JP2008268850A - Pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method in which, in an immersion lithography process applying a protective film, a resist film surface is wetted with a 4-10C higher alcohol before coating with the protective film, so that the migration of resist additives to the protective film can be prevented to minimize a change in pattern profile, and the resist film surface is hydrophilized by slight surface roughing by the alcohol treatment to prevent the occurrence of blob defects and to reduce a dispense amount in coating with the protective film. <P>SOLUTION: The pattern forming method includes: a process of applying a photoresist material on a substrate; a process of wetting a formed photoresist film surface after heat treatment with a solution containing a 4-10C higher alcohol, and exposing the surface with a high energy line after coating with a protective film and heat treatment; and a process of performing development with a developer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pattern formation method in immersion photolithography in which fine processing in a manufacturing process of a semiconductor element or the like, for example, an ArF excimer laser having a wavelength of 193 nm is used as a light source, and water is inserted between a projection lens and a wafer.

  In recent years, with the higher integration and higher speed of LSIs, there is a demand for finer pattern rules. In light exposure currently used as a general-purpose technology, the intrinsic resolution limit derived from the wavelength of the light source Is approaching.

  Conventionally, light exposure using a g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source has been widely used as exposure light used in forming a resist pattern. As a means for further miniaturization, a method of shortening the exposure wavelength is effective, and a mass production process after 64 Mbit (process size is 0.25 μm or less) DRAM (Dynamic Random Access Memory). In this case, a KrF excimer laser (248 nm) having a short wavelength was used as an exposure light source instead of i-line (365 nm).

  However, in order to manufacture DRAMs with a density of 256M and 1G or more that require finer processing technology (processing dimensions of 0.2 μm or less), a light source with a shorter wavelength is required, and an ArF excimer has been used for about 10 years. Photolithography using a laser (193 nm) has been studied in earnest.

  At first, ArF lithography was supposed to be applied from the device fabrication of the 180 nm node, but KrF excimer lithography was extended to 130 nm node device mass production, and full-scale application of ArF lithography is from the 90 nm node. Further, a 65 nm node device is being studied in combination with a lens whose NA is increased to 0.9.

For the next 45 nm node device, the exposure wavelength has been shortened, and F ₂ lithography with a wavelength of 157 nm was nominated. However, the cost of the scanner is increased by using a large amount of expensive CaF ₂ single crystal for the projection lens, the optical system changes due to the introduction of the hard pellicle because the durability of the soft pellicle is extremely low, the resist film etching resistance is reduced Due to various problems, it has been proposed to advance F ₂ lithography and early introduction of ArF immersion lithography (see Non-Patent Document 1).

  In ArF immersion lithography, it has been proposed to impregnate water between the projection lens and the wafer. The refractive index of water at 193 nm is 1.44, and pattern formation is possible even with a lens having an NA of 1.0 or more, and the NA can be increased to 1.35. The resolution is improved by the improvement of NA, and the possibility of a 45 nm node is shown by the combination of a lens of NA 1.2 or higher and strong super-resolution technology (see Non-Patent Document 2).

Development of immersion lithography using a liquid having a higher refractive index than water has been underway. A material with a refractive index of 1.65 has been proposed as a liquid, and an NA of 1.55 is possible by combining it with a front lens using LuAG (Lu ₃ Al ₅ O ₁₂ garnet) with a refractive index of 2.1. Therefore, a resolution of 35 nm LS is expected. However, LuAG has a large secondary refractive index and absorption at present, and there is no prospect of practical use. A liquid with a refractive index of 1.65 has a refractive index change with respect to a temperature change that is about five times greater than that of water, so the temperature control accuracy must be increased by a factor of five over water. There is a problem that it is difficult to design a nozzle for high-speed scanning because it has a higher viscosity than water and a low contact angle with a resist film or top coat. Furthermore, in order to resolve 32 nm LS in combination with an NA lens of 1.7 or more, a liquid having a refractive index of 1.8 or more is required. To increase the refractive index, a compound having an alkyl group having a cyclic structure is required. It is necessary, and since the viscosity further increases, high-speed scanning cannot be performed, and when sulfur is added, the refractive index increases but the absorption increases, so that a practical liquid having a refractive index exceeding 1.65 has not yet been found.

  On the other hand, various problems due to the presence of water on the resist film in water immersion exposure have been pointed out. That is, the photo acid generator in the resist composition, the acid generated by light irradiation, the pattern shape change due to elution of the amine quencher in the water in contact (leaching), and the water swelling of the photoresist film Examples include pattern collapse.

  In particular, with regard to elution of the resist composition in water, studies were initially started from the viewpoint of preventing contamination of the projection lens of the exposure apparatus, and a plurality of exposure apparatus manufacturers proposed elution amount standards.

  As a method for solving this problem, it has been proposed to provide a protective film made of a perfluoroalkyl compound between a resist film and water (see Non-Patent Document 3).

  By forming these protective films, direct contact between the photoresist film and water can be avoided, so that elution of the photoresist composition into water can be suppressed.

  However, in the protective film made of the perfluoroalkyl compound, chlorofluorocarbon or the like is used as a diluent for controlling the coating film thickness. As is well known, chlorofluorocarbon is currently problematic for use from the viewpoint of environmental protection. ing. In addition, since this protective film must be peeled off with chlorofluorocarbon before developing the photoresist film, it is necessary to add a dedicated coating and peeling unit for the protective film to the conventional device, and the cost of chlorofluorocarbon solvents. There were many problems in practical use, such as being voluminous.

  As a means for reducing the practical disadvantages associated with the use of these solvent-peeling protective films, an alkali developer-soluble protective film has been proposed (see Patent Document 1).

  Such an alkaline developer-soluble protective film can be dissolved and removed at the same time in the development process of the photoresist film, which is revolutionary in that it does not require an additional protective film peeling process or a special peeling unit. It can be said that there is. However, the use of such an alkaline developer-soluble protective film still requires a protective film coating step. In addition, the diluting solvent that constitutes the coating solution for the protective film material must be selected from those in which the photoresist film does not dissolve easily because of the restriction that the photoresist film as the underlying film must not be affected. In order to avoid troubles such as resin precipitation due to mixing, a unit dedicated to coating a protective film is required.

  On the other hand, all ArF immersion exposure apparatuses marketed to date do not immerse the entire substrate coated with a resist film in water, but hold water partially between the projection lens and the wafer. The local fill method is used in which exposure is performed while scanning the stage on which the wafer is placed at a speed of 300 to 550 mm per second. Thus, due to high-speed scanning, water cannot be held between the projection lens and the wafer, and there is a problem that droplets remain on the surface of the photoresist or protective film after scanning. . It is believed that leaving the droplets in this way induces pattern formation defects.

  In order to eliminate remaining droplets on the surface of the photoresist film or the protective film after scanning, it is necessary to improve the ease of movement of water on these coating films. In order to reduce the number of defects due to immersion exposure, it has been shown that it is effective to increase the receding contact angle of the photoresist film or the protective film with respect to water (see Non-Patent Document 4).

  In order to reduce the amount of dispensing in the spin coating of the photoresist material, when the photoresist material is dispensed and spin coated in a state where the substrate is coated with a photoresist solvent or a solution mixed with the photoresist solvent, the photoresist solution is applied to the substrate. A method has been proposed in which spread is improved and the amount of dispensed photoresist material is reduced (see Patent Document 2). A similar process can be considered for spin coating of a resist protective film.

  Residual defects called blobs occurring on the resist film after development have been a problem. This occurs remarkably when the resist film after development has high hydrophobicity. In the case of a hydrophilic surface with a low contact angle with water when drying off with pure water rinse after development, the water is dried from the center while covering the entire surface of the resist film, and the water moves on the wafer surface. There is nothing. On the other hand, when the resist film surface is a hydrophobic surface, the wafer surface is moved at a high speed while being repelled. At this time, it moves while scraping the film surface, and after drying, it causes a blob defect such as a stain or a blockage defect in which the hole mouth is buried.

  In a resist film for immersion lithography using a protective film, mixing of the protective film and the resist film leaves a highly hydrophobic protective film on the surface of the developed resist film, resulting in blob defects on the resist film. . It is necessary to prevent mixing between the protective film and the resist film so that the protective film does not remain after development.

  In order to prevent blob defects, it is effective not only to increase the hydrophilicity of the resist film surface after development, but also to make the film surface uneven. In order not to move by forming polka dots by the centrifugal force of shaking, not only the electrostatic force due to the hydrophilicity of the membrane surface but also the anchor effect due to the unevenness of the membrane surface is effective.

  It has been pointed out that the resist film shape is changed by applying a protective film. This is considered to be caused by the movement of the acid generator and amine quencher added to the resist material to the protective film layer and the intermixing of the protective film and the resist film. In particular, in the type of protective film that dissolves in an alkaline developer, the resist pattern after development changes greatly compared to the case where no protective film is applied. To do. In order to prevent unevenness on the resist film surface after development in order to prevent blob defects, it is effective to slightly dissolve the resist film surface with an alkaline developer. However, the fact that the resist film surface is dissolved is not preferable because the film thickness of the pattern is reduced, the line-and-space pattern has a round head shape, and the dense hole pattern causes a film loss of the remaining portion between the holes. There is a need to develop a developer-soluble protective film material that does not cause a shape change in all resist films and that does not generate defects.

JP 2005-264131 A Japanese Patent Laid-Open No. 9-246173 Proc. SPIE Vol. 4690 xxix Proc. SPIE Vol. 5040 p724 2nd Immersion Work Shop, July 11, 2003, Resist and Cover Material Investing for Immersion Lithography 2nd International Symposium on Immersion Lithography, 12-15 / Sept. , 2005, Defectivity data take with a full-field immersion exposure tool, Nakano et. , Al.

  The present invention has been made in view of such problems. In an immersion lithography process in which a protective film is applied, the resist film surface is wetted with a higher alcohol having 4 to 10 carbon atoms before the protective film is applied. By applying a protective film, the change of the pattern shape can be minimized by preventing the resist additive from moving to the protective film layer. It is an object of the present invention to provide a pattern forming method capable of preventing the occurrence of blob defects by reducing the amount of dispensing when applying a protective film and reducing the amount of dispensing when a protective film is applied.

The present invention has been made to solve the above-described problems, and proposes a pattern forming method shown below.
Claim 1:
After applying the photoresist material on the substrate, and after heat treatment, the photoresist film surface is wetted with a solution containing a higher alcohol having 4 to 10 carbon atoms, then a protective film is applied, and after the heat treatment, high energy rays are applied. The pattern formation method characterized by including the process exposed by (3) and the process developed using a developing solution.
Claim 2:
The pattern forming method according to claim 1, wherein the solution containing the higher alcohol is a solution in which an ether compound having 8 to 12 carbon atoms is further mixed.
Claim 3:
The pattern forming method according to claim 1 or 2, wherein the solution containing the higher alcohol is a solution in which hydrochloric acid, nitric acid, sulfuric acid, carboxylic acid, sulfonic acid, or an amine salt of sulfonic acid is further mixed.
Claim 4:
The pattern forming method according to claim 1, wherein the higher alcohol has 4 to 7 carbon atoms.
Claim 5:
5. The exposure according to claim 1, wherein the step of exposing with the high energy beam is performed by immersion exposure in which exposure is performed via a liquid between the lowest surface of the projection lens and the substrate. Pattern forming method.
Claim 6:
In the immersion exposure, an exposure wavelength in the range of 180 to 250 nm is used, a liquid is inserted between the substrate on which the photoresist film and the protective film are formed, and the lowest surface of the projection lens, and the liquid is used. The pattern forming method according to claim 5, wherein the substrate is exposed through the substrate.
Claim 7:
7. The liquid immersion exposure according to claim 5, wherein water is used as a liquid inserted between the substrate on which the photoresist film and the protective film are formed and the lowest surface of the projection lens. The pattern forming method according to 1.
Claim 8:
The protective film material is obtained by dissolving an alkali-soluble polymer having an α-trifluoromethyl alcohol group in an ether compound having 8 to 12 carbon atoms and / or a higher alcohol having 4 to 10 carbon atoms. 8. The pattern forming method according to any one of 7 above.

  According to the pattern forming method of the present invention, the photoresist film is wetted with a higher alcohol having 4 to 10 carbon atoms before applying the protective film in an immersion lithography process in which the protective film is applied. By applying the protective film, the pattern shape change can be minimized by preventing the resist additive from moving to the protective film layer. Also, by making the resist film surface hydrophilic by alcohol treatment, the occurrence of blob defects can be prevented, and the amount of dispensing when applying the protective film can be reduced.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
For immersion exposure using a developer-soluble protective film, as described above, there is no change in the resist shape after development with or without the application of the protective film, and the dispense amount of the protective film is reduced, especially in isolation. Reduction of blob defects in the hole pattern has been demanded.

  As a result of intensive studies and researches to solve this problem, the present inventor has found that the acid generator and the acid generator in the resist material can be obtained by a process of wetting the resist surface with a higher alcohol having 4 to 10 carbon atoms before applying the protective film. It was discovered that amine compounds such as quenchers can be extracted from the resist film surface, thereby preventing intermixing between the resist film and the protective film by preventing the transfer of additives from the resist film to the protective film layer. Thus, the present invention has been completed.

  That is, the present invention includes a step of applying a photoresist material on a substrate, and after the heat treatment, after the photoresist film surface is wetted with a solution containing a higher alcohol having 4 to 10 carbon atoms, a protective film is applied, and heating is performed. It is a pattern formation method characterized by including the process exposed to a high energy ray after a process, and the process developed using a developing solution.

  Specific examples of the higher alcohol having 4 to 10 carbon atoms include 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, and tert- Amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol, 2-hexanol, 3-hexanol, 2, 3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl-1-pentanol, 2-methyl-2 -Pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3- Til-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl-3-pentanol, cyclohexanol, 1-octanol These may be used alone or in combination of two or more, and more preferably a higher alcohol having 4 to 7 carbon atoms is used.

  When the resist film is made of polysilsesquioxane, polynorbornene, a polymer by metathesis ring-opening polymerization (ROMP) or the like, the film thickness may be reduced by 10 nm or more due to the surface treatment of the alcohol. May change. In this case, it is preferable to mix the alcohol and an ether compound having 8 to 12 carbon atoms for the purpose of preventing the film thickness from decreasing.

  Specific examples of the ether compound having 8 to 12 carbon atoms include di-n-butyl ether, di-isobutyl ether, di-sec-butyl ether, di-n-pentyl ether, diisopentyl ether, di-sec-pentyl ether, Examples thereof include one or more solvents selected from di-t-amyl ether and di-n-hexyl ether.

  As a mixing ratio, the higher alcohol having 4 to 10 carbon atoms is 10 to 100% by mass, preferably 20 to 100% by mass, more preferably 30 to 100% by mass with respect to the whole solvent, but the above ether compound is blended. In this case, the proportion of the ether compound is 10% by mass or more, particularly 20% by mass or more. Furthermore, other solvents such as alkane such as n-hexane, n-heptane, n-octane, n-nonane, cyclohexane, cycloheptane and n-decane, toluene and xylene may be mixed. Even in this case, the proportion of the higher alcohol having 4 to 10 carbon atoms is mixed within the range of 10 to 100% by mass, preferably 20 to 100% by mass, and more preferably 30 to 100% by mass with respect to the entire solvent.

In order to enhance the hydrophilicity of the resist film surface, hydrochloric acid, nitric acid, sulfuric acid, carboxylic acid, sulfonic acid, or a compound having an amine salt of sulfonic acid may be mixed in a solvent.
Carboxylic acids include formic acid, acetic acid, propanoic acid, butanoic acid, isobutanoic acid, pentanoic acid, cyclohexyl carboxylic acid, lauric acid, palmitic acid, stearic acid, oxalic acid, malonic acid, oxalic acid, glutaric acid, adipic acid, acrylic acid 0 as an acid, methacrylic acid, propionic acid, crotonic acid, oleic acid, maleic acid or sulfonic acid is an alkyl sulfone such as methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid or camphorsulfonic acid. Perfluoroalkyl sulfones such as acid, benzene sulfonic acid, tosylic acid, dimethylene sulfonic acid, aryl sulfonic acid such as naphthalene sulfonic acid, trifluoromethane sulfonic acid, trifluoroethyl sulfonic acid, perfluorobutane sulfonic acid Acid and the like. Examples of the amine salt include primary, secondary, tertiary, aromatic and heteroaromatic amine salts of the above sulfonic acid. The addition ratio of these compounds is 0.0001-30 mass% with respect to the whole solvent, Preferably it is 0.001-20 mass%, More preferably, it is 0.01-10 mass%.

  In order to wet the photoresist surface with a solution containing a higher alcohol having 4 to 10 carbon atoms, the solution is dispensed on the surface of the resist film after pre-baking, and the wafer is rotated. Dispensing time can be shortened by dispensing while rotating the wafer. In this case, the rotational speed is preferably 500 to 5,000 rpm, particularly preferably 700 to 4,000 rpm, and the treatment is preferably performed for 0.1 to 200 seconds, particularly 0.5 to 60 seconds. Thereafter, the resist protective film solution is continuously dispensed and spin-coated, and baked to form a resist protective film.

  The resist film surface moistened with a higher alcohol having 4 to 10 carbon atoms covers the entire surface of the wafer with a small amount of the resist protective film dispensed because the solution easily spreads when the resist protective film solution is dispensed thereon. Can do. In addition, by extracting the acid generator and amine quencher from the resist film surface with alcohol dispense, the amount of leaching of the acid generator and amine quencher to water can be reduced through the protective film. Furthermore, the surface of the resist film can be made uneven by dispensing a higher alcohol having 4 to 10 carbon atoms, thereby increasing the hydrophilicity of the surface and suppressing the occurrence of blob defects.

  Here, as the protective film, an alkali-soluble polymer having an α-trifluoromethyl alcohol group is added to the ether compound having 8 to 12 carbon atoms, the higher alcohol having 4 to 10 carbon atoms, and a mixed solvent thereof in an amount of 0.5. A material dissolved at a concentration of ˜20 mass%, particularly 1 to 10 mass%, is preferably used.

In this case, the α-trifluoromethyl alcohol group generally includes those represented by the following formula (1).

Here, R ¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or a fluorinated alkyl group, or a linear, branched or cyclic group having 1 to 10 carbon atoms. It is an alkylene group or a fluorinated alkylene group, and may have an ether group (—O—). The alkali-soluble polymer having an α-trifluoromethyl alcohol group represented by the general formula (1) has one of the following repeating units a having the α-trifluoromethyl alcohol group of the formula (1). It is preferable.

（式中、Ｒ²、Ｒ³は水素原子、又は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基で、Ｒ²とＲ³が結合してこれらが結合する炭素原子と共に炭素数３〜１２の脂環を形成していてもよく、Ｒ⁴は水素原子又はメチル基である。） Among the above repeating units, those having a repeating unit of (meth) acrylate are preferable, and a structural unit represented by the following general formula (2) is particularly preferably used.

(Wherein R ² and R ³ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, carbon atoms together with the carbon atom to which R ² and R ³ are bonded to each other) ( ^3-4 alicyclic rings may be formed, and R ⁴ is a hydrogen atom or a methyl group.)

（式中、Ｒ⁵は炭素数２〜１０の少なくとも１つのフッ素原子で置換された直鎖状又は分岐状のアルキル基であり、Ｒ⁶は水素原子又はメチル基である。） In addition to the repeating unit a, a repeating unit b represented by the following general formula (3) can be copolymerized.

(In the formula, R ⁵ is a linear or branched alkyl group substituted with at least one fluorine atom having 2 to 10 carbon atoms, and R ⁶ is a hydrogen atom or a methyl group.)

Specific examples of R ⁵ include the following.

  As the repeating unit of the resist protective film polymer, the above-mentioned unit a, particularly the unit a represented by the general formula (2) is essential, but in order to prevent alkali solubility and mixing with the resist film, a carboxyl group The repeating unit c having can be copolymerized. The repeating unit c is specifically represented by the following general formula (4).

Here, R ⁷ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has an ether group (—O—) or an ester group (—COO—). Alternatively, the alkylene group may be substituted with fluorine. R ⁸ is a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. The repeating unit c is specifically exemplified below.

  The ratio of the repeating units a, b, c is 0 <a ≦ 1.0, 0 ≦ b <1.0, 0 ≦ c <1.0, preferably 0.1 ≦ a ≦ 1.0, 0 ≦ b. ≦ 0.9, 0 ≦ c ≦ 0.9, and a + b + c = 1.

  Here, a + b + c = 1 means that in the polymer compound containing repeating units a, b and c, the total amount of repeating units a, b and c is 100 mol% with respect to the total amount of all repeating units. It shows that.

  The polymer compound for the resist protective film according to the pattern forming method of the present invention has a polystyrene-equivalent weight average molecular weight of 1,000 to 500,000, preferably 2,000 to 30, as determined by gel permeation chromatography (GPC). 000 is desirable. If the weight average molecular weight is too small, mixing with the resist material occurs, or it becomes easy to dissolve in water. If it is too large, there may be a problem in film formability after spin coating, or the alkali solubility may be lowered.

  The resist material according to the pattern forming method of the present invention is preferably a chemically amplified positive resist material, and further has at least a repeating unit having an acid labile group, and an adhesive group of a hydroxy group and / or a lactone ring. It is preferable to include a base resin containing a repeating unit.

  With such a chemically amplified positive resist material, the base resin includes a repeating unit having a hydroxy group and / or an adhesive group of a lactone ring, whereby high adhesion to the substrate can be realized. Furthermore, since the base resin has repeating units having acid labile groups, the acid labile groups are eliminated by the acid generated by the acid generator during exposure, so that the resist exposed area is dissolved in the developer. By doing so, a very highly accurate pattern can be obtained.

  As said base resin, the high molecular compound of polystyrene conversion weight average molecular weight 1,000-100,000 by GPC shown by following formula (R1) and / or following formula (R2), Preferably it is 3,000-30,000 However, it is not limited to these.

In the above formula, R ⁰⁰¹ represents a hydrogen atom, a methyl group, or —CH ₂ CO ₂ R ⁰⁰³ .
R ⁰⁰² represents a hydrogen atom, a methyl group or a -CO ₂ R ^003.
R ⁰⁰³ represents a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, ethylcyclopentyl group, butylcyclopentyl group, ethylcyclohexyl group, butylcyclohexyl group, adamantyl group, ethyladamantyl group, butyl Examples thereof include an adamantyl group.

R ⁰⁰⁴ represents a hydrogen atom, a fluorine-containing substituent having 1 to 15 carbon atoms and / or a carboxy group or a monovalent hydrocarbon group containing a hydroxyl group, specifically a hydrogen atom, carboxyethyl, carboxybutyl, carboxy Examples include cyclopentyl, carboxycyclohexyl, carboxynorbornyl, carboxyadamantyl, hydroxyethyl, hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxynorbornyl, hydroxyadamantyl, hydroxyhexafluoroisopropylcyclohexyl, di (hydroxyhexafluoroisopropyl) cyclohexyl, etc. it can.

At least one of R ^{005 to} R ⁰⁰⁸ represents a fluorine-containing substituent having 1 to 15 carbon atoms and / or a carboxy group and a monovalent hydrocarbon group containing a hydroxyl group, and the rest each independently represents a hydrogen atom or a carbon number of 1 -15 linear, branched or cyclic alkyl groups are shown. Specific examples of the monovalent hydrocarbon group containing a fluorine-containing substituent having 1 to 15 carbon atoms and / or a carboxy group and a hydroxyl group include carboxy, carboxymethyl, carboxyethyl, carboxybutyl, hydroxymethyl, hydroxyethyl, Hydroxybutyl, 2-carboxyethoxycarbonyl, 4-carboxybutoxycarbonyl, 2-hydroxyethoxycarbonyl, 4-hydroxybutoxycarbonyl, carboxycyclopentyloxycarbonyl, carboxycyclohexyloxycarbonyl, carboxynorbornyloxycarbonyl, carboxyadamantyloxycarbonyl, hydroxy Cyclopentyloxycarbonyl, hydroxycyclohexyloxycarbonyl, hydroxynorbornyloxycarbonyl, hydroxyadam Chill oxycarbonyl, hydroxy hexafluoroisopropyl cyclohexyl oxycarbonyl, di (hydroxy hexafluoroisopropyl) cyclohexyl oxycarbonyl like.
Examples of the straight, branched, the alkyl group of cyclic, specifically exemplified the same ones as exemplified for R ^003.

R ^{005 to} R ⁰⁰⁸ (for example, R ^{005 and} R ⁰⁰⁶ , R ^{006 and} R ⁰⁰⁷ ) may be bonded to each other to form a ring, and in that case, at least one of R ^{005 to} R ⁰⁰⁸ involved in the formation of the ring 1 represents a fluorine-containing substituent having 1 to 15 carbon atoms and / or a carboxy group and a divalent hydrocarbon group containing a hydroxyl group, and the remainder involved in ring formation is independently a single bond or 1 to 1 carbon atom. 15 linear, branched or cyclic alkylene groups are shown. The divalent hydrocarbon group containing a fluorine-containing substituent and / or carboxy group or hydroxyl group having 1 to 15 carbon atoms is specifically a monovalent containing the fluorine-containing substituent and / or carboxyl group or hydroxyl group. The thing etc. which remove | excluded one hydrogen atom from what was illustrated by the hydrocarbon group of this can be illustrated. Specific examples of the linear, branched or cyclic alkylene group having 1 to 15 carbon atoms include those obtained by removing one hydrogen atom from those exemplified for ^R003 .

R ⁰⁰⁹ represents a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 3 to 15 carbon atoms, specifically 2-oxooxolan-3-yl, 4,4-dimethyl-2- Examples include oxooxolan-3-yl, 4-methyl-2-oxooxan-4-yl, 2-oxo-1,3-dioxolan-4-ylmethyl, 5-methyl-2-oxooxolan-5-yl and the like it can.

At least one of R ^{010 to} R ^{013 represents} a monovalent hydrocarbon group containing a —CO ₂ — partial structure having 2 to 15 carbon atoms, and the rest each independently represents a hydrogen atom or a straight chain having 1 to 15 carbon atoms. -Like, branched or cyclic alkyl groups. Specific examples of the monovalent hydrocarbon group containing a —CO ₂ — partial structure having 2 to 15 carbon atoms include 2-oxooxolan-3-yloxycarbonyl and 4,4-dimethyl-2-oxooxo. Lan-3-yloxycarbonyl, 4-methyl-2-oxooxan-4-yloxycarbonyl, 2-oxo-1,3-dioxolan-4-ylmethyloxycarbonyl, 5-methyl-2-oxooxolane-5 -Ilyloxycarbonyl and the like can be exemplified. Examples of the straight, branched, the alkyl group of cyclic, specifically exemplified the same ones as exemplified for R ^003.

R ^{010 to} R ⁰¹³ (for example, R ^{010 and} R ⁰¹¹ , R ^{011 and} R ⁰¹² ) may be bonded to each other to form a ring, in which case at least one of R ^{010 to} R ⁰¹³ involved in the formation of the ring 1 represents a divalent hydrocarbon group containing a —CO ₂ — partial structure having 1 to 15 carbon atoms, and the remainder involved in ring formation is each independently a single bond or a straight chain having 1 to 15 carbon atoms. Represents a branched or cyclic alkylene group. Specific examples of the divalent hydrocarbon group containing a —CO ₂ — partial structure having 1 to 15 carbon atoms include 1-oxo-2-oxapropane-1,3-diyl and 1,3-dioxo-2. - oxa-1,3-diyl, 1-oxo-2-Okisabutan-1,4-diyl, other like 1,3-dioxo-2-Okisabutan-1,4-diyl, the -CO ₂ - partial structure The thing etc. which remove | excluded one hydrogen atom from what was illustrated with the monovalent | monohydric hydrocarbon group containing this can be illustrated. Specific examples of the linear, branched or cyclic alkylene group having 1 to 15 carbon atoms include those obtained by removing one hydrogen atom from those exemplified for ^R003 .

R ⁰¹⁴ represents a polycyclic hydrocarbon group having 7 to 15 carbon atoms or an alkyl group containing a polycyclic hydrocarbon group, and specifically includes norbornyl, bicyclo [3.3.1] nonyl, tricyclo [5 .2.1.0 ^2,6 ] decyl, adamantyl, ethyladamantyl, butyladamantyl, norbornylmethyl, adamantylmethyl and the like.

R ⁰¹⁵ represents an acid labile group, and specific examples will be described later.
X represents —CH ₂ or an oxygen atom.
k is 0 or 1.

As the acid labile group for R ⁰¹⁵ , various groups can be used. Specifically, groups represented by the following general formulas (L1) to (L4), tertiary groups having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms are preferred. Examples of the alkyl group include trialkylsilyl groups having 1 to 6 carbon atoms and oxoalkyl groups having 4 to 20 carbon atoms.

In the above formula, a broken line indicates a bond.
In the formula (L1), R ^L01 and R ^L02 represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, specifically a methyl group, Examples thereof include an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, a cyclohexyl group, a 2-ethylhexyl group, an n-octyl group, and an adamantyl group. R ^L03 represents a monovalent hydrocarbon group which may have a hetero atom such as an oxygen atom having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms, and is a linear, branched or cyclic alkyl group, Examples in which a part of these hydrogen atoms are substituted with a hydroxyl group, an alkoxy group, an oxo group, an amino group, an alkylamino group, and the like can be given. Specifically, a linear, branched or cyclic alkyl group Examples thereof include those similar to R ^L01 and R ^L02 above, and examples of the substituted alkyl group include the following groups.

R ^L01 and R ^L02 , R ^L01 and R ^L03 , R ^L02 and R ^L03 may be bonded to each other to form a ring together with the carbon atom or oxygen atom to which they are bonded, and in the case of forming a ring, R ^L01 , R ^L02 and R ^L03 each represents a linear or branched alkylene group having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms.

In the formula (L2), R ^L04 is a tertiary alkyl group having 4 to 20 carbon atoms, preferably 4 to 15 carbon atoms, each alkyl group is a trialkylsilyl group having 1 to 6 carbon atoms, and 4 to 20 carbon atoms. An oxoalkyl group or a group represented by the above general formula (L1) is shown. Specific examples of the tertiary alkyl group include a tert-butyl group, a tert-amyl group, a 1,1-diethylpropyl group, and 2-cyclopentylpropane. 2-yl group, 2-cyclohexylpropan-2-yl group, 2- (bicyclo [2.2.1] heptan-2-yl) propan-2-yl group, 2- (adamantan-1-yl) propane 2-yl group, 1-ethylcyclopentyl group, 1-butylcyclopentyl group, 1-ethylcyclohexyl group, 1-butylcyclohexyl group, 1-ethyl-2-cyclopentenyl group 1-ethyl-2-cyclohexenyl group, 2-methyl-2-adamantyl group, 2-ethyl-2-adamantyl group and the like. Specific examples of the trialkylsilyl group include trimethylsilyl group and triethylsilyl group. Dimethyl-tert-butylsilyl group and the like. Specific examples of the oxoalkyl group include 3-oxocyclohexyl group, 4-methyl-2-oxooxan-4-yl group, and 5-methyl-2-oxooxolane. A -5-yl group etc. can be illustrated. y is an integer of 0-6.

In the formula (L3), R ^L05 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted, or an aryl group which may be substituted having 6 to 20 carbon atoms, Specific examples of the optionally substituted alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a tert-amyl group, and an n-pentyl group. A linear, branched or cyclic alkyl group such as a group, n-hexyl group, cyclopentyl group, cyclohexyl group, bicyclo [2.2.1] heptyl group, and a part of these hydrogen atoms are a hydroxyl group, an alkoxy group, A carboxy group, an alkoxycarbonyl group, an oxo group, an amino group, an alkylamino group, a cyano group, a mercapto group, an alkylthio group, a sulfo group or the like, or these Examples include those in which a part of the methylene group is substituted with an oxygen atom or a sulfur atom. Specific examples of the aryl group which may be substituted include a phenyl group, a methylphenyl group, a naphthyl group, an anthryl group, and a phenanthryl. Examples thereof include a group and a pyrenyl group. m is 0 or 1, and n is 0, 1, 2, or 3, and 2m + n = 2 or 3.

In the formula (L4), R ^L06 represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may be substituted or an aryl group having 6 to 20 carbon atoms which may be substituted; Specifically, the same thing as R ^L05 can be illustrated. R ^{L07 to} R ^L16 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 15 carbon atoms, specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec- Butyl, tert-butyl, tert-amyl, n-pentyl, n-hexyl, n-octyl, n-nonyl, n-decyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl Group, cyclopentylbutyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclohexylbutyl group, etc., linear, branched or cyclic alkyl groups, and some of these hydrogen atoms are hydroxyl groups, alkoxy groups, carboxy groups, alkoxycarbonyl groups Oxo group, amino group, alkylamino group, cyano group, mercapto group, alkylthio group, Or the like can be exemplified those substituted in sulfo group. R ^{L07 to} R ^L16 may be bonded to each other to form a ring (for example, R ^L07 and R ^L08 , R ^L07 and R ^L09 , R ^L08 and R ^L10 , R ^L09 and R ^L10 , R ^L11 and R ^L12). , R ^L13 and R ^L14, etc.), in which case a divalent hydrocarbon group having 1 to 15 carbon atoms is shown. Specifically, one hydrogen atom is removed from those exemplified for the monovalent hydrocarbon group above Can be exemplified. R ^{L07 to} R ^L16 may be bonded to each other adjacent to each other to form a double bond (for example, R ^L07 and R ^L09 , R ^L09 and R ^L15 , R ^L13 and R ^L15 etc.).

Of the acid labile groups represented by the above formula (L1), specific examples of the linear or branched groups include the following groups.

  Among the acid labile groups represented by the above formula (L1), specific examples of cyclic groups include tetrahydrofuran-2-yl group, 2-methyltetrahydrofuran-2-yl group, tetrahydropyran-2-yl group, 2 -A methyltetrahydropyran-2-yl group etc. can be illustrated.

  Specific examples of the acid labile group of the above formula (L2) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1,1-diethyl. Propyloxycarbonyl group, 1,1-diethylpropyloxycarbonylmethyl group, 1-ethylcyclopentyloxycarbonyl group, 1-ethylcyclopentyloxycarbonylmethyl group, 1-ethyl-2-cyclopentenyloxycarbonyl group, 1-ethyl-2 Examples include -cyclopentenyloxycarbonylmethyl group, 1-ethoxyethoxycarbonylmethyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like.

  Specific examples of the acid labile group of the above formula (L3) include 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-isopropylcyclopentyl, 1-n-butylcyclopentyl, 1-sec- Butylcyclopentyl, 1-cyclohexylcyclopentyl, 1- (4-methoxy-n-butyl) cyclopentyl, 1- (bicyclo [2.2.1] heptan-2-yl) cyclopentyl, 1- (7-oxabicyclo [2. 2.1] heptan-2-yl) cyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 3-methyl-1-cyclopenten-3-yl, 3-ethyl-1-cyclopenten-3-yl, 3-methyl- 1-cyclohexen-3-yl, 3-ethyl-1-cyclohexen-3-yl, etc. It can be exemplified.

As the acid labile group of the above formula (L4), groups represented by the following formulas (L4-1) to (L4-4) are particularly preferable.

In the general formulas (L4-1) to (L4-4), a broken line indicates a coupling position and a coupling direction. R ^L41 each independently represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, specifically a methyl group, an ethyl group, a propyl group, an isopropyl group, n Examples include -butyl group, sec-butyl group, tert-butyl group, tert-amyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

  In the general formulas (L4-1) to (L4-4), enantiomers and diastereomers may exist, but the general formulas (L4-1) to (L4-4) may exist. ) Represents all of these stereoisomers. These stereoisomers may be used alone or as a mixture.

（式中、Ｒ^L41は前述と同様である。） For example, the general formula (L4-3) represents one or a mixture of two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2). To do.

(In the formula, R ^L41 is the same as described above.)

（式中、Ｒ^L41は前述と同様である。） The general formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4). And

(In the formula, R ^L41 is the same as described above.)

  The general formulas (L4-1) to (L4-4), (L4-3-1), (L4-3-2), and formulas (L4-4-1) to (L4-4-4) are Their enantiomers and enantiomeric mixtures are also shown representatively.

（式中、Ｒ^L41は前述と同様である。） In addition, the coupling | bonding of Formula (L4-1)-(L4-4), (L4-3-1), (L4-3-2), and Formula (L4-4-1)-(L4-4-4) High reactivity in the acid-catalyzed elimination reaction is realized by the fact that each direction is on the exo side with respect to the bicyclo [2.2.1] heptane ring (see JP 2000-336121 A). In the production of a monomer having a tertiary exo-alkyl group having a bicyclo [2.2.1] heptane skeleton as a substituent, the following general formulas (L4-1-endo) to (L4-4-endo) are used. In some cases, a monomer substituted with the indicated endo-alkyl group may be included, but in order to achieve good reactivity, the exo ratio is preferably 50% or more, and the exo ratio is 80% or more. More preferably.

(In the formula, R ^L41 is the same as described above.)

Specific examples of the acid labile group of the above formula (L4) include the following groups.

Further, tertiary alkyl groups having 4 to 20 carbon atoms, trialkylsilyl groups each having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms are specifically exemplified as R ^L04 . The thing similar to a thing etc. can be illustrated.

In the (R2), ^R016 represents a hydrogen atom or a methyl group. R ⁰¹⁷ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms.

  In (R1), a1 ′, a2 ′, a3 ′, b1 ′, b2 ′, b3 ′, c1 ′, c2 ′, c3 ′, d1 ′, d2 ′, d3 ′, and e ′ are 0 or more and less than 1. A1 ′ + a2 ′ + a3 ′ + b1 ′ + b2 ′ + b3 ′ + c1 ′ + c2 ′ + c3 ′ + d1 ′ + d2 ′ + d3 ′ + e ′ = 1. In the above (R2), f ′, g ′, h ′, i ′, and j ′ are numbers of 0 or more and less than 1, and satisfy f ′ + g ′ + h ′ + i ′ + j ′ = 1. x ′, y ′ and z ′ are integers of 0 to 3, which satisfy 1 ≦ x ′ + y ′ + z ′ ≦ 5 and 1 ≦ y ′ + z ′ ≦ 3.

  In the above formula (R1), specific examples of the repeating unit introduced at the composition ratio a1 'include the following, but are not limited thereto.

  In the above formula (R1), specific examples of the repeating unit introduced at the composition ratio b1 'include the following, but are not limited thereto.

  Specific examples of the repeating unit introduced at the composition ratio d1 ′ in the above formula (R1) include the following, but are not limited thereto.

  In the above formula (R1), specific examples of the polymer compound composed of repeating units having a composition ratio of a3 ′, b3 ′, c3 ′, and d3 ′ include the following, but the polymer compounds are not limited thereto. Absent.

  The polymer compound constituting the base resin is not limited to one type, and two or more types can be added. The performance of the resist material can be adjusted by using a plurality of types of polymer compounds.

  The resist material in the pattern forming method of the present invention may contain an acid generator in order to function as a chemically amplified positive resist material. For example, a compound that generates an acid in response to actinic rays or radiation (photoacid generator) ) May be contained. The component of the photoacid generator may be any compound that generates an acid upon irradiation with high energy rays. Suitable photoacid generators include sulfonium salts, iodonium salts, sulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate type acid generators, and the like. Although described in detail below, these can be used alone or in admixture of two or more.

The sulfonium salt is a salt of a sulfonium cation and a sulfonate or bis (substituted alkylsulfonyl) imide or tris (substituted alkylsulfonyl) methide. As the sulfonium cation, triphenylsulfonium, (4-tert-butoxyphenyl) diphenylsulfonium, bis (4- tert-butoxyphenyl) phenylsulfonium, tris (4-tert-butoxyphenyl) sulfonium, (3-tert-butoxyphenyl) diphenylsulfonium, bis (3-tert-butoxyphenyl) phenylsulfonium, tris (3-tert-butoxyphenyl) ) Sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfoni , Tris (3,4-ditert-butoxyphenyl) sulfonium, diphenyl (4-thiophenoxyphenyl) sulfonium, (4-tert-butoxycarbonylmethyloxyphenyl) diphenylsulfonium, tris (4-tert-butoxycarbonylmethyloxy) Phenyl) sulfonium, (4-tert-butoxyphenyl) bis (4-dimethylaminophenyl) sulfonium, tris (4-dimethylaminophenyl) sulfonium, 2-naphthyldiphenylsulfonium, dimethyl 2-naphthylsulfonium, 4-hydroxyphenyldimethylsulfonium 4-methoxyphenyldimethylsulfonium, trimethylsulfonium, 2-oxocyclohexylcyclohexylmethylsulfonium, trinaphthylsulfonyl , Tribenzylsulfonium, diphenylmethylsulfonium, dimethylphenylsulfonium, 2-oxo-2-phenylethylthiacyclopentanium, 4-n-butoxynaphthyl-1-thiacyclopentanium, 2-n-butoxynaphthyl-1- Examples of the sulfonate include trifluoromethane sulfonate, pentafluoroethane sulfonate, nonafluorobutane sulfonate, dodecafluorohexane sulfonate, pentafluoroethyl perfluorocyclohexane sulfonate, heptadecafluorooctane sulfonate, 2,2, and the like. 2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenes Lulfonate, mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, 4- (4′-toluenesulfonyloxy) benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate Methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propanesulfonate, , 1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert -Butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-adamantanecarbonylcarbonyl-1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1, 1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane Sulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- ( Ruborunan 2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^{2, 5.} 1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate, etc., and bis (substituted alkylsulfonyl) imide includes bistrifluoromethylsulfonylimide, bispentafluoroethylsulfonylimide, bisheptafluoropropylsulfonylimide 1,3-propylenebissulfonylimide and the like, and tris (substituted alkylsulfonyl) methides include tristrifluoromethylsulfonylmethide, and sulfonium salts of these combinations.

Iodonium salt is a salt of iodonium cation and sulfonate or bis (substituted alkylsulfonyl) imide, tris (substituted alkylsulfonyl) methide, diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert-butoxyphenylphenyliodonium. Aryliodonium cations such as 4-methoxyphenylphenyliodonium and sulfonates such as trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2, 2,2-trifluoroethanesulfonate, pentafluorobenzenes Phonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate , Camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro- 2- (4-phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclo Xancarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1, 3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-adamantanecarbonylcarbonyl-1,1,3 , 3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1, , 1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro Ro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate and the like, and bis (substituted alkylsulfonyl) imide includes bistrifluoromethylsulfonylimide, bispentafluoroethylsulfonylimide, bisheptafluoropropylsulfonylimide 1,3-propylenebissulfonylimide and the like, and tris (substituted alkylsulfonyl) methide includes tristrifluoromethylsulfonylmethide, and iodonium salts of these combinations.

  As the sulfonyldiazomethane, bis (ethylsulfonyl) diazomethane, bis (1-methylpropylsulfonyl) diazomethane, bis (2-methylpropylsulfonyl) diazomethane, bis (1,1-dimethylethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane , Bis (perfluoroisopropylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (4-methylphenylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (2-naphthylsulfonyl) diazomethane, bis ( 4-acetyloxyphenylsulfonyl) diazomethane, bis (4-methanesulfonyloxyphenylsulfonyl) diazomethane, bis (4- (4-toluenes) Phonyloxy) phenylsulfonyl) diazomethane, bis (4-n-hexyloxy) phenylsulfonyl) diazomethane, bis (2-methyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2,5-dimethyl-4-) (N-hexyloxy) phenylsulfonyl) diazomethane, bis (3,5-dimethyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2-methyl-5-isopropyl-4- (n-hexyloxy) Phenylsulfonyl) diazomethane, 4-methylphenylsulfonylbenzoyldiazomethane, tertbutylcarbonyl-4-methylphenylsulfonyldiazomethane, 2-naphthylsulfonylbenzoyldiazomethane, 4-methylphenylsulfonyl-2-naphthoyldi Include carbonyl diazomethane - Zometan, bissulfonyldiazomethanes and sulfonyl such as methylsulfonyl benzoyl diazomethane, tert-butoxycarbonyl-4-methylphenyl sulfonyl diazomethane.

Examples of the N-sulfonyloxyimide photoacid generator include succinimide, naphthalene dicarboxylic imide, phthalic imide, cyclohexyl dicarboxylic imide, 5-norbornene-2,3-dicarboxylic imide, 7-oxabicyclo [2. 2.1] An imide skeleton such as 5-heptene-2,3-dicarboxylic acid imide and trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadeca Fluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 4-fluorobenzene sulfonate , Mesitylene sulfonate, 2,4,6-triisopropylbenzene sulfonate, toluene sulfonate, benzene sulfonate, naphthalene sulfonate, camphor sulfonate, octane sulfonate, dodecyl benzene sulfonate, butane sulfonate, methane sulfonate, 2-benzoyloxy-1,1, 3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2 -Pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropanoate Sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-Adamantanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3 3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-naphthyl-ethane sulfonate, 1,1,2, 2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetra Fluoro-2- (tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate and the like.

  Examples of the benzoin sulfonate photoacid generator include benzoin tosylate, benzoin mesylate, and benzoin butane sulfonate.

Pyrogallol trisulfonate photoacid generators include pyrogallol, phloroglucinol, catechol, resorcinol, and hydroquinone all hydroxyl groups trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethyl. Perfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, Camphorsulfonate, octanesulfonate, dodecylbe Zensulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-phenylbenzoyloxy) ) Propane sulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropane sulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1 , 3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-ada Mantanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-penta Fluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-naphthyl-ethane sulfonate, 1,1,2,2-tetra fluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3 And a compound substituted with ene-8-yl) ethanesulfonate.

Examples of the nitrobenzyl sulfonate photoacid generator include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate. Specific examples of the sulfonate include trifluoromethane sulfonate and pentafluoroethane. Sulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethyl perfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2,2,2-trifluoroethanesulfonate, pentafluorobenzenesulfonate, 4-trifluoromethylbenzenesulfonate, 4-Fluorobenzenesulfonate, toluenesulfonate, benzenesulfonate, naphthalenesulfonate, camphor Sulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2- (4-Phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclohexanecarbonyloxy-1,1,3,3,3-pentafluoro Propanesulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropanesulfonate, 2-naphthoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 2- (4- tert-butylbenzoyloxy) -1,1,3,3,3 Pentafluoropropane sulfonate, 2-adamantanecarbonylcarbonyl-1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1 , 3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-naphthyl-ethane sulfonate, 1 , 1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate and the like. A compound in which the nitro group on the benzyl side is replaced with a trifluoromethyl group can also be used.

  Examples of the sulfone photoacid generator include bis (phenylsulfonyl) methane, bis (4-methylphenylsulfonyl) methane, bis (2-naphthylsulfonyl) methane, 2,2-bis (phenylsulfonyl) propane, 2, 2-bis (4-methylphenylsulfonyl) propane, 2,2-bis (2-naphthylsulfonyl) propane, 2-methyl-2- (p-toluenesulfonyl) propiophenone, 2-cyclohexylcarbonyl) -2- ( p-toluenesulfonyl) propane, 2,4-dimethyl-2- (p-toluenesulfonyl) pentan-3-one, and the like.

  Examples of the glyoxime derivative type photoacid generator include compounds described in Japanese Patent No. 2906999 and Japanese Patent Application Laid-Open No. 9-301948, and specifically, bis-O- (p-toluenesulfonyl) -α-. Dimethylglyoxime, bis-O- (p-toluenesulfonyl) -α-diphenylglyoxime, bis-O- (p-toluenesulfonyl) -α-dicyclohexylglyoxime, bis-O- (p-toluenesulfonyl) -2 , 3-pentanedione glyoxime, bis-O- (n-butanesulfonyl) -α-dimethylglyoxime, bis-O- (n-butanesulfonyl) -α-diphenylglyoxime, bis-O- (n-butane Sulfonyl) -α-dicyclohexylglyoxime, bis-O- (methanesulfonyl) -α-dimethylglyoxime, bis O- (trifluoromethanesulfonyl) -α-dimethylglyoxime, bis-O- (2,2,2-trifluoroethanesulfonyl) -α-dimethylglyoxime, bis-O- (10-camphorsulfonyl) -α- Dimethylglyoxime, bis-O- (benzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-fluorobenzenesulfonyl) -α-dimethylglyoxime, bis-O- (p-trifluoromethylbenzenesulfonyl) -Α-dimethylglyoxime, bis-O- (xylenesulfonyl) -α-dimethylglyoxime, bis-O- (trifluoromethanesulfonyl) -nioxime, bis-O- (2,2,2-trifluoroethanesulfonyl) -Nioxime, bis-O- (10-camphorsulfonyl) -nioxime, bis O- (benzenesulfonyl) -nioxime, bis-O- (p-fluorobenzenesulfonyl) -nioxime, bis-O- (p-trifluoromethylbenzenesulfonyl) -nioxime, bis-O- (xylenesulfonyl) -nioxime, etc. Is mentioned.

  Further, oxime sulfonates described in US Pat. No. 6,0047,424, particularly (5- (4-toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (10-camphorsulfonyl) oxyimino-5H- Thiophen-2-ylidene) phenylacetonitrile, (5-n-octanesulfonyloxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, (5- (4-toluenesulfonyl) oxyimino-5H-thiophen-2-ylidene) ( 2-Methylphenyl) acetonitrile, (5- (10-camphorsulfonyl) oxyimino-5H-thiophen-2-ylidene) (2-methylphenyl) acetonitrile, (5-n-octanesulfonyloxyimino-5H-thiof N-2-ylidene) (2-methylphenyl) acetonitrile and the like, and (5- (4- (4-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophene- described in US Pat. No. 6,916,591. 2-ylidene) phenylacetonitrile, (5- (2,5-bis (4-toluenesulfonyloxy) benzenesulfonyl) oxyimino-5H-thiophen-2-ylidene) phenylacetonitrile, and the like.

  U.S. Pat. No. 6,261,738, JP-A-2000-314956, oxime sulfonates, particularly 2,2,2-trifluoro-1-phenyl-ethanone oxime-O-methylsulfonate, 2,2,2- Trifluoro-1-phenyl-ethanone oxime-O- (10-camphoryl sulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (4-methoxyphenyl sulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (1-naphthylsulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2-naphthyl) Sulfonate), 2,2,2-trifluoro-1-phenyl-ethanone oxime-O- (2,4,6-trimethylphenylsulfonate 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate), 2,2,2-trifluoro-1- (4-methylphenyl) ) -Ethanone oxime-O- (methyl sulfonate), 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate), 2,2 , 2-Trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate), 2,2,2-trifluoro-1- (2,4-dimethylphenyl) ) -Ethanone oxime-O- (1-naphthyl sulfonate), 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (2-naphthyl sulfonate), 2 2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10-camphoryl sulfonate), 2,2,2-trifluoro-1- (2,4 , 6-Trimethylphenyl) -ethanone oxime-O- (1-naphthylsulfonate), 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- ( 2-naphthylsulfonate), 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (4-methylthio) Phenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -ethanone oxime-O-methylsulfonate, 2,2,3 , 3,4,4,4-Heptafluoro-1-phenyl-butanone oxime-O- (10-camphoryl sulfonate), 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O -Methyl sulfonate, 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O-10-camphoryl sulfonate, 2,2,2-trifluoro-1- (phenyl) -ethanone Oxime-O- (4-methoxyphenyl) sulfonate, 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (1-naphthyl) sulfonate, 2,2,2-trifluoro-1 -(Phenyl) -ethanone oxime-O- (2-naphthyl) sulfonate, 2,2,2-trifluoro-1- (phenyl) -ethanone oxime-O- (2,4,6-tri Tilphenyl) sulfonate, 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O- (10-camphoryl) sulfonate, 2,2,2-trifluoro-1- (4-methyl) Phenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (2-methylphenyl) -ethanone oxime-O- (10-camphoryl) sulfonate, 2,2,2- Trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime-O- (1-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2,4-dimethylphenyl) -ethanone oxime -O- (2-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (10- Morpholyl) sulfonate, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (1-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2,4,6-trimethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-methylsulfo Narate, 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (3,4-dimethoxyphenyl) -Ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-methylphenyl) sulfur Honate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O- (4-methoxyphenyl) sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) ) -Ethanone oxime-O- (4-dodecylphenyl) sulfonate, 2,2,2-trifluoro-1- (4-methoxyphenyl) -ethanone oxime-O-octylsulfonate, 2,2,2- Trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (4-methoxyphenyl) sulfonate, 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime O- (4-dodecylphenyl) sulfonate, 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O-octyl Sulfonate, 2,2,2-trifluoro-1- (4-thiomethylphenyl) -ethanone oxime-O- (2-naphthyl) sulfonate, 2,2,2-trifluoro-1- (2-methylphenyl) ) -Ethanone oxime-O-methyl sulfonate, 2,2,2-trifluoro-1- (4-methylphenyl) -ethanone oxime-O-phenyl sulfonate, 2,2,2-trifluoro-1 -(4-Chlorophenyl) -ethanone oxime-O-phenyl sulfonate, 2,2,3,3,4,4,4-heptafluoro-1- (phenyl) -butanone oxime-O- (10-camphoryl) Sulfonate, 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-2-naphthyl-ethanone Shim-O-methylsulfonate, 2,2,2-trifluoro-1- [4-benzylphenyl] -ethanone oxime-O-methylsulfonate, 2,2,2-trifluoro-1- [4- (Phenyl-1,4-dioxa-but-1-yl) phenyl] -ethanone oxime-O-methyl sulfonate, 2,2,2-trifluoro-1-naphthyl-ethanone oxime-O-propyl sulfonate 2,2,2-trifluoro-2-naphthyl-ethanone oxime-O-propyl sulfonate, 2,2,2-trifluoro-1- [4-benzylphenyl] -ethanone oxime-O-propyl sulfone Narate, 2,2,2-trifluoro-1- [4-methylsulfonylphenyl] -ethanone oxime-O-propylsulfonate, 1,3-bis [1- (4-phenyl) Enoxyphenyl) -2,2,2-trifluoroethanone oxime-O-sulfonyl] phenyl, 2,2,2-trifluoro-1- [4-methylsulfonyloxyphenyl] -ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [4-methylcarbonyloxyphenyl] -ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [6H, 7H-5,8- Dioxonaphth-2-yl] -ethanone oxime-O-propyl sulfonate, 2,2,2-trifluoro-1- [4-methoxycarbonylmethoxyphenyl] -ethanone oxime-O-propyl sulfonate, 2,2 , 2-Trifluoro-1- [4- (methoxycarbonyl)-(4-amino-1-oxa-pent-1-yl) -fur Nyl] -ethanone oxime-O-propyl sulfonate, 2,2,2-trifluoro-1- [3,5-dimethyl-4-ethoxyphenyl] -ethanone oxime-O-propyl sulfonate, 2,2 , 2-trifluoro-1- [4-benzyloxyphenyl] -ethanone oxime-O-propylsulfonate, 2,2,2-trifluoro-1- [2-thiophenyl] -ethanone oxime-O-propyl Sulfonate and 2,2,2-trifluoro-1- [1-dioxa-thiophen-2-yl] -ethanone oxime-O-propyl sulfonate, 2,2,2-trifluoro-1- (4 -(3- (4- (2,2,2-trifluoro-1- (trifluoromethanesulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) Tanone oxime (trifluoromethanesulfonate), 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (1-propanesulfonyloxyimino) -ethyl) -Phenoxy) -propoxy) -phenyl) ethanone oxime (1-propanesulfonate), 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1) -(1-butanesulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) ethanone oxime (1-butanesulfonate) and the like, and 2,2,2 described in US Pat. No. 6,916,591 -Trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (4- (4-methylphenylsulfonyloxy) phenylsulfo Nyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) ethanone oxime (4- (4-methylphenylsulfonyloxy) phenylsulfonate), 2,2,2-trifluoro-1- (4- (3- ( 4- (2,2,2-trifluoro-1- (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenylsulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) eta Nonoxime (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) phenylsulfonate) and the like.

  JP-A-9-95479, JP-A-9-230588, or oxime sulfonate α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (p-chlorobenzenesulfonyloxyimino)- Phenylacetonitrile, α- (4-nitrobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -4-chlorophenyl Acetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (benzene Sulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile, α- (4-dodecylbenzenesulfonyl) Oxyimino) -phenylacetonitrile, α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxyimino ) -3-thienylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- Isopropylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (isopropylsulfonyloxy) Imino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile, and the like.

（上式中、Ｒ^S1は置換又は非置換の炭素数１〜１０のハロアルキルスルホニル、又はハロベンゼンスルホニル基を表す。Ｒ^S2は炭素数１〜１１のハロアルキル基を表す。Ａｒ^S1は置換又は非置換の芳香族基又はヘテロ芳香族基を表す。） Examples thereof include oxime sulfonates represented by the following formula (for example, specific examples are described in WO2004 / 074242).

(In the above formula, R ^S1 represents a substituted or unsubstituted haloalkylsulfonyl having 1 to 10 carbon atoms or a halobenzenesulfonyl group. R ^S2 represents a haloalkyl group having 1 to 11 carbon atoms. Ar ^S1 represents substituted or non-substituted. Represents a substituted aromatic group or heteroaromatic group.)

  Specifically, 2- [2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) -pentyl] -fluorene, 2- [2,2, 3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) -butyl] -fluorene, 2- [2,2,3,3,4,4,5,5,6,6- Decafluoro-1- (nonafluorobutylsulfonyloxyimino) -hexyl] -fluorene, 2- [2,2,3,3,4,4,5,5-octafluoro-1- (nonafluorobutylsulfonyloxyimino) ) -Pentyl] -4-biphenyl, 2- [2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) -butyl] -4-biphenyl, 2- [2, 2, 3, 3 4,4,5,5,6,6- deca fluoro-1- (nonafluorobutylsulfonyloxy-imino) - hexyl] -4-biphenyl, and the like.

  Further, as bisoxime sulfonate, compounds described in JP-A-9-208554, particularly bis (α- (4-toluenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (benzenesulfonyloxy) imino)- p-phenylenediacetonitrile, bis (α- (methanesulfonyloxy) imino) -p-phenylenediacetonitrilebis (α- (butanesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (10-camphorsulfonyl) Oxy) imino) -p-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -p-phenylenediacetonitrile, Screw (α- (4-Methoxybenzenesulfonyloxy) imino) -p-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (benzenesulfonyloxy) imino) -m -Phenylenediacetonitrile, bis (α- (methanesulfonyloxy) imino) -m-phenylenediacetonitrilebis (α- (butanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (10-camphorsulfonyloxy) ) Imino) -m-phenylenediacetonitrile, bis (α- (4-toluenesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (α- (trifluoromethanesulfonyloxy) imino) -m-phenylenediacetonitrile, bis (Α- (4-methoxybenzenesulfonyloxy) imino) -m-phenylenediacetonitrile and the like.

  Among them, preferred photoacid generators are sulfonium salts, bissulfonyldiazomethane, N-sulfonyloxyimide, oxime-O-sulfonate, and glyoxime derivatives. More preferably used photoacid generators are sulfonium salts, bissulfonyldiazomethanes, N-sulfonyloxyimides, and oxime-O-sulfonates. Specifically, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium camphorsulfonate, triphenylsulfonium pentafluorobenzenesulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium 4- (4′-toluenesulfonyloxy) benzenesulfonate, Triphenylsulfonium-2,4,6-triisopropylbenzenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium p-toluenesulfonate, 4-tert-butoxyphenyldiphenylsulfonium camphorsulfonate, 4-tert-butoxyphenyldiphenylsulfonium 4- ( 4′-Toluenesulfonyloxy) benzenesulfonate, tris (4-methyl) Phenyl) sulfonium, camphorsulfonate, tris (4-tertbutylphenyl) sulfonium camphorsulfonate, 4-tert-butylphenyldiphenylsulfonium camphorsulfonate, 4-tert-butylphenyldiphenylsulfonium nonafluoro-1-butanesulfonate, 4-tert- Butylphenyldiphenylsulfonium pentafluoroethyl perfluorocyclohexanesulfonate, 4-tert-butylphenyldiphenylsulfonium perfluoro-1-octanesulfonate, triphenylsulfonium 1,1-difluoro-2-naphthyl-ethanesulfonate, triphenylsulfonium 1,1 , 2,2-Tetrafluoro-2- (norbornan-2-yl) ethanesulfonate Bis (tert-butylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (2,4-dimethylphenylsulfonyl) diazomethane, bis (4-n-hexyloxy) phenylsulfonyl) diazomethane, bis (2-methyl- 4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (2,5-dimethyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (3,5-dimethyl-4- (n-hexyloxy) Phenylsulfonyl) diazomethane, bis (2-methyl-5-isopropyl-4- (n-hexyloxy) phenylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, N-camphorsulfonyloxy-5-norbornene- 2,3-dicarboxylic imide, Np-toluenesulfonyloxy-5-norbornene-2,3-dicarboxylic imide, 2- [2,2,3,3,4,4,5,5-octafluoro- 1- (nonafluorobutylsulfonyloxyimino) -pentyl] -fluorene, 2- [2,2,3,3,4,4-pentafluoro-1- (nonafluorobutylsulfonyloxyimino) -butyl] -fluorene, 2- [2,2,3,3,4,4,5,5,6,6-decafluoro-1- (nonafluorobutylsulfonyloxyimino) -hexyl] -fluorene and the like.

  The amount of the photoacid generator added to the chemically amplified resist material in the pattern forming method of the present invention may be any, but is 0.1 to 20 parts by weight, preferably 0. 1 to 10 parts by mass. When the photoacid generator is 20 parts by mass or less, the transmittance of the photoresist film is sufficiently large, and there is little possibility that the resolution performance is deteriorated. The photoacid generators can be used alone or in combination of two or more. Further, a photoacid generator having a low transmittance at the exposure wavelength can be used, and the transmittance in the resist film can be controlled by the amount added.

Moreover, you may add the compound (acid propagation compound) which decomposes | disassembles with an acid and generate | occur | produces an acid to the resist material in this invention pattern formation method.
These compounds are described in J. Org. Photopolym. Sci. and Tech. , 8.43-44, 45-46 (1995), J. Am. Photopolym. Sci. and Tech. , 9.29-30 (1996).

  Examples of acid proliferating compounds include, but are not limited to, tert-butyl 2-methyl 2-tosyloxymethyl acetoacetate, 2-phenyl 2- (2-tosyloxyethyl) 1,3-dioxolane, and the like. is not. Of the known photoacid generators, compounds that are inferior in stability, particularly thermal stability, often exhibit the properties of acid-proliferating compounds.

  The addition amount of the acid multiplication compound in the resist material in the pattern forming method of the present invention is 2 parts by mass or less, preferably 1 part by mass or less with respect to 100 parts by mass of the base resin in the resist material. If it is 2 parts by mass or less, diffusion is controlled, and there is little possibility that degradation of resolution and pattern shape will occur.

  The resist material in the pattern forming method of the present invention can further contain any one or more of an organic solvent, a basic compound, and a surfactant.

  The organic solvent used in the resist material in the pattern forming method of the present invention may be any organic solvent that can dissolve the base resin, acid generator, other additives, and the like. Examples of such organic solvents include ketones such as cyclohexanone and methyl-2-n-amyl ketone, 3-methoxybutanol, 3-methyl-3-methoxybutanol, 1-methoxy-2-propanol, 1-ethoxy- Alcohols such as 2-propanol, propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, propylene glycol monomethyl ether acetate, propylene glycol mono Ethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, methyl 3-methoxypropionate, 3-ethoxy Examples thereof include esters such as ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. It can be used in a mixed manner, but is not limited thereto. In the resist for the pattern formation method of the present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate and the like, which have the most excellent solubility of the acid generator in the resist component, and A mixed solvent is preferably used.

  The amount of the organic solvent used is preferably 200 to 3,000 parts by mass, particularly 400 to 2,500 parts by mass with respect to 100 parts by mass of the base resin.

  Furthermore, the resist material in the pattern forming method of the present invention may contain one or more nitrogen-containing organic compounds as basic compounds.

  As the nitrogen-containing organic compound, a compound capable of suppressing the diffusion rate when the acid generated from the acid generator diffuses into the resist film is suitable. By compounding nitrogen-containing organic compounds, the acid diffusion rate in the resist film is suppressed and resolution is improved. Sensitivity changes after exposure are suppressed, and substrate and environment dependence is reduced. Profiles and the like can be improved.

  Such nitrogen-containing organic compounds include primary, secondary and tertiary aliphatic amines, hybrid amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxy group, sulfonyl Nitrogen-containing compounds having a group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amides, imides, carbamates and the like.

  Specifically, primary aliphatic amines include ammonia, methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, tert- Amylamine, cyclopentylamine, hexylamine, cyclohexylamine, heptylamine, octylamine, nonylamine, decylamine, dodecylamine, cetylamine, methylenediamine, ethylenediamine, tetraethylenepentamine, etc. are exemplified as secondary aliphatic amines. Dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, dipentylamine, disi Lopentylamine, dihexylamine, dicyclohexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, didodecylamine, dicetylamine, N, N-dimethylmethylenediamine, N, N-dimethylethylenediamine, N, N-dimethyltetraethylenepenta The tertiary aliphatic amines are exemplified by trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, and tripentylamine. , Tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, Examples include cetylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyltetraethylenepentamine and the like. Is done.

  Examples of hybrid amines include dimethylethylamine, methylethylpropylamine, benzylamine, phenethylamine, and benzyldimethylamine. Specific examples of aromatic amines and heterocyclic amines include aniline derivatives (eg, aniline, N-methylaniline, N-ethylaniline, N-propylaniline, N, N-dimethylaniline, 2-methylaniline, 3- Methylaniline, 4-methylaniline, ethylaniline, propylaniline, trimethylaniline, 2-nitroaniline, 3-nitroaniline, 4-nitroaniline, 2,4-dinitroaniline, 2,6-dinitroaniline, 3,5- Dinitroaniline, N, N-dimethyltoluidine, etc.), diphenyl (p-tolyl) amine, methyldiphenylamine, triphenylamine, phenylenediamine, naphthylamine, diaminonaphthalene, pyrrole derivatives (eg pyrrole, 2H-pyrrole, 1-methylpyrrole, 2,4-dim Lupyrrole, 2,5-dimethylpyrrole, N-methylpyrrole, etc.), oxazole derivatives (eg oxazole, isoxazole etc.), thiazole derivatives (eg thiazole, isothiazole etc.), imidazole derivatives (eg imidazole, 4-methylimidazole, 4 -Methyl-2-phenylimidazole, etc.), pyrazole derivatives, furazane derivatives, pyrroline derivatives (eg pyrroline, 2-methyl-1-pyrroline etc.), pyrrolidine derivatives (eg pyrrolidine, N-methylpyrrolidine, pyrrolidinone, N-methylpyrrolidone etc.) ), Imidazoline derivatives, imidazolidine derivatives, pyridine derivatives (eg pyridine, methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethyl) Lysine, trimethylpyridine, triethylpyridine, phenylpyridine, 3-methyl-2-phenylpyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 4-pyrrolidinopyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine, etc.), pyridazine derivatives, pyrimidine derivatives, pyrazine derivatives, pyrazoline derivatives, pyrazolidine derivatives, piperidine derivatives, piperazine derivatives, morpholine derivatives, indole derivatives, isoindole derivatives, 1H- Indazole derivatives, indoline derivatives, quinoline derivatives (eg, quinoline, 3-quinolinecarbonitrile, etc.), isoquinoline derivatives, cinnoline derivatives, quinazoli Derivatives, quinoxaline derivatives, phthalazine derivatives, purine derivatives, pteridine derivatives, carbazole derivatives, phenanthridine derivatives, acridine derivatives, phenazine derivatives, 1,10-phenanthroline derivatives, adenine derivatives, adenosine derivatives, guanine derivatives, guanosine derivatives, uracil derivatives And uridine derivatives.

  Furthermore, examples of the nitrogen-containing compound having a carboxy group include aminobenzoic acid, indolecarboxylic acid, amino acid derivatives (for example, nicotinic acid, alanine, arginine, aspartic acid, glutamic acid, glycine, histidine, isoleucine, glycylleucine, leucine, methionine. , Phenylalanine, threonine, lysine, 3-aminopyrazine-2-carboxylic acid, methoxyalanine) and the like, and examples of the nitrogen-containing compound having a sulfonyl group include 3-pyridinesulfonic acid, pyridinium p-toluenesulfonate, and the like. Nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, and alcoholic nitrogen-containing compounds include 2-hydroxypyridine, aminocresol, 2,4-quinolinediol, and 3-indolemethanol. Drate, monoethanolamine, diethanolamine, triethanolamine, N-ethyldiethanolamine, N, N-diethylethanolamine, triisopropanolamine, 2,2'-iminodiethanol, 2-aminoethanol, 3-amino-1-propanol 4-amino-1-butanol, 4- (2-hydroxyethyl) morpholine, 2- (2-hydroxyethyl) pyridine, 1- (2-hydroxyethyl) piperazine, 1- [2- (2-hydroxyethoxy) Ethyl] piperazine, piperidineethanol, 1- (2-hydroxyethyl) pyrrolidine, 1- (2-hydroxyethyl) -2-pyrrolidinone, 3-piperidino-1,2-propanediol, 3-pyrrolidino-1,2-propane Diol, 8-hydroxyuroli , 3-cuincridinol, 3-tropanol, 1-methyl-2-pyrrolidineethanol, 1-aziridineethanol, N- (2-hydroxyethyl) phthalimide, N- (2-hydroxyethyl) isonicotinamide, etc. Illustrated. Examples of amides include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, 1-cyclohexylpyrrolidone and the like. Examples of imides include phthalimide, succinimide, maleimide and the like. Examples of carbamates include Nt-butoxycarbonyl-N, N-dicyclohexylamine, Nt-butoxycarbonylbenzimidazole, oxazolidinone, and the like.

Furthermore, the nitrogen-containing organic compound shown by the following general formula (B) -1 is illustrated.
N (X) _n (Y) _3-n (B) -1
(In the above formula, n = 1, 2 or 3. The side chain X may be the same or different and can be represented by the following general formula (X1), (X2) or (X3). Side chain Y Represents the same or different hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs are bonded to form a ring. You may do it.)

In the general formulas (X1) to (X3), R ³⁰⁰ , R ³⁰² and R ³⁰⁵ are linear or branched alkylene groups having 1 to 4 carbon atoms, and R ³⁰¹ and R ³⁰⁴ are hydrogen atoms or carbon atoms. It is a linear, branched or cyclic alkyl group of 1 to 20, and may contain one or a plurality of hydroxy groups, ether groups, ester groups and lactone rings.

R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, R ³⁰⁶ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and a hydroxy group , An ether group, an ester group, or a lactone ring may be contained.

  Specific examples of the compound represented by the general formula (B) -1 include tris (2-methoxymethoxyethyl) amine, tris {2- (2-methoxyethoxy) ethyl} amine, and tris {2- (2- Methoxyethoxymethoxy) ethyl} amine, tris {2- (1-methoxyethoxy) ethyl} amine, tris {2- (1-ethoxyethoxy) ethyl} amine, tris {2- (1-ethoxypropoxy) ethyl} amine, Tris [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] amine, 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo [8.8.8] hexacosane, 4,7 , 13,18-tetraoxa-1,10-diazabicyclo [8.5.5] eicosane, 1,4,10,13-tetraoxa-7,16-di Zabicyclooctadecane, 1-aza-12-crown-4, 1-aza-15-crown-5, 1-aza-18-crown-6, tris (2-formyloxyethyl) amine, tris (2-acetoxyethyl) ) Amine, tris (2-propionyloxyethyl) amine, tris (2-butyryloxyethyl) amine, tris (2-isobutyryloxyethyl) amine, tris (2-valeryloxyethyl) amine, tris (2 -Pivaloyloxyethyl) amine, N, N-bis (2-acetoxyethyl) 2- (acetoxyacetoxy) ethylamine, tris (2-methoxycarbonyloxyethyl) amine, tris (2-tert-butoxycarbonyloxyethyl) Amine, tris [2- (2-oxopropoxy) ethyl] amine, tris 2- (methoxycarbonylmethyl) oxyethyl] amine, tris [2- (tert-butoxycarbonylmethyloxy) ethyl] amine, tris [2- (cyclohexyloxycarbonylmethyloxy) ethyl] amine, tris (2-methoxycarbonylethyl) Amine, tris (2-ethoxycarbonylethyl) amine, N, N-bis (2-hydroxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (methoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (ethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2 -(2-methoxyethoxycarboni ) Ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-methoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-hydroxyethoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (2-acetoxyethoxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2 -Acetoxyethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2 -(2-oxopropoxycarbonyl) ethylamine, N, N- (2-hydroxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- (tetrahydrofurfuryloxycarbonyl) ethylamine, N, N-bis (2-hydroxyethyl) ) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-acetoxyethyl) 2-[(2-oxotetrahydrofuran-3-yl) oxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (4-hydroxybutoxycarbonyl) ethylamine, N, N-bis (2-formyloxyethyl) 2- (4-formyloxybutoxycarbonyl) ethylamine, N, N-bis ( 2-formyloxyethyl) 2- (2-formyloxy) Ethoxycarbonyl) ethylamine, N, N-bis (2-methoxyethyl) 2- (methoxycarbonyl) ethylamine, N- (2-hydroxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-acetoxy) Ethyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-hydroxyethyl) bis [2- (ethoxycarbonyl) ethyl] amine, N- (2-acetoxyethyl) bis [2- (ethoxycarbonyl) Ethyl] amine, N- (3-hydroxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (3-acetoxy-1-propyl) bis [2- (methoxycarbonyl) ethyl] amine, N- (2-methoxyethyl) bis [2- (methoxycarbonyl) ethyl] amine, N-butylbi [2- (methoxycarbonyl) ethyl] amine, N-butylbis [2- (2-methoxyethoxycarbonyl) ethyl] amine, N-methylbis (2-acetoxyethyl) amine, N-ethylbis (2-acetoxyethyl) amine N-methylbis (2-pivaloyloxyethyl) amine, N-ethylbis [2- (methoxycarbonyloxy) ethyl] amine, N-ethylbis [2- (tert-butoxycarbonyloxy) ethyl] amine, tris (methoxy Examples include carbonylmethyl) amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, and β- (diethylamino) -δ-valerolactone.

（上式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドをいずれか１個あるいは複数個含んでいてもよい。） Furthermore, the nitrogen-containing organic compound which has a cyclic structure shown by the following general formula (B) -2 is illustrated.

(In the above formula, X is as described above, R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms, and any one or more of a carbonyl group, an ether group, an ester group, and a sulfide. May be included.)

  Specific examples of the general formula (B) -2 include 1- [2- (methoxymethoxy) ethyl] pyrrolidine, 1- [2- (methoxymethoxy) ethyl] piperidine, 4- [2- (methoxymethoxy) ethyl. ] Morpholine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] pyrrolidine, 1- [2-[(2-methoxyethoxy) methoxy] ethyl] piperidine, 4- [2-[(2-methoxyethoxy) ) Methoxy] ethyl] morpholine, 2- (1-pyrrolidinyl) ethyl acetate, 2-piperidinoethyl acetate, 2-morpholinoethyl acetate, 2- (1-pyrrolidinyl) ethyl formate, 2-piperidinoethyl propionate, 2-morpholinoethyl acetoxyacetate , 2- (1-pyrrolidinyl) ethyl methoxyacetate, 4- [2- (methoxycarbonyloxy) ethyl ] Morpholine, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-pi Methyl peridinopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidino Methoxycarbonylmethyl propionate, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3- Morpholinopropionic acid tetrahydrofur Furyl, glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-pi Cyclohexyl peridinopropionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, Methyl thiomorpholinoacetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate, 2-morpholinoethyl 2-methoxyacetate, 2-morpholinoethyl 2- (2-methoxyethoxy) acetate, 2- [2- (2-methoxy Ethoxy) ethoxy] acetic acid 2-mo Ruphorinoethyl, 2-morpholinoethyl hexanoate, 2-morpholinoethyl octoate, 2-morpholinoethyl decanoate, 2-morpholinoethyl laurate, 2-morpholinoethyl myristate, 2-morpholinoethyl palmitate, 2-morpholinoethyl stearate Is exemplified.

  Furthermore, the nitrogen-containing organic compound containing the cyano group represented by the following general formula (B) -3-(B) -6 is illustrated.

（上式中、Ｘ、Ｒ³⁰⁷、ｎは前述の通り、Ｒ³⁰⁸、Ｒ³⁰⁹は同一又は異種の炭素数１〜４の直鎖状又は分岐状のアルキレン基である。）

(In the above formula, X, R ³⁰⁷ and n are as described above, and R ³⁰⁸ and R ³⁰⁹ are the same or different linear or branched alkylene groups having 1 to 4 carbon atoms.)

  Specific examples of the nitrogen-containing organic compound containing a cyano group represented by the general formulas (B) -3 to (B) -6 include 3- (diethylamino) propiononitrile and N, N-bis (2-hydroxyethyl). ) -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N-bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- ( Methyl 2-methoxyethyl) -3-aminopropionate, methyl N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetate) Xylethyl) -N- (2-cyanoethyl) -3-aminopropionate methyl, N- (2-cyanoethyl) -N-ethyl-3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2- Hydroxyethyl) -3-aminopropiononitrile, N- (2-acetoxyethyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-formyloxy Ethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2-methoxyethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- [2- (methoxymethoxy) ) Ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-hydroxy-1-propyl) -3-aminopropiono Tolyl, N- (3-acetoxy-1-propyl) -N- (2-cyanoethyl) -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (3-formyloxy-1-propyl)- 3-aminopropiononitrile, N- (2-cyanoethyl) -N-tetrahydrofurfuryl-3-aminopropiononitrile, N, N-bis (2-cyanoethyl) -3-aminopropiononitrile, diethylaminoacetonitrile, N , N-bis (2-hydroxyethyl) aminoacetonitrile, N, N-bis (2-acetoxyethyl) aminoacetonitrile, N, N-bis (2-formyloxyethyl) aminoacetonitrile, N, N-bis (2- Methoxyethyl) aminoacetonitrile, N, N-bis [2- (methoxymethoxy) ethyl] aminoa Cetonitrile, methyl N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate, methyl N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate, N- (2-acetoxyethyl) -N-cyanomethyl-3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) aminoacetonitrile, N- (2-acetoxyethyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (2-formyloxyethyl) aminoacetonitrile, N-cyanomethyl-N- (2-methoxyethyl) aminoacetonitrile, N-cyanomethyl-N- [2- (methoxymethoxy) ethyl] aminoacetonitrile, N- (cyanomethyl) -N -(3-Hydroxy-1-propyl) amino Cetonitrile, N- (3-acetoxy-1-propyl) -N- (cyanomethyl) aminoacetonitrile, N-cyanomethyl-N- (3-formyloxy-1-propyl) aminoacetonitrile, N, N-bis (cyanomethyl) amino Acetonitrile, 1-pyrrolidinepropiononitrile, 1-piperidinepropiononitrile, 4-morpholinepropiononitrile, 1-pyrrolidineacetonitrile, 1-piperidineacetonitrile, 4-morpholineacetonitrile, cyanomethyl 3-diethylaminopropionate, N, N-bis Cyanomethyl (2-hydroxyethyl) -3-aminopropionate, N, N-bis (2-acetoxyethyl) -3-aminopropionate cyanomethyl, N, N-bis (2-formyloxyethyl) -3-aminopro Cyanomethyl onate, cyanomethyl N, N-bis (2-methoxyethyl) -3-aminopropionate, cyanomethyl N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionate, 3-diethylaminopropionic acid (2-cyanoethyl), N, N-bis (2-hydroxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-acetoxyethyl) -3-aminopropionic acid (2-cyanoethyl) ), N, N-bis (2-formyloxyethyl) -3-aminopropionic acid (2-cyanoethyl), N, N-bis (2-methoxyethyl) -3-aminopropionic acid (2-cyanoethyl), N , N-bis [2- (methoxymethoxy) ethyl] -3-aminopropionic acid (2-cyanoethyl), 1-pyrrolidine Cyanomethyl lopionate, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholine propionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholine propionic acid (2-cyanoethyl) Is exemplified.

（上式中、Ｒ³¹⁰は炭素数２〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としては水酸基、カルボニル基、エステル基、エーテル基、スルフィド基、カーボネート基、シアノ基、アセタール基のいずれかを１個あるいは複数個含む。Ｒ³¹¹、Ｒ³¹²、Ｒ³¹³は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、アリール基又はアラルキル基である。） Furthermore, a nitrogen-containing organic compound having an imidazole skeleton and a polar functional group represented by the following general formula (B) -7 is exemplified.

(In the above formula, R ³¹⁰ is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, and the polar functional group includes a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide. 1 or a plurality of any of a group, carbonate group, cyano group, and acetal group, wherein R ³¹¹ , R ³¹² and R ³¹³ are a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. An aryl group or an aralkyl group.)

（上式中、Ｒ³¹⁴は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、アリール基、又はアラルキル基である。Ｒ³¹⁵は炭素数１〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としてエステル基、アセタール基、シアノ基のいずれかを一つ以上含み、その他に水酸基、カルボニル基、エーテル基、スルフィド基、カーボネート基のいずれかを一つ以上含んでいてもよい。） Furthermore, a nitrogen-containing organic compound having a benzimidazole skeleton and a polar functional group represented by the following general formula (B) -8 is exemplified.

(In the above formula, R ³¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group, aryl group, or aralkyl group having 1 to 10 carbon atoms. R ³¹⁵ is a linear structure having 1 to 20 carbon atoms. , An alkyl group having a branched or cyclic polar functional group, which includes at least one of an ester group, an acetal group, and a cyano group as a polar functional group, and in addition, a hydroxyl group, a carbonyl group, an ether group, a sulfide group, (One or more carbonate groups may be contained.)

（上式中、Ａは窒素原子又は≡Ｃ−Ｒ³²²である。Ｂは窒素原子又は≡Ｃ−Ｒ³²³である。Ｒ³¹⁶は炭素数２〜２０の直鎖状、分岐状又は環状の極性官能基を有するアルキル基であり、極性官能基としては水酸基、カルボニル基、エステル基、エーテル基、スルフィド基、カーボネート基、シアノ基又はアセタール基を一つ以上含む。Ｒ³¹⁷、Ｒ³¹⁸、Ｒ³¹⁹、Ｒ³²⁰は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、又はアリール基であるか、又はＲ³¹⁷とＲ³¹⁸、Ｒ³¹⁹とＲ³²⁰はそれぞれ結合してこれらが結合する炭素原子と共にベンゼン環、ナフタレン環あるいはピリジン環を形成してもよい。Ｒ³²¹は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、又はアリール基である。Ｒ³²²、Ｒ³²³は水素原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、又はアリール基である。Ｒ³²¹とＲ³²³は結合してこれらが結合する炭素原子と共にベンゼン環又はナフタレン環を形成してもよい。） Furthermore, the nitrogen-containing heterocyclic compound which has a polar functional group shown by the following general formula (B) -9 and (B) -10 is illustrated.

(In the above formula, A is a nitrogen atom or ≡C—R ^322. B is a nitrogen atom or ≡C—R ^323. R ³¹⁶ is a linear, branched or cyclic polarity having 2 to 20 carbon atoms. An alkyl group having a functional group, and the polar functional group includes one or more of a hydroxyl group, a carbonyl group, an ester group, an ether group, a sulfide group, a carbonate group, a cyano group, or an acetal group R ³¹⁷ , R ³¹⁸ , R ³¹⁹ R ³²⁰ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group, or R ³¹⁷ and R ³¹⁸ , R ³¹⁹ and R ³²⁰ are bonded to each other. A benzene ring, a naphthalene ring or a pyridine ring may be formed together with the carbon atom to which R is bonded, and R ³²¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group. R ³²² and R ³²³ are hydrogen atom and carbon A linear, branched or cyclic alkyl group or an aryl group having a number of 1 to 10. R ³²¹ and R ³²³ may be bonded to form a benzene ring or a naphthalene ring together with the carbon atom to which they are bonded. .)

（上式中、Ｒ³²⁴は炭素数６〜２０のアリール基又は炭素数４〜２０のヘテロ芳香族基であって、水素原子の一部又は全部が、ハロゲン原子、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基、炭素数６〜２０のアリール基、炭素数７〜２０のアラルキル基、炭素数１〜１０のアルコキシ基、炭素数１〜１０のアシルオキシ基、又は、炭素数１〜１０のアルキルチオ基で置換されていてもよい。Ｒ³²⁵はＣＯ₂Ｒ³²⁶、ＯＲ³²⁷又はシアノ基である。Ｒ³²⁶は一部のメチレン基が酸素原子で置換されていてもよい炭素数１〜１０のアルキル基である。Ｒ³²⁷は一部のメチレン基が酸素原子で置換されていてもよい炭素数１〜１０のアルキル基又はアシル基である。Ｒ³²⁸は単結合、メチレン基、エチレン基、硫黄原子又は−Ｏ（ＣＨ₂ＣＨ₂Ｏ）_n−基である。ｎ＝０，１，２，３又は４である。Ｒ³²⁹は水素原子、メチル基、エチル基又はフェニル基である。Ｘは窒素原子又はＣＲ³³⁰である。Ｙは窒素原子又はＣＲ³³¹である。Ｚは窒素原子又はＣＲ³³²である。Ｒ³³⁰、Ｒ³³¹、Ｒ³³²はそれぞれ独立に水素原子、メチル基又はフェニル基であるか、あるいはＲ³³⁰とＲ³³¹又はＲ³³¹とＲ³³²が結合してこれらが結合する炭素原子と共に炭素数６〜２０の芳香環又は炭素数２〜２０のヘテロ芳香環を形成してもよい。） Furthermore, the nitrogen-containing organic compound which has an aromatic carboxylic acid ester structure shown by the following general formula (B) -11- (B) -14 is illustrated.

(In the above formula, R ³²⁴ is an aryl group having 6 to 20 carbon atoms or a heteroaromatic group having 4 to 20 carbon atoms, and a part or all of the hydrogen atoms are halogen atoms, straight carbon atoms having 1 to 20 carbon atoms. A linear, branched or cyclic alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an acyloxy group having 1 to 10 carbon atoms, or carbon R ³²⁵ is CO ₂ R ³²⁶ , OR ³²⁷ or cyano group R ³²⁶ is a carbon in which some methylene groups may be substituted with oxygen atoms R ³²⁷ is an alkyl group or acyl group having 1 to 10 carbon atoms in which a part of the methylene group may be substituted with an oxygen atom, R ³²⁸ is a single bond or a methylene group. , an ethylene group, a sulfur atom or -O (CH ₂ CH ₂ O _n - .R ³²⁹ is .n = 0, 1, 2, 3 or 4 is a radical is a hydrogen atom, a methyl group, an ethyl group or a phenyl group .X is a nitrogen atom or CR ³³⁰ .Y nitrogen An atom or CR ^331. Z is a nitrogen atom or CR ^332. R ³³⁰ , R ³³¹ and R ³³² are each independently a hydrogen atom, a methyl group or a phenyl group, or R ³³⁰ and R ³³¹ or R ^331. And R ³³² may be bonded together to form a C 6-20 aromatic ring or a C 2-20 heteroaromatic ring together with the carbon atom to which they are bonded.

（上式中、Ｒ³³³は水素、又は炭素数１〜１０の直鎖状、分枝状又は環状のアルキル基である。Ｒ³³⁴及びＲ³³⁵はそれぞれ独立に、エーテル、カルボニル、エステル、アルコール、スルフィド、ニトリル、アミン、イミン、アミドなどの極性官能基を一つ又は複数含んでいてもよい炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、又は炭素数７〜２０のアラルキル基であって、水素原子の一部がハロゲン原子で置換されていてもよい。Ｒ³³⁴とＲ³³⁵は互いに結合してこれらが結合する炭素原子と共に炭素数２〜２０のヘテロ環又はヘテロ芳香環を形成してもよい。） Furthermore, a nitrogen-containing organic compound having a 7-oxanorbornane-2-carboxylic acid ester structure represented by the following general formula (B) -15 is exemplified.

(In the above formula, R ³³³ is hydrogen or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. R ³³⁴ and R ³³⁵ are each independently an ether, carbonyl, ester, alcohol, C1-C20 alkyl group, C6-C20 aryl group, or C7-C20 aralkyl which may contain one or more polar functional groups such as sulfide, nitrile, amine, imine and amide A part of hydrogen atoms may be substituted with a halogen atom, and R ³³⁴ and R ³³⁵ are bonded to each other and together with the carbon atom to which they are bonded, a C 2-20 heterocycle or heteroaromatic ring May be formed.)

  In addition, the compounding quantity of a nitrogen-containing organic compound is 0.001-2 mass parts with respect to 100 mass parts of base resins, Especially 0.01-1 mass part is suitable. If the amount is 0.001 part by mass or more, a sufficient blending effect is obtained, and if it is 2 parts by mass or less, the sensitivity is less likely to decrease.

  To the resist material in the pattern forming method of the present invention, a surfactant conventionally used for improving the coatability as an optional component can be added in addition to the above components. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  Here, the surfactant is preferably nonionic, such as perfluoroalkyl polyoxyethylene ethanol, fluorinated alkyl ester, perfluoroalkylamine oxide, perfluoroalkyl EO adduct, fluorine-containing organosiloxane compound, and the like. Can be mentioned. For example, Florard “FC-430”, “FC-431” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145”, “KH-10”, “KH-20”, “ KH-30 "," KH-40 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Mega For example, “F-8151” (manufactured by Dainippon Ink Industries, Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Limited), “KH-20”, “KH-30” (all manufactured by Asahi Glass Co., Ltd.), “X-70-093” (Shin-Etsu Chemical Co., Ltd.) Product).

  If necessary, the resist material in the pattern forming method of the present invention may further contain other components such as a dissolution controller, a carboxylic acid compound, and an acetylene alcohol derivative as optional components. In addition, the addition amount of an arbitrary component can be made into a normal amount in the range which does not inhibit the effect of this invention.

  The dissolution control agent that can be added to the resist material of the pattern forming method of the present invention has a weight average molecular weight of 100 to 1,000, preferably 150 to 800, and has two or more phenolic hydroxyl groups in the molecule. A compound in which the hydrogen atom of the phenolic hydroxyl group of the compound is substituted with an acid labile group in an average of 0 to 100 mol% as a whole or a hydrogen atom of the carboxy group of a compound having a carboxy group in the molecule is an acid labile group Thus, the compound substituted at a ratio of 50 to 100 mol% on average as a whole is blended.

  The substitution rate of the hydrogen atom of the phenolic hydroxyl group by an acid labile group is on average 0 mol% or more, preferably 30 mol% or more of the entire phenolic hydroxyl group, and the upper limit is 100 mol%, more preferably 80 mol%. Mol%. The substitution rate of the hydrogen atom of the carboxy group by an acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.

  In this case, as the compound having two or more phenolic hydroxyl groups or the compound having a carboxy group, those represented by the following formulas (D1) to (D14) are preferable.

In the above formula, R ²⁰¹ and R ²⁰² each represent a hydrogen atom, or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, such as a hydrogen atom, a methyl group, an ethyl group, or a butyl group. , A propyl group, an ethynyl group, and a cyclohexyl group.
R ²⁰³ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or — (R ²⁰⁷ ) _h COOH (wherein R ²⁰⁷ is a linear chain having 1 to 10 carbon atoms) And h represents 0 or 1), and examples thereof include those similar to R ²⁰¹ and R ²⁰² , or —COOH and —CH ₂ COOH.
R ²⁰⁴ represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, such as an ethylene group, a phenylene group, A carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, etc. are mentioned.
R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and examples thereof include a methylene group or the same as R ^204. It is done.
R ²⁰⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or a naphthyl group each substituted with a hydroxyl group. For example, a hydrogen atom, a methyl group, an ethyl group Group, butyl group, propyl group, ethynyl group, cyclohexyl group, phenyl group substituted with hydroxyl group, naphthyl group, etc., respectively.
R ²⁰⁸ represents a hydrogen atom or a hydroxyl group.

  j is an integer of 0-5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and at least 1 in each phenyl skeleton The number has two hydroxyl groups. α is a number that makes the weight average molecular weight of the compounds of formulas (D8) and (D9) 100 to 1,000.

  The acid labile group of the dissolution control agent can be variously used. Specifically, the groups represented by the general formulas (L1) to (L4), the tertiary alkyl group having 4 to 20 carbon atoms, and each alkyl Examples thereof include a trialkylsilyl group having 1 to 6 carbon atoms and an oxoalkyl group having 4 to 20 carbon atoms. Specific examples of each group are the same as described above.

  The compounding amount of the dissolution control agent is 0 to 50 parts by mass, preferably 0 to 40 parts by mass, more preferably 0 to 30 parts by mass with respect to 100 parts by mass of the base resin in the resist material. The above can be mixed and used. When the blending amount is 50 parts by mass or less, the film thickness of the pattern is reduced, and there is little possibility that the resolution is lowered.

  In addition, the above solubility control agents are synthesize | combined by introduce | transducing an acid labile group with respect to the compound which has a phenolic hydroxyl group or a carboxy group using an organic chemical prescription.

  As the carboxylic acid compound that can be added to the resist material used in the pattern forming method of the present invention, for example, one or more compounds selected from the following [Group I] and [Group II] can be used. However, it is not limited to these. By blending this component, the PED (Post Exposure Delay) stability of the resist is improved, and the edge roughness on the nitride film substrate is improved.

[Group I]
A part or all of the hydrogen atoms of the phenolic hydroxyl groups of the compounds represented by the following general formulas (A1) to (A10) are converted to —R ⁴⁰¹ —COOH (R ⁴⁰¹ is a linear or branched alkylene having 1 to 10 carbon atoms). The molar ratio of the phenolic hydroxyl group (C) in the molecule to the group (D) represented by ≡C—COOH is C / (C + D) = 0.1 to 1.0. Compound.
[Group II]
Compounds represented by the following general formulas (A11) to (A15).

In the above formula, R ⁴⁰⁸ represents a hydrogen atom or a methyl group.
R ⁴⁰² and R ⁴⁰³ each represent a hydrogen atom or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ⁴⁰⁴ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or a — (R ⁴⁰⁹ ) _h —COOR ′ group (R ′ represents a hydrogen atom or —R ⁴⁰⁹ —COOH). Show.
R ⁴⁰⁵ represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom.
R ⁴⁰⁶ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom.
R ⁴⁰⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group.
R ⁴⁰⁹ represents a linear or branched alkylene group having 1 to 10 carbon atoms.
R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or —R ⁴¹¹ —COOH group (wherein R ⁴¹¹ is a linear or branched group having 1 to 10 carbon atoms) Represents an alkylene group.
R ⁴¹² represents a hydrogen atom or a hydroxyl group.

j is a number from 0 to 3, and s1, t1, s2, t2, s3, t3, s4, and t4 satisfy s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, and each phenyl The number is such that it has at least one hydroxyl group in the skeleton.
s5 and t5 are numbers satisfying s5 + t5 = 5 with s5 ≧ 0 and t5 ≧ 0.
u is a number satisfying 1 ≦ u ≦ 4, and h is a number satisfying 1 ≦ h ≦ 4.
κ is a number that makes the compound of formula (A6) a weight average molecular weight of 1,000 to 5,000.
λ is a number that makes the compound of formula (A7) a weight average molecular weight of 1,000 to 10,000.

  Specific examples of this component include, but are not limited to, compounds represented by the following general formulas (AI-1) to (AI-14) and (AII-1) to (AII-10). It is not a thing.

（上式中、Ｒ’’は水素原子又はＣＨ₂ＣＯＯＨ基を示し、各化合物においてＲ’’の１０〜１００モル％はＣＨ₂ＣＯＯＨ基である。κとλは上記と同様の意味を示す。）

(In the above formula, R ″ represents a hydrogen atom or a CH ₂ COOH group, and in each compound, 10 to 100 mol% of R ″ is a CH ₂ COOH group. Κ and λ have the same meaning as described above. .)

  The amount of the compound having a group represented by ≡C—COOH in the molecule is 0 to 5 parts by mass, preferably 0.1 to 5 parts by mass, and more preferably 0 to 100 parts by mass of the base resin. 0.1-3 parts by mass, more preferably 0.1-2 parts by mass. If it is 5 mass parts or less, there is little possibility that the resolution of a resist material will fall.

  As the acetylene alcohol derivative that can be added to the resist material used in the pattern forming method of the present invention, those represented by the following general formulas (S1) and (S2) can be preferably used.

（上式中、Ｒ⁵⁰¹、Ｒ⁵⁰²、Ｒ⁵⁰³、Ｒ⁵⁰⁴、Ｒ⁵⁰⁵はそれぞれ水素原子、又は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基であり、Ｘ、Ｙは０又は正数を示し、下記値を満足する。０≦Ｘ≦３０、０≦Ｙ≦３０、０≦Ｘ＋Ｙ≦４０である。）

(In the above formula, R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , and R ⁵⁰⁵ are each a hydrogen atom or a linear, branched, or cyclic alkyl group having 1 to 8 carbon atoms, and X and Y are 0 Or it represents a positive number and satisfies the following values: 0 ≦ X ≦ 30, 0 ≦ Y ≦ 30, 0 ≦ X + Y ≦ 40.)

  The acetylene alcohol derivative is preferably Surfinol 61, Surfinol 82, Surfinol 104, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol TG, Surfinol PC, Surfinol 440, Surfinol 465, Surfinol 485 (Air Products and Chemicals Inc.), Surfinol E1004 (Nisshin Chemical Industry Co., Ltd.) and the like.

  The addition amount of the acetylene alcohol derivative is 0.01 to 2% by mass, more preferably 0.02 to 1% by mass in 100% by mass of the resist material. If it is 0.01 mass% or more, the improvement effect of applicability | paintability and storage stability is fully acquired, and if it is 2 mass% or less, there is little possibility that the resolution of a resist material will fall.

  The present invention also includes a step of applying the resist material on the substrate, and after the heat treatment, after wetting the photoresist film surface with a solution containing a higher alcohol having 4 to 10 carbon atoms, and then applying a protective film, After the heat treatment, there is provided a pattern forming method comprising a step of immersion exposure using water with a high energy ray and a step of developing using a developer. It is preferable to set it as the thing of the range of 180-250 nm.

For example, a resist material is applied on a substrate such as a silicon wafer by spin coating or the like so that the film thickness becomes 0.1 to 2.0 μm, and this is applied on a hot plate at 1 to 10 at 60 to 150 ° C. Pre-bake for 1 minute to 5 minutes, preferably 80 to 140 ° C. to form a photoresist film.
Next, after the photoresist film surface is wetted with a solution containing a higher alcohol having 4 to 10 carbon atoms by the above-described method, a protective film is applied and heat treatment is performed at 50 to 130 ° C., particularly 60 to 120 ° C. In some cases, heat treatment may be performed before applying the protective film. The thickness of the protective film is in the range of 5 to 200 nm, preferably 10 to 150 nm.
Next, a mask for forming a target pattern is placed over the above-described photoresist film, and a refractive index of 1.0 at an exposure wavelength is provided between the resist protective film and the projection lens with a high energy beam such as a KrF excimer laser or an ArF excimer laser. The above liquid is inserted and immersion exposure is performed so that the exposure amount is 1 to 200 mJ / cm ² , preferably 10 to 100 mJ / cm ² . Water is most preferably used as the liquid.

  The above-described photoresist protective film used in the pattern forming method of the present invention has a good barrier performance against water, can suppress the elution of the photoresist material into water, and is excellent in lubricity so that it can be scanned at high speed. Exposure is possible.

  Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably at 80 to 140 ° C. for 1 to 3 minutes. Further, 0.1 to 5% by mass, preferably 2 to 3% by mass of an aqueous developer solution such as tetramethylammonium hydroxide (TMAH) is used for 0.1 to 3 minutes, preferably 0.5 to 2%. The target pattern is formed on the substrate by developing by a conventional method such as a dip method, a paddle method, or a spray method for a minute.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these description.

[Examples and Comparative Examples]
(Preparation of polymer compound for resist protective film)
As a polymer compound to be added to the resist protective film material, each monomer is combined and subjected to radical copolymerization reaction in an isopropyl alcohol solvent, crystallized in hexane, further washed with hexane, isolated and dried. A polymer compound having the composition shown below was obtained. The composition of the obtained polymer compound was confirmed by ¹ H-NMR, and the molecular weight and dispersity were confirmed by gel permeation chromatography.

Polymer 1 (Polymer 1)
Molecular weight (Mw) = 9,100
Dispersity (Mw / Mn) = 1.82

Polymer 2
Molecular weight (Mw) = 8,600
Dispersity (Mw / Mn) = 1.79

Polymer 3 (Polymer 3)
Molecular weight (Mw) = 6,300
Dispersity (Mw / Mn) = 1.64

Polymer 4 (Polymer 4)
Molecular weight (Mw) = 7,500
Dispersity (Mw / Mn) = 1.73

Polymer 5 (Polymer 5)
Molecular weight (Mw) = 6,100
Dispersity (Mw / Mn) = 1.68

(Preparation of protective film material)
After mixing and dissolving the base resin and organic solvent in the composition shown below, they are filtered through a high-density polyethylene filter (pore size 0.02 μm), and the protective film material (TC-1 to TC-8) having the composition shown in Table 1 ) Was prepared.

(Preparation of resist material)
After mixing and dissolving the base resin, photoacid generator, basic compound and organic solvent with the composition shown below, they are filtered through a high-density polyethylene filter (pore size 0.02 μm) to obtain a resist material (resist 1, 2 ) Was prepared.

分子量（Ｍｗ）＝７，６００
分散度（Ｍｗ／Ｍｎ）＝１．７６
光酸発生剤（ＰＡＧ）：ノナフルオロブタンスルホン酸トリフェニルスルホニウム
塩基性化合物（クエンチャー）：２−（２−メトキシエトキシメトキシ）エチルモルホリン
有機溶剤：酢酸１−メトキシイソプロピル Resist 1
Mixed composition: base resin 1 (100 parts by mass), photoacid generator (5 parts by mass), basic compound (1 part by mass), organic solvent (1,800 parts by mass), surfactant KH-20 (Asahi Glass ( Co., Ltd.) 0.1 parts by mass base resin 1 (see the following structural formula)

Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.76
Photoacid generator (PAG): Nonafluorobutanesulfonic acid triphenylsulfonium basic compound (quencher): 2- (2-methoxyethoxymethoxy) ethylmorpholine Organic solvent: 1-methoxyisopropyl acetate

Resist 2
Mixed composition: base resin 2 (50 parts by mass), base resin 3 (50 parts by mass), photoacid generator (3.5 parts by mass), basic compound (0.5 parts by mass), organic solvent: acetic acid 1- Methoxyisopropyl (1,200 parts by mass), cyclohexanone (300 parts by mass), surfactant KH-20 (Asahi Glass Co., Ltd.) 0.1 parts by mass

光酸発生剤（ＰＡＧ）：ノナフルオロブタンスルホン酸トリフェニルスルホニウム
塩基性化合物（クエンチャー）（下記構造式参照）

有機溶剤：酢酸１−メトキシイソプロピル、シクロヘキサノン Base resins 2 and 3 (see structural formula below)

Photoacid generator (PAG): Nonafluorobutanesulfonic acid triphenylsulfonium basic compound (quencher) (see structural formula below)

Organic solvent: 1-methoxyisopropyl acetate, cyclohexanone

  A resist solution is applied on an 80 nm film thickness of an anti-reflective film ARC-29A manufactured by Nissan Chemical Industries, Ltd. produced on an 8-inch Si substrate, and baked at 110 ° C. for 60 seconds to produce a 200 nm thick resist film. did. A solution containing various alcohols was statically dispensed for 3 seconds (pre-soaking), rotated at 2,000 rpm for 10 seconds, and a resist protective film TC-1 to 8 was applied thereon with a thickness of 50 nm, and at 100 ° C. for 60 seconds. Baked. Perform a checkered flag exposure that exposes the exposed area and unexposed area of the open frame alternately with a 20 mm square area over the entire surface of the wafer with a Nikon ArF excimer laser scanner S307E (NA0.85 σ0.93, Cr mask), Post exposure baking (PEB) was performed at 110 ° C. for 60 seconds, and development was performed with a 2.38 mass% TMAH developer for 30 seconds. The number of rotations after rinsing after development was 2,000 rpm for 30 seconds.

The number of defects in the unexposed part of the checkered flag was measured at a pixel size of 0.125 μm using a defect inspection apparatus WinWin-50-1200 manufactured by Tokyo Seimitsu Co., Ltd.
In the patterning evaluation, PEB and development processes up to the application of the resist protective film were performed using the same method as described above, ArF excimer laser exposure was performed under the conditions of NA 0.85 σ 0.93, 6% halftone phase shift mask, and 150 nm hole. Using an isolated hole pattern with a size and a pitch of 1,200 nm between holes, the entire surface of the wafer is exposed with an exposure amount that the hole pattern is finished to 120 nm, and the number of closed defects that do not have holes opened is Measurement was performed at a pixel size of 0.125 μm using a Tokyo Seimitsu defect inspection device WinWin-50-1200.
The results are shown in Table 2.

  Table 3 shows the results of the comparative example when the alcohol solution is not pre-soaked.

  Although this embodiment was performed by dry exposure, similar results can be obtained by immersion exposure.

Claims (8)

  After applying the photoresist material on the substrate, and after heat treatment, the photoresist film surface is wetted with a solution containing a higher alcohol having 4 to 10 carbon atoms, then a protective film is applied, and after the heat treatment, high energy rays are applied. The pattern formation method characterized by including the process exposed by (3), and the process developed using a developing solution.   The pattern forming method according to claim 1, wherein the solution containing the higher alcohol is a solution in which an ether compound having 8 to 12 carbon atoms is further mixed.   The pattern forming method according to claim 1 or 2, wherein the solution containing the higher alcohol is a solution in which hydrochloric acid, nitric acid, sulfuric acid, carboxylic acid, sulfonic acid, or an amine salt of sulfonic acid is further mixed.   The pattern formation method according to any one of claims 1 to 3, wherein the higher alcohol has 4 to 7 carbon atoms.   5. The exposure according to claim 1, wherein the step of exposing with the high energy ray is performed by immersion exposure in which a liquid is exposed between the lowest surface of the projection lens and the substrate. Pattern forming method.   In the immersion exposure, an exposure wavelength in the range of 180 to 250 nm is used, a liquid is inserted between the substrate on which the photoresist film and the protective film are formed, and the lowest surface of the projection lens, and the liquid is used. The pattern forming method according to claim 5, wherein the substrate is exposed through the substrate.   7. The liquid immersion exposure according to claim 5, wherein exposure is performed using water as a liquid inserted between the substrate on which the photoresist film and the protective film are formed and the lowest surface of the projection lens. The pattern formation method as described in any one of.   The protective film material is obtained by dissolving an alkali-soluble polymer having an α-trifluoromethyl alcohol group in an ether compound having 8 to 12 carbon atoms and / or a higher alcohol having 4 to 10 carbon atoms. 8. The pattern forming method according to any one of 7 above.