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

Abstract

Provided is a method for producing a radiation-sensitive or radiation-sensitive resin composition having a viscosity of 10 mPa·s or more, the method including: Step 1, in which at least a resin whose polarity is increased by the action of an acid, a photoacid generator, and a solvent are fed as raw materials into a stirring tank; and Step 2, in which the raw materials are stirred in the stirring tank.

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, one example is a method in which a resist film is formed from a photosensitive radioactive or radiosensitive linear resin composition, the obtained resist film is exposed, and then developed to form a resist pattern.

[0004] As a photosensitive or radiosensitive linear resin composition, compositions containing a resin (acid-degradable resin) comprising repeating units having acid-degradable groups are known.

[0005] In recent years, photosensitive radioactive or radiosensitive linear resin compositions suitable for patterning using thick-film resist films have also been proposed (for example, see Patent Document 1).

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2017 / 078031 Summary of the Invention

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

[0010] Patent Document 1 discloses a photosensitive radioactive or radioactive linear resin composition capable of forming patterns with good sensitivity and excellent cross-sectional shape. However, through the research of the inventors, it has been found that in photosensitive radioactive or radioactive linear resin films (especially thick-film photosensitive radioactive or radioactive linear resin films) obtained from the photosensitive radioactive or radioactive linear resin composition, there is room for further improvement in the uniformity of film thickness within the wafer plane (hereinafter also referred to as "in-plane uniformity of film thickness").

[0011] The present invention aims to provide a method for manufacturing a photosensitive or linearly photosensitive resin composition that can form a photosensitive or linearly photosensitive resin film with extremely excellent in-plane uniformity of film thickness, especially when forming a thick film (e.g., 1 μm or more) of photosensitive or linearly photosensitive resin film; a pattern forming method using the above-described method for manufacturing a photosensitive or linearly photosensitive resin composition; and a method for manufacturing an electronic device.

[0012] means for solving technical problems

[0013] The inventors have discovered that the above-mentioned problems can be solved by the following structure. [1]

[0015] A method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition, wherein the photosensitive or radiosensitive linear resin composition has a viscosity of 10 mPa·s or higher, and comprises:

[0016] Step 1 involves adding, as raw materials, at least the resin whose polarity increases due to the action of acid, a photoacid generator, and a solvent into a mixing tank; and

[0017] Step 2: Stir the above-mentioned raw materials in the above-mentioned mixing tank.

[0018] Throughout step 2 described above, the liquid temperature in the stirring tank is controlled to be at least 3.0°C higher than the initial liquid temperature at the beginning of step 2.

[0019] The temperature of the liquid in the stirring tank in step 2 is controlled by passing an inactive gas through the stirring tank. [2]

[0021] According to the method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition described in [1], wherein,

[0022] The temperature of the inactive gas used to pass through the above-mentioned mixing tank is 15℃~20℃. [3]

[0024] According to the method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition described in [1] or [2], wherein,

[0025] The stirring in step 2 above is carried out by a stirring shaft with stirring blades, and the stirring shaft rotates at a speed of 50 to 400 rpm. [4]

[0027] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [3], wherein,

[0028] Throughout step 2 described above, the liquid temperature in the stirring tank is controlled to be 2.0°C or less higher than the liquid temperature at the beginning of step 2. [5]

[0030] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [4], wherein,

[0031] The viscosity of the above-mentioned photosensitive or radiosensitive linear resin composition is 100 mPa·s or higher. [6]

[0033] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [5], wherein,

[0034] The stirring in step 2 above is carried out by a stirring shaft with stirring blades.

[0035] When the viscosity of the above-mentioned photosensitive or radiosensitive linear resin composition is set as X, in the above-mentioned step 2, Y < 40 × Ln(X) + 65 is satisfied, where Y represents the rotational speed of the stirring blade. [7]

[0037] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [6], wherein,

[0038] The temperature of the liquid is controlled by adjusting the flow rate of the inactive gas passing through the aforementioned mixing tank. [8]

[0040] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [7], wherein,

[0041] The concentration of solid components in the above-mentioned photosensitive or radiosensitive linear resin composition is 20% by mass or more. [9]

[0043] The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [8], wherein,

[0044] The resin whose polarity increases due to the action of the above-mentioned acid contains repeating units with acid-decomposable groups and repeating units represented by the following general formula (1), and the resin whose polarity increases due to the action of the above-mentioned acid has aromatic ring groups.

[0045] [Chemical Formula 1]

[0046]

[0047] In general formula (1),

[0048] R1 represents a hydrogen atom, a halogen atom, or an alkyl group.

[0049] R2 indicates an alkyl group having 2 or more carbon atoms.

[10]

[0051] A pattern forming method, which has the following characteristics:

[0052] The process of forming a resist film with a thickness of 3 μm to 20 μm on a substrate using a photosensitive radioactive or radiosensitive linear resin composition manufactured by any one of [1] to [9];

[0053] The process of exposing a photoresist film; and

[0054] The process of developing an exposed resist film using a developer to form a pattern.

[11]

[0056] A method for manufacturing an electronic device, comprising the pattern forming method described in

[10] .

[0057] Invention Effects

[0058] According to the present invention, a method for manufacturing a photosensitive radioactive or radioactive linear resin composition, which can form a photosensitive radioactive or radioactive linear resin film with extremely excellent in-plane uniformity of film thickness, especially when forming a thick film (e.g., 1 μm or more), a pattern forming method using the above-described method for manufacturing the photosensitive radioactive or radioactive linear resin composition, and a method for manufacturing an electronic device are provided. Attached Figure Description

[0059] Figure 1 This is a schematic diagram illustrating an example of an apparatus that can be used in a method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition according to the present invention. Detailed Implementation

[0060] Hereinafter, an example of a method for implementing the present invention will be described.

[0061] 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.

[0062] In this specification, the designations of groups (atomic groups) that do not specify whether they are substituted or unsubstituted include both substituted and unsubstituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). Furthermore, "organic group" in this specification refers to a group containing at least one carbon atom.

[0063] Furthermore, in this specification, the type, position, and number of substituents when "substituents may be present" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups other than hydrogen atoms, and can be selected from the following substituents T.

[0064] (Substituent T)

[0065] Examples of substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxyacetyl; alkylthioalkyl groups such as methylthioalkyl and tert-butylthioalkyl; arylthioalkyl groups such as phenylthioalkyl and p-tolylthioalkyl; alkyl; cycloalkyl; aryl; heteroaryl; hydroxyl; carboxyl; formyl; sulfonyl; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfonamide; silyl; amino; monoalkylamino; dialkylamino; arylamino; nitro; formyl; and combinations thereof.

[0066] Unless otherwise specified, the bonding orientation of the divalent groups marked in this specification is not limited. 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 either *1-OCO-C(CN)=CH-*2 or *1-CH=C(CN)-CO0-*2.

[0067] 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".

[0068] 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 using a 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).

[0069] In this manual, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet radiation represented by an excimer laser, extreme ultraviolet (EUV), X-rays, and electron beams (EB). In this manual, "light" refers to photochemical rays or radiation.

[0070] Unless otherwise stated, “exposure” in this specification includes not only exposures using bright-line spectra of mercury lamps, far-ultraviolet radiation (represented by excimer lasers), extreme ultraviolet radiation, X-rays, and EUV, but also depictions using particle beams such as electron beams and ion beams.

[0071] [Method for manufacturing a photosensitive or radiosensitive linear resin composition with a viscosity of 10 mPa·s or higher]

[0072] The method for manufacturing the photosensitive or radiosensitive linear resin composition of the present invention having a viscosity of 10 mPa·s or higher comprises:

[0073] Step 1 involves adding, as raw materials, at least the resin whose polarity increases due to the action of acid, a photoacid generator, and a solvent into a mixing tank; and

[0074] Step 2 involves stirring the aforementioned raw materials in the aforementioned mixing tank. This method is used to manufacture a photosensitive or radiosensitive linear resin composition with a viscosity of 10 mPa·s or higher.

[0075] Throughout step 2 described above, the liquid temperature in the stirring tank is controlled to be at least 3.0°C higher than the initial liquid temperature at the beginning of step 2.

[0076] The temperature of the liquid in the stirring tank in step 2 is controlled by passing an inactive gas through the stirring tank.

[0077] The inventors have discovered that in the method for manufacturing a photosensitive or radiosensitive linear resin composition (hereinafter, also referred to as "the composition of the present invention" or "the composition") (typically a photoresist composition) with a viscosity of 10 mPa·s or higher (hereinafter, also referred to as "the manufacturing method of the present invention"), as described in step 2 above, throughout step 2, the liquid temperature in the stirring tank is controlled to be 3.0°C or less higher than the liquid temperature at the beginning of step 2. The control of the liquid temperature in the stirring tank in step 2 is achieved by passing an inactive gas through the stirring tank, thereby improving the in-plane uniformity of the film thickness of the photosensitive or radiosensitive linear resin film.

[0078] Although the mechanism by which the manufacturing method of the present invention solves the problem of the present invention may not be clear, the inventors believe the following.

[0079] Typically, in the manufacture of photosensitive radioactive or radioactive linear resin compositions, various components and solvents are mixed and stirred. However, when forming a thick film (e.g., 1 μm or more) of photosensitive radioactive or radioactive linear resin film, a liquid form of the photosensitive radioactive or radioactive linear resin composition with high viscosity (e.g., 10 mPa·s or more) is preferred. Through in-depth research, the inventors discovered that when manufacturing such a high-viscosity photosensitive radioactive or radioactive linear resin composition, the heat generated during stirring easily rises to the liquid temperature of the liquid. As this temperature rises, the solvent in the composition evaporates. Furthermore, the inventors hypothesize that with this solvent evaporation, the viscosity of the final prepared photosensitive radioactive or radioactive linear resin composition increases compared to the originally expected viscosity (target viscosity), thereby reducing the in-plane uniformity of the film thickness.

[0080] Based on this insight, the inventors have confirmed that in step 2, by employing the condition that "the liquid temperature in the stirring tank is controlled to be 3.0°C or less higher than the initial liquid temperature at the beginning of step 2 throughout step 2, and the control of the liquid temperature in the stirring tank in step 2 is achieved by passing an inactive gas through the stirring tank," surprisingly, when forming a photosensitive radioactive or radioactive linear resin film using a high-viscosity (e.g., 10 mPa·s or higher) photosensitive radioactive or radioactive linear resin composition, the in-plane uniformity of the film thickness becomes positively excellent. This is believed to be because, during stirring, the inactive gas introduced into the stirring tank absorbs at least a portion of the heat from the stirring process while being discharged from the stirring tank, thereby suppressing excessive temperature rise of the liquid, preventing solvent evaporation, and inhibiting a significant increase in viscosity of the final photosensitive radioactive or radioactive linear resin composition compared to the target viscosity. Consequently, the properties of the photosensitive radioactive or radioactive linear resin composition become the desired properties. Therefore, it can be considered that the in-plane uniformity of the film thickness is improved.

[0081] In the manufacturing method of the present invention, an inert gas is used. An inert gas is a low-reactivity gas used in chemical synthesis and for the preservation of highly reactive substances. Because the gas contains a low concentration of oxygen, it is possible to suppress the denaturation of photosensitive or radiosensitive linear resin compositions caused by the generation of oxygen free radicals compared to atmospheric conditions. From this perspective, the in-plane uniformity of the film thickness can also be considered improved.

[0082] The following is a detailed explanation of the steps involved in each process.

[0083] Furthermore, the manufacturing method of the present invention is preferably carried out in a clean room. 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.

[0084] <Process 1>

[0085] Step 1 is a process in which at least the resin, photoacid generator and solvent that have increased polarity through the action of acid are added as raw materials to a mixing tank.

[0086] Details about the resin, photoacid generator, and solvent used in step 1, which have increased polarity through the action of acid, will be described later.

[0087] Furthermore, in step 1, other components besides the resin whose polarity increases due to the action of acid, the photoacid generator, and the solvent can also be added to the stirring tank. Examples of these other components include acid diffusion control agents, hydrophobic resins, surfactants, alkali-soluble resins with phenolic hydroxyl groups, carboxylic acid onium salts, and dissolution-inhibiting compounds. Details regarding these other components will be described later.

[0088] The manufacturing method of the present invention can be carried out using an apparatus for manufacturing photosensitive radioactive or radiosensitive linear resin compositions. As the stirring tank in step 1, it is preferable to use the stirring tank in an apparatus for manufacturing photosensitive radioactive or radiosensitive linear resin compositions.

[0089] There are no particular limitations on the manufacturing apparatus that can be used in this invention, and any known manufacturing apparatus can be used.

[0090] Figure 1 The diagram shows an example of a manufacturing apparatus that can be used in the method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition of the present invention.

[0091] like Figure 1 As shown, the manufacturing apparatus 100 has a mixing tank 10 and a stirring shaft 12 rotatably mounted in the mixing tank 10.

[0092] The liquid-contacting parts (parts that come into contact with liquid) within the manufacturing apparatus are preferably lined or coated with fluoropolymers or the like.

[0093] As for the mixing tank 10, there are no particular limitations as long as it is a mixing tank that can accommodate resins, photoacid generators and solvents whose polarity increases through the action of acid, and known mixing tanks can be cited.

[0094] 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.

[0095] To improve mixing efficiency, baffles can be installed inside the mixing tank 10.

[0096] There is no particular limitation on the number of baffles, but 2 to 8 are preferred.

[0097] The width of the baffle in the horizontal direction of the stirring layer 10 is not particularly limited, but is preferably 1 / 8 to 1 / 2 of the diameter of the stirring tank.

[0098] 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.

[0099] The stirring shaft 12 has stirring blades 14 for stirring the liquid contained in the stirring tank 10.

[0100] Preferably, a drive source (e.g., a motor) is installed in the stirring shaft 12. The stirring shaft 12 is rotated by the drive source, thereby rotating the stirring blades 14 and stirring the components introduced into the stirring tank 10.

[0101] The shape of the stirring blade 14 is not particularly limited; for example, swirling submerged blades, propeller blades, and turbine blades can be used.

[0102] The mixing tank 10 is provided with a gas inlet 16 for introducing inactive gas into the mixing tank 10 and a gas outlet 18 for discharging inactive gas from the mixing tank 10.

[0103] Furthermore, the stirring tank 10 has a temperature sensor 20 for measuring the temperature of the liquid inside the stirring tank. For example... Figure 1 As shown, the temperature sensor is preferably installed at the bottom of the stirring tank 10 to measure the liquid temperature in the stirring tank.

[0104] The mixing tank 10 may have a material inlet for feeding various materials into the mixing tank.

[0105] Additionally, a cleaning nozzle (e.g., a sprayer) may be installed at the top of the mixing tank 10.

[0106] In step 1, when the components are placed into the mixing tank, stirring may or may not be performed. That is, refer to... Figure 1 The stirring shaft 12 can rotate or not.

[0107] There are no particular restrictions on the stirring method, but it is preferable to use a stirring shaft with the aforementioned stirring blades. The rotational speed of the stirring shaft with stirring blades is not particularly limited, but is preferably 20 to 500 rpm (rotations per minute), more preferably 40 to 450 rpm, and even more preferably 50 to 400 rpm.

[0108] In step 1, there are no particular limitations on the method of adding the various components as raw materials into the mixing tank.

[0109] For example, one method is to add the components through the material inlet of the mixing tank. The components can be added sequentially or all at once. Furthermore, when adding a single component, it can be added in multiple batches.

[0110] Furthermore, there is no particular restriction on the order in which the components are added to the mixing tank.

[0111] For example, the raw materials (containing at least a resin whose polarity increases through the action of acid, a photoacid generator, and a solvent) can be added to the mixing tank all at once or in batches. Furthermore, for example, the solvent constituting the raw materials can be added to the mixing tank in multiple stages.

[0112] In addition, the end of process 1 (the end of process 1) is the time when the raw materials that should be supplied to the mixing tank are put into the mixing tank in process 1.

[0113] Generally, when adding raw materials to a mixing tank, it is preferable to do so in a way that creates space within the 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 created in the mixing tank 10 that is not occupied by the mixture M of the raw materials.

[0114] There is no particular limitation on the percentage of raw materials in the mixing tank, but it is preferably 50-95% by volume, and more preferably 80-90% by volume.

[0115] In addition, the proportion of the above mixture can be obtained by the following formula (1).

[0116] Equation (1): Occupancy rate = {(volume of mixture in the mixing tank / volume of the mixing tank)} × 100

[0117] 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.

[0118] The porosity mentioned above is obtained by the following formula (2).

[0119] Equation (2): Porosity = {1 - (volume of mixture in the mixing tank / volume of the mixing tank)} × 100

[0120] <Process 2>

[0121] Step 2 is the process of stirring the raw materials in the aforementioned mixing tank.

[0122] Throughout step 2, the liquid temperature in the aforementioned mixing tank is controlled to be 3.0°C or less higher than the initial liquid temperature at the beginning of step 2.

[0123] The temperature of the liquid in the stirring tank in step 2 can be controlled by passing an inactive gas through the stirring tank.

[0124] There are no particular restrictions on the stirring method, but it is preferable to use a stirring shaft with the aforementioned stirring blades. The rotational speed of the stirring shaft with stirring blades (the same as the rotational speed of the stirring blades) is not particularly limited, but is preferably 20 to 500 rpm (rotations per minute), more preferably 40 to 450 rpm, and even more preferably 50 to 400 rpm.

[0125] In step 2, throughout the entire process, the liquid temperature in the mixing tank is controlled to be 3.0°C or less higher than the initial liquid temperature of step 2, preferably 2.0°C or less higher than the initial liquid temperature of step 2.

[0126] If the temperature is higher than the liquid temperature at the beginning of step 2 by more than 3.0°C, liquid evaporation is inevitable, which will cause problems with the in-plane uniformity of the obtained film thickness.

[0127] Here, for reference Figure 1 The start of step 2 is the earliest moment when both the state of all the raw materials to be supplied being contained in the mixing tank 10 and the state of the mixing shaft 12 being rotated are simultaneously satisfied. Therefore, the start of step 2, if the mixing shaft 12 is rotating in step 1, corresponds to the point at which the supply of all the raw materials to be supplied into the mixing tank 10 ends, and if the mixing shaft 12 is not rotating in step 1, corresponds to the point at which the rotation of the mixing shaft 12 begins after the supply of all the raw materials to be supplied into the mixing tank 10 has ended.

[0128] If the liquid temperature in the mixing tank meets the above conditions, there is no particular limitation on the lower limit of the liquid temperature in the mixing tank. In fact, it is preferably a temperature 1.0°C lower than the liquid temperature at the beginning of step 2, more preferably a temperature 0.5°C lower than the liquid temperature at the beginning of step 2, and even more preferably the liquid temperature at the beginning of step 2.

[0129] Furthermore, the liquid temperature range in the stirring tank is preferably 20°C to 28°C, more preferably 21°C to 26°C, and even more preferably 22°C to 24°C.

[0130] The temperature of the liquid in the mixing tank can be controlled by... Figure 1 The temperature is measured by the temperature sensor 20 shown.

[0131] As described above, in step 2, the liquid temperature in the stirring tank is controlled by passing an inactive gas through the stirring tank. Here, passing an inactive gas, in other words, passing an inactive gas through the stirring tank, refers to... Figure 1 Inactive gas is introduced through the gas inlet 16 of the stirring tank 10, and the introduced inactive gas is discharged through the gas outlet 18 of the stirring tank 10. Figure 1The arrows in the diagram schematically indicate the flow path of the inert gas. Additionally, piping is typically connected to the gas inlet 16 and gas outlet 18 of the mixing tank 10, through which the inert gas is introduced and discharged. Furthermore, the gas inlet 16, the flow control device 26 (described later), the gas temperature control device 24 (described later), and the tank 22 (described later) are typically connected via piping to allow the inert gas to flow.

[0132] In this invention, gases with an oxygen partial pressure below 15% of the total pressure are defined as inactive gases.

[0133] Examples of components constituting inert gases include nitrogen, helium, and argon, with nitrogen being preferred.

[0134] As an inactive gas, the gas is preferably a gas in which the total partial pressure of nitrogen and rare gases is 90% or more of the total pressure, more preferably a gas in which the total partial pressure is 95% or more of the total pressure, and even more preferably a gas in which the total partial pressure is 99% or more of the total pressure.

[0135] exist Figure 1 In the manufacturing apparatus 100 shown, a tank 22 containing an inactive gas is prepared, configured such that the inactive gas discharged from the tank 22 can be introduced into the gas inlet 16 of the stirring tank 10 via a gas temperature control device 24.

[0136] The gas temperature control device 24 is a device that can adjust the temperature of the introduced inert gas to a specific temperature and discharge it.

[0137] The temperature of the inactive gas passing through the above-mentioned stirring tank is preferably 15°C to 20°C, and more preferably 16°C to 18°C.

[0138] Here, the temperature of the inactive gas introduced into the stirring tank is represented by the temperature of the inactive gas within the stirring tank. Figure 1 In the manufacturing apparatus 100 shown, the gas temperature is adjusted to the preferred range described above by the gas temperature control device 24. The temperature of the inactive gas used in the stirring tank is preferably below the liquid temperature at the beginning of step 2.

[0139] As a preferred embodiment, the stirring in step 2 is carried out by a stirring shaft with stirring blades. When the viscosity of the above-mentioned photosensitive radioactive or radiosensitive linear resin composition is set as X, in step 2, it is preferable to satisfy Y < 40 × Ln(X) + 65 (Y represents the rotational speed of the stirring blades).

[0140] Furthermore, the liquid temperature is preferably controlled by adjusting the flow rate of the inactive gas passing through the stirred tank. The flow rate of the inactive gas is the flow rate of the inactive gas introduced into the stirred tank.

[0141] The above flow rate is not particularly limited, but is preferably 0 to 15 (L / min), more preferably 0 to 12 (L / min), and even more preferably 0 to 10 (L / min).

[0142] When the liquid temperature is controlled by adjusting the flow rate of the inactive gas passing through the mixing tank, as long as it is controlled to a temperature 3.0°C or less higher than the liquid temperature at the beginning of step 2, step 2 may include a period during which the inactive gas does not flow (equivalent to a period during which the flow rate of the inactive gas is zero).

[0143] exist Figure 1 In the manufacturing apparatus 100 shown, a flow control device 26 capable of measuring and adjusting the flow rate of the inactive gas is provided between the gas temperature control device 24 and the gas inlet 16 of the stirring tank 10. This device can measure the flow rate of the inactive gas passing through the stirring tank. With this structure, especially in step 2, the flow rate of the inactive gas can be monitored continuously.

[0144] Here, throughout step 2, the liquid temperature in the aforementioned stirring tank is controlled to be 3.0°C or lower than the liquid temperature at the beginning of step 2. The control of the liquid temperature in the aforementioned stirring tank in step 2 can be achieved by passing an inactive gas through the aforementioned stirring tank, but the specific method is not particularly limited.

[0145] For example, by simply setting the liquid temperature at the beginning of step 2 and setting the temperature and flow rate of the inactive gas used to pass through the mixing tank, it is possible to control the temperature throughout step 2 to be 3.0°C or less higher than the liquid temperature at the beginning of step 2.

[0146] Furthermore, the liquid temperature at the start of step 2 can be set, as can the temperature and flow rate of the inert gas passing through the mixing tank. When the liquid temperature reaches a predetermined temperature higher than the liquid temperature at the start of step 2 (e.g., 2.5°C, 2.0°C, 1.5°C, etc.), the liquid temperature can be controlled to not exceed 3.0°C higher than the liquid temperature at the start of step 2 by changing the flow rate of the inert gas. The above steps can also be repeated.

[0147] In summary, it is important to actively control the liquid temperature throughout step 2 to a temperature 3.0°C or less higher than the initial liquid temperature at the beginning of step 2.

[0148] Without detecting the liquid temperature in the stirring tank in step 2, and only allowing inactive gas to pass through the stirring tank, it is difficult to accurately control the liquid temperature.

[0149] There is no particular limitation on the stirring time in step 2. It is usually 7 to 24 hours, preferably 7 to 18 hours, and more preferably 8 to 12 hours.

[0150] Throughout step 2, the liquid temperature is actively controlled to be 3.0°C below the initial liquid temperature at the beginning of step 2. This temperature control is achieved through methods such as: Figure 1 As shown, the inactive gas discharged from the tank 22 is discharged by adjusting the temperature of the introduced inactive gas to a specific temperature using the gas temperature control device 24, and a specified flow rate is filled into the mixing tank from the gas inlet 16.

[0151] The flow rate of the inactive gas is measured and controlled by the flow control device 26 mentioned above.

[0152] The viscosity of the photosensitive or radiosensitive linear resin composition of the present invention is 10 mPa·s or higher. The viscosity was measured at 25.0°C using a viscometer (RE-85L) manufactured by TOKISANGYO.

[0153] The viscosity of the composition of the present invention is preferably 50 mPa·s or more, more preferably 100 mPa·s or more, and even more preferably 200 mPa·s or more.

[0154] Furthermore, the upper limit of the viscosity of the composition of the present invention is not particularly limited, and is generally below 1000 mPa·s.

[0155] Resins whose polarity increases through the action of acid.

[0156] A resin whose polarity increases due to the action of an acid (hereinafter, also simply "resin (A)") preferably has a repeating unit (Aa) (hereinafter, also simply "repeating unit (Aa)"), which has an acid-decomposing group.

[0157] 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.

[0158] As a polar group, an alkaline-soluble group is preferred. Examples include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tri(alkylcarbonyl)methylene groups, and tri(alkylsulfonyl)methylene groups, as well as acidic groups such as alcohol hydroxyl groups.

[0159] 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.

[0160] Examples of detaching groups that are released by the action of acid include groups represented by formulas (Y1) to (Y4).

[0161] Equation (Y1): -C(Rx1) (Rx2) (Rx3)

[0162] Equation (Y2): -C(=O)OC(Rx1) (Rx2) (Rx3)

[0163] Equation (Y3): -C(R) 36 ) (R 37 (OR) 38 )

[0164] Equation (Y4): -C(Rn) (H) (Ar)

[0165] 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.

[0166] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0167] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0168] 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.

[0169] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, as well as polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0170] 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.

[0171] 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.

[0172] 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.

[0173] In formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent substituent. R 37 With R 38 They can bond with each other to form a ring. Examples of monovalent substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0174] As formula (Y3), it is preferably a group represented by the following formula (Y3-1).

[0175] [Chemical Formula 2]

[0176]

[0177] 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).

[0178] M represents a single bond or a divalent linker.

[0179] 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).

[0180] 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.

[0181] 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.

[0182] 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).

[0183] 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.

[0184] 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.

[0185] As a repeating unit (Aa), it is more preferably a repeating unit represented by formula (A).

[0186] [Chemical Formula 3]

[0187]

[0188] L1 represents a divalent linking group 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 liberating group that can be liberated by acid and may have a fluorine or iodine atom. At least one of L1, R1, and R2 has a fluorine or iodine atom.

[0189] L1 represents a divalent linking group that may have a fluorine atom or an iodine atom. Examples of divalent linking groups that may have a fluorine atom or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that may have a fluorine atom or an iodine atom (e.g., alkylene, cycloalkylene, alkenyl, arylene, etc.), and linking groups formed by linking multiple of these. From the viewpoint of better performance of the present invention, -CO- or -arylene-alkylene groups having a fluorine atom or an iodine atom are preferred as L1.

[0190] As an arylene group, phenylene is preferred.

[0191] 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.

[0192] The total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine or iodine atoms is not particularly limited, but from the viewpoint of better effect of the present invention, it is preferred to be 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0193] 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.

[0194] Alkyl groups can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in an alkyl group, but it is preferably 1 to 10, more preferably 1 to 3.

[0195] There is no particular limitation on the total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine or iodine atoms, but from the viewpoint of better effect of the present invention, it is preferred to be 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0196] The aforementioned alkyl groups may also have heteroatoms such as oxygen atoms in addition to halogen atoms.

[0197] R2 represents a detached radical that is released by the action of an acid and can have either a fluorine or iodine atom.

[0198] As a detaching radical, groups represented by formulas (Z1) to (Z4) can be cited.

[0199] Equation (Z1): -C(Rx) 11 (Rx) 12 (Rx) 13 )

[0200] Equation (Z2): -C(=O) OC(Rx) 11 (Rx) 12 (Rx) 13 )

[0201] Equation (Z3): -C(R) 136 ) (R 137 (OR) 138 )

[0202] Equation (Z4): -C(Rn1) (H) (Ar1)

[0203] 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.

[0204] 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.

[0205] In equation (Z3), R 136 ~R 138 Each can independently represent a hydrogen atom or a monovalent substituent that may have a fluorine or iodine atom. R 137 With R138 They can bond together to form a ring. Examples of monovalent substituents 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).

[0206] 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.

[0207] As formula (Z3), it is preferably a group represented by the following formula (Z3-1).

[0208] [Chemical Formula 4]

[0209]

[0210] 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).

[0211] M1 represents a single bond or a divalent linker.

[0212] 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).

[0213] 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.

[0214] As a repeating unit (Aa), a repeating unit represented by the general formula (AI) is also preferred.

[0215] [Chemical Formula 5]

[0216]

[0217] In the general formula (AI),

[0218] Xa1 represents a hydrogen atom or an alkyl group that may have substituents.

[0219] T represents a single bond or a divalent linker.

[0220] 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.

[0221] Two of Rx1 to Rx3 can also be bonded together to form cycloalkyl groups (monocyclic or polycyclic).

[0222] 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 substituent represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent substituent. Examples include 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. Preferably, it is an alkyl group with 3 or fewer carbon atoms, and more preferably, it is a methyl group. As Xa1, it is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0223] Examples of divalent linking groups 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] The repeating unit represented by the general formula (AI) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0230] 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.

[0231] As the repeating unit represented by the general formula (AI), the acid-degradable (meth)acrylate tertiary alkyl ester repeating unit is preferred (Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit).

[0232] Resin (A) may have one repeating unit (Aa) or two or more repeating units.

[0233] 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 20 to 70 mol%.

[0234] 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).

[0235] [Chemical Formula 6]

[0236]

[0237] In general formulas (A-VIII), R5 represents tert-butyl, 1,1'-dimethylpropyl, or -CO-O-(tert-butyl)-.

[0238] In the general formula (A-IX), R6 and R7 independently represent monovalent substituents. Examples of monovalent substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups.

[0239] In the general formula (AX), p represents 1 or 2.

[0240] 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.

[0241] In general formula (A-XII), R 10 It refers to alkyl or adamantyl groups having 1 to 3 carbon atoms.

[0242] In addition to repeating units (Aa) with acid-decomposable groups, resin (A) may also have repeating units with polar groups such as acid groups, lactone structures, sulfonyl lactone structures, carbonate structures, and hydroxyadamantane structures.

[0243] (Repeating units with acid groups)

[0244] Resin (A) may also contain repeating units with acid groups.

[0245] As a repeating unit having an acid group, it is preferably a repeating unit represented by the following general formula (B).

[0246] [Chemical Formula 7]

[0247]

[0248] R3 represents a hydrogen atom or a monovalent substituent that may have a fluorine or iodine atom. Preferably, the monovalent substituent 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 groups formed by combining these.

[0249] R4 and R5 represent hydrogen, fluorine, iodine, or alkyl groups that may have fluorine or iodine atoms, respectively.

[0250] L2 represents a single bond or an ester group.

[0251] 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.

[0252] 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.

[0253] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0254] 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.

[0255] n represents an integer of 0 or 1 or higher. n is preferably an integer between 1 and 4.

[0256] In addition, (n+m+1) is preferably an integer from 1 to 5.

[0257] As a repeating unit having an acid group, it is also preferred to be a repeating unit represented by the following general formula (I).

[0258] [Chemical Formula 8]

[0259]

[0260] In general formula (I),

[0261] 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.

[0262] X4 indicates a single bond, -COO-, or -CONR. 64 -, R 64 It represents a hydrogen atom or an alkyl group.

[0263] L4 indicates a single bond or alkylene group.

[0264] 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.

[0265] n represents an integer from 1 to 5.

[0266] 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.

[0267] R in general formula (I) 41 R 42 and R 43The 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.

[0268] 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.

[0269] 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.

[0270] 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.

[0271] 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.

[0272] 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.

[0273] 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.

[0274] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0275] 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.

[0276] 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.

[0277] 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, 2, or 3.

[0278] [Chemical Formula 9]

[0279]

[0280] [Chemical Formula 10]

[0281]

[0282] [Chemical Formula 11]

[0283]

[0284] (Derived from the repeating unit (A-1) of hydroxystyrene)

[0285] The resin (A) preferably has a repeating unit (A-1) derived from hydroxystyrene as the repeating unit having an acid group.

[0286] As a repeating unit (A-1) derived from hydroxystyrene, examples of repeating units represented by the following general formula (1) can be cited.

[0287] [Chemical Formula 12]

[0288]

[0289] In general formula (1),

[0290] A represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group.

[0291] 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.

[0292] a represents an integer from 1 to 3, and b represents an integer from 0 to (5-a).

[0293] As a repeating unit (A-1), the repeating unit preferably represents the following general formula (AI).

[0294] [Chemical Formula 13]

[0295]

[0296] Compositions containing resin (A) having repeating units (A-1) are preferably used for KrF exposure, EB exposure, or EUV exposure. The content of repeating units (A-1) in resin (A) is preferably 30–99 mol%, more preferably 40–99 mol%, and even more preferably 50–99 mol%, relative to all repeating units in resin (A).

[0297] (Having at least one repeating unit selected from lactone, sulcinolone, carbonate, and hydroxyadamantane structures (A-2))

[0298] The resin (A) may contain repeating units (A-2) having at least one selected from lactone, carbonate, sulcinolone and hydroxyadamantane structures.

[0299] There are no particular limitations on the lactone or sulfonolactone structure in the repeating unit having a lactone or sulfonolactone structure. Preferably, it is a 5- to 7-membered ring lactone or 5- to 7-membered ring sulfonolactone structure. More preferably, it is 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, to form other ring structures.

[0300] As repeating units having a lactone structure or a sulcinolone structure, examples can be found in paragraphs 0094 to 0107 of WO2016 / 136354.

[0301] Resin (A) may contain repeating units having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.

[0302] 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.

[0303] 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).

[0304] [Chemical Formula 14]

[0305]

[0306] 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.

[0307] (Repeating units containing fluorine or iodine atoms)

[0308] Resin (A) may contain repeating units with fluorine or iodine atoms.

[0309] 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.

[0310] (Repeating unit with photoacid-generating group)

[0311] Resin (A) may also contain repeating units other than those described above, which have groups that produce acid upon irradiation by photochemical rays or radiation.

[0312] As a repeating unit having fluorine or iodine atoms, the repeating unit described in paragraphs 0092 to 0096 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0313] (Repeating unit with alkali-soluble group)

[0314] Resin (A) may also contain repeating units with alkali-soluble groups.

[0315] 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.

[0316] 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 linking groups. Furthermore, the linking groups can have monocyclic or polycyclic cyclic hydrocarbon structures.

[0317] As a repeating unit having an alkali-soluble group, it is preferably a repeating unit formed of acrylic acid or methacrylic acid.

[0318] (None of them contain repeating units with acid-decomposing groups or polar groups)

[0319] Resin (A) may also have repeating units that do not have acid-decomposable groups or polar groups. The repeating units that do not have acid-decomposable groups or polar groups preferably have an alicyclic hydrocarbon structure.

[0320] 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.

[0321] (Repeating unit represented by general formula (1))

[0322] The resin (A) preferably has repeating units represented by the following general formula (1).

[0323] [Chemical Formula 15]

[0324]

[0325] In general formula (1), R1 represents a hydrogen atom, a halogen atom, or an alkyl group. R2 represents an alkyl group with 2 or more carbon atoms.

[0326] Halogen atoms that can be represented by R1 include fluorine, chlorine, bromine, or iodine.

[0327] The alkyl group of R1 is not particularly limited, and examples include straight-chain or branched alkyl groups. It is preferably an alkyl group with 1 to 10 carbon atoms, and more preferably an alkyl group with 1 to 5 carbon atoms.

[0328] There is no particular limitation on the alkyl group having 2 or more carbon atoms as R2. Examples include straight-chain or branched alkyl groups. Preferably, it is an alkyl group having 2 to 20 carbon atoms, and more preferably, it is an alkyl group having 2 to 10 carbon atoms.

[0329] The aforementioned alkyl groups may have heteroatoms such as oxygen atoms, but they do not constitute acid-decomposing groups.

[0330] As a preferred embodiment, resin (A) comprises repeating units having acid-degradable groups and repeating units represented by the above general formula (1), and resin (A) preferably has aromatic ring groups.

[0331] There is no particular limitation on the aromatic ring in the aromatic ring group; monocyclic or polycyclic aromatic rings can be cited, for example, aromatic rings with 6 to 20 carbon atoms.

[0332] 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.

[0333] (Characteristics of Resin (A))

[0334] As resin (A), it is preferable that all repeating units are composed of repeating units derived from (meth)acrylate monomers (monomers having (meth)acrylate groups). In this case, it is also possible to use a resin in which all repeating units are derived from methacrylate monomers, all repeating units are derived from acrylate monomers, all repeating units are derived from methacrylate monomers, and any one of acrylate monomers. The repeating units derived from acrylate monomers are preferably 50 mol% or less relative to all repeating units in resin (A).

[0335] When the composition of the present invention is for argon fluoride (ArF) exposure, from the viewpoint of ArF light transmittance, it is preferable that the resin (A) does not substantially contain aromatic groups. More specifically, the repeating units containing aromatic groups are preferably 5 mol% or less relative to all repeating units of the resin (A), more preferably 3 mol% or less, ideally 0 mol%, that is, further preferably not containing repeating units containing aromatic groups.

[0336] Furthermore, when the composition of the present invention is used for ArF exposure, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure, and preferably does not contain fluorine atoms or silicon atoms.

[0337] When the composition of the present invention is for krypton fluoride (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.

[0338] Examples of repeating units having phenolic hydroxyl groups include repeating units (A-1) derived from hydroxystyrene and repeating units derived from hydroxystyrene (meth)acrylate.

[0339] Furthermore, when the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, it is also preferable that the resin (A) contains repeating units of a structure protected by a group (detached group) in which the hydrogen atom of the phenolic hydroxyl group is decomposed by the action of acid.

[0340] When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the content of repeating units having aromatic hydrocarbon groups contained in resin (A) is preferably 30 to 100 mol% relative to all repeating units in resin (A), more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%.

[0341] Resin (A) can be synthesized using conventional methods (e.g., free radical polymerization).

[0342] 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.

[0343] 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.

[0344] In the composition of the present invention, 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 above composition.

[0345] Furthermore, resin (A) can be used alone or in combination with two or more types.

[0346] Furthermore, in this specification, solid components refer to components other than solvents. Even if the aforementioned components are in a liquid state, they can still be considered solid components.

[0347] <Photo-acid generator (P)>

[0348] The compositions of the present invention contain a photoacid-producing agent (P). The photoacid-producing agent (P) is not particularly limited to any compound that produces acid upon irradiation by photochemical rays or radiation.

[0349] Photoacid generator (P) can be in the form of a low molecular weight compound or in the form of a component embedded in a polymer. Furthermore, both the low molecular weight compound form and the form embedded in a component of the polymer can be used in combination.

[0350] When the photoacid generator (P) is in the form of a low molecular weight compound, the weight-average molecular weight (Mw) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0351] When the photoacid generator (P) is in the form of being embedded in a part of the polymer, it can be embedded in a part of the resin (A) or in a resin different from the resin (A).

[0352] In this invention, the photoacid generator (P) is preferably in the form of a low molecular weight compound.

[0353] As for the photoacid generator (P), there is no particular limitation as long as it is a known photoacid generator. It is preferred to be a compound that generates organic acids by irradiation with photochemical rays or radiation, and more preferably a photoacid generator having fluorine or iodine atoms in its molecule.

[0354] Examples of the aforementioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonyl sulfonyl imine acids, bis(alkyl sulfonyl) imine acids, and tri(alkyl sulfonyl) methylated acids, etc.

[0355] The volume of acid produced by the photoacid generator (P) is not particularly limited, but from the viewpoint of suppressing the diffusion of acid generated during exposure into the non-exposed areas and improving resolution, it is preferable to... The above, better The above further optimizes The above are particularly preferred. That's all. Furthermore, from the viewpoint of sensitivity or solubility in the coating solvent, the volume of acid produced by the photoacid generator (P) is preferably... The following is preferred The following are further optimizations. the following.

[0356] The volumes mentioned above were calculated using "WinMOPAC" manufactured by Fujitsu Limited. To calculate these volumes, the chemical structure of the acid involved in each example was first entered. Then, using this structure as the initial structure, molecular force field calculations using the MM (Molecular Mechanics) method were performed to determine the most stable conformation of each acid. Subsequently, molecular orbital calculations using the PM (Parameterized Model number) method were performed on these most stable conformations, thereby calculating the "accessible volume" of each acid.

[0357] The structure of the acid produced by the photoacid generator (P) is not particularly limited. However, from the viewpoint of suppressing acid diffusion and improving resolution, it is preferable that the acid produced by the photoacid generator (P) has a stronger interaction with the resin (A). From this perspective, when the acid produced by the photoacid generator (P) is an organic acid, it is preferable that it also has polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonyl sulfonyl imide groups, disulfonyl imide groups, and trisulfonyl methyl acid groups.

[0358] Examples of polar groups include ether, ester, amide, acyl, sulfonyl, sulfonyloxy, sulfonamide, thioether, thioester, urea, carbonate, carbamate, hydroxyl, and mercapto.

[0359] There is no particular limitation on the number of polar groups in the generated acid, but it is preferable to have one or more, more preferably two or more. However, from the viewpoint of suppressing excessive development, it is preferable to have fewer than six polar groups, more preferably fewer than four.

[0360] From the viewpoint of achieving better results, the photoacid generator (P) is preferably a photoacid generator composed of an anionic portion and a cationic portion.

[0361] As a photoacid-generating agent (P), the photoacid-generating agent described in paragraphs 0144 to 0173 of Japanese Patent Application Publication No. 2019-045864 can be cited as an example.

[0362] Furthermore, as a preferred method for photoacid-generating agent (P), compounds represented by the following general formulas (ZI), (ZII) and (ZIII) can be cited as examples.

[0363] [Chemical Formula 16]

[0364]

[0365] In the above general formula (ZI),

[0366] R 201 R 202 and R 203 Each organic group can be represented independently.

[0367] As R 201 R 202 and R 203 The number of carbon atoms in the organic groups is generally 1 to 30, preferably 1 to 20.

[0368] 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 include alkylene groups (e.g., butylene, pentylene) and -CH2-CH2-O-CH2-CH2-.

[0369] Z - It represents anion.

[0370] As preferred embodiments of the cation in the general formula (ZI), examples include the corresponding groups in the compounds (ZI-1), (ZI-2), (ZI-3), and (ZI-4) described later.

[0371] 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 a structure in which at least one of the following is bonded by a single bond or a linking group.

[0372] First, the compound (ZI-1) will be described.

[0373] 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.

[0374] 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.

[0375] Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

[0376] The aryl group 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, nitrogen atom, or 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.

[0377] 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.

[0378] 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.

[0379] Next, compound (ZI-2) will be described.

[0380] 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 an aromatic ring containing a heteroatom.

[0381] 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.

[0382] 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.

[0383] As R 201 ~R 203 Alkyl and cycloalkyl groups, preferably straight-chain alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl and pentyl) and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0384] 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.

[0385] Next, compound (ZI-3) will be described.

[0386] Compound (ZI-3) is a compound represented by the following general formula (ZI-3) and is a compound having a benzoylmethylsulfonium salt structure.

[0387] [Chemical Formula 17]

[0388]

[0389] In the above general formula (ZI-3), R1 represents an alkyl, cycloalkyl, alkoxy, cycloalkoxy, aryl, or alkenyl group. R2 and R3 independently represent a hydrogen atom, alkyl, cycloalkyl, alkoxy, cycloalkoxy, or aryl group, respectively. R2 and R3 can be linked together to form a ring. R1 and R2 can be bonded together to form a ring. X and R y Each of these can be independently represented as alkyl, cycloalkyl, alkenyl, aryl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, or alkoxycarbonylcycloalkyl. R X With R yThey can connect to each other to form a ring, and this ring structure can contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds. - It represents anion.

[0390] The alkyl group used as R1 is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0391] Alkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0392] The cycloalkyl group used as R1 is not particularly limited and can be monocyclic or polycyclic. It is preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0393] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0394] Cycloalkyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0395] There is no particular limitation on the alkoxy group as R1, but it is preferably an alkoxy group with 1 to 20 carbon atoms, more preferably an alkoxy group with 1 to 15 carbon atoms, and even more preferably an alkoxy group with 1 to 10 carbon atoms.

[0396] The alkoxy group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0397] There is no particular limitation on the cycloalkoxy group as R1, but it is preferably a cycloalkoxy group with 3 to 20 carbon atoms, more preferably a cycloalkoxy group with 3 to 15 carbon atoms, and even more preferably a cycloalkoxy group with 3 to 10 carbon atoms.

[0398] Cycloalkoxy groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0399] There is no particular limitation on the aryl group as R1. It can be monocyclic or polycyclic, preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0400] The aryl group may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited, with alkoxy groups being preferred.

[0401] There is no particular limitation on the alkenyl group as R1, but it is preferably an alkenyl group with 1 to 20 carbon atoms, more preferably an alkenyl group with 1 to 15 carbon atoms, and even more preferably an alkenyl group with 1 to 10 carbon atoms.

[0402] Alkenes can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0403] R1 is preferably aryl.

[0404] The alkyl group used as R2 and R3 is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0405] Alkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0406] There is no particular limitation on the cycloalkyl group used as R2 and R3. It can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0407] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0408] Cycloalkyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0409] There are no particular limitations on the aryl group used as R2 and R3. It can be monocyclic or polycyclic, preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0410] Aryl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0411] There is no particular limitation on the alkoxy group used as R2 and R3, but it is preferably an alkoxy group with 1 to 20 carbon atoms, more preferably an alkoxy group with 1 to 15 carbon atoms, and even more preferably an alkoxy group with 1 to 10 carbon atoms.

[0412] The alkoxy group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0413] There is no particular limitation on the cycloalkoxy group used as R2 and R3, but it is preferably a cycloalkoxy group with 3 to 20 carbon atoms, more preferably a cycloalkoxy group with 3 to 15 carbon atoms, and even more preferably a cycloalkoxy group with 3 to 10 carbon atoms.

[0414] Cycloalkoxy groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0415] R2 and R3 are each preferably hydrogen atoms, alkyl groups, cycloalkyl groups or alkoxy groups, more preferably hydrogen atoms or alkyl groups.

[0416] R2 and R3 can be connected to each other to form a ring. As a ring structure, for example, 3 to 10-membered rings can be used, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0417] Furthermore, R1 and R2 can be connected to each other to form a ring. As a ring structure, 3 to 10-membered rings can be used, preferably 4 to 8-membered rings, and more preferably 5 or 6-membered rings.

[0418] As R X and R y The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0419] Alkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0420] As R X and R y The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0421] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0422] Cycloalkyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0423] As R X and R y The alkenyl group is not particularly limited, but is preferably an alkenyl group with 1 to 20 carbon atoms, more preferably an alkenyl group with 1 to 15 carbon atoms, and even more preferably an alkenyl group with 1 to 10 carbon atoms.

[0424] Alkenes can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0425] As R X and R yThe aryl group is not particularly limited and can be monocyclic or polycyclic. It is preferably an aryl group with 6 to 20 carbon atoms, more preferably an aryl group with 6 to 15 carbon atoms, and even more preferably an aryl group with 6 to 10 carbon atoms.

[0426] Aryl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0427] As R X and R y The 2-oxoalkyl group is not particularly limited, but is preferably a 2-oxoalkyl group with 1 to 20 carbon atoms, more preferably a 2-oxoalkyl group with 1 to 15 carbon atoms, and even more preferably a 2-oxoalkyl group with 1 to 10 carbon atoms.

[0428] 2-Oxoalkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0429] As R X and R y The 2-oxocycloalkyl group is not particularly limited, but is preferably a 2-oxocycloalkyl group with 3 to 20 carbon atoms, more preferably a 2-oxocycloalkyl group with 3 to 15 carbon atoms, and even more preferably a 2-oxocycloalkyl group with 3 to 10 carbon atoms.

[0430] 2-Oxocycloalkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0431] As R X and R y The alkoxycarbonyl alkyl group is not particularly limited, but is preferably an alkoxycarbonyl alkyl group with 3 to 22 carbon atoms, more preferably an alkoxycarbonyl alkyl group with 3 to 17 carbon atoms, and even more preferably an alkoxycarbonyl alkyl group with 3 to 12 carbon atoms.

[0432] The alkoxycarbonyl alkyl group may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0433] As R X and R y The alkoxycarbonylcycloalkyl group is not particularly limited, but is preferably an alkoxycarbonylcycloalkyl group with 5 to 24 carbon atoms, more preferably an alkoxycarbonylcycloalkyl group with 5 to 19 carbon atoms, and even more preferably an alkoxycarbonylcycloalkyl group with 5 to 14 carbon atoms.

[0434] Alkoxycarbonylcycloalkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0435] R X With R yThey can connect with each other to form a ring, and the ring structure can contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds.

[0436] The above-mentioned ring structure preferably contains oxygen atoms.

[0437] 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.

[0438] Next, compound (ZI-4) will be described.

[0439] Compound (ZI-4) is a compound represented by the following general formula (ZI-4).

[0440] [Chemical Formula 18]

[0441]

[0442] In general formula (ZI-4),

[0443] l represents an integer from 0 to 2.

[0444] r represents an integer from 0 to 8.

[0445] R 13 It represents a hydrogen atom, fluorine atom, hydroxyl group, alkyl group, cycloalkyl group, alkoxy group, or alkoxycarbonyl group.

[0446] R 14 This indicates hydroxyl, alkyl, cycloalkyl, alkoxy, alkoxycarbonyl, alkylcarbonyl, alkylsulfonyl, or cycloalkylsulfonyl. When multiple R groups are present... 14 At that time, multiple R 14 They can be the same as or different from each other.

[0447] R 15 Each can be independently represented by an alkyl, cycloalkyl, or naphthyl group. Two Rs 15 They can bond together to form a ring. When two Rs 15 When they bond together to form a ring, the ring structure can contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds.

[0448] X - It represents anion.

[0449] As R 13 The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0450] Alkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0451] As R 13 The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0452] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0453] Cycloalkyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0454] As R 13 The alkoxy group is not particularly limited, but is preferably an alkoxy group with 1 to 20 carbon atoms, more preferably an alkoxy group with 1 to 15 carbon atoms, and even more preferably an alkoxy group with 1 to 10 carbon atoms.

[0455] The alkoxy group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0456] As R 13 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group with 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group with 2 to 16 carbon atoms, and even more preferably an alkoxycarbonyl group with 2 to 11 carbon atoms.

[0457] The alkoxycarbonyl group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0458] As R 14 The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0459] Alkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0460] As R 14 The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0461] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0462] Cycloalkyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0463] As R 14 The alkoxy group is not particularly limited, but is preferably an alkoxy group with 1 to 20 carbon atoms, more preferably an alkoxy group with 1 to 15 carbon atoms, and even more preferably an alkoxy group with 1 to 10 carbon atoms.

[0464] The alkoxy group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0465] As R 14 The alkoxycarbonyl group is not particularly limited, but is preferably an alkoxycarbonyl group with 2 to 21 carbon atoms, more preferably an alkoxycarbonyl group with 2 to 16 carbon atoms, and even more preferably an alkoxycarbonyl group with 2 to 11 carbon atoms.

[0466] The alkoxycarbonyl group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0467] As R 14 The alkyl carbonyl group is not particularly limited, but is preferably an alkyl carbonyl group with 2 to 21 carbon atoms, more preferably an alkyl carbonyl group with 2 to 16 carbon atoms, and even more preferably an alkyl carbonyl group with 2 to 11 carbon atoms.

[0468] Alkyl carbonyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0469] As R 14 The alkyl sulfonyl group is not particularly limited, but is preferably an alkyl sulfonyl group with 1 to 20 carbon atoms, more preferably an alkyl sulfonyl group with 1 to 15 carbon atoms, and even more preferably an alkyl sulfonyl group with 1 to 10 carbon atoms.

[0470] The alkyl sulfonyl group may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0471] As R 14 The cycloalkylsulfonyl group is not particularly limited, but is preferably a cycloalkylsulfonyl group with 3 to 20 carbon atoms, more preferably a cycloalkylsulfonyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkylsulfonyl group with 3 to 10 carbon atoms.

[0472] The cycloalkylsulfonyl group may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0473] When there are multiple R 14 At that time, multiple R 14 They can be the same as or different from each other.

[0474] As R 15 The alkyl group is not particularly limited and can be straight-chain or branched. It is preferably an alkyl group with 1 to 20 carbon atoms, more preferably an alkyl group with 1 to 15 carbon atoms, and even more preferably an alkyl group with 1 to 10 carbon atoms.

[0475] Alkyl groups may have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0476] As R 15 The cycloalkyl group is not particularly limited and can be monocyclic or polycyclic, preferably a cycloalkyl group with 3 to 20 carbon atoms, more preferably a cycloalkyl group with 3 to 15 carbon atoms, and even more preferably a cycloalkyl group with 3 to 10 carbon atoms.

[0477] Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, and decahydronaphthyl.

[0478] Cycloalkyl groups can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0479] As R 15 The naphthyl group can have substituents. There are no particular limitations on the substituents; for example, the substituent T mentioned above can be cited.

[0480] 2 Rs 15 They can bond together to form a ring. When two Rs 15 When they bond together to form a ring, the ring structure can contain oxygen atoms, nitrogen atoms, sulfur atoms, ketone groups, ether bonds, ester bonds, and amide bonds.

[0481] The above-mentioned ring structure preferably contains oxygen atoms.

[0482] 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.

[0483] In one preferred embodiment, two Rs are preferred. 15 They are alkylene groups and bonded together to form a ring structure.

[0484] Next, general formulas (ZII) and (ZIII) will be explained.

[0485] In general formulas (ZII) and (ZIII), R 204 ~R 207 Each can be represented independently as aryl, alkyl, or cycloalkyl.

[0486] As R 204 ~R 207The aryl group is preferably phenyl or naphthyl, more preferably phenyl. 204 ~R 207 It can be an aryl group containing a heterocyclic structure with oxygen, nitrogen, or sulfur atoms. Examples of aryl groups with heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

[0487] As R 204 ~R 207 Alkyl and cycloalkyl groups, for example, include 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), and cycloalkyl groups with 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl and norbornyl).

[0488] R 204 ~R 207 The aryl, alkyl, and cycloalkyl groups can each independently have substituents. As R 204 ~R 207 The aryl, alkyl, and cycloalkyl groups may have substituents, for example, alkyl (e.g., having 1 to 15 carbon atoms), cycloalkyl (e.g., having 3 to 15 carbon atoms), aryl (e.g., having 6 to 15 carbon atoms), alkoxy (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.

[0489] Z - It represents anion.

[0490] The above-mentioned (P) photoacid generator preferably contains a compound represented by the above general formula (ZI-3) or a compound represented by the above general formula (ZI-4).

[0491] By using this compound, the transparency of the resist film is improved, thus enabling superior resolution, especially when exposed to ArF light.

[0492] Z in the general formula (ZI) - Z in general formula (ZII) - Z in the above general formula (ZI-3) - and X in the above general formula (ZI-4) - There are no specific limitations; for example, the non-nucleophilic anion Z described in paragraphs 0144 to 0173 of Japanese Patent Application Publication No. 2019-045864 can be cited. - .

[0493] Preferred examples of sulfonium cations in general formula (ZI) and iodonium cations in general formula (ZII) are shown below.

[0494] [Chemical Formula 19]

[0495]

[0496] [Chemical Formula 20]

[0497]

[0498] [Chemical Formula 21]

[0499]

[0500] The following shows the anion Z in general formulas (ZI) and (ZII). - Z in general formula (ZI-3) - and X in general formula (ZI-4) - A preferred example.

[0501] [Chemical Formula 22]

[0502]

[0503] [Chemical Formula 23]

[0504]

[0505] The above-mentioned cations and anions can be combined in any way to use as photoacid generators. Furthermore, the following photoacid generators are also preferred: Bu represents butyl.

[0506] [Chemical Formula 24]

[0507]

[0508] [Chemical Formula 25]

[0509]

[0510] [Chemical Formula 26]

[0511]

[0512] The content of photoacid generator (P) is not particularly limited, but from the viewpoint of better effect of the present invention, it is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.1 to 3% by mass, relative to the total solid content of the composition.

[0513] Photoacid generator (P) can be used alone or in combination with two or more. When two or more photoacid generators (P) are used in combination, it is preferable that their total dosage is within the above-mentioned range.

[0514] <Acid Diffusion Control Agent (Q)>

[0515] The compositions of the present invention may contain an acid diffusion control agent (Q).

[0516] Acid diffusion control agent (Q) captures acid generated from photoacid generators (P) during exposure and functions as a quencher, inhibiting the reaction of acid-degrading resin in the unexposed portion caused by excessive acid generation. Examples of acid diffusion control agents (Q) include basic compounds (DA), basic compounds (DB) whose basicity is reduced or eliminated by irradiation with photochemical rays or radiation, onium salts (DC) that are relatively weak acids relative to photoacid generators (P), 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.

[0517] In the compositions of the present invention, known acid diffusion control agents may be suitably used. For example, compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458 may be used as acid diffusion control agents (Q).

[0518] 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.

[0519] In the compositions of the present invention, an onium salt (DC) that is a relatively weak acid relative to the photoacid generator (P) can be used as an acid diffusion control agent (Q).

[0520] When a photoacid generator (P) is mixed with an onium salt that produces an acid that is relatively weaker than the acid produced by the photoacid generator (P), if the acid produced by the photoacid generator (P) collides with the unreacted onium salt containing a weak acid anion after irradiation by photochemical rays or radiation, the weak acid is released and an onium salt containing a strong acid anion is produced through salt exchange. 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.

[0521] As a type of onium salt that is relatively weak compared to photoacid-producing agent (P), the onium salt described in paragraphs 0226 to 0233 of Japanese Patent Application Publication No. 2019-070676 can be cited as an example.

[0522] When the composition of the present invention contains an acid diffusion control agent (Q), the content of the acid diffusion control agent (Q) (total if multiple agents are present) relative to the total solid content of the composition is preferably 0.001 to 1% by mass, more preferably 0.01 to 0.10% by mass.

[0523] In the compositions of the present invention, the acid diffusion control agent (Q) may be used alone or in combination with two or more.

[0524] <Hydrophobic Resin (E)>

[0525] The composition of the present invention may contain a hydrophobic resin different from the above-described resin (A) as a hydrophobic resin (E).

[0526] The hydrophobic resin (E) is preferably designed to be biased toward the surface of the resist film, but unlike surfactants, it does not necessarily need to have hydrophilic groups in the molecule, and it may not contribute to the uniform mixing of polar and nonpolar substances.

[0527] As an example of the effects of adding hydrophobic resin (E), the static and dynamic contact angle of the resist film surface with respect to water can be controlled, as well as the suppression of outgassing.

[0528] From the viewpoint of favoring the surface layer of the membrane, the hydrophobic resin (E) preferably has one or more of the following: "fluorine atom", "silicon atom", and "CH3 moiety contained in the side chain portion of the resin", more preferably two or more. Furthermore, the hydrophobic resin (E) preferably has a hydrocarbon group having five or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted by the side chain.

[0529] When the hydrophobic resin (E) contains fluorine atoms and / or silicon atoms, the aforementioned fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[0530] When the hydrophobic resin (E) has fluorine atoms, the preferred partial structure having fluorine atoms is an alkyl group having fluorine atoms, a cycloalkyl group having fluorine atoms, or an aryl group having fluorine atoms.

[0531] The alkyl group having fluorine atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a straight-chain or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may also have substituents other than fluorine atoms.

[0532] A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may also have substituents other than a fluorine atom.

[0533] As an aryl group having a fluorine atom, examples include aryl groups such as phenyl and naphthyl in which at least one hydrogen atom is replaced by a fluorine atom, and it can also have substituents other than a fluorine atom.

[0534] As an example of a repeating unit having fluorine or silicon atoms, the repeating unit illustrated in paragraph 0519 of US2012 / 0251948 can be cited.

[0535] Furthermore, as described above, the hydrophobic resin (E) preferably has a CH3 moiety in the side chain portion.

[0536] Here, the CH3 moiety structure of the side chain portion in the hydrophobic resin includes CH3 moiety structures containing ethyl and propyl groups, etc.

[0537] On the other hand, the methyl groups (e.g., α-methyl groups having repeating units of methacrylic acid structure) directly bonded to the main chain of the hydrophobic resin (E) contribute little to the surface bias of the hydrophobic resin (E) due to the influence of the main chain, and are therefore not included in the CH3 part structure in this invention.

[0538] Regarding the hydrophobic resin (E), please refer to the description in paragraphs

[0348] to

[0415] of Japanese Patent Application Publication No. 2014-010245, which is incorporated into this specification.

[0539] In addition, the resins described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859 and Japanese Patent Application Publication No. 2012-032544 may preferably be used as the hydrophobic resin (E).

[0540] When the composition of the present invention contains a hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the composition.

[0541] <Solvent(F)>

[0542] The solvent (also referred to as "solvent (F)") is described.

[0543] The solvent (F) preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylate and (M2), wherein (M2) is selected from at least one of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone and alkylene carbonate. The solvent may also contain components other than (M1) and (M2).

[0544] 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.

[0545] Furthermore, examples of organic solvents (F) include alkylene glycol monoalkyl ether carboxylic esters, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionate esters, cyclic lactones (preferably with 4 to 10 carbon atoms), monoketone compounds that may contain rings (preferably with 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetic acid esters, and alkyl pyruvate esters.

[0546] The solvent (F) content in the composition of the present invention is preferably adjusted such that the solid component concentration of the above composition is 0.5 to 50% by mass, more preferably 3 to 45% by mass.

[0547] From the viewpoint of achieving better results in this invention, the concentration of the solid component is preferably 20% by mass or more.

[0548] Therefore, it is preferable to adjust the amount of solvent (F) added to the stirring tank in step 1 so that the solid content concentration of the photosensitive radioactive or radioactive linear resin composition manufactured by the manufacturing method of the present invention is within the aforementioned range. Furthermore, solid content concentration refers to the mass percentage of the mass of components other than the solvent (components that may constitute the photosensitive radioactive or radioactive linear film) relative to the total mass of the photosensitive radioactive or radioactive linear resin composition.

[0549] <surfactant (H)>

[0550] The compositions of the present invention may contain a surfactant (H). By containing a surfactant (H), it is possible to form patterns with better adhesion and fewer development defects.

[0551] The surfactant (H) is preferably a fluorinated and / or silicone surfactant.

[0552] 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.

[0553] Furthermore, in addition to the known surfactants described above, the surfactant (H) can also be synthesized using fluorinated aliphatic compounds manufactured by telomerization (also known as 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 (H). This fluorinated aliphatic compound can be synthesized by, for example, the method described in Japanese Patent Application Publication No. 2002-90991.

[0554] As a polymer having fluorinated aliphatic groups, copolymers of monomers having fluorinated aliphatic groups with (poly(oxyalkylene)) acrylates and / or (poly(oxyalkylene)) methacrylates are preferred. These copolymers can be irregularly distributed or block copolymers. Furthermore, examples of poly(oxyalkylene) groups include poly(oxyethylene) groups, poly(oxypropylene) groups, and poly(oxybutene) groups. They can also be alkylene 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). In addition, copolymers of monomers having fluorinated aliphatic groups with (poly(oxyalkylene)) acrylates (or methacrylates) are not only binary copolymers but can also be ternary or higher copolymers formed by simultaneously copolymerizing monomers having two or more different fluorinated aliphatic groups with two or more different (poly(oxyalkylene)) acrylates (or methacrylates).

[0555] 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).

[0556] 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.

[0557] These surfactants (H) can be used alone or in combination of two or more.

[0558] The content of surfactant (H) relative to the total solids content of the composition is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass.

[0559] <Other Additives>

[0560] The compositions of the present invention may further contain crosslinking agents, alkali-soluble resins, dissolution-inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and / or compounds that promote solubility in the developing solution.

[0561] [Pattern Formation Method]

[0562] The photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention described above can be used, for example, for pattern formation in the manufacturing process of semiconductor devices.

[0563] Typically, the photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention is a photoresist composition (preferably a chemically amplified photoresist composition), which can be a positive photoresist composition or a negative photoresist composition. Furthermore, the photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention can be a photoresist composition for alkaline development or a photoresist composition for organic solvent development.

[0564] There are no particular limitations on the patterning method using the photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention, but the following steps are preferred.

[0565] Step A: The step of forming a resist film on a substrate using a photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention.

[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 following is a detailed description of each of the above processes.

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

[0570] Step A is the process of forming a resist film on a substrate using a photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention.

[0571] The manufacturing method and composition of the present invention are described above.

[0572] As a method for forming a resist film on a substrate using a photosensitive radioactive or radiosensitive linear resin composition manufactured by the manufacturing method of the present invention, an example is a method of coating the composition onto the substrate.

[0573] Furthermore, it is preferable to filter the 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.

[0574] The composition can be applied to substrates (e.g., silicon, silicon dioxide coating) used in the manufacture of integrated circuit components by 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.

[0575] The resist film can be formed by drying the substrate after coating the composition. In addition, various substrate films (inorganic films, organic films, or anti-reflective films) can be formed under the resist film as needed.

[0576] 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.

[0577] The heating temperature is preferably 80-150℃, more preferably 80-140℃.

[0578] The heating time is preferably 30 to 1000 seconds, more preferably 40 to 800 seconds.

[0579] The thickness of the resist film is not particularly limited, but in the case of resist film for KrF exposure, it is preferably 3 to 20 μm, and more preferably 5 to 18 μm.

[0580] Furthermore, in the case of resist films for ArF exposure or EUV exposure, the wavelength is preferably 30 to 700 nm, and more preferably 40 to 400 nm.

[0581] Alternatively, a topcoat composition can be used to form a topcoat layer on top of the resist film.

[0582] 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.

[0583] The thickness of the top coating is preferably 10–200 nm, more preferably 20–100 nm.

[0584] There are no particular limitations on the top coating. A conventionally known top coating can be formed by 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.

[0585] (Process B: Exposure Process)

[0586] Process B is the process of exposing the resist film.

[0587] As a method of exposure, one example is to irradiate the formed resist film with photochemical rays or radiation through a prescribed mask.

[0588] Examples of photochemical rays or 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 even more 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.

[0589] It is preferable to bake after exposure and before development (post-exposure baking: PEB).

[0590] The heating temperature is preferably 80-150℃, more preferably 80-140℃.

[0591] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds.

[0592] Heating can be achieved using devices found in general exposure machines and / or developing machines, or by using hot plates or the like.

[0593] This process is also described as baking after exposure.

[0594] (Process C: Development Process)

[0595] Process C is the process of developing the exposed resist film with a developer to form a pattern.

[0596] Examples of development methods include: immersing the substrate in a tank filled with developer for a certain time (dip method); using surface tension to accumulate developer on the substrate surface and allowing it to stand for a certain time for development (puddle method); spraying developer onto the substrate surface (spray method); and continuously spraying developer onto a substrate rotating at a constant speed while scanning the developer nozzle at a constant speed (dynamic dispense method).

[0597] Furthermore, after the developing process, a process can be implemented where the developing process is stopped while replacing the solvent with another solvent.

[0598] 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; preferably, it is 10 to 300 seconds, and more preferably 20 to 120 seconds.

[0599] The temperature of the developer is preferably 0–50°C, and more preferably 15–35°C.

[0600] Examples of developing solutions include alkaline developing solutions and organic solvent developing solutions.

[0601] 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 10.0–15.0.

[0602] Organic solvent developer (also known as organic developer) is a developer containing organic solvents.

[0603] 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.

[0604] (Other processes)

[0605] The above-mentioned pattern forming method preferably includes a cleaning step using a rinsing solution after step C.

[0606] As a rinsing solution used in the rinsing process after the development process using an alkaline developer, pure water can be cited as an example. Additionally, an appropriate amount of surfactant can be added to the pure water.

[0607] An appropriate amount of surfactant can be added to the rinsing solution.

[0608] In the rinsing process following the developing step using an organic developer, there are no particular restrictions on the rinsing solution used, as long as it does not dissolve the resist pattern; solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. Additionally, an appropriate amount of surfactant may be added to the rinsing solution.

[0609] 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).

[0610] There are no particular limitations 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).

[0611] 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.

[0612] 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.

[0613] Among these methods, oxygen plasma etching is preferred as a dry etching process.

[0614] The various materials used in the manufacturing method and composition of the present invention (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.

[0615] 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.

[0616] 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.

[0617] As a filter, a filter that reduces the amount of dissolved substances, as disclosed in Japanese Patent Application Publication No. 2016-201426, is preferred.

[0618] 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 for metal adsorbents, examples include those disclosed in Japanese Patent Application Publication No. 2016-206500.

[0619] 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.

[0620] 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.

[0621] Various materials can be used after being diluted with the solvents used in the composition.

[0622] Furthermore, the present invention relates to a method for manufacturing an electronic device including the above-described pattern forming method, and to an electronic device manufactured by the same method.

[0623] The electronic device of the present invention is an electronic device that is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[0624] Example

[0625] 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 is not to be interpreted as limited by the embodiments shown below.

[0626] Synthesis of Resin (A)

[0627] In the examples and comparative examples, the following resin was used as resin (A). All of the following resins were synthesized according to known techniques.

[0628] Table 1 shows the composition ratio (molar ratio; corresponding from left to right), weight-average molecular weight (CMw), and dispersion (Mw / Mn) of each repeating unit in resin (A).

[0629] Furthermore, the weight-average molecular weight (Mw) and dispersity (Mw / Mn) of the resin are converted values ​​of polystyrene determined by the aforementioned GPC method (charge carrier: tetrahydrofuran (THF)). And, through... 13 C-NMR (nuclear magnetic resonance) was used to determine the composition ratio (molar percentage) of repeating units in the resin.

[0630] [Table 1]

[0631]

[0632] [Chemical Formula 27]

[0633]

[0634] <Photo-acid generator>

[0635] The following shows the structures of the compounds used as photoacid generators in the examples and comparative examples.

[0636] [Chemical Formula 28]

[0637]

[0638] <Acid Diffusion Control Agent (Q)>

[0639] The structures of the compounds used as acid diffusion control agents in the examples and comparative examples are shown below.

[0640] [Chemical Formula 29]

[0641]

[0642] Solvent

[0643] The solvents used in the examples and comparative examples are shown below.

[0644] PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0645] PGME: Propylene Glycol Monomethyl Ether

[0646] EL: Ethyl lactate

[0647] <surfactant (H)>

[0648] The following shows the surfactants used in the examples and comparative examples.

[0649] WA: Megaface R-41 (manufactured by DIC Corporation)

[0650] Additive (X)

[0651] The following shows the additives used in the examples and comparative examples.

[0652] [Chemical Formula 30]

[0653]

[0654] Examples 1-21 and Comparative Examples 1-2

[0655] <Preparation of photosensitive or radiosensitive linear resin compositions>

[0656] according to Figure 1 The manufacturing apparatus 100 shown manufactures a resist composition as follows.

[0657] (Process 1)

[0658] The resist composition is prepared in a stirred tank (capacity 200L) in a clean room (National Standard ISO 14644-1, Level 5, room temperature (23°C), atmospheric pressure (101325Pa)) in a manner that constitutes the resist composition described in Table 2. Figure 1 Each component is added to the mixing tank 10).

[0659] After the various components are added, the porosity (the proportion of space (void)) in the mixing tank is 20% by volume. In other words, the occupancy rate of the mixture in the mixing tank is 80% by volume. Additionally, in step 1, the stirring shaft (equivalent to...) Figure 1 The stirring shaft 12) does not rotate.

[0660] (Process 2)

[0661] Next, the mixing tank equipped with stirring blades (equivalent to...) is placed inside the mixing tank. Figure 1 The stirring shaft of the stirring tank 14) (equivalent to Figure 1 The stirring shaft 12) rotates at the stirring speed recorded in Table 2 to mix the components and perform step 2.

[0662] Simultaneously with the start of stirring, in Examples 1-21 and Comparative Example 1, the mixture is subjected to a temperature control device (equivalent to...) Figure 1The temperature control device 24) is adjusted to allow nitrogen gas to be introduced into the mixing tank at the temperature specified in Table 2. The liquid temperature at the start of step 2 (initial mixing temperature) is as specified in Table 2. In Comparative Example 2, atmospheric air is introduced into the mixing tank at the temperature specified in Table 2.

[0663] In Examples 1-20 and Comparative Example 1, the first-stage flow rate of nitrogen gas, as recorded in Table 2, was set and introduced into the stirred tank. If it was confirmed that the temperature in the stirred tank reached the upper temperature limit width recorded in Table 2, the flow rate of nitrogen gas was immediately changed to the second-stage flow rate to lower the liquid temperature.

[0664] Once the liquid temperature has decreased to the initial temperature recorded in Table 2, the nitrogen flow rate is changed back to the first-stage flow rate. The time taken to decrease to the initial temperature at this point is shown in Table 2.

[0665] This process of repeating the first and second stage flow rates continued until the mixing ended 8 hours after the start of mixing.

[0666] During the implementation of step 2 above, nitrogen gas is continuously introduced at a temperature adjusted to allow it to pass through the mixing tank.

[0667] In Example 21, the first-stage flow rate of nitrogen gas recorded in Table 2 was set and introduced into the stirring tank without changing the flow rate. The stirring was stopped 8 hours after the start of stirring.

[0668] For Example 21, the upper temperature limit width recorded in Table 2 represents the value at which the temperature rises the most from the initial stirring temperature during the stirring time.

[0669] Throughout step 2, the temperature of the liquid in the mixing tank is measured using a temperature sensor (equivalent to...). Figure 1 The temperature sensor 20 (HAYASHIDENKO CO., LTD., digital temperature sensor) is used.

[0670] In step 2, the flow rates of nitrogen and atmospheric gas are measured and adjusted via a flow control device (equivalent to...). Figure 1 The flow control device 26 (KEYENCE CORPORATION) is used to measure the flow rate of a gas flow sensor with an amplifier separation.

[0671] After stirring, the mixture (solution) obtained in step 2 is passed through a polyethylene filter with a pore size of 3 μm to produce a photosensitive or radiosensitive linear resin composition (resist composition).

[0672] The viscosity of the resist composition is shown in Table 2.

[0673] The viscosity of the manufactured resist composition is 10 mPa·s or higher. The viscosity was measured at 25.0°C using a viscometer (RE-85L) manufactured by TOKISANGYO.

[0674] In Table 2, the “content” column for each component indicates the content (mass%) of each component relative to the total solid content in the resist composition.

[0675] In Table 2, the values ​​in the "Solvent" column represent the mass ratio of each solvent.

[0676] The total solids concentration (mass%) in the resist composition is shown in Table 2.

[0677]

[0678] [Evaluation of in-plane uniformity]

[0679] Using an ACT-8 spin coater manufactured by Tokyo Electron Ltd., the above-prepared resist composition was coated onto a Si substrate (manufactured by Advanced Materials Technology) that had undergone hexamethyldisilazane treatment, without an anti-reflective layer. The substrate was then heated and dried at 130°C for 60 seconds to form a resist film with a thickness corresponding to the resist compositions shown in Table 2.

[0680] Using a SCREEN VM-3110, film thickness was measured at 300 points concentrically from the center of the Si substrate. The 3σ (nm) of these values ​​was taken as an indicator of in-plane uniformity. The smaller the 3σ, the better the in-plane uniformity.

[0681] The evaluation results are shown in Table 2.

[0682] As shown in Table 2, compared with the resist compositions manufactured by Comparative Examples 1 to 2, the resist compositions of Examples 1 to 21 manufactured according to the manufacturing method of the present invention showed extremely excellent in-plane uniformity of film thickness, especially in the case of forming a thick resist film.

[0683] Patterning was performed on the resist composition prepared by Example 1 by the following method.

[0684] <Pattern Formation>

[0685] Using an ACT-8 spin coater manufactured by Tokyo Electron Ltd., a resist composition was coated onto a Si substrate (manufactured by Advanced Materials Technology) treated with hexamethyldisilazane without an anti-reflective layer. The coating was then heated and dried at 130°C for 60 seconds to form a 10 μm thick resist film. This resist film was then patterned using a KrF excimer laser scanner (ASML, PAS5500 / 850C, wavelength 248 nm) through a mask at the optimal exposure conditions of NA (numerical aperture) = 0.68 and σ = 0.60. After irradiation, the film was baked at 130°C for 60 seconds, immersed in a 2.38% (w / w) tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and then dried.

[0686] Exposure is performed using a mask with a linear and spatial pattern. The resulting spatial pattern after reduced projection exposure is 3 μm in size and 33 μm in spacing. The exposure value with the resulting spatial pattern of 3 μm and spacing of 33 μm is taken as the optimal exposure value (sensitivity) (mJ / cm²). 2 The spatial pattern width was measured using a scanning electron microscope (SEM) (Hitachi, Ltd. 9380I).

[0687] Through the above steps, an evaluation patterned wafer having a substrate and a pattern (resist pattern) formed on the surface of the substrate is obtained.

[0688] One inch is 25.4 millimeters.

[0689] Industrial availability

[0690] According to the present invention, a method for manufacturing a photosensitive radioactive or radioactive linear resin composition, which can form a photosensitive radioactive or radioactive linear resin film with extremely excellent in-plane uniformity of film thickness, especially when forming a thick film (e.g., 1 μm or more), a pattern forming method using the above-described method for manufacturing the photosensitive radioactive or radioactive linear resin composition, and a method for manufacturing an electronic device are provided.

[0691] The present invention has been described in detail with reference to specific embodiments, but various changes or modifications can be made without departing from the spirit and scope of the invention, which will be apparent to those skilled in the art.

[0692] In addition, the contents of this application are incorporated herein by reference based on Japanese patent application filed on August 28, 2020 (Japanese Patent Application 2020-145081).

[0693] Symbol Explanation

[0694] 10-Stirring tank, 12-Stirring shaft, 14-Stirring blade, 16-Gas inlet, 18-Gas outlet, 20-Temperature sensor, 22-Tank, 24-Gas temperature control device, 26-Flow control device, 100-Manufacturing device.

Claims

1. A method for manufacturing a photosensitive radioactive or radiosensitive linear resin composition, wherein the photosensitive radioactive or radiosensitive linear resin composition has a viscosity of 10 mPa·s or higher, comprising: Step 1 involves adding, as raw materials, at least the resin whose polarity increases due to the action of acid, a photoacid generator, and a solvent into a mixing tank; and Step 2: Stir the raw materials in the mixing tank. Throughout step 2, the liquid temperature in the stirring tank is controlled to be at least 1.0°C lower than the initial liquid temperature at the beginning of step 2 and at least 3.0°C higher than the initial liquid temperature at the beginning of step 2. The temperature of the liquid in the stirring tank in step 2 is controlled by passing an inactive gas through the stirring tank.

2. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1, wherein, The temperature of the inactive gas used to pass through the stirring tank is 15℃~20℃.

3. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The stirring in step 2 is carried out by a stirring shaft with stirring blades, and the stirring shaft rotates at a speed of 50 rpm to 400 rpm.

4. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, Throughout step 2, the liquid temperature in the stirring tank is controlled to be at least 1.0°C lower than the initial liquid temperature at the beginning of step 2 and at least 2.0°C higher than the initial liquid temperature at the beginning of step 2.

5. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The viscosity of the photosensitive radioactive or radiosensitive linear resin composition is 100 mPa·s or higher.

6. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The stirring in step 2 is carried out by a stirring shaft with stirring blades. When the viscosity of the photosensitive radioactive or radiosensitive linear resin composition is set as X, in step 2, Y < 40 × Ln(X) + 65 is satisfied, where Y represents the rotational speed of the stirring blade.

7. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The temperature of the liquid is controlled by adjusting the flow rate of the inactive gas passing through the stirring tank.

8. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The solid content concentration of the photosensitive radioactive or radiosensitive linear resin composition is 20% by mass or more.

9. The method for manufacturing the photosensitive radioactive or radiosensitive linear resin composition according to claim 1 or 2, wherein, The resin whose polarity increases through the action of acid comprises repeating units having acid-decomposable groups and repeating units represented by the following general formula (1), wherein the resin whose polarity increases through the action of acid has aromatic ring groups. In general formula (1), R1 represents a hydrogen atom, a halogen atom, or an alkyl group. R2 indicates an alkyl group having 2 or more carbon atoms.

10. A method for forming a pattern, comprising: The process of forming a resist film with a thickness of 3 μm to 20 μm on a substrate using a photosensitive radioactive or radiosensitive linear resin composition manufactured by any one of claims 1 to 9; The process of exposing a photoresist film; and The process of developing an exposed resist film using a developer to form a pattern.

11. A method for manufacturing an electronic device, comprising the pattern forming method of claim 10.

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