JP2009157338A - Pattern forming method and resist material for use therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pattern forming method to cure a first time resist film by irradiation of light extremely short in wavelength of 300 nm or less and to prevent dissolution of a first time resist pattern into a developing agent at first and second time resist film mixing and second time development, and a resist material used for the method. <P>SOLUTION: This pattern forming method has steps of forming a first resist film by applying on a substrate a first positive type resist material containing a high molecular compound obtained by copolymerizing a phenolic group-containing repetition units and repetition units whose alkali solubility improves with an acid, exposing the film with high energy rays after heat treatment, developing the film with a developing agent, then crosslinking and curing a first resist film 30 by irradiation of high energy rays with a wavelength of 300 nm or less, forming a second resist film 50 by applying a second positive type resist material on the substrate additionally, exposing the second resist film 50 with high energy rays after heat-treatment, and developing the second resist film using the developing agent after heat-treatment. Therefore, double patterning can be performed by insolubilizing a first pattern after formation with the first positive type resist material, applying the second resist material on it, and forming a second pattern in a space portion of the first pattern, and thus the substrate can be processed with one time of dry etching. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  In the present invention, the pattern is formed by the first exposure, and the first pattern is made insoluble in an organic solvent or an alkaline aqueous solution by irradiation with ultrashort wavelength light or electron beam (EB). The present invention relates to a pattern forming method effective as a method for reducing a distance between patterns by forming a line pattern in a space portion of a pattern formed by the second exposure and performing a second exposure, and a resist material used therefor.

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. As exposure light used for forming a resist pattern, light exposure using g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source was widely used in the 1980s. As a means for further miniaturization, the method of shortening the exposure wavelength is effective, and mass production after 64 Mbit (process size is 0.25 μm or less) DRAM (Dynamic Random Access Memory) in the 1990s In the process, 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 dimension is 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. Initially, 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 is changed due to the introduction of the hard pellicle because the durability of the soft pellicle is extremely low, and the etching resistance of the resist film is reduced. Due to various problems, F ₂ lithography was postponed and early introduction of ArF immersion lithography was proposed (Non-patent Document 1: Proc. SPIE Vol. 4690 xxix).

  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 (numerical aperture) of 1.0 or more. Theoretically, the NA can be increased to near 1.44. Initially, it was pointed out that the resolution was deteriorated and the focus shifted due to the change in refractive index accompanying the change in water temperature. It was confirmed that the water temperature was controlled within 1/100 ° C. and the influence of the heat generated from the resist film due to exposure was almost no worry, and the problem of refractive index change was solved. It was feared that microbubbles in the water could be transferred to the pattern, but it was confirmed that the water was sufficiently degassed and that there was no risk of bubble formation from the resist film due to exposure. In the early stage of immersion lithography in the 1980s, a method was proposed in which all stages were immersed in water, but water was inserted only between the projection lens and the wafer to accommodate the operation of the high-speed scanner, and water was supplied and drained. A partial fill system with a nozzle was adopted. In principle, lens design with an NA of 1 or more became possible by immersion using water, but the conventional optical system based on the refractive index system became a huge lens, and the lens was deformed by its own weight. There was a problem. A catadioptric optical system has been proposed for a more compact lens design, and a lens design with NA of 1.0 or more has been accelerated. The possibility of a 45 nm node is shown by combining a lens with NA 1.2 or higher and strong super-resolution technology (Non-patent Document 2: Proc. SPIE Vol. 5040 p724), and further, a lens with NA 1.35 has been developed. ing.

  As a lithography technique for the 32 nm node, vacuum ultraviolet light (EUV) lithography with a wavelength of 13.5 nm is cited as a candidate. Problems of EUV lithography include higher laser output, higher resist film sensitivity, higher resolution, lower line edge roughness (LWR), defect-free MoSi laminated mask, lower reflection mirror aberration, etc. There are many problems to overcome.

The resolution that can be reached with the highest NA of water immersion lithography using an NA 1.35 lens is 40 to 38 nm and cannot reach 32 nm. Therefore, development of a high refractive index material for further increasing NA is being carried out. It is the minimum refractive index among the projection lens, liquid, and resist film that determines the limit of the NA of the lens. In the case of water immersion, the refractive index of water is the lowest compared with the projection lens (refractive index of 1.5 for synthetic quartz) and resist film (refractive index of 1.7 for conventional methacrylate system). The lens NA was fixed. Recently, highly transparent liquids having a refractive index of 1.65 have been developed. In this case, it is necessary to develop a projection lens material having the lowest refractive index and a high refractive index of the projection lens made of synthetic quartz. LUAG (Lu ₃ Al ₅ O ₁₂ ) garnet has a refractive index of 2 or more and is the most expected material, but has a problem of large birefringence and absorption. Even if a projection lens material having a refractive index of 1.8 or higher is developed, the NA of the liquid having a refractive index of 1.65 is only 1.55, and 32 nm cannot be resolved. In order to resolve 32 nm, a liquid having a refractive index of 1.8 or more is required. At present, there is a trade-off between absorption and refractive index, and no such material has yet been found. In the case of an alkane compound, a bridged cyclic compound is preferable to a linear compound in order to increase the refractive index. However, the cyclic compound has a high viscosity, so there is a problem that it cannot follow the high-speed scanning of the exposure apparatus stage. It is. Further, when a liquid having a refractive index of 1.8 is developed, since the minimum refractive index becomes a resist film, the resist film needs to have a high refractive index of 1.8 or more.

  Recently, a double patterning process in which a pattern is formed by the first exposure and development and a pattern is formed just between the first pattern by the second exposure (Non-Patent Document 3: Proc.SPIE Vol.5992 p557 (2005)). Many processes have been proposed as a double patterning method. For example, the first exposure and development form a photoresist pattern with 1: 3 line and space spacing, the lower hard mask is processed by dry etching, and another hard mask is laid on the first hard mask. In this exposure method, a line pattern is formed by exposure and development of a photoresist film in a space portion of the exposure, and a hard mask is processed by dry etching to form a line-and-space pattern that is half the pitch of the initial pattern. Further, a photoresist pattern having a space and line spacing of 1: 3 is formed by the first exposure and development, the underlying hard mask is processed by dry etching, and a photoresist film is applied thereon. The second space pattern is exposed to the portion where the hard mask remains, and the hard mask is processed by dry etching. In either case, the hard mask is processed by two dry etchings.

  In the above-described method, it is necessary to lay a hard mask twice. In the latter method, only one hard mask is required, but it is necessary to form a trench pattern that is difficult to resolve compared to a line pattern. In the latter method, there is a method using a negative resist material for forming a trench pattern. This can use the same high contrast light as forming a line with a positive pattern, but the negative resist material has a lower dissolution contrast than the positive resist material. Compared with the case of forming a line, the case of using a negative resist material to form a trench pattern having the same dimensions is compared. In the latter method, a wide trench pattern is formed using a positive resist material, and then the substrate is heated to shrink the trench pattern, or a water-soluble film is coated on the developed trench pattern. Although it is conceivable to apply the RELAX method of shrinking the trench by heating and then crosslinking the resist film surface, the disadvantage that the proximity bias deteriorates and the process becomes more complicated and the throughput decreases. .

  Even in the former method and the latter method, etching for substrate processing is required twice, so that there is a problem in that throughput is reduced and pattern deformation and displacement occur due to the two etchings.

  In order to complete the etching once, there is a method in which a negative resist material is used in the first exposure and a positive resist material is used in the second exposure. There is also a method in which a positive resist material is used in the first exposure, and a negative resist material dissolved in a higher alcohol having 4 or more carbon atoms in which the positive resist material is not dissolved in the second exposure. In these cases, if a negative resist material having low resolution is used, the resolution deteriorates.

A method in which PEB (Post Exposure Bake) and development are not performed between the first exposure and the second exposure is the simplest method. In this case, the first exposure is performed, the pattern is shifted to a mask on which a shifted pattern is drawn, the second exposure is performed, and PEB, development, and dry etching are performed. If the mask is changed for each exposure, the throughput is greatly reduced. Therefore, the second exposure is performed after the first exposure is performed to some extent. Then, depending on the standing time between the first exposure and the second exposure, a dimensional change due to acid diffusion or a change in shape such as generation of a T-top shape occurs. In order to suppress the occurrence of T-top, application of a resist protective film is effective. By applying an immersion resist protective film, a process of performing two exposures, one PEB, development, and dry etching can be performed. Two scanners can be arranged side by side to perform the first exposure and the second exposure continuously. In this case, there arises a problem that the positional deviation caused by the lens aberration between the two scanners and the scanner cost is doubled.
When the second exposure is performed at a position shifted by a half pitch next to the first exposure, the energy of the second time is canceled and the contrast becomes zero. When a contrast enhancement film (CEL) is applied on the resist film, the light incident on the resist becomes nonlinear, and the first and second lights do not cancel each other, and an image with a half pitch is formed (Non-Patent Document 4: Jpn.J. Appl.Phy.Vol. 33 (1994) p6874-6877). In addition, it is expected that a similar effect can be produced by creating a non-linear contrast using a two-photon absorption acid generator as the resist acid generator. However, a CEL agent having a bleaching property at a wavelength of 193 nm and an acid generator having a two-photon absorption property have not been found.

  The most critical problem in double patterning is the alignment accuracy of the first and second patterns. Since the size of the positional deviation is a variation in line dimensions, for example, if it is attempted to form a 32 nm line with an accuracy of 10%, an alignment accuracy within 3.2 nm is required. Since the alignment accuracy of the current scanner is about 8 nm, a significant improvement in accuracy is necessary.

  A technique for modifying a photoresist film by light irradiation has been well known in the past, and has been studied particularly for improving etching resistance. For example, Patent Document 1: JP-A-5-102029 discloses a method of irradiating short wavelength light in a vacuum while heating a substrate coated with a photoresist film with a hot plate, Patent Documents 2-5: JP-A-5 JP-A-190444, JP-A-9-63922, JP-A-2000-331910, and JP-A-2003-158057 propose light irradiation devices. Patent Document 6: Japanese Patent Application Laid-Open No. 2005-189842 discloses a resist pattern in which a solution containing a photocrosslinkable film is applied during development of a photoresist after development, and the photoresist film is hydrophobized by light irradiation at a short wavelength. A method for preventing the fall is proposed.

  It is well known that when novolac resin or polyhydroxystyrene is irradiated with short-wavelength light having a wavelength of 300 nm or less, crosslinking proceeds and becomes insoluble in an organic solvent or an alkali developer. It is believed that the phenolic hydroxy group causes a crosslinking reaction by irradiation with short wavelength light. Etching resistance is improved by crosslinking a pattern after development of an i-line resist having a phenolic hydroxy group and a KrF resist by irradiation with a short wavelength light source by the irradiation apparatus.

Proc. SPIE Vol. 4690 xxix Proc. SPIE Vol. 5040 p724 Proc. SPIE Vol. 5992 p557 (2005) Jpn. J. et al. Appl. Phy. Vol. 33 (1994) p 6874-6877 JP-A-5-102029 Japanese Patent Laid-Open No. 5-190444 Japanese Patent Laid-Open No. 9-63921 JP 2000-331910 A Japanese Patent Laid-Open No. 2003-158057 JP 2005-189842 A

  As described above, when a substrate pattern is processed by dry etching twice, the throughput is reduced by half. In addition, there arises a problem of pattern displacement due to dry etching.

  The present invention is an improvement of the above circumstances. A pattern forming method for enabling a double patterning process for processing a substrate by one dry etching, that is, a first resist pattern (first resist film) is provided. A pattern forming method for curing by irradiation with ultrashort wavelength light having a wavelength of 300 nm or less, and mixing the first and second resist films and the first resist pattern not dissolving in the developer at the second development, and An object is to provide a resist material to be used.

  In order to solve the above-described problem, according to the present invention, the following method is effective in a pattern forming method in which a pattern is formed by applying a second resist film to a space portion after the first resist pattern is formed. I found out.

（式中、Ｒ¹、Ｒ³は同一又は異種の水素原子又はメチル基を示す。Ｘは単結合、又は−Ｃ（＝Ｏ）−Ｏ−であり、Ｙは単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基で、エステル基又はエーテル基を有していてもよい。あるいは、Ｙは、ベンゼン環の互いに隣接する２個の炭素原子と結合して脂環を形成する３価の基である。Ｒ²は同一又は異種の水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜６のアルケニル基、炭素数６〜１０のアリール基、又はトリフルオロメチル基であり、ｍは１〜３の整数、ｎは２〜４の整数であり、ｍ＋ｎ＝５である。Ｒ⁴は酸不安定基を示す。ａ、ｂは０＜ａ＜１．０、０＜ｂ＜１．０、０＜ａ＋ｂ≦１．０の範囲である。）
請求項１１：
フェノール基を有する繰り返し単位と酸によってアルカリ溶解性が向上する繰り返し単位とを共重合してなる高分子化合物が、下記一般式（２）に示される繰り返し単位（ａ）、（ｂ）、（ｃ１）、（ｃ２）を有するものであることを特徴とする請求項１乃至９のいずれか１項記載のパターン形成方法に用いるポジ型レジスト材料。

（式中、Ｒ¹、Ｒ³、Ｒ⁵、Ｒ¹⁰は同一又は異種の水素原子又はメチル基を示す。Ｘは単結合、又は−Ｃ（＝Ｏ）−Ｏ−であり、Ｙは単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基で、エステル基又はエーテル基を有していてもよい。あるいは、Ｙは、ベンゼン環の互いに隣接する２個の炭素原子と結合して脂環を形成する３価の基である。Ｒ²は同一又は異種の水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜６のアルケニル基、炭素数６〜１０のアリール基、又はトリフルオロメチル基であり、ｍは１〜３の整数、ｎは２〜４の整数であり、ｍ＋ｎ＝５である。Ｒ⁴は酸不安定基を示す。Ｒ⁶、Ｒ¹¹は単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基であり、エーテル基又はエステル基を有していてもよいが、炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基の場合、式中のエステル基に連結した炭素原子は１級又は２級である。Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は水素原子、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基である。ａ、ｂ、ｃ１、ｃ２は０＜ａ＜１．０、０＜ｂ＜１．０、０≦ｃ１＜１．０、０≦ｃ２＜１．０、０＜ｃ１＋ｃ２＜１．０、０＜ａ＋ｂ＋ｃ１＋ｃ２≦１．０の範囲である。） Accordingly, the present invention provides the following pattern forming method and a resist material used therefor.
Claim 1:
A first positive resist material containing a polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is applied on a substrate to form a first resist film. Then, after the heat treatment, the resist film is exposed with a high energy beam, and after the heat treatment, the resist film is developed with a developer, and then the first resist film is crosslinked and cured by irradiation with a high energy beam having a wavelength of 300 nm or less. Then, a second positive resist material is applied onto the substrate to form a second resist film, and after the heat treatment, the second resist film is exposed with a high energy beam, and after the heat treatment, a developer A pattern forming method comprising a step of developing the second resist film using
Claim 2:
A first positive resist material containing a polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is applied on a substrate to form a first resist film. Then, after the heat treatment, the resist film is exposed with a high energy beam, and after the heat treatment, the resist film is developed with a developer, and then the first resist film is formed by irradiation and heating with a high energy beam having a wavelength of 300 nm or less. After crosslinking and curing, a second positive resist material is applied onto the substrate to form a second resist film, and after the heat treatment, the second resist film is exposed with a high energy beam, and after the heat treatment A pattern forming method comprising a step of developing the second resist film using a developer.
Claim 3:
A first positive resist material containing a polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is applied on a substrate to form a first resist film. Then, after the heat treatment, the resist film is exposed with a high energy beam, and after the heat treatment, the resist film is developed with a developer, and then heated, and then irradiated with a high energy beam having a wavelength of 300 nm or less. The resist film is cross-linked and cured, and a second positive resist material is applied onto the substrate to form a second resist film. After the heat treatment, the second resist film is exposed with a high energy beam, A pattern forming method comprising a step of developing the second resist film using a developer after the heat treatment.
Claim 4:
High energy rays having a wavelength of 300 nm or less used for crosslinking of the first resist pattern formed by development are emitted from a low-pressure mercury lamp including wavelengths 254 nm and 185 nm, KrF excimer light having a wavelength of 248 nm, KrCl excimer light having a wavelength of 222 nm, wavelength 4. A 193 nm ArF excimer light, a 172 nm Xe ₂ excimer light, a 157 nm F ₂ excimer light, a 146 nm Kr ₂ excimer light, a 126 nm Ar ₂ excimer light, or an electron beam. The pattern formation method of any one of these.
Claim 5:
The exposure for forming the first resist pattern and the second resist pattern is immersion lithography in which a liquid having a refractive index of 1.4 or more is immersed between a lens and a wafer by an ArF excimer laser having a wavelength of 193 nm. The pattern forming method according to claim 1, wherein:
Claim 6:
6. The pattern forming method according to claim 5, wherein the liquid having a refractive index of 1.4 or more is water.
Claim 7:
The pattern forming method according to claim 1, wherein a space between the patterns is reduced by forming a second pattern in a space portion of the first pattern.
Claim 8:
The pattern forming method according to claim 1, wherein a second pattern intersecting with the first pattern is formed.
Claim 9:
The pattern forming method according to claim 1, wherein the second pattern is formed in a direction different from the first pattern in a space portion where the pattern of the first pattern is not formed.
Claim 10:
A polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is a repeating unit (a) and a repeating unit (b) represented by the following general formula (1): The positive resist material used for the pattern formation method of any one of Claims 1 thru | or 9 characterized by the above-mentioned.

(In the formula, R ¹ and R ³ represent the same or different hydrogen atoms or methyl groups. X is a single bond, or —C (═O) —O—, and Y is a single bond, or a carbon number of 1 to A linear, branched or cyclic alkylene group which may have an ester group or an ether group, or Y is bonded to two adjacent carbon atoms of the benzene ring to form an alicyclic ring R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, An aryl group having 6 to 10 carbon atoms or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer of 2 to 4, and m + n = 5, and R ⁴ represents an acid labile group. A and b are in the range of 0 <a <1.0, 0 <b <1.0, and 0 <a + b ≦ 1.0.)
Claim 11:
A polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is a repeating unit (a), (b) or (c1) represented by the following general formula (2). 10) The positive resist material used in the pattern forming method according to claim 1, wherein the positive resist material has (c2).

(In the formula, R ¹ , R ³ , R ⁵ and R ¹⁰ are the same or different hydrogen atoms or methyl groups. X is a single bond, or —C (═O) —O—, and Y is a single bond. Or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms which may have an ester group or an ether group, or Y represents two carbon atoms adjacent to each other in the benzene ring. R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon number 2 6 alkenyl group, an aryl group having 6 to 10 carbon atoms, or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer from 2 to 4, .R ⁴ is a m + n = 5 is An acid labile group, wherein R ⁶ and R ¹¹ are a single bond or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms. In the case of a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, the carbon atom linked to the ester group in the formula is primary. R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. A, b, c1, c2 are 0 <a <1.0, 0 <b <1.0, 0 ≦ c1 <1.0, 0 ≦ c2 <1.0, 0 <c1 + c2 <1.0, 0 <A + b + c1 + c2 ≦ 1.0.

According to the present invention, after forming the first pattern by exposure and development using the first positive resist material, high energy rays having a wavelength of 300 nm or less, particularly KrF excimer light having a wavelength of 248 nm, KrCl having a wavelength of 222 nm Excimer light, light emitted from a low-pressure mercury lamp including wavelengths 254 nm and 185 nm, ArF excimer light with a wavelength of 193 nm, Xe ₂ excimer light with a wavelength of 172 nm, F ₂ excimer light with a wavelength of 157 nm, Kr ₂ excimer light with a wavelength of 146 nm, Ar with 126 nm _{It is} selected from ₂ excimer light and electron beam, and is insolubilized in an alkali developer and a resist solution by a crosslinking reaction. A second resist material is further applied thereon, exposed and developed to form a second pattern in the space portion of the first pattern, thereby performing double patterning that halves the pattern and pattern pitch, The substrate can be processed by one dry etching.

  In the double patterning lithography that obtains a half-pitch pattern by two exposures and developments, the present inventors have intensively studied to obtain a positive resist material for processing a substrate by one dry etching. .

That is, the present inventors use a first positive resist material, which will be described later, form a first pattern by exposure and development, and then crosslink with a high energy ray having a wavelength of 300 nm or less, particularly KrF excimer light having a wavelength of 248 nm. , KrCl excimer light with a wavelength of 222 nm, light emitted from a low-pressure mercury lamp including wavelengths 254 nm and 185 nm, ArF excimer light with a wavelength of 193 nm, Xe ₂ excimer light with a wavelength of 172 nm, F ₂ excimer light with a wavelength of 157 nm, Kr ₂ excimer with a wavelength of 146 nm By insolubilizing the first pattern in an alkali developer or a resist solvent by a cross-linking reaction by irradiation with light, 126 nm Ar ₂ excimer light and electron beam, and further applying a second resist material thereon, and then developing by exposure By forming the second pattern in the space portion of the first pattern Performs double patterning halving the pitch of the pattern and the pattern Te, it found that it is possible to process the substrate by a single dry etching, in which the present invention has been completed.

  The first and second positive resist materials are preferably chemically amplified positive resist materials, and further include a base resin having at least a repeating unit having an acid labile group and a repeating unit having a phenol group. It is preferable that it is included.

It is well known that a phenol compound is crosslinked and cured by irradiation with a wavelength of 300 nm or less (Proc. SPIE Vol. 3678 p1012 (1999)). A mechanism has been reported in which phenoxy radicals are generated by light irradiation and intermolecular crosslinking proceeds by coupling between ortho positions of hydroxy groups.
However, since cresol novolac and polyhydroxystyrene have extremely strong absorption in an ArF excimer laser having a wavelength of 193 nm for forming a pattern, the first pattern cannot be formed when the introduction amount is large. Naphthalene has the effect of reducing absorption at a wavelength of 193 nm by extending the conjugated system and shifting the maximum absorption wavelength to the longer wavelength side. On the other hand, the introduction of fluorine in the benzene ring improves the transmittance by shifting the maximum absorption wavelength to the short wavelength side. JP-A-11-253929 proposes a fluorine-substituted hydroxystyrene copolymer. Moreover, the introduction of bromine and iodine in the benzene ring improves the transparency by shifting the absorption maximum wavelength to the longer wavelength side. These enable pattern formation in ArF excimer laser lithography.

  The 7-oxanorbornane ring has the property of curing the film by a crosslinking reaction with acid and heat. By combining the curing reaction of the phenol group by light irradiation and the crosslinking reaction of the 7-oxanorbornane ring by the acid and heat generated by the light irradiation, a stronger and insoluble film in a solvent and an alkali developer can be formed. .

  With such a chemically amplified positive resist material, the base resin contains a repeating unit having a phenol group adhesive group, whereby high adhesion to the substrate can be realized. In addition, 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, and the resist exposed area is dissolved in the developer. By doing so, a very highly accurate pattern can be obtained.

（式中、Ｒ¹は同一又は異種の水素原子又はメチル基を示す。Ｘは単結合、又は−Ｃ（＝Ｏ）−Ｏ−であり、Ｙは単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基で、エステル基（−ＣＯＯ−）又はエーテル基（−Ｏ−）を有していてもよい。あるいは、Ｙは、ベンゼン環の互いに隣接する２個の炭素原子と結合して脂環を形成する３価の基である。Ｒ²は同一又は異種の水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜６のアルケニル基、炭素数６〜１０のアリール基、又はトリフルオロメチル基であり、ｍは１〜３の整数である。また、ｎは２〜４の整数であり、ｍ＋ｎ＝５である。） As the polymer compound as the base resin in the first positive resist material used in the pattern forming method according to the present invention, those having a phenol group as an adhesive group are preferable, and particularly represented by the following general formula (a). Having a repeating unit.

(In the formula, R ¹ represents the same or different hydrogen atom or methyl group. X is a single bond or —C (═O) —O—, and Y is a single bond or a straight chain having 1 to 6 carbon atoms. A chain, branched or cyclic alkylene group which may have an ester group (—COO—) or an ether group (—O—), or Y represents two adjacent carbon atoms of the benzene ring. A trivalent group which forms an alicyclic ring by combining with an atom, R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon number An alkenyl group having 2 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer of 2 to 4, and m + n = 5 is there.)

Here, as a C1-C6 alkylene group, a methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, sec-butylene group, n-pentylene group, isopentylene group, Examples include a cyclopentylene group, an n-hexylene group, and a cyclohexylene group. Alternatively, Y is a trivalent group that binds to two adjacent carbon atoms of the benzene ring to form an alicyclic ring, for example, a cyclopentyl group, cyclohexyl together with two adjacent carbon atoms of the benzene ring. A group forming a norbornyl group.
Examples of R ² include H, Cl, F, Br, CH ₃ , CF ₃ , a cyclohexyl group, and a phenyl group.

The monomer for obtaining the repeating unit represented by the general formula (a) is represented by the following general formula Ma. Here, R ¹ , R ² , X, Y, m, and n are the same as described above.

Specific examples of Ma include the following.

  These monomers can be converted to hydroxy groups by deprotection after polymerization by replacing the hydroxy group with an acid labile group such as acetal, an acetyl group, a formyl group, a pivaloyl group or the like during polymerization.

  In the case of acetal substitution, acetic acid, formic acid, oxalic acid, etc. are used to deprotect only the acetal while leaving the acid labile group of the (meth) acrylic acid ester of the repeating unit represented by the general formula (b) described later. Deprotection is performed with carboxylic acid. When substituted with an acetyl group or the like, it is converted to a hydroxy group by alkali hydrolysis after polymerization.

（式中、Ｒ³は水素原子又はメチル基を示す。Ｒ⁴は酸不安定基である。） In addition to the repeating unit represented by the general formula (a), the polymer compound as the base resin in the first positive resist material has an acid labile group represented by the following general formula (b). It is preferable to have a repeating unit.

(In the formula, R ³ represents a hydrogen atom or a methyl group. R ⁴ is an acid labile group.)

A monomer for obtaining a repeating unit having an acid labile group represented by the general formula (b) is represented by the following general formula Mb. Here, R ³ and R ⁴ are the same as described above.

In the general formula (1), various acid labile groups represented by R ⁴ are selected. In particular, groups represented by the following formulas (AL-10) and (AL-11), and the following formula (AL-12): The tertiary alkyl group shown, the C4-C20 oxoalkyl group, etc. are mentioned.

In the formulas (AL-10) and (AL-11), R ⁵¹ and R ⁵⁴ are monovalent hydrocarbon groups such as a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms, particularly 1 to 20 carbon atoms. Yes, it may contain heteroatoms such as oxygen, sulfur, nitrogen and fluorine. R ⁵² and R ⁵³ are each a hydrogen atom or a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and includes heteroatoms such as oxygen, sulfur, nitrogen and fluorine. However, a5 is an integer of 0-10. R ⁵² and R ⁵³ , R ⁵² and R ⁵⁴ , R ⁵³ and R ⁵⁴ are bonded to each other to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms, particularly an oil. A ring may be formed.
R ⁵⁵ , R ⁵⁶ , and R ⁵⁷ are each a monovalent hydrocarbon group such as a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, and include heteroatoms such as oxygen, sulfur, nitrogen, and fluorine. But you can. Alternatively, R ⁵⁵ and R ⁵⁶ , R ⁵⁵ and R ⁵⁷ , R ⁵⁶ and R ⁵⁷ are bonded to form a ring having 3 to 20 carbon atoms, particularly 4 to 16 carbon atoms, particularly an alicyclic ring, together with the carbon atoms to which they are bonded. Also good.

  Specific examples of the compound represented by the formula (AL-10) include tert-butoxycarbonyl group, tert-butoxycarbonylmethyl group, tert-amyloxycarbonyl group, tert-amyloxycarbonylmethyl group, 1-ethoxyethoxycarbonyl. Examples include a methyl group, 2-tetrahydropyranyloxycarbonylmethyl group, 2-tetrahydrofuranyloxycarbonylmethyl group and the like, and substituents represented by the following general formulas (AL-10) -1 to (AL-10) -10. .

In the formulas (AL-10) -1 to (AL-10) -10, R ⁵⁸ is the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, aryl having 6 to 20 carbon atoms. Group or a C7-20 aralkyl group is shown. R ⁵⁹ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁰ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

  Examples of the acetal compound represented by the formula (AL-11) are (AL-11) -1 to (AL-11) -34.

  In addition, the base resin may be intermolecularly or intramolecularly crosslinked by an acid labile group represented by the general formula (AL-11a) or (AL-11b).

In the above formula, R ⁶¹ and R ⁶² represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms. Alternatively, R ⁶¹ and R ⁶² may be bonded to form a ring together with the carbon atom to which they are bonded, and when forming a ring, R ⁶¹ and R ⁶² are linear or branched having 1 to 8 carbon atoms. -Like alkylene group. R ⁶³ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, b5 and d5 are 0 or 1 to 10, preferably 0 or an integer of 1 to 5, and c5 is an integer of 1 to 7. . A represents a (c5 + 1) -valent aliphatic or alicyclic saturated hydrocarbon group, aromatic hydrocarbon group or heterocyclic group having 1 to 50 carbon atoms, and these groups are heteroatoms such as O, S, and N. Or a part of hydrogen atoms bonded to the carbon atom may be substituted with a hydroxyl group, a carboxyl group, a carbonyl group or a fluorine atom. B represents —CO—O—, —NHCO—O— or —NHCONH—.

  In this case, A is preferably a divalent to tetravalent C1-C20 linear, branched or cyclic alkylene group, alkanetriyl group, alkanetetrayl group, or C6-C30 arylene group. These groups may have intervening heteroatoms such as O, S, N, etc., and a part of the hydrogen atoms bonded to the carbon atoms are substituted by a hydroxyl group, a carboxyl group, an acyl group or a halogen atom. Also good. C5 is preferably an integer of 1 to 3.

  Specific examples of the crosslinked acetal groups represented by the general formulas (AL-11a) and (AL-11b) include those represented by the following formulas (AL-11) -35 to (AL-11) -42.

  Next, examples of the tertiary alkyl group represented by the formula (AL-12) include tert-butyl group, triethylcarbyl group, 1-ethylnorbornyl group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, tert -An amyl group etc., or the following general formula (AL-12) -1-(AL-12) -16 can be mentioned.

In the above formula, R ⁶⁴ represents the same or different linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. R ⁶⁵ and R ^{67 each} represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms. R ⁶⁶ represents an aryl group having 6 to 20 carbon atoms or an aralkyl group having 7 to 20 carbon atoms.

Furthermore, as shown in the following formulas (AL-12) -17 and (AL-12) -18, a divalent or higher valent alkylene group or an arylene group R ⁶⁸ is included, and the polymer within or between the molecules is It may be cross-linked. In the formulas (AL-12) -17 and (AL-12) -18, R ⁶⁴ represents the same as described above, and R ⁶⁸ represents a linear, branched or cyclic alkylene group having 1 to 20 carbon atoms, or an arylene group. And may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. b6 is an integer of 1 to 3.

Further, R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ may have a heteroatom such as oxygen, nitrogen and sulfur, specifically, the following formulas (AL-13) -1 to (AL-13) It can be shown in -7.

（式中、Ｒ⁶⁹は炭素数１〜８の直鎖状、分岐状又は環状のアルキル基又は炭素数６〜２０の置換されていてもよいアリール基を示す。Ｒ⁷⁰〜Ｒ⁷⁵及びＲ⁷⁸、Ｒ⁷⁹はそれぞれ独立に水素原子又は炭素数１〜１５のヘテロ原子を含んでもよいアルキル基等の１価の炭化水素基を示し、Ｒ⁷⁶、Ｒ⁷⁷は水素原子又は−ＣＨ₂−Ｏ−ＣＨ₃を示す。あるいは、Ｒ⁷⁰とＲ⁷¹、Ｒ⁷²とＲ⁷⁴、Ｒ⁷²とＲ⁷⁵、Ｒ⁷³とＲ⁷⁵、Ｒ⁷³とＲ⁷⁹、Ｒ⁷⁴とＲ⁷⁸、Ｒ⁷⁶とＲ⁷⁷又はＲ⁷⁷とＲ⁷⁸は互いに結合してこれらが結合する炭素原子と共に環を形成していてもよく、その場合には環の形成に関与する基は炭素数１〜１５のヘテロ原子を含んでもよいアルキレン基等の２価の炭化水素基を示す。またＲ⁷⁰とＲ⁷⁹、Ｒ⁷⁶とＲ⁷⁹又はＲ⁷²とＲ⁷⁴は隣接する炭素に結合するもの同士で何も介さずに結合し、二重結合を形成してもよい。また、本式により、鏡像体も表す。） In particular, as the acid labile group of the above formula (AL-12), those having an exo-body structure represented by the following formula (AL-12) -19 are preferable.

(In the formula, R ⁶⁹ represents a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms or an optionally substituted aryl group having 6 to 20 carbon atoms. R ^{70 to} R ⁷⁵ and R ^78. , R ⁷⁹ each independently represents a hydrogen atom or a monovalent hydrocarbon group such as an alkyl group which may contain a hetero atom having 1 to 15 carbon atoms, and R ⁷⁶ and R ⁷⁷ represent a hydrogen atom or —CH ₂ —O—. CH ₃ or R ⁷⁰ and R ⁷¹ , R ⁷² and R ⁷⁴ , R ⁷² and R ⁷⁵ , R ⁷³ and R ⁷⁵ , R ⁷³ and R ⁷⁹ , R ⁷⁴ and R ⁷⁸ , R ⁷⁶ and R ⁷⁷ or R ⁷⁷ and R ⁷⁸ may be bonded to each other to form a ring together with the carbon atom to which they are bonded, in which case the group involved in the formation of the ring is an alkylene which may contain a heteroatom having 1 to 15 carbon atoms a divalent hydrocarbon group such as a group. the one R ⁷⁰ and R ^79, R ⁷⁶ and R ⁷⁹ or R ⁷² and R ⁷⁴ are bonded to the adjacent carbon Bonded without interposing anything in, and may form a double bond. The formula also represents enantiomer.)

を得るためのエステル体のモノマーとしては、特開２０００−３２７６３３号公報に示されている。具体的には下記に示すものを挙げることができるが、これらに限定されることはない。なお、Ｒ¹¹¹、Ｒ¹¹²は、互いに独立に、水素原子、メチル基、−ＣＯＯＣＨ₃、−ＣＨ₂ＣＯＯＣＨ₃等を示す。 Here, the following repeating unit having an exo-body structure represented by the general formula (AL-12) -19

JP-A-2000-327633 discloses an ester monomer for obtaining the above. Specific examples include the following, but are not limited thereto. R ¹¹¹ and R ¹¹² each independently represent a hydrogen atom, a methyl group, —COOCH ₃ , —CH ₂ COOCH ₃ or the like.

  Furthermore, examples of the acid labile group of the above formula (AL-12) include an acid labile group having frangiyl, tetrahydrofurandiyl or oxanorbornanediyl represented by the following formula (AL-12) -20.

（式中、Ｒ⁸⁰、Ｒ⁸¹はそれぞれ独立に炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基等の１価炭化水素基を示す。又は、Ｒ⁸⁰、Ｒ⁸¹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３〜２０の脂肪族炭化水素環を形成してもよい。Ｒ⁸²はフランジイル、テトラヒドロフランジイル又はオキサノルボルナンジイルから選ばれる２価の基を示す。Ｒ⁸³は水素原子又はヘテロ原子を含んでもよい炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基等の１価炭化水素基を示す。）

(In the formula, R ⁸⁰ and R ⁸¹ each independently represent a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or R ⁸⁰ and R ⁸¹ are bonded to each other. Then, an aliphatic hydrocarbon ring having 3 to 20 carbon atoms may be formed together with the carbon atom to which they are bonded, and R ⁸² represents a divalent group selected from flangedyl, tetrahydrofurandiyl or oxanorbornanediyl. ⁸³ represents a monovalent hydrocarbon group such as a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms which may contain a hydrogen atom or a hetero atom.)

を得るためのモノマーとしては、下記に例示される。なお、Ｒ¹¹²は上記の通りである。また、下記式中Ｍｅはメチル基、Ａｃはアセチル基を示す。 Repeating units substituted with acid labile groups having frangyl, tetrahydrofurandiyl or oxanorbornanediyl

Examples of the monomer for obtaining the are as follows. R ¹¹² is as described above. In the following formulae, Me represents a methyl group, and Ac represents an acetyl group.

（式中、Ｒ⁵、Ｒ¹⁰は水素原子又はメチル基を示す。Ｒ⁶、Ｒ¹¹は単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基であり、エーテル基（−Ｏ−）又はエステル基（−ＣＯＯ−）を有していてもよいが、炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基の場合、式中のエステル基に連結した炭素原子は１級又は２級である。Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は水素原子、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基である。） The polymer compound as the base resin in the first positive resist material preferably further has a repeating unit having a 7-oxanorbornane ring represented by the following general formula (c1) or (c2).

(In the formula, R ⁵ and R ¹⁰ represent a hydrogen atom or a methyl group. R ⁶ and R ¹¹ represent a single bond, or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, and an ether group. (-O-) or an ester group (-COO-) may be present, but in the case of a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, it is linked to the ester group in the formula The carbon atom is primary or secondary, and R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , and R ¹⁵ are hydrogen atoms, linear, branched or cyclic having 1 to 6 carbon atoms. The alkyl group of

Monomers for obtaining a repeating unit having a 7-oxanorbornane ring are represented by the following general formulas Mc1 and Mc2. Here, R ^{5 to} R ¹⁵ are the same as described above.

  Specific examples of the monomer for obtaining the repeating units c1 and c2 include the following.

  From the above, the first positive resist material has, as a base resin, a polymer compound having repeating units (a) and (b) represented by the following general formula (1), particularly the following general formula (2). A polymer compound having the repeating units (a), (b), (c1) and (c2) shown is preferable.

（式中、Ｒ¹、Ｒ³は同一又は異種の水素原子又はメチル基を示す。Ｘは単結合、又は−Ｃ（＝Ｏ）−Ｏ−であり、Ｙは単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基で、エステル基又はエーテル基を有していてもよい。あるいは、Ｙは、ベンゼン環の互いに隣接する２個の炭素原子と結合して脂環を形成する３価の基である。Ｒ²は同一又は異種の水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜６のアルケニル基、炭素数６〜１０のアリール基、又はトリフルオロメチル基であり、ｍは１〜３の整数、ｎは２〜４の整数であり、ｍ＋ｎ＝５である。Ｒ⁴は酸不安定基を示す。ａ、ｂは０＜ａ＜１．０、０＜ｂ＜１．０、０＜ａ＋ｂ≦１．０の範囲である。）

(In the formula, R ¹ and R ³ represent the same or different hydrogen atoms or methyl groups. X is a single bond, or —C (═O) —O—, and Y is a single bond, or a carbon number of 1 to A linear, branched or cyclic alkylene group which may have an ester group or an ether group, or Y is bonded to two adjacent carbon atoms of the benzene ring to form an alicyclic ring R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, An aryl group having 6 to 10 carbon atoms or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer of 2 to 4, and m + n = 5, and R ⁴ represents an acid labile group. A and b are in the range of 0 <a <1.0, 0 <b <1.0, and 0 <a + b ≦ 1.0.)

（式中、Ｒ¹、Ｒ³、Ｒ⁵、Ｒ¹⁰は同一又は異種の水素原子又はメチル基を示す。Ｘは単結合、又は−Ｃ（＝Ｏ）−Ｏ−であり、Ｙは単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基で、エステル基又はエーテル基を有していてもよい。あるいは、Ｙは、ベンゼン環の互いに隣接する２個の炭素原子と結合して脂環を形成する３価の基である。Ｒ²は同一又は異種の水素原子、ハロゲン原子、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基、炭素数２〜６のアルケニル基、炭素数６〜１０のアリール基、又はトリフルオロメチル基であり、ｍは１〜３の整数、ｎは２〜４の整数であり、ｍ＋ｎ＝５である。Ｒ⁴は酸不安定基を示す。Ｒ⁶、Ｒ¹¹は単結合、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基であり、エーテル基又はエステル基を有していてもよいが、炭素数１〜６の直鎖状、分岐状又は環状のアルキレン基の場合、式中のエステル基に連結した炭素原子は１級又は２級である。Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵は水素原子、又は炭素数１〜６の直鎖状、分岐状又は環状のアルキル基である。ａ、ｂ、ｃ１、ｃ２は０＜ａ＜１．０、０＜ｂ＜１．０、０≦ｃ１＜１．０、０≦ｃ２＜１．０、０＜ｃ１＋ｃ２＜１．０、０＜ａ＋ｂ＋ｃ１＋ｃ２≦１．０の範囲である。）

(In the formula, R ¹ , R ³ , R ⁵ and R ¹⁰ are the same or different hydrogen atoms or methyl groups. X is a single bond, or —C (═O) —O—, and Y is a single bond. Or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms which may have an ester group or an ether group, or Y represents two carbon atoms adjacent to each other in the benzene ring. R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon number 2 6 alkenyl group, an aryl group having 6 to 10 carbon atoms, or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer from 2 to 4, .R ⁴ is a m + n = 5 is An acid labile group, wherein R ⁶ and R ¹¹ are a single bond or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms. In the case of a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, the carbon atom linked to the ester group in the formula is primary. R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. A, b, c1, c2 are 0 <a <1.0, 0 <b <1.0, 0 ≦ c1 <1.0, 0 ≦ c2 <1.0, 0 <c1 + c2 <1.0, 0 <A + b + c1 + c2 ≦ 1.0.

The polymer compound used in the pattern forming method of the present invention includes at least one repeating unit (a) represented by the general formula (1), the repeating unit (b), the repeating unit (c1) or ( c2), but it is further a repeat derived from a monomer having an adhesive group such as a hydroxy group, a cyano group, a carbonyl group, an ester group, an ether group, a lactone ring, a carbonyl group, or a carboxylic acid anhydride group. Unit d may be copolymerized.
The monomer unit of the repeating unit d is exemplified below.

In the repeating units a, b, c1, c2, and d, the ratio of these repeating units is as follows: 0 <a <1.0, 0 <b <1.0, 0 ≦ c1 <1.0, 0 ≦ c2 <1 0.0, 0 ≦ d <1.0, and 0 <a + b + c1 + c2 + d ≦ 1.0. In this case, 0 <c1 + c2 <1.0 is particularly preferable.
Preferably 0.05 ≦ a ≦ 0.8, 0.1 ≦ b ≦ 0.8, 0 ≦ c1 ≦ 0.8, 0 ≦ c2 ≦ 0.8, 0 ≦ d ≦ 0.8, 0.2 ≦ a + b + c1 + c2 ≦ 1.0. In this case, 0.1 ≦ c1 + c2 ≦ 0.8 and 0.3 ≦ a + b + c1 + c2 + d ≦ 1.0 are particularly preferable.
More preferably, 0.07 ≦ a ≦ 0.7, 0.12 ≦ b ≦ 0.7, 0 ≦ c1 ≦ 0.7, 0 ≦ c2 ≦ 0.7, 0 ≦ d ≦ 0.7. 3 ≦ a + b + c1 + c2 + d ≦ 1.0. In this case, it is particularly preferable that 0.2 ≦ c1 + c2 ≦ 0.7 and 0.5 ≦ a + b + c1 + c2 + d ≦ 1.0.

Note that a + b + c1 + c2 + d = 1.0. Here, for example, a + b + c1 + c2 = 1 means that in the polymer compound containing the repeating units a, b, c1, and c2, the total amount of the repeating units a, b, c1, and c2 is 100 mol with respect to the total amount of all the repeating units. A + b + c1 + c2 <1 means that the total amount of repeating units a, b, c1, and c2 is less than 100 mol% with respect to the total amount of all repeating units, and other than a, b, c1, and c2. It has the repeating unit d.
Furthermore, in the case of a + b + c1 + c2 + d <1, in addition to a, b, c1, c2, and d, indene, acenaphthylene, norbornene, and norbornadiene may be contained as another repeating unit.

  The polymer compound serving as the base polymer of the resist material used in the pattern forming method of the present invention has a weight average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of 1,000 to 500,000, particularly 2,000 to 30. , 000 is preferable. If the weight average molecular weight is too small, the crosslinking efficiency in the thermal crosslinking after development of the resist material is lowered. If it is too large, the alkali solubility is lowered, and the trailing phenomenon may easily occur after pattern formation.

  Furthermore, in the polymer compound serving as the base polymer of the resist material used in the pattern forming method of the present invention, when the molecular weight distribution (Mw / Mn) is wide, a low molecular weight or high molecular weight polymer exists, so that after exposure, There is a possibility that foreign matter is seen on the pattern or the shape of the pattern is deteriorated. Therefore, since the influence of such molecular weight and molecular weight distribution tends to increase as the pattern rule becomes finer, in order to obtain a resist material suitably used for fine pattern dimensions, the multi-component copolymer to be used is obtained. The molecular weight distribution is preferably from 1.0 to 2.0, particularly preferably from 1.0 to 1.5 and narrow dispersion.

  It is also possible to blend two or more polymers having different composition ratios, molecular weight distributions, and molecular weights.

  In order to synthesize these polymer compounds, as one method, a monomer having an unsaturated bond for obtaining the repeating units a, b, c1, c2, and d is added to a radical initiator in an organic solvent and subjected to heat polymerization. There is a method, whereby a polymer compound can be obtained. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane and the like. As polymerization initiators, 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2-azobis (2-methylpropionate) ), Benzoyl peroxide, lauroyl peroxide and the like, and preferably polymerized by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. As the acid labile group, those introduced into the monomer may be used as they are, or the acid labile group may be once removed by an acid catalyst and then protected or partially protected. 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 of the present invention may contain an acid generator, particularly for functioning as a chemically amplified positive resist material. For example, the resist material contains a compound that generates an acid in response to actinic rays or radiation (photoacid generator). May be. 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-butoxy Phenyl) sulfonium, (3,4-ditert-butoxyphenyl) diphenylsulfonium, bis (3,4-ditert-butoxyphenyl) phenylsulfo , 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, trinaphthylsulfo , 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-fluorobenzene Sulfonate, 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-pentafluoropropane sulfonate, 2- (4- tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropanesulfonate, 2-adamantanecarbonylcarbonyl-1,1,3,3,3-pentafluoropropanesulfonate, 2-acetyloxy-1 1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropanesulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxy Propanesulfonate, 1,1-difluoro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- Norbornane-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.

The 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-butoxyphenylphenyl. Aryliodonium cations such as iodonium, 4-methoxyphenylphenyliodonium and sulfonates such as trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2 , 2,2-Trifluoroethanesulfonate, pentafluorobenzene Sulfonate, 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-cycl Hexanecarbonyloxy-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-difur Oro-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, etc., 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 type 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 Mantanylcarbonyloxy-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, nonafluorobutane sulfonate, dodecafluorohexane sulfonate, pentafluoroethyl perfluorocyclohexane sulfonate, heptadecafluorooctane sulfonate, 2,2,2-trifluoroethane sulfonate, pentafluorobenzene sulfonate, 4-trifluoromethylbenzene sulfonate, 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) phenyl sulfonate) and the like.

  As oxime sulfonates described in JP-A-9-95479, JP-A-9-230588, or the prior art in the text, α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (p-chlorobenzenesulfonyloxyimino) ) -Phenylacetonitrile, α- (4-nitrobenzenesulfonyloxyimino) -phenylacetonitrile, α- (4-nitro-2-trifluoromethylbenzenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -4 -Chlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzenesulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- ( Benzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (benzenesulfonyloxyimino) -2-thienylacetonitrile, α- (4-dodecylbenzene) Sulfonyloxyimino) -phenylacetonitrile, α-[(4-toluenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α-[(dodecylbenzenesulfonyloxyimino) -4-methoxyphenyl] acetonitrile, α- (tosyloxy) Imino) -3-thienylacetonitrile, α- (methylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenylacetononitrile , Α- (isopropylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclopentenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α -(Isopropylsulfonyloxyimino) -1-cyclohexenylacetonitrile, α- (n-butylsulfonyloxyimino) -1-cyclohexenylacetonitrile and the like can be mentioned.

（上記式中、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。） Also included are 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 group having 1 to 10 carbon atoms or a halobenzenesulfonyl group. R ^S2 represents a haloalkyl group group having 1 to 11 carbon atoms. Ar ^S1 is substituted or unsubstituted. Represents an aromatic group or a 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 addition amount of the photoacid generator in the chemically amplified resist material of the present invention may be any, but 0.1 to 20 parts by mass, preferably 100 parts by mass with respect to 100 parts by mass of the base resin (the polymer compound) in the resist material. 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 addition amount.

  In addition, a compound capable of decomposing with an acid to generate an acid (acid-growing compound) may be added to the resist material of the present invention.

  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 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 of the present invention can further contain any one or more of an organic solvent, a basic compound, a dissolution controller, and a surfactant.
The organic solvent used in 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 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 present invention, among these organic solvents, diethylene glycol dimethyl ether, 1-ethoxy-2-propanol, propylene glycol monomethyl ether acetate, and mixed solvents thereof, which are most excellent in solubility of the acid generator in the resist component, are 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 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 change after exposure is suppressed, substrate and environment dependency is reduced, and exposure margins and patterns are 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 Examples of tertiary aliphatic amines include 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 (eg, 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.

で表すことができる。側鎖Ｙは同一又は異種の、水素原子、又は直鎖状、分岐状又は環状の炭素数１〜２０のアルキル基を示し、エーテル基もしくはヒドロキシル基を含んでもよい。また、Ｘ同士が結合してこれらが結合する窒素原子と共に環を形成してもよい。） 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 chains X may be the same or different, and the following general formula (X1), (X2) or (X3)

Can be expressed as The 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. Moreover, you may form a ring with the nitrogen atom which X couple | bonds and these couple | bond. )

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.

（上記式中、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、又はスルフィドを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, and R ³⁰⁷ is a linear or branched alkylene group having 2 to 20 carbon atoms and contains one or more carbonyl groups, ether groups, ester groups, or sulfides. You may go out.)

  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 Rumorpholinoethyl, 2-morpholinoethyl hexanoate, 2-morpholinoethyl octoate, 2-morpholinoethyl decanoate, 2-morpholinoethyl laurate, 2-morpholinoethyl myristic acid, 2-morpholinoethyl palmitate, 2-morpholinoethyl stearate Is exemplified.

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

(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, N, N-bis (2-hydroxy). Ethyl) -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-a Toxiethyl) -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-aminopropio Nitrile, 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] amino Acetonitrile, 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 Acetonitrile, 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-aminop Cyanomethyl pionate, 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 propionate, 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.

（上記式中、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, a carbonate group, a cyano group and an 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.)

（上記式中、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 straight chain 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.)

（上記式中、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 atoms and charcoal A linear, branched or cyclic alkyl group or an aryl group having a prime 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. .)

（上記式中、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 part or all of the hydrogen atoms are halogen 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 may be CO ₂ R ³²⁶ , OR ³²⁷ or cyano group, and R ³²⁶ may be 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 ) _N - is a .n = 0, 1, 2, 3 or 4 is a radical .R ³²⁹ is a hydrogen atom, a methyl group, .X an ethyl group or a phenyl group is a nitrogen atom or CR ³³⁰ .Y is A nitrogen 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 combine to form an aromatic ring having 6 to 20 carbon atoms or a heteroaromatic ring having 2 to 20 carbon atoms together with the carbon atom to which these are bonded.

（上記式中、Ｒ³³³は水素、又は炭素数１〜１０の直鎖状、分岐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窒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 independently ether, carbonyl, ester, alcohol, sulfide. An alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, which may contain one or more polar functional groups such as nitrile, amine, imine and amide And R ³³⁴ and R ³³⁵ may be bonded to each other to form a heterocyclic ring or heteroaromatic ring having 2 to 20 carbon atoms together with the nitrogen atom to which they are bonded. It may be formed.)

  In addition, 0.001-2 mass parts with respect to 100 mass parts of base resins, and especially 0.01-1 mass part are suitable for the compounding quantity of a nitrogen-containing organic compound. 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.

  In addition to the above components, a surfactant conventionally used for improving the coating property can be added to the resist material of the present invention. 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”, “FC-4430” (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 Daikin Industries ( ), MegaFuck “F-8151” (Dainippon Ink Industries, Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.), etc. Can be mentioned. Preferably, Florard “FC-430”, “FC-4430” (manufactured by Sumitomo 3M Co., Ltd.), “KH-20”, “KH-30” (both manufactured by Asahi Glass Co., Ltd.), “X-70- 093 "(manufactured by Shin-Etsu Chemical Co., Ltd.).

  If necessary, the resist material 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 present invention is a phenol having a mass average molecular weight of 100 to 1,000, preferably 150 to 800, and a compound having two or more phenolic hydroxyl groups in the molecule. The hydrogen atom of the carboxylic group of the compound having a carboxy group in the molecule or the compound in which the hydrogen atom of the ionic hydroxyl group is substituted with an acid labile group as a whole at an average rate of 0 to 100 mol% is averaged by the acid labile group as a whole A compound substituted at a ratio of 50 to 100 mol% 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 with 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, and the like.
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 mass 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. Note that specific examples of each group are the same as described above.

  The blending 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 of the present invention, for example, one or two or more compounds selected from the following [Group I] and [Group II] can be used, but are not limited thereto. Is not to be done. 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 (where 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 is _{- (CH 2) i - (} i = 2~10), shows 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 mass average molecular weight of 1,000 to 5,000.
λ is a number that makes the compound of formula (A7) a mass 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.

（上記式中、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.

（上記式中、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。） As the acetylene alcohol derivative that can be added to the resist material of the present invention, those represented by the following general formulas (S1) and (S2) can be preferably used.

(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.)

  As acetylene alcohol derivatives, 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.

Here, double patterning will be described. FIGS. 1 to 3 show a conventional double patterning method.
In the double patterning method 1 shown in FIG. 1, a photoresist film 30 is applied and formed on a substrate 20 to be processed on the substrate 10. In order to prevent the pattern collapse of the photoresist pattern, the thickness of the photoresist film has been reduced, and a method of processing a substrate to be processed using a hard mask has been performed in order to compensate for the accompanying decrease in etching resistance. Here, the double patterning method shown in FIG. 1 is a laminated film in which a hard mask 40 is laid between the photoresist film 30 and the substrate 20 to be processed (FIG. 1-A). In the double patterning method, a hard mask is not necessarily required, and instead of the hard mask, an underlayer film of carbon film and a silicon-containing intermediate film may be laid, and an organic antireflection film is provided between the hard mask and the photoresist film. May be laid. The hard _mask, SiO _{2, SiN, SiON,} etc. p-Si is used. In the double patterning method 1, the resist material used is a positive resist material. In this method, the resist film 30 is exposed and developed (FIG. 1-B), then the hard mask 40 is dry-etched (FIG. 1-C), and after removing the photoresist film, the second photoresist film 50 is removed. Is applied, formed, exposed and developed (FIG. 1-D). Next, the substrate 20 to be processed is dry-etched (FIG. 1-E). In order to etch using the hard mask pattern and the second photoresist pattern as a mask, the etching resistance of the hard mask 40 and the photoresist film 50 is etched. Due to the difference, the pattern size after etching of the substrate to be processed is shifted.

  In order to solve the above problem, in the double patterning method 2 shown in FIG. 2, two layers of hard masks are laid, the upper hard mask 42 is processed with the first resist pattern, and the lower hard mask is formed with the second resist pattern. 41 is processed, and the substrate to be processed is dry-etched using two hard mask patterns. The etching selectivity between the first hard mask 41 and the second hard mask 42 needs to be high, and this is a rather complicated process.

The double patterning method 3 shown in FIG. 3 is a method using a trench pattern. In this case, only one hard mask is required. However, since the trench pattern has a lower light contrast than the line pattern, it is difficult to resolve the pattern after development and has a disadvantage that the margin is narrow. Although it is possible to shrink by thermal flow or RELAX method after forming a wide trench pattern, the process becomes complicated. If a negative resist material is used, exposure can be performed with a high optical contrast. However, a negative resist material generally has a disadvantage that the contrast is lower than that of a positive resist material and the resolution performance is low. In the trench process, the positional deviation between the first trench and the second trench leads to the deviation of the line width of the finally remaining line, so that very high-precision alignment is required.
In any case, the double patterning methods 1 to 3 mentioned so far involve etching of the hard mask twice, which is a process defect.

  On the other hand, the double patterning method according to the present invention is as shown in FIG. 4, and the first positive type is formed on the substrate 20 to be processed on the substrate 10 via the hard mask 40 as in FIG. A first photoresist film 30 is formed from a resist material (FIG. 4-A). Next, the first resist film 30 is exposed and developed (FIG. 4-B), and then the resist film 30 is crosslinked and cured by irradiation with ultraviolet rays having a wavelength of 300 nm or less to form a crosslinked resist film 30a (FIG. 4-C). . In this case, crosslinking by heating may be further performed before irradiation with ultraviolet rays having a wavelength of 300 nm or less, or crosslinking by heating may be further performed after irradiation with ultraviolet rays. Crosslinking by heating can form a stronger pattern in combination with crosslinking by ultraviolet irradiation. As heating temperature, the range of 150 to 300 degreeC and 5 to 600 second is preferable. When the temperature is lower than 150 ° C., the first pattern may be dissolved at the time of resist coating for forming the second pattern due to insufficient crosslinking or by the second development. If it exceeds 300 ° C., the pattern may be deformed by decomposition of the polymer main chain or heat flow. Further, a second resist material is applied thereon to form a second resist film 50, which is then exposed and developed, and the first resist film 30 (crosslinked resist film 30a) is exposed to the space portion of the pattern. A pattern of the second photoresist film 50 is formed (FIG. 4-D). Next, the hard mask 40 is etched (FIG. 4-E), and the substrate 20 to be processed is further dry-etched to remove the crosslinked resist film 30a and the second resist film 50 (FIG. 4-F).

  Although FIG. 4 shows a method of forming the second pattern between the first patterns, a second pattern orthogonal to the first pattern may be formed (FIG. 5). An orthogonal pattern can be formed by one exposure, but if the dipole illumination and the modified illumination are combined, the contrast of the line pattern can be made very high. As shown in FIG. 5-A, the Y-direction line is patterned, the pattern is insolubilized by the method of the present invention, and the second resist is applied to form the X-direction line as shown in FIG. 5-B. To do. By combining the X and Y lines to form a lattice pattern, the vacant part is made a hole. What is formed is not limited to the orthogonal pattern, but may be a T-shaped pattern or may be separated as shown in FIG.

In this case, a silicon substrate is generally used as the substrate 10. Examples of the substrate to be processed 20 include SiO ₂ , SiN, SiON, SiOC, p-Si, α-Si, TiN, WSi, BPSG, SOG, Cr, CrO, CrON, MoSi, a low dielectric film, and an etching stopper film thereof. It is done. The hard mask 40 is as described above. Instead of the hard mask, an underlayer film made of a carbon film and an intermediate intervening layer such as a silicon-containing intermediate film or an organic antireflection film may be formed.

  In the present invention, the first resist film made of the first positive resist material is formed directly on the substrate to be processed or via an intermediate intervening layer such as the hard mask. The thickness of the first resist film The thickness is preferably 10 to 1,000 nm, particularly 20 to 500 nm. This resist film is heated (pre-baked) before exposure, and as this condition, it is preferable to carry out at 60 to 180 ° C., particularly 70 to 150 ° C. for 10 to 300 seconds, and particularly 15 to 200 seconds.

  Next, exposure is performed. Here, the exposure is most preferably 193 nm exposure using a high energy beam having a wavelength of 140 to 250 nm, and among these, ArF excimer laser. The exposure may be a dry atmosphere in the air or a nitrogen stream, or may be immersion exposure in water. In ArF immersion lithography, a liquid that has a refractive index of 1 or more and is highly transparent at the exposure wavelength, such as pure water or alkane, is used as the immersion solvent. In immersion lithography, pure water or other liquid is inserted between a pre-baked resist film and a projection lens. As a result, a lens with an NA of 1.0 or more can be designed, and a finer pattern can be formed. Immersion lithography is an important technique for extending the life of ArF lithography to the 45 nm node. In the case of immersion exposure, pure water rinsing (post-soak) after exposure to remove the water droplet residue remaining on the resist film may be performed, and elution from the resist film is prevented, and the surface lubricity of the film is prevented. In order to increase the thickness, a protective film may be formed on the resist film after pre-baking. As a resist protective film used in immersion lithography, for example, a polymer compound having a 1,1,1,3,3,3-hexafluoro-2-propanol residue that is insoluble in water and dissolved in an alkaline developer is used. A base and a material dissolved in an alcohol solvent having 4 or more carbon atoms, an ether solvent having 8 to 12 carbon atoms, or a mixed solvent thereof is preferable. After forming the photoresist film, pure water rinsing (post-soak) may be performed to extract acid generators from the film surface or to wash out particles, or to remove water remaining on the film after exposure. Rinse (post-soak) may be performed.

It is preferable to expose so that the exposure amount in exposure is about 1 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² . Next, post exposure baking (PEB) is performed on a hot plate at 60 to 150 ° C. for 1 to 5 minutes, preferably 80 to 120 ° C. for 1 to 3 minutes.

  Further, 0.1 to 5% by weight, preferably 2 to 3% by weight, using an aqueous developer such as tetramethylammonium hydroxide (TMAH) for 0.1 to 3 minutes, preferably 0.5 to 2 minutes. The target pattern is formed on the substrate by development by a conventional method such as a dip method, a paddle method, or a spray method.

Curing of the resist pattern after development requires light irradiation with a wavelength of 300 nm or less and, in some cases, crosslinking by heating. The light irradiation after development is a high energy ray having a wavelength of 300 nm or less, specifically, KrF excimer light having a wavelength of 248 nm, light emitted from a low-pressure mercury lamp including wavelengths 254 nm and 185 nm, ArF excimer light having a wavelength of 193 nm, Xe having a wavelength of 172 nm. ₂ excimer light, 157 nm F ₂ excimer light, 146 nm Kr ₂ excimer light, and 126 nm Ar ₂ excimer light are preferable. In the case of light, the exposure amount is in the range of 10 mJ / cm ^{2 to} 10 J / cm ² . Irradiation with an excimer laser or excimer lamp having a wavelength of 200 nm or less, particularly 193 nm, 172 nm, 157 nm, 146 nm, and 122 nm, not only generates acid from the photoacid generator, but also promotes a crosslinking reaction by light irradiation. Further, a thermal acid generator of ammonium salt as a photoresist material is added in an amount of 0.001 to 20 parts by mass, preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the base resin of the photoresist material. It is also possible to generate an acid. In this case, the generation of acid and the crosslinking reaction proceed simultaneously. The heating conditions are preferably 100 to 300 ° C., particularly 130 to 250 ° C. and preferably 10 to 300 seconds. Thereby, a crosslinked resist film insoluble in the solvent and the alkaline developer is formed.

（式中、Ｒ^101d、Ｒ^101e、Ｒ^101f、Ｒ^101gはそれぞれ水素原子、炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基、アルケニル基、オキソアルキル基又はオキソアルケニル基、炭素数６〜２０のアリール基、又は炭素数７〜１２のアラルキル基又はアリールオキソアルキル基を示し、これらの基の水素原子の一部又は全部がアルコキシ基によって置換されていてもよい。Ｒ^101dとＲ^101e又はＲ^101dとＲ^101eとＲ^101fとは互いに結合してこれらが結合する窒素原子と共に環を形成してもよく、環を形成する場合には、環の形成に関与するＲ^101dとＲ^101e又はＲ^101dとＲ^101eとＲ^101fは炭素数３〜１０のアルキレン基、又は式中の窒素原子を環の中に有する複素芳香族環を示す。） In addition, the following are mentioned as a thermal acid generator of the said ammonium salt.

Wherein R ^101d , R ^101e , R ^101f and R ^101g are each a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, an alkenyl group, an oxoalkyl group or an oxoalkenyl group, carbon the number 6 to 20 aryl group, or an aralkyl group or an aryl oxoalkyl group having 7 to 12 carbon atoms, some or all of the hydrogen atoms of these groups and may .R ^101d be substituted by an alkoxy group R ^101e or R ^101d and R ^101e and R ^101f may be bonded to each other to form a ring with the nitrogen atom to which they are bonded, and in the case of forming a ring, R ^101d and R involved in the formation of the ring ^101e or R ^101d and R ^101e and R ^{101f each} represents an alkylene group having 3 to 10 carbon atoms or a heteroaromatic ring having a nitrogen atom in the formula.

Specific examples of K ⁻ include imido acids such as perfluoroalkanesulfonic acid such as triflate and nonaflate, bis (trifluoromethylsulfonyl) imide, bis (perfluoroethylsulfonyl) imide, and bis (perfluorobutylsulfonyl) imide. , Methido acids such as tris (trifluoromethylsulfonyl) methide, tris (perfluoroethylsulfonyl) methide, and sulfonate having a fluoro substituted at the α-position represented by the following general formula (K-1), And sulfonates in which the α-position shown in -2) is fluoro-substituted.

In General Formula (K-1), ^R102 represents a hydrogen atom, a linear, branched or cyclic alkyl group or acyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 6 to 6 carbon atoms. 20 aryl groups or aryloxy groups, which may have an ether group, an ester group, a carbonyl group, a lactone ring, or a part or all of the hydrogen atoms of these groups may be substituted with fluorine atoms Good. In general formula (K-2), R ¹⁰³ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or an aryl having 6 to 20 carbon atoms. It is a group.

  When light irradiation with a wavelength of 180 nm or less is performed in the air, the resist surface is oxidized by the generation of ozone, and the film thickness is considerably reduced. Ozone oxidation by light irradiation is used for cleaning organic substances attached to the substrate. Therefore, the resist film is also cleaned by ozone, and the film disappears when the exposure amount is large. Therefore, when irradiating excimer lasers or excimer lamps having wavelengths of 172 nm, 157 nm, 146 nm, and 122 nm, purging with an inert gas such as nitrogen gas, He gas, argon gas, or Kr gas, the oxygen or moisture concentration is 10 ppm. Light irradiation is desirable in the following atmosphere.

  Next, a second resist film is formed by applying a resist material on an intermediate intervening layer such as a hard mask on which the pattern of the crosslinked resist film is formed. The resist material is a positive type, particularly a chemical amplification. A positive resist material is preferred. As a resist material in this case, the same resist material as the first resist material described above can be used, and a known resist material can also be used. In this case, the pattern forming method of the present invention is characterized in that a crosslinking reaction is performed after the development of the first resist pattern, but the crosslinking reaction is not particularly required after the development of the second resist pattern. Therefore, the phenol group represented by the general formula (1) is not essential as a resist material for forming the second resist pattern, and any conventionally known chemically amplified positive resist material can be used.

  About this 2nd resist film, it is preferable to expose and develop according to a conventional method, and to form the pattern of a 2nd resist film in the space part of the said bridge | crosslinking resist film pattern, and to halve the distance between patterns. The conditions for the second resist film thickness, exposure, development, and the like can be the same as those described above.

  Next, an intermediate intervening layer such as a hard mask is etched using the cross-linked resist film and the second resist film as a mask, and the substrate to be processed is further etched. In this case, the intermediate intervening layer such as a hard mask can be etched by dry etching using a fluorocarbon or halogen gas, and the etching of the substrate to be processed has an etching selectivity with respect to the hard mask. The etching gas and conditions for the etching can be selected as appropriate, and can be performed by dry etching using a gas such as chlorofluorocarbon, halogen, oxygen, and hydrogen. Next, the cross-linked resist film and the second resist film are removed. These removals may be performed after etching of the intermediate intervening layer such as a hard mask. The cross-linked resist film can be removed by dry etching using oxygen, radicals, etc., and the second resist film can be removed in the same manner as above, or an amine solvent, or an organic solvent such as sulfuric acid / hydrogen peroxide solution. It can be performed with a stripping solution.

  EXAMPLES Hereinafter, although a synthesis example, an Example, and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example etc. In addition, a weight average molecular weight (Mw) shows the polystyrene conversion weight average molecular weight by GPC.

[Synthesis example]
As a polymer compound added to the resist material, each monomer is combined and subjected to a copolymerization reaction in a tetrahydrofuran solvent, crystallized in methanol, further washed with hexane, isolated and dried, and shown below. Polymer compounds (Polymers 1 to 14 and Comparative polymer 1) having the composition were 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
Molecular weight (Mw) = 8,500
Dispersity (Mw / Mn) = 1.91

Polymer 2
Molecular weight (Mw) = 8,900
Dispersity (Mw / Mn) = 1.78

Polymer 3
Molecular weight (Mw) = 7,700
Dispersity (Mw / Mn) = 1.84

Polymer 4
Molecular weight (Mw) = 7,100
Dispersity (Mw / Mn) = 1.76

Polymer 5
Molecular weight (Mw) = 8,800
Dispersity (Mw / Mn) = 1.73

Polymer 6
Molecular weight (Mw) = 8,600
Dispersity (Mw / Mn) = 1.76

Polymer 7
Molecular weight (Mw) = 8,400
Dispersity (Mw / Mn) = 1.88

Polymer 8
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.78

Polymer 9
Molecular weight (Mw) = 8,100
Dispersity (Mw / Mn) = 1.66

Polymer 10
Molecular weight (Mw) = 9,200
Dispersity (Mw / Mn) = 1.74

Polymer 11
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.95

Polymer 12
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.95

Polymer 13
Molecular weight (Mw) = 9,400
Dispersity (Mw / Mn) = 2.10

Polymer 14
Molecular weight (Mw) = 8,400
Dispersity (Mw / Mn) = 1.80

Comparative polymer 1
Molecular weight (Mw) = 8,900
Dispersity (Mw / Mn) = 1.86

溶解制御剤：ＤＲＲ（下記構造式参照）

有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）
ＣｙＨ（シクロヘキサノン） [Examples 1 to 28, Comparative Examples 1 and 2]
Evaluation of crosslinkability of polymer by light irradiation In order to examine the crosslinkability of the polymer compounds synthesized above (polymers 1 to 14 and comparative polymer 1) by light irradiation, each polymer and acid generation were prepared with the compositions shown in Table 1 below. An agent and a solvent were mixed, and a solution filtered through a 0.2 μm Teflon (registered trademark) filter was prepared.
Each composition in Table 1 is as follows.
Acid generator: PAG (photo acid generator) 1, TAG (thermal acid generator) 1, 2 (see the following structural formula)

Dissolution control agent: DRR (see structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
CyH (cyclohexanone)

Each polymer solution was applied to an 8-inch silicon substrate, baked at 100 ° C. for 60 seconds, and the film thickness was 120 nm as measured by a film thickness optical film thickness meter.
Examples 1 to 10 were baked at 200 ° C. for 60 seconds after irradiating 200 mJ / cm ² of light with an ArF excimer laser having a wavelength of 193 nm. Examples 12 to 21 were baked at 180 ° C. for 60 seconds after irradiation with light of 100 mJ / cm ² with a Xe ₂ excimer lamp having a wavelength of 172 nm and an irradiance of 10 mW. In Example 11, a Kr ₂ excimer lamp having a wavelength of 146 nm and an irradiance of ₂ mW was irradiated with light of 50 mJ / cm ² and then baked at 200 ° C. for 60 seconds. In Examples 22 to 28, after baking at 200 ° C. for 60 seconds, light of 100 mJ / cm ² was irradiated with a Xe ₂ excimer lamp having a wavelength of 172 nm and an irradiance of 10 mW.
When Comparative Example 1 was not irradiated with light, Comparative Example 2 was baked at 200 ° C. for 60 seconds after irradiation with 200 mJ / cm ² of light with an ArF excimer laser.

In film reduction by solvent treatment, a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and cyclohexanone (CyH) 70:30 mass ratio is dispensed on the film for 20 seconds, spin-dried at 2,000 rpm for 30 seconds, and 60 ° C. at 100 ° C. After drying for 2 seconds, the film thickness was measured, and the difference from the film thickness before solvent dispensing was determined. In film reduction by development, paddle development was performed for 30 seconds with a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution, and the difference from the film thickness before development was determined.
The results are shown in Table 1.

  From the results shown in Table 1, it was confirmed that the cross-linking proceeded by the light irradiation because the solvent resistance and the alkali developer resistance were improved by the light irradiation with a wavelength of 300 nm or less.

塩基性化合物：Ｑｕｅｎｃｈｅｒ１（下記構造式参照）

有機溶剤：ＰＧＭＥＡ（プロピレングリコールモノメチルエーテルアセテート）
ＣｙＨ（シクロヘキサノン） [Examples 29 to 44, Comparative Examples 3 and 4]
Preparation of Positive Resist Material Using the polymer compounds synthesized above (Polymers 1 to 14 and Comparative Polymer 1), a solution dissolved in the composition shown in Table 2 below is filtered through a 0.2 μm size filter to form a resist. A solution was prepared.
Each composition in Table 2 is as follows.
Acid generator: PAG1, 2, TAG1 (see the following structural formula)

Basic compound: Quencher 1 (see the structural formula below)

Organic solvent: PGMEA (propylene glycol monomethyl ether acetate)
CyH (cyclohexanone)

Double resist patterning evaluation The resist materials prepared in Examples 29 to 44 and Comparative Examples 3 and 4 shown in Table 2 were deposited on a silicon wafer with ARC-29A (Nissan Chemical Industry Co., Ltd.) having a thickness of 80 nm. The coated substrate was spin-coated and baked at 110 ° C. for 60 seconds using a hot plate, so that the resist film had a thickness of 120 nm.
This was exposed using an ArF excimer laser scanner (manufactured by Nikon Corporation, NSR-S307E, NA0.85, σ0.93, normal illumination, 6% halftone phase shift mask). The film was baked for 2 seconds and developed with an aqueous solution of 2.38% by mass of tetramethylammonium hydroxide for 30 seconds to obtain a positive type isolated pattern (first pattern) having dimensions of 70 nm and a pitch of 350 nm.
In Examples 29 to 39 and 41 to 44, baking was performed at 200 ° C. for 60 seconds after exposure using an ArF excimer laser (200 mJ / cm ² ) having a wavelength of 193 nm. In Example 40, after baking at 200 ° C. for 60 seconds, exposure was performed using an ArF excimer laser (200 mJ / cm ² ) having a wavelength of 193 nm.
When Comparative Example 3 was not irradiated with light, Comparative Example 4 was baked at 200 ° C. for 60 seconds after exposure using an ArF excimer laser (200 mJ / cm ² ) having a wavelength of 193 nm.
Next, the same resist material was applied on the first pattern so as to have a film thickness of 120 nm, and a baked wafer was prepared. Using this wafer, exposure, PEB, and development are performed with an ArF excimer laser scanner in the same manner as the first pattern, using a mask whose pattern is shifted by 170 nm on the wafer, and the dimensions of the first pattern are adjusted. It was measured.
The results are shown in Table 2.

  In the resist materials using Examples 29 to 44, it was confirmed that a second pattern line was formed between the first patterns. In Comparative Example 3, the second pattern was formed, but the first pattern was not formed because it was dissolved when the second resist was applied. In Comparative Example 4 using a resist material based on Comparative Polymer 1 that does not have a phenol group, the first pattern dimension was significantly reduced because the insolubilization of the first pattern was not complete.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

It is sectional drawing explaining an example of the conventional double patterning method, A is the state which formed the to-be-processed substrate, the hard mask, and the resist film on the board | substrate, B is the state which exposed and developed the resist film, C is A state in which the hard mask is etched, D indicates a state in which the second resist film is formed and the resist film is exposed and developed, and E indicates a state in which the substrate to be processed is etched. It is sectional drawing explaining the other example of the conventional double patterning method, A is the state which formed the to-be-processed substrate, the 1st and 2nd hard mask, and the resist film on the board | substrate, B is exposing the resist film , Developed state, C is a state where the second hard mask is etched, D is a state where the first resist film is removed and a second resist film is formed, and then this resist film is exposed and developed, E Indicates a state in which the first hard mask is etched, and F indicates a state in which the substrate to be processed is etched. It is sectional drawing explaining another example of the conventional double patterning method, A is the state which formed the to-be-processed substrate, the hard mask, and the resist film on the board | substrate, B is the state which exposed and developed the resist film, C Is a state in which the hard mask is etched, D is a state in which the first resist film is removed and a second resist film is formed, and this resist film is exposed and developed, and E is a state in which the hard mask is further etched. , F indicates a state in which the substrate to be processed is etched. It is sectional drawing explaining an example of the double patterning method of this invention, A is the state which formed the to-be-processed substrate, the hard mask, and the resist film on the board | substrate, B is the state which exposed and developed the resist film, C is , A state in which the resist film is crosslinked, D is a state in which the second resist film is formed and then exposed and developed, E is a state in which the hard mask is etched, and F is a state in which the substrate to be processed is etched. Indicates. It is the sky figure explaining an example of the double patterning method of the present invention, A is the state where the 1st pattern was formed, B was the 2nd pattern which intersects the 1st pattern after the 1st pattern formation Indicates the state. It is an aerial view explaining another example of the double patterning method of this invention, A is the state which formed the 1st pattern, B is the 2nd which separated from the 1st pattern after 1st pattern formation. The state which formed the pattern is shown.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 Substrate 20 Substrate 30 Resist film 30a Cross-linked resist film 40 Hard mask 50 Second resist film

Claims (11)

  A first positive resist material containing a polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is applied on a substrate to form a first resist film. Then, after the heat treatment, the resist film is exposed with a high energy beam, and after the heat treatment, the resist film is developed with a developer, and then the first resist film is crosslinked and cured by irradiation with a high energy beam having a wavelength of 300 nm or less. Then, a second positive resist material is applied onto the substrate to form a second resist film, and after the heat treatment, the second resist film is exposed with a high energy beam, and after the heat treatment, a developer A pattern forming method comprising a step of developing the second resist film using   A first positive resist material containing a polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is applied on a substrate to form a first resist film. Then, after the heat treatment, the resist film is exposed with a high energy beam, and after the heat treatment, the resist film is developed with a developer, and then the first resist film is formed by irradiation and heating with a high energy beam having a wavelength of 300 nm or less. After crosslinking and curing, a second positive resist material is applied onto the substrate to form a second resist film, and after the heat treatment, the second resist film is exposed with a high energy beam, and after the heat treatment A pattern forming method comprising a step of developing the second resist film using a developer.   A first positive resist material containing a polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is applied on a substrate to form a first resist film. Then, after the heat treatment, the resist film is exposed with a high energy beam, and after the heat treatment, the resist film is developed with a developer, and then heated, and then irradiated with a high energy beam having a wavelength of 300 nm or less. The resist film is cross-linked and cured, and a second positive resist material is applied onto the substrate to form a second resist film. After the heat treatment, the second resist film is exposed with a high energy beam, A pattern forming method comprising a step of developing the second resist film using a developer after the heat treatment. High energy rays having a wavelength of 300 nm or less used for crosslinking of the first resist pattern formed by development are emitted from a low-pressure mercury lamp including wavelengths 254 nm and 185 nm, KrF excimer light having a wavelength of 248 nm, KrCl excimer light having a wavelength of 222 nm, wavelength 4. A 193 nm ArF excimer light, a 172 nm Xe ₂ excimer light, a 157 nm F ₂ excimer light, a 146 nm Kr ₂ excimer light, a 126 nm Ar ₂ excimer light, or an electron beam. The pattern formation method of any one of these.   The exposure for forming the first resist pattern and the second resist pattern is immersion lithography in which a liquid having a refractive index of 1.4 or more is immersed between a lens and a wafer by an ArF excimer laser having a wavelength of 193 nm. The pattern forming method according to claim 1, wherein:   6. The pattern forming method according to claim 5, wherein the liquid having a refractive index of 1.4 or more is water.   7. The pattern forming method according to claim 1, wherein a space between patterns is reduced by forming a second pattern in a space portion of the first pattern.   The pattern forming method according to claim 1, wherein a second pattern intersecting with the first pattern is formed.   The pattern forming method according to claim 1, wherein the second pattern is formed in a direction different from the first pattern in a space portion where the pattern of the first pattern is not formed. A polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is a repeating unit (a) and a repeating unit (b) represented by the following general formula (1): The positive resist material used for the pattern formation method of any one of Claims 1 thru | or 9 characterized by the above-mentioned.

(In the formula, R ¹ and R ³ represent the same or different hydrogen atoms or methyl groups. X is a single bond, or —C (═O) —O—, and Y is a single bond, or a carbon number of 1 to A linear, branched or cyclic alkylene group which may have an ester group or an ether group, or Y is bonded to two adjacent carbon atoms of the benzene ring to form an alicyclic ring R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, alkenyl group having 2 to 6 carbon atoms, An aryl group having 6 to 10 carbon atoms or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer of 2 to 4, and m + n = 5, and R ⁴ represents an acid labile group. A and b are in the range of 0 <a <1.0, 0 <b <1.0, and 0 <a + b ≦ 1.0.) A polymer compound obtained by copolymerizing a repeating unit having a phenol group and a repeating unit whose alkali solubility is improved by an acid is a repeating unit (a), (b) or (c1) represented by the following general formula (2). 10) The positive resist material used in the pattern forming method according to claim 1, wherein the positive resist material has (c2).

(In the formula, R ¹ , R ³ , R ⁵ and R ¹⁰ are the same or different hydrogen atoms or methyl groups. X is a single bond, or —C (═O) —O—, and Y is a single bond. Or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms which may have an ester group or an ether group, or Y represents two carbon atoms adjacent to each other in the benzene ring. R ² is the same or different hydrogen atom, halogen atom, linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, carbon number 2 6 alkenyl group, an aryl group having 6 to 10 carbon atoms, or a trifluoromethyl group, m is an integer of 1 to 3, n is an integer from 2 to 4, .R ⁴ is a m + n = 5 is An acid labile group, wherein R ⁶ and R ¹¹ are a single bond or a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms. In the case of a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, the carbon atom linked to the ester group in the formula is primary. R ⁷ , R ⁸ , R ⁹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ are a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. A, b, c1, c2 are 0 <a <1.0, 0 <b <1.0, 0 ≦ c1 <1.0, 0 ≦ c2 <1.0, 0 <c1 + c2 <1.0, 0 <A + b + c1 + c2 ≦ 1.0.

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