for example, page 4 of JP-A-3-502677, page 3 of WO 2004 / 016526, and pages 9 and 16 of WO 99 / 46309 can also be used. When the inner wall is made of a nonmetallic material, it is preferable that the elution of the nonmetallic material into the developer is suppressed.

[0073] In addition to the above-mentioned fluororesin, quartz and electrolytically polished metal materials (i.e., electrolytically polished metal materials) are also preferably used for the inner wall of the container. When a container with such an inner wall is used, specific metal components and / or organic impurities are less likely to dissolve in the developer stored in the container. The metal material used in the production of the electrolytically polished metal material preferably contains at least one selected from the group consisting of chromium and nickel, and more preferably has a total content of chromium and nickel of more than 25 mass% based on the total mass of the metal material. Examples of usable metal materials include stainless steel and nickel-chromium alloys. The total content of chromium and nickel in the metal material is preferably 25 mass % or more, and more preferably 30 mass % or more, based on the total mass of the metal material. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is generally preferably 90 mass % or less.

[0074] The stainless steel is not particularly limited, and known stainless steels 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. Examples of 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).

[0075] The nickel-chromium alloy is not particularly limited, and any known nickel-chromium alloy can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass % and a chromium content of 1 to 30 mass % is preferable. Examples of 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), etc. More specifically, examples include Hastelloy C-276 (Ni content 63 mass%, Cr content 16 mass%), Hastelloy-C (Ni content 60 mass%, Cr content 17 mass%), Hastelloy C-22 (Ni content 61 mass%, Cr content 22 mass%), etc. In addition to the above-mentioned alloys, the nickel-chromium alloy may further contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like, if necessary.

[0076] The method for electrolytically polishing the metal material is not particularly limited, and any known method can be used, such as the methods described in

[0011] to

[0014] of JP 2015-227501 A and

[0036] to

[0042] of JP 2008-264929 A. It is presumed that the chromium content in the surface passive layer of the metal material is greater than the chromium content in the parent phase by electrolytic polishing, and therefore, it is presumed that the metal components are less likely to flow out of the inner wall covered with the electrolytically polished metal material into the developer, making it possible to obtain a developer with reduced specific metal components. It is preferable that the metal material is buffed. The method of buffing is not particularly limited, and known methods can be used. The size of the polishing grains used for 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 the electrolytic polishing. The metal material may be treated by one or a combination of two or more of multiple steps of buffing using different grit sizes of polishing abrasive grains, acid washing, and magnetic fluid polishing. In the present invention, an entity having the container and the developer contained in the container may be referred to as a developer container. It is preferable to wash the inside of these containers before filling. The content of the metal components contained in the liquid used for washing is preferably within the range of the content of the metal components suitable for the above-mentioned developer. The liquid may be appropriately selected depending on the application, but the effect of the present invention can be significantly obtained when the liquid is a refined organic solvent to have a metal component content within the same range as the above-mentioned developer, the developer of the present invention itself, a diluted developer of the present invention, or a liquid containing at least one of the components added to the developer of the present invention. It is also preferable to remove foreign matter adhering to the lids of various containers by washing them with an acid or an organic solvent before washing the containers, since this prevents the intrusion of foreign matter through the lids.

[0077] The developing solution of the present invention may be bottled in a container such as a gallon bottle or a coated bottle after production, and then transported and stored. The gallon bottle may be made of a glass material or a material other than glass. In order to prevent the components of the developer from changing during storage, the inside of the container may be replaced with an inert gas (nitrogen, argon, etc.) with a purity of 99.99995% or more by volume. In particular, a gas with a low moisture content is preferable. In addition, the developer may be stored at room temperature during transportation and storage, but the temperature may be controlled to a range of -20°C to 20°C to prevent deterioration.

[0078] <Clean room> It is preferable that all of the manufacturing of the developing solution of the present invention, the opening and / or cleaning of the container, the handling including filling of the developing solution, the processing analysis, and the measurement are carried out in a clean room. The clean room preferably meets the 14644-1 clean room standard. It is preferable that the clean room meets any one of ISO (International Organization for Standardization) Class 1, ISO Class 2, ISO Class 3, and ISO Class 4, more preferably ISO Class 1 or ISO Class 2, and even more preferably ISO Class 1.

[0079] [Actinic ray- or radiation-sensitive resin composition (composition)] Next, the actinic ray-sensitive or radiation-sensitive resin composition (also referred to as "composition") used in the pattern forming method of the present invention will be described. The composition of the present invention is preferably a resist composition for KrF exposure. The composition of the present invention is a resist composition for organic solvent development, and is typically a chemically amplified resist composition.

[0080] Among others, the composition of the present invention is (A) a resin having a repeating unit having an aromatic group and a repeating unit having a group that is decomposed by the action of an acid to produce a polar group (also referred to as resin (A)), (B) a compound that generates an acid when exposed to actinic rays or radiation, and It is preferable that the composition contains (C) a solvent. The content of the repeating unit having the aromatic group is 15 mol % or more based on the total repeating units of the resin (A). It is also preferable that the composition further contains (G) a crosslinking agent. The crosslinking agent preferably has two crosslinkable groups in the molecule. Components that may be contained in the composition of the present invention are described in detail below.

[0081] <(A) Resin Having a Repeating Unit Having an Aromatic Group and a Repeating Unit Having a Group That Decomposes When Acted on by an Acid to Generate a Polar Group> The composition of the present invention preferably contains a resin (hereinafter also referred to as resin (A)) having a repeating unit having an aromatic group and a repeating unit having a group that is decomposed by the action of an acid to generate a polar group. Since the resin (A) has a repeating unit having a group that decomposes under the action of an acid to generate a polar group (hereinafter also referred to as an "acid-decomposable group"), it is typically preferred that the resin (A) is a resin whose solubility in a developer containing an organic solvent as a main component decreases under the action of an acid.

[0082] (Repeating unit having an aromatic group) The aromatic ring in the aromatic group constituting the repeating unit having an aromatic group is a monocyclic or polycyclic aromatic ring, and examples thereof include aromatic hydrocarbon rings having 6 to 18 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring, and a phenanthrene ring, which may have a substituent, and aromatic heterocycles including heterocycles such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. Among these, a benzene ring and a naphthalene ring are preferred from the viewpoint of resolution, and a benzene ring is most preferred. The aromatic group may further have a substituent, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group.

[0083] The resin (A) has a repeating unit having an aromatic group, and the content of the repeating unit having an aromatic group is 15 mol % or more based on the total repeating units of the resin (A), which allows a pattern having excellent cross-sectional rectangularity and etching resistance to be formed when exposed to KrF light. The upper limit of the content of the repeating units having the aromatic group is not particularly limited, but is usually 85 mol % or less based on all repeating units in the resin (A). The content of the repeating unit having the aromatic group is preferably from 15 to 70 mol %, more preferably from 15 to 60 mol %, and even more preferably from 15 to 55 mol %, based on all repeating units in the resin (A).

[0084] An example of the repeating unit having an aromatic group is a repeating unit represented by the following general formula (A).

[0085] [ka]

[0086] In the formula, R 01 , R 02 , and R 03 each independently represents, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. 1 represents an aromatic ring group. 03 represents an alkylene group, Ar 1 may be bonded to form a 5- or 6-membered ring together with the --CC-- chain. The n Ys each independently represent a hydrogen atom or a group which is eliminated by the action of an acid, provided that at least one of the Ys represents a group which is eliminated by the action of an acid. n represents an integer of 1 to 4, preferably 1 or 2, and more preferably 1.

[0087] R 01 ~R 03The alkyl group as the alkyl group is, for example, an alkyl group having 20 or less carbon atoms, and specific examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. The alkyl group is preferably an alkyl group having a carbon number of not more than 8. The alkyl group may have a substituent. The alkyl group contained in the alkoxycarbonyl group is the same as the above R 01 ~R 03 The same alkyl groups as those in the above are preferred. The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. Examples of the cycloalkyl group include monocyclic cycloalkyl groups having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. These cycloalkyl groups may have a substituent. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being more preferred.

[0088] R 03 When represents an alkylene group, the alkylene group is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Ar 1 The aromatic ring group as the aromatic ring group is preferably an aromatic ring group having 6 to 14 carbon atoms, and examples thereof include a benzene ring, a toluene ring, and a naphthalene ring. These aromatic ring groups may have a substituent. Suitable examples of the group which is removable by the action of an acid as at least one of the above Y's include those described below in the repeating units having a group which is decomposed by the action of an acid to generate a polar group.

[0089] The group that is eliminated by the action of an acid, which is at least one of the above Y's, is more preferably a structure represented by the following general formula (B).

[0090] [ka]

[0091] In the formula, L 1 and L 2 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. M represents a single bond or a divalent linking group. Q represents an alkyl group, a cycloalkyl group, a cyclic aliphatic group, an aromatic ring group, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group. The cyclic aliphatic group and the aromatic ring group may contain a heteroatom. Q, M, and L 1 At least two of these may be bonded to each other to form a 5- or 6-membered ring.

[0092] L 1 and L 2 The alkyl group as the alkyl group is, for example, an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. L 1 and L 2 The cycloalkyl group as the aryl group is, for example, a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. L 1 and L 2 The aryl group as the aryl group is, for example, an aryl group having 6 to 15 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group. L 1 and L 2 The aralkyl group as the aryl group is, for example, an aralkyl group having 6 to 20 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

[0093] Examples of the divalent linking group as M include an alkylene group (such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group), a cycloalkylene group (such as a cyclopentylene group or a cyclohexylene group), an alkenylene group (such as an ethylene group, a propenylene group, or a butenylene group), an arylene group (such as a phenylene group, a tolylene group, or a naphthylene group), -S-, -O-, -CO-, -SO 2 -, -N(R 0 )-, or a combination of two or more thereof. 0 is a hydrogen atom or an alkyl group. 0 The alkyl group as the alkyl group is, for example, an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group.

[0094] The alkyl group and cycloalkyl group represented by Q are the same as those described above for L 1 and L 2 The same applies to each group as above. Examples of the cyclic aliphatic group or aromatic ring group as Q include the above-mentioned L 1 and L 2 As examples of the cycloalkyl group, a cycloalkyl group and an aryl group are mentioned. These cycloalkyl groups and aryl groups are preferably groups having 3 to 15 carbon atoms. Examples of the cyclic aliphatic group or aromatic ring group containing a heteroatom as Q include groups having a heterocyclic structure such as thiirane, cyclothiolane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, and pyrrolidone, etc. However, the ring is not limited to these as long as it is a ring formed by carbon and a heteroatom, or a ring formed only by a heteroatom. Q, M, and L 1 Examples of the ring structure that can be formed by combining at least two of Q and L include 1 and form a propylene group or a butylene group together. This 5- or 6-membered ring structure contains an oxygen atom.

[0095] L in general formula (B) 1 , L 2 Each of the groups represented by M and Q may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. These substituents preferably have 8 or less carbon atoms. The group represented by -(MQ) is preferably a group having 1 to 20 carbon atoms, more preferably a group having 1 to 10 carbon atoms, and even more preferably a group having 1 to 8 carbon atoms.

[0096] The content of the repeating unit represented by formula (A) is preferably from 5 to 60 mol %, more preferably from 20 to 60 mol %, and even more preferably from 30 to 60 mol %, based on all repeating units in the resin (A).

[0097] As the repeating unit having an aromatic group, for example, it is also preferable to have a repeating unit having a phenolic hydroxyl group. The phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic group with a hydroxyl group. The aromatic ring constituting the aromatic group is as described above. An example of the repeating unit having a phenolic hydroxyl group is a repeating unit represented by the following general formula (B-1).

[0098] [ka]

[0099] In general formula (BH-1), R B1 , R B2 , and R B3 R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. B3 Ar B1may be bonded to form a ring, in which case R B3 represents an alkylene group. X B3 represents a single bond or a divalent linking group. Ar B1 is (n B +1)valent aromatic ring group, R B3 When it is bonded to form a ring, (n B represents a divalent aromatic ring group. n B represents an integer from 1 to 4.

[0100] R in general formula (BH-1) B1 , R B2 , and R B3 The alkyl group represented by the formula (I) is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, which may have a substituent, more preferably an alkyl group having 8 or less carbon atoms, and even more preferably an alkyl group having 3 or less carbon atoms.

[0101] R in general formula (BH-1) B1 , R B2 and R B3 The cycloalkyl group represented by the following formula may be a monocyclic or polycyclic cycloalkyl group. The cycloalkyl group is preferably a monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group, which may have a substituent. R in general formula (BH-1) B1 , R B2 , and R B3 Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. R in general formula (BH-1) B1 , R B2 , and R B3 The alkyl group contained in the alkoxycarbonyl group represented by the above R B1 , R B2 , and R B3The same groups as the alkyl group in the above formula are preferred.

[0102] Preferred examples of the substituent in each of the above groups include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group, and the number of carbon atoms of the substituent is preferably 8 or less.

[0103] Ar B1 is (n B +1)valent aromatic ring group. B When is 1, examples of the divalent aromatic ring group include arylene groups having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, and aromatic ring groups containing a heterocycle, such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole.

[0104] n B When (n B Specific examples of the (n +1)-valent aromatic ring group include those of the (n B -1) groups each having any one of hydrogen atoms removed therefrom.

[0105] X B3 The divalent linking group is -COO- or -CONR 64 -- are some examples. R 64 represents a hydrogen atom or an alkyl group. 64 The alkyl group may have a substituent and is preferably an alkyl group having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, or a dodecyl group, and more preferably an alkyl group having 8 or less carbon atoms. X B3is preferably a single bond, -COO-, or -CONH-, more preferably a single bond or -COO-, and further preferably a single bond.

[0106] Ar B1 As the ring group, an aromatic ring group having 6 to 18 carbon atoms is preferable, a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferable, and a benzene ring group is further preferable.

[0107] n B represents an integer of 1 to 4, with 1 or 2 being preferred, and 1 being more preferred.

[0108] The repeating unit represented by the above general formula (BH-1) is preferably a repeating unit represented by the following general formula (BH-2).

[0109] [ka]

[0110] In general formula (BH-2), R B1 , R B2 , and R B3 each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ar B1 is (n B represents a +1)valent aromatic ring group. n B represents an integer from 1 to 4.

[0111] R in general formula (BH-2) B1 , R B2 , R B3 , Ar B1 , and n B Specific and preferred examples of the above are R B1 , R B2 , R B3 , Ar B1 , and n B The specific and preferred examples are the same as those of the above. B3 Ar B1does not bond to form a ring.

[0112] Specific examples of the repeating unit represented by formula (BH-1) are shown below.

[0113] [ka]

[0114] [ka]

[0115] The content of the repeating unit having a phenolic hydroxyl group (the repeating unit represented by general formula (B-1), more preferably the repeating unit represented by general formula (BH-2)) is preferably 10 to 80 mol %, more preferably 20 to 70 mol %, and even more preferably 30 to 60 mol %, based on the total repeating units of the resin (A).

[0116] (Repeating unit having a group that is decomposed by the action of an acid to generate a polar group (acid-decomposable group)) Resin (A) contains a repeating unit having a group that decomposes under the action of an acid to generate a polar group (also referred to as a "repeating unit having an acid-decomposable group"). The repeating unit having an acid-decomposable group may be a repeating unit different from the repeating unit having an aromatic group, or may satisfy the requirements for a repeating unit having an aromatic group. The group that is decomposed by the action of an acid to generate a polar group (acid-decomposable group) preferably has a structure in which the polar group is protected by a group that is decomposed and eliminated by the action of an acid. Examples of the polar group include acidic groups such as a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group (groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide, which is conventionally used as a developer for resists), and an alcoholic hydroxyl group. A polar group, a carboxyl group, a fluorinated alcohol group (such as a hexafluoroisopropanol group), or a sulfonic acid group is preferred.

[0117] Preferred as the acid-decomposable group are groups in which the hydrogen atom of these polar groups is substituted with a group which is eliminated by the action of an acid. Examples of the group that is eliminated by the action of an acid include -C(R 36 )(R 37 )(R 38 ), -C(R 36 )(R 37 )(OR 39 ), -C(R 01 )(R 02 )(OR 39 ), -C(R 01 )(R 02 )-C(=O)-OC(R 36 )(R 37 )(R 38 ), or -CH(R 36 )(Ar). In the formula, R 36 ~R 39 R each independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. 36 and R 37 may be bonded to each other to form a ring. R 01 and R 02each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Ar represents an aryl group.

[0118] R 36 ~R 39 , R 01 , and R 02 The alkyl group as the aryl group is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a hexyl group, and an octyl group. R 36 ~R 39 , R 01 , and R 02 The cycloalkyl group as may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. As the monocyclic cycloalkyl group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinanyl group, a tricyclodecanyl group, a tetracyclododecyl group, and a androstanyl group. Note that a part of the carbon atoms in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom. R 36 ~R 39 , R 01 , R 02 The aryl group as Ar is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. R 36 ~R 39 , R 01 , and R 02 The aralkyl group as is preferably an aralkyl group having 7 to 12 carbon atoms, for example, a benzyl group, a phenethyl group, or a naphthylmethyl group. R 36 ~R 39 , R01 , and R 02 The alkenyl group as is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.

[0119] R 36 and R 37 The ring that can be formed by bonding with each other may be a monocyclic ring or a polycyclic ring. As the monocyclic ring, a cycloalkane structure having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, and a cyclooctane structure. As the polycyclic ring, a cycloalkane structure having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantane structure, a norbornane structure, a dicyclopentane structure, a tricyclodecane structure, and a tetracyclododecane structure. In addition, a part of the carbon atoms in the ring structure may be substituted with a heteroatom such as an oxygen atom. Each of the above groups may have a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. These substituents preferably have 8 or less carbon atoms.

[0120] The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably a tertiary alkyl ester group.

[0121] The repeating unit having an acid-decomposable group that the resin (A) may have is preferably a repeating unit represented by the following general formula (AI).

[0122] [ka]

[0123] In the general formula (AI), Xa 1 represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx 1 ~Rx 3 each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Rx 1 ~Rx 3 may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

[0124] Xa 1 The alkyl group represented by the formula (I) may or may not have a substituent, and may be, for example, a methyl group or -CH 2 -R 11 Examples of the group represented by R 11 R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. 11 is preferably an alkyl group having 5 or less carbon atoms or an acyl group having 5 or less carbon atoms, more preferably an alkyl group having 3 or less carbon atoms, and even more preferably a methyl group. Xa 1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. Examples of the divalent linking group for T include an alkylene group, a -COO-Rt- group, and a -O-Rt- group, in which Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. Rt is preferably an alkylene group having 1 to 5 carbon atoms, and -CH 2 - group, -(CH 2 ) 2 - group, -(CH 2 ) 3 The - group is more preferred.

[0125] Rx 1 ~Rx 3 The alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. Rx1 ~Rx 3 The cycloalkyl group is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Rx 1 ~Rx 3 The cycloalkyl group formed by combining the above two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable. Rx 1 ~Rx 3 In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, or a group having a heteroatom such as a carbonyl group. The repeating unit represented by the general formula (AI) is, for example, Rx 1 is a methyl group or an ethyl group, and Rx 2 and Rx 3 and are bonded to form the above-mentioned cycloalkyl group.

[0126] Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (preferably having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (preferably having 2 to 6 carbon atoms). The above substituents preferably have 8 or less carbon atoms.

[0127] Preferred specific examples of the repeating unit having an acid-decomposable group are shown below, but the present invention is not limited thereto. In specific examples, Rx, Xa 1 is a hydrogen atom, CH 3 , C.F. 3 , or C.H. 2OH. Rxa and Rxb each independently represent an alkyl group having 1 to 4 carbon atoms. Z represents a substituent containing a polar group, and when a plurality of Zs are present, each is independent. p represents 0 or a positive integer. Examples of the substituent containing a polar group represented by Z include linear or branched alkyl groups and cycloalkyl groups having a hydroxyl group, a cyano group, an amino group, an alkylamide group and / or a sulfonamide group. Among them, the substituent containing a polar group represented by Z is preferably an alkyl group having a hydroxyl group. The branched alkyl group is preferably an isopropyl group.

[0128] [ka]

[0129] The repeating unit having a group that is decomposed by the action of an acid to generate a polar group preferably has an alicyclic hydrocarbon group having a carbon number of 5 to 20. The alicyclic hydrocarbon group is not particularly limited, but examples thereof include cycloalkyl groups. The cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. As the monocyclic cycloalkyl group, a cycloalkyl group having 5 to 8 carbon atoms is preferable, and examples thereof include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinanyl group, a tricyclodecanyl group, a tetracyclododecyl group, and a androstanyl group. In addition, a part of the carbon atoms in the cycloalkyl group may be replaced by a heteroatom such as an oxygen atom. The number of carbon atoms in the alicyclic hydrocarbon group having 5 to 20 carbon atoms represents the number of carbon atoms constituting the skeleton of the alicyclic hydrocarbon ring. The alicyclic hydrocarbon group may further have a substituent.

[0130] It is also preferable that the resin (A) contains a repeating unit represented by general formula (3) as the repeating unit represented by general formula (AI).

[0131] [ka]

[0132] In general formula (3), R 31 represents a hydrogen atom or an alkyl group. R 32 represents an alkyl group or a cycloalkyl group, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a cyclohexyl group. R 33 is R 32 represents an atomic group necessary to form a monocyclic alicyclic hydrocarbon structure together with the carbon atom to which it is bonded. In the alicyclic hydrocarbon structure, some of the carbon atoms constituting the ring may be substituted with a heteroatom or a group having a heteroatom.

[0133] R 31 The alkyl group of R may have a substituent, and examples of the substituent include a fluorine atom and a hydroxyl group. 31 preferably represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R 32 is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, or a cyclohexyl group, and more preferably a methyl group, an ethyl group, an isopropyl group, or a tert-butyl group. R 33 The monocyclic alicyclic hydrocarbon structure which is formed by combining with the carbon atom is preferably a 3- to 8-membered ring, and more preferably a 5- or 6-membered ring. R 33In the monocyclic alicyclic hydrocarbon structure formed by the above together with the carbon atom, examples of heteroatoms that can constitute the ring include an oxygen atom, a sulfur atom, etc., and examples of groups having a heteroatom include a carbonyl group, etc. However, it is preferable that the group having a heteroatom is not an ester group (ester bond). R 33 The monocyclic alicyclic hydrocarbon structure which is formed together with the carbon atom is preferably formed only from carbon atoms and hydrogen atoms.

[0134] The repeating unit represented by formula (3) is also preferably a repeating unit represented by the following formula (3').

[0135] [ka]

[0136] In general formula (3'), R 31 and R 32 have the same meanings as those in the above general formula (3). Specific examples of the repeating unit having the structure represented by formula (3) are listed below, but the invention is not limited thereto.

[0137] [ka]

[0138] The content of the repeating unit having the structure represented by formula (3) is preferably from 10 to 70 mol %, more preferably from 20 to 60 mol %, and even more preferably from 30 to 50 mol %, based on all repeating units in the resin (A).

[0139] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by the above general formula (A). In view of the fact that polarity is easily generated by the action of an acid, it is preferable that the repeating unit having a group that is decomposed by the action of an acid to generate a polar group is a repeating unit corresponding to (meth)acrylic acid.

[0140] The total content of repeating units having an acid-decomposable group is preferably from 20 to 90 mol %, more preferably from 25 to 85 mol %, and even more preferably from 25 to 50 mol %, based on all repeating units in the resin (A). When the resin (A) contains both a repeating unit that has an aromatic group and also has an acid-decomposable group, and a repeating unit that has an acid-decomposable group and does not fall under the category of repeating units having an aromatic group, it is preferable that the total content of both of them falls within the above-mentioned content range. It is also preferable that the above-mentioned content range is satisfied only by repeating units that have a group that can be decomposed by the action of an acid to produce a polar group, and that do not fall under the category of repeating units having an aromatic group.

[0141] Resin (A) has a repeating unit having an aromatic group and a repeating unit having a group that is decomposed by the action of an acid to generate a polar group, but it may have other repeating units in addition to the repeating unit having an aromatic group and the repeating unit having a group that is decomposed by the action of an acid to generate a polar group.

[0142] (Other repeating units) In one embodiment, the resin (A) preferably contains a repeating unit having a cyclic carbonate structure. The cyclic carbonate structure is a structure having a ring containing a bond represented by -OC(=O)-O- as an atomic group constituting the ring. The ring containing a bond represented by -OC(=O)-O- as an atomic group constituting the ring is preferably a 5- to 7-membered ring, more preferably a 5-membered ring. Such a ring may be condensed with another ring to form a condensed ring.

[0143] The resin (A) may also have a repeating unit having a lactone structure or a sultone (cyclic sulfonate ester) structure. It is also preferable that the repeating unit having a lactone structure or a sultone structure is a repeating unit different from the repeating units described above. Any lactone or sultone group can be used as long as it has a lactone or sultone structure, but it is preferably a 5- to 7-membered lactone or sultone structure, and it is preferably a 5- to 7-membered lactone or sultone structure condensed with another ring structure to form a bicyclo or spiro structure. It is more preferable to have a repeating unit having a lactone or sultone structure represented by any of the following general formulas (LC1-1) to (LC1-17), (SL1-1), and (SL1-2). The lactone or sultone structure may be directly bonded to the main chain. A preferred lactone or sultone structure is a lactone structure represented by general formula (LC1-1), (LC1-4), (LC1-5), or (LC1-8), and more preferably a lactone structure represented by general formula (LC1-4). By using a specific lactone or sultone structure, line width roughness (LWR) and development defects are improved.

[0144] [ka]

[0145] [ka]

[0146] The lactone structure portion or the sultone structure portion is a substituent (Rb 2 ) may or may not have a substituent (Rb 2 ) include, for example, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is preferred. 2 represents an integer of 0 to 4. 2When Rb is 2 or more, multiple substituents (Rb 2 ) may be the same or different, and when multiple substituents (Rb 2 ) may be bonded to each other to form a ring.

[0147] A repeating unit having a lactone group or a sultone group usually has optical isomers, and any of the optical isomers may be used. In addition, one type of optical isomer may be used alone, or a mixture of multiple optical isomers may be used. When one type of optical isomer is mainly used, the optical purity (ee) is preferably 90% or more, and more preferably 95% or more.

[0148] The resin (A) may contain a repeating unit having a hydroxyl group or a cyano group other than that represented by formula (AI), which improves the adhesion to the substrate and the affinity for the developer. It is also preferable that the repeating unit having a hydroxyl group or a cyano group is a repeating unit different from the repeating units described above. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and preferably has no acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably an adamantyl group, a diamantyl group, or a norbornane group. The alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group is preferably a partial structure represented by the following general formulas (VIIa) to (VIId).

[0149] [ka]

[0150] In general formulas (VIIa) to (VIIc), R 2 c~R 4 Each c independently represents a hydrogen atom, a hydroxyl group, or a cyano group. 2 c~R 4 At least one of R c represents a hydroxyl group or a cyano group. 2 c~R4 It is preferred that one or two of c are hydroxyl groups and the rest are hydrogen atoms; 2 c~R 4 It is more preferable that two of c's are hydroxyl groups and the remainder is a hydrogen atom.

[0151] Examples of the repeating units having the partial structures represented by general formulas (VIIa) to (VIId) include repeating units represented by the following general formulas (AIIa) to (AIId).

[0152] [ka]

[0153] In the general formula (AIIa) ~ (AIId), R 1 c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R 2 c~R 4 c is R in general formulas (VIIa) to (VIIc). 2 c~R 4 Synonymous with c. When the resin (A) contains a repeating unit having a hydroxyl group or a cyano group, the content thereof is preferably from 5 to 40 mol %, more preferably from 5 to 30 mol %, and even more preferably from 10 to 25 mol %, based on all repeating units in the resin (A). Specific examples of the repeating unit having a hydroxyl group or a cyano group are listed below, but the present invention is not limited to these.

[0154] [ka]

[0155] The resin (A) used in the composition of the present invention may have a repeating unit having an acid group. It is also preferred that the repeating unit having an acid group is a repeating unit different from the repeating units described above. Examples of the acid group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol substituted with an electron-withdrawing group at the α-position (such as a hexafluoroisopropanol group), with the carboxyl group being preferred. By including a repeating unit having an acid group, the resolution in contact hole applications is increased. The repeating unit having an acid group may be any of a repeating unit in which an acid group is directly bonded to the main chain of a resin, such as a repeating unit of acrylic acid or methacrylic acid, a repeating unit in which an acid group is bonded to the main chain of a resin via a linking group, and a repeating unit introduced to the end of a polymer chain using a polymerization initiator or chain transfer agent having an acid group during polymerization. The linking group may have a monocyclic or polycyclic hydrocarbon structure. Among them, the repeating unit having an acid group is a repeating unit based on acrylic acid or methacrylic acid.

[0156] Furthermore, examples of the repeating unit having an acid group in the resin (A) include the repeating unit having a phenolic hydroxyl group.

[0157] The content of the repeating unit having an acid group is preferably from 30 to 90 mol %, more preferably from 35 to 85 mol %, and even more preferably from 40 to 80 mol %, based on all repeating units in the resin (A). When the resin (A) contains both a repeating unit having an aromatic group and also a repeating unit having an acid group, and a repeating unit having an acid group but not corresponding to the repeating unit having an aromatic group, it is preferable that the total content of both of them falls within the above content range, and it is also preferable that only the repeating unit having an acid group but not corresponding to the repeating unit having an aromatic group falls within the above content range.

[0158] Specific examples of the repeating unit having an acid group are shown below, but the present invention is not limited thereto. In the specific examples, Rx is H, CH 3 , C.H. 2 OH or CF3 Represents.

[0159] [ka]

[0160] The resin (A) may further contain a repeating unit that has a cyclic hydrocarbon structure that does not have a polar group (such as an acid group, a hydroxyl group, or a cyano group) and does not exhibit acid decomposability. It is also preferred that such a repeating unit is a repeating unit different from the repeating units described above. An example of such a repeating unit is a repeating unit represented by general formula (IV).

[0161] [ka]

[0162] In the above general formula (IV), R 5 represents a hydrocarbon group having at least one cyclic structure and no polar group. Ra is a hydrogen atom, an alkyl group or -CH 2 -O-Ra 2 In the formula, Ra 2 represents a hydrogen atom, an alkyl group or an acyl group. 2 is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.

[0163] R 5 The cyclic structure contained in includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a cycloalkyl group having 3 to 12 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, a cycloalkenyl group having 3 to 12 carbon atoms, such as a cyclohexenyl group, and a phenyl group. The monocyclic hydrocarbon group is preferably a monocyclic hydrocarbon group having 3 to 7 carbon atoms, and more preferably a cyclopentyl group or a cyclohexyl group. Polycyclic hydrocarbon groups include ring assembly hydrocarbon groups and bridged ring hydrocarbon groups. Examples of ring assembly hydrocarbon groups include bicyclohexyl, perhydronaphthalenyl, biphenyl, and 4-cyclohexylphenyl. Examples of bridged ring hydrocarbon rings include bicyclic hydrocarbon rings such as pinane, bornane, norpinane, norbornane, and bicyclooctane rings (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.), homobredane, adamantane, tricyclo[5.2.1.0]octane, etc. 2,6 ]decane and tricyclo[4.3.1.1 2,5 ]undecane ring and other tricyclic hydrocarbon rings, as well as tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodecane, and tetracyclic hydrocarbon rings such as mperhydro-1,4-methano-5,8-methanonaphthalene ring. The bridged cyclic hydrocarbon ring also includes a condensed ring in which a plurality of condensed cyclic hydrocarbon rings (for example, 5- to 8-membered cycloalkane rings such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings) are condensed.

[0164] The bridged cyclic hydrocarbon ring is a norbornyl group, an adamantyl group, a bicyclooctanyl group, or a tricyclo[5, 2, 1, 0 2,6 ]decanyl group is preferred, and norbornyl or adamantyl group is more preferred. These cyclic hydrocarbon structures may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. The halogen atom is preferably a bromine atom, a chlorine atom, or a fluorine atom. The alkyl group is preferably a methyl, ethyl, butyl, or t-butyl group. The alkyl group may further have a substituent, and examples of the substituent that may further have include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom. Examples of the group in which the hydrogen atom is substituted include an alkyl group, a cycloalkyl group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, and an aralkyloxycarbonyl group. Examples of the alkyl group include an alkyl group having 1 to 4 carbon atoms. Examples of the substituted methyl group include a methoxymethyl group, a methoxythiomethyl group, a benzyloxymethyl group, a t-butoxymethyl group, and a 2-methoxyethoxymethyl group. Examples of the substituted ethyl group include a 1-ethoxyethyl group and a 1-methyl-1-methoxyethyl group. Examples of the acyl group include an aliphatic acyl group having 1 to 6 carbon atoms, such as a formyl group, an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, and a pivaloyl group. Examples of the alkoxycarbonyl group include an alkoxycarbonyl group having 1 to 4 carbon atoms.

[0165] When the resin (A) has a repeating unit that has a cyclic hydrocarbon structure without a polar group and is not acid decomposable, the content thereof is preferably 1 to 40 mol %, more preferably 2 to 20 mol %, based on the total repeating units in the resin (A). When resin (A) contains both a repeating unit which has an aromatic group but at the same time has a cyclic hydrocarbon structure which does not have a polar group and is not acid decomposable, and a repeating unit which does not fall under the category of a repeating unit having an aromatic group, has a cyclic hydrocarbon structure which does not have a polar group and is not acid decomposable, it is preferable that the total content of both of them falls within the above content range. It is also preferable that the above content range is satisfied only by the repeating unit which does not fall under the category of a repeating unit having an aromatic group, has a cyclic hydrocarbon structure which does not have a polar group and is not acid decomposable.

[0166] Specific examples of the repeating unit having a cyclic hydrocarbon structure without a polar group and not exhibiting acid decomposability are given below, but the present invention is not limited thereto. 3 , C.H. 2 OH or CF 3 Represents.

[0167] [ka]

[0168] [ka]

[0169] [ka]

[0170] [ka]

[0171] The resin (A) may further contain a repeating unit that does not have a polar group (such as an acid group, a hydroxyl group, or a cyano group) or a cyclic hydrocarbon structure and does not exhibit acid decomposability. It is also preferred that such a repeating unit is a repeating unit different from the repeating units described above. As such a repeating unit, there is mentioned a repeating unit represented by the above general formula (IV), in which R 5 is replaced by an unsubstituted alkyl group. The alkyl group may be linear or branched and preferably has 1 to 15 carbon atoms, more preferably 2 to 10 carbon atoms. When the resin (A) has a repeating unit that does not have a polar group (an acid group, a hydroxyl group, a cyano group, or the like) and a cyclic hydrocarbon structure and does not exhibit acid decomposability, the content thereof is preferably 1 to 40 mol %, more preferably 2 to 20 mol %, based on the total repeating units in the resin (A).

[0172] In addition to the above repeating structural units, the resin (A) used in the composition of the present invention may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, and furthermore, general required properties of a resist, such as resolution, heat resistance, sensitivity, etc. Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to the following monomers: This enables fine adjustment of the properties required of the resin used in the composition of the present invention, in particular (1) solubility in a coating solvent, (2) film-forming properties (glass transition temperature), (3) alkaline developability, (4) film loss (hydrophilicity / hydrophobicity, acid group selection), (5) adhesion to the substrate in unexposed areas, and (6) dry etching resistance.

[0173] Examples of such monomers include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters, other than the monomers corresponding to the repeating units described above. In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the various repeating structural units described above may be copolymerized. In the resin (A) used in the composition of the present invention, the molar ratio of each repeating structural unit is appropriately set in order to adjust the dry etching resistance, suitability for a standard developer, substrate adhesion, and resist profile of the resist, as well as the general required performance properties of a resist, such as resolution, heat resistance, and sensitivity.

[0174] The resin (A) in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, typical synthesis methods include a bulk polymerization method in which a monomer species and an initiator are dissolved in a solvent and polymerized by heating, and a dropwise polymerization method in which a solution of a monomer species and an initiator is added dropwise to a heated solvent over 1 to 10 hours, and the dropwise polymerization method is preferred. Examples of reaction solvents include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether, ketones such as methyl ethyl ketone and methyl isobutyl ketone, ester solvents such as ethyl acetate, and amide solvents such as dimethylformamide and dimethylacetamide. Other examples include solvents that dissolve the composition of the present invention, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone, which will be described later. It is also preferable to use the same solvent as the reaction solvent used in the composition of the present invention. This can suppress the generation of particles during storage. The polymerization reaction is preferably carried out under an inert gas atmosphere such as nitrogen or argon. Polymerization is initiated using a commercially available radical initiator (azo initiator, peroxide, etc.) as the polymerization initiator. As the radical initiator, azo initiators are preferred, and examples thereof include azo initiators having an ester group, a cyano group, and / or a carboxyl group. Examples of initiators include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). If desired, the initiator is added or added in portions, and after the reaction is completed, the desired polymer is recovered by a method such as pouring into a solvent and recovering a powder or solid. The reaction concentration is preferably 5 to 50% by mass, more preferably 10 to 30% by mass. The reaction temperature is usually preferably 10 to 150°C, more preferably 30 to 120°C, and even more preferably 60 to 100°C.

[0175] The weight average molecular weight of the resin (A) is preferably 5,000 to 200,000, more preferably 8,000 to 50,000, and even more preferably 10,000 to 35,000. By setting the weight average molecular weight within the above range, it is possible to prevent a decrease in heat resistance and dry etching resistance, and also to prevent a deterioration in developability and a deterioration in film formability due to an increase in viscosity. The dispersity (molecular weight distribution) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. When the molecular weight distribution is appropriately small, the resolution and resist shape are excellent, the side walls of the resist pattern are smooth, and roughness is excellent.

[0176] The content of the resin (A) is preferably from 30 to 99 mass %, more preferably from 50 to 97 mass %, based on the total solid content of the composition. The solid content refers to all components in the composition excluding the solvent, and any component that forms a resist film is considered to be a solid content even if it is a liquid at room temperature. The resin (A) may be used alone or in combination of two or more kinds.

[0177] <(X) Resin having a content of repeating units having an aromatic group of 0% by mass or more and less than 15% by mass based on the total mass of the resin> In addition, in the composition of the present invention, a resin (also referred to as "resin (X)") may be used in which the content of repeating units having an aromatic group is from 0 mass % to less than 15 mass % relative to the total mass of the resin. Resin (X) may not contain a repeating unit having an aromatic group, and when it does contain such a repeating unit, the content thereof is more than 0 mass % and less than 15 mass % based on all repeating units of resin (X). Resin (X) is similar to resin (A) except that the content of repeating units having an aromatic group is from 0% by mass to less than 15% by mass based on the total mass of the resin, and the preferred conditions are also similar. Resin (X) may be added separately from resin (A), or may be added to replace a part or all of resin (A). When the composition contains the resin (X), the content thereof is preferably from 30 to 99 mass %, more preferably from 50 to 97 mass %. When the composition contains both the resin (A) and the resin (X), the total content thereof is preferably from 30 to 99 mass %, more preferably from 50 to 97 mass %.

[0178] <(B) Compound that generates an acid when exposed to actinic rays or radiation> The composition of the present invention preferably contains (B) a compound that generates an acid upon exposure to actinic rays or radiation (also referred to as "compound (B)" or "photoacid generator"). A photoacid generator is a compound that generates an acid when exposed to actinic rays or radiation. The photoacid generator is preferably a compound that generates an organic acid upon irradiation with actinic rays or radiation, such as a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzylsulfonate compound.

[0179] As the photoacid generator, known compounds that generate an acid when irradiated with actinic rays or radiation can be appropriately selected and used alone or as a mixture thereof. For example, known compounds disclosed in U.S. Patent Application Publication No. 2016 / 0070167A1, U.S. Patent Application Publication No. 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0237190A1 can be suitably used.

[0180] As the photoacid generator, for example, a compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable.

[0181] [ka]

[0182] In the above general formula (ZI), R 201 , R 202 , and R 203 each independently represents an organic group. R 201 , R 202 , and R 203 The organic group as the substituent generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms. Also, R 201 ~R 203 Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. 201 ~R 203 Examples of groups formed by combining two of these groups include alkylene groups (e.g., butylene and pentylene groups) and -CH 2 -CH 2 -O-CH 2 -CH 2 -- are some examples. Z - represents an anion (preferably a non-nucleophilic anion).

[0183] Suitable embodiments of the cation in general formula (ZI) include corresponding groups in compound (ZI-1), compound (ZI-2), compound represented by general formula (ZI-3) (compound (ZI-3)), and compound represented by general formula (ZI-4) (compound (ZI-4)) described below. The photoacid generator may be a compound having a plurality of structures represented by general formula (ZI). For example, R 201 ~R 203 and R of another compound represented by general formula (ZI) 201 ~R 203 and at least one of the above may be bonded via a single bond or a linking group.

[0184] First, the compound (ZI-1) will be described. Compound (ZI-1) is a compound represented by the formula (ZI) R 201 ~R 203At least one of the above is an aryl group, that is, an arylsulfonium compound having an arylsulfonium cation. Arylsulfonium compounds are R 201 ~R 203 All of R may be aryl groups. 201 ~R 203 A part of R may be an aryl group and the rest may be an alkyl group or a cycloalkyl group. 201 ~R 203 Two of the groups may be bonded to form a ring structure, and the remaining one may be an aryl group. Examples of the arylsulfonium compound include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0185] The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure with an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium compound may have as necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

[0186] R 201 ~R 203The aryl group, alkyl group, and cycloalkyl group may each independently have an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 14 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

[0187] Next, the compound (ZI-2) will be described. Compound (ZI-2) is a compound represented by the formula (ZI) 201 ~R 203 are compounds each independently representing an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom. R 201 ~R 203 The organic group having no aromatic ring as the aromatic ring generally has 1 to 30 carbon atoms, and preferably has 1 to 20 carbon atoms. R 201 ~R 203 are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and further preferably a linear or branched 2-oxoalkyl group.

[0188] R 201 ~R 203 Examples of the alkyl group and cycloalkyl group include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). R 201 ~R 203 is also preferably further substituted with a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

[0189] Next, the compound (ZI-3) will be described.

[0190] [ka]

[0191] In the general formula (ZI-3), M represents an alkyl group, a cycloalkyl group, or an aryl group, and when it has a ring structure, the ring structure may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond. 1c and R 2c R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. 1c and R 2c may be bonded to form a ring. x and R y R each independently represents an alkyl group, a cycloalkyl group, or an alkenyl group. x and R y may be bonded to form a ring. 1c and R 2c may be bonded to form a ring structure, and the ring structure may contain a carbon-carbon double bond. - represents an anion.

[0192] In general formula (ZI-3), the alkyl group and cycloalkyl group represented by M are preferably a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), a branched alkyl group having 3 to 15 carbon atoms (preferably 3 to 10 carbon atoms), or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Specific examples of the alkyl group and cycloalkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and a norbornyl group. The aryl group represented by M is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom or a sulfur atom. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, and a benzothiophene ring.

[0193] The above M may further have a substituent (for example, a substituent group T), and for example, M may be a benzyl group. When M has a ring structure, it is also preferable that the ring structure contains at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbon-carbon double bond.

[0194] R 1c and R 2c The alkyl group, cycloalkyl group, and aryl group represented by the formula (I) include the same as those described above for M, and the preferred embodiments thereof are also the same. 1c and R 2c may be bonded to form a ring. R 1c and R 2c Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0195] R x and R y Examples of the alkyl group and cycloalkyl group represented by the formula (I) include the same as those for M described above, and preferred embodiments thereof are also the same. R x and R y The alkenyl group represented by the formula (I) is preferably an allyl group or a vinyl group. Above R x and R y may further have a substituent (for example, a substituent group T). For example, R x and R y may be a 2-oxoalkyl group or an alkoxycarbonylalkyl group. R x and R yThe 2-oxoalkyl group represented by the following formula is preferably a group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and examples thereof include a 2-oxopropyl group and a 2-oxobutyl group. R x and R y The alkoxycarbonylalkyl group represented by the following formula is preferably a group having 1 to 15 carbon atoms, and more preferably a group having 1 to 10 carbon atoms. Also, R x and R y may be bonded to form a ring. R x and R y The ring structure formed by linking together may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, and / or a carbon-carbon double bond.

[0196] In the general formula (ZI-3), M and R 1c may be linked to form a ring structure, and the ring structure formed may contain a carbon-carbon double bond.

[0197] Of these, the compound (ZI-3) is preferably the compound (ZI-3A). The compound (ZI-3A) is represented by the following general formula (ZI-3A) and is a compound having a phenacylsulfonium salt structure.

[0198] [ka]

[0199] In the general formula (ZI-3A), R 1c ~R 5c each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c is R in the above general formula (ZI-3). 2and R 3 The preferred embodiments thereof are also the same. R x and R y is R in the above general formula (ZI-3). x and R y The preferred embodiments thereof are also the same.

[0200] R 1c ~R 5c Any two or more of the following, R x and R y may be bonded to each other to form a ring structure. The ring structure may each independently contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, and / or a carbon-carbon double bond. 5c and R 6c , R 5c and R x may be bonded to each other to form a ring structure, and each of these ring structures may independently contain a carbon-carbon double bond. 6c and R 7c may be bonded to each other to form a ring structure. The ring structure includes an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings. The ring structure includes, for example, a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

[0201] R 1c ~R 5c Any two or more of the following, R 6c and R 7c , and R x and R y Examples of the group formed by bonding include a butylene group and a pentylene group. R 5c and R 6c , and R 5c and R x The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group. Zc- represents an anion.

[0202] Next, the compound (ZI-4) will be described. The compound (ZI-4) is represented by the following general formula (ZI-4).

[0203] [ka]

[0204] In the general formula (ZI-4), l represents an integer of 0 to 2. r represents an integer of 0 to 8. R 13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent. R 14 When a plurality of groups are present, each independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group, a cycloalkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or an alkoxy group having a monocyclic or polycyclic cycloalkyl skeleton. These groups may have a substituent. R 15 Each of R independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. 15 may be bonded to each other to form a ring. 15 When R are bonded to each other to form a ring, the ring structure may contain a heteroatom such as an oxygen atom or a nitrogen atom. 15 are preferably alkylene groups and are bonded to each other to form a ring structure. Z - represents an anion.

[0205] In general formula (ZI-4), R 13 , R 14 , and R 15The alkyl group is linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like.

[0206] The compound (B) is preferably a compound represented by the general formula (ZI-3) or (ZI-4).

[0207] Next, general formulae (ZII) and (ZIII) will be described. In the general formulas (ZII) and (ZIII), R 204 ~R 207 each independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 ~R 207 The aryl group of R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 204 ~R 207 The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, etc. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R 204 ~R 207 The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, and a norbornyl group).

[0208] R 204 ~R 207 The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. 204 ~R 207Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (preferably having 1 to 15 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 15 carbon atoms), an alkoxy group (preferably having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Z - represents an anion.

[0209] Z in formula (ZI) - , Z in formula (ZII) - In general formula (ZI-3), Z - Zc in formula (ZI-3A) - and Z in general formula (ZI-4) - As the anion, an anion represented by the following general formula (3) is preferable.

[0210] [ka]

[0211] In general formula (3), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0212] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF 3 In particular, it is more preferable that both Xf are fluorine atoms.

[0213] R 4 and R 5R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple, R 4 and R 5 may be the same or different. R 4 and R 5 The alkyl group represented by the following formula (1) may have a substituent and preferably has 1 to 4 carbon atoms. 4 and R 5 is preferably a hydrogen atom. Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in general formula (3).

[0214] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, and -SO 2 -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO 2 -, -COO-alkylene group-, -OCO-alkylene group-, -CONH-alkylene group-, or -NHCO-alkylene group- is preferred, and -COO-, -OCO-, -CONH-, -SO 2 -, -COO-alkylene group-, or -OCO-alkylene group- are more preferred.

[0215] W represents an organic group containing a cyclic structure, and is preferably a cyclic organic group. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl, are preferred.

[0216] The aryl group may be monocyclic or polycyclic, and examples of the aryl group include phenyl, naphthyl, phenanthryl, and anthryl groups. The heterocyclic group may be monocyclic or polycyclic. The polycyclic group can suppress the diffusion of the acid more effectively. The heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocyclic rings having aromaticity include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Examples of heterocyclic rings not having aromaticity include tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring. Examples of lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the above-mentioned resin. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

[0217] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon contributing to the ring formation) may be a carbonyl carbon.

[0218] The anion represented by the general formula (3) is SO 3 - -CF 2 -CH 2 -OCO-(L)q'-W,SO 3 - -CF 2 -CHF-CH 2 -OCO-(L)q'-W,SO 3 - -CF 2 -COO-(L)q'-W,SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 -(L)qW or SO 3 - -CF 2 -CH(CF 3 )-OCO-(L)q'-W is preferred, where L, q and W are the same as in the general formula (3). q' represents an integer of 0 to 10.

[0219] In one embodiment, Z in general formula (ZI) - , Z in formula (ZII) - Zc in general formula (ZI-3) - and Z in general formula (ZI-4) - The anion represented by the following general formula (4) is also preferred.

[0220] [ka]

[0221] In general formula (4), X B1 and X B2 Each of X independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. B1 and X B2 is preferably a hydrogen atom. X B3 and X B4 Each of X independently represents a hydrogen atom or a monovalent organic group. B3 and X B4 At least one of X is preferably a fluorine atom or a monovalent organic group having a fluorine atom, B3 and X B4 It is more preferable that both of X are fluorine atoms or monovalent organic groups having fluorine atoms. B3 and X B4 It is more preferable that both of the above are alkyl groups substituted with a fluorine atom. L, q and W are the same as in formula (3).

[0222] Z in formula (ZI) - , Z in formula (ZII) - Zc in general formula (ZI-3) - and Z in general formula (ZI-4) - may be a benzenesulfonate anion, preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0223] Z in formula (ZI) - , Z in formula (ZII) - Zc in general formula (ZI-3) - and Z in general formula (ZI-4) - Also preferred as the anion are aromatic sulfonate anions represented by the following general formula (SA1).

[0224] [ka]

[0225] In formula (SA1), Ar represents an aryl group, which may further have a substituent other than the sulfonate anion and the -(DB) group, such as a fluorine atom and a hydroxyl group.

[0226] n represents an integer of 0 or more. As n, 1 to 4 is preferable, 2 to 3 is more preferable, and 3 is even more preferable.

[0227] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate group, an ester group, and a group formed by combining two or more of these groups.

[0228] B represents a hydrocarbon group.

[0229] It is also preferred that D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

[0230] Preferred examples of the sulfonium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

[0231] [ka]

[0232] Anion Z in general formula (ZI) and general formula (ZII) - Zc in general formula (ZI-3) - and Z in general formula (ZI-4) - Preferred examples are shown below.

[0233] [ka]

[0234] [ka]

[0235] Any combination of the above cations and anions can be used as the photoacid generator.

[0236] From the viewpoint of the rectangularity of the cross-sectional shape of the pattern, the photoacid generator is preferably a sulfonium salt having no aromatic ring group or only one aromatic ring group.

[0237] From the viewpoints of the cross-sectional shape of the pattern and resistance to ion implantation, it is preferable that the number of fluorine atoms in the photoacid generator is 6 or less.

[0238] The photoacid generator may be in the form of a low molecular weight compound, or may be incorporated into a part of a polymer. Also, the photoacid generator may be in the form of a low molecular weight compound and in the form of a polymer in combination. The photoacid generator is preferably in the form of a low molecular weight compound. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. When the photoacid generator is in a form incorporated into a part of a polymer, it may be incorporated into a part of the above-mentioned resin (A) and / or resin (X), or it may be incorporated into a resin different from resin (A) and resin (X). The photoacid generator may be used alone or in combination of two or more kinds. In the composition of the present invention, the content of the photoacid generator (the total content when multiple types are present) is preferably 0.1 to 35 mass %, more preferably 0.5 to 25 mass %, even more preferably 0.5 to 20 mass %, and particularly preferably 0.5 to 10 mass %, based on the total solid content of the composition. When the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition (the total content when multiple types are present) is preferably 1 to 35 mass %, more preferably 1 to 30 mass %, based on the total solid content of the composition.

[0239] <(C) Solvent> The composition of the present invention preferably contains a solvent. Examples of solvents that can be used when preparing the composition include organic solvents such as alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactates, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates. Specific examples of these solvents include the solvents described in US Patent Application Publication No. 2008 / 0187860, paragraphs

[0441] to

[0455] , isoamyl acetate, butyl butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

[0240] In the present invention, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure with a solvent having no hydroxyl group may be used as the organic solvent. The solvent having a hydroxyl group and the solvent not having a hydroxyl group can be appropriately selected from the above-mentioned exemplified compounds. As the solvent having a hydroxyl group, alkylene glycol monoalkyl ether or alkyl lactate is preferable, and propylene glycol monomethyl ether (PGME, also known as 1-methoxy-2-propanol) or ethyl lactate is more preferable. Furthermore, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxypropionate, a monoketone compound which may have a ring, a cyclic lactone, or an alkyl acetate is preferable, propylene glycol monomethyl ether acetate (PGMEA, also known as 1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, and butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, and 2-heptanone are even more preferable. The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent having no hydroxyl group (solvent having a hydroxyl group / solvent having no hydroxyl group) is preferably 1 / 99 to 99 / 1, more preferably 10 / 90 to 90 / 10, and further preferably 20 / 80 to 60 / 40. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is particularly preferred from the viewpoint of coating uniformity. The solvent preferably contains propylene glycol monomethyl ether acetate, and is preferably a solvent containing propylene glycol monomethyl ether acetate alone or a mixed solvent containing propylene glycol monomethyl ether acetate.

[0241] The solids concentration of the composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably 40% by mass or more. The solids concentration of the composition of the present invention is preferably 70% by mass or less, and more preferably 60% by mass or less, from the viewpoint of ensuring the coatability of the composition. The solids concentration is the mass percentage of the mass of the components other than the solvent relative to the total mass of the composition.

[0242] <(D) Acid diffusion control agent> The compositions of the present invention also preferably include an acid diffusion controller. The acid diffusion controller traps the acid generated from the photoacid generator or the like upon exposure to light and acts as a quencher that inhibits the reaction of the acid-decomposable resin in the unexposed areas caused by excess acid generated. Examples of the acid diffusion controller that can be used include basic compounds (DA), basic compounds (DB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, onium salts (DC) whose acid generators are weaker acids than the acid generators, low molecular weight compounds (DD) having a nitrogen atom and a group that is eliminated by the action of an acid, and onium salt compounds (DE) having a nitrogen atom in the cation moiety. In the composition of the present invention, known acid diffusion controllers can be appropriately used. For example, the known compounds disclosed in U.S. Patent Application Publication No. 2016 / 0070167A1,

[0627] to

[0664] , U.S. Patent Application Publication No. 2015 / 0004544A1,

[0095] to

[0187] , U.S. Patent Application Publication No. 2016 / 0237190A1, and

[0403] to

[0423] , and U.S. Patent Application Publication No. 2016 / 0274458A1,

[0259] to

[0328] can be used as the acid diffusion controller.

[0243] As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferred.

[0244] [ka]

[0245] In the general formulas (A) and (E), R 200 , R 201 , and R 202 may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). R 201 and R 202 may be bonded to each other to form a ring. R 203 , R 204 , R 205 , and R 206 may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

[0246] The alkyl group in the general formulae (A) and (E) may be substituted or unsubstituted. Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. The alkyl groups in the general formulae (A) and (E) are more preferably unsubstituted.

[0247] The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or the like, and more preferably a compound having an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, or an aniline derivative having a hydroxyl group and / or an ether bond.

[0248] A basic compound (DB) (hereinafter, also referred to as "compound (DB)") whose basicity is reduced or eliminated upon irradiation with actinic rays or radiation is a compound that has a proton acceptor functional group and is decomposed upon irradiation with actinic rays or radiation, thereby reducing or eliminating its proton acceptor property, or changing from proton acceptor property to acidic property.

[0249] The proton acceptor functional group is a functional group having a group or electrons capable of electrostatically interacting with a proton, and means, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having an unshared electron pair that does not contribute to π conjugation. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

[0250] [ka]

[0251] Preferred partial structures of the proton acceptor functional group include, for example, crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, etc.

[0252] Compound (DB) decomposes upon irradiation with actinic rays or radiation to generate a compound whose proton acceptor property is reduced or lost, or whose property changes from a proton acceptor property to an acidic property. Here, the reduction or loss of the proton acceptor property, or the change from a proton acceptor property to an acidic property, is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, it means that the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by measuring the pH.

[0253] The acid dissociation constant pKa of the compound generated by the decomposition of compound (DB) upon irradiation with actinic rays or radiation preferably satisfies pKa < -1, more preferably satisfies -13 < pKa < -1, and even more preferably satisfies -13 < pKa < -3.

[0254] The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.). A lower value of the acid dissociation constant pKa indicates a stronger acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by using an infinitely diluted aqueous solution and measuring the acid dissociation constant at 25°C. Alternatively, using the following software package 1, a value based on Hammett's substituent constant and a database of known literature values can also be obtained by calculation. All the pKa values described in this specification indicate values obtained by calculation using this software package.

[0255] Software package 1: Advanced Chemistry Develo pment (ACD / Labs) Software V8.14 for Sola ris (1994-2007 ACD / Labs).

[0256] In the composition of the present invention, an onium salt (DC) that is a relatively weak acid compared to the photoacid generator can be used as an acid diffusion controller. When a photoacid generator is used in combination with an onium salt that generates an acid that is weaker than the acid generated by the photoacid generator, the acid generated by the photoacid generator upon irradiation with actinic rays or radiation collides with an onium salt having an unreacted weak acid anion, releasing the weak acid through salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic activity, and the acid appears to be deactivated, thereby enabling control of acid diffusion.

[0257] As the onium salt which is a relatively weak acid to the photoacid generator, the compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

[0258] [ka]

[0259] In the formula, R 51 is a hydrocarbon group which may have a substituent; Z 2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon adjacent to S is not substituted with a fluorine atom), R 52 is an organic group, and Y 3 is a linear, branched, or cyclic alkylene or arylene group, Rf is a hydrocarbon group containing a fluorine atom, M + are each independently an ammonium cation, a sulfonium cation, or an iodonium cation.

[0260] M +Preferred examples of the sulfonium cation or iodonium cation represented by the following general formula (ZI) and the iodonium cation represented by the following general formula (ZII) are mentioned.

[0261] The onium salt (DC) which is a weak acid relative to the photoacid generator may be a compound having a cationic moiety and an anionic moiety in the same molecule, and in which the cationic moiety and the anionic moiety are linked by a covalent bond (hereinafter also referred to as "compound (DCA)"). The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

[0262] [ka]

[0263] In general formulas (C-1) to (C-3), R 1 , R 2 , and R 3 each independently represents a substituent having 1 or more carbon atoms. L 1 represents a divalent linking group or a single bond that links a cationic moiety and an anionic moiety. -X - -COO - , -SO 3 - , -SO 2 - , and -N - -R 4 R represents an anionic moiety selected from 4 The linking site to the adjacent N atom is a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) 2 It represents a monovalent substituent having at least one of a sulfinyl group (-S(=O)-) and a sulfinyl group (-S(=O)-). R 1 , R 2 , R 3 , R 4 , and L 1may be bonded to each other to form a ring structure. 1 ~R 3 Two of these may be combined to represent one divalent substituent, which may be bonded to the N atom via a double bond.

[0264] R 1 ~R 3 Examples of the substituent having one or more carbon atoms in include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylaminocarbonyl group, and an arylaminocarbonyl group. Among these, an alkyl group, a cycloalkyl group, or an aryl group is preferable.

[0265] L as a divalent linking group 1 L includes linear or branched alkylene groups, cycloalkylene groups, arylene groups, carbonyl groups, ether bonds, ester bonds, amide bonds, urethane bonds, urea bonds, and groups formed by combining two or more of these. 1 is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

[0266] The low molecular weight compound (DD) having a nitrogen atom and a group that can be eliminated by the action of an acid (hereinafter also referred to as "compound (DD)") is preferably an amine derivative having, on the nitrogen atom, a group that can be eliminated by the action of an acid. The group which is eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and even more preferably from 100 to 500. The compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

[0267] [ka]

[0268] In general formula (d-1), Each Rb independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group (preferably having 1 to 10 carbon atoms), or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rbs may be bonded to each other to form a ring. The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb may each independently be substituted with a functional group such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, or an oxo group, an alkoxy group, or a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

[0269] Rb is preferably a linear or branched alkyl group, a cycloalkyl group, or an aryl group, and more preferably a linear or branched alkyl group, or a cycloalkyl group. Examples of the ring formed by two Rb's bonding with each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof. Specific examples of the group represented by formula (d-1) include, but are not limited to, the structures disclosed in US Patent Publication US2012 / 0135348A1,

[0466] .

[0270] The compound (DD) preferably has a structure represented by the following general formula (6).

[0271] [ka]

[0272] In general formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and l+m=3 is satisfied. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra may be the same or different, and the two Ra may be linked together to form a heterocycle together with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula. Rb has the same meaning as Rb in general formula (d-1) above, and preferred examples are also the same. In general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Ra may each independently be substituted with the same groups as those described above as the groups with which the alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb may be substituted.

[0273] Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (which may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. In one embodiment, it is also preferred that in general formula (6), l is 2, m is 1, and the two Ra's are mutually linked to form a heterocycle together with the nitrogen atom in the formula. Specific examples of compound (DD) include the compounds disclosed in paragraph

[0475] of the specification of US Patent Application Publication No. 2012 / 0135348A1.

[0274] The onium salt compound (DE) having a nitrogen atom in the cationic moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic moiety containing a nitrogen atom in the cationic moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is further preferable that all atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Furthermore, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, or a halogen atom) is not directly bonded to the nitrogen atom. Preferred specific examples of compound (DE) include the compounds disclosed in paragraph

[0203] of the specification of U.S. Patent Application Publication No. 2015 / 0309408A1.

[0275] Preferred examples of the acid diffusion controller are shown below.

[0276] [ka]

[0277] [ka]

[0278] In the composition of the present invention, the acid diffusion controller (D) may be used alone or in combination of two or more kinds. The content of the acid diffusion controller (the total content when a plurality of types are present) is preferably from 0.05 to 10 mass %, more preferably from 0.05 to 5 mass %, based on the total solid content of the composition.

[0279] <(E) Hydrophobic resin> The composition of the present invention may contain a hydrophobic resin. The hydrophobic resin is preferably different from the resin (A) and the resin (X). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of polar / non-polar substances.

[0280] Hydrophobic resins are made of fluorine atoms, silicon atoms, and CH atoms contained in the side chains of the resin, from the viewpoint of uneven distribution on the surface of the film. 3 It is preferable that the resin has a repeating unit having at least one selected from the group consisting of “a partial structure”. When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain or in a side chain of the resin.

[0281] When the hydrophobic resin contains a fluorine atom, it is preferable that the hydrophobic resin has, as a partial structure having a fluorine atom, an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

[0282] The hydrophobic resin preferably has at least one group selected from the following group (x) to (z): (x) Acid group (y) A group that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group) (z) Groups that decompose when subjected to the action of acid

[0283] Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group. The acid group is preferably a fluorinated alcohol group (such as hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl)methylene group.

[0284] Examples of the group (y) that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer include a lactone group, a carboxylate group (-COO-), an acid anhydride group (-C(O)OC(O)-), an acid imide group (-NHCONH-), a carboxylate thioester group (-COS-), a carbonate group (-OC(O)O-), a sulfate group (-OSO 2 O-) and sulfonate ester groups (-SO 2 Of these, a lactone group or a carboxylate group (-COO-) is preferred. Examples of the repeating units containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, such as repeating units of acrylic acid esters and methacrylic acid esters. These groups may be bonded to the main chain of the resin via a linking group in these repeating units. Alternatively, these repeating units may be introduced to the end of the resin by using a polymerization initiator or chain transfer agent having these groups during polymerization. Examples of the repeating unit having a lactone group include the repeating units having a lactone structure described above in the section on resin (A).

[0285] The content of the repeating unit having a group (y) that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer is preferably from 1 to 100 mol %, more preferably from 3 to 98 mol %, and even more preferably from 5 to 95 mol %, based on the total repeating units in the hydrophobic resin (E).

[0286] In the hydrophobic resin (E), the repeating unit having a group (z) decomposed by the action of an acid may be the same as the repeating unit having an acid decomposable group as exemplified in the resin (A). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) decomposed by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and even more preferably 20 to 60 mol% based on the total repeating units in the hydrophobic resin (E). The hydrophobic resin (E) may further have a repeating unit other than the repeating units described above.

[0287] The content of the fluorine atom-containing repeating unit is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, based on all repeating units in the hydrophobic resin (E), and the content of the silicon atom-containing repeating unit is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, based on all repeating units in the hydrophobic resin (E).

[0288] On the other hand, the hydrophobic resin (E) has CH 3 In the case where the partial structure is contained, the hydrophobic resin (E) is preferably substantially free of fluorine atoms and silicon atoms. In addition, the hydrophobic resin (E) is preferably substantially composed of repeating units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

[0289] The weight average molecular weight of the hydrophobic resin (E) is preferably from 1,000 to 100,000, and more preferably from 1,000 to 50,000.

[0290] The total content of residual monomer and / or oligomer components contained in the hydrophobic resin (E) is preferably 0.01 to 5 mass%, more preferably 0.01 to 3 mass%, and the dispersity (Mw / Mn) is preferably 1 to 5, more preferably 1 to 3.

[0291] As the hydrophobic resin (E), known resins can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in US Patent Application Publication No. 2015 / 0168830A1,

[0451] to

[0704] and US Patent Application Publication No. 2016 / 0274458A1,

[0340] to

[0356] can be suitably used as the hydrophobic resin (E). In addition, the repeating units disclosed in US Patent Application Publication No. 2016 / 0237190A1,

[0177] to

[0258] are also preferred as repeating units constituting the hydrophobic resin (E).

[0292] Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) are shown below.

[0293] [ka]

[0294] [ka]

[0295] The hydrophobic resin (E) may be used alone or in combination of two or more kinds. It is preferable to use a mixture of two or more hydrophobic resins (E) having different surface energies from the viewpoint of achieving both immersion liquid followability in immersion exposure and development characteristics. The content of the hydrophobic resin (E) in the composition is preferably from 0.01 to 10 mass %, more preferably from 0.05 to 8 mass %, based on the total solid content in the composition of the present invention.

[0296] <(G) Crosslinking agent> The composition of the present invention also preferably includes a crosslinking agent. The crosslinking agent is preferably a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as crosslinking agent (G)). As the crosslinking agent (G), a known compound can be appropriately used. For example, the known compounds disclosed in U.S. Patent Application Publication No. 2016 / 0147154A1, paragraphs

[0379] to

[0431] , and U.S. Patent Application Publication No. 2016 / 0282720A1, paragraphs

[0064] to

[0141] can be suitably used as the crosslinking agent (G). The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking a resin. Examples of the crosslinkable group include a hydroxymethyl group, an alkoxymethyl group (such as a methoxymethyl group), an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, and an oxetane ring. A hydroxymethyl group, an alkoxymethyl group, an oxirane ring, or an oxetane ring is preferable.

[0297] The crosslinking agent (G) is preferably a phenol derivative, a urea compound (a compound having a urea structure), or a melamine compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group, and from the viewpoint of etching resistance, a phenol derivative is more preferable. Among them, the hydroxymethyl group and the alkoxymethyl group are preferably directly bonded to an aromatic ring group. It is also preferable that the aromatic ring group is further bonded to a hydroxyl group and / or an alkyl group having 1 to 6 carbon atoms.

[0298] By including the crosslinker (G), the molecular weight of the exposed area increases, and the solubility in organic solvents decreases. On the other hand, the solubility in organic solvents of the unexposed area increases due to the low molecular weight crosslinker (G), and the difference in dissolution rate between the exposed area and the unexposed area can be increased. As a result, it is possible to improve the shape quality by suppressing film loss in the pattern, and to reduce defects such as eliminating poor removal due to insufficient dissolution rate in the unexposed area. The crosslinking agent (G) is preferably a compound (including a resin) having two or more (e.g., 2 to 10) crosslinkable groups (such as hydroxymethyl groups and / or alkoxymethyl groups), and more preferably a compound (including a resin) having only two crosslinkable groups. When the polymer has only two crosslinkable groups, the increase in molecular weight of the polymer due to the crosslinking reaction proceeds slowly, and gelation that accompanies the increase in molecular weight accompanied by gelation can be suppressed, thereby reducing defects in the formed pattern.

[0299] The crosslinking agent (G) is preferably a compound represented by any one of the following general formulas (G1) to (G3).

[0300] [ka]

[0301] In general formulas (G1) to (G3), L 1 and L 2 each independently represents a crosslinkable group, and is preferably a hydroxymethyl group, a methoxymethyl group, or an ethoxymethyl group.

[0302] The crosslinking agent (G) may be a commercially available product or may be synthesized by a known method.

[0303] For example, a phenol derivative having a hydroxymethyl group can be obtained by replacing the corresponding phenol compound not having a hydroxymethyl group (L in the above general formulae (G1) to (G3)). 1 and L 2It can be obtained by reacting a compound in which 1 is a hydrogen atom or the like) with formaldehyde in the presence of a base catalyst. In this case, in order to prevent resinification or gelation, it is preferable to carry out the reaction at a temperature of 60° C. or less. Specifically, it can be synthesized by the methods described in JP-A-6-282067, JP-A-7-064285, etc.

[0304] Phenol derivatives having an alkoxymethyl group can be obtained by reacting a phenol derivative having a corresponding hydroxymethyl group with an alcohol in the presence of an acid catalyst. In this case, in order to prevent resinification or gelation, it is preferable to carry out the reaction at a temperature of 100° C. or less. Specifically, they can be synthesized by the method described in European Patent Application Publication No. 0632003. Phenol derivatives having a hydroxymethyl group or an alkoxymethyl group thus synthesized are preferable in terms of storage stability, and among them, phenol derivatives having an alkoxymethyl group are more preferable. Such phenol derivatives having two or more (e.g., 2 to 10) hydroxymethyl groups or alkoxymethyl groups concentrated or distributed on any of the benzene rings may be used alone or in combination of two or more.

[0305] Examples of the crosslinking agent (G) also include the following compounds having an N-hydroxymethyl group, an N-alkoxymethyl group, or an N-acyloxymethyl group, and epoxy compounds.

[0306] [ka]

[0307] The crosslinking agent (G) may be used alone or in combination of two or more kinds. The content of the crosslinking agent (G) is preferably from 1 to 50 mass %, more preferably from 2 to 30 mass %, and even more preferably from 2 to 20 mass %, based on the total solid content of the composition of the present invention.

[0308] <(H) Surfactant> The composition of the present invention also preferably comprises a surfactant. The surfactant is preferably a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom).

[0309] By including a surfactant in the composition of the present invention, the spin-coatability is improved, and the in-plane uniformity of the film thickness of the composition after spin-coating on a substrate is improved. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in

[0276] of US Patent Application Publication No. 2008 / 0248425. In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in

[0280] of US Patent Application Publication No. 2008 / 0248425 can also be used.

[0310] The surfactant may be used alone or in combination of two or more kinds. By making the content of the surfactant 10 ppm (parts per million) or more based on the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased, which makes the surface of the actinic ray-sensitive or radiation-sensitive film more hydrophobic and improves water tracking during immersion exposure. In particular, when the composition of the present invention contains a surfactant, the content thereof is preferably from 0.0001 to 2 mass %, and more preferably from 0.0005 to 1 mass %, based on the total solid content of the composition.

[0311] <Other additives> The compositions of the present invention may contain other additives than those mentioned above. Other additives include onium carboxylates, such as the compounds described in

[0605] to

[0606] of U.S. Patent Application Publication No. 2008 / 0187860. These onium carboxylates can be synthesized by reacting a sulfonium hydroxide, iodonium hydroxide, or ammonium hydroxide with a carboxylic acid and silver oxide in a suitable solvent.

[0312] When the composition of the present invention contains an onium carboxylate, the content thereof is preferably from 0.1 to 20 mass %, more preferably from 0.5 to 10 mass %, and even more preferably from 1 to 7 mass %, based on the total solid content of the composition. The composition of the present invention may further contain, as necessary, an acid amplifier, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, and / or a dissolution inhibitor and a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, an alicyclic or aliphatic compound having a carboxyl group), and the like.

[0313] Such phenol compounds having a molecular weight of 1000 or less can be synthesized by referring to the methods described in, for example, JP-A-4-122938, JP-A-2-028531, US Pat. No. 4,916,210, or European Patent No. 219294. Examples of alicyclic or aliphatic compounds having a carboxyl group include carboxylic acid derivatives having a steroid structure, such as cholic acid, deoxycholic acid, and lithocholic acid, adamantanecarboxylic acid derivatives, adamantanedicarboxylic acid, cyclohexanecarboxylic acid, and cyclohexanedicarboxylic acid.

[0314] The composition of the present invention is preferably used by dissolving the above components in a given organic solvent (preferably the above-mentioned mixed solvent), filtering the solution, and then coating the solution on a given substrate. The pore size of the filter used for filtration is preferably 1.0 μm or less, more preferably 100 nm or less, and even more preferably 10 nm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon. In filtration, for example, as in JP-A-2002-62667, cyclic filtration may be performed, or multiple types of filters may be connected in series or parallel to perform filtration. The composition may also be filtered multiple times. Furthermore, the composition may be subjected to degassing treatment before or after filtration.

[0315] The composition of the present invention is usually a composition for forming an actinic ray- or radiation-sensitive film (resist film) having a thickness of 1 μm or more, preferably a composition for forming a resist film having a thickness of 10 μm or more, and more preferably a composition for forming a resist film having a thickness of 15 μm or more. The upper limit of the film thickness is, for example, preferably 30 μm or less, more preferably less than 30 μm, even more preferably less than 25 μm, and particularly preferably less than 20 μm.

[0316] [Pattern Forming Method] A specific procedure for forming a pattern will now be described. As described above, the pattern forming method of the present invention includes the steps of: (i) forming a resist film having a thickness of 10 μm or more using the composition (film forming process); (ii) a step of irradiating the resist film with KrF light (exposure step); and (iii) a step of developing the resist film irradiated with the KrF light using a predetermined developer to form a negative pattern (development step); The pattern forming method includes the steps of: The composition and developer used in the pattern forming method are as described above.

[0317] The pattern forming method of the present invention may include the exposure step (ii) multiple times. (ii) An example of a method including multiple exposure steps is multiple exposure. The term "multiple exposure" refers to exposing a resist film to multiple focal depths using KrF light, with each of these focal depths covering a different region within the resist film. In the multiple exposure, it is preferable to expose a plurality of focal depths in the film thickness direction. The pattern forming method of the present invention also preferably includes, after the exposure step (ii), a heating step (iv). The pattern formation method of the present invention may include the heating step (iv) multiple times.

[0318] In the pattern forming method of the present invention, the step of forming a resist film on a substrate using the composition of the present invention, the exposure step, and the development step can be carried out by generally known methods. Each step will be described below.

[0319] <(i) Film formation process> In the present invention, the substrate on which the resist film is formed is not particularly limited, and examples thereof include silicon, SiN, SiO 2 Substrates that are generally used in the manufacturing process of semiconductors such as ICs (Integrated Circuits), manufacturing processes of circuit boards such as liquid crystals and thermal heads, and other lithography processes of photofabrication can be used. Furthermore, an anti-reflection film may be formed between the resist film and the substrate, as necessary. As the anti-reflection film, known organic and inorganic anti-reflection films can be appropriately used.

[0320] As described above, the thickness of the resist film formed in the pattern forming method of the present invention is 10 μm or more, and preferably 15 μm or more. The upper limit of the thickness of the resist film is, for example, preferably 30 μm or less, more preferably less than 30 μm, even more preferably less than 25 μm, and particularly preferably less than 20 μm. The same applies to the preferred range of the thickness (height) of the pattern formed.

[0321] After the film formation, it is also preferable to include a prebake step (PB) before the exposure step. The heating temperature in the pre-heating step is preferably from 70 to 160°C, and more preferably from 80 to 150°C. The heating time in the pre-heating step is preferably from 30 to 300 seconds, more preferably from 30 to 180 seconds, and even more preferably from 30 to 90 seconds. Heating can be carried out by a means provided in a normal exposure / developing machine, and may also be carried out using a hot plate or the like.

[0322] <(ii) Exposure process> The wavelength of the light source used in the exposure device in the present invention is 200 to 300 nm, and therefore the light source is a KrF excimer laser (248 nm).

[0323] It is also preferable to include a post-exposure bake (PEB) step after the exposure step and before the development step. The heating temperature in the post-exposure baking step is preferably from 70 to 160°C, and more preferably from 80 to 150°C. The heating time in the post-exposure heating step is preferably from 30 to 300 seconds, more preferably from 30 to 180 seconds, and even more preferably from 30 to 90 seconds. Heating can be carried out by a means provided in a normal exposure machine and / or developing machine, and may also be carried out using a hot plate or the like. Heating promotes the reaction of the exposed areas, improving the sensitivity and pattern profile.

[0324] <(iii) Development process> The developing method using the developer used in the present invention will be described below. As a developing method, for example, a method of immersing a substrate 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 substrate surface by surface tension and leaving it to stand for a certain period of time (paddle method), a method of spraying the developing solution on the substrate surface (spray method), and a method of continuously discharging the developing solution while scanning a developing solution discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method) can be applied.

[0325] When the above-mentioned various developing methods include a step of discharging a developer from a developing nozzle of a developing device toward a resist film, the discharge pressure of the discharged developer (flow rate of the discharged developer per unit area) is 2 mL / sec / mm 2 Less than 1.5mL / sec / mm is preferable. 2 Less than 1mL / sec / mm is more preferable. 2 There is no particular lower limit to the flow rate, but 0.2 mL / sec / mm is preferable in consideration of throughput. 2 The above is preferred. By controlling the discharge pressure of the discharged developer within the above range, defects in the pattern caused by resist residues after development can be significantly reduced. Although the details of this mechanism are unclear, it is believed that, by setting the discharge pressure within the above range, the pressure that the developer exerts on the resist film is reduced, thereby preventing the resist film and resist pattern from being inadvertently scraped or crumbled. The discharge pressure of the developer (mL / sec / mm 2 ) is the value at the outlet of the developing nozzle in the developing device.

[0326] Examples of methods for adjusting the discharge pressure of the developer include a method for adjusting the discharge pressure with a pump or the like, and a method for changing the pressure by adjusting the pressure when supplied from a pressure tank. After the step of developing using the developer, a step of stopping the development while replacing the developer with another solvent may be carried out.

[0327] <Rinse process> After the development step, a step of washing with a rinse liquid (rinsing step) may be carried out. The rinse liquid used in the rinse step after the development step is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. For example, the rinse liquid may be a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Specific examples of the hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include the same solvents that can be used in the developer.

[0328] After the development step, it is preferable to carry out a step of cleaning with a rinsing liquid containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and hydrocarbon-based solvents, it is more preferable to carry out a step of cleaning with a rinsing liquid containing an alcohol-based solvent or an ester-based solvent, it is even more preferable to carry out a step of cleaning with a rinsing liquid containing a monohydric alcohol, and it is particularly preferable to carry out a step of cleaning with a rinsing liquid containing a monohydric alcohol having 5 or more carbon atoms.

[0329] Here, examples of the monohydric alcohol used in the rinsing step include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, and 4-octanol can be used. Particularly preferred examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol. The hydrocarbon solvent used in the rinsing step is preferably a hydrocarbon compound having 6 to 30 carbon atoms, more preferably a hydrocarbon compound having 8 to 30 carbon atoms, still more preferably a hydrocarbon compound having 7 to 30 carbon atoms, and particularly preferably a hydrocarbon compound having 10 to 30 carbon atoms. Among these, the use of a rinsing liquid containing decane and / or undecane can suppress pattern collapse.

[0330] Each component may be used in combination with a plurality of other components, or may be used in combination with an organic solvent other than those mentioned above. The water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By keeping the water content at 10% by mass or less, good development characteristics can be obtained. The lower limit of the water content in the rinse solution is 0% by mass.

[0331] The vapor pressure of the rinse liquid used after the step of developing with a developer containing an organic solvent is preferably 0.05 to 5 kPa, more preferably 0.1 to 5 kPa, and even more preferably 0.12 to 3 kPa at 20° C. By setting the vapor pressure of the rinse liquid to 0.05 to 5 kPa, the temperature uniformity within the substrate surface is improved, and further swelling caused by the penetration of the rinse liquid is suppressed, improving the dimensional uniformity within the wafer surface.

[0332] The rinse solution may contain a suitable amount of a surfactant.

[0333] In the rinsing step, the developed substrate is preferably washed with a rinsing liquid containing the above organic solvent. The cleaning method is not particularly limited, and examples of the method that can be used include a method in which a rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed for a certain period of time in a tank filled with a rinsing liquid (dip method), and a method in which a rinsing liquid is sprayed onto the substrate surface (spray method). Among these, the spin coating method is preferable for performing the cleaning method.

[0334] After the developing step or rinsing step, it is also preferable to rotate the substrate at a rotation speed of 2000 to 4000 rpm to remove the developing solution and / or the rinsing solution from the substrate. It is also preferable to include a heating step (Post Bake) after the developing step or the rinsing step. The developer and / or rinsing solution remaining between the patterns and inside the patterns is removed by baking. The heating step is usually performed at 40 to 160°C (preferably 70 to 95°C) for 10 seconds to 3 minutes (preferably 30 to 90 seconds).

[0335] After the developing step or the rinsing step, a treatment can be carried out to remove the developer or rinsing liquid adhering to the pattern using a supercritical fluid.

[0336] <Other processes> A method for improving the surface roughness of a pattern formed by the method of the present invention may be applied. For example, a method for improving the surface roughness of a pattern may be a method for treating a resist pattern with plasma of a gas containing hydrogen, as disclosed in International Publication No. 2014 / 002808. In addition, known methods such as those described in JP 2004-235468 A, U.S. Patent Publication No. 2010 / 0020297, JP 2009-19969 A, or Proc. of SPIE Vol.8328 83280N-1 "EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement" may be applied. The pattern formation method of the present invention can also be used for guide pattern formation in DSA (Directed Self-Assembly) (see, for example, ACS Nano Vol. 4 No. 8 Pages 4815-4823). Furthermore, the resist pattern formed by the above method can be used as a core for the spacer process disclosed in, for example, JP-A-3-270227 and JP-A-2013-164509. EXAMPLES

[0337] The present invention will be described below with reference to examples, but the present invention is not limited thereto.

[0338] [Preparation of actinic ray- or radiation-sensitive resin composition (composition)] The actinic ray-sensitive or radiation-sensitive resin composition (composition) used in the test was prepared by the method described below. A resist solution was prepared by mixing the components shown in Table 1 below, and the resist solution obtained was filtered through a UPE (ultra high molecular weight polyethylene) filter having a pore size of 1.0 μm. In this way, a composition containing each component as shown in Table 1 was prepared.

[0339] [Table 1]

[0340] Details of each component in Table 1 above are as follows.

[0341] ·resin The structures of the resins used in the preparation of the compositions are as follows: The numerical value attached to each repeating unit in the structure shown below indicates the content (molar ratio) of each repeating unit relative to all repeating units in the resin. The resin used in the preparation of the composition had a weight average molecular weight (Mw) of 22,000 and a dispersity (Mw / Mn) of 1.65.

[0342] [ka]

[0343] Photoacid generator The structures of the photoacid generators used in the preparation of the compositions are as follows:

[0344] [ka]

[0345] Acid diffusion control agent The structures of the acid diffusion controllers used in the preparation of the compositions are as follows:

[0346] [ka]

[0347] Crosslinking agent The structure of the crosslinker used in the preparation of the composition is as follows:

[0348] [ka]

[0349] Surfactants The structures of the surfactants used in the preparation of the compositions are as follows:

[0350] [ka]

[0351] ·solvent The solvents used in the preparation of the compositions are as follows: PGMEA: Propylene glycol monomethyl ether acetate PGME: Propylene glycol monomethyl ether EL: Ethyl lactate

[0352] [Refining the developer] An organic solvent (butyl acetate, commercially available) was prepared as the liquid to be purified. Next, the organic solvent was dehydrated using a water adsorbent (Molecular Sieve 3A, manufactured by Union Showa Co., Ltd.) before being purified by a purification apparatus described below. Next, a purification apparatus was prepared in which the following were connected in the order listed from the upstream side: "a first distillation section having a first plate distillation column without a pressure reduction mechanism (used for the distillation process for crude distillation)", "a first packed section having three packed columns packed with cation exchange resin connected in series (used for the ion removal process)", "a second packed section having two packed columns packed with anion exchange resin connected in series (used for the ion removal process)", "a second distillation section having a second plate distillation column without a pressure reduction mechanism and a third plate distillation column equipped with a pressure reduction mechanism connected in series in the above order (used for the distillation process for rectification treatment)", and "a filtration section having a first filter and a second filter connected in series in the above order (used for the filtration process)". The liquid to be purified was purified using the purification device to produce a developing solution. The purification of the liquid to be purified was performed a total of two times, with each time passing the liquid through the purification device being counted as one time.

[0353] The details of each component in the refining apparatus are shown below, starting from the upstream side (primary side). · First tray distillation column (number of theoretical plates: 10) Cation exchange resin (ORLITE DS-4, Organo Corporation) Anion exchange resin (ORLITE DS-6, Organo Corporation) · Second tray distillation column (theoretical plate number: 23 plates) - 3rd plate distillation column (theoretical number of plates: 23, reduced pressure distillation) First filter (Purasol SP / SN solvent purifier, Entegris, UPE (ultra-high molecular weight polyethylene) filter, pore size 5 nm) - Second filter (product name "Torrent", manufactured by Entegris, polytetrafluoroethylene (PTFE) filter, pore size 5 nm)

[0354] The liquid to be purified (butyl acetate) was purified using the purification device to produce developer 3 used in Examples 3 to 6. More specifically, one pass of the liquid to be purified through the purification device was counted as one pass, and the liquid to be purified was passed through the purification device a total of two times to obtain a developer.

[0355] In addition, the above purification method was modified by one or more of the following changes to obtain a developer (butyl acetate) for use in other examples or comparative examples: "changing the type of organic solvent, which is the purified liquid, to propyl acetate or isopentyl acetate," "omitting the first packed section from the purification apparatus," "omitting the second packed section from the purification apparatus," "changing the number of theoretical plates of the second plate distillation column and / or the third plate distillation column of the purification apparatus," "mixing appropriate amounts of unpurified butyl acetate, water, acetic acid, and 1-butanol with the purified liquid after purification," and "changing the number of times the liquid is passed through the purification apparatus." For example, developer 22 used in Comparative Example 5 was prepared in the same manner as in the production method of developer 3, except that the number of times the solution was passed through the purification device was changed to four times. Details of each organic solvent developer are shown in Table 2.

[0356] 〔measurement〕 The contents of each component contained in the developer were measured by the methods described below. All of the following measurements were carried out in a clean room that met ISO (International Organization for Standardization) Class 2 or lower. The results are summarized in Table 2. The content of each component in the developer was measured immediately after preparation of the developer.

[0357] <Measurement of components with hydroxyl groups other than water> The types and contents of compounds having a hydroxyl group other than water in each developer were measured using a gas chromatograph mass spectrometer (product name "GCMS-2020", manufactured by Shimadzu Corporation, measurement conditions are as follows). However, water was not included in the measurement. In all of the developers, the only compounds having a hydroxyl group detected were carboxylic acids having 1 to 5 carbon atoms and alcohols having 1 to 5 carbon atoms.

[0358] (Measurement conditions) Capillary column: InertCap 5MS / NP 0.25mml. Sample introduction method: Split 75kPa constant pressure Vaporizer temperature: 230℃ Column oven temperature: 80℃ (2min) - 500℃ (13min) Heating rate: 15℃ / min Carrier gas: Helium Septum purge flow rate: 5mL / min Split ratio: 25:1 Interface temperature: 250℃ Ion source temperature: 200℃ Measurement mode: Scan_m / z=85~500 Sample introduction volume: 1uL

[0359] <Moisture measurement> The amount of water (water content) in each developer was measured using a Karl Fischer moisture meter (product name "MKC-710M", manufactured by Kyoto Electronics Manufacturing Co., Ltd., Karl Fischer coulometric titration type).

[0360] <Metal component measurement> The content of metal components in each developer was measured by ICP-MS using NexLION350C (trade name, manufactured by PerkinElmer) to measure the content of metal components in the processing solutions of the Examples and Comparative Examples. The specific measurement conditions for the ICP-MS method are as follows: The amount of detection was measured based on the peak intensity against a standard solution of known concentration, and converted into the mass of the metal component to calculate the content of the metal component in the developer used in the measurement. (standard material) Ultrapure water was measured and poured into a clean glass container, and metal particles to be measured with a median diameter of 50 nm were added to a concentration of 10,000 particles / ml. After that, Japanese cedar was treated in an ultrasonic cleaner for 30 minutes and used as a standard substance. (ICP-MS measurement conditions) The ICP-MS used a PFA coaxial nebulizer, a quartz cyclone-type spray chamber, and a quartz torch injector with an inner diameter of 1 mm, and the liquid to be measured was aspirated at approximately 0.2 ml / min. The oxygen addition amount was 0.1 L / min, the plasma output was 1600 W, and the cell was purged with ammonia gas. The analysis was performed with a time resolution of 50 μs. (Analysis software) The metal content was calculated using the following analysis software provided by the manufacturer. Syngistix for ICP-MS Software

[0361] In the developers 1 to 22, the total content of metal components including metal elements selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn was 10 ppt by mass to 1 ppb by mass.

[0362] [test] [Pattern formation] Using a spin coater "ACT-8" manufactured by Tokyo Electron, the composition prepared above was dropped onto an 8-inch Si substrate (manufactured by Advanced Materials Technology Corp. (hereinafter also referred to as "wafer" or "substrate")) that had been treated with hexamethyldisilazane, without providing an anti-reflective layer, while the substrate was stationary. After the dropping, the substrate was rotated and the rotation speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, then at 500 rpm for another 3 seconds, then at 100 rpm for 2 seconds again, and then increased to a film thickness setting rotation speed (a rotation speed at which the resist film formed has a film thickness shown in Table 2) and maintained for 60 seconds. Then, the substrate was baked (PreBake; PB) at 150° C. for 60 seconds on a hot plate to form a resist film having a film thickness (μm) shown in Table 2.

[0363] The wafer on which the resist film was formed was subjected to pattern exposure through an exposure mask using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm, NA 0.8). After that, it was baked at 115°C for 60 seconds (Post Exposure Bake; PEB), developed with the developer shown in Table 2 for 60 seconds, and then spin-dried. As a result, an isolated space pattern with a space width of 400 nm and a pitch width of 3000 nm was obtained.

[0364] <Evaluation of pattern resolution> The substrate having the isolated space pattern thus produced was cut and coated with Pt, and the cut surface was observed using a scanning electron microscope (Hitachi S4800). The rectangularity of the pattern and the presence or absence of insufficient dissolution in the space were observed, and the pattern resolution was evaluated as being classified into A or B as follows. A: The pattern has good rectangularity and there is no incomplete dissolution of the space. B: At least one of the following defects occurs: poor rectangularity of the pattern or insufficient dissolution of the space portion.

[0365] <Evaluation of bridge defect suppression> The number of bridge defects in the formed pattern was confirmed by the following method. That is, the patterns were measured in random mode using a defect inspection device KLA2935 (product name) manufactured by KLA-Tencor Corporation, with the pixel size of the defect inspection device set to 0.05 μm and the threshold set to 50. Differences caused by pixel-by-pixel overlay with a comparison image were extracted to detect defects in the pattern formation area in the wafer of each example or comparative example. The detected defects were observed with an eDR7380 (product name) manufactured by KLA-Tencor Corporation, and the number of bridge defects per unit area (number / cm 2 ) was evaluated. The smaller the number of bridging defects, the better the bridging defect suppression ability.

[0366] [Static electricity generation (charge amount) evaluation] One end of a PFA (tetrafluoroethylene-perfluoroalkylvinylether copolymer) tube 302 (manufactured by Nichias Corporation, outer diameter: 6.35 mm, inner diameter: 4.35 mm, length: 10 m) was connected to a canister can 304 with a volume of 18 L containing a developer. A cock 306 was attached immediately before the piping outlet at the other end, and an aluminum tape 308 with a thickness of 0.05 mm was wrapped around the surface of the PFA tube 302 just before the cock 306, and a probe 312 of a surface potential measuring instrument 310 (manufactured by Kasuga Electric Co., Ltd., KSD-3000) was placed 10 mm from the surface of the aluminum tape. A stainless steel container 314 was placed directly under the outlet of the PFA tube 302 to receive the solvent. Finally, the canister can, the PFA tube, and the stainless steel container were placed on a Teflon (registered trademark) sheet 316 with a thickness of 1 cm. An earth wire 318 was attached to the stainless steel container, and it was grounded so that the charge of the developer could be removed. The canister 304 was pressurized to 0.05 MPa with nitrogen flowing in through the nitrogen inlet line 320, and the tap 306 on the opposite side was opened to discharge the developer. At this time, the potential on the surface of the PFA tube 302 was measured to determine the amount of charge on the developer. A schematic diagram of the charge amount measurement system is shown in Figure 1. The results are shown in Table 2.

[0367] The results of the test are shown in the table below. In the table, the column "Composition" indicates the type of composition used in forming the resist film and pattern. The "film thickness (μm)" column indicates the film thickness (height) of the formed resist film and pattern. The "Developer" column indicates the type of developer used in the examples or comparative examples. The "Solvent type" column indicates the type of organic solvent used as the liquid to be purified to obtain the developer. The column "Carboxylic Acid (ppm)" indicates the total content (ppm by mass) of carboxylic acids having 1 to 5 carbon atoms contained in the developer used relative to the total mass of the developer. The column "Alcohol (ppm)" indicates the total content (ppm by mass) of alcohols having 1 to 5 carbon atoms contained in the developer used relative to the total mass of the developer. The column "Water content (ppm)" indicates the content (mass ppm) of water contained in the developer used relative to the total mass of the developer. The "Total (ppm)" column indicates the total content (ppm by mass) of the carboxylic acid, the alcohol, and the water contained in the developer used relative to the total mass of the developer. The column "Charge Amount (mV)" indicates the charge amount of the developer measured by the method shown in the above-mentioned [Evaluation of Static Electricity Generation Amount (Charge Amount)].

[0368] [Table 2]

[0369] From Table 2, it was confirmed that when a pattern is formed using the pattern formation method of the present invention, even when a resist film having a thickness of 10 μm or more is exposed to KrF light to form a pattern, a fine pattern having an excellent pattern shape and suppressed occurrence of defects can be formed.

[0370] In addition, it was confirmed that the effects of the present invention are more excellent when the total content of carboxylic acids having 1 to 5 carbon atoms, the total content of alcohols having 1 to 5 carbon atoms, and the content of water are each independently 2000 mass ppm or less with respect to the total mass of the developer (see comparison between Examples 1, 11, 15, and 19 and Examples 2 to 3, 8 to 10, 12 to 14, and 16 to 18, etc.).

[0371] In order to further suppress the occurrence of defects, it has been confirmed that the film thickness of the exposed resist film and the formed pattern is preferably less than 30 μm, more preferably less than 25 μm, and even more preferably less than 20 μm (see Examples 3 to 6, etc.).

[0372] From the viewpoint of further suppressing the occurrence of defects, it was confirmed that the content of the compounds having a hydroxyl group is preferably 2500 mass ppm or less, more preferably 2000 mass ppm or less, and even more preferably 1000 mass ppm or less, in total, relative to the total mass of the developer. It was also confirmed that the content of the compounds having a hydroxyl group is preferably 200 mass ppm or more, in total, relative to the total mass of the developer (see Examples 1 to 3, 8 to 19, etc.).

[0373] It was confirmed that it is preferable for the actinic ray- or radiation-sensitive resin composition used to form the resist film to contain a crosslinking agent, since this further suppresses the occurrence of defects (see, for example, a comparison between Examples 4 and 7). [Explanation of symbols]

[0374] 302 PFA tubing 304 Canister 306 Cook 308 Aluminum Tape 310 Surface potential measuring instrument 312 Probe 314 Container 316 Teflon (registered trademark) sheet 318 Earth Wire 320 Nitrogen inlet pipe

Claims

1. (i) forming an actinic ray-sensitive or radiation-sensitive film having a thickness of 10 μm or more using an actinic ray-sensitive or radiation-sensitive resin composition; (ii) irradiating the actinic ray- or radiation-sensitive film with KrF light; and (iii) developing the actinic ray-sensitive or radiation-sensitive film irradiated with the KrF light using a developer to form a negative pattern; A pattern forming method comprising the steps of: The developer contains an organic solvent and a trace component, the developer contains, as the minor component, a compound having a hydroxyl group in a total amount of 150 to 3000 ppm by mass relative to the total mass of the developer, The organic solvent is an acetate solvent, the compound having a hydroxyl group is a carboxylic acid having 1 to 5 carbon atoms, an alcohol having 1 to 5 carbon atoms, and water; the total content of the carboxylic acid having 1 to 5 carbon atoms, the total content of the alcohol having 1 to 5 carbon atoms, and the content of the water are each independently 10 to 2500 ppm by mass with respect to the total mass of the developer.

2. The pattern formation method according to claim 1 , wherein the developer contains the compounds having a hydroxyl group in a total amount of 200 ppm by mass or more based on the total mass of the developer.

3. 3. The method for forming a pattern according to claim 1, wherein the organic solvent is butyl acetate.

4. The pattern formation method according to any one of claims 1 to 3, wherein the total content of the carboxylic acids having 1 to 5 carbon atoms, the total content of the alcohols having 1 to 5 carbon atoms, and the content of the water in the developer are each independently 50 to 2000 ppm by mass with respect to the total mass of the developer.

5. The actinic ray-sensitive or radiation-sensitive resin composition comprises (A) a resin having a repeating unit having an aromatic group and a repeating unit having a group that is decomposed by the action of an acid to produce a polar group; (B) a compound that generates an acid when exposed to actinic rays or radiation, (C) a solvent, and (G) a crosslinking agent, the content of the repeating unit having an aromatic group is 15 mol % or more based on the total repeating units of the resin, 5. The method for forming a pattern according to claim 1, wherein the crosslinking agent has two crosslinkable groups in the molecule.

6. the developer further contains, as the trace components, a metal component containing one or more metal elements selected from the group consisting of Na, K, Ca, Fe, Cu, Mg, Mn, Li, Al, Cr, Ni, Ti, and Zn; 6. The pattern formation method according to claim 1, wherein the total content of metal components in the developer is 10 ppt by mass to 1 ppb by mass.

Images