JP2007297590A - Resist material and pattern formation method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist material that has good barrier performance to water, enables to keep a resist composition from eluting to water, has a high receding contact angle to water, is useful for an immersion lithography due to excellent process applicability without requiring a protective film, and enables to form a fine pattern precisely, as well as to provide a pattern formation method using the material. <P>SOLUTION: This resist material comprises a polymer compound having a repeating unit, as a minimum, represented by general formula (1). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

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

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

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

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

  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, various factors such as an increase in the cost of the scanner by using a large amount of expensive CaF ₂ single crystal for the projection lens, a change in the optical system due to the introduction of a hard pellicle because the durability of the soft pellicle is extremely low, and a reduction in resist etching resistance Because of this problem, it was proposed to postpone F ₂ lithography and early introduction of ArF immersion lithography (see Non-Patent Document 1).

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

  Here, various problems due to the presence of water on the resist film have been pointed out. In other words, the photo acid generator, which is a resist composition, the acid generated by light irradiation, and the amine compound added to the resist film as a quencher elutes in the water in contact (leaching), resulting in a pattern shape Change, pattern collapse due to water swelling of the photoresist film, and the like.

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

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

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

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

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

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

  As described above, in the immersion lithography, there are problems such as an increase in cost due to the use of the protective film. On the other hand, development of a resist material for immersion lithography that does not require a protective film by imparting water barrier performance has been underway. This is intended to reduce the cost.

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

In order to eliminate remaining droplets on the surface of the photoresist or protective film after scanning, it is necessary to improve the ease of movement of water on these coating films. In order to reduce the number of defects due to immersion exposure, it has been shown that it is effective to increase the receding contact angle of the photoresist or the protective film with respect to water (see Non-Patent Document 4).
However, coexistence of barrier performance and a high receding contact angle has not been achieved, and there has been a demand for a resist material that achieves both.

JP 2005-264131 A Proc. SPIE Vol. 4690 xxix Proc. SPIE Vol. 5040 p724 2nd Immersion Work Shop, July 11, 2003, Resist and Cover Material Investing for Immersion Lithography 2nd International Symposium on Immersion Lithography, 12-15 / Sept., 2005, Defectivity data taken with a full-field immersion exposure tool, Nakano et., Al.

  The present invention has been made in view of such problems, has a good barrier performance against water, can suppress the elution of the resist composition into water, has a high receding contact angle with respect to water, An object of the present invention is to provide an effective resist material for immersion lithography that can eliminate residual liquid droplets and does not require a protective film and has excellent process applicability, and a pattern forming method using such a material. .

（式中、Ｒ¹、Ｒ^２は独立して水素原子、炭素数１〜２０の直鎖状、分岐状、又は環状のアルキル基で、Ｒ^１とＲ^２が結合して環を形成していても良く、その場合Ｒ^１とＲ^２との炭素数の総和が２〜２０の二価の有機基を表す。Ｒ^３、Ｒ^４、Ｒ^１１、Ｒ^１４は独立して水素原子又はメチル基、Ｒ^５は炭素数１〜１４の直鎖状、分岐状、又は環状のアルキル基であり、一部またはすべての水素原子がフッ素原子で置換されていてもよく、イミノスルホニル基を含んでもよい。Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は独立して−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−、−Ｏ−、−Ｃ（＝Ｏ）−Ｒ^６−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−Ｃ（＝Ｏ）−Ｏ−のいずれかである。Ｒ^６は炭素数１〜１０の直鎖状、分岐状、又は環状のアルキレン基である。Ｒ^１２は炭素数４〜１２の環状構造を有するアルキレン基またはアルカントリイル基でフッ素で置換されていても良く、Ｒ^１３は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良く、Ｒ^１２とＲ^１３が結合して炭素数３〜１２の環を形成していても良い。Ｒ^１５は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良い。ｎ１は１又は２である。ａ−１、ｂ−１、ｂ−２、ｂ−３は、０＜（ａ−１）≦１、０≦（ｂ−１）＜１、０≦（ｂ−２）＜１、０≦（ｂ−３）＜１、０＜（ａ−１）＋（ｂ−１）＋（ｂ−２）＋（ｂ−３）≦１の範囲を満たす。） The present invention has been made to solve the above problems, and provides a resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (1). 1).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are bonded to form a ring. In this case, the total carbon number of R ¹ and R ² represents a divalent organic group having 2 to 20. R ³ , R ⁴ , R ¹¹ and R ¹⁴ are independently a hydrogen atom or a methyl group. , R ⁵ is a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, part or all of the hydrogen atoms may be substituted with fluorine atoms, and may contain an iminosulfonyl group X ¹ , X ² , X ³ , and X ⁴ are independently —C (═O) —, —C (═O) —O—, —C (═O) —O—R ⁶ —, —O—. , —C (═O) —R ⁶ —C (═O) —, —C (═O) —O—R ⁶ —C (═O) —O—, wherein R ⁶ has 1 carbon atom. -10 linear,岐状, or cyclic alkylene group .R ¹² may be substituted by fluorine alkylene group or alkanetriyl groups having a cyclic structure having 4 to 12 carbon atoms, R ¹³ is a hydrogen atom, C 1 -C 10 linear, branched alkyl groups may be substituted by fluorine, attached R ¹² and R ¹³ is may form a ring of 3 to 12 carbon atoms .R ¹⁵ Is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, n1 is 1 or 2. a-1, b-1, b-2 , B-3 are 0 <(a-1) ≦ 1, 0 ≦ (b-1) <1, 0 ≦ (b-2) <1, 0 ≦ (b-3) <1, 0 <(a -1) + (b-1) + (b-2) + (b-3) ≦ 1.

（式中、Ｒ^４、Ｒ^７、Ｒ^１１、Ｒ^１４は独立して水素原子又はメチル基、Ｒ^８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、１つ以上の水素原子がフッ素原子で置換されていてもよい。Ｒ^５は炭素数１〜１４の直鎖状、分岐状、又は環状のアルキル基であり、一部またはすべての水素原子がフッ素原子で置換されていてもよく、イミノスルホニル基を含んでもよい。Ｒ^９は少なくとも１つ以上の水素原子がフッ素原子で置換された炭素数１〜１０の直鎖状又は分岐状のアルキル基で、Ｒ^８とＲ^９が結合して環を形成していても良く、その場合Ｒ^８とＲ^９との炭素数の総和が２〜１２の三価の有機基を表す。Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は独立して−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−、−Ｏ−、−Ｃ（＝Ｏ）−Ｒ^６−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−Ｃ（＝Ｏ）−Ｏ−のいずれかである。Ｒ^６は炭素数１〜１０の直鎖状、分岐状、又は環状のアルキレン基である。Ｒ^１２は炭素数４〜１２の環状構造を有するアルキレン基またはアルカントリイル基でフッ素で置換されていても良く、Ｒ^１３は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良く、Ｒ^１２とＲ^１３が結合して炭素数３〜１２の環を形成していても良い。Ｒ^１５は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良い。ｎ１は１又は２である。ａ−２、ｂ−１、ｂ−２、ｂ−３は、０＜（ａ−２）≦１、０≦（ｂ−１）＜１、０≦（ｂ−２）＜１、０≦（ｂ−３）＜１、０＜（ａ−２）＋（ｂ−１）＋（ｂ−２）＋（ｂ−３）≦１の範囲を満たす。） The present invention also provides a resist material comprising at least a polymer compound having a repeating unit represented by the following general formula (2) (claim 2).

(In the formula, R ⁴ , R ⁷ , R ¹¹ and R ¹⁴ are independently a hydrogen atom or a methyl group, R ⁸ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, one The above hydrogen atoms may be substituted with fluorine atoms, R ⁵ is a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, and some or all of the hydrogen atoms are fluorine atoms. R ⁹ is a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and may include an iminosulfonyl group. ⁸ and R ⁹ may be bonded to form a ring, and in this case, the total number of carbon atoms of R ⁸ and R ⁹ represents a trivalent organic group having ^{2 to} 12. X ¹ , X ² , X ^{3, X 4} are independently -C (= O) -, - C (= O) -O -, - C (= O) -O-R 6 ^{, -O -, - C (=} O) -R 6 -C (= O) -, - C (= O) -O-R 6 -C (= O) is either -O- .R ⁶ Is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, R ¹² may be substituted with an alkylene group or alkanetriyl group having a cyclic structure having 4 to ¹² carbon atoms by fluorine. R ¹³ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, and R ¹² and R ¹³ are bonded to each other to have 3 to 12 carbon atoms. R ¹⁵ may be a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, and n1 is 1 or 2. a-2, b-1, b-2, b-3 are 0 <(a-2) ≦ 1, 0 ≦ (b-1) <1, 0 ≦ (b-2) <1, 0 ≦ b-3) satisfies the <1,0 <(a-2) + (b-1) + (b-2) + (b-3) ≦ 1 range.)

  Since a photoresist film formed using these resist materials has a good barrier performance against water, elution of the photoresist composition into water during immersion exposure can be suppressed. For this reason, the pattern shape change by an elution thing can be reduced. Accordingly, since a protective film provided to prevent elution is not required in conventional immersion lithography, the cost required for forming the protective film can be reduced.

Moreover, because the photoresist film has a high receding contact angle with respect to water, it is difficult for droplets to remain on the surface of the photoresist film after immersion exposure scanning, and pattern formation is induced by droplets remaining on the film surface. Defects can be reduced.
Therefore, the resist material of the present invention has excellent process applicability, can reduce the cost in immersion lithography, and can form a fine pattern with few defects with high accuracy.

In this case, it is preferable that the polymer compound does not have an alkyl group having 5 or more carbon atoms.
If the above polymer compound does not have an alkyl group having 5 or more carbon atoms, there is little possibility that a spot-like defect called Blob is generated on the resist film, and a pattern with fewer defects can be formed.

  In this case, the resist material is a chemically amplified positive resist material (Claim 4) and includes at least a repeating unit having an acid labile group and a repeating unit having a hydroxy group and / or an adhesive group of a lactone ring. A base resin is preferably included (claim 5).

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

  Moreover, it is preferable that the resist material further contains any one or more of an organic solvent, a basic compound, a dissolution controller, and a surfactant (claim 6).

  Thus, by further blending an organic solvent, for example, the coating property of a resist material on a substrate can be improved, and by blending a basic compound, the diffusion rate of acid in the resist film In addition, the resolution can be further improved, and by adding a dissolution control agent, the difference in dissolution rate between the exposed and unexposed areas can be further increased, and the resolution can be further improved. In addition, the coating property of the resist material can be further improved or controlled by adding a surfactant.

  In addition, there is provided a pattern forming method including at least a step of applying the resist material on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer. 7).

  Needless to say, development may be performed after the post-exposure heat treatment, and various other processes such as an etching process, a resist removal process, and a cleaning process may be performed.

  In this case, it is preferable that the high energy ray has a wavelength in the range of 180 nm to 250 nm.

  Thus, a finer pattern can be formed if exposure is performed with the high energy beam having a wavelength in the range of 180 nm to 250 nm.

  In addition, the step of exposing with the high energy beam can be performed by immersion exposure through a liquid (Claim 9). In the immersion exposure, an exposure wavelength in the range of 180 to 250 nm is used, and the resist A liquid can be inserted between the substrate on which the material is applied and the projection lens, and the substrate can be exposed through the liquid.

  Thus, by performing immersion exposure, the resolution is improved and a finer pattern can be formed.

  Further, water can be used as the liquid (claim 11).

  An example of the liquid used for the immersion exposure is water.

  As described above, since the photoresist film formed using the resist material of the present invention has a good barrier performance against water, the dissolution of the photoresist composition into water can be suppressed. It is possible to reduce the pattern shape change due to the eluate. Accordingly, since a protective film provided to prevent elution is not required in conventional immersion lithography, the cost required for forming the protective film can be reduced.

Moreover, since the photoresist film has a high receding contact angle with respect to water, it is difficult for droplets to remain on the surface of the photoresist film after scanning during immersion exposure, and a pattern that induces droplets remaining on the film surface. Formation defects can be reduced.
Therefore, by using the resist material of the present invention, the cost in immersion lithography can be reduced and a fine pattern with few defects can be formed with high accuracy.

Hereinafter, although embodiment of this invention is described, this invention is not limited to these.
As described above, for immersion exposure, development of a resist material having both barrier performance and a high receding contact angle has been demanded.

  As a result of intensive studies and studies to solve this problem, the present inventors have found that a specific polymer additive is used in an immersion lithography process in which a photoresist film and water are in direct contact without using a protective film. A photoresist film comprising (1) suppressing elution of the photoresist composition into water, and (2) achieving an increase in receding contact angle with respect to water. As a result of various studies on the composition and formulation of the present invention, the present invention was completed.

（式中、Ｒ¹、Ｒ^２は独立して水素原子、炭素数１〜２０の直鎖状、分岐状、又は環状のアルキル基で、Ｒ^１とＲ^２が結合して環を形成していても良く、その場合Ｒ^１とＲ^２との炭素数の総和が２〜２０の二価の有機基を表す。Ｒ^３、Ｒ^４、Ｒ^１１、Ｒ^１４は独立して水素原子又はメチル基、Ｒ^５は炭素数１〜１４の直鎖状、分岐状、又は環状のアルキル基であり、一部またはすべての水素原子がフッ素原子で置換されていてもよく、イミノスルホニル基を含んでもよい。Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は独立して−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−、−Ｏ−、−Ｃ（＝Ｏ）−Ｒ^６−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−Ｃ（＝Ｏ）−Ｏ−のいずれかである。Ｒ^６は炭素数１〜１０の直鎖状、分岐状、又は環状のアルキレン基である。Ｒ^１２は炭素数４〜１２の環状構造を有するアルキレン基またはアルカントリイル基でフッ素で置換されていても良く、Ｒ^１３は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良く、Ｒ^１２とＲ^１３が結合して炭素数３〜１２の環を形成していても良い。Ｒ^１５は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良い。ｎ１は１又は２である。ａ−１、ｂ−１、ｂ−２、ｂ−３は、０＜（ａ−１）≦１、０≦（ｂ−１）＜１、０≦（ｂ−２）＜１、０≦（ｂ−３）＜１、０＜（ａ−１）＋（ｂ−１）＋（ｂ−２）＋（ｂ−３）≦１の範囲を満たす。） That is, the present invention provides a resist material characterized in that it contains at least a polymer compound having a repeating unit represented by the following general formula (1).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are bonded to form a ring. In this case, the total carbon number of R ¹ and R ² represents a divalent organic group having 2 to 20. R ³ , R ⁴ , R ¹¹ and R ¹⁴ are independently a hydrogen atom or a methyl group. , R ⁵ is a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, part or all of the hydrogen atoms may be substituted with fluorine atoms, and may contain an iminosulfonyl group X ¹ , X ² , X ³ , and X ⁴ are independently —C (═O) —, —C (═O) —O—, —C (═O) —O—R ⁶ —, —O—. , —C (═O) —R ⁶ —C (═O) —, —C (═O) —O—R ⁶ —C (═O) —O—, wherein R ⁶ has 1 carbon atom. -10 linear,岐状, or cyclic alkylene group .R ¹² may be substituted by fluorine alkylene group or alkanetriyl groups having a cyclic structure having 4 to 12 carbon atoms, R ¹³ is a hydrogen atom, C 1 -C 10 linear, branched alkyl groups may be substituted by fluorine, attached R ¹² and R ¹³ is may form a ring of 3 to 12 carbon atoms .R ¹⁵ Is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, n1 is 1 or 2. a-1, b-1, b-2 , B-3 are 0 <(a-1) ≦ 1, 0 ≦ (b-1) <1, 0 ≦ (b-2) <1, 0 ≦ (b-3) <1, 0 <(a -1) + (b-1) + (b-2) + (b-3) ≦ 1.

（式中、Ｒ^４、Ｒ^７、Ｒ^１１、Ｒ^１４は独立して水素原子又はメチル基、Ｒ^８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、１つ以上の水素原子がフッ素原子で置換されていてもよい。Ｒ^５は炭素数１〜１４の直鎖状、分岐状、又は環状のアルキル基であり、一部またはすべての水素原子がフッ素原子で置換されていてもよく、イミノスルホニル基を含んでもよい。Ｒ^９は少なくとも１つ以上の水素原子がフッ素原子で置換された炭素数１〜１０の直鎖状又は分岐状のアルキル基で、Ｒ^８とＲ^９が結合して環を形成していても良く、その場合Ｒ^８とＲ^９との炭素数の総和が２〜１２の三価の有機基を表す。Ｘ^１、Ｘ^２、Ｘ^３、Ｘ^４は独立して−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−、−Ｏ−、−Ｃ（＝Ｏ）−Ｒ^６−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^６−Ｃ（＝Ｏ）−Ｏ−のいずれかである。Ｒ^６は炭素数１〜１０の直鎖状、分岐状、又は環状のアルキレン基である。Ｒ^１２は炭素数４〜１２の環状構造を有するアルキレン基またはアルカントリイル基でフッ素で置換されていても良く、Ｒ^１３は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良く、Ｒ^１２とＲ^１３が結合して炭素数３〜１２の環を形成していても良い。Ｒ^１５は水素原子、炭素数１〜１０の直鎖状、分岐状のアルキル基であり、フッ素で置換されていても良い。ｎ１は１又は２である。ａ−２、ｂ−１、ｂ−２、ｂ−３は、０＜（ａ−２）≦１、０≦（ｂ−１）＜１、０≦（ｂ−２）＜１、０≦（ｂ−３）＜１、０＜（ａ−２）＋（ｂ−１）＋（ｂ−２）＋（ｂ−３）≦１の範囲を満たす。） Moreover, this invention contains the high molecular compound which has a repeating unit shown by following General formula (2) at least, The resist material characterized by the above-mentioned.

(In the formula, R ⁴ , R ⁷ , R ¹¹ and R ¹⁴ are independently a hydrogen atom or a methyl group, R ⁸ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, one The above hydrogen atoms may be substituted with fluorine atoms, R ⁵ is a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, and some or all of the hydrogen atoms are fluorine atoms. R ⁹ is a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and may include an iminosulfonyl group. ⁸ and R ⁹ may be bonded to form a ring, and in this case, the total number of carbon atoms of R ⁸ and R ⁹ represents a trivalent organic group having ^{2 to} 12. X ¹ , X ² , X ^{3, X 4} are independently -C (= O) -, - C (= O) -O -, - C (= O) -O-R 6 ^{, -O -, - C (=} O) -R 6 -C (= O) -, - C (= O) -O-R 6 -C (= O) is either -O- .R ⁶ Is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, R ¹² may be substituted with an alkylene group or alkanetriyl group having a cyclic structure having 4 to ¹² carbon atoms by fluorine. R ¹³ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, and R ¹² and R ¹³ are bonded to each other to have 3 to 12 carbon atoms. R ¹⁵ may be a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, and n1 is 1 or 2. a-2, b-1, b-2, b-3 are 0 <(a-2) ≦ 1, 0 ≦ (b-1) <1, 0 ≦ (b-2) <1, 0 ≦ b-3) satisfies the <1,0 <(a-2) + (b-1) + (b-2) + (b-3) ≦ 1 range.)

  When a photoresist film is formed by spin coating or the like using a resist material to which a polymer compound having a repeating unit of the general formula (1) or the general formula (2) is added, the polymer compound is exposed on the surface of the photoresist film. Oriented to Since the polymer compound is highly hydrophobic and excellent in water slidability, the formed photoresist film has a good barrier performance against water, and the elution of the photoresist composition into water during immersion exposure. Can be suppressed. For this reason, the pattern shape change by an elution thing can be reduced. Therefore, since the protective film provided for preventing elution in the conventional immersion lithography is not required, the cost required for forming the protective film can be reduced.

In addition, since the photoresist film has a high receding contact angle with respect to water, it is difficult for droplets to remain on the surface of the photoresist film after scanning during immersion exposure, and a pattern that induces droplets remaining on the film surface. Formation defects can be reduced.
Further, since the polymer compound is soluble in an alkaline aqueous solution, defects such as residues are hardly generated after development.
Therefore, by using the resist material of the present invention, the cost in immersion lithography can be reduced and a fine pattern with few defects can be formed with high accuracy.

（式中Ｒ^３は前述と同様である。） Although the repeating unit (a-1) shown by the said General formula (1) is not specifically limited, The following specific example can be given.

(Wherein R ³ is the same as described above.)

（式中Ｒ^７は前述と同様である。） Although the repeating unit (a-2) shown by the said General formula (2) is not specifically limited, The following specific example can be given.

(Wherein R ⁷ is the same as described above.)

Although the repeating unit (b-1) shown by the said General formula (1) (2) is not specifically limited, The following specific example can be given.

（式中Ｒ^４は前述と同様である。）

(Wherein R ⁴ is the same as described above.)

（式中Ｒ^１１は前述と同様である。） Although the repeating unit (b-2) shown by the said General formula (1) (2) is not specifically limited, The following specific example can be given.

(Wherein R ¹¹ is the same as described above.)

（式中Ｒ^１４は前述と同様である。） The repeating unit (b-3) represented by the general formulas (1) and (2) is not particularly limited, but the following specific examples can be given.

(Wherein R ¹⁴ is the same as described above.)

In addition to the repeating units (a-1), (a-2), (b-1), (b-2), and (b-3), the polymer compound of the present invention has, for example, a hydroxy group shown below. It may contain a repeating unit.

  The polymer compound of the present invention preferably does not have an alkyl group having 5 or more carbon atoms. Alkyl groups having 5 or more carbon atoms have very high water repellency. If the polymer compound does not have an alkyl group having 5 or more carbon atoms, a spot-like defect called Blob, which is caused by excessively high water repellency on the photoresist surface after development, appears on the resist film. Less likely to occur. Therefore, a pattern with fewer defects can be formed.

The mass average molecular weight of the polymer compound having the repeating unit of general formula (1) or general formula (2) added to the resist material is 1,000 to 100,000, preferably 3,000 to 30, respectively. However, it is not limited to these. When the molecular weight is 1,000 or more, sufficient barrier performance against water can be exhibited during immersion exposure, and dissolution of the photoresist composition into water can be sufficiently suppressed. Further, if the molecular weight is 100,000 or less, the dissolution rate of the polymer compound in the alkaline developer is sufficiently high. Therefore, when a pattern is formed using a photoresist film containing the polymer compound, the resin residue is formed on the substrate. There is little fear of adhering to.
In the general formula (1), the repeating units (a-1), (b-1), (b-2), and (b-3) are 0.1 ≦ (a-1) + (b− 1) It is preferable to satisfy + (b-2) + (b-3) ≦ 1. In the general formula (2), the repeating units (a-2), (b-1), (b-2), and (b-3) are 0.1 ≦ (a-2) + (b− 1) It is preferable to satisfy + (b-2) + (b-3) ≦ 1.

  In addition, the polymer compound having the repeating unit of the general formula (1) or the general formula (2) may be blended with the resist material as one kind of polymer compound, or two or more kinds of polymer compounds. May be mixed in an arbitrary ratio and blended with the resist material.

  The compounding ratio of the polymer compound to the resist material is such that the total mass of the polymer compound to be added is 0.1 to 50 parts by mass, preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the base resin of the resist material. Is good. If this is 0.1 part by mass or more, the receding contact angle between the photoresist film surface and water is sufficiently improved. Moreover, if this is 50 mass parts or less, the melt | dissolution rate to the alkaline developing solution of a photoresist film is small, and the height of the formed fine pattern is fully maintained.

  The resist material is preferably a chemically amplified positive resist material, and further includes a base resin including at least a repeating unit having an acid labile group and a repeating unit having an adhesive group of a hydroxy group and / or a lactone ring. It is preferable that it contains.

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

Examples of the base resin include polymer compounds having a mass average molecular weight of 1,000 to 100,000, preferably 3,000 to 30,000, represented by the following formula (R1) and / or the following formula (R2). However, it is not limited to these.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  For example, the general formula (L4-3) represents one or a mixture of two selected from the groups represented by the following general formulas (L4-3-1) and (L4-3-2). To do.

（式中Ｒ^L41は前述と同様である。）

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

  The general formula (L4-4) represents one or a mixture of two or more selected from groups represented by the following general formulas (L4-4-1) to (L4-4-4). And

（式中Ｒ^L41は前述と同様である。）

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

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

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

（式中Ｒ^L41は前述と同様である。）

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

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

Further, tertiary alkyl groups having 4 to 20 carbon atoms, trialkylsilyl groups each having 1 to 6 carbon atoms, and oxoalkyl groups having 4 to 20 carbon atoms are specifically exemplified as ^RL04 . The thing similar to a thing etc. can be illustrated.

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

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

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

  Specific examples of the repeating unit introduced at the composition ratio b1 ′ in the formula (R1) include, but are not limited to, the following.

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

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

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

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

Iodonium salt is a salt of iodonium cation and sulfonate or bis (substituted alkylsulfonyl) imide, tris (substituted alkylsulfonyl) methide, diphenyliodonium, bis (4-tert-butylphenyl) iodonium, 4-tert-butoxyphenylphenyliodonium. Aryliodonium cations such as 4-methoxyphenylphenyliodonium and sulfonates such as trifluoromethanesulfonate, pentafluoroethanesulfonate, nonafluorobutanesulfonate, dodecafluorohexanesulfonate, pentafluoroethylperfluorocyclohexanesulfonate, heptadecafluorooctanesulfonate, 2, 2,2-trifluoroethanesulfonate, pentafluorobenzenes Phonate, 4-trifluoromethylbenzenesulfonate, 4-fluorobenzenesulfonate, mesitylenesulfonate, 2,4,6-triisopropylbenzenesulfonate, toluenesulfonate, benzenesulfonate, 4- (4-toluenesulfonyloxy) benzenesulfonate, naphthalenesulfonate , Camphorsulfonate, octanesulfonate, dodecylbenzenesulfonate, butanesulfonate, methanesulfonate, 2-benzoyloxy-1,1,3,3,3-pentafluoropropanesulfonate, 1,1,3,3,3-pentafluoro- 2- (4-phenylbenzoyloxy) propanesulfonate, 1,1,3,3,3-pentafluoro-2-pivaloyloxypropanesulfonate, 2-cyclo Xancarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-furoyloxypropane sulfonate, 2-naphthoyloxy-1,1, 3,3,3-pentafluoropropane sulfonate, 2- (4-tert-butylbenzoyloxy) -1,1,3,3,3-pentafluoropropane sulfonate, 2-adamantanecarbonylcarbonyl-1,1,3 , 3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-pentafluoro-2-hydroxypropane sulfonate, 1, , 1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro Ro-2-naphthyl-ethanesulfonate, 1,1,2,2-tetrafluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10 ] dodec-3-en-8-yl) ethanesulfonate, 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 Mantanecarbonyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 2-acetyloxy-1,1,3,3,3-pentafluoropropane sulfonate, 1,1,3,3,3-penta Fluoro-2-hydroxypropane sulfonate, 1,1,3,3,3-pentafluoro-2-tosyloxypropane sulfonate, 1,1-difluoro-2-naphthyl-ethane sulfonate, 1,1,2,2-tetra fluoro-2- (norbornan-2-yl) ethanesulfonate, 1,1,2,2-tetrafluoro-2- (tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodeca-3 And a compound substituted with ene-8-yl) ethanesulfonate.

Examples of the nitrobenzyl sulfonate photoacid generator include 2,4-dinitrobenzyl sulfonate, 2-nitrobenzyl sulfonate, and 2,6-dinitrobenzyl sulfonate. Specific examples of the sulfonate include trifluoromethane sulfonate and pentafluoroethane. Sulfonate, 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 ) Ethanone 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-tri) Fluoro-1- (1-butanesulfonyloxyimino) -ethyl) -phenoxy) -propoxy) -phenyl) ethanone oxime (1-butanesulfonate) and the like. 2,2,2-trifluoro-1- (4- (3- (4- (2,2,2-trifluoro-1- (4- (4-methylphenylsulfonyl) described in Japanese Patent No. 6916591 Oxy) phenylsulfonyloxyimino) -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) ethanone oxime (2,5-bis (4-methylphenylsulfonyloxy) benzenesulfonyloxy) fe Rusuruhoneto), and the like.

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

  Examples thereof include oxime sulfonates represented by the following formula (for example, specific examples are described in WO2004 / 074242).

（上式中、Ｒ^S1は置換又は非置換の炭素数１〜１０のハロアルキルスルホニル、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。）

(In the above formula, R ^S1 represents a substituted or unsubstituted haloalkylsulfonyl or halobenzenesulfonyl group having 1 to 10 carbon atoms. R ^S2 represents a haloalkyl 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 is 0.1 to 20 parts by mass, preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the base resin in the resist material. Part. If the photoacid generator is 20 parts by mass or less, the transmittance of the photoresist film is sufficiently large, and there is little risk of degradation of resolution performance. 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 growth 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, the diffusion is controlled and there is little possibility of degradation of resolution and pattern shape.

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 thereof include esters such as ethyl propionate, tert-butyl acetate, tert-butyl propionate, propylene glycol mono tert-butyl ether acetate, and lactones such as γ-butyrolactone. Although it can be used in mixture, it is not limited to these. 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.

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 formula, n = 1, 2, or 3. The side chain X may be the same or different and can be represented by the following general formulas (X1) to (X3). The side chain Y is the same or different. Represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and may contain an ether group or a hydroxyl group, and Xs may be bonded to form a ring. )

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-methoxy). Ethoxymethoxy) 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-diaza Cyclooctadecane, 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-methoxyethoxycarbonyl) 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-acetoxy) Ethyl) 2-[(methoxycarbonyl) methoxycarbonyl] ethylamine, N, N-bis (2-hydroxyethyl) 2- (2-oxopropoxycarbonyl) ethylamine, N, N-bis (2-acetoxyethyl) 2- ( 2-oxopropoxycarbonyl) ethylamine, N, N-bis 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-formyloxye) Xoxycarbonyl) 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-butylbis [ 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 (methoxycarbonylmethyl) ) Amine, tris (ethoxycarbonylmethyl) amine, N-butylbis (methoxycarbonylmethyl) amine, N-hexylbis (methoxycarbonylmethyl) amine, β- (diethylamino) -δ-valerolactone.

（式中、Ｘは前述の通り、Ｒ³⁰⁷は炭素数２〜２０の直鎖状又は分岐状のアルキレン基であり、カルボニル基、エーテル基、エステル基、スルフィドを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 the cyclic structure shown by the following general formula (B) -2 is illustrated.

(In the formula, as described above, 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, and sulfides. May be.)

  Specifically as formula (B) -2, 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, methoxy 2- (1-Pyrrolidinyl) ethyl acetate, 4- [2- (methoxycarbonyloxy) ethyl] mol Phosphorus, 1- [2- (t-butoxycarbonyloxy) ethyl] piperidine, 4- [2- (2-methoxyethoxycarbonyloxy) ethyl] morpholine, methyl 3- (1-pyrrolidinyl) propionate, 3-piperidi Methyl nopropionate, methyl 3-morpholinopropionate, methyl 3- (thiomorpholino) propionate, methyl 2-methyl-3- (1-pyrrolidinyl) propionate, ethyl 3-morpholinopropionate, 3-piperidinopropion Methoxycarbonylmethyl acid, 2-hydroxyethyl 3- (1-pyrrolidinyl) propionate, 2-acetoxyethyl 3-morpholinopropionate, 2-oxotetrahydrofuran-3-yl 3- (1-pyrrolidinyl) propionate, 3-morpholino Tetrahydrofurfuryl propionate Glycidyl 3-piperidinopropionate, 2-methoxyethyl 3-morpholinopropionate, 2- (2-methoxyethoxy) ethyl 3- (1-pyrrolidinyl) propionate, butyl 3-morpholinopropionate, 3-piperidino Cyclohexyl propionate, α- (1-pyrrolidinyl) methyl-γ-butyrolactone, β-piperidino-γ-butyrolactone, β-morpholino-δ-valerolactone, methyl 1-pyrrolidinyl acetate, methyl piperidinoacetate, methyl morpholinoacetate, thiomorpholino Methyl acetate, ethyl 1-pyrrolidinyl acetate, 2-methoxyethyl morpholinoacetate, 2-morpholinoethyl 2-methoxyacetate, 2-morpholinoethyl 2- (2-methoxyethoxy) acetate, 2- [2- (2-methoxyethoxy) Ethoxy] acetic acid 2-morpholino Ethyl, 2-morpholinoethyl hexanoate, 2-morpholinoethyl octoate, 2-morpholinoethyl decanoate, 2-morpholinoethyl laurate, 2-morpholinoethyl myristate, 2-morpholinoethyl palmitate, 2-morpholinoethyl stearate Is exemplified.

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

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

(In the 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 above formulas (B) -3 to (B) -6 include 3- (diethylamino) propiononitrile and N, N-bis (2-hydroxyethyl). -3-aminopropiononitrile, N, N-bis (2-acetoxyethyl) -3-aminopropiononitrile, N, N-bis (2-formyloxyethyl) -3-aminopropiononitrile, N, N -Bis (2-methoxyethyl) -3-aminopropiononitrile, N, N-bis [2- (methoxymethoxy) ethyl] -3-aminopropiononitrile, N- (2-cyanoethyl) -N- (2 -Methoxyethyl) -3-aminopropionate methyl, N- (2-cyanoethyl) -N- (2-hydroxyethyl) -3-aminopropionate methyl, N- (2-acetoxy) Ethyl) -N- (2-cyanoethyl) -3-aminopropionate, 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-aminopropiononito 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] aminoacetate Nitrile, N-cyanomethyl-N- (2-methoxyethyl) -3-aminopropionate methyl, N-cyanomethyl-N- (2-hydroxyethyl) -3-aminopropionate methyl, 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) aminoacetate Nitrile, 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-aminopropio Cyanomethyl acid, 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 propi Cyanomethyl onacid, cyanomethyl 1-piperidinepropionate, cyanomethyl 4-morpholinepropionate, 1-pyrrolidinepropionic acid (2-cyanoethyl), 1-piperidinepropionic acid (2-cyanoethyl), 4-morpholinepropionic acid (2-cyanoethyl) Is exemplified.

  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 formula, R ³¹⁰ is an alkyl group having a linear, branched or cyclic polar functional group having 2 to 20 carbon atoms, and examples of the polar functional group include a hydroxyl group, a carbonyl group, an ester group, an ether group, and a sulfide group. , Carbonate group, cyano group, or 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.)

  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.

(Wherein R ³¹⁴ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group, or an aralkyl group. R ³¹⁵ is a straight chain having 1 to 20 carbon atoms, It is an alkyl group having a branched or cyclic polar functional group, which contains 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, a carbonate One or more of any of the groups may be included.)

  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 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 polar functional group having 2 to 20 carbon atoms. An alkyl group having a 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 , or R ³¹⁹ and R ³²⁰ are bonded to each other to form a benzene ring. May form a naphthalene ring or a pyridine ring, R ³²¹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or an aryl group, and R ³²² and R ³²³ are hydrogen. Atoms, linear, branched or ring having 1 to 10 carbon atoms And R ³²¹ and R ³²³ may combine to form a benzene ring or a naphthalene ring.)

  Furthermore, the nitrogen-containing organic compound which has an aromatic carboxylate structure shown by the following general formula (B) -11, 12, 13, and 14 is illustrated.

(In the 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, straight chain having 1 to 20 carbon atoms. , Branched or cyclic alkyl group, aryl group having 6 to 20 carbon atoms, aralkyl group having 7 to 20 carbon atoms, alkoxy group having 1 to 10 carbon atoms, acyloxy group having 1 to 10 carbon atoms, or carbon number R ³²⁵ may be CO ₂ R ³²⁶ , OR ³²⁷ or cyano group, and R ³²⁶ may be a carbon number in which some methylene groups may be substituted with oxygen atoms. R ³²⁷ is an alkyl group having 1 to 10 carbon atoms or an acyl group in which some of the methylene groups may be substituted with oxygen atoms, R ³²⁸ is a single bond, a methylene group, ethylene, sulfur atom or _{-O (CH 2 CH 2 O)} n -Group, n = 0, 1, 2, 3 or 4. R ³²⁹ is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, X 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 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.

  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.

(Wherein 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 In addition, a part of hydrogen atoms may be substituted with a halogen atom, 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. )

  In addition, the compounding quantity of a nitrogen-containing organic compound is 0.001-2 mass parts with respect to 100 mass parts of base resins, Especially 0.01-1 mass part is suitable. If the blending 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” (all manufactured by Sumitomo 3M Limited), Surflon “S-141”, “S-145”, “KH-10”, “KH-20”, “ KH-30 "," KH-40 "(all manufactured by Asahi Glass Co., Ltd.), Unidyne" DS-401 "," DS-403 "," DS-451 "(all manufactured by Daikin Industries, Ltd.), Mega For example, “F-8151” (manufactured by Dainippon Ink Industries, Ltd.), “X-70-092”, “X-70-093” (all manufactured by Shin-Etsu Chemical Co., Ltd.) can be used. Preferably, Florard “FC-430” (manufactured by Sumitomo 3M Limited), “KH-20”, “KH-30” (all manufactured by Asahi Glass Co., Ltd.), “X-70-093” (Shin-Etsu Chemical Co., Ltd.) Product).

  If necessary, the resist material of the present invention may further contain other components such as a dissolution control agent, 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 a ratio of 0 to 100 mol% as a whole 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 by an acid labile group is 50 mol% or more, preferably 70 mol% or more of the entire carboxy group on average, and the upper limit is 100 mol%.

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

In the above formula, R ²⁰¹ and R ²⁰² each represent a hydrogen atom, or a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, such as a hydrogen atom, a methyl group, an ethyl group, or a butyl group. , A propyl group, an ethynyl group, and a cyclohexyl group.

R ²⁰³ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or — (R ²⁰⁷ ) _h COOH (wherein R ²⁰⁷ is a linear chain having 1 to 10 carbon atoms) And h represents 0 or 1), and examples thereof include those similar to R ²⁰¹ and R ²⁰² , or —COOH and —CH ₂ COOH.

R ²⁰⁴ represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, such as an ethylene group, a phenylene group, A carbonyl group, a sulfonyl group, an oxygen atom, a sulfur atom, etc. are mentioned.
R ²⁰⁵ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom, and examples thereof include a methylene group or the same as R ^204. It is done.

R ²⁰⁶ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a phenyl group or a naphthyl group each substituted with a hydroxyl group. For example, a hydrogen atom, a methyl group, an ethyl group Group, butyl group, propyl group, ethynyl group, cyclohexyl group, phenyl group substituted with hydroxyl group, naphthyl group, etc., respectively.

R ²⁰⁸ represents a hydrogen atom or a hydroxyl group.
j is an integer of 0-5. u and h are 0 or 1. s, t, s ′, t ′, s ″, t ″ satisfy s + t = 8, s ′ + t ′ = 5, s ″ + t ″ = 4, respectively, and at least 1 in each phenyl skeleton The number has two hydroxyl groups. α is a number that makes the 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 represents — (CH ₂ ) _i — (i = 2 to 10), an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom, or a sulfur atom.
R ⁴⁰⁶ represents an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 10 carbon atoms, a carbonyl group, a sulfonyl group, an oxygen atom or a sulfur atom.
R ⁴⁰⁷ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alkenyl group, a phenyl group or a naphthyl group each substituted with a hydroxyl group.

R ⁴⁰⁹ represents a linear or branched alkylene group having 1 to 10 carbon atoms.
R ⁴¹⁰ represents a hydrogen atom, a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, or —R ⁴¹¹ —COOH group (wherein R ⁴¹¹ is a linear or branched group having 1 to 10 carbon atoms) Represents an alkylene group.
R ⁴¹² represents a hydrogen atom or a hydroxyl group.

j is a number from 0 to 3, and s1, t1, s2, t2, s3, t3, s4, and t4 satisfy s1 + t1 = 8, s2 + t2 = 5, s3 + t3 = 4, s4 + t4 = 6, and each phenyl The number is such that it has at least one hydroxyl group in the skeleton.
s5 and t5 are numbers satisfying s5 + t5 = 5 with s5 ≧ 0 and t5 ≧ 0.
u is a number satisfying 1 ≦ u ≦ 4, and h is a number satisfying 1 ≦ h ≦ 4.

κ is a number that makes the compound of formula (A6) a 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.

(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 parts by mass or less, the resolution of the resist material is less likely to decrease.

  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.

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

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

  The acetylene alcohol derivative is preferably Surfinol 61, Surfinol 82, Surfinol 104, Surfinol 104E, Surfinol 104H, Surfinol 104A, Surfinol TG, Surfinol PC, Surfinol 440, Surfinol 465, Surfinol 485 (Air Products and Chemicals Inc.), Surfynol E1004 (manufactured by Nissin 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 composition. If it is 0.01% by mass or more, the effect of improving coating properties and storage stability is sufficiently obtained, and if it is 2% by mass or less, the resolution of the resist material is less likely to deteriorate.

  The present invention also includes a pattern formation comprising: a step of applying the above resist material onto a substrate; a step of exposing to high energy rays after heat treatment; and a step of developing using a developer. Provide a method. At this time, it is preferable that the high energy ray has a wavelength in the range of 180 nm to 250 nm.

  In addition, the step of exposing with the high energy ray can be performed by immersion exposure through a liquid, for example, using an exposure wavelength in the range of 180 to 250 nm, and using a substrate coated with the resist material and a projection lens. A liquid can be inserted in between, and the substrate can be exposed through the liquid. In addition, water etc. are mentioned as a liquid used for immersion exposure.

In order to form a pattern using the resist material of the present invention, a known lithography technique can be employed.
For example, a resist material is applied onto a substrate such as a silicon wafer by spin coating or the like so that the film thickness becomes 0.1 to 2.0 μm, and this is applied on a hot plate at 60 to 150 ° C. for 1 to 10 minutes. Preferably, pre-baking is performed at 80 to 140 ° C. for 1 to 5 minutes to form a photoresist film.

Next, a mask for forming a target pattern is placed over the above-mentioned photoresist film, and a high energy beam such as deep ultraviolet light, excimer laser, X-ray or electron beam is applied in an exposure amount of 1 to 200 mJ / cm ² , preferably 10 Irradiate to 100 mJ / cm ² .

  In addition to the normal exposure method, the exposure can be performed by an immersion method in which the projection lens and the photoresist film are immersed in water or the like.

As described above, the photoresist film formed using the resist material of the present invention has a good barrier performance against water and suppresses elution of the photoresist composition into water. Therefore, the cost required for forming the protective film can be reduced.
In addition, since the photoresist film has a high receding contact angle with respect to water, it is difficult for droplets to remain on the surface of the photoresist film after immersion exposure scanning, and pattern formation is induced by droplets remaining on the film surface. Defects can be reduced.

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

  The resist material of the present invention is particularly suitable for fine patterning using deep ultraviolet rays of 250 to 180 nm or excimer laser, X-rays and electron beams among high energy rays.

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

(Preparation of polymer compound)
As a polymer compound (polymer additive) added to the resist material, each monomer is combined and subjected to a copolymerization reaction in an isopropyl alcohol solvent, crystallized in hexane, and further washed repeatedly with hexane, and then isolated. The polymer compound having the composition shown below was obtained by drying. 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) = 7,300
Dispersity (Mw / Mn) = 1.67

Polymer 2
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.62

Polymer 3
Molecular weight (Mw) = 9,300
Dispersity (Mw / Mn) = 1.93

Polymer 4
Molecular weight (Mw) = 8,000
Dispersity (Mw / Mn) = 1.80

Polymer 5
Molecular weight (Mw) = 8,600
Dispersity (Mw / Mn) = 1.75

Polymer 6
Molecular weight (Mw) = 8,500
Dispersity (Mw / Mn) = 1.64

Polymer 7
Molecular weight (Mw) = 7,700
Dispersity (Mw / Mn) = 1.74

Polymer 8
Molecular weight (Mw) = 7,100
Dispersity (Mw / Mn) = 1.82

Polymer 9
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.79

Polymer 10
Molecular weight (Mw) = 8,500
Dispersity (Mw / Mn) = 1.72

Polymer 11
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.79

Polymer 12
Molecular weight (Mw) = 7,500
Dispersity (Mw / Mn) = 1.82

Polymer 13
Molecular weight (Mw) = 7,600
Dispersity (Mw / Mn) = 1.87

Polymer 14
Molecular weight (Mw) = 7,500
Dispersity (Mw / Mn) = 1.82

Polymer 15
Molecular weight (Mw) = 7,000
Dispersity (Mw / Mn) = 1.85

(Preparation of resist material)
In the composition shown below, the base resin, photoacid generator, basic compound, and organic solvent were mixed and dissolved, and then filtered through a Teflon (registered trademark) filter (pore size 0.2 μm) to obtain a resist material (resist 1. Resist 2) was prepared.

Resist 1
Mixed composition: base resin 1 (100 parts by mass), photoacid generator (5 parts by mass), basic compound (1 part by mass), organic solvent (1800 parts by mass)

分子量（Ｍｗ）＝７，６００
分散度（Ｍｗ／Ｍｎ）＝１．７６
光酸発生剤（PAG）：ノナフルオロブタンスルホン酸トリフェニルスルホニウム
塩基性化合物（クエンチャー）：２−（２−メトキシエトキシメトキシ）エチルモルホリン
有機溶剤：酢酸１−メトキシイソプロピル Base resin 1 (see the structural formula below)

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

Resist 2
Mixed composition: base resin 2 (100 parts by mass), photoacid generator (7 parts by mass), basic compound (0.8 parts by mass), organic solvent 1 (1330 parts by mass), organic solvent 2 (570 parts by mass)

分子量（Ｍｗ）＝５，７００
分散度（Ｍｗ／Ｍｎ）＝１．６９
光酸発生剤（PAG）：１，１，３，３，３−ペンタフルオロ−２−ベンゾイルオキシプロパンスルホン酸４−ｔ−ブトキシフェニルジフェニルスルホニウム
塩基性化合物（クエンチャー）：２−シクロヘキシルカルボキシエチルモルホリン
有機溶剤１：酢酸１−メトキシイソプロピル
有機溶剤２：シクロヘキサノン Base resin 2 (see the structural formula below)

Molecular weight (Mw) = 5,700
Dispersity (Mw / Mn) = 1.69
Photoacid generator (PAG): 1,1,3,3,3-pentafluoro-2-benzoyloxypropanesulfonic acid 4-t-butoxyphenyldiphenylsulfonium basic compound (quencher): 2-cyclohexylcarboxyethylmorpholine Organic solvent 1: 1-methoxyisopropyl acetate Organic solvent 2: Cyclohexanone

  The prepared polymer compounds (Polymers 1 to 15) were blended in an arbitrary ratio to the resist material to be the base material, and resist solution (Examples 1 to 17 and Comparative Examples 1 to 3) were prepared. Table 1 below shows combinations and blending ratios of the polymer compound and the base material resist material. The blending ratio of the polymer compound is expressed as a mixed mass part with respect to 100 parts by mass of the resist base resin.

(Measurement of receding contact angle and sliding angle)
The resist solutions prepared above (Examples 1 to 17 and Comparative Examples 1 to 3) were each applied onto a silicon substrate by spin coating, and baked at 120 ° C. for 60 seconds to form a 200 nm thick photoresist film. .

  Using the tilt method contact angle meter DropMaster500 (manufactured by Kyowa Interface Science Co., Ltd.), keep the wafer on which the photoresist film created by the above method is formed horizontally, and drop 50μL of ultrapure water onto the photoresist film. Formed. Next, this wafer was gradually tilted, and the wafer angle (falling angle) and receding contact angle at which the polka dots began to fall were measured. The results are shown in Table 2 below.

  A small falling angle indicates that water easily flows on the resist film, and a large receding contact angle indicates that it is difficult for droplets to remain on the resist film even in high-speed scanning exposure. The photoresist films (Examples 1 to 17) formed from the resist solution blended with the polymer compound according to the present invention are back contacted as compared with the photoresist films (Comparative Examples 1 to 3) not blended with the polymer compound. The angle is large and the falling angle is small. From this result, it was confirmed that the receding contact angle of the photoresist film can be remarkably improved and the falling angle is not deteriorated by blending the polymer compound according to the present invention.

(Measurement of resist composition elution amount)
The resist solutions prepared in the above (Examples 2, 5 and Comparative Examples 1 and 2) were each applied onto a silicon substrate by spin coating, and baked at 120 ° C. for 60 seconds to form a 200 nm thick photoresist film. . The entire surface of the photoresist film was irradiated with energy of 50 mJ / cm ^{2 with} an open frame using a Nikon ArF scanner S305B.

Next, a 10-cm inner diameter Teflon (registered trademark) ring is placed on the irradiated photoresist film, 10 mL of pure water is carefully poured therein, and the resist film and pure water are contacted at room temperature for 60 seconds. I let you.
Then, pure water was collect | recovered and the anion component density | concentration of the photo-acid generator (PAG) in pure water was quantified with the LC-MS analyzer by Agilent.
The results of calculating the amount of anion elution per unit area of the photoresist film for 60 seconds from the measured anion concentration are shown in Table 3 below.

  As is apparent from Table 3 above, in the photoresist films (Examples 2 and 5) formed from the resist solution containing the polymer compound according to the present invention, the photoacid generator component was eluted from the photoresist film into water. The effect which suppresses was recognized.

(Measurement of intramolecular distribution of polymer compounds)
In order to investigate the distribution of the polymer compound according to the present invention in the resist film, a resin solution comprising the following materials was prepared.
Base material resist material: 100 parts by mass of base resin 2 Polymer compound: 6.3 parts by mass of polymer 2 Organic solvent: 1800 parts by mass of 1-methoxyisopropyl acetate

  The resin solution prepared above was applied on a silicon substrate by spin coating, and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 230 nm.

Next, this coating film was obliquely cut over a length of 200 μm by SAICAS (Surface And Interfacial Cutting Analysis System, manufactured by Daipura Wintex). The resist film exposed by oblique cutting is scanned in a line shape with TOF-SIMS (time-of-flight mass spectrometer, ULVACPHI) with an ion beam diameter of 10 μm and a measurement interval of 20 μm. Negative ion mass spectra at each measurement point Were measured, the count values of various peaks were read from each spectrum, and a profile was created. The result is shown in FIG.
The horizontal axis in FIG. 1 indicates the measurement position. The exposed portion of the silicon substrate is near the measurement position 0 μm, and the outermost layer of the coating film is the measurement position 200 μm.

Looking at the profile of fluorine ions, it was found that the strength was strong at a depth of 40 nm from the outermost layer of the coating film, and fluorine was selectively present in the surface layer portion.
Of the materials constituting the applied resin solution, the only polymer containing fluorine is polymer 2, which is a polymer compound. It became clear that it was localized on the surface.
From this, it is considered that the polymer compound of the present invention imparts good barrier performance against water to the resist film.

  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.

  For example, in the above description, the case where the resist material of the present invention is used in immersion lithography has been mainly described. However, the resist material of the present invention can naturally be used in normal lithography that is not immersion.

It is the profile of the film depth direction of the negative ion in the coating film formed using the resist material of this invention.

Claims (11)

A resist material comprising at least a polymer compound having a repeating unit represented by the following general formula (1).

(In the formula, R ¹ and R ² are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, and R ¹ and R ² are bonded to form a ring. In this case, the total carbon number of R ¹ and R ² represents a divalent organic group having 2 to 20. R ³ , R ⁴ , R ¹¹ and R ¹⁴ are independently a hydrogen atom or a methyl group. , R ⁵ is a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, part or all of the hydrogen atoms may be substituted with fluorine atoms, and may contain an iminosulfonyl group X ¹ , X ² , X ³ , and X ⁴ are independently —C (═O) —, —C (═O) —O—, —C (═O) —O—R ⁶ —, —O—. , —C (═O) —R ⁶ —C (═O) —, —C (═O) —O—R ⁶ —C (═O) —O—, wherein R ⁶ has 1 carbon atom. -10 linear,岐状, or cyclic alkylene group .R ¹² may be substituted by fluorine alkylene group or alkanetriyl groups having a cyclic structure having 4 to 12 carbon atoms, R ¹³ is a hydrogen atom, C 1 -C 10 linear, branched alkyl groups may be substituted by fluorine, attached R ¹² and R ¹³ is may form a ring of 3 to 12 carbon atoms .R ¹⁵ Is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, n1 is 1 or 2. a-1, b-1, b-2 , B-3 are 0 <(a-1) ≦ 1, 0 ≦ (b-1) <1, 0 ≦ (b-2) <1, 0 ≦ (b-3) <1, 0 <(a -1) + (b-1) + (b-2) + (b-3) ≦ 1. A resist material comprising at least a polymer compound having a repeating unit represented by the following general formula (2).

(In the formula, R ⁴ , R ⁷ , R ¹¹ and R ¹⁴ are independently a hydrogen atom or a methyl group, R ⁸ is a linear, branched or cyclic alkylene group having 1 to 6 carbon atoms, one The above hydrogen atoms may be substituted with fluorine atoms, R ⁵ is a linear, branched or cyclic alkyl group having 1 to 14 carbon atoms, and some or all of the hydrogen atoms are fluorine atoms. R ⁹ is a linear or branched alkyl group having 1 to 10 carbon atoms in which at least one hydrogen atom is substituted with a fluorine atom, and may include an iminosulfonyl group. ⁸ and R ⁹ may be bonded to form a ring, and in this case, the total number of carbon atoms of R ⁸ and R ⁹ represents a trivalent organic group having ^{2 to} 12. X ¹ , X ² , X ^{3, X 4} are independently -C (= O) -, - C (= O) -O -, - C (= O) -O-R 6 ^{, -O -, - C (=} O) -R 6 -C (= O) -, - C (= O) -O-R 6 -C (= O) is either -O- .R ⁶ Is a linear, branched, or cyclic alkylene group having 1 to 10 carbon atoms, R ¹² may be substituted with an alkylene group or alkanetriyl group having a cyclic structure having 4 to ¹² carbon atoms by fluorine. R ¹³ is a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, and R ¹² and R ¹³ are bonded to each other to have 3 to 12 carbon atoms. R ¹⁵ may be a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, and may be substituted with fluorine, and n1 is 1 or 2. a-2, b-1, b-2, b-3 are 0 <(a-2) ≦ 1, 0 ≦ (b-1) <1, 0 ≦ (b-2) <1, 0 ≦ b-3) satisfies the <1,0 <(a-2) + (b-1) + (b-2) + (b-3) ≦ 1 range.)   The resist material according to claim 1, wherein the polymer compound does not have an alkyl group having 5 or more carbon atoms.   The resist material according to any one of claims 1 to 3, wherein the resist material is a chemically amplified positive resist material.   The resist according to claim 4, wherein the resist material contains a base resin containing at least a repeating unit having an acid labile group and a repeating unit having a hydroxy group and / or an adhesive group of a lactone ring. material.   6. The resist material according to any one of claims 1 to 5, wherein the resist material further contains one or more of an organic solvent, a basic compound, a dissolution controller, and a surfactant. The resist material described in 1.   At least a step of applying the resist material according to any one of claims 1 to 6 on a substrate, a step of exposing to high energy rays after heat treatment, and a step of developing using a developer; A pattern forming method comprising:   The pattern forming method according to claim 7, wherein the high energy ray has a wavelength in a range of 180 nm to 250 nm.   The pattern forming method according to claim 7, wherein the step of exposing with the high energy beam is performed by liquid immersion exposure using a liquid.   In the immersion exposure, an exposure wavelength in a range of 180 to 250 nm is used, a liquid is inserted between the substrate coated with the resist material and a projection lens, and the substrate is exposed through the liquid. The pattern forming method according to claim 9.   The pattern forming method according to claim 9, wherein water is used as the liquid.

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