阅读说明：本技术 药液、冲洗液、抗蚀剂图案形成方法 (Chemical solution, rinse solution, and resist pattern forming method ) 是由 上村哲也 于 2020-02-18 设计创作，主要内容包括：本发明提供一种残渣去除性能优异的药液、冲洗液及抗蚀剂图案形成方法。本发明的药液含有ClogP值超过-1.00且为3.00以下的醇系溶剂和选自由式(1)表示的化合物及式(2)表示的化合物组成的组中的特定化合物,在所述药液中特定化合物的含量相对于药液总质量为0.0010～10质量ppb。(The invention provides a chemical solution, a rinse solution and a resist pattern forming method with excellent residue removal performance. The chemical solution of the present invention contains an alcohol solvent having a ClogP value of more than-1.00 and not more than 3.00 and a specific compound selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2), and the content of the specific compound in the chemical solution is 0.0010 to 10 ppb by mass relative to the total mass of the chemical solution.)

1. A medical solution comprising:

an alcohol solvent having a ClogP value of more than-1.00 and not more than 3.00; and

a specific compound selected from the group consisting of the compound represented by the formula (1) and the compound represented by the formula (2),

the content of the specific compound is 0.0010 ppb by mass to 10 ppb by mass based on the total mass of the chemical solution,

R¹and R²Each independently represents an alkyl group, or a substituted alkyl group,

R³and R⁵Each independently represents a hydrogen atom or an alkyl group,

R⁴represents a hydrogen atom or a hydroxyl group,

R⁶represents a hydrogen atom or an alkoxy group.

2. The medical solution according to claim 1, wherein,

the content of the specific compound is 0.010 ppb by mass to 5.0 ppb by mass with respect to the total mass of the chemical solution.

3. The medical solution according to claim 1 or 2, wherein,

the alcohol solvent contains 3 to 12 carbon atoms.

4. The liquid medicine according to any one of claims 1 to 3,

the ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol solvent is 3.0 or more.

5. The liquid medicine according to any one of claims 1 to 4,

the alcohol solvent has a vapor pressure of 0.01 to 10.0kPa at 25 ℃.

6. The medical solution according to any one of claims 1 to 5,

the alcohol solvent is selected from methyl isobutyl carbinol, 2, 6-dimethyl-4-heptanol, 2, 4-diethyl-1, 5-pentanediol, 2-ethyl-1-hexanol, 3-methyl-1, 5-pentanediol, 2-octanol, 3-methyl-1-butanol, 2, 4-dimethyl-3-pentanol, 2-methyl-2, 4-pentanediol, 3,5, 5-trimethyl-1-hexanol, 2-methylcyclohexanol, 1, 3-butanediol, 2-ethyl-1, 3-hexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 3-methyl-1, 3-butanediol, and trimethylolpropane.

7. The medical liquid according to any one of claims 1 to 6,

the alcohol solvent is contained in an amount of 85.000 to 99.999% by mass based on the total mass of the drug solution.

8. The medical solution according to any one of claims 1 to 7,

the alcohol solvent is methyl isobutyl carbinol, 3-methyl-1-butanol or 2, 4-dimethyl-3-pentanol.

9. The liquid medicine according to any one of claims 1 to 8, further comprising a metal component,

the content of the metal component is 0.10 to 100 mass ppt relative to the total mass of the liquid medicine.

10. A rinsing liquid containing the liquid medicine according to any one of claims 1 to 9.

11. A method for forming a resist pattern includes the steps of:

a step A of forming a film on a substrate with an actinic ray-sensitive or radiation-sensitive resin composition;

a step B of exposing the film;

step C, developing the exposed film with an alkaline developer; and

step D of washing the developed film with the rinse solution according to claim 10.

12. The method of forming a resist pattern according to claim 11, further comprising a step E of washing the developed film with water between the step C and the step D.

13. The resist pattern forming method according to claim 11 or 12,

the alkaline developer contains a quaternary ammonium salt.

14. The resist pattern forming method according to claim 13,

the content of the quaternary ammonium salt is 0.75 to 7.5 mass% based on the total mass of the alkaline developer.

Technical Field

The invention relates to a chemical solution, a rinse solution, and a resist pattern forming method.

Background

In the case of manufacturing a semiconductor device through a wiring forming process including photolithography, a chemical solution containing water and/or an organic solvent is used as a processing solution such as a developing solution and a rinse solution.

As a chemical solution used for forming a conventional resist pattern, patent document 1 discloses "a method of producing an organic processing liquid for forming a pattern of a chemically amplified resist film, which can reduce the generation of particles in a pattern forming technique" (paragraph [0010 ]). Patent document 1 discloses a method of using the organic processing liquid as a developing liquid or a rinse liquid.

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2015-84122

Disclosure of Invention

Technical problem to be solved by the invention

In recent years, alcohol solvents have been used in some cases for the production of semiconductor devices.

The present inventors have studied the residue removal performance of conventional alcohol solvents and have found that there is room for further improvement.

The invention provides a chemical liquid with excellent residue removal performance.

Another object of the present invention is to provide a rinse solution and a method for forming a resist pattern.

Means for solving the technical problem

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by the following structure.

(1) A medical solution comprising:

an alcohol solvent having a ClogP value of more than-1.00 and not more than 3.00; and

a specific compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2),

the content of the specific compound is 0.0010 to 10 ppb by mass relative to the total mass of the drug solution.

(2) The chemical solution according to (1), wherein the content of the specific compound is 0.010 to 5.0 mass ppb with respect to the total mass of the chemical solution.

(3) The chemical solution according to (1) or (2), wherein the number of carbon atoms contained in the alcohol solvent is 3 to 12.

(4) The chemical liquid according to any one of (1) to (3), wherein a ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol solvent is 3.0 or more.

(5) The chemical liquid according to any one of (1) to (4), wherein the vapor pressure of the alcohol solvent at 25 ℃ is 0.01 to 10.0 kPa.

(6) The chemical solution according to any one of (1) to (5), wherein the alcohol solvent is selected from the group consisting of methyl isobutyl carbinol, 2, 6-dimethyl-4-heptanol, 2, 4-diethyl-1, 5-pentanediol, 2-ethyl-1-hexanol, 3-methyl-1, 5-pentanediol, 2-octanol, 3-methyl-1-butanol, 2, 4-dimethyl-3-pentanol, 2-methyl-2, 4-pentanediol, 3,5, 5-trimethyl-1-hexanol, 2-methylcyclohexanol, 1, 3-butanediol, 2-ethyl-1, 3-hexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 3-methyl-1, 3-butanediol and trimethylolpropane.

(7) The chemical solution according to any one of (1) to (6), wherein the content of the alcohol-based solvent is 85.000 to 99.999% by mass based on the total mass of the chemical solution.

(8) The drug solution according to any one of (1) to (7), wherein the alcohol solvent is methyl isobutyl carbinol, 3-methyl-1-butanol, or 2, 4-dimethyl-3-pentanol.

(9) The chemical liquid according to any one of (1) to (8), which further contains a metal component,

the content of the metal component is 0.10 to 100 mass ppt relative to the total mass of the liquid medicine.

(10) An irrigation solution containing the chemical solution according to any one of (1) to (9).

(11) A method for forming a resist pattern includes the steps of: a step A of forming a film on a substrate with an actinic ray-sensitive or radiation-sensitive resin composition; step B, exposing the film; step C, developing the exposed film with an alkaline developer; and a step D of washing the developed film with the washing liquid described in (10).

(12) The method of forming a resist pattern according to (11), further comprising a step E of washing the developed film with water between the steps C and D.

(13) The method for forming a resist pattern according to (11) or (12), wherein the alkali developer contains a quaternary ammonium salt.

(14) The method for forming a resist pattern according to (13), wherein the content of the quaternary ammonium salt is 0.75 to 7.5% by mass based on the total mass of the alkaline developer.

Effects of the invention

According to the present invention, a chemical solution having excellent residue removal performance can be provided.

Further, according to the present invention, a rinse solution and a resist pattern forming method can be provided.

Detailed Description

The present invention will be described in detail below.

The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.

In the present specification, the numerical range represented by "to" means a range including numerical values before and after "to" as a lower limit value and an upper limit value.

In the present invention, "ppm" means "parts-per-million (10 parts per million)"^-6) "," ppb "means" parts-per-billion "(10)^-9) "," ppt "means" parts-per-trillion "(10 parts ratio)^-12)”。

In the labeling of the group (atomic group) in the present invention, the label not labeled with substitution and unsubstituted includes not only a group having no substituent but also a group having a substituent within a range not impairing the effect of the present invention. For example, the term "hydrocarbon group" includes not only a hydrocarbon group having no substituent (unsubstituted hydrocarbon group) but also a hydrocarbon group having a substituent (substituted hydrocarbon group). This meaning is also the same for each compound.

The term "radiation" in the present invention means, for example, Extreme Ultraviolet (EUV), X-ray, electron beam, or the like. In the present invention, light means actinic rays or radiation. The "exposure" in the present invention includes not only exposure using extreme ultraviolet rays, X-rays, EUV, or the like, but also drawing using a particle beam such as an electron beam or an ion beam, unless otherwise specified.

The present inventors have studied the characteristics of an alcohol solvent, and as a result, have found that a chemical liquid having excellent residue removal performance can be obtained by mixing a predetermined amount of a predetermined specific compound with an alcohol solvent.

The chemical solution of the present invention (hereinafter, also simply referred to as "chemical solution") contains an alcohol-based solvent having a ClogP value of more than-1.00 and 3.00 or less and a specific compound selected from the group consisting of a compound represented by the following formula (1) and a compound represented by the following formula (2).

Hereinafter, the components contained in the chemical liquid of the present invention will be described in detail.

< alcohol-based solvent >

The chemical liquid contains an alcohol solvent having a ClogP value of more than-1.00 and 3.00 or less.

From the viewpoint that the alcohol solvent has a ClogP value of more than-1.00 and not more than 3.00 and has more excellent residue removal performance (hereinafter, also referred to simply as "more excellent effect of the present invention"), it is more preferably-0.50 to 3.00, still more preferably-0.50 to 2.50, and particularly preferably 0.00 to 2.00.

The ClogP value is a value obtained by calculating the log logP of the distribution coefficient P for 1-octanol and water. As for the method and software used in the calculation of the ClogP value, a known method and software can be used, and unless otherwise specified, a ClogP program assembled in chem biodraw Ultra 12.0 of Cambridge soft corporation is used in the present invention.

The alcohol solvent contains hydroxyl groups, but the number of hydroxyl groups contained is not particularly limited, and is preferably 1 to 3, more preferably 1, from the viewpoint of further improving the effect of the present invention.

The alcohol solvent may be linear or branched. The alcohol solvent may have a ring structure.

The number of carbon atoms contained in the alcohol solvent is not particularly limited, but is preferably 3 to 12, more preferably 4 to 10, and still more preferably 5 to 9, from the viewpoint of further improving the effect of the present invention.

The ratio of the number of carbon atoms to the number of oxygen atoms (C/O ratio) contained in the alcohol solvent is not particularly limited, but is usually 2.0 or more, and from the viewpoint of further improving the effect of the present invention, it is preferably 3.0 or more, more preferably 4.0 or more, and still more preferably 5.0 or more. The upper limit is not particularly limited, but is preferably 10.0 or less, more preferably 9.0 or less, and further preferably 8.0 or less, from the viewpoint of further improving the effects of the present invention.

The vapor pressure of the alcohol solvent at 25 ℃ is not particularly limited, but is usually 0.01 to 15kPa, more preferably 0.01 to 10.0kPa, further preferably 0.10 to 1.0kPa, and particularly preferably 0.30 to 0.60kPa, from the viewpoint of further improving the effect of the present invention.

The alcohol solvent is not particularly limited in kind, but from the viewpoint of more excellent effects of the present invention, methyl isobutyl carbinol, 2, 6-dimethyl-4-heptanol, 2, 4-diethyl-1, 5-pentanediol, 2-ethyl-1-hexanol, 3-methyl-1, 5-pentanediol, 2-octanol, 3-methyl-1-butanol, 2, 4-dimethyl-3-pentanol, 2-methyl-2, 4-pentanediol, 3,5, 5-trimethyl-1-hexanol, 2-methylcyclohexanol, 1, 3-butanediol, 2-ethyl-1, 3-hexanediol, 2-butyl-2-ethyl-1, 3-propanediol, 3-methyl-1, 3-butanediol or trimethylolpropane, more preferably methyl isobutyl carbinol, 3-methyl-1-butanol or 2, 4-dimethyl-3-pentanol.

The content of the alcohol solvent in the chemical solution is not particularly limited, but is preferably 85.000 to 99.999% by mass, more preferably 95.000 to 99.999% by mass, still more preferably 99.500 to 99.995% by mass, particularly preferably 99.700 to 99.990% by mass, and most preferably 99.900 to 99.990% by mass, based on the total mass of the chemical solution, from the viewpoint of further improving the effects of the present invention.

< specific Compound >

The chemical solution contains a specific compound selected from the group consisting of a compound represented by formula (1) and a compound represented by formula (2).

[ chemical formula 1]

R¹And R²Each independently representAn alkyl group.

From R¹And R²The alkyl group represented by (a) may be linear or branched.

From R¹And R²The number of carbon atoms contained in the alkyl group is not particularly limited, but is preferably 2 to 10, more preferably 3 to 8, from the viewpoint of further improving the effect of the present invention.

R³And R⁵Each independently represents a hydrogen atom or an alkyl group.

From R³And R⁵The alkyl group represented by (a) may be linear or branched.

From R³And R⁵The number of carbon atoms contained in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 2 to 5, from the viewpoint of further improving the effect of the present invention.

R⁴Represents a hydrogen atom or a hydroxyl group.

R⁶Represents a hydrogen atom or an alkoxy group.

From R⁶The number of carbon atoms contained in the alkoxy group is not particularly limited, but is preferably 3 to 10, more preferably 4 to 8, from the viewpoint of further improving the effect of the present invention.

In the formula (2), R is preferred³～R⁵Is a hydrogen atom and R⁶Mode 1 or R being alkoxy³And R⁵Is alkyl, R⁴Is hydroxy and R⁶Mode 2 is a hydrogen atom.

Specific examples of the compound represented by the formula (1) and the compound represented by the formula (2) include the following specific compounds a to D.

[ chemical formula 2]

The content (total content) of the specific compound in the chemical solution is preferably 0.0010 to 10 mass ppb based on the total mass of the chemical solution, and from the viewpoint of further excellent effects of the present invention, 0.010 to 5.0 mass ppb is more preferred, and 0.10 to 2.0 mass ppb is even more preferred.

When a plurality of compounds are contained in the drug solution as the specific compound, the total amount thereof is within the above range.

The chemical solution may contain other components besides the alcohol solvent and the specific compound.

The other components will be described in detail below.

< Metal component >

The chemical solution may contain a metal component.

In the present invention, the metal component includes metal particles and metal ions, and for example, the content of the metal component indicates the total content of the metal particles and the metal ions.

The chemical solution may contain either or both of metal particles and metal ions.

Examples of the metal element in the metal component include Na (sodium), K (potassium), Ca (calcium), Fe (iron), Cu (copper), Mg (magnesium), Mn (manganese), Li (lithium), Al (aluminum), Cr (chromium), Ni (nickel), Ti (titanium), and Zr (zirconium). The metal component may contain 1 kind of metal element, or may contain 2 or more kinds.

The metal particles may be a single body or an alloy.

The metal component may be a metal component inevitably contained in each component (raw material) contained in the chemical liquid, may be a metal component inevitably contained in the production, storage and/or transfer of the chemical liquid, or may be intentionally added.

When the chemical solution contains a metal component, the content is not particularly limited, and is 0.01 to 500 mass ppt relative to the total mass of the chemical solution. Among them, 0.10 to 100 mass ppt is preferable from the viewpoint of more excellent effect of the present invention.

The types and contents of metal ions and metal particles in the chemical solution can be measured by an SP-ICP-MS (Single Nano Particle Inductively Coupled Plasma Mass Spectrometry) method.

The SP-ICP-MS method is the same as a general ICP-MS method (inductively coupled plasma mass spectrometry) and is different from the conventional ICP-MS method only in data analysis. The data analysis by the SP-ICP-MS method can be carried out by a commercially available software.

In the ICP-MS method, the content of a metal component to be measured is measured regardless of the existence mode thereof. Therefore, the total mass of the metal particles and the metal ions to be measured is quantified as the content of the metal component.

On the other hand, in the SP-ICP-MS method, the content of the metal particles can be measured. Therefore, the content of the metal ions in the sample can be calculated by subtracting the content of the metal particles from the content of the metal components in the sample.

Examples of the apparatus for the SP-ICP-MS method include Agilent8800 triple quadrupole ICP-MS (inductively coupled plasma mass spectrometry, option #200 for semiconductor analysis), manufactured by Agilent Technologies, and can be measured by the methods described in the examples. As an apparatus other than the above, Agilent 8900 manufactured by Agilent Technologies can be used in addition to Nexion350S manufactured by Perkinelmer.

In addition to the above, the liquid medicine may contain water.

< method for producing chemical liquid >

The method for producing the chemical solution is not particularly limited, and a known production method can be exemplified.

For example, a predetermined amount of a specific compound may be added to an alcohol-based solvent to produce a chemical solution, or a commercially available product may be purchased and subjected to a purification treatment to produce a chemical solution. Among these, examples of the method for producing the chemical solution include a method including at least one of a step of distilling the purified material (distillation step) and a step of filtering the purified material (filtration step). Further, examples of the purified product include commercially available alcohol solvents. The commercially available product usually contains impurities, and for example, the specific compound may be contained in an excess amount as impurities in an alcohol solvent (particularly, methyl isobutyl carbinol).

The sequence of the distillation step and the filtration step will be described in detail below.

(distillation step)

The distillation step is a step of distilling the purified product (for example, a solution containing an alcohol-based solvent and a specific compound) to obtain a distilled purified product.

The method of distilling the purified product is not particularly limited, and a known method can be used. Typically, a method is mentioned in which a distillation column is disposed on the primary side of a purification apparatus used in a filtration step described later, and a purified product obtained by distillation is introduced into a production tank.

In this case, the liquid contact portion of the distillation column is not particularly limited, but is preferably formed of a corrosion-resistant material described later.

In the distillation step, the purified product may be passed through the same distillation column a plurality of times, or may be passed through different distillation columns. When the purified product is passed through different distillation columns, for example, the following methods are mentioned: a method of performing a crude distillation process in which a substance to be purified is passed through a distillation column to remove components having a low boiling point, and then performing a rectification process in which the substance is passed through a distillation column different from the crude distillation process to remove other components.

Examples of the distillation column include a trayed distillation column and a vacuum trayed distillation column.

Further, in order to achieve both thermal stability and purification accuracy during distillation, distillation under reduced pressure may be carried out.

(filtration step)

The filtration step is a step of filtering the purified product with a filter.

The method of filtering the purified material using the filter is not particularly limited, but it is preferable to pass the purified material under pressure or without pressure (pass through) a filter unit having a housing and a filter element accommodated in the housing.

The pore diameter of the filter is not particularly limited, and a filter having a pore diameter that is generally used for filtering an object to be purified can be used. Among them, the pore diameter of the filter is preferably 200nm or less, more preferably 20nm or less, and further preferably 10nm or less. The lower limit is not particularly limited, but is preferably 1nm or more in general from the viewpoint of productivity.

In the present specification, the pore diameter of the filter means a pore diameter determined by the bubble point of isopropyl alcohol.

The mode of sequentially using 2 or more filters having different pore diameters is not particularly limited, and a method of arranging a plurality of filter units including a filter along a pipe line for transporting a purified material may be mentioned. In this case, when the flow rate of the purified material per unit time is fixed in the entire pipe line, a larger pressure may be applied to the filter having a smaller pore diameter than to the filter having a larger pore diameter. In this case, it is preferable to increase the filtration area by arranging a pressure regulating valve, a damper, and the like between the filters, and arranging a filter unit containing the same filter along the pipeline or by fixing the pressure applied to the filter having a small pore diameter.

The material of the filter is not particularly limited, and known materials can be used as the material of the filter. Specifically, in the case of a resin, there may be mentioned polyamides such as nylon (e.g., 6-nylon and 6, 6-nylon); polyolefins such as polyethylene and polypropylene; polystyrene; a polyimide; a polyamide-imide; poly (meth) acrylates; fluorine-based resins such as polytetrafluoroethylene, perfluoroalkoxyalkane, perfluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride and polyvinyl fluoride; polyvinyl alcohol; a polyester; cellulose; cellulose acetate, and the like.

Among them, from the viewpoint of more excellent solvent resistance and more excellent defect suppression performance of the obtained chemical solution, at least 1 selected from the group consisting of nylon (among them, 6-nylon is preferable), polyolefin (among them, polyethylene is preferable), poly (meth) acrylate, and fluorine-based resin (among them, Polytetrafluoroethylene (PTFE) or Perfluoroalkoxyalkane (PFA)) is preferable. These polymers can be used alone or in combination of 2 or more.

In addition to the resin, diatomaceous earth, glass, or the like may be used.

In addition, a polymer (such as nylon-grafted UPE) obtained by graft-copolymerizing a polyamide (for example, nylon such as nylon-6 or nylon-6, 6) and a polyolefin (such as UPE (ultra high molecular weight polyethylene) described later) may be used as a material of the filter.

Also, the filter may be a surface-treated filter. The method of surface treatment is not particularly limited, and a known method can be used. Examples of the surface treatment include chemical modification treatment, plasma treatment, hydrophobic treatment, coating, gas treatment, and sintering.

As the chemical modification treatment, a method of introducing an ion exchange group into a filter is preferable.

That is, as the filter, a filter having an ion exchange group can be used.

Examples of the ion exchange group include a cation exchange group and an anion exchange group, examples of the cation exchange group include a sulfonic acid group, a carboxyl group, and a phosphate group, and examples of the anion exchange group include a quaternary ammonium group. The method for introducing the ion-exchange group into the filter is not particularly limited, but a method in which a compound containing the ion-exchange group and the polymerizable group is reacted with the filter (typically, a method of grafting) may be mentioned.

The method for introducing the ion exchange group is not particularly limited, and the filter is irradiated with ionizing radiation (α rays, β rays, γ rays, X rays, electron beams, and the like) to generate an active moiety (radical). The irradiated filter is immersed in a monomer-containing solution to graft-polymerize the monomer to the filter. As a result, the polymer obtained by polymerizing the monomer is grafted to the filter. The ion-exchange group can be introduced into the polymer by subjecting the resulting polymer to a contact reaction with a compound containing an anion-exchange group or a cation-exchange group.

When a filter having an ion exchange group is used, the content of metal particles and metal ions in the chemical solution can be more easily controlled to a desired range. The material constituting the filter having an ion exchange group is not particularly limited, but examples thereof include a material in which an ion exchange group is introduced into a fluororesin or a polyolefin, and a material in which an ion exchange group is introduced into a fluororesin is more preferable.

The pore diameter of the filter having an ion exchange group is not particularly limited, but is preferably 1 to 30nm, more preferably 5 to 20 nm.

As the filter used in the filtration step, 2 or more kinds of filters of different materials can be used, and for example, 2 or more kinds selected from the group consisting of polyolefin, fluorine-based resin, polyamide, and filters of materials in which ion exchange groups are introduced into these can be used.

The pore structure of the filter is not particularly limited, and may be appropriately selected according to the components in the purified product. In the present specification, the pore structure of the filter means pore diameter distribution, pore position distribution in the filter, pore shape, and the like, and can be typically controlled by a filter manufacturing method.

For example, a porous film can be obtained by sintering a powder of a resin or the like, and a fiber film can be obtained by electrospinning (electrospinning), electroblowing (electroblowing), meltblowing (meltblowing), or the like. These pores have different structures.

The "porous membrane" refers to a membrane that retains components in a substance to be purified such as gel, particles, colloid, cells, and oligomer, but allows components smaller than the pores to substantially pass through the pores. The retention of components in the purified product by the porous membrane may depend on the operating conditions, such as the surface velocity, the use of a surfactant, the pH, and a combination thereof, and may depend on the pore size and structure of the porous membrane and the size and structure of the particles to be removed (hard particles, gel, or the like).

The pore structure of the porous membrane (for example, a porous membrane containing UPE, PTFE, and the like) is not particularly limited, and examples of the shape of the pores include a bud shape, a string shape, a node shape, and the like.

The size distribution of the pores in the porous film and the position distribution in the film are not particularly limited. It is possible that the size distribution is smaller and the distribution position in the film is symmetrical. Further, the size distribution may be larger and the distribution position in the film may be asymmetric (the above film is also referred to as an "asymmetric porous film"). In an asymmetric porous membrane, the size of the pores varies in the membrane, typically the pore size becomes larger from one surface of the membrane toward the other surface of the membrane. In this case, the surface having a large number of pores with a large pore diameter is referred to as "open (open) side", and the surface having a large number of pores with a small pore diameter is referred to as "dense (tite) side".

Further, as the asymmetric porous membrane, for example, a membrane in which the size of pores is smallest at a certain position within the thickness of the membrane (this is also referred to as "hourglass shape").

Further, the filter is preferably used after being sufficiently cleaned before use.

When an uncleaned filter (or a filter that has not been sufficiently cleaned) is used, impurities contained in the filter easily enter the drug solution.

As described above, the filtration step may be a multistage filtration step in which the purified material is passed through 2 or more different types of filters. The different filters described above show at least 1 difference in pore diameter, pore structure, and material.

Further, the purified material may be passed through the same filter a plurality of times, or the purified material may be passed through a plurality of filters of the same kind.

In addition, a filter containing a fluorine-based resin is preferably used in view of easy production of the chemical solution of the present invention. Among these, it is preferable to use a plurality of multistage filtration for the filter containing the fluorine-based resin. The filter containing the fluorine-based resin preferably has a pore diameter of 20nm or less.

Among them, it is preferable to sequentially perform the following steps in view of easy production of the chemical solution of the present invention: a first filtration step of filtering the purified product with a filter having a pore size of 100nm or more; and a 2 nd filtration step of filtering the purified product by using a filter containing a fluorine-containing resin having a pore diameter of 10nm or less (preferably, a filter made of PTFE). In the 1 st filtration step, coarse particles are removed.

The material of the liquid contact portion (which represents an inner wall surface or the like that may come into contact with the object to be purified and the liquid chemical) of the purification apparatus used in the filtration step is not particularly limited, but is preferably formed of at least 1 kind selected from the group consisting of a non-metal material (fluorine-based resin or the like) and an electropolished metal material (stainless steel or the like) (hereinafter, these are also collectively referred to as "corrosion-resistant material").

The non-metallic material is not particularly limited, and known materials can be used.

Examples of the non-metallic material include at least 1 selected from the group consisting of a polyethylene resin, a polypropylene resin, a polyethylene-polypropylene resin, and a fluorine-based resin (for example, a tetrafluoroethylene resin, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, a tetrafluoroethylene-hexafluoropropylene copolymer resin, a tetrafluoroethylene-ethylene copolymer resin, a chlorotrifluoroethylene-ethylene copolymer resin, a vinylidene fluoride resin, a chlorotrifluoroethylene copolymer resin, a vinyl fluoride resin, and the like).

The metal material is not particularly limited, and known materials can be used.

Examples of the metal material include metal materials in which the total content of chromium and nickel is more than 25 mass% based on the total mass of the metal material, and among these, 30 mass% or more is more preferable. The upper limit of the total content of chromium and nickel in the metal material is not particularly limited, but is preferably 90 mass% or less in general.

Examples of the metal material include stainless steel and nickel-chromium alloy.

The stainless steel is not particularly limited, and known stainless steels can be exemplified. Among these, an alloy containing 8 mass% or more of nickel is preferable, and an austenitic stainless steel containing 8 mass% or more of nickel is more preferable. Examples of austenitic Stainless Steel include SUS (Steel Use Stainless: Stainless Steel) 304(Ni content 8 mass%, Cr content 18 mass%), SUS304L (Ni content 9 mass%, Cr content 18 mass%), SUS316(Ni content 10 mass%, Cr content 16 mass%), SUS316(Ni content 12 mass%, Cr content 16 mass%), and SUS316L (Ni content 16 mass%).

The nickel-chromium alloy is not particularly limited, and known nickel-chromium alloys can be used. Among them, a nickel-chromium alloy having a nickel content of 40 to 75 mass% and a chromium content of 1 to 30 mass% is preferable.

Examples of the nickel-chromium alloy include hastelloy (trade name, the same as below), monel (trade name, the same as below), and inconel (trade name, the same as below). More specifically, Hastelloy C-276(Ni content: 63 mass%, Cr content: 16 mass%), Hastelloy C (Ni content: 60 mass%, Cr content: 17 mass%), and Hastelloy C-22(Ni content: 61 mass%, Cr content: 22 mass%) are given.

In addition to the above-described alloys, the nickel-chromium alloy may contain boron, silicon, tungsten, molybdenum, copper, cobalt, and the like as necessary.

The method for electropolishing the metal material is not particularly limited, and a known method can be used. For example, the methods described in paragraphs [0011] to [0014] of Japanese patent laid-open No. 2015-227501 and paragraphs [0036] to [0042] of Japanese patent laid-open No. 2008-264929 can be used.

It is presumed that in the metal material, the content of chromium in the passivation layer on the surface by electropolishing becomes larger than the chromium content of the parent phase. Therefore, it is presumed that when a purification apparatus in which the liquid contact portion is formed of an electropolished metal material is used, the metal particles are less likely to flow out into the liquid to be purified.

In addition, the metal material may also be polished. The polishing method is not particularly limited, and a known method can be used. The size of the abrasive grains used for the finish polishing is not particularly limited, but is preferably #400 or less in view of the ease with which the irregularities on the surface of the metal material become smaller. In addition, polishing is preferably performed before electropolishing.

In the purification of the purified product, it is preferable that the unsealing of the container, the cleaning of the container and the apparatus, the storage of the solution, the analysis, and the like all be performed in a clean room. The clean room is preferably a clean room defined in the international organization for standardization international standard ISO 14644-1: a clean room with a level of 4 or more specified in 2015. Specifically, it preferably satisfies any one of ISO class 1, ISO class 2, ISO class 3, and ISO class 4, more preferably satisfies ISO class 1 or ISO class 2, and still more preferably satisfies ISO class 1.

< medicinal liquid containing body >

The chemical liquid can be stored in a container until use. Such a container and the chemical liquid contained in the container are collectively referred to as a chemical liquid container. The liquid medicine is taken out from the stored liquid medicine container and used.

As a container for storing the chemical solution, a container having high cleanliness and less elution of impurities in the container is preferable for semiconductor device manufacturing applications.

The container that can be used is not particularly limited, and examples thereof include AICELLO CHEMICAL CO., manufactured by LTD, "Clean Bottle" series, KODAMA PLASTICS CO., manufactured by LTD, "Pure Bottle".

For the purpose of preventing impurities from being mixed into (contaminated by) the chemical liquid, it is also preferable to use a multilayer bottle having a 6-layer structure made of 6 kinds of resins or a multilayer bottle having a 7-layer structure made of 6 kinds of resins as the inner wall of the container. Examples of such containers include those described in Japanese patent laid-open publication No. 2015-123351.

The liquid contacting portion of the container may be a corrosion resistant material as already described (preferably electropolished stainless steel or fluorine-based resin) or glass. In view of further improving the effect of the present invention, it is preferable that 90% or more of the area of the liquid contact portion is formed of the material, and it is more preferable that the entire liquid contact portion is formed of the material.

The porosity of the chemical solution container in the container is preferably 2 to 35 vol%, more preferably 5 to 30 vol%. That is, in the method for producing the chemical liquid container, the step of containing the obtained chemical liquid in the container is preferably performed so that the porosity in the container becomes 2 to 35 vol%.

In addition, the porosity is calculated according to formula (1).

Formula (1): porosity {1- (volume of drug solution in container/container volume of container) } × 100

The above-mentioned container volume has the same meaning as the internal volume (capacity) of the container.

By setting the porosity within this range, contamination by impurities and the like is restricted, whereby storage stability can be ensured.

< use of medicinal liquid >

The chemical solution of the present invention is preferably used for manufacturing a semiconductor device (preferably, a semiconductor chip).

The chemical solution can be used for other applications than the production of semiconductor devices, and can also be used as a developing solution and a rinse solution for polyimide, a resist for sensors, a resist for lenses, and the like.

The chemical solution can also be used as a solvent for medical use or cleaning use. For example, the cleaning agent can be preferably used for cleaning pipes, containers, substrates (e.g., wafers, glass, etc.), and the like.

The cleaning application is also preferably used as a cleaning liquid (e.g., a pipe cleaning liquid, a container cleaning liquid, etc.) for cleaning a pipe, a container, etc. which come into contact with a liquid such as the pre-wetting liquid.

< method for forming resist Pattern >

The chemical solution of the present invention is preferably used as a rinse solution, and more preferably used as a rinse solution for forming a resist pattern.

Specifically, in the resist pattern forming method having the following steps a to E, the chemical solution is preferably used as the rinse solution. The step E is an optional step and may not be performed. When step E is not performed, step D corresponds to a step of cleaning the developed film (film obtained in step C) with the chemical solution of the present invention.

Step A: step (B) of forming a film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition: process for producing an Exposure film

And a step C: step of developing the exposed film with an alkaline developer

Step E: process for cleaning developed film with water

Step D: step of cleaning the film cleaned in step D with the chemical solution of the present invention

As will be described later, a heating step (PB; Prebake) may be performed between the steps a and B, and a heating step (PEB; Post Exposure Bake) may be performed between the steps (B) and (C).

These steps will be explained below.

(Process A)

The step a is a step of forming a film on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition.

The actinic ray-sensitive or radiation-sensitive resin composition will be described in detail later.

The method for forming a film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition is not particularly limited, and a known method can be used. Among them, from the viewpoint of easier adjustment of the thickness of the film, there is a method of forming a film by coating a actinic ray-sensitive or radiation-sensitive resin composition on a substrate.

The method of coating is not particularly limited, and a known method can be used. Among them, in the field of semiconductor manufacturing, spin coating is preferably used.

After the actinic ray-or radiation-sensitive resin composition is applied, a drying treatment for removing the solvent may be performed as necessary. The method of the drying treatment is not particularly limited, and examples thereof include a heating treatment and an air drying treatment.

The substrate on which the film is formed is not particularly limited, and silicon, SiN, or SiO can be used₂And inorganic substrates such as SiN, coating-type inorganic substrates such as SOG (Spin On Glass), semiconductor manufacturing processes such as IC (Integrated Circuit), manufacturing processes of Circuit boards such as liquid crystal and thermal head, and further substrates generally used in other photolithography processes for photosensitive etching.

Further, an organic antireflection film may be disposed between the film and the substrate as necessary.

The receding contact angle of a film (resist film) formed from the actinic ray-sensitive or radiation-sensitive resin composition is preferably 70 ° or more, more preferably 75 ° or more, and still more preferably 75 to 85 ° at a temperature of 23 ± 3 ℃ and a humidity of 45 ± 5%. When the receding contact angle of the resist film is in the above range, it is suitable for exposure through a liquid immersion medium.

In order to achieve a preferable receding contact angle, it is preferable to include a hydrophobic resin in the actinic-ray-sensitive or radiation-sensitive composition described above. Alternatively, the receding contact angle may be improved by forming a coating layer based on a resin composition having hydrophobicity (so-called "top coat layer") on the resist film. As the top coat layer, a top coat layer known in the art can be suitably used.

Further, as the top coat layer, it is also preferable to apply a top coat layer containing not only a resin but also a basic compound (quencher) as described in Japanese patent laid-open publication No. 2013-061647, in particular, OC-5 to OC-11 in example Table 3 thereof.

The thickness of the resist film is not particularly limited, but is preferably 1 to 500nm, more preferably 1 to 100nm, from the viewpoint of forming a fine pattern with higher accuracy.

(heating Process (PB; Prebake))

The resist pattern forming method preferably has a pre-heating step (PB; Prebake) after the film formation and before the step B described later.

The heating temperature is preferably 70 to 130 ℃, and more preferably 80 to 120 ℃. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds.

The heating may be performed by a mechanism provided in a general exposure machine and/or developing machine, or may be performed using a hot plate or the like. By baking, the reaction of the exposed portion is promoted and the sensitivity and/or pattern profile is improved.

(Process B)

The step B is a step of exposing the film formed in the step a. More specifically, the method is a step of selectively exposing a film to form a desired pattern. Thus, the film is exposed in a pattern, and the solubility of the resist film changes only in the exposed portion.

In addition, "exposure" means irradiation of actinic rays or radiation.

The wavelength of the light source used for exposure is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-ray, electron beam, and the like, and far ultraviolet light having a wavelength of preferably 250nm or less, more preferably 220nm or less, and still more preferably 1 to 200nm, and specific examples thereof include KrF excimer laser (248nm), ArF excimer laser (193nm), and F excimer laser₂Excimer laser (157nm), X-ray, EUV (13nm), electron beam, etc., preferably KrF excimer laser, and,ArF excimer laser, EUV or electron beam, more preferably ArF excimer laser.

The method of selectively exposing the film is not particularly limited, and a known method can be used. For example, a Binary Mask (Binary-Mask) having a light-shielding portion transmittance of 0% or a halftone-type phase shift Mask (HT-Mask) having a light-shielding portion transmittance of 6% can be used.

As the binary mask, a mask having a light shielding portion formed of a chromium film, an acidified chromium film, or the like on a quartz glass substrate is generally used.

As for the halftone type phase shift mask, a mask having a light shielding portion formed of a MoSi (molybdenum silicide) film, a chromium film, an acidified chromium film, a silicon oxynitride film, or the like on a quartz glass substrate is generally used.

In the present invention, the exposure is not limited to the exposure through the photomask, and the exposure may be performed without the photomask, and for example, the selective exposure (pattern exposure) may be performed by drawing with an electron beam or the like.

The process may include multiple exposures.

(preferred embodiment: liquid immersion exposure)

A preferable example of the exposure is immersion exposure. By using liquid immersion exposure, a finer pattern can be formed. In addition, the liquid immersion exposure can be combined with super-resolution techniques such as a phase shift method and an anamorphic illumination method.

As the liquid immersion liquid used in the liquid immersion exposure, a liquid that is transparent to the exposure wavelength and has a temperature coefficient of refractive index as small as possible in order to minimize the distortion of the optical image projected on the resist film is preferable. In particular, when the exposure light source is an ArF excimer laser (wavelength; 193nm), water is preferably used from the viewpoints of availability and ease of handling in addition to the viewpoints described above.

When water is used as the liquid immersion liquid, an additive (liquid) that reduces the surface tension of water and increases the surface activity may be added in a small proportion. The additive is preferably one that does not dissolve the resist film and can neglect the effect on the optical coating under the lens element.

As such an additive, for example, an aliphatic alcohol having a refractive index almost equal to that of water is preferable, and specific examples thereof include methanol, ethanol, and isopropanol. By adding an alcohol having a refractive index almost equal to that of water to the liquid immersion liquid, there is obtained an advantage that even if the alcohol component in water evaporates and the concentration of the alcohol component changes, the refractive index change of the entire liquid can be made extremely small.

As the water used, distilled water is preferable. Further, pure water filtered by an ion exchange filter or the like may be used.

The resistance of water used as the liquid immersion liquid is preferably 18.3 M.OMEGA.cm or more. Alternatively, the TOC (organic matter concentration) in the water is preferably 20 ppb by mass or less. Also, it is preferable that the water is degassed.

Furthermore, the refractive index of the immersion liquid can be increased to improve the lithography performance. From this viewpoint, an additive for increasing the refractive index may be added to water, or heavy water (D) may be used₂O) instead of water.

In the liquid immersion exposure, the surface of the resist film may be cleaned with an aqueous chemical solution before and/or after exposure (before heat treatment).

(heating Process (PEB; Post Exposure Bake))

The resist pattern forming method preferably includes a Post-Exposure heating step (PEB) after the step B and before the step C.

Preferably at a heating temperature of 70 to 130 ℃, more preferably at 80 to 120 ℃. The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and further preferably 30 to 90 seconds.

The heating may be performed by a mechanism provided in a general exposure/development machine, or may be performed using a hot plate or the like. By baking, the reaction of the exposed portion is promoted and the sensitivity or pattern profile is improved.

(Process C)

The step C is a step of developing the exposed film with an alkaline developer. By performing this step, a desired pattern is formed. By this method, a portion having strong exposure intensity is removed.

Examples of the alkali contained in the alkaline developer include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine; secondary amines such as diethylamine and di-n-butylamine; tertiary amines such as triethylamine and methyldiethanamine; alkanolamines such as dimethylethanolamine and triethanolamine; quaternary ammonium salts such as tetraalkylammonium hydroxides, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide and triethylbenzylammonium hydroxide, such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltripentylammonium hydroxide and dibutyldipentylammonium hydroxide; cyclic amines such as pyrrole and piperidine, and quaternary ammonium salts are preferred.

The alkali concentration of the alkali developer is preferably 0.1 to 20% by mass, more preferably 0.75 to 15% by mass, and still more preferably 0.75 to 7.5% by mass, from the viewpoint of further improving the effect of the present invention.

The pH of the alkaline developer is preferably 10.0 to 15.0.

The alkaline developer may contain a chelating agent.

The chelating agent is a compound having a function of chelating a metal ion. Among these, a compound having 2 or more functional groups (ligands) coordinately bonded to a metal ion in 1 molecule is preferable.

Examples of the ligand include a carboxyl group and the like.

Examples of the ligand of the chelating agent include an acid group and a cationic group. Examples of the acid group include a carboxyl group, a phosphonic acid group, a sulfo group, and a phenolic hydroxyl group.

Examples of the chelating agent include an organic chelating agent and an inorganic chelating agent.

The organic chelating agent is a chelating agent composed of an organic compound, and examples thereof include a carboxylic acid chelating agent having a carboxyl group as a ligand and a phosphonic acid chelating agent having a phosphonic acid group as a ligand, and a carboxylic acid chelating agent is preferable.

Examples of the inorganic chelating agent include condensed phosphates.

Examples of the chelating agent having a carboxyl group as a ligand in the molecule include aminopolycarboxylic acid chelating agents (e.g., butanediamine tetraacetic acid, diethylenetriamine pentaacetic acid, etc.), amino acid chelating agents (e.g., glycine, etc.), hydroxycarboxylic acid chelating agents (e.g., malic acid, citric acid, etc.), and aliphatic carboxylic acid chelating agents (e.g., oxalic acid, malonic acid, etc.).

The content of the chelating agent is preferably 10 to 10000 ppm by mass, more preferably 100 to 1000 ppm by mass, based on the total mass of the alkaline developer.

The alkaline developer may contain a surfactant.

The surfactant contained in the alkaline developer is not particularly limited, and examples thereof include a cationic surfactant, an anionic surfactant, and a nonionic surfactant, and an anionic surfactant or a nonionic surfactant is preferable.

The content of the surfactant is preferably 0.001 to 5% by mass, more preferably 0.005 to 2% by mass, and still more preferably 0.01 to 0.5% by mass, based on the total mass of the alkaline developer.

Examples of the developing method include a method in which the substrate is immersed in a tank filled with a developing solution for a certain period of time (immersion method), a method in which the developing solution is accumulated on the surface of the substrate by surface tension and left still for a certain period of time to develop the substrate (spin-coating immersion method), a method in which the developing solution is sprayed onto the surface of the substrate (spray method), and a method in which the developing solution is continuously sprayed onto the substrate rotating at a certain speed while scanning a developing solution nozzle at a certain speed (dynamic dispensing method).

When the above-described various developing methods include a step of discharging the developer from a developing nozzle of a developing device toward the resist film, the discharge pressure of the discharged developer (the flow rate per unit area of the discharged developer) is preferably 2mL/sec/mm²Hereinafter, more preferably 1.5mL/sec/mm²Hereinafter, more preferably 1mL/sec/mm²The following. The lower limit of the flow rate is not particularly limited, but is preferably 0.2mL/sec/mm from the viewpoint of Throughput (Throughput)²The above.

By setting the discharge pressure of the discharged developer to the above range, pattern defects caused by the resist residue after development can be significantly reduced.

The details of this mechanism are not certain, but are believed to be possible for the following reasons: by setting the ejection pressure in the above range, the pressure applied by the developer to the resist film is reduced, and accidental erasure or collapse of the resist film/resist pattern is suppressed.

Further, the discharge pressure of the developer solution (mL/sec/mm)²) Is a value in the outlet of the developing nozzle in the developing device.

Examples of the method of adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure by a pump or the like and a method of adjusting the discharge pressure by supplying the developer from a pressure tank to change the discharge pressure.

(Process E)

Step E is a step of washing the developed film with water. As described above, the step E is an optional step, and the effect of the present invention is more excellent by performing the step E.

The type of water used is not particularly limited, and is preferably ultrapure water which is generally used in a semiconductor process.

The method of the cleaning treatment is not particularly limited, and examples thereof include a method of continuously spraying water onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with water for a constant period of time (immersion method), and a method of spraying water onto the surface of the substrate (spray method).

Among them, a method of performing a cleaning treatment by a spin coating method, and removing water from the substrate by rotating the substrate at 2000 to 4000rpm after the cleaning is preferable.

(Process D)

Step D is a step of cleaning the film cleaned in step E with the chemical solution of the present invention.

The liquid medicine used was as described above.

The method of the cleaning treatment is not particularly limited, and examples thereof include a method of continuously discharging the chemical solution of the present invention onto a substrate rotating at a constant speed (spin coating method), a method of immersing the substrate in a tank filled with the chemical solution of the present invention for a constant time (immersion method), and a method of spraying the chemical solution of the present invention onto the surface of the substrate (spray method).

Further, the step of drying the resist pattern may be performed after the step D.

As a method of the drying treatment, a heat treatment (Post Bake) may be mentioned.

By performing this step, the developer, rinse, and the like remaining between the patterns and inside the patterns can be removed.

When the drying treatment is performed by heating, the heating temperature in the heating treatment is preferably 40 to 250 ℃, more preferably 150 to 220 ℃. The heating time is preferably 10 seconds to 10 minutes, and more preferably 100 to 360 seconds.

< actinic ray-sensitive or radiation-sensitive resin composition >

The actinic ray-or radiation-sensitive resin composition (hereinafter, also simply referred to as "composition") used in the above-described pattern forming method contains at least a resin (a) whose polarity is increased by the action of an acid and a photoacid generator (P).

Hereinafter, the components that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition will be described in detail.

(resin (A))

The actinic ray-sensitive or radiation-sensitive resin composition contains a resin (A) whose polarity is increased by the action of an acid.

(repeating Unit (A-a) having acid-decomposable group)

The resin (a) contains a repeating unit (a-a) having an acid-decomposable group (hereinafter, also simply referred to as "repeating unit (a-a)").

The acid-decomposable group means a group which is decomposed by the action of an acid to form a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected with a leaving group (released by the action of an acid). That is, the resin (a) contains a repeating unit (a-a) having a group which is decomposed by the action of an acid to form a polar group. The resin having the repeating unit (a-a) has increased polarity by the action of an acid to increase the solubility in an alkaline developer, but has decreased solubility in an organic solvent.

The polar group is preferably an alkali-soluble group, and examples thereof include an acidic group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide 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, and an alcoholic hydroxyl group.

Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

Examples of the leaving group to be removed by the action of an acid include groups represented by formulae (Y1) to (Y4).

Formula (Y1): -C (Rx)₁)(Rx₂)(Rx₃)

Formula (Y2): -C (═ O) OC (Rx)₁)(Rx₂)(Rx₃)

Formula (Y3): -C (R)₃₆)(R₃₇)(OR₃₈)

Formula (Y4): -C (Rn) (H) (Ar)

In the formulae (Y1) and (Y2), Rx₁～Rx₃Each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). In addition, all Rx₁～Rx₃Alkyl (when straight-chain or branched, Rx)₁～Rx₃At least 2 of which are preferably methyl groups.

Wherein, Rx₁～Rx₃Preferably independently represent a linear or branched alkyl group, Rx₁～Rx₃More preferably, each independently represents a linear alkyl group.

Rx₁～Rx₃2 of which may be bonded to form a single ring or multiple rings.

As Rx₁～Rx₃The alkyl group of (1) 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, a tert-butyl group and the like.

As Rx₁～Rx₃The cycloalkyl group of (2) is preferably a monocyclic ring such as cyclopentyl or cyclohexylAlkyl groups and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl groups.

As Rx₁～Rx₃The cycloalkyl group in which 2 of them are bonded is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group or an adamantyl group, or more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.

With respect to Rx₁～Rx₃In the cycloalkyl group in which 2 are bonded, for example, 1 methylene group constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

As the group represented by the formula (Y1) or the formula (Y2), for example, Rx is preferable₁Is methyl or ethyl and Rx₂And Rx₃And bonded to form the cycloalkyl group.

In the formula (Y3), R₃₆～R₃₈Each independently represents a hydrogen atom or a 1-valent organic group. R₃₇And R₃₈May be bonded to each other to form a ring. Examples of the 1-valent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R₃₆Also preferred is a hydrogen atom.

As the formula (Y3), a group represented by the following formula (Y3-1) is preferable.

[ chemical formula 3]

Wherein L is₁And L₂Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).

M represents a single bond or a 2-valent linking group.

Q represents an alkyl group which may have, a cycloalkyl group which may have, an aryl group which may have, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).

In the alkyl group and the cycloalkyl group, for example, 1 methylene group may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

In addition, L is preferred₁And L₂One of which is a hydrogen atom and the other is an alkyl group, a cycloalkyl group, an aryl group or a group combining an alkylene group and an aryl group.

Q, M and L₁At least 2 of which may be bonded to form a ring (preferably a 5-or 6-membered ring).

From the viewpoint of miniaturization of the pattern, L₂Preferred are secondary or tertiary alkyl groups, and more preferred are tertiary alkyl groups. Examples of the secondary alkyl group include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of the tertiary alkyl group include a tertiary butyl group and an adamantyl ring group. In these systems, Tg (glass transition temperature) and activation energy are high, and therefore fogging can be suppressed in addition to securing film strength.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As the repeating unit (A-a), a repeating unit represented by the formula (A) is also preferable.

[ chemical formula 4]

L₁Represents a linking group which may have a valence of 2 of a fluorine atom or an iodine atom, R₁Represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom, R₂Represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom. Wherein L is₁、R₁And R₂Has a fluorine atom or an iodine atom.

L₁Represents a linking group having a valence of 2 which may have a fluorine atom or an iodine atom. Examples of the linking group having a valence of 2 which may have a fluorine atom or an iodine atom include-CO-, -O-, -S-, -SO-, -SO₂-, a hydrocarbon group which may have a fluorine atom or an iodine atom (e.g., arylene)Alkyl group, cycloalkylene group, alkenylene group, arylene group, etc.) and a linking group linking a plurality of these groups. Wherein as L₁Alkylene groups having-CO-, -arylene-fluorine atoms or iodine atoms are preferred.

As the arylene group, a phenylene group is preferable.

The alkylene group may be linear or branched. The number of carbon atoms of the alkylene group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and further preferably 3 to 6.

R₁Represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom.

The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and still more preferably 1 to 3.

The alkyl group may have a hetero atom such as an oxygen atom other than a halogen atom.

R₂Represents a leaving group which is released by the action of an acid and may have a fluorine atom or an iodine atom.

Among them, examples of the leaving group include groups represented by the formulae (Z1) to (Z4).

Formula (Z1): -C (Rx)₁₁)(Rx₁₂)(Rx₁₃)

Formula (Z2): -C (═ O) OC (Rx)₁₁)(Rx₁₂)(Rx₁₃)

Formula (Z3): -C (R)₁₃₆)(R₁₃₇)(OR₁₃₈)

Formula (Z4): -C (Rn)₁)(H)(Ar₁)

In the formulae (Z1), (Z2), Rx₁₁～Rx₁₃Each independently represents an alkyl group (linear or branched) which may have a fluorine atom or an iodine atomBranched) or a cycloalkyl group (monocyclic or polycyclic) which may have a fluorine atom or an iodine atom. In addition, all Rx₁₁～Rx₁₃When it is alkyl (linear or branched), Rx₁₁～Rx₁₃At least 2 of which are preferably methyl groups.

Rx₁₁～Rx₁₃In addition to the fluorine atom or iodine atom, the same as Rx in (Y1) and (Y2) above₁～Rx₃The same, and the same definitions and preferred ranges for alkyl and cycloalkyl radicals.

In the formula (Z3), R₁₃₆～R₁₃₈Each independently represents a hydrogen atom or a 1-valent organic group that may have a fluorine atom or an iodine atom. R₁₃₇And R₁₃₈May be bonded to each other to form a ring. As the organic group having a valence of 1 which may have a fluorine atom or an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, an aralkyl group which may have a fluorine atom or an iodine atom, and a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).

In addition, the alkyl group, the cycloalkyl group, the aryl group, and the aralkyl group may contain a hetero atom such as an oxygen atom in addition to the fluorine atom and the iodine atom. That is, as for the alkyl group, the cycloalkyl group, the aryl group and the aralkyl group, for example, 1 methylene group may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

As the formula (Z3), a group represented by the following formula (Z3-1) is preferable.

[ chemical formula 5]

Wherein L is₁₁And L₁₂Each independently represents a hydrogen atom; an alkyl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; a cycloalkyl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; may have a structure selected from the group consisting of fluorine atom, iodine atom and oxygen atomAryl of the heteroatom(s); or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).

M₁Represents a single bond or a 2-valent linking group.

Q₁Represents an alkyl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; a cycloalkyl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; an aryl group selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group which may have a hetero atom selected from the group consisting of a fluorine atom, an iodine atom and an oxygen atom).

In formula (Y4), Ar₁Represents an aromatic ring group which may have a fluorine atom or an iodine atom. Rn₁Represents an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom. Rn₁And Ar₁May be bonded to each other to form a non-aromatic ring.

As the repeating unit (A-a), a repeating unit represented by the general formula (AI) is also preferable.

[ chemical formula 6]

In the general formula (AI) in which,

Xa₁represents a hydrogen atom or an alkyl group which may have a substituent.

T represents a single bond or a 2-valent linking group.

Rx₁～Rx₃Each independently represents an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). Wherein, all Rx are₁～Rx₃When it is alkyl (linear or branched), Rx₁～Rx₃At least 2 of which are preferably methyl groups.

Rx₁～Rx₃2 of which may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

As a result of Xa₁Examples of the optionally substituted alkyl group include a methyl group and a group represented by-CH₂-R₁₁The group shown. R₁₁Examples of the organic group having a halogen atom (e.g., fluorine atom), a hydroxyl group, and a 1-valent organic group include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, with an alkyl group having 3 or less carbon atoms being preferred, and a methyl group being more preferred. As Xa₁Preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the linking group having a valence of 2 in T include an alkylene group, an aromatic ring group, -COO-Rt-group, and-O-Rt-group. Wherein Rt represents an alkylene group or a cycloalkylene group.

T is preferably a single bond or a-COO-Rt-group. When T represents a-COO-Rt-group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, more preferably-CH₂-radical, - (CH)₂)₂-radical or- (CH)₂)₃-a radical.

As Rx₁～Rx₃The alkyl group of (1) 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, a tert-butyl group and the like.

As Rx₁～Rx₃As the cycloalkyl group of (2), a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group and an adamantyl group are preferable.

As Rx₁～Rx₃The cycloalkyl group in which 2 of these groups are bonded is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and is preferably a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferable.

With respect to Rx₁～Rx₃Wherein 2 of the cycloalkyl groups are bonded, for example, 1 methylene group constituting the ring may be substituted with a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl groupAnd (4) substituting the group.

As the repeating unit represented by the general formula (AI), for example, Rx is preferable₁Is methyl or ethyl, Rx₂And Rx₃And bonded to form the cycloalkyl group.

When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

The repeating unit represented by the general formula (AI) is preferably a repeating unit (Xa) of a tert-alkyl ester of an acid-decomposable (meth) acrylic acid₁A repeating unit representing a hydrogen atom or a methyl group, and T represents a single bond).

The resin (a) may have 1 kind of repeating unit (a-a) alone or 2 or more kinds.

The content of the repeating unit (a-a) (the total content when 2 or more repeating units (a-a) are present) is preferably 15 to 80 mol%, more preferably 20 to 70 mol%, based on all the repeating units in the resin (a).

In the resin (a), the content of the repeating unit that decomposes by the action of an acid to form a carboxyl group is preferably 25 to 70 mol% based on all the repeating units in the resin (a).

As the repeating unit (A-a), the resin (A) preferably has at least 1 repeating unit selected from the group consisting of repeating units represented by the following general formulae (A-VIII) to (A-XII).

[ chemical formula 7]

In the general formula (A-VIII), R₅Represents a tert-butyl group or a-CO-O- (tert-butyl) group.

In the general formula (A-IX), R₆And R₇Each independently represents a 1-valent organic group. Examples of the 1-valent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

In the general formula (A-X), p represents 1 or 2.

In the general formulae (A-X) to (A-XII), R₈R represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms₉Represents an alkyl group having 1 to 3 carbon atoms.

In the general formula (A-XII), R₁₀Represents an alkyl group having 1 to 3 carbon atoms or an adamantyl group.

Specific examples of the repeating unit (A-a) are shown below, but the present invention is not limited thereto. In addition, in the formula, Xa₁Representation H, CH₃、CF₃And CH₂Wherein each of OH, Rxa and Rxb represents a linear or branched alkyl group having 1 to 4 carbon atoms.

[ chemical formula 8]

[ chemical formula 9]

[ chemical formula 10]

[ chemical formula 11]

[ chemical formula 12]

(repeating Unit having acid group)

The resin (a) may include a repeating unit having an acid group.

As the repeating unit having an acid group, a repeating unit represented by the following general formula (B) is preferable.

[ chemical formula 13]

R₃Represents a hydrogen atom or an organic group having a valence of 1 of a fluorine atom or an iodine atom. As the organic group having a valence of 1 which may have a fluorine atom or an iodine atom, preferred is a group represented by the formula-L₄-R₈The group shown. L is₄Represents a single bond or an ester group. R₈Examples thereof include an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a combination thereof.

R₄And R₅Each independently represents a hydrogen atom, a fluorine atom, an iodine atom or an alkyl group which may have a fluorine atom or an iodine atom.

L₂Represents a single bond or an ester group.

L₃Represents an aromatic hydrocarbon ring group having a valence of (n + m +1) or an alicyclic hydrocarbon ring group having a valence of (n + m + 1). Examples of the aromatic hydrocarbon ring group include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups.

R₆Represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). In addition, R₆When is hydroxy, L₃An aromatic hydrocarbon ring group having a valence of (n + m +1) is preferable.

R₇Represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

m represents an integer of 1 or more. m is preferably an integer of 1 to 3, preferably an integer of 1 to 2.

n represents 0 or an integer of 1 or more. n is preferably an integer of 1 to 4.

Further, (n + m +1) is preferably an integer of 1 to 5.

As the repeating unit having an acid group, a repeating unit represented by the following general formula (I) is also preferable.

[ chemical formula 14]

In the general formula (I),

R₄₁、R₄₂and R₄₃Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. Wherein R is₄₂And Ar₄May be bonded to form a ring, in which case R₄₂Represents a single bond or an alkylene group.

X₄Represents a single bond, -COO-or-CONR₆₄-，R₆₄Represents a hydrogen atom or an alkyl group.

L₄Represents a single bond or an alkylene group.

Ar₄An (n +1) -valent aromatic ring group, and R₄₂And (n +2) -valent aromatic ring groups when bonded to form a ring.

n represents an integer of 1 to 5.

As R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl group of (3) is preferably an alkyl group having not more than 20 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, and a dodecyl group, more preferably an alkyl group having not more than 8 carbon atoms, and still more preferably an alkyl group having not more than 3 carbon atoms.

As R in the general formula (I)₄₁、R₄₂And R₄₃The cycloalkyl group of (b) may be of a monocyclic type or of a polycyclic type. Among them, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl are preferable.

As R in the general formula (I)₄₁、R₄₂And R₄₃Examples of the halogen atom of (2) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable.

As R in the general formula (I)₄₁、R₄₂And R₄₃The alkyl group contained in the alkoxycarbonyl group of (1), preferably with the above-mentioned R₄₁、R₄₂、R₄₃The alkyl groups in (1) are the same.

Ar₄Representing a valence of (n +1)An aromatic ring group. The 2-valent aromatic ring group in the case where n is 1 may have a substituent, and is preferably an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group, or an aromatic ring group containing a heterocycle such as a thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, or thiazole ring.

Specific examples of the (n +1) -valent aromatic ring group in which n is an integer of 2 or more include groups obtained by removing (n-1) arbitrary hydrogen atoms from the specific examples of the 2-valent aromatic ring group. The (n +1) -valent aromatic ring group may further have a substituent.

Examples of the substituent which the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, and (n +1) -valent aromatic ring group may have include R in the general formula (I)₄₁、R₄₂And R₄₃Alkoxy groups such as alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy groups; aryl groups such as phenyl; and the like.

As a result of X₄Represented by-CONR₆₄-(R₆₄Represents a hydrogen atom or an alkyl group)₆₄Examples of the alkyl group (b) include alkyl groups having not more than 20 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 and a dodecyl group, and preferably alkyl groups having not more than 8 carbon atoms.

As X₄Preferably a single bond, -COO-or-CONH-, more preferably a single bond or-COO-.

As L₄The alkylene group in (1) 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, and an octylene group.

As Ar₄The aromatic ring group has 6 to 18 carbon atoms is preferable, and the benzene ring group, the naphthalene ring group and the biphenyl ring group are more preferable.

Specific examples of the repeating unit represented by the general formula (I) are shown below, and the present invention is not limited thereto. Wherein a represents 1 or 2.

[ chemical formula 15]

[ chemical formula 16]

[ chemical formula 17]

Recurring Unit (A-1) derived from hydroxystyrene

As the repeating unit having an acid group, the resin (a) preferably has a repeating unit (a-1) derived from hydroxystyrene.

Examples of the recurring unit (A-1) derived from hydroxystyrene include a recurring unit represented by the following general formula (1).

[ chemical formula 18]

In the general formula (1) above,

a represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group.

R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and when a plurality of R are present, they may be the same or different. When there are plural kinds of R, they may form a ring together with each other. As R, a hydrogen atom is preferred.

a represents an integer of 1 to 3, and b represents an integer of 0 to (5-a).

As the repeating unit (A-1), a repeating unit represented by the following general formula (A-I) is preferable.

[ chemical formula 19]

The composition containing the resin (A) having the repeating unit (A-1) is preferably used for KrF exposure, EB exposure or EUV exposure. The content of the repeating unit (a-1) in this case is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and still more preferably 50 to 100 mol% based on all the repeating units in the resin (a).

(containing at least 1 kind of repeating unit (A-2) selected from the group consisting of lactone structure, sultone structure, carbonate structure and hydroxyadamantane structure.)

The resin (a) may include a repeating unit (a-2) having at least 1 selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure.

Repeating Unit having lactone Structure or sultone Structure

The lactone structure or the sultone structure in the repeating unit having a lactone structure or a sultone structure is not particularly limited, and a 5-to 7-membered ring lactone structure or a 5-to 7-membered ring sultone structure is preferable, and another ring structure is more preferably condensed on the 5-to 7-membered ring lactone structure in a form of forming a bicyclic structure or a spiro structure, or condensed on the 5-to 7-membered ring sultone structure in a form of forming a bicyclic structure or a spiro structure. Further, it is preferable that the resin composition contains a repeating unit having a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-21) or a sultone structure represented by any one of the following general formulae (SL1-1) to (SL 1-3). The lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures are general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21) or general formula (SL 1-1).

[ chemical formula 20]

The lactone moiety or the sultone moiety may have a substituent (Rb)²) Or may have no substituent (Rb)²). As takingSubstituent (Rb)²) The alkyl group having 1 to 8 carbon atoms, the cycloalkyl group having 4 to 7 carbon atoms, the alkoxy group having 1 to 8 carbon atoms, the alkoxycarbonyl group having 2 to 8 carbon atoms, the carboxyl group, the halogen atom other than the fluorine atom, the hydroxyl group, the cyano group or the acid-decomposable group is preferable, and the alkyl group having 1 to 4 carbon atoms, the cyano group or the acid-decomposable group is more preferable. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of substituents (Rb)²) May be the same or different. And, there are a plurality of substituents (Rb)²) May be bonded to each other to form a ring.

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following formula III is preferable from the viewpoint of the tolerance of the depth of focus and the pattern linearity.

From the viewpoint of the depth of focus tolerance and the pattern linearity, the resin containing a repeating unit having an acid-decomposable group preferably has a repeating unit represented by the following formula III.

[ chemical formula 21]

In the above-mentioned formula III, the compound,

a represents an ester bond (a group represented by-COO-) or an amide bond (a group represented by-CONH-).

n is represented by-R⁰The number of repetitions of the structure represented by-Z-represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R is absent⁰-Z-, A and R⁸By a single bond.

R⁰Represents alkylene, cycloalkylene, or a combination thereof. In the presence of a plurality of R⁰When used, each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.

Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When a plurality of Z's are present, each Z's independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.

R⁸Represents a compound having a lactone structure or a sultone structureA structural 1-valent organic group.

R⁷Represents a hydrogen atom, a halogen atom other than a fluorine atom, or a 1-valent organic group (preferably a methyl group).

R⁰The alkylene group or cycloalkylene group of (a) may have a substituent.

Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

As the repeating unit having a lactone structure or a sultone structure, at least 1 repeating unit selected from the group consisting of repeating units represented by the following general formulae (A-II) to (A-V) is also preferable.

[ chemical formula 22]

In the general formulae (A-II) to (A-V), R₁Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

R₂Represents an alkyl group having 1 to 4 carbon atoms, a cyano group or-CO-O-R₂₁。R₂₁Represents an alkyl group having 1 to 4 carbon atoms.

X₁Represents a single bond, an alkylene group having 1 to 3 carbon atoms or-R₃-CO-O-，R₃Represents an alkylene group having 1 to 3 carbon atoms.

m represents 0 or 1.

Specific examples of monomers that satisfy the repeating unit represented by formula III or the repeating units represented by general formulae (A-II) to (A-V) are given below. The following embodiments conform to R in formula III⁷And R in the general formulae (A-II) to (A-V)₁The methyl group is optionally substituted with a hydrogen atom or an alkyl group having 2 to 3 carbon atoms.

[ chemical formula 23]

In addition to the above monomers, the monomers shown below can also be preferably used as the repeating unit having a lactone structure or a sultone structure.

[ chemical formula 24]

Repeating Unit having carbonate Structure

The resin (a) may contain a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following formula A-1.

[ chemical formula 25]

In the formula A-1, R_A ¹Represents a hydrogen atom, a halogen atom other than a fluorine atom, or a 1-valent organic group (preferably methyl group), n represents an integer of 0 or more, R_A ²Represents a substituent. When n is 2 or more, R_A ²Each independently represents a substituent, a represents a single bond or a 2-valent linking group, and Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by — O — C (═ O) -O — "in the formula.

As the repeating unit having a carbonate structure, a repeating unit represented by the following general formula (A-VI) is more preferable.

[ chemical formula 26]

In the general formulae (A-VI), R₁Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

X₁Represents a single bond, an alkylene group having 1 to 3 carbon atoms or-R₃-CO-O-，R₃Represents an alkylene group having 1 to 3 carbon atoms.

The resin (a) preferably has a repeating unit described in paragraphs 0370 to 0414 of the specification of U.S. patent application publication No. 2016/0070167 as a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure.

Repeating Unit having hydroxyadamantane Structure

The resin (a) may include a repeating unit having a hydroxyadamantane structure. Examples of the repeating unit having a hydroxyadamantane structure include a repeating unit represented by the following general formula (AIIa).

[ chemical formula 27]

In the general formula (AIIa), R_1cRepresents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. R_2c～R_4cEach independently represents a hydrogen atom or a hydroxyl group. Wherein R is_2c～R_4cAt least 1 of them represents a hydroxyl group. Preferably R_2c～R_4c1 or 2 of them are hydroxyl groups, and the remainder are hydrogen atoms.

The repeating unit having a hydroxyadamantane structure is more preferably a repeating unit represented by the following general formula (a-VII).

[ chemical formula 28]

In the general formula (A-VII), R₁Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents 0 or 1.

Specific examples of the repeating unit having a hydroxyadamantane structure will be described below, but the present invention is not limited thereto.

[ chemical formula 29]

When the resin (a) contains a repeating unit having a hydroxyadamantane structure, the content of the repeating unit having a hydroxyadamantane structure is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 10 to 25 mol% based on all repeating units in the resin (a).

The resin (a) may have 1 kind of repeating unit (a-2) alone having at least 1 kind selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure, or may have 2 or more kinds at the same time.

The repeating unit (a-2) is preferably a repeating unit derived from a (meth) acrylate containing at least 1 selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure.

The content of the repeating unit (a-2) contained in the resin (a) (when a plurality of repeating units (a-2) are present, the total content thereof) is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, and further preferably 20 to 60 mol% with respect to all repeating units of the resin (a).

The resin (a) preferably has at least one of the above-described hydroxystyrene-derived repeating unit (a-1) and a repeating unit (a-2) containing at least 1 selected from the group consisting of a lactone structure, a carbonate structure, a sultone structure, and a hydroxyadamantane structure.

Among them, it is preferable that the repeating unit (A-1) is a repeating unit represented by the above general formula (A-I) and the repeating unit (A-2) contains at least 1 selected from the group consisting of repeating units represented by the above general formulae (A-II) to (A-VII).

The repeating unit (A-1), the repeating unit (A-2) and the repeating units represented by the general formulae (A-I) to (A-VII) are as described above, including preferred embodiments thereof.

(other repeating units)

The resin (A) may have a repeating unit other than the repeating unit (A-a) having an acid-decomposable group, the repeating unit having an acid group, and the repeating unit (A-2).

Repeating Unit having fluorine atom or iodine atom

The resin (a) may contain a repeating unit having a fluorine atom or an iodine atom. The repeating unit having a fluorine atom or an iodine atom does not include the repeating unit (A-a) having an acid-decomposable group, the repeating unit having an acid group, and the repeating unit (A-2).

As the repeating unit having a fluorine atom or an iodine atom, a repeating unit represented by the formula (C) is preferable.

[ chemical formula 30]

L₅Represents a single bond or an ester group.

R₉Represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom.

R₁₀Represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these.

The content of the repeating unit having a fluorine atom or an iodine atom is preferably 0 to 50 mol%, more preferably 5 to 45 mol%, and further preferably 10 to 40 mol% based on all the repeating units in the resin (a).

Repeating Unit having photoacid generating group

As the repeating unit other than the above, the resin (a) may contain a repeating unit having a group which generates an acid by irradiation with radiation (hereinafter, also referred to as a "photoacid generating group").

In this case, the repeating unit having a photoacid generating group is considered to correspond to the photoacid generator (P).

Examples of such a repeating unit include a repeating unit represented by the following general formula (4).

[ chemical formula 31]

R⁴¹Represents a hydrogen atom or a methyl group. L is⁴¹Represents a single bond or a 2-valent linking group. L is⁴²Represents a 2-valent linking group. R⁴⁰By irradiationThe irradiation with the light decomposes to generate an acid at the side chain.

Specific examples of the repeating unit represented by the general formula (4) are shown below, but the present invention is not limited thereto.

[ chemical formula 32]

In addition, examples of the repeating unit represented by the general formula (4) include the repeating units described in paragraphs [0094] to [0105] of Japanese patent application laid-open No. 2014-041327.

The content of the repeating unit having a photoacid generating group is preferably 1 to 40 mol%, more preferably 5 to 35 mol%, and further preferably 5 to 30 mol% with respect to all repeating units in the resin (a).

Repeating Unit having alkali-soluble group

The resin (a) may include a repeating unit having an alkali-soluble group.

Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol having an α -position substituted with an electron-withdrawing group (for example, hexafluoroisopropanol group), with a carboxyl group being preferred. By the resin (a) containing a repeating unit having an alkali-soluble group, resolution in contact hole applications is improved.

Examples of the repeating unit having an alkali-soluble group include a repeating unit in which an alkali-soluble group is directly bonded to a main chain of a resin, such as a repeating unit based on acrylic acid or methacrylic acid, or a repeating unit in which an alkali-soluble group is bonded to a main chain of a resin via a linking group. In addition, the linking group may have a monocyclic or polycyclic cyclic hydrocarbon structure.

As the repeating unit having an alkali-soluble group, a repeating unit based on acrylic acid or methacrylic acid is preferable.

The content of the repeating unit having an alkali-soluble group is preferably 0 to 20 mol%, more preferably 3 to 15 mol%, and further preferably 5 to 10 mol% with respect to all repeating units in the resin (a).

Specific examples of the repeating unit having an alkali-soluble group are shown below, but the present invention is not limited thereto. In the specific example, Rx represents H, CH₃、CH₂OH or CF₃。

[ chemical formula 33]

Repeating Unit having neither acid-decomposable group nor polar group

The resin (a) may further contain a repeating unit having no acid-decomposable group or no polar group. The repeating unit having no acid-decomposable group or polar group preferably has an alicyclic hydrocarbon structure.

Examples of the repeating unit having no acid-decomposable group or no polar group include the repeating units described in paragraphs 0236 to 0237 of the specification of U.S. patent application publication No. 2016/0026083 and the repeating unit described in paragraph 0433 of the specification of U.S. patent application publication No. 2016/0070167.

Preferred examples of the monomer having a repeating unit having neither an acid-decomposable group nor a polar group are shown below.

[ chemical formula 34]

The resin (a) may have 1 kind of repeating unit having no acid-decomposable group or no polar group alone, or may have 2 or more kinds at the same time.

The content of the repeating unit having no acid-decomposable group or polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, and still more preferably 5 to 25 mol% based on all the repeating units in the resin (a).

The resin (a) may have various repeating structural units in addition to the above-described repeating structural units for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

(Properties of resin (A))

As the resin (a), it is preferable that all the repeating units are composed of repeating units derived from a (meth) acrylate-based monomer. In this case, any resin in which all the repeating units are derived from a methacrylate monomer, all the repeating units are derived from an acrylate monomer, and all the repeating units are derived from a methacrylate monomer and an acrylate monomer can be used. The repeating unit derived from the acrylate-based monomer is preferably 50 mol% or less with respect to all repeating units in the resin (a).

When the composition is used for argon fluoride (ArF) exposure, the resin (a) preferably has substantially no aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and further preferably 0 mol% or less with respect to all the repeating units of the resin (a), that is, the repeating unit having an aromatic group is not included.

When the composition is used for ArF exposure, the resin (a) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure and preferably does not contain any of a fluorine atom and a silicon atom.

When the composition is used for krypton fluoride (KrF) exposure, EB exposure, or EUV exposure, the resin (a) preferably contains a repeating unit having an aromatic hydrocarbon group, and more preferably contains a repeating unit having a phenolic hydroxyl group.

Examples of the repeating unit having a phenolic hydroxyl group include the above-mentioned repeating unit (a-1) derived from hydroxystyrene and a repeating unit derived from hydroxystyrene (meth) acrylate.

When the composition is used for KrF exposure, EB exposure, or EUV exposure, the resin (a) preferably contains a repeating unit having a structure in which a hydrogen atom of a phenolic hydroxyl group is protected by a group (release group) decomposed and released by the action of an acid.

When the composition is used for KrF exposure, EB exposure, or EUV exposure, the content of the aromatic hydrocarbon group-containing repeating unit in the resin (a) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and still more preferably 50 to 100 mol% based on all the repeating units in the resin (a).

The resin (a) can be synthesized according to a conventional method (e.g., radical polymerization).

The weight average molecular weight (Mw) of the resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and still more preferably 5,000 to 15,000. By setting the weight average molecular weight (Mw) of the resin (a) to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and further prevent deterioration of film formability due to deterioration of developability and increase in viscosity. The weight average molecular weight (Mw) of the resin (a) is a polystyrene equivalent value measured by the GPC method.

The degree of dispersion (molecular weight distribution) of the resin (A) is usually 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The smaller the degree of dispersion, the more excellent the resolution and resist shape, and further, the smoother the side wall of the pattern, the more excellent the roughness.

The content of the resin (a) in the composition is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, based on the total solid content of the composition.

Further, the resin (A) may be used alone in 1 kind, or may be used in combination in 2 or more kinds.

(photoacid Generator (P))

The actinic ray-sensitive or radiation-sensitive resin composition contains a photoacid generator (P). The photoacid generator (P) is not particularly limited as long as it is a compound that generates an acid upon irradiation with radiation.

The photoacid generator (P) may be a low molecular weight compound or may be incorporated in a part of a polymer. Also, a mode of using a low molecular compound and a mode of combining into a part of a polymer may be used at the same time.

When the photoacid generator (P) is a low-molecular-weight compound, the weight average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less.

When the photoacid generator (P) is incorporated in a part of the polymer, it may be incorporated in a part of the resin (a) or may be incorporated in a resin different from the resin (a).

In the present invention, the photoacid generator (P) is preferably a low molecular weight compound.

The photoacid generator (P) is not particularly limited as long as it is a known photoacid generator, but is preferably a compound that generates an organic acid by irradiation with radiation, and more preferably a photoacid generator having a fluorine atom or an iodine atom in the molecule.

Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.), carboxysulfonimide acids, bis (alkylsulfonyl) imide acids, and tris (alkylsulfonyl) methylate acids.

The volume of the acid generated by the photoacid generator (P) is not particularly limited, but is preferably selected from the viewpoint of suppressing diffusion of the acid generated by exposure to a non-exposed portion and optimizing resolutionThe above, more preferred areThe above is more preferableThe above, particularly preferred areThe above. In addition, the volume of the acid generated by the photoacid generator (P) is preferably large from the viewpoint of sensitivity or solubility in a coating solventThe following are more preferableThe following are more preferredThe following.

The volume value was obtained by using "WinMOPAC" manufactured by Fujitsu Limited. When calculating the volume value, the chemical structure of each acid is inputted, the structure is used as an initial structure, the most stable three-dimensional configuration of each acid is determined by Molecular force field calculation using MM (Molecular Mechanics) 3 method, and then the "accessible volume: volume is allowed to pass through.

The structure of the acid generated by the photoacid generator (P) is not particularly limited, and from the viewpoint of suppressing the diffusion of the acid and optimizing the resolution, it is preferable that the interaction between the acid generated by the photoacid generator (P) and the resin (a) be strong. From this viewpoint, when the acid generated by the photoacid generator (P) is an organic acid, it is preferable that the acid has a polar group in addition to an organic acid group such as a sulfonic acid group, a carboxylic acid group, a carboxysulfonylimido acid group, a disulfonylimido acid group, or a trisulfonyl-methylated acid group.

Examples of the polar group include an ether group, an ester group, an amide group, an acyl group, a sulfo group, a sulfonyloxy group, a sulfonamide group, a thioether group, a thioester group, a urea group, a carbonate group, a carbamate group, a hydroxyl group, and a mercapto group.

The number of polar groups of the generated acid is not particularly limited, but is preferably 1 or more, and more preferably 2 or more. However, from the viewpoint of suppressing the excessive development, the number of the polar groups is preferably less than 6, and more preferably less than 4.

As the photoacid generator (P), the following compounds are preferable. In addition, each compound is labeled with a calculated value (unit) of the volume of acid generated from each compound by exposure)。

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

Among them, the photoacid generator (P) is preferably a photoacid generator comprising an anion portion and a cation portion.

As the photoacid generator (P), a compound represented by the following general formula (ZI) or a compound represented by the general formula (ZII) is preferable.

[ chemical formula 38]

In the above-mentioned general formula (ZI),

R₂₀₁、R₂₀₂and R₂₀₃Each independently represents an organic group.

As R₂₀₁、R₂₀₂And R₂₀₃The number of carbon atoms of the organic group (2) is preferably 1 to 30, more preferably 1 to 20.

And may be represented by R₂₀₁～R₂₀₃2 of them are bonded to form a ring structure, and the ring may have an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. As a group consisting of R₂₀₁～R₂₀₃Examples of the group in which 2 members are bonded include an alkylene group (for example, butylene group, pentylene group, or the like).

Z^-Denotes a non-nucleophilic anion (an anion whose ability to cause nucleophilic reactions is significantly low).

Examples of the non-nucleophilic anion include a sulfonic acid anion (aliphatic sulfonic acid anion, aromatic sulfonic acid anion, camphorsulfonic acid anion, etc.), a carboxylic acid anion (aliphatic carboxylic acid anion, aromatic carboxylic acid anion, aralkylcarboxylic acid anion, etc.), a sulfonimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methide anion.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and a linear or branched alkyl group having 1 to 30 carbon atoms and a cycloalkyl group having 3 to 30 carbon atoms are preferable.

The aromatic ring group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group and a naphthyl group.

Specific examples of the substituent that the alkyl group, the cycloalkyl group and the aryl group may have include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy 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 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkylsulfinyl group (preferably having 1 to 15 carbon atoms), an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), an alkylaryloxysulfonyl group (preferably having 7 to 20 carbon atoms), a cycloalkylaryloxysulfonyl group (preferably having 10 to 20 carbon atoms), and the like, Alkoxyalkoxy (preferably having 5 to 20 carbon atoms) and cycloalkylalkoxyalkoxy (preferably having 8 to 20 carbon atoms).

As the aralkyl group in the aralkyl carboxylic acid anion, preferred is an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a naphthylbutyl group.

Examples of the sulfonimide anion include saccharin (saccharorin) anion.

The alkyl group in the bis (alkylsulfonyl) imide anion and the tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of the substituent for the alkyl group include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkoxysulfonyl group, an aryloxysulfonyl group and a cycloalkylaryloxysulfonyl group, and a fluorine atom or an alkyl group substituted with a fluorine atom is preferable.

Further, the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure. Thereby increasing acid strength.

Examples of other non-nucleophilic anions include fluorinated phosphor (e.g., PF)₆ ^-) Boron fluoride (e.g., BF)₄ ^-) And antimony fluoride (e.g., SbF)₆ ^-)。

As the non-nucleophilic anion, an aliphatic sulfonic acid anion substituted with a fluorine atom at least in the α -position of the sulfonic acid, an aromatic sulfonic acid anion substituted with a fluorine atom or a group having a fluorine atom, a bis (alkylsulfonyl) imide anion substituted with a fluorine atom for the alkyl group, or a tris (alkylsulfonyl) methide anion substituted with a fluorine atom for the alkyl group are preferable. Among them, a perfluoroaliphatic sulfonic acid anion (preferably having 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom is more preferable, and a nonafluorobutane sulfonic acid anion, a perfluorooctane sulfonic acid anion, a pentafluorobenzene sulfonic acid anion or a 3, 5-bis (trifluoromethyl) benzenesulfonic acid anion is further preferable.

From the viewpoint of acid strength, it is preferable that the pKa of the acid to be generated is-1 or less because sensitivity is improved.

Further, as the non-nucleophilic anion, AN anion represented by the following general formula (AN1) is also preferable.

[ chemical formula 39]

In the formula (I), the compound is shown in the specification,

each Xf independently represents a fluorine atom or an alkyl group substituted with at least 1 fluorine atom.

R¹And R²Each independently represents a hydrogen atom, a fluorine atom or an alkyl group, and R when a plurality of R's exist¹And R²Each of which may be the same or different.

L represents a linking group having a valence of 2, and L may be the same or different when a plurality of L's are present.

A represents a cyclic organic group.

x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.

The general formula (AN1) will be described in more detail.

The number of carbon atoms in the alkyl group substituted with a fluorine atom in Xf is preferably 1 to 10, more preferably 1 to 4. Further, as the alkyl group substituted with a fluorine atom for Xf, a perfluoroalkyl group is preferable.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specific examples of Xf include fluorine atom and CF₃、C₂F₅、C₃F₇、C₄F₉、CH₂CF₃、CH₂CH₂CF₃、CH₂C₂F₅、CH₂CH₂C₂F₅、CH₂C₃F₇、CH₂CH₂C₃F₇、CH₂C₄F₉And CH₂CH₂C₄F₉Etc., among them, fluorine atom or CF are preferred₃. In particular, both Xf are preferably fluorine atoms.

R¹And R²The alkyl group(s) may have a substituent (preferably a fluorine atom), and the number of carbon atoms in the substituent is preferably 1 to 4. The substituent is preferably a perfluoroalkyl group having 1 to 4 carbon atoms. As R¹And R²Specific examples of the alkyl group having a substituent(s) of (1) include CF₃、C₂F₅、C₃F₇、C₄F₉、C₅F₁₁、C₆F₁₃、C₇F₁₅、C₈F₁₇、CH₂CF₃、CH₂CH₂CF₃、CH₂C₂F₅、CH₂CH₂C₂F₅、CH₂C₃F₇、CH₂CH₂C₃F₇、CH₂C₄F₉And CH₂CH₂C₄F₉Etc., of which CF is preferred₃。

As R¹And R²Preferably fluorine atom or CF₃。

x is preferably an integer of 1 to 10, more preferably 1 to 5.

y is preferably an integer of 0 to 4, more preferably 0.

z is preferably an integer of 0 to 5, more preferably an integer of 0 to 3.

The linking group having a valence of 2 in L is not particularly limited, and examples thereof include-COO-, -CO-, -O-, -S-, -SO-, -₂The alkylene group, the cycloalkylene group, the alkenylene group, and the linking group to which these plural groups are linked are preferably a linking group having 12 or less total carbon atoms. Among them, preferred is-COO-, -OCO-, -CO-or-O-, and more preferred is-COO-or-OCO-.

The cyclic organic group of a is not particularly limited as long as it has a cyclic structure, and examples thereof include an alicyclic group, an aromatic ring group, and a heterocyclic group (including not only aromatic groups but also non-aromatic groups).

The alicyclic group may be monocyclic or polycyclic, and monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl are preferable, and polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl and adamantyl are also preferable in addition to these groups. Among them, from the viewpoint of suppressing the in-film diffusion in the post-exposure heating step and improving the MEEF (Mask Error Enhancement Factor), alicyclic groups having a large integration structure of 7 or more carbon atoms such as a norbornyl group, a tricyclodecyl group, a tetracyclodecyl group, a tetracyclododecyl group, and an adamantyl group are preferable.

Examples of the aromatic ring group include a benzene ring, a naphthalene ring, a phenanthrene ring, and an anthracene ring.

Examples of the heterocyclic group include groups derived from furan, thiophene, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, pyridine, and the like. Among them, groups derived from furan ring, thiophene ring and pyridine ring are preferable.

Examples of the cyclic organic group include groups having a lactone structure, and specific examples thereof include groups having lactone structures represented by the general formulae (LC1-1) to (LC 1-17).

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear, branched or cyclic, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic, and may be spiro in the case of polycyclic, and preferably has 3 to 20 carbon atoms), an aryl group (preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a carbamate group, a urea group, a thioether group, a sulfonamide group, and a sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to the formation of a ring) may be a carbonyl carbon.

As R₂₀₁、R₂₀₂And R₂₀₃Examples of the organic group of (2) include aryl, alkyl and cycloalkyl groups.

R₂₀₁、R₂₀₂And R₂₀₃Preferably at least 1 is aryl, more preferably all three are aryl. The aryl group may be a heteroaryl group such as an indole residue or a pyrrole residue, in addition to a phenyl group or a naphthyl group.

As R₂₀₁～R₂₀₃The alkyl group (b) is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, and more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group or an n-butyl group.

As R₂₀₁～R₂₀₃The cycloalkyl group of (3) is preferably a cycloalkyl group having 3 to 10 carbon atoms, and more preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group.

Examples of the substituent which these groups may have include a halogen atom such as a nitro group or a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy 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 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), and the like.

In the general formula (ZII), the group,

R₂₀₄～R₂₀₅are respectively independentAnd represents an aryl group, an alkyl group or a cycloalkyl group.

As R₂₀₄～R₂₀₅And aryl, alkyl and cycloalkyl groups as R in the above general formula (ZI)₂₀₁～R₂₀₃The aryl, alkyl and cycloalkyl groups in the description are the same.

As R₂₀₄～R₂₀₅The aryl group, the alkyl group and the cycloalkyl group of (4) may have a substituent, and examples thereof include R in the compound (ZI)₂₀₁～R₂₀₃The aryl, alkyl and cycloalkyl groups of (a) may have a substituent.

Z^-The non-nucleophilic anion is represented by the formula (ZI) wherein Z is^-The same non-nucleophilic anion as (a).

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

[ chemical formula 40]

Preferred examples of the photoacid generator (P) include compounds represented by the following general formulae (B-I) to (B-V).

[ chemical formula 41]

In the general formulae (B-I) to (B-V), M⁺Denotes a sulfonium cation or an iodonium cation. M in the general formulae (B-I) to (B-V)⁺Preferred are sulfonium cations of the above general formula (ZI) or iodonium cations of the general formula (ZII), including preferred ones thereof.

In the general formula (B-I), R₁₁Represents an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom. As R₁₁The alkyl group having 1 to 8 carbon atoms substituted with at least 1 fluorine atom is preferable, the perfluoroalkyl group having 1 to 8 carbon atoms is more preferable, and the perfluoroalkyl group having 2 to 4 carbon atoms is further preferable.

In the general formula (B-I)I) In, R₁₂Represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or-CF₃。R₁₂The alkyl group is preferably a C3-6 alkyl group, and a linear or branched C3-6 alkyl group or cyclohexyl group is preferable. And, R₁₂Relative to (-SO)₃ ^-) The radicals are preferably located in the ortho or para position.

In the general formula (B-II), q represents an integer of 1 to 5. q is preferably an integer of 2 to 4, preferably 2 or 3.

In the general formula (B-III), R₁₃Represents a hydrogen atom, a fluorine atom or CF₃. Preferably R₁₃At least 1 of (A) represents a fluorine atom or CF₃。

In the general formula (B-III), X₂represents-CO-O-, -CH₂-CO-O-or-CH₂-O-CO-。

In the general formula (B-III), r represents an integer of 0 to 2. r is preferably 0 or 1.

In the general formula (B-III), s represents an integer of 1 to 3. s is preferably 1 or 2.

In the general formula (B-IV), R₁₃Represents a hydrogen atom, a fluorine atom or CF₃. In the general formula (B-IV), R is preferred₁₃At least 1 of (A) represents a fluorine atom or CF₃More preferably 2 or more R₁₃Represents a fluorine atom or CF₃。

In the general formula (B-IV), R₁₄Represents a 1-valent polycyclic group which may have a substituent. The 1-valent polycyclic group is not particularly limited as long as it is a group having a plurality of ring structures, and examples thereof include groups having a polycyclic structure in a cyclic organic group represented by a in the above general formula (AN 1). More specifically, polycyclic cycloalkyl groups such as norbornanyl ring group, tetracyclodecane ring group, tetracyclododecane ring group, and adamantane ring group are mentioned, and norbornanyl ring group and adamantane ring group are preferred.

In the general formula (B-V), R₁₃Represents a hydrogen atom, a fluorine atom or CF₃. In the general formula (B-V), R is preferred₁₃At least 1 of (A) represents a fluorine atom or CF₃More preferably 2 or more R₁₃Represents a fluorine atom or CF₃。

In the general formula (B-V), R₁₅Represents an organic group having a valence of 1. As a group consisting of R₁₅The 1-valent organic group is preferably an alkyl group having 1 to 6 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

In the general formula (B-V), X₃represents-O-CO-O-, -SO₂-or-SO₂-NR₁₆-。R₁₆Represents a hydrogen atom or an alkyl group, or represents a group with R₁₅Alkylene groups bonded to form a ring structure.

In the compound represented by the general formula (B-V), X₃represents-SO₂-NR₁₆-, preferably from R₁₅And R₁₆A C4-C6 alkylene group bonded with-NR₁₆The nitrogen atom in the group forms a heterocyclic ring which may have a substituent.

The composition preferably contains at least 1 kind selected from the group consisting of compounds represented by the above general formulae (B-I) to (B-V) as the photoacid generator (P).

The photoacid generator (P) can be used in the paragraphs [0368] to [0377] of Japanese patent application laid-open No. 2014-41328 and the paragraphs [0240] to [0262] of Japanese patent application laid-open No. 2013-228681 (corresponding to [0339] of the specification of U.S. patent application laid-open No. 2015/004533), and these contents are incorporated in the present specification. Specific preferred examples include the following compounds, but are not limited thereto.

[ chemical formula 42]

[ chemical formula 43]

[ chemical formula 44]

The content of the photoacid generator (P) in the composition is not particularly limited, but is preferably 5 to 50 mass%, more preferably 10 to 40 mass%, and still more preferably 10 to 35 mass% with respect to the total solid content of the composition.

The photoacid generator (P) may be used alone in 1 kind, or may be used in combination in 2 or more kinds. When 2 or more kinds of photoacid generators (P) are used simultaneously, the total amount thereof is preferably within the above range.

(acid diffusion controller (Q))

The composition may contain an acid diffusion controller (Q).

The acid diffusion controller (Q) functions as a quencher that captures an acid generated from the photoacid generator (P) or the like during exposure and suppresses a reaction of the acid-decomposable resin in the unexposed portion caused by an excessive generated acid. Examples of the acid diffusion controlling agent (Q) include a basic compound (DA), a basic compound (DB) in which the basicity is reduced or eliminated by irradiation with radiation, an onium salt (DC) which is a weak acid with respect to the acid generator (P), a low-molecular compound (DD) having a nitrogen atom and a group which is detached by the action of an acid, and an onium salt compound (DE) having a nitrogen atom at a cation portion.

In the composition, a known acid diffusion controller can be suitably used. For example, known compounds disclosed in paragraphs [0627] to [0664] of specification of U.S. patent application publication No. 2016/0070167, paragraphs [0095] to [0187] of specification of U.S. patent application publication No. 2015/0004544, paragraphs [0403] to [0423] of specification of U.S. patent application publication No. 2016/0237190, and paragraphs [0259] to [0328] of specification of U.S. patent application publication No. 2016/0274458 can be preferably used as the acid diffusion-controlling agent (Q).

When the composition contains the acid diffusion controller (Q), the content of the acid diffusion controller (Q) (the total of the plurality of acid diffusion controllers when present) is preferably 0.1 to 10.0% by mass, more preferably 0.1 to 5.0% by mass, based on the total solid content of the composition.

In the composition, 1 kind of the acid diffusion controlling agent (Q) may be used alone, or 2 or more kinds may be used simultaneously.

(hydrophobic resin (E))

The hydrophobic resin (E) may be a resin having a different hydrophobicity from the resin (a).

The hydrophobic resin (E) is preferably designed to be biased to the surface of the resist film, but unlike the surfactant, does not necessarily have a hydrophilic group in the molecule and may not contribute to uniformly mixing a polar substance and a non-polar substance.

The effect of adding the hydrophobic resin (E) includes control of static and dynamic contact angles of the surface of the resist film with respect to water, suppression of outgassing, and the like.

From the viewpoint of the uneven distribution on the film surface layer, the hydrophobic resin (E) preferably has "fluorine atom", "silicon atom" and "CH contained in the side chain portion of the resin₃The partial structure "may be any 1 or more, and preferably 2 or more. The hydrophobic resin (E) preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted in the side chain.

When the hydrophobic resin (E) 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 of the resin or may be contained in a side chain.

When the hydrophobic resin (E) has 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 is preferably used as the partial structure having a fluorine atom.

The alkyl group having a fluorine atom (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a linear or branched alkyl group in which at least 1 hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least 1 hydrogen atom is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

Examples of the aryl group having a fluorine atom include aryl groups in which at least 1 hydrogen atom of an aryl group such as a phenyl group and a naphthyl group is substituted with a fluorine atom, and may further have a substituent other than a fluorine atom.

Examples of the repeating unit having a fluorine atom or a silicon atom include the repeating unit exemplified in paragraph [0519] of US 2012/0251948.

Further, as described above, the hydrophobic resin (E) preferably has CH in a side chain moiety₃And (4) partial structure.

Wherein the hydrophobic resin has CH in a side chain part₃Part of the structure including CH having ethyl, propyl, etc₃And (4) partial structure.

On the other hand, since a methyl group (for example, an α -methyl group having a repeating unit of a methacrylic acid structure) directly bonded to the main chain of the hydrophobic resin (E) is less influenced by the main chain and has a small effect of making the surface of the hydrophobic resin (E) uneven, CH which is not included in the present invention₃And (4) partial structure.

When the composition contains the hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the composition.

(solvent (F))

The composition may contain a solvent (F).

When the composition is a radiation-sensitive resin composition for EUV, the solvent (F) preferably contains (M1) propylene glycol monoalkyl ether carboxylate and at least one selected from the group consisting of (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate of at least 1. The solvent in this case may contain components other than the components (M1) and (M2).

When a solvent containing the component (M1) or (M2) is used in combination with the resin (a), the coating property of the composition is improved and a pattern with a small number of development defects can be formed, which is preferable.

As the component (M1), at least 1 selected from the group consisting of Propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate is preferable, and Propylene Glycol Monomethyl Ether Acetate (PGMEA) is more preferable.

As the component (M2), the following components are preferable.

As the propylene glycol monoalkyl ether, Propylene Glycol Monomethyl Ether (PGME) or propylene glycol monoethyl ether is preferable.

As the lactate, ethyl lactate, butyl lactate, or propyl lactate is preferable.

As the acetate, methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate or 3-methoxybutyl acetate is preferable.

Also, butyl butyrate is also preferred.

As the alkoxypropionate, methyl 3-Methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) is preferable.

As the chain ketone, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, propiophenone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone (ionone), diacetone alcohol, acetyl methanol, acetophenone, methyl naphthyl ketone or methyl amyl ketone is preferable.

As the cyclic ketone, methylcyclohexanone, isophorone or cyclohexanone is preferable.

As the lactone, gamma-butyrolactone is preferred.

As the alkylene carbonate, propylene carbonate is preferable.

As the component (M2), Propylene Glycol Monomethyl Ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl amyl ketone, cyclohexanone, butyl acetate, amyl acetate, gamma-butyrolactone or propylene carbonate are more preferable.

The solvent (F) is preferably a mixed solvent of 2 or more species containing propylene glycol monomethyl ether acetate.

The content of the solvent (F) in the composition is preferably determined so that the solid content concentration is 0.5 to 30 mass%, more preferably 1 to 20 mass%. When treated in this manner, the composition is more excellent in coatability.

(other additives)

The composition may further contain a surfactant, an alkali-soluble resin having a phenolic hydroxyl group, a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a compound that promotes solubility to a light absorber and/or a developer (for example, a phenol compound having a weight-average molecular weight (Mw) of 1000 or less or an alicyclic or aliphatic compound having a carboxyl group).

For example, those skilled in the art can easily synthesize a phenol compound having a weight average molecular weight (Mw) of 1000 or less by referring to the methods described in, for example, Japanese patent application laid-open No. 4-122938, Japanese patent application laid-open No. 2-28531, U.S. Pat. No. 4,916,210, European patent application No. 219294, and the like.

Specific examples of the alicyclic or aliphatic compound 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.

Examples

The present invention will be described in further detail below with reference to examples. The materials, the amounts used, the ratios, the treatment contents, the treatment steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed in a limiting manner by the following examples.

In addition, when the chemical solutions of examples and comparative examples were prepared, all of the treatment of the container, the preparation, filling, storage, and analysis and measurement of the chemical solutions were performed in a clean room that satisfied the ISO class 2 or 1 level.

(Filter)

As the filter, the following filters were used.

"PP 200 nm": filter made of polypropylene, manufactured by Pall corporation, having a pore size of 200nm

"IEX 50 nm": ion exchange resin filter having a pore size of 50nm, manufactured by Entegris

"PTFE 30 nm": a polytetrafluoroethylene filter having a pore size of 30nm manufactured by Entegris

"PTFE 50 nm": a filter made of Polytetrafluoroethylene (PTFE) having a pore size of 50nm, manufactured by Entegris corporation

"UPE 1 nm": ultra-high molecular weight polyethylene filter having a pore diameter of 1nm, manufactured by Pall corporation

"UPE 3 nm": ultra-high molecular weight polyethylene filter having a pore size of 3nm, manufactured by Pall corporation

< object to be purified >

In order to produce chemical solutions of examples and comparative examples, solvents described in the column of "type of solvent" in the column of "raw material" in table 1 were used as the substances to be purified. In addition, commercially available products were used as the solvents.

< purification Process >

The purified product was subjected to the distillation purification treatment described in table 1.

In addition, "condition 1" in the column of "distillation" in Table 1 indicates that 1 time of atmospheric distillation by a distillation column (theoretical plate number: 15) is performed, "condition 2" indicates that 1 time of atmospheric distillation by a distillation column (theoretical plate number: 10) is performed, "condition 3" indicates that 1 time of atmospheric distillation by a distillation column (theoretical plate number: 25) is performed, "condition 4" indicates that 1 time of atmospheric distillation by a distillation column (theoretical plate number: 30) is performed, and "condition 5" indicates that 1 time of atmospheric distillation by a distillation column (theoretical plate number: 5) is performed.

Next, the purified material purified by distillation is stored in a storage tank, and the purified material stored in the storage tank is filtered by passing it through the filters 1 to 3 shown in table 1 in sequence, and is stored in the storage tank.

Next, as shown in table 1 below, the following cycle filtration treatment was performed: in the example in which "yes" is listed in the column "1 st cycle", the purified material stored in the storage tank is filtered by the filters 4 to 5 (the filter 4 is used only when the filter 4 is present) shown in table 1, and the purified material after being filtered by the filter 5 (after being filtered by the filter 4 when the filter 4 is present only) is circulated to the upstream side of the filter 4 and is filtered again by the filters 4 to 5. After the circulation filtration treatment, the chemical liquid is contained in a container.

In the example in which the column "no" in "1 st cycle" is shown in table 1 below, the above-described cycle treatment is not performed, and the purified product stored in the tank is filtered by the filter 4 shown in table 1.

In the above-described series of purification processes, liquid contact portions of various apparatuses (for example, a distillation column, piping, a storage tank, and the like) that contact the object to be purified are made of electropolished stainless steel.

The chemical solution obtained in the above contains the following 4 specific compounds. In addition, the specific compounds a and B correspond to the compound represented by the formula (1), and the specific compounds C and D correspond to the compound represented by the formula (2).

[ chemical formula 45]

The contents of organic components and metal components in the chemical solution were measured by the following methods.

< content of specific Compound >

The content of the specific compound in the drug solution was measured by a gas chromatography mass spectrometer (GC/MS) (manufactured by Agilent Co., Ltd., GC: 7890B, MS: 5977B EI/CI MSD).

As described later, the column "specific compound a" in table 1 indicates the content of the specific compound a in the chemical solution, the column "specific compound B" indicates the content of the specific compound B in the chemical solution, the column "specific compound C" indicates the content of the specific compound C in the chemical solution, and the column "specific compound D" indicates the content of the specific compound D in the chemical solution.

< content of Metal component >

The contents of metal components (metal ions, metal-containing particles) in the chemical solutions were measured by the methods of ICP-MS and SP-ICP-MS.

The following devices were used.

Manufacturer: PerkinElmer Co

The model number: nexion350S

The following analysis software was used for the analysis.

Syngistix nano application module special for SP-ICP-MS

Syngist for ICP-MS software

< evaluation method >

First, an organic anti-reflective film forming composition ARC29SR (manufactured by NISSAN CHEMICAL CORPORATION) was coated on a silicon substrate having a diameter of 300mm, and baked at 205 ℃ for 60 seconds, thereby forming an anti-reflective film having a film thickness of 78 nm.

In order to improve coatability, a pre-wetting liquid (cyclohexanone, FUJIFILM Electronic Materials co., ltd.) was dropped on the surface of the silicon substrate on the antireflection film side on which the antireflection film was formed, and spin coating was performed.

Next, any of the compositions 1 to 4 described later was applied on the antireflection film, and prebaked under the conditions described in the column of "prebaked" described in table 1, thereby forming a coating film having a thickness of 50 nm.

Next, using an ArF excimer laser scanner (NA0.75), 25[ mJ/cm²]The coating film was subjected to pattern exposure. Then, the plate was heated at 120 ℃ for 60 seconds. Next, spin-immersion development was performed for 30 seconds using the alkaline developer described in table 1. Next, the silicon substrate was rotated at 4000rpm for 30 seconds, thereby forming a positive resist pattern. Next, the positive resist pattern was washed with water. Next, the positive resist pattern was cleaned with the chemical solutions described in the examples and comparative examples. Then, the obtained positive resist pattern was subjected to post-baking at 200 ℃ for 300 seconds. Through the above process, an L/S pattern with a line/space of 1:1 was obtained. In addition, the line width was 65 nm.

The spatial portion of the L/S pattern obtained above was observed, and the residue defect (residual residue) was evaluated according to the following criteria.

"A": the number of residual defects is 5 or less per wafer.

"B": the number of the residual defects exceeds 5/wafer and is less than 10/wafer.

"C": the number of the residual defects exceeds 10/wafer and is less than 20/wafer.

"D": the number of the residual defects exceeds 20/wafer and is less than 30/wafer.

"E": the number of residual defects exceeds 30/wafer.

(composition 1)

An acid-decomposable resin (a resin represented by the following formula (weight average molecular weight (Mw): 7500): the numerical values described in the respective repeating units represent mol%): 100 parts by mass

[ chemical formula 46]

A photoacid generator shown below: 8 parts by mass

[ chemical formula 47]

Quenchers shown below: 5 parts by mass (the mass ratio is 0.1:0.3:0.3:0.2 in order from the left). In addition, among the quenchers described below, the polymer type quencher had a weight average molecular weight (Mw) of 5000. The numerical values described in the respective repeating units represent molar ratios.

[ chemical formula 48]

A hydrophobic resin shown below: 4 parts by mass (the mass ratio is 0.5:0.5 in order from the left). In the hydrophobic resins described below, the weight average molecular weight (Mw) of the left-side hydrophobic resin was 7000, and the weight average molecular weight (Mw) of the right-side hydrophobic resin was 8000. In each hydrophobic resin, the numerical value described in each repeating unit represents a molar ratio.

[ chemical formula 49]

Solvent:

PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

Cyclohexanone: 600 parts by mass

γ -BL (γ -butyrolactone): 100 parts by mass

(composition 2)

An acid-decomposable resin (a resin represented by the following formula (weight average molecular weight (Mw): 8000) wherein the numerical values described in the respective repeating units represent mol%): 100 parts by mass

[ chemical formula 50]

A photoacid generator shown below: 12 parts by mass (mass ratio is 0.5:0.5 in order from left)

[ chemical formula 51]

Quenchers shown below: 5 parts by mass (mass ratio is 0.3:0.7 in order from left)

[ chemical formula 52]

A hydrophobic resin shown below: 5 parts by mass (the mass ratio is 0.8:0.2 in the order from the top). In the hydrophobic resins described below, the weight average molecular weight (Mw) of the upper hydrophobic resin is 8000, and the weight average molecular weight (Mw) of the lower hydrophobic resin is 6000. In each hydrophobic resin, the numerical value described in each repeating unit represents a molar ratio.

[ chemical formula 53]

[ chemical formula 54]

Solvent:

PGMEA (propylene glycol monomethyl ether acetate): 3 parts by mass

Cyclohexanone: 600 parts by mass

γ -BL (γ -butyrolactone): 100 parts by mass

(composition 3)

An acid-decomposable resin (a resin represented by the following formula (weight average molecular weight (Mw): 8000) wherein the numerical values described in the respective repeating units represent mol%): 100 parts by mass

[ chemical formula 55]

A photoacid generator shown below: 15 parts by mass

[ chemical formula 56]

Quenchers shown below: 7 parts by mass (mass ratio is 1:1 in order from left)

[ chemical formula 57]

A hydrophobic resin shown below: 20 parts by mass (the mass ratio is 3:7 in the order from the top). In the hydrophobic resins described below, the weight average molecular weight (Mw) of the upper hydrophobic resin was 10000, and the weight average molecular weight (Mw) of the lower hydrophobic resin was 7000. In the hydrophobic resin shown in the next paragraph, the molar ratio of each repeating unit was 0.67 and 0.33 in the order from the left.

[ chemical formula 58]

[ chemical formula 59]

Solvent:

PGMEA (propylene glycol monomethyl ether acetate): 50 parts by mass

PGME (propylene glycol monomethyl ether): 100 parts by mass

2-heptanone: 100 parts by mass

γ -BL (γ -butyrolactone): 500 parts by mass

(composition 4)

An acid-decomposable resin (a resin represented by the following formula (weight average molecular weight (Mw): 6500): the numerical values described in the respective repeating units represent mol%): 80 parts by mass

[ chemical formula 60]

A photoacid generator shown below: 15 parts by mass

[ chemical formula 61]

Quenchers shown below: 5 parts by mass

[ chemical formula 62]

A hydrophobic resin (weight average molecular weight (Mw) of 5000) shown below: 60 parts by mass

[ chemical formula 63]

Solvent:

PGMEA (propylene glycol monomethyl ether acetate): 70 parts by mass

HBM (methyl-2-hydroxybutyrate): 100 parts by mass

Cyclohexanone: 700 parts by mass

The column "alkaline developer" in table 1 indicates the components contained in the alkaline developer, and each symbol indicates the following.

"TMAH": tetramethyl ammonium hydroxide

"EDTA": ethylenediaminetetraacetic acid

"DTPA": diethylenetriamine 5 acetic acid

"DBSA": p-dodecylbenzene sulfonic acid

“Surfynol 440”：

“Surfynol 480”：

The concentration in the column of "alkaline developer" indicates the concentration of the alkaline developer relative to the total amount of each compound.

In addition, each of the alkaline developers contained water in addition to the components shown in table 1.

The column "ClogP" in table 1 indicates the ClogP value of the solvent used (for example, methyl isobutyl carbinol in example 1). In example 25, the ClogP value of "isopropanol" is shown.

The "vapor pressure (kPa)" shown in table 1 indicates the vapor pressure of the solvent used at 25 ℃. In example 25, the vapor pressure of "isopropyl alcohol" at 25 ℃ is shown.

The "number of carbon atoms" shown in table 1 indicates the number of carbon atoms contained in the solvent used. In example 25, the number of carbon atoms of "isopropyl alcohol" was shown.

The "C/O ratio" shown in table 1 indicates the ratio of the number of carbon atoms to the number of oxygen atoms contained in the solvent used. In example 25, the above ratio of "isopropyl alcohol" is shown.

The column "solvent concentration (% by mass)" in table 1 indicates the content (% by mass) of the solvent (alcohol solvent) in the chemical solutions of the examples and comparative examples with respect to the total mass of the chemical solutions. In example 25, the content of "isopropyl alcohol" is shown.

The column "metal component (mass ppt)" in table 1 indicates the content (mass ppt) of the metal component in the chemical solutions of the examples and comparative examples with respect to the total mass of the chemical solutions.

The column "concentration (mass ppb) of the specific compound a" in table 1 indicates the content (mass ppb) of the specific compound a in the chemical solutions of the respective examples and comparative examples with respect to the total mass of the chemical solutions.

The column "concentration (mass ppb) of the specific compound B" shown in table 1 indicates the content (mass ppb) of the specific compound B in the chemical solutions of the respective examples and comparative examples with respect to the total mass of the chemical solutions.

The column "concentration (mass ppb) of the specific compound C" shown in table 1 indicates the content (mass ppb) of the specific compound C in the chemical solutions of the respective examples and comparative examples with respect to the total mass of the chemical solutions.

The column "concentration (mass ppb) of the specific compound D" shown in table 1 indicates the content (mass ppb) of the specific compound D in the chemical solutions of the examples and comparative examples with respect to the total mass of the chemical solutions.

The column "total amount (mass ppb)" shown in table 1 indicates the total content (mass ppb) of the specific compounds a to D.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

In tables 1 (1 thereof) to 1 (5 thereof), data of each example and comparative example are shown in each row.

For example, in example 1, as shown in table 1 (1 thereof), methyl isobutyl carbinol was used, as shown in table 1 (2 thereof), the distillation conditions were "condition 1", as shown in table 1 (3 thereof), the solvent concentration (mass%) of the drug solution was 99.95 mass%, as shown in table 1 (4 thereof), the type of composition was "composition 1", and as shown in table 1 (5 thereof), the residue was evaluated as "a". The same applies to other examples and comparative examples.

As shown in Table 1, the chemical solutions of the present invention can provide desired effects.

Among them, the comparison of examples 1 to 4 confirmed that the effect is more excellent when the content of the metal component is 0.10 to 100 mass ppt based on the total mass of the chemical solution.

Further, it was confirmed from the comparison between examples 5 and 6 and other examples that the effect is more excellent when the content (total content) of the specific compound is 0.010 to 5.0 mass ppb with respect to the total mass of the chemical solution.

Further, the comparison of examples 7 to 10 confirmed that the effect is more excellent when the content of the quaternary ammonium salt is 0.75 to 7.5 mass% based on the total mass of the alkaline developer.

Further, the comparison of examples 19 to 23 confirmed that the effect is more excellent when the heating temperature in the step G (prebaking) is 80 to 120 ℃ and the heating time is 30 to 180 seconds.

Further, from comparison between examples 24 and 25, it was confirmed that the effect is more excellent when the content of the alcohol solvent is 85.000 to 99.999% by mass based on the total mass of the drug solution.

Further, it was confirmed from the comparison between examples 36 and 40 and other examples that the effect is more excellent when the ratio of the number of carbon atoms to the number of oxygen atoms contained in the alcohol-based solvent is 3.0 or more (when the ClogP value of the alcohol-based solvent is-0.50 to 3.00).

From table 1 above, it was confirmed that the alcohol solvent is methyl isobutyl carbinol, 3-methyl-1-butanol or 2, 4-dimethyl-3-pentanol, and the effect is further excellent.