JP2008003569A - Resist protective film material and pattern forming method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist protective film material capable of securely obtaining a rectangular satisfactory resist pattern, even when a protective film is formed on a photoresist film. <P>SOLUTION: The resist protective film material for forming the protective film on the photoresist film includes a polymer compound, containing a repeating unit having at least one among at least a carboxyl group, an α trifluoro methyl alcohol and an amine compound. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is performed by photolithography for fine processing in a manufacturing process of a semiconductor element or the like, for example, using an ArF excimer laser having a wavelength of 193 nm as a light source, and inserting a liquid (for example, water) between a projection lens and a substrate. In immersion photolithography, the present invention relates to a resist protective film material for forming a protective film on a photoresist film in order to protect the photoresist film, and a pattern forming method using the same.

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

  As exposure light used for forming a resist pattern, light exposure using a g-ray (436 nm) or i-line (365 nm) of a mercury lamp as a light source has been widely used. As a means for further miniaturization, a method of shortening the exposure wavelength is effective, and for mass production processes after 64 Mbit (process size is 0.25 μm or less) DRAM (Dynamic Random Access Memory). As a light source for exposure, a short wavelength KrF excimer laser (248 nm) was used 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. Photography using a laser (193 nm) has been studied in earnest.

Initially, ArF lithography was supposed to be applied from 180 nm node device fabrication, but KrF excimer lithography is 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 has been proposed to advance F ₂ lithography and early introduction of ArF immersion lithography (see Non-Patent Document 1, for example).

  In ArF immersion lithography, it has been proposed to impregnate water between the projection lens and the substrate. 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 1.44. 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 (for example, see Non-Patent Document 2).

  Here, various problems due to the presence of water on the photoresist film were pointed out. This includes shape change caused by dissolution of the generated acid or amine compound added to the resist film as a quencher in water, pattern collapse due to swelling, and the like. Therefore, it has been proposed that it is effective to provide a protective film between the resist film and water (see, for example, Non-Patent Document 3).

  The protective film formed on the photoresist film has been studied as an antireflection film. For example, there is an ARCOR (antireflective coating on resist) method disclosed in Patent Documents 1 to 3. The ARCOR method is a method including a step of forming a transparent antireflection film on a resist film and peeling off after exposure, and is a method of forming a fine pattern with high accuracy and high alignment accuracy by the simple method. When a perfluoroalkyl compound (perfluoroalkyl polyether, perfluoroalkylamine) of a low refractive index material is used as the antireflection film, the reflected light at the resist-antireflection film interface is greatly reduced, and the dimensional accuracy is improved. As the fluorine-based material, in addition to the above-described materials, for example, perfluoro (2,2-dimethyl-1,3-dioxole) -tetrafluoroethylene copolymer, perfluoro (allyl vinyl ether) shown in Patent Document 4, Amorphous polymers such as cyclized polymers of perfluorobutenyl vinyl ether have been proposed.

  However, since the perfluoroalkyl compound has low compatibility with organic substances, chlorofluorocarbon is used as a diluent for controlling the coating film thickness. Therefore, its use has become a problem. Moreover, the said compound had a problem in uniform film formability, and it could not be said that it was enough as an antireflection film. Further, before developing the photoresist film, the antireflection film had to be peeled off with chlorofluorocarbon. For this reason, there have been significant demerits in practical use, such as the need to add a system for removing the antireflection film to the conventional apparatus and the considerable cost of the fluorocarbon solvent.

  When the antireflection film is peeled off without adding to the conventional apparatus, it is most desirable to peel off using the developing unit. Since the solution used in the developing unit of the photoresist film is an alkaline aqueous solution as a developer and pure water as a rinse solution, it can be said that an antireflection film material that can be easily peeled off with these solutions is desirable. Therefore, many water-soluble antireflection film materials and pattern formation methods using these have been proposed (see, for example, Patent Documents 5 and 6).

  However, since the water-soluble protective film is dissolved in water during exposure, it cannot be used for immersion lithography. On the other hand, water-insoluble fluorine-based polymers have the problems that a special fluorocarbon-based release agent is required and that a special cup for fluorocarbon solvents is required. There was a need for a protective film.

  Here, a developer-soluble top coat based on methacrylate pendant of hexafluoroalcohol has been proposed (for example, see Non-Patent Document 4). This has a high Tg of 150 ° C., high alkali solubility, and good compatibility with a photoresist film.

  On the other hand, when a protective film is formed on the photoresist film, the surface portion of the photoresist film after development may be reduced depending on the type of the photoresist film, and the top shape of the photoresist film may be reduced. There are problems such as rounding. In this case, a good rectangular resist pattern cannot be obtained. For this reason, there has been a demand for a resist protective film material that can more reliably obtain a good rectangular resist pattern.

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 J. et al. Photopolymer Sci. and Technol. Vol. No. 18 5 p615 (2005) JP-A-62-62520 JP-A-62-62521 JP 60-38821 A JP-A-5-74700 JP-A-6-273926 Japanese Patent No. 2803549

  The present invention has been made in view of such problems, and even when a protective film is formed on a photoresist film, a resist protective film material that can more reliably obtain a good rectangular resist pattern, and such An object of the present invention is to provide a pattern forming method using various materials.

  The present invention has been made to solve the above-described problems, and is a resist protective film material for forming a protective film on a photoresist film, and includes at least a carboxyl group and an α-trifluoromethyl alcohol group. Provided is a resist protective film material comprising a polymer compound containing a repeating unit having one or more and an amine compound (claim 1).

  And in the resist protective film material of this invention, it is preferable that the said amine compound is one or more compounds of a tertiary amine compound and a sulfonic acid amide compound (Claim 2).

（上記式中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立に、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基であり、Ｒ^１とＲ^２、Ｒ^１とＲ³、Ｒ²とＲ³のいずれかが、それぞれ結合して環を形成していても良く、エステル、エーテル基、アミノ基のいずれか１つ以上を有していても良く、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^４、Ｒ^５、Ｒ^６は、それぞれ独立に、水素原子、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基、−ＳＯ_２Ｒ^７のいずれかであり、Ｒ^４とＲ^５、Ｒ^４とＲ^６、Ｒ^５とＲ^６のいずれかが、それぞれ結合して環を形成していても良く、Ｒ^４、Ｒ^５、Ｒ^６のうち少なくとも１つが−ＳＯ_２Ｒ^７である。Ｒ^７は、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基であり、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。） In this case, at least one of the tertiary amine compound and the sulfonic acid amide compound is a compound represented by the following general formula (1-1) or a compound represented by the following general formula (1-2). It is preferable that it is one or more compounds of (Claim 3).

(In the above formula, R ¹ , R ² and R ³ are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and R ¹ and R ² , R ¹ and R ^3. , R ² and R ³ may be bonded to each other to form a ring, and may have any one or more of an ester, an ether group, and an amino group, and a hydrogen atom of an alkyl group R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. , —SO ₂ R ⁷ , and R ⁴ and R ⁵ , R ⁴ and R ⁶ , or R ⁵ and R ⁶ may be bonded to each other to form a ring, and R ⁴ , at least one of R ^{5, R 6} is a _-SO 2 ^{R 7} .R ⁷ is a straight, branched, or A Jo alkyl group, all or some of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom.)

（上記式中、Ｒ^３００、Ｒ^３０２、Ｒ^３０５は、それぞれ独立に、炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、−Ｏ−を含んでも良い。Ｒ^３０１、Ｒ^３０４は、それぞれ独立に、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基であり、ヒドロキシ基またはエステル基を有していてもよく、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^３０３は、単結合、又は炭素数１〜４の直鎖状又は分岐状のアルキレン基である。Ｒ^３０６は炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基であり、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。） Alternatively, at least one of the tertiary amine compounds is preferably a compound represented by the following general formula (2) (Claim 4).
N (X ¹⁰ ) _n1 (Y ¹⁰ ) _3-n1 (2)
(In the above formula, n1 is any one of 1, 2, and 3. X ¹⁰ may be the same or different, and any one of the following general formulas (X ¹⁰ ) -1 to (X ¹⁰ ) -3. Y ¹⁰ may be the same or different, and represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and Y ¹⁰ may be bonded to each other to form a ring. Well, the ring may contain -O-.)

(In the above formula, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are each independently a linear or branched alkylene group having 1 to 4 carbon atoms, and may include —O—. R ³⁰¹ , R ³⁰⁴ Are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may have a hydroxy group or an ester group, and all or part of the hydrogen atoms of the alkyl group are R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is a linear or branched group having 1 to 30 carbon atoms. A cyclic or cyclic alkyl group, and all or part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.)

  As described above, when a protective film is formed on the photoresist film, depending on the type of the photoresist film, the surface portion of the developed photoresist film may be reduced, and the photoresist film on which the resist pattern is formed is formed. There is a problem that the shape of the top portion is rounded. This is considered to be because the amine compound added to the photoresist film moves to the protective film thereon. On the other hand, the resist protective film material of the present invention contains an amine compound in addition to a polymer compound containing a repeating unit having one or more of a carboxyl group and an α-trifluoromethyl alcohol group. For this reason, if a protective film is formed on the photoresist film using this, the migration of the amine compound from the photoresist film can be effectively prevented. For example, the surface portion of the photoresist film after development It is possible to more reliably prevent film loss. For this reason, a favorable rectangular resist pattern can be obtained more reliably.

（上記式中、Ｒ^１８、Ｒ^２０は、それぞれ独立に、水素原子、フッ素原子、メチル基、トリフルオロメチル基のいずれかである。Ｙは、それぞれ独立に、単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−Ｃ（＝Ｏ）−のいずれかである。Ｒ^２８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り、アルキレン基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^２６は、それぞれ独立に、単結合、炭素数１〜２５の直鎖状、分岐状又は環状のアルキレン基又はアルカントリイル基のいずれかであり、アルキレン基又はアルカントリイル基の水素原子の全部又は一部がフッ素原子で置換されていても良く、Ｒ^１７は、それぞれ独立して、水素原子、フッ素原子、メチル基、トリフルオロメチル基、ジフルオロメチル基のいずれかであり、Ｒ^２６とＲ^１７は、結合して環を形成していても良く、環の中にエーテル基、水素原子の全部又は一部がフッ素原子で置換されたアルキレン基、トリフルオロメチル基のうち１つ以上の基を有していても良い。ｎは、それぞれ独立に、１又は２である。（ａ−１）、（ａ−２）は、０≦（ａ−１）≦０．９、０≦（ａ−２）≦０．９、０≦（ａ−１）＋（ａ−２）≦０．９の範囲である。） In the resist protective film material of the present invention, the repeating unit having an α-trifluoromethyl alcohol group in the polymer compound is preferably a repeating unit represented by the following general formula (3) (Claim 5). .

(In the above formula, each of R ¹⁸ and R ²⁰ is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Y is independently a single bond, —O—, — C (═O) —O—, —C (═O) —O—R ²⁸ —C (═O) —O—, —C (═O) —O—R ²⁸ —O—, —C (═O ) —O—R ²⁸ —O—C (═O) —, wherein R ²⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and is a hydrogen atom of the alkylene group. R ²⁶ may be each independently substituted with a fluorine atom, and each R ²⁶ independently represents a single bond, a linear, branched or cyclic alkylene group having 1 to 25 carbon atoms, or an alkanetriyl group. Any or all of the hydrogen atoms of the alkylene group or alkanetriyl group are substituted with fluorine atoms. May have, R ¹⁷ are each independently hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a difluoromethyl group, R ²⁶ and R ¹⁷ may combine to form a ring The ring may have one or more groups selected from the group consisting of an ether group, an alkylene group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and a trifluoromethyl group. Each independently represents 1 or 2. (a-1) and (a-2) are 0 ≦ (a-1) ≦ 0.9, 0 ≦ (a-2) ≦ 0.9, and 0 ≦. (A-1) + (a-2) ≦ 0.9.)

（上記式中、Ｒ³⁰は水素原子又はメチル基、Ｒ^３１、Ｒ^３２は同一又は異種の水素原子、又は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基で、Ｒ^３１とＲ^３２が結合してこれらが結合する炭素原子と共に環を形成していてもよい。） Furthermore, it is more preferable that the repeating unit having an α trifluoromethyl alcohol group in the polymer compound is a repeating unit represented by the following general formula (4).

(In the formula, R ³⁰ is a hydrogen atom or a methyl ^group, R ^{31, R 32} are identical or different hydrogen atoms or C 1 -C 12 straight, branched or cyclic alkyl ^group, and ^{R 31} R ³² may be bonded to form a ring together with the carbon atoms to which these are bonded.)

（上記式中、Ｒ^２９は、水素原子、フッ素原子、メチル基、トリフルオロメチル基、−ＣＯＯＨ、−ＣＨ_２−ＣＯＯＨのいずれかである。Ｒ^１９は、水素原子、フッ素原子、メチル基、トリフルオロメチル基、−ＣＯＯＨ、−ＣＨ_２−ＣＯＯＨのいずれかである。Ｙは、それぞれ独立に、単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−Ｃ（＝Ｏ）−のいずれかである。Ｒ^２８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り、アルキレン基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^２６は、それぞれ独立に、単結合、炭素数１〜２５の直鎖状、分岐状又は環状のアルキレン基又はアルカントリイル基のいずれかであり、アルキレン基又はアルカントリイル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。ｎは、それぞれ独立に、１又は２である。（ｂ−１）、（ｂ−２）は、０≦（ｂ−１）≦０．９、０≦（ｂ−２）≦０．９、０≦（ｂ−１）＋（ｂ−２）≦０．９の範囲である。） Moreover, in the resist protective film material of this invention, it is preferable that the repeating unit which has a carboxyl group in the said high molecular compound is a repeating unit shown by following General formula (5) (Claim 7).

(In the above formula, R ²⁹ is any one of a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, —COOH, —CH ₂ —COOH. R ¹⁹ is a hydrogen atom, a fluorine atom, a methyl group, Any one of a trifluoromethyl group, —COOH, and —CH ₂ —COOH, each of Y is independently a single bond, —O—, —C (═O) —O—, —C (═O) —; O—R ²⁸ —C (═O) —O—, —C (═O) —O—R ²⁸ —O—, —C (═O) —O—R ²⁸ —O—C (═O) — R ²⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and all or part of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms. R ²⁶ independently represents a single bond, the number 1 to 25 linear, alkylene branched or cyclic Or an alkanetriyl group, and all or part of the hydrogen atoms of the alkylene group or alkanetriyl group may be substituted with fluorine atoms, and n is independently 1 or 2. (B-1) and (b-2) are 0≤ (b-1) ≤0.9, 0≤ (b-2) ≤0.9, 0≤ (b-1) + (b-2) ≦ 0.9.)

  Thus, if the resist protective film material contains a polymer compound containing a repeating unit having one or more of the carboxyl group and α-trifluoromethyl alcohol group, a protective film formed using the polymer compound Is highly soluble in alkali and can be more easily peeled off with an alkaline developer during development. This protective film also has good compatibility with the photoresist film.

  In the resist protective film material of the present invention, the resist protective film material preferably contains a polymer compound containing a repeating unit having one or more of an alkyl group and a fluoroalkyl group. 8).

（上記式中、Ｒ^８、Ｒ^１０は、それぞれ独立に、水素原子、フッ素原子、メチル基、トリフルオロメチル基のいずれかである。Ｘ^２は、それぞれ独立に、単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^１６−Ｃ（＝Ｏ）−Ｏ−のいずれかである。Ｒ^１６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り、アルキレン基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^９は、それぞれ独立に、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良く、エーテル基、エステル基を有していても良い。Ｒ^１１〜Ｒ^１４は、それぞれ独立に、水素原子、フッ素原子、メチル基、トリフルオロメチル基のいずれかであり、Ｒ^１１〜Ｒ^１４の内、いずれかが少なくとも１個以上のフッ素原子を有する。ｍは、１又は２である。（ｃ−１）、（ｃ−２）、（ｃ−３）、（ｃ−４）、（ｃ−５）は、０≦（ｃ−１）≦０．９、０≦（ｃ−２）≦０．９、０≦（ｃ−３）≦０．９、０≦（ｃ−４）≦０．９、０≦（ｃ−５）≦０．９、０≦（ｃ−１）＋（ｃ−２）＋（ｃ−３）＋（ｃ−４）＋（ｃ−５）≦０．９の範囲である。） In this case, the repeating unit having at least one of an alkyl group and a fluoroalkyl group in the polymer compound is preferably a repeating unit represented by the following general formula (6) (claim 9).

(In the above formula, R ⁸ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X ² is independently a single bond, —O—, Or —C (═O) —O— or —C (═O) —O—R ¹⁶ —C (═O) —O—, wherein R ¹⁶ is a straight chain having 1 to 10 carbon atoms, It is a branched or cyclic alkylene group, and all or part of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms, and each R ⁹ is independently a linear or branched group having 1 to 20 carbon atoms. Or all or part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, or may have an ether group or an ester group, R ^{11 to} R ¹⁴ are Each independently of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. And in either ^{displacement,} .m of R 11 ^{to R 14,} either with at least one fluorine atom is 1 or 2. (C-1), (c-2), (c- 3), (c-4), and (c-5) are 0 ≦ (c-1) ≦ 0.9, 0 ≦ (c-2) ≦ 0.9, 0 ≦ (c-3) ≦ 0. 9, 0 ≦ (c−4) ≦ 0.9, 0 ≦ (c−5) ≦ 0.9, 0 ≦ (c−1) + (c−2) + (c−3) + (c−4) ) + (C-5) ≦ 0.9.)

  Thus, if the resist protective film material contains a polymer compound containing a repeating unit having one or more of an alkyl group and a fluoroalkyl group, a protective film is formed using this, Water repellency and water slidability can be further improved, and mixing with a photoresist film can be effectively prevented.

  Moreover, in this invention, it is preferable that the said resist protective film material contains a solvent further (Claim 10).

  Thus, if the resist protective film material further contains a solvent, the film formability is further improved.

  In addition, the present invention includes at least a step of forming a photoresist film on a substrate, a step of forming a resist protective film on the photoresist film using the resist protective film material of the present invention, and exposure. There is provided a pattern forming method comprising a step and a step of developing using a developer.

  Of course, it goes without saying that other various processes such as an etching process, a resist removal process, and a cleaning process may be performed.

  In the pattern forming method of the present invention, it is preferable that the exposure step is performed by immersion lithography performed by inserting a liquid between the projection lens and the substrate.

  In this way, a finer resist pattern can be formed on the photoresist film by performing the exposure process by immersion lithography.

  Moreover, in the pattern formation method of this invention, the said exposure process can be performed using water as a liquid inserted between the said projection lens and the said board | substrate using the light source of the exposure wavelength of the range of 180-250 nm. (Claim 13).

  Thus, water can be used as the liquid used in immersion lithography, for example. Then, by inserting water between the projection lens and the substrate and performing exposure using a light source having an exposure wavelength in the range of 180 to 250 nm, a much finer resist pattern can be formed.

  In the pattern forming method of the present invention, in the development step, development is performed using an alkaline developer to form a resist pattern on the photoresist film, and at the same time, the resist protective film on the photoresist film is peeled off. Preferred (claim 14).

  Thus, in the development process, development is performed using an alkaline developer, and a resist pattern is formed on the photoresist film. At the same time, the resist protective film on the photoresist film is removed. The resist protective film can be removed more easily without increasing the number of layers.

  As described above, the resist protective film material of the present invention contains an amine compound in addition to a polymer compound containing a repeating unit having one or more of a carboxyl group and an α-trifluoromethyl alcohol group. For this reason, if a protective film is formed on the photoresist film using this, the migration of the amine compound from the photoresist film can be effectively prevented. For example, the surface portion of the photoresist film after development It is possible to more reliably prevent film loss. For this reason, a favorable rectangular resist pattern can be obtained more reliably.

Hereinafter, the present invention will be described in more detail.
When a developer-soluble protective film is formed on a positive photoresist film, the surface portion of the photoresist film after development is reduced, and the top portion of the photoresist film on which the resist pattern is formed There are problems such as a rounded shape and a decrease in the side lobe margin of the hole pattern. This is considered to be because the amine compound added to the photoresist film moves to the protective film thereon. This amine compound is added to the photoresist film as a quencher for acid diffusion control, contrast improvement, and sensitivity control. For example, when there is a hexafluoroalcohol group in the protective film, since the hexafluoroalcohol group generally has a high affinity with the amine compound, the amine compound added to the photoresist film moves to the protective film. It becomes easy to do. As a result, the concentration of the amine compound that prevents acid diffusion near the surface of the photoresist film, that is, near the interface with the protective film is reduced, and the photoresist film portion is dissolved, so that the surface portion of the photoresist film after development is reduced. It is thought that caused.

  On the other hand, it is also conceivable to adopt a method of suppressing the movement of the amine compound in the photoresist film by reducing the acidity of an alkali-soluble group such as a carboxyl group or a hexafluoroalcohol group. However, in this case, there is a drawback that the alkali dissolution rate is extremely reduced.

  Therefore, as a result of further studies, the present inventors need to add an amine compound in advance in the protective film in order to prevent migration of the amine compound in the photoresist film to the protective film. The present invention has been completed.

  That is, the present invention provides a resist protective film material for forming a protective film on a photoresist film, which is a high-resisting material containing at least one repeating unit having at least one of a carboxyl group and an α-trifluoromethyl alcohol group. Provided is a resist protective film material comprising a molecular compound and an amine compound.

  Thus, the resist protective film material of the present invention contains an amine compound in addition to a polymer compound containing a repeating unit having one or more of a carboxyl group and an α-trifluoromethyl alcohol group. For this reason, if a protective film is formed on the photoresist film using this, the migration of the amine compound from the photoresist film can be effectively prevented. For example, the surface portion of the photoresist film after development It is possible to more reliably prevent film loss. For this reason, a favorable rectangular resist pattern can be obtained more reliably.

  In the resist protective film material of the present invention, the amine compound is preferably one or more of a tertiary amine compound and a sulfonic acid amide compound.

  Here, as an amine compound to be added to the resist protective film material, there is almost no absorption in ArF light, a boiling point at normal pressure of 200 ° C. or higher in order to suppress evaporation during pre-baking, and elution into water. It is required to be low and basic.

  In order to make ArF light (wavelength 193 nm) almost non-absorbing, it is preferable not to have an aromatic group, an unsaturated bond, or a carboxylic acid amide group. For water insolubility, those which are not hydroxy groups, glyme chains, primary or secondary amines or quaternary ammonium salts are preferred, and tertiary alkylamines are particularly preferred. Furthermore, it is preferably a tertiary amine compound having a fluoroalkyl group, whereby it can be hardly eluted in water.

  Examples of one or more compounds among the tertiary amine compound and the sulfonic acid amide compound include, for example, a compound represented by the following general formula (1-1) and a compound represented by the following general formula (1-2). One or more compounds may be mentioned.

（上記式中、Ｒ¹、Ｒ²、Ｒ³は、それぞれ独立に、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基であり、Ｒ^１とＲ^２、Ｒ^１とＲ³、Ｒ²とＲ³のいずれかが、それぞれ結合して環を形成していても良く、エステル、エーテル基、アミノ基のいずれか１つ以上を有していても良く、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^４、Ｒ^５、Ｒ^６は、それぞれ独立に、水素原子、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基、−ＳＯ_２Ｒ^７のいずれかであり、Ｒ^４とＲ^５、Ｒ^４とＲ^６、Ｒ^５とＲ^６のいずれかが、それぞれ結合して環を形成していても良く、Ｒ^４、Ｒ^５、Ｒ^６のうち少なくとも１つが−ＳＯ_２Ｒ^７である。Ｒ^７は、炭素数１〜１０の直鎖状、分岐状又は環状のアルキル基であり、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。）

(In the above formula, R ¹ , R ² and R ³ are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and R ¹ and R ² , R ¹ and R ^3. , R ² and R ³ may be bonded to each other to form a ring, and may have any one or more of an ester, an ether group, and an amino group, and a hydrogen atom of an alkyl group R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. , —SO ₂ R ⁷ , and R ⁴ and R ⁵ , R ⁴ and R ⁶ , or R ⁵ and R ⁶ may be bonded to each other to form a ring, and R ⁴ , at least one of R ^{5, R 6} is a _-SO 2 ^{R 7} .R ⁷ is a straight, branched, or A Jo alkyl group, all or some of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom.)

  Specific examples of the amine compound represented by the general formula (1-1) include trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec- Butylamine, tripentylamine, tricyclopentylamine, trihexylamine, tricyclohexylamine, triheptylamine, trioctylamine, trinonylamine, tridecylamine, tridodecylamine, tricetylamine, N, N-dimethylcyclohexylamine, N, N-diethylcyclohexylamine, N, N-dibutylcyclohexylamine, N, N, N ′, N′-tetramethylmethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ', N' Tetramethyl tetraethylenepentamine, dimethylethylamine, and the like methylethylpropylamine.

The resist protective film material of the present invention must contain an amine compound. However, in the case of an immersion protective film material, the amount of amine compound added is 100 parts by mass of the base polymer for immersion protective film. The amount is preferably 5 parts by mass or less, more preferably 2 parts by mass or less, and still more preferably 1 part by mass or less.
Moreover, in order to suppress the water repellency fall by addition of an amine compound, in order to suppress the elution to the water of amine itself, the addition of the amine compound which has a C4 or more long-chain alkyl group is preferable.

  It is an amine compound containing an ester group or an ether group represented by the following general formula (2) that has the effect of improving the rectangularity of the pattern when added in a small amount. These amine compounds have been developed as quenchers that are excellent in acid trapping ability and can be added to a resist to improve contrast and obtain a rectangular pattern. The amine compound represented by the following general formula (2) has a high effect of effectively suppressing the film loss of the resist pattern when added to the resist protective film material. Such amine compounds and synthesis methods are disclosed in JP-A-11-84639, JP-A-2001-194776, and JP-A-2002-226470.

（上記式中、Ｒ^３００、Ｒ^３０２、Ｒ^３０５は、それぞれ独立に、炭素数１〜４の直鎖状又は分岐状のアルキレン基であり、−Ｏ−を含んでも良い。Ｒ^３０１、Ｒ^３０４は、それぞれ独立に、炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基であり、ヒドロキシ基またはエステル基を有していてもよく、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^３０３は、単結合、又は炭素数１〜４の直鎖状又は分岐状のアルキレン基である。Ｒ^３０６は炭素数１〜３０の直鎖状、分岐状又は環状のアルキル基であり、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。） N (X ¹⁰ ) _n1 (Y ¹⁰ ) _3-n1 (2)
(In the above formula, n1 is any one of 1, 2, and 3. X ¹⁰ may be the same or different, and any one of the following general formulas (X ¹⁰ ) -1 to (X ¹⁰ ) -3. Y ¹⁰ may be the same or different, and represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and Y ¹⁰ may be bonded to each other to form a ring. Well, the ring may contain -O-.)

(In the above formula, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are each independently a linear or branched alkylene group having 1 to 4 carbon atoms, and may include —O—. R ³⁰¹ , R ³⁰⁴ Are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may have a hydroxy group or an ester group, and all or part of the hydrogen atoms of the alkyl group are R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is a linear or branched group having 1 to 30 carbon atoms. A cyclic or cyclic alkyl group, and all or part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.)

  Specific examples of the compound represented by the general formula (2) include the following compounds.

As a method for synthesizing these amine compounds, for example, the method described in the above publication can be used.
Furthermore, the amine compound which has a fluoroalkyl group can be specifically illustrated below.

  Among the above compounds, a method for synthesizing a fluoroalkyl group-containing amine compound is exemplified in Japanese Patent Application No. 2005-299558. That is, Michael addition reaction of fluoroalkyl acrylate with primary and secondary amine, etherification reaction of fluoroalkyl with amine having alkanol group, acylation reaction of fluoroalkyl with amine having alkanol group.

  In particular, the sulfonic acid amide compound is preferably a non-aromatic compound having no absorption at a wavelength of 193 nm, and examples thereof include a reaction product of an alkylamine and a sulfonic acid. Specifically, methanesulfonylpiperidine, n-butanesulfonylpiperidine, trifluoromethanesulfonylpiperidine, nonafluorobutanesulfonylpiperidine, trifluoromethanesulfonylbutylamine, trifluoromethanesulfonyldibutylamine, trifluoromethanesulfonylpentylamine, trifluoromethanesulfonyloctylamine, trifluoro Lomethanesulfonylnonylamine, trifluoromethanesulfonyldecylamine, trifluoromethanesulfonyldodecylamine, trifluoromethanesulfonyltridecylamine, trifluoromethanesulfonyltetradecylamine, trifluoromethanesulfonylpentadecylamine, trifluoromethanesulfonylhexadecylamine, trifluoromethanesulfur Cycloalkenyl adamantylamine, trifluoromethanesulfonyl noradamantyl amine, mention may be made of trifluoromethanesulfonyl norbornyl amine, trifluoromethanesulfonyl cyclopentylamine, sulfonic acid amides of alkyl amine having 2 to 30 carbon atoms such as trifluoromethanesulfonyl cyclohexylamine.

  In the resist protective film material of the present invention, the compounding amount of the amine compound is preferably 0.0001 to 5 parts, particularly 0.01 to 3 parts with respect to 100 parts of the total base resin. If the blending amount is 0.0001 part or more, the blending effect is sufficiently obtained, and if it is 3 parts or less, the resist shape after development may be a T-top shape or the hole pattern may not be opened. Less is.

  As described above, the resist protective film material of the present invention further contains a polymer compound containing a repeating unit having one or more of a carboxyl group and an α-trifluoromethyl alcohol group.

  Thus, if the resist protective film material contains a polymer compound containing a repeating unit having one or more of a carboxyl group and an α-trifluoromethyl alcohol group, a protective film formed using the same It has high alkali solubility and can be more easily peeled off with an alkaline developer during development. This protective film also has good compatibility with the photoresist film.

（上記式中、Ｒ^１８、Ｒ^２０は、それぞれ独立に、水素原子、フッ素原子、メチル基、トリフルオロメチル基のいずれかである。Ｙは、それぞれ独立に、単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−Ｃ（＝Ｏ）−のいずれかである。Ｒ^２８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り、アルキレン基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^２６は、それぞれ独立に、単結合、炭素数１〜２５の直鎖状、分岐状又は環状のアルキレン基又はアルカントリイル基のいずれかであり、アルキレン基又はアルカントリイル基の水素原子の全部又は一部がフッ素原子で置換されていても良く、Ｒ^１７は、それぞれ独立して、水素原子、フッ素原子、メチル基、トリフルオロメチル基、ジフルオロメチル基のいずれかであり、Ｒ^２６とＲ^１７は、結合して環を形成していても良く、環の中にエーテル基、水素原子の全部又は一部がフッ素原子で置換されたアルキレン基、トリフルオロメチル基のうち１つ以上の基を有していても良い。ｎは、それぞれ独立に、１又は２である。（ａ−１）、（ａ−２）は、０≦（ａ−１）≦０．９、０≦（ａ−２）≦０．９、０≦（ａ−１）＋（ａ−２）≦０．９の範囲である。） In this case, the repeating unit having an α trifluoromethyl alcohol group (hereinafter referred to as a repeating unit a) in the polymer compound may be a repeating unit represented by the following general formula (3). .

(In the above formula, each of R ¹⁸ and R ²⁰ is independently a hydrogen atom, a fluorine atom, a methyl group or a trifluoromethyl group. Y is independently a single bond, —O—, — C (═O) —O—, —C (═O) —O—R ²⁸ —C (═O) —O—, —C (═O) —O—R ²⁸ —O—, —C (═O ) —O—R ²⁸ —O—C (═O) —, wherein R ²⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and is a hydrogen atom of the alkylene group. R ²⁶ may be each independently substituted with a fluorine atom, and each R ²⁶ independently represents a single bond, a linear, branched or cyclic alkylene group having 1 to 25 carbon atoms, or an alkanetriyl group. Any or all of the hydrogen atoms of the alkylene group or alkanetriyl group are substituted with fluorine atoms. May have, R ¹⁷ are each independently hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a difluoromethyl group, R ²⁶ and R ¹⁷ may combine to form a ring The ring may have one or more groups selected from the group consisting of an ether group, an alkylene group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and a trifluoromethyl group. Each independently represents 1 or 2. (a-1) and (a-2) are 0 ≦ (a-1) ≦ 0.9, 0 ≦ (a-2) ≦ 0.9, and 0 ≦. (A-1) + (a-2) ≦ 0.9.)

（上記式中、Ｒ³⁰は水素原子又はメチル基、Ｒ^３１、Ｒ^３２は同一又は異種の水素原子、又は炭素数１〜１２の直鎖状、分岐状又は環状のアルキル基で、Ｒ^３１とＲ^３２が結合してこれらが結合する炭素原子と共に環を形成していてもよい。） In particular, the repeating unit a having an α trifluoromethyl alcohol group in the polymer compound is preferably a repeating unit represented by the following general formula (4).

(In the formula, R ³⁰ is a hydrogen atom or a methyl ^group, R ^{31, R 32} are identical or different hydrogen atoms or C 1 -C 12 straight, branched or cyclic alkyl ^group, and ^{R 31} R ³² may be bonded to form a ring together with the carbon atoms to which these are bonded.)

  If the repeating unit having an α-trifluoromethyl alcohol group in the polymer compound is a repeating unit represented by the above general formula (4), the polymer compound has excellent lubricity and a high dissolution rate in an alkali developer. Obtainable.

Here, the monomer for obtaining the said repeating unit a can be illustrated below. In the following formulae, R ¹⁸ and R ²⁰ are as described above.

（上記式中、Ｒ^２９は、水素原子、フッ素原子、メチル基、トリフルオロメチル基、−ＣＯＯＨ、−ＣＨ_２−ＣＯＯＨのいずれかである。Ｒ^１９は、水素原子、フッ素原子、メチル基、トリフルオロメチル基、−ＣＯＯＨ、−ＣＨ_２−ＣＯＯＨのいずれかである。Ｙは、それぞれ独立に、単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^２８−Ｏ−Ｃ（＝Ｏ）−のいずれかである。Ｒ^２８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り、アルキレン基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^２６は、それぞれ独立に、単結合、炭素数１〜２５の直鎖状、分岐状又は環状のアルキレン基又はアルカントリイル基のいずれかであり、アルキレン基又はアルカントリイル基の水素原子の全部又は一部がフッ素原子で置換されていても良い。ｎは、それぞれ独立に、１又は２である。（ｂ−１）、（ｂ−２）は、０≦（ｂ−１）≦０．９、０≦（ｂ−２）≦０．９、０≦（ｂ−１）＋（ｂ−２）≦０．９の範囲である。） In this case, the repeating unit having a carboxyl group (hereinafter referred to as repeating unit b) in the polymer compound may be a repeating unit represented by the following general formula (5).

(In the above formula, R ²⁹ is any one of a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, —COOH, —CH ₂ —COOH. R ¹⁹ is a hydrogen atom, a fluorine atom, a methyl group, Any one of a trifluoromethyl group, —COOH, and —CH ₂ —COOH, each of Y is independently a single bond, —O—, —C (═O) —O—, —C (═O) —; O—R ²⁸ —C (═O) —O—, —C (═O) —O—R ²⁸ —O—, —C (═O) —O—R ²⁸ —O—C (═O) — R ²⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and all or part of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms. R ²⁶ independently represents a single bond, the number 1 to 25 linear, alkylene branched or cyclic Or an alkanetriyl group, and all or part of the hydrogen atoms of the alkylene group or alkanetriyl group may be substituted with fluorine atoms, and n is independently 1 or 2. (B-1) and (b-2) are 0≤ (b-1) ≤0.9, 0≤ (b-2) ≤0.9, 0≤ (b-1) + (b-2) ≦ 0.9.)

Here, the monomer for obtaining the repeating unit b can be illustrated below. In the following formula, R ²⁹ and R ¹⁹ are as described above.

  In the present invention, the resist protective film material contains a polymer compound containing a repeating unit having one or more of an alkyl group and a fluoroalkyl group (hereinafter referred to as a repeating unit c). preferable.

  As described above, if the resist protective film material contains a polymer compound containing the repeating unit c, the water repellency and the water slidability can be further improved by forming a protective film using this. In addition, mixing with the photoresist film can be effectively prevented.

（上記式中、Ｒ^８、Ｒ^１０は、それぞれ独立に、水素原子、フッ素原子、メチル基、トリフルオロメチル基のいずれかである。Ｘ^２は、それぞれ独立に、単結合、−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−、−Ｃ（＝Ｏ）−Ｏ−Ｒ^１６−Ｃ（＝Ｏ）−Ｏ−のいずれかである。Ｒ^１６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り、アルキレン基の水素原子の全部又は一部がフッ素原子で置換されていても良い。Ｒ^９は、それぞれ独立に、炭素数１〜２０の直鎖状、分岐状又は環状のアルキル基であり、アルキル基の水素原子の全部又は一部がフッ素原子で置換されていても良く、エーテル基、エステル基を有していても良い。Ｒ^１１〜Ｒ^１４は、それぞれ独立に、水素原子、フッ素原子、メチル基、トリフルオロメチル基のいずれかであり、Ｒ^１１〜Ｒ^１４の内、いずれかが少なくとも１個以上のフッ素原子を有する。ｍは、１又は２である。（ｃ−１）、（ｃ−２）、（ｃ−３）、（ｃ−４）、（ｃ−５）は、０≦（ｃ−１）≦０．９、０≦（ｃ−２）≦０．９、０≦（ｃ−３）≦０．９、０≦（ｃ−４）≦０．９、０≦（ｃ−５）≦０．９、０≦（ｃ−１）＋（ｃ−２）＋（ｃ−３）＋（ｃ−４）＋（ｃ−５）≦０．９の範囲である。） In this case, the repeating unit having at least one of an alkyl group and a fluoroalkyl group in the polymer compound is preferably a repeating unit represented by the following general formula (6).

(In the above formula, R ⁸ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X ² is independently a single bond, —O—, Or —C (═O) —O— or —C (═O) —O—R ¹⁶ —C (═O) —O—, wherein R ¹⁶ is a straight chain having 1 to 10 carbon atoms, It is a branched or cyclic alkylene group, and all or part of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms, and each R ⁹ is independently a linear or branched group having 1 to 20 carbon atoms. Or all or part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, or may have an ether group or an ester group, R ^{11 to} R ¹⁴ are Each independently of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. And in either ^{displacement,} .m of R 11 ^{to R 14,} either with at least one fluorine atom is 1 or 2. (C-1), (c-2), (c- 3), (c-4), and (c-5) are 0 ≦ (c-1) ≦ 0.9, 0 ≦ (c-2) ≦ 0.9, 0 ≦ (c-3) ≦ 0. 9, 0 ≦ (c−4) ≦ 0.9, 0 ≦ (c−5) ≦ 0.9, 0 ≦ (c−1) + (c−2) + (c−3) + (c−4) ) + (C-5) ≦ 0.9.)

Here, the monomer for obtaining the repeating unit which has a fluoroalkyl group among the repeating units c can be illustrated below. In the following formula, R ⁸ and R ¹⁰ are as described above.

Moreover, the monomer for obtaining the repeating unit which has an alkyl group among the repeating units c can be illustrated below. In the following formula, R ⁸ and R ¹⁰ are as described above.

Moreover, the monomer for obtaining the repeating unit which has both an alkyl group and a fluoroalkyl group among the repeating units c can be illustrated below. In the following formula, R ⁸ and R ¹⁰ are as described above.

In particular, as a polymer compound to be contained in the resist protective film material, a repeating unit having an α-trifluoromethyl alcohol group which is an alkali-soluble group (repeating unit a), a repeating unit having a carboxyl group (repeating unit b), Balancing water repellency, water slidability, and alkali solubility by copolymerizing a repeating unit (repeat unit c) having one or more of an aqueous alkyl group and a fluoroalkyl group at an appropriate ratio. For example, a resist protective film having a dissolution rate in water of 0.1 Å (angstrom) / s or less and a dissolution rate of a developer composed of a 2.38 mass% tetramethylammonium hydroxide aqueous solution is 300 Å / s or more. Can be formed.
Of course, the polymer compounds having the respective repeating units may be copolymerized or blended at an appropriate ratio.

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

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

  The polymer compound contained in the resist protective film material of the present invention has a polystyrene-reduced mass average molecular weight of 1,000 to 500,000, preferably 2,000 to 30,000 by gel permeation chromatography (GPC). It is desirable to be. When the mass average molecular weight is 1,000 or more, there is little possibility of mixing with the photoresist film, and it becomes difficult to dissolve in a liquid such as water. In addition, when the mass average molecular weight is 500,000 or less, there is little risk of problems in film formability after spin coating and the like, and there is little risk of a decrease in alkali solubility.

  In order to synthesize a polymer compound to be contained in the resist protective film material of the present invention, as one method, a monomer having an unsaturated bond for obtaining the repeating units a to c is added to a radical initiator in an organic solvent. In addition, a polymer compound can be synthesized by performing heat polymerization. Examples of the organic solvent used at the time of polymerization include toluene, benzene, tetrahydrofuran, diethyl ether, dioxane, methanol, ethanol, isopropanol and the like. As polymerization initiators, 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2,4-dimethylvaleronitrile), dimethyl-2,2-azobis (2-methylpropio) Nate), benzoyl peroxide, lauroyl peroxide, and the like, preferably polymerized by heating to 50 to 80 ° C. The reaction time is 2 to 100 hours, preferably 5 to 20 hours. The fluoroalcohol group at the monomer stage is substituted with an acetyl group or an acetal, and may be converted to a fluoroalcohol by alkali treatment or acid treatment after polymerization.

  The resist protective film material of the present invention preferably further contains a solvent. By using the above-described polymer compound dissolved in a solvent, the film formability can be further improved. In this case, it is preferable to use a solvent so that the concentration of the polymer compound is 0.1 to 20% by mass, particularly 0.5 to 10% by mass, from the viewpoint of film formability by a spin coating method or the like.

  The solvent used is not particularly limited, but a solvent that does not dissolve the photoresist film is preferable. Examples of the solvent for dissolving the photoresist film include ketones such as cyclohexanone and methyl-2-n-amyl ketone used as the resist solvent, 3-methoxybutanol, 3-methyl-3-methoxybutanol, and 1-methoxy-2. -Alcohols such as propanol and 1-ethoxy-2-propanol, ethers such as propylene glycol monomethyl ether, ethylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monoethyl ether, propylene glycol dimethyl ether and diethylene glycol dimethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl lactate, ethyl pyruvate, butyl acetate, - methyl methoxypropionate, ethyl 3-ethoxypropionate, acetate tert- butyl, tert- butyl propionate, and esters such as propylene glycol monobutyl -tert- butyl ether acetate.

  In order not to dissolve the photoresist film, examples of the solvent preferably used in the present invention include non-polar solvents such as higher alcohols having 4 or more carbon atoms, toluene, xylene, anisole, hexane, cyclohexane, decane, and ether. In particular, higher alcohols having 4 or more carbon atoms and ethers having 8 to 12 carbon atoms are preferably used. Specifically, 1-butyl alcohol, 2-butyl alcohol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2 -Pentanol, 3-pentanol, tert-amyl alcohol, neopentyl alcohol, 2-methyl-1-butanol, 3-methyl-1-butanol, 3-methyl-3-pentanol, cyclopentanol, 1-hexanol 2-hexanol, 3-hexanol, 2,3-dimethyl-2-butanol, 3,3-dimethyl-1-butanol, 3,3-dimethyl-2-butanol, 2-diethyl-1-butanol, 2-methyl -1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentano , 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2-pentanol, 4-methyl -3-pentanol, cyclohexanol, diisopropyl ether, diisobutyl ether, diisopentyl ether, di-n-pentyl ether, methylcyclopentyl ether, methylcyclohexyl ether, di-n-butyl ether, di-secbutyl ether, diisopentyl ether , Di-sec-pentyl ether, di-t-amyl ether, di-n-hexyl ether.

On the other hand, since a fluorine-based solvent does not dissolve the photoresist film, it can be preferably used in the present invention.
Examples of such fluorine-substituted solvents include 2-fluoroanisole, 3-fluoroanisole, 4-fluoroanisole, 2,3-difluoroanisole, 2,4-difluoroanisole, 2,5-difluoroanisole, 5, 8-difluoro-1,4-benzodioxane, 2,3-difluorobenzyl alcohol, 1,3-difluoro-2-propanol, 2 ′, 4′-difluoropropiophenone, 2,4-difluorotoluene, trifluoroacetaldehyde Ethyl hemiacetal, trifluoroacetamide, trifluoroethanol, 2,2,2-trifluoroethyl butyrate, ethyl heptafluorobutyrate, ethyl heptafluorobutyl acetate, ethyl hexafluoroglutaryl methyl, ethyl-3-hydroxy 4,4,4-trifluorobutyrate, ethyl-2-methyl-4,4,4-trifluoroacetoacetate, ethyl pentafluorobenzoate, ethyl pentafluoropropionate, ethyl pentafluoropropynyl acetate, ethyl perfluoroocta Noate, ethyl-4,4,4-trifluoroacetoacetate, ethyl-4,4,4-trifluorobutyrate, ethyl-4,4,4-trifluorocrotonate, ethyltrifluorosulfonate, ethyl-3 -(Trifluoromethyl) butyrate, ethyl trifluoropyruvate, S-ethyl trifluoroacetate, fluorocyclohexane, 2,2,3,3,4,4,4-heptafluoro-1-butanol, 1,1,1 , 2,2,3,3-heptafluoro-7,7-dimethyl Til-4,6-octanedione, 1,1,1,3,5,5,5-heptafluoropentane-2,4-dione, 3,3,4,4,5,5,5-heptafluoro- 2-pentanol, 3,3,4,4,5,5,5-heptafluoro-2-pentanone, isopropyl 4,4,4-trifluoroacetoacetate, methyl perfluorodenanoate, methyl perfluoro (2 -Methyl-3-oxahexanoate), methyl perfluorononanoate, methyl perfluorooctanoate, methyl-2,3,3,3-tetrafluoropropionate, methyl trifluoroacetoacetate, 1,1, 1,2,2,6,6,6-octafluoro-2,4-hexanedione, 2,2,3,3,4,4,5,5-octafluoro-1-pentanol, 1H, H, 2H, 2H-perfluoro-1-decanol, perfluoro (2,5-dimethyl-3,6-dioxane anionic) acid methyl ester, 2H-perfluoro-5-methyl-3,6-dioxanonane, 1H 1H, 2H, 3H, 3H-perfluorononane-1,2-diol, 1H, 1H, 9H-perfluoro-1-nonanol, 1H, 1H-perfluorooctanol, 1H, 1H, 2H, 2H-perfluoro Octanol, 2H-perfluoro-5,8,11,14-tetramethyl-3,6,9,12,15-pentaoxaoctadecane, perfluorotributylamine, perfluorotrihexylamine, perfluoro-2,5 8-trimethyl-3,6,9-trioxadodecanoic acid methyl ester, perfluorotripentyl Min, perfluorotripropylamine, 1H, 1H, 2H, 3H, 3H-perfluoroundecane-1,2-diol, trifluorobutanol 1,1,1-trifluoro-5-methyl-2,4-hexanedione 1,1,1-trifluoro-2-propanol, 3,3,3-trifluoro-1-propanol, 1,1,1-trifluoro-2-propyl acetate, perfluorobutyltetrahydrofuran, perfluoro (butyl Tetrahydrofuran), perfluorodecalin, perfluoro (1,2-dimethylcyclohexane), perfluoro (1,3-dimethylcyclohexane), propylene glycol trifluoromethyl ether acetate, propylene glycol methyl ether trifluoromethyl acetate, trifluorome Butyl butyl acetate, methyl 3-trifluoromethoxypropionate, perfluorocyclohexanone, propylene glycol trifluoromethyl ether, butyl trifluoroacetate, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione 1,1,1,3,3,3-hexafluoro-2-propanol, 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 2,2,3,4 , 4,4-hexafluoro-1-butanol, 2-trifluoromethyl-2-propanol, 2,2,3,3-tetrafluoro-1-propanol, 3,3,3-trifluoro-1-propanol, 4,4,4-trifluoro-1-butanol and the like can be used, and one of these can be used alone or in admixture of two or more. But it is not limited thereto.

Next, a pattern forming method using the resist protective film material of the present invention will be described.
The pattern forming method of the present invention includes at least a step of forming a photoresist film on a substrate, a step of forming a resist protective film on the photoresist film using the resist protective film material of the present invention, It includes a step of exposing and a step of developing using a developer.

First, a photoresist film is formed on the substrate.
Examples of the film forming method include a spin coating method. At this time, in order to reduce the amount of dispensing in the spin coating of the photoresist film material, it is preferable to dispense and spin coat the photoresist film material while the substrate is coated with a photoresist solvent or a solution mixed with the photoresist solvent. (For example, refer to JP-A-9-246173). Thereby, the spread of the solution of the photoresist film material to the substrate is improved, and the dispense amount of the photoresist film material can be reduced.

  The type of the photoresist film material is not particularly limited. It may be a positive type or a negative type, and may be an ordinary hydrocarbon-based single layer resist material or a bilayer resist material containing silicon atoms.

  In the photoresist film material in KrF exposure, a part or all of hydrogen atoms of hydroxy group or carboxyl group of polyhydroxystyrene or polyhydroxystyrene- (meth) acrylate copolymer as a base resin is substituted with an acid labile group. Those containing a polymer are preferably used.

  The photoresist film material in ArF exposure must have a structure that does not contain an aromatic as a base resin. Specifically, polyacrylic acid and derivatives thereof, norbornene derivative-maleic anhydride alternating polymer and polyacrylic acid or Tri- or quaternary copolymers with derivatives thereof, tetracyclododecene derivatives-maleic anhydride alternating polymers and ternary or quaternary copolymers with polyacrylic acid or derivatives thereof, norbornene derivatives-maleimide alternating polymers and poly A ternary or quaternary copolymer with acrylic acid or a derivative thereof, a tetracyclododecene derivative-maleimide alternating polymer and a ternary or quaternary copolymer with polyacrylic acid or a derivative thereof, and two or more of these, Or one or more selected from polynorbornene and metathesis ring-opening polymers Those containing high molecular polymer are preferably used.

Next, a resist protective film is formed on the photoresist film using the resist protective film material of the present invention.
Examples of the film forming method include a spin coating method. In spin coating of resist protective film material, the same process as the above-mentioned photoresist film can be considered. Before applying the resist protective film material, apply the resist protective film material after applying the surface of the photoresist film with a solvent. May be. The thickness of the resist protective film to be formed is preferably in the range of 10 to 500 nm. For coating the surface of the photoresist film with a solvent, a spin coating method or a vapor prime method can be used, but the spin coating method can be more preferably used. The solvent used at this time is more preferably selected from higher alcohols, ether-based and fluorine-based solvents that do not dissolve the aforementioned photoresist film.

  When exposure is performed by immersion lithography as will be described later, the presence / absence of cleaning of the substrate edge and back surface and the cleaning method are important in order to prevent water from flowing into the back surface of the substrate and elution from the substrate. For this reason, for example, it is preferable to volatilize the solvent by forming a resist protective film by spin coating and then baking it at 40 to 130 ° C. for 10 to 300 seconds. In addition, edge cleaning is performed at the time of spin coating in the case of a photoresist film or dry exposure, but in the case of immersion exposure, when a highly hydrophilic substrate surface comes into contact with water, water may remain on the substrate surface of the edge portion. Yes, not preferable. Therefore, there is a method in which edge cleaning is not performed during spin coating of the resist protective film.

Next, exposure is performed.
Examples of the exposure method include dry exposure in which the space between the projection lens and the substrate is a gas such as air or nitrogen.

  However, in the present invention, the exposure process is preferably performed by immersion lithography performed by inserting a liquid between the projection lens and the substrate. Water is preferably used as the liquid inserted between the projection lens and the substrate. The exposure is preferably performed using a light source having an exposure wavelength in the range of 180 to 250 nm, for example, a KrF excimer laser (248 nm) or an ArF excimer laser (193 nm).

Next, development is performed.
In the development step, for example, development is performed with an alkali developer for 10 to 300 seconds. As the alkali developer, a 2.38 mass% tetramethylammonium hydroxide aqueous solution is generally widely used.

  In this case, it is preferable that in the development step, development is performed using an alkaline developer to form a resist pattern on the photoresist film, and at the same time, the resist protective film on the photoresist film is peeled off. In this way, the resist protective film can be peeled off more easily without adding a peeling apparatus to the conventional apparatus.

  Further, post exposure baking (PEB) is preferably performed after exposure and before development. In the case of immersion lithography using water, water may remain on the resist protective film before PEB. If PEB is performed in a state where water remains, water passes through the resist protective film, and the acid in the photoresist film is sucked out, so that a good pattern may not be formed. Therefore, in order to completely remove the water on the resist protective film before PEB, spin drying before PEB, purging with dry air or nitrogen on the surface of the protective film, or the shape of the water recovery nozzle on the stage after exposure or water recovery It is preferable to dry or recover the water on the protective film by optimizing the process. In this case, by improving the water repellency of the resist protective film, the water recoverability is excellent.

  In addition to the above steps, it goes without saying that other various steps such as an etching step, a resist removal step, and a cleaning step may be performed.

EXAMPLES Hereinafter, although an Example, a comparative example, etc. are shown and this invention is demonstrated further more concretely, this invention is not limited by these description.
In the examples, GPC is gel permeation chromatography, and the polystyrene-reduced mass average molecular weight (Mw) and number average molecular weight (Mn) were determined.

  Here, the amine compound added to the resist protective film material in Examples and Comparative Examples described later is shown. The added amine compounds are tri-n-octylamine, tri-n-dodecylamine, F-amine compound 1, F-amine compound 2, F-amine compound 3, F-amine compound 4, F- Amine compound 5, trifluoromethanesulfonyldecylamine, trifluoromethanesulfonyl-1-adamantylamine, amine compound 1, amine compound 2, amine compound 3, amine compound 4, amine compound 5, and amine compound 6 shown below.

Among the amine compounds, F-amine compounds 1 to 5 were synthesized according to the following synthesis method.
(Synthesis Example 1)
Synthesis of F-amine compound 1 12.2 g of di-n-butylamine was added dropwise to 20.4 g of 2,2,3,3,3-pentafluoropropyl acrylate with ice cooling and stirring. After stirring at room temperature for 1 hour, the reaction mixture was directly purified by distillation to obtain F-amine compound 1.

(Synthesis Example 2)
Synthesis of F-amine compound 2 8.3 g of piperidine was added dropwise to 28.6 g of 2,2,3,3,4,4,5,5-octafluoropentyl acrylate with ice cooling and stirring. After stirring at room temperature for 1 hour, the reaction mixture was directly distilled and purified to obtain F-amine compound 2.

(Synthesis Example 3)
Synthesis of F-amine compound 3 2.2 g of ammonia was added dropwise to 46.2 g of 2,2,2-trifluoroethyl acrylate with ice cooling and stirring. After stirring at room temperature for 1 hour, the reaction mixture was directly distilled and purified to obtain F-amine compound 3.

(Synthesis Example 4)
Synthesis of F-amine compound 4 120 g of 2,2,3,3,4,4,5,5-octafluoro-1-pentanol was added at 0 ° C. to a mixture of 110 g of 1- (2-chloroethyl) piperidine and 500 g of tetrahydrofuran. added. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain F-amine compound 4.

(Synthesis Example 5)
Synthesis of F-amine compound 5 8.3 g of piperidine was added dropwise to 38.6 g of 1-isopropyl-2,2,3,3,4,4,4-heptafluorobutyl acrylate with ice cooling and stirring. After stirring at room temperature for 1 hour, the reaction mixture was directly distilled and purified to obtain F-amine compound 5.

Among the amine compounds, amine compounds 1 to 6 were synthesized according to the following synthesis method.
(Synthesis Example 6)
Synthesis of Amine Compound 1 320 g of nonadecanoyl chloride was added at 0 ° C. to a mixture of 131 g of 1- (2-hydroxyethyl) piperidine, 106 g of triethylamine, and 500 g of tetrahydrofuran. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain amine compound 1.

(Synthesis Example 7)
Synthesis of Amine Compound 2 320 g of 1-adamantaneacetyl chloride was added at 0 ° C. to a mixture of 131 g of 1- (2-hydroxyethyl) piperidine, 106 g of triethylamine, and 500 g of tetrahydrofuran. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain amine compound 2.

(Synthesis Example 8)
Synthesis of Amine Compound 3 To a mixture of 149 g of triethanolamine, 106 g of triethylamine, and 500 g of tetrahydrofuran, 410 g of hexanoyl chloride was added at 0 ° C. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain amine compound 3.

(Synthesis Example 9)
Synthesis of Amine Compound 4 To a mixture of 149 g of triethanolamine, 106 g of triethylamine, and 500 g of tetrahydrofuran was added 640 g of 1-iodohexane at 0 ° C. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain amine compound 4.

(Synthesis Example 10)
Synthesis of Amine Compound 5 To a mixture of 89 g of N, N-dimethylethanolamine, 106 g of triethylamine, and 500 g of tetrahydrofuran, 270 g of chloroacetic acid dodecyl ether was added at 0 ° C. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain amine compound 5.

(Synthesis Example 11)
Synthesis of Amine Compound 6 280 g of palmitoyl chloride was added at 0 ° C. to a mixture of 89 g of N, N-dimethylethanolamine, 106 g of triethylamine and 500 g of tetrahydrofuran. After heating up to 20 degreeC over 10 hours, water was added and reaction was stopped. Ethyl acetate was added thereto for liquid separation, and the organic layer was washed with water and concentrated under reduced pressure. Purification was performed by distillation under reduced pressure to obtain amine compound 6.

Moreover, the following polymers 1-7 were synthesize | combined by radical polymerization by a conventional method.

(Examples and comparative examples)
A polymer compound, an amine compound, and a solvent for the resist protective film material are mixed in the compositions shown in Tables 1 and 2 and filtered through a 0.2 micron-size high-density polyethylene filter. 28, Comparative TC-1 to 3) solution was prepared.

  A resist protective film material solution is spin-coated on a silicon substrate and baked at 100 ° C. for 60 seconds to form 50 nm-thick resist protective films (TC-1 to 28, comparative TC-1 to 3). A. The refractive index of the protective film at a wavelength of 193 nm was determined using spectroscopic ellipsometry manufactured by Woollam. The results are shown in Table 3.

  Next, the silicon substrate on which the resist protective film was formed by the above method was rinsed with pure water for 5 minutes, and the change in film thickness was observed. The results are shown in Table 4.

  From Table 4, it can be seen that the resist protective films TC-1 to TC28 have high water repellency and are difficult to dissolve in water.

  Next, using a silicon substrate on which a resist protective film was formed by the above method, development was performed with an aqueous 2.38 mass% tetramethylammonium hydroxide (TMAH) solution, and the film thickness of the resist protective film after development was observed. The results are shown in Table 5.

  From Table 5, it can be seen that the resist protective films TC-1 to TC28 have high alkali solubility and can be easily removed with an alkaline developer during development.

  Next, using an inclination method contact angle meter Drop Master 500 manufactured by Kyowa Interface Science, 50 μL of pure water was dropped onto a silicon substrate that was kept horizontal by forming a resist protective film by the above method to form polka dots. . Next, the silicon substrate was gradually tilted, and the angle (falling angle) and receding contact angle of the silicon substrate at which the polka dots began to fall were obtained. The results are shown in Table 6.

  A small falling angle indicates that water easily flows, and a large receding contact angle indicates that it is difficult for a droplet to remain even in high-speed scanning exposure. From Table 6, it can be seen that the resist protective films TC-1 to TC-28 are suitable as a resist protective film for immersion lithography because water easily flows and liquid droplets hardly remain even at high-speed scanning exposure. That is, it can be seen that even when an amine compound is added as in the resist protective film of the present invention, there is almost no adverse effect on the sliding angle and receding contact angle.

  Further, 5 g of resist polymer shown below, 0.25 g of PAG, and 0.05 g of amine quencher were dissolved in 75 g of propylene glycol monoethyl ether acetate (PGMEA) solution, filtered through a 0.2 micron polypropylene filter, A resist film material solution was prepared.

Next, an antireflection film ARC-29A manufactured by Nissan Chemical Industries, Ltd. having a film thickness of 87 nm was formed on the silicon substrate.
Next, a solution of the photoresist film material prepared above was applied onto the substrate on which the antireflection film was formed, and baked at 120 ° C. for 60 seconds to form a resist film having a thickness of 150 nm.
Next, a resist protective film material prepared in the same manner as described above is applied onto the photoresist film, and baked at 100 ° C. for 60 seconds to form resist protective films (TC-1 to 28, comparative TC-1 to TC-3). Formed.
Next, in order to reproduce the pseudo immersion exposure, pure water rinsing was performed for 5 minutes on the exposed film. That is, it was exposed with a Nikon ArF scanner S307E (NA0.85 σ0.93 4/5 annular illumination, 6% halftone phase shift mask), rinsed for 5 minutes while applying pure water, and post-treated at 110 ° C. for 60 seconds. Exposure bake (PEB) was performed, and development was performed for 60 seconds with a 2.38% by mass TMAH developer.
On the other hand, a process of performing exposure, pure water rinsing, PEB, and development without forming a resist protective film, and a normal process without performing post-exposure pure water rinsing were also performed.
Next, the silicon substrate was cleaved, and the pattern shape and sensitivity of the 75 nm line and space were compared. In addition, the exposure amount which resolves 75 nm line and space by 1: 1 was made into the sensitivity.
The results are shown in Table 7.

As shown in Table 7, when pure water rinsing was performed after exposure without a protective film, a T-top shape was obtained. This is probably because the generated acid was dissolved in water. On the other hand, when the protective film (TC-1 to 28) of the present invention was used, the shape change hardly occurred.
On the other hand, in the case of the protective film to which the conventional amine compound was not added (Comparative TC-1 to TC-3), the resist shape after development became a reduced film shape.

  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.

Claims (14)

  A resist protective film material for forming a protective film on a photoresist film, the polymer compound containing at least one repeating unit having at least one of a carboxyl group and an α-trifluoromethyl alcohol group, and an amine compound A resist protective film material comprising:   The resist protective film material according to claim 1, wherein the amine compound is one or more of a tertiary amine compound and a sulfonic acid amide compound. One or more compounds among the tertiary amine compound and the sulfonic acid amide compound are compounds represented by the following general formula (1-1) and one of the compounds represented by the following general formula (1-2). The resist protective film material according to claim 2, which is the above compound.

(In the above formula, R ¹ , R ² and R ³ are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and R ¹ and R ² , R ¹ and R ^3. , R ² and R ³ may be bonded to each other to form a ring, and may have any one or more of an ester, an ether group, and an amino group, and a hydrogen atom of an alkyl group R ⁴ , R ⁵ , and R ⁶ are each independently a hydrogen atom, a linear, branched, or cyclic alkyl group having 1 to 30 carbon atoms. , —SO ₂ R ⁷ , and R ⁴ and R ⁵ , R ⁴ and R ⁶ , or R ⁵ and R ⁶ may be bonded to each other to form a ring, and R ⁴ , at least one of R ^{5, R 6} is a _-SO 2 ^{R 7} .R ⁷ is a straight, branched, or A Jo alkyl group, all or some of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom.) The resist protective film material according to claim 2, wherein one or more compounds among the tertiary amine compounds are compounds represented by the following general formula (2).
N (X ¹⁰ ) _n1 (Y ¹⁰ ) _3-n1 (2)
(In the above formula, n1 is any one of 1, 2, and 3. X ¹⁰ may be the same or different, and any one of the following general formulas (X ¹⁰ ) -1 to (X ¹⁰ ) -3. Y ¹⁰ may be the same or different, and represents a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, and Y ¹⁰ may be bonded to each other to form a ring. Well, the ring may contain -O-.)

(In the above formula, R ³⁰⁰ , R ³⁰² , and R ³⁰⁵ are each independently a linear or branched alkylene group having 1 to 4 carbon atoms, and may include —O—. R ³⁰¹ , R ³⁰⁴ Are each independently a linear, branched or cyclic alkyl group having 1 to 30 carbon atoms, which may have a hydroxy group or an ester group, and all or part of the hydrogen atoms of the alkyl group are R ³⁰³ is a single bond or a linear or branched alkylene group having 1 to 4 carbon atoms, and R ³⁰⁶ is a linear or branched group having 1 to 30 carbon atoms. A cyclic or cyclic alkyl group, and all or part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms.) The repeating unit having an α trifluoromethyl alcohol group in the polymer compound is a repeating unit represented by the following general formula (3). Resist protective film material.

(In the above formula, each of R ¹⁸ and R ²⁰ is independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Y is independently a single bond, —O—, — C (═O) —O—, —C (═O) —O—R ²⁸ —C (═O) —O—, —C (═O) —O—R ²⁸ —O—, —C (═O ) —O—R ²⁸ —O—C (═O) —, wherein R ²⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and is a hydrogen atom of the alkylene group. R ²⁶ may be each independently a single bond, a linear, branched or cyclic alkylene group having 1 to 25 carbon atoms, or an alkanetriyl group. Any or all of the hydrogen atoms of the alkylene group or alkanetriyl group are substituted with fluorine atoms. May have, R ¹⁷ are each independently hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a difluoromethyl group, R ²⁶ and R ¹⁷ may combine to form a ring The ring may have one or more groups among an ether group, an alkylene group in which all or part of the hydrogen atoms are substituted with fluorine atoms, and a trifluoromethyl group. Each independently is 1 or 2. (a-1) and (a-2) are 0 ≦ (a-1) ≦ 0.9, 0 ≦ (a-2) ≦ 0.9, 0 ≦. (A-1) + (a-2) ≦ 0.9.) 6. The resist protective film material according to claim 5, wherein the repeating unit having an α-trifluoromethyl alcohol group in the polymer compound is a repeating unit represented by the following general formula (4).

(In the formula, R ³⁰ is a hydrogen atom or a methyl ^group, R ^{31, R 32} are identical or different hydrogen atoms or C 1 -C 12 straight, branched or cyclic alkyl ^group, and ^{R 31} R ³² may be bonded to form a ring together with the carbon atoms to which these are bonded.) The resist protective film according to any one of claims 1 to 6, wherein the repeating unit having a carboxyl group in the polymer compound is a repeating unit represented by the following general formula (5). material.

(In the above formula, R ²⁹ is any one of a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, —COOH, —CH ₂ —COOH. R ¹⁹ is a hydrogen atom, a fluorine atom, a methyl group, Any one of a trifluoromethyl group, —COOH, and —CH ₂ —COOH, each of Y is independently a single bond, —O—, —C (═O) —O—, —C (═O) —; O—R ²⁸ —C (═O) —O—, —C (═O) —O—R ²⁸ —O—, —C (═O) —O—R ²⁸ —O—C (═O) — R ²⁸ is a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and all or part of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms. R ²⁶ independently represents a single bond, the number 1 to 25 linear, alkylene branched or cyclic Or an alkanetriyl group, and all or part of the hydrogen atoms of the alkylene group or alkanetriyl group may be substituted with fluorine atoms, and n is independently 1 or 2. (B-1) and (b-2) are 0≤ (b-1) ≤0.9, 0≤ (b-2) ≤0.9, 0≤ (b-1) + (b-2) ≦ 0.9.)   8. The resist protective film material according to any one of claims 1 to 7, wherein the resist protective film material contains a polymer compound including a repeating unit having at least one of an alkyl group and a fluoroalkyl group. The resist protective film material described in 1. 9. The resist protective film according to claim 8, wherein the repeating unit having one or more of an alkyl group and a fluoroalkyl group in the polymer compound is a repeating unit represented by the following general formula (6). material.

(In the above formula, R ⁸ and R ¹⁰ are each independently a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. X ² is independently a single bond, —O—, Or —C (═O) —O— or —C (═O) —O—R ¹⁶ —C (═O) —O—, wherein R ¹⁶ is a straight chain having 1 to 10 carbon atoms, It is a branched or cyclic alkylene group, and all or part of the hydrogen atoms of the alkylene group may be substituted with fluorine atoms, and each R ⁹ is independently a linear or branched group having 1 to 20 carbon atoms. Or all or part of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, or may have an ether group or an ester group, R ^{11 to} R ¹⁴ are Each independently of a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. And in either ^{displacement,} .m of R 11 ^{to R 14,} either with at least one fluorine atom is 1 or 2. (C-1), (c-2), (c- 3), (c-4), and (c-5) are 0 ≦ (c-1) ≦ 0.9, 0 ≦ (c-2) ≦ 0.9, 0 ≦ (c-3) ≦ 0. 9, 0 ≦ (c−4) ≦ 0.9, 0 ≦ (c−5) ≦ 0.9, 0 ≦ (c−1) + (c−2) + (c−3) + (c−4) ) + (C-5) ≦ 0.9.)   The resist protective film material according to any one of claims 1 to 9, wherein the resist protective film material further contains a solvent.   At least a step of forming a photoresist film on the substrate, and a resist protective film is formed on the photoresist film using the resist protective film material according to any one of claims 1 to 10. The pattern formation method characterized by including the process, the process to expose, and the process to develop using a developing solution.   12. The pattern forming method according to claim 11, wherein the exposure step is performed by immersion lithography performed by inserting a liquid between the projection lens and the substrate.   The pattern formation according to claim 12, wherein the exposure step is performed using water as a liquid inserted between the projection lens and the substrate using a light source having an exposure wavelength in a range of 180 to 250 nm. Method.   14. The developing process according to claim 12 or 13, wherein, in the developing step, development is performed using an alkali developer to form a resist pattern on the photoresist film, and at the same time, the resist protective film on the photoresist film is removed. The pattern forming method according to 1.