Method for producing a photosensitive or radiation-sensitive resin composition, method for forming a pattern, method for producing an electronic device

Abstract

Provided is a method for producing a photosensitive or radiation-sensitive resin composition having a reduced content of particles. Also provided are a pattern forming method and a method for producing an electronic device. The method for producing a photosensitive or radiation-sensitive resin composition includes: Step 1, preparing an intermediate solution containing a photoacid generator and a solvent; and Step 2, mixing the intermediate solution with at least a resin to produce a photosensitive or radiation-sensitive resin composition having a viscosity of 10 mPa·s or more.

Description

Technical Field

[0001] This invention relates to a method for manufacturing a photosensitive or radiosensitive linear resin composition, a patterning method, and a method for manufacturing electronic devices. Background Technology

[0002] In the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), micro-processing is performed using photolithography with photosensitive or linear resin compositions.

[0003] As a photolithography method, for example, a method can be described that after forming a resist film from a photosensitive linear resin composition containing a resin whose polarity is increased by an acid, the obtained film is exposed and then developed.

[0004] In the manufacturing process of semiconductor devices, thick-film (e.g., 0.5–15 μm) resist films may sometimes be used depending on the application process.

[0005] As a resist composition capable of forming such a resist film, for example, Patent Document 1 discloses "a positive resist composition, which is a resist composition for forming a thick-film resist film with a film thickness of 1 to 15 μm, characterized in that a resin component (A) whose alkali solubility increases by the action of acid and an acid-generating component (B) that generates acid by exposure are dissolved in an organic solvent (S), wherein the organic solvent (S) is a mixed solvent of 10 to 95% by mass of propylene glycol monomethyl ether and 5 to 90% by mass of other solvents (S2)."

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent No. 4954576 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] Based on the results of the inventors’ preparation and research of a thick-film resist composition for resist film formation with reference to Patent Document 1, it was found that there is room for further improvement in reducing the particle content in the resist composition.

[0011] Therefore, the objective of this invention is to provide a method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition with reduced particle content.

[0012] Furthermore, the objective of this invention is to provide a pattern forming method and a method for manufacturing electronic devices.

[0013] means for solving technical problems

[0014] The present invention was completed as a result of in-depth research conducted by the inventors to solve the above-mentioned problems. Specifically, it was discovered that the above-mentioned problems can be solved through the following configuration.

[0015] [1] A method for manufacturing a photosensitive or radiosensitive linear resin composition, comprising:

[0016] Step 1: Prepare an intermediate solution containing a photoacid-generating agent and a solvent; and

[0017] Step 2 involves mixing the above intermediate solution with at least a resin to prepare a photosensitive or radiosensitive linear resin composition with a viscosity of 10 mPa·s or higher.

[0018] [2] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to [1], wherein,

[0019] The viscosity of the above intermediate solution is below 50 mPa·s.

[0020] [3] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to [1] or [2], wherein,

[0021] The difference in viscosity between the above intermediate solution and the above photosensitive radioactive or radiosensitive linear resin composition having a viscosity of 10 mPa·s or higher is 50 to 600 mPa·s.

[0022] [4] A method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [3], wherein,

[0023] In step 1 above, the solubility of the photoacid-generating agent relative to 100g of the solvent at 25°C is 0.5g or more.

[0024] [5] A method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [4], wherein,

[0025] The solvents mentioned above include one or more solvents selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, and cyclopentanone.

[0026] [6] A method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [5], wherein,

[0027] The aforementioned photoacid-generating agents include compounds represented by the general formula (ZI-5) described below.

[0028] [7] A pattern forming method, comprising the following steps:

[0029] The step of forming a resist film on a support using a photosensitive or radiosensitive linear resin composition obtained by any one of [1] to [6] of the method for manufacturing a photosensitive or radiosensitive linear resin composition.

[0030] The process of exposing the above-mentioned resist film; and

[0031] The process of developing the photoresist film exposed above using a developing solution.

[0032] [8] A method for manufacturing an electronic device, comprising the pattern forming method described in [7].

[0033] Invention Effects

[0034] According to the present invention, a method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition with reduced particle content can be provided.

[0035] Furthermore, according to the present invention, a pattern forming method and a method for manufacturing electronic devices can be provided. Attached Figure Description

[0036] Figure 1 This is a schematic diagram illustrating one embodiment of the apparatus used in the method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition of the present invention. Detailed Implementation

[0037] Hereinafter, an example of a method for implementing the present invention will be described.

[0038] In this specification, the numerical range indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0039] In this specification, the designations of groups (atomic groups) that do not specify whether they are substituted or unsubstituted include both substituted groups and unsubstituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0040] Unless otherwise stated, the bonding orientation of the divalent groups marked in this specification is not restricted.

[0041] For example, in a compound represented by the general formula "LMN", when M is -OCO-C(CN)=CH-, if the position bonded to the L side is set as *1 and the position bonded to the N side is set as *2, M can be *1-OCO-C(CN)=CH-*2 or *1-CH=C(CN)-COO-*2.

[0042] In this specification, "(meth)acrylic acid" is a general term encompassing acrylic acid and methacrylic acid, specifically referring to "at least one of acrylic acid and methacrylic acid". Similarly, "(meth)acrylic acid" refers to "at least one of acrylic acid and methacrylic acid".

[0043] Furthermore, in this specification, "organic group" refers to a group having one or more carbon atoms.

[0044] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are defined as polystyrene equivalents determined by GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: Refractive Index Detector).

[0045] In this manual, "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet radiation represented by excimer lasers, extreme ultraviolet (EUV), X-rays, and electron beams (EB). In this manual, "light" refers to radiation.

[0046] In this specification, "acid dissociation constant pKa" refers to the acid dissociation constant pKa in aqueous solution, as defined in, for example, the Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, MARUZEN Co., Ltd.). A lower pKa value indicates a stronger acid. Specifically, the acid dissociation constant pKa in aqueous solution can be practically determined by measuring the acid dissociation constant at 25°C using an infinitely diluted aqueous solution. Alternatively, the substituent constants of Hammett and values ​​based on a database of known literature values ​​can be calculated using the software package described below. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0047] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0048] [Method for manufacturing photosensitive or radiosensitive linear resin compositions]

[0049] As a characteristic feature of the method for manufacturing the photosensitive or radiosensitive linear resin composition (hereinafter also referred to as "resist composition") of the present invention, the following feature can be cited: when preparing a high viscosity resist composition with a viscosity of 10 mPa·s or more, as described in steps 1 and 2 below, an intermediate solution containing a photoacid generator and a solvent is prepared in advance, and the intermediate solution is mixed with other raw material components containing resin.

[0050] The inventors discovered through their research on the problems of the prior art that when a photoacid generator, which is a raw material component and is usually a solid raw material, is not dissolved in the solvent and produces a dissolution residue, this is one of the reasons for the particles in the photoacid composition.

[0051] Thick-film resist compositions typically require a high concentration of solid components, resulting in high viscosity (e.g., 10 mPa·s or higher). Therefore, compared to thin-film resist compositions with low solid component concentrations, thick-film resist compositions inevitably have a higher content of each raw material component relative to the solvent. Consequently, it is believed that when manufacturing the resist composition by mixing and stirring the raw materials and solvent, residual photoacid-generating agents, which are solid raw materials, are prone to dissolution. Furthermore, the low stirring efficiency of high-viscosity resist compositions may also be one reason for the residual dissolution of photoacid-generating agents, which are solid raw materials.

[0052] Regarding the above insights, the method for manufacturing the resist composition of the present invention pre-prepares an intermediate solution comprising a photoacid generator as a solid raw material and a solvent. By mixing the intermediate solution with other raw material components comprising a resin, the solubility of the photoacid generator as a solid raw material in the solvent is improved, and the generation of particles in the resist composition is suppressed.

[0053] The method for manufacturing the resist composition of the present invention will be described in detail below.

[0054] The method for manufacturing the resist composition of the present invention is a method for manufacturing a resist composition comprising a resin, a photoacid generator and a solvent and having a viscosity of 10 mPa·s or more, comprising step 1 and step 2 described below.

[0055] Step 1: The process of preparing an intermediate solution containing a photoacid-generating agent and a solvent.

[0056] Step 2: The step of mixing the above intermediate solution with at least resin to prepare a resist composition with a viscosity of 10 mPa·s or higher.

[0057] Furthermore, the manufacturing method of the present invention is preferably carried out in a cleanroom. As for cleanliness, it is preferably level 6 or below according to the internationally unified standard ISO 14644-1, more preferably level 5 or below, and even more preferably level 4 or below.

[0058] In this specification, "solid components" refers to all components other than solvents. Even if the aforementioned components are in liquid form, they can still be considered solid components.

[0059] [Process 1]

[0060] Step 1 is the process of preparing an intermediate solution containing a photoacid-generating agent and a solvent.

[0061] Furthermore, details regarding the photoacid generator and solvent used in step 1 will be described in detail later.

[0062] The intermediate solution may contain components other than the photoacid generator and solvent, and preferably does not contain resin (especially resin whose polarity increases through the action of acid). Here, "the intermediate solution does not contain resin" means that the resin content is 10% by mass or less relative to the total mass of the intermediate solution, preferably 8% by mass or less, more preferably 7% by mass or less, further preferably 6% by mass or less, and especially preferably 5% by mass or less. Furthermore, the lower limit is 0% by mass.

[0063] In the intermediate solution, the content of the photoacid-generating agent relative to the total solid content of the intermediate solution is preferably 80-100% by mass, more preferably 90-100% by mass, even more preferably 95-100% by mass, and particularly preferably 98-100% by mass.

[0064] As an intermediate solution, it is preferable that it substantially does not contain any components other than the photoacid generator and the solvent. Here, "the intermediate solution substantially does not contain any components other than the photoacid generator and the solvent" means that the total content of components other than the photoacid generator and the solvent is less than 1% by mass relative to the total mass of the intermediate solution, preferably 0.5% by mass or less, more preferably 0.3% by mass or less. In addition, the lower limit is 0% by mass. Therefore, when the resist composition contains other components such as acid diffusion control agents, surfactants, plasticizers, carboxylic acid onium salts and dissolution inhibitors, these other components are preferably mixed with the intermediate solution in step 2.

[0065] The viscosity of the intermediate solution is not particularly limited, for example, it is 80 mPa·s or less. From the viewpoint of further reducing the amount of particles generated in the resist composition, it is preferably 50 mPa·s or less, more preferably 30 mPa·s or less, even more preferably 10 mPa·s or less, and particularly preferably 3.0 mPa·s or less. In addition, there is no particular limitation on the lower limit value, for example, it is 1.0 mPa·s or more.

[0066] In this specification, the viscosity of the intermediate solution and the viscosity of the resist composition formed in step 2 (described later) refer to the viscosity at 25°C and are measured by an E-type viscometer.

[0067] The viscosity difference between the intermediate solution and the resist composition formed in step 2 (the difference between the viscosity of the resist composition formed in step 2 and the viscosity of the intermediate solution) is, for example, 30 mPa·s or more. From the viewpoint of further reducing the amount of particles generated in the resist composition, it is more preferably 50 mPa·s or more, and even more preferably 100 mPa·s or more. Furthermore, as an upper limit, it is, for example, 800 mPa·s or less. From the viewpoint of further reducing the amount of particles generated in the resist composition, it is more preferably 600 mPa·s or less, even more preferably 400 mPa·s or less, and particularly preferably 300 mPa·s or less.

[0068] Furthermore, the methods for determining the viscosity of the intermediate solution and the viscosity of the resist composition formed in step 2, as described below, are as follows.

[0069] The content of the photoacid-generating agent in the intermediate solution is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total mass of the intermediate solution. Furthermore, as an upper limit, it is preferably 75% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0070] There is no particular limitation on the concentration of the solid component in the intermediate solution, for example, it is 1 to 75% by mass. The lower limit of the concentration of the solid component in the intermediate solution is more preferably 5% by mass or more, and even more preferably 10% by mass or more. Furthermore, the upper limit is more preferably 60% by mass or less, and even more preferably 50% by mass or less. In addition, the concentration of the solid component in the intermediate solution is the mass percentage of the components other than the solvent relative to the total mass of the intermediate solution.

[0071] In the intermediate solution, the solubility of the photoacid-generating agent relative to 100g of solvent at 25°C is preferably 0.1g or more, and more preferably 0.5g or more, and even more preferably more than 3.0g, from the viewpoint of further reducing the amount of particles generated in the resist composition. Furthermore, there is no particular limitation on the upper limit of the solubility of the acid-generating agent relative to 100g of solvent at 25°C, for example, it is 10g or less.

[0072] Furthermore, from the viewpoint of superior resolution, compounds containing a benzoyl methyl sulfonium salt structure are preferred as photoacid generators. Among compounds containing a benzoyl methyl sulfonium salt structure, as described later, from the viewpoint of further reducing the amount of particles generated in the resist composition, compounds represented by the general formula (ZI-5) are preferred.

[0073] In the intermediate solution, there are no particular limitations on the solvent. From the viewpoint of ensuring the in-plane uniformity of the film thickness when coating the resist composition, an organic solvent with a boiling point (referring to the boiling point at 1 atmosphere) of 160°C or lower is preferred. There are no particular limitations on the type of solvent, but it is preferable to select a solvent that accounts for 20% or more by mass relative to the total mass of the solvent contained in the resist composition formed in step 2. From the viewpoint of further reducing the amount of particles generated in the resist composition, it is preferable to select one or more solvents selected from propylene glycol monomethyl ether acetate (PGMFA), propylene glycol monomethyl ether (PGME), ethyl lactate, cyclohexanone, and cyclopentanone.

[0074] (Preparation method of intermediate solution)

[0075] There are no particular limitations on the preparation method of the intermediate solution, but the preferred method is to mix and stir the photoacid-generating agent and the solvent.

[0076] There are no particular limitations on the temperature of the intermediate solution during stirring and mixing, but it is preferably 15 to 32°C, and more preferably 20 to 24°C.

[0077] Furthermore, the temperature of the intermediate solution is preferably kept constant during stirring and mixing, preferably within ±10°C of the set temperature, more preferably within ±5°C, and even more preferably within ±1°C.

[0078] There is no particular limitation on the stirring and mixing time, but from the viewpoint of further reducing the amount of particles generated in the resist composition, it is preferably 1 to 48 hours, more preferably 15 to 24 hours.

[0079] Ultrasonic waves can be applied to the intermediate solution during stirring and mixing.

[0080] The intermediate solution can be a suspension in which the photoacid generator is dispersed in a solvent, or a solution in which the photoacid generator is dissolved in a solvent. However, from the viewpoint of further reducing the amount of particles generated in the resist composition, a solution in which the photoacid generator is dissolved in a solvent is preferred.

[0081] [Process 2]

[0082] Step 2 is the step of preparing a resist composition by mixing the intermediate solution prepared in step 1 with at least a resin.

[0083] Step 2 preferably includes the following steps 2A and 2B.

[0084] Step 2A: The process of mixing the intermediate solution prepared in Step 1 with at least the resin.

[0085] Step 2B: The process of stirring and mixing the mixture obtained in Step 2A.

[0086] Furthermore, details about the resin used in step 2 will be described in detail later.

[0087] In step 2, other components besides the intermediate solution and resin may also be mixed. Examples of these other components include acid diffusion control agents, surfactants, plasticizers, carboxylic acid onium salts, and dissolution inhibitors. Details of these other components will be described later.

[0088] Step 2 is preferably carried out using a mixing tank. Figure 1 The diagram shows a schematic representation of an embodiment of an apparatus equipped with a stirring tank that can be used in step 2.

[0089] The device 100 includes a mixing tank 10, a stirring shaft 12 rotatably mounted in the mixing tank 10, stirring blades 14 mounted on the stirring shaft 12, a circulation pipe 16 connected at one end to the bottom of the mixing tank 10 and at the other end to the upper part of the mixing tank 10, a filter 18 disposed in the middle of the circulation pipe 16, a discharge pipe 20 connected to the circulation pipe 16, and a discharge nozzle 22 disposed at the end of the discharge pipe 20.

[0090] The liquid contact parts (areas in contact with liquid) inside the device are preferably lined or coated with fluoropolymers or the like.

[0091] Furthermore, it is preferable to pre-clean the apparatus 100 with a solvent before performing step 2. Known methods can be cited as the solvent and cleaning method used, for example, the solvent and cleaning method disclosed in Japanese Patent Application Publication No. 2015-197646.

[0092] As for the mixing tank 10, there is no particular limitation as long as it is a mixing tank capable of containing resin and intermediate solutions, and known mixing tanks can be cited.

[0093] The shape of the bottom of the mixing tank 10 is not particularly limited. Examples of suitable shapes include a disc-shaped mirror plate, a semi-elliptical mirror plate, a flat mirror plate, and a conical mirror plate. A disc-shaped mirror plate or a semi-elliptical mirror plate is preferred.

[0094] To improve mixing efficiency, baffles can be installed inside the mixing tank 10.

[0095] There is no particular limitation on the number of baffles, but 2 to 8 are preferred.

[0096] There is no particular limitation on the width of the baffle, but it is preferably 1 / 8 to 1 / 2 of the diameter of the mixing tank.

[0097] The length of the baffle in the height direction of the mixing tank is not particularly limited, but it is preferably more than 1 / 2 of the height from the bottom of the mixing tank to the liquid surface of the added component, more preferably more than 2 / 3, and even more preferably more than 3 / 4.

[0098] Preferably, a drive source (e.g., a motor) is installed in the stirring shaft 12. The drive source rotates the stirring shaft 12, thereby rotating the stirring blades 14, and the components added into the stirring tank 10 are stirred.

[0099] The shape of the stirring blade 14 is not particularly limited; for example, swirling submerged blades, propeller blades, and turbine blades can be used.

[0100] In addition, the mixing tank 10 may have a material inlet for adding various materials into the mixing tank.

[0101] Furthermore, the stirring tank 10 may have a gas inlet for introducing gas into its interior.

[0102] Furthermore, the mixing tank 10 may have a gas outlet for discharging the gas inside it to the outside of the mixing tank.

[0103] There are no particular restrictions on the steps of adding the resin and intermediate solution into the mixing tank 10.

[0104] For example, a method of adding the above-mentioned components can be described as using a material inlet (not shown) in the mixing tank 10. When adding the components, they can be added sequentially or all at once. Furthermore, when adding one component, it can be added in multiple batches.

[0105] Furthermore, there is no particular restriction on the order in which the components are added to the mixing tank 10. For example, when adding the five components—resin, intermediate solution, solvent, acid diffusion control agent, and additives—to the mixing tank 10, 120 different addition methods can be listed in Tables 1 and 2 below. Additionally, additives refer to components other than resin, intermediate solution, solvent, and acid diffusion control agent.

[0106] In addition, Tables 1 and 2 show the order (1 to 5) of adding the above 5 items into the mixing tank 10.

[0107] [Table 1]

[0108]

[0109] [Table 2]

[0110]

[0111] Furthermore, when adding components other than the solvent and intermediate solution into the stirring tank, the components can also be added to the stirring tank 10 as a solution dissolved in the solvent. In this case, in order to remove insoluble matter from the solution, the solution can be filtered through a filter before being added to the stirring tank 10.

[0112] Furthermore, when the solvent is added to the stirring tank 10, it can be filtered through a filter before being added to the stirring tank 10.

[0113] In addition, a liquid delivery pump can be used when various ingredients are added into the mixing tank 10.

[0114] The concentration of the components in the solution is not particularly limited, but is preferably 10 to 50% by mass relative to the total mass of the solution.

[0115] Alternatively, when adding the intermediate solution to the mixing tank 10, the intermediate solution can be filtered before being added to the mixing tank 10.

[0116] There are no particular restrictions on the type of filter used when filtering with the above filters; any known filter can be used.

[0117] The pore size (pore size) of the filter is preferably 0.20 μm or less, more preferably 0.10 μm or less, and even more preferably 0.05 μm or less.

[0118] As the material for the filter, fluorinated resins such as polytetrafluoroethylene, polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66 are preferred.

[0119] The filter can be a filter that has been pre-cleaned with an organic solvent.

[0120] When using filters, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. Furthermore, when using filters, circulation filtration can be implemented. As a method of circulation filtration, the method disclosed in Japanese Patent Application Publication No. 2002-062667 is preferred, for example.

[0121] As a filter, a filter that reduces the amount of dissolved substances, as disclosed in Japanese Patent Application Publication No. 2016-201426, is preferred.

[0122] In addition, after filtration by the above-mentioned filter, impurities can be further removed by adsorption materials.

[0123] Generally, when adding resin and intermediate solutions to a stirred tank, it is preferable to do so in a manner that creates space within the stirred tank. More specifically, such as... Figure 1 As shown, it is preferable to introduce each component into the mixing tank 10 in such a way that a space S (void S) is not occupied by the mixture M which contains at least the resin and intermediate solution.

[0124] The percentage of the mixture in the mixing tank, which contains at least the resin and intermediate solutions, is not particularly limited, but is preferably 50-95% by volume, more preferably 80-90% by volume.

[0125] In addition, the proportion of the above mixture can be obtained by the following formula (1).

[0126] Equation (1): Occupancy rate = {(volume of mixture in the mixing tank / volume of the mixing tank)} × 100

[0127] Furthermore, the porosity (the proportion of space (void) in the mixing tank) is preferably 5 to 50% by volume, more preferably 10 to 20% by volume.

[0128] The porosity mentioned above is obtained by the following formula (2).

[0129] Equation (2): Porosity = {1 - (volume of mixture in the mixing tank / volume of the mixing tank)} × 100

[0130] After adding the mixture, which contains at least a resin and an intermediate solution, into a mixing tank, step 2B is performed for mixing. Step 2B preferably involves... Figure 1 The space S shown is filled with a gas (hereinafter also referred to as "specific gas") with a concentration of 90% or more (preferably 90 to 100% by volume) of inactive gas.

[0131] Examples of inert gases include nitrogen, helium, and argon. Examples of gases other than inert gases include oxygen and moisture.

[0132] In step 2B, as long as the various components can be stirred and mixed in the presence of a specific gas, there is no particular limitation on the time (timing) at which the gas in the stirring tank is replaced with the specific gas.

[0133] For example, a method can be described as performing step 2C, which involves replacing the gas in the mixing tank with a specific gas, before step 2A. That is, a method can be described as replacing the gas in the mixing tank with a specific gas before adding the resin and intermediate solution into the mixing tank. As a replacement method, a method of supplying (introducing) an inactive gas into the mixing tank can be described. When performing step 2C, in order to maintain the state of the gas in the mixing tank as the specific gas, it is preferable to perform steps 2A and 2B while introducing the specific gas into the mixing tank. That is, it is preferable to start introducing the specific gas into the mixing tank before step 2A, and to perform steps 2A and 2B in the presence of the specific gas (in a state where the space of the mixing tank is filled with the specific gas).

[0134] Furthermore, a method can be given for replacing the gas in the mixing tank with a specific gas during step 2A. That is, a method can be given for replacing the gas in the mixing tank with a specific gas simultaneously when the resin and intermediate solution are added to the mixing tank. As a replacement method, a method of supplying (introducing) an inactive gas into the mixing tank can be given. When replacing the gas in the mixing tank with a specific gas during step 2A, in order to maintain the state of the specific gas in the mixing tank, it is preferable to perform step 2B while introducing the specific gas into the mixing tank. That is, it is preferable to start introducing the specific gas into the mixing tank during step 2A, and perform step 2B in the presence of the specific gas (in a state where the space of the mixing tank is filled with the specific gas).

[0135] Furthermore, a method can be described as performing step 2D, which involves replacing the gas in the mixing tank with a specific gas, between steps 2A and 2B. That is, a method can be described as replacing the gas in the mixing tank with a specific gas after the resin and intermediate solution are added to the mixing tank. As a replacement method, a method of supplying (introducing) an inactive gas into the mixing tank can be described. When performing step 2D, in order to maintain the state of the gas in the mixing tank as the specific gas, it is preferable to perform step 2B while introducing the specific gas into the mixing tank. That is, it is preferable to start introducing the specific gas into the mixing tank after step 2A, and perform step 2B in the presence of the specific gas (in a state where the space of the mixing tank is filled with the specific gas).

[0136] Among them, process 2C is preferred.

[0137] Alternatively, when supplying (introducing) inactive gas into the mixing tank, it can also be supplied through a gas filter for inactive gas or compressed air.

[0138] In step 2B, the air pressure inside the mixing tank is preferably adjusted to be higher than the air pressure outside the mixing tank. By maintaining this state, it is possible to prevent gases containing moisture and oxygen from outside the mixing tank from mixing into the mixing tank.

[0139] As a method to maintain the above state, one example is the method of continuously introducing a specific gas into the stirred tank.

[0140] Furthermore, in step 2B, the pressure difference between the gas inside and outside the mixing tank is preferably adjusted to 2.0 kPa or less. In other words, the pressure difference between the specific gas inside the mixing tank and the gas pressure outside the mixing tank is preferably adjusted to 2.0 kPa or less. By maintaining this state, it is possible to suppress the dissolution of the specific gas into the mixture inside the mixing tank, and further suppress the formation of defects in the formed pattern. The aforementioned pressure difference is preferably 0.8 kPa or less. There is no particular limitation on the lower limit, but it is preferably 0.1 kPa or more.

[0141] In addition, there are no particular restrictions on the methods for measuring the air pressure inside and outside the mixing tank; commercially available barometers can be used.

[0142] There are no particular limitations on the mixing method in step 2B, but it is preferable to use the aforementioned stirring blades. Furthermore, when mixing, it is preferable to consider the shape, size, placement, and stirring speed of the stirring blades to ensure thorough mixing of the liquid.

[0143] There is no particular limitation on the temperature of the mixture containing the resin and intermediate solution during stirring and mixing, but it is preferably 15 to 32°C, and more preferably 20 to 24°C.

[0144] Furthermore, the temperature of the mixture is preferably kept constant during stirring and mixing, preferably within ±10°C of the set temperature, more preferably within ±5°C, and even more preferably within ±1°C.

[0145] There is no particular limitation on the mixing time, but from the viewpoint of balancing the uniformity of the obtained resist composition and productivity, it is preferably 1 to 48 hours, and more preferably 10 to 24 hours.

[0146] There is no particular limitation on the rotation speed of the stirring blades during mixing, but it is preferably 20 to 500 rpm, more preferably 40 to 350 rpm, and even more preferably 50 to 300 rpm.

[0147] In addition, when stopping stirring and mixing, it is preferable to confirm that all components are dissolved in the solvent.

[0148] Ultrasonic waves can be applied to the mixture during stirring and mixing.

[0149] The water content in the resist composition is not particularly limited, but is preferably 0.10% by mass or less, more preferably 0.06% by mass or less, and even more preferably 0.04% by mass or less. The lower limit of the water content is not particularly limited, and is generally 0.01% by mass or more.

[0150] As a method for determining the moisture content in a corrosion resist composition, one example is the method using a Karl Fischer moisture measuring apparatus.

[0151] The oxygen content in the resist composition is not particularly limited, but is preferably 0.030 μg / μL or less, more preferably 0.027 μg / μL or less. The lower limit of the oxygen content is not particularly limited, but is generally 0.001 μg / μL or more.

[0152] The content of dissolved gases in the resist composition is not particularly limited, but is preferably 0.210 μg / μL or less, more preferably 0.190 μg / μL or less. The lower limit of the above-mentioned dissolved gas content is not particularly limited, but is generally 0.001 μg / μL or more.

[0153] As a method for determining the content of dissolved gases in a resist composition, one example is the method using gas chromatography analysis (GC390 manufactured by GL Sciences Inc.) with a TCD (Thermal Conductivity Detector) detector.

[0154] In addition, in this specification, the content of dissolved gas corresponds to the total content of nitrogen and oxygen.

[0155] After performing step 2B, the manufactured resist composition can be filtered.

[0156] For example, one could cite examples in Figure 1 In the apparatus 100 shown, a method is used to transport the resist composition manufactured in the mixing tank 10 to the circulation pipe 16 and filter it with the filter 18. Additionally, when the resist composition is transported from the mixing tank 10 to the circulation pipe 16, it is preferable to open a valve (not shown) and transport the resist composition into the circulation pipe 16.

[0157] The above-described circulating filtration can be performed continuously multiple times. That is, the resist composition can be continuously supplied to the circulating piping and can pass through filter 18 multiple times.

[0158] There are no particular limitations on the method of conveying the resist composition from the mixing tank 10 to the circulation pipe 16. Examples include gravity-based liquid delivery, applying pressure from the liquid surface side of the resist composition, creating a negative pressure on the circulation pipe 16 side, and combining two or more of these methods.

[0159] In the case of applying pressure from the liquid surface side of the resist composition, methods that utilize the flow pressure generated by the liquid delivery and methods that pressurize the gas can be cited.

[0160] The liquid pressure is preferably generated by, for example, a pump (such as a delivery pump and a circulation pump). Examples of pumps include rotary pumps, diaphragm pumps, metering pumps, chemical pumps, plunger pumps, bellows pumps, gear pumps, vacuum pumps, gas pumps, and liquid pumps. In addition, commercially available pumps can be appropriately listed. There are no particular limitations on the location of the pump.

[0161] The gas used for pressurization is preferably a gas that is inactive or non-reactive to the corrosion inhibitor composition; specifically, nitrogen, helium, argon, and other rare gases are examples. Furthermore, the pressure on the circulation piping 16 side is not reduced and is preferably at atmospheric pressure.

[0162] As a method to make the circulation piping 16 side negative pressure, it is preferable to reduce the pressure by a pump, and more preferably to reduce the pressure to a vacuum.

[0163] As filter 18, the filter used during filtration as described in step 2A can be cited as an example.

[0164] The differential pressure applied to the filter 18 (the pressure difference between the upstream and downstream sides) is preferably 200 kPa or less, more preferably 100 kPa or less.

[0165] Furthermore, when filtering with filter 18, it is preferable that the differential pressure during filtration changes little. Preferably, the differential pressure before and after filtration, from the time when liquid is first introduced into the filter until the time when 90% by mass of the filtered solution is introduced into the filter, is maintained within ±50 kPa of the differential pressure before and after filtration at the time when liquid is first introduced, and more preferably within 20 kPa.

[0166] When using filter 18, the preferred linear velocity is 3 to 150 L / (hr·m). 2 The range is more preferably 5–120 L / (hr·m). 2 ), more preferably 10-100 L / (hr·m 2 ).

[0167] In addition, Figure 1 In the device 100 described herein, a buffer tank for storing the filtered resist composition may be provided downstream of the filter 18.

[0168] The corrosion resist composition manufactured in the stirred tank 10 is as follows: Figure 1 As shown, liquid can be supplied to the discharge pipe 20, discharged from the discharge nozzle 22 located at the end of the discharge pipe 20, and contained in a specified container.

[0169] When the resist composition is filled into a container, for example, a container with a volume of 0.75L or more but less than 5L, the filling rate is preferably 0.3 to 3L / min, more preferably 0.4 to 2.0L / min, and even more preferably 0.5 to 1.5L / min.

[0170] To improve filling efficiency, multiple discharge nozzles can be arranged in parallel to fill simultaneously.

[0171] Examples of containers include glass containers treated with Bloom and containers with liquid contact parts treated with fluoropolymer.

[0172] When the resist composition is contained within a container, the space within the container (the area within the container not occupied by the resist composition) can also be replaced with a specified gas. Preferably, the gas is inactive or non-reactive to the resist composition; examples include nitrogen and rare gases such as helium and argon.

[0173] Additionally, a degassing treatment to remove dissolved gases from the resist composition can be performed before it is contained in the container. Examples of degassing methods include ultrasonic treatment and degassing treatment.

[0174] The viscosity of the resist composition obtained after step 2 is 10 mPa·s or more, preferably 100 mPa·s or more, more preferably 200 mPa·s or more, further preferably 250 mPa·s or more, and especially preferably 300 mPa·s or more. As an upper limit for the above viscosity, it is, for example, 1000 mPa·s or less, preferably 800 mPa·s or less, more preferably 700 mPa·s or less, especially preferably 500 mPa·s or less, and most preferably 400 mPa·s or less. Furthermore, the method for measuring the viscosity is as described above.

[0175] The concentration of solid components in the resist composition obtained through step 2 is not particularly limited, and is, for example, 15 to 70% by mass. A lower limit for the concentration of solid components in the resist composition is more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. Furthermore, an upper limit is more preferably 60% by mass or less, further preferably 55% by mass or less, and particularly preferably 50% by mass or less, in order to avoid an excessive difference between the viscosity of the resist composition and the viscosity of the intermediate solution. Additionally, the concentration of solid components in the resist composition is the mass percentage of the components other than the solvent relative to the total mass of the resist composition.

[0176] [Photosensitive or radiosensitive linear resin composition]

[0177] Hereinafter, a preferred embodiment of the resist composition (hereinafter also simply referred to as "resist composition") formed by the method for manufacturing the resist composition of the present invention will be described.

[0178] The resist composition comprises a resin, a photoacid generator, and a solvent, and has a viscosity of 10 mPa·s or higher.

[0179] The preferred methods for the viscosity and solids concentration of the resist composition are as described below, for example, the viscosity and solids concentration of the resist composition obtained through step 2.

[0180] The following describes the various components that may be contained in an anti-corrosion composition.

[0181] Resin

[0182] The resist composition comprises a resin.

[0183] As a resin, a resin whose polarity increases under the action of an acid (hereinafter, also simply referred to as "resin (A)") is preferred, and a repeating unit (Aa) (hereinafter, also simply referred to as "repeating unit (Aa)") is more preferred, wherein the repeating unit (Aa) has an acid-decomposable group.

[0184] <Repeating unit with acid-decomposing groups>

[0185] An acid-degradable group refers to a group that decomposes to produce a polar group through the action of an acid. Preferably, the acid-degradable group has a structure protected by a release group, where the polar group is released through the action of an acid. That is, the resin (A) contains a repeating unit (Aa) containing a group that decomposes to produce a polar group through the action of an acid. The resin containing this repeating unit (Aa) becomes more polar through the action of an acid, thereby increasing its solubility in alkaline developing solutions and decreasing its solubility in organic solvents.

[0186] As a polar group, an alkaline-soluble group is preferred. Examples include carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, sulfonamide, sulfonylimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, as well as acidic groups such as alcohol hydroxyl groups.

[0187] Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group.

[0188] Examples of detaching groups that are released by the action of acid include groups represented by formulas (Y1) to (Y4).

[0189] Equation (Y1): -C(Rx1)(Rx2)(Rx3)

[0190] Equation (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0191] Equation (Y3): -C(R) 36 (R) 37 (OR) 38 )

[0192] Equation (Y4): -C(Rn)(H)(Ar)

[0193] In formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0194] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0195] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0196] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0197] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0198] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0199] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0200] The group represented by formula (Y1) or formula (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0201] In formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R 37 With R 38 They can bond with each other to form rings. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0202] As formula (Y3), it is preferably a group represented by the following formula (Y3-1).

[0203] [Chemical Formula 1]

[0204]

[0205] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining them (e.g., groups formed by combining alkyl and aryl).

[0206] M represents a single bond or a divalent linker.

[0207] Q represents an alkyl group that may have heteroatoms, a cycloalkyl group that may have heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group that may have heteroatoms, or a group composed of combinations thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0208] In alkyl and cycloalkyl groups, for example, one of the methylene groups can be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0209] In addition, it is preferred that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkylene and aryl groups.

[0210] At least two of Q, M and L1 can be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0211] From the viewpoint of miniaturizing the pattern, L2 is preferably a secondary alkyl or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl, while examples of tertiary alkyl groups include tertiary butyl or adamantanecycloyl. In these cases, the increased Tg (glass transition temperature) and activation energy ensure film strength and suppress blurring.

[0212] In formula (Y4), Ar represents an aromatic cycloalgyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0213] As a repeating unit (Aa), it is more preferably a repeating unit represented by formula (A).

[0214] [Chemical Formula 2]

[0215]

[0216] L1 represents a divalent linker that may have a fluorine or iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine or iodine atom, or an aryl group that may have a fluorine or iodine atom; and R2 represents a desorbed group that may have a fluorine or iodine atom and can be desorbed by acid. At least one of L1, R1, and R2 has a fluorine or iodine atom.

[0217] L1 represents a divalent linker that can have either a fluorine or an iodine atom. Examples of divalent linkers that can have either a fluorine or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that can have either a fluorine or an iodine atom (e.g., alkylene, cycloalkylene, alkenyl, arylene, etc.), and linkers formed by linking multiple of these. Among these, -CO- or -arylene-alkylene groups having either a fluorine or an iodine atom are preferred as L1.

[0218] As an arylene group, phenylene is preferred.

[0219] The alkylene group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkylene group, but it is preferably 1 to 10, more preferably 1 to 3.

[0220] There is no particular limitation on the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0221] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom.

[0222] Alkyl groups can be straight-chain or branched. The number of carbon atoms in an alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.

[0223] The total number of fluorine and iodine atoms contained in the alkyl group having fluorine or iodine atoms is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0224] The aforementioned alkyl groups may also have heteroatoms such as oxygen atoms in addition to halogen atoms.

[0225] R2 represents a detached radical that is released by the action of an acid and can have either a fluorine or iodine atom.

[0226] Among them, groups represented by formulas (Z1) to (Z4) can be cited as detaching groups.

[0227] Equation (Z1): -C(Rx) 11 (Rx) 12 (Rx) 13 )

[0228] Equation (Z2): -C(=O)OC(Rx) 11 (Rx) 12 (Rx) 13 )

[0229] Equation (Z3): -C(R) 136 (R) 137 (OR) 138 )

[0230] Equation (Z4): -C(Rn1)(H)(Ar1)

[0231] In equations (Z1) and (Z2), Rx 11 ~Rx 13 Each can independently represent an alkyl group (straight-chain or branched) that may have fluorine or iodine atoms, or a cycloalkyl group (monocyclic or polycyclic) that may have fluorine or iodine atoms. Additionally, when Rx... 11 ~Rx 13 When all components are alkyl groups (linear or branched), Rx is preferred. 11 ~Rx 13 At least two of them are methyl groups.

[0232] Rx 11 ~Rx 13 Except for the fact that it can have fluorine or iodine atoms, it is the same as Rx1 to Rx3 in the above formulas (Y1) and (Y2), and is the same as the definition and preferred range of alkyl and cycloalkyl.

[0233] In equation (Z3), R 136 ~R138 Each can independently represent a hydrogen atom or a monovalent organic group that may have a fluorine or iodine atom. R 137 With R 138 They can bond together to form a ring. Examples of monovalent organic groups that can have fluorine or iodine atoms include alkyl groups that can have fluorine or iodine atoms, cycloalkyl groups that can have fluorine or iodine atoms, aryl groups that can have fluorine or iodine atoms, aralkyl groups that can have fluorine or iodine atoms, and groups formed by combining them (e.g., groups formed by combining alkyl and cycloalkyl groups).

[0234] In addition to fluorine and iodine atoms, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may also contain heteroatoms such as oxygen atoms. That is, for example, one of the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, such as the methylene group, may be replaced by a group having heteroatoms such as oxygen atoms or carbonyl groups.

[0235] As formula (Z3), it is preferably a group represented by the following formula (Z3-1).

[0236] [Chemical Formula 3]

[0237]

[0238] Here, L 11 and L 12 Each of these groups can independently represent a hydrogen atom; an alkyl group may have a heteroatom selected from the group consisting of fluorine, iodine, and oxygen atoms; a cycloalkyl group may have a heteroatom selected from the group consisting of fluorine, iodine, and oxygen atoms; an aryl group may have a heteroatom selected from the group consisting of fluorine, iodine, and oxygen atoms; or a group formed by combining these groups (for example, a group formed by combining alkyl and cycloalkyl groups that may have a heteroatom selected from the group consisting of fluorine, iodine, and oxygen atoms).

[0239] M1 represents a single bond or a divalent linker.

[0240] Q1 represents an alkyl group that may have heteroatoms selected from the group consisting of fluorine, iodine, and oxygen atoms; a cycloalkyl group that may have heteroatoms selected from the group consisting of fluorine, iodine, and oxygen atoms; an aryl group; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a combination thereof (e.g., a group consisting of an alkyl group and a cycloalkyl group that may have heteroatoms selected from the group consisting of fluorine, iodine, and oxygen atoms).

[0241] In formula (Z4), Ar1 represents an aromatic cyclic group that may have fluorine or iodine atoms. Rn1 represents an alkyl group that may have fluorine or iodine atoms, a cycloalkyl group that may have fluorine or iodine atoms, or an aryl group that may have fluorine or iodine atoms. Rn1 and Ar1 can bond with each other to form a non-aromatic ring.

[0242] As a repeating unit (Aa), a repeating unit represented by the general formula (AI) is also preferred.

[0243] [Chemical Formula 4]

[0244]

[0245] In the general formula (AI),

[0246] Xa1 represents a hydrogen atom or an alkyl group that may have substituents.

[0247] T represents a single bond or a divalent linker.

[0248] Rx1 to Rx3 each independently represent an alkyl group (straight-chain or branched) or a cycloalkyl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups.

[0249] Two of Rx1 to Rx3 can also be bonded together to form cycloalkyl groups (monocyclic or polycyclic).

[0250] As an alkyl group represented by Xa1, which can have substituents, examples include methyl groups or groups consisting of -CH2-R groups. 11 The group indicated by R. 11 The organic group representing a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group can be exemplified by alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom. Alkyl groups with 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. As Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0251] Examples of divalent linkers for T include alkylene groups, aromatic cycloalkanes, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

[0252] 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, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0253] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0254] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0255] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred.

[0256] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0257] The repeating unit represented by the general formula (AI) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 and Rx3 are bonded to form the above-mentioned cycloalkyl group.

[0258] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0259] As the repeating unit represented by the general formula (AI), the acid-degradable tertiary alkyl methacrylate repeating unit is preferred (Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit).

[0260] Resin (A) may have one repeating unit (Aa) or two or more repeating units.

[0261] The content of repeating unit (Aa) (total content when there are two or more repeating units (Aa)) relative to all repeating units in resin (A) is preferably 15 to 80 mol%, more preferably 15 to 70 mol%, and even more preferably 15 to 60 mol%.

[0262] The resin (A) preferably has at least one repeating unit (Aa) selected from the group consisting of repeating units represented by the following general formulas (A-VIII) to (A-XII).

[0263] [Chemical Formula 5]

[0264]

[0265] In general formula (A-VIII), R5 represents tert-butyl or -CO-O-(tert-butyl) group.

[0266] In general formulas (A-IX), R6 and R7 independently represent monovalent organic groups. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups.

[0267] In the general formula (AX), p represents 1 or 2.

[0268] In the general formulas (AX) to (A-XII), R8 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R9 represents an alkyl group having 1 to 3 carbon atoms.

[0269] In general formula (A-XII), R 10 It refers to alkyl or adamantyl groups having 1 to 3 carbon atoms.

[0270] <Repeating unit with acid group>

[0271] Resin (A) may also contain repeating units with acid groups.

[0272] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following general formula (B).

[0273] [Chemical Formula 6]

[0274]

[0275] R3 represents a hydrogen atom or a monovalent organic group that may have a fluorine or iodine atom. Preferably, the monovalent organic group that may have a fluorine or iodine atom is a group represented by -L4-R8. L4 represents a single bond or an ester group. Examples of R8 include alkyl groups that may have a fluorine or iodine atom, cycloalkyl groups that may have a fluorine or iodine atom, aryl groups that may have a fluorine or iodine atom, or combinations thereof.

[0276] R4 and R5 represent hydrogen, fluorine, iodine, or alkyl groups that may have fluorine or iodine atoms, respectively.

[0277] L2 represents a single bond or an ester group.

[0278] L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1). Examples of aromatic hydrocarbon cyclic groups include benzene and naphthyl groups. Examples of alicyclic hydrocarbon cyclic groups include monocyclic and polycyclic groups, such as cycloalkyl groups.

[0279] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon cyclic group with a (n+m+1) valence.

[0280] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0281] m represents an integer greater than or equal to 1. m is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0282] n represents an integer of 0 or 1 or higher. n is preferably an integer between 1 and 4.

[0283] In addition, (n+m+1) is preferably an integer from 1 to 5.

[0284] As a repeating unit having an acid group, it is also preferred to be a repeating unit represented by the following general formula (I).

[0285] [Chemical Formula 7]

[0286]

[0287] In general formula (I),

[0288] R 41 R 42 and R 43 Each of these groups independently represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or alkoxycarbonyl group. Wherein, R... 42 It can bond with Ar4 to form a ring, at which point R 42 Indicates a single bond or an alkylene group.

[0289] X4 indicates a single bond, -COO-, or -CONR. 64 -, R 64 It represents a hydrogen atom or an alkyl group.

[0290] L4 indicates a single bond or alkylene group.

[0291] Ar4 represents an aromatic ring group with an (n+1) valence, when it is combined with R 42 When bonded to form a ring, it represents an aromatic ring group with an (n+2) valence.

[0292] n represents an integer from 1 to 5.

[0293] R in general formula (I) 41 R 42 and R 43 The alkyl group is preferably an alkyl group with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably an alkyl group with 8 or fewer carbon atoms, and even more preferably an alkyl group with 3 or fewer carbon atoms.

[0294] R in general formula (I) 41 R 42and R 43 The cycloalkyl group can be monocyclic or polycyclic. Preferably, it is a monocyclic cycloalkyl group with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, or cyclohexyl.

[0295] R in general formula (I) 41 R 42 and R 43 The halogen atom can be fluorine, chlorine, bromine, or iodine, with fluorine being the preferred atom.

[0296] R in general formula (I) 41 R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably a derivative of the above-mentioned R. 41 R 42 and R 43 The alkyl group in the text is the same as the alkyl group in the text.

[0297] Ar4 represents an aromatic cyclic group with an (n+1) valence. When n is 1, the divalent aromatic cyclic group can have substituents, such as arylene groups with 6 to 18 carbon atoms, such as phenylene, tolylene group, naphthylene, and anthracene, or aromatic cyclic groups containing heterocycles, such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring.

[0298] Specific examples of (n+1) valence aromatic cyclic groups when n is an integer greater than or equal to 2 can be exemplified by groups obtained by removing (n-1) arbitrary hydrogen atoms from the above-described examples of divalent aromatic cyclic groups. (n+1) valence aromatic cyclic groups may also have substituents.

[0299] Substituents that can be present as the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, alkylene, and (n+1) valence aromatic cyclic groups include, for example, R in general formula (I). 41 R 42 and R 43 The examples listed include alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy alkoxy groups; aryl groups such as phenyl groups; etc.

[0300] As represented by X4 -CONR 64 -(R 64 R in (representing hydrogen atom or alkyl group) 64 Alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are alkyl groups with 20 or fewer carbon atoms, and preferably alkyl groups with 8 or fewer carbon atoms.

[0301] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0302] The alkylene group in L4 is preferably an alkylene group with 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene.

[0303] Ar4 is preferably an aromatic cyclic group with 6 to 18 carbon atoms, and more preferably a benzene cyclic group, a naphthyl cyclic group, or a biphenylene cyclic group.

[0304] The following are specific examples of repeating units represented by general formula (I), but the present invention is not limited thereto. In the formula, a represents 1 or 2.

[0305] [Chemical Formula 8]

[0306]

[0307] [Chemical Formula 9]

[0308]

[0309] [Chemical Formula 10]

[0310]

[0311] (Derived from the repeating unit (A-1) of hydroxystyrene)

[0312] The resin (A) preferably has a repeating unit (A-1) derived from hydroxystyrene as the repeating unit having an acid group.

[0313] As a repeating unit (A-1) derived from hydroxystyrene, examples of repeating units represented by the following general formula (1) can be cited.

[0314] [Chemical Formula 11]

[0315]

[0316] In general formula (1),

[0317] A represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group.

[0318] R represents a halogen atom, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl, or aryloxycarbonyl. When multiple Rs are present, they can be the same or different. When multiple Rs are present, they can collectively form a ring. Hydrogen atoms are preferred as Rs.

[0319] a represents an integer from 1 to 3, and b represents an integer from 0 to (5-a).

[0320] As a repeating unit (A-1), it is preferred to use a repeating unit represented by the following general formula (AI).

[0321] [Chemical Formula 12]

[0322]

[0323] Compositions containing resin (A) having repeating units (A-1) are preferably used for KrF exposure. The content of repeating units (A-1) in the resin (A) is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably 50 mol% or more. Furthermore, there are no particular limitations on the upper limit; for example, it is 100 mol% or less, more preferably 95 mol% or less.

[0324] <A repeating unit having at least one of the following groups: lactone, sulfonyl lactone, carbonate, and hydroxyadamantane (A-2)>

[0325] Resin (A) may contain repeating units (A-2) having at least one of the following: selected from lactone structure, carbonate structure, sulcinolone structure and hydroxyadamantane structure.

[0326] The lactone or sulfonolactone structure in the repeating unit having a lactone or sulfonolactone structure is not particularly limited, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sulfonolactone structure is preferred. More preferably, other ring structures are formed by forming a bicyclic or spirocyclic structure in the 5- to 7-membered ring lactone structure or by forming a bicyclic or spirocyclic structure in the 5- to 7-membered ring sulfonolactone structure.

[0327] As repeating units having a lactone structure or a sulcinolone structure, examples can be found in paragraphs 0094 to 0107 of WO2016 / 136354.

[0328] Resin (A) may contain repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0329] As a repeating unit having a carbonate structure, the repeating unit described in paragraphs 0106 to 0108 of WO2019 / 054311 can be cited as an example.

[0330] Resin (A) may contain repeating units having a hydroxyadamantane structure. Examples of repeating units having a hydroxyadamantane structure include repeating units represented by the following general formula (AIIa).

[0331] [Chemical Formula 13]

[0332]

[0333] In the general formula (AIIa), R1c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. R2c to R4c each independently represent a hydrogen atom or a hydroxyl group. At least one of R2c to R4c represents a hydroxyl group. Preferably, one or two of R2c to R4c are hydroxyl groups and the remainder are hydrogen atoms.

[0334] <Repeating units containing fluorine or iodine atoms>

[0335] Resin (A) may contain repeating units having fluorine or iodine atoms.

[0336] As a repeating unit having fluorine or iodine atoms, the repeating unit described in paragraphs 0080 to 0081 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0337] <Repeating unit with photoacid-producing group>

[0338] Resin (A) may contain repeating units other than those described above, which have groups that generate acid upon irradiation with radiation.

[0339] As a repeating unit having a photoacid-producing group, the repeating unit described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0340] <Repeating unit with alkali-soluble group>

[0341] Resin (A) may also contain repeating units with alkali-soluble groups.

[0342] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups substituted at the α-position with an electron-withdrawing group (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units having alkali-soluble groups in the resin (A), the resolution in contact hole applications is improved.

[0343] Examples of repeating units with alkali-soluble groups include repeating units formed from acrylic acid and methacrylic acid where the alkali-soluble groups are directly bonded to the resin backbone, or repeating units where the alkali-soluble groups are bonded to the resin backbone via linkers. Furthermore, the linkers can have monocyclic or polycyclic cyclic hydrocarbon structures.

[0344] As a repeating unit having an alkali-soluble group, it is preferably a repeating unit formed of acrylic acid or methacrylic acid.

[0345] <None of them contain repeating units with acid-decomposing groups or polar groups>

[0346] Resin (A) may also have repeating units that do not have acid-decomposable groups or polar groups. Preferably, the repeating units that do not have acid-decomposable groups or polar groups have hydrocarbon structures on their side chains.

[0347] As a repeating unit that does not have acid-decomposing groups or polar groups, an example of a repeating unit represented by the following general formula (CX-1) can be cited.

[0348] [Chemical Formula 14]

[0349]

[0350] In general formula (CX-1), R X1 It represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0351] R X2 It represents a hydrocarbon group.

[0352] As a result of R X2 The number of carbon atoms in the hydrocarbon group is preferably 6 to 20, more preferably 6 to 10.

[0353] The hydrocarbon group can be any of the following: straight-chain, branched, or cyclic.

[0354] Furthermore, when the hydrocarbon group is a cyclic structure or contains a cyclic structure, the aforementioned cyclic structure can be any of aromatic rings and alicyclic rings, or any of monocyclic and polycyclic rings. Additionally, the aforementioned cyclic structure can form a spirostructure and / or a bicyclic structure.

[0355] As a result of R X2 Specifically, examples of hydrocarbon groups that can be represented include straight-chain or branched hydrocarbon groups with 6 to 20 carbon atoms (e.g., 2-ethylhexyl), alicyclic hydrocarbon groups with 6 to 20 carbon atoms (e.g., cyclohexyl), and alkyl groups (benzyl) with 7 to 20 carbon atoms.

[0356] As repeating units that do not have acid-decomposable groups or polar groups, examples include the repeating units described in paragraphs 0236-0237 of U.S. Patent Application Publication No. 2016 / 0026083 and the repeating units described in paragraph 0433 of U.S. Patent Application Publication No. 2016 / 0070167.

[0357] When resin (A) comprises repeating units that do not have acid-degradable groups or polar groups, the content of repeating units that do not have acid-degradable groups or polar groups relative to all repeating units in resin (A) is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more. Furthermore, there is no particular limitation on the upper limit; for example, it is 30 mol% or less, more preferably 25 mol% or less.

[0358] <Other repeating units>

[0359] In addition to the repeating structural units mentioned above, resin (A) may also have various repeating structural units for purposes such as adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0360] <Properties of Resin (A)>

[0361] When the resist composition is for KrF exposure, EB exposure, or EUV exposure, the resin (A) preferably contains repeating units having aromatic hydrocarbon groups, and more preferably contains repeating units having phenolic hydroxyl groups. Examples of repeating units having phenolic hydroxyl groups include repeating units (A-1) derived from the above-mentioned hydroxystyrene and repeating units derived from hydroxystyrene (meth)acrylate.

[0362] Furthermore, when the resist composition is for KrF exposure, it is also preferable that the resin (A) contains repeating units of a structure protected by groups (detached groups) in which hydrogen atoms of phenolic hydroxyl groups are decomposed and removed by the action of acid.

[0363] When the photoresist composition is for KrF exposure, the content of repeating units having aromatic hydrocarbon groups in the resin (A) is preferably 30 to 100 mol% relative to all repeating units in the resin (A), more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%.

[0364] Resin (A) can be synthesized using conventional methods (e.g., free radical polymerization).

[0365] The weight-average molecular weight (Mw) of resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight-average molecular weight (Mw) of resin (A) to 1,000 to 200,000, it is possible to prevent the deterioration of heat resistance and dry etching resistance, thereby preventing the deterioration of developability and the deterioration of film-forming properties due to increased viscosity. In addition, the weight-average molecular weight (Mw) of resin (A) is the polystyrene conversion value determined by the above-described GPC method.

[0366] The dispersion (molecular weight distribution) of resin (A) is typically 1 to 5, preferably 1 to 3, and more preferably 1.1 to 2.0. The smaller the dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the pattern, resulting in better roughness.

[0367] In the resist composition, the content of resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, relative to the total solids content of the composition.

[0368] Furthermore, resin (A) can be used alone or in combination with two or more types.

[0369] Photo-acid generator (B)

[0370] The resist composition contains a photoacid generator (hereinafter also referred to as "photoacid generator (B)").

[0371] Photoacid generators are compounds that produce acids through irradiation with photochemical rays or radiation, and they are components that facilitate the deprotection reaction of resin components (the deprotection reaction of acid-degrading resins).

[0372] As a photoacid-producing agent (B), a compound that generates organic acids by irradiation with photochemical rays or radiation is preferred. Examples include sulfonium salt compounds, iodine salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazonium disulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

[0373] As a photoacid generator (B), known compounds that produce acid by irradiation with photochemical rays or radiation can be used alone or suitably selected as a mixture thereof. For example, known compounds disclosed in paragraphs

[0125] to

[0319] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0086] to

[0094] of U.S. Patent Application Publication No. 2015 / 0004544A1, and paragraphs

[0323] to

[0402] of U.S. Patent Application Publication No. 2016 / 0237190A1 can be used as photoacid generator (B).

[0374] As a photoacid generator (B), a compound represented by the following general formula (ZI), general formula (ZII) or general formula (ZIII) is preferred.

[0375] [Chemical Formula 15]

[0376]

[0377] In the above general formula (ZI),

[0378] R 201 R202 and R 203 Each organic group can be represented independently.

[0379] As R 201 R 202 and R 203 The number of carbon atoms in the organic groups is usually 1 to 30, preferably 1 to 20.

[0380] Furthermore, R 201 ~R 203 The two atoms in the ring can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester bonds, amide bonds, or carbonyl groups. As R... 201 ~R 203 Examples of groups formed by the bonding of two molecules within a single molecule include alkylene groups (e.g., butylene and pentylene) and -CH2-CH2-O-CH2-CH2-.

[0381] Z - It represents anion.

[0382] As preferred embodiments of the cation in the general formula (ZI), examples include the corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3), (ZI-4), and (ZI-5) described below.

[0383] Furthermore, the photoacid-generating agent (B) can be a compound having multiple structures represented by the general formula (ZI). For example, it can be R, a compound having the general formula (ZI). 201 ~R 203 At least one of them has an R with another compound represented by the general formula (ZI). 201 ~R 203 A compound having at least one structure formed by bonding via a single bond or a linker group.

[0384] First, the compound (ZI-1) will be described.

[0385] Compound (ZI-1) is R of the above general formula (ZI). 201 ~R 203 At least one of them is an arylsulfonium compound, that is, a compound with arylsulfonium as a cation.

[0386] In arylsulfonium compounds, it can be R 201 ~R 203 All are aryl, or can be R 201 ~R 203 One part of it is aryl, and the rest is alkyl or cycloalkyl.

[0387] Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0388] The aryl group contained in the arylsulfonium compound is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups can be the same or different.

[0389] The alkyl or cycloalkyl group in the arylsulfonium compound is preferably a straight-chain alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms. Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0390] By R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may each independently have alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl or phenylthio group as substituents.

[0391] Next, compound (ZI-2) will be described.

[0392] Compound (ZI-2) is R in formula (ZI). 201 ~R 203 Each of these refers independently to a compound that does not have an aromatic ring. Here, the aromatic ring also includes aromatic rings containing heteroatoms.

[0393] As R 201 ~R 203 Organic groups that do not have aromatic rings, typically have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

[0394] R 201 ~R 203 Each of the following is preferably alkyl, cycloalkyl, allyl, or vinyl, more preferably linear or branched 2-oxoalkyl, 2-oxocycloalkyl, or alkoxycarbonylmethyl, and even more preferably linear or branched 2-oxoalkyl.

[0395] As R 201 ~R 203Alkyl and cycloalkyl groups, preferably straight-chain alkyl groups with 1 to 10 carbon atoms or branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) or cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0396] R 201 ~R 203 It can be further substituted by halogen atoms, alkoxy groups (e.g., carbon atoms of 1 to 5), hydroxyl groups, cyano groups, or nitro groups.

[0397] Next, compound (ZI-3) will be described.

[0398] Compound (ZI-3) is a compound represented by the following general formula (ZI-3) and having a benzoylmethylsulfonium salt structure.

[0399] [Chemical Formula 16]

[0400]

[0401] In general formula (ZI-3),

[0402] R 1c ~R 5c Each of these can be independently represented as a hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio, or arylthio.

[0403] R 6c and R 7c Each can be independently represented by a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or aryl group.

[0404] R x and R y Each can be independently represented as alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl, or vinyl.

[0405] R 1c ~R 5c Any two or more of them, R 5c With R 6c R 6c With R 7c R 5c With R x and R x With R y They can be bonded separately to form ring structures, and each ring bond can independently contain oxygen atoms, sulfur atoms, ketone groups, ester bonds, or amide bonds.

[0406] Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0407] As R 1c ~R 5c Any two or more of them, R 6c With R 7c and R x With R y Examples of groups formed by bonding include butylene and pentylene.

[0408] As R 5c With R 6c and R 5c With R x The bonded group is preferably a single bond or an alkylene group. Examples of alkylene groups include methylene and ethylene.

[0409] Zc - It represents anion.

[0410] Next, compound (ZI-4) will be described.

[0411] The compound (ZI-4) is represented by the following general formula (ZI-4).

[0412] [Chemical Formula 17]

[0413]

[0414] In general formula (ZI-4),

[0415] l represents an integer from 0 to 2.

[0416] r represents an integer from 0 to 8.

[0417] R 13 This refers to a hydrogen atom, fluorine atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, alkoxycarbonyl group, or a group containing a cycloalkyl group. These groups may also have substituents.

[0418] R 14 This indicates a hydroxyl, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, cycloalkylsulfonyl, or a group containing a cycloalkyl group. These groups may also have substituents. When multiple R groups are present... 14 When, each of the above groups, such as hydroxyl, is represented independently.

[0419] R 15 Each group can independently represent an alkyl, cycloalkyl, or naphthyl group. These groups may also have substituents. Two R groups15 They can bond together to form a ring. When two Rs 15 When bonds are formed into a ring, heteroatoms such as oxygen or nitrogen atoms can be contained within the ring framework. In one embodiment, two R atoms are preferred. 15 They are alkylene groups and are bonded together to form a ring structure.

[0420] Z - It represents anion.

[0421] In the general formula (ZI-4), R 13 R 14 and R 15 The alkyl group is either straight-chain or branched. The alkyl group preferably has 1 to 10 carbon atoms. Methyl, ethyl, n-butyl, or tert-butyl are preferred alkyl groups.

[0422] Next, compound (ZI-5) will be described.

[0423] Compound (ZI-5) is a compound represented by the following general formula (ZI-5) and having a benzoylmethylsulfonium salt structure.

[0424] [Chemical Formula 18]

[0425]

[0426] R1 to R5 independently represent hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio.

[0427] The number of carbon atoms in the aforementioned alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, and alkylthioyl groups is preferably 1 to 20, and more preferably 1 to 10.

[0428] The number of carbon atoms in the aryl, aryloxy, and arylthio groups mentioned above is preferably 6 to 20, and more preferably 6 to 10.

[0429] In this embodiment, at least one of R1 to R5 is an alkyl group having 3 or more carbon atoms or an alkoxy group having 3 or more carbon atoms. From the viewpoint of being able to further reduce the amount of particles generated in the resist composition, the number of carbon atoms of the alkyl group and alkoxy group is preferably 3 to 10, and more preferably 3 to 6.

[0430] Alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, alkylthio and arylthio groups represented by R1 to R5 may further have substituents.

[0431] R6 and R7 independently represent a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or aryl group, respectively.

[0432] The number of carbon atoms in the alkyl and cycloalkyl groups mentioned above is preferably 1 to 20, and more preferably 1 to 10.

[0433] The number of carbon atoms in the aryl group is preferably 6 to 20, and more preferably 6 to 10.

[0434] Alkyl, cycloalkyl, and aryl groups represented by R6 and R7 can further have substituents.

[0435] R8 and R9 independently represent alkyl, cycloalkyl, or alkenyl groups, respectively.

[0436] The number of carbon atoms in the alkyl and cycloalkyl groups mentioned above is preferably 1 to 20, and more preferably 1 to 10.

[0437] The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 10, and even more preferably allyl or vinyl.

[0438] Alkyl, cycloalkyl, and alkenyl groups represented by R8 and R9 can further have substituents.

[0439] R8 and R9 can be bonded separately to form a ring structure. The ring structure formed by the separate bonding of R8 and R9 can contain heteroatoms within the ring framework (examples of heteroatoms include oxygen and nitrogen atoms, which can be in the form of ketone groups, ester bonds, or amide bonds). Examples of the above-mentioned ring structures include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0440] Furthermore, any two or more of R1, R5, R6, and R7 can be bonded separately to form a ring structure. The ring structure formed by bonding any two or more of R1, R5, R6, and R7 separately can contain carbon-carbon double bonds within the ring framework. Examples of the aforementioned ring structures include aromatic or non-aromatic hydrocarbon rings and polycyclic fused rings formed by combining two or more of these rings. Examples of ring structures include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0441] Z - It represents anion.

[0442] Next, general formulas (ZII) and (ZIII) will be explained.

[0443] In general formulas (ZII) and (ZIII), R 204 ~R207 Each can be represented independently as aryl, alkyl, or cycloalkyl.

[0444] As a result of R 204 ~R 207 The aryl group represented is preferably phenyl or naphthyl, more preferably phenyl. (From R) 204 ~R 207 The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of aryl groups with heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0445] As a result of R 204 ~R 207 The alkyl and cycloalkyl groups represented are preferably straight-chain alkyl groups with 1 to 10 carbon atoms, branched alkyl groups with 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl), or cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl).

[0446] By R 204 ~R 207 The aryl, alkyl, and cycloalkyl groups represented can each independently have substituents. As a group composed of R... 204 ~R 207 The aryl, alkyl, and cycloalkyl groups may have substituents, for example, alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 15 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl and phenylthio group, etc.

[0447] Z - It represents anion.

[0448] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - Preferably, the anion is represented by the following general formula (3).

[0449] [Chemical Formula 19]

[0450]

[0451] In general formula (3),

[0452] o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0453] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred.

[0454] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is even more preferred that Xf in both cases is a fluorine atom.

[0455] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R4 and R5 are present, R4 and R5 can be the same or different.

[0456] The alkyl groups represented by R4 and R5 may have substituents, and the number of carbon atoms is preferably 1 to 4. R4 and R5 are preferably hydrogen atoms.

[0457] Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as those of Xf in general formula (3).

[0458] L represents a binary linker. When multiple Ls exist, they can be the same or different.

[0459] Examples of divalent linkers include COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these. Preferably, the linkers are -COO-, -CONH-, -CO-, -O-, -SO2-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene-, and more preferably -COO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene-.

[0460] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group.

[0461] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0462] The alicyclic group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Among these, alicyclic groups with a large volume structure having 7 or more carbon atoms, such as norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, are preferred.

[0463] Aryl groups can be monocyclic or polycyclic. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, and anthracene.

[0464] The heterocyclic group can be monocyclic or polycyclic. Polycyclic heterocyclic groups can better suppress acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocyclic groups include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocyclic groups include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Examples of lactone and sulfonyl lactone rings include the lactone and sulfonyl lactone structures illustrated in the aforementioned resins. The heterocycle in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0465] The aforementioned cyclic organic groups may have substituents. Examples of such substituents include alkyl groups (which may be linear or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atom constituting the cyclic organic group (the carbon atom that contributes to ring formation) may be a carbonyl carbon.

[0466] As the anion represented by general formula (3), SO3 is preferred. - -CF2-CH2-OCO-(L)q'-W、SO3 - -CF2-CHF-CH2-OCO-(L)q'-W、SO3 - -CF2-COO-(L)q'-W、SO3 - -CF2-CF2-CH2-CH2-(L)qW or SO3 - -CF2-CH(CF3)-OCO-(L)q'-W. Here, L, q, and W are the same as in general formula (3). q' represents an integer from 0 to 10.

[0467] In one approach, Z is used as the general formula (ZI). - Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - It is also preferred to use an anion represented by the following general formula (4).

[0468] [Chemical Formula 20]

[0469]

[0470] In general formula (4),

[0471] X B1 and X B2 Each can be represented independently as either a hydrogen atom or a monovalent organic group without a fluorine atom. X B1 and X B2 Hydrogen atoms are preferred.

[0472] X B3 and X B4 Each can independently represent a hydrogen atom or a monovalent organic group. X is preferred. B3 and X B4 At least one of them is a fluorine atom or a monovalent organic group having a fluorine atom, more preferably X B3 and X B4 Both are fluorine atoms or monovalent organic groups having fluorine atoms. X is further preferred. B3 and X B4 Both of these are alkyl groups that have been substituted with fluorine.

[0473] L, q, and W are the same as in general formula (3).

[0474] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - Preferably, the anion is represented by the following general formula (5).

[0475] [Chemical Formula 21]

[0476]

[0477] In general formula (5), Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb independently represents a hydrogen atom or an organic group without a fluorine atom. The definitions and preferred methods of o, p, q, R4, R5, L and W are the same as in general formula (3).

[0478] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - It can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0479] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - It is also preferred to be an aromatic sulfonic acid anion represented by the following general formula (SA1).

[0480] [Chemical Formula 22]

[0481]

[0482] In formula (SA1),

[0483] Ar represents an aryl group, and may also have substituents other than sulfonic acid anions and -(DB) groups. Examples of substituents that may be present include fluorine atoms and hydroxyl groups.

[0484] n represents an integer greater than or equal to 0. Preferably, n is 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0485] D represents a single bond or a divalent linker. Examples of divalent linkers include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate groups, ester groups, and groups formed by combinations of two or more of these.

[0486] B represents a hydrocarbon group.

[0487] Preferably, D is a single bond and B is an aliphatic hydrocarbon structure. More preferably, B is isopropyl or cyclohexyl.

[0488] Z in the general formula (ZI) - Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - It is also preferred to use perfluoroalkyl sulfonate anions.

[0489] The number of carbon atoms in the perfluoroalkyl sulfonic acid anion is preferably 1 to 12, more preferably 2 to 10, and even more preferably 2 to 6. Specifically, C4F9SO3 can be cited as an example. - wait.

[0490] Preferred examples of sulfonium cations in general formula (ZI) and iodonium cations in general formula (ZII) are shown below.

[0491] [Chemical Formula 23]

[0492]

[0493] The following shows the anion Z in the general formula (ZI). - The anion Z in general formula (ZII) - Zc in general formula (ZI-3) - Z in general formula (ZI-4) - and Z in general formula (ZI-5) - A preferred example.

[0494] In addition, as Z - In addition to the following, C4F9SO3 is preferred. - Perfluoroalkyl sulfonic acid anions, etc.

[0495] [Chemical Formula 24]

[0496]

[0497] The above-mentioned cations and anions can be combined in any way to be used as photoacid generators (B).

[0498] The photoacid generator (B) can be in the form of a low-molecular-weight compound or in the form of being embedded in a part of the polymer. Furthermore, it can be in both the form of a low-molecular-weight compound and the form of being embedded in a part of the polymer.

[0499] The photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0500] When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.

[0501] When the photoacid generator (B) is in the form of being embedded in a part of the polymer, it can be embedded in a part of the aforementioned resin (A) or in a resin different from resin (A).

[0502] From the viewpoint of superior resolution, compounds containing a benzoyl methyl sulfonium salt structure are preferred as photoacid generators. Among these compounds, those represented by the above-described general formula (ZI-5) are preferred from the viewpoint of further reducing the amount of particles generated in the resist composition.

[0503] The content of photoacid generator (B) is not particularly limited, but is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content of the composition.

[0504] Photoacid generator (B) can be used alone or in combination with two or more. When two or more photoacid generators (B) are used in combination, it is preferable that their total dosage is within the above-mentioned range.

[0505] The acid dissociation constant pKa, which is the acid produced by decomposing a photoacid-producing agent (B) through irradiation with photochemical rays or radiation, is, for example, -0.01 or less, preferably -1.00 or less, more preferably -1.50 or less, and even more preferably -2.00 or less. There is no particular limitation on the lower limit of pKa, for example, it is -5.00 or more. pKa can be determined by the method described above.

[0506] Solvent (F)

[0507] The resist composition contains a solvent (F).

[0508] There are no particular restrictions on the solvent, but from the viewpoint of ensuring the in-plane uniformity of the film thickness during coating, an organic solvent with a boiling point (referring to the boiling point at 1 atmosphere) of 160°C or lower is preferred.

[0509] As a solvent, it is preferred to contain at least one of (M1) propylene glycol monoalkyl ether carboxylic acid ester and (M2), wherein (M2) is selected from at least one of the group consisting of propylene glycol monoalkyl ether, lactate, acetate, butyl butyrate, alkoxypropionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Additionally, the solvent may also contain components other than (M1) and (M2).

[0510] If a solvent containing component (M1) or (M2) is used in combination with the above-mentioned resin (A), the coatability of the composition is improved and a pattern with fewer development defects can be formed, which is therefore preferred.

[0511] As component (M1), it is preferably selected from one or more of the group consisting of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, and more preferably propylene glycol monomethyl ether acetate (PGMEA).

[0512] The following components are preferred as components (M2).

[0513] As a propylene glycol monoalkyl ether, propylene glycol monomethyl ether (PGME) or propylene glycol monoethyl ether (PGEE) is preferred.

[0514] As a lactate ester, ethyl lactate, butyl lactate or propyl lactate are preferred.

[0515] The preferred acetates are methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate.

[0516] As an alkoxypropionate, methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP) are preferred.

[0517] As a chain ketone, the preferred choices are 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, ionone, diacetonyl alcohol, acetoethanol, acetophenone, methyl naphthyl ketone, or methyl pentyl ketone.

[0518] As a cyclic ketone, methylcyclohexanone, isophorone, cyclohexanone, or cyclopentanone are preferred.

[0519] As a lactone, γ-butyrolactone is preferred.

[0520] As an alkylene carbonate, propylene carbonate is preferred.

[0521] As a component (M2), more preferably it is propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl pentyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone or propylene carbonate, and even more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, cyclohexanone or γ-butyrolactone.

[0522] In addition to the above-mentioned components, it is preferable to use an ester solvent with 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or fewer heteroatoms.

[0523] As an ester solvent having 7 or more carbon atoms and 2 or fewer heteroatoms, amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, or butyl butyrate are preferred, and isoamyl acetate is more preferred.

[0524] As component (M2), a flash point (hereinafter also referred to as fp) of 37°C or higher is preferred. Such component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl pentyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), amyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C), or propylene carbonate (fp: 132°C). Among these, propylene glycol monoethyl ether, ethyl lactate, amyl acetate, or cyclohexanone are more preferred, and propylene glycol monoethyl ether or ethyl lactate are even more preferred.

[0525] Additionally, here, "flash point" refers to the value listed in the reagent product catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

[0526] The mixing mass ratio (M1 / M2) of component (M1) and component (M2) in the mixed solvent is preferably in the range of "100 / 0" to "15 / 85", and more preferably in the range of "100 / 0" to "40 / 60". If this configuration is adopted, the number of development defects can be further reduced.

[0527] As described above, the solvent may also contain components other than components (M1) and (M2). In this case, the content of components other than components (M1) and (M2) is preferably in the range of 30% by mass or less, and more preferably in the range of 5% to 30% by mass, relative to the total amount of solvent.

[0528] Furthermore, from the viewpoint of further reducing the amount of particles generated in the resist composition, it is preferable to include one or more solvents selected from propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (PGME), ethyl lactate, cyclohexanone, and cyclopentanone.

[0529] The solvent (F) content in the resist composition is preferably set to a solid component concentration of 15-70% by mass.

[0530] The lower limit of the solid component concentration of the photoresist composition is more preferably 20% by mass or more, further preferably 25% by mass or more, and especially preferably 30% by mass or more. Furthermore, the upper limit is more preferably 60% by mass or less, further preferably 55% by mass or less, and especially preferably 50% by mass or less. Additionally, the solid component concentration of the photoresist composition is the mass percentage of the components other than the solvent relative to the total mass of the photoresist composition.

[0531] Acid Diffusion Control Agent (C)

[0532] The resist composition may contain an acid diffusion control agent (C).

[0533] The acid diffusion control agent (C) functions as a quencher, capturing the acid generated during exposure by the photoacid generator (B) and suppressing the reaction of acid-degrading resin in the unexposed portion due to excessive acid production. Examples of acid diffusion control agents (C) include basic compounds (DA), basic compounds (DB) whose basicity is reduced or eliminated by radiation, onium salts (DC) that are relatively weak acids relative to the photoacid generator (B), low-molecular-weight compounds (DD) having nitrogen atoms and groups that are removed by acid action, and onium salt compounds (DE) having nitrogen atoms in the cationic portion.

[0534] In the resist composition, a known acid diffusion control agent may be suitably used. For example, compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458 may be used as acid diffusion control agents (C).

[0535] As a basic compound (DA), the repeating unit described in paragraphs 0188 to 0208 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0536] In the resist composition, an onium salt (DC) that is a relatively weak acid relative to the photoacid generator (B) can be used as an acid diffusion control agent (C).

[0537] When a photoacid generator (B) is mixed with an onium salt that produces an acid that is relatively weaker than the acid produced by the photoacid generator (B), if the acid produced by the photoacid generator (B) collides with the onium salt containing unreacted weak acid anions through irradiation with photochemical rays or radiation, the weak acid is released through salt exchange, and an onium salt containing strong acid anions is produced. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, thus seemingly deactivating the acid and controlling acid diffusion.

[0538] As a relatively weak acid relative to photoacid generator (B), the onium salt described in paragraphs 0226 to 0233 of Japanese Patent Application Publication No. 2019-070676 can be cited as an example.

[0539] When the resist composition contains an acid diffusion control agent (C), the content of the acid diffusion control agent (C) (total if multiple agents are present) relative to the total solid content of the composition is preferably 0.01 to 10.0% by mass, more preferably 0.01 to 5.0% by mass.

[0540] In the resist composition, the acid diffusion control agent (C) can be used alone or in combination with two or more.

[0541] Plasticizer (D)

[0542] The resist composition may contain a plasticizer (D).

[0543] When the resist composition contains a plasticizer (D), the plasticity of the formed resist film is improved, and as a result, the solvent in the film is more easily volatilized, for example, during pre-exposure heating (pre-baking: PB (PreBake)).

[0544] Examples of plasticizers (D) include compounds having a poly(oxyethylene) structure. In compounds having a poly(oxyethylene) structure, the number of carbon atoms in the olefin unit is preferably 2 to 6, more preferably 2 to 3. Furthermore, the average number of addition atoms in the olefin unit is preferably 2 to 10, more preferably 2 to 6.

[0545] Furthermore, the compound having a poly(oxyethylene) structure preferably has polar groups such as hydroxyl, carboxyl, and amino groups. Because the compound having a poly(oxyethylene) structure possesses these polar groups, after exposure and development of the resist film, the polar groups in the compound having a poly(oxyethylene) structure readily bond with the polar groups in the resin through electrostatic interactions, resulting in a film with superior pattern density.

[0546] As a plasticizer (D), specifically, the following can be cited as examples.

[0547] [Chemical Formula 25]

[0548]

[0549] When the resist composition contains a plasticizer (D), the content of the plasticizer (D) (total if multiple plasticizers are present) is 1% by mass or more, preferably 3% by mass or more, and more preferably 5% by mass or more, relative to the total solids content of the composition. Furthermore, the upper limit is, for example, 30% by mass or less, preferably 25% by mass or less.

[0550] In the resist composition, plasticizer (D) can be used alone or in combination with two or more.

[0551] Surfactants (E)

[0552] The resist composition may contain a surfactant (E). By containing a surfactant (E), it is possible to form patterns with better adhesion and fewer development defects.

[0553] The surfactant (E) is preferably a fluorinated and / or silicone surfactant.

[0554] As fluorinated and / or silicone surfactants, examples include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431, or 4430 (manufactured by Sumitomo 3MLimited); Megaface F171, F173, F176, F189, F113, F110, F177, F120, or R08 (manufactured by DICCORPORATION); Surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by ASAHI GLASS CO., LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.); and Surflon S-393 (manufactured by SEIMI CHEMICAL) can be used. (manufactured by Gemco Co., Ltd.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA Solutions Inc.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos Corporation). Additionally, as a silicone surfactant, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used.

[0555] Furthermore, in addition to the known surfactants described above, the surfactant (E) can also be synthesized using fluorinated aliphatic compounds manufactured by telomerization (also known as short-chain polymer telomerization) or oligomerization (also known as oligomerization). Specifically, a polymer having fluorinated aliphatic groups derived from the fluorinated aliphatic compound can be used as the surfactant (E). This fluorinated aliphatic compound can be synthesized by, for example, the method described in Japanese Patent Application Publication No. 2002-90991.

[0556] As a polymer having fluorinated aliphatic groups, copolymers of monomers having fluorinated aliphatic groups with (poly(oxyolefin)) acrylates and / or (poly(oxyolefin)) methacrylates are preferred. These copolymers can be irregularly distributed or block copolymers. Furthermore, examples of poly(oxyolefin) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutene) groups. Additionally, units with different chain lengths within the same chain length, such as poly(oxyethylene, oxypropylene, and oxyethylene block copolymers) or poly(oxyethylene and oxypropylene block copolymers), can also be used. Moreover, copolymers of monomers having fluorinated aliphatic groups with (poly(oxyolefin)) acrylates (or methacrylates) are not only binary copolymers but can also be ternary or higher copolymers formed by simultaneously copolymerizing two or more different monomers having fluorinated aliphatic groups and two or more different (poly(oxyolefin)) acrylates (or methacrylates).

[0557] For example, commercially available surfactants include Megaface F178, F-470, F-473, F-475, F-476, and F-472 (manufactured by DIC CORPORATION), which contain C6F. 13 A copolymer of acrylate (or methacrylate) with (poly(oxyethylene)) acrylate (or methacrylate), acrylate (or methacrylate) having C3F7 group, and a copolymer of (poly(oxyethylene)) acrylate (or methacrylate) with (poly(oxypropylene)) acrylate (or methacrylate).

[0558] Furthermore, surfactants other than those of fluorine and / or silicon as described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may also be used.

[0559] These surfactants (E) can be used alone or in combination of two or more.

[0560] When the resist composition contains a surfactant (E), the content of surfactant (E) (total if multiple surfactants are present) relative to the total solid content of the composition is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.

[0561] Other Additives

[0562] The resist composition may also contain crosslinking agents, alkali-soluble resins, dissolution-inhibiting compounds, dyes, photosensitizers, light absorbers, and / or compounds that promote solubility in the developer.

[0563] [Pattern Formation Method]

[0564] The resist composition manufactured by the above method is used for pattern forming. Furthermore, the steps of the pattern forming method using the above resist composition are not particularly limited, but the following steps are preferred.

[0565] Step A: Step of forming a resist film on a substrate using the resist composition manufactured by the above manufacturing method.

[0566] Process B: The process of exposing the resist film.

[0567] Step C: The process of developing the exposed resist film with a developer to form a pattern.

[0568] The steps of each of the above processes will be explained in detail below.

[0569] (Process A: Resist film formation process)

[0570] Step A is the step of forming a resist film on a substrate using the resist composition manufactured by the above-described manufacturing method. Furthermore, regarding the resist composition manufactured by the above-described manufacturing method, as described above...

[0571] As a method for forming a resist film on a substrate using the above-described resist composition, one example is a method of coating the above-described resist composition onto a substrate.

[0572] Furthermore, it is preferable to filter the above-mentioned resist composition as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0573] The above-described resist composition can be applied to substrates (e.g., silicon, silicon dioxide coatings) used in the manufacture of integrated circuit components using a suitable coating method such as a spin coater or a coating machine. Spin coating with a spin coater is preferred as the coating method.

[0574] After coating the above-mentioned resist composition, the substrate can be dried to form a resist film. In addition, various substrate films (inorganic films, organic films, or anti-reflective films) can be formed under the resist film as needed.

[0575] As a drying method, heating methods (pre-baking: PB) can be cited. Heating can be performed using devices available in general exposure machines and / or developing machines, or by using hot plates or the like.

[0576] The heating temperature is preferably 80-150℃, more preferably 80-140℃.

[0577] The heating time is preferably 30 to 1000 seconds, more preferably 40 to 800 seconds.

[0578] There is no particular limitation on the thickness of the resist film, but it is preferably 0.2 to 15 μm, and more preferably 1.0 to 15 μm.

[0579] Alternatively, a topcoat composition can be used to form a topcoat layer on top of the resist film.

[0580] The topcoat composition is preferably not mixed with the resist film so that it can be further and uniformly coated on the top layer of the resist film.

[0581] The thickness of the top coating is preferably 10–200 nm, more preferably 20–100 nm.

[0582] There are no particular restrictions on the top coating. A conventionally known top coating can be formed using conventionally known methods. For example, the top coating can be formed based on the content described in paragraphs 0072 to 0082 of Japanese Patent Application Publication No. 2014-059543.

[0583] (Process B: Exposure Process)

[0584] Process B is the process of exposing the resist film.

[0585] One method of exposure is to irradiate the formed resist film with radiation through a prescribed mask.

[0586] Examples of radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and EB (Electron Beam). Preferably, the wavelength is below 250 nm, more preferably below 220 nm, and especially preferably far ultraviolet light of 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and EB, with KrF excimer laser (248 nm) being the most preferred.

[0587] It is preferable to bake after exposure and before development (post-exposure bake: PEB).

[0588] The heating temperature is preferably 80-150℃, more preferably 80-140℃.

[0589] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds.

[0590] Heating can be achieved using devices found in general exposure machines and / or developing machines, or by using hot plates or the like.

[0591] This process is also known as post-exposure baking.

[0592] (Process C: Development Process)

[0593] Process C is the process of developing the exposed resist film with a developer to form a pattern.

[0594] Examples of development methods include: immersing the substrate in a tank filled with developer for a certain time (dip method); developing the substrate by causing the developer to bulge on the substrate surface through surface tension and then allowing it to stand for a certain time (puddle method); spraying developer onto the substrate surface (spray method); and continuously spraying developer onto a substrate rotating at a certain speed while scanning the developer nozzle at a certain speed (dynamic dispense method).

[0595] Furthermore, after the developing process, a process can be implemented where the developing process is stopped while replacing the solvent with another solvent.

[0596] There are no particular limitations as long as the development time is the time it takes for the resin in the unexposed area to fully dissolve. It is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds.

[0597] The temperature of the developer is preferably 0–50°C, and more preferably 15–35°C.

[0598] Examples of developing solutions include alkaline developing solutions and organic solvent developing solutions.

[0599] As an alkaline developer, an aqueous alkaline solution containing alkali is preferred. The alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is typically 0.1–20% by mass. Furthermore, the pH of the alkaline developer is typically 10.0–14.0.

[0600] Organic solvent developer refers to a developer that contains organic solvents.

[0601] Organic solvents used in organic solvent developers include well-known organic solvents, such as ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0602] (Other processes)

[0603] The above-mentioned pattern forming method preferably includes a cleaning step using a rinsing solution after step C.

[0604] As the rinsing solution used in the rinsing process after the developing process using developer, pure water can be an example. Additionally, an appropriate amount of surfactant can be added to the pure water.

[0605] An appropriate amount of surfactant can be added to the rinsing solution.

[0606] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in step C can also be used as a mask to form a pattern on the substrate by processing the substrate (or the lower film and substrate).

[0607] There are no particular restrictions on the processing method of the substrate (or the lower film and the substrate), but a preferred method is to form a pattern on the substrate by using the pattern formed in step C as a mask and performing dry etching on the substrate (or the lower film and the substrate).

[0608] Dry etching can be a single-stage etching process or an etching process consisting of multiple stages. When etching consists of multiple stages, the etching processes in each stage can be the same or different.

[0609] Etching can be performed using any known method, with various conditions appropriately determined based on the type and application of the substrate. For example, etching can be performed according to the minutes of the International Society for Optical Engineering (SPIE), Proc. 6924, 692420 (2008), and Japanese Patent Application Publication No. 2009-267112. Furthermore, the method described in Chapter 4, Etching, of the "Semiconductor Process Textbook, Fourth Edition, 2007, Publisher: SEMI Japan" can also be used.

[0610] Among these methods, oxygen plasma etching is preferred as a dry etching process.

[0611] The various materials used in the manufacturing method of the present invention and the above-described resist composition (e.g., solvents, developers, rinsing solutions, compositions for forming antireflective films, compositions for forming topcoats, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, further preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. Examples of metallic impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Mo, Zr, Pb, Ti, V, W, and Zn.

[0612] As a method for removing impurities such as metals from the various materials mentioned above, filtration using a filter can be cited as an example. The filter pore size is preferably 0.20 μm or less, more preferably 0.05 μm or less, and even more preferably 0.01 μm or less.

[0613] As the filter material, fluoropolymers such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkylene (PFA), polyolefin resins such as polypropylene and polyethylene, and polyamide resins such as nylon 6 and nylon 66 are preferred. Filters that have been pre-cleaned with an organic solvent can be used. In the filter filtration process, multiple or various filters can be connected in series or parallel. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. Furthermore, various materials can be filtered multiple times; the multiple filtration process can be a circulating filtration process. As a circulating filtration process, the method disclosed in Japanese Patent Application Publication No. 2002-62667 is preferred, for example.

[0614] As a filter, a filter that reduces the amount of dissolved substances, as disclosed in Japanese Patent Application Publication No. 2016-201426, is preferred.

[0615] Besides filtration, impurities can be removed by adsorption materials, and filtration and adsorption materials can be used in combination. As adsorption materials, known adsorption materials can be used, such as inorganic adsorption materials like silica gel or zeolite, or organic adsorption materials like activated carbon. As metal adsorption materials, examples include those disclosed in Japanese Patent Application Publication No. 2016-206500.

[0616] Furthermore, as methods to reduce impurities such as metals contained in the aforementioned materials, examples include selecting raw materials with low metal content as constituent materials, filtering the constituent materials using filters, or performing distillation under conditions that minimize contamination, such as lining or coating the apparatus with fluoropolymers. The preferred conditions for filtering the constituent materials are the same as those described above.

[0617] To prevent the introduction of impurities, the aforementioned materials are preferably stored in containers described in U.S. Patent Application Publication No. 2015 / 0227049, Japanese Patent Application Publication No. 2015-123351, and Japanese Patent Application Publication No. 2017-13804.

[0618] Various materials can be used after being diluted with solvents.

[0619] Example

[0620] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be construed as limited to the embodiments shown below.

[0621] [Preparation of the resist composition]

[0622] The following section will first explain the various components incorporated into the corrosion inhibitor composition.

[0623] [Various ingredients]

[0624] Intermediate solutions

[0625] The intermediate solutions shown in Table 4 will be described below.

[0626] Table 3 shows the intermediate solutions (X-1 to X-12) shown in Table 4.

[0627] The following section describes the various components contained in the intermediate solutions shown in Table 3, followed by an explanation of the preparation method of the intermediate solutions.

[0628] <Various Ingredients>

[0629] (Photo-acid generator)

[0630] The photoacid generators (photoacid generators B-1 to B-5) shown in Table 3 are listed below. Furthermore, photoacid generators B-1 to B-5 are all solid raw materials (powder form).

[0631] [Chemical Formula 26]

[0632]

[0633] (solvent)

[0634] The solvents shown in Table 3 are listed below.

[0635] PGME: Propylene glycol monomethyl ether (boiling point 121℃)

[0636] PGMEA: Propylene glycol monomethyl ether acetate (boiling point 146℃)

[0637] Butyl acetate: boiling point 126℃

[0638] Ethyl lactate: Boiling point 154℃

[0639] Cyclohexanone: Boiling point 156℃

[0640] Cyclopentanone: Boiling point 131℃

[0641] <Solubility (g) of photoacid-generating agent relative to 100g of solvent at 25°C>

[0642] The solubility (g) of the photoacid-generating agent relative to 100g of solvent at 25°C was determined and differentiated according to the following criteria. Furthermore, the solubility (g) of the photoacid-generating agent relative to 100g of solvent at 25°C represents, for example, the solubility (g) of photoacid-generating agent B-3 relative to 100g of PGME at 25°C in the case of intermediate solution X-1 in Table 3. The evaluation is shown in Table 3.

[0643] (Benchmark)

[0644] "A": Solubility exceeds 3g

[0645] "B": Solubility is 0.5-3g

[0646] "C": Solubility less than 0.5g

[0647] <Preparation of intermediate solution>

[0648] The solvents shown in Table 3 were passed through a polyethylene filter with a pore size of 0.01 μm. The solvents and photoacid generators shown in Table 3 were mixed to achieve the concentrations shown in Table 3. The mixture was stirred for 8 hours at 23°C within ±2°C of the set temperature to prepare intermediate solutions (solutions X-1 to X-12).

[0649] The viscosity (mPa·s) of the prepared intermediate solution at 25 °C was determined using the methods described above.

[0650] [Table 3]

[0651]

[0652] Resin

[0653] The following shows the resins shown in Table 4 (resins A-1 to A-3).

[0654] Resins A-1 to A-3 were synthesized using known synthesis methods.

[0655] In addition, the weight-average molecular weight (Mw) and dispersity (Mw / Mn) of resins A-1 to A-3 were determined by GPC (charge carrier: tetrahydrofuran (THF)) (converted to polystyrene). Furthermore, through... 13 The composition ratio (molar percentage) of the resin was determined by C-NMR (nuclear magnetic resonance).

[0656] [Chemical Formula 27]

[0657]

[0658] In addition, the molar percentage (from left to right), weight-average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit of resins A-1 to A-3 are as follows.

[0659] • Resin A-1:

[0660] Mole percentage of each repeating unit: 60 / 19 / 21

[0661] Mw: 20,000

[0662] Mw / Mn: 1.5

[0663] • Resin A-2:

[0664] Mole percentage of each repeating unit: 60 / 30 / 10

[0665] Mw: 22,000

[0666] Mw / Mn: 1.4

[0667] • Resin A-3:

[0668] Mole percentage of each repeating unit: 60 / 30 / 10

[0669] Mw: 26,000

[0670] Mw / Mn: 1.6

[0671] Acid diffusion control agent

[0672] The structures of the acid diffusion control agents (C-1 to C-4) shown in Table 4 are shown below.

[0673] [Chemical Formula 28]

[0674]

[0675] Additive 1

[0676] The structure of additive 1 (additive D-1) shown in Table 4 is shown below.

[0677] [Chemical Formula 29]

[0678]

[0679] Additives 2

[0680] The following shows Additive 2 (Additive E-1) (surfactant) as shown in Table 4.

[0681] "E-1": Megaface R-41 manufactured by DIC Corporation

[0682] [Preparation of resist compositions 1-19]

[0683] The operations described later were carried out in a Class 1000 cleanroom to prepare the resist compositions shown in Table 4 below.

[0684] First, to those configured in cleanrooms, such as Figure 1 The stirred tank shown contains the various components to form the resist compositions 1 to 19 described in Table 4. Regarding the solvent, it is passed through a polyethylene filter with a pore size of 0.01 μm and then added to the stirred tank. The photoacid generator is added to the stirred tank in the form of the aforementioned intermediate solution. The intermediate solution is then passed through a polyethylene filter with a pore size of 0.05 μm before being added to the stirred tank. Regarding the resin, firstly, a portion of the solvent used in the preparation of the resist composition is passed through a polyethylene filter with a pore size of 0.01 μm to pre-dissolve the resin in the solvent, preparing a diluted solution (dilution concentration: 50% by mass). Then, the obtained diluted solution is passed through a polyethylene filter with a pore size of 0.1 μm and added to the stirred tank. Furthermore, the components other than the solvent, photoacid generator, and resin (acid diffusion control agent, additive 1, additive 2) are added to the stirred tank according to their respective composition. Specifically, a portion of the solvent used in the preparation of the resist composition was passed through a polyethylene filter with a pore size of 0.01 μm. Other components (acid diffusion control agent, additive 1, and additive 2) were pre-dissolved in the solvent to prepare a diluted solution (dilution concentration: 20% by mass). Then, each of the obtained diluted solutions was passed through a 0.05 μm polyethylene filter and placed into a stirred tank.

[0685] Next, as Figure 1 As shown, the stirring shaft equipped with stirring blades, which is located in the stirring tank, is rotated to stir and mix the various components.

[0686] The temperature of the mixture during stirring is set to 23°C and adjusted to be maintained within ±2°C of the set temperature. The stirring time is set to 12 hours.

[0687] After stirring, as follows Figure 1 As shown, the mixture in the mixing tank is pumped to a circulation piping connected to the mixing tank. The circulation piping is connected at one end to the bottom of the mixing tank and at the other end to the top of the mixing tank, with a filter installed along its length. Filtration is performed by circulating the mixture through the filter. The circulation continues until the volume of the mixture passing through the filter is four times the total volume of the piping.

[0688] In addition, the above-mentioned filter type uses a two-stage filter consisting of a polyethylene filter with a pore size of 0.02μm and a nylon filter with a pore size of 0.15μm.

[0689] After the above cyclic filtration process is completed, as follows: Figure 1 As shown, the obtained resist composition was filled into an evaluation container via a discharge pipe and a discharge nozzle. Resist compositions 1 to 19 were obtained through the above sequence.

[0690] In addition, in the preparation of the resist composition 14, the concentration of the resin dilution solution was changed to 66.5% by mass.

[0691] [Preparation of resist composition 20]

[0692] Without pre-preparing an intermediate solution, the photoacid generator was added as powder to a stirring tank. Otherwise, the photoresist composition 20 was manufactured by the same method as the photoresist compositions 1 to 19 described above.

[0693] [evaluate]

[0694] [Viscosity Evaluation]

[0695] The viscosity of the prepared resist compositions 1-20 was determined using the methods described above.

[0696] [Measurement of particle number]

[0697] The number of particles with a diameter of 0.3 μm or larger contained in 10 mL of the resist composition was measured using a liquid particle analyzer (KS-18FX; manufactured by RION CO., LTD.), and the number of particles per 1 mL of the resist composition was calculated from this.

[0698] In Table 4, the "Content" column for "Resin", "Photoacid Generator", "Acid Diffusion Control Agent", "Additive 1" and "Additive 2" indicates the content (mass %) of each component relative to the total solids content in the resist composition. Furthermore, in resist compositions 1 to 19, the photoacid generator is formulated in the form of an intermediate solution so that its content (mass %) relative to the total solids content in the resist composition is as shown in Table 4.

[0699] In Table 4, the values ​​in the "Solvent" column represent the mass ratio of each component.

[0700] In Table 4, the "Solids Concentration" column indicates the total solids concentration (mass%) in the resist composition.

[0701] In Table 4, under the column "Structure of Photoacid Generator," compounds with a benzoylmethyl sulfonium salt structure are indicated by "A" or "B," while compounds without a benzoylmethyl sulfonium salt structure are indicated by "-". Furthermore, when the photoacid generator is a compound with a benzoylmethyl sulfonium salt structure, "A" indicates that the photoacid generator corresponds to a compound represented by the above general formula (ZI-5), and "B" indicates that the photoacid generator does not correspond to a compound represented by the above general formula (ZI-5).

[0702]

[0703] As shown in Table 4, it is confirmed that the manufacturing method according to the present invention can achieve the desired effect.

[0704] Furthermore, a comparison of resist compositions 10 to 12 confirmed that when the solubility of the photoacid generator relative to 100g of solvent at 25°C is 0.5g or more (preferably more than 3g), the amount of particles generated in the resist composition can be further reduced.

[0705] Furthermore, a comparison of resist compositions 10 to 12 confirmed that when the photoacid generator contains a compound having a benzoyl methyl sulfonium salt structure, and the compound having the benzoyl methyl sulfonium salt structure is a compound represented by the general formula (ZI-5), the amount of particles generated in the resist composition can be further reduced.

[0706] Furthermore, a comparison of resist compositions 1-3, 6-9 and 14 confirmed that when the difference between the viscosity of the intermediate solution and the viscosity of the resist composition is less than 600 mPa·s, the amount of particles generated in the resist composition can be further reduced.

[0707] Furthermore, a comparison of resist compositions 12 and 13, as well as a comparison of resist compositions 1, 10 and 16, confirmed that when the viscosity of the intermediate solution is below 50 mPa·s, the amount of particles generated in the resist composition can be further reduced.

[0708] Furthermore, a comparison of resist compositions 1-3, 6-9, 15, and 17-19 confirmed that when the solvent of the intermediate solution contains one or more solvents selected from PGMEA, PGME, ethyl lactate, cyclohexanone, and cyclopentanone, the amount of particles generated in the resist composition can be further reduced.

[0709] [KrF Exposure Experiment]

[0710] (Pattern Formation)

[0711] Using a spin coater "ACT-8" manufactured by Tokyo Electron Limited, instead of applying an anti-reflective film, the prepared resist compositions (resist compositions 1 to 19) were coated onto silicon wafers (8-inch diameter) treated with HMDS (hexamethyldisilazane). The wafers were then baked at 130°C for 180 seconds (PB) to form resist films with thicknesses corresponding to the resist compositions shown in Table 4.

[0712] The obtained resist film was patterned using a KrF excimer laser scanner (ASML; PAS5500 / 850C, wavelength 248nm, NA=0.60, σ=0.75) through a mask with a line and spatial pattern that makes the spatial width of the pattern 5μm and the spacing width 20μm.

[0713] After baking the exposed resist film at 120°C for 60 seconds (PEB), it was developed with a developer (2.38% TMAH solution) for 60 seconds and then rotated to dry, resulting in an isolated spatial pattern with a spatial width of 5 μm and a spacing of 20 μm.

[0714] In addition, the pattern size was measured using a scanning electron microscope (Hitachi High-Tech Corporation, 9380II).

[0715] The resulting patterns were confirmed to have good verticality and rectangular shape.

[0716] Symbol Explanation

[0717] 10-Agitator, 12-Agitator shaft, 14-Agitator blades, 16-Circulation piping, 18-Filter, 20-Discharge piping, 22-Discharge nozzle.

Claims

1. A method for manufacturing a photosensitive or radiosensitive linear resin composition, comprising: Step 1: Prepare an intermediate solution containing a photoacid-generating agent and a solvent; and Step 2 involves mixing the intermediate solution with a resin whose polarity has increased at least through the action of acid to prepare a photosensitive radioactive or radiosensitive linear resin composition with a viscosity of 10 mPa·s or higher. In step 1, the solubility of the photoacid-generating agent relative to 100g of the solvent at 25°C is 0.5g or more.

2. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1, wherein, The viscosity of the intermediate solution is below 50 mPa·s.

3. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The viscosity difference between the intermediate solution and the photosensitive radioactive or radiosensitive linear resin composition having a viscosity of 10 mPa·s or higher is 50 mPa·s to 600 mPa·s.

4. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The solvent comprises one or more solvents selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, cyclohexanone, and cyclopentanone.

5. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The photoacid-producing agent comprises a compound represented by the following general formula (ZI-5). In the formula, R1 to R5 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkylcarbonyloxy, halogen atoms, hydroxyl, nitro, alkylthio, or arylthio. At least one of R1 to R5 is an alkyl or alkoxy group having 3 or more carbon atoms. R6 and R7 independently represent hydrogen atoms, alkyl, cycloalkyl, halogen atoms, cyano, or aryl. R8 and R9 independently represent alkyl, cycloalkyl, or alkenyl groups. Furthermore, any two or more of R1, R5, R6, and R7 are optionally bonded together to form a ring. Additionally, R8 and R9 are optionally bonded together to form a ring. Z - It represents anion.

6. A pattern forming method, comprising the following steps: The step of forming a resist film on a substrate using the photosensitive radioactive or radioactive linear resin composition obtained by the manufacturing method of any one of claims 1 to 5. The process of exposing the resist film; and The process of developing the exposed resist film using a developing solution.

7. A method for manufacturing an electronic device, comprising the pattern forming method of claim 6.

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